N-heterocyclic carbene palladium complex crystal, synthetic method thereof, and application thereof in preparation of amide compounds

A technology for amide compounds and aniline compounds, which is applied in the field of azacarbene palladium complex crystals to achieve the effects of high electron affinity, large bond energy and increasing electron density

Active Publication Date: 2019-11-22
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Therefore, it is challenging to develop highly chemoselective aminocarbonylation reactions at mild temperatures.

Method used

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  • N-heterocyclic carbene palladium complex crystal, synthetic method thereof, and application thereof in preparation of amide compounds
  • N-heterocyclic carbene palladium complex crystal, synthetic method thereof, and application thereof in preparation of amide compounds
  • N-heterocyclic carbene palladium complex crystal, synthetic method thereof, and application thereof in preparation of amide compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Synthesis of the azacarbene palladium complex crystal A with the following structural formula

[0023]

[0024] With 367.19mg (1mmol) azacarbene ligand shown in formula I and 115.9mg (0.5mmol) Ag 2 O was dissolved in 5 mL of acetonitrile, and 259.43 mg (1 mmol) of Pd(CH 3 EN) 2 Cl 2 , stirred and reacted at room temperature for 1 hour, after the reaction was completed, assisted filtration with diatomaceous earth, and recrystallized with a mixture of acetonitrile and n-hexane with a volume ratio of 1:3 to obtain azacarbene palladium complex crystal A , the yield is 55%, and the X-ray single crystal structure is shown in figure 1 As shown, it belongs to the triclinic crystal system, the space group P-1, and the unit cell parameters are: α=75.1030(10), β=86.4900(10), γ=88.6250(10), Z=2, Pd01-Cl02=2.3156(6), Pd01-Cl03=2.3285(6), Pd01-N006=2.079(2), Pd01-C00B=1.934(3), N008-C00E=1.333(3), N008 -C00F=1.328(3), N009-C00E=1.333(3), N009-C00G=1.334(3), Cl02-Pd01-Cl0...

Embodiment 2

[0026] Synthesis of the azacarbene palladium complex crystal B with the following structural formula

[0027]

[0028] In this embodiment, the azacarbene ligand shown in formula I in Example 1 is replaced with the azacarbene ligand shown in formula II in equimolar form, and the other steps are the same as in Example 1 to obtain the azacarbene palladium complex B, which produces The ratio is 57%, and the X-ray single crystal structure diagram is as follows figure 2 As shown, it belongs to the monoclinic crystal system, the P21 / n space group, and the unit cell parameters are: α=90°, β=103.435(4)°, γ=90°, Z=4, N005-Pd01-Cl02=175.49(8), N00B-Pd01-Cl02=85.99(10), N00B-Pd01-N005=98.45(12), C00J-Pd01-Cl02=96.53(10), C00J- Pd01-N005 = 79.00 (13), C00J-Pd01-N00B = 177.01 (14). The NMR data of the complex crystal are: 1 H NMR (600MHz, CD 3 CN)δ7.85(d,J=2.3Hz,1H),7.23(d,J=2.3Hz,1H),4.20(s,6H),4.12(s,3H),1.97(s,3H),1.94 (dt,J=4.9,2.5Hz,5H). 13 C NMR (101MHz, DMSO) δ177.61(s),...

Embodiment 3

[0030]The following structural formula is prepared: N-phenylbenzamide

[0031]

[0032] To a 20 mL reaction tube, add 0.485 mg (0.001 mmol) azacarbene palladium complex crystal A, 112 μL (1 mmol) iodobenzene, 182 μL (1.5 mmol) aniline, 278 μL (2 mmol) triethylamine, 3 mL 1,4-dioxo Hexacyclic ring, and CO gas was introduced, and the reaction was stirred for 6 hours at a CO pressure of 3 atm and a temperature of 100 ° C. After the reaction was stopped, 15 mL of dichloromethane was added, and the dichloromethane was removed by rotary evaporation, and separated by a silica gel column (the eluent was The volume ratio of dichloromethane and sherwood oil is the mixed solution of 2:1), obtains N-phenylbenzamide, and its productive rate is 100%, and the spectral data of product is: 1 H NMR (600MHz, CDCl 3 )δ7.85(s,1H),7.81-7.76(m,2H),7.57(d,J=7.8Hz,2H),7.48-7.44(m,1H),7.39(t,J=7.6Hz,2H ),7.29(dd,J=10.8,5.0Hz,2H),7.07(t,J=7.4Hz,1H); 13 C NMR (151MHz, CDCl 3 )δ164.78(s), 136.92(s)...

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Abstract

The invention discloses an N-heterocyclic carbene palladium complex crystal, a synthetic method thereof and application thereof in preparation of amide compounds. The structural formula of the complexcrystal is shown in the specification, or the complex crystal is prepared from an N-heterocyclic carbene ligand, Pd(CH3CN)2Cl2 and Ag2O in acetonitrile serving as a solvent. The N-heterocyclic carbene palladium complex crystal is relatively stable, wherein the raw materials used in the synthesis method are cheap and easy to obtain, so that the synthetic method is simple, convenient and easy to implement is simple in post-treamtent and is high in yield; and the N-heterocyclic carbene palladium complex crystal is used for catalyzing carbonylation carbon-nitrogen bond coupling reaction to prepare amide compounds and is high in catalytic activity, easy to operate and high in atom economy.

Description

technical field [0001] The invention relates to an azacarbene palladium complex crystal and its application as a catalyst in the preparation of amide compounds. Background technique [0002] The formation of carbon-nitrogen bonds in amides is one of the most important reactions in organic chemistry. The special structure of amides exists in a series of drugs such as atorvastatin, mosapride, and imatinib, and is also an important cornerstone for the synthesis of various pesticides and color dyes. However, the traditional method of synthesizing amides is obtained through the coupling reaction of carboxylic acid derivatives and amines, which has very tedious operation steps and poor atom economy in the synthesis process. Therefore, there is a continuing interest in the continued development of new and improved synthetic methods for amides. Among the various methods for the synthesis of amides, the palladium-catalyzed aminocarbonylation of aryl halides is the most attractive m...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00B01J31/22C07C231/10C07C233/65C07C235/64C07C233/75C07C233/66
CPCC07F15/006B01J31/1805B01J31/181C07C231/10C07B2200/13B01J2531/824C07C233/65C07C235/64C07C233/75C07C233/66
Inventor 高子伟张刊文锐张伟强孙华明
Owner SHAANXI NORMAL UNIV
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