CN112138718B - 一种共价有机框架材料光催化c-c键偶联合成联芳香类化合物的方法 - Google Patents
一种共价有机框架材料光催化c-c键偶联合成联芳香类化合物的方法 Download PDFInfo
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- CN112138718B CN112138718B CN201910562747.9A CN201910562747A CN112138718B CN 112138718 B CN112138718 B CN 112138718B CN 201910562747 A CN201910562747 A CN 201910562747A CN 112138718 B CN112138718 B CN 112138718B
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
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- 238000005859 coupling reaction Methods 0.000 title description 9
- 239000000463 material Substances 0.000 title description 6
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- 238000007146 photocatalysis Methods 0.000 title description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 37
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- 239000000852 hydrogen donor Substances 0.000 claims abstract description 9
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- 125000003118 aryl group Chemical group 0.000 claims description 13
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- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 8
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- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 6
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
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- 235000011009 potassium phosphates Nutrition 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052736 halogen Inorganic materials 0.000 claims description 3
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- DGRVQOKCSKDWIH-UHFFFAOYSA-N 1-chloro-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1Cl DGRVQOKCSKDWIH-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
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- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
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- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
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- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- CPWJKGIJFGMVPL-UHFFFAOYSA-K tricesium;phosphate Chemical compound [Cs+].[Cs+].[Cs+].[O-]P([O-])([O-])=O CPWJKGIJFGMVPL-UHFFFAOYSA-K 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
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- 239000003426 co-catalyst Chemical class 0.000 claims 1
- ABTWCNHNRLMBFR-UHFFFAOYSA-N hydroxy-tris(trimethylsilyl)silane Chemical compound C[Si](C)(C)[Si](O)([Si](C)(C)C)[Si](C)(C)C ABTWCNHNRLMBFR-UHFFFAOYSA-N 0.000 claims 1
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Abstract
一种卤代芳香类化合物与芳香类化合物通过光化学催化脱卤化氢合成联芳香类化合物的方法，包括以下步骤：在光、光催化剂、助催化剂、氢供体和碱的存在下，卤代芳香类化合物和芳香类化合物反应得到联芳香类化合物。本申请的方法相对于现有技术中采用贵金属催化氢化卤代芳香类化合物脱卤反应条件更为绿色、温和。本发明的制备工艺简单，通过一步反应即可得到产物，经济环保，且操作方便。
Description
技术领域
本发明属于光化学有机合成技术领域，具体涉及一种共价有机框架材料光催化C-C键偶联合成联芳香类化合物的方法。
背景技术
C-C键偶联反应在最近逐渐引起科学界的重视。将卤代芳烃的脱卤和芳烃的C-H活化实现C-C键偶联反应可以合成很多工业上重要的联芳烃类药物以及农药分子。其意义在于可以利用自然界中大量存在的未官能化的芳烃类和卤代芳烃类化合物，然后脱去卤化氢合成C-C键偶联的联芳烃类化合物。
联芳香类化合物是有机合成中一类常见且重要的结构片段，它广泛存在于天然和人工合成药物中。联芳香类化合物是指在分子结构中包含联芳基(Ar-Ar)的有机化合物。
联芳香类化合物的经典合成方法主要依靠Pd催化的交叉偶联反应，包括Suzuki-Miyaura反应、Stille反应、Negishi反应等，但以上方法均需使用化学计量的金属有机试剂。并且这些反应存在条件不温和、不环保、成本高、催化剂与产物难分离、催化剂再生利用困难等问题。因全球性能源与环境问题，社会与科技的发展使得以绿色环保为首要目的的化工生产势在必行，再加上对于一些化工产品的迫切需求，这些都促使我们寻找一种更为简单、绿色、低廉并且高产率、高效率、高选择性的合成方法。
近年来，异相光催化的研究取得了长足的进展。作为一种新型的异相有机光催化材料，共价有机框架(COF)具有结晶性高，比表面积大，孔道结构规整，结构可调控性高，水、酸、碱稳定性高，易于分离，重复利用性好等优点。
在可见光照射下，一些COF光催化剂能够发生电荷分离，产生空穴和电子对，在导带和价带引发各自的表面氧化和还原反应，同时生成的二级自由基氧化物种如超氧阴离子自由基，单线态氧等。超氧阴离子自由基，单线态氧可以发生有机物的矿化反应生成CO2和H2O。但是因为COF材料中激发态载流子寿命短，而C-C键偶联反应往往需要毫秒级以上的反应时间，这使得利用导带电子实现具有合成价值的C-C键偶联反应变得很困难，因而较少用于诸如卤代芳烃与芳烃的C-C键偶联脱除卤化氢合成联芳烃类化合物。
发明内容
为改善上述问题，本发明提供一种卤代芳香类化合物与芳香类化合物通过光化学催化脱卤化氢合成联芳香类化合物的方法，包括以下步骤：
在光、光催化剂、助催化剂、氢供体和碱的存在下，卤代芳香类化合物和芳香类化合物反应得到联芳香类化合物。
根据本发明的实施方案，所述光催化剂为TpTta、TAPA-TFP COF、TpPa-1中的至少一种。
根据本发明的实施方案，所述TAPA-TFP COF的结构为：
根据本发明的实施方案，所述TpPa-1的结构为：
根据本发明的实施方案，所述光催化剂TpTta的制备方法参考文献ChemCommun.2017,53,11469-11471。
根据本发明的实施方案，所述TAPA-TFP COF的制备方法参考文献Chem.Commun.,2019,55,2680-2683。
根据本发明的实施方案，所述TpPa-1的制备方法参考文献J.Am.Chem.Soc.2012，134，19524-19527。
根据本发明的实施方案，所述光的光源为395nm LED、420nm LED、太阳光或模拟太阳光；所述LED光源功率可以为50-150瓦，例如100瓦；所述模拟太阳光的功率可以为200-400瓦，例如300瓦；
根据本发明的实施方案，所述芳香类化合物选自芳环类化合物或杂芳环类化合物，所述芳环类化合物或杂芳环类化合物可进一步被一个、两个或更多个Rs取代，所述Rs选自OH、氰基、COOH、COH、NH2、C1-12烷基、C1-12烷氧基、C3-12环烷基、C3-12环烷基氧基、-C(O)-C1-12烷基；
所述Rs可进一步被一个、两个或更多个如下基团取代：卤素、OH、氰基、COOH、NH2、C1-12烷基、C1-12烷氧基；
所述卤代芳香类化合物为上述芳香类化合物芳环或杂芳环上至少一个H被卤素取代形成的化合物。
根据本发明优选的实施方案，所述芳香类化合物选自无取代或任选被一个、两个或更多个如下基团取代的C6-12芳环或5-12元杂芳环类化合物：OH、氰基、COOH、COH、NH2、C1-6烷基、C1-6烷氧基、C3-6环烷基、C3-6环烷基氧基、-C(O)-C1-6烷基、卤代C1-6烷基；
根据本发明优选的实施方案，所述卤代芳香类化合物选自被溴或氯取代的芳香类化合物。
作为实例，所述芳香类化合物选自均三甲氧基苯、吡咯或呋喃。
作为实例，所述卤代芳香类化合物选自对溴苯乙酮、对溴苯甲腈、邻氯三氟甲苯、溴苯、对三氟甲基溴苯中的至少一种。
根据本发明的实施方案，所述助催化剂选自奎宁环、苯硫酚、二苯基二硫醚、三(三甲基硅)硅烷、三(三甲基硅)硅醇、四丁基十聚钨酸铵中的至少一种。
根据本发明的实施方案，所述氢供体选自醇类化合物和/或有机胺(如一级胺、二级胺和三级胺)，例如选自甲醇、乙醇、异丙醇、乙胺、丙胺、丁胺、异丙胺、二乙基甲胺、二甲基乙胺、二异丙基乙基胺、三乙胺、三丁胺中的至少一种。
根据本发明的实施方案，所述碱选自有机碱或无机碱，优选为无机碱，例如选自碳酸钾、碳酸铯、碳酸钠、磷酸钾、磷酸钠、磷酸铯、氢氧化钾、叔丁醇钾、氢氧化钠中的至少一种。
根据本发明的实施方案，所述反应任选地加入或不加入溶剂，当使用溶剂时，所述溶剂可以是惰性有机溶剂，其可选自在上述反应条件下呈惰性，特别是不与原料和产品发生化学反应的任何有机溶剂，包括例如选自下列的一种、两种或多种的混合物：酯类溶剂，例如乙酸乙酯或者乙酸丁酯；碳氢化合物类溶剂，例如苯、甲苯、二甲苯、己烷和环己烷；卤代烃类溶剂，例如二氯甲烷、三氯甲烷、1,2-二氯乙烷和氯苯；醇类溶剂，例如甲醇、乙醇、异丙醇、正丙醇、正丁醇；或者其它溶剂，例如N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、N-甲基吡咯烷酮(NMP)、乙腈或者吡啶；
根据本发明的实施方案，所述卤代芳香类化合物、芳香类化合物、助催化剂、氢供体、碱的摩尔比为1:(1-100):(1-200):(0.0005-0.005):(1-200)，优选为1:(1-50):(1-10):(0.001-0.005):(1-10)，例如1:20:8:0.005:2、1:50:0.001:10:3或1:40:8:0.005:2。
根据本发明的实施方案，所述光催化剂在反应体系中的浓度为0.1-50g/L，优选为1-8g/L，例如1g/L、2g/L、5g/L。
根据本发明的实施方案，所述反应在透明反应器中进行，例如密闭的透明反应器中进行；
根据本发明的实施方案，所述反应优选在惰性气氛中进行；所述惰性气氛可以为氮气、氦气、氩气等气氛；
根据本发明的实施方案，所述惰性气氛的压力为0.01-2MPa；
根据本发明的实施方案，所述反应的反应时间是10分钟-24小时，优选为8分钟-24小时，例如8-20小时，如8、10、12、18、20小时；
根据本发明的实施方案，反应温度为10-50℃，例如25℃。
根据本发明的实施方案，所述反应可以先加入光催化剂、卤代芳香类化合物、芳香类化合物、氢供体、碱、及任选地溶剂进行搅拌，然后再光照，或者一开始搅拌时光照，继续搅拌得到联芳香类化合物；
根据本发明的实施方案，若先搅拌再光照，则在光照前搅拌的时间为10分钟-1小时，优选20-50分钟。
术语解释和定义
术语“更多个”表示三个以上。
术语“芳环类化合物”表示具有6～20个碳原子的芳香性或部分芳香性的单环、双环或三环烃环，优选“C6-14芳环”。术语“C6-14芳环”应理解为优选表示具有6、7、8、9、10、11、12、13或14个碳原子的芳香性或部分芳香性的单环、双环或三环烃环，特别是具有6个碳原子的环，例如苯。所述芳环可以选自联苯，或者是具有9个碳原子的环，例如茚满或茚，或者是具有10个碳原子的环，例如四氢化萘、二氢萘或萘，或者是具有13个碳原子的环，例如芴，或者是具有14个碳原子的环，例如蒽。
术语“杂芳环类化合物”应理解为包括这样的单环、双环或三环芳族环系，其具有优选5～20个环原子且优选包含1-5个独立选自N、O和S的杂原子，例如“5-14元杂芳环”。术语“5-14元杂芳环”应理解为包括这样的单环、双环或三环芳族环系，其具有5、6、7、8、9、10、11、12、13或14个环原子，特别是5或6或9或10个碳原子，且其包含1-5个，优选1-3各独立选自N、O和S的杂原子，并且，另外在每一种情况下可为苯并稠合的。特别地，杂芳环选自噻吩、呋喃、吡咯、噁唑、噻唑、咪唑、吡唑、异噁唑、异噻唑、噁二唑、***、噻二唑、噻-4H-吡唑等以及它们的苯并衍生物，例如苯并呋喃、苯并噻吩、苯并噁唑、苯并异噁唑、苯并咪唑、苯并***、吲唑、吲哚、异吲哚等；或吡啶、哒嗪、嘧啶、吡嗪、三嗪等，以及它们的苯并衍生物，例如喹啉、喹唑啉、异喹啉等；或吖辛因、吲嗪、嘌呤等以及它们的苯并衍生物；或噌啉、酞嗪、喹唑啉、喹喔啉、萘啶、蝶啶、咔唑、吖啶、吩嗪、吩噻嗪、吩噁嗪等。
术语“C1-12烷基”应理解为优选表示具有1～12个碳原子的直链或支链饱和一价烃基，优选为C1-10烷基。“C1-10烷基”应理解为优选表示具有1、2、3、4、5、6、7、8、9或10个碳原子的直链或支链饱和一价烃基。所述烷基是例如甲基、乙基、丙基、丁基、戊基、己基、异丙基、异丁基、仲丁基、叔丁基、异戊基、2-甲基丁基、1-甲基丁基、1-乙基丙基、1,2-二甲基丙基、新戊基、1,1-二甲基丙基、4-甲基戊基、3-甲基戊基、2-甲基戊基、1-甲基戊基、2-乙基丁基、1-乙基丁基、3,3-二甲基丁基、2,2-二甲基丁基、1,1-二甲基丁基、2,3-二甲基丁基、1,3-二甲基丁基或1,2-二甲基丁基等或它们的异构体。特别地，所述基团具有1、2、3、4、5、6、个碳原子(“C1-6烷基”)，例如甲基、乙基、丙基、丁基、异丙基、异丁基、仲丁基、叔丁基，更特别地，所述基团具有1、2或3个碳原子(“C1-3烷基”)，例如甲基、乙基、正丙基或异丙基。
术语“C3-12环烷基”应理解为表示不饱和的一价单环或双环烃环，其具有3～12个碳原子，优选“C3-10环烷基”。术语“C3-10环烷基”应理解为表示饱和的一价单环或双环烃环，其具有3、4、5、6、7、8、9或10个碳原子。所述C3-10环烷基可以是单环烃基，如环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环壬基或环癸基，或者是双环烃基如十氢化萘环。
术语“C1-12烷氧基”为上述C1-12烷基与O相连构成的基团。
术语C1-12烷基、C3-12环烷基、C1-12烷氧基的定义适用于其他含C1-12烷基、C3-12环烷基、C1-12烷氧基的基团，例如C3-12环烷基氧基、-C(O)-C1-12烷基。
有益效果
本发明公开了一种共价有机框架光催化卤代芳香类和芳香类化合物选择性发生C-C键偶联反应合成联芳香类化合物的方法。本发明的反应体系，例如在惰性有机溶剂、光催化剂、助催化剂、氢供体、碱的作用下，可以使卤代芳香类化合物选择性脱卤合成联芳香类化合物，产物的分离产率为65％以上。
本申请的方法相对于现有技术中采用贵金属催化氢化卤代芳香类化合物脱卤反应条件更为绿色、温和。本发明的制备工艺简单，通过一步反应即可得到产物，经济环保，且操作方便。并且，本发明的催化体系中光催化剂生物毒性低，成本低，催化剂与产物易分离，易再生利用。
附图说明
图1为4-(1H-吡咯-2-基)苯甲腈的核磁氢谱(氘代试剂为氘代丙酮)。
图2为4-(1H-吡咯-2-基)苯甲腈的质谱图。
具体实施方式
以下通过示例性的具体实施例对本发明的技术方案进行详细说明。但不应将这些实施例解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明，所记载的原料及试剂均为市售产品，或者通过已知方法制备。
制备例1 TpTta的制备参考文献Chem Commun.2017,53,11469-11471
TpTta采用溶剂热方法进行合成。将2,4,6-三羟基-1,3,5-苯三甲醛(0.15mmol)，2,4,6-三(4-氨基苯基)-s-三嗪(0.15mmol)，3mL1,4-二氧六环，0.25mL 6M醋酸水溶液加入Schlenk管中。在77K(液氮浴)中快速冷冻后，进行三次冷冻-抽真空-解冻操作完全除去体系中的氧气，对Schlenk管进行火焰封管。Schlenk管在120℃加热3天。沉淀通过离心收集，收集的沉淀用DMF洗三次，DCM洗两次。洗好的粉末在真空烘箱中干燥12小时。
制备例2 TAPA-TFP COF的制备参考文献Chem Commun.55,2680-2683
将1mmol 2,4,6-三羟基-1,3,5-苯三甲醛和1mmol三(4-氨基苯基)胺加入到装有10ml THF:均三甲苯(体积比为3:1)混合溶剂的Schlenk管中。将Schlenk管在室温下超声10分钟，然后加入1ml 6M的醋酸水溶液。在77K(液氮浴)中快速冷冻后，进行三次冷冻-抽真空-解冻操作完全除去体系中的氧气，在N2气氛下对Schlenk管进行火焰封管。然后在120℃下油浴加热三天。反应液冷却后将不溶的产物进行真空抽滤，用丙酮彻底冲洗反应瓶，收集的固体转移到125ml锥形瓶中，在热的丙酮溶剂搅拌，趁热过滤，总共重复四次以上操作。合并的固体转移到棕色试管中120℃真空干燥12小时。
制备例3 TpPa-1的制备参考文献J.Am.Chem.Soc.2012，134，19524-19527
向一个耐热玻璃管(10×8mm2×18cm)加入2,4,6-三羟基-1,3,5-苯三甲醛63mg，(0.3mmol)1,4-苯二胺(Pa-1)48mg(0.45mmol)，1.5mL均三甲苯，1.5mL1,4-二氧六环，0.5mL3M醋酸水溶液。混合物超声10分钟。耐热玻璃管在77K(液氮浴)中快速冷冻后，进行三次冷冻-抽真空-解冻操作完全除去体系中的氧气，在N2气氛下火焰封管，在120℃加热三天。离心得到红色沉淀，用无水丙酮洗涤沉淀。收集的粉末再用无水丙酮溶剂交换6次。然后粉末在真空烘箱中180℃加热24小时得到深红色粉末。
实施例1
将对溴苯甲腈、吡咯、二异丙基乙胺、奎宁环、叔丁醇钾按1:20:8:0.005:2的摩尔比(0.1mmol:2mmol:0.0005mmol:0.2mmol)加入到盛有乙腈的控温透明反应瓶中并控温25℃，加入光催化剂TpTta并使其在反应体系中的浓度为2g/L，对溴苯甲腈、吡咯、二异丙基乙胺、奎宁环、叔丁醇钾在反应体系中的浓度分别为0.1mol/L、2mol/L、0.0005mol/L、0.2mol/L，密闭封口，通入惰性气体，并使控温透明反应瓶中的惰性气体压力为0.01MPa，控制温度为25℃并搅拌半小时使对溴苯乙甲腈吸附达到平衡，然后用100W 395nm LED照射控温透明反应瓶并保持温度25℃，照射8个小时后停止反应，柱色谱分离反应产物，反应产物为4-(1H-吡咯-2-基)苯甲腈，其分离产率为65％。
采用高速离心方法对催化剂TpTta进行回收利用。按照上述方法再次催化制备4-(1H-吡咯-2-基)苯甲腈，由催化结果可知，循环利用5次后产物产率基本没有变化。
实施例2
将对溴苯甲腈、吡咯、四丁基十聚钨酸铵、三乙胺、碳酸铯按1:50:0.001:10:3(0.2mmol:10mmol:0.0002mmol：2mmol:0.6mmol)的摩尔比例加入到盛有丙酮的控温透明反应瓶中并控温25℃，加入光催化剂TAPA-TFP COF，并使TAPA-TFP COF光催化剂在反应体系中的浓度为1g/L。对溴苯甲腈、吡咯、四丁基十聚钨酸铵、三乙胺、碳酸铯在反应体系中的浓度分别为0.2mol/L、10mol/L、0.0002mol/L、2mol/L、0.6mol/L。密闭封口，通入惰性气体，并使控温透明反应瓶中的惰性气体压力为0.01MPa，控制温度为25℃并搅拌半小时使对溴苯甲腈吸附达到平衡，然后用100W 420nm LED的照射控温透明反应瓶并保持温度25℃，照射10个小时后停止反应，柱色谱分离产物，反应产物为4-(1H-吡咯-2-基)苯甲腈，其分离产率为80％。4-(1H-吡咯-2-基)苯甲腈的核磁氢谱表征结果如图1所示。质谱图如图2所示。
1H NMR(300MHz,丙酮-d6)：δ＝6.24(s,1H),6.77(s,1H),6.99(s,1H),7.70,7.79(AA’BB’,J＝9Hz,4H),10.78(br,s,1H)。
MS(ESI):m/z＝167.1(M-H)+。
实施例3
将对溴苯甲腈、吡咯、三(三甲基硅)硅烷、异丙醇、磷酸钾按1：40:0.002:15:10(0.5mmol:2mmol:0.001mmol:7.5mmol:5mmol)的摩尔比例加入到盛有二甲基亚砜的控温透明反应瓶中并控温25℃，加入光催化剂TpPa-1，并使TpPa-1光催化剂在反应体系中的浓度为5g/L，对溴苯甲腈、吡咯、三(三甲基硅)硅烷、异丙醇、磷酸钾在反应体系中的浓度分别为0.5mol/L、2mol/L、0.001mol/L、7.5mol/L、5mol/L，密闭封口，通入惰性气体，并使控温透明反应瓶中的惰性气体压力为0.01MPa，控制温度为25℃并搅拌半小时使吡咯吸附达到平衡，然后用300W模拟太阳光照射控温透明反应瓶并保持温度25℃，照射12个小时后停止反应，柱色谱分离产物，反应产物为4-(1H-吡咯-2-基)苯甲腈，其分离产率为90％。
对比例1
将对溴苯甲腈、吡咯、三乙胺、碳酸铯按1:50:10:3(0.2mmol:10mmol:2mmol:0.6mmol)的摩尔比例加入到盛有丙酮的控温透明反应瓶中并控温25℃，加入光催化剂TAPA-TFP COF，使TAPA-TFP COF催化剂在反应体系中的浓度为1g/L，对溴苯甲腈、吡咯、三乙胺、碳酸铯在反应体系中的浓度分别为0.2mol/L、10mol/L、2mol/L、0.6mol/L，密闭封口，通入惰性气体，并使控温透明反应瓶中的惰性气体压力为0.01MPa，控制温度为25℃并搅拌半小时使对溴苯甲腈吸附达到平衡，然后用100W 420nm LED的照射控温透明反应瓶并保持温度25℃，照射10个小时后停止反应，利用薄层色谱分析以及GC-MS分析，没有目标产物生成。
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种卤代芳香类化合物与芳香类化合物通过光化学催化脱卤化氢合成联芳香类化合物的方法，其特征在于，包括以下步骤：
在光、光催化剂、助催化剂、氢供体和碱的存在下，卤代芳香类化合物和芳香类化合物反应得到联芳香类化合物；
所述光的光源为395nm LED、420nm LED、太阳光或模拟太阳光；
所述光催化剂为TpTta、TAPA-TFPCOF、TpPa-1中的至少一种；
所述助催化剂选自奎宁环、苯硫酚、二苯基二硫醚、三(三甲基硅)硅烷、三(三甲基硅)硅醇、四丁基十聚钨酸铵中的至少一种；
所述碱选自有机碱或无机碱；
所述芳香类化合物选自芳环类化合物或杂芳环类化合物，所述芳环类化合物或杂芳环类化合物可进一步被一个、两个或更多个Rs取代，所述Rs选自OH、氰基、COOH、COH、NH2、C1-12烷基、C1-12烷氧基、C3-12环烷基、C3-12环烷基氧基、-C(O)-C1-12烷基；
所述卤代芳香类化合物为上述芳香类化合物芳环或杂芳环上至少一个H被卤素取代形成的化合物。
2.根据权利要求1所述的方法，其特征在于，所述芳香类化合物选自无取代或任选被一个、两个或更多个如下基团取代的C6-12芳环或5-12元杂芳环类化合物：OH、氰基、COOH、COH、NH2、C1-6烷基、C1-6烷氧基、C3-6环烷基、C3-6环烷基氧基、-C(O)-C1-6烷基、卤代C1-6烷基；
所述卤代芳香类化合物选自被溴或氯取代的芳香类化合物。
3.根据权利要求1或2所述的方法，其特征在于，所述芳香类化合物选自均三甲氧基苯、吡咯或呋喃；
所述卤代芳香类化合物选自对溴苯乙酮、对溴苯甲腈、邻氯三氟甲苯、溴苯、对三氟甲基溴苯中的至少一种。
4.根据权利要求1所述的方法，其特征在于，所述氢供体选自甲醇、乙醇、异丙醇、乙胺、丙胺、丁胺、异丙胺、二乙基甲胺、二甲基乙胺、二异丙基乙基胺、三乙胺、三丁胺中的至少一种。
5.根据权利要求1所述的方法，其特征在于，所述碱选自碳酸钾、碳酸铯、碳酸钠、磷酸钾、磷酸钠、磷酸铯、氢氧化钾、叔丁醇钾、氢氧化钠中的至少一种。
6.根据权利要求1所述的方法，其特征在于，所述卤代芳香类化合物、芳香类化合物、助催化剂、氢供体、碱的摩尔比为1:(1-50):(1-10):(0.001-0.005):(1-10)。
7.根据权利要求1所述的方法，其特征在于，所述光催化剂在反应体系中的浓度为0.1-50g/L。
8.根据权利要求1所述的方法，其特征在于，所述反应在惰性气氛中进行。
9.根据权利要求1所述的方法，其特征在于，反应温度为10-50℃。
10.根据权利要求1所述的方法，其特征在于，所述反应在密闭的透明反应器中进行。
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