Forcipate thioacid amide ligand, complex compound thereof and application of thioisophthalamide framework

Abstract

The invention relates to the forcipate thioacid amide ligand of thioisophthalamide framework and a complex compound thereof, the constitutional formula thereof is the formula 1 and the formula 2, wherein, R in the formula is propyl, sec-butyl, tert-butyl group, C5 to C8 alkyl, and phenyl-substituted alkyl or phenyl-substituted 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, so that the condition during the catalytic reaction can not be extra critical like that during the catalytic reaction of phosphine ligand, and lone pair electrons on the nitrogen in the thioacid amide can adjust the electric property of the sulfur, a substitutional group on the nitrogen can adjust and control the electron and the spatial configuration of the whole ligand; particularly 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.

Description

technical field

[0001] The present invention relates to clamp-shaped thioamide ligands of thioisophthalamide skeleton and nickel, palladium or platinum complexes thereof, their synthesis method and use and their application in catalytic cross-coupling reaction. Background technique

[0002] Transition metal-catalyzed cross-coupling reactions are one of the important methods for forming carbon-carbon bonds. In the past three decades, such reactions have been extensively studied and made great progress, and have also received a lot of attention in organic synthesis. Applications. In the coupling reaction, the catalyst plays a very important role. It plays a pivotal role in yield, selectivity, compatibility and so on. Catalysts are generally composed of catalytic metal precursors and ligands. Ligands 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 ar...

Examples

Embodiment 1

[0031] Synthesis of Thioisophthalamide

[0032] In a 100mL three-necked flask pumped by nitrogen, add 40mL SOCl 2 , Add isophthalic acid powder (0.4mol, 66.81g) under the condition of flowing nitrogen, stir evenly while adding, add 0.5ml DMF to catalyze the reaction, heat to reflux. At the beginning of reflux, isophthalic acid is incompletely dissolved in thionyl chloride to form a white suspension. As the reaction progresses, a large amount of gas is generated and enters the tail gas treatment device. The product acid chloride can be completely dissolved, so when the solution becomes When it is clear and no gas is produced, it indicates that the reaction is basically completed; the excess thionyl chloride is evaporated by vacuum distillation to obtain a crude product that can be directly put into the next step reaction.

[0033] In a 1000mL round bottom flask, weigh 75.11g (0.37mol) of isophthaloyl chloride, add 300mL of acetonitrile, stir well, add Et 3 N 111.2g (1.11mol),...

Embodiment 2

[0036] Preparation of Thioisophthaloyl Octylamide and Its Palladium Complex

[0037] In a 500mL round bottom flask, weigh isophthaloyl chloride (0.15mol, 30.6g), add acetonitrile 100mL, stir well, add Et 3 N 62.5mL (0.45mol, 45.5g), then add n-octylamine 48.47 (0.375mol, 27.4g), the reaction is exothermic, use ice water to cool, when the reaction is not exothermic, heat up to 55°C for reaction; spot plate Monitor, when the reaction is complete, spin the system dry first, grind the obtained solid finely, then suspend in 100mL ethanol and water mixed solvent with a volume ratio of 1:3, stir in a water bath at 50-60°C for 10-30 minutes, and filter with suction , washed once with cold ethanol to obtain 48.38 g of pure product octyl isophthalamide, yield: 83%.

[0038]Add 13.98 g (0.036 mol) of isophthalamide octylamide and 17.25 g (0.0425 mol) of Lawesson’s reagent into a 100 mL Schlenk bottle under nitrogen, add 50 mL of freshly distilled toluene, heat to reflux, and put The mo...

Embodiment 3

[0041] Synthesis of Thioisophthaloyl (2,4,6-Trimethylphenyl)amine

[0042] In a 250mL round bottom flask, weigh 14.59g (0.072mol) of isophthaloyl chloride, add 100mL of acetonitrile, stir well, add Et 3 N 21.80g (0.216mol), then slowly add 21.36g (0.158mol) of amine, the reaction is exothermic, use ice water to cool, when the reaction is not exothermic, heat up to 55°C for reaction; spot plate monitoring, when the reaction is complete , spin the system to dry first, grind the obtained solid finely, then suspend in 40mL ethanol and water mixed solvent with a volume ratio of 1:3, stir in a water bath at 50-60°C for 10-30 minutes, filter with suction, and wash once with cold ethanol , 22.89 g of the pure product isophthaloyl (2,4,6-trimethylphenyl)amine was obtained, and the yield was 80.0%.

[0043] Add 4.0 g (0.010 mol) of isophthaloyl (2,4,6-trimethylphenyl) amine and 4.44 g (0.128 mol) of Lawesson's reagent into a 50 mL Schlenk bottle under a nitrogen atmosphere. Add 15mL o...

technical field

[0001] The present invention relates to clamp-shaped thioamide ligands of thioisophthalamide skeleton and nickel, palladium or platinum complexes thereof, their synthesis method and use and their application in catalytic cross-coupling reaction. Background technique

[0002] Transition metal-catalyzed cross-coupling reactions are one of the important methods for forming carbon-carbon bonds. In the past three decades, such reactions have been extensively studied and made great progress, and have also received a lot of attention in organic synthesis. Applications. In the coupling reaction, the catalyst plays a very important role. It plays a pivotal role in yield, selectivity, compatibility and so on. Catalysts are generally composed of catalytic metal precursors and ligands. Ligands 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 ar...

Examples

Embodiment 1

[0031] Synthesis of Thioisophthalamide

[0032] In a 100mL three-necked flask pumped by nitrogen, add 40mL SOCl 2 , Add isophthalic acid powder (0.4mol, 66.81g) under the condition of flowing nitrogen, stir evenly while adding, add 0.5ml DMF to catalyze the reaction, heat to reflux. At the beginning of reflux, isophthalic acid is incompletely dissolved in thionyl chloride to form a white suspension. As the reaction progresses, a large amount of gas is generated and enters the tail gas treatment device. The product acid chloride can be completely dissolved, so when the solution becomes When it is clear and no gas is produced, it indicates that the reaction is basically completed; the excess thionyl chloride is evaporated by vacuum distillation to obtain a crude product that can be directly put into the next step reaction.

[0033] In a 1000mL round bottom flask, weigh 75.11g (0.37mol) of isophthaloyl chloride, add 300mL of acetonitrile, stir well, add Et 3 N 111.2g (1.11mol),...

Embodiment 2

[0036] Preparation of Thioisophthaloyl Octylamide and Its Palladium Complex

[0037] In a 500mL round bottom flask, weigh isophthaloyl chloride (0.15mol, 30.6g), add acetonitrile 100mL, stir well, add Et 3 N 62.5mL (0.45mol, 45.5g), then add n-octylamine 48.47 (0.375mol, 27.4g), the reaction is exothermic, use ice water to cool, when the reaction is not exothermic, heat up to 55°C for reaction; spot plate Monitor, when the reaction is complete, spin the system dry first, grind the obtained solid finely, then suspend in 100mL ethanol and water mixed solvent with a volume ratio of 1:3, stir in a water bath at 50-60°C for 10-30 minutes, and filter with suction , washed once with cold ethanol to obtain 48.38 g of pure product octyl isophthalamide, yield: 83%.

[0038]Add 13.98 g (0.036 mol) of isophthalamide octylamide and 17.25 g (0.0425 mol) of Lawesson’s reagent into a 100 mL Schlenk bottle under nitrogen, add 50 mL of freshly distilled toluene, heat to reflux, and put The mo...

Embodiment 3

[0041] Synthesis of Thioisophthaloyl (2,4,6-Trimethylphenyl)amine

[0042] In a 250mL round bottom flask, weigh 14.59g (0.072mol) of isophthaloyl chloride, add 100mL of acetonitrile, stir well, add Et 3 N 21.80g (0.216mol), then slowly add 21.36g (0.158mol) of amine, the reaction is exothermic, use ice water to cool, when the reaction is not exothermic, heat up to 55°C for reaction; spot plate monitoring, when the reaction is complete , spin the system to dry first, grind the obtained solid finely, then suspend in 40mL ethanol and water mixed solvent with a volume ratio of 1:3, stir in a water bath at 50-60°C for 10-30 minutes, filter with suction, and wash once with cold ethanol , 22.89 g of the pure product isophthaloyl (2,4,6-trimethylphenyl)amine was obtained, and the yield was 80.0%.

[0043] Add 4.0 g (0.010 mol) of isophthaloyl (2,4,6-trimethylphenyl) amine and 4.44 g (0.128 mol) of Lawesson's reagent into a 50 mL Schlenk bottle under a nitrogen atmosphere. Add 15mL o...

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