UNSTABLE 1,1,2-ENETRIOLS AS (PROBABLE) INTERMEDIATES IN THE DECARBOXYLATION OF ALPHA,BETA-DIKETO ACIDS
UNSTABLE 1,1,2-ENETRIOLS AS (PROBABLE) INTERMEDIATES IN THE DECARBOXYLATION OF ALPHA,BETA-DIKETO ACIDS
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DOI：
10.1021/jo00009a029
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发表时间：
1991-04-26
影响因子：
3.6
通讯作者：
ROTZLER, G
中科院分区：
文献类型：
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作者：
DAHN, H;ROTZLER, G
在（水合）4-芳基-2,3-二酮丁酰胺2（芳基=苯基，邻氯苯基，对甲氧基苯基）的酸水解过程中，中间体二酮酸(3)快速脱羧生成3-芳基乳酸(5)。在脱羧步骤中，形成另一种不稳定的中间体。后者表现为在水解-脱羧反应中减少1 mol碘，从而形成分离的3-芳基丙酮酸(6)，而不是5。因此，碘对不稳定中间体的氧化比它的酮化要快。它被配制成1,1,2-烯三醇(4)，比α -羟基烯酮更可能。
During the acid hydrolyis of (hydrated) 4-aryl-2,3-diketobutyramide 2 (aryl = phenyl, o-chlorophenyl, p-methoxyphenyl), 3-aryllactic acid (5) is formed by rapid decarboxylation of the intermediate diketo acid (3). In the decarboxylation step, a further unstable intermediate is formed. The latter manifests itself by reducing 1 mol of added iodine during the hydrolysis-decarboxylation reaction, thereby forming 3-arylpyruvic acid (6), isolated instead of 5. Thus, the oxidation of the unstable intermediate by iodine is more rapid than its ketonization. It is formulated as an 1,1,2-enetriol (4), more probable than an alpha-hydroxyketene.