CN102250015B - 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 PDFInfo
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Abstract
本发明公开一种聚集诱导发光的五取代四氢嘧啶及其制备方法和应用。所述聚集诱导发光的五取代四氢嘧啶具有如式(I)所示结构,R1选自直链或支链烷基或取代烷基;R2、R4各独立选自直链或支链烷基、取代烷基、环烷基、取代环烷基、芳香基、取代芳香基、稠环芳香基、取代稠环芳香基、杂环基、取代杂环基、芳杂环基或取代芳杂环基;R3选自芳香基、取代芳香基、稠环芳香基、取代稠环芳香基、芳杂环基或取代芳杂环基。所述聚集诱导发光的五取代四氢嘧啶可以通过多组分反应制备得到。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,可以应用于制备有机电致或光致发光器件或化学及生物荧光传感器和探针。
Description
技术领域
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
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一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。
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)。
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AlE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。
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II(J. 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
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。
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。
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。
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:
(Ⅰ)
式中:
R1选自C1-8直链或支链烷基或取代的C1-8烷基;
R2、R4各自独立选自C1-8直链或支链烷基、取代的C1-8烷基、C5-8环烷基、取代的C5-8环烷基、C5-6芳香基、取代的C5-6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C5-6杂环基、C5-6芳杂环基或取代的C5-6芳杂环基;
R3选自C5-6芳香基、取代的C5-6芳香基、C9-18稠环芳香基、取代的C9-18稠环芳香基、C5-6芳杂环基或取代的C5-6芳杂环基。
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C1-2烷基。
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C1-5直链或支链烷基、取代的C1-5烷基、C5-8环烷基、C5-6芳香基或取代的C5-6芳香基。
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C5-6芳香基或取代的C5-6芳香基。
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C1-5直链或支链烷基、取代的C1-5烷基、C5-8环烷基、C5-6芳香基或取代的C5-6芳香基。
作为一种优选方案,上述的取代基,优选为卤素、全卤代的C1-2烷基、卤代C1-4烷基、羟基、C1-6直链或支链烷氧基、硝基、氰基、氨基、C1-6单烷基氨基、C1-6二烷基氨基、C5-8单环烷基氨基、C5-6单杂环基氨基、C5-6单芳基氨基、C1-6烷基酰氨基、C5-6芳基酰氨基、氨基羰基、C1-6单烷基氨基羰基、C1-6二烷基氨基羰基、C1-6烷基酰基、C5-8芳基酰基、氨基砜基、C1-6单烷基氨基砜基、C1-6二烷基氨基砜基、C5-8芳基氨基砜基、C1-6烷基磺酰氨基、羧基、C1-6单烷基砜基、直链或支链烷基、C5-8环烷基、C5-8取代的环烷基、C2-4烯基、C2-4炔基、芳基C1-3烷基、C5-6芳香基、C5-6取代的芳香基、C9-18稠环芳香基、C5-6杂环基、C5-6芳杂环基或C9-18稠环芳杂环基。
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。
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1~10mL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℃下搅拌10~60分钟;
(2)在1~10mL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℃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℃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、N,N-二甲基甲酰胺、二甲亚砜或乙腈中的一种或几种。
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。
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。
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。
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。
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
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=365nm下的发光情况;其中,白色晶体A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=365nm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=365nm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
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。
实施例1
(1)将1mmol(170mg)的丁炔二酸二乙酯、1mmol (93mg)的苯胺依次加入到2mL乙醇中,室温下搅拌20min。
(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℃下搅拌20min。
将(1)和(2)的反应液混合,40℃下,加入2mmol(212mg)的苯甲醛,0.1mmol(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。
1,2,3-三苯基-1,2,3,6-四氢嘧啶-4,5-二甲酸乙酯(diethyl 1,2,3,6-tetrahydro-1,2,3-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℃; 绿色荧光的浅绿色晶体, mp = 119.5~120.5℃; IR (KBr): νmax = 2980, 1739, 1697, 1592, 1495, 1234, 1108, 761, 696 cm-1; 1H NMR(400 MHz, CDCl3):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, CDCl3): δ=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 C28H28N2O4: C, 73.66; H, 6.18; N, 6.14; Found: C, 73.91; H, 6.10; N, 6.21。
实施例2
(1)将1mmol(170mg)的丁炔二酸二乙酯、1mmol (107mg)的苄胺依次加入到1mL N,N-二甲基甲酰胺中,室温下搅拌10min。
(2)将1mmol(107mg)的苄胺和1mmol(80mg) 的30%甲醛加入到2mL N,N-二甲基甲酰胺中,室温下搅拌10min。
(3)将(1)和(2)的反应液混合,80℃下,加入1mmol(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),洗脱剂为乙酸乙酯,用真空旋蒸法除去溶剂得140mg的化合物2。
1,3-二苄基-2-苯基-1,2,3,6-四氢嘧啶-4,5-二甲酸乙酯(diethyl 1,3-dibenzyl-1,2,3,6-tetrahydro-2-phenylpyrimidine-4,5-dicarboxylate, 化合物2)产率29%, 白色固体, 熔点= 107.2-108.0℃; IR (KBr): ν max = 2983, 2358, 1735, 1688, 1575, 1447, 1285, 1147, 1109, 746, 688 cm-1; 1H NMR(400 MHz, CDCl3): 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), 4.01(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, CDCl3): 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。
实施例3
(1)将1mmol(170mg)的丁炔二酸二乙酯、1mmol (107mg)的对甲苯胺依次加入到1mL正己烷中,室温下搅拌1h。
(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。
(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。
1,3-二(4-甲基苯基)-2-苯基-1,2,3,6-四氢嘧啶-4,5-二甲酸乙酯(diethyl1,2,3,6-tetrahydro-2-phenyl-1,3-dip-tolylpyrimidine-4,5-dicarboxylate, 化合物3);产率51%,黄色固体, 熔点= 146.5-148.2℃; IR (KBr): ν max =3059, 3029, 2924, 1740, 1698, 1595, 1511, 1423, 1390, 1289, 1234, 1107, 1007, 817, 760, 698 cm-1; 1H NMR(400 MHz, CDCl3): 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, CDCl3) δ=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。
实施例4
(1)将1mmol(170mg)的丁炔二酸二乙酯、1mmol (127mg)的对氯苯胺依次加入到1mL甲醇中,60℃下搅拌10min。
(2)将1.5mmol(190mg)的对氯苯胺和1mmol(80mg) 的30%甲醛加入到10mL二氯甲烷中,常温下搅拌10min。
(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。
1,3-二(4-氯苯基)-2-苯基-1,2,3,6-四氢嘧啶-4,5-二甲酸乙酯(diethyl 1,3-bis(4-chlorophenyl)-1,2,3,6-tetrahydro-2-phenylpyrimidine-4,5- dicarboxylate, 化合物4);产率50%,黄色固体, 熔点= 166.8-167.6℃; IR (KBr): ν max = 2983, 2357, 1740, 1697, 1601, 1492, 1232, 1104, 1007, 825, 756, 700 cm-1; 1H NMR(400 MHz, CDCl3): δ= 7.63-6.86(m, 13H), 5.60(s, 1H), 4.21(d, J=18.0Hz, 1H), 4.15-4.11(m, 4H), 3.56(d, J=18.0Hz, 1H), 1.22(t, J=7.2Hz, 3H), 1.10(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDCl3): 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 C28H26Cl2N2O4: 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1mmol(170mg)的丁炔二酸二乙酯、1mmol (170mg)的对溴苯胺依次加入到3mL甲醇中,室温下搅拌30min。
(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。
(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。
1,3-二(4-溴苯基)-2-苯基-1,2,3,6-四氢嘧啶-4,5-二甲酸乙酯(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℃; IR (KBr): ν max = 2982, 2360, 1738, 1696, 1597, 1490, 1232, 1109, 1005, 820, 756, 700 cm-1; 1H NMR(400 MHz, CDCl3): δ= 7.62-7.31(m, 9H), 6.90-6.81(m, 4H), 6.01(s, 1H), 4.21(d, J=18.0Hz, 1H), 4.15-4.10(m, 4H), 3.55(d, J=18.0Hz, 1H), 1.22(t, J=7.2Hz, 3H), 1.11(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDCl3): 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 C28H26Br2N2O4: C, 54.74; H, 4.27; N, 4.56; Found: C, 54.81; H, 4.35; N, 4.61。
实施例6
(1)将1mmol(170mg)的丁炔二酸二乙酯、1mmol (161mg)的间三氟甲基苯胺依次加入到1mL甲醇中,室温下搅拌60min。
(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。
(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。
1,3-二(3-三氟甲基苯基)-2-苯基-1,2,3,6-四氢嘧啶-4,5-二甲酸乙酯;(diethyl1,3-bis(3-(trifluoromethyl)phenyl)-1,2,3,6-tetrahydro-2-phenylpyrimidine-4,5- dicarboxylate, 化合物6);产率50%,白色固体,熔点= 104.4-105.2℃; IR (KBr): ν max = 2986, 2357, 1741, 1700, 1600, 1499, 1234, 1125, 866, 758, 695 cm-1; 1H NMR(400 MHz, CDCl3): 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, CDCl3): 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。
实施例7
(1)将1mmol(170mg)的丁炔二酸二乙酯、1mmol (107mg)的间甲基苯胺依次加入到1mL甲醇中,室温下搅拌60min。
(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。
(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。
1,3-二(3-甲基苯基)-2-苯基-1,2,3,6-四氢嘧啶-4,5-二甲酸乙酯(diethyl 1,3-bis(3-methylphenyl)-1,2,3,6-tetrahydro-2-phenylpyrimidine-4,5- dicarboxylate, 化合物7);产率46%,黄色固体, 熔点= 100.0-100.8℃; IR (KBr): ν max = 2980, 1740, 1698, 1582, 1492, 1249, 1178, 1108, 759, 698 cm-1; 1H NMR(400 MHz, CDCl3): 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, CDCl3): 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。
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。
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 2-(4-bromophenyl)-1,2,3,6-tetrahydro-1,3-diphenylpyrimidine-4,5-dicarboxylate化合物8);产率31%,黄色固体, 熔点= 162.4-164.6℃; IR (KBr): ν max = 2981, 2352, 1739, 1697, 1592, 1495, 1372, 1293, 1236, 1107, 1009, 910, 747, 696 cm-1; 1H NMR(400 MHz, CDCl3): 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, CDCl3): 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 C28H27BrN2O4: C, 62.81; H, 5.08; N, 5.23; Found: C, 62.93; H, 5.18; N, 5.16.
实施例9
1,3-二苯基-2-(3-甲氧基-4-羟基苯基)-1,2,3,6-四氢嘧啶-4,5-二甲酸乙酯(diethyl 1,2,3,6-tetrahydro-2-(4-hydroxy-3-methoxyphenyl)-1,3- diphenylpyrimidine-4,5-dicarboxylate,化合物9);产率53%,黄色固体,熔点= 164.1-164.6℃; IR (KBr): ν max = 2981, 2360, 1735, 1697, 1579, 1496, 1282, 1235, 1109, 763, 696 cm-1; 1H NMR(400 MHz, CDCl3): 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, CDCl3): 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 1-benzyl-1,2,3,6-tetrahydro-2,3-diphenylpyrimidine-4,5-dicarboxylate,化合物10);产率37%,白色固体, 熔点= 100.0-100.8℃; IR (KBr): ν max = 3061, 3030, 2980, 2930, 2362, 1736, 1697, 1630, 1578, 1496, 1283, 1104, 1056, 752, 698 cm-1;1H NMR (400 MHz, CDCl3): 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, CDCl3) δ=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 3-benzyl-1,2,3,6-tetrahydro-1,2-diphenylpyrimidine-4,5-dicarboxylate,化合物11);产率21%,白色固体, 熔点= 102.4-103.4℃; IR (KBr): ν max = 3061, 3029, 2980, 2935, 2903, 1737, 1692, 1593, 1496, 1452, 1367, 1284, 1223, 1147, 1108, 1032, 749, 697 cm-1; 1H NMR(400 MHz, CDCl3): 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, J = 16.0 Hz, 1H), 4.33-4.22 (m, 2H), 4.10-4.02 (m, 4H), 3.43 (d, J = 16.8 Hz, 1H), 1.21-1.15 (m, 6H) ppm; 13C NMR(101MHz, CDCl3): 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 1-benzyl-1,2,3,6-tetrahydro-3-(3-methylphenyl)-2-phenylpyrimidine-4,5- dicarboxylate,化合物12);产率38%,黄色油状物; IR (KBr): ν max = 3061, 3029, 2978, 2852, 1738,1697, 1581, 1492, 1450, 1366, 1249, 1217, 1177, 1105, 1061, 781, 699cm-1; 1H NMR (400 MHz, CDCl3): δ=7.52-6.85(m, 14H), 5.12(s, 1H), 4.14-4.07(m, 2H), 4.00(q, J = 7.2 Hz, 2H), 3.83(s, 2H), 3.43(d, J = 18.0 Hz, 1H), 3.20(d, J = 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, CDCl3): 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 1-benzyl-3-(4-bromophenyl)-1,2,3,6-tetrahydro-2-phenylpyrimidine-4,5- dicarboxylate,化合物13);产率29%, 白色固体, 熔点= 119.9-121.4℃; IR (KBr): ν max = 3278, 2929, 2358, 1690, 1621, 1548, 1193, 1070, 737, 670 cm-1; 1H NMR(400 MHz, CDCl3): 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, J = 13.6 Hz, 1H), 3.89(d, J = 13.6 Hz, 1H), 3.55(d, J=18.4Hz, 2H), 3.33(d, J=18.4Hz, 2H), 1.23-1.19(m, 6H) ppm; 13C NMR (101 MHz, CDCl3): 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 C29H29BrN2O4: 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-4,5-二甲酸乙酯(diethyl1-benzyl-1,2,3,6-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℃ ; IR (KBr): ν max = 3434, 2980, 2358, 1734, 1696, 1581, 1515, 1251, 1107, 736, 670 cm-1; 1H NMR(400 MHz, CDCl3): 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), 3.31(d, J=18.0 Hz, 1H), 2.26(s, 3H), 1.20-1.12(m, 6H) ppm; 13C NMR (101 MHz, CDCl3) δ=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 C31H34N2O6: 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 3-(4-chlorophenyl)-1,2,3,6-tetrahydro-1,2-diphenylpyrimidine-4,5- dicarboxylate,化合物15);产率47%,黄色固体, 熔点= 141.7-142.3℃; IR (KBr): ν max = 2981, 1738, 1698, 1599, 1492, 1237, 1102, 828, 750, 697 cm-1; 1H NMR(400 MHz, CDCl3): 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=7.2 Hz, 3H), 1.09(t, J=7.2 Hz, 3H) ppm; 13C NMR (101 MHz, CDCl3): 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 C28H27ClN2O4: 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 3-(4-methylphenyl)-1,2,3,6-tetrahydro-1,2-diphenylpyrimidine-4,5- dicarboxylate,化合物16);产率37%,黄色固体, 熔点= 123.9-125.2℃; IR (KBr): ν max = 3073, 2357, 1742, 1699, 1508, 1234, 1107, 911, 757, 683 cm-1; 1H NMR(400 MHz, CDCl3): δ= 7.71-6.87(m, 14H), 6.11(s, 1H), 4.31(d, J=17.6Hz, 1H), 4.18-4.10 (m, 4H), 3.61(d, J=17.6Hz,1H), 2.29(s, 3H), 1.25(t, J=7.2Hz, 3H), 1.09(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDCl3) 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 1-(4-chlorophenyl)-1,2,3,6-tetrahydro-2,3-diphenylpyrimidine-4,5- dicarboxylate,化合物17);产率53%,白色固体,熔点= 139.3-139.9℃; IR (KBr): ν max = 3115, 2359, 1702, 1515, 966, 676 cm-1; 1H NMR(400 MHz, CDCl3): δ= 7.47-6.88(m, 14H), 6.02(s, 1H), 4.23(d, J=18.0Hz, 1H), 4.17-4.11(m, 4H), 3.58(d, J=18.0Hz, 1H), 1.25 (t, J=7.2Hz, 3H), 1.12 (t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDCl3): 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 C28H27ClN2O4: C, 68.50; H, 5.54; N, 5.71; Found: C, 68.30; H, 5.51; N, 5.83.
实施例18
1-(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 1-(4-methylphenyl)-1,2,3,6-tetrahydro-2,3-diphenylpyrimidine-4,5- dicarboxylate,化合物18);产率36% ,白色固体,熔点= 131.1-132.2℃; IR (KBr): ν max =2984, 2358, 1742, 1698, 1508, 1232, 1108, 1008, 756, 683 cm-1; 1H NMR(400 MHz, CDCl3): δ= 7.67-6.84(m, 14H), 6.04(s, 1H), 4.23(d, J=18.0Hz, 1H), 4.13-4.08(m, 4H), 3.57(d, J=18.0Hz, 1H), 2.26(s, 3H), 1.21(t, J=7.2Hz, 3H), 1.03(t, J=7.2Hz, 3H) ppm; 13C NMR (101 MHz, CDCl3): δ=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-4,5-二甲酸甲酯(dimethyl 1,2,3,6-tetrahydro-1-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 oC; 1H NMR(600 MHz, CDCl3):δ= 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, CDCl3):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 C26H25N3O4: 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 1,2,3,6-tetrahydro-1-(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℃; IR (KBr): ν max = 3510, 2948, 2353, 1741, 1695, 1583, 1495, 1236, 1111, 756, 697 cm-1; 1H NMR(400 MHz, CDCl3): δ= 7.56-7.11(m, 10H), 5.31(s, 1H), 3.77-3.75(m, 1H), 3.68(s, 3H), 3.66(b, 1H), 3.63(s, 3H), 3.50 (d, J=18.0Hz, 1H), 3.18(d, J=18.0Hz, 1H), 3.97-3.91(m, 2H), 2.58(s, 1H) ppm; 13C NMR (101 MHz, CDCl3): 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 C22H24N2O5: 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 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℃; IR (KBr): ν max = 2950, 2356, 1743, 1699, 1589, 1496, 1234, 1112, 917, 756, 696 cm-1; 1H NMR(400 MHz, CDCl3):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, CDCl3) 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 C26H24N2O4: 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 1,2,3,6-tetrahydro-2-(naphthalen-2-yl)-1,3-dip-tolylpyrimidine-4,5-dicarboxylate,化合物36)产率29%, 白色固体,熔点 = 158.0-159.0℃; IR (KBr): ν max = 3027, 2948, 2920, 2860, 1742, 1701, 1592, 1511, 1434, 1366, 1236, 1111, 1064, 818, 739, 480 cm-1; 1H NMR(600 MHz, CDCl3):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, CDCl3): δ=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 1,3- bis(4-methylphenyl)-1,2,3,6-tetrahydro-2-phenylpyrimidine-4,5-dicarboxylate,化合物23);产率63%,黄色固体,熔点= 164.1-164.6℃;IR (KBr): ν max = 3688, 3031, 1742, 1699, 1593, 1510, 1239, 1110, 1064, 913, 821, 747 cm-1; 1H NMR(400 MHz, CDCl3): 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, CDCl3) 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 C28H28N2O4: 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 1,3-bis(4-chlorophenyl)-1,2,3,6-tetrahydro-2-phenylpyrimidine-4,5-dicarboxylate,实施例24);产率55%,浅黄色固体, 熔点= 153.1-153.9℃; IR (KBr): ν max = 3675, 3064, 1741, 1699, 1590, 1493, 1240, 1115, 913, 830, 737, 709 cm-1; 1H NMR(400 MHz, CDCl3): δ= 7.62-6.84(m, 13H), 6.00(s, 1H), 4.19(d, J=18.0Hz, 1H), 3.68(s, 3H), 3.66(s, 3H), 3.56(d, J=18.0Hz, 1H) ppm; 13C NMR (101 MHz, CDCl3): 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 C25H27N3O5: C26H22Cl2N2O4: C, 62.79; H, 4.46; N, 5.63; Found: C, 62.87; H, 4.29; N, 5.51.
实施例25
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 1,3-bis(4-bromophenyl)-1,2,3,6-tetrahydro-2-phenylpyrimidine-4,5-dicarboxylate,化合物25);产率47%,浅黄色固体, 熔点= 144.5-145.0℃; IR (KBr): ν max = 2950, 2356, 1741, 1699, 1596, 1490, 1236, 1113, 913, 823, 737, 640 cm-1; 1H NMR(400 MHz, CDCl3): 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, CDCl3): 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 C26H22Br2N2O4: 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-4,5-二甲酸甲酯(dimethyl 1,3-bis(3-(trifluoromethyl)phenyl)-1,2,3,6-tetrahydro-2-phenylpyrimidine-4,5-dicarboxylate,化合物26);产率48%, 白色固体, 熔点= 152.3-153.0℃; IR (KBr): ν max = 3687, 2954, 1742, 1704, 1590, 1595, 1235, 1125, 1073, 909, 735, 670,650 cm-1; 1H NMR(400 MHz, CDCl3): δ= 7.65-7.14(m, 13H), 6.16(s, 1H), 4.32(d, J=18.0Hz, 1H), 3.70(s, 3H), 3,68(s, 3H), 3.67(d, J=18.0Hz, 1H) ppm; 13C NMR (101 MHz, CDCl3): 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 C28H22F6N2O4: 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 1,2,3,6-tetrahydro-2-phenyl-1,3-dim-tolylpyrimidine-4,5-dicarboxylate,化合物27);产率52%,黄色固体, 熔点= 112.9-113.9℃; IR (KBr): ν max = 2949, 1742, 1702, 1582, 1492, 1251, 1230, 1179, 1112, 758, 698 cm-1; 1H NMR(400 MHz, CDCl3): 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, CDCl3): 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 C28H28N2O4: C, 73.66; H, 6.18; N, 6.14; Found: C, 73.78; H, 6.31; N, 6.09.
实施例28
1,3-二正丁基-2-苯基-1,2,3,6-四氢嘧啶-4,5-二甲酸甲酯(dimethyl 1,3-dibutyl-1,2,3,6-tetrahydro-2-phenylpyrimidine-4,5-dicarboxylate,化合物28);产率41% ,黄色油状物; IR (KBr): ν max = 2954, 2868, 2358, 1743, 1689, 1577, 1432, 1286, 1140, 1096, 7534, 683 cm-1; 1H NMR(400 MHz, CDCl3):δ= 7.29-7.19(m, 5H), 4.86(s, 1H), 3.89 (s, 3H), 3.52(s, 3H), 3.25(d, J=16.8Hz, 1H), 3.18-3.14(m, 1H), 2.97(d, J=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, CDCl3): δ=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 C22H32N2O4: 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)-1,2,3,6-四氢嘧啶-4,5-二甲酸甲酯(dimethyl 2-(3-bromophenyl)-1,2,3,6-tetrahydro-1,3-diphenylpyrimidine-4,5-dicarboxylate,化合物29);产率47%,黄色固体, 熔点= 142.5-144.3℃; IR (KBr): ν max = 3036, 2949, 2925, 2853, 1741, 1701, 1592, 1581, 1496, 1472, 1456, 1273, 1113, 1046, 782, 696 cm-1; 1H NMR(400 MHz, CDCl3): δ= 7.80-6.90(m, 14H), 6.06(s, 1H), 4.29(d, J=18.0Hz, 1H), 3.68(s, 3H), 3.65(s, 3H), 3.61(d, J=18.0Hz, 1H) ppm; 13C NMR (101 MHz, CDCl3) δ=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 C26H23BrN2O4: C, 61.55; H, 4.57; N, 5.52; Found: C, 61.38; H, 4.39; N, 5.61.
实施例30
1,3-二苯基-2-(4-三氟甲基苯基)-1,2,3,6-四氢嘧啶-4,5-二甲酸甲酯(dimethyl-2-(4-(trifluoromethyl)phenyl)-1,2,3,6-tetrahydro-1,3-diphenylpyrimidine-4,5-dicarboxylate,化合物30);产率25%,黄色固体,熔点= 145.3-146.2℃; IR (KBr): ν max = 2925, 2852, 2360, 1704, 1596, 1580, 1495, 1435, 1324, 1236, 1111, 1068, 1033, 747, 695cm-1; 1H NMR(400 MHz, CDCl3): δ= 7.84-6.93(m, 14H), 6.16(s, 1H), 4.32(d, J=18.0Hz, 1H), 3.70(s, 3H), 3.68(s, 3H), 3.56(d, J=18.0Hz, 1H) ppm; 13C NMR (101 MHz, CDCl3): δ=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 C27H23F3N2O4: 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(dimethyl-2-(4-bromophenyl)-1,2,3,6-tetrahydro-1,3-diphenylpyrimidine-4,5-dicarboxylate,化合物31);产率51% ,黄色固体, 熔点= 164.5-165.9℃; R (KBr): ν max = 2981, 2352, 1739, 1697, 1592, 1495, 1372, 1293, 1236, 1107, 1009, 910, 747, 696 cm-1; 1H NMR(400 MHz, CDCl3): δ= 7.59-6.90(m, 14H), 6.04(s, 1H), 4.27(d, J=18.0Hz, 1H), 3.66(s, 3H), 3.64(s, 3H), 3.57(d, J=18.0Hz, 1H) ppm; 13C NMR (101 MHz, CDCl3): 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 C26H23BrN2O4: C, 61.55; H, 4.57; N, 5.52; Found: C, 61.38; H, 4.62; N, 5.47.
实施例32
1,3-二苯基-2-(3-甲氧基-4羟基苯基)-1,2,3,6-四氢嘧啶-4,5-二甲酸甲酯(dimethyl1,2,3,6-tetrahydro-2-(4-hydroxy-3-methoxyphenyl)-1,3-diphenylpyrimidine-4,5-dicarboxylatea,化合物32);产率52%,黄色固体, 熔点 = 158.5-160.1℃; IR (KBr): ν max = 3061, 2950, 1740, 1697, 1580, 1514, 1495, 1434, 1282, 1237, 1115, 762, 696 CM-1; 1H NMR(400 MHz, CDCl3): δ= 7.25-6.89(m, 13H), 6.09(s, 1H), 5.72(s.1H), 4.26(d, J=18.0Hz, 1H), 3.88(s, 3H), 3.66(s, 3H), 3.65(s, 3H), 3.60(d, J=18.0Hz, 1H) ppm; 13C NMR (101 MHz, CDCl3): 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 C27H26N2O6: 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(1-butyl-1,2,3,6-tetrahydro-2,3-diphenylpyrimidine-4,5-dicarboxylate, 化合物33);产率21% , 白色固体,熔点 = 122.1-122.6℃; IR (KBr): ν max = 2951, 1742, 1700, 1578, 1495, 1407, 1240, 1108, 750, 698 cm-1; 1H NMR(400 MHz, CDCl3):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, J = 17.8 Hz, 1H), 2.78-2.75 (m, 2H), 1.53-1.42 (m, 4H), 0.93 (t, J = 7.2 Hz, 3H) ppm; 13C NMR (101 MHz, CDCl3): 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 C24H28N2O4: C, 70.57; H, 6.91; N, 6.86; Found: C, 70.33; H, 6.79; N, 6.93.
实施例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 1-benzyl-1,2,3,6-tetrahydro-2,3-diphenylpyrimidine-4,5-dicarboxylate, 化合物34);产率19% , 白色固体, 熔点 = 133.0-134.1℃; IR (KBr): νmax = 3030, 2949, 1742, 1699, 1578, 1495, 1434, 1359, 1290, 1244, 1110, 1058, 910, 735, 698 cm-1; 1H NMR(400 MHz, CDCl3):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, 1H)ppm; 13C NMR (101 MHz, CDCl3): δ=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 C27H26N2O4: 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。
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5×10-5M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λ=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λ=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λ=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λ=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。
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5×10-5M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λ=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λ=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。
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,ΦDPA=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:
其中Φunknown是未知样品的荧光量子产率;ΦDPA是参比DPA的荧光量子产率(ΦDPA=0.95);Sunknown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;Aunknown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λ=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λ=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。
实施例1–32中浓度为5×10-5M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(Φs)、在乙醇-水(1:9)混合液中的最大发射波长()和量子产率(Φa)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量子产率比值见表1。
表1化合物1-34的光学性能
a 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5×10-5M,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; d 测定样品的乙醇-水混合液(5:95)。
从表1可以看出,化合物1–34 均具有聚集诱导发光性能(Φa/Φs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 (5)
3.权利要求1或2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1~10mL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℃下搅拌10~60分钟;
(2)在1~10mL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℃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℃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、N,N-二甲基甲酰胺、二甲亚砜或乙腈中的一种或几种;
其中,R1、R2、R3、R4选自如权利要求1或2所述的相应基团。
4.权利要求1或2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。
5.权利要求1或2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 |
CN103411961B (zh) * | 2013-07-15 | 2016-01-06 | 南方医科大学 | 一种测定表面活性剂临界胶束浓度灵敏的荧光点亮探针法 |
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 |
CN104193666B (zh) * | 2014-07-30 | 2017-07-11 | 南方医科大学 | 一种1,3‑二取代马来酰亚胺化合物及其作为表面活性剂临界胶束浓度荧光探针的应用 |
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 |
CN105713598B (zh) * | 2016-03-07 | 2018-05-04 | 南方医科大学 | 五取代四氢嘧啶衍生物在制备具有压致荧光变色材料中的应用 |
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 |
CN106588782B (zh) * | 2016-12-20 | 2019-03-26 | 四川大学 | 3,4-二氢嘧啶-2(1h)-酮及其衍生物及其合成方法和应用 |
CN108387559B (zh) * | 2018-01-15 | 2023-05-12 | 南方医科大学 | 一种表面活性剂临界胶束浓度试纸及其制备方法 |
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