Substituted derivatives of sulfonylurea, or applicable to agriculture, salt and herbicide tool

 

(57) Abstract:

Derivatives of sulfonylurea of the formula (I)

< / BR>
in which R1means respectively substituted alkyl or phenyl; alkenyl or propargyl; alkylamino or dialkylamino; R2denotes hydrogen, halogen, respectively, halogen-substituted methyl, methoxy or ethoxy, alkylsulfonyl, nitro or cyano; R3indicates deformedarse, triptoreline, bromodifluoromethane, chloroformate or fluorine; R4denotes halogen, respectively, halogen-substituted methyl, ethyl, methoxy or ethoxy, or methyl - or dimethylaminopropyl; R5denotes hydrogen, alkyl, alkenyl or quinil; Z represents CH or N, indicating that (a) if R3denotes dipterocarp, R1does not denote di(alkyl)amino group, R2doesn't mean alkylsulfonyl, R4does not denote a methyl or methoxy group, (b) if R3denotes a fluorine atom, and Z denotes N, R4doesn't mean alkylamino, as well as their salts. Derivatives of sulfonylurea used as herbicides. 2 s and 5 C.p. f-crystals, 8 PL.

The invention relates to new substituted sulfonylurea derivatives of General formula (I)

C2-alkoxygroup; C1-C3-alkylamino or di-(C1-C4-alkyl)amino group;

R2hydrogen, halogen, methyl;

R3deformedarse, triptoreline, bromodifluoromethane, chloroformate or fluorine;

R4halogen, under certain conditions, halogen-substituted methyl, ethyl, C1-C2-alkoxygroup; methoxy - or ethoxypropan, methyl or dimethylaminopropan;

R5hydrogen;

Z is CH or N, provided that

a) when R3means dipterocarp, R1cannot be di(alkyl)amino group, and R4the stands or methoxy group,

b) when R3means a fluorine atom, and Z is N, R4can't be alkylaminocarbonyl;

or applicable to agriculture salts with herbicide activity and herbicide tool.

In the descriptions of the inventions (EP, NN 30433, 44212, 125205, 135332, 136061, 158600 and in the description of the invention to the U.S. patent NN 4534789 and 4127405) presents various substituted complex esters of alkyl - or arylsulfonyl, TU N 125205 and descriptions of invention to the U.S. patent NN 4576633 and 4515624 describes substituted sulfonylureas with aminosulfonates remains.

However, they do not satisfy the requirements of g is their basis can be used for effective weed control for crops such as, for example, rice, wheat and maize, at a low rate and do not damage plants.

Preferred derivatives of the sulfonylureas of the formula (I), where R1means C1-C4is an alkyl group which may be substituted with one or three halogen atom or C1-C2-alkoxygroup, and R2-R5and Z have the values listed above.

Among the preferred compounds include compounds of formula (I), where R1means C1-C3-alkylamino - or di-(C1-C4-alkyl)amino group, and R2-R5and Z have the meanings stated above; or substituted derivatives of sulfonylurea of the formula (I) in which R1means C1-C4is an alkyl group which may have 1 to 3 halogen atoms; methylamino or dimethylaminopropyl; R3means deformedarse or cryptometer or fluorine, and R2, R4, R5and Z have the meanings stated above; or substituted derivatives of sulfonylurea of the formula (I) in which R1means C1-C4is an alkyl group which may have 1 to 3 halogen atoms; methylamino or dimethylaminopropyl; R3means deformedarse - or the Z have the meanings above.

C1-C4-alkyl residues indicate, for example, methyl, ethyl, n-propyl or isopropyl, n-butyl, sec.-butyl or tert.-butyl, preferably methyl or ethyl;

C1-C3-halogenoalkane remains indicate, for example, vermeil, chloromethyl, methyl bromide, 2-foretel, 2-chloroethyl, deformity, dichloromethyl, trifluoromethyl, trichloromethyl, 2,2,2-triptorelin or 2,2,2-trichlorethyl, preferably 2,2,2-triptorelin;

C2-C5-alkoxyalkyl residues mean, for example, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 2-ethoxypropan or 3-ethoxypropan, preferably methoxymethyl, ethoxymethyl or 2-methoxyethyl;

C1-C3-acylaminoacyl mean, for example, methyl-, ethyl-, n-propyl or isopropylamino, preferably methylamine; di(C1-C4-alkyl) radicals, such as dimethyl-, diethyl-, di(n-propyl)-, di(isopropyl)-, di(tert.-butyl)-, methylethyl or methyl(isopropyl)amino, preferably dimethylamino;

Halogen denotes fluorine, chlorine, bromine, iodine.

Sulfonylureas of the formula (I) can be obtained by various methods described in the literature. Especially preferred are South in a known manner (EP 162723 or EP 44212) using approximately stoichiometric amount of a derivative of 2-amino-1,3,5-triazine or pyrimidine III at a temperature of from 0 to 120oC, preferably from 10 to 100oC. the Reaction may be carried out at normal pressure or low pressure (50 bar), preferably at 1-5 bar, continuously or periodically.

For the reaction, it is advisable to use inert solvents and thinners under appropriate reaction conditions. As solvents are used, for example, kalogeropoulou, in particular, chlorinated hydrocarbons, such as tetrachloroethylene, 1,1,2,2 - or 1,1,1,2-tetrachlorethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, chloronaphthalene, dichloronaphthalene, carbon tetrachloride, 1,1,1 - or 1,1,2-trichloroethane, trichloroethylene, pentachloroethane, o-, m-, p-differental, 1,2-dichloroethane, 1,1-dichloroethane, 1,2-CIS-dichloroethylene, chlorobenzene, torbenson, Brabanthal, idental, o-, m-, p-dichlorobenzene, o-, p-, m-dibromobenzyl, o-, m-, p-chlorotoluene, 1,2,4 - trichlorobenzene; simple ether, for example, a simple ethylpropyl ether, simple tert.-butyl ether, a simple n-butylethylamine ether, a simple di-n-butyl ether, simple diisobutenyl ether, simple dietarily ether, simple diisopropyl ether, anisole, phenetol, simple, cyclohexyl methyl ether, simple diethyl ether, simple etilenglikolevye ether, tetrahydrofuran, nitrobenzene, o-, m-, p-chloronitrobenzene, o-nitrotoluene; NITRILES, such as acetonitrile, butyronitrile, isobutyronitrile, benzonitrile, m-chlorobenzonitrile; aliphatic or cycloaliphatic hydrocarbons, e.g. heptane, pinan, Noonan, o-, m-, p-timol, gasoline fractions within a boiling point of from 70 to 190oC, cyclohexane, methylcyclohexane, decalin, petroleum ether, hexane, naphtha, 2,2,4-trimethylpentane, 2,2,3-trimethylpentane, 2,3,3-trimethylpentane, octane; esters, e.g. ethyl acetate, complex acetoacetic ether, isobutyl acetate; amides, for example, formamide, methylformamide, dimethylformamide; ketones, such as acetone, methyl ethyl ketone and the corresponding mixture. The solvent should be used in amount of about 100 to 2000 wt. preferably from 200 to 700 wt. with respect to the starting substances II.

Compound II, required for a conversion, is generally used in approximately equimolar amounts (excess or lack of, for example, from 0 to 20% based on the corresponding starting material III). Starting material III can be added beforehand in the previously specified diluent, and then add the starting material II.

However, the method of obtaining new compounds suitable the representatives and then was added to the starting material III. For the end of the reaction after addition of the components, the mixture is stirred for further 20 min to 24 h at a temperature of from 0 to 120oC, preferably at a temperature of from 10 to 100oC, in particular from 10 to 100oC.

To accelerate the reaction can be added preferably a tertiary amine, e.g. pyridine, ,,-picoline, 2,4-, 2,6-lutidine, 2,4,6-kallidin, p-dimethylaminopyridine, trimethylamine, triethylamine, three(n-propyl)amine, 1,4-diaza[2,2,2] bicicletta (DABCO) or 1,8-diazabicyclo[5,4,0]undec-7-ene in an amount of from 0.01 to 1 mol per mol of the original substance II.

The product I is allocated from the reaction mixture in the usual way, for example by distillation of the solvent or directly by filtration. The remaining residue can be washed with water or dilute acid to remove basic impurities. In addition, you can also dissolve the residue in a solvent not miscible with water, and rinsed as described above. The target compounds fall in pure form and, if necessary, they can be purified by recrystallization, mixing in an organic solvent, adsorbing impurities, or chromatographic means.

This interaction is carried out preferably in acetonitrile, easy-methyl-Ino from 0 to 50 molar equivalents of a tertiary amine, as, for example, 1,4-diazabicyclo[2,2,2]octane or triethylamine.

Method B.

The corresponding sulfonylureas formula IV transform a known manner (EP 120814, EP 101407) in an inert organic solvent at a temperature in the range from 0 to 120oC, preferably from 10 to 100oC, using a derivative of 2-amino-1,3,5-triazine or pyrimidine III. If this can be added bases, such as tertiary amines, which accelerates the reaction and improves the quality of the product.

Suitable bases for this purpose are, for example, tertiary amines, as described in method A, in particular, triethylamine or 1,4-diazabicyclo[2,2,2] octane in an amount of from 0.01 to 1 mol per starting material IV. As solvents it is expedient to apply the solvents specified in method A.

The solvent used in amounts of from 0 to 2000 wt. preferably from 200 to 700 wt. relative to the original substances IV.

Compound IV, required for a conversion, is generally used in approximately equimolar amounts (excess or lack of, for example, from 0 to 20% based on starting material (III). Starting material IV can be added to one of the above diluents and C and can be added to the base.

The final product I can be isolated from the reaction mixture in the usual way as described in method A.

Method C.

The sulfonamide of the formula V convert a known manner (EP 141777 and EP 101670) in an inert organic solvent, using approximately stoichiometric amount of phenylcarbamate VI at a temperature of from 0 to 120oC, preferably at a temperature of 20-100oC. the Reaction may be carried out at normal pressure or at pressures up to 50 bar, preferably at 1-5 bar, continuously or periodically.

If this can be added bases, such as tertiary amines, accelerating the reaction and improves the quality of the product. Suitable bases for this purpose are the reasons specified in the method And, in particular, triethylamine, 2,4,6-kallidin, 1,4-diazabicyclo[2,2,2]octane (DABCO) or 1,8-diazabicyclo[5,4,0] undec-7-ene (DBU) in an amount of from 0.01 to 1 mol per mol of the original substance V.

As solvents or diluents it is advisable to use these in the way And solvents and thinners.

The solvent used in quantities of from 100 to 2000 wt. preferably from 200 to 700 wt. relative to the educt V

Connection V, from 0 to 20% based on starting material (VI). Can the original substance VI to add in one of the above diluents, and then add the original substance V.

In addition, you can also educt V be added in the solvent and then to add to the carbamate VI. In both cases, before or during the reaction as a catalyst, you can add one of the specified grounds.

For the end of the reaction after addition of the components, the mixture is stirred for further 20 min to 24 h at a temperature of from 0 to 120oC, preferably from 10 to 100oC, in particular from 20 to 80oC.

Sulfonylureas of the formula (I) is recovered from the reaction mixture by conventional methods, as described in method A.

Method D.

The sulfonamide of the formula V turn in a known manner (EP 234352) in an inert organic solvent with approximately the stoichiometric amount of isocyanate VII at a temperature of from 0 to 150oC, preferably from 10 to 100oC. the Reaction may be carried out at normal pressure up to 50 bar), preferably at 1-5 bar, continuously or periodically.

At the same time or before the time of reaction may be added to the base, as, for example, tertiary amines, uskorea in method A, in particular, triethylamine or 2,4,6-kallidin in an amount of from 0.01 to 1 mol per mol of the original substance V.

As solvents it is expedient to apply the solvents specified in the method And in the amount of from 100 to 2000 wt. preferably from 200 to 700 wt. relative to the educt V

Compound V is generally used in about equimolar amounts (excess or lack of, from about 0 to 20% based on starting material (VII). Starting material VII can be added to one of the above diluents, and then add the original substance V. However, you can also sulfonamide add in the diluent and then adding the isocyanate VII.

For the end of the reaction after addition of the components, the mixture is stirred for further 20 min to 24 h at a temperature of from 0 to 120oC, preferably from 10 to 100oC, in particular from 20 to 80oC. Target product I can be isolated from the reaction mixture in the usual way as described in method A.

Sulfonylation formula II used as starting substances can be obtained in a known manner from the corresponding sulfonamides by vosganian [EP 44212, Hoybev-Weyl 11/2 (1985) 1106, U.S. patent 4379769) or by processing the sulfones the formula III and subsequent transformation of the resulting intermediates can be shared methods described in special heterocyclic literature (pyrimidines: D. J. Brown in "The Chemistry of Heterocyclic Compounds", A. Weissberger. E. C. Teylor (Hrsg.), Wiley, New York, 1985, I. 16; D. J. Brown in "Comprehensive Heterocyclic Chemistry", A. R. Katritzki (Hrsg.), Pergamon Press, New York, 1984, T. 3, 57 ff. triazine: E. M. Smolin and L. Rapoport in "The Chemistry of Heterocyclic Compounds", A. Weissberger, Interscience Publ. New York, 1959, I. 13; J. E. Quirke in "Comprehensive Heterocyclic Chemistry", A. R. Katritzki (Hrsg.), Pergamon Press. New York, 1984, T. 3, 457 ff.).

2-Aminopyrimidine and 2-amino-1,3,5-triazine, that in the 4 or 6 position have triptoreline or chlordiftormethane Deputy, can be obtained, in particular, the techniques described in the application DE 4007316.5, 4007317.3, 4007683.0, 4024761.9, 4024755.4 and 4024754.6.

Thus it is possible to obtain a derivative of formula IIIa, in which R4denotes methylamino, dimethylamino, methoxy, ethoxy or C2-haloalkoxy (see diagram 2).

Scheme 2.

< / BR>
n 0,1; R4NHCH3N(CH3)2, OCH3OC2H5C1-C2-haloalkoxy; Z is CH, n

Accordingly obtain derivatives of 2-amino-6-trifluoromethyl-1,3,5-triazine or 2-amino-6-cryptomaterial IIIc, 2,4-dihalogen-6-trichloromethyl-1,3,5-triazine or 2,4-dihalogen-6-cryptomaterial formula XV according to the scheme 3.

Scheme 3.

3OH, 2. Cl2, 3. SbF3), with subsequent treatment of R5NH2get smart products IIId

< / BR>
Similarly receive a 4-alkyl-2-amino-1,3,5-triazine or 4-alkyl-2-aminopyrimidine IIIe, if you use 2-alkoxy-4-alkyl-6-halogenfrei or 4-alkoxy-6-alkyl-2-halogenopyrimidines (see diagram 4).

Scheme 4.

< / BR>
Used as starting compounds 2-alkoxy-4-alkyl-6-halogen-1,3,5-triazine and 4-alkoxy-6-alkyl-2-halogenopyrimidines known in the literature (for example, 2-chloro-4-methoxy-6-methylpyrimidin in Bull. Soc. Chim Belg. 68 (1959) 30; 2-chloro-4-methoxy-6-methyl-1,3,5-triazine in Monatsh. Chem. 101 (1970) 724) or can be obtained in a similar way.

Chlorination of 2-methoxy-1,3,5-triazines or 2-methoxypyridine VIII, XV or XVIII chlorine derivatives in trichlormethane IX, XVI, or XIX is carried out, for example, at a temperature of from 100 to 180oC.

As gloriously means suitable elemental chlorine or chemicals, giving chlorine, such as, for example, sulfurylchloride or gospocentric.

The conversion can be carried out in the presence of an inert solvent, e.g. a chlorinated hydrocarbon, such as chlorobenzene, 1,2-, 1,3 - or 1,4-dichlorobenzene, th acid, anhydride of the acid, as, for example, chloracetamide, chloride-chloropropionic acid, a chloride,dichloropropionic acid, an inorganic acid halide, such as, for example, phosphorotrithioite or phosphoroxychloride, or preferably without solvent in the melt of the source materials VIII, XV or XVIII.

Accordingly, it is possible to accelerate the reaction by accelerating the formation of radicals. This is the irradiation with light, preferably ultraviolet radiation, or add a-azoisobutyronitrile in an amount of from 0.2 to 7 mol. in relation to the original substances XIII, XV and XVIII. The reaction can be accelerated by adding a catalyst; a catalyst suitable gospocentric, preferably in quantities of from 0.5 to 7 mol. from the original substances VIII, XV or XVIII. In this case, the original substance is added together with the catalyst and begin chlorination. Instead of phosphorochloridate you can also add a source component, forming it under the reaction conditions, for example, postarticle or yellow phosphorus, and then start chlorination.

Source materials VIII, XV and XVIII may be converted by chlorine, approximately stoichiometric amount, or preferably in excess of equival is 00 180oC, preferably from 120 to 150oC, without pressure or under pressure, continuously or periodically.

Glorious at a pressure of 1 bar, when this is used, preferably from 3.3 to 5 mol of gaseous chlorine per one equivalent metaxylene group in the original substances VIII, XV and XVIII, which leads to the conversion of chlorine from 91 to 60% By using appropriate conditions, for example, a moderate excess pressure, preferably from 1 to 10 bar, or bubble columns can increase the percentage of conversion of chlorine. Typically, gaseous chlorine is stirred for a long time with an organic phase or pass through a thick layer of the organic phase.

The duration of the reaction reaches typically from about 0.5 to 12 hours

In a preferred embodiment of the method proceed in such a way that in the course of from 0.5 to 12 h, preferably from 1 to 10 h, the required amount of gaseous chlorine under vigorous stirring injected into the liquid source materials VIII, XV and XVIII, and first start at a temperature of from 120 to 130oC and, taking into account ekzotermicheskie reaction, continuously raising the temperature so that at the end of the reaction is carried out at a temperature of from 135 to 150oC. In some cases, uchitelle reaction remove the tub with the cooling mixture and then heated.

Processing and secretion of the produced substances can be carried out in the usual way. For example, from the hot organic phase using an inert gas can be extracted residues of hydrogen chloride, chlorine or catalyst; this is already quite pure crude product with high yield. The crude product can be further purified by distillation or chromatography, or be used directly for further transformation.

The transformation of the derivatives of trichlormethane IX, XVI, or XIX using halogenoalkane funds is carried out, for example, at temperatures from 0 to 180oC.

As halogenoalkane means of suitable antimony TRIFLUORIDE in the presence or absence of catalytic amounts of salts of antimony (V) or fluoride.

It is advisable to use an excess of from 1 to 200, preferably from 5 to 25 mol. antimony TRIFLUORIDE to the equivalent of trichloromethyl. A catalytic amount of a salt of antimony (V) ranges from 1 to 20, preferably from 5 to 18 mol. trichlormethine. Source materials IX, XVI, or XIX metered preferably at a temperature of from 90 to 130oC for mixing with halogenoalkane means and then heated for from about 10 to about 240 minutes to also continuously source materials IX, XVI, or XIX add at a temperature of from 110 to 180oC for from 10 to about 240 minutes and at the same time under reduced pressure formed is distilled off end of matter XII, XVII or XX. The remaining traces of salts of antimony is removed by extraction with concentrated hydrochloric acid.

If the reaction of lead without the addition of salts of antimony (V) or apply only a small amount, for example, from 0.5 to 5 mol. and reduce the amount of antimony TRIFLUORIDE from 60 to 90 mol. the equivalent of trichloromethyl, the reaction proceeds with the formation of chloroformate.

Instead of antimony TRIFLUORIDE halogenoalkane can also be carried out using hydrogen fluoride at a temperature from 0 to 150oC, preferably at a temperature of from 40 to 120oC. To this mixed in an autoclave educt IX, XVI, or XIX with an excess of 300 to 700, preferably from 350 to 400 mol. of fluoride on the equivalent of trichloromethyl, and stirred for 10 minutes to 10 hours, Respectively, it is possible to accelerate the reaction in the same way as described in case of the use of antimony TRIFLUORIDE, by adding a catalyst, such as, for example, pentachloride antimony. After termination of the reaction and removal of the volatile components of the process peresa with amines XIII, for example, at temperatures from -80oC to 40oC.

2-Halogen-1,3,5-triazine or pyrimidines XII, XVII or XX can respond in an aprotic polar solvent with amines XIII at a temperature of from -80oC to 40oC; used amine XIII or in excess of, or use of organic auxiliary base.

For the reaction triazines or pyrimidines XII, XVII or XX with the amine XIII fit the following solvents are: ethers, such as, for example, a simple tert. -butyl ether, simple diethyl ether, simple ethylpropyl ether, a simple n-butylethylamine ether, a simple di-n-butyl ether, simple diisobutenyl ether, simple dietarily ether, simple diisopropyl ether, simple cyclohexylmethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, simple, dimethyl ether of diethylene glycol and anisole; esters, such as ethyl acetate, n-butyl acetate and isobutyl acetate; and chlorinated hydrocarbons, such as methylene chloride, 1,1,2,2-tetrachlorethane, 1,1-dichloroethylene, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene and 1-chloronaphthalene and mixtures of these solvents.

It is advisable to use the solvent in an amount of from 100 to 2000 wt. preferably from 400 to 1200 wt. relatively ishola at a temperature of -80oC to 40oC, preferably from -70oC to 25oC add preferably from 1.8 to 2.5, in particular, from 1.95 to 2.2 mol-equivalent of amine XIII relative to the original substances XII, XVII or XX for 0.5-2 h, stirred for 3 h and then heated for processing until the 25oC.

If used in about stoichiometric amount of amine XIII, it is advisable to use from 0.9 to 1.1 equivalents of an organic base from the original substances XII, XVII or XX. As the basis of a suitable organic base, such as, for example, triptorelin, triethylamine, N-ethyldiethanolamine, triisopropanolamine, N,N-dimethylaniline, N,N-dimethylcyclohexylamine, N-methylpyrrolidine, pyridine, quinoline, -, -, - picoline, 2,4 - and 2,6-lutidine, triethylenediamine.

The reaction may be carried out in the absence of pressure or under pressure, continuously or periodically.

For separation of the reaction mixture is extracted with water to remove salts, dried and purified organic phase, for example, chromatography method. However, you can also directly concentrating the organic phase and the residue is mixed with a solvent.

2-Amino-4-feralcode-1,3,5-triazine or 2-amino-4-peralkaline Fotini formula IIIb

< / BR>
in which Hal represents fluorine, chlorine or bromine, R5, n and Z have the previously mentioned meaning,

is treated with a nucleophile of the formula XIV

R4-H XIV

in which R4denotes methylamino, dimethylamino, methoxy, ethoxy or C1-C2-haloalkoxy,

or its salt XIVa.

The processing of 2-amino-4-feralcode-1,3,5-triazines or 2-amino-4-pcoralcalciumonline IIIb the nucleophile XIV or its salt XIVa carried out, for example, at temperatures from -80oC to 80oC, preferably from -30oC to 20oC, and either nucleophiles used in excess, or is added an organic base.

For processing 4-halogenated derivatives of IIIb fit the following solvents are: ethers, such as, for example, a simple tert.-butyl ether, simple diethyl ether, simple ethylpropyl ether, a simple n-butylethylamine ether, a simple di-n-butyl ether, simple diisobutenyl ether, simple dietarily ether, simple diisopropyl ether, simple cyclohexylmethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, simple, dimethyl ether of diethylene glycol and anisole; esters, such as ethyl acetate, n-butyl acetate and isobutyl acetate, and chlorinated plemental and 1 - chloronaphthalene, and mixtures of these solvents.

It is advisable to use the solvent in an amount of from 100 to 2000 wt. preferably from 400 to 1200 wt. relative to the original substances IIIb.

To a mixture of original substances IIIb in the previously mentioned solvent at a temperature of from -80oC to 80oC, preferably from -80oC to 25oC add preferably from 1.8 to 2.5, in particular, from 1.95 to 2.2, mol-equivalents of nucleophile XIVa of the original substance IIIb for 0.5-2 h, stirred until the reaction is completed (up to 3 h) and then heated to 25oC.

If you use only approximately stoichiometric amount of nucleophile XIV, XIVa or, it is advisable to add from 0.9 to 1.1 equivalents of an organic base in the calculation of the starting material IIIb. As organic bases suitable organic bases, such as trimethylamine, triethylamine, N-ethyldiethanolamine, triisopropanolamine, N,N - dimethylaniline, N, N-dimethylcyclohexylamine, N-methylpyrrolidine, pyridine, quinoline, -, -, - picoline, 2,4 - and 2,6-lutidine, triethylenediamine.

The reaction may be carried out in the absence of pressure or under pressure, continuously or periodically.

To separate the mixture of extras the reaction in most cases, fairly clean, so you only need to filter the precipitated salt and spend the concentration of the organic phase.

2-Aminopyrimidine with 4 or 6 position of the fluorine atom, can be obtained by analogy with the methods described in the European patent 378092 or in Yakugaku Zasshi 87 (1967) 1315. The corresponding 1,3,5-triazine can be obtained in a similar way. Relevant source materials, as, for example, 2,4-debtor-6-methoxy-1,3,5-triazine known in the literature (application for French patent 1561876 (CA 72, 90530), tiled application Germany 2901498 (CA91, 194627) or Chem. Ber. 102 (1969) 2330).

2-Aminopyrimidine or 1,3,5-triazine formula III, in which 4 or 6 position are bromodifluoroacetate described in the European patent 169815.

2-Aminopyrimidine, that in the 4 or 6 position are dipterocarp, can be obtained by the methods described in the European patent 84020.

Sulfanilamide formula IV were obtained by analogy with the known reactions (for example, European patent 120814). However, you can also translate sulfonylation formula I in normal conditions in an inert solvent, such as, for example, a simple ether or dichloromethane, treatment with phenol in the carbamates of the formula IV.

The carbamates of the formula VI can palousa isocyanates VII by treatment with phenol.

The isocyanates of the formula VII is obtained from the amines of formula III by treatment with oxalylamino or phosgene (by analogy with Angew. Chem. 83 (1971), 407, EP 388873).

The sulfonamides of the formula V can be obtained by reaction of the corresponding chlorides of sulfonic acids with ammonia (Houben Weyl, Methods der organischen Chemie, T. 9, (1955) 605). Chlorides of sulfonic acids are produced either by the reaction of Meerwein (diazotization of the corresponding amines, sulfachlorpyridazine, catalyzed copper salt), or by chlorosulfonylphenyl corresponding aromatic hydrocarbons (F. Muth in "Methods der organischen Chemie", Houben Weyl, Thieme Verlag, Stuttgart (1955) 557 ff). The sulfonamides of the formula V can also be obtained from the correspondingly substituted 2-hydroxybenzenesulfonate by processing the corresponding substituted sulphonylchloride in the presence of an auxiliary base.

Typical examples of the preparation of the intermediate compounds are given in the experimental part.

Salts of compounds I can be obtained in a known manner (EP 304282, U.S. patent 4599412). They are obtained by deprotonation of the corresponding sulfonylureas I in water or an inert organic solvent at temperatures from -80oC to 120oC, preferably from 0 to 60oC, in the presence of lacnych or alkaline-earth metals, as, for example, sodium hydroxide, potassium and lithium, methanolate, ethanolate and tert.-butanolate sodium, sodium hydride and calcium and calcium oxide.

As solvents, along with water, are also considered, for example, alcohols, such as methanol, ethanol and tert.-butanol; ethers, such as tetrahydrofuran and dioxane, acetonitrile, dimethylformamide; ketones, such as acetone and methyl ethyl ketone; and halogenated hydrocarbons.

The deprotonation can be carried out at normal pressure or at pressures up to 50 bar, preferably at normal pressure to 5 bar gauge pressure.

The compounds I or herbicide products containing these compounds, and their salts with alkali or alkaline-earth metals, acceptable for the environment, can be effectively used to control weeds in such crops, such as wheat, rice and corn, without damaging the cultivated plants; the effect is also achieved when a low consumption rate.

Therefore, an object of the present invention is also an herbicide agent, comprising the active substance derived sulfonylureas and targeted supplements that are acceptable in agriculture, sidereal, di(C1-C4)-alkylamino, R2is hydrogen, R3triptoreline, fluorine, R4methoxy, R5is hydrogen, Z is CH, in an effective amount.

The tool can be used in the form of directly sprayable solutions, powders, suspensions, and high-grade water, oil and other suspensions or dispersions, emulsions, oil dispersions, pastes, powdered drugs, scattering agents or granules by spraying, dusting, spraying or spreading. Forms used compositions depend on the task; in each case they should ensure, whenever possible, the fine distribution of the proposed invention the active substances.

The compounds I are suitable mainly for getting directly sprayable solutions, emulsions, pastes or oil dispersions. As inert additives are mainly used in the mineral oil fraction having a boiling range from medium to high, such as kerosene or diesel oil, furthermore coal oil resin and oil of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffin, Teton, cyclohexanone, chlorobenzene, isophorone or strongly polar solvents, such as N,N-dimethylformamide, dimethylsulfoxide, N is an organic or water.

Water forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water dispersible granules by adding water. To obtain emulsions, pastes or oil dispersions, the substrates as such or dissolved in an oil or solvent homogenizers in the water with wetting, adhesive, dispersant or emulsifying means. Can be manufactured concentrates consisting of active substance, wetting, adhesive, dispersant or emulsifying means and, accordingly, solvent or oil, which is diluted with water.

As surface-active substances are considered alkaline salts, alkaline earth metals, ammonium, aromatic sulfonic acids, for example lignin-, phenol-, naphthalene - and dibutylaminoethanol, as well as the fatty acid series, alkyl - and alkylarylsulfonates, alkyl-, lauric ethers, and sulfates of fatty alcohol series, and salt hexa-, hepta - and octadecanol and simple glycol ether of a fatty alcohol ragnatela or naphthalenesulfonate with phenol and formaldehyde, simple polyoxyethyleneglycol ether, ethoxylated simple isooctyl, octyl - or Nonylphenol, alkylphenol-, tributyltinchloride ether, alkylaromatic alcohols, isotridecyl alcohol, condensates of ethylene oxide and fatty alcohol series, ethoxylated castor oil, easy oksietilenovym ether or polyoxypropylene, acetate simple polyglycolide ester lauric alcohol, sorbitol complex ether, lignin-spent sulfite liquor or methylcellulose.

Powder, spray and spray preparations can be produced by mixing or grinding the active substances with a solid filler.

Granulates, for example, the pellets in the shell, impregnating the granules and homogeneous granules can be manufactured by attaching the active substances to a solid fillers. Solid fillers are mineral soils, such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium, magnesium oxide, ground synthetic materials, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and resteasy powder or other solid fillers.

The compositions usually contain from 0.1 to 95 wt. preferably from 0.5 to 90 wt. the active substance.

Examples of formulations:

I. 90 wt.h. compound No. 1 are mixed with 10 wt.h. N-methyl-pyrrolidine and get the solution suitable for use in the form of tiny droplets.

II. 20 wt.h. connection N 5 dissolved in a mixture consisting of 80 wt.h. xylene, 10 wt.h. product accession 8-10 mol of ethylene oxide to 1 mol of N-monoethanolamide butyric acid, 5 wt.h. calcium salts of dodecylbenzenesulfonate and 5 wt.h. product accession of 40 mol of ethylene oxide to 1 mol of castor oil. By mixing and fine distribution of the solution in 100000 wt.h. water get a water dispersion containing 0.02 wt. the active substance.

III. 20 wt.h. connection N 1 dissolved in a mixture consisting of 40 wt.h. cyclohexanone, 30 wt. including Isobutanol, 20 wt.h. the product of the joining of 7 mol of ethylene oxide to 1 mol of isooctylphenol and 10 wt.h. product accession of 40 mol of ethylene oxide to 1 mol of castor oil. By mixing and fine distribution of the solution in 100000 wt.h. water receive water dispersion consisting of 0.02 wt. the active substance.

IV. 20 wt.h. the active substance N 5 dissolved in a mixture consisting of 25 wt.h. cycle accession of 40 mol of ethylene oxide to 1 mol of castor oil. By mixing and fine distribution of the solution in 100000 wt. including water get a water dispersion containing 0.02 wt. the active substance.

V. 20 wt.h. the active substance N 1 is well mixed with 3 wt.h. parts of the sodium salt diisobutyrate-a-sulfonic acids, 17 wt.h. salt sodium ligninsulfonate from spent sulfite liquor and 60 wt.h. powdery silicic acid gel and ground in a hammer mill. By finely distributing the mixture in 20000 wt.h. water get the solution for spraying, containing 0.1 wt. the active substance.

VI. 3 wt. including the active substance N 14 mixed with 97 wt.h. superfine kaolin. Thus obtained pulverized product containing 3 wt. the active substance.

VII. 30 wt.h. the active substance No. 14 mix well with a mixture of 92 wt. including powdery silicic acid gel and 8 wt.h. paraffin oil, which is sprayed on the surface of the silicic acid gel. In this way, get prepared active material with good adhesion.

VIII. 20 wt. including the active substance N 5 well mixed with 2 wt.h. calcium salts of dodecylbenzenesulfonate, 8 mass.h. simple polyglycolic ether is real butter. Get a stable oil dispersion.

The application can be carried out according to the method before or after germination. If the active substance is poorly tolerated by some cultivated plants, you can apply a special technique by which herbicide means of spraying devices are applied in such a way that, if possible, do not contact with the leaves of sensitive plants, while the active substances on the leaves growing among them undesirable plants or fall on an exposed surface.

The consumption rate of the active substance, depending on the purpose of application, time of year, plants and the growth stage reach from 0.001 to 1.0 kg/ha, preferably from 0.01 to 0.5 kg/ha of active substance.

Given the variety of methods of application proposed in the invention compounds or products containing these compounds may also be used for a large number of cultivated plants to remove weeds. Discusses, for example, the following crops (table. 1).

To broaden the spectrum of action and to achieve synergistic effect of sulfonylurea derivatives of the formula (I) can be mixed with megaalisa with them. As components for mixing are considered, for example, diasen, 4H-3,1-benzoxazin-derivatives, benzothiadiazine, 2,6-dinitroanilines, N-phenylcarbamates, thiocarbamates, halogenecarbonate acid, triazine, amides, urea, simple diphenyl ether, triazinone, orally, benzoguanamine, cyclohexane-1,3-dione derivatives, derivatives of quinoline-carboxylic acid, phenyloxy or heterooligomerization acid, and their salts, esters and amides, and others.

In addition, useful compounds of the formula I to be used not only individually but also in combination with other herbicides, also mixed with other means for protection of plants, for example, with means for weed control or phytopathogenic fungi or bacteria. In addition, interest mixed with solutions of mineral salts, which are used to correct the lack of nutrients and trace elements. Can also be added neotomine oils and oil concentrates.

Below are examples of synthesis of compounds I.

The manufacture of intermediate products:

Complex 2-amino-4-hlorfenilovy broadcast methansulfonate

of 174.5 g methanesulfonanilide (1,52 mol), food (of 1.52 mol) in 400 ml of methylene chloride. Stirred for 18 h at a temperature of 25oC, the mixture is introduced into ice water and the separated organic phase. The organic phase is washed twice with water and dried with Na2SO4. After removal of the solvent remains gradually crystallizing the residue product, sufficiently pure for further conversion (329,5 g, 98% theoretical. ). The product can be recrystallized from methanol/water (so pl. 70-71oC).

1H-NMR spectrum (250 MHz, CDCl3, int. TMS): 7,10 (d, 1H), 6.75 in (dd, 1H), to 6.67 (dd, 1H), 4,10 (ush. 2H), and 3.16 (s, 3H).

Complex 2-chlorosulfonylphenyl broadcast methansulfonate

The solution of diazonium salts obtained by simultaneous injection of a solution of 39.5 g of sodium nitrate (or 0.57 mol) in 60 ml of water and 105 g of complex 2-aminophenylamino ether methanesulfonate (or 0.57 mol) in 200 ml of concentrated hydrochloric acid at a temperature of 0-5oC and stirring for 1 h at a temperature of 0oC, prikapivatsya in saturated sulfur dioxide solution of 1.7 g CuCl2and 4.5 g of chloride of benzyltriethylammonium in 200 ml of 1,2-dichloroethane and 10 ml of water at a temperature of 0 to 10oC. Remove the cooling and stirred at a temperature of 25oC for 30 min, then at slow increase in the temperature of the reaction mixture, ESEA2SO4. After removal of the solvent an oily residue remains, which can crystallize by trituration with a small amount of ethanol. Thus obtain 139 g of compound indicated in heading (90% of theory.) with so pl. 94-95oC.

1H-NMR (300 MHz, CDCl3, int. TMS): 8,10 (d, 1H), 7.68 per-a 7.85 (m, 2H), 7,51 (1H), 3,42 (s, 3H).

Complex (2-aminosulfonyl)phenyl ester methanesulfonate

Ammonia at a temperature of -30oC is introduced into a solution of 130 g of complex (2-chlorosulfonyl)phenyl ether methanesulfonate in 1 l of tetrahydrofuran and control transformations by thin-layer chromatography. After the implementation of the reaction, the tetrahydrofuran is distilled off in vacuum, obtained using a water-jet pump, and the residue triturated with water and simple diethyl ether. So get 110,2 g of compound indicated in heading (91%) with T. pl. 131-132oC.

1H-NMR (300 MHz, CD3SOCD3, int. TMS): of 7.90 (d, 1H), to 7.61 (ush, 2H), 7,45-7,74 (m, 3H), 3,50 (s, N).

2-(dimethylaminomethylene)benzosulfimide

A solution of 5.0 g of 2-oxybenzenesulfonate (29 mmol) in 200 ml of acetonitrile is mixed at a temperature of 25oC with 4.0 g of potassium carbonate (29 mmol). After 10 min stirring at ka and the temperature. Volatile components are removed under vacuum, obtained using a water-jet pump, the residue absorb complex ethyl ester acetic acid, the solution is dried over Na2SO4and the solvent is removed in vacuum, obtained using a water-jet pump. The balance is strongly stirred for 1 h with 100 ml simple diethyl ether. The crystalline product is sucked off and dried at a temperature of 40oC in vacuum. Thus obtain 5.7 g of the compound indicated in the heading.

1H-NMR spectrum (250 MHz, CD3SOCD3, int. TMS) d: to $ 7.91 (d, 1H), EUR 7.57-7,74 (m, 2H), 7,49 (ush, 2H), was 7.36-7,52 (m, 1H), to 3.02 (s, 6N).

Obtaining intermediates III

2,4-debtor-6-trichlormethane-1,3,5-triazine

In a mixture of 300 g (2,041 mol) 2,4-debtor-6-methoxy-1,3,5-triazine and 0.3 g (a,-azoisobutyronitrile at a temperature of 130oC and by UV rays enter the stream of gaseous chlorine in such a way that within 2 hours the temperature from 140 to 145oC. After the NMR spectroscopic monitoring of the reaction by external heating of the injected chlorine gas for 3 hours at 135-140oC. After extraction of the precipitated sludge and distillation of the filtrate in vacuo get 444 g (87% of theory.) the specified connection with tempg (1,048 mol) of antimony TRIFLUORIDE and 35.2 g (0,117 mol) pentachloride antimony add half of 210 g (0,838 mol) 2,4-debtor-6-trichlormethane-1,3,5-triazine at a temperature of 110oC with stirring so that the first set temperature 125oC; while establishing sustainable boil add lead with additional heating. Within 1 h and stirred at a temperature of 125-130oC and boiling at a temperature of 100-105oC fraction is distilled through a 25-cm Packed column. After the decay reaction for 30 min added dropwise remaining half trichlorophenoxypropionic and the fraction at a temperature of 100-105oC continuously distilled off. The total duration of the reaction reaches 3 o'clock Receive RUR 134.4 g (79.8 per cent theoretical.) the connection specified in the header, c n2D41,3550.

6 chloroformate-2,4-debtor-1,3,5-triazine

210 g (0,838 mol) 2,4-debtor-6-trichlormethane-1,3,5-triazine for 10 min with stirring at a temperature of 110oC is added to 110 g (0,614 mol) of antimony TRIFLUORIDE. After submitting 3/4 of 9,38 g (0,0313 mol) pentachloride antimony is heated to 145oC and stirred for 1 hour Add the remaining catalyst and again stirred for 2 h, and in the form of a low-boiling fraction through a 30 cm Packed column in the range from 95 to 105oC get 20 grams (11.8% of theory. ) 2,4-debtor-6-triptoreline-1,3,5-triazine. The residue boiling 125-130oC; n2D41,4042.

2,4-dichloro-6-triptoreline-1,3,5-triazine

To a mixture of 40.9 g (0,229 mol) fluoride, antimony and 7,03 g (0,0234 mol) pentachloride antimony added with stirring to 52 g (0,183 mol) of 2,4-dichloro-6-trichlormethane-1,3,5-triazine for 5 min at a temperature of 90oC, and the temperature was raised to 180oC. Stirred for 20 minutes at a temperature of from 170 to 180oC and then the crude product is distilled at a temperature 90-103oC/70 mbar. By re-distillation and 32.3 g (75,5% of theory. ) of the compounds with a boiling point 165-173oC.

2-amino-4-fluoro-6-triptoreline-1,3,5-triazine

4.4 g (0,295 mol) of gaseous ammonia for 45 min at a temperature of from -70 to -65oC under stirring injected into a mixture of 26.0 g (0,1293 mol) 2,4-debtor-6-triptoreline-1,3,5-triazine in 100 ml of tetrahydrofuran. The mixture is stirred for 2 h at -70oC and during the night when heated to the 22oC. After concentration in vacuo the residue is mixed with water, sucked off and washed. After drying obtain 22 g (85,9% of theory.) the specified connection with so pl. from 138 to 139oC.

2,4-beltramino-6-triptoreline-1,3,5-triazine and

2-methylamino-4-fluoro-6-trismus from 19,0 g (0,0945 mol) 2,4-debtor-6-triptoreline-1,3,5-triazine in 100 ml of diethyl simple alcohol. The mixture is stirred for 2 h at -70oC and during the night when heated to the 22oC. the Reaction mixture was concentrated in vacuo, absorb with methylene chloride and washed with water. After drying separated into fractions by chromatographic method through silikagelevye column, and at first both factions receive 5.0 g (25% of theory.) 2-methylamine-4-fluoro-6-triptoreline-1,3,5-triazine with so pl. 68-72oC. the following fractions 4-7 allocate 10.7 g (51% of theory.) poorly soluble 2,4-beltramino-6-triptoreline-1,3,5-triazine with so pl. 150-152oC.

2-amino-4-chloroformate-6-fluoro-1,3,5-triazine and

2,4-diamino-6-diamino-6-deformedarse-1,3,5-triazine

7,8 g (0.46 mol) of ammonia injected for 45 min with stirring at -70oC in a mixture of 50.0 g (0.23 mol) of 2,4-debtor-6-chloroformate-1,3,5-triazine in 150 ml of tetrahydrofuran. For 2 h at -70oC and during the night when heated to the 22oC the mixture is stirred. The reaction mixture was concentrated in vacuo, washed with water and dried. Then the reaction product Usacheva using methylene chloride to silikagelevye the column and elute in a similar solvent. In the fractions 1-8 gain of 21.5 g (43,6% of theory. ) 2-amino-4-fluoro-6-hardif is Ricci 9-14 poorly soluble 2,4-diamino-6-chloroformate-1,3,5-triazine (11.2 g, 23% of theoretical.) with so pl. 114oC.

2 chloroformate-4-fluoro-6-methylamino-1,3,5-triazine and

2,4-beltramino-6-chloroformate-1,3,5-triazine

to 5.2 g (0,166 mol) of methylamine administered for 20 min with stirring at -70oC in the mixture of 18.1 g (0,083 mol) of 4-diperchlorate-2,6-debtor-1,3,5-triazine. The mixture is stirred for 2 h at -70oC and during the night when heated to the 22oC. the Reaction mixture was concentrated in vacuo, absorb with methylene chloride, washed with water and dried. After chromatographic separation on silica gel get in the first fractions of 5.5 g (29% of theory.) 2 chloroformate-4-fluoro-6-methylamino-1,3,5-triazine with so pl. 62-64oC. In the last chase allocate 8.7 g (44% of theory.) 2,4-beltramino-6-chloroformate-1,3,5-triazine with so pl. 118-120oC.

2-amino-4-methoxy-6-triptoreline-1,3,5-triazine

of 9.1 g (0.05 mol) 30-aqueous sodium methylate added at 0oC for 15 min with stirring in a mixture of 10 g (0.05 mol) 2-amino-4-fluoro-6-triptoreline-1,3,5-triazine in 100 ml of methanol. After stirring for 1 h at a temperature of 0oC the mixture was concentrated in vacuo, absorb with methylene chloride and extracted with water. After drying and concentration of Potocki-6-methoxy-1,3,5-triazine

8,4 g (0,047 mol) of 30% sodium methylate was added when the temperature at 0oC for 15 min with stirring in a mixture of 10 g (0,047 mol) 2-amino-4-chloroformate-6-fluoro-1,3,5-triazine in 100 ml of methanol. After stirring for 1 h at 0oC the mixture was concentrated in vacuo, absorb with methylene chloride and extracted with water. After drying and concentrating obtain 10.4 g (98.5% of theory. the connection specified in the header, so pl. 109-110oC.

2-amino-4-methoxy-6-triptoreline-1,3,5-triazine

of 9.1 g (0.05 mol) of 30% sodium methylate added at 0oC for 15 min with stirring in a mixture of 10 g (0.05 mol) 2-amino-4-fluoro-6-triptoreline-1,3,5-triazine in 100 ml of methanol. After stirring for 1 h at 0oC the mixture was concentrated in vacuo, absorb with methylene chloride and extracted with water. After drying and concentrating receive a 10.5 g (99% of theory.) the connection specified in the header, so pl. 96-101oC.

2-amino-4-chloroformate-6-methoxy-1,3,5-triazine

8,4 g (0,047 mol) of 30% sodium methylate added at 0oC for 15 min with stirring in a mixture of 10 g (0,047 mol) 2-amino-4-chloroformate-6-fluoro-1,3,5-triazine in 100 ml of methanol. After stirring for 1 h at 0o is interevene obtain 10.4 g (98.5% of theory.) connection specified in the header, so pl. 109-110oC.

2-amino-4-ethoxy-6-triptoreline-1,3,5-triazine

2.3 g (0,093 mol) of 97% sodium hydride in portions at a temperature of from 20 to 35oC is added to 300 ml of ethanol and stirred for 15 min to obtain a solution. At a temperature of 0oC while stirring add to 18.5 g (0,093 mol) 2-amino-4-fluoro-6-triptoreline-1,3,5-triazine for 10 minutes, stirred for 1 h at 0oC and over night at a temperature of 22oC. After concentration in vacuo the residue is absorbed with methylene chloride, extracted with water and dried. After concentrating obtain 17.9 g (85,9% of theory.) the specified connection with so pl. from 96 to 91oC.

2-amino-4-chloroformate-6-ethoxy-1,3,5-triazine

1.2 g (0,047 mol) of 97% sodium hydride was added when the temperature from 20 to 35oC portions to 150 ml of ethanol and stirred for 15 min before the formation of the solution. Then at 0oC while stirring, add 10 g (0,047 mol) 2-amino-4-chloroformate-6-fluoro-1,3,5-triazine, stirred for 1 h at a temperature of 0oC and over night at a temperature of 22oC. After concentration in vacuo the residue is absorbed with methylene chloride, extracted with water and dried. After concentri-6-triptoreline-1,3,5-triazine

3.5 g (0,111 mol) of methylamine injected at 0oC for 20 min with stirring into a solution of 11 g (by 0.055 mol) of 2-amino-4-fluoro-6-triptoreline-1,3,5-triazine in 150 ml of tetrahydrofuran. Stirred for 1 h at 0oC and over night at a temperature of 22oC. the Reaction mixture was concentrated in vacuo, mixed with water, and dried. Obtain 10.8 g (93.1% of theory.) the specified connection with so pl. from 155 to 157oC (decomposition).

2-amino-4-chloroformate-6-methylamino-1,3,5-triazine

2.9 g (0,093 mol) of methylamine administered for 20 min with stirring at 0oC in a solution of 10 g (0,047 mol) 2-amino-4-chloroformate-6-fluoro-1,3,5-triazine in 150 ml of simple diethyl ether. Stirred for 1 h at 0oC and during the night when the 22oC. After washing with water, drying and concentrating obtain 9.4 g (89.5% of theory.) the specified connection with so pl. 143oC (decomposition).

2-amino-4-dimethylamino-6-triptoreline-1,3,5-triazine

5.0 g (0,111 mol) of dimethylamine administered for 20 min while stirring at a temperature of 0oC in a solution of 11 g (by 0.055 mol) of 2-amino-4-fluoro-6-triptoreline-1,3,5-triazine in 150 ml of tetrahydrofuran. Stirred for 1 h at a temperature of 0oC and over night at a temperature of 22so pl. 114-118oC (decomposition).

2-amino-4-chloroformate-6-dimethylamino-1,3,5-triazine

of 4.2 g (0,093 mol) of dimethylamine administered for 20 min while stirring at a temperature of 0oC in a solution of 10 g (0,047 mol) 2-amino-4-chloroformate-6-fluoro-1,3,5-triazine in 150 ml of simple diethyl ether. Stirred for 1 h at a temperature of 0oC and over night at a temperature of 22oC. After washing with water, drying and concentration gain of 9.8 g (87,8% of theory. the connection specified in the header, so pl. from 130 to 133oC (decomposition).

2-chloro-4-trichlormethane-6-trichloromethylpyridine

a) 2-chloro-4-methoxy-6-trichloromethylpyridine

293,1 g (1,692 mol) of 30% aqueous solution of sodium methylate added for 1.5 h at a temperature of from 0 to 5oC to a solution of 434 g (1,692 mol) of 2,6-dichloro-4-trichloromethylpyridine in 1 l of 1,2-dichloroethane. Stirred for 1 h at a temperature of from 0 to 5oC and 12 h at a temperature of 25oC. the Reaction mixture is extracted four times with water and three times with a saturated solution of salt. After drying over magnesium sulfate and concentrating receive 423 g (95% of theory.) the connection specified in the header, in the form of almost colorless oil.

1N-I is pyrimidin

In a solution of 210 g (0,802 mol) of 2-chloro-4-methoxy-6-trichloromethylpyridine and 260 mg (0,0016 mol), azoisobutyronitrile injected chlorine by UV radiation and monitoring the progress of the reaction by gas chromatography at a temperature of first 110oC, and also after removal of the heating bath set temperature of 140 reactionoC. After decay reactions for 5.5 h at 20oC enter total 341 g (4.8 mol) of chlorine. To the cooled reaction mixture from the 40oC add n-pentane for sediment. The precipitate is sucked off, washed with petroleum ether and dried, and get to 163 g (55% of theory. the connection specified in the header, so pl. 67-69oC.

The filtrate (113,8 g) after the gas chromatogram consisted of 83% of the compound indicated in the title, 4% 2-chloro-4-dichloromethoxy-6-trichloromethylpyridine and 9% of 2,4-dichloro-6-trichloromethylpyridine. The overall yield of the connection specified in the header, amounted to 87.6% of theory.

2,4-debtor-6-trichloromethylpyridine

210 g (2,96 mol) of chlorine by UV radiation and monitoring the progress of the reaction by gas chromatography for 2.5 h with stirring at 130oC enter in 123 g (0,843 mol) of 2,2-debtor-6-methoxypyridine, poluchennogo in vacuum, and get 190,2 g (90,5% of theory.) the connection specified in the header, with a boiling point of 40 -43oC/0.2 mbar.

2,4-dichloro-6-trichloromethylpyridine

303 g (4,27 mol) of chlorine by UV radiation and monitoring the progress of the reaction by gas chromatography, with stirring administered for 0.5 h at 80oC, 1 h at 100 ° oC, 3 hours at a temperature of 120oC and 3 h at 150oC in a mixture of 209 g (1,168 mol) of 2,6-dichloro-4-methoxypyridine and 2 g (0.012 mol), azoisobutyronitrile. Then the reaction mixture is distilled in vacuum. Get 241,3 g (73% of theory.) the connection specified in the header, with a boiling point 87-88oC/0.4 mbar; melting point 55-56oC.

2,4-debtor-6-cryptomaterial

to 49.9 g (0.2 mol) of 2,4-debtor-6-trichloromethylpyridine added at a temperature of 100oC for 15 min with stirring to a mixture of to 39.3 g (0.22 mol) of antimony TRIFLUORIDE and 9,38 g (0,031 mol) pentachloride antimony. Within 25 minutes raise the temperature from 100 to 150oC and again stirred for 30 min, and at a temperature in the range from 120 to 125oC is set to reflux. By subsequent distillation of 37.1 g (92.7% of theory.) the connection specified in the header, with a boiling point of 125 is amidine add 100oC for 10 min with stirring to a mixture of 44.5 g (0,249 mol) of antimony TRIFLUORIDE and 0.94 g (0,0031 mol) pentachloride antimony. Within 25 minutes raise the temperature from 100 to 175oC, and at a temperature of 145oC comes reflux. After stirring for 1.5 h the reaction product is distilled at 146-150oC. the Distillate was dissolved in methylene chloride, extracted with 6 N. hydrochloric acid and dried over magnesium sulfate. After concentration in vacuo get as a remainder the connection specified in the header, with the release of 63.7 g (78.8% of theory.).

2-fluoro-4-triptoreline-6-cryptomaterial

80 g (0,219 mol) of 2-chloro-4-trichloromethyl-6-trichloromethylpyridine added dropwise within 5 min while stirring at a temperature of 100oC to the mixture of 93,9 g (0,525 mol) of antimony TRIFLUORIDE and 18.7 g (0,0627 mol) pentachloride antimony. Within 10 minutes the bath temperature was raised to 140oC and stirred for 1 h, and comes with more severe reflux. The reaction product is distilled at a temperature of 135-140oC, to end at 95oC/50 mbar. The distillate is taken with methylene chloride, extracted with 6 N. hydrochloric acid and dried over magnesium sulfate. After concentration in vacuo get the connection specified the ENT-6-trichloromethylpyridine added dropwise within 5 min with stirring at 100oC to a mixture of 80 g (0,447 mol) of antimony TRIFLUORIDE and 18,77 g (0,0627 mol) pentachloride antimony, and the reaction temperature was raised to 140oC. Stirred for 45 min at 150oC. For distillation set pressure 210 mbar, and the connection specified in the header goes at a temperature of 128oC; the last volatile components distilled at a temperature of 110oC/22 mbar. The distillate is dissolved in methylene chloride, extracted with 6 N. hydrochloric acid and dried over magnesium sulfate. After concentration in vacuo get the connection specified in the header, with a yield of 80 g (84.4 per cent of theoretical.) in the form of a colorless oil, n2D51,4604.

2-amino-4-chloroformate-6-ftorpirimidinu

of 9.8 g (0,578 mol) of gaseous ammonia is injected within 1 h at temperatures from -75 to -70oC with stirring in a mixture of 62.5 g (0,289 mol) 2,4-debtor-6-chlordiftormethane in 300 ml of tetrahydrofuran. Stirred for 1 h at -70oC and then warmed to room temperature. The precipitation is sucked off, share with acetic ether and water and the organic phase is dried over magnesium sulfate. The reaction filtrate is concentrated and dissolved in the above-mentioned phase WC 5:1 and concentrate. Get 46,5 g (75.3% of theory.) the connection specified in the header, in the form of colorless crystals with a melting point of 77 -80oC.

2-amino-4-fluoro-6-cryptomaterial

8.7 g (0.51 mol) of gaseous ammonia is injected within 1 h at temperatures from -75 to -70oC with stirring in a mixture of 51 g (0,255 mol) 2,4-debtor-6-cryptomaterial 200 ml simple diethyl ether. Stirred for another 1.5 h at -70oC and 1 h at room temperature. The reaction mixture was concentrated in vacuo, absorb with methylene chloride and extracted with water. After drying the organic phase, concentration and chromatographic separation through silica gel using petroleum ether and simple ether in a ratio of 8:1 are of 38.1 g (75.6% of theory.) the connection specified in the header, in the form of colorless crystals with a melting point 86-89oC.

2-amino-4-chloro-6-cryptomaterial

4.3 g (0.25 mol) of gaseous ammonia is injected within 45 min while stirring at a temperature of from -50 to -45oC in a mixture of 23.3 g (0.1 mol) of 2,4-dichloro-6-cryptomaterial in 150 ml methyl-tert.-butyl ether. Stirred for 30 min at -50oC, for 1 h at -30oC for 1 h prior.) 4-amino-2,4-dichloropyrimidine with a melting point 270-272oC as a by-product. The filtrate is washed with water, dried, partially concentrated in vacuo and separated into fractions by chromatographic method using petroleum ether and simple ether in a ratio of 5:1, and in the first fractions obtained 3 g (12.8% of theory.) the source material in the form of a colorless oil and the last chase 9 g (42% of theory. the connection specified in the header, in the form of colorless crystals with a melting point of 55 -56oC. Conversion are 48.3%

4 chloroformate-6-fluoro-2-methylaminopropane

of 20.3 g (0,0938 mol) of 4-chloroformate-2,6-giftability placed in 150 ml of tetrahydrofuran and at a temperature of from -70 to -60oC mixed for 30 min with 5.8 g (0,188 mol) of gaseous methylamine. Mix respectively 1 h at temperatures of -70oC, 0, and 25oC. After concentrating the reaction mixture under vacuum, the residue is mixed with water, twice extracted with acetic ether and the extract was dried over magnesium sulfate. Partially concentrated in vacuo and then separated into fractions by chromatographic method through silica gel using a simple ether and petroleum ether in the ratio 1:5. The first fractions contain 12.5 g (58.5 per cent) of the compound indicated in the title>4.7 g (0,278 mol) of gaseous ammonia are introduced with stirring at a temperature of from -75 to -70oC for 1 h in a mixture of 38.0 g (0.147 mol) of 2-fluoro(chloro)-4-triptoreline-6-cryptomaterial 150 ml simple diethyl ether. Mix, respectively, for 2 h at a temperature of -75oC and after heating at 25oC. After extraction of the precipitated residue of the organic phase is extracted with water, dried and partially concentrated. After chromatographic separation using methyl-tert.-butyl ether through silica gel gain of 20.4 g (56.1% of theory.) the connection specified in the header, with a melting point 47-49oC.

2-amino-4-methoxy-6-cryptomaterial

2.7 g (0.015 mol) of 30% sodium methylate for 15 min while stirring at a temperature of from -5oC and 0oC add to 2,95 g (0.015 mol) of 2-amino-4-fluoro-6-cryptomaterial in 50 ml of methanol. After stirring for 1 h at 0oC and heated to 25oC the reaction mixture was concentrated in vacuo, mixed with water and extracted twice with methylene chloride. After drying and concentration in vacuo obtain 3.1 g (98% of theory.) the connection specified in the header, c n2D51,4770.

<15 min while stirring at a temperature of from -10oC and 0oC to 31.0 g (0,145 mol) 2-amino-4-chloroformate-6-ftorpirimidinu in 300 ml of methanol. Stirred for 30 minutes at a temperature of 0oC and for 1 h at a temperature of 25oC. the Reaction mixture was concentrated in vacuo, processed, as indicated above. Receive 31.6 (96,6% of theory.) the connection specified in the header, in the form of a colourless oil with n2D21,5039.

4 chloroformate-2-methylamino-6-methoxypyridine

4.7 g (0,026 mol) of 30% sodium added dropwise within 10 minutes while stirring at 0oC to 6.0 g (0,0263 mol) of 4-chloroformate-6-fluoro-2-methylaminopropane in 100 ml of methanol. Accordingly stirred for 1 h at a temperature of 0oC and at 25oC. After the usual processing gain of 6.3 g (100% of theory.) the connection specified in the header, with a melting point 49-53oC.

4 chloroformate-6-dimethylamino-2-methylaminopropane

1.9 grams (0,0417 mol) of gaseous dimethylamine is administered for 10 min with stirring at 0oC in a mixture of 8,9 g (0,0417 mol) 2-amino-4-chloroformate-6-ftorpirimidinu in 100 ml of tetrahydrofuran. Stirred for 1 h at 0oC and 2 h at a temperature of 25oC. After the usual processing gain of 9.7 g (97.5% of Theo products I.

1. Complex [2-[[(4-methoxy-6-cryptomaterial-2-yl)amino - carbonyl]aminosulfonyl]phenyl ether]methansulfonate

A solution of 3 g of 2-amino-4-methoxy-6-cryptomaterial (14 mmol) in 10 g of 1,2-dichloroethane are mixed at 25oC with 4 g of complex 2-isocyanatophenyl ether methanesulfonate (14 mmol). Stirred for 10 min, remove the solvent in a simple ether/pentane (1:1, volume:volume). The crystalline product is sucked off and dried in a vacuum produced by water-jet pump, at a temperature of 40oC. are Thus obtained 5 g of compound indicated in heading (73% of theory. ), with a melting point 146-149oC.

2. Complex [2-[[(4-fluoro-6-methoxypyridine-2-yl)aminocarbonyl]aminosulfonyl]phenyl ester methanesulfonate

A suspension of 2 g of 2-amino-4-methoxy-6-cryptomaterial (14 mmol) in 10 g of 1,2-dichloroethane are mixed at a temperature of 25oC with 4 g of complex (2-isocyanatophenyl) ether methanesulfonate (14 mmol). The homogeneous solution is formed, from which after about 30 minutes allocated voluminous white precipitate. The product is sucked off, washed with a small amount of 1,2-dichloroethane and dried in a vacuum produced by the nd melting point 168 169oC.

3. [2-[[(4-Methoxy-6-triptoreline-1,3,5-triazine-2-yl)aminocarbonyl] aminosulfonyl]phenyl ester, sodium salt methansulfonate

A solution of 3 g of complex [2-[[(4-methoxy-6-triptoreline-1,3,5-triazine-2-yl)aminocarbonyl] aminosulfonyl] phenyl ether methanesulfonate (6.2 mmol) in 30 ml of methanol is mixed at a temperature of 25oC with 1.1 g (6.2 mmol) of a solution of sodium methylate (30 wt.) in methanol. Stirred for 2 min at 25oC and remove the solvent at a temperature of 80oC in vacuum obtained using a water-jet pump. Get the connection specified in the header, with a quantitative yield by decomposition temperature 130-135oC.

Specified in the following table. 2 active substances get in the same way.

< / BR>
Examples of other herbicide active sulfonylureas I received a similar manner, are shown below in table. 3. For this purpose a basis for taking the simplified formula (I') and (I")

Ax-y-SO2-NH-CO-NH-Tn(I')

Ax-y-SO2-NH-CO-NH-Pn(I")

where Ax-ydenotes an aromatic radical of the formula

< / BR>
the value x represents the radical R1and the value of the y radical R2is easyradio, this means:

< / BR>
(see tab. 5).

The combination of Ax-y1-1 and Pn/Tn1 indicates the sulfonylureas and

< / BR>
Accordingly, the other numeric combinations can be attributed to the corresponding derivative of the sulfonylureas.

Examples of the application

Herbicide derivative action of the sulfonylureas of the formula I can be traced to the experiments conducted in the greenhouse:

As containers for crops are plastic flower pots with sandy land containing approximately 3.0% of humus as a substrate. Seeds of the test plants are sown separately by type of seeds.

When handling to the emergence suspended or emulsified in water of the active substance directly after sowing by means of finely distributing nozzles are applied to the surface. Vessels lightly sprayed to accelerate germination and growth and then cover with clear plastic cover until you grow plants. This cover promotes uniform germination of the tested plants, as the active ingredients do not produce harmful effects.

For post-harvest processing, subjects plants suspended processed by plants or directly planted and grow in the same vessels, either grow separately and a few days before treatment, the seedlings are transplanted into the vessels of the experiment. The consumption rate for post-harvest processing is 0.015 kg/ha of active substance or 0.5 kg/ha of active substance.

Plants are depending on the type at temperatures from 10 to 25oC or from 20 to 35oC. the Duration of the experiment from 2 to 4 weeks. During this time the plants care and is determined by their reaction to certain types of processing.

The assessment is carried out on a scale from 0 to 100. 100 means no germination of the plants or complete destruction of at least the aerial parts and 0 no injury or growth process.

Plants used for experiments in the greenhouse, composed of the following types (see tab.6)

Application of 0.015 kg/ha of active substance in the post-harvest way has had a very good effect on undesirable broadleaf plants (compounds of examples 1 and 5), while endurance crops of wheat and corn.

The compound of example 14 with a consumption rate of 0.5 kg/ha in post-harvest method shows very good herbicide effects against harmful plants which shall be filled with the compound A, known from European patent 44212, and connection To, falling within specified there a General formula

< / BR>
< / BR>
The results of the experiments listed in table. 3 and 7, show unexpectedly high selectivity of the used compounds in comparison with the comparative substances with simultaneously good herbicide activity.

Table. 7 shows the results of tests for combating undesirable broadleaf plants and tolerability of cultures, given as examples, when post-harvest application rate of 0.015, 0,008 kg of active substance per hectare in the greenhouse.

Table. 8 shows the results of tests for combating undesirable broadleaf plants and tolerability of cultures, given as examples, when post-harvest application rate of 0.015, 0,008 kg of active substance per hectare in the greenhouse.

0.5 kg/ha

The connection 14 Damage,

AMARE 98

GALAP 98

CENCY 100.

1. Substituted derivatives of sulfonylurea General formula I

< / BR>
where R1C1C4is an alkyl group, optionally substituted by a halogen atom or WITH1WITH2-alkoxygroup,1WITH3-alkylamino or di-(C1the XI, bromodifluoromethane, chloroformate or fluorine;

R4halogen, under certain conditions, halogen-substituted methyl, ethyl,1WITH2-alkoxygroup, methoxy - or ethoxypropan, methyl or dimethylaminopropan;

R5hydrogen;

Z is CH or N, provided that when R3dipterocarp, R1cannot be di(alkyl)amino group, and R4the stands or a methoxy group; b) when R3fluorine atom, and Z is N, R4can't be alkylaminocarbonyl,

or applicable to agriculture salt.

2. Derivatives of formula I on p. 1, where R1WITH1- C4is an alkyl group which may be substituted with one or three halogen atom, or WITH1WITH2-alkoxygroup, and R2- R5and Z have the values listed in paragraph 1.

3. Derivatives of formula I on p. 1, where R1WITH1- C3-alkylamino - or di-(C1WITH4-alkyl)amino group, and R2R5and Z have the values listed in paragraph 1.

4. Derivatives of formula I on p. 1, where R1WITH1- C4is an alkyl group which may carry from one to three halogen atoms, methylamino or dimethylaminopropan, R3deformedarse or tripterocarpa or fluorine, 1- C4is an alkyl group which may carry from one to three halogen atoms, methylamino or dimethylaminopropan, R3deformedarse-, or triptoreline-or Hortiflorexpo or fluorine, R4- methoxy group, and R2, R5and Z have the values listed in paragraph 1.

6. Derivatives of formula I under item 1, with herbicide activity.

7. Herbicide agent, comprising the active substance derived sulfonylureas and targeted supplements that are acceptable in agriculture, characterized in that as a function of sulfonylureas it contains a compound of General formula I, where R1C1C4-alkyl, di-(C1WITH4)-alkylamino, R2hydrogen, R4- methoxy, R3triptoreline, fluorine, R5hydrogen, Z is CH, in an effective amount.

 

Same patents:

The invention relates to the derived O-carbamidomethylation, specifically to methyl ether, 2-[[N-(4-methoxy-6-methyl-1,3,5-triazine-2-yl)-N-methylaminomethyl]aminosulfonyl]benzoi Noi acid of the formula I

< / BR>
have a weed-killing activity, and herbicide compositions based on it

Poroelasticity // 2047607
The invention relates to the sulfonylureas, in particular to new ferroelasticgadolinium General formula I:SO2NHNH(I) where R1-C4alkyl;

R1CH3CH2SP, CH2OCH3CH2OCH2CH3C1-C3alkoxy, CH2F, СНFCH3or CF2H;

X NHCH3or N(CH3)2provided that if R1is the co2CH3or CH2OCH3then R is different from the CH3that may find application in agriculture, as shown herbicide activity

The invention relates to new derivatives of phenylsulfonylacetate General formula I

where R is C1 (1A) or SOON3(1B), and their alkali and ammonium salts, which can find application in agriculture as herbicides and plant growth regulators

The invention relates to new derivatives of sulfamethoxypyrazine and herbicides containing them as active ingredients

The invention relates to allpresan replacement pyrimidines, in particular 2-amino - and 2-substituted amino-4-substituted-5-hydroxypyrene-dyn, which may be substituted in the 6 position, pharmaceutical compositions containing these compounds as active ingredients and methods of treatment using these compounds

The invention relates to a method of obtaining a new connection group 6-(4)-dipyrimidine, specifically dipyrimidine containing zenatello group with a cyclic nitrogen atom, and in the 4th and 5th position of the molecule OCH3and NH2groups, respectively, formula 1

(I)

Known the proposed synthesis of 4-carbomethoxy-5-(N-formyl-N-(2-cyanoethyl-amino)-1,2,3-thiadiazole of the formula (A)

(A)A study of biological activity of compounds (A)

The invention relates to new biologically active compounds derived pyrimidine-4-or their pharmaceutically acceptable salts with serotoninergicheskoi, dopaminergically, antihistaminic activity, and compositions on their basis

The invention relates to the derived O-carbamidomethylation, specifically to methyl ether, 2-[[N-(4-methoxy-6-methyl-1,3,5-triazine-2-yl)-N-methylaminomethyl]aminosulfonyl]benzoi Noi acid of the formula I

< / BR>
have a weed-killing activity, and herbicide compositions based on it

The invention relates to new derivatives of sulfamethoxypyrazine and herbicides containing them as active ingredients

The invention relates to herbicides that can be used against monocotyledonous and dicotyledonous weeds

The invention relates to methods seleting suppression of undesirable plant species in the presence of agricultural crops

The invention relates to a preparation containing a synergistic mixture of bromoxynil or one of its derivatives (I) c 2-[[(4,6-dimethoxypyrimidine-2-yl] amino-arbonyl] (aminosulfonyl)-N, N - dimethyl-3-pyridinecarboxamide (II)

The invention relates to a method of controlling undesirable vegetation using sulfonylureas

The invention relates to synergistic herbicide composition, comprising as active components 1-[4,6-dimethoxypyrimidine-2-yl]-3-[3-trifluromethyl-2 - pyridylsulfonyl] urea ( hereinafter called "Compound a") and salt Isopropylamine or trimethylsulfonium N-(phosphonomethyl)glycine (hereafter referred to as "Compound B") in a mass ratio of 1:2.5 to 40

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention describes a synergistic composition of herbicides comprising components (A) and (B) wherein (A) represents herbicide taken among the group of the formula (I):

wherein R1 means (C1-C4)-alkyl; R2 means (C1-C4)-alkyl; R3 means hydrogen atom; X and Y mean (C1-C4)-alkoxy-group; (B) represents one or two herbicides taken among the group of compounds or their acceptable forms: alachlor, metolachlor, acetochlor, dimetenamide, atrazine, cyanasin, metribusin, fluthiamide, nicosulfuron, rimsulfuron, primisulfuron, pendimetalin, sulcotrion, dicamba, mesotrion, isoxachlortol, metosulam, anilofos, fenoxaprop-ethyl, setoxydim, diclofop-methyl, MCPA, bromoxynil, pyridat, clopyralid, iodosulfuron-methyl, ethoxysulfuron, amidosulfuron, gluphosinat-amminium, isopropylammonium-glyphosate, imasetapir wherein components (A) and (B) are taken in the effective doses. Also, invention describes a method for control of weeds by using above indicated herbicide composition. Invention provides the development of the synergistic herbicide composition eliciting high activity.

EFFECT: improved method for control, valuable properties of composition.

6 cl, 26 tbl, 3 ex

FIELD: organic chemistry, agriculture.

SUBSTANCE: claimed mixture from herbicides and antidotes contains (A) herbicidically active substance based on phenylsulfonylureas of formula I and salts thereof (in formula R1 is hydrogen or C1-C6-alkyl; R2 is C1-C3-alkyl; R3 is C1-C3-alkoxy; R4 is hydrogen or C1-C4-alkyl; Hal is fluorine, chlorine, bromine, or iodine); and (B) antidote of formulae II or III , wherein X is hydrogen, halogen, C1-C4-alkyl; C1-C4-alkoxy, nitro or C1-C4-haloalkyl; Z is hydroxyl, C1-C8-alkoxy, C3-C6-cycloalkoxy, C2-C8-alkenyloxy, C2-C8-alkynyloxy; R5 is C1-C2-alkandiyl chain optionally substituted with one or two C1-C4 alkyl residues or (C1-C3-alcoxy)carbonyl; W is bivalent heterocyclic residue; n = 1-5; in weight ratio herbicide/antidote of 100:1-1:100. Also disclosed is method for protection of cultural plants against phytotoxic side effect of herbicidically active substance of formula I. Claimed method includes antidote application of formulae II or III on plant, plant parts, plant seeds or seeding areas before or together with herbicidically active substance in amount of 0.005-0.5 kg/hectare in weight ratio of 100:1-1:100.

EFFECT: mixture for effective selective weed controlling in cultural plant, particularly in maize and grain cultures.

8 cl, 2 ex, 7 tbl

FIELD: agriculture, in particular herbicide compositions.

SUBSTANCE: invention relates to weed controlling method for tolerant grain crops using (A) road spectrum herbicides selected from group (A1) glufosinate (salt) and related compounds; (A2) glyphosate (salt) and related compounds; and (B) one or more herbicides selected from group containing (B1) herbicides selectively effecting in grain crops especially against monocotyledonous weeds effecting on folia and/or soil (residual benefit); or (B2) herbicides selectively effecting in grain crops against monocotyledonous or dicot weeds effecting especially on folia; or (B3) herbicides selectively effecting in grain crops against monocotyledonous or dicot weeds effecting on folia or soil; or (B4) herbicides selectively effecting in grain crops against monocotyledonous or dicot weeds effecting on folia; wherein components (A) and (B) are used in synergic ration. Also are described herbicide compositions containing (A1) ) glufosinate (salt) and related compounds and herbicide from group (B); as well as herbicide compositions containing(A2) glyphosate (salt) and related compounds and herbicide from group (B); wherein components (A) and (B) are used in synergically effective ration.

EFFECT: effective controlling of weeds in grain crops.

6 cl, 70 tbl, 3 ex

Up!