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Forcipate thioacid amide ligand, complex compound and application of sulfo-2, 6-pyridine diformamide framework

A technology of pyridinedicarboxamide and pincer thioamide, which is applied in the field of pincer thioamide ligands and their complexes, to achieve the effects of amplification reaction, good structural stability, and easy adjustment and modification

Inactive Publication Date: 2009-06-03
WUHAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are few reports on pincer thioamide nickel, palladium or platinum complexes as catalysts for cross-coupling reactions.

Method used

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  • Forcipate thioacid amide ligand, complex compound and application of sulfo-2, 6-pyridine diformamide framework
  • Forcipate thioacid amide ligand, complex compound and application of sulfo-2, 6-pyridine diformamide framework
  • Forcipate thioacid amide ligand, complex compound and application of sulfo-2, 6-pyridine diformamide framework

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Synthesis of thio-2,6-pyridinediformamide

[0040] Add 120mL of thionyl chloride into the drained 250mL three-necked flask, add 2,6-pyridinedicarboxylic acid powder (0.4mol, 66.81g) under nitrogen flow, stir evenly while adding, add 1ml N, N -Dimethylformamide catalyzed the reaction and heated to reflux; at the beginning of reflux, 2,6-pyridinedicarboxylic acid was not completely dissolved in thionyl chloride to form a white suspension. As the reaction progressed, a large amount of gas was generated and entered Exhaust gas treatment device, the product 2,6-pyridine diacid chloride can be completely dissolved, so when the solution becomes clear and no gas is generated, it indicates that the reaction is basically complete; vacuum distillation removes excess thionyl chloride to obtain a crude product that can be directly Put into the next step reaction.

[0041] In a 250mL round bottom flask, weigh 20.4g (0.10mol) of 2,6-pyridinedicarboxylic acid chloride, add 50mL of dichloro...

Embodiment 2

[0044] Synthesis of thio-2,6-pyridinedicarboxylic acid butylamide

[0045] In a 500mL round bottom flask, weigh 2,6-pyridinedicarbonyl chloride (0.15mol, 30.6g), add 100mL of acetonitrile, stir well, add 62.5mL of triethylamine (0.45mol, 45.5g), and then add n-butyl Amine 37mL (0.375mol, 27.4g), the reaction exotherms, and ice water is used for cooling. After the reaction is not exothermic, heat to make the reaction react at 50-60°C; point plate monitoring, when the reaction is complete, the system is spin-dried first, the obtained solid is ground, and then the volume ratio of ethanol and water in 100mL (3: Suspend in the mixed solution of 1), stir in a water bath at 50-60°C for 10-30 minutes, filter with suction, and wash once with cold ethanol to obtain 17.9 g of pure product 2,6-pyridinedicarboxylic acid butylamine, yield: 73 %.

[0046] Add 10.0g (0.036mol, 1eq) of 2,6-pyridinedicarboxylic acid butylamine weighed and 17.25g (0.0425mol,) of Lawesson's reagent into a 100mL Schle...

Embodiment 3

[0049] Synthesis of thio-2,6-pyridinedicarbonyl(2,4,6-trimethylaniline)amine

[0050] In a 250mL round-bottom flask, weigh 20.4g (0.1mol) of 2,6-pyridinedicarbonyl chloride, add 50mL of dichloromethane, stir well, add 30.3g (0.3mol) of triethylamine, and then add 2,4, 29.7 g (0.22 mol) of 6-trimethylaniline, the reaction exotherms, and ice water is used for cooling. When the reaction does not exotherm, the reaction is refluxed; monitoring by the dot plate, when the reaction is complete, the system is spin-dried first, the obtained solid is ground, and then suspended in a mixed solution of 70 mL (ethanol and water volume ratio 3: 1), Stir in a water bath at 50-60°C for 10-30 minutes, filter with suction, and wash once with cold ethanol to obtain 30.60g of pure 2,6-pyridinedicarbonyl (2,4,6-trimethylphenyl)amine, yield 76.2%.

[0051] Add 4.015g (0.01mol) of the weighed 2,6-pyridinedicarbonyl (2,4,6-trimethylphenyl)amine and 4.449g (0.011mol) of Lawesson's reagent to 50mL Schlenk un...

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Abstract

The invention relates to forcipate thioacid amide ligand of sulfo-2, 6-pyridine diformamide framework and a complex compound thereof, the constitutional formula thereof is as above, wherein, R in the formula is C2 to C8 alkyl, and phenyl-substituted alkyl or phenyl-substituted by alkoxy; and M is nickel, palladium or platinum. The ligand provided by the invention is non-phospine ligand and keeps stable against air and water, and lone pair electrons on nitrogen in the thioacid amide can adjust the electric property of sulfur, substitutional group on nitrogen can adjust the electron and the spatial configuration of the whole ligand; the ligand has the advantages of convenient compound, high total yield, and numerous compound. The complex compound provided by the invention has the advantages of high stability owing to the special forcipate structure, high catalytic activity during the catalytic reaction, wide application range, good selectivity and mild reaction condition, and is widely applicable to the cross coupled reaction of the transition metal catalyze, such as the Heck reaction and the like.

Description

Technical field [0001] The present invention relates to pincer-shaped thioamide ligands of thio-2,6-pyridinedicarboxamide skeleton and their complexes, their synthesis methods and their application in palladium-catalyzed cross-coupling reactions. Background technique [0002] Transition metal-catalyzed cross-coupling reactions are one of the important methods for the formation of carbon-carbon bonds. In the past thirty years, such reactions have been extensively studied and made great progress, as well as a large number of organic synthesis. Applications. In the coupling reaction, the catalyst plays a very important role. It plays a pivotal role in terms of productivity, selectivity, and compatibility. The catalyst is generally composed of a catalytic metal precursor and a ligand. The ligand can appropriately change the performance of the catalyst, amplify or expand a certain effect, and perform the coupling reaction more perfectly. The more commonly used ligands are generally ph...

Claims

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Application Information

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IPC IPC(8): C07D213/83C07F15/04C07F15/00B01J31/22B01J31/30
Inventor 雷爱文王海波刘婧
Owner WUHAN UNIV
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