DD252114A5 - HERBICIDE MEDIUM - Google Patents

Abstract

The invention relates to herbicidal compositions containing novel 2- (2-imidazolin-2-yl) -pyridine-3-carboxylic acid derivatives of the general formula (I) in which R 1, R 2, A, B, W, X, Y and Z are those described in have the meanings described in the description, in mixture with carriers and / or auxiliaries, formula (I)

Description

Field of application of the invention

The invention relates to novel agents containing imidazolinyl derivatives with herbicidal activity.

Characteristic of the known state of the art

It is already known that imidazolines have herbicidal properties (DE-OS 2,833,274 and DE-OS 3,121,736). Often, however, this herbicidal action is not sufficient, or occur with appropriate herbicidal selectivity problems in major agricultural crops.

Object of the invention

The aim of the present invention is to provide new means which do not have these disadvantages and are superior in their biological properties to the previously known agents.

Explanation of the essence of the invention

The invention has for its object to find new imidazolinyl derivatives, as the active ingredient in herbicidal agents with the

desired properties are suitable. ,

It has been found that compositions containing 2- (2-imidazolin-2-yl) -pyridine-3-carboxylic acid derivatives of general formula I.

in the

R 'is a Ci-C-alkyl radical,

R ^{2 is} a C ₁ -C ₆ -alkyl radical or a C ₃ -C ₆ -cycloalkyl radical or

R ¹ and R ² together with the adjacent carbon atom denote an optionally methyl-substituted C ₃ -C ₈ -cycloalkyl radical,

W is an oxygen or sulfur atom,

A is one of the groups CH ₂ OH, COOR ³ or CONR ⁴ R ⁵ ,

R ^{3 is} a hydrogen atom, an optionally interrupted by one or more oxygen or sulfur atoms and optionally by C ₁ -C ₃ -alkoxy, halogen, hydroxy, C ₃ -C ₆ -cycloalkyl, benzyl, furyl, tetrahydrofuryl, phenyl, halogenphenyl, C 1 -C ₄ -alkyl, C ₁ -C ₄ -alkoxyphenyl, nitrophenyl, cyano, carboxyl, C 1 -C ₄ -alkoxycarbonyl or C ₁ -C ₄ -alkylthio-substituted C ₁ -C ₁₂ -alkyl, optionally C ₁ -C ₃ -Alkoxy, phenyl or halogen substituted Cj-Qj alkenyl radical, an optionally substituted by C, -C ₃ alkoxy, phenyl or halogen substituted C ₃ -C ₈ -AlkInYlTeSt, an optionally substituted by methyl Cs-Cg cycloalkyl radical or a cation the group of alkali metals, alkaline earth metals, manganese, copper, iron, zinc, ammonium and organic ammonium compounds,

R ⁴ and R ⁵ independently of one another represent a hydrogen atom, a hydroxy group or a C 1 -C -alkyl radical and in the case where R ^{4 is} a hydrogen atom, R ⁵ also denotes an amino, dimethylamine, acetylamino or anilino radical,

X is a hydrogen atom, a nitro group, a C 1 -C ₃ -alkyl radical, a C ₁ -C -haloalkyl radical or a C 1 -C ₃ -alkoxy radical and one of the two radicals

Y or Z is one of the groups SR ⁶ or OR ⁷ and the other is a hydrogen atom, a halogen atom, a C, -C ₄ -AII <yl radical, a C ₁ -Ct-haloalkyl radical, a Cj-Cj-alkoxy radical or a C ₁ -C ₄ -AlkVItHiOrBSt,

R ^{6 represents} a hydrogen atom, a phenyl radical, a halophenyl radical, a C ₁ -C ₃ -alkylprienyl radical, a di-C ₁ -C -alkylphenyl radical, a nitrophenyl radical, a C ₁ -C 8 -alkoxyphenyl radical, a pyridyl radical, a C ₁ -C 8 -alkyl pyridyl radical, a C ₂ -C ₈ -alkyl radical interrupted once or several times by oxygen, an optionally interrupted by oxygen, sulfur, the imino or C ₁ -C ₄ -alkylimino group and optionally one or more times by C ₁ -C ₄ Alkyl, C ₁ -C ₄ -alkoxy or halogen-substituted C ₁ -C 8 -cycloalkyl radical, a C 5 -C 8 -cycloalkenyl radical or an optionally mono- or polysubstituted by cyano, halogen, hydroxyl, mercapto, amino, C ₁ -C ₆ -Alkoxy, C 1 -C ₄ -alkylthio, carboxyl, carbamoyl, C ₁ -C ₄ -alkoxycarbonyl, C ₁ -C ₄ -alkylthiocarbonyl, oxo, thioxo, di-C ₁ -C -alkoxy, hydroxyimino, C ₁ -C -cycloalkyl, C C ₃ -C ₈ cycloalkenyl, phenyl, halophenyl, C ₁ -C ₃ alkylphenyl, nitrophenyl, C ₁ -C ₃ alkoxyphenyl, furyl, tetrahydrofuryl, dioxolanyl, C ₁ -C 8 alkylamino, C s-Ce-cycloalkylamino, pyridyl, C ₁ -C ₄ -alkylpyridyl, pyrrolidinyl, piperidinyl, N, C ₁ -C -alkylpiperidinyl, C ₂ -C ₄ -alkylcyclopropyl, C ₁ -C ₄ -alkyldioxolanyl-substituted C 1 -C ₁₂ -alkyl- , C ₃ -C ₁₂ -alkenyl or C3-C ₁₂ alkynyl,

R ^{7 is} a hydrogen atom, an optionally interrupted by oxygen, sulfur, the imino or Ct-d-alkylimino group and optionally mono- or polysubstituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen substituted Cj-Cs Cycloalkyl radical, a Cj-Cs-cycloalkenyl radical or an optionally mono- or polysubstituted by cyano, hydroxy, mercapto, amino, hydroxy-d-Cü-alkyl, C ₁ -C ₆ -alkoxy, C ^ C ^ alkylthio, carboxyl, carbamoyl , Acetyl, C ₁ -C ₄ -alkoxycarbonyl, C ₁ -C -alkylthiocarbonyl, oxo, thioxo, di-C ₁ -C ₃ -bikoxy, hydroxyimino, C ₃ -C ₈ -cycloalkyl, dioxolanyl, Cs-Cg-cycloalkenyl, Furyl, tetrahydrofuryl, C ₁ -C ₆ -alkyl BmInO, C ₃ -C ₈ -cycloalkylamino, di-C ₁ -C ₆ -alkylamino, pyranyl, tetrahydropyranyl, pyridyl, C ₁ -C ₄ -alkylpyridyl, pyrrolidinyl, piperidinyl, NC ₁ - C ₄ -alkylpiperidinyl, C ₁ -C ₄ -alkylCyClOPrOPyI, di-C ₁ -C ₄ -alkyldioxolanyl-substituted C ₁ -C ₁₂ -alkyl, C ₃ -C ₁₂ -alkenyl or C ₃ -C ₁₂ -alkynyl radical,

B represents a hydrogen atom and, in the case where A = COOR ³ , but where R ³ does not denote a hydrogen atom, also the groups COR ⁸ or SO ² R ⁹ ,

R ^{8 is} a d-Ca-alkyl radical, a Cj-Ce-haloalkyl radical or an optionally mono- or polysubstituted by halogen, nitro, methyl or methoxy-substituted phenyl radical and

R ^{9 is} a C ₁ -C ₈ -alkyl radical, a trifluoromethyl radical, a trichloromethyl radical or a phenyl radical optionally substituted by halogen, nitro or C ₁ -C ₆ -alkyl

surprisingly, have greater effectiveness or improved selectivity.

The compounds of the general formula I to be used according to the invention can be prepared, for example, by reacting

A) if A = COOH and B = hydrogen, a compound of general formula II

(II)

in which R ', R ³ , W, X, Y and Z have the meanings given under the general formula I, cyclized under alkaline conditions,

B) if A = COOR ³ , R ³ but not a hydrogen atom, and B = hydrogen, a compound of general formula III

(Ill),

in which R ', R ² , R ³ , W, X, Y and Z have the meanings given under the general formula I, but R ³ does not represent a hydrogen atom, with a mixture of phosphorus oxychloride and phosphorus pentachloride, C) if A = COOR ³ , but R ³ is not a hydrogen atom, CONR ⁴ R ⁵ or CH ₂ OH and B = hydrogen, a. Imidazopyrrolopyridine of general formula IV

(Iv;

in which R ¹ , R ² , W, X, Y and Z have the meanings given under the general formula I, Cl) with an alcohol of the general formula R ³ -OH,

in which R ^{3 has} the meanings given under the general formula I, but does not stand for a hydrogen atom, and

corresponding alkali metal alkoxide, if appropriate in the presence of a solvent, or C2) with an amine of the general formula

HNR ⁴ R ⁵ ,.

in which R "and R ^{5 have} the meanings given under the general formula I, if appropriate using a solvent, or

C3) with a reducing agent such as sodium borohydride, D) if A = COOH, a compound of general formula V

in which B, R \ R ² , W, X and Y have the meaning given under the general formula I, with a compound of the general formula

ZH, wherein Z has the meaning given under the general formula I, or a compound of the general formula XI

(XI)

in which X, Z, B, R ', R ² and W have the meaning given in formula I, with a compound of the formula YH, where Y has the meaning given in formula I,

E) if R ^e or R ⁷ in the substituent Y or Z is not hydrogen, a compound of the general formula I in which A, B, R ¹ , R ² , W, X, Y and Z are those specified under the general formula I. But Y or Z represent an SH or OH group, alkylated,

F) if desired, a obtained according to the process variants A) and D) compound of the general formula I, in which R ³ in the substituent A is hydrogen, converted by reaction with one equivalent of a base as a salt-forming agent in a compound of general formula I, in the R ³ in the substituent A is a cation, or

G) if B = COR ⁸ or SO ₂ R ⁹ , a compound of the general formula I in which A is COOR ³ , obtained according to process variants B) or C), is reacted with an acyl halide, acyl anhydride or sulfonyl halide.

The process variant A) is suitably carried out so that the starting material of general formula II over a longer period, such as 0.5 to 20 hours, at a temperature in the range of 20 to 100 ⁰ C with an aqueous or aqueous-alcoholic alkali metal hydroxide solution, as sodium or potassium hydroxide solution, the amount of the. Hydroxide, based on the starting material of general formula II, 2 to 10 molar equivalents. Subsequently, the reaction mixture is cooled and acidified with a strong mineral acid such as sulfuric or hydrochloric acid. The amides of general formula II used as starting material can be prepared according to the following formula scheme from compounds of general formula VI, in which X, Y and Z have the meaning defined under general formula I, by topping into a carboxylic anhydride of general formula VII by conventional Methods and subsequent reaction with an amino acid amide of the general formula VIII, in which R 'and R ^{2 have} the meaning defined under the general formula I, obtained:

, - COOR 'COOR-

(VI)

(VII)

NH-C-CONH. (VIII).

JLc-NK-C-CONH ₀ (II) 0 R "

The preparation of compounds of general formula II is carried out in the presence of an organic solvent, such as diethyl ether, tetrahydrofuran, acetonitrile or ethyl acetate, or in a halogenated solvent, such as methylene chloride or chloroform. The reaction takes place in a temperature range of 20 ° to 100 ° C. In the reaction in small amounts resulting isomeric Pyridincarbonsäurederivate can be easily removed by Umkristaliisation or chromatography.

The starting compounds of the general formula VI are known in some cases or can be obtained by methods known per se, for example by reacting 6-chloropyridine-2,3-dicarboxylic acid derivatives of the general formula IX (X, Y =H, R ³ CHCH ₃ , J. Chem. Soc [B], 289-296 [1971]) or B-halopyridine ^ .S-dicarboxylic acid derivatives of the general formula X (X, Z = H, Hal = Cl, R ³ = CH _3; J. Med. Chem., 1067-1071 [1974]) according to the following formula scheme with compounds of the general formula YH or ZH, and X, Y, Z and R ^{3 have} the meaning defined under the general formula I:

COOR COOR

Hal Z

N-

.COOR "

(IX)

ZH

COOR-C00R ^J

(VI)

The reaction takes place between 0 ° and 150 ⁰ C, but generally between room temperature and the reflux temperature of the reaction mixture. The reaction time is 0.5 to 48 hours. YH or ZH are reacted between 1 and 5 moles, based on the starting material, if appropriate in the presence of a suitable base such as, for example, sodium hydride, sodium hydroxide, potassium hydroxide or potassium tert-butoxide. The reaction is carried out without or using suitable solvents, such as dimethyl sulfoxide, halogenated hydrocarbons such as methylene chloride or chloroform, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, acid amides such as dimethylformamide, or other solvents inert to the reactants such as diethyl ether or; Tetrahydrofuran.

Process variant B) is expediently carried out by reacting the starting material of general formula III directly with a mixture of phosphorus pentachloride and phosphorus oxychloride at room temperature.

The reaction may also be carried out in the presence of a solvent inert under the reaction conditions, such as toluene, xylene or chloroform, in a temperature range of 0 to 100 ^° C. The free bases are isolated from the resulting hydrochlorides by conventional methods, for example by reaction with sodium carbonate or sodium bicarbonate.

The starting material of general formula III is obtained from compounds of general formula II by esterification according to conventional methods with the corresponding alcohols of general formula R ³ -OH.

The process variant C1) is conveniently carried out by reacting the starting material of general formula IV with a mixture of alkali metal hydride, such as sodium hydride, and the corresponding alcohol of the formula R ³ -OH in excess 0.5 to 5 hours at a temperature in the range of Room temperature to the boiling point of the reaction mixture.

The alcohol used in this reaction serves both as a reactant and as a solvent. However, additional solvents such as tetrahydrofuran, dioxane or other non-protic solvents may also be used

become. '

Process variant C2) is expediently carried out by reacting the starting material of the general formula IV with a primary or secondary amine of the general formula

HNR ⁴ R ⁵ ,

wherein R ⁴ and R ^{5 have} the meanings given under the general formula I, in a temperature range from 20 to 100 ⁰ C optionally with the use of a solvent, such as dimethylformamide, tetrahydrofuran or dioxane, brings to reaction.

The process variant C 3) is advantageously carried out by reacting the starting material of the general formula IV with a reducing agent such as sodium borohydride in a temperature range from -10 to 30 ⁰ C in a suitable solvent or solvent mixture, such as ethanol / tetrahydrofuran Reaction brings. The starting material of the formula IV can be prepared from compounds of the general formula I, in which A = COOH and B = hydrogen, by reaction with dicyclohexylcarbodiimide.

The reaction takes place in an inert solvent, using an equimolar amount of the carbodiimide in a temperature range of from 20 to 6O ⁰ C..

The process variant D) is advantageously carried out by reacting the starting material of the general formula V in a solvent with a compound ZH, wherein Z has the meaning given in the general formula I, at temperatures between 0 and 170 ⁰ C, preferably between room temperature and the boiling temperature of the reaction mixture, reacted. The reaction is completed in 0.5 to 48 hours, depending on the reactants. The compounds of general formula ZH, which per se are an alcohol or a mercaptan, are used in an amount of from 1 to 5 molar equivalents, relative to the starting material of general formula V, optionally in the presence of a base, for example sodium hydride, sodium hydroxide, potassium hydroxide or potassium tert-butoxide, reacted.

The reaction is carried out without or using a suitable inert solvent. Suitable solvents include, for example, dimethylsulfoxide, halohydrocarbons such as methylene chloride and chloroform, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, as well as other solvents inert to the reactants such as diethyl ether, tetrahydrofuran or dimethylformamide. The starting materials of the general formula V are known in some cases or can be prepared by known literature methods.

Process variant E) is expediently carried out in such a way that the starting material is alkylated in a manner known per se, a compound of general formula I in which R ⁶ or R ^{7 is} hydrogen.

For this purpose, the corresponding 5-hydroxy or 5-mercapto or 6-hydroxy or 6-mercapto derivative is reacted in an appropriate solvent with an alkylating agent, preferably an alkyl halide, in the presence of a base at room temperature. Suitable solvents include dimethylsulfoxide, ethers, such as tetrahydrofuran and dioxane, acid amides, such as dimethylformamide and dimethylacetamide, and acetonitrile.

The reaction is preferably carried out at room temperature, but it is also possible to work at elevated temperature, whereby the reaction time is naturally shortened. Preferred halides are the chlorides, bromides and iodides. Suitable bases are alkali metal hydrides and hydroxides such as sodium hydride and potassium hydroxide. For the preparation of compounds of the general formula I according to process variant F), whose radical R ³ in the substituent A is a cation, the starting material used is a compound of the general formula I in which R ^{3 is} hydrogen. This is conveniently reacted in a suitable solvent with a base as a salt former, such as alkali metal or alkaline earth metal hydroxide, ammonium hydroxide or an alkylamine, such as isopropylamine, at room temperature.

According to process variant G), the corresponding compounds of general formula I synthesized according to process variants B) and C) are reacted with an excess amount of an acyl halide of general formula R ⁸ -CO-CI, acylanhydride of general formula R ⁸ -CO-O-CO- R ⁸ or sulfonyl halides of the general formula CI-SO ₂ -R ⁹ , where R ⁸ and R ^{9 have} the meaning given under the general formula I, optionally in the presence of a solvent such as pyridine or toluene, at a temperature between 50 and 130 "C. implemented.

The compounds prepared by the abovementioned process variants can be isolated from the reaction mixture by conventional methods, for example by adding the reaction mixture to ice-water and separating off the product by extraction with a suitable solvent or by filtration.

The compounds to be used according to the invention are generally crystalline or viscous substances, some of which are readily soluble in halogenated hydrocarbons, such as chloroform, sulfoxides, such as dimethyl sulfoxide, or esters, such as ethyl acetate,

The present inventive compositions have excellent herbicidal activity against economically important mono- and dicotyledonous weeds. Even difficult to control perennial weeds are well detected by the active ingredients.

It does not matter whether the substances are applied in ante-chamber, pre-emergence or post-emergence spraying. If the agents according to the invention are applied to the earth's surface prior to germination, the emergence of the seedlings is not completely prevented. The weeds grow to the cotyledon stage but then stop growing and eventually die

The agents according to the invention can be used, for example, against the following plant genera:

Dicotyledonous weeds of the genera Abutilon, Chrysanthemum, Brassica, Helianthus, Mentha, Sinapis, Lepidium, Galium, Stellaria, Anthemis, Chenopodium, Atriplex, Senecio, Portulaca, Ipomoea, Matricaria, Galinsoga, Urtica, Amaranthus, Convolvulus, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Lamium, Veronica, Datura, Viola, Centaurea and Galeopsis.

Monocotyledonous weeds of the genera Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Agropyrone, Sagittaria, Cynodon, Monochoria, Fimbristylis, Eleocharis, Ischaemum and Apera.

The agents can be used in major agricultural crops such as cotton, soy, rice, corn, wheat, barley, oats, sorghum and sugar cane.

The use of the agents according to the invention is by no means limited to the aforementioned weed genera and crop plants, but extends in the same way to other plants.

Depending on the concentration, the agents are also suitable for total weed control, for example on industrial and track systems and on paths and squares. Similarly, weed control products may be used in permanent crops such as forest, ornamental, fruit, wine, citrus, nut, banana, coffee, tea, gum, oil palm, cocoa, berry and hop plants, are used.

In addition, the agents have growth regulatory properties in crops at appropriately low levels of application by regulatory action in the plant's metabolism without killing the plants so that they can be used, for example, for general control and inhibition of undesirable vegetative growth.

The amount of active ingredient used can vary within a substantial range. It depends essentially on the type of effect desired. In general, the application rates are between 0.01 and 5 kg of active ingredient per hectare of soil surface, preferably, for example, in weed control between 0.1 and 0.5 kg of active ingredient per hectare.

The compositions according to the invention can be used either alone, in admixture with one another or with other active ingredients.

If necessary, other crop protection or pest control agents may be added according to the desired purpose.

If a widening of the spectrum of action is intended, other herbicides can be added.

For example, the herbicidally active mixture partners are those active substances which are described in Weed Abstracts, Vol. 3, 1985, entitled "List of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts".

A promotion of the effective intensity and the rate of action can be achieved, for example, by means of action-enhancing additives, such as organic solvents, wetting agents and oils. Such additives may therefore allow a reduction in the dosage of active ingredient.

In addition, phospholipids, for example those from the group phosphatidylcholine, the hydrogenated phosphatidylcholines, phosphatidylethanolamine, the N-acyl-phosphatidylethanoiamines, phosphatidylinositol, phosphatidylserine, lysolecithin and phosphatidylglycerol can be used as the mixing partner.

Appropriately, the marked active substances or mixtures thereof in the form of preparations such as powders, scattering agents, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and optionally adhesive, wetting, emulsifying and / or Dispersing aids applied.

Suitable liquid carriers are, for example, aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide, furthermore mineral oil fractions and vegetable oils.

Suitable solid carriers are minerals, for example bentonite, silica gel, talc, kaolin, attapulgite, limestone, and vegetable products, for example flours.

Surfactants include, for example, calcium lignosulfonate, polyethylene alkylphenyl ethers, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates and substituted benzenesulfonic acid and its salts.

The proportion of the active ingredient (s) in the various preparations can vary within wide limits.

For example, the agents contain about 10 to 90% by weight of active compound, about 90 to 10% by weight of liquid or solid carriers and optionally up to 20% by weight of surface-active substances.

The application of the agents can be carried out in the usual manner, for example with water as a carrier in Spritzbrühemengen of about 1 000 liters / ha. An application of the funds in the so-called low-volume and ultra-low-volume method is just as possible as their application in the form of so-called microgranules.

The preparation of these preparations can be carried out in a manner known per se, for example by milling or mixing processes. If desired, preparations of the individual components can also be mixed shortly before use, as is carried out, for example, in the so-called tank mix process in practice.

For the preparation of the various preparations, for example, the following constituents are used:

A) Spray powder

1. 80% by weight of active ingredient 15% by weight of kaolin

5 wt .-% surfactants based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of lignosulfonic acid

2. 20% by weight of active compound 35% by weight of bentonite

8 wt .-% calcium salt of lignosulfonic acid

2 wt .-% sodium salt of N-methyl-N-oleyl-taurine 35 wt .-% silica

B) paste

"45% by weight of active ingredient.

5% by weight of sodium aluminum silicate 15% by weight of cetyl polyglycol ether with 8 mol of ethylene oxide

2% by weight spindle oil 10% by weight polyethylene glycol 23% by weight water

C) emulsion concentrate 20% by weight of active ingredient

50% by weight of cyclohexanone 25% by weight of aromatic hydrocarbons 5% by weight of combination emulsifier of calcium dodecylbenzenesulfonate and nonylphenol polyglycol ether

embodiment

The invention is explained in more detail below with reference to some examples.

The following examples illustrate the preparation of the compounds to be used according to the invention:

Example 1 (Method A). , '.

6-benzylthio-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid

7.5 g (0.028 mmol) of 6-benzylthiopyridine-2,3-dicarboxylic anhydride are slurried with 30 ml of acetonitrile and combined with stirring with a solution of 3.6 g (0.028 mol) of 2-methyl-valinamide in 20 ml of acetonitrile. After 15 minutes, the mixture is concentrated and the resulting e-benzylthio - ^ - tN-i-carbamoyl-i ^ -dimethylpropyl-carbamoylJ-nicotinic acid with 50 ml of 2.6 N sodium hydroxide and heated with stirring to 100 ⁰ C for 6 hours. At room temperature, acidified with concentrated hydrochloric acid, extracted with methylene chloride, dried over magnesium sulfate and concentrated.

Yield: 3.6 g (33.5% of theory)

Fp .:. 190 ⁰ C

The starting material was prepared as follows:

6-benzylthiopyridin-2,3-dicarboxylate

3.7 g (0.03 mol) of benzylmercaptan are added to a mixture of 8.3 g (0.06 mol) of potassium carbonate in 20 ml of dimethylformamide and stirred for 10 minutes. Subsequently, 6.9 g (0.03 mol) of 6-chloropyridine-2,3-dicarboxylic acid dimethyl ester are added and the reaction mixture is stirred at 100 ° C. for 6 hours. After cooling to room temperature, the reaction mixture is poured into ice-water, the product extracted with methylene chloride, the organic phase washed with dilute hydrochloric acid and water, dried over magnesium sulfate and concentrated by rotary evaporation. From the oily residue, the product crystallizes out.

Yield: 7.3 g (76.8% of theory)

Mp .: 80-84 ⁰ C

6-benzylthiopyridin-2,3-dicarboxylic acid

15.0 g (0.375 mol) of sodium hydroxide are dissolved in 40 ml of water and added to a stirred mixture of 7.3 g (0.023 mol) of dimethyl 6-benzylthiopyridine-2,3-dicarboxylate in 40 ml of ether. It is stirred for 4 hours at 40 ⁰ C, acidified the aqueous phase with concentrated hydrochloric acid and the product extracted with ethyl acetate, the solvent dried over magnesium sulfate and concentrated. From the residue, the product crystallizes out.

Yield: 6.36 g (95.6% of theory)

Mp .: 175 ° C

6-benzylthio-pyridine-2,3-dicarboxylic anhydride

8.5 g (0.029 mol) of 6-8enzylthiopyridin-2,3-dicarboxylic acid are stirred in 150 ml of acetic anhydride for 6 hours at 110 ⁰ C, the substance dissolves completely. The solvent is distilled off in vacuo and the residue used without further purification in the next stage.

Yield: 7.5 g (78.6% of theory)

Example 2 (Method F)

6-Benzylthio-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl-nicotinic acid, isopropylammonium salt To a solution of 1.0 g (2.7 mmol) of 6-benzylthio-2- (4-isopropyl-4-methyl-5-oxo-2-imidazoiin-2-yl) nicotinic acid in 50 ml of ether and 50 ml of tetrahydrofuran are added 0.16 g (2.7 mmol) of isopropylamine, the precipitate is filtered off with suction and dried Yield: 0.93 g (80.75% of theory) mp: 174-175 ° C

Example 3 (Method B) -.

5-Hydroxy-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -6-methyl-nicotinic acid methyl ester A solution of 47 g (0.129 mol) of 5-acetoxy-2- (1 -carbamoyl-1,2-dimethylpropyl-carbamoyl) -6-methyl-nicotinic acid methyl ester and 93.8 g of phosphorus pentachloride in 470 ml of phosphorus oxychloride is stirred for 12 hours at room temperature. It is then hydrolyzed with ice and the solution is neutralized with sodium carbonate. The product is extracted with ethyl acetate, the extracts dried over magnesium sulfate and concentrated. The crude product is recrystallized from ethyl acetate / isopropyl ester. Yield: 22 g (55.9% of theory) M.p .: 206 ^° C.

The starting material was prepared as follows:

B-acetoxy-e-methyl-pyridine ^ .S-dicarboxylic acid anhydride

A suspension of 1.0 g (5.1 mmol) of B-hydroxy-e-methylpyridine ^. S-dicarboxylic acid and 5 ml of acetic anhydride are heated at a bath temperature of 140 ⁰ C until a clear solution is formed. After concentration, the desired product is obtained.

Yield: 1.1 g (97.5% of theory)

Mp .: 123-125 "C. '·

5-Acetoxy-2- (1-carbamoyl-1,2-dimethylpropyl-carbamoyl) -6-methyl-nicotinic acid 6.3 g (28.48 mmol) of S-acetoxy-6-methyl-pyridine-1-dicarboxylic anhydride and 4 , 1 g (31.33 mmol) of 2-methyl-valinamide are stirred under nitrogen for 2 days at room temperature and then the precipitated crystalline product is filtered off.

Yield: 9.5 g (95% of theory)

Mp .: from 143 ⁰ C

Methyl 5-acetoxy-2- (1-carbamoyl-1,2-dimethyl-propyl-carbamoyl) -6-methyl-nicotinate. A refluxing solution of 53 g (0.151 mol).

5-Acetoxy-2- (1-carbamoyl-1,2-dimethylpropyl-carbarnoyl) -6-methylnicotinic acid in 500 ml of absolute methanol is passed for 3 hours hydrochloric acid gas. The solvent is then evaporated off and the product is dried in vacuo.

Yield: 47.1 g (85.5% of theory)

Mp .: 145 ° C

Example 4 (Method C) G-Benzylthio-1-isopropyl-methyl-S-oxo -imidazoline-1-yl-nicotinic acid methyl ester 4.0 g (0.011 mol) of 2-isopropyl-2-methyl-5H-imidazo [1 ', 2': 1,2] -pyrrolo [3,4-b] -2-benzylthiopyridin-3 (2H) -5-dione is added to a mixture of 0.2 g of sodium hydride in 40 ml of methanol and 2 hours under Heated reflux. After cooling, the mixture is poured into ice-water and the product is extracted with chloroform.

Yield: 2.7 g (61.8% of theory)

Mp .: 157-158 "C.

The starting material was prepared as follows:

2-Isopropyl-2-methyl-5H-imidazo [1 ', 2': 1,2] -pyrrolo [3,4-b] -2-benzylthiopyridine-3 (2H) -5-dione 1.0g (0.005 mol) dicyclohexylcarbodiimide and 2.0 g (0.005 mol)

6-Benzylthio-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -nicotinic acid are dissolved in 30 ml of methylene chloride, stirred for 4 hours at room temperature and allowed to stand overnight. The reaction mixture is filtered and the filtrate is then concentrated. The oily residue crystallizes after some time.

Yield: 1.7 g (93.4% of theory)

Mp: 155-157 ⁰ C

Example 5 (Method D) -

2- (4-Isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -6-tetrahydrofurfuryloxy-nicotinic acid. 1.0 ml (0.01 mol) of tetrahydrofurfuryl alcohol are added to a mixture of 1.0 g ( 0.033 mol) of sodium hydride (80%) in 10 ml of dimethylformamide and stirred for 1 hour. Subsequently, 2.95 g (0.01 mol) of 6-chloro-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid, dissolved in 10 ml of dimethylformamide, added dropwise. The mixture is stirred at 50 to 6O ⁰ C for 1 hour, cooled to room temperature, is added 10 ml of water and acidified with concentrated hydrochloric acid. The product is extracted with methylene chloride, the extract dried over magnesium sulfate, filtered and concentrated. From the resulting oil crystallized after some time, the product

Yield: ί, 8 g (50% of theory) M.p .: 155-160 ⁰ C.

Example 6 (Method E) 2- (4-Isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -6-methyl-5-methylthiomethoxy-nicotinic acid methyl ester A solution of 2.5 g (8.19 mmol) S-Hydroxy ^ - ^ - isopropyl ^ -methyl-S-oxo ^ -imidazolin ^ -ylje-methyl-nicotinic acid methyl ester in 25 ml of dimethyl sulfoxide is treated with 0.26 g (8.19 mmol) of sodium hydride (80%) and after stirring for 10 minutes, 0.87 g (9.01 mmol) of chlorodimethylsulfide are added. It is stirred overnight, then added to 500 ml of ice water, the product extracted with ethyl acetate, the extracts dried over magnesium sulfate and concentrated. The residue is chromatographed over silica gel with ethyl acetate / hexane 1: 1

Yield: 0.53 g (17.7% of theory) M.p .: 96-98 ⁰ C.

Analogously, the compounds of the formula I listed by formula in the following table were prepared according to the process variants described:

table

H

example

No . YZ

Fp. Procedural

v arianta '

[ ⁰ CI

COOH 105-103

H

COOH χ NH - (

COOH oil 1 55

0 H

COOH χ NH 91-95

1 H

- CH - '

COOH 208

2 H

O - C H -

S- (CH ₃ )

COOH

COOH χ HO 1 64 1 50

COOC ₂ H ₅ 125-121

8eis piel

No . YZ

Fp. Procedural

C Cl variant

5 H

S-CH "-Ph

COO-_i-CH

175-177

16 H

S-CH ₂ -Ph 100

17 H

S-CH ₂ -Ph

, α

138

18 H

S-CH-Ph

Cl

19 H S-CH- (O) - ^{01 C00H}

COO-1 40 171

2 0 - H

COOH 1 SO

2 1 H

S-CH-CH = CHCOOH 155-1

22 H

COOH 170-180

2 3 H

S-

COOH 125-129

2'-, H

COOH 136

25 H

COOH 1 22

26 H

S- (CH) - <

COOH 1 20

27 H

COOH 1 15

28 h

COOH 1 20

29 H

COOH 1 53

30 H S- (CH) -OH COOH 1 80

3 1 H

O-CH

COOH 170

example

No . YZ Fp. Process CC] variant

32 H

O-CH -

COOH 130

3 3 m

O-CH

:-O

COOH 142

34 H

O-CH -

COOH 1 30

35 H

SH

COOH 175 / Zers.

36 H

CONH. 198-204

37 H

S-CH, -

CONHNH. > 250

38 H

COOH 1 30-1 40

39 H

COOH 95

40 H

-c " ₂ - <I

COOH 140

41 CH O-CH-S-CHCOOH 146-150

42 H

COOH 196

43 H

O-CH -

COOH χ HN - \

1 57 / Zers.

44 H

O-CH -

COOH χ 1 69 / dec.

45 H

S-

COOH χ Η 1 58 / Zers.

4 6 H

S-

COOH χ Η N

16 7 / Zers.

47 H 43 H

O-CH -

-O

COOH χ H N

COOH χ HN - ^ 1 46 / dec.

151 / Zers.

-13- IOl Π 4

example

No. YZ Fp. Procedure va riante

C ⁰ Cl

49 H 50 H

S-CH

COOH χ H ₂ N- (

COOH χ

158 / dec. F .1 4 WZers. F

5 1 H ⁵²

53 S-CH ₂ -ko ^ H

COOH

COOH

COOH

COOH

208 / dec. D 1 12

130 1 4 1

55 O-CH 5 S 0 - C H 5?

53 H 59 H

.-Σ

COOH

COOH

COOH

COOH

COOH

1 53 1 1 0 154 139-191 188-192

6 (3 H

COOH χ H

157 / dec. F

S 1 H 62 H 63 H 64 H 65 H

O-

Ο

ι

ο-Q

o-O

6 6 0- / 0 H

COOH

COOH

COOH

COOH χ ^H ₂ ^N - \

COOH χ Η N- (

COOH

1 45 140-143 135 1 82 / Zer3. F 157 / Zers. F 150-156

Example 7 (Method D) B-iCyclopropylmethoxy J ^ - ^ - isopropyl-methyl-B-oxo -imidazoline-1-yl-nicotinic acid, hydrate 1.0 g (0.033 mol) of 80% sodium hydride is dissolved in 15 ml of dimethylformamide and with 1.0 g (0.015 mol) of cyclopropylmethyl alcohol. With stirring, 3.4 g (0.01 mol) of 5-bromo-1- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid are added and 2 hours at 100 ⁰ C. Bath temperature stirred. After cooling, the reaction mixture is poured onto ice, acidified with concentrated hydrochloric acid and extracted with ethyl acetate. The organic phase is dried over magnesium sulfate and

concentrated. The oily residue crystallizes from isopropyl ether. ^l

Yield: 1.7 g (48.6% of theory)

Mp .: 105-110 ⁰ C

RF: 0.0

The following examples serve to illustrate the possible uses of the compounds according to the invention, which were carried out in the form of the abovementioned preparations:

Example A

In the greenhouse, the compounds according to the invention were emulsified in an application rate of 3 kg of active ingredient / ha in 100 l of water / ha on Brassica spp. and Solanum spp. sprayed as test plants in the pre- and post-emergence process. 3 weeks after the treatment, the treatment result was scored using the following scheme:

0 = no effect

1 = little effect or weak inhibition of plant growth

2 = mean effect or inhibition of plant growth

3 = total growth inhibition

4 = total destruction of the plants.

It was found that the compounds of Examples 1, 2, 5-8, 11-13, 19-26, 33-59 and 66 caused 100% annihilation (= 4) of the plants in this test.

Example B

In the greenhouse, the listed plants were treated before emergence with the compound to be tested in an application rate of 1 kg of active ingredient / ha. The compound was sprayed for this purpose as a suspension with 500 l of water / ha evenly over the ground. 3 weeks after the treatment, the compounds according to the invention showed a selectivity in maize with excellent action against the weed. The comparison agent was significantly less effective. In the following table mean:

0 = no effect

1 = low activity or weak inhibition of plant growth .2 = medium activity or inhibition of plant growth

3 = total growth inhibition

4 = total destruction of the plants Ze = Zea mays

Br = Brassica sp.

So = Solanum sp.

Me = Medicago sp.

He = Helianthus sp.

St = Stellaria sp.

Ab = Abutilon sp.

Ma = Matricaria sp.

Vi = Viola sp.

Ch = Chrysanthemum sp.

Sr = Sorghum sp.

Av = Avena sp.

Al = Alopecurus sp.

Ec = Echinochloa sp.

Se = Setaria sp.

Cy = Cyperus sp.

invention

Connections Ze Br So Me He St From Ma Vi Ch Sr Av Al Ec Se Cv

Example 5 0333334433444444

Example 12 0333333433 3 3 3

Comparative agent (according to DE-OS 3 121 736)

6-butylthio-2- 0220102421011102

(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid

Example C

In the greenhouse, the listed plants were treated prior to emergence with the compounds listed in a Äufwandmenge of 1 kg / ha. The compounds were sprayed for this purpose as a suspension with 500 liters of water / ha evenly over the ground. 3 weeks after treatment, the compounds of the invention showed a selectivity in soy (Glycine max.) With excellent activity against the chew.

In the following table mean:

0 = no effect -

1 = little effect or weak inhibition of plant growth

2 = mean effect or inhibition of plant growth

3 = total growth inhibition,

4 = total destruction of the plants Gl = Glycine max.

Br = Brassica sp.

So = Solanum sp.

Me = Medicago sp.

He = Helianthus sp.

St = Stellaria sp.

Ma = Matricaria sp.

Ch = Chrysanthemum sp.

Se = Setaria sp.

invention

Compounds Gl Br So Me He St Ma Ch Se

Example 58 044444444.

Example 59 044444444

Claims (1)

A herbicidal composition, characterized by a content of at least one 2- (2-imidazolin-2-yl) -pyridine-3-carboxylic acid derivative of general formula I. Y - -Τ Ν- Α Z- in the R ^{1 is} a C ₁ -C ₄ -alkyl, R ^{2 is} a C, -C ₆ alkyl radical or a C ₃ -C _e -cycloalkyl radical or R ¹ and R ² together with the adjacent carbon atom optionally substituted by methyl C ₃ -Ce-cycloalkyl, W is an oxygen or sulfur atom, A is one of the groups CH ₂ OH, COOR ³ or CONR ⁴ R ⁵ , R ^{3 is} a Wasserstoffatbm, optionally interrupted by one or more oxygen or sulfur atoms and optionally by C ₁ -C ₃ -alkoxy, halogen, hydroxy, C ₃ -C ₆ -cycloalkyl, benzyl, furyl, tetrahydrofuryl, phenyl, Halgenphenyl, C C 1 -C ₄ -alkylphenyl, C 1 -C ₄ -alkoxyphenyl, nitrophenyl, cyano, carboxyl, C 1 -C ₄ -alkoxycarbonyl or C ₁ -C -alkylthio-substituted C ₁ -C ₁₂ -alkyl radical, optionally substituted by C ₁ -C ₃ AIkOXy, phenyl or halogen-substituted C ₃ -Ce-alkenyl radical, an optionally substituted by C ₁ -C ₃ -alkoxy, phenyl or halogen-substituted Gj-Ce-alkynyl, an optionally substituted by methyl C ₃ -C ₆ -cycloalkyl or a cation from the group of alkali metals, alkaline earth metals, manganese, copper, iron, zinc, ammonium and organic ammonium compounds, R ⁴ and R ^{5 are} independently of one another a hydrogen atom, a hydroxy group or a C ₁ -C ₄ -alkyl radical and, in the case where R ^{4 is} a hydrogen atom, R ^{5 is} also an amino, dimethylamino, acetylamino or anilino radical, X is a hydrogen atom, a nitro group, a C, -C ₃ alkyl, C ₁ -C ₃ haloalkyl group or a C ₁ -C ₃ -AIkOXyTeSt and one of the two radicals Y orZ one of the groups SR ⁶ or OR ⁷ and the other is a hydrogen atom, a halogen atom, a C ₁ -C ₄ -AIkYlTeSt, a C ₁ -C ₄ haloalkyl group, a C ₁ -C ₄ -AIkOXyTeSt or a C, C ₄ alkylthio radical, R ^{6 represents} a hydrogen atom, a phenyl radical, a halophenyl radical, a C ₁ -C ₃ -alkylphenyl radical, a di-CT-03-alkylphenyl radical, a nitrophenyl radical, a C ₁ -C ₃ -alkoxyphenyl radical, a pyridyl radical, a CT-Q 1 -alkyl -pyridyl radical, a C ₁ -C 5 -alkyl radical which is mono- or polysubstituted by oxygen, an optionally interrupted by oxygen, sulfur, the imino or C ₁ -C ₄ -alkyl radical and optionally mono- or polysubstituted by C ₁ -C ₄ -alkyl , C ₁ -C ₄ -alkoxy or halogen-substituted C ₁ -C 8 -cycloalkyl radical, a C 5 -C -cycloalkenyl radical or an optionally mono- or polysubstituted by cyano, halogen, hydroxyl, mercapto, amino, C ₁ -C ₆ -alkoxy, -C ^ alkylthio, carboxyl, carbamoyl, C ₁ -C 4 alkoxycarbonyl, C ₁ -C 4 alkylthiocarbonyl, oxo, thioxo, C ₁ -C ₃ ^ -OXOX, hydroxyimino, C ₃ -C ₈ -cycloalkyl, GjCa-cycloalkenyl , Phenyl, halophenyl, C ₁ -C 4 -alkylphenyl, nitrophenyl, C ₁ -C 4 -alkoxyphenyl, furyl, tetrahydrofuryl, dioxolanyl, C ₁ -C ₆ -alkylamino, C ₃ -C ₈ -cycloal kylamino, pyridyl, C 1-6 -alkylphyridyl, pyrrolidinyl, piperidinyl, N - ^ - C 1-4 -alkylpiperidinyl, C 1-6 -alkylcyclopropyl, C 1 -C 12 -alkyl-dioxolanyl-substituted C 1 -C ₂ -alkyl-, C 1 -C 4 -alkyl Alkenyl or C ₃ -C ₁₂ alkynyl, R ^{7 is} a hydrogen atom, an optionally interrupted by oxygen, sulfur, the imino or C ₁ -C ₄ -AlkYMmInOgTUPPe interrupted and optionally mono- or polysubstituted by C ₁ -C ₄ -AlkYl, C ₁ -C ₄ -alkoxy or halogen substituted C C ₃ -C ₈ -cycloalkyl-C ₁ -C ₅ -cycloalkenyl radical or an optionally mono- or polysubstituted by cyano, hydroxyl, mercapto, amino, hydroxy-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -cyclothio , Carboxyl, carbamoyl, acetyl, C ₁ -C ₄ -alkoxyCaTbOnYl, C ₁ -C ₄ -alkylthiocarbonyl, oxo, thioxo, di-C ₁ -C ₃ -bikoxy, hydroxyimino, C ₃ -C ₈ -cycloalkyl, dioxolanyl, Cs -Cg -cycloalkenyl, furyl, tetrahydrofuryl, C, -C ₆ -alkylamino, C 1 -C 5 -cycloalkylamino, C 1 -C 4 -alkylamino, pyranyl, tetrahydropyranyl, pyridyl, C 1 -C 4 -alkylpyridyl, pyrrolidinyl, piperidinyl, N-C 1 -C 4 -alkylpiperidinyl, C 1 -C 4 -alkylcyclopropyl, C 1 -C 4 -alkyl, C ₄ -alkyldioxolanyl substituted C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkenyl or C ₃ -C ₁₂ alkynyl, B. a hydrogen atom and in the case that A = COOR ³ , but wherein R ^{3 is} not a hydrogen atom means also the groups COR ⁸ or SO ² R ⁹ ,
R ^{8 is} a C ₁ -C ₈ -AlkYlTeSt, a C ₁ -C ₆ halo! K'ylrest or optionally one or more times phenyl, which is substituted by halogen, nitro, methyl or methoxy, and R ^{9 is} a C ₁ -C ₆ -alkyl radical, a trifluoromethyl radical, a trichloromethyl radical or an optionally by halogen, nitro or C ₁ -C ₆ -Alkyl substituted phenyl, in.Mischung with carriers and / or excipients.