Derivatives of 3-(het)arylcarbamoyl acid herbicide preparation and agent for suppressing the growth

 

(57) Abstract:

Describes new derivatives of 3-(het)arylcarbamoyl acid of General formula I, where the values of R, R2- R6, Z, Y, X, specified in paragraph 1 of the formula expressing herbicide activity. Also describes herbicide-based preparation of compounds of formula I and a means to suppress plant growth. 3 S. and 4 C.p. f-crystals, 8 PL.

The present invention relates to new derivatives of 3-(het)arylcarbamoyl acid of General formula I,

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in which R denotes a group-COOH or a hydrolyzable to COOH radical-COR1in which R1denotes a radical OR10where R10is:

cation of an alkali metal, an equivalent of a cation of the alkali earth metal, a cation of ammonium, organic ammonium ion, or C1- C8-alkyl;

R2- C1-C4-alkoxygroup;

X represents CR14where R14is hydrogen;

R3represents C1-C4-alkoxygroup;

R4denotes phenyl which may be substituted by one or more residues selected from the group comprising halogen, C1-C4-alkyl, C1-C4-halogenated, C1-C4-alkoxygroup or sulfur, or 6-membered nitrogen-containing heteroaromatic residue;

R5denotes hydrogen, C1-C4-alkyl;

R6represents C1-C8-alkyl, which can be singly or multiply substituted by phenyl or by phenyl substituted by one or more residues selected from halogen and C1- C4-halogenoalkane;

Y represents sulfur or oxygen;

Z represents oxygen;

provided that R6represents unsubstituted C1-C4-alkyl, where R4denotes unsubstituted phenyl, Z represents oxygen and simultaneously R5denotes methyl or hydrogen.

In known publications relating to the prior art, for example in European application EP-A 347811, EP-A 400741, EP-A 409368, EP-A 481512, EP-A 517215, Chemical Abstracts, 119, N 139254e (1993) and in the earlier German application P 4142570 (European application EP-A 548710), describes similar similar derivatives of carboxylic acids, including 3-alkoxybenzenes, however, in these publications there are no derivatives with hearily radical in position 3.

In European application EP-A 0409368 described herbicide and suppressing plant growth composition based on heteroarylboronic derived karst and selectivity of known compounds far always been satisfactory. Therefore, the present invention is the finding compounds with higher selective effect in relation to cultivated plants and/or higher herbicide or Bioregulation activity.

Derivatives of 3-(het)arylcarbamoyl acid of General formula I of the present invention have a very good herbicide and regulating plant growth properties. In addition, compounds I are pharmacological action, especially with regard to cardiovascular system.

Preferred compounds of General formula I, in which R4denotes phenyl, possibly substituted, as described above, and the remaining substituents have the meanings mentioned above.

Especially preferred compounds of formula I in which Z represents oxygen, R4denotes phenyl which may be substituted, as defined above, R5denotes methyl, X denotes CH, R2and R3denote methoxy, and Y, R1and R6have the values specified above;

or the compounds of formula I in which R4represents a five - or six-membered heteroaromatic hydrocarbon mentioned above, and the remaining substituents have the meanings mentioned dstanley a five - or six-membered heteroaromatic hydrocarbon, above, R5denotes methyl, X denotes CH, R2and R3denote methoxy, a Y, R1and R6have the values specified above.

The present invention relates also to the herbicide product containing the active principle on the basis of the (het)aryl-substituted carboxylic acid derivative and an inert additive, which as the active agent contains a compound of the formula (I).

The invention also relates to means for suppressing the growth of plants containing the active principle on the basis of heteroaromatic carboxylic acid derivative and an inert additive, which, as the active agent contains a compound of the formula (I).

Compounds according to the invention are derived from epoxides of the formula IV obtained by well known techniques, e.g. as described in J. March, Advanced Organic Chemistry, 2nd edition, 1983, page 862, respectively, page 750, aldehydes, ketones respectively of formula II or of olefins of the formula III:

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Derivatives of 3-(het)arylcarbamoyl acid of General formula VI can be obtained by the interaction of the epoxides of General formula IV (e.g., with R denoting COOR10with alcohols of General formula V in which R6and Z have the meanings yasaitachi number, components, for example, 1.2 to 7, preferably 2-5 molar equivalents of the compounds of formula V, to a temperature of 50-200oC, preferably 80-150oC.

This reaction can be carried out in the presence of a diluent. For this purpose you can use any solvents that are inert to the reagents. Examples of such solvents, respectively diluents are water, aliphatic, alicyclic and aromatic hydrocarbons and their chlorinated derivatives, such as, for example, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, telengard and trichloroethylene, ethers, such as diisopropyl ether, disutility ether, propylene oxide, dioxane and tetrahydrofuran, ketones, such as acetone, methyl ethyl ketone, methylisobutylketone and methyl isobutyl ketone, NITRILES, such as acetonitrile and propionitrile, alcohols, such as methanol, ethanol, isopropanol, butanol and ethylene glycol, esters, such as, for example, ethyl acetate and amylacetate, acid amides, such as dimethylformamide and dimethylacetamide, sulfoxidov and sulfones, such katom carried out preferably in the interval 0oC to the boiling point of the solvent or solvent mixture, respectively.

Can also be used in the reaction of the catalyst, which may provide certain advantages. As catalysts there can be considered a strong organic acid and inorganic acid, and Lewis acid. Examples of such acids are, for example, sulfuric acid, hydrochloric acid, triperoxonane acid, apirat boron TRIFLUORIDE and an alcoholate of titanium (IV).

Proposed according to the invention compounds in which Y denotes oxygen, and the remaining substituents have the meanings mentioned for the General formula I, can be obtained, for example, the interaction of derivatives of 3-(het)arylcarbamoyl acid of General formula VI, in which the substituents have the abovementioned meanings, with compounds of General formula VII,

< / BR>
in which R15denotes halogen or R16- -SO2- where R16can be a C1-C4-alkyl, C1-C4-halogenated or phenyl. The reaction proceeds preferably in one of the abovementioned inert solvents with additives of the Foundation, i.e. such grounds, which can diprotodon> As the base can serve hydrides of alkali and alkaline earth metals, such as sodium hydride, potassium hydride or calcium hydride, a carbonate, for example, carbonates of alkali metals such as sodium carbonate or potassium carbonate, hydroxides of alkaline or alkaline earth metals such as sodium hydroxide or potassium hydroxide, ORGANOMETALLIC compounds such as utility, or amides of alkali metals, such as diisopropylamide lithium.

Compounds according to the invention in which Y represents sulfur, and the remaining substituents have the meanings mentioned for the General formula I, can be obtained, for example, the interaction of derivatives of 3-(het)arylcarbamoyl acid of General formula VIII, which can be obtained by known methods from compounds of General formula VI in which the substituents have the above meaning, with compounds of General formula IX in which R2, R3and X have the meanings indicated in the General formula I.

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The reaction proceeds preferably in one of the abovementioned inert solvents with additives of the Foundation, i.e. such grounds, which can deprotonate intermediate IX, in the temperature range from room temperature up to the organic base, as tertiary amines, such as triethylamine, pyridine, imidazole or diazabicyclo.

Compounds of General formula I can be obtained from the corresponding carboxylic acid, i.e. compounds of the formula I, in which R1represents a hydroxyl group, which is translated by well-known methods first, in activated form, such as a halide, anhydride or imidazole, and then subjected to the interaction with the corresponding hydroxyl compound HOR10. This interaction can be carried out in conventional solvents, preferably with the addition of one of the grounds listed above. The implementation of both of the above stages can be simplified, in particular by carrying out the reaction of carboxylic acid in the presence of a chip off the water tools, such as carbodiimide, with a hydroxyl compound.

In addition, compounds of General formula I can be obtained from the salts of the corresponding carboxylic acid, i.e. compounds of the formula I in which R represents a group COR1and R1represents OM, where M may be a cation of an alkali metal or an equivalent of a cation of the alkali earth metal. These salts may be interacting with a lot of the what aka as chlorine, bromine, iodine, or possibly substituted with halogen, alkyl or halogenation aryl - or alkylsulfonyl, such as, for example, toluensulfonyl and methylsulphonyl, or A stands for any other equivalent tsepliaeva group. The compounds of formula R1-A reactive Deputy A known or can be easily obtained by using well-known methods. This reaction can be carried out in conventional solvents and it is carried out mainly in the presence of one of the above grounds.

The radical R in the formula I varies within wide limits. This radical can represent, for example, a group

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in which R1has the following value:

a) hydrogen;

b) R1is a further radical OR10where R10represents: hydrogen, a cation of an alkali metal or cation of the alkaline earth metal, such as lithium, sodium, potassium, respectively, calcium, magnesium and barium, or an environmentally safe organic ammonium ion as tert.- C1-C4- alkylammonium, or ammonium cation;

C1-C8-alkyl means above all methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2 - methylpropyl, 1,1-dimethylethyl, pentyl, 1-IU the 1-methylpentyl, 2 - methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3 - dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2 - dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2 - trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl.

R2represents C1-C4-CNS group which may be substituted with halogen, such as, methoxy, ethoxy, deformedarse, triptoreline, particularly preferably methoxy;

X represents CR14where

R14represents hydrogen;

R3represents C1-C4-CNS group, such as methoxy, ethoxy;

R4represents 5 - or 6-membered heteroaryl as furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, isoxazolyl, oxazolyl, isothiazolin, thiazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, for example 2 - furanyl, 3-furanyl, 2-thienyl, 3-thienyl, 3 - isoxazolyl, 4 - isoxazolyl, 5-isoxazolyl, 3-isothiazole, 4 - isothiazole, 5 - isothiazole, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2 - thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 5 - imidazolyl, 2-pyrrolyl, 3-pyrrolyl, 4-pyrrolyl, 3-pyrazolyl, 4 - pyrazolyl, 5 - pyrazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, oxa-2,4 - diazole, oxa-3,4-diazo what Ohm halogen, first of all fluorine and chlorine, and/or from one to three residues selected from among the following:

C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, cyano, nitro, C1-C8- alkylsulphonyl, C1-C8-alkoxycarbonyl, phenyl, phenoxy, phenylcarbinol, as stated above, in particular;

R4means further phenyl which may be substituted by one or more, for example one or three, residues of the following: halogen, nitro, hydroxy, C1-C4-alkyl, C1-C4-halogenated, C1-C4-alkoxy, such as 3-hydroxyphenyl;

R5represents hydrogen, C1-C4-alkyl;

R6represents C1-C8-alkyl, singly or multiply substituted by phenyl or by phenyl substituted by halogen and/or C1-C4-halogenation;

Y represents sulfur, oxygen;

Z represents oxygen,

provided that R6represents unsubstituted C1-C4-alkyl, where R4denotes unsubstituted phenyl, Z represents oxygen and simultaneously R5denotes methyl or hydrogen.

Among the compounds of formula I are preferred those in which R2and R3about the table. 1. (see end of description). Represented in it, as well as in tables 2 and 3, the values of R4it should also be considered as preferred, regardless of the combinations of the values of other radicals R4.

The compound I, as well as their environmentally safe salts, for example salts of alkali and alkaline earth metals, and respectively containing these compounds herbicide drugs can highly be used to control weeds and unwanted plants in such crops as wheat, rice, corn, soybeans and cotton without causing damage to cultivated plants, - effect, which can be achieved primarily when using small quantities of active substances.

The compounds I or containing these compounds herbicide preparations can be applied in various forms, for example in the form intended for direct spraying of solutions, powders, suspensions, as well as high-grade aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, preparations for the dusting, spraying or granules. Using various methods, namely: spraying, dusting, aerosol processing a most uniform and extremely fine distribution of the active substances.

The compounds I are suitable in principle for the manufacture of them intended for direct spraying of solutions, emulsions, pastes or oil dispersions. As inert additives can be used, for example, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further, oil-based coal tar, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone or strongly polar solvents, such as N,N-dimethylformamide, dimethylsulfoxide, N-methyl - pyrrolidone or water.

Water forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or dispersible in water granules by water additives. To prepare emulsions, pastes or oil dispersions of active ingredients, either in their original form or after their dissolution in oil or solvent, can be homogenized in water by means of wetting, adhesives, dispergator is ligation and if necessary, solvents and oils can be produced corresponding concentrates suitable for dilution with water.

As surface-active substances can be used salts of alkali and alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsulfonate, phenolsulfonate, naphthalenesulfonate and dibutyldithiocarbamate, and also of fatty acids, alkyl - and alkylarylsulfonates, alkyl sulphates, sulphates lauric ester and fatty alcohols, further, salts of sulfated hexa-, hepta - and octadecanol, and glycol ether of a fatty alcohol, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or of naphthalenesulfonic with phenol and formaldehyde, simple polyoxyethyleneglycol ether, ethoxylated isooctyl, octyl - or Nonylphenol, simple alkyl phenol or tributyltinchloride ether, alkylarylsulfonate alcohols, isotridecyl alcohol, the condensation products of ethylene oxide fatty alcohol, ethoxylated castor oil, easy polyoxyethyleneglycol ether or polyoxypropylene, acetate, lauric alcohol and polyglycolide embrasse drugs preparations for dusting and atomization can be produced by the mixing or simultaneous grinding of active substances together with a solid filler.

The granules such as pellets with sheath, impregnated granulates and homogeneous granulates can be produced by binding of active substances with solid fillers. Such particulate fillers include mineral lands, in particular silicic acid, kieselgel, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and products of vegetable origin, such as flour of cereals, flour, bark, wood flour and flour from a nutshell, cellulose powders or other solid fillers.

Compositions containing active substances, usually in amounts of from 0.01 to 95 wt.%, preferably from 0.5 to 90 wt.%. The degree of purity of the applied active substances is thus 90-100%, preferably 95-100% (according to NMR spectrum).

Examples of such compositions are after is Sola, 10 mass.parts of the product of the merger 8-10 moles of ethylene oxide to 1 pray N-monoethanolamide oleic acid, 5 mass. parts of the calcium salt of dodecylbenzenesulfonate and 5 of the masses.parts of the product of the joining of 40 moles of ethylene oxide to 1 pray castor oil. After draining this solution into 100,000 masses.parts of water and its uniform and fine distribution in the water get a water dispersion containing 0.02 wt.% the active substance.

II. 20 mass.parts connection N 2.1 dissolved in a mixture consisting of 40 wt. parts of cyclohexanone, 30 mass. parts of Isobutanol, 20 mass.parts of the product of the joining of 7 moles of ethylene oxide to 1 pray isooctylphenol and 10 mass. parts of the product of the joining of 40 moles of ethylene oxide to 1 pray castor oil. After draining the solution into 100,000 masses.parts of water and its uniform and fine distribution in the water get a water dispersion containing 0.02 wt. % active ingredient.

III. 20 mass. parts of the active substance N 2.1 dissolved in a mixture consisting of 25 mass.parts of cyclohexanone, 65 mass.parts of mineral oil fraction with a boiling point 210-280oC and 10 mass.parts of the product of the joining of 40 moles of ethylene oxide to 1 pray castor oil. After levanderi, containing 0.02 wt.% the active substance.

IV. 20 mass.parts of the active substance N 2.1 thoroughly mixed with 3 wt. parts of the sodium salt of Diisobutylene- - sulfonic acids, 17 weight. parts of the sodium salt of ligninsulfonate from spent sulfite liquor and 60 mass. parts of powdered silica gel, and then pulverized in a hammer mill. Through a uniform and fine distribution of the mixture in 20,000 masses.the parts of water to obtain a solution for spraying, containing 0.1 wt.% the active substance.

V. 3 masses.part of the active substance N 2.1 mixed with 97 mass.parts of fine kaolin. In this way receive the drug for dusting containing 3 wt. % active ingredient.

VI. 20 mass.parts of the active substance N 2.1 thoroughly mixed with 2 wt. parts of the calcium salt of dodecylbenzenesulfonate, 8 mass.parts polyglycolic ether fatty alcohol, 2 mass.parts of the sodium salt of a condensate of a phenol-urea-formaldehyde and 68 mass.parts of a paraffinic mineral oil. In this way get a stable oil dispersion.

Herbicide preparations and, accordingly, the active substances can be used as in pedshed what estimatio with certain cultivated plants, can be applied such technology processing, in which the spraying herbicide preparations using an appropriate sprayers produce so that not to damage the leaves of sensitive cultural plants and that at the same time active ingredients get to the leaves growing under them undesirable plants or the open areas of soil (post-effect, strip tests).

Depending on the goals of treatment, time of year, species of cultivated plants and the growth stage, the amount of applied active substance is from 0.001 to 5.0 kg/ha, preferably from 0.01 to 2.0 kg of active substance (as.C.)/ha.

Considering the diversity of processing methods proposed according to the invention compounds, respectively preparations containing these compounds, can be used for controlling undesirable plants in the cultivation not only of the above cultivated plants, but a number of others. It is, in particular, on the following crops:

Allium CEPA, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spp. altissima, Beta vulgaris spp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea libericauus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago saliva, Musa spp., Nicotiana tabacum (N. rustica), Olea europaea, Oryza saliva, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum L., Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba L., Vitis vinifera, Zea mays.

The compounds of formula I can have a different impact on virtually all stages of development of different plants and are therefore used as growth regulators. The diversity of effects of plant growth regulators depends primarily

a) from the species and varieties of plants,

b) from time to time, in relation to the stage of plant development, and the time of year,

b) from the place and method of processing (e.g., seed treatment, soil treatment, processing leaves or injection into the trunk (tree crops)),

g) from climatic factors such as temperature, rainfall, and length of day length and light intensity,

d) from soils (including fertilizer),

e) from compositions, respectively, form of application active substances and, finally,

A. using the applied compounds of the invention are able to significantly inhibit the vegetative growth of plants, which is manifested primarily in the reduction of growth in height. As a consequence, the treated plants have shortened, "squat" form; in addition, such plants is more dark the colour of the leaves.

A significant advantage is that the reduced growth rate of grasses and such is subject to the lodging of crops as cereals, maize, sunflower and soybean. This decrease in growth rate contributes to the formation in plants shortened and thickened stem, resulting in adverse weather conditions before harvesting reduces or completely eliminates the danger of lodging (breaking) of plants.

Application of growth regulators is also important for the inhibition of growth in height and to change the time of the maturation process of cotton. This provides an opportunity for full mechanical harvesting of this important culture.

When caring for fruit trees and other woody vegetation due to regulator the SQL restorecolor on fruit trees.

Due to application of growth regulators can also promote lateral branching plants or to suppress it. This may be of interest, for example, in the cultivation of tobacco, when you want to suppress the formation of side shoots (summer shoots) to stimulate the growth of leaves.

Using growth regulators it is possible to improve the frost resistance of some plants, such as winter rape. Thus, on the one hand, depressed growth in height and suppressed the formation of too overgrown (and for this reason are particularly sensitive to frost) leaves, respectively blockage. On the other hand, after sowing and before the onset of winter, the young plants of rape despite the favourable growing conditions constrained in their vegetative stage of development. This eliminates the danger of frost damage of such plants, which have the ability to premature overcoming the negative impact on their flowering and the transition to the generative phase. In the cultivation of other crops such as winter cereals, it is also advisable to handle the crops compounds of the invention, so that in the autumn the plants though and well knoi monosaccharose and - due to the relatively sparse foliage, respectively herbal weight will prevent the risk of various diseases, such as fungal disease.

B. using growth regulators it is possible to increase the yield both in terms of vegetation, and plants contain substances. For example, it is possible to induce the formation of a larger number of buds, flowers, leaves, fruits, grains, roots and tubers, to increase the content of sugar in sugar beet, sugar cane and citrus fruits, to increase the protein content in grains and soybeans or to stimulate rubber trees to increased allocation of latex.

Thus the compounds of formula I can contribute to yield increase due to the impact on metabolism in plants or stimulation, respectively, inhibition of vegetative and/or generative growth.

C. With the aid of growth regulators can be reduced, thus increasing the duration of those or other stages of plant development, and accelerate, respectively, to slow down the ripening of the crop before or after harvest.

Interest from an economic point of view can imagine, N. the structure adhesiveness to the citrus tree, olives or other species and varieties of pome and stone fruits and nuts can greatly facilitate their removal. The same mechanism, i.e. creating conditions for the formation of the dividing tissue between fruit, leaves and shoots of plants, plays an important role for well-controlled defoliation of useful crops, such as cotton.

, And, finally, using growth regulators it is possible to reduce the water consumption of the plants. Thanks to the use of compounds according to the invention can reduce the intensity of irrigation and thereby improve the efficiency of farming, which is manifested, in particular, that

decreases the width of the stomata,

- formed a thicker epidermis and cuticle,

- improves root penetration in the soil and

- due to the more compact growth turns out to be a positive influence on the microclimate vegetation.

Particularly positive effect is obtained by applying the compounds I for the formation of shorter stems from such crops as barley, canola and wheat.

Used according to the invention the active substances of formula I can be made available to cultivated plants in various ways, ranging from proschaniem leaves.

Used quantity of active substances due to the high compatibility of the latter with plants is not critical. The optimal rate of consumption should be selected depending on the purpose of application, time of year, characteristics of the treated plants and the growth stage.

In the processing of seed consumption rates of active ingredient are generally from 0.001 to 50 g, preferably from 0.01 to 10 g, per 1 kg of seeds.

For processing of leaves and soil admittedly mostly sufficient consumption rates in the range from 0.001 to 10 kg/ha, preferably 0.01 to 3 kg/ha, especially from 0.01 to 0.5 kg/ha

To broaden the spectrum of action and achieve sinergeticheskogo effect of compounds of General formula I can be mixed with various other groups of active substances with herbicide and growth regulators properties, and performing the processing in conjunction with them. As components of such mixtures may be, for example, diazine, derivatives of 4H-3,1-benzoxazine, benzothiadiazine, 2,6 - dinitroanilines, N-phenylcarbamates, thiolcarbamate, halogenecarbonate acid, triazine, amides, urea, simple diphenyl ethers, triazinones, orally, be derived is nogroup, derivatives of quinoline-carboxylic acid, imidazolinones, sulfonamides, sulfonylureas, aryloxy-, respectively heterooligomerization acid, and their salts, esters and amides, and other substances.

In addition, the compounds of formula I without additives or in combination with other herbicides can also be used in mixture with other crop protection agents, for example with the means of combating pests or phytopathogenic fungi and bacteria. You might be interested in the possibility of mixing with solutions of mineral salts, which are used to compensate for the lack of nutrients and trace elements. Along with this can be entered supplements revitalising oils and oil concentrates.

Examples of the synthesis of

The synthesis of compounds of General formula VI

Example 1

Methyl ester of 3-methoxy-3-(3-methoxyphenyl)-2-hydroxybutiric acid

19.5 g (88 mmol) of the methyl ester 3-(3-methoxyphenyl)-2,3 - epoxybutane acid are dissolved in 200 ml of absolute methanol and mixed with 0.1 ml of epirate boron TRIFLUORIDE. Then stirred for 12 h at room temperature and the solvent is distilled off. The residue is dissolved in acetic ether, washed 1 g of pale yellow oil.

Yield: 94% (mixture of diastereomers 1:1).

Example 2

Methyl ester of 3-benzyloxy-3-phenyl-2-hydroxybutiric acid

9.6 g (50 mmol) of methyl ester of 3-phenyl-2,3-epoxybutane acid are dissolved in 150 ml of benzyl alcohol and mixed with 0.5 ml of concentrated sulfuric acid. Then stirred for 6 h at 50oC and cooled down to room temperature. After neutralization with sodium bicarbonate solution is distilled off excess benzyl alcohol under high vacuum and purify the residue by rapid chromatography on kieselgel using the solvent system n-hexane/acetic ether 9:1. After distillation of the solvent to obtain 6.5 g of colorless oil.

Yield: 43% (mixture of diastereoisomers 3:2).

Similarly received are presented in table. 2 connections (see the end of the description).

The synthesis of compounds of General formula I

Example 3

Methyl ester of 3-benzyloxy-3-phenyl-2- (4,6 - dimethoxypyrimidine-2-yl)hydroxybutyric acid

3 g (10 mmol) of methyl ester of 3-benzyloxy-3-phenyl-2-hydroxybutiric acid (compound 1.1) is dissolved in 40 ml of dimethylformamide and mixed with 0.3 g (12 mmol) of sodium hydride. Then stirred for 1 h, then added 2.2 g (10 mmol who goad hydrolyzing 10 ml of water, using acetic acid establish a pH value of 5 and the solvent is distilled under high vacuum. The residue is dissolved in 100 ml of acetic ether, washed with water, dried over sodium sulfate and the solvent is removed by distillation. The residue is mixed with 10 ml methyl - tert.-butyl ether and the formed precipitate is sucked off. After drying obtain 2.4 g of a white powder.

Yield: 55% (mixture of diastereomers 1:1).

Ttech115-117oC.

Example 4

3-benzyloxy-3-phenyl-2-(4,6-dimethoxypyrimidine-2-yl)hydroxybutyric acid

1.4 g (3 mmole) of methyl ester of 3-benzyloxy-3-phenyl-2-(4,6 - dimethoxypyrimidine-2-yl)-hydroxybutyric acid (example 3) was dissolved in 20 ml methanol and 20 ml of tetrahydrofuran and mixed with 3.7 g of 10% aqueous NaOH solution. Then stirred for 6 h at 60oC for 12 h at room temperature, after which the solvent is removed in vacuum and the residue is dissolved in 100 ml of water to obtain an aqueous solution of sodium salt of (R-COONa), next, to remove unreacted ester is extracted with acetic ester. Then the aqueous phase is set using diluted hydrochloric acid to pH 1-2 and extracted with a target product (R-COOH) with acetic ether. After drying over self is to suck. After drying obtain 1.2 g of white powder.

Yield: 88%.

Ttech165oC (decomposition, the mixture of diastereomers of 3:2).

Example 5

Methyl ester of 3-benzyloxy-3-phenyl-2-[(4,6-dimethoxypyrimidine-2-yl) thio]-butyric acid

11 g (25 mmol) of methyl ester of 3 - benzyloxy-3-phenyl-2-hydroxybutiric acid (compound 1.1) is dissolved in 50 ml of dichloromethane, then add 3 g (30 mmol) of triethylamine and stirring is added dropwise a further 3.2 g (28 mmol) of the chloride methansulfonate. Then stirred for 2 h at room temperature, washed with water, dried over magnesium sulfate and concentrated in vacuo. The residue is dissolved in DMF and at temperatures of 0oC added dropwise to a suspension of 12.9 g (75 mmol) of 4,6-dimethoxypyrimidine-2-thiol and 8.4 g (100 mmol) of sodium bicarbonate in 100 ml of DMF. After stirring for 2 h at room temperature and further stirring for 2 h at 60oC is poured into 1 l of ice water and the precipitate is sucked off.

After drying obtain 3.2 g of white powder.

Yield: 29% (mixture of diastereomers 1:1).

In a similar way, as described in the above examples, the received connection prestanic 3- (het)arylcarbamoyl acid of General formula I confirm the results of the experiments, conducted in the greenhouse.

As pots served plastic flower pots with soil type on sandy loam containing about 3% of humus as a substrate. The seeds of the experimental plants were sown separately.

When predsjedava processing directly after sowing was carried atomized spraying suspended or emulsified in water active ingredients with suitable nozzles. The vessels were subjected to light sprinkling, in order to promote germination and development of plants, after which the pots were covered with transparent plastic covers until the plants started to grow. Thanks to such covers shall be provided for uniform germination of the experimental plants, because thus neutralized the effect of the active substances.

When conducting post-harvest processing pilot plant, depending on their exterior handle suspended or emulsified in water active ingredients only when they reach a height of about 3-15 see With this objective of the pilot plants are either sown directly and grown in the same containers, or their first you the dy. When conducting post-harvest processing of the active substance (and.in.) the use of a 0.125, respectively 0.06 kg/ha Plants kept separately by type at temperatures in the range from 10 to 25oC, respectively, from 20 to 35oC. the Experiments were continued for 2-4 weeks. During this period of time the plants were thorough care and recorded their reaction conducted after each treatment. The evaluation was made on a scale of values from 0 to 100. Where 100 means that plants do not sprout, i.e. is the complete destruction of at least their aerial parts, and 0 means no damage and there is a normal process of growth.

Summarized in tables 4-8 data suggests a high weed-killing activity of the claimed compounds. In addition, table 5 illustrates the selective effect of the compounds in figure 2.16 and table 6 - selective effect connection 2.52 on spring wheat.

1. Derivatives of 3-(het)arylcarbamoyl acid of the formula I

< / BR>
in which R denotes a group-COOH or a hydrolyzable to COOH radical-COR1in which R1denotes a radical OR10where R10represents: the alkaline cation m is8alkyl;

R2represents C1- C4- alkoxygroup;

X represents CR14where R14is hydrogen;

R3represents C1- C4- alkoxygroup;

R4denotes phenyl which may be substituted by one or more residues selected from the group comprising halogen, C1-C4-alkyl, C1-C4-halogenated, C1-C4-alkoxygroup and the nitro-group, or a 5-membered heteroaromatic residue, containing 1-2 nitrogen atom and/or one oxygen atom or sulfur, or 6-membered nitrogen-containing heteroaromatic residue;

R5denotes hydrogen, C1- C4-alkyl;

R6represents C1- C8- alkyl, which can be singly or multiply substituted by phenyl or by phenyl substituted by one or more residues selected from halogen and C1-C4-halogenoalkane;

Y represents sulfur or oxygen;

Z represents oxygen;

provided that R6represents unsubstituted C1- C4-alkyl, where R4denotes unsubstituted phenyl, Z represents oxygen and simultaneously R5denotes methyl or hydrogen.

2. Connections are important, specified in paragraph 1.

3. Connection on p. 1, in which Z represents oxygen, R4denotes phenyl which may be substituted, as indicated in paragraph 1, R5denotes methyl, X denotes a CN, R2and R3denotes methoxy, and Y, R1and R6shall have the meaning specified in paragraph 1.

4. Connection on p. 1, in which R4represents a five - or six-membered heteroaromatic hydrocarbon under item 1, and the remaining substituents have the meanings set out in paragraph 1.

5. Connection on p. 1, in which Z represents oxygen, R4represents a five - or six-membered heteroaromatic hydrocarbon under item 1, R5denotes methyl, X denotes a CN, R2and R3denote methoxy, and Y, R1and R6shall have the meaning specified in paragraph 1.

6. Herbicide product containing the active principle on the basis of the (het)aryl-substituted carboxylic acid derivative and an inert additive, characterized in that the active agent contains a compound of formula I under item 1.

7. Means for inhibiting the growth of plants containing the active principle on the basis of the (het)aryl-substituted carboxylic acid derivative and an inert additive, characterized in that the quality and

 

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