以甲醛与酰亚胺的縮合为基础的化学研究——Ⅰ.N-羟甲基-d-樟脑酰亚胺

CHEMICAL RESEARCH BASED ON THE CONDENSATION BETWEEN FORMALDEHYDE AND IMIDE——Ⅰ. N-METHYLOL-d-CAMPHORIMIDE

1.甲醛与d-樟脑酰亚胺,在碳酸钾的催化作用下,极易缩合为N-羟甲基-d-樟脑酰亚胺。 2.和其它N-羟甲基酰亚胺一样,这个化合物中的羟基是相当活泼的,用乙酰氯即可把它换成氯,也制成了相应溴化及碘化物。 3.从N-卤甲基-d-樟脑酰亚胺制得了一系列衍生物,其中体现了C-C键、C-S键与C-N键的形成。 4.尝试用溴化d-樟脑酰亚胺甲基三乙基季铵拆解dl-苦杏仁酸,未获明确结果。北京大学化学系有机化学教研室曾为我们提供使用旋光仪的方便,谨致深切谢意。

The condensation between formaldehyde and d-camphorimide has been found to proceed as smoothly as those reported in the literature for phthalimide, succinimide and maleimide. From the condensation product, N-methylol-d-camphorimide, were prepared the acetate and benzoate. Reaction of acetyl chloride, however, instead of yielding the acetate, gave good yield of N-chloromethyl-d-camphorimide. N-Bromomethyl- and N-iodomethyl-d-camphorimide have been also prepared. The N-halomethyl-d-camphorimide served as starting material for the preparation of a number of derivatives, through nucleophilic substitution of the halogen by CN, SCN, SH, SC(NH_2)_2^+, and N(C_2H_5)_3^+groups.