离子液体中6-(2,3-环氧丙氧基)-2(1H)-喹啉酮及其衍生物的合成

6-(3-氨基-2-羟基丙基)-2-(1H)-喹啉酮衍生物被发现具有新的正性肌力的活性. 设计合成了一系列新的氨丙醇类喹啉酮化合物. 首先研究了6-羟基-2-(1H)-喹啉酮环氧化物2在离子液体中的合成, 该反应后处理简便, 收率高, 对环境友好. 然后用合成得到的2-(1H)-喹啉酮环氧化合物在离子液体中与一系列具有生物活性的有机碱反应, 合成了氨丙醇类2-(1H)-喹啉酮化合物3. 然后由6-羟基-2-(1H)-喹啉酮出发, 在离子液体中, 进行了一锅法合成氨丙醇类2-(1H)-喹啉酮化合物的研究. 制得的2b, 3b～3f 6个新化合物用IR, ¹H NMR, MS和元素分析进行了结构表征.     

Odd-Even Effects in the Dielectric Properties of Nematics 4-(Trans-4'-N-Alkylcyclohexyl)Isothiocyanatobenzenes

The anisotropy of the static electric permittivity and conductivity for the homologous series of nematics: 4-(trans-4'-n-alkylcyclohexyl)isothiocyanato-benzenes (n-CHBT) for n = 3-10 have been measured. It is shown that the odd-even effect in the dielectric anisotropy Ac is related to the perpendicular component of electric permittivity. The odd-even effect is found in n-CHBT for both the anisotropy in the conductivity and the activation energy for ionic movement.     

Odd-Even Effects in the Dielectric Properties of Nematics 4-(Trans-4′-N-Alkylcyclohexyl)Isothiocyanatobenzenes

Abstract

The anisotropy of the static electric permittivity and conductivity for the homologous series of nematics: 4-(trans-4′-n-alkylcyclohexyl)isothiocyanato-benzenes (n-CHBT) for n = 3–10 have been measured. It is shown that the odd-even effect in the dielectric anisotropy Ac is related to the perpendicular component of electric permittivity. The odd-even effect is found in n-CHBT for both the anisotropy in the conductivity and the activation energy for ionic movement.     

1-(4-氯苯胺基)-4-(4-吡啶甲基)-2,3-二氮杂萘琥珀酸盐的合成与抑制肿瘤活性

研究了1-(4-氯苯胺基)-4-(4-吡啶甲基)-2,3-二氮杂萘琥珀酸盐的合成工艺,采用苯酞和吡啶甲醛为起始原料,经加成、重排、取代和成盐4步反应得到目标化合物。 中间体及目标化合物通过1H NMR、MS和HPLC进行了表征。 重结晶纯化后的目标化合物纯度为98.1%。 对荷瘤（人大肠癌HT 29细胞）裸鼠的抑癌活性测定表明,该化合物具有明显的抑制肿瘤生长作用。     

Dielectric and switching properties of a highly tilted AFLC material (S)-(+)-4-(1-methylheptyloxycarbonyl)-2,3-difluorophenyl 4′-[3-(2,2,3,3,4,4,4-heptafluorobutoxy)prop-1-oxy]biphenyl-4-carboxylate

Thermodynamic, dielectric, optical and switching parameters of a single-phase antiferroelectric (AF) liquid crystalline material (S)-(+)-4-(1-methylheptyloxycarbonyl)-2,3-difluorophenyl 4′-[3-(2,2,3,3,4,4,4-heptafluorobutoxy)prop-1-oxy]biphenyl-4-carboxylate have been studied. These studies show wide temperature range (~97.8°C–25.3°C) of AF SmC^*_A phase in the material. The dielectric studies have been carried out in the frequency range of 1 Hz–35 MHz under planar anchoring conditions of the molecules. The dielectric spectrum of the SmC^*_A phase exhibits three relaxation modes due to the collective as well as individual molecular processes. Relaxation frequencies of these modes lie in the range of kHz–MHz regions. Relative permittivity of the material (at 10 kHz) varies from ~8.8 at 98.8°C to 9.9 at 41.0°C. Maximum tilt of the molecule in the SmC^*_A phase is ~43°C. Spontaneous polarisation, switching time and rotational viscosity have also been determined. The maximum value of P_S is ~439 nC/cm² and switching time is the order of 1–5 millisecond, whereas viscosity is moderate.     

Mesogenic 4-acryloyloxy- and 4-(2,3-epoxypropoxy)phenyl 4-alkoxybenzoates

Procedures were developed which made it possible to synthesize in good yields homologs of 4-acryloyloxyphenyl 4-alkoxybenzoates (C₃, C₅, C₇, C₈) and of 4-(2,3-epoxypropoxy)phenyl 4-alkoxybenzoates (C₅, C₇). The substituted phenylbenzoates obtained exhibit the enantiotropic nematic mesomorphism in a sufficiently wide temperature range. The studied compounds have absorption maxima in the near UV region and a high temperature of decomposition beginning.     

Dielectric Properties of Diols and Triols: 2,3-Butanediol

The results of experimental studies of the dielectric properties of 2,3-butanediol are reported. Static dielectric constant ɛ_s was measured at 1 MHz; dielectric constant ɛ′ and dielectric loss ɛ″ were determined by the balance method over the frequency range 2–37.5 GHz and the temperature range 293–423 K. Original Russian Text ? V.I. Zhuravlev, N.V. Lifanova, T.M. Usacheva, E.P. Vydrina, 2008, published in Zhurnal Fizicheskoi Khimii, 2008, Vol. 82, No. 4, pp. 780–781.     

Synthesis of 4-(2-chloroethyl)-2,3-dihydro[1,4]oxazino[2,3-b]quinoline and 4-(2-chloroethyl)2,3-dihydropyrido[2,3-b][1,4]oxazine

The title compounds were synthesized from 3-[bis(2-hydroxyethyl)amino]quinolin-2(1H)-one 11a and 3-[bis(2-hydroxyethyl)amino]pyridin-2(1H)-one 18 respectively. The preparation involved a tandem chlorination/cyclization reaction.     

Electroentrapment of Polyaniline in [3-(2,3-Epoxypropoxy)propyl]trimethoxysilane-Derived Xerogel: A Facile Methodology Towards Molecularly Imprinted Xerogels

A novel polyaniline (PANI)/silica hybrid composite, as a selective coating, was synthesized by the simultaneous sol–gel process and in situ electro-polymerization of aniline and employed for imprinting naproxen. The synthesized composite was chemically bonded inside a copper tube for online capillary microextraction (CME) in combination with high-performance liquid chromatography (HPLC). The copper tube was intended for use as an unbreakable substrate for CME and the HPLC injection loop. Four copper tubes containing different coatings were prepared accordingly to achieve the most appropriate extracting medium for naproxen. Coating 1 was a xerogel of [3-(2,3-epoxypropoxy)propyl]trimethoxysilane (EPPTMOS) synthesized by sol–gel technology and PANI as a conductive polymer (CP) was electrochemically prepared as coating 2. Coating 3 (sol–gel–CP) included the electroentrapped PANI into the xerogel of EPPTMOS, representing the non-imprinted xerogel (NIX) and coating 4, the molecularly imprinted xerogel (MIX), contained entrapped PANI into the xerogel of EPPTMOS, while naproxen template was already imprinted into the composite structure. Extraction efficiency of MIX towards naproxen was about 4–30 times greater than the others. Electroentrapped PANI into the silica xerogel might be responsible for the enhanced extraction efficiency, originating from high surface area of PANI as well as its role in π–π interactions. The mild conditions used in this process enabled the incorporation of organic species such as PANI into the silica particles without degradation. The main advantage of addition of PANI during the sol–gel process was the reduction of gelation time from more than a week to a few hours and, therefore, achieving a facile and controllable method for preparation of selective media. Furosemide, clodinafop-propargyl and haloxyfop-etotyl were also selected to investigate selectivity of the prepared MIX towards naproxen. Ratio of MIX/NIX, a criterion of selectivity, was 3.8, 1.1, 1.2, and 1.4 for naproxen, clodinafop, haloxyfop and furosemide, respectively. The linearity of the HPLC method for naproxen was in the range of 10–1,000 µg L^?1. The limit of detection value was found to be 5 µg L^?1 and RSD % of 2.9 (n = 5) was obtained. Real samples such as blood plasma and urine species were analyzed by the developed method and the relative recovery percentages of 76 and 94 % were obtained for the spiked samples.     

Electroentrapment of Polyaniline in [3-(2,3-Epoxypropoxy)propyl]trimethoxysilane-Derived Xerogel: A Facile Methodology Towards Molecularly Imprinted Xerogels

A novel polyaniline (PANI)/silica hybrid composite, as a selective coating, was synthesized by the simultaneous sol–gel process and in situ electro-polymerization of aniline and employed for imprinting naproxen. The synthesized composite was chemically bonded inside a copper tube for online capillary microextraction (CME) in combination with high-performance liquid chromatography (HPLC). The copper tube was intended for use as an unbreakable substrate for CME and the HPLC injection loop. Four copper tubes containing different coatings were prepared accordingly to achieve the most appropriate extracting medium for naproxen. Coating 1 was a xerogel of [3-(2,3-epoxypropoxy)propyl]trimethoxysilane (EPPTMOS) synthesized by sol–gel technology and PANI as a conductive polymer (CP) was electrochemically prepared as coating 2. Coating 3 (sol–gel–CP) included the electroentrapped PANI into the xerogel of EPPTMOS, representing the non-imprinted xerogel (NIX) and coating 4, the molecularly imprinted xerogel (MIX), contained entrapped PANI into the xerogel of EPPTMOS, while naproxen template was already imprinted into the composite structure. Extraction efficiency of MIX towards naproxen was about 4–30 times greater than the others. Electroentrapped PANI into the silica xerogel might be responsible for the enhanced extraction efficiency, originating from high surface area of PANI as well as its role in π–π interactions. The mild conditions used in this process enabled the incorporation of organic species such as PANI into the silica particles without degradation. The main advantage of addition of PANI during the sol–gel process was the reduction of gelation time from more than a week to a few hours and, therefore, achieving a facile and controllable method for preparation of selective media. Furosemide, clodinafop-propargyl and haloxyfop-etotyl were also selected to investigate selectivity of the prepared MIX towards naproxen. Ratio of MIX/NIX, a criterion of selectivity, was 3.8, 1.1, 1.2, and 1.4 for naproxen, clodinafop, haloxyfop and furosemide, respectively. The linearity of the HPLC method for naproxen was in the range of 10–1,000 µg L⁻¹. The limit of detection value was found to be 5 µg L⁻¹ and RSD % of 2.9 (n = 5) was obtained. Real samples such as blood plasma and urine species were analyzed by the developed method and the relative recovery percentages of 76 and 94 % were obtained for the spiked samples.

     

Dielectric,viscous and elastic properties of nematogenic 1-(4- trans -propylcyclohexyl)-2-(4-cyanophenyl)ethane

This paper presents the results of measurements of the static and dynamic electric permittivity, the shear viscosity of a freely flowing sample, and the splay and bend elastic constants for 1-(4-trans -propylcyclohexyl)-2-(4-cyanophenyl)ethane (C3H7-CyHx-CH2CH2-Ph-C=N) (3CCPE). The static permittivity of the isotropic phase shows pre-nematic critical behaviour which is discussed in the frame of the fluid-like model of Mukherjee. From the temperature dependence of the dielectric relaxation time (corresponding to the molecular rotation around the short axis) and the shear viscosity, the strength of the nematic potential and the effective length of the 3CCPE molecule (in the isotropic phase), were estimated. The splay and bend elastic constants were determined from the voltage dependence of the capacitance of a planar nematic cell.     

Dielectric, viscous and elastic properties of nematogenic 1-(4- trans -propylcyclohexyl)-2-(4-cyanophenyl)ethane

This paper presents the results of measurements of the static and dynamic electric permittivity, the shear viscosity of a freely flowing sample, and the splay and bend elastic constants for 1-(4- trans -propylcyclohexyl)-2-(4-cyanophenyl)ethane (C 3 H 7 -CyHx-CH 2 CH 2 -Ph-C=N) (3CCPE). The static permittivity of the isotropic phase shows pre-nematic critical behaviour which is discussed in the frame of the fluid-like model of Mukherjee. From the temperature dependence of the dielectric relaxation time (corresponding to the molecular rotation around the short axis) and the shear viscosity, the strength of the nematic potential and the effective length of the 3CCPE molecule (in the isotropic phase), were estimated. The splay and bend elastic constants were determined from the voltage dependence of the capacitance of a planar nematic cell.     

1,4-二哌啶基-2,3-二(4-甲基苯基)-2,3-丁二醇的结构研究

测定了1,4-二哌啶基-2,3-二(4-甲基苯基)-2,3-丁二醇(dl)的晶体结构,并在此基础上用半经验分子轨道理论方法研究了该分子的电子结构,讨论了分子结构的一些特征。     

2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯的合成、晶体结构及性能研究

以硝基甲烷为起始原料,经缩合、环化、氧化耦合、脱缩酮及硝化等5步反应合成了2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯(BHDBT),总收率为36.1％,并采用核磁共振谱、红外光谱以及元素分析等进行了结构表征.用浓盐酸代替氯化氢气体,改进了关键中间体2,3-二羟甲基-2,3-二硝基-1,4-丁二醇(BHDB)的合成方法,并确定最佳反应条件为:刀(浓盐酸):n(BDND)=1.1∶1,反应温度55℃,时间4h,收率为94.8％.首次发现了BHDB和BHDBT的亚甲基质子具有磁不等价性,并从理论上分析其产生的原因.培养了BHDBT单晶,四元衍射晶体结构解析表明:BHDBT属于单斜晶系,空间群P2(1)/n,晶胞参数:a=0.81944(11) nm,b=2.3365(3) nm,c=0.85838(11) nm,a=90°,β=113.501(2)°,y=90°,V=1.5072(3) nm3,Z=4,Dc=1.852 g·cm-3,μ=0.189 mm-1,F(000)=856.BHDBT熔点为86.37℃,分解峰温度为185.79℃(DSC),摩擦感度为100％ (3.92 MPa,90°),特性落高H50为10.0 cm(5 kg).     

Synthesis of 4-Substituted-4-(Diethylphosphono)-2-Methylbuta-2,3-dien-1-oles

Several 4-substituted 4-(diethylphosphono)-2-methylbuta-2,3-dien-1-oles 4a-f were synthesized by a simple and efficient three-step procedure starting from acetylene derivatives.     

2,3-二硫苄基-6,7-二(2-氰基乙硫基)四硫富瓦烯的合成及其性质研究

设计合成了2,3-二硫苄基-6,7-二(2-氰基乙硫基)四硫富瓦烯. 以UV-Vis, ¹H NMR, IR, MS和元素分析进行了表征, 测定了产物的循环伏安图. 运用Gaussian 98量子化学程序包, 采用密度泛函 (DFT) 的方法, 在B3LYP/6-31G(d) 水平上对分子的几何构型进行了优化. 计算结果表明, 由于取代基的引入使体系的HOMO能量降低, 分子趋于稳定, 这与分子的设计是一致的.     

Synthesis and Complexing Properties of Alkyl (3-Oxo-2,3-dihydrothiophen-2-ylidene)- and (4-Oxothiazolidin-5-ylidene)acetate Derivatives

Condensation of dimethyl and diethyl acetylenedicarboxylate with thioacetamides gave the corresponding alkyl (3-oxo-2,3-dihydrothiophen-2-ylidene)- and (4-oxothiazolidin-5-ylidene)acetates. Treatment of these compounds with zinc in acetic acid resulted in reduction of the exocyclic double bonds. The products can be used in membrane processes as sodium cation carriers.     

含3-甲基苯基-2,3-二氮杂萘-1-酮结构聚醚酰胺的合成、表征与性能

合成了一种新型芳香二胺双-(4-氨基苯基)-4-(3-甲基-4-苯氧基)-2,3-二氮杂萘-1-酮(1)[2-(4-aminophenyl)-4-(3-methyl-4-phenoxy)-2,3-phthalazinone-1,DAMPP].采用Yamazaki体系,二胺(1)能与多种芳香二酸进行溶液亲核缩聚反应,制得一类新型聚芳醚酰胺,其特性粘度为0.40～0.60dL/g;以MS,FTIR和¹HNMR等分析手段研究了新型二胺单体及其聚合物的结构;利用DSC和TGA研究了聚合物的耐热性能,结果表明,新型聚芳酰胺具有高的玻璃化转变温度为598～620K,N2气气氛中10%热质量损失温度在673K以上.聚合物2a～2c的表面电阻系数为3.75×10¹⁴～9.87×10¹⁵Ω,体积电阻系数为1.39×10¹⁶～4.09×10¹⁶Ω·cm.聚合物在二甲基甲酰胺、1-甲基吡咯烷酮和间甲酚等极性有机溶剂中可溶解,并经浇注得到透明、韧性薄膜.     

Properties and Application Prospects of 1-(Vinyloxyalkoxy)propylene 2,3-Oxide Copolymers

Thermal stability, impact strength, folding resistance, and adhesion were studied for copolymers of vinyl chloride and 1-(vinyloxyalkoxy)propylene 2,3-oxides prepared in acetone and dimethyl sulfoxide.