多亚甲基桥连双(2-氨基-5-甲基-1,3,4-噻二唑)化合物的合成与表征

通过２－氨基－５－甲基－１,３,４－噻二唑与对甲基苯磺酰氯反应后再与多亚甲基双澳反应得到新化合物（１ａ～１ｅ）,１ａ～１ｅ醇解得５个新标题化合物。并由元素分析、ＩＲ和１ＨＮＭＲ确定了所有新化合物的结构。     

BaCe1—xRExO3—0.5x的溶胶—凝胶法合成及离子导电性

用溶胶－凝胶法合成了系列钙钛矿结构的ＢａＣｅ１－ｘＲＥｘＯ３－０．５ｘ（ＲＥ＝Ｌａ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｄｙ，Ｈｏ，Ｅｒ和Ｙ）复合氧化物，通过ＸＲＤ和热分析对样品结构及生成过程进行了研究．测定了不同温度下样品的交流阻抗谱，讨论了稀土离子掺杂对ＢａＣｅＯ３电性质的影响．溶胶－凝胶法比固相反应法合成温度降低了６００～８００℃，稀土掺杂使ＢａＣｅＯ３离子导电率提高了１０～４０倍．     

2－芳酰氨基－5－（5－苯基－2H－四唑2－甲基）－1，3，4－噻二唑类化合物的合成

在浓硫酸作用下，由５－（５－苯基－２Ｈ四唑－２－乙酰基）－４－芳酰氨基硫脲１ａ～ｎ制得了一系列新的２－芳酰氨基－５－（５－苯基－２Ｈ－四唑－２－甲基）－１，３，４－噻二唑化合物（２ａ～ｎ）。所有化合物的结构均经元素分析、ＭＳ分析，部分代表化合物经ＩＲ、￣ＨＮＭＲ分析确证；初步观察了２ａ～ｎ在１％浓度下对大肠杆菌（Ｇ￣－）的抑制作用，发现２ｄ，２ｅ，２ｆ，２ｎ显示出较强的活性。     

新显色剂2-(5-羧基-1,3,4-三氮唑偶氮)-5-二乙氨基酚的合成及其与铋的显色反应

首次合成了新显色剂２－（５－羧基－１，３，４－三氮唑偶氮）－５－二乙氨基酚（简称ＣＴＺＡＰＮ），研究了它的性质及其与铋显色反应的条件。结果表明：试剂的分子式Ｃ１３Ｈ１６Ｎ６Ｏ３分子量３０４．３２，ｍ．ｐ． ２５２℃，各级酸离解常数为ＰＫａ１＝３．１，ＰＫａ２＝７．５，ＰＫａ＝９．６；在ＰＨ ７的 ＮＨ４Ａｃ介质中，试剂与铋形成紫红色络合物，λｍａｘ为 ５４０ ｎｍ，对比度△λ为 １２０ ｎｍ，络合比Ｂｉ３＋：Ｒ＝１：２，摩尔吸光系数５．１３ ×１０４Ｌ·ｍｏｌ－１·ｃｍ－１，Ｂｉ３＋在０～１．８ ｍｇ／Ｌ范围内遵守比耳定律，在掩蔽剂的作用下，可不经分离直接测定合金样品及合成工业废水中微量铋，结果满意。     

双羰基侧链取代喹喔啉－1，4－二氧化物的合成

应用改良的Ｂｅｉｒｕｔ反应合成了５个双羰基侧链取代喹喔啉－１，４－二氧化物（３ａ～３ｅ）。     

1,3,5-三苯基苯的简便合成方法

采用氯化亚砜-无水乙醇为催化剂，以苯乙酮为原料一步合成了1，3，5-三苯基苯。研究了最佳反应配比和反应条件：反应时间为45～60min时，n(苯乙酮)／n(氯化亚砜)／n(乙醇)=3／15／5时反应产率达到最高，产率80％～85％，并对反应机理进行了讨论。     

3，3-二硝基氮杂环丁烷和1，1′-亚甲基-双（3，3-二硝基-1-氮杂环丁烷）的合成研究

3，3-二硝基氮杂环丁烷(DNAZ)的含能盐及衍生物是一类重要的高能量密度材料，因此DNAZ的合成和应用受到了密切关注．采用新的合成方法，以1-叔丁基-3，3-二硝基氮杂环丁烷为起始原料，以76．3％的总收率得到了DNAZ，然后以DNAZ为原料，与多聚甲醛反应，得到了1，1′-亚甲基-双(3，3-二硝基-1-氮杂环丁烷)(DNAZ-CH2-DNAZ)．用红外和核磁共振光谱等对各化合物的结构进行了表征．     

Fe-Al-α,α′-联吡啶络合催化聚合马来酸酐与环氧氯丙烷研究

研究了马来酸酐与环氧氯丙烷交替共聚，及Ｆｅ（ａｃａｃ）３ Ａｌ（ｉ Ｂｕ）３ α，α’ 联吡啶络合物（ａｃａｃ＝ 乙酰丙酮） 催化马来酸酐（ＭＡ） 和环氧氯丙烷交替共聚的特征，并用红外光谱，核磁共振谱研究了共聚物的结构。动力学研究表明共聚反应与单体浓度和催化剂浓度均呈一级关系。     

5-取代-1H-1,2,4-三氮唑-3-羧酸的合成及结构表征

以5-氨基-1H-1，2，4-三氮唑-3-羧酸为原料，经重氮化反应和Sandmeyer反应得到5-X(X=Cl，Br，I，CN)-1H-1，2，4-三氮唑-3-羧酸，通过元素分析、UV，IR，1H NMR和MS对所有产物的结构进行了表征。     

3-硝基-1,2,4-三唑-5-酮镱配合物的制备及其晶体结构

３硝基１，２，４三唑５酮（ＮＴＯ）的锂盐水溶液与Ｙｂ２Ｏ３的稀硝酸溶液反应，制备了标题配合物，其化学式为Ｙｂ（ＮＴＯ）３·１０Ｈ２Ｏ。用Ｘ射线衍射法测定配合物的晶体结构，其分子式为［Ｙｂ（ＮＴＯ）３（Ｈ２Ｏ）４］·６Ｈ２Ｏ。属单斜晶系，空间群为Ｃ２／ｃ。晶胞参数如下：ａ＝３６９３１（５）ｎｍ，ｂ＝０６６８３（１０）ｎｍ，ｃ＝２５６５６（３）ｎｍ，β＝１３０９７４（５）°，Ｖ＝４７８１１（１１）ｎｍ３，Ｚ＝８，Ｄｃ＝２０１３ｇ·ｃｍ－３，μ＝４０１７ｍｍ－１，Ｆ（０００）＝２８５０。镱离子的配位数为７，其配位多面体为五角双锥。     

The modern mass spectrometer—a complete chemical laboratory

Using nitrobenzene as an example, various ways in which a contemporary mass spectrometer can be utilized to yield a wealth of information about the compound studied are reviewed. Applying a variety of different techniques and procedures, in addition to the conventional low resolution mass spectrum, the following nitrobenzene spectra have been obtained: collision induced dissociation mass spectrum, mass analysed ion kinetic energy spectra, collision induced dissociation mass analysed ion kinetic energy spectra, spectra obtained at constant B/E, spectra obtained at constant B²/E, high voltage scans of metastable ion fragmentation processes, consecutive fragmentations in different field free regions, charge exchange mass spectra, charge stripping mass spectra, doubly charged ion mass spectra, chemical ionization mass spectra, negative ion mass spectra, negative ion mass analysed ion kinetic energy spectra, negative ion mass analysed ion kinetic energy collision induced dissociation spectra, charge inversion spectra, etc. The complementary types of information available from the above studies are discussed to show the unique versatility of mass spectrometry as a technique for the examination of organic compounds.     

Sites of protonation in phenothiazines: Methane and ammonia chemical ionization mass spectra

Positive ion methane and ammonia chemical ionization mass spectra for ten phenothiazine derivatives are reported. The fragmentations observed in the chemical ionization mass spectra are rationalized in terms of the location of the added proton. High-resolution measurements are used to confirm empirical formulae of the ions in the mass spectra. Changes in the mass spectra with a change in the chemical ionization reagent gas from methane to ammonia are described. A comparison with positive ion secondary ion mass spectra of the same compounds show that the amount of fragmentation is higher in the secondary ion mass spectra, but the same types of ions are observed in spectra produced by both ionization methods.     

顺,反式环丙烷衍生物异构体的区分

在化学电离条件下，研究了４种顺、反式环丙烷衍生物与丙酮和醋酸乙烯酸乙烯酯的分子离子反应。异构体１，２的丙酮ＣＩ谱及其加合离子「Ｍ＋Ｈ＋Ａ」的ＣＩＤ谱都 可以区分该对异构体。化合物２，３和４可以和质子化丙酮及质子化二聚体发生加合反应，但化合物１仅能与质子化丙酮发生加合反应。在醋酸乙烯酯的ＣＩ谱中，观察到４个化合物的质子化二聚体，其中异构体１，２的质子化二聚体的ＣＩＤ谱也能反映它们立体结构的差异。     

The mass spectrometry of polychlorinated dibenzo-p-dioxins

The negative ion chemical ionization mass spectra of polychlorinated dibenzo-p-dioxins using oxygen, methane and methane/oxygen are reported together with their methane positive ion chemical ionization mass spectra and conventional electron impact spectra. The methane/oxygen negative ion chemical ionization mass spectra proved to be the most useful of the negative ion spectra for structure determination.     

Comparison of electron ionization mass spectra of some organic compounds (MW < 200 Da) recorded on mass spectrometers of various types

Low-resolution electron ionization mass spectra recorded on various types of mass spectrometers (time-of-flight, quadrupole, and three-dimensional ion trap) were compared. A model mixture of 10 organic compounds (MW < 200 Da) was analyzed by gas chromatography-mass spectrometry. Pure mass spectra of analytes were extracted using the AMDIS software. The best repeatability was achieved for the time-of-flight mass spectrometer. The mass spectra recorded by a quadrupole and a time-of-flight mass spectrometer were quite similar. In the case of these instruments, library search using a commercial mass spectral data base (NIST’05) gave satisfactory result for each analyte (rank 1 or 2 in the “hit list”; Match > 900). In some cases, the mass spectra of model compounds recorded by the ion trap mass spectrometer differed in intensity of certain mass spectral peaks (but not in the set of peaks) from the mass spectra presented in the library and from the experimental mass spectra recorded by the time-of-flight and quadrupole instruments.     

硫逐磷酸酯和二硫代磷酸酯的电喷雾电离质谱lectrosprayIon

研究了9种硫逐磷酸酯及二硫代磷酸酯的电喷雾电离 (ESI)质谱并归纳了谱图特征。根据碰撞诱导解离 (CID)的结果 ,讨论了其在ESI质谱的规律。     

High-pressure collisional activation mass spectrometry of aromatic halides

The high-pressure collisional activation mass spectra with methane as the reagent/collision gas are reported for five aromatic halides. The major decomposition of the protonated aromatic halides is hydrogen halide elimination. The energy-resolved mass spectra and the chemical reactivities of fragment ions with the methane collision gas are used to establish dissociation pathways and structures of fragment ions. The high-pressure collisional activation mass spectra are compared with conventional collisionally induced dissociation and chemical ionization mass spectra.     

有机磷化合物的质谱研究(Ⅵ)——磷酰二胺酯类化合物的电子轰击质谱和化学电离质谱

本文报道了7种新的N-烷基-N′-乙氧羰基甲基-N′-芳磺酰基-O-乙基磷酰二胺酯化合物的电子轰击质谱(EIMS)和化学电离质谱(CIMS,甲烷为反应气)。结果表明,无论是EIMS,还是CIMS均存在较多的骨架重排离子峰;取代基对谱图有较大的影响;EIMS中P—N键的断裂为重要质谱特征,CIMS中MH~+准分子离子为重要特征离子,还存在分子离子反应的产物。     

甘草次酸及其衍生物的质谱研究

本文通过应用ＥＩ质谱和高分辨质谱对甘草次酸及其衍生物进行研究，阐明了分子离子的各种裂解、重排机理，讨论了主要离子的形成过程以及不同取代基对分子离子峰强度的影响。并用软电离手段──快原子轰击正、负离子（ＰＦＡＢ和ＮＦＡＢ）质谱，使ＥＩ谱上不出现分子离子峰的两个化合物而获得满意结果。