3-ELECTRON OXIDATIONS .16. CHROMIC-ACID OXIDATION OF MANDELIC-ACID

被引:37
作者
IP, D [1 ]
ROCEK, J [1 ]
机构
[1] UNIV ILLINOIS,DEPT CHEM,CHICAGO,IL 60680
关键词
D O I
10.1021/ja00515a027
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The chromic acid oxidation of mandelic acid (MA) obeys the rate law-d[Cr(VI)]/dt=[HCrO4-] [MA](k1+ k2[H+] + k3[MA]). The reactions corresponding to the two first-order kinetic terms (k, and k2) yield benzaldehyde, benzoic acid, and carbon dioxide in a 1:1:2 ratio, while the second-order reaction (k3) produces a benzaldehyde, phenylglyoxylic acid, and carbon dioxide in a 2:1:2 ratio. Neither benzaldehyde nor phenylglyoxylic acid is intermediate in the formation of benzoic acid. Both the first-order and the second-order reactions are three-electron oxidations. It is proposed that in the first-order reaction mandelic acid is oxidized to carbon dioxide and a benzoyl radical. This reaction represents the first example of an intramolecular three-electron oxidation in which a carbon hydrogen and a carbon-carbon bond to the same carbon atom are broken simultaneously in the rate-limiting step. © 1979, American Chemical Society. All rights reserved.
引用
收藏
页码:6311 / 6319
页数:9
相关论文
共 44 条
[11]   3-ELECTRON OXIDATIONS .2. CHROMIUM(VI) OXIDATION OF OXALIC-ACID [J].
HASAN, F ;
ROCEK, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (26) :9073-9081
[12]   3-ELECTRON OXIDATIONS .10. COOXIDATION OF ISOPROPYL-ALCOHOL AND GLYCOLIC ACID [J].
HASAN, F ;
ROCEK, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (13) :3762-3766
[13]   3-ELECTRON OXIDATIONS .4. CHROMIC ACID COOXIDATION OF TERTIARY HYDROXY-ACIDS AND ALCOHOLS [J].
HASAN, F ;
ROCEK, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (16) :5421-5422
[14]   3-ELECTRON OXIDATIONS .3. CHROMIUM(V) OXIDATION STEP [J].
HASAN, F ;
ROCEK, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (25) :8946-&
[15]   3-ELECTRON OXIDATIONS .7. PRE-STEADY-STATE PHASE OF CHROMIC ACID OXIDATION OF OXALIC-ACID [J].
HASAN, F ;
ROCEK, J .
JOURNAL OF ORGANIC CHEMISTRY, 1974, 39 (17) :2612-2615
[16]   COOXIDATION OF ISOPROPYL ALCOHOL AND OXALIC-ACID BY CHROMIC ACID - ONE-STEP THREE-ELECTRON OXIDATION [J].
HASAN, F ;
ROCEK, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (09) :3181-&
[17]   3-ELECTRON OXIDATIONS .6. CHROMIC ACID COOXIDATION OF CYCLOBUTANOL AND OXALIC-ACID - CHROMIUM(V) OXIDATION OF CYCLOBUTANOL [J].
HASAN, F ;
ROCEK, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1974, 96 (02) :534-539
[18]   KINETICS AND MECHANISM FOR OXIDATION REACTIONS OF CHROMIUM(VI) .3. SOLVENT EFFECT ON RATE CONSTANTS AND ISOTOPIC EFFECTS IN OXIDATION OF SECONDARY ALCOHOLS BY CHROMIUM(VI) [J].
HECKNER, KH ;
LANDSBER.R ;
GRUPE, KH .
JOURNAL FUR PRAKTISCHE CHEMIE, 1971, 313 (01) :161-&
[19]  
HECKNER KH, 1971, J PHYS CHEM LEIPZIG, V247, P91
[20]  
HECKNER KH, 1969, J PHYS CHEM LEIPZIG, V242, P225