A process for the manufacture of new unsaturated alcohols

摘要

An alcohol of the formula RR1C=CR11CH (OH)C­CR111, wherein R, R1 and R11 are hydrogen or alkyl groups with not more than six carbon atoms and R111 is hydrogen, alkyl groups with not more than four carbon atoms, vinyl, methylvinyl or divinyl, is treated with mineral or organic acids or esterifying derivatives thereof or mineral acid salts, whereby the hydroxy group migrates, and may be to a greater or lesser extent esterified. R and R1 may not both be hydrogen and when one of them is methyl the other, and also R11 and R111 may not all be hydrogen. In examples, the following alcohols and acids are employed: (1) 2-methylpropenylethinylcarbinol and sulphuric acid: (2) 4-ethyloctene-4-in-1-ol-3 and sulphuric acid: (3) 3-methylnonadiene-2 : 7-in-4-ol-6 and sulphuric acid: (4) 2-methyloctadiene-1 : 6-in-3-ol-5- and sulphuric acid: (5) octadiene-1 : 6-in-3-ol-5 and sulphuric acid: (6) decene-8-in-5-ol-7 and sulphuric acid: (7) decene-8-in-5-ol-7 and hydrochloric acid: (8) 3-methylnonadiene-2: 7-in-4-ol-6 and hydrochloric acid: (9) decene-8-in-5-ol-7 and hydrochloric acid: (10) decene-8-in-5-ol-7 and acetic anhydride with potassium acetate: (11) octadiene-1 : 6-in-3-ol-5 and hydrochloric acid: (12) 2-methyloctadiene-1 : 6-in-3-ol-5 and hydrochloric acid. When concentrated hydrochloric or sulphuric acid is used the product is esterified; the product of example (10) is an acetate. The phenylurethane of the product of example 1 is obtained by treatment with phenylisocyanate. 2-Methylpropenylethinylcarbinol may be made by condensing acetylene with 2-methylcrotonaldehyde in liquid ammonia in the presence of sodium. It reacts with phenylisocyanate to give a urethane. 4-Ethyloctene-4-in-1-ol-3 may be made by condensing 2-ethylhexene-2-ol-1 with acetylene in liquid ammonia. It gives a urethane by reacting with a -naphthylisocyanate. 3-Methylnonadiene-2 : 7-in-4-ol-6 may be made by condensing 1 : 2-dimethylvinylacetylene in cooled liquid ammonia with crotonaldehyde dissolved in ether while carefully adding sodium. 2-Methyloctadiene-1 : 6-in-3-ol-5 may be made by condensing methylvinylacetylene with crotonaldehyde in liquid ammonia in the presence of sodium. Octadiene-1 : 6-in-3-ol-5 may be made by mixing an ether solution of vinylacetylene with ethylmagnesium bromide and reacting with crotonaldehyde. Decene-8-in-5-ol-7 may be made by condensing the sodio derivative of hexin-1 with crotonaldehyde.