Method for preparing aryl formic acid compound with microchannel continuous flow reactor

A technology of aryl formic acid and microchannel, which is applied in the preparation of organic compounds, chemical instruments and methods, preparation of carboxylate, etc., can solve problems such as potential safety hazards, achieve safety assurance, small liquid holding capacity, and reduce environmental toxicity The effect of the formation of harmful by-products

Inactive Publication Date: 2018-10-09
杭州陶瑞生物科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] However, these liquid-phase oxidations often present significant safety concerns when performed in conventional tank reactors
How to solve the safety problem has become the biggest obstacle to its industrial application

Method used

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  • Method for preparing aryl formic acid compound with microchannel continuous flow reactor
  • Method for preparing aryl formic acid compound with microchannel continuous flow reactor
  • Method for preparing aryl formic acid compound with microchannel continuous flow reactor

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0025] Example 1: Preparation of p-bromobenzoic acid

[0026]

[0027] P-bromotoluene (Formula I, R=4-Br) 1.71g (10mmol), cobalt naphthenate 0.0156g (0.05mmol), manganese acetate 0.0087g (0.05mmol), iron nitrate 0.0404g (0.1mmol), 30 % mass concentration hydrogen peroxide 0.034g (1mmol), acetonitrile 30ml, mix well. Mix this solution with 0.2L / min O in a mixer at a flow rate of 0.5ml / min 2 (O 2 Pressure is 2MPa) mixed and flows through the microreactor (the microreactor has 20 microchannel mixer substrates) heated to 100 ℃ in advance, the reaction residence time is 47.89s, and the reaction mixture flows into the beaker through the back pressure valve, Sodium sulfite was added to remove excess hydrogen peroxide, and the solvent was distilled off under reduced pressure to obtain 1.42 g of p-bromobenzoic acid with a yield of 83%.

[0028] Proton NMR spectrum: (400MHz, Chloroform-d) δ13.205(s, 1H), 7.905(d, J=8Hz, 2H), 6.97(d, J=8Hz, 2H)

example 2

[0029] Example 2: Preparation of p-toluic acid

[0030]

[0031] P-methyltoluene (Formula I, R=4-CH 3 ) 1.06g (10mmol), cobalt stearate 0.1251g (0.2mmol), manganese acetate 0.0346g (0.2mmol), ferric chloride 0.0811g (0.5mmol), 30% mass concentration hydrogen peroxide 1.02g (3mmol), acetic acid 25ml, mix well. Mix this solution with 0.4L / min O in a mixer at a flow rate of 1ml / min 2 (O 2 The pressure is 10MPa) mixed and flows through the microreactor (the microreactor has 35 microchannel mixer substrates) preheated to 120°C, the reaction residence time is 42s, the reaction mixture flows into the beaker through the backup valve, and cools , solids were precipitated, and filtered by suction to obtain 0.99 g of p-toluic acid with a yield of 93%.

[0032] Proton NMR spectrum: (400MHz, Chloroform-d) δ12.830(s, 1H), 7.875(d, J=8Hz, 2H), 7.318(d, J=8Hz, 2H), 2.377(s, 1H),

example 3

[0033] Example 3: Preparation of m-methoxybenzoic acid

[0034]

[0035] 1.22g (10mmol) of m-methyltoluene (Formula I, R=3-OMe), 0.0125g (0.05mmol) of cobalt acetate, 0.0173g (0.1mmol) of manganese acetate, 0.1398g (0.3mmol) of ferric oxalate pentahydrate, 0.034g (1mmol) of 30% mass concentration hydrogen peroxide and 10ml of acetonitrile were mixed uniformly. Put this solution in a mixer at a flow rate of 0.5ml / min at 0.1L / min O 2 (O 2 The pressure is 0.5MPa) mixed and flowed through the microreactor preheated to 25°C (the microreactor has a microchannel mixer substrate), the reaction residence time is 4.78s, and the reaction mixture flows into the beaker through the back pressure valve , adding sodium sulfite to remove excess hydrogen peroxide, and distilling off the solvent under reduced pressure to obtain 0.7686 g of m-methoxybenzoic acid with a yield of 63%.

[0036] Proton NMR spectrum: (400MHz, Chloroform-d) δ9.973(s, 1H), 7.468(d, J=8.1Hz, 2H), 7.388(d, J=8.0Hz, ...

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Abstract

The invention discloses a method for preparing an aryl formic acid compound with a microchannel continuous flow reactor. The method comprises the following steps: with methyl aromatics represented bythe formula (I) as a raw material, a mixture of cobalt salt, manganese salt and iron salt as a ternary complex catalyst, hydrogen peroxide with mass concentration of 30% as a cocatalyst, and acetonitrile or acetic acid as an organic solvent, uniformly mixing to form a homogeneous solution, pumping the homogeneous solution into the microchannel continuous flow reactor through a metering pump, reacting at 25 to 150 DEG C in an oxygen atmosphere of 0.5 to 10 MPa for 4 to 100 seconds to obtain a reaction mixture, and carrying out post-treatment to obtain the aryl formic acid compound represented by the formula (II). According to the invention, with cleaning agents such as oxygen and hydrogen peroxide as oxidants and cocatalysts, by-products toxic and harmful to the environment are reduced, thesystem is greener and cleaner, the reaction can be continuously carried out, the production efficiency is high, and industrialized amplified production is facilitated.

Description

(1) Technical field [0001] The invention relates to a method for preparing aryl formic acid compounds using a microchannel continuous flow reactor. (2) Background technology [0002] Aryl formic acid compounds are a very important class of organic synthesis intermediates, widely used in the synthesis of dyes, pesticides, spices, medicines and so on. [0003] Among many synthetic methods, the method of directly oxidizing methyl aromatic hydrocarbons to prepare aromatic formic acid compounds with oxygen (or air) as oxidant and transition metal as catalyst has attracted widespread attention. This is because oxygen (or air) is cheap and easy to obtain, and the by-product after its reduction is only water, which is non-toxic, harmless and pollution-free to the environment, and is a green and clean oxidant. Among the many reports on oxygen oxidation, the gas-phase fixed-bed oxidation is the most. Although this type of oxidation has the advantages of convenient equipment maintenan...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C63/70C07C63/04C07C65/21C07C51/265
CPCC07C51/265C07C63/70C07C63/04C07C65/21C07C63/06
Inventor 张国富杨文英毛宁郑卫华
Owner 杭州陶瑞生物科技有限公司
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