Preparation, 13C NMR/DFT/IGLO study of benzylic mono- and dications, and attempted preparation of a trication

被引:26
|
作者
Olah, GA
Shamma, T
Burrichter, A
Rasul, G
Prakash, GKS
机构
[1] Univ So Calif, Donald P & Katherine B Loker Hydrocarbon Res, Los Angeles, CA 90089 USA
[2] Univ So Calif, Dept Chem, Los Angeles, CA 90089 USA
关键词
D O I
10.1021/ja971287b
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Substituted benzylic mono- and dications were prepared and investigated by H-1 and C-13 NMR spectroscopy and DFT/IGLO calculations. Combined experimental and theoretical study suggest that the structure la is the major resonance contributor to the 2,4,6-trimethylbenzyl cation 1. Similar results were also found for the 2,4,6-dimethyl-4-tert-butylbenzyl 2 and 2,3,4,5,6-pentamethyIbenzyl cation 3. It was found that the structure 4a is the predominant resonance contributor to the overall structure of 2,6-dimethylmesityldiyl dication 4 wherein the dienyl and allylic cation units are insulated from each other. Similar studies indicate structure 5a as the predominant canonical structure for 5-methoxy-2,6-dimethyl-m-xylyldiyl dication 5 wherein the dienyl and oxoallylic cation units are insulated from each ether. Attempts to generate the 2,3,5,6-tetramethyl-1,4-dimethylbenzenediyl dication 8 was, however, not successful as were the generation of the 2,4,6-trimethylmesityltriyl trication 10 by ionization of 2,4,6-bis(chloromethyl)mesitylene. The resulting ion was characterized as a chloromethyl substituted dication 9.
引用
收藏
页码:12923 / 12928
页数:6
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