Studies on 4-Chloropyrido [2, 3-d] pyrimidine and Pyrido [2, 3-d] pyrimidine

抄録

Ketone carbanion reacted as nucleophilic reagent with 4-chloropyrido [2, 3-d] pyrimidine (I). Reaction of I in the presence of sodium amide with acetophenone and acetone gave 2-(4-pyrido [2, 3-d] pyrimidinyl) acetophenone (III) and 1-(4-pyrido [2, 3-d] pyrimidinyl)-2-propanone (IV), respectively. The reaction with propiophenone, 3-pentanone and 2-butanone afforded 4-ethylpyrido [2, 3-d] pyrimidine (V). The reaction with 2-pentanone gave 1-(4-pyrido [2, 3-d] pyrimidinyl)-2-pentanone (VII) and 4-propylpyrido [2, 3-d] pyrimidine (VI). Quinazoline (XIII) has been shown to add several nucleophilic reagents across the 3, 4-position. These investigation have now been extended to pyrido [2, 3-d] pyrimidine (X). The reaction of X with methylmagnesium iodide, benzylmagnesium chloride and phenylmagnesium bromide afforded 4-methyl-(XIVa), 4-benzyl-(XIVb) and 4-phenyl-3, 4-dihydropyrido [2, 3-d] pyrimidine (XIVc), respectively. These compounds was derived to 4-methyl- (IX), 4-benzyl- (XVII) and 4-phenyl-pyrido [2, 3-d] pyrimidine (XVIII), respectively, by oxidation with potassium ferricyanide in alkali medium. The reaction with acetophenone in sodium methoxide solution afforded 2-(3, 4-dihydro-4-pyrido [2, 3-d] pyrimidinyl) acetophenone (XV). The reaction with hydrogen cyanide afforded 3, 4-dihydro-4-pyrido [2, 3-d] pyrimidinecarbonitrile (XVI) which was derived to 4-pyrido [2, 3-d] pyrimidinecarbonitrile (XIX). XIX was also derived to 4-methoxypyrido [2, 3-d] pyrimidine (XX) and 4 (3H)-pyrido-[2, 3-d] pyrimidinone, respectively from the reaction with methoxide and hydroxide ion. It may be concluded through the foregoing experimental results that the addition is occured across the 3, 4-position as similar as that of XIII already reported.