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A method for direct oxidation of benzylic c-h bond into ketone or acid

A benzylic and direct technology, applied in the field of chemical catalytic oxidation, can solve problems such as environmental pollution, high equipment requirements, and impact on healthy life

Active Publication Date: 2020-12-04
ANHUI QINGYUN PHARMA & CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The oxidant heavy metal salt used in the catalytic oxidation of benzylic C-H causes serious pollution to the environment and directly or indirectly affects people's healthy life; most of the reaction conditions are relatively harsh, such as high pressure and high temperature reflux, etc. These harsh conditions On the one hand, the requirements for reaction equipment are high, and on the other hand, there are potential safety hazards. Therefore, it has always been a research hotspot to find green alternative oxidants and mild reaction conditions to facilitate the development of new green and environmentally friendly oxidation systems.

Method used

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  • A method for direct oxidation of benzylic c-h bond into ketone or acid
  • A method for direct oxidation of benzylic c-h bond into ketone or acid
  • A method for direct oxidation of benzylic c-h bond into ketone or acid

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Preparation of o-nitrobenzoic acid:

[0028]

[0029] Take 0.2mol of o-nitrotoluene, 200ml of dichloromethane, 20ml of water, 0.02mol of sodium bromide, 0.001mol of tetramethylpiperidine nitrogen oxide and mix well, raise the temperature to 40°C, and add a total of 0.24mol of Trichloroisocyanuric acid, keep stirring for 12 hours, add 50ml methanol to quench the reaction, filter the filtrate, extract 3 times with dichloromethane, each time with 100ml dichloromethane, combine the organic phases, wash with 400ml saturated aqueous sodium chloride solution , dried over anhydrous sodium sulfate, distilled off the organic solvent under reduced pressure, and recrystallized with a mixed solvent of ethyl acetate and petroleum ether to obtain o-nitrobenzoic acid with a yield of 94.2%.

Embodiment 2

[0031] To prepare acetophenone:

[0032]

[0033] Take 0.2mol ethylbenzene, 200ml dichloromethane, 20ml water, 0.02mol sodium bromide, 0.001mol tetramethylpiperidine nitrogen oxide and mix well, raise the temperature to 40°C, add a total of 0.24mol trichloride in 4 times Isocyanuric acid, keep stirring for 12 hours, add 50ml of methanol to quench the reaction, filter the filtrate, extract 3 times with dichloromethane, each time with 100ml of dichloromethane, combine the organic phases, wash with 400ml saturated aqueous sodium chloride solution, no Dry over sodium sulfate, distill off the organic solvent under reduced pressure, and recrystallize with a mixed solvent of ethyl acetate and petroleum ether to obtain acetophenone with a yield of 96.2%.

Embodiment 3

[0035] Preparation of phthalic acid:

[0036]

[0037] Take 0.2mol of o-xylene, 200ml of dichloromethane, 20ml of water, 0.04mol of sodium bromide, and 0.002mol of tetramethylpiperidine nitrogen oxide, mix them evenly, raise the temperature to 40°C, and add a total of 0.48mol of three Chloroisocyanuric acid, keep stirring for 12h, add 50ml methanol to quench the reaction, filter the filtrate, extract 3 times with dichloromethane, each time with 100ml dichloromethane, combine the organic phases, wash with 400ml saturated aqueous sodium chloride solution, Dry over anhydrous sodium sulfate, distill off the organic solvent under reduced pressure, and recrystallize with a mixed solvent of ethyl acetate and petroleum ether to obtain phthalic acid with a yield of 75%.

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PUM

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Abstract

The invention discloses a method for directly oxidizing benzylic C-H bonds into ketone or acid. A target product is obtained through an oxidation reaction with a compound containing benzylic C-H bondsas a substrate, trichloroisocyanuric acid as an oxidizing agent and sodium bromide and tetramethyl piperidine nitrogen oxide as catalysts. The oxidizing agent and the catalysts are cheap and easy toobtain, transport and store; the oxidative catalysis effect is good; the reaction condition is mild, the requirement and effect of harsh reaction conditions on equipment are avoided, and the method issuitable for industrial mass production. The use of a large quantity of heavy metal salts is avoided, and environmental pollution is further avoided.

Description

technical field [0001] The invention relates to the technical field of chemical catalytic oxidation, in particular to a method for directly oxidizing a C-H bond at a benzylic position to form a ketone or an acid. Background technique [0002] Oxidation of the benzylic C-H to prepare the corresponding carbonyl or carboxyl compound refers to the reaction of the substrate with the oxidant to directly oxidize the benzylic C-H bond in the organic molecule into a carbonyl or carboxyl. [0003] [0004] The selective oxidation of benzylic C-H to corresponding carbonyl compounds is an important chemical reaction in drug synthesis, and the direct oxidation of benzylic C-H is also widely used in agrochemical and pharmaceutical industries. Most of the oxidants used in the traditional benzylic C-H oxidation process adopt stoichiometric oxidants such as chromium trioxide (J.Org.Chem., 1985,50 (14): 2435-2438), permanganate (Synth.Commun., 2003, 33(6):1057-1065.) ] , high-priced iodi...

Claims

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Application Information

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IPC IPC(8): C07C201/12C07C205/57C07C45/28C07C49/78C07C51/16C07C63/16C07C49/67
Inventor 黄欢黄庆国李凯
Owner ANHUI QINGYUN PHARMA & CHEM
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