超细固体酸TiO2—SO4^2—催化α—蒎烯异构反应研究

通过Ｔｉ（ＳＯ４）２与Ｈ２Ｏ２反应生成的配合物沉淀来制备超细ＴｉＯ２－ＳＯ４＾２－固体酸催化剂，考察了催化剂焙烧过程的热分解性质，确定了催化剂的焙烧温度。用ＸＲＤ及ＴＥＭ测定了催化剂的晶形及颗粒大小，并研究了催化剂对α－蒎烯异构反应的产物分布，主要异构产物为莰烯。α－蒎烯转化率为９１％，莰烯选择率为６７％。     

1，3，4，6－四硫代戊搭烯－2，5－二酮制备含硫取代基的四硫富瓦烯的研究

以１，３，４，６－四硫代戊搭烯－２，５－二酮为原料，经偶联、醇解、烃化或醇解、烃化、偶联等步骤，制得四甲硫基四硫富瓦烯、四乙硫基四硫富瓦烃、二喹喔啉硫醚、４－甲硫基－５－甲氧甲酰硫基－１，３－二硫环戊烯－２－酮、四甲硫基乙烯和４，４＇－二甲硫基－５，５＇－二甲氧甲酰硫基四硫富瓦烯及它的异构体混合物．提出了１，３，４，６－四硫代戊搭烯－２，５－二酮醇解机理．讨论了未得到某些预期产物的原因．报道了３种四硫富瓦烯衍生物的循环伏安图及电化学性质．     

气相色谱-质谱法测定姜黄挥发油化学成分

采用水蒸气蒸馏法提取姜黄挥发油,用气相色谱－质谱联用技术分离和鉴定姜黄挥发油的化学成分。经计算机ＮＢＳ谱库检索,发现姜黄挥发油中至少有１５个峰,鉴定出α－姜黄烯、α－姜烯、桉叶油素和球姜酮等１５种组分;另外还有１－（３－环戊基醛）－２,４－二甲基苯、β－倍半水芹烯、大根香叶酮、大根香叶烷、顺双环［３,３,１］酮－２－烯－９－醇等成分。姜黄挥发油中主要成分为α－姜黄烯。     

1,3,4,6—四硫代戊搭烯—2,5—二酮制备含硫取代基的四硫富瓦…

以１，３，４，６－四硫代戊搭烯－２，５－二酮为原料，经偶联，醇解，烃化或醇解，烃化，偶联等步骤，制得四甲硫基四硫富瓦烯，四乙硫基四硫富瓦烃，二喹喔啉硫醚，４－甲硫基－５－甲氧甲酰硫基－１，３－二硫环戊烯－２－酮。四甲基乙烯和４，４＇－二甲硫基－５，５＇－二甲氧甲酰硫基四硫富瓦烯及它的异构体混合物，提出了１，３，４，６－四硫代戊搭烯－２，５－二酮醇解机理。讨论了未得到某些预期产物的原因，报道了３种四     

萘酰亚胺类共聚色素的合成

以６－溴－１Ｈ，３Ｈ－萘并［１，８－ｃｄ］吡喃－１，３－二酮为原料，经亚胺化、Ｕｌｍａｍｎ缩合后与丙烯酰氯酯化得到具有荧光的可聚合单体６－（Ｎ－丙烯酰氧乙基）氨基－２－（２ ’，４ ’－Ｎ，Ｎ－二甲基）苯基－１Ｈ－苯并［ｄｅ］异喹啉－１，３（２Ｈ）－二酮，它与甲基丙烯酸甲酯经自由基共聚得到具有强烈荧光的聚合色素。     

紫玉兰叶油化学成分的气相色谱/质谱法分析

采用常规水蒸汽蒸馏法提取出紫玉兰叶油,经气相色谱－质谱联机分析,分离出４０多个峰,鉴定出３２种化合物,主要是大根香叶烯、檀紫三烯,石竹烯３,７二甲基－１,３,７－辛三烯、莰烯等,占总峰面积的９５％。     

手性助剂诱导下的α,β-不饱和酮的不对称加氢反应及其在合成(R)-麝香酮中的应用

在ＴＨＦ溶液中，４０－６０℃及０．３－０．５ＭＰａ氢压条件下，［ＲｕＣｌ２（ｃｈｔ）］２＋（Ｓ）－ＢＩＮＡＰ手性催化剂体系催化不饱和手性缩酮２选择加氢，再经脱去手性二醇，即可高立体选择性地制得（Ｒ）－３－甲基环十五烷酮（４，（Ｒ）－（－）－麝香酮），化学收率≥９５％，光学纯度≥９７％．手性缩酮２由Ｄ－苏糖醇或Ｄ－葡萄糖衍生的手性二醇３与３－甲基环十五烯－２－酮１生成．     

八面沸石在精细有机合成中的催化作用Ⅸ．脱铝超稳Y沸石催化α－蒎烯的异构化反应

研究了脱铝超稳Ｙ沸石催化α－蒎烯的异构化反应，主要产物是：莰烯、宁烯、α－松油烯、异松油烯和对异丙基甲苯．同时，还考察了催化剂硅铝比及反应条件对转化率和产物选择性的影响．结果表明，溶剂对催化剂的催化性能有很大的影响     

TTF·M（dmit）2型电荷转移配合物的合成及其拉曼光谱

合成了８种四硫富瓦烯·二－（１，３－二硫杂环戊－４－烯－２－硫酮－４，５－二巯基）金属（缩写为ＴＴＦ·Ｍ（ｄｍｉｔ）－２）电荷转移配合物，其中７种配合物为首次合成，拉曼光谱的研究结果表明，对同一种电子受体，电子给体的还原电势Ｅｐ越小，配合物的电荷转移度ρ值越大。     

银环蛇蛇蜕新化学成分的研究

从银环蛇蛇蜕中分离及鉴定出Ｚ－１７－三十四碳烯－４，３１－二酮（Ⅰ），６，２１－三十五碳二烯－醇－１（Ⅱ），２－二十烷氧基乙醇（Ⅲ）和胆甾醇４个化合物。其中（Ⅰ）和（Ⅱ）为文献上未有记载的新化合物，（Ⅲ）是在蛇蜕中首次发现。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

解决能源问题的新途径——光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。