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Patented Feb. 16, 1943 2,311,062

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Patented Feb. 16, 1943 2,311,062 Patented Feb. 16, 1943 2,311,062 UNITED STATES PATENT OFFICE 2,311,062 HALOGEN SUBSTITUTED ACAMNO SULP BONCACDS Henry Martin, Basel, Hans Heinrich. Zaeslin, Glatthar,Riehen, near and Basel,Alfred and staub, Rudolf Basel, Hirt switter Curt land, assignors to J. R. Geigy A. G., Basel, Switzerland No Drawing. Application June 13, 1939, Serial No. 278,954. In Switzerland June 16, 1938 8 Claims. (C. 260-507) This invention relates to the production of heterocyclic, especially halogen and/or alkyl halogen Substituted acyl amino sulphonic acids, substituted amino Sulphonic acids leads to inter the products being useful for various purposes in esting water-soluble products. But also other industry. e. g., for protecting wool and other sub methods as for example treatment of carbon di stances against damage by moths, the protection Sulphide with the specified amino sulphonic acids being very fast to washing and fulling, and in in the presence of Suitable catalysts, for example Some cases as disinfecting agents, bactericides, hydrogen-peroxide or sulphur, leads to water fungicides, and seed steeping materials. Soluble thio-carbonic acid derivatives. It will be According to the present invention halogen understood that similar products can be obtained Substituted acyl amino sulphonic acids of the 10 by warming, melting or heating, in suitable sol aromatic or heterocyclic series are produced by vents or suspension media, the amino sulphonic the treatment of carbonic acid derivatives or acids with urea or thio-urea or urethanes, with thio-carbonic acid derivatives, or substances or separation of ammonia or alcohol. Furthermore, mixtures of substances forming these com by sulphonating completely condensed, difficultly pounds which may also contain sulphonic acid 5 Soluble or insoluble ureas, thio-ureas and ure groups with isocyclic or heterocyclic amines or thanes, containing at least one halogen atom, aminOSulphonic acids containing replaceable Sulphonic acids with surprisingly good properties hydrogen at the nitrogen atom, the reaction can be obtained. Or alkyl- and aryl-carbonic components being so chosen that at least one acid azides lead by condensation with amino halogen atom and a sulphonic acid group are 20 sulphonic acids, with the development of nitro present in the final product. gen, to urea derivatives. Both substituents may also be introduced by In all these methods the substitution of the after-treatment, that is by halogenation of the components must be effected in such a manner not or not highly halogenated acylamino com that at least one halogen-atom and one sul pounds or by Subsequent Sulphonation of the not phonic acid group are present in the final prod or not sufficiently sulphonated compounds. luct. These may be present in either of the re As carbonic acid derivatives or thio-carbonic action components or even in both at the same acid derivatives, which may be used for conden time. sation, there are suitable chlorides or esters, The carbamic acid chlorides, chlorocarbonic anides, imides, or anhydrides of carbonic acid or 30 acid esters, isocyanic acid esters and oils of mus thio-carbonic acid, whilst under carbonic acid tard, used as initial material, can be obtained chlorides and thio-carbonic acid chlorides there by the kriown processes. By treatment of pri are understood: carbonylchloride, thio-carbonyl mary or secondary aliphatic, aliphatic-aromatic, chloride, aliphatic, araliphatic, aliphatic-aro aromatic, heterocyclic, araliphatic, araliphatic matic, arOrnatic and heterocyclic carbamic acid 35 aromatic amines, such as aniline, toluidine, 4 chlorides, and also aliphatic and aromatic chlo chloraniline, 3:4-dichloraniline, 2:5-dichlorani rocarbonic acid esters. There have proved par line, 2:4-dichloraniline, 5:8-dichloro-1-naph ticularly valuable halogen and/or alkyl substi thylamine, 3-chloro-4-methyl-6-methoxy- ani tuted aromatic, aliphatic-aromatic and hetero line, 3-chloro-4-methyl-6-ethoxyaniline, 3:4-di cyclic carbanic acid chlorides, and also halogen 40 chloro-6-methoxyaniline, 4-nitraniline, ethyl and/or alkyl substituted aromatic chlorocarbonic aniline, 4-laurylaniline, laurylphenylarnine, di acid esters. phenylamine, 4:4'-dichloro diphenyl ether, 4'- The condensation products in question may, chloro-4-aminodiphenyl-sulphone, 2-amino-2- however, also be obtained by the addition of iso amino-benzthiazol, 3:4:5-trichloraniline, 2:4:5- cyanates, especially of halogen- and/or alkyl 45 trichloraniline, laurylamine, ex-dodecylbenzyl substituted aromatic-isocyanic acid esters, to amine etc., with phosgene a simple reaction pro aromatic or heterocyclic amino Sulphonic acids. duces the carbamic acid chlorides. By suitable Similar bodies are formed by the addition of aro conversion known perse the latter, obtained from matic or heterocyclic carbamic acid-chloride sul the corresponding primary amines, can be con phonic acids and isocyanate sulphonic acids re 50 verted easily into isocyanic acid ester. By the spectively to suitable aromatic or heterocyclic treatment of alcohols, for example dodecyl alco amines. Further the addition of Saturated or hol or phenols, especially halogen substituted unsaturated aliphatic, araliphatic or aromatic phenols such as 4-chlorophenol, 3:4-dichloro iso-thio-cyanic acid esters, especially halogen phenol, 3-methyl-4-chlorophenol, 2:4-dichloro substituted oils of mustard, to aromatic and 55 phenol and 4-nitrophenol with phosgene in the 2 2,3,032 presence of tertiary bases, there are formed the coradition however aways remains that after chlorocarbonic acid esters capable of reaction. codensation at east one halogen atom and One On the other hand isothiocyanates can be obs sulphonic acid group are present in the reaction tained from amines according to known proc product. esses; those which have been obtained by reas The Same or similar compounds are obtained rangement from thiocyanic acid esters have is the most cases if the condensations are per proved particularly accessible and Valuable. formed with the sulphonic-acid-group-free Benzylhalides, nuclear halogenated benzy armines &nd at the end of the reaction only the halides, and Saturated or unsaturated alkyl solubility of the end products is produced by a halides form a suitable initial material. succeeding Sulphonation. If the solubility of As aromatic amines there are preferably suit Stiphonic-acid groups containing acylamino able amino sulphonic acids, for example the sul compounds should still be enhanced, this can phonic acids of the arminOdiphenyls, &minosis likewise be done by subsequent sulphonation. phenylethers, annodiphenylmethanes, amino he use of halogen substituted aminosulphonic diphenylsulphides, aminodiphenylsulphoxides, 5 acids of the aromatic and heterocyclic series, arminOdiphenylsulphones, aminodiphenyanines, Row, is bound to determined, technically avail aninodiphenylketones, an in Ober 2, a nilides, able halogenated: compounds which owing to aminodiphenyl reas, aminOdiphenylthio areas, their tire ananufacture, that is the separation also simpie sulphonic acids of aniline, naphthyl of isoxers of by-products simultaneously formed amine, anisidine or nitraniline, are valuable. In 20 at the halogenation, are relatively expensive. this case there are especially suitable halogen Further the selection is rather limited by rea and/or alkyl substituted derivatives of the above SOE of the deterrained regularities of substitu mentioned amino- or polyamino-Sulphonic acids, tion at the halogenation. such as 3:4-dichlorandline-6-sulphonic acid, 4 From the iso- or heterocyclic aminosulphonic chlorandline Sulphonic acid, 4:4'-dichloro-2- acids containing exchangeable hydrogen at the amino-i:1'-diphenylether-2'-sulphonic acid, 4 25 2nitrogen atom there may be named amongst chloro - 4a amino - :' a diphenylethere 2'-Suia others halogenated aminodiphenylether-sul phonic acid, 4:2'-dichloro-3'-amino-1:1'-di phonic acids as particularly convenient. The phenylether - 2 - sulphonic acid, 3-methyl - &- same are for example obtained by condensation chloro - 4' - amino - :1 a diphenylether-2'-sul SC) of 0- or p-chloronitrobenzene-sulphonic acids phonic acid, 3:4 - dichloros 4's amino-1:1'-di With halogen phenols and subsequent reduction. phenylsulphide-2'-sulphonic acid, 3:4-dichloros he production of such halogenated aminodi 2' - amino - i:1' - diphenylsulphide-4'-sulphonic phenylether-sulphonic acids frequently involves acid, 4 - chloro-4-amino-1'-diphenylsulpho;K- certain difficulties in so far as the manufacture: ide - 2 - Sulphonic acid, é a chloroe?'-aminodi of the halogen phenols used as intermediate phenylsulphone - 2' a sulphonic acid, 3:4 is ti - 2 Sproducts, particularly that of the higher sub amino-1:1-diphenylmethane-2-sulphonic acid, stituted halogen phenols, is not so easy. Thus, 4. a chloro-chloro-4-aminodiphenylannine-2-sale one stacceeds for example easily in producing phonic acid, 4:4'-dichloro - 4's animodiphenyi gure p-chlorophenol and therefrom condensa ketOne-3-sulphonic acid, 3'-animobenzoyi-3:6a A.C. to products with nalogen nitrobenzene-sul dichloranilide-6-sulphonic acid. Of the heteroa phonic acids in pus are for . On the contrary it cyclic amino-Sulphonic acids may be mentioned is very difficult to aanufacture a sufficiently pure the anninobenzthiazolsulphonic acids, aminocar 2:4-dichloropheroi, as the admixtures of p bazolsulphonic acids, anninoacylcarazoso chlorophenoi and 2:6-dichlorophenol always phonic acids, aminodiphenylenoxide sulphonic present in the technical product can not be acids, and
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