ABINITIO QUANTUM-MECHANICAL AND EXPERIMENTAL MECHANISTIC STUDIES OF DIELS-ALDER REACTIONS BETWEEN UNSUBSTITUTED AND PHENYL-SUBSTITUTED ACETYLENES AND 1,2,4,5-TETRAZINES

被引:52
作者
CIOSLOWSKI, J
SAUER, J
HETZENEGGER, J
KARCHER, T
HIERSTETTER, T
机构
[1] FLORIDA STATE UNIV,SUPERCOMP COMPUTAT RES INST,TALLAHASSEE,FL 32306
[2] UNIV REGENSBURG,INST ORGAN CHEM,W-8400 REGENSBURG,GERMANY
关键词
D O I
10.1021/ja00057a019
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
1,2,4,5-tetrazine (2a) undergoes thermal addition to phenylacetylene (1b) in dioxane with DELTAH(double dagger) = 15.8 kcal/mol and DELTAS(double dagger) = -31 cal/(mol.K). The activation parameters for the corresponding addition of lb to 3-phenyl-1,2,4,5-tetrazine (2b) are DELTAH(double dagger) = 16.3 kcal/mol and DELTAS(double dagger) = -31 cal/(mol.K). The (4+2)-cycloaddition of 2b to lb yields a mixture (with the ratios of 90.5:9.5 in dioxane and 94.5:5.5 in acetonitrile) of 3,4-diphenylpyridazine (6b) and 3,5-diphenylpyridazine (6c). Detailed ab initio electronic structure calculations are carried out in order to explain these experimental findings, and the computed electronic wave functions are analyzed with the help of rigorous interpretive tools. At the MP2/6-311G** level, the activation energy for the Diels-Alder cycloaddition of acetylene (1a) to 2a is estimated at 12.6 kcal/mol. The activation energy for the decomposition of the resulting intermediate (4a) to pyridazine (6a) and nitrogen (7a) is only 5.5 kcal/mol at the HF/6-31G* level. At the MP2/6-311G** level, the reaction barrier for the decomposition of 4a is so small that the corresponding transition state cannot be located. The head-to-tail cycloaddition of lb to 2b, which results in 6c as a final product, is preferred to the head-to-head cycloaddition (leading to 6b) by 0.9 kcal/mol at the HF/6-31G* level. However, when the attractive dispersion interactions between the phenyl rings are taken into account, formation of 6b is found to be favored over that of 6c by 4.0 kcal/mol, in agreement with the experimental observations. This unexpected conclusion provides the first documented example of regiospecificity being primarily controlled by the dispersion (attractive van der Waals) interactions.
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页码:1353 / 1359
页数:7
相关论文
共 23 条
[1]  
Almstrom GK, 1913, LIEBIGS ANN CHEM, V400, P131
[2]  
[Anonymous], [No title captured]
[3]   THE DIELS-ALDER REACTION OF 1-VINYLNAPHTHALENE WITH ALPHA,BETA-UNSATURATED AND ALPHA,BETA,GAMMA,DELTA-UNSATURATED ACIDS AND DERIVATIVES [J].
BACHMANN, WE ;
DENO, NC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1949, 71 (09) :3062-3072
[4]  
Bader R.F.W., 1994, ATOMS MOL QUANTUM TH
[5]   CALCULATION OF THE AVERAGE PROPERTIES OF ATOMS IN MOLECULES .2. [J].
BIEGLERKONIG, FW ;
BADER, RFW ;
TANG, TH .
JOURNAL OF COMPUTATIONAL CHEMISTRY, 1982, 3 (03) :317-328
[6]   DIPHENYLCYCLOPROPENONE [J].
BRESLOW, R ;
EICHER, T ;
KREBS, A ;
PETERSON, RA ;
POSNER, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1965, 87 (06) :1320-&
[7]   TOPOLOGICAL PROPERTIES OF ELECTRON-DENSITY IN SEARCH OF STERIC INTERACTIONS IN MOLECULES - ELECTRONIC-STRUCTURE CALCULATIONS ON ORTHO-SUBSTITUTED BIPHENYLS [J].
CIOSLOWSKI, J ;
MIXON, ST .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (11) :4382-4387
[8]   WEAK BONDS IN THE TOPOLOGICAL THEORY OF ATOMS IN MOLECULES [J].
CIOSLOWSKI, J ;
MIXON, ST ;
EDWARDS, WD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (04) :1083-1085
[9]   COVALENT BOND ORDERS IN THE TOPOLOGICAL THEORY OF ATOMS IN MOLECULES [J].
CIOSLOWSKI, J ;
MIXON, ST .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (11) :4142-4145
[10]   QUANTIFYING THE HAMMOND POSTULATE - INTRAMOLECULAR PROTON-TRANSFER IN SUBSTITUTED HYDROGEN CATECHOLATE ANIONS [J].
CIOSLOWSKI, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (18) :6756-6760