Hydration of carbonyl compounds, an analysis in terms of multidimensional marcus theory

被引：120

作者：

Guthrie, JP ^{[1
]}

机构：

[1] Univ Western Ontario, Dept Chem, London, ON N6A 5B7, Canada

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2000年 / 122卷 / 23期

关键词：

D O I：

10.1021/ja992992i

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Rate constants for base-catalyzed, uncatalyzed, and acid-catalyzed additions of water to 50 compounds (aldehydes, ketones, esters, thioesters, and amides) have been calculated using Multidimensional Marcus Theory. For all of these reactions except hydroxide addition to reactive aldehydes a single average value of the intrinsic barrier (8.51 kcal/mol) can be used to give calculated values within 1 kcal/mol (root-mean-square error) of the observed values. For the addition of hydroxide to reactive aldehydes it is necessary to use an intrinsic barrier linearly related to the equilibrium constant for hydroxide addition. The work term in Marcus Theory is approximated by a detailed model of the solvation and statistical cost of bringing reactants together.

引用

页码：5529 / 5538

页数：10

共 63 条

[1]

ALBERY WJ, 1967, PROGR REACTION KINET, V4, P353

[2] KINETICS OF REVERSIBLE HYDRATION OF 1,3-DICHLOROACETONE IN DIOXAN AND ACETONITRILE SOLUTION [J].

BELL, RP ;

MILLINGT.JP ;

PINK, JM .

PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1968, 303 (1472) :1-&

[3] REACTION ORDERS AND ISOTOPE EFFECTS IN REVERSIBLE ADDITION OF WATER TO 1,3-DICHLOROACETONE IN AQUEOUS DIOXAN [J].

BELL, RP ;

CRITCHLO.JE .

PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1971, 325 (1560) :35-&

[4] THERMODYNAMIC AND ACTIVATION PARAMETERS IN REVERSIBLE HYDRATION OF 1,3-DICHLOROACETONE IN DIOXAN [J].

BELL, RP ;

SORENSEN, PE .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1972, (12) :1740-&

[5] KINETICS OF ADDITION OF HYDROXIDE IONS TO SUBSTITUTED BENZALDEHYDES [J].

BELL, RP ;

SORENSEN, PE .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1976, (13) :1594-1598

[6] CONCURRENT ALKALINE HYDROLYSIS AND ISOTOPIC OXYGEN EXCHANGE OF A SERIES OF P-SUBSTITUTED ACETANILIDES [J].

BENDER, ML ;

THOMAS, RJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1961, 83 (20) :4183-&

[7] THE EFFECT OF STRUCTURE ON KINETICS AND MECHANISM OF THE ALKALINE HYDROLYSIS OF ANILIDES [J].

BIECHLER, SS ;

TAFT, RW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1957, 79 (18) :4927-4935

[8] SOLVENT EFFECTS ON OPTICAL-ABSORPTION SPECTRA - THE 1A1-]1A2 TRANSITION OF FORMALDEHYDE IN WATER [J].

BLAIR, JT ;

KROGHJESPERSEN, K ;

LEVY, RM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (18) :6948-6956

[9] REACTIONS OF CARBONYL-COMPOUNDS IN BASIC SOLUTIONS .14. THE ALKALINE-HYDROLYSIS OF SUBSTITUTED N-METHYLFORMANILIDES, N-METHYLACETANILIDES, 1-PHENYLAZETIDIN-2-ONES, 1-PHENYL-2-PYRROLIDONES, AND 1-PHENYL-2-PIPERIDONES [J].

BOWDEN, K ;

BROMLEY, K .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1990, (12) :2103-2109

[10] THE USE OF VARIABLE INTRINSIC BARRIERS FOR THE PREDICTION OF BRONSTED SLOPES FOR THE DEPROTONATION OF CARBON ACIDS [J].

BUNTING, JW ;

STEFANIDIS, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (15) :5834-5839

← 1 2 3 4 5 6 7 →