卟啉化合物的热化学研究 Ⅱ. 四苯基卟啉及其衍生物的标准燃烧能和生成焓

用自行安装的精密静弹燃烧量热计测定了四苯基卟啉(TPP)、四甲苯基卟啉(T_((PCH)_3)PP)、四对甲氧苯基卟啉(T_((P-OCH)_3)PP)和四邻氨苯基卟啉(T_((O-NH)_2)PP)的标准燃烧能,并计算出标准生成焓。样品 1.将苯甲醛加入沸腾的丙酸中迥流30分钟后冷至50～60℃,加入乙醇,冷却,过滤,紫色产物用甲醇洗,干燥后得TPP粗品。将粗品溶于迥流的二氯甲烷,加入溶于苯的DDQ迥流30分钟,蒸除溶剂,残渣溶于氯仿,氧化铝-氯仿柱层析,氯仿-甲醇重结晶制得纯TPP.

STUDIES ON THERMOCHEMISTRY OF PORPHYRINS Ⅱ. THE STANDARD ENERGIES OF COMBUSTION AND STANDARD ENTHALPIES OF FORMATION OF TETRAPHENYLPORPHYRIN AND ITS DERIVATIVES

Using precision static oxygen bomb combustion calorimeter, the standard energies of combustion of tetraphenylpophyrin, tetra (ρ-methylphenyl)-porphyrin, tetra(ρ-methoxyphenyl) porphyrin, and tetra(o-aminophenyl)-porphyrin at 298.15 K were determined to be -36.1279±0.0103, -36.9368±0.0120, -32.8427±0.0104, and -33.5453±0.0240 kJg~(-1), respectively. The corresponding standard enthalpies of formation at 298.15 K were calculated to be 621.3±8.5, 478.6±10.3, -171.1±9.7, and 474.2±17.2 kJ mol~(-1). The uncertainties of the results were given twice the final overall standard deviation of mean.