聚合物催化剂——Ⅰ.季铵盐聚合物试剂作三氯乙酸分解的催化剂

本文合成了一些季铵盐聚合物试剂,研究了这些试剂对三氯乙酸分解生成三氯乙酰氯的催化作用。不同季铵盐聚合物催化剂对三氯乙酸分解的催化活性顺序如下: (?) (?) 聚合物催化剂经重复使用后,活性并无明显降低。     

SAXS对NLO芪唑盐LB薄膜稳定性的研究

具有优良NLO性质的芪唑盐(记为S)已被用于制备LB薄膜,但其成膜性不好,稳定性差;S和花生酸镉(记为A)的混合系虽可改善成膜性,但在此混合膜系中,S相的稳定性仍然不佳。应用SAXS和微机模型拟合(MCMI)研究了上述两类LB薄膜的凝聚态结构,结果指出:在LB薄膜的二维类晶系结构中,S分子中呈哑铃形的芪唑基倾向于作倾斜状的密堆砌,S分子中的丙条脂肪链则倾向于采取全反式燕尾式构象,而且脂肪链只占S分子长的2/3,这就导致了S分子在二维类晶系结构中凝聚力的下降,以及造成LB薄膜层状超分子结构的破坏和崩塌。     

Regioselective Synthesis of Substituted Triazolium Salts <Emphasis Type="Italic">via</Emphasis> 1,3-Dipolar Cycloaddition Reactions

Summary. The regioselectivity of 1,3-dipolar cycloaddition reactions of 1-aza-2-azoniaallene salts with ,-unsaturated nitriles such as acrylonitrile or cyclohexylidene acetonitrile afforded only 1,2,4-triazolium salts via addition to the nitrile group, while the other expected pyrazolium salts were not observed. Moreover, 1-aza-2-azonia-allene salts reacted with other competitive systems such as -iminonitrile derivatives yielding only triazolium salts via addition to the nitrile and not to the imino group. Treatment of cumulene with 3-pyridylnitrile afforded the pyridinium salt. However, 2,3-dimethyl-5-(2,6-dimethoxyphenyl)-[1,2,4]triazole could be prepared from cumulene and 2,6-dimethoxybenzonitrile. Some reactions of nitriles with 1-aza-2-azonia-allene salts prepared from 1,2,3-indantrione and 9-acetylphenanthrene are discussed.     

Facile Desulfurization of Thioamides and Thioureas with Tetrabutylammonium Periodate under Mild Conditions

Summary. Thioamides and thioureas were reacted with tetrabutylammonium periodate at room temperature to afford the corresponding amides and ureas, respectively, under aprotic conditions.     

S-(1-二茂铁烷基)硫代乙醇酸与胺的反应——一类新型二茂铁衍生物的合成与性质研究

Ratajczak等研究了S-(1-二茂铁烷基)疏代乙醇酸的合成与反应(?)Ugi等将它们与羟胺反应,合成了一种有用的手性模板试剂。最近,Czech等用键合载体液相色谱对它们进行了光学拆分研究。本文报导了此类化合物与胺的反应,合成了一类新的化合物(?)二茂铁烷基)硫代乙醇酸胺。     

吗啡烷型生物碱类药物的化学发光分析法研究

雷氏盐（ＮＨ４Ｃｒ（ＮＨ３）２（ＳＣＮ）４）．Ｈ２Ｏ）是生物碱类物质的沉淀剂，经研究发现，雷氏盐可以催化鲁米诺与过氧化氢的化学发光反应，而吗啡烷型生物碱能沉淀雷氏盐，可导致鲁米诺－过氧化氢－雷氏盐体系化学发光强度的降低，根据这一发现，本文建立了吗啡烷型生物碱类药物（吗啡，青藤碱，可待因）的流动注射化学发光分析方法，方法有较低的检出限，较宽的线性范围和较好精密度用于一些药物的测定，结果较为满意。     

Lanthanum-based perovskites obtained in molten nitrates or nitrites

Lanthanum-based perovskites, LaMO₃ (where M = Mn, Fe, Co, Ni), have been synthesised from lanthanum precursors and corresponding 3d transition metal salts in molten alkali metal nitrates or nitrites. The reactivity of eight precursors in three molten salts of different basicity was analysed. Single phase orthorhombic LaMnO_3.11, and orthorhombic LaFeO₃ have been obtained in molten NaNO₂ at 723 K, for 2 h. LaCoO₃ is also formed in molten nitrite, but an increase of basicity, by adding Na₂O₂, was necessary to obtain LaNiO₃. The reaction systems were investigated by thermal analysis. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and specific surface area measurements (BET method) were used to characterise the synthesised nanopowders.     

双显色剂高灵敏协同显色反应的研究——钴(Ⅲ)-亚硝基R盐-结晶紫体系

在水溶液中钴(Ⅱ)与亚硝基R盐所形成的配合阴离子可以与有机碱阳离子(结晶紫)缔合形成中性缔合分子。在聚乙烯醇存在下,配合物可稳定存在于水溶液中。钴(Ⅲ)-亚硝基R盐-结晶紫配合物在510nm处有一最大吸收,摩尔吸光系数ε_(510)=1.47×l0~5L·mol~(-1)·cm(-1)。配合物中各组分的摩尔比为:Co:R:CV=1:3:6。反应具有较高的选择性,采用双峰双波长法测定钴可使灵敏度得到进一步提高,相应的摩尔吸光系数ε_(510-640)=4.09×10~5L·mol~(-1)·cm~(-1)。方法用于合成试样中钴的测定,结果满意。     

Thermodynamic parameters of interaction of HC1 with alcohols in water Ⅲ.HCl-ethanol-water system at 278.15-318.15 K

Pt,H2(g,p0)HCl(mE)|AgCl-AgPt, H2(g, p0)|HCl(mE), EtOH(mN)|AgCl-Ag have been measured at 10 degree intervals from 278.15 to 318.15 K, where EtOH refers to ethanol, mE=0.005-0.1 mol.kg-1, mN=0.4-1.0 mol.kg-1. The salting constant kS of EtOH by HCl and the thermodynamic parameters of interaction, fEN(gEN> hEN, sEN] cP,EN)> of EtOH with HCI in water have been evaluated. It has been shown that kS>0, gEN>0,hEN>0, SEN>0 ,and cp,EN<0.The signs of these parameters and the temperature dependence of them have been discussed on the basis of structural interaction and the group additivity models.     

Efficient and mild benzoin condensation reaction catalyzed by simple 1-N-alkyl-3-methylimidazolium salts

The benzoin reaction, catalyzed by simple 1-N-alkyl-3-methylimidazolium salt-based ionic liquid via carbene intermediate, to give the α-hydroxyl ketone proceeds in CH₂Cl₂ under mild conditions.