Prodn. of vinyl carbonyl cpds. from acetylenic alcohol cpds

Prodn. of vinyl carbonyl cpds. of formula C(R1)(R2)=CH-CO-R3 (I) is effected by heating an acetylenic alcohol of formula (II) in the presence of a catalyst comprising a Ti cpd. and a Cu or Ag cpd., opt. in the presence of a mineral or organic acid ester, an acid anhydride or pref. an organic acid. - In formulae, R1-R3=H, or opt. unsatd. aliphatic, opt. unsatd. cycloaliphatic, aromatic or arylaliphatic gp., opt. substd. by halogen, OH, alkoxy, phenoxy, acyl or acyloxy, or R1+R2 is a divalent gp. The Ti cpd. is pref (a) of formula Ti(R)4, where each R is independently halogen, OR', OCOR' or OSiR1R2R3, R'=1-20C alkyl and R1-R3=alkyl or aryl; (b) a Ti chelate; (c) TiCl3, (d) titanocene dichloride; (e) a cyclopentadienyl titanium (IV) deriv. of (f) TiO(X)2, where X=halogen, OR' or OCOR'. The Cu or Ag cpd. is a salt of a mineral or organic acid, esp. CuCl, CuCl2, cupric oxalate or Ag trifluoroacetate. The reaction is effected at 80-180 deg.C in the presence of 0.005-0.05 mole of the Ti cpd., 0.005 -0.1 mole of the Cu or Ag cpd. and 0.01-1 mole of a carboxylic acid per mole of (II), in an organic solvent. Prodn. of vinyl carbonyl cpds. of formula C(R1)(R2)=CH-CO-R3 (I) is effected by heating an acetylenic alcohol of formula (II) in the presence of a catalyst comprising a Ti cpd. and a Cu or Ag cpd., opt. in the presence of a mineral or organic acid ester, an acid anhydride or pref. an organic acid. - In formulae, R1-R3=H, or opt. unsatd. aliphatic, opt. unsatd. cycloaliphatic, aromatic or arylaliphatic gp., opt. substd. by halogen, OH, alkoxy, phenoxy, acyl or acyloxy, or R1+R2 is a divalent gp. The Ti cpd. is pref (a) of formula Ti(R)4, where each R is independently halogen, OR', OCOR' or OSiR1R2R3, R'=1-20C alkyl and R1-R3=alkyl or aryl (b) a Ti chelate (c) TiCl3, (d) titanocene dichloride (e) a cyclopentadienyl titanium (IV) deriv. of (f) TiO(X)2, where X=halogen, OR' or OCOR'. The Cu or Ag cpd. is a salt of a mineral or organic acid, esp. CuCl, CuCl2, cupric oxalate or Ag trifluoroacetate. The reaction is effected at 80-180 deg.C in the presence of 0.005-0.05 mole of the Ti cpd., 0.005 -0.1 mole of the Cu or Ag cpd. and 0.01-1 mole of a carboxylic acid per mole of (II), in an organic solvent. (Machine-translation by Google Translate, not legally binding) PROCEDIMIENTO PARA LA PREPARACION DE COMPUESTOS CARBONILADOS ETILENICOS DE FORMULA GENERAL (II) POR ISOMERIZACION DE UN ALCOHOL ACETILENICO DE FORMULA GENERAL (I) EN PRESENCIA DE UN CATALIZADOR CONSTITUIDO PO