LIGHT-SENSITIVE AMIDES - PHOTOSOLVOLYSIS OF SUBSTITUTED 1-ACYL-7-NITROINDOLINES
LIGHT-SENSITIVE AMIDES - PHOTOSOLVOLYSIS OF SUBSTITUTED 1-ACYL-7-NITROINDOLINES
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DOI：
10.1021/ja00419a038
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发表时间：
1976-01-01
影响因子：
15
通讯作者：
PATCHORNIK, A
中科院分区：
文献类型：
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作者：
AMIT, B;BENEFRAIM, DA;PATCHORNIK, A
羧基官能团通常通过转化成酯来保护。由于酰胺基一般比酯基更耐碱性和酸性溶剂分解，因此需要在相当剧烈的条件下才能将其断裂，而酰胺键在溶剂分解条件下的稳定性，如果能找到一种特异而温和的断裂方法，则可使其发挥优势。直到几年前，才发现酰胺光解产生大量的游离羧酸。我们最近描述了由N-取代邻硝基苯胺2和8-硝基-1，2，3，4-四氢喹啉3衍生的酰胺，它们在苯或醇中光解时高产率地得到游离羧酸。我们现在希望报道新的光敏酰胺，其经历平稳的光溶剂分解。在水存在下，对衍生自5-溴-7-硝基二氢吲哚（2a）和5，7-二硝基二氢吲哚（2b）的酰胺1进行辐照，以几乎定量的产率（当量1）提供游离羧酸（表I）和起始二氢吲哚2a和2b。类似地，在醇的存在下照射酰胺1以高产率得到相应的酯（表I）和二氢吲哚（eq 1）。这些光溶剂分解反应可以容易地进行la，R= Ph; X= Br B，R= p-MeOCTL; X= Br c，R= m-NO，C6 H4; X= Br d，R=
Carboxyl functions are generally protected by conversion to esters. Their protection via their amides is rarely encoun-tered since the amide group is generally more resistant to basic and acidic solvolysis than the ester group, and therefore rather vigorous conditions are needed to cleave it. On the other hand, the stability of the amide bond towards sol-volytic conditionscould be turned to an advantage, if a spe-cific and mild method for its cleavage were available. The photolysis of amides to furnish free carboxylic acids in sig-nificant yields has not been reported1 until a few years ago. We have recently described amides derived from N-substituted o-nitroanilines2 and 8-nitro-1, 2, 3, 4-tetrahydroquino-lines, 3 which on photolysis in benzene or alcohol afford the free carboxylic acids in high yields. We now wish to report new light sensitive amides which undergo smooth photosolvolysis. Irradiation of amides 1, derived from 5-bromo-7-nitroindoline (2a) and 5, 7-dinitroindoline (2b), in the presence of water, furnished the free carboxylic acids (Table I) and the starting indolines 2a and 2b in nearly quantitative yields (eq 1). Similarly, irradiation of amides 1 in the presence of alcohols afforded in high yields the corresponding esters (Table I) and indolines (eq 1). These photosolvolytic reactions can easily be followed by la, R= Ph; X= Br b, R= p-MeOCTL; X= Br c, R= m-NO, C6H4; X= Br d, R=