Preparation method of 3-o-alkylation quinoxaline-2(1H)-ketone compound

A technology of ketone compounds and oxyalkylquinones, which is applied in the field of preparation of 3-oxoalkylquinoxalin-2-ones, can solve the problems of complex reaction steps, harsh reaction conditions, and long reaction time, and achieve The effect of saving reaction costs, mild reaction conditions, and simplifying post-processing steps

Active Publication Date: 2018-11-06
QUFU NORMAL UNIV
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  • Abstract
  • Description
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Problems solved by technology

In recent years, chemists have been trying to introduce ether genes into complex organic molecular frameworks to enhance their biological activity, but due to the inertness of the α-carbon-hydrogen bonds of ether compounds, there are many problems, such as: complex reaction steps, harsh reaction conditions, reaction Long time, many by-products, low yield, metal reagents, strong oxidants and other non-environmental reagents are needed, etc.

Method used

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  • Preparation method of 3-o-alkylation quinoxaline-2(1H)-ketone compound
  • Preparation method of 3-o-alkylation quinoxaline-2(1H)-ketone compound
  • Preparation method of 3-o-alkylation quinoxaline-2(1H)-ketone compound

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Experimental program
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Effect test

Embodiment 1

[0030]

[0031] At 25°C, in a 15mL reaction tube, add 1-methylquinoxalin-2 (1H)-one 1a (0.2mmol), Rose Bengal (0.002mmol), triethylenediamine (0.2mmol), tert-butanol peroxide (0.2mmol), THF 2a (12 mmol, 1mL), mix well, and then stir the reaction for 24h under the irradiation of 3w blue LED light. After the reaction was detected by TLC, the reaction solution was concentrated to no solvent in vacuum (0.08Mpa) to obtain a crude product, which was washed with a mixed eluent of petroleum ether and ethyl acetate at a volume ratio of 3:1, Flash column chromatography on a silica gel column yielded 41.4 mg of the 1-methyl-3-(tetrahydrofuran-2-yl)quinoxalin-2(1H)-one product 3aa of this example as a colorless liquid with a yield of 90%.

[0032] The obtained product nuclear magnetic spectrum data are: 1 H NMR (CDCl 3 , 500 MHz, ppm): δ 7.81-7.78 (m,1H), 7.63-7.60 (m, 1H), 7.55 (t, J =8.3, 1H), 7.40-7.35 (m, 1H), 5.26-5.23 (m,1H), 4.04-4.00 (m, 1H), 3.87-3.83 (m, 1H), 3.61 (s, 3H...

Embodiment 2

[0035]

[0036] In a 15mL reaction tube, add 1,6,7-trimethylquinoxalin-2 (1H)-one 1b (0.2mmol), Rose Bengal (0.002mmol), triethylenediamine (0.2mmol), tert-butanol peroxide (0.2 mmol), THF 2a (12 mmol, 1 mL), mix well, then under the irradiation of 3w blue LED light, 20 ℃, stirring reaction for 24h. After detecting that the reaction is completed with TLC, the reaction solution is concentrated to solvent-free under vacuum (0.08Mpa) to obtain a crude product, which is then washed with a mixed eluent of petroleum ether and ethyl acetate with a volume ratio of 3:1, Flash column chromatography on a silica gel column yielded 37.1 mg of the 1,6,7-trimethyl-3-(tetrahydrofuran-2-yl)quinoxalin-2(1H)-one product 3ba in this example as a yellow oil. The rate is 72%.

[0037] The obtained product nuclear magnetic spectrum data are: 1 H NMR (CDCl 3 , 500 MHz, ppm): δ 7.56 (s, 1H),7.33 (s, 1H), 5.23-5.21 (m, 1H), 4.02-3.97 (m, 1H), 3.86-3.82 (m, 1H), 3.58(s, 3H), 2.37 ( s, 3H), 2.29...

Embodiment 3

[0040]

[0041] In a 15mL reaction tube, sequentially add 6-fluoro-1-methylquinoxalin-2 (1H)-one 1c (0.2mmol), water-soluble eosin (0.002mmol), triethylenediamine (0.2mmol), over Oxidized tert-butanol (0.2 mmol), THF 2a (12 mmol, 1 mL), mixed well, and then reacted with stirring at 60°C for 24 hours under the irradiation of a 3w blue LED light. After detecting that the reaction is completed by TLC, the reaction solution is concentrated to solvent-free under vacuum (0.08Mpa) to obtain a crude product, which is then washed with a mixed eluent of petroleum ether and ethyl acetate with a volume ratio of 3:1, Silica gel column flash column chromatography, the 6-fluoro-1-methyl-3-(tetrahydrofuran-2-yl)quinoxalin-2(1H)-one product 3ca of this example was obtained as a white solid 37.2 mg, yield 75%.

[0042] The obtained product nuclear magnetic spectrum data are: 1 H NMR (CDCl 3 , 500 MHz, ppm): δ 7.62-7.49 (m,3H), 5.25-5.22 (m, 1H), 4.05-4.01 (m, 1H), 3.89-3.84 (m, 1H), 3.6...

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Abstract

The invention belongs to the field of organic synthesis, and particularly discloses a preparation method of a 3-o-alkylation quinoxaline-2(1H)-ketone compound. The method includes the steps that a quinoxaline-2(1H)-ketone compound, an ether compound, alkaline, an oxidizing agent and a photocatalyst are added into a reacting bottle and react for 18-30 hours under illumination of a visible light lamp, after the reaction is ended, extracting treatment and concentrating treatment are performed, and the 3-o-alkylation substitution quinoxaline-2(1H)-ketone compound is obtained after column chromatography isolation purification treatment is performed. According to the method, the raw materials are easy to obtain, reaction conditions are simple and convenient to implement, using of metal reagents,high temperature and complex operation are avoided, reaction time is short, energy consumption is low, the compatibility of substrate functional groups is good, the safety and efficiency of the reaction are high, and high application values are obtained.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of 3-oxoalkylquinoxaline-2(1H)-one compounds. Background technique [0002] Quinoxalin-2(1H)-ones and their derivatives are an important class of nitrogen heterocyclic compounds, which are widely used in important fields such as agrochemicals, natural products, materials science and pharmacy. In particular, the 3-position functionalized substituted quinoxalin-2(1H)-one has attracted the research interest of many organic synthesis workers, because the 3-position substituent can regulate the quinoxalin-2(1H)-one skeleton. biological activity ( Arch.Pharm . 2006, 339, 564; J. Heterocycl. Chem ., 2006, 43, 541; J. Med. Chem. 2015, 58, 1254). On the other hand, cyclic or chain ether groups as core structural units widely exist in bioactive molecules, natural products and drug molecules with various biological activities, which are us...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D405/04C07D241/44
CPCC07D241/44C07D405/04
Inventor 魏伟王雷雷吕玉芬杨道山王桦
Owner QUFU NORMAL UNIV
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