DE1188582B - Process for the preparation of derivatives of trichloromethylsulfenyl chloride - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

C07c

German class: 12 ο -23/03

1188 582
B72147IVb / 12o
June 1, 1963
March 11, 1965

It is known that derivatives of trichloromethylsulfenyl chloride, z. B. the connection

CH ₃
CH ₃

\ / CH ₃

/ Ν - SO ₂ - NC ^XX S - CCl ₃

obtained when trichloromethylsulfenyl chloride with substituted sulfonyl diamides which have at least one unsubstituted water atom bonded to nitrogen, e.g. B. converts the compound (CH ₃ ) ₂ N · SO ₂ · NHCH ₃ (cf. German Patent 975 295). It is also known to prepare substituted sulfonyl diamides by reacting amidosulfonyl chlorides with amines (cf. Houben-Weyl Vol. XI / 2, 4th edition, 1958, p. 715).

It has been found that derivatives of trichloromethylsulfenyl chloride the general formula

Ri \ / R ₃

/ Ν - SO2 - NC
R ₂ ^XX S -CCl ₃

in which Ri is an optionally substituted aryl or cycloalkyl radical, R _{2 is} an optionally substituted alkyl, cycloalkyl or aryl radical and R _{3 is} an alkyl radical having 1 to 4 carbon atoms, in particular the methyl or ethyl radical, if one is in a Stage trichloromethylsulfenyl chloride and an N-monosubstituted amidosulphonyl chloride in the presence of an organic solvent and a compound that binds hydrogen chloride with an amine of the general formula

Ri
R ₂ -

Ν —Η

in which Ri and R _{2 have} the meaning given above. It is surprising that the secondary aryl- or cycloalkylamine only reacts with the amidosulfonyl chloride and not with the trichloromethylsulfenyl chloride.

N-monosubstituted amidosulfonyl chlorides and their preparation are described in German Patent 1,121,060. As secondary amines can be used for the preparation process according to the invention, for. Use e.g. N-methylaniline, N-ethylaniline, N-propylaniline, diphenylamine, N-methyl-m-nitroaniline, N-ethylnaphthylamine, N-methylcyclohexylamine or N-propylcyclohexylamine. Compounds that bind hydrogen chloride are tertiary amines, processes for the preparation of derivatives of
Trichloromethylsulfenyl chloride

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Named as inventor:

Dr. Gerhard Schulze,

Dr. Günter Weiß, Ludwigshafen / Rhine

z. B. trimethylamine, triethylamine or pyridine, suitable.

The only liquids that can be used as organic solvents are those which are inert to are all reaction components. These are, for example, benzene, toluene, tetrahydrofuran, diethyl ether or acetonitrile. Mixtures of several solvents, e.g. B. Mixtures of methylene chloride and pentane can be used.

The reaction temperature is not tied to any specific temperature range, but it is advisable to ^{carry out the reaction in a temperature range between about +10 and + 10O 0} C, the upper limit of the temperature range being given by the boiling point of the solvent used in each case.

It is advisable to use stoichiometric amounts of the starting materials for the implementation, since an excess of one of the starting components does not improve the conversion and only leads to contamination of the end product.

To carry out the method according to the invention, a mixture of equimolar Amounts of N-alkylamidosulfonyl chloride and trichloromethylsulfenyl chloride Submit in an inert organic solvent and the mixture of a secondary amine and a hydrogen chloride Component, advantageously also dissolved in an organic solvent, add. It is however, it is also possible to react the reaction components in reverse order, d. H. Submit a mixture of amines and add the mixture of acid chlorides. Further one can use the mixture of two in each case

509 518/474

Connections add the two remaining connections separately, but at the same time.

The compounds obtainable in this way are sparingly soluble in water. They arise according to the invention Process in very pure form and in most cases do not need to be additionally cleaned will. You can e.g. B. found as fungicidal active ingredients use.

The following examples explain the process according to the invention. The parts are parts by weight.

example 1

15th

of 10.7 parts of N-methylaniline and 20.2 parts of triethylamine. The precipitated triethylamine hydrochloride is separated off and the solvent is removed from the filtrate. According to a yield of 95% of theory, 33 parts of N ^ '- dimethyl-N-phenyl-N'-trichloromethylmercaptosulfonyldiamide with a melting point of 86 ^° C. are obtained.

Example 4

NO ₂

H ₃ C

S-CCl ₃

- SO ₂ - N

C2H5
S - CCl ₃

12.9 parts of N-methylamidosulfonyl chloride and 18.6 parts of trichloromethylsulfenyl chloride are dissolved in 100 parts of benzene, heated to 50 ^° C. and a benzene solution of 11.3 parts of N-methylcyclohexylamine and 20.2 parts of triethylamine is added with vigorous stirring. The quantitatively precipitated triethylamine hydrochloride is filtered off and the solvent is distilled off from the filtrate. There remain 35 parts of RN'-dimethyl-N-cyclohexyl-N'-trichloromethylmercaptosulfonyldiamide (mp = 97 ° C.), which corresponds to a yield of 98% of theory.

30th

Example 2

So ₂ -N:

-CH ₃
S-CCh

35

12.9 parts of N-methylamidosulfonyl chloride are dissolved together with 18.6 parts of trichloromethylsulfenyl chloride in 100 parts of benzene, ^{heated to 50 °} C. and a benzene solution of 16.9 parts of diphenylamine and 20.2 parts of triethylamine are slowly added to this with stirring. After stirring for a further 1 hour, the quantitatively precipitated triethylamine hydrochloride is filtered off with suction, washed with benzene and the filtrate is freed from the solvent. 41 parts of Ν, Ν-diphenyl-N'-methyl-N'-trichloromethylmercaptosulfonyldiamide with a melting point of 119 ° C. are obtained. The yield is 99% of theory.

Example 3

—SO ₂ -N

/ CH ₃
(

S-CCl ₃

14.1 parts of triethylamine are dissolved together with 20.6 parts of N-methyl-m-nitroaniline in 50 parts of tetrahydrofuran. At 0 ⁰ C was added thereto a solution of 10 parts of N-Äthylamidosulfonylchlorid and 13 parts Trichlormethylsulfenylchlorid. The precipitated triethylamine hydrochloride is separated off and the solvent is removed from the filtrate. 27.5 parts of N-methyl-N- (3'-nitrophenyO-N'-ethyl-N'-trichloromethylmercaptosulfonyldiamide (this corresponds to 97% of theory) are obtained. After recrystallization from methanol, the orange-red compound melts at 65 ^° C.

Claims (1)

Claim: Process for the preparation of derivatives of trichloromethylsulfenyl chloride of the general formula 55 12.9 parts of N-methylamidosulfonyl chloride and 18.6 parts of trichloromethylsulfenyl chloride are dissolved in 100 parts of benzene. This solution is added to a benzene solution ^R1 > ^{heated to 50 ° C.} R ₂ ^X ; —CCi ₃ in which Ri is an optionally substituted aryl or cycloalkyl radical, R _{2 is} an optionally substituted alkyl, cycloalkyl or aryl radical and R _{3 is} an alkyl radical having 1 to 4 carbon atoms, in particular the methyl or ethyl radical, characterized in that in one stage trichloromethylsulfenyl chloride and an N-monosubstituted amidosulphonyl chloride in the presence of an organic solvent and a hydrogen chloride-binding compound with an amine of the general formula R ₁
R ₂ Ν —Η in which Ri and R _{2 have} the meaning given above. 509 518/474 3.65 © Bundesdruckerei Berlin