| 摘要 |
Substituted allyl ethers are produced by reacting a conjugated diene with an organic compound containing a hydroxyl group in presence of a cuprous salt catalyst and acid co-catalyst. The diene is preferably butadiene, but it may also be a hydrocarbon-, alkoxy- or halo-substituted butadiene; either or both double bonds can form part of an alicyclic ring as in vinyl-cyclopentene, -cyclohexene, -cycloheptene, or in cyclohexadiene. The hydroxyl compound may be a mono- or polyhydric alcohol, aliphatic alicyclic or aromatic; it may be substituted by halogen or it may contain ether groups; the hydroxyl compound may be a phenol (including a naphthol), which optionally may be substituted with a halogen atom or an alkoxy group. A number of cuprous salts and acid co-catalysts (including Lewis acids) are listed; a sulphonic resin in which some of the hydrogen ions are replaced by cuprous ions may be used to function as both catalyst and co-catalyst. In examples (1) n-butyl a -methallyl and crotyl ethers are obtained from n-butanol and butadiene with cuprous bromide + HBr-butadiene addition product as catalysts; (2) ethyl a -methallyl and crotyl ethers from ethanol and butadiene with cuprous bromide and HBr; (3) 2-chloroethyl a -methallyl and crotyl ethers from 2-chloroethanol and butadiene with cuprous chloride and HCl and (4) mixed partial a -methallyl and crotyl ethers were obtained from polyethylene glycol (MW200), butadiene, cuprous chloride and HCl. In Examples (1) and (3) the method of isolating the desired products included reacting excess alcohol with boric acid. Other specific products which may be obtained by the process of the invention are methyl crotyl and a -methallyl ethers, 1,3-propanediol dicrotyl ether, benzyl a -ethallyl ether, phenyl a -methallyl ether, butyl b -methylcrotyl ether and butyl d -chlorocrotyl ether. |
