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

我们研究了双平面化合物（芳烃[4+4]异二聚体）1、过氧化物lophine 2和环丁基[b]吡咯3的热禁环裂变或开环反应，这是一个富能体系。用Nd-Yag红外激光对9-蒽羧酸-苯双平面化合物进行化学发光热环还原和对蒽-对二氟苯双平面化合物进行化学发光多光子环还原，只在固相发出化学发光。由于没有任何尝试从热力学角度揭示固态化学发光的决定因素，这促使我们通过差示扫描量热法（DSC）收集热力学参数。在1的情况下，化学发光晶体的两个主要放热过程叠加，而非化学发光粉末样品的一个主要放热过程被观察到。收集了热循环逆转的热力学参数。固相制备的化学发光工艺具有较高的活化能的特点。在液相和固相热反应中均观察到高效的化学发光。得到了几乎相同的活化能。对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平类化合物的热开环反应进行了固体动力学和热化学研究，分别获得了12 kcal/mol和24 kcal/mol的活化能。

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.