Experimental and computational study of the intramolecular reactivity of free tert-butylphenylmethylene.: Modification of the chemistry of tert-butylmethylene by the introduction of a phenyl group

被引:9
作者
Armstrong, BM [1 ]
McKee, ML [1 ]
Shevlin, PB [1 ]
机构
[1] Auburn Univ, Dept Chem, Auburn, AL 36849 USA
关键词
D O I
10.1021/jo981153w
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The chemistry of tert-butylphenylmethylene, 2, has been investigated experimentally and computationally. Free carbene 2 was generated by the thermal rearrangement of p-tert-butylphenylmethylene and observed to rearrange by C-H insertion to give 1,1-dimethyl-2-phenylcyclopropane, 3, and by C-C insertion to yield 2-methyl-3-phenyl-2-butene, 4. An examination of the 3:4 ratio led to the conclusion that C-H insertion is favored over C-C insertion by 1.6 +/- 0.1 kcal/mol in good agreement with a calculated (PMP2/6-31G(d)//MP2/6-31G(d)+ZPC/6-31(d)) value of 2.0 kcal/mol. The S-T gap in 2 is estimated to be 5-6 kcal/mol.
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收藏
页码:7408 / 7412
页数:5
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