CN111675650B - 一种芳香乙烯基溴衍生物的制备方法 - Google Patents
一种芳香乙烯基溴衍生物的制备方法 Download PDFInfo
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07—ORGANIC CHEMISTRY
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
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- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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Abstract
一种芳香乙烯基溴衍生物的制备方法,本发明涉及一种芳香乙烯基溴衍生物的制备方法。本发明的目的是为了解决现有方法合成芳香乙烯基溴衍生物反应条件苛刻、底物兼容性差且污染环境的问题,本发明室温下,在氮气气氛下,将炔烃衍生物、溴代芳香环类化合物和催化剂溶解在有机溶剂中,进行光照反应,待反应结束后,旋蒸溶剂,提纯,即完成;本发明解决了现有芳香乙烯基溴衍生物合成需要有毒有害物质激发和过渡金属催化体系导致的产率低、方法环保性差、底物兼容性差的问题,本发明应用于有机合成领域。
Description
技术领域
本发明涉及一种芳香乙烯基溴衍生物的制备方法。
背景技术
炔烃是一类常见的功能性结构,存在于多种多样的有价值的结构分子中。因为其特殊 的结构骨架,所以大量的研究用于修饰其骨架结构。炔烃的双官能团化便是其中重要的研 究之一。炔烃双官能团化得到的高度功能化烯烃,是一类重要的合成复杂分子的前体结构。 针对该研究项目中炔烃双官能团化引入溴原子(Br)而言,其在建筑材料中有广泛的应用, 同时也是一种常用的、有价值的化学转换中间体。
目前,对于炔烃衍生物双官能团化的研究报道有很多。其中原子转移自由基加成(ATRA)策略因其原子经济性被广泛的应用于实现炔烃分子的双官能团化研究。传统的ATRA过程中,自由基的生成通常需要化学当量的有毒有害引发剂,如过氧化物、有机锡 试剂、三烷基硼烷或高强度紫外线。此外,传统的ATRA方法反应条件苛刻、底物兼容 性差。这在某种程度上,造成了合成经济效益降低,同时对环境产生极大的污染和破坏。 所以在环境问题日益严重的今天,高效利用绿色无污染、可再生的光能变得尤为重要。因 此,寻求一种绿色高效、条件温和、方法简单且操作方便的方法是合成芳香乙烯基溴衍生 物亟待解决的关键问题。
发明内容
本发明的目的是为了解决现有方法合成芳香乙烯基溴衍生物反应条件苛刻、底物兼容 性差且污染环境的问题,提供一种芳香乙烯基溴衍生物的制备方法。
本发明一种芳香乙烯基溴衍生物的制备方法,按以下步骤进行:室温下,在氮气气氛 下,将炔烃衍生物、溴代芳香环类化合物和催化剂溶解在有机溶剂中,混合均匀后置于蓝 色LEDs灯光下进行光照反应,待反应结束后,旋蒸溶剂,再经过硅胶柱柱层析分离提纯,即可得到芳香乙烯基溴衍生物;其中炔烃衍生物、溴代芳香环类化合物和催化剂的投料摩尔比为2:1:0.2;其中炔烃衍生物的化学结构式为:其中,R1为取代芳香 基或者烷基,R2为氢原子或羧基取代基;溴代芳香环类化合物的化学结构式为:Ar-Br。
本发明的有益效果为:
本发明提供了一种简洁的一步法合成芳香乙烯基溴衍生物的方法。该方法选择环保、 绿色、自然丰度大的可见光蓝光作为自由基引发条件,成功避免了使用有毒有害的引发剂。 同时该方法适用于苯乙炔类化合物、脂肪族炔类化合物、末端炔烃、非末端炔烃以及炔丙 酸类化合物,大大增加了底物的兼容性,丰富了底物的种类。该方法解决了现有芳香乙烯 基溴衍生物合成需要有毒有害物质激发和过渡金属催化体系导致的产率低、方法环保性 差、底物兼容性差的问题,寻求到一条绿色高效、条件温和、方法简单且操作方便的合成 芳香乙烯基溴衍生物的路线,也为现代工业化的发展奠定了一定的基础。
附图说明
图1为实施例1所得Z型双取代4-(2-溴-2-苯基乙烯基)吡啶衍生物的1H NMR谱图;
图2为实施例1所得Z型双取代4-(2-溴-2-苯基乙烯基)吡啶衍生物的13C NMR谱图;
图3为实施例1所得E型双取代4-(2-溴-2-苯基乙烯基)吡啶衍生物的1H NMR谱图;
图4为实施例1所得E型双取代4-(2-溴-2-苯基乙烯基)吡啶衍生物的13C NMR谱图。
具体实施方式
具体实施方式一:本实施方式一种芳香乙烯基溴衍生物的制备方法,按以下步骤进行: 室温下,在氮气气氛下,将炔烃衍生物、溴代芳香环类化合物和催化剂溶解在有机溶剂中, 混合均匀后置于蓝色LEDs灯光下进行光照反应,待反应结束后,旋蒸溶剂,再经过硅胶 柱柱层析分离提纯,即可得到芳香乙烯基溴衍生物;其中炔烃衍生物、溴代芳香环类化合 物和催化剂的投料摩尔比为2:1:0.2;其中炔烃衍生物的化学结构式为:其中,R1为取代芳香基或者烷基,R2为氢原子或羧基取代基;溴代芳香环类化合物的化学 结构式为:Ar-Br;催化剂为CuBr。
本实施方式制得的衍生物的结构式如式(Ⅰ)所示:
其中,R1为取代芳香基或者烷基,Ar为吡啶环或者对位带强吸电子基的苯环;所述取代芳香基为苯环上带有烷基、卤素、烷氧基的苯基或者为噻吩环等芳香杂环;烷基通常包括但不限于:叔丁基。
其反应路线为:
本实施方式提供了一种简洁的一步法合成芳香乙烯基溴衍生物的方法。该方法选择环 保、绿色、自然丰度大的可见光蓝光作为自由基引发条件,成功避免了使用有毒有害的引 发剂。同时该方法适用于苯乙炔类化合物、脂肪族炔类化合物、末端炔烃、非末端炔烃以 及炔丙酸类化合物,大大增加了底物的兼容性,丰富了底物的种类。该方法解决了现有芳 香乙烯基溴衍生物合成需要有毒有害物质激发和过渡金属催化体系导致的产率低、方法环 保性差、底物兼容性差的问题,寻求到一条绿色高效、条件温和、方法简单且操作方便的 合成芳香乙烯基溴衍生物的路线,也为现代工业化的发展奠定了一定的基础。
具体实施方式二:本实施方式与具体实施方式一不同的是:炔烃衍生物为苯乙炔类化 合物、烷基乙炔类化合物或炔丙酸类化合物。其他与具体实施方式一相同。
具体实施方式三:本实施方式与具体实施方式一或二不同的是:溴代芳香环类化合物 为4-溴吡啶、4-氰基溴苯或4-酯基溴苯。其他与具体实施方式一或二相同。
具体实施方式四:本实施方式与具体实施方式一至三之一不同的是:有机溶剂为丙酮、 乙腈、四氢呋喃、二氯乙烷或二甲基亚砜。其他与具体实施方式一至三之一相同。
具体实施方式五:本实施方式与具体实施方式一至四之一不同的是:溴代芳香环类化 合物和有机溶剂的摩尔体积比为1mmol:10mL。其他与具体实施方式一至四之一相同。
具体实施方式六:本实施方式与具体实施方式一至五之一不同的是:通过TLC监测光照反应进程。其他与具体实施方式一至五之一相同。
具体实施方式七:本实施方式与具体实施方式一至六之一不同的是:置于蓝色LEDs 灯下反应的时间为24-36h。其他与具体实施方式一至六之一相同。
具体实施方式八:本实施方式与具体实施方式一至七之一不同的是:硅胶柱层析分离 纯化所用溶剂为石油醚与乙酸乙酯的混合溶剂。其他与具体实施方式一至七之一相同。
具体实施方式九:本实施方式与具体实施方式一至八之一不同的是:石油醚与乙酸乙 酯的体积比为(10-20):1。其他与具体实施方式一至八之一相同。
为验证本发明的有益效果进行了以下实验:
实施例1
向10mL光反应器皿(青霉素小瓶)中,加入20.4mg(0.2mmol)苯乙炔,15.7mg(0.1mmol)4-溴吡啶化合物,2.8mg(20mol%)催化剂和1mL二甲基亚砜,氮气保护,用 胶塞和封口膜密封后,在室温条件下,置于36W蓝色LEDs灯下光照反应24h。用TLC 监测反应进度。
后处理:反应结束后,反应溶剂经旋转蒸发仪浓缩旋干后,再以体积比20:1的石油醚:乙酸乙酯的混合溶液作为洗脱剂,进行硅胶柱层析纯化分离,得到相应的双取代4- (2-溴-2-苯基乙烯基)吡啶类衍生物,其反应式为:
产物为无色粘稠状液体,纯度为99%,产率为54%,Z/E=5/11;其中Z型结构式为:E型结构式为:其Z型结构1H NMR谱图见附图1,Z 型结构13CNMR谱图见附图2;E型结构1H NMR谱图见附图3,E型结构13C NMR谱图 见附图4。核磁数据分析为:Z型结构NMR:1H NMR(500MHz,CDCl3)δ8.64(d,J=5.1Hz, 2H),7.65(d,J=7.4Hz,2H),7.57(d,J=5.1Hz,2H),7.39(t,J=7.2Hz,3H),7.13(s,1H); 13C NMR(101MHz,CDCl3)δ149.83,143.72,140.20,129.42,128.45,128.25,127.77,127.31, 123.39.E型结构NMR:1HNMR(400MHz,CDCl3)δ8.30(d,J=5.1Hz,2H),7.33–7.23(m, 5H),7.02(s,1H),6.74(d,J=5.2Hz,2H);13C NMR(151MHz,CDCl3)δ149.87,143.26, 138.64,130.60,129.52,128.89,128.81,128.38,122.84.
实施例2
向10mL光反应器皿(青霉素小瓶)中,加入31.6mg(0.2mmol)4-叔丁基苯乙炔,15.7mg(0.1mmol)4-溴吡啶化合物,2.8mg(20mol%)催化剂和1mL二甲基亚砜,氮气保 护,用胶塞和封口膜密封后,在室温条件下,置于36W蓝色LEDs灯下光照反应24h。 用TLC监测反应进度。
后处理:反应结束后,反应溶剂经旋转蒸发仪浓缩旋干后,再以体积比20:1的石油醚:乙酸乙酯的混合溶液作为洗脱剂,进行硅胶柱层析纯化分离,得到相应的双取代4- (2-溴-2-(4-叔丁基苯基)乙烯基)吡啶类衍生物,其反应式为:
产物为无色粘稠状液体,纯度为99%,产率为78%,Z/E=3/10;其中Z型结构式为:E型结构式为:核磁数据分析为:Z型结构1HNMR(400MHz, CDCl3)δ8.56(dd,J=4.7,1.4Hz,2H),7.56–7.44(m,4H),7.40–7.30(m,2H),7.04(s,1H), 1.27(s,9H);13C NMR(151MHz,CDCl3)δ152.85,149.85,143.80,137.32,128.32,127.51, 126.58,125.42,123.41,34.69,31.18.E型结构NMR:1H NMR(400MHz,CDCl3)δ8.30(dd,J =4.6,1.6Hz,2H),7.31–7.24(m,2H),7.22–7.14(m,2H),6.98(s,1H),6.75(dd,J=4.8,1.3 Hz,2H),1.24(s,9H);13C NMR(151MHz,CDCl3)δ152.84,149.81,143.43,135.51,130.16,128.79,128.53,125.70,122.79,34.75,31.15.
实施例3
向10mL光反应器皿(青霉素小瓶)中,加入34.0mg(0.2mmol)4-三氟甲基苯乙炔,15.7mg(0.1mmol)4-溴吡啶化合物,2.8mg(20mol%)催化剂和1mL二甲基亚砜,氮气保 护,用胶塞和封口膜密封后,在室温条件下,置于36W蓝色LEDs灯下光照反应24h。 用TLC监测反应进度。
后处理:反应结束后,反应溶剂经旋转蒸发仪浓缩旋干后,再以体积比20:1的石油醚:乙酸乙酯的混合溶液作为洗脱剂,进行硅胶柱层析纯化分离,得到相应的双取代4- (2-溴-2-(4-三氟甲基苯基)乙烯基)吡啶类衍生物,其反应式为:
产物为无色粘稠状液体,纯度为99%,产率为69%,Z/E=3/2。其中Z型结构式为:E型结构式为:核磁数据分析为:Z型结构1H NMR(400 MHz,CDCl3)δ8.60(d,J=5.6Hz,2H),7.69(d,J=8.3Hz,2H),7.59(d,J=8.3Hz,2H),7.50 (d,J=6.0Hz,2H),7.13(s,1H);13C NMR(151MHz,CDCl3)δ149.97,143.53,143.16,131.69 –130.72(t,J=31.9Hz),129.13,128.16,126.32,126.42,124.61,123.71(q,J=272.3Hz),123.34.E型结构NMR:1H NMR(400MHz,CDCl3)δ8.35(d,J=5.7Hz,2H),7.53(d,J=8.2 Hz,2H),7.38(d,J=8.1Hz,2H),7.11(s,1H),6.73(d,J=6.0Hz,2H);13C NMR(151MHz, CDCl3)δ150.07,142.68,142.03,131.88,131.29(q,J=32.6Hz),129.40,125.87,125.85, 125.82,123.56(q,J=272.6Hz),122.75.
实施例4
向10mL光反应器皿(青霉素小瓶)中,加入21.6mg(0.2mmol)2-乙炔基噻吩,15.7mg(0.1mmol)4-溴吡啶化合物,2.8mg(20mol%)催化剂和1mL二甲基亚砜,氮气保护, 用胶塞和封口膜密封后,在室温条件下,置于36W蓝色LEDs灯下光照反应26h。用TLC 监测反应进度。
后处理:反应结束后,反应溶剂经旋转蒸发仪浓缩旋干后,再以体积比20:1的石油醚:乙酸乙酯的混合溶液作为洗脱剂,进行硅胶柱层析纯化分离,得到相应的双取代4- (2-溴-2-(2-噻吩基)乙烯基)吡啶类衍生物,其反应式为:
产物为无色粘稠状液体,纯度为99%,产率为52%,Z/E=5/18。其中Z型结构式为:E型结构式为:核磁数据分析为:Z型结构1H NMR(400MHz, CDCl3)δ8.56(dd,J=4.6,1.5Hz,2H),7.49(d,J=6.1Hz,2H),7.38(dd,J=3.7,1.0Hz,1H), 7.29(d,J=1.1Hz,1H),7.17(s,1H),6.99–6.97(m,1H);13C NMR(151MHz,CDCl3)δ 149.81,143.22,143.18,128.78,127.54,127.23,124.74,123.41,119.60.E型结构NMR:1H NMR(400MHz,CDCl3)δ8.40(dd,J=4.6,1.5Hz,2H),7.30(dd,J=5.0,0.9Hz,1H),7.02 (dd,J=3.6,1.0Hz,1H),7.00(s,1H),6.93(d,J=6.1Hz,2H),6.88(dd,J=5.1,3.7Hz,1H); 13C NMR(151MHz,CDCl3)δ150.02,143.53,139.85,131.43,129.68,128.48,127.15,122.89,119.39.
实施例5
向10mL光反应器皿(青霉素小瓶)中,加入16.4mg(0.2mmol)3,3-二甲基-1-丁炔,15.7mg(0.1mmol)4-溴吡啶化合物,2.8mg(20mol%)催化剂和1mL二甲基亚砜,氮气保 护,用胶塞和封口膜密封后,在室温条件下,置于36W蓝色LEDs灯下光照反应28h。 用TLC监测反应进度。
后处理:反应结束后,反应溶剂经旋转蒸发仪浓缩旋干后,再以体积比20:1的石油醚:乙酸乙酯的混合溶液作为洗脱剂,进行硅胶柱层析纯化分离,得到相应的双取代4- (2-溴-3,3-二甲基-1-丁烯基)吡啶类衍生物,其反应式为:
产物为无色粘稠状液体,纯度为99%,产率为55%,Z/E=13/7。其中Z型结构式为:E型结构式为:核磁数据分析为:Z型结构1H NMR(400MHz,CDCl3) δ8.46(dd,J=4.5,1.5Hz,2H),7.05–6.98(m,2H),6.96(s,1H),1.06(s,9H);13C NMR(151MHz,CDCl3)δ149.35,146.87,142.79,128.73,123.43,41.31,31.22.E型结构NMR:1H NMR(400MHz,CDCl3)δ8.50(dd,J=4.6,1.5Hz,2H),7.31(d,J=6.0Hz,2H),6.66(s,1H),1.24(s,9H);13C NMR(151MHz,CDCl3)δ149.58,144.88,144.22,123.74,122.54,40.58,29.54.
实施例6
向10mL光反应器皿(青霉素小瓶)中,加入26.4mg(0.2mmol)苯基炔丙基醚,15.7mg(0.1mmol)4-溴吡啶化合物,2.8mg(20mol%)催化剂和1mL二甲基亚砜,氮气保护, 用胶塞和封口膜密封后,在室温条件下,置于36W蓝色LEDs灯下光照反应30h。用TLC 监测反应进度。
后处理:反应结束后,反应溶剂经旋转蒸发仪浓缩旋干后,再以体积比20:1的石油醚:乙酸乙酯的混合溶液作为洗脱剂,进行硅胶柱层析纯化分离,得到相应的双取代4- (2-溴-3-苯氧基-1-丙烯基)吡啶类衍生物,其反应式为:
产物为无色粘稠状液体,纯度为99%,产率为58%,其中Z型结构式为: E型结构式为:E型结构所占百分比太低所以不能提供其核磁数据。核磁 数据分析为:Z型结构1H NMR(400MHz,CDCl3)δ8.54(dd,J=4.6,1.6Hz,1H),7.51– 7.37(m,1H),7.31–7.21(m,1H),7.06(s,1H),6.95(t,J=7.4Hz,1H),6.93–6.87(m,1H), 4.76(d,J=1.5Hz,1H);13C NMR(151MHz,CDCl3)δ157.60,149.52,142.89,129.69,125.78,124.67,123.38,121.88,114.93,72.82.
实施例7
向10mL光反应器皿(青霉素小瓶)中,加入29.2mg(0.2mmol)苯丙炔酸,15.7mg(0.1mmol)4-溴吡啶化合物,2.8mg(20mol%)催化剂和1mL二甲基亚砜,氮气保护,用 胶塞和封口膜密封后,在室温条件下,置于36W蓝色LEDs灯下光照反应28h。用TLC 监测反应进度。
后处理:反应结束后,反应溶剂经旋转蒸发仪浓缩旋干后,再以体积比20:1的石油醚:乙酸乙酯的混合溶液作为洗脱剂,进行硅胶柱层析纯化分离,得到相应的双取代4- (2-溴-2-苯基乙烯基)吡啶衍生物,其反应式为:
产物为无色粘稠状液体,纯度为99%,产率为69%,Z/E=2/3。其中Z型结构式为:E型结构式为:核磁数据分析为:Z型结构NMR:1H NMR(500 MHz,CDCl3)δ8.64(d,J=5.1Hz,2H),7.65(d,J=7.4Hz,2H),7.57(d,J=5.1Hz,2H),7.39 (t,J=7.2Hz,3H),7.13(s,1H);13C NMR(101MHz,CDCl3)δ149.83,143.72,140.20,129.42,128.45,128.25,127.77,127.31,123.39.E型结构NMR:1H NMR(400MHz,CDCl3)δ8.30(d, J=5.1Hz,2H),7.33–7.23(m,5H),7.02(s,1H),6.74(d,J=5.2Hz,2H);13C NMR(151 MHz,CDCl3)δ149.87,143.26,138.64,130.60,129.52,128.89,128.81,128.38,122.84.
实施例8
向10mL光反应器皿(青霉素小瓶)中,加入32.0mg(0.2mmol)3-(对甲基苯基) -2-炔-1-丙酸,15.7mg(0.1mmol)4-溴吡啶化合物,2.8mg(20mol%)催化剂和1mL二甲基 亚砜,氮气保护,用胶塞和封口膜密封后,在室温条件下,置于36W蓝色LEDs灯下光 照反应28h。用TLC监测反应进度。
后处理:反应结束后,反应溶剂经旋转蒸发仪浓缩旋干后,再以体积比20:1的石油醚:乙酸乙酯的混合溶液作为洗脱剂,进行硅胶柱层析纯化分离,得到相应的双取代4- (2-溴-2-(对甲基苯基)乙烯基)吡啶衍生物,其反应式为:
产物为无色粘稠状液体,纯度为99%,产率为75%,Z/E=1/3。其中Z型结构式为:E型结构式为:核磁数据分析为:Z型结构1H NMR(400MHz, CDCl3)δ8.56(d,J=5.7Hz,2H),7.55–7.43(m,4H),7.13(d,J=8.1Hz,2H),7.03(s,1H), 2.32(s,3H);13C NMR(151MHz,CDCl3)δ149.84,143.85,139.70,137.43,129.14,128.43, 127.70,126.49,123.43,21.18.E型结构NMR:1H NMR(400MHz,CDCl3)δ8.30(d,J=5.9 Hz,2H),7.14(d,J=8.1Hz,2H),7.06(d,J=8.0Hz,2H),6.97(s,1H),6.75(d,J=6.0Hz, 2H),2.29(s,3H);13C NMR(151MHz,CDCl3)δ149.80,143.36,139.68,135.68,130.15, 129.50,128.77,128.68,122.77,21.34.
实施例9
向10mL光反应器皿(青霉素小瓶)中,加入28.4mg(0.2mmol)3-(三甲基硅基)丙炔酸,15.7mg(0.1mmol)4-溴吡啶化合物,2.8mg(20mol%)催化剂和1mL二甲基亚砜,氮 气保护,用胶塞和封口膜密封后,在室温条件下,置于36W蓝色LEDs灯下光照反应28 h。用TLC监测反应进度。
后处理:反应结束后,反应溶剂经旋转蒸发仪浓缩旋干后,再以体积比20:1的石油醚:乙酸乙酯的混合溶液作为洗脱剂,进行硅胶柱层析纯化分离,得到相应的双取代4- (2-溴-2-(三甲基硅基)乙烯基)吡啶衍生物,其反应式为:
产物为无色粘稠状液体,纯度为99%,产率为18%,Z/E=1/4。其中Z型结构式为:E型结构式为:核磁数据分析为:Z型和E型混合结构1H NMR(400MHz,CDCl3)δ8.55(dd,J=4.6,1.4Hz,1.2H),8.50(dd,J=4.5,1.5Hz,0.8H),7.74(s,0.4H),7.45(dd,J=4.7,1.3Hz,1.2H),7.09(s,0.6H),7.05–6.99(m,0.8H),0.22(s,5.4H),0.02(s,3.6H);13C NMR(151MHz,CDCl3)δ149.84,149.63,145.67,143.95,143.75,135.87,135.82,135.79,123.27,123.04,0.03,-2.01.
实施例10
向10mL光反应器皿(青霉素小瓶)中,加入20.4mg(0.2mmol)苯乙炔,18.0mg(0.1mmol)4-氰基溴苯化合物,2.8mg(20mol%)催化剂和1mL二甲基亚砜,氮气保护, 用胶塞和封口膜密封后,在室温条件下,置于36W蓝色LEDs灯下光照反应28h。用TLC 监测反应进度。
后处理:反应结束后,反应溶剂经旋转蒸发仪浓缩旋干后,再以体积比20:1的石油醚:乙酸乙酯的混合溶液作为洗脱剂,进行硅胶柱层析纯化分离,得到相应的双取代4- (2-溴-2-苯基乙烯基)苯甲腈衍生物,其反应式为:
产物为无色粘稠状液体,纯度为99%,产率为38%,只有Z型结构。核磁数据分析为:1H NMR(400MHz,CDCl3)δ7.72(d,J=8.1Hz,2H),7.64–7.53(m,4H),7.32(d,J=6.9 Hz,3H),7.13(s,1H);13C NMR(101MHz,CDCl3)δ140.80,140.26,131.95,129.73,129.41,128.49,128.08,127.79,127.50,118.76,111.29.
由上述实施例可知,本发明利用溴化亚铜做催化剂、在可见光蓝光诱导下使炔类化合 物与溴代芳香类化合物发生ATRA过程生成芳香乙烯基溴衍生物,解决了现有芳香乙烯 基溴衍生物合成需要有毒有害物质激发和过渡金属催化体系导致的产率低、方法环保性 差、底物兼容性差的问题,寻求到一条绿色高效、条件温和、方法简单且操作方便的合成芳香乙烯基溴衍生物的路线,也为现代工业化的发展奠定了一定的基础。
以上所述的实施例只是本发明的一种较佳的方案,并非对本发明作任何形式上的限 制,在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。
Claims (4)
1.一种芳香乙烯基溴衍生物的制备方法,其特征在于该方法包括如下步骤:
室温下,在氮气气氛下,将炔烃衍生物、溴代芳香环类化合物和催化剂溶解在有机溶剂中,混合均匀后置于蓝色LEDs灯光下进行光照反应,反应的时间为24-36h,待反应结束后,旋蒸溶剂,再经过硅胶柱柱层析分离提纯,即得到芳香乙烯基溴衍生物;其中炔烃衍生物、溴代芳香环类化合物和催化剂的投料摩尔比为2:1:0.2;其中溴代芳香环类化合物和有机溶剂的摩尔体积比为1mmol:10mL;炔烃衍生物为苯乙炔、4-叔丁基苯乙炔、4-三氟甲基苯乙炔、2-乙炔基噻吩、3,3-二甲基-1-丁炔、苯基炔丙基醚、苯丙炔酸、3-(对甲基苯基)-2-炔-1-丙酸或3-(三甲基硅基)丙炔酸;溴代芳香环类化合物为4-溴吡啶或4-氰基溴苯,有机溶剂为二甲基亚砜,催化剂为CuBr;
2.根据权利要求1所述的一种芳香乙烯基溴衍生物的制备方法,其特征在于通过TLC监测光照反应进程。
3.根据权利要求1所述的一种芳香乙烯基溴衍生物的制备方法,其特征在于硅胶柱层析分离纯化所用溶剂为石油醚与乙酸乙酯的混合溶剂。
4.根据权利要求3所述的一种芳香乙烯基溴衍生物的制备方法,其特征在于石油醚与乙酸乙酯的体积比为(10-20):1。
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