七元杂环桥连联苯化合物的合成、晶体结构及性质的研究 I.含双氧桥连杂环衍生物的合成与结构表征

合成了一系列含七元内杂环联苯化合物 ( 6,6′位不同取代的 2 ,10 二溴 6H 双苯 [d ,f] [1,3 ]双氧杂和 2 ,10 二醛 6H 双苯 [d ,f] [1,3 ]双氧杂 ) ,通过元素分析、核磁共振氢谱、紫外可见吸收光谱对它们的结构进行了表征 ,用X ray单晶衍射测定了部分化合物的晶体结构 .结果表明这类化合物具有相同的刚性扭曲构型 ,其二个苯环扭曲角的大小受 6,6′取代基团的影响可以发生 8° ( 3 5°～ 43 .1°)的变化 .     

1,7-双(N-取代氨基甲基)-2,8-二羟基-朝格尔碱的合成及其催化的Aldol-Ullmann反应（英文）

合成了新型1,7-双(N-取代氨基甲基)-2,8-二羟基-朝格尔碱(4),以4为催化剂催化了4-羟基香豆素和2-亚苄基丙二腈[或甲基(乙基)-2-氰基-3-苯基丙烯酸]的Aldol反应,获得了一系列化合物8;以4为配体与钯联合催化了串联Aldol-Ullmann反应,得到了化合物10和12.测试了所有化合物对人三阳性乳腺癌细胞(MCF-7)、人三阴性乳腺癌细胞(MDA-MB-231)、人肝癌细胞(HepG2)和人肝癌细胞(MHCC-97H)的抗癌活性以及对人肝细胞(LO2)的细胞毒性.其中,1,7-双((甲基氨基)甲基)-6H,12H-5,11-甲二苯并[b,f][1,5]二氮芳辛-2,8-二醇(4b)对MCF-7(抑制率30%)、1,7-双((((1-苯乙基)氨基)甲基)-6H,12H-5,11-甲二苯并[b,f][1,5]二氮芳辛-2,8-二醇(4d)和1,7-双(((吡啶-2-基甲基)氨基)甲基)-6H,12H-5,11-甲基二苯并[b,f][1,5]重氮-2,8-二醇(4e)对MDA-MB-231具有较高的选择性和抑制活性, 2-氨基-5-氧代-4-(3,4,5-三甲氧基苯基)-4H,5H-二氢吡喃并[3,2-c]亚甲基-3-腈(8q)对除MDA-MB-231外其他癌细胞均具有很强的抑制活性,而2-氨基-4-(4-溴苯基)-5-氧代-4H, 5H-吡喃并[3,2-c]亚甲基-3-腈(8a), 2-氨基-4-(2,4-二氯苯基)-5-氧代-4H,5H-二氢吡喃[3,2-c]亚甲基-3-腈(8e),2-氨基-4-(3-氟苯基)-5-氧代-4H,5H-吡喃[3,2-c]亚甲基-3-腈(8m)和2-氨基-4-(3-溴苯基)-5-氧代-4H,5H-二氢吡喃[3,2-c]亚甲基-3-腈(8n)对四种癌细胞均具有较高的抑制率,但所有的化合物对正常人细胞都具有细胞毒性,需要对其结构进行修饰.     

含1H-苯并[d]咪唑或1H-苯并[d][1,2,3]三唑结构的新型查尔酮衍生物的合成及PTP1B抑制活性研究

蛋白酪氨酸磷酸酶1B(PTP1B)作为胰岛素和瘦素信号转导通路的负调节因子,PTP1B抑制剂有希望成为治疗II型糖尿病和肥胖症的候选药物.为了寻找非酸类PTP1B抑制剂,设计、合成了一系列含1H-苯并[d]咪唑或1H-苯并[d][1,2,3]三唑的查尔酮类化合物,并对化合物进行了PTP1B抑制活性测定.结果显示,所有化合物对PTP1B均显示出较强的抑制活性,其中2-(1H-苯并[d][1,2,3]三唑-1-基)-N'-(4-(3-(2'-萘基)-3-氧亚基-丙-1-烯基)苯亚甲基)乙酰肼(10i)活性最佳,IC_(50)为(2.98±0.04)μmol·L~(-1).更重要的是,2-(1H-苯并[d][1,2,3]三唑-1-基)-N'-(4-(3-(4-甲基苯基)-3-氧亚基-丙-1-烯基)苯亚甲基)乙酰肼(10h)在20μg/m L的浓度下对T细胞蛋白酪氨酸磷酸酶(TCPTP)没有活性,显示了较好的选择性.     

X射线单晶衍射研究系列功能七元杂环桥联联苯构象

含有七元杂环桥联联苯的π-共轭聚合物是重要的宽禁带光电材料, 其发光性质决定于两苯环间扭曲角. 利用X射线单晶衍射仪确定了系列功能的七元杂环桥联联苯化合物的晶体结构, 比较了桥联原子, 6,6位取代基及分子间弱氢键对这类桥联联苯扭曲构象的影响. 桥联键是—CH2—O—CH2—和—CH2—S—CH2—的七元杂环桥联联苯两苯环间的扭曲角分别为39°和51°, 在6,6位上含有不同取代基的双氧桥联七元杂环桥联联苯的扭曲角存在5°的差异. 在双氧桥联的七元杂环桥联联苯的二聚物中, 桥联的氧原子与非桥联的苯亚基-苯亚基2,2’位置上的两个氢原子之间形成的氢键网络结构导致中心联苯呈现平面构象, 但氢键并没有改变桥联联苯的构象. 七元杂环桥联联苯的构象主要由桥联原子决定, 同时分子间相互作用亦能轻微调控这类桥联联苯的扭曲角.     

新型多取代Trger’s base衍生物的合成及其晶体结构

以邻氨基二苯甲酮为原料,经两分子环化缩合反应制得6,12-二芳基二苯并[b,f][1,5]二氮杂环辛四烯(2a~2d);2a~2d经Li Al H4还原制得6,12-二芳基-5,6,11,12-四氢二苯并[b,f][1,5]二氮杂环辛(3a~3d);3a~3d与醛(或酮)反应,合成了一系列新型的多取代Trger’s base衍生物(4a~4d和5a~7a),其结构经1H NMR,13C NMR,HR-MS(ESI)和X-射线单晶衍射表征。通过分析架桥前后3a(CCDC:1498564)和6a(CCDC:1498555)的晶体结构,解释了该类化合物1H NMR中NCH质子及桥上取代基质子裂分的原因,并进一步证实了4~7为非C2轴对称结构。     

新型多取代Tr(o)ger's base衍生物的合成及其晶体结构

以邻氨基二苯甲酮为原料,经两分子环化缩合反应制得6,12-二芳基二苯并[b,f][1,5]二氮杂环辛四烯(2a~2d);2a~2d经LiAlH4还原制得6,12-二芳基-5,6,11,12-四氢二苯并[b,f][1,5]二氮杂环辛(3a~3d);3a~3d与醛(或酮)反应,合成了一系列新型的多取代Tr(o)ger's base衍生物(4a~4d和5a~7a),其结构经1H NMR, 13C NMR, HR-MS(ESI)和X-射线单晶衍射表征.通过分析架桥前后3a(CCDC: 1498564)和6a(CCDC: 1498555)的晶体结构,解释了该类化合物1H NMR中NCH质子及桥上取代基质子裂分的原因,并进一步证实了4~7为非C2轴对称结构.     

替格瑞洛中间体的合成

以(3a S,4R,6S,6aR)-6-羟基-2,2-二甲基-四氢-3a H-环戊烷并[d][1,3]-二氧环戊烯-4-氨基甲酸苄酯为原料,经烯丙基取代、双键双羟基化、Smith降解、脱保护基和成盐反应,合成了替格瑞洛中间体(3a S,4R,6S,6aR)-6-(2-羟基乙氧基)-2,2-二甲基-四氢-3a H-环戊烷并[d][1,3]-二氧环戊烯-4-氨基草酸盐,总收率56.0%,其结构经1H NMR,13C NMR和ESI-MS确证。     

氨基清除树脂辅助合成2-(7-氟-3-氧-3,4-2H-苯并[b][1,4]噁嗪-6-基)异吲哚1,3-二酮

采用氨基清除树脂辅助合成方法,由6-氨基-7-氟-4-取代基-3(4H)-酮与取代邻苯二甲酸酐在冰醋酸中加热反应制备了2-(7-氟-3-氧-3,4-2H-苯并[b][1,4]噁嗪-6-基)异吲哚-1,3-二酮类化合物,纯度86％～95％．其结构经^1H NMR,IR和MS表征。     

五氯代-12H-双苯并[1, 3, 2]二氧磷杂八环的合成与化学

以双(2-羟基-3,5-二氯苯基)甲烷(4)与PSCl3关环,高收率地得到2,4,6,8,10-五氯-6-硫-12H-双苯并[d,g][1,3,2]二氧磷杂八环(5)。5与酚在无水K2CO3及铜粉存在下,或与醇在醇钠存在下反应,生成2,4,8,10-四氯-6-硫-6-芳氧基-12H-双苯并[1,3,2]二氧磷杂八环(6),或6-烷氧基的类似物(7)。5与醇在三乙胺存在下反应的产物为2,4,8,10-四氯-6-硫-6-羟基-12H-双苯并[1,3,2]二氧磷杂八环三乙胺盐(8)。8在DMSO中回流则氧化为它的氧类似物9。     

卤代双酚及其环合物 6 _ 取代 _ 12H _ 双苯并 [d,g][1,3,2]二氧磷杂八环的质谱研究

对双（2－羟基－溴、氯代苯基）甲烷及其环化的衍生物6－取代－12H－双苯并[d,g][1,3,2]二氧磷杂八环－6－硫化合物进行了质谱分析并探讨了其裂解规律。母体化合物主要在苯基及亚甲基处开裂,环合后的衍生物主要以硫和氮原子为中心进行反应。溴、氯代双氧环离子（m/z422)为环合衍生物的特征离子。     

螯形主体分子的设计、包结性能及其在细辛挥发油 有效成分选择分离中的应用

设计了两种新的具有螯形骨架的主体分子反式-1,2-二苯基-1,2-苊二醇(1)和顺式-1,2-二(1'-萘基)-1,2-苊二醇(2),主体(1),(2)可与许多有机小分子化合物形成配位包合物。用IR和粉末XRD表征了主体分子(1)和(2)的包结物,用^1NMR测定了包结物的主客体分子摩尔比：(1)·DMF(1:2),(1)·DMSO(1:2),(1)·THF(1:2),(1)·二氧六环(1:1),(1)·吡啶(1:1),(2)·DMF(1:1)和(2)·DMSO(1:1)。单晶X射线衍射分析了包结物的晶体结构,(1)·DMF：空间群Pnaa,a=0.9377(1)nm,b=1.4351(1)nm,c=4.0463(3)nm;(1)·DMSO：空间群Pbcn,a=1.6278(1)nm,b=1.0751(1)nm,c=1.4980(1)nm;(2)·DMF：P2~1/n,a=0.9796(1)nm,b=1.2377(1)nm,c=2.2344(3)nm,β=93.02(1)°;游离主体(1)：空间群P1,a=1.0461(1)nm,b=1.1213(1)nm,c=1.5496(1)nm,α=81.74(1)°,β=75.71(1)°,γ=89.00(1)°;分析了主体分子的刚性和柔韧性对包结性能的影响。并研究了主体分子(1)选择分离细辛挥发油,将顺甲基异丁香酚从挥发油中分离出来。     

2,3-二取代-4-(IH-l,2,4-三唑-l-基)-5-苯基氢基噻吩的合成及生物活性研究

合成了九个以噻吩为母体环的含三唑环的化合物——2，3-二取代-4-(1H-1， 2，4．三唑-1-基)-5-苯基氨基噻吩(2a-2i)，并测定了2a的晶体结构．晶体为三斜 晶系，P-1空间群，晶胞参数为：a=0．79816(15)nm，b=1．00259(13)nm，c=1． 4478(4)nm，a=100．326(16)°，β=94．69(2)°，r=106．083(9)°，V=1．0845 (4)nm～3，z=2，D_c=1．396 g／cm～3．初步生物活性表明所有目标化合物杀菌活 性较低，有一定的植物生长调节活性．     

Synthesis,characterization, and chiroptical property of optically active poly(urea-urethane)s

Five new optically active poly(urea-urethane)s were synthesized by solution polyaddition of (1S,2S)-(+)-2-amino-3-methoxy-1-phenyl-1-propanol ( 4 ) with diisocyanates (diphenylmethane-4,4′-diisocyanate, toluene-2,4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, m-xylylene diisocyanate) at 80°C for 60 h. In some cases, the reaction mixture transformed into a gel when cooled to room temperature. The reduced viscosities are between 0.14 and 0.63 dL/g depending on the solvents and diisocyanates. Thermal behaviors of these polymers were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The T_g and crystallization temperature (T_c) were in the range of 80–200°C and 220–238°C, respectively. Thermal decomposition started at about 275°C, and the residual weights at 400°C were 15–60% depending on the polymers. The conformation of the polymers in film state was studied by circular dichroism (CD) spectra, by comparison with the corresponding model compounds which were synthesized from 4 and phenyl isocyanate or propyl isocyanate. Polymers derived from aromatic diisocyanates formed as ordered conformation in the film state, while those from aliphatic diisocyanates did not. After packing as chiral stationary phases of high-performance liquid chromatography (HPLC), the polymers showed selective resolution to trans-stilbene oxide and trans-1,2-cyclopentanedicarboxanilide. © 1993 John Wiley & Sons, Inc.     

Preparation and mesomorphic properties of 1-methyl-1H-benzimidazole-based compounds

A series of 1-methyl-1H-benzimidazole-based compounds, 2-(4?-alkoxy-1,1?-biphenyl-4-yl)-1-methyl- 1H-1,3-benzimidazole derivatives (nPPMx-M) with terminal hydrogen, methyl and nitro moieties (coded as nPPMH-M, nPPMM-M and nPPMN-M, respectively), were prepared and their structures were characterised. The compounds display enantiotropic smectic mesophases for hydrogen and methyl terminated compounds (nPPMH-M and nPPMM-M), and enantiotropic nematic mesophases for nitro terminated compounds (nPPMN-M) with short alkoxy chain below than 10 carbon atoms, where the mesophase ranges are 24–72°C and 74–104°C on heating and cooling processes for nPPMH-M, 90–119°C and 110–135°C for nPPMM-M, and 102–129°C and 113–207°C for nPPMN-M, respectively. It is noted that the compounds nPPMx-M exhibit much lower melting points and much wider mesophase range both in heating and cooling than non-1-methyl substituted analogs, which are ascribed to the disruption of hydrogen bonding among the molecules caused by methyl substitution at 1-position of benzimidazole. Meanwhile, among the compounds nPPMx-M, much wider mesophase ranges are obtained for nPPMM-M and nPPMN-M, indicating a much high mesophase stability for the compounds bearing terminal moiety (CH₃ and NO₂).     

[1-芳基甲羰基-2-(1,2,4-三唑-1-基)]乙基-N,N-二烷基二硫代氨基甲酸酯衍生物的合成、结构表征及生物活性研究

以芳香基三唑类杀菌剂三唑酮为先导物设计并合成了5个含N,N-二烷基二硫代氨基甲酸酯的芳香三唑类化合物, 通过元素分析、红外光谱、核磁共振氢谱和质谱对其结构进行了表征. 用X射线单晶衍射测定了[α-(4-甲氧基苯甲酰基)-2-(1,2,4-三唑-1-基)]乙基-N,N-二甲基二硫代氨基甲酸酯的晶体结构, 晶体属于三斜晶系, 空间群, 晶胞参数为: a＝0.73482(15) nm, b＝1.1051(2) nm, c＝1.1209(2) nm, α＝90.32(3)°, β＝101.97(3)°, γ＝105.13(3)°, V＝0.8578(3) nm³, Z＝2, D_c＝1.357 g/cm³, F(000)＝368, µ＝0.324 mm^－1. 生物测试结果显示这5种有机化合物都具有杀菌性和植物生长调节活性     

两个环己烷螺含氮杂环化合物的合成和晶体结构

环己酮与硫代碳酰肼在不同介质中的反应，合成出两个不同的环己烷螺含氮杂环化合物。经Ｘ－射线结构分析确定它们分别为１，２，４，５－四氮螺［５，５］十一烷－３－硫酮，Ｃ＿７Ｈ＿（１４）Ｎ＿４Ｓ（Ⅰ）和１，２，４，－三氮螺［４，５］癸－１－烯－４－氨基－３－硫酮。Ｃ＿７Ｈ＿（１２）Ｎ＿４Ｓ＿ｘ（Ｓ＿ｘ＝０．８Ｓ＋０．２Ｏ）（Ⅱ）。晶体学参数分别为（Ⅰ）：Ｐ２＿１／ｃ，ａ＝１２．０２６（４），ｂ＝２６．８１７（６），ｃ＝１２．０４２（３），β＝１１５．９４（２）°，Ｚ＝４，Ｖ＝９３３．４（１０），Ｍ＿ｒ＝１８６．２８；（Ⅱ）：Ｐ２＿１／ｍ，ａ＝６．５９５（７），ｂ＝６．８１７（６），ｃ＝１０．５７２（６），β＝１０６．３（１）°，Ｖ＝４５６（１），Ｚ＝２，Ｍ＿ｒ＝１８１．０５。最终一致因子分别为Ｒ＝０．０５４，Ｒ＿ｗ＝０．０６５和Ｒ＝０．０８９，Ｒ＿ｗ＝０．０９６。两个化合物中，环己烷都为椅式构型，它与其螺联的６员氮杂环，５员氮杂环的最小二乘平面间的夹角分别为６８．９４和９０°。并对合成反应途径作了初步讨论。     

Identification of markers of thermal processing (“roasting”) in aqueous extracts of Coffea arabica L. seeds through NMR fingerprinting and chemometrics

Roasting of Coffea arabica L. seeds gives rise to chemical reactions that produce more than 800 compounds, some being responsible for the desired organoleptic properties for which the beverage called “coffee” is known. In the industry, the “roasting profile,” that is, the times and temperatures applied, is key to influence the composition of roasted coffee beans and the flavour of the beverage made from them. The impact of roasting on the chemical composition of coffee has been the subject of numerous studies, including by nuclear magnetic resonance (NMR) spectroscopy. However, the roasting equipment and profiles applied in these studies are often far from real industrial conditions. In this work, the effects of two critical technological parameters of the roasting process, namely, the “development time” (the period of time after the “first crack,” a characteristic noise due to seed disruption) and the final roasting temperature on coffee extracts, were investigated. Seeds were roasted at pilot scale according to 13 industrial roasting profiles and extracted in D₂O. The extracts were analysed by ¹H NMR experiments. The NMR spectra were compared using (a) quantitative analysis of main signals by successive orders of magnitude and (b) chemometric tools (principal component analysis, partial least squares and sparse-orthogonal partial least squares analysis). This allowed to identify compounds, which may serve as markers of roasting and showed that changes in chemical composition can be detected even for slight change in final temperature (~1°C) or in total roasting time (~25 s).     

α-羟基二茂铁类衍生物的合成及其晶体结构

通过甲酰基二茂铁与苯乙酮，硝基甲烷及丙酮的缩合反应，我们制得了其缩合产物-α-羟基-β-羰基化合物。并对甲酰基二茂铁与苯乙酮的缩合产物进行了X射线单晶结构分析。结果表明：该晶体属于单斜晶系，空间群为P 2~1/n，a=0.6022(1)，b=2.735(1)，c=0.9416(1)nm，β=99.02(1)°，V=1.532(1)(nm)^3，Mr=334.20，Z=4，Dx=1.45g/cm^3，μ=9.68cm^-^1，F(000)=696。     

Study of thermal behaviour and stability of Co-doped malayaite ceramic pigments

This contribution deals with the preparation and characterization of Co-doped malayaite pigments. Pigment samples were prepared by solid-state reaction at different firing temperatures (1200–1400 °C). For characterization of thermal behaviour, pigment formation and thermal stability were studied by the methods of thermal analyses. The compounds were evaluated from standpoint of their phase composition and particle size distribution. The XRD analysis of samples prepared at 1,300–1,400 °C indicates the occurrence of two-phase compounds, i.e. the malayaite and the cassiterite. Average value of mean particle size of tested malayaites is moved ~10 μm. The great attention was focused on determination of impact of firing temperature on the pigment-application properties. Because the malayaite compounds belong into ceramic pigments, the pigment-application properties were observed after application into organic matrix in mass tone and middle-temperature glaze in different pigment amounts. Generally, the colour appearance of tested malayaites is dependent on the firing temperature and it moves in different shades of blue colour. From pigmentary point of view, it is possible to recommend 15 % of mass pigment for sufficient colouring of middle-temperature glaze. The higher firing temperature provides the formation of pigment samples with the higher saturation and the higher values of hue angle. For preparation of Co-doped malayaite pigments with the excellent colour properties, the firing temperature 1,350 °C is necessary.     

Ln(ClO~4)~3-PCBAAP-H~2O系统在30℃时的溶解度研究

测定了两个三元系统Ln(ClO~4)~3-PCBAAP-H~2O(Ln=La,Yb;PCBAAP：4-(对氯苯酰基)氨基安替比林,C~1~8H~1~6O~2N~3Cl)在30℃时的溶解度,发现两系统各有一个组成为Ln(PCBAAP)~4(ClO~4)~3·nH~2O(Ln=La,n=6;Ln=Yb,n=2)的不一致溶解化合物生成。参考系统的溶解度研究结果,合成了系列化合物Ln(PCBAAP)~4(ClO~4)~3·nH~2O(Ln=La,n=6;Ln=Pr,Nd,Sm,Gd,Yb,n=2),通过化学分析及元素分析,IR光谱,TG-DTG,XRD和密度测定对其进行了表征。