DE4040118A1 - SUBSTITUTED (ALPHA) -PYRIMIDINYLOXY (THIO) - AND (ALPHA) -TRIAZINYLOXY (THIO) VINYL ACID DERIVATIVES, METHODS FOR THE PRODUCTION THEREOF AND THEIR USE AS AGENTS WITH HERBICIDES, FUNGALIZERS AND PLANTING AGENTS - Google Patents

Abstract

Herbicidal acetic acid derivatives of formula (I) where: R is a group -CO2R<1>, -CH2OH, -CONHSO2R<a> or -CONHSO2NR<a>R<b>, where R<1> is hydrogen or a salt- or ester-forming group, R<a> is alkyl or aryl, and R<b> is hydrogen, alkyl or aryl; R<2> and R<3>, which may be the same or different, are each halogen, alkyl, alkoxy, alkylthio, alkylamino or dialkylamino; A is a substituted or unsubstituted aryl, heterocyclyl or benzoheterocyclyl group, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl group; X is oxygen or sulfur; Y is -CH= or -N=; and Z is oxygen or sulfur; and salts thereof, herbicidal compositions containing them, processes for their preparation, and methods of using them.

Description

The invention relates to new substituted α-pyrimidinyloxy (thio) - and α-Triazinyloxy (thio) acetic acid derivatives, process for their preparation and their use as agents with herbicidal, fungicidal and plant growth-regulating action.

It is already known that pyrimidine derivatives have a herbicidal action (EP applications 02 23 406, 02 49 707, 02 49 708, 02 87 072 and 02 87 079). However, the herbicidal activity of the known compounds is frequent not sufficient, or occur with a corresponding herbicide effect Selectivity problems in main agricultural crops.

The object of the present invention is to provide new compounds, that do not have these disadvantages and that in their biological Properties are superior to previously known compounds.

It has now been found that substituted α-pyrimidinyloxy (thio) - and α-Triazinyloxy (thio) acetic acid derivatives of the general formula I

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

a C₁-C₁₀ alkyl radical, one or more, identical or different by C₁-C₄-alkoxy, C₁-C₄-alkylthio, amino, C₁-C₄-alkylamino, di-C₁-C₄-alkylamino, nitro, halogen or phenyl substituted C₁-C₁₀ alkyl, a C₂-C₁₀ alkenyl, one or more, the same or different by C₁-C₄-alkoxy, C₁-C₄-alkylthio, amino, C₁-C₄-alkylamino, di-C₁-C₄- alkylamino, nitro, halogen or phenyl substituted C₂-C₁₀ alkenyl, a C₂-C₁₀ alkynyl, one or more, the same or different by C₁-C₁-alkoxy, C₁-C₄-alkylthio, amino, C₁-C₄-alkylamino , Di-C₁-C₄-alkylamino, nitro, halogen or phenyl substituted C₂-C₁₀-alkynyl radical, a C₃-C₈-cycloalkyl radical, one or more, the same or different, by C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, amino, C₁-C₄-alkylamino, di-C₁-C₄-alkylamino, nitro, halogen or phenyl substituted C₃-C₈-cycloal kylrest, a C₄-C₈-cycloalkenyl radical or one or more, the same or different, by C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, amino, C₁-C₄-alkylamino, di-C₁-C₄ alkylamino, nitro, halogen or phenyl substituted C₄-C₈-cycloalkenyl radical,
D is an oxygen atom, a sulfur atom or a group -NR⁹-,
R¹ is a hydrogen atom, a C₁-C₁₂-alkyl radical, one by hydroxy, halogen, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, benzyl, furyl, tetrahydrofuryl, phenyl, halophenyl, C₁-C₄-alkylphenyl , C₁-C₄-alkoxyphenyl, nitrophenyl, cyano, carboxyl, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylamino or di-C₁-C₄-alkylamino substituted C₁-C₁₂-alkyl radical, a C₂- interrupted by one or more oxygen atoms or sulfur atoms C₁₂-alkyl radical, one interrupted by one or more oxygen atoms or sulfur atoms and by hydroxy, halogen, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, benzyl, furyl, tetrahydrofuryl, phenyl, halophenyl, C₁-C₄ -Alkylphenyl, C₁-C₄-alkoxyphenyl, nitrophenyl, cyano, carboxyl, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylamino or di-C₁-C₄-alkylamino substituted C₂-C₁₂-alkyl radical, a C₃-C₈-alkenyl radical, one by C₁-C₃ alkoxy, phenyl or halogen substituie rten C₃-C₈-alkenyl, a C₃-C₈-alkynyl, a C₃-C₃-alkoxy, phenyl or halogen substituted C₃-C₈-alkynyl, a C₃-C₆-cycloalkyl, a methyl-substituted C₃-C₆-cycloalkyl, one Di-C₁-C₄-alkylmethyleneimino or a C₃-C₆-cycloalkyleneimino,
R² is a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, a C₁-C₄-alkylthio radical, a C₁-C₄-alkylamino radical, a di-C₁-C₄-alkylamino radical or a halogen atom,
R³ is a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, a C₁-C₄-alkylthio radical, a C₁-C₄-alkylamino radical, a di-C₁-C₄-alkylamino radical or a halogen atom,
R⁴ is a hydrogen atom, a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, an amino radical, a di-C₁-C₄-alkylamino radical, a nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical,
R⁵ is a hydrogen atom, a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, an amino radical, a di-C₁-C₄-alkylamino radical, a nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical,
R⁶ is a hydrogen atom, a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, an amino radical, a di-C₁-C₄-alkylamino radical, a nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical,
R⁷ is a hydrogen atom, a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, an amino radical, a di-C₁-C₄-alkylamino radical, a nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical,
R⁸ is a hydrogen atom, a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, an amino radical, a di-C₁-C₄-alkylamino radical, a nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical,
R⁹ is a hydrogen atom or a C₁-C₄ alkyl radical,
X is an oxygen atom or a sulfur atom,
Y is a methine group or a nitrogen atom and
Z is an oxygen atom or a sulfur atom
mean, and their alkali metal salts, alkaline earth metal salts, ammonium salts, or organically substituted ammonium salts and their optically active isomers show an interesting herbicidal, fungicidal and plant growth-regulating action.

The term halogen includes fluorine, chlorine, bromine and iodine. Under the label Alkali metal is lithium, sodium and potassium, under the name Alkaline earth metal to understand calcium, strontium and barium.

The compounds of general formula I according to the invention can for example be made by

• A) Compounds of the general formula II in which R², R³ and Y have the meanings given under the general formula I and V represents a halogen atom, an alkylsulfinyl group, a phenylsulfinyl group, an alkylsulfonyl group or a phenylsulfonyl group, with compounds of the general formula III in which A, R¹, X and Z have the meanings given under the general formula I, in a suitable solvent in the presence of a suitable base, or
• B) Compounds of the general formula IV in which A, R¹, R², R³, X, Y and Z 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. in which A, R², R³, X, Y and Z have the meanings given under the general formula I and M¹ represents an alkali metal atom or an equivalent of an alkaline earth metal atom, or
• C) Compounds of the general formula V in which A, R², R³, M¹, X, Y and Z 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 in which A, R², R³, X, Y and Z have the meanings given under the general formula I, or
• D) Compounds of the general formula VI in which A, R², R³, X, Y and Z 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 in which A, R², R³, X, Y and Z have the meanings given under the general formula I and M² represents an all-alkali metal atom, an equivalent of an alkaline earth metal atom, an ammonium ion or an organically substituted ammonium group, or
• E) Compounds of the general formula VIII in which R², R³, X and Y have the meanings given under general formula I, with a compound of general formula IX in which A, R¹ and Z have the meanings given under the general formula I and W represents a halogen atom, an alkylsulfonyloxy group, a phenylsulfonyloxy group or a p-methylphenylsulfonyloxy group, in the presence of a suitable solvent and a suitable, or
• F) a compound of the general formula X in which R¹, R², R³, X and Y have the meanings given under the general formula I, with a suitable halogenating reagent, such as, for example, N-halosuccinimide, in a suitable solvent and reacting the compounds of the general formula XI thus obtained in which R¹, R², R³, X and Y have the meanings given under the general formula I and Hal represents a halogen atom, with a compound of the general formula XIIA-ZH (XII), in which A and Z those under the general formula I have the meanings given, reacted in a suitable solvent with a suitable base.

The individual process variants are preferably in the presence of a Diluent carried out. For this purpose, everyone can face the solvents used are inert solvents.

Examples of such solvents or diluents are Water, aliphatic, alicyclic and aromatic hydrocarbons, the may each be optionally chlorinated, such as hexane, cyclohexane, Petroleum ether, ligrion, 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 Example 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 dimethyl sulfoxide and sulfolane, and bases such as pyridine.

The presence of a reaction catalyst can be advantageous. As catalysts potassium iodide and onium compounds are suitable, such as quaternary Ammonium, phosphonium and arsonium compounds as well as sulfonium compounds. Also suitable are polyglycol ethers, especially cyclic, such as 18-crown-6, and tertiary amines such as tributylamine. Preferred compounds are quaternary ammonium compounds, such as Example benzyltriethylammonium chloride and tetrabutylammonium bromide.

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

Process variant A) is preferred 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 dimethyl sulfoxide, and in other solvents, such as acetonitrile or water.

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 or potassium carbonate, or a metal hydroxide, such as sodium hydroxide or potassium hydroxide can be used.

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

However, the reaction can also take place in the absence of a solvent Temperature range from 120 to 160 ° C, using an alkali metal carbonate, such as anhydrous potassium carbonate.

To produce the α-hydroxy- or α-mercaptocarboxylic acid derivatives can, for example, the following Literature methods are used: Tetrahedron Lett. 26 (10), 1343-1344 [1985]; Bull, Soc. Chim. Fr. (9-10) Pt. 2, 552-558 [1979]; Chem. Ber. 97 (6), 1713-1715 [1964]; U.S. Patent 3,037,905.

Process variants B) and C) are preferred 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 carried out.

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

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

If R¹ in the general formula IV represents a benzyl group, one can Compound of the general formula VI also by catalytic reduction (hydrogenation) be preserved.

For process variant D), 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 can be used.

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 is used will. 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 Boiling point of the respective solvent or solvent mixture. The Response time is 5 minutes to 10 hours.

Process variant E) can be carried out in aprotic solvents such as benzene, Toluene, tetrahydrofuran, diethyl ether, hexane, dimethylformamide or Dimethyl sulfoxide.

To deprotonate the compounds of the general formula VIII, bases, such as sodium hydride, potassium hydride, calcium hydride, sodium carbonate, Potassium carbonate, potassium tert-butylate or potassium hydroxide, be used.

If reaction variant E) is carried out in polar solvents, such as water, Methanol or ethanol, through, are used to deprotonate the compounds of the general formula VIII, preferably alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, are used.  

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

The compounds of general formula VIII are described in the literature or can be prepared by methods given in the literature become: Chem. Ber. 36, 3196 [1903]; Helv. Chim. Acta 72, 742 [1989]; Zh. Org. Khim. 10 (1), 109-113 [1974].

The compounds of general formula IX can be given in the literature Processes are produced: Angew. Chem. 93, 594-595 [1981]; Synth. Comm. 16 (11), 1431-1438 [1986]; U.S. Patent 4,049,424.

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 the general formula X can bases such as sodium hydride, potassium tert-butylate or lithium diisopropylamide can be used.

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

The compounds of the general formula X are described in the literature or can be prepared by methods given in the literature (Khim. Farm. Zh. 16 (8), 931-4 [1982]; Ukr. Khim. Zh. (Russ. Ed.) 49 (11), 1205-8 [1983]; Fizol. Akt. Veshchestva, 18, 75-9 [1986]; USSR PS 791746).

The compounds according to the invention produced by the abovementioned processes can be isolated from the reaction mixture by the customary methods be, for example by distilling off the solvent used at normal or reduced pressure, through precipitation with water or by extraction.

An increased degree of purity can usually be determined by column chromatography Purification and by fractional distillation or crystallization be preserved.  

The compounds of the invention are generally colorless and odorless Liquids, as well as crystals, are soluble in water, slightly 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, carboxamides such as dimethylformamide, and Are sulfoxides such as dimethyl sulfoxide.

The compounds according to the invention show a good herbicidal activity broad-leaved weeds and grasses. A selective use of the invention Active ingredients are possible in different cultures, for example in rapeseed, beets, soybeans, cotton, rice, barley, wheat and other cereals. Individual active ingredients are selective herbicides in beets, Cotton, soybeans and cereals are particularly suitable. Likewise, the connections for weed control in permanent crops, such as forestry, Ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, Oil palm, cocoa, berry fruit and hop plants, and for selective weed control in annual crops.

The compounds of the present invention can include, for example, the following Plant genera are used:

Dicot weeds of the genera Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senecio, Ama ranthus, portulaca, xanthium, convolvulus, ipomoea, polygonum, sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Lamium, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum.

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

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

The active compounds according to the invention can also be used as defoliants, desiccants and can be used as an herbicide. They also affect plant growth and can therefore influence the growth of crops be used. Some of these active ingredients also show a fungicidal effect Effect.

The compounds according to the invention can either be used alone or in a mixture with one another or with other active ingredients. Possibly other pesticides or pesticides may vary depending on the desired purpose can be added. If a broadening of the spectrum of activity other herbicides may also be added. For example, those suitable as herbicidally active mixture partners Active ingredients described in Weed Abstracts, Vol. 39, No. 1, 1990, under the title "List of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts ".

A promotion of the intensity and speed of action can Example by adding additives, such as organic solvents, Wetting agents and oils can be achieved. Such additives may therefore be left out a reduction in drug dosage.

The labeled active ingredients or their mixtures are expediently in Form of preparations, such as powders, sprinkling agents, granules, solutions, Emulsions or suspensions, with the addition of liquid and / or solid Carriers or diluents and, if necessary, adhesives, 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, mineral oil fractions and Vegetable oils.  

Minerals are suitable as solid carriers, for example bentonite, silica gel, Talc, kaolin, attapulgite, limestone, and herbal products, for Example flour.

Examples of surface-active substances include calcium lignin sulfonate, Polyethylene alkylphenyl ether, naphthalenesulfonic acids and their salts, Phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates as well as substituted benzenesulfonic acids and their salts.

The proportion of the active ingredient (s) in the different preparations can vary widely. For example, the Average about 10 to 90 percent by weight of active ingredient, about 90 to 10 percent by weight liquid or solid carriers and optionally up to 20 percent by weight surfactants.

The funds can be applied in the customary manner, for example with water as a carrier in spray liquor quantities about 100 to 1000 liters / ha. A Use of the funds in the so-called low-volume and ultra-low-volume process is just as possible as their application in the form of so-called microgranules.

These preparations can be prepared in a manner known per se, for example by grinding or mixing processes. If desired can only prepare the individual components briefly be mixed before use, for example in the so-called Tank mix procedure is carried out in practice.  

For the preparation of the various preparations, for example following components:

A) wettable powder

1.) 25% by weight of active ingredient
60% by weight kaolin
10% by weight of silica
10 wt .-% of a mixture of the calcium salt of lignosulfonic acid and the sodium salt of N-methyl-N-oleyl-taurine

2.) 40% by weight of active ingredient
25% by weight of 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 sodium aluminum silicate
15% by weight of cetyl polyglycol ether with 8 moles of ethylene oxide
2% by weight spindle oil
10% by weight polyethylene glycol
23% by weight of water

C) Emulsion concentrate

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

The following examples illustrate the preparation of the invention Links:

Example 1 Methyl 2- (4,6-dimethoxy-2-pyrimidinylthio) -2-phenylthioacetic acid-r

5 g (27.4 mmol) methyl phenylmercaptoacetate, 5.8 g (32.8 mmol) N-bromosuccinimide and 0.1 g benzoyl peroxide are dissolved in 150 ml carbon tetrachloride suspended and heated to reflux for 45 minutes. Then you cool the batch to 5 ° C, the solid is filtered off and the yellow solution is concentrated Rotary evaporator. The oil thus obtained (7.1 g) is dissolved in 50 ml of dimethylformamide and dropwise the solution to a suspension of 4.68 g (27.1 mmol) 2-mercapto-4,6-dimethoxypyridine and 1.87 g (13.5 mmol) potassium carbonate in 50 ml of dimethylformamide. The approach is 16 hours at room temperature touched. Then the reaction mixture is poured onto 150 ml of ice water and extracted three times with 100 ml of ethyl acetate. The combined ethyl acetate phases are washed with water, dried over magnesium sulfate and constricted. The oil thus obtained is purified by column chromatography on silica gel cleaned with hexane / ethyl acetate mixtures.

Yield: 3.64 g = 37.9% of theory
Mp: 69-70 ° C

Example 2 2- (4,6-Dimethoxy-2-pyrimidinylthio) -2-phenylthioacetic acid

1.5 g (4.3 mmol) of 2- (4,6-dimethoxy-2-pyrimidinylthio) -2-phenylthioacetic Acid methyl ester are suspended in 25 ml of water and 10 ml of methanol, with 0.24 g (4.3 mmol) of potassium hydroxide were added and the mixture was heated at 80 ° C. for 3 hours. The solution is then acidified to pH 2 with 10% hydrochloric acid and extracted three times with 50 ml of ethyl acetate, the organic phase washes with water, dries them with sodium sulfate and concentrates them on a rotary steamer Dry one.

Yield: 0.41 g = 29.3 of theory
Mp: 114-115 ° C

Example 3 2-Ethoxy-2- (4,6-dimethoxy-2-pyrimidinyloxy) acetic acid methyl ester

6.4 g (36.3 mmol) of 2-ethoxy-2-hydroxyacetic acid ethyl ester (85%) are in 50 ml of dimethylformamide dissolved and mixed with 2.5 g (36.3 mmol) of potassium carbonate puts. After stirring for 20 minutes, 8.0 g (36.3 mmol) of 4,6-dimethoxy-2- methylsulfonylpyrimidine added and heated to 90 ° C for 12 hours. The Re Action mixture is poured onto 100 ml of ice water and three times with 100 ml each Extracted ethyl acetate. The combined ethyl acetate phases are with water washed, dried over sodium sulfate and concentrated. The backlog will by column chromatography on silica gel with hexane / ethyl acetate mixtures cleaned. The oil obtained after chromatography is made from diisopropyl ether recrystallized.

Yield: 2.3 g = 21.1 of theory
Mp .: 71-72 ° C

Example 4 2- (4,6-Dimethoxy-2-pyrimidinylthio) -2-phenoxyacetic acid methyl ester

10 g (60.2 mmol) methyl phenoxyacetate, 12.8 g (72.2 mmol) N-bromo succinimide and 0.1 g benzoyl peroxide in 300 ml carbon tetrachloride sus oscillated and heated to reflux for 45 minutes. Then you cool the Approach to 5 ° C, the solid is filtered off and the yellow solution is concentrated on a ro station steamer. The oil thus obtained (14.7 g) is dissolved in 100 ml of di methylformamide and drips the solution into a suspension of 10.3 g (60 mmol) 2-mercapto-4,6-dimethoxypyrimidine and 4.1 g (30 mmol) potassium carbonate in 150 ml of dimethylformamide. The approach is 16 hours at room temperature touched. Then the reaction mixture is poured onto 200 ml of ice water and extracted three times with 150 ml of ethyl acetate. The combined ethyl acetate phases are washed with water, dried over sodium sulfate and a narrowed. The oil obtained in this way is obtained by column chromatography on silica gel cleaned with hexane / ethyl acetate mixtures.

Yield: 2.8 g = 13.9 of theory
Mp .: 67-68 ° C

The following examples explain the possible uses of the inventions connections according to the invention.

Example A

The plant species listed were in the greenhouse before emergence with the compound according to the invention in an application rate of 0.3 kg Active ingredient / ha treated. The compound was used as an emulsion for this purpose sprayed evenly over the plants with 500 liters of water / ha. Here showed the compound of the invention 3 weeks after treatment high crop selectivity in wheat (TRZAX), cotton (GOSHI), So jabohne (GLXMA) and maize (ZEAMX) with excellent effects against the Un herb. The comparative agent did not show the same 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

GLXMA = Glycine max
GOSHI = Gossypium hirsutum
TRZAX = Triticum aestivum
ZEAMX = Zea mays
MATCH = Matricaria chamomilla
POLSS = Polygonum sp.
SOLSS = Solanum sp.
VERPE = Veronica persica

Example B

The plant species listed were in the greenhouse after emergence with the compound according to the invention in an application rate of 0.1 kg of active ingredient fabric / ha treated. The compound was used as an emulsion for this purpose Sprayed 500 liters of water / ha evenly over the plants. Here showed 2 Weeks after treatment, the compound according to the invention has a high cult Plant selectivity in wheat (TRZAX), maize (ZEAMX) and soybean (GLXMA) with excellent activity against weeds. The means of comparison 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

GLXMA = Glycine max
TRZAX = Triticum aestivum
ZEAMX = Zea mays
SEBEX = Sesbania exaltata
SOLSS = Solanum sp.
VERPE = Veronica persica

Claims (7)

1. Substituted α-pyrimidinyloxy (thio) - and α-triazinyloxy (thio) acetic acid derivatives of the general formula I in the
A is one of groups A-1 to A-6 of the general formulas a C₁-C₁₀ alkyl radical, one or more, the same or different by C₁-C₄-alkoxy, C₁-C₄-alkylthio, amino, C₁-C₄-alkylamino, di-C₁-C₄-alkylamino, nitro, halogen or Phenyl substituted C₁-C₄-alkyl radical, a C₂-C₁₀ alkenyl radical, one or more, the same or different by C₁-C₄-alkoxy, C₁-C₄-alkylthio, amino, C₁-C₄-alkyl amino, di-C₁ -C₄-alkylamino, nitro, halogen or phenyl substituted C₂-C₁₀ alkenyl radical, a C₂-C₁₀ alkenyl radical, one or more, identically or differently by C₁-C₄-alkoxy, C₁-C₄-alkylthio, amino, C₁- C₄-alkylamino, di-C₁-C₄-alkylamino, nitro halogen or phenyl substituted C₂-C₁₀-alkenyl radical, a C₃-C₈-cycloalkyl radical, one or more, the same or different, by C₁-C₄-alkyl, C₁-C₄- Alkoxy, C₁-C₄-alkylthio, amino, C₁-C₄-alkylamino, di-C₁-C₄-alkylamino, nitro, halogen or phenyl substituted C₃-C₈-cycloa lkylrest, a C₄-C₈-cycloalkenyl radical or one or more, identical or different by C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, amino, C₁-C₄-alkylamino, di-C₁-C₄ alkylamino, nitro, halogen or phenyl substituted C₄-C₈-cycloalkenyl radical,
D is an oxygen atom, a sulfur atom or a group -NR⁹-,
R¹ is a hydrogen atom, a C₁-C₁₂ alkyl radical, a gene by hydroxy, halo, C₁-C₄-alkoxy, C₁-C Alkyl-alkylthio, C₃-C₆-cycloalkyl, benzyl, furyl, Te trahydrofuryl, phenyl, halophenyl, C₁-C₄ -Alkylphenyl, C₁-C₄-alkoxy phenyl, nitrophenyl, cyano, carboxyl, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylamino or di-C₁-C₄-alkylamino substituted C₁-C₁₂-alkyl, one or more oxygen atoms or Sulfur atoms interrupted C₂-C₁₂-alkyl radical, one interrupted by one or more oxygen atoms or sulfur atoms and by hydroxy, halogen, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, benzyl, furyl, tetrahydrofuryl, phenyl, Halophenyl, C₁-C₄-alkylphenyl, C₁-C₄-alkoxyphenyl, nitrophenyl, cyano, carboxyl, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylamino or di-C₁-C₄-alkylamino substituted C₂-C₁₂-alkyl radical, a C₃-C₈ -Alkenylrest, egg nen by C₁-C₃-alkoxy, phenyl or halogen sub substituted C₃-C₈-alkynyl radical, a C₃-C₈-alkynyl radical, a C₃-C₃-alkoxy, phenyl or halogen-substituted C₃-C₈-alkynyl radical, a C₃-C₆-cycloalkyl radical, a methyl-substituted C₃-C₆-cycloalkyl radical, a di-C₁-C₄- alkylmethyleneimino or a C₃-C₆-cycloalkyleneimino,
R² is a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, a C₁-C₄-alkylthio radical, a C₁-C₄-alkylamino radical, a di-C₁-C₄-alkylamino radical or a halogen atom,
R³ is a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, a C₁-C₄-alkylthio radical, a C₁-C₄-alkylamino radical, a di-C₁-C₄-alkylamino radical or a halogen atom,
R⁴ is a hydrogen atom, a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, an amino radical, a di-C₁-C₄-alkylamino radical, a nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical,
R⁵ is a hydrogen atom, a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, an amino radical, a di-C₁-C₄-alkylamino radical, a nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical,
a trifluoromethyl radical or a phenyl radical,
R⁶ is a hydrogen atom, a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, an amino radical, a di-C₁-C₄-alkylamino radical, a nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical,
R⁷ is a hydrogen atom, a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, an amino radical, a di-C₁-C₄-alkylamino radical, a nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical,
R⁸ is a hydrogen atom, a C₁-C₄-alkyl radical, a C₁-C₄-alkoxy radical, an amino radical, a di-C₁-C₄-alkylamino radical, a nitro radical, a halogen atom, a trifluoromethyl radical or a phenyl radical,
R⁹ is a hydrogen atom or a C₁-C₄ alkyl radical,
X is an oxygen atom or a sulfur atom,
Y is a methine group or a nitrogen atom and
Z is an oxygen atom or a sulfur atom
mean, and their alkali metal salts, alkaline earth metal salts, ammonium salts, or organically substituted ammonium salts and their optically active isomers. 2. A process for the preparation of compounds of general formula I, according to claim 1, characterized in that

• A) Compounds of the general formula II in which R², R³ and Y have the meanings given under the general formula I and V represents a halogen atom, an alkylsulfinyl group, a phenylsulfinyl group, an alkylsulfonyl group or a phenylsulfonyl group, with compounds of the general formula III in which A, R¹, X and Z have the meanings given under the general formula I, in a suitable solvent in the presence of a suitable base, or
• B) Compounds of the general formula IV in which A, R¹, R², R³, X, Y and Z 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 form compounds of the general formula V. in which A, R², R³, X, Y and Z have the meanings given under the general formula I and M¹ represents an alkali metal atom or an equivalent of an alkaline earth metal atom, or
• C) Compounds of the general formula V in which A, R², R³, M¹, X, Y and Z 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 in which A, R², R³, X, Y and Z have the meanings given under the general formula I, or
• D) Compounds of the general formula VI in which A, R², R³, X, Y and Z 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 in which A, R², R³, X, Y and Z have the meanings given under the general formula I and M² represents an all-alkali metal atom, an equivalent of an alkaline earth metal atom, an ammonium ion or an organically substituted ammonium group, or
• E) Compounds of the general formula VIII in which R², R³, X and Y have the meanings given under general formula I, with a compound of general formula IX in which A, R¹ and Z have the meanings given under the general formula I and W represents a halogen atom, an alkylsulfinyl group or an alkylsulfonyloxy group, in the presence of a suitable solvent and a suitable base, or
• F) a compound of the general formula X in which R¹, R², R³, X and Y have the meanings given under the general formula I, with a suitable halogenating reagent, in a suitable solvent and the compounds thus obtained of the general formula XI in which R¹, R², R³, X and Y have the meanings given under the general formula I and Hal represents a halogen atom, with a compound of the general formula XIIA-ZH (XII), in which A and Z are those under the general Formula I have meanings, reacted in a suitable solvent with a suitable base.

3. Agents with herbicidal, fungicidal and plant growth regulating Effect, characterized by a content of at least one compound according to claim 1. 4. Use of agents according to claim 3 for combating monocotyledons and dicotyledonous weed species in main agricultural crops. 5. Use of agents according to claim 3 for combating a fungus fall in agricultural crops. 6. Use of agents according to claim 3 for influencing the growth of Crops. 7. Process for the preparation of herbicidal, fungicidal and growth-regulating effect, characterized in that Verbin extensions of general formula I according to claim 1 with carrier and / or Auxiliary materials mixed.