Investigation of Isomerization of 2—Seleno—1,3,2—diazaphospholidine Derivatives

For the first time the isomerization of 1,3,2-diazaphospholidine-2-sclenide dervatives in refluxing benzene in the presence of trace water was observed. The structures of isomerized products were determined by IR, ^1H NMR,^31P NMR, elemental analysis and X-ray crystallography. The mechanism of isomerization was also proposed.     

Initiation of cationic polymerization of n-butyl vinyl ether by stable cation radicals of substituted phenothiazines

3,7-Diethyl- 10-phenylphenothiazine (DEPPT), a phenothiazine derivative whose 3,7- and 10-positions are blocked, was synthesized. Potentiostatic electrolysis of DEPPT in acetonitrile (ACN) in the presence of 0.1M of LiClO₄ at 0.7 V (vs. Ag/Ag/Cl) yielded the stable cation radical of DEPPT (DEPPT^+·) which was characterized by cyclic voltammetry, UV-visible spectroscopy, and ESR spectrometry. Stable cation radicals of 10-phenylphenothiazine and 3,7-diethyl-10-methylphenothiazine were also prepared. The cationic polymerization of n-butyl vinyl ether was initiated by these cation radicals, including DEPPT^·+. The electron transfer mechanism for the initiation step, which we proposed previously, was supported by the fact that DEPPT^·+ was capable of initiating the polymerization; dimerization of DEPPT^·+ by releasing protons is precluded because 3,7- and 10-positions are all blocked. © 1994 John Wiley & Sons, Inc.     

碱金属沸石上乙醇双分子缩合反应及其机理

首次发现在碱金属Ｘ沸石上乙醇能够发生以正丁醇为主产物的双分子缩合反应，在所研究的催化剂中，含Ｒｂ的ＬｉＸ沸石表现出较高的反应活性和选择性。反应机理的研究表明，反应不经过ａｌｄｏｌ缩合步骤。在此基础上，对反应机理提出了新建议：在碱性沸石作用下，乙醇的β－位Ｃ－Ｈ键被活化，双分子脱水导致缩合。碳链的增长按此模式进行。     

用动力学方法研究8,9-苯并-2-亚甲基-1,4,6-三氧螺[4,4]壬烷的聚合反应机理

根据在自由基引发剂存在下,8,9-苯并-2-亚甲基-1,4,6-三氧螺(4,4)壬烷(Ⅰ)可能存在的竞争反应,推导了动力学方程式。用红外光谱法测定了单体的消失速率和苯酞的生成速率。实验结果与推导动力学方程式相符。进一步证明了单体(Ⅰ)的增长反应由加成聚合和开环—异构化—加成这两个反应组成。这两个反应对总速率的相对贡献与单体浓度有关。得到了共聚物的结构。     

(2E,4E)-3-苯基-2-[2-(N-乙氧羰基甲基氨基)-苯硫基]-2,4-己二烯酸乙酯——一个新的分子内重排反应产物

２，３－二氢－２－甲基－４－苯基－１，５－苯并硫氮杂卓与重氮乙酸乙酯反应，得到非预期的分子内重排的开环产物。通过元素分析、ＩＲ，１ＨＮＭＲ，ＭＳ及Ｘ－晶体衍射分析确定了它的结构，并根据产物的结构，对这一新反应的反应机理进行了探讨和研究。     

DPPH (= 2,2‐Diphenyl‐1‐picrylhydrazyl = 2,2‐Diphenyl‐1‐(2,4,6‐trinitrophenyl)hydrazyl) Radical‐Scavenging Reaction of Protocatechuic Acid Esters (= 3,4‐Dihydroxybenzoates) in Alcohols: Formation of Bis‐alcohol Adduct

Protocatechuic acid esters (= 3,4‐dihydroxybenzoates) scavenge ca. 5 equiv. of radical in alcoholic solvents, whereas they consume only 2 equiv. of radical in nonalcoholic solvents. While the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents as compared to that in nonalcoholic solvents is due to a nucleophilic addition of an alcohol molecule at C(2) of an intermediate o‐quinone structure, thus regenerating a catechol (= benzene‐1,2‐diol) structure, it is still unclear why protocatechuic acid esters scavenge more than 4 equiv. of radical (C(2) refers to the protocatechuic acid numbering). Therefore, to elucidate the oxidation mechanism beyond the formation of the C(2) alcohol adduct, 3,4‐dihydroxy‐2‐methoxybenzoic acid methyl ester ( 4 ), the C(2) MeOH adduct, which is an oxidation product of methyl protocatechuate ( 1 ) in MeOH, was oxidized by the DPPH radical (= 2,2‐diphenyl‐1‐picrylhydrazyl) or o‐chloranil (= 3,4,5,6‐tetrachlorocyclohexa‐3,5‐diene‐1,2‐dione) in CD₃OD/(D₆)acetone 3 : 1). The oxidation mixtures were directly analyzed by NMR. Oxidation with both the DPPH radical and o‐chloranil produced a C(2),C(6) bis‐methanol adduct ( 7 ), which could scavenge additional 2 equiv. of radical. Calculations of LUMO electron densities of o‐quinones corroborated the regioselective nucleophilic addition of alcohol molecules with o‐quinones. Our results strongly suggest that the regeneration of a catechol structure via a nucleophilic addition of an alcohol molecule with a o‐quinone is a key reaction for the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents.     

CePO_4/Ce-ZrO_2可加工陶瓷性能与断裂机制研究

以Ce ZrO2为基体,通过复合不同加入量的第二相CePO4颗粒,研究了陶瓷材料力学性能的变化,并借助加载能谱仪(EDS)的扫描电子显微镜(SEM)对材料弯曲断口及压痕裂纹扩展方式进行分析。当CePO4加入量为25%时,虽然材料力学性能有一定下降,但已经能用WC刀具进行加工。材料的弯曲断口显示,CePO4在两相体系中的断裂呈层片状形式;加入CePO4后,由于两相之间弱结合界面的存在,压痕裂纹扩展形式发生明显变化,由连续扩展机制过渡为不连续扩展。由这两种机制形成的材料断裂过程是阶段性的,在实际中可以用作材料最终破坏前的预报。     

5－（4－氯苯基）－10，15，20－三苯基卟啉及其配合物的合成、结构表征及热分解机理

合成了标题卟啉配体及其钴、镍、铜、锌和铁的五种配合物．对它们进行了元素分析、ＵＶ、ＩＲ和荧光光谱等结构表征．用ＤＴＡ、ＴＧ、ＤＳＣ等手段研究了这些新化合物的热稳定性及热分解机理，实验结果与ＨＭＯ方法计算的结果一致．     

Cr_2O_7~(2-)对B-Z振荡反应的影响及其分析应用

研究了Cr2O72-对B-Z化学振荡反应的影响.结果表明,Cr2O27-的加入明显改变该振荡反应的诱导期,且诱导期的改变值Δtin与所加入Cr2O72-的浓度有良好的线性关系,线性范围3.45×10-6~6.20×10-4mol·L-1,相关系数为0.9992,对Cr2O72-扰动B-Z振荡反应的机理进行了探讨.     

Novel polysiloxane formation process from dimethyldiethoxysilane in the presence of oxalic acid

Polysiloxane formation in dimethyldiethoxysilane (DMDES)-ethyl alcohol (EtOH(D))-oxalic acid (OA) (DMDES:EtOH(D):OA=1:2:0.5) and DMDES-dimethylsulfoxide (DMSO)-OA (DMDES:DMSO:OA=1:2:0.5) systems was investigated by gas chromatography-mass spectrometry and ²⁹Si-nuclear magnetic resonance. While the DMDES-EtOH(D)-OA system was homogeneous, the DMDES-DMSO-OA system consisted of two immiscible phases. In both systems, ethoxy-terminated linear oligomers ((EtO)Me₂SiO(Me₂SiO)_nSiMe₂(OEt); n=0–4, Et = C₂H₅, Me = CH₃) and cyclic tetramer ((Me₂SiO)₄) were identified. The reaction mechanism for polysiloxane formation is discussed.