Reduction of acetophenone using supercritical 2-propanol: the substituent effect and the deuterium kinetic isotope effect

被引：18

作者：

Kamitanaka, T ^{[1
]}

Matsuda, T ^{[1
]}

Harada, T ^{[1
]}

机构：

[1] Ryukoku Univ, Fac Sci & Technol, Dept Chem Mat, Shiga 5202194, Japan

来源：

TETRAHEDRON LETTERS | 2003年 / 44卷 / 24期

关键词：

supercritical; 2-propanol; reduction; Meerwein-Ponndorf-Verley reduction; Hammett equation; kinetic isotope effect; acetophenone;

D O I：

10.1016/S0040-4039(03)00975-4

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The reductions of several substituted acetophenones using supercritical 2-propanol were carried out to estimate the Hammett's reaction constant (rho=0.33). Also, the reduction of acetophenone using supercritical deuteriated 2-propanol was carried Out to determine the rate-determining step. The kinetic isotope effects were observed in the reduction using 2-deuterio-2-propanol (k(H)/k(D) = 1.6) and O-deuterio-2-propanol (k(H)/k(D) = 2.0). These findings suggest that the reaction proceeds via a cyclic transition state between acetophenone and 2-propanol similar to that of the Meerwein-Ponndorf-Verley reduction. (C) 2003 Elsevier Science Ltd. All rights reserved.

引用

页码：4551 / 4553

页数：3

共 23 条

[1] THE EFFECT OF STRUCTURE ON REACTIVITY IN SEMICARBAZONE FORMATION [J].

ANDERSON, BM ;

JENCKS, WP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1960, 82 (07) :1773-1777

[2]

[Anonymous], 1999, CHEM SYNTHESIS USING

[3] REDUCTION OF ACETOPHENONES OVER PD ALPO4 CATALYSTS - LINEAR FREE-ENERGY RELATIONSHIP (LFER) [J].

ARAMENDIA, MA ;

BORAU, V ;

GOMEZ, JF ;

HERRERA, A ;

JIMENEZ, C ;

MARINAS, JM .

JOURNAL OF CATALYSIS, 1993, 140 (02) :335-343

[4] Supercritical fluids in heterogeneous catalysis [J].

Baiker, A .

CHEMICAL REVIEWS, 1999, 99 (02) :453-473

[5]

Bröll D, 1999, ANGEW CHEM INT EDIT, V38, P2999

[6] 40 YEARS OF HYDRIDE REDUCTIONS [J].

BROWN, HC ;

KRISHNAMURTHY, S .

TETRAHEDRON, 1979, 35 (05) :567-607

[7] MEERWEIN-PONNDORF-VERLEY REDUCTIONS AND OPPENAUER OXIDATIONS - AN INTEGRATED APPROACH [J].

DEGRAAUW, CF ;

PETERS, JA ;

VANBEKKUM, H ;

HUSKENS, J .

SYNTHESIS-STUTTGART, 1994, (10) :1007-1017

[8] REACTIVITY OF PERFLUORO-N-ALKYL RADICALS - A HAMMETT STUDY OF HYDROGEN-TRANSFER FROM ARENE THIOLS [J].

DOLBIER, WR ;

RONG, XX .

TETRAHEDRON LETTERS, 1994, 35 (34) :6225-6228

[9]

Gubin SP, 1995, DOKL AKAD NAUK+, V345, P490

[10] Alkylation and acetal formation using supercritical alcohol without catalyst [J].

Horikawa, Y ;

Uchino, Y ;

Sako, T .

CHEMISTRY LETTERS, 2003, 32 (03) :232-233

← 1 2 3 →