2-异丙基喹喔啉衍生物的合成及应用

以邻苯二胺化合物和α-溴代酮类化合物为原料,经过串联环化反应合成喹喔啉类化合物。部分未知的喹喔啉衍生物经过质谱和核磁分析加以确证。同时研究了2-异丙基喹喔啉在过渡金属Ag参与下的sp3C—H键硝化反应。     

2-多氟芳基喹喔啉衍生物的合成及制备工艺研究

以2-羟基喹喔啉衍生物为原料,通过溴化反应制备中间产物2-溴喹喔啉衍生物,与多氟芳烃在碘化亚铜的催化作用下发生偶联反应,合成了2-多氟芳基喹喔啉衍生物,产物结构经过了~1H NMR、~(13)C NMR、~(19)F NMR和MS表征。研究了催化剂种类及用量、物料比、反应温度、碱和溶剂对产物收率的影响。结果表明,2-多氟芳基喹喔啉衍生物优化工艺条件为:n(2-溴喹喔啉衍生物)∶n(多氟芳烃)∶n(碘化亚铜)∶n(1,10-菲啰啉):n(磷酸钾)=1.0∶1.5∶0.1∶0.1∶2.0,二甲苯-二甲基甲酰胺V/V=1/1为反应溶剂,在110℃下反应12 h,收率81%。     

2-多氟芳基喹喔啉衍生物的合成及制备工艺研究

以2-羟基喹喔啉衍生物为原料,通过溴化反应制备中间产物2-溴喹喔啉衍生物,与多氟芳烃在碘化亚铜的催化作用下发生偶联反应,合成了2-多氟芳基喹喔啉衍生物,产物结构经过了¹H NMR、1H NMR、⁽¹³⁾C NMR、(13)C NMR、⁽¹⁹⁾F NMR和MS表征。研究了催化剂种类及用量、物料比、反应温度、碱和溶剂对产物收率的影响。结果表明,2-多氟芳基喹喔啉衍生物优化工艺条件为:n(2-溴喹喔啉衍生物)∶n(多氟芳烃)∶n(碘化亚铜)∶n(1,10-菲啰啉):n(磷酸钾)=1.0∶1.5∶0.1∶0.1∶2.0,二甲苯-二甲基甲酰胺V/V=1/1为反应溶剂,在110℃下反应12 h,收率81%。     

新型砜基喹喔啉衍生物的合成和体外抗肿瘤活性研究

合成了新型的砜基喹喔啉衍生物并对其体外抗肿瘤活性进行初步评价。采用Kinase-Glo Luminescent Assay,Lance Ultra Assay,SRB法测试砜基喹喔啉类衍生物的体外抗肿瘤活性。9个砜基喹喔啉衍生物经NMR,MS表征;砜基喹喔啉衍生物对PI3Kα、哺乳动物雷帕霉素靶蛋白(mTOR)均无明显的抑制作用;其中,化合物3-(3-氨基苯磺酰基)-N-(3,5-二甲氧基苯基)喹喔啉-2-胺(12),N-(3-(3-(3,5-二甲氧基苯胺基)喹喔啉-2-基砜基)苯基)乙酰胺(13)、1-(3-(3-(3,5-二甲氧基苯胺基)喹喔啉-2-基砜基)苯基)-3-乙基脲(15)和N-(3-(3-(3,5-二甲氧基苯胺基)喹喔啉-2-基砜基)苯基)吗啉-4-甲酰胺(16)对PC3细胞的增殖抑制活性(IC₅₀)均<3μmol/L。砜基喹喔啉类衍生物具有中等强度的抗肿瘤活性。     

新型三线态喹喔啉铱(Ⅲ)配合物的微波合成及其光致发光

在微波辅助加热下,4,4'-二氟-2,3-二苯基喹喔啉(DPQF)与水合三氯化铱(IrCl3·H2O)反应,合成了一种新型三环喹喔啉铱配合物[Ir(DPQF)3],通过1HNMR、元素分析和质谱方法对配合物结构进行了表征,并研究了配合物的吸收光谱和光致发光光谱.结果表明,配合物Ir(DPQF),在391和453 nm处...     

喹喔啉化合物的脂质过氧化活性

研究了一系列先前合成的喹喔啉化合物的抑制脂质过氧化活性,实验得到了这些化合物的体内和体外脂质过氧化抗氧化活性数据,发现这类喹喔啉化合物具有优异的抗氧化活性,其中,脂质过氧化清除率最高的化合物是2-(3-(3-甲氧基-4-羟基苯基)-2氧喹喔啉-1(2H)-烷基)乙酸,它在浓度为100μmol/L时,对应的清除率达到了57.7%。构效关系研究认为对羟基苯乙烯这一结构单元对于喹喔啉化合物在提高抗氧化活性有重要意义。     

喹喔啉类化合物的合成研究进展

喹喔啉是一种重要的精细化工中间体,广泛用于农药,医药等行业,本文以二羰基,二硫代碳基,环氧化合物,α-羟基酮,α,β-二醇以及α-卤代酮与邻苯二胺为原料,综述了近些年来过渡金属与无过渡金属条件下喹喔啉合成方法的研究进展。报道了化学家们在合成喹喔啉这一领域里的合成方法,并对喹喔啉合成的研究前景进行了展望。     

3-氯-2,6-二硝基喹喔啉的合成工艺研究

喹喔啉为一类重要的苯并吡嗪类杂环化合物,喹喔啉衍生物在医药及化工合成领域具有重要的作用.3-氯-2,6-二硝基喹喔啉是一种重要医药化工中间体.本文以2-羟基喹喔啉为原料,经硝化反应和氯代反应两步反应得到目标化合物.该合成方法操作简便、后处理操作简便,花费时间少且产物纯度高、收率也较高,产品收率为58.2％,适合工业化生...     

富勒烯-C_(60)衍生物与2-溴甲基-3-(二溴甲基)喹喔啉的合成研究

以 2 ,3 二 (溴甲基 )喹喔啉和N 溴代丁二酰亚胺 (NBS)为原料 ,以偶氮二异丁腈 (AIBN)为催化剂 ,在氮气中反应制得 2 溴甲基 3 (二溴甲基 )喹喔啉 (A) ,收率为 2 0 %。以此为中间体与富勒烯C60 反应 ,以 18 冠 6为催化剂 ,按n(A)∶n(C60 ) =1 1∶1 0的物质量比在氮气气氛中经Diels-Alder环加成反应合成了C60 并夹二氮杂蒽 (B) ,收率为 10 6 6 %。并对A和B进行了结构表征。     

三组分“一锅法”合成6-溴-2-芳基喹喔啉衍生物

以4-溴苯-1,2-二胺、芳香醛和对甲基磺酰甲基异腈(TOSMIC)为原料，甲苯为反应溶剂，在三乙烯二胺(DABCO)碱性条件下，三组分“一锅法”合成了5种目标化合物6-溴-2-芳基喹喔啉衍生物1a～1e,产物经¹H NMR、¹³C NMR和电喷雾离子源质谱(ESI-MS)表征。其中，6-溴-2-苯基喹喔啉(1a)的结构进一步通过X射线衍射(XRD)确定。并以4-溴苯-1,2-二胺(2)、苯甲醛(3a)和TOSMIC的三组分反应合成6-溴-2-苯基喹喔啉(1a)的反应为模型，研究了影响产物1a收率的主要因素，确定了适宜的反应条件为：n(3a)∶n(TOSMIC)∶n(2)比为1.2∶1.1∶1.0、n(DABCO)∶n(2)=1.2∶1.0、反应温度80℃、反应时间5 h条件下，产物1a收率为56.1%。     

新型含噻吩类衍生物的合成与光谱特性

在四(三苯基膦)钯(Pd(PPh3)4催化作用下,通过催化偶合法可合成5,8-二噻基-萘基喹喔啉(DThQx(ace))和3,6-二噻基-哒嗪(DThPD)两种新型噻吩衍生物,同时也可合成了4,7-二噻基-2,1,3-苯并噻二唑(DThB)和1,4-二噻基-苯(DThPh),上述化合物产率分别为75%,78%,82%和67%。用红外光谱、核磁共振谱、元素分析等方法进行了表征,并对噻吩与不同芳香环构成的衍生物的紫外-可见吸收光谱和荧光光谱进行了对比研究。这四种化合物的紫外-可见吸收光谱中分别在435,336,446,325 nm处有最大吸收波长。其中DThQx(ace)、DThB和DThPh的荧光光谱中分别在564,568 nm和384 nm处观察到荧光,而DThPD无荧光。     

Fluorene-based narrow-band-gap copolymers for red light-emitting diodes and bulk heterojunction photovoltaic cells

A series of narrow band-gap conjugated copolymers (PFO-DDQ) derived from 9,9-dioctylfluorene (DOF) and 2,3-dimethyl-5,8-dithien-2-yl-quinoxalines (DDQ) is prepared by the palladium-catalyzed Suzuki coupling reaction with the molar feed ratio of DDQ at around 1%, 5%, 15%, 30% and 50%, respectively. The obtained polymers are readily soluble in common organic solvents. The solutions and the thin solid films of the copolymers absorb light from 300–590 nm with two absorbance peaks at around 380 and 490 nm. The intensity of 490 nm peak increases with the increasing DDQ content in the polymers. Efficient energy transfer due to exciton trapping on narrow-band-gap DDQ sites has been observed. The PL emission consists exclusively of DDQ unit emission at around 591–643 nm depending on the DDQ content in solid film. The EL emission peaks are red-shifted from 580 nm for PFO-DDQ1 to 635 nm for PFO-DDQ50. The highest external quantum efficiency achieved with the device configuration ITO/PEDOT/PVK/PFO-DDQ15/Ba/Al is 1.33% with a luminous efficiency 1.54 cd/A. Bulk heterojunction photovoltaic cells fabricated from composite films of PFO-DDQ30 copolymer and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) as electron donor and electron acceptor, respectively in device configuration: ITO/PEDOT:PSS/PFO-DDQ30:PCBM/PFPNBr/Al shows power conversion efficiencies of 1.18% with open-circuit voltage (V_oc) of 0.90 V and short-circuit current density (J_sc) of 2.66 mA/cm² under an AM1.5 solar simulator (100 mW/cm²). The photocurrent response wavelengths of the PVCs based on PFO-DDQ30/PCBM blends covers 300–700 nm. This indicates that these kinds of low band-gap polymers are promising candidates for polymeric solar cells and red light-emitting diodes.     

不对称联苯醌电子传输材料的合成及光导性应用

以2,6烷-基取代苯酚合成了3,5二-甲基-3′,5′-二叔丁基联苯醌(Ⅰ)和3,3′-二甲基-5,5′-二叔丁基联苯醌(Ⅱ)。适宜的合成条件是以三氯甲烷作溶剂,颗粒度低于200目的KMnO4作氧化剂,在50℃反应3 h,收率分别为90.01%和89.87%。分离提纯采用硅胶色谱柱,V(石油醚)∶V(乙酸乙酯)=60∶1的混合液作流动相,HPLC面积归一法测得Ⅰ和Ⅱ色谱纯度分别为100%和99.5%。对合成产物进行了组成和结构鉴定。用Ⅰ和Ⅱ制成有机光导器件,静电特性数据分别为Ⅰ:充电电位Vm ax=340 V,残余电势Vr=80 V,光敏性E1/2=1.60 lux.s;Ⅱ:Vm ax=840 V,Vr=160 V,E1/2=2.67 lux.s。说明化合物Ⅰ和Ⅱ有较好的静电特性。     

疏水缔合型聚合物P(AM/TA)溶液性质的研究

采用沉淀聚合法制备了疏水缔合型聚合物丙烯酰胺 /丙烯酸十四酯共聚物P(AM/TA)。研究了在链结构中引入不同疏水基团摩尔分数的共聚物的溶液性质。结果表明该共聚物在w(NaCl) =1 5 %的溶液中的黏度较之水溶液有较大提高 ,表现出明显的抗盐性质 ,而临界缔合质量分数和特性黏度均出现下降趋势。该聚合物是一种性能优异的疏水缔合型增稠剂。作者对共聚物溶液的黏度 -温度性质和剪切速度对溶液黏度的影响也进行了研究。     

Synthesis and photoluminescence properties of fluorine-containing poly(phenylene vinylene) bearing hexafluorocyclopentene-fused phenanthrene unit

The intramolecular oxidative photocyclization of 1,2-diarylhexafluorocyclopentene ( 1 ) under light irradiation (λ = 365 nm) provided hexafluorocyclopentene-fused phenanthrene with formyl groups ( 2 ) in moderate yield. The copolymerization of 2 with tetraethyl(2,5-bis(dodecyloxy)-1,4-phenylene)bis(methylene)diphosphonate by the Horner–Wadsworth–Emmons reaction gave a fluorine-containing poly(phenylene vinylene), Polymer-2, in 41% yield. For comparison, a diphenylethene-type copolymer, Polymer-1, was also prepared analogously. The number-average molecular weights of Polymer-1 and Polymer-2 were 8900 and 3300 g mol^?1, respectively. The copolymers showed high thermal stability, as revealed by their thermogravimetric analysis. UV–visible spectra of the copolymers in CHCl₃ showed π–π* transition peaks at around 420 nm, and the peaks shifted to longer wavelengths by ca 10 nm for samples in film form. The photoluminescence spectra of Polymer-1 and Polymer-2 exhibited peaks at 542 and 560 nm in CHCl₃, respectively, whereas the photoluminescence intensity of Polymer-2 was very low in the solid state, presumably owing to the partial aggregation of the polymer molecules. © 2021 Society of Industrial Chemistry.     

Preparation and properties of new π-conjugated polyquinoxalines with aromatic fused rings in the side chain

Summary New π-conjugated polyquinoxalines with aromatic fused rings in their side chain have been prepared. Dehalogenative organometallic polycondensation of 5,8-dibromo[2,3-b]-acenaphthenequinoxaline and 5,8-dibromo[2,3-b]phenanthrenequinoxaline with a zerovalent nickel complex afforded poly([2,3-b]acenaphthenequinoxaline-5,8-diyl) (P(5,8-Qx(ace))) and poly([2,3-b]phenanthrenequinoxaline-5-8-diyl) (P(5,8-Qx(phen))) in high yields. P(5, 8-Qx(ace)) had an [η] value of 0.23 dL g⁻¹ and showed absorption and photoluminescence peaks at 445 and 565 nm, respectively. (P(5,8-Qx(phen))) gave absorption and photoluminescence peaks at 400 and 514 nm, respectively. XRD data indicated formation of ordered structures of the polymers in the solid. Preparation of related copolymer with thiophene is also reported. Received: 15 February 2000/Accepted: 2 March 2000     

Fluorene-based narrow-band-gap copolymers for red light- emitting diodes and bulk heterojunction photovoltaic cells

A series of narrow band-gap conjugated copolymers (PFO-DDQ) derived from 9,9-dioctylfluorene (DOF) and 2,3-dimethyl-5,8-dithien-2-yl-quinoxalines (DDQ) is prepared by the palladium-catalyzed Suzuki coupling reaction with the molar feed ratio of DDQ at around 1%, 5%, 15%, 30% and 50%, respectively. The obtained polymers are readily soluble in common organic solvents. The solutions and the thin solid films of the copolymers absorb light from 300–590 nm with two absorbance peaks at around 380 and 490 nm. The intensity of 490 nm peak increases with the increasing DDQ content in the polymers. Efficient energy transfer due to exciton trapping on narrow-band-gap DDQ sites has been observed. The PL emission consists exclusively of DDQ unit emission at around 591–643 nm depending on the DDQ content in solid film. The EL emission peaks are red-shifted from 580 nm for PFO-DDQ1 to 635 nm for PFO-DDQ50. The highest external quantum efficiency achieved with the device configuration ITO/PEDOT/PVK/PFO-DDQ15/Ba/Al is 1.33% with a luminous efficiency 1.54 cd/A. Bulk heterojunction photovoltaic cells fabricated from composite films of PFO-DDQ30 copolymer and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) as electron donor and electron acceptor, respectively in device configuration: ITO/PEDOT:PSS/PFODDQ30: PCBM/PFPNBr/Al shows power conversion efficiencies of 1.18% with open-circuit voltage (V _oc) of 0.90 V and short-circuit current density (J _sc) of 2.66 mA/cm² under an AM1.5 solar simulator (100 mW/cm²). The photocurrent response wavelengths of the PVCs based on PFO-DDQ30/PCBM blends covers 300–700 nm. This indicates that these kinds of low band-gap polymers are promising candidates for polymeric solar cells and red light-emitting diodes. __________ Translated from Acta Polymerica Sinica (China), 2007, 10: 952–958 [译自: 高分子学报]     

电合成法制备纳米材料及纳米材料电极上的电催化合成

通过电化学合成前驱体直接水解法制备纳米TiO2 粉体和纳米TiO2 膜电极。用循环伏安法、循环方波伏安法和电解合成法研究了纳米TiO2 膜电极对有机合成反应的电催化活性。发现纳米TiO2 膜电极在 0 2～ - 1 2V扫描电位区间有两对氧化还原峰 (峰电位Epc1=- 0 5 6V ,峰电位Epc2 =- 0 95V ,扫描速度 10 0mV·s-1) ,具有异相氧化还原催化行为。电解结果表明 ,纳米TiO2 膜中的Ti(Ⅳ ) /Ti(Ⅲ )氧化还原电对作为媒质 ,异相间接电还原硝基苯为对氨基苯酚 (收率91 6 % ,电流效率 95 2 % )和草酸为乙醛酸 (收率 96 5 % ,电流效率 90 % )。     

Synthesis and electroluminescent properties of copolymers based on PPV with fluoro groups in vinylene units

New electroluminescent copolymers with fluoro groups in vinylene unit, poly(2-ethylhexyloxy-5-methoxy-p-phenylenevinylene-co-2-dimethyloctylsilyl-p-phenylenedifluorovinylene) (MEH-PPV-co-DMOS-PPDFV) and poly(2-dimethyloctylsilyl-p-phenylenevinylene-co-2-dimethyloctylsilyl-p-phenylenedifluorovinylene) (DMOS-PPV-co-DMOS-PPDFV), have been synthesized by the Gilch polymerization. The fluoro groups were introduced on vinylene units to increase the electron affinity of the copolymers. In both types of the copolymers, the band gaps were increasing with higher ratio of DMOS-PPDFV. As compared to the PL spectra in solution state, PL spectra in solid state and EL spectra of both types of copolymers showed red shifted and broad peaks caused by the aggregation. The polymer LEDs of MEH-PPV-co-DMOS-PPDFVs emit light with maximum peaks at around 538-577 nm. By adjusting the feed ratios of DMOS-PPDFV in the copolymers, we could tune the emission colors from orange yellow to green. DMOS-PPV-co-DMOS-PPDFVs showed the maximum EL peaks at about 514-543 nm. DMOS-PPV-co-DMOS-PPDFV with 1:9 feed ratio showed the highest luminescence efficiency of 1.31 lm/W.     

纳米TiO_2膜电极上乙醛酸的电催化合成研究

运用电化学循环伏安法 (CV)对纳米TiO2 膜电极 (Ti/nano TiO2 )在硫酸和草酸溶液中的电化学行为进行了研究。在c(H2 SO4 ) =1mol/L溶液中的循环伏安图上Epac1=- 0 .5 6V(vs.SCE)和Epac2 =- 0 96V(vs.SCE)处 ,出现两对可逆氧化还原峰 ,而在相同扫描速度下草酸溶液中的循环伏安曲线上 ,这两对电极反应氧化峰基本消失 ,还原峰电流增大 ,表明Ti/nano TiO2 膜电极对电还原草酸成为乙醛酸的反应具有较高的电催化活性和选择性。常温常压下 ,控制电位Epc=- 1 0V左右电解合成乙醛酸 ,乙醛酸的产率和电流效率分别达到 96 5 %和 90 %。