Patent GB-482524-A (GB)
Title: Process for the manufacture of aromatic polysulphonamido compounds
IPC: C14C3/18
Filed: 1936-10-03
Abstract: Processes are described for the preparation of compounds containing at least five aryl nuclei linked by at least four -SO2NH-groups; the compounds contain also at least two sulphonic acid groups, and when more than five aryl nuclei are present the linkages between them may include -CONH- groups.  In one method of preparation, the starting material is a compound in which two or more aryl nuclei are linked by a group or groups -SO2NH- and/or -CONH-, one of the terminal aryl nuclei containing an acylatable amino group and at least one of the aryl nuclei containing a sulphonic acid group; the starting material may also contain an additional amino group or an aliphatic acylamino group (A) or a nitro group.  Two mols. of a starting material of the type defined are condensed with an aromatic disulphonic or dicarboxylic acid halide, an aliphatic dicarboxylic acid halide or phosgene, and if the product still contains free amino groups, or if amino groups are producible in the product from a nitro group or an aliphatic acylamino group (A) in the starting material, these amino groups are finally acylated with an arylsulphonic or arylcarboxylic acid residue, the reagents being so selected that the final products have the features set out above.  Disulphonic or dicarboxylic acid halides for use in this process include those derivable from benzenedisulphonic acids, toluenedisulphonic acids, naphthalene-1 : 5- or -2 : 6-disulphonic acid, diphenylsulphonedisulphonic acids, phthalic acid and isophthalic acid.  In an alternative process, an aromatic disulphonic acid halide is condensed with between one and two mols. of an aromatic diamine containing at least one sulphonic acid group; this leads, in the first instance, to products of the type R1NHSO2 RSO2NHR1, where R is the aryl residue of the aromatic disulphohalide and R1 is the aryl residue of the aromatic diamine, each residue R1 containing an amino and a sulphonic group; further condensation may then occur with the production of products of the type R1NHSO2RSO2NHR1NHSO2 RSO2 NHR1NH SO2 RSO2 NHR1, where R and R1 are as above except that only the terminal radicles R1 contain a free amino group; in any event, the final step consists in acylating the free amino groups with an arylsulphonic or arylcarboxylic acid residue, the reagents being so selected that the final products have the features set out above.  Aromatic disulphohalides for use in this process include those derivable from benzenedisulphonic acids and their substitution products, naphthalene-1 : 5-or -2 : 6-disulphonic acid, and diphenyldisulphonic acids.  Aromatic diamines for use in the process include 2 : 6-toluylenediamine-4-sulphonic acid, benzidine-2 : 21-disulphonic acid, 1 : 3-phenylenediamine-4-sulphonic acid, 2 : 4 - toluylenediamine - 5 - sulphonic acid, 1 : 4-phenylenediamine-2-sulphonic acid, benzidine- and tolidine-monosulphonic acids, 4 : 41-diaminostilbenedisulphonic acids, 4 : 41-diamino dibenzyldisulphonic acids, and bis(31-aminobenzene-11-sulphonyl)-2 : 6-toluylenediamine-4-sulphonic acid.  The products are useful as reserving agents for animal fibres against coloration with substantive dyes, as precipitating agents for basic dyes for dyeing lacquers, and, in some cases, as mordants for basic dyes. Weakly acidified solutions of the alkali and ammonium salts of the products are useful as tanning agents.  The following examples are given: (1) 311-Aminobenzene-111-sulphonyl-31 - aminobenzene - 11 - sulphonylaniline - 4-sulphonic acid is first prepared by condensing the sodium salt of aniline-4-sulphonic acid in aqueous solution with 3-nitrobenzene sulphochloride, reducing the product by means of iron, condensing again with 3-nitrobenzenesulphochloride, and reducing again; 2 mols. of the compound are then condensed with 1 mol. of 1 : 2-dichlorobenzene-4 : 6-disulphochloride, obtainable from 1 : 2-dichlorobenzene and chlorosulphonic acid; the specified starting material may be replaced by analogous compounds in which the aryl nuclei may be of the benzene, naphthalene or diphenyl series and may carry halogen atoms or alkyl groups, while in place of 1 : 2-dichlorobenzene-4 : 6-disulphochloride there may be used other halogen-substituted benzenedisulphochlorides, benzene - 1 : 3 - disulphochloride, toluene-disulphochlorides, naphthalene- or diphenyldisulphochlorides or aromatic or aliphatic dicarboxylic acid chlorides or phosgene. (2) Mono (31 : 41 - dichlorobenzenesulphonyl)-2 : 6 - toluylenediamine : 4 - sulphonic acid is first prepared by condensing 6-oxalylamino-2-toluidine-4-sulphonic acid with 3 : 4-dichlorobenzenesulphochloride and splitting off the oxalyl group; two mols. of this product are then condensed with one mol. of benzene-1 : 3-disulphochloride.  (3) Mono(m-nitrobenzoyl)-2 : 6 - toluylenediamine - 4 - sulphonic acid (obtainable from 6-oxalylamino-2-toluidine-4-sulphonic acid and m-nitrobenzoyl chloride and subsequent removal of the oxalyl group) is condensed with benzene-1 : 3-disulphochloride and the product is reduced with iron and hydrochloric acid; the reduced product contains two amino groups (it yields an orange-red dye when tetrazotized and coupled with the sodium salt of 2-naphthol-3 : 6-disulphonic acid), and these amino groups are finally acylated by reaction with 3 : 4-dichlorobenzenesulphochloride.  (4) Mono(m-nitrobenzenesulphonyl) - 2 : 6 - tolyulenediamine - 4 - sulphonic acid (obtainable by condensing 6-oxalylamino-2 - toluidine - 4 - sulphonic acid with m-nitrobenzenesulphochloride and then removing the oxalyl group) is condensed with benzene-1 : 3-disulphochloride and the product is reduced as in example 3; the reduced product contains two amino groups (it yields an orange-red dye when tetrazotized and coupled with the sodium salt of 2-naphthol-3 : 6-disulphonic acid), and these amino groups are finally acylated by reaction with benzoyl chloride. (5) 2 - (m - Aminobenzenesulphonyl)amino - 6-oxalylaminotoluene - 4 - sulphonic acid (obtainable by condensing 6-oxalylamino-2-toluidine-4-sulphonic acid with m-nitrobenzenesulphochloride and reducing the nitro group) is condensed with benzene-1 : 3-disulphochloride and the product is heated with aqueous hydrochloric acid to saponify the oxalylamino groups; the diamino compound so obtained is then condensed with 3 : 4-dichlorobenzenesulphochloride.  (6) The product of example 5 is obtained by condensing benzene-1 : 3-disulphochloride with 6-(31-aminobenzenesulphonyl)amino - 2 - (311 : 411 - dichlorobenzenesulphonyl)aminotoluene - 4 - sulphonic acid, which is obtainable by condensing 3 : 4-dichlorobenzenesulphochloride with 6 - oxalyl - amino - 2 - toluidine - 4 - sulphonic acid, saponifying the oxalylamino group, condensing the saponified product with 3-nitrobenzenesulphochloride, and reducing the nitro group.  (7) The polynuclear starting material of example 6 is condensed with diphenylsulphone-3 : 31-disulphochloride, or (example 8) with naphthalene-1 : 5- or -2 : 6-disulphochloride, or (example 9) with phosgene, or (example 10) with isophthalyl chloride: the toluylenediamine derivatives used in examples 2-10 may be replaced by analogous derivatives of 1 : 3 - phenylenediamine - 4 - or 5 - sulphonic acid, 2 : 4 - toluylenediamine - 5-(or 6-)sulphonic acid, or 1 : 4-phenylenediamine-2-sulphonic acid. (11) Bis(m-aminobenzenesulphonyl)benzidine - m, m - disulphonic acid (Specification 333,559, [Class 2 (iii)]) is condensed with 3 : 4-dichlorobenzenesulphochloride and the product, which contains a free amino group, is condensed with benzene-1 : 3-disulphochloride; the benzidine derivative used as starting material may be replaced by bis (m - aminobenzenesulphonyl) - tolidine - m, m-disulphonic acid or bis(m-aminobenzenesulphonyl) - diaminostilbenedisulphonic acids or a bis(m-aminobenzenesulphonyl)-phenylenediamine- or -toluylenediamine-sulphonic acid.  (12) 2 : 6-Toluylenediamine - 4 - sulphonic acid is condensed with benzene-1 : 3-disulphochloride and the product, which contains amino groups, is condensed with 2 : 4 : 5-trichlorobenzenesulphochloride; in place of benzene-1 : 3-disulphochloride there may be used monochlorobenzenedisulphochlorides, 1 : 2-dichlorobenzene - 4 : 6 - disulphochloride, or a toluenedisulphochloride, while in place of 2 : 6 - toluylenediamine - 4 - sulphonic acid there may be used 1 : 3-phenylenediamine-4-(or 5-)sulphonic acid or 2 : 4-toluylenediamine-5-(or 6-)sulphonic acid; the trichlorobenzenesulphochloride used in the final acylation may be replaced by benzenesulphochloride or other halogen- or alkyl-substituted benzenesulphochlorides or a naphthalenesulphochloride.  (13) 2 : 6 - Toluylenediamine - 4 - sulphonic acid is condensed with 1 : 2-dichlorobenzene-4 : 6-disulphochloride and the product, which still contains amino groups, is condensed with 1 : 2 - dichlorobenzene - 4 - sulphochloride; the alternative reagents indicated in example 12 may also be used, as well as mixtures of such reagents, e.g. a mixture of dichlorobenzene disulphochloride with benzenedisulphochloride or monochlorobenzenedisulphochloride, while in the final acylation use may be made of a mixture of 3 : 4-dichlorobenzenesulphochloride with 2 : 5-dichlorobenzenesulphochloride or 2 : 3 : 4- (or 2 : 4 : 5-)trichlorobenzenesulphochloride.  (14) A product prepared, as in example 12, from 2 : 6-toluylenediamine-4-sulphonic acid and benzene-1 : 3-disulphochloride is condensed first with 1 : 2-dichlorobenzene - 4 : 6 - disulphochloride and then with 3 : 4-dichlorobenzenesulphochloride.  (15) 2 : 6 - Toluylenediamine-4-sulphonic acid is condensed with naphthalene-1 : 5- (or 2 : 6-)disulphochloride, and the product, which still contains amino groups, is condensed with 3 : 4-dichlorobenzenesulphochloride. (16) 2 : 6 - Toluylenediamine-4-sulphonic acid is condensed with diphenylsulphone-3 : 31-disulphochloride and the product, which still contains amino groups, is condensed with 3