THE MECHANISM OF ETHYLENE ELIMINATION FROM THE OXONIUM IONS CH3CH2CH=O+CH2CH3 AND (CH3)2C=O+CH2CH3

被引：10
|
作者：
BOWEN, RD [1 ]
DERRICK, PJ [1 ]
机构：
[1] UNIV WARWICK,INST MASS SPECTROMETRY,COVENTRY CV4 7AL,W MIDLANDS,ENGLAND
来源：
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 1992年 / 07期
关键词：
D O I：
10.1039/p29920001033
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The reactions of the metastable oxonium ions CH3CH2CH=O+CH2CH3 and (CH3)2C=O+CH2CH3 are reported and discussed. Various mechanisms for ethylene elimination, which is the principal dissociation route for these ions, are considered. It is shown by means of H-2-labelling experiments and analysis of collision-induced dissociation spectra that routes involving ion-neutral complexes pre-empt 'conventional' mechanisms for these processes. In contrast, the behaviour of the lower homologues CH3CH2CH=OR+ and (CH3)2C=OR+ (R = H, CH3) is consistent with the operation of 'conventional' mechanisms for ethylene expulsion. This contrast is interpreted in energetic terms. The significance of these results for the chemistry of homologous and analogous 'onium' ions containing a Z+-R function (Z = O, S, NH, NCH3; R = CnH2n+2m n greater-than-or-equal-to 2) is explained.
引用
收藏
页码：1033 / 1039
页数：7
相关论文
共 50 条
  • [21] Synthesis and characterization of oxo-rhenium(V) complexes with monodentate P(OCH3)3 and bidentate [OC(CH3)2C(CH3)2O]POC(CH3)2C(CH3)2 OP[OC(CH3)2C(CH3)2O] phosphite ligands
    Glowiak, T
    Rybak, WK
    Skarzynska, A
    POLYHEDRON, 1998, 17 (18) : 3153 - 3160
  • [22] Theoretical calculational studies on the mechanism of thermal dissociations for RN3 (R = CH3, CH3CH2, (CH3)2CH, (CH3)3C)
    Zeng, YL
    Sun, Q
    Meng, LP
    Zheng, SJ
    Wang, DX
    CHEMICAL PHYSICS LETTERS, 2004, 390 (4-6) : 362 - 369
  • [23] The Cl-initiated oxidation of CH3C(O)OCH=CH2, CH3C(O)OCH2CH=CH2, and CH2=CHC(O)O(CH2)3CH3 in the troposphere
    María B. Blanco
    Iustinian Bejan
    Ian Barnes
    Peter Wiesen
    Mariano A. Teruel
    Environmental Science and Pollution Research, 2009, 16 : 641 - 648
  • [24] Regarding bimethyl allyl-carbinol 3-3 CH3/CH3 > C=CH=CH2-CH2(OH)
    Van Aerde, M
    RECUEIL DES TRAVAUX CHIMIQUES DES PAYS-BAS ET DE LA BELGIQUE, 1909, 28 : 171 - 179
  • [25] The Cl-initiated oxidation of CH3C(O)OCH=CH2, CH3C(O)OCH2CH=CH2, and CH2=CHC(O)O(CH2)3CH3 in the troposphere
    Blanco, Maria B.
    Bejan, Iustinian
    Barnes, Ian
    Wiesen, Peter
    Teruel, Mariano A.
    ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH, 2009, 16 (06) : 641 - 648
  • [26] RADICAL-INITIATED HYDROSILYLATION-CYCLIZATION REACTIONS OF BIS(VINYLDIMETHYLDIMETHYLSILYL) COMPOUNDS, CH2=CH(CH3)(2)SIXSI(CH3)(2)CH=CH2 (X=O, CH2, NH, NCH3, NSI(CH3)(3)
    SEYFERTH, D
    FRIEDRICH, H
    KRSKA, SW
    ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES, 1994, 49 (12): : 1818 - 1826
  • [27] Concerning 1-ethyl-2-methyl-valerianic acid CH3-CH2-CH(CH3)-CH(CH2-CH3)-COOH
    Katznelson, M
    Kondakova, M
    COMPTES RENDUS DE L ACADEMIE DES SCIENCES DE L URSS, 1934, 3 : 21 - 25
  • [28] RATE CONSTANTS FOR THE GAS-PHASE REACTIONS OF OH RADICALS AND CL ATOMS WITH CH3CH2NO2, CH3CH2CH2NO2, CH3CH2CH2CH2NO2, AND CH3CH2CH2CH2CH2NO2
    NIELSEN, OJ
    SIDEBOTTOM, HW
    OFARRELL, DJ
    DONLON, M
    TREACY, J
    CHEMICAL PHYSICS LETTERS, 1989, 156 (04) : 312 - 318
  • [29] Thermal reaction of (CH3)(2)C=C(CH3)(2) in the presence of di-tert-butyl peroxide; Reactions of the radicals center dot CH3,(CH3)(3)C center dot C(CH3)(2) and (CH3)(2)C=C(CH3)center dot CH2
    Kortvelyesi, T
    Seres, L
    JOURNAL DE CHIMIE PHYSIQUE ET DE PHYSICO-CHIMIE BIOLOGIQUE, 1996, 93 (02) : 253 - 273
  • [30] REACTIONS OF CH3, CH3O, AND CH3O2 RADICALS WITH O3
    SIMONAITIS, R
    HEICKLEN, J
    JOURNAL OF PHYSICAL CHEMISTRY, 1975, 79 (04): : 298 - 302
12345