Oxime derivative and fungicide for agricultural and horticultural use

BACKGROUND OF THE INVENTION
This invention relates to a novel oxime derivative and a fungicide for agricultural and horticultural use containing said derivative as an active ingredient.
Disease damage caused by plant pathogenic fungi belonging to the class phycomycetes including downy mildew and phytophthora rot is one of serious problems in agricultural production. The specific physiological and morphological properties of these fungi make it difficult to prevent the disease damage caused thereby. Thus it has been urgently required to develop an effective fungicide. Downy mildew and phytophthora rot seriously damage various crops.
Known fungicides which are widely used at present against the disease damage caused by plant pathogenic fungi belonging to the class phycomycetes include captan (common name), captafol (common name), dithiocarbamate fungicides such as zineb and chlorotalonil (common name). However these fungicides mostly exert not therapeutic but preventive effects. Thus they have a serious disadvantage that no satisfactory effect can be achieved when they are used after the occurrence of the disease damage. On the other hand, fungicides comprising acylalanine compounds such as metharaxyl (common name), which have been recently developed and put into practical use, exert both of preventive and therapeutic effects. However strains resistant thereto have already appeared, which considerably lowers the effects of these fungicides.
Prior arts comprising a compound whose structure is somewhat similar to that of the compound of the present invention include European Patent Laid-Open No. 0268892 which has been filed by the present inventors.
The present invention aims at providing a fungicide which simultaneously exerts both of preventive and therapeutic effects on disease caused by plant pathogenic fungi belonging to the class Phycomycetes without giving any chemical damage to useful crops. There has been urgently required to develop such an excellent fungicide as described above.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a novel oxime derivative.
It is another object of the present invention to provide a fungicide containing said oxime derivative as an active ingredient.
Further, it is another object of the present invention to provide a fungicide which exerts both of preventive and therapeutic effects on disease caused by plant pathogenic fungi belonging to the class Pycomycetes without giving any chemical damage to useful crops.
It is still another object of the present invention to provide an intermediate for the preparation of the abovementioned fungicide.
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have conducted extensive studies in order to overcome the above problems. As a result, they have found that compounds represented by the following general formula [1] simultaneously exert both of preventative and therapeutic effects on phytophthora rot and downy mildew of various plants while causing little chemical damage to crops, thus completing the present invention.
The compound of the present invention, which is an active ingredient of a fungicide for agricultural and horticultural use, is a novel one which has never been found in any report so far.
Compared with compounds described in the European Patent Laid-Open No. 0268892, which has been filed by the present inventors, the compound of the present invention is highly advantageous in that the chemical damage to crops is further lowered.
Accordingly, the present invention relates to an oxime derivative represented by the following general formula [1]: ##STR2## wherein A represents an optionally substituted aryl group or an optionally substituted heterocyclic group, B represents an optionally substituted phenyl group, an optionally substituted furyl group, an optionally substituted thienyl group, an optionally substituted pyrazolyl group, an alkenyl group having 2 to 10 carbon atoms, a halogenated alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms or an alkylthio group having 1 to 10 carbon atoms, Y represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an optionally substituted phenyl group, an alkylcarbonyl group, an optionally substituted phenylcarbonyl group, an optionally substituted heterocyclic carbonyl group, an alkylaminocarbonyl group, an optionally substituted phenylaminocarbonyl group, an optionally substituted heterocyclic aminocarbonyl group, an alkylaminothiocarbonyl group or an alkoxycarbonyl group, W represents a hydrogen atom, a halogen atom, an amino group, an alkylamino group, an optionally substituted phenylamino group, an optionally substituted heterocyclic amino group, an alkylsulfonyl group, an optionally substituted phenylsulfonyl group or a dialkylaminosulfonyl group, an optically active isomer thereof and a fungicide for agricultural and horticultural use containing one or more of these compounds as active ingredients(s).
Particular examples of the group A in the above general formula [1] are as follows. ##STR3##
In the above definition of the group A, the substituents R.sup.1 and R.sup.2 independently represent each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylsulfoxide group having 1 to 6 carbon atoms, an alkylsulfone group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, an alkoxyalkylcarbonyl group having 3 to 6 carbon atoms, an N,N-dialkylaminocarbonyl group having 3 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkoxycarbonylalkyl group having 3 to 6 carbon atoms, a cyanoalkyl group having 2 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, an alkylamino group having 1 to 6 carbon atoms, a phenyl group optionally substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an optionally substituted cycloalkyl group having 3 to 10 carbon atoms, an optionally substituted cycloalkylalkyl group having 4 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an optionally substituted epoxy having 2 to 10 carbon atoms, an optionally substituted oxetyl having 3 to 10 carbon atoms, an optionally substituted tetrahydrofuryl having 4 to 10 carbon atoms, an optionally substituted tetrahydrothienyl having 4 to 10 carbon atoms, an optionally substituted epoxyalkyl group having 3 to 10 carbon atoms, an optionally substituted oxetylalkyl group having 4 to 10 carbon atoms, an optionally substituted tetrahydrofurylalkyl group having 5 to 10 carbon atoms or an optionally substituted 1,3-dioxolylalkyl group having 4 to 10 carbon atoms.
The compounds of the present invention represented by the general formula [I] may be present in the form of syn-anti isomers. The present invention involves these isomers.
Among the compounds of the present invention represented by the general formula [I], those satisfying the following requirements are particularly preferable from the viewpoints of, for example, effects. Namely, A represents an optionally substituted pyrazolyl group, an optionally substituted pyridyl group, an optionally substituted phenyl group, an optionally substituted thiazolyl group or an optionally substituted oxazolyl group; B represents an optionally substituted furyl group, an optionally substituted thienyl group, an optionally substituted pyrazolyl group, an alkenyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; Y represents a hydrogen atom, an alkyl group, an alkenyl group, an optionally substituted phenylcarbonyl group, an alkylaminocarbonyl group, a phenylaminocarbonyl group, an alkylaminothiocarbonyl group or an alkoxycarbonyl group; and W represents a hydrogen atom, a halogen atom, an amino group or an alkyl amino group.
Particularly preferable compounds are those represented by the general formula [I] wherein A is an optionally substituted pyrazolyl group; B is an optionally substituted furyl group, an optionally substituted thienyl group or an alkenyl group having 2 to 10 carbon atoms; Y is a hydrogen atom; and W is a hydrogen atom, a halogen atom, an amino group or an alkylamino group.
Particular examples of these preferable compounds are those having the following numbers in Tables 1 to 4 which will be given hereinafter. Compound No.: 13, 25, 26, 27, 100, 101, 104, 156, 157, 158, 159, 173, 175, 176, 179, 180, 181, 182, 306, 311, 316, 317, 321, 343, 439, 448, 1007, 1013, 1023, 1024, 1028, 1033, 1034, 1035, 1037, 1038, 1039, 1040, 1042, 1043 and 1539. More particularly, the following compounds may be cited. ##STR4##
Now processes for the preparation of the compounds of the present invention will be described by referring to the reaction schemes. ##STR5## In the above reaction scheme, A and B are as defined above, R.sup.3 represents an alkyl group having 1 to 4 carbon atoms, Z represents a hydrogen atom or an alkali metal such as lithium, sodium or potassium, and X represents a halogen atom.
DESCRIPTION OF PROCESS 1
In the first step, an aminoacetonitrile derivative [5] may be synthesized by two methods.
In the process a-1, the aimed compound is obtained through Strecker's reaction. Namely, an aldehyde [3], which is the starting material, is reacted with aqueous ammonia and/or ammonium chloride and an alkali cyanide such as sodium or potassium cyanide in a binary solvent system comprising an ether such as ethyl ether or tetrahydrofuran or an aromatic hydrocarbon such as benzene or toluene and water. The reaction may be preferably carried out at 0.degree. to 100 .degree. C.
In the process a-2, the starting aldehyde [3] is reacted with trialkylsilylnitrile such as trimethylsilylnitrile in the presence of, if required, a catalytic amount of a Lewis acid such as zinc iodide to thereby give an intermediate [4]. Next, the compound [4] is reacted with ammonia dissolved in a solvent such as methanol or ethanol. thus the aimed aminoacetonitrile derivative [5] is obtained.
The obtained aminoacetonitrile derivative [5] may be purified and isolated by, for example, forming a salt together with a hydrogen halide such as hydrogen chloride in an ether solvent such as diethyl ether.
In the second step, the aminoacetonitrile derivative [5] obtained in the first step is reacted with an acid halide represented by the general formula [6] in the presence of an acid acceptor.
Examples of the acid acceptor include organic bases such as triethylamine, dimethylaniline and pyridine and inorganic bases such as ammonia, potassium carbonate, sodium carbonate, ammonium hydrogencarbonate, sodium hydroxide and ammonium carbonate.
This reaction may be preferably conducted in the presence of a solvent. Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran and diisopropyl ether, esters such as methyl acetate and ethyl acetate, halogenated hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethane, and acetonitrile. It is desirable to conduct this reaction, which is an exothermic one, under cooling, i.e., at a temperature of -30.degree. to 50 .degree. C., still preferably -20.degree. to 30 .degree. C. Thus the aimed amide-substituted acetonitrile derivative can be obtained.
DESCRIPTION OF PROCESS 2
In this process, a carboxylic acid derivative [8], which is a starting material, is dehydrated and condensed with the aminoacetonitrile derivative [5] obtained in Process 1 in the presence of a dehydrating agent to thereby give an amide-substituted acetonitrile derivative.
Preferable examples of the dehydrating agent include carbodiimides such as dicyclohexylcarbodiimide (DCC) and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and inorganic ones such as silicon tetrachloride.
DESCRIPTION OF PROCESS 3
It is preferable that an amide derivative [9] is reacted with a glyoxylate in an ester solvent such as ethyl acetate or isobutyl acetate or acetone under heating to 50.degree. to 100 .degree. C.
The resulting hydroxycompound [11] is reacted with an excessive amount of thionyl chloride below or around room temperature to thereby give a chlorinated compound. After the completion of the reaction, the excessive thionyl chloride is distilled off and the residue is reacted with a compound represented by the general formula BZ [12] in a solvent in the presence of, if required, a base. Thus an ester [13] is obtained.
Examples of the solvent to be used above include esters such as ethyl acetate and isobutyl acetate, ethers and acetonitrile. Examples of the base include organic bases such as triethylamine and pyridine and inorganic ones such as sodium carbonate and ammonium carbonate.
Next, the ester [13] is reacted with ammonia to thereby give an amide. This reaction may be preferably conducted in a solvent such as an alcohol, e.g., methanol or ethanol or an ether, e.g., diethyl ether or tetrahydrofuran at -50 .degree. C. to room temperature. The amide may be further reacted in an organic amine such as pyridine by using a dehydrating agent such as absolute trifluoroacetic acid, in an amide solvent such as N,N-dimethylformamide (DMF) by using a dehydrating agent such as phosphorus oxychloride or by using a dehydrating agent such as polyphosphoric acid (PPA), a polyphosphoric acid alkyl ester (PPE) or a polyphosphoric acid alkylsilyl ester (PPSE) to thereby give an amide derivative 7.
DESCRIPTION OF PROCESS 4
An acylaminoacetonitrile derivative [14] may be readily obtained by reacting aminoacetonitrile with an acid chloride [6] under condensation conditions commonly used in the art. It is generally preferable to use a base in this reaction. Examples of the base include inorganic bases such as sodium carbonate and ammonium carbonate and organic ones such as triethylamine and pyridine.
The acylaminoacetonitrile derivative [14] may be converted into a halide [15] by using a halogenating agent. Preferable examples of the halogenating agent include chlorine, bromine, N-chlorosuccinimide and N-bromosuccinimide. Since this halogenated intermediate is unstable to heat, it is neither isolated nor purified but subjected to the subsequent step as such. After the completion of the halogenation, namely, the halogenated intermediate [15] is reacted with BZ [12] in a solvent in the presence of, if required, a base to thereby give an amide derivative [7].
This reaction may be conducted under the same conditions as those described in Process 3. ##STR6## In the above reaction scheme, A, B, W, X, Y and Z are as defined above, Y.sup.1 represents an alkyl, an alkenyl, an alkynyl, an optionally substituted phenyl, an optionally substituted heterocyclic or an alkoxycarbonyl group, and W.sup.1 and W.sup.2 independently represent each an alkyl, an alkenyl, an alkynyl, an optionally substituted phenyl or an optionally substituted heterocyclic group.
DESCRIPTION OF PROCESS 5
(a) An aminoacetamidoxime derivative or an inorganic or organic acid salt thereof [2] can be readily obtained by reacting the aminoacetonitrile derivative [5] obtained in Process 1 with hydroxylamine or an inorganic or organic acid salt thereof in a solvent such as methanol or ethanol. It is preferable to conduct this reaction at 0 .degree. C. to room temperature. The reaction is completed within 2 to 10 hours.
(b) When the aminoacetamidoxime derivative obtained in the above step (a) is an inorganic or organic acid salt, it may be neutralized with a base such as triethylamine or sodium methoxide and then reacted with an acid chloride [6] in the presence of a base such as triethylamine or pyridine. thus the aimed acetamidoxime derivative [1--1] of the present invention can be obtained. Preferable examples of the solvent to be used in the above reaction include nitriles such as acetonitrile, ethers such as tetrahydrofuran and halogenated hydrocarbons such as chloroform.
The reaction may be preferably conducted at -20 .degree. C. to room temperature. The reaction is completed within 2 to 5 hours.
DESCRIPTION OF PROCESS 6
The aimed acetamidoxime derivative [1--1] of the present invention may be readily obtained by reacting the amide-substituted acetonitrile derivative [7] obtained by the above Processes 1 to 4 with hydroxylamine.
In the above reaction, a solvent such as methanol or ethanol is used. The reaction may be preferably conducted at the reflux temperature of the employed solvent. The reaction is completed within 2 to 10 hours.
In addition to the above reactions, processes which are generally known for the preparation of amidoxime derivatives, e.g., the following reactions (1) to (3) may be employed in the present invention. ##STR7## wherein E and G represent each an organic group.
In the above reaction (1), an iminoether or a thioamide is reacted with hydroxylamine. In the above reaction (2), a hydroxyimino acid chloride or a hydroxyimino ether is reacted with ammonia. In the reaction (3), a nitroso oxime is reduced with hydrogen sulfide.
DESCRIPTION OF PROCESS 7
(a) The aimed oxime derivative [1-2] may be obtained by reacting the oxime derivative [1--1] with a halide [16] in the presence of a base. Preferable examples of the base include alcholate such as sodium methoxide and potassium tertbutoxide and metal hydrides such as sodium hydride and potassium hydride.
(b) The aimed oxime derivative [1-3] may be obtained by reacting the oxime derivative [1--1] with a carboxylic acid halide [17] in the presence of a base. Preferable examples of the base include organic bases such as triethylamine and pyridine and inorganic ones such as sodium carbonate and ammonium carbonate.
DESCRIPTION OF PROCESS 8
(a) The aimed oxime derivative [1-4] may be obtained by reacting the oxime derivative [1--1] with an isocyanate.
(b) The aimed oxime derivative [1-5] may be obtained by reacting the oxime derivative [1--1] with a thioisocyanate [19].
DESCRIPTION OF PROCESS 9
(a) The aimed halide [1-6] may be obtained by reacting the amidoxime derivative [1--1] with sodium nitrite in a mineral acid amidoxime derivative [1--1] with sodium nitrite in a mineral acid to thereby form a diazonium salt and then neutralizing the obtained diazonium salt with a base such as sodium hydrogencarbonate to a pH value of 3 to 4.
As the mineral acid, hydrofluoric, hydrochloric, hydrobromic or hydriodic acid may be selected to thereby give the corresponding halide.
(b) The diazonium salt obtained in the above step (a) is treated with hypophosphorous acid to thereby give a hydride (oxime derivative) [1-7].
DESCRIPTION OF PROCESS 10
(a) The halide [1-6] obtained in the above Process 9-(a) is reacted with an amine (21), preferably in the presence of a base, to thereby give the aimed oxime derivative [1-8]).
(b) The halide [1-6) obtained in the above Process 9-(a) is reacted with a sulfinic acid metal salt [22] to thereby give the aimed oxime derivative [1-9].

To further illustrate the present invention, and not by way of limitation, the following Examples will be given.
EXAMPLE 1 ##STR8##
To 10 g of 3-furylaldehyde and 11 g of trimethylsilyl cyanide was added a catalytic amount (50 mg) of zinc iodide under ice-cooling. The obtained mixture was stirred at room temperature for one hour. Next, 80 ml of ammonia-saturated methanol was added thereto and the mixture was stirred at 40 .degree. C. for two hours. The reaction mixture was concentrated, extracted with ethyl acetate and then dried. After distilling off the solvent, 11.6 g of .alpha.-(3-furyl)aminoacetonitrile was obtained.
2.3 g of the .alpha.-(3-furyl)aminoacetonitrile and 4.1 g of triethylamine were dissolved in 100 ml of THF. Then 3.6 g of nicotinic acid chloride hydrochloride was added thereto under ice-cooling. The obtained mixture was stirred for one hour and then at room temperature for six hours. After filtering the solid matter thus formed, the solvent was distilled off. The obtained oily substance was purified by column chromatography to thereby give 2.7 g of .alpha.-(nicotinylamino)-(3-furyl) acetonitrile in the form of crystals.
m.p.: 80.degree.-82.degree. C.
Next, 1.4 g of hydroxylamine hydrochloride was neutralized in 30 ml of methanol with 1.2 g of sodium methoxide. Subsequently 4.6 g of the .alpha.-(nicotinylamino)-(3-furyl)-acetonitrile was added thereto followed by stirring.
After 15 minutes, the mixture was heated under reflux for two hours.
After the completion of the reaction, the solid matter thus formed was filtered and the solvent was distilled off. The resulting solid substance was purified by column chromatography and recrystallized from a solvent mixture of ethyl acetate with diethyl ether. Thus 4.2 g of the aimed N-(3-pyridylcarbonyl).alpha.-(3-furyl)acetamidoxime was obtained in the form of crystals.
EXAMPLE 2 ##STR9##
To 7.7 g of ammonium chloride and 4.9 g of potassium cyanide was added 80 ml of aqueous ammonia under ice-cooling. After stirring, 8.0 g of 2-thienylaldehyde dissolved in 80 ml of diethyl ether was added thereto and the obtained mixture was stirred at room temperature for 20 hours.
After the completion of the reaction, the diethyl ether phase was recovered while the aqueous phase was extracted with diethyl ether thrice. These diethyl ether phases were combined, dehydrated and dried. Then the solvent was distilled off to thereby give 7.8 g of .alpha.-(2-thienyl)aminoacetonitrile.
5.6 g of the .alpha.-(2-thienyl)aminoacetonitrile thus obtained was dissolved in 30 ml of methanol and 2.8 g of hydroxylamine hydrochloride was added thereto in a water bath. After stirring for a while, the mixture began to crystallize while showing slight heat generation. The mixture was stirred at room temperature for several hours thereafter. After the completion of the reaction, the reaction mixture was concentrated and the solvent was distilled off. After recrystallizing from ethanol, 7.6 g of the aimed .alpha.-(2-thienyl)aminoacetamidoxime hydrochloride was obtained.
The following Table 1 shows physical data of novel amidoxime derivatives each obtained in a manner similar to the one described in Example 2.
TABLE 1______________________________________Compounds represented by the general formula: ##STR10## .sup.1 H-NMR (reference material: TMS) (solvent:Ex. B m.p. (.degree.C.) DMSO d-6 + CDCI.sub.3) 8 ppm______________________________________ ##STR11## 225.about.230 (decomp.) 5.32(s, 1H), 6.95.about.7.17(m, 1H), 7.30.about.7.75(m, 2H), 8.17(brs, 2H), 8.85(brs, 2H)3 ##STR12## 173.about.175 (decomp.) 5.05(s, 1H), 5.90(brs, 2H), 6.40.about.6.60(m, 1H), 6.60.about.6.80(m, 1H), 7.65.about.7.80(m, 1H), 9.15(brs, 2H)4 ##STR13## 186.about.188 (decomp.) 5.00(s, 1H), 5.88(brs, 2H), 7.27.about.7.90(m, 3H), 8.85(brs, 2H)5 ##STR14## 185.about.187 (decomp.) 4.90(s, 1H), 5.85(brs, 2H), 6.68.about.6.85(m, 1H), 7.60.about.7.75(m, 1H), 7.80.about.7.95(m, 1H), 8.50(brs, 2H)______________________________________
EXAMPLE 6 ##STR15##
A mixture comprising 2.1 g of ethyl 3-methyl-1H-pyrazole-5-carboxylate, 2.1 g of cyclobutyl methanesulfonate and 2.6 g of tri-n-butylamine was allowed to react at 110 .degree. C. for three hours without using any solvent. Then the reaction mixture was allowed to cool and diethyl ether was added thereto. The obtained mixture was successively washed with 1 N hydrochloric acid, an aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of common salt and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the obtained residue was purified by column chromatography (eluent: hexane : ethyl acetate=14 : 1). Thus 0.5 g of the aimed ethyl 1-cyclobutyl-3-methyl-1H-pyrazole-5-carboxylate (compound No. 1001) (yield: 17.6 %) and 1.54 g of ethyl 1-cyclopropylmethyl-3-methyl-1H-pyrazole-5-carboxylate(yield: 54.3 %) were obtained.
EXAMPLE 7 ##STR16##
A mixture comprising 3.8 g of ethyl 3-methyl-1H-pyrazole-5-carboxylate, 3.8 g of cyclopropylmethyl methanesulfonate and 4.6 g of tri-n-butylamine was allowed to react at 110 .degree. C. for three hours without using any solvent. Then the reaction mixture was allowed to cool and diethyl ether was added thereto. The obtained mixture was successively washed with 1 N hydrochloric acid, an aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of common salt and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the obtained residue was purified by column chromatography (eluent: hexane:ethyl acetate=14 : 1). Thus 0.62 g of the aimed ethyl 1-cyclobutyl-3-methyl-1H-pyrazole-5-carboxylate (compound No. 1001) (yield: 12.1 %) and 2.45 g of ethyl 1-cyclopropylmethyl-3-methyl-1H-pyrazole-5-carboxylate (yield: 54.3 %) were obtained.
EXAMPLE 8 ##STR17##
6.0 g of ethyl 1-cyclobutyl-3-methyl-1H-pyrazole-5-carboxylate was added to a mixture of 60 ml of a 1 N aqueous solution of potassium hydroxide with 80 ml of ethanol.
The mixture was allowed to react at room temperature for two hours. Then the ethanol was distilled off under reduced pressure and ethyl acetate was added to the residue. The pH value of the mixture was adjusted to 1.0 with 1 N hydrochloride and the organic phase was recovered, washed with a saturated aqueous solution of common salt and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and thus 4.78 g of 1-cyclobutyl-3-methyl-1H-pyrazole-5-carboxylic acid was obtained in the form of white crystals (yield: 91.6 %).
EXAMPLE 9 ##STR18##
To 3.02 g of 1-cyclobutyl-3-methyl-1H-pyrazole-5-carboxylic acid were added 60 ml of benzene and 10 ml of thionyl chloride. The mixture was refluxed for two hours. Then the solvent was distilled off under reduced pressure and thus 3.2 g of 1-cyclobutyl-3-methyl-1H-pyrazole-5-carboxylic acid chloride was obtained (yield: 96.1%).
The following Table 2 shows the physical properties of the compounds No. 1001 to 1003.
TABLE 2______________________________________.sup.1 H-NMR data and m.p.Cpd. No. Solvent .sup.1 H-NMR 8ppm (reference: TMS) m.p.______________________________________ (.degree.C.)1001 CDCl.sub.3 1.32(t, 3H, J=7.2H.sub.z), 1.53.about.2.18(m, 2H), 2.25(s, 3H), 2.18.about.3.04(m, 4H), oil 4.25(q, 2H, J=7.2H.sub.z), 5.53 (quint, 1H, J=8.4H.sub.z), 6.48(s, 1H)1002 CDCl.sub.3 1.47.about.2.16(m, 2H), 2.30(s, 3H), 2.16.about.3.07(m, 4H), 150.about.151 5.58 (quint, 1H, J=8.4H.sub.z), 6.62(s, 1H), 12.37(s, 1H)1003 CDCl.sub.3 1.47.about.2.11(m, 2H), 2.26(s, 3H), 2.11.about.3.01(m, 4H), oil 5.21(quint, 1H, J=7.8H.sub.z), 6.74(s, 1H)______________________________________
EXAMPLE 10 ##STR19##
6.3 g (0.03 mol) of the .alpha.-(2-thienyl)aminoacetamidoxime hydrochloride obtained in Example 2 was neutralized in 80 ml of acetonitrile with 6.7 g (0.066 mol) of triethylamine. Then the solution was ice-cooled and 6.0 g (0.03 mol) of 1-cyclobutyl-3-methyl-1H-pyrazole-5-carboxylic acid chloride was added thereto dropwise. After stirring under ice-cooling for two hours, the mixture was further stirred at room temperature for three hours.
After the completion of the reaction, the reaction mixture was concentrated and the residue was dispersed in a solution comprising water and chloroform. After concentrating the chloroform phase, crude crystals were obtained. These crude crystals were recrystallized from a solvent mixture of ethanol with diethyl ether. Thus 7.5 g of the aimed .alpha.-(1-cyclobutyl-3-methyl-pyrazole-5-yl-carboxylamino)-(2-thienyl)acetamidoxime was obtained in the form of crystals.
EXAMPLE 11 ##STR20##
6.3 g (0.03 mol) of the .alpha.-(2-thienyl)aminoacetamidoxime hydrochloride obtained in Example 2 was neutralized in 80 ml of acetonitrile with 6.7 g (0.066 mol) of triethylamine. Then the solution was ice-cooled and 4.8 g (0.03 mol) of 1,3-dimethyl-(1H)-pyrazole-5-carboxylic acid chloride was added thereto dropwise. After stirring under ice-cooling for two hours, the mixture was further stirred at room temperature for three hours.
After the completion of the reaction, the reaction mixture was concentrated and the residue was dispersed in a solution comprising water and chloroform. After concentrating the chloroform phase, crude crystals were obtained. These crude crystals were recrystallized from a solvent mixture of ethanol with diethyl ether.
Thus 6.5 g of the aimed .alpha.-(1,3-dimethyl-pyrazole-5-yl-carboxylamino)-(2-thienyl)acetamidoxime was obtained in the form of crystals.
EXAMPLE 12 ##STR21##
5.86 g (0.02 mol) of the .alpha.-(1,3-dimethyl-pyrazole-5-yl-carbonylamino)-(2-thienyl)acetamidoxime obtained in Example 11 was added to 70 ml of 4 N hydrochloric acid under ice-cooling and stirred. Then 1.66 g (0.024 mol) of sodium nitrite dissolved in 10 ml of water was added thereto dropwise.
The obtained mixture was stirred for additional three hours under ice-cooling.
Next, sodium hydrogencarbonate was slowly added thereto to thereby adjust the pH value of the mixture to 3 to 4. Thus the mixture crystallized.
The obtained crystals were filtered, washed with water and dried.
The crystals were purified by column chromatography to thereby give 3.44 g of the aimed .alpha.-(1,3-dimethylpyrazole-5-yl-carbonylamino)-(2-thienyl)-8-chloroacetoxime.
The following Tables 3 and 4 show the compounds of the present invention each synthesized in a manner similar to the one described above. In Tables 3 and 4, n represents normal, i represents iso, t represents tertiary and p represents para.
TABLE 3______________________________________In a compound represented by the general formula: ##STR22##Com-poundNo.A R.sup.1 R.sup.2 B Y______________________________________1 A1 H H B1 H2 A1 H H B2 H3 A1 H H B3 H4 A1 H H B4 H5 A1 H H B5 H6 A1 H H B6 H7 A1 3-F H B3 H8 A1 4-Cl H B3 H9 A1 2-Cl 4-Cl B3 H10 A1 3-Cl H B3 H11 A1 3-Cl 5-Cl B1 H12 A1 3-Cl 5-Cl B2 H13 A1 3-Cl 5-Cl B3 H14 A1 3-Cl 5-Cl B4 H15 A1 3-Cl 5-Cl B5 H16 A1 3-Cl 5-Cl B6 H17 A1 3-Cl 5-Cl CHC(CH.sub.3).sub.2 H18 A1 3-Cl 5-Cl CHCClCH.sub.3 H19 A1 3-Cl 5-Cl OCH.sub.2 CH.sub.3 H20 A1 3-Cl 5-Cl SCH.sub.2 CH.sub.3 H21 A1 3-Cl 5-Cl OCH(CH.sub.3).sub.2 H22 A1 3-Cl 5-Cl CH.sub. 2 CHCH.sub.2 H23 A1 3-Cl 5-Cl CH.sub.2 CCH H24 A1 3-Cl 5-Cl O-Q1 H25 A2 H H B1 H26 A2 H H B2 H27 A2 H H B3 H28 A2 H H B4 H29 A2 H H B5 H30 A2 H H B6 H31 A2 H H CHC(CH.sub.3).sub.2 H32 A2 H H CHCClCH.sub.3 H33 A2 H H OCH.sub.2 CH.sub.3 H34 A2 H H SCH.sub.2 CH.sub.3 H35 A2 H H OCH(CH.sub.3).sub.2 H36 A2 H H CH.sub.2 CHCH.sub.2 H37 A2 H H CH.sub.2 CCH H38 A2 H H O-Q1 H39 A2 5-Br H B3 H40 A3 H H B3 H41 A3 4-CH.sub.3 H B3 H42 A3 5-CH.sub.3 H B3 H43 A4 H H B1 H44 A4 H H B2 H45 A4 H H B3 H46 A4 H H B4 H47 A4 H H B5 H48 A4 H H B6 H49 A4 H H CHC(CH.sub.3).sub.2 H50 A4 H H CHCClCH.sub.3 H51 A4 H H OCH.sub.2 CH.sub.3 H52 A4 H H SCH.sub.2 CH.sub.3 H53 A4 H H O-Q1 H54 A4 2-CH.sub.3 5-CH.sub.3 B3 H55 A5 H H B3 H56 A5 H H B5 H57 A6 H H B3 H58 A6 4-CH.sub.3 H B3 H59 A6 CH.sub.3 H B5 H60 A7 CH.sub.3 H B3 H61 A7 CH.sub.3 H B5 H62 A8 CH.sub.3 H B3 H63 A8 CH.sub.3 H B5 H64 A8 CH.sub.3 H B3 H65 A8 CH.sub.3 H B5 H66 A9 CH.sub.3 H B1 H67 A9 CH.sub.3 H B2 H68 A9 CH.sub.3 H B3 H69 A9 CH.sub.3 H B4 H70 A9 CH.sub.3 H B5 H71 A9 CH.sub.3 H B6 H72 A9 CH.sub.3 H CHC(CH.sub.3).sub.2 H73 A9 CH.sub.3 H CHCClCH.sub.3 H74 A9 CH.sub.3 H OCH.sub.2 CH.sub. 3 H75 A9 CH.sub.3 H SCH.sub.2 CH.sub.3 H76 A9 CH.sub.3 H OCH(CH.sub.3).sub.2 H77 A9 CH.sub.3 H CH.sub.2 CHCH.sub.2 H78 A9 CH.sub.3 H CH.sub.2 CCH H79 A9 CH.sub.3 H O-Q1 H80 A9 C.sub.2 H.sub.5 H B1 H81 A9 C.sub.2 H.sub.5 H B2 H82 A9 C.sub.2 H.sub.5 H B3 H83 A9 C.sub.2 H.sub.5 H B4 H84 A9 C.sub.2 H.sub.5 H B5 H85 A9 C.sub.2 H.sub.5 H B6 H86 A9 C.sub.3 H.sub.7 -i H B1 H87 A9 C.sub.3 H.sub.7 -i H B2 H88 A9 C.sub.3 H.sub.7 -i H B3 H89 A9 C.sub.3 H.sub.7 -i H B4 H90 A9 C.sub.3 H.sub.7 -i H B5 H91 A9 C.sub.3 H.sub.7 -i H B6 H92 A9 C.sub.4 H.sub.9 -t H B1 H93 A9 C.sub.4 H.sub.9 -t H B2 H94 A9 C.sub.4 H.sub.9 -t H B3 H95 A9 C.sub.4 H.sub.9 -t H B4 H96 A9 C.sub.4 H.sub.9 -t H B5 H97 A9 C.sub.4 H.sub.9 -t H B6 H98 A9 CH.sub.3 CH.sub.3 B1 H99 A9 CH.sub.3 CH.sub.3 B2 H100 A9 CH.sub.3 CH.sub.3 B3 H101 A9 CH.sub.3 CH.sub.3 B4 H102 A9 CH.sub.3 CH.sub.3 B5 H103 A9 CH.sub.3 CH.sub.3 B6 H104 A9 CH.sub.3 CH.sub.3 CHC(CH.sub.3).sub.2 H105 A9 CH.sub.3 CH.sub.3 CHCClCH.sub.3 H106 A9 CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.3 H107 A9 CH.sub.3 CH.sub.3 SCH.sub.2 CH.sub.3 H108 A9 CH.sub.3 CH.sub.3 OCH(CH.sub.3).sub.2 H109 A9 CH.sub.3 CH.sub.3 CH.sub.2 CHCH.sub.2 H110 A9 CH.sub.3 CH.sub.3 CH.sub.2 CCH H111 A9 CH.sub.3 CH.sub.3 O-Q1 H112 A9 CH.sub.3 C.sub.2 H.sub.5 B1 H113 A9 CH.sub.3 C.sub.2 H.sub.5 B2 H114 A9 CH.sub.3 C.sub.2 H.sub.5 B3 H115 A9 CH.sub.3 C.sub.2 H.sub.5 B4 H116 A9 CH.sub.3 C.sub.2 H.sub.5 B5 H117 A9 CH.sub.3 C.sub.2 H.sub.5 B6 H118 A9 CH.sub.3 C.sub.3 H.sub.7 -i B1 H119 A9 CH.sub.3 C.sub.3 H.sub.7 -i B2 H120 A9 CH.sub.3 C.sub.3 H.sub.7 -i B3 H121 A9 CH.sub.3 C.sub.3 H.sub.7 -i B4 H122 A9 CH.sub.3 C.sub.3 H.sub.7 -i B5 H123 A9 CH.sub.3 C.sub.3 H.sub.7 -i B6 H124 A9 CH.sub.3 C.sub.4 H.sub.9 -t B1 H125 A9 CH.sub.3 C.sub.4 H.sub.9 -t B2 H126 A9 CH.sub.3 C.sub.4 H.sub.9 -t B3 H127 A9 CH.sub.3 C.sub.4 H.sub.9 -t B4 H128 A9 CH.sub.3 C.sub.4 H.sub.9 -t B5 H129 A9 CH.sub.3 C.sub.4 H.sub.9 -t B6 H130 A9 CH.sub.3 H B1 CH.sub.3131 A9 CH.sub.3 H B2 CH.sub.3132 A9 CH.sub.3 H B3 CH.sub.3133 A9 CH.sub.3 H B4 CH.sub.3134 A9 CH.sub.3 H B5 CH.sub.3135 A9 CH.sub.3 H B6 CH.sub.3136 A9 CH.sub.3 H B3 Q4137 A9 CH.sub.3 H B3 Q55138 A9 C.sub.2 H.sub.5 CH.sub.3 B1 H139 A9 C.sub.2 H.sub.5 CH.sub.3 B2 H140 A9 C.sub.2 H.sub.5 CH.sub.3 B3 H141 A9 C.sub.2 H.sub.5 CH.sub.3 B4 H142 A9 C.sub.2 H.sub.5 CH.sub.3 B5 H143 A9 C.sub.2 H.sub.5 CH.sub.3 B6 H144 A9 C.sub.3 H.sub.7 -i CH.sub.3 B1 H145 A9 C.sub.3 H.sub.7 -i CH.sub.3 B2 H146 A9 C.sub.3 H.sub.7 -i CH.sub.3 B3 H147 A9 C.sub.3 H.sub.7 -i CH.sub.3 B4 H148 A9 C.sub.3 H.sub.7 -i CH.sub.3 B5 H149 A9 C.sub.3 H.sub.7 -i CH.sub.3 B6 H150 A10 CH.sub.3 H B1 H151 A10 CH.sub.3 H B2 H152 A10 CH.sub.3 H B3 H153 A10 CH.sub.3 H B4 H154 A10 CH.sub.3 H B5 H155 A10 CH.sub.3 H B6 H156 A10 CH.sub.3 CH.sub.3 B1 H157 A10 CH.sub.3 CH.sub.3 B2 H158 A10 CH.sub.3 CH.sub.3 B3 H159 A10 CH.sub.3 CH.sub.3 B4 H160 A10 CH.sub.3 CH.sub.3 B5 H161 A10 CH.sub.3 CH.sub.3 B6 H162 A10 CH.sub.3 CH.sub.3 CHC(CH.sub.3).sub.2 H163 A10 CH.sub.3 CH.sub.3 CHCClCH.sub.3 H164 A10 CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.3 H165 A10 CH.sub.3 CH.sub.3 SCH.sub.2 CH.sub.3 H166 A10 CH.sub.3 CH.sub.3 OCH(CH.sub.3).sub.2 H167 A10 CH.sub.3 CH.sub.3 CH.sub.2 CHCH.sub.2 H168 A10 CH.sub.3 CH.sub.3 CH.sub.2 CCH H169 A10 CH.sub.3 CH.sub.3 B3 CH.sub.3170 A10 CH.sub.3 CH.sub.3 B3 CH.sub.3171 A10 CH.sub.3 CH.sub.3 B3 Q4172 A10 CH.sub.3 CH.sub.3 B3 Q55173 A10 C.sub.2 H.sub.5 CH.sub.3 B1 H174 A10 C.sub.2 H.sub.5 CH.sub.3 B2 H175 A10 C.sub.2 H.sub.5 CH.sub.3 B3 H176 A10 C.sub. 2 H.sub.5 CH.sub.3 B4 H177 A10 C.sub.2 H.sub.5 CH.sub.3 B5 H178 A10 C.sub.2 H.sub.5 CH.sub.3 B6 H179 A10 C.sub.3 H.sub.7 -i CH.sub.3 B1 H180 A10 C.sub.3 H.sub.7 -i CH.sub.3 B2 H181 A10 C.sub.3 H.sub.7 -i CH.sub.3 B3 H182 A10 C.sub.3 H.sub.7 -i CH.sub.3 B4 H183 A10 C.sub.3 H.sub.7 -i CH.sub.3 B5 H184 A10 C.sub.3 H.sub.7 -i CH.sub.3 B6 H185 A10 C.sub.4 H.sub.9 -t CH.sub.3 B1 H186 A10 C.sub.4 H.sub.9 -t CH.sub.3 B2 H187 A10 C.sub.4 H.sub.9 -t CH.sub.3 B3 H188 A10 C.sub.4 H.sub.9 -t CH.sub.3 B4 H189 A10 C.sub.4 H.sub.9 -t CH.sub.3 B5 H190 A10 C.sub.4 H.sub.9 -t CH.sub.3 B6 H191 A10 C.sub.3 H.sub.7 -i F B3 H192 A10 C.sub.3 H.sub.7 -i Cl B3 H193 A10 C.sub.3 H.sub.7 -i Br B3 H194 A10 C.sub.3 H.sub.7 -i CH.sub.3 SO B3 H195 A10 C.sub.3 H.sub.7 -i CH.sub.3 SO.sub.2 B3 H196 A10 C.sub.3 H.sub.7 -i NH.sub.2 B3 H197 A10 C.sub.3 H.sub.7 -i N(CH.sub.3).sub.2 B3 H198 A10 C.sub.3 H.sub.7 -i CF.sub.3 B3 H199 A10 C.sub.3 H.sub.7 -i OH B3 H200 A10 C.sub.3 H.sub.7 -i OCH.sub.3 B3 H201 A10 C.sub.3 H.sub.7 -i C.sub.3 H.sub.7 -i B3 H202 A10 C.sub.3 H.sub.7 -i C.sub.4 H.sub.9 -t B3 H203 A10 C.sub.3 H.sub.7 -i C.sub.2 H.sub.5 B3 H204 A10 C.sub.3 H.sub.7 -i Q1 B3 H205 A10 C.sub.3 H.sub.7 -i Q2 B3 H206 A10 C.sub.3 H.sub.7 -i Q3 B3 H207 A10 C.sub.3 H.sub.7 -i Q4 B3 H208 A10 C.sub.3 H.sub.7 -i CH.sub.3 CHC(CH.sub.3).sub.2 H209 A10 C.sub.3 H.sub.7 -i CH.sub.3 CHCClCH.sub.3 H210 A10 C.sub.3 H.sub.7 -i CH.sub.3 OCH.sub.2 CH.sub.3 H211 A10 C.sub.3 H.sub.7 -i CH.sub.3 SCH.sub.2 CH.sub.3 H212 A10 C.sub.3 H.sub.7 -i CH.sub.3 OCH(CH.sub.3).sub.2 H213 A10 C.sub.3 H.sub.7 -i CH.sub.3 CH.sub.2 CHCH.sub.2 H214 A10 C.sub.3 H.sub.7 -i CH.sub.3 CH.sub.2 CCH H215 A10 C.sub.3 H.sub.7 -i CH.sub.3 O-Q1 H216 A10 C.sub.3 H.sub.7 -i CH.sub.3 O-Q2 H217 A10 C.sub.3 H.sub.7 -i CH.sub.3 O-Q3 H218 A10 C.sub.3 H.sub.7 -i CH.sub.3 O-Q4 H219 A10 C.sub.3 H.sub.7 -i Q1 B1 H220 A10 C.sub.3 H.sub.7 -i Q1 B2 H221 A10 C.sub.3 H.sub.7 -i Q2 B1 H222 A10 C.sub.3 H.sub.7 -i Q2 B2 H223 A10 C.sub.3 H.sub.7 -i CH.sub.3 B1 CH.sub.3224 A10 C.sub.3 H.sub.7 -i CH.sub.3 B2 CH.sub.3225 A10 C.sub.3 H.sub.7 -i CH.sub.3 B3 CH.sub.3226 A10 C.sub.3 H.sub.7 -i CH.sub.3 B4 CH.sub.3227 A10 C.sub.3 H.sub.7 -i CH.sub.3 B5 CH.sub.3228 A10 C.sub.3 H.sub.7 -i CH.sub.3 B6 CH.sub.3229 A10 C.sub.3 H.sub.7 -i CH.sub.3 B1 Q1230 A10 C.sub.3 H.sub.7 -i CH.sub.3 B1 Q2231 A10 C.sub.3 H.sub.7 -i CH.sub.3 B1 Q3232 A10 C.sub.3 H.sub.7 -i CH.sub.3 B1 Q4233 A10 C.sub.3 H.sub.7 -i CH.sub.3 B1 Q55234 A10 C.sub.3 H.sub.7 -i CH.sub.3 B2 Q1235 A10 C.sub.3 H.sub.7 -i CH.sub.3 B2 Q2236 A10 C.sub.3 H.sub.7 -i CH.sub.3 B2 Q3237 A10 C.sub.3 H.sub.7 -i CH.sub.3 B2 Q4238 A10 C.sub.3 H.sub.7 -i CH.sub.3 B2 Q55239 A10 C.sub.3 H.sub.7 -i CH.sub.3 B3 Q1240 A10 C.sub.3 H.sub.7 -i CH.sub.3 B3 Q2241 A10 C.sub.3 H.sub.7 -i CH.sub.3 B3 Q3242 A10 C.sub.3 H.sub.7 -i CH.sub.3 B3 Q4243 A10 C.sub.3 H.sub.7 -i CH.sub.3 B3 Q55244 A10 C.sub.3 H.sub.7 -i CH.sub.3 B4 Q1245 A10 C.sub.3 H.sub.7 -i CH.sub.3 B4 Q2246 A10 C.sub.3 H.sub.7 -i CH.sub.3 B4 Q3247 A10 C.sub.3 H.sub.7 -i CH.sub.3 B4 Q4248 A10 C.sub.3 H.sub.7 -i CH.sub.3 B4 Q55249 A10 C.sub.3 H.sub.7 -i CH.sub.3 B5 Q2250 A10 C.sub.3 H.sub.7 -i CH.sub.3 B5 Q3251 A10 C.sub.3 H.sub.7 -i CH.sub.3 B5 Q4252 A10 C.sub.3 H.sub.7 -i CH.sub.3 B5 Q55253 A10 C.sub.3 H.sub.7 -i CH.sub.3 B6 Q1254 A10 C.sub.3 H.sub.7 -i CH.sub.3 B6 Q2255 A10 C.sub.3 H.sub.7 -i CH.sub.3 B6 Q3256 A10 C.sub.3 H.sub.7 -i CH.sub.3 B6 Q4257 A10 C.sub.3 H.sub.7 -i CH.sub.3 B6 Q55258 A10 C.sub.4 H.sub.9 -t CH.sub.3 B1 Q1259 A10 C.sub.4 H.sub.9 -t CH.sub.3 B1 Q2260 A10 C.sub.4 H.sub.9 -t CH.sub.3 B1 Q3261 A10 C.sub.4 H.sub.9 -t CH.sub.3 B1 Q4262 A10 C.sub.4 H.sub.9 -t CH.sub.3 B1 Q55263 A10 C.sub.4 H.sub.9 -t CH.sub.3 B2 Q1264 A10 C.sub.4 H.sub.9 -t CH.sub.3 B2 Q2265 A10 C.sub.4 H.sub.9 -t CH.sub.3 B2 Q3266 A10 C.sub.4 H.sub.9 -t CH.sub.3 B2 Q4267 A10 C.sub.4 H.sub.9 -t CH.sub.3 B2 Q55268 A10 C.sub.4 H.sub.9 -t CH.sub.3 B3 Q1269 A10 C.sub.4 H.sub.9 -t CH.sub.3 B3 Q2270 A10 C.sub.4 H.sub.9 -t CH.sub.3 B3 Q3271 A10 C.sub.4 H.sub.9 -t CH.sub.3 B3 Q4272 A10 C.sub.4 H.sub.9 -t CH.sub.3 B3 Q55273 A10 C.sub.4 H.sub.9 -t CH.sub.3 B4 Q1274 A10 C.sub.4 H.sub.9 -t CH.sub.3 B4 Q2275 A10 C.sub.4 H.sub.9 -t CH.sub.3 B4 Q3276 A10 C.sub.4 H.sub.9 -t CH.sub.3 B4 Q4277 A10 C.sub.4 H.sub.9 -t CH.sub.3 B5 Q55278 A10 C.sub.4 H.sub.9 -t CH.sub.3 B5 Q1279 A10 C.sub.4 H.sub.9 -t CH.sub.3 B5 Q2280 A10 C.sub.4 H.sub.9 -t CH.sub.3 B5 Q3281 A10 C.sub.4 H.sub.9 -t CH.sub.3 B5 Q4282 A10 C.sub. 4 H.sub.9 -t CH.sub.3 B5 Q55283 A10 C.sub.4 H.sub.9 -t CH.sub.3 B6 Q1284 A10 C.sub.4 H.sub.9 -t CH.sub.3 B6 Q2285 A10 C.sub.4 H.sub.9 -t CH.sub.3 B6 Q3286 A10 C.sub.4 H.sub.9 -t CH.sub.3 B6 Q4287 A10 C.sub.4 H.sub.9 -t CH.sub.3 B6 Q55288 A10 C.sub.4 H.sub.9 -t CH.sub.3 B4 H289 A10 C.sub.4 H.sub.9 -t CH.sub.3 B4 H290 A10 Q1 CH.sub.3 B3 CH.sub.3291 A10 Q2 CH.sub.3 B3 CH.sub.3292 A10 Q3 CH.sub.3 B3 CH.sub.3293 A10 Q4 CH.sub.3 B3 CH.sub.3294 A10 Q55 CH.sub.3 B3 CH.sub.3295 A10 Q1 CH.sub.3 B3 Q1296 A10 Q2 CH.sub.3 B3 Q1297 A10 Q3 CH.sub.3 B3 Q1298 A10 Q4 CH.sub.3 B3 Q1299 A10 Q55 CH.sub.3 B3 Q1300 A10 Q1 CH.sub.3 B3 Q55301 A10 Q2 CH.sub.3 B3 Q55302 A10 Q3 CH.sub.3 B3 Q55303 A10 Q4 CH.sub.3 B3 Q55304 A10 Q55 CH.sub.3 B3 Q55305 A10 Q1 CH.sub.3 B1 H306 A10 Q2 CH.sub.3 B1 H307 A10 Q3 CH.sub.3 B1 H308 A10 Q4 CH.sub.3 B1 H309 A10 Q55 CH.sub.3 B1 H310 A10 Q1 CH.sub.3 B2 H311 A10 Q2 CH.sub.3 B2 H312 A10 Q3 CH.sub.3 B2 H313 A10 Q4 CH.sub.3 B2 H314 A10 Q55 CH.sub.3 B2 H315 A10 Q1 CH.sub.3 B3 H316 A10 Q2 CH.sub.3 B3 H317 A10 Q3 CH.sub.3 B3 H318 A10 Q4 CH.sub.3 B3 H319 A10 Q55 CH.sub.3 B3 H320 A10 Q1 CH.sub.3 B4 H321 A10 Q2 CH.sub.3 B4 H322 A10 Q3 CH.sub.3 B4 H323 A10 Q4 CH.sub.3 B4 H324 A10 Q55 CH.sub.3 B4 H325 A10 Q1 CH.sub.3 B5 H326 A10 Q2 CH.sub.3 B5 H327 A10 Q3 CH.sub.3 B5 H328 A10 Q4 CH.sub.3 B5 H329 A10 Q55 CH.sub.3 B5 H330 A10 Q1 CH.sub.3 B6 H331 A10 Q2 CH.sub.3 B6 H332 A10 Q3 CH.sub.3 B6 H333 A10 Q4 CH.sub.3 B6 H334 A10 Q55 CH.sub.3 B6 H335 A10 C.sub.3 H.sub.7 -n CH.sub.3 B1 H336 A10 C.sub.3 H.sub.7 -n CH.sub.3 B2 H337 A10 C.sub.3 H.sub.7 -n CH.sub.3 B3 H338 A10 C.sub.3 H.sub.7 -n CH.sub.3 B4 H339 A10 C.sub.3 H.sub.7 -n CH.sub.3 B5 H340 A10 C.sub.3 H.sub.7 -n CH.sub.3 B6 H341 A10 C.sub.4 H.sub.9 -s CH.sub.3 B1 H342 A10 C.sub.4 H.sub.9 -s CH.sub.3 B2 H343 A10 C.sub.4 H.sub.9 -s CH.sub.3 B3 H344 A10 C.sub.4 H.sub.9 -s CH.sub.3 B4 H345 A10 C.sub.4 H.sub.9 -s CH.sub.3 B5 H346 A10 CH.sub.2 F CH.sub.3 B3 H347 A10 CHF.sub.2 CH.sub.3 B3 H348 A10 CF.sub.3 CH.sub.3 B3 H349 A10 CH.sub.2 CH.sub.2 F CH.sub.3 B3 H350 A10 CH.sub.2 CHF.sub.2 CH.sub.3 B3 H351 A10 CH.sub.2 CF.sub.3 CH.sub.3 B3 H352 A10 CFCF.sub.2 CH.sub.3 B3 H353 A10 CH.sub.2 CN CH.sub.3 B3 H354 A10 COCH.sub.3 CH.sub.3 B3 H355 A10 CON(CH.sub.3).sub.2 CH.sub.3 B3 H356 A10 COCH.sub.2 OCH.sub.3 CH.sub.3 B3 H357 A10 CH.sub.2 OH CH.sub.3 B3 H358 A10 CH.sub.2 COOCH.sub.3 CH.sub.3 B3 H359 A10 Q56 CH.sub.3 B3 H360 A10 CHCH.sub.2 CH.sub.3 B3 H361 A10 CHCCH.sub.2 CH.sub.3 B3 H362 A10 CH.sub.2 CHCH.sub.2 CH.sub.3 B3 H363 A10 CH.sub.2 CCH CH.sub.3 B3 H364 A10 CH.sub.2 Cl CH.sub.3 B3 H365 A10 CHClCH.sub.3 CH.sub.3 B3 H366 A11 CH.sub.3 H B3 H367 A11 CH.sub.3 CH.sub.3 B3 H368 A11 C.sub.2 H.sub.5 H B3 H369 A11 C.sub.2 H.sub.5 CH.sub.3 B3 H370 A12 H H B3 H371 A12 CH.sub.3 H B3 H372 A12 H CH.sub.3 B3 H373 A12 CH.sub.3 CH.sub.3 B3 H374 A13 H H B3 H375 A13 CH.sub.3 H B3 H376 A13 H CH.sub.3 B3 H377 A13 CH.sub.3 CH.sub.3 B3 H378 A14 H H B3 H379 A14 CH.sub.3 H B3 H380 A14 H CH.sub.3 B3 H381 A14 CH.sub.3 CH.sub.3 B3 H382 A15 H H B3 H383 A15 CH.sub.3 H B3 H384 A15 H CH.sub.3 B3 H385 A15 CH.sub.3 CH.sub.3 B3 H386 A15 H C.sub.3 H.sub.7 -i B3 H387 A15 H C.sub.2 H.sub.5 B3 H388 A15 CH.sub.3 C.sub.3 H.sub.7 -i B3 H389 A15 CH.sub.3 C.sub.2 H.sub.5 B3 H390 A16 CH.sub.3 H B3 H391 A16 CH.sub.3 CH.sub.3 B3 H392 A17 CH.sub.3 H B1 H393 A17 CH.sub.3 CH.sub.3 B1 H394 A17 CH.sub.3 H B2 H395 A17 CH.sub.3 CH.sub.3 B2 H396 A17 CH.sub.3 H B3 H397 A17 CH.sub.3 CH.sub.3 B3 H398 A17 CH.sub.3 H B4 H399 A17 CH.sub.3 CH.sub.3 B4 H400 A17 CH.sub.3 H B5 H401 A17 CH.sub.3 CH.sub.3 B5 H402 A17 CH.sub.3 H B6 H403 A17 CH.sub.3 CH.sub.3 B6 H404 A17 CH.sub.2 CH.sub.3 H B3 H405 A17 C.sub.3 H.sub.7 -i CH.sub.3 B3 H406 A17 C.sub.4 H.sub.9 -t CH.sub.3 B3 H407 A17 CH.sub.3 H B3 CH.sub.3408 A17 CH.sub.3 CH.sub.3 B3 CH.sub.3409 A17 CH.sub.3 H B3 Q55410 A17 CH.sub.3 CH.sub.3 B3 Q55411 A18 CH.sub.3 H B3 H412 A18 CH.sub.3 CH.sub.3 B3 H413 A19 H -- B3 H414 A19 CH.sub.3 -- B3 H415 A20 H -- B3 H416 A20 CH.sub.3 -- B3 H417 A21 H -- B3 H418 A21 CH.sub.3 -- B3 H419 A22 H -- B3 H420 A22 CH.sub.3 -- B3 H421 A23 H H B1 H422 A23 H H B2 H423 A23 H H B3 H424 A23 H H B4 H425 A23 H H B5 H426 A23 H H B6 H427 A24 H H B1 H428 A24 H H B2 H429 A24 H H B3 H430 A24 H H B4 H431 A24 H H B5 H432 A24 H H B6 H433 A25 H H B1 H434 A25 H H B2 H435 A25 H H B3 H436 A25 H H B4 H437 A25 H H B5 H438 A25 H H B6 H439 A9 CH.sub.2 F H B5 H440 A10 CH.sub.2 CH.sub.3 H B1 H441 A10 CH.sub.2 CH.sub.3 H B2 H442 A10 CH.sub.2 CH.sub.3 H B3 H443 A10 CH.sub.2 CH.sub.3 H B4 H444 A10 CH.sub.2 CH.sub.3 H B5 H445 A10 CH.sub.2 CH.sub.3 H B6 H446 A10 C.sub.3 H.sub.7 -i H B1 H447 A10 C.sub.3 H.sub.7 -i H B2 H448 A10 C.sub.3 H.sub.7 -i H B3 H449 A10 C.sub.3 H.sub.7 -i H B4 H450 A10 C.sub.3 H.sub.7 -i H B5 H451 A10 C.sub.3 H.sub.7 -i H B6 H452 A10 C.sub.4 H.sub.9 -t H B1 H453 A10 C.sub.4 H.sub.9 -t H B2 H454 A10 C.sub.4 H.sub.9 -t H B3 H455 A10 C.sub.4 H.sub.9 -t H B4 H456 A10 C.sub.4 H.sub.9 -t H B5 H457 A10 C.sub.4 H.sub.9 -t H B6 H______________________________________
TABLE 4__________________________________________________________________________In a compound represented by the general formula: ##STR23##CompoundNo. A R.sup.1 R.sup.2 B W Y__________________________________________________________________________1005 A10 Q5 CH.sub.3 B1 NH.sub.2 H1006 A10 Q5 CH.sub.3 B2 NH.sub.2 H1007 A10 Q5 CH.sub.3 B3 NH.sub.2 H1008 A10 Q5 CH.sub.3 B4 NH.sub.2 H1009 A10 Q5 CH.sub.3 B5 NH.sub.2 H1010 A10 Q5 CH.sub.3 B6 NH.sub.2 H1011 A10 C.sub.4 H.sub.9 -i CH.sub.3 B1 NH.sub.2 H1012 A10 C.sub.4 H.sub.9 -i CH.sub.3 B2 NH.sub.2 H1013 A10 C.sub.4 H.sub.9 -i CH.sub.3 B3 NH.sub.2 H1014 A10 C.sub.4 H.sub.9 -i CH.sub.3 B4 NH.sub.2 H1015 A10 C.sub.4 H.sub.9 -i CH.sub.3 B5 NH.sub.2 H1016 A10 C.sub.4 H.sub.9 -i CH.sub.3 B6 NH.sub.2 H1017 A10 CH.sub.3 CH.sub.3 B1 F H1018 A10 CH.sub.3 CH.sub.3 B2 F H1019 A10 CH.sub.3 CH.sub.3 B3 F H1020 A10 CH.sub.3 CH.sub.3 B4 F H1021 A10 CH.sub.3 CH.sub.3 B1 Cl H1022 A10 CH.sub.3 CH.sub.3 B2 Cl H1023 A10 CH.sub.3 CH.sub.3 B3 Cl H1024 A10 CH.sub.3 CH.sub.3 B4 Cl H1025 A10 CH.sub.3 CH.sub.3 B1 Br H1026 A10 CH.sub.3 CH.sub.3 B2 Br H1027 A10 CH.sub.3 CH.sub.3 B3 Br H1028 A10 CH.sub.3 CH.sub.3 B4 Br H1029 A10 CH.sub.3 CH.sub.3 B1 I H1030 A10 CH.sub.3 CH.sub.3 B2 I H1031 A10 CH.sub.3 CH.sub.3 B3 I H1032 A10 CH.sub.3 CH.sub.3 B4 I H1033 A10 CH.sub.3 CH.sub.3 B4 NH.sub.2 CH.sub.31034 A10 CH.sub.3 CH.sub.3 B4 NH.sub.2 CH.sub.2 CHCH.sub.21035 A10 CH.sub.3 CH.sub.3 B4 NH.sub.2 C.sub.4 H.sub.9 n1036 A10 CH.sub.3 CH.sub.3 B4 NH.sub.2 COCH.sub.31037 A10 CH.sub.3 CH.sub.3 B4 NH.sub.2 COC.sub.6 H.sub.51038 A10 CH.sub. 3 CH.sub.3 B4 NH.sub.2 CONHCH.sub.31039 A10 CH.sub.3 CH.sub.3 B4 NH.sub.2 CONHCH(CH.sub.3).sub.21040 A10 CH.sub.3 CH.sub.3 B4 NH.sub.2 CONHC.sub.6 H.sub.51041 A10 CH.sub.3 CH.sub.3 B4 NH.sub.2 CONHC.sub.6 H.sub.4 Cl-p1042 A10 CH.sub.3 CH.sub.3 B4 NH.sub.2 CSNHCH.sub.31043 A10 CH.sub.3 CH.sub.3 B4 NH.sub.2 CO.sub.2 C.sub.2 H.sub.51044 A10 CH.sub.3 CH.sub.3 B4 NHCH.sub.3 H1045 A10 CH.sub.3 CH.sub.3 B4 NHC.sub.6 H.sub.5 H1046 A10 CH.sub.3 CH.sub.3 B4 NHQ6 H1047 A10 CH.sub.3 CH.sub.3 B4 NH.sub.2 H1048 A10 CH.sub.3 CH.sub.3 B4 SO.sub.2 CH.sub.3 H1049 A10 CH.sub.3 CH.sub.3 B4 SO.sub.2 C.sub.6 H.sub.5 CH.sub.3 -p H1050 A10 CH.sub.3 CH.sub.3 B4 SO.sub.2 N(CH.sub.3).sub.2 H1051 A1 H H B1 H H1052 A1 H H B2 H H1053 A1 H H B3 H H1054 A1 H H B4 H H1055 A1 3-Cl 5-Cl B1 H H1056 A1 3-Cl 5-Cl B2 H H1057 A1 3-Cl 5-Cl B3 H H1058 A1 3-Cl 5-Cl B4 H H1059 A2 H H B1 H H1060 A2 H H B2 H H1061 A2 H H B3 H H1062 A2 H H B4 H H1063 A3 H H B1 H H1064 A3 H H B2 H H1065 A3 H H B3 H H1066 A3 H H B4 H H1067 A4 H H B1 H H1068 A4 H H B2 H H1069 A4 H H B3 H H1070 A4 H H B4 H H1071 A5 H H B1 H H1072 A5 H H B2 H H1073 A5 H H B3 H H1074 A5 H H B4 H H1075 A6 H H B1 H H1076 A6 H H B2 H H1077 A6 H H B3 H H1078 A6 H H B4 H H1079 A7 CH.sub.3 H B1 H H1080 A7 CH.sub.3 H B2 H H1081 A7 CH.sub.3 H B3 H H1082 A7 CH.sub.3 H B4 H H1083 A8 CH.sub.3 H B1 H H1084 A8 CH.sub.3 H B2 H H1085 A8 CH.sub.3 H B3 H H1086 A8 CH.sub.3 H B4 H H1087 A9 CH.sub.3 H B1 H H1088 A9 CH.sub.3 H B2 H H1089 A9 CH.sub.3 H B3 H H1090 A9 CH.sub.3 H B4 H H1091 A9 CH.sub.3 H B5 H H1092 A9 CH.sub.3 H B6 H H1093 A9 CH.sub.3 H CHC(CH.sub.3).sub.2 H H1094 A9 CH.sub.3 H CHCClCH.sub.3 H H1095 A9 CH.sub.3 H OCH.sub.2 CH.sub.3 H H1096 A9 CH.sub.3 H SCH.sub.2 CH.sub.3 H H1097 A9 CH.sub.3 H OCH(CH.sub.3).sub.2 H H1098 A9 CH.sub.3 H CH.sub.2 CHCH.sub.2 H H1099 A9 CH.sub.3 H CH.sub.2 CCH H H1100 A9 CH.sub.3 H OQ1 H H1101 A9 CH.sub.3 H OQ2 H H1102 A9 CH.sub.3 H OQ3 H H1103 A9 CH.sub.3 H OQ4 H H1104 A9 CH.sub.3 CH.sub.3 B1 H H1105 A9 CH.sub.3 CH.sub.3 B2 H H1106 A9 CH.sub.3 CH.sub.3 B3 H H1107 A9 CH.sub.3 CH.sub.3 B4 H H1108 A9 CH.sub.3 CH.sub.3 B5 H H1109 A9 CH.sub.3 CH.sub.3 B6 H H1110 A9 CH.sub.3 CH.sub.3 CHC(CH.sub.3).sub.2 H H1111 A9 CH.sub.3 CH.sub.3 CHCClCH.sub.3 H H1112 A9 CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.3 H H1113 A9 CH.sub.3 CH.sub.3 SCH.sub.2 CH.sub.3 H H1114 A9 CH.sub.3 CH.sub.3 OCH(CH.sub.3).sub.2 H H1115 A9 CH.sub.3 CH.sub.3 CH.sub.2 CHCH.sub.2 H H1116 A9 CH.sub.3 CH.sub.3 CH.sub.2 CCH H H1117 A9 CH.sub.3 CH.sub.3 OQ1 H H1118 A9 CH.sub.3 CH.sub.3 OQ2 H H1119 A9 CH.sub.3 CH.sub.3 OQ3 H H1120 A9 CH.sub.3 CH.sub.3 OQ4 H H1121 A10 CH.sub.3 CH.sub.3 B1 H H1122 A10 CH.sub.3 CH.sub.3 B2 H H1123 A10 CH.sub.3 CH.sub.3 B3 H H1124 A10 CH.sub.3 CH.sub.3 B4 H H1125 A10 CH.sub.3 CH.sub.3 B5 H H1126 A10 CH.sub.3 CH.sub.3 B6 H H1127 A10 CH.sub.3 CH.sub.3 CHC(CH.sub.3).sub.2 H H1128 A10 CH.sub.3 CH.sub.3 CHCClCH.sub.3 H H1129 A10 CH.sub.3 CH.sub.3 OCH.sub.2 CH.sub.3 H H1130 A10 CH.sub.3 CH.sub.3 SCH.sub.2 CH.sub.3 H H1131 A10 CH.sub.3 CH.sub.3 OCH(CH.sub.3).sub.2 H H1132 A10 CH.sub.3 CH.sub.3 CH.sub.2 CHCH.sub.2 H H1133 A10 CH.sub.3 CH.sub.3 CH.sub.2 CCH H H1134 A10 CH.sub.3 CH.sub.3 OQ1 H H1135 A10 CH.sub.3 CH.sub.3 OQ2 H H1136 A10 CH.sub.3 CH.sub.3 OQ3 H H1137 A10 CH.sub.3 CH.sub.3 OQ4 H H1138 A10 C.sub.2 H.sub.5 CH.sub.3 B1 H H1139 A10 C.sub.2 H.sub.5 CH.sub.3 B2 H H1140 A10 C.sub.2 H.sub.5 CH.sub.3 B3 H H1141 A10 C.sub.2 H.sub.5 CH.sub.3 B4 H H1142 A10 C.sub. 2 H.sub.5 CH.sub.3 B5 H H1143 A10 C.sub.2 H.sub.5 CH.sub.3 B6 H H1144 A10 C.sub.2 H.sub.5 CH.sub.3 CHC(CH.sub.3).sub.2 H H1145 A10 C.sub.2 H.sub.5 CH.sub.3 CHCClCH.sub.3 H H1146 A10 C.sub.2 H.sub.5 CH.sub.3 OCH.sub.2 CH.sub.3 H H1147 A10 C.sub.2 H.sub.5 CH.sub.3 SCH.sub.2 CH.sub.3 H H1148 A10 C.sub.2 H.sub.5 CH.sub.3 OCH(CH.sub.3).sub.2 H H1149 A10 C.sub.2 H.sub.5 CH.sub.3 CH.sub.2 CHCH.sub.2 H H1150 A10 C.sub.2 H.sub.5 CH.sub.3 CH.sub.2 CCH H H1151 A10 C.sub.2 H.sub.5 CH.sub.3 OQ1 H H1152 A10 C.sub.2 H.sub.5 CH.sub.3 OQ2 H H1153 A10 C.sub.2 H.sub.5 CH.sub.3 OQ3 H H1154 A10 C.sub.2 H.sub.5 CH.sub.3 OQ4 H H1155 A10 C.sub.3 H.sub.7 -i CH.sub.3 B1 H H1156 A10 C.sub.3 H.sub.7 -i CH.sub.3 B2 H H1157 A10 C.sub.3 H.sub. 7 -i CH.sub.3 B3 H H1158 A10 C.sub.3 H.sub.7 -i CH.sub.3 B4 H H1159 A10 C.sub.3 H.sub.7 -i CH.sub.3 B5 H H1160 A10 C.sub.3 H.sub.7 -i CH.sub.3 B6 H H1161 A10 C.sub.3 H.sub.7 -i CH.sub.3 CHC(CH.sub.3).sub.2 H H1162 A10 C.sub.3 H.sub.7 -i CH.sub.3 CHCClCH.sub.3 H H1163 A10 C.sub.3 H.sub.7 -i CH.sub.3 OCH.sub.2 CH.sub.3 H H1164 A10 C.sub.3 H.sub.7 -i CH.sub.3 SCH.sub.2 CH.sub.3 H H1165 A10 C.sub.3 H.sub.7 -i CH.sub.3 OCH(CH.sub.3).sub.2 H H1166 A10 C.sub.3 H.sub.7 -i CH.sub.3 CH.sub.2 CHCH.sub.2 H H1167 A10 C.sub.3 H.sub.7 -i CH.sub.3 CH.sub.2 CCH H H1168 A10 C.sub.3 H.sub.7 -i CH.sub.3 OQ1 H H1169 A10 C.sub.3 H.sub.7 -i CH.sub.3 OQ2 H H1170 A10 C.sub.3 H.sub.7 -i CH.sub.3 OQ3 H H1171 A10 C.sub.3 H.sub.7 -i CH.sub.3 OQ4 H H1172 A10 Q1 CH.sub.3 B1 H H1173 A10 Q1 CH.sub.3 B2 H H1174 A10 Q1 CH.sub.3 B3 H H1175 A10 Q1 CH.sub.3 B4 H H1176 A10 Q1 CH.sub.3 B5 H H1177 A10 Q1 CH.sub.3 B6 H H1178 A10 Q1 CH.sub.3 CHC(CH.sub.3).sub.2 H H1179 A10 Q1 CH.sub.3 CHCClCH.sub.3 H H1180 A10 Q1 CH.sub.3 OCH.sub.2 CH.sub.3 H H1181 A10 Q1 CH.sub.3 SCH.sub.2 CH.sub.3 H H1182 A10 Q1 CH.sub.3 OCH(CH.sub.3).sub.2 H H1183 A10 Q1 CH.sub.3 CH.sub.2 CHCH.sub.2 H H1184 A10 Q1 CH.sub.3 CH.sub.2 CCH H H1185 A10 Q1 CH.sub.3 OQ1 H H1186 A10 Q1 CH.sub.3 OQ2 H H1187 A10 Q1 CH.sub.3 OQ3 H H1188 A10 Q1 CH.sub.3 OQ4 H H1189 A10 Q2 CH.sub.3 B1 H H1190 A10 Q2 CH.sub.3 B2 H H1191 A10 Q2 CH.sub.3 B3 H H1192 A10 Q2 CH.sub.3 B4 H H1193 A10 Q2 CH.sub.3 B5 H H1194 A10 Q2 CH.sub.3 B6 H H1195 A10 Q2 CH.sub.3 CHC(CH.sub.3).sub.2 H H1196 A10 Q2 CH.sub.3 CHCClCH.sub.3 H H1197 A10 Q2 CH.sub.3 OCH.sub.2 CH.sub.3 H H1198 A10 Q2 CH.sub.3 SCH.sub.2 CH.sub.3 H H1199 A10 Q2 CH.sub.3 OCH(CH.sub.3).sub.2 H H1200 A10 Q2 CH.sub.3 CH.sub.2 CHCH.sub.2 H H1201 A10 Q2 CH.sub.3 CH.sub.2 CCH H H1202 A10 Q2 CH.sub.3 OQ1 H H1203 A10 Q2 CH.sub.3 OQ2 H H1204 A10 Q2 CH.sub.3 OQ3 H H1205 A10 Q2 CH.sub.3 OQ4 H H1206 A10 Q3 CH.sub.3 B1 H H1207 A10 Q3 CH.sub.3 B2 H H1208 A10 Q3 CH.sub.3 B3 H H1209 A10 Q3 CH.sub.3 B4 H H1210 A10 Q3 CH.sub.3 B5 H H1211 A10 Q3 CH.sub.3 B6 H H1212 A10 Q3 CH.sub.3 CHC(CH.sub.3).sub.2 H H1213 A10 Q3 CH.sub. 3 CHCClCH.sub.3 H H1214 A10 Q3 CH.sub.3 OCH.sub.2 CH.sub.3 H H1215 A10 Q3 CH.sub.3 SCH.sub.2 CH.sub.3 H H1216 A10 Q3 CH.sub.3 OCH(CH.sub.3).sub.2 H H1217 A10 Q3 CH.sub.3 CH.sub.2 CHCH.sub.2 H H1218 A10 Q3 CH.sub.3 CH.sub.2 CCH H H1219 A10 Q3 CH.sub.3 OQ1 H H1220 A10 Q3 CH.sub.3 OQ2 H H1221 A10 Q3 CH.sub.3 OQ3 H H1222 A10 Q3 CH.sub.3 OQ4 H H1223 A10 Q4 CH.sub.3 B1 H H1224 A10 Q4 CH.sub.3 B2 H H1225 A10 Q4 CH.sub.3 B3 H H1226 A10 Q4 CH.sub.3 B4 H H1227 A10 Q4 CH.sub.3 B5 H H1228 A10 Q4 CH.sub.3 B6 H H1229 A10 Q4 CH.sub.3 CHC(CH.sub.3).sub.2 H H1230 A10 Q4 CH.sub.3 CHCClCH.sub.3 H H1231 A10 Q4 CH.sub.3 OCH.sub.2 CH.sub.3 H H1232 A10 Q4 CH.sub.3 SCH.sub.2 CH.sub.3 H H1233 A10 Q4 CH.sub.3 OCH(CH.sub.3).sub.2 H H1234 A10 Q4 CH.sub.3 CH.sub.2 CHCH.sub.2 H H1235 A10 Q4 CH.sub.3 CH.sub.2 CCH H H1236 A10 Q4 CH.sub.3 OQ1 H H1237 A10 Q4 CH.sub.3 OQ2 H H1238 A10 Q4 CH.sub.3 OQ3 H H1239 A10 Q4 CH.sub.3 OQ4 H H1240 A10 Q5 CH.sub.3 B1 H H1241 A10 Q5 CH.sub.3 B2 H H1242 A10 Q5 CH.sub.3 B3 H H1243 A10 Q5 CH.sub.3 B4 H H1244 A10 Q5 CH.sub.3 B5 H H1245 A10 Q5 CH.sub.3 B6 H H1246 A10 Q5 CH.sub.3 CHC(CH.sub.3).sub.2 H H1247 A10 Q5 CH.sub.3 CHCClCH.sub.3 H H1248 A10 Q5 CH.sub.3 OCH.sub.2 CH.sub.3 H H1249 A10 Q5 CH.sub.3 SCH.sub.2 CH.sub.3 H H1250 A10 Q5 CH.sub.3 OCH(CH.sub.3).sub.2 H H1251 A10 Q5 CH.sub.3 CH.sub.2 CHCH.sub.2 H H1252 A10 Q5 CH.sub.3 CH.sub.2 C CH H H1253 A10 Q5 CH.sub.3 OQ1 H H1254 A10 Q5 CH.sub.3 OQ2 H H1255 A10 Q5 CH.sub.3 OQ3 H H1256 A10 Q5 CH.sub.3 OQ4 H H1257 A10 Q6 CH.sub.3 B1 H H1258 A10 Q6 CH.sub.3 B2 H H1259 A10 Q6 CH.sub.3 B3 H H1260 A10 Q6 CH.sub.3 B4 H H1261 A10 Q6 CH.sub.3 B5 H H1262 A10 Q6 CH.sub.3 B6 H H1263 A10 Q6 CH.sub.3 CHC(CH.sub.3).sub.2 H H1264 A10 Q6 CH.sub.3 CHCClCH.sub.3 H H1265 A10 Q6 CH.sub.3 OCH.sub.2 CH.sub.3 H H1266 A10 Q6 CH.sub.3 SCH.sub.2 CH.sub.3 H H1267 A10 Q6 CH.sub.3 OCH(CH.sub.3).sub.2 H H1268 A10 Q6 CH.sub.3 CH.sub.2 CHCH.sub.2 H H1269 A10 Q6 CH.sub.3 CH.sub.2 CCH H H1270 A10 Q6 CH.sub.3 OQ1 H H1271 A10 Q6 CH.sub.3 OQ2 H H1272 A10 Q6 CH.sub.3 OQ3 H H1273 A10 Q6 CH.sub. 3 OQ4 H H1274 A10 CH.sub.2 F CH.sub.3 OQ4 H H1275 A10 CH.sub.2 OCH.sub.3 CH.sub.3 B3 H H1276 A10 Q7 CH.sub.3 B3 H H1277 A10 Q8 CH.sub.3 B3 H H1278 A10 Q9 CH.sub.3 B3 H H1279 A10 Q10 CH.sub.3 B3 H H1280 A10 Q11 CH.sub.3 B3 H H1281 A10 Q12 CH.sub.3 B3 H H1282 A10 Q13 CH.sub.3 B3 H H1283 A10 Q14 CH.sub.3 B3 H H1284 A10 Q15 CH.sub.3 B3 H H1285 A10 Q16 CH.sub.3 B3 H H1286 A10 Q17 CH.sub.3 B3 H H1287 A10 Q18 CH.sub.3 B3 H H1288 A10 Q19 CH.sub.3 B3 H H1289 A10 Q20 CH.sub.3 B3 H H1290 A10 Q21 CH.sub.3 B3 H H1291 A10 Q22 CH.sub.3 B3 H H1292 A10 Q23 CH.sub.3 B3 H H1293 A10 Q24 CH.sub.3 B3 H H1294 A10 Q25 CH.sub.3 B3 H H1295 A10 Q26 CH.sub.3 B3 H H1296 A10 Q27 CH.sub.3 B3 H H1297 A10 Q28 CH.sub.3 B3 H H1298 A10 Q29 CH.sub.3 B3 H H1299 A10 Q30 CH.sub.3 B3 H H1300 A10 Q31 CH.sub.3 B3 H H1301 A10 Q32 CH.sub.3 B3 H H1302 A10 Q33 CH.sub.3 B3 H H1303 A10 Q34 CH.sub.3 B3 H H1304 A10 Q35 CH.sub.3 B3 H H1305 A10 Q36 CH.sub.3 B3 H H1306 A10 Q37 CH.sub.3 B3 H H1307 A10 Q38 CH.sub.3 B3 H H1308 A10 Q39 CH.sub.3 B3 H H1309 A10 Q40 CH.sub.3 B3 H H1310 A10 Q41 CH.sub.3 B3 H H1311 A10 Q42 CH.sub.3 B3 H H1312 A10 Q43 CH.sub.3 B3 H H1313 A10 Q44 CH.sub.3 B3 H H1314 A10 Q45 CH.sub.3 B3 H H1315 A10 Q46 CH.sub.3 B3 H H1316 A10 Q47 CH.sub.3 B3 H H1317 A10 Q48 CH.sub.3 B3 H H1318 A10 Q49 CH.sub.3 B3 H H1319 A10 Q50 CH.sub.3 B3 H H1320 A10 Q51 CH.sub.3 B3 H H1321 A10 Q52 CH.sub.3 B3 H H1322 A10 Q53 CH.sub.3 B3 H H1323 A10 Q54 CH.sub.3 B3 H H1324 A11 CH.sub.3 H B3 H H1325 A11 CH.sub.3 CH.sub.3 B3 H H1326 A12 H H B3 H H1327 A12 CH.sub.3 H B3 H H1328 A12 H CH.sub.3 B3 H H1329 A12 CH.sub.3 CH.sub.3 B3 H H1330 A13 H H B3 H H1331 A13 CH.sub.3 H B3 H H1332 A13 H CH.sub.3 B3 H H1333 A13 CH.sub.3 CH.sub.3 B3 H H1334 A14 H H B3 H H1335 A14 CH.sub.3 H B3 H H1336 A14 H CH.sub.3 B3 H H1337 A15 H H B3 H H1338 A15 CH.sub.3 H B3 H H1339 A15 H CH.sub.3 B3 H H1340 A15 CH.sub.3 CH.sub.3 B3 H H1341 A16 CH.sub.3 H B3 H H1342 A16 CH.sub.3 CH.sub.3 B3 H H1343 A17 CH.sub.3 H B3 H H1344 A17 CH.sub.3 CH.sub.3 B3 H H1345 A18 CH.sub.3 CH.sub.3 B3 H H1346 A18 CH.sub.3 CH.sub.3 B3 H H1347 A19 H -- B3 H H1348 A19 CH.sub.3 -- B3 H H1349 A20 H -- B3 H H1350 A20 CH.sub.3 -- B3 H H1351 A21 H -- B3 H H1352 A21 CH.sub.3 -- B3 H H1353 A22 H -- B3 H H1354 A22 CH.sub.3 -- B3 H H1355 A23 H H B3 H H1356 A24 H H B3 H H1357 A25 H H B3 H H1364 A10 Q1 CH.sub.3 CHC(CH.sub.3).sub.2 NH.sub.2 H1365 A10 Q1 CH.sub.3 CHCClCH.sub.3 NH.sub.2 H1366 A10 Q1 CH.sub.3 OCH.sub.2 CH.sub.3 NH.sub.2 H1367 A10 Q1 CH.sub.3 SCH.sub.2 CH.sub.3 NH.sub.2 H1368 A10 Q1 CH.sub.3 OCH(CH.sub.3).sub.2 NH.sub.2 H1369 A10 Q1 CH.sub.3 CH.sub.2 CHCH.sub.2 NH.sub.2 H1370 A10 Q1 CH.sub.3 CH.sub.2 CCH NH.sub.2 H1371 A10 Q1 CH.sub.3 OQ1 NH.sub.2 H1372 A10 Q1 CH.sub.3 OQ2 NH.sub.2 H1373 A10 Q1 CH.sub.3 OQ3 NH.sub.2 H1374 A10 Q1 CH.sub.3 OQ4 NH.sub.2 H1381 A10 Q2 CH.sub.3 CHC(CH.sub.3).sub.2 NH.sub.2 H1382 A10 Q2 CH.sub.3 CHCClCH.sub.3 NH.sub.2 H1383 A10 Q2 CH.sub.3 OCH.sub.2 CH.sub.3 NH.sub.2 H1384 A10 Q2 CH.sub.3 SCH.sub.2 CH.sub.3 NH.sub.2 H1385 A10 Q2 CH.sub.3 OCH(CH.sub.3).sub.2 NH.sub.2 H1386 A10 Q2 CH.sub.3 CH.sub.2 CHCH.sub.2 NH.sub.2 H1387 A10 Q2 CH.sub.3 CH.sub.2 CCH NH.sub.2 H1388 A10 Q2 CH.sub.3 OQ1 NH.sub.2 H1389 A10 Q2 CH.sub.3 OQ2 NH.sub.2 H1390 A10 Q2 CH.sub.3 OQ3 NH.sub.2 H1391 A10 Q3 CH.sub.3 OQ4 NH.sub.2 H1395 A10 Q3 CH.sub.3 CHC(CH.sub.3).sub.2 NH.sub.2 H1396 A10 Q3 CH.sub.3 CHCClCH.sub.3 NH.sub.2 H1397 A10 Q3 CH.sub.3 OCH.sub.2 CH.sub.3 NH.sub.2 H1398 A10 Q3 CH.sub.3 SCH.sub.2 CH.sub.3 NH.sub.2 H1399 A10 Q3 CH.sub.3 OCH(CH.sub. 3).sub.2 NH.sub.2 H1400 A10 Q3 CH.sub.3 CH.sub.2 CHCH.sub.2 NH.sub.2 H1401 A10 Q3 CH.sub.3 CH.sub.2 CCH NH.sub.2 H1402 A10 Q3 CH.sub.3 OQ1 NH.sub.2 H1403 A10 Q3 CH.sub.3 OQ2 NH.sub.2 H1409 A10 Q4 CH.sub.3 CHC(CH.sub.3).sub.2 NH.sub.2 H1410 A10 Q4 CH.sub.3 CHCClCH.sub.3 NH.sub.2 H1411 A10 Q4 CH.sub.3 OCH.sub.2 CH.sub.3 NH.sub.2 H1412 A10 Q4 CH.sub.3 SCH.sub.2 CH.sub.3 NH.sub.2 H1413 A10 Q4 CH.sub.3 OCH(CH.sub.3).sub.2 NH.sub.2 H1414 A10 Q4 CH.sub.3 CH.sub.2 CHCH.sub.2 NH.sub.2 H1415 A10 Q4 CH.sub.3 CH.sub.2 CCH NH.sub.2 H1416 A10 Q4 CH.sub.3 OQ1 NH.sub.2 H1417 A10 Q4 CH.sub.3 OQ2 NH.sub.2 H1418 A10 Q4 CH.sub.3 OQ3 NH.sub.2 H1419 A10 Q4 CH.sub.3 OQ4 NH.sub.2 H1420 A10 Q6 CH.sub.3 B1 NH.sub.2 H1421 A10 Q6 CH.sub.3 B2 NH.sub.2 H1422 A10 Q6 CH.sub.3 B3 NH.sub.2 H1423 A10 Q6 CH.sub.3 B4 NH.sub.2 H1424 A10 Q6 CH.sub.3 B5 NH.sub.2 H1425 A10 Q7 CH.sub.3 B1 NH.sub.2 H1426 A10 Q7 CH.sub.3 B2 NH.sub.2 H1427 A10 Q7 CH.sub.3 B3 NH.sub.2 H1428 A10 Q7 CH.sub.3 B4 NH.sub.2 H1429 A10 Q7 CH.sub.3 B5 NH.sub.2 H1430 A10 Q10 CH.sub.3 B1 NH.sub.2 H1431 A10 Q10 CH.sub.3 B2 NH.sub.2 H1432 A10 Q10 CH.sub.3 B3 NH.sub.2 H1433 A10 Q10 CH.sub.3 B4 NH.sub.2 H1434 A10 Q10 CH.sub.3 B5 NH.sub.2 H1435 A10 Q11 CH.sub.3 B1 NH.sub.2 H1436 A10 Q11 CH.sub.3 B2 NH.sub.2 H1437 A10 Q11 CH.sub.3 B3 NH.sub.2 H1438 A10 Q11 CH.sub.3 B4 NH.sub.2 H1439 A10 Q11 CH.sub.3 B5 NH.sub.2 H1440 A10 Q12 CH.sub.3 B1 NH.sub.2 H1441 A10 Q12 CH.sub.3 B2 NH.sub.2 H1442 A10 Q12 CH.sub.3 B3 NH.sub.2 H1443 A10 Q12 CH.sub.3 B4 NH.sub.2 H1444 A10 Q12 CH.sub.3 B5 NH.sub.2 H1445 A10 Q14 CH.sub.3 B1 NH.sub.2 H1446 A10 Q14 CH.sub.3 B2 NH.sub.2 H1447 A10 Q14 CH.sub.3 B3 NH.sub.2 H1448 A10 Q14 CH.sub.3 B4 NH.sub.2 H1449 A10 Q14 CH.sub.3 B5 NH.sub.2 H1450 A10 Q8 CH.sub.3 B1 NH.sub.2 H1451 A10 Q8 CH.sub.3 B2 NH.sub.2 H1452 A10 Q8 CH.sub.3 B3 NH.sub.2 H1453 A10 Q8 CH.sub.3 B4 NH.sub.2 H1454 A10 Q9 CH.sub.3 B1 NH.sub.2 H1455 A10 Q9 CH.sub.3 B2 NH.sub.2 H1456 A10 Q9 CH.sub.3 B3 NH.sub.2 H1457 A10 Q9 CH.sub.3 B4 NH.sub.2 H1458 A10 Q13 CH.sub.3 B1 NH.sub.2 H1459 A10 Q13 CH.sub.3 B2 NH.sub.2 H1460 A10 Q13 CH.sub.3 B3 NH.sub.2 H1461 A10 Q13 CH.sub.3 B4 NH.sub.2 H1462 A10 Q15 CH.sub.3 B1 NH.sub.2 H1463 A10 Q15 CH.sub.3 B2 NH.sub.2 H1464 A10 Q15 CH.sub.3 B3 NH.sub.2 H1465 A10 Q15 CH.sub.3 B4 NH.sub. 2 H1466 A10 Q16 CH.sub.3 B1 NH.sub.2 H1467 A10 Q16 CH.sub.3 B2 NH.sub.2 H1468 A10 Q16 CH.sub.3 B3 NH.sub.2 H1469 A10 Q16 CH.sub.3 B4 NH.sub.2 H1470 A10 Q17 CH.sub.3 B1 NH.sub.2 H1471 A10 Q17 CH.sub.3 B2 NH.sub.2 H1472 A10 Q17 CH.sub.3 B3 NH.sub.2 H1473 A10 Q17 CH.sub.3 B4 NH.sub.2 H1474 A10 Q18 CH.sub.3 B1 NH.sub.2 H1475 A10 Q18 CH.sub.3 B2 NH.sub.2 H1476 A10 Q18 CH.sub.3 B3 NH.sub.2 H1477 A10 Q18 CH.sub.3 B4 NH.sub.2 H1478 A10 Q19 CH.sub.3 B1 NH.sub.2 H1479 A10 Q19 CH.sub.3 B2 NH.sub.2 H1480 A10 Q19 CH.sub.3 B3 NH.sub.2 H1481 A10 Q19 CH.sub.3 B4 NH.sub.2 H1482 A10 Q20 CH.sub.3 B1 NH.sub.2 H1483 A10 Q20 CH.sub.3 B2 NH.sub.2 H1484 A10 Q20 CH.sub.3 B3 NH.sub.2 H1485 A10 Q20 CH.sub.3 B4 NH.sub.2 H1486 A10 Q21 CH.sub.3 B1 NH.sub.2 H1487 A10 Q21 CH.sub.3 B2 NH.sub.2 H1488 A10 Q21 CH.sub.3 B3 NH.sub.2 H1489 A10 Q21 CH.sub.3 B4 NH.sub.2 H1490 A10 Q22 CH.sub.3 B1 NH.sub.2 H1491 A10 Q22 CH.sub.3 B2 NH.sub.2 H1492 A10 Q22 CH.sub.3 B3 NH.sub.2 H1493 A10 Q22 CH.sub.3 B4 NH.sub.2 H1494 A10 Q23 CH.sub.3 B1 NH.sub.2 H1495 A10 Q23 CH.sub.3 B2 NH.sub.2 H1496 A10 Q23 CH.sub.3 B3 NH.sub.2 H1497 A10 Q23 CH.sub.3 B4 NH.sub.2 H1498 A10 Q24 CH.sub.3 B1 NH.sub.2 H1499 A10 Q24 CH.sub.3 B2 NH.sub.2 H1500 A10 Q24 CH.sub.3 B3 NH.sub.2 H1501 A10 Q24 CH.sub.3 B4 NH.sub.2 H1502 A10 Q26 CH.sub.3 B1 NH.sub.2 H1503 A10 Q26 CH.sub.3 B2 NH.sub.2 H1504 A10 Q26 CH.sub.3 B3 NH.sub.2 H1505 A10 Q26 CH.sub.3 B4 NH.sub.2 H1506 A10 Q27 CH.sub.3 B1 NH.sub.2 H1507 A10 Q27 CH.sub.3 B2 NH.sub.2 H1508 A10 Q27 CH.sub.3 B3 NH.sub.2 H1509 A10 Q27 CH.sub.3 B4 NH.sub.2 H1510 A10 Q28 CH.sub.3 B1 NH.sub.2 H1511 A10 Q28 CH.sub.3 B2 NH.sub.2 H1512 A10 Q28 CH.sub.3 B3 NH.sub.2 H1513 A10 Q29 CH.sub.3 B1 NH.sub.2 H1514 A10 Q29 CH.sub.3 B2 NH.sub.2 H1515 A10 Q29 CH.sub.3 B3 NH.sub.2 H1516 A10 Q29 CH.sub.3 B4 NH.sub.2 H1517 A10 Q30 CH.sub.3 B1 NH.sub.2 H1518 A10 Q30 CH.sub.3 B2 NH.sub.2 H1519 A10 Q30 CH.sub.3 B3 NH.sub.2 H1510 A10 Q30 CH.sub.3 B4 NH.sub.2 H1521 A10 Q31 CH.sub.3 B1 NH.sub.2 H1522 A10 Q31 CH.sub.3 B2 NH.sub.2 H1523 A10 Q31 CH.sub.3 B3 NH.sub.2 H1524 A10 Q31 CH.sub.3 B4 NH.sub.2 H1525 A10 Q32 CH.sub.3 B1 NH.sub.2 H1526 A10 Q33 CH.sub.3 B2 NH.sub.2 H1527 A10 Q33 CH.sub.3 B3 NH.sub.2 H1528 A10 Q33 CH.sub.3 B4 NH.sub.2 H1529 A10 Q34 CH.sub.3 B1 NH.sub.2 H1520 A10 Q34 CH.sub.3 B2 NH.sub.2 H1521 A10 Q34 CH.sub.3 B3 NH.sub.2 H1532 A10 Q34 CH.sub. 3 B4 NH.sub.2 H1533 A10 Q35 CH.sub.3 B1 NH.sub.2 H1534 A10 Q35 CH.sub.3 B2 NH.sub.2 H1535 A10 Q35 CH.sub.3 B3 NH.sub.2 H1536 A10 Q35 CH.sub.3 B4 NH.sub.2 H1537 A10 Q36 CH.sub.3 B1 NH.sub.2 H1538 A10 Q36 CH.sub.3 B2 NH.sub.2 H1539 A10 Q36 CH.sub.3 B3 NH.sub.2 H1530 A10 Q36 CH.sub.3 B4 NH.sub.2 H1531 A10 Q37 CH.sub.3 B1 NH.sub.2 H1532 A10 Q37 CH.sub.3 B2 NH.sub.2 H1543 A10 Q37 CH.sub.3 B3 NH.sub.2 H1544 A10 Q37 CH.sub.3 B4 NH.sub.2 H1545 A10 Q38 CH.sub.3 B1 NH.sub.2 H1546 A10 Q38 CH.sub.3 B2 NH.sub.2 H1547 A10 Q38 CH.sub.3 B3 NH.sub.2 H1548 A10 Q39 CH.sub.3 B1 NH.sub.2 H1549 A10 Q39 CH.sub.3 B2 NH.sub.2 H1550 A10 Q39 CH.sub.3 B3 NH.sub.2 H1551 A10 Q39 CH.sub.3 B4 NH.sub.2 H1552 A10 Q40 CH.sub.3 B1 NH.sub.2 H1553 A10 Q40 CH.sub.3 B2 NH.sub.2 H1554 A10 Q40 CH.sub.3 B3 NH.sub.2 H1555 A10 Q40 CH.sub.3 B4 NH.sub.2 H1556 A10 Q41 CH.sub.3 B1 NH.sub.2 H1557 A10 Q41 CH.sub.3 B2 NH.sub.2 H1558 A10 Q41 CH.sub.3 B3 NH.sub.2 H1559 A10 Q41 CH.sub.3 B4 NH.sub.2 H1560 A10 Q42 CH.sub.3 B1 NH.sub.2 H1561 A10 Q43 CH.sub.3 B2 NH.sub.2 H1562 A10 Q43 CH.sub.3 B3 NH.sub.2 H1563 A10 Q43 CH.sub.3 B4 NH.sub.2 H1564 A10 Q44 CH.sub.3 B1 NH.sub.2 H1565 A10 Q44 CH.sub.3 B2 NH.sub.2 H1566 A10 Q44 CH.sub.3 B3 NH.sub.2 H1567 A10 Q44 CH.sub.3 B4 NH.sub.2 H1568 A10 Q45 CH.sub.3 B1 NH.sub.2 H1569 A10 Q45 CH.sub.3 B2 NH.sub.2 H1570 A10 Q45 CH.sub.3 B3 NH.sub.2 H1571 A10 Q45 CH.sub.3 B4 NH.sub.2 H1572 A10 Q46 CH.sub.3 B1 NH.sub.2 H1573 A10 Q46 CH.sub.3 B2 NH.sub.2 H1574 A10 Q46 CH.sub.3 B3 NH.sub.2 H1575 A10 Q46 CH.sub.3 B4 NH.sub.2 H1576 A10 Q47 CH.sub.3 B1 NH.sub.2 H1577 A10 Q47 CH.sub.3 B2 NH.sub.2 H1578 A10 Q47 CH.sub.3 B3 NH.sub.2 H1579 A10 Q47 CH.sub.3 B4 NH.sub.2 H1580 A10 Q48 CH.sub.3 B1 NH.sub.2 H1581 A10 Q48 CH.sub.3 B2 NH.sub.2 H1582 A10 Q48 CH.sub.3 B3 NH.sub.2 H1583 A10 Q49 CH.sub.3 B1 NH.sub.2 H1584 A10 Q49 CH.sub.3 B2 NH.sub.2 H1585 A10 Q49 CH.sub.3 B3 NH.sub.2 H1586 A10 Q49 CH.sub.3 B4 NH.sub.2 H1587 A10 Q50 CH.sub.3 B1 NH.sub.2 H1588 A10 Q50 CH.sub.3 B2 NH.sub.2 H1589 A10 Q50 CH.sub.3 B3 NH.sub.2 H1590 A10 Q50 CH.sub.3 B4 NH.sub.2 H1591 A10 Q51 CH.sub.3 B1 NH.sub.2 H1592 A10 Q51 CH.sub.3 B2 NH.sub.2 H1593 A10 Q51 CH.sub.3 B3 NH.sub.2 H1594 A10 Q51 CH.sub.3 B4 NH.sub.2 H1595 A10 Q52 CH.sub.3 B1 NH.sub.2 H1596 A10 Q53 CH.sub.3 B2 NH.sub.2 H1597 A10 Q53 CH.sub.3 B3 NH.sub.2 H1598 A10 Q53 CH.sub.3 B4 NH.sub.2 H1599 A10 Q54 CH.sub.3 B1 NH.sub.2 H1600 A10 Q54 CH.sub.3 B2 NH.sub.2 H1601 A10 Q54 CH.sub.3 B3 NH.sub.2 H1602 A10 Q54 CH.sub.3 B4 NH.sub.2 H1603 A9 CH.sub.3 Q1 B1 NH.sub.2 H1604 A9 CH.sub.3 Q2 B1 NH.sub.2 H1605 A9 CH.sub.3 Q3 B1 NH.sub.2 H1606 A9 CH.sub.3 Q4 B1 NH.sub.2 H1607 A9 CH.sub.3 Q44 B1 NH.sub.2 H1608 A9 CH.sub.3 Q46 B1 NH.sub.2 H1609 A9 CH.sub.3 Q47 B1 NH.sub.2 H1610 A9 CH.sub.3 Q1 B2 NH.sub.2 H1611 A9 CH.sub.3 Q2 B2 NH.sub.2 H1612 A9 CH.sub.3 Q3 B2 NH.sub.2 H1613 A9 CH.sub.3 Q4 B2 NH.sub.2 H1614 A9 CH.sub.3 Q44 B2 NH.sub.2 H1615 A9 CH.sub.3 Q46 B2 NH.sub.2 H1616 A9 CH.sub.3 Q47 B2 NH.sub.2 H1617 A9 CH.sub.3 Q1 B3 NH.sub.2 H1618 A9 CH.sub.3 Q2 B3 NH.sub.2 H1619 A9 CH.sub.3 Q3 B3 NH.sub.2 H1620 A9 CH.sub.3 Q4 B3 NH.sub.2 H1621 A9 CH.sub. 3 Q44 B3 NH.sub.2 H1622 A9 CH.sub.3 Q46 B3 NH.sub.2 H1623 A9 CH.sub.3 Q47 B3 NH.sub.2 H1624 A9 CH.sub.3 Q1 B4 NH.sub.2 H1625 A9 CH.sub.3 Q2 B4 NH.sub.2 H1626 A9 CH.sub.3 Q3 B4 NH.sub.2 H1627 A9 CH.sub.3 Q4 B4 NH.sub.2 H1628 A9 CH.sub.3 Q44 B4 NH.sub.2 H1629 A9 CH.sub.3 Q46 B4 NH.sub.2 H1630 A9 CH.sub.3 Q47 B4 NH.sub.2 H1631 A9 C.sub.2 H.sub.5 Q1 B1 NH.sub.2 H1632 A9 C.sub.2 H.sub.5 Q2 B1 NH.sub.2 H1633 A9 C.sub.2 H.sub.5 Q3 B1 NH.sub.2 H1634 A9 C.sub.2 H.sub.5 Q4 B1 NH.sub.2 H1635 A9 C.sub.2 H.sub.5 Q44 B1 NH.sub.2 H1636 A9 C.sub.2 H.sub.5 Q46 B1 NH.sub.2 H1637 A9 C.sub.2 H.sub.5 Q47 B1 NH.sub.2 H1638 A9 C.sub.2 H.sub.5 Q1 B2 NH.sub.2 H1639 A9 C.sub.2 H.sub.5 Q2 B2 NH.sub.2 H1640 A9 C.sub.2 H.sub.5 Q3 B2 NH.sub.2 H1641 A9 C.sub. 2 H.sub.5 Q4 B2 NH.sub.2 H1642 A9 C.sub.2 H.sub.5 Q44 B2 NH.sub.2 H1643 A9 C.sub.2 H.sub.5 Q46 B2 NH.sub.2 H1644 A9 C.sub.2 H.sub.5 Q47 B2 NH.sub.2 H1645 A9 C.sub.2 H.sub.5 Q1 B3 NH.sub.2 H1646 A9 C.sub.2 H.sub.5 Q2 B3 NH.sub.2 H1647 A9 C.sub.2 H.sub.5 Q3 B3 NH.sub.2 H1648 A9 C.sub.2 H.sub.5 Q4 B3 NH.sub.2 H1649 A9 C.sub.2 H.sub.5 Q44 B3 NH.sub.2 H1650 A9 C.sub.2 H.sub.5 Q46 B3 NH.sub.2 H1651 A9 C.sub.2 H.sub.5 Q47 B3 NH.sub.2 H1652 A10 C.sub.2 H.sub.5 Q1 B4 NH.sub.2 H1653 A10 C.sub.2 H.sub.5 Q2 B4 NH.sub.2 H1654 A10 C.sub.2 H.sub.5 Q3 B4 NH.sub.2 H1655 A10 C.sub.2 H.sub.5 Q4 B4 NH.sub.2 H1656 A10 C.sub.2 H.sub.5 Q44 B4 NH.sub.2 H1657 A10 C.sub.2 H.sub.5 Q46 B4 NH.sub.2 H1658 A10 C.sub.2 H.sub.5 Q47 B4 NH.sub.2 H1659 A9 C.sub.3 H.sub. 7 -i Q1 B1 NH.sub.2 H1660 A9 C.sub.3 H.sub.7 -i Q2 B1 NH.sub.2 H1661 A9 C.sub.3 H.sub.7 -i Q3 B1 NH.sub.2 H1662 A9 C.sub.3 H.sub.7 -i Q4 B1 NH.sub.2 H1663 A9 C.sub.3 H.sub.7 -i Q44 B1 NH.sub.2 H1664 A9 C.sub.3 H.sub.7 -i Q46 B1 NH.sub.2 H1665 A9 C.sub.3 H.sub.7 -i Q47 B1 NH.sub.2 H1666 A9 C.sub.3 H.sub.7 -i Q1 B2 NH.sub.2 H1667 A9 C.sub.3 H.sub.7 -i Q2 B2 NH.sub.2 H1668 A9 C.sub.3 H.sub.7 -i Q3 B2 NH.sub.2 H1669 A9 C.sub.3 H.sub.7 -i Q4 B2 NH.sub.2 H1670 A9 C.sub.3 H.sub.7 -i Q44 B2 NH.sub.2 H1671 A9 C.sub.3 H.sub.7 -i Q46 B2 NH.sub.2 H1672 A9 C.sub.3 H.sub.7 -i Q47 B2 NH.sub.2 H1673 A9 C.sub.3 H.sub.7 -i Q1 B3 NH.sub.2 H1674 A9 C.sub.3 H.sub.7 -i Q2 B3 NH.sub.2 H1675 A9 C.sub.3 H.sub.7 -i Q3 B3 NH.sub.2 H1676 A9 C.sub.3 H.sub.7 -i Q4 B3 NH.sub.2 H1677 A9 C.sub.3 H.sub.7 -i Q44 B3 NH.sub.2 H1678 A9 C.sub.3 H.sub.7 -i Q46 B3 NH.sub.2 H1679 A9 C.sub.3 H.sub.7 -i Q47 B3 NH.sub.2 H1680 A9 C.sub.3 H.sub.7 -i Q1 B4 NH.sub.2 H1681 A9 C.sub.3 H.sub.7 -i Q2 B4 NH.sub.2 H1682 A9 C.sub.3 H.sub.7 -i Q3 B4 NH.sub.2 H1683 A9 C.sub.3 H.sub.7 -i Q4 B4 NH.sub.2 H1684 A9 C.sub.3 H.sub.7 -i Q44 B4 NH.sub.2 H1685 A9 C.sub.3 H.sub.7 -i Q46 B4 NH.sub.2 H1686 A9 C.sub.3 H.sub.7 -i Q47 B4 NH.sub.2 H1687 A9 C.sub.3 H.sub.7 -i CH.sub.3 B4 NH.sub.2 H1688 A9 Q1 H B1 NH.sub.2 H1689 A9 Q2 H B1 NH.sub.2 H1690 A9 Q3 H B1 NH.sub.2 H1691 A9 Q4 H B1 NH.sub.2 H1692 A9 Q44 H B1 NH.sub.2 H1693 A9 Q46 H B1 NH.sub.2 H1694 A9 Q47 H B1 NH.sub.2 H1695 A9 Q1 H B2 NH.sub.2 H1696 A9 Q2 H B2 NH.sub.2 H1697 A9 Q3 H B2 NH.sub.2 H1698 A9 Q4 H B2 NH.sub.2 H1699 A9 Q44 H B2 NH.sub.2 H1700 A9 Q46 H B2 NH.sub.2 H1701 A9 Q47 H B2 NH.sub.2 H1702 A9 Q1 H B3 NH.sub.2 H1703 A9 Q2 H B3 NH.sub.2 H1704 A9 Q3 H B3 NH.sub.2 H1705 A9 Q4 H B3 NH.sub.2 H1706 A9 Q44 H B3 NH.sub.2 H1707 A9 Q46 H B3 NH.sub.2 H1708 A9 Q47 H B3 NH.sub.2 H1709 A9 Q1 H B4 NH.sub.2 H1710 A9 Q2 H B4 NH.sub.2 H1711 A9 Q3 H B4 NH.sub.2 H1712 A9 Q4 H B4 NH.sub.2 H1713 A9 Q44 H B4 NH.sub.2 H1714 A9 Q46 H B4 NH.sub.2 H1715 A9 Q47 H B4 NH.sub.2 H1716 A10 Q57 CH.sub.3 B1 NH.sub.2 H1717 A10 Q57 CH.sub.3 B2 NH.sub.2 H1718 A10 Q57 CH.sub.3 B3 NH.sub.2 H1719 A10 Q57 CH.sub.3 B4 NH.sub.2 H1720 A10 Q57 CH.sub.3 B5 NH.sub.2 H1721 A10 Q57 CH.sub.3 B6 NH.sub.2 H__________________________________________________________________________ ##STR24##
TABLE 5__________________________________________________________________________Compound 'H-NMR .delta. ppm (Reference MeltingNo. Solvent substance TMS) point (.degree.C.)__________________________________________________________________________13 CDCl.sub.3 5.96(d, 1H, J=8.4Hz), 210.about.215 + 6.88.about.8.10(m, 9H), DMSO d-6 9.25(d, 1H, J=8.4Hz)25 CDCl.sub.3 5.41(brs, 2H), 5.83(d, 1H, J=8.4Hz), 169.about.172 + 6.12.about.6.45(m, 2H), 7.16.about.7.55(m, 2H), DMSO d-6 7.96.about.8.44(m, 2H), 8.44.about.8.70(m, 1H), 8.87(d, 1H, J=8.4Hz), 8.87.about.9.10(m, 1H)26 CDCl.sub.3 5.53(brs, 2H), 5.81(d, 1H, J=8.4Hz), 208.about.209 + 6.55(s, 1H), 7.26.about.7.70(m, 3H), DMSO d-6 8.15.about.9.53(m, 5H)27 CDCl.sub.3 5.51(brs, 2H), 5.99(d, 1H, J=8.4Hz), 177.about.180 + 6.63.about.7.53(m, 4H), (decomposed) DMSO d-6 7.90.about.8.46(m, 2H), 8.46.about.8.71(m, 1H), 8.77.about.9.11(m, 1H), 8.99(d, 1H, J=8.4Hz)100 CDCl.sub.3 2.35(s, 3H), 3.75(S, 3H), 5.30(brs, 2H), 184.about.189 + 5.90(d, 1H, J=8.4Hz), 6.70.about.7.29(m, 3H), (decomposed) DMSO d-6 7.89(s, 1H), 7.99(d, 1H, J=8.4Hz), 9.06(brs, 1H)101 CDCl.sub.3 2.35(s, 3H), 3.73(s, 3H), 5.34(brs, 173.about.177 + 2H), 5.77(d, 1H, J=8.4Hz), 6.91.about.7.37 (decomp.) DMSO d-6 (m, 3H), 7.94(s, 1H), 7.97(d, 1H, J=8.4Hz), 8.27(brs, 1H)104 CDCl.sub.3 1.19(s, 6H), 2.32(s, 3H), 3.72(s, 3H) 160.about.164 + 4.83.about.5.81(m, 2H), 5.29(brs, 2H), (decomposed) DMSO d-6 7.59(d, 1H, J=7.2Hz), 7.87(s, 1H) 7.91(brs, 1H)156 CDCl.sub.3 2.17(s, 3H), 3.98(s, 3H), 5.23(brs, 159.about.162 + 2H), 5.79(d, 1H, J=8.4Hz), 6.10.about.6.37 DMSO d-6 (m, 2H), 6.46(s, 1H), 7.09.about.7.43(m, 1H), 8.21(d, 1H, J=8.4Hz), 8.97(brs, 1H)157 CDCl.sub.3 2.22(s, 3H), 4.04(s, 3H), 5.45 139.about.141 + (brs, 2H), 5.73(d, 1H, J=8.4Hz) DMSO d-6 6.45.about.6.70(m, 1H), 6.68(S, 1H) 7.35.about.7.70(m, 2H), 8.55((d, 1H, J=8.4Hz) 9.10(brs, 1H)158 CDCl.sub.3 2.15(s, 3H), 3.95(s, 3H), 168.about.170 + 5.38(brs, 2H), 5.86(d, 1H, J=8.4Hz), DMSO d-6 6.48(s, 1H), 6.64.about.7.28(m, 3H), 8.47((d, 1H, J=8.4Hz), 9.08(brs, 1H)159 CDCl.sub.3 2.24(s, 3H), 4.10(s, 3H), 5.06.about.5.46 176.about.178 + (m, 2H), 5.94(d, 1H, J=8.4Hz), 6.62(s, DMSO d-6 1H), 7.11.about.7.51(m, 3H), 8.37(d, 1H, J=8.4Hz), 9.26(brs, 1H)173 CDCl.sub.3 1.33(t, 3H, J=6.60Hz), 2.21(S, 3H) 164.about.166 + 4.45(q, 2H, J=6.60Hz), 5.50(brs, 2H) DMSO d-6 5.80(d, 1H, J=9.00Hz), 6.25.about.6.50 (m, 2H), 6.68(S, 1H), 7.45.about.7.60(m, 1H), 8.71(d, 1H, J=9.00Hz), 9.38(brs, 1H)175 CDCl.sub.3 1.33(t, 3H, J=7.20Hz), 2.21(S, 3H) 177.about.179 + 4.46(q, 2H, J=7.20Hz), 5.60(brs, 2H) DMSO d-6 5.97(d, 1H, J=9.00Hz), 6.68(s, 1H) 6.80.about.7.50(m, 3H), 8.83(d, 1H, J=9.00Hz), 9.47(brs, 1H)176 CDCl.sub.3 1.30(t, 3H, J=7.20Hz), 2.15(S, 3H) 174.about.177 + 4.38(q, 2H, J=7.20Hz), 5.38(brs, 2H) DMSO d-6 5.71(d, 1H, J=9.00Hz), 6.54(s, 1H) 6.80.about.7.30(m, 4H), 8.42(d, 1H, J=9.00Hz)179 CDCl.sub.3 1.42(d, 6H, J=6.60Hz), 2.23(S, 3H) 165.about.166 + 5.24(bs, 2H), 5.35(qq, 1H, J=6.60Hz), DMSO d-6 5.76(d, 1H, J=8.40Hz), 6.15.about.6.35 (m, 2H), 6.41(S, 1H), 7.15.about.7.35(m, 1H), 8.00.about.8.50(m, 2H)180 CDCl.sub.3 1.42(d, 6H, J=6.60Hz), 2.24(S, 3H) 171.about.173 + 5.45(brs, 2H), 5.45(qq, 1H, J=6.60Hz), DMSO d-6 5.74(d, 1H, J=8.40Hz), 6.45.about.6.60 (m, 1H), 6.61(S, 1H), 7.45.about.7.70(m, 2H), 8.47(d, 1H, J=8.40Hz), 9.40(brs, 1H)181 CDCl.sub.3 1.43(d, 6H, J=6.60Hz), 2.26(S, 3H) 190.about.192 + 5.53(brs, 2H), 5.45(qq, 1H, J=6.60Hz), DMSO d-6 6.03(d, 1H, J=8.40Hz), 6.61(s, 1H) 6.90.about.7.50(m, 3H), 8.74(d, 1H, J=8.40Hz), 9.40(brs, 1H)182 CDCl.sub.3 1.50(d, 6H, J=6.60Hz), 2.23(S, 3H) 208.about.209 + 5.55(brs, 2H), 5.50(qq, 1H, J=6.60Hz), DMSO d-6 5.87(d, 1H, J=9.00Hz), 6.66(s, 1H) 7.10.about.7.55(m, 3H), 8.71(d, 1H, J=9.00Hz), 9.47(brs, 1H)306 CDCl.sub.3 1.36.about.2.83(m, 6H), 2.19(s, 3H), 179.about.180 + 5.38(brs, 2H), 5.51(quint, 1H, J=8.4Hz), DMSO d-6 5.71(d, 1H, J=9.0Hz), 6.05.about.6.35(m, 2H), 6.50(s, 1H), 7.22.about.7.40(m, 1H), 8.45(d, 1H, J=9.0Hz), 9.07(brs, 1H)311 CDCl.sub.3 1.35.about.2.82(m, 6H), 2.17(s, 3H), 178.about.183 + 5.40(brs, 2H), 5.47(quint, 1H, J=8.4Hz), (decomposed) DMSO d-6 5.61(d, 1H, J=8.4Hz), 6.30.about.6.48(m, 1H), 6.53(s, 1H), 7.26.about.7.60(m, 2H), 8.40(d, 1H, J=8.4Hz), 9.10(brs, 1H)316 CDCl.sub.3 1.45.about.2.90(m, 6H), 2.21(s, 3H), 192.about.196 + 5.40(brs, 2H), 5.50(quint, 1H, J=8.4Hz), (decomposed) DMSO d-6 5.80(d, 1H, J=9.0Hz), 6.47(s, 1H), 6.71.about.7.00(m, 2H), 7.02.about.7.26(m, 1H), 8.50(d, 1H, J=9.0Hz), 9.10(brs, 1H)317 CDCl.sub.3 1.33.about.2.35(m, 8H), 2.16(s, 3H), 194.about.201 + 5.50(brs, 2H), 5.10.about.5.65(m, 1H), (decomposed) DMSO d-6 5.79(d, 1H, J=7.8Hz), 6.50(s, 1H), 6.70.about.7.08(m, 2H), 7.10.about.7.28(m, 1H), 8.58(d, 1H, J=7.8Hz), 9.11(brs, 1H)321 CDCl.sub.3 1.37.about.2.96(m, 6H), 2.19(s, 3H), 193.about.194 + 5.33(brs, 2H), 5.51(quint, 1H, J=8.4Hz), DMSO d-6 5.71(d, 1H, J=9.0Hz), 6.45(s, 1H), 6.85.about.7.33(m, 3H), 8.34(d, 1H, J=9.0Hz), 9.08(brs, 1H)343 CDCl.sub.3 0.80(t, 3H, J=6.6Hz), 169.about.173 + 1.37(d, 3H, J=6.6Hz), 1.48.about.2.00(m, 2H), DMSO d-6 2.19(s, 3H), 5.13(qt, J=6.6Hz), 5.47(brs, 2H), 5.85(d, 1H, J=9.0Hz), 6.46(s, 1H), 6.70.about.7.30(m, 3H), 8.55(d, 1H, J=9.0Hz), 9.22(brs, 1H)439 CDCl.sub.3 5.32(bs, 2H), 6.11(d, 2H, J=52.8Hz), 113.about.116 + 6.10.about.6.30(m, 1H), 6.70(d, 2H, J=9.0Hz), DMSO d-6 7.40.about.7.55(m, 1H), 7.75.about. 7.90(m, 1H), 7.95.about.8.25(m, 1H), 8.40.about.8.70(m, 1H), 9.33(d, 1H, J=9.0Hz), 9.55(bs, 1H)448 CDCl.sub.3 1.40(d, 6H, J=6.6Hz), 133.about.135 + 5.45(qq, 1H, J=6.6Hz), 5.60(brs, 2H), DMSO d-6 5.85.about.6.15(m, 2H), 6.80.about.7.60(m, 4H), 8.70(d, 1H, J=8.4Hz), 8.92(brs, 1H)1007 CDCl.sub.3 0.20.about.0.60(m, 4H), 0.95.about.1.55(m, 1H), 177.about.180 + 2.20(s, 3H), 4.24(d, 2H, J=7.8Hz), DMSO d-6 5.37(brs, 2H), 5.91(d, 1H, J=9.0Hz), 6.49(s, 1H), 6.72.about.7.25(m, 3H), 8.48(d, 1H, J=9.0Hz), 8.55(brs, 1H)1013 CDCl.sub.3 0.83(d, 3H, J=6.6Hz), 2.17(s, 3H), 190.about.193 + 1.75.about.2.35(m, 1H), 4.22(d, 2H, J=7.8Hz), DMSO d-6 5.39(brs, 2H), 5.91(d, 1H, J=9.0Hz), 6.50(s, 1H), 6.70.about.7.25(m, 3H), 8.45(d, 1H, J=9.0Hz), 8.60(brs, 1H)1023 CDCl.sub.3 2.23(s, 3H), 4.11(s, 3H), -- + 6.18(s, 1H), 6.68(s, 1H), DMSO d-6 6.88.about.7.48(m, 5H)1024 CDCl.sub.3 2.26(s, 3H), 4.15(s, 3H), 144.about.145 + 5.93(s, 1H), 6.68(s, 1H), DMSO d-6 7.07.about.7.53(m, 5H)1028 CDCl.sub.3 2.25(s, 3H), 4.10(s, 3H), -- 6.64(s, 1H), 7.05.about. 7.70(m, 3H) 8.18.about.8.32(m, 1H), 9.25(brs, 1H)1033 CDCl.sub.3 2.22(s, 3H), 3.83(s, 3H), 4.03(s, 3H), -- 4.82(brs, 2H), 5.76(d, 1H, J=7.2Hz), 6.39(s, 1H), 7.07.about.7.67(m, 4H)1034 CDCl.sub.3 2.23(s, 3H), 4.07(S, 3H), -- + 4.40(d, 2H, J=6.0Hz), 4.97.about.6.02(m, 4H), DMSO d-6 5.62(brs, 2H), 6.67(S, 1H), 7.07.about.7.52(m, 3H), 7.99(d, 1H, J=8.4Hz)1035 CDCl.sub.3 0.70.about.1.90(m, 9H), 2.21(s, 3H), -- 4.02(s, 3H), 4.73(brs, 2H), 5.72(d, 1H, J=7.2Hz), 6.35(s, 1H), 7.03.about.7.68(m, 4H)1037 CDCl.sub.3 2.17(s, 3H), 3.96(s, 3H), 187.about.189 5.88(d, 1H, J=9.0Hz), 6.54(brs, 2H), 6.61(s, 1H), 7.00.about.7.55(m, 6H), 7.85.about.8.15(m, 2H), 8.57(d, 1H, J=9.0Hz)1038 CDCl.sub.3 2.23(s, 3H), 2.80(d, 3H, J=4.8Hz), 102.about.104 4.08(s, 3H), 5.63.about.6.58(m, 3H), 6.59(s, 1H), 6.35.about.6.80(brs, 1H), 7.05.about.7.45(m, 3H), 7.80(d, 1H, J=9.0Hz)1039 CDCl.sub.3 1.14(d, 6H, J=7.2Hz), 2.20(s, 3H), -- 4.03(s, 3H), 5.60.about.6.10(m, 3H), 6.38(d, 1H, J=7.8Hz), 6.58(s, 1H), 6.98.about.7.48(m, 4H), 7.85(d, 1H, J= 9.6Hz)1040 CDCl.sub.3 2.25(s, 3H), 4.10(S, 3H), 185.about.188 + 6.06(d, 1H, J=8.0Hz), 6.31(brs, 2H), DMSO d-6 6.71(s, 1H), 6.96.about.7.71(m, 8H), 8.66(d, 1H, J=8.0Hz), 8.98(s, 1H)1041 CDCl.sub.3 2.25(s, 3H), 4.10(s, 3H), 181.about.185 + 6.09(d, 1H, J=9.6Hz), 6.73(brs, 2H) DMSO d-6 6.92(s, 1H), 7.18.about.7.85(m, 7H), 9.00(d, 1H, J=9.6Hz)1042 CDCl.sub.3 2.20(s, 3H), 3.12(s, 3H), 4.04(s, 3H) 101.about.103 5.93(brs, 2H), 6.54(s, 1H), 7.04.about.7.77(m, 6H)1043 CDCl.sub.3 1.31(t, 3H, J=6.6Hz), 2.22(s, 3H), -- + 4.06(s, 3H), 4.24(q, 2H, J=6.6Hz), DMSO d-6 5.92(d, 1H, J=9.6Hz), 6.46(brs, 2H), 6.72(s, 1H), 7.23.about.7.68(m, 3H), 8.69(d, 1H, J=9.6Hz)1539 CDCl.sub.3 1.80.about.2.72(m, 4H), 2.16(s, 3H), 187.about.188 + 5.28.about.6.34(m, 6H), 6.51(s, 1H), DMSO d-6 6.65.about.7.03(m, 2H), 7.08.about.7.26(m, 1H), 8.57(d, 1H, J=9.0Hz), 9.18(brs, 1H)__________________________________________________________________________
The intermediates obtained during the course of the production of the compounds of the present invention are novel compounds. Thus the present invention further involves these compounds.
Accordingly, the present invention provides a compound represented by the general formula: ##STR25## wherein B represents a thienyl or a furyl group; and a salt thereof as well as a compound represented by the general formula: ##STR26## wherein R.sup.11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R.sup.12 represents hydroxyl or an alkoxy group having 1 to 8 carbon atoms or a halogen group.
The present invention further provides a fungicide containing an oxime derivative represented by the above general formula [I] as an active ingredient.
The fungicide of the present invention is effective not only on downy mildew and phytophthora rot of various crops but also on other diseases. Examples of major plant diseases include cucumber downy mildew, grape downy mildew, lettuce downy mildew, Chinese cabbage downy mildew, hop downy mildew, potato phytophthora rot, tomato phytophthora rot, cucumber gray phytophthora rot, green pepper phytophthora rot, damping-off of tomato, cucumber and rice caused by Pythium, and beat damping off caused by Aphanomyces.
The fungicide of the present invention may be applied by, for example, seed treatment, foliage application or soil application. The dose and concentration thereof may vary depending on the crop, the disease and its degree and the application method. Generally speaking, it may be applied at a ratio of 2 to 2000 g per ha, preferably 10 to 1000 g per ha, in terms of the active ingredient.
The concentration at the application may range from 1 to 1000 ppm, preferably from 5 to 500 ppm.
Since the agrohorticultural fungicide of the present invention exerts both of preventive and therapeutic effects, it may be applied over a wide range of time. Namely, it may be applied either before or after the occurrence of a disease.
It is needless to say that the fungicide of the present invention may be used together with various other biologically active compounds, for example, agricultural chemicals such as similar or supplementative fungicides, insecticides, herbicides and plant growth regulators, fertilizers and soil conditioners. Furthermore, the fungicide may be formulated into a product together with these materials.
The fungicide of the present invention may be mixed with an appropriate carrier, for example, a solid carrier such as clay, talc, bentonite or diatomaceous earth; or a liquid one such as water, an alcohol such as methanol or ethanol, an aromatic hydrocarbon such as benzene, toluene or xylene, a chlorinated hydrocarbon, an ether, a ketone, an ester such as ethyl acetate or an acid amide such as dimethylformamide. Further, various additives such as emulsifiers, dispersants, suspending agents, penetrating agent spreaders or stabilizers may be added thereto if desired. Thus the fungicide of the present invention may be formulated into any desirable form such as emulsion, oil, wettable powder, dust, granules or flowable.
Now examples of the compositions of these formulations will be given, though the present invention is not restricted thereby. In the following compositions, all parts are by weight.
______________________________________(1) Wettable powder______________________________________ compound of the invention 5 to 75 parts solid carrier 9 to 86 parts surfactant 5 to 10 parts other components 0 to 5 parts______________________________________
Examples of the solid carrier include calcium carbonate, kaolinite, Zeeklite A, Zeeklite PEP, diatomaceous earth and talc. Examples of the surfactant include Lunox 1000C, Solpol 5039, Solpol 5050, Solpol 005D, Solpol 5029-0, calcium sulfonate and sodium dodecylsulfonate.
An example of other components is Carplex #80.
______________________________________(2) Emulsion______________________________________ compound of the invention 5 to 50 parts liquid carrier 35 to 90 parts surfactant 5 to 15 parts______________________________________
Examples of the liquid carrier include xylene, dimethylformamide, methylnaphthalene and isophorone.
Examples of the surfactant include Solpol 2680, Solpol 3005X and Solpol 3346.
______________________________________(3) Flowable______________________________________ compound of the invention 5 to 75 parts liquid carrier 14.5 to 68 parts surfactant 5 to 10 parts other components 1 to 10 parts______________________________________
Water is used as the liquid carrier.
Examples of the surfactant include Lunox 1000C, Solpol 3353, Solpol FL, Nippol, Agrisol S-710 and sodium ligninsulfonate.
Examples of other components include ethylene glycol, propylene glycol and xanthan gum.
______________________________________(4) Dust______________________________________ compound of the invention 0.03 to 20 parts solid carrier 94 to 98.97 parts other components 0 to 3 parts______________________________________
Examples of the solid carrier include calcium carbonate, kaolinite, Zeeklite and talc.
Examples of other components include diisopropyl phosphate and Carplex #80.
______________________________________(5) Granules______________________________________ compound of the invention 0.3 to 10 parts solid carrier 92 to 98.7 parts other components 0 to 5 parts______________________________________
Examples of the solid carrier include calcium carbonate, kaolinite, bentonite and talc.
Examples of other components include calcium ligninsulfonate and polyvinyl alcohol.
Now, particular examples of the formulation of the fungicide of the present invention containing the oxime derivative of the present invention represented by the general formula [1] as an active ingredient will be given, though the present invention is not restricted thereby. In the following composition, all parts are by weight.
FORMULATION EXAMPLE 1
______________________________________Wettable powder______________________________________compound of the invention 5 partsZeeklite PFP 87 parts(mixture of kaolinite andsericite; mfd. byZeeklite Kogyo)Solpol 5039 5 parts(mixture of anionic surfactantand white carbon; mfd. byToho Chemical IndustryCo., Ltd.)Carplex #80 3 parts(white carbon; mfd. byShionogi & Co., Ltd.)______________________________________
The above components were homogeneously mixed together and ground to thereby give a wettable powder. At the use, the product was diluted 100 to 10,000-fold and applied in such a manner as to give a dose of the active ingredient of 10 to 1000 g/ha.
FORMULATION EXAMPLE 2
______________________________________Wettable powder______________________________________compound of the invention 25 partsZeeklite PFP 69 parts(mixture of kaolinite andsericite; mfd. byZeeklite Kogyo)Solpol 5039 3 parts(mixture of anionic surfactantand white carbon; mfd. byToho Chemical IndustryCo., Ltd.)Carplex #80 3 parts(white carbon; mfd. byShionogi & Co., Ltd.)______________________________________
The above components were homogeneously mixed together and ground to thereby give a wettable powder. At the use, the product was diluted 500 to 50,000-fold and applied in such a manner as to give a dose of the active ingredient of 10 to 1000 g/ha.
FORMULATION EXAMPLE 3
______________________________________Wettable powder______________________________________compound of the invention 20 partscalcium carbonate (powder) 69 partsSolpol 5050 10 parts(mixture of anionic surfactantand white carbon; mfd. byToho Chemical IndustryCo., Ltd.)Carplex #80 1 parts(white carbon; mfd. byShionogi & Co., Ltd.)______________________________________
The above components were homogeneously mixed together and ground to thereby give a wettable powder. At the use, the product was diluted 400 to 40,000-fold and applied in such a manner as to give a dose of the active ingredient of 10 to 1000 g/ha.
FORMULATION EXAMPLE 4
______________________________________Emulsion______________________________________compound of the invention 5 partsxylene 70 partsN,N-dimethylformamide 20 partsSolpol 2680 5 parts(mixture of nonionic surfactantand anionic surfactant; mfd.by Toho Chemical IndustryCo., Ltd.)______________________________________
The above components were homogeneously mixed together to thereby give an emulsion. At the use, the product was diluted 100 to 10,000-fold and applied in such a manner as to give a dose of the active ingredient of 10 to 1000 g/ha.
FORMULATION EXAMPLE 5
______________________________________Emulsion______________________________________compound of the invention 50 partsxylene 25 partsN,N-dimethylformamide 10 partsSolpol 3346 15 parts(mixture of nonionic surfactantand anionic surfactant; mfd.by Toho Chemical IndustryCo., Ltd.)______________________________________
The above components were homogeneously mixed together to thereby give an emulsion. At the use, the product was diluted 500 to 50,000-fold and applied in such a manner as to give a dose of the active ingredient of 10 to 1000 g/ha.
FORMULATION EXAMPLE 6
______________________________________Flowable______________________________________compound of the invention 5 partsSolpol 3353 5 parts(nonionic surfactant; mfd. byToho Chemical IndustryCo., Ltd.)Lunox 1000C 3 parts(anionic surfactant; mfd. byToho Chemical IndustryCo., Ltd.)1% aqueous solution of 20 partsxanthan gum(natural polymer)water 57 partsethylene glycol 10 parts______________________________________
The above components other than the active ingredient, i.e., the compound of the invention, were homogeneously dissolved. Then the compound of the invention was added thereto and the mixture was thoroughly stirred and wet-ground with a sand mill to thereby give a flowable. At the use, the product was diluted 100 to 10,000-fold and applied in such a manner as to give a dose of the active ingredient of 10 to 1000 g/ha.
FORMULATION EXAMPLE 7
______________________________________Flowable______________________________________compound of the invention 75 partsSolpol 3353 5 parts(nonionic surfactant; mfd. byToho Chemical IndustryCo., Ltd.)Lunox 1000C 0.5 parts(anionic surfactant; mfd. byToho Chemical LndustryCo., Ltd.)1% aqueous solution of 10 partsxanthan gum(natural polymer)water 4.5 partspropylene glycol 5 parts______________________________________
The above components other than the active ingredient, i.e., the compound of the invention, were homogeneously dissolved. Then the compound of the invention was added thereto and the mixture was thoroughly stirred and wet-ground with a sand mill to thereby give a flowable. At the use, the product was diluted 1500 to 150,000-fold and applied in such a manner as to give a dose of the active ingredient of 10 to 1000 g/ha.
FORMULATION EXAMPLE 8
______________________________________Dust______________________________________compound of the invention 10 partsclay 90 parts______________________________________
The above components were homogeneously mixed together to thereby give a dust. At the use, the product was applied as such to thereby give a dose of the active ingredient of 10 to 1000 g/ha.
FORMULATION EXAMPLE 9
______________________________________Granules______________________________________compound of the invention 5 partsbentonite 25 partstalc 70 parts______________________________________
The above components were homogeneously mixed together and ground. Then a small amount of water was added thereto and the mixture was stirred and granulated with an extruder. After drying, granules were obtained.
At the use, the product was applied as such so as to give a dose of the active ingredient of 10 to 1000 g/ha.
To illustrate the effects of the compounds of the present invention examined by biological tests, the following Test Examples will be given.
TEST EXAMPLE 1
Preventive effect on cucumber downy mildew
Cucumber seedlings (variety: Sagami Hanpaku were grown in pots of 7 cm in diameter. When these seedlings grew into the mono- or difoliate stage, an emulsion of a test compound, which had been prepared according to the method described in Formulation Example 4 or 5 and diluted with water at a concentration of 500 ppm was sprayed with a spray gun in a dose of 20 ml/pot. On the next day of the application, a spore suspension (2.times.10.sup.5 /ml) of Pseudoperonospora cubensis was sprayed to the seedlings, which were then stored in an inoculation box at 25.degree. C. at a humidity of at least 95% over day and night. Next, these seedlings were placed in a greenhouse. Seven days after the inoculation, the ratio of lesions thus formed on the inoculated leaves was determined and the preventive value was calculated according to the following equation: ##EQU1##
The following Table 6 shows the results.
TABLE 6______________________________________(Application conc.: 500 ppm)Cpd. No. Preventive value Chemical damage______________________________________ 25 100 none 26 100 do. 27 100 do.100 100 do.101 100 do.104 100 do.156 100 do.157 100 do.158 100 do.159 100 do.173 100 do.175 100 do.176 100 do.179 100 do.180 100 do.181 100 do.182 100 do.306 100 do.311 100 do.316 100 do.317 100 do.321 100 do.343 100 do.439 100 do.1007 100 do.1013 100 do.1023 100 do.1024 100 do.1028 100 do.1033 100 do.1037 100 do.1042 100 do.1043 100 do.1539 100 do.______________________________________
TEST EXAMPLE 2
Therapeutic effect on cucumber downy mildew
Cucumber seedlings (variety: Sagami Hanpaku) were grown in pots of 7 cm in diameter. When these seedlings grew into the mono- or difoliate stage, a spore suspension (2.times.10.sup.5 /ml) of Pseudoperonospora cubensis was sprayed to the seedlings, which were then stored in an inoculation box at 25.degree. C at a humidity of at least 95% over day and night. 0n the next day, an emulsion of a test compound, which had been prepared according to the method described in Formulation Example 4 or 5 and diluted with water to a concentration of 500 ppm, was sprayed with a spray gun in a dose of 20 ml/pot. Next, these seedlings were placed in a greenhouse. Seven days after the inoculation, the ratio of lesions thus formed on the inoculated leaves was determined and the preventive value was calculated according to the following equation: ##EQU2##
The following Table 7 shows the results.
TABLE 7______________________________________(Application conc.: 500 ppm)Cpd. No. Preventive value Chemical damage______________________________________ 25 100 none 26 100 do. 27 100 do.100 100 do.101 100 do.104 100 do.156 100 do.157 100 do.158 100 do.159 100 do.173 100 do.175 100 do.176 100 do.179 100 do.180 100 do.181 100 do.182 100 do.306 100 do.311 100 do.316 100 do.317 100 do.321 100 do.439 100 do.1007 100 do.1013 100 do.1023 100 do.1024 100 do.1033 100 do.1037 100 do.1042 100 do.1043 100 do.1539 100 do.______________________________________
TEST EXAMPLE 3
Preventive effect on tomato phytophthora rot
Tomato seedlings (variety: Fukuju) were grown in pots of 8 cm in diameter. When these seedlings grew into the trifoliate stage, a wettable powder, which had been prepared according to the method described in Formulation Examples 1 to 3 and diluted with water to a given concentration of the active ingredient was sprayed with a spray gun in a dose of 20 ml/pot. On the next day of the application, a spore suspension (2.times.10.sup.5 /ml) of Phytophthora infestans was sprayed to the seedlings, which were then stored in an inoculation box at 20.degree. C. at a humidity of at least 95% for five days. Then the ratio of lesions thus formed on the inoculated leaves was determined and the preventive value was calculated according to the following equation: ##EQU3##
The following Table 8 shows the results.
TABLE 8______________________________________(Application conc.: 500 ppm)Cpd. No. Preventive value Chemical damage______________________________________ 25 100 none 26 100 do. 27 100 do.100 100 do.101 100 do.104 100 do.156 100 do.157 100 do.158 100 do.159 100 do.173 100 do.175 100 do.176 100 do.179 100 do.180 100 do.181 100 do.182 100 do.306 100 do.311 100 do.316 100 do.317 100 do.321 100 do.439 100 do.1007 100 do.1013 100 do.1023 100 do.1024 100 do.1037 100 do.1042 100 do.1043 100 do.1539 100 do.______________________________________
TEST EXAMPLE 4
Therapeutic effect on tomato phytophthora rot
Tomato seedlings (variety: Fukuju) were grown in pots of 8 cm in diameter. When these seedlings grew into the trifoliate stage, a spore suspension (2.times.10.sup.5 /ml) of Phytophthora infestans was sprayed to the seedlings, which were then stored in an inoculation box at 20.degree. C. at a humidity of at least 95% over day and night. On the next day, a wettable powder, which had been prepared according to the method described in Formulation Examples 1 to 3 and diluted with water to a given concentration of the active ingredient, was sprayed with a spray gun in a dose of 20 ml/pot. After air-drying, these seedlings were placed in the above inoculation box. After five days, the ratio of lesions thus formed on the inoculated leaves was determined and the preventive value was calculated according to the following equation: ##EQU4##
The following Table 9 shows the results.
TABLE 9______________________________________(Application conc.: 500 ppm)Cpd. No. Preventive value Chemical damage______________________________________ 25 100 none 26 100 do. 27 100 do.100 100 do.101 100 do.104 100 do.156 100 do.157 100 do.158 100 do.159 100 do.173 100 do.175 100 do.176 100 do.179 100 do.180 100 do.181 100 do.182 100 do.306 100 do.311 100 do.316 100 do.317 100 do.321 100 do.439 100 do.1013 100 do.1023 100 do.1024 100 do.1028 100 do.1037 100 do.1042 100 do.1043 100 do.1539 100 do.______________________________________

Number	Date	Country
1-156079	Jun 1988	JPX
63-239538	Sep 1988	JPX
1-151055	Jun 1989	JPX

Oxime derivative and fungicide for agricultural and horticultural use

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