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 aminophenothiolinesulphonic acids; easily separated off on account of the likeness in this case also the halogen substitution prod of their boiling points. As the latter compounds lucts have proved particularly valuable. also condense with the halogen nitrobenzene By a suitable selection of the substitution it sulphonic acids-and this still easier than the is possible to construct products with one or 50 2:4-dichlorophenol-there result after the re more sulphonic acids. For example by the ac duction in the most cases mixtures of halo tion of phosgene, thiophOSgene or carbondisul genated animodiphenylether-sulphonic acids in phide on halogenated aminodiphenylether more or less good yield, which are less adapted monosulphonic acids, there result ureas or thioa for Smooth condensation with carbonic acid ureas with two sulphonic acid groups. On the or thiocarbonic acid derivatives. Although such other hand, for example by the action of speci 55 inist are (may be used for many technical pur fied carbamic acid chlorides, especially of halo poses, it is preferable to employ more uniform genated, aliphatic-aromatic &nd heterocyclic products for other applications. carbamic acid chlorides on arminOSulphonic acids, By usual halogenation of completely formed, there are formed ureas with One Sulphonic acid not or not highly halogenated acylamino sul group. The invention thus concerns symmetris 30 phonic acids which are obtained according to cal and unsymmetrica urea, Sulphonic acids and the above process from reactive carbonic acid thiourea sulphonic acids, as well as those which or thiocarbonic acid-derivatives or such com at the nitrogen appear more or less completely pounds yielding substances or mixtures of sub alkylated, aralkylated or arylated. By condiensae stances and isocyclic or heterocyclic amines or tion of aminOSulphonic acids or alkylaminosula 65 aminosulphonic acids having exchangeable phonic acids with N-primary or secondary car hydrogen at the nitrogen atom, one obtains how bamic acid chlorides it is possible to produce ever also easily the corresponding halogenation di-, tri- and tetra-substituted ureas. By conver products which are also well adapted for deter sion of aminosulphonic acids and alkylamino mined purposes. By this means, there are ob. sulphonic acids with nitro-urea of cyanate, there 70 tained in part the same acylamino-sulphonic are formed mono- and di-substituted unsym acids as they are obtainable by use of halo metrical urea derivatives, the atter can for genated amines or aminosulphonic acids, in part, example be further condensed with acid chlo however, also substitution products halogenated ridies, alkyl chlorides, aldehydes or the like. The 75 in other positions. It is particularly to be noted 2,311,062 3 that by use of different halogens one obtains mild Sulphonation of 2-amino-4:4'-dichloro new compounds technically not available up to 1:1-diphenylether are dissolved in 200 parts of today. water, 30 parts of Crystalline sodium acetate are The herein claimed symmetrical and especially added and at 40-50 C. phosgene is introduced. unsymmetrical urea, -thio ureau and urethane The separated product is taken up in soda and sulphonic acids are predominantly suitable for thereupon salted out with Saturated cooking salt protecting wool, feathers, furs, hair, paper, tex solution, whereupon the urea, alone precipitates tiles, leather, natural or artificial fibres, or in crystalline form. The yield in N:N'-2:2'- articles containing these substances from moths (4':4'-dichloro-2':2'-disulphodiphenoxy)- and other textile destructive grubs. O 5:5'-dichlorodiphenylurea is a theoretical one. The pronounced fastness to Washing and full Instead of the above mentioned sulphonic acid ing of the products claimed is particularly worth it is possible to use other diphenylethersulphonic mentioning. By suitable substitution they are acids, namely those which are obtained by the also suitable as disinfecting agents, as bac after-Sulphonation of unsulphonated diphenyl tericides, fungicides and insecticides, as excellent 5 ethers, for example 4-amino-4'-chloro-1:1'-di mercury-free seed steeping materials, as valuable phenylether - 2 - Sulphonic acid, 4-amino-4'- agents against blood parasites and also as agents chloro-5'- methyl - 1:1'-diphenylether - 2'-sul for use in the textile industry. phonic acid, 4 - amino - 2:4' - dichloro-1:1'di The following examples illustrate the process, phenylether-2'-sulphonic acid, 2-amino-4:4'-di the parts being by weight, where nothing other 20 chloro-5'- methyl - 1:1'-diphenylether - 2'-sul is said. phonic acid, 4-amino-2:4'-dichloro-5'-methyl Eacample 1 1:1-diphenylether-2'-Sulphonic acid, 2-amino 16 parts of 4-amino-4'-chloro-5'-methyl-1:1'- 4:4:5' - trichloro - 1:1-diphenylether - 2'-sul diphenylether-2-sulphonic acid are dissolved in phonic acid, 4-amino-2:4:5'-trichloro-1:1'-di 250 parts of water with the necessary quantity 25 phenylether-2'-sulphonic acid, 2-amino-4:2'- of 10% soda solution. To this solution are dichloro-1:1'-diphenylether-4'-sulphonic acid, added 30 parts of crystalline Sodium acetate, and 4-amino - 4:6'-dichloro - 1:1-diphenylether-2'- phosgene is introduced at 40-50° C. until a sample sulphonic acid, 2-amino-4:4:6'-trichloro-1:1'- no longer indicates free amine. The Solution is diphenylether-2'-sulphonic acid, 2-amino-4:6'- then exactly neutralised by means of soda, the 30 dichloro-1:1'-diphenylether - 2'-sulphonic acid, urea, a N:N'-4:4'-(3':3'-dimethyl-4':4'- 2- annino - 4:4:5-trichloro - 5'- methyl-1:1'-di dichlorodiphenylhydroxy) - 3 : 3' - disulphodi phenylether-2'-Sulphonic acid, 2-amino-4:4:5- phenylurea, precipitates as a pasty mass, it is trichloro-1:1'-diphenylether-2'-sulphonic acid, separated, dried, ground and obtained as a bright 2-amino-4-chloro - 4'-amyl-1:1'-diphenylether excellently water-soluble powder. The yield is 35 2'-sulphonic acid or 4-amino-2-chloro-4-amyl quantitative. 1:1'-diphenylether-2'-sulphonic acid. Instead of the 4-amino-4'-chloro-5'-methyl Eacample 3 1:1-diphenylether-2-sulphonic acid there may also be used 4-amino - 4' - amyl - 6 - chloro 20 parts of 3-amino-4'-chloro-4-(4'-chloro 1:1'-diphenylether-2-Sulphonic acid, 4-amino 40 5'-methyl-2'-sulphophenoxy)-1:1' - diphenyl 2:4:5' - trichloro - 1:1 - diphenylethere 2 - Sul sulphone, produced by Condensation of 4-4'-di phonic acid, 2-amino-2:4:5'-trichloro-1:1'- chloro-3-nitro - 1:1 - diphenylsulphone and 3 diphenylether-4-sulphonic acid, 2-amino-5:4'- methyl-4-chlorophenol by means of potash lye dichloro-1:1'-diphenylether-i-Sulphonic acid, at 120-150° C., reduction and Sulphonation of the 2-amino-5:4'-dichloro-5'-methyl-1:1-diphenyl condensation product at 95 C. With Sulphuric ether-4-sulphonic acid, 4-amino-2'-chloro-1:1'- monohydrate for 3 hours, are dissolved in 250 diphenylether-2-sulphonic acid, 4-amino-4':6'- parts of water by means of Soda, 30 parts of so dichloro-1:1'-diphenylether-2-sulphonic acid, 2 dium acetate are added and at 40-50° C. phos amino-4:6'-dichloro- 1:1'-diphenylether-i-Sul gene is introduced until amine can no longer be phonic acid, 4-amino-4'-chloro-1:1'-diphenyl 50 traced, eventually further acetate must be add ether-2-sulphonic acid, 2-amino-4'-chloro-li ed. When acidifying, the urea. Sulphonic acid diphenylether-4-sulphonic acid, 2-amino-4'- precipitates in the form of a paste. It is pressed chloro-5'-methyl-1:1'-diphenylether-4-Sulphonic and dried. The yield is quantitative. acid, 4-amino - 4:5 - dichloro-1:1'-diphenyl It is also possible to use other phenoxydiphen ether-2-sulphonic acid, 4-amino-4'-chloro-3:5'- 55 ylsulphone Sulphonic acids as for example 3 dimethyl-1:1'-diphenylether-2-sulphonic acid, amino-4'-chloro-2-(4'-chloro-3'- methyl - 2'- 2-amino - 4'-chloro - 3:5’- dimethyl- i:1'-di Sulphophenoxy)-1:1' - dipenhyl - Sulphone or 3 phenylether - 4 - sulphonic acid, 4-amino-4- amino-4:5'-dichloro-4-(4'-chloro-3'- methyl chloro-3'- methyl- 6'-isopropyl-1:1'-diphenyl 2'-sulphophenoxy)-1:1'-diphenylsulphone. ether-2-sulphonic acid, 2-amino-4'-chloro-3'- 60 Eacample 4 methyl-6-isopropyl - 1:1'-diphenyl-ether-4-sul 17 parts of 2-amino-4'-chloro-1:1'-diphenyl phonic acid, 2-amino-3:6'-dichloro-i:1'-di sulphide-4-sodium-sulphonate, obtained by con phenylether-4-sulphonic acid, 4-amino-3:6'- densation and subsequent reduction of 4-chloro dichloro-1:1'-diphenylether-2-sulphonic acid, or thiophenol and o-chloro-nitrobenzene-Sulphonic 2-amino-4-amyl-6'-chloro - 1:1-diphenylether 65 acid, are dissolved in 250 parts of water, 50 parts 4-sulphonic acid. These diphenylether Sul of crystalline Sodium acetate are added thereto phonic acids are obtained by known processes and phosgene is introduced at 40-50 C. until by condensation and subsequent reduction, from amine is no longer traceable. The separated p-chloronitrobenzene sulphonic acid and/or pasty maSS is drawn off, Converted into the SOdi o-chloronitrobenzene sulphonic acid with corre 70 um salt and evaporated in vacuo, The urea sponding phenols. forms a bright coloured powder, which dissolves Eacample 2 clear in water. The yield is quantitative. 17.8 parts of 2-amino-4:4'-dichloro-1:1'-di Instead of 2-amino-4'-chloro-1:1'-diphenyl phenylether-2'-sodium sulphonate, produced by 5 sulphide-4-Sulphonic acid there may be used 4 4. 8,83,032 amino-4'-chloro-i:i-diphenylsulphée e 2 s still at 90-100°C. for 2 hours; tied it is cooled, poured phonic acid, 2-amino-4:5' a dicoso a 'a gi on to ice, sucked of, Washed with water and phenylsulphide-4-sulphonic acid, 4-3aino-45's dried. The 2-8-22 no-4:4'-dichloro-2'-diphen dichloro-2: il-diphenylsulphide-2-sulphonic acid, Sferaethane-2-3-phonic acid forms a white pow 4-amino-3':6'odichloro-i:' ... diphenylsulphide der of very Sweet taste. ( parts of this diphen 2-sulphonic acid, 2-amino - 3:6 - dichloro-2:1'- ymethane Sulphonic acid are dissolved in 50 diphenysulphide-4-sulphonic acid, 8-&mino-4's parts of Water by means of sodia, treated with roao-:'-dighenylsulphide-2-Sulphonic acidi, 2 the necessary quantity of crystaline sodium sce amino-4'-bromo-'-diphenylsulphide a 4: a gue tate and phosgene is introduced at 30-40 C, n phonic acid, 4-amino-5'-chloro-3'-(ethyl-'o C til the azo Reaction has disappeared. The dia ciphenylsuliphide-3-sulphonic acid, 4-amino-3'- phenylmethane area is treated as a 3xampie chloro-6'-methoxy - i:1' a diphenylsulphide - 2 - After drying under reduced pressure it forms a sulphonic acid, 4-amino-3:4:6'etachioro-3'a oright powder which dissolveg clear a Water, diphenylsulphide-2 - sulphonic acid, 2 - a minoe Ecgfrage 3 3:4:6'-trichloro-i:'-diphenylsulphide - 4-sul 5 phonic acid, 4-amino - 2:4' - dichloro as 'od is 22 parts of 4-2.0-4'-calcro-: adiphenyi phenylsulphide-2-sulphonic acid, o' 2-3 aroe ether and 19 parts of 3:4-dichlorophenyigocy 3:3'-dichloroa: 1'-dipherylsulphide-4-Signonic an Ete bog point 3 ER. 23-26 C. Sneing acid. point, 45-48 C., produced Sroatia 3:3-dichorasailine Facciarage 5 20 &nd phosgene acco''dig to 2 EOWS process, are 10 parts of 4-amino-4'-chloro-i: l'adiphenyl thoroughly integralized a legated to 120° C. anine-3-sulphonic acid, produced oy the K2OWE, At this experature the Areaction saxes place and process from p-chlor-aniline and p-chloronitroe the temperature increases attomatically to 45° benzenesulphonic acid, are dissolved in 50 parts C. Then it is heated for g, further 3 hours up to of water and the necessary quantity of sodia, 25 25 60-70° C. and then allowed to cool. There are parts of crystalline sodium acetate are added and obtained 39 parts of an unsymmetrical urea de phosgene is passed through at 36-40° C. Rati 20 rivative. 39 parts of this N'-(4'-chlorophe nore amine is present. The paste precipitated noxy)-phenyl-N'-3:4-dichloropheny rea, are With acid is separated, converted with SOda, into introduced into 200 parts by weight of sulphuric 30 acid nonohydrate at 50 C. he sixture is then the sodium salt and salted out with cooking Sait. cooled to -0 to -5 C. and at this temperature The product, a grey powder, dried in vacuo, is there are dropped in 35 parts by Weight of 25% clearly soluble in water. The yield is excellent. oleum and stirring takes place at this tempera Instead of the above diphenylaminesulphonic ture until a sample is solube in diluted alkali, acid there may also be used another one 2s for It is then poured on ice, the acid is netraised example 4-amino-3:4'-dichloro-3'-dipienyl and salting out is effected. Yies 4 parts of a anine-2-sulphonic acid or 4-initioné':6'-dio clear water-solubie product. 2-play there has chloro-1: '-diphegyiszaine-2-Suipoic acid. been formed the N-4'-(2'-gugphc-4'-chloro Eagitage 6 phenoxy)-phenyl-N'-3:4-dichlorophenyi area. 20 parts of 4-amino-4'-chloro-1:3'-diphenyl 40 Egarape 9 sulphone-2-sulphonic acid are dissolved in 250 parts of water with the necessary quantity of 44 parts of 4-amino-4'-chloro-1:1'-diphenyl soda, 30 parts of sodiurn acetate are added there ether are treated with 50 parts by voiune of al to and phosgene is passed therethrough a 40 cohol, 50 parts by volune of carbon disulphide 50° C. When amino is no longe traceable the and 0.3 part by Weight of sulphur and heated precipitated sulphonic acid is coverted into the to boiling for 6 hours in the leftig cooler; streaRRs sodium salt and this is dried Ander reduced of Sulphuretted hydrogen escape. The resulting pressure. The yield is quantitative. N,N'-4:4'-(4':4'-dichlorodiphenoxy) - diphen Instead of 4-amino-4-chloro-i:1'-diphenyl ylthio urea is sucked off and washed with a lite sulphone-2-sulphonic acid there may be used 2 50 tle alcohol. it forms silvery sparking scales with amino-4'-chloro-i:1'-diphenylsulphone - 4 - Sull a melting point of 92 C. phonic acid, 4-amino-3':4' - dichloro - 1:1 - di 43 parts of N:N'-4:4-(4':4'-dichlorodiphe phenylsulphone-2-sulphonic acid or 2-arino noxy)-diphenylthio rea, are introduced into 200 3:6'-dichloro-1:1' - diphenylsulphone - 4 - still parts of Sulphuric acid monohydrate at about 10' phonic acid. 55 C. and slowly heated to 20 C, until a sangple tea Eacample 7 comes clearly water-soluble. The sulphonating Irass is poured on to ice and Salted out. The 103 parts by weight of nitro-p-chlorobenzyl N:N'-4:4'-(2':2'-disulpho - 4':4's dichloro chloride, boiling point 11 mm. 160-iO C. pro diphenoxy)-diphenylthio urea then separates. duced by nitrating p-chlorobenzylchloride, are stirred with 300 parts by volume of chloroben 60 Eacgmaple it zene and 100 parts of aluminium chloride at 25 16.5 parts of the 2-amino-4:4'-dichloro-1:'- C. until hydrochloric acid ceases to be foraried. diphenylmethane-2'-sulphonic acid, described The excess chlorobenzene, after decomposition in Example 7, are dissolved in 100 parts by Wol of the aluminium chloride with ice is driven of une of dry pyridine, and into the solution there with steam, the residue is ethered out, dried and 65 are introduced at 10-15 C., whilst thoroughly distilled under reduced pressure. The conden stirring, 10 parts of 3:4-dichlorophenylisocy sation product, probably. 2-nitro-4:4'-dichloro anate in Small portions. After hour the azo 1:1-diphenylmethane boils at boiling point 5 reaction has disappeared, the reaction mixture is mm. 220-230 C. then treated with steam until no further pyridine By reduction with iron there is obtained the 2 70 passes Over. The residue is received in one tre amino-4:4' - dichloro - 1:1' - diphenylmethane, of Water and filtered hot. From the hot filtrate boiling point 15 mm. 220-230 C. there separates on cooling the N-2'-(4'-chloro 55 parts of this base are introduced into 500 2'-sulphobenzyl)-5'-chlorophenyl- N's 3:4 - di parts of sulphuric acid monohydrate and stirred 75 chlorophenyl urea, in white fakes. They are 2,811,062 5 sucked of, washed with a little water and dried volume of 10% soda solution and the mixture in vacuo. The yield is quantitative. is treated with steam until all the pyridine has Instead of 3:4-dichlorophenylisocyanate there passed over. The residue is cooled, the separated may be used 4-chlorophenylisocyanate, 3-chloro resin removed and received in 500 parts of hot phenylisocyanate, 2-chlorophenylisocyanate, 4 water, faltered hot, and from the filtrate there is nitrophenylisocyanate, 2:4-dichlorophenylisocy precipitated with a little brine the N-2'-(4'- anate, 2:5 dichlorophenylisocyanate, 2:4:5-tri chloro - 2'' - Sulpho-phenoxy)-5'-chloro-N'-3:4- chlorophenylisocyanate, 3:4:5-trichlorophenyl dichlorophenyl urea, as a thick bright resin. It is0cyanate. is separated from the aqueous layer and dried Eacample 11 0 in vacuo, whereby the product is obtained as a 23 parts of 4-amino-4'-chloro-l:1'-diphenyl bright brittle mass. The yield is quantitative. ether-2'-sodium sulphonate (70%) are suspend Instead of 2-amino-4:4'-dichloro-1:1'-diphen ed in 100 parts by volume of dry pyridine and ylether-2'-sulphonic acid other Sulphonic acids there are added thereto at 20 C., whilst thor of the diphenylether series may be used, for ex oughly stirring, 10 parts of phenyl oil of mustard. 5 ample 4-amino-4'-chloro - 5' - methyl - 1:1'-di The temperature rises slowly automatically up to phenylether-2-Sulphonic acid, 4-amino-4-amyl 35 C., whereby the sulphonic acid passes slowly 6'-chloro-1:1'-diphenylether-2-sulphonic acid, 4 into solution. After hour no further annine is amino-2:4:5'-trichloro - 1:1'-diphenylether-2'- traceable, the Solution is then treated with SOme Sulphonic acid, 4-amino-4':6'-dichloro-1:1'-di sodium bicarbonate and the pyridine is driven 20 phenylether-2-Sulphonic acid, 2-amino-4':6'-di off with steam. After an addition of 250 parts chloro-1:1'-diphenylether - 4 - sulphonic acid, 4 of hot water it is again boiled and then filtered amino-4:5'-dichloro - 1.1'-diphenylether-2-sul hot. From the clear filtrate there is precipitated phonic acid. The aminodiphenylsulphides such by means of a cooking salt solution, the Condensa as the 4-amino-4':5'-dichloro-1:1'-diphenylsul tion product, a N-4'-(4'-chloro-2'-Sulphophe 25 phide-2-sulphonic acid condense quantitatively noxy)-phenyl-N'-phenylthio rea, as a thick with 3:4-dichlorophenyl carbamic acid chloride. resin. It is dried in vacuo and then forms a brit- . Instead of the 3:4-dichlorophenyl carbamic acid tle easily water-soluble mass. chloride the equivalent quantity of 3:4-dichloro Instead of the 4-amino-4'-chloro-1'-diphen phenylisocyanate can be treated with the enum ylether-2'-sulphonic acid, a sulphonic acid (as 30 erated amino-Sulphonic acids. enumerated in Example 1) may be used. In ad Eacample 14 dition to phenyl oil of mustard there may also be used ally oil of mustard, benzyl-oil of mus 12 parts of 1-amino-3:4-dichlorobenzene-6- tard, 4-chlorobenzyl oil of mustard, 3:4 dichloro sulphonic acid are dissolved in 75 parts by vol benzyl oil of mustard, 2-chlorobenzyl oil of mus 35 ume of dry pyridine. Then whilst stirring there tard, 3-chlorophenyl oil of mustard. are introduced at 10-15 C. in small portions, 15 parts of 3:4-dichlorophenyl carbamic acid chlo Eacample 12. ride and the whole is stirred for 1 hour at 15 parts of 4-amino-4'-chloro-1:1'-diphenyl 40-50° C. When no further free amine is trace ether-2'-sodium sulphonate are suspended in 150 40 able, the reaction mixture is treated with soda parts by volume of acetone and there are then Solution and the reaction mixture is then treated added 3 parts of carbon disulphide. At 10-15 C. with steam until no further pyridine passes over. there are added in drops, whilst thoroughly stir The residue is boiled with water, filtered and ring 50 parts by weight of hydrogen peroxide treated with a little cooking salt solution. The (3%). Stirring then takes place for 3 hours at 45 condensation product, the N-3:4-dichloro-6-sul 15-20 C.; should the azo reaction after this pe phophenyl-N'-3':4'-dichlorophenyl urea is ob riod of time be not yet negative, treatment is tained in beautiful laminae which after washing again carried out with 3 parts by weight of car and drying in vacuo give the following analysis: bon disulphide and thereupon with 50 parts by weight of hydrogen peroxide and further stirring Found Cl:31.67% S:7.06% Yield very good. for 1 hour at 15-20° C. It is now poured into a 50 Calculated Cl:31.5% S:7.08% concentrated cooking salt solution, the separat Instead of the 1-amino-3:4-dichlorobenzene-6- ed resin is removed and distilled with Water Wa Sulphonic acid another halogenated aniline sul pour. The distillation residue is freed from any phonic acid may be used, for example 4-chloro sulphur and the clear filtrate is treated with 55 andlineSulphonic acid or 2:4-dichloraniline-5- brine, whilst the condensation product separates Sulphonic acid. as a rudy-grey resin. It is separated and dried Eacample 15 in vacuo, whereby it solidifies to a brittle grey mass which by rubbing is converted into a bright 10 parts of metanilic acid are dissolved in 75 powder. The product is clearly Water-soluble. parts by volume of dry pyridine and the solu Instead of the 4-amino-4'-chloro-1:1'-diphen 60 tion is treated slowly at 5-10° C. whilst thor ylether-2'-sulphonic acid other sulphonic acids Oughly stirring with the equivalent quantity of of the diphenylether series may be used, those 3-chloro-6-(4'-chlorophenoxy)-phenyl carbamic for example mentioned in Examples 1 and 2. acid chloride, produced from 2-amino-4:4'-di chloro-1:1'-diphenylether and phosgene accord Eacample 13 65 ing to known processes. It is then further stirred 9 parts by Weight of 2-amino-4:4'-dichloro for 1 hour at 40-50° C., then treated with soda 1:1'-diphenyl-ether-2'-sulphonic acid are dis and the pyridine removed as in Example 1. The solved in 50 parts by volume of dry pyridine. residue is received in hot water, filtered and the The Solution whilst thoroughly stirring is treated clear filtrate is treated with a little cooking salt at 10-15 C. in small portions with 10 parts of Solution. There thus separates the N-3'-chloro 3:4-dichlorophenyl carbamic acid chloride and 6'-(4'-chloro - phenoxy)-phenyl-N'-3-sulpho after all the carbamic acid chloride has been in phenyl urea. It is separated, dried in vacuo and troduced it is heated for a further hour at then forms a bright rose coloured powder which 40-50° C. Then it is treated with 100 parts by 75 dissolves well in water. S 2,311,062 Eacample 16 Eacample 20 44 parts of 4-amino-4'-chloro-1:1'-diphenyl 10 parts of 4-amino-4'-chloro-l:1'-diphenyl ether are intimately mixed with 7 parts of urea ether-2-sulphonic acid are dissolved by means and slowly heated to 160-170° C. until no further of soda in 150 parts of water and treated in the ammonia escapes, which occurs as a rule after presence of acetate with a slight excess of thio 3 hours. The yield in N,N'-4:4'-(4':4'-di phosgene. The temperature is here maintained chloro-diphenoxy)-diphenyl urea, amounts to 46 at 40-50 C., whereby the azo reaction should parts. disappear slowly, otherwise there is added fur The above urea is introduced at 10 C. into ther acetate and a little thiophosgene. Then it is 200 parts of sulphuric acid monohydrate, then 0 cooled, acidified with dilute hydrochloric acid cooled to -10° C. and 65 parts of 26% oleum and the thio-urea isolated. It is again received are added in drops. After half an hour a sample in soda and precipitated with brine, filtered and is easily soluble in water; the reaction mixture dried in vacuo. is poured on to ice and salted out. After drying Eacample 21 in vacuo 48 parts of a water-soluble disulphonic 5 acid are obtained. 18 parts of 2-amino-4:4'-dichloro-1:1'-di Eacample 17 phenylether-2'-sodium sulphonate are dissolved in 200 parts of water and at room temperature 40 mol. of m-aminobenzoyl-3:4-dichloran there are added in drops ill parts of 4-chloro ilide-6-sulphonic acid are dissolved in 100 parts 20 phenol carbonic acid chloride, produced accord by volume of dry pyridine, and the solution, ing to German Patent 516,285; the resulting hy whilst stirring and cooling, is treated slowly at drochloric acid is neutralised by means of SOda. 10-15 C. with 10 parts of 3:4-dichlorophenyl The urethane-sulphonic acid precipitates in the carbamic acid chloride. After introducing the form of a paste, is separated and dried in vacuo latter the whole is stirred for another A hours 2. and then forms a powder which is fairly difficult until the azo reaction disappears. Then it is to dissolve in Water. treated with Some Soda and the pyridine is blown It is also possible to use other phenyl- or of With Steam. The residue is introduced into alkyl-chloro-carbonic acid esters. litre of hot water, rapidly boiled, filtered hot and the filtrate is treated with brine. The con 30. Eacample 22 densation product is precipitated as a grey resin; Phosgene is passed according to the above ex it is separated and dried in vacuo. amples through 3'-methyl - 4 - a nirodiphenyl na - Aminobenzoyl - 3:4 - dichloranilide-6-sul ether-2-sulphonic acid to produce Syngetrical phonic acid is obtained by conversion of 3 urea. The new compound is obtained as City nitrobenzoylchloride With 1-amino-3:4-dichloro 35 liquid, which is easily soluble in Water, from benzene-6-sulphonic acid in pyridine. The nitro which solution it can again be separated by addi body is reduced with iron according to known tion of hydrochloric acid. The new compound is processes and is precipitated from the soda insoluble in chloroform and carbon tetrachloride, alkaline filtrate obtained by means of hydro but soluble in glacial acetic acid. choric acid. 40 2 parts of this urea derivative are dissolved Eacample 18 in 50 parts by Volume of glacial acetic acid and 30 noi. of 4-amino-4-alkyl-1:1'-diphenyl chlorine is passed therethrough for about 1 hour ether-2-sulphonic acid is dissolved in 200 parts up to saturation. The chlorination product is by volume of dried pyridine or acetone and, precipitated by means of water containing hy whilst stirring, is treated at 10-15° C., in por 45. drochloric acid, in form of yellow, semi-solid tions, with 10 parts of 3:4-dichlorophenyliso mass soluble in Water. Content of chlorine: Cyanic acid ester, then further stirred at room 20.2% or about 4 atoms per Inoiecule. temperature until the azo reaction has disap Eaccomple 23 peared. After the addition of 50 parts of 10% SOda, Solution, the pyridine or acetone is blown 50 12 parts of the urea, derivative according to off with steam, the residue boiled with 2 litres the preceding example are dissolved with the of Water whilst introducing steam, filtered hot calculated quantity of soda in iOO parts of Water and the condensation product is precipitated and chlorine is introduced thereinto at 30-40 C., from the filtrate as a thick resin by means, of whereby the reaction is maintained alkaline by brine. It is separated and dried in vacuo. The 55 a drop-by-drop addition of caustic Soda lye. N:4'- (4'-amylphenoxy) - 5 - sulphophenyl-N'- After 2 hours, the chlorinated product is pre schlorophenyl urea is readily soluble in hot cipitated by means of hydrochloric acid and Water. obtained as friable brownish maSS which contains Eacample 19 34.6% of bound chlorine. This content lies in 60. the neighbourhood of the theoretical Value for 8 18 parts of 2-amino-4:4'-dichloro-1:1'-di atoms of chlorine per molecule (33.1%). phenylether-2'-sulphonic acid (40 mol.) are dis Similar halogen substitution products are ob Solved in 100 parts by volume of dry pyridine and tained if the chlorination, for example in glacial treated at 5-10 C., whilst stirring, with 20 parts acetic acid, is interrupted after some time and of 2:5-dichlorophenyl carbamic acid chloride. 65 the halogenation is continued with a calculated After the first reaction further stirring takes quantity of bromine. place at 40-50° C. and then the treatment is Instead of the aforesaid urea derivative, the carried out (as indicated in Example 1). The other acylaminosulphonic acids enumerated in No. 2'-(4'-chloro-2'-sulphophenoxy)-5'-chloro great number in the specification and the ex phenyl-N'-2:5-dichlorophenyl urea is readily O amples and their halogen-poorer or halogen-free soluble in hot water. Instead of the 2:5-dichlorophenyl carbamic parent bodies may be used. acid chloride there may be used the diphenyl Eacample 24 carbamic acid chloride or the N'-laurylpheny is mol. of 4:4'-dichloro-2-amino-l:1'-di carbamic acid chloride, 75 phenylether-2'-sulphonic acid are dissolved in 2,811,062 7 100 parts by volume of water-free pyridine and wherein Y, m and X have the above-defined the solution is introduced while stirring and cool meanings, there beling at least one SO3H group ing at 10-15 C. in small portions into mol. of in at least one of the aforesaid benzene nuclei 3:4-dimethylphenylisocyanate, obtained in the and at least one halogen atom in at least one manner above referred to from 3:4-dimethyl of said nuclei, said derivatives being useful for aminobenzene and phosgene. Thereupon stir durably protecting wool and other substances ring is continued for One hour without cooling, against moths and for disinfecting and like pur then a little soda solution is added and the pOSes. pyridine distilled off by means of steam. The 2. The urea derivatives of the formula distillation residue is filtered hot and the filtrate 10 mixed with a solution of common salt, whereby Z, NHE CONHR, the condensation product is precipitated as a wherein Z represents the radical of a halogen thick grey resin. The mass is separated off from substituted diphenyl ether, and R represents a the aqueous solution and dried in vacuo. The member of the group consisting of new compound is obtained as a grey brittle mass 15 which is easily soluble in water. Eacample 25 102 parts of 5-chloro-2-hydroxydiphenyl are melted together with 86.5 parts of 2-chloro 20 wherein Y represents a member of the group nitrobenzene and mixed at 130-140° C. With 28 consisting of H, alkyl and halogen, and n is parts of potash lye dissolved in 30 parts of one of the integers 1 and 2, at least one of water. Then the whole is heated during 8 the benzene nuclei present containing an SO3H hours to 150-160° C., thereupon the reaction mass group, said derivatives being useful for durably is poured into water, rendered alkaline and 25 protecting wool and other substances against treated with steam. After cooling the nitro-body moths and for disinfecting and like purposes. is filtered off, washed and reduced in acid solu 3. The urea derivatives of the following gen tion with iron. From the residue of reduction eral formula the base is extracted by means of chlorobenzene and distilled in high vacuo. Boiling point at 0.2 mm. pressure: 185 C. 30 2-NH.C. oNH-{X 35 parts of this base are slowly introduced, while being cooled by ice and stirred, into 250 . parts of sulphuric acid monohydrate, then Wherein Z. means the radical of a halogen stirred during 4 hours at 15-20° C. and finally substituted diphenyl ether, Y means substituents the violet solution is poured onto ice. The selected from the group consisting of H, alkyl separated sulphonic acid is sucked off, dissolved and halogen and n is one of the integers 1 and 2, in dilute caustic Soda lye, the Solution is filtered at least one of the benzene nuclei present con and the filtrate acidulated with acetic acid. By taining one SO3H group, these compounds being addition of an equal volume of common salt 40 useful for durably protecting wool and other solution, the sodium salt of the new Sulphonic Substances against moths and for disinfecting acid is precipitated out. The same is sucked off, and like purposes. washed with dilute brine and dried in vacuo. 4. The urea derivatives of the following gen 18 parts of this compound are dissolved in 100 eral formula parts by volume of dry pyridine and this solu tion is mixed at 10-15 C. with 70 parts of a 15 per cent solution of 3:4-dichloro-phenylisocyan HOSKXXiong> ate in nitrobenzene. After stirring during 5 L. Y. hours without cooling the solvents are distilled wherein Y means a substituent selected from off by means of steam, the distillation residue 50 the group consisting of H, alkyl and halogen, is dissolved in hot water and the whole filtered and 72 means one of the integers 1 and 2, these off. From the filtrate the new condensation compounds being useful for durably protecting product separates out on cooling, it is sucked wool and other substances against moths and off, washed with some water and dried in vacuo. for disinfecting and like purposes. Instead of the carbonic acid- or thiocarbonic 55 acid derivatives mentioned in the above exam 5. The urea derivatives of the following gen ples, there can obviously also be used the other eral formula, compounds cited in the preamble or general part of this specification. What we claim is: OS-- 1. The urea derivatives of the formula: 60 L wherein Y means a substituent selected from the group consisting of H, alkyl and halogen, and n. { X-X-XX-Nhic O.NH-R means one of the integers 1 and 2, these com Y. Y. 65 pounds being useful for durably protecting wool wherein X represents a linking member selected and other substances against moths and for dis from the group consisting of O, S, and SO2, infecting and like purposes. Y represents a member of the group consisting 6. The halogen substituted urea of the fol of H, alkyl and halogen, n is one of the integers i lowing formula and 2, and R represents a member of the group consisting of 70 SONa NBC on- a 75 S 2,311,062 being particularly useful for durably protecting 8. The halogen Substituted urea of the follow wool and other substances against moths. ing formula 7. The halogen substituted urea of the foll- CH lowing formula C.I .

5 C-C-0 soNa soon (C-ONa Hick)-0 NB.CO.NB Cl being particularly useful for durably protecting wool and other substances against moths. ONa 0. HENRY MARTIN. HANS HENRICH ZAESLIN. being particularly1. useful- for durably protecting CURTRUDOLF GLATTHAAR. HRT. wool and other substances against moths. ALFRED STAUB. Certificate of Correction Patent No. 2,311,062. February 16, 1943. HENRY MARTIN ET AL. It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Column 7, lines 57 to 60, inclusive, claim 5, for that portion of the formula reading

22A

THOMAS F. MURPHY, Assistant Oommissioner of Patents.