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Measurement of Quantity of Heat and Thermodynamical Prameters for the Chemiluminescent Cycloreversion specific in the Solid State

固态化学发光环回反应的热量和热力学参数的测量

基本信息

批准号：
05453022
负责人：
KIMURA Masaru
金额：
$ 3.2万
依托单位：
Okayama University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1995
项目状态：
已结题

项目摘要

We have investigated a thermally forbidden ring fission or ring opening reaction of biplanemers ([4+4] heterodimers of arenes) 1, lophine peroxides 2 and cyclobuta [b] pyroles 3 which are an energy rich system. The chemiluminescent thermal cycloreversion of 9-anthracenecarboxylic acid-benzene biplanemer and the chemiluminescent multiphoton cycloreversion of anthracene- p-difluoro-benzene biplanemer with Nd-Yag IR laser light gave off chemiluminescent light only in the solid phase. As there has not been any attempt to reveal the determinants in the solid state for the chemiluminescence from thermodynamical view points, this prompted us to collect the thermodynamic parameters by differential scanning calorimetry (DSC). In the cases of 1, two substantial exothermal processes are superimposed for the chemiluminescent crystals, whereas one main exothermal process is observed for a nonchemiluminescent powder sample. The thermodynamic parameters for the thermal cycloreversions were collected. Higher activation energy is characteristic of the chemiluminescent process prepared in the solid phase. Efficient chemiluminescence was observed in the thermal reaction of lophineperoxides 2 in both solid and liquid phases. Virtually same activation energies were obtained. The kinetic and thermochemical study of thermal ring opening reaction of 3,5- and 2,4-di-tert-butyl-3a, 5a-dihydro-3H-cyclobuta- [b] pyroles 3a and 3b to the corresponding di-tert-butyl substituted azepines was performed in the solid state, and provided activation energies 12 kcal/mol and 24 kcal/mol, respectively.

我们研究了能量丰富的双平面分子([4+4]芳烃杂二聚体)1、Lopine Peroxide 2和环丁烷[b]吡咯3的热禁戒裂环或开环反应。9-苯甲酸-苯双平面的化学发光热回旋和对二氟苯-9-二氟苯双平面的化学发光多光子回旋只在固相中发出化学发光。由于还没有人试图从热力学的角度揭示固态化学发光的决定因素，这促使我们用差示扫描量热法(DSC)收集热力学参数。在1的情况下，化学发光晶体有两个明显的放热过程，而非化学发光的粉末样品则观察到一个主要的放热过程。收集了热环反转反应的热力学参数。在固相中制备的化学发光过程具有较高的激活能。在固、液两相热反应中观察到了高效的化学发光。得到了几乎相同的活化能。研究了3，5-和2，4-二叔丁基-3a，5a-二氢-~3H-环丁基-[b]吡咯3a和3b与相应的二叔丁基取代氮杂环丙烷在固相中的热开环反应动力学和热化学，分别得到了12kcal/mol和24kcal/mol的反应活化能。