The method of producing aminophenylacetylene (options), intermediate products

 

(57) Abstract:

The invention relates to a new method of production (its variants) aminophenylalanine formula I, having the properties of plant growth regulators or herbicides, as well as intermediate products for their production. The method of producing aminophenylacetylene formula I, values radicals which are specified in the claims, lies in the fact that the compound of formula II or its salt is subjected to processing halogenation agent to obtain the corresponding carboxylic acid halide, which programmirovaniya, obtaining the compounds of formula III. Further, the compound of formula III is subjected to ammonolysis in the group of SO2Cl2obtaining the compounds of formula IV, then this connection restore group NO2obtaining the compounds of formula V, which is subjected to interaction with the corresponding carbamate or its salt of the formula VI, where Ar denotes unsubstituted or substituted phenyl, and M stands for hydrogen, C1-C4-alkyl or a metal cation. Either the compound of formula III is subjected to ammonolysis in the group of SO2Cl2and then the obtained compound of formula IV is subjected to interaction sootvetstvovali III is subjected to interaction with the cyanate or with a heterocyclic amine of the formula VIII with obtaining the compounds of formula VII, which restore. Intermediate compounds corresponding to formulae III, IV, V, VI, VII, are new. It is also proposed a method of obtaining the compounds of formula III. The proposed new method allows to obtain the compounds of formula I in high yields and good purity. 12 C. and 2 h.p. f-crystals.

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The invention relates to the technical field of methods of obtaining aminophenylacetylene possessing properties of herbicides or plant growth regulators.

It is known that geterotsiklicheskikh substituted phenylsulfonylacetate bearing phenyl ring amino-, respectively functionalized with an amino group, possess herbicide and regulating plant growth properties (EP-A-1515; EP-A-7687 (=US-A 4,383,113); EP-A-30138 (=US-A 4,394,506); US-A-4,892,946; US-A-4,981,509; EP-A-116518 (= US-A-4,664,695, US-A-4,632,695)), WO -94/10154. Furthermore, in German patent application P 4415049.0 (WO 94/29899) have been proposed as herbicides acylaminoalkyl. In this literature also describes how to obtain the sulfonylureas. Compounds with a free amino group at the phenyl ring are themselves herbicide-active substances or suitable as starting substances for polycotton with only minor outcrops or low purity of the product due to the presence of many reactive functional groups in the molecule.

The disadvantage is that in many ways it is necessary to apply a protective group, for example tert-boutelou group to sulfonamides, the removal of which requires the use of special and difficult to use reagents, such as triperoxonane acid. In addition, known methods for producing compounds sulfonylureas are mostly multi-stage and, therefore, generally provide only a moderate overall yield.

Object of the invention is thus to provide a method suitable for obtaining a large group of herbicides from a number of aminophenylacetylene and free from many of the above disadvantages.

The subject of the invention is a method of obtaining compounds of formula (I) and their salts

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where (R)nmeans n identical or different residues from the group of halogen, alkyl and alkoxy,

n means 0, 1, 2 or 3, preferably 0 or 1, in particular 0,

A denotes hydrogen or acyl residue,

R1means hydrogen or unsubstituted or substituted hydrocarbon or uglevodorodov-residue containing 1 to 6 C-atoms, preferably 1 to 4 C-atoms,

R2means hydrogen or unsubstituted or substituted PLR>R2means heterocyclic ring of 3-8 atoms in the ring which is not substituted or substituted and contains in the ring N-atom of the group NR1R2as heteroatom and may contain in the ring one or two heteroatoms from the group N, O and S,

R3means hydrogen or C1-C4-alkyl,

X, Y means independently of one another halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, each of the last three residues are not substituted or substituted by one or more residues from the group halogen, C1-C4-alkoxy, C1-C4-alkylthio, or C3-C6-cycloalkyl, C2-C6alkenyl, C2-C6-quinil, C3-C6-alkenylamine or C3-C6-alkyloxy and

Z denotes CH or N,

characterized in that

1. (stage 1) compound of formula (II)

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or its salt is subjected to interaction in the presence of a halogenation means with the formation of gelegenheid carboxylic acid and its rearrangement in the compound of formula (III)

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2. (stage 2) then

a) ammonolysis the compound (III) SO2Cl-group to obtain the compounds of formula (IV),

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then restore with the accordance with the carbamate, accordingly salt of carbamate of formula (VI),

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where Ar denotes unsubstituted or substituted phenyl, and M denotes H, C1-C4-alkyl or a metal cation with obtaining the compounds of formula (I) in which R3in accordance with the M in the formula (VI) means H or C1-C4-alkyl, or, if M = metal cation, R3means a hydrogen atom and A denotes H, or

b) monolithium compound of formula (III) SO2Cl-group to obtain the compounds of formula (IV), then the compound (IV) is subjected to interaction with the carbamate, respectively, with the salt of carbamate mentioned formula (VI) with a compound of formula (VII),

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in which R3in accordance with the M in the formula (VI) means H or C1-C4-alkyl or, if M = metal cation, R3means a hydrogen atom, and restore the connection of the formula (VII) nitro-group to obtain the compounds of formula (I) in which A denotes H, or

C) subjecting the interaction of the compound of formula (III) with cyanate or with a heterocyclic amine of the formula (VIII),

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where R3defined as in formula (I) receiving sulfonylureas of the formula (VII), after which restore the nitrogroup network connection ormrod, and acyl residue, acelerou obtained in stage 2 of the compound of formula (I) in which A denotes H, and in formulas (II)-(VIII) residues (R)n, R1, R2X, Y, Z have the same meaning as in the final product of formula (I).

In formulas (I) - (VIII) used in the following formulas remains of alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino, alkylthio, and also the corresponding unsaturated and/or saturated hydrocarbon residues in the skeleton can be linear or branched. Unless specifically stated otherwise, these residues are lower hydrocarbon skeletons, for example, preferably with 1-4 C-atoms, respectively, in the case of unsaturated groups with 2-4 C-atoms.

Alkyl residues, including complex values, such as alkoxy, haloalkoxy, etc. mean, for example, methyl, ethyl, n - or ISO-propyl, n-, ISO-, tert - or 2-butyl, Penteli, sexily, such as n-hexyl and 1,3-dimethylbutyl, reptile, such as n-heptyl, 1-etylhexyl and 1,4-dimethylpentyl.

Alkeneamine or alkyline residues have the value of the corresponding alkyl residues of the possible unsaturated residues; alkenyl means, for example, allyl, 1-methyl-prop-2-EN-1-yl, 2-methylprop-2-EN-1-yl, but-2-EN-1-yl, but-3-EN-1-yl, 1-meth is-INF-1-yl.

Halogen means, for example, fluorine, chlorine, bromine or iodine.

Haloalkyl, haloalkyl and haloalkyl mean partially or completely replaced by halogen, preferably fluorine, chlorine and/or bromine, in particular fluorine or chlorine, alkyl, alkenyl, respectively quinil, for example, CF3, CHF2CH2F, CF3CF2CH2FCHCl, CCl2, CHCl2CH2CH2Cl; haloalkoxy means, for example, OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3and OCH2CH2Cl; the same applies to haloalkenes and other substituted by halogen residues.

The hydrocarbon residue is a linear, branched or cyclic, saturated or unsaturated aliphatic or aromatic hydrocarbon residue such as alkyl, alkenyl, quinil, cycloalkyl, cycloalkenyl or aryl, preferably alkyl, of alkenyl or quinil with the number of C-atoms to 12 or Croaker with 5 or 6 atoms in the ring or phenyl; the same applies to uglevodorodyonogo.

Heterocyclic residue or ring may be saturated, unsaturated or heteroaromatic; it contains in the ring one or more heteroatoms, preferably from the group N, O and S; predpochtitaemye residue or ring with the above value or partially gidrirovanny balance, such as oxiranyl, pyrrolidyl, piperidyl, piperazinil, DIOXOLANYL, morpholinyl, tetrahydrofuryl. As the substituents in the substituted heterocyclic residue can be seen below substituents, and optionally also the carbonyl group. Oxoprop can meet also have heteroatoms in the ring, can exist in various oxidation States, for example, N and s

Substituted residues, such as hydrocarbon residues, for example substituted alkyl, alkenyl, quinil, aryl, phenyl and benzyl, or substituted heteroaryl, substituted bicyclic residue or ring or substituted bicyclic residue, if necessary containing aromatic components, means, for example, derived from unsubstituted baseline substituted residue, and the alternate means, for example, one or more, preferably 1, 2 or 3 residue from the group of halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, cyano, azido, alkoxycarbonyl, alkylsulphonyl, formyl, carbarnoyl, mono - and dialkylaminoalkyl, substituted amino, such as acylamino, mono - and dialkylamino, and alkylsulfonyl, haloalkylthio, alkylsulfonyl, haloalkaliphilic in the case of cyclic residues teenie aliphatic residue, such as alkenyl, quinil, alkenylacyl, alkyloxy, etc. Of the residues with the C atoms are preferred those with 1 to 4 C-atoms, in particular 1 or 2 C-atoms. Preferred, generally, substituents from the group halogen, for example fluorine and chlorine, C1-C4-alkyl, mainly methyl or ethyl, C1-C4-haloalkyl, mainly trifluoromethyl, C1-C4-alkoxy, mainly methoxy or ethoxy, C1-C4-haloalkoxy, nitro and cyano. Especially preferred when the substituents methyl, methoxy and chlorine.

If necessary substituted phenyl is preferably phenyl which is not substituted or substituted one or more times, preferably up to three identical or different residues from the group halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-halogenated, C1-C4-halogenoalkane and nitro, for example o-, m - and p-tolyl, dimethylphenyl, 2-, 3 - and 4-chlorophenyl, 2-, 3-and 4-Cryptor and trichlorophenyl, 2,4-, 3,5-, 2,5-and 2,3-dichlorophenyl, o-, m - and p-methoxyphenyl.

Acyl residue means a residue of an organic acid, such as carboxylic acid residue, and the remains of a derivative of acids, such as thiocarbonyl, if necessary, replaced carbamino acid, sulfonic acids, Sultanovich acids, phosphonic acids, phosphinic acids. Acyl means, for example, formyl, alkylsulphonyl, such as (C1-C4-alkyl)-carbonyl, phenylcarbinol, and the phenyl ring may be substituted, for example as indicated above for phenyl, or allyloxycarbonyl, vinyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfonyl, N-alkyl-1-aminoalkyl and other residues of organic acids.

Of particular interest are proposed according to the invention methods of making compounds of formula (I) or their salts, in which Rnmeans n identical or different residues from the group halogen, C1-C4-alkyl and C1-C4-alkoxy,

n means 0 or 1, in particular 0,

A denotes H or acyl with 1 to 8 C-atoms, in particular 1 to 4 C-atoms,

R1means H, C1-C6-alkyl, C2-C6alkenyl, C2-C6-quinil, C1-C6-alkoxy, C2-C6-alconox, C2-C6-alkyloxy or C5-C6-cycloalkyl, each of 7 named last residue is not substituted or substituted by one or more residues from the group halogen,SUB>-alkyl)amino, cyano, azido, formyl, (C1-C4-alkyl)-carbonyl, (C1-C4-alkoxy)-carbonyl, C1-C4-alkylsulfonyl and C1-C4-alkylsulfonyl or phenyl, unsubstituted or substituted by residues from the group halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-halogenated, C1-C4-halogenoalkane and nitro.

R2denotes H, C1-C6-alkyl, C2-C6alkenyl, C2-C6-quinil, each of these three latter residue is not substituted or substituted by one or more residues from the group halogen, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio-, mono - and di-(C1-C4-alkyl)-amino, cyano, azido, formyl, (C1-C4-alkyl)-carbonyl, (C1-C4-alkoxy)-carbonyl, C1-C4-alkylsulfonyl and C1-C4-alkylsulfonyl,

or group

NR1R2means a heterocyclic ring of 4, 5 or 6 atoms in the ring which may contain in the ring even up to two heteroatoms from the group N and O and which is not substituted or substituted by one or more residues from the group of C1-C4-alkyl,

R3means H or CH3-C2-alkylthio, each of these three latter residue is not substituted or substituted by one or more residues from the group halogen, C1-C2-alkoxy and C1-C2-alkylthio, or mono-or di(C1-C2-alkyl)-amino, preferably halogen, methyl or methoxy, and

another of the residues X and Y

means C1-C2-alkyl, C1-C2-haloalkyl, C1-C2-alkoxy, C1-C2-haloalkoxy or C1-C2-alkylthio, preferably methyl or methoxy,

Z denotes CH or N, preferably CH.

Preferred is also proposed according to the invention methods for producing compounds or their salts of the formula (I), in which mean:

A is hydrogen, formyl, (C1-C4-alkyl)-carbonyl, which is not substituted or substituted by one or more residues from the group of halogen and (C1-C4)-alkoxy,

or (C1-C4-alkoxy)-carbonyl, phenoxycarbonyl, phenylcarbamoyl, phenyl-(C1-C4-alkyl)-carbonyl or phenyl-(C1-C4-alkoxy)-carbonyl, and phenyl in each of the 4 mentioned last residue is not substituted or substituted, preferably A denotes formyl, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl -alkoxy)-carbonyl. Are preferred by the invention methods of making compounds of formula (I) and their salts, in which

R1- H, C1-C2-alkyl, C1-C2-alkoxy, phenyl, unsubstituted or substituted by one or more residues from the group halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-halogenated, C1-C2-halogenoalkane, in particular methyl or ethyl,

R2- H or C1-C2-alkyl, in particular methyl or ethyl, or a group

NR1R2- heterocyclic ring of 5 or 6 atoms in the ring which may contain in the ring one another heteroatom from the group N and O and which is not substituted or substituted by one or more C1-C2-alkyl residues, in particular pyrrolidinyl or piperidinyl,

R3- H or CH3in particular H.

Of the methods according to the invention preferred that in compounds of formula (I) a group of the formula NH2in the phenyl residue is located in the para-position to the group CO-NR1R2and in the meta-position to the group of SO2.

The subject invention are also inventive separate step of the method in General and their new p the salts carbamate (VI), in which M denotes a cation.

The conversion of compounds (II) in compound (III) can be carried out using a conventional halogenation agent used to obtain the carboxylic acid anhydrides, for example, using thionyl chloride or thienylboronic. For this purpose, conduct the reaction of nitro-ortho-sulfamoyl-benzoic acid (II) with an excess of halogenation agent in an aprotic solvent and then heated to a temperature at which the reaction begins rearrangement. As organic solvents suitable aprotic organic solvents which are inert towards the reagents (the so-called "inert solvents") and the boiling point of which lies above the temperature required for the rearrangement reaction. To obtain the target products can be the interaction of these reagents, e.g., in homogeneous solution or in a heterogeneous mixture (e.g., suspension). For example, the reaction can be carried out if necessary in halogenated aromatic hydrocarbons such as toluene, xylene, chlorobenzene or chlorotoluene. The reaction temperature of the halogenation lie in the range of about from 50 to 100oC and the temperature of the rearrangement reaction in Predosa the rearrangement occurs sufficiently already at lower temperatures, for example, if 70oC. thionyl chloride can be used, for example, in equimolar amounts or in excess, calculated on the moles of benzoic acid. Instead of derivatives of benzoic acid can also be used the corresponding salts, such as salts of alkaline or alkaline-earth metals (for example, salts of Na, K, Li, Mg and Ca) for reaction with a halogenation agent such as thionyl chloride, to obtain the corresponding derivative (III) 2-chlorosulfonylbenzoic.

Already known the way of interaction of 2-(N,N-dialkylaminoalkyl)-benzoic acid, unsubstituted or bearing simple alkyl groups on the phenyl ring, a 4 - to 8-fold excess of thionyl chloride or thienylboronic in benzene, dichloromethane or chloroform to obtain N,N-dialkylamides 2-(chlorosulfonyl)-, 2-(Braselton)-benzoic acid at room temperature (25oC); see K. Hovius et al., Tetrahedron Lett. 1983, 3137-3140. The corresponding reaction of interaction of N,N-dialkyl-o-sulfamoyl-nitrobenzoic acids (II) still was not known and under these conditions it was not possible up to now to spend. Only by modification of known conditions with regard to temperature and solvents in this reaction are able to spend with ispytanijami ways. Thus, oxidation of the methyl group of compounds of formula (IX)

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leads to the formation of compounds of formula (II). The oxidation can be carried out, for example, analogously to known methods of obtaining benzoic acid from toluene. A derivative of toluene of the formula (IX) may be obtained by interaction of sulfochloride formula (X) with an amine of the formula NR1R2,

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Another access to the compound (II) provides the ammonolysis of sulfochloride formula (XI)

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in which Ra means an alkyl residue, for example methyl or ethyl, with an amine of the formula HNR1R2getting sulfonamida and subsequent saponification of the obtained compound in the ester group of carboxylic acid. A separate reaction interaction can be carried out analogously to known methods of this type. For example, the ester function can be amylene using hydroxides of alkaline or alkaline-earth metals, such as LiOH, NaOH, KOH, Mg(OH)2Ca(OH)2in various polar solvents, such as methanol, ethanol, isopropanol, chlorobenzene, chlorotoluene, tetrahydrofuran, 1,2-dimethoxyethane ((DME), diglyme, dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-methyl-pyrrolidone (NMP) or water, or in mixtures of solvents composed of the public from -10oC to 100oC.

The sulfonamides of the formula (IV) can be obtained in high yields by reacting sulfochloride (III) with ammonia (ammonolysis). The reaction is carried out mainly at temperatures from -20oC to 150oC, mostly at temperatures from -10oC to 100oC. Suitable solvents are under the reaction conditions, for example, the following inert organic solvents:

- dipolar aprotic solvents such as dimethylformamide, dimethylacetamide, organic, acetonitrile,

- ethers, such as tert-butyl methyl ether, dimethoxyethane, tetrahydrofuran, diethyl ether, diisopropyl ether,

- esters, such as ethyl acetate, butyl acetate,

- chlorinated or unsubstituted hydrocarbons, such as toluene, o-chlorotoluene, chlorobenzene,

- alcohols, such as methanol, ethanol, isopropanol,

water

- a mixture of inert solvents.

Especially preferred solvents are NITRILES, such as acetonitrile, ethers such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran (THF), dimethoxyethane (DME) or esters, such as ethyl and butyl acetate, or chlorinated or nezamescennych formula (IV) can be carried out, for example, by catalytic hydrogenation (stage 2, section a). For hydrogenation fit a large number of commercially available catalysts, for example platinum, palladium or Raney Nickel, which are used similar to that used in the standard way. Suitable reaction conditions inert organic or inorganic solvents are, for example, the following:

- dipolar aprotic solvents such as dimethylacetamide (DMA), dimethylformamide (DMF), organic (NMP) or CH3CN;

- esters, such as ethyl acetate or butyl acetate,

- ethers, such as dimethoxyethane (DME), diglyme, tetralin, tetrahydrofuran (THF) or diethyl ether;

- alcohols, such as methanol or ethanol,

organic acids such as acetic or propionic acid;

water

- a mixture of suitable inert solvents.

The reaction temperature can vary, for example, between -20oC to 150oC, mainly from -10oC to 100oC. the hydrogen Pressure may also vary within wide limits and can be, for example, from 1 bar to 299 bar, preferably from 1 bar to 100 bar, in particular from 1 bar to 50 bar.

The reaction of the interaction is on sulfonamidnuyu group, and not by an alternative amino groups in the phenyl residue. If the reaction of the compound (V) is carried out with the carbamates of the formula (IV) in a standard way, for example, in acetonitrile in the presence of sterically constrained bases, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), reactivity sulfonamidnuyu and amine functions are similar to each other, i.e., chemoselectivity reaction is completely unsatisfactory. So, for example, the reaction of interaction of 5-amino-2-dimethylaminocarbonylmethyl with 4,6-dimethoxy-2-phenoxycarbonylamino in the presence of DBU leads to the formation of two products in a ratio of 2:1, namely 5-amino-2-dimethyl-aminocarbonyl-N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl]-benzosulfimide and 5-([4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl]-2-dimethylaminoethyl-N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl]- benzosulfimide (by-product) (see the example for comparison). However, the reaction of interaction can be unexpectedly selective in the case of interaction with urethane salts. According to the invention the best selectivity in comparison with the selectivity obtained by reaction with carbamates of the formula (XI) in which M denotes hydrogen, is achieved if primestyle, carbamate (VI) (M = H) is subjected to interaction with suitable bases, such as hydroxides of alkali or alkali-metals facilities, such as LiOH, NaOH, KOH, Mg(OH)2Ca(OH)2, hydroxides of tetralkylammonium, such as hydroxides of Tetramethylammonium, hydrides of alkali or alkaline earth metals, such as NaH, KH, CaH2, alcoholate of alkaline or alkaline-earth metals, such as NaOCH3, NaOC2H5isopropylate sodium tert-butyl sodium, KOCH3, KOC2H5isopropylate potassium, tert-butyl potassium, or mixtures of bases in a suitable solvent to obtain a salt of the formula (VI) (M = cation).

As suitable solvents are inert organic solvents, preferably aprotic non-polar or aprotic polar solvents, such as ethers (e.g. tetrahydrofuran, dimethoxyethane, diethyl ether, diisopropyl ether, dioxane, tert-butyl methyl ether), amides (e.g. dimethylformamide, dimethylacetamide, organic, if necessary, halogenated aromatic hydrocarbons such as toluene, chlorotoluene or chlorobenzene. For salts of alkaline or alkaline-earth metals suitable solvents are tacinelli metal and tetraalkylammonium a suitable solvent, or component of the solvent is water. Particularly preferred ethers, such as tetrahydrofuran, dimethoxyethane or dioxane.

Thus obtained salt of the formula (VI) (M = cation) get profitable in solution and used in further reactions without prior selection. To this end, for example, salts in solution is subjected to interaction with the sulfonamides of the formula (V) at temperatures from -40oC to 150oC, preferably from -40oC to 80oC, in particular from -20oC to 80oC. After acidification of the reaction solution acids, for example organic acids such as formic or acetic acid, or mineral acids such as hydrochloric or sulfuric acid, sulfonyl.keviny of formula I (A=H) (= compounds (1')) was isolated by standard methods. The optimal solution is achieved, typically at a molar ratio of sulfonamides (V) to urethane salt (VI) in the range from 1:0.7 to 1:1,5.

The preferred options are the reaction of the carbamates of the formula (VI) (M = H) with hydroxides and alkali metal alcoholate, such as KOH, NaOH3, KOCH3, tert-butyl sodium or potassium, isopropylate sodium or potassium, in particular with sterically demanding alkali metal alcoholate, in a dipolar eastmost in tetrahydrofuran (THF), dimethoxyethane (DME) or dioxane.

An alternative approach to sulfonylurea (1') (= formula (I) in which A = H) is called option 2B. According to this variant of the compounds (III) first, as at the 1st stage, stage 2A, by ammonolysis get nitrobenzenesulfonamide formula (IV), which are then subjected to the interaction with the carbamates of the formula (VI) is similar to the standard conditions in the presence of bases, such as organic nitrogen bases, such as DBU or triethylamine, hydroxides of alkaline or alkaline-earth metals, such as LiOH, NaOH, KOH, Mg(OH)2Ca(OH)2, alcoholate of alkaline or alkaline-earth metals, such as NaOH3, KOCH3isopropylate sodium or potassium, trebuchet sodium or potassium, getting nitrosodiphenylamine formula (VII). The ratio of reagents are preferably the following: 0.7 to 1.5 equivalents of carbamate (VI) and 0.7-2.2 equivalent basis, respectively, in terms of 1 equivalent sulfonamida (IV).

The reaction between compounds (IV) with a compound (VII) is carried out at temperatures of, for example, -20oC to 100oC, preferably from -10oC to 70oC, in inert organic solvents, such as APRO is ethical, dimethylformamide, dimethylacetamide, organic, alcohols, esters, such as ethyl acetate or butyl acetate, chlorinated aliphatic or aromatic hydrocarbons, such as dichloromethane, trichloroethane, chlorobenzene or o-chlorotoluene, or proton solvents, such as methanol, ethanol, isopropanol, or water, or in suitable mixtures of solvents.

Nitrosodiphenylamine formula (VII) can be selected the same as the above interaction urethane salts of the formula (VI) (M = cation) with a sulfonamide of the formula (V) to sulfonylureas (I') (=formula (I) in which A = H) by reaction of sulfonamides of formula (IV) (M = cation) with urethane salts (M = cation) (VI).

Then nitrosodiphenylamine (VII) a catalytically hydronaut with getting aminosulphonylphenyl (I') of the formula (I) in which A = H. the Hydrogenation can be carried out similarly to the above-mentioned hydrogenation of compounds of the formula (IV) by standard methods. When applying the water environment as a solvent is particularly suitable basic solutions or bateriafina aqueous solutions with pH from 5 to 13, preferably from 7 to 11. Alternative instead of neutral nitrosodiphenylamine (VII) for the hydrogenation can be used or alkaline-earth metals, such as Li+, Na+, K+Cs+, Mg2+Ca2+or ammonium cations, such as NH4+, HN(CH3)3+N(CH3)4+N(C2H5)4+, HN(C2H5)3+, (DBU-H)+or mixtures of these cations.

Communication method of sulfochloride (III) cyanate, for example with sodium cyanate or potassium cyanate, and heterocyclic amines (VIII) to obtain the compounds (VII) (option 2B), in principle, described in the above literature, see , for example, German patent application P 4415049.0 (WO 95/29899). The subsequent restoration of the nitro group may, as in the case of the compound (IV), carried out by conventional methods, preferably, for example, catalytically, as already described above for the compounds (VII).

On the 3rd stage of the method obtained in stage 2 of compound (I') of the formula (I) in which A = H, can be etilirovany with getting herbicide active substances (I) of the formula (I) in which A denotes an acyl residue. The acylation can spend on the amino group attached to the phenyl ring, unexpectedly very selectively using conventional acylation agents. The acylation is carried out, for example, in an aprotic organic solvent anhydrides, halides of carboxylic acids, activated esters (=active esters such as esters of carbonic acid and harpalinae acid, sulfonic acid anhydrides, etc., for Example, for the formation of the amine functions of the sulfonylureas (I') of the formula (I) in which A = H), there are a number of very good standard ways. Thus, the amine function can be transferred to the mixed anhydrides of the formula (XII)

H-COO-CO-R, (XII) R = alkyl

or formic acid in formylamino group.

Mixed anhydrides can be obtained well-known from the literature by means of formic acid and anhydrides of carboxylic acids, such as acetanhydride, or salts of formic acid, for example formate, sodium, and carboxylic acid anhydrides, such as acetylchloride or pivaloyloxy.

The individual intermediate products of the method according to the invention are new and they are the subject of invention.

To achieve optimal outputs per unit time per unit volume of the individual stages of the reaction just described method can be carried out in homogeneous and saturated, i.e., kinetically stable solution or in a heterogeneous som separate stages, you can get such a common exit the sulfonylureas of the formula (I), preferably such that allumina function is in the para-position relative to carbonamide group that exceed described in the literature (DE 4415049, WO 95/29899) exit.

Selecting the proper reaction conditions, it is possible to combine several stages in the reaction carried out in a single reactor, respectively held in the cascade. It also can be upgraded, in part significantly, the output per unit time per unit volume.

It is preferable to obtain compounds of formula (I) in which n = 0 and R3denotes H and the amino group at the phenyl ring is in the para-position to carbonamide group in meta-position to SO2function (=compound (1a)).

Especially preferred are the method according to the invention and its individual stages, characterized in that the compound of formula (IIa)

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where R1and R2defined as in formula (I), is subjected to the reaction of interaction in the presence of a halogenation means with the formation of gelegenheid acid and regrouping in the compound of formula (IIIa),

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then translate the compound (IIIa) of ammonia (Va)

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and subjecting the compound (Va) interaction with urethane salt of the formula (VIa)

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obtaining the compound (Ia).

In the following examples, get the number and percentages relate to weight, because otherwise indicated. The abbreviation "Fp" means melting point ("so square").

Examples of making

Example 1

Chloride 2-dimethylaminoethyl-5-nitrobenzenesulfonate

To a suspension of 195,2 g dimethylamide 2-carboxy-5-nitrobenzenesulfonic acid in 800 ml of chlorobenzene was added 40 ml of thionyl chloride. Then the mixture under vigorous stirring slowly heated to 70-75oC. After adding 120 ml of thionyl chloride, the reaction mixture is heated to boiling. Upon completion of the reaction, the reaction mixture was concentrated under reduced pressure. Get so 209 g is specified in the header of the product, which has a sufficient purity for use in subsequent reactions, so pl. 129-131oC.

Example 2

2-Dimethylaminoethyl-5-nitrobenzenesulfonamide

In a mixture of 77,8 g of acid chloride of 2-dimethylaminoethyl-5-nitrobenzenesulfonate and 780 ml of tetrahydrofuran at 5oC with stirring, added dropwise 37 ml of concentrated ammonia solution (33 the hinnon pressure and the residue stirred in a little water. After drying receive 66,9 g is specified in the header of the product, so pl. 159-160oC.

Example 3

5-Amino-2-dimethylaminocarbonylmethyl

A solution of 12.5 g of 2-dimethylaminoethyl-5-nitrobenzenesulfonamide in 250 ml of methanol is mixed with 1 g of wet Raney Nickel and vigorously stirred at 60oC and a hydrogen pressure of 50 bar. Upon completion of hydrogen absorption, the catalyst is separated and the filtrate concentrated. Get so 11,0 g is specified in the header of the product.

Example 4

5-Amino-2-dimethylaminoethyl-N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl]-benzosulfimide

Method a:

128,4 g of 4,6-dimethoxy-2-(phenoxycarbonylamino)pyrimidine placed at 0oC in 1250 ml of tetrahydrofuran (THF). After adding to 44.8 g of tert-butyl sodium this solution at 0 to 2oC added dropwise to a mixture of 108,1 g of 5-amino-2-dimethylaminocarbonylmethyl in 1250 ml of tetrahydrofuran. Upon completion of the reaction, the reaction mixture was concentrated. The residue is partitioned between 1500 ml of water and 780 ml of petroleum ether and carefully acidified with concentrated hydrochloric acid (100 ml). Precipitated precipitated solid is washed with petroleum ether and ethyl ester of acetic acid. Polniy out of 3.78 g of sodium cyanate, the 4.7 ml of pyridine and 100 ml of acetonitrile sequentially added to 5.3 g of 2-amino-4,6-dimethoxypyrimidine and 10 g of acid chloride of 2-dimethylaminoethyl-5-nitrobenzene sulfonic acids. The mixture is stirred at room temperature until complete conversion and then bring in diluted cooled hydrochloric acid. Phase precipitate the crude product is purified by chromatography on a column (CH2Cl2/CH3OH = 95/5). Get so 3.1 g specified in the header of the product; so pl.: 182-186oC with decomposition.

b) 1.4 g 2-dimethylaminoethyl-5-nitro-N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl] -benzosulfimide suspended in 25 ml of water and mixed with 5.5 ml of 1 n sodium hydroxide solution. After adding 0.1 g of palladium on coal (10%, 50% water) the mixture is vigorously stirred at room temperature in hydrogen atmosphere (1 bar). Upon completion of the reaction, the catalyst was separated by filtration and washed with a small amount of water. After acidification of the aqueous phase with concentrated hydrochloric acid to obtain 1.1 g specified in the header of the product; so pl.: 192-193oC with decomposition.

Example 5

N,N-dimethyl-2-methoxycarbonyl-5-nitrobenzenesulfonamide

To a mixture of 202,8 g 2-methoxycarbonyl-5-nitrobenzylamine 250,6 g of potassium carbonate. Upon completion of the reaction, the solid is filtered and washed with ethyl acetate. The combined organic phase is then concentrated under reduced pressure. So get 206,7 g is specified in the header of the product; so pl. 93-96oC.

Example 6

N,N-dimethyl-2-carboxy-5-nitrobenzenesulfonamide

To a solution of 206,7 g dimethylamide 2-methoxycarbonyl-5-nitrobenzenesulfonic acid in 1500 ml of methanol, add a 60.2 g of lithium hydroxide-monohydrate. The mixture was then stirred until complete conversion at 50oC. After concentrating the reaction mixture under reduced pressure the residue is dissolved in water and mixed with concentrated hydrochloric acid (pH 1) at 0oC. After extraction and drying are covered in the title acid. Output: 162,9 g; so pl. 160-163oC.

Example 7

2-Dimethylaminoethyl-5-nitro-N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl]-benzosulfimide

1st method:

and 31.7 g of 4,6-dimethoxy-2-(phenoxycarbonylamino)-pyrimidine placed at 0oC in 400 ml of tetrahydrofuran. After adding 11,08 g of tert-butyl sodium, this solution is added dropwise to a mixture of 30.0 g of 2-dimethylaminoethyl-5-nitrobenzenesulfonamide in 400 ml of tetrahydrofuran at 0aqueous ether and acidified with concentrated hydrochloric acid. Precipitated precipitated solid is washed with petroleum ether and ethyl ester of acetic acid. After drying receive a 43.4 g is specified in the header of the product; so pl.: 182-186oC with decomposition.

2-method:

To a suspension of 5.0 g of 2-dimethylaminoethyl-5-nitrobenzenesulfonamide in 20 ml of water at room temperature and vigorous stirring is added dropwise to 18.6 ml of 1 n sodium hydroxide solution. Then add 5,04 g of 4,6-dimethoxy-2-phenoxycarbonylamino-pyrimidine. The reaction mixture is heated to a temperature of approximately 50-60oC and stirred at this temperature until complete conversion. The aqueous phase is washed with diisopropyl ether. The aqueous phase is acidified with concentrated hydrochloric acid (pH 2 to 3). Precipitated precipitated solid is separated, washed with water and dried. Get so 7.6 g is specified in the header of the product, which has a sufficient purity for use in subsequent reactions.

Example 8

N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl] -2-dimethylaminoethyl-5-acetamidobenzenesulfonyl

To a mixture of 0.64 g of N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl]-5-amino-2 - dimethylaminocarbonylmethyl and 10 ml of dimethylacetamide slow the leaders introduce pressure and the residue is washed with water and ethyl ester of acetic acid. Get that way 0.45 g is specified in the header of a product of high purity (> 92%, ghvd).

Example 9

N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl] -5-formylamino-2-dimethylaminocarbonylmethyl

To the mixed anhydride obtained by a standard method from 0.5 ml of formic acid and 1.0 ml of acetic anhydride are added dropwise to 1.9 g of N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl]-5 - amino-2-dimethylaminocarbonylmethyl and 10 ml dichloromethane. After the reaction, the reaction mixture was concentrated and the residue is washed with water and ethyl acetate. Get so 1.8 g specified in the header of a product of high purity (>92%, ghvd).

Example 10

N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl] -2-dimethylaminoethyl-5-propynylbutylcarbamate

To a solution of 0.64 g of 5-amino-N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl] -2-dimethylaminoethyl-benzosulfimide in 10 ml of dimethylacetamide is slowly added dropwise with 0.13 ml of propionitrile. After the reaction, the reaction mixture was concentrated under reduced pressure and the residue is washed with water and ethyl ester of acetic acid. Get that way 0.45 g is specified in the header of the product VI-dimethoxypyrimidine-2-yl)-aminocarbonyl]-benzosulfimide

To a suspension of 1.0 g of 5-amino-2-dimethylaminoethyl-benzosulfimide and 1.1 g of 4,6 dimethoxy-2-(phenoxycarbonylamino) pyrimidine in 10 ml of acetonitrile was added at 0oC and under stirring, 0.6 ml of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The mixture is stirred until complete conversion. After distillation of the volatile components, the residue is dissolved in a small amount of water and washed with diethyl ether. The aqueous phase is then acidified with concentrated hydrochloric acid (pH 2 to 3). The selected solid is washed with diisopropyl ether and then dried. Get so 1.4 g of solid, which contains both compounds, namely 5-amino-2-dimethylaminoethyl-N-[(4,6-dimethoxypyrimidine-2 - yl)-aminocarbonyl]-benzosulfimide and 5-[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl] -2-dimethylaminoethyl-N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl]-benzosulfimide in the ratio of approximately 2:1.

1. The method of producing aminophenylacetylene formula (I) and its salts

< / BR>
where (R)nmeans n identical or different residues from the group of halogen, alkyl and alkoxy;

n means 0, 1, 2 or 3;

A represents hydrogen or the acyl residue;

R1means hydrogen or nezaket hydrogen or unsubstituted or substituted hydrocarbon residue, containing in the amount of 1-10 C-atoms;

or the group NR1R2means heterocyclic ring of 3-8 atoms in the ring which is not substituted or substituted and contains in the ring N-atom of the group NR1R2as heteroatom and may contain in the ring one or two heteroatoms from the group N, O and S;

R3means hydrogen or C1-C4alkyl;

X, Y means independently of each other halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, each of these three latter residue is not substituted or substituted by one or more residues from the group halogen, C1-C4-alkoxy and C1-C4-alkylthio or3-C6-cycloalkyl, C2-C6alkenyl,2-C6-quinil,3-C6-alkenylamine or3-C6-alkyloxy; Z denotes CH or N,

characterized in that the compound of formula (II)

< / BR>
or its salt is subjected to interaction in the presence of a halogenation means with the formation of the halide of carboxylic acid and its rearrangement in the compound of formula (III)

< / BR>
then the compound of formula (III) ammonolysis on SO2Cl-group to obtain the compounds of formula (IV)
is rmula (VI)

< / BR>
obtaining the compounds of formula (VII)

< / BR>
in which R3in accordance with the M in the formula (VI) denotes N or C1-C4-alkyl or, if M is a cation of the metal, means a hydrogen atom, and restore the connection of the formula (VII) nitro-group to obtain the compounds of formula (I) in which a represents N, or for the case, And if desired in the final product of formula (I) is not hydrogen and acyl residue, acelerou obtained in stage 2 of the compound of formula (I) in which a represents N, and in formulas (II)-(VII) residues (R)n, R1, R2X, Y, Z have the same meaning as in the final product of formula (I).

2. The method of producing aminophenylacetylene formula (I) and its salts

< / BR>
where (R)nmeans n identical or different residues from the group of halogen, alkyl and alkoxy;

n means 0, 1, 2 or 3;

A represents hydrogen or the acyl residue;

R1means hydrogen or unsubstituted or substituted hydrocarbon or uglevodorodokislyayuschih containing 1-6 C-atoms;

R2means hydrogen or unsubstituted or substituted hydrocarbon residue containing in the amount of 1-10 C-atoms;

or the group NR1R2means heterocy is
R2as heteroatom and may contain in the ring one or two heteroatoms from the group N, O and S;

R3means hydrogen or C1-C4-alkyl;

X, Y means independently of each other halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, each of these three latter residue is not substituted or substituted by one or more residues from the group halogen, C1-C4-alkoxy and C1-C4-alkylthio or3-C6-cycloalkyl,2-C6alkenyl,

WITH2-C6-quinil,3-C6-alkenylamine or3-C6-alkyloxy;

Z denotes CH or N,

characterized in that the compound of formula (II)

< / BR>
or its salt is subjected to interaction in the presence of a halogenation means with the formation of the halide of carboxylic acid and its rearrangement in the compound of formula (III)

< / BR>
then ammonolysis the compound (III) SO2Cl-group to obtain the compounds of formula (IV)

< / BR>
then reconnect (IV) the nitro-group to obtain the compound (V)

< / BR>
and then subjecting the compound (V) interaction with carbamate, respectively, with urethane SUB>-alkyl or a metal cation, to obtain the compounds of formula (I) in which R3in accordance with the M in the formula (VI) means N or C1-C4-alkyl, or, if M is a cation of the metal, means a hydrogen atom and a represents N, or for the case, And if desired in the final product of formula (I) is not hydrogen and acyl residue, acelerou obtained in stage 2 of the compound of formula (I) in which a represents N, and in formulas (II)-(VI) residues (R)n, R1, R2X, Y, Z have the same meaning as in the final product of formula (I).

3. The method of producing aminophenylacetylene formula (1) and its salts

< / BR>
where (R)nmeans n identical or different residues from the group of halogen, alkyl and alkoxy;

n means 0, 1, 2 or 3;

A represents hydrogen or the acyl residue;

R1means hydrogen or unsubstituted or substituted hydrocarbon or uglevodorodokislyayuschih containing 1-6 C-atoms;

R2means hydrogen or unsubstituted or substituted hydrocarbon residue containing in the amount of 1-10 C-atoms.;

or the group NR1R2means heterocyclic ring of 3-8 atoms in the ring which is not substituted or substituted and contains in the ring N-atom of g is p, N, O and S;

R3means hydrogen or C1-C4-alkyl;

X, Y means independently of each other halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, each of these three latter residue is not substituted or substituted by one or more residues from the group halogen, C1-C4-alkoxy and C1-C4-alkylthio or3-C6-cycloalkyl, C2-C6alkenyl,2-C6-quinil,3-C6-alkenylamine or3-C6-alkyloxy; Z denotes CH or N,

characterized in that the compound of formula (II)

< / BR>
or its salt is subjected to interaction in the presence of a halogenation means with the formation of the halide of carboxylic acid and its rearrangement in the compound of formula (III)

< / BR>
then subjected to the interaction of the compound of formula (III) with cyanate and with the heterocyclic amine of formula (VIII)

< / BR>
in which R3defined as in formula (I),

getting sulfonylureas of the formula (VII), after which restore the nitrogroup gives the compounds of formula (I) in which a represents N, or for the case, And if desired in the final product of formula (I) is not hydrogen, and Aah (II)-(VIII) residues (R)n, R1, R2X, Y, Z have the same meaning as in the final product of formula (I).

4. The method according to p. 1, characterized in that (R)nmeans n identical or different residues from the group halogen, C1-C4-alkyl and C1-C4-alkoxy; n is 0 or 1; a represents H or acyl with 1 to 8 C-atoms; R1means H, C1-C6-alkyl, C2-C6alkenyl, C2-C6-quinil, C1-C6-alkoxy, C2-C6-alconox,

WITH2-C6-alkyloxy or5-C6-cycloalkyl, each of the 7 last residue is not substituted or substituted by one or more residues from the group halogen, C1-C4-alkoxy, C1-C4-haloalkoxy,1-C4-alkylthio, mono - and di-(C1-C4-alkyl)-amino, cyano, azido, formyl, (C1-C4-alkyl)-carbonyl, (C1-C4-alkoxy)-carbonyl, C1-C4-alkylsulfonyl and C1-C4-alkylsulfonyl or phenyl not substituted or is substituted by residues from the group halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-halogenated, C1-C4-halogenoalkane and nitro; R2means H, C1-C6-alkyl, C2-C61-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, mono - and di-(C1-C4-alkyl)-amino, cyano, azido, formyl, (C1-C4-alkyl)-carbonyl, (C1-C4-alkoxy)-carbonyl, C1-C4-alkylsulfonyl and C1-C4-alkylsulfonyl; or a group NR1R2means a heterocyclic ring of 4, 5 or 6 atoms in the ring which may contain in the ring even up to two heteroatoms from the group N and O and which is not substituted or substituted by one or more residues from the group of C1-C4-alkyl; R3means N or CH3; one of the residues X and Y means halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-alkylthio, each of the last three residues are not substituted or substituted by one or more residues from the group halogen, C1-C2-alkoxy and C1-C2-alkylthio, or mono - or di-(C1-C2-alkyl)-amino and the other of the residues X and Y means WITH1-C2-alkyl, C1-C2-haloalkyl,1-C2-alkoxy, C1-C2-haloalkoxy or1-C2-alkylthio; Z denotes CH or n

5. The method according to p. 1 or 4, characterized in that a represents hydrogen, foppa halogen and (C1-C4)-alkoxy, or (C1-C4-alkoxy)-carbonyl, phenoxycarbonyl, phenylcarbamoyl, phenyl-(C1-C4-alkyl)-carbonyl or phenyl-(C1-C4-alkoxy)-carbonyl, and phenyl in each of the 4 mentioned last residue is not substituted or substituted; R1means H, C1-C2-alkyl, C1-C2-alkoxy, phenyl not substituted or substituted by one or more residues from the group halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-halogenated,1-C2-halogenoalkane; R2means N or C1-C2-alkyl; or a group NR1R2means a heterocyclic ring of 5 or 6 atoms in the ring which may contain in the ring before one heteroatom from the group N and O and which is not substituted or substituted by one or more C1-C2-alkyl residues; R3means N or CH3.

6. The method of obtaining the compounds of formula (III)

< / BR>
where R, n, R1and R2have the meanings as in formula (I ) according to one of paragraphs.1-3,

characterized in that the compound of formula (II)

< / BR>
or its salts, in which R, n, R1and R2have the meanings as in formula (III) is subjected to vzaimodeistviyami in the compound of formula (III).

7. The method of obtaining the compounds of formula (I'),

< / BR>
in which R, R1, R2X, Y, Z and n have the meanings as in formula (I) according to one of paragraphs.1-3;

R3denotes H,

characterized in that the compound of formula (V)

< / BR>
where R, R1, R2n have the meanings as in formula (I),

subjected to interaction with urethane salt of the formula (VI)

< / BR>
where X, Y, Z and n have the meanings as in formula (I);

AG denotes unsubstituted or substituted phenyl;

M denotes a metal cation,

with the formation of the compounds of formula (I').

8. The method of obtaining the compounds of formula (I")

< / BR>
where R, n, R1, R2, R3, A3X, Y, Z have the meanings as in formula (I) according to one of paragraphs.1-3;

And means acyl residue,

characterized in that acelerou compound of formula (I) in which a represents N.

9. Aminophenylacetylene formula (I), under item 1, in which a represents N.

10. The compounds of formula (III) and (VII) as defined in paragraphs.1-3.

11. The compound of formula (IV), as defined in paragraph 2.

12. The compounds of formula (VII), as defined in paragraph 1.

13. The compounds of formula (V), as defined in paragraph 1, except soedinenii in anthopology to carbonamide group of the formula CO-NR1R2and (R)ndenotes a chlorine atom in paraprotein to carbonamide group.

14. The compounds of formula VI, as they are presented in paragraph 1 and in which M denotes a cation.

 

Same patents:

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The invention relates to chemical means of weed control in crops based on derivatives sulfonilmocevina, in particular salts of 2-chloro-N-/(4-methoxy-6-methyl-1,3,5-triazine-2-yl) aminocarbonyl/benzosulfimide(chlorsulfuron) and specifically to its potassium salt of formula I:

< / BR>
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The invention relates to a new derived arylsulfonyl-triethynylbenzene formula I

which can find application in agriculture as a herbicide for weed control in cereal crops and flax, as well as herbicide composition based on it

The invention relates to novel acylated to aminophenylacetylene General formula I which possess herbicide action and selectivity of action in comparison with the previously known compounds of this series

The invention relates to chemical means of weed control in crops based on derivatives sulfonilmocevina, in particular salts of 2-chloro-N-/(4-methoxy-6-methyl-1,3,5-triazine-2-yl) aminocarbonyl/benzosulfimide(chlorsulfuron) and specifically to its potassium salt of formula I:

< / BR>
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< / BR>
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< / BR>
where R is C1-C6-alkyl, R1-halogen, n=0-1, V=0 or NH, U=CH or N
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