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Palladium catalyst for catalyzing Suzuki coupling reaction, synthesis method, application and ligand

A technology of palladium catalyst and synthesis method, applied in the direction of physical/chemical process catalyst, organic compound/hydride/coordination complex catalyst, chemical instrument and method, etc., can solve the problems of oxidation and toluene toxicity, and reach the reaction temperature and time reduction, the effect of less alkali usage

Inactive Publication Date: 2012-10-24
SHANDONG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The traditional catalyst is Pd (PPh 3 ) 4 The most common, but the Pd in ​​the catalyst is zero-valent palladium, which is easily absorbed by O in the air 2 Oxidation, so anaerobic operation must be used
The solvent generally needs toluene with higher catalyst solubility, and toluene is more toxic

Method used

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  • Palladium catalyst for catalyzing Suzuki coupling reaction, synthesis method, application and ligand
  • Palladium catalyst for catalyzing Suzuki coupling reaction, synthesis method, application and ligand
  • Palladium catalyst for catalyzing Suzuki coupling reaction, synthesis method, application and ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] The synthesis route of the catalyst synthesized by the present invention is as follows:

[0049] 1. Preparation of Ligand L:

[0050]

[0051]Weigh 2.94g (10mmol) of intermediate A into a 100ml round bottom flask, add 20ml of thionyl chloride, and reflux until the system is clarified. First evaporate most of the thionyl chloride at normal pressure, then add two droppers of benzene, evaporate to dryness under reduced pressure, repeat three times, finally add two droppers of anhydrous ether, and evaporate to dryness under reduced pressure to obtain a yellow solid in a flask for later use. Intermediate B. Intermediate A References Sather, A.C., Berryman, O.B., Rebek, J.Jr.J.AM. Chem Soc, 2010, 132, 13572-13574; Kolotuchin, V.S., Thiessen, A.P., Fenlon, E.T., Wilson, R.S., Loweth, J.C., Zimmerman, C.S. Chem. Eur. J. 1999, 5, 2537-2547.

[0052]

[0053] Add 4.41g of 5-(4-pyridyl)tetrazole and 10ml of anhydrous pyridine to the prepared intermediate B, and react at 1...

experiment example 1

[0056] Experimental Example 1: PhBr and PhB(OH) 2 Reaction to form biphenyl

[0057] Add Ph-Br (10mmol), PhB (OH) to a 25ml single-necked round bottom flask 2 (12mmol), K 2 CO 3 (10mmol), catalyst 1mg (100ppm), H 2 O / EtOH 5ml (1 / 1), oil bath temperature control 60 ℃, constant temperature reaction 1h. Stop heating, add 5ml H to the system 2 O, extracted with 3 x 10 ml ethyl acetate, combined organic phases, MgSO 4 Dry, spin dry, and use Dichloromethane / Petroleun ether=1:1 column chromatography to obtain a white product with a yield of 95%. The H NMR of the product is as Figure 7 As shown, IR as Figure 8 shown.

[0058] Traditional Pd (PPh 3 ) 4 The amount of catalyst used in catalyzing this type of reaction is usually 1% to 5%. See references Castanet, A.S.; Colobert, F.; Schlama, T.Org.Lett.2000, 23, 3559-3561. 1 mg of new catalyst, the amount of Pd is 0.1 mg. while Pd (PPh 3 ) 4 The catalyst requires 115.6 mg based on 1%, and the amount of Pd is 10.6 mg.

experiment example 2

[0059] Experimental Example 2: PhI and PhB(OH) 2 Reaction to form biphenyl

[0060] Add Ph-I (10mmol), PhB (OH) to a 25ml single-necked round bottom flask 2 (12mmol), K 2 CO 3 (10mmol), catalyst 1mg (100ppm), H 2 O / EtOH 5ml (1 / 1), oil bath temperature control 60 ℃, constant temperature reaction 1h. Stop heating, add 5ml H to the system 2 O, extracted with 3 x 10 ml ethyl acetate, combined organic phases, MgSO 4 Dry, spin dry, and use Dichloromethane / Petroleun ether=1:1 column chromatography to obtain a white product with a yield of 96%. H NMR of the product as Figure 9 As shown, IR as Figure 10 shown.

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Abstract

The invention discloses a palladium catalyst for catalyzing a Suzuki coupling reaction, a synthesis method, application and a ligand. The chemical structural formula of the palladium catalyst is Pd6(L11)8(NO3)12. The synthesis method comprises the following steps: (A) heating 2,4,6-triethyl-1,3,5-trimesic acid and SOCl2 of a refluxing volume to carry out a refluxing reaction until the system is clear; (B) adding 5-(4-pyridyl) tetrazole to the reaction system, keeping the refluxing reaction for 2-3 hours in anhydrous pyridine, separating and purifying to obtain the ligand L; and (C) heating the ligand L and palladium nitrate in DMSO (dimethylsulfoxide) at the temperature of 60-70 DEG C for carrying out the refluxing reaction for 2-3 hours, separating and purifying to obtain the catalyst Pd6L8(NO3)12. The invention further provides the application of the palladium catalyst in catalyzing the Suzuki coupling reaction and the ligand. An oxygen-free operation is not needed for the novel palladium catalyst provided by the invention, reagents with larger toxicity, such as toluene, are avoided, the reaction temperature and the reaction time are greatly reduced and shortened, and the activity of the catalyst is higher. The invention is hopefully widely applied on the aspects of medicinal molecules requiring a Suzuki coupling technology and the cleaner production of the ligand.

Description

technical field [0001] The invention relates to a palladium catalyst for catalyzing Suzuki coupling reaction, a synthesis method, an application and a ligand. Background technique [0002] The Suzuki coupling reaction is an important reaction for the formation of carbon-carbon single bonds. The method is simple, easy to operate, high in yield, and the reagent used has little toxicity and less pollution, and is a relatively green reaction. This reaction has become a powerful method for the preparation of many pharmaceutical ligands. The traditional catalyst is Pd (PPh 3 ) 4 The most common, but the Pd in ​​the catalyst is zero-valent palladium, which is easily absorbed by O in the air 2 Oxidation, so anaerobic operation must be used. The solvent generally needs toluene with higher catalyst solubility, but toluene is more toxic. In addition, common catalysts for this reaction include Pd(PPh 3 ) 2 Cl 2 , Pd(OAc) 2 Wait. Contents of the invention [0003] The purpos...

Claims

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Application Information

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IPC IPC(8): B01J31/22C07F15/00C07B37/04C07C15/14C07C1/32C07C255/50C07C253/30C07C49/784C07C45/68C07C43/205C07C41/30C07D413/14
Inventor 董育斌赵朝委
Owner SHANDONG NORMAL UNIV
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