聚铝氨烷－钌－镧对1－己烯醛化反应的催化作用

聚铝氨烷－钌－镧对１－己烯醛化反应的催化作用杨荣华，吴晓龙，黄美玉，江英彦（黑龙江大学化学系哈尔滨１５００８０）（黑龙江省科学技术协会哈尔滨）（中国科学院化学研究所北京）关键词高分子催化剂，己烯，醛化，聚铝氨烷－钌－镧配合物醛化反应通常以羰基铑、羰基...     

水溶剂中芳醛与5，5－二甲基－1，3－环己二酮的反应

芳醛1与5，5－二甲基－1，3－环己二酮（2）在氯化三乙基苄基铵（TEBA）催 化下在水中生成2，2'－芳业甲基双（3－羟基－5，5－二甲基－2－环己烯－1－酮 ）（3），若在体系中有对甲苯磺酸存在时则生成3，3，6，6－四甲基－9－芳基－ 1，8－二氧代八氢化氧杂蒽（4）或3，3－二甲基－9－（3－羟基－5，5－二甲基 －2－环己烯－1－酮－2－基）－1－氧代四氢代氧杂蒽（6）而不是生成3，产率接 近定量。     

光皮木瓜果实中香气成分的GC-MS分析

以成熟光皮木瓜为试样,采用顶空固相微萃取与气质联用方法分析检测木瓜果实中的香气成分,共鉴定出43种香气成分,占总峰面积的92.89%。含量较高的依次为2-己烯醛、反式-2-甲基-环戊醇、(E,E)-2,4-己二烯醛、2-丁酮、(Z)-3-己烯醛、醋酸乙酯、(E)-3-己烯-1-醇、茶香螺烷等。其中C6化合物占总量的70%以上,因此可以确定C6化合物是构成光皮木瓜果实清香味的主要成分。     

(9Z,12Z,15Z)-十八碳三烯醛的GC-MS分析

（9Z，12Z，15Z）－十八碳三烯醛是美国白蛾信息素的主要成效成分之一，在其合成的过程中，采用气相色谱监测分离提纯效果；提纯的样品成分在化学方法、IR、^1H NMR波谱分析基础上用气相色谱－质谱鉴定为该化合物，并用气相色谱的面积归一化法测得其含量大于99％；该法简单、准确可靠、无需标样。     

高立体选择性合成及鉴定(9E,11E)-十四碳二烯-1-乙酸酯(淡褐苹果蛾性信息素)

根据Schlosser-Wittig反应，采用溴代ω－羟基壬烷基三苯基膦盐与2E－戊烯醛反应，产物经进一步酯化生成淡褐苹果蛾性信息素－（9E，11E）－十四碳二烯－1－乙烯酯，产物中（9E，11E）异构体含量可达98％。     

环己烯水合制备环己醇的研究 I．分子筛结构及晶粒大小的影响

考察了三种不同结构的分子筛（ZSM－5，MCM－22及-β）以及不同晶粒大小的ZSM－5分子筛对环己烯水合反应的催化活性。结果表明，具有12元环孔道体系的β分子筛对环己烯的转化率（9．6％）最高，但对环己醇的选择性（35．4％）最差。MCM－22分子筛的活性很低，其环己烯转化率只有0．8％。而孔口为10元环结构的ZSM－5分子筛则具有较高的活性环己烯转化率7．5％）和产物选择性（99．2％），因此是较好的水合催化剂。ZSM－5分子筛的晶粒大小对其环己烯水合反应活性有明显的影响，分子筛晶粒越细，则水合反应活性越高，其原因大于晶粒变细增大了分子筛的外比表面积，从而增加了接近孔口处的活性中心的数量。     

E—1、Z—2（1—咪唑基）—O—（α—甲基对卤苄基）2′，4′—二氯苯乙酮肟硝酸盐的合成与结构表征

首先以2,4－二氯氯代苯乙酮、咪唑、羟胺和对卤苯乙酮为原料,分别合成E－、Z－2－1（1－咪唑基）－2′,4－′二氯苯乙酮肟（IE、IZ）和对卤α－氯乙苯（ⅡA和ⅡB）,ⅠE和ⅠZ分别与ⅡA和ⅡB反应,生成E－、Z－2－1（1－咪唑基）－O－（α－甲基对卤苄基）－2′,4′－二氯苯乙酮肟硝酸盐四个新化合物,产率炒52．0％－60．0％,并经元素分析、IR和^1HNMR进行了表征。     

2—（2‘吡啶基）—5—甲苯并噻唑及其二氯二乙基锡（Ⅳ）络合物的结构以及抗

X－射线单晶衍射法测定了2－（2'-吡啶基）－5－甲苯并噻唑（I）及其二氯二乙基锡（IV）络合物（2）的结构，晶体（I）属单斜晶系，《空间群为P21／n，晶胞参数a=5.808(2),b=10.283(3),C=18.373(3)A,β=91.48(2)°，Z=4,Dc=1.370g.cm^-3，偏离因子R＝0．047。晶体（2）属单斜晶系，空间群p21/c,晶胞参数a=17.271(2),b=9.411(1),c=14.015(2)A,β122．98（1）°，Z＝4，D＝1．648g.cm^-3，偏因子R－0．047，络合物中Sn-N平均键长已达2．5－A，参考顺铂类药物研究经验，展望了抗肿瘤有机锡络合物发展的前景。     

柱色谱分离纯化茉莉醛

柱色谱分离纯化茉莉醛梁达文（广西玉林高等师范专科学校化学系玉林５３７０００）茉莉醛是一种广泛用于洗涤剂、化妆品和食品的重要香料￣［１－４］。利用苯甲醛与庚醛在碱性条件下合成的茉莉醛，其主要副产物庚醛自缩物（２－正戊基－２－壬烯醛）对茉莉醛的香气质量影...     

不同种兰花香气成分分析

利用固相微萃取和气相色谱-质谱联用(GC-MS)技术分析了5种兰花的香气成分。结果表明,5种兰花香气成分的种类和含量存在明显差异。绿苹果(Den.LittleGreen Apples)主要由反-2-己烯醛、己醛、丁羟甲苯、乙酸乙酯和3-己烯-1-醇等化合物构成,其中乙酸乙酯和反-2-己烯醛可能是花朵中苹果香的主要来源。香水文心兰(Onc.Sharry Baby)的主要香气化合物是顺-3,7-二甲基-1,3,6-辛三烯、3,7-二甲基-2,6-辛二烯-1-醇和3,7-二甲基-1,6-辛二烯-3-醇,三者的相对含量总和为84.57%。台北小姐(Cym.Miss Taipei)香气成分的主要特征不明显,除4-甲基苯酚和2-乙基丁醛外,其他化合物的相对含量均低于5%。夕阳红(Phal.Taida Salu)有香气成分50种,相对含量为87.01%,主要成分为柯巴烯、正己烷、甲酸己酯和3-己烯-1-醇。绿世界(Blc.Sung Ya Green‘green world’)有香气成分37种,主要由丙基环丙烷、2-(4-甲氧基苯基)乙醇、反-2-己烯-1-醇、3-己烯-1-醇、反-2-己烯醛、丁基呋喃和3,7,11-三甲基-1,6,10-十二碳三烯-3-醇等组成。     

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。     

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.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

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.     

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.