On the mechanism of the organocatalyzed Beckmann rearrangement of cyclohexanone oxime by trifluoroacetic acid in aprotic solvent

被引：33

作者：

Ronchin, L. ^{[1
]}

Vavasori, A. ^{[1
]}

机构：

[1] Univ Ca Foscari Venezia, Dept Chem, I-30123 Venice, Italy

来源：

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 2009年 / 313卷 / 1-2期

关键词：

Beckmann rearrangement; epsilon-Caprolactam; Trifluoroacetic acid; Mechanism; Reaction rate; IONIC LIQUIDS; PICRYL ETHERS; ACETIC ACID; KETOXIMES; TOLUENESULFONATES; CAPROLACTAM; CHLOROFORM; CATALYSTS; KINETICS; AMIDES;

D O I：

10.1016/j.molcata.2009.07.016

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The Beckmann rearrangement of cyclohexanone oxime to epsilon-caprolactam in high yield catalyzed by trifluoroacetic acid in aprotic solvents is described. The influence of the concentration of reagents, intermediates, solvents on reaction rate and selectivity in e-caprolactam is studied. The identification of the key intermediate and its role in the catalysis are reported together with the influence of the acid on the reaction rate. In addition, the study of the hydrolysis reactions of reagent and intermediates highlights what are the parameters that influence the selectivity to epsilon-caprolactam. On the basis of these results a likely catalytic cycle based only on the experimentally verified intermediates is also given. (C) 2009 Elsevier B.V. All rights reserved.

引用

页码：22 / 30

页数：9

共 28 条

[1] CAREY FA, 1990, ADV ORGANIC CHEM B, V540
[2] Studies of the Beckmann change Part I The spontaneous rearrangement of oxime picryl ethers
Chapman, AW
Howis, CC
[J]. JOURNAL OF THE CHEMICAL SOCIETY, 1933, : 806 - 811
[3] Beckmann rearrangement of oximes under very mild conditions
De Luca, L
Giacomelli, G
Porcheddu, A
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2002, 67 (17) : 6272 - 6274
[4] Fisher G, 2003, FIBRES TEXT EAST EUR, V11, P14
[5] FISHER WB, 1982, KIRK OTHMER ENCY CHE, V18, P874
[6] BECKMANN REARRANGEMENT .1. SYNTHESES OF OXIME PARA-TOLUENESULFONATES AND BECKMANN REARRANGEMENT IN ACETIC ACID, METHYL ALCOHOL AND CHLOROFORM
HELDT, WZ
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1958, 80 (21) : 5880 - 5885
[7] BECKMANN REARRANGEMENT .3. REARRANGEMENT OF OXIME P-TOLUENESULFONATES IN CHLOROFORM, ACETIC ACID, AND METHANOL
HELDT, WZ
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1961, 26 (06) : 1695 - &
[8] Solid phase synthesis of amides by the Beckmann rearrangement of ketoxime carbonates
His, S
Meyer, C
Cossy, J
Emeric, G
Greiner, A
[J]. TETRAHEDRON LETTERS, 2003, 44 (47) : 8581 - 8584
[9] Holderich WF, 2003, US Pat, Patent No. [6,531,595 B2, 6531595, 6531595B2]
[10] HUITRIC AC, 1969, J ORG CHEM, V34, P1232

← 1 2 3 →