Method for hydrogen transfer reduction of nitrogenous heterocyclic compounds

A nitrogen heterocyclic compound and hydrogen transfer technology, applied in organic chemistry and other fields, can solve the problems of expensive raw materials and achieve good reproducibility, high yield, and high yield

Active Publication Date: 2018-12-21
SOUTHWEST PETROLEUM UNIV
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

However, some transition metal catalysts are noble metal catalysts, such as gold, silver, palladium, platinum and other catalysts, and these raw materials are all expensive [Tu Xifeng; GongLiuzhu.Angew.Chem.Int.Ed.2012,51(45),11346-11349 .Pi Danwei; Zhou Haifeng; Cui Peng; He Renke; Sui Yuebo.ChemistrySelect.2017,2(13):3976-3979.

Method used

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  • Method for hydrogen transfer reduction of nitrogenous heterocyclic compounds
  • Method for hydrogen transfer reduction of nitrogenous heterocyclic compounds
  • Method for hydrogen transfer reduction of nitrogenous heterocyclic compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Embodiment 1: the preparation of 2-methyl-1,2,3,4-tetrahydroquinoline

[0026] Weigh ethanolamine (61.08mg, 1.0mmol) into a Shrek tube, under the protection of an inert gas, cool to 0°C, add borane tetrahydrofuran complex (1M, 2.0mmol), stir at room temperature for 24h, vacuum the solvent The obtained oxazoboridine was directly used in the next step. Add 2-methylquinoline (71.5 mg, 0.5 mmol), tetrahydrofuran (2.0 mL), copper perchlorate hexahydrate (37.05 mg, 0.2 equiv). The reaction was stirred at room temperature for 24h. The obtained reactant was purified by silica gel column (petroleum ether / ethyl acetate=10:1) to obtain 2-methyl-1,2,3,4-tetrahydroquinoline (69.0 mg) with a yield of 93.9%.

[0027]

[0028] 2-Methyl-1,2,3,4-tetrahydroquinoline

[0029] 1 H NMR (400MHz, CDCl 3 )δ7.03-6.97 (m, 2H), 6.65 (td, J = 7.4Hz, 1.2Hz, 1H), 6.51 (dd, J = 8.2Hz, 1.2Hz, 1H), 3.70 (br, NH), 3.48 -3.38(m,1H),2.93-2.83(m,1H),2.81-2.73(m,1H),2.01-1.93(m,1H),1.68-1.58(m,1H),...

Embodiment 2

[0030] Embodiment 2: Preparation of 2-methyl-1,2,3,4-tetrahydroquinoline

[0031]Weigh ethanolamine (61.08mg, 1.0mmol) into a Shrek tube, under the protection of an inert gas, cool to 0°C, add borane tetrahydrofuran complex (1M, 2.0mmol), stir at room temperature for 24h, vacuum the solvent The obtained oxazoboridine was directly used in the next step. Add 2-methylquinoline (71.5 mg, 0.5 mmol), tetrahydrofuran (2.0 mL), copper trifluoromethanesulfonate (72.34 mg, 0.2 equiv). The reaction was stirred at room temperature for 24h. The obtained reactant was purified by silica gel column (petroleum ether / ethyl acetate=10:1) to obtain 2-methyl-1,2,3,4-tetrahydroquinoline (61.45 mg) with a yield of 83.5%.

[0032]

[0033] 2-Methyl-1,2,3,4-tetrahydroquinoline

[0034] 1 H NMR (400MHz, CDCl 3 )δ7.03-6.97 (m, 2H), 6.65 (td, J = 7.4Hz, 1.2Hz, 1H), 6.51 (dd, J = 8.2Hz, 1.2Hz, 1H), 3.70 (br, NH), 3.48 -3.38(m,1H),2.93-2.83(m,1H),2.81-2.73(m,1H),2.01-1.93(m,1H),1.68-1.58(m,1H),1....

Embodiment 3

[0035] Embodiment 3: Preparation of 2-methyl-1,2,3,4-tetrahydroquinoline

[0036] Weigh ethanolamine (61.08mg, 1.0mmol) into a Shrek tube, under the protection of an inert gas, cool to 0°C, add borane tetrahydrofuran complex (1M, 2.0mmol), stir at room temperature for 24h, vacuum the solvent The obtained oxazoboridine was directly used in the next step. Add 2-methylquinoline (71.5 mg, 0.5 mmol), methanol (2.0 mL), copper perchlorate hexahydrate (37.05 mg, 0.2 equiv). The reaction was stirred at room temperature for 24h. The obtained reactant was purified by silica gel column (petroleum ether / ethyl acetate=10:1) to obtain 2-methyl-1,2,3,4-tetrahydroquinoline (48.5mg) with a yield of 65.9%.

[0037]

[0038] 2-Methyl-1,2,3,4-tetrahydroquinoline

[0039] 1 H NMR (400MHz, CDCl 3 )δ7.03-6.97 (m, 2H), 6.65 (td, J = 7.4Hz, 1.2Hz, 1H), 6.51 (dd, J = 8.2Hz, 1.2Hz, 1H), 3.70 (br, NH), 3.48 -3.38(m,1H),2.93-2.83(m,1H),2.81-2.73(m,1H),2.01-1.93(m,1H),1.68-1.58(m,1H),1.25(d,J= 6...

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Abstract

The invention discloses a method for hydrogen transfer reduction of nitrogenous heterocyclic compounds. The method comprises the following steps: under the mild condition, taking the nitrogenous heterocyclic compounds (including a quinoline derivative, a quinoxaline derivative, 1,10-phenanthroline derivative and the like) as raw materials; taking oxazaborolidine as a hydrogen transfer reagent; taking low-cost metal salts such as copper, iron, cobalt and silver as catalysts, catalyzing and carrying out a hydrogen transfer reaction in 1,2,3,4-substituted positions, so as to prepare a series of hydrogen transfer reduction products of the nitrogenous heterocyclic compounds, wherein the oxazaborolidine is obtained by reacting amino-alcohol with a tetrahydrofuran complex of borane. The method disclosed by the invention has the advantages of high yield of a product, mild reaction conditions, good general applicability of the raw materials and low-cost and easily-obtained raw materials; extensive quantity reaction still shows good reproducibility. Therefore, the invention provides an effective scheme for industrial production of other high-value compounds containing the structure.

Description

Technical field: [0001] The invention belongs to the field of organic chemistry including the preparation of pharmaceutical intermediates and related chemical technologies, and specifically relates to a method for hydrogen transfer reduction of nitrogen-containing heterocyclic compounds. Background technique: [0002] The reduction products of nitrogen-containing heterocyclic compounds, especially the reduced quinoline compounds, are important structural units of many natural products, drugs and other biologically active substances, as well as structural fragments of some new functional materials. Compounds containing reduced quinoline structural units have a variety of physiological activities, and are widely used in dyes, drugs, insecticides, anti-oxidation and anti-corrosion [Wang Xuan, Wang Ting, Zhang Zhenming, Wang Runnan, Zhang Dandan, Li Shuan. Advances in Hydrogenation Reduction Technology of Quinoline and Its Derivatives. Chemical Industry Times, 2014,28(11):36-39....

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D215/06C07D405/04C07D219/02C07D471/04C07D241/38
CPCC07D215/06C07D219/02C07D241/38C07D405/04C07D471/04
Inventor 周太刚张灼华钟远海
Owner SOUTHWEST PETROLEUM UNIV
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