Journal of the American Chemical Society p. 5240 - 5247 (1989)
Update date:2022-08-17
Topics:
Nakata, Munetaka
Frei, Heinz
Reaction was induced between trans-2-butene and nitrogen dioxide by exciting trans-butene-NO2 pairs, isolated in solid Ar at red, yellow, and green wavelengths (NO22B2 <-- <*>2A1).The chemistry was monitored by FT-infrared spectroscopy, and Ar ion and cw dye lasers were used for photolysis.Products formed were 2-butene oxide + NO, the former under complete retention of stereochemistry, and an addition product that was identified by (18)O isotopic substitution as a butyl nitrite radical, reported here for the first time.Analysis of the photolysis-wavelengthdependence of the butyl nitrite radical and trans-2-butene oxide (NO) growth kinetics revealed that epoxide + NO is formed along two reaction pathways.The first gives trans-2-butene oxide + NO and butyl nitrite radical upon absorption of a single photon by trans-2-butene-NO2 pairs (one photon path).The second path is formation of trans-2-butene oxide + NO by photodissociation of trapped butyl nitrite radical by a (second) red or shorter wavelength photon (two-photon path).Two alternative transients are proposed for the one-photon path, namely a hot butyl nitrite radical and an oxirane biradical, respectively.The wavelength dependence of the product branching along the one-photon path indicates that branching occurs from a vibrationally unrelaxed transient.This suggests that the observed stereochemical integrity originates from insufficient coupling of the stretching and bending vibrations of the transient with torsion around its central C-C bond on the time scale of reaction to epoxide + NO and its stabilization as butyl nitrite radical.
View MoreNINGBO YINZHOU PRECISE COLOR CO.,LTD.
Contact:86-574-88139809 86-574-83033159
Address:Qiming Road,Yinzhou,Ningbo,China
Contact:86 21 3772 9386
Address:Rm.1803,Starry Bldg.1,1505 Meijiabang Road,Shanghai 201620 China
Contact:+(852) 301-98033
Address:Flat C, 23/F, Lucky Plaza, 315-321 Lockhart Road, Wan Chai, Hong Kong
Liao Cheng All Win Chemicals Co.,LTD
Contact:86+0635-2991582
Address:Room 402,Unit 1,No.27 building.Zhong tong shi dai haoyuan,liaocheng city,Shan dong Province.China
Contact:+86 18616952870
Address:Area
Doi:10.1016/j.physb.2006.03.024
(2007)Doi:10.1016/S0040-4039(00)85906-7
(1983)Doi:10.1002/pola.26435
(2013)Doi:10.1021/ic302827s
(2013)Doi:10.1002/aoc.3764
(2017)Doi:10.1002/aoc.3468
(2016)