DE1210792B - Process for the preparation of carbonylsulfonylimides - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C07c

German KL: 12 ο-16

Number: 1 210 792

File number: B 72285IV b / 12 ο

Filing date: June 14, 1963

Opening day: February 17, 1966

It is known that N-carbonyl-sulfamic acid chloride with compounds containing an active hydrogen atom, can react and thereby the N-carbonyl-sulfamic acid chloride in the same Way isocyanate reacts. It is known from German Patent 941 847 that N-carbonyl-sulfamic acid chloride with olefins whose double bond is terminal, with the formation of a mixture of / 3-lactam-N-sulfochlorides and N-sulfochlorides unsaturated carboxamides react, ι ο Precise information on the conditions under which the one or the other compound class arises are not made. The one in the German Patent specification 1 010 958 described processes are hydrocarbons containing at least one aromatic ι j cal ring system, with N-carbonyl-sulfamic acid chlorides converted to carboxamides in the presence of Friedel-Crafts catalysts. Carbonylsulfonylimides, as they are after Process described here are to be produced, can be used when working according to the in the German Patent 1 010 958 do not produce the method described.

It has been found that carbonylsulfonylimides are obtained when N-carbonyl-sulfamic acid chloride or fluoride is used with a compound of the general formula _/ .

^R τ r ^0R

R "-4-

in which R is an alkyl group, R 'and R "hydrogen

CH ₃ O

+ OCN- SO ₂ - Cl

Ethers derived from phenols whose hydroxyl group is etherified with an alkyl radical with preferably 1 to 6 carbon atoms can be used as starting materials. Such compounds are e.g. B. anisole, phenetole, phenyl butyl ether or phenyl hexyl ether. But you can also use the corresponding ethers of dihydric phenols, such as the ethers of catechol, resorcinol or hydroquinone. The phenyl radical of the ether can also contain a fused aromatic ring, e.g. B. ct-naphthyl propyl ether, ß-naphthyl methyl ether. The phenyl ethers can also by halogen atoms, preferably chlorine or bromine atoms, alkyl groups with 1 to 4 carbon processes for the preparation of
Carbonylsulfonylimides

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Matthias Seefelder, Ludwigshafen / Rhine -

or halogen atoms, alkyl, nitro or cyano groups and R 'can also be an alkoxy group, where R' and R "can also jointly be members of a fused aromatic ring, optionally in the presence of inert solvents, at temperatures between about 0 and 120 ⁰ C, preferably between about 20 and 50 ⁰ C, converts.

The carbonylsulfonylimide group occurs in the o- or p-position to the - OR radical.

The implementation can be z. B. when using anisole and N-carbonylsulfamic acid chloride represented by the following reaction scheme:

CH ₃ O

^co ~~ ^NH ~ ^S ° ^2C1

atoms, nitro or cyano groups may be substituted. Representatives of this type are e.g. m-cresyl ethyl ether, ο - chlorine - phenyl methyl ether, thymyl methyl ether, o-nitroanisole, ο, ο'-drnitroanisole, o-cyananisole and o-bromophenetol.

The reaction is preferably carried out in the presence of an inert solvent, e.g. B. a hydrocarbon, such as benzene, toluene, xylene, cyclohexane or methylcyclohexane, or an ether, such as dibutyl ether, dioxane, tetrahydrofuran, glycol dimethyl ether, carried out. The end products crystallize from the inert solvents mentioned mostly easily and can therefore from the Reaction mixture can be easily separated. the

609 508/290

Starting materials are preferably used in a molar ratio of 1: 1. But it can also be a Excess, e.g. B. used a 1.1 to 5-fold excess of one or the other reactant will. Since heat is released during the reaction, it can be useful to cool it down to dissipate.

The new compounds obtainable by the process are valuable intermediates for Manufacture of textile auxiliaries and pharmaceuticals.

The following examples illustrate the process of the invention. The parts indicated are parts by weight.

example 1

To a solution of 17.2 parts JOE Naphthyläthyläther in 17 parts of benzene are added with stirring at about 20 ⁰ C, 14 parts of N-carbonyl-sulfaminsäureehlorid dissolved in 10 parts of benzene, slowly. After 2 hours, the separated crystals are filtered off with suction. 30 parts of a compound of the formula are obtained

CO-NH-SO ₂ Cl

C ₂ H ₅ - O

CO-NH-SO ₂ Cl

CH ₃ O

CO-NH-SO ₂ Cl

OCH ₃
which melts at 131 to 133 ^{° C.}

IO

Example 4

To a solution of 16 parts of jS-Naphthylmethyläther in 16 parts of benzene are added with stirring at about 20 ⁰ C 14.2 parts of N-carbonyl-sulfaminsäurechlorid dissolved in 10 parts of benzene, slowly. After 5 hours, the separated crystals are filtered off with suction. 27 parts of a compound of the formula are obtained

CO-NH-SO ₂ Cl

OCH ₃

which melts at 130 to 133 ⁰ C with decomposition.
Example 5

To a solution of 15.8 parts | S Naphthylmethyläther in 25 parts of benzene 12.5 parts of N-carbonyl sulfaminsäurefluorid are slowly added at 25 ⁰ C. After one hour, heated to 7O ⁰ C and kept at that temperature for 4 hours. It is cooled, the precipitated colorless product is filtered off with suction, washed with petroleum ether and dried under reduced pressure. 18 parts of a compound of the formula are obtained

OC ₂ H ₅

which melts at 125 to 127 ° C. .

Example 2

To a solution of 17.2 parts a-Naphthyläthyläther in 17 parts of benzene are added with stirring at about 20 ⁰ C 14.2 parts of N-carbonyl-sulfaminsäurechlorid dissolved in 15 parts of benzene, slowly. After 2 hours, the separated crystals are filtered off with suction. 29.5 parts of a compound of the formula are obtained

CONHSO2F

OCH ₃

40 which melts at 170 to 171 ⁰ C with decomposition.

Claims (1)

Claim: Process for the preparation of carbonylsulfonylimides, characterized in that N-carbonyl-sulfamic acid chloride or fluoride with compounds of the general formula R ' which is sensitive to humidity and melts at 109 to 111 ° C. Example 3 A solution of 14 parts of resorcinol dimethyl ether in 20 parts of dioxane is added with stirring about 20 to 30 ° C., with external cooling, 14 parts of N-carbonyl-sulfamic acid chloride in 10 parts of dioxane solved, slowly to. After stirring for 8 hours, the crystals which have separated out are filtered off with suction. Man receives 17 parts of a compound of the formula 45 OR in which R is an alkyl group, R 'and R "are hydrogen or halogen atoms, alkyl, nitro or cyano groups and R' can also be an alkoxy group, where R 'and R" can also jointly be members of a fused aromatic ring, optionally in the presence inert solvent, at temperatures between about 0 and 120 ⁰ C, preferably between about 20 and 50 ⁰ C, reacted. Considered publications:
German Patent Nos. 931 225, 941 847, 1010 958; Chemical Reports, Vol. 96, 1963, pp. 56-67; Houben-Weyl, Methods of Organic Chemie, 4th edition, Vol. VIII ,oxidverbindungen III, 1952, p. 660.