有机光化学的几个反应及其在有机天然产物合成方面的应用

本文简要叙述了有机光化学合成中的ｄｅ Ｍａｙｏ反应，Ｐａｔｅｒｍｏ－Ｂｕｃｈｉ反应、烯烃对芳香化合物的加反应及氧杂双π甲烷重排反应（ＯＤＰＭ），并列举了上述反应在有机天然产物合成方面的一些新应用。     

聚苯并咪唑金属复合物的X-射线光电子能谱(XPS)研究

本文报道以聚苯并咪唑(PBI)与某些过渡金属卤化物所形成的金属复合物的XPS研究,由反映在金属复合物N_(1s)和C_(1s)振起(Shake-up)伴峰的消失,反映在PBI中N_(1s)双峰变为复合物中的具有高结合能的单峰以及与其复合金属离子结合能的降低,这就从施受两个侧面确证金属复合物的形成。XPS结果也说明在金属复合物的制备中,不同溶剂条件所制得的复合物在硅氢加成中活性丧失归结於溶剂导致的金属离子的还原。     

聚苯基单醚喹噁啉的合成及性能

聚苯基单醚喹噁啉是从芳香族四胺和芳香族四酮缩聚制得。我们以对苯二甲腈为原料,采用二甲基亚砜为氧化剂,简便地合成芳香族四酮。聚合时系统地研究了单体不同克分子比合成的树脂对各种性能的影响,从而对这类树脂的加工成型提供了实验的数据。我们认为这种树脂可以作为在水、化学介质或油环境中使用的绝缘材料。     

含次环己基的有机硅单体及其低聚体的合成

硅氯仿和环己二烯-1,3进行硅氢加成反应,生成1,3-双(三氯硅基)环己烷,经醇解制得1,3-双(三乙氧硅基)环己烷,与溴化甲基镁反应,制得1,3-双(二乙氧甲硅基)环己环、1-(乙氧二甲硅基)-3-(二乙氧甲硅基)环己烷和1,3-双(乙氧二甲硅基)环己烷,它们在盐酸溶液中分别进行水解,得到各种含次环己基的有机硅低聚体,其中2,2,4,4,11,11,13,13-八甲基-3,12-二氧(杂)-2,4,11,13-四硅(杂)三环[11,3,1,1~(5,9)]十八烷和D_4相似,可能经开环聚合得到聚硅次环己基硅氧烷。     

SYNTHESIS OF SILICON MONOMERS AND OLIGOMERS CONTAINING CYCLOHEXYLENE RING

1,3-Bis(trichlorosilyl) cyclohexane was obtained by addition of HSiCl_3, to cyclohexadiene-1,3in the presence of H_2PtCl_6.6H_2O in isopropyl alcohol. The new compound was ethanolysed andmethylated to form di-methyl tetra-ethoxy disilyl, tri-methyl tri-ethoxy disilyl and terta-methyldi-ethoxy disilyl cyclohexanes. These di-to tetra-functional monomers were hydrolyzed by hydrochloric acid in ether. The di-functional monomer yielded cyclic dimer similar to octamethylcyclotetrasiloxane and the tri-functionalmonomer, a cyclic tetramer, while in the case of tetra-functional monomer a cyclic octamer wasobtained. These compounds have not been reported in literature.     

聚酰亚胺和聚苯基喹噁啉的水解研究

聚酰亚胺和聚苯基喹嘿啉同属耐高温高分子,热氧化稳定性能好,但前者的耐水解性能却比后者逊色得多。本文对它们的模型化合物作了量子化学计算,对模型化合物和高聚物分别进行了水解反应,从理论上和实验方面都证实了聚酰亚胺是不耐水解的,而聚苯基喹嗯啉的耐水解性却十分突出。     

STUDY ON HYDROLYSIS OF POLYIMIDE AND POLYPHENYLQUINOXALINE

Although polyimide (PI) and polyphenylquinoxaline (PPQ) are both heat resistant polymers, their hydrolytic stabilities are quite different. In this paper, the electron densities of two model compounds——N-phenylphthalimide and 2,3-diphenylquinoxaline are calculated by moans of CNDO/2 method. On the other hand, hydrolysis of model compounds and polymers is carried out. The theoretical calculation and experiments both prove that PPQ has excellent hydrolytic stability while PI is completely hydrolyzed under the same experimental condition. The mechanism of hydrolysis is also predicted.