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1,3-二甲氧基-2-吗啉-N-基戊-1-烯-4-酮(11a)的酸水解经证实发生部分重排,生成1,3-(1a)和1,5-二甲氧基乙酰丙酮(2a)的混合物,并通过与氰基乙酰胺缩合,分别形成3-氰基-4-甲氧甲基-5-甲氧基-6-甲基吡啶-2-醇(3a)和3-氰基-4,6-双(甲氧甲基)吡啶-2-醇(4a)加以证实,前者还转化为维生素 B_6.在相应的乙氧基序列中,除得到1b、2b、3b 和4b 外,还分离了反向缩合产物3-氰基-4-甲基-5-乙氧基-6-乙氧甲基吡啶-2-醇(5b).对 Fedoronko 等为1,3-二甲氧基丙酮的重排-水解为丙酮醛提出的烯丙型重排机制提出了质疑.事实上,这一重排更可能是一种热过程的[1.3]单键迁移过程和提供了支持的事例.
Acid hydrolysis of 1,3-dimethoxy-2-morpholino-N-pentyl-1-en-4-one (11a) was confirmed to undergo partial rearrangement to give 1,3- (1a) and 1, 5-dimethoxyacetylacetonate (2a) and condensation with cyanoacetamide to form 3-cyano-4-methoxymethyl-5-methoxy-6-methylpyridin-2 (3a) and 3-cyano-4,6-bis (methoxymethyl) pyridin-2-ol (4a) were confirmed, the former also converted to vitamin B_6 in the corresponding ethoxy sequence, in addition to The reverse condensation product 3-cyano-4-methyl-5-ethoxy-6-ethoxymethylpyridin-2-ol (5b) was also obtained in addition to 1b, 2b, 3b and 4b. Etc., raised the question of the allyl rearrangement mechanism proposed by the rearrangement-hydrolysis of 1,3-dimethoxyacetone to pyruvaldehyde. In fact, this rearrangement is more likely to be a thermal process [1.3] Key migration process and provide examples of support.