DD296598A5 - SUBSTITUTED ALPHA-PYRIMIDINYLOXY (THIO) AND ALPHA-TRIAZINYLOXY (THIO) CARBONSAEUREDERIVATE-CONTAINING AGENTS WITH HERBICIDER, FUNGICIDER AND PLANT GROWTH-REGULATORY EFFECT - Google Patents

Abstract

The invention relates to compositions with herbicidal, fungicidal and plant growth-regulating action containing novel substituted a-pyrimidinyloxy (thio) - and a-triazinyloxy (thio) carboxylic acid derivatives of the general formula I in which A, R1, R2, R3, X and Y in the Described meanings, as well as their alkali metal salts, alkaline earth metal salts and organic ammonium salts and their optical isomers in admixture with Traeger- and / or adjuvants. The compositions according to the invention avoid the disadvantages of the prior art and are superior in their biological properties to the previously known compounds. Formula (I) {means; herbicidal, fungicidal, plant growth regulating action; new, substituted, a-pyrimidinyloxy (thio) and a-triazinyloxy (thio) carboxylic acid derivatives; carrier materials}

Description

Field of application of the invention

The invention relates to novel substituted a-pyrimidinyloxy (thio) and a-triazinyloxy (thio) carboxylic acid derivatives containing agents having herbicidal, fungicidal and plant growth-regulating action.

Characteristic of the known state of the art

It is already known that pyrimidine and triazine derivatives have a herbicidal action (EP applications 0223406, 0249707, 0249708, 0287072, 0287079 and 0347811). Often, however, the herbicidal action of the known agents is not sufficient, or it comes with appropriate herbicidal selectivity problems in main agricultural crops.

Object of the invention

The invention eliminates these disadvantages.

Explanation of the essence of the invention

The object of the present invention is the provision of new agents which are superior in their biological properties to previously known compounds.

It has now been found that compositions containing substituted a-pyrimidinyloxy (thio) - and a-triazinyloxy (thio) carboxylic acid derivatives of the general formula I.

COOR

in the

A is one of the groups A-1 to A-6 of the general formulas

f --Ч

A - 2

A - 3

4 Jr.

A -

A - 5

A - 6

a C ₁ -C ₄ -alkoxy or halogen-substituted C ₁ -C ₆ -AIkVlTeSt, an unbranched C ₂ -C ₆ -alkyl keny I radical, a cyclopropyl radical, substituted by C ₁ -C ₄ -alkoxy or halogen Сз- Ce-cycloalkyl radical or a benzyl radical substituted on the aliphatic carbon atom by hydrogen or methyl and C 1 -C ₄ -alkoxy or halogen,

D represents an oxygen atom, a sulfur atom or a group-NR ⁹ -, R ¹ is a hydrogen atom, a C ₁ -C ₄ -AIkYlrest or a benzyl radical, R ^{2 is} a C ^ Q-alkyl group, a C -C ₄ alkoxy radical, a! Ci-C ^ alkylthio, a Ci-Q-alkylamino, a

Di - ^ - C ^ alkylamino or a halogen atom, R ^{3 is} a C ^ C ^ alkyl, a Ci-C ^ alkoxy, a Ci-Q-alkylthio, a C ₁ -C ₄ alkylamino, a di-C ^ CA-alkylamino radical or a halogen atom, with the proviso that the radicals R ² and R ^{3 are} not both methyl and not

represent a methyl and the other is tert-butyl, when A is unsubstituted phenyl, X is sulfur and Y is a methine group, R ⁴ einWassestoffatom, a C, -C ₄ alkyl, C ₁ -C ₄ -alkoxy ^ St, an amino radical, a di - ^ - C ^ alkylamino radical, a

Nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical, R ^{5 is} a hydrogen atom, a C 1 -C 4 alkyl radical, a C 1 -C 4 alkoxy radical, an amino radical, a di-C 1 -C 4 alkylamino radical, a

Nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical, R ^{6 is} a hydrogen atom, a Ci-Gi-alkyl radical, a C ₁ -C ₄ alkoxy, an amino radical, a di - ^ - C ^ alkylamino radical, a

Nitrorest, a halogen atom, a trifluoromethyl radical or a phenyl radical, R ^{7 is} a hydrogen atom, a Ci-Q-alkyl radical, a Ci-C ₄ alkoxy, an amino radical, a di - ^ - C ^ alkylamino radical, a

Nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical, R ^{8 is} a hydrogen atom, a C 1 -C 4 alkyl radical, a C 1 -C 4 alkoxy radical, an amino radical, a C 1 -C 4 -alkylamino radical, a

Nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical, R ^{9 is} a hydrogen atom or a C ₁ -C ₄ -alkyl radical,

X is an oxygen atom or a sulfur atom, with the proviso that X is not oxygen when A is allyl, and Y is a methine group or a nitrogen atom, with the proviso that Y is not a methine group, when A is 1-chloroethyl or 1-methyl- 2,2,2-trifluoroethyl,

and their alkali metal salts, alkaline earth metal salts and organic ammonium salts and their optical isomers show an interesting herbicidal, fungicidal and plant growth-regulating action.

The term halogen includes fluorine, chlorine, bromine and iodine. The term alkali metal lithium, sodium and potassium, to understand the term alkaline earth metal calcium, strontium and barium.

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

.10

in which R ² , R ³ and Y have the meanings given under the general formula I and R ^{10 represents} a halogen atom, an alkylsulfonyl group or a phenylsulfonyl group, with compounds of general formula III

HX COOR ¹

wherein A, ^R: and X have the meanings given under general formula I, in a suitable solvent in the presence of a suitable base, or B) compounds of the general formula IV

R ²

COOR

¹ (IV),

in which A, R ¹ , R ² , R ³ , X and Y have the meanings given under the general formula I, in a suitable polar solvent with an alkali metal base or an alkaline earth metal base to give compounds of the general formula V

У-х "\ оон '<«

^ ^N

in which A, R ² , R ³ , X and Y have the meanings given under general formula I and M ^{1 represents} an alkali metal atom or one equivalent of an alkaline earth metal atom, or C) compounds of general formula V

R ²

X COOM ¹ (V).

in which A, R ² , R ³ , M ¹ , X and X have the meanings given under the general formula V, with a suitable acid in a suitable solvent to give compounds of the general formula VI

N ^A

x '^ COOH (VI),

in which A, R ² , R ³ , X and Y have the meanings given under the general formula I, or D) compounds of the general formula VI

R ² \ _N A

\ -X COOH (VI),

in which A, R ² , R ³ , X and Y have the meanings given under the general formula I, with a suitable base in a suitable solvent to give a compound of the general formula VII

\\ _ y г η η м

• X COOM

(VII), N

in which A, R ² , R ³ , X and Y have the meanings given under the general formula I and M ^{2 represents} an alkali metal atom, one equivalent of an alkaline earth metal atom or an organic ammonium group, or E) compounds of the general formula VIII

(VIII)

in which R ² , R ³ , X and Y have the meanings given under the general formula I, with a compound of the general formula IX

(IX), Z COOR ¹

in which A and R ^{1 have} the meanings given under general formula I and Z represents a halogen atom or an alkylsulfonyloxy group, in the presence of a suitable solvent and a suitable base, or F) a compound of general formula X.

in which R ¹ , R ² , R ³ , X and Y have the meanings given under the general formula I, with a compound of general formula XI

A ¹ -R ¹⁰ (XI),

in which A ^{1 has} the meanings given for general formula (I) except for groups A-1 to A-6 and R ^{10 represents} a halogen atom, an alkylsulfonyloxy group or phenylsulfonyloxy group in a suitable solvent in the presence of a suitable base.

The individual process variants are preferably carried out in the presence of a diluent. For this purpose, all solvents inert to the reagents used can be used. Examples of such solvents or diluents are water, aliphatic, alicyclic and aromatic hydrocarbons, each of which may optionally be chlorinated, such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and trichlorethylene, Ethers, such as diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles, such as acetonitrile and propionitrile, alcohols, such as methanol, ethanol, isopropanol, butanol and Ethylene glycol, esters such as ethyl acetate and amyl acetate, acid amides such as dimethylformamide and dimethylacetamide, sulfoxides and sulfones such as dimethylsulfoxide and sulfolane, and bases such as pyridine.

The presence of a reaction catalyst may be advantageous. Suitable catalysts are potassium iodide and onium compounds, such as quaternary ammonium, phosphonium and arsonium compounds and sulfonium compounds. Also suitable are polyglycol ethers, especially cyclic ones, such as 18-kępep-б, and tertiary amines, such as tributylamine. Preferred compounds are quaternary ammonium compounds, such as benzyltriethylammonium chloride and tetrabutylammonium bromide.

The reactions can be carried out at the pressure of the environment, although they can be carried out at elevated or reduced pressure.

Process variant A) is preferably used in aromatic hydrocarbons, such as benzene, toluene or xylene, halogenated hydrocarbons, such as methylene chloride or chloroform, alcohols, such as methanol, ethanol or isopropanol, ethers, such as

Ethyl ether, isopropyl ether, tetrahydrofuran or 1,4-dioxane, ketones such as acetone or methyl ethyl ketone, esters such as methyl acetate or ethyl acetate, polar aprotic solvents such as dimethylformamide, dimethylacetamide or dimethylsulfoxide, and in other solvents such as acetonitrile or water.

As the base, an alkali metal such as sodium or potassium, an alkali or alkaline earth metal hydride such as sodium hydride, potassium hydride or calcium hydride, a carbonate such as sodium carbonate or potassium carbonate or a metal hydroxide such as sodium hydroxide or potassium hydroxide may be used.

The reaction is preferably carried out in a temperature range between room temperature and the boiling point of the solvent or solvent mixture. The reaction time is 1 to 24 hours.

However, the reaction may also be carried out in the absence of a solvent, in a temperature range of 120 to 160 ^° C, using an alkali metal carbonate such as anhydrous potassium carbonate.

The following literature methods can be used, for example, to prepare the α-hydroxy or α-mercaptocarboxylic acid derivatives required in this process variant: J. Org. Chem. 33, 2565 [1968]; J. Amer. Chem. Soc. 95,7146 [1973]; J. Chem. Soc. 1957.3262; J. Org. Chem. 33, 1831 [1968]; Can. J. Chem. 60 [1982] 2707; Soc. Soc. Chim. Fri 1969,2721.

Process variants B) and C) are preferably carried out in alcohols, such as methanol, ethanol or isopropanol, in ketones, such as acetone or methyl ketones, in water or in a mixture of water and a polar solvent.

As the base, a carbonate such as sodium carbonate, potassium carbonate or calcium carbonate and a metal hydroxide such as sodium hydroxide or potassium hydroxide may be used.

The temperature range of the reactions is between room temperature and the boiling point of the respective solvent or solvent mixture. The reaction time is 0.5 to 36 hours.

If R ¹ in the general formula IV is a benzyl group, a compound of the general formula VI can also be obtained by catalytic reduction (hydrogenation).

For process variant D), the solvents used may be hydrocarbons, such as benzene, toluene or xylene, halogenated hydrocarbons, such as methylene chloride or chloroform, alcohols, such as methanol, ethanol or isopropanol, ethers, such as ethyl ether, isopropyl ether, tetrahydrofuran or 1,4-dioxane, ketones such as acetone or methyl ethyl ketone, esters such as methyl acetate or ethyl acetate, or nitriles such as acetonitrile.

As the base, an alkali metal such as sodium or potassium, an alkali metal or alkaline earth metal hydride such as sodium hydride, potassium hydride or calcium hydride, a carbonate such as sodium carbonate, potassium carbonate or calcium carbonate, or a metal hydroxide such as sodium hydroxide or potassium hydroxide can be used. As the organic base, ammonia, an alkylamine (primary amine), a dialkylamine (secondary amine) or a trialkylamine (tertiary amine) can be used.

The temperature range of the reaction is between room temperature and the boiling point of the respective solvent or solvent mixture. The reaction time is 5 minutes to 10 hours.

For the process variant E) can be used as the solvent hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as methylene chloride or chloroform, ethers such as ethyl ether, isopropyl ether, tetrahydrofuran or 1,4-dioxane, ketones such as acetone or methyl ethyl ketone, esters such Methyl acetate or ethyl acetate, aprotic polar solvents such as dimethylformamide, dimethylacetamide or dimethyl sulfoxide, and other solvents such as acetonitrile.

As bases, alkali metals such as sodium or potassium, alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride or calcium hydride, carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate or potassium hydrogencarbonate, or metal hydroxides such as sodium hydroxide or potassium hydroxide can be used.

The temperature range of the reaction is between room temperature and the boiling point of the respective solvent or solvent mixture. The reaction time is 5 minutes to 24 hours.

Process variant F) is preferably carried out in aprotic solvents, such as benzene, toluene, xylene, tetrahydrofuran, diethyl ether, hexane, dimethylformamide or dimethyl sulfoxide. For deprotonation of the compounds of general formula X, bases such as sodium hydride, potassium tertiary butylate or lithium diisopropylamide may be used.

The reaction temperature is between -78 ° C and the boiling point of the respective solvent or solvent mixture. The reaction time is 0.5 to 24 hours.

Compounds of general formula X are described in the literature or can be prepared by literature procedures (Khim.-Farm, Zh. 16 [8], 931-934 [1982]; Ukr. Khim. Zh. [Russ. Ed.] 49 [11], 1205-1208 [1983]; Fizol.

Act Veshchestva, 18, 75-79 [1986]; USSR-PS 791746).

The novel compounds prepared by the abovementioned processes can be isolated from the reaction mixture by the customary processes, for example by distilling off the solvent used under normal or reduced pressure, by precipitation with water or by extraction.

An increased degree of purity can be obtained as a rule by column chromatographic purification as well as by fractional distillation or crystallization.

The new compounds are usually colorless and odorless liquids and crystals which are soluble in water, sparingly soluble in aliphatic hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane, readily soluble in halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride, aromatic Hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, carbonitriles such as acetonitrile, alcohols such as methanol and ethanol, carboxylic acid amides such as dimethylformamide, and sulfoxides such as dimethyl sulfoxide are.

The agents of the invention show a good herbicidal action in broad-leaved weeds and grasses. Selective use of the agents of the invention is possible in various crops, for example, rapeseed, beet, soybean, cotton, rice, barley, wheat and other cereals. Individual agents are particularly suitable as selective herbicides in beets, cotton, soybeans and cereals. 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 hops plants, and for selective weed control in annual crops.

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

Dicotyledonous weeds of the genera Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium,

Carduus, Sonchus, Solanum, Rorippa, Lamium, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum.

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

Depending on the type of application, the application rates in the pre-emergence and post-emergence range from 0.001 to 5 kg / ha.

The agents of the invention may also be used as defoliants, desiccants and herbicides. They also influence plant growth and can therefore be used to influence the growth of crops. Some of these agents also show a fungicidal action.

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 compound partners are those active compounds which are listed in Weed Abstracts, Vol. 38, No.3, 1989, under the title "List of common names and abbreviations employed 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.

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 acids and their 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 Spritzbrühmengen about 100 to 1000 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) 25 wt .-% active ingredient 60 wt .-% kaolin 10 wt .-% silica 5 wt .-% of a mixture of the calcium salt of lignosulfonic acid and the sodium salt of

N-methyl-N-oleyl-taurine 2.) 40 wt .-% of active ingredient

25% by weight clay minerals

25% by weight of silica

10% by weight of a mixture of the calcium salt of lignin sulfonic acid and alkylphenyl polyglycol ethers

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

25% by weight of active compound 15% by weight of cyclohexanone 55% by weight of xylene 5% by weight of a mixture of the calcium salt of dodecylbenzenesulfonic acid and nonylphenylpolyoxyethylene

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

Example 1 Methyl 2- (3-methoxyphenyl) -2- (4,6-dimethoxy-2-pyrimidinyloxy) acetate 8 g (40.7 mmol) of 2- (3-methoxyphenyl) -glycolic acid methyl ester are dissolved in 100 ml of dimethylformamide and treated with 2 , 8g (20.4mmol) of potassium carbonate. After 20 minutes of stirring, 8.8 g (40,7mmol) was added 4,6-dimethoxy-2-methylsulfonylpyrimidine and heated for one hour at 90 ⁰ C. The mixture is poured onto 100 ml of water and

extracted three times with 10OmI ethyl acetate. The combined ethyl acetate phases are washed with water, dried over magnesium sulfate and evaporated. The residue is recrystallized from diisopropyl ether. Yield: 9.8 g = 73% of theory m.p .: 97-100 ⁰ C.

Example 2 2- (4,6-Dimethoxy-2-pyrimidinyloxy) -2-phenylacetic acid

5 g (16 mmol) of 2- (4,6-dimethoxy-2-pyrimidinyloxy) -2-phenylacetic acid methyl ester are dissolved in 50 ml of water / ethanol (1: 1) and admixed with 0.9 g of potassium hydroxide. After stirring for 16 hours at room temperature, it is extracted with ethyl acetate. The aqueous phase is acidified to pH 2 with 10% strength hydrochloric acid and extracted with ethyl acetate. After drying over magnesium sulfate, the ethyl acetate phase is concentrated and the resulting solid is recrystallized from a diisopropyl ether / ethyl acetate mixture

Yield: 2.45 g = 51% of theory mp: 158-161 ⁰ C

Example 3 Methyl 2- (4,6-dimethoxy-2-pyrimidinylthio) -4-pentenoate

1.22 g (12.2 mmol) of diisopropylamine are initially charged in 10 ml of tetrahydrofuran under nitrogen and treated with 7.8 ml (12.2 mmol) of 1.6M n-butyllithium dissolved in hexane at -78 ° C to -50 ⁰ C. , After stirring for 20 minutes, 3 g (12.2 mmol) of methyl 2- (4,6-dimethoxy-2-pyrimidinylthio) acetate, dissolved in 30 ml of tetrahydrofuran, are slowly added to the reaction solution and stirring is continued for a further 30 minutes. Thereafter, 1.45 g (12.2 mmol) of 3-bromopropene are slowly added dropwise to the solution. With stirring, the reaction solution is allowed to warm slowly to room temperature and stirred for 20 hours. The batch is added to 100 ml of ice-water and extracted thoroughly with ethyl acetate. The dried over magnesium sulfate ethyl acetate phase is evaporated and then purified by medium pressure chromatography with hexane / ethyl acetate as eluent.

Yield: 0.9 g = 25.9% of theory

Preparation of the starting material for Example 3

2- (4,6-dimethoxy-2-pyrimidinylthio) -acetic acid methylester

25 g (230 mmol) of thioglycolic acid methyl ester are initially charged in 250 ml of dimethylformamide and admixed with 16.3 g (115 mmol) of potassium carbonate. After stirring for 20 minutes at room temperature, is 50 g (230 mmol) of 4,6-Diemthoxy-2-methylsulfonylpyrimidine and heated three hours 9O ⁰ C. It is the reaction mixture into water and extracted with Essigester, the organic phase washed with water, dried over magnesium sulfate , filtered, the solvent is distilled off and the resulting crude product of diisopropyl ether recrystallized.

Yield: 44.6 g = 79.4% of theory

Fp.:67-69°C

Example 4 Methyl 2- (4,6-dimethoxy-2-pyrimidinyloxy) -3-fluoro-3-methylbutanoate 4g (26.6 mmol) of methyl S-fluoro-hydroxy-S-methylbutanoate and 5.81 g (26.6 mmol) of 4 , 6-Dimethoxy-2-methylsulfonylpyrimidine are dissolved in 75 ml of dimethylformamide at 20 ° C and treated with 1.84 g (13.3 mmol) of potassium carbonate. The suspension is stirred for 5 hours at 20 ° C and then heated for one hour to 6O ⁰ C. The reaction mixture is added to 150 ml of ice water and extracted three times with 75 ml of ethyl acetate. The combined ethyl acetate phases are washed with water, dried over magnesium sulfate, filtered and concentrated. The resulting solid is purified by column chromatography on silica gel with hexane / ethyl acetate mixtures. Yield: 2.9 g = 37.7% of theory mp: 73-74 ° C

Example 5 2- (4,6-Dimethoxy-2-pyrimidinyloxy) -3-fluoro-3-methylbutanoic acid

2 g (6.9 mmol) of 2- (4,6-dimethoxy-2-pyrimidinyloxy) -3-fluoro-3-methylbutanoic acid methyl ester are dissolved in a mixture of 20 ml of water and 10 ml of methanol, with 387 mg (6.9 mmol) Added potassium hydroxide and stirred at 50 ° C for 4 hours. The reaction solution is added to 50 ml of water and extracted with 50 ml of ethyl acetate. The aqueous phase is then acidified to pH 2 with hydrochloric acid and extracted three times with 100 ml of ethyl acetate. The combined ethyl acetate phases are washed with water, dried over magnesium sulfate, filtered and concentrated.

Yield: 1.0g = 54.5% of theory

Fp.:107-108°C

In an analogous manner, the following compounds of general formula I were prepared:

example A R ¹ R ² R ³ X Y physical No. constant 6 3-pyridyl H OCH ₃ OCH ₃ O CH Mp .: 191-193 ⁰ C 7 2- (N-methyl) - CH ₃ OCH ₃ OCH ₃ O CH Fp.:148-149°C indolyl 8th phenyl C (CH ₃ I ₃ OCH ₃ OCH ₃ O CH Fp.:126-127°C 9 3-methoxyphenyl H OCH ₃ OCH ₃ O CH Fp.:141-144°C 10 4-methoxyphenyl CH ₃ OCH ₃ OCH ₃ O CH Mp .: 91-92 ° C 11 4-methoxyphenyl H OCH ₃ OCH ₃ O CH Fp.:132-133°C 12 phenyl CH ₃ OCH ₃ OCH ₃ O CH Mp .: 89-9O ⁰ C

example A R ¹ R ² R ³ X Y physical No. constant 13 phenyl CH ₃ OCH ₃ OCH ₃ 0 CH Mp .: 80-81 ⁰ C (S-lsomeres) 14 phenyl H OCH ₃ OCH ₃ 0 CH Mp .: 153-154 ° C (S-lsomeres) 15 phenyl CH ₃ OCH ₃ OCH ₃ 0 CH Fp.:83-84°C (R-lsomeres) 16 phenyl H OCH ₃ OCH ₃ 0 CH Mp .: 148-149 ° C (R-lsomeres) 17 2-thienyl CH ₂ CH ₃ OCH ₃ OCH ₃ 0 CH Fp.:87-88°C 18 2-thienyl H OCH ₃ OCH ₃ 0 CH Mp .: 136-137 ⁰ C 19 phenyl CH ₂ CH ₃ OCH ₃ OCH ₃ O CH Fp.:82-84°C 20 4-FIuorphenyl CH ₃ OCH ₃ 0CH3 O CH Fp.:92-95°C 21 4-fluorophenyl H OCH ₃ OCH ₃ 0 CH Fp.:134-138°C 22 3-pyridyl CH ₂ CH ₃ OCH ₃ OCH ₃ 0 CH Fp.:66-67°C 23 phenyl CH ₃ SCH ₃ SCH ₃ 0 N Mp .: 79-81 ⁰ C 24 2,6-difluorophenyl CH ₃ OCH ₃ OCH ₃ 0 CH Mp .: 78-80 ⁰ C 25 2,6-difluorophenyl H OCH ₃ OCH ₃ 0 CH Mp .: 189-192 ° C 26 4-trifluoro- CH ₃ OCH ₃ OCH ₃ 0 CH Fp.:117-119°C methylphenyl 27 4-trifluoro- H OCH ₃ OCH ₃ 0 CH Fp.:152-155°C methylphenyl 28 3-thienyl CH ₂ CH ₃ 0CH3 OCH3 0 CH Mp .: 94-95 ° C 29 3-Tienyl H OCH ₃ OCH ₃ 0 CH Fp.:147-148°C(Zers.) 30 4-bromophenyl CH ₃ OCH ₃ OCH ₃ 0 CH Mp .: 104-105 ⁰ C 31 4-bromophenyl H OCH ₃ OCH ₃ 0 CH Fp.:168-170°C 32 3,5-difluorophenyl CH ₃ OCH ₃ OCH ₃ 0 CH Fp.:125-126°C 33 3,5-difluorophenyl H OCH ₃ OCH ₃ 0 CH Mp: 128-131 ⁰ C 34 CH = CH ₂ CH ₃ OCH ₃ OCH ₃ 0 CH RF value: 0.92 (in ethyl acetate) 35 CH = CH ₂ H OCH ₃ OCH ₃ 0 CH Rf value: 0.26 (in ethyl acetate) 36 phenyl CH ₃ OCH ₃ NHCH ₃ 0 N Foam, mp .: from 59 ^° C. 37 phenyl CH ₃ CH ₃ NHCH ₃ 0 N Mp .: 125-130 ⁰ C 38 phenyl CH ₃ OCH ₃ N (CH ₃ I ₂ 0 N Fp.:94-98°C 39 Cii2-Сг "і ⁼ СгІ2 H OCH ₃ OCH ₃ S CH Mp .: 91-94 ° C 40 phenyl benzyl OCH ₃ OCH ₃ 0 CH Mp .: 123-124 ° C 41 2-naphthyl CH ₃ OCH ₃ OCH ₃ 0 CH Fp.:129-130°C 42 2-naphthyl H OCH ₃ OCH ₃ 0 CH Mp: 170-171 ° C 43 1-naphthyl CH ₃ 0CH3 OCH ₃ 0 CH Mp: 126-127 ° C 44 1-naphthyl H OCH ₃ OCH ₃ 0 CH Mp .: 169-171 ° C 45 phenyl H CH ₂ CH ₃ CH ₂ CH ₃ 0 CH Fp.:135-137°C 46 phenyl CH ₃ OCH ₃ OCH ₃ S CH Mp .: 94-95 ° C 47 phenyl H OCH ₃ OCH ₃ S CH Mp .: 158-16O ⁰ C 48 2-thienyl CH ₃ OCH ₃ OCH ₃ 0 CH Mp: 101-103 ⁰ C 49 -CH = CH-CH ₃ CH ₃ OCH ₃ OCH ₃ 0 CH Mp .: 60-61 ° C 50 -CH = CH-CH ₃ H OCH ₃ OCH ₃ 0 CH Mp .: 126-128 ⁰ C 51 2-nitrophenyl CH ₃ OCH ₃ OCH ₃ 0 CH Fp.:103°C 52 2-nitrophenyl H OCH ₃ OCH ₃ 0 CH Fp.:162°C 53 2-chlorophenyl CH ₃ OCH ₃ OCH ₃ 0 CH Fp.:118°C 54 2-chlorophenyl H OCH ₃ OCH ₃ 0 CH Mp .: 180 ^° C 55 phenyl CH ₃ OCH ₂ CH ₃ OCH ₂ CH ₃ 0 CH Mp .: 59-61 ⁰ C 56 phenyl H SCH ₃ SCH ₃ 0 CH ng ⁰ : 1.5745 57 phenyl H OCH ₂ CH ₃ OCH ₂ CH ₃ 0 CH Mp .: 158-16O ⁰ C 58 cyclopropyl CH ₃ 0CH3 OCH ₃ 0 CH Mp .: 83-84 ° C 59 cyclopropyl H OCH ₃ OCH ₃ 0 CH Mp .: 147-148 ° C 60 CF (CH ₃ ) ₂ CH ₂ CH ₃ OCH ₃ OCH ₃ 0 CH Mp .: 73-74 ° C 61 CF (CH ₃ ) -phenyl CH2CH3 OCH ₃ OCH ₃ 0 CH Fp.:106°C 62 C (CH ₃ ) HIGH ₃ ) CH ₃ OCH ₃ OCH ₃ 0 CH Mp .: 102-103 ° C 63 CCI (CH ₃ J ₂ CH ₃ OCH ₃ OCH ₃ 0 CH Fp.:109°C 64 C (CH ₃ J ₂ - (OCH ₃ ) H OCH ₃ OCH ₃ 0 CH Mp: 139-141 ° C 65 CF (CH ₃ J ₂ CH ₂ CH ₃ OCH ₃ OCH ₃ 0 N ng ⁰ : 1.4754 66 CCI (CH ₃ ) ₂ CH ₂ CH ₃ OCH ₃ OCH ₃ 0 CH Fp.:95-96°C 67 1-fluorocyclohexyl CH ₃ OCH ₃ 0CH3 0 CH Mp .: 99-100 ° C 68 CF (CH ₃ ) -phenyl CH ₂ CH ₃ OCH ₃ OCH ₃ 0 N Mp .: 79-80 ⁰ C

example A R ¹ R ² R ³ X Y physical No. constant 69 1-methoxy- CH ₃ OCH ₃ OCH ₃ O CH Fp.:72-75°C cyclopentyl 70 1-methoxy- CH ₃ OCH ₃ OCH ₃ O CH Mp .: 128-130 ⁰ C cyclohexyl 71 CF (CH ₃ ) -phenyl H OCH ₃ OCH ₃ O CH Mp .: 135-136 "C 72 1-fluoro- CH ₃ OCH ₃ OCH ₃ O CH Mp .: 89-90 ⁰ C cyclopentyl 73 C (CH ₂ CH ₃ ) - CH ₃ OCH ₃ OCH ₃ O CH Fp.:72-74°C (CH ₃ ) (OCH ₃ ) 74 C (OCH ₂ CH ₃ ) - CH ₂ CH ₃ OCH ₃ OCH ₃ O H Fp.:71-72°C (CH ₃ MPhenyl) 75 1-fluorocyclohexyl H OCH ₃ OCH ₃ O CH Mp: 140-141 ° C 76 CHF-phenyl H OCH ₃ OCH ₃ O CH ng ⁰ : 1.5374 77 CHF-phenyl CH ₂ CH ₃ OCH ₃ OCH ₃ O CH Fp.:57-59°C 78 CHF-phenyl H OCH ₃ OCH ₃ O N 79 CHF-phenyl CH ₂ CH ₃ OCH ₃ OCH ₃ O N 80 CF (CH ₃ ) -phenyl H OCH ₃ OCH ₃ O N 81 C (OCH ₂ CH ₃ ) - H OCH ₃ OCH ₃ O CH Mp: 128-13O ⁰ C (CH ₃ ) (phenyl) 82 C (OCH ₂ CH ₃ ) - H OCH ₃ OCH ₃ O N (CH ₃ ) (phenyl) 83 C (OCH ₂ CH ₃ ) - CH ₂ CH ₃ OCH ₃ OCH ₃ O N (CH ₃ ) (phenyl) 84 CCI (CH ₃ ) -phenyl H OCH ₃ OCH ₃ O CH 85 CCI (CH ₃ ) -phenyl CH ₂ CH ₃ OCH ₃ OCH ₃ O CH Fp.:103-105°C 86 CCI (CH ₃ ) -phenyl H OCH ₃ OCH ₃ O N 87 CCI (CH ₃ ) -phenyl CH ₂ CH ₃ OCH ₃ OCH ₃ O N 88 CHF-phenyl H OCH ₃ OCH ₃ S CH 89 CHF-phenyl CH ₂ CH ₃ OCH ₃ OCH ₃ S CH 90 CHF-phenyl H OCH ₃ OCH ₃ S N 91 CHF-phenyl CH ₂ CH ₃ OCH ₃ OCH ₃ S N 92 CF (CH ₃ ) -phenyl H OCH ₃ OCH ₃ S CH 93 CF (CH ₃ ) -phenyl CH ₂ CH ₃ OCH ₃ OCH ₃ S CH 94 CF (CH ₃ ) -phenyl H OCH ₃ OCH ₃ S N 95 CF (CH ₃ ) -phenyl CH ₂ CH ₃ OCH ₃ OCH ₃ S N 96 1-fluoro- H OCH ₃ OCH ₃ O CH Mp .: 138-14O ⁰ C cyclopentyl 97 1-fluoro CH ₃ OCH ₃ OCH ₃ O N cyclopentyl 98 1-fluoro- H OCH ₃ OCH ₃ O N cyclopentyl 99 1-fluoro- CH ₃ OCH ₃ OCH ₃ O N ng ⁰ : 1.4963 cyclohexyl 100 1-fluoro- H OCH ₃ OCH ₃ O N cyclohexyl 101 CF (CH ₃ I ₂ H OCH ₃ OCH ₃ O N ng ⁰ : 1.4747 102 C (CH ₂ CH ₃ ) - H OCH ₃ OCH ₃ O CH Mp .: 137-140 ° C (CH ₃ ) (OCH ₃ ) 103 1-methoxy- H OCH ₃ OCH ₃ O CH Mp .: 150-153 ⁰ C cyclopentyl

The following examples illustrate the possible uses of the agents according to the invention:

Example A

In the greenhouse, the listed plant species were treated after emergence with the listed agents in an application rate of 1.0 kg / ha. The agents were sprayed uniformly over the plants for this purpose as emulsion or suspensions containing 500 liters of water / ha. Here, two weeks after treatment, the compositions according to the invention showed a high crop selectivity in sunflower with excellent action against the weeds. The comparison agent did not show the same high selectivity.

In the following table mean:

0 = no damage

1 = 1- 24% damage

2 = 25-74% damage

3 = 75- 89% damage

4 = 90-100% damage

HELAN = Helianthus annuus ABUTH = Abutilon theophrasti GALAP = Galium aparine SEBEX = Sesbania exaltata SOLSS = Solanumsp. VERPE = Veronica persica

H A G S S V e B A e O e L U L B L R invention A T A e S P medium N H P X S e Example 12 1 3 3 3 3 3 Example 49 0 3 3 2 3 3 Example 50 1 3 3 3 3 3 untreated 0 0 0 0 0 0 comparison means 2- (4-isopropyl-4-methyl- 3 2 3 2 3 2 5-oxo-2-imidazolin-2-yl) - 4 (5) -methylbenzoe- säuremethylester

Example B

In the greenhouse, the listed plant species were treated before emergence with the listed agents in an application rate of 1.0kg drug / ha. The compositions were sprayed uniformly over the soil as emulsions or suspensions containing 500 liters of water / ha for this purpose. Here, three weeks after the treatment, the compositions of the invention showed a high crop selectivity in soybean, cotton, sunflower, wheat and corn with excellent weed control. The comparison agent did not show the same high selectivity. In the following table mean:

0 = no damage

1 = 1- 24% damage

2 = 25-74% damage

3 = 75- 89% damage

4 = 90-100% damage

GLXMA = Glycine maxima GOSHI = Gossypium hirsutum HELAN = Helianthus annuus TRZAX = Triticum aestivum ZEAMX = Zea mays PANSS = Panicum maximum GALAP = Galium aparine SOLSS = Solanum sp. VERPE = Veronica persica

G G H T Z P G S V L O e R e A A O e X S L Z A N L L R invention M H A A M S A S P medium A I N X X S P S e Example 12 1 0 1 0 1 3 3 4 3 Example 48 1 0 0 0 - - 3 3 4 untreated 0 0 0 0 0 0 0 0 0 comparison means 2- {4-isopropyl-4-methyl 3 2 3 2 3 3 4 4 3 5-oxo-2-imidazolin-2-yl) - 4 (5) -methylbenzoe- säuremethylester

Example С

In the greenhouse, the agent listed in the table was applied at the rate of application also mentioned. For this purpose, the agent was added in the form of preparations in containers containing 1500 ml of water. The test plant species were used at the 2- to 5-leaf stage. Three weeks after the application, the damage to the plants was scored. The agent according to the invention showed a strong action against important rice weeds with simultaneous selectivity to water rice. In the following table mean:

0 = no damage

1 = weak damage

2 = mean damage

3 = severe damage

4 = totally annihilated

ORYSA logo CNRS logo INIST kg of active ingredient / ha O e S S M C ECHCG = I2 1.0 R C A C O Y SAGPY = Y H G P O P SCPJU = S C P J V S MOOVA A G Y U A e CYPSE = 0 3 4 4 4 4 = Oryza sativa = Echinochloa crus-galli = Sagittaria pygmaea = Scirpus juncoides = Monochoria vaginalis = Cyperus serotinus Water application according to the invention medium Example'

Example D

In the greenhouse, the listed plant species were treated before emergence with the listed funds in an application rate of 1.0 kg / active ingredient / ha. The compositions were sprayed uniformly over the soil as emulsions or suspensions containing 500 liters of water / ha for this purpose. Here, three weeks after the treatment, the agents according to the invention showed an excellent activity against the weeds. In the following table mean:

0 = no damage A S C A I M P S V V 1 = 1- 24% damage V e Y B P A O O F I 2 = 25-74% damage e T P U O T L L R O 3 = 75- 89% damage Inventive F V e T S C S S P S 4 = 90-100% damage Mean A I S H S H S S e S AVEFA = Avena fatua Example 4 3 4 4 3 3 3 - - - - SETVI = Setaria viridis Example 5 3 4 4 3 3 4 - - - - CYPES = Cyperus esculentu: Example 15 3 4 3 3 3 4 3 3 4 4 Example 28 3 3 3 - 3 - 3 3 3 4 Example 58 3 3 3 3 3 - - - - Example 59 - 4 3 3 3 3 - - - - Untreated 0 0 0 0 0 0 0 0 0 0 ABUTH = Abutilontheophrasti IPOSS = Ipomoea purpurea MATCH = Matricaria chamomilla POLSS = Polygonum sp. SOLSS = Solanum sp. VERPE = Veronica persica VIOSS = Viola sp.

Example E

In the greenhouse, the listed plant species were treated after emergence with the listed agents in an application rate of 0.1 kg / ha. The funds were sprayed for this purpose as an emulsion with 500 liters of water / ha evenly over the plants. Here, two weeks after the treatment, the agent according to the invention showed a high crop selectivity in cotton with excellent activity against the weed. The comparator did not show the same high potency.

In the following table mean:

0 = no damage 1 = 1 - 24% damage

2 = 25-74% damage

3 = 75- 89% damage

4 = 90-100% damage

GOSHI = G A I Y P A I P S V V ALOMY O L Example 4 1 3 A B P 0 0 e I PANSS = S O Untreated 0 0 N U 0 L L R O ABUTH = Inventive H M S T S S S P S IPOSS = medium S H S S S e S POLSS = 3 4 3 3 3 3 3 SOLSS = 0 0 0 0 0 0 0 VERPE = VIOSS = = Gossypium hirsutum = Alopecurus myosuroides = Panicum maximum = Abutilontheophrasti Ipomoea purpurea = Polygonum sp. = Solanumsp. = Veronica persica   Viola sp.

comparison means

(according to EP application

Connection No. 243 0

Example F

In the greenhouse, the listed plant species were treated after emergence with the listed agents in an application rate of 0.1 kg / ha. The funds were sprayed for this purpose as an emulsion with 500 liters of water / ha evenly over the plants. Here, two weeks after the treatment, the agent according to the invention showed a high crop selectivity in cotton with excellent activity against the weed. The comparison agent did not show the same high effectiveness. In the following table mean:

0 = no damage

1 = 1- 24% damage

2 = 25-74% damage

3 = 75- 89% damage

4 = 90-100% damage

GOSHI = Gossypium hirsutum AGRRE = Elymus repens BROTE = Bromidectorum SETVI = Setaria viridis PANSS = Panicum maximum SORHA = Sorghum halepense ABUTH = Abutilon theophrasti GALAP = Galium aparine IPOSS = Ipomoea purpurea MATCH = Matricariachamomilla POLSS = Polygonum sp. SEBEX = Sesbania exaltata VERPE = Veronica persica

GABSPSAGI MPSV OGREAOBAPAOEE SROTNRULOTLBR

Inventive HETVSHTASCSEP Agent I EEI SAHPSHSXE

Example 5 1

Untreated 0

Comparative agent (according to EP application

Compound No. 4 0

3 0

3 0

3 0

4 0

Claims (1)

Claim: a C ₁ -C ₄ -alkoxy or halogen-substituted C ₁ -C ₆ -AIkYlrest, an unbranched C ^ Ce-alkenyl group, a cyclopropyl group, a substituted C ₁ -C ₄ -alkoxy or halogen Cy-Ce-cycloalkyl, or at the aliphatic carbon atom by hydrogen or methyl and C ₁ -C ₄ -alkoxy or halogen-substituted benzyl radical, an oxygen atom, a sulfur atom or a group -NR ⁹ -, a hydrogen atom, a C ₁ -C ₄ -alkyl radical or a benzyl radical, R ^{2 is} a C ₁ -C ₄ -AIkYlrest, a C ₁ -C ₄ alkoxy, C ^ d-alkylthio, C ^ CrAlkylaminorest, a di-Ci-C ^ alkylamino group or a halogen atom, a C! -C ₄ Alkyl radical, a C ₁ -C ₄ alkoxy radical, a C ₁ -C ₄ alkylthio radical, a C ₁ -C ₄ alkylamino radical, a di-C ₁ -C ₄ -alkylamino radical or a halogen atom, with the proviso that the radicals R ² and R ^{3 are} not both Methyl and not a methyl and the other tert-butyl, when A is unsubstituted phenyl, X is sulfur and Y is a methine group, R ^{4 is} a hydrogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -alkoxy radical, an amino radical, a di-C ₁ -C ₄ -alkylamino radical, a nitrogen radical, a halogen atom, a trifluoromethyl radical or a phenyl radical, R ^{5 is} a hydrogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -alkoxy radical, an amino radical, a di-C ₁ -C -alkylamino radical, a nitrogen radical, a halogen atom, a trifluoromethyl radical or a phenyl radical, R ⁶ a hydrogen atom, a C ₁ -C ₄ -alkyl rest ky I, C ₁ -C ₄ -alkyl koxyrest, an amino group, a di-C _n -C ₄ alkylamino group, a nitro group, a halogen atom, a trifluoromethyl or a phenyl radical, R ^{7 is} a hydrogen atom, a C ₁ -C ₄ -AlkYlTeSt, a dC ^ alkoxy, an amino group, a di-Ci-Ci-alkylamino, a nitro group, a halogen atom, a trifluoromethyl radical or a phenyl,
R ⁸ is a hydrogen atom, a C ₁ -C ₄ -A ^ yIrest, a Ci-C ₄ -AIkOXYrOSt, an amino group, a di-C ^ Q-alkylamino, a nitro group, a halogen atom, a trifluoromethyl radical or a phenyl radical, R ^{9 is} a hydrogen atom or a C ₁ -C ₄ -alkyl radical,
X is an oxygen atom or a sulfur atom, with the proviso that X is not oxygen means if AAIIyI is, and
Y is a methine group or a nitrogen atom, with the proviso that Y is not a methine group when A is 1-chloroethyl or 1-methyl-2,2,2-trifluoroethyl, and their alkali metal salts, alkaline earth metal salts and organic ammonium salts and their optical isomers, in admixture with carriers and / or auxiliaries.