苯乙炔衍生物的合成

苯乙炔及取代苯乙炔，是重要的工业原料和有机合成中间体，在药物合成，昆虫信息素的合成，液晶材料等方面均有十分广泛的应用，目前，国内在这些方面的研究尚少，因此，研究探讨其合成方法有非常重要的意义。本文结合研究工作以及前人的经验，按合成方法进行概述。     

苯乙炔衍生物的合成

苯乙炔及取代苯乙炔,是重要的工业原料和有机合成中间体,在药物合成、昆虫信息素的合成、液晶材料等方面均有十分广泛的应用。目前,国内在这些方面的研究尚少,因此,研究探讨其合成方法有非常重要的意义。本文结合研究工作以及前人的经验,按合成方法进行概述。     

苯乙烯存在下的苯乙炔选择性加氢技术

去除苯乙烯(ST)中的苯乙炔(PA)是生产高品质苯乙烯单体产品的重要环节。除去苯乙烯中苯乙炔杂质的最有效的主要方法是将苯乙炔在催化剂的作用下，将其选择性加氢转化成苯乙烯。本文较详细地介绍了当前各专利厂商的苯乙炔选择性加氢催化剂的开发研究情况。主要对各种催化剂的制备方法、操作条件和主要问题进行了介绍。另外介绍两种苯乙烯存在下苯乙炔选择性加氢的工艺过程。最后对几种适用于不同操作条件下的催化剂进行了对比，指出了今后研究工作的重点。     

1,4-二苯乙炔基苯衍生物的合成和发光性能研究

以对二溴苯衍生物和苯乙炔为原料,通过Sonogashira钯催化偶联反应,获得标题化合物.并通过紫外光谱和荧光光谱研究了其发光性能.     

苯乙炔选择性加氢催化剂的研究进展

对各种苯乙炔选择性加氢催化剂的开发研究情况进行了详细介绍。由于负载型钯催化剂和镍催化剂在加氢反应领域应用广泛,本文对这两种催化剂进行了重点介绍。阐述了各种催化剂的性能、使用条件、存在的主要问题、失活原因以及改进措施。提出今后对苯乙炔选择性加氢催化剂的改进应以高空速、适当提高操作温度、改善对原料的适应性等为目标。     

含苯乙炔基的酰亚胺低聚物及其复合材料研究

制备了一种侧链含苯乙炔基的二胺单体2,4-二氨基[4'-(4-苯乙炔基酞酰亚胺基)]二苯醚(DPED),并合成了基于2,3',3,4'-联苯四甲酸二酐(3,4'-BPDA)和DPED的酰亚胺低聚物,通过热重分析,示差扫描量热分析,1H NMR,熔点和力学性能测试研究了DPED的结构及固化行为,低聚物和其固化物及其碳纤维增强复合材料的性能。结果表明:在主链化学结构相同的情况下,将DPED引入到分子质量约为5 000 g/mol的低聚物中,低聚物熔体粘度会有显著降低,侧链苯乙炔基含量越高,其熔体粘度越低,含侧链苯乙炔基的树脂基复合材料的压缩强度高于不含侧链苯乙炔基复合材料,其值分别为570 MPa和415 MPa。     

苯乙炔的合成研究

苯乙烯与溴在四氯化碳中于１０～１５℃反应生成１,２ 二溴乙苯,后者与氢氧化钾在甲醇中回流脱溴化氢生成苯乙炔,总收率６０％。     

取代聚苯乙炔环状三聚体的合成

以对溴苯酚为原料,经四步反应合成一种取代苯乙炔单体4-乙炔基-(2,6)二羟甲基-1-十二烷基酚醚。利用手性的铑催化剂引发聚合,得到高分子量的螺旋聚合物,通过GPC和CD对分子量和螺旋结构进行表征。最后通过光环化反应高效合成了环状三聚体,并通过1HNMR和GPC确认其化合物结构。     

苯乙烯存在下苯乙炔选择性加氢过程的研究

用高压反应釜对一种骨架Ni催化剂和八种Pd/Al₂O₃催化剂在苯乙烯环境下,对连串反应苯乙炔的选择性加氢性能进行了实验评价。通过一系列实验考察了催化剂活性组分负载量、反应温度、反应压力、反应时间和搅拌速率对反应结果的影响。反应结果的评价指标为苯乙炔转化率、苯乙烯收率和二者的综合。研究结果表明,骨架Ni催化剂的活性和选择性均较差,不适宜用作苯乙烯环境下的苯乙炔加氢过程。对Pd/Al₂O₃型催化剂而言,较低的反应温度和微正压的反应条件对苯乙炔的选择性加氢有利;延长反应时间无助于苯乙炔转化率的提高,相反却会导致苯乙烯收率的迅速降低;提高搅拌速率可以消除相间扩散传质对反应过程的影响,因此对苯乙炔的选择性加氢是有利的。另外,在实验研究的反应条件范围内,苯乙炔的转化率似乎存在一个极限值,分析认为这可能是由于催化剂的比表面积和活性组分负载量太高引起的。     

2-(苯乙炔基)烟碱醛的合成研究

以2-氯烟碱醛和苯乙炔为原料,在双三苯基膦二氯化钯催化作用下,发生Sonogashira偶联反应,得到目标化合物2-(苯乙炔基)烟碱醛,产物结构通过核磁共振氢谱和质谱表征.并研究该偶联反应最佳条件为:物料比n(苯乙炔)∶n(2-氯烟碱醛)=1.8∶1;钯催化剂用量为n(双三苯基膦二氯化钯)∶n(2-氯烟碱醛)=0.06...     

一种酚羟基苄基保护基的脱除方法

提出了一种脱除酚类化合物羟基苄基保护基的方法。采用多聚磷酸(PPA)-浓盐酸-乙醇体系脱除苄基保护基,通过单因素实验考察PPA物质的量、浓盐酸与PPA体积比、反应时间以及反应温度对产率的影响。结果表明,n(PPA)=0.2 mmol、V(浓盐酸)∶V(PPA)=100∶1、反应时间3 h、反应温度85℃为最佳反应条件。采用优化条件得到9个脱苄基化合物,产率为70.4%~92.7%,其中2'-苄氧基取代查尔酮脱掉苄基的同时环合得到二氢黄酮。所得产物结构经MS、1HNMR及13CNMR进行确证。     

Hexokinase 2 Inhibition and Biological Effects of BNBZ and Its Derivatives: The Influence of the Number and Arrangement of Hydroxyl Groups

Hexokinase 2 (HK2), an enzyme of the sugar kinase family, plays a dual role in glucose metabolism and mediating cancer cell apoptosis, making it an attractive target for cancer therapy. While positive HK2 expression usually promotes cancer cells survival, silencing or inhibiting this enzyme has been found to improve the effectiveness of anti-cancer drugs and even result in cancer cell death. Previously, benitrobenrazide (BNBZ) was characterized as a potent HK2 inhibitor with good anti-cancer activity in mice, but the effect of its trihydroxy moiety (pyrogallol-like) on inhibitory activity and some cellular functions has not been fully understood. Therefore, the main goal of this study was to obtain the parent BNBZ (2a) and its three dihydroxy derivatives 2b–2d and to conduct additional physicochemical and biological investigations. The research hypothesis assumed that the HK2 inhibitory activity of the tested compounds depends on the number and location of hydroxyl groups in their chemical structure. Among many studies, the binding affinity to HK2 was determined and two human liver cancer cell lines, HepG2 and HUH7, were used and exposed to chemicals at various times: 24 h, 48 h and 72 h. The study showed that the modifications to the structures of the new BNBZ derivatives led to significant changes in their activities. It was also found that these compounds tend to aggregate and exhibit toxic effects. They were found to contribute to: (a) DNA damage, (b) increased ROS production, and (c) disruption of cell cycle progression. It was observed that, HepG2, occurred much more sensitive to the tested chemicals than the HUH7 cells; However, regardless of the used cell line it seems that the increase in the expression of HK2 in cancer cells compared to normal cells which have HK2 at a very low level, is a serious obstacle in anti-cancer therapy and efforts to find the effective inhibitors of this enzyme should be intensified.     

铝酸钙玻璃中羟基对红外透过性能的影响

采用不同熔化方法制备了铝酸钙红外玻璃并考察了其红外透过性能。研究了结构中的羟基对玻璃红外透过性能的影响。通过红外光谱和固体核磁共振技术对玻璃中羟基的结构特征、氢键结合状态以及红外吸收情况进行了研究和探讨。结果表明:羟基会引起铝酸钙玻璃在近红外2.9μm左右的宽带吸收,这是由于玻璃中羟基结构形式的多样化所造成的;在玻璃结构中,羟基与氢键结合会造成振动频率下降,红外吸收峰向长波移动,羟基氢键结合强度越大,长波移动越严重,羟基与氢键结合形式越多,羟基的红外吸收范围越宽;在铝酸钙红外玻璃中主要存在3种羟基存在形式:孤立羟基基团、邻近的羟基对和带有氢键的单个羟基。不同制备方法获得的玻璃结构中羟基存在形式基本相同。     

Studies on Methylation of Anomeric Hydroxyl Groups Under Phase-Transfer Catalysed Conditions

Reaction derivatives of monosaccharides possessing a free anomeric hydroxyl group with methyl sulfate under phase-transfer catalysed conditions is described. Under phase-transfer conditions, which permit equilibrium control, the proportions of α- to β-glycosides are determined by the relative acidity of anomers. In the presence of alcohols the proportions of α to β-D-gluco- and galactopyranosides have been shifted in favor of the equatorial anomer.     

甲基丙烯甲酯及其衍生物的共聚研究

以甲基丙烯酸甲酯和一缩二乙二醇为原料,甲醇钠为催化剂,石油醚为溶剂,合成了一缩二乙二醇甲基丙烯酸酯。然后,以单酯和甲基丙烯酸羟乙酯为原料,偶氮二异丁腈为引发剂,合成了一缩二乙二醇甲基丙烯酸酯与甲基丙烯酸羟乙酯的共聚物(2-p-HEMA)。     

Synthesis of Novel D-Pi-A Chromophore with Two Hydroxyl Groups in Electron Donor

New electro optical chromophore with 4-(diethylamino)-2,6-bis((6-hydroxyhexyl)oxy)benzaldehyde as electron donor was synthesized and characterized by ¹H NMR spectra and mass spectra. Two long branches were introduced to the electron donor to reduce the interaction among the chromophores and improve the chromophores’ solubility. Hydroxyl groups were introduced to branches’ end, which could be easily reacted with isocyanate affording us polyurethane. In this article, novel polyurethane with this new chromophore as side chains was prepared and used as thermo optical films by spin coating. These films showed us low optical absorption at communication wavelength, good thermal stability and large thermo-optics coefficients.     

Estimation of Phenolic Hydroxyl Groups in Wood by a Periodate Oxidation Method

Oxidation of woodmeals with an excess of aqueous sodium periodate solution at 4°C released an amount of methanol approximately equivalent to the phenolic hydroxyl content of the lignin as determined by the aminolysis method. The periodate and aminolysis methods gave very comparable data for Norway spruce and aspen woodmeal samples.