CN113717396A - 一种催化炔烃硼氢化反应的铜(i)基共价金属有机框架材料及其制备方法 - Google Patents
一种催化炔烃硼氢化反应的铜(i)基共价金属有机框架材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种催化炔烃硼氢化反应的铜(I)基共价金属有机框架材料及其制备方法,涉及多孔框架材料的催化应用领域。具体公开了:将均苯四甲酸酐、3,5‑二甲基‑4‑氨基吡唑和铜源混合于N,N‑二甲基甲酰胺、乙醇和吡啶的混合溶液中,恒温加热反应结束后,洗涤、干燥,即得铜(I)基共价金属有机框架材料。本发明通过结合配位反应和酰亚胺反应,利用便宜易得的原料一步合成了具有铜(I)三核节点的共价金属有机框架,为异相多孔催化剂,该催化剂能够高效、高选择性、可循环性的催化炔烃硼氢化。
Description
技术领域
本发明涉及多孔框架材料的催化应用领域,特别是涉及一种催化炔烃硼氢化反应的铜(I)基共价金属有机框架材料及其制备方法。
背景技术
近年来,MOF(metal organic framework,金属有机框架)化学和COF(covalentorganic frameworks,共价有机框架)化学的“二合一”策略引起了极大的关注。科学家尝试在COF框架中引入金属离子或单核金属配合物,所得的新型材料既具有COF的高稳定性,又具有由金属离子带来的催化、传感、分子吸附和分离等的新功能,为新型功能材料的构筑指明了新的方向。与单个金属离子单元相比,金属簇或多核金属配合物因其结构多样性和独特的物理化学性质而更具吸引力。然而,由于金属团簇的形成条件与动态共价键的形成条件兼容性差,存在团簇基团的稳定性和溶解性问题,通过动态共价键连接金属团簇构建簇基框架材料,即共价金属有机框架(covalent metal organic framework,CMOF),仍是一个极具挑战性的课题。
有机硼化合物是有机合成领域中最被广泛使用的中间体之一。在合适的催化剂和反应条件下,有机硼化物可以转化为各种具有特定官能团的化合物,因而受到广泛的关注。例如,有机硼化合物可以作为Suzuki-Miyaura交叉偶联的中间体,在Pd催化剂的作用下,可以转化为各种具有优异性能的有机半导体材料和具有复杂结构的药物分子。炔烃的硼氢化反应是合成烯基硼酸盐的一种简便和高效的方法。烯基硼化合物分子中具有不饱和双键,因而容易作为中间体进一步转化。近年来,科学家们开发了大量过渡金属催化剂用于催化炔烃转化为烯基硼酸盐的硼氢化反应,使该领域得到了长足的发展。然而,该类催化剂多为均相催化剂,不易回收和循环利用。应用于硼氢化反应需要较为苛刻的无氧反应条件,反应时间较长,效率不高。因此,需要开发一种可以高效、简便催化炔烃的硼氢化反应的、易回收、可循环使用的异相催化剂。
发明内容
本发明的目的是提供一种催化炔烃硼氢化反应的铜(I)基共价金属有机框架材料及其制备方法,以解决上述现有技术存在的问题,实现高效、简便地催化炔烃硼氢化反应,且催化剂具有易回收、可循环使用的特点。
为实现上述目的,本发明提供了如下方案:
本发明的技术方案之一是提供一种铜(I)基共价金属有机框架材料,结构如式1所示:
本发明的技术方案之二是提供上述铜(I)基共价金属有机框架材料的制备方法,包括以下步骤:
将均苯四甲酸酐、3,5-二甲基-4-氨基吡唑和铜源混合于N,N-二甲基甲酰胺、乙醇和吡啶的混合溶液中,恒温加热反应结束后,洗涤、干燥,即得所述铜(I)基共价金属有机框架材料;
所述铜源为Cu2O或Cu(NO3)2·3H2O。
进一步地,所述均苯四甲酸酐、3,5-二甲基-4-氨基吡唑和Cu2O的摩尔为1:2:1;所述均苯四甲酸酐、3,5-二甲基-4-氨基吡唑和Cu(NO3)2·3H2O的摩尔为1:2:2;
所述混合溶液中N,N-二甲基甲酰胺、乙醇和吡啶的体积比为(0.5~1.5):(0.5~1.5):(0.05~0.15)。
进一步地,所述恒温加热反应的温度为100~120℃,反应时间为12~24h。
进一步地,所述洗涤的操作为:用氨水、N,N-二甲基甲酰胺和乙醇依次进行洗涤。
本发明的技术方案之三是提供上述铜(I)基共价金属有机框架材料在催化炔烃硼氢化反应中的应用。
进一步地,所述炔烃硼氢化反应为炔烃和双联频哪醇硼酸酯的反应。
进一步地,所述应用包括以下步骤:将上述铜(I)基共价金属有机框架材料、碱、双联频哪醇硼酸酯和炔烃加入到溶剂中,常温搅拌反应,得到烯基硼酸酯类化合物。
进一步地,所述溶剂为乙腈和水的混合溶剂。
进一步地,所述常温搅拌反应的时间为0.5~1h。
进一步地,所述铜(I)基共价金属有机框架材料的用量为炔烃摩尔数的5~20%。
进一步地,炔烃与双联频哪醇硼酸酯的摩尔比为1:2;所用的碱为K2CO3,用量为炔烃摩尔数的2倍。
本发明公开了以下技术效果:
到目前为止,尚未有催化炔烃硼氢化反应的铜(I)基共价金属有机框架材料制备技术的报道,本发明通过结合配位反应和酰亚胺反应,利用便宜易得的原料一步合成了具有铜(I)三核节点的共价金属有机框架,为异相催化剂,并将其应用于催化炔烃的硼氢化反应,该反应条件温和、无需惰性气体保护、效率高、产率高、应用范围广,催化剂易于回收,可循环使用而不降低催化效果,具有重要的应用价值。
本发明通过金属铜(I)和有机配体的缩合反应,即可制备高晶性的碳氮单键连接的铜(I)共价金属有机框架材料,该材料具有多孔结构,作为活性位点的金属铜(I)可以均匀地分布在多孔材料的框架上,并满足在炔烃的硼氢化反应中的催化应用,填补了目前没有关于催化炔烃硼氢化反应的铜(I)基共价金属有机框架材料的技术空白,本发明制备的该材料能够高效、高选择性、可循环性的催化炔烃硼氢化。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为实施例1制备的铜(I)基共价金属有机框架材料1的红外谱图;
图2为实施例1制备的铜(I)基共价金属有机框架材料1的600MHz下13C固体核磁共振谱图;
图3为实施例1制备的铜(I)基共价金属有机框架材料1的X-射线粉末衍射图及其Pawley精修结果;
图4为实施例1制备的铜(I)基共价金属有机框架材料1的二维重叠蜂窝结构模拟图;
图5为实施例1制备的铜(I)基共价金属有机框架材料1的扫描电镜图;
图6为实施例1制备的铜(I)基共价金属有机框架材料1的高分辨透射电镜图;
图7为实施例1制备的铜(I)基共价金属有机框架材料1的氮气吸附脱附曲线;
图8为实施例1制备的铜(I)基共价金属有机框架材料1的孔径分布图;
图9为实施例1制备的铜(I)基共价金属有机框架材料1的热重分析图;
图10为实施例1制备的铜(I)基共价金属有机框架材料1在实施例3条件下催化苯乙炔的硼氢化反应,经过不同轮数催化实验后的X-射线粉末衍射图。
图11为实施例1制备的铜(I)基共价金属有机框架材料1在实施例3条件下催化苯乙炔硼氢化反应不同轮数后的效果图。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见的。本发明说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。
本发明铜基(I)共价金属有机框架材料的结构如下所示:
反应式如下:
制备方法具体包括以下步骤:
将均苯四甲酸酐、3,5-二甲基-4-氨基吡唑和铜源混合于DMF、EtOH和吡啶体积比1:1:0.1的溶液中(其中,铜源为Cu2O或Cu(NO3)2·3H2O:当铜源为Cu2O时,均苯四甲酸酐、3,5-二甲基-4-氨基吡唑和Cu2O的摩尔为1:2:1;当铜源为Cu(NO3)2·3H2O时,均苯四甲酸酐、3,5-二甲基-4-氨基吡唑和Cu(NO3)2·3H2O的摩尔为1:2:2),所得混合物放置在120℃的烘箱中恒温加热12小时,结束后过滤,所得橙色固体依次用氨水、热DMF和乙醇洗涤,再真空加热干燥,即可得到铜(I)基共价金属有机框架材料1。
以本发明的铜(I)基共价金属有机框架材料为催化剂,催化炔烃和双联频哪醇硼酸酯(B2Pin2)在碱性环境中反应得到烯基硼酸酯类化合物,具体步骤如下:依次将铜(I)基共价金属有机框架材料、碱、B2Pin2和炔烃加入到乙腈和水的混合溶剂中,常温搅拌反应0.5h后得到烯基硼酸酯类化合物。
铜(I)基共价金属有机框架材料的用量为炔烃摩尔数的5~20%;炔烃与B2Pin2的摩尔比为1:2;所用的碱为K2CO3,用量为炔烃摩尔数的2倍。
本发明铜(I)基共价金属有机框架材料在催化炔烃硼氢化反应中的循环性测试,包括以下步骤:催化反应后,催化剂通过过滤分离,再依次以水、乙醇洗涤,真空加热干燥后即可用于下一轮催化实验。
实施例1以Cu2O为铜源制备铜(I)基共价金属有机框架材料1
将均苯四甲酸酐(4mmol,0.872g)、3,5-二甲基-4-氨基吡唑(8mmol,0.888g)、Cu2O(4mmol,0.572g)在20mL DMF、20mL无水乙醇和2mL吡啶中混合,并将其密封于300mL的反应器中,在120℃的烘箱中恒温加热12小时。所得橙色固体依次用氨水、热DMF(120℃)和乙醇洗涤后真空干燥,得到铜(I)基共价金属有机框架材料1,产量:1.523g(74.2%)。元素分析的计算值:C27H21Cu3N9O6,C,42.77;H,2.79;N,16.63,测试值:C,43.30;H,2.91;N,16.86,红外光谱数据(KBr,cm-1):3435(m),1779(m),1723(s),1454(w),1525(w),1469(w),1386(w),1355(w),1127(m),1083(w),845(m),724(m),569(w),497(w)。
实施例2以Cu(NO3)2·3H2O为铜源制备铜(I)基共价金属有机框架材料1
将均苯四甲酸酐(4mmol,0.872g)、3,5-二甲基-4-氨基吡唑(8mmol,0.888g)、Cu(NO3)2·3H2O(8mmol,1.932g)在20mL DMF、20mL无水乙醇和2mL吡啶中混合,并将其密封于300mL的反应器中,在120℃的烘箱中恒温加热12小时。所得橙色固体依次用氨水、热DMF(120℃)和乙醇洗涤后真空干燥,得到铜(I)基共价金属有机框架材料1,产量:1.570g(76.5%)。
实施例3铜(I)基共价金属有机框架材料1用于催化炔烃的硼氢化反应
在10mL试管中,依次加入炔烃(0.2mmol)、铜(I)基共价金属有机框架材料1(15mg,0.02mmol,10mol%)、K2CO3(65mg,0.4mmol,2.0equiv)、B2Pin2(120mg,0.4mmol,2.0equiv)和乙腈/水(9:1,2mL),然后在常温搅拌反应0.5h。反应结束后将溶液用200-300目硅胶快速柱层析,使用石油醚/乙酸乙酯(1:1)的淋洗剂洗脱得到相应产物。
利用不同烯烃反应得到的产物及对应的收率如下:
以上产物的具体表征数据如下:
(E)-4,4,5,5-tetramethyl-2-styryl-1,3,2-dioxaborolane.1H NMR(400MHz,CDCl3):δ7.51(d,J=8Hz,2H),7.43(d,J=20Hz,1H),7.30-7.39(m,3H),6.20(d,J=20Hz,1H),1.34(s,12H).13C NMR(CDCl3):δ147.53,137.43,128.92,128.58,127.07,83.38,25.29.11B NMR(CDCl3):δ30.12.
(E)-4,4,5,5-tetramethyl-2-(2-methylstyryl)-1,3,2-dioxaborolane.1H NMR(400MHz,CDCl3):δ7.67(d,J=20Hz,1H),7.59-7.57(m,1H),7.29-7.16(m,3H),6.11(d,J=16Hz,1H),2.44(s,3H),1.34(s,12H).13C NMR(CDCl3):δ147.13,136.67,136.33,130.41,128.41,126.12,125.76,83.33,24.84,19.86.11B NMR(CDCl3):δ30.15.
(E)-4,4,5,5-tetramethyl-2-(3-methylstyryl)-1,3,2-dioxaborolane.1H NMR(400MHz,CDCl3):δ7.40(d,J=16Hz,1H),7.32-7.23(m,2H),7.13(d,J=8Hz,1H),6.17(d,J=16Hz,1H),2.39(s,3H),1.34(s,12H).13C NMR(CDCl3):δ149.69,138.10,137.41,129.73,128.46,127.79,124.25,83.34,24.83,21.42.11B NMR(CDCl3):δ30.23.
(E)-4,4,5,5-tetramethyl-2-(4-methylstyryl)-1,3,2-dioxaborolane.1H NMR(400MHz,CDCl3):δ7.39(d,J=8Hz,2H),7.32(d,J=28Hz,1H),7.14(d,J=8Hz,1H),6.11(d,J=20Hz,1H),2.37(s,3H),1.31(s,12H).13C NMR(CDCl3):δ149.48,138.96,134.73,129.27,127.00,83.28,24.78,21.03.11BNMR(CDCl3):δ29.96.
(E)-2-(3-methoxystyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.1HNMR(400MHz,CDCl3):δ7.38(d,J=20Hz,1H),7.30-7.26(m,1H),7.11(d,J=8Hz,1H),7.07-7.03(m,1H),7.05(s,1H),6.88(d,J=8Hz,1H),6.18(d,d,J=16Hz,1H),3.89(s,1H),1.34(s,12H).13C NMR(CDCl3):δ159.72,149.39,138.90,129.55,119.84,114.81,111.89,83.14,55.20,24.82.11B NMR(CDCl3):δ30.21.
(E)-2-(4-methoxystyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.1HNMR(400MHz,CDCl3):δ7.43(d,J=8Hz,2H),7.35(d,J=16Hz,1H),6.87(d,J=8Hz,2H),6.01(d,J=16Hz,1H),3.81(s,3H),1.31(s,12H).13C NMR(CDCl3):160.26,149.06,130.35,128.44,113.93,83.20,53.42,24.57.11BNMR(CDCl3):δ30.11.
(E)-2-(3-fluorostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.1H NMR(400MHz,CDCl3):δ7.38-7.25(m,3H),7.19(d,J=8Hz,1H),7.01(t,J=8Hz,1H),6.18(d,J=20Hz,1H),1.33(s,12H).13C NMR(CDCl3):δ164.28,148.10,139.85,130.08,123.03,115.60,113.40,83.52,24.82.11B NMR(CDCl3):δ30.01.
(E)-2-(4-fluorostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.1H NMR(400MHz,CDCl3):δ7.45-7.42(m,2H),7.35(d,J=16Hz 1H),7.01-6.97(m,2H),6.07(d,J=16Hz,1H)1.27(s,12H).13CNMR(CDCl3):δ164.34,148.15,133.66,128.72,115.63,83.37,24.77.11B NMR(CDCl3):δ29.95.
(E)-2-(3-chlorostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.1H NMR(400MHz,CDCl3):δ7.47(s,1H),7.38-7.34(m,1H),7.33(d,J=20Hz,1H),7.29-7.27(m,2H),6.19(d,J=20Hz,1H),1.33(s,12H).13C NMR(CDCl3):δ147.86,139.31,134.56,129.82,128.77,126.94,125.21,83.53,24.82.11B NMR(CDCl3):δ30.02.
(E)-2-(4-chlorostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.1H NMR(400MHz,CDCl3):δ7.43(d,J=8Hz,2H),7.36(d,J=16Hz,1H),7.32(d,J=8Hz,2H),6.13(d,J=16Hz,1H),1.31(S,12H).13C NMR(CDCl3):δ148.04,135.92,134.61,128.80,128.24,83.49,24.83.11B NMR(CDCl3):δ30.21.
(E)-2-(3-bromostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.1H NMR(400MHz,CDCl3):δ7.63(s,1H),7.41(t,J=8Hz,2H),7.32(d,J=20Hz,2H)7.22(t,J=8Hz,1H),6.17(d,J=16Hz,1H),1.33(s,12H).13C NMR(CDCl3):δ147.74,139.60,132.01,129.92,122.78,83.52,24.80.1B NMR(CDCl3):δ29.83.
(E)-2-(4-bromostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.1H NMR(400MHz,CDCl3):δ7.48(d,J=8Hz,2H),7.36(d,J=8Hz,2H),7.34(d,J=16Hz,1H),6.17(d,J=16Hz,1H),1.33(s,12H).13C NMR(CDCl3):δ148.09,136.35,131.76,128.52,122.92,83.50,24.82.11B NMR(CDCl3):δ30.42.
(E)-4,4,5,5-tetramethyl-2(4-(trifluoromethyl)styryl)-1,3,2-dioxaborolane.1H NMR(400MHz,CDCl3):δ7.38-7.25(m,1H),7.19(d,J=20Hz,1H),7.64-7.50(m,4H),7.39(d,1H),6.25(d,J=20Hz,1.32(s,12H).13C NMR(CDCl3):147.70,140.74,130.29,127.16,125.63,122.73,83.64,24.59.11B NMR(CDCl3):δ30.32.
Methyl(E)-4-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)benzoate.1H NMR(400MHz,CDCl3):δ8.02(d,J=8Hz,2H),7.55(d,J=8Hz,2H),7.42(d,J=20Hz,1H),6.29(d,J=16Hz,1H),3.92(s,3H),1.33(s,12H).13C NMR(CDCl3):δ148.14,141.67,130.20,129.68,128.22,126.90,83.59,24.58.11B NMR(CDCl3):δ30.13.
(E)-3-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)aniline.1HNMR(400MHz,CDCl3):δ7.33(d,J=16Hz,1H),7.15(t,J=8Hz,1H),6.93(d,J=8Hz,1H),6.84(s,1H),6.67(d,J=8Hz,1H),6.17(d,J=16Hz,1H),3.33(br,2H),1.27(s,12H).13CNMR(CDCl3):δ149.70,146.21,138.56,129.48,118.10,116.05,113.53,83.34,24.82.11B NMR(CDCl3):δ30.32.
(E)-3-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)pyridine.1H NMR(400MHz,CDCl3):δ8.70(s,1H),8.53-8.48(m,1H),7.83(d,J=8Hz,1H),7.39(d,J=20Hz 1H),7.32-7.28(m,1H),6.26(d,J=20Hz,1H),1.33(s,12H).13C NMR(CDCl3):δ152.65,149.51,147.96,133.34,132.88,123.64,83.63,24.66.11B NMR(CDCl3):δ30.10.
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (9)
2.如权利要求1所述的铜(I)基共价金属有机框架材料的制备方法,其特征在于,包括以下步骤:
将均苯四甲酸酐、3,5-二甲基-4-氨基吡唑和铜源混合于N,N-二甲基甲酰胺、乙醇和吡啶的混合溶液中,恒温加热反应结束后,洗涤、干燥,即得所述铜(I)基共价金属有机框架材料;
所述铜源为Cu2O或Cu(NO3)2·3H2O。
3.根据权利要求2所述的制备方法,其特征在于,所述均苯四甲酸酐、3,5-二甲基-4-氨基吡唑和Cu2O的摩尔为1:2:1;所述均苯四甲酸酐、3,5-二甲基-4-氨基吡唑和Cu(NO3)2·3H2O的摩尔为1:2:2;
所述混合溶液中N,N-二甲基甲酰胺、乙醇和吡啶的体积比为(0.5~1.5):(0.5~1.5):(0.05~0.15)。
4.根据权利要求2所述的制备方法,其特征在于,所述恒温加热反应的温度为100~120℃,反应时间为12~24h。
5.根据权利要求2所述的制备方法,其特征在于,所述洗涤的操作为:用氨水、N,N-二甲基甲酰胺和乙醇依次进行洗涤。
6.如权利要求1所述的铜(I)基共价金属有机框架材料在催化炔烃硼氢化反应中的应用。
7.根据权利要求6所述的应用,其特征在于,所述炔烃硼氢化反应为炔烃和双联频哪醇硼酸酯的反应。
8.根据权利要求7所述的应用,其特征在于,包括以下步骤:将权利要求1所述的铜(I)基共价金属有机框架材料、碱、双联频哪醇硼酸酯和炔烃加入到溶剂中,常温搅拌反应,得到烯基硼酸酯类化合物。
9.根据权利要求8所述的应用,其特征在于,所述铜(I)基共价金属有机框架材料的用量为炔烃摩尔数的5~20%。
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