GB1168000A - Novel 2-Acyl Acrylonitriles and processes for the preparation thereof - Google Patents

Abstract

1,168,000. Acylated acrylonitrile and the preparation thereof. TOYO RAYON K.K. 27 July, 1967 [28 July, 1966; 18 March, 1967; 13 April, 1967], No. 34660/67. Heading C2C. [Also in Division C3] 2-Acyl acrylonitriles of the formula wherein R is a hydrogen atom or a hydrocarbon group having not more than 12 carbon atoms, may be obtained by (A) reacting a compound of the formula with a conjugated diene at 100-250‹ C., contacting the adduct obtained with an oxidizing or dehydrogenating agent, and heating the compound obtained to 100-500‹ C. under conditions where the moisture content in the reaction system is below 0À1 mol based on 1 mol of the keto compound, or (B) by heating a 2-acyl acrylonitrile polymer of the formula to a temperature of 140-280‹ C. under dry conditions where the moisture content in the reaction system is below 0.1 mol based on 1 mol of the monomer. In process (A) the starting material may be prepared by condensing acrylonitrile with an aldehyde in the presence of an organic phosphorus compound and the Diels-Alder adducts which are formed as intermediates during the process may be isolated; the first step of process (A) may be effected in the presence of a Lewis acid catalyst, optionally in the presence of an inert solvent and a stabilizer under an inert atmosphere. The second step of process A may be effected by employing as oxidizing agent chromic anhydride, potassium permanganate, " Jones " reagent or Oppernauer reagent or by employing a dehydrogenation process using, for example, nickel or palladium. The third step of process (A) is suitably effected in the presence of a drying agent, e.g. P 2 0 5 or silica gel, or in the presence of a pre-dried stream of S0 2 , NO, HCI, HF, HBr, BF 3 or a mixture thereof with nitrogen or argon; the reaction is preferably effected under reduced pressure in the presence of an inert organic solvent, e.g. tricresyl phosphate, triphenyl phosphate or dioctyl phthalate, and a polymerization inhibitor, e.g. a protonic acid, a Lewis acid, a phosphoric acid or an acid anhydride or a mixture thereof. The reaction of process (B) is suitably effected in the presence of a stabilizer, an inert solvent, e.g. tricresyl or triphenyl phosphate, dioctyl phthalate, and a polymerization inhibitor, e.g. a Lewis or protonic acid or a mixture thereof, under reduced pressure; moisture is suitably removed by using a drying agent, e.g. P 2 O 5 , CaCl 2 or silica gel, by azeotropic distillation or by carrying out the reaction in a stream of S0 2 , NO, HCI, HF, HBr, BF 3 or a mixture thereof with nitrogen or argon. The products possess adhesive properties.