Facile 1,3-shift of chlorine in a chlorocarbonylketene

被引：45

作者：

Finnerty, J ^{[1
]}

Andraos, J ^{[1
]}

Yamamoto, Y ^{[1
]}

Wong, MW ^{[1
]}

Wentrup, C ^{[1
]}

机构：

[1] Univ Queensland, Dept Chem, Brisbane, Qld 4072, Australia

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1998年 / 120卷 / 08期

关键词：

D O I：

10.1021/ja973242g

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Chlorocarbonyl(phenyl)ketene (2) undergoes a degenerate 1,3-shift of chlorine, as determined by C-13 NMR spectroscopy. The two carbonyl signals (183 and 157 ppm) coalesce at -30 degrees C, and from this as well as line-shape analysis, an activation barrier for the 1,3-Cl shift interconverting 2a and 2a' of Delta G double dagger = 41.8 +/- 4 kJ mol(-1) (10.0 +/- 1 kcal mol(-1)) is calculated. These data are in excellent agreement with calculated (G2(MP2,SVP) and B3-LYP/6311+G(3df,2p)//6-31G* + ZPVE) 1,3-Cl shift and rotational barriers. Analogous 1,3-halogen shifts in acyl isocyanates are predicted.

引用

页码：1701 / 1704

页数：4

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