CS276238B6 - herbicide agent and method for producing an active substance thereof - Google Patents

Abstract

5-Imidazolecarboxylic acid derivs. of formula (I), stereoisomers and salts are new, where R1=H or SH; R2=H, 1-7C alkyl, 3-7C alkenyl or alkynyl, 1-7C alkoxy-1-7C alkyl, aryl-1-5C-alkyl or 3-7C cycloalkyl; and X=1-indanyl, 1-tetrahydronaphthalenyl, 5-benzocycloheptanyl, 4-tetrahydrobenzothienyl, 4-tetrahydrobenzofuryl, 5-tetrahydroquinolyl, 5-tetrahydroisoquinolyl, 8-tetrahydroquinolyl, 8-tetrahydroisoquinolyl, 9,10-dihydro-9-anthracenyl, 9H-fluoren-9-yl, 5-dibenzo(a,d)cycloheptenyl, 5-dibenzo(a,d)cycloheptanyl or 1-dihydronaphthanenyl, each opt. substd. by 1-6 of 1-5C alkyl, mono- or di-aryl-1-5C-alkyl, 1-5Calkoxy, halogen, 3-7C alkenyl, NH2, NO2, 1-6C alkylcarbonylamino, CF3 or OCF3, where 2 geminal substits. together with the C atom may form a 3-7C cycloalkyl gp; where 'aryl'=phenyl opt. substd. by 1-3 or 1-5C alkyl or alkoxy, or halogen; provided that x is other than unsubstd. 1-indanyl or unsubstd. 1-tetrahydronaphthalenyl. - New herbicidal compsns. and methods employ (I) where x may be unsubstd. 1-indanyl or 1-tetrahydronaphthalenyl.

Description

The invention relates to a herbicidal composition and a process for the preparation of an active ingredient.

According to the invention, weeds can be controlled by the application of a herbicidally effective amount of a 5-inidazolecarboxylic acid derivative of the formula I

or a stereochemically isomeric form or salt thereof, wherein A is hydrogen or mercapto,

R is hydrogen, alkyl of 1 to 7 carbon atoms, alkenyl of 3 to 7 carbon atoms or alkoxyalkyl of 1 to 4 atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety,

X is 1-indanyl, 1-tetrahydronaphthyl, 5-benzocycloheptyl, 4-tetrabydrobenzothienyl, or 9H-fluoren-9-yl, each of which may be unsubstituted or substituted with 1 to 6 substituents from the group consisting of 1 to 5 alkyl carbon atoms, benzyl, C 1 -C 5 alkoxy or halogen and wherein the two substituents, when attached to the same atom, may form together with the carbon atom to which they are attached a C 3 -C 7 cycloalkyl group.

Some of the active compounds of formula I, their preparation and their pharmaceutical use as antifungal agents are known from U.S. Pat. No. 3,485,917. Furthermore, some of these compounds are described as effective agents in the method of inhibiting bud growth in U.S. Patent No. 3,873,297. Most of the compounds of formula I are novel and can be used in particular in the process of the invention.

Unexpectedly, the compounds of formula I exhibit potent herbicidal properties and are therefore useful in weed control. This property becomes an important fact that some crops of the plants used are not destroyed or only slightly damaged at high doses when treated with the compounds of formula I. Thus, the compounds of formula I are merit selective herbicides of plants such as rice and corn. In particular for rice, a wide range of application rates can be used, preferably when the rice is transplanted and the compound of formula I is applied after transplanting. In maize, a selective herbicidal effect is observed in preemergence as well as in postemergence.

The active compounds of the formula I are usually applied at application rates of 0.01 to 5.0 kg of active ingredient per ha in order to obtain satisfactory results. Sometimes, depending on environmental conditions, the application rates may exceed the above range. However, a preferred application rate is in the range of 0.02 kg to 1.0 kg of active ingredient per hectare.

As used in the preceding definitions, C 1 -C 5 alkyl means a straight or branched saturated C 1 -C 5 hydrocarbon radical, for example methyl, ethyl, n-proplyl, isopropyl, four butyl isomers, pentyl isomers, alkyl of 1 to 7 carbon atoms include alkyl radicals having 1 to 5 carbon atoms and higher homologues having 6 or 7 carbon atoms, halogen is fluorine, chlorine, bromine or poison, with fluorine and chlorine being preferred, alkenyl of 3 to 7 carbon atoms being straight or branched hydrocarbon a radical containing one double bond and having from 3 to 7 carbon atoms, such as allyl,

3-butanyl, 2-butenyl, 2-pentenyl, 3-pentenyl, methalyl or 3-methyl-2-butenyl, allyl and methalyl are preferred.

C 1 -C 5 alkoxy means, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy, four butyloxy isomers or pentyloxy isomers, alkoxy and 1 to 7 carbon atoms - alkyl of 1 to 7 carbon atoms means, for example, methoxymethyl, methoxyethyl, methoxypropyl, ethoxy- methyl, ethoxy-ethyl, ethoxy-propyl, propoxy-methyl, propoxy-ethyl, propoxy-propyl, isopropoxymethyl, isopropoxyethyl, isopropoxypropyl, 2-methoxypropyl, 2-ethoxypropyl, 2-methoxybutyl, 3-methoxybutyl, 2-ethoxybutyl, or 3 -ethoxybutyl.

It will be appreciated that the substituents on the radical X may be attached to different carbon atoms or two of them may have a paired position.

Depending on the nature of group X and / or group R? the compounds of formula I contain asymmetric carbon atoms. Unless otherwise indicated, the chemical name of the compounds means a mixture of all stereochemically isomeric forms. These mixtures contain all diastereomers and enantiomers of the basic molecular structure.

Pure isomeric forms of these compounds can be separated from the mixture by conventional separation methods. Preferably, if a specific stereohemic form is desired, said compound is synthesized by stereoselective methods of preparation. Optically active starting materials are preferably used in these methods.

The invention also includes the use of salts which the compounds of formula I are capable of forming with organic or inorganic bases such as amines, alkali metal or alkaline earth metal bases or quaternary ammonium bases or with organic or inorganic acids such as mineral acids, sulfonic acids, carboxylic acids acids or phosphorus-containing acids.

Examples of salt-forming mineral acids are hydrofluoric, hydrochloric, hydrobromic, hydroiodic, sulfuric, nitric, chloric, perchloric or phosphoric acid. A preferred salt-forming sulfonic acid is toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, or trifluoromethanesulfonic acid. Preferred salt-forming carboxylic acid is acetic, trifluoroacetic, benzoic, chloroacetic, phthalic, maleic, malonic, and citric acid. Phosphorous-containing acids are various alkyl phosphoric acids, alkyl phosphonic acids and dialkyl phosphonic acids.

Preferred alkali metal and salt-forming alkaline earth metal hydroxides are lithium, sodium, potassium, magnesium or calcium hydroxides, most preferably sodium or potassium. Examples of suitable salt-forming amines are primary, secondary and tertiary aliphatic and aromatic amines such as methylamine, ethylamine, propylamine, isopropylamine, four butylamine isomers, dimethylamine, diethylamine, diethylamine. nolamine, dipropylamine, diisopropylamine, di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine, quinoline and isoquinoline. Preferred amines are ethylamine, propylamine, diethylamine, or triethylamine, most preferably isopropylamine, diethanolamine and 1,4-diazabicyclo {2.2.2J octane. Examples of quaternary ammonium bases are generally cations of haloammonium salts, for example tetramethylammonium cation, trimethylbenzylammonium cation, triethylbenzylammonium cation, tetraethylammonium cation, trimethylethylammonium cation and also ammonium cation.

Most preferred novel compounds are;

1- (2-methyl-1,2,3,4-tetrahydro-1-naphthyl) -5-thioidazolecarboxylic acid methyl ester, 1- (2,2-dimethyl-1,2,3,4-tetrahydro-1- naphthyl / -5-imidazolecarboxylic acid,. - - 1- (5,7-Dimethyl-1,2,3,4-tetrahydro-1-naphthyl) -5-imidazolecarboxylic acid methyl ester, - 2,2-Dimethyl-indindan-1-yl) -2-mercapto-methyl ester -5-imidazolecarboxylic acid and 1- (2,2-dimethylindan-1-yl) -5-imidazolecarboxylic acid methyl ester; - 3

CS 276238 Βδ

The process for preparing the active ingredient is characterized by condensing the compound of formula II ¹¹ 2

HC - H - CH 2 - COOR 4/11 /

I x

wherein R and X are as defined above, with an alkyl formate of 1 to 4 carbon atoms in the presence of a base in an inert solvent and reaction of the resulting intermediate of formula III

0-Z /

HC

II 11 _p

NC-R-C-COOR (111) i

X p

wherein R and X are as defined above and Z is an alkali metal atom with an alkali metal isothiocyanate in the presence of an acid to give a 2-mercaptoimidazole compound of formula Ia r ² ooc

S-H

AND

X / 1 «/ o

wherein R and X are as defined above, optionally converted to a compound of Formula 1b

R ² 00C-f-H (lb)

IN

X by treatment with sodium nitrite in the presence of nitric acid in water or by reaction with Raney nickel in the presence of a lower aliphatic alcohol, preferably ethanol, at a temperature in the range of 40 to 80 ° C or by reaction with an aqueous hydrogen peroxide solution. in the presence of a carboxylic acid, and optionally the compound of formula I is converted to a salt by treatment with an acid or base, and the stereochemically isomeric forms are prepared.

In the above processes, for example, aromatic hydrocarbons such as benzene, toluene or xylene, ethers such as diethyl ether, tetrahydrofuran or dioxane or other aprotic organic solvents are used as the inert solvent. For the cyclization reaction of an imidazole ring structure, strong mineral acids such as hydrohalic acids such as hydrochloric acid are most commonly used. Most preferably, an excess of 5 to 50, preferably 15 to 40 times the desired molar amount is used. The excess of the ammonium salt in this process is 2 to 50, preferably 10 to 30 times the desired molar amount.

The substituent R on the carboxylic acid group ee can be converted to the other substituents included in the definition of R by conventional reactions known in the art to modify the carboxylic acid function, for example by hydrolysis and esterification and / or transesterification.

If the synthesis of stereochemically pure isomers is involved, stereoselective reaction steps and conditions are recommended. On the other hand, conventional separation methods can be used to obtain pure isomers from a mixture of stereochemical isomers.

The starting materials for the preparation of the novel compounds of the formula I are known or can be obtained by known synthetic procedures.

For example, a compound of formula II can be obtained by reacting a glycine ester of formula IV from -nh-ch ₂ -coor ² (IV) wherein R and Z are as defined above, with formic acid in the presence of acetic anhydride. Compounds of formula IV may be prepared by reacting an amine of formula V from -nh ₂ (V) wherein Z is as defined in formula I with an o-bromoacetic acid ester of formula VI

Br-CH ₂ - COOR ² (VI) wherein R is as defined for Formula I, in the presence of an acid binding agent such as sodium carbonate.

Compounds of formula I are stable compounds and need not be handled with care.

When used at the indicated application rates, the compounds of formula I have good selective herbicidal properties, making them very suitable for use preferably in corn and rice. In some cases, weed damage also occurs, which until now has been regulated only by total herbicides.

At higher application rates, all test compounds are so severely damaged in their development that they die.

The invention also relates to herbicidal mixtures comprising as active ingredient a compound of formula I as mentioned above. Preferred mixtures contain as active ingredient a novel compound of formula I, and the novel compounds can be used in preferred weed control methods.

In the weed control method of the invention, the compounds of formula I are used in unmodified form or preferably together with an adjuvant conventionally used in the formulation process and are therefore formulated in known manner into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders. dusts, granules, and also encapsulated materials in, for example, polymeric compounds. Depending on the nature of the compositions, the method of application, such as spraying, spraying, dusting or pouring, is chosen according to the intended use and the prevailing conditions of application.

Formulations, i.e., formulations or mixtures containing a compound (active ingredient) of the formula I and optionally a solid or liquid adjuvant, are prepared in a known manner, for example by homogeneously mixing and / or comminuting the active ingredients with extenders, for example solvents, solid carriers and optionally surfactants. reagents.

Suitable solvents are aromatic hydrocarbons, preferably C8-C12 fractions, for example 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, dimethylsulfoxide or dimethylformamide and vegetable oils or epoxidized vegetable oils such as epoxidized coconut oil or soybean oil or water.

Solid carriers used, for example, for dusts and dispersible powders are normally natural mineral fillers such as calcite, talc, kaloin, montmorillonite or attapulgite. It is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers to improve physical properties. Suitable granulated adsorbent carriers are of the porous type, for example pumice, broken brick, sepiolite or bentonite, and suitable non-adsorbent carriers are materials such as calcite or sand. In addition, a large amount of pre-granulated material of an inorganic or organic nature, for example in particular dolomite or pulverulent plant residues, may be used.

Depending on the nature of the compound of formula I, suitable surfactants are nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also understood as meaning mixtures of surfactants.

Suitable anionic surfactants may be water-soluble soaps and water-soluble synthetic surfactants.

Suitable soaps are alkali metal salts, alkaline earth metal salts, or substituted or substituted ammonium salts of higher fatty acids (C1 -C6), for example sodium or potassium salts of oleic or stearic acid, or mixtures of natural fatty acids, which can be obtained, for example, from coconut oil or tall oil. Fatty acid methyltaurin salts may also be mentioned.

More commonly, however, so-called synthetic surfactants are used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

Fatty sulphonates or sulphates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain an alkyl radical of 8 to 22 carbon atoms which also includes an alkyl portion of the acyl radicals, for example sodium or calcium lignosulphonic acid, dodecyl sulphate or fatty alcohol-sulfate mixtures obtained from natural fatty acids. These compounds also contain salts of a sulfuric acid ester and a sulfonic acid fatty alcohol / ethylene oxide adduct. The sulfonated benzimidazole derivatives preferably contain two 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, dibutyl naphthalenesulfonic acid or the naphthalenesulfonic acid / formaldehyde condensation product.

Appropriate phosphates, for example phosphoric acid ester salts, are also suitable

CS 276238 Βδ of a pnonylphenol adduct with 4 to 14 moles of ethylene oxide, or phospholipids.

The nonionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols or saturated or unsaturated fatty acids and alkylphenol, said derivatives having 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 parts of alkylphenol.

Other suitable nonionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopropylene glycol and an alkylpolypropylene glycol containing from 1 to 10 carbon atoms in the alkyl chain, the adducts containing 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.

Typical examples of nonionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene / polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Suitable nonionic surfactants are also polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are preferably quaternary ammonium salts containing as the N-substituent at least one alkyl radical of 8 to 22 carbon atoms, as further substituents unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of a halide, methylsulfates or ethylsulfates, for example stearyltrimathylammonium chloride or benzyldi [2-chloroethyl] ethylammonium bromide.

The surfactants commonly used in the formulation process are described, for example, in the following publications:

McCutcheon's Detergents and Emulsifiers

Mc Publishing Corp., Ridgewood, New Jersey, 1581; H.Stache,

Tensid-Taschenbuch, 2nd Edition, by C. Hanser Verlag,

Munisch & Vienna, 1981; M, and J. Ash, Encyclopedia of Suffactants,

St. I-III, Chemical Publishing Co., New York, 1980-81.

The herbicidal mixtures which are preferably used in the process according to the invention usually contain 0.1 to 95%, preferably 0.1 to 80% of the compound of formula I, 1 to 99.9% of a solid or liquid adjuvant and 0 to 25%, preferably 0.1 to 25% of a surfactant.

Preferred compositions are comprised in particular of the following components (% = weight percent):

Emulsifiable concentrate active 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%

The active ingredient will be dusted from 0.1 to 10%. preferably 0.1 to 1%.

solid support: 99.9% to 90%, preferably 99.9 to 99%

Suspension concentrate active ingredient:

water:

surfactant:

Wettable powders active ingredient surfactant: solid carrier:

Granulate active ingredient:

solid carrier:

up to 75%, preferably 10 to 50% to 25, preferably 88 to 30% to 40, preferably 2 to 30%

0.5 to 90%, preferably 1 to 80% 0.5 to 20%, preferably 1 to 15% to 95%, preferably 15 to 90%

0.5 to 30%, preferably 3 to 15% 99.5 to 70%, preferably 97 to 85%

Some compounds of formula I which are used as active ingredients in the weed control method of the invention are listed in the following tables for illustrative purposes without limiting the scope of the invention.

At the same time, the results of the herbicidal activity tests according to the following method are reported for some compounds.

Postemergence herbicidal effect

In the greenhouse, the seeds of the test plants are sown in plastic pots filled with sandy soil, which is then covered with a 0.5 cm layer of the same soil. Test compounds were dissolved in acetone (100 mg of compound in 4 mL of acetone) and further diluted immediately prior to application with tap water. Each pot receives 20 ml of the test solution, which is equally distributed on the soil surface using a plastic syringe. Dilution of the test solution is carried out in such a way that the amount of active ingredient is 4 kg per hectare.

During the whole test period (4 weeks), the pots are kept on the bench under the normal greenhouse conditions. Temperature and humidity vary with the time of day and time of year.

The herbicidal effect is evaluated by recording the above growth of plants according to the following semi-logarithmic scale:

: no effect / growth comparable to untreated plants /: 2.5% effect: 5% effect: 10% effect: 15% effect: 25% effect: 35% effect.

7.8: 50% effect 8: 67.5% effect.

Note: A score of 8.9 indicates that the herbicidal effect is about 85% while the score. (8/9) indicates that said effect is closer to 9 than -8 and 8/9 / closer to 8 than 9s N.T. indicates not tested.

Tab. 1:

Slouc, C. R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ Physical data Digitaria Poa Ecbinocbloa 1.01 H ch ₃ H H H H Ή M.p. 149-151.5 ° C 9 9 / 8/9 1.02 H ch ₃ H H H H H m.p. High: 63 ° C 9 9 9 1.03 H ch ₃ ch ₃ ch ₃ H H H mp 100-101 ° C 9 / 8/9 9 1.04 H ch ₃ H H ch ₃ H H ₃ tt117 to 118 ° C · 1.06 H ch ₃ H H H ch ₃ ch ₃ , HHO ₃ / mp36 ° C / dec./ 8/9 8.9 8.9 1.07 H CH ₃ H H H ch ₃ H HNO ₃ / mp 139-140 ° C 9 / 8/9 0 1.08 H CH ₃ CH ₃ ch ₃ H H H ° C / ° C /rozkl./ Q 9 9 1.10 H CH ₃ H H H H P , HIT0 ₃ / ttl6l ° C 8.9 9 9 1.11 SH CH ₃ H H ch ₃ H H mp.171-172 ° C 1.12 SH CH ₃ CH ₃ H H H H mp 154-155 ° C 1.13 SH CH ₃ H H H H och ₃ mp.184-186 ° C 1.14 SH CH ₃ H H H ch ₃ ch ₃ mp 190-190.5 ° C 1.15 SH CH ₃ H H H och ₃ H mp.170-171 ° C 1.16 SH CH ₃ H H H H H mp 157-158 ° C 1.17 SH CH ₃ ch ₃ ch ₃ H H H mp.171-172 ° C 9 8.9 9 1.18 H c ₂ H ₅ H H H H H HNO ₃ mp 135-136 ° C 9 9 R.T. 1.19 H _ H H H H H HNCl ₃ / mp 109-110 ° C 1.35 K C 6 ^H 11- cy l.H H H H H .RO- / m.p. 144 až 145 ° C 1.41 H H H H H H . H mp 206-221 ° C 1.42 H C 3 ^H 7 ^-i H H H H H H! TO ₃ / ttl38 to 140 ° C 1.44 SH ch ₃ H H H H F. mp 205 ° C 8.9 8.9 8.9 1.45 H CH ₃ H H H H p mp.161 ° C

Tab.l./pokrač/

Merge. C. R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ R ⁷ Physical data Digitaria Poa Echino- chloa 1.46 SH CH 2 H H H H Br mp 206 ° C 8.9 8.9 8 1.47 H CH 2 H H H H Br mp.172 ° C 8.9 9 8.9 1.48 SH CH 2 H H H H Cl mp 218 ° C 8.9 / 3/9 / 8/9 1.49 H CH 2 H H H. H Cl mp 135 ° C 8.9 9 / 8/9 1.50 SH ch ₃ H H H H H mp 149-150 ° C 9 8 / 8/9 1.51 H CH, H H H H H ./C00H/ ₂ / tt Mp 136-138.5 ° C 9 8.9 9 1.52 H CH ₂ -CH = ch, ₂ H H H H H M.p. BNO ₃ / mp 103-104 ° C 9 7.8 N.T. 1.53 H C ₄ H ₉ -n H H H H H , HN0 ₃ / ttl26 127 ° C 1.54 H ^C 5 ^H 11 ' ⁿ H H H H H HNO ₃ mp 103-103.5 ° C 1.55 H / CH _3/2 CH Oh ₂ - H Η H H .EN0 ₃ / ttl39 to 140 ° C 1.56 H 0 ^ Η H H H H HNO 3 / m.p. 92.5 ° C 9 9 9 1.57 H / ch ₃ / _? ch CH, | ^d H ₃ C-CH- H H H H .HH0 ₃ / ttl33,5 136 ° C 1.59 H CH ₃ ch ₃ H H H H mp 90-91 ° C 9 9 9 1.61 H ^C 2 ^H 5 CH ₃ ch ₃ H H H mp 74-75 ° C 9 9 9 1.62 H ° 4 ^H 9 ^y ch ₃ CH ₃ H H H mp 64.5 - 66.5 ° C 1.63 H ° 5 ^H -n ch ₃ CH ₃ H H H mp 72-75 ° C 1.64 H CH ₃ ch ₃ CH ₃ H H och ₃ HNO ₃ / mp 163 ° C 9 9 9 1.65 H CH ₃ CH ₃ CH ₃ H H och ₃ mp 62.1 ° C 9 / 8/9 9 1.66 H CH, CH, CH ₃ H ch ₃ ch ₃ .HH0 ₃ / ttl63 ° C /rozkl./ 9 8 H.T. 1.67 H ch ₃ CH ₃ CH ₃ H ch ₃ ch ₃ mp 133-134 ° C 1.68 SH CH ^ ch ₃ CH ₃ H CH ₃ CH ₃ mp 200 - 201 ° C 1.69 SH CH ₃ ch ₃ CH ₃ H H ° ch ₃ mp.166-167 ° C 9 / 8/9 / 8/9 1.70 H H CH ₃ ch ₃ H H H mp 238 ° C /rozkl./ 8 17. T. 8 1.71 H ch ₃ CH ₃ CH ₃ H H H CH ₃ -SO ₃ H / mp 141-151 ° C

Tab.l. /continue./

Merge. C. R ¹ R ² R ³ R ⁴ R ⁵ Η ⁶ Physical data Digitarie Poa Echino- cbloa 1.72 H ch ₃ ch ₃ ch ₃ Η Η Η M.p. 146 ° C /rozkl./ 1.73 H CH ₃ h H Η Η Η M.p. 145 ° C '·' * /rozkl./ 1.74 H CH ₃ h H Η Η Η , CH ₃ - ^ 2y> - SO ₃ H / mp178 to 179 ⁰ C 1.75 H ch ₃ ch ₃ ch ₃ Η Η Η HCl / mp.158 ° C / rozkl, / 1.76 H ch ₃ ch ₃ ch ₃ Η Η Η .cj? ₃ cooh / mp 92-93 ° C 1.81 H Ο ^ Ηγ-η H Η Η Η - Η mp 60-63 ° C 1.82 H C 1 H 4 -cycl. H Η Η Η Η mp 86-88 ° C 1.83 H ch ₂ -ch ₂ -o 3 H Η Η Η Η mp 66.8 ° C 8.9 8.9 H.T. 1.84 H ch _{2 -} c = ch Η Η Η Η Η mp 101-103 ° C 1.85 H CH ₂ -CH = CH ₂ / H Η Η Η Η mp 81-82 ° C 1.86 H benzyl H Η Η Η Η .HHO ₃ / tt 133.5 to 134.5 ° C 1.88 H _C-CH3 Η Η Η Η mp 83-95 ° C /trance 1.89 SH ch ₃ c ₂ h ₅ Η Η Η Η mp 118-120 ° C 9 9 9 1.91 H ch ₃ c ₃ h _7- i Η Η Η Η mp 123-124.5 ° C 9 9 1.92 SH ch ₃ c ₃ h _7- i Η Η Η Η m.p.174-175 ° C 1.93 H ch ₃ % Η Η Η HNO ₃ / t155 to 151 [deg.] C 1.94 H CH ₃ % Η Η Η mp 109-110 ° C 9 9 9 1.95 SH CH ₃ C ₈ H 8 ^ 5 Η Η Η m.p.164.5-165 Noc: 2 ° C 1.97 H c ₃ h ₇ h Η Η Η Η mp 77-79 ° C 1.103 H CH ₃ Cl 2 -n Η Η Η -Η HNO ₃ / mp 37 ° C /rozkl./ - 9. / 8/9 9 1.104 SH CH ₃ C ₃ H ₇ -n - - -  '- - - - Η Η Η Η mp.160-161 ° C . / 8/9 / 9/9 / 8 / 9_ 1.106 SH CH ₃ -C ₄ H _g -n Η - Η Η; Η tt139 to ^- 140 ° C / 8/9 7.8 'Ό / 9 / 1.107 . H ch ₃ C ^ - η _ - - “· Η - Η ·· Η ^- Η - 1,2-trans - '- - mp 79.5-80 ° C - / 8/9 ' 8 ^ 9 / 8/9 ' - · - -

CS 276238 36

Tab.l. /continue./

Merge. C. R ^L R ² r3 r ⁴ R ⁵ R ⁶ R ⁷ Physical data Digitaria Poa Echino- cbloa 1.109 H ch ₃ H H H κο ₂ H m.p.148-152 ° C 1.125 H CH ₃ CH ₃ H H H H 1.2-cis / mp 101-102 ° C 1.126 SR CH ₃ ch ₃ H H H H 1,2-trans / mp, 156-157 ° C 9 / 8/9 9 1.127 H CH ₃ CH ₃ H H H H 1,2-trans / mp. 110-110.5 ° C 0.9 8.9 8.9 1.128 H ch ₂ -ch ₂ -OCH ₃ Ή H H H H .HN0 ₃ / mp 115-117 ° C 1.129 H C ₂ H ₄ -OC ₂ H ₅ H H H H. H .HN0 ₃ / mp 117-118 ° C 9 7.0 N.T. 1.130 SH ^ 5 H H H H H , HN0 ₃ / mp 155.5 157 ° C 1.131 H CH ₃ CH ₃ ch ₃ H H P Mp ₃ / mp 44.5 ° C 9 9 9 1.142 SH H CH ₃ ch ₃ H H H mp 196-198 ° C 1.144 H H H H H F H H ₂ O / mp 129.9 ° C 1.159 Sil ch ₃ benzyl H H H H 1,2-trans m.p. 210.3 ° C 1.160 SH ch ₃ benzyl H H H H M.p. 180.2 ° C 1.162 H ch ₃ benzyl H H H H 1,2-cis / mp 129.1 ° C 8.9 9 R.T. 1.163 H ch ₃ benzyl H H H H 1,2-trans / mp ₃ mp 126.5 ° C 8.9 9 9 1.165 SH CH ₃ benzyl H H H H mp 201.3 ° C 1.166 H CH ₃ benzyl H H H H HNO ₃ / mp 44.3 ° C / 8/9 7.8 N.T. 1.168 H CH ₃ C ₄ H _g -n H H H H 1,2-trans / m.p. Mp 90-90.5 ° C 1.169 SH CH ₃ C ₅ H ₁₁ -n H H H H 1,2-cis / m.p. Mp 170-172 ° C 8.9 N.R. 8/9 / 1.174 H CH ₃ C ₄ H _g -n H H H H HNOj / trans / mp 90 °, 5 ° C 8/9 /. 8 8/9 / 1.177 H- CH ₃ ch ₃ CHj- Cl H H cis / m.p. Mp 146-147 ° C - 1.178 H CH ₃ - CH ₃ ch ₃ Cl H H 94-96 ° C ₌ -

CS 276238 Βδ

Tab.l /continue/

Merge. C. R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ R ⁷ Physical data Digitaria Poa Echinochloa 1.179 H CH 2 H H H H H _CH3 what tt148 ₃ h 151 ° C 1.180 H CH ₃ ch ₃ ch ₃ H H H ch ₃ cooh / tt 48-52 ° C 1.181 H ch ₃ ch ₃ ch ₃ H H H h ₃ c - ^^ sat ₃ h Mp 159-160 ° C 1.206 H CH ₃ ch ₃ ch ₃ Ή H /+/-//t.t. Mp 66-67.5 ° C 9 9 9

Tab. 2:

Merge. C. R ¹ R ² R ³ R ⁶ R ⁷ Physical data Digitaria Poa Echinochloa 2.19 H ch ₃ H ch ₃ H mp 66-69 ° C 2.20 H CH, H H H , HHO ₃ / tt 139.5-140.5 ° C 9 9 8/9 / 2.21 H ch ₃ H H H mp.82-83 ° C 2.22 H H H H HNO ₃ / tt 39 to 140 [deg.] C 2.23 H % H H H mp 139-140 ° C 2.24 SH CH ₃ H P H m.p.191 ° C 9 8 8.9 2.25 H CH ₃ H P H mp 187 ° C 9 / 8/9 / 8/9 2.26 SH CH ₃ H Cl H mp 218 ° C 2.27 H CH ₃ H Cl H mp 214 ° C 9 7.8 8 2.28 H CH ₃ H Br H mp.164 ° C 2.29 SH CH ₃ ch ₃ Cl Cl mp 203 ° C 2.30 H CH ₃ ch ₃ Cl Cl mp 126 ° C 9 8.9 8.9

Tab.2. /continue./

Merge. C. R ¹ R ² R ³ R ⁶ R ⁷ Physical data Digitaria Poa Ecbionocbloa 2.32 SH ch ₃ H H H mp.158-160.5 Noc: 2 ° C 2.33 H H H H H mp 209-211.5 Noc: 2 ° C 2.34 SH CH ₃ ch ₃ H H mp.176.6 ° C 8/9 / / 8/9 8/9 / 2.35 H CH ₃ CH ₃ H H MNO _{3 /} tt.l4O.3 Low: 9 ° C 9 9 2.36 H H CH ₃ H ch ₃ mp 209.9 ° C 2.37 H CH ₃ H H ch ₃ mp 77-80 ° C

Tab.3.

Merge. C. R ¹ R ² R ⁶ R ⁷ R ⁸ Physical data Digitaria Poa Echinocbloa 3.01 SH ch ₃ H H H mp 230 ° C /,rozkl./ 3.02 H CH, H H H .HNO ₃ / tt M.p. 141-144 ° C 8.9 8.9 8.9

Tab.4

Merge. C. R ¹ R ² R ³ R ⁴ R ⁶ Physical data Digitaria Poa Echinocbloa 4.01 SH CH3 _{2-CH3 2-CH3} H mp.171-172 ° C / 8/9 / 8/9 9 4.02 H ch _{3 2-CH3 2-CH3} H HNO ₃ / mp 172-173 ° C 9 9 9 4.03 H CH _{3 2-CH3 2-CH3} H mp 96.5 to 97.5 ° C 9. / 8/9 9 4.04 SH CH ₃ 2-0 ^ 5 2 -¾ H mp.164 to 165 [deg.] C 9 / 8/9 9 4.06 H CH ₃ 2-¾ 2-¾ H 83.5 to m.p. 85 C 9 / 8/9 9 4.08 H CH ₃ 2-C ₃ H ₇ -i H H t.v.150 až 155 ° C at 1 Pa 4.11 H CH _{3 2-CH3} H 5-Cl n ³ p = 1,5600 cis / trans 4/1 4.20 SH CH _{3 2-CH3} H H m.p.155 to 157 ° C cis / trans / 1/3 / 9 9 8.9 4.24 H H _{2-CH3 2-CH3} H mp.208 to 209 ° C (dec.) 4-26 H CH _{3 2-CH3 2-CH3 6-CH3} mp 79.3 ° C 9 9 9 4.28 H CH _{3 2-CH3 2-CH3} 6-C1 mp, 156-158 ° C 8.9 '9 9 4.32 H CH _{3 2-CH3 2-CH3} 6-0GH ₃ mp 105-106 ° C 4.34 H CH _{3 2-CH3 2-CH3 5-CH3} [nu] D = 1.5502 9 9 9 4.35 H _{2-CH3 2-CH3} H mp 124-125 ° C 9 9 / 8/9 4.36 H C ₃ ^H 7 -n 2-CH ₃ 2-CH ₃ H mp 90-91.5 ° C / 8/9 / 8/9 / 8/9 / 4.37 H c ₃ h ₇ -and - _{2-CH3 2-CH3} H. mp 140-141 ° C 9 / 8/9 8.9 4.43 H CH ₃ _ _2-CH3 - H H trans (HNO ₃ ) mp 160-162 ° C - - 4.45 H. CH ₃ 2-CH ₃ 'H H cis / HNOj / mp.160 to 9.62 ° C - 4.46 ' SH .. CHj 2-CH, 2-benzyl H trance/ - - mp.183-184 ° 8.9 ’8 H.T.

Tab, 4 /continue/

Merge. C. R ¹ R ² R ³ R ⁴ R ⁶ Physical data Digitaria Poa Ecbinochloa 4.48 H ch _{3 2-CH3 2-CH3} H HC1 / mp 152-154 ° C 4.49 H CH _{3 2-CH3 2-CH3} H ch ₃ so ₃ h / t 193-195 ° C 4.50 H CH _{3 2-CH3 2-CH3} H 4-CH ₃ -C ₈ H ₄ -SO ₃ H mp 189-191 ° C 4.51 SH CH _{3 2-CH3 2-CH3} H ZZ7 -14O = ^20, 5 ° // S / tt115 118 ° C / mixture of atropisomers 4.52 SH CH _{3 2-CH3} 2-CK ₃ H / R // 5Z / ²⁰ = + 144 ° (tt 110 to 112 ° C / atropisomer mixture 8/9) 8.9 8.9 4.53 H CH _{3 2-CH3 2-CH3} H / s /// A / § ° = + 76.3 ° mp.73 to 75 ° 0 8.9 8.9 N.T. 4.54 H CH _{3 2-CH3 2-CH3} H MiW ξ ° = -72.9 ° mp 73-75 ° C 4.57 H CH _{3 2-CH3} 2-¾ H mp ₃ / mp 137-139 ° C 4.58 SH CH _{3 2-CH3} 2-Benzyl H cis / 225.5 to 226 ° C (dec.) 4.59 H CH _{3 2-CH3} 2-Benzyl H cis / mp 152-153 ° C 4.60 H CH _{3 2-CH3} 2-Benzyl H trance/ mp.88.5 to 89.5 ° C 9 8.9 9 4.65 ' SH CH ₃ 3-CH ₃ 3-CH ₃ H mp 190.0 ° C 9 8.9 9 4.66 H CH ₃ 3-CH ₃ 3-CH ₃ H HNO ₃ / mp 52.4 ° C 9 / 8/9 9 4.68 · H H 3-CH ₃ 3-CH ₃ H mp 180 ° C 8 8.9 9 4.70 H CH ₃ 2-Benzyl H H HNO ₃ (trans / t) 142.8 ° C / 8/9 9 / 8/9 4.72 H CH ₃ 2-Benzyl H H HNO ₃ (cis / t) 133.7 ° C / 8/9 9 8.9 4.73 H CH ₃ 2-CH3 H 5- -och ₃ cis / trans (2/5) mp 78-81 ° C -4.74 H_ CH _{3 2-CH3} H 5-P cis / trans / 4/1 / np ⁰ = 1.5412 4.75 H CH _{3 2-CH3} H_ 5-P - trans / np ⁰ = 1.5405 - 4.7-7 H CH _{3 2-CH3} H 7-P cis / trans (1/1) m / z «1.5410“.

íTab.4 /continue/

Merge. C. R ¹ R ² R ³ R ⁴ R ⁶ Physical data Digitaria Poa Echinochloa 4.78 H ch ₃ 2- / 2.4-Cl ₂ CgH ₃ / H H 180-185 ° C at 2 Pa 4.79 SH ch _{3 2-CH3 2-CH3} H (R) -atropisomer A / mp.176-177 ° C F 3 ° = 16.9 ° ⁺ 4.80 SH ch _{3 2-CH3 2-CH3} H /R/-atropis.B/0,25 g ^{H c} 1 = + ₂ tt75 296® + 4.81 SH CH _{3 2-CH3 2-CH3} H /S/-atropia.A/ mp.175.5 to 176.5 ° c / [.alpha.] D @ ²⁰ = 16.4 DEG 4.82 SH CH _{3 2-CH3} 2-0H ₃ H /S/-atropisB/0.25 ^C 6 ^H 12 mp 75 ° C / ° F = 303 ° ⁺ 4.83 SH CH _{3 2-CH3 2-CH3} H / RS / -atropisoraer / mp 142-143 ° C 4.99 H C 4 ^H 9 ⁿ _{2-CH3 2-CH3} H c ₄ h ₉ -oos ₃ / mp 130-131 ° C 4.100 H ch _{3 2-CH3 2-CH3} H HN0 ₃ // R // mp 144.5-147.5 ° C 4.102 H ch _{3 2-CH3 2-CH3 4-CH3} mp 125-128 ° C 9 9 9 4.103 TO ch _{3 2-CH3 2-CH3} 4-F mp 97-100 ° C 9 9 9 4.104 H ch _{3 2-CH3 2-CH3} 4-C1 . mp 111-113 ° C 4.105 H ch _{3 2-CH3 2-CH3} 5-OCH ₃ n ³⁰ = 1.55O4 4.106 H ch _{3 2-CH3 2-CH3} 5-E n ³ ° = 1.5385 D 4.107 H CH _{3 2-CH3 2-CH3} 5-Cl mp.88 to 90 ° C 8.9 8.9 9 4.108 H CH _{3 2-CH3 2-CH3} 5-Cl HNO ₃ / mp 200 ° C 9 9 9 4.110 H CH _{3 2-CH3 2-CH3 7-CH3} m.p. Mp 95-98 ° C 9 9 9 4.111 H CH _{3 2-CH3 2-CH3} 7_F m.p. Mp 95-98 ° C 9 9 9 4.112 H H _2-CH3 2-CH., H Mp 215 ° C

/ dec./f/J ² = -72 ° D

4.128

109.5 C ^U £ <Rev. ²⁰ = -75 °

D

4.129 H ch _{3 2-CH3} 2-0 ^ 5H cis./ mp 77.5 to 82 Noc: 2 ° C 4.132 H CH _{3 2-CH3} 2-0 ₃ Ηγ-η H m.p.150 to 153 ° c 4.133 H CH _{3 2-CH3} 2-0 ₃ Ηγ-η H cis / m.p.109 to 111 ° c

Tab.4 /continue/

Merge. C. R ¹ R ² R ³ R ⁶ Physical data Digitaria Poa Ecbinochloa 4.134 SH CH ₃ 2-CH ₃ 2-C ₄ H ₉ -h H m.p.109 to 120 Noc: 2 ° C • 4.136 SH CH ₃ 2-0 2-Cl 2 H atropisomer / m.p.160-162 ° c 4.137 H H 2 -C 1 ^2_C 2 ^H 5 H 215-217 Noc: 2 ° C 4.138 H CH 2 2 -CH ₃ 2-Cl 2 7-C1 189-192 Low: 9 ° C 9 9

+ = 7 ²⁰ trichloromethane

D

Tab.5

Merge, C. R ¹ R ² R ⁴ Physical data Digitaria Poa Ecbinochloa 5,05 H ch _{3 2-CH3 2-CH3} ΗΝ0, mp 135.6 ° C / rozkl, / 9 9 H.T. 5.06 SH CH _{3 2-CH3 2-CH3} mp.209 to 209.5 ° C 7.8 N.T. 7.8

Tab. 6

Merge. C. R ¹ R ² tn Physical data Digitaria Boa Ecbinochloa 6.01 SH ch ₃ 3 mp.161-164 ° C 9 9 9 6.02 H ch ₃ 3 ₃ / mt132 ° C / dec./ 6.03 H CH ₃ 3 mp 155-154 ° C 9 9 9 6.04 SH CH ₃ 4 mp 196-197 ° C 6.05 H CH ₃ 4 m.p.177-178 ° C / 8/9 8.9 / 8/9 6.06 H CH ₃ 4 .hro ₃ / mp. 145.2 ° C

Tab. 7

Merge. R ¹ R ² Art. R ³ R ⁶ Physical data 7.01 SH CH ₃ H 2 -CH ₃ m.p.233 ° /rozkl./

Tab. 8

Merge. C. R ¹ R ² R ³ R ⁴ OF Physical data Digitaria Poa Echiochloa 8.01 SH ch ₃ 6-CH ₃ 6-CH 0 mp 180-182 ° C 8.02 SH CH ₃  H H WITH mp.166 ° C 8.9 8.9 / 8/9 8.03 H CH ₃ H H WITH HNO ₃ / mp, 154 ° C 9 9 9 8.17 G H H H WITH HCl / mp

Tab. 9

Merge, C. R ¹ R ² R ³ R ⁴ R ^é R ⁷ Physical data Digitaria Poa Eohinochloa 9.13 SH ch ₃ H H 6-C1 H m.p.181 ° C 8.9 B.T. 8.9 9.14 H ch ₃ H H 6-C1 H HNO ₃ / mp 51 ° C 9 8.9 9 9.15 SH ch ₃ H H 6-C1 7-C1 mp 212 ° C 9.16 H ch ₃ H H 6-C1 7-C1 HNO ₃ / t 200 ° C 9.24 H ch ₃ 3-CH ₃ 3-CH _{3 6-CH3} 8-CH ₃ mp 111-114 ° C 9.25 H H 3-CH ₃ 3-CH _{3 6-CH3} 8-CH ₃ mp 190-192 ° C

Tab. 10

Merge. C. R ¹ R ² R ³ R ⁴ R ⁵ Physical data 10.01 H ch ₃ ch ₃ ch ₃ H mp 60-62 ° C 10.09 H ch ₃ CH ₃ ch ₃ «4 mp 101-103 ° C 10.10 H CH ₃ CH ₃ ch ₃ OCH ₃ mp, 102-104 ° C

Tab. 11

Merge. C. R ¹ R ² R ³ R ⁴ Physical data Digitaria Poa Echinochloa 11.01 SH ch ₃ H H + 97.1 ° mp 141 ° C 9 8.9 9 11.02 SH ch ₃ H H -87.9 ° mp 141 ° C 8.9 8 8 11.03 H ch ₃ H H -25.8 ° resin 9 / 8/9 9 11.04 H ch ₃ H H + 22 ° resin 9 / 8/9 9

Tab. 12

Merge. 0. R ¹ R ² .R ⁶ Physical data Digitaria Poa Echinoobloa 17.01 H ch ₃ H m.p.146 ° C / 8/9 / 8/9 / 8/9 17.02 SH ch ₃ H m.p.208 ° C (dec.) 17.07 H H H m.p. 237.2 ° C

Tab. 13

Merge. C. R ¹ R ² m Physical data Digitaria Poa Ecbinocbloa 19.05 SH gh ₃ 3 mp.160-161.5 ° C 9 / 8/9 9 19.07 SH ch ₃ 4 mp 210-212 ° C 19.08 H ch ₃ 4 mp 133-135 ° C

CS 276238 Βδ

Tab. 14

Merge. C. R ¹ R ² R ³ R ⁴ r5 R ⁶ Physical data Digitaria Poa Echinochloa 20.02 H ch ₃ ch ₃ ch ₃ CH ₃ H cis / HNO ₃ / m.p. 133.1 ° C 9 9 9 20.04 H ch ₃ ch ₃ ch ₃ CH ₃ ch ₃ HNO ₃ / mp 55.6 ° C 9 9 9 20.07 H ch ₃ ch ₃ CH ₃ HHC0CH ₃ H 70 ° C (dec.) 20. 09 H ch ₃ ch ₃ CH ₃ Br Br m.p.138 ° C (dec.) 20.10 H ch ₃ ch ₃ CH ₃ och ₃ och ₃ mp 140-141 ° C 20.11 H ch ₃ ch ₃ ch ₃ 00 ^ 5 mp.112-115 ° C 20.12 H ch ₃ CH ₃ CH ₃ F F mp, 96-97 ° C

Tab. 15 Dec

Merge. C. R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ Physical data 21.01 H ch ₃ ch ₃ ch ₃ Br Br /1^.34,4^/ . 130-132 ° C. 21.02 H- ch ₃ ch ₃ ch ₃ Br och ₃ /1^,3/5.4^/, - - - mp 103-105 ° C - 21.04 her .ch ₃ " ^CH 3 CH ₃ H Cl cis -7t, mp 144-147 ° C 21.05 H '3 oh ₃ ch ₃ _CH ₃ - H _ Cl - mp 94-96 ° C

The following examples illustrate the invention without limiting its scope.

A. Examples of mixtures

Example 1: Formulation examples for solid compound of formula I (percent by weight) a) Wettable powder Compound No. 1.02 sodium lignosulfonate sodium lauryl sulfate sodium diisobutylnaphthalenesulfonate octylphenolpolyethylene glycol ether (7-8 moles of ethylene oxide) highly dispersed silica kaolin sodium a / b / c % 50% 0.5%% 5% 5%%

6%% 2%% 27% 27%%

59.5%

The active ingredient is intimately mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to give a wettable powder which can be diluted with water to form a suspension of the desired concentration.

b) Emulsifiable concentrate and / Compound No. 1.03 10% octylphenolpolyethylene glycol ether / 4-5 moles ethylene oxide / 3% calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether / 36 moles ethylene oxide / 4% cyclohexanone 30% xylene mixture 50%

Emulsion of any desired concentration with water.

b /%

%%

%%

% can obtain from this concentrate by dilution c / Dust Compound No. 1.03 talc kaolin s / b /

0.1% 1%

99.9%

- 99%

Dusts that are ready for use with the carrier and comminuting the mixture in a suitable mill.

<3 / Extruded granulate Compound No. 1.03 Sodium lignosulfonate Carboxymethyl cellulose Kaolin a / b /% 1%% 2%% 1%% 96%

The active ingredient is mixed and ground with adjuvants The mixture is extruded and then dried in a stream of air.

and the mixture is then moistened with water.

e / Coated granulate Compound No. 1.03 3% polyethylene glycol / mol.hm.200/ 2% kaolin 94 Jo

The finely divided active ingredient is uniformly applied in a kaolin mixer moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

f) Suspension concentrate and/ b / Compound No. 1.02 40% 5% ethylene glycol 10% 10% nonylphenolpolyethylene glycol ether (15 moles of ethylene oxide) 6% 1% sodium lignosulfonate 10% 5% carboxymethylcellulose; 1% 1% 37% aqueous formaldehyde solution 0.2% 0.2% silicone oil in the form of 75% aqueous emulsion 0.8% 0.8% water 32% 77%

The finely divided active ingredient is intimately mixed with adjuvants to give a suspension concentrate from which a suspension of any desired concentration can be obtained by dilution with water.

g / saline Compound No. 1.02 5% isopropylamine 1% octylphenolpolyethylene glycol ether / 78 moles ethylene oxide / 3% water 91%

Example 2

Formulation examples for the liquid active ingredient of formula I (percent are by weight)

a / Emulsifiable concentrate and/ b / C/ Compound No. 1.60 20% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 5.8% castor oil polyethylene glycol- ether (36 moles of ethylene oxide) 5% - - tributylphenolpolyethylene glycol- ether (30 moles of ethylene oxide) - 12% 4.2% cyclohexenone - 15% 20% xylene mixture 70% 25% 20% An emulsion of any desired concentration is can produce from this concentrate diluted water.

b / Solution and/ b / C/ d / Compound No. 1.60 80% 10% 5% 95% ethylene glycol monomethyl ether 20% '- - - polyethylene glycol (MG 400) - 70% - - 1'-Methyl-2-pyrrolidone - 20% - - epoxidized coconut oil - - 1% 5% petroleum distillate (distillation range 160 - 190 °) - - 94% - These solutions are suitable for application in in the form of microdroplets.

c / Granulate and/ b / Compound No. 1.60 5% 10% kaolin 94% - highly dispersed acid siliceous 1% - attapulgit - 90%

The active ingredient is dissolved in methylene chloride, the solution is sprayed onto a carrier and the solvent is then evaporated off under vacuum.

d / Dusts and/ b / Compound No. 1.60 2% 5% highly dispersed acid siliceous 1% 5% talc 97% - kaolin - 90%

Ready-to-use bachs are obtained by thoroughly mixing the carrier with the active ingredient.

CS 276238 Βδ

B. Biological examples

Example 3: Preemergence herbicidal effect

In the greenhouse, immediately after sowing the test compounds in the seed trays, the soil surface is treated with an aqueous dispersion of the test compound obtained from the 25% emulsified concentrate or 25% wettable powder of the test compounds which cannot be formulated as an emulsifiable concentrate. Two different concentrations are used, corresponding to 1 and 0.5 kg of test compound per hectare. The seed pans are kept in a greenhouse at a temperature of 22-25 ° C and 50-70% relative humidity. The test is evaluated in three weeks according to the following scale:

= plants did not sprout or die completely up to 3 = very strong effect up to 6 = average effect up to 8 s weak effect = no effect

In this test, the test compounds of formula I are most effective against grass weeds, whereas at given application rates there is no or only insignificant damage to the cultivated plants.

Results: Preemergence test

Dose kg.oc.sl / ha Merge. 1.01 Merge. 1.02 Merge. 1.03 Merge. 1.08 test.plant 1 0.5 1 0.5 1 0.5 1 0.5 maize 9 9 8 9 8 9 9 9 alopecurus myos. 2 2 2 2 2 2 2 2 digitaria sang. - - 1 1 1 1 1 1 echinochloa c.g. 1 1 1 3 1 1 1 1 sida spinosa - - 4 4 1 1 2 3 amaranthus ret. - - 4 4 1 1 2 2 chenopodium sp. 3 3 3 3 1 1 1 1 solanum nigrum - - 3 3 1 1 1 1 chrysanthe leuc. - - 2 2 2 2 2. 2 galium aparine 3 4 2 2 1 1 2 3 viola tricolor 3 3 2 3 1 1 1 1 vsronica sp. - - 2 2 1 1 1 1

- Not tested

Results: Preemergence test

dose kg cp / ba Merge. 1.16 Merge. 1.17 Merge. 4.01 1 0.5 you try. plant 1 0.5 1 0.5 maize 9 9 9 9 8 9 alopecurus myos. 5 6 2 2 3 4 digitaria sang. 1 1 1 1 1 1 ecbinochloa c.g. 2 2 1 1 1 1 sida spinosa 3 3 1 2 2 3 amarantbus ret. 3 3 2 2 2 3 cbenopodium sp. 3 4 1 1 1 1 solanum nigrum 2 2 1 1 2 2 chrysanthe. leuc. '3 3 2 2 4 6 galium aparine 4 5 2 3 2 3 viola tricolor 3 4 1 1 2 2 veronica sp. 2 2 1 1 1 1

Example 4: Post-emergence herbicidal action (contact herbicide):

A large number of weeds and cultivated plants are sprayed postemergence at the 4-6 leaf stage with an aqueous dispersion of the active ingredient at a dose of 4 and 2 kg of test compound per hectare and maintained at 24-26 ° C and 45-60%. relative humidity The test is evaluated at least 15 days after treatment in the same manner as in the preemergence test.

In this test, the compounds of formula I are also most effective against the test pleels. Cultured plants such as corn and rice are either not damaged or only damaged at higher rates of application of the test compound.

Results: Postemergence test

dose g.act 8l / ba Merge. 1.06 test plant 4 2 maize 8 9 rice, dry 9 9 xanthium sp. 3 4 chenopodium sp. 4 5 ipomosa 4 5 sinapis 4 7 galium aparine 5 5 viola tricolor 4 6

Example 5: The herbicidal effect of the transplanted rice of a day-old Yamabiko rice plant is transplanted into large plastic containers. scirpus and monochoria. The wannabes are watered to the extent that the surface is covered by a 2.5 cm water layer. After three days in the greenhouse, a diluted aqueous dispersion of the active compound is added to the water layer at an application rate of 500, 250, 125, 60, 30 and 15 g of active ingredient per hectare. The wannabes are then kept with a layer of water at 25 ° C and high humidity for 4 weeks in a greenhouse. The test evaluation is performed according to the scale in Example 3.

Results: (-: not tested)

Compound No. 1.01 1.02 15 Dec in 500 úč.sl. per hectare in 500 úč.sl. per hectare Tested grew. 250 125 60 30 15 Dec 25 0 125 60 30 rice Yamabiko 8 9 9 9 9 9 8 9 9 9 9 9 alisma , 1 1 1 1 2 3 1 2 2 3 3 3 ammania 1 2 2 2 2 2 - - - - - cyperus difformia 1 1 1 1 1 1 1 1 1 1 1 1 echinochloa c.g. 1 1 1 1 6 8 1 1 1 1 3 6 eleocharis - - - - - 1 1 1 1 1 1 fimbristylis 1 1 1 1 1 1 1 1 1 1 1 1 scirpus 1 1 1 1 2 4 1 1 1 3 4 4 j monochoria 1 1 1 1 1 3 * 1 1 1 1 1 1

Compound No. 1.03 in g úč.sl. per hectare 1.04 in 500 úč.sl. me hectare Tested grew. 500 250 125 60 30 15 Dec 250 125 60 30 15 Dec rice Yamabiko ” 9 9 9 9 9 9 8 9 9 9 9 9 alisma 1 13 3 3 6 1 1 2 3 5 7 cyperus difformia 1 1 1 1 2 2 1 1 1 1 3, 3 echinochloa c.g. 1 13 6 9 9 2 5 8 8 9 9 eleocharis 1 13 5 5 5 3 5 6 7 8 8 fimbristylis 1 1 1 1 1 1 1 1 1 1 1 1 scirpus 1 13 5 7 9 1 7 7 7 9 9 monochoria 1 1 1 1 3 9 1 1 3 5 5 6

Compound No. 1.11 1.12 in 500 úč.sl. per hectare in 500 úč.sl. per hectare Tested grew. > 50 125 60 30 15 Dec > 50 125 60 30 15 Dec rice Yamabiko 8 9 9 9 9 9 9 9 9 9 9 9 alisma 1 1 3 3 3 6 1 1 1 2 6 7 ammania - - - - - - 1 2 2 2 2 3 cyperus difformia 1 1 1 1 1 1 1 1 1 1 1 1 ecbinoohloa c.g. 1 2 6 8 9 9 1 3 4 8 9 9 eleocbaris 1 1 1 1 1 1 - - - - - - fimbristylis 1 1 1 1 1 1 1 1 1 1 1 2 scirpus 1 1 5 6 7 8 1 1 3 7 9 9 monochoria 1 1 1 2 4 6 1 1 2 2 4 7

Compound No. 1.16 in g úč.sl. per hectare Tested grew. 500 250 125 60 rice Yamabiko 8 9 9 9 echinochloa c.g. 1 1 2 3 scirpus 1 1 1 2 monochoria 2 3 3 3

Compound No. 3.01 4.01 in 500 úč.sl. per hectare in g 250 úč.sl. per hectare Tested grew. > 50 125 L25 60 rice Yamabiko 9 9 9 9 9 9 echinochloa c.g. 3 4 5 1 1 1 scirpus 1 2 3 1 2 3 monochoria 2 2 4 2 2 3

C. Preparation Examples

Example 6: 1- (7-Methoxy-1,2,3,4-tetrahydro-1-naphthyl) -2-mercapto-5-imidazolecarboxylic acid methyl ester (Compound 1.13) a (N-) 7-methoxy-1,2 3,4-tetrahydro-1-naphthyl / glycine methyl ester

367.0 g of 1-amino-7-methoxy-1,2,3,4-tetrabydronaphthalene are dissolved in 1500 ml of diethyl ether. To this solution was added dropwise a solution of 158.3 g of methyl bromoacetate in 450 ml of diethyl ether. The mixture was stirred at room temperature for 70 hours, the precipitate was collected and the solution was concentrated to dryness to afford quantitatively N- (7-methoxy-1,2,3,4-tetrabydro-1-naphthyl) glycine methyl ester.

b) N-formyl-N- (7-methoxy-1,2,3,4-tetrahydro-1-naphthyl) glycine methyl ester

2.40 g of N- (7-methoxy-1,2,3,4-tetrahydro-1-naphthyl) glycine methyl ester were added dropwise to 5.52 g of formic acid under cooling at 5 ° C. 1.79 g of acetic anhydride are then added and the mixture is kept at room temperature for 70 hours. Distillation in vacuo afforded 2.7 g (97% of theory) of N-formyl-N- (7-methoxy-1,2,3,4-tetrahydro-1-naphthyl) glycine methyl ester as a colorless resin.

c) A solution of 1.85 g of sodium methylate in 38 ml of tetrahydrofuran is prepared by adding a suitable amount of methanol and sodium hydride to tetrahydrofuran. While cooling to room temperature, 6.5 g of formic acid methyl ester and 10.0 g of N-formyl-N- (7-methoxy-1,2,3,4-tetrahydro-1-naphthyl) glycine methyl ester are added. After 20 hours, 30 ml of deionized water and 50 ml of diethyl ether are added to the mixture. The aqueous phase was separated and 30 ml of methanol and 8.6 ml of 36% hydrochloric acid were added. The solution is heated to 40-45 ° C and a solution of 5.8 g of potassium thiocyanate in 10 ml of deionized water is added. After 24 hours, the mixture was heated at 80 ° C for 5 hours. 7.3 g (64% of theory) of 1- (7-methoxy-1,2,3,4-tetrahydro-1-naphthyl) -2-mercapto-5-imidazolecarboxylic acid methyl ester, m.p. 184-186, are precipitated after cooling. Deň: 32 ° C.

Example 7: 1- (7-Methoxy-1,2,3,4-tetrahydro-1-naphthyl) -5-imidazolecarboxylic acid methyl ester (Compound 1.05)

Dissolve 0.22 g of sodium nitrite and 2.85 g of nitric acid in 7 ml of deionized water. 3.2 g of 1- (7-methoxy-1,2,3,4-tetrahydro-1-naphthyl) -2-mercapto-5 methyl ester are added portionwise at 25-30 ° C over one hour. -imidazolecarboxylic acids. The precipitate was collected to give 2.72 g of the nitric acid addition salt of 1- (7-methoxy-1,2,3,4-tetrahydro-1-naphthyl) -5-imidozolecarboxylic acid methyl ester. To this salt was added 10 mL of 10% aqueous sodium carbonate solution. Extraction of the aqueous phase with chloroform and evaporation of the organic solvent gave 2.72 g of 1- [7-methoxy-1,2,3,4-tetrahydro-1-naphthyl] -5-imidazolecarboxylic acid methyl ester as a colorless resin.

Example 8: 1- (1,2,3,4-Tetrahydro-1-naphthyl) -5-imidazolecarboxylic acid methyl ester (Compound 1.02).

A mixture of 16.5 g of 1 H -bis-formyl-N- (1,2,3,4-tetrahydro-1-naphthyl) glycine methyl ester, 65.0 g of ammonium acetate and 100 ml of acetic acid is heated under heating for 8 hours. reflux condenser. An additional 50 g of ammonium acetate was then added and refluxed for an additional 4 hours. The solution was diluted with 300 mL water and extracted with 2 x 100 mL toluene. The organic phases were combined, concentrated and separated by silica gel chromatography. Concentration of the eluate gave 1- (1,2,3,4-tetrahydro-1-naphthyl) -5-imidazolecarboxylic acid methyl ester, m.p. 63 ° C.

Example 9: 1- (2,2-Dimethyl-1,2,3,4-tetrahydro-1-naphthyl) -2-mercapto-5-imidazolecarboxylic acid methyl ester (Compound 1.17) a) N- (2,2-Dimethyl) 1,2,2,4-tetrahydro-1-naphthyl / glycine methyl ester 65.2 g of 1-amino-2,2-dimethyl-1,2,3,4-tetrahydronaphthalene are dissolved in 250 ml of diethyl ether. To this solution was added dropwise a solution of 28.5 g of bromoethyl ester in 150 ml of diethyl ether. The mixture was stirred at room temperature for 70 hours. The precipitate was collected and the solution was concentrated to dryness to give quantitatively the N- (2,2-dimethyl-1,2,3,4-tetrahydro-1-naphthyl) glycine methyl ester.

b) N-formyl-N- (2,2-dimethyl-1,2,3,4-tetrahydro-1-naphthyl) -glycine methyl ester

Complete yield of N- (2,2-dimethyl-1,2,3,4-tetrahydro-1-naphthyl) glycine methyl ester according to procedure a) was added dropwise to 67.8 ml of formic acid with cooling at 5 ° C. 24.9 ml of acetic anhydride are then added and the mixture is kept at room temperature for 70 hours. Distillation in vacuo afforded 35.2 g of N-formyl-N- (2,2-dimethyl-1,2,3,4-tetrahydro-1-naphthyl) -glycine methyl ester, m.p. 74-75 ° C.

c) A solution of 24.6 g of sodium methylate in 500 ml of tetrahydrofuran is prepared by adding a suitable amount of methanol and sodium hydride to tetrahydrofuran. While cooling to room temperature, 73.7 g of formic acid methyl ester and 35.2 g of N-formyl-N- (2,2-dimethyl-1,2,3,4-tetrahydro-1-methyl) glycine methyl ester are added. After 20 hours, 350 ml of deionized water and 700 ml of diethyl ether are added to the mixture. The aqueous phase was separated and 350 ml of methanol and 97.7 ml of 36% hydrochloric acid were added. The solution is heated to 40-45 ° C and a solution of 66.1 g of potassium thiocyanate in 200 ml of deionized water is added. After 24 hours at 40 ° C, the mixture was heated at 80 ° C for 5 hours. After cooling, 35.8 g of 1- (2,2-dimethyl-1,2,3,4-tetrahydro-1-naphthyl) -2-mercapto-5-imidazolecarboxylic acid methyl ester of melting point 171 DEG-172 DEG C. are precipitated. .

Example 10: 1- (2,2-Dimethyl-1,2,3,4-tetrahydro-1-naphthyl) -5-imidazolecarboxylic acid methyl ester (Compound 1.03)

Dissolve 5.8 g of sodium nitrite and 55 g of nitric acid in 3100 ml of deionized water. It is added in portions at a temperature between 25 ° C and 30 ° C over one hour

92.2 g of 1- (2,2-dimethyl-1,2,3,4-tetrahydro-1-naphthyl) -2-mercapto-5-imidazolecarboxylic acid methyl ester. The precipitate was collected to give 100.0 g of the nitric acid addition salt of 1- (2,2-dimethyl-1,2,3,4-tetrahydro-1-naphthyl) -5-imidazolecarboxylic acid methyl ester. To this salt was added 250 mL of a 10% aqueous sodium carbonate solution. Extraction of the aqueous phase with chloroform and evaporation of the organic solvent gave 80.4 g of 1- (2,2-dimethyl-1,2,3,4-tetrahydro-1-naphthyl) -5-imidazole-carboxylic acid methyl ester, m.p. 101 ° C.

Example 11: R1- (2,2,3,4-tetrahydro-1-naphthyl) -2-mercapto-5-imidazolecarboxylic acid methyl ester (compound 11.01) and (RH-) 1,2,3,4-tetrahydro-1 -naphthyl / -glycine methyl ester

The optically pure isomer of R-1-amino-1,2,3,4-tetrahydronaphthalene is prepared as described in U.S. Patent No. 3,953,506. 51.4 g of R-1-amino-1,2,3,4-tetrabydronaphthalene and 37.1 g of sodium carbonate are dispersed in 300 ml of methanol. To this dispersion was added dropwise 53.6 g of methyl bromoacetate. The mixture was stirred at room temperature for 100 hours. The precipitate was collected and the solution was concentrated to dryness to give R-R- (1,2,3,4-tetrabydro-1-naphthyl) glycine methyl ester quantitatively.

b) R-N-formyl-N- (1,2,3,4-tetrahydro-1-naphthyl) glycine methyl ester

64.9 of R-N- [1,2,3,4-1-naphthyl] glycine methyl ester was added dropwise to 5 &lt; 0 &gt; C with cooling to 134 ml formic acid. 48.9 ml of acetic anhydride are then added and the mixture is kept at room temperature for 70 hours. Distillation in vacuo gave 50.6 g of R-H-formyl-R- [1,2,3,4-tetrahydro-1-naphthyl] glycine methylster, m.p. 83-84 ° C.

c) A solution of 11.2 g of sodium methylate in 250 ml of tetrahydrofuran is prepared by adding a suitable amount of methanol and sodium hydride to tetrahydrofuran. While cooling to room temperature, 35.1 g of formic acid methyl ester and R-N-formyl-11- [1,2,3,4-tetrahydro-1-naphthyl] glycine methyl ester obtained in process b) are added. After 2 hours 130 ml of deionized water and 250 ml of diethyl ether are added to the mixture. The aqueous phase was separated and 130 ml of methanol and 46.9 ml of 36% hydrochloric acid were added. The solution is heated to 40-50 ° C and a solution of 31.5 g of potassium thiocyanate in 60 ml of deionized water is added. The mixture was stirred at room temperature for 24 hours. It precipitates during this time

24.4 g of R-1- (1,2,3,4-tetrahydro-1-naphthyl) -2-mercapto-5-imidazolecarboxylic acid methyl ester. After recrystallization from methanol, the product had a melting point of 141-142 ° C, α d ²⁰ = + 97.1 °.

^LJ D

Example 12: R-1- (1,2,3,4-Tetrahydro-1-naphthyl) -5-imidazolecarboxylic acid methyl ester (Compound 11.03)

1.4 g of sodium nitrite and 11.7 ml of nitric acid are dissolved in 75 ml of deionized water. 17.9 g of methyl R-1- [1,2,3,4-tetrahydro-1-naphthyl] -2-mercapto-5-imidazolecarboxylic acid methyl ester are added portionwise at 25-30 ° C over one hour. The precipitate is isolated to give the nitric acid addition salt of methyl ester R1- [1,2,3,4-tetrahydro-1-naphthyl] -5-imidazolecarboxylic acid. A 10% aqueous sodium carbonate solution was added to the salt. Extraction of the aqueous phase with chloroform and evaporation of the organic solvent gave 7.4 g of R- (1,2,3,4-tetrahydro-1-n-phenyl) -5-imidazolecarboxylic acid methyl ester as a colorless resin, which was purified by chromatography on silica gel. oupci. The pure resin product has a refractive index [α] ^{20 20} -25.80 °.

- - - - D

Example 13: S1- (1,2,3,4-tetrahydro-1-naphthyl) -2-mercapto-5-imidazole-8-carboxylic acid methyl ester (compound 11.02) and (SN-) 1,2,3,4-tetrahydro-hydro -1-naphthyl / glycine methyl ester

The optically pure isomer of S-1-amino-1,2,3,4-tetrahydronaphthalene is prepared as described in U.S. Patent No. 3,953,506. ...

26.0 g of S-1-amino-1,2,3,4-tetrahydronaphthalene and 18.8 g of sodium carbonate are dispersed in 150 ml of methanol. To this dispersion was added dropwise 27.1 g of methyl bromoacetate. The mixture was stirred at room temperature for 100 hours. The precipitate was collected and the solution was concentrated to dryness to yield S-K- (1,2,3,4-tetrahydro-1-naphthyl) glycine methyl ester quantitatively.

b) S-K-formyl-N- (1,2,3,4-tetrahydro-1-naphthyl) glycine methyl ester

35.0 g of S-N- (1,2,3,4-tetrahydro-1-naphthyl) glycine methyl ester are added dropwise to 72.3 ml of formic acid under cooling at 5 ° C. 26.4 ml of acetic anhydride are then added and the mixture is kept at room temperature for 70 hours. Distillation in vacuo afforded 20.4 g of S-N-formyl-R- [1,2,3,4-tetrahydro-1-naphthyl] glycine methyl ester, m.p. 86-87 ° C.

c) A solution of 4.77 g of sodium methylate in 100 ml of tetrahydrofuran is prepared by adding a suitable amount of methanol and sodium hydride to tetrahydrofuran. 14.4 g of formic acid methyl ester and S-N-formyl-N- (1,2,3,4-tetrahydro-1-naphthyl) glycine methyl ester obtained in process b) are added while cooling to room temperature. After 20 hours, 55 ml of deionized water and 110 ml of diethyl ether are added to the mixture. The aqueous phase was separated and 55 ml of methanol and 19.2 ml of 36% hydrochloric acid were added. The solution is heated to 40-50 ° C and a solution of 12.9 g of potassium thiocyanate in 25 ml of deionized water is added. The mixture was stirred at room temperature for 24 hours. 9.5 g of S-1- [1,2,3,4-tetrahydro-1-naphthyl] -2-mercapto-5-imidazolecarboxylic acid methyl ester precipitated during this time. After recrystallization from methanol, the product had a melting point of 141-142 ° C.

M = - ⁸⁷ ' ⁹ °'

Example 14: S-1- (1,2,3,4-Tetrahydro-1-naphthyl) -5-imidazolecarboxylic acid methyl ester (Compound 11.04)

Dissolve 0.5 g of sodium nitrite and 4.2 ml of nitric acid in 50 ml of deionized water. 6.4 g of S-1- [1,2,3,4-tetrahydro-1-naphthyl] -2-mercapto-5-imidazolecarboxylic acid methyl ester is added portionwise at 25-30 ° C. The precipitate is collected to give an acid addition salt of nitric acid rethylester S-1 / 1,2,3,

4-tetrahydro-1-naphthyl] -5-imidazolecarboxylic acid. To this salt was added a 10% aqueous sodium carbonate solution. Extraction of the aqueous phase with chloroform and evaporation of the organic solvent gave 2.1 g of S1,2,3,4-tetrahydro-1-naphthyl / -5-imidazolecarboxylic acid methyl ester as a colorless resin, which was purified by silica gel column chromatography. The pure resin product has a refractive index [α] ²⁰ ° + 23.6 °.

D

All other compounds listed in Table 1 can be obtained by analogous methods of preparation.

Claims (3)

A herbicidal composition comprising, as an active ingredient, a 5-imidazolecarboxylic acid derivative of the formula I R ² 00C-TV / v, or a stereochemically isomeric form thereof or a salt thereof wherein R ¹ is hydrogen or mercapto, R is hydrogen, alkyl of 1 to 7 carbon atoms, alkenyl of 3 to 7 carbon atoms or alkoxyalkyl of 1 to 4 atoms in the alkoxy moiety and 1 to 7 carbon atoms in the alkyl moiety, X is 1-indanyl, 1-tetrabydronaphthyl, 5-benzocycloheptyl, 4-tetrahydrobenzothienyl, or 9H-fluoren-9-yl, each of which may be unsubstituted or substituted by 1 to 6 substituents selected from the group consisting of 1 to 5 alkyl carbon atoms, benzyl, C 1 -C 5 alkoxy or halogen and two substituents, when attached to the same atom, may form together with the carbon atom to which they are attached a C 3 -C 7 cycloalkyl group. 2, wherein R and X are as defined above, optionally converted to a compound of formula Ib by reaction with sodium nitrite in the presence of nitric acid in water or by reaction with Raney nickel in the presence of a lower aliphatic alcohol, preferably ethanol, at a temperature in the range 40 to 80 ° C, or by reaction with an aqueous solution of hydrogen peroxide, preferably in the presence of a carboxylic acid, and optionally from a compound of formula I converted into a salt by reaction with an acid or base and the stereochemically isomeric forms are prepared, 2. A process for the preparation of an active ingredient of the formula I according to claim 1, characterized in that the compound of the formula II is condensed C JI ₂ HC - N - CN _O - COOR *, I * X wherein R and X are as defined above, with an alkyl formate of 1 to 4 carbon atoms in the presence of a base in an inert solvent and reaction of the resulting intermediate of formula III 0-Z OF O líc NC-C-COOR AND X (111), wherein R and X are as defined above and 2 is an alkali metal atom, and an alkali metal isothiocyanate in the presence of an acid to give a 2-mercaptoimidazole compound of formula Ia CS 276238 Βδ B ² OOC - - SB / i / l / l and A 5-imidazolecarboxylic acid derivative of the formula I of the formula I AND R OOC or a stereochemically isomeric form or salt thereof, wherein R ¹ is hydrogen or mercapto, o R is hydrogen, alkyl of 1 to 7 carbon atoms, alkenyl of 3 to 7 carbon atoms or alkoxyalkyl of 1 to 4 carbon atoms in the alkoxy moiety and 1 to 7 carbon atoms in the alkyl moiety, X is 1-indanyl, 1-tetrahydronaphthyl, 5-benzocyclobeptyl, 4-tetrahydrobenzothienyl or 9H-fluoren-9-yl, each of which is optionally substituted with 1 to 6 substituents selected from the group consisting of C 1 -C 5 alkyl, benzyl, C 1 -C 5 alkoxy and halogen, the two geminal substituents taken together, together with the carbon atom to which they are attached, optionally form a C 3 -C 7 cycloalkyl group.