Patent GB-401142-A (GB)
Title: Improved process for the preparation of higher ethers
Filed: 1933-02-03
Abstract: Higher ethers are manufactured by reacting oxyacid esters of higher aliphatic or hydroaromatic alcohols containing at least 8 carbon atoms in the molecule with alcohols or phenols in an alkaline medium or with alcoholates or phenolates.  Suitable oxyacid esters are the sulphuric or phosphoric acid esters of dodecyl, myristic, cetyl or oleic alcohol, resin alcohols, naphthene alcohols, or mixtures thereof.  These may be reacted with alcohols, e.g. methyl, butyl, or dodecyl alcohol, phenols or naphthols in an alkaline medium, or with the corresponding alcoholates or phenolates.  The reaction components may be substituted by any groups which do not exert an unfavourable influence on the reaction, e.g. ether groups, sulpho groups, alkyl or aryl residues.  The oxyacid esters may also be reacted with polyhydric alcohols or alcoholates, e.g. with the monoalcoholates of glycol or glycerol, to produce either multiple ethers or ethers substituted by hydroxy groups.  The products may be employed as such, e.g. as softening agents or in the cosmetic industry, or may serve as starting substances for the preparation of other compounds.  In examples: (1) a solution of sodium glycol in glycol (obtained by reacting a small quantity of sodium with anhydrous glycol) is boiled with a solution in glycol of the sodium salt of the sulphuric acid ester of dodecyl alcohol, yielding b -hydroxyethyldodecyl ether; (2) the monosodium compound of glycerol (obtained by treating glycerol with caustic soda solution) is dissolved in glycerol and heated with a solution in glycerol of the commercial sodium salt of dodecyl sulphuric acid ester, to produce b -g -dihydroxypropyldodecyl ether; (3) monosodium glycerol is dissolved in glycerol and heated with a solution of sodium dodecyl sulphate in glycerol yielding glycerol monododecyl ether; (4) a solution of sodium glycerol in glycerol is heated with a solution of sodium tetradecyl sulphate in glycerol to produce glycerol monotetradecyl ether; (5) glycerol monohexadecyl ether is similarly produced from sodium glycerol and sodium hexadecyl sulphate; (6) glycerol monooctodecyl ether is similarly produced from sodium glycerol and sodium octodecyl sulphate; (7) sodium dodecyl sulphate and sodium phenolate are heated in phenol.  Samples have been furnished under Sect. 2 (5) of products prepared as follows: (A) a solution of monosodium glycerol in glycerol (prepared by heating a mixture of glycerol and caustic soda solution under reduced pressure) is heated with the sodium salt of the sulphonic ester of octyl alcohol, yielding octyl-(b -g -dioxypropyl) ether; (B) decyl-(b -g -dioxypropyl) ether is similarly produced from the sodium salt of the sulphuric acid ester of decyl alcohol; (C) a solution of sodium glycerol in glycerol is heated with a mixture of sodium salts of the sulphuric acid esters of naphthenic alcohols containing at least 8 carbon atoms in the molecule (obtained from the esters which are prepared by treating the naphthenic alcohols with chlorsulphonic acid in ethereal solution at low temperature), yielding a mixture of naphthene alcohol glycerol ethers; (D) the sulphuric acid ester of 1-methoxydecanol-10 (obtained by treating 1-methoxydecanol-10 with chlorsulphonic acid in ethereal solution at 5-10 DEG  C.) is heated with a solution of sodium glycerol in glycerol to produce the 1-methoxydecyl ether of glycerol; (E) a solution of sodium glycerol in glycerol is heated with the sodium salt of the disulphuric ester of decandiol-1 : 10 (obtained from the ester which is prepared by treating decandiol-1 : 10 with chlorsulphonic acid in ethereal solution at low temperature), producing di-(b -g -dihydroxypropylhydroxy)-1 : 10-decane.