Patent GB-494769-A (GB)
Title: Aryloxy polyalkylene ether sulfonates
Filed: 1937-05-04
Abstract: Sulphonates of the formula ROAOASO3M or ROAOAOASO3M, where R is an aromatic hydrocarbon radicle of the benzene or naphthalene series, A is an alkylene group of at least two carbon atoms, and M is a metal, are prepared by heating with a metal sulphite a halogenated ether of the formula ROAOAX or ROAOAOAX, where X is halogen.  The halogenated ethers may be prepared, as described in Specifications 494,767 and 494,768, [both in Group IV], by condensing a phenol or a naphthol with an appropriate dihalogendialkyl ether in the presence of an alkaline condensing agent.  Specified phenols or naphthols are phenol, a - or b -naphthol, m- or p-cresol, xylenols, thymol, carvacrol, any of the straight- or branched-chain butyl-, amyl-, hexyl-, heptyl-, octyl-, nonyl-, decyl-, dodecyl-, hexadecyl- or octadecyl-phenols or -cresols, phenyl-, cyclohexyl- and benzyl-phenols, and the correspondingly substituted naphthols. Specified dihalogendialkyl ethers are b , b 1-dichlorodiethyl ether, g , g 1-dichlorodipropyl ether, b , b 1-dichlorodiisopropyl ether, b -chloro-b 1- (b 11-chloroethoxy) diethyl ether, and b , b 1-dichlorodiisobutyl ether; the corresponding bromo and iodo compounds may also be used.  Specified sulphites are those of the alkali metals, calcium magnesium, zinc and copper. The sulphonates are useful as emulsifying agents.  In examples, (1) b -(p-tert.-octylphenoxy)-b 1-chlorodiethyl ether is heated with aqueous sodium or potassium sulphite; the product may be used as an emulsifying and spreading agent for oil-soluble contact insecticides, such as organic thiocyanates; (2) b -(p-tert.-butylphenoxy)-b 1-chlorodiethyl ether is heated with aqueous sodium sulphite. Examples are given also of the preparation of sulphonates by heating aqueous sodium or potassium sulphite with (3) b -(p-tert.-amylphenoxy)-b 1-chlorodiethyl ether, (4) b  - (p - tert.- octylphenoxy)-b 1- (b 11-chloroethoxy) diethyl ether, (5) b -(p-a , a , g , g -tetramethylbutylphenoxy) - b 1 - chlorodiisopropyl ether, (6) b -(o- or p-phenylphenoxy)-b 1-chlorodiethyl ether, (7) b -(o- or p-cyclohexylphenoxy)-b 1-chlorodiethyl ether, (8) b -(o- or p-benzylphenoxy)-b 1-chlorodiethyl ether, (9) b -(b -naphthyloxy)-b 1-chlorodiethyl ether, (10) b -(o-methyl-p-a , a , g , g -tetramethylbutylphenoxy)-b 1-(b 11-chloroethoxy) diethyl ether, (11) b -(p-sec.-octylphenoxy)-b 1-chlorodiethyl ether, (12) b -(p-dodecylphenoxy)-b 1-chlorodiethyl ether, and (13) b -(p-cetylphenoxy)-b 1-chlorodiethyl ether.ALSO:Sulphonates of the formula ROAOASO3M or ROAOAOASC3M, where R is an aromatic hydrocarbon radicle of the benzene or naphthalene series, A is an alkylene group of at least two carbon atoms, and M is a metal, are prepared by heating with a metal sulphite a halogenated ether of the formula ROAOAX or ROAOAOAX, where X is halogen.  The halogenated ethers may be prepared, as described in Specifications 494,767 and 494,768, by condensing a phenol or a naphthol with an appropriate dihalogendialkyl ether in the presence of an alkaline condensing agent.  Specified phenols or naphthols are phenol, a - or b -naphthol, o-, m- or p-cresol, xylenols, thymol, carvacrol, any of the straight- or branched-chain butyl-, amyl-, hexyl-, heptyl-, octyl-, nonyl-, decyl-, dodecyl-, hexadecyl- or octadecyl-phenols or -cresols, phenyl-, cyclohexyl- and benzyl-phenols, and the correspondingly substituted naphthols.  Specified dihalogendialkyl ethers are b , b 1-dichlorodiethyl ether, g , g 1-dichlorodipropyl ether, b , b 1-dichlorodiisopropyl ether, b -chloro-b 1-(b 11-chloroethoxy)diethyl ether, and b , b 1-dichlorodiisobutyl ether; the corresponding bromo and iodo compounds may also be used. Specified sulphites are those of the alkali metals, calcium, magnesium, zinc and copper. When a chlorinated ether is used, the reaction with a metal sulphite may be effected in an aqueous or aqueous-alcoholic medium at above 125 DEG  C. under pressure; when a bromo- or iodo-ether is used, the reaction with a sulphite may be effected under reflux at atmospheric pressure.  The sulphonates are useful as wetting, cleansing, and emulsifying agents.  In examples, (1) b  - (p - tert. - octylphenoxy) - b 1 - chlorodiethyl ether is heated with aqueous sodium or potassium sulphite; the product may be purified by dissolving it in alcohol and evaporating the solution; it may be used as a wetting-agent for cotton yarn and as an emulsifying and spreading agent for oil-soluble contact insecticides, such as organic thiocyanates; it is useful also as a levelling agent in dyeing; (2) b  - (p - tert. - butylphenoxy) - b 1 - chlorodiethyl ether is heated with aqueous sodium sulphite, and the sulphonate is isolated by evaporating the product and extracting it with alcohol. Examples are given also of the preparation of sulphonates by heating aqueous sodium or potassium sulphite with (3) b -(p - tert. - amylphenoxy) - b 1-chlorodiethyl ether; (4) b -(p-tert.-octylphenoxy)-b 1 - (b 11 - chloroethoxy)diethyl ether; (5) b  - (p-a , a , g , g -tetramethylbutylphenoxy)-b 1-chlorodiisopropyl ether; (6) b -(o- or p-phenylphenoxy) - b 1 - chlorodiethyl ether; (7) b -(o- or p-cyclohexylphenoxy)-b 1-chlorodiethyl ether; (8) b -(o- or p-benzylphenoxy)-b 1-chlorodiethyl ether; (9) b -(b -naphthyloxy)-b 1-chlorodiethyl ether; (10) b -(o-methyl-p-a , a , g , g -tetramethylbutylphenoxy)-b 1-(b 11-chloroethoxy) diethyl ether; (11) b -(p-sec.-octylphenoxy)-b 1-chlorodiethyl ether; (12) b -(p - dodecylphenoxy) - b 1 - chlorodiethyl ether; and (13) b -(p-cetylphenoxy)-b 1-chlorodiethyl ether.