Photorelease of Alcohols from 2-Nitrobenzyl Ethers Proceeds via Hemiacetals and May Be Further Retarded by Buffers Intercepting the Primary aci-Nitro Intermediates
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- 作者：Bruno Hellrung ; Yavor Kamdzhilov ; Markus Schwö ; rer ; and Jakob Wirz
- 刊名：Journal of the American Chemical Society
- 出版年：2005
- 出版时间：June 29, 2005
- 年：2005
- 卷：127
- 期：25
- 页码：8934 - 8935
- 全文大小：74K
- 年卷期：v.127,no.25(June 29, 2005)
- ISSN：1520-5126
文摘
The mechanism for the photoinduced release of glycolic acid from its 2-nitrobenzyl ether was reinvestigated. The pH-dependent rate constants of the thermal reactions initiated by irradiation are similar to those reported previously for 2-nitrobenzyl methyl ether. A hemiacetal intermediate that limits the release rate of glycolic acid at pH values 
7 was identified by time-resolved IR and UV measurements. Furthermore, 2-(2'-nitrosophenyl)-1,3-dioxolan-4-one, a long-lived intermediate formed by intramolecular trapping of the aci-tautomer, was observed and characterized.
7 was identified by time-resolved IR and UV measurements. Furthermore, 2-(2'-nitrosophenyl)-1,3-dioxolan-4-one, a long-lived intermediate formed by intramolecular trapping of the aci-tautomer, was observed and characterized.