| abstract |
1,256,184. Allylic alcohols. RHONE POULENC S.A. 30 Dec., 1969 [30 Dec., 1968], No. 63395/69. Heading C2C. Allylic primary or secondary alcohols having the general formula are prepared by heating an allylic tertiary alcohol having the formula wherein R 1 and R 2 are each saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or araliphatic radicals, optionally substituted by a halogen or a hydroxy, alkoxy, acyl or acyloxy group, and optionally having their carbon chain interrupted by hetero-atoms, such as O, N or S, or functional groups such as -CO- or -CONH, to together form a single, divalent, saturated or unsaturated aliphatic radical of 2 or more carbon atoms optionally substituted by a halogen or an alkyl, cycloalkyl, aryl, aralkyl, hydroxy, alkoxy, acyl or acyloxy radical, and optionally having their carbon chain interrupted as above, and R 3 is hydrogen or the same as R 1 and R 2, in the liquid phase in the presence of a catalyst comprising a derivative of a transition metal from Group VA, VIA or VIIA of the Periodic Table. Suitable specified tertiary alcohols include linalol, nerolidol, 3- methyl - 1 - penten - 3 - ol, 2 - methyl - 3- nonen - 2 - ol, 2,2,6 - trimethyl - 1 - vinylcyclohexanol and 3-methyl-l-buten-3-ol. Suitable specified catalysts include, ammonium metavanadate, t-butyl-, t-amyl-, cyclohexyl-, and tetrahydrolinalyl - orthovanadates, ammonium molybdate and vanadyl acetylacetonate. The reaction is preferably carried out continuously at a temperature of from 50‹ to 250‹ C. under an anhydrous atmosphere in the presence of a co-catalyst e.g. ammonia. |