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Trinuclear n-heterocyclic carbene-palladium compound, synthetic method and application

A technology of nitrogen heterocyclic carbene and palladium compounds, which is applied in the synthesis and application of metal organic compounds, can solve the problems that have not been reported in the literature, and achieve the effects of simple and easy operation, high product yield and good catalytic effect

Active Publication Date: 2015-12-09
SHANGQIU NORMAL UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0008] Although nitrogen-heterocyclic carbene palladium compounds have attracted people's attention and achieved certain research results, tri-nuclear and multi-nuclear nitrogen-heterocyclic carbene palladium compounds and their applications have not been reported in the literature.
In addition, from the examples reported in the literature, we can see that the preparation of most of the dinuclear nitrogen heterocyclic carbene palladium compounds is completed step by step through further depolymerization of the carbene palladium dimer compound. There are relatively few reports on palladium compounds

Method used

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  • Trinuclear n-heterocyclic carbene-palladium compound, synthetic method and application
  • Trinuclear n-heterocyclic carbene-palladium compound, synthetic method and application
  • Trinuclear n-heterocyclic carbene-palladium compound, synthetic method and application

Examples

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Embodiment 1

[0038] Embodiment one: the preparation of trinuclear nitrogen heterocyclic carbene palladium compound I:

[0039] Tris[4-(pyridin-4-yl)phenyl]amine compound (47.6mg, 0.10mmol), 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (IPr.HCl ) (127.5mg, 0.30mmol), PdCl 2(53.2mg, 0.30mmol) and potassium carbonate (41.5mg, 0.30mmol) were added to a 25mL one-necked flask, then tetrahydrofuran (5mL) was added, and the reaction was stirred at 65°C under an argon atmosphere for 16h. The reaction was stopped, cooled to room temperature, concentrated, and separated by thin-layer chromatography to obtain compound I with a yield of 57%. The experimental data of this compound: 1 HNMR (400MHz, CDCl 3 ): δ8.53(d, J=6.5Hz, 2H, ArH), 7.49(t, J=7.7Hz, 2H, ArH), 7.37-7.34(m, 6H, ArH), 7.24(d, J=6.6 Hz,2H,ArH),7.13-7.09(m,4H,ArH),3.22-3.15(m,4H,CH(CH 3 ) 2 ), 1.49(d, J=6.5Hz, 12H, CH(CH 3 ) 2 ), 1.12(d, J=6.8Hz, 12H, CH(CH 3 ) 2 ). 13 CNMR (100MHz, CDCl 3 ): δ155.2, 151.4, 148.8, 148.0, ...

Embodiment 2

[0040] Embodiment two: the preparation of trinuclear nitrogen heterocyclic carbene palladium compound II:

[0041] Tris[4-(pyridin-4-yl)phenyl]amine compound (47.6mg, 0.10mmol), 1,3-bis(2,4,6-trimethylphenyl)imidazole chloride (IMes.HCl ) (102.1mg, 0.30mmol), PdCl 2 (53.2mg, 0.30mmol) and potassium carbonate (41.5mg, 0.30mmol) were added to a 25mL one-necked flask, then tetrahydrofuran (5mL) was added, and the reaction was stirred at 75°C under an argon atmosphere for 14h. The reaction was stopped, cooled to room temperature, concentrated, and separated by thin-layer chromatography to obtain compound II with a yield of 50%. The experimental data of this compound: 1 HNMR (400MHz, CDCl 3 ): δ8.50(d, J=6.4Hz, 2H, ArH), 7.39(d, J=8.6Hz, 2H, ArH), 7.24(d, J=6.6Hz, 2H, ArH), 7.12-7.05( m,8H,ArH),2.37(s,18H,CH 3 ). 13 CNMR (100MHz, CDCl 3 ): δ153.0, 151.5, 148.8, 148.0, 139.2, 136.4, 135.1, 129.3, 128.2, 124.7, 124.2, 121.1, 21.2, 19.2.

Embodiment 3

[0042] Embodiment three: the preparation of trinuclear nitrogen heterocyclic carbene palladium compound III:

[0043] Tris[4-(pyridin-4-yl)phenyl]amine compound (47.6mg, 0.10mmol), 1,3-dibenzyl benzimidazolium salt (100.5mg, 0.30mmol), PdBr 2 (79.9mg, 0.30mmol) and potassium carbonate (31.8mg, 0.30mmol) were added to a 25mL one-necked flask, then tetrahydrofuran (5mL) was added, and the reaction was stirred at 80°C for 12h under an argon atmosphere. The reaction was stopped, cooled to room temperature, concentrated, and separated by thin-layer chromatography to obtain compound III with a yield of 50%. The experimental data of this compound: 1 HNMR (400MHz, CDCl 3 ): δ8.99(d, J=5.3Hz, 2H, ArH), 7.64-7.51(m, 8H, ArH), 7.40-7.24(m, 8H, ArH), 7.10-7.08(m, 4H, ArH) ,6.28(s,4H,CH 2 ). 13 CNMR (100MHz, CDCl 3 ): δ165.0, 151.3, 149.4, 148.3, 135.1, 134.6, 131.7, 128.9, 128.4, 128.2, 128.0, 124.9, 123.3, 121.6, 111.5, 53.2.

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Abstract

The invention provides a trinuclear n-heterocyclic carbene-palladium compound, a synthetic method and an application of the trinuclear n-heterocyclic carbene-palladium compound in catalyzing a Suzuki coupled reaction and belongs to the field of synthesis of organic compounds. The compound has the general formula in the specification, wherein R represents 2,6-diisopropyl or 2,4,6-trimethyl; R1 represents isopropyl or benzyl; X represents chlorine atoms and bromine atoms. A series of trinuclear n-heterocyclic carbene-palladium compounds are obtained through one-step reaction and synthesis of raw materials of nitrogen-containing heterocyclic compounds, carbene salt, palladium sources and the like, the operation is simple, convenient and easy to implement, the product yield is high, and a new way for synthesizing the trinuclear n-heterocyclic carbene-palladium compound is provided. A novel metal catalyst is provided for formation of C-C bonds by means of the compound, few catalysts are used when the compound is used for catalyzing the Suzuki coupled reaction of chlorinated aromatic hydrocarbon and arylboronic acids, alkaline which is cheap and easy to obtain is used, water is used as a reaction solvent, and the catalytic effect is better.

Description

technical field [0001] The invention belongs to the technical field of synthesis and application of metal-organic compounds, and relates to a trinuclear nitrogen-heterocyclic carbene palladium compound, a preparation method thereof and its application in catalyzing the Suzuki coupling reaction of chlorinated aromatic hydrocarbons and arylboronic acids. Background technique [0002] Metallic palladium-catalyzed reactions occupy a pivotal position in modern organic synthetic chemistry and industrial catalysis, and have attracted widespread interest from chemists. In 1995, the Herrmann research group (references Angew.Chem.Int.Ed.1995,34,2371.) reported for the first time that two carbene palladium catalysts realized the combination of nitrogen heterocyclic carbene and metal palladium, and applied to Heck and Suzuki couple The combined reaction has a better catalytic effect, and since then it has opened up a precedent for using nitrogen heterocyclic carbene palladium compounds ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00B01J31/22C07C41/30C07C43/205C07C43/225C07C205/06C07C201/12
Inventor 王涛许凯刘澜涛赵文献刘双李峰孟团结谢焕平
Owner SHANGQIU NORMAL UNIVERSITY