Method for preparing carbonyl compound by oxidizing alcohol

A carbonyl compound and alcohol oxidation technology, applied in the field of alcohol oxidation to prepare aldehydes or ketones, can solve problems such as water resistance and strong carcinogens

Active Publication Date: 2021-09-07
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] The invention overcomes the use of highly toxic organic solvents, water resistance or the use of strong carcinogen NaNO in the existing iron catalytic system 2 etc., provide a kind of under mild conditions, in water phase, with hydrated ferric nitrate (Fe(NO 3 ) 3 9H 2 O), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (4-OH-TEMPO) and carboxylic acid as a catalyst, oxygen or air as an oxidant, the selective oxidation of alcohol to aldehyde or The Keto Method

Method used

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  • Method for preparing carbonyl compound by oxidizing alcohol
  • Method for preparing carbonyl compound by oxidizing alcohol
  • Method for preparing carbonyl compound by oxidizing alcohol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] Embodiment 1: the synthesis of benzaldehyde

[0017]

[0018] Under oxygen atmosphere, Fe(NO 3 ) 3 9H 2 O (60.6 mg, 0.15 mmol), H 2 C 2 o 4 2H 2 O (18.9 mg, 0.15 mmol), 4-OH-TEMPO (25.8 mg, 0.15 mmol), 2 mL H 2 O, benzyl alcohol (324.4 mg, 3 mmol), react at 50 ℃ for 2 h. After the reaction, sodium chloride was added to the mixture for salting out. After filtration, it was extracted with 12 mL of ethyl acetate and dried over anhydrous sodium sulfate. Purified by column chromatography (using a mixed solvent of ethyl acetate / petroleum ether volume ratio of 1:15 as eluent), the isolated yield was 93%. 1 H NMR (400 MHz, CDCl 3 , TMS): δ 10.00 (s, 1H), 7.86 (d, 2H), 7.61 (t, 1H), 7.51 (t, 2H).

[0019] The above 50 ℃ was replaced with room temperature, and the rest remained unchanged. After 2 hours of reaction, the yield was 40%; after 7 hours of reaction, the yield was 91%.

[0020] The above-mentioned oxygen was replaced by air, and the rest remained unchange...

Embodiment 2

[0025] Embodiment 2: the synthesis of p-chlorobenzaldehyde

[0026]

[0027] Under oxygen atmosphere, Fe(NO 3 ) 3 9H 2 O (60.6 mg, 0.15 mmol), H 2 C 2 o 4 2H 2 O (18.9 mg, 0.15 mmol), 4-OH-TEMPO (25.8 mg, 0.15 mmol), 2 mL H 2 O, p-chlorobenzyl alcohol (427.7 mg, 3 mmol), react at 50 ℃ for 4 h. After the reaction, add a small amount of ethyl acetate to the mixture, then add sodium chloride for salting out, filter and extract with 12 mL of ethyl acetate, dry over anhydrous sodium sulfate, and purify by column chromatography (in the form of ethyl acetate / petroleum ether volume The mixed solvent that ratio is 1: 10 is eluent), and yield is 86%. 1 H NMR (400 MHz, CDCl 3 ): δ 9.99 (s, 1H), 7.83 (d, 2H), 7.52 (d, 2H).

[0028] The above-mentioned oxygen was replaced by air, and the rest remained unchanged. The reaction was carried out for 4 h, and the yield was 81%.

Embodiment 3

[0029] Embodiment 3: the synthesis of p-methoxybenzaldehyde

[0030]

[0031] Under oxygen atmosphere, Fe(NO 3 ) 3 9H 2 O (60.6 mg, 0.15 mmol), H2 C 2 o 4 2H 2 O (18.9 mg, 0.15 mmol), 4-OH-TEMPO (25.8 mg, 0.15 mmol), 2 mL H 2 O, p-methoxybenzyl alcohol (414.5 mg, 3 mmol), react at 50 ℃ for 2 h. After the reaction, sodium chloride was added to the mixture for salting out. After filtration, it was extracted with 12 mL of ethyl acetate, dried over anhydrous sodium sulfate, and purified by column chromatography (using a mixed solvent of ethyl acetate / petroleum ether volume ratio of 1:10 as eluent), and the yield was 89%. 1 H NMR (400 MHz, CDCl 3 , TMS): δ 9.89 (s, 1 H), 7.84 (d, 2 H), 7.01 (d, 2 H), 3.89 (s, 3H).

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Abstract

The invention provides a method for preparing aldehydes or ketones through alcohol oxidation. According to the method, alcohol is oxidized into aldehyde or ketone by taking water as a solvent, iron nitrate hydrate (Fe (NO3)3.9H2O), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (4-OH-TEMPO) and carboxylic acid as catalysts and oxygen or air as an oxidizing agent. Compared with the prior art, the method provided by the invention takes water as a solvent, avoids the use of polluting halogenated hydrocarbon or strong cancerogen sodium nitrite (NaNO2), is more environment-friendly, greatly reduces the cost, and is a method suitable for industrial production.

Description

technical field [0001] The invention relates to a method for preparing aldehydes or ketones by oxidizing alcohols, in particular to a method in which hydrated ferric nitrate (Fe(NO 3 ) 3 9H 2 O), a mixture of 4-hydroxy-2, 2, 6, 6-tetramethylpiperidine nitrogen oxide (4-OH-TEMPO) and carboxylic acid as catalyst, oxygen or air as oxidant, prepared by oxidation of alcohol Aldehyde or ketone method. Background technique [0002] Aldehydes and ketones, as two types of carbonyl compounds, widely exist in nature, and also play a very important role in organic synthesis, and are intermediates in the synthesis of perfumes, drugs and functional materials. Oxidation of alcohols is one of the important methods to prepare aldehydes or ketones. Compared with traditional oxidants, oxygen is an ideal oxidant because it has the advantage of being cheap and readily available, and produces only water as the only by-product. Therefore, in the past 30 years, transition metal-catalyzed oxida...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C47/54C07C47/55C07C47/575C07C47/542C07C47/228C07C47/232C07C47/546C07C49/78C07C49/403C07C45/38C07C69/76C07C67/313C07C205/44C07C201/12C07D307/48
CPCC07C45/38C07C67/313C07C201/12C07D307/48C07C2601/14C07C47/54C07C47/55C07C47/575C07C47/542C07C47/228C07C49/78C07C49/403C07C47/232C07C47/546C07C69/76C07C205/44
Inventor 孙宏枚谢振彪鞠恒伟何明羽
Owner SUZHOU UNIV
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