ABINITIO STUDY OF THE CONROTATORY RING-OPENING OF PHOSPHACYCLOBUTENES AND AZACYCLOBUTENES .1. MONOPHOSPHACYCLOBUTENES AND MONOAZACYCLOBUTENES

被引:33
作者
BACHRACH, SM
LIU, MX
机构
[1] Department of Chemistry, Northern Illinois University, DeKalb
关键词
D O I
10.1021/jo00027a039
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The allowed conrotatory ring-opening reactions of 1,2-dihydrophosphete (1), 2,3-dihydrophosphete (2), 1,2-dihydroazete (3), and 3,4-dihydroazete (4) were examined at the HF/6-31G* and MP2/6-31G* levels. Reasonable activation barriers were obtained only with the inclusion of electron correlation; however, geometry optimization at MP2 did not significantly change the geometry from those obtained at the HF level. The opening of the dihydrophosphetes is thermoneutral or slightly endothermic, while the opening of the dihydroazetes is exothermic. The calculated activation barriers for the opening of 2 and 4 are 40.76 and 37.08 kcal mol-1, respectively. The opening of 1 and 3 can occur via two diastereomeric pathways. Inward rotation of the heteroatom lone pair is favored for both systems; the lower barrier is 24.59 kcal mol-1 for 1 and 29.76 kcal mol-1 for 2. The differences in these reactions are compared and explained in terms of ring strain and orbital interactions.
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页码:209 / 215
页数:7
相关论文
共 49 条
[1]   FTIR DETECTION OF UNSTABLE MOLECULES - INFRARED-SPECTRUM OF 1-AZETINE [J].
AMATATSU, Y ;
HAMADA, Y ;
TSUBOI, M .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1987, 123 (02) :267-275
[2]   STRUCTURE AND INVERSION BARRIER OF PHOSPHIRENE AND 1,2-DIHYDROPHOSPHETE - AN ABINITIO STUDY [J].
BACHRACH, SM .
JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (06) :2205-2209
[3]   ROTATIONAL ENERGY SURFACES OF AZA-1,3-BUTADIENES AND PHOSPHA-1,3-BUTADIENES - A THEORETICAL-STUDY [J].
BACHRACH, SM ;
LIU, MX .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (21) :7929-7937
[4]   STRUCTURE, TOPOLOGICAL ELECTRON-DENSITY ANALYSIS AND AROMATICITY OF 4-HETEROSUBSTITUTED METHYLENECYCLOPROPENES - CH2 = CCH = CH, NH = CCH = CH, O = CCH = CH, SIH2 = CCH = CH, PH = CCH = CH AND S = CCH = CH [J].
BACHRACH, SM ;
LIU, MX .
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 1991, 4 (04) :242-250
[5]   THEORETICAL-STUDIES OF PHOSPHIRANE AND PHOSPHETANE [J].
BACHRACH, SM .
JOURNAL OF PHYSICAL CHEMISTRY, 1989, 93 (23) :7780-7784
[7]  
BACHRACH SM, IN PRESS THEOCHEM
[8]  
BACHRACH SM, 1990, PHOSPHORUS SULFUR, V53, P7
[9]  
Bader R. F. W., 1990, ATOMS MOL QUANTUM TH, V22
[10]   QUANTUM TOPOLOGY OF MOLECULAR CHARGE-DISTRIBUTIONS .1 [J].
BADER, RFW ;
ANDERSON, SG ;
DUKE, AJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (06) :1389-1395