Preparation method of 2-(2, 2, 6, 6-tetramethyl piperidine nitroxide radical-4-subunit) acetic acid derivative and application thereof

A technology of tetramethylpiperidine nitroxide free radicals and derivatives, which is applied in the field of preparation of 2-acetic acid derivatives, can solve the problems of high cost of TEMPO, restrictions on application and development, unstable compounds, etc., and achieve low cost, Easy to obtain, stable effect

Inactive Publication Date: 2021-05-28
陕西海辰风扬医药科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Secondly, the cost of industrial preparation and production of TEMPO is high, the compound itself is not very stable, and has an unpleasant tast

Method used

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  • Preparation method of 2-(2, 2, 6, 6-tetramethyl piperidine nitroxide radical-4-subunit) acetic acid derivative and application thereof
  • Preparation method of 2-(2, 2, 6, 6-tetramethyl piperidine nitroxide radical-4-subunit) acetic acid derivative and application thereof
  • Preparation method of 2-(2, 2, 6, 6-tetramethyl piperidine nitroxide radical-4-subunit) acetic acid derivative and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Example 1: Preparation of 4-carbonyl-2,2,6,6-tetramethylpiperidine nitroxide radical 2,2,6,6-tetramethyl-4-piperidone (50g, 0.322mol , 1eq) was dissolved in a mixture of methanol (300mL) and water (200mL), slowly added dropwise a mixture of sodium tungstate dihydrate (17.6g, 0.055mol, 0.17eq) and hydrogen peroxide (110mL, aq 30%, 3eq), at room temperature Reaction for 8h, TLC detected that the reaction was complete, saturated the aqueous layer with K2CO3, extracted with methyl tert-butyl ether, dried, and spin-dried to give an orange-red solid 4-carbonyl-2,2,6,6-tetramethylpiperidine nitrogen oxide Free radical 48.8g, yield 89%.

Embodiment 2

[0037] Example 2: Preparation of 2-(2,2,6,6-tetramethylpiperidine nitroxide radical-4-ylidene) acetic acid (compound A)

[0038]NaH (3.5g, 88.3mmol, 1.5eq) was added to a 500mL reaction flask, under nitrogen protection, 100mL of dry THF was added, and after stirring at 0°C for 15min, triethyl phosphoroacetate (19.8g, 88.3mmol, 1.5eq), added in about 15 minutes, after the reaction solution in the reaction bottle was clarified and no gas was emitted, add 4-carbonyl-2,2,6,6-tetramethylpiperidine nitroxide radical (10g, 28.7mmol , 1eq), naturally rose to room temperature, and reacted for 4h. After HPLC showed that the reaction of the raw materials was complete, it was quenched with 30mL saturated ammonium chloride solution, extracted with ethyl acetate, and concentrated to obtain a red oily liquid.

[0039] The red oily liquid obtained in the previous step was dissolved in 150mL (MeOH / H 2 (0 / =3 / 1) in the mixed solution, add 4.7g of sodium hydroxide, stir at room temperature for 5...

Embodiment 3

[0040] Example 3: Preparation of 2-(2,2,6,6-tetramethylpiperidinyl nitroxide radical-4-ylidene) propionic acid (compound B)

[0041] The operation process was the same as in Example 2, and the phosphorylating reagent used was triethyl 2-phosphonopropionate to obtain 9.7 g of off-white solid with a purity of 98.1% and a total yield of 73%.

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Abstract

The invention discloses a preparation method of a 2-(2, 2, 6, 6-tetramethyl piperidine nitroxide radical-4-subunit) acetic acid derivative and an application thereof. According to the 2-(2, 2, 6, 6-tetramethylpiperidine nitroxide radical-4-subunit) acetic acid derivative, commercialized 2, 2, 6, 6-tetramethyl-4-piperidone is subjected to simple oxidation to obtain 4-carbonyl-2, 2, 6, 6-tetramethylpiperidine nitroxide radicals, then the 4-carbonyl-2, 2, 6, 6-tetramethylpiperidine nitroxide radicals react with corresponding phosphorylation reagents, hydrolysis is carried out, the raw materials used in the method are cheap and easy to obtain, compared with the 2, 2, 6, 6-tetramethylpiperidine nitroxide radicals in the production process, the production efficiency is high, and the production cost is low, the compound is stable in property, basically free of any smell, convenient to store and capable of being stored at the room temperature, meanwhile, the preparation method is simple and easy to obtain, and when the compound is used as a catalyst, due to the fact that the compound is high in activity, large in solubility in a water phase and extremely small in catalyst dosage.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a preparation method and application of 2-(2,2,6,6-tetramethylpiperidine nitroxide radical-4-ylidene) acetic acid derivatives. Background technique [0002] Oxidation of alcohols to corresponding aldehydes or ketones is one of the most widely used functional group conversion reactions in organic synthesis, and occupies a very important position in the field of basic research and fine chemical production. The catalytic oxidation method using 2,2,6,6-tetramethylpiperidine nitroxide radical ("TEMPO" for short) is currently considered to be one of the best oxidation methods. In this method, TEMPO is converted into an active intermediate of oxyammonium salts with oxidation activity under the action of an oxidizing agent, which can oxidize alcohols into aldehydes or ketones at 0°C to room temperature; at the same time, the oxidation process The sodium hypochlorite...

Claims

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Application Information

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IPC IPC(8): C07D211/94B01J31/00C07C45/29C07C45/80C07C45/82C07C47/54C07B60/00
CPCC07D211/94B01J31/006C07C45/29C07C45/80C07C45/82C07B61/02C07B2200/03B01J2231/763
Inventor 王灿辉黄治炎杨爽王伟李文亮李敬强胡西儒
Owner 陕西海辰风扬医药科技有限公司
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