Patent GB-866116-A (GB)
Title: Preparation of allyl ethers
IPC: C07C43/14
Filed: 1957-07-31
Abstract: Allyl ethers of polyethoxyethanols having a terminal hydrocarbon group of sufficient size to impart a hydrophobic balance, such as dodecyl or octyl phenyl, and especially allyl ethers of alkyl phenoxy polyethoxy ethanols having 3-22 carbon atoms in the alkyl group and 5-100 ether groups, are prepared by reacting allyl alcohol with the polyethoxyethanol with splitting of water under the influence of a catalyst which is soluble and ionizable in the reaction system and comprises a mercury salt of a strong acid, a mixture of a mercury salt of a weak acid and a strong acid or acidic salt thereof, or a mixture of mercuric oxide and a strong acid, the reaction being preferably effected at 75-150 DEG  C., if desired in the presence of a solvent, desirably under reflux with separation of the water formed.  The strong acids are defined as HF, the ansolvo acids and acids stronger than these and which provide mercury salts soluble and ionizable in the reaction system, e.g. sulphuric acid and sulphonic acids.  The weak acids are those weaker than HF and the ansolvo acids, e.g. acetic and benzoic acids.  Ansolvo acids may be formed in situ from BF3 and the alcoholic reagents.  Suitable acidic salts are silver nitrate, ferric sulphate, ferrous ammonium sulphate and ferrous sulphate with sulphuric acid.ALSO:Allyl ethers of non-tertiary alcohols free from reactive groups, are prepared by reacting allyl alcohol with the non-tertiary alcohol, which may be allyl alcohol itself, with splitting off of water under the influence of a catalyst which is soluble and ionizable in the reaction system and comprises a mercury salt of a strong acid, a mixture of a strong acid or acidic salt thereof and a mercury salt of a weak acid, or a mixture of mercuric oxide and a strong acid, the reaction preferably being effected at 75 DEG -150 DEG C. if desired in the presence of a solvent and desirably under reflux with separation of the water formed.  The strong acids are defined as hydrofluoric acid, ansolvo acids and acids stronger than these and which provide mercury salts soluble and ionizable in the reaction system.  The weak acids are defined as those which are weaker than hydrofluoric acid and ansolvo acids.  Specified strong acids are sulphuric acid, HF, sulphonic acids and numerous ansolvo acids namely BF3 complexes with carboxylic acids, esters, ketones, aldehydes, ethers and alcohols; acetic and benzoic acids are named as weak acids.  The BF3 complexes may be formed in situ from BF3 and one of the alcoholic reagents.  Silver nitrate, ferric sulphate, ferrous sulphate with sulphuric acid and ferrous ammonium sulphate are suitable acidic salts.  In typical examples, there are prepared diallyl ether and the allyl ethers of methanol, butanol, n-octadecanol, 5-pentenol, 5,5,7,7-tetramethyl-2-octenol, cyclohexanol, benzyl alcohol and cinnamyl alcohol.  In some cases, the ethers are purified by treating with phosphoric acid anhydride followed by distillation or by refluxing with boric acid in benzene, to remove unchanged alcohol. Numerous other non-tertiary alcohols are mentioned including various alkoxy, cycloalkoxy and aryloxy ethanols, and polyethoxy ethanols having a terminal hydrocarbon radical of sufficient size to provide hydrophobic balance e.g. dodecyl or octyl phenyl for example alkylphenoxy polyethoxy ethanols containing 3-22 carbon atoms in the alkyl group and 5-100 ether groups.