Patent GB-456214-A (GB)
Title: Alcohol sulphation process
IPC: C07C303/24
Filed: 1935-05-04
Abstract: Sulphuric esters of alcohols having more than eight carbon atoms are obtained by reacting a dilute solution of a sulphating agent in a high boiling ether with a solution of the alcohol in a high-boiling ether which is a common solvent for the alcohol and sulphating agent, and preferably also for the ester produced. Gaseous sulphating agents, e.g. sulphur trioxide, are diluted with inert gases, e.g. industrial gases may be used.  Temperatures of -20 to 60 DEG  C. are used; secondary and tertiary alcohols being treated at a lower temperature than primary alcohols.  Preferably sulphating agents are used which do not yield water during reaction, e.g. chlorosulphonic acid and dry sulphur trioxide and suitable solvents include dichlorethyl ether, dichlorisopropyl ether and b -chlorethyl ethoxy chlorethyl ether, boiling at 170 DEG  C. or over.  During the reaction, a dry inert gas, e.g. air, nitrogen, hydrogen, methane or carbon dioxide, is preferably forced through the liquid mixture to minimize side reactions and assist the removal of the hydrogen chloride formed when chlorsulphonic acid is used.  According to examples: (1) a solution of 7-ethyl-2-methyl undecanol in bis-beta chlorethyl ether (or dichlorethyl ether) cooled to 16 DEG  C. was treated with a solution of chlorsulphonic acid in the same solvent, agitation by bubbling air being used.  The temperature rose to 23,5 DEG  C. and was maintained there.  The effluent hydrogen chloride was absorbed in fuming sulphuric acid for re-use.  The product, the neutral sulphuric ester, was a white solid, soluble in water, methanol, acetone and ether, and having a drop number of 80 at 30 DEG C.; (2) the neutral sulphuric ester of b -phenylethyl isobutyl carbinol was obtained in a similar manner, being a colourless waxy solid with a drop number of 36 at 30 DEG  C.; (3) b -hexahydrophenylethylisobutyl carbinol was treated in a similar manner, giving a colourless waxy solid having a drop number of 44 at 30 DEG  C.; (4) a solution of 7-ethyl-2-methyl-undecanol-4 in dichlorethyl ether was flowed through a spiral of glass tubing, thus causing it to form a thin body, i.e. of small cross-section, and was treated by a countercurrent stream of dilute sulphur trioxide.  The spiral was maintained at -10 DEG  C.  The product was a white solid with a drop number of 80 at 36 DEG  C.  This modification exposes a large surface area of the alcohol to the sulphur trioxide and assists heat transfer.  Other alcohols which are mentioned are butyloctanol and dibenzylbutanol.  The products may be used as dispersing agents, detergents and penetrants, e.g. for textiles, leather or felt.  They are frothing and foaming agents in acid, neutral or alkaline solutions, and possess soluble calcium and magnesium salts.  The Specification as open to inspection under Sect. 91 is not restricted to the use of high-boiling ethers, and relates to the use of high-boiling solvents in general.  This subject-matter does not appear in the Specification as accepted.ALSO:Sulphuric esters of alcohols having more than eight carbon atoms, which may be used as dispersing agents, are obtained by reacting a dilute solution of a sulphating agent in a high-boiling ether, which is a common solvent for the alcohol and sulphating agent.  Examples describe the production of the sulphuric esters of 7-ethyl-2-methyl undecanol; b -phenylethyl isobutyl carbinol; b -hexahydrophenylethyl isobutyl carbinol.