Patent GB-907777-A (GB)
Title: A process for the preparation of tertiary acid amides
IPC: C07F9/26
Filed: 1960-11-30
Abstract: Acid amides in which the nitrogen atom has one valency linked to a carbon, phosphorus or silicon atom, the other two valencies being linked to carbon atoms one of which is linked to a further carbon atom by an olefinic double bond (see Group IV(b)), may be polymerized, copolymerized with other unsaturated compounds, used for modifying the properties of known polymers and copolymers, and used in the preparation of polymeric oil additives.  The invention also comprises compounds of the general formula <FORM:0907777/IV(a)/1> wherein alk and R represent alkyl groups which may be the same or different and R1, R11 and R111 are alkyl groups and/or hydrogen. These compounds are prepared by treating an aldimine or ketimine of the general formula R-N=CR1-CHR11R111 wherein R, R1, R11 and R111 are as defined above, with a dialkylamino-trichlorosilane at a temperature of below 30 DEG C. and subsequently splitting of a molecule of hydrogen chloride by heating in the presence of a tertiary amine.  Several suitable aldimines are specified and in Example (7) diethylamino-(propyl-prop-1-enylamino)-dichlorosilane is prepared from diethylaminotrichlorosilane and N-propyl-propanaldimine in the presence of triethylamine and benzene.  Specification 539,332 is referred to.ALSO:Acid amides in which the nitrogen atom has one valency linked to a carbon, phosphorus or silicon atom (see Group IV(a)), the other two valencies being linked to carbon atoms one of which is linked to a further carbon atom by an olefinic double bond, are prepared by treating an aldimine or ketimine of the general formula R-N = CR1-CHR11R111 wherein R is an alkyl radical and R1, R11 and R111 are hydrogen atoms and/or alkyl groups, with a carboxylic acid anhydride, a carboxylic acid chloride or a phosphorus oxyhalide at a temperature below 30 DEG C. and subsequently splitting off a molecule of the hydrogen halide corresponding to the acid halide used or the carboxylic acid corresponding to the acid anhydride used by heating in the presence of a tertiary amine.  The invention also comprises dichlorophosphoric amides of the general formula Cl2.P(O).N(R).C(R1)=CR11R111 R, R1, R11 and R111 being as defined above.  The addition of acid halide or carboxylic acid anhydride may also be carried out in the presence of a tertiary amine.  The reaction is preferably carried out in the presence of an inert hydrocarbon solvent such as benzene, toluene, xylene or hexane.  The reaction is preferably carried out with approximately stoichiometric proportions of the imine and acid halide or carboxylic acid anhydride and a slight excess of tertiary amine.  The products may be recovered from the reaction mixture by distillation, any insoluble salts present being optionally filtered off before-hand. Specified tertiary amines are triethylamine and pyridine. Specified starting materials are N - propyl - propanaldimine, N - propyl-acetaldimine and N - propyl - butanaldimine, acetic, propionic and butyric anhydrides, acetyl, propionyl and benzoyl chlorides and phosphorus oxychloride. In examples the following compounds are prepared: (1) N-propyl-N-vinyl-acetamide; (2), (4) and (5) N-propyl-N-prop-1-enyl-acetamide; (3) N-propyl-N-but-1-enyl-acetamide; (6) N-propyl-N-prop-1-enyl-benzamide; (8) propyl-(prop-1-enyl)-amino-phosphoryl dichloride.  In Example (3) N-propyl acetamide is formed as a by-product.  The products may be used as intermediates in the preparation of insecticides and may be polymerized or co-polymerized (see Group IV(a)).  Specification 539,332 is referred to.