Theoretical study of factors controlling rates of cyclization of radical intermediates from diallylamine and diallylammonium monomers in radical polymerizations

N. S. Tüzün, V. Aviyente*, K. N. Houk

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

22 Citations (Scopus)

Abstract

The radical cyclization reactions of models for the growing radical chains formed from N,N-diallylamine (1), N-methyl-N,N-diallylamine (2), N,N-diallylammonium (3), N-methyl-N,N-diallylammonium (4) and N,N-dimethyl-N,N-diallylammonium (5) have been investigated computationally by DFT theory, using the B3LYP functional. Models formed by hydrogen atom addition to dienes 1-5 undergo five-membered ring cyclization reactions with activation energies predicted to be 7.2, 5.0, 8.6, 6.4, and 6.2 kcal/mol, respectively. Methyl substitution on nitrogen decreases the barrier to cyclization. One methyl has a larger effect on the cyclization rate than the second methyl. This rate enhancement is attributed to a decrease in gauche interactions in the transition state as compared to the initial structure and to different destabilizing effects when an H is replaced by a methyl group. These predicted rate effects are in agreement with the experimental data on polymerization efficiencies.

Original languageEnglish
Pages (from-to)5068-5075
Number of pages8
JournalJournal of Organic Chemistry
Volume67
Issue number15
DOIs
Publication statusPublished - 26 Jul 2002
Externally publishedYes

Fingerprint

Dive into the research topics of 'Theoretical study of factors controlling rates of cyclization of radical intermediates from diallylamine and diallylammonium monomers in radical polymerizations'. Together they form a unique fingerprint.

Cite this