新型芴类衍生物的合成研究
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摘要
芴及其衍生物因其卓越的电学性能和光学性能，是一种良好的电致发光材料。在过去几年中，由于这类化合物优良的光电性能，使其在发光二极管，激光器件，光电池，生物传感器器件等方面得到了广泛应用。
为了改善芴的综合电致发光性能，目前主要采用制备小分子的芴发光材料，其中，小分子的电致发光材料结构明确，材料的性能与结构之间的正交关系比较直接，实验也比较容易控制。此外，该类材料在溶解性以及可加工性等方面具有高分子材料所不可替代的优势，因此为改善芴类材料的综合发光性能，合成各种结构的芴类小分子发光材料就成为国内外科研工作者的研究热点。
我们以芴和查尔酮以及芳香醛为原料经Michael加成反应和Knoevenagel反应合成出了一系列未见文献报道的9-取代芴类小分子化合物。本研究工作包括三部分：
（1）以芴和查尔酮为原料，经Michael加成反应，方便地制备一系列未见文献报道的9-(3-氧代-1,3-二芳基丙基)芴衍生物，目标化合物的结构经IR、MS和1HNMR予以表征。培养了目标化合物Ⅰa的单晶，并用X-ray单晶衍射分析法测定其晶体结构。
（2）以2-硝基芴与芳香醛为原料通过Knoevenagel反应方便地制备一系列2-硝基-10-（芳基亚甲基）芴衍生物，目标化合物的结构经IR、MS、1H NMR和元素分析方法予以表征。测定了部分化合物的荧光性能，结果表明所测化合物有很好的荧光性能。
（3）以芴和3,4-二氯苯甲醛为原料，在微波辐射下，通过Knoevenagel反应，合成了9-(3,4-二氯苯基亚甲基)芴，培养了目标化合物Ⅲa的单晶，并用X-ray单晶衍射分析法测定其晶体结构。
Fluorene and its derivatives are very useful electroluminescent materials becauseof its excellent electrical properties and optical properties. In the past few years, thesecompounds are widely used in the light emitting diode, laser devices, photovoltaiccells and biosensor devices because of its excellent electrical properties and opticalproperties.
In order to improve the fluorene’s electroluminescent properties, currently themain use of the preparation of small molecules fluorene light emitting materials.Thestructure of the small molecule fluorene electroluminescent materials is explicit, theorthogonal relationship between the performance and structure of the material isrelatively straightforward and the experiment is also relatively easy to control. Inaddition，such materials have irreplaceable advantages with polymer materials in thesolubility and processability. Therefore, in order to improve the luminescentproperties of fluorene material, the synthesis of various structures fluorene smallmolecular luminescent materials has become the research focus of scientists at homeand abroad.
We use the fluorene、chalcones and aromatic aldehydes as raw materials,synthesize a series of9-substituted fluorene small molecule compounds that have notbeen reported by Michael addition reaction and Knoevenagel reaction.Three aspects were included in this paper:
（1）The fluorene and chalcones as raw materials, a series of9-(3-Oxo-1,3-bisarylpropyl) fluorene derivatives were synthesized by Michael addition reaction.The structures of all the title compounds were characterised by IR、MS、1H NMR andelementary analysis. The single crystal of target of compoundⅠa was cultured and thecrystal structure was determined by X-ray diffraction analysis.
（2）The aromatic aldehydes and2-nitro-fluorene as raw materials，a series of2-nitro-10-(arylpropylmethylidyne) fluorene derivatives were synthesized byKnoevenagel reaction. The structures of all the title compounds were characterised by IR、MS、1H NMR and elementary analysis. At the same time the fluorescence propertyof the part of the material Ⅱ series were determined very good.
（3）A novel compound of9-(3,4-dichlorophenymethylidyne) fluorene wassynthesized via Knoevenagel reaction under microwave irradiation. The single crystalof target of compound Ⅲa was cultured. The crystal structure was determined byX-ray diffraction analysis.
为了改善芴的综合电致发光性能，目前主要采用制备小分子的芴发光材料，其中，小分子的电致发光材料结构明确，材料的性能与结构之间的正交关系比较直接，实验也比较容易控制。此外，该类材料在溶解性以及可加工性等方面具有高分子材料所不可替代的优势，因此为改善芴类材料的综合发光性能，合成各种结构的芴类小分子发光材料就成为国内外科研工作者的研究热点。
我们以芴和查尔酮以及芳香醛为原料经Michael加成反应和Knoevenagel反应合成出了一系列未见文献报道的9-取代芴类小分子化合物。本研究工作包括三部分：
（1）以芴和查尔酮为原料，经Michael加成反应，方便地制备一系列未见文献报道的9-(3-氧代-1,3-二芳基丙基)芴衍生物，目标化合物的结构经IR、MS和1HNMR予以表征。培养了目标化合物Ⅰa的单晶，并用X-ray单晶衍射分析法测定其晶体结构。
（2）以2-硝基芴与芳香醛为原料通过Knoevenagel反应方便地制备一系列2-硝基-10-（芳基亚甲基）芴衍生物，目标化合物的结构经IR、MS、1H NMR和元素分析方法予以表征。测定了部分化合物的荧光性能，结果表明所测化合物有很好的荧光性能。
（3）以芴和3,4-二氯苯甲醛为原料，在微波辐射下，通过Knoevenagel反应，合成了9-(3,4-二氯苯基亚甲基)芴，培养了目标化合物Ⅲa的单晶，并用X-ray单晶衍射分析法测定其晶体结构。
Fluorene and its derivatives are very useful electroluminescent materials becauseof its excellent electrical properties and optical properties. In the past few years, thesecompounds are widely used in the light emitting diode, laser devices, photovoltaiccells and biosensor devices because of its excellent electrical properties and opticalproperties.
In order to improve the fluorene’s electroluminescent properties, currently themain use of the preparation of small molecules fluorene light emitting materials.Thestructure of the small molecule fluorene electroluminescent materials is explicit, theorthogonal relationship between the performance and structure of the material isrelatively straightforward and the experiment is also relatively easy to control. Inaddition，such materials have irreplaceable advantages with polymer materials in thesolubility and processability. Therefore, in order to improve the luminescentproperties of fluorene material, the synthesis of various structures fluorene smallmolecular luminescent materials has become the research focus of scientists at homeand abroad.
We use the fluorene、chalcones and aromatic aldehydes as raw materials,synthesize a series of9-substituted fluorene small molecule compounds that have notbeen reported by Michael addition reaction and Knoevenagel reaction.Three aspects were included in this paper:
（1）The fluorene and chalcones as raw materials, a series of9-(3-Oxo-1,3-bisarylpropyl) fluorene derivatives were synthesized by Michael addition reaction.The structures of all the title compounds were characterised by IR、MS、1H NMR andelementary analysis. The single crystal of target of compoundⅠa was cultured and thecrystal structure was determined by X-ray diffraction analysis.
（2）The aromatic aldehydes and2-nitro-fluorene as raw materials，a series of2-nitro-10-(arylpropylmethylidyne) fluorene derivatives were synthesized byKnoevenagel reaction. The structures of all the title compounds were characterised by IR、MS、1H NMR and elementary analysis. At the same time the fluorescence propertyof the part of the material Ⅱ series were determined very good.
（3）A novel compound of9-(3,4-dichlorophenymethylidyne) fluorene wassynthesized via Knoevenagel reaction under microwave irradiation. The single crystalof target of compound Ⅲa was cultured. The crystal structure was determined byX-ray diffraction analysis.
引文
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[2]臧洪俊,李正名,王宝雷.固态有机合成反应进展[J]有机化学,2003,10(23)：1058-1063
[3]荣良策,李小跃,王海营,史达清,屠树江,水介质中1,6-二氧-5-氧代-1,4,5,6-四氢化菲衍生物的三组分-锅合成[J].有机化学,2007,27(10),121-124.
[4] Wilkes J S.Properties of ionic liquid solvents for catalysis[J].J Mol Catal A:Chem,2004,214(1):11-17.
[5] Noda A, Hayamizu K, Watanabe M. Pulsed-gradient spin-echo1H and19F NMR ionic diffusioncoefficient, viscosity, and ionic conductivity of non–chloro alu-minateroom-temperature ionic liquids[J].Journal of Physical Chemistry B,2001,105(20):4603-4610.
[6] E.J.Gau，S.C．Macdiarmjol．Electrical Conductivity in Doped Polya cet ylene[J].Phys．Rev．Lett．1977,39(4):1098-1099
[7] Gustufsson，Y．Cao，G．M．Treacy，et a1．Flexible light-emitting diodes madefrom soluble conducting polymers[J].Nature,1992,10(2):357-477.
[8] Bahrami K, Khodei M M, Shahbazi F [J]. Tetrahedron Letters,2008,49(6):3931-3934
[9] Q．B．Pei，Y．Yang，Efficient photoluminescence and electroluminesCenCefrom a solublepolyfluorene[J].J.Am.Chem.Soc,1996,118(31):7416-7417
[10] Bernius M, Inbasekaran M, Woo E, et al. Fluorene-based polymer-preparationand applications [J]. J Mater Sci: Mater Electronics,2000,119(6):111-116.
[11]胡将军,刘慧龙,邓德明.高效干法脱硫剂的研究[J].环境保护科学,1999,93(3):1-3.
[12]郝莉萍.干法/半干法高效脱硫吸附剂的制备研究[J].化工技术与开发,2003,32(4):13-15.
[13]魏庆开.用重质洗油精制工业芴[J].鞍山钢铁学院学报,1997,20(1):40-42.
[14]匡春香,范圣第.生物工程用稠环芳烃衍生物[J].精细石油化工,1998,10(3):38-43.
[15] Zhang J T, Huang S W, Xue Y N,et al poly(N-isopropylacry-amide)nanoparticle-incorporated PNIPAAm hydrogels with fast shringing kinetics [J].Macrommolecular Rapid Communications,2005,26(3):1346-1352.
[16] Mitsukami Y,Donovan M S, Lowe A B,et al,Water-soluble polymers,81, Directsynthesis of hydrophilic styrenic-based homopolymers and block copoly mers inaqueous solution via RAFT[J],Macromolecules,2001,34(2):2248-2256.
[17]姜鸿基,冯嘉春,温贵安.芴类电致发光材料研究进展[J].化学进展，2005，9(5):201-202
[18] D．M．Leeuw；Simenon,M．M．J．；Brown,A．R．；Einerhand，R．E．EStability ofn-type doped conducting polymers and consequences for polymericmicroelectronicdevices[J].Synth.Met.1997,87(1):53-59．
[19] Wang E G, Li C, Peng J B, Cao Y. J.[J].Polym. Sci. Part A: Polym.Chem.,2007,45(21):4941-4949.
[20] Tanaka K,Toda F.Solvent-free organic synthesis [J]. Chem. Rev.,2000,100(6):1025-1074.
[21] Liu B, Yu W-L, Lai Y-H, et al. Synthesis, characterization, and structure-propertyrelationship of no-vel fluorene-thiophene-based conjugated copolymers [J].Macromolecules,2000,33(2):8945-8952
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