CN111909217A - 一种双（二叔丁基-4-二甲氨基苯基膦）四溴双钯(ⅱ)化合物及其制备方法和用途 - Google Patents
一种双（二叔丁基-4-二甲氨基苯基膦）四溴双钯(ⅱ)化合物及其制备方法和用途 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 39
- IQTHEAQKKVAXGV-UHFFFAOYSA-N 4-ditert-butylphosphanyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(P(C(C)(C)C)C(C)(C)C)C=C1 IQTHEAQKKVAXGV-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 74
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 39
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
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- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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Abstract
本发明公开了一种双(二叔丁基‑4‑二甲氨基苯基膦)四溴双钯(Ⅱ)化合物及其制备方法和用途。本发明的化合物是[Pd(Amphos)Br]单元通过共享两个桥连的Br原子形成该双核钯化合物，其中Pd采取平面四配位与溴形成[Pd2Br2]的四元环结构，配体(Amphos)和溴原子占据钯原子剩余的配位位点，Amphos代表二叔丁基‑4‑二甲氨基苯基膦。该化合物制备方法是：在氮气气氛下，将溴化钯在乙腈溶剂加热回流，溶解后冷却室温，加入二叔丁基‑4‑二甲氨基苯基膦，搅拌反应2小时，析出橘黄粉末状目标产物。本发明的化合物对Suzuki偶联反应显示出高催化活性，明显优于目前常用的偶联催化剂四(三苯基膦)合钯[Pd(PPh3)4]和对于的单核化合物[Pd(Amphos)2Cl2]，可用作新型的有机偶联催化剂。
Description
技术领域
本发明涉及有机合成用钯基偶联催化剂及其制备方法，具体涉及一种双(二叔丁基-4-二甲氨基苯基膦)四溴双钯(II)化合物及其制备方法和用途，属于化学催化技术领域。
背景技术
偶联反应是构建有机新结构和新骨架(C-C,C-N,C-O等)重要手段之一，已广泛用于有机光电功能材料、有机药物和天然产物的合成和生产中。
偶联反应离不开催化剂，其中以四(三苯基膦)合钯Pd(PPh3)4为代表有机膦钯催化剂应用最为广泛。Pd(PPh3)4为Pd(0)的化合物，在空气中不稳定，同时对某些偶联反应活性和选择性均不高。
为此，人们通过选择具有大的空间阻型和富电性的膦配体如t-B双(二叔丁基苯基膦)、Xantphos双[二叔丁基-(4-二甲基氨基苯基)膦]、dppf二茂铁膦、Amphos双(二叔丁基-4-二甲氨基苯基膦)等替代三苯基膦，合成有机膦钯催化剂，以调控催化活性和选择性，并采用Pd(II)替代Pd(0)为中心原子，以提高催化剂的稳定性。
尽管对应的催化剂Pd[(t-Bu)2PPh]2Cl2[Pd(Amphos)2Cl2]、[Pd(dppf)Cl2]、Pd(Xantphos)Cl2已在有机化工行业涉及的一些偶联催化反应中得到应用，但它们在一些特定的偶联反应中仍存在催化活性和选择性不理想的问题，因此，有必要开发新型的有机膦钯催化剂，以满足不断出现的偶联反应的需求。
发明内容
对于有机膦钯(II)催化剂，目前常用的解离基团为氯离子。在偶联催化反应循环机理中，配位的氯离子的解离是反应的第一步，也是反应速率控制步骤。氯离子为卤素离子，与它化学性质比较接近的是溴离子。从配位化学来看，虽然Pd-Br键比Pd-Cl键稳定，但动力学上Pd-Br解离速率更高。
基于此，本发明用溴离子取代氯离子合成了一系列二溴有机膦钯(II)。在这些化合物中，[Pd(Amphos)Br]单元通过共享两个桥连的Br原子形成该双(二叔丁基-4-二甲氨基苯基膦)四溴双钯(II)化合物，其中Pd采取平面四配位与溴形成[Pd2Br2]的四元环结构；配体(Amphos)和溴原子占据钯原子剩余的配位位点，所述(Amphos)代表二叔丁基-4-二甲氨基苯基膦，其结构式为：
本发明的本发明的化合物是一种具有全新结构的双(二叔丁基-4-二甲氨基苯基膦)四溴双钯(II)化合物。
更重要的是，在单边Suzuki偶联反应模型中，它催化4,7-二溴苯并噻二唑与对羟基苯硼酸片呐醇酯之间偶联反应的转化率达到83％。在等钯的摩尔浓度下，本发明的化合物催化偶联反应的转化率明显高于目前常用的偶联催化剂四(三苯基膦)钯(0)[Pd(PPh3)4](60％)和单核化合物二氯-二叔丁基-(4-二甲基氨基苯基)膦钯(II)[Pd(Amphos)2Cl2](56％)，因此可替代[Pd(PPh3)4]的和[Pd(Amphos)2Cl2]应用于一些有机偶联反应。
本发明的[Pd2(Amphos)2Br4]可以采用如下的方法合成：在一定的气氛下，将钯源在有机介质加热回流，溶解后冷却至室温，加入二叔丁基-4-二甲氨基苯基膦，搅拌反应2小时，析出橘黄色粉末状目标产物，过滤收集、有机溶剂洗涤、干燥，产率大于98％，纯度(以钯含量计算)大于99％.
本发明的制备方法的工艺条件如下：
反应气氛：由于游离的双二叔丁基-4-二甲氨基苯基膦对氧敏感，易在空气中氧化降解，因此，需要惰性气体保护下进行合成反应，惰性气体优选氮气；
钯源：可以是常用的钯(II)化合物，如溴钯酸(H2PdCl4)、溴钯酸钠(Na2PdCl4)溴化钯(PdBr2)，优选溴化钯，因为溴化钯可溶于多种有机溶剂；
有机介质：可以是四氢呋喃(THF)、二甲基亚砜(DMSO)或乙腈(CH3CN)，优选乙腈(CH3CN)，因为PdBr2更易溶于乙腈中；
将钯源加入有机介质中，在80℃下加热回流3-4小时，直至溶解完全；
加料比PdBr2(克)：CH3CN(mL)：二叔丁基-4-二甲氨基苯基膦(克)优选1:200:1。
本发明的制备方法的具体步骤如下：
S1，以PdBr2为钯源，加入四氢呋喃(THF)、二甲基亚砜(DMSO)或乙腈(CH3CN)中，在80℃下加热回流4小时，冷却至室温；
S2，在惰性气体气氛中，缓慢滴加二叔丁基-4-二甲氨基苯基膦于以上溶液中，搅拌反应2小时以析出橘红色沉淀；
S3，将S2获得的沉淀物过滤收集，用乙腈(CH3CN)洗涤三次，得到所述的双(二叔丁基-4-二甲氨基苯基膦)四溴双钯(II)化合物。
附图说明
图1是本发明的化合物的单晶结构图。
具体实施方式
A)本发明的化合物的制备方法实施例
为更好的对本发明进行详细说明，举本发明的化合物的制备实施例如下：
1)称取26.6g PdBr2于反应瓶中,加入2000mL乙腈，80℃下搅拌、加热回流4小时，溴化钯完全溶解，形成澄清的深红色溶液，冷却至室温。
2)向反应瓶通入氮气，在搅拌下用恒压滴液漏斗缓慢滴加二叔丁基-4-二甲氨基苯基膦的乙腈溶液(例如，称取Amphos 26.6g溶于400mL乙腈中，30min加毕)，继续搅拌反应2小时，析出橘红色沉淀。
3)过滤收集、用乙腈洗涤三次，得到本发明的化合物52.1g，产率98％，纯度为99％，其结构式如下：
本发明的化合物的特征结构参数为：
钯含量测定：采用还原－重量法对钯含量进行测定，三次平行实验数据得到钯含量：19.8％，与本发明的化合物的计算值一致；
FAB+-MS(m/e,RI):940(M+,100％)，780(M+-2Br,60％)，287(PdL+,20％)。分子离子峰对应分子式为C23H41Br4N2P2Pd2，与本发明的化合物分子式相符合；
IR(cm-1,KBr压片)：3087(s，ν苯环上＝C-H),2965-2897(w,ν-C-H),1598(ws,νas苯环C＝C),1471(s,饱和碳氢叔丁基上饱和碳氢νs(-CH3))，符合本发明的化合物的主要特征基团；
1H NMR(500MHz,CDCl3)δ(ppm):7.70(m,4H),6.61(d,J＝8.6Hz,4H),2.94(s,12H),1.62(m,36H)，符合本发明的化合物的质子的位置和数量。
本发明的化合物的X-单晶衍射分析：
采用溶剂扩散法培养单晶，将上述目标配合物称取20mg溶于乙腈和二氯甲烷比为1:1.5的混合溶剂中静置，两周后得到黄色条状晶体。用单晶X射线衍射仪及相应的软件测得其晶体学数据，如表1和表2所示。
表1.本发明的化合物的晶体结构数据和实验参数
表2 Pd2(amphos)2Br4部分键长和部分键角
这些参数符合所发明的化合物的化学结构。
B)本发明的化合物的用途实施例
在Suzuki偶联反应模型上催化性能评价：
建立目标4,7-二溴苯并噻二唑与对羟基苯硼酸片呐醇酯之间的Suzuki偶联反应模型。THF:H2O＝1:1(10mL)混合溶剂中，分别加入4,7-二溴苯并噻二唑(1.0equiv.)、羟基苯硼酸片呐醇酯(1.0equiv.)、K2CO3(2.0equiv.)、Pd催化剂(以钯计算，相对于4,7-二溴苯并噻二唑量的5mol％)，通入氮气作保护气氛，在75℃反应12h后，采用HPLC测定产物的浓度，计算产率，结果见表3。
表3.不同钯催化剂对苯并噻二唑单边选择性偶联结果列表。
本发明的化合物Pd2(Amphos)2Br4催化Suzuki偶联反应的产率达到了83％，在等钯浓度和相同的反应条件下，四(三苯基膦)合钯[Pd(PPh3)4]和对应的单核配合物[Pd(Amphos)2Cl2]的产率分别为60％和56％，现比较，所发明的化合物明显优于[Pd(PPh3)4]和[Pd(Amphos)2Cl2]，可替代[Pd(PPh3)4]的和[Pd(Amphos)2Cl2]应用于一些有机偶联反应。
Claims (5)
1.一种双(二叔丁基-4-二甲氨基苯基膦)四溴双钯(Ⅱ)化合物，其特征在于：
[Pd(Amphos)Br]单元通过共享两个桥连的Br原子形成该双(二叔丁基-4-二甲氨基苯基膦)四溴双钯(Ⅱ)化合物，其中Pd采取平面四配位与溴形成[Pd2Br2]的四元环结构，配体(Amphos)和溴原子占据钯原子剩余的配位位点；所述(Amphos)代表二叔丁基-4-二甲氨基苯基膦；所述双(二叔丁基-4-二甲氨基苯基膦)四溴双钯(Ⅱ)化合物的结构式为：
2.一种根据权利要求1所述的双(二叔丁基-4-二甲氨基苯基膦)四溴双钯(Ⅱ)化合物的制备方法，其特征在于包括以下步骤：
S1，以PdBr2为钯源，加入四氢呋喃(THF)、二甲基亚砜(DMSO)或乙腈(CH3CN)中，在80℃下加热回流4小时，冷却至室温；
S2，在惰性气体气氛中，缓慢滴加二叔丁基-4-二甲氨基苯基膦于以上溶液中，搅拌反应2小时以析出橘红色沉淀；
S3，将S2获得的沉淀物过滤收集，用乙腈(CH3CN)洗涤三次，得到所述的双(二叔丁基-4-二甲氨基苯基膦)四溴双钯(Ⅱ)化合物。
3.根据权利要求2所述的双(二叔丁基-4-二甲氨基苯基膦)四溴双钯(Ⅱ)化合物的制备方法，其特征在于：
所述PdBr2、CH3CN、二叔丁基-4-二甲氨基苯基膦的加料比为1(克):200(mL):1(克)。
4.根据权利要求2或3所述的双(二叔丁基-4-二甲氨基苯基膦)四溴双钯(Ⅱ)化合物的制备方法，其特征在于：
所述惰性气体为氮气。
5.一种根据权利要求1所述的双(二叔丁基-4-二甲氨基苯基膦)四溴双钯(Ⅱ)化合物的用途，其特征在于：
替代[Pd(PPh3)4]和[Pd(Amphos)2Cl2]应用于Suzuki偶联反应。
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|---|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102203089A (zh) * | 2008-09-05 | 2011-09-28 | 伊兰医药品公司 | N-磺酰氨基多环吡唑基化合物 |
| CN108659054A (zh) * | 2018-07-16 | 2018-10-16 | 陕西瑞科新材料股份有限公司 | 一种二氯二叔丁基-4-二甲基氨基苯基膦钯的制备方法 |
-
2020
- 2020-08-20 CN CN202010844597.3A patent/CN111909217B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102203089A (zh) * | 2008-09-05 | 2011-09-28 | 伊兰医药品公司 | N-磺酰氨基多环吡唑基化合物 |
| CN108659054A (zh) * | 2018-07-16 | 2018-10-16 | 陕西瑞科新材料股份有限公司 | 一种二氯二叔丁基-4-二甲基氨基苯基膦钯的制备方法 |
Non-Patent Citations (3)
| Title |
|---|
| B. E. MANN等: "Preparative and Proton and Phosphorus-31 Nuclear Magnetic Resonance Studies on Palladium(II) Complexes with t-Butylphosphines", 《JOURNAL OF THE CHEMICAL SOCIETY》 * |
| D. F. GILL等,: "Transition Metal-Carbon Bonds. Part XXXIII. Internal Metallations of Secondary and Tertiary Carbon Atoms by Platinum(II) and Palladium(II)", 《JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS: INORGANIC CHEMISTRY》 * |
| RHETT C. SMITH等: "Suzuki reactions catalyzed by palladium complexes bearing the bulky (2,6-dimesitylphenyl)dimethylphosphine", 《TETRAHEDRON LETTERS》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN114805449B (zh) * | 2022-05-18 | 2023-11-14 | 云南贵金属实验室有限公司 | 一种水溶性Pd(II)配合物及其合成方法和作为催化前驱体的用途 |
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