CN105152897B - 一种利用原位产生的CO实现羰基化Suzuki偶联的方法 - Google Patents

一种利用原位产生的CO实现羰基化Suzuki偶联的方法 Download PDF

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CN105152897B
CN105152897B CN201510594029.1A CN201510594029A CN105152897B CN 105152897 B CN105152897 B CN 105152897B CN 201510594029 A CN201510594029 A CN 201510594029A CN 105152897 B CN105152897 B CN 105152897B
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carbonylation
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phen
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suzuki coupling
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CN105152897A (zh
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李朝晖
封雪
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Fuzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
    • B01J2231/4227—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group with Y= Cl

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  • Organic Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

本发明公开了一种利用原位产生的CO实现羰基化Suzuki偶联的方法，属于有机化学和光催化技术领域。在不通入有毒气体CO的情况下实现了光催化的羰基化偶联反应，反应无需高能量微波物理作用和额外添加剂或配体的加入，同时避免了一般羰基化反应中高温高压的苛刻条件以及处理有毒气体CO的繁琐操作。此外，该方法操作简便易行，成本不高，有利于大规模的工业推广。

Description

一种利用原位产生的CO实现羰基化Suzuki偶联的方法
技术领域
本发明属于有机化学及光催化领域，具体涉及一种利用原位产生的CO实现羰基化Suzuki偶联的方法。
背景技术
羰基化反应是有机合成化学中最有用的方法之一，广泛应用于农药、医药、胶粘剂、聚合物等化工领域中。均相催化剂在羰基化反应中通常有较高选择性和产率，但反应往往要求高温、高压或使用贵金属催化剂(如铑、钌、铱等)，并且催化剂不好从产品中分离，这就限制了其工业适用性。因此，非均相催化剂就成为近年来关注的热点。例如，B.M.Bhanage课题组和M.Z. Cai课题组分别使用碳材料和MCM-41作为均相催化剂的载体来实现羰基化Suzuki偶联反应。虽然这些方法已经克服了工业化生产的困难，但是有毒气体一氧化碳作为羰基源的通入是必不可少的。
近年来，为了避免处理一氧化碳有毒气体固有的困难，有机羰基化合物（醛类、羧酸）已被报道可以作为羰基化反应中的羰基源，但是在反应体系中必须加入特定的添加剂。金属羰基化合物，比如[Ni(CO)4]、[Mo(CO)6]、[Cr(CO)6]和[W(CO)6]，已被发现在加热时可以放出一氧化碳，也是有用的羰基源。然而它的制备相对困难，成本较高，并且在一氧化碳的释放过程中，往往需要添加特异性配体。N，N-二甲基甲酰胺（DMF）作为一种价格便宜的有机溶剂，也可以释放一氧化碳作为羰基源。 早在1999年， Larhed和Alterman等人已经使用DMF作为羰基化反应中的一氧化碳源，但这是基于微波辅助热分解的原理。其他报道的以DMF作为羰基源的方法都需要添加额外的配位体或强碱。因此，探索一种温和廉价的羰基化反应体系具有重大的意义。
发明内容
本发明的目的在于提供一种利用原位产生的CO实现羰基化Suzuki偶联的方法。该方法利用光催化剂在光激发下产生的光生电子和光生空穴促进分解DMF产生CO，以原位产生的CO为羰基源实现羰基化偶联反应。该方法操作简单，避免了高温高压的苛刻条件以及处理有毒气体CO的繁琐操作，同时光催化剂的制备方法简便易行，有利于大规模的工业推广。
为实现上述目的，本发明采用如下技术方案：
一种利用原位产生的CO实现羰基化Suzuki偶联的方法：利用光催化促进DMF分解生成CO，以原位生成的CO作为羰基源来实现羰基化Suzuki偶联反应。
将光催化剂和均相催化剂相结合形成复合型催化剂，在溶剂DMF中，加入反应底物和有机碱，在光照下进行羰基化Suzuki偶联反应。
所述的复合型光催化剂为PdⅡ- TiO2。
PdⅡ- TiO2采用浸渍法合成：将摩尔比=1：1：1的PdCl2、NaCl和邻菲罗啉溶解于30mL水中，再加入300mg TiO2，滴入盐酸调节pH值，在80℃下搅拌3h，经过滤、洗涤、烘干，得到Pd(phen)Cl2-TiO2。
本发明的显著优点在于：
（1）本发明首次采用光催化原位产生CO实现羰基化Suzuki偶联反应。
（2）本发明首次以光催化下反应溶剂分解产生的CO作羰基源，不需要加入额外的配体或添加剂，同时避免了有毒气体CO的处理。
（3）本发明操作简单易行，无需高温高压，无需高能量微波作用。
（4）本发明所使用的光催化剂的制备方法简单易行，廉价实用，具有很高的实用价值和应用前景。
具体实施方式
（1）光催化剂的具体制备步骤如下：
分别将一定化学计量的PdCl2、NaCl和邻菲罗啉（摩尔比=1：1：1）溶解于30mL水中，再加入300mg TiO2，滴入少量盐酸，在80℃下搅拌3h，经过滤洗涤、烘干，即得到Pd(phen)Cl2-TiO2粉末。
（2）光催化下，原位产生的CO作羰基源的羰基化Suzuki偶联反应的步骤如下：
称取10mg Pd(phen)Cl2-TiO2作为光催化剂，取2mL DMF作反应溶剂，加入0.1mmol碘苯、0.2mmol苯硼酸和1.5mmol三乙胺，在氮气气氛下，紫外灯（λ=365nm，4×4W）光照。
以碘苯和苯硼酸为反应底物，以苯甲醚、DMSO、DMF为溶剂，加入10mg光催化剂和TEA，光照反应15h。反应结果如表1所示，只有在DMF溶剂中能实现羰基化Suzuki偶联反应。当不加催化剂时，只有微量CO产生；当不光照时，没有CO和羰基偶联产物生成；当使用TiO2为光催化剂时， CO 产量明显提高，但没有相应的羰基偶联产物。综上，光催化剂可以促进溶剂DMF分解，原位生成的CO可以作羰基源实现羰基化Suzuki偶联反应。相对比Pd/TiO2，Pd(phen)Cl2-TiO2有更好的催化活性，当光催化剂中钯的质量百分含量为10.0wt.%时，反应的催化活性最高。当减少TEA的用量时，反应的催化活性有所提高，这是由于TEA又可以作为牺牲剂中和光生空穴，使光催化剂催化分解DMF的效率降低。当反应在CO2气氛中进行时，反应产率有所提高，这是由于呈酸性的CO2可以中和DMF分解产生的碱性二甲胺，同时半导体TiO2还可以作为CO2还原产生CO的催化剂，这两方面都可以促进CO的产生，从而使反应产率有所提高。
表1
因此，本发明中利用光催化剂促进DMF分解生成CO，以原位产生的CO为羰基源来实现羰基化Suzuki偶联反应，不需要加入额外的配体或添加剂，无需高温高压，且避免了处理有毒气体CO的繁琐操作，为实现不以CO为羰基源的羰基化偶联反应提供了一种更温和的方法。
以上所述仅为本发明的一个实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (2)

1.一种利用原位产生的CO实现羰基化Suzuki偶联的方法，其特征在于：利用光催化促进DMF分解生成CO，以原位生成的CO作为羰基源来实现羰基化Suzuki偶联反应；
具体步骤如下：称取10mg Pd(phen)Cl2-TiO2作为光催化剂，取2mL DMF 作反应溶剂，加入0.1mmol 碘苯、0.2mmol 苯硼酸和1.5mmol 三乙胺，在氮气气氛下，紫外灯光照15h。
2.根据权利要求1所述的方法，其特征在于：Pd(phen)Cl2-TiO2采用浸渍法合成：将摩尔比=1：1：1的PdCl2、NaCl和邻菲罗啉溶解于30mL水中，再加入300mg TiO2，滴入盐酸调节pH值，在80℃下搅拌3h，经过滤、洗涤、烘干，得到Pd(phen)Cl2-TiO2。
CN201510594029.1A 2015-09-18 2015-09-18 一种利用原位产生的CO实现羰基化Suzuki偶联的方法 Expired - Fee Related CN105152897B (zh)

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