Insecticidal N' substituted-N-N'-disubstituted-hydrazines

BACKGROUND OF THE INVENTION
This invention relates to N'-substituted-N,N'-disubstitutedhydrazines, which are useful as insecticides, compositions containing those compounds and methods of their use. More particularly, the invention relates to
The search for compounds which have a combination of excellent insecticidal activity and low undesirable toxicity is a continuing one because of factors such as the desire for compounds exhibiting greater activity, better selectivity, low undesirable environmental impact, low production cost and effectiveness against insects resistant to many known insecticides.
Compounds of the present invention are particularly suitable for controlling plant-destructive insects in crops of cultivated plants, ornamentals and forestry.
Certain hydrazine derivatives have been disclosed in the literature. However, none of the prior art literature suggests hydrazines derivatives having insect growth regulating characteristics.
U.S. Pat. No. 3,481,972 discloses 2-(betahydroxyethyl)-2-methyl acid hydrazine compounds of the formula ZC(O)NHN(CH.sub.3)CH.sub.2 CH.sub.2 OH where Z represents furyl, cyclohexyl, phenyl, benzyl, styryl, dihydrostyryl or substituted phenyl. The compounds are stated to be useful as pesticides for the control of such organisms as insects, arachnids, nematodes, fungi, plants and helminth organisms.
U.S. Pat. No. 4,062,934 discloses compounds of the formula ##STR2## where R.sub.3 and R.sub.4 represent a hydrogen atom or a one to four alkyl and n is an integer from zero to four. These compounds are used as X-ray contrast media.
U.S Pat. No. 4,189,482 discloses compounds of the formula ##STR3## where R.sub.3 is lower alkyl, or substituted or unsubstituted phenyl, benzyl, phenethyl, thienyl or furyl; R.sub.4 is hydrogen or lower alkyl; ##STR4## as intermediates to penicillins having an imino substituted piperazindioncarbonylamino aceyl side chains.
U.S. Pat. No. 4,317,741 discloses a poly(oxyalkylated)hydrazine of the formula ##STR5## where R is hydrogen, (C.sub.1 -C.sub.4)alkyl, phenyl or mixtures thereof and the sum of w, x, y and z is from about four to about 20. These compounds are used as corrosion inhibitors.
U.S. Pat. No. 4,357,351 discloses five specific compounds (Compound Nos. 400 and 402-404) of the formula ##STR6## where n averages 7.7 and n' averages 11. These compounds are disclosed to have leptericidal activity. However, they are not claimed and it is not seen how these five compounds are included in the generic formula disclosed in the patent.
U.S. Pat. No. 4,547,524 discloses a class of benzoyl hydrazone derivatives which have insecticidal activity. However, the unsaturated carbon is bonded to hydrogen, lower alkyl, or phenyl, or forms part of a cyclohexane ring. Further the N'-substituent is not taught to include a tertiary carbon atom.
U.S. Pat. No. 4,564,611 discloses (di)thiophosphoric and -phosphonic acid derivatives having the formula ##STR7## in which R denotes (C.sub.1 -C.sub.4)-alkyl; R.sub.1 denotes (C.sub.1 -C.sub.4)-alkyl, (C.sub.1 -C.sub.4)-alkoxy, (C.sub.1 -C.sub.4)-alkylmercapto, (C.sub.1 -C.sub.4)-alkylamino or di(C.sub.1 -C.sub.4)alkylamino; R.sub.2 and R.sub.3 independently of one another denote hydrogen, (C.sub.1 -C.sub.4)-alkyl, (C.sub.5 -C.sub.6)-cycloalkyl, benzyl or furylmethyl; R.sub.4 denotes (C.sub.1 -C.sub.4)-alkyl, (C.sub.1 -C.sub.3)-alkoxymethyl, (C.sub.1 -C.sub.3)-alkylmercaptomethyl or phenyl and X denotes oxygen or sulfur, which have activity against sucking and biting insects, acarides and nematodes, and display good fungicidal activity. Insect growth regulating activity is not disclosed. Further, R.sub.2 is not taught to include a tertiary carbon.
The Chemical Abstracts citation CA 84(21):150168j indicates that Azerb Khim Zh, 1975, (5), 47-8 discloses Me.sub.2 CHCH.sub.2 CH.dbd.NN(Ac)CH.sub.2 CH.sub.2 OH, PhCH.dbd.NN(Ac)CH.sub.2 CH.sub.2 OH and Me.sub.2 CHCH.dbd.NN(Ac)CH.sub.2 CH.sub.2 OH which have pesticidal activity.
In 88 J.A.C.S, 4677-4681 (1966) N'-t-butyl-N'-methylcarbonyl-N-benzoylhydrazine is disclosed. No biological activity is disclosed.
In 37 Tetrahedron Letters, 3575-3578 (1979), the result of an electron spin resonance study is reported. The hydrazyl radicals produced included PhC(O)N(t-Bu)NC(O)Ph and PhC(O)N(Et.sub.3 Si)NC(O)Ph. No utility was suggested for the radicals which were studied.
In 25 Aust. J. Chem., 523-529 (1972), several N,N'-dibenzoylhydrazine derivatives are disclosed including (3-methylbutyl)-; N'-benzyl- and N'-phenyl-N,N'-dibenzoylhydrazine in which one or both nitrogen atoms are alkylated or phenylated. No biological activity is disclosed for those compounds.
In 61 Helv. Chim. Acta, 1477-1510 (1978), several N,N'-dibenzoylhydrazine and hydrazide derivatives including N'-t-butyl-N-benzoyl-N'-(4-nitrobenzoyl)hydrazine are disclosed. No biological activity is disclosed for those compounds.
In 44 J.A.C.S., 2556-2567 (1922), isopropylhydrazine (CH.sub.3).sub.2 CH--NH--NH.sub.2, symmetrical diisopropylhydrazine, dibenzoylisopropylhydrazine and certain derivatives are disclosed. No biological activity is disclosed for those compounds.
In 44 J.A.C.S., 1557-1564 (1972), isopropyl, methyl and bornyl semicarbazides are disclosed. No biological activity is disclosed for those compounds.
In 48 J.A.C.S., 1030-1035 (1926), symmetrical di-methylphenylmethylhydrazine and certain related compounds including 1,2-bis-methylphenylmethyl-4-phenylsemicarbazide are disclosed. No biological activity is disclosed for those compounds.
In 27 Bull. Chem. Soc. Japan, 624-627 (1954), certain hydrazine derivatives including alpha,beta-dibenzoylphenylhydrazine are disclosed. No biological activity is disclosed for those compounds.
In J. Chem. Soc. (C), 1531-1536 (1966), N,N'-dibenzoylphenylhydrazine and N-acetyl-N'-benzoyl-p-nitrophenylhydrazine are disclosed. No biological activity is disclosed for those compounds.
In 56B Chem. Berichte, 954-962 (1923), symmetrical di-isopropylhydrazines, symmetrical diisobutyl- and certain derivatives including N,N'-diisobutyldibenzoylhydrazine are disclosed. No biological activity is disclosed for those compounds.
In 590 Annalen der Chemie, 1-36 (1954), certain N,N'-dibenzoylhydrazine derivatives are disclosed including N'-methyl- and N'-(2-phenyl)-isopropyl-N,N'-dibenzoylhydrazine. No biological activity is disclosed for those compounds.
In J. Chem. Soc., 4191-4198 (1952), N,N'-di-n-propylhydrazine, N,N'-dibenzoylhydrazine and bis-3,5-dinitrobenzoyl are disclosed. No biological activity is disclosed for those compounds.
In 32 Zhur. Obs. Khim., 2806-2809 (1962), N'-2,4-methyl-2,4-pentadiene-N,N'-dibenzoylhydrazine is disclosed. No biological activity is disclosed.
In 17 Acta. Chim. Scand., 95-102 (1963), 2-benzoyloylhydrazide (C.sub.6 H.sub.5 --CS--NHNH--CO--C.sub.6 H.sub.5) and certain hydrazone and hydrazine derivatives are disclosed including 1,2-dibenzoyl-benzylhydrazine. No biological activity is disclosed for those compounds.
In 25 Zhur. Obs. Khim, 1719-1723 (1955), N,N'-biscyclohexylhydrazine and N,N'-dibenzoylcyclohexylhydrazine are disclosed. No biological activity is disclosed for those compounds.
In J. Chem. SOc., 4793-4800 (1964), certain dibenzoylhydrazine derivatives are disclosed including tribenzoylhydrazine and N,N'-dibenzoylcyclohexylhydrazine. No biological activity is disclosed for those compounds.
In 36 J. Prakt. Chem., 197-201 (1967), certain dibenzoylhydrazine derivatives including N'-ethyl-; N'-n-propyl-; N'-isobutyl-; N'-neopentyl-; N'-n-heptyl-; and N'-cyclohexylmethyl-N,N'-dibenzoylhydrazines are disclosed. No biological activity is disclosed for those compounds.
In 26 J.O.C., 4336-4340 (1961) N'-t-butyl-N,N'-di-(t-butoxycarbonyl)hydrazide is disclosed. No biological activity is disclosed.
In 41 J.O.C., 3763-3765 (1976), N'-t-butyl-N-(phenylmethoxycarbonyl)-N'-(chlorocarbonyl)hydrazide is disclosed. No biological activity is disclosed.
In 94 J.A.C.S., 7406-7416 (1972) N'-t-butyl-N,N'-dimethoxycarbonylhydrazide is disclosed. No biological activity is disclosed.
In 43 J.O.C., 808-815 (1978), N'-t-butyl-N-ethoxycarbonyl-N'-phenylaminocarbonylhydrazide and N'-t-butyl-N-ethoxycarbonyl-N'-methylaminocarbonylhydrazide are disclosed. No biological activity is disclosed for those compounds.
In 39 J. Econ. Ent., 416-417 (1946), certain N-phenyl-N'-acylhydrazines are disclosed and evaluated for their toxicity against codling moth larvae.
Compounds of the present invention are distinguished by their excellent insecticidal activity, particularly against insects of the orders Lepidoptera and Coleoptera, and most particularly by their insect growth regulating activity without material adverse impact on beneficial insects.
SUMMARY OF THE INVENTION
In accordance with the present invention, there are provided novel insect growth regulating compositions including compounds having the formula: ##STR8## where one G.sub.1 is C, N, O or S, and both G.sub.2 's and the other G.sub.1 are carbon; or one G.sub.2 is S or P, and both G.sub.1 's and the other G.sub.2 are carbon; where the bond shown as -- is a single or double bond: or an agronomically acceptable salt thereof.
The invention also relates to compounds having the nucleus of the formula ##STR9## where N is nitrogen; where A', B', D and J are independently any atom or group of atoms; where E is a tertiary carbon containing organic radical, a haloalkyl having a total of at least four carbon and halogen atoms but not more than six halogen atoms, or a non-tertiary carbon containing non-haloalkyl organic or organometallic radical having at least five atoms other than hydrogen, oxygen and halogen, and is attached to the nitrogen shown in the formula by a carbon-to-nitrogen single bond; where one G.sub.1 is carbon, nitrogen, oxygen or sulfur, and both G.sub.2 's and the other G.sub.1 are carbon; or one G.sub.2 is sulfur or phosphorus, and both G.sub.1 --s and the other G.sub.2 are carbon; where the bonds shown as -- are independently single or double bonds; provided that when the G.sub.2 adjacent D is carbon or phosphorus, one of D--G.sub.2 and G.sub.2 --N is a double bond the other is a single bond; provided that when the G.sub.2 adjacent D is sulfur, D--G.sub.2 is a double bond and G.sub.2 --N is a single bond; where the A'-?-G.sub.1 and G.sub.1 -?-B' bonds are independently single bond, double bonds or aromatic bonds; provided that the D--G.sub.2 bond is other than a carbon-to-carbon or hydrogen-to-carbon single bond; provided that the J--G.sub.2 bond is a double bond or a hydrogen-to-carbon single bond; provided that at least one of A' and B' is other than hydrogen when the D--G.sub.2 bond is a double bond; provided that A' comprises at least two non-hydrogen atoms when the G.sub.1 adjacent A' is a carbon; provided that B' is other than a hydrogen atom when the G.sub.1 adjacent B' is a carbon; provided that E is not a straight chain alkyl, --CH.sub.2 CH.sub.2 N(CH.sub.2 CH.sub.3).sub.2, cyclohexyl, a six-membered cyclic containing organic radical, a cyclic aromatic radical, or an organic radical containing ##STR10## provided that E is not a sulfur or oxygen containing organic radical; provided that E does not have a chain length of non-hydrogen atoms greater than five; provided that when A'-?-G.sub.1 and G.sub.1 -?-B' are phenyl, and J--G.sub.2 are carbonyl and hydrogen is bonded to the nitrogen adjacent the D--G.sub.2, E is not neopentyl; provided that when A'-?-G.sub.1 is phenyl, D--G.sub.2 and J--G.sub.2 are carbonyl, hydrogen is bonded to the nitrogen adjacent the D--G.sub.2 and E is t-butyl, G.sub.1 -?-B' is not 4-nitrophenyl; where organic radical is a radical comprising at least one carbon atom, but no metal atoms; and where organometallic radical is a radical containing a carbon-to-metal bond; or an agronomically acceptable salt thereof.
The invention also relates to a method of regulating insect growth which comprises contacting insects with a compound having the nucleus of the formula ##STR11## where one G.sub.1 is carbon, nitrogen, oxygen or sulfur, and both G.sub.2 's and the other G.sub.1 are carbon; or one G.sub.2 is sulfur or phosphorus, and both G.sub.1 's and the other G.sub.2 are carbon; where the bond shown as -- is a single or double bond; or an agronomically acceptable salt thereof.
DETAILED DESCRIPTION OF THE INVENTION
The term "halo" should be understood as including chloro, fluoro, bromo and iodo. The term "alkyl" by itself or as a part of another substituent, unless otherwise stated, includes straight or branched chain groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, neopentyl and the like and where indicated higher homologues and isomers such as n-octyl, isooctyl and the like. The term "haloalkyl" by itself or as part of another substituent is an alkyl group of the stated number of carbon atoms having one or more halo atoms bonded thereto such as chloromethyl, 1- or 2-bromoethyl, trifluoromethyl and the like. Analogously, "cyanoalkyl" by itself or as part of another group is an alkyl group of the stated number of carbon atoms having one or more cyano groups bonded thereto; "haloalkoxy" by itself or as part of another group is an alkoxy group of the stated number of carbon atoms having one or more halo atoms bonded thereto such as difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2,2,2-trifluoroethoxy and the like. "Alkenyl" and "alkynyl" by themselves or as part of another substituent comprise straight and branched chain groups of the stated number of carbon atoms. "Alkadienyl" is a straight or branched chain alkenyl group comprising two carbon-to-carbon double bonds that can be conjugated such as 1,3-butadienyl, cumulated such as 1,2-propadienyl or isolated such as 1,4-pentadienyl.
The term "organic radical" should be understood to mean a radical comprising at least one carbon atom but no metal atoms. Examples of organic radicals include alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocycles, esters, ethers, thio derivatives and amine derivatives.
The term "organometallic radical" should be understood to include radicals containing a carbon-to-metal bond. Examples of such radicals include trimethylsilyl.
The term "tertiary carbon" is meant to refer to a carbon having at least three carbon-to-carbon single bonds.
The term "aryl" should be understood to include those molecules which have a ring structure characteristic of benzene, naphthalene, phenanthrene and anthracene, that is either the six-carbon ring of benzene or the condensed six-carbon rings of other aromatic derivatives. Examples of aryl radicals include unsubstituted and substituted phenyl, benzyl and naphthalene.
The term "cyclic aromatic radical" should be understood to mean unsaturated cyclic compounds including heterocyclic compounds. Examples of cyclic aromatic radicals include aryl, indolyl, thienyl, furyl, pyrrolyl, triazolyl and tetrazolyl.
Representative examples of six-membered heterocycles having one, two, three or four nitrogen atoms and two to five nuclear carbon atoms include 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 5-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 3-pyrazinyl, 2-(1,3,5-triazinyl), 3-(1,2,4-triazinyl), 5-(1,2,4-triazinyl), 6-(1,2,4-triazinyl), 4-(1,2,3-triazinyl) and 5-(1,2,3-triazinyl).
Representative examples of five-membered heterocycles include 2-furyl; 3-furyl; 2-thienyl; 3-thienyl; 4-(1,2,3-triazolyl); 3-(1,2,4-triazolyl); 5-(1,2,4-triazolyl), 2-pyrrolyl; 2-oxazolyl; and the like.
Those N'-substituted-N,N'-diacylhydrazines of Formula I which possess acidic or basic functional groups may be further reacted to form novel salts with appropriate bases or acids. These salts also exhibit pesticidal activity. Typical salts are the agronomically acceptable metal salts, ammonium salts and acid addition salts. Among the metal salts are those in which the metal cation is an alkali metal cation such as sodium, potassium, lithium or the like; alkaline earth metal cation such as calcium, magnesium, barium, strontium or the like; or heavy metal cation such as zinc, manganese, cupric, cuprous, ferric, ferrous, titanium, aluminum or the like. The ammonium salts include those in which the ammonium cation has the formula NR.sup.5 R.sup.6 R.sup.7 R.sup.8 wherein each of R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are independently hydrogen, hydroxy, (C.sub.1 -C.sub.4)alkoxy, (C.sub.1 -C.sub.20)-alkyl, (C.sub.3 -C.sub.8)alkenyl, (C.sub.3 -C.sub.8)alkynyl, (C.sub.2 -C.sub.8)hydroxyalkyl, (C.sub.2 -C.sub.8)alkoxyalkyl, (C.sub.2 -C.sub.6)aminoalkyl, (C.sub.2 -C.sub.6)haloalkyl, amino, (C.sub.1 -C.sub.4)alkyl- or (C.sub.1 -C.sub.4)dialkylamino, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, having up to four carbon atoms in the alkyl moiety, or any two of R.sup.5, R.sup.6, R.sup.7 or R.sup.8 can be taken together to form with the nitrogen atom a 5- or 6-membered heterocyclic ring, optionally having up to one additional hetero atom (e.g., oxygen, nitrogen, or sulfur) in the ring, and preferably saturated, such as piperidino, morpholino, pyrrolidino, piperazino or the like, or any three of R.sup.5, R.sup.6, R.sup.7 or R.sup.8 can be taken together to form with the nitrogen atom a 5- or 6-membered aromatic heterocyclic ring, such as piperazole or pyridine. When R.sup.5, R.sup.6, R.sup.7 or R.sup.8 substituent in the ammonium group is a substituted phenyl or substituted phenylalkyl, the substituents on the phenyl and phenalkyl will generally be selected from halo, (C.sub.1 -C.sub.8)alkyl, (C.sub.1 -C.sub.4)alkoxy, hydroxy, nitro, trifluoromethyl, cyano, amino, (C.sub.1 -C.sub.4)alkylthio and the like. Such substituted phenyl groups preferably have up to two such substituents. Representative ammonium cations include ammonium, dimethylammonium, 2-ethylhexylammonium, bis(2-hydroxyethyl)ammonium, tris(2-hydroxyethyl)ammonium, dicyclohexylammonium, t-octylammonium, 2-hydroxyethylammonium, morpholinium, piperidinium, 2-phenethylammonium, 2-methylbenzylammonium, n-hexylammonium, triethylammonium, trimethylammonium, tri(n-butyl)-ammonium, methoxyethylammonium, diisopropylammonium, pyridinium, dialkylammonium, pyrazolium, propargylammonium, dimethylhydrazinium, octadecylammonium, 4-dichlorophenylammonium, 4-nitrobenzylammonium, benzyltrimethylammonium, 2-hydroxy-ethyldimethyloctadecylammonium, 2-hydroxyethyldiethyloctylammonium, decyltrimethylammonium, hexyltriethylammonium, 4-methylbenzyltrimethylammonium, and the like. Among the acid addition salts are those in which the anion is an agronomically acceptable anion such as hydrochloride, hydrobromide, sulfate, nitrate, perchlorate, acetate, oxalate and the like.
For insects to successfully grow, that is progress from one larval stage to the next larger larval stage or metamorphose to an adult stage, they must moult or shed the old cuticle. Compounds of this invention are insect growth regulators in that they interfere with this natural moulting and other growth-regulated processes.
Growth regulatory effects are not usually expressed rapidly after treatment. This is contrary to conventional insecticides, such as neurotoxins, respiratory poisons and the like, which affect vital processes and which are noted for rapidity of effect.
For example, compounds such as: (R.sup.1).sub.2 --P(X)X(CH.sub.2).sub.n C(O)NHN(R")C(O)C.sub.5 H.sub.6, where
R.sup.1 =lower alkyl, alkoxy, thioalkyl and may be identical or different
X=0 or S, n=0-5 and R"=t-butyl
would constitute conventional, fast-acting, cholinesterese-inhibiting neurotoxins with efficacy anticipated against a comparatively broad range of insect orders and acarides as well as non-target organisms such as mammals, fish and birds. By contrast insect growth regulators as claimed herein would be somewhat less rapid in effect with activity being confined to particular insects which are largely pestiferous and including those strains resistant to organophosphate insecticides. Although somewhat slower to act than conventional cholinesterese-inhibiting neurotoxins, compounds of this invention are sufficiently rapid-acting so as to protect agricultural crops and are therefore superior to other known insect growth regulators which are quite slow to elicit effects.
The present inventors have found that the following parameters are important to yield compounds having the nucleus of Formula Ia which are insect growth regulators. At least one of the moieties attached to one of the G.sub.1 's should have at least some bulk, i.e., at least two or three non-hydrogen atoms. However, if the bulk becomes too great, the compounds become less effective as insect growth regulators. Therefore, the moieties attached to the G.sub.1 's should be no greater than about 21 non-hydrogen atoms.
The size of the moiety E of Formula I is important. E should have at least 4 non-hydrogen atoms. Oxygen containing radicals have been found to be generally not preferred. If oxygen is present, generally E should be bulkier. Moieties containing two oxygen atoms or one oxygen and one sulfur atom are less preferred. It is preferred that E have no greater than 10 non-hydrogen atoms. Preferably, E does not include a chain of greater than four or five non-hydrogen atoms but is highly branched.
The size of the radical D and any moiety attached to the nitrogen adjacent to G.sub.2 --D of Formula I are found to be less important.
The compounds of this invention or their precursors can be prepared according to the following processes. Process A can be used when preparing compounds according to Formula II below where X and X' are both oxygen and A and B are the same (for example, both A and B are phenyl or 4-chlorophenyl) or different (for example, A is 4-methylphenyl and B is 4-chlorophenyl). ##STR12## wherein
A and B are organic radicals attached to the carbon shown in Formula II by a carbon-to-carbon single bond and R.sup.1 is other than hydrogen. ##STR13## where R.sup.1, A and B are as defined above for Formula II and X and X' are oxygen.
When R.sup.1 is cyano substituted alkyl the intermediate Va may be made as follows: ##STR14## where M is K or Na, X and X' are oxygen, A and B are as defined above for Formula II, and R.sub.3 and R.sub.4 are the same or different hydrogen or (C.sub.2 -C.sub.9) straight or branched chain unsubstituted or substituted alkyl having one or two of the same or different (C.sub.3 -C.sub.6)cycloalkyl; Process B can be used when preparing compounds according to Formula II where X and X' are oxygen, and R.sup.1, A and B are as defined above for Formula II. ##STR15## where X and X' are oxygen, A and B are as defined above for Formula II, and R.sup.3 and R.sup.4 are the same or different hydrogen or (C.sub.2 -C.sub.9) straight or branched chain unsubstituted or substituted alkyl having one or two of the same or different (C.sub.3 -C.sub.6)cycloalkyl. As can be seen above, the intermediate product of Step 2, the compounds of Formula X, corresponds to the compounds of Formula V. In addition, the compound of Formula XI corresponds to the compounds of Formula II where X and X' are oxygen. ##STR16## where R.sup.1, A and B are as defined above for Formula II and W is a good leaving group such as halo, for example, chloro; an alkoxy, for example, ethoxy; methyl sulfonate (--OSO.sub.2 CH.sub.3); or an ester, for example, acetate (--OC(O)CH.sub.3).
Process C can be used when preparing compounds according to Formula II where A, B and R.sup.1 are as defined for Formula II and one or both X and X' are sulfur. ##STR17## where A, B and R.sup.1 are as defined above for Formula II and one or both X and X' are sulfur, and Y is a good leaving group such as carboxyalkylthio (for example, carboxymethylthio, --SCH.sub.2 CO.sub.2 H); alkylthio (for example, methylthio); or halo (for example, chloro).
Process D can be used when preparing compounds according to Formula II where X and X' are oxygen and R.sup.1, A and B are as defined above for Formula II. ##STR18## wherein A, B and R.sup.1 are as defined above for Formula II and Z is t-butyl; ethyl; phenyl; or benzyl.
The starting materials for each process are generally commercially available, or can be prepared by generally customary and known methods.
Other compounds of this invention or their precursors can be prepared by reacting a suitably substituted hydrazine (Formula II) with an alkyl halide, allyl halide or phenylmethylhalide in the presence of a base in an inert or substantially inert solvent or mixture of solvents according to the following process: ##STR19## where X, X', R.sup.1, R.sup.2, A and B are as defined above for Formula II and Hal is halogen (chloro, fluoro or bromo).
Suitable bases for use in the above process include metal hydrides such as sodium hydride or potassium hydride; metal alkoxides such as sodium alkoxides or potassium alkoxides; sodium hydroxide; potassium hydroxide; or lithium diisopropyl amide. If desired, mixtures of these bases may be used. The preferred base is potassium t-butoxide.
Suitable solvents for use in the above process include ethers such as tetrahydrofuran (THF), glyme and the like; dimethylformamide (DMF); dimethylsulfoxide (DMSO); acetonitrile; or a mixture of water and benzene or toluene. If desired, mixtures of these solvents may be used. The preferred solvent is dimethylformamide.
The above process can be carried out at temperatures between about --20.degree. C. and about 100.degree. C. Preferably, this reaction is carried out between about -5.degree. C. and about 50.degree. C.
Preparation of the compounds of the present invention by the above process is preferably carried out at about atmospheric pressure although higher or lower pressures can be used if desired.
Substantially equimolar amounts of reactants are preferably used although higher or lower amounts can be used if desired.
Generally one equivalent of base is used per equivalent of starting material of Formula XXI.
The compounds of Formula XXI are generally commercially available or can be prepared by known procedures.
Modifications to the above process may be necessary to accommodate reactive functionalities of particular substituents. Such modifications would be apparent and known to those skilled in the art.
In process A, a compound of Formula III is reacted with a monosubstituted hydrazine of Formula IV or a corresponding acid addition salt such as the hydrochloride salt or the like in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford an intermediate product of Formula V which can be isolated or further reacted with a compound of Formula VI in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford the desired product of Formula II.
When A and B are the same, for example, both A and B are 4-chlorophenyl, two equivalents of a compound of Formula III or VI are reacted with a monosubstituted hydrazine of Formula IV in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford the desired product of Formula II.
Examples of the compounds of Formula III and/or Formula VI which can be used in the above processes include benzoyl chloride, 4-chlorobenzoyl chloride, 4-methylbenzoyl chloride, 3,5-dichlorobenzoyl chloride, 2-bromobenzoyl chloride, 3-cyanobenzoyl chloride, 3-toluoyl chloride, 4-toluoyl chloride, 4-ethylbenzoyl chloride, 2-nitrobenzoyl chloride, 2,3-dimethylbenzoyl chloride, 2-nitro-5-toluoyl chloride, cyclohexylcarbonyl chloride, n-butanoyl chloride, n-pentanoyl chloride, phenylacetyl chloride, 1-cyclohexenecarbonyl chloride, pivaloyl chloride, trichloroacetyl chloride, methacryloyl chloride and the like. The compounds of Formula III and/or Formula VI are generally commercially available or can be prepared by known procedures.
Examples of the compounds of Formula IV which can be used in the above processes include isopropylhydrazine, t-butylhydrazine, neopentylhydrazine, alpha-methylneopentylhydrazine, isobutylhydrazine, isopentylhydrazine, isooctylhydrazine, 1,1-dimethyl-3-butenylhydrazine, (trimethylsilylmethyl)hydrazine, (1,1,1-trifluoro-2-propyl)hydrazine, (2,2,2-trifluoroethyl)hydrazine, (1-cyano-1-methyl)ethylhydrazine and the like. The compounds of Formula IV are generally commercially available or can be prepared by known procedures. For example, the Grignard reagent addition product of acetone azine in diethyl ether is hydrolyzed by the addition of an acid (such as oxalic acid), in a suitable solvent or mixture of solvents (such as ethanol and diethyl ether, 1:1) to afford the monosubstituted hydrazine of Formula IV.
Suitable solvents for use in the above processes include water; alcohols such as methanol, ethanol, isopropanol and the like; hydrocarbons such as toluene, xylene, hexane, heptane and the like; glyme; tetrahydrofuran; acetonitrile; pyridine; or haloalkanes such as methylene chloride or mixtures of these solvents.
Preferred solvents are water, toluene, methylene chloride or a mixture of these solvents.
Examples of bases for use in the above processes include tertiary amines such as triethylamine; pyridine; potassium carbonate; sodium carbonate; sodium bicarbonate; sodium hydroxide; or potassium hydroxide. Preferred bases are sodium hydroxide, potassium hydroxide or triethylamine.
In Process B, Method 1, a compound of Formula VII is reacted with a ketone or aldehyde of Formula VIII in an inert or substantially inert solvent or mixture of solvents and optionally in the presence of a catalyst to afford an intermediate product of Formula IX. The intermediate product of Formula IX is then further reacted with a reducing agent in an inert or substantially inert solvent or mixture of solvents to afford a second intermediate product of Formula X which can be isolated or further reacted with a compound of Formula VI in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford the desired product of Formula XI.
Examples of the compounds of Formula VII which can be used in the above Process B, Method 1, include benzoylhydrazine, 4-chlorobenzoylhydrazine, 2-methylbenzoylhydrazine, 4-methylbenzoylhydrazine, 3,5-dichlorobenzoylhydrazine and the like. The compounds of Formula VII are generally commercially available or can be prepared by known procedures.
Examples of the compounds of Formula VIII which can be used in the above Process B, Method 1, include 1,1,1-trimethylacetaldehyde, methylethylketone, diethylketone, trifluoroacetone, methacrolein, ethyl pyruvate and the like. The compounds of Formula VIII are generally commercially available or can be prepared by known procedures.
Optionally, a catalyst may be used in Step 1, Method of of Process B. Suitable catalysts generally include organic acids such as acetic acid, trifluoroacetic acid, oxalic acid and the like; mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and the like; arylsulfonic acids such as toluenesulfonic acid; or pyridinium toluenesulfonate. Preferred catalysts are organic acids or arylsulfonic acids. Most preferred catalysts are acetic acid or trifluoroacetic acid.
Suitable solvents for use in the above Process B, Method 1, Step 1, include alcohols such as methanol, ethanol, isopropanol and the like; hydrocarbons such as toluene, benzene; ethers such as tetrahydrofuran (THF), glyme and the like; or dimethylformamide. Preferred solvents are alcohols and hydrocarbons. Most preferred solvents are alcohols such as methanol or ethanol.
Examples of suitable reducing agents for use in the above Process B, Method 1, Step 2, include hydrides such as sodium borohydride and derivatives thereof such as sodium cyanoborohydride, lithium aluminum hydride and derivatives thereof and the like; or diborane. Preferred reducing agents are sodium borohydride and derivatives thereof or lithium aluminum hydride and derivatives thereof. Most preferred as reducing agents are borane and diborane.
Optionally, in Process B, Method 1, Step 2, a catalyst may be included. Examples of suitable catalysts include organic acids such as acetic acid, trifluoroacetic acid; or mineral acids such as hydrochloric acid, sulfuric acid and the like. Preferred catalysts are organic acids or hydrochloric acid. Most preferred catalysts are acetic acid, trifluoroacetic acid or hydrochloric acid.
Suitable solvents for use in the above Process B, Method 1, Step 2, include alcohols such as methanol, ethanol, isopropanol and the like; ethers such as tetrahydrofuran (THF), diethylether, glyme and the like; or halohydrocarbons such as methylene chloride, chloroform and the like. Preferred solvents are alcohols and most preferred are methanol or ethanol.
Step 3 of Process B, Method 1 corresponds to Step 2 of Process A. Consequently, those bases and solvents suitable for use in Step 2 of Process A are suitable for use in Step 3, Method 1 of Process B including the preferred bases and solvents described above.
In Process B, Method 2, N'-substituted-N'-benzoylhydrazine of Formula XIII or N'-substituted-N-benzoylhydrazine of Formula XIIIa is reacted with a compound of Formula XII in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford the desired product of Formula II.
The compounds of Formula XII are generally commercially available or can be prepared from commercially available compounds by procedures well known to those skilled in the art as described below.
Examples of the compounds of Formula XIII which can be used in the above Process B, Method 2, include N'-t-butyl-N'-benzoylhydrazine; N'-t-butyl-N'-(3-methylbenzoyl)hydrazine; N'-t-butyl-N'-(4-chlorobenzoyl)hydrazine; N'-t-butyl-N'-(2-fluorobenzoyl)hydrazine; N'-isopropyl-N'-benzoylhydrazine; N'-neopentyl-N'-(4-chlorobenzoyl)hydrazine, N'-isopropyl-N-benzoylhydrazine; N'-sec-butyl-N-benzoylhydrazine; N'-(1-methyl)neopentyl-N-benzoylhydrazine; N'-neopentyl-N-benzoylhydrazine; N'-isobutyl-N-benzoylhydrazine; N'-(1,2,2-trimethylpropyl)-N-benzoylhydrazine; N'-diisopropylmethyl-N-benzoylhydrazine; N'-t-butyl-N-benzoylhydrazine; N'-t-butyl-N-(4-methylbenzoyl)hydrazine; N'-t-butyl-N-(4-chlorobenzoyl)hydrazine; N'-(1,1-dimethyl-3-butenyl)-N'-benzoylhydrazine, N'-(trimethylsilylmethyl)-N'-(4-methylbenzoyl)hydrazine, N'-(1,1,1-trifluoro-2-propyl)-N'-(2,4-dichlorobenzoyl)hydrazine, N'-(1-cyano-1-methyl)ethyl-N'-(2-methylbenzoyl)hydrazine and the like.
Suitable solvents for use in the above Prccess B, Method 2, include water; hydrocarbons such as toluene, xylene, hexane, heptane and the like; alcohols such as methanol, ethanol, isopropanol, and the like; glyme; tetrahydrofuran; acetonitrile; pyridine; or haloalkanes such as methylene chloride; or mixtures of these solvents. Preferred solvents are water, toluene, methylene chloride or a mixture of these solvents.
Examples of bases suitable for use in the above Process C includes tertiary amines such as triethylamine; pyridine; potassium carbonate; sodium carbonate; sodium bicarbonate; sodium hydroxide; or potassium hydroxide. Preferred bases are sodium hydroxide, or triethylamine.
The compounds of Formula XII are commercially available, such as nicotinoyl chloride hydrochloride, isonicotinoyl chloride hydrochloride and ethyl picolinate or can be prepared from commercially available materials by procedures known to those skilled in the art.
The compounds of Formula XIII can be prepared by procedures known to those skilled in the art from commercially available reactants. By way of example, a suitably substituted hydrazine (such as t-butyl-hydrazine or (1,1,1-trifluoro-2-propyl)hydrazine) is reacted with an aldehyde or ketone (such as acetone) in the presence of a base (such as triethylamine) to afford a hydrazone which is then reacted with a benzoyl chloride in an inert or substantially inert solvent or mixture of solvents in the presence of a base (such as sodium hydroxide) to afford an N'-substituted-N'-benzoylhddrazone which is then reacted with an acid (such as hydrochloric acid) to afford the compound of Formula XIII. Alternatively, a suitable substituted hydrazine (such as t-butyl-hydrazine or (trimethylsilylmethyl)hydrazine) is reacted with di-tertbutyldicarbonate in an inert or substantially inert solvent or mixture of solvents (such as toluene/water) to afford an N'-t-butyl-N-t-butoxycarbonylhydrazine or an N'-(trimethylsilylmethyl)-N-t-butoxycarbonylhydrazine which is then reacted with a benzoylchloride in an inert or substantially inert solvent or mixture of solvents to afford N'-t-butyl-N'-benzoyl-N-t-butoxy-carbonylhydrazine or an N'-(trimethylsilylmethyl)-N'-benzoyl-N-t-butoxycarbonylhydrazine which is then reacted with an acid to afford the desired compound of Formula XIII.
In Process C, a compound of Formula XIV is reacted with a monosubstituted hydrazine of Formula IV or a corresponding acid addition salt such as the hydrochloride salt or the like in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford an intermediate compound of Formula XV which can be isolated or further reacted with a compound of Formula XVI in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford the desired product of Formula I.
In Process D, a monosubstituted hydrazine of Formula IV or a corresponding acid addition salt, such as the hydrochloride salt or the like, is reacted with a compound of Formula XVII in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford an intermediate product of Formula XVIII. The intermediate product of Formula XVIII is then further reacted with a compound of Formula VI in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford a second intermediate product of Formula XIX. The second intermediate product of Formula XIX is then further reacted with an acid in an inert or substantially inert solvent or mixture of solvents to afford a third intermediate product of Formula XX. The third intermediate product of Formula XX is then further reacted with a compound of Formula III in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford the desired product of Formula II.
Examples of the compounds of Formula XVII which can be used in the above Process D include di-t-butyldicarbonate, diethyldicarbonate, diphenyldicarbonate, dibenzyldicarbonate and the like. The compounds of Formula XVII are generally commercially available or can be prepared by known procedures.
Suitable solvents for use in the above Process D, Steps 1, 2 and 4 include water; tetrahydrofuran; dioxane; toluene; alcohols such as methanol, ethanol and isopropanol; hexane; acetonitrile; pyridine; and haloalkanes such as methylene chloride; or mixtures of these solvents.
Preferred solvents are dioxane; toluene; tetrahydrofuran; pyridine; methylene chloride or water.
Most preferred solvents are dioxane; water or toluene.
Examples of the bases for use in the above Process D, Steps 1, 2 and 4 include tertiary amines such as triethylamine; pyridine; potassium carbonate, sodium carbonate; sodium bicarbonate; sodium hydroxide; and potassium hydroxide.
Preferred bases are sodium hydroxide; potassium hydroxide; pyridine or triethylamine.
Suitable solvents for use in the above Process D, Step 3 include alcohols such as methanol, ethanol and isopropanol; water; tetrahydrofuran; dioxane; and acetonitrile.
Preferred solvents are methanol or ethanol.
Examples of acids for use in the above Process D, Step 3 include concentrated hydrochloric acid or concentrated sulfuric acid.
When A and B are the same, for example, both A and B are unsubstituted phenyl, two equivalents of a compound Formula XIV or XVI are reacted with a monosubstituted hydrazine of Formula IV in the presence of a base in an inert or substantially inert solvent or mixure of solvents to afford the desired product of Formula II.
Examples of the compounds of Formula XIV and/or Formula XVI which can be used in the above Process C include 3-methyl-methylthio-thiobenzoate, 4-chloromethylthio-thiobenzoate, 4-methyl-methylthio-thiobenzoate, carboxymethylthio-thiobenzoate and the like. The compounds of Formula XIV and/or Formula XVI are generally commercially available or can be prepared by known procedures.
Suitable solvents for use in the above Process C are generally polar high-boiling solvents such as dimethylformamide (DMF); glyme; tetrahydrofuran (THF); and pyridine. The preferred solvent is pyridine.
Suitable bases for use in the above Process C include tertiary amines such as triethylamine; and pyridine. The preferred base is pyridine.
The above Processes A and B, Method 1, can be carried out at temperatures between about -20.degree. C. and about 100.degree. C. Preferably, these reactions are carried out between about -5.degree. C. and about 50.degree. C.
The above Process B, Method 2, can be carried out at temperatures between about -50.degree. C. and about 150.degree. C. Preferably when W is a halo radical, the reaction is carried out between about 0.degree. C. and about 30.degree. C. When W is alkoxy, the reaction is preferably carried out between about 100.degree. C. and about 150.degree. C. When W is methyl sulfonate, the reaction is preferably carried out between about -20.degree. C. to about 20.degree. C. When W is an ester, the reaction is preferably carried out between about 0.degree. C. and about 50.degree. C.
Process C can be carried out at temperatures between about 10.degree. C. and 200.degree. C. Preferably, this reaction is carried out between about 70.degree. C. and about 100.degree. C.
Process D can be carried out at temperatures between about 0.degree. C. and 100.degree. C. Preferably, these reactions are carried out between about 0.degree. C. and about 50.degree. C.
Preparation of the compounds of the present invention by processes A, B, C and D are preferably carried out at about atmospheric pressure, although higher or lower pressures can be used if desired.
Substantially equimolar amounts of reactants are preferably used in processes A, B and C, although higher or lower amounts can be used if desired.
Generally, about one equivalent of base is used per equivalent of starting material of Formula III, VI, XII and/or XIV. Where the acid addition salt of the mono-substituted hydrazine of Formula IV is used, one additional equivalent of base is used. For example, in Process A, when substituents A and B are the same and a monosubstituted hydrazine is used, about two equivalents of base are used since about two equivalents of a suitably substituted benzoyl chloride of Formula III or VI are employed. In Process A, when substituents A and B are different and an acid addition salt of the monosubstituted hydrazines of Formula IV is used, about two equivalents of base are used in Step 1 and about one equivalent of base is used in Step 2.
Modifications to the above processes may be necessary to accommodate reactive functionalities of particular A and/or B substituents. Such modifications would be apparent and known to those skilled in the art.
It will be appreciated by those skilled in the art that electronic forces may give rise to more than one isomer of the compounds of Formula II such as enantiomers, conformers and the like. There may be a difference in properties such as physical characteristics and degree of biological activity between such isomers. Separation of a specific isomer can be accomplished by standard techniques well known to those skilled in the art such as silica gel chromatography.
The agronomically acceptable salts embraced by Formula I of the invention can be prepared by reacting a metal hydroxide, a metal hydride or an amine or ammonium salt, such as a halide, hydroxide or alkoxide with a compound of Formula I having one or more hydroxy or carboxy groups or reacting a quaternary ammonium salt, such as chloride, bromide, nitrate or the like with a metal salt of a compound of Formula I in a suitable solvent. When metal hydroxides are used as reagents, useful solvents include water; ethers such as glyme and the like; dioxane; tetrahydrofuran; alcohols such as methanol, ethanol, isopropanol and the like. When metal hydrides are used as reagents, useful solvents include nonhydroxylic solvents, for example, ethers such as dioxane, glyme, diethylether and the like; tetrahydrofuran; hydrocarbons such as toluene, xylene, hexane, pentane, heptane, octane and the like; dimethylformamide, and the like. When amines are used as reagents, useful solvents include alcohols, such as methanol or ethanol; hydrocarbons, such as toluene, xylene, hexane and the like; tetrahydrofuran; glyme; dioxane; or water. When ammonium salts are used as reagents, useful solvents include water; alcohols, such as methanol or ethanol; glyme; tetrahydrofuran; or the like. When the ammonium salt is other than a hydroxide or alkoxide, an additional base, such as potassium or sodium hydroxide, hydride, or alkoxide is generally used. The particular choice of solvent will depend on the relative solubilities of the starting materials and the resultant salts, and slurries rather than solutions of certain reagents may be used to obtain the salts. Generally, equivalent amounts of the starting reagents are used and the salt-forming reaction is carried out at about 0.degree. C. to about 100.degree. C., preferably at about room temperature.
The acid addition salts of the present invention can be prepared by reacting hydrochloric, hydrobromic, sulfuric, nitric, phosphoric, acetic, propionic, benzoic or other suitable acid with a compound of Formula I having a basic functional group in a suitable solvent. Useful solvents include water, alcohols, ethers, esters, ketones, haloalkanes and the like. The particular choice of solvent will depend on the relative solubilities of the starting materials and the resulting salts and slurries rather than solutions of certain reagents may be used to obtain the salts. Generally, equivalent molar amounts of starting materials are used and the salt-forming reaction is carried out at from about -10.degree. C. to about 100.degree. C., preferably at about room temperature.
The following examples will further illustrate this invention but are not intended to limit it in any way. In Table I, some N'-substituted-N,N'-disubstitutedhydrazines of the present invention that have been made are listed. The structure of these compounds was confirmed by NMR and in some cases by IR and/or elemental analysis. Specific illustrative preparation of the compounds of Examples 1, 3, 16, 44, 102, 103, 148, 220, 295, 324, 625, 635, 636, 637, 638, 639, 642, 646, 648, 654, 656, 659, 660, 682, 683, 688, 689, 691, 699, 702, 722, 723, 724, 727, 729, 733, 737, 738, 739, 743, 754, 755, 764, 765, 766, 767, 772, 778, 787, 802, 809, 822, 829, 837, 853, 855, 864, 870 to 873, 878, 880, 882, 883, 893, 905, 914, 918, 922, 923, 933, 941, 942, 944, 948, 1002, 1008, 1013 and 1015 to 1018 are described after Table I.
TABLE I ##STR20## where G.sub.2 N is a single bond when R.sup.2 is "H" and is a double bond when R.sup.2 is "" Ex. No. G.sub.2 (X) G.sub.2 (X') R.sup.1 R.sup.2 A B 1 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.4 Cl-4 2 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-3 C.sub.6 H.sub.4 Cl-3 3 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.5 4 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.3 Cl.sub.2 -3,4 C.sub.6 H.sub.3 Cl.sub.2 -3,4 5 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -4 C.sub.6 H.sub.4 CH.sub.3 -4 6 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 NO.sub.2 -4 C.sub.6 H.sub.4 NO.sub.2 -4 7 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 OCH.sub.3 -4 C.sub.6 H.sub.4 OCH.sub.3 -4 8 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 NO.sub.2 -3 C.sub.6 H.sub.4 NO.sub.2 -3 9 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 OCH.sub.3 -3 C.sub.6 H.sub.4 OCH.sub.3 -3 10 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 NO.sub.2 -2 C.sub.6 H.sub.4 NO.sub.2 -2 11 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-2 C.sub.6 H.sub.4 Cl-2 12 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 OCH.sub.3 -2 C.sub.6 H.sub.4 OCH.sub.3 -2 13 C(O) C(O) C(CH.sub.3 ).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -4 C.sub.6 H.sub.5 14 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CN-4 C.sub.6 H.sub.4 CN-4 15 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -4 C.sub.6 H.sub.4 Cl-4 16 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 Cl-4 17 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 Cl-3 18 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 Cl-2 19 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -3 C.sub.6 H.sub.4 CH.sub.3 -3 20 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -2 C.sub.6 H.sub.4 CH.sub.3 -2 21 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 CH.sub.3 -4 22 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 CH.sub.3 -3 23 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 CH.sub.3 -2 24 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 OCH.sub.3 -4 25 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 OCH.sub.3 -3 26 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 OCH.sub.3 -2 27 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 C(CH.sub.3).sub.3 -4 28 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 CN-4 29 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 NO.sub.2 -4 30 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 NO.sub.2 -3 31 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 NO.sub.2 -2 32 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 C(CH.sub.3).sub.3 -4 C.sub.6 H.sub.4 C(CH.sub.3).sub.3 -4 33 C(O) C(O) C (CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -4 C.sub.6 H.sub.3 Cl.sub.2 -3,4 34 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 F-4 35 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 F-3 36 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 F-2 37 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.3 Cl.sub.2 -3,5 C.sub.6 H.sub.3 Cl.sub.2 -3,5 38 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 Cl.sub.2 -2,4 39 C(O) C(O) CH(CH.sub.3).sub.2 H C .sub.6 H.sub.5 C.sub.6 H.sub.5 40 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 CF.sub.3 -4 41 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 CF.sub.3 -3 42 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 CF.sub.3 -2 43 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 F.sub.2 -2,5 44 C(O) C(O) CH.sub.2 C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.5 45 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 CN-3 46 C(O) C(O) CH(CH.sub.3)CH.sub.2 CH.sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.5 47 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 F.sub.2 -2,6 48 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.5 49 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 Cl.sub.2 -3,4 50 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 Cl.sub.2 -3,5 51 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 Cl.sub.2 -2,6 52 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 C(CH.sub.3).sub.3 -4 C.sub.6 H.sub.5 53 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-2 C.sub.6 H.sub.5 54 C(O) C(O) C(CH.sub.3).sub.3 H ##STR21## C.sub.6 H.sub.5 55 C(O) C(O) C(CH.sub.3).sub.3 H ##STR22## ##STR23## 56 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-3 C.sub.6 H.sub.5 57 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.3 Cl.sub.2 -3,4 58 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-2 C.sub.6 H.sub.3 Cl.sub.2 -3,4 59 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -2 C.sub.6 H.sub.5 60 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 Cl-2-NO.sub.2 -4 61 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 (NO.sub.2).sub.2 -3,5 62 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 Cl.sub.2 -2,3 63 C(O) C(O) CH(CH.sub.3)C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.5 64 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub. 6 H.sub.3 Cl-2-CH.sub.3 -5 65 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 (CH.sub.3).sub.2 -3,5 66 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 NO.sub.2 -2-CH.sub.3 -5 67 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 CH.sub.3 -2-Cl-3 68 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 Cl-3-CH.sub.3 -4 69 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 NO.sub.2 -2-Cl-3 70 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 OCH.sub.3 -3-NO.sub.2 -4 71 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 NO.sub.2 -2-OCH.sub.3 -3 72 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.3 (NO.sub.2).sub.2 -2,4 73 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.4 Cl-2 74 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.4 Cl-3 75 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.4 CH.sub.3 -4 76 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.3 Cl.sub.2 -3,5 77 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.3 Cl.sub.2 -2,4 78 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.4 CF.sub.3 -4 79 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 OSO.sub.2 CH.sub.3 -4 80 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 CH(CH.sub.3).sub.2 -4 81 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 OCOCH.sub.3 -2 82 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 CH.sub.2 CH.sub.3 -4 83 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 Br-2 84 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 OH-4 85 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -4 C.sub.6 H.sub.4 CH.sub.3 -2 86 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -4 C.sub.6 H.sub.4 CH.sub.3 -2 87 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -4 C.sub.6 H.sub.3 Cl.sub.2 -2,4 88 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -4 C.sub.6 H.sub.3 Cl.sub.2 -3,5 89 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub. 3 -4 C.sub.6 H.sub.4 Cl-2 90 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -4 C.sub.6 H.sub.4 F-4 91 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -4 C.sub.6 H.sub.4 CF.sub.3 -4 92 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.3 -4 C.sub.6 H.sub.4 Cl-3 93 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.4 CH.sub.2 Cl-3 94 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.4 CH.sub.2 Cl-4 95 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.4 CH.sub.3 -2 96 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.4 OCH.sub.3 -3 97 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.4 CH.sub. 3 -3 98 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 F-4 C.sub.6 H.sub.4 F-4 99 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 F-3 C.sub.6 H.sub.4 F-3 100 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 F-2 C.sub.6 H.sub.4 F-2 101 C(O) C(O) C(CH.sub.3).sub.3 H ##STR24## ##STR25## 102 C(S) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 Cl-4 C.sub.6 H.sub.5 103 C(O) C(S) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.5 104 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 Br-4 105 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 Br-3 106 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 -4 107 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.4 CH.sub.2 CH.sub.3 -4 C.sub.6 H.sub.5 108 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.3 Cl.sub.2 -3,4 C .sub.6 H.sub.5 109 C(O) C(O) C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 COCH.sub.3 -4 110 C(O) C(O) CH.sub.2 C(CH.sub.3).sub.3 H C.sub.6 H.sub.5 C.sub.6 H.sub.4 ##STR26##

EXAMPLE NO. 1
-Preparation of N'-t-butyl-N,N'-(4-chlorobenzoyl)hydrazine
A suspension of t-butylhydrazine hydrochloride (12.5 g, 0.1 mole) in toluene (100 ml) at 0.degree.-5.degree. C. was treated slowly with 1 equivalent of NaOH solution, prepared from diluting 8 g of 50% NaOH commercially available solution to 20 ml of the volume with H.sub.2 O. At 0.degree. to 5.degree. C. with mechanical stirring, 2 equivalents of 4-chlorobenzoyl chloride (35.9 g, 0.2 mole) and 2 equivalents of NaOH (16 g of 50% NaOH diluted with H.sub.2 O to 40 ml) were added dropwise separately and simultaneously from dropping funnels. The exothermic reaction was cooled down by an ice-water bath through the entire addition. After the addition was completed, the resulting suspension was stirred at room temperature (RT) for one hour. The white precipitate (p.p.t.) was collected by suction-filtration and washed with a small amount of toluene and 100 ml of H.sub.2 O. The material was then air-dried, then crystallized from 95% aqueous CH.sub.3 OH to afford 24.65 g of N'-t-butyl-N,N'-(4-chlorobenzoyl)hydrazine as needles: m.p. 246.degree.-248.degree. C.
Additional product can be obtained by concentrating the mother liquor of crystallization.
EXAMPLE NO. 3
Preparation of N'-t-buty-1-N,N'-dibenzoylhydrazine
To a stirred suspension of t-butylhydrazine hydrochloride (1.24 g, 10 mmoles) in toluene (50 ml) at room temperature, was added dropwise a solution of 50% aqueous sodium hydroxide (0.8 g, 10 ml). After 15 minutes, the reaction mixture was cooled to 5.degree. C. and solutions of benzoyl chloride (2.82 gm, 20 ml) in toluene (7 ml) and 50% aqueous sodium hydroxide (1.6 g) were added dropwise and simultaneously from separate addition funnels while maintaining the temperature below 10.degree. C. Following the addition, the reaction mixture was warmed to room temperature and stirred for 1 hr. The reaction mixture was diluted with ether and the product isolated by filtration. The product was washed with water and ether and dried. The product was recrystallized from ethermethanol to afford N'-t-butyl-N,N'-dibenzoylhydrazine as a white powder: m.p. 174.degree.-176.degree. C.
EXAMPLE NO. 16
Preparation of N'-t-butyl-N'-(4-chlorobenzoyl)-N-benzoylhydrazine
To a stirred suspension of t-butylhydrazine hydrochloride (1.24 g, 10 mmoles) in toluene (30 ml) at room temperature was added dropwise a 50% aqueous solution of sodium hydroxide (0.8 g, 10 mmole). After 15 min., the reaction mixture was cooled to 5.degree. C. and a solution of benzoyl chloride (1.42 g, 10 mmoles) in toluene (5 ml) and a solution of aqueous 50% sodium hydroxide (0.8 g, 10 mmole) were added dropwise simultaneously from separate addition funnels while maintaining the temperature at or below 10.degree.. Following the addition, the reaction mixture was warmed to room temperature and stirred for 1 hr. The reaction mixture was diluted with toluene washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent removed under vacuum to afford a yellow oil which slowly solidifies on standing. The product was recrystallized from ether-hexane to afford white crystals.
To a stirred solution of the monobenzoylated compound (1.92 g, 10 mmoles) in toluene (30 ml) at 5.degree. C., were added dropwise simultaneously from separate addition funnels, solutions of p-chlorobenzoyl chloride (1.75 g, 10 mmoles) in toluene (5 ml) and aqueous 50% sodium hydroxide solution (0.8 g) while maintaining the temperature below 10.degree. C. Following the addition, the reaction mixture was warmed to room temperature and stirred for 1 hr. The mixture was then diluted with hexane and the precipitated product isolated by filtration. The product was washed with water and hexane and dried. The crude product was recrystallized from ether-methanol to afford N'-t-butyl-N'-(4-chlorobenzoyl)-N-benzoylhydrazine as a white powder: m.p. 201.degree.-204.degree. C.
EXAMPLE NO. 44
Preparation of N'-neopentyl-N,N'-dibenzoylhydrazine
A solution of benzoylhydrazine (1.36 g, 10 mmoles), 1,1,1-trimethylacetaldehyde (0.86 g, 10 mmoles), and acetic acid (catalytic amount) in methanol are stirred at room temperature until hydrazone formation is complete. The reaction mixture is brought to a pH of 4 and sodium cyanoborohydride (0.75 g, 12.5 mmoles) is added slowly portionwise (the reaction is connected to an aqueous sodium hydroxide trap). Upon compleiion, the reaction is diluted with excess aqueous sodium hydroxide and the methanol is removed under vacuum. The product is partitioned into methylene chloride and washed with aqueous base and water. The organic layer is separated and dried over anhydrous magnesium sulfate The magnesium sulfate is filtered, and the methylene chloride removed under vacuum to afford the product as a yellow oil which solidifies on standing. The crude 2-neopentyl-1-benzoylhydrazine is benzoylated directly.
To a stirred solution of the 2-neopentyl-1-benzoylhydrazine in toluene (40 ml) at 5.degree. C., were added dropwise and simultaneously solutions of benzoyl chloride (1.4 g, 10 mmoles) in toluene (5 ml) and aqueous 50% sodium hydroxide solution (0.8 g) while maintaining the temperature below 10.degree. C. After the addition, the reaction mixture was warmed to room temperature and stirred for 1 hour. The reaction mixture was diluted with hexane and the precipitated product isolated by filtration. The product was washed with water and hexane and dried. The crude product was recrystallized from methanol to afford N'-neopentyl-N,N'-dibenzoylhydrazine as a white powder: m.p. 237.degree.-239.degree. C.
EXAMPLE NO. 102
Preparation of N'-t-butyl-N'-benzoyl-N-4-chlorothiobenzoylhydrazine
A mixture of 4-chloro-methylthio-thiobenzoate (3.0 g, 0.015 mol) and t-butyl hydrazine hydrochloride (2.0 g, 0.016 mol) in 5 ml of pyridine was heated at 90.degree. C. for 18 hours. The mixture was poured into 0.1N HCl/ether. The layers were separated and the organic extracts were washed with 3 portions of 0.1N HCl followed by saturated aqueous NaHCO. After the extracts were dried over anhydrous magnesium sulfate, the solvents were removed under vacuum to afford 1.9 g of a brown solid. Chromatography on silica gel using ether (25%)-methylene chloride (25%)-hexane as eluant afforded 0.8 g of a golden yellow solid. The solid was dissolved in 3 ml of methylene chloride and treated with pyridine (1 ml) and benzoyl chloride (0.6 ml). After 24 hours at 23.degree. C., the reaction mixture was poured onto 0.1N HCl/ether. The organic layer was washed with saturated aqueous sodium bicarbonate and was dried over anhydrous magnesium sulfate. Evaporation of solvents gave a yellow oil which was chromatographed on silica gel using ether (25%)-methylene chloride (25%)-hexane as eluant to give 0.15 g of N'-t-butyl-N'-benzoyl-N-4-chlorothiobenzoylhydrazine as a yellow solid: m.p. 160.degree.-162.degree. C.
EXAMPLE NO. 103
Preparation of N'-t-butyl-N'-thiobenzoyl-N-benzoylhydrazine
A mixture of N'-t-butyl-N-benzoyl hydrazine (60% purity, 1.0 g, 0.0031 mol) and S-(thiobenzoyl)-thioglycolic acid (1.0 g, 0.0047 mol) in 3 ml of pyridine was heated at about 90.degree. C. for 24 hours. The dark colored mixture was cooled and poured into 0.1N HCl/ether. The organic layer was washed with three 15 ml portions of 0.1N HCl followed by saturated aqueous sodium bicarbonate. The organic extracts were dried over anhydrous magnesium sulfate. Evaporation of the solvents afforded 0.5 g of a brown oil which was recrystallized from ether-hexane to yield 0.2 g of N'-t-butyl-N'-thiobenzoyl-N-benzoylhydrazine as a tan solid m.p. 169.degree.-171.degree. C.
EXAMPLE NO. 14
Preparation of N'-t-butyl-N-(2-hydroxymethylbenzoyl)-N'-benzoylhydrazine
t-Butylhydrazine (0.1 mol) in 75 ml ethanol was treated with 50% aqueous sodium hydroxide (0.11 mol). Phthalide (0.1 mol) was added and the mixture was refluxed for 5 days. After cooling, water was added and the crude product was isolated by
filtration. Filtration through silica gel afforded N'-t-butyl-N-(2-hydroxymethylbenzoyl)hydrazine (3.0 g). m.p. 116.degree.-118.degree. C.
0.7 g of N'-t-butyl-N-(2-hydroxymethylbenzoyl)-hydrazine and 1.1 g benzoyl chloride are combined in 10 ml of 5% NaOH and stirred at room temperature for 1.5 hours. The solids are filtered off, washed with water, then ether, to afford 0.6 g of white solid N'-t-butyl-N-(2-(benzoyloxymethyl)benzoyl)-N'-benzoylhydrazine. m.p. 190.degree.-191.degree. C.
EXAMPLE NO. 220
Preparation of N-(3-toluoyl)-N'-t-butyl-N'-benzoylhydrazine
Step 1
To a stirred suspension of t-butylhydrazine (51 g) in a mixture of dioxane and water (2:1) (150 ml) was added sodium hydroxide (32 g of a 50% aqueous solution). After 10 min., the solution was cooled to 5.degree. C. and di-t-butyldicarbonate (42 g) was added dropwise so as to maintain the reaction temperature below 10.degree. C. The reaction mixture was warmed and stirred 2 hours at room temperature. The reaction mixture was filtered, washed with water and dried to afford N-t-butyloxycarbonyl-N'-t-butylhydrazine (74 g) as a white crystalline solid. m.p. 69.degree.-71.degree. C.
Step 2
To a stirred solution of N-t-butyloxycarbonyl-N'-t-butylhydrazine (61 g) in toluene (120 ml) was added benzoyl chloride (45 g) and sodium hydroxide (31 g of a 50% aqueous sodium hydroxide solution) dropwise and simultaneously. After stirring for 1 hour at room temperature, the solid N-t-butyloxycarbonyl-N'-t-butyl-N'-benzoylhydrazine was filtered, washed with water, hexane and dried to afford 52 g of product. m.p. 167.degree.-170.degree. C.
Step 3
The N-t-butoxycarbonyl-N'-t-butyl-N'-benzoylhydrazine (52 g, 0.18 mol) was stirred at room temperature in a methanolic hydrochloric acid solution for 4 days. The reaction mixture was neutralized with saturated aqueous sodium bicarbonate. The whte precipitate was filtered, washed with water and dried in vacuo to give 30 g of N'-t-butyl-N'-benzoylhydrazine. m.p. 124.degree.-125.degree. C.
Step 4
To a stirred mixture of N'-t-butyl-N'-benzoylhydrazine (1.0 g) in 15 ml toluene and aqueous sodium hydroxide (0.5 g of 50% NaOH) was added 3-toluoylchloride (0.9 g). After stirring for 2 hours, the product was isolated by filtration to give N'-t-butyl-N-(3-toluoyl)-N'-benzoylhydrazine in good yield. m.p. 111.degree.-114.degree. C.
EXAMPLE NO. 295
Preparation of N'-(1,1-dimethylethyl)-N,N'-dibenzoylhydrazine
To a gently refluxing solution of ethyl magnesium bromide (150 ml of 1M solution) was added acetone azine (20 g) dissolved in diethyl ether (80 ml). The solution was refluxed for three days. Upon cooling, a saturated solution of ammonium chloride (75 ml) was added. The aqueous layer was separated and washed twice with diethyl ether (150 ml). The combined ether extracts were dried over anhydrous magnesium sulfate, filtered and the ether removed at reduced pressure. The product was distilled through a vigreux column at 3 torr and collected in a dry ice/acetone cooled receiving flask. The boiling point was 40.degree.-50.degree.. 15 g of product was collected.
Oxalic acid (17 g) was dissolved in a solution of ethanol:diethyl ether (1:1) (150 ml) and water (3.3 g) was added. To this acid solution was added the hydrazone (13 g) dissolved in diethyl ether (30 ml). The solution was stirred for 24 hours then filtered. The solid is washed once with diethyl ether. The filtrate was concentrated and combined with the solid to afford a 77% yield (16.3 g) of the hydrazine oxalate.
The 1,1-dimethylethylhydrazine oxalate (2 g) was dissolved in toluene and neutralized with 50% aqueous sodium hydroxide. To this solution was added benzoyl chloride (4.02 g) and sodium hydroxide (50% Aq. solution) (2.45 g) at 25.degree. C. The reaction mixture was warmed to room temperature and stirred 3 hours. The mixture was diluted with hexane and filtered to afford the product as a white solid (0.5 g).
EXAMPLE NO. 324
Preparation of N'-t-butyl--N-(thiobenzoyl)-N'-(3-toluoyl)hydrazine
S-(thiobenzoyl)thioglycolic acid (3.0 g) was dissolved in 20 ml pyridine, treated with t-butyl hydrazine hydrochloride (excess, ca. 4 g) and then was heated at ca. 120.degree. C. for 14 hours. Water (120 ml) was added and the mixture was extracted with ether. The organic extracts were dried over anhydrous magnesium sulfate, filtered and evaporated to give crude N'-t-butyl-N-(thiobenzoyl)hydrazine as a viscous yellow oil.
N't-butyl-N-(thiobenzoyl)hydrazine (ca. 1 g), m-toluoyl chloride (approx. 0.7 g) and 50% aqueous sodium hydroxide (6 drops) were mixed in 1 ml water and 10 ml toluene at 23.degree. C. After stirring for 3 hours, ether-hexane was added and the product was isolated by filtration (0.25 g). m.p. 165.degree.-168.degree. C.
EXAMPLE NO. 344
Preparation of N'-t-butyl-N-[3-(N N-dimethylcarbamoyl)benzoyl)-N'-benzoylhydrazine
N-(3-hydroxybenzoyl)-N'-t-butyl-N'-benzoylhydrazine (0.2 g) was stirred in tetrahydrofuran (15 ml) at 23.degree. C. Solid potassium t-butoxide (0.1 g) was added and the solution went from clear colorless to cloudy yellow. After stirring 10 minutes at room temperature, N,N-dimethylcarbamoyl chloride was added dropwise (0.1 g). With the addition the solution turned colorless and a precipitate appeared. Saturated aqueous NaHC03 and ether were added, the layers separated and the organic dried over magnesium sulfate, filtered and rotavapped to afford an oily solid.
EXAMPLE NO. 625
Preparation of N'-t-butyl-N-(4-(4,4-dimethyloxazol-2-yl)benzoyl)-N'-(3-toluoyl)hydrazine
1.2 g of N'-t-butyl-N-(4-carbomethoxybenzoyl)-N'-(3-toluoyl)hydrazine was heated in 2 ml of 2-amino-2-methyl-1-propanol at 90.degree.-100.degree. C. for 5 hours. After cooling, the mixture was diluted with ether/methylene chloride and washed with 0.1N HCl. The organic layer was evaporated to afford 1.0 g of the corresponding amide.
The amide in 10 ml of chloroform was treated with 0.25 g of thionyl chloride and stirred at 23.degree. C. for 1.5 hours. Saturated aqueous sodium bicarbonate was added and the layers separated. Evaporation of the organic layer afforded the product as a foam.
EXAMPLE NO. 635
Preparation of N-methyl-N'-t-butyl-N,N'-dibenzoylhydrazine
To a stirred solution of N'-t-butyl-N,N'-dibenzoylhydrazine (2.5 g, 0.008M) in dimethylformamide (DMF) (30 ml) at room temperature under nitrogen was added portionwise sodium hydride (60% oil dispersion) (0.4 g, 0.009M). The mixture was stirred at room temperature for 0.5 hours, and then methyl iodide (1.0 g, 0.008M) was added dropwise. The reaction mixture was allowed to stir for 1 hour. The mixture was then diluted with water (50 ml), neutralized with 10% HCl, and the product extracted into methylene chloride (50 ml). The methylene chloride layer was washed with water (5.times.20 ml), dried over anhydrous magnesium sulfate, and the methylene chloride removed under vacuum to afford N-methyl-N'-t-butyl-N,N'-dibenzoylhydrazine as an oil.
EXAMPLE NO. 636
Preparation of N-benzyl-N'-t-butyl-N,N'-dibenzoylhydrazine
To a stirred solution of N'-t-butyl-N,N'-dibenzoylhydrazine (2 g, 0.006M) in DMF (25 ml) at room temperature under nitrogen was added portionwise sodium hydride (60% oil dispersion) (0.3 g, 0.007M). The mixture was stirred at room temperature for 0.5 hours, and then benzyl bromide (1.2 g, 0.007M) was added dropwise. The reaction mixture was warmed to 60.degree. C. and allowed to stir for 2 hours. The mixture was then diluted with water (50 ml), neutralized with 10% HCl, and the product extracted into methylene chloride (50 ml). The methylene chloride layer was washed with water (5.times.20 ml), dried over anhydrous magnesium sulfate, and the methylene chloride removed under vacuum to afford N-benzyl-N'-t-butyl-N,N'-dibenzoylhydrazine as an oil.
EXAMPLE NO. 637
Preparation of N-allyl-N'-t-butyl-N,N'-dibenzoylhydrazine
To a stirred solution of N'-t-butyl-N,N'-dibenzoylhydrazine (3 g, 0.011M) in DMF (30 ml) at room temperature under nitrogen was added portionwise sodium hydride (60% oil dispersion) (0.5 g, 0.012M). The mixture was stirred at room temperature for 0.5 hours, and then allyl iodide (1.8 g, 0.01M) was added dropwise. The reaction mixture was warmed to 60.degree. C. and stirred for 2 hours. The mixture was then diluted with water (50 ml), neutralized with 10% HCl, and the product extracted into methylene chloride (50 ml). The methylene chloride layer was washed with water (5.times.20 ml), dried over anhydrous magnesium sulfate, and the methylene chloride removed under vacuum to afford N-allyl-N'-t-butyl-N,N'-dibenzoylhydrazine as an oil.
EXAMPLE NO. 638
Preparation of N-methoxymethyl-N'-t-butyl-N-N'-dibenzoylhydrazine
N'-t-butyl-N,N'-dibenzoylhydrazine (2 g, 0.007M) was stirred at room temperature in a two phase system of toluene-50% sodium hydroxide with 100 mg of phase transfer catalyst (tetra-n-butylammonium hydrogen sulfate). Methoxymethyl chloride (1.2 g, 0.015M) was added dropwise and the mixture was stirred 3 hours. The layers were separated and the toluene layer was washed several times with water (until the water washes were neutral). The toluene solution was dried over anhydrous magnesium sulfate and the toluene removed under vacuum to afford N-methoxymethyl-N'-t-butyl-N,N'-dibenzoylhydrazine as a thick oil.
EXAMPLE NO. 639
Preparation of N-methylthiomethyl-N'-t-butyl-N,N'-dibenzoylhydrazine
To a stirred suspension of sodium hydride (a 50% oil dispersion washed 2 times with 20 ml pentane) (0.21 g, 0.0043M) in dry DMF (20 ml) under nitrogen at room temperature, was added N'-t-butyl-N,N'-dibenzoylhydrazine (1 g, 0.0034M) portionwise as a solid. The mixture was stirred at room temperature for 1/2 hour and methylthiomethylchloride (0.34 g, 0.0035M) was added dropwise. The resulting mixture was heated at 50.degree. C. overnight, cooled, diluted with methylene chloride and washed repeatedly with water. The organic layer was dried over anhydrous magnesium sulfate and the methylene chloride removed under vacuum. The oily residue was chromatographed on silica gel using methylene chloride to afford N-methylthiomethyl-N'-t-butyl-N,N'-dibenzoylhydrazine as an oil (60% yield).
EXAMPLE NO. 642
Preparation of N-(2-propynyl)-N'-t-butyl-N-benzoyl-N'-(3,5-dimethylbenzoyl)hydrazine
To a stirred suspension of N'-t-butyl-N-benzoyl-N'-(3,5-dimethylbenzoyl)hydrazine (1.5 g) in dimethylformamide (DMF) (20 ml) was added sodium hydride (200 mg of 60% oil dispersion) portionwise. After 15 min., propargyl bromide (0.6 g) was added to the reaction mixture dropwise and the reaction stirred for 1 hour. The reaction mixture was diluted with ethyl acetate (50 ml) and washed with water (5.times.20 ml). The organic layer was then dried over magnesium sulfate and the solvent removed under vacuum to afford N-(2-propynyl)-N'-t-butyl-N-benzoyl-N'-(3,5-dimethylbenzoyl)hydrazine as a yellow amorphous solid. The product, N-(2-propynyl)-N'-t-butyl-N-benzoyl-N'-(3,5-dimethylbenzoyl)hydrazine, was purified by column chromatography on silica gel (solvent system:methylene chloride) to afford a 70% yield as a white solid.
EXAMPLE NO. 646
Preparation of N'-t-butyl-N-cyclohexyl-carbonyl-N'-benzoylhydrazine
To a stirred suspension of t-butylhydrazine hydrochloride (2.0 g, 0.016M) in toluene (30 ml) was added 50% sodium hydroxide (1.3 g, 0.016M). After 15 minutes, the mixture was cooled to 5.degree. C. and cyclohexanecarbonylchloride (2.4 g, 0.016M) and 50% sodium hydroxide (1.3 g, 0.016M) were added separately and simultaneously so as to maintain the reaction temperature below 10.degree. C. After the addition, the reaction mixture was allowed to warm to room temperature and stirred for 1 hr. The mixture was diluted with hexane and the solid product isolated by filtration. This product (1.5 g, 0.008M) was dissolved in a stirred mixture of toluene (30 ml) and cooled on ice. To this mixture was added benzoylchloride (1.1 g, 0.008M) and 50% sodium hydroxide (0.6 g, 0.008M) simultaneously. After addition, the mixture was stirred for 1/2 hr., diluted with hexane and the solid product, N'-t-butyl-N-cyclohexylcarbonyl-N'-benzyylhydrazine, isolated by filtration.
EXAMPLE NO. 648
Preparation of N'-t-butyl-N-valeryl-N-benzoylhydrazine
To a stirred suspension of t-butylhydrazine hydrochloride (24.8 g, 0.20 mole) in toluene (150 ml) at 5.degree. C. was added one equivalent of NaOH, prepared by diluting 16 g of 50% aqueous (aq.) NaOH to 30 ml. After addition, valeryl chloride (24 g, 0.2 mole) and another one equivalent of NaOH solution (30 ml) were dropwise added separately and simultaneously. The reaction mixture was warmed to room temperature and stirred for 40 min. The two phase mixture was separated and the organic layer was washed with water and brine. The organic layer was dried over Na.sub.2 SO.sub.4 and concentrated under vacuum to give a colorless oil.
To a stirred solution of 1-t-butyl-2-valerylhydrazine (4 g, 0.023M) in toluene (40 ml) at 5.degree. C. was added benzoyl chloride (3.4 g, 0.024M) and 50% aq. sodium hydroxide (0.98 g, 0.024M). After addition, the mixture was warmed to room temperature and stirred 2.5 hr. The mixture was diluted with ethyl acetate (50 ml) and washed with water (2.times.25 ml) and brine (1.times.25 ml). The organic layer was dried over magnesium sulfate and concentrated under vacuum to afford N'-t-butyl-N-valeryl-N'-benzoyl-hydrazine as a yellow oil.
EXAMPLE NO. 654
Preparation of N'-t-butyl-N-phenylacetyl-N'-benzoylhydrazine
To a stirred suspension of t-butylhydrazine hydrochloride (2.0 g, 0.016M) in toluene (30 ml) was added 50% sodium hydroxide (1.3 g, 0.016M). After 15 minutes, the mixture was cooled to 5.degree. C. and phenylacetyl chloride (2.4 g, 0.016M) and 50% sodium hydroxide (1.3 g, 0.016M) were added separately and simultaneously so as to maintain the reaction temperature below 10.degree. C. After the addition, the reaction mixture was allowed to warm to room temperature and stirred for 1 hr. The mixture was diluted with hexane and the solid product isolated by filtration. This product (3.2 g, 0.015M) was water (100 ml) and the solids were air dried overnight. The solids were dissolved in 10% aq. hydrochloric acid (300 ml) and were washed with ethyl acetate (3.times.300 ml). The ethyl acetate washes were combined and extracted with 10% aq. hydrochloric acid (250 ml). The 10% aq. hydrochloric acid layers were combined and were neutralized with 50% aq. sodium hydroxide while being stirred. Stirring was continued for 1 hour at room temperature. The mixture was suction filtered and rinsed with water (100 ml) and the solids were air-dried yielding a white solid (m.p. 125.degree.-126.degree. C.).
To a stirred solution of 1-t-butyl-1-benzoylhydrazine (1 g, 0.005M) in toluene (40 ml) cooled to 5.degree. C. was added 3-chloro-2,2-dimethylpropionylchloride (1.2 g, 0.007M) and 50% aq. sodium hydroxide (0.45 g, 0.0056M) so as to maintain the temperature below 10.degree. C. The mixture was warmed to room temperature and stirred 1 hr. The mixture was diluted with hexane (40 ml) and water (10 ml). The white solid product N'-t-butyl-N-(betachloropivaloyl)-N'-benzoylhydrazine was isolated by suction filtration, washed with 50 ml hexane and 50 ml water and- dried.
EXAMPLE NO. 661
Preparation of N'-t-butyl-N-(1,2,2-trichlorovinyl)carbonyl-N'-benzoylhydrazine
To a stirred suspension of tert-butylhydrazine hydrochloride (200 g, 1.61 mole) in acetone (400 ml) was dropwise added triethylamine (200 g, 1.98 mole). After addition, the mixture was refluxed for 3 hours while periodically adding magnesium sulfate (100 g total). The mixture was cooled to room temperature and funnel filtered. The filtrate was was dropwise added triethylamine (200 g, 1.98 mole). After addition, the mixture was refluxed for 3 hours while periodically adding magnesium sulfate (100 g total). The mixture was cooled to room temperature and funnel filtered. The filtrate was dried over magnesium sulfate and concentrated under vacuum at 5.degree. C. until a slurry formed. The mixture was diluted with ethyl acetate (100 ml) and was filtered. The filtrate was distilled yielding a yellow oil (b.p. 121.degree.-127.degree. C.).
Into a stirred suspension of 1-t-butyl-2-acetonehydrazone (43 g, 0.34 mole) in toluene (250 ml) at 5.degree. C. was added 10% aq. sodium hydroxide (200 ml, 0.50 mole). After addition, benzoylchloride (70 g, 0.50 mole) was added dropwise to this mixture. Stirring was continued for 2 hours at 5.degree. C. and 72 hours at room temperature. The mixture was diluted with ethyl acetate (300 ml) and washed with water (3 x 200 ml) and brine (200 ml). The organic layer was dried over magnesium sulfate and concentrated at 35.degree. C. under vacuum to afford a yellow oil.
A mixture of 1-t-butyl-1-benzoyl-2-acetone hydrazone (90 g, approximately 60% pure,approximately 0.3 mole), ethanol (500 ml, 200 proof) and 10% aq. hydrochloric acid (500 ml) was stirred overnight at room temperature. The mixture was concentrated under vacuum to a thick slurry. The slurry was suction filtered with a water wash (400 ml). The solids were air-dried overnight.
The solids were dissolved in a water (200 ml) and methanol (100 ml) solution on a steam bath. The mixture stood at room temperature overnight. The mixture was suction filtered and rinsed with cold water (100 ml) and the solids were air dried overnight. The solids were dissolved in 10% aq. hydrochloric acid (300 ml) and were washed with ethyl acetate (3.times.300 ml). The ethyl acetate washes were combined and extracted with 10% aq. hydrochloric acid (250 ml). The 10% aq. hydrochloric acid layers were combined and were neutralized with 50% aq. sodium hydroxide while being stirred. Stirring was continued for 1 hour at room temperature. The mixture was suction filtered and rinsed with water (100 ml) and the solids were air-dried yielding a white solid (m.p. 125.degree.-126.degree. C.).
To a stirred solution of 1-t-butyl-1-benzoylhydrazine (1 g, 0.005M) in toluene (40 ml) cooled to 5.degree. C. was added 3-chloro-2,2-dimethylpropionylchloride (1.2 g, 0.007M) and 50% aq. sodium hydroxide (0.45 g, 0.0056M) so as to maintain the temperature below 10.degree. C. The mixture was warmed to room temperature and stirred 1 hr. The mixture was diluted with hexane (40 ml) and water (10-20 ml). The white solid product N'-t-butyl-N-(betachloropivaloyl)-N'-benzoylhydrazine was isolated by suction filtration, washed with 50 ml hexane and 50 ml water and dried.
EXAMPLE NO. 660
Preparation of N'-t-butyl-N-(1,2,2-trichlorovinyl)carbonyl-'-benzoylhydrazine
To a stirred suspension of tert-butylhydrazine hydrochloride (200 g, 1.61 mole) in acetone (400 ml) was dropwise added triethylamine (200 g, 1.98 mole). After addition, the mixture was refluxed for 3 hours while periodically adding magnesium sulfate (100 g total). The mixture was cooled to room temperature and funnel filtered. The filtrate was dried over magnesium sulfate and concentrated under vacuum at 5.degree. C. until a slurry formed. The mixture was dilued with ethylacetate (100 ml) and was filtered The filtrate was distilled yielding a lightly yellow tinted oil (b.p. 121.degree.-127.degree. C.).
To a stirred suspension of 1-t-butyl-2-acetonehydrazone (43 g, 0.34 mole) in toluene (250 ml) at 5.degree. C. was added 10% aq. sodium hydroxide (200 ml, 0.50 mole). After addition, benzoylchloride (70 g, 0.50 mole) was added dropwise to the mixture. Stirring was continued for 2 hours at 5.degree. C. and 72 hours at room temperature. The mixture was diluted with ethyl acetate (300 ml) and washed with water (3.times.200 ml) and brine (200 ml). The organic layer was dried over magnesium sulfate and concentrated at 35.degree. C. under vacuum yielding a yellow oil.
A mixture of 1-t-butyl-1-benzoyl-2-acetone hydrazone (90 g, approximately 60% pure,approximately 0.3 mole), ethanol (500 ml, 200 proof) and 10% aq. hydrochloric acid (500 ml) was stirred overnight at room temperature. The mixture was concentrated under vacuum to a thick slurry. The slurry was suction filtered and washed with water (400 ml). The solids were air-dried overnight.
The solids were dissolved in a water (200 ml) and methanol (100 ml) solution on a steam bath. The mixture stood at room temperature overnight. The mixture was suction filtered and rinsed with cold water (100 ml) and the solids were air dried overnight. The solids were dissolved in 10% aq. hydrochloric acid (300 ml) and were washed with ethyl acetate (3.times.300 ml). The ethyl acetate washes were combined and extracted with 10% aq. hydrochloric acid (250 ml). The 10% aq. hydrochloric acid layers were combined and were neutralized with 50% aq. sodium hydroxide while being stirred. Stirring was continued for 1 hour at room temperature. The mixture was suction filtered and rinsed with water (100 ml) and the solids were air-dried yielding a white solid (m.p. 125.degree.-126.degree. C.).
To a stirred solution of 1-t-butyl-1-benzoylhydrazine (1.5 g, 0.008M) in methylene chloride at 5.degree. C. was added, simultaneously and separately, trichloroacryloylchloride (1.7 g, 0.009M) and triethylamine (0.9 g, 0.009M). After addition, the reaction was warmed to room temperature and stirred for 3 h. The flask's contents were diluted with 50 ml methylene chloride and washed with water (3.times.75 ml) and brine solution (1.times.75 ml). The organic layer was dried over magnesium sulfate and the solvent removed under vacuum to afford N'-t-butyl-N-(1,2,2-trichlorovinyl)carbonyl-N'-benzoylhydrazine as a white solid product.
EXAMPLE 682
Preparation of N'-t-butyl-N-benzoyl-N'-n-pentanecarbonylhydrazine
To a stirred suspension of t-butylhydrazine hydrochloride (1 g, 0.008M) in toluene (30 ml) at room temperature was added dropwise a 50% aqueous solution of sodium hydroxide (0.64 g, 0.008M). After 15 min., the reaction mixture was cooled to 5.degree. C. and a solution of benzoyl chloride (1.12 g, 0.008M) in toluene (5 ml) and a solution of aqueous 50% sodium hydroxide (0.64 g, 0.008M) were added dropwise simultaneously from separate addition funnels while maintaining the temperature at or below 10.degree. C. Following the addition, the reaction mixture was warmed to room temperature and stirred for 1 hr. The reaction was diluted with hexane and the solid N'-t-butyl-N'-benzoylhydrazine was isolated by filtration.
To a stirred solution of the monobenzoylated compound (1.4 g, 0.0073M) in toluene (30 ml) at 5.degree. C., were added dropwise simultaneously from separate addition funnels, solutions of hexanoyl chloride (1 g, 0.0073M) in toluene (5 ml) and aqueous 50% sodium hydroxide solution (0.58 g, 0.0073M) while maintaining the temperature below 10.degree. C. Following the addition, the reaction mixture was warmed to room temperature and stirred for 1 hr. The mixture was then diluted with hexane and the solid product isolated by filtration. The product was washed with water and hexane and dried. The crude product was recrystallized from ether-methanol to afford N'-t-butyl-N-benzoyl-N'-n-pentanecarbonylhydrazine as a white powder. m.p. 117.degree.-118.degree. C.
EXAMPLE 683
Preparation of N'-t-butyl--N-benzoyl-N'-cyclohexanecarbonylhydrazine
To a stirred suspension of t-butylhydrazine hydrochloride (1 g, 0.008M) in toluene (30 ml) at room temperature was added dropwise a 50% aqueous solution of sodium hydroxide (0.64 g, 0.008M). After 15 min., the reaction mixture was cooled to 5.degree. C. and a solution of benzoyl chloride (1.12 g, 0.008M) in toluene (5 ml) and a solution of aqueous 50% sodium hydroxide (0.64 g, 0.008M) were added dropwise and simultaneously from separate addition funnels while maintaining the temperature at or below 10.degree. C. Following the addition, the reaction mixture was warmed to room temperature and stirred for 1 hr. The reaction was diluted with hexane and the solid N'-t-butyl-N-benzoylhydrazine was isolated by filtration.
To a stirred solution of the monobenzoylated compound (1.4 g, 0.0073M) in toluene (30 ml) at 5.degree. C., were added dropwise and simultaneously from separate addition funnels, solutions of cyclohexanecarbonyl chloride (1.1 g, 0.0073M) in toluene (5 ml) and aqueous 50% sodium hydroxide solution (0.58 g, 0.0073 M) while maintaining the temperature below 10.degree. C. Following the addition, the reaction mixture was warmed to room temperature and stirred for 1 hr. The mixture was then diluted with hexane and the solid product isolated by filtration. The product was washed with water and hexane and dried. The crude product was recrystallized from ether-methanol to afford N'-t-butyl-N-benzoyl-N'-cyclohexanecarbonylhydrazine as a white powder. m.p. 202.degree.-204.degree. C.
EXAMPLE 688
Preparation of N'-t-butyl-N-benzoyl-N'-pivaloylhydrazine
To a stirred suspension of t-butylhydrazine hydrochloride (2 g, 0.016M) in toluene (50 ml) at room temperature was added dropwise a 50% aqueous solution of sodium hydroxide (1.28 g, 0.016M). After 15 min., the reaction mixture was cooled to 5.degree. C. and a solution of benzoyl chloride (2.3 g, 0.017M) in toluene (5 ml) and a solution of aqueous 50% sodium hydroxide (1.36 g, 0.017M) were added dropwise simultaneously from separate addition funnels while maintaining the temperature at or below 10.degree. C. Following the addition, the reaction mixture was warmed to room temperature and stirred for 1 hr. The reaction mixture was diluted with hexane and the solid N'-t-butyl-N-benzoylhydrazine was isolated by filtration.
To a stirred solution of the monobenzoylated compound (2 g, 0.010M) in pyridine (15 ml) was added pivaloyl chloride (1.8 g, 0.015M) and a catalytic amount of 4-dimethylamino pyridine. The mixture was heated to 60.degree. C. and stirred for approximately 1 hr., cooled and diluted with methylene chloride. The organic layer was washed with 10% HCl (3.times.25 ml) and water (50 ml), dried over magnesium sulfate and the solvent removed under vacuum. The solid product was recrystallized from methanol-ether to afford N'-t-butyl-N-benzoyl-N'-pivaloylhydrazine in 60% yield as a white-solid. m.p. 217.degree.-220.degree. C.
EXAMPLE 689
Preparation of N'-t-buty-1-N-benzoyl-N'-phenylacetylhydrazine
To a stirred suspension of t-butylhydrazine hydrochloride (1 g, 0.008M) in toluene (30 ml) at room temperature was added dropwise a 50% aqueous solution of sodium hydroxide (0.64 g, 0.008M). After 15 min., the reaction mixture was cooled to 5.degree. C. and a solution of benzoyl chloride (1.12 g, 0.008M) in toluene (5 ml) and a solution of aqueous 50% sodium hydroxide (0.64 g, 0.008M) were added dropwise simultaneously from separate addition funnels while maintaining the temperature at or below 10.degree. C. Following the addition, the reaction mixture was warmed to room temperature and stirred for 1 hr. The reaction was diluted with hexane and the solid N'-t-butyl-N-benzoylhydrazine was isolated by filtration.
To a stirred solution of the monobenzoylated compound (1.5 g, 0.0078M) in toluene (30 ml) at 5.degree. C., were added dropwise and simultaneously from separate addition funnels, solutions of phenylacetyl chloride (1.2 g, 0.008M) in toluene (5 ml) and aqueous 50% sodium hydroxide solution (0.63 g, 0.0078M) while maintaining the temperature below 10.degree. C. Following the addition, the reaction mixture was warmed to room temperature and stirred for 1 hr. The mixture was then diluted with hexane and the solid product isolated by filtration. The product was washed with water and hexane and dried. The crude product was recrystallized from ether-methanol to afford N'-t-butyl-N-benzoyl-N'-phenylacetylhydrazine as a white powder. m.p. 167.degree.-169.degree. C.
EXAMPLE 691
Preparation of N'-t-butyl-N-benzoyl-N'-(beta-trifluoromethylcrotonyl)hydrazine
N'-t-butyl-N-benzoylhydrazine (1.0 g,) in 2 ml toluene was added dropwise to a solution of beta-trifluoromethylcrotonyl chloride (prepared by addition of oxalyl chloride (1.3 g) to a solution of 1.5 g beta-trifluoromethylcrotonic acid in 5 ml toluene at 23.degree. C.). After 30 min. at 23.degree. C., the reaction mixture was partitioned between saturated aqueous sodium bicarbonate (20 ml) and ether (20 ml). The ether layer was evaporated under reduced pressure to about 10 ml and the excess hydrazine was removed by filtration. The filtrate was evaporated to give N'-t-butyl-N-benzoyl-N'-(beta-trifluoromethylcrotonyl)hydrazine as a colorless oil.
EXAMPLE 699
Preparation of N'-t-butyl-N-benzoyl-N'-methacryloylhydrazine
N'-t-butyl-N-benzoylhdyrazine (0.9 g) suspended in 10 ml toluene and 1 ml H20 containing 0.3 g 50% sodium hydroxide was treated with 1.2 g of methacryloyl chloride at 23.degree. C. After 18 hours, 5 ml of hexane was added and N'-t-butyl-N-benzoyl-N'-methacryloylhydrazine was collected by filtration. m.p. 148.degree.-152.degree. C.
EXAMPLE 702
Preparation of N'-t-butyl-N'-cyclobutanecarbonyl-N-(4-chlorobenzoyl)hydrazine
To a stirred solution of N'-t-butyl-N-(4-chlorobenzoyl)hydrazine (2.0 9, 8.8 mmole) in toluene (35 ml) at 5.degree. C. was added cyclobutanecarboxylic acid chloride (1.25 g, 10.5 mmole) in one portion. To the above mixture was dropwise added 50% NaOH solution (0.85 g, 10.6 mmole). After addition, the ice water bath was removed and the reaction mixture was stirred at room temperature overnight.
The mixture was diluted with hexane (30 ml) and H20 (30 ml) and stirred for another 30 min. The solid product was collected by suction-filtration and washed with H20 (100 ml) and hexane (100 ml) to yield 1.5 g of N'-t-butyl-N'-cyclobutanecarbonyl-N-(4-chlorobenzoyl)hydrazine.
EXAMPLE 722
Preparation of N'-t-buyl-N-benzoyl-N'-isonicotinoylhydrazine
N'-t-butyl-N-benzoylhydrazine (1.0 g, 0.0052 mol) was suspended in 20 ml of toluene. Isonicotinoyl chloride hydrochloride (0.93 g, 0.0052 mol) was added and then a solution of sodium hydroxide (1.25 g of 50% aqueous NaOH) in 5 ml of water was added dropwise. After stirring at 23.degree. C. for 2 hours, the solids were removed by filtration, washed with water and dried in air. The crude product was chromatographed on silica gel using 5% methanol/methylene chloride as eluant to afford pure N'-t-butyl-N-benzoyl-N'-isonicotinoylhydrazine. m.p. >210.degree. C.
EXAMPLE 723
Preparation of N'-t-butyl-N-(2-pyridinecarbonyl)-N'-benzoylhydrazine
A solution of N'-t-butyl-N-(2-pyridinecarbonyl)hydrazine (1.0 g, 0.00518 mol) in 20 ml of toluene at 23.degree. C. was treated sequentially with 50% sodium hydroxide (1.3 g) and benzoyl chloride (0.728 g). The mixture was stirred overnight. The solids were removed by filtration and washed with water to afford N'-t-butyl-N-(2-pyridinecarbonyl)-N'-benzoylh-ydrazine.
EXAMPLE 724
Preparation of N'-t-butyl-N-benzoyl-N'-nicotinoylhydrazine
A solution of N'-t-butyl-N-benzoylhydrazine (2.0 g) and nicotinoyl chloride hydrochloride in 20 ml of methylene chloride at 23.degree. C. was treated dropwise with triethylamine (4 ml). The reaction mixture was stirred at 23.degree. C. for 0.5 hours. Solids were removed by filtration. The filtrate was diluted with 10N HCl and ether. The layers were separated and the organic layer was washed with 10N HCl. The aqueous layer was neutralized with solid sodium bcarbonate and extracted with ether. The ether extracts were treated with charcoal and then dried with magnesium sulfate. Evaporation of solvents afforded a yellow oil which was chromatographed on silica gel using as eluant a mixture of 10% CH.sub.3 OH, 40% CH.sub.2 Cl.sub.2, 50% Et.sub.2 O to afford N'-t-butyl-N-benzoyl-N'-nicotinoylhydrazine as a yellow foam. m.p. 60.degree.-63.degree. C.
EXAMPLE 727
Preparation of N'-t-butyl-N-(2-pyridinecarbonyl)-N'-(2-nitrobenzoyl)hydrazine
A solution of N'-t-butyl-N-(2-pyridinecarbonyl)hydrazine (1.0 g, 0.00518 mol) in 20 ml of toluene was treated dropwise simultaneously with a solution of sodium hydroxide (1.24 g of 50% aqueous solution) in 5 ml of water and 2-nitrobenzoyl chloride (0.96 g). The resulting mixture was stirred at 23.degree. C. overnight. Water was added and the mixture was extracted with ether. A second extraction was performed with methylene chloride and the combined organic extracts were dried over magnesium sulfate. Evaporation afforded 0.4 g of N'-t-butyl-N-(2-pyridinecarbonyl)-N'-(2-nitrobenzoyl)hydrazine as a yellow solid. m.p. 137.degree.-140.degree. C.
EXAMPLE 729
Preparation of N'-t-butyl-N-(2-pyridinecarbonyl)-N'-(2-bromobenzoyl)hydrazine
An aqueous solution of sodium hydroxide (1.24 g of 50% NaOH diluted with 5 ml of water) was added to a solution of N'-t-butyl-N-(2-pyridinecarbonyl)hydrazine (1.0 g, 0.00518 mol) in 20 ml of toluene at 23.degree. C. The mixture was cooled and treated with 2-bromobenzoyl chloride (1.137 g, 0.00518 mol). The mixture was then stirred at 23.degree. C. overnight. The solids were removed by filtration, washed with water and dried to afford 0.96 g of N'-t-butyl-N-(2-pyridinecarbonyl)-N'-(2-bromobenzoyl)hydrazine as a white solid. m.p. 179.degree.-180.degree. C.
EXAMPLE 733
Preparation of N'-t-butyl-N-(2-pyridinecarbonyl)-N'-(3,4-dichlorobenzoyl)hydrazine
A solution of N'-t-butyl-N-(2-pyridinecarbonyl)hydrazine (0.5 g) in 10 ml of toluene was treated with 50% sodium hydroxide (0.61 g). 3,4-dichlorobenzoyl chloride (0.6 g) was added and the mixture was stirred rapidly for 4 hours at 23.degree. C. and then was allowed to stand for 48 hours. The solids were removed by filtration and washed with water to afford 0.75 g of N'-t-butyl-N-(2-pyridinecarbonyl)-N'-(3,4-dichlorobenzoyl)hydrazine as a white solid. m.p. 175.degree.-178.degree. C.
EXAMPLE 737
Preparation of N'-t-butyl-N-(5-bromonicotinoyl-N'-(4-chlorobenzoyl)hydrazine
N'-t-butyl-N'-(4-chlorobenzoyl)hydrazine was prepared substantially according to the procedure for preparing N'-t-butyl-N'-benzoylhydrazine described for Example 220 step 3 except 4-chlorobenzoyl chloride was used in place of benzoyl chloride.
A solution of N'-t-butyl-N'-(4-chlorobenzoyl)hydrazine (0.5 g, 0.0022 mol) and 5-bromonicotinic acid (0.44 g, 0.0022 mol) in 10 ml of methylene chloride containing triethylamine (0.33 g) was added to a solution of methanesulfonyl chloride (0.25 g, 0.0022 mol) in 10 ml of methylene chloride at 0.degree. C. The resulting mixture was stirred at 23.degree. C. for 2 hours and then was allowed to stand overnight at 23.degree. C. Aqueous sodium bicarbonate was added and the layers were separated. The aqueous layer was re-extracted with methylene chloride. The organic extracts were evaporated to give a yellow solid which was triturated with hexane/methylene chloride to afford N'-t-butyl-N-(5-bromonicotinoyl)-N'-(4-chlorobenzoyl)hydrazine as an off-white solid. m.p. 193.degree.-197.degree. C.
EXAMPLE 738
Preparation of N'-t-butyl-N-(pyrazinecarbonyl)-N'-benzoylhydrazine
To a mechanically stirred solution of t-butylhydrazine hydrochloride (51 g, 0.41 mol) in dioxane (100 ml) and water (50 ml), cooled in an ice bath was treated with 50% sodium hydroxide (32 g). The resulting mixture was treated dropwise with di-t-butyl-dicarbonate (92 g, 0.42 mol) over about one-half of an hour. After complete addition, the reaction mixture was warmed to room temperature and stirred for 2 hours. The resulting white solid was filtered off, washed with water and air-dried to afford 74 g of N'-t-butyl-N-t-butoxycarbonylhydrazine, mp. 69.degree.-71.degree. C.
A mechanically stirred solution of N'-t-butyl-N-t-butoxycarbonylhydrazine (61 g, 0.32 mol) in toluene (120 ml) cooled in an ice bath, was treated dropwise and simultaneously with 50% sodium hydroxide (31 g) in water (50 ml) and benzoyl chloride (45 g). The addition was complete in 20 minutes and the resulting mixture was warmed to room temperature and allowed to stir for one hour. The resulting white solid was filtered, washed with water and air dried to afford 94 g of N-t-butoxycarbonyl-N'-benzoyl-N'-t-butylhydrazine, mp. 167.degree.-170.degree. C.
To a mechanically stirred solution of N-t-butoxycarbonyl-N'-benzoyl-N'-t-butylhydrazine (52 g, 0.18 mol) in methanol (100 ml) was added concentrated hydrochloric acid (35 ml). The resulting mixture was stirred at room temperature for 4 days and then neutralized with saturated aqueous sodium bicarbonate. The resulting white solid was filtered, washed with water and dried under vacuum to afford N'-t-butyl-N-benzoylhydrazine (39 g) mp. 124.degree.-125.degree. C. solution of N'-t-butyl-N'-benzoylhydrazine (0.86 g, 0.0031 mol) and pyrazine carboxylic acid (0.56 g, 0.0045 mol) in 10 ml of methylene chloride at 23.degree. C. This mixture was added to a solution of methane-sulfonyl chloride (0.6 g, 0.0052 mol) in 10 ml of methylene chloride at 0.degree. C. The mixture was stirred at 23.degree. C. for 3 hours and then allowed to stand at 23.degree. C. overnight. Aqueous sodium bicarbonate was added and evaporated to give crude product which was triturated th ether to afford N'-t-butyl-N-(pyrazinecarbonyl)-N'-benzoylhydrazine as a white solid. m.p. 181.degree.-83.degree. C.
EXAMPLE 739
Preparation of N'-t-butyl-N-isonicotinoyl-N'-benzoylhydrazine
A solution of N'-t-butyl-N'-benzoylhydrazine (0.5 g, 0.00026 mol) in 10 ml of toluene was treated with 50% sodium hydroxide (0.6 g) followed by isonicotinyl chloride hydrochloride (0.47 g, 0.0026 mol). The mixture was stirred at 23.degree. C. overnight. The solids were removed by filtration and washed with isonicotinyl-N'-benzoylhydrazine.
EXAMPLE 743
Preparation of N'-t-butyl-N-(2-pyridinecarbonyl)-N'-(4-fluorobenzoyl)hydrazine)
By substantially following the procedures described above for Example 2, except using 4-fluorobutyl-N((2-pyridinecarbonyl)-N'-(4-fluorobenzoyl)-N'-t-hydrazine was afforded.
EXAMPLES 754 AND 755
Preparation of N'-t-butyl-N'-(2-pyridinecarbonyl)-N-benzoylhydrazine
To a suspension of 2-picolinic acid (12.8 g, 0.104 mol.) in methylene chloride (80 ml) were added dropwise triethylamine (14 g, 0.139 mol.) in 10 ml methylene chloride followed by methanesulfonyl chloride (13 g, 0.113 mol.) in 10 ml methylene chloride at 0.degree. C. The resulting mixture was stirred for half an hour before the dropwise addition of N'-t-butyl-N-benzoylhydrazine (20.0 g, 0.10 mole) in 80 ml methylene chloride at 0.degree. C. to 23.degree. C. The final dark brown mixture was allowed to stir at 23.degree. C. for one hour, and to stand at 23.degree. C. overnight.
Aqueous sodium bicarbonate was added and the layers were separated. The aqueous layer was re-extracted with methylene chloride. The organic extracts were combined, and dried over magnesium sulfate. Evaporation under reduced pressure gave 25 g of a light green, brown solid. Recrystalization on a steam bath with ethyl acetate:hexane (80:20v/v) afforded a light yellow solid.
Column chromatography on silica gel, eluted first with methylene chloride and ether and then with ethyl acetate afforded two separate isomers of N'-t-butyl-N'-(2-pyridinecarbonyl)-N-benzoylhydrazine.
EXAMPLE 764
Preparation of N'-t-butyl-N-benzoyl-N'-(2-furoyl)hydrazine
N'-t-butyl-N-benzoylhydrazine (1 g) was dissolved in 20 ml toluene. Water (5 ml) and 50% aqueous sodium hydroxide (1.25 g) was added followed by 2-furoylchloride (0.68 g). After stirring for 7 hours at room temperature, 0.3 g 2-furoylchloride was added and the mixture stirred for a further 6 hours. The solid product, N'-t-butyl-N-benzoyl-N'-(2-furoyl)hydrazine, was removed by filtration and washed with water. m.p. 155.degree.-175.degree. C.
EXAMPLE 765
Preparation of N'-t-butyl-N-benzoyl-N'-(2-thiophenecarbonyl)hydrazine
N'-t-butyl-N-benzoylhydrazine (1.0 g) was dissolved in 20 ml toluene. 50% aqueous sodium hydroxide (1.25 g) was added followed by 2-thiophenecarbonylchloride (0.76 g). The mixture was stirred at room temperature for 14 hours. The solid product, N'-t-butyl-N-benzoyl-N'-(2thiophenecarbonyl)hydrazine, was removed by filtration and washed with water. m.p. >200.degree. C.
EXAMPLE 766
Preparation of N'-t-butyl-N-(2-thiophenecarbonyl)-N'-benzoylhydrazine
N'-t-butyl-N-(2-thiophenecarbonyl)hydrazine (1 g) was dissolved in 10 ml toluene and treated with 50% aqueous sodium hydroxide (1.0 g) and water (2 ml) followed by benzoylchloride (0.8 g). After stirring for 14 hours at room temperature, the solid product, N'-t-butyl-N-(2-thiophenecarbonyl)-N'-benzoylhydrazine, was removed by filtration and washed with water. m.p. >190.degree. C.
EXAMPLE 76
Preparation of N'-t-butyl-N-(2-furoyl)-N'-benzoylhydrazine
N'-t-butyl-N-(2-furoyl)hydrazine (1.0 g) was dissolved in 10 ml toluene and 2 ml water. 50% aqueous sodium hydroxide (1.0 g) was added followed by benzoylchloride (0.8 g). After stirring for 14 hours at room temperature, the solid product, N'-t-butyl-N-(2-furoyl)-N'-benzoylhydrazine, was removed by filtration and washed with water. m.p. 160.degree.-162.degree. C.
EXAMPLE 722
Preparation of N'-t-butyl-N-(4-methylbenzoyl)-N'-(2,5-dichlorothiophene-3-carbonyl)hydrazine
N'-t-butyl-N-4-methylbenzoylhydrazine (0.7 g) was dissolved in 35 ml toluene. Water (5 ml) and 50% aqueous sodium hydroxide (0.8 g) were added followed by 2,5-dichlorothiophene-3-carbonylchloride (2.0 g). After stirring for 3 hours at room temperature, ether was added and the organic layer separated. Evaporation afforded a solid which was triturated with 10% ether-hexane to afford N'-t-butyl-N-(4-methylbenzoyl)-N'-(2,5-dichlorothiophene-3carbonyl)hydrazine. m.p. 163.degree.-165.degree. C.
EXAMPLE 778
Preparation of N'-t-butyl-N-(N-methyl-2-pyrrolecarbonVI)-N'-benzoylhydrazine
N'-t-butyl-N-(N-methyl-2carbonylpyrrole)hydrazine (0.8 g) was dissolved in 10 ml toluene and 1 ml water. 50% aqueous sodium hydroxide (10 drops) was added followed by benzoylchloride (1.2 g). After 14 hours stirring at room temperature, ether was added and the product, N'-t-butyl-N-(N-methyl-2-pyrrolecarbonyl)-N'-benzoylhydrazine, was isolated by filtration and washed with ether. m.p. 182.degree.-185.degree. C.
EXAMPLE 787
Preparation of N'-t-butyl-N-(1,2,3-triazole-4-carbonyl)-N'-(3-methylbenzoyl)hydrazine
1,2,3-triazole-4-carboxylic acid (1.0 g) and triethylamine (0.9 g) were dissolved in 40 ml methylene chloride and cooled in an ice bath. Methanesulfonylchloride (1.0 g) was added dropwise. After addition was complete, the reaction mixture was stirred for 0.5 hours. N'-t-butyl-N'-(3methylbenzoyl)hydrazine (1.84 g) in 10 ml CH.sub.2 Cl.sub.2 was added dropwise. The resulting mixture was allowed to stand for 14 hours. Aqueous sodium bicarbonate was added. The organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated to give a yellow oil. Chromatography on silica gel using acetone as eluant afforded N'-t-butyl-N-1,2,3-triazole-4-carbonyl-N'-(3-methylbenzoyl)hydrazine.
EXAMPLE NO. 802
Preparation of N'-(1-cyano-1-methyl)ethyl-N,N'-dibenzoylhydrazine
To a suspension of benzoylhydrazine (13.6 g, 0.1 mole) in deionized water (50 ml) at 5.degree. C. with stirring was dropwise added concentrated hydrogen chloride (9.8 g, 0.1 mole). To the resulting clear solution was added sodium cyanide (5.2 g, 0.1 mole) and acetone (6.5 g, 0.11 mole). A white and thick precipitate appeared. The cooling bath was removed and the reaction flask was stoppered tightly. The reaction mixture was stirred for 18 hours. The precipitate was collected by suction-filtration and was washed with a small amount of water to give 17.5 g (86.2% yielded) of the desired intermediate, N'-(1-cyano-1-methyl)ethyl-N-benzoic acid hydrazide, as the starting material for the next step. (m.p. 82.degree.-92.degree. C.)
To the solution of N'-(1-cyano-1-methyl)ethyl-N-benzoic acid hydrazide (2 g, 0.01 mole) in dry methylene chloride (25 ml) under nitrogen at room temperature with stirring was added benzoyl chloride (2.02 g, 0.014 mole). To the above mixture was dropwise added triethylamine (1.31 g, 0.013 mole). The reaction mixture was stirred at room temperature for 5 hours. The reaction mixture was diluted with methylene chloride (50 ml), washed with water and brine. The organic layer was dried over MgSO.sub.4 and the solvent was evaporated at reduced pressure to give a residue. The residue was treated with ethyl acetate/hexane mixture (1:1) affording a crude solid product which was collected by suction-filtration (1 g, 33% yield). An analytical sample was obtained by crystallization from ethyl acetate/hexane (4:1), m.p. 202.degree.-204.degree. C. NMR and IR spectra showed the desired product.
EXAMPLE NO. 809
Preparation of N'-(1-cyano-1-methyl)ethyl-N,N'-di-4-toluoylhydrazine
To the suspension of 4-toluic acid hydrazide (15.0 g, 0.1 mole) in water (150 ml) and ethanol (20 ml) at 5.degree. C. with stirring was dropwise added concentrated hydrogen chloride (10 g, 0.1 mole). To the above suspension was carefully added sodium cyanide (5.3 g, 0.1 mole) and acetone (6.6 g, 0.11 mole). The reaction flask was stoppered tightly and the cooling bath was removed. The resulting viscous reaction mixture was stirred at room temperature for more than 24 hours. The precipitate was collected by suction-filtration and was washed with a small amount of diluted hydrogen chloride and water affording 14.6 g. (64.8%) of N'-(1-cyano-1-methyl)ethyl-4-toluic acid hydrazide as the starting material for the next step. Analytical sample was obtained by crystallization from ethyl acetate/hexane (3:1), m.p. 146.degree.-148.degree. C.
To the solution of N'-(1-cyano-1-methyl)ethyl-4-toluic acid hydrazide (2.17 g, 0.01 mole) in dry methylene chloride (65 ml) under nitrogen with magnetic stirring was added 4-dimethylaminopyridine catalyst (1.34 g, 0.011 mole) followed by 4-methylbenzoyl chloride (2.52 g, 0.017 mole). To the above mixture was dropwise added triethylamine (1.1 g, 0.011 mole). The reaction mixture was slightly exothermic. After stirring at room temperature for 40 minutes the reaction mixture was diluted with methylene chloride (50 ml), washed with diluted HCl solution (2.times.50 ml), dil NaOH (50 ml), H.sub.2 O (50 ml) and brine. The organic layer was dried over MgS04, and the solvent was evaporated under reduced pressure to give a residue. The residue was treated with ethyl acetate/hexane mixture (1:1) and the resulting solid was collected by suction-filtration and affording 2.75 g (82% yield) of almost pure product. (m.p. 192.degree.-198.degree. C.) NMR and IR spectra showed the desired product.
EXAMPLE NO. 822
Preparation of N'-(1,1-dimethyl-3-butenyl)-N,N'-dibenzoylhydrazine
To a gently refluxing solution of allyl magnesium bromide (380 ml of lM solution) was added acetone azine (20 g) dissolved in diethyl ether (200 ml). The solution was refluxed for three days. Upon cooling, a saturated solution of ammonium chloride (50 ml) was added. The aqueous layer was separated and washed twice with diethyl ether (200 ml). The combined ether extracts were dried over anhydrous magnesium sulfate, filtered and the ether removed at reduced pressure. The product was distilled through a vigreux column at 3.1 torr and collected in a dry ice/acetone cooled receiving flask. The boiling point was 60.degree.-65.degree. C. 15 g of product was collected.
Oxalic acid (16.7 g) was dissolved in a solution of ethanol:diethyl ether (1:1) (150 ml) and water (3.3 g) was added. To this acid solution was added the hydrazone (13 g) dissolved in diethyl ether (75 ml). The solution was stirred for 24 hours then filtered. The solid is washed once with diethyl ether. The filtrate was concentrated and combined with the solid to afford a 71% yield (17.2 g) of the hydrazine oxalate.
The 1,1-dimethyl-3-butenylhydrazine oxalate (2 g) was dissolved in toluene and neutralized with 50% aqueous sodium hydroxide. To this solution was added benzoyl chloride (2.8 9) and sodium hydroxide (50% Aq. solution) (3.2 g) at 25.degree. C. The reaction mixture was warmed to room temperature and stirred. The mixture was diluted with hexane and filtered to afford an oily product which solidified upon standing. (m.p. 105.degree.-112.degree. C.)
EXAMPLE NO. 829
Preparation of N'-t-butyl-N-benzoyl-N'-benzylhydrazine
Benzyl bromide (0.9 g), 1-benzoyl-2-t-butyl hydrazine (1 g) and triethylamine (0.52 g) were warmed in dimethylformamide (50 ml) at 50.degree. C. for 2 hours. The reaction mixture was cooled to room temperature, diluted with diethylether (100 ml) and washed three times with 25 ml of water. The organic layer was dried over magnesium sulfate, filtered, and the solvent removed in vacuo to afford the product as a white solid. The product was chromatographed on silica gel (G:70 to 230 mesh) using methylene chloride as eluent to afford a 75% yield of a white solid: m.p. 147.degree.-149.
EXAMPLE NO. 837
Preparation of N'-t-butyl-N-furoyl-N'-benzylhydrazine
Benzyl bromide (1.8 g), 1-furoyl-2-t-butyl hydrazine (2 g) and excess powdered potassium carbonate were stirred in dimethylformamide (50 ml) at 50.degree. C. for 2 hours. The reaction mixture was cooled to room temperature, diluted with diethyl ether and washed several times with water. The organic layer was dried over magnesium sulfate, filtered, and the solvent removed in vacuo. The white solid product was chromatographed on silica gel (G:70.degree.-230 mesh) using methylene chloride as eluent to afford the product in good yield: m.p. 152.degree.-153.
EXAMPLE NO. 853
Preparation of N'-t-butyl-N-benzoyl-N'-methylpyridinylhydrazine
N'-t-butyl-N-benzoyl hydrazine (1.2 g), 2-chloromethyl pyridine (1.0 g) and triethylamine (2 equivalents) were stirred in dimethyl sulfoxide (15 ml) at room temperature for 2 hours. The reaction mixture was then warmed to 50.degree. C. for 2 hours. The mixture was diluted with ether and washed with water. The organic layer was dried over magnesium sulfate, filtered and rotavapped to afford a yellow oil. The oil was chromatographed on silica gel (G:70.degree.-230 mesh) using a methylene chloride-ether mixture (1:1) as eluent to afford the purified product as a yellow gum in approximately 20% yield.
EXAMPLE NO. 855
Preparation of N'-t-butyl--N-benzyl-N'-benzoylhydrazine
N'-t-butyl-N'-benzoyl benzaldehyde hydrazone (1.8 g) and sodium cyanoborohydride (1.5 equivalents) were stirred in dry methanol (30 ml) at room temperature. Ten percent HCl was added to bring the pH of the reaction mixture to pH 3.degree.-4 and stirred at room temperature for 1 hour. The methanol was removed in vacuo and the residue was dissolved in methylene chloride. The methylene chloride layer was washed with saturated aqueous sodium bicarbonate and then with water. The organic layer was dried over magnesium sulfate, filtered and the solvent removed in vacuo to afford in good yield a white solid: m.p. 110.degree.-115.
EXAMPLE NO. 864
Preparation of N'-t-butyl-N'-benzoylbenzaldehyde hydrazone
Benzaldehyde (10.6 g), t-butylhydrazine, hydrochloride (12.4 g) and triethylamine (10.1 g) were stirred in toluene (150 ml) at room temperature. The reaction mixture was washed with water and dried over magnesium sulfate. The mixture was filtered and the solvent was removed in vacuo to afford N'-t-butyl benzaldehyde hydrazone as a yellow oil in good yield.
The N'-t-butyl benzaldehyde hydrazone (1.76 g) and benzoyl chloride (1.4 g) were stirred in a pyridine-methylene chloride solvent system (1:1, 50 ml), diluted with methylene chloride and washed several times with 10% HCl. The organic layer was dried over magnesium sulfate, filtered and the solvent removed in vacuo to afford a low melting solid in good yield: m.p. 69.degree.-72.degree. C.
EXAMPLE NO. 870
Preparation of N-benzoyl-N'-t-buty-1-N'-phenylethylhydrazine
N'-t-butyl-N-benzoylhydrazine (2.2 g), powdered potassium carbonate (5 g) and beta-phenethyl bromide (1.8 g) were stirred in dimethylformamide (15 ml) at 60.degree. for 18 hours. The reaction mixture was cooled, and diluted with ether and water. The white solid product was filtered off and recrystallized from ether/hexane to afford 0.3 g of product: m.p. 150.degree.-152.degree. C.
EXAMPLE NO. 871
Preparation of N-benzoyl-N'-t-butyl-N'-(ethoxycarbonyl)methylhydrazine
N'-t-butyl-N-benzoylhydrazine (2.0 g), powdered potassium carbonate (5 g) and bromoethyl acetate (1.6 g) were stirred in dimethylformamide (20 ml) at 60.degree. C. for 14 hours. The reaction mixture was diluted with water and ether, and the organic layer was separated. The organic layer was washed several times with water, dried over magnesium sulfate and rotavaped to afford an oil. Chromatographic purification gave the pure oil product (0.25 g).
EXAMPLE NO. 872
Preparation of N'-t-butyl-N'-benzoyl-N-(4-tolyl)aminocarbonyl]hydrazine
N't-butyl-N'-benzoylhydrazine (0.8 g) and pmethylphenylisocyanate (0.9 g) were stirred in diethylether (10 ml) at 23.degree. C. for 15 hours. The reaction mixture was diluted with ether and filtered to afford 0.5 g of solid product: m.p. 208.degree.-210.degree. C.
EXAMPLE 873
Preparation of N'-t-butyl-N'-benzoylcarbonyl-N-benzoylhydrazine
N'-t-butyl-N'-benzoylhydrazine (1 g), benzoyl formic acid (0.7 g) and methanesulfonyl chloride (0.7 g) were stirred in toluene (30 ml) and saturated sodium bicarbonate (10 ml) at approximately 5.degree. C. Triethylamine was added slowly, dropwise to the reaction mixture and stirred 1 hour at room temperature. After stirring for 1 hour, the reaction mixture was diluted with toluene (25 ml) and washed with water several times. The organic layers were dried over magnesium sulfate, filtered and the toluene rotavapped off to afford a white solid. After column chromatography, the product was obtained as a white solid in approximately 70% yield.
EXAMPLE NO. 878
Preparation of N'-t-butyl-N-benzoylcarbonyl-N'-benzoylhydrazine
N'-t-butyl-N-benzoylhydrazine (1 g), benzoyl formic acid (1 g), and methanesulfonyl chloride (0.7 g) were stirred in toluene (35 ml) and saturated sodium bicarbonate (15 ml) at approximately 5.degree. C. Triethylamine was added slowly, dropwise to the reaction mixture, and slowly warmed to room temperature. After stirring for 1 hour, the reaction mixture was diluted with toluene (20 ml) and the organic layer was washed several times with water. The organic layers were dried over magnesium sulfate, filtered and the toluene rotavapped off to afford a white gum. The crude product was chromatographed on silica gel (G:230-400 mesh) using a methylene chloride ether solvent system as eluent to afford a 65% yield of a white solid.
EXAMPLE NO. 880
Preparation of N'-t-butyl-N-(1,2,3,4-tetrahydronaphthyl-2-carbonyl)-N'-(3-toluoyl)hydrazine
To a stirred suspension of N'-t-butyl-N'-(3toluoyl)hydrazine (1.2 g) in toluene (10 ml) and aqueous sodium hydroxide (3 ml of 50% solution) was added 1,2,3,4-tetrahydronaphthyl-2-carbonyl chloride (0.007 mol). After stirring 1 hour, hexane and ether were added and the solids filtered off and dried by vacuum oven at 45.degree. C.
EXAMPLE NO. 882
Preparation of N'-t-butyl-N-benzoyl-N'-(alpha-chlorophenylacetylhydrazine)
N'-t-butyl-N-benzoylhydrazine (10 g) was stirred in toluene (100 ml) and saturated sodium bicarbonate (50 ml) at approximately 5.degree.-10.degree. C. Alphachlorophenylacetylchloride (9.8 g) in toluene (20 ml) was added slowly, dropwise to the cooled reaction mixture, warmed to room temperature and stirred several hours Hexane (100 ml) was added to the reaction mixture and the solid product was filtered. The filter cake was washed several times with hexane and then water. The product was air dried to afford a 92% yield.
EXAMPLE NO. 883
Preparation of N'-t-butyl-N-benzoyl-N'-phenylacetylhydrazine
N'-t-butyl-N-benzoylhydrazine (2 g) was stirred in toluene (35 ml) and 50% aqueous sodium hydroxide (1 g) at 5.degree. C. Phenylacetylchloride (1.5 g) was added slowly, dropwise to the reaction mixture, warmed to room temperature and stirred 1 hour. The reaction mixture was diluted with hexane (50 ml) and filtered off to yield a solid product. The filter cake was washed with hexane and water and allowed to air dry. The white solid product obtained in 90% yield melted at 167.degree.-169.degree. C.
EXAMPLE NO. 893
Preparation of N'-t-butyl-N'-benzoylalpha-furoyloxybenzaldehyde hydrazone
N'-benzoyl-N'-t-butyl hydrazine (1.5 g) was stirred in a two-phase solvent system consisting of toluene (20 ml) and 50% aqueous sodium hydroxide (10 ml). First, a phase transfer catalyst, (n-Bu).sub.4 N+-I (25-50 mg) was added and then 2-furoyl chloride was added dropwise. After the addition, the suspended white solid hydrazine went slowly into solution as it reacted to form the acylated product. After stirring at room temperature for 1 hour, the reaction mixture was diluted with 35 ml water and 30 ml of ethyl acetate. The layers were separated and the organic layer was washed several times with water, dried over magnesium sulfate, filtered and concentrated in vacuo to afford the product as a clear oil. The product was chromatographed on silica gel (G:230-400 mesh) using methylene chloride as the eluting solvent affording a clear, colorless oil (85% yield).
EXAMPLE NO. 905
Preparation of N'-t-butyl-N'-2,4-dichlorobenzoyl-alpha-methoxy-2,3-dimethylbenzaldehyde hydrazone
To a stirred solution of N'-t-butyl-N-(2,3-dimethylbenzoyl)hydrazine (4.2 g) and triphenylphosphine (5.5 g) in dry acetonitrile (60 ml) at room temperature under nitrogen was dropwise added carbon tetrachloride (3.5 g). The reaction mixture was stirred overnight at room temperature. The acetonitrile was removed in vacuo and the crude reaction mixture was chromatographed on silica gel (6, 230-400 mesh) using hexane/ethyl acetate (3:1) to afford the corresponding hydrazinoyl chloride as a yellow oil.
To a stirred suspension of powdered potassium carbonate (2 g) in methanol (75 ml) was added dropwise a solution of the above hydrazinoyl chloride (2.2 g) in methanol (40 ml). The reaction mixture was stirred overnight at room temperature, concentrated in vacuo and the carbonate was filtered off. The filtrate was rotavapped to afford methoxyhydrazine as a while solid (1.9 g).
To a stirred solution of the methoxyhydrazine (1.5 g) in toluene (25 ml) and 50% sodium hydroxide (2 g diluted with 8 g of water) was added 2,4-dichlorobenzoyl chloride (2.5 g) dropwise while the reaction mixture was kept at approximately 0.degree. C. After warming to room temperature, the reaction mixture was diluted with ether and the layers separated. The organic layer was washed twice with water, once with saturated oodium chloride solution and dried over sodium sulfate. Concentration of the reaction gave a product which was chromatographed on silica gel (6, 230.degree.-400 mesh) using a hexane/ethyl acetate (4:1) solvent system.
EXAMPLE NO. 914
Preparation of N'-t-butyl-N-benzenesulfonyl-N'-benzoylhydrazine
N'-t-butyl-N'-benzoylhydrazine (0.4 g) was stirred in pyridine (3 ml) at room temperature. Benzenesulfonyl chloride (0.5 g) was added slowly, dropwise and stirred for 2 hours, diluted with diethyl ether (20 ml) and washed several times with a 10% HCl solution and then water. The organic layer was dried over magnesium sulfate, filtered and the solvent rotavapped off to afford a white solid in good yield.
EXAMPLE NO. 918
Preparation of N'-t-butyl-N-benzoyl-N'-benzenesulfonylhydrazine
N-benzoyl-N'-t-butyl hydrazine (0.8 g) was stirred in pyridine (2 ml) at room temperature. Benzenesulfonyl chloride (0.8 g) was added slowly dropwise, stirred about 1 hour, diluted with diethyl ether (10 ml) and washed several times with a 10% HCl solution and then water. The organic layer was dried over magnesium sulfate. The mixture was filtered and the solvent rotavapped off to afford a white solid in good yield.
EXAMPLE NO. 922
Preparation of N'-t-butyl-N'-[methyl-(2-chlorophenylamino)phosphinyl]-N-benzoylhydrazine
Methyl dichlorophosphine (1.3 g) in ether (10 ml) and triethylamine (2 ml) were added to a stirred solution of N-benzoyl-N'-t-butyl hydrazine (1.0 g) in methylene chloride (3 ml). After stirring 5 minutes at room temperature, o-chloroaniline was added neat producing a mild exotherm. The reaction was quenched 2 minutes later with water (20 ml) and ether (20 ml), separated and the organic washed with 0.1N HCl, dried over MgSO.sub.4, filtered and rotavapped to a colorless oil weighing 0.5 g.
EXAMPLE NO. 923
Preparation of N'-t-butyl-N-methylphenylphosphinyl-N'-benzoylhydrazine
Triethylamine (7 ml) and t-butyl hydrazine HCl (4 g) were stirred in methylene chloride (20 ml) at about 0.degree. C. To this was added, slowly, methylphenylphosphinyl chloride (0.03 mol). The mixture was stirred at 0.degree. C. for 15 minutes and quenched with a sodium bicarbonate solution. The reaction mixture was extracted with diethyl ether, washed with water and dried over magnesium sulfate. After filtering the drying agent, the solvent was removed in vacuo to afford an oily product which was used directly in the subsequent step.
N'-t-butyl-N-(methylphenyl)phosphinylhydrazine (0.7 g) and triethylamine (3 ml) were stirred in diethyl ether (30 ml) at room temperature. Slowly, dropwise benzoyl chloride (1.2 g) was added to the reaction mixture. After stirring 1 hour at room temperature, the reaction mixture was diluted with hexane and the solid product filtered off. The white solid melted at 175.degree.-178.degree. C.
EXAMPLE NO. 933
Preparation of N'-t-butyl-N-(2-phenyl-3-methylpentanoyl)-N'-(3-toluoyl)hydrazine
To a stirred suspension of N'-t-butyl-N'-(3toluoyl)hydrazine (0.7 g) in toluene (10 ml) and aqueous sodium hydroxide (12 drops of 50% aqueous sodium hydroxide) was added dropwise 2-phenyl-3-methyl-pentanoyl chloride (1.0 g). The reaction mixture was stirred overnight, diluted with hexanes and the solids filtered. The solids were washed with hexane and air dried.
EXAMPLE NO. 941
Preparation of N'-t-butyl-N-phenylpropiolyl-N'-(3-toluoyl)hydrazine
To a stirred solution of N'-(3-toluoyl)-N'-t-butyl hydrazine (1.0 g) in toluene (15 ml) and aqueous sodium hydroxide was added phenylpropiolyl chloride (0.01 mol) dropwise at room temperature. After stirring the reaction mixture for 3 hours, hexane and ether were added and the solids filtered. The solids were vacuum dried at 60.degree. C.
EXAMPLE NO. 942
Preparation of N'-t-butyl-N-(2,3-di-methylbenzoyl)-N'-phenylpropiolylhydrazine
To a stirred solution of N-(2,3-dimethylbenzoyl)-N'-t-butyl hydrazine (1.0 g) in toluene (15 ml) and aqueous sodium hydroxide was added phenylpropiolyl chloride (0.006 mol) dropwise. After stirring 15 minutes at room temperature, ether and hexane were added and the solid product was filtered off.
EXAMPLE NO. 944
Preparation of N'-t-butyl-N-(3,4-epoxycyclohexane carbonyl)-N'-(3-toluoyl)hydrazine
To a stirred solution of N'-t-butyl-N'-(3toluoyl)hydrazine (20 g) in toluene (150 ml) and aqueous sodium hydroxide at 10.degree. C. was added 3-cyclohexenecarbonyl chloride (14.3 g) dropwise at a rate which maintained the temperature at or below 10.degree. C. After stirring at room temperature for 2 hours, hexane was added and the solids filtered. The filler cake was washed with hexane and water and dried overnight.
A mixture of N-(3-cyclohexenecarbonyl)-N'-t-butyl-N'-(3-toluoyl)hydrazine (2 g) and m-chloroperbenzoic acid (1.1 mol equivalents of 80% material) was stirred in methylene chloride (50 ml) overnight. The reaction mixture was diluted with methylene chloride (50 ml) and washed with saturated aqueous sodium bicarbonate solution (3.times.25 ml), dried over magnesium sulfate, filtered and rotavapped to afford the white solid epoxide in 78% overall yield.
EXAMPLE NO. 948
Preparation of N'-t-butyl-N-pyrenonecarbonyl-N'-(3-toluoyl)hydrazine
To a stirred suspension of t-butyl hydrazine hydrochloride (0.02 mol) in toluene (20 ml) and aqueous hydroxide (5 ml of 50% solution) at room temperature was added pyrenonecarbonyl chloride (0.01 mol). After stirring the reaction mixture for 20 minutes, ether and hexane were added and the solid product was filtered and washed with water. The solid product (0.5 g) was stirred in toluene (10 ml) and aqueous sodium hydroxide and m-toluoyl chloride (0.8 g) was added dropwise. After stirring for 5 hours, hexane and ether were added and the solid product filtered and air dried.
EXAMPLE NO. 1002
Preparation of 1-t-butyl-1-(3-toluoyl)-4-(4-chlorobenzenesulfonyl)semicarbazide
To a solution of N'-t-butyl-N'-3-toluoyl hydrazine (4.03 g, 0.02 mole) in methylene chloride (25 ml) under nitrogen was added 4-chlorobenzenesulfonyl isocyanate (5 g, 80%, 0.02 mole) at room temperature. The exothermic reaction mixture was stirred at room temperature for 30 minutes. The solvent was evaporated under reduced pressure to give an oil. A precipitate appeared after treating with ether. The pure product was collected by suctionfiltration and washed with a small amount of ether affording 4.8 g of 1-t-butyl-1-(3-toluoyl)-4-(4-chlorobenesulfonyl)semicarbazide as a white solid. m.p 184.degree.-188.degree. C.
EXAMPLE NO. 1008
Preparation of N'-(1-methyl-1-carbamyl)ethyl-N-3-toluoyl-N-4-chlorobenzoyl hydrazine
To concentrated hydrochloric acid (10 ml) at 0.degree. C. was added N'-(1-methyl-1-cyano)ethyl-N'-3-toluoyl-N-4-chlorobenzoyl hydrazine (0.8 g, 2.25 mmole) in one portion with stirring. After stirring for 40 minutes at a temperature below 20.degree. C., the reaction mixture was diluted with water (50 ml) and hexane (50 ml). The resultant suspension was suction-filtered to give the product, N'-(1-methyl-1-carbamyl)ethyl-N'-3-toluoyl-N-4-chlorobenzoyl hydrazine, as a white solid. m.p. 213.degree.-218.degree. C. Yield is 0.5 g (59%).
EXAMPLE NO. 1013
Preparation of N'-t-butyl-N'-3-toluoylmucochloric acid hydrazone
To a solution of N'-t-butyl-N'-3-toluoylhydrazine (1.03 g, 5 mmole) in 80% methanol (25 ml) was added mucochloric acid (0.85 g, 5 mmole). The reaction mixture was held at room temperature for 2 hours with occasional shaking. The resultant viscous suspension was suction-filtered and washed with water. After air-drying overnight, the product, N'-t-butyl-3-toluoyl mucochloric acid hydrazone, weighed 1.50 g. m.p. 167.degree.-168.degree. C.
EXAMPLE NO. 1015
Preparation of N'-t-butyl-N'-3-toluoylethylpyruvate hydrazone
To a solution of N'-t-butyl-N'-3-toluoyl hydrazine (2.06 g, 10 mmole) in methylene chloride (20 ml) and water (20 ml) at room temperature with stirring was added ethylpyruvate (2.4 g, 21 mmole). The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture turned to two phases. The aqueous phase was extracted with methylene chloride (2.times.50 ml) and the extracts were combined with the organic phase. The combined organic solution was washed with water and brine, dried over magnesium sulfate, filtered and evaporated to give a liquid product. The product was further dried in vacuum to give 1.9 g of N'-t-butyl-N'-3-toluoyl ethylpyruvate hydrazone as an oil.
EXAMPLE NO. 1016
Preparation of N'-t-butyl-N'-3-toluoylacetone hydrazone
To a solution of t-butyl acetone hydrazone (5 g, 39 mmole) in methylene chloride (50 ml) at 0.degree. C. under nitrogen was added 3-toluoyl chloride (6.1 g, 39 mmole), followed by slowly adding triethylamine (3.94 g, 39 mmole). After the addition the reaction mixture was stirred at between 0.degree.-5.degree. C. for one hour. The reaction mixture was diluted with methylene chloride (100 ml) and washed subsequently with water, dilute HCl, water, and brine. The organic layer was dried over MgSO.sub.4 and filtered. The solvent was evaporated under a reduced pressure to give a light brown liquid. The desired product, N'-t-butyl-N'-3-toluoyl acetone hydrazone, was obtained (2.45 g) by a vacuum distillation. b.p. 96.degree.-104.degree. C. at 0.05 mm Hg.
EXAMPLE NO. 1017
Preparation of N'-t-butyl-N'-3-toluoyl-N-isopropylhydrazine
To a solution of N'-t-butyl-N'-3-toluoyl acetone hydrazone (1.5 g, 6.08 mmole) in methanol (50 ml) at room temperature with stirring was added, in small portions, sodium borocyanohydride (0.5 g, 8 mmole). To the above reaction mixture was added 10% HCl (5 ml) and the mixture stirred for 10 minutes. A white precipitate appeared. To this was added water (50 ml) and dilute NaOH until the solution turned basic. The resultant white solid was collected by suction-filtration and washed with water. The product was further dried in vacuum to give 0.9 g (60%) of N'-t-butyl-N'-3-toluoyl-N-isopropylhydrazine as a fluffy white powder. m.p. 107.degree.-109.degree. C.
EXAMPLE NO. 1018
Preparation of N'-t-butyl-N'-benzoyl-N-(1-cyano-1-methyl)ethylhydrazine
To a suspension of N'-t-butyl-N'-benzoyl/hydrazine (1.92 g, 10 mmole) in water (30 ml) at 0.degree.-5.degree. C. was added concentrated HCl (1 g, 10 mmole), followed by NaCN (0.52 g, 10.6 mmole) and acetone (0.75 g, 12.9 mmole). After the addition, the reaction flask was stoppered tightly and the reaction mixture was stirred at room temperature for 16 hours. The resultant suspension was suction-filtered and washed with water. The product, N'-t-butyl-N'-benzoyl-N-(1-cyano-1-methyl)ethylhydrazine, was further dried in vacuum to give 2.1 g as a white powder. m.p. 117.degree.-120.degree. C.
By following substantially the procedures in Examples and 3 and using the reactants shown below in Table II the products of Example Nos. 2, 4 through 12, 14, 19, 20, 32, 37, 55, 98 through 101, 145, 169, 174, 181, 234, 250, 260, 264, 289, 295, 298, 308, 364, 390, 391, 394, 449, 613, 632, 924 through 928, 937, 938, 939, 943, 949, 950, 951, 954, 959, 961, 963, 964, 965, 967, 968, 990 and 996 were prepared.
TABLE II__________________________________________________________________________Ex. No. Compound of Formula III or VI Compound of Formula IV Base Solvents__________________________________________________________________________ 3 3-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 4 3,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 5 4-methylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 6 4-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 7 4-methoxybenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 8 3-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 9 3-methoxybenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water10 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 11 2-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 12 2-methoxybenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 14 4-cyanobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 19 3-methylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 20 2-methylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 32 4- .sub.- t-butylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 37 3,5-dichlorobenzoyl- .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 55 1-naphthoylchloride .sub.- t-butylhydrazine sodium toluene hydrochloride hydroxide and water 98 4-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 99 3-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water100 2-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water101 2-naphthoylchloride .sub.- t-butylhydrazine sodium toluene hydrochloride hydroxide and water145 4-biphenylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water169 2-chloromethyl- .sub.- t-butylhydrazine sodium toluene benzoyl chloride hydrochloride hydroxide and water174 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water181 4-ethylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water234 3-methoxy benzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water250 benzoyl chloride 2,2-dimethyl- sodium toluene pentylhydrazine hydroxide and water oxalic acid salt260 2-nitro-4-chloro- .sub.- t-butylhydrazine sodium toluene benzoyl chloride hydrochloride hydroxide and water264 2,6-difluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water289 4-vinylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water295 benzoyl chloride 2,2-dimethyl- sodium toluene propylhydrazine hydroxide and water oxalic acid salt298 2-bromobenzoyl 2,2-dimethyl- sodium toluene chloride propylhydrazine hydroxide and water oxalic acid salt308 4-(1-propenyl)- .sub.- t-butylhydrazine sodium toluene benzoyl chloride hydrochloride hydroxide and water364 4-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water390 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoyl chloride hydrochloride hydroxide and water391 2,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water394 2,3-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoyl chloride hydrochloride hydroxide and water449 3,4-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoyl chloride hydrochloride hydroxide and water613 2-acetoxybenzoyl .sub.- t-butylhydrazine NaHCO.sub.3 toluene chloride hydrochloride i.e. sodium and water bicarbonate632 2-methyl-3-chloro- .sub.- t-butylhydrazine sodium toluene benzoyl chloride hydrochloride hydroxide and water924 4-chlorobenzoyl methylhydrazine sodium toluene chloride hydroxide and water925 3,5-dichlorobenzoyl methylhydrazine sodium toluene chloride hydroxide and water926 -n-pentanoylchloride .sub.- t-butylhydrazine sodium toluene hydrochloride hydroxide and water927 -n-heptanoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water928 chloroacetyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water937 .beta.,.beta.-dimethyl .sub.- t-butylhydrazine sodium toluene acryloyl chloride hydrochloride hydroxide and water938 2,3,3-trichloro- .sub.- t-butylhydrazine sodium toluene acryloyl chloride hydrochloride hydroxide and water939 cinnamoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water943 cyclohexanecarbonyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water949 2-furoylchloride .sub.- t-butylhydrazine sodium toluene hydrochloride hydroxide and water950 2-thiophene .sub.- t-butylhydrazine sodium toluene carboxylic acid hydrochloride hydroxide and water chloride951 pyrrolidine .sub.- t-butylhydrazine sodium toluene carbonylchloride hydrochloride hydroxide and water954 N,N-diethylcarbamoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water959 benzoylchloride 2-tolyhydrazine sodium toluene hydroxide and water961 benzoylchloride phenylhydrazine sodium toluene hydroxide and water963 benzoylchloride 2-chloropphenyl sodium toluene hydroazine hydroxide and water964 benzoylchloride 4-chlorophenyl sodium touene hydrazine hydroxide and water965 benzoylchloride benzylhydrazine sodium toluene hydroxide and water967 3,5-dichlorobenzoyl benzylhydrazine sodium toluene chloride hydroxide and water968 benzoylchloride 4-chloropyrazinyl sodium toluene hydrazine hydroxide and water990 -n-butanoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water996 benzoyl N'-(1,1-dimethyl)- sodium toluene chloride benzyl-N-benzoyl hydroxide and water hydrazine__________________________________________________________________________
By following substantially the procedures in Example 16 and using the reactants shown below in Table III, the products of Example Nos. 13, 15, 17, 18, 21 through 31, 33 through 36, 38, 40 through 43, 45, 47 through 54, 56, 57 through 62, 64 through 97, 104 through 109, 113, 117, 118, 119, 121, 122, 123, 125, 126, 130 through 135, 137 through 142, 146, 147, 150, 152 through 154, 160, 163, 167, 173, 175 through 180, 182, 183, 184, 190, 194 through 202, 204 through 211, 214 through 219, 224 through 231, 235 through 249, 251 through 259, 261 through 263, 265 through 270, 272 through 284, 287, 288, 290 through 292, 296, 297, 299 through 307, 309 through 322, 325, 327, 328, 334, 341 through 343, 346 through 348, 355 through 357, 370, 371, 377, 378, 380, 381, 387 through 389, 392, 393, 395, 396, 401 through 413, 419, 420, 422 through 424, 426 through 433, 437 through 448, 450 through 452, 454 through 457, 459 through 469, 474 through 483, 485 through 540, 542 through 545, 548 through 612, 615 through 624, 626 through 631, 633, 929 through 932, 934, 935, 936, 940, 946, 947, 952, 953, 962, 966, 993, 994, 995, 997 and 998 were prepared.
TABLE III__________________________________________________________________________Example Compound of Compound of Compound ofNo. Formula III Formula VI Formula IV Base Solvents__________________________________________________________________________ 13 4-toluoyl chloride benzoylchloride .sub.- t-butylhydrazine sodium toluene hydrochloride hydroxide and water 15 4-toluoyl chloride 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 17 benzoylchloride 3-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 18 benzoylchloride 2-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 21 benzoylchloride 4-methylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 22 benzoylchloride 3-methylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 23 benzoylchloride 2-methylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 24 benzoylchloride 4-methoxybenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 25 benzoylchloride 3-methoxybenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 26 benzoylchloride 2-methoxybenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 27 benzoylchloride 4- .sub.- t-butylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 28 benzoylchloride 4-cyanobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 29 benzoylchloride 4-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 30 benzoylchloride 3-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 31 benzoylchloride 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 33 4-methylbenzoyl 3,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 34 benzoylchloride 4-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 35 benzoylchloride 3-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 36 benzoylchloride 2-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 38 benzoylchloride 2,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 40 benzoylchloride 4-trifluoromethyl .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water 41 benzoylchloride 3-trifluoromethyl .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water 42 benzoylchloride 2-trifluoromethyl .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water 43 benzoylchloride 2,5-difluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 45 benzoylchloride 3-cyanobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 47 benzoylchloride 2,6-difluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 48 4-chlorobenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 49 benzoylchloride 3,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 50 benzoylchloride 3,5-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 51 benzoylchloride 2,6-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 52 4- .sub.- t-butylbenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 53 2-chlorobenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 54 1-naphthoylchloride benzoylchloride .sub.- t-butylhydrazine sodium toluene hydrochloride hydroxide and water 56 3-chlorobenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 57 4-chlorobenzoyl 3,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 58 2-chlorobenzoyl 3,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 59 2-methylbenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 60 benzoylchloride 2-chloro-4-nitro .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water 61 benzoylchloride 3,5-dinitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 62 benzoylchloride 2,3-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 64 benzoylchloride 2-chloro-5-methyl .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water 65 benzoylchloride 3,5-dimethylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 66 benzoylchloride 2-nitro-5-methyl .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water 67 benzoylchloride 2-methyl-3-chloro .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water 68 benzoylchloride 3-chloro-4-methyl .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water 69 benzoylchloride 2-nitro-3-chloro .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water 70 benzoylchloride 3-methoxy-4-nitro .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water 71 benzoylchloride 2-nitro-3-methoxy .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water 72 benzoylchloride 2,4-dinitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 73 4-chlorobenzoyl 2-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 74 4-chlorobenzoyl 3-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 75 4-chlorobenzoyl 4-methylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 76 4-chlorobenzoyl 3,5-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 77 4-chlorobenzoyl 2,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 78 4-chlorobenzoyl 4-trifluoromethyl .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water 79 benzoylchloride 4-methanesulfonyl .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water 80 benzoylchloride 4-isopropylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 81 benzoylchloride 2-acetoxybenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 82 benzoylchloride 4-ethylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 83 benzoylchloride 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 84 benzoylchloride 4-hydroxybenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water 85 4-methylbenzoyl 2-methylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 86 4-methylbenzoyl 3-methylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 87 4-methylbenzoyl 2,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 88 4-methylbenzoyl 3,5-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 89 4-methylbenzoyl 2-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 90 4-methylbenzoyl 4-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 91 4-methylbenzoyl 4-trifluoromethyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 92 4-methylbenzoyl 3-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 93 4-chlorobenzoyl 3-chloromethyl .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water 94 4-chlorobenzoyl 4-chloromethyl .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water 95 4-chlorobenzoyl 2-methylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 96 4-chlorobenzoyl 3-methoxybenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water 97 4-chlorobenzoyl 3-methylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water104 benzoylchloride 4-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water105 benzoylchloride 3-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water106 benzoylchloride 4- -n-butylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water107 4-ethylbenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water108 3,4-dichloro- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water109 benzoylchloride 4-acetylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water113 benzoylchloride 2-iodobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water117 benzoylchloride 4-phenoxybenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water118 4-trifluoromethyl- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water119 4-trifluoromethyl- 3,4-dichlorobenoyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water121 benzoylchloride 2-chloro-4-bromo- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water122 benzoylchloride 4-phenylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water123 benzoylchloride 3,4,5-trimethoxy- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water125 benzoylchloride 3-thiocyanomethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water126 benzoylchloride 3-cyanomethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water130 4-ethylbenzoyl 3-toluoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water131 4-ethylbenzoyl 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water132 4-ethylbenzoyl 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water133 benzoylchloride 3-ethylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water134 4-ethylbenzoyl 3-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water135 4-ethylbenzoyl 2-iodobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water137 benzoylchloride 4-carbomethoxy .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water138 2-bromobenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water139 2-trifluoromethyl- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water140 benzoylchloride 3-iodobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water141 benzoylchloride 2-ethylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water142 benzoylchloride 3-methoxymethyl .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water146 benzoylchloride 2-nitro-4-(2-chloro- .sub.- t-butylhydrazine sodium toluene 4-trifluoro- hydrochloride hydroxide and water methyl phenoxy) benzoylchloride147 2-nitro-4-(2-chloro- benzoylchloride .sub.- t-butylhydrazine sodium toluene 4-trifluoromethyl hydrochloride hydroxide and water phenoxy) benzoyl chloride150 benzoylchloride 4-methylthio- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water152 benzoylchloride 3-bromo-4-methyl .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water153 benzoylchloride 3-methyl-4-bromo .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water154 benzoylchloride 2,4-dibromo .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water160 benzoylchloride 3-phenoxy .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water163 benzoylchloride 4-formyl benzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water167 benzoylchloride 2-acetoxybenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water173 2-methyl-5-tri- 2-toluoyl chloride .sub.- t-butylhydrazine sodium toluene fluoromethyl hydrochloride hydroxide and water benzoylchloride175 4-ethylbenzoyl 3-ethyl .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water176 benzoylchloride 4- -n-propyl .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water177 4-toluoyl chloride 3-bromo .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water178 4-toluoyl chloride 3,5-dimethyl .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water179 benzoylchloride 4-iodobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water180 4-toluoyl chloride 4-ethyl benzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water182 4-toluoyl chloride 3-ethyl benzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water183 benzoylchloride 2-isopropylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water184 3-ethyl benzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water190 3-ethyl benzoyl 2,4-dichloro .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water194 4-methoxybenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water195 4-methoxybenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water196 2-chlorobenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water197 2-chlorobenzoyl 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water198 2-chlorobenzoyl 4-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water199 2-chlorobenzoyl 4-ethyl benzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water200 4-ethyl benzoyl 3,5-dimethyl .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water201 4-ethyl benzoyl 2-chloro-4-methyl .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water202 benzoylchloride 3-acetoxybenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water204 4-ethyl benzoyl 2-nitro-3-methyl .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water205 4-methoxybenzoyl 3,5-dimethyl .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water206 4-methoxybenzoyl 2,4-dichloro .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water207 2-chlorobenzoyl 2,6-dichloro .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water208 2-chlorobenzoyl 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water209 2-chlorobenzoyl 2,5-difluoro .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water210 2-chlorobenzoyl 4-methoxy .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water211 2-chlorobenzoyl 2-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water214 2-chlorobenzoyl 2,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water215 2-chlorobenzoyl 3-methoxy .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water216 2-chlorobenzoyl 3-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water217 2-chlorobenzoyl 2-trifluoromethyl .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water218 2-chlorobenzoyl 3-trifluoromethyl .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water219 2-chlorobenzoyl 4-trifluoromethyl .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water224 2-chlorobenzoyl 4-cyanobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water225 2-chlorobenzoyl 4-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water226 2-chlorobenzoyl 4-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water227 2-chlorobenzoyl 4-chloro .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water228 2-chlorobenzoyl 2-methoxy .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water229 2-chlorobenzoyl 4-nitro .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water230 2-chlorobenzoyl 2-fluoro .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water231 2-chlorobenzoyl 2,6-difluoro .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water235 3-methoxybenzoyl 2,5-difluoro .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water236 3-methoxybenzoyl 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water237 3-methoxybenzoyl 3,4-dichloro .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water238 3-methoxybenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water239 3-methoxybenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water240 3-methoxybenzoyl 3,4-dichloro .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water241 3-methoxybenzoyl 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water242 3-methoxybenzoyl 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water243 benzoylchloride 4-trifluoromethoxy .sub.- t-butylhydrazine pyridine pyridine benzoylchloride hydrochloride244 4-trifluoromethoxy benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water245 4-trifluoromethoxy 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water246 4-trifluoromethoxy 4-chloro benzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water247 4-trifluoromethoxy 3,4-dichloro .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water248 4-trifluoromethoxy 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water249 4-trifluoromethoxy 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water251 4-ethoxybenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water252 4-ethoxybenzoyl 3,5-dimethyl .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water253 4-ethoxybenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water254 4-ethoxybenzoyl 2-nitro-4-chloro .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water255 3-chloro-4-methoxy- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water256 4-methylthio benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water257 4- -n-butyloxy 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water258 2-methylthio- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water259 2-nitro-4-chloro- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water261 2-nitro-4-chloro- 4- .sub.- t-butylbenzoyl .sub.- t-butylhydrazine triethyl- methylene benzoylchloride chloride hydrochloride amine chloride262 2-nitro-4-chloro- 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water263 4-toluoyl chloride 2-chloro-5-methyl .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water265 4-phenoxybenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water266 4-phenoxybenzoyl 4-toluoyl chloride .sub. - t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water267 4- -n-butylbenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water268 4- -n-butylbenzoyl 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water269 4-isopropylbenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water270 4-isopropylbenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water272 4-cyanobenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water273 4-cyanobenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water274 2-methyl-4-chloro- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water275 4-ethylbenzoyl 4-trifluoromethoxy .sub.- t-butylhydrazine pyridine pyridine chloride benzoylchloride hydrochloride276 benzoylchloride 2,3,4,5,6-penta- .sub.- t-butylhydrazine sodium toluene fluoro benzoyl hydrochloride hydroxide and water chloride277 2,3,4,5,6-penta- benzoylchloride .sub.- t-butylhydrazine sodium toluene fluoro benzoyl hydrochloride hydroxide and water chloride278 4-cyanobenzoyl 3,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water279 2-methyl-4-chloro- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water280 4-trifluoromethyl 3,5-dimethylbenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water281 2-methyl-4-chloro- 3,5-dimethylbenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water282 benzoylchloride 3-vinylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water283 4-ethylbenzoyl 3-vinylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water284 4-trifluoromethyl- 3-vinylbenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water287 4- -n-propylbenzoyl 3,4-dichloro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water288 4- -n-propylbenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water290 4-vinylbenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water291 2,6-difluoro- 3,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water292 2,6-difluoro- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water296 4-chlorobenzoyl 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water297 4-toluoyl chloride 3-toluoyl chloride 2,2-dimethyl- sodium toluene propylhydrazine hydroxide and water oxalic acid salt299 4-chlorobenzoyl 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water300 3-methoxybenzoyl 3,5-dimethylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water301 4-chlorobenzoyl 4-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water302 4- -n-propylbenzoyl 3,5-dimethylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water303 4-vinylbenzoyl 3,5-dimethylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water304 4-acetoxybenzoyl 3,5-dimethylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride bicarb- and water onate305 3,5-dimethyl- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water306 3,5-dimethyl- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water307 3,5-dimethyl- 4-ethylbenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water309 4-isopropyl- 3,5-dimethyl .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water310 4-ethylbenzoyl 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water311 3-chloro-4-methyl- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water312 3-chloro-4-methyl- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water313 3-chloro-4-methyl- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water314 3-chloro-4-methyl- 3,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water315 4-ethylbenzoyl 2-nitrobenzoyl 2,2-dimethyl- sodium toluene chloride chloride propylhydrazine hydroxide and water oxalic acid salt316 2,6-difluoro- 2-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water317 2,6-difluoro- 3-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water318 2,6-difluoro- 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water319 2,6-difluoro- 3,5-dimethylbenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water320 4-ethylbenzoyl 3,5-dimethylbenzoyl 2,2-dimethyl- sodium toluene chloride chloride propylhydrazine hydroxide and water oxalic acid salt321 3-trifluoromethyl- 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water322 3-trifluoromethyl- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water325 2-nitro-3-methoxy- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water327 4-chlorobenzoyl 4-carboxymethyl- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water328 4-ethylbenzoyl 4-carboxymethyl- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water334 4-ethylbenzoyl 3,5-dichloro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water341 4-chlorobenzoyl 2-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water342 4-ethylbenzoyl 3,4-dichloro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water343 4-ethylbenzoyl 2-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water346 4-carboxymethyl- 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride bicar- and water bonate347 4-carboxymethyl- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride bicar- and water bonate348 4-carboxymethyl- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride bicar- and water bonate355 3-phenoxybenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water356 3-phenoxybenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water357 4-acetylbenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water370 4-biphenylbenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water371 3-cyanobenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water377 3-chloromethyl- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water378 4-ethylbenzoyl 2,3-dimethylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water380 benzoylchloride 2,3-dimethylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water381 4-toluoyl chloride 2,3-dimethylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water387 benzoylchloride 1-naphthoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water407 2-naphthoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water408 benzoylchloride 3-trifluoromethoxy- .sub.- t-butylhydrazine pyridine pyridine benzoylchloride hydrochloride409 4-isothiocyanato- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water410 2,6-difluoro- 2,4-difluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water411 2,6-difluoro- 3,5-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water412 4-toluoyl 3,5-bis-(trifluoro- .sub.- t-butylhydrazine sodium toluene chloride methyl)benzoyl hydrochloride hydroxide and water chloride413 benzoylchloride 3,5-bis-(trifluoro- .sub.- t-butylhydrazine sodium toluene methyl)benzoyl hydrochloride hydroxide and water chloride419 benzoylchloride 3-chloro-4-fluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water420 4-chlorobenzoyl 3-chloro-4-fluoro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water422 4-chlorobenzoyl 3,5-bis-(trifluoro- .sub.- t-butylhydrazine sodium toluene chloride methyl)benzoyl hydrochloride hydroxide and water chloride423 2,3-dimethyl- 3,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water388 1-naphthoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water389 4-isothiocyanato- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water392 2-fluorobenzoyl 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water393 2-fluorobenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water395 2-fluorobenzoyl 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water396 2-fluorobenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water401 4-bromobenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water402 2,3-dichloro- 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water403 2,3-dichloro- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water404 2-fluorobenzoyl 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water405 2,3-dichloro- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water406 benzoylchloride 2-naphthoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water424 4-toluoyl chloride 3-chloro-2-methyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water426 2,6-dimethyl- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water427 2,6-dimethyl- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water428 2,3-dimethyl- 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water429 2,3-dimethyl- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water430 2,3-dimethyl- 3-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water431 3-trifluoro- benzoylchloride .sub.- t-butylhydrazine sodium toluene methoxybenzoyl hydrochloride hydroxide and water chloride432 3-trifluoro- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene methoxybenzoyl hydrochloride hydroxide and water chloride433 2,3-dimethyl- 2-methyl-3-chloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water437 2,6-difluoro- 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water438 2-methyl-3-chloro- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water439 2-methyl-3-chloro- 3-chloro-4-fluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water440 2,3-dimethyl- 3-chloro-4-fluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water441 4-ethylbenzoyl 3-chloro-4-fluoro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water442 3,4-dimethyl benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water443 3,4-dimethyl- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water444 3,4-dimethyl- 2-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water445 3,4-dimethyl- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water446 3,4-dimethyl- 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water447 3,4-dimethyl- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water448 3,4-dimethyl- 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water450 benzoylchloride 3,4-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water451 4-ethylbenzoyl 3,4-dimethyl- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water452 2-fluoro-6-chloro- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water454 4-chloromethyl benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water455 2,3-dimethoxy- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water456 2,3-dimethoxy- 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water457 2,3-dimethoxy- 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water459 4- .sub.- t-butylbenzoyl 3,4-dimethyl- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water460 4- .sub.- t-butylbenzoyl 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water461 4- .sub.- t-butylbenzoyl 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water462 4- .sub.- t-butylbenzoyl 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride bicar- and water bonate463 4- .sub.- t-butylbenzoyl 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water464 4- .sub.- t-butylbenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water465 4- .sub.- t-butylbenzoyl 2-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water466 4- .sub.- t-butylbenzoyl 3,4-dichloro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water467 3,4-dimethyl- 3,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water468 3,4-dimethyl- 4-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water469 4- .sub.- t-butylbenzoyl 4-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water474 1-naphthoyl 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water475 1-naphthoyl 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water476 2-methyl-3-nitro- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water477 2-methyl-3-nitro- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water478 2-methyl-3-nitro- 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water479 2-methyl-3-nitro- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water480 3-bromo-2-methyl- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water481 3-bromo-2-methyl- 3-toluoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water482 3-bromo-2-methyl- 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water483 3-bromo-2-methyl- 2,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water485 2-toluoyl chloride 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water486 2-toluoyl chloride 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride bicar- and water bonate487 2-toluoyl chloride 3-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water488 2-toluoyl chloride 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water489 2-toluoyl chloride 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene hydrochloride hydroxide and water490 2-toluoyl chloride 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water491 2-toluoyl chloride 3,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water492 2-toluoyl chloride 3,5-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water493 2-methyl-3-fluoro- benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water494 2-methyl-3-fluoro- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water495 2-fluoro-6-chloro- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water496 2-fluoro-6-chloro- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water497 2-fluoro-6-chloro- 4-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water498 4-(2-chloroethyl)- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water499 2,4,6-trifluoro- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water500 2,4,6-trifluoro- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water501 2,4,6-trifluoro- 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water502 2,4,6-trifluoro- 3,5-dimethyl .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water503 2-nitro-3-chloro- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water504 2-nitro-3-chloro- 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water505 2-nitro-3-chloro- 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water506 2-nitro-3-chloro- 3-toluoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water507 2-nitro-3-chloro- 3-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water508 2-nitro-3-chloro- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water509 2-nitro-3-chloro- 3,5-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide510 2-nitro-3-chloro- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide511 4-ethylbenzoyl 2,3-difluoro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide512 4-ethylbenzoyl 2,3-dichloro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide513 2,3-difluoro- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide514 2,3-dichloro- 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide515 benzoylchloride 2,3-difluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide516 2,3-dichloro- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water517 2,3-dichloro- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water518 2,3-dichloro- 3,5-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water519 2,3-dichloro- 3-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water520 2,3-dichloro- 2,3-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water521 2,3-difluoro- 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water522 2,3-dimethyl- 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water523 2,3-dimethyl- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water524 2,3-dimethyl- 2,6-difluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water525 2,3-dimethyl- 2,4-difluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water526 2,3-dimethyl- 3-methoxybenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water527 2,3-dimethyl- 2-methoxybenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water528 2,3-dimethyl- 2-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water529 2,3-dimethyl- 4-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water530 2-methyl-3-chloro- 2,4-dichlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water531 4-(2-chloro- benzoylchloride .sub.- t-butylhydrazine sodium toluene ethyl)benzoyl hydrochloride hydroxide and water chloride532 4-(2-chloro- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene ethyl)benzoyl benzoylchloride hydrochloride hydroxide and water chloride533 3-fluoro-4-methyl- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water534 3-fluoro-4-methyl- 3,5-difluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water535 3-fluoro-4-methyl- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water536 3-fluoro-4-methyl- 3,5-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water537 3-fluoro-4-methyl- 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water538 3-fluoro-4-methyl- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water539 4-ethylbenzoyl 3,5-difluoro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water540 2,3-dimethyl- 2-iodobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water542 2,6-difluoro-3- benzoylchloride .sub.- t-butylhydrazine sodium toluene methylbenzoyl hydrochloride hydroxide and water chloride543 2,6-difluoro-3- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene methylbenzoyl hydrochloride hydroxide and water chloride544 2,6-difluoro-3- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene methylbenzoyl benzoylchloride hydrochloride hydroxide and water chloride545 4-chlorobenzoyl 2,3-dimethyl- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water548 2-fluoro-6-chloro- 2,3-difluorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water549 2,3-difluoro- 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water550 2,3-difluoro- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water551 2,3-difluoro- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water552 2,3-difluoro- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water553 2,3-dimethyl- 2,3-difluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water554 2,3-dimethyl- 2,3-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water555 2,3-dimethyl- 3,4-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water556 2,3-dimethyl- 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water557 4-ethylbenzoyl 2-methyl-5-chloro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water558 2,3-dimethyl- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water559 benzoylchloride 2-methyl-5-chloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water560 2,6-difluoro- 2-methyl-5-chloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water561 2,3-dimethyl- 2-methyl-5-chloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water562 2-methyl-3-chloro- 2-methyl-5-chloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water563 2,6-difluoro- 2-chloro-5-methyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water564 2,3-dimethyl- 2-chloro-5-methyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water565 2-methyl-3-chloro- 2-chloro-5-methyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water566 4-chlorobenzoyl 2-methyl-5-chloro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water567 4-chlorobenzoyl 2-chloro-5-methyl- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water568 2-fluoro-4-chloro- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water569 2-fluoro-4-chloro- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water570 2-fluoro-4-chloro- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water571 2-fluoro-4-chloro- 3,5-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water572 2-fluoro-4-chloro- 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water573 2-fluoro-4-chloro- 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water574 2-chloro-3-methyl- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water575 2-chloro-3-methyl- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water576 2-chloro-3-methyl- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water577 2-chloro-3-methyl- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water578 2-chloro-3-methyl- 3,5-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water579 2-bromo-3-methyl- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water580 2-bromo-3-methyl- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water581 2-bromo-3-methyl- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water582 2-bromo-3-methyl- 3,5-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water583 2-bromo-3-methyl- 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water584 2,3-dimethyl- 2-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water585 2,3-dimethyl- 2-trifluoromethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water586 2,3-dimethyl- 4-ethylbenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water587 2,3-dimethyl- 3,5-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water588 2,6-difluoro- 3-chloro-4-fluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water589 4-chlorobenzoyl 3,5-difluoro- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water590 2,3-dimethyl- 3,5-difluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water591 2-methyl-3-chloro- 3,5-difluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water592 benzoylchloride 3,5-difluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water593 4-ethylbenzoyl 2,5-dimethyl- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water594 2,6-difluoro- 3,5-difluoro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water595 2-methyl-3-chloro- 3,5-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water596 2,3-dimethyl- 2,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water597 2-bromobenzoyl 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene chloride benzoylchloride hydrochloride hydroxide and water598 2-bromo-3-methyl- 3-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water599 2-chloro-3-methyl- 3-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water600 2-chloro-3-methyl- 3-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water601 2-chloro-3-methyl- 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water602 2,3-dimethyl- 2-nitro-3-methyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water603 2,3-dimethyl- 2-nitro-5-methyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water604 2,6-difluoro- benzoylchloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water605 2,6-dimethyl- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water606 2,4,6-trimethyl- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water607 2,4,6-trimethyl- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water608 2,6-difluoro- 4-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water609 2,6-difluoro- 2,5-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water610 2,4,6-trimethyl- 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water611 2,4,6-trimethyl- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water612 2,4,6-trimethyl- 3,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water615 2,4-dimethyl- 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene benzoylchloride hydrochloride hydroxide and water616 2,4-dimethyl- 2,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water617 2,4-dimethyl- 3,5-dimethyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water618 2,4-dimethyl- 3,5-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water619 2,4-dimethyl- 3-bromobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water620 2,4-dimethyl- 3,4-dichloro- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water621 2-bromo-3-methyl- 2-nitrobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water622 piperonyl chloride benzoylchloride .sub.- t-butylhydrazine sodium toluene hydrochloride hydroxide and water623 piperonyl chloride 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water624 piperonyl chloride 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene hydrochloride hydroxide and water626 2-pyrrolobenzoyl benzoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water627 2-pyrrolobenzoyl 3-toluoyl chloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water628 2,3-dimethyl- 2-bromo-5-methyl- .sub.- t-butylhydrazine sodium toluene benzoylchloride benzoylchloride hydrochloride hydroxide and water629 2-methyl-3-chloro- 3-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water630 2-methyl-3-chloro- 4-fluorobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water631 2-methyl-3-chloro- 2-bromobenzoyl .sub.- t-butylhydrazine sodium toluene benzoylchloride chloride hydrochloride hydroxide and water633 2-methyl-3-chloro- 3,5-dimethyl-4- .sub.- t-butylhydrazine sodium toluene benzoylchloride chlorobenzoyl hydrochloride hydroxide and water chloride929 -n-pentanoyl 2-furoylchloride .sub.- t-butylhydrazine sodium toluene chloride hydrochloride hydroxide and water930 ethylchloroformate -n-pentanoylchloride .sub.- t-butylhydrazine sodium toluene hydrochloride hydroxide and water931 ethylchloroformate 4-chlorobenzoyl .sub.- t-butylhydrazine sodium toluene hydrochloride hydroxide and water932 benzoylchloride ethylchoro .sub.- t-butylhydrazine sodium toluene formate hydrochloride hydroxide and water934 phenylchloro- benzoylchloride .sub.- t-butylhydrazine sodium toluene formate hydrochloride hydroxide and water935 benzoylchloride phenylchloro .sub.- t-butylhydrazine sodium toluene formate hydrochloride hydroxide and water936 benzoylchloride 4-nitrophenyl .sub.- t-butylhydrazine sodium toluene chloroformate hydrochloride hydroxide and water940 4-ethylbenzoyl phenylpropiolyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water945 4-chlorobenzoyl 4-phenylbenzoyl .sub.- t-butylhydrazine sodium toluene chloride chloride hydrochloride hydroxide and water946 benzoylchloride 1,2,3,4-tetrahydro- .sub.- t-butylhydrazine sodium toluene 2-naphthoylchloride hydrochloride hydroxide and water947 prolinecarboxylic 3-toluoylchloride .sub.- t-butylhydrazine sodium toluene acid chloride hydrochloride hydroxide and water952 benzoylchloride N,N-diethylcar- .sub.- t-butylhydrazine sodium toluene bamoyl chloride hydrochloride hydroxide and water953 benzoylchloride p-chlorophenyl .sub.- t-butylhydrazine none methylene isocyanate hydrochloride chloride962 3,5-dichlorobenzoyl chloroacetyl phenylhydrazine sodium toluene chloride chloride hydroxide and water966 3,5-dichlorobenzoyl chloracetyl benzylhydrazine sodium toluene chloride chloride hydroxide and water993 -n-pentanoyl ethylchloro .sub.- t-butylhydrazine sodium toluene formate hydrochloride hydroxide and water994 4-chlorobenzoyl- ethylchloro .sub.- t-butylhydrazine sodium toluene chloride formate hydrochloride hydroxide and water995 2,6-difluoro- ethylchloro .sub.- t-butylhydrazine sodium toluene benzoylchloride formate hydrochloride hydroxide and water997 benzoylchloride 3-chlorobenzoyl N'-(1,1-di- sodium toluene chloride methyl)benzyl-N- hydroxide and water benzoyl hydrazine998 benzoylchloride 2,3-dichloro- N'-(1,1-di- sodium toluene benzoylchloride methyl)benzyl-N- hydroxide and water benzoyl hydrazine__________________________________________________________________________
By following substantially the procedures in Example 44 and using the reactants shown below in Table IV, the products of Example Nos. 39, 46, 63, 110, 111, 112, 114, 115, 116, 120, 124, 127, 128, 129, 136, 143, 155 through 158, 185 through 189, 332, 336 through 340, 382, 383, 384, 399, 400, 414 through 418, 421, 435, 436, 453, 470, 471, 472, 546, 547, 634 and 955 through 960 were prepared.
TABLE IV______________________________________Ex.No. Reactants______________________________________ 39 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Dimethyl ketone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of acetone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-isopropyl-1-benzoyl- hydrazine Compound of Formula VI: Benzoylchloride Base: Sodium hydroxide Solvent: Toluene and water 46 Compound of Formula VII: Benzoylhydrazine Compound of Formula VII: Methylethyl ketone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of 2-butanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-sec-butyl-1-benzoyl- hydrazine Compound of Formula VI: Benzoylchloride Base: Sodium hydroxide Solvent: Toluene and water 63 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Methyl- .sub.- t-butyl ketone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of methyl-t-butylketone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-(1,2,2-trimethylpropyl)-1- benzoylhydrazine Compound of Formula VI: Benzoylchloride Base: Sodium hydroxide Solvent: Toluene and water110 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: 1,1,1-trimethylacetaldehyde Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of 1,1,1- trimethylacetaldehyde Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-neopentyl-1-benzoyl- hydrazine Compound of Formula VI: 2-bromobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water111 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: 1,1,1-trimethylacetaldehyde Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of 1,1,1- trimethylacetaldehyde Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-neopentyl-1-benzoyl- hydrazine Compound of Formula VI: 2-nitrobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water112 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: 1,1,1-trimethylacetaldehyde Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of 1,1,1- trimethylacetaldehyde Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-neopentyl-1-benzoyl- hydrazine Compound of Formula VI: 2-anisoyl chloride Base: Sodium hydroxide Solvent: Toluene and water114 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Isobutyraldehyde Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of isobutyraldehyde Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-isobutyl-1-benzoyl- hydrazine Compound of Formula VI: Benzoylchloride Base: Sodium hydroxide Solvent: Toluene and water115 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Acetone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of acetone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-isopropyl-1-benzoyl- hydrazine Compound of Formula VI: 2-bromobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water116 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Acetone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of acetone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-isopropyl-1-benzoyl- hydrazine Compound of Formula VI: 3,4-dichlorobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water120 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Dicyclopropylketone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of dicyclopropylketone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-dicyclopropylmethyl-1- benzoylhydrazine Compound of Formula VI: Benzoylchloride Base: Sodium hydroxide Solvent: Toluene and water124 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Methyl- .sub.- t-butyl ketone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of methyl- .sub.- t-butylketone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-(1,2,2-trimethylpropyl)-1- benzoylhydrazine Compound of Formula VI: 2-nitrobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water127 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Methyl- .sub.- t-butyl ketone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of methyl- .sub.- t-butylketone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-(1,2,2-trimethylpropyl)-1- benzoylhydrazine Compound of Formula VI: Benzoylchloride Base: Sodium hydroxide Solvent: Toluene and water128 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Diisopropyl ketone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of diisopropylketone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-diisopropylmethyl-1- benzoylhydrazine Compound of Formula VI: Benzoylchloride Base: Sodium hydroxide Solvent: Toluene and water129 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Cyclopropylmethyl ketone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of cyclopropylmethylketone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-(1-cyclopropylethyl)-1- benzoylhydrazine Compound of Formula VI: Benzoylchloride Base: Sodium hydroxide Solvent: Toluene and water136 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Methyl- .sub.- t-butyl ketone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of methyl- .sub.- t-butylketone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 2-(1-methyl)neopentyl-1- benzoylhydrazine Compound of Formula VI: 2-bromobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water143 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Methyl cyclohexyl ketone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of methyl cyclohexyl ketone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-benzoyl-2-(1-cyclohexyl- ethyl)hydrazine Compound of Formula VI: benzoylchloride Base: Sodium hydroxide Solvent: Toluene and water155 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Acetone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of acetone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-benzoyl-2-isopropyl hydrazine Compound of Formula VI: 2,6-dichlorobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water156 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Trimethylacetaldehyde Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of trimethylacetaldehyde Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-benzoyl-2-(2,2-dimethyl- propyl)hydrazine Compound of Formula VI: 3,4-dichlorobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water157 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-benzoyl-2-(1,2,2-trimethyl- propyl)hydrazine Compound of Formula VI: 4-cyanobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water158 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Trimethylacetaldehyde Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of trimethyl acetaldehyde Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-benzoyl-2-(2,2-dimethyl- propyl)hydrazine Compound of Formula VI: 4-ethylbenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water185 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-benzoyl-2-(1,2,2-tri- methylpropyl)hydrazine Compound of Formula VI: 3-nitrobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water186 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Trimethylacetaldehyde Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of trimethyl acetaldehyde Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-benzoyl-2-(2,2-dimethyl- propyl)hydrazine Compound of Formula VI: 3-nitrobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water187 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Trimethylacetaldehyde Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of trimethyl acetaldehyde Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-benzoyl-2-(2,2-dimethyl- propyl)hydrazine Compound of Formula VI: 3-toluoyl chloride Base: Sodium hydroxide Solvent: Toluene and water188 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Trimethylacetaldehyde Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of trimethyl acetaldehyde Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-benzoyl-2-(2,2-dimethyl- propyl)hydrazine Compound of Formula VI: 4-chlorobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water189 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Trimethylacetaldehyde Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: Benzoylhydrazone of trimethyl acetaldehyde Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-benzoyl-2-(2,2-dimethyl- propyl)hydrazine Compound of Formula VI: 2,4-dinitrobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water332 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(1,2,2- trimethylpropyl)hydrazine Compound of Formula VI: 2-nitrobenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water336 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(1,2,2- trimethylpropyl)hydrazine Compound of Formula VI: 3,5-dimethylbenzoylchloride Base: Sodium hydroxide Solvent: Toluene and water337 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(1,2,2- trimethylpropyl)hydrazine Compound of Formula VI: 2-nitro-3-methyl benzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water338 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(1,2,2- trimethylpropyl)hydrazine Compound of Formula VI: 2-nitro-5-methylbenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water339 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(1,2,2- trimethylpropyl)hydrazine Compound of Formula VI: 3-toluoyl chloride Base: Sodium hydroxide Solvent: Toluene and water340 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(1,2,2- trimethylpropyl)hydrazine Compound of Formula VI: 2-iodobenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water382 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(1,2,2- trimethylpropyl)hydrazine Compound of Formula VI: 2-toluoyl chloride Base: Sodium hydroxide Solvent: Toluene and water383 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(1,2,2- trimethylpropyl)hydrazine Compound of Formula VI: 2-trifluoromethylbenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water384 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(1,2,2- trimethylpropyl)hydrazine Compound of Formula VI: benzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water399 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: 4,4-dimethyl-2-pentanone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of 3,4-dimethyl-2-pentanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(4,4- dimethyl-2-pentyl)hydrazine Compound of Formula VI: 3,5-dimethylbenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water400 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: 4,4-dimethyl-2-pentanone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of 4,4-dimethyl-2-pentanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(4,4- dimethyl-2-pentyl)hydrazine Compound of Formula VI: 3,4-dichlorobenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water414 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: 3-methyl-3-ethyl-2-pentanone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of 3-methyl-3-ethyl-2-pentanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(3-methyl-3- ethylpent-2-yl)hydrazine Compound of Formula VI: benzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water415 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: 3-methyl-3-ethyl-2-pentanone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of 3-methyl-3-ethyl-2-pentanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(3-methyl-3- ethylpent-2-yl)hydrazine Compound of Formula VI: benzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water416 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: 3-methyl-3-ethyl-2-pentanone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoyl hydrazone of 3-methyl-3-ethyl-2-pentanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(3-methyl-3- ethylpent-2-yl)hydrazine Compound of Formula VI: 2-nitrobenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water417 Compound of Formula VII: 4-ethylhydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-ethylbenzoyl hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-ethylbenzoyl)-2-(1,2,2- trimethylpropyl)hydrazine Compound of Formula VI: 3,5-dimethylbenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water418 Compound of Formula VII: 4-ethylbenzoyl hydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-ethylbenzoyl hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-ethylbenzoyl)-2-(1,2,2- trimethylpropyl)hydrazine Compound of Formula VI: 2-nitro-5-methylbenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water421 Compound of Formula VII: 4-ethylbenzoyl hydrazine Compound of Formula VIII: Acetone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-ethylbenzoyl hydrazone of acetone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-ethylbenzoyl)-2- isopropyl hydrazine Compound of Formula VI: 3,5-dimethylbenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water434 Compound of Formula VII: 4-ethylbenzoyl hydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-ethylbenzoyl hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-ethylbenzoyl)-2-(1,2,2- trimethylpropyl)hydrazine Compound of Formula VI: 2,4-dichlorobenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water435 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: 3-methyl-3-ethyl-2-pentanone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoylhydrazone of 3-methyl-3-ethyl-2-pentanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(3-methyl- 3-ethylpent-2-yl)hydrazine Compound of Formula VI: 2-nitro-5-methylbenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water436 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: 3-methyl-3-ethyl-2-pentanone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoylhydrazone of 3-methyl-3-ethyl-2-pentanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(3-methyl- 3-ethylpent-2-yl)hydrazine Compound of Formula VI: 2-nitro-5-methylbenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water453 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: 2,2-dimethyl-3-pentanone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoylhydrazone of 2,2- dimethyl-3-pentanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(2,2-dimethyl pent-3-yl)hydrazine Compound of Formula VI: Benzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water470 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: 2,2-dimethyl-3-pentanone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoylhydrazone of 2,2- dimethyl-3-pentanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(2,2- dimethylpent-3-yl)hydrazine Compound of Formula VI: 2-nitrobenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water471 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: 2,2-dimethyl-3-butanone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoylhydrazone of 2,2- dimethyl-3-pentanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(2,2- dimethylpent-3-yl)hydrazine Compound of Formula VI: 2-nitro-5-methylbenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water472 Compound of Formula VII: 4-toluoylhydrazine Compound of Formula VIII: 2,2-dimethyl-3-pentanone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: 4-toluoylhydrazone of 2,2- dimethyl-3-pentanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(4-toluoyl)-2-(2,2- dimethylpent-3-yl)hydrazine Compound of Formula VI: 3,5-dimethylbenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water546 Compound of Formula VII: 2,3-dimethylbenzoyl hydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: (2,3-dimthylbenzoyl)- hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(2,3-dimethylbenzoyl)-2- (1,2,2-trimethylpropyl) hydrazine Compound of Formula VI: 3,5-dimethylbenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water547 Compound of Formula VII: 2,3-dimethylbenzoyl hydrazine Compound of Formula VIII: Pinacolone Solvent: Methanol Catalyst: Acetic acid Compound of Formula IX: (2,3-dimethylbenzoyl)- hydrazone of pinacolone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Acetic acid Compound of Formula X: 1-(2,3-dimethylbenzoyl)- (1,2,2-trimethylpropyl) hydrazine Compound of Formula VI: 3-toluoyl chloride Base: Sodium hydroxide Solvent: Toluene and water634 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Methyl- .sub.- t-butyl ketone Solvent: Methanol Catalyst: Hydrochloric acid Compound of Formula IX: Benzoylhydrazone of methyl .sub.- t-butyl ketone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Hydrochloric acid Compound of Formula X: 1-(1,2,2-trimethylpropyl)-2- benzoylhydrazine Compound of Formula VI: 2-methyl-3-chlorobenzoyl chloride Base: Sodium hydroxide Solvent: Toluene and water955 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Deoxybenzoin Solvent: Methanol Catalyst: Hydrochloric acid Compound of Formula IX: Benzoylhydrazone of deoxybenzoin Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Hydrochloric acid Compound of Formula X: 1-(1,2-diphenylethyl)- 2-benzoylhydrazine Compound of Formula VI: 3-toluoyl chloride Base: Sodium hydroxide Solvent: Toluene and water956 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Cyclopentanone Solvent: Methanol Catalyst: Hydrochloric acid Compound of Formula IX: Benzoylhydrazone of cyclopentanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Hydrochloric acid Compound of Formula X: 1-cyclopentyl-2-benzoyl hydrazine Compound of Formula VI: 3-toluoyl chloride Base: Sodium hydroxide Solvent: Toluene and water957 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Cyclohexanone Solvent: Methanol Catalyst: Hydrochloric acid Compound of Formula IX: Benzoylhydrazone of Cyclohexanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Hydrochloric acid Compound of Formula X: 1-cyclohexyl-2-benzoyl hydrazine Compound of Formula VI: 3-toluoyl chloride Base: Sodium hydroxide Solvent: Toluene and water958 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: 2-methyl cyclohexanone Solvent: Methanol Catalyst: Hydrochloric acid Compound of Formula IX: Benzoyl hydrazone of 2-methyl-cyclohexanone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Hydrochloric acid Compound of Formula X: 1-(2-methylcyclohexyl)- 2-benzoylhydrazine Compound of Formula VI: 3-toluoyl chloride Base: Sodium hydroxide Solvent: Toluene and water960 Compound of Formula VII: Benzoylhydrazine Compound of Formula VIII: Phenylcyclopentyl ketone Solvent: Methanol Catalyst: Hydrochloric acid Compound of Formula IX: Benzoylhydrazone of phenyl- cyclopentylketone Reducing Agent: Sodium cyanoborohydride Solvent: Methanol Catalyst: Hydrochloric acid Compound of Formula X: 1-(alpha-cyclopentyl- benzyl)-2-benzoyl hydrazine Compound of Formula VI: 3-toluoyl chloride Base: Sodium hydroxide Solvent: Toluene and water______________________________________
By following substantially the procedures in Example 220 and using the reactants shown below in Table V, the products of Examples 168, 170, 171, 172, 191, 192, 193, 212, 213, 221 through 223, 232, 233, 293, 326, 331, 379, 397, 398, 425 and 458 were prepared.
TABLE V______________________________________Ex. Compound of Compound of Sol-No. Formula XII Formula XIII Base vent______________________________________168 3,4-dimethoxy- N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride benzoylhydrazine hydroxide and water170 2-chloromethyl- N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride benzoylhydrazine hydroxide and water171 4- -n-propylbenzoyl N'- .sub.- t-butyl-N'- sodium toluene chloride benzoylhydrazine hydroxide and water172 2-nitrobenzoyl N'- .sub.- t-butyl-N'- sodium toluene chloride benzoylhydrazine hydroxide and water191 3,4-dichloro- N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride (4-chlorobenzoyl) hydroxide and hydrazine water192 4- -n-heptyl- N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride (4-chlorobenzoyl) hydroxide and hydrazine water193 4- -n-propyl- N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride (4-chlorobenzoyl) hydroxide and hydrazine water212 2-fluoro- N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride (4-chlorobenzoyl) hydroxide and hydrazine water213 2,4-dichloro- N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride (4-chlorobenzoyl) hydroxide and hydrazine water221 3-nitrobenzoyl N'- .sub.- t-butyl-N'- sodium toluene chloride benzoylhydrazine hydroxide and water222 2,6-dichloro- N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride benzoylhydrazine hydroxide and water223 2,4-difluoro- N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride benzoylhydrazine hydroxide and water232 4-nitrobenzoyl N'- .sub.- t-butyl-N'- sodium toluene chloride benzoylhydrazine hydroxide and water233 4-cyanobenzoyl N'- .sub.- t-butyl-N'- sodium toluene chloride benzoylhydrazine hydroxide and water293 2-chloromethyl N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride (4-chlorobenzoyl) hydroxide and hydrazine water326 3-bromo-4-methyl- N'- .sub.- t-butyl-N'- triethyl meth- benzoic methane- benzoylhydrazine amine ylene sulfonic anhydride chlor- ide331 4-fluorobenzoyl N'- .sub.- t-butyl-N'- sodium toluene chloride benzoylhydrazine hydroxide and water379 2,3-dimethyl N'- .sub.- t-butyl-N' sodium toluene benzoylchloride (3-toluoyl)- hydroxide and hydrazine water397 2-methyl-3-chlor- N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride (3-toluoyl)- hydroxide and hydrazine water398 2-methyl-3-chloro- N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride benzoylhydrazine hydroxide and water425 3-chloro-4-fluoro- N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride benzoylhydrazine hydroxide and water458 3-chloro-4-fluoro- N'- .sub.- t-butyl-N'- sodium toluene benzoyl chloride (3,4-dichloro- hydroxide and benzoyl)hydrazine water______________________________________
TABLE VI__________________________________________________________________________Ex. No. Compound of Formula II Reactant Base or Acid Solvent__________________________________________________________________________162 N-benzoyl-N'- .sub.- t-butyl- sodium methanol N'-(4-formylbenzoyl)- borohydride hydrazine329 N-benzoyl-N'- .sub.- t-butyl-N'- zinc dust acetic (3-nitrobenzoyl)- acid hydrazine330 N-benzoyl-N'- .sub.- t-butyl-N'- zinc dust acetic (2-nitrobenzoyl)- acid hydrazine350 N-(2-nitro-3-methoxy- zinc dust acetic benzoyl)-N'- .sub.- t-butyl-N'- acid (3-toluoyl)hydrazine351 N-(4-nitrobenzoyl)-N'- hydrogen, ethyl .sub.- t-butyl-N'(4-chloro- platinum acetate- benzoyl)hydrazine on carbon methanol352 N-(4-aminobenzoyl)-N'- methyl pyridine methylene .sub.- t-butyl-N'-(4-chloro- chloro- chloride benzoyl)hydrazine formate353 N-(4-aminobenzoyl)-N'- acetic .sub.- t-butyl-N'-(4-chloro- anhydride benzoyl)hydrazine354 N-(2-nitro-3-methoxy- 1. H.sub.2 /catalyst 1. ethyl acetate benzoyl)-N'- .sub.- t-butyl- 2. AC.sub.2 O 2. none N'-(3-toluoyl)hydrazine372 N-(3-nitrobenzoyl)-N'- zinc aqueous .sub.- t-butyl-N'-(3-toluoyl)- dust acetic hydrazine acid375 N-(3-aminobenzoyl)-N'- methacryloyl sodium water .sub.- t-butyl-N'-(3-toluoyl)- chloride hydroxide hydrazine473 N-(2-nitro-3-mehtoxy- zinc amonium aqueous benzoyl)-N'- .sub.- t-butyl-N'- dust chloride ethanol benzoylhydrazine484 N-(2-methyl-3-nitro zinc ammonium aqueous benzoyl)-N'- .sub.- t-butyl-N'- dust chloride ethanol (3-toluoyl) hydrazine__________________________________________________________________________
Using a chloromethylbenzoyl compound of Formula II as a reactant and performing a substitution reaction under the conditions (base or acid, and solvent) set forth in Table VII, the products of Examples 159, 161, 162, 294, 361, 362, 363 and 367 were prepared.
TABLE VII__________________________________________________________________________Ex. No. Compound of Formula II Reactant Base or Acid Solvent__________________________________________________________________________159 N-benzoyl-N'- .sub.- t-butyl-N'- sodium N,N- (3-chloromethylbenzoyl) acetate dimethyl- hydrazine formamide161 N-benzoyl-N'- .sub.- t-butyl-N'- -p-thiocersol sodium toluene- (3-chloromethylbenzoyl) hydroxide water hydrazine294 N-(2-chloromethyl- diethylamine tetra- benzoyl)-N"- .sub.- t-butyl- hydro- N'-(4-chlorobenzoyl)- furan hydrazine361 N-(4-chloromethyl sodium N,N- benzoyl)N'- .sub.- t-butyl-N'- acetate dimethyl- benzoyl hydrazine formamide362 N-(4-chloromethyl potassium ethanol benzoyl)-N'- .sub.- t-butyl-N'- thiocyanate benzoyl hydrazine363 N-(4-acetoxymethyl sodium methanol benzoyl)-N'- .sub.- t-butyl-N'- hydroxide benzoylhydrazine367 N-(4-chloromethyl potassium dimethyl benzoyl)-N'- .sub.- t-butyl-N'- cyanide formamide benzoyl hydrazine__________________________________________________________________________
Using an acetyloxybenzoyl compound of Formula II as a reactant and performing a hydrolysis, under the conditions (base and solvent) set forth in Table VIII, the products of Examples 151, 165, 203, 271, 285, 333, 349 and 614 were prepared.
TABLE VIII______________________________________Ex. Compound of Base orNo. Formula II Reactant Acid Solvent______________________________________151 N-benzoyl-N'- .sub.- t-butyl- sodium methanol N'-(2-acetoxybenzoyl)- hydroxide hydrazine165 N-benzoyl-N'-(1,2,2- sodium methanol trimethylpropyl)-N'- hydroxide 2-acetoxybenzoyl) hydrazine203 N-benzoyl-N'- .sub.- t-butyl-N'- potassium methanol (3-acetoxybenzoyl) hydroxide hydrazine271 N-(4-acetoxybenzoyl)- potassium methanol N'- .sub.- t-butyl-N'-benzoyl hydroxide hydrazine285 N-(4-acetoxybenzoyl)- potassium methanol N'- .sub.- t-butyl-N'-(3-toluoyl) hydroxide hydrazine333 N-(3-acetoxybenzoyl)- potassium methanol N'- .sub.- t-butyl-N'-benzoyl hydroxide hydrazine349 N-(4-carbomethoxy sodium aqueous benzoyl)-N'- .sub.- t-butyl- hydroxide tetra- N'-(3-toluoyl)hydrazine hydro- furan614 N,N'-bis-(2-acetoxy- sodium methanol benzoyl)-N'- .sub.- t-butyl hydroxide hydrazine______________________________________
Using a hydroxybenzoyl compound of Formula II as a reactant and performing an alkylation or esterification, under the conditions (base and solvent) set forth in Table IX, the products of Examples 144, 286, 335, 345, 358, 359, 360, 365, 366 and 385 were prepared.
TABLE IX______________________________________Ex. Compound ofNo. Formula II Reactant Base Solvent______________________________________144 N-benzoyl-N'- .sub.- t-butyl- allyl potassium tetra- N'-(4-hydroxybenzoyl) bromide .sub.- t-butoxide hydro- hydrazine furan286 N-(4-hydroxybenzoyl)- allyl potassium tetra- N'- .sub.- t-butyl-N'-benzoyl- bromide .sub.- t-butoxide hydro- hydrazine furan335 N-(3-hydroxybenzoyl)- allyl sodium dimethyl- N'- .sub.- t-butyl-N'-benzoyl- bromide hydride form- hydrazine amide345 N-(3-hydroxybenzoyl)- vinyl potassium tetra- N'- .sub.- t-butyl-N'-benzoyl- chloro- .sub.- t-butoxide hydro- hydrazine formate furan358 N-(4-hydroxybenzoyl)- chloro- potassium tetra- N'- .sub.- t-butyl-N'-benzoyl- methyl- .sub.- t-butoxide hydro- hydrazine methyl furan ether359 N-(4-hydroxybenzoyl)- N,N-di- potassium tetra- N'- .sub.- t-butyl-N'-benzoyl- methyl- .sub.- t-butoxide hydro- hydrazine carbamoyl furan chloride360 N-(4-hydroxybenzoyl)- ethyl potassium tetra- N'- .sub.- t-butyl-N'-benzoyl- bromo- .sub.- t-butoxide hydro- hydrazine acetate furan365 N-(4-hydroxybenzoyl)- chloro- sodium dimethyl- N'- .sub.- t-butyl-N'-benzoyl- methyl- hydride form- hydrazine methyl amide sulfide366 N-(4-hydroxybenzoyl)- isobutyl potassium dimethyl N'- .sub.- t-butyl-N'-benzoyl- bromide .sub.- t-butoxide form- hydrazine amide385 N-(4-hydroxybenzoyl)- chloro- potassium tetra- N'- .sub.- t-butyl-N'-benzoyl- methyl- .sub.- t-butoxide hydro- hydrazine methyl furan ether______________________________________
Using a compound of Formula II as a reactant and performing the stated reaction under the conditions (additional reactant, base or acid, and solvent) set forth in Table X, the products of Examples 149, 164, 166, 368, 369, 373, 374, 376, 386 and 541 were prepared.
TABLE X______________________________________ Compound Prepared, Reactants, ReactionExample No. Conducted and Conditions______________________________________149 N-benzoyl-N'- .sub.- t-butyl-N'-(4-methane- sulfonylbenzoyl)hydrazine was prepared from N-benzoyl-N'- .sub.- t-butyl-N'-(4- methylthiobenzoyl)hydrazine using meta- chloroperbenzoic acid in methylene chloride in an oxidation reaction.164 N-benzoyl-N'- .sub.- t-butyl-N'-(4-carboxybenzoyl)- hydrazine was prepared from N-benzoyl-N'- .sub.- t- butyl-N'-(4-methoxycarbonyl- benzoyl)hydrazine sodium hydroxide as a base and methanol as solvent in a hydrolysis reaction.166 N-benzoyl-N'- .sub.- t-butyl-N'-(4-(2,2- dichloroethenyl)benzoyl)hydrazine was prepared from N-benzoyl-N'- .sub.- t-butyl-N'- (4-formylbenzoyl)hydrazine using triphenylphosphine in carbon tetra- chloride as solvent in a Witting-type reaction.368 N-(4-(1,2-epoxypropyl)benzoyl)-N'- .sub.- t-butyl- N'-benzoylhydrazine was prepared from N- (4-(1-propenyl)benzoyl)-N'- .sub.- t-butyl-N'- benzoylhydrazine using meta-chloroperbenzoic acid in methylene chloride as solvent in an oxidation reaction.369 N-(4-acetylsemicarbazone)-N'- .sub.- t-butyl- N-(3-toluoyl)hydrazine was prepared from N- (4-acetylbenzoyl)-N'- .sub.- t-butyl-N'-(3-toluoyl) hydrazine using semicarbazide in ethanol solvent with hydrochloric acid catalyst in a condensation reaction.373 N-(4-(2-hydroxy-1,1-dimethylethylamino- carbonyl)benzoyl)-N'- .sub.- t-butyl-N'-(3-toluoyl)- hydrazine was prepared from N-(4- methoxycarbonylbenzoyl)-N'- .sub.- t-butyl-N'- (3-toluoyl)hydrazine using 2-amino-2- methylpropanol in a condensation reaction.374 N-(4-(2-hydroxyethyl)benzoyl)-N'- .sub.- t-butyl- N'-(3-toluoyl)hydrazine was prepared from N-(4-acetylbenzoyl)-N'- .sub.- t-butyl-N'- (3-toluoyl)hydrazine using sodium borohydride in methanol solvent in a reduction reaction.376 N-(3-carboxybenzoyl)-N'- .sub.- t-butyl-N'- (3-toluoyl)hydrazine was prepared from N-(3-cyanobenzoyl)-N'- .sub.- t-butyl-N'-(3- toluoyl)hydrazine using potassium hydroxide as base in methanol solvent in a hydrolysis reaciton.386 N-(4-(1-methylethenyl)benzoyl)-N'- .sub.- t-butyl- N'-(3-toluoyl)hydrazine was prepared form N- (4-acetylbenzoyl)-N'- .sub.- t-butyl-N'-(3-toluoyl) hydrazine using methyltriphenylphosphonium bromide and -n-butyl lithium as base and tetra- hydrofuran solvent in a Wittig reaction.541 N-(4-(2-hydroxyethyl)benzoyl)-N'- .sub.- t-butyl-N'- (3,5-dimethylbenzoyl)hydrazine was prepared from N-(4-(2-acetoxyethyl)benzoyl)-N'- .sub.- t-butyl- N'-(3,5-dimethylbenxoyl)hydrazine using sodium hydroxide as base and methanol as solvent in a hydrolysis.______________________________________
By following substantially the processes for preparing the compounds of the present invention as described above and as exemplified by the illustrative preparation of the compounds of Examples 635 to 639 and 642 and using the appropriately substituted reactants, the compounds of Examples 640, 641 and 643 to 645 were prepared.
By following substantially the processes for preparing the compounds as described above and as exemplified by the illustrative preparation of the compounds of Examples 646, 648, 654, 656, 659 and 660 and using the appropriately substituted reactants, the compounds of Examples 647, 649 to 653, 655, 657, 658 and 661 to 681 were prepared.
By following substantially the procedures in processes described above as exemplified above by the preparation of the compounds of Examples 682, 683, 688, 689, 691, 699 and 702 and using the appropriately substituted reactants, the compounds of Examples 684 to 687, 690, 692 to 698, 700, 701, 703 to 721 and 991 were prepared.
By following substantially the procedures in the processes described above and as exemplified by the preparation of the compounds of Examples 722, 723, 724, 727, 729, 733, 737, 738, 739, 743, 754 and 755 and using the appropriately substituted reactants, the compounds of Examples 725, 726, 728, 730 to 732, 734 to 736, 740 to 742, 744 to 753, 756 and 992 were prepared.
By following substantially the procedures in the processes described above and as exemplifed by the preparation of the compounds of Examples 764, 765, 766, 767, 772, 778 and 787 and using the appropriately substituted reactants, the compounds of Examples 768 to 771, 773 to 777, 779 to 786 and 788 to 794 were prepared.
By following substantially the procedures in Example 802 (without catalyst) or 809 (with catalyst) and using the reactants shown below in Table XI, the products of Examples 802 to 818 were prepared.
TABLE XI______________________________________Ex. Compound of Compound of Compound ofNo. Formula VII Formula VIIIa Formula VI______________________________________802 benzoylhydrazine acetone benzoyl chloride803 benzoylhydrazine acetone 4-chlorobenzoyl chloride804 4-toluoylhydrazine acetone 3-methylbenzoyl chloride805 benzoylhydrazine acetone 3-methylbenzoyl chloride806 4-chlorobenzoyl- acetone 4-chlorobenzoyl hydrazine chloride807 4-toluoylhydrazine acetone 3,5-dimethylbenzoyl chloride808 4-toluoylhydrazine acetone 4-fluorobenzoyl chloride809 4-toluoylhydrazine acetone 4-methylbenzoyl chloride810 benzoylhydrazine methyl- benzoyl chloride ethylketone811 thienoylhydrazine acetone 3-methylbenzoyl chloride812 4-ethylbenzoyl- acetone 3,5-dimethylbenzoyl hydrazine chloride813 2-toluoylhydrazine acetone 3,5-dimethylbenzoyl chloride814 4-chlorobenzoyl- acetone 3-methylbenzoyl hydrazine chloride815 2,4-difluorobenzoyl- acetone 4-chlorobenzoyl hydrazine chloride816 2-toluoylhydrazine acetone 3-methylbenzoyl chloride817 2-nitrobenzoyl- acetone 3-methylbenzoyl hydrazine chloride818 2-chlorobenzoyl- acetone 3-methylbenzoyl hydrazine chloride______________________________________
Examples 820 and 821 were made generally in accordance with the procedures for Example 822 above.
The (trimethylsilymethyl)hydrazine, trifluoroalkyl hydrazine and (2-carbomethoxy-2-propyl)hydrazine were made generally in accordance with the procedures from Noll, J. E.; Sprier, J. L.; Daubert, B. F.; JACS 73, 3867, 1951; Hung, S. C.; Le; Breton, G. C.; JOC 46, 5413, 1981; and Organic Synthesis Vol 5, pg. 43, respectively. From these starting materials Examples 795-801, 819 and 823-828 were made generally in accordance with the procedure for Example 822 above.
The reactant shown below in Table XII were used to prepare Examples 795-801, 819-828 and 969-978.
TABLE XII______________________________________Ex. Compound of Compound of Compound ofNo. Formula III Formula IV Formula VI______________________________________795 2,3-dimethyl (1-methyl-2,2,2- 2,4-dichloro benzoylchloride trifluorethyl) benzoylchloride hydrazine796 2,3-dimethyl (1-methyl-2,2,2- 3,5-dimethyl benzoylchloride trifluoroethyl) benzoylchloride hydrazine797 2-3-dimethyl (1-methyl-2,2,2- 2-nitro-5- benzoylchloride trifluoroethyl) toluoylchloride hydrazine798 benzoylchloride (1-methyl-2,2,2- benzoylchloride trifluoroethyl) hydrazine799 3,4-dichloro (2,2,2-trifluoroethyl) 3,4-dichloro benzoylchloride hydrazine benzoylchloride800 4-chlorobenzoyl (2,2,2-trifluoroethyl) 4-chlorobenzoyl chloride hydrazine chloride801 benzoylchloride (2,2,2-trifluoroethyl) benzoylchloride hydrazine819 benzoylchloride (1-carbmethoxy-1- benzoylchloride methylethyl) hydrazine820 4-toluoylchloride (1,1-dimethyl-3- 4-toluoylchloride butenyl)hydrazine821 3-toluoylchloride (1,1-dimethyl-3- 3-toluoylchloride butenyl)hydrazine822 benzoylchloride (1,1-dimethyl-3- benzoylchloride butenyl)hydrazine823 4-ethylbenzoyl (trimethylsilyl- 2-nitro-5-toluoyl chloride methyl)hydrazine chloride824 4-chlorobenzoyl (trimethylsilyl- 4-chlorobenzoyl chloride methyl)hydrazine chloride825 2-toluoyl (trimethylsisly- 2-toluoyl chloride methyl)hydrazine chloride826 2-nitrobenzoyl (trimethylsilyl- 2-nitrobenzoyl chloride methyl)hydrazine chloride827 benzoyl (trimethylsilyl- benzoyl chloride methyl)hydrazine chloride828 4-ethylbenzoyl (trimethylsilyl- 3,5-dimethyl chloride methyl)hydrazine benzoylchloride969 4-toluoyl (2-methyl-2- benzoylchloride chloride propenyl)hydrazine970 4-toluoyl (2-methyl-2- 3-toluoylchloride chloride propenyl)hydrazine971 benzoyl (1,5-dimethyl-1- 2-bromobenzoyl chloride heptenyl)hydrazine chloride973 4-methylbenzoyl (2-bromo-2,2-di- 3-toluoylchloride chloride methylethyl) hydrazine974 4-toluoyl (1-carbethoxyethyl) benzoylchloride chloride hydrazine975 4-toluoyl (1-carbethoxyethyl) 2-nitrobenzoyl chloride hydrazine chloride976 4-toluoyl (2-dimethylamino- 3,5-dimethyl chloride 1-methylethyl) benzoylchloride hydrazine977 4-toluoyl (2-hydroxy-2,2- benzoylchloride chloride dimethylethyl)978 4-toluoyl (2-hydroxy-2l,2- 3,5-dimethyl chloride dimethylethyl) benzoyolchloride hydrazine______________________________________
By following substantially the procedure in Examples 829, 837 and 853 and using the reactants shown in Table XIII, the products of Example Nos. 830-836, 838-852 and 854 were prepared.
TABLE XIII__________________________________________________________________________Ex.No. Halide Hydrazine Base Solvent__________________________________________________________________________830 4-chlorobenzyl N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide bromide hydrazine831 2,4-dichloro- N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide benzyl bromide hydrazine832 3,4-dichloro- N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide benzyl bromide hydrazine833 4-trifluoromethyl- N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide benzyl bromide hydrazine834 4-methoxycarbonyl- N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide benzyl bromide hydrazine835 2-nitrobenzyl N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide bromide hydrazine836 4-fluorobenzyl N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide bromide hydrazine838 2-bromobenzyl N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide bromide hydrazine839 2-cyanobenzyl N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide bromide hydrazine840 benzyl bromide N'- .sub.- t-butyl-N- triethylamine dimethylformamide thienoyl hydrazine841 4-cyanobenzyl N'- .sub.- t-butyl-N-(4- triethylamine dimethylformamide bromide methylbenzoyl) hydrazine842 benzyl bromide N'- .sub.- t-butyl-N-(4- triethylamine dimethylformamide methylbenzoyl) hydrazine843 3-nitrobenzyl N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide bromide hydrazine844 4-methoxybenzyl N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide bromide hydrazine845 3-methoxybenzyl N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide bromide hydrazine846 3-methylbenzyl N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide bromide hydrazine847 3-methylbenzyl N'- .sub.- t-butyl-N-(4- triethylamine dimethylformamide bromide methylbenzoyl) hydrazine848 4-methylbenzyl N'- .sub.- t-butyl-N-benzoyl triethylamine dimethylformamide bromide hydrazine849 4-methylbenzyl N'- .sub.- t-butyl-N-(4- triethylamine dimethylformamide bromide methylbenzoyl) hydrazine850 benzyl bromide N'- .sub.- t-butyl-N-(3,4- triethylamine dimethylformamide dichlorobenzoyl) hydrazine851 4-methylbenzyl N'- .sub.- t-butyl-N-(3,4- triethylamine dimethylformamide bromide dichlorobenzoyl) hydrazine852 benzyl bromide N'- .sub.- t-butyl-N- triethylamine dimethylformamide (2-pyridinyl) hydrazine854 2-methylbenzyl N'- .sub.- t-butyl-N- triethylamine dimethylformamide bromide benzoyl hydrazine__________________________________________________________________________
By following substantially the procedures in Example 855 and using the reactants shown in Table XIV, the products of Example Nos. 856-863 were prepared.
TABLE XIV______________________________________Ex.No. Hydrazone Base Solvent______________________________________856 N'- .sub.- t-butyl-N'-(4-fluorobenzoyl)- sodium dry benzaldehyde hydrazone cyanobo- methanol rohydride857 N'- .sub.- t-butyl-N'-(2-bromobenzoyl)- sodium dry benzaldehyde hydrazone cyanobo- methanol rohydride858 N'- .sub.- t-butyl-N'-(3,4-dichloro- sodium dry benzoyl) benzaldehyde cyanobo- methanol hydrazone rohydride859 N'- .sub.- t-butyl-N'-(2-methylbenzoyl) sodium dry benzaldehyde hydrazone cyanobo- methanol rohydride860 N'- .sub.- t-butyl-N'-(3,4-dichloro- sodium dry benzoyl)-3-methylbenzaldehyde cyanobo- methanol hydrazone rohydride861 N'- .sub.- t-butyl-N'-benzoyl-3-methyl- sodium dry benzaldehyde hydrazone cyanobo- methanol rohydride862 N'- .sub.- t-butyl-N'-2-thienoyl-3- sodium dry methylbenzaldehyde hydrazone cyanobo- methanol rohydride863 N'- .sub.- t-butyl-N'-benzoyl-methyl-2- sodium dry pyridinylbenzaldehyde hydrazone cyanobo- methanol rohydride______________________________________
By following substantially the procedures in Example 864 and using the reactants shown in Table XV, the products of Example Nos. 865-869 were prepared.
TABLE XV__________________________________________________________________________ExNo. Benzaldehyde Halide Base Solvent Solvent System__________________________________________________________________________865 benzaldehyde 4-fluorobenzoyl triethylamine toluene pyridine/methylene chloride chloride866 benzaldehyde 3,4-dichloro- triethylamine toluene pyridine/methylene benzoyl chloride chloride867 benzaldehyde 2-bromobenzoyl triethylamine toluene pyridine/methylene chloride chloride868 3-methyl- benzoyl triethylamine toluene pyridine-methylene benzaldehyde chloride chloride869 benzaldehyde 2-thienoyl triethylamine toluene pyridine/methylene chloride chloride__________________________________________________________________________
Example No. 874 was prepared by following substantially the procedures in Example 873 and using N'-t-butyl-N'-benzoylhydrazine, 3-methylbenzoyl formic acid, methanesulfonyl chloride in toluene and saturated sodium bicarbonate.
By following substantially the procedures in Example 878 and using the hydrazine shown in Table XVI and the reactants in Example 878, the products of Example Nos. 875-877 were prepared.
TABLE XVI______________________________________Ex. No. Hydrazine______________________________________875 N'- .sub.- t-butyl-N-(2,3-dimethylbenzoyl) hydrazine876 N'- .sub.- t-butyl-N-(4-methylbenzoyl) hydrazine877 N'- .sub.- t-butyl-N-(4-ethylbenzoyl) hydrazine______________________________________
By following substantially the procedure in Example Nos. 882 and 883 and using the reactants shown in Table XVII, the products of Example Nos. 879-881 and 884-886, were prepared.
TABLE XVII__________________________________________________________________________Ex.No. Hydrazine Base Solvent Halide__________________________________________________________________________879 N'- .sub.- t-butyl-N- sodium hydroxide toluene alpha-isopropyl-4- (2,3-dimethyl- chlorophenylacetyl benzoyl)hydrazine chloride881 N'- .sub.- t-butyl-N- sodium hydroxide toluene phenylacetyl chloride (4-chlorobenzoyl) hydrazine884 N'- .sub.- t-butyl-N- sodium bicarbonate toluene alpha-chlorophenyl- (4-chlorobenzoyl) acetyl chloride hydrazine885 N'- .sub.- t-butyl-N- sodium hydroxide toluene phenylacetyl chloride (2,3-dimethyl- benzoyl) hydrazine886 N'- .sub.- t-butyl-N- sodium hydroxide toluene phenylacetyl chloride (4-ethylbenzoyl) hydrazine__________________________________________________________________________Ex.No. Hydrazine Halide__________________________________________________________________________902 N'- .sub.- t-butyl-N-2,3-dimethylbenzoyl- methacryloyl N'-3-methylbenzoyl hydrazine chloride903 N'- .sub.- t-butyl-N-2,3-dimethylbenzoyl- 2-furoyl chloride N'-3-methylbenzoyl hydrazine907 N'- .sub.- t-butyl-N-4-ethylbenzoyl-N'- acryloyl chloride 2,3-dimethylbenzoyl hydrazine908 N,N'-benzoyl-N'- .sub.- t-butyl hydrazine acryloyl chloride909 N,N'-benzoyl-N'- .sub.- t-butyl hydrazine 4-ethylbenzoyl chloride910 N,N'-benzoyl-N'- .sub.- t-butyl hydrazine 4-pentenoyl chloride911 N,N'-benzoyl-N'- .sub.- t-butyl hydrazine tigloyl chloride912 N'- .sub.- t-butyl-N-benzoyl-N'- acetyl chloride 2,4-dichlorobenzoyl hydrazine913 N'- .sub.- t-butyl-N-benzoyl-N'- methacryloyl 2,4-dichlorobenzoyl hydrazine chloride__________________________________________________________________________
Example Nos. 904 and 906 were prepared by following substantially the procedures in Example 905 and using N'-t-butyl-N-(2,3-diemthylbenzoyl) hdyrazine and ethanol, and N'-t-butyl-N-benzoylhydrazine and methanol, respectively.
Example Nos. 915 and 916 were prepared by following substantially the procedures in Example 914 and using 4-methylbenzene sulfonyl and 4-fluorobenzene sulfonyl, respectively.
By following substantially the procedure in Example 893 and using the hydrazine and halide shown in Table XVIII and the other reactants in Example 893, the products of Example Nos. 887-892, 894-903 and 907-913 were prepared.
TABLE XVIII______________________________________Ex.No. Hydrazine Halide______________________________________887 N,N'-benzoyl-N'- .sub.- t-butyl hydrazine acetyl chloride888 N,N'-benzoyl-N'- .sub.- t-butyl hydrazine methylchloroformate889 N,N'-benzoyl-N'- .sub.- t-butyl hydrazine methoxyacetyl chloride890 N,N'-benzoyl-N'- .sub.- t-butyl hydrazine vinyl chloroformate891 N,N'-benzoyl-N'- .sub.- t-butyl hydrazine crotonyl chloride892 N,N'-benzoyl-N'- .sub.- t-butyl hydrazine tigloyl chloride894 N'- .sub.- t-butyl-N-4-ethylbenzoyl-N'- methylacryloyl 3,5-dimethylbenzoyl hydrazine chloride895 N'- .sub.- t-butyl-N-4-ethylbenzoyl-N'- acetyl chloride 3,5-dimethylbenzoyl hydrazine896 N'- .sub.- t-butyl-N-4-ethylbenzoyl-N'- methylchloroformate 3,5-dimethylbenzoyl hydrazine897 N'- .sub.- t-butyl-N-4-ethylbenzoyl-N'- methoxyacetyl 3,5-dimethylbenzoyl hydrazine chloride898 N'- .sub.- t-butyl-N-4-ethylbenzoyl-N'- vinyl chloroformate 3,5-dimethylbenzoyl hydrazine899 N'- .sub.- t-butyl-N-4-ethylbenzoyl-N'- 2-furoyl chloride 3,5-dimethylbenzoyl hydrazine900 N'- .sub.- t-butyl-N-4-ethylbenzoyl-N' - propionyl chloride 3,5-dimethylbenzoyl hydrazine901 N'- .sub.- t-butyl-N-2,3-dimethylbenzoyl- acetyl chloride N'-3-methylbenzoyl hydrazine______________________________________
Example Nos. 917 and 919-921 were prepared by following substantially the procedures in Example 918 except using the hydrazine and halide shown in Table XIX.
TABLE XIX______________________________________Ex.No. Hydrazine Halide______________________________________917 N'- .sub.- t-butyl-N-benzoyl hydrazine 4-fluorobenzene sulfonyl chloride919 N'- .sub.- t-butyl-N-benzoyl hydrazine 4-methylbenzene sulfonyl chloride920 N'- .sub.- t-butyl-N-(2-pyridinoyl) benzene sulfonyl hydrazine chloride921 N'- .sub.- t-butyl-N-benzoyl hydrazine 2-thienyl sulfonyl chloride______________________________________
Example No. 1014 was prepared by following substantially the procedure in Example 1013 and using mucobromic acid.
Example Nos. 999 to 1007 and 1012 were prepared by following substantially the procedure of Example 872 and using the appropriately substituted reactants.
Example Nos. 1009 to 1011 were prepared by following substantially the procedure of Example 1008 and using the appropriately substituted reactants.
It will be appreciated by those skilled in the art that compounds of Formula I can be used as precursors for preparing other compounds of Formula I by procedures well known to those skilled in the art. For example, a suitable compound of Formula I can be reduced, alkylated, substituted, esterified, hydrolyzed or the like.
As previously noted, the compounds of the present invention exhibit excellent insecticidal activity and are most active against insects of the orders Lepidoptera and Coleoptera.
In general, for the control of insects in agriculture, horticulture and forestry, the compounds of the present invention may be used at a dosage corresponding to from about 10 grams to about 10 kilograms of the active substance per hectare and from about 100 grams to about 5 kilograms per hectare of the active substance is preferred. The exact amount of dosage for a given situation can be routinely determined and depends on a variety of factors, for example, the substance used, the kind of insect, the formulation used, the state of the crop infested with the insect and the prevailing weather conditions. The term "insecticidal" as employed in the specification and claims of this application is to be construed as any means which adversely affects the existence or growth of the target insects at any stage in their life cycle. Such means can comprise a complete killing action, eradication, arresting in growth, inhibition, reducing in number, reproductive inhibition (such as ovicidal or chemisterilant) or any combination thereof. The term "control" as employed in the specification and claims of this application is to be construed as meaning "insecticidal" or protecting plants from insect damage. By "insecticidally effective amount" is meant that dosage of active substance sufficient to exert insect "control."
The compounds of the present invention, for practical applications, can be utilized in the form of compositions or formulations. Examples of the preparation of compositions and formulations can be found in the American Chemical Society publication "Pesticidal Formulation Research," (1969), Advances in Chemistry Series No. 86, written by Wade Van Valkenburg; and the Marcel Dekker, Inc. publication "Pesticide Formulations," (1973), edited by Wade Van Valkenburg. In these compositions and formulations, the active substance or substances are mixed with conventional inert agronomically acceptable (i.e., plant compatible and/or pesticidally inert) diluents or extenders such as solid carrier material or liquid carrier material, of the type usable in conventional compositions or formulations. By agronomically acceptable carrier is meant any substance which can be used to dissolve, disperse or diffuse the active ingredient in the composition without impairing the active ingredient's effectiveness and which by itself has no significant detrimental effect on the soil, equipment, desirable plants or agronomic environment. If desired, conventional adjuvants such as surfactants, stabilizers, antifoam agents and antidrift agents may also be added.
Examples of compositions and formulations according to the invention are aqueous solutions and dispersions, oily solutions and oil dispersions, pastes, dusting powders, wettable powders, emulsifiable concentrates, flowables, granules, baits, invert emulsions, aerosol compositions and fumigating candles.
Wettable powders, pastes, flowables and emulsifiable concentrates are concentrated preparations which are diluted with water before or during use.
Baits are preparations generally comprising a food or other substance attractive to the target pest, that includes at least one lethal or non-lethal toxicant. Lethal toxicants kill the pest upon ingesting the bait while non-lethal toxicants change the behavior, feeding habits and physiology of the pest for the purpose of control.
The invert emulsions are mainly used for air application, where large areas are treated with a comparatively small amount of preparation. The invert emulsion may be prepared in the spraying apparatus shortly before, or even during, the spraying operation by emulsifying water in an oil solution or an oil dispersion of the active substance.
Compositions and formulations are prepared in a known manner, for instance by extending the active compounds with conventional dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g., conventional surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as halogenated hydrocarbons, e.g., dichlorodifluoromethane and trifluorochloromethane, as well as butane, propane, nitrogen and carbon dioxide; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g., benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g., chlorobenzenes, etc.), cycloalkanes (e.g., cyclohexane, etc.), paraffins (e.g., petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g., methylene chloride, chloroethylenes, etc.), vegetable oils (e.g., soybean oil, cottonseed oil, corn oil, etc.), alcohols (e.g., methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g., glycol monomethyl ether, etc.), amines (e.g., ethanolamine, etc.), amides (e.g., dimethyl formamide, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, etc.), and/or water; solid carriers including ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates; solid carriers for granules include crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. The following may be chiefly considered for use as conventional carrier vehicle assistants: emulsifying agents, such as cationic and/or nonionic and/or anionic emulsifying agents (e.g., polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolysates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
If desired, it is possible to use colorants in compositions and formulations containing compounds of the present invention such as inorganic pigments, for example, iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The active compounds of the present invention may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, arthropodicides, nematicides, fungicides, bactericides, rodenticides, herbicides, fertilizers, growth-regulating agents, synergists, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.
As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1% and 99% by weight, and preferably between about 1% and 75% by weight, of the mixture. Carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is used in an amount substantially between about 0.0001% and 5%, preferably between about 0.001% and 3%, by weight of the mixture. Thus the present invention contemplates overall formulations and compositions which comprise mixtures of a conventional dispersible carrier such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water, preferably including a surface-active effective amount of a carrier vehicle assistant (e.g., a surface-active agent, such as an emulsifying agent and/or a dispersing agent), and an amount of the active compound generally, between about 0.0001% and about 99% by weight of the composition, preferably between about 0.001% and about 90% by weight of the composition, and more preferably between about 0.01% and about 75% by weight of the composition, which is effective for the purpose in question.
The active compounds can be applied as sprays by methods commonly employed, such as conventional high-gallonage hydraulic sprays, low gallonage sprays, ultra-low-volume sprays, airblast spray, aerial sprays, and dusts. If low volume applications are desired, a solution of the compound is usually used. In ultra-low-volume applications, a liquid composition containing the active compound is usually applied as a spray (e.g., mist) by means of atomizing equipment in finely divided form (average particle size of from about 50 to about 100 microns or less) using airplane crop spraying techniques. Typically only a few liters per hectare are needed and often amounts up to about 15 to 1000 g/hectare, preferably about 40 to 600 g/hectare are sufficient. With ultra-low-volume, it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound.
Furthermore, the present invention contemplates methods of killing, combatting or controlling insects, which comprises contacting insects with a correspondingly combative or toxic amount (i.e., an insecticidally effective amount) of at least one active compound of the invention alone or together with a carrier vehicle (composition or formulation) as noted above. The term "contacting" as employed in the specification and claims of this application is to be construed as applying to at least one of (a) such insects and (b) the corresponding habitat thereof (i.e., the locus to be protected, for example, to a growing crop or to an area where a crop is to be grown) the active compound of this invention alone or as a constituent of a composition or formulation. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, dry dressing, moist dressing, wet dressing, slurry dressing, encrusting and the like.
It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon such factors as the type of equipment employed, method of application, area to be treated, types of pests to be controlled and degree of infestation. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.
Granular preparations are produced for example, by taking up the active substance in a solvent and by using the resulting solution, as the case may be in the presence of a binder, to impregnate a granular carrier material, such as porous granules (for example, pumice and attaclay), or chopped tobacco stems or the like.
A granular preparation (frequently termed a "pellet") may alternatively be produced by compressing the active substance together with powdered minerals in the presence of lubricants and binders and by disintegrating and straining the composite to the desired grain size.
Dusts are obtainable by intimately mixing the active substance with an inert solid carrier material in a concentration of from about 1 to about 50% by weight. Examples of suitable solid carrier materials are talc, kaolin, pipe clay, diatomaceous earth, dolomite, gypsum, chalk, bentonite, attapulgite and colloidal Si02 or mixtures of these and similar substances. Alternatively organic carrier materials such as, for example, ground walnut shells may be used.
Wettable powders and flowables are produced by mixing from about 10 to about 99 parts by weight of a solid inert carrier such, for example, as the aforementioned carrier materials with from about 1 to about 80 parts by weight of the active substance optionally dissolved in a volatile solvent such as acetone, from about 1 to about 5 parts by weight of a dispersing agent such, for example, as the lignosulfonates or alkylnaphthalene sulfonates known for this purpose and preferably also from about 0.5 to about 5 parts by weight of a wetting agent, such as fatty alcohol sulfates, or alkylarylsulfonates of fatty acid condensation products. In the case of flowables, a liquid inert carrier such as water is also included.
To produce emulsifiable concentrates the active compound is dissolved or finely divided in a suitable solvent which preferably is poorly miscible with water, an emulsifier being added to the resulting solution. Examples of suitable solvents are xylene, toluene, high-boiling aromatic petroleum distillates, for example solvent naphtha, distilled tar oil and mixtures of these liquids. Examples of suitable emulsifiers are alkylphenoxypolyglycol ethers, polyoxyethylene sorbitan esters of fatty acids or polyoxyethylene sorbitol esters of fatty acids. The concentration of the active compound in these emulsifiable concentrates is not restricted within narrow limits and may vary between about 2% and about 50% by weight depending upon toxicant solubility. A suitable liquid highly concentrated primary composition other than an emulsifiable concentrate is a solution of the active substance in a liquid which is readily miscible with water, for example, acetone, to which solution a dispersant and, as the case may be, a wetting agent are added. When such a primary composition is diluted with water shortly before or during the spraying operation an aqueous dispersion of the active substance is obtained.
An aerosol preparation according to the invention is obtained in the usual manner by incorporating the active substance or a solution thereof in a suitable solvent in a volatile liquid suitable for use as a propellant such, for example, as a mixture of chlorine and fluorine derivatives of methane and ethane.
Fumigating candles or fumigating powders, i.e., preparations which when burning are capable of emitting a pesticidal smoke, are obtained by taking up the active substance in a combustible mixture which may, for example, comprise a sugar or a wood, preferably in the ground form, as a fuel, a substance to sustain combustion such, for example, as ammonium nitrate or potassium chlorate, and furthermore a substance for retarding combustion, for example kaolin, bentonite and/or colloidal silicic acid.
A bait preparation comprises a food or other substance attractive to pests, a carrier, the toxicant and may optionally include other substances commonly used in preparations of this kind, such as, a preservative to inhibit bacterial and fungal growth, a waterproofing agent to prevent disintegration under wet conditions and dyes or colorants as described above.
In addition to the aforementioned ingredients, the preparations according to the invention may also contain other substances commonly used in preparations of this kind.
For example, a lubricant, such as calcium stearate or magnesium stearate, may be added to a wettable powder or to a mixture to be granulated. Furthermore, there may, for example, be added "adhesives" such as polyvinylalcohol cellulose derivatives or other colloidal materials, such as casein, to improve the adherence of this pesticide to the surface to be protected.
Representative preparation of compositions and formulations including the compounds of the present invention are set forth below as Examples A through I by way of illustration but not limitation.
______________________________________Example AGranularIngredient %/wt.______________________________________Toxicant and toxicant impurities 0.25Triton .RTM. X-305 (binder) 0.25(Octylphenyl-30-ethyleneoxide ethanol)Agsorb .RTM. 24/48 (diluent) 99.50(Montmorillonite clay)______________________________________
Preparation: The toxicant and Triton.RTM. X-305 are dissolved into methylene chloride and the mixture is added to the Agsorb.RTM. with continuous mixing. The methylene chloride is then allowed to evaporate.
______________________________________Example BDustIngredient %/wt.______________________________________Toxicant and toxicant impurities 1.0Talc 99.0______________________________________
Preparation: Toxicant is dissolved in excess acetone and the mixture is impregnated onto the talc. The acetone is then permitted to evaporate.
______________________________________Example CWettable PowderIngredient %/wt.______________________________________Toxicant and toxicant impurities 31.3Duponal .RTM. WA Dry (wetter) 2.0(Sodium lauryl sulfate)Reax .RTM. 45A (dispersant) 5.0(Sodium lignin sulfonate)Barden clay (diluent) 31.7HiSil .RTM. 233 (diluent) 30.0(Sodium silica)______________________________________
Preparation: The toxicant, optionally dissolved in a volatile solvent, is absorbed onto the Barden clay and HiSil.RTM. carriers The Duponal.RTM. and Reax.RTM. are then added and the entire dry mixture blended until homogeneous. The composition is then micronized to a fine particle size.
______________________________________Example DEmulsifiable ConcentrateIngredient %/wt.______________________________________Toxicant and toxicant impurities 15.0Sponto .RTM. 232T (emulsifier) 6.0(Anionic and nonionic blend of thefollowing surfactants: calciumdodecyl benzene sulfonate; andethoxylated alkylphenol)Sponto .RTM. 234T (emulsifier) 4.0(Anionic and nonionic blend of thefollowing surfactants: calciumdodecyl benzene sulfonate; andethoxylated alkylphenol)Cyclohexanone (solvent) 22.5Tenneco .RTM. 500-100 (solvent) 52.5(Aromatic solvent mixtureprincipally comprising xylene,cumene and ethyl benzene havinga boiling point range of 290-345.degree. F.)______________________________________
Preparation: All ingredients are mixed together with continuous agitation until a homogeneous clear solution is obtained.
______________________________________Example EAerosolIngredient %/wt.______________________________________Toxicant and toxicant impurities 0.5Freon 12 99.5______________________________________
Preparation: The components are mixed and packaged under pressure in a suitable container equipped with a release spray valve.
______________________________________Example FFumigating Candle or Fumigating PowderIngredient %/wt.______________________________________Toxicant and toxicant impurities 1.0Wood dust 96.0Starch 3.0______________________________________
Preparation: Toxicant, wood dust, and starch are blended together and then molded into a candle using a small amount of water to activate the starch.
Example G______________________________________BaitMethod AIngredient %/wt.______________________________________Toxicant and toxicant impurities 1.00Wheat Bran (carrier and attractant) 89.95Corn Syrup (attractant) 7.00Corn Oil (attractant) 2.00Kathon .sup..RTM. 4200 (preservative) 0.05(2- -n-octyl-4-isothiazolin-3-one)______________________________________
Preparation: The corn oil and corn syrup are added to the wheat bran with adequate mixing. The toxicant and Kathon.RTM. are premixed with excess acetone and this solution is added to the wheat bran base with continued mixing. The acetone is then permitted to evaporate.
______________________________________Method BIngredient %/wt.______________________________________Toxicant and toxicant impurities 0.06Granulated Sugar (carrier and attractant) 99.94______________________________________
EXAMPLE H
Pellet
Same as Example G, Method A, with this addition: the bait composition is formed into 1/4" diameter by 3/8" long pellets using a suitable die and press apparatus.
Example I______________________________________FlowableIngredient %/wt.______________________________________Toxicant and toxicant impurities 31.3Duponal .sup..RTM. WA Dry (wetter) 2.0(Sodium lauryl sulfate)Reax .sup..RTM. 45A (dispersant) 5.0(Sodium lignin sulfonate)HiSil .sup..RTM. 233 (diluent) 30.0(Sodium silica)Kelzan .sup..RTM. (thickener) 0.5(Xanthan gum)Water 31.2______________________________________
Preparation: The toxicant is absorbed onto the HiSil.RTM. carrier. The Duponal.RTM. and Reax.RTM. are then added and the entire dry mixture blended until homogeneous. The composition is then micronized to a fine particle size. The resulting powder is suspended in water and the Lekzan.RTM. added.
Compositions and formulations according to the present invention may also include known pesticidal compounds. This expands the spectrum of activity of the preparations and may give rise to synergism.
The following known insecticidal, fungicidal and acaricidal compounds are suitable for use in such a combined preparation.
Insecticides such as:
Chlorinated hydrocarbons, for example, 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane and hexachloroepoxyoctahydrodimethanonaphthalene;
Carbamates, for example, N-methyl-1-naphthylcarbamate;
Dinitrophenols, for example, 2-methyl-4,6-dinitrophenol and 2-(2-butyl)-4,6-dinitrophenyl-3,3-dimethylacrylate;
Organic phosphorus compounds, such as dimethyl-2-methoxy-3-carbonyl-1-methylvinyl phosphate, O,O-diethyl-O-p-nitrophenylphosphorothioate; N-monomethylamide of O,O-dimethyldithiophosphorylacetic acid;
Diphenylsulfides, for example, p-chlorobenzyl or p-chlorophenyl sulfide and 2,4,4',5-tetrachlorodiphenylsulfide;
Diphenylsulfonates, for example, p-chlorophenylbenzenesulfonate;
Methylcarbinols, for example, 4,4-dichloro-1-trichloromethylbenzhydrol;
Quinoxaline compounds, such as methylquinoxaline dithiocarbonate;
Amidines such as N'-(4-chloro-2-methylphenyl) N,N-dimethylformamidine;
Pyrethroids such as Allethrin;
Biologicals such as Bacillus thuringiensis preparations;
Organic tin compounds such as tricyclohexyltin hydroxide;
Synergists such as piperonyl butoxide;
Insect growth regulators such as N-benzoyl-phenyl ureas, for example, diflubenzuron.
Fungicides such as:
Organic mercury compounds, for example, phenylmercuryacetate and methylmercurycyanoguanide;
Organic tin compounds, for example, triphenyltin hydroxide and triphenyltin acetate;
Alkylenebisdithiocarbamates, for example, zinc ethylenebisthiocarbamate and manganese ethylenebisdithiocarbamate; and
2,4-dinitro-6-(2-octyl-phenylcrotonate), 1-bis(dimethylamino)phosphoryl-3-phenyl-5-amino-1,2,4-triazole, 6-methylquinoxaline-2,3-dithiocarbonate, 1,4-dithioanthraquinone-2,3-dicarbonitrile, N-trichloromethylthiophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, N-dichlorofluoromethylthio-N-phenyl-N'-dimethylsulfonyldiamide and tetrachloroisophthalonitrile.
BIOLOGICAL ACTIVITY
It has been found by biological evaluation that compounds according to the present invention have pesticidal activity and are capable of controlling larvae and adult forms of pests, especially insects from the orders Lepidoptera and Coleoptera and most especially insects from the order Lepidoptera. One skilled in the art will know how to determine the activity of a given compound against a given insect and the dosage required to obtain general or selective insecticidal effects. The compounds of the present invention in part affect the normal development of insects, particularly insects from the order Lepidoptera, by directly and/or indirectly influencing the moulting process.
As previously noted, the compounds of the present invention are particularly suitable for controlling plant destructive insects in crops of cultivated plants, such as, but not limited to, cotton, vegetables, corn and other cereals and the like; forestry, such as, but not limited to, birch, spruce, pine, fir and the like; and ornamental plants, flowers and trees. Compounds of the present invention are also particularly suitable for controlling insects destructive to stored commodities such as seeds and the like; fruit crops, such as, but not limited to fruit and/or citrus trees, raspberry bushes and the like; and turf, such as, but not limited to, lawns, sod and the like.
In evaluating the pesticidal activity of the compounds of this invention, the following test procedures were employed.
Unless a different application rate is indicated in Table XX, a test solution containing 600 parts per million (ppm) was made by dissolving the test compound in a solvent (acetone:methanol, 1:1), adding water to give an acetone:methanol:water system of 5:5:90 and then a surfactant. A 1:1 mixture of an alkylarylpolyetheralcohol (sold under the trademark Triton.RTM. X-155) and a modified phthalic glycerol alkyl resin (sold under the trademark Triton.RTM. B-1956) was utilized at the equivalent of 1 ounce per 100 gal. of test solution as a surfactant.
Initial evaluations were made on one or more of the following pests:
______________________________________CodeSymbol Common Name Latin Name______________________________________SAW Southern Armyworm Spodoptera eridaniaMBB Mexican Bean Beetle Epilachna varivestisBW Boll Weevil Anthonomus grandis grandis______________________________________
For the foliar bean beetle and armyworm tests, individual bean (Phaseolus limensis var. Woods' Prolific) leaves are placed on moistened pieces of filter paper in Petri dishes. The leaves are then sprayed with the test solution using a rotating turntable and allowed to dry. The dishes are infested with 10 third instar larvae of Southern armyworm or Mexican bean beetle. The dishes are then covered.
For the Boll Weevil test ten adult weevils are placed in a 0.5 pint glass Mason jar containing a small cube of apple. The weevils are confined to the jars by fiberglass screen mesh secured by a screw-type rim cap. The jars are then sprayed with the test solution using a rotating turntable, directing the spray through the mesh into the jar.
The rotating turntable consists of a fixed, continuously operating spray nozzle under which targets are rotated at a fixed speed and distance. If the target is a Petri dish (such as for the armyworm), the distance from the nozzle is 15 inches. If the target is a Mason jar, the distance between the screened lid and the nozzle is 6 inches (10 inches from the base of the jar to the nozzle). The nozzle is located 8 inches from the rotating shaft. The targets on individual platforms revolve around the shaft at 1 revolution per 20 seconds but only a brief portion of this time occurs in the spray path. Targets pass only once under the nozzle and then are removed to drying hoods.
The nozzle used is a 1/4 JCO Spraying Systems (Wheaton, Ill.) air atomizing nozzle equipped with a No. 2850 fluid cap and No. 70 air cap. At the 10 psig air pressure used and with liquid siphon feed 0.5 GPH (gallons per hour) are delivered in a round spray pattern with a 21.degree. spray angle. Targets are misted with spray droplets to the point that the droplets coalesce to form a uniform thin film insufficient to drown test organisms.
All treatments are maintained at 75-80.degree. F. under continuous fluorescent light in a well-ventilated room.
For soil treatment (systemic) trials, a portion of the 600 ppm test solution is diluted to 150 ppm. Ten (10) ml of the 150 ppm test solution is pipetted into soil (approximately 200 g of standard greenhouse soil) in a 3-inch pot containing a lima bean seedling. This results in a soil concentration of approximately 8 ppm. Treated plants are maintained under existing greenhouse conditions for one week. Two bean leaves are removed and placed individually on moist filter paper in Petri dishes. One leaf is infested with 10 third instar larvae of Mexican bean beetle. The other leaf is infested with 10 third instar larvae of Southern armyworm. The dishes are then covered and held for 3 days at which time the percent control (mortality) is determined. A second observation may be made 6 days after infesting the dishes if the experimenter feels the effect may not be complete or moribund insects appear to evidence signs of some recovery. Where necessary, untreated bean leaves are introduced into dishes held for a second observation to preclude insect starvation.
The results of the initial insecticidal evaluations are given in Table XX.
Armyworm and bean beetle spray (foliar) results are 96 hour observations unless otherwise noted. Boll weevil spray results are 48 hour observations unless, in the discretion of the experimenter, particular evaluations were held for 96 hour observations if it is believed the effect of a test compound may not be complete or moribund insects appear to evidence some signs of recovery. If, after 96 hours, there was a change in the percent control, it is shown in parentheses. Soil treatment results are 72 hour observations. At the discretion of the experimenter, particular evaluations were held for 144 hour observations. If, after 144 hours, there was a change in the percent control, it is shown in parentheses. Evaluations are based on a scale of 0-100 percent in which 0 equals no activity and 100 equals total kill.
TABLE XX______________________________________Initial Biological Evaluations Foliar Application Soil Application Test Species Test SpeciesExample No. SAW MBB BW MBB SAW______________________________________ 1 100.sup.a 0 0 80 0 2 100 0 0 20 0 3 100 60.sup.a 0 100 100 4 100 0 0 60 0 5 100 0 0 50 0 6 40 0 0 .sup. --.sup.b -- 7 100 0 0 50 0 8 10 0 0 -- -- 9 100 0 0 70 100 10 100 0 0 60 0 11 100 0 0 20 100 12 20.sup.d 100 0 50 0 13 100 0 0 20 100 14 20.sup.d 0.sup.d 60.sup.d 0.sup.d 0.sup.d 15 100 0 0 20 0 16 100 0 0 30 100 17 100 0 0 40 100 18 100 100 0 100 100 19 100 0 100 20 0 20 100 0 0 -- -- 21 100 0 0 -- -- 22 100 0 0 40 100 23 100 0 100 -- -- 24 100 0 80 -- -- 25 100 0 0 -- -- 26 100 100 0 0 100 27 100.sup.d 0.sup.d 20.sup.d 20(40).sup.d 70.sup.d 28 10 0 0 -- -- 29 100 0 0 0 40 30 100 0 0 0 10 31 100 100 0 40 100 32 0.sup.d 20.sup.a,c 20.sup.c -- -- 33 100 40 0 20 0 34 100 20 0 70 100 35 100 100 0 100 100 36 100 100 20 90 100 37 100 0 0 -- -- 38 100 90 20 0(60) 100 39 100 0 0 0 20 40 40 20 20 0 0 41 100 0 20 20 100 42 100 100 0 100 100 43 100 100 0 100 100 44 100 10 0 0(20) 0 45 100 0 0 0(40) 0(40) 46 100 0 60 40(80) 60(80) 47 100 100 0 80(90) 100 48 100 100 0(40) 40(60) 100 49 100 100 40(80) 10(60) 100 50 100 0 40(80) 40(70) 0(10) 51 100 100 0 70(100) 30 52 100 100 0 20(30) 20(50) 53 100 0 40 20(60) 100 54 100 20 0 0 0 55 100 10 0 0 0 56 100 100 0 60(80) 100 57 100 0 0 40(60) 0 58 100 20 0 20 0 59 100 70 20 20 100 60 100 40 0 0 0 61 80.sup.d 0 0 60(80) 0 62 100 40 0 20 100 63 100 10 0 20 0 64 100 20 0 0(100) 10(50) 65 100 20 0 0(40) 100 66 100 70 0 40(80) 40(50) 67 100 40 0 20(80) 100 68 100 10 20 20 0 69 100 40 0 20 0 70 100 40 20 0(20) 0 71 100.sup.c 60 0 0(20) 0 72 60 0 0 20 0 73 100 100 0 40(80) 100 74 100 80 0 20 0 75 100 60 0 0 0 76 100 60 0 0(20) 0 77 100 100 0 0 0 78 90 40 0 20 0 79 0.sup.d 0 20 0 0 80 20.sup.d 0 20 0 0 81 100 0 20 0 20 82 100 0 0 0 0 83 100 100 0 60(100) 100 84 10 0 0 0 0 85 100 30 0 0 20 86 100 30 20 0 80(100) 87 100 40 40 0 40(50) 88 100 20 0 0 0 89 100 0 0 0 100 90 100 0 0 0 90 91 100.sup.a,c 0 40 0 0 92 100 50 0 0 90(100) 93 100 0 0 0 0 94 0.sup.d 10 0 0 0 95 100 100 20 40(100) 100 96 100 30 0 0 0 97 100 0 20 0 0 98 100 0 0 0 100 99 100 60 0 40(80) 100100 100 100 0 80(100) 100101 100.sup.c 0 0 20 0102 100 0 0 20 0(40)103 100 100 0 0(60) 100104 100 0 0(20) 0 40(100)105 100 0 40 0 100106 80 0 60 0 0(100)107 100 0 0 0(40) 100108 100 0 0 0 0109 100 20 0 0(100) 100110 100 70 0 100 90(100)111 100 100 0 0 0112 100 100 20 20(40) 90(100)113 100 100 0 100 100114 100 0 0 0 10115 100 100 0 20(60) 90(100)116 100 10 0 0 0117 100 10 0 40(80) 100118 100 10 0 0 90(100)119 100 0 0 0 0120 100 30 20 0 0121 100 100 0 20(40) 100122 70 20 0 0 20(50)123 100 0 0 0(100) 100124 100 100 0 0 20(30)125 100 0 0 0 0126 100 10 0 0 0127 100 10 0 20 0128 100 0 0 0 0129 100 40 40(60) 100(80) 80(100)130 100 0 0 0(20) 100131 100 0 0 0 100132 100 0 0 20(40) 0133 100 10 0 0 0134 100 10 0 0 10(30)135 100 0 0 20(40) 60136 100 70 0 20 30(50)137 100 10 0 40(60) 0138 100 0 0 0 90(100)139 100 0 0 0(20) 0140 100 0 0 20 0141 100 100 0 20(100) 100142 100 0 0 20 40143 0.sup.d 0 0 20 0144 0.sup.d 10.sup.a,c 20.sup.c 0 0145 30.sup.c 0 0.sup.c 0 0146 100 20 40(60) 0 0147 0.sup.d 20.sup.d 20.sup.d 0.sup.d 0.sup.d148 60.sup.d 0 40 0 20(0)149 20.sup.c 20.sup. a,c 0.sup.c 0 0150 20.sup.c 0 0.sup.c 0 0151 0 0 0 0 0152 100 0 0 0 0153 100 0 0 0 89(90)154 100 10 0 0 0155 0.sup.d 30 0 0(20) 0156 10.sup.c 0 0.sup.c 0 0157 0.sup.d 10 20 0 0158 20 0 0 0 0159 10 0 0 0 0160 20.sup.d 0 0 20 0161 30 0 0 0(20) 0162 70 20 0 40(60) 0163 20 20 0 0(20) 0164 100.sup.d 0 20 40 0165 20.sup.c 10 0 0 0166 10 10 0 0 0167 30 0 0 0 0168 10 40 0 0 0169 0.sup.d 30 0 0 0170 0.sup.d 10 0 0 0171 100 40 0 0 0172 100 0 0 0 0173 60 30 20 0 0174 100 0 0 0 80(100)175 100 0 0 0 0176 0.sup.d 10 0 0 0177 100 30 0 0 10178 100 10 0 0 10179 90 0 20 0 0180 100 0 0 0 0181 100 10 0 0 0182 100 0 0 0 0183 30 80 0 0(100) 0(100)184 100 10 0 0 0185 30.sup.c 20.sup.a,c 0.sup.c 0 0186 30.sup.c 10.sup.d 30.sup.d 20.sup.d 0.sup.d187 100 0 0 0(20) 0(10)188 100.sup.c 0 0.sup.c 0 0189 100.sup.c 0 20 0 0190 100 0 0 0(40) 20(60)191 90 0 0 0 0192 20 0 0 0 0193 100 0 0 0 0194 100 80 20 20(60) 100195 100 80 0 80(100) 100196 100 0 0 0 100197 100 0 20 0(20) 100198 100 0 0 20 90(100)199 20 10 0 20 30200 100 0 0 0(20) 90201 100 0 0(60) 0 20(30)202 40 20 0 40 0203 60 0 20(60) 0 0204 50 0 0 0 0205 100 10 0 20 100206 100 10 0 0 100207 0.sup.d 20.sup.d 20.sup.d 0.sup.d 0(10).sup.d208 100 0 0 0(20) 100209 100 10 0 60(20) 100210 20.sup.c 10 40 0 0211 20 10 0 0 0212 100 0 0 0 90(100)213 100 0 40 0 0214 100 0 0 0 40(60)215 100 10 0 0(20) 100216 100 0 20 20 50(60)217 100 60 0 20 100218 90 10 0 0 0219 60.sup.c 0 0.sup.c 0 0220 100 0 0 0 100221 60 10 0 20 0222 100.sup.c 10.sup.a,c 0.sup.c 0 0223 100 10 0 40 100224 40 10 20 0 0225 100 20 0 0(20) 100226 100 10 0 0 0227 100 0 0 0 30(40)228 100 0 20 0(40) 100229 60 20 0 0 0230 100 50 0 60(80) 100231 60 20 0 40 60232 100 0 0 20 0233 100 0 0 40 60234 100 10 0 0 100235 100 60 0 100 100236 100 10 0 0 30237 100 20 0 0 0238 90 60 0 0 0239 100 0 0 0 0240 30 10 0 0 0241 100 0 0 0 0242 50 30 0 0 0243 10 20 0 0 0244 100 0 0 0 70(80)245 100 0 0 0 80(90)246 100 10 0 0 0247 100 0 0 0 0248 100 0 0 0 0249 100 0 0 0 0250 80 50 0 0 10251 100 20 20 20(40) 60252 100 0 0 0(20) 100253 100 10 20(40) 0 20(30)254 100 0 0 0 0255 100 100 0 0 0256 100 0 0 0 0257 100 0 0 20 20258 40.sup.c 90 40 100 0259 100 10 0 0 0260 100 20 0 0 0261 0.sup.d 10 0 0 0262 60 0 0 0 0263 100 30 0 20 40264 80 0 80(100) 0 10(30)265 0.sup.c 10 0 0 0266 0.sup.d 10 0 0 0267 100 0 0 0 0268 40 0 0 0 0269 100 0 60(80) 0 0270 100 0 0 20(40) 0271 100 10 0 20(0) 70272 40 10 0 0 0273 100 0 40(100) 0 0274 100 10 0 20 50(90)275 40.sup.c 30.sup.a,c 0.sup.c 0 0276 100 10 20(60) 0 0277 100 30 0 20 0278 60 0 0 0 0279 100 10 0 0 0280 100 10 20(80) 0 0281 100 0 0 0 0282 100 30 0 0 0283 100 0 0 0 0284 90 50 0 0 0285 100 50 0 0 0286 100 0 0 0 0287 100 10 0 0 0288 100 0 0 0 0289 100 40 0 20 0290 100 50 0 0 0291 100 30 0 0 80(90)292 100 10 0 0 100293 20 30 20 0 0294 0.sup.d 10.sup.a,c 0.sup.c 0 0295 100 100 0 0 60(80)296 100 50 0 60(100) 100297 100 40 0 0 0298 80 30 0 0 0299 100 20 0 0 0300 100 0 0 0(20) 100301 100 0 0 0 70(100)302 100 0 0 0 0303 100 30 0 0 0304 70 90 0 0 0305 100 40 0 0 60(100)306 100 40 0 0 0307 100 60 0 0 0308 0.sup.d 40 0 0 0309 100 60 0 0 0310 100 40 0 0 0311 100 100 0 40(60) 90(100)312 100 0 0 0 10313 100 20 0 0 0314 100 0 0 0 0315 100 0 0 20(40) 0316 100 0 0 20 100317 100 20 0 0 80(100)318 100 20 0 0 90(100)319 100 20 0 0 100320 100 0 0 40 0321 80 0 0 -- --322 100 0 0 -- --323 100 20 0 -- --324 100 20 0 -- --325 100 10 0 -- --326 100 30 0 -- --327 30 30 0 -- --328 0.sup.d 50 0 -- --329 100 30 0 -- --330 100 30 0 -- --331 100 30 0 -- --332 100 70 0 -- --333 30 0 0 -- --334 100 0 0 -- --335 90 70 0 -- --336 100 30 0 -- --337 50.sup.c 30 0 -- --338 100 40 0 -- --339 100 0 20(80) -- --340 100 0 0 -- --341 100 100 0 -- --342 100 0 0 -- --343 100 10 20(60) -- --344 0.sup.c 0 40 -- --345 20 0 0 -- --346 40.sup.c 10.sup.a,c 0.sup.c -- --347 100 20 0 -- --348 100.sup.c 0 0.sup.c -- --349 60 0 0 -- --350 100 20 0 -- --351 100 0 0 -- --352 50 20 0 -- --353 100 0 0 -- --354 100 30 0 -- --355 100.sup.c 90 0 -- --356 40.sup.c 0 0.sup.c -- --357 100 20 0 -- --358 100 0 0 -- --359 100 0 0 -- --360 70.sup.c 0 0.sup.c -- --361 100 10 0 -- --362 100 70 0 -- --363 100 20 0 -- --364 100 10 0 -- --365 100 0 0 -- --366 100 40 0 -- --367 100 30 0 -- --368 100 0 0 -- --369 100 0 0 -- --370 30 30 0 -- --371 100 10 20 -- --372 30 0 0 -- --373 90 10 0 -- --374 100 10 0 -- --375 100.sup.d 10 0 -- --376 100.sup.c 20 0 -- --377 100 20 0 -- --378 100 20 0 -- --379 100 20 0 -- --380 100 10 0 -- --381 100 30 0 -- --382 100 0 20 -- --383 100 20 0 -- --384 80 20 0 -- --385 100 100 0 -- --386 100 20 20 -- --387 100 0 0 -- --388 100 30 20(40) -- --389 0.sup.d 70 0 -- --390 100 30 0 -- --391 100 0 20(60) -- --392 100 100 0 -- --393 100 20 0 -- --394 100 0 0 -- --395 100 70 0 -- --396 100 100 0 -- --397 100 0 0 -- --398 100 40 0 -- --399 100 0 0 -- --400 90 0 0 -- --401 100 70 0 -- --402 100 40 0 -- --403 100 0 0 -- --404 100 20 20(40) -- --405 100 10 0 -- --406 100 0 20 -- --407 100 20 0 -- --408 90 60 0 -- --409 40 0 0 -- --410 100 90 0 -- --411 100 10 0 -- --412 30 30 0 -- --413 100 10 0 -- --414 60 50 40 -- --415 60 20 20(60) -- --416 100 30 0 -- --417 100 20 0 -- --418 100 0 20 -- --419 100 10 0 -- --420 100 0 40 -- --421 100 10 0 -- --422 100 0 0 -- --423 100 0 0 -- --424 100 10 0 -- --425 100 70 0 -- --426 100 0 0 -- --427 100 20 0 -- --428 100 10 20(80) -- --429 100 20 0 -- --430 100 0 0 -- --431 90 40 0 -- --432 100 20 0 -- --433 100 0 0 -- --434 100 10 20 -- --435 100 20 0 -- --436 0.sup.d 30 0 -- --437 100 10 0 -- --438 100 40 0 -- --439 100 0 0 -- --440 100 20 0 -- --441 100 20 0 -- --442 100 30 0 -- --443 100 20 0 -- --444 100 0 0 -- --445 100 20 0 -- --446 100 20 20 -- --447 100 20 0 -- --448 100 20 0 -- --449 100 20 0 -- --450 100 20 0 -- --451 100 50 0 -- --452 100 30 0 -- --453 100 30 0 -- --454 100 0 0 -- --455 100 50 0 -- --456 100 20 0 -- --457 100 50 0 -- --458 100 0 0 -- --459 100 0 20 -- --460 100 0 0 -- --461 0.sup.d 10.sup.a,c 0.sup.c -- --462 40 20 0 -- --463 50 10 0 -- --464 100 10 0 -- --465 70 0 0 -- --466 100 0 40 -- --467 100 0 0 -- --468 100 10 0 -- --469 60.sup.c 20 0 -- --470 100 10 0 -- --471 100 10 0 -- --472 100 0 0 -- --473 100 20 0 -- --474 100.sup.c 20 0 -- --475 50.sup.c 0 0.sup.c -- --476 100 0 0 -- --477 100 10 20 -- --478 100 20 0 -- --479 100 0 0 -- --480 100 20 0 -- --481 100 0 0 -- --482 100 20 0 -- --483 100 10 0 -- --484 100 20 0 -- --485 100 40 0 -- --486 100 20 0 -- --487 100 50 0 -- --488 100 0 0 -- --489 100 40 20 -- --490 100 0 0 -- --491 60 20 0 -- --492 100 0 0 -- --493 100 20 0 -- --494 100 0 0 -- --495 100 10 0 -- --496 100 0 0 -- --497 100 10 0 -- --498 100 0 60(80) -- --499 100 40 0 -- --500 100 10 0 -- --501 100 30 0 -- --502 100 10 20 -- --503 90 30 0 -- --504 100 40 0 -- --505 100 30 20 -- --506 100 0 0 -- --507 60 20 0 -- --508 100 0 0 -- --509 100 70 0 -- --510 100 10 0 -- --511 100 10 0 -- --512 90 20 0 -- --513 100 10 0 -- --514 100 30 0 -- --515 100 100 0 -- --516 100 10 0 -- --517 100 10 0 -- --518 100 30 0 -- --519 100 10 0 -- --520 100 30 0 -- --521 100 50 0 -- --522 100 10 0 -- --523 100 10 0 -- --524 90 30 0 -- --525 100 30 0 -- --526 100 10 0 -- --527 100 0 0 -- --528 100 0 0 -- --529 100 10 0 -- --530 100 10 0 -- --531 100 10 0 -- --532 100 20 0 -- --533 100 0 0 -- --534 100 10 0 -- --535 100 0 0 -- --536 100 10 0 -- --537 100 0 0 -- --538 100 20 0 -- --539 100 0 0 -- --540 100 10 0 -- --541 100 0 0 -- --542 100 0 0 -- --543 100 0 0 -- --544 100 0 0 -- --545 100 0 0 -- --546 100 0 0 -- --547 100 0 0 -- --548 100 30 20 -- --549 100 30 0 -- --550 100 40 0 -- --551 100 0 0 -- --552 100 30 20 -- --553 100 40 0 -- --554 100 20 0 -- --555 100 20 0 -- --556 100 10 0 -- --557 30 30 0 -- --558 100 20 0 -- --559 100 50 0 -- --560 90 0 0 -- --561 100 30 20 -- --562 100 0 0 -- --563 100 10 0 -- --564 100 0 0 -- --565 100 0 0 -- --566 40 70 0 -- --567 100 40 20 -- --568 100 0 0 -- --569 100 20 0 -- --570 100 10 0 -- --571 100 50 0 -- --572 100 80 0 -- --573 100 20 0 -- --574 100 0 0 -- --575 100 0 20 -- --576 100 20 0 -- --577 100 0 0 -- --578 100 40 0 -- --579 100 40 0 -- --580 100 0 0 -- --581 100 0 0 -- --582 100 0 0 -- --583 100 30 0 -- --584 100 0 0 -- --585 100 0 0 -- --586 100 0 0 -- --587 100 10 0 -- --588 100 40 0 -- --589 100 40 0 -- --590 100 30 0 -- --591 100 0 0 -- --592 100 40 0 -- --593 100 40 0 -- --594 100 10 0 -- --595 100 10 20 -- --596 100 80 0 -- --597 100 40 0 -- --598 100 10 20 -- --599 100 40 0 -- --600 100 30 0 -- --601 100 10 0 -- --602 100 10 0 -- --603 100 20 0 -- --604 100 10 0 -- --605 100 20 20(80) -- --606 80.sup.d 20 0 -- --607 80 10 0 -- --608 100 30 0 -- --609 100 20 0 -- --610 0.sup.d 20 0 -- --611 30 30 0 -- --612 0(30).sup.a 20 0 -- --613 0(70).sup.a 50 0 -- --614 10 20 0 -- --615 100 20 0 -- --616 100 0 0 -- --617 100 10 0 -- --618 100 10 0 -- --619 100 0 0 -- --620 70 30 20(40) -- --621 100 10 0 -- --622 100 70 0 60(100) 100623 100 0 0 0 20(50)624 100 80 0 0 80(100)625 100 10 20 -- --626 100 90 0 -- --627 100 0 0 -- --628 100 40 0 -- --629 100 0 0 -- --630 100 0 0 -- --631 100 0 0 -- --632 100 30 0 -- --633 100 10 0 -- --634 100 90 0 -- --635 0.sup.d 100 0 0 0636 80.sup.d 100 0 0 0637 100 100 0 20(60) 100638 100 10 20 -- --639 10 20 0 -- --640 100 80 0 0 0641 100 30 0 -- --642 100 100 0 -- --643 100 20 0 -- --644 100 40 0 -- --645 100 20 0 -- --646 100 0 0 20 100647 100 60 20 20 40(60)648 70 100 0 80(20) 40(100)649 100 40 0 40 0(80)650 100.sup.c 10 0 0(40) 0(20)651 90 60 40 80(60) 0(20)652 20 10 0 0(40) 40(60)653 0.sup.d 0 0 0(20) 0654 70 100 0 20(40) 0655 80 70 0 40(100) 40(80)656 100 0 0 0 100657 30 0 0 0 0658 40.sup.c 90 20 80(100) 0659 30.sup.c 80 0 0(80) 0660 80.sup.c 70 0 0 0661 100 20 0 0 0662 70 40 20 0 0663 100 0 0 -- --664 100.sup.c 0 0 0 0665 60 30 20(40) 0(20) 0666 100 0 0 -- --667 100 0 0 -- --668 60.sup.d 20 0 -- --669 20.sup.d 30 0 -- --670 90 40 0 -- --671 100 30 0 -- --672 100 100 0 -- --673 20 40 0 -- --674 100 50 80 -- --675 100 30 0 -- --676 100.sup.c 80 0 -- --677 70.sup.c 40 0 -- --678 50 30 0 -- --679 100 30 0 -- --680 100 10 0 -- --681 100 100 0 -- --682 10 40 0 -- --683 100 0 0 0 20684 20.sup.a 100.sup.a 0 -- --685 10.sup.c 10.sup.a,c 40 -- --686 20.sup.c 0.sup.a,c 0 -- --687 0.sup.d 30.sup.a,c 0 -- --688 100 100 0 60(100) 100689 90 50 0 40(100) 0(20)690 0.sup.d 10.sup.d 0.sup.d 0.sup.d 0.sup.d691 30.sup.c 10 0 0 0692 80 0.sup.a 0 -- --693 0.sup.d 20 0 0 0694 80 80 40 0 0695 60.sup.d 30 0 0 0696 0.sup.d 40 20 20 0697 20.sup.c 0 0 0 0698 100 0 20 0 100699 100 100 0 60(100) 90700 0.sup.d 100.sup.a,c 0 0 0701 90.sup.c 10 20 40(20) 0702 0.sup.d 100 0 0 0703 10.sup.a 0.sup.a 0 -- --704 0.sup.d 30 0 -- --705 80 0 0 -- --706 30 30 20 -- --707 100 40 0 -- --708 100 10 0 -- --709 80.sup.d 100 20(40) -- --710 100 30 0 -- --711 100 30 0 -- --712 100 20 0 -- --713 100 60 0 -- --714 100 40 0 -- --715 100 20 0 -- --716 100 0 0 -- --717 100 40 0 -- --718 10.sup.c 70 0 -- --719 0.sup.d 20 0 -- --720 100 0 0 -- --721 100 30 0 -- --722 50 0 40 0 0723 100 80 40 60(100) 90(100)724 90 10 0 0(20) 0725 100 0 0 0 0726 100 30 0 20 100727 100 30 0 100 100728 0.sup.d 0.sup.d 20.sup.d 0.sup.d 0.sup.d729 100 70 0 100 100730 100 0 0 0 10731 70 50 0 40(20) 50(60)732 100 0 20 0 100733 100 50 0 0 80(100)734 10.sup.c 0 20 0 0735 100 10 0 20 80(100)736 100 0 0 0 90(100)737 100 0 0 0 0738 100 80 0 80 100739 100 20 0 0 0740 30 30 0 0 0741 100 0 0 -- 0742 100 0 0 -- 0743 100 40 0 -- 0744 100 20 0 -- 0745 100 10 0 -- 0746 100 0 0 -- 0747 70 20 0 -- 0748 100.sup.d 100.sup.d 0.sup.d 0.sup.d 0(10).sup.d749 100 0 0 -- 0750 20 30 0 -- 0751 100 0 20 -- 0752 10 20 0 -- 0753 100 20 0 -- 0754 100 70 0 -- 0755 100 10 0 -- 0756 100 0 0 -- --757 100 0 0 -- --758 100 100 0 -- --759 100 10 0 -- --760 100.sup.c 40 20(40) -- --761 0.sup.d 90 0 -- --762 100 40 0 -- --763 100 90 0 -- --764 80 80 0 0 50(90)765 100 10 0 40(100) 100766 100 20 20 0(20) 100767 100 0 0 0 0768 50 10 40 0 0769 100 20 20 0(20) 0770 50 30 20 0(20) 0771 50.sup.c 0 0 0(20) 0772 90 10 0 0(20) 0773 20 40 0 0 0774 100 0 20 20 90775 100 30 0 0 20(30)776 40 0 0 0 0777 60.sup.c 30.sup.a,c 20.sup.c 0 0778 100 10 0 0 0779 90 20 0 0 0780 100 0 0 0 0781 100 80 0 40(100) 100782 40 70 0 0(20) 40783 100 10 0 0 10784 100 30 0 0 0785 100 20 0 40(0) 80(100)786 60 0 0 0 0787 30 30 0 -- --788 70 30 0 -- --789 100 0 0 -- --790 100 90 0 -- --791 20.sup.c 10 0 0 0792 0.sup.d 10.sup.a,c .sup. 0.sup.c 0 0793 20 0 0 -- --794 0.sup.d 10 0 0 0795 100 30 0 -- --796 100 30 0 -- --797 100 0 0 -- --798 100 10 0 -- --799 10.sup.a 0.sup.a 0 0 0800 30.sup.a 30.sup.a 20 0 0801 20.sup.c 10 0 0 0802 100 40 0 80 80(100)803 100 60 0 0 0804 100 30 0 0 0805 100 30 0 -- --806 100 20 0 -- --807 100 0 0 -- --808 100 20 0 -- --809 100 0 0 -- --810 100 50 0 -- --811 50 0 0 -- --812 100 0 60 -- --813 100 0 0 -- --814 100 20 20 -- --815 100 0 0 -- --816 100 0 0 -- --817 100 30 0 -- --818 100 40 0 -- --819 30 10 0 0(20) 0820 100 0.sup.a 0 0(20) 0821 100.sup.a 70 0 0(20) 0822 100.sup.a 100 40(100) 0(100) 100823 100.sup.a 0.sup.a 0 -- --824 0.sup.d 10 0 -- --825 100.sup.a 30 0 -- --826 100.sup.a 0.sup.a 0 -- --827 60 10.sup.a 0 -- --828 0.sup.a 0.sup.a 20 -- --829 100 100 0 20(80) 80(90)830 0 10 0 0 20831 100 0 0 0 0832 100 0 0 0 0833 60 0 0 0 20834 0 0 40 0 0835 100 90 0 60 100836 0 50 0 0 0837 0 0 20 0 0838 0 100 0 0 70839 100 40 0 0 100840 0 0 0 0 0841 0 0 20 0(20) 0842 10 20 0 0(20) 0843 40 50 0 20(60) 50(90)844 0 10 0 0 0845 70 10 0 0(40) 0846 40 0 40 20 0847 0 30 0 20 0848 40 30 20 0(60) 20(80)849 0 10 40 0 0850 10 0 0 0 0851 0 0 0 20 0852 0 0 0 20(40) 0853 0 0 0 0 0854 0 60 0 60 0855 0 90 0 0 0856 100 0 0 0 0857 50 20 20 0(20) 0858 0 10 0 0 0859 0 60 0 60 0860 0 10 0 0 0861 0 10 0 0 0862 0 10 0 0(40) 0863 0 20 0 0 0864 40 0 0 0 0865 100 50 0 0 0(20)866 0 100 0 0 0867 0 100 0 0 0868 10 0 20 0 0869 0 0 0 40 0870 100 10 0 0 80(90)871 0 0 0 0 0872 0 10 20 0 0873 0 20 0 -- --874 100 0 0 -- --875 20 20 0 -- --876 100 20 0 -- --877 80 10 0 -- --878 100 10 0 -- --879 30 30 20 -- --880 100 10 -- -- --881 80 80 40 0 0882 100 0 0 -- --883 90 50 0 0(20) 40(100)884 0 0 0 -- --885 90 30 0 -- --886 100 10 0 -- --887 100 100 0 -- --888 30 100 0 -- --889 100 40 0 -- --890 100 70 0 -- --891 100 20 0 -- --892 100 30 20 -- --893 0 40 0 -- --894 100 0 0 -- --895 100 20 0 -- --896 100 30 0 -- --897 100 0 0 -- --898 100 30 0 -- --899 100 10 0 -- --900 100 0 0 -- --901 100 10 0 -- --902 100 0 0 -- --903 100 30 0 -- --904 100 0 0 -- --905 100 0 0 -- --906 0 10 0 -- --907 100 0 0 -- --908 100 30 40 -- --909 100 30 0 -- --910 100 50 0 -- --911 100 0 0 -- --912 100 10 0 -- --913 100 0 0 -- --914 0 0 0 0 0915 90 10 0 0 0916 0 0 0 0 0917 0 0 20 0 0918 0 0 0 0 0919 100 40 20 0(20) 0920 0 0 0 0 0921 0 90 20 20 0922 0 0 0(40) 0 0923 0 30 0 -- --924 0.sup.a 10.sup.a 0 -- --925 -- -- -- -- --926 0 100 20 0 60(100)927 0 0 0 0 20928 20 30 0 0 20929 0 60 0 0 0(20)930 0 80 0 0 0931 0 100 0 20(20) 20932 100 40 0 40 0(20)933 0 0 -- -- --934 100 100 0 20 0935 0 0 0 -- --936 0 40 0 0 40937 0 10 0 0 40938 0 0 0 0 20939 0 0 0 0 0940 10 10 -- -- --941 0 10 -- -- --942 0 0 -- -- --943 0 0 0 -- --944 0 0 -- -- --945 0 0 0 0 0946 0 20 -- -- --947 0 20 0 -- --948 0 20 -- -- --949 0 10 0 0 20950 0 0 0 0 0951 0 0 0 0 20(40)952 0 20 0 0 0953 0 0 0 -- --954 0 0 20 0 0955 0 0 20 0 20(40)956 40 10 0(20) 0 0957 40 60 0 0 0958 0 0 0 0 0959 0 0 0 0 20960 0 0 0 0 0961 0 100 40 0(20) 0962 -- -- -- -- --963 0 50 0 20 0964 20 100 0 20 0965 0 60 60 20(40) 0966 0.sup.a 0.sup.a 0 -- --967 0.sup.a 0.sup.a 0 -- --968 0 30 0 0 20969 0 -- -- -- --970 0 -- -- -- --971 0 -- -- -- --972 0 -- -- -- --973 0 -- -- -- --974 0 -- -- -- --975 0 -- -- -- --976 10 -- -- -- --977 0 -- -- -- --978 60 -- -- -- --979 100(80) 0(20) 0 -- --980 100 0(30) 0 -- --981 100 0 0 -- --982 100 10(40) 0 -- --983 0(30) 10(20) 0 -- --984 30 10 0 -- --985 0 20 0 -- --986 0 0 0 -- --987 0 0 0 -- --988 0 0 0 -- --989 0 0 0 -- --990 0 30 0 -- --991 0 0 0 -- --992 0 0 0 -- --993 0 0 0 -- --994 0 0 0 -- --995 0 0 0 -- --996 20 20 0 -- --997 0 30 0 -- --998 0 0 0 -- --999 0 0 0 -- --1000 0 0 0 -- --1001 0 10 0 -- --1002 0 0 20 -- --1003 0 10 0 -- --1004 0 0 0 -- --1005 0 -- -- -- --1006 0 -- -- -- --1007 100 0 0 -- --1008 0 20 0 -- --1009 0 30 0 -- --1010 0 20 0 -- --1011 0 0 0 -- --1012 0 0 0 -- --1013 0 40 0 -- --1014 0 0 20 -- --1015 0 10 0 -- --1016 100 0 0 -- --1017 100 40 0 -- --1018 10 0 20 -- --______________________________________ .sup.a 48 hour observation .sup.b Not tested .sup.c Tested at 1200 ppm .sup.d Tested at 2400 ppm
Not all compounds were tested by soil application. The results of the compounds tested are reported.
It should be understood that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention as defined by the appended claims.

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Number	Date	Country
1668893	Oct 1971	DEX
2757584	Aug 1978	DEX
8005	Jul 1970	FRX
1481388	Jul 1977	GBX
1573668	Aug 1980	GBX

	Number	Date	Country
	274635	Nov 1988
	207081	Jun 1988
	024660	Mar 1987
	012380	Feb 1987

	Number	Date
Parent	911177	Sep 1986
Parent	789797	Oct 1985
Parent	858482	May 1986
Parent	005824	Feb 1987
Parent	835073	Feb 1986
Parent	821187	Jan 1986
Parent	885508	Jul 1986

Insecticidal N' substituted-N-N'-disubstituted-hydrazines

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CPC

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US Referenced Citations (46)

Foreign Referenced Citations (5)

Non-Patent Literature Citations (55)

Related Publications (4)

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Entry
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Chemical Abstracts, 95:132148a (1981).
Chemical Abstracts, 85:142768k (1976).
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