SOLVENT EFFECT ON THE DECARBONYLATION OF ACYL RADICALS STUDIED BY LASER FLASH-PHOTOLYSIS

被引：82

作者：

TSENTALOVICH, YP

FISCHER, H

机构：

[1] Physikalisch-Chemisches Institut, Universität Zürich, CH-8057

来源：

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 1994年 / 04期

关键词：

D O I：

10.1039/p29940000729

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Absorption spectra of transient radicals generated from dibenzyl and di-tert-butyl ketones and rate constants for their fragmentation and termination reactions were obtained by laser flash photolysis in various solvents. Whereas the pivaloyl radical absorbs only for lambda less than or equal to 240 nm, the first absorption band of phenylacetyl is red shifted which is ascribed to a phenyl-carbonyl conjugation. The rate constant for the decarbonylation of the acyl radicals decreases markedly with increasing solvent polarity. This is explained by the dipole moment which decreases during the scission process.

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页码：729 / 733

页数：5

相关论文

共 47 条

[1] ACETYL RADICAL STUDIED BY FLASH-PHOTOLYSIS AND KINETIC SPECTROSCOPY [J].

ADACHI, H ;

BASCO, N ;

JAMES, DGL .

CHEMICAL PHYSICS LETTERS, 1978, 59 (03) :502-505

[2] THE ACETYL RADICALS CH3CO. AND CD3CO. STUDIED BY FLASH-PHOTOLYSIS AND KINETIC SPECTROSCOPY [J].

ADACHI, H ;

BASCO, N ;

JAMES, DGL .

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1981, 13 (12) :1251-1276

[3]

ARBOUR C, 1984, CHEM PHYS LETT, V159, P520

[4] SPECTRA AND REACTIONS OF ACETYL AND ACETYLPEROXY RADICALS [J].

BASCO, N ;

PARMAR, SS .

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1985, 17 (08) :891-900

[5]

BLANK B, 1971, 23 INT C PUR APL CHE, V4, P1

[6] A NOVEL RADICAL-TRIPLET PAIR MECHANISM FOR CHEMICALLY-INDUCED ELECTRON POLARIZATION (CIDEP) OF FREE-RADICALS IN SOLUTION [J].

BLATTLER, C ;

JENT, F ;

PAUL, H .

CHEMICAL PHYSICS LETTERS, 1990, 166 (04) :375-380

[7] CIDEP DURING THE PHOTOLYSIS OF DI-TERT.BUTYL KETONE [J].

CARMICHAEL, I ;

PAUL, H .

CHEMICAL PHYSICS LETTERS, 1979, 67 (2-3) :519-523

[8] ACTINOMETRY-FREE DETERMINATION OF OPTICAL-ABSORPTION COEFFICIENTS AND 2ND-ORDER RATE CONSTANTS OF TRANSIENT RADICALS [J].

CHEN, T ;

PAUL, H .

JOURNAL OF PHYSICAL CHEMISTRY, 1985, 89 (13) :2765-2767

[9] SELF-TERMINATION AND ELECTRONIC-SPECTRA OF SUBSTITUTED BENZYL RADICALS IN SOLUTION [J].

CLARIDGE, RFC ;

FISCHER, H .

JOURNAL OF PHYSICAL CHEMISTRY, 1983, 87 (11) :1960-1967

[10] PHOTOREACTIVITY OF N,PI! EXCITED STATES OF ALKYL KETONES [J].

DALTON, JC ;

TURRO, NJ .

ANNUAL REVIEW OF PHYSICAL CHEMISTRY, 1970, 21 :499-&

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