Hg(3P1) photosensitized reactions of cyclopropane
Under static conditions the major reaction product is a polymer. Polymerization is inhibited by free radical scavengers such as NO, O 2 , butadiene-1,3, etc. with a simultaneous large increase in propylene yields. The NO inhibited reaction affords propenaldoxime and acrylonitrile as principal produc...
Saved in:
Published in | Canadian journal of chemistry Vol. 46; no. 8; pp. 1317 - 1323 |
---|---|
Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
Ottawa, Canada
NRC Research Press
15.04.1968
|
Online Access | Get full text |
Cover
Loading…
Summary: | Under static conditions the major reaction product is a polymer. Polymerization is inhibited by free radical scavengers such as NO, O
2
, butadiene-1,3, etc. with a simultaneous large increase in propylene yields. The NO inhibited reaction affords propenaldoxime and acrylonitrile as principal products, indicating the presence of allyl radicals, and N
2
O which is indicative of H atoms. Polymerization can also be suppressed by rapid flow: it is entirely a secondary process. The products of the flow experiments are: propylene, biallyl, allylcyclopropane, 4-methyl pentene-1, hexene-1, 2,3-dimethyl butane, C
5
and C
9
hydrocarbons, H
2
, CH
4
, C
3
H
8
, and traces of bicyclopropyl. Most of the products can be accounted for by the self-scavenging of H atoms by propylene and the ensuing reactions of isopropyl and allyl radicals. The major primary step is the formation of an electronically excited cyclopropane, possibly the ground state triplet of trimethylene with a large excess of vibrational energy. The primary decomposition is retarded by pressure. Φ(decomp.) > 0.38, at 20 Torr, but is less than unity. |
---|---|
ISSN: | 0008-4042 1480-3291 |
DOI: | 10.1139/v68-218 |