| 摘要 |
Preparation of 4-haloalkyl-nicotinonitriles (I) comprises reacting a 3-amino-1-haloalkyl-2-propenone (II) with a nitrile (III) selected from 3,3-disubstituted propionitriles, 3-substituted acrylonitriles and propiolonitrile, and cyclizing the obtained 3-oxo-haloalkenylamino-substituted nitrile (IV). Intermediates (IV) are new compounds. Also new are tetra- or dihydropyridine derivative intermediates (XV)-(VII). Preparation of 4-haloalkyl-nicotinonitriles of formula (I) comprises: (a) reacting a 3-amino-1-haloalkyl-2-propenone of formula R-C(O)-NH-CH=CH-NH2 (II) with a nitrile (III) of formula Q-CH=CH-CN (IIIa), Q2-CH-CH2-CN (IIIb) or H-CC-CN (IIIc); and (b) cyclizing the obtained alkenylamino-substituted nitrile (IV) of formula R-C(O)-NH-CH=CH-NH-CH=CH-CN (IVa) or R-C(O)-NH-CH=CH-NH-CH(Q)-CH2-CN (IVb). R = 1-4C haloalkyl; Q = Cl, Br or -YR1; R1 = alkyl; and Y = O, S, NR1 or OCO; provided that the two Q groups in (IIIb) are both Cl and/or Br or both -YR1. Independent claims are also included for: (1) preparation of 4-haloalkyl-nicotinamides of formula (XI), by hydrolyzing (I) obtained by the above method; (2) intermediates (IVa) and (IVb) as new compounds; and (3) new tetra- or dihydropyridine derivative intermediates of formula (XV)-(XVII). R2 = 1-6C alkyl; and M = H or monovalent cation.
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