DE3124010A1 - Novel sulphonamides - Google Patents

Abstract

The invention relates to novel sulphonamides of the general formula I <IMAGE> in which R<1> denotes hydrogen, alkali metal, optionally substituted ammonium or optionally substituted alkyl, and R<2> denotes optionally substituted alkyl, alkenyl, aralkyl or cycloalkyl, or a radical of the formula <IMAGE> in which R<3> and R<4> are alkyl groups or, together with the nitrogen atom, form a 5-membered or 6-membered ring which is optionally interrupted by a heteroatom. The compounds according to the invention are very suitable for use as diazo components.

Description

New sulfonamides

The invention relates to new sulfonamides of the general formula I. in which R1 is hydrogen, alkali, optionally substituted ammonium or optionally substituted alkyl and R2 is optionally substituted alkyl, alkenyl, aralkyl or cycloalkyl or a radical of the formula mean, where R3 and R4 are alkyl groups or together with the nitrogen atom form a five- or six-membered ring, optionally interrupted by a heteroatom, The process for the preparation of the compounds according to the invention is characterized in that compounds of the general formula II in which R1 has the abovementioned meaning, selectively with a sulfonyl halide of the formula III Hal-SO2-R² III, in which R2 has the abovementioned meaning and Hal stands for fluorine, chlorine or bromine, in the presence of an alkaline earth oxide or carbonate at a pH -Value from 3 to 7 in the presence of a diluent at temperatures from -20 to +40 ° C.

As alkyl substituents for R1 to R4, for. B. Considero methyl, Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3 Pentyl, tert. Amyl, neopentyl, 2 «methylbutyl, 3-methylbutyl, 3-methyl-2-butyl, n-hexyl 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methylpentyl, 3-methyl-2-pentyl, 3-methyl-3-pentyl, 4-methyl-2-pentyl, 2,3-dimethylbutyl, 4,4-dimethylbutyl, 1-fluoroethyl, 2-fluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2-fluorobutyl, 2-fluoro-2-methyl-3-propyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1-chloromethyl, 1-chloroethyl, 2-chloroethyl, 1-chloropropyl, 3-chloropropyl, 1-chloro-2-propyl, 2-chlorobutyl, 2-chloro-3-methyl-3-propyl, 4-chlorobutyl, 2,2,2-trichloroethyl, 2-bromomethyl, 3-bromopropyl, 4-bromobutyl, 2-bromo-2-methyl-3-propyl, 2,3-dibromo-1-propyl, 2-methoxyethyl, 2,2-dimethoxyethyl, 1-ethoxyethyl, 2-phenoxyethyl, 2-tolyloxyethyl, 3-methoxypropyl, methoxyisopropyl, 3-methoxybutyl, ethoxy-tert . -butyl, 2-methylmercaptoethyl, 2-methylsulfonyl-ethyl, methylsulfonyloxymethyl, 3-ethylmercapto-propyl, 1-methylmercapto-2-butyl, diethylaminomethyl, 2-dimethylamino-ethyl 2-N-phenylamino-ethyl; Piperidinomethyl, morpholinomethyl, N-methylaminosulfonyloxymethyl, 2-cyanoethyl, 2-acetoxyethyl, carbomethoxymethyl, 2-carbomethoxyethyl or 2-carbopropoxyethyl.

can, for example, also hydrogen, sodium, potassium, ammonium, trimethylammonium or triethylammonium mean.

For R2 are also z. B. to name: Cyclopentyl, Cyclohexyl, Cycloheptyl, 1-methyl-cyclopentyl, 1-methyl-cyclohexyl, 4-ethoxy-cyclohexyl, 2-chloro-cyclohexyl, 4-bromo-cyclohexyl, benzyl, 2-ethylphenyl, 4-tolylmethyl, 2-chlorobenzyl, 4-chlorobenzyl, 3,5-dichlorobenzyl, 3-nitrobenzyl, 4-methoxybenzyl, 4-acetoxybenzyl, 4- (2'-chloroacetyl) benzyl, Benzoylmethyl or 4'-chlorobenzoyl-2-ethyl, propen-2-yl-1, buten-2-yl-1, 3-chlorobuten-1-yl-4, 2-methylbuten-2-yl-1, 2-methylbuten-1-yl-3, allyl, methallyl, crotyl, 2-ethylhexen-2-yl-1, Hexen-5-yl-1, cyclohexen-2-yl-1, dimethylamino, diethylamino, methylethyiamino, 2-cyanoethylmethylamino, methyl-n-propylamino, di-n-propylamino, diisopropylamino, Di-n-butylamino, di-n-hexylamino, di-2-methoxyethylamino, N-pyrrolidinyl, N-piperidinyl, N-morpholinyl, N'-methylpiperazinyl, N'-isopropylpiperazinyl or N'-butylpiperazinyl.

Preferably R1 is hydrogen, methyl or ethyl, R2 is methyl, Ethyl, di-C1- to C4-alkylamino, pyrrolidino, piperidino, morpholino or N-methylpiperazino R3 and R4 for methyl or ethyl.

For Hal are z. B. to name fluorine, chlorine and bromine.

Hal is preferably chlorine.

Alkaline earth oxides or carbonates can be used as the base.

Calcium carbonate is preferably used.

As a diluent, for example, water, acetone, methanol, Ethanol, ethylanglycol dimethyl ether, r N, -N -D imethylformamide and N-methylpyrrolidone, aqueous solutions of the diluents mentioned or two-phase systems of water and methyl tert-butyl ether, diethyl ketone or ethyl acetate can be used.

Preferred diluents are water, acetone and aqueous methanol or ethanol solutions.

Compounds of the formula II are mesylated in the presence of sodium hydroxide solution at a pH of 3.5 to 4.5, as in DE-OS 29 38 633 for selective mesylation of 4-chloro-1,3-phenylenediamine, only a mixture of two is obtained isomeric sulfonamides in a ratio of 1: 1; also when using other basic ones Connections such as B. sec. Alkali phosphates and alkali carbonates or others pH ranges, no isomerically pure sulfonamides are obtained.

Surprisingly, however, according to the process according to the invention the new sulfonamides of the formula I simple, inexpensive and isomer-free in very much good yields are produced if alkaline earth oxides are used as acid-binding agents or carbonates are used.

For the implementation of the diamines of the formula II with the sulfonyl halides of the formula III, for example, molar amounts in a ratio of 1: 1 are used. A small excess of 10-40 mol% (based on the diamines of the formula II) sulfonyl halides are used.

The alkaline earth oxide or carbonate can either be presented or during are added to the reaction. The reaction takes place, for example, at one temperature from -20 to +40 OC, especially from -5 to +10 OC and a pH value of 3 to 7, preferably from 4 to 5.

The process according to the invention is expediently carried out in such a way that if the compound of the formula II is introduced into a diluent, the pH value optionally adjusts to 4 to 8 with the alkaline earth oxide or carbonate, the sulfonyl halide of the formula III in pure or in dissolved form at -5 to +10 OC in 1 to 3 hours metered in, the pH value being increased by adding the alkaline earth oxide or carbonate 4 to 5 is held and the mixture is stirred for 1 to 5 hours at -5 to +20 OC. The course of condensation can be z. B. track by thin layer chromatography.

After the reaction has ended, the pH of the mixture, e.g. B. by Addition of sodium hydroxide solution or hydrochloric acid can be changed and the invention is obtained Compounds of formula I by suction or by extracting the mixture as free bases or, for example, as hydrochlorides. Further details can be found in the Examples are taken.

The isomeric purity of the compounds of general formula I was confirmed by HPLC and by NMR spectra.

The method according to the invention is particularly suitable for production of compounds of the general formula IE in which R1 is hydrogen, methyl or Ethyl and R2 methyl, ethyl, di-C1- to C4-alkylamino, pyrrolidino, piperidino, morpholino or mean N-methylpiperazino.

Particularly technically important are compounds of the formula Is in which R1 stands for hydrogen, the new sulfonamides of the formula I are valuable diazo components for highly lightfast azo dyes.

Example 1 56.4 parts (parts by weight) of metamic acid in 500 parts of water are adjusted to pH = 4 to 5 with calcium carbonate. At 0 ° C., it is added dropwise over a period of 3 hours 40 parts of methylsulfonyl chloride are added, with the addition of calcium carbonate (consumption a total of about 36 parts) the pH of the mixture is kept at 4 to 5, stirs about 3 hours at 0 to 20 OC and acidify the mixture in an ice bath with conc. Hydrochloric acid to pH = 1 to 2. The precipitated product is filtered off with suction and dried. 77 parts of 2-amino-4-methylsulfonylamino-benzenesulfonic acid with a melting point are obtained > 300 OC.

Example 2 Instead of methylsulfonylchlorld, 60 parts of methylsulfonyl bromide are used and if the rest of the procedure is analogous to Example 1, 71 parts of 2-amino-4-methylsulfonylamino are obtained -benzenesulfonic acid with a melting point> 300 OC.

Example 3 50 parts of allylsulfonyl chloride are used instead of methylsulfonyl chloride and if the rest of the procedure is analogous to Example 1, 84 parts of 2-amino-4-allylsulfonylamino are obtained -benzenesulfonic acid with a melting point of 284 - 286 OC.

Example 4 Instead of methylsulfonyl chloride, 50 parts of N, N-dimethylaminosulfonyl chloride are used and if the rest of the procedure is analogous to Example 1, 82 parts of 2-amino-4- (N ', N'-dimethylsulfamoylamino) -benzenesulfonic acid are obtained with a melting point of 275-277 ° C. Example 5 To 56.4 parts of metamic acid, 36 parts Calcium carbonate and 500 parts of water are added dropwise to 40 parts at 0 ° C. in the course of 3 hours Methylsulfonyl chloride, stirred for another 3 hours at 0 to 20 ° C. and acidified the mixture to pH = 1 to 2.

The precipitated product is filtered off with suction and dried.

74 parts of 2-amino-4-methylsulfonylamino-benzene sulphonic acid are obtained with a melting point> 300 OC.

Claims (1)

9 claims sulfonamides of the general formula in which R¹ is hydrogen, alkali, optionally substituted ammonium or optionally substituted alkyl and R2 is optionally substituted alkyl, alkenyl, aralkyl or cycloalkyl or a radical of the formula mean, where R3 and R4 are alkyl groups or together with the nitrogen atom form a five- or six-membered ring optionally interrupted by a heteroatom, 2. Use of the compounds according to Claim 1 as diazo components.