Generation of Methylene by the Liquid Phase Oxidation of Isobutene with Nitrous Oxide
Full article
| Common |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
Tetrahedron
ISSN: 0040-4020
, E-ISSN: 1464-5416
|
| Output data |
Year: 2018,
Volume: 74,
Number: 27,
Pages: 3589-3595
Pages count
: 7
DOI:
10.1016/j.tet.2018.05.022
|
| Tags |
Olefins; Nitrous oxide; 1,3-Dipolar cycloaddition; Oxidation; Methylene |
| Authors |
Semikolenov Sergey
1
,
Ivanov Dmitry
1
,
Babushkin Dmitry
1
,
Malykhin Sergey
1
,
Kharitonov Alexander
1
,
Dubkov Konstantin
1
|
| Affiliations |
| 1 |
Boreskov Institute of Catalysis, Pr. Lavrentieva 5, 630090, Novosibirsk, Russia
|
|
Funding (1)
|
1
|
Federal Agency for Scientific Organizations
|
0303-2016-0006 (V.44.1.6)
|
The application of nitrous oxide as an alternative oxidant provides new opportunities for selective oxidation of olefins. Here, we studied for the first time the thermal oxidation of isobutene with N2O in the liquid phase. The study revealed that the oxidation proceeds via 1,3-dipolar cycloaddition of N2O to the Cdouble bond; length as m-dashC bond by two routes forming unstable 4,5-dihydro-[1,2,3]-oxadiazole intermediates. The main route (the contribution of 91%) includes the addition of the N2O oxygen to the second carbon atom in olefin. In this case, the oxadiazole decomposes with the Csingle bondC bond cleavage yielding acetone, methylene (:CH2), and N2. The methylene then readily reacts with isobutene and benzene (solvent). The minor route involves the addition of the N2O oxygen to the first carbon atom and the oxadiazole decomposition with a hydrogen shift leading to isobutanal and N2.
The main distinctive feature of the studied reaction is the formation of methylene in high yield.