CS203943B2 - Selective herbicide - Google Patents

Abstract

Novel phenylurea derivatives of the general formula <IMAGE> (wherein R1 represents H, C1-C4- alkyl, C2-C4-alkenyl, C2-C4-alkynyl or OCH3, R2 and R3 each represents H or C1-C4-alkyl, R4 and R5 each represents halogen, each X represents H, C1-C4-alkyl, halogen or OCH3 and n represents 1 or 2) have a herbicidal action and accordingly may be made up with suitable carriers into herbicidal preparations and may be used for protecting living plants, crop areas and waste lands against weeds.

Description

The present invention relates to a selective herbicidal composition comprising, as an active ingredient, at least one of the following new phenylurea derivatives. ·

Phenylurea derivatives having herbicidal activity are already known, for example 1- (3,4-dichlorophenyl) -3,3-dimethylurea according to US Pat. However, they exhibit a very narrow spectrum of activity relative to useful plants.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a composition which, in addition to an excellent herbicidal activity against weeds, has a wide spectrum of selectivity to useful plants.

The object of the present invention is to provide at least one phenylurea derivative of the formula I as an active ingredient

a C 2-4 alkyl group or a methoxy group, a R 2 hydrogen atom, a C 1 -C 4 alkyl group, a R 5 carbon atom, a C 1 -C 4 alkyl group, R 1 and R 5 a halogen atom, X a hydrogen atom and / or an alkyl group having from 1 to 5 carbon atoms; 4 carbon atoms and / or halogen and / or methoxy, and n is 1 or 2.

The compounds are characterized by both excellent soil and leaf activity and a wide spectrum of selectivity to useful plants. So they can. preferably used to control monocotyledonous and dicotyledonous weeds, especially in crops of useful plants.

The compounds kill in the pre-emergence and also in the post-emergence process of field weeds such as mustard (Sinapis sp.), Chickweed (SteHaria media), ragwort (Senecio vulgaris), chamomile (Matricaria chamomiila), purple moth (Ipomoeapurpuren), Chrysanthemum segetum), Lamium amplexicaule, Cornflower (Centaurea cyanus), Amaranthus retroflexus, Alopecurus myosuroides, Hedgehog Corn. (Echinochloa crus galii), Italian legumes (Setaria italica), perennial ryegrass (Lolium perenne) and other weeds.

203943 (I) is used to control seed weeds where R 1 is hydrogen, C 1 -C 4 alkyl, alkynyl generally has an application rate of 1 kg of active ingredient to 5 kg of active ingredient per hectare. The active compounds according to the invention appear to be selective in crops of useful plants such as bush beans, peanuts, potatoes, rice, sorghum, maize, winter grain and soya.

At larger application rates, these compounds are also useful as total herbicides to eradicate or suppress eel flora during the growing season.

The compounds of the invention may be used alone, in admixture with each other or with other active ingredients. If desired, other defoliants, plant protection or pest control agents may also be added as desired.

If it is desired to broaden the spectrum of activity, other herbicides may be added. Suitable herbicidally active ingredients are active compounds from the group of triazines, aminotriazoles, anilides, diazinium, uracils, aliphatic carboxylic acids and halocarboxylic acids, hydrazides, amides, nitriles, esters of these carboxylic acids, esters of carbamic acid, urea, 2,3,6- trichlorobenzyloxypropanil, rhodamide compositions and other additives.

Other additives include, for example, non-phytotoxic additives that can provide synergistic enhancement with herbicides, including, but not limited to, wetting agents, emulsifiers, solvents, and oily additives.

The active compounds or mixtures thereof according to the invention are advantageously used in the form of preparations such as powders, dusts, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and optionally wetting, emulsifying and / or dispersing auxiliaries. substances.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethylsulfoxide, dimethylformamide, and petroleum fractions.

Suitable solid carriers are mineral soils such as tonsil, silica gel, talc, kaolin, attaclay clay, limestone, silica, plant products such as flours.

Surfactants include, for example, calcium ligninsulfonate, polyoxyethylene alkyl phenol ethers, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates, and substituted benzenesulfonic acids and their salts.

The proportion of the active compound (s) in the various preparations can vary within wide ranges. For example, the compositions comprise from 10 to 80% by weight of active ingredients, from 0 to 20% by weight of liquid or solid carriers, and optionally up to 20% by weight of surfactants.

The compositions can be applied in a conventional manner, for example with water as carrier in spray slurries in an amount of about 100 to 1000 liters / ha. The use of the compositions in the so-called low-volume and ultralow-volume processes is as possible as their application in the form of microgranules.

In the general formula (I) of the active compounds, for the radical R 1, for example, in addition to hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, allyl, propynyl, butynyl and methoxy; the radicals R2 and R3, in addition to hydrogen, also methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl. The radicals R 4 and R 5 can be fluorine, chlorine or bromine.

For example, X may be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, fluoro, chloro, bromo, iodo, methoxy and others.

Among the compounds, the compounds of the formula I in which R1 is methyl or methoxy, R2 is hydrogen or methyl, R3 is hydrogen or methyl, R4 is chlorine or bromine, R5 is chlorine or bromine, X is hydrogen, and / or methyl, and / or chlorine and / or methoxyl an number 1 or 2.

For example, the novel active compounds of the formula I can be prepared by the process of:

A. the compounds of formula IIh, w X.3 and ^H where R ^@ 2 to R ^{@ 5} , X and n are as defined above, react in the reaction:

a) with carbamic acid halides of the formula Til

R 1 - N - CO - hal

AND

Wherein R 1 is as defined above, optionally in the presence of a solvent and an acid-binding agent;

b) with methyl isocyanate of formula IV

N, N = C = O (IV), optionally in the presence of a solvent and a catalyst;

B. compounds of formula V

R1-NH

CH3 (VI)

O-C-N wherein R 1 is as defined above, optionally in the presence of a solvent and a catalyst, or wherein R 2 to R 5, X and n are as defined above, reacted with amines of formula VI

C. with compounds of formula VII

O-CO-NH

z s

OCH 2 C-CH 2 R 3, R ₂ (VII) wherein R 2 to R 5, X and n are as defined above, react with amines of formula VI

R = NH

CH 3 (VI), wherein R 1 is as defined above, optionally in the presence of a solvent;

D. The compounds of formula VIII (VIII) wherein Ri, X and n have the abovementioned meaning, are reacted with halides of general formula IX ^{R @} HCR ^R5 hal £ -CH-CH-C and I ^R * ^r i. (X) wherein R 2 to R 5 are as defined above, in the presence of a solvent and an acid-binding agent, optionally in the presence of a catalyst, and the reaction products are isolated.

Suitable solvents for the reactants in all reactions are inert aliphatic and aromatic hydrocarbons such as hexane, benzene and toluene, chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and dichloroethane, ethers such as diethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone and butanone, nitriles such as aceeonitrile, amides such as dimethylformamide and hexamethyl phosphoric triamide.

Suitable acid-binding agents for all reactions are organic bases, such as tertiary amines, for example triethylamine, pyridine and dimethylaniline, or inorganic bases, such as alkali or alkaline earth metal oxides, hydroxides or carbonates.

Suitable catalysts for the reaction with isocyanates are tertiary amines, such as triethylamine, and for the reaction of phenols with halides, metal iodides such as sodium iodide.

The reaction of the components is carried out at temperatures between 0 and 150 ° C for all reactions.

The aniline derivatives used as starting materials are obtained by etherification of the respective nitrophenols and subsequent reduction of the nitro group according to known methods.

Conversely, aminophenols can be intentionally acylated on nitrogen first and etherification chosen as the last operation. .....

Dihalogenacylpropane derivatives,. used for etherification are in part known per se and can be prepared by known methods.

A process has now been found which makes it possible to produce these compounds more easily and in a higher yield using cheaper raw materials. According to the novel process, the allyl halide of formula X is reacted

Rž — CH = C — CHhalhal

Rs (X), in a two-phase system, consisting of a haloform of the formula CHR a R shal, wherein R 4 and R 5 are as hereinbefore defined, optionally diluted with an inert solvent and an alkali metal or solid alkali metal hydroxide. aqueous solution, in the presence of a catalyst. Surprisingly, the allyl halides used do not saponify or saponify the alkali metal hydroxides only slightly.

Of the haloforms, chloroform or bromoform is preferred, of the hydroxides sodium hydroxide, preferably as a 50% aqueous solution.

Suitable catalysts are onium compounds, such as quaternary ammonium, phosphonium and arsonium compounds, as well as sulfonium compounds.

Also suitable are polyglycol ethers, especially cyclic ones such as 18-crown-6, and tertiary amines such as trbutylamine. Preferred compounds are quaternary ammonium compounds such as benzyltriethylammonium chloride and tetrabutylammonium bromide.

The relative amounts of reactants can be varied within wide limits. Preferably, the reactions are carried out with a 1 to 10-fold excess of either haloform or hydroxide. An amount of 0.02 equivalents is sufficient for the catalyst.

The reaction proceeds between 20 and 100 ° C, but usually between 20 and 60 ° C. The reaction time is 1 to 72 hours. Good agitation is required throughout the reaction time.

The dihalogenocyclopropane derivatives required as starting materials are surprisingly obtained in this way with a higher yield and a technically simpler process than in the known processes.

The following examples illustrate the preparation of compounds used as active ingredients in a selective herbicidal composition of the invention.

Example 1

1- [4- (2,2-dichlorocyclopropylmethoxy] -phenyl] -3,3-dimethylurea

To 100 ml (1.16 mol) of 3-bromopropene in 600 ml of chloroform was added 2 g of benzyltriethylammonium chloride. 600 ml of 50% sodium hydroxide solution are added with good stirring over 30 minutes. The temperature rises and is maintained by cooling between 56 and 60 ° C. Stirring is continued at this temperature, then 750 ml of chloroform and 750 ml of water are added. The organic phase was separated, evaporated and fractionated in vacuo. Yield 162 g l-bromomethyl-2,2-dichlorcyklopropanu TV 17 mbar: 63-70 ° C, n _D ² ° = 1.5096.

4 g (0.5 mol) of 4-nitrophenol are dissolved in 250 ml of dimethylformamide and 108 g (0.53 mol) of 1-bromomethyl-2,2-dichlorocyclopropane, 83 g of potassium carbonate and 1.5 sodium iodide are added under stirring. Then it was stirred at 90 ° C for 2 hours. Allow to cool, pour into water and extract with ethyl acetate. The organic phase is washed with dilute sodium hydroxide, then with water, dried and evaporated. The residue was recrystallized with pentane. Yield: 113 g of 4- (2,2-dichlorocyclopropylmethoxynitrobenzene, m.p. 66-67 ° C).

108 g (1.73 mol) of hydrazine hydrate are dissolved in 500 ml of ethanol and 10 g of nickel catalyst are added. 113 g (0.43 mol) of the above nitro compound are added in small portions over 45 minutes. The temperature rises to 60 ° C. Stirring is continued for 1 hour, filtered, the filtrate is concentrated and poured into water. It is extracted with ethyl acetate, dried and evaporated. A yellowish oil remains, which is used without purification for the next reaction. Yield 96 g of 4- (2,2-dichlorocyclopropylmethoxy) aniline.

g (0.086 mol) of 4- (2,2-dlchlorocyclopropylmethoxy) aniline was dissolved in 100 ml of pyridine. While stirring, 8.7 ml of dimethylcarbamoyl chloride are added dropwise over 5 minutes, the temperature rising to 53 ° C. Stirring is continued for a further 2 hours and evaporated under a pressure of 50 mm Hg. The residue was taken up in ethyl acetate, washed once. water, once with 5% hydrochloric acid, dried, evaporated and recrystallized from isopropyl ether.

Yield: 16 g of 1- (4- (2,2-dichlorocyclopropylmethoxy) phenyl) -3,3-dimethylurea.

Melting point 108-110 ° C.

Example 2

1- (3- (2,2-dichlorocyclopropylmethoxy) phenyl) -3,3-dimethylurea

To 17 g (0.094 mol) of 1,1-dimethyl-3- (3-hydroxyphenyl) urea dissolved in 60 ml of dimethylformamide, 22 g (0.108 mol) of 1-bromomethyl-2,2-dichlorocyclopropane, 16 g of potassium carbonate are added. as well as 2 g of sodium iodide and stirred at room temperature. After 20 hours, 6 g of 1-bromomethyl-2,2-dichlorocyclopropane and 5 g of potassium carbonate are again added and stirred for a further 6 hours. It is then strongly concentrated, taken up in ethyl acetate, shaken with water, dried and recrystallized from a mixture of ethyl acetate and ether. Yield

19.9 g. M.p. 140-142 ° C.

The 1,1-dimethyl-3- (3-hydroxyphenyl) urea used as the starting material is known per se and can be prepared by known methods, for example from 3-aminophenol and dimethylcarbamoyl chloride.

The following compounds can be prepared in an analogous manner.

Physical constant

Physical

Compound name constant

Name of the compound

1- [4- (2,2-dichlorocyclopropylmethoxy) -3-methoxyphenyl] -

3,3-dimethylurea 1.1. 163-164 ° C

1- (4- (2,2-dichlorocyclopropylmethoxy) -3-methoxyphenyl] -3-methoxy-3-methylurea m.p. 105-106 ° C 1- [3-chloro-4- (2,2-dichlorocyclopropylmethoxy) phenyl] -3,3-dimethylurea mp: 130-131 ° C

1- [3-chloro-4- (2,2-dichlorocyclopropylmethoxy) phenyl] -3-methoxy-3-methylurea 1.1. Mp 79-80 ° C

1- (4- (2,2-dichlorocyclopropylmethoxy) phenyl) -3-methoxy-3-methylurea m.p. 88 DEG-89 DEG C. 1-butyl-3- [4- (2,2-dichlorocyclopropylmethoxy) phenyl] -1-methylurea mp 87-88 ° C

1- (4- (2,2-dichlorocyclopropylmethoxy) phenyl) -3-methyl- (1-methyl-2-propionyl) urea mp 111-111 ° C

1- (4- (2,2-dichlorocyclopropylmethoxy) -3,5-dimethylphenyl] -3,3-dimethylurea m.p. 135-136 ° C

1- [4- (2,2-Dichloro-cyclopropylmethoxy) -3,5-dimethyl-phenyl] -3-methoxy-3-methyl-urea 1.1. Mp 66-67 ° C

1- (4- (2,2-dichlorocyclopropylmethoxy) -3,5-dichlorophenyl) -3,3-dimethylurea m.p. 146-147 ° C

1- (4- (2,2-dichlorocyclopropylmethoxy) -3-methylphenyl) -3,3-dimethylurea m.p. 111-111 ° C 1-butyl-3- (3- (2,2-dichlorocyclopropylmethoxy) phenyl)] -1-methylurea mp 71-72 ° C

1- (4- (2,2-dichloro-1-methylcyclopropylmethoxy) phenyl) -3-methoxy-3-methylurea m.p. 103-104 ° C

1- (3- (2,2-dichloro-1-methyl-1-cyclopropylmethoxy) phenyl) -3,3-dimethylurea mp 105-106 ° C

1- (4- (2,2-dichloro-1-methylcyclopropylmethoxy) phenyl) -3,3-dimethylurea m.p. 127-128 ° C

1- (3- (2,2-dibromocyclopropylmethoxy) phenyl) -3,3-dimethylurea m.p. 112-113 ° C

1- (4- (2,2-dibromocyclopropylmethoxy) phenyl) -3,3-dimethylurea m.p. 99-101 ° C

1- (4- (2,2-dichloro-3-methylcyclopropylmethoxy) phenyl) -3,3-dimethylurea m.p. 140-142 ° C

1- (3- (2,2-dichloro-3-methylcyclopropylmethoxy) phenyl) -3,3-dimethylurea m.p. 102-104 ° C

Said derivatives according to the invention are colorless, odorless crystalline substances which are readily soluble in ethyl acetate, acetone and alcohol. They dissolve partially only slightly in benzene and are practically insoluble in saturated hydrocarbons and water.

The following examples serve to illustrate the possibilities of use and the predominant selectively herbicidal effect of the compounds of the invention.

Example 3

In the greenhouse, the compounds of the invention listed in the table were sprayed at an application rate of 5 kg of active ingredient in 500 l of water / ha in the form of aqueous emulsions on mustard (Sinapis sp.) And aubergine (Solanum sp.) As test plants. before and after emergence. Three weeks after treatment, the result of the treatment was evaluated, indicating = no effect and = complete killing of the plants.

As can be seen from the table, the killing of test plants was generally achieved.

Compounds of the Invention Pre-emergence Post-emergence

Eggplant Mustard

1- [4- (2,2-Dichlorocyclopropyl) methylmethoxy- -3-methoxyphenyl] -3,3-dimethylurea 4 4 4 4 1- [4- (2,2-dichlorocyclopropylmethoxy) -3-methoxyphenyl] -3-methoxy-3-methylurea 4 4 4 4 1- [3-Chloro-4- [2,2-dimethyl-cyclopropyl-imethoxy] -phenyl] -3,3-dimethyl-urea. 4 4 4 4 1- [3-chloro-4--2,2-dichlorocyclopropylmetho- xy) phenyl] -3-methoxy-3-methylurea 4 4 4 4 1- [4- (2,2-Dichloro-cyclopropylmethyl) -phenyl] -3-methoxy-3-methyl-urea 4 4 4 4 1-butyl-3- [4- (2,2-dichlorocyclopropylmethoxy] phenyl] -1-methylurea 4 4 4 4 1- (4- (2,2-dichlorocyclopropylmethoxy) phenyl) -3-methyl-3- (1-methyl-2-propynyl) urea .......... 4 4 4 4 1- [4- (2-, 2-Chlorocyclopropylmethoxy) phenyl] -3,3-dimethylurea 4 4 4 4 1- [4- (2,2-dichlorocyclopropylmethoxy) -3,5-dimethylphenyl] -3,3-dimethylurea - -. ' 4 4 1- [4- (2,2-dichlorocyclopropylmethyl) -3,5-dimethylmethylphenyl] -3-methoxy-3-methyl urea _ _ 4 4 1- [4- (2,2-dichlorocyclopropylmethoxy] -3-methylphenyl] -3,3-dimethylurea 4 4 4 4 1- [4- (2,2,2-dichlorocyclopropylmethoxy) - -3,5-dichlorophenyl. -3,3-dimethylurea - - 4 4 1- (4- (2,2-dibromocyclopropylmethoxy) phenyl) -3,3-dimethylurea 4 4 4 4 1- [4- (4-Dichloro-1-methylcyclopropylmethoxy) phenyl] -3-methoxy-3-methylurea _ 4 - 4 1- [3- (2,2-dibromocyclopropylmethoxy) - phenyl] -N-4-methylurea 4 4 4 4 l- [. 3- (2,2'-ΜΙΜ) )ί '··^^^^^^^!) Op op op op op op op op op) - yl opyl op op op fenyl op fenyl fenyl fenyl fenyl fenyl 3,3 3,3] 4 4 4 4 1-Butyl-3- [3- (2 ', 4' - (1 ') - (1') - (1 ', 3'-propylmethoxy) phenyl) -1-methylurea - 4 - 4 1- (4- (2,2-dichloro-1-methylcyclopropylmethoxy) phenyl] -3,3-dimethylurea . - 4 4 4 4 1- [3- (2,2-dichlorocyclopropylmethoxy] phenyl] -3,3-dimethylurea 4 4 4 4 1- (4- (2,2-Dichloro-3-methyl-phenyl) -3,3-methyl-urea) - 4 - 4 1- (3- (2,2-Dichloro-3-methylcyclopropylmethoxy) phenyl] -3,3-dimethylurea - 4 - 4

Example 4

In the greenhouse, the plants listed in the following table were treated after emergence with the compositions according to the invention in an application rate of 1 kg of active substance / ha. For this purpose, the compositions were sprayed in the form of an aqueous emulsion evenly over the plants. Here again, the compositions of the invention showed high crop tolerance 3 weeks after treatment with excellent weed control. The reference means did not show this selectivity. The result of the treatment was evaluated to mean = completely destroyed, = undamaged.

ti φ φ ω φ .O WITH > 0 Φ Compositions of the invention .ti φ W) ti ti and

4 ti ti 'Cti ti q O cd i - <r — I Φ £ N «m \ rH YrH>> P-l cn &

ж φ ti s> 'ti _ Ph Λ &

ti ti

Φ M t-C & ^g oo Л4 O

1- [4- (2,2-dichlorocyclopropylmethoxy) phenyl] -3,3-dimethylurea 10 10 10 10 0 0 0 0 0 1- [4- (2,2-dichlorocyclopropylmethoxy) -3-methylphenyl] -3,3-dimethylurea 10 10 10 10 - 0 0 0 0 0 1- [4- (2,2-dichlorocyclopropylmethoxy) phenyl] -3-methoxy-3-methylurea 10 10 10 10 - 0 0 0 0 0 untreated _ 10 10 10 10 10 10 10 10 10 10 The reference means of U.S. Pat. US 2,655,445] 1- (3,4-Dichlorophenyl) -3,3-dimethylurea 3 4 6 3 0 2 5 1 0 0

= completely destroyed = undamaged

Claims (1)

OBJECT OF THE INVENTION A selective herbicidal composition comprising at least one derivative of a compound of formula (I) RN-CO-NH (I) wherein R 1 is hydrogen, C 1 -C 4 alkyl, C 2 -C 4 alkynyl or methoxy, R 2 is hydrogen, C 1 -C 4 alkyl, R 3 a hydrogen atom, a C 1 -C 4 alkyl group, R 4 and R 5 are a halogen atom, X a hydrogen atom and / or a C 1 -C 4 alkyl group and / or a halogen atom and / or a methoxy group, an number 1 or 2; an amount of 10 to 80% by weight, 90 to 20% by weight of liquid or solid carriers, and optionally up to 20% by weight of surfactants.