WO2012155516A1 - 聚集诱导发光的五取代四氢嘧啶及其制备方法和应用 - Google Patents

聚集诱导发光的五取代四氢嘧啶及其制备方法和应用 Download PDF

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WO2012155516A1
WO2012155516A1 PCT/CN2011/084601 CN2011084601W WO2012155516A1 WO 2012155516 A1 WO2012155516 A1 WO 2012155516A1 CN 2011084601 W CN2011084601 W CN 2011084601W WO 2012155516 A1 WO2012155516 A1 WO 2012155516A1
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tetrahydropyrimidine
aryl
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朱秋华
刘叔文
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南方医科大学
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    • C07D239/02Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/06Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
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    • C07D401/02Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
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    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to the field of organic light-emitting materials, and in particular to a penta-substituted tetrahydropyrimidine which aggregates and induces luminescence, and a preparation method and application thereof.
  • organic fluorescent compounds have good luminescent properties in dilute solutions, but in the aggregated state, especially in the crystalline state, the fluorescence is weakened or even quenched. This is because as the concentration of the fluorescent substance increases, the interaction between the molecules of the fluorescent substance is enhanced, and it is easy to form an excimer of the same kind of molecule or an exciplex between different kinds of molecules. Its fluorescence intensity is reduced (Nature, 1999, 397, 121-128; Science, 1994, 265, 765-768). In particular, organic fluorescent molecules with a rigid large planar structure have strong fluorescence in solution, but the fluorescence is weak when aggregated into solids.
  • ACQ Aggregation-caused Quenching
  • organic fluorescent substances having AIE properties have rapidly become objects of extensive research in various fields such as organic synthetic chemistry, luminescent material chemistry, biochemistry, and analytical chemistry.
  • organic fluorescent substances with AIE properties have been used in OLEDs (Patent CN101659865A, 2010; J. Phys. Chem. C. 2008, 112(10), 3975-3981; J. Am. Chem. Soc. 2002, 124(22), 6469-6479; J. Am. Chem. Soc. 2005, 127 ( 25), 9071-9078; J. Am. Chem. Soc.
  • the molecular structure of the known AIE compound has the following two characteristics: (1) The molecule contains at least two or more rigid aromatic rings which can rotate and form a conjugated system; (2) the steric hindrance generated by these rigid aromatic rings The effect is such that the entire molecule has a distorted non-planar spatial configuration, rather than a rigid planar configuration like a common organic fluorescent compound molecule.
  • the results of Tang Benzhong's research team have played a guiding role in the design and synthesis of AIE molecules.
  • the discovered AIE compounds can be simply classified into cyclic and chain compounds depending on whether a plurality of aromatic rings are attached to the ring double bonds by a single bond or to the ring double bonds. Since cyclic AIE compounds are more difficult to synthesize than chain AIE compounds, most of the reported AIE compounds belong to chain compounds.
  • the cyclic AIE compound is mainly composed of the polyphenyl silicon heterocyclic compound Silole discovered by the Tang Benzhong group (see Compound I in Figure 1, the fluorescence quantum yield of the aggregated state is better than the fluorescence of the solution). The quantum yield is increased by 330 times) (Chem. Commun. 2001, (18), 1740 - 1741).
  • the chain AIE compound is represented by a polyphenylethylene compound, such as the compound IKJ. Org. Chem. 2005, 70(7), 2778-2792) and III (J. Am. Chem. Soc. 2002 124 (48), 14410-14415).
  • the object of the present invention is to provide a novel structure of aggregation-induced luminescence penta-substituted tetrahydropyrimidine, the fluorescence quantum yield of the penta-substituted tetrahydropyrimidine in the aggregate state is 5,553 times higher than that in the solution. .
  • Another object of the present invention is to provide a process for the preparation of the aggregation-induced luminescence penta-substituted tetrahydropyrimidine.
  • the method is carried out by using a multi-component reaction.
  • the experimental materials of the method are easy to obtain, the substrate has a wide application range, and the experimental steps are simple and easy, and a large number of aggregate-induced luminescence penta-substituted tetrahydropyrimidines can be synthesized efficiently and simply.
  • Another object of the present invention is to provide the use of the aggregation-induced luminescence penta-substituted tetrahydropyrimidine.
  • R 1 is selected from a linear or branched alkyl group or a substituted d 8 alkyl group
  • R 2 and R 4 are each independently selected from d- 8 straight or branched alkyl, substituted d- 8 alkyl, ⁇ -8 cycloalkyl, substituted C 5 -8 cycloalkyl, ⁇ 6 aryl, substituted _ 6 aryl, C 9 -18 fused ring aryl, substituted C 9 -18 fused ring aryl, C 5 -6 heterocyclic, substituted ⁇ 6 heterocyclyl, C 5 -6 aromatic a cyclic or substituted C 5 -6 aromatic heterocyclic group;
  • R 3 is selected from the group consisting of ⁇ 6 aryl, substituted _ 6 aryl, C 9 -18 fused ring aryl, substituted C 9 -18 fused ring aryl, ⁇ 6 aryl heterocyclyl or substituted C 5 _ 6 aromatic heterocyclic group.
  • the aggregation-induced luminescent penta-substituted tetrahydropyrimidine, R 1 is preferably an alkyl group.
  • the aggregation-induced luminescent penta-substituted tetrahydropyrimidine, R 2 is preferably d- 5 straight or branched alkyl, substituted alkyl, ⁇ -8 cycloalkyl, ⁇ _ 6 aryl or substituted ⁇ 6 aryl.
  • the aggregation-induced luminescent penta-substituted tetrahydropyrimidine, R 3 is preferably a 1-6 aryl group or a substituted 1-6 aryl group.
  • the aggregation-induced luminescent penta-substituted tetrahydropyrimidine, R 4 is preferably d- 5 straight or branched alkyl, substituted alkyl, ⁇ -8 cycloalkyl, ⁇ _ 6 aryl or substituted ⁇ 6 aryl.
  • the above substituent is preferably a halogen, a perhalogenated alkyl group, a halogenated d 4 alkyl group, a hydroxyl group, a linear or branched alkoxy group, a nitro group, a cyano group, an amino group.
  • the aggregation-induced luminescence penta-substituted tetrahydropyrimidine preferably: wherein, in formula (I), R 1 is selected from methyl or ethyl;
  • R 2 is selected from the group consisting of phenyl, benzyl, methylphenyl, chlorophenyl, bromophenyl, trifluoromethylphenyl, n-butyl;
  • R 3 is selected from the group consisting of phenyl, bromophenyl, methoxyhydroxy substituted phenyl, bromophenyl, trifluoromethylphenyl, naphthyl, pyridyl;
  • R 4 is selected from the group consisting of phenyl, benzyl, methylphenyl, chlorophenyl, bromophenyl, trifluoromethylphenyl, hydroxyethyl, n-butyl.
  • the method for preparing the aggregation-induced luminescence penta-substituted tetrahydropyrimidine comprises the following steps:
  • the acid is one of hydrochloric acid, sulfuric acid, phosphoric acid, benzenesulfonic acid, trifluoroacetic acid or acetic acid or a mixture thereof;
  • the catalyst is any one or more of copper sulfate, copper acetate, zinc chloride, palladium acetate, thiourea, valine or urea;
  • the organic solvent is alcohol, benzene, toluene, hexane, halogenated One or more of a hydrocarbon, an ether, N,N-dimethylformamide, dimethyl sulfoxide or acetonitrile.
  • the use of the aggregation-inducing luminescent penta-substituted tetrahydropyrimidine in the preparation of an organic electroluminescent or photoluminescent device can be used as a light-emitting layer material of an organic electroluminescent or photoluminescent device.
  • the penta-substituted tetrahydropyrimidine compound having the AIE property according to the present invention is a novel class of compounds whose structure is completely different from the structure of a compound having an AIE property.
  • the molecules of the compounds contain 1 to 3 aromatic groups, these aromatic groups do not form a conjugated system between the aromatic groups in the reported AIE compounds. Even if the molecule contains only one aromatic group, such as methyl 1,3-di-n-butyl-2-phenyl-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylate, the compound still has Strong aggregation induces luminescent properties. Such compounds are by far the least conjugated AIE compounds.
  • the pentavalent tetrahydropyrimidine compound of the present invention has an aggregated fluorescence quantum yield of up to 0.8, which is higher than the aggregated fluorescence quantum yield of compound III of Figure 1 of 0.69.
  • the present invention adopts a five-component reaction method to prepare the penta-substituted tetrahydropyrimidine, and has the characteristics of multi-component reaction such as atomic economy, easy availability of raw materials, simple operation, high total yield, and diverse product structure.
  • a four component reaction of one component per component produces 10 8 structurally distinct products.
  • the synthesis method of the present invention is a five-component reaction which is easy to obtain raw materials, wide in substrate range, and simple in operation, and therefore can be used for rapidly synthesizing a large number of penta-substituted tetrahydropyrimidine compounds having extremely strong AIE properties.
  • the synthetic methods of the present invention have incomparable advantages in the ability and speed of developing new AIE compounds relative to the reported methods of synthesizing AIE properties. Since different molecular structures have different fluorescence spectra, AIE fluorescent compounds having various emission wavelengths can be synthesized by the synthesis method of the present invention.
  • the penta-substituted tetrahydropyrimidine compound of the present invention has 1 to 3 aromatic groups in the structure, and has strong aggregation-induced luminescent properties; the fluorescence intensity in the aggregate state is 5,553 times stronger than that in the solution;
  • the present invention employs an MCR reaction to prepare a penta-substituted tetrahydropyrimidine compound having a very strong AIE property, and the ability and speed of the synthesis method of the present invention in developing a new AIE compound relative to the reported method for synthesizing a compound of AIE properties It has an incomparable advantage.
  • 1 is an example of a conventional compound having AIE properties, wherein the numbers following the compound number are the fluorescence quantum yield ratio of the aggregate state of the compound to the solution and the fluorescence quantum yield of the aggregated state, respectively;
  • the compound is available under the registration number CCDC 818027 at the Cambridge Crystallographic Data Centre (CCDC), University of Cambridge, UK. ;
  • the developing solvent was n-hexane + ethyl acetate (10:1), and the eluent was ethyl acetate.
  • the solvent was removed by vacuum evaporation to give 246 mg of 1,2,3-triphenyl- 1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylic acid ethyl ester (Compound 1).
  • the compound was recrystallized to obtain a white crystal which emitted blue fluorescence at a wavelength of 365 nm and a pale green crystal which emitted green fluorescence (see Fig. 2).
  • the X-ray diffraction analysis charts of the white and green single crystals are shown in Fig. 3 and Fig. 4, respectively.
  • the product was purified by plate, and the developing solvent was n-hexane + ethyl acetate (10:1). The eluent was ethyl acetate, and the solvent was removed by vacuum rotary to give 246 mg of Compound 3.
  • Example 8-32 The synthesis method of the following Example 8-32 was the same as that of Example 6, except that the corresponding raw materials were replaced.
  • Example 27 3-bis(3-methylphenyl)-2-phenyl- 1 ,2,3,6-tetrahydropyrimidine-4,5-dicarboxylic acid methyl ester (dimethyl
  • the aggregation of the compound 134 was evaluated by measurement of the ultraviolet absorption and fluorescence emission spectrum of the compound solution, measurement of the fluorescence emission spectrum of the suspension of the compound nanoparticle, and measurement of the fluorescence quantum yield of the suspension of the compound solution and the compound nanoparticle. Induced luminescent properties.
  • the sample concentration was formulated as 5X10- 5 M ethanol solution.
  • the UV-visible absorption spectrum of the solution was measured by a Beijing-based TU-901 UV-Vis spectrophotometer.
  • the ultraviolet absorption spectrum of the fluorescent compound 1 in an ethanol solution and in an ethanol-water mixture (5:95) is shown in Fig. 6.
  • the fluorescence emission spectrum of the solution was measured on an RF5301PC fluorescence spectrophotometer of Shimadzu Corporation, Japan.
  • the poor solvent water was slowly added dropwise to the ethanol solution of the sample under ultrasonic vibration to prepare a nanoparticle suspension having a final concentration of 5 ⁇ 10 - 5 M ethanol-water (40:60-5:95).
  • the fluorescence emission spectrum in the suspension was measured on an RF5301PC fluorescence spectrophotometer of Shimadzu Corporation, Japan.
  • the fluorescence emission spectra of the nanoparticle suspensions in different ratios are shown in Figure 10.
  • Wn is the fluorescence quantum yield of the unknown sample
  • Wn and S DPA are the integrated areas of the fluorescence emission spectra of the sample and the reference excitation at a wavelength of 350 nm, respectively
  • Wn and A DPA are the absorbance of the sample and reference at a wavelength of 350 nm, respectively.
  • the fluorescence quantum yields in different ratios of ethanol-water mixture are shown in Figure 12.
  • Example 1-32 The maximum absorption wavelength ( ⁇ ), molar absorption coefficient ( ⁇ ) and quantum yield ( ⁇ 8 ) of the compound 1 -32 in a concentration of 5 ⁇ 10 - 5 M in ethanol solution, in ethanol - Maximum emission wave max in water (1:9) mixture
  • the quantum yield of cm" 1 - M" 1 ) and the compound can reach 0.81.
  • the ratio of the fluorescence quantum yield of the aggregated state of the compound 1, 8, 13, 17, 19, 22-25 to the fluorescence quantum yield of the solution is more than 1000, and has strong aggregation-induced luminescence characteristics. Therefore, such compounds are a class of aggregation-inducing luminescent substances excellent in optical properties.

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Description

聚集诱导发光的五取代四氢嘧啶及其制备方法和应用 技术领域
[0001] 本发明涉及有机发光材料技术领域, 具体涉及聚集诱导发光的五取代四氢嘧啶及其制 备方法和应用。
背景技术
[0002] 大多数有机荧光化合物在稀溶液中有很好的发光性能, 但在聚集状态, 尤其是在晶态 时, 荧光减弱甚至猝灭。 这是由于随着荧光物质浓度的增加, 荧光物质分子间的作用增强, 很容易形成同种分子间的激基缔合物 (excimer)或者不同种分子间的激基复合物 (exciplex)而使 其荧光强度降低(Nature, 1999, 397, 121-128; Science, 1994, 265, 765-768 )。尤其是有着刚性大 平面结构的有机荧光分子, 在溶液中有着很强的荧光, 但聚集成固体时荧光很弱。 这种现象 被称为荧光的 "聚集产生的淬灭效应"(Aggregation-caused Quenching, ACQ)。 ACQ限制了 荧光物质在制备有机发光二极管 (Organic Light-Emitting Diode, OLED)、化学与生物传感器等 多种领域中的应用。 如在实际制造具有驱动电压低、 重量轻、 全固化主动发光、 超薄、 发光 亮度强、 效率高、 响应速度快、 广视角、 可制作柔性可弯曲显示面板以及适合大面积显示等 多种优点的 OLED时, 需要将有机发光材料制成固体薄膜或其他聚集形式, 这就不可避免地 会产生 ACQ, 从而影响有机荧光物质的发光效率及 OLED的使用寿命。而在荧光传感器或探 针的应用方面, 由于存在 ACQ, 使得用于荧光传感器或探针的荧光物质的浓度必须在很低, 这就降低了该方法用于定量分析的准确度, 另外, 荧光物质在生物大分子活性位点的聚集也 会对对检测方法的准确度造成很大的影响。 因此, ACQ—直是有机荧光物质在实际应用过程 中一个难以克服却又必须解决的难题。 长期以来, 人们一直尝试用各种化学、 物理以及加工 工艺等方法来减弱荧光物质的 ACQ, 但取得的效果非常有限。
[0003] 在人们致力发展各种性能更加优异的新型发光材料的过程中,唐本忠 (Tang Ben Zhong) 课题组于 2001 年发现了一种在溶液中不发光, 而在固态时却呈现很强的发光特性的化合物 silole I (见图 1中化合物 I ) (Chem. Commun. 2001, 18, 1740-1741; J. Mater. Chem., 2001, 11, 2974-2978)。 他们将这一现象命名为聚集诱导发光特性 (aggregation-induced emission, AIE) 。 聚集诱导发光特性化合物的发现为 ACQ带来的 OLED使用寿命短的问题以及荧光传感器或 探针检测准确度低的问题提供了一种根本的解决方法。 因此, 具有 AIE性质的有机荧光物质 迅速成为近年来有机合成化学、 发光材料化学、 生物化学、 分析化学等多种领域广泛研究的 对象。短短的十来年间,具有 AIE性质的有机荧光物质已在 OLED(Patent CN101659865A, 2010; J. Phys. Chem. C. 2008, 112(10), 3975-3981; J. Am. Chem. Soc. 2002, 124(22), 6469-6479; J. Am. Chem. Soc. 2005, 127(25), 9071-9078; J. Am. Chem. Soc. 2006, 128(31), 10163-10170)、荧光传感 器 (Patent US20080220407A1, 2008; Patent US20100009362A1, 2010; Patent JP2010112777A, 2010; J. Am. Chem. Soc. 2010, 132(40), 13951-13953; Macromolecules 2009, 42(5), 1421-1424; Chem. Commun. 2009, (33), 4974-4976)、 荧光探针 (Org. Biom. Chem. 2011, 9(7), 2219-2226; Chem. Commun. 2010, 46(23), 4067-4069; Chem-Eur. J. 2010, 16(28), 8433-8438; Chem. Commun. 2009, (33), 4974-4976; Chem. Commun. 2006, (35), 3705-3707) 以及生物活性检测 (Org. Lett. 2009, 11(17), 4014-4017; Org. Lett. 2010, 12(10), 2274-2277) 等多种应用领域中显 示了其独特性质的优势(Curr. Org. Chem. 2010, 14(18), 2109-2132; J. Mater. Chem. 2010, 20(10), 1858-1867; Chem. Commun. 2009, (29), 4332-4353; J. Inorg. Organomet. P. 2009, 19(3), 249-285 ) o
[0004] 虽然具有 AIE性质的有机荧光物质在多种领域有广泛的应用前景, 但目前该类化合物 的种类很少。 唐本忠课题组对影响 AIE性质的因素及产生的原因进行了深入的研究, 提出了 产生 A1E现象的机制:认为在溶液中 AIE分子可以通过苯环的转动或振动而发生非辐射衰变, 所以不发荧光,而在聚集态时 AIE分子的转动或振动受到限制,使其可以以辐射的形式衰变, 从而导致其在固态时发光(Angew. Chem. Int. Ed. 2009, 48, 7608-7611; J. Am. Chem. Soc, 2005, 127, 6335-6346; Chem. Mater., 2003, 15, 1535-1546; J. Phys. Chem. C, 2007, 111, 2287-2294)。 已 知的 AIE化合物分子结构具有以下两个特点: (1)分子中至少含有两个或多个可旋转并相互形 成共轭体系的刚性芳香环; (2)这些刚性芳香环产生的空间位阻效应使得整个分子呈扭曲的非 平面空间构型, 而不是像普通的有机荧光化合物分子具有刚性的平面空间构型。 唐本忠课题 组的研究结果对 AIE分子设计合成起到了指导的作用。 近年来发展了许多具有聚集诱导发光 增强现象 (aggregation, induced emission enhancement, AIEE)的化合物, 即化合物在溶液中具 有发光性, 在聚集态下其发光性有一度程度 (一般小于 100倍) 的增加 (J. Mater. Chem. 2011, 21(11), 3760-3767; Chem-Eur. J. 2011, 17(9), 2647-2655; Chem. Commun. 2010, 46(47), 9013-9015; J. Phys. Chem. C, 2010, 114(43), 18702-18711)。 但在溶液中几乎没有发光性, 而在 聚集态下才发荧光的化合物, 即具有 AIE性质的化合物却不多。 其中聚集态发光强度比溶液 发光强度强两个数量级的 AIE化合物只有少数几种, 如图 1中的化合物 I和化合物 III。
[0005] 根据多个芳香环是通过单键连在环内双键上还是连在环外双键上, 可将已发现的 AIE 化合物简单的分为环状和链状化合物。 由于环状的 AIE化合物较链状 AIE化合物更难合成, 所以报道的 AIE化合物大多数属于链状化合物。环状的 AIE化合物主要以唐本忠课题组发现 的多苯基硅杂环化合物 Silole (如图 1中的化合物 I, 其聚集态的荧光量子产率比溶液的荧光 量子产率提高 330倍)为主 (Chem. Commun. 2001, (18), 1740 - 1741 )。 将 Silole中的 Si原子 换成 Ge、 Sn原子时也有一定的 AIE性质, 但 AIE效应很弱, 聚集态的荧光量子产率仅提高 几倍(Inorg. Chem. 2005, 44(6), 2003 - 2011 )。 链状的 AIE化合物则以多苯基乙烯类化合物为 代表,如图 1中的化合物 IKJ. Org. Chem. 2005, 70(7), 2778—2792)与 III(J. Am. Chem. Soc. 2002 124(48), 14410-14415)。 另外还有几种结构特别的 AIE化合物, 如两个或多个苯环直接由单 键相连形成共轭体系的化合物 IV和 V (该类化合物的荧光波长在紫外区非可见光区, 没有测 聚集态与溶液的荧光量子产率, Chem. Commun., 2007, 70 - 72), 以及共轭体系中含 C=N双键 的化合物 VI(J. Org. Chem.2009, 74, 2163 - 2166)。 由于 AIE化合物的用途广泛, 因此需要发 展多种发光效率优良的 AIE荧光化合物。
发明内容
[0006] 本发明的目的在于提供一类结构新颖的聚集诱导发光的五取代四氢嘧啶, 该五取代四 氢嘧啶在聚集态的荧光量子产率比溶液中的荧光量子产率强达 5553倍。
[0007] 本发明的另一目的在于提供所述聚集诱导发光的五取代四氢嘧啶的制备方法。 该方法 采用多组分反应进行, 该方法的实验原料易得、 底物适用范围宽、 实验步骤简单易行, 可高 效简便地合成数量庞大的聚集诱导发光的五取代四氢嘧啶。
[0008] 本发明的另一目的在于提供所述聚集诱导发光的五取代四氢嘧啶的应用。
[0009] 本发明的上述目的通过如下技术方案予以实现:
聚集诱导发光的五取代四氢嘧啶, 具有如式 ( I ) 所示结构:
Figure imgf000005_0001
式中:
R1选自 直链或支链烷基或取代的 d_8烷基;
R2、 R4各自独立选自 d_8直链或支链烷基、 取代的 d_8烷基、 ^_8环烷基、 取代的 C5_8环烷 基、 ^_6芳香基、 取代的 ^_6芳香基、 C9_18稠环芳香基、 取代的 C9_18稠环芳香基、 C5_6杂环 基、 取代的 ^_6杂环基、 C5_6芳杂环基或取代的 C5_6芳杂环基;
R3选自 ^_6芳香基、 取代的 ^_6芳香基、 C9_18稠环芳香基、 取代的 C9_18稠环芳香基、 ^_6芳 杂环基或取代的 C5_6芳杂环基。 [0010] 作为一种优选方案, 所述的聚集诱导发光的五取代四氢嘧啶, R1优选为 烷基。
[0011] 作为一种优选方案, 所述的聚集诱导发光的五取代四氢嘧啶, R2优选为 d_5直链或支 链烷基、 取代的 烷基、 ^_8环烷基、 ^_6芳香基或取代的 ^_6芳香基。
[0012] 作为一种优选方案, 所述的聚集诱导发光的五取代四氢嘧啶, R3优选为 ^_6芳香基或 取代的 ^_6芳香基。
[0013] 作为一种优选方案, 所述的聚集诱导发光的五取代四氢嘧啶, R4优选为 d_5直链或支 链烷基、 取代的 烷基、 ^_8环烷基、 ^_6芳香基或取代的 ^_6芳香基。
[0014] 作为一种优选方案, 上述的取代基, 优选为卤素、全卤代的 烷基、 卤代 d_4烷基、 羟基、 直链或支链烷氧基、 硝基、 氰基、 氨基、 d_6单烷基氨基、 d_6二烷基氨基、 C5_8 单环烷基氨基、 ^_6单杂环基氨基、 C5_6单芳基氨基、 d_6烷基酰氨基、 c5_6芳基酰氨基、 氨 基羰基、 _6单烷基氨基羰基、 d_6二烷基氨基羰基、 d_6烷基酰基、 c5_8芳基酰基、 氨基砜 基、 单烷基氨基砜基、 d_6二烷基氨基砜基、 ^_8芳基氨基砜基、 d_6烷基磺酰氨基、 羧 基、 单烷基砜基、直链或支链烷基、 ^_8环烷基、 ^_8取代的环烷基、 C2_4烯基、 C2_4块基、 芳基 Cw烷基、 ^_6芳香基、 ^_6取代的芳香基、 C9_18稠环芳香基、 ^_6杂环基、 C5_6芳杂环 基或 c9_18稠环芳杂环基。
[0015] 作为一种优选方案, 所述的聚集诱导发光的五取代四氢嘧啶, 优选为: 式 ( I ) 中, R1选自甲基或乙基;
R2选自苯基, 苄基, 甲基苯基, 氯苯基, 溴苯基, 三氟甲基苯基, 正丁基;
R3选自苯基, 溴苯基, 甲氧基羟基取代的苯基, 溴苯基, 三氟甲基苯基, 萘基, 吡啶基;
R4选自苯基, 苄基, 甲基苯基, 氯苯基, 溴苯基, 三氟甲基苯基, 羟乙基, 正丁基。
[0016] 所述聚集诱导发光的五取代四氢嘧啶的制备方法, 包括如下步骤:
以下物质用量按毫摩尔份数计算:
( 1 ) 在 l〜10mL的有机溶剂中, 加入 1份式 ( II ) 化合物和 1份式 (III) 化合物, 在 0〜60 °C下搅拌 10〜60分钟;
(2)在 l〜10mL的有机溶剂中, 分别加入 1〜5份式 (IV)、 1〜5份甲醛, 同时加入 0〜4份酸, 在 20〜100°C下搅拌 10分钟〜 5小时;
(3) 将步骤 (1 ) 和步骤 (2) 的反应液混合后, 加入 1〜5份式 (V ) 化合物和 0.1〜0.5份催 化剂, 在 -15〜100°C下搅拌 1〜7天, 分离纯化得到产品;
R1 OOC ^≡ COOR1
( II ), R NH2
(III) ,
R4NH2
( IV ) ,
R3CHO
( V ) ;
所述酸为盐酸、 硫酸、 磷酸、 苯磺酸、 三氟乙酸或乙酸中的一种或其混合物;
所述催化剂为硫酸铜、 醋酸铜、 氯化锌、 醋酸钯、 硫脲、 脯氨酸或脲中的任意一种或几种; 所述有机溶剂为醇、 苯、 甲苯、 己烷、 卤代烃、 醚、 N,N-二甲基甲酰胺、 二甲亚砜或乙腈中 的一种或几种。
[0017] 所述聚集诱导发光的五取代四氢嘧啶在制备有机电致或光致发光器件中的应用。 所述 的五取代四氢嘧啶可以作为有机电致或光致发光器件的发光层材料。
[0018] 所述聚集诱导发光的五取代四氢嘧啶在制备化学及生物荧光传感器或探针中的应用。
[0019] 本发明涉及的具有 AIE性质的五取代四氢嘧啶化合物是一类全新的化合物, 其结构完 全不同于已有 AIE性质化合物的结构。 该类化合物的分子中虽然含有 1〜3个芳香基, 但这些 芳香基并不像已报道的 AIE化合物中的芳香基之间形成共轭体系。 即使分子中只含有一个芳 香基, 如 1,3-二正丁基 -2-苯基 -1,2,3,6-四氢嘧啶 -4,5-二甲酸甲酯, 该类化合物仍然具有很强的 聚集诱导发光性质。 这类化合物是至今为止分子共轭程度最低的 AIE化合物。 本发明涉及的 五取代四氢嘧啶化合物在溶液中 (如四氢呋喃、 二氯甲烷、 乙酸乙酯及乙醇中) 完全没有荧 光, 但在混合溶液中 (乙醇-水 =1 :9) 及在晶态下发很强的荧光; 在聚集态荧光强度比在溶液 中的荧光强度高达 5553倍, 比图 1中化合物 III的 AIE性质更强。 本发明涉及的五取代四氢 嘧啶化合物的聚集态荧光量子产率高达 0.8, 比图 1中化合物 III的聚集态荧光量子产率 0.69 更高。
[0020] 本发明采用五组分反应法制备所述的五取代四氢嘧啶, 具有原子经济性、 原料易得、 操作简单、总产率高、产物结构多样等多组分反应特点。理论上来说, 一个各组份原料为 100 种的四组分反应可产生 108个结构不同的产物。 本发明涉及的合成方法是一种原料易得、 底 物范围宽、 操作简单的五组分反应, 因此, 可用于快速合成数量庞大的具有极强 AIE性质的 五取代四氢嘧啶类化合物。 因而, 相对于已报道的合成 AIE性质化合物的方法, 本发明的合 成方法在发展新的 AIE化合物的能力及速度上具有不可比拟的优势。 由于不同的分子结构具 有不同的荧光光谱,因此可通过本发明的合成方法合成具有多种发射波长的 AIE荧光化合物。
[0021] 与现有技术相比, 本发明具有如下有益效果: ( 1 )本发明所述五取代四氢嘧啶化合物结构中含有 1〜3个芳香基, 具有很强的聚集诱导发光 性质; 在聚集状态的荧光强度比溶液中的荧光强度强达 5553倍;
(2)本发明采用 MCR反应制备具有极强 AIE性质的五取代四氢嘧啶类化合物, 相对于已报 道的合成 AIE性质化合物的方法, 本发明的合成方法在发展新的 AIE化合物的能力及速度上 具有不可比拟的优势。
附图说明
[0022] 图 1为现有的具有 AIE性质的化合物示例, 其中, 化合物编号后面的数字分别为该化 合物聚集态与溶液的荧光量子产率比值和聚集态的荧光量子产率;
图 2为实施例 1化合物的白色和浅绿色两种晶体在 λ =365ηηι下的发光情况;其中, 白色晶体 Α发蓝色荧光, 浅绿色晶体 B发绿色荧光;
图 3为在 λ =365nm下发蓝色荧光的实施例 1化合物单晶 X-射线衍射分析图, 化合物在英国 剑桥大学的剑桥晶体数据中心 (Cambridge Crystallographic Data Centre, CCDC)的登记号为 CCDC 818027;
图 4为在 λ =365nm下发绿色荧光的实施例 1化合物单晶 X-射线衍射分析图,化合物在 CCDC 的登记号为 CCDC 818026;
图 5为在 λ =365nm下发蓝色荧光的实施例 1化合物在乙醇溶液及在乙醇-水混合液 (5:95)中的 紫外吸收光谱;
图 6为在 λ =365nm下发绿色荧光的实施例 1化合物在乙醇溶液及在乙醇-水混合液 (5:95)中的 紫外吸收光谱;
图 7为在 λ =365nm下发蓝色荧光的实施例 1化合物在乙醇溶液中的荧光发射光谱; 图 8为在 λ =365nm下发绿色荧光的实施例 1化合物在乙醇溶液中的荧光发射光谱; 图 9为在 λ =365ηηι下发蓝色荧光的实施例 1化合物在不同比例的乙醇-水混合溶液中的荧光 发射光谱;
图 10为在 λ =365nm下发绿色荧光的实施例 1化合物在不同比例的乙醇-水混合溶液中的荧光 发射光谱;
图 11为在 λ =365ηηι下发蓝色荧光的实施例 1化合物在不同比例的乙醇-水混合溶液中的荧光 量子产率;
图 12为在 λ =365nm下发绿色荧光的实施例 1化合物在不同比例的乙醇-水混合溶液中的荧光 量子产率。
具体实施方式 [0023] 以下结合实施例来进一步解释本发明, 但实施例并不对本发明做任何形式的限定。
[0024] 实施例 1
( 1 )将 lmmol(170mg)的丁块二酸二乙酯、 lmmol (93mg)的苯胺依次加入到 2mL乙醇中, 室 温下搅拌 20min。
[0025] (2)将 2mmol(186mg)的苯胺、2mmol(160mg) 的 30重量%甲醛水溶液、 2mmol( 120mg) 的乙酸加入到 2mL乙醇中, 40 °C下搅拌 20min。
[0026] 将(1 )禾卩 (2)的反应液混合, 40°C下, 加入 2mmol(212mg)的苯甲醛, O.lmmol ( 6mg) 脲, 反应 48h后, 加饱和氯化钠水溶液 20mL, 用二氯甲烷 20mL萃取, 重复三次, 合并的二 氯甲烷溶液, 再用饱和氯化钠水溶液 20mL萃取, 重复三次, 所得二氯甲烷溶液用硫酸镁干 燥, 减压蒸馏除溶剂, 再用制备薄层析板纯化产物, 展开剂为正己烷 +乙酸乙酯 (10: 1 ), 洗 脱剂为乙酸乙酯, 用真空旋蒸法除去溶剂得 246mg的 1,2,3-三苯基 -1,2,3,6四氢嘧啶 -4,5-二羧 酸乙酯 (化合物 1)。 化合物通过重结晶得到在 365nm波长下发蓝色荧光的白色晶体和发绿色 荧光的浅绿色晶体(见附图 2)。白色和绿色单晶的 X-射线衍射分析图分别见附图 3和附图 4。
三 苯基 -1,2,3,6- 四 氢 嘧 啶 -4,5- 二 甲 酸 乙 酯 ( diethyl
Figure imgf000009_0001
l,2,3,6-tetrahydro-l,2,3-triphenylpyrimidine-4,5-dicarboxylate, 化合物 1 ); 产率 54%, 蓝色荧光 的白色晶体, 熔点 = 129.6-130.5 °C ; 绿色荧光的浅绿色晶体, mp = 119.5-120.5 °C ; IR (KBr): v max = 2980, 1739, 1697, 1592, 1495, 1234, 1108, 761, 696 cm"1; 1H NMR(400 MHz, CDC13): δ =7.67-6.90(m, 15H), 6.12(s, 1H), 4.30(d, J=17.6Hz, 1H), 4.12-4.07(m, 4H), 3.61-3.56(d, J=17.6Hz, 1H), 1.22(t, J=7.2Hz, 3H), 1.03(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): =165.45, 164.24, 149.57, 144.94, 144.44, 138.46, 129.35, 129.09, 129.07, 128.34, 126.99, 126.08, 124.46, 121.45, 118.98, 101.48, 79.87, 61.65, 60.16, 42.62, 14.22, 13.57 ppm; MS (ESI): m/z 457(M + H+, 28), 276(100); Anal. Calcd for C28H28N204: C, 73.66; H, 6.18; N, 6.14; Found: C, 73.91; H, 6.10; N: 6.21。
[0028] 实施例 2
( 1 ) 将 lmmol(170mg)的丁块二酸二乙酯、 lmmol (107mg)的苄胺依次加入到 lmL Ν,Ν-二 ψ 基甲酰胺中, 室温下搅拌 10min。 [0029] (2) 将 lmmol(107mg)的苄胺和 lmmol(80mg) 的 30%甲醛加入到 2mL N,N-二甲基甲 酰胺中, 室温下搅拌 10min。
[0030] ( 3 )将 (1 )和 (2) 的反应液混合, 80°C下, 加入 lmmol(106mg)的苯甲醛, 0.5mmol ( 55mg) 脯氨酸, 反应 24h后, 加饱和氯化钠水溶液 20mL, 用二氯甲烷 20mL萃取, 重复 三次, 合并的二氯甲烷溶液, 再用饱和氯化钠水溶液 20mL萃取, 重复三次, 所得二氯甲烷 溶液用硫酸镁干燥, 减压蒸馏除溶剂, 再用制备薄层析板纯化产物, 展开剂为正己烷 +乙酸乙 酯 (10:1 ), 脱剂为乙酸乙酯, 用真空旋蒸法除去溶剂得 140mg的化合物 2。
[0031] 1,3-二苄基 -2-苯基 -1,2,3,6-四氢嘧啶 -4,5-二甲酸乙酯 ( diethyl
Figure imgf000010_0001
l,3-dibenzyl-l,2,3,6-tetrahydro-2-phenylpyrimidine-4,5-dicarboxylate, 化合物 2)产率 29%, 白色 固体, 熔点 = 107.2-108.0°C ; IR (KBr): max = 2983, 2358, 1735, 1688, 1575, 1447, 1285, 1147, 1109, 746, 688 cm"1; 1H NMR(400 MHz, CDC13): δ= 7.43-7.06(m, 15H), 4.79(s, 1H), 4.57(d, J=15.6Hz, 1H), 4.54-4.50(m, 2H), 4.13-4.09(m, 2H), 4.0 l(d, J=15.6Hz, 1H), 3.69(d, J=13.6Hz, 1H) 3.44(d, J=13.6Hz, 1H), 3.39(d, J=16.8Hz, 1H), 3.26(d, J=16.8Hz, 1H), 1.47(t, J=7.2Hz, 3H), 1.22(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): δ= 166.50, 165.41, 147.75, 136.49, 128.88, 128.78, 128.72, 128.25, 128.16, 126.96, 91.06, 74.12, 62.32, 59.59, 57.68, 53.38, 42.56, 14.39, 14.06 ppm; MS (ESI): m/z 485(M + H+, 67), 290(100); Anal. Calcd for C30H32N2O4: C, 74.36; H, 6.66; N, 5.78; Found: C, 74.15; H, 6.71; N, 5.83。
[0032] 实施例 3
( 1 ) 将 lmmol(170mg)的丁块二酸二乙酯、 lmmol (107mg)的对甲苯胺依次加入到 lmL正己 烷中, 室温下搅拌 lh。
[0033] (2) 将 5mmol(107mg)的对甲苯胺和 3mmol(240mg) 的 30%甲醛加入到 10mL二氯甲 烷中, 室温下搅拌 10min。
[0034] ( 3 )将 ( 1 )和 (2) 的反应液混合, 室温下, 加入 5mmol(530mg)的苯甲醛, 0.5mmol 醋酸铜, 反应 36h后, 加饱和氯化钠水溶液 20mL, 用二氯甲烷 20mL萃取, 重复三次, 合并 的二氯甲烷溶液, 再用饱和氯化钠水溶液 20mL萃取, 重复三次, 所得二氯甲烷溶液用硫酸 镁干燥, 减压蒸馏除溶剂, 再用制备薄层析板纯化产物, 展开剂为正己烷 +乙酸乙酯 (10: 1 ), 洗脱剂为乙酸乙酯, 用真空旋蒸法除去溶剂得 246mg的化合物 3。
[0035] 1,3-二 (4-甲基苯基) -2-苯基 -1,2,3,6-四氢嘧啶 -4,5-二甲酸乙酉 ί
Figure imgf000011_0001
(diethyll , 2,3, 6-tetrahydro-2 -phenyl- l ,3-dip-tolylpyrimidine-4,5-dicarboxylate, 化合物 3); 产率 51%, 黄色固体, 熔点 = 146.5-148.2 °C ; IR (KBr): max =3059, 3029, 2924, 1740, 1698, 1595, 1511 , 1423, 1390, 1289, 1234, 1107, 1007, 817, 760, 698 cm"1; 1H NMR(400 MHz, CDC13): δ= 7.66-6.84(m, 13H), 5.99(s, 1H), 4.22 (d, J=17.6Hz, 1H), 4.19-4.07(m, 4H), 3.55(d, J=17.6Hz, 1H), 2.27(s, 3H), 2.26(s, 3H), 1.21(t, J=7.2Hz, 3H), 1.06(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDCls) =165.58, 164.37, 147.38, 145.45, 141.78, 138.69, 135.99, 130.90, 129.84, 129.62, 128.98, 128.23, 127.07, 124.67, 119.30, 100.14, 80.19, 77.38, 77.06, 76.75, 61.58, 60.03, 42.69, 20.95, 20.61 , 14.25, 13.63 ppm; MS (ESI): m/z 485(M + H+, 31), 290 (100); Anal. Calcd for C30H32N2O4: C, 74.36; H, 6.66; N, 5.78; Found: C, 74.05; H, 6.61 ; N, 5.69。
[0036] 实施例 4
( 1 ) 将 lmmol(170mg)的丁块二酸二乙酯、 lmmol (127mg)的对氯苯胺依次加入到 lmL甲醇 中, 60°C下搅拌 10min。
[0037] ( 2 )将 1.5mmol(190mg)的对氯苯胺和 lmmol(80mg) 的 30%甲醛加入到 10mL二氯甲 烷中, 常温下搅拌 10min。
[0038] ( 3 )将(1 )和 ( 2 )的反应液混合, 室温下, 加入 1.5mmol(159mg)的苯甲醛, 0.5mmol ( 55mg) 硫脲, 反应 36h后, 加饱和氯化钠水溶液 20mL, 用二氯甲烷 20mL萃取, 重复三 次, 合并的二氯甲烷溶液, 再用饱和氯化钠水溶液 20mL萃取, 重复三次, 所得二氯甲烷溶 液用硫酸镁干燥, 减压蒸馏除溶剂, 再用制备薄层析板纯化产物, 展开剂为正己烷 +乙酸乙酯 ( 10: 1 ) , 洗脱剂为乙酸乙酯, 用真空旋蒸法除去溶剂得 262mg的化合物 4。
[0039] 1,3-二 ( 4-氯苯基) -2-苯基 -1,2,3,6-四氢嘧啶 -4,5-二甲酸乙酉 ί
Figure imgf000011_0002
(diethyl l,3-bis(4-chlorophenyl)-l,2,3,6-tetrahydro-2-phenylpyrimidine-4,5- dicarboxylate, 化合物 4);产率 50%,黄色固体, 熔点 = 166.8-167.6°C ; IR (KBr): = 2983 2357, 1740, 1697, 1601, 1492, 1232, 1104 1007, 825, 756, 700 cm"1; 1H NMR(400 MHz, CDC13): δ= 7.63-6.86(m, 13H), 5.60(s 1H), 4.21(d, J=l 8.0Hz, 1H), 4.15-4.11 (m, 4H), 3.56(d, J=l 8.0Hz, 1H), 1.22(t, J=7.2Hz, 3H): 1.10(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): δ= 165.19, 164.00, 148.07, 144.30, 142.93, 137.71, 131.71, 129.36, 129.26, 128.67, 126.81, 126.66, 125.42, 120.45, 102.21, 80.31, 61.94, 60.41 42.57, 14.20, 13.68 ppm; MS (ESI): m/z 525(M + H+ 45), 310 (100); Anal. Calcd for C28H26C12N204: C 64.01; H 4.99; N 5.33; Found: C 64.23; H 4.83; N 5.45.
实施例 5
( 1 ) 将 lmmol(170mg)的丁块二酸二乙酯、 lmmol (170mg)的对溴苯胺依次加入到 3mL甲醇 中, 室温下搅拌 30min
[0040] (2) 将 1.5mmol(285mg)的对溴苯胺和 1.2mmol(120mg) 的 30%甲醛、 5mmol(300mg) 乙酸加入到 5mL甲醇中, 室温下搅拌 10min
[0041] ( 3 ) 将 (1 ) 和 (2) 的反应液混合, 室温下, 加入 1.5mmol(159mg)的苯甲醛, 反应 36h后, 加饱和氯化钠水溶液 20mL, 用二氯甲烷 20mL萃取, 重复三次, 合并的二氯甲烷溶 液, 再用饱和氯化钠水溶液 20mL萃取, 重复三次, 所得二氯甲烷溶液用硫酸镁干燥, 减压 蒸馏除溶剂, 再用制备薄层析板纯化产物, 展开剂为正己烷 +乙酸乙酯 (10: 1 ), 洗脱剂为乙 酸乙酯, 用真空旋蒸法除去溶剂得 318mg的化合物 5
[0042] 1 3-二 ( 4-溴苯基) -2-苯基 -1 2 3 6-四氢嘧啶 -4 5-二甲酸乙酉 ί
Figure imgf000012_0001
(diethyl 1 ,3 -bis(4-bromophenyl)- 1 ,2,3 ,6-tetrahydro-2-phenylpyrimidine-4,5- dicarboxylate, 化合物 5); 产率 52%,黄色固体, 熔点 = 154.6-155.4°C ; IR (KBr): max = 2982, 2360, 1738, 1696, 1597, 1490, 1232, 1109, 1005, 820, 756, 700 cm 1; 1H NMR(400 MHz, CDC13): δ= 7.62-7.31(m, 9H), 6.90-6.81(m, 4H), 6.01(s 1H), 4.2 l(d, J=l 8.0Hz, 1H), 4.15-4.10(m, 4H), 3.55(d, J=l 8.0Hz, 1H), 1.22(t, J=7.2Hz, 3H), l .l l(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): δ= 165.12, 163.97 148.49, 144.10, 143.45, 137.66, 132.34, 132.30, 129.27, 128.68, 126.79, 125.61, 120.68, 119.50, 114.01, 102.52, 79.92, 61.95 60.42, 42.60, 14.19, 13.68 ppm; MS (ESI): m/z 613(M + H+ 15), 615(M + H+ 31), 354 (90), 356 (100); Anal. Calcd for C28H26Br2N204: C 54.74; H 4.27; N 4.56; Found: C, 54.81; H, 4.35; N, 4.61。
[0043] 实施例 6
( 1 )将 lmmol(170mg)的丁块二酸二乙酯、 lmmol (161mg)的间三氟甲基苯胺依次加入到 lmL 甲醇中, 室温下搅拌 60min。
[0044] (2)将 3mmol(483mg)的间三氟甲基苯胺和 1.4mmol(112mg) 的 30%甲醛、 4mmol(240mg) 乙酸加入到 5mL甲醇中, 常温下搅拌 10min。
[0045] ( 3 )将( 1 )和(2)的反应液混合,室温下,加入 1.5mmol(159mg)的苯甲醛, 0.2mmol(12mg) 脲反应 48h后, 加饱和氯化钠水溶液 20mL, 用二氯甲烷 20mL萃取, 重复三次, 合并的二氯 甲烷溶液, 再用饱和氯化钠水溶液 20mL萃取, 重复三次, 所得二氯甲烷溶液用硫酸镁干燥, 减压蒸馏除溶剂, 再用制备薄层析板纯化产物, 展开剂为正己烷 +乙酸乙酯 (10: 1 ), 洗脱剂 为乙酸乙酯, 用真空旋蒸法除去溶剂得 291mg的化合物 6。
Figure imgf000013_0001
乙 酉旨 ; ( diethyll,3-bis(3-(trifluoromethyl)phenyl)-l,2,3,6-tetrahydro-2-phenylpyrimidine-4,5- dicarboxylate, 化合物 6); 产率 50%, 白色固体, 熔点 = 104.4-105.2 °C ; IR (KBr): max = 2986, 2357, 1741, 1700, 1600, 1499, 1234, 1125, 866, 758, 695 cm"1; 1H NMR(400 MHz, CDC13): δ= 7.64-7.14(m, 13H), 6.14(s, 1H), 4.33(d, J=18.4Hz, 1H), 4.16-4.10(m, 4H), 3.66(d, J=18.4Hz, 1H), 1.23(t, J=7.2Hz, 3H), 1.12(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): δ= 164.90, 163.98, 149.65, 144.95, 143.46, 137.25, 130.15, 130.03, 129.40, 128.84, 126.73, 126.54, 122.53, 121.87, 120.41, 118.19, 115.25, 104.65, 79.21, 62.13, 60.61, 43.29, 14.17, 13.42 ppm; MS (ESI): m/z 593(M + H+, 45), 344 (100); Anal. Calcd for C30H26F6N2O4: C, 60.81; H, 4.42; N, 4.73; Found: C, 60.98; H, 4.53; N, 4.61。
[0047] 实施例 7
( 1 ) 将 lmmol(170mg)的丁块二酸二乙酯、 lmmol (107mg)的间甲基苯胺依次加入到 lmL甲 醇中, 室温下搅拌 60min。
[0048] (2)将 3mmol(321mg)的间甲基苯胺和 1.4mmol(112mg) 的 30%甲醛、 0.1mmol(9.8mg) 硫酸加入到 5mL甲醇中, 常温下搅拌 10min。
[0049] ( 3 )将( 1 )和(2)的反应液混合,室温下,加入 1.5mmol(159mg)的苯甲醛, 0.2mmol(12mg) 脲反应 48h后, 加饱和氯化钠水溶液 20mL, 用二氯甲烷 20mL萃取, 重复三次, 合并的二氯 甲烷溶液, 再用饱和氯化钠水溶液 20mL萃取, 重复三次, 所得二氯甲烷溶液用硫酸镁干燥, 减压蒸馏除溶剂, 再用制备薄层析板纯化产物, 展开剂为正己烷 +乙酸乙酯 (10: 1 ), 洗脱剂 为乙酸乙酯, 用真空旋蒸法除去溶剂得 291mg的化合物 7。
[0050] 1 ,3-二 (3-甲基苯基) -2-苯基 -1,2,3,6-四氢嘧啶 -4,5-二甲酸乙酉 ί
Figure imgf000014_0001
( diethyl l ,3-bis(3-methylphenyl)-l ,2,3,6-tetrahydro-2-phenylpyrimidine-4,5- dicarboxylate, 化合 物 7 ) ; 产率 46%, 黄色固体, 熔点 = 100.0-100.8 °C ; IR (KBr): max = 2980, 1740, 1698, 1582, 1492, 1249, 1178, 1108, 759, 698 cm"1; 1H NMR(400 MHz, CDC13): δ= 7.65-6.72(m, 13H), 6.10(s, 1H), 4.29(d, J=17.6Hz, 1H), 4.15-4.07(m, 4H), 3.57(d, J=17.6Hz, 1H), 1.21(t, J=7.2Hz, 3H): 1.07(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): δ= 165.46, 164.42, 149.56, 144.81 , 144.45, 139.05, 138.60, 129.14, 129.04, 128.88, 128.25, 127.03, 126.82, 124.90, 121.99, 121.40, 119.45, 115.63, 101.85, 78.90, 61.60, 60.12, 43.10, 21.69, 21.31 , 14.24, 13.62 ppm; MS (ESI): m/z 485(M + H+, 50), 290(100); Anal. Calcd for C30H32N2O4: C, 74.36; H, 6.66; N, 5.78; Found: C, 74.13; H, 6.69; N, 5.84。
[0051] 以下实施例 8-32的合成方法与实施例 6相同, 区别在于替换了相应的原料。
[0052] 实施例 8
1 ,3-二苯基 -2- ( 4-溴苯基) -1,2,3,6-四氢嘧啶 -4,5-二甲酸乙酯; (diethyl
Figure imgf000014_0002
2-(4-bromophenyl)-l ,2,3,6-tetrahydro-l ,3-diphenylpyrimidine-4,5-dicarboxylate化合物 8); 产率 31%,黄色固体, 熔点 = 162.4-164.6 °C ; IR (KBr): vmax = 2981 , 2352, 1739, 1697, 1592, 1495, 1372, 1293, 1236, 1107, 1009, 910, 747, 696 cm 1; 1H NMR(400 MHz, CDC13): δ= 7.59-6.92(m, 14H), 6.04(s, 1H), 4.29(d, J=17.6Hz, 1H), 4.14-4.08(m, 4H), 3.56(d, J=17.6Hz, 1H), 1.23(t, J=7.2Hz, 3H), 1.03(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): δ= 165.28, 164.15, 149.32, 144.61 , 144.24, 137.55, 132.27, 129.40, 129.20, 128.89, 126.17, 124.22, 122.49, 121.68, 118.99, 102.05, 79.30, 61.75, 60.29, 42.75, 14.22, 13.58 ppm; MS (ESI): m/z 535(M + H+, 49), 537(M + H+ 49), 276(100); Anal. Calcd for C28H27BrN204: C 62.81 ; H 5.08; N 5.23; Found: C 62.93; H, 5.18; N, 5.16.
实施例 9
( 3-甲氧基 -4-羟基苯基) -1 2 3 6-四氢嘧啶 -4,5-二甲酸乙
Figure imgf000015_0001
酉旨 ( diethyl 1 ,2,3,6-tetrahydro-2-(4-hydroxy-3-methoxyphenyl)-l ,3- diphenylpyrimidine-4,5-dicarboxylate, 化合物 9 ) ; 产率 53%, 黄色固体, 熔点 = 164.1-164.6°C ; IR (KBr): max = 2981 , 2360, 1735, 1697, 1579, 1496, 1282, 1235, 1109, 763, 696 cm"1; lH NMR(400 MHz, CDC13): δ= 7.26-6.89(m, 13H), 6.08(s 1H), 5.69(s 1H), 4.28(d, J=17.6Hz, 1H), 4.14-4.05(m, 4H), 3.88(s, 3H), 3.63(d, J=17.6Hz, 1H), 1.22(t, J=7.2Hz, 3H), 1.05(t J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): δ= 165.39, 164.37, 149.51 , 146.90, 145.53, 144.53, 144.48, 130.23, 129.32, 129.13, 125.84, 123.86, 121.35, 119.90, 118.88 114.85 109.52, 102.26, 79.24, 61.65, 60.18 56.02, 53.45, 42.85, 14.23, 13.63ppm; MS (ESI): m/z 503(M + H+ 34), 276(30), 228(100); Anal. Calcd for C29H30N2O6: C 69.31 ; H 6.02; N 5.57; Found: C 69.24; H 6.16; N 5.45.
实施例 10
1-苄基 -2,3-二苯基 -1 ,2,3,6-四氢嘧啶 -4,5-二甲酸乙酯 ( diethyl
Figure imgf000015_0002
l-benzyl-l ,2,3,6-tetrahydro-2,3-diphenylpyrimidine-4,5-dicarboxylate, 化合物 10); 产率 37%,白 色固体, 熔点 = 100.0-100.8 °C ; IR (KBr): = 3061 3030, 2980, 2930, 2362, 1736, 1697, 1630, 1578, 1496 1283, 1104, 1056 752, 698 cm"VH NMR (400 MHz, CDC13): δ= 7.62-7.15(m, 15H), 5.22(s, 1H), 4.24-4.08 (m 4H), 3.95(s, 2H), 3.56(d, J=17.6Hz, 1H), 3.34(d, J=17.6Hz, 1H), 1.22(t, J=7.2Hz, 3H), 1.13(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13) =166.16 164.52, 144.78, 143.92, 129.11 , 128.96, 128.81 , 128.35, 128.07, 127.33, 127.12, 125.72, 123.89, 99.89 79.28, 61.73, 60.01 57.60, 44.12, 14.22, 13.66 ppm; MS (ESI): m/z 471(M + H+ 100); Anal. Calcd for
C29H30N2O4: C 74.02; H 6.43; N 5.95; Found: C 74.31 ; H 6.54; N 5.83. 实施例 11
1 ,2-二苯基 -3-苄基 -1,2,3,6-四氢嘧啶 -4,5-二甲酸乙酯 ( diethyl
Figure imgf000016_0001
3-benzyl-l ,2,3,6-tetrahydro-l ,2-diphenylpyrimidine-4,5-dicarboxylate, 化合物 11 ) ; 产率 21%, 白色固体, 熔点 = 102.4-103.4°C ; IR (KBr): vmax = 3061 , 3029, 2980, 2935, 2903, 1737, 1692, 1593, 1496, 1452, 1367, 1284, 1223, 1147, 1108, 1032, 749, 697 cm"1; 1H NMR(400 MHz, CDC13): δ= 7.36-7.25 (m, 4H), 7.19 (s, 1H), 7.06 (m, 5H), 6.92 (m, 5H), 5.62 (s, 1H), 4.43 (d, / = 16.0 Hz, 1H), 4.33-4.22 (m, 2H), 4.10-4.02 (m, 4H), 3.43 (d, / = 16.8 Hz, 1H), 1.21-1.15 (m, 6H) ppm; 13C NMR(101MHz, CDC13): δ= 165.69, 165.05, 149.11, 148.47, 137.40, 135.91 , 129.19, 128.92, 128.47, 128.36, 127.72, 127.69, 126.69, 121.16, 118.84, 93.52, 75.64, 62.14, 59.82, 53.81 , 40.16, 14.40, 13.86 ppm; MS (ESI): m/z 471(M + H+, 45); Anal. Calcd for C29H30N2O4: C, 74.02; H, 6.43; N, 5.95; Found: C, 74.13; H, 6.33; N, 5.79.
实施例 12
1-苄基 -2-苯基 -3- ( 3-甲基苯基) -1,2,3,6-四氢嘧啶 -4,5-二甲酸乙酯(diethyl
Figure imgf000016_0002
l-benzyl-l ,2,3,6-tetrahydro-3-(3-methylphenyl)-2-phenylpyrimidine-4,5- dicarboxylate, 化合物 12); 产率 38%, 黄色油状物; IR (KBr): vmax = 3061 , 3029, 2978, 2852, 1738, 1697, 1581 , 1492, 1450, 1366, 1249, 1217, 1177, 1105, 1061, 781 , 699cm—1; 1H NMR (400 MHz, CDC13): δ =7.52-6.85(m, 14H), 5.12(s, 1H), 4.14-4.07(m, 2H), 4.00(q, / = 7.2 Hz, 2H), 3.83(s, 2H), 3.43(d, J = 18.0 Hz, 1H), 3.20(d, / = 18.0 Hz, 1H), 2.18(s, 3H), 1.10(t, J=7.2Hz, 3H), 1.05(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): δ= 166.22, 164.64, 144.77, 143.97, 139.41 , 139.04, 138.32, 128.95, 128.87, 128.80, 128.32, 128.00, 127.28, 127.14, 126.52, 124.38, 120.96, 99.85, 79.42, 61.69, 59.98, 57.57, 44.02, 21.35, 14.22, 13.69 ppm; MS (ESI): m/z 485(M + H+, 100); Anal. Calcd for C30H32N2O4: C, 74.36; H, 6.66; N, 5.78; Found: C, 74.16; H, 6.57; N, 5.69.
实施例 13 1 -苄基 -2-苯基 -3 -(4-溴苯基 )- 1,2,3,6-四氢嘧啶 -4,5-二甲酸乙酯 ( diethyl
Figure imgf000017_0001
l-benzyl-3-(4-bromophenyl)-l,2,3,6-tetrahydro-2-phenylpyrimidine-4,5- dicarboxylate, 化合物 13 );产率 29%, 白色固体, 熔点 = 119.9-121.4°C; IR (KBr): ^max= 3278, 2929, 2358, 1690, 1621 1548, 1193, 1070, 737, 670 cm"1; 1H NMR(400 MHz, CDC13): δ = 7.59-7.03(m, 14H), 5.17(s, 1H), 4.25-4.22(m, 2H), 4.13-4.08(m, 2H), 3.95(d, / = 13.6 Hz, 1H), 3.89(d, / = 13.6 Hz, 1H), 3.55(d, /= 18.4Hz, 2H), 3.33(d, J=18.4Hz, 2H), 1.23-1.19(m, 6H) ppm; 13C NMR (101 MHz, CDC13): δ = 165.97, 164.38, 144.00, 143.06, 138.90, 137.92, 132.19, 128.93, 128.88, 128.44, 128.22, 127.46, 126.99, 125.03, 118.69, 101.37, 79.18, 61.93, 60.17, 57.64, 44.21, 14.19, 13.76 ppm; MS (ESI): m/z 549(M + H+, 80), 551(M + H+, 100); Anal. Calcd for C29H29BrN204: C, 63.39; H, 5.32; N, 5.10; Found: C, 63.51; H, 5.42; N, 5.0.
实施例 14
1 -苄基 -2- ( 3-甲氧基 -4-羟基苯基) -3-(3-甲基苯基 )-1,2,3,6-四氢嘧啶 -4,5-
Figure imgf000017_0002
二 甲 酸 乙 酉旨 ( diethyll-benzyl-l,2,3,6-tetrahydro-2-(4-hydroxy-3-methoxyphenyl)-3- m-tolylpyrimidine-4,5-dicarboxylate,化合物 14);产率 31%, 黄色固体, 熔点 = 170.3-171.6°C ; IR (KBr): max = 3434, 2980, 2358, 1734, 1696, 1581, 1515, 1251, 1107, 736, 670 cm"1; 1H NMR(400 MHz, CDC13): δ= 7.26-6.93 (m, 12H), 5.65(s, 1H), 5.16(s, 1H), 4.19-4.04(m, 4H), 3.88(s, 3H), 3.87(s, 2H), 3.48(d, J=18.0 Hz, 1H), 3.3 l(d, J=18.0 Hz, 1H), 2.26(s, 3H), 1.20-1.12(m, 6H) ppm; 13C NMR (101 MHz, CDC13) =166.13, 164.74, 146.65, 145.22, 144.95, 143.50, 139.06, 138.39, 131.30, 128.89, 128.29, 127.23, 126.24, 123.71, 120.28, 120.01, 114.71, 109.77, 100.97, 79.11, 61.65, 59.99, 57.48, 55.96, 44.08, 21.37, 14.22, 13.74ppm; MS (ESI): m/z 531(M + H+, 41), 242 (100); Anal. Calcd for C31H34N206: C, 70.17; H, 6.46; N, 5.28; Found: C, 70.23; H, 6.38; N, 5.19. 实施例 15
1,2-二苯基 -3 -(4-氯苯基 )-1,2,3,6-四氢嘧啶 -4,5-二甲酸乙酯 ( diethyl
Figure imgf000018_0001
3-(4-chlorophenyl)-l,2,3,6-tetrahydro-l,2-diphenylpyrimidine-4,5- dicarboxylate, 化合物 15 ); 产 率 47%, 黄色固体, 熔点 = 141.7-142.3 °C ; IR (KBr): = 2981, 1738, 1698, 1599, 1492, 1237, 1102, 828, 750, 697 cm 1; 1H NMR(400 MHz, CDC13): δ= 7.66-6.86(m, 14H), 6.06(s, 1H), 4.28(d, J=18.0 Hz, 1H), 4.14-4.08(m, 4H), 3.58(d, J=18.0 Hz, 1H), 1.22(t, J=l .2 Hz, 3H), 1.09(t, J=l 2 Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): δ= 165.30, 164.13, 149.45, 144.29, 143.13, 138.10, 131.49, 129.42, 129.23, 129.19, 128.50, 126.89, 125.48, 121.71, 119.06, 102.67, 80.25, 61.84, 60.31, 42.55, 14.21, 13.68 ppm; MS (ESI): m/z 491 (M + H+, 56), 276 (100); Anal. Calcd for C28H27C1N204: C, 68.50; H, 5.54; N, 5.71; Found: C, 68.39; H, 5.50; N, 5.85.
实施例 16
1,2-二苯基 -3-(4-甲基苯基) - 1 ,2,3,6-四氢嘧啶 -4,5-二甲酸乙酯 ( diethyl
Figure imgf000018_0002
3-(4-methylphenyl)-l,2,3,6-tetrahydro-l,2-diphenylpyrimidine-4,5- dicarboxylate, 化合物 16); 产 率 37%, 黄色固体, 熔点 = 123.9-125.2 °C ; IR (KBr): = 3073, 2357, 1742, 1699, 1508, 1234, 1107, 911, 757, 683 cm"1; 1H NMR(400 MHz, CDC13): δ = 7.71-6.87(m, 14H), 6.11(s, lH), 4.31(d, J=17.6Hz, 1H), 4.18-4.10 (m, 4H), 3.61(d, J=17.6Hz,lH), 2.29(s, 3H), 1.25(t, J=7.2Hz, 3H), 1.09(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13) δ= 165.52, 164.34, 149.63, 145.40, 141.78, 138.55, 136.07, 129.66, 129.35, 129.08, 129.03, 128.30, 127.02, 124.65, 124.45, 121.39, 119.03, 118.99, 100.34, 79.91, 61.61, 60.09, 42.48, 20.95, 14.25, 13.63 ppm; MS (ESI): m/z 471(M + H+, 48), 276(100); Anal. Calcd for C29H30N2O4: C, 74.02; H, 6.43; N, 5.95; Found: C, 74.29; H, 6.27; N, 5.78.
实施例 17 1 -(4-氯苯基 )-2,3-二苯基 - 1,2,3,6-四氢嘧啶 -4,5-二甲酸乙酯 ( diethyl
Figure imgf000019_0001
l-(4-chlorophenyl)-l ,2,3,6-tetrahydro-2,3-diphenylpyrimidine-4,5- dicarboxylate, 化合物 17); 产 率 53%, 白色固体, 熔点 = 139.3-139.9°C ; IR (KBr): vmax = 3115, 2359, 1702, 1515, 966, 676 cm 1; 1H NMR(400 MHz, CDC13): δ = 7.47-6.88(m, 14H), 6.02(s, 1H), 4.23(d, J=l 8.0Hz, 1H), 4.17-4.11(m, 4H), 3.58(d, J=l 8.0Hz, 1H), 1.25 (t, J=7.2Hz, 3H), 1.12 (t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): δ = 165.17, 163.98, 148.07, 142.94, 137.72, 131.72, 129.36, 129.25, 128.65, 126.80, 125.43, 120.43, 102.22, 80.32, 61.92, 60.40, 42.56, 14.19, 13.66 ppm; MS (ESI): m/z 491 (M + H+, 100), 310 (80); Anal. Calcd for C28H27C1N204: C, 68.50; H, 5.54; N, 5.71 ; Found: C, 68.30; H, 5.51 ; N, 5.83.
实施例 18
l-(4-甲基苯基) -2,3-二苯基 -1,2,3,6-四氢嘧啶 -4,5-二甲酸乙酯 (diethyl
Figure imgf000019_0002
l-(4-methylphenyl)-l ,2,3,6-tetrahydro-2,3-diphenylpyrimidine-4,5- dicarboxylate, 化合物 18); 产 率 36% , 白色固体,熔点 = 131.1-132.2°C ; IR (KBr): max =2984, 2358, 1742, 1698, 1508, 1232, 1108, 1008, 756, 683 cm 1; 1H NMR(400 MHz, CDC13): δ = 7.67-6.84(m, 14H), 6.04(s, 1H), 4.23(d, /= 18.0Hz, 1H), 4.13-4.08(m, 4H), 3.57(d, J=l 8.0Hz, 1H), 2.26(s, 3H), 1.21(t, J=7.2Hz, 3H): 1.03(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): = 165.53, 164.29, 147.32, 145.01 , 144.45, 138.60, 130.98, 129.84, 129.62, 129.06, 129.03, 128.98, 128.29, 127.05, 126.01 , 124.69, 124.48, 119.27, 101.27, 80.18, 61.63, 60.11 , 60.02, 42.83, 20.58, 14.22, 13.58 ppm; MS (ESI): m/z 471(M + H+, 90), 290 (100); Anal. Calcd for C29H30N2O4: C, 74.02; H, 6.43; N, 5.95; Found: C, 74.32; H, 6.57; N, 5.76.
实施例 19 1-苯基 -3-对甲苯基 -2- ( 4-吡啶基) -1,2,3,6-四氢嘧啶 -4,5-二甲酸甲酉 ί
Figure imgf000020_0001
( dimethyl l,2,3,6-tetrahydro-l-phenyl-2-(pyridin-4-yl)-3-p-tolylpyrimidine-4,5-dicarboxylate, 化 合物 35 ); 产率 11%, 白色固体, 熔点 = 202.2-203.1 °C; ^ NMR^OO MHz, CDC13): = 8.71 (d, J = 5.2 Hz, 2H), 7.62 (d, J = 5.6 Hz, 2H), 7.24 - 6.90 (m, 9H), 5.99 (s, 1H), 4.23 (d, J = 18.0 Hz, 1H), 3.67 (s, 3H), 3.66 (s, 3H), 3.52 (d, J = 18.0 Hz, 1H), 2.27 (s, 3H) ppm; 13C NMR (151 MHz, CDC13): δ= 165.54, 164.64, 150.46, 147.83, 146.72, 144.56, 143.99, 131.66, 129.98, 129.36, 126.30, 123.86, 122.10, 119.16, 102.52, 79.19, 52.66, 51.57, 43.07, 20.54. ppm; MS (ESI): m/z 444(M + H+, 100), 248(30), 197(80); Anal. Calcd for C26H25N304: C, 70.41; H, 5.68; N, 9.47; Found: C, 70.53; H, 5.54; N, 9.22.
实施例 20
1- ( 2-羟乙基) -2,3-二苯基 -1,2,3,6-四氢嘧啶 -4,5-二甲酸甲酯 (dimethyl
Figure imgf000020_0002
l,2,3,6-tetrahydro-l-(2-hydroxyethyl)-2,3-diphenylpyrimidine-4,5- dicarboxylate, 化合物 20); 产 率 23%, 白色固体, 熔点 = 49.9-50.8°C; IR (KBr): max = 3510, 2948, 2353, 1741, 1695, 1583, 1495, 1236, 1111, 756, 697 cm 1; 1H NMR(400 MHz, CDC13): δ= 7.56-7.1 l(m, 10H), 5.3 l(s, 1H), 3.77-3.75(m, 1H), 3.68(s, 3H), 3.66(b, 1H), 3.63(s, 3H), 3.50 (d, /=18.0Hz, 1H), 3.18(d, /=18.0Hz, 1H), 3.97-3.91(m, 2H), 2.58(s, 1H) ppm; 13C NMR (101 MHz, CDC13): δ= 166.39, 164.82, 144.45, 144.34, 138.48, 129.36, 129.01, 128.44, 126.97, 126.29, 124.01, 98.66, 81.82, 59.14, 55.04, 52.65, 51.38, 42.52 ppm; MS (ESI): m/z 397(M + H+, 100), 419 (M + Na+, 47); Anal. Calcd for C22H24N205: C, 66.65; H, 6.10; N, 7.07; Found: C, 66.45; H, 6.21; N, 7.12.
实施例 21 1,2,3-三苯基 -1 2 3 6- 四 氢嘧 啶 -4,5-二 甲 酸 甲 酯 ( dimethyl
Figure imgf000021_0001
1 ,2,3,6-tetrahydro- 1 ,2,3-triphenylpyrimidine-4,5-dicarboxylate , 化合物 21 ); 产率 61% , 黄色固 体, 熔点 = 145.8-146.5 °C; IR (KBr): = 2950 2356, 1743, 1699 1589 1496 1234, 1112, 917 756, 696 cm 1; 1H NMR(400 MHz, CDC13): δ= 7.67-6.91(m, 15H), 6.12(s, 1H), 4.28(d, J=17.6Hz, 1H), 3.66(s, 3H), 3.64(s, 3H), 3.59(d, J=17.6Hz, 1H) ppm; 13C NMR (101 MHz, CDC13) δ =165.88, 164.89, 149.47, 145.00, 144.33, 138.28, 129.37, 129.23, 129.12, 128.43, 126.96, 126.12, 124.04, 121.58, 119.01 101.33, 79.96, 52.60, 51.48 42.57 ppm; MS (ESI): m/z 429(M + H+ 41), 248 (100); Anal. Calcd for C26H24N204: C 72.88; H 5.65; N 6.54; Found: C 72.97; H 5.49; N 6.61.
实施例 22
1 3-二对甲苯基 -2-萘基 - 1 2,3 6-四氢嘧啶 -4,5-二甲酸甲酯 ( dimethyl
Figure imgf000021_0002
1 ,2,3,6-tetrahydro-2-(naphthalen-2-yl)-l,3-dip-tolylpyrimidine-4,5-dicarboxylate, 化合物 36)产率 29%, 白色固体, 熔点 = 158.0-159.0°C; IR (KBr): max = 3027, 2948, 2920, 2860, 1742, 1701, 1592, 1511, 1434, 1366, 1236, 1111, 1064, 818 739, 480 cm"1; 1H NMR(600 MHz, CDC13): δ= 8.19 (s 1H), 7.96 - 7.88 (m 3H), 7.76 (dd J = 8.5 1.2 Hz, 1H), 7.55 (dd J = 6.2, 3.2 Hz, 2H), 7.11 (d J = 8.4 Hz, 2H), 7.03 (dd J = 14.8, 8.4 Hz, 4H), 6.92 (d J = 8.3 Hz, 2H), 6.19 (s, 1H), 4.28 (d J = 17.9 Hz, 1H), 3.73 (s, 3H), 3.65 (s, 3H), 3.62 (d J = 17.9 Hz, 1H), 2.32 (s, 3H), 2.29 (s, 3H) ppm; 13C NMR (151 MHz, CDC13): = 165.83 164.94, 147.27, 145.46, 141.70, 135.95, 135.72, 133.32, 133.22, 131.05, 129.81, 129.72, 128.93, 128.59, 127.55, 126.44, 126.37, 126.19, 124.61, 124.18, 119.36, 100.04, 80.38, 52.46, 51.23, 42.71, 20.85, 20.52 ppm; MS (ESI): m/z 507(M + H+ 28), 262(55), 246(100); Anal. Calcd for C32H30N2O4: C 75.87; H 5.97; N 5.53; Found: C 75.61; H: 5.83; N, 5.67.
实施例 23 1,3-二 (4-甲基苯基) -2-苯基 -1,2,3,6-四氢嘧啶 -4,5-二甲酸甲酯 (dimthyl
Figure imgf000022_0001
1,3- bis(4-methylphenyl)-l,2,3,6-tetrahydro-2-phenylpyrimidine-4,5-dicarboxylate, 化合物 23); 产率 63%, 黄色固体, 熔点 = 164.1-164.6°C ; IR (KBr): max = 3688, 3031, 1742, 1699, 1593, 1510, 1239, 1110, 1064, 913, 821, 747 cm"1; 1H NMR(400 MHz, CDC13): δ= 7.65-6.81(m, 13H), 6.00(s, 1H), 4.20(d, J=17.6Hz, 1H), 3.65(s, 6H), 3.64(s, 6H), 3.55(d, J=17.6Hz, 1H), 2.27(s, 3H), 2.26(s, 3H) ppm; 13C NMR (101 MHz, CDC13) δ= 166.00, 164.98, 147.26, 145.52, 141.69, 138.51 136.03, 131.04, 129.85, 129.76, 129.02, 128.30, 127.02, 124.31, 119.32, 99.98, 80.34, 52.53, 51.38, 42.57, 20.96, 20.60 ppm; MS (ESI): m/z 457(M + H+, 34), 262 (100); Anal. Calcd for C28H28N204: C, 73.66; H, 6.18; N, 6.14; Found: C, 73.51; H, 6.23; N, 6.25.
实施例 24
1,3-二 (4-氯苯基 )-2-苯基 -1,2,3,6-四氢嘧啶 -4,5-二甲酸甲酯 (dimethyl
Figure imgf000022_0002
l,3-bis(4-chlorophenyl)-l,2,3,6-tetrahydro-2-phenylpyrimidine-4,5-dicarboxylate, 实施例 24); 产 率 55%, 浅黄色固体, 熔点 = 153.1-153.9°C; IR (KBr): 3675, 3064, 1741, 1699, 1590
1493, 1240, 1115, 913, 830, 737, 709 cm"1; Ή NMR(400 MHz, CDC13): δ= 7.62-6.84(m, 13H), 6.00(s, 1H), 4.19(d, J=l 8.0Hz, 1H), 3.68(s, 3H), 3.66(s, 3H), 3.56(d, J=l 8.0Hz, 1H) ppm; 13C NMR (101 MHz, CDCls): δ= 165.59, 164.58, 147.97, 144.37, 142.83, 137.55, 131.79, 129.48, 129.38, 129.29, 128.73, 126.77, 125.11, 120.47, 102.04, 80.43, 52.79, 51.63, 42.49 ppm; MS (ESI): m/z 497(M + H+, 29), 282(100); Anal. Calcd for C25H27N305: C26H22C12N204: C, 62.79; H, 4.46; N, 5.63; Found: C, 62.87; H, 4.29; N, 5.51.
实施例 25 ;Me¾c f Ύ, 1,3-二 (4-溴苯基 )-2-苯基 -1,2,3,6-四氢嘧啶 -4,5-二甲酸甲酯 ( dimethyl
8r
l ,3-bis(4-bromophenyl)-l ,2,3,6-tetrahydro-2-phenylpyrimidine-4,5-dicarboxylate, 化合物 25 ); 产 率 47%, 浅黄色固体, 熔点 = 144.5-145.0 °C ; IR (KBr): vmax = 2950, 2356, 1741 , 1699, 1596, 1490, 1236, 1113, 913, 823, 737, 640 cm"1; JH NMR(400 MHz, CDC13): δ= 7.61-6.79(m, 13H), 6.01(s, 1H), 4.19(d, J=18.4Hz, 1H), 3.68(s, 3H), 3.66(s, 3H), 3.56(d, J=18.4Hz, 1H) ppm; 13C NMR (101 MHz, CDCls): δ= 165.54, 164.57, 148.40, 144.19, 143.34, 137.49, 132.47, 132.32, 129.31 , 128.75, 126.75, 125.29, 120.72, 119.60, 114.15, 102.32, 80.05, 52.83, 51.65, 42.52 ppm; MS (ESI): m/z 585(M + H+, 50), 587 (100); Anal. Calcd for C26H22Br2N204: C, 53.27; H, 3.78; N, 4.78; Found: C, 53.43; H, 3.91 ; N, 4.61.
实施例 26
1,3-二 (3-三氟甲基苯基 )-2-苯基 -1,2,3,6-四氢嘧啶 -4,5-二甲酸甲酉 ί
Figure imgf000023_0001
( dimethyl l ,3-bis(3-(trifluoromethyl)phenyl)-l ,2,3,6-tetrahydro-2-phenylpyrimidine-4,5-dicarboxylate , 化合 物 26); 产率 48%, 白色固体, 熔点 = 152.3-153.0°C ; IR (KBr): vmax = 3687, 2954, 1742, 1704, 1590, 1595, 1235, 1125, 1073, 909, 735, 670,650 cm 1; 1H NMR(400 MHz, CDC13): δ = 7.65-7.14(m, 13H), 6.16(s, 1H), 4.32(d, J=l 8.0Hz, 1H), 3.70(s, 3H), 3,68(s, 3H), 3.67(d, J=l 8.0Hz, 1H) ppm; 13C NMR (101 MHz, CDC13): δ= 165.29, 164.57, 149.57, 144.84, 143.50, 137.09, 132.04, 131.71 , 130.23, 130.07, 129.45, 128.93, 126.69, 126.11 , 125.22, 122.51 , 121.84, 119.92, 118.32, 118.29, 115.25, 115.21 , 104.54, 79.15, 52.75, 51.78, 43.28 ppm; MS (ESI): m/z 565(M + H+, 32), 316 (100); Anal. Calcd for C28H22F6N204: C, 59.58; H, 3.93; N, 4.96; Found: C, 59.39; H, 3.81 ; N, 4.86.
实施例 27 1 3-二 (3-甲基苯基 )-2-苯基- 1 ,2,3,6-四氢嘧啶 -4,5-二甲酸甲酯( dimethyl
Figure imgf000024_0001
l,2,3,6-tetrahydro-2-phenyl-l,3-dim-tolylpyrimidine-4,5-dicarboxylate, 化合物 27); 产率 52%, 黄色固体, 熔点 = 112.9-113.9°C; IR (KBr): max = 2949, 1742, 1702, 1582, 1492, 1251, 1230, 1179, 1112, 758, 698 cm"1; 1H NMR(400 MHz, CDC13): δ= 7.65-6.72(m, 13H), 6.11(s, 1H), 4.26(d, J=17.6Hz, 1H), 3.66(s, 3H), 3.64(s, 3H), 3.57(d, J=17.6Hz, 1H), 2.25(s, 3H), 2.23(s, 3H) ppm; 13C NMR (101 MHz, CDC13): δ= 165.87, 165.05 149.47, 144.87, 144.39, 139.23, 139.08, 138.44, 129.17, 129.09, 128.95, 128.33, 126.99, 126.89, 124.43, 122.13, 121.03, 119.49, 115.67, 101.75, 79.05, 52.52, 51.44 43.02, 21.69, 21.35 ppm; MS (ESI): m/z 457(M + H+ 21), 262 (100); Anal. Calcd for C28H28N204: C 73.66; H 6.18; N 6.14; Found: C 73.78; H 6.31; N 6.09.
28
1 3-二正丁基 -2-苯 ¾ -1,2,3,6-四氢嘧啶 -4,5-二甲酸甲酯 ( dimethyl
Figure imgf000024_0002
l,3-dibutyl-l,2,3,6-tetrahydro-2-phenylpyrimidine-4,5-dicarboxylate, 化合物 28); 产率 41% 黄色油状物; IR (KBr): = 2954 2868, 2358, 1743, 1689 1577, 1432, 1286, 1140 1096 7534, 683 cm"1; 1H NMR(400 MHz, CDC13): δ = 7.29-7.19(m, 5H), 4.86(s, 1H), 3.89 (s, 3H), 3.52(s, 3H), 3.25(d, /=16.8Hz 1H), 3.18-3.14(m, 1H), 2.97(d, /=16.8Hz 1H), 2.91-2.88(m, 2H), 2.57-2.54(m, 2H), 1.47-1.35(m, 6H), 1.19-1.14(m, 2H), 0.90(t J=7.2Hz, 3H), 0.80(t J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): =167.06 165.57, 147.78, 138.96, 129.46, 128.64, 128.02, 126.81, 115.42, 90.33, 65.57, 52.96, 52.76, 50.90 50.52, 41.84 31.87, 30.45, 20.46, 19.86, 14.08, 13.66 ppm; MS (ESI): m/z 389(M + H+ 100); Anal. Calcd for C22H32N204: C 68.01; H 8.30; N 7.21; Found: C 68.24; H 8.19; N 7.32.
实施例 29 1,3-二苯基 -2-(3-溴苯基 )-l 2 3 6-四氢嘧啶 -4,5-二甲酸甲酯 (dimethyl
Figure imgf000025_0001
2-(3-bromophenyl)-l,2,3,6-tetrahydro-l,3-diphenylpyrimidine-4,5-dicarboxylate, 化合物 29); 产 率 47%, 黄色固体, 熔点 = 142.5-144.3 °C ; IR (KBr): = 3036 2949, 2925, 2853, 1741, 1701, 1592, 1581, 1496 1472, 1456, 1273, 1113, 1046, 782, 696 cm"1; 1H NMR(400 MHz, CDC13): δ= 7.80-6.90(m, 14H), 6.06(s 1H), 4.29(d, J=l 8.0Hz, 1H), 3.68(s, 3H), 3.65(s, 3H), 3.61(d, J=l 8.0Hz, 1H) ppm; 13C NMR (101 MHz, CDC13) =165.71 149.25, 144.12, 140.78, 131.68, 130.74, 130.16, 129.42, 129.31, 126.21, 125.68, 123.87, 123.21, 121.91, 119.15 101.88, 79.38, 52.66, 51.57, 42.75 ppm; MS (ESI): m/z 507(M + H+ 100), 509(100); Anal. Calcd for C26H23BrN204: C 61.55; H 4.57; N 5.52; Found: C 61.38; H 4.39; N 5.61.
施例 30
1 3-二苯基 -2-(4-三氟甲基苯基 )-l 2 3 6-四氢嘧啶 -4 5-二甲酸甲酉 ί
Figure imgf000025_0002
( dimethyl-2-(4-(trifluoromethyl)phenyl)-l 2 3 6-tetrahydro-l 3-diphenylpyrimidine-4 5-dicarboxy late,化合物 30);产率 25%,黄色固体,熔点 = 145.3-146.2 °C ; IR (KBr): max = 2925 2852, 2360, 1704, 1596, 1580, 1495 1435, 1324, 1236, 1111, 1068, 1033, 747, 695cm—1; 1H NMR(400 MHz, CDC13): δ = 7.84-6.93(m, 14H), 6.16(s 1H), 4.32(d, J=l 8.0Hz, 1H), 3.70(s, 3H), 3.68(s, 3H), 3.56(d, J=l 8.0Hz, 1H) ppm; 13C NMR (101 MHz, CDC13): = 165.63 164.72, 149.18, 144.64, 144.10, 142.32, 129.47, 129.37, 127.51, 126.29, 126.21, 126.17, 123.84, 121.94, 119.02, 102.20, 79.48, 77.23, 52.68, 51.60 42.77, 31.60, 22.67, 14.14 ppm; MS (ESI): m/z 497(M + H+ 32), 248(100); Anal. Calcd for C27H23F3N204: C 65.32; H 4.67; N 5.64; Found: C 65.46; H 4.58; N 5.76.
实施例 31 1,3-二苯基 -2-(4-溴苯基 )-1,2,3,6-四氢嘧啶 -4,5-二甲酸甲酯
Figure imgf000026_0001
(dimethyl-2-(4-bromophenyl)-l 2 3 6-tetrahydro-l 3-diphenylpyrimidine-4 5-dicarboxylate, 化合 物 31 ); 产率 51% , 黄色固体, 熔点 = 164.5-165.9°C; R (KBr): = 2981 2352 1739 1697 1592, 1495 1372, 1293, 1236, 1107, 1009 910 747, 696 cm"1; 1H NMR(400 MHz, CDC13): δ = 7.59-6.90(m, 14H), 6.04(s, 1H), 4.27(d, J=l 8.0Hz, 1H), 3.66(s, 3H), 3.64(s, 3H), 3.57(d, J=l 8.0Hz, 1H) ppm; 13C NMR (101 MHz, CDC13): δ = 165.71, 164.81 149.23, 144.68 144.15 137.37, 132.32, 129.43, 129.34, 128.86, 126.23, 123.83, 122.59, 121.82, 119.03, 101.91 79.43, 52.68, 51.58, 42.69 ppm; MS (ESI): m/z 507(M + H+ 49), 509(M + H+ 51), 248(100); Anal. Calcd for C26H23BrN204: C 61.55; H 4.57; N 5.52; Found: C 61.38; H 4.62; N 5.47.
施例 32
(3-甲氧基 -4羟基苯基) -1 2 3 6-四氢嘧啶 -4,5-二甲酸
Figure imgf000026_0002
( dimethyll 2 3 6-tetrahydro-2-(4-hydroxy-3-methoxyphenyl)-l 3-diphenylpyrimidine-4 5-dicarbo xylatea,化合物 32);产率 52%,黄色固体, 熔点 = 158.5-160.1 °C; IR (KBr): max = 3061, 2950, 1740, 1697, 1580 1514 1495 1434, 1282, 1237, 1115 762, 696 CM-1; 1H NMR(400 MHz, CDC13): δ= 7.25-6.89(m, 13H), 6.09(s 1H), 5.72(s.lH), 4.26(d, J=l 8.0Hz, 1H), 3.88(s, 3H), 3.66(s, 3H),
3.65(s, 3H), 3.60(d, J=l 8.0Hz, 1H) ppm; 13C NMR (101 MHz, CDC13): δ= 165.81, 165.03, 149.42, 146.98, 145.62, 144.62, 144.39, 130.06, 129.34, 129.24, 125.89, 123.51, 121.47, 119.86, 118.90, 114.88 109.48 102.12, 79.40, 56.04 52.57, 51.47, 42.74 ppm; MS (ESI): m/z 475(M + H+ 31), 248(100); Anal. Calcd for C27H26N206: C 68.34; H 5.52; N 5.90; Found: C 68.48; H 5.61; N 5.88.
实施例 33 1-正丁基 -2 3-二苯基 -1 2 3 6- 四氢嘧啶 -4,5-二 甲 酸 甲 酯
Figure imgf000027_0001
(l-butyl-l,2,3,6-tetrahydro-2,3-diphenylpyrimidine-4,5-dicarboxylate, 化合物 33); 产率 21%, 白 色固体, 熔点 = 122.1-122.6°C; IR (KBr): = 2951, 1742, 1700, 1578, 1495 1407, 1240, 1108, 750, 698 cm 1; 1H NMR(400 MHz, CDC13): δ= 7.61-7.14 (m 10H), 5.33 (s 1H), 3.70 (s 3H), 3.65 (s, 3H), 3.49 (d J = 18.4 Hz, 1H), 3.19 (d, / = 17.8 Hz, 1H), 2.78-2.75 (m 2H), 1.53-1.42 (m 4H), 0.93 (t, / = 7.2 Hz, 3H) ppm; 13C NMR (101 MHz, CDC13): δ= 166.70, 165.06 144.80 144.15, 139.30, 129.25, 128.85, 128.07, 127.08, 125.88, 123.84, 99.18 81.13, 52.90, 52.55, 51.28, 43.13, 30.20, 20.38, 13.97 ppm; MS (ESI): m/z 409(M + H+ 50), 228(100); Anal. Calcd for C24H28N204: C 70.57; H 6.91; N 6.86; Found: C 70.33; H 6.79; N 6.93.
施例 34
1-苄基 -2,3-二苯基 -1 2 3 6-四氢嘧啶 -4,5-二甲酸甲酯 ( dimethyl
Figure imgf000027_0002
l-benzyl-l,2,3,6-tetrahydro-2,3-diphenylpyrimidine-4,5-dicarboxylate, 化合物 34);产率 19% , 白 色固体, 熔点 = 133.0-134.1 °C; IR (KBr): v = 3030, 2949, 1742, 1699, 1578, 1495, 1434, 1359, 1290, 1244, 1110, 1058, 910, 735, 698 cm"1; JH NMR(400 MHz, CDC13): δ= 7.73 -7.08 (m, 15H), 5.25 (s 1H), 3.94 (s 2H), 3.75 (s 3H), 3.64 (s 3H), 3.53 (d J = 18.0 Hz, 1H), 3.32 (d J = 17.6 Hz, lH)ppm; 13C NMR (101 MHz, CDC13): =166.58 165.11 144.69 143.93, 129.24, 128.93, 128.86, 128.37, 128.15, 127.37, 127.07, 125.75, 123.49, 99.82, 79.47, 57.57, 52.65, 51.33, 43.88 ppm; MS (ESI): m/z 443(M + H+ 45), 262(100); Anal. Calcd for C27H26N204: C 73.28; H: 5.92; N 6.33; Found: C 73.11; H 5.76; N 6.28.
以下通过化合物溶液的紫外吸收和荧光发射光谱的测定、 化合物纳米颗粒悬浮液的荧光发射 光谱的测定、 以及通过化合物溶液和化合物纳米颗粒悬浮液的荧光量子产率的测定来评估化 合物 1 34的聚集诱导发光性质。
[0053] 实施例 35 化合物溶液的紫外吸收和荧光发射光谱的测定:
将样品浓度为配制为 5X10—5M乙醇溶液。溶液的紫外可见吸收光谱用北京仪通公司的 TU-901 紫外可见分光光度计测定。实施例 1中在 J=365nm下发蓝色荧光的化合物 1在乙醇溶液及在 乙醇-水混合液 (5:95)中的紫外吸收光谱见图 5, 实施例 1中在 =365nm下发绿色荧光的化合 物 1在乙醇溶液及在乙醇-水混合液 (5:95)中的紫外吸收光谱见图 6。溶液的荧光发射光谱用日 本 Shimadzu公司的 RF5301PC荧光分光光度计上测定。 实施例 1中在 =365nm下发蓝色荧 光的化合物 1的乙醇溶液的荧光发射光谱见图 7, 实施例 1中在 J=365nm下发绿色荧光的化 合物 1的乙醇溶液的荧光发射光谱见图 8。
[0054] 化合物纳米颗粒悬浮液的荧光发射光谱的测定:
在超声波振荡下往样品的乙醇溶液中缓慢滴加不良溶剂水, 配制终浓度为 5X10—5M 乙醇-水 (40:60-5:95) 的纳米颗粒悬浮液。 悬浮液中的荧光发射光谱用日本 Shimadzu 公司的 RF5301PC荧光分光光度计上测定。 实施例 1中在 =365nm下发蓝色荧光的化合物 1在不同 比例的乙醇-水的纳米颗粒悬浮液的荧光发射光谱见图 9, 实施例 1 中在 J=365nm下发绿色 荧光的化合物 1在不同比例的纳米颗粒悬浮液的荧光发射光谱见图 10。
[0055] 化合物溶液和化合物纳米颗粒悬浮液的荧光量子产率 (Φ)的测定
以 9,10-二苯基蒽 (DPA)(乙醇溶液, ODPA=0.95)作为参比, 采用稀溶液方法测定。 量子产率 通过以下方程计算:
S A
Φ — unknown DAP ^ ^DAP^
其中 Ounkn。Wn是未知样品的荧光量子产率; ΦΟΡΑ是参比 DPA的荧光量子产率 ( Φ DPA=0.95); Sunknwn和 SDPA分别为样品和参比在 350nm波长激发下的荧光发射光谱的积分面积; Aunknwn 和 ADPA分别为样品和参比在 350nm波长下的吸光度。 实施例 1中在 J =365nm下发蓝色荧光 的化合物 1在不同比例的乙醇 -水混合液中的荧光量子产率见图 11, 实施例 1中在 J=365nm 下发绿色荧光的化合物 1在不同比例的乙醇 -水混合液中的荧光量子产率见图 12。
[0056] 实施例 1 -32 中浓度为 5X10—5M 的化合物 1 -32 在乙醇溶液中的最大吸收波长 ( ^ )、 摩尔吸收系数 ( ε ) 和量子产率 (Φ8)、 在乙醇-水 (1:9) 混合液中的最大发射波 max
长 (^™ ) 和量子产率 (Φ ) 以及在乙醇-水 (1:9) 混合液中的量子产率与在乙醇溶液中的 max
量子产率比值见表 1。 s/uu O soosld ssssoiAV
Figure imgf000029_0001
33 316 15044 411 0.00926 0.3723 40.2
34 335 5754 450 0.003 0.0644 21.5
"测定样品的乙醇溶液; b测定样品的乙醇-水混合液(1 :9); c 以 9,10-二苯基蒽(测定浓度 为 5 X 10—5M, 在乙醇溶液的量子产率 Φ=0.95, 激发波长为 350nm)为标准物计算量子产率 测定样品的乙醇-水混合液 (5:95 )。
[0058] 从表 1可以看出, 化合物 1 - 34 均具有聚集诱导发光性能 ( Da/ Ds大于 12.5, 其中多 数比值大于 100)、 有很好的吸收光的性能 ( ε =5754〜100500 cm"1 - M"1 ) 以及化合物的量子 产率可达到 0.81。 其中, 化合物 1、 8、 13、 17、 19、 22-25的聚集态的荧光量子产率与其溶 液的荧光量子产率的比值大于 1000, 具有很强的聚集诱导发光特性。 因此, 该类化合物是一 类光学性能优良的聚集诱导发光物质。

Claims

1. 聚集诱导发光的五取代四氢 其特征在于, 具有如式 ( I ) 所示结构:
Figure imgf000031_0001
( I )
式中:
R1选自 8直链或支链烷基或取代的 — 8烷基;
R2、 R4各独立选自 d— 8直链或支链烷基、 取代的 d— 8烷基、 C58环烷基、 取代的 C58环烷 基、 C56芳香基、 取代的 C56芳香基、 C918稠环芳香基、 取代的 C918稠环芳香基、 C56杂环 基、 取代的 C56杂环基、 C56芳杂环基或取代的 C56芳杂环基;
R3选自 C56芳香基、 取代的 C56芳香基、 C918稠环芳香基、 取代的 C918稠环芳香基、 C56 芳杂环基或取代的 C56芳杂环基。
2. 如权利要求 1所述的聚集诱导发光的五取代四氢嘧啶, 其特征在于, R1选自 d— 2烷基。
3. 如权利要求 1 所述的聚集诱导发光的五取代四氢嘧啶, 其特征在于, R2选自 — 5直链或 支链烷基、 取代的 — 5烷基、 C58环烷基、 C56芳香基或取代的 C56芳香基。
4. 如权利要求 1 所述的聚集诱导发光的五取代四氢嘧啶, 其特征在于, R3选自 C56芳香基 或取代的 — 6芳香基。
5. 如权利要求 1 所述的聚集诱导发光的五取代四氢嘧啶, 其特征在于, R4选自 — 5直链或 支链烷基、 取代的 — 5烷基、 C58环烷基、 C56芳香基或取代的 C56芳香基。
6. 如权利要求 1、 3、 4或 5 中任意一项权利要求所述的聚集诱导发光的五取代四氢嘧啶, 其特征在于, 所述取代基选自下列基团: 卤素、 全卤代的 — 2烷基、 卤代 d— 4烷基、 羟基、 — 6直链或支链烷氧基、 硝基、 氰基、 氨基、 — 6单烷基氨基、 — 6二烷基氨基、 C58单环烷 基氨基、 C56单杂环基氨基、 C56单芳基氨基、 — 6烷基酰氨基、 C56芳基酰氨基、 氨基羰 基、 Ci— 6单烷基氨基羰基、 d— 6二烷基氨基羰基、 d— 6烷基酰基、 C58芳基酰基、 氨基砜基、 — 6单烷基氨基砜基、 — 6二烷基氨基砜基、 C58芳基氨基砜基、 — 6烷基磺酰氨基、 羧基、 — 6单烷基砜基、 直链或支链烷基、 C58环烷基、 C58取代的环烷基、 C24烯基、 C24块基、 芳基 Ci— 3烷基、 C56芳香基、 C56取代的芳香基、 C918稠环芳香基、 C56杂环基、 C56芳杂环 基或 C918稠环芳杂环基。
7. 如权利要求 1所述的聚集诱导发光的五取代四氢嘧啶, 其特征在于, 式 ( I ) 中, R1选自甲基或乙基;
R2选自苯基, 苄基, 甲基苯基, 氯苯基, 溴苯基, 三氟甲基苯基, 正丁基;
R3选自苯基, 溴苯基, 甲氧基羟基取代的苯基, 溴苯基, 三氟甲基苯基, 萘基, 吡啶基;
R4选自苯基, 苄基, 甲基苯基, 氯苯基, 溴苯基, 三氟甲基苯基, 羟乙基, 正丁基。
8. 权利要求 1~5 中任意一项权利要求所述聚集诱导发光的五取代四氢嘧啶的制备方法, 其 特征在于, 包括如下步骤:
以下物质用量按毫摩尔份数计算:
(1) 在 l~10mL的有机溶剂中, 加入 1份式 ( II ) 化合物和 1份式 (III) 化合物, 在 0~60 °C下搅拌 10~60分钟;
(2) 在 l~10mL 的有机溶剂中, 分别加入 1~5份式 (IV)、 1-5份甲醛, 同时加入 0~4份 酸, 在 20~100°C下搅拌 10分钟〜 5小时;
(3) 将步骤 (1) 和步骤 (2) 的反应液混合后, 加入 1~5份式 (V) 化合物和 0.1 0.5份催 化剂, 在 -15~100°C下搅拌 1~7天, 分离纯化得到产品;
( II),
R2NH2
(III) ,
R4NH2
(IV) ,
R3CHO
(V) ;
所述酸为盐酸、 硫酸、 磷酸、 苯磺酸、 三氟乙酸或乙酸中的一种或其混合物;
所述催化剂为硫酸铜、 醋酸铜、 氯化锌、 醋酸钯、 硫脲、 脯氨酸或脲中的任意一种或几种; 所述有机溶剂为醇、 苯、 甲苯、 己烷、 卤代烃、 醚、 Ν,Ν-二甲基甲酰胺、 二甲亚砜或乙腈中 的一种或几种。
9. 权利要求 1~5 中任意一项权利要求所述聚集诱导发光的五取代四氢嘧啶在制备有机电致 或光致发光器件中的应用。
10. 权利要求 1~5 中任意一项权利要求所述聚集诱导发光的五取代四氢嘧啶在制备化学及生 物荧光传感器或探针中的应用。
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CN102885817A (zh) * 2012-10-15 2013-01-23 南方医科大学 一种1,3-二环戊基取代的四氢嘧啶类化合物在制备治疗类风湿关节炎药物中的应用
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CN103484103B (zh) * 2013-09-03 2014-11-12 福建师范大学 一种聚集诱导发光材料及其制备方法
CN103529017B (zh) * 2013-10-09 2017-02-08 国家纳米科学中心 一种酶响应性自聚集发光分子及其在监测酶活性中的应用
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CN104897628B (zh) * 2015-04-28 2018-04-10 扬州大学 一种荧光探针在测定表面活性剂临界胶束浓度上的应用
CN104845613B (zh) 2015-04-29 2017-01-04 南方医科大学 五取代四氢嘧啶在制备温度敏感荧光材料中的应用
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CN105837513B (zh) * 2016-04-07 2018-10-26 南方医科大学 五取代四氢嘧啶衍生物在制备细胞成像染料中的应用
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