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 PhD
Department Chemistry
Advisory Committee
Advisor Name Title
Bell, Harold M.
Brewer, Karen J.
Castagnoli, Neal Jr.
Kingston, David G. I.
Tanko, James M.
Tanko, James M. Committee Chair
  • 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
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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