OXIDATIVE DECARBOXYLATION OF 3,4-DIHYDROXYMANDELIC ACID TO 3,4-DIHYDROXYBENZALDEHYDE - ELECTROCHEMICAL AND HPLC ANALYSIS OF THE REACTION-MECHANISM

被引:6
作者
CZAPLA, TH
CLAEYS, MR
MORGAN, TD
KRAMER, KJ
HOPKINS, TL
HAWLEY, MD
机构
[1] KANSAS STATE UNIV AGR & APPL SCI,DEPT CHEM,MANHATTAN,KS 66506
[2] KANSAS STATE UNIV AGR & APPL SCI,DEPT ENTOMOL,MANHATTAN,KS 66506
[3] USDA ARS,N CENT REG,US GRAIN MKT RES LAB,MANHATTAN,KS 66502
基金
美国国家科学基金会;
关键词
3,4-DIHYDROXYMANDELIC ACID; OXIDATIVE DECARBOXYLATION; PARA-BENZOQUINONE METHIDE; ELECTROCHEMICAL OXIDATION; 3,4-DIHYDROXYBENZALDEHYDE; ORTHO-BENZOQUINONE;
D O I
10.1016/0167-4838(91)90557-G
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
Cyclic voltammetric and chronoamperometric data are consistent with a process in which 3,4-dihydroxymandelic acid (DOMA) is oxidized initially in a two-electron step to its corresponding o-benzoquinone. This species is unstable and undergoes the rate-determining loss of CO2 (k = 1.6 s-1 at pH 6 and 25-degrees-C) to give an unobserved p-benzoquinone methide intermediate that rapidly isomerizes to 3,4-dihydroxybenzaldehyde (DOBAL), DOBAL is also electroactive at the applied potential and is oxidized in a two-electron step to 4-formyl-1,2-benzoquinone. Subsequent reactions of 4-formyl-1,2-benzoquinone include the oxidation of unreacted DOMA and the hydration of its aldehyde functional group. Oxidation of DOMA directly to its p-benzoquinone methide apparently does not occur. Derivatives of mandelic acid (e.g., 4-hydroxymandelic acid) that are expected to give only their corresponding p-benzoquinone methides upon oxidation afford redox behavior that differs distinctly from that for DOMA.
引用
收藏
页码:400 / 406
页数:7
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