光致变色剂5－甲基螺噁嗪的改良合成

报道了先致变色剂５－甲基螺嗪的改良合成，关键中间体２，３，３，５－四甲基－３Ｈ－吲哚由相应芳胺经Ｍｏｈｌａｕ－Ｂｉｓｈｌｅｒ反应制备。所需原料３－溴－３－甲基－２－丁酮由相应酮在四氯化碳中，无催化剂条件下与溴反应制得。改进了由５－甲基费歇尔碱和１－亚硝基－２－萘酚制备目标分子的操作方法，对有关反应机理进行了探讨并研制出光致变色油墨。     

α-萘乙酰芳胺的相转移催化合成

报道了以α－萘乙酸为原料，经与ＳＯＣl2回流反应，得到α－萘乙酰氯，再在液－液相转移催化剂ＰＥＧ－４００的催化作用下，α萘乙酰氯与芳胺的反应，合成了１０析的α－萘乙酰芳胺，并经ＩＲ、^1HNMR、^13CNMR及元素分析确定了它们的结构。     

光致变色剂5—甲基螺恶嗪的改良合成

报道了光致变色剂５－甲基螺恶嗪的改良合成，关键中间体２，３，３，５－四甲基－３Ｈ－吲哚由相应芳胺经Ｍｏｈｌａｕ－Ｂｉｓｈｌｅｒ反应制备。所需原料３－溴－３－甲基－２－丁酮由相应酮在四氯化碳中，无催化剂条件下与溴反应制得。改进了由５－甲基费歇尔碱和１－亚硝基－２－萘酚制备目标分子的操作方法，对有关反应机理进行了探讨并研制出光致变色油墨。     

[3+3]环化反应合成1-芳基-4-芳甲酰基吡啶衍生物

选择性修饰吡啶骨架.以3-芳甲酰亚甲基-2-氧化吲哚和烯胺酮为原料,在乙醇钠作催化剂,乙醇作溶剂,100℃条件下反应.通过[3+3]环化反应,合成了四环稠合的吡啶衍生物.条件温和、产率高、原料廉价,体现了原子经济性和成键有效性.实现了吡啶骨架1位的芳基化,4位的芳甲酰基化.     

二茂铁酮亚胺的合成和鉴定

三氧化二铝为催化剂,乙酰基二茂铁与芳伯胺进行缩合反应,分离出十种稳定的酮亚胺。元素分析,红外光谱和核磁共振谱研究测定了它们的结构。比较乙酰基二茂铁和苯乙酮与芳伯胺的缩合反应条件,发现所需催化剂不同.     

N，N－双－（苯并咪唑基甲基）芳胺的合成及与芳香酮的交换反应

苯并咪唑、甲醛与芳胺在甲苯溶液中回流分水，得到６个未见文献报道的Ｎ，Ｎ－双－（苯并咪唑基甲基）芳胺，Ｎ，Ｎ－双－（苯并咪唑基甲基）芳胺与芳香酮在氯化氢－无水乙醇溶液中可发生交换反应，得到β－芳氨基双酮或β－芳氨基酮，β－芳氨基双酮在碱性条件下发生分子内醇醛缩合，得到环化产物４－羟基－４－苯基哌啶。用ＩＲ，１ＨＮＭＲ和元素分析确定了它们的结构。     

4—苯基—2—丁酮与芳香醛和芳香胺的Mannich反应

在催化量浓盐酸作用下，４－苯基－２－丁酮与芳香醛和芳香胺直接发生Ｍａｎｎｉｃｈ反应，生成５－苯基－１－芳基－１芳胺基－３－戊酮，产率７５％～９２％，共得到１５个新化合物，它们的结构都经元素分析。ＩＲ和ＭＳ证实。     

苯并三唑-N-Mannich碱与酮的交换反应

用苯并三唑、甲醛与芳香胺生成的N-Mannich碱,分别与苯乙酮、苯丙酮、β-苯乙酮、α-四氢萘酮进行交换反应,取得了成功。共合成了15个β-芳氨基酮,其中3个为未知物,交换反应在HCl-EtOH存在下于室温进行,具有反应条件温和、方法简便、产率尚可的特点。     

固-液相转移催化法合成N-芳基-N′-(α-萘甲酰基)硫脲和芳撑-二(α-萘甲酰基)硫脲衍生物

在固 液相转移催化下 ,以PEG 4 0 0为催化剂 ,通过α 萘甲酰氯与硫氰酸铵以及芳胺和芳二胺反应 ,合成了一系列N 芳基 N′ (α 萘甲酰基 )硫脲和芳撑 二 (α 萘甲酰基 )硫脲衍生物     

二元芳胺的双重氮盐与二茂铁的反应

由二茂铁与二元芳胺的双重氮盐的芳基化反应,得到了几种二茂铁衍生物。由双重氮化的联苯胺得到橙色的4-二茂铁基联苯,m.p.162.5—163.5℃,和橙紅色的4,4′-双二茂铁基联苯,260℃分介,产率分別为7.4％和8.5％。由隣联二茴香胺的双重氮盐得到4-二茂铁基-3,3′-二甲氧基联苯,m.p.162—164℃;产率9％。由对苯二胺的双重氮盐得到苯基二茂铁,产率9％。     

多杂原子化合物的设计与合成

通过Vilsmeier反应合成了4-[N-甲基-N-苯基]氨基苯甲醛中间体,该中间体与芳香胺类化合物反应,设计合成了3个新的多杂原子稠环化合物,并通过核磁氢谱、红外光谱、元素分析对它们进行了结构表征。     

Mixed aromatic-aliphatic organic nanoparticles as carriers of unidentified infrared emission features

Unidentified infrared emission bands at wavelengths of 3-20 micrometres are widely observed in a range of environments in our Galaxy and in others. Some features have been identified as the stretching and bending modes of aromatic compounds, and are commonly attributed to polycyclic aromatic hydrocarbon molecules. The central argument supporting this attribution is that single-photon excitation of the molecule can account for the unidentified infrared emission features observed in 'cirrus' clouds in the diffuse interstellar medium. Of the more than 160 molecules identified in the circumstellar and interstellar environments, however, not one is a polycyclic aromatic hydrocarbon molecule. The detections of discrete and broad aliphatic spectral features suggest that the carrier of the unidentified infrared emission features cannot be a pure aromatic compound. Here we report an analysis of archival spectroscopic observations and demonstrate that the data are most consistent with the carriers being amorphous organic solids with a mixed aromatic-aliphatic structure. This structure is similar to that of the organic materials found in meteorites, as would be expected if the Solar System had inherited these organic materials from interstellar sources.     

计算芳烃折光指数的新方法—基团键贡献法

根据分子中基团的特性和连接性,将基团贡献法和化学键贡献法有机地结合在一起,发展了一种计算芳烃折光指数的方法－基团键贡献法,该方法同时具有基团贡献法和化学贡献法的特点。应用基团键法对212种芳烃（烷基苯、烷基萘和烷基联苯）折光指数的计算结果表明,折光指数计算值与实验值之间的一致性令人满意,平均误差0.15%。     

3－乙酰基酚酮与TMB等芳醛缩合反应的研究

本文探讨了３－乙酰基酚酮与ＴＭＢ等芳香醛的羟醛缩合反应．３－乙酰基酚酮与ＴＭＢ、丁香醛、胡椒醛等取代醛反应分别生成３－［３，４，５－三甲氧基］肉桂酰基酚酮、３－［４－羟基－３，５－二甲氧基］肉桂酰基酚酮、３－［３，４－亚甲二氧基］肉桂酰基酚酮，与桂皮醛反应生成３－［５－苯基－２，４－戊二烯酰基］酚酮等四种新化合物．其结构经红外光谱、核磁共振谱及元素分析得以证实     

2-乙酰基-7-甲胺基酮与芳肼的缩合反应

系2-乙酰基-7-甲胺基酮与芳肼进行缩合反应,得到3种未见文献报道的新化合物。其结构经红外光谱、核磁共振谱及元素分析证实均为2-(1-芳亚肼基乙基)-7-甲胺基草酮。     

计算芳烃摩尔体积的新方法——基团键贡献法

根据分子中基团的特性和连接性,发展了一种计算芳烃摩尔体积的新方法——基团键贡献法,该方法将基团贡献法和化学键贡献法有机地结合在一起,既考虑分子中基团的特性,又考虑基团间的连接性(化学键),同时具有基团贡献法和化学键贡献法的特点。应用基团键贡献法对211种芳烃摩尔体积的计算结果表明,计算值十分接近实验值,平均误差0.354％,计算精度显著优于文献方法。     

Identification of petroleum aromatic fraction by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry

Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS) is com-mercially available in the 1990s, with the characteristics of large peak capacity, high resolution, high sensitivity, etc. However, its application to the petroleum and geological analyses is just emerging in China and overseas. In this research, the analytical method for petroleum aromatic fraction using GC×GC-TOFMS is set up, via the choice of the column system and optimization of setting parameters, such as temperature programming, modulation time, hot pulse time, flow rate of carrier gas, data acquisition rate and data processing. The results indicate that different polar compounds of aromatic fraction distribute as bands on structured GC×GC chromatogram. Within each band, homologous compounds appear as a roof-tile structure based on the number of substituent residues. The aromatic compounds are identified and characterized according to the GC×GC chromatogram and mass spectra. According to the polarity and the number of rings, aromatic compounds are spatially present on one chromatogram, which directly reflects the distribution characteristics of complex compounds of aromatic hydrocarbons. In addition, quantitative analysis is favored as some overlapped peaks on traditional GC-MS chromatogram have been separated completely on GC×GC. Some heterocyclic atom aromatic compounds at trace level can be clearly identified using this method, for polarity differences from other interfered aromatic compounds. The development of this method and chromatogram recognition offer petroleum geologists a practical example for the application performance of GC×GC-TOFMS.     

基于可见光-近红外光谱的煤种分类方法

利用便携式地物光谱仪SVC HR-1024对92个烟煤和58个褐煤样本进行光谱测试,烟煤和褐煤在可见光-近红外波段光谱特征差异明显,褐煤的光谱反射率及其斜率均明显高于烟煤.在光谱特征分析的基础上,利用MAO模型法、随机森林法、BP神经网络法和ELM算法进行煤种分类.结果表明:MAO模型法和随机森林法的分类结果较优.若进行大面积、快速遥感识别时,对分类时间要求较高,应选择MAO模型法;若是小面积单一矿区分类,对分类准确率要求较高,选择随机森林法较为恰当.     

多输出函数的自相关函数特征及Walsh谱特征

给出了多输出函数自相关函数的定义,并得到了多输出函数的自相关函数特征和Walsh谱特征的关系式;证明了多输出函数的Walsh谱的两种变换的关系式、Plancheral公式、能量守恒公式、卷积公式;得到了谱的平稳性．有助于进一步研究多输出函数的密码学性质．     

Molecular recognition study on a supramolecular system (VIII)

The fluorescence spectral titrations have been performed in phosphate buffer solution (pH 7.2) at room temperature to give the stability constants for inclusion complexation of a series of chemically modified β-cyclodextrins bearing aromatic groups with adamantanol. Thc molecular recognition mechanism is discussed from the viewpoint of the structural factors, electron effect of the substitutent groups and thc size and chain length of the fluorophore. The results indicate that the complex stability of the cyclodextrin derivatives bearing a positively charged pyridinio moiety can be enhanced by the electrostatic interaction between the host cyclodextrins and the adamantanol guest and the microenvironment change plays a crucial role in the inclusion complexation.