Addition of Dihalocarbenes to Vinyl Fluorides. Chemical Consequences of Fluorine Substitution. Part 3

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Title:Addition of Dihalocarbenes to Vinyl Fluorides. Chemical Consequences of Fluorine Substitution. Part 3
Creators:
Haufe, Günter
Meyer, Oliver G. J.
Mück-Lichtenfeld, Christian
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 67, 10, pp. 1493-1504
Uncontrolled Keywords:Dihalogen carbenes, Cyclopropanation, Cyclopropanes, AM1 calculations, Cyclopropyl-allyl rearrangement, [2+1]-Cycloaddition, Fluoroalkenes

Abstract

1-Fluoro-1-phenylethene (<strong>1a</strong>) or 1-(4-chlorophenyl)-1-fluoroethene (<strong>1b</strong>) and 2-fluorooct-1-ene (<strong>4</strong>), on reaction with chloroform and sodium hydroxide, in a two-phase system in the presence of a phase transfer catalyst, gave the corresponding dichlorocyclopropanes in good yields. In a competition experiment, <strong>1a</strong> was shown to be slightly more reactive than styrene itself. AM1 calculations predict reasonable activation barriers for these reactions although the relative reactivity observed in the experiment is not reproduced. For the (<i>E</i>)- and (<i>Z</i>)-1-fluoro-2-phenylethenes (<strong>3</strong>), higher activation barriers were calculated, in agreement with the observation that these alkenes did not react with dichlorocarbene under these conditions. The dibromocarbene addition to <strong>1a</strong> gave 1,1-dibromo-2-fluoro-2-phenylcyclopropane (<strong>8</strong>), which on heating with silver salts in acetic acid yielded 3-acetoxy- 2-bromo-1-fluoro-1-phenylprop-1-ene (<strong>9</strong>) by a cyclopropyl-allyl rearrangement. <p>

Title:Addition of Dihalocarbenes to Vinyl Fluorides. Chemical Consequences of Fluorine Substitution. Part 3
Creators:
Haufe, Günter
Meyer, Oliver G. J.
Mück-Lichtenfeld, Christian
Uncontrolled Keywords:Dihalogen carbenes, Cyclopropanation, Cyclopropanes, AM1 calculations, Cyclopropyl-allyl rearrangement, [2+1]-Cycloaddition, Fluoroalkenes
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:67
Number:10
Page Range:pp. 1493-1504
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20021493UNSPECIFIED
ID Code:2010
Item Type:Article
Deposited On:06 Feb 2009 17:14
Last Modified:06 Feb 2009 16:14

Citation

Haufe, Günter; Meyer, Oliver G. J.; Mück-Lichtenfeld, Christian (2002) Addition of Dihalocarbenes to Vinyl Fluorides. Chemical Consequences of Fluorine Substitution. Part 3. Collection of Czechoslovak Chemical Communications, 67 (10). pp. 1493-1504. ISSN 0010-0765

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