Derivatives of 3-halogen-3-heterylcarbonyl acid herbicide tool

 

(57) Abstract:

The present invention relates to derivatives of 3-halogen-3-hetaryl-carboxylic acid of the formula I

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in which R denotes the group-C(O)R1where R1represents C1-C4-alkoxygroup or9where R9represents hydrogen or the cation of an alkali metal; R2and R3denote C1-C4-alkoxygroup; X represents CR13where R13is hydrogen; R4denotes a five - or six-membered heteroaromatic ring containing one to two nitrogen atoms and/or one sulfur atom or one oxygen atom, which may carry one or more residues selected from among the following: C1-C4-alkyl, or phenyl; R5denotes hydrogen or C1-C4-alkyl; Y represents sulfur or oxygen; Z is a halogen, and herbicide tool based on them. These compounds possess herbicide activity and can find application in agriculture. 2 S. and 2 C.p. f-crystals, 9 PL.

The present invention relates to derivatives of 3 - halogen-3-heterylcarbonyl acid and herbicide means containing these compounds.

Known sigogneau application P 4142570 (European application EP-A 548710), describes similar derivatives of carboxylic acids, in particular 3-halogen derivatives, however, in these publications there are no derivatives bearing wearily radical in position 3.

Based on the fact that the biological effectiveness and selectivity of known compounds far always been satisfactory, the basis of the invention was based on the task to obtain compounds with more sophisticated selective effect in relation to cultivated plants and/or higher herbicide or Bioregulation efficiency.

This object is achieved by the creation of derivatives of 3-halogen-3-heterylcarbonyl acid of General formula I

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in which R denotes the group-C(O)R1where R1represents C1-C4-alkoxygroup or9where R9represents hydrogen or the cation of an alkali metal;

R2and R3denote C1-C4-alkoxygroup;

X represents CR13where R13is hydrogen;

R4denotes a five - or six-membered heteroaromatic ring containing one to two nitrogen atoms and/or one sulfur atom or one oxygen atom, which stands for hydrogen or C1-C4-alkyl;

Y represents sulfur or oxygen;

Z represents halogen.

Preferred derivatives of 3-halogen-3-heterylcarbonyl acid of General formula I, in which R5denotes methyl, X denotes CH, R2and R3denote methoxy, a Y, Z, R1and R4have the meanings specified above.

Preferred derivatives of 3-halogen-3-heterylcarbonyl acid of General formula I, in which Z represents fluorine, R5denotes methyl, X denotes CH, R2and R3denote methoxy, a Y, R1and R4have the meanings specified above.

This object is achieved also by the creation of herbicide products containing derived halogencarbonic acid and conventional inert additives, which according to the invention as derived halogencarbonic acid use one of the compounds of General formula I.

Also describes derivatives of 3-halogen-3-heterylcarbonyl acid of General formula I'

< / BR>
in which R denotes formulabuy group, a group of CO2H or a hydrolyzable to COOH radical, and the remaining substituents have the following meanings:

R2denotes halogen, C1-C4-alkyl,/SUB>-alkylthio;

X is nitrogen or CR13and R13is hydrogen or together with R3form 3-4-tier alkylenes or alkenylamine circuit, in which a methylene group is replaced by oxygen;

R3denotes halogen, C1-C4-alkyl, C1-C4-halogenated, C1-C4-alkoxy, C1-C4-halogenoalkane, C1-C4-alkylthio or R3together with R13in the same way as described above, are connected to each other to form a 5 - or 6-membered ring;

R4denotes a five - or six-membered containing one to three nitrogen atoms and/or one sulfur atom or one oxygen atom, heteroaromatic hydrocarbon, which may carry one or more residues selected from among the following: halogen, nitro, cyano, hydroxy, mercapto, amino, C1-C4-alkyl, C1-C4-halogenated, C1-C4-alkoxy, C1-C4-halogenoalkane, C1-C4-alkylthio, C1-C4-alkylamino, di-C1-C4- alkylamino, C1-C4-alkylsulphonyl, C1-C4-alkoxycarbonyl or phenyl;

R5denotes hydrogen, C1-C4-alkyl, C3-C6alkenyl, C3-C6->C4-alkylthiol or phenyl;

Y represents sulphur or oxygen, or a simple bond;

Z represents halogen.

It was found that the above-mentioned derivatives of 3-halogen-3-hetaryl-carboxylic acid have a very good herbicide and regulating plant growth properties.

Upon receipt of the described compounds come from the epoxides of formula IV, which get 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-halogen-3-heterylcarbonyl acid of the formula VI can be obtained by the interaction of the epoxides of formula IV (e.g., with R denoting COOR9with halogen derivatives MZ formula V in which Z has the meaning indicated above, and M denotes hydrogen, a cation of an alkali metal or an equivalent of a cation of the alkali earth metal:

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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 which can be chlorinated, 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 the ethyl acetate and amylacetate, acid amides, such as dimethylformamide and dimethylacetamide, sulfoxidov and sulfones, such as dimethyl sulfoxide and sulfolane, and bases, such as pyridine.

The reaction when carried out preferably in the temperature range from 0oC to the boiling point of the solvent, respectively diluent.

The presence in the reaction catalyst may provide certain advantages. As catalysts may be considered organic acid, inorganic acid, and Lewis acid. Examples of such acids are, among others, sulfuric acid, hydrochloric acid, triperoxonane acids is no oxygen, and the remaining substituents have the meanings indicated in the General formula I' can be obtained, for example, the interaction of derivatives of 3-halogen-3-heterylcarbonyl acid of General formula VI with compounds of General formula VII

< / BR>
in which R14denotes halogen or R15SO2-, and R15represents 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 deprotonate compound VI, in the temperature range from room temperature up to the boiling point of the solvent.

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 alkaline metals such as sodium carbonate or potassium carbonate, hydroxides of alkaline metals such as sodium hydroxide or potassium hydroxide, ORGANOMETALLIC compounds, as utility, or amides of alkali metals, as diisopropylamide lithium.

Compounds in which Y represents sulfur, and the remaining substituents have the meanings indicated in the General formula I' can R>< / BR>
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

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in which R2, R3and X have the meanings indicated in the General formula I'.

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 boiling point of the solvent.

As grounds along with the above can serve as organic bases like triethylamine, pyridine, imidazole or diazabicyclo.

Compounds of General formula I' can be obtained also thanks to the fact that originate from the corresponding carboxylic acid, i.e. compounds of the formula I' in which R represents COOH, then translate them by well-known methods first, in activated form, such as a halide, anhydride or imidazole, and these latter are subjected after this interaction with the corresponding hydroxyl compound HOR9. This interaction can be carried out in conventional solvents and s stages can be simplified, in particular, due to the fact that the carboxylic acid in the presence of a chip off the water funds, as carbodiimide affect hydroxyl compound.

In addition, compounds of General formula I' can be obtained due to the fact that proceed from the salts of the corresponding carboxylic acids, i.e., for example, from compounds of the formula I' in which R represents a group C(O)R1and R1represents OM, where M may be, for example, a cation of an alkali metal or an equivalent of a cation of the alkali earth metal. Named salt can be subjected to interaction with many of the compounds of the formula R1-A, where a denotes the usual oleophobol tsepliaeva group, for example halogen such as chlorine, bromine, iodine, or when certain conditions are replaced by halogen, alkyl or halogenated aryl - or alkylsulfonyl, such as toluensulfonyl and methylsulphonyl, or A stands for any other equivalent tsepliaeva group. The compounds of formula R1-A reactive Deputy A known or can easily be obtained using well-known methods. This reaction can be carried out in conventional solvents and it is conducted preferably in the presence of one of either the conduct themselves, for example, a group

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in which R1has the following value:

a) hydrogen;

b) actinomycetoma;

b) linked through a nitrogen atom of a 5-membered heteroaromatic hydrocarbon, as pyrrolyl, pyrazolyl, imidazolyl and triazolyl, which may carry one or two halogen atom, especially fluorine and chlorine, and/or one or two remnant from among the following:

C1-C4-alkyl, like methyl, ethyl, 1-propyl, 2-propyl, 2-methyl-2-propyl, 2-methyl-1-propyl, 1-butyl, 2-butyl;

C1-C4-halogenated primarily C1-C2-halogenated, as, for example, vermeil, deformity, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl, 1-foretel, 2-foretel, 2,2-dottorati, 2,2,2 - triptorelin, 2-chloro-2,2-dottorati, 2,2-dichloro-2-foretel, 2,2,2-trichlorethyl and pentafluoroethyl;

C1-C4-halogenoalkane primarily C1-C2-halogenoalkane as deformedarse, triptoreline, chloroformate, 1 floratone, 2-floratone, 2,2-diflorasone, 1,1,2,2-tetrafluoroethoxy, 2,2,2-triptoreline, 2-chloro-1,1,2-triptoreline, pentaborate, primarily triptoreline;

C1-C4-alkoxy like methoxy, ethoxy, propoxy, 1 - methylethoxy, butoxy, 1 methylpropoxy, 2-methylpropoxy is about, ethylthio, propylthio, 1 metalicity, butylthio, 1 methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, especially methylthio, ethylthio;

g) R1represents the next residue(O)m-NR6R7in which m denotes 0 or 1, a R6and R7which may be identical or different, have the following meanings:

hydrogen;

C1-C8-alkyl, especially C1-C4is alkyl having the above values;

C3-C6alkenyl as 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl - 2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl - 2-pentenyl, 4-methyl-2-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, Il, 2-butenyl, 3-methyl-2 - butenyl and 3-methyl-2-pentenyl;

C3-C6-quinil as 2-PROPYNYL, 2-butynyl, 3-butynyl, 1-methyl-2-PROPYNYL, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1,1-dimethyl-2-PROPYNYL, 1-ethyl-2-PROPYNYL, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-2-pentenyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butinyl, 1-ethyl-2-butinyl, 1 - ethyl-3-butinyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-PROPYNYL, preferably 2-PROPYNYL, 2-butynyl, 1-methyl-2-PROPYNYL and 1 - methyl-2-butenyl, primarily 2-PROPYNYL;

C3-C8-cycloalkyl as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, and these alkyl, cycloalkyl, alkeline and alkyline groups may carry from one to five, especially from one to three halogen atoms, preferably fluorine or chlorine, and/or one or two groups selected from among the following:

C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-halogenoalkane in the above description, C is quinitio, moreover, existing in these residues alkeneamine and alkyline fragments preferably correspond to the above-mentioned values;

C1-C4-alkylsulphonyl as primarily methylcarbamyl, ethylcarboxyl, propylmalonic, 1-methylethylketone, butylcarbamoyl, 1-methylpropylamine, 2-methylpropionyl, 1,1-dimethylethylamine;

C1-C4-alkoxycarbonyl as methoxycarbonyl, etoxycarbonyl, propylenecarbonate, 1-methylethanolamine, butyloxycarbonyl, 1-methyl-propylenecarbonate, 2-methylpropionitrile, 1,1-dimethylethoxysilane;

C3-C6-alkenylboronic, C3-C6-alkenylboronic, C3-C6- alkenylacyl and C3-C6-alkyloxyaryl, and alkeneamine, respectively alkyline residues preferably have the above meanings;

phenyl, under certain conditions, singly or multiply substituted by halogen, nitro, cyano, C1-C4-alkyl, C1-C4-halogenated, C1-C4-alkoxy, C1-C4-halogenoalkane or C1-C4-alkylthio, as, for example, 2-forfinal, 3-chlorophenyl, 4-bromophenyl, 2-were, 3-nitrophenyl, 4-cyanophenyl, 2-triptoreline, 3-methoxyphenyl, 4-trif 2,6 - differenl; di-C1-C4-alkylamino, primarily as dimethylamino, dipropylamino, N-propyl-N-methylamino, N-propyl-N-ethylamino, diisopropylamino, N-isopropyl-N-methylamino, N-isopropyl-N-ethylamino, N-isopropyl-N-propylamino;

R6and R7represent a further phenyl which may be substituted by one or more residues selected from among the following: halogen, nitro, cyano, C1-C4-alkyl, C1-C4-halogenated, C1-C4-alkoxy, C1-C4-halogenoalkane or C1-C4-alkylthio having the meanings given above;

or R6and R7both together form a closed ring, with optional substitution of C4-C7-alkylenes chain, which may contain a heteroatom selected from the group oxygen, sulfur or nitrogen, as -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)2-O-(CH2)2-, -CH2-S-(CH2)3-, -(CH2)2-O-(CH2)3-, -NH-(CH2)3-, -CH2-NH-(CH2)2-, -CH2-CH= CH-CH2-, -CH= CH-(CH2)3- and as Vice-treated primarily C1-C4-alkyl residues;

d) R1represents the Yes is C4-alkyl, C1-C4-halogenated, C3-C6alkenyl, C3-C6-quinil or under certain conditions, substituted phenyl, as it is, in particular, specified when the characteristic of R6and R7;

e) R1is a further radical OR9where R9means:

I) hydrogen, a cation of an alkali metal or cation of the alkaline earth metal, such as lithium, sodium, potassium, calcium, magnesium and barium, or an environmentally safe organic ammonium ion as tert.-C1-C4-alkylammonium or ammonium [NH4+];

II) C3-C8-cycloalkyl with the above values, which may carry from one to three C1-C4is an alkyl group;

III) C1-C8-alkyl, primarily as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1 - methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 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, which can -C4-alkoxy, C1-C4-alkylthio, cyano, C1-C4- alkylsulphonyl, C3-C8-cycloalkyl, C1-C4-alkoxycarbonyl, phenyl, phenyl, singly or multiply substituted by halogen, nitro, cyano, C1-C4-alkyl, C1-C4-halogenated, C1-C4-alkoxy, C1-C4-halogenoalkane and/or C1-C4-alkylthio or phenoxy, primarily having the above meanings;

IV) C1-C8is an alkyl group having the above-mentioned values, which may carry from one to five, preferably one to three halogen atoms, especially fluorine and/or chlorine, and which is one residue selected from among the following: 5-membered heteroaromatic hydrocarbon containing from one to three nitrogen atoms or a 5-membered heteroaromatic hydrocarbon containing one nitrogen atom and one oxygen atom or one sulfur atom as pyrazolyl, imidazolyl, benzimidazolyl, triazolyl, benzotriazolyl, isooxazolyl, oxazolyl, thiazolyl, linked through the C-atom or, if possible, via the N-atom, and heteroaromatic hydrocarbons can carry one to four halogen atoms and/or one or two remnant from among the following: nitro, cyano, C1-C41-C4-alkylthio. First of all we should mention: 1-pyrazolyl, 3-methyl-1-pyrazolyl, 4-methyl-1-pyrazolyl, 3,5-dimethyl-1-pyrazolyl, 3-phenyl-1-pyrazolyl, 4-phenyl-1-pyrazolyl, 4-chloro-1-pyrazolyl, 4-bromo-1-pyrazolyl, 1-imidazolyl, 1-benzimidazolyl, 1,2,4-triazole-1-yl, 3-methyl-1,2,4-triazole-1-yl, 5-methyl-1,2,4-triazole-1-yl, 1-benzotriazolyl, 3-isopropylthiazole-5-yl, 3-methylisoxazol-5-yl, oxazol-2-yl, thiazol-2-yl, imidazol-2-yl, 3-utilization-5-yl, 3 - phenylisoxazol-5-yl, 3-tert.-butylisoxazole-5-yl;

V) C2-C6is an alkyl group, bearing in position 2 one residue selected from among the following: C1-C4-alkoxyimino, C3-C6-alkynylamino, C3-C6- halogenocarboxylic or benzylamino;

VI) C3-C6-alkenylphenol or C3-C6-alkylamino group, and these groups in turn may carry from one to five halogen atoms;

VII) R9can be a further phenyl radical which can carry one to five halogen atoms and/or from one to three residues selected from among the following: nitro, cyano, C1-C4-alkyl, C1-C4-halogenated, C1-C4-alkoxy, C1-C4-halogenoalkane and/or C1-C4-alkylthio shown in arearomance hydrocarbon, as pyrazolyl, imidazolyl, benzimidazolyl, triazolyl, benzotriazolyl, preferably linked via position 1, and heteroaromatic hydrocarbons can carry one or two halogen atom and/or one or two remnant from among the following: C1-C4-alkyl, C1-C4-halogenated, C1-C4-alkoxy, phenyl, C1-C4-halogenoalkane and/or C1-C4- alkylthio. First of all we should mention: 1-pyrazolyl, 3-methyl-1 - pyrazolyl, 4-methyl-1-pyrazolyl, 3,5-dimethyl-1-pyrazolyl, 3-phenyl-1-pyrazolyl, 4-phenyl-1-pyrazolyl, 4-chloro-1-pyrazolyl, 4-bromo-1-pyrazolyl, 1-imidazolyl, 1-benzimidazolyl, 1,2,4-triazole-1-yl, 3-methyl-1,2,4-triazole-1-yl, 5-methyl-1,2,4-triazole-1-yl, 1-benzotriazolyl, 3,4-dichloroimidazole-1-yl;

IX) R9represents the next group

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where R10and R11which may be identical or different, denote:

C1-C8-alkyl, C3-C6alkenyl, C3-C6- quinil, C3-C8-cycloalkyl, and these radicals can carry C1-C4-CNS, C1-C4-acitivy and/or under certain conditions, a substituted phenyl residue, which has the above meanings; phenyl which may be substituted by one or more of the1-C4-alkoxy, C1-C4-halogenoalkane or C1-C4-alkylthio, and these residues correspond to residues mentioned as preferred for R1;

or R10and R11both together form a C3-C12-alkylenes chain, which may carry from one to three C1-C4-alkyl groups and which may contain a heteroatom from the group of oxygen, sulfur and nitrogen, as indicated in preferred values for R6and R7;

W) R1represents the next residue-NH-SO2-R12where R12has the following values:

C1-C4-alkyl, C3-C6alkenyl, C3-C6-quinil, C3-C8-cycloalkyl with the above values, preferred for R1and these radicals can carry C1-C4-CNS, C1-C4-acitivy and/or phenyl residue in the above decoding;

phenyl, under certain conditions substituted as indicated above.

Taking into account their biological effectiveness to the preferred derivatives of 3-halogen-3-heterylcarbonyl acid of General formula I' are those in which the remaining substituents have the following Sychev>-C4-halogenation, C1-C4-CNS, C1-C4- halogenalkyls, C1-C4-allylthiourea and halogen atoms, especially chlorine, methyl, methoxy, ethoxy, deformedarse, triptoreline, especially preferred methoxy;

X is nitrogen or CR13where

R13represents preferably hydrogen or forms together with R34-5-tier alkylenes or alkenylamine circuit, in which a methylene group is replaced by oxygen, CH2-CH2-O-, -CH=CH-O-, -CH2-CH2-CH2-O-, -CH=CH-CH2O-primarily hydrogen and-CH2-CH2-O-;

R3means mentioned above, when the characteristic of R1C1-C4-alkyl, C1-C4-halogenation, C1-C4-CNS, C1-C4-halogenalkyls,

C1-C4-allylthiourea and halogen atoms, especially chlorine, methyl, methoxy, ethoxy, deformedarse, triptoreline, especially preferred methoxy, or, as stated above, is associated with R13forming a 5 - or 6-membered ring;

R4represents 5 - or 6-membered heteroaryl as furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl 2-furyl, 3-furyl, 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-diazole, thia-2,4-diazole, thia-3,4-diazole and triazolyl, and heteroaromatic hydrocarbons can carry one or more residues selected from among the following:

halogen, nitro, cyano, hydroxy, mercapto, amino, C1-C4-alkyl, C1-C4-alkoxy, C1-C4- alkylthio, C1-C4-halogenated, C1-C4-halogenoalkane, C1-C4-alkylamino, di-C1-C4-alkylamino, C1-C4- alkylsulphonyl, C1-C4- alkoxycarbonyl and phenyl, as stated above in General and in particular;

R5represents hydrogen, C1-C4- alkyl, C3-C6alkenyl, C3-C6-quinil, C3-C8-cycloalkyl, C1-C4-halogenated, C1-C4-alkoxyalkyl, C1-C4-alkylthiol or phenyl, as described above;

Y represents sulfur, oxygen or simple which R5denotes methyl, X denotes CH, R2and R3represent methoxy. For the preferred compounds of formula I further include those in which R5represents methyl, X represents CH, Z represents fluorine and R2and R3represent methoxy. In addition, R1preferably represents a group OR9first of all OH and OC1-C4-alkyl.

The variable Y represents preferably sulfur, and above all the oxygen.

The most preferred compounds of formula I' are presented in table. 1. Represented in it, as well as in table. 2 and 3 the values of R4it should also be considered as preferred, regardless of other values for this radical.

The compounds of formula I', respectively containing these compounds herbicide preparations, as well as their environmentally safe salts, for example salts of alkali and alkaline earth metals, 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.

They can the cross-sections, powders and 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, such as spraying, dusting, aerosol processing in the form of mists and fumes or watering. These forms and methods are determined by the purpose of the application, but in all cases should be provided the most uniform and extremely fine distribution of the active substances according to the invention.

The compounds of formula 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, among other fractions of mineral oil with medium and 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, cyclohexanediamine or water.

Aquatic forms of application 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, dispersants or emulsifiers. Along with this, of active substance, wetting, adhesives, dispersants or emulsifiers and, if possible, 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 NAF is m and formaldehyde, simple polyoxyethyleneglycol ether, ethoxylated isooctyl, octyl - or Nonylphenol, simple alkyl phenol-, tributyltinchloride ether, alkylarylsulfonate alcohols, isotridecyl alcohol, condensates of fatty alcohol and ethylene oxide, ethoxylated castor oil, easy polyoxyethyleneglycol ether or polyoxypropylene, acetate polyglycolide ester lauric alcohol, complex sorbitol esters, exhaust ligninolytic liquor or methylcellulose.

Powdered drugs, drugs 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 granules and homogeneous granules, can be produced by binding of active substances with solid fillers. Such particulate fillers include mineral lands, in particular silicic acid, silica gel, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers as ammonium sulfate, ammonium phosphate, nebesna 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 the following:

I. 20 wt.parts connection N 2.17 dissolved in a mixture consisting of 80 wt. parts of alkylated benzene, 10 wt.parts of the product of the merger 8-10 moles of ethylene oxide to 1 pray N-monoethanolamide oleic acid, 5 wt. parts of the calcium salt of dodecylbenzenesulfonate and 5 wt.parts of the product of the joining of 40 moles of ethylene oxide to 1 pray castor oil. After draining this solution in 100000 wt.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 wt.parts connection N 2.1 dissolved in a mixture consisting of 40 wt.parts of cyclohexanone, 30 wt.parts of Isobutanol, 20 wt.parts of the product of the joining of 7 moles of ethylene oxide to 1 pray isooctylphenol and 10 wt.parts of the product of the joining of 40 moles of ethylene oxide to 1 pray castor oil. Posdnous dispersion, containing 0.02 wt.% the active substance.

III. 20 wt.parts of the active substance N 2.17 dissolved in a mixture, consisting of soup from 25 wt.parts of cyclohexanone, 65 wt.parts of the fraction of mineral oil with a boiling point 210-280oC and 10 wt.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 wt.parts of water and its uniform and fine distribution in the water get a water dispersion containing 0.02 wt.% the active substance.

IV. 20 wt. parts of the active substance N 2.2 thoroughly mixed with 3 wt. parts of the sodium salt of diisobutylamine-- sulfonic acids, 17 wt.parts of the sodium salt of ligninsulfonate from spent sulfite liquor and 60 wt.parts of powdered silica gel, and then pulverized in a hammer mill. Through a uniform and fine distribution of the mixture in 20000 wt.the parts of water to obtain a solution for spraying, containing 0.1 wt.% the active substance.

V. 3 wt.part of the active substance N 2.17 mixed with 97 wt.parts of fine kaolin. In this way receive the drug for dusting containing 3 wt.% the active substance.

VI. 20 wt.parts deistviyami polyglycolic ether fatty alcohol, 2 wt.parts of the sodium salt of a condensate of formatively-formaldehyde and 68 wt. parts of a paraffinic mineral oil. In this way get a stable oil dispersion.

Herbicide preparations, respectively, the active substances can be applied using the method predsjedava processing, and the method of post-harvest processing. If the active substances are less compatible with certain cultivated plants that can be used 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/ha of active substance (as.S.).

Considering the diversity of processing methods proposed according to the invention, the soybean plants in the cultivation not only of the above culture 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 liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaesis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum (Gossypium country, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, lpomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus mungo, 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' may 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 growth stage of the plants, and the time of year,

b) from the place and method of processing (e.g., seed treatment, the treatment is such as temperature, the amount of precipitation, as well as the duration of day length and light intensity,

d) from soils (including fertilizer),

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

W) from the applied concentration of the active substance.

Below are some of the many different applications of the plant growth regulators of the formula I', used in crop production, agriculture and horticulture.

A. use used according to the invention compounds could 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 for the practice is that reduced the 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 from the 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 fully mechanized harvesting of this important culture. When caring for fruit trees and other woody vegetation due to growth regulators can significantly reduce costs when pruning. In addition, by using growth regulators it is possible to vary restorecolor on fruit trees.

Due to application of growth regulators can also promote lateral branching plants or, respectively, 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 opasnaya 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 according to the invention, so that in the autumn the plants, even though well costalis, wintered, but not too overgrown. Thus, it will be a preventive measure to increased monosaccharose and due to the relatively small leaves, respectively herbal weight will prevent the risk of various diseases, such as mushrooms.

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.

the x stages of plant development, and also to accelerate, respectively, to slow down the ripening of the crop before or after harvest.

Interest from an economic point of view may represent, for example, the following factor. Thanks concentrated in a certain period of time to reduce or minimize adhesion to the tree, citrus fruit, 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.

Used according to the invention the active substances of the formula I' can be brought to cultivated plants in various ways, ranging from seed and soil treatment, i.e., through the root system, and ending, which is particularly preferably by spraying the leaves.

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

When processing the seed quantity of active ingredient is usually 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 to achieve synergistic effects, the compounds of General formula I' can be mixed with numerous representatives of other groups of active substances with herbicide and growth regulators properties, and performing the processing with which oxazine, benzothiadiazine, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamate, halogenecarbonate acid, triazine, amides, urea, simple diphenyl ethers, triazinones, orally, derivatives benzofuran, derivatives, cyclohexane-1,3-dione, bearing in position 2, for example, carboxyl group, or carbiener, derivatives of quinoline-carboxylic acid, imidazolinones, sulfonamides, sulfonylureas, aryloxy-, respectively heterooligomerization acid, and their salts, esters and amides, and other substances.

In addition, it may be desirable compounds of the formula I' without any additives or in combination with other herbicides be applied in a mixture with other crop protection agents, for example with the means of combating pests or phytopathogenic fungi and bacteria. You might be interested in further opportunity 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-fluoro-3-(2-titty dissolved in 50 ml of dry dichloromethane and added dropwise into a solution of 100 ml of a complex of hydrogen fluoride-pyridine (70% HF) in 100 ml of dry dichloromethane. After 1 h at room temperature the reaction solution is mixed with 150 ml of ice water. Then the organic phase is washed with bicarbonate solution and water, dried over magnesium sulfate and concentrated. The residue is recrystallized from petroleum ether, adding a small amount of acetic ether.

Output: 17,2 g (79%).

Example 2

Methyl ether 3-chloro-3-(3-pyridyl)-2-hydroxybutiric acid.

0.8 g (20 mmol) of LiCl dissolved in 100 ml of absolute tetrahydrofuran (THF), cooled to a temperature of -20oC and added dropwise 20 ml of titanium tetrachloride (1 M in dichloromethane). After stirring for 30 min at -20oC is cooled to -78oC and added dropwise 3.8 g (20 mmol) of methyl ester of 3-(3-pyridyl)-2,3-epoxybutane acid in 50 ml of THF. After heating to room temperature, stirring is continued for another 6 h, then the solvent is removed by distillation and the residue is partitioned between acetic ether and water. The aqueous phase is extracted with acetic ether, the combined organic phases are dried over sodium sulfate and concentrated. The residue is purified further by chromatography on silica gel using the solvent system n-hexane/UKS is illogical by received are presented in table. 2 connections.

The synthesis of compounds of General formula I

Example 3

Methyl ester 3-(2-thienyl)-3-fluoro-2-[(4,6-dimethoxypyrimidine - 2-yl)oxy] butyric acid

2.2 g (10 mmol) of methyl ester of 3-(2-thienyl)-3-fluoro-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) of 4,6-dimethoxy-2-methylsulfonylamino. After stirring for 24 h at room temperature hydrolyzing 10 ml of water using acetic acid establish a pH value of 5 and the solvent is distilled in a high vacuum. The residue is dissolved in acetic ether, washed with water, dried over sodium sulfate and distillation to remove the solvent. The residue is mixed with 10 ml methyl - tert.-butyl ether and the formed precipitate is sucked off. After drying obtain 1.8 g of white powder.

Yield: 61% (mixture of diastereomers 1:1).

Example 4

3-(2-thienyl)-3-fluoro-2-[(4,6-dimethoxypyrimidine-2-yl)oxy]butyric acid

0.9 g (3 mmole) of methyl ester of 3-(2-thienyl)-3-fluoro-2-(4,6-dimethoxypyrimidine-2-yl)-hydroxybutyric acid (from example 3) was dissolved in 20 ml methanol and 20 ml of tetrahydrofuran and mixed with 3.7 g of 10% nogura, then the solvent is distilled off in vacuo, and the residue is dissolved in 100 ml of water. Next extracted with acetic ether, then the aqueous phase was adjusted with diluted hydrochloric acid to pH 1-2 and extracted with acetic ether. After drying over magnesium sulfate and removal of the solvent the residue is mixed with a small amount of acetone and the precipitate is sucked off. After drying obtain 0.8 g of a white powder.

Yield: 89% (mixture of diastereoisomers 3:2).

Example 5

Methyl ester 3-(2-thienyl)-3-fluoro-2-[(4,6-dimethoxypyrimidine-2-yl)thio] butyric acid.

5.5 g (25 mmol) of methyl ester of 3-(2-thienyl)-3-fluoro-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. Stirring is continued for another 2 h at room temperature, washed with water, dried over magnesium sulfate and concentrated in vacuo. The residue is dissolved in dimethylformamide (DMF) at temperatures 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 Ave anywayt. After drying obtain 2.5 g of white powder.

Yield: 31% (mixture of diastereomers 1:1):

In the same way as described in the examples were obtained compounds are shown in table. 3.

Examples for the application

Herbicide action derivatives of 3-(het)arylcarbamoyl acid of General formula I' checked in 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 a 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.

Prervannyj or emulsified in water active ingredients only when they reach a height of about 3-15 see With this purpose, the experimental plants either sown directly and grown in the same containers, or their first grown separately until seedlings and a few days before processing transplanted in the experimental pots. 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, respectively, is the total destruction of at least their aerial parts, and 0 means no damage and there is a normal process of growth.

Plants, for which studies have been conducted in greenhouse conditions, are given in table. 4.

Are given in table. 5 - 9 data show high herbicide activity of the studied compounds. In particular, for example, from table 5 visible high selectivity of herbicide action of the compounds in relation to cultural plants of winter wheat.

1. Pro where R1represents C1- C4-alkoxygroup or9where R9represents hydrogen or the cation of an alkali metal;

R2and R3denote C1- C4-alkoxygroup;

X represents CR13where R13is hydrogen;

R4denotes a five - or six-membered heteroaromatic ring containing one to two nitrogen atoms and/or one sulfur atom or one oxygen atom, which may carry one or more residues selected from among the following: C1- C4-alkyl, or phenyl;

R5denotes hydrogen or C1- C4-alkyl;

Y represents sulfur or oxygen;

Z represents halogen.

2. Derivatives of 3-halogen-3-heterylcarbonyl acid of formula I under item 1, in which R5denotes methyl, X denotes CH, R2and R3denote methoxy, and Y, Z, R1and R4shall have the meaning specified in paragraph 1.

3. Derivatives of 3-halogen-3-heterylcarbonyl acid under item 1, in which Z represents fluorine, R5denotes methyl, X denotes CH, R2and R3denote methoxy, and Y, R1and R4shall have the meaning specified in paragraph 1.

4. Herbicide tool that contains proizvodi inkarbaeva acid contains one of the compounds of formula I on p. 1.

 

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