Crystal Structure and Binding Properties of a New Molecular Clip Based on Diethoxycarbonyl Glycoluril: C_(42)H_(36)N_6O_6

A new molecular clip based on diethoxycarbonyl glycoluril 5： C42H36N6O6, has been synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space group Pbca with a = 12.7639（5）, b = 16.9727（7）, c = 34.2069（14） A, V = 7410.5（5） A3, Z = 8, Dc= 1.292 g/cm3, p（MoKa） = 0.088 mm-1, F（000） = 3024, the final R = 0.0655 and wR = 0.1566 for 5123 observed reflections with I 〉 2tr（/）. The crystal structural analysis shows that intermolecular C-H...O and C-H...N hydrogen bonds stabilized the whole crystal structure. The binding study by fluorescence spectroscope titration showed that the title molecule can selectively recognize Fe3~ with fluorescence quenching.

Syntheses, Crystal Structures and Hydrogen-bonding Motif of Two Glycoluril Derivatives

The synthesis and aggregation behavior of two glycoluril derivatives were descrybed.The crystal of compound 1 belongs to the triclinic system,space group P1,with a=8.946(1),b=13.445(2),c=20.361(3)?,α=89.517(3),β=84.405(3),γ=86.325(3)°,Z=2,V=2432.1(6)?3,Dc=1.293 g·cm-3,C48H34N6O6·2DMSO,Mr=947.07,F(000)=992,μ=0.170 mm-1,the final R=0.1606 and wR=0.2410 for 4382 observed reflections(Ⅰ>2σ(Ⅰ)).The crystal of compound 2belongs to the monoclinic system,space group P21/c,with a=9.500(3),b=24.522(8),c=17.997(6)A,Z=2,V=4054(2)A^3,Dc=1.296 g·cm^-3,C48H34N6O6,Mr=790.81,F(000)=1648,μ=0.087mm-1,the final R=0.2146 and wR=0.2535 for 2878 observed reflections(Ⅰ>2σ(Ⅰ)).Unlike the highly conserved R22(8)hydrogen-bonding amide···amide homosynthon,the structural analysis indicated that compound 1 selected the C(20)hydrogen-bonding motif and 2 selected the R22(34)hydrogen-bonding motif,which revealed the competition from remote solvent molecule and the interference of the molecular hydrocarbon core in crystal packing.The supramolecular structure revealed molecule 1 is further linked into a one-dimensional chain and 2 into a two-dimensional interwoven plane by N–H···N hydrogen bonds.

Synthesis and Crystal Structure of a New Macrocycle Based on Diethoxycarbonyl Glycoluril: C_(26)H_(30)N_6O_(10)

A new macrocycle based on diethoxycarbonyl glycoluril 3,C26H30N6O10,has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21/c with a = 12.7291（10）,b = 25.157（2）,c = 8.5489（7） A,β = 104.4760（10）°,V = 2650.7（4） A^3,Z = 4,C26H30N6O10,Mr = 586.56,F（000） = 1232,T = 292（2） K,Dc = 1.470 g/cm^3,μ = 0.115 mm^-1,the final R = 0.0590 and wR = 0.1299 for 4918 observed reflections with I 〉 2σ（I）. In the structure of the title compound,a three-dimensional microporous architecture is formed via intermolecular hydrogen bonding interactions.

Crystal Structure and Binding Properties of a New Diethoxycarbonyl Glycoluril Derivative:C_(46)H_(34)Cl_4N_4O_8

A new clip molecule 1 based on diethoxycarbonyl glycoluril, C46H34ChN4O8, has been synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1 with a = 11.3674（8）, b = 11.3674（8）, c = 16.9704（12） A, a = 70.0690（10）, β= 72.2310（10）, y = 78.0880（10）°, V= 1993.2（2） A3, Z = 2, Dc = 1.521 g/cm3, μ（MoKa） = 0.361 mml, F（000） = 940, the final R = 0.0422 and wR = 0.1144 for 22997 observed reflections with 1 〉 2o（I）. The crystal structural analysis shows that C-H……O and C-H……Cl hydrogen bonds, C-H-……π, C-CI……π supramolecular interactions, andπ-π packing interaction stabilized the whole crystal structure. The binding study by fluorescence spectroscope titration showed that the title molecule can selectively recognize Fe3＋ with fluorescence quenching.

Synthesis and X-ray Crystal Structure of a Methylene-bridged Glycoluril Dimer

The synthesis and X-ray crystal structure of a methylene-bridged glycoluril dimer 2 was reported.The methylene-bridged glycoluril dimer 2（C38H36Br4N8O12,Mr=1116.35） crystallizes in space group P1 with a=10.5802（6）,b=16.8469（9）,c=24.7673（14） ,α=98.00,β=96.263（1）,γ=101.606（1）o,V=4239.3（4）3,Z=4,Dc=1.749 g/cm3,μ=3.869 mm-1 and F（000）=2224.It crystallizes in an S-shaped conformation that displays two ethoxycarbonyl groups on each face of the molecule.

Syntheses and Crystal Structure of a New Molecular Clip Based on Diethoxycarbonyl Glycoluril: C_(54)H_(38)N_8O_6·H_2O

A new glycoluril derivative 2 has been synthesized and characterized by single- crystal X-ray diffraction. It crystallizes in triclinic, space group Pī with a = 13.128（7）, b = 13.245（7）, c = 14.016（8） ？, α = 98.805（10）, β = 102.036（9）, γ = 101.470（10）°, V = 2287（2） ？3, Z = 2, C54H38N8O6·H2O, Mr= 912.94, F（000） = 952, T = 298（2） K, Dc = 1.326 g/cm3 and μ = 0.090 mm-1. Due to the intermolecular C–H… interactions, two monomeric molecular clips dimerize as a dimeric building block in the crystalline state. Those building blocks form tape-like supramolecular polymers driven by intermolecular C–H…N interactions and water molecules which stabilized in the packing structure served as hydrogen-bonding donors.

Synthesis and Crystal Structure of a Novel Bis(ethoxycarbonyl)glycoluril Macrocycle

A novel [2＋4＋2]-macrocyclic compound 3（C52H69N16O12, Mr = 1109.53） con- taining bis（ethoxycarbonyl）glycoluril groups was synthesized via the Mannich three-component reaction in one pot and its structure was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 10.077（3）, b = 10.642（3）, c = 15.324（5） , α = 96.704（5）, β = 102.304（5）, γ = 104.546（5）°, Z = 2, V = 1528.7（8）3, Dc = 1.283 g/cm3, μ = 0.097 mm-1, F（000） = 628, R = 0.0818 and wR（I 〉 2σ（I）） = 0.2346 for 3034 observed reflections.

Kinetics and Mechanism of the Exothermic First-stage Decomposition Reaction for 1,5-Dimethyl-2,6-bis(2,2,2-trinitroethyl)-glycoluril

The thermal behavior, mechanism and kinetic parameters of the exothermic first-stage decomposition reaction of the title compound in a temperature-programmed mode have been investigated by means of DSC, TG-DTG and IR. The reaction mechanism was proposed. The empirical kinetic model functions in differential form, apparent activation energy (Ea) and pre-exponential factor (A) of this reaction are (1 - α) ?1.119, 211.3 kj/mol and 1020.2 s?1, respectively. The critical temperature of thermal explosion of the compound is 202.2 °C. The values of ΔS≠, ΔH≠ and CΔG≠ of this reaction are 143.8 J.mol?1.K?1, 208.7 kj/mol and 141.7 kj/mol, respectively.

一种新型甘脲荧光分子夹的合成及其性能研究

甘脲分子夹是一类以甘脲为基本结构单元的“长臂型”超分子主体。设计合成了一种新型甘脲荧光分子夹,通过IR、^(1)HNMR、^(13)CNMR、MS对其结构进行了表征,并研究了其对金属离子的选择性。结果表明,甘脲荧光分子夹在216 nm、236 nm、265 nm、301 nm处均有较强的紫外吸收,在381 nm处有强的荧光发射峰;甘脲荧光分子夹对Ca^(2+)有很好的识别能力,Ca^(2+)浓度在0.1-3.2μmol•L^(-1)范围内与甘脲荧光分子夹的荧光强度呈良好的线性关系,线性相关系数R^(2)为0.989,检测限为0.047μmol•L^(-1)。甘脲荧光分子夹是一种高选择性、高灵敏度的Ca^(2+)荧光探针。

甘脲用作气相色谱固定相的色谱性能研究

甘脲具有双环双脲结构,既是质子给体,又是质子受体,能与溶质产生氢键作用等多种作用力。本文制备了以甘脲作为固定相的填充柱,并对它的色谱性能进行了研究。结果表明:甘脲固定相热稳定性高、柱性能稳定,是一种良好的气相色谱固定相。该固定相对烷烃、卤代烃、芳烃、醇、酯、酮、酸、胺等类物质具有良好的分离能力,尤其是对位置异构体(如二取代苯位置异构体)有较好的分离选择性。本文还初步探讨了甘脲固定相的分离机理。

甘脲和羟基葫芦[6]脲气相色谱固定相的制备及其色谱分离性能比较研究

甘脲是羟基葫芦[6]脲(HOCB6)的前体,本文设计了一种在酸性条件下均匀涂渍固定液的新方法,首次将甘脲和羟基葫芦[6]脲用作气相色谱固定相.将甘脲和HOCB6填装成气相色谱填充柱后,以烷烃、卤代烃、芳香烃、醇、酮、酯、酸、胺等物质为探针,用复杂样品花露水对它们的色谱分离性能进行了比较研究.结果表明,甘脲和HOCB6都是良好的气相色谱固定相,热稳定性高,柱性能稳定.两种固定相对以上溶质探针都有较好的分离能力,HOCB6固定相(PSP)与甘脲固定相(GSP)相比较,总体上具有更好的分离选择性,对难分离的芳香族位置异构体(如二甲苯、甲基苯胺)具有良好的分离能力,显示出较高的立体选择性,对花露水中的高沸点组分有较好的分离效果.上述研究也表明,由于溶质在载气中传质比葫芦脲内腔快得多,全包结尽管有利于提高分离选择性,但展宽后的柱效不理想;适当的高柱温既保留了部分包结作用,同时存在端口协同作用,能兼顾高选择性和高柱效.

硝基脲类含能材料的合成及性能研究进展

系统综述了国内外关于硝基脲类含能材料的合成和性能研究进展。重点介绍了硝基五元环脲类尤其是甘脲类含能材料的合成与性能。认为,硝基脲类含能材料具有较好的热稳定性、较高的密度和能量水平,但双硝基脲类化合物的水解稳定性差限制了其应用。指出,甘脲类含能材料和七、八元环硝基脲类含能材料研究相对较少。可考虑设计良好的氮杂环骨架分子,骨架分子中引入硝仿基(—C(NO2)3)、硝基(—NO2)、氨基(—NH2)和硝氨基(N—NO2)等含能基团来合成新型化合物,以提高硝基脲类化合物的实际应用价值。提出了设计与合成新型硝基脲类含能材料的研究方向,附参考文献52篇。

1,10-邻菲咯啉取代苷脲及其一维Ag(Ⅰ)配位聚合物的合成及晶体结构

合成了1,10-邻菲咯啉取代苷脲(L),并用L与硝酸银反应得到一维配位聚合物[AgLNO3]n,利用X-射线衍射方法测定了它们的晶体结构。L:单斜晶系,空间群P21/c,a=1.8545nm,b=1.2504nm,c=1.2818nm,β=108.476°,V=2.8192nm3,Z=7,F(000)=1176,finalGOF=1.093,R1=0.060,wR2=0.1654,。[AgLNO3]n:正交晶系,空间群Pca21,a=1.55149nm,b=1.04907nm,c=1.15892nm,V=1.8863nm3,Z=4,F(000)=1024,finalGOF=1.038,R1=0.042,wR2=0.110。晶体结构表明配体L与Ag髣形成了一维配位聚合物[AgLNO3]n。

四硝基甘脲的合成工艺改进及热分析

以尿素和乙二醛为原料,在盐酸催化下经微波加热制得甘脲（GU）,用发烟硝酸醋酐对GU硝化合成了四硝基甘脲（TNGU）。考察了反应温度、反应时间和发烟硝酸用量等对硝化反应过程的影响。采用红外光谱、核磁共振光谱及元素分析对TNGU结构进行了表征,用DSC对其进行了热分析,用Kissger和Ozawa法确定了TNGU的反应动力学参数,估算了热爆炸临界温度（Tb）及热分解反应的活化熵变（ΔS≠）、活化函变（ΔH≠）和活化吉布斯自由能变化值（ΔG≠）。结果表明,TNGU的较佳合成工艺条件为：GU5g时,发烟硝酸70mL,醋酸酐35mL,反应温度25～30℃,反应时间4h,TNGU收率为84%（以GU计）。此工艺较文献废酸液量减少30mL,硝化时缩短4h。TNGU的Tb为465.34K,ΔS≠、ΔH≠和ΔG≠分别为171.46J·mol-1、195.00kJ·mol-1和194.99kJ·mol-1,TNGU的热分解为放热熵增的过程。

甘脲的合成与鉴定

以乙二醛和尿素为原料,通过酸催化缩合合成甘脲(又称尿缩醛),研究了尿素/乙二醛摩尔比、pH值、反应时间和加料温度等对甘脲收率的影响,并测定了甘脲的物理参数。

四溴甘脲对枯草杆菌黑色变种芽胞损伤作用的电镜观察

为探索四溴甘脲消毒剂杀灭细菌的机理,采用透射电镜技术对四溴甘脲消毒剂处理过的枯草杆菌黑色变种芽胞的超微结构进行了分析和比较。结果显示,以含有效溴274mg/L的四溴甘脲消毒剂作用30m in,可使枯草杆菌黑色变种芽胞杀灭率达到100%。在透射电镜下观察到,经该消毒剂作用的枯草杆菌黑色变种芽胞壳质破损断裂明显,壳内结构模糊,核心溶解,有的芽胞近似空壳。结果显示,四溴甘脲消毒剂杀灭芽胞效果优于普通含氯消毒剂,对细菌芽胞超微结构破坏明显。

1,3,4,6-四氯-3α,6α二苯甘脲的合成

一、引言1,3,4,6-四氯-3α,6α-二苯甘脲是迄今为止在放射性碘标记中性能最佳的非水溶性氧化剂,使用时具有操作简便、快速、标记率高、重现性好、反应条件温和,适用范围广等优点,即可用于标记氨基酸及嘧啶类小分子,又可标记多肽类、激素。

甘脲及其衍生物的研究进展

甘脲自1877年首次合成,随后制备了一系列的甘脲及其衍生物,在涂料、炸药、水处理、电子器材、超分子识别及药物、农药缓释、分子催化等方面具有广泛的用途。简要介绍迄今为止甘脲及其衍生物的制备方法及应用方面的研究进展。

二溴二氯甘脲对枯草杆菌黑色变种芽胞损伤作用的电镜观察

目的探索二溴二氯甘脲消毒剂杀灭细菌的机制。方法采用透射电镜技术对二溴二氯甘脲消毒剂处理过的枯草杆菌黑色变种芽胞的超微结构进行分析和比较。结果以含有效成分284mg/L的二溴二氯甘脲消毒剂作用30min,可使枯草杆菌黑色变种芽胞杀灭率达到99.99%。在透射电镜下观察到,经该消毒剂作用的枯草杆菌黑色变种芽胞壳质破损断裂明显,壳内结构模糊,核心溶解,有的芽胞近似空壳。结论二溴二氯甘脲消毒剂通过破坏细菌芽胞超微结构发挥其消毒作用。

硫代甘脲衍生物合成与电化学性质

在硫酸催化的条件下以硫脲和乙二醛为原料合成硫代甘脲衍生物,采用IR,13CNMR,LC-MS,UV和电化学循环伏安法对其结构和性能进行了表征和分析。该硫代甘脲衍生物分子结构具有很好的对称性,分子中存在离域π键;其难溶于酸,易溶于碱性水溶液和有机碱;在乙二胺中的电导率随溶解量增大而增大,且具有电化学活性。