六次甲基四胺与溴代丙烯加合物的晶体结构

我们对六次甲基四胺(HMT)加合物的研究早感兴趣。为探讨Sommelet反应机理,我们证实氯化苄与HMT加合物为季胺盐阳离子[(CH_2)_6N_4·CH_2C_6H_5]~ 与Cl~-交错堆积组成的离子晶体。晶体中与四配位N联结的C-N键长有明显的增长效应。本文为其平行的工作。实验HMT与溴代丙烯加合物晶体的制备0.8g HMT溶于30 mL 1∶1三氯甲烷-丙酮,滴入0.7mL溴丙烯,待有细小晶体析     

1,5-二(2-羟基-5-氯苯基)-3-氰基甲 催化动力学光度法测定痕量锰(II)

The aerial oxidation of 1, 5-bis (2-hydroxy-5-chlorophenyl)- 3-cyanoformazan (HCPCF) in ammoniacal medium catalyzed by Mn(II) has been investigated and used for spectrophotometric determination of trace Mn(II) in water. The effect of various experimental factors was studied and the optimal conditions for Mn(II) determination were found. It has been shown that the reaction follows the rate expression:     

汞(II)-甲基百里酚兰-X(SCN^-,Br^-,I^-)三元混合配位化合物稳定常数的测定

With mercury (II)-methyl thymol blue-X (SCN, Br, I) as example, two methods are investigated in this paper. The first one bases on the variation experimental design, so that classical method of degree of dissociation can be used to calculate the stability constant from the molar ratio curve obtained. This method is simple, adaptable to cases where the decomposition is relatively weak. The second method requires the preliminary acquisition of the equilibrium constant of the decomposition reaction, with the calculation of the stability constant of the preceding formation reaction thereon. The evaluation procedure is more strict. Thhis method is applicable whether the decomposition reaction is strong or weak. Thus, we obtain stability constants of ternary complexes with rather strong subsequent decomposition reaction, such as Hg.MTB.I. Results obtained are rather satisfactory.     

Nd(OR)3-nCln-AlEt3催化体系对丁二烯的聚合 II.聚合物微观结构和催化剂诱导效应指数的关系

With a new series of binary catalyst Nd(OR)3-nCln-AlEt3 prepared in our laboratory, the effect to catalyst composition on the microstructure of polybutadiene was studied in detail. A linear relationship is found between the variation of the microstructure of the polymer obtained and the iductive effect index (I) which reprepresents the magnitude of the displacement of paired valence electrons on transition metal-halogen bond (MT-X) of the catalyst. This linear relationship also holds in dealing with the data published in the literature.     

超声波辐射下固-液相转移催化法合成N-(α -萘乙酰基)-N'- 芳基硫脲化合物

利用超声波辐射固－液相转移催化法合成了十三种未见文献报道的N(α-萘乙酰基)-N'-芳基硫脲新化合物,并经IR,1^HNMR,13^CNMR和元素分析确定了它们的结构。初步考查它们对玉米生长的促进作用,初步生物活性实验结果表明所有合成的化合物在(0.1～10)×10^-6的浓度内对玉米的根部生长具有显著的促进作用,部分化合物对玉米的幼苗具有促生长作用。     

Sm(Ⅲ)催化的三级环氧醇高度非对映选择性重排还原 反应-1, 3-二醇单酯的新 合成方法

本文报道了一个α-羟基环氧化物被Sm(Ⅲ)催化的新颖的串联反应。此反应一步完成了两个连续反应,高度非对映选择性地构筑了三个连续的立体中心。它可以成为一种高度非对映选择性地构筑2-季碳-1,3-二醇结构的一般方法。该反应的条件和机理在文中也作了详细的讨论。     

芳基脲类衍生物的合成、活性和量子化学计算

芳基脲类化合物是抑制细胞分裂生长的一种抑制剂。本研究报导合成的六个芳基脲类化合物,并利用油菜试法测定了它们抑制油菜胚根生长的生物活性;采用MOPAC程序中的PM3方法进行了量化计算,计算结果较好地解释了新合成化合物结构与生物活性的相关性。     

多氰基立方烷生成热的DFT-B3LYP和半经验MO研究

运用密度泛函理论(DFT)B3LYP方法和半经验MO(MINDO/3,MNDO,AM1和PM3)方法系统计算了全部21种多氰基立方烷的生成热,首先,在DFT-B3LYP/6-31G^*水平下通过不破裂立方烷笼状骨架(亦即选择立方烷为参考物)的等键反应设计,精确计算了9种多氰基立方烷的生成热;发现B3LYP/6-31G^*结果分别地均与上述四种半经验MO方法求得的生成热之间存在良好的线性关系(相关系数均在0.9994以上),且以AM1生成热与B3LYP/6-31G^*计算值最为接近,其次,其它12种多氰基立方烷的精确生成热借助上述线性关系通过校正对应的AM1结果而获得,多氰基立方烷的生成热很高,且随-CN基数目的增加而线性地增大,表明它们属于极具潜力的“新一低高能炸药”而具开发价值。     

NH2(X^2B1)与C2H4反应机理的从头算研究

用从头算MP2方法,在6-311G^**基组下,对NH2X^2B1)与C2H4的加成和氢迁移反应机理进行了研究,优化得到反应的过渡态,并通过振动分析和内禀反应坐标(IRC)加以证实,计算了两个反应的能垒和1500K～2000K温度范围内的速率常数。结果表明：在1500K～2000K温度范围内加成反应是NH2(XX^2B1)与C2H4的反应的主要通道,同时报道了两个反应沿反应路径变化信息。