Patent GB-701103-A (GB)
Title: Improvements in the production of watersoluble condensation products
IPC: C14C3/20
Filed: 1950-07-11
Abstract: Water soluble condensation products used as tanning agents are made by condensing at elevated temperatures the addition compounds of bisulphites and saturated aliphatic keto- or aldehydo-methylene compounds with formaldehyde and phenols or their substitution products, except their sulphuric acids, or the corresponding methylol compounds or higher condensed phenol-formaldehyde resins, and if desired reacting the resulting water-soluble condensation products containing carbinol groups at elevated temperatures with further organic compounds free from sulphuric acid groups but capable of condensing with the carbinol groups with the splitting off of water. Not all of the hydrogen atoms of the bisulphite compound need be substituted by hydroxyaryl methyl groups. Compounds mentioned as condensing with carbinol groups are mono-and poly-hydric phenols, hydroxyaryl carboxylic acids, naphthols, arylsulphones and sulphonamides or their functional derivatives and condensation products.  Specified compounds for this stage are phenol, cresol, resorcinol, pyrocatechol, salicylic acid, betanaphthol, dimethyldiphenylmethane, dinaphtholmethane, dihydroxydiphenyl sulphone and urea. Condensation products, functional derivatives or substitution products of the said classes of substances may also be used, e.g. hydroxyethylated phenols and naphthols, phenol-sulphur resins and phenolformaldehyde resins.  The reaction of the carbinol group takes place the more readily the more exchangeable hydrogen atoms of the adjacent carbon atoms have been replaced by hydroxyarylmethyl groups.  Specified saturated aliphatic keto- or aldehydo-methylene compounds are acetaldehyde, levulin aldehyde, acetone, acetonyl acetone, aceto-acetic ester and acetone dicarboxylic acid.  The reaction of the bisulphite addition compounds may be effected with phenol alcohols made from phenol and formaldehyde or with insoluble phenol-formaldehyde resins or in alkaline solution with phenol and formaldehyde.  Temperatures of reaction for both stages are generally 60-100 DEG C., advantageously 80-90 DEG C.  The final products may be coupled with diazo compounds or reacted with ethylene oxide.  Ash free products are obtained when ammonium bisulphite addition products are reacted with phenol alcohols and resins.  In examples the sodium bisulphite compound of acetone is reacted with (1) cresol and aqueous caustic soda and formaldehyde and the product with resorcinol, (2) phenol and cresol after reaction together in aqueous caustic soda with formaldehyde the product in (3) being reacted with beta-naphthol and in (4) with dihydroxydiphenylsulphone, in (5) the sodium bisulphite compound of acetaldehyde is reacted with a cresol-phenol condensation product prepared as in (2) and the product reacted with resorcinol, in (6) the ammonium bisulphite compound of acetone is reacted with a cresol-phenol condensation product prepared as in (2), and in (7) a product similar to that of (6) is reacted with decalcified sulphite cellulose waste liquor neutralised with ammonia, in (8) and (9) the sodium bisulphite compound of acetone is reacted with a condensation product from o-chlorphenol and formaldehyde in aqueous caustic soda and the product may be treated with resorcinol or salicylic acid and in (10) the sodium bisulphite addition compound of acetone is reacted with a condensation product of p, p1 dihydroxydiphenyldimethylmethane, formaldehyde and aqueous caustic soda.ALSO:Water-soluble condensation products are made by condensing at elevated temperatures the addition compounds of bisulphites and saturated aliphatic keto- or aldehydo-methylene compounds with formaldehyde and phenols or their substitution products, except their sulphonic acids, or the corresponding methylol compounds or higher condensed phenol-formaldehyde resins, and if desired reacting the resulting water-soluble condensation products containing carbinol groups at elevated temperatures with further organic compounds free from sulphonic acid groups but capable of condensing with the said carbinol groups with the splitting off of water.  Not all of the hydrogen atoms of the bisulphite addition compound need be substituted by hydroxyaryl methyl groups. Compounds mentioned as condensing with carbinol groups are mono- and poly-hydric phenols, hydroxyaryl carboxylic acids, naphthols, arylsulphones and sulphonamides or their functional derivatives and condensation products.  Specified compounds for this stage are phenol, cresol, resorcinol, pyrocatechol, salicylic acid, dimethyldiphenylmethane, beta-naphthol, dinaphtholmethane, dihydroxy-diphenyl sulphone and urea.  Condensation products, functional derivatives or substitution products of the said classes of substances may be used, e.g. hydroxy-ethylated phenols and naphthols, phenol-sulphur resins and phenol-formaldehyde resins.  The reaction of the carbinol groups takes place the more readily the more exchangeable hydrogen atoms of the adjacent carbon atoms have been replaced by hydroxyarylmethyl groups. Specified saturated aliphatic keto- or aldehydomethylene compounds are acetaldehyde, levulin aldehyde, acetone, acetonyl acetone, acetoacetic ester and acetone dicarboxylic acid.  The reaction of the bisulphite addition compounds may be effected with phenol alcohols made from phenol and formaldehyde or with insoluble phenol-formaldehyde resins or in an alkaline solution with phenol and formaldehyde.  Temperatures of reaction for both stages are generally 60-100 DEG  C., advantageously 80-90 DEG  C.  The final products may be coupled with diazo compounds or reacted with ethylene oxide.  The products may be used as tanning agents, as dyestuff intermediates, as disinfectants or preserving agents and in chemo-therapeutic preparations by, e.g. coupling with diazotized 4-aminobenzene sulphonamide or by reacting the carbinol groups with 4-aminobenzene sulphonamide, cf.  German Patent 686,903, or by reacting the carbinol groups with N1-heterocyclic substituted aminobenzene sulphonamides, e.g. 2-(p-amino-benzene sulphonamido)-pyridine or 2-(p-aminobenzene-sulphonamido)-thiazole.  Ash free products are obtained when ammonium bisulphite addition products are reacted with phenol alcohols and resins.  In examples, the sodium bisulphite compound of acetone is reacted with (1) cresol and aqueous caustic soda and formaldehyde and the product with resorcinol, (2) phenol and cresol after reaction in aqueous caustic soda with formaldehyde the product in (3) being reacted with beta-naphthol and in (4) with dihydroxydiphenyl sulphone, in (5) the sodium bisulphite compound of acetaldehyde is reacted with a cresol-phenol condensation product prepared as in (2) and the product reacted with resorcinol in (6) the ammonium bisulphite compound of acetone is reacted with a cresol-phenol condensation product prepared as in (2), and in (7) a product similar to that of (6) is reacted with decalcified sulphite cellulose waste liquor neutralized with ammonia, in (8) and (9) the sodium bisulphite compound of acetone is reacted with the condensation product from d -chlorphenol and formaldehyde in aqueous caustic soda and the product may be treated with resorcinol or salicylic acid and in (10) the sodium bisulphite compound of acetone is reacted with a condensation product of p, p1-dihydroxydiphenyldimethylmethane, formaldehyde and aqueous caustic soda.ALSO:Water soluble condensation products made by condensing at elevated temperatures the addition compounds of bisulphates and saturated aliphatic keto- or aldehydo-methylene compounds with formaldehyde and phenols or their substitution products, except their sulphonic acids, or the corresponding methylol compounds or higher condensed phenol-formaldehyde resins, and if desired reacting the resulting water-soluble condensation products containing carbinol groups at elevated temperatures with further organic compounds free from sulphonic acid groups but capable of condensing with the carbinol groups with the splitting off of water, may be coupled with diazo-compounds to produce initial materials and intermediates for dyestuffs.  Not all of the hydrogen atoms of the bisulphite compound need be substituted by hydroxyaryl methyl groups.  Compounds mentioned as condensing with carbinol groups are mono- and polyhydric phenols, hydroxyaryl carboxylic acids, naphthols, arylsulphones and sulphonamides or their functional derivatives and condensation products. Specified compounds for this stage are phenol, cresol, resorcinol, pyrocatechol, salicylic acid, betanaphthol, dimethyldiphenylmethane, dinaphtholmethane, dihydroxydiphenyl sulphone and urea.  Condensation or substitution products and functional derivatives, of the said classes of substances may also be used, e.g. hydroxyethylated phenols and naphthols, phenol-sulphur resins and phenol-formaldehyde resins.  The reaction of the carbinol group takes place the more readily the more exchangeable hydrogen atoms of the adjacent carbon atoms have been replaced by hydroxyaryl methyl groups.  Specified saturated aliphatic keto- or aldehydo-methylene compounds are acetaldehyde, levulin aldehyde, acetone, acetonyl acetone, aceto-acetic ester and acetone dicarboxylic acid.  The reaction of the bisulphite addition compounds may be effected with phenol alcohols made from phenol and formaldehyde or with insoluble phenol-formaldehyde resins or in alkaline solution with phenol and formaldehyde. Temperatures of reaction for both stages are generally 60-100 DEG C., advantageously 80-90 DEG C.  Coupling with diazotized 4-aminobenzene sulphonamide is specifically referred to.