不同取代三氟苯乙烯交叉环加成反应过渡态的额外极性相互作用 1. 对三氟甲基苯乙烯和对甲氧基三氟苯乙烯环加成反应的动力学研究

利用KINETICS-1计算机程序, 测定了在120-160℃四个温度下对甲氧基三氟苯乙烯与对三氟甲基三氟苯乙烯的交叉和均环加成反应的速率常数. 我们的数据, 特别是与交叉环加成反应的趋向有关的, 并由方程(10)所定义的φ函数值(1.4-1.9)表明, 在电子基取代的和吸电子基取代的三氟苯乙烯之间的交叉环加成反应的过渡态中, 非常可能存在着一个额外的极性相互作用.     

Electron-transfer fluorescence quenching processes in coaggregates between excited N-alkylcarbazoles as electron donors and 2, 4-dinitrophenyl carboxylates or pentafluorophenyl carboxylates as acceptors

Electron-transfer processes facilitated by hydrophobic-lipophilic interaction ( HLI) between excited N-alkylcar-bazoles (1-n, n=4, 8, 12, 16) as electron donors and 2,4-dintrophenyl carboxylates (2-n, n = 4, 8, 12, 16) or pentafluorophenyl carboxylates (3-n, n = 4, 8, 12, 16) as electron acceptors have been investigated by means of fluorescence spectroscopy in aqueous or aquiorgano binary mixtures. The fluorescence quenching of -n * by 2-n or -n indicates that preassociation precedes the electron transfer. The extent of HLI-driven coaggregation of the acceptor and the donor may be assessed from the B value of the equation I0/I = A B [Q]. The chain-length effect and possibly also a chain-fold-ability effect, as well as the solvent aggregating power (SAgP) effect have been observed. Comparison of the quenching constants (B) for 1-n * /2-n combinations and 1-n * / 3-n combinations shows that the order of increasing R values for the quenching processes is 3-n < 2-n.     

Pom-Pom分子在平面收缩流场中的流变行为

用基于管子理论发展的XPP(extended Pom-Pom)模型描述支化高分子熔体——低密度聚乙烯(LDPE)的分子流变特性,实现了从分子微观结构到宏观响应的跨尺度模拟.引入有限增量微积分(FIC)过程重构了压力稳定质量守恒方程以克服因流体不可压缩性引发的压力场空间分布虚假振荡现象.采用离散的弹性——黏性应力分裂技术(DEVSS)以在缺失纯黏性项情况下保持动量方程弱形式中的椭圆项贡献.利用迎风流线(SU)方法离散黏弹性XPP本构方程中的对流项,以基于Crank-Nicolson隐式差分格式的迭代稳定分步算法求解质量、动量守恒方程和本构方程.采用等低阶有限元模拟了平面黏弹性收缩流,考察了不同Weissenberg数、支化程度和分子结构参数对Pom-Pom分子在收缩流场中流变行为的影响,数值结果与相关文献和试验结果吻合得较好.     

2,5-二甲氧基苯基烷基酮与t-BuMgCl反应的机理研究

2,5-二甲氧基苯基烷基酮1_(a-d)(烷基分别为甲基、乙基、异丙基和叔丁基)与t-BuMgCl反应后,主要生成了1,2-加成产物、1.6-共轭加成产物及还原产物,产物及其分布在不同程度上受酮的结构、反应介质以及金属镁中过渡金属杂质的含量等因素的影响。据此,提出了反应的可能机理。     

Study on the Aggregation and Deaggregation Behaviors of Phosphatidylcholines

Phosphatdylcholines and their analogs, the functional building block of the membrane, are recently found to mediate multiple physiological processes and exhibit a broad range of desirable pharmacological effects, which involve hydrophobic lipophilic interactions (HLI) between the phospholipid and the cell membrane. The HLI behavior of phosphatJdylcholines (Ln) and their analogues 1, 2-diacyl-sn-glycerol-3-phosphoric acid bromoethyl ester (Pn), have been investigated in MeOH-H20 binary systems of different volume fractions (designated as Φ) of the organic component, by employing α-nephthylethyl lauryl ether (Np-12) as fluorescent probe. A very interesting observation is that the Ln possesses double character, i. e., it behaves both as an aggregator and as a deaggregator. The effects of the structure and the environment on the coaggregation and deaggregtion are also discussed.     

并入两个四氢键组装单体的卟啉衍生物的合成研究

报道了一个新的卟啉四氢键超分子聚合物组装单体29的合成研究。通过对 Gong等最近报道的四氢键二聚体组装板块进行修饰，合成了两个相应的新的苯甲酸 衍生物中间体11和21，以间－硝基苯甲醛为原料以较高产率合成了一个二硝基四苯 基卟啉26，氯化亚锡还原得到另－卟啉二胺中间体28。以DCC为缩合剂，该卟啉二 胺与其中一个酸11发生缩合反应得到相应卟啉组装单体目标分子29。化合物29在弱 极性溶剂中具有良好的溶解度。     

二环辛二烯二酮的合成

本文报告烯酮(Ⅲ)的合成,与(Ⅲ)相当的烯醇体即1,2-二羟二环辛四烯(Ⅱ)。合成的关键中間物,二酮(Ⅳ),由一新合成步驟制备,总产率19—36％:低温加氯化氫于环戊二烯得3-氯环戊烯(85—92％),再用鎂使之双合而成二烯(Ⅴ)(80—92％)。(Ⅴ)的臭氧化合物經过氧乙酸分解而形成四元酸(Ⅵ),酯化后得其四甲酯(Ⅶ)(由(Ⅴ)至(Ⅶ)总产率66—75％);后者可环化为二甲氧羰基二酮(Ⅷ)(52—67％),(Ⅷ)經水解脫羧即生成二酮(Ⅳ)(79—84％)。二酮(Ⅳ)可还元为二醇(Ⅸ)(65％)。由二酮(Ⅳ)再經四步反应后即得烯酮(Ⅲ):氯化二酮(Ⅳ)得二氯二酮(Ⅹ)(64—74％);將(Ⅹ)与乙二醇一同脫水縮合得縮二酮(Ⅺ)(52—66％);自(Ⅺ)脫氯化氫后得二烯縮二酮(Ⅻ)(69％),后者与丙酮經交換反应即变为烯酮(Ⅲ)(76％)。上述各化合物的分子結構,均經証明。烯酮(Ⅲ)不含其相当的烯醇体(Ⅱ);在鹼性溶液中亦不能形成稳定的二环幸四烯二醇-陰离子。因此可以相信,二环辛四烯体系具有芳族性的可能性極微。     

自旋离域参数δT之研究 3: 四种取代α,β,β-三氟苯乙烯的合成和环化二聚反应动力学参数的测定

本文报道了四种不同取代的三氟苯乙烯(TFS)的合成和在120-160℃范围内测定了p-Me3Si和p-CH3C(O)取代的TFS热环化二聚反应速率常数k2并计算出相应的Arrhenius参数和活化参数. 从^1^9F NMR的化学位移计算出四种取代TFS的极性参数σ^P. 并求出其中1和3的取代基自旋离域参数σT, 说明1和3都是拉电子取代基, 它们的σ^P分别为0.145和0.56, 但又是有相当自旋离域能力的取代基, 在140℃时其σT分别为0.29和0.50.     

双[1,3-二苯基-2-咪唑烷叉]和几种卤代烷的自由基型反应

在促进自由基型反应的条件(紫外光照射、无溶剂、室温振荡48小时)下,双[1,3-二苯基-2-咪唑烷叉](Ⅰ)与过量四氯化碳反应后生成较复杂产物(转化率约24%),自其中可分离检定二氯化物Ⅲe(约39%),一氯化物Ⅳ(约15%)及少量六氯乙烷.双体Ⅰ与1-氯丁烷反应(转化率约11%),亦可得二氯化物Ⅲe(约52%).同样,自过量1-溴丙烷可得二溴化物Ⅲd(产率约59%,反应转化率约29%),自过量碘乙烷可得二碘化物Ⅲb(产率约70%,反应转化率约41%).在离子型或异裂性的反应条件(室温、乙腈溶液、无引发自由基因素)下,各卤素与双体Ⅰ迅速反应,并以100%转化率及高产率形成其相应二卤化物Ⅲ.计:二氯化物Ⅲe,产率98%;二溴化物Ⅲd,产率90%;二碘化物Ⅲb,产率90%.新化合物Ⅲe及Ⅲd的结构通过几近定量的化学转化、紫外吸收光谱的对比、不同方法合成同一产物的熔点及混合烷点的对比以及元素分析得到证明.本工作说明,双体Ⅰ的反应方式不仅限于作为亲核卡宾Ⅱ的来源.双体Ⅰ本身是活泼分子,既能参与离子型反应,也能参与自由基型反应.     

MICROENVIRONMENTAL EFFECTS OF THE HELICAL CONFORMATIONS OF AMYLOSE AND ITS DERIVATIVES——CATALYTIC EFFECTS OF SODIUM CARBOXYMETHYLAMYLOSE ON THE HYDROLYSIS OF VARIOUS ESTERS OF N-ALKYL-3-HYDROXYPYRIDINIUM IODIDE

Hydrolysis of various carboxylic esters of N-alkyl-3-hydroxypyridinium iodide(2—5) has been studied, both in the absence and in the presence of sodium carboxymethylamylose(NaCMA 1). In the absence of Na-CMA, the hydrolysis of all four substrates follows 2nd-order kinetics when HPO_4~- and CH_3CO_2~- ions are used as the attacking nucleophites. In the presence of 1, however, the course of the reaction depends on the structure of the substrates. For 2 and 3, the observed rate constants k_(obs) are independent of the eoncentration of 1 added, but for those with long hydrocarbon chains, i. e. 4 and 5, the hydrolysis follows MichaelisMenten kinetics. All other experimental results also indicate the formation of supramolecular(incluston) complexes between the Na-CMA host molecules in helical conformations and theesters 4 and 5. In comparison with the bimolecular processes in the bulk phase, the catalytic efficiencies(k_c/K_d) of these supramolecular systems are 3.7×10~4 and 1.7×10~4 times that of the aceta