KR810001277B1 - Process for the preparation of phenylthio-carbamoil alkylcarbaminate derivatives - Google Patents

Abstract

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Description

Process for the preparation of phenylthio carbamoyl alkyl carbamate derivatives

The present invention relates to the preparation of phenylthionocarbamoyl alkylcarbamate derivatives.

The present invention provides a compound of formula (2)

Wherein R ₁ is an alkyl group having 1 to 4 carbon atoms, R ₂ and R ₃ are each different from each other and hydrogen or alkoxy having 1 to 4 halogens, alkyl having 1 to 4 carbon atoms or trifluoromethyl or cyano group and X Is —O—SO ₂ or SO ₂ —O.

The compound of formula (2) has an antiparasitic activity.

These are useful as precursors for the preparation of 3-alkoxycarbonylamino-1 H-2,1,4-benzothiadiazine derivatives of the general formula (1) described in the parent application No. 1501 of the present application.

In the above structural formula, R ₁ , R ₂ , R ₃ and X are as described above, R ₄ is hydrogen, acyl or benzoyl group having 2 to 4 carbon atoms and n is an integer of 0 to 1.

Alkyl groups represented by R ₁ , R ₂ and / or R ₃ are, for example, methyl, ethyl, propyl, isopropyl, butyl, secondary butyl and tertiary butyl.

Alkoxy groups represented by R ₂ and / or R ₃ are, for example, methoxy, ethoxy, propoxy, isopropoxy and butoxy.

Halogens represented by R ₂ and / or R ₃ are, for example, fluorine, chlorine, bromine and iodine atoms.

Especially preferably, R ₁ is a methyl, ethyl, propyl, or butyl group, R ₂ is a hydrogen atom, R ₃ is hydrogen, chlorine or bromine atom or trifluoromethyl, methyl, ethylmethoxy or ethoxy and R ₃ Is preferable when is at the 3-position of the phenyl ring.

Examples of 0-nitro-phenyl-thionocarbamoyl-carbaminate of the general formula (2) of the present invention are as follows.

2-nitro-4-phenoxysulfonyl-fanyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-chloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-chloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-chloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2,5-dichloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3,5-dichloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-bromo-dichloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-bromo-dichloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-bromo-dichloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-methyl-dichloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-methyl-dichloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-methyl-dichloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-tertbutyl-dichloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2,4-dimethyl-dichloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-chloro-4-methyl-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-chloro-6-methyl-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-chloro-4-methyl-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-chloro-6-methyl-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-chloro-2-methyl-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-chloro-3-methyl-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-trifluoromethyl-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-methoxy-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-methoxy-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-methoxy-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-propoxy-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-isopropoxy-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-butoxy-phenoxysulfonyl) -phenyl-thioo carbamoyl-ethylcarbamate,

2-nitro-4- (4-isobutoxy-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-cyano-phenoxysulfonyl) -phenyl-thionocarbamoyl-ethylcarbamate,

2-nitro-4-phenoxysulfonyl-phenyl-thionocarbamoyl-ethylcarbamate,

2-nitro-4-phenoxysulfonyl-phenyl-thionocarbamoyl-propyl-carbamate,

2-nitro-4-phenoxysulfonyl-phenyl-thionocarbamoyl-isopropylcarbamate,

2-nitro-4-phenoxysulfonyl-phenyl-thionocarbamoyl-butylcarbamate,

2-nitro-4-phenoxysulfonyl-phenyl-thionocarbamoyl-isobutyl carbaminecarbamate,

2-nitro-4-phenoxysulfonyl-phenyl-thionocarbamoyl-tert-butylcarbamate,

2-nitro-4-phenoxysulfonyl-phenyloxy-thionocarbamoyl-methyl-carbamate,

2-nitro-4- (4-chloro-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-chloro-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-chloro-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2,5-dichloro-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3,4-dichloro-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3,5-dichloro-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-bromo-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-bromo-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-bromo-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-methyl-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-methyl-phenyl-sulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-methyl-phenylsulfonyloxy-phenyl-thioo carbamoyl methylcarbamate,

2-nitro-4- (4-tertbutyl-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-chloro-4-methyl-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-chloro-6-methyl-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-chloro-4-methyl-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-chloro-6-methyl-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-chloro-2-methyl-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-chloro-2-methyl-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-trifluorofluoromethyl) -phenylsulfonyloxyphenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (4-methoxy-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (3-methoxy-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-methoxy-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-isooxy-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-2- (2-isopropoxy-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4- (2-isobutoxy-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate,

2-nitro-4-phenylsulfonyloxy-phenyl-thionocarbamoyl-ethylcarbamate,

2-nitro-4-phenylsulfonyloxy-phenyl-thionocarbamoyl-propylcarbamate,

2-nitro-4-phenylsulfonyloxy-phenyl-thionocarbamoyl-isopropylcarbamate,

2-nitro-4-phenylsulfonyloxy-phenyl-thionocarbamoyl-butylcarbamate,

2-nitro-4-phenylsulfonyloxy-phenyl-thionocarbamoyl-isobutylcarbamate,

2-nitro-4-phenylsulfonyloxy-phenyl-thionocarbamoyl-tertbutylbutyl carbamate,

2-nitro-4- (3-triflouromethyl-phenylsulfonyloxy) -phenyl-thionocarbamoyl-ethylcarbamate,

2-nitro-4- (3-trifluoro methyl-phenylsulfonyloxy) -phenyl-thioo carbamoyl-isopropyl carbamate,

2-nitro-4- (3-trifluoromethyl-phenylsulfonyloxy) -phenyl-thionocarbamoyl-isobutylcarbamate.

The compound of formula (2) of the present invention is prepared by reacting the 0-nitro-aniline derivative of formula (3) with alkyl-isothiocyanato-formate of formula (4),

Wherein R ₁ , R ₂ , R ₃ and X are as described above.

The method of the present invention is described in more detail as follows.

The o-nitroaniline derivative of formula (3) is reacted at a temperature of from 20 to 120 ° C. for at least one hour, depending on the reactivity of the starting material of alkyl-iso-thiocyanato-formate and for use as a solvent in this reaction. It is suitable to use an excess of isothiocyanato-formate.

The reaction product is separated off by evaporation of excess alkyl-isocyanato-formate and the residue is inert (e.g. acetic acid ester, diethyl ether, diisopropyl ether, methylene chloride, chloroform, benzene and the like). ) Extract with solvent.

Representative examples of the o-nitroaniline derivative of the general formula (3) include the following compounds.

2-nitro-4-phenyloxasulfonyl-aniline,

2-nitro-4- (4-chloro-phenoxysulfonyl) -aniline,

2-nitro-4- (3-chloro-phenoxysulfonyl) -aniline,

2-nitro-4- (2-chloro-phenoxysulfonyl) -aniline,

2-nitro-4- (2,5-dichloro-phenoxysulfonyl) -aniline,

2-nitro-4- (3,5-dichloro-phenoxysulfonyl) -aniline,

2-nitro-4- (4-bromo-phenoxysulfonyl) -aniline,

2-nitro-4- (3-bromo-phenoxysulfonyl) -aniline,

2-nitro-4- (2-bromo-phenoxysulfonyl) -aniline,

2-nitro-4- (4-methyl-phenoxysulfonyl) -aniline,

2-nitro-4- (3-methyl-phenoxysulfonyl) -aniline,

2-nitro-4- (2-methyl-phenoxysulfonyl) -aniline,

2-nitro-4- (4-tertbutyl-phenoxysulfonyl) -aniline,

2-nitro-4- (2,4-dimethyl-phenoxysulfonyl) -aniline,

2-nitro-4- (2-chloro-4-methyl-phenoxysulfonyl) -aniline,

2-nitro-4- (2-chloro-6-methyl-phenoxysulfonyl) -aniline,

2-nitro-4- (3-chloro-4-methyl-phenoxysulfonyl) -aniline,

2-nitro-4- (4-chloro-2-methyl-phenoxysulfonyl) -aniline,

2-nitro-4- (4-chloro-3-methyl-phenoxysulfonyl) -aniline,

2-nitro-4- (3-trifluoromethyl-phenoxysulfonyl) -aniline,

2-nitro-4- (4-methoxy-phenoxysulfonyl) -aniline,

2-nitro-4- (3-methoxy-phenoxysulfonyl) -aniline,

2-nitro-4- (2-methoxy-phenoxysulfonyl) -aniline,

2-nitro-4- (4-propoxy-phenoxysulfonyl) -aniline,

2-nitro-4- (4-isopropoxy-phenoxysulfonyl) -aniline,

2-nitro-4- (4-butoxy-phenoxysulfonyl) -aniline,

2-nitro-4- (4-isobutoxy-phenoxysulfonyl) -aniline,

2-nitro-4-phenoxysulfonyloxy-aniline,

2-nitro-4- (4-chloro-phenylsulfonyloxy) -aniline,

2-nitro-4- (3-chloro-phenylsulfonyloxy) -aniline,

2-nitro-4- (2-chloro-phenylsulfonyloxy) -aniline,

2-nitro-4- (2,5-dichloro-phenylsulfonyloxy) -aniline,

2-nitro-4- (3,4-dichloro-phenylsulfonyloxy) -aniline,

2-nitro-4- (3,5-dichloro-phenylsulfonyloxy) -aniline,

2-nitro-4- (4-bromo-phenylsulfonyloxy) -aniline,

2-nitro-4- (3-bromo-phenylsulfonyloxy) -aniline,

2-nitro-4- (2-bromo-phenylsulfonyloxy) -aniline,

2-nitro-4- (4-methyl-phenylsulfonyloxy) -aniline,

2-nitro-4- (3-methyl-phenylsulfonyloxy) -aniline,

2-nitro-4- (2-methyl-phenylsulfonyloxy) -aniline,

2-nitro-4- (4-tertbutyl-phenylsulfonyloxy) -aniline,

2-nitro-4- (2-chloro-4-methyl-phenylsulfonyloxy) -aniline,

2-nitro-4- (2-chloro-6-methyl-phenylsulfonyloxy) -aniline,

2-nitro-1- (3-chloro-3-methyl-phenylsulfonyloxy) -aniline,

2-nitro-4- (3-chloro-6-methyl-phenylsulfonyloxy) -aniline,

2-nitro-4- (4-chloro-2-methyl-phenylsulfonyloxy) -aniline,

2-nitro-4- (4-chloro-3-methyl-phenylsulfonyloxy) -aniline,

2-nitro-4- (3-trifluoromethyl-phenylsulfonyloxy) -aniline,

2-nitro-4- (4-methoxy-phenylsulfonyloxy) -aniline,

2-nitro-4- (3-methoxy-phenylsulfonyloxy) -aniline,

2-nitro-4- (2-methoxy-phenylsulfonyloxy) -aniline,

2-nitro-4- (4-propoxy-phenylsulfonyloxy) -aniline,

2-nitro-4- (4-isopropoxy-phenylsulfonyloxy) -aniline,

2-nitro-4- (4-butoxy-phenylsulfonyloxy) -aniline,

2-nitro-4- (4-isobutoxy-phenylsulfonyloxy) -aniline.

Alkyl-isothio cyanato-formates of the general formula (4) used in the present invention include methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl and tert-butyl-isothiocyanato, There is a formate.

The 0-nitroaniline derivative of the general formula (3) which is the starting material of the present invention can be prepared as follows.

1. When X in formula (3) is -O-SO ₂ , the corresponding chloro-nitro compound of formula (5), wherein R 2 and R 3 are as described in Structural Formula (1) above, The compound of formula (3) is prepared by reaction with ammonia in a suitable solvent (for example dioxane or methanol) under pressure. The chloro-nitro compound of formula (5) is formulated with 3-nitro-4-chloro-benzenesulfonsal chloride of formula (6) in an inert solvent in the presence of a base (e.g. triethylamine). And phenol of which R ₂ and R ₃ are as described for formula (1).

2. When X in formula (3) is -SO ₂ -O-, 3-nitro-4-amino-phenol of formula (8) is dissolved in an inert solvent in the presence of a base (for example triethylamine). The corresponding 0-nitroaniline derivatives of formula (3) are prepared by reaction with benzene-sulfonic acid-chloride of formula (9), wherein R ₂ and R ₃ are as described for formula (1).

The reaction steps are explained in the following diagram.

0-nitrophenyl-thionocarbamoyl-carbamate of formula (2) has an antiparasitic action. Furthermore, when preparing the 1H-2,1,4-benzothiadiazine derivative of the general formula (1) having an antiparasitic effect, it is effectively used as a precursor.

Compound (2) of the present invention can be used in many forms, such as insects, nematodes, austergia, tapeworms, couperia, cabertia, espagostoms, hyostromgirus, ankylosoma, roundworms, heterakis It is highly active against parasites. Above all, it is a strong parasitic gastrointestinal that harms ruminants and has an excellent effect on the genus Ides.

The active substance is administered orally or subcutaneously with appropriate pharmaceutically acceptable solvents and / or carriers, the method of administration choosing whichever is preferred depending on the circumstances. The following examples detail the invention.

Example 1

2-nitro-4-phenoxysulfonylphenyl-thionocarbamoyl-methylcarbamate

29.4 g of 2-nitro-4-phenoxysulfonylfonyl-aniline in 30 ml of methyl-isothiaosinato-formate is prepared by stirring and warming to 100 ° C. for 1 hour. After cooling to 30 DEG C, a total amount of 200 ml of diisopropyl ether was gradually added to the mixed solution, and then cooled in an ice bath to produce 2-nitro-4-phenoxysulfonyl-phenyl-thionocarbamoyl-methylcarbamate precipitate. Filter out. This precipitation is of sufficient purity for the next step reaction. Yield is 25 g and melting point is 137 ° C.

To prepare 2-nitro-4-phenoxy sulfonylaniline, 54 g of 3-nitro-4-chlorobenzene-sulfonsal-phenylester in 500 ml of dioxane was added over 5 hours of ammonia gas at 50 ° C. for 5 hours. The solvent is then evaporated off in vacuo. The residue is mixed with 200 ml of a mixed mixture of methanol and water in the same amount, at which time a solid precipitate forms and is filtered off. After recrystallization from methanol and benzene, 28 g of 2-nitrophenoxysulfonyl-aniline was obtained and the melting point was 104 캜.

3-nitro-4-chloro-benzene-sulfonic acid-phenyl ester was mixed with 51 g of 3-nitro-4-chlorobenzene-sulfonic acid-chloride with 18.8 g of phenol in 120 ml of acetone at a temperature not exceeding 10 ° C. While cooling, 28 ml of triethylamine is added dropwise. The mixture is stirred for several hours at room temperature, then water is added and the resulting oil is extracted and separated by ether. After recrystallization of the residue with methanol, 54 g of 3-nitro-4-chlorobenzene-sulfonic acid-phenylester were obtained and the melting point was 71 占 폚.

Using the following starting materials, which are slightly modified in a similar manner, the following compounds are prepared.

2. 2-nitro-4- (4-chloro via 3-nitro-4- (4-chlorophenoxysulfonyl-aniline) from 3-nitro-4-chloro benzene-sulfonic acid-4-chloro-phenylester Phenoxysulfonyl) -phenyl-thionocarbamoyl-methyl-carbamate.

3. 3-nitro-4-chloro-benzene-sulfonic acid-3-chloro-phenyl

2-nitro-4- (3-chloro-phenoxysulfonyl) -phenyl-thionocarbamoyl-methyl-carbamate from esters via 2-nitro-4- (3-chloro phenoxysulfonyl) -aniline box.

4. 2-nitro-4 from 3-nitro-4-chloro-benzene-sulfonic acid-3,5-dichloro-phenyl ester via 2-nitro-4- (3,5-dichloro-phenoxysulfonyl) -aniline Obtain-(3,5-Dichloro-phenoxysulfonyl) -phenyl-thionocarbamoyl methylcarbamate.

5. 2-nitro-4- (3 from 3-nitro-4-chlorobenzene-sulfonic acid-3-bromo-phenylester via 2-nitro-4- (3-bromo-phenoxysulfonyl) aniline -Bromo-phenoxysulfonyl) phenylthionocarbamoylmethyl-carbamate.

6. 2-nitro-4- (4 from 3-nitro-4-chloro-benzene-sulfonic acid-4-methyl-phenylester via 2-nitro-4- (4-methyl-phenoxysulfonyl) -aniline -Methyl-phenoxy sulfonyl) -phenyl-thioo carbamoyl-methyl-carbamate.

7. 2-nitro-4- (3 through 3-nitro-4-chloro-benzene-sulfonic acid-3-methyl-phenylester via 2-nitro-4- (3-methyl-phenoxysulfonyl) -aniline -Methyl-phenoxysulfonyl) -phenyl-thionocarbamoyl-methyl-carbamate.

8. 2-nitro-4- (4 from 3-nitro-4-chlorobenzene-sulfonic acid-4-methoxy-phenyl ester via 2-nitro-4- (4-methoxy-phenoxysulfonyl) -aniline -Methoxy-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate.

9. 2-nitro-4- (3-nitro-4-chloro-benzene-sulfonic acid-3-methoxy-phenyl ester via 2-nitro-4- (3-methoxy-phenoxysulfonyl) -aniline 3-Methoxy-phenoxysulfonyl) -phenyl-thionocarbamoyl-methyl carbamate is obtained.

10. 2-Nitro-4- (3-nitro-4-chloro-benzene-sulfonic acid-3-ethoxy-phenylester via 2-nitro-4- (3-ethoxy-phenoxysulfonyl) -aniline 3-ethoxy-phenoxysulfonyl) -phenyl-thionocarbamoyl-methyl carbamate is obtained.

11. 3-Nitro-4-chloro-benzene-sulfonic acid-3-cyano-phenylester via 2-nitro-4- (3-cyano-phenoxysulfonyl) -aniline to 2-nitro-4- ( 3-Cyano-phenoxysulfonyl) -phenyl-thionocarbamoyl-methyl-carbamate is obtained.

12. 2-nitro-4- (3-trifluoromethyl-phenoxysulfonyl)-from 3-nitro-4-chloro-benzene-sulfonic acid-3-trifluoro methyl-phenylester having a melting point of 65 deg. Aniline (melting point 131 ° C.) affords 2-nitro-4- (3-trifluoromethyl-phenoxysulfonyl) -phenyl-thionocarbamoyl-methylcarbamate (melting point 157 ° C.).

13. 2-nitro-4-phenylsulfonyloxyphenylthioo carbamoyl methylcarbamate

29.4 g of 2-nitro-4-phenylsulfonyloxy-aniline in 30 ml of methyl-isothiocyanato-formate are heated at 100 ° C. for one hour with stirring.

After cooling to 30 ° C., 200 ml of diisopropyl ether was slowly added to the mixed solution, followed by cooling with an ice bath, and the precipitated 2-nitro-4-phenylsulfonyloxy-phenyl-thionocarbamoyl-methyl-carbamate was filtered by suction. do.

The product was recrystallized from a mixture of methyl glycol and methanol to obtain 30 g of the material having a melting point of 134 ° C.

To prepare 2-nitro-4-phenylsulfonyloxy-aniline, 15.4 g of 3-nitro-4-aminophenol in 100 ml of acetone was mixed with 14 ml of triethylamine, and then 17.6 dissolved in 30 ml of acetone. g of benzene-sulfonic acid-chloride is stirred and added dropwise in an ice bath so that the internal temperature does not exceed 20 ° C.

After stirring the mixture further for 3 hours at room temperature, triethylamine-hydrochloride is filtered off and the filtrate is evaporated to dryness. The residue is stirred with 50 ml of methanol and filtered. After washing with methanol and drying, 18.2 g of 2-nitro-phenylsulfonyloxy-aniline having a melting point of 140 ° C. are obtained.

The following compounds are prepared using the following starting materials with slight modifications in a similar manner.

14. 2-nitro-4- (4-chloro-phenylsulfonyloxy) -phenyl-thioo carbamoyl-methyl carbamate from 2-nitro-4- (4-chloro-phenyl sulfonyloxy) -aniline To obtain.

15. 2-nitro-4- (3-chloro-phenylsulfonyloxy) -aniline from 2-nitro-4- (3-chloro-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate To obtain.

16. 2-nitro-4- (3,4-dichloro-phenylsulfonyloxy) -aniline from 2-nitro-4 (3,4-dichloro-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarba Obtain a minate.

17. 2-Nitro-4- (3,5-dichloro-phenylsulfonyloxy) -aniline from 2-nitro-4- (3,5-dichloro-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methyl Obtained carbamate.

18. 2-Nitro-4- (3-bromo-phenylsulfonyloxy) -phenyl-thioo carbamoyl methyl carbonate from 2-nitro-4- (3-bromo-phenylsulfonyloxy) -aniline Obtained.

19. 2-Nitro-4- (4-methyl-phenylsulfonyloxy) -phenyl-thioo carbamoyl-methylcarbamide from 2-nitro-4- (3- (methyl-phenylsulfonyloxy) -aniline Obtained Nate.

20. 2-Nitro-4- (3-methylphenylsulfonyloxy)-(from aniline to 2-nitro-4- (3-methyl-phenylsulfonyloxy) -phenyl-thionocarbamoyl-methylcarbamate Obtained.

21. 2-nitro-4- (3-trifluoromethyl-phenylsulfonyloxy) 2-nitro-4- (3-trifluoromethyl-phenylsulfonyloxy) phenyl- from aniline (melting point 12 ° C.) Obtained thionocarbamoyl-methylcarbamate (melting point 126 ° C.).

22. 2-Nitro-4- (3-trifluoro methyl-phenylsulfonyloxy) -aniline from 2-nitro-4- (3-trifluoro methyl) -phenylsulfonyloxy) -phenyl-thiono Obtained carbamoyl-ethylcarbamate

23. 2-nitro-4 (3-trifluoromethyl-phenylsulfonyloxy) -phenyl-thionocarbamoyl from 2-nitro-4- (3-trifluoro methyl-phenyl sulfonyloxy) -aniline To obtain isopropylcarbamate.

24. 2-Nitro-4- (3-trifluoromethyl-phenylsulfonyloxy)-from aniline 2-nitro-4-3-trifluoromethyl-phenylsulfonyloxy) -phenyl-thio carbamoyl- Obtain isopropyl carbamate.

Claims (1)

A process for preparing a compound of formula (2) by reacting a 0-nitro-aniline derivative of formula (3) with an alkyl-isothiocyanato-formate of formula (4).

In the above structure, R ₁ is alkyl having 1 to 4 carbon atoms, R ₂ and R ₃ are each different from each other, hydrogen, alkoxy having 1 to 4 carbon atoms, halogen, trifluoromethyl, alkyl having 1 to 4 carbon atoms or cyano, X is -O-SO₂ or -SO ₂ -O-.