KETO-ENOL EQUILIBRIUM-CONSTANTS OF SIMPLE MONOFUNCTIONAL ALDEHYDES AND KETONES IN AQUEOUS-SOLUTION

被引：101

作者：

KEEFFE, JR ^{[1
]}

KRESGE, AJ ^{[1
]}

SCHEPP, NP ^{[1
]}

机构：

[1] UNIV TORONTO,DEPT CHEM,TORONTO M5S 1A1,ONTARIO,CANADA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1990年 / 112卷 / 12期

关键词：

D O I：

10.1021/ja00168a035

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Keto-enol equilibrium constants, KE, were determined for five aliphatic ketones (2-butanone, 3-methyl-2-butanone, 3,3-dimethyl-2-butanone, 3-pentanone, and 2,4-dimethyl-3-pentanone) and three alicyclic ketones (cyclopentanone, cyclohexanone, and cycloheptanone) in aqueous solution at 25 °C by combining acid-catalyzed enolization and ketonization rate constants according to the relationship KE = kE/kK. Enolization rate constants were measured by halogen scavenging and ketonization rate constants were measured by monitoring the decay of enols generated flash photolytically through photooxidation of the corresponding alcohols. The effects of structure on KE, kE, and kK are discussed. © 1990, American Chemical Society. All rights reserved.

引用

收藏

页码：4862 / 4868

页数：7

相关论文

共 46 条

[1] CONFORMATIONAL ANALYSIS .55. ON ENOL CONTENTS OF CYCLANONES AND ALTERNATION OF ENOL CONTENT WITH CHAIN LENGTH IN ALKANONES [J].

ALLINGER, NL ;

CHOW, LW ;

FORD, RA .

JOURNAL OF ORGANIC CHEMISTRY, 1967, 32 (06) :1994-&

[2] ENOL CONTENT AND ACIDITY OF CYCLOPENTANONE CYCLOHEXANONE AND ACETONE IN AQUEOUS SOLUTION [J].

BELL, RP ;

SMITH, PW .

JOURNAL OF THE CHEMICAL SOCIETY B-PHYSICAL ORGANIC, 1966, (03) :241-+

[3]

BEVINGTON PR, 1969, DATA REDUCTION ERROR, pCH11

[4] KINETICS OF ACID-CATALYSED EQUILIBRATIONS OF ENDO-CYCLIC AND EXO-CYCLIC OLEFINS [J].

BIGLEY, DB ;

MAY, RW .

JOURNAL OF THE CHEMICAL SOCIETY B-PHYSICAL ORGANIC, 1970, (09) :1761-&

[5] ENOL INTERMEDIATES IN PHOTOREDUCTION AND TYPE-I CLEAVAGE REACTIONS OF ALIPHATIC-ALDEHYDES AND KETONES [J].

BLANK, B ;

HENNE, A ;

LAROFF, GP ;

FISCHER, H .

PURE AND APPLIED CHEMISTRY, 1975, 41 (04) :475-494

[6] AN INTERPRETATION OF THE CHEMICAL BEHAVIOR OF 5-MEMBERED AND 6-MEMBERED RING COMPOUNDS [J].

BROWN, HC ;

BREWSTER, JH ;

SHECHTER, H .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1954, 76 (02) :467-474

[7] DIPHENYLACETALDEHYDE AND ITS ENOL - DETERMINATION OF THE KETO ENOL AND HYDRATION EQUILIBRIUM-CONSTANTS AND THE PKAS OF THE ALDEHYDE, ENOL, AND HYDRATE - COMPARISON WITH STERICALLY HINDERED SYSTEMS [J].

CHIANG, Y ;

KRESGE, AJ ;

KROGH, ET .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (08) :2600-2607

[8] PKA AND KETO-ENOL EQUILIBRIUM-CONSTANT OF ACETONE IN AQUEOUS-SOLUTION [J].

CHIANG, Y ;

KRESGE, AJ ;

TANG, YS ;

WIRZ, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (02) :460-462

[9] ACID-CATALYZED HYDROLYSIS OF VINYL ACETALS - REACTION THROUGH THE ACETAL RATHER THAN THE VINYL ETHER FUNCTIONAL-GROUP [J].

CHIANG, Y ;

CHWANG, WK ;

KRESGE, AJ ;

YIN, Y .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (18) :7185-7190

[10] PHENYLACETALDEHYDE AND ITS CIS-ENOLS AND TRANS-ENOLS AND ENOLATE IONS - DETERMINATION OF THE CIS TRANS RATIO UNDER EQUILIBRIUM AND KINETIC CONTROL [J].

CHIANG, Y ;

KRESGE, AJ ;

WALSH, PA ;

YIN, Y .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (13) :869-871

← 1 2 3 4 5 →