TREA

Novel herbicides

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  • Patent Grant
  • 4995902
  • Patent Number
    4,995,902
  • Date Filed
    Tuesday, July 11, 1989
    35 years ago
  • Date Issued
    Tuesday, February 26, 1991
    33 years ago
Information
Abstract
The invention relates to novel herbicidally active cyclohexanediones of formula I or I' ##STR1## in which R.sup.1 and R.sup.2 independently of one another are each hydrogen; halogen; nitro; cyano; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 alkoxy; C.sub.1 -C.sub.4 alkyl-S(O).sub.n --; COR.sup.8 ; C.sub.1 -C.sub.4 haloalkoxy; or C.sub.1 -C.sub.4 haloalkyl; R.sup.3, R.sup.4 and R.sup.5 independently of one another are each hydrogen; C.sub.1 -C.sub.4 alkyl; or phenyl or benzyl each unsubstituted or substituted by up to three identical or different substituents from halogen, nitro, cyano, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkyl-S(O).sub.n --, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 haloalkyl-S(O).sub.n -- and C.sub.1 -C.sub.4 haloalkoxy; R.sup.6 is hydrogen; C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxycarbonyl; or cyano; R.sup.7 is OH; or O.sup..crclbar. M.sup..sym. ; R.sup.8 is OH; C.sub.1 -C.sub.4 alkoxy; NH.sub.2 ; C.sub.1 -C.sub.4 alkylamino; or di-C.sub.1 - C.sub.4 alkylamino; n is 0, 1 or 2; M+ is a cation equivalent of a metal ion or of an ammonium ion that is unsubstituted or substituted by up to three C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 hydroxyalkyl or C.sub.1 -C.sub.4 alkoxy-C.sub.1 -C.sub.4 alkyl groups, to herbicidal compositions, to processes for the preparation of novel compounds and to novel intermediates and the preparation thereof.
Description

The present invention relates to novel cyclohexanediones having herbicidal activity, to agrochemical compositions containing those cyclohexanediones, to the use thereof for controlling undesired plant growth and to processes for the preparation of the compounds of the invention. The invention also relates to novel intermediates and to processes for the preparation thereof.
Numerous substituted cyclohexane-1,3-diones having herbicidal activity are already known. These compounds are not always satisfactory in terms of strength of activity, duration of activity, selectivity and applicability. It has surprisingly been found that, in contrast to these known compounds, the novel cyclohexane-1,3-diones of the general formula I and I' have good herbicidal activity.
The invention relates to the novel cyclohexane-1,3-diones of formula I or I' ##STR2## in which R.sup.1 and R.sup.2 independently of one another are each hydrogen; halogen; nitro; cyano; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 alkoxy; C.sub.1 -C.sub.4 alkyl--S(O)n-; COR.sup.8 ; C.sub.1 -C.sub.4 haloalkoxy; or C.sub.1 -C.sub.4 haloalkyl; R.sup.3, R.sup.4 and R.sup.5 independently of one another are each hydrogen; C.sub.1 -C.sub.4 alkyl; or phenyl or benzyl each unsubstituted or substituted by up to three identical or different substituents from halogen, nitro, cyano, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkyl-S(O)n--, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 haloalkyl-S(O).sub.n -- and C.sub.1 -C.sub.4 haloalkoxy; R.sup.6 is hydrogen; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 alkoxycarbonyl; or cyano; R.sup.7 is OH; or O.sup..crclbar. M.sup..sym. ; R.sup.8 is OH; C.sub.1 -C.sub.4 alkoxy; NH.sub.2 ; C.sub.1 -C.sub.4 alkylamino; or di-C.sub.1 -C.sub.4 alkylamino; n is 0, 1 or 2; M.sup..sym. is a cation equivalent of a metal ion or of an ammonium ion that is unsubstituted or substituted by up to three C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 hydroxyalkyl or C.sub.1 -C.sub.4 alkoxy-C.sub.1 C.sub.4 alkyl groups.
In the definitions used in this description, the generic terms used, and the substituents obtainable by combining individual sub-terms, include, for example, the following specific individual substituents, but this list does not imply any limitation of the invention.
Alkyl: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl and tert.-butyl; preferably methyl, ethyl and isopropyl.
Halogen: fluorine, chlorine, bromine and iodine; preferably fluorine, chlorine and bromine; especially preferably (for R: and R ) fluorine and chlorine and bromine.
Haloalkyl: fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl and dichlorofluoromethyl. Alkoxy: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, iso-butoxy, sec.-butoxy and tert.-butoxy; preferably methoxy.
Haloalkoxy: fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
Alkoxycarbonyl: methoxycarbonyl, ethoxycarbonyl, 4-propoxycarbonyl, isopropoxycarbonyl and n-butoxycarbonyl; preferably methoxycarbonyl and ethoxycarbonyl.
Alkylthio: methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec.-butylthio or tert.-butylthio; preferably methylthio and ethylthio.
Alkylsulfinyl: methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, sec.-butylsulfinyl, isobutylsulfinyl; preferably methylsulfinyl and ethylsulfinyl.
Alkylsulfonyl: methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, sec.-butylsulfonyl, isobutylsulfonyl; preferably methyl- and ethyl-sulfonyl.
In view of their chemical structure, the compounds of formula I can be regarded as 1,3-cyclohexanediones acylated in the 2-position. Numerous tautomeric forms can be derived from this basic structure. The invention includes all tautomers.
The individual meanings of the substituents R.sup.1 to R.sup.7, which are separated from each other by semi-colons, are to be regarded as sub-groups of those substituents. The invention includes also the definitions of compounds of formula I that can be obtained by deleting one or more of those subgroups.
The compounds of formula I and I' exist in an equilibrium of the two forms according to the following equation: ##STR3##
In the case of the hydroxy compounds (R.sup.7 =OH), apart from the three enol forms Ia, Ia"' and Ia', the triketo form Ia" may occur in accordance with the following tautomeric equilibrium: ##STR4## The invention includes all the tautomeric structures that can be derived from the basic structures I and I' and the salts thereof (R.sup.7 =O.sup..crclbar. M.sup..sym.).
Furthermore, the compounds of formula I and I" may be asymmetrically substituted (especially by the radicals R.sup.3 to R.sup.6 in the cyclohexane system). The invention includes both the racemate and the enriched and optically pure forms of the respective stereoisomers.
The asymmetrically substituted compounds of formula I are generally obtained in the form of racemates in the processes described in this application, provided chiral educts are not used. The stereoisomers can thus be resolved according to methods that are known per se, such as, for example, by fractional crystallisation after salt formation with optically pure bases, acids or meal complexes, or by chromatographic processes on the basis of the physicochemical properties.
Both the racemate and the stereoisomeric forms are included in the present invention.
Attention is drawn to the compounds of formula I or I' ##STR5## in which the pyridinecarbonyl radical is bonded by way of the 2-position of the pyridine system.
Attention is drawn also to the compounds of formula I or I' ##STR6## in which the radicals R.sup.1 and R.sup.2 are bonded in the 3- and 5-positions of the pyridine system.
Compounds of formula I or I' ##STR7## in which the radicals R.sup.1 and R.sup.2 are bonded in the 3- and 5-positions of the pyridine ring and the pyridinecarbonyl system is bonded by way of the 2-position of the pyridine ring are preferred.
Especially preferred are the compounds of formula I or I' ##STR8## in which R.sup.1 is hydrogen; halogen; nitro; cyano; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 alkoxy; C.sub.1 -C.sub.4 alkyl-S(O).sub.n -; COR.sup.8 ; C.sub.1 -C.sub.4 haloalkoxy; or C.sub.1 -C.sub.4 haloalkyl; R.sup.2 is hydrogen; halogen; nitro; cyano; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 alkoxy; C.sub.1 -C.sub.4 haloalkoxy; C.sub.1 -C.sub.4 alkyl-S(O).sub.n --; or C.sub.1 -C.sub.4 haloalkyl; R.sup.3, R.sup.4 and R.sup.5 independently of one another are each hydrogen; C.sub.1 -C.sub.4 alkyl; or phenyl or benzyl each unsubstituted or substituted by up to three identical or different substituents from halogen, nitro, cyano, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkyl-S(O).sub.n --, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 haloalkyl-S(O).sub.n -- and C.sub.1 -C.sub.4 haloalkoxy; R.sup.6 is hydrogen; C.sub.1 -C.sub.4 alkoxycarbonyl; or cyano; R.sup.7 is OH; or O.sup..crclbar. M.sup. .sym. ; R8 is OH; C.sub.1 -C.sub.4 alkoxy; NH.sub.2 ; C.sub.1 -C.sub.4 alkylamino; or di-C.sub.1 -C.sub.4 alkylamino; n is 0, 1 or 2; M.sup..sym. is a cation equivalent of an alkali metal ion, an alkaline earth metal ion or an ammonium ion; of a mono-C.sub.1 -C.sub.4 -alkylammonium ion; of a di-C.sub.1 -C.sub.4 alkylammonium ion; of a tri-C.sub.1 -C.sub.4 alkylammonium ion; or of a triethanolammonium ion.
Of the afore-mentioned compounds of formula I or I' within the scope of the broadest generic meaning, and also of the emphasised, preferred and especially preferred generic definitions, attention is drawn in each case especially to the sub-groups mentioned below:
(a) Compounds of formula I or I' in which at least one of the radicals R.sup.3 to R.sup.6 is hydrogen,
(b) Compounds of formula I or I' in which at least two of the radicals R.sup.3 to R.sup.6 are hydrogen,
(c) Compounds of formula I or I' in which R.sup.6 is cyano and R.sup.5 is hydrogen,
(d) Compounds of formula I or I' in which R.sup.6 is cyano, R.sup.5 is hydrogen and R.sup.3 and R.sup.4 independently of one another are each hydrogen or C.sub.1 -C.sub.14 alkyl,
(e) Compounds of formula I or I' in which R.sup.6 is C.sub.1 -C.sub.4 alkoxycarbonyl,
(f) Compounds of formula I or I' in which R.sup.7 is OH,
(g) Compounds of formula I or I' in which R.sup.7 is O.sup..crclbar. --M.sup..sym.,
(h) Compounds of formula I or I' in which R.sup.1 is hydrogen, chlorine, fluorine, nitro, trifluoromethyl, methoxy, bromine, methylthio, methylsulfonyl, carboxy, trichloromethyl or methyl,
(i) Compounds of formula I or I' in which R.sup.2 is hydrogen, chlorine, nitro, methylthio, methylsulfinyl, methylsulfonyl, methyl, fluorine, trifluoromethyl or trichloromethyl.
Attention is drawn especially to combinations of the sub-groups (a) to (e) with (h) and (i) both in the form of the free acid (group f)) and in the form of salts (group g)).
Especially preferred are compounds of formula I or I' in which R.sup.1 is hydrogen; fluorine; chlorine; bromine; nitro; cyano; methyl; trifluoromethyl; trichloromethyl; methoxy; methylthio; methylsulfinyl; methylsulfonyl; carboxy; carbamoyl; methoxycarbonyl; or ethoxycarbonyl; R.sup.2 is hydrogen; fluorine; chlorine; nitro; trifluoromethyl; trichloromethyl; methylthio; methylsulfinyl; or methylsulfonyl; R.sup.3 is hydrogen; C.sub.1 -C.sub.3 alkyl; phenyl; benzyl; or chlorophenyl; R.sup.4 is hydrogen; or methyl; R.sup.5 is hydrogen; or methyl; R.sup.6 is hydrogen; cyano; methyl; or C.sub.1 -C.sub.2 alkoxycarbonyl; R.sup.7 is OH; or O.sup..crclbar. M.sup..sym. ; is a cation equivalent of a sodium, lithium, calcium, trimethylammonium or triethanolammonium ion.
The following may be mentioned as individual compounds: 2-(3-chloro-5-trifluoromethylpyridin-2-ylcarbonyl) -cyclohex-1-en-1-ol-3-one and 2-(3-chloro-5-methylsulfonylpyridin-2-ylcarbonyl)-cyclohex-1-en-1-ol-3-one.
The compounds of formula Ia or Ia' in which the radicals R.sup.1 to R.sup.6 are as defined hereinbefore and R.sup.7 is OH can be prepared by
(a) reacting a cyclohexanedione of formula II, in which the radicals R.sup.3 to R.sup.6 are as defined hereinbefore, with a pyridine of formula III, in which R.sup.1 and R.sup.2 are as defined hereinbefore and X is halogen, preferably chlorine or bromine or the radical ##STR9## and R.sup.8 is C.sub.1 -C.sub.4 alkyl, phenyl or benzyl, in the presence of a base ##STR10## (b) thermal rearrangement of an ester of formula IV or IV' in which the radicals R.sup.1 to R.sup.6 are as defined hereinbefore ##STR11## preferably in the presence of cyanide.
The salts of formula Ib and Ib' in which the radicals R.sup.1 to R.sup.6 are as defined hereinbefore and R.sup.7 is O.sup..crclbar. M.sup..sym. can be prepared by
(c) reacting a cyclohexanedione Ia or Ia' in which R.sup.1 to R.sup.6 are as defined hereinbefore and R.sup.7 is OH with a base V in which B is OH.sup..crclbar. M.sup..sym., M.sup..sym. being as defined hereinbefore ##STR12##
The esters of formula IV and IV' are valuable intermediates for the preparation of the herbicidal end products Ia and Ia' respectively according to process variant (b). The invention thus also relates to the novel esters Iv and IV'. The esters IV and IV' can, however, also be formed as by-products in the acylation according to process variant (a).
(d) Furthermore, the compounds of formula Ic or Ic' in which one or more of the radicals R.sup.1 to R.sup.6 is (are) C.sub.1 -C.sub.4 alkyl-S(O).sub.n --, n representing 1 or 2, and the remaining radicals are as defined hereinbefore, can be prepared by oxidising a thioether of formula Id or Id', wherein the radical from the group R.sup.1 to R.sup.6 that is to be oxidised is C.sub.1 -C.sub.4 alkyl-S(O).sub.n --with n representing 0, and the remaining radicals are as defined hereinbefore. ##STR13##
Such oxidations are familiar to the person skilled in the art (for example Methodicum Chimicum, Ed. F. Korte, 9. Thieme Verlag Stuttgart 1976, vol. 7, pages 696-698 and the literature sources mentioned there for oxidation to sulfenes, and vol. 7, pages 751-755 and the literature mentioned there for oxidation to sulfones).
Oxidation with H.sub.2 O.sub.2 and with per acids, especially with 3-chloroperbenzoic acid, is preferred.
By appropriate selection of bases, solvents and other reaction parameters, such as temperature, concentration etc., the O-acylation may become the main reaction in accordance with the following scheme: ##STR14##
In the C-acylation according to process variant (a) it has proved advantageous to carry out the reaction in the presence of small amounts of cyanide. A low cyanide concentration can be ensured, for example, by the addition of acetone cyanohydrin.
The rearrangement of the esters IV and IV' can also advantageously be carried out under the action of cyanide ions and in the presence of a base.
Although the synthesis of the compounds of formula Ia and Ia' outlined as reaction (a) describes a process by which in principle all compounds included within the scope of formula Ia and Ia' can be produced, for reasons concerning economy and industrial scale production it may be appropriate to convert certain compounds of formula Ia and Ia' into other derivatives included within the scope of formula I and I'. Examples of such conversions, apart from reaction (c) and (d), are, for example, processes in which R.sup.6 represents an ester, halogen or cyano radical. These radicals can be converted analogously to the reactions illustrated hereinafter in Scheme 1 (IIa.fwdarw.IIb, IIc or IId) also even at the stage of compounds of formula I. Such derivatisation reactions are familiar to the person skilled in the art.
The above reactions are advantageously carried out in a solvent that is inert with respect to the reactions. Suitable inert solvents are hydrocarbons, such as benzene, toluene or xylene; ethers, such as diethyl ether, methyl isopropyl ether, glyme, diglyme; cyclic ethers, such as tetrahydrofuran and dioxane; ketones, such as acetone, methyl ethyl ketone; amides, such as dimethylformamide, N-methylpyrrolidone; sulfoxides, such as dimethyl sulfoxide; or chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or tetrachloroethane, alcohols, such as methanol, ethanol, isopropanol, propanol, butanol etc..
In some cases it is also advantageous to use mixtures of solvents in the form of organic solvents in admixture with water.
The reaction temperature can be varied within wide limits. Suitable reaction temperatures range, for example, from -20.degree. C. to the reflux temperature of the reaction mixture. The reaction is preferably carried out at a temperature of from 0.degree. C. to 100.degree. C.
In the case of reactions (a) and (b) a base is advantageously added. Suitable bases are, inter alia, sodium, potassium and calcium hydroxide, alkali metal and alkaline earth metal carbonates, amines, such as, for example triethylamine, or heterocycles, such as pyridine, 4-dimethylaminopyridine, DABCO and also alkali metal hydrides.
Reactions (a) and (b) can also advantageously be carried out under phase transfer conditions in two-phase systems. Such reactions are familiar to the person skilled in the art (for example described in Dehmlow and Dehmlow, Phase Transfer Catalysis, Verlag Chemie, Weinheim 1983; W. E. Keller, Phase Transfer Reactions Vol. 1 and Vol. 2, G. Thieme Verlag, Stuttgart 1986, 1987).
The cyclohexanediones of formula II are either known or can be prepared analogously to processes known in the literature.
The following malonic ester synthesis is a general method of obtaining the cyclohexanediones II in which first of all, in accordance with the scheme below, the specifically substituted cyclohexanediones IIa, IIb or IIc can be produced from an aldehyde or ketone VI and acetone: ##STR15##
The compounds of formula IIc in which the radicals R.sup.3 to R.sup.5 are as defined hereinbefore and R.sup.6 is cyano can be prepared in a modification of reaction scheme 1 by Michael addition of cyanoacetic acid ester XIII, in which R.sup.5 is as defined hereinbefore and R' is C.sub.1 -C.sub.4 alkyl, to the ketone VIII, in which R.sup.3 and R.sup.4 are as defined hereinbefore. ##STR16##
Of the pyridinecarboxylic acid derivatives III, it is especially the acid chlorides that are preferred.
The pyridine-2-carboxylic acid chloride IIIa may advantageously be prepared by a Pd-catalysed carbonylation reaction in accordance with the following reaction scheme 3: ##STR17##
In the above scheme, Hal is halogen (especially chlorine); R' is C.sub.1 -C.sub.4 alkyl and Pd-Cat is preferably PdCl.sub.2 (TPP).sub.2 a triphenylphosphine complex of palladium.
The picolinic acid derivatives XI, IIIa and XIV mentioned in scheme 3 are valuable intermediates for the synthesis of the cyclohexanediones I of the invention. Most of these compounds are novel.
The invention thus also relates to the novel picolinic acid derivatives of formula XV ##STR18## in which Y is OH; C.sub.1 -C.sub.4 alkoxy; or halogen; and R.sup.1 and R.sup.2 independently of one another are each halogen; nitro; cyano; C.sub.1 -C.sub.4 haloalkyl; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 alkoxy; or C.sub.1 -C.sub.4 alkyl-S(O).sub.n --; n is 0; 1; or 2; with the proviso that when Y is chlorine and the radical R.sup.1 is bonded in position 3 and the radical R.sup.2 is bonded in position 5, R.sup.1 and R.sup.2 are not simultaneously chlorine or simultaneously methyl, or when R.sup.1 is nitro R.sup.2 is not methyl.
Preferred are picolinic acid derivatives of formula XV' ##STR19## in which Y is OH; C.sub.1 -C.sub.4 alkoxy; or halogen; and R.sup.1 and R.sup.2 independently of one another are each halogen; nitro; cyano; C.sub.1 -C.sub.4 haloalkyl; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 alkoxy; or C.sub.1 -C.sub.4 alkyl-S(O).sub.n --; and n is 0; 1; or 2; with the proviso that when Y is chlorine, R.sup.1 and R.sup.2 are not simultaneously chlorine or simultaneously methyl, or R.sup.1 nitro and R methyl.
Especially preferred are the compounds of formula XV' in which Y is OH; C.sub.1 -C.sub.4 alkoxy; or halogen; R.sup.1 is hydrogen; and R.sup.2 is C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkyl; or cyano.
Also especially preferred are compounds of formula XV' in which Y is OH; C.sub.1 -C.sub.4 alkoxy; or halogen; R.sup.1 is C.sub.1 -C.sub.4 alkoxy; C.sub.1 -C.sub.4 haloalkyl; or cyano; and R.sup.2 is hydrogen.
Of the compounds of formula XV, and the compounds XV' mentioned as preferred and especially preferred, attention is drawn to the acid chlorides, that is to say those compounds in which Y is chlorine.
The compounds of formula I are highly active ingredients for plants that at suitable rates of application are excellently suitable as selective herbicides for controlling weeds in crops of useful plants. That is to say, at such rates of application the active ingredients of formula I are distinguished by a good selective herbicidal property against weeds. In particular, cereals, such as rye, barley, oats, wheat and maize, but also other crop plants, such as sorghum, rice, cotton, sugar cane or soybeans or also permanent crops (such as, for example, vines or plantations) remain virtually undamaged at low rates of application. At increased rates of application the growth of the crop plants is influenced only to a small extent. If the rates of application are very high, the substances of formula I have total herbicidal properties. The rates of application are generally from 0.001 to 4 kg. preferably from 0.005 to 2 kg of active substance per hectare.
At high rates of application the compounds of formula I can also be used as total herbicides. They are especially suitable for controlling weeds on paths, in public areas, on railway tracks or in other areas in which a total kill of the plants growing there is desired.
The selective herbicidal activity of the compounds of the invention is observed both in pre-emergence and post-emergence application. These compounds can therefore be used with equal success pre- or post-emergence in selective weed control.
Advantageously, the compounds or compositions of the invention can be applied also to the propagation material of the crop plant. Seed dressing, especially, may be mentioned here. Propagation material is seeds, plantlets or other parts of the plant from which the crop plants can be reared. The invention also relates to the propagation material treated with an effective amount of a compound of formula I.
The invention relates also to herbicidal compositions that contain a novel compound of formula I, and to methods for pre-and post-emergence weed control.
The compounds of formula I are used in unmodified form or, preferably, in the form of compositions together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant or extender, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Suitable solvents or extenders are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Both so-called water-soluble soaps and also water-soluble synthetic surface-active compounds are suitable anionic surfactants.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C.sub.10 -C.sub.22), e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C.sub.8 -C.sub.22 alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide, or phospholipids.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 10 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C.sub.8 -C.sub.4 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
Surfactants customary in the art of formulation are described, inter alia, in the following publications: "1986 International Mc Cutcheon's Emulsifiers and Detergents", Glen Rock, N.J., USA, 1986; H. Stache "Tensid Taschenbuch", 2nd edition, C. Hanser Verlag, Munich/Vienna, 1981; M. and J. Ash. "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.
The active ingredient preparations usually contain 0.1 to 95%, preferably 0.1 to 80%, of a compound of formula I, 1 to 99.9% of one or more solid or liquid adjuvants, and 0 to 25% of a surfactant.
Preferred formulations are composed especially as follows (throughout, percentages are by weight)
______________________________________Emulsifiable concentratesactive ingredient 1 to 20%, preferably 5 to 10%surfactant 5 to 30%, preferably 10 to 20%liquid carrier 50 to 94%, preferably 70 to 85%.Dustsactive ingredient 0.1 to 10%, preferably 0.1 to 1%solid carrier 99.9 to 90%, preferably 99.9 to 99%.Suspension concentratesactive ingredient 5 to 75%, preferably 10 to 50%water 94 to 25%, preferably 88 to 30%surfactant 1 to 40%, preferably 2 to 30%.Wettable powdersactive ingredient 0.5 to 90%, preferably 1 to 80%surfactant 0.5 to 20%, preferably 1 to 15%solid carrier 5 to 95%, preferably 15 to 90%.Granulatesactive ingredient 0.5 to 30%, preferably 3 to 15%solid carrier 99.5 to 70%, preferably 97 to 85%.______________________________________
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The formulations can be diluted to a concentration as low as 0.001% active ingredient.
The compositions may also contain further additives such as stabilisers, antifoams, viscosity regulators, binders, tackifiers and also fertilisers or other active ingredients for obtaining special effects.
The following Examples illustrate the invention.





P. PREPARATION EXAMPLES
P.1. Compounds of formula I
P.1.1. Reactions with cyclohexanediones of formula II
P.1.1.1. 2-(3-chloro-5-trifluoromethylpyridin-2-ylcarbonyl)-cyclohex1-en-1-ol-3-one
4.9 g (20 mmol) of 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid chloride are added dropwise to a solution of 2.2 g (20 mmol) of 1,3-cyclohexanedione and 7 ml (50 mmol) of triethylamine in 25 ml of dichloromethane, the temperature rising to 35.degree. C. The whole is then stirred at room temperature for 15 hours to complete the reaction. The black suspension is diluted with 250 ml of dichloromethane, adjusted to pH 1 with 1N HCl at from 0.degree. to 5.degree., and washed twice with H.sub.2 O. The product is subsequently extracted with 5% NaHCO.sub.3 solution, precipitated cold with 37% HCl, filtered with suction and dried. 4.0 g (63%) of the title compound of formula ##STR20## are isolated in the form of crystals having a melting point of 102.degree.-105.degree. C. (Compound No. 1.005).
P.1.1.2. 2-(5-trifluoromethylpyrid-2-ylcarbonl)-cyclohex-1-en-1-ol-3-one 20.4 g (85 mmol) of 5-trifluoromethylpyridine-2-carboxylic acid chloride are added dropwise at from 20.degree. to 25.degree. C. to a solution of 9.5 g (85 mmol) of 1,3-cyclohexanedione and 24 ml (170 mmol) of triethylamine in 85 ml of dichloromethane. After the whole has been stirred for 4 hours at room temperature, 0.8 ml of acetone cyanohydrin is added and stirring is continued for a further 15 hours. The reaction solution is diluted with 200 ml of dichloromethane, adjusted to pH 1 with 1N HCl at from 0.degree. to 5.degree. C., washed twice with water and extracted with 5% NaHCO.sub.3 solution. The extract is washed with dichloromethane, adjusted to pH 1 with 37% HCl, and the precipitated product is filtered with suction and dried.
17.2 g (71%) of the title compound of formula ##STR21## are isolated in the form of crystals having a melting point of 95.degree.-97.degree. C. (Compound No. 1.010).
The compounds of Table 1 can be synthesised analogously to the aforedescribed preparation process.
P.1.1.3. 2-(3-chloro-5-methylthiopyridin-2-ylcarbonyl)-cyclohex-1-en-1-ol-3-one
4.4 g (0.048 mol) of 1,3-cyclohexanedione and 10.6 g (0.048 mol) of 3-chloro-5-methylthiopyridine-2-carboxylic acid chloride are reacted analogously to P.1.1.1. and purified.
7.2 g (50.4%) of the title compound of formula ##STR22## are isolated in the form of crystals having a melting point of 113.degree. C. (decomp.) (Compound No. 1.018).
P.1.1.4. 2-(3-Chloro-5-methylsulfonyl-pyridin-2-yl-carbonyl)-cyclohex-1-en-1-ol-3-one
A solution of 5.6 g (50 mmol) 1.3-cyclohexanedione and 14 ml (100 mmol) of triethylamine in 50 ml dichloromethane is added at 0.degree. to 5.degree. C. to a suspension of 10.2 g (40 mmol) 3-chloro-5-methylsulfonyl-pyridine-2-carboxylic acid chloride in 80 ml dichloromethane. After stirring for 3 hours at room temperature 0.5 ml of aceton cyanhydrin are added to the suspension thus obtained. Stirring is continued for 3 hours at room temperature. The dark brown suspension is then diluted with 200 ml dichloromethane, adjusted to pH 1 with 1N HCl, and washed twice with water. The product is subsequently extracted with 5% NaHCO.sub.3 solution, precipitated cold with 37% HCl, filtered with suction and dried.
10.4 g (78.9%) of the title compound of formula ##STR23## are isolated in the form of white crystals having a melting point of >200.degree. C. (under decomp.) (Compound No. 1.020).
P.1.2.1. Preparation of 2-(3-chloro-5-methylsulfonylpyridin-2-yl-carbonyl) -cyclohex-1-en-1-ol-3one
A solution of 4.1 g (0.02 mol) of 85% 3-chloroperbenzoic acid in 50 ml of dichloromethane is added dropwise to a solution of 3 g (0.01 mol) of 2-(3-chloro-5-methylthiopyridin-2-ylcarbonyl)-cyclohex-1-en-1-ol-3-one in 25 ml of dichloromethane with cooling at from 20.degree. to 30.degree. C. The whole is then stirred at room temperature for 4 hours. The yellow suspension is filtered off from the chlorobenzoic acid and concentrated by evaporation on a rotary evaporator. The resulting mass is triturated with 50 ml of ether, filtered with suction and dried.
1.8 g (51.6%) of the title compound of formula ##STR24## are obtained in the form of crystals having a melting point of 150.degree. C. (decomp.) (Compound No. 1.020).
TABLE 1__________________________________________________________________________Compounds of formula ##STR25##Comp. No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 phys. data__________________________________________________________________________1.001 Cl Cl H H H H m.p. 144-146.degree. C.1.002 Cl H H H H H1.003 H Cl H H H H m.p. 106-107.degree. C.1.004 H H H H H H resin1.005 Cl CF.sub.3 H H H H m.p. 102-105.degree. C.1.006 NO.sub.2 H H H H H1.007 H NO.sub.2 H H H H1.008 NO.sub.2 Cl H H H H1.009 CF.sub.3 H H H H H1.010 H CF.sub.3 H H H H m.p. 95-97.degree. C.1.011 OCH.sub.3 H H H H H1.012 CN H H H H H1.013 OCH.sub.3 Cl H H H H1.014 CN Cl H H H H1.015 Br Cl H H H H1.016 SCH.sub.3 Cl H H H H1.017 SO.sub.2 CH.sub.3 Cl H H H H1.018 Cl SCH.sub.3 H H H H m.p. >113.degree. C. (decomp.)1.019 Cl SOCH.sub.3 H H H H m.p. 134-136.degree. C.1.020 Cl SO.sub.2 CH.sub.3 H H H H m.p. >150.degree. C. (decomp.)1.021 SOCH.sub.3 Cl H H H H1.022 SO.sub.2 CH.sub.3 H H H H H1.023 H SO.sub.2 CH.sub.3 H H H H1.024 H CH.sub.3 H H H H1.025 Cl F H H H H m.p. 113-115.degree. C.1.026 H CF.sub.3 H H H H1.027 F F H H H H1.028 F CF.sub.3 H H H H1.029 CF.sub.3 F H H H H1.030 H CCl.sub.3 H H H H1.031 CCl.sub.3 H H H H H1.032 Cl CCl.sub.3 H H H H1.033 CCl.sub.3 Cl H H H H1.034 CH.sub.3 H H H H H1.035 Cl Cl CH.sub.3 H H H m.p. 117-124.degree. C.1.036 Cl H CH.sub.3 H H H1.037 H Cl CH.sub.3 H H H1.038 H H CH.sub.3 H H H1.039 Cl CF.sub.3 CH.sub.3 H H H Fp. 93-103.degree. C.1.040 NO.sub.2 H CH.sub.3 H H H1.041 H NO.sub.2 CH.sub.3 H H H1.042 NO.sub.2 Cl CH.sub.3 H H H1.043 CF.sub.3 H CH.sub.3 H H H1.044 H CF.sub.3 CH.sub.3 H H H m.p. 99-101.degree. C.1.045 OCH.sub.3 H CH.sub.3 H H H1.046 CN H CH.sub.3 H H H1.047 OCH.sub.3 Cl CH.sub.3 H H H1.048 CN Cl CH.sub.3 H H H1.049 Br Cl CH.sub.3 H H H1.050 SCH.sub.3 Cl CH.sub.3 H H H1.051 SO.sub.2 CH.sub.3 Cl CH.sub.3 H H H1.052 Cl SCH.sub.3 CH.sub.3 H H H1.053 Cl SOCH.sub.3 CH.sub.3 H H H1.054 Cl SO.sub.2 CH.sub.3 CH.sub.3 H H H1.055 SOCH.sub.3 Cl CH.sub.3 H H H1.056 SO.sub.2 CH.sub.3 H CH.sub.3 H H H1.057 H SO.sub.2 CH.sub.3 CH.sub.3 H H H1.058 H CH.sub.3 CH.sub.3 H H H1.059 Cl F CH.sub.3 H H H1.060 H CF.sub.3 CH.sub.3 H H H1.061 F F CH.sub.3 H H H1.062 F CF.sub.3 CH.sub.3 H H H1.063 CF.sub.3 F CH.sub.3 H H H1.064 H CCl.sub.3 CH.sub.3 H H H1.065 CCl.sub.3 H CH.sub.3 H H H1.066 Cl CCl.sub.3 CH.sub.3 H H H1.067 CCl.sub.3 Cl CH.sub.3 H H H1.068 CH.sub.3 H CH.sub.3 H H H1.069 Cl Cl C.sub.2 H.sub.5 H H H1.070 Cl H C.sub.2 H.sub.5 H H H1.071 H Cl C.sub.2 H.sub.5 H H H1.072 H H C.sub.2 H.sub.5 H H H1.073 Cl CF.sub.3 C.sub.2 H.sub.5 H H H1.074 NO.sub.2 H C.sub.2 H.sub.5 H H H1.075 H NO.sub.2 C.sub.2 H.sub.5 H H H1.076 NO.sub.2 Cl C.sub.2 H.sub.5 H H H1.077 CF.sub.3 H C.sub.2 H.sub.5 H H H1.078 H CF.sub.3 C.sub.2 H.sub.5 H H H1.079 OCH.sub.3 H C.sub.2 H.sub.5 H H H1.080 CN H C.sub.2 H.sub.5 H H H1.081 OCH.sub.3 Cl C.sub.2 H.sub.5 H H H1.082 CN Cl C.sub.2 H.sub.5 H H H1.083 Br Cl C.sub.2 H.sub.5 H H H1.084 SCH.sub.3 Cl C.sub.2 H.sub.5 H H H1.085 SO.sub.2 CH.sub.3 Cl C.sub.2 H.sub.5 H H H1.086 Cl SCH.sub.3 C.sub.2 H.sub.5 H H H1.087 Cl SOCH.sub.3 C.sub.2 H.sub.5 H H H1.088 Cl SO.sub.2 CH.sub.3 C.sub.2 H.sub.5 H H H1.089 SOCH.sub.3 Cl C.sub.2 H.sub.5 H H H1.090 SO.sub.2 CH.sub.3 H C.sub. 2 H.sub.5 H H H1.091 H SO.sub.2 CH.sub.3 C.sub.2 H.sub.5 H H H1.092 H CH.sub.3 C.sub.2 H.sub.5 H H H1.093 Cl F C.sub.2 H.sub.5 H H H1.094 H CF.sub.3 C.sub.2 H.sub.5 H H H1.095 F F C.sub.2 H.sub.5 H H H1.096 F CF.sub.3 C.sub.2 H.sub.5 H H H1.097 CF.sub.3 F C.sub.2 H.sub.5 H H H1.098 H CCl.sub.3 C.sub.2 H.sub.5 H H H1.099 CCl.sub.3 H C.sub.2 H.sub.5 H H H1.100 Cl CCl.sub.3 C.sub.2 H.sub.5 H H H1.101 CCl.sub.3 Cl C.sub.2 H.sub.5 H H H1.102 CH.sub.3 H C.sub.2 H.sub.5 H H H1.103 Cl Cl n-C.sub.3 H.sub.7 H H H1.104 Cl H n-C.sub.3 H.sub.7 H H H1.105 H Cl n-C.sub.3 H.sub.7 H H H1.106 H H n-C.sub.3 H.sub.7 H H H1.107 Cl CF.sub.3 n-C.sub.3 H.sub.7 H H H1.108 NO.sub.2 H n-C.sub.3 H.sub.7 H H H1.109 H NO.sub.2 n-C.sub.3 H.sub.7 H H H1.110 NO.sub.2 Cl n-C.sub.3 H.sub.7 H H H1.111 CF.sub.3 H n-C.sub.3 H.sub.7 H H H1.112 H CF.sub.3 n-C.sub.3 H.sub.7 H H H1.113 OCH.sub.3 H n-C.sub.3 H.sub.7 H H H1.114 CN H n-C.sub.3 H.sub.7 H H H1.115 OCH.sub.3 Cl n-C.sub.3 H.sub.7 H H H1.116 CN Cl n-C.sub.3 H.sub.7 H H H1.117 Br Cl n-C.sub.3 H.sub.7 H H H1.118 SCH.sub.3 Cl n-C.sub.3 H.sub.7 H H H1.119 SO.sub.2 CH.sub.3 Cl n-C.sub.3 H.sub.7 H H H1.120 Cl SCH.sub.3 n-C.sub.3 H.sub.7 H H H1.121 Cl SOCH.sub.3 n-C.sub.3 H.sub.7 H H H1.122 Cl SO.sub.2 CH.sub.3 n-C.sub.3 H.sub.7 H H H1.123 SOCH.sub.3 Cl n-C.sub.3 H.sub.7 H H H1.124 SO.sub.2 CH.sub.3 H n-C.sub.3 H.sub.7 H H H1.125 H SO.sub.2 CH.sub.3 n-C.sub.3 H.sub.7 H H H1.126 H CH.sub.3 n-C.sub.3 H.sub.7 H H H1.127 Cl F n-C.sub.3 H.sub.7 H H H1.128 H CF.sub.3 n-C.sub.3 H.sub.7 H H H1.129 F F n-C.sub.3 H.sub.7 H H H1.130 F CF.sub.3 n-C.sub.3 H.sub.7 H H H1.131 CF.sub.3 F n-C.sub.3 H.sub.7 H H H1.132 H CCl.sub.3 n-C.sub.3 H.sub.7 H H H1.133 CCl.sub.3 H n-C.sub.3 H.sub.7 H H H1.134 Cl CCl.sub.3 n-C.sub.3 H.sub.7 H H H1.135 CCl.sub.3 Cl n-C.sub.3 H.sub.7 H H H1.136 CH.sub.3 H n-C.sub.3 H.sub.7 H H H1.137 Cl Cl i-C.sub.3 H.sub.7 H H H1.138 Cl H i-C.sub.3 H.sub.7 H H H1.139 H Cl i-C.sub.3 H.sub.7 H H H1.140 H H i-C.sub.3 H.sub.7 H H H1.141 Cl CF.sub.3 i-C.sub.3 H.sub.7 H H H m.p. 72-75.degree. C.1.142 NO.sub.2 H i-C.sub.3 H.sub.7 H H H1.143 H NO.sub.2 i-C.sub.3 H.sub.7 H H H1.144 NO.sub.2 Cl i-C.sub.3 H.sub.7 H H H1.145 CF.sub.3 H i-C.sub.3 H.sub.7 H H H1.146 H CF.sub.3 i-C.sub.3 H.sub.7 H H H m.p. 103-106.degree. C.1.147 OCH.sub.3 H i-C.sub.3 H.sub.7 H H H1.148 CN H i-C.sub.3 H.sub.7 H H H1.149 OCH.sub.3 Cl i-C.sub.3 H.sub.7 H H H1.150 CN Cl i-C.sub.3 H.sub.7 H H H1.151 Br Cl i-C.sub.3 H.sub.7 H H H1.152 SCH.sub.3 Cl i-C.sub.3 H.sub.7 H H H1.153 SO.sub.2 CH.sub.3 Cl i-C.sub.3 H.sub.7 H H H1.154 Cl SCH.sub.3 i-C.sub.3 H.sub.7 H H H1.155 Cl SOCH.sub.3 i-C.sub.3 H.sub.7 H H H1.156 Cl SO.sub.2 CH.sub.3 i-C.sub.3 H.sub.7 H H H1.157 SOCH.sub.3 Cl i-C.sub.3 H.sub.7 H H H1.158 SO.sub.2 CH.sub.3 H i-C.sub.3 H.sub.7 H H H1.159 H SO.sub.2 CH.sub.3 i-C.sub.3 H.sub.7 H H H1.160 H CH.sub.3 i-C.sub.3 H.sub.7 H H H1.161 Cl F i-C.sub.3 H.sub.7 H H H1.162 H CF.sub.3 i-C.sub.3 H.sub.7 H H H1.163 F F i-C.sub.3 H.sub.7 H H H1.164 F CF.sub.3 i-C.sub.3 H.sub.7 H H H1.165 CF.sub.3 F i-C.sub.3 H.sub.7 H H H1.166 H CCl.sub.3 i-C.sub.3 H.sub.7 H H H1.167 CCl.sub.3 H i-C.sub.3 H.sub.7 H H H1.168 Cl CCl.sub.3 i-C.sub.3 H.sub.7 H H H1.169 CCl.sub.3 Cl i-C.sub.3 H.sub.7 H H H1.170 CH.sub.3 H i-C.sub.3 H.sub.7 H H H1.171 Cl Cl n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.172 Cl H n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.173 H Cl n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.174 H H n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.175 Cl CF.sub.3 n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.176 NO.sub.2 H n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.177 H NO.sub.2 n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.178 NO.sub.2 Cl n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.179 CF.sub.3 H n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.180 H CF.sub.3 n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.181 OCH.sub.3 H n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.182 CN H n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.183 OCH.sub.3 Cl n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.184 CN Cl n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.185 Br Cl n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.186 SCH.sub.3 Cl n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.187 SO.sub.2 CH.sub.3 Cl n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.188 Cl SCH.sub.3 n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.189 Cl SOCH.sub.3 n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.190 Cl SO.sub.2 CH.sub.3 n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.191 SOCH.sub.3 Cl n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.192 SO.sub.2 CH.sub.3 H n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub. 51.193 H SO.sub.2 CH.sub.3 n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.194 H CH.sub.3 n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.195 Cl F n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.196 H CF.sub.3 n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.197 F F n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.198 F CF.sub.3 n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.199 CF.sub.3 F n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.200 H CCl.sub.3 n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.201 CCl.sub.3 H n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.202 Cl CCl.sub.3 n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.203 CCl.sub.3 Cl n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.204 CH.sub.3 H n-C.sub.3 H.sub.7 H H COOC.sub.2 H.sub.51.205 Cl Cl i-C.sub.3 H.sub.7 H H COOCH.sub.31.206 Cl H i-C.sub.3 H.sub.7 H H COOCH.sub.31.207 H Cl i-C.sub.3 H.sub.7 H H COOCH.sub.31.208 H H i-C.sub.3 H.sub.7 H H COOCH.sub.31.209 Cl CF.sub.3 i-C.sub.3 H.sub.7 H H COOCH.sub.3 m.p. 91-92.degree. C.1.210 NO.sub.2 H i-C.sub.3 H.sub.7 H H COOCH.sub.31.211 H NO.sub.2 i-C.sub.3 H.sub.7 H H COOCH.sub.31.212 NO.sub.2 Cl i-C.sub.3 H.sub.7 H H COOCH.sub.31.213 CF.sub.3 H i-C.sub.3 H.sub.7 H H COOCH.sub.31.214 H CF.sub.3 i-C.sub.3 H.sub.7 H H COOCH.sub.31.215 OCH.sub.3 H i-C.sub.3 H.sub.7 H H COOCH.sub.31.216 CN H i-C.sub.3 H.sub.7 H H COOCH.sub.31.217 OCH.sub.3 Cl i-C.sub.3 H.sub.7 H H COOCH.sub.31.218 CN Cl i-C.sub.3 H.sub.7 H H COOCH.sub.31.219 Br Cl i-C.sub.3 H.sub.7 H H COOCH.sub.31.220 SCH.sub.3 Cl i-C.sub.3 H.sub.7 H H COOCH.sub.31.221 SO.sub.2 CH.sub.3 Cl i-C.sub.3 H.sub.7 H H COOCH.sub.31.222 Cl SCH.sub.3 i-C.sub.3 H.sub.7 H H COOCH.sub.31.223 Cl SOCH.sub.3 i-C.sub.3 H.sub.7 H H COOCH.sub.31.224 Cl SO.sub. 2 CH.sub.3 i-C.sub.3 H.sub.7 H H COOCH.sub.31.225 SOCH.sub.3 Cl i-C.sub.3 H.sub.7 H H COOCH.sub.31.226 SO.sub.2 CH.sub.3 H i-C.sub.3 H.sub.7 H H COOCH.sub.31.227 H SO.sub.2 CH.sub.3 i-C.sub.3 H.sub.7 H H COOCH.sub.31.228 H CH.sub.3 i-C.sub.3 H.sub.7 H H COOCH.sub.31.229 Cl F i-C.sub.3 H.sub.7 H H COOCH.sub.31.230 H CF.sub.3 i-C.sub.3 H.sub.7 H H COOCH.sub.31.231 F F i-C.sub.3 H.sub.7 H H COOCH.sub.31.232 F CF.sub.3 i-C.sub.3 H.sub.7 H H COOCH.sub.31.233 CF.sub.3 F i-C.sub.3 H.sub.7 H H COOCH.sub.31.234 H CCl.sub.3 i-C.sub.3 H.sub.7 H H COOCH.sub.31.235 CCl.sub.3 H i-C.sub.3 H.sub.7 H H COOCH.sub.31.236 Cl CCl.sub.3 i-C.sub.3 H.sub.7 H H COOCH.sub.31.237 CCl.sub.3 Cl i-C.sub.3 H.sub.7 H H COOCH.sub.31.238 CH.sub.3 H i-C.sub.3 H.sub.7 H H COOCH.sub.31.239 Cl Cl CH.sub.3 H H COOCH.sub.31.240 Cl H CH.sub.3 H H COOCH.sub.31.241 H Cl CH.sub.3 H H COOCH.sub.31.242 H H CH.sub.3 H H COOCH.sub.31.243 Cl CF.sub.3 CH.sub.3 H H COOCH.sub.31.244 NO.sub.2 H CH.sub.3 H H COOCH.sub.31.245 H NO.sub.2 CH.sub.3 H H COOCH.sub.31.246 NO.sub.2 Cl CH.sub.3 H H COOCH.sub.31.247 CF.sub.3 H CH.sub.3 H H COOCH.sub.31.248 H CF.sub.3 CH.sub.3 H H COOCH.sub.31.249 OCH.sub.3 H CH.sub.3 H H COOCH.sub.31.250 CN H CH.sub.3 H H COOCH.sub.31.251 OCH.sub.3 Cl CH.sub.3 H H COOCH.sub.31.252 CN Cl CH.sub.3 H H COOCH.sub.31.253 Br Cl CH.sub.3 H H COOCH.sub.31.254 SCH.sub.3 Cl CH.sub.3 H H COOCH.sub.31.255 SO.sub.2 CH.sub.3 Cl CH.sub.3 H H COOCH.sub.31.256 Cl SCH.sub.3 CH.sub.3 H H COOCH.sub.31.257 Cl SOCH.sub.3 CH.sub.3 H H COOCH.sub.31.258 Cl SO.sub.2 CH.sub.3 CH.sub.3 H H COOCH.sub.31.259 SOCH.sub.3 Cl CH.sub.3 H H COOCH.sub.31.260 SO.sub.2 CH.sub.3 H CH.sub.3 H H COOCH.sub.31.261 H SO.sub.2 CH.sub.3 CH.sub.3 H H COOCH.sub.31.262 H CH.sub.3 CH.sub.3 H H COOCH.sub.31.263 Cl F CH.sub.3 H H COOCH.sub.31.264 H CF.sub.3 CH.sub.3 H H COOCH.sub.31.265 F F CH.sub.3 H H COOCH.sub.31.266 F CF.sub.3 CH.sub.3 H H COOCH.sub.31.267 CF.sub.3 F CH.sub.3 H H COOCH.sub.31.268 H CCl.sub.3 CH.sub.3 H H COOCH.sub.31.269 CCl.sub.3 H CH.sub.3 H H COOCH.sub.31.270 Cl CCl.sub.3 CH.sub.3 H H COOCH.sub.31.271 CCl.sub.3 Cl CH.sub.3 H H COOCH.sub.31.272 CH.sub.3 H CH.sub.3 H H COOCH.sub.31.273 Cl Cl CH.sub.3 CH.sub.3 H H m.p. 131-133.degree. C.1.274 Cl H CH.sub.3 CH.sub.3 H H1.275 H Cl CH.sub.3 CH.sub.3 H H1.276 H H CH.sub.3 CH.sub.3 H H1.277 Cl CF.sub.3 CH.sub.3 CH.sub.3 H H m.p. 95-98.degree. C.1.278 NO.sub.2 H CH.sub.3 CH.sub.3 H H1.279 H NO.sub.2 CH.sub.3 CH.sub.3 H H1.280 NO.sub.2 Cl CH.sub.3 CH.sub.3 H H1.281 CF.sub.3 H CH.sub.3 CH.sub.3 H H1.282 H CF.sub.3 CH.sub.3 CH.sub.3 H H1.283 OCH.sub.3 H CH.sub.3 CH.sub.3 H H1.284 CN H CH.sub.3 CH.sub.3 H H1.285 OCH.sub.3 Cl CH.sub.3 CH.sub.3 H H1.286 CN Cl CH.sub.3 CH.sub.3 H H1.287 Br Cl CH.sub.3 CH.sub.3 H H1.288 SCH.sub.3 Cl CH.sub.3 CH.sub.3 H H1.289 SO.sub.2 CH.sub.3 Cl CH.sub.3 CH.sub.3 H H1.290 Cl SCH.sub.3 CH.sub.3 CH.sub.3 H H1.291 Cl SOCH.sub.3 CH.sub.3 CH.sub.3 H H1.292 Cl SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H H1.293 SOCH.sub.3 Cl CH.sub.3 CH.sub.3 H H1.294 SO.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 H H1.295 H SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H H1.296 H CH.sub.3 CH.sub.3 CH.sub.3 H H1.297 Cl F CH.sub.3 CH.sub.3 H H1.298 H CF.sub.3 CH.sub.3 CH.sub.3 H H1.299 F F CH.sub.3 CH.sub.3 H H1.300 F CF.sub.3 CH.sub.3 CH.sub.3 H H1.301 CF.sub.3 F CH.sub.3 CH.sub.3 H H1.302 H CCl.sub.3 CH.sub.3 CH.sub.3 H H1.303 CCl.sub.3 H CH.sub.3 CH.sub.3 H H1.304 Cl CCl.sub.3 CH.sub.3 CH.sub.3 H H1.305 CCl.sub.3 Cl CH.sub.3 CH.sub.3 H H1.306 CH.sub.3 H CH.sub.3 CH.sub.3 H H1.307 Cl Cl CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.308 Cl H CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.309 H Cl CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.310 H H CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.311 Cl CF.sub.3 CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.312 NO.sub.2 H CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.313 H NO.sub.2 CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.314 NO.sub.2 Cl CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.315 CF.sub.3 H CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.316 H CF.sub.3 CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.317 OCH.sub.3 H CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.318 CN H CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.319 OCH.sub.3 Cl CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.320 CN Cl CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.321 Br Cl CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.322 SCH.sub.3 Cl CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.323 SO.sub.2 CH.sub.3 Cl CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.324 Cl SCH.sub.3 CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.325 Cl SOCH.sub.3 CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.326 Cl SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.327 SOCH.sub.3 Cl CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.328 SO.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.329 H SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.330 H CH.sub.3 CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.331 Cl F CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.332 H CF.sub.3 CH.sub.3 CH.sub. 3 H COOC.sub.2 H.sub.51.333 F F CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.334 F CF.sub.3 CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.335 CF.sub.3 F CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.336 H CCl.sub.3 CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.337 CCl.sub.3 H CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.338 Cl CCl.sub.3 CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.339 CCl.sub.3 Cl CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.340 CH.sub.3 H CH.sub.3 CH.sub.3 H COOC.sub.2 H.sub.51.341 Cl Cl C.sub.6 H.sub.5 H H H1.342 Cl H C.sub.6 H.sub.5 H H H1.343 H Cl C.sub.6 H.sub.5 H H H1.344 H H C.sub.6 H.sub.5 H H H1.345 Cl CF.sub.3 C.sub.6 H.sub.5 H H H m.p. >150.degree. C. (decomp.)1.346 NO.sub.2 H C.sub.6 H.sub.5 H H H1.347 H NO.sub.2 C.sub.6 H.sub.5 H H H1.348 NO.sub.2 Cl C.sub. 6 H.sub.5 H H H1.349 CF.sub.3 H C.sub.6 H.sub.5 H H H1.350 H CF.sub.3 C.sub.6 H.sub.5 H H H1.351 OCH.sub.3 H C.sub.6 H.sub.5 H H H1.352 CN H C.sub.6 H.sub.5 H H H1.353 OCH.sub.3 Cl C.sub.6 H.sub.5 H H H1.354 CN Cl C.sub.6 H.sub.5 H H H1.355 Br Cl C.sub.6 H.sub.5 H H H1.356 SCH.sub.3 Cl C.sub.6 H.sub.5 H H H1.357 SO.sub.2 CH.sub.3 Cl C.sub.6 H.sub.5 H H H1.358 Cl SCH.sub.3 C.sub.6 H.sub.5 H H H1.359 Cl SOCH.sub.3 C.sub.6 H.sub.5 H H H1.360 Cl SO.sub.2 CH.sub.3 C.sub.6 H.sub.5 H H H1.361 SOCH.sub.3 Cl C.sub.6 H.sub.5 H H H1.362 SO.sub.2 CH.sub.3 H C.sub.6 H.sub.5 H H H1.363 H SO.sub.2 CH.sub.3 C.sub.6 H.sub.5 H H H1.364 H CH.sub.3 C.sub.6 H.sub.5 H H H1.365 Cl F C.sub.6 H.sub.5 H H H1.366 H CF.sub. 3 C.sub.6 H.sub.5 H H H1.367 F F C.sub.6 H.sub.5 H H H1.368 F CF.sub.3 C.sub.6 H.sub.5 H H H1.369 CF.sub.3 F C.sub.6 H.sub.5 H H H1.370 H CCl.sub.3 C.sub.6 H.sub.5 H H H1.371 CCl.sub.3 H C.sub.6 H.sub.5 H H H1.372 Cl CCl.sub.3 C.sub.6 H.sub.5 H H H1.373 CCl.sub.3 Cl C.sub.6 H.sub.5 H H H1.374 CH.sub.3 H C.sub.6 H.sub.5 H H H1.375 Cl Cl H H CH.sub.3 CH.sub.31.376 Cl H H H CH.sub.3 CH.sub.31.377 H Cl H H CH.sub.3 CH.sub.31.378 H H H H CH.sub.3 CH.sub.31.379 Cl CF.sub.3 H H CH.sub.3 CH.sub.31.380 NO.sub.2 H H H CH.sub.3 CH.sub.31.381 H NO.sub.2 H H CH.sub.3 CH.sub.31.382 NO.sub.2 Cl H H CH.sub.3 CH.sub.31.383 CF.sub.3 H H H CH.sub.3 CH.sub.31.384 H CF.sub.3 H H CH.sub.3 CH.sub.31.385 OCH.sub.3 H H H CH.sub.3 CH.sub. 31.386 CN H H H CH.sub.3 CH.sub.31.387 OCH.sub.3 Cl H H CH.sub.3 CH.sub.31.388 CN Cl H H CH.sub.3 CH.sub.31.389 Br Cl H H CH.sub.3 CH.sub.31.390 SCH.sub.3 Cl H H CH.sub.3 CH.sub.31.391 SO.sub.2 CH.sub.3 Cl H H CH.sub.3 CH.sub.31.392 Cl SCH.sub.3 H H CH.sub.3 CH.sub.31.393 Cl SOCH.sub.3 H H CH.sub.3 CH.sub.31.394 Cl SO.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.31.395 SOCH.sub.3 Cl H H CH.sub.3 CH.sub.31.396 SO.sub.2 CH.sub.3 H H H CH.sub.3 CH.sub.31.397 H SO.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.31.398 H CH.sub.3 H H CH.sub.3 CH.sub.31.399 Cl F H H CH.sub.3 CH.sub.31.400 H CF.sub.3 H H CH.sub.3 CH.sub.31.401 F F H H CH.sub.3 CH.sub.31.402 F CF.sub.3 H H CH.sub.3 CH.sub.31.403 CF.sub.3 F H H CH.sub.3 CH.sub.31.404 H CCl.sub.3 H H CH.sub.3 CH.sub.31.405 CCl.sub.3 H H H CH.sub. 3 CH.sub.31.406 Cl CCl.sub.3 H H CH.sub.3 CH.sub.31.407 CCl.sub.3 Cl H H CH.sub.3 CH.sub.31.408 CH.sub.3 H H H CH.sub.3 CH.sub.31.409 Cl Cl C.sub.6 H.sub.5CH.sub.2 H H H1.410 Cl H C.sub.6 H.sub.5CH.sub.2 H H H1.411 H Cl C.sub.6 H.sub.5CH.sub.2 H H H1.412 H H C.sub.6 H.sub.5CH.sub.2 H H H1.413 Cl CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H1.414 NO.sub.2 H C.sub.6 H.sub.5CH.sub.2 H H H1.415 H NO.sub.2 C.sub.6 H.sub.5CH.sub.2 H H H1.416 NO.sub.2 Cl C.sub.6 H.sub.5CH.sub.2 H H H1.417 CF.sub.3 H C.sub.6 H.sub.5CH.sub.2 H H H1.418 H CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H1.419 OCH.sub.3 H C.sub.6 H.sub.5CH.sub.2 H H H1.420 CN H C.sub.6 H.sub.5CH.sub.2 H H H1.421 OCH.sub.3 Cl C.sub.6 H.sub.5CH.sub.2 H H H1.422 CN Cl C.sub.6 H.sub.5CH.sub.2 H H H1.423 Br Cl C.sub.6 H.sub.5CH.sub.2 H H H1.424 SCH.sub.3 Cl C.sub.6 H.sub.5CH.sub.2 H H H1.425 SO.sub.2 CH.sub.3 Cl C.sub.6 H.sub.5CH.sub.2 H H H1.426 Cl SCH.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H1.427 Cl SOCH.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H1.428 Cl SO.sub.2 CH.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H1.429 SOCH.sub.3 Cl C.sub.6 H.sub.5CH.sub.2 H H H1.430 SO.sub.2 CH.sub.3 H C.sub.6 H.sub.5CH.sub.2 H H H1.431 H SO.sub.2 CH.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H1.432 H CH.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H1.433 Cl F C.sub.6 H.sub.5CH.sub.2 H H H1.434 H CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H1.435 F F C.sub.6 H.sub.5CH.sub.2 H H H1.436 F CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H1.437 CF.sub.3 F C.sub.6 H.sub.5CH.sub.2 H H H1.438 H CCl.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H1.439 CCl.sub.3 H C.sub.6 H.sub.5CH.sub.2 H H H1.440 Cl CCl.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H1.441 CCl.sub.3 Cl C.sub.6 H.sub.5CH.sub.2 H H H1.442 CH.sub.3 H C.sub.6 H.sub.5CH.sub.2 H H H1.443 Cl Cl 4-ClC.sub.6 H.sub.4 H H H1.444 Cl H 4-ClC.sub.6 H.sub.4 H H H1.445 H Cl 4-ClC.sub.6 H.sub.4 H H H1.446 H H 4-ClC.sub.6 H.sub.4 H H H1.447 Cl CF.sub.3 4-ClC.sub.6 H.sub.4 H H H1.448 NO.sub.2 H 4-ClC.sub.6 H.sub.4 H H H1.449 H NO.sub.2 4-ClC.sub.6 H.sub.4 H H H1.450 NO.sub.2 Cl 4-ClC.sub.6 H.sub.4 H H H1.451 CF.sub.3 H 4-ClC.sub.6 H.sub.4 H H H1.452 H CF.sub.3 4-ClC.sub.6 H.sub.4 H H H1.453 OCH.sub.3 H 4-ClC.sub.6 H.sub.4 H H H1.454 CN H 4-ClC.sub.6 H.sub.4 H H H1.455 OCH.sub.3 Cl 4-ClC.sub.6 H.sub.4 H H H1.456 CN Cl 4-ClC.sub.6 H.sub.4 H H H1.457 Br Cl 4-ClC.sub.6 H.sub.4 H H H1.458 SCH.sub.3 Cl 4-ClC.sub.6 H.sub.4 H H H1.459 SO.sub.2 CH.sub.3 Cl 4-ClC.sub.6 H.sub.4 H H H1.460 Cl SCH.sub.3 4-ClC.sub.6 H.sub.4 H H H1.461 Cl SOCH.sub.3 4-ClC.sub.6 H.sub.4 H H H1.462 Cl SO.sub.2 CH.sub.3 4-ClC.sub.6 H.sub.4 H H H1.463 SOCH.sub.3 Cl 4-ClC.sub.6 H.sub.4 H H H1.464 SO.sub.2 CH.sub.3 H 4-ClC.sub.6 H.sub.4 H H H1.465 H SO.sub.2 CH.sub.3 4-ClC.sub.6 H.sub.4 H H H1.466 H CH.sub.3 4-ClC.sub.6 H.sub.4 H H H1.467 Cl F 4-ClC.sub.6 H.sub.4 H H H1.468 H CF.sub.3 4-ClC.sub.6 H.sub.4 H H H1.469 F F 4-ClC.sub.6 H.sub.4 H H H1.470 F CF.sub.3 4-ClC.sub.6 H.sub.4 H H H1.471 CF.sub.3 F 4-ClC.sub.6 H.sub.4 H H H1.472 H CCl.sub.3 4-ClC.sub.6 H.sub.4 H H H1.473 CCl.sub.3 H 4-ClC.sub.6 H.sub.4 H H H1.474 Cl CCl.sub.3 4-ClC.sub.6 H.sub.4 H H H1.475 CCl.sub.3 Cl 4-ClC.sub.6 H.sub.4 H H H1.476 CH.sub.3 H 4-ClC.sub.6 H.sub.4 H H H1.477 Cl Cl CH.sub.3 H CH.sub.3 H1.478 Cl H CH.sub.3 H CH.sub.3 H1.479 H Cl CH.sub.3 H CH.sub.3 H1.480 H H CH.sub.3 H CH.sub.3 H1.481 Cl CF.sub.3 CH.sub.3 H CH.sub.3 H1.482 NO.sub.2 H CH.sub.3 H CH.sub.3 H1.483 H NO.sub.2 CH.sub.3 H CH.sub.3 H1.484 NO.sub.2 Cl CH.sub.3 H CH.sub.3 H1.485 CF.sub.3 H CH.sub.3 H CH.sub.3 H1.486 H CF.sub.3 CH.sub.3 H CH.sub.3 H1.487 OCH.sub.3 H CH.sub.3 H CH.sub.3 H1.488 CN H CH.sub.3 H CH.sub.3 H1.489 OCH.sub.3 Cl CH.sub.3 H CH.sub.3 H1.490 CN Cl CH.sub.3 H CH.sub.3 H1.491 Br Cl CH.sub.3 H CH.sub.3 H1.492 SCH.sub.3 Cl CH.sub.3 H CH.sub.3 H1.493 SO.sub.2 CH.sub.3 Cl CH.sub.3 H CH.sub.3 H1.494 Cl SCH.sub.3 CH.sub.3 H CH.sub.3 H1.495 Cl SOCH.sub.3 CH.sub.3 H CH.sub.3 H1.496 Cl SO.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 H1.497 SOCH.sub.3 Cl CH.sub.3 H CH.sub.3 H1.498 SO.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 H1.499 H SO.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 H1.500 H CH.sub.3 CH.sub.3 H CH.sub.3 H1.501 Cl F CH.sub.3 H CH.sub.3 H1.502 H CF.sub.3 CH.sub.3 H CH.sub.3 H1.503 F F CH.sub.3 H CH.sub.3 H1.504 F CF.sub.3 CH.sub.3 H CH.sub.3 H1.505 CF.sub.3 F CH.sub.3 H CH.sub.3 H1.506 H CCl.sub.3 CH.sub.3 H CH.sub.3 H1.507 CCl.sub.3 H CH.sub.3 H CH.sub.3 H1.508 Cl CCl.sub.3 CH.sub.3 H CH.sub.3 H1.509 CCl.sub.3 Cl CH.sub.3 H CH.sub.3 H1.510 CH.sub.3 H CH.sub.3 H CH.sub.3 H1.511 Cl Cl H H H CN1.512 Cl H H H H CN1.513 H Cl H H H CN1.514 H H H H H CN1.515 Cl CF.sub.3 H H H CN1.516 NO.sub.2 H H H H CN1.517 H NO.sub.2 H H H CN1.518 NO.sub.2 Cl H H H CN1.519 CF.sub.3 H H H H CN1.520 H CF.sub.3 H H H CN1.521 OCH.sub.3 H H H H CN1.522 CN H H H H CN1.523 OCH.sub.3 Cl H H H CN1.524 CN Cl H H H CN1.525 Br Cl H H H CN1.526 SCH.sub.3 Cl H H H CN1.527 SO.sub.2 CH.sub.3 Cl H H H CN1.528 Cl SCH.sub.3 H H H CN1.529 Cl SOCH.sub.3 H H H CN1.530 Cl SO.sub.2 CH.sub.3 H H H CN1.531 SOCH.sub.3 Cl H H H CN1.532 SO.sub.2 CH.sub.3 H H H H CN1.533 H SO.sub.2 CH.sub.3 H H H CN1.534 H CH.sub.3 H H H CN1.535 Cl F H H H CN1.536 H CF.sub.3 H H H CN1.537 F F H H H CN1.538 F CF.sub.3 H H H CN1.539 CF.sub.3 F H H H CN1.540 H CCl.sub.3 H H H CN1.541 CCl.sub.3 H H H H CN1.542 Cl CCl.sub.3 H H H CN1.543 CCl.sub.3 Cl H H H CN1,544 CH.sub.3 H H H H CN1.545 Cl Cl CH.sub.3 H H CN1.546 Cl H CH.sub.3 H H CN1.547 H Cl CH.sub.3 H H CN1.548 H H CH.sub.3 H H CN1.549 Cl CF.sub.3 CH.sub.3 H H CN1.550 NO.sub.2 H CH.sub.3 H H CN1.551 H NO.sub.2 CH.sub.3 H H CN1.552 NO.sub.2 Cl CH.sub.3 H H CN1.553 CF.sub.3 H CH.sub.3 H H CN1.554 H CF.sub.3 CH.sub.3 H H CN1.555 OCH.sub.3 H CH.sub.3 H H CN1.556 CN H CH.sub.3 H H CN1.557 OCH.sub.3 Cl CH.sub.3 H H CN1.558 CN Cl CH.sub.3 H H CN1.559 Br Cl CH.sub.3 H H CN1.560 SCH.sub.3 Cl CH.sub.3 H H CN1.561 SO.sub.2 CH.sub.3 Cl CH.sub.3 H H CN1.562 Cl SCH.sub.3 CH.sub.3 H H CN1.563 Cl SOCH.sub.3 CH.sub.3 H H CN1.564 Cl SO.sub.2 CH.sub.3 CH.sub.3 H H CN1.565 SOCH.sub.3 Cl CH.sub.3 H H CN1.566 SO.sub.2 CH.sub.3 H CH.sub.3 H H CN1.567 H SO.sub.2 CH.sub.3 CH.sub.3 H H CN1.568 H CH.sub.3 CH.sub.3 H H CN1.569 Cl F CH.sub.3 H H CN1.570 H CF.sub.3 CH.sub.3 H H CN1.571 F F CH.sub.3 H H CN1.572 F CF.sub.3 CH.sub.3 H H CN1.573 CF.sub.3 F CH.sub.3 H H CN1.574 H CCl.sub.3 CH.sub.3 H H CN1.575 CCl.sub.3 H CH.sub.3 H H CN1.576 Cl CCl.sub.3 CH.sub.3 H H CN1.577 CCl.sub.3 Cl CH.sub.3 H H CN1.578 CH.sub.3 H CH.sub.3 H H CN1.579 Cl Cl C.sub.6 H.sub.5 H H COOCH.sub.31.580 Cl H C.sub.6 H.sub.5 H H COOCH.sub.31.581 H Cl C.sub.6 H.sub.5 H H COOCH.sub.31.582 H H C.sub.6 H.sub.5 H H COOCH.sub.31.583 Cl CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 m.p. >180 decomp.1.584 NO.sub.2 H C.sub.6 H.sub.5 H H COOCH.sub.31.585 H NO.sub.2 C.sub.6 H.sub.5 H H COOCH.sub.31.586 NO.sub.2 Cl C.sub.6 H.sub.5 H H COOCH.sub.31.587 CF.sub.3 H C.sub.6 H.sub.5 H H COOCH.sub.31.588 H CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.31.589 OCH.sub.3 H C.sub.6 H.sub.5 H H COOCH.sub.31.590 CN H C.sub.6 H.sub.5 H H COOCH.sub.31.591 OCH.sub.3 Cl C.sub.6 H.sub.5 H H COOCH.sub.31.592 CN Cl C.sub.6 H.sub.5 H H COOCH.sub.31.593 Br Cl C.sub. 6 H.sub.5 H H COOCH.sub.31.594 SCH.sub.3 Cl C.sub.6 H.sub.5 H H COOCH.sub.31.595 SO.sub.2 CH.sub.3 Cl C.sub.6 H.sub.5 H H COOCH.sub.31.596 Cl SCH.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.31.597 Cl SOCH.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.31.598 Cl SO.sub.2 CH.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.31.599 SOCH.sub.3 Cl C.sub.6 H.sub.5 H H COOCH.sub.31.600 SO.sub.2 CH.sub.3 H C.sub.6 H.sub.5 H H COOCH.sub.31.601 H SO.sub.2 CH.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.31.602 H CH.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.31.603 Cl F C.sub.6 H.sub.5 H H COOCH.sub.31.604 H CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.31.605 F F C.sub.6 H.sub.5 H H COOCH.sub.31.606 F CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.31.607 CF.sub.3 F C.sub.6 H.sub.5 H H COOCH.sub.31.608 H CCl.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.31.609 CCl.sub.3 H C.sub.6 H.sub. 5 H H COOCH.sub.31.610 Cl CCl.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.31.611 CCl.sub.3 Cl C.sub.6 H.sub.5 H H COOCH.sub.31.612 CH.sub.3 H C.sub.6 H.sub.5 H H COOCH.sub.31.613 H SCH.sub.3 H H H H m.p. >140.degree. Z1.614 H SOCH.sub.3 H H H H1.615 H SO.sub.2 CH.sub.3 H H H H1.616 CO.sub.2 H H H H H H m.p. >150.degree. Z1.617 CO.sub.2 H H CH.sub.3 H H H1.618 CO.sub.2 H H H C.sub.3 H.sub.7 (i) H H1.619 CO.sub.2 H H H Phenyl H H1.620 CO.sub.2 CH.sub.3 H H H H H1.621 CO.sub.2 C.sub.2 H.sub.5 H H H H H1.622 CO.sub.2 NH.sub.2 H H H H H1.623 CN H H H H H1.624 CO.sub.2 H CH.sub.3 H H H H1.625 CO.sub.2 CH.sub.3 CH.sub.3 H H H H1.626 CO.sub.2 H C.sub.2 H.sub.5 H H H H1.627 CO.sub.2 CH.sub.3 C.sub.2 H.sub.5 H H H H1.628 CO.sub.2 CH.sub.3 Br H H H H1.629 CO.sub.2 H Br H H H H1.630 Cl CF.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H m.p. 65-70.degree. C.1.631 H CF.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H1.632 Cl OCH.sub.3 H H H H1.633 Cl SC.sub.2 H.sub.5 H H H H1.634 Cl SOC.sub.2 H.sub.5 H H H H1.635 Cl SO.sub.2 C.sub.2 H.sub.5 H H H H1.636 SC.sub.2 H.sub.5 Cl H H H H1.637 SOC.sub.2 H.sub.5 Cl H H H H1.638 SO.sub.2 C.sub.2 H.sub.5 Cl H H H H1.639 H SO.sub.2 C.sub.2 H.sub.5 H H H H1.640 Cl SO.sub.2 C.sub.3 H.sub.7 (i) H H H H1.641 Cl SOC.sub.3 H.sub.7 (i) H H H H1.642 Cl SC.sub.3 H.sub.7 (i) H H H H1.643 Cl OCH.sub.3 H H H H1.644 Cl OC.sub.3 H.sub.7 (i) H H H H1.645 Cl Br H H H H1.646 H OCH.sub.3 H H H H m.p. 79-85.degree. C.__________________________________________________________________________
P.1.2. Preparation of salts of formula I
P.1.2.1. Sodium salt of 2-(3-chloro-5-trifluoromethylpyridin-2-ylcarbonyl) -cyclohex-1-en1-ol-3one
3.222 g of 2-(3-chloro-5-trifluoromethylpyridin-2-ylcarbonyl)-cyclohex-1-en-1-ol-3-one are dissolved in 20 ml of methanol, 0.54 g of sodium methoxide is added and the whole is stirred at room temperature for 15 minutes and then concentrated to dryness on a rotary evaporator. The residue is triturated with diethyl ether, filtered and dried.
The title compound of formula ##STR26## is isolated in quantitative yield in the form of a colourless solid (Compound No. 2.006).
The salts of Table 2 can be synthesised analogously to the above preparation processes.
TABLE 2__________________________________________________________________________Compounds of formula ##STR27##Comp. No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 M.sup..sym. phys. data__________________________________________________________________________2.001 Cl Cl H H H H Na.sup..sym.2.002 Cl Cl H H H H Li.sup..sym.2.003 Cl Cl H H H H 1/2Ca.sup.2.sym.2.004 Cl Cl H H H H NH(CH.sub.3).sub.3.sup..sym.2.005 Cl Cl H H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.006 Cl CF.sub.3 H H H H Na.sup..sym. colourless solid2.007 Cl CF.sub.3 H H H H Li.sup..sym.2.008 Cl CF.sub.3 H H H H 1/2Ca.sup.2.sym.2.009 Cl CF.sub.3 H H H H NH(CH.sub.3).sub.3.sup..sym.2.010 Cl CF.sub.3 H H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.011 NO.sub.2 H H H H H Na.sup..sym.2.012 NO.sub.2 H H H H H Li.sup..sym.2.013 NO.sub.2 H H H H H 1/2Ca.sup.2.sym.2.014 NO.sub.2 H H H H H NH(CH.sub.3).sub.3.sup..sym.2.015 NO.sub.2 H H H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.016 H NO.sub.2 H H H H Na.sup..sym.2.017 H NO.sub.2 H H H H Li.sup..sym.2.018 H NO.sub.2 H H H H 1/2Ca.sup.2.sym.2.019 H NO.sub.2 H H H H NH(CH.sub.3).sub.3.sup..sym.2.020 H NO.sub.2 H H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.021 H H H H H H Na.sup..sym.2.022 H H H H H H Li.sup..sym.2.023 H H H H H H 1/2Ca.sup.2.sym.2.024 H H H H H H NH(CH.sub.3).sub.3.sup..sym.2.025 H H H H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.026 Cl CCl.sub.3 H H H H Na.sup..sym.2.027 Cl CCl.sub.3 H H H H Li.sup..sym.2.028 Cl CCl.sub.3 H H H H 1/2Ca.sup.2.sym.2.029 Cl CCl.sub.3 H H H H NH(CH.sub.3).sub.3.sup..sym.2.030 Cl CCl.sub.3 H H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.031 F CF.sub.3 H H H H Na.sup..sym.2.032 F CF.sub.3 H H H H Li.sup..sym.2.033 F CF.sub.3 H H H H 1/2Ca.sup.2.sym.2.034 F CF.sub.3 H H H H NH(CH.sub.3).sub.3.sup..sym.2.035 F CF.sub.3 H H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.036 Cl Cl CH.sub.3 H H H Na.sup..sym.2.037 Cl Cl CH.sub.3 H H H Li.sup..sym.2.038 Cl Cl CH.sub.3 H H H 1/2Ca.sup.2.sym.2.039 Cl Cl CH.sub.3 H H H NH(CH.sub.3).sub.3.sup..sym.2.040 Cl Cl CH.sub.3 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.041 Cl CF.sub.3 CH.sub.3 H H H Na.sup..sym.2.042 Cl CF.sub.3 CH.sub.3 H H H Li.sup..sym.2.043 Cl CF.sub.3 CH.sub.3 H H H 1/2Ca.sup.2.sym.2.044 Cl CF.sub.3 CH.sub.3 H H H NH(CH.sub.3).sub.3.sup..sym.2.045 Cl CF.sub.3 CH.sub.3 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.046 NO.sub.2 H CH.sub.3 H H H Na.sup..sym.2.047 NO.sub.2 H CH.sub.3 H H H Li.sup..sym.2.048 NO.sub.2 H CH.sub.3 H H H 1/2Ca.sup.2.sym.2.049 NO.sub.2 H CH.sub.3 H H H NH(CH.sub.3).sub.3.sup..sym.2.050 NO.sub.2 H CH.sub.3 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.051 H NO.sub.2 CH.sub.3 H H H Na.sup..sym.2.052 H NO.sub.2 CH.sub.3 H H H Li.sup..sym.2.053 H NO.sub.2 CH.sub.3 H H H 1/2Ca.sup.2.sym.2.054 H NO.sub.2 CH.sub.3 H H H NH(CH.sub.3).sub.3.sup..sym.2.055 H NO.sub.2 CH.sub.3 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.056 H H CH.sub.3 H H H Na.sup..sym.2.057 H H CH.sub.3 H H H Li.sup..sym.2.058 H H CH.sub.3 H H H 1/2Ca.sup.2.sym.2.059 H H CH.sub.3 H H H NH(CH.sub.3).sub.3.sup..sym.2.060 H H CH.sub.3 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.061 Cl CCl.sub.3 CH.sub.3 H H H Na.sup..sym.2.062 Cl CCl.sub.3 CH.sub.3 H H H Li.sup..sym.2.063 Cl CCl.sub.3 CH.sub.3 H H H 1/2Ca.sup.2.sym.2.064 Cl CCl.sub.3 CH.sub.3 H H H NH(CH.sub.3).sub.3.sup..sym.2.065 Cl CCl.sub.3 CH.sub.3 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.066 F CF.sub.3 CH.sub.3 H H H Na.sup..sym.2.067 F CF.sub.3 CH.sub.3 H H H Li.sup..sym.2.068 F CF.sub.3 CH.sub.3 H H H 1/2Ca.sup.2.sym.2.069 F CF.sub.3 CH.sub.3 H H H NH(CH.sub.3).sub.3.sup..sym.2.070 F CF.sub.3 CH.sub.3 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.071 Cl Cl n-C.sub. 3 H.sub.7 H H H Na.sup..sym.2.072 Cl Cl n-C.sub.3 H.sub.7 H H H Li.sup..sym.2.073 Cl Cl n-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.074 Cl Cl n-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.075 Cl Cl n-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.076 Cl CF.sub.3 n-C.sub.3 H.sub.7 H H H Na.sup..sym.2.077 Cl CF.sub.3 n-C.sub.3 H.sub.7 H H H Li.sup..sym.2.078 Cl CF.sub.3 n-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.079 Cl CF.sub.3 n-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.080 Cl CF.sub.3 n-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.081 NO.sub.2 H n-C.sub.3 H.sub.7 H H H Na.sup..sym.2.082 NO.sub.2 H n-C.sub.3 H.sub.7 H H H Li.sup..sym.2.083 NO.sub.2 H n-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.084 NO.sub.2 H n-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.085 NO.sub.2 H n-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.086 H NO.sub.2 n-C.sub.3 H.sub.7 H H H Na.sup..sym.2.087 H NO.sub.2 n-C.sub.3 H.sub.7 H H H Li.sup..sym.2.088 H NO.sub.2 n-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.089 H NO.sub.2 n-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.090 H NO.sub.2 n-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.091 H H n-C.sub.3 H.sub.7 H H H Na.sup..sym.2.092 H H n-C.sub.3 H.sub.7 H H H Li.sup..sym.2.093 H H n-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.094 H H n-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.095 H H n-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.096 Cl CCl.sub.3 n-C.sub.3 H.sub.7 H H H Na.sup..sym.2.097 Cl CCl.sub.3 n-C.sub. 3 H.sub.7 H H H Li.sup..sym.2.098 Cl CCl.sub.3 n-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.099 Cl CCl.sub.3 n-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.100 Cl CCl.sub.3 n-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.101 F CF.sub.3 n-C.sub.3 H.sub.7 H H H Na.sup..sym.2.102 F CF.sub.3 n-C.sub.3 H.sub.7 H H H Li.sup..sym.2.103 F CF.sub.3 n-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.104 F CF.sub.3 n-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.105 F CF.sub.3 n-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.106 Cl Cl i-C.sub.3 H.sub.7 H H H Na.sup..sym.2.107 Cl Cl i-C.sub.3 H.sub.7 H H H Li.sup..sym.2.108 Cl Cl i-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.109 Cl Cl i-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.110 Cl Cl i-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.111 Cl CF.sub.3 i-C.sub.3 H.sub.7 H H H Na.sup..sym.2.112 Cl CF.sub.3 i-C.sub.3 H.sub.7 H H H Li.sup..sym.2.113 Cl CF.sub.3 i-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.114 Cl CF.sub.3 i-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.115 Cl CF.sub.3 i-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.116 NO.sub.2 H i-C.sub.3 H.sub.7 H H H Na.sup..sym.2.117 NO.sub.2 H i-C.sub.3 H.sub.7 H H H Li.sup..sym.2.118 NO.sub.2 H i-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.119 NO.sub.2 H i-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.120 NO.sub.2 H i-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.121 H NO.sub.2 i-C.sub.3 H.sub.7 H H H Na.sup..sym.2.122 H NO.sub.2 i-C.sub.3 H.sub.7 H H H Li.sup..sym.2.123 H NO.sub.2 i-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.124 H NO.sub.2 i-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.125 H NO.sub.2 i-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.126 H H i-C.sub.3 H.sub.7 H H H Na.sup..sym.2.127 H H i-C.sub.3 H.sub.7 H H H Li.sup..sym.2.128 H H i-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.129 H H i-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.130 H H i-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.131 Cl CCl.sub.3 i-C.sub.3 H.sub.7 H H H Na.sup..sym.2.132 Cl CCl.sub.3 i-C.sub.3 H.sub.7 H H H Li.sup..sym.2.133 Cl CCl.sub.3 i-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.134 Cl CCl.sub.3 i-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.135 Cl CCl.sub.3 i-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub. 3.sup..sym.2.136 F CF.sub.3 i-C.sub.3 H.sub.7 H H H Na.sup..sym.2.137 F CF.sub.3 i-C.sub.3 H.sub.7 H H H Li.sup..sym.2.138 F CF.sub.3 i-C.sub.3 H.sub.7 H H H 1/2Ca.sup.2.sym.2.139 F CF.sub.3 i-C.sub.3 H.sub.7 H H H NH(CH.sub.3).sub.3.sup..sym.2.140 F CF.sub.3 i-C.sub.3 H.sub.7 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.141 Cl Cl C.sub.6 H.sub.5 H H H Na.sup..sym.2.142 Cl Cl C.sub.6 H.sub.5 H H H Li.sup..sym.2.143 Cl Cl C.sub.6 H.sub.5 H H H 1/2Ca.sup.2.sym.2.144 Cl Cl C.sub.6 H.sub.5 H H H NH(CH.sub.3).sub.3.sup..sym.2.145 Cl Cl C.sub.6 H.sub.5 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.146 Cl CF.sub.3 C.sub.6 H.sub.5 H H H Na.sup..sym.2.147 Cl CF.sub.3 C.sub.6 H.sub.5 H H H Li.sup..sym.2.148 Cl CF.sub.3 C.sub.6 H.sub.5 H H H 1/2Ca.sup.2.sym.2.149 Cl CF.sub.3 C.sub.6 H.sub.5 H H H NH(CH.sub.3).sub.3.sup..sym.2.150 Cl CF.sub.3 C.sub.6 H.sub.5 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.151 NO.sub.2 H C.sub.6 H.sub.5 H H H Na.sup..sym.2.152 NO.sub.2 H C.sub.6 H.sub.5 H H H Li.sup..sym.2.153 NO.sub.2 H C.sub.6 H.sub.5 H H H 1/2Ca.sup.2.sym.2.154 NO.sub.2 H C.sub.6 H.sub.5 H H H NH(CH.sub.3).sub.3.sup..sym.2.155 NO.sub.2 H C.sub.6 H.sub.5 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.156 H NO.sub.2 C.sub.6 H.sub.5 H H H Na.sup..sym.2.157 H NO.sub.2 C.sub.6 H.sub.5 H H H Li.sup..sym.2.158 H NO.sub.2 C.sub.6 H.sub.5 H H H 1/2Ca.sup.2.sym.2.159 H NO.sub.2 C.sub.6 H.sub.5 H H H NH(CH.sub.3).sub.3.sup..sym.2.160 H NO.sub.2 C.sub.6 H.sub.5 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.161 H H C.sub.6 H.sub.5 H H H Na.sup..sym.2.162 H H C.sub.6 H.sub.5 H H H Li.sup..sym.2.163 H H C.sub.6 H.sub.5 H H H 1/2Ca.sup.2.sym.2.164 H H C.sub.6 H.sub.5 H H H NH(CH.sub.3).sub.3.sup..sym.2.165 H H C.sub.6 H.sub.5 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.166 Cl CCl.sub.3 C.sub.6 H.sub.5 H H H Na.sup..sym.2.167 Cl CCl.sub.3 C.sub.6 H.sub.5 H H H Li.sup..sym.2.168 Cl CCl.sub.3 C.sub.6 H.sub.5 H H H 1/2Ca.sup.2.sym.2.169 Cl CCl.sub.3 C.sub.6 H.sub.5 H H H NH(CH.sub.3).sub.3.sup..sym.2.170 Cl CCl.sub.3 C.sub.6 H.sub.5 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.171 F CF.sub.3 C.sub.6 H.sub.5 H H H Na.sup..sym.2.172 F CF.sub.3 C.sub.6 H.sub.5 H H H Li.sup..sym.2.173 F CF.sub.3 C.sub.6 H.sub.5 H H H 1/2Ca.sup.2.sym.2.174 F CF.sub.3 C.sub.6 H.sub.5 H H H NH(CH.sub.3).sub.3.sup..sym.2.175 F CF.sub.3 C.sub.6 H.sub.5 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.176 Cl Cl CH.sub.3 CH.sub.3 H H Na.sup..sym.2.177 Cl Cl CH.sub.3 CH.sub.3 H H Li.sup..sym.2.178 Cl Cl CH.sub.3 CH.sub.3 H H 1/2Ca.sup.2.sym.2.179 Cl Cl CH.sub.3 CH.sub.3 H H NH(CH.sub.3).sub.3.sup..sym.2.180 Cl Cl CH.sub.3 CH.sub.3 H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.181 Cl CF.sub.3 CH.sub.3 CH.sub.3 H H Na.sup..sym.2.182 Cl CF.sub.3 CH.sub.3 CH.sub.3 H H Li.sup..sym.2.183 Cl CF.sub.3 CH.sub.3 CH.sub.3 H H 1/2Ca.sup.2.sym.2.184 Cl CF.sub.3 CH.sub.3 CH.sub.3 H H NH(CH.sub.3).sub.3.sup..sym.2.185 Cl CF.sub.3 CH.sub.3 CH.sub.3 H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.186 NO.sub.2 H CH.sub.3 CH.sub.3 H H Na.sup..sym.2.187 NO.sub.2 H CH.sub.3 CH.sub.3 H H Li.sup..sym.2.188 NO.sub.2 H CH.sub.3 CH.sub.3 H H 1/2Ca.sup.2.sym.2.189 NO.sub.2 H CH.sub.3 CH.sub.3 H H NH(CH.sub.3).sub.3.sup..sym.2.190 NO.sub.2 H CH.sub.3 CH.sub.3 H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.191 H NO.sub.2 CH.sub.3 CH.sub.3 H H Na.sup..sym.2.192 H NO.sub.2 CH.sub.3 CH.sub.3 H H Li.sup..sym.2.193 H NO.sub.2 CH.sub.3 CH.sub.3 H H 1/2Ca.sup.2.sym.2.194 H NO.sub.2 CH.sub.3 CH.sub.3 H H NH(CH.sub.3).sub.3.sup..sym.2.195 H NO.sub.2 CH.sub.3 CH.sub.3 H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.196 H H CH.sub.3 CH.sub.3 H H Na.sup..sym.2.197 H H CH.sub.3 CH.sub.3 H H Li.sup..sym.2.198 H H CH.sub.3 CH.sub.3 H H 1/2Ca.sup.2.sym.2.199 H H CH.sub.3 CH.sub.3 H H NH(CH.sub.3).sub.3.sup..sym.2.200 H H CH.sub.3 CH.sub.3 H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.201 Cl CCl.sub.3 CH.sub.3 CH.sub.3 H H Na.sup..sym.2.202 Cl CCl.sub.3 CH.sub.3 CH.sub.3 H H Li.sup..sym.2.203 Cl CCl.sub.3 CH.sub.3 CH.sub.3 H H 1/2Ca.sup.2.sym.2.204 Cl CCl.sub.3 CH.sub.3 CH.sub.3 H H NH(CH.sub.3).sub.3.sup..sym.2.205 Cl CCl.sub.3 CH.sub.3 CH.sub.3 H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.206 F CF.sub.3 CH.sub.3 CH.sub.3 H H Na.sup..sym.2.207 F CF.sub.3 CH.sub.3 CH.sub.3 H H Li.sup..sym.2.208 F CF.sub.3 CH.sub.3 CH.sub.3 H H 1/2Ca.sup.2.sym.2.209 F CF.sub.3 CH.sub.3 CH.sub.3 H H NH(CH.sub.3).sub.3.sup..sym.2.210 F CF.sub.3 CH.sub.3 CH.sub.3 H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.211 Cl Cl CH.sub.3 H CH.sub.3 H Na.sup..sym.2.212 Cl Cl CH.sub.3 H CH.sub.3 H Li.sup..sym.2.213 Cl Cl CH.sub.3 H CH.sub.3 H 1/2Ca.sup.2.sym.2.214 Cl Cl CH.sub.3 H CH.sub.3 H NH(CH.sub.3).sub.3.sup..sym.2.215 Cl Cl CH.sub.3 H CH.sub.3 H NH(C.sub.2 H.sub.5 OH).sub.3.sup. .sym.2.216 Cl CF.sub.3 CH.sub.3 H CH.sub.3 H Na.sup..sym.2.217 Cl CF.sub.3 CH.sub.3 H CH.sub.3 H Li.sup..sym.2.218 Cl CF.sub.3 CH.sub.3 H CH.sub.3 H 1/2Ca.sup.2.sym.2.219 Cl CF.sub.3 CH.sub.3 H CH.sub.3 H NH(CH.sub.3).sub.3.sup..sym.2.220 Cl CF.sub.3 CH.sub.3 H CH.sub.3 H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.221 NO.sub.2 H CH.sub.3 H CH.sub.3 H Na.sup..sym.2.222 NO.sub.2 H CH.sub.3 H CH.sub.3 H Li.sup..sym.2.223 NO.sub.2 H CH.sub.3 H CH.sub.3 H 1/2Ca.sup.2.sym.2.224 NO.sub.2 H CH.sub.3 H CH.sub.3 H NH(CH.sub.3).sub.3.sup..sym.2.225 NO.sub.2 H CH.sub.3 H CH.sub.3 H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.226 H NO.sub.2 CH.sub.3 H CH.sub.3 H Na.sup..sym.2.227 H NO.sub.2 CH.sub.3 H CH.sub.3 H Li.sup..sym.2.228 H NO.sub.2 CH.sub.3 H CH.sub.3 H 1/2Ca.sup.2.sym.2.229 H NO.sub.2 CH.sub.3 H CH.sub.3 H NH(CH.sub.3).sub.3.sup..sym.2.230 H NO.sub.2 CH.sub.3 H CH.sub.3 H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.231 H H CH.sub.3 H CH.sub.3 H Na.sup..sym.2.232 H H CH.sub.3 H CH.sub.3 H Li.sup..sym.2.233 H H CH.sub.3 H CH.sub.3 H 1/2Ca.sup.2.sym.2.234 H H CH.sub.3 H CH.sub.3 H NH(CH.sub.3).sub.3.sup..sym.2.235 H H CH.sub.3 H CH.sub.3 H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.236 Cl CCl.sub.3 CH.sub.3 H CH.sub.3 H Na.sup..sym.2.237 Cl CCl.sub.3 CH.sub.3 H CH.sub.3 H Li.sup..sym.2.238 Cl CCl.sub.3 CH.sub.3 H CH.sub.3 H 1/2Ca.sup.2.sym.2.239 Cl CCl.sub.3 CH.sub.3 H CH.sub.3 H NH(CH.sub.3).sub.3.sup..sym.2.240 Cl CCl.sub.3 CH.sub.3 H CH.sub.3 H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.241 F CF.sub.3 CH.sub.3 H CH.sub.3 H Na.sup..sym.2.242 F CF.sub.3 CH.sub.3 H CH.sub.3 H Li.sup..sym.2.243 F CF.sub.3 CH.sub.3 H CH.sub.3 H 1/2Ca.sup.2.sym.2.244 F CF.sub.3 CH.sub.3 H CH.sub.3 H NH(CH.sub.3).sub.3.sup..sym.2.245 F CF.sub.3 CH.sub.3 H CH.sub.3 H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.246 Cl Cl H H H CN Na.sup..sym.2.247 Cl Cl H H H CN Li.sup..sym.2.248 Cl Cl H H H CN 1/2Ca.sup.2.sym.2.249 Cl Cl H H H CN NH(CH.sub.3).sub.3.sup..sym.2.250 Cl Cl H H H CN NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.251 Cl CF.sub.3 H H H CN Na.sup..sym.2.252 Cl CF.sub.3 H H H CN Li.sup..sym.2.253 Cl CF.sub.3 H H H CN 1/2Ca.sup.2.sym.2.254 Cl CF.sub.3 H H H CN NH(CH.sub.3).sub.3.sup..sym.2.255 Cl CF.sub.3 H H H CN NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.256 NO.sub.2 H H H H CN Na.sup..sym.2.257 NO.sub.2 H H H H CN Li.sup..sym.2.258 NO.sub.2 H H H H CN 1/2Ca.sup.2.sym.2.259 NO.sub. 2 H H H H CN NH(CH.sub.3).sub.3.sup..sym.2.260 NO.sub.2 H H H H CN NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.261 H NO.sub.2 H H H CN Na.sup..sym.2.262 H NO.sub.2 H H H CN Li.sup..sym.2.263 H NO.sub.2 H H H CN 1/2Ca.sup.2.sym.2.264 H NO.sub.2 H H H CN NH(CH.sub.3).sub.3.sup..sym.2.265 H NO.sub.2 H H H CN NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.266 H H H H H CN Na.sup..sym.2.267 H H H H H CN Li.sup..sym.2.268 H H H H H CN 1/2Ca.sup.2.sym.2.269 H H H H H CN NH(CH.sub.3).sub.3.sup..sym.2.270 H H H H H CN NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.271 Cl CCl.sub.3 H H H CN Na.sup..sym.2.272 Cl CCl.sub.3 H H H CN Li.sup..sym.2.273 Cl CCl.sub.3 H H H CN 1/2Ca.sup.2.sym.2.274 Cl CCl.sub.3 H H H CN NH(CH.sub.3).sub.3.sup..sym.2.275 Cl CCl.sub.3 H H H CN NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.276 F CF.sub.3 H H H CN Na.sup..sym.2.277 F CF.sub.3 H H H CN Li.sup..sym.2.278 F CF.sub.3 H H H CN 1/2Ca.sup.2.sym.2.279 F CF.sub.3 H H H CN NH(CH.sub.3).sub.3.sup..sym.2.280 F CF.sub.3 H H H CN NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.281 Cl Cl H H H CN Na.sup..sym.2.282 Cl Cl H H H CN Li.sup..sym.2.283 Cl Cl H H H CN 1/2Ca.sup.2.sym.2.284 Cl Cl H H H CN NH(CH.sub.3).sub.3.sup..sym.2.285 Cl Cl H H H CN NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.286 Cl CF.sub.3 H H H CN Na.sup..sym.2.287 Cl CF.sub.3 H H H CN Li.sup..sym.2.288 Cl CF.sub.3 H H H CN 1/2Ca.sup.2.sym.2.289 Cl CF.sub.3 H H H CN NH(CH.sub.3).sub.3.sup..sym.2.290 Cl CF.sub.3 H H H CN NH(C.sub.2 H.sub.5 OH).sub.3.sup. .sym.2.291 NO.sub.2 H CH.sub.3 H H CN Na.sup..sym.2.292 NO.sub.2 H CH.sub.3 H H CN Li.sup..sym.2.293 NO.sub.2 H CH.sub.3 H H CN 1/2Ca.sup.2.sup..sym.2.294 NO.sub.2 H CH.sub.3 H H CN NH(CH.sub.3).sub.3.sup..sym.2.295 NO.sub.2 H CH.sub.3 H H CN NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.296 H NO.sub.2 CH.sub.3 H H CN Na.sup..sym.2.297 H NO.sub.2 CH.sub.3 H H CN Li.sup..sym.2.298 H NO.sub.2 CH.sub.3 H H CN 1/2Ca.sup.2.sym.2.299 H NO.sub.2 CH.sub.3 H H CN NH(CH.sub.3).sub.3.sup..sym.2.300 H NO.sub.2 CH.sub.3 H H CN NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.301 H H CH.sub.3 H H CN Na.sup..sym.2.302 H H CH.sub.3 H H CN Li.sup..sym.2.303 H H CH.sub.3 H H CN 1/2Ca.sup.2.sym.2.304 H H CH.sub.3 H H CN NH(CH.sub.3).sub.3.sup..sym.2.305 H H CH.sub.3 H H CN NH(C.sub.2 H.sub. 5 OH).sub.3.sup..sym.2.306 Cl CCl.sub.3 CH.sub.3 H H CN Na.sup..sym.2.307 Cl CCl.sub.3 CH.sub.3 H H CN Li.sup..sym.2.308 Cl CCl.sub.3 CH.sub.3 H H CN 1/2Ca.sup.2.sym.2.309 Cl CCl.sub.3 CH.sub.3 H H CN NH(CH.sub.3).sub.3.sup..sym.2.310 Cl CCl.sub.3 CH.sub.3 H H CN NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.311 F CF.sub.3 CH.sub.3 H H CN Na.sup..sym.2.312 F CF.sub.3 CH.sub.3 H H CN Li.sup..sym.2.313 F CF.sub.3 CH.sub.3 H H CN 1/2Ca.sup.2.sym.2.314 F CF.sub.3 CH.sub.3 H H CN NH(CH.sub.3).sub.3.sup..sym.2.315 F CF.sub.3 CH.sub.3 H H CN NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.316 Cl Cl C.sub.6 H.sub.5CH.sub.2 H H H Na.sup..sym.2.317 Cl Cl C.sub.6 H.sub.5CH.sub.2 H H H Li.sup..sym.2.318 Cl Cl C.sub.6 H.sub.5CH.sub.2 H H H 1/2Ca.sup.2.sym.2.319 Cl Cl C.sub.6 H.sub.5CH.sub. 2 H H H NH(CH.sub.3).sub.3.sup..sym.2.320 Cl Cl C.sub.6 H.sub.5CH.sub.2 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.321 Cl CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H Na.sup..sym.2.322 Cl CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H Li.sup..sym.2.323 Cl CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H 1/2Ca.sup.2.sym.2.324 Cl CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H NH(CH.sub.3).sub.3.sup..sym.2.325 Cl CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.326 NO.sub.2 H C.sub.6 H.sub.5CH.sub.2 H H H Na.sup..sym.2.327 NO.sub.2 H C.sub.6 H.sub.5CH.sub.2 H H H Li.sup..sym.2.328 NO.sub.2 H C.sub.6 H.sub.5CH.sub.2 H H H 1/2Ca.sup.2.sym.2.329 NO.sub.2 H C.sub.6 H.sub.5CH.sub.2 H H H NH(CH.sub.3).sub.3.sup..sym.2.330 NO.sub. 2 H C.sub.6 H.sub.5CH.sub.2 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.331 H NO.sub.2 C.sub.6 H.sub.5CH.sub.2 H H H Na.sup..sym.2.332 H NO.sub.2 C.sub.6 H.sub.5CH.sub.2 H H H Li.sup..sym.2.333 H NO.sub.2 C.sub.6 H.sub.5CH.sub.2 H H H 1/2Ca.sup.2.sym.2.334 H NO.sub.2 C.sub.6 H.sub.5CH.sub.2 H H H NH(CH.sub.3).sub.3.sup..sym.2.335 H NO.sub.2 C.sub.6 H.sub.5CH.sub.2 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.336 H H C.sub.6 H.sub.5CH.sub.2 H H H Na.sup..sym.2.337 H H C.sub.6 H.sub.5CH.sub.2 H H H Li.sup..sym.2.338 H H C.sub.6 H.sub.5CH.sub.2 H H H 1/2Ca.sup.2.sym.2.339 H H C.sub.6 H.sub.5CH.sub.2 H H H NH(CH.sub.3).sub.3.sup..sym.2.340 H H C.sub.6 H.sub.5CH.sub.2 H H H NH(C.sub.2 H.sub.5 OH).sub. 3.sup..sym.2.341 Cl CCl.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H Na.sup..sym.2.342 Cl CCl.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H Li.sup..sym.2.343 Cl CCl.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H 1/2Ca.sup.2.sym.2.344 Cl CCl.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H NH(CH.sub.3).sub.3.sup..sym.2.345 Cl CCl.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.346 F CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H Na.sup..sym.2.347 F CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H Li.sup..sym.2.348 F CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H 1/2Ca.sup.2.sym.2.349 F CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H NH(CH.sub.3).sub.3.sup..sym.2.350 F CF.sub.3 C.sub.6 H.sub.5CH.sub.2 H H H NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.351 Cl Cl C.sub.6 H.sub.5 H H COOCH.sub. 3 Na.sup..sym.2.352 Cl Cl C.sub.6 H.sub.5 H H COOCH.sub.3 Li.sup..sym.2.353 Cl Cl C.sub.6 H.sub.5 H H COOCH.sub.3 1/2Ca.sup.2.sym.2.354 Cl Cl C.sub.6 H.sub.5 H H COOCH.sub.3 NH(CH.sub.3).sub.3.sup..sym.2.355 Cl Cl C.sub.6 H.sub.5 H H COOCH.sub.3 NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.356 Cl CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 Na.sup..sym.2.357 Cl CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 Li.sup..sym.2.358 Cl CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 1/2Ca.sup.2.sym.2.359 Cl CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 NH(CH.sub.3).sub.3.sup..sym.2.360 Cl CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.361 NO.sub.2 H C.sub.6 H.sub.5 H H COOCH.sub.3 Na.sup..sym.2.362 NO.sub.2 H C.sub.6 H.sub.5 H H COOCH.sub.3 Li.sup..sym.2.363 NO.sub.2 H C.sub.6 H.sub.5 H H COOCH.sub.3 1/2Ca.sup.2.sym.2.364 NO.sub.2 H C.sub.6 H.sub.5 H H COOCH.sub.3 NH(CH.sub.3).sub.3.sup..sym.2.365 NO.sub.2 H C.sub.6 H.sub.5 H H COOCH.sub.3 NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.366 H NO.sub.2 C.sub.6 H.sub.5 H H COOCH.sub.3 Na.sup..sym.2.367 H NO.sub.2 C.sub.6 H.sub.5 H H COOCH.sub.3 Li.sup..sym.2.368 H NO.sub.2 C.sub.6 H.sub.5 H H COOCH.sub.3 1/2Ca.sup.2.sym.2.369 H NO.sub.2 C.sub.6 H.sub.5 H H COOCH.sub.3 NH(CH.sub.3).sub.3.sup..sym.2.370 H NO.sub.2 C.sub.6 H.sub.5 H H COOCH.sub.3 NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.371 H H C.sub.6 H.sub.5 H H COOCH.sub.3 Na.sup..sym.2.372 H H C.sub.6 H.sub.5 H H COOCH.sub.3 Li.sup..sym.2.373 H H C.sub.6 H.sub.5 H H COOCH.sub.3 1/2Ca.sup.2.sym.2.374 H H C.sub.6 H.sub.5 H H COOCH.sub.3 NH(CH.sub.3).sub.3.sup..sym.2.375 H H C.sub.6 H.sub.5 H H COOCH.sub.3 NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.376 Cl CCl.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 Na.sup..sym.2.377 Cl CCl.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 Li.sup..sym.2.378 Cl CCl.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 1/2Ca.sup.2.sym.2.379 Cl CCl.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 NH(CH.sub.3).sub.3.sup..sym.2.380 Cl CCl.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.2.381 F CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 Na.sup..sym.2.382 F CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 Li.sup..sym.2.383 F CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 1/2Ca.sup.2.sym.2.384 F CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 NH(CH.sub.3).sub.3.sup..sym.2.385 F CF.sub.3 C.sub.6 H.sub.5 H H COOCH.sub.3 NH(C.sub.2 H.sub.5 OH).sub.3.sup..sym.__________________________________________________________________________
P.2.1. Preparation of the pyridinecarboxylic acid halides of formula II
P.2.1.1. Preparation of 5-trifluoromethylpyridine-2-carboxylic acid chloride
9.8 ml (0.11 mol) of oxalyl chloride are added dropwise to a suspension of 22.9 g (0.1 mol) of the potassium salt of 5-trifluoromethylpyridine2-carboxylic acid and 10 drops of DMF in 250 ml of toluene, the temperature rising to 40.degree. C. and brisk evolution of gas occurring. The whole is then stirred for 2 hours at 40.degree. C. The light-brown suspension is subsequently concentrated by evaporation on a rotary evaporator, stirred with 250 ml of absolute ether, filtered and concentrated by evaporation again.
17.8 g (85%) of the title compound of formula ##STR28## are isolated in the form of a brown oil (Compound No. 3.078).
P.2.1.2. Preparation of 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid ethyl ester
216 g (1 mol) of 2,3-dichloro-5-trifluoromethylpyridine, 16.7 g of [PdCl.sub.2 (PPh.sub.3).sub.2 ] and 420 ml (3 mol) of triethylamine are stirred for 14 hours at 50 bar and 100.degree. C. in 3.3 1 of ethanol in a CO atmosphere. The whole is then concentrated by evaporation on a rotary evaporator at 40.degree. C. The resulting mass is stirred with 2 1 of ether, the triethylamine hydrochloride is filtered off, and the filtrate is concentrated by evaporation on a rotary evaporator. 245 g of a brown oil are obtained, which is purified on silica gel with ethyl acetate/hexane (1:9).
206.8 g (81.6%) of the title compound of formula ##STR29## are isolated in the form of a yellow oil (Compound No. 3.005).
P.2.1.3. Preparation of 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid
76 g (0.3 mol) of 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid ethyl ester are stirred for 6 hours with 165 ml (0.33 mol) of 2N NaOH. The resulting solution is washed twice with methylene chloride. The aqueous solution is then adjusted to pH 1 with 37% hydrochloric acid and the product is filtered off with suction and dried at room temperature in vacuo.
65 g (96%) of the title compound of formula ##STR30## are isolated in the form of white crystals having a melting point of 135.degree. C. (decomp.) (Compound No. 3.039).
P.2.1.4. Preparation of 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid chloride
16.9 g (75 mmol) of 3-chloro-5-trifluoromethylpyridine-2-carboxylic acid are suspended in 75 ml of hexane. After the addition of 2 drops of DMF 7 ml (80 mmol) of oxalyl chloride in 25 ml of hexane are added dropwise. The whole is then stirred for 4 hours at 50.degree. C. until the evolution of gas has ceased. The reaction solution is filtered and concentrated by evaporation on a rotary evaporator.
18 g (98%) of the title compound of formula ##STR31## are isolated in the form of a yellow oil (Compound No. 3.073).
The compounds of Table 3 can be synthesised analogously to the above preparation processes.
P.2.1.5. Preparation of 3,5-dichloropyridine-2-carboxylic acid ethyl ester
250 g (1.3 mol) of 95% 2,3,5-trichloropyridine are reacted and purified as described in P.2.1.2.
147 g (51.5%) of the title compound of formula ##STR32##
P.2.1.6. Preparation of 3-chloro-5-methylthio-2-carboxylic acid ethyl ester
8.6 g (0.18 mol) of methylmercaptan are introduced into a suspension of 17.9 g (0.16 mol) of potassium tert.-butoxide and 4.8 g of polyethylene glycol 1500 in 480 ml of toluene at from 25.degree. to 30.degree. C. The whole is then stirred for 15 minutes at 35.degree. C. The resulting white suspension is cooled to -30.degree. C. and 35.2 g (0.16 mol) of 3,5-dichloropyridine-2-carboxylic acid ethyl ester are added, the whole is warmed to from 20.degree. to 25.degree. C. and stirred at that temperature for 15 hours. The potassium chloride is filtered off from the reaction mixture and the filtrate is concentrated by evaporation on a rotary evaporator. 41 g of a yellow oil are obtained, which is purified on silica gel with petroleum ether/ether (3:1).
16 g (43.3% of the title compound of formula ##STR33## are isolated in the form of a yellow oil (Compound No. 3.018).
P.2.1.7. Preparation of 3-chloro-5-methylthiopyridine-2-carboxylic acid
22 g (0.095 mol) of 3-chloro-5-methylthiopyridine-2-carboxylic acid ethyl ester are reacted and purified analogously to P.2.1.3..
18.3 g (94.7%) of the title compound of formula ##STR34## are isolated in the form of white crystals (Compound No. 3.052).
P.2.1.8. Preparation of 3-chloro-5-methylthiopyridine-2-carboxylic acid chloride
9.8 g (0.048 mol) of 3-chloro-5-methylthiopyridine-2-carboxylic acid are suspended in 65 ml of hexane and 25 ml of dichloroethane. After the addition of 2 drops of DMF and heating to 55.degree. C., 4.9 ml (0.055 mol) of oxalyl chloride are added dropwise. The whole is then stirred for 4 hours at 55.degree. C., until the evolution of gas has ceased. The reaction solution is filtered and concentrated by evaporation on a rotary evaporator.
10.6 g (99.5%) of the title compound of formula ##STR35## are isolated in the form of yellow, wax-like crystals (Compound No. 3.086).
P.2.2.1. 3-Chloro-5-methylsulfonyl-pyridin-2-carboxylic acid ethylester
44 g (140 mmol) 55% 3-chloroperbenzoic acid in 150 ml dichloromethane are added to a solution of 16.2 g (70 mmol) of 3-chlor-5-methylthiopyridin-2-carboxylic acid ethylester in such a manner that the temperature does not exced 30.degree. C. The mixture is then stirred for 15 hours at room temperature and again 19 g (70 mmol) 3-chloroperbenzoic acid in 75 ml dichloromethane are added to this suspension to complete reaction. It is then stirred for another 3 hours at room temperature. The white suspension is diluted with 200 ml dichloromethane and filtered off from the 3-dichlorobenzoic acid. The filtrate is washed with 5% NaHCO.sub.3 solution and water and concentrated by evaporation on a rotary evaporator.
15.3 g (83%) of the title compound of formula ##STR36## are isolated in the form of crystals of a m.p. of 90.degree.-93.degree. C. (Compound No. 3.017).
P.2.2.2. 3-Chloro-5-methylsulfonyl-pyridine-2-carboxylic acid
13.2 g (0.05 mol) 3-chloro-5-methylsulfonyl-pyridine-2-carboxylic acid ethylester are added to a mixture of 55 ml (0.055 mol) 1N NaOH and 5.5 ml ethanol. The temperature rises to 32.degree. C. It is stirred for 3 hours at room temperature. This solution is then diluted with 150 ml of water, washed twice with dichloromethane and is then adjusted at a low pH by adding 37% HCl. The product is filtered off, washed with ice water and dried.
10.4 g (88.3%) of the title compound of formula ##STR37## are isolated in the form of crystals with a m.p. of >150.degree. C. (decomp.) (Compound No. 3.051).
P.2.2.3. 3-Chloro-5-methylsulfonyl-pyridin-2-carboxylic acid chloride
9.9 g (0.042 mol) of 3-chloro-5-methanesulfonyl-pyridine-2-carboxylic acid in 100 ml toluene and 4.4 ml (0.06 mol) thionylchloride are heated up to the boiling point for 2 hours. The brown suspension is then concentrated by evaporation on a rotary evaporator.
10.4 g (97.5%) of the title compound of formula ##STR38## are isolated in the form of a brown wax (Compound No. 3.086).
TABLE 3______________________________________Compounds of formula ##STR39##Comp.No. R.sup.1 R.sup.2 Y phys. data______________________________________3.001 Cl Cl OC.sub.2 H.sub.5 oil3.002 Cl H OC.sub.2 H.sub.5 oil3.003 H Cl OC.sub.2 H.sub.5 m.p. 56-58.degree. C.3.004 H H OC.sub.2 H.sub.53.005 Cl CF.sub.3 OC.sub.2 H.sub.5 oil3.006 NO.sub.2 H OC.sub.2 H.sub.53.007 H NO.sub.2 OC.sub.2 H.sub.5 m.p. 89-91.degree. C.3.008 NO.sub.2 Cl OC.sub.2 H.sub.53.009 CF.sub.3 H OC.sub.2 H.sub.53.010 H CF.sub.3 OC.sub.2 H.sub.5 m.p. 43-45.degree. C.3.011 OCH.sub.3 H OC.sub.2 H.sub.53.012 CN H OC.sub.2 H.sub.53.013 OCH.sub.3 Cl OC.sub.2 H.sub.53.014 CN Cl OC.sub.2 H.sub.53.015 Br Cl OC.sub.2 H.sub.53.016 SCH.sub.3 Cl OC.sub.2 H.sub.5 m.p. 77-80.degree. C.3.017 SO.sub.2 CH.sub.3 Cl OC.sub.2 H.sub.5 m.p. 90-93.degree. C.3.018 Cl SCH.sub.3 OC.sub.2 H.sub.5 oil3.019 Cl SOCH.sub.3 OC.sub.2 H.sub.53.020 Cl SO.sub.2 CH.sub.3 OC.sub.2 H.sub.53.021 SOCH.sub.3 Cl OC.sub.2 H.sub.53.022 SO.sub.2 CH.sub.3 H OC.sub.2 H.sub.53.023 H SO.sub.2 CH.sub.3 OC.sub.2 H.sub.53.024 H CH.sub.3 OC.sub.2 H.sub.5 oil3.025 Cl F OC.sub.2 H.sub.5 oil3.026 H CF.sub.3 OC.sub.2 H.sub.53.027 F F OC.sub.2 H.sub.53.028 F CF.sub.3 OC.sub.2 H.sub.53.029 CF.sub.3 F OC.sub.2 H.sub.53.030 H CCl.sub.3 OC.sub.2 H.sub.53.031 CCl.sub.3 H OC.sub.2 H.sub.53.032 Cl CCl.sub.3 OC.sub.2 H.sub.53.033 CCl.sub.3 Cl OC.sub.2 H.sub.53.034 CH.sub.3 H OC.sub.2 H.sub.53.035 Cl Cl OH m.p. 157.degree. C. (decomp.)3.036 Cl H OH m.p. >125.degree. C. (decomp.)3.037 H Cl OH m.p. 135.degree. C. (decomp.)3.038 H H OH3.039 Cl CF.sub.3 OH m.p. 135.degree. C. (decomp.)3.040 NO.sub.2 H OH3.041 H NO.sub.2 OH3.042 NO.sub.2 Cl OH3.043 CF.sub.3 H OH m.p. 129-131.degree. C.3.044 H CF.sub.3 OH3.045 OCH.sub.3 H OH3.046 CN H OH3.047 OCH.sub.3 Cl OH3.048 CN Cl OH3.049 Br Cl OH3.050 SCH.sub.3 Cl OH3.051 SO.sub.2 CH.sub.3 Cl OH m.p. >150.degree. C. (decomp.)3.052 Cl SCH.sub.3 OH solid3.053 Cl SOCH.sub.3 OH3.054 Cl SO.sub.2 CH.sub.3 OH3.055 SOCH.sub.3 Cl OH3.056 SO.sub.2 CH.sub.3 H OH3.057 H SO.sub.2 CH.sub.3 OH3.058 H CH.sub.3 OH m.p. >135.degree. C. (decomp.)3.059 Cl F OH m.p. >143.degree. C. (decomp.)3.060 H CF.sub.3 OH3.061 F F OH3.062 F CF.sub.3 OH3.063 CF.sub.3 F OH3.064 H CCl.sub.3 OH3.065 CCl.sub.3 H OH3.066 Cl CCl.sub.3 OH3.067 CCl.sub.3 Cl OH3.068 CH.sub.3 H OH3.069 Cl Cl Cl m.p. 54-56.degree. C.3.070 Cl H Cl solid3.071 H Cl Cl solid3.072 H H Cl3.073 Cl CF.sub.3 Cl oil3.074 NO.sub.2 H Cl3.075 H NO.sub.2 Cl3.076 NO.sub.2 Cl Cl3.077 CF.sub.3 H Cl oil3.078 H CF.sub.3 Cl oil3.079 OCH.sub.3 H Cl3.080 CN H Cl3.081 OCH.sub.3 Cl Cl3.082 CN Cl Cl3.083 Br Cl Cl3.084 SCH.sub.3 Cl Cl3.085 SO.sub.2 CH.sub.3 Cl Cl3.086 Cl SCH.sub.3 Cl solid3.087 Cl SOCH.sub.3 Cl3.088 Cl SO.sub.2 CH.sub.3 Cl3.089 SOCH.sub.3 Cl Cl3.090 SO.sub.2 CH.sub.3 H Cl3.091 H SO.sub.2 CH.sub.3 Cl3.092 H CH.sub.3 Cl oil3.093 Cl F Cl oil3.094 H CF.sub.3 Cl3.095 F F Cl3.096 F CF.sub.3 Cl3.097 CF.sub.3 F Cl3.098 H CCl.sub.3 Cl3.099 CCl.sub.3 H Cl3.100 Cl CCl.sub.3 Cl3.101 CCl.sub.3 Cl Cl3.102 CH.sub.3 H Cl3.103 Cl OCH.sub.3 OC.sub.2 H.sub. 53.104 Cl OCH.sub.3 OH solid3.105 Cl OCH.sub.3 Cl solid3.106 H OCH.sub.3 OC.sub.2 H.sub.53.107 H OCH.sub.3 OH3.108 H OCH.sub.3 Cl3.109 H OC.sub.3 H.sub.7 (i) OC.sub.2 H.sub.53.110 H OC.sub.3 H.sub.7 (i) OH3.111 H OC.sub.3 H.sub.7 (i) Cl3.112 H OCH.sub.3 OCH.sub.3 m.p. 27-74.degree. C.3.113 H SCH.sub.3 OC.sub.2 H.sub.5 m.p. 46-48.degree. C.3.114 H SCH.sub.3 OH m.p. 159-160.degree. C.3.115 H SCH.sub.3 Cl solid3.116 Cl SC.sub.2 H.sub.5 OH3.117 Cl SC.sub.2 H.sub.5 OC.sub.2 H.sub.53.118 Cl SC.sub.2 H.sub.5 Cl3.119 Cl SOC.sub.2 H.sub.5 OH3.120 Cl SOC.sub.2 H.sub.5 OC.sub.2 H.sub.53.121 Cl SOC.sub.2 H.sub.5 Cl3.122 Cl SO.sub.2 C.sub.3 H.sub.7 (i) OH3.123 Cl SOC.sub.3 H.sub.7 (i) OH3.124 Cl SC.sub.3 H.sub.7 (i) OH3.125 Cl SO.sub.2 C.sub.3 H.sub.7 (i) OC.sub.2 H.sub.53.126 Cl SOC.sub.3 H.sub.7 (i) OC.sub.2 H.sub.53.127 Cl SC.sub.3 H.sub.7 (i) OC.sub.2 H.sub.53.128 Cl SO.sub.2 C.sub.3 H.sub.7 (i) Cl3.129 Cl SOC.sub.3 H.sub.7 (i) Cl3.130 Cl SC.sub.3 H.sub.7 (i) Cl3.131 Cl OC.sub.3 H.sub.7 (i) OH3.132 Cl OC.sub.3 H.sub.7 (i) OC.sub.2 H.sub.53.133 Cl OC.sub.3 H.sub.7 (i) Cl3.134 SCH.sub.3 SCH.sub.3 OC.sub.2 H.sub.5 m.p. 60-70.degree. C.3.135 Cl Br OH3.136 Cl Br OC.sub.2 H.sub.53.137 Cl Br Cl3.138 Cl OCH.sub.3 OCH.sub.3 m.p. 72-74.degree. C.3.139 Cl Cl COOC.sub.2 H.sub.5 oil______________________________________
F. FORMULATION EXAMPLES
Example F1
Formulation Examples for active ingredients of formula I (throughout, percentages are by weight)
______________________________________(a) Emulsifiable concentrates (a) (b) (c)______________________________________a compound according to Table 1 or 2 20% 40% 50%calcium dodecylbenzenesulfonate 5% 8% 5.8%castor oil polyethylene glycol ether 5% -- --(36 moles of ethylene oxide)tributylphenol polyethylene glycol -- 12% 4.2%ether (30 moles of ethylene oxide)cyclohexanone -- 15% 20%xylene mixture 70% 25% 20%______________________________________
Emulsions of any desired concentration can be produced from such concentrates by dilution with water.
______________________________________(b) Solutions (a) (b) (c)______________________________________a compound according Table 1 or 2 80% 10% 5%ethylene glycol monomethyl ether 20% -- --polyethylene glycol MW 400 -- 70% --N-methyl-2-pyrrolidone -- 20% 5%epoxidised coconut oil -- -- 90%______________________________________
These solutions are suitable for application in the form of micro-drops.
______________________________________(c) Granulates (a) (b)______________________________________a compound according to Table 1 or 2 5% 10%kaolin 94% --highly dispersed silicic acid 1% --attapulgite -- 90%______________________________________
The active ingredient is dissolved, sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
______________________________________(d) Dusts (a) (b) (c)______________________________________a compound according to Table 1 or 2 2% 5% 8%highly dispersed silicic acid 1% 5% 5%talcum 97% -- 10%kaolin -- 90% 77%______________________________________
Ready-for-use dusts are obtained by homogeneously mixing the carriers with the active ingredient.
______________________________________(e) Wettable powders (a) (b)______________________________________a compound according Table 1 or 2 20% 60%sodium lignosulfonate 5% 5%sodium lauryl sulfate 3% 6%octylphenol polyethylene glycol ether -- 2%(7-8 moles of ethylene oxide)highly dispersed silicic acid 5% 27%kaolin 67% --______________________________________
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
______________________________________(f) Extruder granulate______________________________________a compound according to Table 1 or 2 10%sodium lignosulfonate 2%carboxymethylcellulose 1%kaolin 87%______________________________________
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a steam of air.
______________________________________(g) Coated granulate______________________________________a compound according to Table 1 or 2 3%polyethylene glycol (MW 200) 3%kaolin 94%______________________________________
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
______________________________________(h) Suspension concentrate______________________________________a compound according to Table 1 or 2 40%ethylene glycol 10%nonylphenol polyethylene glycol 6%ether (15 moles of ethylene oxide)sodium lignosulfonate 10%carboxymethylcellulose 1%37% aqueous formaldehyde solution 0.2%silicone oil in the form of a 75%aqueous emulsion 0.8%water 32%______________________________________
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be produced by dilution with water.
B. Biological Examples
Example B1
Pre-emergence herbicical action
In a greenhouse, immediately after sowing the test plants in seed trays the surface of the soil is treated with an aqueous dispersion of the test compound obtained from a 25% emulsifiable concentrate. Various rates of application of active ingredient/hectare are tested. The seed trays are kept in the greenhouse at 22.degree.-25.degree. C. and 50-70% relative humidity and the test is evaluated after 3 weeks.
The herbicidal action is assessed in comparison with an untreated control group using a nine-stage evaluation scale (1=total damage of the test plants, 9=no herbicidal action on the test plants).
Ratings of 1 to 4 (especially 1 to 3) indicate a good to very good herbicidal action. Ratings of 6 to 9 (especially 7 to 9) indicate a good tolerance (especially in the case of crop plants). The test results for compound No. 1.005 are compiled in Table 4.
TABLE 4______________________________________ Rate of application [g/ha]Test plant 2000 1000 5000 250 125 60______________________________________barley 7 7 9 9 9 9wheat 8 9 9 9 9 9maize 8 9 9 9 9 9sorghum 7 8 9 9 9 9Abutilon 1 1 2 2 2 5Chenopodium Sp. 1 1 1 1 1 1Solanum nigrum 1 1 1 1 2 3Veronica Sp. 1 1 1 1 4 6______________________________________
Example B2
Post-emergence herbicidal action
A number of weeds, both monocotyledons and dicotyledons, are sprayed after emergence (at the 4- to 6-leaf stage) with an aqueous dispersion of active ingredient at a rate of 250 g to 2 kg of active ingredient per hectare and kept at 24.degree.-26.degree. C. and 45-60% relative humidity. 15 days after the treatment the test is evaluated in accordance with the evaluation scheme described in Example B1.
The test results for compound 1.005 are compiled in Table 5.
TABLE 5______________________________________ rate of application [g/ha]Test plant 2000 1000 5000 250______________________________________barley 9 9 9 9wheat 8 9 9 9maize 8 9 9 9sorghum 7 8 9 9rice (dry) 7 8 9 9Abutilon 1 1 2 3Chenopodium Sp. 1 1 1 2Solanum nigrum 1 1 1 2Sinapis 2 2 3 3______________________________________
Example B3
Herbicidal action in paddy
The water weeds Echinochloa crus galli and Monocharia vag. are sown in plastics beakers (60 cm.sup.2 surface area, 500 ml volume). After sowing, the beakers are filled to the soil surface with water. 3 days after sowing, the water level is raised to slightly above (3-5 mm) the surface of the soil. Application is carried out 3 days after sowing by spraying an aqueous emulsion of the test substances onto the vessels at a rate of application of 60 to 250 g of active ingredient per hectare. The plant beakers are then placed in a greenhouse under optimum growth conditions for the rice weeds, i.e. at 25.degree.-30.degree. C. and high humidity. The tests are evaluated 3 weeks after the application. The compounds of Table 1 damage the weeds but not the rice.
Claims
  • 1. A compound of formula I or I' ##STR40## in which R.sup.1 and R.sup.2 independently of one another are each hydrogen; halogen; nitro; cyano; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 alkoxy; C.sub.1 -C.sub.4 alkyl-S(O).sub.n --; COR.sup.8 ; C.sub.1 -C.sub.4 haloalkoxy; or C.sub.1 -C.sub.4 haloalkyl; R.sup.3, R.sup.4 and R.sup.5 independently of one another are each hydrogen; C.sub.1 -C.sub.4 alkyl; or phenyl or benzyl each unsubstituted or substituted by up to three identical or different substituents from halogen, nitro, cyano, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkyl-S(O).sub.n --, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 haloalkyl-S(O).sub.n -- and C.sub.1 -C.sub.4 haloalkoxy; R.sup.6 is hydrogen; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 alkoxycarbonyl; or cyano; R.sup.7 is OH; or O.sup..crclbar. M.sup..sym. ; R.sup.8 is OH; C.sub.1 -C.sub.4 alkoxy; NH.sub.2 ; C.sub.1 -C.sub.4 alkylamino; or di-C.sub.1 - C.sub.4 alkylamino; n is 0, 1 or 2; M.sup..sym. is a cation equivalent of a metal ion or of an ammonium ion that is unsubstituted or substituted by up to three C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 hydroxyalkyl or C.sub.1 -C.sub.4 alkoxy-C.sub.1 -C.sub.4 alkyl groups.
  • 2. A compound according to claim 1 of formula I or I' ##STR41## in which the radicals R.sup.1 and R.sup.2 are bonded in the 3- and 5-positions of the pyridine ring and the pyridinecarbonyl system is bonded by way of the 2-position of the pyridine ring.
  • 3. A compound according to claim 1 of formula I or I' ##STR42## in which R.sup.1 is hydrogen; halogen; nitro; cyano; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 alkoxy; C.sub.1 -C.sub.4 alkyl-S(O).sub.n --; COR.sup.8 ; C.sub.1 -C.sub.4 haloalkoxy; or C.sub.1 -C.sub.4 haloalkyl; R.sup.2 is hydrogen; halogen; nitro; cyano; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 alkoxy; C.sub.1 -C.sub.4 haloalkoxy; C.sub.1 -C.sub.4 alkyl-S(O).sub.n --; or C.sub.1 -C.sub.4 haloalkyl; R.sup.3, R.sup.4 and R.sup.5 independently of one another are each hydrogen; C.sub.1 -C.sub.4 alkyl; or phenyl or benzyl each unsubstituted or substituted by up to three identical or different substituents from halogen, nitro, cyano, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkyl-S(O).sub.n--, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 haloalkyl-S(O).sub.n -- and C.sub.1 -C.sub.4 haloalkoxy; R.sup.6 is hydrogen; C.sub.1 -C.sub.4 alkoxycarbonyl; or cyano; R.sup.7 is OH; or O.sup..crclbar. M.sup..sym. ; R.sup.8 is OH; C.sub.1 -C.sub.4 alkoxy; NH.sub.2 ; C.sub.1 -C.sub.4 alkylamino; or di-C.sub.1 -C.sub.4 alkylamino; n is 0, 1 or 2; M.sup..sym. is a cation equivalent of an alkali metal ion, an alkaline earth metal ion or an ammonium ion; of a mono-C.sub.1 -C.sub.4 alkylammonium ion; of a di-C.sub.1 -C.sub.4 alkylammonium ion; of a tri-C.sub.1 -C.sub.4 alkylammonium ion; or of a triethanolammonium ion.
  • 4. A compound of formula I or I' in which at least one of the radicals R.sup.3 to R.sup.6 is hydrogen, according to claim 1.
  • 5. A compound of formula I or I' in which at least two of the radicals R.sup.3 to R.sup.6 are hydrogen, according to claim 1.
  • 6. A compound of formula I or I' in which R.sup.6 is cyano and R.sup.5 is hydrogen, according to claim 1.
  • 7. A compound of formula I or I' in which R.sup.6 is cyano, R.sup.6 is hydrogen and R.sup.3 and R.sup.4 independently of one another are each hydrogen or C.sub.1 -C.sub.4 alkyl, according to claim 1.
  • 8. A compound of formula I or I' in which R.sup.6 is C.sub.1 -C.sub.4 alkoxycarbonyl, according to claim 1.
  • 9. A compound of formula I or I' in which R.sup.7 is OH, according to claim 1.
  • 10. A compound of formula I or I' in which R.sup.7 is O.sup..crclbar. --M.sup..sym., according to claim 1.
  • 11. A compound of formula I or I' in which R.sup.1 is hydrogen, chlorine, fluorine, nitro, trifluoromethyl, methoxy, bromine, methylthio, methylsulfonyl, carboxy, trichloromethyl or methyl, according to claim 1.
  • 12. Cyclohexanediones of formula I or I' in which R.sup.2 is hydrogen, chlorine, nitro, methylthio, methylsulfinyl, methylsulfonyl, methyl, fluorine, trifluoromethyl or trichloromethyl, according to claim 1.
  • 13. 2-(3-chloro-5-trifluoromethylpyridin-2-ylcarbonyl)-cyclohex-1-en-1-ol-3-one or 2-(3-chloro-b 5-methylsulfonylpyridin-2-ylcarbonyl)-cyclohex-1-en-1-ol-3-one as a compound of formula I according to claim 1.
  • 14. A herbicidal composition which comprises a herbicidally effective amount of a compound of formula I or I' according to claim 1, together with a carrier or other adjuvant.
  • 15. A method of controlling undesired plant growth, which comprises allowing a herbicidally effective amount of a compound of formula I or I' according to claim 1 to act on the plants to be controlled or the locus thereof.
Priority Claims (2)
Number Date Country Kind
2825/88 Jul 1988 CHX
29/89 Jan 1989 CHX
US Referenced Citations (6)
Number Name Date Kind
4319916 Abdulla Mar 1982
4631081 Watson et al. Dec 1986
4708732 Carter Nov 1987
4781751 Chin Nov 1988
4783213 Lee Nov 1988
4872902 Brunner Oct 1987
Foreign Referenced Citations (6)
Number Date Country
0090262 Mar 1983 EPX
0283152 Feb 1988 EPX
283261 Sep 1988 EPX
0317158 Nov 1988 EPX
316491 May 1989 EPX
2206114 Jun 1988 GBX
Non-Patent Literature Citations (1)
Entry
193087D CA vol. 83, 1975.