CN114805106B - Preparation method of amide compound - Google Patents
Preparation method of amide compound Download PDFInfo
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- CN114805106B CN114805106B CN202210595632.1A CN202210595632A CN114805106B CN 114805106 B CN114805106 B CN 114805106B CN 202210595632 A CN202210595632 A CN 202210595632A CN 114805106 B CN114805106 B CN 114805106B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/06—Formation or introduction of functional groups containing nitrogen of amide groups
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/86—Hydrazides; Thio or imino analogues thereof
- C07D213/87—Hydrazides; Thio or imino analogues thereof in position 3
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Abstract
The invention provides a preparation method of an amide compound, and relates to the technical field of organic synthesis. The invention mixes primary amine compound, nano porous palladium, alkaline reagent and solvent, and carries out selective oxidation reaction in air to obtain amide compound. According to the preparation method provided by the invention, the nano porous palladium is used as a catalyst, the nano porous palladium catalyst has a nano-scale three-dimensional bicontinuous porous structure, a large number of communicated nano pores are formed in the nano porous palladium catalyst, the specific surface area is large, a large number of step atoms and low coordination atoms exist on the surface of the nano porous palladium catalyst, more catalytic active sites can be provided, the catalytic activity and the catalytic stability for preparing the amide compound through the selective oxidation of the primary amine compound are high, the product selectivity and the product yield are high, the catalyst is easy to recycle, and the repeated catalytic effect of the catalyst is not obviously reduced.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of an amide compound.
Background
The selective oxidation of primary amines to form amides is an important step in organic synthesis, especially in the synthesis of some important high value compounds (e.g. biologically active molecules, natural products and other important industrial materials of natural products), the synthesis of highly pure amides being a key step.
Traditional methods for preparing amides by selective oxidation of primary amines are mainly divided into two main classes, namely, homogeneous catalysts with Ru, cu and other transition metals combined with ligands, which have higher activity but suffer from more drawbacks such as poor selectivity, more formation of by-products of nitriles, aldehydes and carboxylic acids, and more sensitivity and extremely instability of the catalysts, difficult separation and recovery, unrepeatable use, etc. (XU W, jingay, FU h. Synlett.2012,23, 801-804; YADAV S, RESHI N U D, PAL S, BERAJ K.Catal.Sci.technology.2021, 11,70187028); secondly, more heterogeneous catalysts are being studied, such catalysts comprising Ru (OH) x /Al 2 O 3 Gold nanoparticles, gold nanoclusters, nano manganese oxide, etc., but are often required to be highly oxidized at high oxygen pressure (O 2 The pressure is more than 10 bar), the reaction danger coefficient is high, and the industrial application of the catalyst is limited (KIM J W, YAMAGUCHI K, MIZUNO N.Angew.chem.Int.ed.2008,47,9249-9251; WANG H, WANG L, WANG S, DONG X, et al ChemCatchem 2019,11,401-406.). Therefore, the preparation method of the amide compound has important significance, and the product selectivity is high and the reaction condition is safe.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method of amide compounds, which has high product selectivity and safe reaction conditions.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an amide compound, which comprises the following steps:
mixing a primary amine compound, nano porous palladium, an alkaline reagent and a solvent, and performing selective oxidation reaction in air to obtain an amide compound with a structure shown in a formula I;
r in the primary amine compound is the same as R in the formula I, and R is aryl or alkyl.
Preferably, the aryl group includes phenyl, alkyl-substituted phenyl, alkoxy-substituted phenyl, halogen-substituted phenyl, hydroxy-substituted phenyl, nitro-substituted phenyl, amino-substituted phenyl, trifluoromethyl-substituted phenyl, thienyl, pyridyl, furyl or naphthyl; the alkyl group includes a C1-C20 alkyl group.
Preferably, the molar ratio of the primary amine compound to the nanoporous palladium is 1: (0.01-0.5).
Preferably, the pore diameter of the nano porous palladium is 1-50 nm.
Preferably, the molar ratio of primary amine compound to alkaline agent is 1: (0.1-10).
Preferably, the alkaline agent comprises one or more of alkali metal hydroxide, alkali metal carbonate, alkali metal alkoxide and organic amine.
Preferably, the solvent comprises one or more of water, diethyl ether, acetonitrile, dimethyl sulfoxide, dioxane, triethylamine, tetrahydrofuran, toluene, ethanol, isopropanol, tertiary butanol, chloroform, dichloromethane, acetone and N, N-dimethylformamide.
Preferably, the temperature of the selective oxidation reaction is 0-150 ℃ and the time is 12-36 h.
Preferably, the selective oxidation reaction further comprises separating and purifying the obtained selective oxidation reaction liquid, wherein the separating and purifying comprises recrystallization or column chromatography.
Preferably, the organic solvent for recrystallization comprises one or more of chloroform, cyclohexane, dioxane, benzene, toluene, ethanol, petroleum ether, acetonitrile, N-dimethylformamide, tetrahydrofuran and ethyl acetate;
the stationary phase adopted by the column chromatography comprises silica gel or alkaline alumina; the eluent for column chromatography comprises a mixed solvent of large polarity and small polarity; the volume ratio of the large polar solvent to the small polar solvent in the eluent is 1: (1-50); the large polar solvent comprises ethyl acetate, dichloromethane or methanol; the small polar solvent comprises petroleum ether, n-hexane or ethyl acetate.
The invention provides a preparation method of an amide compound, which comprises the following steps: mixing a primary amine compound, nano porous palladium, an alkaline reagent and a solvent, and performing selective oxidation reaction in air to obtain an amide compound with a structure shown in a formula I; r in the primary amine compound is the same as R in the formula I, and R is aryl or alkyl. The preparation method provided by the invention takes nano porous palladium as a catalyst, and the nano porous palladium catalyst has a nano-scale three-dimensional bicontinuous porous structure, and is characterized in that a large number of communicated nano pores are formed in the nano porous palladium catalyst, the specific surface area is large, and a large number of step atoms and low coordination atoms exist on the surface of the nano porous palladium catalyst, so that more catalytic active sites can be provided, and the nano porous palladium catalyst has high catalytic activity and high catalytic stability for preparing amide compounds by selectively oxidizing primary amine compounds, and has high product selectivity and yield; the nano porous palladium is easy to recycle, and the repeated catalytic effect is not obviously reduced. The invention takes air as oxidant, has high safety of reaction conditions, is environment-friendly, has low production cost and is suitable for industrial production. As shown in the test results of examples, the selectivity of the product of the preparation method provided by the invention is up to 100%, and the yield is up to 95%.
Detailed Description
The invention provides a preparation method of an amide compound, which comprises the following steps:
mixing a primary amine compound, nano porous palladium, an alkaline reagent and a solvent, and performing selective oxidation reaction in air to obtain an amide compound with a structure shown in a formula I;
r in the primary amine compound is the same as R in the formula I, and R is aryl or alkyl.
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
In the present invention, the aryl group preferably includes phenyl, alkyl-substituted phenyl, alkoxy-substituted phenyl, halogen-substituted phenyl, hydroxy-substituted phenyl, nitro-substituted phenyl, amino-substituted phenyl, trifluoromethyl-substituted phenyl, thienyl, pyridyl, furyl, or naphthyl. In the present invention, the alkyl groups in the alkyl group and the alkyl-substituted phenyl group are independently preferably a C1-C20 alkyl group, more preferably include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group or a pentyl group, and the substitution site of the alkyl substituent preferably includes an ortho, meta or para position. In the present invention, the halogen in the halogen-substituted phenyl group preferably includes fluorine, chlorine, bromine or iodine, and the substitution site of the halogen substituent preferably includes ortho, meta or para.
In the present invention, the amide-based compound preferably has any one of the structures shown below:
in the present invention, the pore diameter of the nano-porous palladium (PdNPore) is preferably 1 to 50nm, more preferably 10 to 40nm, and further preferably 20 to 30nm. In the present invention, the molar ratio of the primary amine compound to the nanoporous palladium is preferably 1: (0.01 to 0.5), more preferably 1: (0.05 to 0.45), more preferably 1: (0.1 to 0.4), most preferably 1: (0.2-0.3).
In the present invention, the alkaline agent preferably includes one or more of alkali metal hydroxide, alkali metal carbonate, alkali metal alkoxide and organic amine, more preferably includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, diethylamine and triethylamine. In the present invention, the molar ratio of the primary amine compound to the alkaline agent is preferably 1: (0.1 to 10), more preferably 1: (1 to 8), more preferably 1: (3-7), most preferably 1: (4-5).
In the present invention, the pressure of the air is preferably 1atm.
In the present invention, the solvent preferably includes one or more of water, an ether solvent, a nitrile solvent, a sulfone solvent, a heterocyclic solvent, an organic amine solvent, a benzene solvent, an alcohol solvent, a halogenated hydrocarbon solvent, a ketone solvent, and an amide solvent, and more preferably includes one or more of water, diethyl ether, acetonitrile, dimethyl sulfoxide, dioxane, triethylamine, tetrahydrofuran, toluene, ethanol, isopropanol, t-butanol, chloroform, dichloromethane, acetone, and N, N-dimethylformamide. In the present invention, the ratio of the amount of the substance of the primary amine compound to the volume of the solvent is preferably 0.01 to 2mmol:1mL, more preferably 0.1 to 1.5mmol:1mL, more preferably 0.5 to 1mmol:1mL.
In the present invention, the temperature of the selective oxidation reaction is preferably 0 to 150 ℃, more preferably 40 to 120 ℃, still more preferably 50 to 100 ℃; the time for the selective oxidation reaction is preferably 12 to 36 hours, more preferably 12 to 30 hours, and still more preferably 20 to 25 hours. In the present invention, the reaction occurring during the selective oxidation reaction is as follows:
in the invention, the selective oxidation reaction further comprises the steps of separating and purifying the obtained selective oxidation reaction liquid to obtain an amide compound; the separation and purification preferably comprises recrystallization or column chromatography. In the present invention, the stationary phase used for the column chromatography preferably comprises silica gel or basic alumina; the eluent for column chromatography preferably comprises a mixed solvent of large polarity and small polarity; the volume ratio of the large polar solvent to the small polar solvent in the eluent is preferably 1: (1 to 50), more preferably 1: (1 to 30), more preferably 1: (1-20); the highly polar solvent preferably comprises ethyl acetate, dichloromethane or methanol; the small polar solvent preferably comprises petroleum ether, n-hexane or ethyl acetate; the eluent preferably comprises an ethyl acetate-petroleum ether mixed solvent, an ethyl acetate-normal hexane mixed solvent, a dichloromethane-petroleum ether mixed solvent, a dichloromethane-normal hexane mixed solvent, a methanol-petroleum ether mixed solvent or a methanol-ethyl acetate mixed solvent.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Benzamide compoundIs synthesized by (a)
Catalyst PdNPore (1.6 mg,3 mol%), substrate benzylamine (53.58 mg,0.5 mmol) and sodium tert-butoxide (48.05 mg,0.5 mmol) were added into a 25mL reactor, then 3mL ethanol solvent was added, the reactor was left open to air, and the reaction was carried out under stirring at 50℃for 24 hours, and the mixture was separated and purified by column chromatography (silica gel, 200-300 mesh; eluent: ethyl acetate-petroleum ether in a volume ratio of 1:5) to give benzamide (48.46 mg, yield 80%, selectivity 100%).
1 H NMR(DMSO-d 6 ,500MHz)δ8.00(b,1H),7.90-7.88(m,2H),7.53-7.50(m,1H),7.46-7.43(m,2H),7.39(b,1H)。
Example 2
Synthesis of benzamide
Catalyst PdNPore (2.7 mg,5 mol%), substrate benzylamine (53.58 mg,0.5 mmol) and potassium tert-butoxide (112.21 mg,1.0 mmol) were added into a 25mL reactor, then 3mL of tert-butanol solvent was added, the reactor was left open to air, and the reaction was carried out under stirring at 80℃for 24 hours, and the mixture was separated and purified by column chromatography (silica gel, 200-300 mesh; eluent: ethyl acetate-petroleum ether in a volume ratio of 1:5) to give benzamide (57.54 mg, yield 95%, selectivity 100%).
1 H NMR(DMSO-d 6 ,500MHz)δ8.00(b,1H),7.90-7.88(m,2H),7.53-7.50(m,1H),7.46-7.43(m,2H),7.39(b,1H)。
Comparative example 1
Synthesis of benzamide
Catalyst PdNPore (2.7 mg,5 mol%), substrate benzylamine (53.58 mg,0.5 mmol) and potassium tert-butoxide (112.21 mg,1.0 mmol) were added into a 25mL reactor, then 3mL of tert-butanol solvent was added, the reactor was placed in air, the reactor was subjected to selective oxidation reaction at 170℃with stirring for 24 hours, and the mixture was separated and purified by column chromatography (silica gel, 200-300 mesh; eluent: ethyl acetate-petroleum ether in a volume ratio of 1:5) to give benzamide (21.20 mg, yield 35%, selectivity 40%).
1 H NMR(DMSO-d 6 ,500MHz)δ8.00(b,1H),7.90-7.88(m,2H),7.53-7.50(m,1H),7.46-7.43(m,2H),7.39(b,1H)。
Comparative example 2
Synthesis of benzamide
Catalyst PdNPore (2.7 mg,5 mol%), substrate benzylamine (53.58 mg,0.5 mmol) and potassium tert-butoxide (112.21 mg,1.0 mmol) were added into a 25mL reactor, then 3mL of tert-butanol solvent was added, the reactor was left open to air, and the reaction was selectively oxidized at 80℃under stirring for 10 hours, and the mixture was separated and purified by column chromatography (silica gel, 200-300 mesh; eluent: ethyl acetate-petroleum ether in a volume ratio of 1:5) to give benzamide (27.86 mg, yield 46%, selectivity 75%).
1 H NMR(DMSO-d 6 ,500MHz)δ8.00(b,1H),7.90-7.88(m,2H),7.53-7.50(m,1H),7.46-7.43(m,2H),7.39(b,1H)。
Comparative example 3
Synthesis of benzamide
A25 mL reactor was charged with commercial catalyst Pd/C (2.7 mg,5 mol%), substrate benzylamine (53.58 mg,0.5 mmol) and potassium tert-butoxide (112.21 mg,1.0 mmol), then 3mL of tert-butanol solvent was added, the reactor was left open to air, and the reaction was selectively oxidized at 80℃with stirring for 24 hours, and the mixture was separated and purified by column chromatography (silica gel, 200 to 300 mesh; eluent: ethyl acetate-petroleum ether in a volume ratio of 1:5) to give benzamide (18.17 mg, yield 30%, selectivity 34%).
1 H NMR(DMSO-d 6 ,500MHz)δ8.00(b,1H),7.90-7.88(m,2H),7.53-7.50(m,1H),7.46-7.43(m,2H),7.39(b,1H)。
Comparative example 4
Synthesis of benzamide
Catalyst Pd/CaCO was charged into a 25mL reactor 3 (2.7 mg,5 mol%), substrate benzylamine (53.58 mg,0.5 mmol) and potassium tert-butoxide (112.21 mg,1.0 mmol) were added, then 3mL of a tert-butanol solvent was added, the reactor was left open in air, and the reaction was carried out under stirring at 80℃for 24 hours, and the mixture was separated and purified by column chromatography (silica gel, 200 to 300 mesh; eluent: ethyl acetate-petroleum ether in a volume ratio of 1:5) to give benzamide (10.90 mg, yield 1)8%, selectivity 21%).
1 H NMR(DMSO-d 6 ,500MHz)δ8.00(b,1H),7.90-7.88(m,2H),7.53-7.50(m,1H),7.46-7.43(m,2H),7.39(b,1H)。
Comparative example 5
Synthesis of benzamide
Catalyst PdNPore (2.7 mg,5 mol%), substrate benzylamine (750.12 mg,7 mmol) and potassium tert-butoxide (112.21 mg,1.0 mmol) were added into a 25mL reactor, then 3mL of tert-butanol solvent was added, the reactor was left open to air, and the reaction was carried out under stirring at 80℃for 24 hours, and the mixture was separated and purified by column chromatography (silica gel, 200-300 mesh; eluent: ethyl acetate-petroleum ether in a volume ratio of 1:5) to give benzamide (356.15 mg, yield 42%, selectivity 65%).
1 H NMR(DMSO-d 6 ,500MHz)δ8.00(b,1H),7.90-7.88(m,2H),7.53-7.50(m,1H),7.46-7.43(m,2H),7.39(b,1H)。
Comparative example 6
Synthesis of benzamide
Catalyst PdNPore (0.27 mg,0.5 mol%), substrate benzylamine (53.58 mg,0.5 mmol) and potassium tert-butoxide (112.21 mg,1.0 mmol) were added into a 25mL reactor, then 3mL of tert-butanol solvent was added, the reactor was placed in air, and the reaction was carried out under stirring at 80℃for 24 hours, and the mixture was separated and purified by column chromatography (silica gel, 200-300 mesh; eluent: ethyl acetate-petroleum ether in a volume ratio of 1:5) to give benzamide (6.66 mg, yield 11%, selectivity 100%).
1 H NMR(DMSO-d 6 ,500MHz)δ8.00(b,1H),7.90-7.88(m,2H),7.53-7.50(m,1H),7.46-7.43(m,2H),7.39(b,1H)。
Comparative example 7
Synthesis of benzamide
Catalyst PdNPore (2.7 mg,5 mol%), substrate benzylamine (53.58 mg,0.5 mmol) and potassium tert-butoxide (673.27 mg,6.0 mmol) were added into a 25mL reactor, then 3mL of tert-butanol solvent was added, the reactor was placed in air, and the reaction was carried out under stirring at 80℃for 24 hours, and the mixture was separated and purified by column chromatography (silica gel, 200-300 mesh; eluent: ethyl acetate-petroleum ether in a volume ratio of 1:5) to give benzamide (43.61 mg, yield 72%, selectivity 85%).
1 H NMR(DMSO-d 6 ,500MHz)δ8.00(b,1H),7.90-7.88(m,2H),7.53-7.50(m,1H),7.46-7.43(m,2H),7.39(b,1H)。
Example 3
4-methylbenzamideIs synthesized by (a)
Catalyst PdNPore (5.4 mg,10 mol%), substrate 4-methylbenzylamine (121.18 mg,1 mmol) and sodium hydroxide (80.00 mg,2 mmol) were added into a 25mL reactor, then 5mLN, N-dimethylformamide solvent was added, the reactor was placed in air, and the reaction was selectively oxidized at 70℃under stirring for 20 hours, and the separation and purification by column chromatography (silica gel, 200-300 mesh; eluent: ethyl acetate-n-hexane) were performed to obtain 4-methylbenzamide (113.54 mg, yield 84%, selectivity 98%). After recycling the catalyst 6 times, 4-methylbenzamide (113.54 mg, yield 84%, selectivity 98%) was obtained.
1 H NMR(DMSO-d 6 ,500MHz)δ7.80(d,J＝8.0Hz,2H),7.24(d,J＝8.0Hz,2H),2.33(s,3H).
Example 4
Synthesis of 4-methylbenzamide
Catalyst PdNPore (1.1 mg,2 mol%), substrate 4-methylbenzylamine (36.35 mg,0.3 mmol) and sodium carbonate (63.59 mg,0.6 mmol) were added into a 25mL reactor, then 5mL acetonitrile solvent was added, the reactor was left open to air, and the reaction was selectively oxidized under stirring at 50℃for 30 hours, and the mixture was separated and purified by column chromatography (silica gel, 200-300 mesh; eluent: ethyl acetate-n-hexane in a volume ratio of 1:10) to give 4-methylbenzamide (30.82 mg, yield 76%, selectivity 97%).
1 H NMR(DMSO-d 6 ,500MHz)δ7.80(d,J＝8.0Hz,2H),7.24(d,J＝8.0Hz,2H),2.33(s,3H).
Example 5
4-fluorobenzamideIs synthesized by (a)
Catalyst PdNPore (2.7 mg,5 mol%), substrate 4-fluorobenzylamine (62.58 mg,0.5 mmol) and cesium carbonate (162.91 mg,0.5 mmol) were added to a 25mL reactor, then 6mL tetrahydrofuran solvent was added, the reactor was left open to air, and the reaction was selectively oxidized at 80℃under stirring for 24 hours, and the separation and purification by column chromatography (silica gel, 200 to 300 mesh; eluent: ethyl acetate-petroleum ether in a volume ratio of 1:20) were performed to obtain 4-fluorobenzamide (61.22 mg, yield 88%, selectivity 99%). After recycling the catalyst 8 times, 4-fluorobenzamide (61.22 mg, yield 88%, selectivity 99%) was obtained.
1 H NMR(DMSO-d 6 ,500MHz)δ8.00(b,1H),7.97-7.92(m,2H),7.39(b,1H),7.30-7.26(m,2H).
Example 6
Synthesis of 4-fluorobenzamide
Catalyst PdNPore (2.7 mg,5 mol%), substrate 4-fluorobenzylamine (62.58 mg,0.5 mmol) and potassium hydroxide (56.11 mg,1 mmol) were added into a 25mL reactor, then 3mL dioxane solvent was added, the reactor was placed in air, and the reaction was carried out under stirring at 70℃for 19h, and the separation and purification were carried out by column chromatography (silica gel, 200-300 mesh; eluent: ethyl acetate-petroleum ether in a volume ratio of 1:20) to give 4-fluorobenzamide (57.04 mg, yield 82%, selectivity 99%).
1 H NMR(DMSO-d 6 ,500MHz)δ8.00(b,1H),7.97-7.92(m,2H),7.39(b,1H),7.30-7.26(m,2H).
Example 7
3-pyridinecarboxamidesIs synthesized by (a)
Catalyst PdNPore (1.6 mg,3 mol%), substrate 3-aminomethylpyridine (108.14 mg,1 mmol) and potassium tert-butoxide (224.42 mg,2 mmol) are added into a 25mL reactor, then 5mL of tert-butanol solvent is added, the reactor is placed in air at the open mouth, and the selective oxidation reaction is carried out for 24 hours under the condition of 60 ℃ and stirring, and the column chromatography separation and purification (silica gel, 200-300 meshes; eluent: methanol-petroleum ether with the volume ratio of 1:15) are carried out, thus obtaining 3-pyridine amide (103.81 mg, yield 85%, selectivity 100%). After recycling the catalyst 10 times, 3-pyridineamide (103.81 mg, yield 85%, selectivity 100%) was obtained.
1 H NMR(DMSO-d 6 ,500MHz)δ9.05-9.02(m,1H),8.70(dd,J＝4.8,1.7Hz,1H),8.22-8.20(m,1H),8.17(b,1H),7.61(b,1H),7.51-7.48(m,1H).
Example 8
Synthesis of 3-pyridinecarboxamides
Catalyst PdNPore (2.7 mg,5 mol%), substrate 3-aminomethylpyridine (54.07 mg,0.5 mmol) and potassium tert-butoxide (112.21 mg,1 mmol) were added into a 25mL reactor, then 3mL of tert-butanol solvent was added, the reactor was placed in air, and the reaction was carried out under stirring at 80℃for 24 hours, and the 3-pyridine amide (56.18 mg, 92% yield, 100% selectivity) was obtained after separation and purification by column chromatography (silica gel, 200-300 mesh; eluent: methanol-petroleum ether in a volume ratio of 1:15).
1 HNMR(DMSO-d 6 ,500MHz)δ9.05-9.02(m,1H),8.70(dd,J＝4.8,1.7Hz,1H),8.22-8.20(m,1H),8.17(b,1H),7.61(b,1H),7.51-7.48(m,1H).
Example 9
2-naphthalenamidesIs synthesized by (a)
Catalyst PdNPore (5.4 mg,10 mol%), substrate 2- (aminomethyl) naphthalene (47.17 mg,0.3 mmol) and sodium tert-butoxide (96.10 mg,1 mmol) were added into a 25mL reactor, then 3mL of tert-butanol solvent was added, the reactor was placed in air, and the reaction was carried out under stirring at 80℃for 24 hours, and the separation and purification by column chromatography (silica gel, 200-300 mesh; eluent: ethyl acetate-petroleum ether in a volume ratio of 1:10) were obtained to give 2-naphthoamide (47.76 mg, yield 93%, selectivity 100%). After recycling the catalyst 10 times, 2-naphthoamide (47.76 mg, yield 93%, selectivity 100%) was obtained.
1 H NMR(DMSO-d 6 ,500MHz)δ8.54(s,1H),8.22(b,1H),8.02-7.95(m,4H),7.61-7.57(m,3H).
Example 10
Synthesis of 2-naphthalamide
Catalyst PdNPore (3.2 mg,6 mol%), substrate 2- (aminomethyl) naphthalene (47.17 mg,0.3 mmol) and triethylamine (60.71 mg,0.6 mmol) were added into a 25mL reactor, then 5mL ethanol solvent was added, the reactor was placed in air, and the reaction was selectively oxidized at 60℃under stirring for 24 hours, and the separation and purification by column chromatography (silica gel, 200-300 mesh; eluent: ethyl acetate-petroleum ether in a volume ratio of 1:10) were obtained to give 2-naphthoamide (44.68 mg, yield 87%, selectivity 100%).
1 H NMR(DMSO-d 6 ,500MHz)δ8.54(s,1H),8.22(b,1H),8.02-7.95(m,4H),7.61-7.57(m,3H).
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The preparation method of the amide compound is characterized by comprising the following steps of:
mixing a primary amine compound, nano porous palladium, an alkaline reagent and a solvent, and performing selective oxidation reaction in air to obtain an amide compound with a structure shown in a formula I;
r in the primary amine compound is the same as R in the formula I, and R is aryl or alkyl;
the molar ratio of the primary amine compound to the nano-porous palladium is 1: (0.01-0.5);
the temperature of the selective oxidation reaction is 0-150 ℃ and the time is 12-36 h;
the aryl is phenyl, alkyl substituted phenyl, alkoxy substituted phenyl, halogen substituted phenyl, hydroxy substituted phenyl, nitro substituted phenyl, amino substituted phenyl, trifluoromethyl substituted phenyl, thienyl, pyridyl, furyl or naphthyl; the alkyl is C1-C20 alkyl;
the aperture of the nano porous palladium is 1-50 nm.
2. The method according to claim 1, wherein the molar ratio of the primary amine compound to the alkaline agent is 1: (0.1-10).
3. The method according to claim 1, wherein the alkaline agent is one or more of an alkali metal hydroxide, an alkali metal carbonate, an alkali metal alkoxide and an organic amine.
4. The preparation method according to claim 1, wherein the solvent is one or more of water, diethyl ether, acetonitrile, dimethyl sulfoxide, dioxane, triethylamine, tetrahydrofuran, toluene, ethanol, isopropanol, tert-butanol, chloroform, dichloromethane, acetone and N, N-dimethylformamide.
5. The method according to claim 1, wherein the selective oxidation reaction is followed by separation and purification of the obtained selective oxidation reaction solution, the separation and purification being recrystallization or column chromatography.
6. The preparation method according to claim 5, wherein the organic solvent for recrystallization is one or more of chloroform, cyclohexane, dioxane, benzene, toluene, ethanol, petroleum ether, acetonitrile, N-dimethylformamide, tetrahydrofuran and ethyl acetate;
the stationary phase adopted by the column chromatography is silica gel or alkaline alumina; the eluent for column chromatography is a mixed solvent of large polarity and small polarity; the volume ratio of the large polar solvent to the small polar solvent in the eluent is 1: (1-50); the large polar solvent is ethyl acetate, dichloromethane or methanol; the small polar solvent is petroleum ether, normal hexane or ethyl acetate.
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