CN109053460B - Method for catalyzing amination of benzyl alcohol compound - Google Patents
Method for catalyzing amination of benzyl alcohol compound Download PDFInfo
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- CN109053460B CN109053460B CN201810803944.0A CN201810803944A CN109053460B CN 109053460 B CN109053460 B CN 109053460B CN 201810803944 A CN201810803944 A CN 201810803944A CN 109053460 B CN109053460 B CN 109053460B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Abstract
The invention belongs to the field of organic synthesis, and discloses a method for catalyzing amination of benzyl alcohol compounds, which comprises the steps of mixing the benzyl alcohol compounds with aniline compounds, adding a solvent and a catalyst of trifluorophenylborane, and reacting at 85-120 ℃ for 12-24 hours to obtain benzyl alcohol amination products. According to the reaction, commercially available tris (pentafluorophenyl) borane is used as a catalyst to perform dehydration amination on a series of benzyl alcohol compounds, the reaction does not need to pre-activate or protect alcohol, atom economy is improved, chemical pollution is reduced, and a series of organic amine compounds with different substituents can be efficiently constructed by the method.
Description
Technical Field
The invention relates to a method for synthesizing an organic compound, in particular to a method for catalyzing alcohol compound amination reaction by using a nonmetal Lewis acid catalyst and synthesizing a series of different types of amine compounds.
Background
As an important organic compound, the alcohol compound not only has wide sources, but also has the characteristics of low toxicity, stability and the like, and has important positions in industry, medicine and fine chemical industry. The synthesis of nitrogen atom-containing compounds by alcohol compounds is an important chemical transformation, but because the alcoholic hydroxyl group itself has chemical properties of difficult leaving, the alcoholic hydroxyl group is mostly required to be pre-activated or protected in the common chemical transformation so as to enhance the leaving performance, and unnecessary atom waste and chemical pollution are generated in the process. At present, green chemistry and atom economy are two important indexes in chemical production. In conclusion, it is necessary and important to develop a green and efficient amination reaction of alcohol compounds.
The direct amination reaction of alcohol compounds by using a chemical catalysis method is an important method for quickly obtaining amine compounds. The Prim project group in 2006 reported direct amination of benzyl alcohols using metal lewis acid gold catalysts, which use gold sodium chloride trichloride as the catalyst and dichloromethane as the solvent to perform the sulfonylamination reaction on a series of differently substituted benzyl alcohols. In this reaction, an amine source (formula 1) having weak acidity such as sulfonamide must be used.
Subsequently, the chinese scientist schooling professor in charchun, 2012 developed a direct amination reaction of benzyl alcohol using sulfonic acid ionic liquid catalysis, which can obtain benzhydrol sulfonylation amination product (formula 2) at 80 ℃ with 1, 4-dioxane as solvent.
In the direct amination reaction of alcohol compounds reported at present, metal lewis acid is generally used, and an amine source must be a series of weakly acidic organic amines such as sulfonamide and amide, and these limiting conditions cannot meet the practical application in chemical production, so that it is very necessary to develop an alcohol amination reaction in which the amine source is an arylamine compound and a non-metal catalyst is used.
Disclosure of Invention
The invention aims to provide a method for catalyzing direct amination of benzyl alcohol compounds by using trifluoropentafluorobenzyl borane.
The purpose of the invention is realized by the following technical scheme:
a method for catalyzing amination of benzyl alcohol compounds comprises the steps of mixing the benzyl alcohol compounds with aniline compounds, adding a solvent and a catalyst of trifluorophenylborane, and reacting at 85-120 ℃ for 12-24 hours to obtain benzyl alcohol amination products.
The method comprises the following specific steps:
the benzyl alcohol compound is
Wherein the R1 radical is hydrogen atom, alkyl, aryl, ester group, halogen; the R2 group is alkyl, aryl, or cyano.
Preferably, the benzyl alcohol compound is benzhydrol and its analogs, phenethyl alcohol and its analogs (1-phenyl ethanol) or mandelonitrile.
The aniline compound is
The R3 group is methoxy, alkyl or aryl.
Preferably, the aniline compound is p-anisidine or p-methylaniline.
Preferably, the molar ratio of the benzyl alcohol compound to the arylamine compound is 1: 2.
Preferably, the amount of the catalyst added is 1% to 20%.
Preferably, the addition amount of the catalyst is 1 to 20 mole percent.
Preferably, the molar ratio of the benzyl alcohol compound to the catalyst is 1: 0.1.
Preferably, the solvent is nitromethane, toluene, 1, 2-dichloroethane, tetrahydrofuran or chloroform.
Compared with the prior art, the invention has the following advantages:
(1) the present invention utilizes trispentafluorophenylborane to catalyze the amination reaction on benzyl alcohol type substrates. According to the reaction, commercially available tris (pentafluorophenyl) borane is used as a catalyst to realize dehydration amination on a series of benzyl alcohol compounds, the reaction does not need to pre-activate or protect alcohol, and the method can efficiently construct a series of organic amine compounds with different substituents.
(2) The method has the advantages of simple operation, high reaction efficiency, no generation of redundant chemical pollution and high atom utilization rate.
Drawings
FIG. 1 shows the NMR chart of the product obtained in example 1, wherein (a) is a hydrogen spectrum and (b) is a carbon spectrum.
FIG. 2 shows the NMR chart of the product obtained in example 2, wherein (a) is a hydrogen spectrum and (b) is a carbon spectrum.
FIG. 3 shows the NMR chart of the product obtained in example 3, wherein (a) is a hydrogen spectrum and (b) is a carbon spectrum.
FIG. 4 shows the NMR chart of the product obtained in example 4, wherein (a) is a hydrogen spectrum and (b) is a carbon spectrum.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
Benzhydrol (36.8mg) was placed in a 10 ml reaction tube, 1 ml of nitromethane was added as a solvent, followed by addition of 11mg of trifluorophenylborane and p-anisidine (49.2mg), the reaction temperature was raised to 120 ℃, the reaction was cooled to room temperature after 12 hours of reaction and the product was isolated by column chromatography after removal of the solvent: N-Diphenylmethyl-4-methoxyaniline (49mg, 86% yield) was obtained as a brown liquid, 86% yield. Analyzing data:1H NMR(400MHz,CDCl3)δ7.34(m,8H),7.27–7.22(m,2H),6.71(d,J＝8.9Hz,2H),6.50(d,J＝8.9Hz,2H),5.41(s,1H),3.70(s,3H).13C NMR(100MHz,CDCl3)δ152.14,143.22,141.70,128.74,127.42,127.31,114.74,114.63,63.84,55.75.HRMS(ESI)m/z[M+H]+:Calcd for C20H20NO:290.1545.Found:290.1524.
example 2
1-Phenylethanol (24.4mg) was placed in a 10 ml reaction tube, 1 ml of nitromethane was added as a solvent, followed by addition of 11mg of trifluorophenylborane and p-anisidine (49.2mg), the reaction temperature was raised to 120 degrees Celsius, the reaction was cooled to room temperature after 12 hours of reaction and the product was isolated by column chromatography after removal of the solvent: 4-methoxy-N- (1-phenylethyl) aniline (30mg, 67% yield) was a colorless liquid, 67% yield. Analyzing data:1H NMR(400MHz,CDCl3)δ7.33(dt,J＝13.1,7.4Hz,4H),7.21(t,J＝7.8Hz,1H),6.68(d,J＝8.9Hz,2H),6.46(d,J＝8.9Hz,2H),4.40(q,J＝6.7Hz,1H),3.68(s,3H),1.49(d,J＝6.7Hz,3H).13C NMR(100MHz,CDCl3)δ151.89,145.51,141.58,128.64,126.84,125.91,114.77,114.55,55.75,54.27,25.17.HRMS(ESI)m/z[M+H]+:Calcd for C15H18NO:228.1388.Found:228.1370.
example 3
Mandelonitrile (26.6mg) was placed in a 10 ml reaction tube, 1 ml of nitromethane was added as a solvent, followed by addition of 11mg of trifluorophenylborane and p-anisidine (49.2mg), the reaction temperature was raised to 120 ℃, after 12 hours of reaction, the reaction was cooled to room temperature, followed by removal of the solvent and isolation of the product by column chromatography: 2- (4-methoxyphenyl) amine-2-phenylacetonitrile (33mg, 68% yield) as a colorless liquid, 68% yield. Analyzing data:1H NMR(400MHz,CDCl3)δ7.66–7.56(m,2H),7.45(dt,J＝11.9,4.1Hz,3H),6.85(d,J＝8.9Hz,2H),6.76(d,J＝6.7Hz,2H),5.34(d,J＝8.4Hz,1H),3.77(s,3H).13C NMR(100MHz,CDCl3)δ154.16,138.59,134.16,129.47,129.29,127.28,118.48,116.34,115.02,55.68,51.61.HRMS(ESI)m/z[M+H]+:Calcd for C15H15N2O:239.1184.Found:239.1165.
example 4
2-hydroxy-2-acetophenone (42.4mg) was placed in a 10 ml reaction tube, 1 ml of nitromethane was added as a solvent, followed by addition of 11mg of trifluorophenylborane and p-methoxyaniline (49.2mg), the reaction temperature was raised to 120 ℃, the reaction was cooled to room temperature after 12 hours of reaction and the product was isolated by column chromatography after removal of the solvent: 2- (4-methoxyphenyl) imine-1, 2-tolane-1-one (51.2mg, 81% yield). Colorless liquid, 81% yield. Analyzing data:1H NMR(400MHz,CDCl3)δ7.86(d,J＝7.9Hz,2H),7.77(d,J＝7.9Hz,2H),7.44(dt,J＝21.7,7.5Hz,4H),7.33(t,J＝7.6Hz,2H),6.90(d,J＝8.6Hz,2H),6.67(d,J＝8.6Hz,2H),3.66(s,3H).13C NMR(100MHz,CDCl3)δ198.66,165.41,157.04,142.33,135.39,134.54,134.29,131.41,129.27,128.87,128.76,127.98,122.26,113.95,55.27.HRMS(ESI)m/z[M+H]+:Calcd for C21H18NO:316.1338.Found:316.1335.
the above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (5)
1. A method for catalyzing amination of benzyl alcohol compounds is characterized in that the benzyl alcohol compounds and aniline compounds are mixed, solvent and catalyst trifluorophenylborane are added, and the mixture reacts for 12 to 24 hours at 85 to 120 ℃ to obtain benzyl alcohol amination products;
the benzyl alcohol compound is
Wherein the R1 radical is hydrogen atom, alkyl, aryl, ester group, halogen; the R2 group is alkyl, aryl, or cyano;
the aniline compound is
The R3 group is methoxyl, and the solvent is nitromethane.
2. The method of claim 1, wherein the benzyl alcohol compound is benzhydrol or mandelonitrile.
3. The method of claim 2, wherein the molar ratio of benzyl alcohol compound to aniline compound is 1: 2.
4. The method of claim 3, wherein the catalyst is added in an amount of 1 to 20 mole percent.
5. The method of claim 4, wherein the molar ratio of benzyl alcohol compound to catalyst is 1: 0.1.
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| CN115677568B (en) * | 2022-10-27 | 2024-04-19 | 南京晓庄学院 | One-step amination method of p-methylphenol |
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| CN1696121A (en) * | 2005-05-19 | 2005-11-16 | 天津大学 | 4-[2-(artyl sulfo) benzyl]-1-derivative of aryl-piperazine, preparation method and application |
| CN104447354A (en) * | 2014-12-02 | 2015-03-25 | 温州大学 | Green method for preparing amine derivatives from alcohols and amines |
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| US6495658B2 (en) * | 2001-02-06 | 2002-12-17 | Folia, Inc. | Comonomer compositions for production of imide-containing polyamino acids |
| JP2008037822A (en) * | 2006-08-08 | 2008-02-21 | Osaka Univ | Method for forming carbon-nitrogen or carbon-carbon bond |
| CN103073372B (en) * | 2011-10-25 | 2016-03-02 | 中国科学院兰州化学物理研究所 | The method of functionalized ion liquid catalytically synthesizing aminated compounds |
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| CN1696121A (en) * | 2005-05-19 | 2005-11-16 | 天津大学 | 4-[2-(artyl sulfo) benzyl]-1-derivative of aryl-piperazine, preparation method and application |
| CN104447354A (en) * | 2014-12-02 | 2015-03-25 | 温州大学 | Green method for preparing amine derivatives from alcohols and amines |
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| A münchnonimine-based method for the synthesis of 3,6-diaryl-2(1H)-pyridones;Sylvain Burger，等;《Journal of Chemical Research》;20020801;第2002卷(第8期);第355-356页 * |
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