DD249840A5 - HERBICIDES AND METHODS OF COMBATING UNCRAFT - Google Patents

Abstract

The invention relates to a herbicidal composition and a method for controlling weeds. The herbicidal agent contains, in addition to conventional inert solid and / or liquid carriers and / or dismutating agents as the active ingredient 0.01-95 wt .-% of a phenoxy-benzoyl malonsaeureester derivative of the general formula (I) wherein R1 is halogen, cyano, nitro , Methylthio, C14 alkyl or trifluoromethyl, R2 and R3 independently of one another are hydrogen, halogen or trifluoromethyl, R4 is hydrogen, halogen, cyano or nitro and R5 is C14 alkyl. Formula I

Description

Herbicidal agents and methods of controlling weeds

Field of application of the invention:

The invention relates to a new herbicidal composition and a method for controlling weeds.

Characteristic of the known state of the art;

It is known that certain phenoxy-benzoic acid derivatives have a herbicidal activity. Such compounds are described in U.S. Patents 3,979,437 and 3,652,645.

In addition, of course, numerous other compounds with herbicidal activity are known. Nevertheless, there is still a great need for new herbal remedies.

Object of the invention:

The object of the invention is to provide an improved herbicidal agent and method for controlling weeds.

., Ι "]. 402937

- 2 -. Explanation of the essence of the invention:

It has been found that novel phenoxybenzoyl malonic acid ester derivatives of the general formula (I) wherein R is halogen, cyano, nitro, methylthio, ' G ^ _a alkyl or trifluoromethyl;

2 λ

R and R independently of one another represent hydrogen, halogen,

or trifluoromethyl;

R ^{4 is} hydrogen, halogen, cyano or nitro and RC ₁ is alkyl, have good herbicidal properties.

The new compounds of the general formula (I) differ from the known derivatives in the structure of the group bonded to the carbonyl group.

The new compounds are in their herbicidal activity - especially in pre-emergent treatment - the known derivatives of similar structure substantially superior. The novel compounds of the general formula (I) can be used successfully in a number of cultivated crops, in particular in maize, for the selective control of grassy and broadleaf weeds.

In an advantageous representative of the compounds of general

1 2 ^

mean formula (I), R is trifluoromethyl, R and R ^

Chlorine, R ⁴ nitro and R ⁵ ethyl.

In another advantageous representative of the compounds

1 2

of the general formula (I), R and R are chlorine,

Ή? for offspring, R ⁴ for nitro and R ⁵ for ethyl.

By the term "C 1-6 alkyl" is meant straight chain or branched alkyl groups of 1-4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, η-butyl, etc.).

The invention thus provides a herbicidal composition containing as active ingredient in an amount of 0.01-95 wt.% A

Compounds of general formula (I) (wherein R, R, R, R and R have the above meaning) and suitable inert solid and / or liquid carriers or diluents and optionally adjuvants (eg surfactants, antifoaming agents, adhesives, antifreeze agents etc.).

The herbicidal composition of the present invention can be formulated in forms common in agriculture and crop protection (e.g., powder blends, spray powders, granules, pastes, emulsions, solutions, suspensions, etc.). The herbicidal compositions may contain conventional carriers and excipients.

As solid carriers, e.g. the following substances are used: minerals or synthetic substances such as kaolin, silica, talc, attapulgite, diatomaceous earth, aluminum oxide, silicic acid and various silicates. As liquid diluents, e.g. the following liquids are used: petroleum fractions with different boiling point intervals (e.g., gas oil, keratin), oils of animal or vegetable origin; aromatic, aliphatic or alicyclic hydrocarbons (e.g., benzene, toluene, xylene, cyclohexane, tetrahydronaphthalene) and their derivatives (e.g., chlorobenzene, carbon tetrachloride, alkylated haphthalene derivatives, cyclohexanone, butanol, etc.); strong polar solvents (such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc.) ·

The surfactants (e.g., emulsifying, dispersing, whitening and antifoaming agents, antiaggregating agents, etc.) may be ionic or nonionic compounds. As ionic surfactants, e.g. the following compounds are used:

Salts of saturated or unsaturated garboxylic acids; Sulfonates of aliphatic, aromatic or araliphatic hydrocarbons; Sulfonates of alkyl, aryl or aralkyl alcohols; Sulfonates of alkyl ,. Aryl or aralky1-carboxylic acids, esters and ethers; Sulfonates of condensation products of phenols, cresols or haphthalene 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 following substances can be exemplified: condensation products of ethylene oxide and fatty alcohols: alkylaryl polyglycol ether; Ethylene oxide and / or propylene oxide Block polymers and derivatives thereof: Alkyl cellulose.

As foam control agents, e.g. Low molecular weight ethylene oxide / propylene oxide condensation products; aliphatic alcohols, special silicone oils or fatty acid anides can be used.

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

As the antifreeze, ethylene glycol and propylene glycol or glycerin may suitably be used.

The herbicidal compositions according to the invention can be prepared in a manner known per se by mixing a compound of the general formula (I) with suitable inert solid and / or liquid carriers or diluents and, if appropriate, with excipients.

The invention furthermore relates to a method of controlling weeds, characterized in that the objects to be protected - e.g. Plants, plant parts or the soil - treated with an effective amount of a compound of general formula (I) or an agent containing such a compound.

EXAMPLES

Further details of the invention can be found in the following examples, without limiting the scope of protection to these examples.

Preparation Examples of Active Ingredients: Example 1

Preparation of 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoyl-malonic acid diethyl ester

a) To a solution of 38.0 g of 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoyl chloride in 50 ml of benzene at room temperature with stirring within 20 minutes, a solution of 17 »6 g Diethyl malonate Athoxymagnesiummalonat prepared in 50 ml of benzene added dropwise. After completion of the addition, the reaction mixture is refluxed for one hour and then cooled. 50 ml of 20% sulfuric acid are added to the viscous solution with stirring. The phases are separated and the aqueous layer is extracted twice with 50 ml of benzene each time. The extracts are combined, washed with water and a sodium bicarbonate solution and concentrated. 47.8 g of the titled compound are obtained in porin of a yellow oil. Pp .: 72-76 ⁰ C.

b) A mixture of 19.7 g of 2-chloro-4-trifluoromethyl-phenol,

32.7 g of diethyl 2-hitro-4-fluoro-benzoyl-malonate,

13.8 g of potassium carbonate and 100 ml of anhydrous Dirnethylsulfoxyd is stirred at 50 ⁰ C. After a reaction time of 24 hours, the reaction mixture is diluted with 100 ml of water and extracted three times with 50 ml of benzene each time. The benzene phase is dried over anhydrous magnesium sulfate, whereupon the solvent is distilled off. The resulting yellow oil is recrystallized from a mixture of benzene and hexane. 40.3 g of the title compound are obtained. Pp .: 72-76 ⁰ G.

c) A mixture of 21.9 g of 2-chloro-4-chloro-4-trifluoromethyl-phenolate, diethyl 32.7 g .2-litro-4-fluoro-benzoyl-malonate and 100 ml of anhydrous dimethyl sulfoxide is stirred at 50 G. After a reaction 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 resulting yellow oil is recrystallized from a mixture of benzene and hexane. There are obtained 39.8 g of the title compound. Pp .: 72-76

'G.

Example 2

Preparation of diethyl 5 ~ (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoyl-malonate

To a solution of 45.8 g of 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoylbromide and 50 ml of ither is added, while stirring at room temperature within 20 minutes, a solution of 17.6 g Diethyl malonate produced Diäthyl- potassium malonate and 50 ml of ether added dropwise, liach completion of the addition, the reaction mixture is heated for one hour under reflux, then cooled, whereupon 50 ml of 20% sulfuric acid are added with stirring. The phase

sen are separated from each other, the aqueous layer is extracted twice with 50 ml of ether. The organic phases are combined, washed successively with water and with a: sodium bicarbonate solution and. concentrated. The resulting yellow oil solidifies slowly. There are obtained 49 ₅ 9 g of the title compound. Pp .: 84-88 ⁰ C.

Example 3

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

A mixture of 35.0 g of 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-chloro-benzoic acid, 10.0 g of triethylamine and 100 ml of toluene, cooled to 0 C with a salt-ice mixture, becomes 12 , 1 g of pivaloyl chloride added at such a rate that the temperature does not exceed 0 C. During the addition and subsequent stirring (about 15-20 minutes), triethylamine hydrochloride precipitates. The feeder for the pivaloyl chloride is replaced with a dropping funnel containing an ethereal ethoxymagnesium malonate solution prepared from 17> 6 g of diethyl malonate. The ethereal solution is added dropwise keeping the temperature between -5 and 0 ^° C. The reaction mixture is allowed to stand overnight, after which 200 ml of a 5% sulfuric acid solution are added. The aqueous phase is extracted twice with 50 ml of ether. The combined organic phases are washed with dilute sulfuric acid and a sodium bicarbonate solution, dried over anhydrous sodium sulfate and concentrated. There are obtained in the form of pale yellow crystals 44j3 g of the title compound. Pp .: 59-65 ⁰ G.

- 8 Example 4

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

In a provided with a stirrer and a dropping funnel 500 ml flask 9 ₅ 52 g of anhydrous magnesium chloride and 100 ml of anhydrous acetonitrile are weighed. 16.0 g of diethyl malonate are added to the heterogeneous mixture, whereupon the flask is placed in an ice bath and 28 ml of triethylamine are added. The solution is stirred for 15 minutes at 0 ⁰ C, after which 38.1 g of 5- (2,4 ₅ 6-trichloro-phenoxy) -2-nitro-benzoyl chloride was added dropwise -Be. The reaction mixture is stirred for one hour at 0G and for 12 hours at room temperature and finally cooled to 0 ° C. To the mixture is added 60 ml of a 5M hydrochloric acid solution. The resulting solution is extracted three times with 100 ml of ether, then the combined extracts are dried over magnesium sulfate. Upon removal of the solvent and traces of diethyl malonate, a pale yellow oil is obtained which slowly solidifies. There are 45% of the compound mentioned in the title. Pp .: 71-73 ⁰ C.

Example 5

The following 19 compounds of the general formula (I) are prepared analogously to the previous Examples 1-4

1 S produced. The definition of the substituents R-R, the melting points and the characteristics of the EMR spectra are summarized in Table I.

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Pormulierungsbeispiele

Example 6 ;

0.01 % active ingredient containing granules

From 2.3 g of active ingredient No. 1 (technical grade, purity 89 %) and 97.7 g of methylene chloride, a 2 % solution is prepared. In. 4000 g of an acidic silicate stabilizer prepared from calcined diatomaceous earth is weighed into a Lödige 20 fluidized-bed mixer (average particle diameter 0.5-2 mm). On the granular carrier are passed 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, wherein the mixture in the mixer at a speed of 50 revolutions / min, stirred. The granules of the sorption type are finally packed.

Example 7

95 % active ingredient containing sprayable powder

240 g of active ingredient Ir. 2 (purity 97 %) are ground in a hammer mill. The millbase is in a mortar with 2.5 g of an amorphous silica (Cab-O-Sil M5: carrier) and 7.5 g of a dispersant ITr. 1495 (latriurnsalz 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 at a feed rate of 250 g / piece. Although the spray powder thus obtained contains no additional wetting agent, it is good. wettable. The maximum particle diameter is 20 / Um. In a spray mixture with a concentration of 10 g / l is at 30 ⁰ C after 30 minutes the

floatability

in CIPAC Standard D water 84 % and in CIPAC Standard A water 91%.

Example 8

24 % active ingredient containing emulsion concentrate

In 400 g of cyclohexanone, 40 g of Tween 85 (ethoxylated sorbitan trioleate) and 30 g of Sapogenat be T-180 (ethoxylated tributylphenol) as Bmulgierungsmittel and 25Og drug Hr at 40-45 ⁰ C. 7 (technical quality, purity 96 %) solved. The dissolution is promoted by stirring. After completion of the dissolution, the drug solution (temperature 40-45 ⁰ C) is poured into a mixture of 200 g of ion-exchanged water and 700 g of ethylene glycol with vigorous stirring, after which the mixture is slowly cooled back to 15-20 ⁰ C. Before the end of the stirring, 10 g of a foam remover (Silicon SRE, a 30 % emulsion of a dimethyl silicone oil) are added to the emulsion. After 5 minutes, stirring is stopped.

Example 9 "

Biological application example

Grass seeds and seeds of crops are sown in a plastic vessel (size 10 χ 10 χ 10 cm) in sand from the Danube. Various amounts of the diluted amulable concentrates containing the test compounds are sprayed on the sand surface (pre-emergent treatment) and three weeks after sowing (post-emergent treatment), respectively. The plastic containers are poured daily with the amount of water required for normal plant growth and kept in a greenhouse. The results of the experiments are

after 4 weeks using a scale between 0 and 10: 0 = no symptoms; 10 = 100 % infected, destroyed plants.

As reference compounds, two herbicidal commercially available products are used:

Acifluorfen (according to chemical nomenclature: sodium 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoate) and

Oxiflurfen (according to chemical nomenclature: 2-chloro-1- (3-ethoxy-3-nitro-p.heno2cy) -4-trifluoromethylbenzene),

The results are summarized in Table II. These data indicate that the average potency of the new compounds against grassy and broadleaf weeds - especially in the case of pre-emergent treatment - is clearly superior to the efficacy of the control substances.

The tolerance of different crops to the agents of the invention is determined by the methods described in this example. The test results show that dicotyledonous crops tolerate all the compositions according to the invention well. Within the usual herbicidal doses, no phytotoxic symptoms occur at all. It has also been found that maize, sunflower and legumes tolerate the agents of the invention very well in the case of preemergence treatment. In contrast, the reference compounds oxifluorfen and acifluorfen are tolerated in the treatment mentioned only by soybean plants.

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

Test Doais Amaranth. Ghenopod. Echinoch. Setaria soy green corn sun verb, kg / ha retrofle. album crus gal. italica beans peas flowers ITr. Wirks. pre post pre post pre post pre post pre post pre post pre post

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Table II (port setting)

Test verb. No. Dose kg / ha Active. Amaranth, retrofle. pre pro 4 5 Reference compounds: 0.3 1.0 6 8 7 10 Cheiiopod. album pre pro 4 5 Echinoch. crus-gal. pre post 4 Setaria italica pre post 6 Soy bean pre post roo Green peas pre post 2 6 Corn pre post Office • Sunflowers pre post I 6 10 CO cn 9 0.3 1.0 4 β 10 10 Aci fluorene 0.3 1.0 6 8 6 10 4 6 10 10 C-CO 8 10 COVJl 8 10 0 1 0 2 0 1 OJ C- 0 0 i 0 0 6 10 6 10 10 0.3 1.0 8 10 4 5 Oxi- fluorfen 6 9 VDCO 8 10 VD C- 8 10 5 8 0 1 0 2 0 1 0 6 0 2 4 8 0 2 5 10 11 0.3 1.0 Co cn 4 5 VD C- 6 8 c-ro 6 10 6 10 5 6 0 0 0 1 0 1 VJl O 0 1 4 6 0 2 6 8 12 0.3 1.0 6 7 4 6 5 7 4 5 8 10 5 6 7 8 5 6 0 0 0 2 0 1 0 3 Ot 6 1 2 5 6 13 0.3 1.0 4 7 5 6 4 6 VD C- 5 8 03 cn '5 8 C-O 0 1 0 2 0 1 OVO 0 1 VJl VjJ 0 1 6 8 14 0.3 1.0 6 8 7 9 c-ro 7 9 7 9 6 9 ' 8 10 6 10 0 0 roo 0 1 0 6 0 1 4 8 0 0 6 10 VJL 0.3 1.0 CO cn. 6 10 6 9 5 10 0 0 0 1 0 1 4 8 0 2 7 10 6 9 7 10 0 2 OJ C- 6 10 5 8 6 10 ro ro 8 10 8 10 7 10 3 6 0 3 4 8 3 8 6 8 4 8 6 10 I VJl 6 8 6 8 6 10 3 6 4 9 6 8 4 9

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(I)

Claims (4)

Claim: 1. A herbicidal composition, characterized in that it contains as active ingredient in an amount of 0.01-95 Gew./S phenoxybenzoyl malonesäureester derivative of the general] ormel (I), wherein -1 R is halogen, cyano, ITitrO, methylthio, Cj ^ alkyl or Trifluoromethyl;
R and R ^ independently of one another represent hydrogen, Halogen or trifluoromethyl; RY / asserstof-f, halo, cyano or nitro and Rr is C ₁ . Alkyl means and suitable inert solid and / or liquid carriers and diluents, preferably silica, silicic acid and / or cyclohexanone, and optionally other excipients, preferably surfactants, e.g. ethoxylated tributylphenol or alkylsulfonates. 2. A herbicidal composition according to claim 1, characterized in that it is a compound of the general -1 , in which "R" is trifluoromethyl, R ^{2 is} chloro, R ^{3 is} hydrogen, R ^{4 is} nitro and R ^{5 is} ethyl. 3. A herbicidal composition according to claim 1, characterized in that it contains as active ingredient a compound of general formula (I), wherein R is trifluoromethyl, R ² and B? Chlorine, R ^{4 is} nitro and R ^{5 is} ethyl. 4. A herbicidal composition according to claim 5>, characterized in that it contains as active ingredient a compound of general formula (I), wherein R and R are chlorine, R ^J Hydrogen, R ^ nitro and R ethyl means. Method of controlling weeds, characterized in that. the objects to be protected, e.g. the plants, the parts of plants or the soil, with a herbicidally effective amount of a compound -ι ρ ο Λ of the general formula (I), wherein R, R, R, S and Br are as defined above, or treated with an agent according to claims 1 to 4.