Fragmentation of cyclobutoxychlorocarbene: the cyclopropylcarbinyl/cyclobutyl cations revisited

Authors
Moss, RA Zheng, FM Johnson, LA Sauers, RR
Citation
Ra. Moss et al., Fragmentation of cyclobutoxychlorocarbene: the cyclopropylcarbinyl/cyclobutyl cations revisited, J PHYS ORG, 14(7), 2001, pp. 400-406
Citations number
31
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
ISSN journal
08943230 → ACNP
Volume
14
Issue
7
Year of publication
2001
Pages
400 - 406
Database
ISI
SICI code
0894-3230(200107)14:7<400:FOCTC>2.0.ZU;2-2
Abstract
Fragmentations of cyclobutoxychlorocarbene (13, k(frag) = 7.1 x 10(5) s(-1) ) and cyclopropylmethoxychlorocarbene (14, k(frag) = 7.6 x 10(5) s(-1)) in MeCN proceed to tight and distinct [R+ OC Cl-] ion pairs, which collapse to different distributions of cyclopropylcarbinyl, cyclobutyl and allylcarbin yl chlorides. B3LYP/6-31G* calculations support these conclusions, affordin g computed fragmentation activation energies of 6.4 (13) and 3.0 (14) kcal mol(-1) Copyright (C) 2001 John Wiley & Sons, Ltd.