EDGEWISE PROTONATED CYCLOPROPANE IN GAS PHASE-COUPLING OF UNIMOLECULAR [1.1]-H2-ELIMINATION FROM C3H7+ AND RING-OPENING OF CYCLOPROPYL CATION

被引:36
作者
SCHWARZ, H [1 ]
FRANKE, W [1 ]
CHANDRASEKHAR, J [1 ]
SCHLEYER, PV [1 ]
机构
[1] UNIV ERLANGEN NURNBERG, INST ORGAN CHEM, D-8520 ERLANGEN, GERMANY
关键词
D O I
10.1016/0040-4020(79)85056-5
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Based on energetic data (activation energy), kinetic isotope effects and MINDO/3 calculations it is suggested that unimolecular loss of H2 from C3H7+ proceeds via a transition state (10) involving synchronous loss of a hydrogen molecule (symmetry allowed [1.1]-elimination) and ring opening of the cyclopropyl to the allyl cation. Alternative mechanisms are discussed. © 1979.
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收藏
页码:1969 / 1976
页数:8
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共 77 条
[51]   FREE RADICALS BY MASS SPECTROMETRY .42. IONIZATION POTENTIALS AND IONIC HEATS OF FORMATION FOR C1-C4 ALKYL RADICALS [J].
LOSSING, FP ;
SEMELUK, GP .
CANADIAN JOURNAL OF CHEMISTRY, 1970, 48 (06) :955-&
[52]   ION-CYCLOTRON RESONANCE SPECTROSCOPY IN STRUCTURE DETERMINATION .2. PROPYL IONS [J].
MCADOO, DJ ;
MCLAFFER.FW ;
BENTE, PF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (06) :2027-&
[53]   STRUCTURE OF TRANSITION-STATES - ARE THEY SYMMETRIC [J].
MCIVER, JW .
ACCOUNTS OF CHEMICAL RESEARCH, 1974, 7 (03) :72-77
[54]   ENERGETICS OF LOSS OF H-2 FROM [C3H7]+ [J].
MEAD, PT ;
TRAEGER, JC ;
CHRISTIE, JR ;
DERRICK, PJ .
ORGANIC MASS SPECTROMETRY, 1978, 13 (07) :386-388
[55]   AB-INITIO SCF AND CI STUDY OF ELECTROCYCLIC TRANSFORMATIONS OF CYCLOPROPYL AND ALLYL SYSTEMS [J].
MERLET, P ;
PEYERIMH.SD ;
BUENKER, RJ ;
SHIH, S .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1974, 96 (04) :959-969
[56]   SYMMETRIES OF ACTIVATED COMPLEXES [J].
MURRELL, JN ;
LAIDLER, KJ .
TRANSACTIONS OF THE FARADAY SOCIETY, 1968, 64 (542P) :371-&
[57]   SIGMA-BRIDGED 2-NORBORNYL CATION AND ITS SIGNIFICANCE TO CHEMISTRY [J].
OLAH, GA .
ACCOUNTS OF CHEMICAL RESEARCH, 1976, 9 (02) :41-52
[58]   11-METHYL-11-TRICYCLO[4.4.1.01,6]UNDECYL CATION - 1ST LONG-LIVED, DISTINCT CYCLOPROPYL CATION SHOWING SIGNIFICANT 2-PI-HOMOAROMATIC NATURE [J].
OLAH, GA ;
LIANG, G ;
LEDLIE, DB ;
COSTOPOULOS, MG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (12) :4196-4198
[59]   METASTABLE IONS IN MASS SPECTRA OF PROPANE AND DEUTERATED PROPANES [J].
OTTINGER, C .
JOURNAL OF CHEMICAL PHYSICS, 1967, 47 (04) :1452-&
[60]   CALCULATION OF TRANSITION-STATES [J].
POPPINGER, D .
CHEMICAL PHYSICS LETTERS, 1975, 35 (04) :550-554