CN110105382B - 1,1,2,2-四硼酸酯乙烯及其制备方法和应用 - Google Patents
1,1,2,2-四硼酸酯乙烯及其制备方法和应用 Download PDFInfo
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Abstract
Description
技术领域
本发明属于有机合成技术领域,具体涉及1,1,2,2-四硼酸酯乙烯及其制备方法和应用。
背景技术
有机硼化合物具有无毒、稳定性好以及反应活性可调等重要性质,是一类重要的有机合成试剂。不饱和双硼酸酯与卤代芳烃进行Suzuki-Miyaura偶联反应可以构建一系列结构复杂且有用的产物,从而引起重视。
有机光电器件的性能通常取决于材料的固态特性,具有高效固态荧光的有机材料的设计和合成引起了广泛的关注。作为AIE(aggregation-induced emission)染料的代表成员,四苯乙烯(tetraphenylethene TPE)因其具有固相发光效率高,易官能化等优点而备受研究关注。此外,TPE与多种多环芳烃(polycyclic aromatic hydrocarbons)相结合,已经获得大量新型且性能优异的TPE衍生物。因此,对于新型TPE衍生物的合成也引起了广泛的关注。
1974年J.E.McMurry小组使用TiCl3/LiAlH4或Zn/TiCl4的反应体系实现了羰基化合物自身的还原偶联反应制备四芳基乙烯(J.E.McMurry and M.P.Felming,J.Am.Chem.Soc.1974,96,4708.J.E.McMurry,Chem.Rev.1989,89,1513.)。后来,RajendraRathore小组发展了以有机锂试剂作为亲核试剂去进攻羰基化合物,再经过脱水得到四芳基乙烯类化物(M.Banerjee,S.J.Emond,S.V.Lindeman and R.Rathore,J.Org.Chem.,2007,72,8054.)。McMurry偶联的底物中一般只能带有一个羰基,否则将会有其他还原偶联的副产物生成,这在一定程度上限制了后续的官能团衍生化。后一种方法因为使用了强碱,因此在一定程度上限制了其底物适用范围,例如其底物中不能带有亲电型官能团,例如氰基、醛基、酯基等。由此可见,发展一种新型且适用性广泛的四芳基乙烯类化合物的合成方法具有重要的实际意义。
发明内容
本发明的目的在于提供1,1,2,2-四硼酸酯乙烯及其制备方法和应用,该方法操作简便,所使用的反应试剂无毒,绿色环保,制得的1,1,2,2-四硼酸酯乙烯与卤代芳烃的偶联反应得到四芳基取代乙烯类化合物,为四芳基取代乙烯类化合物的合成提供新型且快捷的途径。
本发明采用的技术方案如下:
1,1,2,2-四硼酸酯乙烯,其结构式为:
本发明还提供了所述1,1,2,2-四硼酸酯乙烯的制备方法,保护性气氛下,以1,2-二硼酸酯乙炔和联硼酸频那醇酯为原料,四三苯基膦铂为催化剂,有机溶剂中于80~130℃下反应即得1,1,2,2-四硼酸酯乙烯,反应方程式如式(2)所示:
优选的,所述1,2-二硼酸酯乙炔和联硼酸频那醇酯的摩尔比为1:1.2~1.5,1,2-二硼酸酯乙炔的浓度为0.8~1.2mol/L。
优选的,所述四三苯基膦铂的量为1,2-二硼酸酯乙炔摩尔量的0.6~1mol%。
优选的,所述有机溶剂选自甲苯、环己烷、N,N-二甲基甲酰胺的至少一种。
优选的,所述反应时间为72~96h。
优选的,反应完成后加入正己烷,于冰浴下搅拌30min,再转移至-20℃冷却2h,将得到的固体过滤,滤饼用正己烷洗涤2-3遍,即得1,1,2,2-四硼酸酯乙烯。
本发明还提供了所述1,1,2,2-四硼酸酯乙烯的应用,1,1,2,2-四硼酸酯乙烯和卤代芳烃在有机溶剂、水、碱和催化剂存在的条件下,于70-100℃条件下进行偶联反应即得四芳基取代乙烯类化合物,反应方程式如式(3)所示:
其中,Ar为选自以下芳基中的一种:
X为卤素,*表示连接卤素的位置;R为氢、烷基,烷氧基、羰基、氰基、甲硫基、苯基或取代苯基;n为0、1、2。
优选的,所述R为氢、C1~C10的烷基、羰基、氰基、甲硫基;X为Cl、Br、I。
进一步优选的,所述R为C1~C3的烷基、羰基、氰基;X为Br。
更进一步优选的,所述R为酮羰基、醛羰基、酯羰基。
优选的,所述1,1,2,2-四硼酸酯乙烯和卤代芳烃的摩尔比为1:4.8~6.0,1,1,2,2-四硼酸酯乙烯的浓度为0.06~0.1mol/L。
优选的,所述有机溶剂选自四氢呋喃、二恶烷、乙二醇二甲醚中的至少一种。
优选的,所述碱选自碳酸铯、氢氧化钠、氢氧化钾、磷酸钾、碳酸钾中的至少一种。
优选的,所述催化剂选自四三苯基膦钯、[1,1-双(二苯基磷)二茂铁]二氯化钯、二(三叔丁基膦)钯中的至少一种。
优选的,所述碱的量为1,1,2,2-四硼酸酯乙烯摩尔量的4.8~6.0eq;所述水的量为1,1,2,2-四硼酸酯乙烯摩尔量的10~20eq。
优选的,所述催化剂的量为1,1,2,2-四硼酸酯乙烯摩尔量的3~5mol%。
优选的,所述反应时间为42~48h。
本发明的有益效果:
本发明以1,1,2,2-四硼酸酯乙烯为原料,通过与卤代芳烃的偶联反应得到四芳基取代乙烯类化合物,操作简便,所使用的反应试剂无毒,为四芳基取代乙烯类化合物的合成提供新型且快捷的途径。通过该方法制备得到的四芳基取代乙烯类化合物,还可以进一步通过氧化关环或修饰芳环上的取代基团进行衍生化。
附图说明
图1为本发明实施例1制得的样品的核磁氢谱图;
图2为本发明实施例1制得的样品的核磁碳谱图;
图3为本发明实施例2制得的样品的核磁氢谱图;
图4为本发明实施例2制得的样品的核磁碳谱图;
图5为本发明实施例3制得的样品的核磁氢谱图;
图6为本发明实施例3制得的样品的核磁碳谱图;
图7为本发明实施例4制得的样品的核磁氢谱图;
图8为本发明实施例4制得的样品的核磁碳谱图;
图9为本发明实施例5制得的样品的核磁氢谱图;
图10为本发明实施例5制得的样品的核磁碳谱图;
图11为本发明实施例6制得的样品的核磁氢谱图;
图12为本发明实施例6制得的样品的核磁碳谱图。
具体实施方式
下面结合具体实施例,进一步阐述本发明。值得说明,这些实施例仅用于说明本发明,而不用于限定本发明的保护范围。在实际应用中技术人员根据本发明做出的改进和调整,仍属于本发明的保护范围。
实施例1
1.1,1,2,2-四硼酸酯乙烯的制备方法,其步骤为:氮气氛围下,向反应瓶中加入1.39g 1,2-二硼酸酯乙炔,1.52g联硼酸频那醇酯,62mg四三苯基膦铂催化剂以及溶剂甲苯5ml。混合体系于110℃下反应4d。反应结束后,待反应体系冷却至室温,往体系中加入5ml正己烷;将反应体系于0℃下搅拌30min,转移到-20℃冰箱中冷却2h。用布什漏斗将沉淀滤出,滤饼用正己烷洗涤3遍,得白色固体(1,1,2,2-四硼酸酯乙烯)1.96g,产率为74%。
氢谱、碳谱数据分别如下:
1H NMR(400MHz,CDCl3)δ1.24(s,48H);
13C NMR(101MHz,CDCl3)δ83.35,24.95。
实施例2
氮气氛围下,向反应瓶中加入1,1,2,2-四硼酸酯乙烯(107mg,0.2mmol),对溴甲苯(164mg,0.96mmol),[1,1'-双(二苯基膦基)二茂铁]二氯化钯(7.5mg,0.01mmol),碳酸铯(391mg,1.2mmol),溶剂二恶烷(3ml),水(40uL)。混合体系于70℃下反应48h。反应结束后,待反应体系冷却至室温,用乙醚和水进行萃取;合并有机层,干燥,旋干溶剂,进行柱层析分离,得到目标产物四对甲苯基乙烯(61mg,产率为78%)。
氢谱、碳谱数据分别如下:
1H NMR(400MHz,CDCl3)δ6.92(s,12H),2.28(s,16H);
13C NMR(101MHz,CDCl3)δ141.48,139.98,135.78,131.36,128.44,21.34。
实施例3
氮气氛围下,向反应瓶中加入1,1,2,2-四硼酸酯乙烯(107mg,0.2mmol),对溴苯甲醛(178mg,0.96mmol),[1,1'-双(二苯基膦基)二茂铁]二氯化钯(7.5mg,0.01mmol),碳酸铯(391mg,1.2mmol),溶剂二恶烷(3ml),水(40uL)。混合体系于70℃下反应48h。反应结束后,待反应体系冷却至室温,用乙醚和水进行萃取;合并有机层,干燥,旋干溶剂,进行柱层析分离,得到目标产物(80mg,产率为90%)。
氢谱、碳谱数据分别如下:
1H NMR(400MHz,CDCl3)δ9.92(s,4H),7.68(d,8Hz,8H),δ7.19(d,8Hz,8H);
13C NMR(101MHz,CDCl3)δ191.52,147.98,142.29,135.42,131.85,129.69。
实施例4
氮气氛围下,向反应瓶中加入1,1,2,2-四硼酸酯乙烯(107mg,0.2mmol),对溴苯甲酸甲酯(206mg,0.96mmol),[1,1'-双(二苯基膦基)二茂铁]二氯化钯(7.5mg,0.01mmol),碳酸铯(391mg,1.2mmol),溶剂二恶烷(3ml),水(40uL)。混合体系于70℃下反应48h。反应结束后,待反应体系冷却至室温,用乙醚和水进行萃取;合并有机层,干燥,旋干溶剂,进行柱层析分离,得到目标产物(105mg,产率为93%)。
氢谱、碳谱数据分别如下:
1H NMR(400MHz,CDCl3)δ7.79(d,J=7.9Hz,8H),7.06(d,J=7.9Hz,8H),3.87(s,12H);
13C NMR(101MHz,CDCl3)δ166.68,146.94,141.78,131.21,129.47,129.08,52.21。
实施例5
氮气氛围下,向反应瓶中加入1,1,2,2-四硼酸酯乙烯(107mg,0.2mmol),6-溴-2-萘甲酸甲酯(255mg,0.96mmol),[1,1'-双(二苯基膦基)二茂铁]二氯化钯(7.5mg,0.01mmol),碳酸铯(391mg,1.2mmol),溶剂二恶烷(3ml),水(40uL)。混合体系于70℃下反应48h。反应结束后,待反应体系冷却至室温,用乙醚和水进行萃取;合并有机层,干燥,旋干溶剂,进行柱层析分离,得到目标产物(86mg,产率为56%)。
氢谱、碳谱数据分别如下:
1H NMR(400MHz,CDCl3)δ8.46(s,4H),7.93(d,J=8.6Hz,4H),7.69–7.61(m,8H),7.57(d,J=8.7Hz,4H),7.29(d,J=8.9Hz,4H),3.94(s,12H);
13C NMR(101MHz,CDCl3)δ167.17,143.13,142.43,135.34,131.53,130.77,130.75,130.13,129.03,128.32,127.81,125.65,52.33.
实施例6
氮气氛围下,向反应瓶中加入1,1,2,2-四硼酸酯乙烯(107mg,0.2mmol),5-溴苯并噻吩(205mg,0.96mmol),[1,1'-双(二苯基膦基)二茂铁]二氯化钯(7.5mg,0.01mmol),碳酸铯(391mg,1.2mmol),溶剂二恶烷(3ml),水(40uL)。混合体系于70℃下反应48h。反应结束后,待反应体系冷却至室温,用乙醚和水进行萃取;合并有机层,干燥,旋干溶剂,进行柱层析分离,得到目标产物(68mg,产率为61%)。
氢谱、碳谱数据分别如下:
1H NMR(400MHz,CDCl3)δ7.56(d,J=8.3Hz,8H),7.32(d,J=5.4Hz,4H),7.11(m,8H);
13C NMR(101MHz,CDCl3)δ141.01,140.66,139.60,138.10,128.33,126.71,126.35,124.24,121.80。
Claims (10)
3.根据权利要求2所述的1,1,2,2-四硼酸酯乙烯的制备方法,其特征在于:所述1,2-二硼酸酯乙炔和联硼酸频那醇酯的摩尔比为1:1.2~1.5,1,2-二硼酸酯乙炔的浓度为0.8~1.2mol/L。
4.根据权利要求2所述的1,1,2,2-四硼酸酯乙烯的制备方法,其特征在于:所述四三苯基膦铂的量为1,2-二硼酸酯乙炔摩尔量的0.6~1mol%;
所述有机溶剂选自甲苯、环己烷、N,N-二甲基甲酰胺的至少一种。
6.根据权利要求5所述的1,1,2,2-四硼酸酯乙烯的应用,其特征在于:所述R为氢、C1~C10的烷基、羰基、氰基、甲硫基;X为Cl、Br、I。
7.根据权利要求6所述的1,1,2,2-四硼酸酯乙烯的应用,其特征在于:所述R为C1~C3的烷基、羰基、氰基;X为Br。
8.根据权利要求7所述的1,1,2,2-四硼酸酯乙烯的应用,其特征在于:所述R为酮羰基、醛羰基、酯羰基。
9.根据权利要求5-8任一项所述的1,1,2,2-四硼酸酯乙烯的应用,其特征在于:所述1,1,2,2-四硼酸酯乙烯和卤代芳烃的摩尔比为1:4.8~6.0,1,1,2,2-四硼酸酯乙烯的浓度为0.06~0.1mol/L。
10.根据权利要求5-8任一项所述的1,1,2,2-四硼酸酯乙烯的应用,其特征在于:所述有机溶剂选自四氢呋喃、二噁 烷、乙二醇二甲醚中的至少一种;
所述碱选自碳酸铯、氢氧化钠、氢氧化钾、磷酸钾、碳酸钾中的至少一种;碱的量为1,1,2,2-四硼酸酯乙烯摩尔量的4.8~6.0eq;
所述催化剂选自四三苯基膦钯、[1,1-双(二苯基磷)二茂铁]二氯化钯、二(三叔丁基膦)钯中的至少一种;催化剂的量为1,1,2,2-四硼酸酯乙烯摩尔量的3~5mol%;
所述水的量为1,1,2,2-四硼酸酯乙烯摩尔量的10~20eq。
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