Patent GB-656590-A (GB)
Title: Manufacture of new amine derivatives and application thereof in industrial processes, in particular as optical bleaching agents
Filed: 1948-11-16
Abstract: Water-solubilizing groups are introduced into the amino group of a blue-fluorescent compound (other than an amino-coumarin or an amino-naphthalene sulphonic acid) by treating it with (a) an aldehyde bisulphite or with an aldehyde and sulphur dioxide, or (b) an alkyl or aralkyl halide containing at least one sulphonic or carboxylic acid group preferably in the presence of an p  acid-binding agent, or (c) the addition product of pyridine and sulphur dioxide, or (d) an N-methylolamide of a carboxylic acid with at least one water-solubilizing group in the acyl radical or a mixture of formaldehyde and an amide of such a carboxylic acid, or (e) a mercapto compound which contains a water-solubilizing group in the presence of an aldehyde or acetal.  Suitable blue-fluorescent starting materials are 1,5-naphthylene - diamine, 4 - amino - acenaphthene, 3 - amino - pyrene, 2 - amino - crysene, 4,41-diaminostilbene - 2,21 - disulphonic acid and its 4 - aminobenzoyl and 4 - (41 - aminobenzoylamino) - benzoyl derivatives, 2 - (41 - aminophenyl) - 6 - methyl benzothiazole and 2-(41 - aminophenyl) - benzimidazole.  The products may be used for whitening undyed material or for brightening dyed material, and may be applied together with soaps or other washing agents such as salts of sulphonated fatty compounds.  In examples: (1) 2-(41-aminophenyl) - 6 - methylbenzothiazole (compound I) is reacted with formaldehyde disulphite solution; (2) 4,41-bis-(411-aminobenzoylamino) - stilbene - 2,21 - disulphonic acid (compound II) is reacted with formaldehyde bisulphite; (3) compound II is reacted with chlorsulphonic acid in the presence of pyridine; (4) compound II is reacted with mono-chloracetic acid; (5) 3-aminopyrene or 3-aminochrysene is reacted with formaldehyde bisulphite; (6) 4-amino-41-(aminobenzoylamino)-2,21-disulphonic acid is reacted with formaldehyde bisulphite; (7) compound II is reacted with formaldehyde and thioglycollic acid; (8) the compound obtained by reducing the reaction product of benzidine-3,31-disulphonic acid and p-nitro-benzoyl chloride is reacted with formaldehyde bisulphite; (9) compound II is reacted with benzaldehyde bisulphite; (10) compound II is reacted with furfurol bisulphite; (11) compound I is reacted with chlorosulphonic acid in the presence of pyridine; (12) 2-(41-aminophenyl)-6-methylbenzothiazole monosulphonic acid (obtained by sulphonation of compound I with fuming sulphuric containing 10 per cent of sulphur trioxide at 20-25 DEG  C.) is reacted with benzaldehyde bisulphite; (13) compound I is reacted with furfurol bisulphite; (14) 2-(41-aminophenyl)-benzimidazole is reacted with formaldehyde bisulphite; (15) compound I is reacted with the quarternary addition product of trimethylamine and N-methylol-chloracetamide; and (16) the condensation product obtained from 4,41-diaminostilbene-2,21-disulphonic acid, cyanuric chloride, aniline and ammonia is reacted with formaldehyde bisulphite.ALSO:Water-solubilizing groups are introduced into the amino group of a blue-fluorescent compound (other than an amino-coumarin or an amino-naphthalene sulphonic acid) by treating it with (a) an aldehyde bisulphite or with an aldehyde and sulphur dioxide; or (b) an alkyl or aralkyl halide containing at least one sulphonic or carboxylic acid group, preferably in the presence of an acid-binding agent; or (c) the addition product of pyridine and sulphur dioxide; or (d) an N-methylolamide of a carboxylic acid with at least one water-solubilizing group in the acyl radical or a mixture of formaldehyde and an amide of such a carboxylic acid; or (e) a mercapto compound which contains a water-solubilizing group in the presence of an aldehyde or acetal.  Suitable blue-fluorescent starting materials are 1,5 - naphthylene - diamine, 4 - amino - acenaphthene, 3 - amino - pyrene, 2 - amino - crysene, 4,41 - diaminostilbene - 2,21 - disulphonic acid and its 4-aminobenzoyl and 4 - (41 - aminobenzoyl - amino) - benzoyl derivatives, 2 - (41 - aminophenyl) - 6 - methyl benzothiazole and 2-(41-aminophenyl)-benzimidazole.  The products may be used for whitening undyed material or for brightening dyed material, and may be applied together with soaps or other washing agents such as salts of sulphonated fatty compounds.  In examples: (1) 2-(41-aminophenyl) - 6 - methyl - benzothiazole (compound I) is reacted with formaldehyde disulphite solution; (2) 4,41 - bis - (411 - aminobenzoylamino) - stilbene - 2,21 - disulphonic acid (compound II) is reacted with formaldehyde bisulphite; (3) compound II is reacted with chlorosulphonic acid in the presence of pyridine; (4) compound II is reacted with monochloracetic acid; (5) 3-aminopyrene or 3-aminochrysene is reacted with formaldehyde bisulphite; (6) 4 - amino - 41 - (aminobenzoylamino) - 2,21 - disulphonic acid is reacted with formaldehyde bisulphite; (7) compound II is reacted with formaldehyde and thioglycollic acid; (8) the compound obtained by reducing the reaction product of benzidine-3,31-disulphonic acid and p-nitro-benzoyl chloride is reacted with formaldehyde bisulphite; (9) compound II is reacted with benzaldehyde bisulphite; (10) compound II is reacted with furfurol bisulphite; (11) compound I is reacted with chlorosulphonic acid in the presence of pyridine; (12) 2-(41-aminophenyl)-6-methylbenzothiazole monosulphonic acid (obtained by sulphonation of compound I with fuming sulphuric containing 10 per cent of sulphur trioxide at 20-25 DEG  C.) is reacted with benzaldehyde bisulphite; (13) compound I is reacted with furfurol bisulphite; (14) 2-(41-aminophenyl)-benzimidazole is reacted with formaldehyde bisulphite; (15) compound I is reacted with the quarternary addition product of trimethylamine and N-methylol-chloracetamide; (16) the condensation product obtained from 4,41 - diaminostilbene - 2,21 - disulphonic acid, cyanuric chloride, aniline and ammonia is reacted with formaldehyde bisulphite; (17) the product of (2) is mixed with soap and used for washing textiles; (18) silk is whitened by treatment with the product of (1) in presence of acetic acid; (19) cotton is whitened by treatment with the product of (7); (20) acetate artificial silk is whitened by treatment with the product of (1); (21) a paper of high degree of whiteness is obtained by adding the product of (2) to the pulp in a hollander together with resin size and aluminium sulphate; (22) cellulose fabric dyed with a triazo dye is printed with a discharge containing sodium formaldehyde sulphoxylate and the product of (2); and (23) staple fibres of regenerated cellulose are treated with a bath usual for crease-proofing to which is added the product of (2).ALSO:Water-solubilizing groups are introduced into the amino group of a blue-fluorescent compound (other than an amino-coumarin or an aminonaphthalene sulphonic acid) by treating it with (a) an aldehyde bisulphite or with an aldehyde and sulphur dioxide; or (b) an alkyl or aralkyl halide containing at least one sulphonic or carboxylic acid group preferably in the presence of an acid-binding agent; or (c) the addition product of pyridine and sulphur dioxide; or (d) an N-methylolamide of a carboxylic acid with at least one water-solubilizing group in the acyl radical or a mixture of formaldehyde and an amide of such a carboxylic acid; or (e) a mercapto compound which contains a water-solubilizing group in the presence of an aldehyde or acetal.  Suitable blue-fluorescent starting materials are 1,5 - naphthylene - diamine, 4 - amino-acenaphthene, 3-amino-pyrene, 2-amino-crysene, 4,41-diaminostilbene-2,21-disulphonic acid and its 4-aminobenzoyl and 4-(41-aminobenzoyl - amino) - benzoyl derivatives, 2 - (41 - aminophenyl) - 6 - methyl benzothiazole and 2 - (41 - aminophenyl) - benzimidazole. The products may be used for whitening undyed material or for brightening dyed material, may be applied together with soaps or other washing agents such as salts of sulphonated fatty compounds. In example (17) the condensation product of 4,41-bis-(411-aminobenzoyl-amino)-stilbene-2, 21-disulphonic acid and formaldehyde bisulphite is mixed with soap and used for washing textiles.