CN111777540B - 一种连续光诱导催化合成吡咯酮类化合物的方法 - Google Patents
一种连续光诱导催化合成吡咯酮类化合物的方法 Download PDFInfo
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- CN111777540B CN111777540B CN202010716089.7A CN202010716089A CN111777540B CN 111777540 B CN111777540 B CN 111777540B CN 202010716089 A CN202010716089 A CN 202010716089A CN 111777540 B CN111777540 B CN 111777540B
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Images
Classifications
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- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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Abstract
本发明公开了一种连续光诱导催化合成吡咯酮类化合物的方法,将有机催化剂、烯烃类有机化合物、溴代乙酸酯类化合物和胺类化合物溶于溶剂中,得到均相溶液;将所述的均相溶液泵入设有光源的微通道反应装置中进行反应,即得含有吡咯酮类化合物的反应液。与现有技术相比,本发明通过有机光催化代替催化剂,绿色高效,无金属残留,在合成医药产物方面有广泛的应用前景。
Description
技术领域
本发明涉及于医药化学与精细化学合成领域,具体涉及一种连续光诱导催化合成吡咯酮类化合物的方法
背景技术
吡咯酮类化合物具有与吲哚、氮杂吲哚等类似的特殊结构和良好的生物活性,在医药和农药工业有着广泛的应用(例如治疗癌症、治疗乙型病毒性肝炎、治疗心脏病等)。
目前一般采用金属催化剂(Pd、Fe、Cu、Ni、Co、Au)催化环合合成吡咯酮类化合物,但是往往存在反应温度高,反应时间较长,产率较低的问题,并且金属残留限制着其在医药等领域的应用。
近些年来,烯烃的双官能团化反应得到了飞速的发展,该反应不仅可以通过经济的方法仅用一步就合成多个位点反应产物,而且为构建多种多样的化学结提供了更丰富的可能性,采用烯烃进行双官能化后,对环合过程形成势能更低的化合物具有显著优势,经过这种反应可以结构多样的药物活性分子或功能性化合物,然而由于烯烃的管能化过程往往通过自由基引发,但是在引发过程中极易造成引发烯烃的聚合副反应,在间歇反应模式中,往往通过优化参数难以达到较好效果,需要找到尽可能高的转化率、高产率和低量副产物的平衡点,会存在过程稳定性差的问题,产品产率低,后处理繁琐等问题。
此外,采用光引发自由基过程,是一种目前认为较为绿色的化工过程,但光源产生的热点不均衡,光源功率提高会引起副反应和能耗利用低的问题,光源效率低又会引发反应转化效率低的难题,这也是为什么光化学反应在自由基反应中工程应用成功率低的原因。根据动力学和热力学的分析,采用微反应过程,光源离所有传递过程的物料等距离,短距离,能够解决上述转化效率低、均一性差、热点差异、能量转化低、副反应难以控制的问题。
发明内容
发明目的:本发明所要解决的技术问题是针对现有技术的不足,提供一种连续光诱导催化合成吡咯酮类化合物的方法,以解决现有技术存在的反应效率低和金属残留大的问题。
为了解决上述技术问题,本发明公开了一种连续光诱导催化合成吡咯酮类化合物的方法,其反应式如下:
其中,R1为CH3,H,F,Cl,Br,NO2和OCH3中的任意一种或几种组合;
R2,R3分别独立地为CH3,H,F,Cl,Br,Aryl,OCH3和CO2R中的任意一种或几种组合;其中,所述的R为任意烷基。
R4为Aryl或Alkyl;
PC为有机光催化剂。
具体的反应过程为:将有机催化剂、烯烃类有机化合物、溴代乙酸酯类化合物和胺类化合物溶于溶剂中,得到均相溶液;将所述的均相溶液泵入设有光源的微通道反应装置中,在光照充分反应,收集产物,即得含有吡咯酮类化合物的反应液,提纯,即得目标产物吡咯酮类化合物。
其中,所述的有机催化剂选自5,10-二(4-(三氟甲基)苯基)-5,10-二氢吩嗪、5,10-二(4-(甲氧基)苯基)-5,10-二氢吩嗪、5,10-二苯基-5,10-二氢吩嗪、5,10-二(2-萘基)-5,10-二氢吩嗪、5,10-二(1-萘基)-5,10-二氢吩嗪、10-苯基吩噻嗪、10-(4-甲氧基苯基)吩噻嗪、10-(1-萘基)吩噻嗪、二萘嵌苯、3,7-二(4-(1,1'-联苯))-(10-(1-萘基))-10-吩恶嗪或5,10-二(4-(腈基)苯基)-5,10-二氢吩嗪;优选地,所述的有机催化剂为5,10-二(4-(三氟甲基)苯基)-5,10-二氢吩嗪。
其中,所述的烯烃类有机化合物选自苯乙烯、2-氟苯乙烯、3-氟苯乙烯、4-氟苯乙烯、2-氯苯乙烯、3-氯苯乙烯、4-氯苯乙烯、2-溴苯乙烯、3-溴苯乙烯、4-溴苯乙烯、2-甲氧基苯乙烯、3-甲氧基苯乙烯、4-甲氧基苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、2-硝基苯乙烯、3-硝基苯乙烯、4-硝基苯乙烯或a-溴苯乙烯;优选地,所述的烯烃类有机化合物为苯乙烯。
其中,所述的溴代乙酸酯类化合物选自2-溴-2-甲基丙二酸二乙酯、2-溴-2-甲基丙酸乙酯、2-溴丙酸甲酯、2-溴丙酸乙酯、α-溴苯乙酸乙酯、溴苯乙酸乙酯或二氟溴乙酸乙酯;优选地,所述的溴代乙酸酯类化合物为2-溴-2-甲基丙酸乙酯。
其中,所述的胺类化合物选自苯胺、邻甲苯胺、间甲苯胺、对甲苯胺、2-氟苯胺、3-氟苯胺、4-氟苯胺、2-硝基苯胺、3-硝基苯胺、4-硝基苯胺、2-氯苯胺、3-氯苯胺、4-氯苯胺、2,6-二甲基苯胺、2,4,6-三溴苯胺、2-溴苯胺、3-溴苯胺、4-溴苯胺、2-甲氧基苯胺、3-甲氧基苯胺、4-甲氧基苯胺、2-三氟甲基苯胺、3-三氟甲基苯胺、4-三氟甲基苯胺、苄胺、a-甲基苄胺、2-氯-5-氨基三氟甲苯、邻苄基苯胺、4-氟-α-甲基苄胺、2-溴-5-甲基苯胺或4-溴-a-甲基苯乙胺;优选地,所述的胺类化合物为苯胺。
其中,所述的溶剂选自二氯乙烷(1,2-二氯乙烷)、二甲基亚砜、乙二醇二甲醚、乙腈、苯、N,N-二甲基甲酰胺或N,N-二甲基苯胺;优选地,所述的溶剂为二氯乙烷。
进一步优选地,上述反应的反应式如下:
其中,所述的均相溶液中有机催化剂与烯烃类有机化合物、溴代乙酸酯类化合物和胺类化合物的摩尔比为0.005~0.025:1:2:1。
其中,所述的均相溶液中烯烃类有机化合物的浓度为0.01~1mmol/mL。
其中,所述微反应装置包括进样器、微通道反应器、接收器、光源;所述进样器、微通道反应器和接收器串联连接;所述光源位于微通道反应器外侧,其光照范围覆盖微通道反应器;所述连接为通过管道连接。
优选地,所述微通道反应器使用石英盘管,保留体积为1~2mL,管径为0.2~2mm。
优选地,所述的均相溶液在微反应装置中的流速为0.05~0.2mL/min,优选为0.1mL/min。
进一步优选地,所述的进样器与微通道反应器之间的连接管长度为10~50cm,微通道反应器与接收器之间的连接管长度为10~50cm。
其中,所述的光源为模拟太阳光灯(300W,230V),波长为250~780nm。
其中,所述的反应中,反应温度为室温,反应停留时间为5~40min。
有益效果:与现有技术相比,本发明具有如下优势:
(1)本发明通过有机光催化代替催化剂,绿色高效,无金属残留,反应时间短、不需要加热、产率高;其在生物医用材料领域应用更有竞争力。
(2)本专利采用有机催化剂催化烯烃双官能化反应合成吡咯酮类化合物,并且与微流场技术相结合,建立微尺度下高效合成的新方法,本发明大幅度提升物料混合、传质和传热的效率,加快了反应速度;同时反应温度分布更加均匀,光照更加均匀,连续流过程控制更加精确,能够有效避免副产物的产生。
(3)本发明反应条件温和、反应速度快、转化率高、副反应少、有利于连续化生产。
附图说明
下面结合附图和具体实施方式对本发明做更进一步的具体说明,本发明的上述和/或其他方面的优点将会变得更加清楚。
图1为本发明的反应装置图。
图2为实施例1、2、3产物的氢谱和碳谱图。
图3为实施例4产物的氢谱和碳谱图。
图4为实施例5产物的氢谱和碳谱图。
图5为实施例6产物的氢谱、碳谱图和质谱图。
图6为实施例7产物的氢谱和碳谱图。
图7为实施例8产物的氢谱和碳谱图。
具体实施方式
以下实施例中,所述的微通道反应器的反应装置如图1所示,该装置包括进样器、微通道反应器、接收器、光源;所述进样器、微通道反应器和接收器串联连接;所述光源位于微通道反应器外侧,其光照范围覆盖微通道反应器;所述连接为通过管道连接;其中,所述的光源为模拟太阳光灯(300W,230V),波长为250~780nm;其中,所述微通道反应器使用石英盘管,保留体积为1mL。
实施例1:
室温下,将5,10-二(4-(三氟甲基)苯基)-5,10-二氢吩嗪(23.5mg,50μmol,5%当量)、2-溴-2-甲基丙酸乙酯(294.0μL,2mmol,2当量)、苯胺(91.1μL,1mmol,1当量)和苯乙烯(116.8μL,1mmol,1当量)溶解于溶剂DCE(4mL)中,并加入搅拌子搅拌,在模拟太阳光下照射4h。用石油醚与乙酸乙酯10:1(体积比)的洗脱剂分离,将所得产物真空干燥4h。转化率86%。
1H NMR(400MHz,Chloroform-d)δ7.42–7.25(m,7H),7.24–7.01(m,3H),5.42(dd,J=10.2,6.0Hz,1H),2.43(dd,J=12.7,6.0Hz,1H),2.04(s,1H),1.44(d,J=13.4Hz,6H).13CNMR(101MHz,Chloroform-d)δ139.20,127.70,127.59,127.53,127.32,127.08,124.39,124.29,122.52,121.71,121.67,121.43,79.14,45.06,40.83,39.74,25.30,25.18.HRMS计算值C18H19NO[M+H+]:266.1539;实测值:266.1508。
实施例2:
室温下,将5,10-二(4-(三氟甲基)苯基)-5,10-二氢吩嗪(23.5mg,50μmol,5%当量)、2-溴-2-甲基丙酸乙酯(294.0μL,2mmol,2当量)、苯胺(91.1μL,1mmol,1当量)和苯乙烯(116.8μL,1mmol,1当量)溶解于溶剂DCE(4mL)中,得到均相溶液,将上述均相溶液泵入微通道反应器中,控制泵流速均为0.1mL/min,在模拟太阳光照射的微通道反应器中,保留时间为10min;用接样烧瓶收集流出液体。用石油醚与乙酸乙酯10:1(体积比)的洗脱剂分离,将所得产物真空干燥4h。转化率97%。
1H NMR(400MHz,Chloroform-d)δ7.42–7.25(m,7H),7.24–7.01(m,3H),5.42(dd,J=10.2,6.0Hz,1H),2.43(dd,J=12.7,6.0Hz,1H),2.04(s,1H),1.44(d,J=13.4Hz,6H).13CNMR(101MHz,Chloroform-d)δ139.20,127.70,127.59,127.53,127.32,127.08,124.39,124.29,122.52,121.71,121.67,121.43,79.14,45.06,40.83,39.74,25.30,25.18.HRMS计算值C18H19NO[M+H+]:266.1539;实测值:266.1508。
实施例3:
室温下,将5,10-二(4-(三氟甲基)苯基)-5,10-二氢吩嗪(23.5mg,50μmol,5%当量)溶解于溶剂DCE(2mL)中,得到第一均相溶液;将2-溴-2-甲基丙酸乙酯(294.0μL,2mmol,2当量)、苯胺(91.1μL,1mmol,1当量)和苯乙烯(116.8μL,1mmol,1当量)溶解于溶剂DCE(2mL)中,得到第二均相溶液;再将上述第一第二均相溶液泵入微通道反应器中,控制泵流速均为0.05mL/min,在模拟太阳光照射的微通道反应器中,保留时间为10min;用接样烧瓶收集流出液体。用石油醚与乙酸乙酯10:1(体积比)的洗脱剂分离,将所得产物真空干燥4h。转化率96%。核磁见图2。
1H NMR(400MHz,Chloroform-d)δ7.42–7.25(m,7H),7.24–7.01(m,3H),5.42(dd,J=10.2,6.0Hz,1H),2.43(dd,J=12.7,6.0Hz,1H),2.04(s,1H),1.44(d,J=13.4Hz,6H).13CNMR(101MHz,Chloroform-d)δ139.20,127.70,127.59,127.53,127.32,127.08,124.39,124.29,122.52,121.71,121.67,121.43,79.14,45.06,40.83,39.74,25.30,25.18.HRMS计算值C18H19NO[M+H+]:266.1539;实测值:266.1508。
实施例4:
室温下,将5,10-二(4-(三氟甲基)苯基)-5,10-二氢吩嗪(23.5mg,50μmol,5%当量)、2-溴-2-甲基丙酸乙酯(294.0μL,2mmol,2当量)、4-氯苯胺(89.2μL,1mmol,1当量)和苯乙烯(116.8μL,1mmol,1当量)溶解于溶剂DCE(4mL)中,得到均相溶液,将上述均相溶液泵入微通道反应器中,控制泵流速均为0.1mL/min,在模拟太阳光照射的微通道反应器中,保留时间为10min;用接样烧瓶收集流出液体。用石油醚与乙酸乙酯10:1(体积比)的洗脱剂分离,将所得产物真空干燥4h。转化率93%。核磁见图3。
1H NMR(400MHz,Chloroform-d)δ7.45–7.21(m,7H),7.08(d,J=8.2Hz,2H),5.41(dd,J=10.3,5.9Hz,1H),2.42(dd,J=12.7,5.9Hz,1H),2.12–1.95(m,1H),1.42(d,J=13.3Hz,6H).13C NMR(101MHz,Chloroform-d)δ168.80,145.74,140.01,128.89,128.76,128.71,128.64,128.59,128.25,127.49,125.43,124.28,80.32,47.10,41.96,26.31,26.17,24.35.HRMS计算值C18H18NOCl[M+H+]:300.115;实测值:300.1129。
实施例5:
室温下,将5,10-二(4-(三氟甲基)苯基)-5,10-二氢吩嗪(23.5mg,50μmol,5%当量)、2-溴-2-甲基丙酸乙酯(294.0μL,2mmol,2当量)、4-甲基苯胺(107.15mg,1mmol,1当量)和苯乙烯(116.8μL,1mmol,1当量)溶解于溶剂DCE(4mL)中,得到均相溶液,将上述均相溶液泵入微通道反应器中,控制泵流速均为0.1mL/min,在模拟太阳光照射的微通道反应器中,保留时间为10min;用接样烧瓶收集流出液体。用石油醚与乙酸乙酯10:1(体积比)的洗脱剂分离,将所得产物真空干燥4h。转化率91%。核磁见图4。
1H NMR(400MHz,Chloroform-d)δ7.38–7.27(m,5H),7.15–6.97(m,4H),5.39(dd,J=10.1,6.0Hz,1H),2.41(dd,J=12.7,6.0Hz,1H),2.29(s,3H),2.01(dd,J=12.6,10.1Hz,1H),1.42(d,J=12.1Hz,6H).13C NMR(101MHz,Chloroform-d)δ167.92,140.39,132.86,129.13,128.58,128.03,125.41,125.31,122.67,79.95,47.31,41.75,29.70,26.37,26.22,20.91.13C NMR(101MHz,Chloroform-d)δ167.92,144.33,140.39,132.86,129.13,128.72,128.58,128.03,127.25,125.41,125.31,122.67,79.95,77.23,47.31,41.75,29.70,26.37,26.22.HRMS计算值C19H21NO[M+H+]:280.1696;实测值:280.1689。
实施例6:
室温下,将5,10-二(4-(三氟甲基)苯基)-5,10-二氢吩嗪(23.5mg,50μmol,5%当量)、2-溴-2-甲基丙酸乙酯(294.0μL,2mmol,2当量)、4-三氟甲基苯胺(125.6μL,1mmol,1当量)和苯乙烯(116.8μL,1mmol,1当量)溶解于溶剂DCE(4mL)中,得到均相溶液,将上述均相溶液泵入微通道反应器中,控制泵流速均为0.1mL/min,在模拟太阳光照射的微通道反应器中,保留时间为10min;用接样烧瓶收集流出液体。用石油醚与乙酸乙酯10:1(体积比)的洗脱剂分离,将所得产物真空干燥4h。转化率90%。核磁见图5。
1H NMR(400MHz,Chloroform-d)δ7.53–7.24(m,7H),7.23–6.83(m,2H),5.48–5.38(m,1H),2.51–2.41(m,1H),2.11–2.02(m,1H),1.46–1.31(m,6H).13C NMR(101MHz,Chloroform-d)δ149.36,139.45,128.77,128.73,127.21,126.45,125.97,125.81,125.77,125.42,125.33,122.73,77.64,60.99,54.86,47.04,41.37,24.95,23.18.19F NMR(376MHZ,Chloroform-d)δ-60.88,-61.18,-61.80.HRMS计算值C19H18F3NO[M+H+]:334.1413;实测值:334.1393。
实施例7:
室温下,将5,10-二(4-(三氟甲基)苯基)-5,10-二氢吩嗪(23.5mg,50μmol,5%当量)、2-溴-2-甲基丙酸乙酯(294.0μL,2mmol,2当量)、2-甲基苯胺(107.15mg,1mmol,1当量)和苯乙烯(116.8μL,1mmol,1当量)溶解于溶剂DCE(4mL)中,得到均相溶液,将上述均相溶液泵入微通道反应器中,控制泵流速均为0.1mL/min,在模拟太阳光照射的微通道反应器中,保留时间为10min;用接样烧瓶收集流出液体。用石油醚与乙酸乙酯10:1(体积比)的洗脱剂分离,将所得产物真空干燥4h。转化率92%。核磁见图6。
1H NMR(400MHz,Chloroform-d)δ7.38–7.27(m,5H),7.15–6.97(m,4H),5.39(dd,J=10.1,6.0Hz,1H),2.41(dd,J=12.7,6.0Hz,1H),2.29(s,3H),2.01(dd,J=12.6,10.1Hz,1H),1.42(d,J=12.1Hz,6H).13C NMR(101MHz,Chloroform-d)δ167.92,140.39,132.86,129.13,128.58,128.03,125.41,125.31,122.67,79.95,47.31,41.75,29.70,26.37,26.22,20.91.13C NMR(101MHz,Chloroform-d)δ167.92,144.33,140.39,132.86,129.13,128.72,128.58,128.03,127.25,125.41,125.31,122.67,79.95,77.23,47.31,41.75,29.70,26.37,26.22.HRMS计算值C19H21NO[M+H+]:280.1693;实测值:280.1663。
实施例8:
室温下,将5,10-二(4-(三氟甲基)苯基)-5,10-二氢吩嗪(23.5mg,50μmol,5%当量)、2-溴-2-甲基丙二酸二乙酯(382.1μL,2mmol,2当量)、苯胺(91.1μL,1mmol,1当量)和苯乙烯(116.8μL,1mmol,1当量)溶解于溶剂DCE(4mL)中,得到均相溶液,将上述均相溶液泵入微通道反应器中,控制泵流速均为0.1mL/min,在模拟太阳光照射的微通道反应器中,保留时间为10min;用接样烧瓶收集流出液体。用石油醚与乙酸乙酯10:1(体积比)的洗脱剂分离,将所得产物真空干燥4h。转化率97%。核磁见图7。
1H NMR(400MHz,Chloroform-d)δ7.41–7.26(m,7H),7.15(d,J=7.8Hz,2H),7.05(t,J=7.3Hz,1H),5.57(dd,J=10.3,5.9Hz,1H),4.35–4.26(m,2H),3.01(dd,J=13.2,6.0Hz,1H),2.05(dd,J=13.2,10.3Hz,1H),1.67(s,3H),1.35(t,J=7.1Hz,3H).13C NMR(101MHz,Chloroform-d)δ172.36,162.07,146.65,139.60,128.72,128.57,128.38,125.51,123.87,122.73,81.27,78.98,77.25,61.96,52.73,44.83,22.23,14.23.HRMS计算值C20H21NO3[M+H+]:324.1594;实测值:324.1599。
本发明提供了一种连续光诱导催化合成吡咯酮类化合物的方法的思路及方法,具体实现该技术方案的方法和途径很多,以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。
Claims (6)
1.一种连续光诱导催化合成吡咯酮类化合物的方法,其特征在于,将有机催化剂、烯烃类有机化合物、溴代乙酸酯类化合物和胺类化合物溶于溶剂中,得到均相溶液;将所述的均相溶液泵入设有光源的微通道反应装置中进行反应,即得含有吡咯酮类化合物的反应液;
其中,所述有机催化剂为5,10-二(4-(三氟甲基)苯基)-5,10-二氢吩嗪;
其中,所述烯烃类有机化合物为苯乙烯;
其中,所述溴代乙酸酯类化合物为2-溴-2-甲基丙二酸二乙酯和2-溴-2-甲基丙酸乙酯中的任意一种或两种组合;
其中,所述胺类化合物为苯胺、4-氯苯胺、4-甲基苯胺、4-三氟甲基苯胺和2-甲基苯胺中的任意一种或几种组合。
2.根据权利要求1所述的方法,其特征在于,所述的溶剂选自二氯乙烷、二甲基亚砜、乙二醇二甲醚、乙腈、苯、N,N-二甲基甲酰胺或N,N-二甲基苯胺。
3.根据权利要求1所述的方法,其特征在于,所述的均相溶液中有机催化剂与烯烃类有机化合物、溴代乙酸酯类化合物和胺类化合物的摩尔比为0.005~0.025:1:2:1。
4.根据权利要求1所述的方法,其特征在于,所述的均相溶液中烯烃类有机化合物的浓度为0.01~1 mmol/mL。
5.根据权利要求1所述的方法,其特征在于,所述的光源为模拟太阳光灯,300 W,230V,波长为250~780 nm。
6.根据权利要求1所述的方法,其特征在于,所述的反应中,反应温度为室温,反应停留时间为5~40 min。
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