Method for synthesizing acridone derivatives by means of palladium-copper co-catalysis

A copper co-catalyzed synthesis of acridone and derivatives, which is applied in chemical instruments and methods, chemical/physical processes, physical/chemical process catalysts, etc., achieving the effects of large application potential, high atom economy, and simple preparation methods

Active Publication Date: 2016-12-07
SUQIAN XINYA TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

It is worth noting that the direct construction of ketones by C-H / C-H oxidative carbonylation is undoubtedly the most convenient and effective method, but it is also extremely challenging.

Method used

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  • Method for synthesizing acridone derivatives by means of palladium-copper co-catalysis
  • Method for synthesizing acridone derivatives by means of palladium-copper co-catalysis
  • Method for synthesizing acridone derivatives by means of palladium-copper co-catalysis

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Palladium chloride (0.025mmol), copper pivalate (0.05mmol), and diphenylamine (0.25mmol) were added to a dry Schlenk reaction tube, and the system was replaced three times under an atmospheric pressure of carbon monoxide to obtain a pure carbon monoxide atmosphere. Then add solvent anhydrous dimethyl sulfoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulfoxide (2.0mL) successively, stop the reaction after reacting at 100°C for 24 hours, cool to room temperature, and Ethyl acetate was added to the reaction system to quench the reaction, and saturated potassium carbonate solution (30.0 mL) was added, extracted with dichloromethane (20×3), separated by column chromatography to obtain an acridone derivative, and the separation yield reached 85%. The NMR characterization data are as follows:

[0020]

[0021] NMR data: 1 H NMR (400MHz, DMSO-d 6 )δ=11.77(s,1H),8.25(d,J=7.7,2H),7.74(t,J=7.1,2H),7.56(d,J=8.1,2H),7.26(t,J=7.1 ,2H). 13 C NMR (101MHz, DMSO-d ...

Embodiment 2

[0023] Palladium chloride (0.025mmol), copper pivalate (0.05mmol) and p-methyldiphenylamine (0.25mmol) were added to a dry Schlenk reaction tube, and the system was replaced three times under an atmospheric pressure of carbon monoxide. Then add solvent anhydrous dimethyl sulfoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulfoxide (2.0mL) successively, stop the reaction after reacting at 100°C for 24 hours, cool to room temperature, and Dichloromethane was added to the reaction system for dilution, and saturated potassium carbonate solution (30.0mL) was added, extracted with dichloromethane (20×3), and separated by column chromatography to obtain acridone derivatives with a separation yield of 79%. NMR The characterization data are as follows:

[0024]

[0025] NMR data: 1 H NMR (400MHz, DMSO-d 6 )δ=11.70(s,1H),8.22(d,J=8.1,1H),8.02(s,1H),7.71(t,J=7.7,1H),7.59–7.44(m,3H),7.23( t,J=7.5,1H),2.41(s,3H). 13 C NMR (101MHz, DMSO-d 6 ) δ = 177.0, 141.2, 139.4, ...

Embodiment 3

[0027] Palladium chloride (0.025mmol), copper pivalate (0.05mmol) and p-methoxydiphenylamine (0.25mmol) were added into a dry Schlenk reaction tube, and the system was replaced three times under an atmospheric pressure of carbon monoxide. Then add solvent anhydrous dimethyl sulfoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulfoxide (2.0mL) successively, stop the reaction after reacting at 100°C for 24 hours, cool to room temperature, and Ethyl acetate was added to the reaction system to quench the reaction, and saturated potassium carbonate solution (30.0 mL) was added, extracted with dichloromethane (20×3), separated by column chromatography to obtain an acridone derivative, and the separation yield reached 81%. The NMR characterization data are as follows:

[0028]

[0029] NMR data: 1 H NMR (400MHz, DMSO-d 6 )δ=11.78(s,1H),8.24(d,J=8.1,1H),7.71(t,J=7.7,1H),7.64(d,J=2.9,1H),7.55(d,J=3.1 ,1H),7.53(d,J=2.2,1H),7.42(dd,J=9.0,3.0,1H),7.24(t,J=7.5,1H),3.87(...

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Abstract

The invention discloses a method for synthesizing acridone derivatives by means of palladium-copper co-catalysis. The method comprises the steps that on the condition that palladium chloride, copper pivalate and di-tert-butyl peroxide or oxygen co-exist, diphenylamine compounds including symmetric diphenylamine and asymmetric diphenylamine are dissolved in an anhydrous organic solvent, all the materials are mixed to be uniform, a reaction is conducted for 20 h to 30 h under the condition of 80 DEG C to 120 DEG C in a carbon monoxide atmosphere, separation and purification are conducted, and the acridone derivatives can be obtained. According to the method for synthesizing the acridone derivatives by means of palladium-copper co-catalysis, the preparation method is simple, the diphenylamine compounds which are simple and easy to obtain are used as the raw materials, and the acridone derivatives are directly constructed through C-H / C-H oxidative carbonylation; the preparation condition is mild, and the target product can be obtained in a high-selectivity mode at 80 DEG C to 120 DEG C; the acridone derivatives have good substrate applicability, the range of substrates is greatly expanded, and the acridone derivatives have a great application prospect in biological medicine and materials and the like.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a method for synthesizing acridone derivatives by palladium-copper co-catalysis. Background technique [0002] Acridone compounds are a very important class of nitrogen-containing molecular skeletons, which have been widely used in research fields such as medicine, dyes, and biological materials, and play a pivotal role. Synthesizing such compounds through simple and effective methods can effectively promote the development of the fields of medicine and materials. The traditional synthetic method usually promotes the cyclization of N-phenylanthranilic acid compounds or the intramolecular nucleophilic substitution of N-phenyl-2-halogenated aniline compounds by acid, but the reaction conditions are relatively harsh and the initial Raw materials are difficult to prepare. With the development of transition metal-catalyzed aromatic hydrocarbon C-H bond activation methodo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D219/06C07D221/18C07D219/08B01J31/30
CPCB01J31/30C07D219/06C07D219/08C07D221/18
Inventor 雷爱文文江伟
Owner SUQIAN XINYA TECH
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