NL8602481A - HERBICIDE EFFECTIVE PHENOXYBENZOYL MALONATES. - Google Patents

Description

NL 33742-Kp / cs ** "

Herbicidal active phenoxybenzoyl malonates.

The present invention relates to herbicidally active phenoxybenzoyl malonates, to a method for their preparation, to herbicidal compositions containing such malonates, as well as to a method of controlling weeds using said compositions.

Certain phenoxybenzoic acid derivatives are known to have herbicidal activity. Such compounds are described in U.S. Pat. Nos. 3,979,437 and 3,652,645.

In accordance with one aspect of the present invention, these are new phenoxybenzoyl malonates of the general formula 1 0 n l (5 o, c-0 yr> 2 c-CHv.

ir ~ K / rO c-or5 r II (1> where 15 R represents C1-4 alkyl / halogen, cyan, nitro, methylthio or trifluoromethyl, o 3 R and R which may or may not be equal to each other, hydrogen, halogen or trifluoromethyl, R4 is hydrogen, halogen, cyano or nitro, while R5 represents C1-4 alkyl (not the same).

The new compounds of the general formula 1 differ from the known derivatives in the structure of the moiety, which is attached to the carbonyl group.

The new compounds of the general formula (I) have significantly stronger herbicidal activity - especially a pre-emergence herbicidal activity - than the chemically related known derivatives. The compounds according to the invention are particularly suitable when used before the emergence of the plants in the selective control of grassy and broad-leaved weeds S6Ö248 1 * i S * - 2 - in various crops, in particular maize .

In a preferred subgroup of the compounds with the

1 2 general formula 1 R represents chlorine or trifluoromethyl, R.

3 4 chlorine, R hydrogen or chlorine, R nitro, halogen or cyano and 5 R5 ethyl.

Preferred compounds of general formula 1 are 1 2 3 4

those in which R trifluoromethyl, R chlorine, R hydrogen, R

Nitro and R is ethyl.

Another preferred group is represented by those compounds of the general formula 1, wherein R is trifluoro-2 3 4 5

methyl is, R and R represent chlorine, R is nxtro and R.

ethyl.

Another preferred group consists of compounds 12 3

of the general formula 1, wherein R and R are chlorine, R

4 5 15 is hydrogen, R represents nitro and R is ethyl.

The term alkyl "refers to straight or branched chain alkyl groups of 1-4 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.).

In accordance with a further aspect of the present invention, these are herbicidally active preparations having as active ingredient 0.01-95% by weight of a compound of the general formula 1 (wherein R, R, R and R have the above meanings mixed with suitable inert solid and / or liquid carriers or diluents and optionally auxiliaries (eg surfactants, anti-foaming agents, antifreeze and adhesives, etc.).

The compositions of the invention can be solid or liquid and can be incorporated in conventional forms (eg powder mixture, fine powder, granules, paste, emulsion, suspension, solution, spray, concentrate, etc.). The preparations contain diluents and carriers as well as auxiliaries commonly used in agriculture and in plant protection.

The solid supports can be mineral or synthetic materials, for example, Chinese clay, silica, talc, attapulgite, diatomaceous earth, aluminum oxide, silica and various silicates. As liquid diluent, for example, mineral oil fractions (e.g. gas oil or kerosene), oils of animal or vegetable origin; aromatic 8602431-3 - aliphatic or alicyclic hydrocarbons (e.g. benzene, toluene, xylene, cyclohexane, tetrahydronaphthalene, etc.) and derivatives thereof (e.g. chlorobenzene, alkylnaphthalenes, cyclohexanol, butanol, etc.) or strong polar solvents ( for example dimethylformamide, dimethylsulfoxide, N -methyl-pyrrolidone, water, etc.) are used.

The surfactants (emulsifying agents, dispersing agents, wetting agents, anti-foaming agents or anti-aggregating agents) may be of the ionic or non-ionic type. As ionic surfactants, the following compounds can be used: salts of saturated or unsaturated carboxylic acids; sulfonates of aliphatic, aromatic or aliphatic-aromatic hydrocarbons, sulfonates of alkyl, aryl and aralkyl alcohols; sulfonates of alkyl, aryl and aralkyl carboxylic acids and their esters and ethers; sulfonates of condensation products of phenols, cresols or naphthalene; sulfated oils of animal or vegetable origin; alkyl, aryl or aralkyl-20 phosphate esters; sulfonates and phosphates of polyglycol ethers of ethylene oxide formed with fatty acid alcohols or alkyl phenols.

As the nonionic surfactants, the following compounds can be used, for example: condensation products of ethylene oxide formed with fatty acid alcohols; Alkylaryl polyglycol ethers; polymers of ethylene oxide and / or propylene oxide and derivatives thereof; alkyl cellulose.

As anti-foaming agents, for example, low molecular weight ethylene oxide / propylene oxide condensation products; aliphatic alcohols; special silicon oils or fatty acid amides are used.

As an adhesive or thickening agent, use can be made, for example, of alkaline earth metal soaps; salts of sulfosuccinic acid esters; or macromolecular natural or synthetic macromolecular materials which are soluble or swellable in water.

As anti-flocculant, one can use, for example, ethylene glycol, propylene glycol or glycerol.

The herbicidal compositions according to the invention can be prepared according to methods known in the field of pesticide industry 8602481, by mixing at least one compound of the general formula 1 with suitable inert solid and / or or liquid carriers or diluents and optionally with auxiliary substances.

In accordance with a further aspect of the invention, it is a method of controlling weeds to be applied in the protected areas - preferably on plants, parts of plants or on earth - an effective amount of a compound with the general formula 1 or a preparation containing such a compound is applied therein.

According to a further aspect of the invention, it is a process for the preparation of compounds 1 2 3 4 5 of the general formula 1 (wherein R, R, R, R and R have the above meanings), characterized in that 15 a ) a phenoxybenzoic acid derivative of the general formula 2 2 1 ΙΓ C-ï (2) 12 3 4 (wherein R, R, R and R have the meanings indicated in the preamble and Y represents halogen, cyano or alkyl-carbonyloxy ) is reacted with a metal derivative of a malonate of the general formula 3 0 II 5

C-OIT

CH2 (3) ^ C-OR1 0 * 8602481 (wherein R · has the meanings stated in the preamble) or in the presence of a metal compound - preferably magnesium chloride - with a malonate of the general formula 3; or b) a phenol of the general formula 4 - 5 - 'R2 r1' ^ ^ H (4) 12 3 (wherein R, R and R have the meanings stated in the preamble) or an alkali metal salt thereof is reacted with a benzoic acid derivative with the general formula 5 0 0 ft 5 1. C-On / C-CH'-CO5 (5> z- (0} ^ 4 5 (where R and R have the meanings indicated in the preamble and Z is halogen).

According to method a), the use of a sodium, potassium or magnesium derivative of the malonate of the general formula 3 is preferred. If the malonic acid derivative of the general formula (3) is used by itself, it is preferred that the reaction be carried out in the presence of a magnesium compound, in particular magnesium chloride, as the metal compound. The reaction can preferably be carried out in an inert solvent. As a solvent, a hydrocarbon (e.g. benzene, toluene or xylene), an ether (e.g. diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or dioxane), an amide (e.g. dimethylformamide, hexamethylphosphoric acid-triamide), a ketone are advantageously used. (e.g. acetone or diethyl ketone) or a nitrile (e.g. acetonitrile), etc.

The malonic acid derivatives of the general formula 3 are reacted in the form of a metal salt thereof with the compound of the general formula 2. The metal salts of the malonates can be prepared in advance, for example by reacting a malonate of the general formula 3 with an alkali or alkaline earth metal compound or a metal-organic compound. According to another alternative, the reaction of the compounds of the general formulas 2 and 3 is carried out in the presence of a metal compound - preferably magnesium 8602481? - 6 -. * * * Chloride. In this case, the metal salt of the malonate of the general formula 3 is formed in situ in the reaction mixture.

The reaction can be carried out at a temperature between -10 ° C and + 180 ° C, preferably at 30-100 ° C. The desired compound is isolated by known methods after removal of the by-products formed.

The malonates of the general Formula 3 and metal salts thereof, as well as the starting materials of the general Formula 2, are partly known compounds. Such compounds are described in U.S. Pat. Nos. 3,979,437 and 3,652,645 and in publications Org. Synth. Coll. Full. 285, and J. Org. Chem. 5Ό, 2622 (1985). The new compounds of the general formula II can be prepared according to a method which is analogous to the methods described in the mentioned publications.

According to method b), the compounds of the general formulas 4 and 5 are reacted preferably in the presence of an inert solvent or diluent. As the reaction medium, the solvents described under method a) can be used. It is preferred to operate in the presence of an acid binding agent, for example, an alkali metal hydroxide, alkali metal carbonate, alkali metal ethylate or alkali metal tert-butylate or any other suitable organic base (eg triethylamine).

Further details of the invention can be found in the following examples, to which the scope of the invention is by no means limited.

EXAMPLE I

Preparation of diethyl 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzoylmalonate a) To a solution of 38.0 g of 5- (2-chloro-4-trifluoromethyl-phenoxy) -2 nitrobenzoyl chloride and 50 ml of benzene, an ethoxy magnesium malonate solution, which was prepared from 17.6 g of diethyl malonate in 50 ml of benzene, was added at room temperature with stirring over 20 min. After completion of the addition, the reaction mixture was heated to reflux for one hour and then cooled. 50 ml of a 20% sulfuric acid was added to the 8 2 2 2 S 1 ψ «i i - 7 viscous solution with stirring. The phases were separated and the aqueous layer was extracted twice with 50 ml of benzene each. The combined extracts were washed with water and a sodium hydrogen carbonate solution and the solvent was distilled off. The residual yellow oil gradually became crystalline. 47.8 g of the desired compound with a melting point of 72-76 ° C were obtained.

b) A mixture of 19.7 g of 2-chloro-4-trifluoromethyl-10-phenol, 32.7 g of diethyl-2-nitro-4-fluoro-benzoyl malonate and 100 ml of anhydrous dimethyl sulfoxide was stirred at 50 ° C. After a reaction time of 24 hours, the reaction mixture was diluted with 100 ml of water and then extracted three times with 50 ml of benzene each. The benzene phase was dried over magnesium sulfate and the solvent was distilled off. The residual yellow oil was recrystallized from a mixture of benzene and hexane. This gave 40.3 g of the desired compound, melting point: 72-76 ° C.

c) A mixture of 21.9 g of sodium 2-chloro-4-trifluoro-20 methyl phenolate, 32.7 g diethyl 2-nitro-4-fluoro-benzoyl malonate and 100 ml anhydrous dimethyl sulfoxide was added for 24 hours stirred at 50 ° C. The reaction mixture was diluted with 100 ml of water and then extracted three times with 50 ml of benzene. The benzene phase was dried over magnesium sulfate and the solvent was distilled off. The residual yellow oil was recrystallized from a mixture of benzene and hexane. 39.8 g of the desired compound were obtained with a melting point of 72-76 ° C.

EXAMPLE II

Preparation of diethyl 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoylmalonate

To a solution of 45.8 g of 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoyl bromide in 50 ml of ether, a diethyl potassium malonate solution prepared from 17.6 g of diethyl-35 malonate in 50 ml ether, added dropwise with stirring at room temperature over 20 min. After completion of the addition, the reaction mixture was heated to reflux for one hour, then cooled, followed by addition of 50 ml of 860248 1% -8-20% sulfuric acid with stirring. Phase separation occurred, the aqueous layer being extracted twice with 50 ml of ether each time. The organic solutions were combined, washed successively with water and a sodium hydrogen carbonate solution, and the solvent was removed. The remaining yellow oil gradually solidified. 49.9 g of the desired compound are obtained, melting point: 84-88 ° C.

EXAMPLE III

Preparation of diethyl 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-chlorobenzoylmalonate

To a mixture of 35.0 g of 5- (2-chloro-4-trifluoro-methyl-phenoxy) -2-chlorobenzoic acid, and 10.1 g of triethylamine formed in 100 ml of toluene and cooled to 0 ° C with mixture of ice and salt, 12.1 g of pivaloyl chloride was added at such a rate that the temperature did not exceed 0 ° C. During the addition and the subsequent stirring period (15-20 min), triethylamine hydrochloride precipitated. The dropper funnel of pivaloyl chloride was replaced by a dropper funnel containing an ethoxy magnesium malonate solution prepared from 17.6 g diethyl malonate. During the dropwise addition of the ether solution, the temperature was maintained at a value between -5 ° C and 0 ° C. The reaction mixture was left overnight, after which 200 ml of a 5% sulfuric acid solution was added. The water phase was extracted twice with 50 ml of ether each time. The combined organic extracts were washed with dilute sulfuric acid and a sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate and evaporated. 44.3 g of the desired compound are obtained in the form of slightly yellow crystals, mp 59-65 ° C.

EXAMPLE IV

Preparation of diethyl 5- (2,4,6-trichloro-phenoxy) -2-nitro-benzoylmalonate 35 'In a 500 ml flask equipped with a stirrer and a dropping funnel, 9.52 g anhydrous magnesium chloride and 100 ml anhydrous . acetonitrile transferred. 16.2 g of diethyl malonate was added to the heterogeneous 86 0 2 48 1 - 9 mixture. The flask was transferred to an ice bath and 28 ml of triethylamine was added. 38.1 g of 5- (2,4,6-tri-chloro-phenoxy) -2-nitro-benzoyl chloride was added dropwise to the solution at 0 ° C over a period of 15 min. The reaction mixture was stirred at 0 ° C for an hour, then at room temperature for 12 hours and then cooled to 0 ° C, adding 60 ml of a 5 M hydrochloric acid solution. The resulting solution was extracted three times with 100 ml of ether each, then the combined extracts were dried over magnesium sulfate and the solvent and traces of diethyl malonate were removed. The residual slightly yellow oil slowly solidified. 45.0 g of the desired compound were obtained, m.p. 71-73 ° C.

EXAMPLE V

The following compounds of the general formula 1 from Table A were prepared in a manner analogous to that of the previous examples. Table A describes the definition of the symbols R-R, the melting points and the characteristic data of the NMR spectra.

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Preparation of herbicidally active preparations EXAMPLE VI

Granules with: an active ingredient content of 0.01% 2.3 g of compound No. 1 of technical quality 5 (purity: 89%) was dissolved in 97.7 g of methylene chloride to give a solution with a concentration of 2% by weight. An acidic pearl silica carrier, prepared from 4000 g of diatomaceous earth, was transferred to a Loedige 20-type turbin stirrer; the mean particle size of the support was between 0.5-2 mm. 20 g of the active ingredient pre-mix (2% mm / m solution) was sprayed over the granulated carrier using Tee-Jet 10080 nozzles at a rate of 5 g / min, stirring the granules in the Loedige type stirrer at a speed of 50 rpm. The sorption type 15 granules were packaged.

EXAMPLE VII

Sprayable powder with an active ingredient content of 95% 240 g of compound No. 2 (purity 97%), previously powdered in a mill, equipped with a rotating blade, was mixed with 2.5 g Cab-O-Sil M5 (amorphous silica; carrier) and 7.5 g of the 1494-type dispersant (sodium salt of the condensation product of sulfonated cresol and formaldehyde) in a mortar. The powdered mixture was ground in a tur-25 mill (Alpine LMRS-80) at an injected air pressure of 5 bar and a grinding air pressure of 4.5 bar at a feed rate of 250 g / h. Although the sprayable powder thus obtained did not contain a wetting agent, it was found to be readily wettable and has a minimum particle size of 20 µ.

In a spray with a concentration of 10 g / l, the floating power at 30 ° C after 30 min was found to be as follows: 84% in CIPAC standard D water; and 91% in CIPAC standard A water.

EXAMPLE VIII

Emulsifiable concentrate with an active ingredient content of 24% 40 g Tween 85 (ethoxylated sorbitan trioleate) and 8602481 '1 - 12 - 30 g Sapogenat T-180 (ethoxylated tributylphenol) emulsifiers and 250 g of compound No. Technical grade 7 (purity: 96%) were dissolved in 400 g of cyclohexanone at 40-45 ° C with stirring. After all the components have dissolved, the solution of the active ingredient (temperature 40-45 ° C) is poured into a mixture of 200 g of water, which has passed through an ion exchanger, and 70 g of ethylene glycol with vigorous stirring, after which the mixture is was cooled to 15-20 ° C. Before the end of the stirring period, 10 g of Silicon S RE anti-foaming agent (a 30% emulsion of dimethylsilicon oil) was added to the emulsion, while stirring was stopped 5 min later.

EXAMPLE IX

Biological application of the preparation. Grass seed and seeds of cultivated plants were sown in sand of the river Danube in plastic pots (size 10x10x10 cm), after which preparations prepared from the emulsifiable concentrates of the tested compounds were sprayed on the surface. of the sand (treatment before the emergence of the plants) and three weeks after sowing (treatment after the emergence of the plants). The plastic pots were watered at a rate required for normal plant growth, while the pots were kept in a greenhouse. Treatment results were evaluated after a four-week test-25 period and graded using a 0-10 scale, with 0 = no symptoms and 10 = completely destroyed infected plants (100%).

Two commercially available herbicides were used as reference compounds, namely acifluorfen (chemical name: sodium 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoate) and oxifluorfen (chemical name: 2-chloro-1- (3-ethoxy-4-nitro-phenoxy) -4-trifluoromethylbenzene).

The results are shown in Table B. The data shows that the efficacy of the present compounds - as the average activity against grassy and broad-leaved weeds - is better than that of the reference compounds, especially when applied prior to plant emergence.

8602481

V

- 13 -

The tolerance of some cultivated plants to the compositions of the invention was determined by the treatment methods described in this example. It has been found that dicotyledonous plants tolerate the compositions of the present invention well, while at the herbicidal dosage none of the compounds of the invention cause phytotoxic symptoms. It has been found that while in the treatment of corn, sunflower and leguminous plants prior to the emergence of the plantlets, the compounds of the invention are well tolerated, only soy oxifluorfen and acifluorfen used as reference compounds.

8602481 - 14 -

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Claims (12)

1. C-Cm C-CHCf C (5) 15-X, C-OR 3 s 4 5 (wherein R and R have the meanings mentioned above and Z represents halogen). 8602481 - 19 - 1. Phenoxybenzoyl malonates of the general formula [0105] o c c c-r r r r r c c - c - CH. Γ ~ ζ / - \ A C-OR5 R “(O / · 0 * '\ 2 /' R ü (1) where R is C1-4 allyl, halogen, cyano, nitro, methylthio or trifluoromethyl, R and R represents the same or different from each other hydrogen, halogen or trifluoromethyl, R4 represents hydrogen, halogen, cyano or nitro, while R represents C1-4 alky3./ which are the same or different. 2. A compound according to claim 1, characterized in that R 1 represents trifluoromethyl, R chlorine, R hydrogen, R nitro and R 3 ethyl. 3. A compound according to claim 1, characterized in that R 1 is trifluoromethyl, R and R represent chlorine, 4 R is nitro and R represents ethyl. 4. A compound according to claim 1, characterized in that R and R are chlorine, R is hydrogen, R is nitro and R3 is ethyl. 5. Herbicidal composition having the active ingredient in an amount of 0.01-95% by weight of a phenoxybenzoyl malonate of the general formula 1 0 0. I 5 2 »/ C- ° R ΛΖ S - CH. jf ° R <1> N3 where R1 represents C1-4 alkY1 / halogen, cyano, nitro, methylthio or trifluoromethyl, 3602481 - 17 - "2 3 R and R are the same or different and represent hydrogen, halogen or trifluoromethyl, 4 R hydrogen, halogen, cyano or nitro, while R ^ c1-4 represents al ^ yl (whether or not equal to one another), mixed with suitable solid and / or liquid carriers - preferably silicic acid, silicon dioxide and / or cyclohexanone - and optionally auxiliary substances - preferably surfactants, such as ethoxylated tributylphenol or an alkyl sulfonate. 6. Herbicidal composition according to claim 5, characterized in that it contains as active ingredient a compound 1 2 of the general formula 1, in which R represents trifluoromethyl, R 3 4 5 chlorine, R hydrogen, R nitro and R ethyl. Herbicidal composition according to claim 5, characterized in that it contains as active ingredient a compound of the general formula 1, in which R is trifluoromethyl, R 3 and R 5 represent chlorine, R is nitro and R represents ethyl. 8. Herbicidal composition according to claim 5, characterized in that it contains as active ingredient a compound 12 of the general formula 1, in which R and R are chlorine, 3 4 5 20 represents hydrogen, R is nitro and R is ethyl. 9. Process for the preparation of phenoxybenzoyl malonates of the general formula 1 0 0 ^ 5 I / C-0B R2 - CH> S ^ «k <-i-o- <öH r5 <1» ^ SR3 in which 25. C 1-4 alkyl, halogen, cyano, nitro, methylthio, or trifluoromethyl, 2 3 R and R are the same or different from each other hydrogen, halogen or trifluoromethyl, 4 R is warmer, halogen, cyan or nitro, while 5 <RTI ID = 0.0> R </RTI> 1-4 alkyl then not equal to each other), characterized in that a) a phenoxybenzoic acid derivative of the general formula 2 (6) 2 4 3 1 <n - + Μ: - 18 -O 2 * R CY r1-®-0-®-r4 <2) 12 3 4 (where R, R, R and R have the meanings indicated in the preamble and Y represents halogen, cyano or alkyl-carbonyloxy) is converted with a metal derivative of a malonate 5 of the general formula 3, q II 5 C-OR5 CH2 (3) ^ C-OR5 II o 5 (in which R has the meaning indicated in the opening paragraph) or in the presence of a metal compound - preferably magnesium- chloride - with a malonate of the general formula 3, or 10 b) a phenol of the general formula 4 R2 Η ^^ ΟΗ (4) 12 3 (in which R, R and R have the meanings stated) or an alkali metal salt thereof is reacted with a benzoic acid derivative of the general formula 5 0 0 11 5 10. Process for the preparation of phenoxybenzoylmalonates of the general formula 1 in which • R 1 Cl 4 alkY! halogen, cyano, nitro, methylthio or 5 is trifluoromethyl, 2 3 R and R are the same or different and represent hydrogen, halogen or trifluoromethyl, 4 R is hydrogen, halogen, cyano or nitro, while R ^ ^ 1-4 aifcY1 (not equal to each other), 10. characterized in that a phenoxybenzoic acid derivative 12 3 4 of the general formula 2 (wherein R, R, R and R have the meanings mentioned above, while Y represents halogen, cyano , ethoxycarbonyloxy or tert.butoxycarbonyloxy) is reacted with a metal derivative of a malonic ester of the general formula 3 (wherein R ~ has the meaning as defined in the preamble of this claim). Process for the preparation of a herbicidal composition according to any one of the preceding claims 5-8, characterized in that a compound of the general formula 1 1 2 3 4 5 20 (wherein R, R, R, R and R the Claim 5 have the meanings stated) in an amount of 0.01-95% by weight, are mixed with suitable inert solid or liquid carriers and / or diluents and optionally with further auxiliaries. 12. A method of weed control, characterized in that in the areas to be protected - preferably on plants, parts of plants or soil - an effective amount of a compound of the general formula 1 or a preparation containing that compound , is applied. 3602481