两级吸收法制备固体光气

提出了一种制备固体光气的新工艺－两级吸收法。该反应反应5h，固体光气的收率大于95％，与其它文献报道的方法相比收率明显提高。     

2,6-二氯吡啶的定向合成及结构测定

研究了以吡啶为原料,通过光氯化反应定向合成2,6-二氯吡啶。并对光氯化反应的工艺进行了研究。当吡啶与氯气配比为1:2.3,反应温度为200℃,反应5h时,光氯化反应的转化率可达95.7%。反应的进程和产品的纯度通过GC-MS进行控制。并用元素分析、红外光谱、质谱对产物的结构进行了表征。     

Tunneling dynamics and spatial correlations of long chain growth in solid-state photochlorination of ethylene at low temperatures

A novel method is described for preparing reactive cryocrystals by deposition of argondiluted reactant beams and subsequent crystallization during evaporation of the inert gas. Photochlorination of equimolecular ethylene—chlorine mixtures obtained by this method and studied by means of kinetic UV- and IR-spectroscopy reveals activationless chain growth with mean length 300 units in the temperature range 17–45 K. Mean chain lengths greater than 100 are observed up to the conversion degree of 0.6–0.7. Comparison of the experimental data with computer simulations shows that the tunneling reaction is due to the formation of a closely packed reaction complex with high amplitudes of zero-point vibrations which lower the reaction barrier. The commensurability of reactant and product crystal lattices results in linear propagation of chains without accumulation of deformation strain. The chain termination mechanism associated with the spatial correlations of chains is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 687–700, April, 1993.The authors are grateful to Academician V.I. Goldanskii, Dr. D.E.Makarov, and Prof. S. Sato for useful discussion and to A.U.Goldschleger for assistance with the experiments.