Crop protection agents based on 1-aryl- or 1-hetarylimidazolecarboxylic esters

The present invention relates to 1-aryl- and 1-hetarylimidazolecarboxylic esters of the general formulae Ia and Ib ##STR2## where R.sup.1 is halogen or C.sub.1 -C.sub.4 -alkyl which may carry from one to three chlorine atoms,
R.sup.2 is C.sub.1 -C.sub.6 -alkyl which may carry from one to three of the radicals halogen, C.sub.1 -C.sub.4 -alkoxy and/or C.sub.1 -C.sub.4 -alkoxy-C.sub.1 -C.sub.4 -alkoxy, or is C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.6 -alkynyl or C.sub.3 -C.sub.6 -cycloalkyl,
R.sup.3 is hydrogen or C.sub.1 -C.sub.4 -alkyl and
R.sup.4 is a phenyl ring or a 5-membered or 6-membered heteroaromatic containing as heteroatoms one or two nitrogen atoms and/or an oxygen or a sulfur atom in the ring, and these aromatic rings may carry from one to three of the following groups: halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -haloalkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -haloalkylthio, C.sub.1 -C.sub.4 -alkylsulfinyl, C.sub.1 -C.sub.4 -alkylsulfonyl, C.sub.1 -C.sub.4 -alkylcarbonyl, C.sub.1 -C.sub.4 -alkoxycarbonyl, carboxyl, nitro and/or cyano.
The present invention furthermore relates to a process for the preparation of the compounds Ia and Ib and herbicides which contain the 2-(4-hetaryloxy)- or 2-(4-aryloxy)-phenoxyacetic or -propionic acid derivatives and/or cyclohexenone derivatives as herbicidal active ingredients and aryl- or hetarylimidazolecarboxylic acid derivatives as antidotes, and methods for selectively controlling undesirable plant growth with these herbicides.
EP-A 174 562 discloses 1-aryltriazolecarboxylic acid derivatives having crop-protecting activity. 1-Arylimidazolecarboxylic esters having growth-regulating properties (EP-A 243 615, EP-A 264 577) and 2-haloimidazolecarboxylic esters having a herbicidal action are also described (EP-A 127 446; EP-A 180 787; U.S. Pat. Nos. 4,711,962; 4,591,377 and 4,578,106).
Herbicidal active ingredients from the group consisting of the 2-(4-hetaryloxy)- or 2-(4-aryloxy)phenoxyacetic acid derivatives of the formula IV ##STR3## where R.sup.a is phenyl, pyridyl, benzoxazyl, benzothiazyl or benzopyrazinyl, and these aromatic ring systems may carry up to two of the following radicals: halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl and/or C.sub.1 -C.sub.4 -halophenoxy,
R.sup.b is hydrogen, C.sub.1 -C.sub.5 -alkyl, C.sub.3 -C.sub.5 -alkylideneimino, C.sub.3 -C.sub.5 -alkylideneiminooxy-C.sub.2 - or -C.sub.3 -alkyl or one equivalent of a plant-tolerated cation and
R.sup.c is hydrogen or methyl,
are used for controlling undesirable plants from the family of the gramineae (for example DE-A 22 23 894, DE-A 24 33 067, DE-A 25 76 251, DE-A 30 04 770, BE-A 868 875 and BE-A 858 618). However, the toleration of these substances by crops varies from commercially acceptable to non-tolerated, depending on the substituents and application rate.
The same situation is encountered with the cyclohexenone derivatives of the formula V ##STR4## where R.sup.d is C.sub.1 -C.sub.4 -alkyl,
R.sup.e is C.sub.1 -C.sub.4 -alkyl; C.sub.3 - or C.sub.4 -alkenyl, C.sub.3 - or C.sub.4 -alkynyl, C.sub.3 - or C.sub.4 -haloalkenyl or thenyl which may carry a halogen atom;
R.sup.f is C.sub.1 -C.sub.4 -alkyl which may be monosubstituted by C.sub.1 -C.sub.4 -alkylthio or C.sub.1 -C.sub.4 -alkoxy;
a 5-membered or 6-membered saturated or monounsaturated ring system which may contain, in addition to carbon members, an oxygen or sulfur atom or a sulfoxyl or sulfonyl group, and this ring may carry up to three of the following radicals: hydroxyl, halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy and/or C.sub.1 -C.sub.4 -alkylthio;
a 10-membered saturated or monounsaturated heterocyclic structure which contains two oxygen atoms or sulfur atoms and may be subtituted by up to three C.sub.1 -C.sub.4 -alkyl groups and/or methoxy groups;
phenyl, pyridyl or isoxazolyl, where these groups may carry up to three of the following radicals: C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.3 -C.sub.6 -alkenyloxy, C.sub.3 -C.sub.6 -alkynyloxy, C.sub.1 -C.sub.4 -alkoxy-C.sub.1 -C.sub.3 -alkyl, C.sub.1 -C.sub.4 -dialkoxy-C.sub.1 -C.sub.3 -alkyl, formyl, halogen and/or benzoylamino;
R.sup.g is hydrogen or hydroxyl or, when R.sup.f is C.sub.1 -C.sub.6 -alkyl, is C.sub.1 -C.sub.6 -alkyl;
R.sup.h is hydrogen, cyano, halogen or C.sub.1 -C.sub.4 -alkoxycarbonyl and
R.sup.i is hydrogen or one equivalent of an environmentally compatible cation.
They are also described in the literature as herbicides (e.g. EP-A 228 598, EP-A 230 235, EP-A 238 021, U.S. Pat. No. 4,432,786, DE-A 24 39 104) and serve predominantly for controlling undesirable grasses in dicotyledon crops and in grasses which do not belong to the gramineae family. Depending on the structure of the substituents and the dose used, compounds from this group can also be employed for selectively controlling undesirable grasses in gramineous crops, such as wheat and rice.
It is an object of the present invention to provide compounds which overcome or greatly reduce the disadvantages encountered when using the abovementioned herbicides of the formulae IV and V. Such compounds are also referred to as antidotes or safeners.
We have found that this object is achieved by the 1-aryl- and 1-hetarylimidazonecarboxylic esters Ia and Ib defined at the outset. We have furthermore found processes for the preparation of these compounds Ia and Ib and methods for using these compounds together with the herbicides IV and V for influencing undesirable plant growth. The present invention furthermore relates to agents which contain the compounds Ia and Ib and/or herbicides of type IV or V, it being immaterial whether the herbicidal active ingredient and the antidote are formulated and applied together or separately or, if they are applied seperately, which is applied first.
The novel compounds of the formulae Ia and Ib are obtainable by various methods.
Thus, the compounds Ia are obtained, for example, by reacting an imidazolecarboxylic ester of the formula II with an aryl or hetaryl derivative III in a conventional manner in an inert organic solvent in the presence of a base to give Ia. ##STR5##
In formula III, X is halogen, such as fluorine, chlorine or bromine, preferably fluorine or chlorine.
The reaction can be carried out continuously or batchwise, under atmospheric pressure or pressures up to 30, preferably from 1 to 10, bar and at from 20.degree. C. to 200.degree. C., preferably from 50.degree. C. to 170.degree. C.
Examples of suitable solvents are n-hexane, decalin, toluene, xylene, chlorobenzene, tetrahydrofuran, dioxane, dimethylformamide, diethylformamide, dimethyl sulfoxide, acetone and ethanol. Toluene and dimethylformamide are preferred.
Suitable bases are sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, sodium methylate, sodium ethylate, potassium tert-butylate, triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, isoquinoline, N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine and 1,8-diazabicyclo[5.4.0]undec-7-ene. However, sodium hydride, sodium methylate and triethylamine are preferred bases.
The preparation of the imidazolecarboxylic esters required for this purpose is described in, inter alia, ES-A 512 649 and EP-A 127 446.
The compounds Ib can be prepared from aryl- or hetarylimidazolecarboxylic esters Ia, in which R.sup.3 is hydrogen, in a conventional manner by reaction with a chlorinating agent. ##STR6##
Examples of suitable chlorinating agents are phosphorus oxytrichloride, sulfuryl chloride, thionyl chloride, phosgene, phosphorus pentachloride, phosphorus trichloride and sulfur tetrachloride, sulfuryl chloride being preferred.
The reaction is usually carried out in the presence or absence of an inert organic solvent, such as chlorobenzene or dichlorobenzene, continuously or batchwise at from 20.degree. C. to 200.degree. C. preferably from 80.degree. C. to 150.degree. C., under atmospheric or slightly superatmospheric pressure (1-5 bar).
If the reaction is carried out in the presence of one of the abovementioned solvents, it is advisable also to use a free radical initiator, such as dibenzoyl peroxide or azobisisobutyronitrile, to accelerate the reaction.
In view of the intended use of the compounds Ia and Ib as crop protection agents, suitable substituents are the following radicals:
R.sup.1 is alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl or ethyl;
haloalkyl, such as chloromethyl, dichloromethyl, trichloromethyl, 1,1-dichloroethyl or 1-chloroethyl, preferably chloromethyl, dichloromethyl or trichloromethyl; halogen, such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine;
R.sup.2 is alkyl as stated under R.sup.1, and n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl or 2-ethylbutyl, preferably methyl or ethyl;
alkenyl, such as allyl, 2-butenyl, 3-butenyl, 1-methyl2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1,2-dimethyl-2-propenyl, 1,1-dimethyl-2-propenyl, 1-methyl-3-butenyl, 1-ethyl-2-propenyl, 2-hexenyl, 1-methyl-2-pentenyl, 1-ethyl-2-butenyl and 2-ethyl-2-butenyl, preferably allyl, 2-butenyl or 1-methyl-2-propenyl;
alkynyl, such as 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-methyl-2-butynyl, 1-ethyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl or 1-methyl-2-pentynyl, preferably 2-propynyl, 1-methyl-2-propynyl or 2-butynyl;
cycloalkyl, such as cyclopropane, cyclobutane, cyclopentane or cyclohexane, preferably cyclopropane, cyclopentane or cyclohexane;
haloalkyl as stated under R.sup.1, and fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2-difluoroethyl or 2,2,2-trifluoroethyl, preferably difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl or 2-chloroethyl;
alkoxyalkyl, such as 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 3-methoxypropyl or 3-ethoxypropyl, preferably methoxyethyl or 2-ethoxyethyl;
alkoxyalkoxyalkyl, such as 2-methoxymethoxyethyl, 2-ethoxymethoxyethyl or 2-ethoxyethoxyethyl;
R.sup.3 is hydrogen or alkyl as stated under R.sup.1, preferably hydrogen, methyl or ethyl;
R.sup.4 is a phenyl ring or
a 5-membered or 6-membered heteroaromatic, such as pyrrole, pyrazole, imidazole, furan, thiophene, oxazole, thiazole, isoxazole, isothiazole, pyridine, pyridazine, pyrimidine or pyrazine, preferably pyridine or pyrimidine.
Preferred substituents of R.sup.4 are
alkyl as stated under R.sup.1, in particular methyl, ethyl or isopropyl;
haloalkyl as stated under R.sup.2, in particular trifluoromethyl or difluoromethyl;
alkoxy, such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methoxy, 2-methoxy or 1,1-dimethylethoxy, in particular methoxy, ethoxy or 2-propoxy;
haloalkoxy, such as trifluoromethoxy, trichloromethoxy, fluoromethoxy, 2,2,2-trifluoroethoxy, 1,2,2-trifluoromethoxy or 1,1,2,2-tetrafluoroethoxy, in particular trifluoromethoxy or 2,2,2-trifluoroethoxy;
alkylthio, such as methylthio, ethylthio, propylthio, 2-propylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio or 1,1-dimethylethylthio, in particular methylthio or ethylthio;
haloalkylthio, such as trifluoromethylthio or trichloromethylthio;
alkylsulfinyl, such as methylsulfinyl or ethylsulfinyl;
alkylsulfonyl, such as methylsulfonyl or ethylsulfonyl;
alkylcarbonyl, such as acetyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl or 1,1-dimethylethylcarbonyl, in particular acetyl, 1-methylpropylcarbonyl or 1,1-dimethylethylcarbonyl;
alkoxycarbonyl, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl or 1-methylethoxycarbonyl;
halogen, such as fluorine, chlorine or bromine, in particular fluorine or chlorine, or carboxyl, nitro or cyano.
Particularly preferred compounds Ia and Ib are those in which R.sup.4 is unsubstituted or monosubstituted or disubstituted.
Specific examples of herbicidal (hetaryloxy)- or aryloxyphenoxyacetic acid derivatives of the formula IV whose toleration by crops can be improved by aryl- or hetarylimidazolecarboxylic esters of the formulae Ia and Ib are listed in Table A below:
TABLE A______________________________________ ##STR7## IVNo. R.sup.a R.sup.b R.sup.c Lit______________________________________IV.1 ##STR8## CH.sub.3 CH.sub.3 DE-A 22 23 894IV.2 ##STR9## n-C.sub.4 H.sub.9 CH.sub.3 BE-A 868 875IV.3 ##STR10## C.sub.2 H.sub.5 CH.sub.3 BE-A 858 618IV.4 ##STR11## CH.sub.3 CH.sub.3 BE-A 868 875IV.5 ##STR12## C.sub.2 H.sub.5 CH.sub.3 DE-A 30 04 770______________________________________ Specific examples of cyclohexenones of the formula V whose crop plant compatibility can be improved by 1aryl- and 1hetarylimidazolecarboxylates of the formulae Ia and Ib are given in Table B.
TABLE B__________________________________________________________________________ ##STR13## VNo. R.sup.d R.sup.e R.sup.f R.sup.g R.sup.h R.sup.i Literature__________________________________________________________________________V.1 C.sub.3 H.sub.7 CH.sub.2 CHCH.sub.2 CH.sub.3 CH.sub.3 CO.sub.2 CH.sub.3 Na DE-A 2 439 104V.2 C.sub.3 H.sub.7 CH.sub.2 CH.sub.3 CH.sub.2 CH(CH.sub.3)SCH.sub.2 CH.sub.3 H H H DE-A 2 822 304V.3 C.sub.2 H.sub.5 CH.sub.2 CHCHCl CH.sub.2 CH(CH.sub.3)SCH.sub.2 CH.sub.3 H H H US-A 4 440 566V.4 C.sub.3 H.sub.7 CH.sub.2 CHCHCl CH.sub.2 CH(CH.sub.3)SCH.sub.2 CH.sub.3 H H H US-A 4 440 566V.5 C.sub.3 H.sub.7 C.sub.2 H.sub.5 ##STR14## H H H EP-A 71 707V.6 C.sub.2 H.sub. 5 C.sub.2 H.sub.5 ##STR15## H H H EP-A 71 707V.7 CH.sub.3 CH.sub.2 CHCHCH.sub.3 ##STR16## H H H EP-A 71 707V.8 C.sub.3 H.sub.7 C.sub.2 H.sub.5 ##STR17## H H H EP-A 71 707V.9 C.sub.2 H.sub.5 CH.sub.2 CHCHCl ##STR18## H H H EP-A 142 741V.10 C.sub.3 H.sub.7 C.sub.2 H.sub.5 ##STR19## H H H EP-A 66 195V.11 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR20## H H H DE-A 24 39 104V.12 C.sub.2 H.sub.5 CH.sub.2 CHCHCH.sub.3 ##STR21## H H H DE-A 38 08 072V.13 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR22## H H H EP-A 880 301V.14 C.sub.3 H.sub.7 CH.sub.2 CHCHCl ##STR23## H H H EP-A 88 299V.15 C.sub.3 H.sub.7 CH.sub.2 CHCHCH.sub.3 ##STR24## H H H EP-A 88 299V.16 C.sub.2 H.sub.5 CH.sub.2 CHCHCH.sub.3 ##STR25## H H H EP-A 238 021V.17 C.sub.3 H.sub.7 CH.sub.2 CHCHCH.sub.3 ##STR26## H H H EP-A 238 021V.18 C.sub.2 H.sub.5 CH.sub.2 CHCHCl ##STR27## H H H EP-A 137 174V.19 C.sub.3 H.sub.7 C.sub.2 H.sub.5 ##STR28## H H H EP-A 2 137 200V.20 C.sub.3 H.sub.7 C.sub.2 H.sub.5 ##STR29## H H H EP-A 230 235V.21 C.sub.3 H.sub.7 CH.sub.2 CHCHCl ##STR30## H H H EP-A 230 235V.22 C.sub.3 H.sub.7 CH.sub.2 CHCHCl ##STR31## H H H EP-A 46 860V.23 C.sub.3 H.sub.7 C.sub.2 H.sub.5 ##STR32## H H H JP-A 540 191 945V.24 C.sub.3 H.sub.7 C.sub.2 H.sub.5 ##STR33## H H H EP-A 46 860V.25 CH.sub.3 CH.sub.2 CHCHCl ##STR34## H H H EP-A 88 299V.26 C.sub.3 H.sub.7 C.sub.2 H.sub.5 ##STR35## H H K EP-A 137 174V.27 C.sub.2 H.sub.5 CH.sub.2 CHCHCl ##STR36## H H H EP-A 46 860__________________________________________________________________________
The herbicidal active ingredients and antidotes may be applied together or separately to the leaves and shoots of the crop plants and unwanted plants. Preferably, the antidote is applied together with the herbicidal active ingredient. If the components are applied separately, the antidote is applied first to the field and then the herbicidal active ingredient. The herbicidal active ingredient and antidote may be formulated together or separately as spray agents in the form of suspensions, emulsions or solutions.
Treatment of the crop plant seed with the antidote prior to sowing is also feasible. The herbicidal active ingredient is then applied to the field on its own in conventional manner.
For herbicidal (heteroaryloxy)-phenoxyacetic or -propionic acid derivatives of the formula IV, the amount of antidotally active compound varies, depending on the crop. The ratios may vary over a wide range, and are also dependent on the structure of the (heteroaryloxy)phenoxyacetic or -propionic acid derivatives IV and on the crop involved. Suitable ratios of herbicidal active ingredient to antidote are from 1:4 to 1:0.01, and preferably from 1:4 to 1:0.1, parts by weight.
For the same cyclohexenone derivative V, the amount of antidote varies, depending on the crop. The ratios in which a cyclohexenone derivative V and an aryl- or heteroarylimidazolecarboxylate of the formula Ia and/or Ib are used may vary over a wide range, and are dependent on the structure of the cyclohexenone derivative, the aryl- or heteroarylimidazolecarboxylate of the formula Ia and/or Ib and the crop involved. Suitable ratios of herbicidal active ingredient to safener are from 1:4 to 1:0.01, and preferably from 1:4 to 1:0.25, parts by weight.
The novel herbicidal agents may contain, in addition to the aryl- or heteroarylimidazolecarboxylate of the formula Ia and/or Ib as safener and the herbicide from the group of the (heteroaryloxy)phenoxyacetic acids IV or cyclohexenones V, other herbicidal or growth-regulating active ingredients and inert additives without the safening effect being impaired.
The agents according to the invention, or--when applied separately--the herbicidal active ingredients and the safener, are applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or others), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents or granules by spraying, atomizing, dusting, broadcasting or pouring. The forms of application depend entirely on the purpose for which the active ingredients are to be used.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, and salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

MANUFACTURING EXAMPLES
The directions given in the examples below may be used, after appropriate modifications of the starting materials, to obtain further compounds of the formula Ia and Ib. The compounds obtained are listed with their physical data in the tables below; compounds without these data may be prepared from the appropriate materials in analogous manner. In view of their close structural relationship to the compounds which have been manufactured and investigated, they are expected to have a similar action.
EXAMPLE 1
Ethyl 1-(2,4-dinitrophenyl)-2-methylimidazole-4-carboxylate
16 ml of triethylamine was added to 14.5 g (0.078 mol) of 2,4-dinitrofluorobenzene, 12 g (0.078 mol) of ethyl 2-methylimidazole-4-carboxylate and 500 ml of toluene, and the mixture was refluxed for 18 hours. The solvent was then distilled off under reduced pressure and the residue was chromatographed using pentane/ethyl acetate as mobile phase.
Yield: 19.5 g (81% of theory); m.p.: 150.degree.-152.degree. C. (Active ingredient example 1.015).
EXAMPLE 2
Isopropyl 1-(2,4-dinitrophenyl)-2-bromo-5-methyl-4-imidazolecarboxylate
4.2 ml of triethylamine was added dropwise to 5 g (0.02 mol) of isopropyl 2-bromo-5-methyl-4-imidazolecarboxylate, 3.9 g of 1-fluoro-2,4-dinitrobenzene and 200 ml of toluene, and the mixture was refluxed for 16 hours. The toluene solution was then washed with water, dried and concentrated. The residue was stirred with diethyl ether and the solid obtained in this manner was isolated.
Yield: 5.7 g (69%); m.p.: 161.degree.-162.degree. C. (Active ingredient example 1.025).
EXAMPLE 3
Methyl 1-(2,4-dibromophenyl)-2-methylimidazole-4-carboxylate
14.1 g of 30% strength sodium methylate solution was added to 10.9 g (0.078 mol) of methyl 2-methylimidazole-4-carboxylate in 100 ml of dimethylformamide; the methanol which formed was removed completely. 38.1 g (0.15 mol) of 1-fluoro-2,4-dibromobenzene was added to the dimethylformamide solution remaining, and the mixture was refluxed for 2 hours. Water was then added, extraction carried out with ethyl acetatem and the ethyl acetate phase was washed with water. After removal of the solvent from the organic phase, there was obtained a residue which crystallized on trituration with diisopropyl ether.
Yield: 10.8 g (36.7%); m.p.: 162.degree.-163.degree. C. (Active ingredient example 1.059).
EXAMPLE 4
Ethyl 1-(2,4-dinitrophenyl)-2-methyl-5-chloroimidazole-4-carboxylate and ethyl 1-(2,4-dinitrophenyl)-2-trichloromethyl-5-chloroimidazole-4-carboxylate
16.5 g (0.1225 mol) of sulfuryl chloride and 0.2 g of dibenzoyl peroxide were added to 9.8 g (0.03 mol) of ethyl 1-(2,4-dinitrophenyl)-2-methylimidazole-4-carboxylate in 200 ml of chlorobenzene, and the mixture was heated at 100.degree. C. for 90 minutes. When gas evolution had ceased, the mixture was concentrated to dryness, the residue was adjusted to a pH of 7 with dilute aqueous ammonia and extracted with methylene chloride, and the organic phase was dried with sodium sulfate, concentrated and chromatographed.
Yield: 4.7 g (43% of theory); m.p.: 181.degree.-182.degree. C. (Active ingredient example 2.001).
TABLE 1__________________________________________________________________________ ##STR37##No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 mp (.degree.C.); NMR(ppm)__________________________________________________________________________1.001 CH.sub.3 CH.sub.3 H phenyl1.002 CH.sub.3 CH.sub.2 CH.sub.3 H phenyl1.003 Cl CH.sub.3 CH.sub.3 phenyl1.004 Cl CH.sub.2 CH.sub.3 CH.sub.3 phenyl1.005 Cl CH(CH.sub.3).sub.2 CH.sub.3 phenyl1.006 Br CH.sub.3 CH.sub.3 phenyl1.007 Br CH.sub.2 CH.sub.3 CH.sub.3 phenyl1.008 CH.sub.3 CH.sub.3 H 4-nitrophenyl1.009 CH.sub.3 CH.sub.2 CH.sub.3 H 4-nitrophenyl1.010 CH.sub.3 CH(CH.sub.3).sub.2 H 4-nitrophenyl1.011 CH.sub.3 CH.sub.2 CHCH.sub.2 H 4-nitrophenyl1.012 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-nitrophenyl1.013 Br CH.sub.2 CH.sub.3 CH.sub.3 4-nitrophenyl1.014 CH.sub.3 CH.sub.3 H 2,4-dinitrophenyl1.015 CH.sub.3 CH.sub.2 CH.sub.3 H 2,4-dinitrophenyl 150-1521.016 CH.sub.3 CH(CH.sub.3).sub.2 H 2,4-dinitrophenyl1.017 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 H 2,4-dinitrophenyl1.018 CH.sub.3 CH.sub.2 CHCH.sub.2 H 2,4-dinitrophenyl1.019 CH.sub.3 CH.sub.2 CCH H 2,4-dinitrophenyl1.020 Cl CH.sub.3 CH.sub.3 2,4-dinitrophenyl1.021 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,4-dinitrophenyl1.022 Cl CH(CH.sub.3).sub.2 CH.sub.3 2,4-dinitrophenyl1.023 Br CH.sub.3 CH.sub.3 2,4-dinitrophenyl1.024 Br CH.sub.2 CH.sub.3 CH.sub.3 2,4-dinitrophenyl 148-1501.025 Br CH(CH.sub.3).sub.2 CH.sub.3 2,4-dinitrophenyl 161-1621.026 CH.sub.3 CH.sub.3 H 2-nitrophenyl1.027 CH.sub.3 CH.sub.2 CH.sub.3 H 2-nitrophenyl1.028 Cl CH.sub.2 CH.sub.3 CH.sub.3 2-nitrophenyl1.029 Br CH.sub.2 CH.sub.3 CH.sub.3 2-nitrophenyl1.030 CH.sub.3 CH.sub.3 H 4-chlorophenyl1.031 CH.sub.3 CH.sub.2 CH.sub.3 H 4-chlorophenyl1.032 Cl CH.sub.3 CH.sub.3 4-chlorophenyl1.033 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-chlorophenyl1.034 Br CH.sub.3 CH.sub.3 4-chlorophenyl1.035 Br CH.sub.2 CH.sub.3 CH.sub.3 4-chlorophenyl1.036 CH.sub.3 CH.sub.3 H 2-chlorophenyl1.037 CH.sub.3 CH.sub.2 CH.sub.3 H 2-chlorophenyl1.038 CH.sub.3 CH.sub.3 H 2,4-dichlorophenyl 162-1631.039 CH.sub.3 CH.sub.2 CH.sub.3 H 2,4-dichlorophenyl 121-1221.040 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 H 2,4-dichlorophenyl1.041 CH.sub.3 CH(CH.sub.3).sub.2 H 2,4-dichlorophenyl1.042 Cl CH.sub.3 CH.sub.3 2,4-dichlorophenyl1.043 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,4-dichlorophenyl1.044 Cl CH(CH.sub.3).sub.2 CH.sub.3 2,4-dichlorophenyl1.045 Cl cyclopentyl CH.sub.3 2,4-dichlorophenyl1.046 Cl cyclohexyl CH.sub.3 2,4-dichlorophenyl1.047 Br CH.sub.3 CH.sub.3 2,4-dichlorophenyl1.048 Br CH.sub.2 CH.sub.3 CH.sub.3 2,4-dichlorophenyl1.049 Br CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 2,4-dichlorophenyl1.050 Br CH(CH.sub.3).sub.2 CH.sub.3 2,4-dichlorophenyl1.051 CH.sub.3 CH.sub.3 H 4-bromophenyl1.052 CH.sub.3 CH.sub.2 CH.sub.3 H 4-bromophenyl1.053 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-bromophenyl1.054 Br CH.sub.2 CH.sub.3 CH.sub.3 4-bromophenyl1.055 CH.sub.3 CH.sub.3 H 2-bromophenyl1.056 CH.sub.3 CH.sub.2 CH.sub.3 H 2-bromophenyl1.057 Cl CH.sub.2 CH.sub.3 CH.sub.3 2-bromophenyl1.058 Br CH.sub.2 CH.sub.3 CH.sub.3 2-bromophenyl1.059 CH.sub.3 CH.sub.3 H 2,4-dibromophenyl 162-1631.060 CH.sub.3 CH.sub.2 CH.sub.3 H 2,4-dibromophenyl1.061 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 H 2,4-dibromophenyl1.062 CH.sub.3 CH(CH.sub.3).sub.2 H 2,4-dibromophenyl1.063 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,4-dibromophenyl1.064 Cl CH(CH.sub.3).sub.2 CH.sub.3 2,4-dibromophenyl1.065 Br CH.sub.2 CH.sub.3 CH.sub.3 2,4-dibromophenyl1.066 Br CH(CH.sub.3).sub.2 CH.sub.3 2,4-dibromophenyl1.067 CH.sub.3 CH.sub.3 H 2,4,6-trichlorophenyl1.068 CH.sub.3 CH.sub.2 CH.sub.3 H 2,4,6-trichlorophenyl1.069 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 H 2,4,6-trichlorophenyl1.070 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,4,6-trichlorophenyl1.071 Br CH.sub.2 CH.sub.3 CH.sub.3 2,4,6-trichlorophenyl1.072 Br CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 2,4,6-trichlorophenyl1.073 CH.sub.3 CH.sub.3 H 4-cyanophenyl1.074 CH.sub.3 CH.sub.2 CH.sub.3 H 4-cyanophenyl1.075 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 H 4-cyanophenyl1.076 CH.sub.3 CH(CH.sub.3).sub.2 H 4-cyanophenyl1.077 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-cyanophenyl1.078 Cl CH(CH.sub.3).sub.2 CH.sub.3 4-cyanophenyl1.079 Br CH.sub.2 CH.sub.3 CH.sub.3 4-cyanophenyl1.080 Br CH(CH.sub.3).sub.2 CH.sub.3 4-cyanophenyl1.081 CH.sub.3 CH.sub.3 H 2,4-dicyanophenyl1.082 CH.sub.3 CH.sub.2 CH.sub.3 H 2,4-dicyanophenyl1.083 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,4-dicyanophenyl1.084 Br CH.sub. 2 CH.sub.3 CH.sub.3 2,4-dicyanophenyl1.085 CH.sub.3 CH.sub.3 H 4-trifluoromethylphenyl1.086 CH.sub.3 CH.sub.2 CH.sub.3 H 4-trifluoromethylphenyl1.087 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 H 4-trifluoromethylphenyl1.088 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-trifluoromethylphenyl1.089 Br CH.sub.2 CH.sub.3 CH.sub.3 4-trifluoromethylphenyl1.090 CH.sub.3 CH.sub.3 H 4-chloro-2-nitrophenyl1.091 CH.sub.3 CH.sub.2 CH.sub.3 H 4-chloro-2-nitrophenyl1.092 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-chloro-2-nitrophenyl1.093 Br CH.sub.2 CH.sub.3 CH.sub.3 4-chloro-2-nitrophenyl1.094 CH.sub.3 CH.sub.3 H 4-chloro-2-fluorophenyl1.095 CH.sub.3 CH.sub.2 CH.sub.3 H 4-chloro-2-fluorophenyl1.096 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-chloro-2-fluorophenyl1.097 Br CH.sub.2 CH.sub.3 CH.sub.3 4-chloro-2-fluorophenyl1.098 CH.sub.3 CH.sub.3 H 4-chloro-2-cyanophenyl1.099 CH.sub.3 CH.sub.2 CH.sub.3 H 4-chloro-2-cyanophenyl1.100 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-chloro-2-cyanophenyl1.101 Br CH.sub.2 CH.sub.3 CH.sub.3 4-chloro-2-cyanophenyl1.102 CH.sub.3 CH.sub.3 H 4-chloro-2-trifluoro- methylphenyl1.103 CH.sub.3 CH.sub.2 CH.sub.3 H 4-chloro-2-trifluoro- methylphenyl1.104 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-chloro-2-trifluoro- methylphenyl1.105 Br CH.sub.2 CH.sub.3 CH.sub. 3 4-chloro-2-trifluoro- methylphenyl1.106 CH.sub.3 CH.sub.3 H 4-chloro-2-methylphenyl1.107 CH.sub.3 CH.sub.2 CH.sub.3 H 4-chloro-2-methylphenyl1.108 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-chloro-2-methylphenyl1.109 Br CH.sub.2 CH.sub.3 CH.sub.3 4-chloro-2-methylphenyl1.110 CH.sub.3 CH.sub.3 H 4-bromo-2-nitrophenyl1.111 CH.sub.3 CH.sub.2 CH.sub.3 H 4-bromo-2-nitrophenyl1.112 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-bromo-2-nitrophenyl1.113 Br CH.sub.2 CH.sub.3 CH.sub.3 4-bromo-2-nitrophenyl1.114 CH.sub.3 CH.sub.3 H 4-bromo-2-chlorophenyl1.115 CH.sub.3 CH.sub.2 CH.sub.3 H 4-bromo-2-chlorophenyl1.116 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-bromo-2-chlorophenyl1.117 Br CH.sub.2 CH.sub.3 CH.sub.3 4-bromo-2-chlorophenyl1.118 CH.sub.3 CH.sub.3 H 4-bromo-2-fluorophenyl1.119 CH.sub.3 CH.sub.2 CH.sub.3 H 4-bromo-2-fluorophenyl1.120 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-bromo-2-fluorophenyl1.121 Br CH.sub.2 CH.sub.3 CH.sub.3 4-bromo-2-fluorophenyl1.122 CH.sub.3 CH.sub.3 H 4-bromo-2-cyanophenyl1.123 CH.sub.3 CH.sub.2 CH.sub.3 H 4-bromo-2-cyanophenyl1.124 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-bromo-2-cyanophenyl1.125 Br CH.sub.2 CH.sub.3 CH.sub.3 4-bromo-2-cyanophenyl1.126 CH.sub.3 CH.sub.3 H 4-bromo-2-trifluoro- methylphenyl1.127 CH.sub.3 CH.sub.2 CH.sub.3 H 4-bromo-2-trifluoro- methylphenyl1.128 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-bromo-2-trifluoro- methylphenyl1.129 Br CH.sub.2 CH.sub.3 CH.sub.3 4-bromo-2-trifluoro- methyphenyl1.130 CH.sub.3 CH.sub.3 H 4-bromo-2-methylphenyl1.131 CH.sub.3 CH.sub.2 CH.sub.3 H 4-bromo-2-methylphenyl1.132 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-bromo-2-methylphenyl1.133 Br CH.sub.2 CH.sub.3 CH.sub.3 4-bromo-2-methylphenyl1.134 CH.sub.3 CH.sub.3 H 4-cyano-2-nitrophenyl1.135 CH.sub.3 CH.sub.2 CH.sub.3 H 4-cyano-2-nitrophenyl1.136 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-cyano-2-nitrophenyl1.137 Br CH.sub.2 CH.sub.3 CH.sub.3 4-cyano-2-nitrophenyl1.138 CH.sub.3 CH.sub.3 H 4-cyano-2-chlorophenyl1.139 CH.sub.3 CH.sub.2 CH.sub.3 H 4-cyano-2-chlorophenyl1.140 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-cyano-2-chlorophenyl1.141 Br CH.sub.2 CH.sub.3 CH.sub.3 4-cyano-2-chlorophenyl1.142 CH.sub.3 CH.sub.3 H 4-cyano-2-fluorophenyl1.143 CH.sub.3 CH.sub.2 CH.sub.3 H 4-cyano-2-fluorophenyl1.144 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-cyano-2-fluorophenyl1.145 Br CH.sub.2 CH.sub.3 CH.sub.3 4-cyano-2-fluorophenyl1.146 CH.sub.3 CH.sub.3 H 4-cyano-2-bromophenyl1.147 CH.sub.3 CH.sub.2 CH.sub.3 H 4-cyano-2-bromophenyl 171-1731.148 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 H 4-cyano-2-bromophenyl1.149 CH.sub.3 CH(CH.sub. 3).sub.2 H 4-cyano-2-bromophenyl1.150 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-cyano-2-bromophenyl1.151 Cl CH(CH.sub.3).sub.2 CH.sub.3 4-cyano-2-bromophenyl1.152 Cl Cyclopentyl CH.sub.3 4-cyano-2-bromophenyl1.153 Cl Cyclohexyl CH.sub.3 4-cyano-2-bromophenyl1.154 Br CH.sub.2 CH.sub.3 CH.sub.3 4-cyano-2-bromophenyl1.155 CH.sub.3 CH.sub.3 H 4-cyano-2-methylphenyl1.156 CH.sub.3 CH.sub.2 CH.sub.3 H 4-cyano-2-methylphenyl1.157 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-cyano-2-methylphenyl1.158 Br CH.sub.2 CH.sub.3 CH.sub.3 4-cyano-2-methylphenyl1.159 CH.sub.3 CH.sub.3 H 4-cyano-2-trifluoro- methylphenyl1.160 CH.sub.3 CH.sub.2 CH.sub.3 H 4-cyano-2-trifluoro- methylphenyl1.161 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-cyano-2-trifluoro- methylphenyl1.162 Br CH.sub.2 CH.sub.3 CH.sub.3 4-cyano-2-trifluoro- methylphenyl1.163 CH.sub.3 CH.sub.3 H 4-nitro-2-chlorophenyl1.164 CH.sub.3 CH.sub.2 CH.sub.3 H 4-nitro-2-chlorophenyl 128-1291.165 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-nitro-2-chlorophenyl1.166 Br CH.sub.2 CH.sub.3 CH.sub.3 4-nitro-2-chlorophenyl1.167 CH.sub.3 CH.sub.3 H 4-nitro-2-bromophenyl1.168 CH.sub.3 CH.sub.2 CH.sub.3 H 4-nitro-2-bromophenyl1.169 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-nitro-2-bromophenyl1.170 Br CH.sub.2 CH.sub.3 CH.sub. 3 4-nitro-2-bromophenyl1.171 CH.sub.3 CH.sub.3 H 4-nitro-2-cyanophenyl1.172 CH.sub.3 CH.sub.2 CH.sub.3 H 4-nitro-2-cyanophenyl1.173 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-nitro-2-cyanophenyl1.174 Br CH.sub.2 CH.sub.3 CH.sub.3 4-nitro-2-cyanophenyl1.175 CH.sub.3 CH.sub.3 H 4-trifluoromethyl-2- chlorophenyl1.176 CH.sub.3 CH.sub.2 CH.sub.3 H 4-trifluoromethyl-2- chlorophenyl1.177 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-trifluoromethyl-2- chlorophenyl1.178 Br CH.sub.2 CH.sub.3 CH.sub.3 4-trifluoromethyl-2- chlorophenyl1.179 CH.sub.3 CH.sub.3 H 4-trifluoromethyl-2- bromophenyl1.180 CH.sub.3 CH.sub.2 CH.sub.3 H 4-trifluoromethyl-2- bromophenyl1.181 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-trifluoromethyl-2- bromophenyl1.182 Br CH.sub.2 CH.sub.3 CH.sub.3 4-trifluoromethyl-2- bromophenyl1.183 CH.sub.3 CH.sub.3 H 4-trifluoromethyl-2- cyanophenyl1.184 CH.sub.3 CH.sub.2 CH.sub.3 H 4-trifluoromethyl-2- cyanophenyl1.185 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-trifluoromethyl-2- cyanophenyl1.186 Br CH.sub.2 CH.sub.3 CH.sub.3 4-trifluoromethyl-2- cyanophenyl1.187 CH.sub. 3 CH.sub.3 H 4-tert-butyl-2- chlorophenyl1.188 CH.sub.3 CH.sub.2 CH.sub.3 H 4-tert-butyl-2- chlorophenyl1.189 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-tert-butyl-2- chlorophenyl1.190 Br CH.sub.2 CH.sub.3 CH.sub.3 4-tert-butyl-2- chlorophenyl1.191 CH.sub.3 CH.sub.3 H 4-tert-butyl-2- bromophenyl1.192 CH.sub.3 CH.sub.2 CH.sub.3 H 4-tert-butyl-2- bromophenyl1.193 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-tert-butyl-2- bromophenyl1.194 Br CH.sub.2 CH.sub.3 CH.sub.3 4-tert-butyl-2- bromphenyl1.195 CH.sub.3 CH.sub.3 H 4-tert-butyl-2- cyanophenyl1.196 CH.sub.3 CH.sub.2 CH.sub.3 H 4-tert-butyl-2- cyanophenyl1.197 Cl CH.sub.2 CH.sub.3 CH.sub.3 4-tert-butyl-2- cyanophenyl1.198 Br CH.sub.2 CH.sub.3 CH.sub.3 4-tert-butyl-2- cyanophenyl1.199 CH.sub.3 CH.sub.3 H 2,6-dichloro-4-tri- fluoromethylphenyl1.200 CH.sub.3 CH.sub.2 CH.sub.3 H 2,6-dichloro-4-tri- fluoromethylphenyl1.201 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,6-dichloro-4-tri- fluoromethylphenyl1.202 Br CH.sub.2 CH.sub.3 CH.sub.3 2,6-dichloro-4-tri- fluoromethylphenyl1.203 CH.sub.3 CH.sub.3 H 2,6-dichloro-4- 205-207 nitrophenyl1.204 CH.sub.3 CH.sub.2 CH.sub.3 H 2,6-dichloro-4- 149-151 nitrophenyl1.205 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,6-dichloro-4- nitrophenyl1.206 Br CH.sub.2 CH.sub.3 CH.sub.3 2,6-dichloro-4- nitrophenyl1.207 CH.sub.3 CH.sub.3 H 2,6-dinitro-4-tri- fluoromethylphenyl1.208 CH.sub.3 CH.sub.2 CH.sub.3 H 2,6-dinitro-4-tri- fluoromethylphenyl1.209 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,6-dinitro-4-tri- fluoromethylphenyl1.210 Br CH.sub.2 CH.sub.3 CH.sub.3 2,6-dinitro-4-tri- fluoromethylphenyl1.211 CH.sub.3 CH.sub.3 H 2,4-dinitro-6-cyano- phenyl1.212 CH.sub.3 CH.sub.2 CH.sub.3 H 2,4-dinitro-6-cyano- phenyl1.213 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,4-dinitro-6-cyano- phenyl1.214 Br CH.sub.2 CH.sub.3 CH.sub.3 2,4-dinitro-6-cyano- phenyl1.215 CH.sub.3 CH.sub.3 H 2,4-dinitro-6-tri- fluoromethylphenyl1.216 CH.sub.3 CH.sub.2 CH.sub.3 H 2,4-dinitro-6-tri- fluoromethylphenyl1.217 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,4-dinitro-6-tri- fluoromethylphenyl1.218 Br CH.sub.2 CH.sub.3 CH.sub.3 2,4-dinitro-6-tri- fluoromethylphenyl1.219 CH.sub.3 CH.sub.3 H 2,4-dinitro-6-carb- ethoxyphenyl1.220 CH.sub.3 CH.sub.2 CH.sub.3 H 2,4-dinitro-6-carb- ethoxyphenyl1.221 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,4-dinitro-6-carb- ethoxyphenyl1.222 Br CH.sub.2 CH.sub.3 CH.sub.3 2,4-dinitro-6-carb- ethoxyphenyl1.223 CH.sub.3 CH.sub.3 H 2-nitro-4-carb- ethoxyphenyl1.224 CH.sub.3 CH.sub.2 CH.sub.3 H 2-nitro-4-carb- ethoxyphenyl1.225 Cl CH.sub.2 CH.sub.3 CH.sub.3 2-nutro-4-carb- ethoxyphenyl1.226 Br CH.sub.2 CH.sub.3 CH.sub.3 2-nitro-4-carb- ethoxyphenyl1.227 CH.sub.3 CH.sub.3 H 2-nitro-4-acetyl- phenyl1.228 CH.sub.3 CH.sub.2 CH.sub.3 H 2-nitro-4-acetyl- phenyl1.229 Cl CH.sub.2 CH.sub.3 CH.sub.3 2-nitro-4-acetylphenyl1.230 Br CH.sub.2 CH.sub.3 CH.sub.3 2-nitro-4-acetylphenyl1.231 CH.sub.3 CH.sub.3 H 2-chloro-4-acetylphenyl1.232 CH.sub.3 CH.sub.2 CH.sub.3 H 2-chloro-4-acetylphenyl1.233 Cl CH.sub.2 CH.sub.3 CH.sub.3 2-chloro-4-acetylphenyl1.234 Br CH.sub.2 CH.sub.3 CH.sub.3 2-chloro-4-acetylphenyl1.235 CH.sub.3 CH.sub.3 H 2,4-dinitro-6-chlorophenyl1.236 CH.sub.3 CH.sub.2 CH.sub.3 H 2,4-dinitro-6-chlorophenyl1.237 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,4-dinitro-6-chlorophenyl1.238 Br CH.sub.2 CH.sub.3 CH.sub.3 2,4-dinitro-6-chlorophenyl1.239 CH.sub.3 CH.sub.3 H 2,6-dinitro-4-methyl- sulfonylphenyl1.240 CH.sub.3 CH.sub.2 CH.sub.3 H 2,6-dinitro-4-methyl- sulfonylphenyl1.241 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,6-dinitro-4-methyl- sulfonylphenyl1.242 Br CH.sub.2 CH.sub.3 CH.sub.3 2,6-dinitro-4-methyl- sulfonylphenyl1.243 CH.sub.3 CH.sub.3 H 2,6-dinitro-4-carbo- methoxyphenyl1.244 CH.sub.3 CH.sub.2 CH.sub.3 H 2,6-dinitro-4-carbo- methoxyphenyl1.245 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,6-dinitro-4-carbo- methoxyphenyl1.246 Br CH.sub.2 CH.sub.3 CH.sub.3 2,6-dinitro-4-carbo- methoxyphenyl1.247 CH.sub.3 CH.sub.3 H 2,6-dinitro-4-methylphenyl1.248 CH.sub.3 CH.sub.2 CH.sub.3 H 2,6-dinitro-4-methylphenyl1.249 Cl CH.sub.2 CH.sub.3 CH.sub.3 2,6-dinitro-4-methyl- phenyl1.250 Br CH.sub.2 CH.sub.3 CH.sub.3 2,6-dinitro-4-methylphenyl1.251 CH.sub.3 CH.sub.3 H 3,5-dichloro-4-pyridyl1.252 CH.sub.3 CH.sub.2 CH.sub.3 H 3,5-dichloro-4-pyridyl1.253 Cl CH.sub.2 CH.sub.3 CH.sub.3 3,5-dichloro-4-pyridyl1.254 Br CH.sub.2 CH.sub.3 CH.sub.3 3,5-dichloro-4-pyridyl1.255 CH.sub.3 CH.sub.3 H 3-chloro-5-trifluoro- methyl-2-pyridyl1.256 CH.sub.3 CH.sub.2 CH.sub.3 H 3-chloro-5-trifluoro- methyl-2-pyridyl1.257 Cl CH.sub.2 CH.sub.3 CH.sub.3 3-chloro-5-trifluoro- methyl-2-pyridyl1.258 Br CH.sub.2 CH.sub.3 CH.sub.3 3-chloro-5-trifluoro- methyl-2-pyridyl1.259 CH.sub.3 CH.sub.3 H 3-chloro-5-nitro- 2-pyridyl1.260 CH.sub.3 CH.sub.2 CH.sub.3 H 3-chloro-5-nitro- 2-pyridyl1.261 Cl CH.sub.2 CH.sub.3 CH.sub.3 3-chloro-5-nitro- 2-pyridyl1.262 Br CH.sub.2 CH.sub.3 CH.sub.3 3-chloro-5-nitro- 2-pyridyl1.263 CH.sub.3 CH.sub.3 H 5-chloro-3-trifluoro- methyl-2-pyridyl1.264 CH.sub.3 CH.sub.2 CH.sub.3 H 5-chloro-3-trifluoro- methyl-2-pyridyl1.265 Cl CH.sub.2 CH.sub.3 CH.sub.3 5-chloro-3-trifluoro- methyl-2-pyridyl1.266 Br CH.sub.2 CH.sub.3 CH.sub.3 5-chloro-3-trifluoro- methyl-2-pyridyl1.267 CH.sub.3 CH.sub.2 CH.sub.3 H 3-chloro-2-cyanophenyl 136-1391.268 CH.sub.3 CH.sub.2 CH.sub.3 H 3-chloro-4-nitrophenyl 102-1031.269 CH.sub.3 CH.sub.2 CH.sub.3 H 2,6-dibromo-4-nitrophenyl 205-207__________________________________________________________________________
TABLE 2__________________________________________________________________________ ##STR38##No. R.sup.1 R.sup.2 R.sup.4 mp (.degree.C.)__________________________________________________________________________2.001 CH.sub.3 CH.sub.2 CH.sub.3 2,4-dinitrophenyl 181-1822.002 CCl.sub.3 CH.sub.2 CH.sub.3 2,4-dinitrophenyl 149-1512.003 CH.sub.3 CH.sub.2 CH.sub.3 2,4-dichlorophenyl2.004 CCl.sub.3 CH.sub.2 CH.sub.3 2,4-dichlorophenyl2.005 CH.sub.3 CH.sub.2 CH.sub.3 2,4-dibromophenyl2.006 CCl.sub.3 CH.sub.2 CH.sub.3 2,4-dibromophenyl2.007 CH.sub.3 CH.sub.2 CH.sub.3 2,4,6-trichlorophenyl2.008 CCl.sub.3 CH.sub.2 CH.sub.3 2,4,6-trichlorophenyl2.009 CH.sub.3 CH.sub.2 CH.sub.3 2,4-dicyanophenyl2.010 CCl.sub.3 CH.sub.2 CH.sub.3 2,4-dicyanophenyl2.011 CH.sub.3 CH.sub.2 CH.sub.3 4-chloro-2-nitrophenyl2.012 CCl.sub.3 CH.sub.2 CH.sub.3 4-chloro-2-nitrophenyl2.013 CH.sub.3 CH.sub.2 CH.sub.3 4-chloro-2-fluorophenyl2.014 CCl.sub.3 CH.sub.2 CH.sub.3 4-chloro-2-fluorophenyl2.015 CH.sub.3 CH.sub.2 CH.sub.3 4-chloro-2-cyanophenyl2.016 CCl.sub.3 CH.sub.2 CH.sub.3 4-chloro-2-cyanophenyl2.017 CH.sub.3 CH.sub.2 CH.sub.3 4-chloro-2-trifluoromethylphenyl2.018 CCl.sub. 3 CH.sub.2 CH.sub.3 4-chloro-2-trifluoromethylphenyl2.019 CH.sub.3 CH.sub.2 CH.sub.3 4-bromo-2-nitrophenyl2.020 CCl.sub.3 CH.sub.2 CH.sub.3 4-bromo-2-nitrophenyl2.021 CH.sub.3 CH.sub.2 CH.sub.3 4-bromo-2-chlorophenyl2.022 CCl.sub.3 CH.sub.2 CH.sub.3 4-bromo-2-chlorophenyl2.023 CH.sub.3 CH.sub.2 CH.sub.3 4-bromo-2-fluorophenyl2.024 CCl.sub.3 CH.sub.2 CH.sub.3 4-bromo-2-fluorophenyl2.025 CH.sub.3 CH.sub.2 CH.sub.3 4-bromo-2-cyanophenyl2.026 CCl.sub.3 CH.sub.2 CH.sub.3 4-bromo-2-cyanophenyl2.027 CH.sub.3 CH.sub.2 CH.sub.3 4-bromo-2-trifluoromethylphenyl2.028 CCl.sub.3 CH.sub.2 CH.sub.3 4-bromo-2-trifluoromethylphenyl2.029 CH.sub.3 CH.sub.2 CH.sub.3 4-cyano-2-chlorophenyl2.030 CCl.sub.3 CH.sub.2 CH.sub.3 4-cyano-2-chlorophenyl2.031 CH.sub.3 CH.sub.2 CH.sub.3 4-cyano-2-fluorophenyl2.032 CCl.sub.3 CH.sub.2 CH.sub.3 4-cyano-2-fluorophenyl2.033 CH.sub.3 CH.sub.2 CH.sub.3 4-cyano-2-nitrophenyl2.034 CCl.sub.3 CH.sub.2 CH.sub.3 4-cyano-2-nitrophenyl2.035 CH.sub.3 CH.sub.2 CH.sub.3 4-cyano-2-bromophenyl2.036 CCl.sub.3 CH.sub.2 CH.sub.3 4-cyano-2-bromophenyl2.037 CH.sub.3 CH.sub.2 CH.sub.3 4-cyano-2-trifluoromethylphenyl2.038 CCl.sub.3 CH.sub.2 CH.sub.3 4-cyano-2-trifluoromethylphenyl2.039 CH.sub.3 CH.sub.2 CH.sub.3 4-nitro-2-chlorophenyl 119-1202.040 CCl.sub.3 CH.sub.2 CH.sub.3 4-nitro-2-chlorophenyl 157-1582.041 CH.sub.3 CH.sub.2 CH.sub.3 4-nitro-2-bromophenyl2.042 CCl.sub.3 CH.sub.2 CH.sub. 3 4-nitro-2-bromophenyl2.043 CH.sub.3 CH.sub.2 CH.sub.3 4-nitro-2-cyanophenyl2.044 CCl.sub.3 CH.sub.2 CH.sub.3 4-nitro-2-cyanophenyl2.045 CH.sub.3 CH.sub.2 CH.sub.3 4-trifluoromethyl-2-chlorophenyl2.046 CCl.sub.3 CH.sub.2 CH.sub.3 4-trifluoromethyl-2-chlorophenyl2.047 CH.sub.3 CH.sub.2 CH.sub.3 4-trifluoromethyl-2-bromophenyl2.048 CCl.sub.3 CH.sub.2 CH.sub.3 4-trifluoromethyl-2-bromophenyl2.049 CH.sub.3 CH.sub.2 CH.sub.3 4-trifluoromethyl-2-cyanophenyl2.050 CCl.sub.3 CH.sub.2 CH.sub.3 4-trifluoromethyl-2-cyanophenyl2.051 CH.sub.3 CH.sub.2 CH.sub.3 2,6-dichloro-4-trifluoromethylphenyl2.052 CCl.sub.3 CH.sub.2 CH.sub.3 2,6-dichloro-4-trifluoromethylphenyl2.053 CH.sub.3 CH.sub.2 CH.sub.3 2,6-dinitro-4-trifluoromethylphenyl2.054 CCl.sub.3 CH.sub.2 CH.sub.3 2,6-dinitro-4-trifluoromethylphenyl2.055 CH.sub.3 CH.sub.2 CH.sub.3 2,4-dinitro-6-cyanophenol2.056 CCl.sub.3 CH.sub.2 CH.sub.3 2,4-dinitro-6-cyanophenol2.057 CH.sub.3 CH.sub.2 CH.sub.3 2,4-dinitro-6-trifluoromethylphenyl2.058 CCl.sub.3 CH.sub.2 CH.sub.3 2,4-dinitro-6-trifluoromethylphenyl2.059 CH.sub.3 CH.sub.2 CH.sub.3 2,4-dinitro-6-carbethoxyphenyl2.060 CCl.sub.3 CH.sub.2 CH.sub.3 2,4-dinitro-6-carbethoxyphenyl2.061 CH.sub.3 CH.sub.2 CH.sub.3 2-nitro-4-carbethoxyphenyl2.062 CCl.sub.3 CH.sub.2 CH.sub.3 2-nitro-4-carbethoxyphenyl2.063 CH.sub.3 CH.sub.2 CH.sub.3 2,6-dichloro-4-nitrophenyl2.064 CCl.sub.3 CH.sub.2 CH.sub.3 2,6-dichloro-4-nitrophenyl 185-187__________________________________________________________________________
USE EXAMPLE
The influence of various representatives of the herbicidal agents, or combinations of agent and antidote, according to the invention on the growth of unwanted and crop plants compared with that of the herbicidal active ingredient alone is demonstrated in the following greenhouse experiments.
The vessels employed were plastic flowerpots having a volume of 300 cm.sup.3 and filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown separately, according to species, and the soil was moistened. Transparent plastic covers were then placed on the vessels to ensure uniform germination and plant growth.
For the postemergence treatment, the plants were grown, depending on growth form, to a height of 3 to 15 cm before being treated with the active ingredients, which were suspended or emulsified in water and sprayed through finely distributing nozzles.
In the biological experiments, compound V.2 was used as cyclohexenone derivative V: ##STR39##
The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient and safener. The amounts of herbicidal active ingredient applied range from 0.001 to 0.5 kg/ha.
The herbicidal active ingredient V.2 was used (on its own and together with the safener) in the spray liquor as a commercially formulated product (184 g/l EC) together with the same amounts of solvent system XXII given in the table for the safener.
All the safeners were formulated in a mixture consisting of 80% of cyclohexenones and 20% of Emulphor EL (formulation XXII) with 10 wt % of active ingredient.
The vessels were set up in the greenhouse-heat-loving species at from 18.degree. to 35.degree. C., and those from more moderate climates at from 10.degree. to 25.degree. C.
The experiment was run for from 3 to 5 weeks. During this period, the plants were tended and their reaction to the various treatments was assessed. Damage caused by the chemical agents was evaluated on a 0 to 100 scale, compared with untreated control plants. 0 denotes no damage, and 100 denotes complete destruction (Triticum aestivum, wheat).
The table below demonstrates the safening action of compounds nos. 1.038 and 1.039; the tolerance of the cyclohexenone derivative V.2 by the crop plant was improved considerably.
TABLE A______________________________________Reduction in the damage caused by the herbicide V.2to wheat as a result of combination with compounds1.038 and 1.039 according to the inventionApp. rateHerbicidalact. ingr. Safener Damage to wheatNo. [kg/ha] No. [kg/ha] in %______________________________________V.2 0.015 -- 44 0.03 -- 80V.2 0.015 1.038 0.06 0 0.03 0.125 20V.2 0.015 1.039 0.06 0 0.03 0.125 10______________________________________

Number	Name	Date
4578106	Leone-Bay et al.	Mar 1986
4591377	Leone-Bay et al.	May 1986
4595400	Leone-Bay et al.	Jun 1986
4639266	Heubach et al.	Jan 1987
4711962	Leone-Bay	Dec 1987
4755213	Schmierer et al.	Jul 1988
4808213	Schmierer et al.	Feb 1989

Crop protection agents based on 1-aryl- or 1-hetarylimidazolecarboxylic esters

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