Patent GB-1015927-A (GB)
Title: Preparation of tertiary amino unsaturated ketones
IPC: C07D213/85
Filed: 1962-07-26
Abstract: Stabilizers for polyvinyl chloride comprise compounds prepared by reacting tertiaryamino unsaturated ketones with an acid salt of a hydrazine, a hydroxylamine or a C-substituted acetamide (see Division C2C).  Compounds 4 - ethyl - 5 - methyl pyrazole; 5 - isopropylpyrazole; 5 - isopropyl - isoxazole; and 3-cyano - 2 - hydroxy - 6 - isopropyl pyridine are specified and prepared.ALSO:b  - t - amino - a ,b  - unsaturated ketones of formula X-CH = CR1-CO-CH(R2)R3 in which X is a group containing an N atom bonded to 3 C atoms one of which is the -CH =, R1 is H or an organic group and R2 and R3 are each an organic group, or with the C atom form a carbocyclic or heterocyclic group, are prepared by reacting at above 10 DEG  C. an enamine of formula X-CH = C(R2)R3 with a ketene of formula R1-CH = CO. Compounds in which R2 and R3 are R4 and R5 and are each H or an organic group or with the C to which they are bonded form a carbocyclic or heterocyclic group are also included.  X may be R1(R11)N-, <FORM:1015927/C2/1> or <FORM:1015927/C2/2> wherein R1 and R11 are monovalent organic groups, e.g. alkyl (1-8 C) groups, piperidine, methyl substituted piperidines, pyrrolidine, 3-azabicyclo [3.2.2] nonane, piperazine, and methyl substituted piperazine.  R1-R5 may include alkyl (1-18 C), phenyl, thienyl, allyl and carbalkoxy groups, and R2 and R3 or R4 and R5 with the C atom may represent phenyl, cyclopentane, cyclohexane, norbornane, norbornene and pyron rings.  Inert solvents may be present in the reaction and the products purified by fractional distillation or crystallization, solvent extraction or chromatographic adsorption.  Examples describe the preparation of 2-ethyl-4-methyl-1-piperidino-1-penten-3 - one; 2 - ethyl - 1 - piperidino - 1 - buten - 3 - one; 1 - morpholino - 2 - pentyl - 1 - buten - 3 - one: 2 - ethyl - 4 - methyl - 1 - piperidino - 1 - hexen - 3 - one; 2,4 - diethyl - 1 - piperidino - 1 - hexen - 3 - one, and 1 - octen - 3 - one; 2 - ethyl - 4,4 - diphenyl - 1 - piperidino - 1 - buten - 3 - one; 2,4 - dimethyl - 1 - piperidino - 1 - penten - 3 - one; 2 - ethyl - 4 - methyl - 1 - pyrrolidino - 1 - penten - 3 - one; 2 - ethyl - 4 - methyl - 1 - dimethylamino - 1 - penten - 3 - one; 2 - ethyl - 4 - methyl - 1 - dibutylamino - 1 - penten - 3 - one; 1 - dimethylamino - 4 - methyl - 1 - penten - 3 - one; 4 - methyl - 1 - piperidino - 1 - penten - 3 - one; 4 - methyl - 1 - morpholino - 1 - penten - 3 - one; 1 - (N - iminodipropionitrile) - 4 - methyl - 1 - penten - 3 - one; 1 - (dibenzylamino) - 4 - methyl - 1 - penten - 3 - one; 1,4 - piperazinyl - 1,11 - bis - [4 - methyl - 1 - penten - 3 - one]; 1 - (N - methylanilino) - 4 - methyl - 1 - penten - 3 - one; 3 - cyclohexyl - 1 - piperidino - 1 - propen - 3 - one; 1 - (3 - azabicyclo[3.2.2]nonan - 3 - yl) - 4 - methyl - 1 - penten - 3 - one; 4 - ethyl - 1 - piperidino - 1 - hexen - 3 - one; and dimethylamino - 4 - ethyl - 1 - hexen - 3 - one.  The products may be reacted with an acid salt of a hydrazine, a hydroxylamine or C-substituted acetamide to form substituted pyrazoles, e.g. 4-ethyl-5-methyl-pyrazole, 5-isopropylpyrazole, 5-isopropyl - iso-oxazole and 3 - cyano - 2 - hydroxy - 6 - isopropylpyridine which are suitable as stabilizers for polyvinyl chloride.  Specifications 951,110,965,769 and 985,816 are referred to.