42348-92-5Relevant academic research and scientific papers
The Role of Single-Electron Transfer in SN2-Type Substitution Reactions of Anions with Alkyl Halides
Bordwell, F.G.,Harrelson, John A.
, p. 4893 - 4898 (2007/10/02)
Rate constants (kobsd) for reactions of electrophiles with: (a) various carbanions, including 9-substituted fluorenide ions (9-GFl-), 9-substituted xanthenide ions, α-cyano carbanions, anb β-diketo enolate ions, (b) phenothiazinide (PTZ-) and carbazole (Cb-) nitranions, (c) 4-substituted phenoxide ions, and (d) thiphenoxide ions, have been campared with rate constants for single-electron transfer (kSET) calculated using a Marcus-type equation.For both 9-GFl- carbanion and 2-GPTZ- nitranion families reacting with SET acceptors, such as 1,1-dinitrocyclohexane, the kobsd/kSET ratio is near unity.For 9-GFl- carbanions reacting with Ph2CHCl the kobsd/kSET ratios range from 2 to 105, those for 2-PTZ- nitranions from 370 to 1.3*104, and those for Cb- nitranions from 108 to 1010.For reactions of 4-GC6H4O- oxanions with Ph2CHCl the ratios range from 103 for G = Me2N to 1013 for G = CN; for PhS- ion reacting with n-BuBr the ratio is 1017.The significance of these results with respect to the role of an outer sphere SET mechanism in substitution reactions of anions with alkyl halides is discussed.
REACTIVITY OF CARBANIONS. XIV. KINETICS OF THE ALKYLATION OF CARBANIONS OF THE FLUORENYL TYPE AND THEIR ION PAIRS BY BUTYL BROMIDE
Solov'yanov, A. A.,Beletskaya, I. P.,Reutov, O. A.
, p. 1592 - 1603 (2007/10/02)
The reaction rate constants were determined for the free carbanions and their ion pairs in the reaction of the lithium and cesium salts of 9-cyano-, 9-methoxycarbonyl-, 9-phenyl-, 9-triphenylmethyl-, 9-trimethylsilyl-, 9-benzyl-, 9-methyl-, 9-tert-butyl-, 2-cyano-, 2-bromo-, 2-methyl-, and 2-dimethylaminofluorenes, fluorene, 1-azafluorene, 3-methyl-2-azafluorene, 1,2-benzofluorene, and fluoradene with butyl bromide in dimethoxyethane at 25 gradC.The obtained data can be used as the basis for the creation of a scale of relative nucleophilicity in the carbanions.
