THERMAL REARRANGEMENTS .23. THE THERMOGRAM OF A C6H6 CHEMISTRY IN THE TEMPERATURE-RANGE FROM 450-DEGREES-C TO 730-DEGREES-C

被引:15
作者
ZIMMERMANN, G
NUCHTER, M
REMMLER, M
FINDEISEN, M
HOPF, H
ERNST, L
MLYNEK, C
机构
[1] UFZ HELMHOLTZ CTR ENVIRONM RES, SEKT SANIERUNGSFORSCH, D-04303 LEIPZIG, GERMANY
[2] UNIV LEIPZIG, INST ANALYT CHEM, D-04103 LEIPZIG, GERMANY
[3] TECH UNIV CAROLO WILHELMINA BRAUNSCHWEIG, INST ORGAN CHEM, D-38023 BRAUNSCHWEIG, GERMANY
来源
CHEMISCHE BERICHTE-RECUEIL | 1994年 / 127卷 / 09期
关键词
ISOMERIZATION; THERMAL; RADICALS; D-LABELING; 1,5-HEXADIYNE; PENTAFULVENE; REARRANGEMENT; HOMOALLYL;
D O I
10.1002/cber.19941270926
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The thermal isomerization of 1,5-hexadiyne (1) and its [1,6-D-2]-labeled derivative (1a) was studied in the temperature range 450-730 degrees C and in the presence of different carrier gases (N-2, H-2, D-2, N-2/toluene). By detailed analysis (GC, GC MS, NMR) all volatile reaction products were identified and determined quantitatively by using hexafluorobenzene as an internal standard. The experimental data show clearly that the reaction products are formed by two different routes: (i) electrocyclization leading to dimethylene cyclobutene (3) at temperatures up to about 600 degrees C and (ii) radical reaction leading to benzene (4) and pentafulvene (5) at temperatures above 550 degrees C. Cyclopentadienylmethyl radicals are supposed to be the essential radical intermediates.
引用
收藏
页码:1747 / 1753
页数:7
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