Facile 1,3-shift of chlorine in a chlorocarbonylketene

Finnerty J., Andraos J., Yamamoto Y., Wong M.W. and Wentrup C. (1998) Facile 1,3-shift of chlorine in a chlorocarbonylketene. Journal of the American Chemical Society, 120 8: 1701-1704. doi:10.1021/ja973242g


Author Finnerty J.
Andraos J.
Yamamoto Y.
Wong M.W.
Wentrup C.
Title Facile 1,3-shift of chlorine in a chlorocarbonylketene
Journal name Journal of the American Chemical Society   Check publisher's open access policy
ISSN 0002-7863
Publication date 1998-03-04
Year available 1998
Sub-type Article (original research)
DOI 10.1021/ja973242g
Open Access Status Not yet assessed
Volume 120
Issue 8
Start page 1701
End page 1704
Total pages 4
Place of publication WASHINGTON
Publisher AMER CHEMICAL SOC
Language eng
Subject 1600 Chemistry
Abstract 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.
Keyword Cycloadditions
Rearrangement
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Scopus Import - Archived
 
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