CN107814751B - Method for preparing nitrile by catalytic oxidation of amine - Google Patents
Method for preparing nitrile by catalytic oxidation of amine Download PDFInfo
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Abstract
The invention provides a method for preparing nitrile by catalytic oxidation of amine, under the irradiation of visible light, oxygen is used as an oxidant, lithium tert-butoxide is used as alkali, copper salt and tris (2, 2' -bipyridyl) ruthenium dichloride form a co-catalyst, and the amine is catalyzed to synthesize a nitrile compound. The method can prepare the nitrile compound by visible light irradiation without adding a ligand, and is simple and easy to implement; the method has wide oxidant source, and oxygen has no pollution to the environment; the method has mild reaction conditions and high yield. The method of the present invention is of great significance in the synthesis of drugs, dyes, pesticides and heterocyclic compounds.
Description
Technical Field
The invention relates to a method for preparing nitrile by catalyzing amine oxide, in particular to a method for preparing a nitrile compound by catalyzing amine oxide through a copper salt and tris (2, 2' -bipyridyl) ruthenium dichloride, belonging to the field of organic synthesis.
Background
Nitrile compounds are important chemical intermediates and are widely applied to the synthesis of drugs, dyes, pesticides and heterocyclic compounds; in addition, cyano-containing compounds are also present in pharmaceuticals (Fleming, f.f., j.med.chem.2010, 53, 7902) and functional materials (Miller, j.s., acc.chem.res.2001, 34, 563). The traditional method for synthesizing nitrile compounds is a reaction of halide and inorganic cyanide or Sandmeyer reaction of aryl diazonium salt, and the methods generate excessive waste, and the cyanide is extremely toxic and pollutes the environment. In recent years, chemists have discovered novel synthesis methods, amide, aldoxime, alcohol and amine are used as raw materials, the nitrile compound is prepared by transition metal catalysis, the use of highly toxic substances is avoided, and the conditions are mild.
In the transition metal catalysis method, copper is an environment-friendly and low-cost metal, and the preparation of a nitrile compound by using copper salt as a catalyst has important significance in large-scale production; on the other hand, the ligand used in the copper salt catalytic reaction is usually a non-phosphine ligand, so that the pollution to the environment is reduced. For example, benzyl alcohol or benzaldehyde compounds are used as raw materials, ammonia water is used as a nitrogen source, and a nitrile compound (Tao, C. -Z., org.biomol.chem.,2013, 11, 3349) is prepared by copper catalytic oxidation; for example, in the synthesis of nitrile compounds by copper-catalyzed aerobic oxidation using primary amines as raw materials, heterogeneous catalysts are often used in such methods (Cao, x. -q.; gu, h. -w., chem. Commun.,2014, 50, 5637, likhar, p.r., adv. Synth. Final. 2014, 356, 189. In the homogeneous catalysis method of copper catalysis, stahl reports a cocatalyst (Stahl, S.S., ACS Catal.2013,3, 1652) formed by CuI and a nitrogen oxide free radical (ABNO), 4 '-di-tert-butyl-2, 2' -bipyridyl is added as a ligand, and 4-dimethylaminopyridine is used as an alkali, so that the catalytic oxidation synthesis of a nitrile compound by primary amine is realized. The method uses active free radicals, needs additional ligands and makes the system too complex.
Under the irradiation of visible light, oxygen is used as oxidant, tert-butyl lithium alkoxide is used as alkali, and copper salt and tris (2, 2' -bipyridine) ruthenium dichloride constitute co-catalyst to catalyze and oxidize primary amine directly to synthesize nitrile compound. The method can prepare the nitrile compound by visible light irradiation without adding a ligand and a nitrogen oxide free radical, and is simple and easy to implement; the source of the oxidant in the method is wide, and the oxygen has no pollution to the environment; the reaction can be carried out at room temperature, the conditions are mild, and the yield is high.
Disclosure of Invention
The invention aims to provide a method for preparing nitrile by catalytic oxidation of amine, which comprises the following steps: under the irradiation of visible light, oxygen is used as an oxidant, lithium tert-butoxide is used as a base, copper salt and tris (2, 2' -bipyridyl) dichlororuthenium are used as catalysts to catalyze amine oxide to synthesize a nitrile compound.
In order to achieve the above purpose, the present invention provides a method for preparing nitrile by catalytic oxidation of amine, the synthetic route of which is as follows:
the invention provides a method for preparing nitrile by catalytic oxidation of amine, which comprises the following steps:
adding copper salt, tris (2, 2' -bipyridyl) ruthenium dichloride and lithium tert-butoxide into a Schlenk reaction tube, vacuumizing by using a Schlenk double-row tube, adding the amine and the solvent under the condition of introducing oxygen, continuously introducing oxygen into a reaction system, controlling the temperature of the reaction system to be 20-35 ℃, irradiating the reaction system by using visible light (the wavelength is 400-760 nm), stirring and reacting for 18-36 hours, adding saturated sodium bisulfite aqueous solution and ethyl acetate, extracting and separating liquid, drying the separated organic phase by using anhydrous magnesium sulfate, removing the magnesium sulfate, concentrating the obtained organic phase, and separating the concentrated solution by using a silica gel column chromatography to obtain the nitrile compound,
wherein R in the general formula 1 and the general formula 2 is selected from aryl and alkyl.
In the steps of the method, the copper salt is CuI, cuBr, cuCl, cu (OAc) 2 Or Cu (NO) 3 ) 2 。
In the steps of the method, the molar ratio of the amine compound 1, copper salt, tris (2, 2' -bipyridyl) dichlororuthenium and lithium tert-butoxide is 1.0: 0.05-0.2: 0.005-0.05: 0.2-0.4.
In the steps of the method, the solvent is dimethyl sulfoxide, N, N-dimethylformamide.
Detailed Description
The invention will be better understood by the following examples of implementation, but not limiting the content of the invention.
Example 1: preparation of benzonitrile by catalytic oxidation of benzylamine
To a Schlenk reaction tube 1 was added0.0mg (0.10 mmol) of cuprous chloride, 12.8mg (0.02 mmol) of tris (2, 2' -bipyridyl) ruthenium dichloride and 12.0mg (0.15 mmol) of lithium tert-butoxide, wherein 55uL (0.5 mmol) of benzylamine and 3.0mL of N, N-dimethylformamide are added under the condition of introducing oxygen, oxygen is continuously introduced into the reaction system by using a Schlenk double-row tube, the temperature of the reaction system is controlled to be 25 ℃, a white light LED lamp (with the wavelength of 400-760 nm) is irradiated, the mixture is stirred and reacted for 18 hours, 3mL of saturated sodium bisulfite aqueous solution and 10mL of ethyl acetate are added, extraction and liquid separation are carried out, anhydrous magnesium sulfate is dried, magnesium sulfate is removed, the obtained organic phase is concentrated, and the concentrated solution is separated by silica gel column chromatography to obtain benzonitrile with the yield of 75%; 1 H NMR(300MHz，CDCl 3 )δ7.67-7.54(m，3H)，7.45(t，J＝7.7Hz，2H)； 13 C NMR(75MHz，CDCl 3 )δ132.5，131.7，128.8，118.5，112.0。
example 2: preparation of 4-methoxybenzonitrile by catalytic oxidation of 4-methoxybenzylamine
Adding 214.mg (1.5 mmol) of cuprous bromide, 32mg (0.05 mmol) of tris (2, 2' -bipyridyl) ruthenium dichloride and 160.0mg (2.0 mmol) of lithium tert-butoxide into a Schlenk reaction flask, vacuumizing by using a Schlenk double-row tube, adding 1.3mL (10.0 mmol) of 4-methoxybenzylamine and 20.0mL of dimethyl sulfoxide under the condition of introducing oxygen, continuously introducing oxygen into the reaction system by using the Schlenk double-row tube, controlling the temperature of the reaction system to be 30 ℃, under the irradiation of a blue light LED lamp (with the wavelength of 450-500 nm), stirring for reacting for 24 hours, adding 30mL of saturated sodium bisulfite aqueous solution and 100mL of ethyl acetate, extracting, separating, drying anhydrous magnesium sulfate, removing the magnesium sulfate, concentrating the obtained organic phase, and separating the concentrated solution by using a silica gel column chromatography to obtain 4-methoxybenzonitrile with the yield of 86%; 1 H NMR(300MHz，CDCl 3 )δ7.60-7.53(m，2H)，6.99-6.91(m，2H)，3.85(s，3H)； 13 C NMR(75MHz，CDCl 3 )δ162.8，133.8，119.1，114.7，103.8，55.4。
example 3: preparation of 4-trifluoromethyl benzonitrile by catalytic oxidation of 4-trifluoromethyl benzylamine
Adding 7.2mg (0.05 mmol) of cuprous bromide, 6.4mg (0.01 mmol) of tris (2, 2' -bipyridyl) ruthenium dichloride and 8.0mg (0.01 mmol) of lithium tert-butoxide into a Schlenk reaction tube, vacuumizing by using a Schlenk double-calandria tube, adding 71uL (0.5 mmol) of 4-trifluoromethylbenzylamine and 3.0mL of dimethyl sulfoxide under the condition of introducing oxygen, continuously introducing oxygen into a reaction system by using the Schlenk double-calandria tube, controlling the temperature of the reaction system to be 25 ℃, irradiating by a blue light LED lamp (with the wavelength of 450-500 nm), stirring for reacting for 18 hours, adding 3mL of saturated sodium bisulfite aqueous solution and 10mL of ethyl acetate, extracting for separating, drying by anhydrous magnesium sulfate, removing the magnesium sulfate, concentrating the obtained organic phase, and separating the concentrated solution by using a silica gel column chromatography to obtain 4-trifluoromethylbenzonitrile with the yield of 50%; 1 H NMR(500MHz，CDCl 3 )δ7.81(d，J＝8.2Hz，2H)，7.77(d，J＝8.2Hz，12H)； 19 F NMR(471MHz，CDCl 3 )δ-63.54； 13 C NMR(126MHz，CDCl 3 )δ134.68(q，J＝33.6Hz)，132.81(s)，126.31(q，J＝3.7Hz)，123.17(q，J＝273.4Hz)，117.55(s)，116.20(s)。
example 4: preparation of 2, 4-dimethoxybenzonitrile by catalytic oxidation of 2, 4-dimethoxybenzylamine
Adding 18.1mg (0.10 mmol) of copper acetate, 16.0mg (0.025 mmol) of tris (2, 2' -bipyridyl) ruthenium dichloride and 16.0mg (0.02 mmol) of lithium tert-butoxide into a Schlenk reaction tube, vacuumizing the tube by using a Schlenk double-row tube, adding 79uL (0.5 mmol) of 2, 4-dimethoxybenzylamine and 2.5mL of dimethyl sulfoxide under the condition of introducing oxygen, continuously introducing oxygen into the reaction system by using the Schlenk double-row tube, controlling the temperature of the reaction system to be 35 ℃, adding 3mL of saturated sodium bisulfite aqueous solution and 10mL of ethyl acetate under the irradiation of a white light LED lamp (with the wavelength of 400-760 nm), stirring the mixture to react for 20 hours, extracting and separating,drying anhydrous magnesium sulfate, removing magnesium sulfate, concentrating the obtained organic phase, and separating the concentrated solution by silica gel column chromatography to obtain 2, 4-dimethoxy benzonitrile with yield of 90%; 1 H NMR(500MHz，CDCl 3 )δ7.48(d，J＝8.5Hz，1H)，6.51(d，J＝8.6Hz，1H)，6.46(s，1H)，3.90(s，3H)，3.86(s，3H)； 13 C NMR(126MHz，CDCl 3 )δ164.77，163.00，135.08，117.06，105.87，98.66，94.23，56.11，55.84。
example 5: preparation of dodecanitrile by catalytic oxidation of 1-dodecylamine
Adding 14.4mg (0.10 mmol) of cuprous bromide, 6.4mg (0.01 mmol) of tris (2, 2' -bipyridyl) ruthenium dichloride and 8.0mg (0.01 mmol) of lithium tert-butoxide into a Schlenk reaction tube, vacuumizing by using a Schlenk double-row tube, adding 93mg (0.5 mmol) of 1-dodecylamine and 3.0mL of dimethyl sulfoxide under the condition of introducing oxygen, continuously introducing oxygen into the reaction system by using the Schlenk double-row tube, controlling the temperature of the reaction system to be 35 ℃, irradiating by a blue light LED lamp (with the wavelength of 450-500 nm), stirring for reacting for 36 hours, adding 3mL of saturated sodium bisulfite aqueous solution and 10mL of ethyl acetate, extracting, separating, drying anhydrous magnesium sulfate, removing the magnesium sulfate, concentrating the obtained organic phase, and separating the concentrated solution by using a silica gel column chromatography to obtain the dodecanitrile with the yield of 78%; 1 H NMR(500MHz，CDCl 3 )δ2.33(t，J＝7.2Hz，2H)，1.69-1.61(m，2H)，1.48-1.40(m，2H)，1.33-1.24(m，14H)，0.88(t，J＝6.9Hz，3H)； 13 C NMR(126MHz，CDCl 3 )δ119.99，32.03，29.85，29.69，29.65，29.44，28.91，28.82，25.54，22.82，17.28，14.24。
Claims (4)
1. a process for the catalytic oxidation of an amine to produce a nitrile comprising the steps of:
adding copper salt, tris (2, 2' -bipyridyl) ruthenium dichloride and lithium tert-butoxide into a Schlenk reaction tube, vacuumizing by using a Schlenk double-row tube, adding the amine and the solvent under the condition of introducing oxygen, continuously introducing oxygen into a reaction system, controlling the temperature of the reaction system to be 20-35 ℃, irradiating the reaction system by using visible light, stirring for reacting for 18-36 hours, adding saturated sodium bisulfite aqueous solution and ethyl acetate, extracting and separating liquid, drying the separated organic phase by using anhydrous magnesium sulfate, removing the magnesium sulfate, concentrating the obtained organic phase, and separating the concentrated solution by using a silica gel column chromatography to obtain the nitrile compound;
wherein the amine chemical structure is represented by formula 1, and the nitrile chemical structure is represented by formula 2:
wherein R in the general formula 1 and the general formula 2 is selected from aryl and alkyl.
2. The method of claim 1, wherein the copper salt is CuI, cuBr, cuCl, cu (OAc) 2 Or Cu (NO) 3 ) 2 。
3. The method of claim 1, wherein the molar ratio of the amine compound 1, the copper salt, the tris (2, 2' -bipyridyl) ruthenium dichloride and the lithium tert-butoxide is 1.0: 0.05-0.2: 0.005-0.05: 0.2-0.4.
4. The process according to claim 1, wherein the solvent is dimethyl sulfoxide, N, N-dimethylformamide.
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| CN111635334B (en) * | 2020-07-13 | 2021-11-30 | 四川大学 | Method for generating nitrile by catalyzing primary amine acceptor-free dehydrogenation through Ru complex |
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Non-Patent Citations (5)
| Title |
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| Daniil S. Ovoshchnikov等.Visible-Light-Driven Aerobic Oxidation of Amines to Nitriles over Hydrous Ruthenium Oxide Supported on TiO2.《ACS Catal.》.2015,(第5期),第34−38页. * |
| FRANCESCA PORTA等.OXIDATION OF AMINES IN THE PRESENCE OF RUTHENIUM COMPLEXES: MOLECULAR OXYGEN AND IODOSYLBENZENE AS OXIDANTS.《Journal of Catalysis》.1989,第50卷第333-341页. * |
| Jinho Kim，Shannon S. Stahl.Cu/Nitroxyl-Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature.《ACS Catal.》.2013,(第3期),第1652−1656页. * |
| N. Mizuno，Noritaka Mizuno.Scope, Kinetics, and Mechanistic Aspects of Aerobic Oxidations Catalyzed by Ruthenium Supported on Alumina.《Chem. Eur. J.》.2003,第4353-4361页. * |
| REGINALD TANG等.Homogeneous Catalytic Oxidation of Amines and Secondary Alcohols by Molecular Oxygen.《J.C.S. CHEM. COMM.》.1978,第562页. * |
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