CN106187890A - A kind of method utilizing palladium copper to catalyze and synthesize acridone derivatives altogether - Google Patents

A kind of method utilizing palladium copper to catalyze and synthesize acridone derivatives altogether Download PDF

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CN106187890A
CN106187890A CN201610541378.1A CN201610541378A CN106187890A CN 106187890 A CN106187890 A CN 106187890A CN 201610541378 A CN201610541378 A CN 201610541378A CN 106187890 A CN106187890 A CN 106187890A
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diphenylamines
copper
acridone derivatives
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synthesize
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CN106187890B (en
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雷爱文
文江伟
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SUQIAN XINYA TECHNOLOGY Co.,Ltd.
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Wuhan University WHU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C07D219/06—Oxygen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30—Halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C07D219/08—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/18—Ring systems of four or more rings

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Abstract

The invention discloses a kind of method utilizing palladium copper to catalyze and synthesize acridone derivatives altogether, under conditions of Palladous chloride., pivalic acid copper and di-t-butyl peroxide or oxygen exist jointly, diphenylamine compound (including symmetrical and asymmetric diphenylamines) is dissolved in anhydrous organic solvent, mix homogeneously, then in carbon monoxide atmosphere, react 20 30 hours under the conditions of 80 120 DEG C, isolated and purified, acridone derivatives.Preparation method of the present invention is simple, and using diphenylamine compound simple and easy to get is raw material, by C H/C H oxidative carbonylation direct construction acridone derivatives；Its preparation condition is gentle, just can obtain target product by highly selective at 80 120 DEG C；And the present invention has good substrate applicability, greatly expand the scope of substrate, had great application prospect at the aspect such as biological medicine, material.

Description

A kind of method utilizing palladium-copper to catalyze and synthesize acridone derivatives altogether
Technical field
The invention belongs to organic synthesis field, be specifically related to a kind of utilize palladium-copper to catalyze and synthesize acridone derivatives altogether Method.
Background technology
Acridones compound is a very important nitrogenous molecular skeleton of class, has been widely deployed in medicine, dyestuff And in the research field such as biomaterial, there is its very important effect.This kind ofization is synthesized by simple effective method Compound can promote the development of medicine, Material Field effectively.Typically by acid, traditional synthetic method promotes that N-phenyl is adjacent The cyclisation of aminobenzoic acid compounds or N-phenyl-2-halogeno-benzene aminated compounds internal nucleophilic substitution, but reaction condition Relatively harshness, and initiation material is difficult to prepare.Along with the development of transition metal-catalyzed arene C-H bonds activation method, closely Nian Lai, the research of double c h bonds activation receives much concern.It should be noted that by C-H/C-H oxidative carbonylation direct construction ketone Compound is undoubtedly method the easiest, effective, but is also great challenge simultaneously.Therefore, the present invention is at transition metal Under catalytic action, with diphenylamine compound as raw material, it is a kind of by oxidative carbonylation direct construction acridones compound Simply, economic synthetic method.
Summary of the invention
For solving above technical problem, the present invention is that acridone derivatives provides a kind of palladium, copper is catalyzed altogether, reaction condition Gentleness and the synthetic method of wide application range of substrates.
The technical solution adopted in the present invention particularly as follows:
A kind of method utilizing palladium-copper to catalyze and synthesize acridone derivatives altogether, comprises the following steps: first by Palladous chloride., Pivalic acid copper and diphenylamine compound together add in dry reactor, then the atmosphere in reactor are replaced as an oxygen Change carbon, add anhydrous organic solvent, in reactant liquor, then add oxidant, described diphenylamine compound, Palladous chloride., The mol ratio of pivalic acid copper is 0.1-1.0:0.3-3.0:0.01-0.1:0.02-0.2, and described oxidant is peroxidating two uncle Butyl (DTBP) or oxygen (O2)；Then react 20-30 hour under the conditions of 80-120 DEG C, purification, obtain acridone derivatives.
Described diphenylamine compound be diphenylamines, to methyldiphenylamine, di-p-methoxy-diphenylamine, to ethoxy diphenyl Amine, to tert-butyl diphenylamine, to trifluoromethyl diphenylamines, to fluorine diphenylamines, p-dichlorobenzene amine, to bromine diphenylamines, 4,4 '-diformazan Base diphenylamines, 3,5-dimethyl diphenylamines, 3,5-difluorodiphenyl amine, 3-chloro-4-methyldiphenylamine, adjacent methyldiphenylamine, 2,2- One in dinaphthylamine.
Preferably:
Described organic solvent is dimethyl sulfoxide.
The mol ratio of Palladous chloride. and pivalic acid copper is 1:2.
The mol ratio of diphenylamine compound and oxidant is 1:3.
The present invention utilizes DTBP or O2As oxidant, under conditions of catalytic amount palladium, copper are co-catalysis agent, with hexichol Aminated compounds (including asymmetric and symmetrical diphenylamines) is raw material, by C-H/C-H oxidative carbonylation direct construction acridone Compounds, for the synthesis of acridones compound provide a kind of raw material be easy to get, simple to operate, economic method.
The present invention has the following advantages and beneficial effect:
1, preparation method of the present invention is simple, uses raw material diphenylamine compound simple and easy to get to be aoxidized by C-H/C-H Carbonylation one step builds acridone derivatives, has the advantage that Atom economy is high.
2, preparation condition of the present invention is gentle, just can obtain target product by highly selective at 80-120 DEG C.
3, the present invention has good substrate applicability, has greatly expanded the scope of substrate, consequently facilitating preferably should With.
4, preparation method of the present invention is by laboratory amplification test, can meet the extensive of the industry such as medicine, material Application and exploitation.
5, the present invention has the biggest application potential at aspects such as biological medicine synthesis, fluorescent materials.
Detailed description of the invention
The following examples are in order to make those of ordinary skill in the art be more clearly understood that the present invention, but never in any form Limit the present invention.The present invention is raw materials used is all known compound, can be buied by market or use synthesis side known in the art Method synthesizes.Embodiment 1
Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), hexichol is added in dry Schlenk reaction tube Amine (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure, to obtain pure carbon monoxide atmosphere Enclose.Then solvent anhydrous dimethyl sulphoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide it are sequentially added into (2.0mL), stopped reaction after reacting 24 hours at 100 DEG C, it is cooled to room temperature, in reaction system, adds ethyl acetate cancellation anti- Should, adding unsaturated carbonate potassium solution (30.0mL), extract (20 × 3) with dichloromethane, column chromatography for separation obtains acridone and derives Thing, separation yield reaches 85%, and it is as follows that nuclear-magnetism characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) 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).13C NMR(101MHz,DMSO-d6) δ= 177.2,141.3,133.9,126.5,121.5,120.9,117.8。
Embodiment 2
In dry Schlenk reaction tube add Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), to first Base diphenylamines (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then solvent it is sequentially added into Anhydrous dimethyl sulphoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL), react 24 at 100 DEG C Stopped reaction after hour, is cooled to room temperature, adds dichloromethane and is diluted, add unsaturated carbonate potassium solution in reaction system (30.0mL), extracting (20 × 3) with dichloromethane, column chromatography for separation obtains acridone derivatives, and separation yield reaches 79%, core It is as follows that magnetic characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) 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).13C NMR (101MHz,DMSO-d6) δ=177.0,141.2,139.4,135.4,133.7,130.6,126.5,125.5,121.2, 120.8,120.8,117.8,117.7,21.1。
Embodiment 3
In dry Schlenk reaction tube add Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), to first Epoxide diphenylamines (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then it is sequentially added into molten Agent anhydrous dimethyl sulphoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL), 100 DEG C of reactions Stopped reaction after 24 hours, is cooled to room temperature, adds ethyl acetate cancellation reaction, add saturated potassium carbonate molten in reaction system Liquid (30.0mL), extracts (20 × 3) with dichloromethane, and column chromatography for separation obtains acridone derivatives, and separation yield reaches 81%, It is as follows that nuclear-magnetism characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) 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 (s, 3H).13C NMR(101MHz,DMSO-d6) δ=181.3, 159.2,145.7,140.9,138.3,131.1,129.5,126.2,125.9,124.8,124.4,122.5,110.0,60.6。
Embodiment 4
In dry Schlenk reaction tube add Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), to second Epoxide diphenylamines (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then it is sequentially added into molten Agent anhydrous dimethyl sulphoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL), 100 DEG C of reactions Stopped reaction after 24 hours, is cooled to room temperature, adds ethyl acetate cancellation reaction, add saturated potassium carbonate molten in reaction system Liquid (30.0mL), extracts (20 × 3) with dichloromethane, and column chromatography for separation obtains acridone derivatives, and separation yield reaches 76%, It is as follows that nuclear-magnetism characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=11.77 (s, 1H), 8.24 (d, J=8.1,1H), 7.71 (t, J=7.6,1H), 7.62 (d, J=2.9,1H), 7.53 (d, J=9.0,2H), 7.40 (dd, J=9.0,2.9,1H), 7.24 (t, J=7.5,1H), 4.11 (q, J=6.9,2H), 1.38 (t, J=6.9,3H).13C NMR(101MHz,DMSO-d6) δ= 176.6,153.6,140.9,136.1,133.5,126.4,125.0,121.4,121.2,120.1,119.6,117.8, 105.9,63.8,15.1.HRMS (EI) Theoretical Calculation C15H13NO2[M+H]+:240.1019；Discovery value: 240.1018.
Embodiment 5
In dry Schlenk reaction tube add Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), to uncle Butyl diphenylamines (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then it is sequentially added into molten Agent anhydrous dimethyl sulphoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL), 100 DEG C of reactions Stopped reaction after 24 hours, is cooled to room temperature, adds ethyl acetate cancellation reaction, add saturated potassium carbonate molten in reaction system Liquid (30.0mL), extracts (20 × 3) with dichloromethane, and column chromatography for separation obtains acridone derivatives, and separation yield reaches 75%, It is as follows that nuclear-magnetism characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=11.75 (s, 1H), 8.25 (d, J=8.1,1H), 8.20 (d, J=2.3,1H), 7.86 (dd, J=8.8,2.4,1H), 7.72 (t, J=7.6,1H), 7.58 7.49 (m, 2H), 7.24 (t, J=7.5,1H), 1.36 (s, 9H).13C NMR(101MHz,DMSO-d6) δ=181.9,148.5,145.9,144.2, 138.4,136.9,131.3,126.0,125.6,125.1,122.5,122.4,39.5,36.3。
Embodiment 6
In dry Schlenk reaction tube add Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), to three Methyl fluoride diphenylamines (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then it is sequentially added into Solvent anhydrous dimethyl sulphoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL), anti-at 100 DEG C Answer stopped reaction after 24 hours, be cooled to room temperature, in reaction system, add ethyl acetate cancellation reaction, add saturated potassium carbonate Solution (30.0mL), extracts (20 × 3) with dichloromethane, and column chromatography for separation obtains acridone derivatives, and separation yield reaches 62%, it is as follows that nuclear-magnetism characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=12.18 (s, 1H), 8.49 (s, 1H), 8.26 (d, J= 8.1,1H), 8.02 (dd, J=8.8,1.7,1H), 7.82 (t, J=7.7,1H), 7.73 (d, J=8.8,1H), 7.60 (d, J= 8.3,1H), 7.35 (t, J=7.5,1H).13C NMR(101MHz,DMSO-d6) δ=176.8,143.4,141.3,134.7, 129.7 (d, J=35.5), 126.5,124.2 (dd, J=60.7,1.5), 123.5,122.6,121.2,119.9,119.4, 118.2。
Embodiment 7
In dry Schlenk reaction tube add Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), to fluorine Diphenylamines (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then be sequentially added into solvent without Water dimethyl sulfoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL) are little 100 DEG C of reactions 24 Stopped reaction time after, is cooled to room temperature, adds ethyl acetate cancellation reaction, add unsaturated carbonate potassium solution in reaction system (30.0mL), extracting (20 × 3) with dichloromethane, column chromatography for separation obtains acridone derivatives, and separation yield reaches 80%, core It is as follows that magnetic characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=11.91 (s, 1H), 8.22 (d, J=7.7,1H), 7.87 (dd, J=9.3,2.7,1H), 7.74 (t, J=7.6,1H), 7.69 7.57 (m, 2H), 7.54 (d, J=8.3,1H), 7.27 (t, J=7.4,1H).13C NMR(101MHz,DMSO-d6) δ=176.6,158.5,156.1,141.2,138.1,134.1, (d, J=6.5), 126.3,122.9,121.7,121.4 120.4 (d, J=7.8), 117.9,110.2.
Embodiment 8
In dry Schlenk reaction tube add Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), to chlorine Diphenylamines (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then be sequentially added into solvent without Water dimethyl sulfoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL) are little 100 DEG C of reactions 24 Stopped reaction time after, is cooled to room temperature, adds ethyl acetate cancellation reaction, add unsaturated carbonate potassium solution in reaction system (30.0mL), extracting (20 × 3) with dichloromethane, column chromatography for separation obtains acridone derivatives, and separation yield reaches 78%, core It is as follows that magnetic characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=11.97 (s, 1H), 8.23 (d, J=8.1,1H), 8.15 (d, J=2.5,1H), 7.76 (dd, J=6.9,1.9,2H), 7.57 (dd, J=14.5,8.6,2H), 7.30 (t, J=7.5, 1H).13C NMR(101MHz,DMSO-d6) δ=176.2,141.2,139.9,134.3,133.9,126.5,125.9,125.2, 122.0,121.7,120.7,120.3,118.0。
Embodiment 9
In dry Schlenk reaction tube add Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), to bromine Diphenylamines (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then be sequentially added into solvent without Water dimethyl sulfoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL) are little 100 DEG C of reactions 24 Stopped reaction time after, is cooled to room temperature, adds ethyl acetate cancellation reaction, add unsaturated carbonate potassium solution in reaction system (30.0mL), extracting (20 × 3) with dichloromethane, column chromatography for separation obtains acridone derivatives, and separation yield reaches 67%, core It is as follows that magnetic characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=11.96 (s, 1H), 8.29 (s, 1H), 8.22 (d, J= 7.9,1H), 7.85 (d, J=8.8,1H), 7.76 (t, J=7.5,1H), 7.53 (t, J=9.0,2H), 7.28 (t, J=7.4, 1H).13C NMR(101MHz,DMSO-d6) δ=176.1,141.2,140.2,136.5,134.4,130.1,128.4,126.5, 122.1,120.8,120.5,118.0,113.6。
Embodiment 10
In dry Schlenk reaction tube add Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), 4,4 '- Dimethyl diphenylamines (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then it is sequentially added into Solvent anhydrous dimethyl sulphoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL), anti-at 100 DEG C Answer stopped reaction after 24 hours, be cooled to room temperature, in reaction system, add ethyl acetate cancellation reaction, add saturated potassium carbonate Solution (30.0mL), extracts (20 × 3) with dichloromethane, and column chromatography for separation obtains acridone derivatives, and separation yield reaches 84%, it is as follows that nuclear-magnetism characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=11.64 (s, 1H), 8.02 (s, 2H), 7.56 (d, J= 2.0,1H), 7.54 (d, J=2.0,1H), 7.45 (d, J=8.5,2H), 2.42 (s, 6H).13C NMR(101MHz,DMSO-d6) δ=176.8,139.4,135.2,130.3,125.5,120.7,117.7,21.1.HRMS (EI) Theoretical Calculation C15H13NO[M+ H]+:224.1070；Discovery value: 224.1068.
Embodiment 11
Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), 3,5-is added in dry Schlenk reaction tube Dimethyl diphenylamines (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then it is sequentially added into Solvent anhydrous dimethyl sulphoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL), anti-at 100 DEG C Answer stopped reaction after 24 hours, be cooled to room temperature, in reaction system, add ethyl acetate cancellation reaction, add saturated potassium carbonate Solution (30.0mL), extracts (20 × 3) with dichloromethane, and column chromatography for separation obtains acridone derivatives, and separation yield reaches 59%, it is as follows that nuclear-magnetism characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=11.45 (s, 1H), 8.16 (d, J=7.5,1H), 7.69 7.63 (m, 1H), 7.46 (d, J=8.3,1H), 7.22 7.16 (m, 1H), 7.13 (s, 1H), 6.79 (s, 1H), 2.83 (s, 3H),2.37(s,3H).13C NMR(101MHz,DMSO-d6) δ=183.7,147.9,147.8,145.5,145.4,138.1, 131.4,130.6,127.0,125.8,122.3,1219,120.0,28.8,26.5。
Embodiment 12
Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), 3,5-is added in dry Schlenk reaction tube Difluorodiphenyl amine (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then it is sequentially added into molten Agent anhydrous dimethyl sulphoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL), 100 DEG C of reactions Stopped reaction after 24 hours, is cooled to room temperature, adds ethyl acetate cancellation reaction, add saturated potassium carbonate molten in reaction system Liquid (30.0mL), extracts (20 × 3) with dichloromethane, and column chromatography for separation obtains acridone derivatives, and separation yield reaches 61%, It is as follows that nuclear-magnetism characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=11.92 (s, 1H), 8.15 (d, J=7.3,1H), 7.72 (s, 1H), 7.47 (d, J=7.6,1H), 7.27 (s, 1H), 7.02 (dd, J=21.5,10.5,2H).13C NMR(101MHz, DMSO-d6) δ=179.9,170.0 (dd, J=104.3,15.9), 167.5 (d, J=118.3), 148.9 (d, J=8.9), (145.4,139.0,131.1,127.1,126.8,122.2,113.1,103.6 dd, J=24.5,4.4), 102.4 (dd, J= 27.2,25.4) .HRMS (EI) Theoretical Calculation C13H7F2NO[M+H]+:232.0568；Discovery value: 232.0567.
Embodiment 13
Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), 3-is added chloro-in dry Schlenk reaction tube 4-methyldiphenylamine (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then it is sequentially added into Solvent anhydrous dimethyl sulphoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL), anti-at 100 DEG C Answer stopped reaction after 24 hours, be cooled to room temperature, in reaction system, add ethyl acetate cancellation reaction, add saturated potassium carbonate Solution (30.0mL), extracts (20 × 3) with dichloromethane, and column chromatography for separation obtains acridone derivatives, and separation yield reaches 61% (wherein, the productivity ratio of two kinds of isomers products is 2:1), it is as follows that nuclear-magnetism characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=11.75 (s, 1H), 11.71 (s, 0.5H), 8.20 (d, J= 8.0,1H), 8.15 (d, J=8.1,0.5H), 8.11 (d, J=8.7,1H), 7.70 (t, J=7.6,1H), 7.54 (t, J= 8.0,0.5H), 7.48 (d, J=8.5,1H), 7.24 (t, J=5.8,1H), 7.23 7.16 (m, 2H), 2.30 (s, 3H).13C NMR(101MHz,DMSO-d6) δ=176.3,165.7,163.2,141.4,141.2,133.9,129.6,129.5,126.5, 126.4,121.6,120.8,119.5,119.3,117.9,117.7,117.4,102.6,10 2.4,14.5.HRMS (EI) is theoretical Calculate C14H10ClNO[M+H]+:243.0451；Discovery value: 243.0450.
Embodiment 14
Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), adjacent first is added in dry Schlenk reaction tube Base diphenylamines (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then solvent it is sequentially added into Anhydrous dimethyl sulphoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL), react 24 at 100 DEG C Stopped reaction after hour, is cooled to room temperature, adds ethyl acetate cancellation reaction, add unsaturated carbonate potassium solution in reaction system (30.0mL), extracting (20 × 3) with dichloromethane, column chromatography for separation obtains acridone derivatives, and separation yield reaches 60%, core It is as follows that magnetic characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=10.64 (s, 1H), 8.23 (d, J=8.1,1H), 8.13 (d, J=7.9,1H), 7.94 (d, J=8.4,1H), 7.74 (m, 1H), 7.60 (d, J=7.0,1H), 7.28 (t, J=7.1, 1H), 7.21 7.16 (t, J=7.4,1H), 2.61 (s, 3H).13C NMR(101MHz,DMSO-d6) δ=182.3,146.3, 144.7,139.3,138.5,130.9,130.5,129.2,126.5,125.9,125.9,125.5,123.4,23.1。
Embodiment 15
Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), 2,2-is added in dry Schlenk reaction tube Dinaphthylamine (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.Then be sequentially added into solvent without Water dimethyl sulfoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL) are little 100 DEG C of reactions 24 Stopped reaction time after, is cooled to room temperature, adds ethyl acetate cancellation reaction, add unsaturated carbonate potassium solution in reaction system (30.0mL), extracting (20 × 3) with dichloromethane, column chromatography for separation obtains acridone derivatives, and separation yield reaches 66%, core It is as follows that magnetic characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=12.52 (s, 1H), 10.48 (d, J=8.6,2H), 8.20 (d, J=9.0,2H), 8.01 (d, J=7.8,2H), 7.82 7.72 (m, 4H), 7.60 (t, J=7.4,2H).13C NMR (101MHz,DMSO-d6) δ=180.3,140.1,134.9,131.9,129.8,129.0,128.9,126.7,125.6, 118.4,115.5.HRMS (EI) Theoretical Calculation C21H13NO[M+H]+:296.1070；Discovery value: 296.1066.
Embodiment 16
Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), N is added in dry Schlenk reaction tube1,N3- Diphenyl-1,3-diphenylamines (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.The most successively Add solvent anhydrous dimethyl sulphoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL), 100 DEG C reaction 24 hours after stopped reaction, be cooled to room temperature, toward reaction system in add ethyl acetate cancellation reaction, addition saturated carbon Acid potassium solution (30.0mL), extracts (20 × 3) with dichloromethane, and column chromatography for separation obtains acridone derivatives, and separation yield reaches To 59%, it is as follows that nuclear-magnetism characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=11.38 (s, 1H), 8.91 (s, 1H), 8.17 (d, J= 8.0,1H), 8.07 (d, J=8.9,1H), 7.64 (t, J=7.6,1H), 7.46 7.35 (m, 3H), 7.30 (d, J=7.5, 2H), 7.19 (t, J=7.5,1H), 7.06 (t, J=7.3,2H), 6.89 (dd, J=8.9,2.1,1H).13C NMR(101MHz, DMSO-d6) δ=175.7,149.3,143.5,141.7,141.4,133.1,129.9,128.2,126.3,12 2.7,121.1, 120.9,120.5,117.2,114.2,112.7,97.1, HRMS (EI) Theoretical Calculation C19H14N2O[M+H]+:287.1179；Send out Present worth: 287.1178.
Embodiment 17
Palladous chloride. (0.025mmol), pivalic acid copper (0.05mmol), N is added in dry Schlenk reaction tube1,N4- Diphenyl-Isosorbide-5-Nitrae-diphenylamines (0.25mmol), system is replaced three times under the carbon monoxide atmosphere of an atmospheric pressure.The most successively Add solvent anhydrous dimethyl sulphoxide (1.0mL), DTBP (0.75mmol) and solvent anhydrous dimethyl sulphoxide (2.0mL), 100 DEG C reaction 24 hours after stopped reaction, be cooled to room temperature, toward reaction system in add ethyl acetate cancellation reaction, addition saturated carbon Acid potassium solution (30.0mL), extracts (20 × 3) with dichloromethane, and column chromatography for separation obtains acridone derivatives, and separation yield reaches To 42%, it is as follows that nuclear-magnetism characterizes data:
Nuclear magnetic data:1H NMR(400MHz,DMSO-d6) δ=11.90 (s, 1H), 11.79 (s, 1H), 9.84 (d, J= 8.3,1H), 8.39 (d, J=8.1,1H), 8.02 (d, J=8.8,1H), 7.77 7.63 (m, 2H), 7.63 7.47 (m, 3H), 7.41 (t, J=7.4,1H), 7.28 (t, J=7.4,1H), 7.17 (t, J=7.5,1H), 7.03 6.82 (m, 1H).13C NMR (101MHz,DMSO-d6) δ=177.7,140.4,139.9,137.9,135.2,132.9,128.7,126.6,125.7, 123.5,121.8,121.1,119.8,118.3,117.3,116.8,111.2.HRMS (EI) Theoretical Calculation C19H14N2O[M+H ]+:287.1179；Discovery value: 287.1178.

Claims (5)

1. one kind utilizes the method that palladium-copper catalyzes and synthesizes acridone derivatives altogether, it is characterised in that comprise the following steps: first Palladous chloride., pivalic acid copper and diphenylamine compound are together added in dry reactor, then by the atmosphere in reactor It is replaced as carbon monoxide, adds anhydrous organic solvent, in reactant liquor, then add oxidant, described diphenylamine chemical combination Thing, oxidant, Palladous chloride., the mol ratio of pivalic acid copper are 0.1-1.0:0.3-3.0:0.01-0.1:0.02-0.2, described oxygen Agent is di-t-butyl peroxide or oxygen；Then react 20-30 hour under the conditions of 80-120 DEG C, purification, obtain acridone Derivant.
The method utilizing palladium-copper to catalyze and synthesize acridone derivatives altogether the most according to claim 1, it is characterised in that: institute The diphenylamine compound stated be diphenylamines, to methyldiphenylamine, di-p-methoxy-diphenylamine, to oxethyl diphenylamine, to tertiary fourth Base diphenylamines, to trifluoromethyl diphenylamines, to fluorine diphenylamines, p-dichlorobenzene amine, to bromine diphenylamines, 4,4 '-dimethyl diphenylamines, In 3,5-dimethyl diphenylamines, 3,5-difluorodiphenyl amine, 3-chloro-4-methyldiphenylamine, adjacent methyldiphenylamine, 2,2-dinaphthylamine A kind of.
The method utilizing palladium-copper to catalyze and synthesize acridone derivatives altogether the most according to claim 1 and 2, it is characterised in that: Described organic solvent is dimethyl sulfoxide.
The method utilizing palladium-copper to catalyze and synthesize acridone derivatives altogether the most according to claim 1 and 2, it is characterised in that: The mol ratio of Palladous chloride. and pivalic acid copper is 1:2.
The method utilizing palladium-copper to catalyze and synthesize acridone derivatives altogether the most according to claim 4, it is characterised in that: two The mol ratio of amino benzenes compounds and oxidant is 1:3.
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CN108456166A (en) * 2018-04-19 2018-08-28 遂成药业股份有限公司 A method of acridone acetic acid is synthesized using phase transfer catalysis process
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CN108276334A (en) * 2018-02-08 2018-07-13 南京邮电大学 A kind of preparation method of acridone and its derivative
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CN108456166A (en) * 2018-04-19 2018-08-28 遂成药业股份有限公司 A method of acridone acetic acid is synthesized using phase transfer catalysis process
CN108456166B (en) * 2018-04-19 2021-02-05 遂成药业股份有限公司 Method for synthesizing acridone acetic acid by adopting phase transfer catalysis method
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