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A kind of green synthesis method of 2-hydroxyl-3-nitroacetophenone

A technology of nitroacetophenone and green synthesis, which is applied in the direction of chemical instruments and methods, copper organic compounds, organic compound preparation, etc., can solve the problems of low yield, achieve environmental friendliness, save production costs, and increase yield Effect

Active Publication Date: 2020-11-06
KUNSHAN RIKITA PHARMA +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0010] 2-Hydroxy-3-nitroacetophenone, as an important pharmaceutical intermediate, can be used in the synthesis of anti-allergic and anti-asthma drug Pranlukast. At present, 2-hydroxy-3-nitroacetophenone is mainly Isolated by nitration of o-hydroxyacetophenone in less than 40% yield

Method used

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  • A kind of green synthesis method of 2-hydroxyl-3-nitroacetophenone
  • A kind of green synthesis method of 2-hydroxyl-3-nitroacetophenone
  • A kind of green synthesis method of 2-hydroxyl-3-nitroacetophenone

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[0032] A green synthesis method for 2-hydroxy-3-nitroacetophenone, comprising the following synthetic reaction steps: using carboxylic acid as a solvent, adding a metal salt catalyst to m-nitroacetophenone to carry out catalytic oxidation reaction, and making m-nitrobenzene The ethyl ketone is directional hydroxylated to obtain 2-hydroxy-3-nitroacetophenone, and its reaction equation is as follows:

[0033]

[0034] The invention provides a green synthesis method for 2-hydroxy-3-nitroacetophenone. The green synthesis reaction cleverly utilizes the ketone carbonyl and nitro groups in the molecule of m-nitroacetophenone as bidentate guiding groups. Carboxylic acid is used as a solvent, and m-nitroacetophenone is added with a metal salt catalyst to carry out catalytic oxidation reaction to make m-nitroacetophenone directional hydroxylation, and the yield of 2-hydroxy-3-nitroacetophenone obtained by the synthesis reaction is obtained. Significantly improved, the synthesis react...

Embodiment 1

[0046] In the autoclave, add 163 grams (1 mole) of m-nitroacetophenone, 20 grams (0.1 moles) of copper acetate monohydrate and 326 grams of 50% W / W (mass percent concentration) acetic acid, and pressurize by air in the autoclave to 0.8MPa, the temperature was raised to 100-105°C, the reaction was stirred for 10h, and the residual rate of m-nitroacetophenone was 1.55% by sampling and testing (detected by high performance liquid chromatography (HPLC) or gas chromatography (GC) ), the temperature dropped to 90 °C, the material was discharged while it was still hot, the temperature of the material liquid was lowered to 5 °C, and then filtered, and finally vacuum-dried at 60 °C-70 °C for 5 hours to obtain 160 grams of 2-hydroxy-3-nitroacetophenone , the yield is 89%, and the content is 98.2% (detected by high performance liquid chromatography (HPLC) or gas chromatography (GC)).

Embodiment 2

[0048] 163 grams (1 mole) of m-nitroacetophenone, 12.44 grams (0.05 moles) of nickel acetate tetrahydrate and 326 grams of 49% W / W (mass percent concentration) propionic acid were added to the autoclave, and air was added to the autoclave. Pressed to 1MPa, the temperature was raised to 100-105°C, the reaction was stirred for 10h, the residual rate of m-nitroacetophenone was 1.1% by sampling and detected (by high performance liquid chromatography (HPLC) or gas chromatography (GC) to detect and obtain ), the temperature dropped to 90°C, the material was discharged while it was still hot, the feed liquid was cooled to 0°C, filtered, and finally vacuum-dried at 60°C-70°C for 8 hours to obtain 165 grams of 2-hydroxy-3-nitroacetophenone, Its yield is 92%, and its content is 98.5% (detected by high performance liquid chromatography (HPLC) or gas chromatography (GC)).

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Abstract

The invention discloses a green synthesis method of 2-hydroxy-3-nitroacetophenone. The method comprises the following synthesis reaction steps: using carboxylic acid as a solvent, adding a metal saltcatalyst to m-nitroacetophenone, and performing a catalytic oxidation reaction so as to achieve oriented hydroxylation on m-nitroacetophenone and obtain the 2-hydroxy-3-nitroacetophenone. The reactionequation is shown as follows. The yield of the 2-hydroxy-3-nitroacetophenone obtained by using the synthesis reaction is improved remarkably, and the method not only is environmentally friendly, butalso saves the production cost.

Description

technical field [0001] The invention relates to the technical field of pharmaceutical intermediates, in particular to a green synthesis method of 2-hydroxy-3-nitroacetophenone. Background technique [0002] In the past decade, transition metal and noble metal-catalyzed directing-based activation of SP 2 Hydroxylation of carbon-hydrogen bonds has been reported continuously: [0003] In 1990, Reinaud's group reported that copper catalyzed the ortho-hydroxylation of aromatic hydrocarbons (ref: J.Chem.Soc.chem.commun.1990, 566). The reaction formula is as follows: [0004] [0005] In 2006, Chen et al. reported that pyridine-directed copper catalyzed the hydroxylation of 2-phenylpyridine (ref: J.Am.Chem.Soc, 2006, 128, 6790), and the reaction formula is as follows: [0006] [0007] In 2012, Ackermann's group reported that Ru(II) catalyzed the ortho-hydroxylation of keto groups to benzene rings (ref: Org.Lett.2012, 14, 6206), the reaction formula is as follows: [0008]...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C201/12C07C205/45
CPCC07C201/12C07F1/08C07C205/45
Inventor 易章国熊付超武乾刚张小亚
Owner KUNSHAN RIKITA PHARMA