PL101469B1 - A WORMHOUSE - Google Patents

Description

The present invention relates to a herbicide containing N-carbamoyl as active ingredient substituted oxanilic acid ethyl esters of general formula I, in which X and Y are each independently represent chlorine, bromine or trifluoromethyl, n is zero or one, m is zero or one, and R and Ri each independently represent 1-3 carbon lower alkyl, 1-3 carbon lower alkoxy carbon, or R and Ri together form groups represented by formulas 2, 3 or 4.

Due to the N-carbamoyl substitution of the compound of formula 1, the structure is similar to effluent ureas. Examples of such ureas in which the monocarbonyl radical is combined with a nitrogen atom that Jaóry is also attached to the halophenyl group are described in the French description Patent No. 1,250,422.

The compounds of formula I, being the active ingredient of the agent according to the invention, differ from these compounds. described in the above-mentioned patent in that they contain a pair of adjacent carbonyl groups, characteristic of oxanilic compounds.

The novel active ingredient compounds according to the invention are produced by acting on 1,3,3-tris urea with sodium hydride, and the resulting sodium salt of urea by treatment with ester chloride monoethyl oxalic acid as described below. The description of the manufacture of the two substances is followed by tables I, compounds produced the same way. The compound numbers given in Table I are used for identifying the results of the tests of the agent according to the invention listed in Table II.

Preparation of N7-dimethylcarbamoyl (-3'-trifluoromethyl-oxanilic acid) ethyl ester.

21.6 g (0.9 mol) are dispersed in 300 ml of tetrahydrofuran (dried on a molecular sieve) sodium hydride, then a solution of 191 g (0.823 mol) is added dropwise at room temperature under an argon shield 1- (m- trifluoromethylphenyl) - 3,3-dimethylurea in 1700 ml of dry tetrahydrofuran.

The mixture was stirred for an hour at room temperature, then another hour for another hour temperature 40-45 ° C.

The solution is decanted under argon and then added dropwise to a solution of 120 g (0.88 mol) of chloride oxalic acid monoethyl ester in 200 ml of tetrahydrofuran. The reactor is cooled during the dropwise addition. 101469 water, maintaining a temperature of 43 C or less. The precipitate formed and the mixture was stirred for about 16 hours at room temperature, then another hour at 45 ° C. Volatile components are removed under vacuum, and the residue is dissolved in 600 ml of benzene and 200 ml of 5% sodium acid carbonate solution.

The organic layer is washed with an additional 200 ml of acidic sodium carbonate and then dried over magnesium sulfate. The solvent is removed in a vacuum and the crude residue recrystallizes from benzene-hexane mixtures. The product yield is 175.7 g (65% of theory). Melting temperature 67-69 ° C. The structure of the compound is confirmed by infrared and NMR spectra.

Preparation of N7-dimethylcarbamoyl (-3 ', 4'-dichlorooxanilic acid ethyl ester).

24.5 g (1.02 mol) of sodium hydride are dispersed in 300 ml of dry tetrahydrofuran and then added dropwise 217 g (0.93 mol) of 1- (3,4-dichlorophenyl) -3,3-dimethylurea in 1600 ml of tetrahydrofuran in room temperature under argon. The whole thing is stirred for 1 hour at room temperature and 1 hour at a temperature of 40-45 ° C. The solution is transferred under an argon blanket to an addition funnel and then dripped into 136.5 g (1.0 mol) of oxalic acid monoethyl ester chloride dissolved in 180 ml of tetrahydrofuran. morning, allowing the temperature to rise to 43 ° C. The whole thing is stirred for 2 hours at room temperature, after then another 1.5 hours at 40-45 ° C, followed by a further 16 hours at room temperature.

Volatiles are removed under vacuum and the remainder is mixed with 800 ml of benzene and 400 ml of a 5% solution sodium acid carbonate. The undissolved material is filtered off, washed with benzene and dried. Original The benzene filtrate is washed twice with 200 ml of 5% sodium carbonate acid solution and dried over magnesium sulfate. This solution is concentrated in vacuo, filtered, and the filter cake washed in hexane and dried. The combined filter cakes give 249.8 g (80% of theory) of a product of mp 123-124 ° C. The product structure is confirmed by infrared and NMR spectra.

A particularly preferred method of preparing the compounds of formula I as active ingredients A measure according to the invention is to react to one stage in an inert solvent substituted urea of formula C6 H3 / X / n / Y / m-NH-CO-NRRi, where X and Y have the meaning given above and are substituents of the phenyl group in the ortho, meta- or para- position, n, m, R and Ri have the above-mentioned the meaning, with oxalic acid monoethyl ester halide of formula C2H5 O-CO-CO-Z, where Z denotes a chlorine or bromine atom, and in contrast to the method described above, the cheaper one is used solvent, for example a chlorinated hydrocarbon such as methylene chloride, chloroform, tetrachloride carbon or perchlorethylene, a hydrocarbon such as benzene or toluene, or diethyl ether. Tetrahydrofuran it can also be used as a solvent, however low chlorinated hydrocarbons have been found to be beneficial molecular substances such as methylene chloride and chloroform.

The reactions are carried out at the reflux temperature of the solvent used. These reactions are generally carried out in temperature range 40-120 ° C, preferably 40-80 ° C, depending on the solvent used. Solvent and the reaction temperature is chosen to prevent thermal decomposition of the product.

During the reaction, in addition to the desired N-carbamoyl-substituted oxanilic acid ethyl ester a hydrohalide is formed, i.e. a hydrochloride or a hydrobromide, depending on the ester halide used monoethyl oxalic acid. The pressure is at or slightly below atmospheric pressure to enable the removal of the by-product - hydrogen halide.

The preparation of the compounds of formula I by the preferred method described above is as follows: Preparation of N7-dimethylcarbannoyl (-3'-trifluoromethyloxanilic acid) ethyl ester. (Associate zek III in the table). 116 g (0.50 mol) of 1,1-dimethyl-3- (3'-trifluoromethyl) are introduced into a glass reactor. l-phenyl) -urea, 250 ml of methylene chloride and 82 g (0.60 mol) of acid monoethyl ester chloride oxalic. The resulting solution is boiled under reflux for 7 hours during which it all the urea is converted over time. The solvent and excess acid chloride are removed through evaporation, yielding 161 g of a white solid with a melting point of 67-69 ° C, the analysis of which is 96% pure and the achieved yield is 97%.

Preparation of N- (dimethyl-carbamoyl) -3 ', 4'-dichloro-oxanilic acid ethyl ester (Compound II in the table). 902 g (3.88 moles) of 1 / 3,4-dichloro is placed in a round bottom 5 liter, four necked flask. phenyl) -3,3-dimethyl urea and 2 liters of dry chloroform. The mixture is cooled with ice water, then • 610 g (4.46 moles) of oxalic acid monoethyl ester chloride are slowly added while maintaining the temperature below 20 ° C. After adding all of the acid chloride, the reaction mixture is warmed gently boiling under reflux for 8-9 hours until the reaction is completely complete, the course of which is monitored by liquid phase chromatography. Concentrate the solution on a rotary evaporator to about 1/4 volume the original, the resulting white compound is separated and dried, obtaining 1182 g (91% yield) of the desired compound 98% pure (mp 123-124 ° C). 101 469 In the blackboard! lists compounds of Formula 1, prepared by the described method.

Ta bI and ca I. Example compound n X m Y R Rt formula 1 AND II III IV V VI VII VIII 0 1 0 1 1. 1 1 1 ' 3CI 1 - 3-CI 3-CI 1 3-CI 3-CI 3-CI 1 1 4-CI 1 4-CI, 1 3-CF3 1 5-CI 1 4-CI 1 4-Br 1 4-CI 1 4-CI CH3 CH3 CH3 OCH3 OCH3 CH3 CH3 CH3 pattern 2 CH3 CH3 pattern 3 pattern 4 As already mentioned the compounds of formula I, prepared in the above-mentioned manner have properties phytotoxic and are useful as an active agent of the invention for controlling various kinds plant. <¦ \ The agent according to the invention, which contains the compounds of formula I as active ingredient, can be used before and after emergence of plants at different concentrations of the active substance. The measure is prepared known methods, using inert carriers and selecting its usable form for the method of application as powder, spray or aerosol, etc. The mixture can be dispersed in water with the addition of wetting agents or in the form of mixtures in an organic liquid, oil-water emulsions or water-oil emulsions with with or without wetting, dispersing or emulsifying agents.

The herbicide-effective amount depends on the type of seed or plant to be used controlled and the amount is 0.01-5.6 g / m2. The concentration of the active substance, enabling the selection of an effective amount a specialist can determine for best use.

The agent according to the invention containing an effective herbicidal amount of active ingredient can be used in a conventional manner.

Both powders and liquid mixtures can be applied to crops using sprayers powders, hand or draft sprayers, or aerosol sprayers.

The agent can be used by airplanes, both as a powder and as a spray, because it is effective at very low doses.

As a rule, to modify or limit the growth of germinating seeds or emerging seedlings the powder or liquid mixture is incorporated into the soil by conventional method to a depth of at least 13 mm. • It is not necessary for the phytotoxic to be mixed with soil particles, but these agents can only be applied to the soil surface by the spraying route. A measure according to the invention with properties Phytotoxic can be used by addition to water used for irrigation of the field. This method of application allows the penetration of the agent into the soil together with the adsorbed water.

The agent in the form of a powder, granules or liquid forms applied to the soil surface can be spread under the surface of the soil by conventional methods, by disking, harrowing or cultivating.

The herbicide according to the invention may contain other additives such as, for example, fertilizers, pesticides etc. used as admixtures or in combination with one of the listed additives.

Other phytotoxic substances useful as admixtures in the present invention include acid 2,4-dichlorophenoxyacetic, 2,4,5-trichlorophenoxyacetic, 2-methyl-4-chlorophenoxyacetic, and their salts, esters or amides, triazine derivatives such as 2,4-bis- (3-methoxy-propylaminoA 6-methylthio-s-triazine), 2-chloro-4- ethylamino-6- isopropylamino-s-triazine and 2-ethylamino-4- isopropylamino-6- methyl mercapto- -s-triazine, urea derivatives such as 3- (3,4-dichlorophenyl) -1,1-dimethyl urea, acetamides such as N, N-diallyl-α-chloroacetamide, N- / α-chloroacetylA hexamethyleneimine and N, N and the like, benzoic acids such as 3-amino-2,5-dichlorobenzoic, S-ethyl dipropyl carbamate; six- dihydrogen-1 H- azepine-1 - s-ethyl carbothionate etc. 4 101 469 According to the invention, fertilizers may be suitable for use with the active ingredient used, for example, ammonium nitrate, urea and superphosphate.

Other additives can be such materials in which plant organisms take root and grow such as compost, manure, humus, sand, etc.

Various modifications are possible without changing the scope of the subject matter of the invention, with the exact scope thereof they specify

Claims (9)

patent claims. Example 1 Testing the herbicidal properties before emergence On an analytical balance, 20 mg of a compound of formula I to be tested on a piece of glossy paper is weighed. The paper and the substance are placed in a wide-necked flask, 3 ml of acetone containing 1% Tween® (polyoxyethylene glycol sorbitol ether monolaurate) are added to dissolve the substance. If the material is insoluble in acetone, another solvent such as water, alcohol or dimethylformamide (DMF) is used. If DMF is used, only 0.5 ml or less is added, making up 3 ml with another solvent. 3 ml of the solution is sprayed evenly over a small surface of the soil one day after sowing plants. The liquid is sprayed with air with a pressure of 1.34 kg / cm2. 0.89 g / m2 is used with a spray volume of 0.133 l / m28 cm, width 12.7 cm and height 7 cm, a 5 cm layer of sandy loam is filled. The seeds of seven different types of plants are sown in single rows across the vessel. The seeds are covered with a layer of earth of 13 mm. 20-50 seeds are placed in one row, depending on the size of the plant. 3 ml of the solution is sprayed evenly over a small surface of the soil one day after sowing plants. The liquid is sprayed with air at a pressure of 1.34 kg / cm2. The amount used is 0.89 g / m2 with a spray volume of 0.133 l / m2. The day before spraying, trays 17.8 cm long, 12.7 cm wide and 7 cm high are filled with a 5 cm layer of clay-sand soil. Seeds of seven different types of plants are sown in individual rows located across the vessel The seeds are covered with a layer of earth of 13 mm. 20-50 seeds are placed in one row, depending on the size of the plants. ^ - ~ The seeds of Trichinella-Setaria spp, Watergrasu-Echinochloa crusgalli, red oats - Avena sativa; Amaranth - Amarc nthus retroflexus; mustard -Brassica juncea; riffle sorrel-Rumex cripus and bloodstaff - Digitaria sanguinalis. After spraying, the trays are placed in a greenhouse at 21-29 ° C and moistened by spraying. the same age for damage or growth limitation. Damage was rated from 0 to 100% for each type of plant tested, with no damage as 0% and total damage as by 100%. An example! I. Examination of herbicidal properties post-emergence Seeds of six plants namely bloodstain, watergras, red oats, mustard, curd sorrel and beans (Phaseolus vulgaria) were sown in trays as described above in the pre-emergence test. The trays were placed in a greenhouse at 21-29 ° C and irrigated daily by spraying. After 10-14 days after sowing, when the bean shoots had completely pierced and when the grass shoots started to form plants, the plants were sprayed with the agent prepared by weighing out 20 mg of the active substance dissolved in 5 ml of acetone containing 1% Tween® and adding 5 ml of water. The solution was applied with a sprayer using air at a pressure of 1.34 kg / cm2. The spray concentration is 0.2% and the amount of substance is 0.89 g / m2. Solution volume 0.44 l / m2. The test results are summarized in Table II. Table II Herbicidal activity results as a percentage for a dose of 0.89 g / cm2 Example of a compound of formula I II III IV V VI VII VIII Before emergence, the average of 7 types of plants (Example I) 98 99 99.6 0 100 94 26 55 After emergence average of 6 types of plants (Example II) 99 100 100 44 99 100 92 96 101 469 5 Patent claims 1.A herbicide containing a neutral carrier and a biologically active substance, characterized in that the active substance contains a phytotoxic compound of formula I, in which X and Y independently represent a chlorine, bromine or trifluoromethyl group, n is zero or one, m is zero or one, and R and Ri each independently represent 1-3 carbon lower alkyl, 1-3 carbon lower alkoxy, or Ri and R2 together form the groups represented by the formulas 2, 3 or 4. 2. "The measure according to claim A compound according to claim 1, characterized in that the active ingredient is a compound of formula I in which Y is a chlorine atom in the para position, n is zero, m is one and RiRi each is methyl. 3. The measure according to claim A compound according to claim 1, characterized in that the active ingredient is a compound of formula I, in which Y is trifluoromethyl, in meta position, n is zero, m is one, and R and Ri each are methyl. A composition according to claim 1, characterized in that the active ingredient is a compound of formula I, in which X is chlorine in meta position, Y is chlorine in para position, before each is one and R and Ri each are methyl group. 5. The measure according to claim A compound according to claim 1, characterized in that the active ingredient is a compound of formula I, in which X is a chlorine atom in the meta position, Y is a bromo atom in the para position, n is one, m is one, R is a methyl group and Rj is a group methoxy. 6. The measure according to claim 1; characterized in that the active ingredient is a compound of formula I, in which X is chlorine in meta position, Y is chlorine in para position, n is one, m is one, R is methyl and Ri is methoxy. 7. The measure according to claim A compound according to claim 1, characterized in that the active ingredient is a compound of formula I, in which X is chlorine in position 3, Y is chlorine in position 5, n is one, m is one, and R and Ri together form a group of formula 2. 8. The measure according to claim A compound according to claim 1, characterized in that the active ingredient is a compound of formula I, in which X is chlorine in meta position, Y is para chlorine, n is one, m is one, and R and Ri together form a group of formula 3. 9. The measure according to claim A compound according to claim 1, characterized in that the active ingredient is a compound of formula I, in which X is chlorine in meta position, Y is para chlorine, n is one, m is one, and R and Ri together form a group of formula 4. V v JL-f oo NCC-0C2Hs C = 0 INRR, Hz · M a · o *. • r * Pattern 2 Pattern 3 Pattern4