CN110483308B - Method for preparing secondary amine compound by imine hydrogenation reduction - Google Patents
Method for preparing secondary amine compound by imine hydrogenation reduction Download PDFInfo
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- C07C209/52—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of imines or imino-ethers
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- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The invention belongs to the technical field of chemical intermediates of medicines and natural compounds and related chemistry, and provides a method for preparing a secondary amine compound by imine hydrogenation reduction. The imine and the derivative thereof are used as raw materials, nano porous palladium is used as a catalyst, hydrogen is used as a hydrogen source, and the imine compound is efficiently hydrogenated and reduced, wherein the pressure of the hydrogen is 0.1-20.0 MPa; the molar concentration of the N-benzylalkenylphenylimine and the derivatives thereof in the solvent is 0.01-2 mmol/mL. The size of the adopted catalyst pore framework is 1-50nm, and the molar ratio of the imine and the derivative thereof to the used catalyst is 1: 0.01-1: 0.5. the method has the advantages of high product yield, very mild reaction conditions, simple operation and post-treatment, good catalyst repeatability, no obvious reduction of the catalytic effect after multiple use, and possibility for realizing industrialization.
Description
Technical Field
The invention belongs to the technical field of chemical intermediates of medicines and natural compounds and related chemistry, and relates to a method for preparing secondary amine compounds by imine hydrogenation reduction.
Background
Amine compounds are used as bases in many synthetic transformations, as key intermediates in organic synthesis, and are also important building blocks for many common polymers such as nylon. Due to its importance, people pay attention to the research on the synthetic amine compounds, and the research focuses on changing the types of catalysts and hydrogen sources in the reaction process, so as to improve the performance of the synthetic amine compounds.
There are many methods for synthesizing amines, such as reduction with a nitrogen atom-containing group (amide, cyano, nitro, etc.), alkylation of ammonia, primary or secondary amines, and the like. However, the most commonly used method is a reductive amination method, which is classified into a direct reductive amination method and an indirect reductive amination method according to reaction steps. The direct reductive amination method is to directly react aldehyde or ketone and ammonia or amine with a reducing agent to synthesize a target amine compound. In this case, the choice of the reducing agent is very critical to the success of the reaction, the reducing agent must selectively reduce imine (or imine ion) under the same reaction conditions rather than aldehyde or ketone, the reaction is prone to produce by-products, making its separation difficult, and sometimes toxic metal tin is used as a catalyst, causing metal contamination and other disadvantages [ Tararov V I, Kadyrov R, Riermeier T H, et al, chem, commun.,2000, 1867-; apodaca R, Xiao W.org.Lett.,2001,3,1745-](ii) a The indirect reductive amination method is to perform imine and then perform hydrogenation reduction on the imine to form amine compounds. The choice of reducing agent in this way is relatively simple compared to direct reductive amination, since there is no competition or interference from the carbonyl compound. However, catalysts with higher activity and harsh reaction conditions are required, and disadvantages such as complex catalyst preparation, poor atom economy, low yield, etc. are likely to occur [ Fernandes AC,
C C.Tetrahedron Lett.,2005,46,8881-8883；Ramaraj A,Nethaji M,Jagirdar B R.J.Org.Chem.,2019,883,25-34]. The nano porous palladium catalyst (PdNPore) is a novel nano catalyst, has a unique bicontinuous three-dimensional porous structure, has the pore canal diameter of about 1-50nm, large specific surface area and stable structure, is easy to prepare and recover, can be repeatedly used, and overcomes the defects of the traditional nano structure catalyst [ TANAKA S, KANEKO T, ASAO N, YAMAMOTO Y, CHEN M-W, ZHANG W, INOUE A.chem.Commun.2011, 47, 5985-; KANEKO T, TANAKA S, ASAO N, YAMAMOTO Y, et al, adv, Synth, Catal.,2011,353, 2927-.]。
Disclosure of Invention
The invention provides a method for preparing secondary amine compounds by imine hydrogenation reduction, the reaction conditions of the method are very mild, the highest yield can reach 96%, the used catalyst has the advantages of high activity, good stability and the like, and the catalytic activity of the catalyst is basically unchanged after repeated use.
The technical scheme of the invention is as follows:
a method for preparing secondary amine compounds by imine hydrogenation reduction takes imine and derivatives thereof as raw materials, hydrogen is taken as a hydrogen source under the action of a catalyst, and imine and derivatives thereof are efficiently hydrogenated and reduced in an organic solvent to generate secondary amine, wherein the reaction route is as follows:
the reaction temperature is 25-80 ℃, and the reaction time is 12-36 h;
R1one selected from hydrogen, alkyl, methoxy, halogen, hydroxyl, ester group, cyano and nitro;
R2one selected from hydrogen, alkyl, methoxy, halogen, hydroxyl, ester group, cyano and nitro;
R1and R2The same or different;
wherein the catalyst is a nano porous palladium catalyst (PdNPore), and the pore size is 1-50 nm; the molar ratio of imine and derivatives thereof to the catalyst used is 1: 0.01-1: 0.5; the pressure of the hydrogen is 0.1-20.0 MPa; the molar concentration of the imine and the derivative thereof in the organic solvent is 0.01-2 mmol/mL.
The organic solvent is one or more of diethyl ether, acetonitrile, cyclohexane, N-hexane, tetrahydrofuran, toluene, ethanol, isopropanol, chloroform, dichloromethane, acetone, N-dimethylformamide, and water.
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 is a scheme showing the preparation of N-benzylaniline of example 11H nuclear magnetic spectrum.
FIG. 2 is a scheme showing the preparation of N-benzylaniline of example 113C nuclear magnetic spectrum.
FIG. 3 is a scheme showing the preparation of 4- (4-methoxybenzyl) benzonitrile in example 21H nuclear magnetic spectrum.
FIG. 4 is a scheme showing the preparation of 4- (4-methoxybenzyl) benzonitrile in example 213C nuclear magnetic spectrum.
FIG. 5 is a scheme showing the preparation of N- (4-hydroxybenzyl) aniline of example 31H nuclear magnetic spectrum.
FIG. 6 is a scheme showing the preparation of N- (4-hydroxybenzyl) aniline of example 313C nuclear magnetic spectrum.
FIG. 7 is a drawing showing the preparation of methyl 4- (benzylamino) benzoate in example 41H nuclear magnetic spectrum.
FIG. 8 is a scheme showing the preparation of methyl 4- (benzylamino) benzoate in example 413C nuclear magnetic spectrum.
FIG. 9 is a scheme showing the preparation of 4-methoxy-N- (4-methylbenzyl) aniline in example 51H nuclear magnetic spectrum.
FIG. 10 is a block diagramPreparation of 4-methoxy-N- (4-methylbenzyl) aniline from example 513C nuclear magnetic spectrum.
FIG. 11 is a scheme showing the preparation of N- (3, 4-dimethoxybenzyl) -4-methoxyaniline in example 61H nuclear magnetic spectrum.
FIG. 12 is a scheme showing the preparation of N- (3, 4-dimethoxybenzyl) -4-methoxyaniline in example 613C nuclear magnetic spectrum.
FIG. 13 is a scheme showing the preparation of N- (2-cyanobenzyl) aniline of example 71H nuclear magnetic spectrum.
FIG. 14 is a scheme showing the preparation of N- (2-cyanobenzyl) aniline of example 713C nuclear magnetic spectrum.
FIG. 15 is a drawing of 3, 5-dimethylbenzylaniline from example 81H nuclear magnetic spectrum.
FIG. 16 is a drawing of 3, 5-dimethylbenzylaniline from example 813C nuclear magnetic spectrum.
Detailed Description
The imine hydrogenation reduction method has the advantages that the highest reaction yield reaches 96%, the selected catalyst has good catalytic reaction repeatability, the operation and the post-treatment are simple, the catalytic effect is not obviously reduced after repeated utilization, and favorable conditions are provided for industrial production of the imine hydrogenation reduction method.
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-benzylaniline
To an ethanol (2mL) solvent added with PdNPore (2.7mg,5 mol%) catalyst, substrate N-benzylalkenylbenzimide (90.5mg,0.5mmol) was added, a balloon connected with hydrogen gas was placed on a magnetic stirrer to react for 24h at 30 ℃, and column chromatography (silica gel, 200 mesh 300 mesh; developing agent, petroleum ether: ethyl acetate: 10: 1; 3% triethylamine was added to the developing agent) was performed to obtain 87.9mg of N-benzylaniline with a yield of 96%.
A yellow solid;1H NMR(400MHz,CDCl3):δ7.47–7.41(m,4H),7.38–7.36(m,1H),7.28–7.24(m,2H),6.83–6.79(m,1H),6.72(d,J＝8.0Hz,2H),4.40(s,2H),4.09(s,1H).13C NMR(400MHz,CDCl3)δ148.2,139.5,129.3,128.7,127.6,127.3,117.6,112.9,48.4.
example 2: synthesis of 4- (4-methoxybenzyl) benzonitrile
To an isopropanol (2mL) solvent charged with PdNPore (2.7mg,5 mol%) catalyst was added the substrate 4- [ (4-methoxybenzylidene) amino ] cyanobenzene (118.1mg,0.5mmol), the reaction was carried out for 24h with a balloon connected to a hydrogen-filled gas on a magnetic stirrer at 50 deg.C, and column chromatography (silica gel, 200 mesh 300; developing solvent, petroleum ether: ethyl acetate 10: 1; 3% triethylamine was added to the developing solvent) gave 112.9mg of 4- (4-methoxybenzyl) benzonitrile in 95% yield.
A white solid;1H NMR(400MHz,CDCl3)δ7.36(d,J＝8.8Hz,2H),7.23(d,J＝8.8Hz,2H),6.87(d,J＝8.8Hz,2H),6.56(d,J＝8.8Hz,2H),4.69(s,1H),4.27(d,J＝8.0Hz,2H),3.78(s,3H).13C NMR(100MHz,CDCl3)δ159.1,151.2,133.7,129.8,128.7,120.6,114.2,112.4,98.6,55.3,46.9.
example 3: synthesis of N- (4-hydroxybenzyl) aniline
To an N-hexane (2mL) solvent to which PdNPore (2.7mg,5 mol%) catalyst was added, a substrate of N- (4-hydroxybenzylidene) aniline (98.5mg,0.5mmol) and a balloon connected with a hydrogen-filled gas were placed on a magnetic stirrer to react at 40 ℃ for 24 hours, and column chromatography (silica gel, 200 mesh, 300 mesh; developing solvent, petroleum ether: ethyl acetate: 10: 1; 3% triethylamine was added to the developing solvent) was performed to obtain N- (4-hydroxybenzyl) aniline 95.5mg, with a yield of 96%.
A yellow solid;1H NMR(400MHz,CDCl3)δ7.24–7.06(m,4H),6.79–6.63(m,5H),4.51(s,1H),4.22(s,2H).13C NMR(100MHz,CDCl3)δ154.9,148.1,131.4,129.3,129.1,117.7,115.5,113.0,47.9.
example 4: synthesis of methyl 4- (benzylamino) benzoate
To a solvent of PdNPore (2.7mg,5 mol%) in tetrahydrofuran (2mL) with a catalyst was added N-benzylidene (4-carbomethoxy) aniline (119.5mg,0.5mmol) as a substrate, a balloon filled with hydrogen was connected and placed on a magnetic stirrer at 30 ℃ for reaction for 24h, and column chromatography (silica gel, 200 mesh 300; developing solvent, petroleum ether: ethyl acetate 10: 1, 3% triethylamine was added to the developing solvent) was performed to obtain 114.4mg of methyl 4- (benzylamino) benzoate with a yield of 95%.
A yellow solid;1H NMR(400MHz,CDCl3)δ7.85(d,J＝8.4Hz,2H),7.35–7.25(m,5H),6.58(d,J＝8.8Hz,2H),4.53(s,1H),4.37(d,J＝8.0Hz,2H),3.83(s,3H).13C NMR(100MHz,CDCl3)δ167.2,151.7,138.3,131.5,128.7,127.5,127.4,118.6,111.6,51.5,47.6.
example 5: synthesis of 4-methoxy-N- (4-methylbenzyl) aniline
To a solvent of PdNPore (2.7mg,5 mol%) in dichloromethane (2mL) added with a catalyst, 4-methoxy-N- [ (4-methylphenyl) methylene ] aniline (112.5mg,0.5mmol) as a substrate, a balloon connected with hydrogen gas was placed on a magnetic stirrer and reacted at 60 ℃ for 24h, and column chromatography (silica gel, 200 mesh 300; developing solvent, petroleum ether: ethyl acetate 10: 1; 3% triethylamine was added to the developing solvent) was performed to obtain 102.1mg of 4-methoxy-N- (4-methylbenzyl) aniline with a yield of 90%.
A yellow solid;1H NMR(400MHz,CDCl3)δ7.24(d,J＝8.0Hz,2H),7.13(d,J＝8.0Hz,2H),6.76(d,J＝8.0Hz,2H),6.58(d,J＝8.0Hz,2H),4.21(s,2H),3.72(s,3H),2.33(s,3H).13C NMR(100MHz,CDCl3)δ152.1,142.5,136.7,136.6,129.2,127.5,114.8,114.0,55.7,48.9,21.0.
example 6: synthesis of N- (3, 4-dimethoxybenzyl) -4-methoxyaniline
To acetone (2mL) solvent added with PdNPore (2.7mg,5 mol%) catalyst was added substrate (3, 4-dimethoxybenzylidene) - (4-methoxyphenyl) amine (135.5mg,0.5mmol), balloon connected with hydrogen gas was placed on a magnetic stirrer and reacted for 22h, column chromatography (silica gel, 200 mesh 300; developing solvent, petroleum ether: ethyl acetate 10: 1, 3% triethylamine was added to the developing solvent) was performed to obtain 128.3mg of N- (3, 4-dimethoxybenzyl) -4-methoxyaniline, yield 94%.
A yellow solid;1H NMR(400MHz,CDCl3)δ6.91(d,J＝8.0Hz,2H),6.83(d,J＝8.0Hz,1H),6.79–6.77(m,2H),6.63–6.60(m,2H),4.21(s,2H),3.87(d,J＝8.0Hz,6H),3.74(s,3H),3.71(s,1H).13C NMR(100MHz,CDCl3)δ152.2,149.1,148.1,142.5,132.2,119.7,114.9,114.1,111.1,110.8,55.9,55.8,55.8,49.2.
example 7: n- (2-cyanobenzyl) aniline
To an ethanol (2mL) solvent added with PdNPore (2.7mg,5 mol%) catalyst was added substrate (2-cyanobenzylidene) aniline (103.1mg,0.5mmol), balloon connected with hydrogen gas was placed on a magnetic stirrer and reacted for 20h at 30 ℃, and column chromatography (silica gel, 200 mesh 300; developing solvent, petroleum ether: ethyl acetate: 10: 1; 3% triethylamine was added to the developing solvent) was performed to obtain N- (2-cyanobenzyl) aniline 99.8mg, with a yield of 96%.
A yellow solid; mp 86-87 ℃;1H NMR(400MHz,CDCl3)δ7.66–7.53(m,3H),7.35–7.14(m,3H),6.74–6.59(m,3H),4.58(s,2H),4.31(s,1H).13C NMR(100MHz,CDCl3)δ147.1,143.6,133.0,133.0,129.3,128.1,127.5,118.1,117.5,112.9,111.1,46.3.IR(KBr)3410,3035,2930,2220,1600,1510,1450,1270,867,762,744,689cm-1.HRMS Calcd for C14H12N2:208.1000[M]+；found:208.0999.
example 8: 3, 5-dimethylbenzylaniline
To a toluene (2mL) solvent charged with PdNPore (2.7mg,5 mol%) catalyst was added the substrate N- (3, 5-dimethylbenzylidene) aniline (104.5mg,0.5mmol), the balloon connected with hydrogen gas was placed on a magnetic stirrer and reacted for 24h at 70 deg.C, and column chromatography (silica gel, 200 mesh 300; developing solvent, petroleum ether: ethyl acetate 10: 1; 3% triethylamine was added to the developing solvent) gave 99.2mg of 3, 5-dimethylbenzylaniline with a yield of 94%.
A yellow solid;1H NMR(400MHz,CDCl3)δ7.18–7.14(m,2H),6.97(s,2H),6.90(s,1H),6.72–6.68(m,1H),6.61(d,J＝8.0Hz,2H),4.21(s,2H),3.92(s,1H),2.30(s,6H).13C NMR(100MHz,CDCl3)δ148.4,139.4,138.3,129.3,129.0,125.5,117.5,112.9,48.4,21.4.
comparative example 1: completely consistent with the reaction conditions and substrates of example 1, only the catalyst was changed to Pd/C catalyst, to obtain 26.3mg of N-benzylaniline with a yield of 29%.
Comparative example 2: the reaction conditions and substrates were completely the same as those in example 1 except that the catalyst was changed to Pd20Al80alloy catalyst, N-benzylaniline can not be obtained.
Comparative example 3: completely consistent with the reaction conditions and substrates of example 1, N-benzylaniline could not be obtained by changing the catalyst to a nanoporous gold catalyst (AuNPore).
Claims (2)
1. A method for preparing secondary amine compounds by imine hydrogenation reduction is characterized in that imine and derivatives thereof are used as raw materials, hydrogen is used as a hydrogen source under the action of a catalyst, and imine and derivatives thereof are hydrogenated and reduced in an organic solvent to generate secondary amine, wherein the reaction route is as follows:
the reaction temperature is 25-80 ℃, and the reaction time is 12-36 h;
R1one selected from hydrogen, alkyl, methoxy, halogen, hydroxyl, ester group and cyano;
R2one selected from hydrogen, alkyl, methoxy, halogen, hydroxyl, ester group and cyano;
R1and R2The same or different;
wherein the catalyst is a nano porous palladium catalyst, and the pore size is 1-50 nm; the molar ratio of imine and derivatives thereof to the catalyst used is 1: 0.01-1: 0.5; the pressure of the hydrogen is 0.1-20.0 MPa; the molar concentration of the imine and the derivative thereof in the organic solvent is 0.01-2 mmol/mL.
2. The method according to claim 1, wherein the organic solvent is one or more of ethyl ether, acetonitrile, cyclohexane, N-hexane, tetrahydrofuran, toluene, ethanol, isopropanol, chloroform, dichloromethane, acetone, N-dimethylformamide, and water.
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Non-Patent Citations (4)
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| Celite‐Polyaniline supported palladium catalyst for chemoselective hydrogenation reactions;Heta A. Patel等;《Applied Organometallic Chemistry》;20190217;1-11 * |
| Synthesis and Evaluation of Antitumor Activity of Novel 1,4-Naphthoquinone Derivatives (IV);Bok Hee Kim等;《Arch Pharm Res》;20061231;第29卷(第2期);123-130 * |
| Unsupported nanoporous palladium‐catalyzed chemoselective hydrogenation of quinolines: Heterolytic cleavage of H2 molecule;Ye Lu等;《催化学报》;20181105;第39卷(第11期);1746–1752 * |
| 去合金化制备纳米多孔金属材料的研究进展;谭秀兰 等;《材料导报: 综述篇》;20090331;第23卷(第3期);68-76,71 * |
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