二铬氢四吡啶合钴（II）存在下吡啶叶立德与1,4－萘醌的反应

研究了在[(Py)_4Co(HCrO_4)_2]存在下，吡啶叶立德、喹啉叶立德或异喹啉叶 立德分别和1,4-萘醌反应，一步法合成萘并[2,3-a]中氮茚－7，12－二酮类衍生物 （6a～6d,8a～8c,10a～10c）的结果。该方法原料易得，反应条件容易控制，从而 提供了一种合成这类化合物的新方法。     

ω-氯氟烷基醇,烯烃及环氧化物的合成

本文报道在引发剂存在下, ω-氯氟烷基碘与烯丙基化合物(CH~2=CH-CH~2X, X=OH,OAC) 及乙烯基化合物CH~2=CH-OAC 发生自由基加成反应, 生成相应的加成产物Cl(CF~2)~nCH~2CHICH~2OH (2a～d), Cl(CF~2)~nCH~2CHICH~2OAC (3a～d)和Cl(CF~2)~nCH~2CHIOAC (4a～d) , 产率较好.2a～d用LiAlH~4脱碘生成Cl(CF~2)~nCH~2CH~2CH~2OH(5a～d), 反应条件温和. 2a～d与KOH-CH~3OH反应， 主要得到醇Cl(CF~2)~nCH=CHCH~2OH (6a～c), 若2a～d与NaOH-水溶液反应则得到环氧丙烷化合物. 在少量HOAC存在下， 异丙醇溶剂中， 锌粉与2a～d和3a～d反应得到消除产物Cl(CF~2)~n-CH~2CH=CH~2 (8a～d) . 4a～d与锌反应，再经KOH-CH~3OH-H~2O水解得到Cl(CF~2)~n(CH~2)~2OH(10a～d).     

Synthesis and Bioactivity of Novel Bis‐heterocyclic Compounds Containing Pyrazole and Oxadiazoline

Nucleophilic addition of the starting material 3‐aryl‐1‐phenyl‐4‐formylpyrazoles ( 1～3 ) and 4‐substituted aryloxyacetyl hydrazine ( 4a～4e ) afford hydrazone compounds containg pyrazolyl ( 5a～5e, 6a～6e, 7a～7e ) in the ethanol. These adducts were refluxed in Ac₂O and furnished a series of novel bis‐hetero‐cyclic compounds. ( 8a～8e, 9a～9e, 10a～10e ) via cyclic reaction. The structures of all newly synthesized compounds were established by IR, ¹H NMR, MS and elemental analysis. New compounds conducted preliminary tests of antibacterial activities about Fusarium oxyaporium, Verticillium dahliae, Rhizoctonia solani, Pychium aphanidermatum, Alternaria solani, Sclerotinia sclerotiorum. The results showed that the inhibiting rate of the bis‐heterocyclic compounds ( 8a～8e, 9a～9e, 10a～10e ) was higher than the pyrazolyl hydrazones ( 5a～5e, 6a～6e, 7a～7e ) obviously.     

Facile Microwave‐assisted Synthesis of 1,3,5‐Trisubstituted Pyrazoline Derivatives Incorporating Sulfonyl Moiety

We developed an environmentally benign, convenient microwave‐assisted process for the construction of 1,3,5‐trisubstitued pyrazolines ( 10a ～ 10f , 11a ～ 11f , 12a ～ 12f , 13a ～ 13f ). Chalcones, as the key intermedi‐ ates, were obtained by the condensation of each of appropriately substituted aromatic aldehydes ( 1 ～ 4 ) with 4‐substituted acetophenones ( 5a ～ 5f ) via a Claisen‐Schmidt reaction under the action of microwave irradiation. Cyclization of the chalcones ( 6a ～ 6f , 7a ～ 7f , 8a ～ 8f , 9a ～ 9f ) with p‐toluene sulfonhydrazide af‐ forded 1,3,5‐trisubstitued pyrazoline derivatives using microwave‐assisted process in 25 min and 140 watt power in glycol. The structures of targeted compounds were established by IR, ¹H NMR, MS and ele‐ mental analysis. The results indicate that microwave‐assisted synthetic process presents advantages in terms of enhancement in rate, decrease in reaction time, clean reaction and convenient operation.     

2-芳基-5-(6-哒嗪酮-3-基)-1,3,4-噁二唑的合成

1,4,5,6-四氢-6-哒嗪酮-3-甲酰肼(1)和1,6-二氢-6-哒嗪酮-3-甲酰肼(2)与芳香醛反应得到相应的芳香醛腙3a～3g和5a～5g, 再将3a～3g, 5a～5g在溴的作用下, 合环得到一系列1,3,4-噁二唑的衍生物4a～4g和6a～6g. 化合物的结构经1H NMR, IR, MS和元素分析得以证实.     

新型Co(salen)化合物的合成，表征及其硫醚不对称氧化反应(英)

合成并表征了新的Co(salen)化合物（2a～2c和3a～3c）。手性Co^Ⅱ(salen)化合物2a～2c在硫醚的不对称氧化反应中显示了中等的反应活性，但只获得了较低对映选择性（8%～21% ee），而手性Co^Ⅲ(salen)化合物3a～3c在该反应中没有反应活性。通过研究整个配体的构象影响对化合物的低对映选择性进行了讨论。     

富马酸单正烷基酯的合成和表征

马来酸酐(1)和C1～C8正烷基醇(2a～2h)发生醇解反应生成马来酸单正烷基酯,后者接着在无水AlCl3存在下加热发生异构化反应,得到富马酸C1～C8单正烷基酯(3a～3h),醇解反应和异构化反应的总收率79.2%～87.3%。其结构经ESI-MS,IR和1H NMR表征。     

香豆素酰胺类化合物的合成及光谱特性

用(取代)香豆素-3-甲酰氯(Ⅰa～Ⅰc)和取代2-氨基苯并噻唑(Ⅱa～Ⅱd)作用合成了12种新的目标化合物(Ⅲa～Ⅲl),用HRMS、IR、1H NMR对化合物结构进行了表征,确定了化合物的结构,并对其紫外吸收光谱和荧光光谱进行了分析。研究发现:在紫外光谱中,新化合物(Ⅲa～Ⅲl)和原料化合物(Ⅰa～Ⅰc)相比,因共轭链的增长而使其最大吸收波长(λmax)红移;12种化合物表现出比原料化合物(Ⅰa～Ⅰc)较强的荧光性能。     

一步法合成2-芳基咪唑并[2，1-a]异喹啉等杂环化合物

由异喹啉、喹啉或酞腈与α-卤代苯乙酮反应生成的鎓盐在二氢铬酸四吡啶合? 埽═PCD）存在下与乙酸铵反应，可一步法合成咪唑并[2,1-a]异喹啉(2a～2b)、? 溥虿1,2-a]喹啉(4a～4b)或咪唑并[1,2-a]酞腈(6a～6c)衍生物，该方法原料易? 茫从μ跫子诳刂疲佣峁┝艘恢趾铣烧饫嗷衔锏男路椒ā?     

Ultrasound Assisted Synthesis of Coumarin Thioglycopyranoside Derivatives

The methyl coumarins reacted with N‐bromo‐succinimide gave compounds ( a～c ) which on further reacted with various peracetyl sulfhydryl glycose ( 1～3 ) afforded a series of novel coumarin thioglycopyranoside compounds ( 1a～1c, 2a～2c, 3a～3c ). And when used ultrasonic irradiation, this method offered several advantages such as good yields and short reaction time than the silent reaction. All the new compounds were characterized on the basis of the IR, ¹H NMR, ¹³C NMR and elemental analysis.     

冠醚酮酸和烷酸的合成

本文介绍了在PPA存在下，由B15C5和DB18C6同过量的二羧酸发生酰化作用，得到酮酸1a～e和3a～c。再把所得相应的酮酸1a～e和3a～c利用黄鸣龙法制得4'-(ω－羧基多亚甲基)苯并-15-冠-5(2a～e)和4',4'(5')-二(ω-羧基多亚甲基)二苯并-18-冠-6(4a～c)等一系列ω-冠醚酮酸。     

Effect of the cationic composition of cryolite-alumina melts on the anodic overvoltage

Steady-state polarization of anodes prepared from platinum or glassy carbon is studied in a laboratory cell in a cryolite-alumina melt containing small amounts of potassium and lithium fluorides and various alumina amounts. The surface area of the anodes reaches a few centimeters squared. An insignificant depolarization of the anodic process is discovered following the replacement of a fraction of sodium ions in the electrolyte by potassium ions in an amount of ～3.9 mol % KF (～4.1 wt %) and a noticeable depolarization, following the substitution of K⁺ in an amount of ～7.1 mol % KF (～7.6 wt %). Substituting lithium ions in an amount of ～3.7 mol % LiF (～1.8 wt %) for a fraction of sodium ions leads to an insignificant polarization. A significant effect of a general cryolite ratio on polarization is discovered. A noticeable increase in the anodic polarization is fixed at an alumina concentration equal to 5–5.5 wt %.     

含手性侧链结构的1, 5-二氮环辛烷的合成

手性α-氨基醇和原氯乙酸三乙酯作用,可同时分离得到两种手性侧链：酰胺醇(2a,2b)和恶唑啉(2c,2d);分别和1,5-二氮环辛烷反应,生成带手性侧臂的1,5-二氮环辛烷化合物(1a～1d),其结构经红外、核磁、质谱和元素分析等得到了证实。     

新型含1,2,4-三唑基的1,5-苯并硫氮杂的合成和表征

以α-溴代苯乙酮为原料,在三乙胺作用下制备α-(1,2,4-三唑-1-基)-芳基乙酮(1a～1c),再与芳香醛发生羟醛缩合反应制备相应的含三唑基的查尔酮2a～2l,将中间体2a～2l同邻氨基硫酚合成新型的2,4-二芳基-3-(1,2,4-三唑-1-基)-2,3-二氢-1,5-苯并硫氮杂(3a～3l).所得化合物的结构经元素分析,IR,MS和1HNMR确认,同时用X射线衍射法测定了化合物2a和3a的晶体结构.     

Effect of film thickness on the antifouling performance of poly(hydroxy-functional methacrylates) grafted surfaces

The development of nonfouling biomaterials to prevent nonspecific protein adsorption and cell/bacterial adhesion is critical for many biomedical applications, such as antithrombogenic implants and biosensors. In this work, we polymerize two types of hydroxy-functional methacrylates monomers of 2-hydroxyethyl methacrylate (HEMA) and hydroxypropyl methacrylate (HPMA) into polymer brushes on the gold substrate via surface-initiated atom transfer radical polymerization (SI-ATRP). We systematically examine the effect of the film thickness of polyHEMA and polyHPMA brushes on their antifouling performance in a wide range of biological media including single-protein solution, both diluted and undiluted human blood serum and plasma, and bacteria culture. Surface plasmon resonance (SPR) results show a strong correlation between antifouling property and film thickness. Too thin or too thick polymer brushes lead to large protein adsorption. Surfaces with the appropriate film thickness of ～25-45 nm for polyHPMA and ～20-45 nm for polyHEMA can achieve almost zero protein adsorption (<0.3 ng/cm(2)) from single-protein solution and diluted human blood plasma and serum. For undiluted human blood serum and plasma, polyHEMA brushes at a film thickness of ～20-30 nm adsorb only ～3.0 and ～3.5 ng/cm(2) proteins, respectively, while polyHPMA brushes at a film thickness of ～30 nm adsorb more proteins of ～13.5 and ～50.0 ng/cm(2), respectively. Moreover, both polyHEMA and polyHPMA brushes with optimal film thickness exhibit very low bacteria adhesion. The excellent antifouling ability and long-term stability of polyHEMA and polyHPMA brushes make them, especially for polyHEMA, effective and stable antifouling materials for usage in blood-contacting devices.     

基于配合共保护策略合成γ-L-谷氨酰二肽的新方法

提出了一种采用谷氨酸席夫碱Ni(II)配合物共保护L-谷氨酸的α-氨基和α-羧基合成γ-L-谷氨酰二肽的新方法. 首先由手性助剂——2-[N-(N-苄基-脯氨酰)氨基]二苯甲酮(1)、六水合氯化镍和L-谷氨酸反应, 得到谷氨酸席夫碱Ni(II)配合物2, 产率为98.2%; 进而采用二异丙基碳二亚胺(DIC)/1-羟基-苯并三唑(HOBt)复合缩合剂法分别与L-氨基酸3a～3h反应, 得到相应的γ-L-谷氨酰二肽席夫碱Ni(II)配合物4a～4h, 产率为93.1%～99.0%; 最后稀酸水解配合物, 得到γ-L-谷氨酰二肽5a～5h, 产率为73.0%～86.4%, 高收率(92.2%～97.4%)回收手性助剂. 中间产物和终产物的结构经由旋光, 1H NMR, 13C NMR和HRMS表征.     

3-(2-卓二唑啉基) - 色酮类化合物的合成研究

报道了取代的邻羟基苯乙酮(1a～1e)经Vilsmeier-Haack反应一步制得3－醛基色酮(2a～2e),2a～2e与取代的芳酰肼(3a～3c)缩合制得15个酰腙类化合物(4a～4o),4a～4o在醋酸酐作用下关环得15个3-(2-卓二唑啉基)-色酮(5a～5o),并通过元素分析,IR,^1^HNMR和MS谱数据确证了上述化合物的结构。     

丙二酸单苯酰胺的固相法合成及其在Eaton试剂或多聚磷酸作用下的环化反应

苯胺及取代的苯胺和Meldrum’s acid在固相无催化剂条件下反应,合成了丙二酸单苯酰胺（1a-1f）,收率81．0％～92．2％．化合物1a-1f在Eaton试剂（五氧化二磷＋甲基磺酸）或多聚磷酸为环化试剂的条件下发生Friedel—Crafts分子内环化反应,以63．2％～93．8％和56．5％～81．3％的收率方便地得到4-羟基喹啉-2-酮衍生物（2a-2f）．产物的结构通过IR,^1H NMR和元素分析得以证实．     

含均苯四甲酸二酰亚胺受体单元的共轭高分子的合成及其在有机太阳能电池上的应用

通过Stille反应合成了一系列含有均苯四甲酸二酰亚胺受体单元的共轭聚合物P1～P7.该系列聚合物在常见有机溶剂中溶解性良好,在370～600 nm范围内有较强吸收.通过循环伏安法测量其LUMO能级范围在-3.66～-3.90 eV之间,HOMO能级在-5.25～-6.17 eV之间,在同类分子中接近最低值.通过改变主链中噻吩单元的数量和给电子单元,可以调节分子的能隙,使其电化学能隙在2.45～1.55 eV范围内变化.将含均苯四甲酸二酰亚胺受体单元的P1～P7应用于有机太阳能电池中,作为给体材料与PC61BM共混制成本体异质结聚合物电池,器件开路电压普遍较高.其中基于均苯四甲酸二酰亚胺与二噻吩并噻咯的聚合物P7的器件,在AM 1.5 G,86 mW/cm2光照条件下,开路电压为0.72 V,短路电流为1.22 mA/cm2,能量转换效率为0.27%.     

邻甲基取代杂萘联苯型聚芳酰胺的合成与性能

二氮杂萘酮;物理性能;邻甲基取代杂萘联苯型聚芳酰胺的合成与性能