Patent GB-455086-A (GB)
Title: Improved manufacture of surface-active substances
IPC: C07G99/00
Filed: 1935-03-07
Abstract: Soap substitutes, having wetting, dispersing and foaming properties are prepared from compounds having the formula RArOH, in which R is an aliphatic residue containing at least four carbon atoms and Ar an aromatic residue, by hydrogenating and introducing directly or indirectly a water solubilizing group or a residue containing the same.  The water solubilizing groups are the sulphonic group, phosphoric, sulphuric or thiosulphuric ester groups, the carboxylic group and polyhydroxy or polyether groups. One hydroxy or ether group may be introduced when complete solubility is not necessary; the products thus obtained have emulsifying properties.  The sulphonic and sulphuric ester groups are introduced by sulphonation, e.g. by means of additive compounds of sulphur trioxide or chlorsulphonic acid with dipropyl or dibutylethers, ethyl acetate or tertiary amines.  Phosphoric ester groups are introduced by treatment with phosphorus pentoxide and a tertiary base, e.g. pyridine.  The carboxylic group is introduced by forming the halides of the hydroaromatic alcohols obtained after hydrogenation, converting the halides into the corresponding Grignard compounds and treating with carbondioxide. By treating the said halides with sodium thiosulphate, thiosulphuric ester groups are introduced.  One or more hydroxy groups may be introduced by treating the alkali compounds of the alcohols with glycolchlorhydrin or glycerol chlorhydrin.  The polyhydroxy or polyether groups may be introduced by treating with alkylene oxides, glycide or epichlorhydrin.  The water solubilizing groups may be introduced indirectly, e.g. the hydroaromatic alcohols may be esterified with acids such as lactic, glycollic or glyceric acid and a sulphuric ester group introduced.  Water may be removed from the hydroaromatic alcohols and the unsaturated product, possibly after introducing halogen treated with mercaptoacetic acid or sulphuric acid.  The alkylated aromatic hydroxy compounds used as starting materials may be prepared by condensing olefines, halogenated aliphatic compounds or primary, secondary or tertiary alcohols or their mixtures with phenols, cresols, xylenols, thymol, carvacrol, hydroxydiphenyls, naphthols, hydroxyanthracenes, hydroxyphenanthrenes or benzenehydroxy quinolines.  Olefine mixtures prepared from carbonmonoxide and hydrogen, olefines obtained by the thermal decomposition of wood or brown coal or by cracking petroleum or paraffins, dodecyl chlorides or bromides, dodecylalcohol, penthylmethyl carbinol and methylbutylcarbinol are examples of components which may be used for the condensation. The aliphatic residue R of the aromatic hydroxy compounds used as starting material include the ketonic compounds obtained by condensing aliphatic carboxylic acids or their derivatives with phenols.  In examples: (1) n - heptyl - o - cresylketone, n - undecyl-o cresylketone and the mixture of ketones prepared from coconut fatty acids and cresols are hydrogenated and sulphonated; (n) a mixture of alkylcresols prepared from cresols and a mixture of natural higher fatty alcohols or higher alcohols obtained from the methanol synthesis is hydrogenated and sulphonated; (3) dodecene is condensed with o-cresol by means of boron fluoride and the product hydrogenated and sulphonated; (4) synthetic benzines and other olefine containing mixtures are condensed with phenol, p-cresol, m-cresol, mixtures of the three cresols, xylenols and with a -naphthol and the products then hydrogenated and sulphonated; (5) cracked petroleums obtained by the Dubbs process or by a modified Gyro process are hydrogenated and sulphonated with anhydro pyridinium or picolinium sulphonic acid; (6) a cracked gas oil is condensed with o-cresol and the product hydrogenated and sulphonated; (7) alkylated cresols obtained from chlorinated paraffins and cresols are hydrogenated and sulphonated; (8) water is removed from the alcohols obtained by condensing synthetic benzines with m-cresols and hydrogenating, and the resulting alkyl methylhexenes sulphonated by means of a mixture of sulphuric acid and acetic anhydride; after neutralization the products may be used as foaming and cleansing agents; (9) iso-alkylmethylcyclohexanols, obtained by hydrogenating the product of condensation of cresol with mixtures of olefines prepared from coke oven gases or by a cracking process are converted into the corresponding cyclohexenes by removal of water and are then sulphonated; (10) alkyl phenols prepared from an olefine mixture and phenol are hydrogenated and thioglycollic acid condensed with the alkylated cyclohexenes obtained by the removal of water; the product may be neutralized and mixed with tetrasodium pyrophosphate.  Samples have been furnished under Sect. 2(5) of products prepared as follows: (a) a mixture of 4-sec-alkyl-2-methylcyclohexanols is esterified with chloracetic acid and a sulphonic group introduced by means of sodium sulphite; (b) a cracked benzine is condensed with commercial o-cresol, the resulting higher alkylcresols hydrogenated and finally sulphonated after treatment with ethylene oxide; (c) the higher alkyl methylcyclohexanols employed in the preparation of sample (b) are treated with trioxymethylene and dry hydrogenchloride, the resulting p  chlormethylethers condensed with aniline ethylalcohol and the products sulphonated; (d) the same higher alkyl methylcyclohexanols are condensed with oxyethoxyacetic acid lactone and sulphonated; (e) sec-dodecylmethylcyclohexanol is esterified with chloracetic acid, reacted with anilinoethylalcohol and sulphonated; (f) sec-dodecylmethylcyclohexanol is esterified with chloracetic acid and treated with sodium thiosulphate; (g) isododecyl-2-methylcyclohexanol is treated with ethyleneoxide in the presence of nickel sulphate. Specifications 443,487 and 449,607 are referred to.ALSO:Soap substitutes, having, dispersing properties are prepared from compounds having the formula RArOH, in which R is an aliphatic residue containing at least four carbon atoms and Ar an aromatic residue, by hydrogenating and introducing directly or indirectly a water-solubilizing group or a residue containing the same.  The water solubilizing groups are the sulphonic group, phosphoric, sulphuric or thiosulphuric ester groups, the carboxylic group, and polyhydroxy or polyether groups.  One hydroxy or ether group may be introduced when complete solubility is not necessary; the products thus obtained have emulsifying properties.  The sulphonic and sulphuric ester groups are introduced by sulphonation, e.g. by means of additive compounds of sulphurtrioxide or chlorsulphonic acid with dipropyl or dibutylethers, ethyl acetate or tertiary amines.  The carboxylic group is introduced by forming the halides of the hydroaromatic alcohols obtained after hydrogenation, converting the halides into the corresponding Grignard compounds and treating with carbondioxide. By treating the said halides with sodium thiosulphate, thiosulphuric ester groups are introduced.  The polyhydroxy or polyether groups are introduced by treating with alkylene oxides, glycide, or epichlorhydrin.  One or more hydroxy groups may be introduced by treating the alkali compounds of the alcohols with glycolchlorhydrin or glycerol chlorhydrin. Phosphoric esters are produced by treatment of the alcohols with phosphorus pentoxide and a tertiary base, e.g. pyridine.  The water solubilizing groups may be introduced indirectly, e.g. the hydroaromatic alcohols may be esterified with acids such as lactic, glycollic or glyceric acid and a sulphuric ester group introduced.  Water may be removed from the hydroaromatic alcohols and the unsaturated product, possibly after introducing halogen treated with mercaptoacetic acid or sulphuric acid.  The aliphatic residue R of the aromatic hydroxy compounds used as starting material include the ketonic compounds obtained by condensing aliphatic carboxylic acids or their derivatives with phenols.  In examples: (1) n - heptyl - o - cresylketone, n - undecyl - o - cresylketone and the mixture of ketones prepared from coconut fatty acids and results are hydrogenated and sulphonated; (2) a mixture of alkylcresols prepared from cresols and a mixture of natural higher fatty alcohols or higher alcohols obtained from the methanols syntheses is hydrogenated and sulphonated; (3) dodecene is condensed with o-cresols by means of boron fluoride and the product hydrogenated and sulphonated; (4) synthetic benzines and other olefine containing mixtures are condensed with phenol, p-cresol, m-cresol, mixtures of the three cresols, xylenols and with naphthol and the products then hydrogenated and sulphonated; (5) cracked petroleums obtained by the Dubbs process or by a modified Gyro process are hydrogenated and sulphonated with anhydro pyridinium or picolinium sulphonic acid; (6) a cracked gas oil is condensed with o-cresol and the product hydrogenated and sulphonated; (7) alkylated cresols obtained from chlorinated paraffins and cresols are hydrogenated and sulphonated; (8) water is removed from alcohols obtained by condensing synthetic benzines with m-cresols and hydrogenating, and the resulting alkyl methylhexenes sulphonated by means of a mixture of sulphuric acid and acetic anhydride; after neutralization the products may be used as foaming and cleansing agents; (9) isoalkylmethyl cyclohexanols, obtained by hydrogenating the product of condensation of cresol with mixtures of olefines prepared from coke oven gases or by a cracking process, are converted into the corresponding cyclohexenes by removal of water and are then sulphonated; (10) alkyl phenols prepared from an olefine mixture and phenol are hydrogenated and thioglycollic acid condensed with the alkylate cyclohexenes obtained by the removal of water; the product may be neutralized and mixed with tetrasodium pyrophosphate.  Samples have been furnished under Sect. 2 (5) of prod