Dichlorocarbene



 Dichlorocarbene is a cyclopropanone in a gem halide hydrolysis. The preparation of dichlorocarbene from chloroform and its utility in synthesis was discovered by William von Eggers Doering in 1954 [2] based on functionalizion of cyclohexene. A Geuther in 1862 was the first to propose dichlorocarbene.

Related reactions

The Doering-LaFlamme carbon chain extension [3]describes the conversion of alkenes to allenes (a chain extension) with Reimer-Tiemann reaction. Closely related is the more reactive dibromocarbene CBr2.

Synthetic methods

Other dichlorocarbene precursors are methanol [4] and phenyl(trichloromethyl)mercury by thermal decomposition [5] . Dichlorodiazirine is an experimental dichlorocarbene precursor [6]. It is stable in the dark at photolysis.

[7]

The reaction mechanism for the formation of dichloroaziridine is depicted below:

Dichlorocarbene can also be obtained by reaction of base.

References

  1. ^ Organic Syntheses, Coll. Vol. 5, p.874 (1973); Vol. 41, p.76 (1961).Online Article
  2. ^ The Addition of Dichlorocarbene to Olefins W. von E. Doering and A. Kentaro Hoffmann J. Am. Chem. Soc.; 1954; 76(23) pp 6162 - 6165; doi:10.1021/ja01652a087
  3. ^ A two-step of synthesis of allenes from olefins Tetrahedron, Volume 2, Issues 1-2, 1958, Pages 75-79 W. von E. Doering and P. M. LaFlamme doi:10.1016/0040-4020(58)88025-4
  4. ^ Organic Syntheses, , Coll. Vol. 6, p.731 (1988); Vol. 54, p.11 (1974).Online Article
  5. ^ Organic Syntheses, , Coll. Vol. 5, p.969 (1973); Vol. 46, p.98 (1966).Online Article
  6. ^ Dichlorodiazirine: A Nitrogenous Precursor for Dichlorocarbene Gaosheng Chu, Robert A. Moss, and Ronald R. Sauers J. Am. Chem. Soc., 127 (41), 14206 -14207, 2005 DOI Abstract
  7. ^ a) Starting from ionic liquid
  8. ^ A Facile Procedure for the Generation of Dichlorocarbene from the Reaction of Carbon Tetrachloride and Magnesium using Ultrasonic Irradiation Haixia Lin, Mingfa Yang, Peigang Huang and Weiguo Cao Molecules 2003, 8, 608-613 Online Article
 
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