阅读说明：本技术 一种甲酰胺类化合物的制备方法 (Preparation method of formamide compound ) 是由 冯秀娟 王继虓 包明 于 2021-07-22 设计创作，主要内容包括：本发明属于CO-(2)的活化转化及相关化学技术领域,提供了一种甲酰胺类化合物的制备方法,以二氧化碳、胺类化合物和苯基硅烷为原料,在纳米多孔钯催化剂的作用下,合成甲酰胺类化合物。本发明主要是提供一种新的简单的催化体系,利用CO-(2)作为C-(1)源合成甲酰胺类化合物,该催化体系具有反应条件温和、实验操作简单、官能团兼容性好等优点。由于二氧化碳是储量丰富、廉价易得且可再生的C-(1)源,因此,本发明具有较大的应用价值和社会经济效益。(The invention belongs to CO 2 The related chemical technology field, provides a preparation method of formamide compounds, which uses carbon dioxideAmine compounds and phenyl silane are used as raw materials, and the formamide compounds are synthesized under the action of a nano porous palladium catalyst. The invention mainly provides a new simple catalytic system, which utilizes CO 2 As C 1 The source synthesis formamide compound has the advantages of mild reaction conditions, simple experimental operation, good functional group compatibility and the like. Because the carbon dioxide is C which has rich reserves, low price, easy obtaining and regeneration 1 Therefore, the invention has great application value and social and economic benefits.)

1. the preparation method of the formamide compound is characterized in that carbon dioxide, an amine compound and phenyl silane are used as raw materials, and under the action of a nano porous palladium catalyst, the synthesis route of the formamide compound is as follows:

in the formula, R¹Selected from the group consisting of hydrogen, methyl, methoxy, ethoxy, halo, t-butyl, n-butyl, hydroxy, methylthio, phenyl, cyano, trifluoromethyl and phenoxy; r²Selected from hydrogen, methyl, ethyl, benzyl, allyl, and isopropyl; r³Selected from the group consisting of hydrogen, benzyl, cyclohexyl, and allyl; r⁴Selected from benzyl, cyclohexyl, allyl, pyridyl, hexyl, and quinoline;

the method comprises the following specific steps: sequentially adding a nano porous palladium catalyst, an amine compound, phenyl silane, an organic solvent and water into a reaction kettle, and filling carbon dioxide to 0.5-3.0 MPa; then placing the reaction kettle in an oil bath at 50-120 ℃ for reaction for 12-36 h, cooling to room temperature after the reaction is finished, discharging residual carbon dioxide, removing the solvent in the obtained reaction liquid by rotary evaporation, and separating by silica gel column chromatography to obtain a target product formamide compound; simultaneously, cleaning the nano porous palladium catalyst by using acetone, and drying in vacuum to be used in the next reaction; wherein, the eluent in the silica gel column chromatography is petroleum ether and ethyl acetate with the volume ratio of 2: 1;

wherein the molar ratio of the amine compound to the phenyl silane is 1: 1.0-1: 5.0;

the mol ratio of the amine compound to the nano porous palladium catalyst is 1: 0.01-1: 0.5;

the molar concentration of the amine compound in the organic solvent is 0.01-1 mmol/mL;

the volume ratio of water to organic solvent is 1: 100-500.

2. The method according to claim 1, wherein the organic solvent is acetonitrile, 1, 4-dioxane, tetrahydrofuran, methanol, ethyl acetate, dichloromethane, or n-hexane.

3. The method of claim 1 or 2, wherein the nanoporous palladium catalyst has a pore size of between 1 nm and 50 nm.

Technical Field

The invention belongs to CO₂Relates to CO and the related chemical technology field₂As C₁A process for the preparation of a source carboxamide compound.

Background

Carbon dioxide is C which is abundant in reserves, cheap, readily available and renewable₁The research on the catalytic conversion of the source of the fine chemicals into high value-added fine chemicals has attracted a great deal of attention. Many methods have been reported over the past decades for the fixation of carbon dioxide and its conversion [ see: (a) katagiri, t.; amao, y.green chem.2020,22,6682 (b) He, m.; sun, y.; han, b. angelw.chem.int.ed.2013, 57,9620.]. Among these methods, the method of catalyzing the conversion of carbon dioxide to form a new C — N bond is an effective method for synthesizing fine chemicals with high added values because of its characteristics of high selectivity, good functional group compatibility, mild reaction conditions, and the like. [ see: (a) hu, x.; wu, y.chem.commu.2017, 53,8046.(b) Hasegawa, j.; ema, t.chem.commun.2020,56,5783.(c) He, l.angelw.chem.int.ed.2017, 56,7425.]. However, no report has been made on a method for constructing a novel C-N bond-to-formamide compound by catalyzing carbon dioxide with a nanoporous palladium catalyst. Thus developing a simple nano-porous palladium catalytic system and utilizing CO₂As C₁The source synthesis of the formamide compound has important research significance.

Disclosure of Invention

The invention provides a method for utilizing CO₂As C₁The method for source synthesis of the formamide compound uses nano porous palladium as a catalyst, and realizes the catalysis of CO by the nano porous palladium₂Transforming to construct C-N bond. The method has the advantages of mild reaction conditions, simple experimental operation, good substrate compatibility, high activity of the used catalyst, good stability and the like, and the catalytic activity of the catalyst is basically unchanged after repeated use.

Technical scheme of the invention

A preparation method of formamide compounds takes carbon dioxide, amine compounds and phenyl silane as raw materials, and under the action of a nano porous palladium catalyst, the synthesis route of the formamide compounds is as follows:

in the formula, R¹Selected from the group consisting of hydrogen, methyl, methoxy, ethoxy, halo, t-butyl, n-butyl, hydroxy, methylthio, phenyl, cyano, trifluoromethyl and phenoxy; r²Selected from hydrogen, methyl, ethyl, benzyl, allyl, and isopropyl; r³Selected from the group consisting of hydrogen, benzyl, cyclohexyl, and allyl; r⁴Selected from benzyl, cyclohexyl, allyl, pyridyl, hexyl, and quinoline;

the method comprises the following specific steps: sequentially adding a nano porous palladium catalyst, an amine compound, phenyl silane, an organic solvent and water into a reaction kettle, and filling carbon dioxide to 0.5-3.0 MPa; then placing the reaction kettle in an oil bath at 50-120 ℃ for reaction for 12-36 h, cooling to room temperature after the reaction is finished, discharging residual carbon dioxide, removing the solvent in the obtained reaction liquid by rotary evaporation, and separating by silica gel column chromatography to obtain a target product formamide compound; simultaneously, cleaning the nano porous palladium catalyst by using acetone, and drying in vacuum to be used in the next reaction; wherein, the eluent in the silica gel column chromatography is petroleum ether and ethyl acetate with the volume ratio of 2: 1;

wherein the molar ratio of the amine compound to the phenyl silane is 1: 1.0-1: 5.0;

the mol ratio of the amine compound to the nano porous palladium catalyst is 1: 0.01-1: 0.5;

the molar concentration of the amine compound in the organic solvent is 0.01-1 mmol/mL;

the volume ratio of water to organic solvent is 1: 100-500.

The organic solvent is acetonitrile, 1, 4-dioxane, tetrahydrofuran, methanol, ethyl acetate, dichloromethane or n-hexane.

The pore size of the nano porous palladium catalyst is 1-50 nm.

The separation method uses column chromatography, silica gel or alkaline alumina as stationary phase, and the developing agent is generally polar and nonpolar mixed solvent, such as ethyl acetate-petroleum ether, ethyl acetate-n-hexane, dichloromethane-petroleum ether, and methanol-petroleum ether.

The method has the advantages of very mild reaction conditions, high product yield, simple operation and post-treatment, good catalyst repeatability, no obvious reduction of the catalytic effect after repeated utilization, and possibility of realizing industrialization.

Drawings

FIG. 1 shows the preparation of the compound N-methylformanilide¹H nuclear magnetic spectrum.

FIG. 2 shows the preparation of the compound N-methylformanilide¹³C nuclear magnetic spectrum.

FIG. 3 shows the preparation of the compound N-methyl-4-methoxy formanilide¹H nuclear magnetic spectrum.

FIG. 4 shows the preparation of the compound N-methyl-4-methoxy formanilide¹³C nuclear magnetic spectrum.

FIG. 5 shows the preparation of the compound N-allylformanilide¹H nuclear magnetic spectrum.

FIG. 6 shows the preparation of the compound N-allylformanilide¹³C nuclear magnetic spectrum.

FIG. 7 shows the preparation of the compound N, N-dibenzylformamide¹H nuclear magnetic spectrum.

FIG. 8 shows the preparation of the compound N, N-dibenzylformamide¹³C nuclear magnetic spectrum.

FIG. 9 shows preparation of compound N- (4-ethoxyphenyl) carboxamide¹H nuclear magnetic spectrum.

FIG. 10 shows the preparation of the compound N- (4-ethoxyphenyl) carboxamide¹³C nuclear magnetic spectrum.

FIG. 11 is a scheme showing the preparation of the compound N- (8-quinolyl) carboxamide¹H nuclear magnetic spectrum.

FIG. 12 is a scheme showing the preparation of the compound N- (8-quinolyl) carboxamide¹³C nuclear magnetic spectrum.

FIG. 13 is a scheme showing the synthesis of the compound N- (4-chlorophenyl) carboxamide¹H nuclear magnetic spectrum.

FIG. 14 is a compoundProcess for preparing N- (4-chlorophenyl) formamide¹³C nuclear magnetic spectrum.

FIG. 15 is a schematic representation of compound N-formyl N-hexylamine¹H nuclear magnetic spectrum.

FIG. 16 is a scheme showing the preparation of the compound N-formyl-N-hexylamine¹³C nuclear magnetic spectrum.

Detailed Description

The method for synthesizing formamide has the advantages of good repeatability of catalytic reaction by selecting the catalyst, simple operation and post-treatment, no obvious reduction of catalytic effect after repeated utilization, and provision of favorable conditions for industrial production.

The invention will be further illustrated with reference to the following specific examples. The simple replacement or improvement of the present invention by those skilled in the art is within the technical scheme of the present invention.

Example 1: synthesis of N-methyl formanilide

Adding PdNPore-1(2.7mg, 0.025mmol), N-methylaniline (53.5mg, 0.5mmol), phenyl silane (216.4mg, 2mmol), acetonitrile (2mL), deionized water (10 mu L) and carbon dioxide (1.0MPa) into a 20mL high-pressure reaction kettle, placing the mixture on a magnetic stirrer, reacting at 60 ℃ for 20h, and carrying out column chromatography (silica gel, 200 meshes, 300 meshes; developing agent, petroleum ether and ethyl acetate ═ 2: 1) to obtain 53.7mg of N-methylformanilide, wherein the yield is 85%

A yellow oily liquid;¹H NMR(CDCl₃,400MHz)δ8.46(s,1H),7.42-7.37(m,2H),7.28-7.24(m,1H),7.16(d,J＝8.0Hz,2H),3.30(s,3H)；¹³C NMR(CDCl₃,100MHz)δ162.3,142.2,129.6,126.4,122.3,32.0.

example 2: synthesis of N-methyl-4-methoxy formanilide

In a 20mL high-pressure reaction kettle, a nano-porous palladium catalyst PdNPore-1(2.7mg, 0.025mmol), N-methyl-4-methoxyaniline (68.5mg, 0.5mmol), phenylsilane (216.4mg, 2mmol), acetonitrile (2mL), deionized water (10 uL) and carbon dioxide (2.0MPa) are added, the mixture is placed on a magnetic stirrer to react for 24 hours at 70 ℃, and column chromatography (silica gel, 200 meshes, 300 meshes; developing agent, petroleum ether and ethyl acetate ═ 2: 1) is carried out to obtain 75.1mg of N-methyl-4-methoxyformanilide with the yield of 91%.

A yellow oily liquid;¹H NMR(CDCl₃,400MHz)δ8.34(s,1H),7.10(d,J＝8.0Hz,2H),6.93(d,J＝8.0Hz,2H),3.83(s,3H),3.27(s,3H)；¹³C NMR(CDCl₃,100MHz)δ162.5,158.3,135.3,124.7,114.8,55.5,32.7.

example 3: synthesis of N-allyl formanilide

Adding PdNPore-1(2.7mg, 0.025mmol), N-allylaniline (66.5mg, 0.5mmol), phenyl silane (270.5mg, 2.5mmol), acetonitrile (2mL), deionized water (10 muL) and carbon dioxide (1.0MPa) into a 20mL high-pressure reaction kettle, placing the mixture on a magnetic stirrer, reacting at 70 ℃ for 24h, and carrying out column chromatography (silica gel, 200 meshes, 300 meshes; developing agent, petroleum ether, ethyl acetate ═ 2: 1) to obtain 64.5mg of N-allylformanilide, wherein the yield is 80%

A yellow oily liquid.¹H NMR(CDCl₃,400MHz)δ8.40(s,1H),7.32-7.27(m,2H),7.20-7.17(m,1H),7.10(d,J＝8.0Hz,2H),5.81-5.71(m,1H),5.12-5.07(m,2H),4.33(d,J＝8.0Hz,2H)；¹³C NMR(CDCl₃,100MHz)δ162.0,141.2,132.5,130.0,126.7,123.5,117.6,47.8.

Example 4: synthesis of N, N-dibenzyl formamide

In a 20mL high-pressure reaction kettle, a nano porous palladium catalyst PdNPore-1(2.7mg, 0.025mmol), dibenzylamine (98.6mg, 0.5mmol), phenyl silane (216.4mg, 2mmol), acetonitrile (3mL), deionized water (15 muL) and carbon dioxide (3.0MPa) are added, the mixture is placed on a magnetic stirrer to react for 20h at the temperature of 60 ℃, and column chromatography (silica gel, 200 meshes, a developing agent, petroleum ether and ethyl acetate ═ 2: 1) is carried out to obtain 83.3mg of N-allyl formanilide, the yield is 74%

A white solid;¹H NMR(CDCl₃,400MHz)δ8.42(s,1H),7.39-7.29(m,6H),7.21-7.17(m,4H),4.42(s,2H),4.27(s,2H)；¹³C NMR(CDCl₃,100MHz)δ162.9,136.0,135.7,129.0,128.7,128.6,128.2,127.7,127.7,50.2,44.7.

example 5: synthesis of N- (4-ethoxyphenyl) formamide

In a 20mL high-pressure reaction kettle, a nano porous palladium catalyst PdNPore-1(2.7mg, 0.025mmol), 4-ethoxyaniline (66.5mg, 0.5mmol), phenylsilane (216.4mg, 2mmol), acetonitrile (3mL), deionized water (10 muL) and carbon dioxide (1.0MPa) are added, the mixture is placed on a magnetic stirrer to react for 20 hours at the temperature of 60 ℃, and column chromatography (silica gel, 200 meshes, 300 meshes; developing agent, petroleum ether and ethyl acetate ═ 5: 1) is carried out to obtain 68.5mg of N- (4-ethoxyphenyl) formamide with the yield of 83 percent.

A yellow solid;¹H NMR(CDCl₃,400MHz)δ8.50(d,J＝8.0Hz,0.48H),8.31(,s,0.5H),8.09(s,0.44H),7.43(d,J＝12.0Hz,1H),7.02(d,J＝8.0Hz,1H),6.88-6.83(m,2H),4.04-3.98(m,2H),1.42-1.38(m,3H)；¹³C NMR(CDCl₃,100MHz)δ163.5,160.0,156.9,156.0,130.1,129.7,121.9,121.4,115.4,114.8,63.8,63.7,14.8.

example 6: synthesis of N- (8-quinolyl) formamide

In a 20mL high-pressure reaction kettle, a nano porous palladium catalyst PdNPore-1(2.7mg, 0.025mmol), 8-aminoquinoline (72.1mg, 0.5mmol), phenylsilane (216.4mg, 2mmol), acetonitrile (2mL), deionized water (10 muL) and carbon dioxide (1.0MPa) are added, the mixture is placed on a magnetic stirrer to react for 24h at the temperature of 60 ℃, and column chromatography (silica gel, 200 meshes, 300 meshes; developing agent, petroleum ether and ethyl acetate ═ 5: 1) is carried out to obtain 70.5mg of N- (8-quinolyl) formamide with the yield of 82%.

A white solid;¹H NMR(CDCl₃,400MHz)δ9.80(s,0.71H),9.52(s,0.11H),9.13(d,J＝12.0Hz,0.11H),8.81-8.69(m,3H),8.16(d,J＝8.0Hz,1H),7.55-7.44(m,3H)；¹³C NMR(CDCl₃,100MHz)δ160.6,159.3,149.0,148.5,138.3,136.4,136.1,134.4,133.6,128.6,128.0,127.3,126.7,122.6,122.3,121.8,117.6,111.0.

example 7: synthesis of N- (4-chlorophenyl) formamide

In a 20mL high-pressure reaction kettle, a nano porous palladium catalyst PdNPore-1(2.7mg, 0.025mmol), 4-chloroaniline (63.7mg, 0.5mmol), phenylsilane (216.4mg, 2mmol), acetonitrile (2mL), deionized water (10 muL) and carbon dioxide (1.0MPa) are added, the mixture is placed on a magnetic stirrer to react for 28h at the temperature of 60 ℃, and column chromatography (silica gel, 200 meshes, a developing agent, petroleum ether and ethyl acetate ═ 5: 1) is carried out to obtain 70.5mg of N- (4-chlorophenyl) formamide with the yield of 82%.

A yellow solid;¹H NMR(CDCl₃,400MHz)δ8.85(d,J＝8.0Hz,0.33H),8.66d,J＝12.0Hz,0.42H),8.35(s,0.56H),7.90(s,0.44H),7.49(d,J＝8.0Hz,1H),7.32-7.28(m,2H),7.04(d,J＝8.0Hz,1H)；¹³C NMR(CDCl₃,100MHz)δ162.6,159.1,135.4,135.3,130.8,129.8,129.2,121.3,120.1.

example 8: synthesis of N-formyl N-hexylamine

In a 20mL high-pressure reaction kettle, a nano porous palladium catalyst PdNPore-1(216.4mg, 2mmol), N-hexylamine (50.5mg, 0.5mmol), phenylsilane (270.5mg, 2.5mmol), acetonitrile (2mL), deionized water (10 muL) and carbon dioxide (1.0MPa) are added, the mixture is placed on a magnetic stirrer to react for 20h at the temperature of 60 ℃, and column chromatography (silica gel, 200 meshes, 300 meshes; developing agent, petroleum ether and ethyl acetate are 5: 1) is carried out to obtain 53.6mg of N-formyl N-hexylamine with the yield of 83 percent.

A light yellow oily liquid;¹H NMR(CDCl₃,400MHz)δ8.20(s,1H),4.42(s,1H),2.84-2.77(m,2H),1.67-1.61(m,2H),1.36-1.31(m,6H),0.90-0.87(m,3H)；¹³CNMR(CDCl₃,100MHz)δ167.2,43.6,31.2,29.0,26.2,22.4,14.0.