轴手性2,2'-联吡啶衍生物的合成、表征与催化性质研究

轴手性2, 2'-联吡啶衍生物具有性质稳定、反应条件温和、易于制备等优点,因此被广泛应用于复杂分子的合成及不对称催化等领域。本文设计合成了一系列轴手性2, 2'-联吡啶衍生物L1-L4,通过~1H NMR、~(13)C NMR、X-射线单晶衍射对其组成和结构进行了表征。该类轴手性2,2'-联吡啶衍生物与Pd(II)形成的配合物,能有效催化2-环己烯-1-酮与芳基硼酸的不对称1, 4-加成反应,目标产物具有较好的对映选择性和高达94%的产率。     

(5R)-1-(2,3-二羟基丙基)-5-异丙基-3-取代苯基-2-硫代-4-咪唑烷酮衍生物的合成

咪唑烷酮结构具有重要的生物活性,广泛的存在于已上市药物及临床活性分子中。本文以L-缬氨酸与取代异氰酸苯酯为主要原料,经2步反应,设计合成了6个新型的2-硫代-4-咪唑烷酮衍生物,其结构经~1H NMR与MS确证。可作为候选化合物进行进一步化学结构修饰与活性筛选研究。     

镉基手性金属-有机框架材料的合成与结构表征

以5-氨基间苯二甲酸为起始原料,L-Boc-脯氨酸为手性源,设计合成了一种V型结构的手性配体L-H2,并利用"一锅法"与金属镉离子制备了一种配合物单晶(1),其结构通过X-射线衍射和红外光谱等技术进行了表征,证实(1)是一种具有21螺旋结构的手性金属-有机框架材料.     

一种单手螺旋MOF用于高效液相色谱手性固定相的研究

高效液相色谱(HPLC)手性固定相法因其简单、快速、准确等优点,已成为手性药物对映体分离的重要方法之一。手性金属-有机骨架化合物(MOFs)因结构独特、具有手性官能团或敞开的手性孔穴等特点,在手性识别领域有着广泛的应用潜能。一种单手螺旋的手性MOF材料[{Cu(sala)}n](H2sala=N-(2-hydroxybenzyl)-L-alanine)在气相色谱手性固定相的应用中表现了较好的手性识别能力,但目前尚未见到将其用于HPLC手性固定相的应用报道。成功合成了手性[{Cu(sala)}n]晶体,将其用作固定相制成HPLC手性柱,并采用XRD、TG、SEM等表征其结构。结果表明,[{Cu(sala)}n]晶体制备的HPLC手性柱对特罗格尔碱、1-(1-萘基)-乙醇、联糠醛、1,1'-联-2-萘酚、布洛芬、1,2-二苯乙醇酮和1-(9-蒽基)-2,2,2-三氟乙醇等7种外消旋化合物实现了分离,具有一定的手性识别能力。为开发新型HPLC固定相提供了新途径。     

2-咪唑烷酮合成工艺的研究进展

2-咪唑烷酮及其衍生物作为一类具有广泛市场前景的精细化学品,特别是2-咪唑烷酮在甲醛捕获方面的高效性,探索2-咪唑烷酮具有市场潜力的合成制备方法非常重要。本文在调研国内外大量文献的基础上,对2-咪唑烷酮的光气法、碳氧化物法、碳酸酯法、尿素法等制备方法进行了概述和对比,并指出尿素法和CO2法具有原料及绿色环保优势,是2-咪唑烷酮工业化生产的最大潜力军。     

(-)-1R,2S,5R-8-(4-甲氧基甲基苯)薄荷醇的合成表征

以R-( )-长叶薄荷酮为起始原料,经1,4-加成、还原两步反应合成了手性辅助试剂(-)-1R,2S,5R-8-(4-甲氧基甲基苯)薄荷醇及其反向异构体( )-1S,2S,5R-8-(4-甲氧基甲基苯)薄荷醇,总产率88%.其结构用 1HNMR和 13CNMR进行了表征.     

淀粉三(4-三氟甲氧基苯基氨基甲酸酯)手性固定相的制备及其手性识别能力

制备了基于淀粉三(4-三氟甲氧基苯基氨基甲酸酯)衍生物的涂敷型手性固定相(CSP1),并考察了其手性识别能力。研究表明:与商品化Chiralpak AD柱相比,CSP1显示出较低的手性识别能力;CSP1的手性识别能力随流动相中异丙醇含量的降低而升高;与以乙醇为流动相添加剂相比,使用异丙醇为添加剂更有利于对映体的分离。此研究拓展了多糖类衍生物手性固定相的种类。     

基于β-环糊精/SiO_2手性固定相的薄层色谱法拆分DL-萘普生的研究

用β-环糊精(-βCD)键合硅胶合成了一种新型的β-环糊精/S iO2手性固定相,用红外对其进行了结构鉴定。将该手性固定相用于薄层色谱分离萘普生外消旋体,考察多种溶剂对萘普生外消旋体的展开效果,结果表明,乙酸乙酯∶氯仿(体积比)=1∶4为展开剂时,合成的手性固定相对DL-萘普生的分离度为1.45,具有很好的拆分DL-萘普生的能力。     

1-(1,4-苯并二噁烷-2-羰基)哌嗪对映体的分离研究

1 (1, 4 苯并二口恶烷2 羰基)哌嗪是制备抗高血压药物多沙唑嗪的重要中间体,手性多沙唑嗪可以通过中间体的手性分离来制备。用柱前衍生化-反相高效液相色谱法对1 (1, 4 苯并二口恶烷2 羰基)哌嗪对映体进行了分离。结果表明,用乙酰葡萄糖异硫氰酸酯(GITC)为柱前手性衍生化试剂,C18柱(4 6mm×250mm)为色谱柱,可以将1 (1, 4 苯并二口恶烷2 羰基)哌嗪对映体分离,其他色谱条件为:流动相组成为V(甲醇)∶V(0 02mol/L磷酸二氢钾水溶液) = 53∶47,流速为0 5mL/min,检测波长为250nm。在选择的测定条件下,非对映异构体分离度约等于1 3(R=1 3)。     

N-取代手性吡咯化合物的合成

将2,5-二甲氧基四氢呋喃分别与(R)-4-甲氧基-α-甲基苄胺、(S)-1,2,3,4-四氢萘胺及反式-(1S,2S)-2-氨基环戊醇盐酸盐反应,制备得到3个光学纯的N-取代手性吡咯化合物。目标化合物的结构经过~1H NMR、~(13)C NMR及高分辨率质谱仪(HRMS)表证,旋光度经过旋光测定仪测定。推测了该改良的Paal-Knorr反应机理。     

The Fourth Wake Memorial Lecture

A cyanoalkylation and reduction process was used to synthesize novel imidazolidinone diamine monomers. The diamine monomers, characterized using wet methods and Nuclear Magnetic Resonance, were incorporated into anionic polyurethane/urea dispersion adhesives. Our studies have shown that small amounts of imidazolidinone monomer in anionic polymers can improve adhesion of polyvinyl chloride to itself three-fold, and the adhesion of acrylonitrile/butadiene/styrene copolymer to vinyl at high-temperatures in the presence of a polyfunctional isocyanate. Adhesion improvements are attributed to the polarity and hydrogen-bonding capabilities of the pendant imidazolidinone groups. Gloss improvements correlated well to levels of incorporated diamine.     

Imidazolidinone Diamine Modified Polyurethane Dispersions

A cyanoalkylation and reduction process was used to synthesize novel imidazolidinone diamine monomers. The diamine monomers, characterized using wet methods and Nuclear Magnetic Resonance, were incorporated into anionic polyurethane/urea dispersion adhesives. Our studies have shown that small amounts of imidazolidinone monomer in anionic polymers can improve adhesion of polyvinyl chloride to itself three-fold, and the adhesion of acrylonitrile/butadiene/styrene copolymer to vinyl at high-temperatures in the presence of a polyfunctional isocyanate. Adhesion improvements are attributed to the polarity and hydrogen-bonding capabilities of the pendant imidazolidinone groups. Gloss improvements correlated well to levels of incorporated diamine.     

Off-line monitoring of styrene/butyl acrylate copolymerizations in toluene using ATR-FTIR spectroscopy

The solution copolymerization of styrene/butyl acrylate in toluene was monitored off-line using an ATR-FTIR probe. The probe was used to track the concentration of the starting materials, thereby providing conversion and polymer composition data. Off-line gravimetry and ¹H NMR spectroscopy were used as standard methods to provide a comparison to the ATR-FTIR data. A non-calibrated univariate method was first used to calculate individual monomer conversions by monitoring the peak height of characteristic IR absorbances for each monomer. An alternative, calibrated method using partial least squares (PLS) regression to relate the whole IR spectral changes to monomer concentration was also attempted. The ATR-FTIR spectroscopy with multivariate analysis showed improvement in monitoring the monomer conversion compared to the univariate method. The results agreed with those determined by traditional gravimetric and ¹H NMR spectroscopy analysis.     

溶剂对分子印迹聚合物分子识别能力的影响：实验研究与计算量子化学分析

以茶碱为印迹分子，甲基丙烯酸为功能单体，二甲基丙烯酸乙二醇酯为交联剂，以氯仿、二甲基亚砜和四氢呋喃为溶剂，合成了分子印迹聚合物并测定了其对茶碱分子的识别能力，实验结果显示，在氯仿中合成的MIPs的分子识别性能最佳.综合Scatchard分析吸附行为、¹H NMR测定氢键以及量子化学中的密度泛函计算印迹分子和单体分子的溶剂化能等方法，研究聚合反应的溶剂体系对于印迹聚合物分子识别能力的影响及其作用机制.计算结果显示：采用与印迹分子和单体相互作用力较弱的溶剂体系所合成的印迹聚合物具有较高的分子识别性能.这与¹H NMR分析结果和吸附测定实验结果具有一致性.上述结果表明，溶剂对于分子印迹聚合物的分子识别性能具有重要的影响，而计算量子化学分析对于分子印迹介质合成时的溶剂体系选取和优化具有很好的指导作用.     

Synthesis and characterization of novel fluoropolymers containing sulfonyl and perfluorocyclobutyl units

A novel sulfonyl-containing monomer, 4,4′-sulfonyl-bis(trifluorovinyloxy)biphenyl, and the resulting fluoropolymers with good thermal stability have been prepared. The monomer was synthesized by two steps using 4,4′-sulfonyldiphenol as starting material and characterized by FT-IR, ¹H NMR, ¹³C NMR, ¹⁹F NMR and element analysis in detail. Fluoropolymers containing sulfonyl and perfluorocyclobutyl units were prepared by different polymerization methods. A series of fluoropolymers with higher molecular weights were obtained by solution polymerization in diphenyl ether. The molecular weight is dependent on the polymerization time, polymerization temperature and the concentration of the monomer. The resulting polymers show excellent solubility in conventional solvents and good thermal stability with a high decomposition temperature about 500 °C measured by TGA.     

室温自交联功能单体N,N'-二双丙酮丙酰胺基乙二胺的合成与应用

利用乙二胺与双丙酮丙烯酰胺间的Michael加成反应合成了含酮羰基的新型扩链剂N,N'-二双丙酮丙酰胺基乙二胺,用¹H NMR和¹³C MNR证实了结构。聚己二酸新戊二醇酯、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)预聚后加入N,N'-二双丙酮丙酰胺基乙二胺扩链得到含酮聚氨酯预聚物,预聚物经分散、乙二胺扩链后得到聚氨酯分散体。研究了含酮扩链剂用量对分散体及其膜性能的影响。结果表明随N,N'-二双丙酮丙酰胺基乙二胺的增加,聚氨酯分散体的粒径增大、黏度减小。己二酸二酰肼交联后能明显提高WPU胶膜的力学性能。     

聚合物微球支载L-脯氨酸磺酰胺的合成

以L-羟脯氨酸为手性原料,经过O-烷基化、氨化、磺酰化,制备L-脯氨酸磺酰胺手性单体,在AIBN引发下,与苯乙烯和二乙烯基苯溶液聚合制备了聚苯乙烯微球支载的L-脯氨酸磺酰胺化合物,用IR,1H NMR,13C NMR及元素分析对其进行表征,其支载容量为0.70 mmol/g,总产率27.66%,所得结果与其结构相吻合。     

Synthesis of UV‐curable difunctional silane monomer based on 3‐methacryloxy propyl trimethoxysilane (3‐MPTS) and its UV‐curing characteristics and thermal stability

In the present investigation, silicon containing UV‐curable difunctional monomer was synthesized by reacting 3‐methacryloxy propyl trimethoxysilane (3‐MPTS) with acrylic acid using anhydrous ether as a solvent under inert atmosphere. The synthesized acryloxymethacryloxy silane monomer was characterized by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. The silane monomer along with 4 wt % photoinitiator (Darocure 1173) was cured under UV‐light for different exposure time. The curing characteristic of the monomer was investigated using FTIR spectroscopy. The conversion of the double bond due to curing has been evaluated from the peak intensity of the C?C double bond (at 1636 cm^?1) in the FTIR spectrum considering the peak intensity at 1720 cm^?1 due to C?O as internal standard. The maximum double bond conversion is observed to be 72%. The optimum cure time for the silane monomer has been estimated to be 7.8 sec. The UV‐cured sample decomposes at 440°C. The char residue is 35% at 700°C. The synthesized UV‐curable silane monomer may be useful for UV‐coating formulations, for fabrication of 3D‐objects by lithographic technique and as a precursor for organic–inorganic hybrid materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

二甲基二烯丙基氯化铵合成工艺研究

本文研究了反应物料投加比对产物二甲基二烯丙基氯化铵（DMDAAC）单体收率及其参加与丙烯酰胺（AM）共聚反应活性的影响。以二甲胺、氯丙烯、氢氧化钠为原料一步法制备DMDAAC,以10%阳离子度二甲基二烯丙基氯化铵-丙烯酰胺共聚物PDA的聚合反应为模板,采用单体产物收率和聚合产物特征黏度为主要考核指标,对制备DMDAAC单体的投料比对上述两考核指标的影响进行了系统研究。结果表明,反应物投料比不仅对单体收率,而且对其参加共聚反应的反应活性有直接影响。反应物投料比为n氯丙烯:n氢氧化钠:n二甲胺 =2.08:0.965:1时,以二甲胺计的DMDAAC单体收率为92.7%,DMDAAC单体产物制备10%阳离子度PDA聚合产物较佳特征黏度为12.8dL/g。对单体和共聚产物进行了红外光谱和核磁表征。研究结果可为进一步研制高收率、高纯度、高反应活性DMDAAC单体产物奠定实验基础。     

Synthesis, characterization, and cyclopolymerization of a functional non-symmetric divinyl monomer

A non-symmetric divinyl monomer with terminal carboxylic acid functionality was readily synthesized from the reaction of ethyl α-hydroxymethylacrylate (EHMA) with maleic anhydride. The new monomer (EHMA-MA) was homopolymerized in both bulk and ethyl acetate using AIBN as an initiator to give cyclopolymers. The synthesis of the monomer and cyclopolymers were followed by ¹³C NMR, ¹H NMR, and FTIR. ¹H NMR was also utilized to obtain the degree of cyclization of the polymers, which were found to be 95% or higher in all cases. The molecular weights of the cyclopolymers were around 40-60,000 g/mol as estimated by SEC. The cyclopolymers were thermally stable up to 150 °C. Although the cyclopolymers obtained were not water-soluble; they were soluble in aqueous 1 M NaOH solution. In addition to the carboxylic acid functionality present, the cyclopolymers also had an ethyl ester and a lactone moiety. These functional groups were reacted with hexylamine to obtain a polymer with imide and amide moieties.