CN114702438A - 一种双金属有机框架异相催化的Kumada偶联反应 - Google Patents
一种双金属有机框架异相催化的Kumada偶联反应 Download PDFInfo
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- CN114702438A CN114702438A CN202210296229.9A CN202210296229A CN114702438A CN 114702438 A CN114702438 A CN 114702438A CN 202210296229 A CN202210296229 A CN 202210296229A CN 114702438 A CN114702438 A CN 114702438A
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- organic framework
- kumada coupling
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- 239000013384 organic framework Substances 0.000 title claims abstract description 30
- 238000005577 Kumada cross-coupling reaction Methods 0.000 title claims abstract description 24
- 238000007210 heterogeneous catalysis Methods 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000002904 solvent Chemical class 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 23
- -1 aryl Grignard reagent Chemical class 0.000 claims abstract description 15
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000006880 cross-coupling reaction Methods 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 72
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 37
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 229910003321 CoFe Inorganic materials 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000004440 column chromatography Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
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- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
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- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 2
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
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- 239000011572 manganese Substances 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 125000004076 pyridyl group Chemical group 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
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- RBWRWAUAVRMBAC-UHFFFAOYSA-M magnesium;methoxybenzene;bromide Chemical compound [Mg+2].[Br-].COC1=CC=[C-]C=C1 RBWRWAUAVRMBAC-UHFFFAOYSA-M 0.000 description 8
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- FKUUDDGRDRPAQQ-UHFFFAOYSA-M magnesium;methoxybenzene;bromide Chemical compound [Mg+2].[Br-].COC1=CC=C[C-]=C1 FKUUDDGRDRPAQQ-UHFFFAOYSA-M 0.000 description 1
- BVUQKCCKUOSAEV-UHFFFAOYSA-M magnesium;methylbenzene;bromide Chemical compound [Mg+2].[Br-].CC1=CC=[C-]C=C1 BVUQKCCKUOSAEV-UHFFFAOYSA-M 0.000 description 1
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 1
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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
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D215/14—Radicals substituted by oxygen atoms
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了一种双金属有机框架异相催化的Kumada偶联方法，该Kumada偶联方法以双金属有机框架(MOF)材料为催化剂，将双金属MOF材料、芳基格氏试剂、卤代杂环化合物和溶剂混合至Schlenk反应瓶，在无水无氧条件下进行交叉偶联反应。本发明工艺简单绿色，催化剂易与产物分离，且催化剂可循环利用。
Description
技术领域
本发明属于无机-有机化学催化合成技术领域，具体涉及以双金属有机框架(MOF)为催化剂，异相催化Kumada偶联反应的方法。
背景技术
过渡金属催化的交叉偶联反应是一种高效构筑碳-碳键的强有力工具。该方法已广泛应用于药物、除草剂、天然产物等重要分子的合成。为大幅度地提高其反应活性，如何选择合适的催化剂是至关重要的。目前，常用的催化剂主要包括：贵金属(Pd)及其衍生物、过渡金属及其配合物。所述催化剂均展现出较高的催化活性，但其属于均相催化体系的范畴。对于均相催化体系，它们表现出较高的催化活性，但面临分离和回收困难，价格昂贵，且目标产物中的金属残留难以除去等问题，这将限制其在工业中的大规模合成应用。所以可使催化剂与产物易于分离的非均相体系逐渐引起广泛关注。
金属有机框架(MOF)因具有独特的孔洞框架结构、比表面积大、活性位点可设计性及可修饰等特点，已被考虑作为合适的异相催化剂用于催化各类有机反应(如Suzuki，Sonogashira,，Heck反应等)。然而，金属有机框架用作异相催化剂时，常需经掺杂或者后修饰等处理，如将金属有机框架孔道内嵌入活性金属纳米颗粒或其配体功能化等。经调研发现，关于以未经修饰的金属有机框架为催化剂催化有机反应的报道甚是少见，尤其是用于催化Kumada偶联反应。在本发明中，我们提出使用未经修饰的金属有机框架材料为催化剂，催化芳基格氏试剂和芳烃卤代物间的Kumada偶联反应，由此构建一系类结构多样的联杂芳烃类化合物。
发明内容
本发明目的在于克服现有技术的不足，提供一种以未经修饰的双金属有机框架材料作为异相催化剂，催化Kumada交叉偶联反应。该发明工艺简单，异相催化剂无需修饰，避免使用昂贵金属，最重要的是催化剂易于分离且可循环使用。
为实现上述目的，本发明采用如下技术方案：
氮气氛围下，向干燥的Schlenk反应瓶中加入式(I)所示的双金属有机框架材料、式(II)所示的卤代杂芳烃化合物和溶剂，随后将反应瓶至于一定温度下边搅拌边逐滴加入式(III)所示的芳基格氏试剂，经TLC监测反应进程，至原料完全反应后，经后处理得到式(IV)所示的联杂芳烃化合物，
所述双金属有机框架材料的结构如式(I)所示：
所述的卤代杂芳烃化合物如式(II)所示：
所述的芳基格氏试剂如式(III)所示：
所述的联杂芳烃化合物如式(IV)所示：
反应式如下：
本发明中，可选用的后处理过程包括：萃取，洗涤，硅胶拌样，经柱层析纯化得到偶联产物。
作为优选，R1为氢、卤素、C1-C5烷基、氨基或芳基；
为C5-C14氮或氧或硫杂芳基；
作为优选，R2为氢、卤素、C1-C4烷基、C1-C3烷氧基；
作为优选，X为氯、溴或碘。
上述各R1-R2取代基中的具有所述碳原子数目的芳基、烷基和烷氧基任选地被取代基取代，所述的取代基选自氢、卤素、C1-C5烷基、C5-C14氮或氧或硫杂芳基、C1-C3烷氧基。
作为优选，以摩尔量计，卤代芳烃:芳基格氏试剂＝1.0:1.0～1.0:3.0。作为进一步的优选，以摩尔量计，卤代芳烃:芳基格氏试剂＝1.0:1.2。
作为优选，所述的反应的时间为12～24小时，反应时间过长过短都会影响反应的产率，优选为15小时。
作为优选，所述的一定温度为0～50℃，优选为25℃。
作为优选，所述的双金属有机框架催化剂(MOF)的金属组合为NiFe，MnFe或CoFe中的一种，优选为CoFe。
作为优选，所述的双金属有机框架催化剂(MOF)的用量为0％-10％mmol，优选为5％mmol。
作为优选，所述的有机溶剂为乙醚、四氢呋喃、甲苯、乙苯、三氟甲苯和二氧六环中的任意一种，优选为四氢呋喃。
同现有技术相比较，本发明的有益效果在于：
(1)相对于均相过渡金属催化剂，非均相MOF催化剂易与产物分离，且可循环利用，从而最大化的降低了产物中的金属残留；
(2)相较于其他金属有机框架催化有机反应体系而言，该发明工艺简单，异相催化剂无需修饰即可直接用于催化Kumada偶联反应，此方法还可轻易地扩大至克级，为Kumada偶联反应的绿色、便捷、规模化催化应用提供了可能。
附图说明
图1为实施例1得到的产物的核磁共振氢谱；
图2为实施例1得到的产物的核磁共振碳谱；
图3为实施例9得到的产物的核磁共振氢谱；
图4为实施例9得到的产物的核磁共振碳谱；
图5为实施例10得到的产物的核磁共振氢谱；
图6为实施例10得到的产物的核磁共振碳谱；
图7为实施例11得到的产物的核磁共振氢谱；
图8为实施例11得到的产物的核磁共振碳谱；
图9为实施例12得到的产物的核磁共振氢谱；
图10为实施例12得到的产物的核磁共振碳谱；
图11为实施例13得到的产物的核磁共振氢谱；
图12为实施例13得到的产物的核磁共振碳谱；
图13为实施例14得到的产物的核磁共振氢谱；
图14为实施例14得到的产物的核磁共振碳谱；
图15为实施例15得到的产物的核磁共振氢谱；
图16为实施例15得到的产物的核磁共振碳谱；
图17为实施例16得到的产物的核磁共振氢谱；
图18为实施例16得到的产物的核磁共振碳谱；
图19为实施例17得到的产物的核磁共振氢谱；
图20为实施例17得到的产物的核磁共振碳谱；
图21为实施例18双金属有机框架循环实验图。
具体实施方式
为了使本发明所述的内容更加清晰，下面将结合具体实施例，对本发明进行进一步详细的描述，但本发明并不局限于此。
下述实施例中所述实验方法，如无特殊说明，均为常规方法；所述试剂和原料，如无特殊说明，均可以从商业途径获得和/或根据已知的方法制备获得。
双金属有机框架(MOFs)的制备方法：将不同种类的金属硝酸盐(0.6mmol)和有机配体置于N,N-二甲基甲酰胺(2mL)、乙醇(2mL)及水(2mL)的混合溶液中，室温下搅拌使之充分溶解，后将其置于120℃烘箱反应两天后，冷却至室温，乙醇洗涤-干燥，最终得到双金属有机框架材料.
上述制备方法中：硝酸盐为六水合硝酸钴、九水合硝酸铁(III)或四水合硝酸锰；
上述制备方法中：不同种类的硝酸盐摩尔比例约为1：1；
上述制备方法中：有机配体为均苯三酸(BTC)和硫代二乙酸(tda)；
上述制备方法中：硝酸盐、均苯三酸(BTC)和硫代二乙酸(tda)的摩尔比约为1：0.3：1；
实施例1-8为反应条件优化实验。
实施例1
在无水无氧条件下，向Schlenk瓶中加入式1所示的3-氯吡啶II-1(0.8mmol)和双金属有机框架材料[CoFe(tda)H2O](5mol％)溶于无水乙醚(4mL)溶剂中。在0℃温度下搅拌10min后，将对甲氧基苯基溴化镁III-1(1.2mmol)逐滴滴入反应体系中，后将其置于25℃下反应15h。反应结束后，向反应体系中加入3mL饱和氯化铵溶液进行淬灭后，再加入10mL乙酸乙酯进行萃取。所得有机相经过滤并减压浓缩除去溶剂，将残余物经柱层析分离，洗脱溶剂为：乙酸乙酯/石油醚，得到黄色油状产物IV-1(70％产率)。
1H NMR(400MHz,CDCl3)δ8.81(d,J＝2.4,1H),8.54(dd,J＝4.8,1.6Hz,1H),7.84–7.81(m,1H),7.53–7.50(m,2H),7.34–7.31(m,1H),7.03–6.99(m,2H),3.85(s,3H).13C NMR(101MHz,CDCl3)δ159.9,148.1,148.0,136.4,134.0,130.4,128.4,123.6,114.7,55.5.
实施例2
溶剂用四氢呋喃替代乙醚，其余条件同实施例1，得到目标产物IV-1的收率为78％。
实施例3
催化剂用量提升至10mol％，其余条件同实施例1，得到目标产物IV-1的收率为78％。
实施例4
反应温度升高至50℃，其余条件同实施例1，得到目标产物IV-1的收率为71％。
实施例5
将对甲氧基苯基溴化镁用量提高至1.5mmol，其余条件同实施例1，得到目标产物IV-1的收率为67％。
实施例6
催化剂用Fe(tda)H2O代替CoFe(tda)H2O，其余条件同实施例1，得到目标产物IV-1的收率为13％。
实施例7
溶剂乙醚的用量降低至2mL，其余条件同实施例1，得到目标产物IV-1的收率为65％。
实施例8
催化剂用NiFe(tda)H2O代替CoFe(tda)H2O，其余条件同实施例1，得到目标产物IV-1的收率为22％。
由上述实施例1-8可以看出，最佳的催化剂为实施例2的反应条件，即溶剂为四氢呋喃，所用催化剂为CoFe(tda)H2O。在获得最佳反应条件的基础上，发明人进一步在该条件下，选择不同取代的卤代杂芳烃和芳基格氏试剂为底物发展高效的Kumada偶联催化方法。
实施例9
在无水无氧条件下，向Schlenk瓶中加入式2所示的3-氯吡啶II-1(0.8mmol)和双金属有机框架材料[CoFe(tda)H2O](5mol％)溶于无水四氢呋喃(4mL)溶剂中。在0℃温度下搅拌10min后，将对氯苯基溴化镁III-2(1.2mmol)逐滴滴入反应体系中，后将其置于室温下反应13h。反应结束后，向反应体系中加入3mL饱和氯化铵溶液进行淬灭后，再加入10mL乙酸乙酯进行萃取。所得有机相经过滤并减压浓缩除去溶剂，将残余物经柱层析分离，洗脱溶剂为：乙酸乙酯/石油醚，得到油状产物IV-3(64％产率)。
1H NMR(400MHz,CDCl3)δ8.82(d,J＝2.2Hz,1H),8.60(dd,J＝4.8,1.5Hz,1H),7.84(dt,J＝7.9,1.8Hz,1H),7.51(d,J＝8.5Hz,1H),7.45(d,J＝8.5Hz,1H),7.37(dd,J＝7.9,4.8Hz,1H).
13C NMR(101MHz,CDCl3)δ148.9,148.3,136.4,135.6,134.5,134.3,129.4,128.5,123.7.
实施例10
在无水无氧条件下，向Schlenk瓶中加入式3所示的3-氯吡啶II-1(0.8mmol)和双金属有机框架材料[CoFe(tda)H2O](5mol％)溶于无水四氢呋喃(4mL)溶剂中。在0℃温度下搅拌10min后，将苯基溴化镁III-3(1.2mmol)逐滴滴入反应体系中，后将其置于室温下反应12h。反应结束后，向反应体系中加入3mL饱和氯化铵溶液进行淬灭后，再加入10mL乙酸乙酯进行萃取。所得有机相经过滤并减压浓缩除去溶剂，将残余物经柱层析分离，洗脱溶剂为：乙酸乙酯/石油醚，得到油状产物IV-3(44％产率)。
1H NMR(400MHz,CDCl3)δ8.85(d,J＝2.4Hz,1H),8.59(dd,J＝4.9,1.7Hz,1H),7.87(dt,J＝7.8,2.0Hz,1H),7.59–7.57(m,2H),7.50–7.46(m,2H),7.43–7.35(m,2H).
13C NMR(101MHz,CDCl3)δ148.5,148.4,137.8,136.6,134.4,129.1,128.1,127.2,123.6.
实施例11
在无水无氧条件下，向Schlenk瓶中加入式4所示的3-氯吡啶III-1(0.8mmol)和双金属有机框架材料[CoFe(tda)H2O](5mol％)溶于无水四氢呋喃(4mL)溶剂中。在0℃温度下搅拌10min后，将对甲基苯基溴化镁III-4(1.2mmol)逐滴滴入反应体系中，后将其置于室温下反应15h。反应结束后，向反应体系中加入3mL饱和氯化铵溶液进行淬灭后，再加入10mL乙酸乙酯进行萃取。所得有机相经过滤并减压浓缩除去溶剂，将残余物经柱层析分离，洗脱溶剂为：乙酸乙酯/石油醚，得到油状产物IV-4(71％产率)。
1H NMR(400MHz,CDCl3)δ8.84(d,J＝1.5Hz,1H),8.56(dd,J＝4.8,1.6Hz,1H),7.85(ddd,J＝7.9,2.3,1.6Hz,1H),7.48(d,J＝8.2Hz,2H),7.34(ddd,J＝7.9,4.8,0.9Hz,1H),7.29(d,J＝7.9Hz,2H),2.41(s,3H).
13C NMR(101MHz,CDCl3)δ148.3,138.1,136.7,135.0,134.2,129.9,127.1,123.6,21.3.
实施例12
在无水无氧条件下，向Schlenk瓶中加入式5所示的3-氯吡啶II-1(0.8mmol)和双金属有机框架材料[CoFe(tda)H2O](5mol％)溶于无水四氢呋喃(4mL)溶剂中。在0℃温度下搅拌10min后，将间甲氧基苯基溴化镁III-5(1.2mmol)逐滴滴入反应体系中，后将其置于室温下反应12h。反应结束后，向反应体系中加入3mL饱和氯化铵溶液进行淬灭后，再加入10mL乙酸乙酯进行萃取。所得有机相经过滤并减压浓缩除去溶剂，将残余物经柱层析分离，洗脱溶剂为：乙酸乙酯/石油醚，得到油状产物IV-5(79％产率)。
1H NMR(400MHz,CDCl3)δ8.84(d,J＝1.6Hz,1H),8.59(dd,J＝4.8,1.6Hz,1H),7.88–7.85(m,1H),7.42–7.34(m,2H),7.16(ddd,J＝7.6,1.7,0.9Hz,1H),7.11–7.10(m,1H),6.95(ddd,J＝8.3,2.6,0.9Hz,1H),3.87(s,3H).
13C NMR(101MHz,CDCl3)δ160.3,148.8,148.5,139.5,136.7,134.6,130.3,123.7,119.7,113.6,113.1,55.5.
实施例13
在无水无氧条件下，向Schlenk瓶中加入式6所示的2-氯-1,3-苯并噁唑II-2(0.8mmol)和双金属有机框架材料[CoFe(tda)H2O](5mol％)溶于无水四氢呋喃(4mL)溶剂中。在0℃温度下搅拌10min后，将对甲氧基苯基溴化镁III-1(1.2mmol)逐滴滴入反应体系中，后将其置于室温下反应20h。反应结束后，向反应体系中加入3mL饱和氯化铵溶液进行淬灭后，再加入10mL乙酸乙酯进行萃取。所得有机相经过滤并减压浓缩除去溶剂，将残余物经柱层析分离，洗脱溶剂为：乙酸乙酯/石油醚，得到白色固体产物IV-6(58％产率)。
1H NMR(400MHz,CDCl3)δ8.20–8.17(m,2H),7.76–7.71(m,1H),7.56–7.52(m,1H),7.35–7.28(m,2H),7.03–6.99(m,2H),3.86(s,3H).
13C NMR(101MHz,CDCl3)δ163.3,162.4,150.8,142.4,129.5,124.7,124.5,119.8,119.7,114.4,110.5,55.5.
实施例14
在无水无氧条件下，向Schlenk瓶中加入式7所示的2-氯-1,3-苯并噻唑II-3(0.8mmol)和双金属有机框架材料[CoFe(tda)H2O](5mol％)溶于无水四氢呋喃(4mL)溶剂中。在0℃温度下搅拌10min后，将对甲氧基苯基溴化镁III-1(1.2mmol)逐滴滴入反应体系中，后将其置于室温下反应24h。反应结束后，向反应体系中加入3mL饱和氯化铵溶液进行淬灭后，再加入10mL乙酸乙酯进行萃取。所得有机相经过滤并减压浓缩除去溶剂，将残余物经柱层析分离，洗脱溶剂为：乙酸乙酯/石油醚，得到白色固体产物IV-7(62％产率)。
1H NMR(400MHz,CDCl3)δ8.08–7.99(m,3H),7.88(d,J＝7.9Hz,1H),7.49–7.45(m,1H),7.37–7.33(m,1H),7.02–6.98(m,2H),3.88(s,3H).
13C NMR(101MHz,CDCl3)δ168.0,162.1,154.4,135.0,129.3,126.6,126.4,124.9,123.0,121.7,114.5,55.6.
实施例15
在无水无氧条件下，向Schlenk瓶中加入式8所示的2-氯喹啉II-4(0.8mmol)和双金属有机框架材料[CoFe(tda)H2O](5mol％)溶于无水四氢呋喃(4mL)溶剂中。在0℃温度下搅拌10min后，将对甲氧基苯基溴化镁III-1(1.2mmol)逐滴滴入反应体系中，后将其置于室温下反应22h。反应结束后，向反应体系中加入3mL饱和氯化铵溶液进行淬灭后，再加入10mL乙酸乙酯进行萃取。所得有机相经过滤并减压浓缩除去溶剂，将残余物经柱层析分离，洗脱溶剂为：乙酸乙酯/石油醚，得到白色固体产物IV-8(72％产率)。
1H NMR(400MHz,CDCl3)δ8.15(d,J＝8.5Hz,1H),8.16–8.14(m,3H),7.82(d,J＝8.7Hz,1H),7.80(d,J＝8.2Hz,1H),7.73–7.69(m,1H),7.50(t,J＝7.5Hz,1H),7.05(d,J＝8.8Hz,2H),3.88(s,3H).
13C NMR(101MHz,CDCl3)δ160.9,157.0,148.4,136.7,132.4,129.7,129.7,129.0,127.6,127.0,126.0,118.7,114.3,55.5.
实施例16
在无水无氧条件下，向Schlenk瓶中加入式9所示的2-氨基-5-氯吡嗪II-5(0.8mmol)和双金属有机框架材料[CoFe(tda)H2O](5mol％)溶于无水四氢呋喃(4mL)溶剂中。在0℃温度下搅拌10min后，将对甲氧基苯基溴化镁III-1(1.2mmol)逐滴滴入反应体系中，后将其置于室温下反应15h。反应结束后，向反应体系中加入3mL饱和氯化铵溶液进行淬灭后，再加入10mL乙酸乙酯进行萃取。所得有机相经过滤并减压浓缩除去溶剂，将残余物经柱层析分离，洗脱溶剂为：乙酸乙酯/石油醚，得到白色固体产物IV-9(69％产率)。
1H NMR(400MHz,CDCl3)δ8.31(s,1H),7.90–7.85(m,3H),6.98(d,J＝8.8Hz,2H),4.69(s,2H),3.85(s,3H).
13C NMR(101MHz,CDCl3)δ160.9,153.9,150.0,130.9,129.8,129.4,128.3,114.3,55.5.
实施例17
在无水无氧条件下，向Schlenk瓶中加入式10所示的6-氯喹啉II-6(0.8mmol)和双金属有机框架材料[CoFe(tda)H2O](5mol％)溶于无水四氢呋喃(4mL)溶剂中。在0℃温度下搅拌10min后，将对甲氧基苯基溴化镁III-1(1.2mmol)逐滴滴入反应体系中，后将其置于室温下反应13h。反应结束后，向反应体系中加入3mL饱和氯化铵溶液进行淬灭后，再加入10mL乙酸乙酯进行萃取。所得有机相经过滤并减压浓缩除去溶剂，将残余物经柱层析分离，洗脱溶剂为：乙酸乙酯/石油醚，得到白色固体产物IV-10(57％产率)。
1H NMR(400MHz,CDCl3)δ8.87(dd,J＝4.2,1.6Hz,1H),8.14(d,J＝8.5Hz,2H),7.95–7.91(m,2H),7.63(d,J＝8.6Hz,2H),7.39–7.36(m,1H),7.01(d,J＝8.7Hz,2H),3.85(s,3H).
13C NMR(101MHz,CDCl3)δ159.6,150.1,147.4,139.0,136.2,132.8,129.8,129.1,128.6,128.5,124.7,121.5,114.5,55.4.
实施例18
催化剂循环实验
在无水无氧条件下，向Schlenk瓶中加入式11所示的3-氯吡啶II-1(4mmol)和双金属有机框架材料[CoFe(tda)H2O](5mol％)溶于无水四氢呋喃(20mL)溶剂中。在0℃温度下搅拌10min后，将对甲氧基苯基溴化镁III-1(6mmol)逐滴滴入反应体系中，后将其置于室温下反应15h。反应结束后，向反应体系中加入3mL饱和氯化铵溶液进行淬灭后，再加入10mL乙酸乙酯进行萃取。所得有机相经过滤并减压浓缩除去溶剂，将残余物经柱层析分离，洗脱溶剂为：乙酸乙酯/石油醚，得到白色固体产物IV-1(69％产率)。所得无机相加入去离子水和乙醇洗涤，后经离心处理，可回收相应的催化剂。所得催化剂经干燥后，再投入下次催化循环。结果表明，催化剂可循环四次，且产率并没有明显的降低。
由上述催化剂循环实验的顺利实施可知，该催化剂易与产物分离且可循环使用。因此该方法的发展极大地推动了异相催化的Kumada偶联反应的发展，为工业化、绿色催化合成提供了一条可供选择的方法。
以上所述实施例仅为本发明的优选实施例，而并非本发明可行实施的穷举。对于本领域技术人员而言，在不背离本发明原理和精神的前提下，对其所作出的任何显而易见的改动，都应当被认为包含在本发明的权利要求保护范围之内。
Claims (10)
1.一种双金属有机框架异相催化的Kumada偶联方法，其特征在于：将双金属有机框架材料、卤代杂芳烃和芳基格氏试剂一起溶于有机溶剂中，在无水无氧条件下，经Kumada偶联得到联杂芳基交叉偶联产物；
所述双金属有机框架材料的分子式为M(tda)H2O，其中M可分别为NiFe，MnFe或CoFe；tda为硫代二乙酸；
所述的氯代杂芳烃的结构如式(II)所示：
所述的芳基格氏试剂的结构如式(III)所示：
所述的联杂芳基交叉偶联产物的结构如式(IV)所示：
在通式(I)、(II)和(III)中:
R1为氢、卤素、C1-C5烷基、氨基或芳基；
为C5-C14氮或氧或硫杂芳环；
R2为氢、卤素、C1-C4烷基或C1-C3烷氧基；
X为卤素。
2.根据权利1要求所述的Kumada偶联方法，其特征在于，所述的R1为氢、氟、氯、溴、碘、甲基、乙基、叔丁基、氨基或苯基；
3.根据权利1要求所述的Kumada偶联方法，其特征在于，所述的R2为氢、氟、氯、溴、碘、甲基、乙基、甲氧基或异丙基。
4.根据权利1要求所述的Kumada偶联方法，其特征在于，所述的X为氯、溴或碘。
5.根据权利要求1-4任一项所述的Kumada偶联方法，其特征在于，以卤代杂芳烃计，双金属有机框架催化Kumada偶联反应时，双金属有机框架材料的用量为0％-10％mmol。
6.根据权利要求1-4任一项所述的Kumada偶联方法，其特征在于，以卤代杂芳烃计，所述的芳基格氏试剂的用量为1-3当量。
7.根据权利要求1-4任一项所述的Kumada偶联方法，其特征在于，所述的Kumada偶联反应温度为0-50℃，反应时间为12-24小时。
8.根据权利要求1-4任一项所述的Kumada偶联方法，其特征在于，所述的有机溶剂为乙醚、四氢呋喃、甲苯、乙苯、三氟甲苯和二氧六环中的任意一种。
9.根据权利要求1-4任一项所述的Kumada偶联方法，其特征在于，所述的后处理操作如下：将反应完成后的反应液先用饱和氯化铵溶液进行淬灭，后用乙酸乙酯萃取再经减压浓缩除去溶剂，将残余物经柱层析分离，洗脱溶剂为：乙酸乙酯/石油醚，最终得到目标产物。
10.根据权利要求1所述的双金属有机框架异相催化的Kumada偶联方法，其特征在于：所述的双金属有机框架材料的制备方法如下：
将金属硝酸盐和有机配体置于N,N-二甲基甲酰胺、乙醇和水的混合溶液中，搅拌溶解，然后置于110～130℃反应1～3天，冷却至室温，乙醇洗涤，干燥，最终得到所述的双金属有机框架材料；
所述硝酸盐为钴、锰和镍的硝酸盐中的一种和铁的硝酸盐；
所述有机配体为均苯三酸和硫代二乙酸。
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