2,7-二溴-9-亚(β-萘胺)基芴的合成

以芴为原料,通过空气氧化、水中溴代再与β-萘胺缩合,合成了2,7-二溴-9-亚(β-萘胺)基芴,较佳合成反应条件是:以四氢呋喃为溶剂,空气为氧化剂,n(芴):n(氢氧化钾)=1:2,室温反应6h,得芴酮,产率95.6%,再以芴酮为原料,水为溶剂,n(芴酮):n(溴)=1:2.5,回流反应10h,得2,7-二溴芴酮,然后以四氢呋喃为溶剂,冰乙酸为催化剂,n(2,7-二溴芴酮):n(β-萘胺)=1:1.3,回流反应12h,得2,7-二溴-9-亚(β-萘胺)基芴,产率为87.2%,所得产物的结构经IR、1HNMR、UV-Vis、MS和X射线单晶表征。     

9,9-二辛基-2,7-二溴代芴的合成研究

确定了一种以2,7-二溴代芴、溴辛烷为原料合成9,9-二辛基-2,7-二溴代芴的方法。确定了碱的类型氢氧化钾最佳;用量3.14eq最佳,合成过程中保护气体氩气最佳;可以避免反应过程中生成2,7-二溴代芴酮;通过以上最佳合成条件的确定,使目标产物的转化率可达到97%,收率达到88.32%。     

可光固化单体2,7-二溴-9,9-双[4′-(1″,4″-戊二烯-3″-氧基酰基戊基氧基)苯基]芴的合成

以芴为原料,经溴代、氧化反应首先合成了2,7-二溴芴酮,再与苯酚反应合成2,7-二溴-9,9-双(4′-羟基苯基)芴.利用2,7-二溴-9,9-双(4′-羟基苯基)芴与1,4-戊二烯-3-醇-6′-溴己酸酯经醚化反应合成了用于发光聚合物制备的可光固化单体标题化合物.反应总收率66％.中间产物和目标产物结构经1HNMR、13CNMR和元素分析表征.     

2,7-二溴-9,9-二辛基芴的合成工艺改进

以芴、溴素为原料,三氯甲烷为溶剂,铁粉为催化剂,0℃下合成得到2,7-二溴芴,然后以二甲基亚砜为溶剂,四丁基溴化铵为相转移催化剂,室温下与1-溴辛烷反应得到标题化合物,总收率为53.2%。通过1HNMRI、R和元素分析确证了2,7-二溴芴与标题化合物的结构。与目前常用的3种合成方法相比较,该合成工艺具有反应条件温和,后处理简单,收率较高等优点。     

2,7-二溴-9,9-双(4-氨基苯基)芴的合成及精制研究

以2,7-二溴-9-芴酮和苯胺盐酸盐为原料,以甲苯为溶剂,亚硫酸氢钠为助催化剂,在氮气保护一定温度下催化合成9,9-双(4-氨基苯基)-2,7-二溴芴。粗产品采用重结晶的方法进行精制,精制溶剂选用甲苯与无水乙醇的混合液,重结晶产品经抽滤、干燥等处理得到相应的精制产品,并对产品进行了红外核磁等表征。产品通过液相测定纯度为99.50%,精制后产品收率为67.91%。     

溴代芴的合成研究

以碳酸丙烯酯为溶剂、以N-溴代丁二酰亚胺（NBS）为溴化试剂,进行芴的溴代反应研究,合成了2-溴芴和2,7-二溴芴。通过对反应温度、NBS的用量以及加入方式等的考察,确定合成2-溴芴的最佳反应条件。最佳反应条件为：反应温度23℃、NBS和芴的物质的量比为1．1：1、NBS分批加入。先将芴和碳酸丙烯酯预热至60℃,使得芴全部溶解,然后降至反应温度,分批加入NBS。2-溴芴和2,7-二溴芴分别以无水乙醇和冰醋酸重结晶,目标产物的液相色谱纯度均可达到99％以上。     

2,7-二溴芴酮与锌汞齐和浓盐酸还原反应制备2,7-二溴芴

以2,7-二溴芴酮为原料,锌汞齐和浓盐酸为还原剂,在乙醇中还原反应制备得到了2,7-二溴芴。对反应过程中还原剂用量、溶剂、反应温度、反应时间、盐酸用量及其加入方式进行了优化选择。实验结果表明,较佳的反应条件为:以质量分数95%的乙醇为溶剂,锌汞齐和浓盐酸为还原剂,分8~10次加入浓盐酸,回流反应8 h,产率84.9%~85.4%,质量分数高于99.0%。对2,7-二溴芴酮与还原剂的摩尔比以及还原剂中的锌汞齐与盐酸的摩尔比进行了考察,其中n(2,7-二溴芴酮)∶n(锌)=1∶5,锌汞齐中n(锌)∶n(汞)=48∶1,还原剂中n(锌)∶n(HCl)=1∶6时取得了较好效果。所合成化合物的结构通过红外、核磁共振波谱进行了表征。该方法的新颖性,已为山西省科学技术情报研究所2007年3月9日提供的《检索报告》所证实。     

新型三苯胺类空穴传输材料合成与性能研究

以3-N-联苯基氨基-9-苯基咔唑和2,7-二溴-9.9-二苯基芴为原料,经Buchwald-Hartwig偶联反应,合成了一种含芴咔唑类空穴传输材料N~2,N~7-二(联苯-4-基)-N~2,N~7-二(9-苯基咔唑-3-基)-9,9-二苯基芴-2,7-二胺。利用~1H NMR、IR和元素分析等方法对产物结构进行了表征,并通过DSC-TG、UV-Vis和荧光光谱研究了物质的热稳定性和光学性能。     

手性3-[9-(3-吡啶基)芴基]环氧丙烷的合成

以芴和手性环氧氯丙烷为原料,合成了标题化合物.芴与丁基锂反应得到的芴基锂与3-溴吡啶反应得9-(3-溴吡啶)芴.9-(3-溴吡啶)与丁基锂反应生成的9-(3-溴吡啶)-9-芴锂与手性环氧氯丙烷反应即得标题化合物.所得产物的光学纯度与原料环氧氯丙烷相近.     

一种含芴的炔类聚合物的合成及其光学性能研究

以9,9-二癸基-2,7-二溴芴为原料,用炔基来取代2位和7位上的溴原子,所得产物在碱性条件下,以双三苯基磷二氯化钯/碘化亚铜为催化剂,与2,5-二溴吡啶聚合得到一种含芴的炔类聚合物。对所合成的化合物都进行了核磁等表征,初步确证了其分子结构。并测试了它们的紫外-可见光谱,发现在300~400 nm范围内,其与单体相比有更好的光吸收性能。     

Push-pull-Butadiene. XII. Darstellung von Hetrocyclen aus 2,6-Bis[bis(alkylthio)methylen]cyclohexylidenmalononitrilen

Preperations of Heterocycles by using of 2,6-Bis[bis(alkylthio)methylene]cyclohexylidenemalononitriles . 2,6-Bis[bis(alkylthio)methylene]cyclohexylidenemalonitriles 1 react with alkanethioles to give 1,3-bis(alkylthio)-5-[bis(alkylthio)methylene]-5,6, #7,8-tetrahydro-isoquinoline-4-carbonitriles 2 . Treatment of 1 with hydrogen bromide yields 4,6,7,9-tetrakis(alkylthio)-2,3-dihydro-5,8-diaza-phenalenes 3 . On the other hand, 1 can be converted with bromine to 6,9-bis(alkylthio)-4,7-dibromo-2,3-dihydro-5,8-diaza-phenalenes 5 . However, the reaction of 1 and N-bromosuccinimide afforded 2,6-bis[bis(alkylthio)methylene]-3-bromo-cyclohexylidenemalononitriles 8 .     

9-二硫代芳甲酸酯基芴的合成

以9-溴芴和卤代芳烃为原料,首次经由格氏反应合成了5种有望做为可逆加成-断裂链转移试剂的双硫酯类化合物,并用1HNMR、13CNMR、IR、MS和元素分析对所得化合物结构进行了表征。     

一种绿色高效的溴代硝基芴酮的制备方法

以芴为原料,通过氧化、溴代、硝化反应,制得2-溴-7-硝基芴酮及2,7-二溴-4-硝基芴酮,对硝化反应条件进行了优化。2-溴-7-硝基芴酮最佳合成条件为:水作溶剂,质量分数65%的硝酸和质量分数96%的硫酸混合酸为硝化试剂,回流反应3h,其中n(HNO3)∶n(H2SO4)∶n(2-溴芴酮)=29∶36∶1,m(2-溴芴酮)∶m(H2O)=1∶7.7,所得2-溴-7-硝基芴酮的产率为92.8%,质量分数高于98.0%;2,7-二溴-4-硝基芴酮最佳合成条件为:水作溶剂,质量分数85%的硝酸和质量分数95%的硫酸混合酸为硝化试剂,回流反应4h,其中n(HNO3)∶n(H2SO4)∶n(2,7-二溴芴酮)=40∶36∶1,m(2,7-二溴芴酮)∶m(H2O)=1∶5.9,所得2,7-二溴-4-硝基芴酮的产率为90.9%,质量分数高于98.0%。产品结构经红外、核磁共振波谱确证。     

Electrochemistry and electron transport properties of copolymers of electron deficient fluorenes with thiophene

Copolymers of fluoren-9-one and (fluoren-9-ylidene)malononitrile with thiophene have been prepared by the electrochemical polymerization of 2-(2-thienyl)fluoren-9-one, 2,7-di(2-thienyl)fluoren-9-one, and (2,7-di(2-thienyl)fluoren-9-ylidene)malononitrile. 2-(2-Thienyl)fluoren-9-one gave polymer films with low conjugation lengths, indicating poorly defined coupling, while both monomers with two terminal thiophenes gave high quality copolymers. Poly-[2,7-di(2-thienyl)fluoren-9-one] was the most easily p-doped material, and gave the highest p-type conductivity of ca. 0.4 mS cm⁻¹. In contrast poly-[(2,7-di(2-thienyl)fluoren-9-ylidene)malononitrile] was more easily reduced by over 0.5 V (formal potential = −0.60 V versus Ag/AgCl), and exhibited the higher n-type conductivity of ca. 6 μS cm⁻¹. Comparisons between the three copolymers reveal differences in the mechanisms of p-type and n-type conduction, with the former dominated by hole transport along the polymer chains and the latter involving electron hopping between localized sites.     

Bornane with integrated push–pull butadienes

The {3-[bis(alkylthio)methylene]-1,7,7-trimethyl-bicyclo[2.2.1]hept-2-ylidene}malononitriles ((1R,4S)- 2 , (1S,4R)- 2 and (1R,4S)- 3 ) were prepared starting from 1,7,7-trimethyl-bicyclo[2.2.1]hept-2-ylidenemalononitriles (1R, 4R)- 1 and (1S,4S)- 1 ) arisen from (+)-, (–)-camphor. The reaction of (1R,4S)- 2 with bromine yielded the (1S,8R)-8,11,11-trimethyl-3-methylthio-5-oxo-4-thiatricyclo-[6.2.1.0^2,7]undeca-2,6-diene-6-carbonitrile ( 8 ) after hydrolysis of the initially formed (1S,8R)-6-cyano-8,11,11-trimethyl-3-methylthio-4-thia-tricyclo[6.2.1.0^2,7]undeca-2,6-diene-5-iminium bromide ( 7 ).     

Synthesis and performances of 9,9-bis(perfluorohexylethyl propionate) fluorene copolymers

2,7-dibromo-9,9-bis(perfluorohexylethyl propionate) fluorene was synthesized by Michael addition reaction using 2,7-dibromofluorene and perfluorohexyl ethyl acrylate as the reactants. 9,9-Bis(perfluorohexylethyl propionate) fluorene copolymers were then synthesized by Suzuki coupling reaction with 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane-diyl)-9,9 -dioctyl fluorene, 2,7-dibromo-9,9-dioctyl fluorene and 2,7-dibromo-9,9-bis(perfluorohexylethyl propionate) fluorene as the monomers. The fluorinated fluorene copolymers were characterized and investigated via Fourier infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance spectroscopy (¹HNMR), ultraviolet absorption spectroscopy (UV–vis), cyclic voltammetry (CV) and photoluminance spectroscopy (PL). Because of the long fluorine-containing alkyl side chain, the ultraviolet absorption peak of 9,9-bis(perfluorohexylethyl propionate) fluorene is blue-shifted compared with poly(9,9-dioctylfluorene)(PF8). The LUMO energy level increases and the energy band gap of copolymers widens. Due to the self-assembly of the long fluoroalkyl side chain, the photoluminance spectra of 9,9-bis(perfluorohexylethyl propionate) fluorene copolymers exhibit a new excimer emission peak at 550 nm. The photoluminance stabilities of the copolymers under irradiation and humid conditions are significantly improved due to protective effect from the long fluoroalkyl side chain. After being irradiated under 500 W iodine tungsten lamp or kept under 70% relative humid conditions, the 9,9-bis(perfluorohexylethyl propionate) fluorene copolymers showed much better photoluminance stability than that of poly(9,9-dioctylfluorene) (PF8). These show that introducing long fluoroalkyl side chain into conjugated polymer main chain is a promising strategy to improve environmental stability of devices based on organic conjugated polymers.     

Synthesis and characterization of amino-functional, blue light-emitting copolymers and their composites with CdTe nanocrystals

Random side-chain functionalized copolymers were synthesized, utilizing a facile Yamamoto protocol by applying 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene, (E)-1,2-bis(4-bromophenyl)ethene, 2,7-dibromo-9,9-dioctyl-9H-fluorene as comonomers. The precursor copolymers were post-functionalized utilizing di-n-propylamine and the resulting target copolymers were fully characterized. The optical classification parameters have been determined in solutions and in thin films as well. The copolymers revealed blue light emission, wide optical bandgaps Eg_opt of at least 2.84 eV and remarkable quantum yields up to 0.78 in chloroform solutions. The amino-functional copolymers allowed tying semiconductor CdTe nanocrystals.     

New Strategy for Synthesis of Polyphenylene Substituted Dendronized Monomers Containing Fluorene Unit and the Study of Their Properties

A mild and efficient synthetic strategy has been developed for the synthesis of polyphenylene substituted dendronized monomers containing fluorene unit, namely 2,7-dibromo-9,9-di(4-(pentaphenylphenyl)benzyl) fluorene 5a and 2,7-dibromo-9,9-di(4-(2,3,4,5-tetraphenylphenyl)benzyl) fluorene 5b. The present synthetic route was found efficient, which avoids the unwanted by-product formation and has fewer column chromatography purification requirements. The synthesized compounds 5a and 5b showed promising optical properties. Moreover, TGA study revealed good thermal stability of the synthesized compounds.     

Synthesis of soluble poly(9,10-dihydrophenanthrene-2,7-diyl)s. A new class of luminescent poly(p-phenylene)s with ethylene type bridges

Poly(9,10-dihydrophenanthrene-2,7-diyl)s with -OSi(R)₂(R′) groups at the 9,10-positions were synthesized by dehalogenative polycondensation of the corresponding monomers by using a zerovalent nickel complex. They showed number average molecular weights (M_n's) of 9800-69,000 and high quantum yields (62%-quantitative) in photoluminescence. Palladium catalyzed copolymerization of 2,7-dibromo-9,10-dihydrophenanthrene having -OCH₃ or -OSi(R)₂(R′) groups at the 9,10-positions with diethynyl- or diboronic-aromatic compounds also gave photoluminescent polymers with high quantum yields.