Pyridinesulfonamide or acceptable for agriculture salt composition for combating the growth of unwanted vegetation, the method of producing pyridinesulfonamide and acceptable in agriculture salts

 

(57) Abstract:

The invention relates to new pyridinesulfonamide General formula I or their acceptable for agriculture salts, have a weed-killing activity, as well as to a method for their production and compositions for combating the growth of unwanted vegetation. The described compounds of formula I have the following structure:

< / BR>
where R is H or CH3; R1- Rfor Rg; Rf- H, C1-C3-alkyl, C1-C3-haloalkyl, halogen, C1-C3-alkoxy or C1- C3-alkylthio; Rg- C1-C3-haloalkyl, C1-C3-alkyl, substituted C1-C3-alkoxyl, C1-C3-alkylamino, di-C1-C3-alkylamino or W2R11; R2- C1-C4-alkylsulfonyl, C1-C4-alkylsulfonyl,

SO2NH2, SO2NRdRe, SO2NR7R8, SO2NR'7R8, OSO2R8, CO2R9, CO2R'9, CF2H, CH2Cl, C2-H4-haloalkyl or N3; R7- H, R'7- C1-C4-alkyl, Rd- C1-C2-alkyl, Re- C1-C2-alkoxyl, R8- C1-C4-and the B>2)4- or -(CH2)5; R9- C3-C4-quinil, C4-C7-cycloalkyl, C3-C5-cycloalkyl or-CH2CH2OH; R'9- C1-C4-alkyl; R11- C1-C3-alkyl or C1-C3-haloalkyl; W2Is O or S; X is C1-C4-alkyl, C1-C4-alkoxy, C2-C4-haloalkoxy or halogen; Y is C1-C4-alkyl, C1-C4-alkoxy, C1-C3-alkylamino or di-C1-C3-alkylamino; Z is CH or N

provided that when X is halogen, then Z denotes CH, and Y represents C1-C4-alkoxy, C1-C3-alkylamino or di-C1-C3-alkylamino; when the total number of carbon atoms of X and Y is greater than four, the total number of carbon atoms of R1and R2less than or equal to six, and when R2means CO2R'9or SO2NR'7R8, R1means Rgand when R2different from CO2R'9or-SO2NR'7R8, R1means Rf. The method of obtaining these compounds is that of the sulfonamide of the formula

< / BR>
where R1and R2have the above meanings, is subjected to the interaction with phenylcarbamate formulae solvent followed, if necessary, transfer the received pyridinesulfonamide in salt, for example, the interaction with the hydroxide of alkali or alkaline earth metal or an appropriate amine. The composition includes 0.1 to 99 wt.% the compounds of formula I and an additive selected from the group comprising surfactant, solid or liquid inert diluents or mixtures thereof. Described compounds have high activity as prescheduled and post-harvest herbicides. 3 S. and 18 C.p. f-crystals, 23 PL.

The present invention relates to new pyridinesulfonamide with high herbicide activity in predsjedava and post-harvest processing, retrieval method and composition for combating the growth of unwanted vegetation.

In EP-A-13480 described sulfonamides of General formula

,

where

R1represents H, Cl, Br, F, C1-C4-alkoxy, C1-C4-alkyl, C1-C4-alkylthio, NO2, CO2R5.

In U.S. patent N 4435206, publ. 06.03.85 and N 4522645, publ. 11.06.85 disclosed 2-pyridinesulfonamide, substituted in the 3 position of the pyridine ring with radical R1represents H, Cl, Br, F, C1-C4- THE NR6R7. In U.S. patent N 4339267 disclosed herbicide sulfonamides of the formula

,

where

R4represents H, Cl, Br, F, C1-C4-alkyl, C1-C4-alkoxy, NO2, CO2R6or SR13.

EP-A-30433 reveals herbicide sulfonamides of the formula

,

where

X represents H, R14- H or CH3; and R3Is H, F, Cl, Br, CH3, OCH3, NO2, CO2R11or S(O)nR12.

In U.S. patent N 4456469 disclosed herbicide sulfonamides of the formula

,

where

R - C1-C6-alkyl, C3-C6alkenyl, C2-C4-alkoxyalkyl, C5-C6-cycloalkyl, R OCH2CH2CH2OCH2, R OCH2CH2OCH2CH2, CF3, CF3CH2HCl2CCF2or HCF2;

Z represents H, F, Cl, Br, CH3, OCH3or SCH3.

In U.S. patent N 4487626 disclosed herbicide sulfonamides of the formula

,

where

A represents a group

,

R2represents H, F, Cl, Br, C1-C4-alkyl, C1-C4-alkoxy, NO2, CO2R15, S(O)nR16, SO2NR18R19or SO2N(OCH3)CH3
,

and R16represents a C1-C4-alkyl, C1-C4-alkoxy, F, Cl, Br, CF3, CO2R20, SO2NR10R11, SO2N(OCH3)CH3or S(O)nR13.

U.S. patent N 4496392 reveals herbicide sulfonamides of the formula

,

where

R1represents Cl, SO2CH3or SO2N(CH3)2.

In EP-A-84224 disclosed herbicide sulfonamides of the formula

,

where a designated group

,

and R16represents H, C1-C4-alkyl, C1-C4-alkoxy, F, Cl, Br, CF3, CO2R9, SO2NR10R11, SO2N(OCH3)CH3or S(O)nR13.

In EP-A-125846 disclosed herbicide sulfonamides of the formula

,

where the symbol J defined groups

< / BR>
and R3represents Cl, SO2CH3, SO2N(CH3)2, OCH3, NO2or N(CH3)2.

In EP-A-155767 disclosed herbicide sulfonamides of the formula

,

where the symbol J defined groups

< / BR>
and R5represents H, CH3, Cl, Br, CO2R15C(O)NR16R17, SO2NR16R17, SO2N(OCH3)C>,

where

R4represents CH3CH2CH3, OCH3, OCH2CH3, F, Cl, Br, SO2NR16R17, SO2N(OCH3)CH3, S(O)nR19C3-C4-alkenylamine or C3-C4-alkyloxy.

In EP-A-164269 disclosed herbicide sulfonamides of the formula

,

where

R4represents CH3CH2CH3, OCH3, OCH2CH3, R, Cl, Br, SO2NR11R12, SO2N(OCH3)CH3or S(O)nR13.

In EP-A-171286 disclosed herbicide sulfonamides of the formula

.

where

R4represents CH3CH2CH3, OCH3, OCH2CH3, F, Cl, Br, SO2NR18R19, SO2N(OCH3)CH3, S(O)nR21C3-C4-alkenylamine, CH2OCH3or CH2OCH2CH3. In the application of South Africa 83/4305, published on December 14, 1983, discloses herbicides sulfonamides of the formula

,

where

R2represents H, C1-C3-alkyl, C1-C3-haloalkyl, halogen, NO2C1-C3-alkoxy, C(W)R8, SO2NR6R7, S(O)nC1-C3-alkyl or C(O)R9;

R32, F, Cl, Br, CH3, CF3, S(O)nC1-C3-alkyl, C(O)C1-C4-alkoxy or C1-C3-alkoxy;

Y represents O or S.

In the application of South Africa 83/6639, published March 8, 1984, discloses herbicide sulfonamides of the formula

,

where

A represents a C3-C6-alkynylaryl radical, C1-C6is an alkyl radical, which is substituted by halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulfonyl, C1-C4-alkylsulfonyl, C1-C4-haloalkoxy, C1-C4-haloalkylthio, C1-C4-haloalkaliphilic or C1-C4-haloalkaliphilic, or represents a C2-C4-alkanniny radical, which is unsubstituted or substituted in the same way as C1-C6-alkyl, or represents a phenyl radical which is unsubstituted or substituted with halogen, cyano, nitro, C1-C4-alkyl, C1-C4-haloalkyl, -X-C1-C4-alkyl, C1-C4-alkoxycarbonyl, amino, mono - or di-(C1-C4-alkyl)-amino, carbarnoyl, mono - or di-(C1-C4-alkyl)-carbarnoyl, sulfamoyl, mono or di(C1-C4-alkyl)-sulfamoyl radicai, C1-C4-haloalkyl, C1-C4-haloalkoxy, C2-C5-alkoxyalkane, C1-C5-alkylthio, C1-C5-alkylsulfonyl or C1-C5-alkylsulfonyl; and

X represents O, S, SO or SO2.

In U.S. patent N 4518776 disclosed is a method of obtaining herbicide sulfonamides of the formula

,

where

R1represents S(O)nC1-C4-alkyl, SO2di(C1-C4-alkyl)-amino or CO2(C1-C2)-alkyl; and

R2represents H, halogen, CF3, NO2C1-C4-alkyl or C1-C4-alkoxy.

In this patent in the General form disclosed some connections, but not described in any one of the compounds of this invention.

In EP-A-101670, published on February 29, 1984, disclosed is a method of obtaining herbicide sulfonamides of the formula

,

where

R1is a Q-C1-C4-alkyl, SO2di(C1-C4)-alkylamino or CO2(C1-C4)alkyl;

Q represents S or S(O)n;

R2represents H, halogen, CF3, NO2C1-C4-alkyl or C1-C4-alkoxy.

In this proposal in the June 1986., revealed the following connection for selective weed control in tomatoes and turf

,

In the application of the U.S. N 874307 disclosed herbicide on-alkylarylsulfonates.

In the application of the U.S. N 943137 disclosed herbicide on-substituted pyridinesulfonamide.

In U.S. patent N 4521597 describes a method of obtaining a wide range of the sulfonylureas of the formula

,

where

R3represents H, F, Cl, Br, NO2, OCH3, CF3;

R5represents S(O)mC1-C5-alkyl, SO2NR8R9; COR7;

R6represents H, F, CH3, OCH3.

U.S. patent N 4521597 applies only to the method of obtaining a wide range of the sulfonylureas, and not of the compounds or their use as herbicides. The amount of the claims in this patent includes not only compounds with heteroaromatic groups, but also phenyl and naphthalenesulfonates. Heteroaromatic residues are not only pyridinium, but also furans, typenum and pyrrole. In contrast, the present invention relates to a small class herbicide-active pyridinesulfonamide. The relative position of the substituents in ukny bridge of the present invention should be positioned vicinal to each other and sulfonylurea bridge must be in the 2nd position, as evidenced by the submitted data.

The essence of any invention is selectivity. In U.S. patent N 4521597 only one connection from a number of sulfonation was obtained and described. Others described compounds are sulfanilamidnami that do not belong to the sulfonylureas of the present invention. The only open connection represents substituted benzosulfimide, while the compounds of the present invention relate to pyridylamine the ureas and, thus, the proposed compounds differ in structure. The pyridine nitrogen atom may form a hydrogen bond with the proton solvents, other parts of the sulfonylurea molecule and an acid proton sites in biomolecules that play an important role in metabolic processes. Thus, U.S. patent N 4521597 in no way includes pyridinesulfonamide of the present invention.

Below are data showing improved herbicide activity of the compounds of the invention in comparison with the compounds specified in the patent.

EP-A-97122 reveals a wide range of heterocyclic sulfonylureas, in which the heterocycle vbolshoy subgroup of pyridinesulfonamide. In addition, the relative position of the substituents analogue and sulfonylamino bridge is not marked, while the substituents of the present invention and the sulfonylurea bridge should be positioned vicinal to each other, and the sulfonylurea bridge should be in the 2nd position of the pyridine ring, in addition, in EP-A-97122 you want one of the substituents of the pyridine/triazine was OCF2H or SCF2H, while the substituents of the pyridine/triazine of the present invention cannot be OCF2H or SCF2H.

In European application EP-A-97122 disclosed 369 compounds, only 84 of which are pyridinesulfonamide, and all 84 connections have HCF2O-substituted pyrimidine residues. The compounds of this invention may not contain HCF2O-group as Deputy pyrimidine or triazine ring. These compounds completely not mentioned in EP-A-97122.

The following data shows the advantage of the proposed compounds in comparison with similar compounds of EP-A-97122 on herbicide activity.

EP-A-103543 relates to compounds of the formula

,

where

A may indicate, for example, C36-alkyl, possibly substituted by halogen or C1-C4-alkoxy and others,

X is O, S, S(O) or S(O)2or

A-X - NR6R7,

R1can mean, for example, H1,

R2may mean, for example, C1-C3-alkyl or C1-C3-alkoxy,

R3can mean, for example, C1-C3-alkyl or C1-C3-alkoxy,

R6and R7each can mean, for example, H or C1-C4-alkyl,

E is CH or n

EP-A-103543 refers to a wide range of different pyridinesulfonamide, in which the relative position of Deputy to the sulfonylurea bridge is not specified. In contrast, the present invention relates to a narrow range of pyridinesulfonamide, in which the substituents and the sulfonylurea bridge should be positioned vicinal to each other, and the sulfonylurea bridge should be in the 2nd position of the pyridine ring. In addition, the group X-A in the compounds of EP-A-103543 limited alkynes, alkenes, phenyl groups and substituted alkyl groups, each of which is attached to oxygen, thio, sulfinilbis or sulfonylurea groups, or a group X-A can be aminogroup is raised to any of the above groups of compounds.

In EP-A-103543 disclosed 400 pyridinesulfonamide. 400 connection only 27 are pyridinesulfonamide with bridge group at the 2nd position of the pyridine ring. However, none of the disubstituted compounds (OCF2H or possibly substituted, phenoxy) does not apply to the present invention, according to which the group R2cannot be OCF2H or substituted by phenoxypropane. Transnistria compounds of EP-A-103543 relate to a wide range alkinilovymi, alkenyl, alilovic, phenyl and amino substituents, which are different from sulfonamidnuyu, alkylsulfonyl and the other R2the substituents in the compounds of the present invention. In EP-A-103543 there is no indication on the proposed disubstituted of pyridinesulfonamide. The following shows the advantage of the proposed connection on herbicide activity compared to the same compound according to EP-A-103543.

Thus, in some patent publication proposes a General structural formula pyridinesulfonamide, which fall under the proposed connection. But none of these sources does not disclose compounds proposed according to the present invention and their herbicide activity.

This is SUB>;

R1- Rfor Rg;

Rf- H, C1-C3-alkyl, C1-C3-haloalkyl, halogen, C1-C3-alkoxy or C1-C3-alkylthio;

Rg- C1-C3-haloalkyl, C1-C3-alkyl, substituted C1- C3-alkoxyl, C1-C3-alkylamino, di-C1-C3-alkylamino or W2R11;

R2- C1-C4-alkylsulfonyl, C1-C4-alkylsulfonyl, SO2NH2, SO2NRdRe, SO2NR7R8, SO2NR'7R8, OSO2R8, CO2R9, CO2R'9, CF2H, CH2Cl, C1-C4-haloalkyl or N3;

R'7- C1-C4-alkyl;

Rd- C1-C2-alkyl;

Re- C1-C2-alkoxyl;

R8- C1-C4-alkyl or C1-C4-haloalkyl;

R7and R8taken together, could mean -(CH2)3-, -(CH2)4- or -(CH2)5-;

R9- C1-C4-quinil, C4- C7-cycloalkyl, C1-C3-cycloalkyl or CH2CH2OH;

R'9- C1-C4-alkyl;

R11- C1-C3-alkyl or C1-C4-haloalkoxy or halogen;

Y - C1-C4-alkyl, C1-C4-alkoxy, C1-C3-alkylamino or di-C1-C3-alkylamino; and

Z is CH or N;

provided that

when X is halogen, then Z denotes CH, and Y represents C1-C4-alkoxy, C1-C3-alkylamino or di-C1-C3-alkylamino;

when the total number of carbon atoms of X and Y is greater than four, the number of carbon atoms of R1and R2less than or equal to six; and

when R2means CO2R'9or SO2NR'7R8, R1means Rgor, if R2differently from CO2R'9or SO2NR'7R8, R1means Rf,

or acceptable for agriculture of salt.

The compounds of formula I and their salts have a high selective herbicide activity, many of them are safe for cultivated plants and can be used in agriculture. These compounds may be used because of its properties and as plant growth regulators.

Preferred compounds of formula I,

where

X represents a C1-C2-alkyl, C1-C2-alkoxy, Cl, Br, F, I, OCHB>1-C2-alkoxyl, NHCH3or N(CH3)2,

as well as the compounds of formula I,

where

Rfrepresents H, CH3C1-haloalkyl, halogen or OCH3;

Rgis a W2R11CH2OCH3C1-C2-alkylamino or N(CH3)2,

or the compounds of formula I,

where

R'7- C1-C3- alkyl;

R8- C1-C3-alkyl;

R9- cyclopropylmethyl or CH2CH2OH;

R'9- C1-C3-alkyl.

Of these the most preferred compounds, where

X represents CH3, OCH3, OCH2CH3, Cl or OCH2CF3;

Y - CH3, OCH3CH2CH3or NHCH3. 2 it is advisable to

Z represents CH or

Z represents n

The most preferred compounds, where

Z represents CH;

R2- C1-C4-alkylsulfonyl or C1-C4-alkylsulfonyl;

Rf- H, C1-C2-alkyl, C1-haloalkyl, C1-C2-alkoxy or C1-C2-alkylthio,

in particular, compounds where

Rf- H;

R2- C1

Alkoxy denotes methoxy, ethoxy, n-propyloxy or isopropoxy.

Alkenyl means an unbranched or branched alkenes, such as 1-propenyl, 2-propenyl, 3-propenyl and various isomers butenyl.

Quinil means straight or branched alkynes such as ethinyl, 1-PROPYNYL, 2-PROPYNYL and the different isomers of butenyl.

Alkylsulfonyl means methylsulphonyl, ethylsulfonyl and various isomers propylsulfonyl and butylsulfonyl.

Cycloalkyl means cyclopropyl, cyclobutyl and cyclopentyl.

The term "halogen" as such or in combination with other words such as "haloalkyl" means fluorine, chlorine, bromine, or iodine. In addition, when used in combination with other key words, such as "haloalkyl" specified alkyl may be partially halogenated or fully substituted by halogen atoms, which may be the same or different. Examples of haloalkyl include CH

The total number of carbon atoms in the replacement group is indicated subscript digit Ci-Cjwhere i and j are numbers from 1 to 5. For example, C1-C3-alkylsulfonyl will mean radicals from methylsulfonyl to propylsulfonyl, C2-alkoxyalkane will mean OCH2OCH3C2-cianelli will mean CH2CN and C3-cianelli will mean CH2CH2CN and CH(CN)CH3.

Especially preferred from the viewpoint of simplicity of the method of obtaining and/or the highest herbicide activity are the following connections:

-N-//of 4,6-dimethoxypyrimidine-2-yl/aminocarbonyl/-3- /1-propylsulfonyl/-2-pyridinesulfonamide;

-N-//of 4,6-dimethoxypyrimidine-2-yl/aminocarbonyl/-3- /1-propylsulfonyl/-2-pyridinesulfonamide;

-N-//of 4,6-dimethoxypyrimidine-2-yl/aminocarbonyl/-3- /ethylsulfonyl/-2-pyridinesulfonamide;

-N-2-//of 4,6-dimethoxypyrimidine-2-yl/aminocarbonyl-N - 3-ethyl-2,3-pyridinesulfonamide;

-N-//of 4,6-dimethoxypyrimidine-2-yl/aminocarbonyl/-3- /methylsulfonylamino/-2-pyridinesulfonamide; and

-N-2-//of 4,6-dimethoxypyrimidine-2-yl/aminocarbonyl/-N 3-methyl-2,3-pyridinesulfonamide.

The present invention also relates to compositions for combating rocheste active component a compound of the formula I in an amount of 0.1 to 99 wt.%, and as the inert additive is at least one of the following ingredients: surfactant, solid inert diluent, inert liquid diluent or a mixture thereof.

The preferred composition containing as an active ingredient a compound of General formula I, where

X represents a C1-C2-alkyl, C1-C2-alkoxy, Cl, F, Br, I, OCH2CH2F, OCH2CHF2, OCH2CF3;

Y represents a C1-C2-alkyl, C1-C2-alkoxyl, NHCH3N(CH3)2and the compounds of formula I, where

Rf- H, CH3C1-haloalkyl, halogen, OCH3.

This invention describes new compounds of the following formulas

,

where

Xarepresents Cl, NH2, HNC(CH3)3and , which are intermediate compounds in obtaining herbicide sulfonylureas.

Especially preferred are. 3-ethylsulfonyl-2-pyridinesulfonamide and 3-N-methyl-2,3-pyridinesulfonamide.

The synthesis of compounds of formula I can be performed according to one or more of the techniques described in U.S. patent N 4456469, or by the reaction of sulfonamides II complex penisnula Foundation, such as 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), as shown in equation 1.

Equation 1

,

where

J is a group of the formula

,

in which

R1and R2have the above values.

Thus, according to the present invention proposes a method of obtaining pyridinesulfonamide General formula I or their acceptable in agriculture salts

,

where

R is H or CH3;

R1- Rfor Rg;

Rf- H, C1-C3-alkyl, C1-C3-haloalkyl, halogen, C1-C3-alkoxy or C1-C3-alkylthio;

Rg- C1-C3-haloalkyl, C1-C3-alkyl, substituted C1-C3-alkoxyl, C1-C3-alkylamino, di-C1-C3-alkylamino or W2R11;

R2- C1-C4-alkylsulfonyl, C1-C4-alkylsulfonyl, SO2NH2, SO2NR7R8, OSO2R8, SO2NRdRe, SO2NR'7R8, CO2R9, CO2R'9, CF2H, CH2Cl, C2-C4-haloalkyl or N3;

R7- H;

R7' - C1-C4;

R8- C1-C4-alkyl or C12)5-;

R9- C3-C4-quinil, C4-C7- cycloalkyl, C3-C5-cycloalkyl or CH2CH2OH;

R'9- C1-C4-alkyl;

R11- C1-C3-alkyl or C1-C3-haloalkyl;

W2Is O or S;

X - C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy or halogen;

Y - C1-C4-alkyl, C1-C4-alkylamino or di-C1-C3-alkylamino;

Rd- C1-C2-alkyl;

Re- C1-C2-alkoxyl;

Z is CH or N;

provided that

when X is halogen, then Z denotes CH, and Y represents C1-C4-alkoxy, C1-C3-alkylamino;

when the total number of carbon atoms of X and Y is greater than four, the total number of carbon atoms of R1and R2less than or equal to six, and

when R2means CO2R9' or SO2NR7'R8, R1means Rgand when R2differently from CO2R9' or SO2NR7'R8, R1means Rf.

The method consists in the fact that the sulfonamide of the formula

,

where

R1and R2have the above values,

in the presence of 1,8-diazabicyclo [5,4,0] undec-7-ene and solvent, followed, if necessary, transfer the received pyridinesulfonamide in salt, for example, the interaction with the hydroxide of alkali or alkaline earth metal or an appropriate amine.

The method is best carried out at 25oC in a solvent such as dioxane or acetonitrile, for 1 to 2 h in an inert atmosphere, as described in the European patent N 70804 (publ. on January 26, 1983). Target products of formula I can be selected, podkolis the reaction solution with an aqueous solution of hydrochloric acid. Conversely, the water layer can be proektirovanii solvent such as methylene chloride or ethyl acetate. After evaporation of the solvent and drying remains the target product. Phenylcarbamates can be obtained by treatment of the corresponding heterocyclic amines of the formula ANHR diphenylcarbonate or phenylcarbamates in the presence of such bases as sodium hydride, pyridine or potassium carbonate, in the presence of catalytic amounts of 4-dimethylaminopyridine. The mixture is stirred at a temperature lying in the range 25oup to 65oC, in an environment suitable solvent, such as tetrahydrofuran, within the bathrooms of the following equations 2 and 3.

Equation 2 shows the reaction of sulphonylchloride formula IV with ammonia, which are formed sulfonamides of the formula II.

Equation 2

,

where the values of the radical J are the same as defined above.

Amination in accordance with equation 2 is conveniently made by adding at least two molar equivalents of either anhydrous ammonia or concentrated ammonium hydroxide to a solution of sulphonylchloride IV in an environment suitable solvent, such as diethyl ether, tetrahydrofuran or methylene chloride, at temperatures lying in the range from -30oup to 25oC. Target sulfonamides of the formula II allocate or filtering, in this case formed as a by-product ammonium chloride is removed by washing with water or by extraction of an appropriate organic solvent, such as methylene chloride or ethyl acetate. After drying and evaporation of solvent to obtain compound II, which are usually quite clean and can be used directly to implement the next stage.

The sulfonamides of the formula II can also be obtained as shown in equation 3 by treatment of the corresponding N-tert-bulcontrola acid (p-TAC).

Equation 3

,

where

the radical J has the same values as specified above.

The reaction in accordance with equation 3 is conveniently made by mixing the solution of the compounds of formula VI with an excess triperoxonane acid (about 0.3 M) for about 1 to 72 hours and Then target the sulfonamides of formula II exhale, removing them under vacuum with the implementation of subsequent crystallization from an appropriate solvent, such as diethyl ether, 1-chlorobutane or ethyl acetate. In another embodiment, N-tributylstannyl formula VI can be treated with a catalytic amount of monohydrate para-toluensulfonate acid in the environment of such a solvent like toluene or xylene, boiling for 1 to 6 hours Then the target products emit similar to one of the methods mentioned above. About the use of polyphosphoric acid for removing the protective groups from N-tert-butylsulfonyl see J. G. Lombardino, J. Org. Chem. , 36, 1843 (1971); usage triperoxonane acid, see J. D. Catt., W. L. Matier, J.Org. Chem., 38, 1974 (1973).

Sulfonamides of formula VI can be obtained by the reaction of sulphonylchloride formula IV with an excess of tert-butylamine, as shown in equation 4.

,

where

the radical J has the same sence USA N 4456469. Another option may be used with the techniques described in the application of South Africa 84/8844 and revealing way of transformation of a mercapto - or arylmethylidene in sulphonylchloride by treatment with hypochlorite solution.

Sulphonylchloride formula IVa can also be obtained by treating the derivatives of 2-herperidin diisopropylamide lithium (LDA) in accordance with the method of T. Gungor, F. Marsais, G. Gueguiner, J. were obtained. Chem., 1981; 215, 139-150, followed by treatment with sulfur dioxide and N-chlorosuccinimide (NXC), as shown in equation 5.

Equation 5

,

where

the radical R1has the same values as specified above.

Sulphonylchloride formula IV can be obtained from compounds of formula VII according to equation 6 and as described in U.S. patent N 4420325.

Equation 6.

,

where

the radical J has the same meaning indicated above and X is acceptable halogenation reagent, which can choose any specialist in this field.

Sulfides of formula VIII can be obtained by the reaction haloperidol compounds of the formula IX with an appropriate mercaptan in the presence of base as described in U.S. patent N 4456469 and shown in equation 7.

Equation 7

,

where

B>-cycloalkyl or benzyl.

Sulfides of formula VIIIa can be obtained by treating the pyridine compounds of formula X and two equivalents of a strong base such as n-utility or diisopropylamide lithium (LDA), as described in P. Breant, F. Marsais, G. Queguiner Synthesis, 1983, 822-824, followed by treatment of the corresponding disulfide, as shown in equation 8.

Equation 8

,

where

the radical R' represents a C1-C4-alkyl, C3-C5-cycloalkyl or benzyl, and the radical R1has the values listed above.

Sulfides of formula VIIIb can be obtained by treatment of the derivatives of 2-herperidin, as described above, and again with subsequent treatment of the corresponding disulfide, as shown in equation 9.

Equation 9

,

where

the radical R' represents a C1-C4-alkyl, C3-C5-cycloalkyl or benzyl, and the radical R1has the values listed above.

Sulfides and sulfoxidov General formula XI can be obtained from the corresponding sulfides of formula VIIId using any of the numerous agents of oxidation [O], known in this area, such as hydrogen peroxide or nagkalat, as shown in equation 10.

Y
-C4-alkyl, C3-C5-cycloalkyl, n is 1 or 2.

Chloropyridin formula IXa can be obtained by diazotization of 3-amino-2-chloropyridine with subsequent substitution by cyanide of copper, as shown in equation 11. The diazonium group can also be replaced by other groups such as SO2Cl and N3any known methods described in the literature.

Equation 11

,

where

the radical R1has the values listed above.

Sulfides of the General formula VIIIf can be obtained, as shown in equation 12. In the alkylation derivative of 3-hydroxy-2-mercaptopyridine alkylhalogenide using a variety of bases such as potassium carbonate or tert-piperonyl potassium, are formed sulfides of formula VIIIe, which are then treated with the appropriate sulphonylchloride in the presence of an acid acceptor, such as triethylamine, and get the sulfides of formula VIIIf.

Equation 12

,

where

the radical R' represents a C1-C4-alkyl, C3-C5-cycloalkyl or benzyl; the radical X' represents Cl, Br or I, and the radicals R1and R8have the values specified above.

Esters of formula VIIIg, VIIIh, VIIIj can polyporpylene, as described for equation 5, followed by treatment of ethyl - or methylchloroform, resulting in formation of esters of formula XIII. As a result of replacement of mercaptan as described for equation 7, are formed esters of the formula VIIIg. As a result of transesterification in the presence of acid catalyst to the corresponding alcohol as solvent are formed esters of the formula VIIIh.

The second method involves the alkylation derivative of 2-mercaptonicotinic acid eighth alkylhalogenide using a variety of bases such as potassium carbonate or tert-piperonyl potassium, with subsequent transformation into galvanized using any of the standard reagents, such as chloride thionyl, phosphorus trichloride or patially phosphorus chloride or oxalyl. Then galvanized treated with the appropriate alcohols in the presence of an acid acceptor, such as triethylamine, and get esters of the formula VIIIh. Conversion of sulfides VIIIh in sulfonamides VIIIj was carried out as described above.

Equation 13

,

where

the radical R' represents a C1-C4-alkyl or benzyl; the radical R9can also be the radical R'9and rediculous to be obtained, as shown in equation 14. However, for primary and uncomplicated secondary sulfonamides necessary protective group for the implementation of later stages of the synthesis process. The example presented in equation 15, where for the synthesis sulfonamida IIa used tert-bucilina protective group.

Equation 14

,

where

[D] is an RdRe, R'7R8, R'7R8or H2and the radicals R1, Rd, Re, R7, R8and R'7have the values specified above.

Equation 15

,

where

the radicals R1have the values specified above

Diploidy formula XIa in equation 16 can be obtained by the above reactions. As a result of processing one equivalent of various R1of nucleophiles (which are used for these purposes) is formed of a mixture of products, which can be divided. Presents an example of using sodium methoxide as a reactive nucleophile. Intermediate compound XIVb and XIVc can be divided further use, as described above.

Equation 16

,

where

the radical R2has the above values.

An alternative method given after conversion to sulfonamida XVa, as explained above. Treatment with two equivalents of a strong base such as n-utility, similar to that described in P. Breant, F. Marsais, G. Queguiner, Synthesis 1983, 822-824, after treatment with carbon dioxide leads to the production of acids of formula XVb. Then acid can handle the different R1nucleophiles such as alkoxides, mercaptide or amines, and to obtain the acid of formula XVc (using as example the sodium methoxide), which can then be atrificial corresponding alcohols under normal conditions in the presence of 1,3-dicyclohexylcarbodiimide (DCC) and get esters of formula XVd.

Equation 17

,

where the radical R9can also be the radical R'1the radical X' represents F or Cl, and the radicals R', R9and R'9have the values specified above.

Similarly, you can get sulfonamides of General formula XVIb, as shown in equation 18. As a result of processing XVa strong base followed by treatment of the corresponding disulfide formed sulfides of formula XVIa. In the further transformations, as described above, are formed sulfonamides of formula XVIb.

Equation 18

,

where the radical X' represents the methods of preparing compounds of formula I it is necessary to consider the nature of the substituents R1-R11and Rd-Rgand their chemical compatibility under the reaction conditions according to equations 1-18.

Heterocyclic amines of the formula A-NRH in equation 1, above, can be obtained by known methods described in the literature, or slightly modified ways. For example, in EP-A-84224 (published. 27.07.1983,) and W. Braker et al., J. Chem. Soc. 69, 3072 (1974) described ways of getting aminopyridine and triazines, substituted acetylene groups such as dialkoxybenzene or 1,3-dioxolane-2-ilen group apart from other groups. In addition, in South African patent applications N 82/5044 and 82/5673 described, for example, ways of getting aminopyrimidines and triazines, substituted haloalkyl or haloalkylthio groups such as OCH2CH2F, OCH2CF3, CF2H or OCF2H, among other groups. In South African patent application N 83/7434 (published 5.10.1983 g) described ways of getting cyclopropylamino and triazines substituted by such groups as alkyl, haloalkyl, alkoxy, haloalkoxy, alkylamino, dialkylamino or alkoxyalkyl.

5,6-Dihydrofuro[2,3-d]pyrimidine-2-amines, the cyclopent[d]pyridine-2-amines (A represents A-2) and the 6,7-dihydro-5H-pyrano[2,3-d] pyrimidine-2-amines (predstavljaet a A-4) described in EP-A-46677.

The compounds of formula A-other, where A is A-5, described in EP-A-73562. Compounds where A is A-6, described in EP-A-94260.

In addition, General methods of obtaining aminopyrimidines and triazines described in the following publications:

- The Chemistry of Heterocyclic Compounds., a series published by interscience publishers, Inc., New York, London;

- "pirimidines". Vol.16 of the Same series by D. J. Brown;

s - Triazines and Derivatives, Vol. 13 by R. M. Smolin, L. Rappoport, of the same series.

- F. C. Schaefer, US patent 3, 154, 547; K. R. Huffman and F. C. Schaefer, J. Org. Chem., 28, 1812 (1963)

where is described the synthesis of triazines.

In light of the above professionals are clear ways of getting.

Acceptable for agriculture salts of compounds of formula I are valuable herbicides and can be obtained by known methods. For example, metal salts can be obtained by reacting compounds of the formula I with a solution of salts of alkaline or alkaline earth metal having a sufficiently basic anion (e.g., hydroxide, alkoxy, carbonate or hydroxide). Quaternary amine salts can be obtained in a similar way.

Salts of compounds of formula I can also be obtained by the reaction of exchange of one cation for another. Cationic exchange can be done by Pramogu the metal) with a solution, containing the cation to be exchanged. This method is most effective when the target salt containing substituted cation, insoluble in water and can be filtered.

Currency can also be made by passing an aqueous solution of salts of the compounds of formula I (for example, salts of alkali metal or Quaternary amine salt) through a column Packed with cation exchange resin containing the cation to which you want to exchange the cation source of salt, and elwira target product from the column. This method is especially effective when the target salt is water soluble, such as potassium, sodium or calcium salt.

Salt obtained by adding acids and is the subject of this invention, can be obtained by the coupling of compounds of formula I of the acid, for example p-toluensulfonate acid, trichloroacetic acid, etc.,

Most preferred are salts pyridinesulfonamide formula.

,

where

M denotes Li, Ca, K, (CH3)2N(H)CH2CH2OH, [(CH3)2CH]2NH2, (CH3CH2)2N(H)CH2CH2OH, (CH3)2CHNH3, (CH3CH2)3NH.

SPO is Rami. Temperatures are given in degrees Celsius; the reduction for the spectrum of nuclear magnetic resonance (NMR) as follows: s = singlet, d = doublet, t = triplet, q = Quartet, m = multiplet, and the peak positions are given in parts per million from internal standard tetramethylsilane. The position of the infrared peaks (IR) is given in reciprocal centimeters (cm-1).

Example 1. Getting 2-fluoro-3-(propylthio)-pyridine

To a stirred solution of 59 ml (0,113 mole) of 1.9 molar diisopropylamide lithium (in hexane) in 150 ml dry tetrahydrofuran cooled to -70oC, under nitrogen atmosphere dropwise added a solution of 10.0 g of 2-herperidin (0,103 mole) in 30 ml dry tetrahydrofuran so that the temperature remained below -65oC. the Solution was stirred at -70oC for 4 h and dropwise added a solution of 17 g of n-propylthiourea (0,113 mole) in 45 ml of dry tetrahydrofuran, maintaining the temperature below -65oC. After stirring for another hour at -70oC the solution was poured into water and was Proektirovanie ether. The combined organic extracts washed a strong salt solution, dried by magnesium sulfate and boiled away, the result obtained 14.5 g (82%) of a red oil: NMR (CDCl3, 200 MHz), and 1.0 (3H, m), 1,7 (2H, m), 2,9 (2H, m) and 7.1 (1H, m), and 7.7 (1H, m), is on

To a suspension of 0.62 g (0,013 mol) of 50% sodium hydride (in mineral oil), which is washed with hexane in 20 ml of dry dimethylformamide, cooled to -5oC, with stirring, under a nitrogen atmosphere is added dropwise was added 1.6 g (0,013 mol) benzylmercaptan so that the temperature did not exceed 5oC. the Suspension was stirred at room temperature for 1 h, cooled to 0oC and dropwise added a solution of 2.0 g (0,0112 mol) of product of example 1. Maintaining the temperature, the solution was poured into water and was Proektirovanie ether. The combined organic extracts were washed with water and a strong salt solution, dried by magnesium sulfate and boiled away, resulting in an oil that was purified chromatographically, and obtained 0.9 g (27%) of an oil; NMR (CDCl3, 200 MHz) of 1.02 (3H, t, J=7 Hz), 1,6 (2H, m), 2,9 (2H, t, J=7 Hz), of 4.45 (2H, s), 6,9-7,6 (7H, m), and 8.3 (1H, m); IR (pure) 1560, 1370 cm-1.

Example 3. Obtaining N-(1,1-dimethylethyl)-2-(propylsulfonyl)-2 - pyridinesulfonamide

It will smeet 0.5 g (0,0018 mol) of product of example 2 in 9 ml of methylene chloride and 4 ml of water, cooled to 0oC, under vigorous stirring was added 0.7 ml (0,008 mole) of concentrated hydrochloric acid, and then dropwise added to 8.9 ml (0,006 mole) of 5% hypochlorite solution napolnitele for 30 min at a temperature of 0oC, the reaction mixture was poured into water and was Proektirovanie methylene chloride. The combined organic extracts washed a strong salt solution, dried by magnesium sulfate and filtered. The filter was mixed and cooled to -70oC under nitrogen atmosphere and dropwise added to 0.53 g (0,0072 mole) of tert-butylamine, and the mixture allowed to warm to room temperature. The reaction mixture is poured into water and was Proektirovanie methylene chloride. The organic extracts were combined and washed a strong salt solution, dried by magnesium sulfate and boiled away, the resulting mixture was purified chromatographically and received 0.4 g (69%) white matter Tpl.138 - 140oC; NMR (CDCl3, 200 MHz) of 1.09 (3H, m), and 1.7 (1H, m), 2,0 (1H, m), 2,8 (1H, m), and 3.3 (1H, m), 5,2 (NH), and 7.7 (1H, m), and 8.6 (1H, m), and 8.6 (1H, m), and 8.8 (1H, m), IR (nujol) 3400, 1375, 1325, 1160, 1065, 1015 cm-1.

Example 4. Obtaining 3-(propylsulfonyl)-2-pyridinesulfonamide

To a solution of 8.8 g (0,029 mole) of the product from example 3 in 400 ml of methylene chloride, cooled to -5oC, with stirring, under a nitrogen atmosphere was added 6.6 g (of 0.038 mole) of 3-chlormadinone acid and stirred at room temperature for 30 hours, the Reaction mixture was poured into water and was Proektirovanie methylene chloride. Organic extrem magnesium and boiled away, the result has been a solid mixture, which was washed with hexane and obtained a white crystalline substance. The substance was dissolved and stirred in 150 ml triperoxonane acid within 72 hours the Solution was boiled away and was treated with ether, the resulting received 5,3 g (46%) of white crystalline substance: Tpl.153 - 157o; NMR (CDCl3, 200 MHz) of 1.06 (3H, t, J = 7 Hz), 1,8 (2H, m), 3,7 (2H, m), 5,8 (NH2), and 7.8 (1H, m), and 8.6 (1H, m), of 8.95 (1H, m); IR (nujol) 3390, 3180, 1360, 1310, 1175, 1150 cm-1.

Example 5. Obtaining N-[(4,6-dimethoxypyrimidine-2 - yl/aminocarbonyl]-3-(propylsulfonyl)-2-pyridine - sulfonamida.

To a suspension of 0.4 g (0,0015 mol) of product of example 4 and 0.63 g (0,0023 mole) of phenyl(4,6-dimethoxypyrimidine-2-yl)carbamate in 4 ml of acetonitrile under stirring was added 0.35 g (0,0023 mole) of 1,8-diazabicyclo[5,4,0]under-7-ene and stirred for 30 minutes the Solution was diluted with water and acidified using 1 N. hydrochloric acid. The precipitation was filtered and washed with water and ether. The result obtained 0.45 g (67%) white matter: Tpl.168 - 170oC; NMR (CDCl3, 200 MHz) of 1.07 (3H, t, J = 7 Hz), of 1.85 (2H, m), 3,7 (2H, m), of 3.97 (6H, s), and 5.8 (1H, s), 7,26 (NH), and 7.8 (1H, m), and 8.6 (1H, m), 8,9 (1H, m), 12,9 (NH); IR (nujol) 3320, 1740, 1610, 1580, 1375, 1195, 1170 cm-1.

Example 6. Obtaining 3-ethylthio-2-ftoruridina3
, 200 MHz) of 1.3 (3H, t, J = 7 Hz), 2,95 (2H, q, J = 7 Hz), and 7.1 (1H, m), and 7.7 (1H, m), and 8.0 (1H, m); IR (pure) 1585, 1565, 1410, 1230 cm-1.

Example 7. Obtaining 3-ethylthio-2-(feniletilic)-pyridine

By the same method described in example 2, 25,0 g (0,160 mole) of the product from example 6 was turned into 44,8 g (100%) of the indicated compound as a yellow liquid: NMR (CDCl3, 200 MHz) of 1.28 (3H, t, J = 7 Hz), 2,9 (2H, q, J = 7 Hz), of 4.45 (2H, s), of 7.0 and 7.6 (7H, m), 8,35 (1H, m); IR (pure) 1610, 1405 cm-1.

Example 8. Obtaining N-(1,1-dimethylethyl)-3-ethylsulfinyl-2 - pyridinesulfonamide.

By the same method described in example 3 was carried out the conversion of 35.0 g (0,134 mole) of the product from example 7 21.2 g (56%) of the specified compounds: Tpl.129 - 131oC; NMR (CDCl3, 200 MHz) of 1.23 (9H, s), of 1.28 (3H, t, J = 7 Hz), 2,9 (1H, m), and 3.3(1H, m), 5,2 (NH), and 7.7 (1H, m), 8,55 (1H, m), is 8.75 (1H, m), IR (nujol) 3100, 1320, 1155 cm-1.

Example 9. Obtaining N-(1,1-dimethylethyl)-3-ethylsulfonyl-2 - pyridinesulfonamide

Using the first part of the method described in example 4 (for example, the reaction of 3-chlormadinone acid), carried out the conversion of 9.0 g (0,033 mole) of the product from example 9 10.1 g (100%) specified connection: Tpl.58 - 63oC; NMR (CDCl3, 200 MHz), 1,2 (3H, t, J = 7 Hz), 1,2 (9H, s), 3,7 their 3-ethylsulfonyl-2-pyridinesulfonamide

Using the second part of the method described in example 4 (for example, the reaction triperoxonane acid), carried out the conversion of 9.0 g (0,029 mole) of the product from example 9 4.2 g (38%) of the specified compounds: Tpl.211 - 212,5oC; NMR (DMSO-d6, 200 MHz) and 1.15 (3H, t, J = 7 Hz), 3,4 (NH2), 3,7 (2H, q, J = 7 Hz), and 7.9 (1H, m), and 8.5 (1H, m), of 8.95 (1H, m), IR (nujol) 3370, 3190, 1350, 1310, 1180 cm-1.

Example 11. Obtaining N-[(4,6-dimethoxypyrimidine-2-yl)- aminocarbonyl]-3-ethylsulfonyl-2-pyridinesulfonamide

According to the method described in example 5 was carried out the conversion of 0.60 g (0,0024 mole) of the product from example 10 0,70 g (70%) of the specified compounds: Tpl.160 - 162oC; NMR (CDCl3, 200 MHz) of 1.35 (3H, t, J = 7 Hz), 3,7 (2H, q, J = 7 Hz), of 3.97 (6H, s), and 5.8 (1H, s), and 7.3 (NH), of 7.75 (1H, m), and 8.6 (1H, m), 8,9 (1H, m), 12,95 (NH); IR (nujol) 3260, 1740, 1610, 1360, 1195, 1175 cm-1.

Example 12. Obtaining 2,6-debtor-3-pyridineboronic acid complex methyl ester

To a solution of 91 ml (of 0.182 mole) of 2.0 molar diisopropylamide lithium (in hexane) in 200 ml dry tetrahydrofuran cooled to -70oC, with stirring under nitrogen atmosphere dropwise added a solution of 20.0 g of 2,6-diphereline (0,174 mole) in 75 ml of dry tetrahydrofuran so that the temperature was maintained below 60oC. the Solution was stirred at -70is trageriemen, cooled to -70oC, under nitrogen atmosphere. After stirring for another hour at -70oC the mixture was poured into water and was Proektirovanie ether. The combined organic extracts washed a strong salt solution, dried by magnesium sulfate and boiled away, resulting in a semi-solid substance, which was purified chromatographically and received 16.0 g (43%) orange oil: NMR (CDCl3, 200 MHz) of 3.95 (3H, s), 6,9 (1H, m), and 8.5 (1H, m), IR (net) 1745, 1730, 1610, 1415, 1280 cm-1.

Example 13. Getting 2-fluoro-6-methoxy-3-pyridineboronic acid complex methyl ester

To a solution of 15.0 g (0,0867 mol) of product of example 12 in 24 ml of dry tetrahydrofuran, cooled to -78oC, with stirring, dropwise added to 22.7 ml (0,0993 mole) of 25% aqueous solution of sodium methoxide in methanol for 45 min After warming to -20oC the mixture was poured into ice water, acidified using 1 N. hydrochloric acid and Proektirovanie ether. The combined organic extracts washed a strong salt solution, dried by magnesium sulfate and boiled away before the formation of semi-crystalline substance, which was purified chromatography and obtained 3.2 g (17%) of pale yellow solid: Tpl.81 - 82oC; NMR (CDCl3that 200 is naletili)-3 - piridincarbonova acid, difficult methyl ester

To a solution of 0.8 g (0,0161 mole) 50% sodium hydride (in mineral oil), which is washed with hexane in 20 ml of dry dimethylformamide, cooled to -5oC, with stirring, under a nitrogen atmosphere is added dropwise was added 1.9 ml (0,0161 mole) of benzylmercaptan. The suspension was stirred at room temperature for 1 h, cooled to 0oC and dropwise added a solution of 3.2 g (0,0147 mole) of the product from example 13 in 20 ml of dry dimethylformamide. After heating to room temperature the solution was poured into water and was Proektirovanie ether. The combined organic extracts were washed with water and a strong salt solution, dried by magnesium sulfate and boiled away before formation of the oil, which was purified chromatographically and received 3.0 g (64%) of yellow solid: Tpl.67 - 71oC; NMR (CDCl3, 200 MHz), 3,88 (3H, s), 2,96 (3H, s), to 4.46 (2H, s), 6,44 (1H, q, J = 9 Hz), 7,2 - 7,5 (5H, m) and 8.1 (1H, d, J = 9 Hz), IR (nujol) 1700, 1580, 1305, 122 cm-1.

Example 15. Getting 2-[(1,1-dimethyl)-aminosulfonyl]-6-methoxy-3-pyridineboronic acid complex methyl ester

To a mixture of 3.7 g (0,0129 mole) of the product from example 14 in 79 ml of methylene chloride and 41 of water, cooled to 0oC, under vigorous stirring was added 6.3 ml (0,0759 matria so, the temperature was maintained below 5oC. After stirring the mixture for 30 min at 0oC, the reaction mixture was poured into water and was Proektirovanie methylene chloride. The combined organic extracts washed a strong salt solution, dried by magnesium sulfate and was filtered. The filtrate was stirred and cooled to -70oC under nitrogen atmosphere and dropwise added to 4.7 (0,0645 mole) of tert-butylamine. The reaction mixture is allowed to warm to -20oC, poured into water, acidified using 1 N. hydrochloric acid and Proektirovanie methylene chloride. The combined organic extracts washed a strong salt solution, dried by magnesium sulfate and boiled away before the formation of semi-crystalline substance, which was purified chromatographically, and received 3.0 g (77%) of yellow solid: Tpl.128-130oC; NMR (CDCl3, 200 MHz) of 1.27 (9H, s), of 3.94 (3H, s), of 4.05 (3H, s), 5,75 (NH) and 6.9 (1H, d, J=9 Hz), 7,95 (1H, d, J=7 Hz); IR (nujol) 3260, 1740, 1605, 1325, 1125 cm-1.

Example 16. Obtaining 1-(aminosulfonyl)-6-methoxy-3-pyridineboronic acid complex methyl ester

A solution of 2.9 g (0,0096 mole) of the product from example 15 were mixed in 50 ml triperoxonane acid at room temperature for 20 hours the Solution was boiled away and p is 3H, s), 5,6 (NH2) and 6.9 (1H, d, J=9 Hz), and 8.1 (1H, d, J=9 Hz); IR (nujol) 3305, 3205, 1715, 1590, 1355, 1320, 1175 cm-1.

Example 17. Getting 2-[[4,6-dimethoxypyrimidine-2-yl]-aminocarbonyl aminosulfonyl]-6-methoxy-3-pyridineboronic acid complex methyl ester

To a suspension of 0.4 g (0,0016 mol) of product of example 16 and 0.54 g (0,002 mol) of phenyl-(4,6-dimethoxypyrimidine-2-yl)-carbamate in 4 ml of acetonitrile with stirring dropwise added to 0.30 g (0,002 mol) of 1,8-diazabicyclo [5.4.0] undec-7-ene, was stirred for 30 minutes the Solution was diluted with water and acidified using 1 N. hydrochloric acid. The precipitation was collected and washed with water and ether and received 0,57 g (84%) of white crystalline substance: Tpl.194-196oC; NMR (CDCl3, 200 MHz), 3,83 (3H, s), 3,95 (9H, s), and 5.8 (1H, s), to 6.95 (1H, d, J=9 Hz), 7,4 (NH) and 8.1 (1H, d, J=9 Hz), 12,8 (NH); IR (nujol) 3140, 1740, 1720, 1640, 1360, 1195, 1140 cm-1.

Example 18. Obtaining N-(1,1-dimethylethyl)-2-fluoro-3-pyridinesulfonamide

To a solution of 396 ml (0,740 mole) of 1.9 molar diisopropylamide lithium (in hexane) in 1.5 l of dry tetrahydrofuran cooled to -70oC, with stirring, under nitrogen atmosphere, dropwise added a solution of 65 g (0,670 mole) of 2-herperidin in 150 ml of dry tetrahydrofuran so that the temperature was maintained below -65oC. Suspension who -65oC. After stirring for 15 min at -70oC the reaction mixture allowed to warm to 0oC and boiled away the half volume, then diluted with ether. A white precipitate was collected under nitrogen atmosphere, washed with ether and dried. The solid was dissolved in 800 ml of acetic acid and cooled to 10 - 20oC. To this solution with stirring parts added and 99.4 g (0,740 mole) N-chlorosuccinimide, keeping the temperature below 20oC. After stirring for 30 min, the suspension is boiled away, diluted with water and was Proektirovanie methylene chloride. The combined organic extracts were washed with saturated aqueous sodium bicarbonate solution until the evolution of gas, washed the strong salt solution, dried by magnesium sulfate and was filtered. The filtrate was cooled to -70oC under a nitrogen atmosphere, to this solution with stirring dropwise added to 199 g (2.7 mol) of tert-butylamine. The suspension is poured into ice water, acidified with concentrated hydrochloric acid and was Proektirovanie methylene chloride. The combined organic extracts washed a strong salt solution, dried by magnesium sulfate and boiled away, resulting in an oil that was purified chromatographically got 22,47 (14,5%) of white crystalline substance: Tpl.95-97oC; NMR (CDCl3, 200 MHz) of 1.25 (9H, s), 4,9 (NH), 7,35 (1H, m), 8,3-8,5 (2H, m).

Example 19. Obtaining N-(1,1-dimethylethyl)-2-fluoro-N-methyl-3-pyridinesulfonamide

To a suspension of 3.4 g (0,071 mole) of a 50% aqueous lithium hydride (in mineral oil), which is washed with hexane, in 120 ml of dry dimethylformamide, cooled to 0oC, with stirring, under nitrogen atmosphere, dropwise added a solution of 15.0 g (0,065 mole) of the product from example 18 in 120 ml of dry dimethylformamide. After stirring at room temperature for 1 h the mixture was cooled to 0oC and dropwise added to 12.2 (0,086 mole) methylene iodine. After heating to room temperature the reaction mixture was poured into ice water and was Proektirovanie ether. The combined organic extracts washed a strong salt solution, dried by magnesium sulfate and boiled away, resulting in a received 15.9 g (99%) of an oil: NMR (CDCl3, 200 MHz) of 1.32 (9H, s), 3,1 (3H, s), and 7.3 (1H, m), 8,3 an 8.4 (2H, m); IR (pure) 1590, 1570, 1335, 1155 cm-1.

Example 20. Obtaining N-(1,1-dimethylethyl)-N-methyl-2-(feniletilic)-3 - pyridinesulfonamide

By the same method described in example 14, carried out the conversion of 15.9 g (0,065 mole) of the product from example 19 19.5 g (86%) of yellow crystalline substance: Tpl.92-9LASS="ptx2">

Example 21. Obtaining N2,N3,bis(1,1-dimethylethyl)-N3-methyl-2,3-pyridinesulfonamide

By the same method described in example 15 was carried out by conversion of 19.5 g (0,056 mol) of product of example 20 in the matter, which was washed with n-butyl chloride, and got to 13.1 g (66%) white matter: Tpl.155-156,5oC; NMR (CDCl3, 200 MHz) of 1.23 (9H, s), 3,1 (3H, s), 6,0 (NH), (1H, m), and 8.5 (1H, m), and 8.8 (1H, m); IR (nujol) 3320, 1340, 1325, 1160, 1120 cm-1.

Example 22. Obtaining N3-methyl-2,3-pyridinesulfonamide

A solution of 13.1 g (being 0.036 mole) of the product from example 21 in 150 ml triperoxonane acid was boiled under stirring for 5 hours After cooling to room temperature, the solution was boiled away and got a solid, which was washed with ether, and obtained 9.6 g (100%) of white crystalline substance: Tpl.220-223oC; NMR (DMSO-d6, 200 MHz), and 3.5 (3H, d), 6,9 (NH), 7,65 (NH2), a 7.85 (1H, m), to 8.45 (1H, m), 8,9 (1H, m); IR (nujol) 3380, 3320, 3180, 1355, 1170 cm-1.

Example 23. Obtain N2-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl]- N3-methyl-2,3-pyridinesulfonamide

To a suspension of 4.15 g (0,0165 mole) of the product from example 22 and 5.0 g (0,018 mole) of phenyl-(4,6-dimethoxypyrimidine-2-yl)-carbamate in 50 ml of acetonitrile with stirring dropwise added 2.8 g (0,018 mole) of 1,8-diazabicyclo [5.4.0] undec-4-ene and Ali and washed with water and ether, the result obtained 6.4 g (82%) white matter: Tpl.147-148oC; NMR (CDCl3, 200 MHz), 2,7 (3H, d, J=9 Hz), of 3.97 (6H, s), and 5.8 (1H, s), x 6.15 (1H, m), and 7.3 (NH), and 7.7 (1H, m), 8,55 (1H, m), and 8.8 (1H, m), 13,1 (NH); IR (nujol) 3310, 1740, 1610, 1340, 1190, 1165 cm-1.

When applying the procedures of examples 1-23 and equations 1-18 specialists in this field of technology can be obtained the compounds shown in tables 1-14.

The following are the data showing the advantages of the proposed compounds known before (see tab. 15, 16, 17).

The closest counterpart of U.S. patent N 4521597 is the connection 1 in column 10, example 10. Comparison of lead connection 68 of the present invention. The method described in test A.

As can be seen from the table. 15, at the tested dose of a compound of the present invention is perfectly safe for corn, while a similar connection damage the corn to the extent that recovery is no longer possible. In addition, the compound of the present invention exhibits improved herbicide activity against almost all of these types of weed. Obviously, this astounding degree of safety for crops and improved herbicide efficacy is the connection 1.30 in table 1. Comparison of lead connection 34 of the present invention. The test method described below in the test A.

As can be seen from the table. 16, the connection according to the invention has excellent protivosokovm effect at the tested dose compared with the equivalent for all of these types of weeds. This applies in particular to Petulia millet and starry average. While similar shows weak activity against batoshevo millet and chickweed average, the compound of the invention shows almost complete control of these two important species of weed. Excellent herbicide activity of the compounds of the invention startling and unexpected in light of the results disclosed in patent EP-A-97122.

The closest analogue of EP-A-103543 is the connection 167 table 1 in comparison with the connection 92 of the present invention. The test method described in test B of the present invention.

As can be seen from the table. 17, the connection of the invention is perfectly safe for corn at the dose of 16 g/ha, while similar damages the corn at this dose. In addition, the compound of the invention has excellent protivosokovm action compared with similar relative Chicago sorghum. While analog has no herbicide activity against wild sorghum, the compound of the invention shows almost complete control over this important type of weed. Excellent protective action in relation to vegetable crops and weed-killing activity of the compounds of the invention are surprising and unexpected in light of the results disclosed in EP-A-103543.

Compounds

Designed for use formulations based on the compounds of formula I can be prepared by traditional methods. They can be manufactured in the form of Farrukh Dustov, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, etc., Many of them can be used directly. Sprayable formulations can be obtained by using the appropriate media and to use in containers for spraying from a few liters to several hundred liters per hectare. Highly effective compositions are mainly used as an intermediate to obtain the target compounds. Such formulations contain generally from about 0.1 to 99 wt.% activitiesthese ingredient(s) and at least one of(a) surfactant(a) in an amount of from about 0.1 to 20%, and (b) about 1%/99.9% of a solid relationship (see table. 18).

The compositions can include, of course, more or fewer activitiesthese ingredient depending on the intended use and the physical properties of the compound. Sometimes it is desirable to use a higher ratio of surfactant to activetestsuite ingredient, which is achieved by introducing into the composition or by mixing in the tank.

Typical solid diluents are described in the book Watkins et al., "Handbook of Insecticide Dust Diluents and Carriers". 2 nd Ed., Dortland Books, Caldwell, New Jersey, but can be used and other solid diluents are either natural or artificial. More adsorption-capable diluents are preferred for wettable powders and more heavy - Farrukh Dustov. Typical liquid diluents and solvents are described in the book Marsden, "Solvents Guide", 2nd Ed., Interscience, New York, 1950. For suspension concentrates, it is preferable solubility of about 0.1%. The concentrated solutions are generally stable against phase separation at 0oC. In the books "McCutcheon''s Detergents and Emulsifiers Annual", McPublishing Corp. , Ridgewood, New Jersey; Sisely Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co. Inc., New York, 1964, lists surfactants and recommended areas of use. In microbiological growth, etc.

Methods of obtaining such compositions are well known. The solutions are simply mixing the ingredients. Fine solid composition is produced by mixing and, as a rule, joint by grinding in ball or water mills. Suspensions are prepared by wet-mixing (see, for example, U.S. patent 3060084, Littler). Granules and tablets can be obtained by spraying activitiesthese ingredient on the pre-molded granular media or the sintering method. See J. E. Browing, "Agglomeration", Chemical Engineering, December 4, 1967, pp. 147 ff; "Perry's Chemical Engineer''s Handbook", 5th Ed., McGraw - Hill; New York, 1963, pp. 8-57 ff.

More detailed information relating to the preparation of compositions, can be obtained from the following sources:

H. M. Loux, U.S. patent 3235361, February 15, 1966, column 6, line 16 to column 7, line 19 and examples 10 - 41;

R. W. Luckenbaugh U.S. patent 3309192, 14 March 1967, column 5, line 43 to column 7, line 62 and examples 8, 12, 15, 39, 41, 52, 53: 58, 132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knasli, U.S. patent 2891844, 23 June 1959, column 3, line 6, line 17 and examples 1-4;

G. C. Klingman, "Weed Control asa Science", John Wiley and sons, Inc., New York, 1961, pp. 81-96;

J. D. Fryer and S. A. Evens, "Weed Control Handbook", 5th Ed., Blakcwell Scientific publications, Oxford, 1968, pp. 101-103.

The following examples all the main concentrates, %:

N2-[(4,6-Dimethoxypyrimidine-2-yl)aminocarbonyl] -N3-methyl-2,3 - pyridinesulfonamide - 99

Trimethylene polietilenglikolya simple ether - 1

Surfactant is sprayed over activedayton ingredient in the mixer and the mixture is sieved through a sieve V. S. S. N 40 (the size of the holes 0,42 mm) before packaging. The concentrate can be used to obtain the target compounds.

Example 25

Wettable powders, %:

[(4,6-Dimethoxypyrimidine-2-yl)aminocarbonyl]-aminosulfonyl]-3 - pyridinecarboxamide acid, methyl ester - 65

Dodecylphenol polietilenglikolya simple ether - 2

Ligninsulfonate sodium - 4

Silicoaluminate sodium - 6

Montmorillonite (calcined) - 23

All the ingredients are thoroughly mixed. Add liquid surface-active substance, spraying it over the solid ingredients in the mixer. After grinding in a hammer mill to obtain a particle size below 100 microns, the material is again mixed and sieved V. S. S. No. 50 (size of holes 0.3 mm) and Packed.

Example 26

Water suspension, %:

N2-[(4,6-Dimethoxypyrimidine-2-yl)aminocarbonyl] -N3-methyl-2,3 - pyridinesulfonamide - 40,0

G about the at - 1

Monolatrist - 0,5

Polyvinyl alcohol - 1,0

Water - 56,7

The ingredients are mixed together and milled in a sand mill and get particles down to 5 microns.

Example 27

Oil suspensions, %:

N-[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl-3-(1-propylsulfonyl)-2 - pyridinesulfonamide, methyl ester - 35

The mixture of esters of polyatomic alcohols and carboxylic acids and soluble petroleum sulfonates - 6

Xylene - 59

The ingredients are mixed together and milled in a sand mill and get a particle size greater than 3 microns. The product can be used directly, filled with oil or emulsified in water.

Example 28

Oil suspensions, %:

N-[(4,6-Dimethoxypyrimidine-2-yl)aminocarbonyl-3-(1-methylsulfonylamino)- 2-pyridinesulfonamide, methyl ester - 25

Polyoxyethyleneglycol - 5

Vyisokoellipticheskoy hydrocarbon oil - 70

All the ingredients are crushed together in a sand mill until then, until the particle size reaches about 5 microns. Received a thick slurry can be used directly, but preferably after dilution oils or arbonyl-3-(1-ethylsulfonyl)-2 - pyridinesulfonamide, methyl ester - 25

Hydrated attapulgite - 3

Raw ligninsulfonate calcium - 10

Acidic sodium phosphate and 0.5

Water - 61,5

All the ingredients are pulverized in a ball or roller mill until then, until the particle size reaches below 10 microns in diameter.

Example 29

Wettable powder, %:

N2-[(4,6-Dimethoxypyrimidine-2-yl)aminocarbonyl-N3-methyl-2,3 - pyridinesulfonamide - 40,0

Dictinary sulfosuccinate - 1,5

Ligninsulfonate sodium - 3

Low viscosity methyl cellulose and 1.5

Attapulgite - 54

All the ingredients are thoroughly blended, passed through an air mill and get the average particle size below 15 microns, newly mixed and sieved V. S. S. No. 50 (size of holes 0.3 mm) before packaging.

All the compounds of this invention can be used in such compositions the same way.

Example 30

The granulate, %:

Wettable powder of example 29 - 15

Gypsum - 69

Potassium sulfate - 16

All the ingredients are mixed in a rotary mixer and sprayed water to perform granulation. When the main part of the material reaches the particle size of the required values from 1.0 to 0.42 cm to obtain additional material with a particle size of the desired value. These granules contain % activitiesthese ingredient.

Example 31

Wettable powder, %:

N-[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl-3-(ethylsulfonyl)-2 - pyridinesulfonamide, methyl ester - 50

Alkylnaphthalene sodium - 2

Low viscosity methyl cellulose - 2

Diatomaceous earth - 46

All the ingredients are blended, coarsely ground in hammer mills and air and get a particle size below 10 microns in diameter. Before packing the product re-mix.

Example 32

Spriteme pills, %:

N-[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl-3-(ethylsulfonyl)-2 - pyridinesulfonamide - 25

Anhydrous sodium sulphate - 10

Raw ligninsulfonate calcium - 5

Alkylnaphthalene sodium - 1

Bentonite calcium/magnesium - 59

All the ingredients are mixed, ground in a hammer mill, and then moisturize approximately 12% of water, the mixture is then spazout in the form of cylinders with a diameter of approximately 3 mm, which are cut and get pills, length 3 mm, They can be used directly after drying or dried tablets may be crushed to pass through a sieve V. S. S. N 20 (size of holes 0.84 mm). Granules, hold the measure be put in the recycling.

Example 33

Wettable powder, %:

N-[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl-3-(1-ethylsulfonyl)-2 - pyridinesulfonamide - 80

Alkylnaphthalene sodium - 2

Ligninsulfonate sodium - 2

Synthetic amorphous silicon dioxide - 3

Kaolinite - 13

All the ingredients are mixed and then pulverized in a hammer mill and get particles with an average size of less than 25 microns in diameter, the material is again mixed and sieved V. S. S. No. 50 (size of holes 0.3 mm) before packaging.

Example 34

Highly concentrated concentrates, %:

N-[(4,6-Dimethoxypyrimidine-2-yl)aminocarbonyl] -3-(1-ethylsulfonyl)-2 - pyridinesulfonamide - 98,5

The aerogel silica - 0,5

Synthetic amorphous fine silica - 1,0

All the ingredients are mixed and ground in a hammer mill and get a highly concentrated concentrate the particles of which almost all pass through a sieve V. S. S. No. 50 (size of holes 0.3 mm). This material can then be used to obtain different compositions.

Example 35

Wettable powder, %:

2-[[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-aminosulfonyl]-3 - piridinkarbonovaya
Synthetic amorphous silicon dioxide - 3

Kaolinite - 13

All the ingredients are mixed and then ground in a hammer mill and get particles with an average size of less than 25 microns in diameter, the material is again mixed and sieved V. S. S. No. 50 (size of holes 0.3 mm) before packaging.

Example 36

High performance concentrates, %:

N2-[(4,6-Dimethoxypyrimidine-2-yl)aminocarbonyl] -N3-methyl-2,3 - pyridinesulfonamide - 98,5

The aerogel silica - 0,5

Synthetic amorphous fine silica - 1,0

All the ingredients are mixed and ground in a hammer mill and get a highly effective concentrate the particles of which almost all pass through a sieve V. S. S. No. 50 (size of holes 0.3 mm). This material can then be used in various compositions.

Use

The test results indicate that the compounds of this invention are highly effective pre-emergence and post-harvest herbicides or plant growth regulators. Many of them are used for large-scale pre - and/or postemergence weed control where necessary to completely destroy all rastitelnosty for motorists outdoors around the Bulletin boards and posters, near highways and Railways.

Some of the compounds used for the selective destruction of weeds among crops of cultivated plants: plants of the family Solanaceae, such as tomatoes, potatoes and peppers, and other crops such as wheat, barley, corn, cotton or soybeans or their parousia land. In particular, some of the compounds of this invention can destroy weeds in corn (maize) before and after germination without substantial damage to the main crop. Some of the compounds of this invention also destroy the weeds in potato (Solanum Tuberosum) and tomato (Lycopersicon esculentum) without significant damage to the main crop. They are especially acceptable for the destruction of such common weeds as spickle (Setaria spp.), millet (Panicum dichotomiflorum), millet plushie (Echinochloa crusgalli), sorghum Halep (Sorghum Halepense) and sorghum bicolor (Sorghum bicolor). They can be used before or after germination and are most effective when they treat the young shoots of weeds. They are also effective against some broadleaf weeds, such as pigweed white (Chenopofium album), SYRIZA (Amaranthus spp.) and canetic Theophrastus (Abution Theofphrasti).

the eskers of application for the compounds of this invention are determined by a number of factors, including their use as modifiers in the rate of growth of plants or herbicides, types of cultivated crops, the types of weeds to be destroyed, weather and climate, the selected compositions, type of treatment, number of leaves, etc., In General, the compounds of this invention should be used in an amount of about 0.001 to 20 kg/ha, lower dosages are recommended for use on light soils and/or those that contain little organic matter, to regulate the speed of growth or for those occasions when you need short-term preservation.

The compounds of this invention can be used in conjunction with any other industrial herbicide, an example of which can be the triazine, triazole, imidazoline, uracil, urea, amide, diphenyl simple ether, cineole, carbamate and connections BIPYRIDILIUM type. They are particularly effective in combination with the following herbicides.

Common name Chemical name

Alachlor - 2-chloro-2',6'-diethyl-N-(methoxymethyl)-acetanilide

Atrazine - 2-chloro-4-(ethylamino)-6-(isopropylamino)-S-triazine

Butyl - S-ethyl-diisobutylaluminum

Lunasin - 2-[[4-chloro-6(ethylamino)-S-triazine-2-yl] amino]-2 - methylpropionitrile

Dimetoxy-1-metalmachine

Metolachlor - 2-chloro-N - (2-ethyl-6-were)-N-(2-methoxy-1 - methylethyl)ndimethylacetamide

Metribuzin - 4-amino-6-tert-butyl-3-(methylthio)-as-triazine-5(4H)-he

Tridian - 2-(3,5-dichlorophenyl)-2-(2,2,2-trichlorethyl)oxiran

2,4-D (2,4-dichlorophenoxy)acetic acid

Bromoxynil - 3,5-dibromo-4-oxfenicine

Paraquat - 1,1'-dimethyl-4,4-bipyridine ion

Glyphosate - N-(phosphonomethyl)glycine

DHFA - dimethyl tetrachloroterephthalate

Dalapon - 2,2-dichloropropionic acid

Dinoseb - 2-(1-methylpropyl)-4,6-dinitrophenol

Diphenamid - N,N-dimethyl-2,2-diphenylacetamide

Pendimethalin - N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline

Oryzalin - 3,5-dinitro-N,N-dipropylacetamide

Trifluralin - , , -Cryptor-2,6-dinitro-N,N-dipropyl-p-toluidine

Chloramben - 3-amino-2,5-dichlorobenzene acid

Napropamide - 2-( -naphthoxy)-N,N-diethylpropane

Populat - S-propyl an butilmethacrylat

Chlorpropham - Isopropyl-m-chlorocarbonyl

Bensulide - S-(O, O-aminobutiramida phosphorodithioate) ester N-(2-mercaptoethyl)benzosulfimide

Trade name Chemical name

HarmonyTM- 3-[[(4-methoxy-6-methyl-1,3,5-triazine-2-yl)- aminocarbonyl] aminosulfonyl]-2-thiophenecarbonitrile KIS is ptan

---- - 2 ethoxy-N-[[4-(2,2,2-triptoreline)-6-methoxy-1,3,5-triazine-2-yl] aminocarbonyl]benzosulfimide

Experience A

Seeds Rosicky blood (Digitoria Sanguinalis), batoshevo millet (Echinochloa crus - galli), spickle (Setaris faberi), wild oats (Aven fatua), fire roofing (Bromus secalinus), cantica Theophrastus (Abutilon Theophracti), ipomea (Ipomea coccinea, varieties Scartel O'hara), cocklebur (Kathinm pensylvanicum), sorghum G 522 (Sorghum vulgare, varieties Funle G 522), corn G 4646 (Zea Mays, variety G Funk 4646), soybean Williams (Glycine max cultivar Williams), beet sugar USHII (Beta valgaris, varieties Union Sugarbeet COUSH II), cotton Cocker (Gossypium hirsutum, variety Coker 315), dry rice planting (Oryza Sativa, cultivar California Rice Coop. MIOI), wheat EPA (Triticum aestivum, variety Era spring), Klages barley (Hordeum vulgars, varieties Klages spring) and tubers site (Cyperus rotunodus) were sown and crops processed before the germination test chemicals dissolved in nepatologickou solvent. At the same time, these types of crops and weeds treated, causing the compound to the soil and foliage. At the time of processing the height of the seedlings reach 2 to 18 see the Treated and control plants were kept in a greenhouse for sixteen days, after which all samples were compared with the control was evaluated visually on the response to treatment. Estimates are summarized in table A, osnovnym the following values:

C = chlorosis/necrosis;

B = burn;

D = defoliation;

E = delay germination;

G = growth retardation;

H = the ability to growth;

U = unusual pigmentation;

X = axial stimulation;

S = albinism; and

6Y = dropping of buds or flowers.

"POSOL" and "PRSOL" in table A mean after - and pre-emergence treatment, respectively.

Draws attention to the fact that some compounds, such as compounds 6, 19, 20, 26, 32, 37 - 39, 44, 49, 54 - 59, 76 - 78 and 88 have a minor or do not have a weed-killing effect at the tested dosages. Suppose that at higher doses they will have herbicide action.

Experience B

Post-harvest processing

Three round cuvette (with a diameter of 25 cm and a depth of 12.5 cm) were filled with sandy loam soil Sassabras. One cuvette was put nodules of sniti (Cyperus rotundus), Rosicky blood (Digitaria sanguinalis), nesuhi (Cassia obtusifolia), jimson weed (Datura stramonium), cantica Theophrastus (Abutilow Theofrast), Marie white (Chenopadium album), dry rice planting (Oryza sativa varieties of California Rice. Coop. M101) and breast barbed (Sida spinosa). The second cell was inoculated spickle green (Seteria viridis), cocklebur (Xanthium pensylvanicum), morning glory (Ipomea coccinea, varieties Scarlet O'hara), cotton Cocker (Jossypium hirzutum, Sorsa (Jlycine max, grades Williams) and the results of the analysis of the giant (Setaria faberi). In the third cell was inoculated wheat (Friticum aestivum, variety Era spring), Klages barley (Hordeum vulgare, varieties Klages spring), Highlander Curling (Polgonum convolvulus), fire roofing (Bromus secalinus), sugar beet USHII (Beta vulgarus, varieties Union Sugarbeet Co. USHII), wild oat (Avena fataa), viola (Viola arvensis), Alopecurus myservername (Alopecurus myosuroides) and radish (Brassia napus, cultivar Altex). The plants were grown for approximately fourteen days, then sprayed after emergence chemical compounds dissolved in negoitations solvent.

Pre-emergence treatment

Three round cuvette (with a diameter of 25 cm and a height of 12.5 cm) filled in Sassafras sandy loam soil. One cell was inoculated nodules of sniti, Rosicky blood, nesuhi, jimson weed, cantica Theophrastus, Marie white, rice and brisket barbed. The second cell planted spickle green, cocklebur, morning glory, cotton, sorghum, chicken millet, corn, soybeans and spickle giant. In the third cell planted wheat, barley, Highlander Curling, fire roofing, sugar beets, oats, viola, Alopecurus myservername and radishes. Before the emergence of all three cell sprayed with chemical compounds dissolved in nepatologickou solvent.

The evaluation was performed on a scale from 0 to 100, where 0 = no effect and 100 = complete destruction. A dash (-) means that the experience did not.

Assessing the response of the plants in this treatment are presented in table B.

In table B in the link quality comparison used the connection 2 of U.S. patent N 4522645, characterized in that the connection 149 in the 6-position has ethoxypropan.

From these data it is seen that the connection 149 has an excellent herbicide activity. The comparison shows that the pre - and post-harvest activity of the compounds is higher than the connection of the comparison. At a concentration of 4 g/ha in post-harvest processing connection shows full tolerance of wheat and corn, and at the same time, controls the growth of bindweed purple and mountain climbing, and also reduces the activity of growth annoying Alopecurus field.

Experience B.

Six round cuvettes (with a diameter of 17 cm and 15 cm deep) were used for growing seedlings to the processing stage. Four seeds were sown or nodules of four species each, and the remaining soy, as the primer used sandy loam soil Sassafras (SAS). In the sixth cell sowed corn, using silt with the observed effect was only due to the absorption of the reagent sheet. In the experiment used a separate cell with corn (with a diameter of 25.5 cm and a depth of 19.5 cm) grown in Sassafras sandy loam soil to evaluate the treatment effect foliage/soil on the growth rate. Seedlings were grown in 10-20 days to the stage 2-5 worksheet, and then sprayed the compounds of this invention postemergence. As prototypes used the following types: corn (maize) G4646 (Zea mays, variety G Funk 4646), soy Williams (Jlycine max, cultivar Williams), spickle green (Setaria viridis), spickle giant (Setaria faberi), millet creeping (Panicum dichotomiflorum), weed blood (Digitaria sanguinalis), plushie millet (Echinochioa crus-galli), sorghum Halep (Sorghum halepense), sorghum G 522 (Sorghum vulgare, varieties Funk G 522), goutweed (Cyperus rotundus), canetic Theophrastus (Abutilow Theofrast), cocklebur (Xanthium pensyivanicum), Highlander pepper (polygonum persicaria), pigweed white (Chenopadium album), SYRIZA spiked (Amaranthus retroflexus), morning glory Ivy Morningylo (Ipomea hederacea), jimson weed (Datura stramonium), ragweed (Ambrosia artemiciifolia).

Pre-emergence treatment

Shoots were obtained, as described above, but all in silt loam Tama. Compounds were sprayed to the emergence on the next day after seeding, then all the cuvette was moistened, simulating rain.

After processing all the seedlings were kept in a greenhouse at approximately the course is= no effect and 100 = complete destruction. Evaluation of the response are shown in table B.

Experience

Potatoes (Solanum tuberosum, the "Green Mountain") has grown in soil 350 Metro in plastic cuvettes with a diameter of 20 cm By the time of spraying, the seedlings were 17-day. Chicken millet (Echinochia crus-galli), sorghum Halep (Sorghum halepense), spickle giant (Setaria faberi), sorghum Halep (Sorghum halepense), spickle giant (Setaria faberi), weed blood (Digitaria sangunalis), goutweed (Cyperus rotundus), jimson weed (Datura stramonium), canetic Theophrastus (Abutilon Theofrast), cocklebur (Xanthium pensylvanicum), morning glory (Ipomea hederacea) grown on sandy loam soil Sassafras (pH of 6.5, the organic content of 1%) half pans with plastic coated with a diameter of 25 cm By the time processing it was a 9-day shoots.

The investigated compounds were sprayed at a dose of 62, 16, 4 and 1 g/ha Compounds were sprayed with each dosage of one cell with the shoots of potatoes and at the same time on one cell with the other species. Compounds were dissolved in nepatologickou solvent, 4.0 percent, and sprayed at a dose of 374 l/ha Plants were kept in the greenhouse and 11 days after treatment assessed.

All treated plants were evaluated according to the degree of damage compared to the control plants. The degree of damage was assessed visually on a scale from 0 to 100%, g is ersicon esculentum species "Rutgers") and pepper (Capsicum frutesceus type "Jolo") were grown in soil 350 Metro in plastic cuvettes with a diameter of 10 cm By the time of processing the seedlings of tomato and pepper were 19-day. Goutweed (Cyperus rotundus), weed blood (Digitaria sanguinsalis), wall-cress (Cassia tora), bacon prickly Sida spinosa), jimson weed (Datura stramonium), canetic Theophrastus (Abutilon Theofrast), pigweed white (Chenopadium album), spickle green (Seteria viridis), cocklebur (Xanthium pensylvanicum), morning glory (Ipomea hederacia), sorghum Halep (Sorghum halepense), plushie millet (Echinochloa crus-galli), spickle giant (Setaria faberi), Highlander Curling (Polygonum convolvulus), the fire roofing (Bromus secalinus), wild oat (Avena fatua), starry (Stellaria spp.) and Alopecurus myservername (Alopecurus myosuroides) were grown in sandy loam soil Sassafras (pH of 6.5, the organic content of 1%) half pans with plastic coated with a diameter of 25 cm By the time processing it was 7-11-day shoots.

Compounds were sprayed at a dose of 62, 16, 4 and 1 g/ha Compounds were sprayed with each dosage of one cell with seedlings of tomatoes, one cell with pepper and three cuvettes with other species. Compounds were dissolved in nepatologickou solvent and sprayed at a dose of 374 l/ha Plants were kept in the greenhouse and 16 days after treatment assessed their condition. All treated plants were evaluated according to the degree of damage compared to the control plants. The degree of damage was assessed visually is SS="ptx2">

1. Pyridinesulfonamide General formula I

< / BR>
where R is H or CH3;

R1- Rfor Rq;

Rf- H, C1-C3-alkyl, C1-C3-haloalkyl, halogen, C1-C3-alkoxy or C1-C3-alkylthio;

Rq- C1-C3-haloalkyl; C1-C3-alkyl, substituted C1-C3-alkoxyl; C1-C3-alkylamino; di (C1-C3-alkylamino or W2R11;

R2- C1-C4-alkylsulfonyl, C1-C4-alkylsulfonyl, -SO2NH2, -SO2NRdRe, -SO2NR7R8, -OSO2R8, -CO2R9, -CF2H, -CH2Cl, C2-C4-haloalkyl, or N3;

R7- H;

C1-C4-alkyl;

Rd- C1-C2-alkyl;

Re- C1-C2-alkoxyl;

R8- C1-C4-alkyl or C1-C4-haloalkyl;

R7and R8taken together, could mean: -(CH2)3-, -(CH2)4- or -(CH2)5-;

R9- C3-C4-quinil, C4-C7-cycloalkyl, C3-C5-cycloalkyl or-CH2CH2OH;

C1-C4-alkyl;

R11- , 1-C4-alkoxy, C2-C4-haloalkoxy or halogen;

Y-C1-C4-alkyl, C1-C4-alkoxy, C1-C3-alkylamino or di-C1-C3-alkylamino; and

Z is CH or N;

provided that when X is halogen, then Z denotes CH, Y represents C1-C4-alkoxy, C1-C3-alkylamino or di-C1-C3-alkylamino; when the total number of carbon atoms of X and Y is greater than four, the total number of carbon atoms of R1and R2less than or equal to six; and when R2means or R1means Rqand when R2different from, or R1means Rf,

or acceptable for agriculture of salt.

2. Pyridinesulfonamide or acceptable for agriculture salts of formula I under item 1, with herbicide activity.

3. Salt pyridinesulfonamide formula I on p. 1 of General formula

< / BR>
where M is Zi, Ca, K, (CH3)2N(H)CH2CH2OH, [(CH3)2CH]2NH2, (CH3CH2)2N(H)CH2CH2OH, (CH3)2CHNH3, (CH3CH2)3NH.

4. Connection under item 1 or 2, characterized in that X represents a C1-C2-alkyl, C1-alkyl, C1-C2-alkoxyl, -NHCH3or-N(CH3)2.

5. Connection on p. 4, characterized in. what Rfrepresents H, -CH3C1-haloalkyl, halogen, or-OCH3; Rq- W2R11CH2OCH3C1-C2-alkylamino or N(CH3)2C1-C2-haloalkyl;

6. Connection on p. 5, characterized in that C1-C3-alkyl; R8- C1-C3-alkyl; R9- cyclopropylmethyl or-CH2CH2OH or propargyl; C1-C3-alkyl.

7. Connection on p. 6, characterized in that X represents-CH3, -OCH3, -OCH2CH3, Cl or-OCH2CF3; Y IS-CH3, -OCH3CH2CH3or NHCH3.

8. Connection on p. 7, characterized in that Z represents CH.

9. Connection on p. 7, characterized in that Z represents n

10. Connection on p. 8, characterized in that Z represents CH; R2- C1-C4-alkylsulfonyl or C1-C4-alkylsulfonyl; Rf-H, C1-C2-alkyl, C1-haloalkyl, C1-C2-alkoxy or C1-C2-alkylthio.

11. Connection on p. 10, wherein Rthe PoE represents N-[(4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-3-(1-propylsulfonyl)- 2-pyridinesulfonamide.

13. Connection on p. 1, which is N-[-4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-3-(1-propylsulfonyl)-2 - pyridinesulfonamide.

14. Connection on p. 1, which is N-[-4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-3-(1-ethylsulfonyl)-2 - pyridinesulfonamide.

15. Connection on p. 1, which represents the N2-[-4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-N3-ethyl - 2,3-pyridinesulfonamide.

16. Connection on p. 1, which is N-[-4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-3-(methylsulfonylamino)- 2-pyridinesulfonamide.

17. Connection on p. 1, which represents the N2-[-4,6-dimethoxypyrimidine-2-yl)aminocarbonyl]-N3-methyl-2,3-pyridinesulfonamide.

18. Composition for combating the growth of unwanted vegetation, containing the active ingredient and inert additives, characterized in that the active ingredient it contains a connection on p. 1 in an amount of 0.1 - 99 wt. % as inert additives at least one of the following ingredients: surfactant, solid inert diluent, inert liquid diluent or a mixture thereof.

19. The composition according to p. 18, characterized in that in km, as the active ingredient it contains a connection on p. 5.

21. The method of producing pyridinesulfonamide General formula I and their acceptable in agriculture salts

< / BR>
where R is H or CH3;

R1- Rfor Rq;

Rf- H, C1-C3-alkyl, C1-C3-haloalkyl, halogen, C1-C3-alkoxy or C1-C3-alkylthio;

Rq- C1-C3-haloalkyl; C1-C3-alkyl, substituted C1-C3-alkoxyl; C1-C3-alkylamino; di-C1-C3-alkylamino or W2R11;

R2- C1-C4-alkylsulfonyl, C1-C4-alkylsulfonyl, -SO2NH2, -SO2NR7R, -OSO2R8, -SO2NRdRe, -CO2R9, -CF2H, -CH2Cl, C2-C4-haloalkyl or N3;

R7- H;

C1-C4-alkyl;

R8- C1-C4-alkyl or C1-C4-haloalkyl;

R7and R8taken together, means -(CH2)3-, -(CH2)4- or -(CH2)5-;

R9- C3-C4-quinil, C4-C7-cycloalkyl, C3-C5-cycloalkyl or CH2CH2OH;

C
X - C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy or halogen;

Y-C1-C4-alkyl, C1-C4-alkoxy, C1-C3-alkylamino or di (C1-C3-alkylamino;

Rd- C1-C2-alkyl;

Re- C1-C2-alkoxyl;

Z is CH or N;

provided that when X is halogen, then Z is CH, and J means C1-C4-alkoxy, C1-C3-alkylamino or di-C1-C3-alkylamino; when the total number of carbon atoms of X and Y is greater than four, the total number of carbon atoms of R1and R2less than or equal to six; when R2means or R1means Rqand when R2different from, or R1means Rfcharacterized in that the sulfonamide of the formula

< / BR>
where R1and R2have the above values,

subjected to interaction with phenylcarbamate formula

< / BR>
where R, X, Y and Z have the above values,

in the presence of 1,8-diazabicyclo [5.4.0] undecen-7-ene and solvent, followed, if necessary, transfer the received pyridinesulfonamide in salt, for example, the interaction with the hydroxide of alkali or alkaline earth metal or Rf- H, C1-C3-alkyl, C1-C3-haloalkyl, halogen, C1-C3-alkoxy or C1-C3-alkylthio, R2- C1-C4-alkylsulfonyl, C1-C4-alkylsulfonyl, SO2NH2or SO2NR7R8, R7- H, R8- C1-C4-alkyl or C1-C4-haloalkyl, R7and R8taken together can be -(CH2)3-, -(CH2)4- or -(CH2)5- X - C1-C4-alkyl, C1-C4-alkoxy, C2-C4-haloalkoxy or halogen, Y is C1-C4-alkyl, C1-C4-alkoxy, C1-C3-alkylamino or di-C1-C3-alkylamino, Z is CH or N;

16.04.87 when R2- OSO2R8, CO2R9, CF2H, CH2Cl or C2-C4-haloalkyl, R9- C3-C4-quinil, C4-C7-cycloalkyl, C3-C5-cycloalkyl or CH2CH2OH; 28.08.87 when R1-Rq, Rq- C1-C3-alkyl, substituted C1-C3-alkoxyl, C1-C3-alkylamino, di-C1-C3-alkylamino or W2R11, R2- SO2NRdReor , R7- C1-C4-alkyl; Rd- C1-C2-alkyl, Re- O;

25.09.87 the other signs listed in the formula.

 

Same patents:

The invention relates to heterocyclic amines of formula I:

,

in which

X represents-CH2-group or-S-group;

B denotes a group selected from a number containing-CO -, - CH2OCO-, -CH2OCS-, -CH2NHCO - CH2NHCS-group;

D represents benzhydryl or phenyl group, optionally substituted by halogen atoms, and heterocyclic group, selected from a number containing 1,3,5-triazine-2-yl, pyridin-2-yl and pyrimidine-4-yl, and optionally substituted by one or two substituents selected from the group comprising amino, mono - or di-(C1C6) alkylamino, mono- (C3-C7)-alkynylamino, mono-(C3-C7)-quinil-amino group and pyrrolidin-1-yl group;

The is a simple carbon-carbon bond or a group of the formula: -CH2CH2or CRaRb-, where Raand Rbis a hydrogen atom, (C1-C3)alkyl, or taken together with the carbon atom to which they are attached, form a (C3-C6) cycloalkyl;

A is selected from the group comprising (a) carboxyl group optionally esterified (C1-C4) Ukrspirt the crystals: -C–ěNHRgOH, where Rcand Rdidentical or different, represent a hydrogen atom, (C1-C6) alkyl, benzyl, pyridin-2-yl, or taken together with the nitrogen atom to which they are bound, form piperidino, morpholino-, 4-thiomorpholine-, 4,5-diazepino, 4-(C1-C4)alkylpiperazine; Rfis a tolyl; Rgis a (C1-C4) alkyl;

(b) (C1-C3) alkyl;

(c) the group-NRcRdwhere Rcand Rddefined above,

(d) a cyano, if "y" does not mean a simple carbon-carbon bond

in the form of S-enantiomers, diastereomers, in the form of various racemic mixtures and their salts with pharmaceutically acceptable acids and bases

The invention relates to new methods of stereoselective obtain derivatives substituted piperidino

The invention relates to the compound N-pyridylsulfonyl-N'-pyrimidinylidene formula 1

< / BR>
where R1denotes methyl or methoxy and R2denotes hydrogen or methyl; compounds and salts of these compounds with amines, bases, alkali or alkaline earth metal or Quaternary ammonium bases have good herbicide and regulating plant growth properties during selective use before and after germination

The invention relates to compounds of formula (I) listed in the description, where R1represents a hydrogen atom or unsubstituted or substituted alkyl group; and A represents the number of cyclic or acyclic nitrogen containing groups

The invention relates to a new derived pikolinos acid, useful as components of the herbicide compositions, herbicide compositions containing it, which can be used in rice fields, cultivated fields and non-agricultural land

The invention relates to certain new derivative thimerisol, provides a way of obtaining them and relates to methods and compositions for use as antibacterial agents

The invention relates to the field of chemistry and agriculture, and in particular to substituted SIMM-triazines as postregulation and means for pre-processing based on them

The invention relates to new chemical compounds, specifically to N-chloramination SIMM

The invention relates to new chemical compounds, specifically to N-chloramination SIMM

The invention relates to the derivatives of triazolopyrimidine General formula (I), method of production thereof and to pharmaceutical compositions based on

The invention relates to a series of substituted 5-arylpyrimidines, to methods for their preparation, to pharmaceutical remedies containing these compounds and to their use in therapy, in particular in the treatment of a range of diseases and disorders of the Central nervous system (CNS)

The invention relates to the derivatives of triazolopyrimidine General formula (I), method of production thereof and to pharmaceutical compositions based on

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)
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