Title page for ETD etd-61598-21627

Type of Document

Dissertation

Author

Sadeghipour, Mitra Jr.

Author's Email Address

Mitra@vt.edu

URN

etd-61598-21627

Title

Hydrocarbon Functionalization via a New Free Radical-Based Condensation Reaction

Degree

Ph.D.

Department

Chemistry

Advisory Committee

Advisor Name	Title
D. G. I. Kingston
H. M. Bell
J. M. Tanko
K. J. Brewer
N. Castagnoli, Jr.
J. M. Tanko	chair

Keywords

Addition
Allylation
Allyl bromide
Alkyl aromatic
Bromine
Condensation
Fragmentation
Free Radical
Hydrocarbon
2-Propanol
Reaction Mechanism
Synthesis

Date of Defense

1998-07-07

Availability

unrestricted

Abstract

A new free radical chain process for the allylation of
hydrocarbons and some other substrates utilizing
substituted allyl bromides (R-H + C=C-C-Br -> R-C-C=C + HBr)
has been developed. Good to excellent yields were observed
in all cases. Kinetic chain measurements and competition
experiments were performed in order to elucidate the
mechanism of the reaction. Overall, the results are
consistent with a free radical chain process with bromine
atom as the chain carrier. Substitution effects on the
reactivity of the allyl bromides (CH2=C(Z)CH2Br) and their
influence on the overall reaction rate were studied by
conducting several competition experiments. The relative
rate constants for addition of benzyl radical to
CH2=C(Z)CH2Br are: Z=CN(180), COOEt(110), Ph(65), H(1.0).
The trend of electronegativity/reactivity of these
reactions was very similar to that reported for addition
of benzyl radical to substituted alkenes. Other than alkyl
aromatics (PhCH3, PhCH(CH3)2), other substrates (i.e.,
2- propanol, phenyl cyclopropane) were also tested for
this allylation reaction. The magnitude and scope of
these reactions, and their synthetic utility is discussed.

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