螺[二苯并[a,j]氧杂蒽-14,9’-芴]的合成及性质简

芴酮与2-萘酚在硫酸和3-巯基丙酸的作用下反应得到化合物螺[二苯并[a,j]氧杂蒽-14,9’-芴]. 采用核磁共振、质谱、红外光谱和元素分析等对该化合物进行了表征,并通过X射线衍射法测得了其晶体结构,确定该化合物是通过二苯并[a,j]氧杂蒽中的含氧六元杂环和芴中的五元环共用一个碳原子形成一个螺环. 利用荧光光谱和热分析等手段对该化合物的性质进行了研究,结果表明其最大荧光发射峰为366 nm,熔点为297 ℃,热分解温度为329 ℃,具有较高的热稳定性.     

基于螺(芴-9,9'-氧杂葸)和芴的共聚物蓝光材料的合成与表征

通过控制缩合反应物中溴取代基的位置,得到了3种基于螺(芴-9,9'-氧杂蒽)的单体.利用Suzuki 偶联反应得到3种蓝光聚合物CSSFX,USSFX和DSSFX.聚合物USSFX和DSSFX具有较高的玻璃化转变温度和热分解温度.3种聚合物表现出较低并且相近的最高占有轨道能级(-5.80 eV至-5.93 eV)和最低未占有轨道能级(-2.80 eV至-3.01 eV).螺(芴-9,9'-氧杂蒽)单元的引入可降低聚合物DSSFX的最低未占有轨道能级到-3.01 eV,同时降低聚合物USSFX的最高占有轨道能级到-5.93 eV,聚合物USSFX较低的最高占有轨道能级使其具有较好的空穴注入性能.不同气氛下的高温退火实验表明,聚合物USSFX即使在空气中长时间高温退火以后,仍能保持稳定的蓝光发射.不同拓扑结构螺(芴-9,9'-氧杂蒽)单元的引入,可以有效调节蓝光聚合物的综合发光性能.     

生物质炭基磺酸催化合成14-苯基-14H-二苯并[a,j]氧杂蒽的研究

以松树皮为原料,通过炭化和磺化得到炭基磺酸;以该新型固体磺酸催化合成14-苯基-14H-二苯并[a,j]氧杂蒽化合物,考察了催化剂制备过程中的炭化方式、反应温度、反应时间、催化剂用量等因素对反应的影响。结果表明,萘酚/苯甲醛=4 mmol∶2 mmol、8%mol炭基磺酸催化剂(相对于醛)、反应时间为1 h、反应温度为100℃,无溶剂条件下收到最好的效果。     

硫酸氢钠催化合成14-烷基(芳基)-14H-二苯并[a,j]氧杂蒽类化合物

以β-萘酚,芳醛为原料,硫酸氢钠为催化剂,在无溶剂条件下合成了8个14-烷基(芳基)-14H-二苯并[a,j]氧杂蒽类化合物,其结构经1H NMR和IR表征。     

“黄-解方法”低成本合成有机半导体明星构筑单元螺芴氧杂蒽

螺芴氧杂蒽(SFX)是有机/高分子半导体材料的明星单元,在构筑发光、电荷传输与俘获材料领域应用广泛。早期SFX母体仅能通过邻卤二芳基法多步合成,2006年,黄维、解令海(黄-解)偶然发现了SFX的一锅法合成工艺,有效解决了非平面有机半导体构筑单元合成步骤复杂的问题,并进一步拓展制备了氮杂芴和含氮的螺环结构,最终形成了螺芴杂蒽类的“黄-解方法”。该方法有着步骤简单、产率高与成本低的优点,被MIT材料合成化学家高度评价和日本科学家以人名称谓,被多个领域的同行普遍采用,工业界凭借黄-解方法的高效性成功实现了SFX的量产。目前,SFX已经替代螺二芴(SBF)被学术界、工业界广泛应用,特别是韩国LG公司将其应用于有机发光二极管(OLED)显示技术。     

基于三苯胺和螺(芴-9,9'-氧杂蒽)的星射形蓝光寡聚材料的合成与光电性质

通过Sonogashira 反应合成了基于三苯胺、螺(芴-9,9'-氧杂蒽)及芴的星射形寡聚物. 三种寡聚物(TPA-F、TPA-SFX和TPA-SFXCz)都具有很高的热分解温度, 分别为417、439和425 °C. 差示扫描量热(DSC)分析研究表明, 它们也具有高的玻璃化转变温度(T_g), 都在100 °C以上, 其中两种螺芴取代的寡聚物(TPA-SFX和TPA-SFXCz)的T_g分别达到141和127 °C. 光物理的研究发现, 在薄膜中, TPA-F具有很宽的双发射峰, 峰值为424 和455 nm; 而TPA-SFX 和TPA-SFXCz 仍保持单一蓝光发射, 发射峰分别为434 和442 nm. 这表明将三苯胺非平面结构和螺形取代基团相结合, 能有效抑制在薄膜中聚集和激基缔合物的产生. 电化学的研究表明, 由于引入富电子的三苯胺核心结构, 三者都具有-5.4 eV左右的较高的HOMO能级. 通过旋涂法制备了结构为ITO(氧化铟锡)/PEDOT:PSS(聚3,4-乙撑二氧噻吩:聚苯乙烯磺酸盐)/寡聚物/TPBI(1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯)/LiF/Al 电致发光器件. 器件测试结果表明, TPA-SFX的器件具有最好的光电性能. 以它为发光层, 获得最大亮度为2680 cd·m^-2、最大电流效率为0.35 cd·A^-1、色坐标为(0.17, 0.13)的蓝光器件.     

氰基取代的螺芴氧杂蒽衍生物:激基复合物发光与性质调控

热活化延迟荧光分子因具有高效发光、价格低廉等优点,在发展有机发光二极管方面显示出巨大潜力.与单分子相比,激基复合物容易实现小的单线态-三线态能隙差,在开发延迟荧光材料方面备受关注.然而,相应受体材料的种类仍较为稀少,且激基复合物延迟荧光性质与受体材料结构之间的关系还需深入探讨.本工作设计合成出两个新型的基于螺芴氧杂蒽的电子受体材料（CNSFDBX和DCNSFDBX）.结果表明,它们与给体材料TCTA掺杂后均呈现激基复合物发射,其中TCTA：DCNSFDBX掺杂体系显示更高的发光效率,其原因归结为双氰基取代使得DCNSFDBX具有更强的接收电子的能力.该工作为开发新型电子受体材料用于激基复合物延迟荧光提供了思路.     

无溶剂条件下煤基活性炭负载硫酸作为固体酸催化合成 14-烷基(芳基)-14H-二苯并[a,j]氧杂蒽类化合物

以自制的煤基活性炭负载硫酸为催化剂, β-萘酚、醛和脂肪醛为原料, 用一锅法成功合成了11个14-烷基(芳基)-14H-二苯并[a,j]氧杂蒽类化合物, 反应时间0.1～1 h, 收率71%～96%. 该方法不仅反应时间短, 产率高, 而且催化剂价廉易得, 对环境友好, 可重复利用5次, 活性没有明显降低, 并测得催化剂的酸值为3.06 mmol/g.     

Synthesis of polyoxygenated dibenzo[a,e]cycloheptatrienes

A successive route for the synthesis of substituted dibenzo[a,e]cycloheptatriene 1 was established by the reduction of 2-allylbenzaldehyde 4, the BF₃·OEt₂-mediated intermolecular coupling of 2-allylphenylmethanol 5 with oxygenated benzenes 6, the olefinic oxidative cleavage of 7 and the intramolecular ring-closure of 8. Functionalized anthracene 13 were prepared from 2-vinylbenzaldehyde 9. The key structures were confirmed by X-ray single crystal diffraction analysis.     

Spiro,ansa-derivatives of cyclotetraphosphazenes with a tetrafluorobutane-1,4-diol

The reaction of the octachlorocyclotetraphosphazene, N₄P₄Cl₈ (1), in three stoichiometries (1:1, 1:2 and 1:3) with the sodium derivative of the fluorinated diol, 2,2,3,3-tetrafluorobutane-1,4-diol (2), in THF solution at room temperature produced seven products, whose structures have been characterized by elemental analysis, mass spectrometry, ¹H, ¹⁹F, ³¹P NMR spectroscopy and by X-ray crystallography, where suitable single crystals were obtained: the mono-spiro compound, N₄P₄Cl₆(OCH₂CF₂CF₂CH₂O) (3), its ansa isomer (4), cis- and trans-bis-spiro derivatives N₄P₄Cl₄(OCH₂CF₂CF₂CH₂O)₂ (5 and 6), tris-spiro compound N₄P₄Cl₂(OCH₂CF₂CF₂CH₂O)₃ (7), its mono-spiro-bis-ansa isomer (8) and tetrakis-spiro compound N₄P₄(OCH₂CF₂CF₂CH₂O)₄, (9). X-ray crystallographic studies confirmed that the structure of the mono-spiro-bis-ansa isomer (8) has been reported as a first example in the literature. The results of all reactions were compared with previous work on the reaction of hexachlorocyclotriphosphazene, N₃P₃Cl₆ with the sodium derivative of the diol (2), in a 1:1.2 mole ratio in the in the same solvent, THF, and with the reaction of octafluorocyclotetraphosphazene, N₄P₄F₈, with the silyl derivative of the diol (2), (Me₃SiOCH₂CF₂)₂, in a 1:0.4 mole ratio in THF.     

Synthesis and characterization of polybrominated fluorenes and their conversion to polyphenylated fluorenes and cyclopenta[def]triphenylene

We report the synthesis and characterization of polyphenylated fluorene derivatives and a ring cyclized product containing cyclopenta[def]triphenylene core. Polybromination on fluorene was achieved either by solid state reaction with bromine or utilizing Br₂/KBrO₃ in AcOH/H₂SO₄ mixture. The bromofluorenes were converted to the corresponding polyphenylated fluorenes by Suzuki coupling protocol. A hexabromofluorene underwent a multifold Suzuki coupling followed by C–H activation to produce a cyclopenta[def]triphenylene derivative. Fluorene ring showed a severe distortion from planarity beyond tetra-substitution which manifested in the optical properties.     

Synthesen mit Nitrilen, 88. Mitt.: Spiro[indol- und Spiro[inden-pyrano[2,3-c]pyrazole]aus Cyanmethylenderivaten und Pyrazolonen

Summary The reactivity of cyanomethylene-indolones (1 a–e) and 2-(dicyanomethylene)-indan-1,3-dione (4) towards 1,5-disubstituted 3-pyrazolones (2 a–c) was investigated. The reactions yield spiro[indene- and spiro[indole-4- and 6-pyrano[2,3-c]pyrazoles] (3 a–e,5 a–c). The structures are proven by¹³C-NMR-spectroscopy. The mechanisms of the reactions are discussed.

     

Spiro[3.3]heptane as a Saturated Benzene Bioisostere**

The spiro[3.3]heptane core, with the non-coplanar exit vectors, was shown to be a saturated benzene bioisostere. This scaffold was incorporated into the anticancer drug sonidegib (instead of the meta-benzene), the anticancer drug vorinostat (instead of the phenyl ring), and the anesthetic drug benzocaine (instead of the para-benzene). The patent-free saturated analogs obtained showed a high potency in the corresponding biological assays.     

Addition of thiophenols and arylamines to dibenzo[a,j]-phenoxazin-9-one

Thiophenols undergo nucleophilic addition to dibenzo[a,j]phenoxazin-9-one (II) in position 5, forming 5-arylthiodibenzo[a,j]phenoxazin-9-ones (III–V). With arylamines in the presence of their hydrochlorides,II is converted on heating into N-aryldibenzo[a,j]phenazine derivatives.     

Application of Nanosized Cu0.5Co0.5Fe2O4 Spinel Ferrite as a Nanocatalyst in the Synthesis of 14‐Aryl‐14H‐dibenzo[a,j]xanthene Derivatives under Solvent‐free Conditions

Copper and cobalt substituted spinel ferrites Cu_1‐xCo_xFe₂O₄ (0≤X≤1) have been synthesized by using hydrothermal method. The resultant spinel ferrites were systematically characterized by different techniques such as X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDX), and Fourier transform infrared spectroscopy (FT‐IR). It was indicated that all the resultant spinel ferrites obtained by the hydrothermal method had the single‐phase crystalline. The resultant spinel ferrites were employed in the synthesis of 14‐aryl‐14‐H‐dibenzo[a,j]xanthene derivatives. It was found that the nanocatalyst Cu_0.5Co_0.5Fe₂O₄ displays the best performance in the synthesis of 14‐aryl‐14H‐dibenzo[a,j]xanthenes. The catalyst was reused several times without significant loss of its activity for the preparation of desired product. In addition high yields of the products, solvent‐free conditions and reusability of the catalyst are other worthwhile advantages of the present study.     

Perhydroxylated 1,7-Dioxaspiro[5.5]undecanes (“Spiro Sugars”): Synthesis,Stereochemistry, and Structure

As spiro sugars is an apt way of considering perhydroxylated 1,7-dioxaspiro[5.5]undecanes–a class of compounds which has not been found in nature up to now. The crystal structure of such a spiroacetal, in which the two pyran rings show the β-D -manno configuration, is depicted. Note that the all-trans arrangement of C-6, C,-5, O_pyr, C_spiro, O_pyr^′, C-5′, and C-6′ does not allow any of the stereoelectronic effects that are typical of carbohydrates.