Derivatives isoxazol, methods for their preparation, herbicide composition, method of weed control

 

(57) Abstract:

Derivatives isoxazol formula I where Ar is phenyl, substituted by 1 to 3 groups of R2and where two of the substituents on adjacent positions of the phenyl ring together with the two atoms to which they are attached, form a 5-6-membered heterocyclic ring containing 1 or 2 heteroatoms selected from O, S and N, which may be substituted by one or more groups R21R-N; R1-C3-6cycloalkyl group; R2is a halogen atom, a C1-6alkyl, possibly substituted with halogen, group SR5, -SOR5, -SO2R5, -OR5, -(CR9R10)t-S(O)pR5; R21are R2or = O, R5- C1-6alkyl; R9and R10-H; p = 0, 1, or 2; t = I. the compounds of formula I can be used as herbicides.

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5 C. p. and 10 C.p. f-crystals, 2 tab.

The invention relates to new isoxazol derivative, compositions containing them, methods of obtaining and use as herbicides.

The invention offers the isoxazoles of formula I:

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where Ar represents phenyl possibly substituted by one to three groups R2that may be the same or different and in which two St 5 - 7 - membered ring which may be substituted with one or more groups R21and which may be the same or different;

R represents a hydrogen atom or a group-CO2R3;

R1represents an alkyl group with straight or branched chain, containing from one to six carbon atoms which may be substituted by one or more halogen atoms, or cycloalkyl group containing from three to six carbon atoms, with the possibility of substitution of one or more groups selected from R4, -CO2R4, -SR4, halogen and-OR4;

R2represents a halogen atom, alkyl group with straight or branched chain, containing from one to six carbon atoms, which is substituted by a group or SIG4; a group selected from R4, -CO2R4,-COR4, -SR5-THE SEPARATOR R S O5, SO2R5, -OSO2R5, -OR SIG5, -O/CH2/m-OR SIG4, -NR6R7, -N/R8/SO2R5, -/CR9R10/tS /O/pR5, nitro, cyano and NR11R12;

R21- as previously defined for R2or is =O, =S, cyclic ketal or cyclic thioketal;

R3and R4to or branched chain, containing up to six carbon atoms which may be substituted by one or more halogen atoms;

R5represents a group R4or phenyl, possibly substituted with one to five groups which may be the same or different and selected from halogen, R4, -CO2R4,-COR4, -OR SIG4, nitro, cyano, and-O/CH2/m-OR SIG4;

R6and R7that may be the same or different, each represent a hydrogen atom or alkyl group with straight or branched chain, containing from one to six carbon atoms which may be substituted by one or more halogen atoms;

Represents an integer from one to three;

R8represents a hydrogen atom; an alkyl group, alkenyl or quinil straight or branched chain containing up to six carbon atoms, with the possibility of substitution by one or more halogen atoms; cycloalkyl group containing from three to six carbon atoms; or phenyl, possibly substituted with one to five groups of R2that may be the same or different;

R9and R10that may be the same or different, each represents: a hydrogen atom; alkylene is more halogen atoms; or phenyl, possibly substituted by one to five groups which may be the same or different, selected from halogen, R4, -CO2R4,-COR4, -OR SIG4, nitro, cyano, and-O/CH2/m-PR4;

R11is-COR4and-CO2R4; R12represents: a hydrogen atom; alkyl group with straight or branched chain containing up to six carbon atoms, with the possibility of substitution by one or more halogen atoms; or cycloalkyl group containing from three to six carbon atoms;

p =0, 1, or 2;

t represents an integer from one to three, and if t is greater than one, the group CR9R10may be the same or different;

and their agricultural acceptable salts, which possess valuable herbicide properties.

In some cases, the substituents R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10and R21influence of optical and/or stereoisomer. All such forms are embraced by the present invention.

5 - to 7 - membered ring, which forms part of the group And is carbocyclic or heterocyclic containing one or more heteroatom sulfur, if any can be in the form of a group-SO - or-SO2and may be aromatic, saturated or partially saturated.

If R21is cyclic ketal or thioketal ring contains 5 or 6 elements.

Examples of the group And may include the following substituted ring system and the corresponding Dihydrocodeine /where applicable/:

benzo-1,2,3-thiadiazole, benzo[b] thiophene, benzo[b]furan, benzo[c]thiophene, benzo[c] furan, benzthiazole, 1,2-benzisothiazol, 2.1-benzisothiazol, 1,2-benzothiazin, 2,1-benzothiazin, 1,3-benzothiazin, 1,4-benzothiazin, benzimidazole, indazole, thiochroman, chroman 2N-chromen 2N-thiochroman, 4H-thromin, 4H-chromen, sociodrama, isochroman, sociograms, isochroman, benzofurazan, 1,3-benzodithiol, 1,3-benzodioxol, 1,3-benzodithiol, 1,4-benzodithiol, 1,4-benzoxazin, 1,3-benzoxazin, 3,1-benzoxazin, 1,3-benzodithiol, benzoxazol and 1,3-benzoxazol-2-it, indole, isoindole, 1,4-benzodioxin, 1,3-benzodioxin.

The term "agricultural acceptable salts" is meant salts the cations of which are known and acceptable in the field of machinery for the formation of salts for agricultural or horticultural use. Better if salt is water soluble.

Suitable acid additive salts formed compounds I with organic acids, for example acetic acid.

Preferred compounds of formula I in which Ar represents a possibly substituted 1,3-benzodioxole, benzo[b]thiophene, benzoxazole or benzo-1,2,3-thiadiazole.

Another preferred class of compounds of formula I are those in which: a /a/ R2located at the C-2 phenyl ring, if the condensation takes place at C-3 and C-4 of this ring, and // R2located at the C-4 phenyl ring, if condensation occurs on the C-2 and C-3 of the ring.

Preferably R2represents a halogen atom or a group selected from-SR5-THE SEPARATOR R S O5, SO2R5, R4, -OR SIG5.

Preferably R21represents a halogen atom (for example, fluorine/,1-4alkyl /for example butyl/or-or SIG5/for example, methoxy/.

Preferably R1represents an alkyl group with straight or branched chain containing up to four carbon atoms; or cyclopropylethyl group, possibly substituted by a group R4.

Preferred are also the compounds of formula I in which R represents hydrogen.

Another preferred class of compounds of formula I are those in which: Ar represents a Hairdryer is the place with two atoms, to which they are attached, form a 5 - or 6-membered ring selected from dioxolane, thiophene, thiophene S, S-dioxide, thiadiazole, oxazole, pyrrole and darsana, a ring which may be substituted with one or two groups R21that may be the same or different;

R represents a hydrogen atom; R1is cyclopropylethyl group; R2represents a halogen atom or a group selected from-SR5-THE SEPARATOR R S O5, SO2R5, -CH2S/O/pR5, R4and or SIG5;

R21represents a halogen atom (for example, fluorine/,1-4alkyl, -O2R5or-or SIG5;

R4is methyl;

R5represents methyl or ethyl; and

p=0,1 or 2 /preferably 2/.

The most important compounds include the following:

1. 5-cyclopropyl-4-/2,2-Diptera-7-methylsulfanyl-1,3-benzodioxol-4 oil/isoxazol;

2. 5-cyclopropyl-4-/2,2-Diptera-1,3-benzodioxol-4-oil/-isoxazol;

3. 5-cyclopropyl-4-/3,4-dimethoxybenzo[b]Tien-5-oil/-isoxazol;

4. 5-cyclopropyl-4-/benzo-1,2,3-thiadiazole-5-IOL/isoxazol:

5. 5-cyclopropyl-4-/2,2-Diptera-7-methylsulphonyl-1,3-benzodioxol-4 oil/isoxazol;

6. 5-cyclopropyl-4-/2,2-Diptera-4-methylsulphonyl-1,3-benzodioxane[b]Tien-5-oil/-5-cyclopropylethanol;

9. 5-cyclopropyl-4-/2,2-Diptera-4-methylsulfanyl-1,3-benzodioxol-5 oil/isoxazol;

10. 5-cyclopropyl-4-/2,2-Diptera-4-methylsulfanyl-1,3-benzodioxol-5 oil/isoxazol;

11. 5-cyclopropyl-4-[1-/methylsulphonyl/indole-4-carbonyl]isoxazol;

12. 5-cyclopropyl-4-/4-methyl-1,3-benzodioxol-5 oil/isoxazol;

13. 5-cyclopropyl-4-[4-/metalformer/-1,3-benzodioxol-5-oil] isoxazol;

14. 5-cyclopropyl-4-[2,2-Diptera-4-/metalformer/-1,3-benzodioxol-5 oil/isoxazol;

15. 5-cyclopropyl-4-4-/methylsulfanyl/-1,3-benzodioxol-5 oil/isoxazol;

16. 5-cyclopropyl-4-[3-ethoxy-4-/methylsulfanyl/bestien-5-oil]isoxazol;

17. 5-cyclopropyl-4-/4-chloro-3-ethoxy-2-ethylbenzo[b]Tien-5 oil/isoxazol;

18. 5-cyclopropyl-4-/4-chloro-3-ethoxybenzo[b]Tien-5 oil/isoxazol;

19. 5-cyclopropyl-4-[5-/methylsulphonyl/-1,4-benzodioxan-6-carbonyl] isoxazol;

20. 5-cyclopropyl-4-[4-/methylsulphonyl/-1,3-benzodioxol-5-oil] isoxazol;

21. 5-cyclopropyl-4-[5-/methylsulphonyl/-1,4-benzodioxan-6-carbonyl] isoxazol;

22. 5-cyclopropyl-4-[4-/methylsulfinyl/-1,3-benzodioxol-5-oil] isoxazol;

23. 5-cyclopropyl-4-/4-chloro-3-methoxybenzo[b] Tien-5 oil/isoxazol-1,1-dioxide;

24. 5-cyclopropyl-4-/3,4-dimethoxybenzo[b]Tien-5 oil/isoxazol-1,1-dioxi is 5-/methylsulfanyl/-1,4-benzodioxan-6-carbonyl] isoxazol; and

27. 5-cyclopropyl-4-/4-chloro-3-methoxy-2-methylbenzo[b]Tien-5 oil/isoxazol.

Numbers from 1 to 27 assigned to these compounds for links and further instructions.

The compounds of formula 1 can be obtained by application or adaptation of known methods, i.e. methods used so far and described in the literature/, for example, as described below.

It should be understood that the following process sequence may have a different order and that to obtain the desired compounds may be required suitable protective group.

In accordance with one of the features of the present invention the compounds of formula I in which R represents hydrogen, can be obtained by reaction of compounds of formula (II):

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where Ar and R1is as defined above and L is a leaving group, with a salt or hydroxylamine. Generally preferred hydroxylamine hydrochloride. L usually alkoxy, for example, ethoxy, or N, N-dialkylamino, for example N, N-dimethylamino. The reaction is usually carried out in a solvent such as ethanol or acetonitrile, in the presence of acceptor basic type or acid type, such as triethylamine or sodium acetate.

According to another characteristic of the present izopet the
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where R1as described above, and V represents a carboxy group or its reactive derivative /such as a carboxylic acid chloride or ester of carboxylic acid, or a cyano group with a metal-organic reagent of formula /IV/:

Ar - M, /IV/

where Ar is as defined above and M represents an alkaline metal, connected with one or more ligands or a group of the Grignard reagent. Better, if M is lithium or a group of Grignano containing magnesium. The reaction is usually conducted in an inert solvent, such as diethyl ether or tetrahydrofuran at temperatures between -78oC to the reflux temperature of the mixture.

In accordance with another characteristic of the invention the compounds of formula I, where R represents a group-CO2R3can be obtained by reaction of the compound of the formula /V/:

ArCOCH=C/P/R1/V/

where Ar and R1is as defined above and P is a leaving group, with a compound of formula R3O2CC/X/= NOH, where R3is as defined above and X is a halogen atom. Usually X is chlorine or bromine and R represents an N, N-dialkylamino. The reaction is usually conducted in an inert solvent, such as toluene or dichloromethane, or in the presence of a base such as triethylamine, or catalyst, such as mole which R represents a group-CO2R3can be obtained by reaction of compounds of formula /VI/:

ArCOC=R1/VI/

where Ar and R1is as defined above,

with the compound of the formula R3O2CC/X/=NOH, where R3and X is as defined above. The reaction is usually conducted in an inert solvent, such as toluene or dichloromethane is possible in the presence of a base such as triethylamine or catalyst such as molecular sieve 4 angstroms or fluoride ion. The reaction may be conducted at a temperature between room temperature and the temperature of phlegmasia mixture.

In accordance with another characteristic of the present invention the compounds of formula I where R is-CO2R3can be obtained by the reaction of salts of the compounds of formula /VII/:

ArCOCH2-COR1,

where Ar and R1is as defined above,

with the compound of the formula R3O2CC/X/=NOH, where R3and X is as defined above. Preferred salts include salts of sodium or magnesium. The reaction can be carried out in an inert solvent, such as dichloromethane or acetonitrile at a temperature of phlegmasia mixture.

According to another characteristic of the invention the compounds of formula I in which R represents hydrogen, can be obtained by reaction of the compound formusa. The reaction is usually conducted in the presence of a catalyst is a Lewis acid, such as trichloride aluminum in an inert solvent at a temperature of from 0oC to the temperature of phlegmasia mixture.

Intermediate compound in the formation of compounds of formula I can be obtained by application of known methods or their adaptation, for example, as described below.

The compounds of formula II, in which L is O-alkyl or N, N-dimethylamino, can be obtained by reaction of the corresponding compounds of formula /VII/ or trialkyl orthoformates, such as triethyl orthoformate or dialkylamino of dimethylformamide, such as dimethyl N, N - dimethylformamide acetal. Reaction with triethyl orthoformiate usually conducted in the presence of acetic anhydride at a temperature of reflux distilled mixture and reaction with N, N - dimethylformamide dialkyl acatalog can be carried out in the presence of an inert solvent at a temperature from room temperature up to the reflux temperature of the mixture.

The compounds of formula /V/ can be obtained by reaction of compounds of formula /IX/:

R1/R/C=CH2,

where R1and R is as defined above,

with an acid chloride of the formula /X/:

ArCOCL, /X/

where Ar is as defined above. The reaction is usually toluol or dichloromethane at a temperature between -20oC and room temperature.

The compounds of formula /VI/, you can get a replacement Metla hydrogen of the corresponding acetylene formula /XI/:

R1-C=CH,

where R1is as defined above,

with the subsequent reaction of the thus obtained metal salt with an acid chloride of the formula /X/. Replacement metal hydrogen is usually carried out using n-butyl lithium in an inert solvent such as ether or tetrahydrofuran at temperatures between -78oC and 0oC. Subsequent reaction with the acidic solvent is carried out in the same solvent at a temperature between -78oC and room temperature.

The compounds of formula /VII/ can be obtained by reaction of the ester of the formula /XII/:

Ar-CO2Z /XII/

where Ar is as defined above and Z is an alkyl group,

with a ketone of the formula

R1C/O/CH3,

in which R1is as defined above,

in the presence of a base. Commonly used base is sodium hydride and the reaction is carried out in an inert solvent at a temperature of from 0oC to phlegmasia.

The compounds of formula /VII/ can be obtained by reaction of compounds of formula /XIII/:

Ar-COCH3, /XIII/

where Ar is as defined above,

I Foundation. Preferably Z represents methyl, ethyl or t-butyl group. As the base is used usually, sodium hydride and the reaction is carried out in an inert solvent at a temperature of from 0oC to reflux.

The compounds of formula /VII/ can also be obtained by reaction of the acid chloride of the formula /X/ salt of the metal compounds of the formula /XIV/:

R1COCH2CO2TBU, /XIV/

where R1is as defined above, to obtain the connection formula /XV/:

Ar COCH/COR1/CO2TBU, /XV/

where Ar and R1is as defined above, which is decarboxylated to give a compound of the formula /VII/. Usually the reaction to obtain compounds of formula /XIV/ is carried out in a solvent such as a lower alcohol, preferably methanol, in the presence of metal, preferably magnesium. The decarboxylation is carried out by delegacia the compounds of formula /XV/ in the presence of a catalyst, such as para-toluensulfonate, in an inert solvent, for example toluene.

The compounds of formula /XIII/ known or can be obtained by application or adaptation of known methods. For example, the compounds of formula /XIII/ in which Ar represents a possibly substituted 1,2,3-benzothiadiazole, mo as defined above;

U is 0 or an integer from 1 to 3;

V represents hydrogen or a group which can be split during the cyclization. Better, if V is hydrogen or benzyl. The reaction preferably being conducted using an aqueous solution of nitrite in the presence of a strong acid, preferably Hydrobromic at a temperature of from 0oC to 20oC.

Intermediate compounds of formulas /III/, /IV/, /VIII/, /IX/, /X/, /XI/, /XII/, and /XVI/ known or can be obtained by application or adaptation of known methods.

Professionals it is clear that such compounds of formula I can be obtained by the mutual transformation of other compounds of formula I and such products are other features of the invention. Examples of such mutual transformations described below.

According to another characteristic of the present invention compounds in which R2and/or R21- -SOR5, -/CR910/t - SOR5or/CR910/t - SO2R5can be obtained by oxidation of the sulfur atom of the corresponding compounds in which R2and/or R21- -SR2, -SOR5, -/CR910/t - SR5or/CR910/t - SO2R5.

One further characteristic of the present invention compounds follenius the corresponding compounds of formula (I), in which the ring contains unoxidized sulfur atom. In both of these cases, the oxidation of the sulfur atom is usually performed using, for example, 3-chloroperoxybenzoic acid in an inert solvent such as dichloromethane at a temperature from -40oC to room temperature.

In accordance with another characteristic of the present invention compounds in which R2and/or R21is -/CR910/t - S/O/pR5where R5and R is as defined above, can be obtained by reaction of the corresponding compounds in which R2and/or R21substituted -/CR910/t-L1in which L1- halogen /preferably bromine with a compound of formula HS/O/pR5in which R5and R is as defined above. The reaction is usually conducted in a solvent such as tetrahydrofuran or ethanol, possibly in the presence of a base such as sodium hydride or sodium alkoxide /e.g. ethoxide sodium/, and at a temperature of from 0oC to the temperature phlegmy solvent.

Compounds in which R2and/or R21is -/CR910/t-L1where t - 1 can be obtained by reaction of the corresponding compounds in which R2and/or Ris cinimod/. If the halogenation agent is N - glowczewski, the reaction is usually conducted in an inert solvent such as carbon tetrachloride or dichloromethane with ultraviolet irradiation or a tungsten light at a temperature of from room temperature to the temperature of phlegmy solvent.

The compounds of formula I can be converted to agricultural acceptable salt by known methods or the application and adaptacja known methods.

The following examples illustrate the formation of compounds of formula I, and reference examples illustrate the production of intermediate compounds of the invention. In the present description because it means the boiling point; so pl. means melting point. NMR indicates the characteristic proton nuclear magnetic spectrum.

Example 1

A solution of 4-/3-cyclopropyl-2-dimethylaminomethylene-1,3-disopropyl/-2,2-Diptera-7-methylsulfanyl-1,3-benzodioxole /6.24 g/ and hydroxylamine hydrochloride /1.36 g/ was stirred overnight in ethanol. After cooling to -15oC precipitated solid was filtered and washed with cold ethanol. The filtrate is evaporated and chromatographically on silica gel with elution with elution by ethyl acetate/cyclohexane to obtain the P>o
C.

Thus were obtained the following compounds:

5-cyclopropyl-4-/2,2-Diptera-1,3-benzodioxol-4 oil/isoxazol/connection 2/ in the form of resin, NMR /ODCL3/1.3 /2N, m/ 1.4 /2N, m/, 2.8 /1H, m, 7.25 /2N, m/, 7.45 /1H, m, 8.35 /1H, s/.

5-cyclopropyl-4-[1-/methylsulphonyl/indole-4-carbonyl]isoxazol /connection 11/ in a solid green color, so pl. 142 - 144oC.

5-cyclopropyl-4-/4-methyl-1,3-benzodioxol-5 oil/isoxazol/the data connection 12/ in the form of a white solid substance, so pl. 124 - 126oC.

5-cyclopropyl-4-[4-/methylsulfonylmethyl/-1,3-benzodioxol-5-oil] isoxazol/connection 13/ in the form of a solid white color, so pl. 206 - 208oC.

5-cyclopropyl-4-[2,2-Diptera-4-/methylsulfonylmethyl/-1,3-benzodioxol-5-oil]isoxazol/connection 14/ in a solid yellow color, so pl. 180 - 181oC.

5-cyclopropyl-4-[4-/methylsulfanyl/-1,3-benzodioxol-5 oil/isoxazol/connection 15/ in the form of a yellow resin, NMR /CDCL3/1.2 /2N, m/ 1.3 /2N, m/ 2.4 /3H/, 2.7 /1H, m, 6.1 /2N,/, 6,8 /1H, d/, 7.0 /1H, d/, 8.2 /1H, s/.

5-cyclopropyl-4-[5-/methylsulfanyl/-1,4-benzodioxan-6-carbonyl] isoxazol/connection 26/ in the form of a cream solid color, so pl. 135 - 136oC.

Example 2

Dissolve is hydroxylamine /0.137 g/ was stirred for 15 minutes in ethanol. Was added sodium acetate /bezvadny, 0.161 g/ and the mixture was stirred for 4 hours to evaporate the ethanol and adding water. The mixture was extracted with ethyl acetate, dried /anhydrous magnesium sulfate/ and evaporated in vacuum. The residue was purified column chromatography on silica gel, was suirable ether /cyclohexane, to obtain 5-cyclopropyl-4-/3,4-dimethoxybenzo[b] Tien-5 oil/isoxazol/connection 3, 0.24 g/ in the form of oil, AMR.20 /2H, m/ 1.35 /2H, m/ 2.80 /1H, m, 3.84 /3H, c/, 4.00 /3H, c/, 6.39 /1H, c/, 7,40 /1H, d/, to 7.59 /1H, d/, 8.29 /1H, c/,

In a similar manner there were obtained the following compounds:

5-cyclopropyl-4-/benzo-1,2,3-thiadiazole-5-oil/isoxazol/connection 4/ in the form of a pale yellow oil, NMR/CDCL3/1.23 /2H, m, 3.4 /2H, m, 27.0 /1H, m, 8.07 /1H, d/, 8.17 /1H, d/, 8.40 /1H/, 8.96 /1H, d/.

5-cyclopropyl-4-[3-ethoxy-4-/methylsulfanyl/benzo[b]Tien-5 oil/isoxazol/connection 16/ as an orange resin, NMR/CDCL3/1.1 /2H, m/ 1.3 /2H, m/ 1.5 /2H, m, 2.4 /3H, c/, 2.5 /1H, m, 4.1 /2H, q/, 6.4 /1H, c/, 7.2 /1H, d/, 7.7 /1H, d/, 8.1 /1H, c/.

5-cyclopropyl-4-/4-chloro-3-ethoxy-2-ethylbenzo[b]Tien-5 oil/isoxazol/connection 17/ received in the form of orange resin, NMR/CDCL3/1.1 /2H, m/ 1.3 /5H, m/ 1.4 /3H, m/, 2,6 /1H, m, 2.9 /2H, q/, 3.9 /2H, q/, 7.1 /1H, d/, 7.6 /1H, d/, 8.1 /1H, c/.

5-cyclopropyl-4-/4-chloro-3-ethoxybenzo-[b]Tien-5 oil/isoxazol/connect, /.

5-cyclopropyl-4-/4-chloro-3-methoxy-2-methylbenzo[b]Tien-5 oil/isoxazol/connection 27/ resin yellow, NMR/CDCL3/1.2 /2H, m, 1.4 /2H, m/ 2.5 /3H, c/, 2.6 /1H, m/ 3.9 /3H, c/, 7.3 /1H, d/, 7.7 /1H, d/, 8.2 /1H, c/.

Example 3

A solution of 5-cyclopropyl-4-[2,2-Diptera-7-methylsulfanyl-1,3-benzodioxol-4 oil/isoxazol /0.64 g/ in dichloromethane was treated with m-chloroperbenzoic acid /55%, 1.5 g/. After 2 hours the mixture was cooled to 1oC was added a IM solution of metabisulfite sodium. The filtered solution was separated and the organic phase is washed with sodium acetate solution, brine, dried over anhydrous sodium sulfate and evaporated to obtain 5-cyclopropyl-4-[2,2-Diptera-7-methylsulfanyl-1,3-benzodioxol-4 oil/isoxazol/soedinenie 5, 0.35 g/ in the form of a solid white color, so pl. 164 - 165oC.

In a similar manner there were obtained the following compounds:

5-cyclopropyl-[5-/methylsulphonyl/-1,4-benzodioxan-6-carbonyl] isoxazol/connection 19/ in the form of a cream solid color, so pl. 174 - 175oC.

5-cyclopropyl-4-[4-/methylsulphonyl/-1,3-benzodioxol-5-oil] isoxazol/connection 20/ matter peach color, so pl. 178 - 180oC.

Example 4

A solution of 2-t-butyl-4-chloro-7-/3-the CSOs sodium acetate /0.73 g/ in ethanol was mixed for 2 hours. Water was added and the mixture was extracted with ether. The extract was washed with water, dried /magnesium sulfate/ and evaporated. Purification by chromatography on silica gel with elution with hexane/ethyl acetate gave 4-/2-t-chlorobenzoxazol-7-oil/-5-cyclopropylethanol/connection 7, 0.15 g/ in the form of a cream-colored substance, so pl. 166 -168oC.

In a similar manner there were obtained the following compounds:

4-/4-chloro-3-methoxybenzo[b]Tien-5-oil/-5-cyclopropylethanol/connection 8/, in the form of a yellow resin, NMR/CDCL3/1.23 /2H, m/ 1.34 /2H, m/ 267 /1H, m, 4.0 /3H/, 6.5 /1H/, 7.3 /1H, d/, 7.73 /1H, d/, 8.17 /1H/;

5-cyclopropyl-4-/2,2-Diptera-4-methylsulfanyl-1,3-benzodioxol-5 oil/isoxazol/connection 10/ as an orange resin, NMR/CDCL3/1.25 /2H, m/ 1.35 /2H, m/ 2.6 /3H/, 2.75 /1H, m/ 7.05 /1H, d/, 7.23 /1H, d/, 8.25 /1H, s/.

Example 5

A solution of 5-cyclopropyl-4-/2,2-Diptera-4-methylsulfanyl-1,3-benzodioxol-5 oil/isoxazol /1.0 g/ in dichloromethane was mixed with M=chloroperbenzoic acid /55%, 1.33 g/ 5 hours, then was washed in turn with a solution of metabisulfite sodium, saturated sodium bicarbonate solution and water. The solution was dried /magnesium sulfate) and evaporated to dryness and the residue was recrystallizes from toluene/cyclohexane to obtain 5-cyclopropene, so pl. 162 - 163oC.

In a similar manner there were obtained the following compounds:

5-cyclopropyl-4-/2,2-Diptera-4-methylsulphonyl-1,3-benzodioxol-5 oil/isoxazol/connection 9/ in the form of a solid substance, colorless, so pl. 162 - 164oC.

5-cyclopropyl-4-[5-/methylsulfinyl/-1,4-benzodioxan-6-carbonyl] isoxazol /connection 21/ in the form of a cream solid color, so pl. 135 - 136oC.

5-cyclopropyl-4-[4-/methylsulfinyl/-1,3-benzodioxol-5-oil] isoxazol /connection 22/ in the form of a cream solid color, so pl. 171 - 173oC.

Example 6 a Solution of 5-cyclopropyl-4-/4-chloro-3-methoxybenzo[b] Tien-5 oil/isoxazol/0.28 g/ in dichloromethane was processed m/chlorbenzoyl acid /55%, 0.72 g/. After 18 hours the mixture was cooled to -20oC, was filtered and was washed with 0.5 M sodium bisulfate and water, dried over anhydrous magnesium sulfate and evaporated. Purification by chromatography on silica gel with euromania cyclohexane/ether gave 5-cyclopropyl-4-/4-chloro-3-methoxybenzo[b] Tien-5 oil/isoxazol-1,1-dioxide /connection 23, 0.19 g/ in the form of a white solid substance, so pl. 215 - 217oC.

By analogy were obtained the following compounds: 5-cyclopropyl-4-/3,4-dimethoxybenzo[b] Tien-5 oil/isok the Il-4-/4-chloro-3-methoxy-2-methylbenzo[b]Tien-5 oil/isoxazol-1,1-dioxide /connection 25/ in the form of a white solid, so pl. 143 - 144oC.

Reference example 1

A solution of 4-/3-cyclopropyl-1,3-dioxolo-1-yl/-2,2-Diptera-1,3-benzodioxole /12.0 g/ dry toluene was treated with N, N - dimethylformamide dimethyl-acatalog and the mixture stirred overnight. After evaporation in vacuo and re-evaporated after addition of toluene, the residue was recrystallizes of cyclohexane-ethanol to obtain 4-/3-cyclopropyl-2-dimethylaminomethylene-1,3-disopropyl/-2,2-Diptera-1,3-benzodioxol /6.5 g/ in the form of a pale yellow solid, so pl. 118 - 119oC.

In a similar manner there were obtained the following compounds: 4-/3-cyclopropyl-2-dimethylaminomethylene-1,3-disopropyl/-2,2-Diptera-7-methylsulfanyl-1,3-benzodioxol as an orange resin.

4-/3-cyclopropyl/-2-dimethylaminomethylene-1,3-disopropyl/-1-methylsulfonylbenzoyl in the form of brown glass.

5-/3-cyclopropyl-2-dimethylaminomethylene-1,3-disopropyl/-4-methyl-1,3-benzodioxol in the form of a brown resin.

5-/3-cyclopropyl-2-dimethylaminomethylene-1,3-disopropyl/-4-/methylsulfonylmethyl/-1,3-benzodioxol in the form of a brown resin.

5-/3-cyclopropyl-2-dimethylaminomethylene-1,3-disopropyl/-2,2-Diptera-4-/methylsulfonylmethyl/-1,3-benzodioxol as ptx2">

5-/3-cyclopropyl-2-dimethylaminomethylene-1,3-disopropyl/-4-/methylsulphonyl/-1,3-benzodioxol in the form of an orange oil.

6-/3-cyclopropyl-2-dimethylaminomethylene-1,3-disopropyl/-1.4-benzodioxan as an orange resin.

Reference example 2

A solution of 4-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-2,2-Diptera-7-methylsulfanyl-1,3-benzodioxole /10.3 g/ and paratoluenesulfonyl /0.5 g/ was heated under reflux with toluene for 3 hours. After cooling, the solvent was evaporated in vacuum and was added ethyl acetate. The solution was washed with water, dried over anhydrous magnesium sulfate and evaporated. The residue was purified column chromatography, Eduardovna with ethyl acetate/cyclohexane to obtain 4-/3-vicoprofen-1,3-dioxolo-1-yl/-2,2-Diptera-7-methylsulfanyl-1,3-benzodioxol /6.61 g/ T. pl. 117.5 - 118.5oC.

In a similar manner there were obtained the following compounds 4-/3-cyclopropyl-1,3-dioxolo-1-yl/-2,2-Diptera-1,3-benzodioxol, so pl. 46 - 47oC. 2-t-butyl-4-chloro-7-/3-cyclopropyl-1,3-dioxolo-1-yl/benzoxazol in the form of a yellow oil, NMR /CDCL3/1.1 /2H, m/ 1.25 /2H, m/ 1.55 /9H, s/, 1.85 /1H, m/ 6.7 /1H/, 7.4 /1H, d/, 7.95 /1H, d/, 16.3 /1H, Shir.s/.

7-/3-cyclopropyl-1,3-disopropyl/-4-fluorescent-1,3-benzox is 16.2 /1H, Shir.s/.

5-/3-cyclopropyl-1,3-dioxolo-1-yl/-2,2-Diptera-4-methylsulfanyl-1,3-benzodioxol, NMR /CDCL3/1.05 /2H, m/ 1.25 /2H, m/ 1.75 /1H, m/ 2.05 /3H/, 6.0 /1H/, 7.0 /1H, d/, 7.45 /1H, d/, 16.3 /1H, Shir.s/.

4-chloro-5-/3-cyclopropyl-1,3-dioxolo-1-yl/-3-methoxybenzo[b] thiophene in the form of oil red, NMR /CDCL3/1.0 /2H, m/ 1.24 /2H, m/ 1.76 /1H, m/ 3.96 /3H/, 6.14 /1H/, 6.46 /1H/,7.46 /1H, d/, 7.66 /1H, d/, 15.9 /1H, Shir.s/.

2-t-butyl-4-methylsulfanyl-7-/3-cyclopropyl-1,3-dioxolo-1-yl/benzoxazol in the form of a yellow solid, NMR /CDCL3/1.05 /2H, m/ 1.25 /2H, m/ 1.57 /H,/, 1.88 /1H, m/ 2.67 /3H/, 6.70 /1H/, 7.16 /2H, d/, 7.92 /1H, d/.

4-chloro-5-/3-cyclopropyl-1,3-dioxolo-1-yl/-3-methoxy-2-methylbenzo[b] thiophene in the form of oil red, NMR /CDCL3/1.1 /2H, m/ 1.3 /2H, m/ 1.8 /1H, m/ 2.5 /3H, C/ a 3.9 /3H/, 6.1 /1H/, 7.4 /1H, d/, 7.6 /1H, d/, 16.0 /1H, Shir.s/.

4-chloro-5-/3-cyclopropyl-1,3-oxoprop-1-yl/-ethoxybenzo[b] thiophene as an orange resin, NMR /CDCL3/1.0 /2H, m, 1.2 /2H, m/ 1.5 /3H, t/, 1.7 /1H, m, 4.1 /2H, q/, 6.1 /1H/, 6.4 /1H/, 7.4 /1H, d/, 7.6 /1H, d/, 16.0 /1H, sh.s./; and 4-chloro-5-/3-cyclopropyl-1,3-dioxolo-1-yl/-3-ethoxy-2-ethylbenzo[b] thiophene as an orange resin, NMR /CDCL3/1.0 /2H, m, 1.2 /2H, m/ 1.3 /3H, t/, 1.4 /3H, t/, 1.7 /1H, m, 2.9 /2H, q/, 4.0 /2H, q/, 6.1 /1H/, 7.3 /1H, d/, 7.6 /1H, d/, 15.9 /1H, sh.s./, each of these compounds separately oxoprop-1-yl/3-ethoxy-4-/methylsulfanyl/benzo[b] thiophene as a yellow resin, NMR /CDCL3/1.0 /2H, m, 1.2 /2H, m/ 1.6 /3H, t/, 1.7 /1H, m/ 2.5 /3H, t/, 4.2 /2H, q/, 6.0 /1H/, 6.5 /1H/, 7.4 /1H, d/, 7.7 /1H, d/, 16.0 /1H, sh.s./,

4-/3-cyclopropyl-1,3-dioxolo-1-yl/-1-/methylsulfanyl/indole in the form of a solid brown color, NMR /CDCL3/1.0/2H, m/ 1.3 /2H, m/ 1.8 /1H, m/ 3.1 /3H/, 6.3 /1H/, 7.2 - 7.6 /3H, m/ 7.7 /1H, d/, 8.1 /1H, d/.

5-/3-cyclopropyl-1,3-disopropyl/-4-methyl-1,3-benzodioxol as an orange resin, NMR /CDCL3/0.9 /2H, m, 1.1 /2H, m, 1.7 /1H, m, 2.3 /3H/, 5.9 /1H/, 6.0 /2H,/, 6.6 /1H, d/, 7.1 /1H, d/.

5-/3-cyclopropyl-1,3-disopropyl/-4-/methylsulfonylmethyl/-1,3-benzodioxol in the form of a brown resin, NMR /CDCL3/ 1.0 /2H, m, 1.2 /2H, m, 1.7 /1H, m, 2.9 /3H/, 4.9 /2H,/, 6.10 /1H/, 6.12 /2H,/, 6.9 /1H/, 7.3 /1H, d/.

5-/3-cyclopropyl-1,3-disopropyl/-2,2-Diptera-4-/methylsulfonylmethyl/-1,3-benzodioxol as an orange resin, NMR /CDCL3/ 1.0 /2H, m/ 1.3 /2H, m, 1.7 /1H, m, 2.9 /3H/, 4.9 /2H,/, 6.1 /1H/, 7.2 /1H, d/, 7.5 /1H, d/.

5-/3-cyclopropyl-1,3-disopropyl/-4-/methylsulphonyl/-1,3-benzodioxol in the form of an orange oil, NMR /CDCL3/ 1.0 /2H, m, 1.2 /2H, m, 1.7 /1H, m/ 2.5 /3H/, 6.0 /1H/, 6.1 /2H,/, 6.7 /1H, d/, 7.1 /1H, d/.

6-/3-cyclopropyl-1,3-disopropyl/-5-/methylsulphonyl/-1,4-benzodioxan in the form of an orange oil, NMR /CDCL3/1.0 /2H, m, 1.2 /2H, m, 1.7 /1H, m, 2.4 /3H/, 4.3 /4H, m/ 6.0 /1H/, 6.9 /1H, d/, 7.1 /1H, d/.

In a similar way there were obtained the following compounds:

4-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-2,2-Diptera-1,3-benzodioxol.

2-t-butyl-4-chloro-7-/3-cyclopropyl/2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/benzoxazol.

7-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-4-fluorescent-1,3-benzoxazol-2-it.

5-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-2,2-Diptera-4-methylsulfanyl-1,3-benzodioxol.

4-chloro-5-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/benzoxazol.

4-chloro-5-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-3-methoxy-2-methylbenzo[b]thiophene.

A mixture of 4-chloro-5-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-3-ethoxybenzo[b] thiophene and 4-chloro-5-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-3-ethoxy-2-ethylbenzo[b]thiophene /obtained from the product of reference example 17/.

5-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-3-ethoxy-4-/methylsulfanyl/benzo[b]thiophene.

4-/3-cyclopropyl-1-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-1-/methylsulphonyl/indole.

5-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-4-methyl-1,3-benzodioxol.

5-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-4-/methylsulfonylmethyl/-1,3-benzodioxol.

5-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-2,2-Diptera-4-/methylsulfonylmethyl/-1,3-benzodioxol.

5-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-4-/methylsulfanyl/-1,3-benzodioxol.

6-/3-cyclopropyl-2-t-butyloxycarbonyl-1,3-dioxolo-1-yl/-5-/methylsulfanyl/-1,4-benzodioxan.

Reference example 4

2,2-Diptera-1,3-benzodioxol-4-carboxylic acid /15.0 g/ were dissolved in 1,2-dichloroethane was added N, N-dimethylformamid the E. The residue was dissolved in toluene and re-evaporated to obtain 2,2-Diptera-1,3-benzodioxol-4 oil chloride /17.35 g/.

Similarly, there was obtained 2,2-Diptera-7-methylsulfanyl-1,3-benzodioxol-4-oil-chloride.

Reference example 5

A solution of n-utility/88 ml of 2.5 M solution in hexane/ was diluted with dry hexane in an inert atmosphere, was cooled to 5oC and was added dropwise N, N, N, N - tetramethylethylenediamine /33 ml dry hexane. At -35oC was added dry tetrahydrofuran, and the mixture was cooled to -70oC, and within 1.5 hours with maintaining the temperature below -62oC was added 2,2-Diptera-1,3-benzodioxol-4-carboxylic acid. After 20 hours at -75oC for 30 minutes was added dimethyl disulfide /25 ml and the mixture is stirred at this temperature overnight and then at room temperature for 24 hours.

The mixture was poured into ice water, washed with ether and oxidized to pH 1 with concentrated hydrochloric acid. Then Ekstrand anhydrous magnesium sulfate. Evaporation of fastwrites gave 2,2-Diptera-7-methylsulfanyl-1,3-benzodioxol-4-carboxylic acid /17.75 g/NMR /D6DMCO/; 7,65 /1H, d/, 7,25 /1H, d/, 2,6 /3H, c/,

2,2 - Diptera-1.3 benzodioxol-4-carboxylic acid described is ethoxybenzo[b] thiophene /0.5 g/ and triethyl of orthoformate /0.73 g/ was heated under reflux with acetic anhydride /10ml/ 3 hours. After cooling and addition of toluene, the solution was evaporated to dryness to obtain 5-/3-cyclopropyl-2-ethoxymethylene-1,3-dioxolo-1-yl/-3,4-dimethoxybenzo[b]thiophene in the form of a red oil.

In a similar manner there were obtained the following compounds:

5-/3-cyclopropyl-2-ethoxymethylene-1,3-dioxolo-1-yl/benzo-1,2,3-thiadiazole.

2-t-butyl-4-chloro-7-/3-cyclopropyl-2-ethoxymethylene-1,3-dioxolo-1-yl/benzoxazol in the form of an orange oil.

5-/3-cyclopropyl-2-ethoxymethylene-1,3-dioxolo-1-yl/-2,2-Diptera-4-methylsulfanyl-1,3-benzodioxol.

4-chloro-5-/3-cyclopropyl-2-ethoxymethylene-2,3-voxopop-1-yl/-3-methoxybenzo[b]thiophene.

2-t-butyl-4-methylsulfanyl-7-/3-cyclopropyl-2-ethoxymethylene-1,3-dioxolo-1-yl/benzoxazol.

4-chloro-5-/3-cyclopropyl-2-ethoxymethylene-1,3-dioxolo-1-yl/-3-methoxy-2-methylbenzo[b]thiophene.

4-chloro-5-/3-cyclopropyl-2-ethoxymethylene-1,3-dioxolo-1-yl/-3-ethoxy-2-ethylbenzo[b]thiophene.

5-/3-cyclopropyl-2-ethoxymethylene-1,3-dioxolo-1-yl/-3-ethoxy-4-methylsulfonylbenzoyl[b]thiophene.

4-chloro-5-/3-cyclopropyl-2-ethoxymethylene-1,3-dioxolo-1-yl/-3-ethoxybenzo[b]thiophene.

Reference example 7

A solution of methyl 4-chloro-3-methoxybenzo[b]thio is bound atmosphere with warming to 50 - 60oC. for 3 hours at 50 -60oC was added cyclopropyl methyl ketone /2.59 g/ with stirring. After cooling, was carefully added isopropanol /5 ml/ s followed by the addition of water /5 ml/. The mixture was taken up in 2N hydrochloric acid and extracted with ether. The ether extracts were dried over anhydrous magnesium sulfate and evaporated in vacuum. The residue was purified column chromatography on siegele with elution with ether/cyclohexane to obtain 5-/3-cyclopropyl-1,3-dioxolo-1-yl/-3,4-dimethoxybenzo thiophene in the form of a solid yellow /1.47 g/, so pl. 77.5 - 80oC.

Similarly, there was obtained 5-/3-cyclopropyl-1,3-dioxolo-1-yl/benzo-1,2,3-thiadiazole in the form of a light orange substance, so pl. 141.5 - 144.5oC.

Reference example 8

A mixture of 4-chloro-3-hydrobenzo[b]thiophene-5-carboxylic acid /23.4 g/ cesium carbonate /70.07 g/, methyl iodide /50 ml/ Teather-n-butylammonium iodide /1.89 g/ was heated in acetone under reflux overnight. The solvent was evaporated and the residue was dissolved in ethyl acetate. The solution was washed with a saturated solution of sodium carbonate, water, dried over anhydrous magnesium sulfate and evaporated in vacuum. The residue was purified colonello-3-methoxybenzo[b]thiophene-5-carboxylate /8.35 g/ in the form of a pale yellow solid, so pl. 67 - 70oC and methyl 4-chloro-3-methoxy-2-methylbenzo[b] thiophene-5-carboxylate /3.4 g/ NMR /CDCL3/2.5 /3H, C/ a 3.9 /2H,/, 4.0 /3H/, 7.6 /2H,/.

Reference example 9

A mixture of dimethyl-4-chloro-3-hydroxybenzo[b]thiophene-2,5-in primary forms /12.62 g/ and 2N sodium hydroxide was heated under reflux for 2 hours. The mixture was kind of balanced out 2N hydrochloric acid at 100oC. the Solution was oxidized with concentrated hydrochloric acid was mixed in terms of phlegmasia another 30 minutes. Substance Magenta was filtered and dried /7.72 g/ in a desiccator, and this, as shown by analysis, was 4-chloro-3-hydrobenzo[b] thiophene-5-carboxylic acid, NMR /DMCOD6/6.67 /1H/, 7.54 /1H, d/, 7.87 /1H, d/, 10.3 /1H/, 13.34 /1H, with/ 4.07 /2H,/, 7.63 /1H, d/, 7.93 /1H, d/, 13.34 /1H, d/, /40% in the form of keto/.

Reference example 10

Dmutil-2,4-dichloroisatin /11.95 g/ and methyl thioglycolate /7.23 g/ were dissolved in N, N - dimethylformamide, and added the monohydrate of lithium hydroxide /3.81 g/. The mixture is stirred at ambient temperature for 2 hours, it was diluted with water and brought to pH 1 with hydrochloric acid. The solid was filtered, washed with boiling cyclohexane and dried by azeotropic removal of toluene to obtain dimethyl 4-chloro

Reference example 11

2,4-d sodium dichloro-3-methoxycarbonylmethylene /34.76 g/ stirred and heated under reflux with methanol for 15 hours. After cooling, the solvent was evaporated and the residue was recrystallizes from cyclohexane to obtain dimethyl 2,4-dichloroisatin /16.04 g/ in the form of a solid beige color, NMR /DMCOD6/3.87 /3H/, 3.94 /3H/, 7.74 /1H, d/, 7.94 /1H, d/.

Reference example 12

2,4-d sodium dichloro-3-methoxycarbonylbenzyl acid /32.37 g/ and thionyl chloride /100 ml/ heater under reflux with stirring for 3 hours. The mixture was cooled and evaporated in vacuo, then was re-evaporated after addition of toluene to obtain 2,4-d sodium dichloro-3-methoxycarbonylmethylene /34.76 g/ in the form of a dark brown oil. It was used in the next stage without purification.

Reference example 13

To a stirred solution of Diisopropylamine /22 ml/ dry tetrahydrofurane /160 ml) cooled to 0oC in an inert atmosphere was added dropwise n-butyl lithium /2.5 M, 67 ml/. The solution was mixed for 30 minutes at 0oC, then added to a solution of methyl 2,6-dichlorobenzoate /26.62 g/ dry tetrahydrofuran /160 ml) cooled to -78oC in an inert atmosphere. After 1.5 chalsa in vacuum and the residue was oxidized 3N hydrochloric acid. Then it was extracted with ethyl acetate, dried over anhydrous magnesium sulfate and evaporated in vacuum to obtain 2,4-d sodium dichloro-3-methoxycarbonylmethylene acid /32.37 g/ in the form of solids, NMR /DMCOD6/3.93 /3H/, 7.70 /1H, d/, 7.91 /1H, d/.

Reference example 14

A solution of Ethyl-3-amino-4-sensitivedata /6.11 g/ ethanol /20 ml was added to a vigorously stirred solution of sodium nitrite /3.23 g/ and 48% Hydrobromic acid /21 ml/ water /2500 ml/ cooled to 0oC. the Mixture was left to warm to room temperature overnight and was made basic with solid sodium carbonate /12 g/. The red precipitate was filtered, dissolved in ethyl acetate, dried over anhydrous magnesium sulfate and was evaporated to obtain ethyl benzo-1,2,3-thiadiazole-5-carboxylate /2.97 g/ as a red crystalline substance, so pl. 74.5 - 77oC.

Reference example 15

Ethyl-4-benzylthio-3-nitrobenzoate /10.16 g/ suspenderbelt in ethanol was mixed. Was added concentrated hydrochloric acid /60 ml/ s followed by the addition of portions of the iron powder /12.51 g/. The mixture Molino were warmed to 60 - 70oC and stirred overnight. After cooling, the mixture was poured n is connected by ethyl acetate and the filtrate was extracted with ethyl acetate. The extracts were dried over anhydrous magnesium sulfate and was evaporated to obtain ethyl-3-amino-4-antidiabetic /6.11 g/ in the form of an oil, NMR /CDCL3/1.37 /3H, t/, 3.97 /2H,/, 4.33 /2H, q/, 7.1 - 7.4 /8H/.

Reference example 16

Ethyl-4-benzylthio-3-nitrobenzoate /10 g/ and benzyl mercaptan /5.41 g/ were dissolved in N, N - dimethylformamide and stirring was added monohydrate of lithium hydroxide /1.83 g/. The mixture is stirred overnight, then poured into ether and 2N chlorotoluron acid. The organic phase was washed with water, dried over anhydrous magnesium sulfate and was evaporated to obtain ethyl 4-benzylthio-3-nitrobenzoate /10.16 g/; in the form of an oil, NMR /CDCL3/1.41 /3H, t/, 4.24 /2H,/, and 4.40 /2H, q/, 7.3 - 7.47 /5H/, 7.53 /1H, d/, 8.14 /1H, DD/, 8.86 /1H, q/.

Reference example 17

Stirred suspension of 4-fluorescent-1,3-benzoxazol-2-one-7-carboxylic acid /1.79 g/ dry dichloromethane was treated oxalyl chloride /0.97 g/ followed by the addition of N, N - dimethylformamide /3 drops/ to initiate the reaction. Stirring is continued under conditions of phlegmasia 1.5 hours and the mixture was evaporated to dryness to obtain 4-fluorescent-1,3-benzoxazol-2-one-7-carboxylic acid chloride used in the next step without purification.

Analogion in the form of an orange substance, used directly in the next stage.

2,2-Diptera-4-methylsulfanyl-1,3-benzodioxol-5-chloride - carboxylic acid, obtained in the form of semi-solid substances orange.

4-chloro-3-methoxybenzo[b]thiophene-5-chloride - carboxylic acid.

2-t-butyl-4-methylsulfonylbenzoyl-7-chloride - carboxylic acid.

4-chloro-3-methoxy-2-methylbenzo[b] thiophene-5-chloride - carboxylic acid in a solid yellow color.

A mixture of 4-chloro-3-ethoxybenzo[b]thiophene-5-carboxylic acid chloride and 4-chloro-3-methoxy-2-ethylbenzo[b] thiophene-5-chloride - carboxylic acid, obtained from the product of reference example 18.

3 ethoxy-4-methylsulfonylbenzoyl[b] thiophene-5-chloride - carboxylic acid as a brown liquid.

1-/methylsulphonyl/-4-carboxylic acid chloride in a solid yellow color.

4-methyl-1,3-benzodioxol-5-chloride - carboxylic acid as an orange solid.

4-/methylsulfonylmethyl/-1,3-benzodioxol-5-carboxylic acid chloride as a brown resin.

2,2-Diptera-4-/methylsulfonylmethyl/-1,3-benzodioxol-5-chloride - carboxylic acid as a yellow solid.

4-/METI/methylsulfanyl/-1,4-benzodioxan-6-carboxylic acid chloride as an orange oil.

4-fluorescent-1,3-benzoxazol-2-one-7-carboxylic acid described in Synthetie Communicat, 1990, 20, 1423 D. R. Peabill and S. K. Pichardson,

Reference example 18

A mixture of methyl 4-chloro-3-methoxybenzo[b]thiophene-5-chloride-carboxylate /8.35 g/ and hydrate of lithium hydroxide /1.37 g/ stirred in methanol /75 ml/ and water /25 ml at room temperature for 4 days. The methanol was evaporated in vacuum and the mixture was poured into an excess of cold dilute hydrochloric acid. The solid was filtered, washed with cold cyclohexane and dried to obtain 4-chloro-3-ethoxybenzo[b] thiophene-5-carboxylic acid chloride /7.28 g/ in the form of a white solid, NMR /D6D// 3.9 /3H/, 7.0 /1H/, 7.6 /1H, d/, 7.95 1H, d/ a, 13.3 /1H, Shir. s/.

In a similar manner there were obtained the following compounds 4-chloro-3-methoxy-2-methylbenzo[b] thiophene-5-carboxylic acid as a pale yellow solid, so pl. 185 - 192oC.

Thus was obtained the following compound: 2-t-butyl-4-methylsulfonylbenzoyl-7-carboxylic acid, so pl. 203 - 204oC using hydroida potassium instead of a hydrate of lithium hydroxide.

In a similar manner from the product of reference example 24 a mixture of ethyl-4-chloro-3-ethoxybenzo[b] thiophene-5-carboxylate the s was obtained a mixture of 4-chloro-3-ethoxybenzo[b]thiophene-5-carboxylic acid in the form of a solid white color.

The modified method was obtained 3-ataki-4-/methylsulfanyl/benzo[b] thiophene-5-carboxylic acid as a brown solid, NMR /CDCL3/1.6 /3H/, 2.6 /3H/, 4.2 /2N,q/, 6.5 /1H/, 7.8 /2N, m/, 8,2 /1H,d/.

Similarly, it was obtained the following compound:

1-/methylsulfanyl/indole-4-carboxylic acid in the form of a solid white color, so pl. 220 - 222oC using potassium hydroxide in industrial methylated spirits instead of hydrate of lithium hydroxide in methanol.

With a modification of the method was also obtained following link:

4-/methylsulfanyl/-1,3-benzodioxol-5 - carboxylic acid as an orange resin, NMR /CDCL3/2.7 /3H/, 4.9 /2N,/, 6.0 /2N,/, 6.7 /1H, d/, 7.6 /1H, d/.

Reference example 19

n-Utility /11.6 ml of 2.5 M solution in hexano/ added dropwise to peremeshivaemogo solution of 2,2-Diptera-1,3-benzodioxol-5-carboxylic acid /2.8 g/ dry tetrahydrofurane maintaining at -78oC in an inert atmosphere. Ambassador 6 hours at -78oC was added dropwise a solution of dimethyl disulfide /3.75 ml and the mixture was left overnight to reach room temperature. Was added a solution of sodium hydroxide /2M/, and the mixture was washed with ether, OK the axis, to obtain 2,2-Diptera-4-methylsulfanyl-1,3-benzodioxol-5-carboxylic acid /2.59 g/ in the form of a cream solid color. A pure sample was obtained as colorless crystals, so pl. 190 - 192oC by recrystallization from toluene/cyclohexane.

Thus were obtained the following compounds: 4-/methylsulfanyl/-1,3-benzodioxol-5-carboxylic acid in the form of a cream-colored substance, so pl. 196 - 198oC.

5-/methylsulfanyl/-1,4-benzodioxan-6-carboxylic acid in the form of a creamy substance, so pl. 122 - 124oC.

1.4-benzodioxan-6-carboxylic acid, as described in G. Coudert and other Tetrahedron Letters, 1978, 1059.

Reference example 20 n-Utility /101.6 ml of 2.5 M solution in hexane/ was added during 30 minutes to a stirred solution of 2,5-sodium dichloro-1-/dimethylacetamide/benzene /25.0 g/ dry tetrahydrofuran at -40oC and the solution stirred at -20oC 1.5 hours and poured onto solid carbon dioxide in dry tetrahydrofuran. The mixture had reached room temperature, was added a solution of sodium hydroxide 2M and was extracted with ethyl acetate. An aqueous solution of oxidized /concentrated hydrochloric acid and the precipitated solid was collected and dried to obtain 2-t - stirred mixture of 2,5-dichloraniline /15.0 g/, triethylamine /dry 14.1 ml/ and 4-dimethylaminopyridine /0.45 g/ dry dichloromethane /100 ml was added a solution of di-t-BUTYLCARBAMATE /22.2 g/ dry dichloromethane. The mixture was mixed in nitrogen for 18 hours and was extinguished by the addition of saturated solution of ammonium chloride and was extracted with dichloromethane. The extract was dried /magnesium sulfate) and evaporated and purified by chromatography on silica gel with elution with cyclohexane to obtain 2,5-sodium dichloro-1-/trimethylacetamido/benzene/12.2 g/ in the form of a cream substances used in the next step without further purification.

Reference example 22

A mixture of methyl 2-t-butyl-4-chloro-1,3-benzoxazol-7-carboxylate /5.7 g/ and timelocked sodium /1.64 g/ stirred at reflux for 48 hours in dry tetrahydrofuran. Water was added and the mixture was extracted /ether/, dried /anhydrous magnesium sulfate/ and evaporated. Purification by chromatography on silica gel gave methyl 2-t-butyl-4-methylsulfanyl-1,3-benzoxazol-7-carboxylate in the form of a creamy substance, NMR /CDCL3/1.53 /N,/, 2.64 /3H/, 3.98 /3H/, 7.09 /1H, d/, 7.85 /1H, d/.

In the same way there was obtained the following compound:

Ethyl-3-ethoxy-4-methylsulfonylbenzoyl[b]thiophene-5-carboxylate in>/P>Similarly in the reaction at room temperature were obtained the following compounds:

Methyl-4-/methysulfonylmethane/-1,3-benzodioxol-5-carboxylate as a yellow oil, NMR /CDCL3/2.1 /3H, C/ a 3.9 /3H/, 4.1 /2N,/, 6.7 /1H, d/, 7.6 /1H, d/.

Methyl-2,2-Diptera-4-/methysulfonylmethane/-1,3-benzodioxol-5-carboxylate in the form of a solid yellow color. so pl. 64 - 66oC.

Reference example 23 Oxalyl chloride was dropwise added /2.6 ml/ moved to a suspension of 2-t-butyl-4-chloro-1,3-benzoxazol-7-carboxylic acid /6.2 g/. Was added dry N, N-dimethylformamide /3 drops/ mixture stirred at reflux for 2 hours and evaporated. Was added dichloromethane and the solution was added dropwise to a mixed solution of methanol /dry, 3.0 ml/ triethylamine /dry, 10ml/ in dichloromethane at 0oC. After stirring at ambient temperature for 18 hours, the mixture was rinsed with water hydrochloric acid /2M/ sodium carbonate /2M/, then dried /magnesium sulfate/ and evaporated to obtain methyl 2-t-butyl-4-chloro-1,3-benzoxazol-7-carboxylate /5.7 g/ in the form of a solid light brown color. so pl. 130 - 131oC.

Similarly we have received the following with the l-5-carboxylate/ as an orange resin.

Methyl 2,2-Diptera-4-methyl-1,3-benzodioxol-5-carboxylate as an orange substance, so pl. 39 - 41oC.

Reference example 24

A mixture of 4-chloro-3-hydroxybenzo[b] thiophene-5-carboxylic acid /45.2 g/, cesium carbonate /135.4 g/, ethyl iodide /247 g/ and Tetra-n-butylammonium iodide /3.65 g/ was heated in acetonitrile under reflux for 18 hours. The solvent was evaporated and the residue was divided between acetate and water. The organic phase was washed with water three times, dried over anhydrous magnesium sulfate and evaporated in vacuum. The residue was purified column chromatography with elution by ethyl acetate/ petroleum ether, because 60 - 80oC obtaining approximately 5 : 1 mixture of 4-chloro-3-ethoxy-2-ethylbenzo[b]thiophene in the form of a solid yellow /23.04 g/.

Reference example 25

Sodium hydride /1.1 g of 80% dispersion in mineral oil, methyl 1H-indole-4-carboxylate /5.46 g/ and anhydrous acetonitrile were mixed in an inert atmosphere at 0oC and stirred at room temperature for one hour. Methanesulfonyl chloride /1.8 g/ was added at 0oC and the mixture stirred at room temperature for 18 hours. Then doublelist methanol and water and the mixture was extracted with dichloromethane. denim magnesium sulfate and evaporated in vacuum. The residue was purified column chromatography with elution by ethyl acetate/hexane to obtain methyl 1-/methylsulphonyl/indole-4-carboxylate /4.7 g/ in the form of a white substance, so pl. 102 - 104oC.

Methyl 1H-indole-4-carboxylate is described in A. R. zikowsky and other Journ of Organie Chew 1980, 45, 3350.

Reference example 26

A solution of n-utility /5.1 ml of 2.5 M solution in hexano/ was added to a stirred suspension of 1,3-benzodioxol-5-carboxylic acid /1.0 g/ in anhydrous tetrahydrofuran in an inert atmosphere, maintaining the temperature below -60oC. the mixture is Then stirred at -78oC 7hours and was added methyl iodide /0.50 g/ and the mixture is stirred at room temperature for 18 hours. Then the mixture was treated with water and 2N sodium hydroxide. The aqueous phase was washed with ether, oxidized and filtered. The solid was rinsed with hexane and dried to obtain 4-methyl-1,3-benzodioxol-5-carboxylic acid in the form of a cream-colored substance /0.91 g/, so pl. 217 - 219oC.

In the same way it was received and the following connection /2.2-Diptera-1,3-benzodioxol-5-carboxylic acid, which is described in U.S. patent 4895871/ 2,2-Diptera-4-methyl-1,3-benzodioxol-5-carboxylic acid in the form of a solid substance of agevolato /9.9 g/, N - bromosuccinic /9.6 g/ tetrachloride was irradiated with ultraviolet lamp with an average pressure of 500 watts for 6 hours at phlegmasia. The mixture was cooled to 0oC, filtered and the filtrate was evaporated to obtain an oil, which crystallized from toluene/hexane and was recrystallizations from cyclohexane to give methyl 4-bromomethyl-1,3-benzodioxol-5-carboxylate /3.0 g/ in the form of a beige solid. so pl. 95 - 98oC.

Similarly, it was obtained the following compound:

Methyl 4-bromomethyl-2,2-Diptera-1,3-benzodioxol-5-carboxylate in the form of a solid yellow color, so pl. 56 - 58oC.

Reference example 28

A mixture of methyl 4-/methysulfonylmethane/-1,3-benzodioxol-5-carboxylate /1.6 g/, m-chloroperbenzoic acid /55%, 4.6 g/ and dichloromethane were mixed for 24 hours and then were washed with a 10% solution of sodium metabisulfite, was saturated with sodium bicarbonate and water, dried over anhydrous magnesium sulfate and was evaporated to obtain methyl 4-/methylsulfonylmethyl/-1,3-benzodioxol-5-carboxylate as a yellow resin /1.5 g/ NMR /CDCL3/2.8 /3H/, 3.8 /3H/, 4.9 /2N,/, 6.1 /2N,/, 6.8 /1H, d/, 7.6 /1H, d/.

Reference example 29

A mixture of methyl 2,2-Diptera-4-/metasul gerousia suspension of sodium hydride /0.98 g of 80% dispersion in mineral oil/ tetrahydrofuran in an inert atmosphere. After two hours at a temperature of phlegmasia the reaction mixture was cooled and was added to the methanol /15 ml/. Then the mixture was added to saturated sodium bicarbonate and the organic phase was rinsed with dichloromethane and oxidized to pH 1 with concentrated hydrochloric acid. The precipitate was dried in vacuum to obtain 2,2-Diptera-4-/methylsulfonylmethyl/-1,3-benzodioxol-5-carboxylic acid /3.3 g/ in the form of a yellow substance, so pl. 107 - 109oC.

Reference example 30

35% hydrogen peroxide /3.1 ml was slowly added to a stirred solution of 2,2-Diptera-4-/methylsulfonylmethyl/-1,3-benzodioxol-5-carboxylic acid /3.3 g/ in glacial acetic acid at 0oC. the mixture is Then stirred at 50oC 18 hours, cooled and diluted with water, collecting the precipitate by filtration. Drying under vacuum gave 2,2-Diptera-4-/methylsulfonylmethyl/-1,3-benzodioxol-5-carboxylic acid /2.2 g/ in the form of a creamy substance, so pl. 185 - 186oC.

In accordance with one of the features of the present invention proposes a method of preventing growth of weeds /ie unwanted vegetation/ in the hearth, which includes applying to the hearth herbicide effective amount of at least one proizvodace used in the form of herbicide compositions /ie together with compatible diluents or carriers and/or surfactant /surfactant/ for use in herbicide compositions/, for example, as described below.

The compounds of formula 1 exhibit herbicide activity against monocotyledonous and dicotyledonous /ie broadleaf/ and monocots (for example, grass/ weeds use before and after germination.

The term "prior to germination" means the application to the soil in which the seeds or sprouts of weeds are about appearance above the soil surface. The term "after germination" means the application to open parts of the weeds that have emerged above the soil surface. For example, the compounds of formula I can be used to combat the growth:

broadleaf weeds, for example, Abutilon theophrasti, Amaraufhus refroflexus, Bidens pilosa, Chenopodium album, Galium aparine, Jpomoca, e.g. Jpomoca purpurea, Sesbama exaltafa, Sinapis arvensis, Solanum nigrum n Xanthium Sfrumarium and grassy weeds, for example. Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinjchloa crus-galli, Eleusine indica and Setaria. spp, for example, Setariafaberii or Setaria viridis and sedges, for example, Cyperus esculenfus. The number is used in such compounds of formula I will depend on the nature of the weeds, the compositions used, time of application, the climatic and soil conditions and/is a change should be sufficient to control the growth of weeds without causing permanent damage to the culture. In General, given these factors, good results dosage of between 0.01 kg and 5 kg of active material per hectare. However, it should be understood that it is possible to use higher or lower concentrations depending on the particular case.

The compounds of formula I can be used to combat selective for example, struggle with the growth of those species mentioned previously, the use of before or after germination, directly or indirectly; for example, direct or indirect irrigation nidus of infection, which is an area used, or predpolagaemoi to use for growing crops, for example, zhrnovih, wheat, oats, barley, corn and rice, soybeans, field and dwarf beans, peas, alfalfa, cotton, flax, onions, carrots, cabbage, canola, sunflowers, sugar beet and permanent or sown pastures before or after sowing of the crops before or after emergence of the crop. For selective weed control in the focus of infection weeds in the fields for growing crops, for example, those mentioned above, are usually acceptable dosage applied between 0.01 kg and 4.0 kg, preferably between 0.01 kg and 2.0 kg aktio or after germination in groves and other trees grow, for example, forests, parks and plantations such as sugar plantations, palm and rubber plantations. For this purpose and can be applied directly or indirectly to the weed or the soil in which they are located before or after the kept trees or plantations with a dosage of between 0.25 kg and 5.0 kg, and preferably between 0.5 kg and 4.0 kg of active material per hectare.

The compounds of formula I can be used to control weeds listed above in centers that are not fields for growing crops, but where the need to control the growth of weeds.

Examples of such lesions are airports, industrial areas, Railways, roadsides, slopes, rivers, irrigation and other water plants, shrubs, empty or rekultivirovanie land, particularly where it is desirable to control weeds, to reduce the risk of fires. For such purposes, when necessary full herbicide effect, the active compounds are used with a dosage higher than for field crops. The exact dosage will depend on the nature of the vegetation and the desired effect.

For this purpose the application before or after germination direct or indirect way, and it is better to germination requires dosiro the growth of weeds until germination of the compounds of formula I can be introduced into the soil. When using compounds of formula I in the fight against the growth of weeds after germination, i.e. the use of the open parts of the weeds, the compounds of formula (I usually come in contact with the soil and can then control the weeds that appear later.

If you want a longer control the use of compounds of formula I can be repeated if desired.

In accordance with another characteristic of the invention provides a composition for herbicide use, including one or more isoxazol derivative of the formula I or their agricultural-acceptable salt, together with-and better dispersed uniformly in one or more compatible agricultural acceptable diluents or carriers and/or surfactants /i.e. diluents or carriers and/or carriers and/or surfactants of the type commonly used in this area for herbicide compositions and which are compatible with compounds of the formula I/. The term "homogeneously dispersed" includes compositions in which the compounds of formula I dissolved in other components. The term "herbicide composition is used in a broad sense, and includes not only compositions which are ready for use as herbicides, as well as the 5 to 90% by weight of one or more compounds of formula I.

Herbicide compositions may contain a diluent or carrier, and surfactants /for example, wetting, dispersing or emulsifying/. Surface-active agents that may be present in the herbicide compositions of the present invention may be ionic or non-ionic type, for example, sulfonylureas, derivatives of Quaternary ammonium, products based on condensates of ethylene oxide with alkylamine or Polyarylamide phenols, for example, nonyl or octyl-phenol, or ether carboxylic acid anhydromannitol, which are made soluble by etherification of the free hydroxy groups by condensation of ethylene oxide, salts of alkaline and alkaline earth metal derivatives of sulfonic acids with high molecular weight, such as sodium lignosulfonate and calcium and alkylbenzenesulfonate sodium and calcium.

Herbicide composition according to the invention can include up to 10% by weight, for example from 0.05 to 10% by weight surfactant, but if you want a valid and higher proportions of surfactants, for example, up to 15% by weight in the liquid emulsion suspension concentrates and up to 25% by weight in liquid water soluble concentrates.

Examples of suitable solid diluents or carriers are aluminium silicate which I soot and clay, such as kaolin and bentonite, Solid compositions which can take the form of Farrukh Dustov, granules or wettable powders/ prepared by grinding the compounds of formula I with solid diluents or by saturation of the solid diluents or carriers with solutions of compounds of the formula I in volatile solvents and, if desired, by grinding products to powders. Granular forms can be prepared by absorption of the compound of formula I is /are dissolved in suitable solvents, which, if desired, can be volatile/ solid diluents or carriers in granular form and, if desired, by evaporation of the solvents, or by granulating compositions in powder obtained as described above. Solid herbicide compounds, in particular, wettable powders and granules may contain a wetting or dispersing agents, for example, of the types described above which in the solid state can serve as diluents or carriers.

Liquid compositions according to the invention can take the form of aqueous, organic or aqueous-organic solutions, suspensions and emulsions which may include surfactants. Suitable liquid diluents for inclusion in liquid compositions include water, glycols, tetrahydrofurfuryl the light of aromatic and naphthenic fractions of oil and mixtures of these diluents/. Surfactants that may be present in the liquid composition may be ionic or non-ionic /for example, of the types described above and the liquid state can serve as diluents or carriers.

Powders, dispersible granules and liquid compositions in the form of concentrates can be diluted with water or other suitable diluents, for example, mineral or vegetable oils, especially in the case of liquid concentrates, in which the diluent or carrier is an oil, to obtain a composition ready for use.

If desired, liquid compositions of the compounds of formula I can be used in the form of self-mulgirigala concentrates containing the active substances dissolved in the emulsifying agents or in solvents containing emulsifying agents compatible with the active substances, the simple addition of water to such concentrates makes the composition is ready for use.

Liquid concentrates, in which the diluent or carrier is an oil, can be used without further dilution using the technique of electrostatic spraying.

Herbicide composition according to the invention can also contain conventional adjuvants, t the agents, dyes and corrosion inhibitors. These adjuvants can also serve as carriers or diluents.

Unless otherwise stated, percentages are given by weight. Preferred herbicide compositions according to the invention are:

aqueous suspension concentrates which comprise from 10 to 70% of one or more compounds of the formula I, from 2 to 10% surfactant, from 0.1 to 5% of thickener and from 15 to 87.9% water;

Wettable powders which comprise from 10 to 90% of one or more compounds of the formula I, from 2 to 10% surfactant, and from 8 to 88% of solid diluent or carrier;

water-soluble or photodisplaytype powders, which contain from 10 to 90% of one or more compounds of the formula I, from 2 to 40% of sodium carbonate and from 0 to 88% of solid diluent:

liquid water soluble concentrates which comprise from 5 to 50%, for example, 10 to 30%, of one or more compounds of the formula I, from 5 to 25% surfactant and from 25 to 90%, for example, 45 to 85%, of water-miscible solvent, such as dimethylformamide, or a mixture of water mixed from solvent and water;

liquid emulsion suspension concentrates which comprise from 10 to 70% of one or more compounds of the formula I, 5 to 15% of surfactants, from 0.1 to 5% of thickener and from 10 to 84.9% organics formula I, from 0.5 to 7%, for example 0.5 - 2 surfactant, and from 3 to 98.5%, for example 88 - 97.5%, granular media and

emulsion concentrates, which contain 0.05 to 90%, and preferably from 1 to 10% surfactant and from 9.99 to 99.94%, better from 39 to 98.99% organic solvent.

Herbicide compositions of the present invention can also contain compounds of formula I together - and it is better to be dispergirovannykh in one or more other pesticide active compounds and, if desired, one or more pesticide acceptable diluents or carriers, surfactants and traditional adjuvant, as described above. Examples of other pesticide active compounds that can be included or used together with the herbicide compositions of the present invention include herbicides, for example to increase the range of weeds controlled, - alachlor [2-chloro-2.6'-diethyl-N-/methoxy-methyl-acetanilide] , atrazine[2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine] , bromoxynil[3,5-dibromo-4-hydroxybenzonitrile], chlortoluron[N'-/3-chloro-4-were/-N, N] -dimethyloxetane, cyanazine[2-chloro-4-/1-cyano-1-methylethylamine/-6-ethylamino-1,3,5-triazine], 2,5-D[2,4-dichlorophenoxy-acetic acid] , dicamba[3,6-sodium dichloro-2-methoxybenzoic acid] , difenzoquat[1,2-Diuron [N'-/3-trifluromethyl/-N, N-demethylation], Isoproturon [N'-/4-isopropylphenyl/-N, N - dimethylation] , insecticides such as synthetic pyrethroids, such as permethrin and cypermethrin and fungicides, for example, carbamates, for example, methyl N-/1-t-butyl-carbarnoyl-benzimidazole-2-yl/carbamate, and triazoles, for example, 1-/4-chloro-phenoxy/-3,3-dimethyl-1-/1,2,4-triazole-1-yl-butane-2-on.

Pesticide active compounds and other biologically active materials which may be included or used in conjunction with herbicide compounds of the present invention, for example, those mentioned above can be applied in the form of a traditional derivatives, for example, salts and esters of alkali metals and amines.

The following examples illustrate herbicide compositions in accordance with the present invention:

Example C1

Soluble concentrate is prepared from:

Active ingredient /compound 1/ - 20% weight/vol.

Solution of potassium hydroxide - 10% weight/vol.

Tetrahydrofurfuryl alcohol /TGPS/ - 10% weight/vol.

Water to 100 volumes

mixing TGFS, active ingredient /compound 1/ and 90% of the volume of water and slowly adding a solution of potassium hydroxide to obtain stabilin is arranged as described above, replacement isoxazol /connection 1/ other compounds of formula I.

Example C2

Wettable powder is prepared from:

Active ingredient /compound 1/ - 50% weight/weight

Sodium dodecylbenzene sulfonate - 3% weight/weight

Of sodium lignosulphonate 5% weight/weight

Sodium formaldehyde alkylnaphthalene sulfonate - 2% weight/weight

Crushed silicon dioxide - 3% weight/weight

China clay - 37 % weight/weight

mix these ingredients together powders can be prepared as described above by replacing isoxazol /connection 1/ other compounds of formula I.

Example C3

Water-soluble powder is prepared from:

Active ingredient /compound 1/ - 50% weight/weight

Dodecylbenzenesulfonate sodium - 1 % weight/weight

Crushed silica - 2% weight/weight

Sodium bicarbonate - 47% weight/weight

mix the above and gradients, and grinding this mixture in a hammer mill.

Similar water-soluble powders can be obtained as described above by replacing isoxazol /connection 1/ other compounds of formula I.

The compounds of formula I, presented here, was used as herbicides in accordance with the following procedures is icesta compounds, used for treatment of plants, was dissolved in acetone to obtain solutions of equivalent doses of applications up to 4000 g testremove connections per hectare /year/ha/. These solutions were applied from standard laboratory sprayer with the equivalent of 290 liters of spray fluid per hectare.

in/ weed Control: to shoots

The change was sown in 70 mm square, with a depth of 75 mm plastic pots of sterile soil. The number of seeds per pot was as follows: (see table.1)

Compounds of the invention was applied to the surface of the soil containing the seeds, as described in /a/. One pot of each culture and each weed was subjected to each treatment, were also in control plants without treatment and treated only one with acetone.

After treatment, the pots were placed on capillary Mat in a glass-enclosed greenhouse and watered from above. Visual assessment of crop damage was done after 20 to 24 days after spraying. The results were expressed in percentage reduction in the growth of or damage to crops or weeds in comparison with the control pots.

with/ Control of weeds: after shoots

Weeds and crops were sown directly in whom the AI sprout in a pot for a week before spraying. Plants were grown in the greenhouse. The number of plants per pot was as follows: (see table.2)

The compounds used for the processing plant has changed to the plants, as described in /a/. Each treatment was subjected to one pot of each crop and type of weed control plants were without processing plants that were sprayed only acetone.

After treatment, the pots were placed on capillary Mat in a greenhouse and watered from above once in 24 hours and then controlled irrigation under the ground. Visual assessment of damage to crops and weeds was conducted from 20 to 24 days after spraying. The results were expressed in percentage as the reduction in growth or damage crops or weeds in comparison with the plants in the control pots.

When applied before or after germination at the dosage of 4 kg/ha or less, the connection 1 - 27 provide control at least 90% of one or more weed species and showed selectivity for at least one crop species.

1. Derived isoxazol formula I

< / BR>
where Ar is phenyl, substituted by one to three groups R2and where two of the substituents on adjacent positions of the phenyl ring instead of the or two heteroatoms, selected from O, S and N, which may be substituted by one or more groups R21,

R represents a hydrogen atom;

R1is cycloalkyl group containing from three to six carbon atoms;

R2may be the same or different, represent a halogen atom, alkyl group with straight or branched chain, containing from one to six carbon atoms which may be optionally substituted by one or more halogen, a group selected from-SR5, -SOR5, -SO2R5, -OR5, -(CR9R10)t-S(O)pR5;

R21may be the same or different, represent R2or = 0;

R5represents alkyl straight or branched chain containing up to six carbon atoms;

R9and R10each represents a hydrogen atom;

p is 0, 1 or 2;

t = 1,

or agricultural acceptable salt.

2. Connection on p. 1, in which Ar represents a possibly substituted 1,3-benzodioxole, benzo[b]thiophene, benzoxazole or benzo - 1,2,3-thiadiazole.

3. Connection under item 1 or 2, characterized in that: (a) R2located in the C-2 position of the phenyl ring, when condensation takes place € place at C-2 and C-3 of the ring.

4. Connection on p. 1, 2 or 3, in which R2is a halogen atom or a group selected from-SR5, -SOR5, -OR5, -SO2R5where R5- as defined in paragraph 1.

5. The compound according to any one of paragraphs.1-4, wherein R21is a halogen atom C1-4the alkyl or-OR5and R5- as defined in paragraph 1.

6. Connection on p. 5, wherein R21represents fluorine, t-butyl or methoxy.

7. The compound according to any one of paragraphs.1-6, in which R1is cyclopropyl group.

8. The compound according to any one of paragraphs.1-7, where R1is cyclopropyl group, and R2represents halogen.

9. Connection on p. 1, where Ar is phenyl, optionally substituted by a group R2and where two of the substituents on adjacent positions of the phenyl ring together with the two atoms to which they are attached, form a 5 - or 6-membered ring selected from dioxolane, thiophene, thiophene-S, S-dioxide, thiadiazole, oxazole, pyrrole and dioxane, and the ring optionally substituted by one or two groups R21that may be the same or different;

R1is cyclopropyl group;

R2represents the atom UP>;

R21represents a halogen atom, a C1-4alkyl, SO2R5or5,

R5represents methyl or ethyl;

p = 0, 1, or 2.

10. Connection on p. 1, which is:

5-cyclopropyl-4-/2,2-Diptera-7-methylsulfanyl-1,3-benzodioxol-4 oil/ isoxazol;

5-cyclopropyl-4-/2,2-Diptera-1,3-benzodioxol-4 oil/ isoxazol;

5-cyclopropyl-4-/3,4-dimethoxybenzo/b/ Tien-5 oil/ isoxazol;

5-cyclopropyl-4-/benzo-1,2,3-thiadiazole-5-oil/isoxazol;

5-cyclopropyl-4-/2,2-Diptera-7-methylsulphonyl-1,3-benzodioxol-4 oil/isoxazol;

5-cyclopropyl-4-/2,2-Diptera-4-methylsulphonyl/-1,3-benzodioxol-5 oil/isoxazol;

4-/2-t-butyl-4-chlorobenzoxazol-7-oil/-5-cyclopropylethanol;

4-/4-chloro-3-methoxybenzo/b/Tien-5-oil/-cyclopropylethanol;

5-cyclopropyl-4-/2,2-Diptera-4-methylsulfanyl-1,3-benzodioxol-5 oil/isoxazol;

5-cyclopropyl-4-/2,2-Diptera-4-methylsulfanyl-1,3-benzodioxol-5 oil/isoxazol;

5-cyclopropyl-4-/1-/methylsulphonyl/indole-4-charboil/isoxazol;

5-cyclopropyl-4-/4-methyl-1,3-benzodioxol-5 oil/isoxazol;

5-cyclopropyl-4-/4-/methanesulfonyl-1,3-benzodioxol-5 oil/ isoxazol;

5-cyclopropyl-4-/2,2-Diptera-4-/methysulfonylmethane/-1,3-benzodioxol-5-ooxy-4-/methylsulfanyl/benzo[b] Tien-5 oil/ isoxazol;

5-cyclopropyl-4-/4-chloro-3-ethoxy-2-ethylbenzo/b/Tien-5 oil/isoxazol;

5-cyclopropyl-4-/4-chloro-3-ethoxybenzo/b/Tien-5-oil/-isoxazol;

5-cyclopropyl-4-/2,3-dihydro-5-/methylsulphonyl/-1,3-benzodioxol-5 oil/isoxazol;

5-cyclopropyl-4-/4-/methylsulphonyl/-1,3-benzodioxol-5 oil/isoxazol;

5-cyclopropyl-4-/5-/methylsulfinyl/-1,4-benzodioxan-6-carbonyl/isoxazol;

5-cyclopropyl-4-/4-/methylsulfinyl/-1,3-benzodioxol-5 oil/isoxazol;

5-cyclopropyl-4-/4-chloro-3-methoxybenzo[b] Tien-5 oil/isoxazol-1,1-dioxide;

5-cyclopropyl-4-/3,4-dimethoxybenzo[b]Tien-5 oil/isoxazol-1,1-dioxide;

5-cyclopropyl-4-/4-chloro-3-methoxy-2-methylbenzo[b]Tien-5 oil/isoxazol-1,1-dioxide;

5-cyclopropyl-4-/5-/methylsulfanyl/-1,4-benzodioxan-6-carbonyl/isoxazol; or

5-cyclopropyl-4-/4-chloro-3-methoxy-2-methylbenzo[b]Tien-5 oil/isoxazol.

11. Herbicide composition comprising the active ingredient is derived and agricultural isoxazol acceptable diluent or carrier and/or surface-active agent, characterized in that the quality of the derived isoxazol it contains a compound of the formula (I) as defined in any of paragraphs. 1 - 10, or agricultural acceptable salt herbicide-effective the shock, water-soluble powder, liquid, soluble concentrate,

13. Method of preventing growth of weeds in the hearth, which includes the use of derivative isoxazol, characterized in that the quality of the derived isoxazol used as a compound of formula (I) as defined in any of paragraphs.1 - 10, or agricultural acceptable salt herbicide effective amount.

14. The method of obtaining the derived isoxazol formula (I), as defined in paragraph 1, including the interaction of the compounds of formula (II):

< / BR>
where Ar and R1as defined in paragraph 1, and L is a leaving group,

with a salt of hydroxylamine.

15. The method of obtaining the derived isoxazol formula (I), as defined in paragraph 1, which contains oxidized sulfur atom, SO or SO2that includes oxidation of the corresponding compounds of formula (I), which contains unoxidized sulfur atom.

 

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The invention relates to new derivatives of 4-benzoimidazole formula I where R is hydrogen or-CO2R4; R1- C3-6-cycloalkyl; R2- halogen, n-alkyl, possibly substituted by one or more halogen atoms, or5, -S(O)pR6; R3IS-S(O)qR7; X IS -(CR9R10)t-; n = 0, 1, and 2; when n is greater than 1, the groups R2may be the same or different; R4, R5and R6-n-alkyl; R7-n-alkyl, possibly substituted by one or more atoms of hydrogen, C3-C6alkenyl straight chain or phenyl; R9and R10is hydrogen or C1-C6-alkyl straight chain; p and q = 0, 1, or 2; t is an integer from 1 to 4, when t > 1, group-CR9R10may be the same or different; or acceptable for agriculture salt

The invention relates to new derivatives of 4-benzoimidazole, containing compositions, methods for their preparation, intermediate substances for their preparation and their use as herbicides

The invention relates to new derivatives of 4-benzoimidazole, to compositions containing them, to processes for their preparation, intermediate compounds for their production and to their use as germicidal

The invention relates to derivatives of 5-aryl-isoxazol of, compositions containing them, methods for their preparation and their use as herbicides

The invention relates to new derivatives of 4-benzoimidazole formula I where R is hydrogen or-CO2R4; R1- C3-6-cycloalkyl; R2- halogen, n-alkyl, possibly substituted by one or more halogen atoms, or5, -S(O)pR6; R3IS-S(O)qR7; X IS -(CR9R10)t-; n = 0, 1, and 2; when n is greater than 1, the groups R2may be the same or different; R4, R5and R6-n-alkyl; R7-n-alkyl, possibly substituted by one or more atoms of hydrogen, C3-C6alkenyl straight chain or phenyl; R9and R10is hydrogen or C1-C6-alkyl straight chain; p and q = 0, 1, or 2; t is an integer from 1 to 4, when t > 1, group-CR9R10may be the same or different; or acceptable for agriculture salt

The invention relates to new derivatives of 4-benzoimidazole, containing compositions, methods for their preparation, intermediate substances for their preparation and their use as herbicides

The invention relates to a new simple cyclohexanehexol esters and herbicide compositions on their basis

The invention relates to new derivatives of 4-benzoimidazole, compositions containing them and their use as herbicides

The invention relates to new derivatives of 4-benzoimidazole, to compositions containing them, to processes for their preparation, intermediate compounds for their production and to their use as germicidal

The invention relates to derivatives of 4-benzoimidazole, compositions containing these derivatives, and their use as herbicides

The invention relates to the following compounds:

A) 4-(4-chloro-2-methylsulfonylbenzoyl)-5-cyclopropylmethoxy;

C) 5-cyclopropyl-4-(2-methylsulphonyl-4-trifloromethyl)- isoxazol; and

C) 4-(4-bromo-2-methylsulfonylbenzoyl)-5-cyclopropylmethoxy

The invention relates to derivatives of 5-aryl-isoxazol of, compositions containing them, methods for their preparation and their use as herbicides

The invention relates to cyclic Amida substituted in-the position of different aryl groups, agricultural suitable salts and their mixtures, and their use as fungicides systemic or selective action

The invention relates to new derivatives of 4-benzoimidazole formula I where R is hydrogen or-CO2R4; R1- C3-6-cycloalkyl; R2- halogen, n-alkyl, possibly substituted by one or more halogen atoms, or5, -S(O)pR6; R3IS-S(O)qR7; X IS -(CR9R10)t-; n = 0, 1, and 2; when n is greater than 1, the groups R2may be the same or different; R4, R5and R6-n-alkyl; R7-n-alkyl, possibly substituted by one or more atoms of hydrogen, C3-C6alkenyl straight chain or phenyl; R9and R10is hydrogen or C1-C6-alkyl straight chain; p and q = 0, 1, or 2; t is an integer from 1 to 4, when t > 1, group-CR9R10may be the same or different; or acceptable for agriculture salt

The invention relates to new derivatives of 4-benzoimidazole, containing compositions, methods for their preparation, intermediate substances for their preparation and their use as herbicides

The invention relates to a new simple cyclohexanehexol esters and herbicide compositions on their basis

The invention relates to new derivatives of 4-benzoimidazole, compositions containing them and their use as herbicides

The invention relates to new derivatives of 4-benzoimidazole, to compositions containing them, to processes for their preparation, intermediate compounds for their production and to their use as germicidal
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