DE3632492A1 - HERBICIDES PHENOXY-BENZOYL-MALONIC ACID ESTER DERIVATIVES - Google Patents

Description

The invention relates to new phenoxy-benzoyl-malonic acid esters. Derivatives, a process for their preparation, herbicidal compositions containing these compounds and Weed control method using above means.

It is known that certain phenoxy-benzoic acid Derivatives show a herbicidal effect. Such connections are disclosed in U.S. Patent Nos. 39 79 437 and 36 52 645 described.

The invention relates on the one hand to new phenoxy-benzoyl-malonic acid ester derivatives of the general formula I / wherein R ^{1 is} halogen, cyano, nitro, methylthio, trifluoromethyl or C _1-4 alkyl;
R ² and R ^{3 are} independently hydrogen, halogen or trifluoromethyl;
R ^{4 is} hydrogen, halogen, cyano or nitro and R ^{5 is} C _1-4 alkyl /.

Differentiate the new compounds of general formula I. from the known derivatives in the structure of the to the Carbonyl group bound group.

The new compounds according to the invention are in their herbicidal activity - especially in pre-emergent Treatment - the known derivatives of similar structure significantly superior. The new connections of the general Formula I can be used in several crops - especially in corn - for the selective control of grassy  and broad-leaved weeds can be used successfully.

It is an advantageous representative of the compounds of the general formula I in which R ^{1 is} trifluoromethyl, R ^{2 is} chlorine, R ^{3 is} hydrogen, R ^{4 is} nitro and R ^{5 is} ethyl.

It is a further advantageous representative of the compounds of the general formula I in which R ^{1 is} trifluoromethyl, R ² and R ^{3 are} chlorine, R ^{4 is} nitro and R ^{5 is} ethyl.

It is another advantageous representative of the compounds of the general formula I in which R ¹ and R ^{2 are} chlorine, R ^{3 is} hydrogen, R ^{4 is} nitro and R ^{5 is} ethyl.

The term "C _1-4 alkyl" means straight-chain or branched alkyl groups with 1-4 carbon atoms / z. As methyl, ethyl, n-propyl, isopropyl, n-butyl etc./.

The invention further relates to herbicidal compositions which, as an active ingredient in an amount of 0.01-95% by weight, contain a compound of the general formula I / in which R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the above meaning / and suitable inert solid and / or liquid carriers or diluents and optionally auxiliaries / z. B. surfactants, anti-foaming agents, adhesives, antifreezes, etc./ contain.

The herbicidal compositions according to the invention can in Agriculture and crop protection usual forms completed will / z. B. powder mixtures, spray powder, granules, Pastes, emulsions, solutions, suspensions, etc./. The herbicidal Agents can contain conventional carriers and auxiliaries.

As solid supports such. B. used the following products minerals or synthetic substances such as kaolin, Silica, talc, attapulgite, diatomaceous earth, aluminum oxide, Silica and various silicates. As a liquid diluent can e.g. B. Use the following liquids find: petroleum fractions with different boiling point intervals / z. B. gas oil, kerosene /, oils of animal or vegetable origin; aromatic, aliphatic or alicyclic hydrocarbons / z. B. benzene, toluene, xylene, cyclohexane, tetrahydronaphthalene / and their derivatives / z. B. chlorobenzene, carbon tetrachloride, alkylated naphthalene derivatives, cyclohexanone,  Butanol, etc./; strongly polar solvents / such as dimethylformamide, Dimethyl sulfoxide, N-methyl pyrrolidone, water, etc /.

The surfactants / e.g. B. emulsification, dispersion, Wetting and foam control agents, anti-aggregation agents, etc./ can be ionic or non-ionic Connections. As an ionic surfactant can e.g. B. the following connections are used: Salts of saturated or unsaturated carboxylic acids; Aliphatic, aromatic or araliphatic sulfonates Hydrocarbons; Sulfonates of alkyl, aryl or Aralkyl alcohols; Sulfonates of alkyl, aryl or aralkyl carboxylic acids, star and ether; Sulfonates from condensation products of phenols, crezoles or naphthalene derivatives; sulfated vegetable or animal oils, alkyl, aryl or aralkyl phosphate esters; or sulfonates or phosphates of polyglycol ethers of ethylene oxide and fatty alcohols or Alkylphenols.

As nonionic surfactants, the the following substances are mentioned: condensation products from Ethylene oxide and fatty alcohols: alkylaryl polyglycol ether; Ethylene oxide and / or propylene oxide block polymers and derivatives of which: alkyl cellulose.

As a foam control agent such. B. condensation products of ethylene oxide / propylene oxide with a low Molecular weight; aliphatic alcohols, special silicone oils or fatty acid anides can be used.

Suitable adhesives or thickeners are first row the alkaline earth metal soaps; Sulfosuccinic acid ester salts and the natural or synthetic water-soluble ones or macromolecular substances swellable in water.

As an antifreeze agent, ethylene glycol can be used and propylene glycol or glycerin.

The herbicidal compositions according to the invention can in known way to be made by connecting of general formula I with suitable inert solid and / or liquid carriers or diluents and optionally mixed with auxiliaries.  

The invention further relates to a method for Fight weeds by looking at the objects to be protected - such as B. plants, parts of plants or soil - with an effective amount of a compound of the general Formula I or an agent containing such a compound treated.

The invention further relates to a process for the preparation of compounds of the general formula I / in which R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the above meaning / by
a / a phenoxy-benzoic acid derivative of the general formula II / wherein R ¹ , R ² , R ³ and R ^{4 have} the above meaning and Y represents halogen, cyano or C _1-6 alkyl-carbonyloxy / with a metal derivative of a malonic ester of the general formula III / wherein R ^{5 has} the above meaning / or in the presence of a metal compound - preferably magnesium chloride - with a malonic ester of the general formula III; or b / a phenol of the general formula IV / wherein R ¹ , R ² and R ^{3 have} the above meaning / or an alkali metal salt thereof with a benzoic acid derivative of the general formula V converts / in which R ⁴ and R ^{5 have} the above meaning and Z represents halogen /.

According to process variant a / of the invention Process can preferably be the sodium, potassium or Magnesium derivatives of the malonates of the general formula III be used. If you use a free connection the general formula III, the implementation is preferred in the presence of magnesium compounds - especially magnesium chloride - performed as a metal compound. The implementation can be advantageously carried out in an inert solvent will. Hydrocarbons come as inert solvents / z. B. benzene, toluene, xylene /, ether / z. B. diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or dioxane /, Amides / z. B. Dimethylformamide, Hexamethylphosphorsäuretriamid /, Ketones / e.g. B. acetone or diethyl ketone /, nitriles / z. B acetonitrile /, etc. into consideration.

The malonic esters of the general formula III are in the form their metal salts with the compounds of general formula II implemented. The malonic ester metal salts can be obtained from the Compounds of general formula III by reaction with Alkali metal or alkaline earth metal compounds / or organometallic Connections / to be established beforehand. Man can however also proceed in such a way that the connections of the general formulas II and III in the presence of metal compounds - advantageous magnesium chloride - is implemented, wherein the metal salts of the compounds of general formula III be formed in situ in the reaction mixture.

The reaction is carried out at a temperature between -10 and  +180 C ° - preferably at 30-100 C ° - carried out. The Products obtained can - if necessary after removal of the by-products formed - according to known methods be isolated.

The malonic esters of the general formula III, the metal salts thereof and the starting materials of the general formula II are partially known. Such connections are in the U.S. Patent Nos. 39 79 437 and 36 52 645 and in the publications Org. Synth. Coll. Vol. 285 IV. And J. Org. Chem. 50, 2622/1985 /. The new connections of the general Formula II can be analogous to that in the cited references disclosed methods prepared will.

According to process variant b /, the starting materials of the general formulas IV and V appropriately in the presence of a inert solvent or diluent implemented. As a reaction medium can those listed in process variant a / Serve solvents. The reaction can be beneficial be carried out in the presence of an acid binder. Alkali metal hydroxides are suitable for this purpose; -carbonates, ethylates or tert. butylates / z. B. sodium or potassium hydroxide, carbonate, ethylate or tert. Butylate / or organic Bases / like triethylamine, etc./.

Further details of the invention are as follows Take examples without the scope of protection on these examples restrict.

Example 1 Preparation of 5- / 2-chloro-4-trifluoromethylphenoxy / -2- nitro-benzoyl-malonic acid diethyl ester

a / A solution of 38.0 g of 5- / 2-chloro-4-trifluoromethyl phenoxy / -2-nitro-benzoyl chloride and 50 ml of benzene Room temperature with stirring within 20 minutes of ethoxy magnesium malonate made from 17.6 g of diethyl malonate  added dropwise in 50 ml of benzene. After completion The reaction mixture is added for one hour heated under reflux and then cooled. The viscous 50 ml of 20% sulfuric acid are added to the solution with stirring. The phases are separated and the aqueous layer is extracted twice with 50 ml of benzene. The extracts are combined with water and a sodium bicarbonate solution washed and concentrated. It comes in the form of a yellow oil Obtained 47.8 g of the compound mentioned in the title. Mp .: 72-76 ° C.

b / a mixture of 19.7 g of 2-chloro-4-trifluoromethylphenol, 32.7 g of 2-nitro-4-fluoro-benzoyl-malonic acid diethyl ester, 13.8 g of potassium carbonate and 100 ml of anhydrous dimethyl sulfoxide is stirred at 50 ° C. After a response time of 24 hours the reaction mixture is diluted with 100 ml of water and extracted three times with 50 ml of benzene. The benzene phase is dried over anhydrous magnesium sulfate and the solvent is distilled off. The yellow oil obtained is removed recrystallized from a mixture of benzene and hexane. It will Obtained 40.3 g of the compound mentioned in the title. Mp .: 72-76 ° C.

c / A mixture of 21.9 g sodium 2-chloro-4-trifluoromethyl phenolate, 32.7 g of 2-nitro-4-fluoro-benzoyl-malonic acid diethyl ester and 100 ml of anhydrous dimethyl sulfoxide stirred at 50 ° C. After a response time of 24 hours the reaction mixture is diluted with 100 ml of water and extracted three times with 50 ml of benzene. The benzene phase is Dried over anhydrous magnesium sulfate and evaporated. The yellow oil obtained is made from a mixture of benzene and recrystallized hexane. There will be 39.8 g of the in the title receive the named connection. Mp .: 72-76 ° C.  

Example 2 Preparation of 5- / 2,6-dichloro-4-trifluoromethylphenoxy / - 2-nitro-benzoyl-malonic acid diethyl ester

A solution of 45.8 g of 5- / 2,6-dichloro-4-trifluoromethyl phenoxy / -2-nitro-benzoyl bromide and 50 ml of ether is added Stir a solution of at room temperature within 20 minutes Diethyl potassium malonate prepared from 17.6 g of diethyl malonate and 50 ml ether added dropwise. After completing the The reaction mixture is added under reflux for one hour heated, then cooled, whereupon 50 ml of 20% with stirring Sulfuric acid can be added. The phases are different from each other separated, the aqueous layer is twice with 50 ml Ether extracted. The organic phases are combined, one after the other washed with water and a sodium carbonate solution and constricted. The yellow oil obtained solidifies slowly. There will be 49.9 g of the compound mentioned in the title receive. Mp .: 84-88 ° C.

Example 3 Preparation of 5- / 2-chloro-4-trifluoromethylphenoxy / - 2-chloro-benzoyl-malonic acid diethyl ester

One cooled to 0 ° C with a salt-ice mixture Mixture of 35.0 g 5- / 2-chloro-4-trifluoromethyl-phenoxy / -2- chlorobenzoic acid, 10.0 g triethylamine and 100 ml toluene become 12.1 g of pivaloyl chloride at such a rate admitted that the temperature does not exceed 0 ° C. During the addition and subsequent stirring period / approximately 15-20 minutes / excretes triethylamine hydrochloride. The Feeding device of pivaloyl chloride is against a dropping funnel exchanged which one from 17.6 g of diethyl malonate prepared etheric ethoxymagnesium malonate solution contains. The ethereal solution is added dropwise, with the Temperature is kept between -5 and 0 ° C. The reaction mixture is left overnight, after which 200 ml of a 5% sulfuric acid solution are added. The watery  Phase is extracted twice with 50 ml ether. The United organic phases are diluted with sulfuric acid and a sodium bicaronate solution, over anhydrous Dried sodium sulfate and concentrated. It will in the form of pale yellow crystals 44.3 g of that in the title receive the named connection. Mp: 59-65 ° C.

Example 4 Preparation of 5- / 2,4,6-trichlorophenoxy / -2-nitro-benzoyl malonic acid diethyl ester

In a 500 ml provided with a stirrer and dropping funnel Flasks are 9.52 g of anhydrous magnesium chloride and 100 ml Weighed in anhydrous acetonitrile. The heterogeneous mixture 16.0 g of diethyl malonate are added, followed by the flask is placed in an ice bath and 28 ml of triethylamine are added will. The solution is stirred at 0 ° C. for 15 minutes, followed by 38.1 g of 5- / 2,4,6-trichlorophenoxy / -2-nitro-benzoyl chloride be added dropwise. The reaction mixture becomes a Hour at 0 ° C and 12 hours at room temperature stirred and finally cooled to 0 ° C. The mixture will 60 ml of a 5 M hydrochloric acid solution were added. The resulting one Solution is extracted three times with 100 ml ether, and the combined extracts are dried over magnesium sulfate. After removing the solvent and traces of diethyl malonate a pale yellow oil is obtained which slowly solidifies. There will be 45.0 g of the compound mentioned in the title receive. Mp .: 71-73 ° C.

Example 5

The following 19 compounds of the general formula I are prepared in an analogous manner to the previous examples 1-4. The definition of the substituents R ¹ -R ⁵ , the melting points and the characteristic features of the NMR spectra are summarized in Table I.

Table I

Formulation examples Example 6 Granules containing 0.01% of active ingredient

From 2.3 g of active ingredient No. 1 / technical quality, purity 89% / and 97.7 g methylene chloride becomes a 2% solution produced. In a Lödige 20 eddy current mixer 4000 g of one are made from diatomaceous earth by calcination acidic pearl silicic acid weighed / average Particle diameter 0.5-2 mm /. On the granular support through a nozzle head Tee-Jet 10080 at a speed of 5 g / min. 20 g of an active ingredient mixture / a 2% mm / m Solution / sprayed, the mixture in the mixer with a Speed of 50 revolutions / min. is stirred. The granules of the sorption type are finally packed.

Example 7 Sprayable powder containing 95% of active ingredient

240 g of the active ingredient No. 2 / purity 97% / are ground in a mill equipped with a rotating steel / of the coffee grinder type / and the ground material is ground in a grater with 2.5 g of an amorphous silica / Cab-O-Sil M5: Carrier / and 7.5 g of a dispersant No. 1495 / sodium salt of the condensation product of sulfonated cresol and formaldehyde / mixed. The powdery mixture is ground in an eddy current mill / Alpine JMRS-80 / under an injector air pressure of 5 bar and a grinding air pressure of 4.5 bar with a feed rate of 250 g / piece. Although the wettable powder obtained in this way does not contain a separate wetting agent, it is readily wettable. The maximum particle diameter is 20 µm. In a spray liquor with a concentration of 10 g / l at 30 ° C after 30 minutes, the suspension in CIPAC Standard D water is 84% and
in CIPAC Standard A 91%.

Example 8 Emulsion concentrate containing 24% of active ingredient

In 400 g of cyclohexanone at 40-45 ° C 40 g of Tween 85 / ethoxylated sorbitan trioleate / and 30 g sapogenate T-180 / ethoxylated tributylphenol / as an emulsifier and 250 g active ingredient no.7 / technical quality, purity 96% / solved. Dissolution is promoted by stirring. After completion the dissolution becomes the active ingredient solution / temperature 40-45 ° C / with vigorous stirring in a mixture of 200 g ion-exchanged water and 700 g of ethylene glycol poured, after which the mixture slowly to 15-20 ° C is cooled back. Before stirring is complete, the Emulsion 10 g of a foam control agent / silicone SRE; a 30% emulsion of a dimethyl silicone oil / added and 5 minutes later the stirring is stopped.

Example 9 Biological application example

Grass seeds and seeds of the crops are in one Plastic container / size 10 × 10 × 0 cm / in sand of the Danube river sown. Different amounts of the test compounds containing withered emulsifiable concentrates the sand surface / pre-emergent treatment / or three Weeks after sowing / post-emergent treatment / sprayed. The plastic containers are used for normal plant growth watered and in required amount of water daily kept in a greenhouse. The results of the trials will be after 4 weeks using a scale between 0 and 10 rated: 0 = no symptoms; 10 = 100% infected, destroyed Plants.

Two herbicidal commercial products are used as reference compounds:
Acifluorfen / chemical nomenclature: sodium 5- / 2-chloro-4-trifluoromethyl-phenoxy / -2-nitro-benzoate and
Oxifluorfen / chemical nomenclature: 2-chloro-1- / 3-ethoxy-3-nitro-phenoxy / 4-trifluoromethyl-benzene /.

The results are summarized in Table II. It appears from these figures that the average Effectiveness of the new compounds according to the invention against grassy and broad-leaved weeds - especially in pre-emergent treatment - the same of the reference reference substances is clearly superior.

The tolerance of different crops The compositions according to the invention are based on the in this Example described treatment methods determined. It works the test results showed that dicotyledonous crops well tolerated all compositions according to the invention; there are no phytotoxic at all in the herbicidal doses Symptoms. It was also found that with pre-emergent treatment corn, sunflower and legumes tolerate the compositions according to the invention very well. In contrast, the reference compounds are oxifluorfen and acifluorfen only from the soybean plant in such treatment tolerate.

Table II Herbicidal activity of the compounds of the general formula I on various weeds and crop plants in the case of pre-emergent and post-emergent treatment

Claims (12)

1. Phenoxy-benzene-malonic ester derivatives of the general formula I / wherein R ^{1 is} halogen, cyano, nitro, methylthio, trifluoromethyl or C _1-4 alkyl;
R ² and R ^{3 are} independently hydrogen, halogen or trifluoromethyl;
R ^{4 is} hydrogen, halogen, cyano or nitro and
R ^{5 is} C _1-4 alkyl /. 2. Compounds according to claim 1, characterized in that R ^{1 is} trifluoromethyl, R ^{2 is} chlorine, R ^{3 is} hydrogen, R ^{4 is} nitro and R ^{5 is} ethyl. 3. compounds according to claim 1, characterized in that R ^{1 is} trifluoromethyl, R ² and R ^{3 are} chlorine, R ^{4 is} nitro and R ^{5 is} ethyl. 4. Compounds according to claim 1, characterized in that R ¹ and R ^{2 are} chlorine, R ^{3 is} hydrogen, R ⁴ nitro and R ^{5 is} ethyl. 5. Herbicidal preparation, characterized in that it is an active ingredient in an amount of 0.01-95% by weight of a phenoxy-benzoyl-malonic acid ester derivative of the general formula I. / wherein R ^{1 is} halogen, cyano, nitro, methylthio, trifluoromethyl or C _1-4 alkyl;
R ² and R ^{3 are} independently hydrogen, halogen or trifluoromethyl;
R ^{4 is} hydrogen, halogen, cyano or nitro and R ^{5 is} C _1-4 alkyl /,
and suitable inert solid and / or liquid carriers and diluents - preferably silica, silica and / or cyclohexanone - and optionally other auxiliaries - preferably surface-active agents, such as. B. ethoxylated tributylphenol or alkyl sulfonates - contains. 6. Herbicidal composition according to claim 5, characterized in that it contains as active ingredient a compound of general formula I, in which R ^{1 is} trifluoromethyl, R ^{2 is} chlorine, R ^{3 is} hydrogen, R ^{4 is} nitro and R ^{5 is} ethyl. 7. Herbicidal composition according to claim 5, characterized in that it contains as active ingredient a compound of general formula I in which R ^{1 is} trifluoromethyl, R ² and R ^{3 are} chlorine, R ^{4 is} nitro and R ^{5 is} ethyl. 8. Herbicidal composition according to claim 5, characterized in that it contains as active ingredient a compound of general formula I, wherein R ¹ and R ^{2 are} chlorine, R ^{3 is} hydrogen, R ⁴ nitro and R ^{5 is} ethyl. 9. Process for the preparation of compounds of general formula I. / wherein R ^{1 is} halogen, cyano, nitro, methylthio, trifluoromethyl or C _1-4 alkyl;
R ² and R ^{3 are} independently hydrogen, halogen or trifluoromethyl;
R ^{4 is} hydrogen, halogen, cyano or nitro and R ^{5 is} C _1-4 alkyl /,
characterized in that one
a / a phenoxy-benzoic acid derivative of the general formula II / wherein R ¹ , R ² , R ³ and R ^{4 have} the above meaning and Y represents halogen, cyano or C _1-6 alkyl-carbonyloxy / with a metal derivative of a malonic ester of the general formula III / wherein R ^{5 has} the above meaning / or in the presence of a metal compound - preferably magnesium chloride - with a malonic ester of the general formula II; or
b / a phenol of the general formula IV / wherein R ¹ , R ² and R ^{3 have} the above meaning / or an alkali metal salt thereof with a benzoic acid derivative of the general formula V converts / in which R ⁴ and R ^{5 have} the above meaning and Z represents halogen /. 10. Process for the preparation of phenoxy-benzoyl-malonic acid esters of the general formula I / wherein R ^{1 is} halogen, cyano, nitro, methylthio, trifluoromethyl or C _1-4 alkyl;
R ² and R ^{3 are} independently hydrogen, halogen or trifluoromethyl;
R ^{4 is} hydrogen, halogen, cyano or nitro and R ^{5 is} C _1-4 alkyl /,
characterized in that a benzoic acid derivative of the general formula II / wherein R ¹ , R ² , R ³ and R ^{4 have} the above meaning and Y is halogen, cyano, nitro, ethyl carbonyloxy or tert. Butylcarbonyl stands / with a metal derivative of a malonic ester of the general formula III / where R ^{5 has} the meaning given above /. 11. A process for the preparation of herbicidal compositions according to any one of claims 5 to 8, characterized in that a compound of general formula I / wherein R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meaning given in claim 3 / in an amount of 0.01-95 wt.% With inert, solid and / or liquid carriers or diluents and optionally mixed with other auxiliaries. 12. Weed control method, thereby characterized in that the objects to be protected - e.g. B. the plants, parts of plants or soil - with an effective amount of a compound of the general Formula I or an agent containing such a compound treated.