PHOTOCYCLIZATION OF DIPHENYLAMINE STUDIED BY TIME-RESOLVED THERMAL LENSING - HEAT OF REACTION, ENERGETICS, AND REACTIVITY OF INTERMEDIATES

被引：21

作者：

SUZUKI, T ^{[1
]}

KAJII, Y ^{[1
]}

SHIBUYA, K ^{[1
]}

OBI, K ^{[1
]}

机构：

[1] TOKYO INST TECHNOL, DEPT CHEM, 2-12-1 OHOKAYAMA, MEGURO KU, TOKYO 152, JAPAN

来源：

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN | 1992年 / 65卷 / 04期

关键词：

D O I：

10.1246/bcsj.65.1084

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The time-resolved thermal lensing (TRTL) technique was employed to study the photocyclization of diphenylamine (DPA) to form intermediate 4a,4b-dihydrocarbazole (DHC) in methanol solution at room temperature. The heat of reaction, DELTA-H, was determined to be (2.6 +/- 0.2) x 10(2) kJ mol-1 (1DPA --> 1DHC): The reaction proceeds endothermically. The ring closure step proceeds on the triplet surface (3DPA* --> 3DHC*). These triplet states are found to be isoenergetic by analyzing the time evolution of the TRTL signal. 3DHC* is located at 21 kJ mol-1 above 1DHC. Furthermore, two-color laser flash photolysis experiments have revealed that the photoexcitation of intermediate 1DHC leads to the recovery of parent DPA and therefore inhibits the formation of carbazole.

引用

页码：1084 / 1088

页数：5

共 13 条

[1] EFFECT OF MOLECULAR GEOMETRY ON SPIN-ORBIT COUPLING OF AROMATIC-AMINES IN SOLUTION - DIPHENYLAMINE, IMINOBIBENZYL, ACRIDAN, AND CARBAZOLE [J].