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Method for preparing tetrahydroquinoline compounds by catalytic hydrogenation of ruthenium catalyst

A technology of catalytic hydrogenation and tetrahydroquinoline, which is applied in the field of synthetic chemistry, can solve the problems of discharging a large amount of silicon-containing waste, low atom economy, and high price of silane, and achieves a simple and green synthesis method, high reaction atom economy, and highly selective effect

Active Publication Date: 2021-01-22
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Other methods such as using AgOTf as a catalyst and silane as a reducing agent have also been reported, but the price of silane used is relatively high, and the atomic economy of the reaction is not high, and a large amount of silicon-containing waste will be emitted.

Method used

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  • Method for preparing tetrahydroquinoline compounds by catalytic hydrogenation of ruthenium catalyst
  • Method for preparing tetrahydroquinoline compounds by catalytic hydrogenation of ruthenium catalyst
  • Method for preparing tetrahydroquinoline compounds by catalytic hydrogenation of ruthenium catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] A method for preparing tetrahydroquinoline compounds by catalytic hydrogenation of a ruthenium catalyst, the reaction formula is as follows:

[0028]

[0029] The catalyst [(cymene)RuCl 2 ] 2 (0.03mmol), phosphine ligand triphenylphosphine PPh 3 (0.07mmol), quinoline (1.0mmol), then add solvent methanol 2mL, pump and exchange air three times under hydrogen atmosphere, connect hydrogen balloon under normal pressure, react at room temperature for 8 hours, and concentrate by vacuum rotary evaporation after the reaction The reaction solution was separated by column chromatography to obtain the corresponding product with a separation yield of 90%, high selectivity and no other by-products. 1 H NMR (400MHz, CDCl 3 )δ:6.97-6.93(m,2H),6.60(td,J=7.2,1.2Hz,1H),6.46(d,J=7.8Hz,1H),3.73(s,1H),3.30-3.28(m ,2H),2.76(t,J=6.0Hz,2H),1.96-1.92(m,2H);HRMS(ESI):calcd for C 9 h 12 N[M+H] + 134.2012, found 134.2013.

Embodiment 2

[0031] A method for preparing tetrahydroquinoline compounds by catalytic hydrogenation of a ruthenium catalyst, the reaction formula is as follows:

[0032]

[0033] The catalyst [(cymene)RuCl 2 ] 2 (0.05mmol), phosphine ligand tricyclohexylphosphine PCy 3 (0.12mmol), 2-methylquinoline (1.0mmol), and then add solvent ethanol 2mL, pump and change air three times under hydrogen atmosphere, connect hydrogen balloon under normal pressure, react at room temperature for 10 hours, and use reducing The reaction solution was concentrated by rotary evaporation, and the corresponding product was obtained by column chromatography separation, with an isolated yield of 93%, high selectivity, and no other by-products. 1 H NMR (400MHz, CDCl 3 )δ:6.96-6.94(m,2H),6.59(td,J=7.2,1.2Hz,1H),6.45(dd,J=7.2,1.2Hz,1H),3.67(s,1H),3.41-3.37 (m,1H),2.85-2.80(m,1H),2.74-2.70(m,1H),1.93-1.89(m,1H),1.59-1.56(m,1H),1.19(d,J=6.0Hz ,3H); HRMS(ESI):calcd for C 10 h 14 N[M+H] + 148.1126, found 148.1123...

Embodiment 3

[0035] A method for preparing tetrahydroquinoline compounds by catalytic hydrogenation of a ruthenium catalyst, the reaction formula is as follows:

[0036]

[0037] The catalyst [(cymene)RuCl 2 ] 2 (0.04mmol), phosphine ligand trimethylphosphine PMe 3(0.10mmol), 4-methylquinoline (1.0mmol), and then add solvent methanol 2mL, pump and change air three times under hydrogen atmosphere, connect a hydrogen balloon under normal pressure, and react at room temperature for 12 hours. The reaction solution was concentrated by rotary distillation, and the corresponding product was obtained by column chromatography separation with an isolated yield of 94%, high selectivity and no other by-products. 1 H NMR (400MHz, CDCl 3 )δ:7.05(d,J=7.8Hz,1H),6.97-6.94(m,1H),6.63(td,J=7.2,0.6Hz,1H),6.46(d,J=7.8Hz,1H), 3.85(s,1H),3.35-3.31(m,1H),3.29-3.25(m,1H),2.94-2.88(m,1H),2.01-1.96(m,1H),1.70-1.65(m,1H ), 1.29 (d, J=7.2Hz, 3H); HRMS (ESI): calcd for C 10 h 14 N[M+H] + 148.1126, found 148....

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Abstract

The invention relates to a method for preparing tetrahydroquinoline compounds by catalytic hydrogenation of a ruthenium catalyst, which comprises the following steps: by using p-cymene ruthenium chloride dimer as a catalyst and hydrogen as a reducing agent, mixing the p-cymene ruthenium chloride dimer, phosphine ligand and quinoline compounds, and dissolving the mixture in an organic solvent to react, and carrying out post-treatment to obtain the tetrahydroquinoline derivative. Compared with the prior art, the method has the advantages of easily available raw materials, mild conditions, simpleoperation, atom economy, simple and green synthesis process, mild reaction conditions, excellent selectivity, high yield and good reaction universality, and has a wide application value in fine chemical intermediate synthesis.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry, and in particular relates to a method for preparing tetrahydroquinoline compounds by catalytic hydrogenation of a ruthenium catalyst. Background technique [0002] 1,2,3,4-Tetrahydroquinolines are an important class of organic compounds, which exist in a variety of active natural products, have a wide range of biological activities, and have many applications in production and life. Many drugs contain tetrahydroquinoline structures, such as Levonantradol which has antiemetic and analgesic properties, and drugs such as virantmycin and helquinoline which have antibacterial activity. In addition, this type of compound can also be used as an organic ligand to coordinate with different transition metals to prepare transition metal complexes with different new structures. [0003] At present, the main synthetic method of 1,2,3,4-tetrahydroquinoline compounds is still the Aza-Diels-Alder re...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D215/06C07D215/18
CPCC07D215/06C07D215/18Y02P20/584
Inventor 姚子健零春
Owner SHANGHAI INST OF TECH
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