含有喹啉-2-甲醇单元的光学纯固有手性杯[4]芳烃衍生物：合成与在二乙基锌对苯甲醛催化不对称加成中的应用

合成并表征了一系列由含有喹啉-2-甲醇单元的具有锥式或部分锥式构象的光学纯固有手性杯[4]芳烃衍生的新型N,O-型手性配体,并且研究了这些手性配体在二乙基锌对苯甲醛催化不对称加成反应中的应用,这是首例有关固有手性杯芳烃作为手性配体用于催化不对称合成.     

BICYCLO[2. 2. 1] HEPT-5-ENE-2,3-DICARBOXYLIC ANHYDRIDE CAPPED ‘PMR'''' TYPE POLYAMIDE-IMIDE

The resin solution of NA capped ‘PMR' type polyamide-imide was prepared from bicyclo [2.2.1]-hept-5-ene-2, 3-dicarboxylic acid ethyl ester,1, 2, 4-trimellitic acid-2-(or-1-) ethyl ester and 4,4'-methylenedianiline in ethanol. This resin solution is specially suitable for the preparation of compo-sites. The fiexural strength of the glass cloth reinforced plastics was 6000--7000 kg/cm~2 (RM) and4000--kg/cm~2 (260°--300℃), respectively. The result of isothermal aging for 800 hours in-dicated that this composite can be used at 26℃. The mechanism of the formation of polyamide-imide was discussed by using appropriate model compounds.     

双环[2.2.1]庚-5-烯-2,3-二羧酸酐封端的“PMR”型聚酰胺-酰亚胺树脂及其复合材料

以乙醇作溶剂,双环[2.2.1]庚-5-烯-2,3-二羧酸单乙酯、1,2,4-偏苯三羧酸-2-(或-1-)乙酯和4,4’-二氮基二苯甲烷为原料,合成了“PMR”型(Polymerization of Monomer Reactants)聚酰胺-酰亚胺树脂。用它制成的复合材料能在260℃长期使用。利用模型化合物对聚酰胺-酰亚胺形成的机理进行了研究。     

几种酚醛树脂热裂解的研究

采用热失重、差热分析、热机分析、裂解气体容积分析及组分的色谱分析等方法,对几种热固性酚醛树脂的热裂解进行了研究。结果表明酚醛树脂的热稳定性与二亚甲基醚键的存在很有关系,随着醚键的增多而热稳定性降低。对树脂的热裂解机理进行了讨论。     

具有苯并噻唑环的二腈的聚合物

六十年代以来,国外对耐高温高分子,特别是耐高温杂环高分子,进行了大量工作,取得了很多成果,国内也进行了广泛的研究工作。但在这些工作中,既具有优良的耐高温性能,又具有良好的成型工艺性能,并能付诸实际应用的品种却不很多。我们根据自己的工作实践以及国外的一些发展趋势,认为先合成一种具有耐高温结构并含有能进行加成聚合的基团的单体或低聚物,然后在成型过程中聚合成交联结构,如此所得的高分子既具有耐高温性能,又可克服难以成型的缺点,适合作为增强塑料、模压塑料、涂料等方面的应用。对具体的结构设计,我们是这样考虑的:对耐温结     

~(13)C NMR SUBSTITUENT EFFECTS IN A SERIES OF 2-PHENYL BENZOTHIAZOLES

According to ~(13)C NMR determinations and analyses of 14 compounds of 2-phenyl benzothiazole, we have studied the substituent effects on aromatic hetero rings. The different substituents have effects on the charge densities in the molecules. We have also analyzed the structural factors of effects on ~nJ_(13C-1H). The perturbations of benzothiazole to benzene ring were studied by the method of comparison analysis. The substituent induced chemical shifts of benzothiazole were obtained. The experiential calculations of ~(13)C chemical shifts for aromatic carbons have been done, the calculated velues agreed with the experimental ones. The theoretical calculations for the compounds 2, 3, 9 have been made using the EHMO method (the Enlarged Hiickel Molecular Orbital Method). The relationships between the ~(13)C experimental chemical shifts and the total charge densities of the corresponding carbon atoms were obtained by the regression analysis. The correlation coefficient is—0.96.     

四种(3,4),(8,9)-双环氧-三环[5.2.1.02,6]癸烷的合成和构型

以内式及外式-三环[5.2.1.0^2,6]癸二烯-3,8为原料进行部分环氧化反应,先制得在[2.2.1]庚烷环上具有环氧基的单氧化物.然后分别以过醋酸环氧化,或进行次氯酸酯加成,继而脱去氯化氢而环氧化,制得四种立体构型不同的(3,4),(8,9)-双环氧-三环[5.2.1.0^2,6]癸烷.对它们的构型进行了讨论.