S(N)2 REACTION VERSUS ELECTRON-TRANSFER IN THE OXYGEN-TRANSFER BY DIMETHYLDIOXIRANE TO NITROGEN HETEROARENES

被引：20

作者：

ADAM, W

GOLSCH, D

机构：

[1] Institut Für Organische Chemie, Universität Würzburg, D-W-8700, Am Hubland

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 1993年 / 32卷 / 05期

关键词：

D O I：

10.1002/anie.199307371

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The rates of the N oxidation of aromatic amines with dimethyldioxirane (DMD) have been compared with those of the methylation of the same compounds with methyl iodide, and an excellent correlation (r = 0.977) for the log k values was obtained. The correlation with the ionization potentials was significantly worse. Thus, the N oxidation with DMD proceeds through an S(N)2 rather than an electron transfer (ET) mechanism [Eq. (a)]. [GRAPHICS]

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页码：737 / 739

页数：3

相关论文

共 31 条

[1] SPECTRAL AND CHEMICAL-PROPERTIES OF DIMETHYLDIOXIRANE AS DETERMINED BY EXPERIMENT AND ABINITIO CALCULATIONS [J].

ADAM, W ;

CHAN, YY ;

CREMER, D ;

GAUSS, J ;

SCHEUTZOW, D ;

SCHINDLER, M .

JOURNAL OF ORGANIC CHEMISTRY, 1987, 52 (13) :2800-2803

[2] ONE-ELECTRON REDUCTION OF METHYL(TRIFLUOROMETHYL)DIOXIRANE BY IODIDE-ION - EVIDENCE FOR AN ELECTRON-TRANSFER CHAIN-REACTION MEDIATED BY THE SUPEROXIDE ION [J].

ADAM, W ;

ASENSIO, G ;

CURCI, R ;

GONZALEZNUNEZ, ME ;

MELLO, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (22) :8345-8349

[3] DIOXIRANE EPOXIDATION OF ALPHA,BETA-UNSATURATED KETONES [J].

ADAM, W ;

HADJIARAPOGLOU, L ;

SMERZ, A .

CHEMISCHE BERICHTE, 1991, 124 (01) :227-232

[4] DIOXIRANES - A NEW CLASS OF POWERFUL OXIDANTS [J].

ADAM, W ;

CURCI, R ;

EDWARDS, JO .

ACCOUNTS OF CHEMICAL RESEARCH, 1989, 22 (06) :205-211

[5] A CONVENIENT PREPARATION OF ACETONE SOLUTIONS OF DIMETHYLDIOXIRANE [J].

ADAM, W ;

BIALAS, J ;

HADJIARAPOGLOU, L .

CHEMISCHE BERICHTE, 1991, 124 (10) :2377-2377

[6] PHOTOLYSIS OF DIOXIRANES IN THE PRESENCE OF A NITROXIDE RADICAL SCAVENGER - THE INTERMEDIACY OF RADICAL-ANION AND DIYL SPECIES IN THE PRODUCTION AND TRAPPING OF METHYL AND TRIFLUOROMETHYL RADICALS [J].

ADAM, W ;

BOTTLE, SE ;

MELLO, R .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1991, (11) :771-773

[7]

Adam W., 1992, ORGANIC PEROXIDES, P221

[8]

ADAM W, IN PRESS TOP CURR CH

[9] IONIZATION CONSTANTS OF HETEROCYLIC SUBSTANCES .2. HYDROXY-DERIVATIVES OF NITROGENOUS SIX-MEMBERED RING-COMPOUNDS [J].

ALBERT, A ;

PHILLIPS, JN .

JOURNAL OF THE CHEMICAL SOCIETY, 1956, (JUN) :1294-1304

[10] THERMODYNAMIC ANALYSIS OF SUBSTITUENT EFFECTS ON PROTON DISSOCIATION EQUILIBRIA OF SUBSTITUTED PYRIDINES [J].

BELLOBONO, IR ;

MONETTI, MA .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1973, (06) :790-793

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