Patent GB-748571-A (GB)
Title: Process for sulphonating alcohols
IPC: C07B45/02
Filed: 1953-09-18
Abstract: A process for sulphonating alcohols, preferably of higher molecular weight (i.e. with at least 6 carbon atoms), comprises sulphonating the alcohol with an addition compound formed from chlorosulphonic acid and a polyether of the type which contains at least 3 ether oxygen atoms in an ether chain.  The alcohols may be of the aliphatic, cycloaliphatic or araliphatic series.  The addition compounds may be made by the process of Specification 748,570.  The polyethers may be polyethylene oxide, polypropylene oxide or mixed polyethers; the end of the polyether chains can be ester or ether groups, and the chains can also be contiguous to hetero-atoms, such as sulphur or nitrogen atoms.  If the polyethers contain hydroxyl groups or other atoms or groups, e.g. amino or amido nitrogen atoms, which react preferentially with chlorosulphonic acid, they are reacted first with the chlorosulphonic acid and the excess chlorosulphonic acid becomes added to the ether oxygen atoms.  The maximum excess amount of chloro-sulphonic acid should be that which is about the molecular equivalent of the ether oxygen atoms.  The addition compound may be formed at temperatures of - 50 DEG  to +60 DEG  C.  As compounds to be sulphonated compounds with 6 to 24 carbon atoms are of special interest.  Alcohols with the hydroxy group contiguous to primary or secondary carbon atoms, straight or branched chain and saturated or unsaturated can be used.  As primary alcohols are mentioned alcohols occurring in sperm oil or bees' wax or obtained by reduction of natural or synthetic fatty acids, by reaction of carbon monoxide and hydrogen, by reaction of carbon monoxide with straight- or branched-chain olefines, or by extraction of the neutral oxidation products of paraffins. Specified are octyl, decyl, dodecyl and octadecyl alcohols. Unsaturated alcohols suitable include those obtained by the splitting or reduction of sperm oil, castor oil or linseed oil. As cyclic alcohols are specified hexahydrobenzyl alcohols which comprise aliphatic, cycloaliphatic or aromatic residues, e.g. compounds obtained by splitting out water from the corresponding cyclohexanols, catalytic reaction of the resulting cyclohexenes with carbon monoxide and hydrogen, and reducing aldehydes formed. Benzyl and alkylbenzyl alcohols and methylolnaphthalenes are also mentioned.  Secondary alcohols include those obtained by reduction of the products resulting on ketonizing fatty acids and perhydrogenated aromatic hydroxy compounds substituted by alkyl or cycloalkyl residues.  The sulphonation can be effected batchwise or continuously.  Reaction temperatures of - 10 DEG  to +60 DEG , preferably +20 DEG  to +40 DEG  C. are suitable. Solvents such as liquid sulphur dioxide, carbon disulphide, ethylene dichloride and perchloroethylene, and bases such as sodium or potassium hydroxide, ammonia, triethanolamine, cyclohexylamine and pyridine can be present.  The polyethers liberated from the addition compounds need not be separated from the reaction mixture.  Double bonds in the alcohols to be sulphonated are not affected.  In examples, oleyl alcohol is reacted with addition compounds of chlorosulphonic acid and (1) a polyethyleneglycol monomethyl ether of average molecular weight 360; (2) a polyethylene oxide of average molecular weight 5000; (4) a reaction product of 8 to 9 mols. of ethylene oxide and a fatty alcohol mixture of chain length C12 to C18 obtained by the reduction of coconut fatty acid; (5) a reaction product of about 10 mols. of ethylene oxide with 1 mol. of a coconut fatty acid amide of the chain length C12 to C18.  In further examples: (3) a mixture of secondary alcohols (chain length C13 to C17) obtained by reduction of the products obtained by the ketonization of fatty acids with 7 to 9 carbon atoms in the molecule obtained by the oxidation of paraffins is treated with an addition compound of chlorosulphonic acid with a polyethylene oxide of average molecular weight 9000; (6) coconut fatty acid mono-ethanolamide is treated with an addition compound of chlorosulphonic acid with a polyglycol monomethyl ether as specified in Example (1); (7) and (9) dodecyl-cyclohexanol is treated with an addition compound of chlorosulphonic acid with (7) a similar addition compound to that employed in Example (1), and (9) an addition compound of chlorosulphonic acid with a reaction product of 12 mols. of ethylene oxide with 1 mol. of a dodecyl mercaptan.