Method for preparing aldehyde/ketone by catalyzing alcohol oxidation with ferric salt

A technology for ferric salts to catalyze alcohols and ferric salts. It is applied in the preparation of carbon-based compounds, chemical instruments and methods, and the preparation of organic compounds. It can solve the problems of limited substrate range and inapplicability of acid-sensitive substrates. broad effect

Active Publication Date: 2016-02-03
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In addition, these systems are all acidic, and cannot be applied to acid-sensitive substrates, and the scope of substrates is relatively limited.

Method used

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  • Method for preparing aldehyde/ketone by catalyzing alcohol oxidation with ferric salt
  • Method for preparing aldehyde/ketone by catalyzing alcohol oxidation with ferric salt
  • Method for preparing aldehyde/ketone by catalyzing alcohol oxidation with ferric salt

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037]

[0038] Add p-methylbenzyl alcohol (12.22g, 100.0mmol, R in the formula (I) 1 is 4-methyl, R 2 hydrogen, X is carbon, n is 1, m is 0), ferric chloride (0.81g, 5mmol), L-isoleucine (1.31g, 10mmol), TEMPO (1.56g, 10mmol), toluene 300.0mL , and then replace the air in the reaction flask with oxygen, and stir at reflux for 6h. After the reaction, the reaction solution was cooled to room temperature, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by column chromatography and eluted with a mixture of n-hexane:ethyl acetate (volume ratio 10:1) , collected the eluate containing the target compound, evaporated the solvent and dried to obtain 10.93 g of the product p-tolualdehyde with a yield of 91%.

[0039] H NMR spectrum 1 HNMR (500MHz, CDCl 3 ): δ2.38(s,3H),7.27(d,J=4.3Hz,2H),7.73(d,J=4.0Hz,2H),9.91(s,1H).

[0040] C NMR spectrum 13 CNMR (125MHz, CDCl 3 ): δ21.5, 129.4, 129.5, 134.0, 145.2, 191.6.

Embodiment 2

[0042]

[0043] The reactant used is p-methoxybenzyl alcohol (12.22g, 100.0mmol, R in the formula (I) 1 is 4-methoxy, R 2 Be hydrogen, X is carbon, n is 1, m is 0), experimental method and step are with embodiment 1, difference is: ferrous chloride (2.54g, 20mmol), L-isoleucine (1.31g , 10mmol), TEMPO (1.56g, 10mmol), chlorobenzene 300.0mL, reflux and stir under air condition for 24h. Finally, 12.53 g of the product was obtained with a yield of 92%.

[0044] H NMR spectrum 1 HNMR (500MHz, CDCl 3 ): δ3.71(s,3H),6.84(d,J=4.3Hz,2H),7.67(d,J=4.3Hz,2H),9.72(s,1H).

[0045] C NMR spectrum 13 CNMR (125MHz, CDCl 3 ): δ55.4, 114.2, 129.9, 131.8, 164.6, 190.6.

Embodiment 3

[0047]

[0048] The reactant used is 3,4,5-trimethoxybenzyl alcohol (12.22g, 100.0mmol, R in formula (I) 1 is 3,4,5-trimethoxy, R 2 Be hydrogen, X is carbon, n is 1, m is 0), experimental method and step are with embodiment 1, difference is: iron trifluoromethanesulfonate (25.15g, 50mmol), 2-methylalanine (5.16g, 50mmol), TEMPO (4.69g, 30mmol), xylene 300.0mL, replace the air in the reaction bottle with oxygen, and then reflux and stir for 1h. Finally, 18.05 g of the product was obtained with a yield of 92%.

[0049] H NMR spectrum 1 HNMR (500MHz, CDCl 3 ): δ3.89(d,J=4.0Hz,9H),7.09(s,2H),9.83(s,1H).

[0050] C NMR spectrum 13 CNMR (125MHz, CDCl 3 ): δ56.2, 60.8, 106.7, 131.7, 143.6, 153.6, 190.8.

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Abstract

The invention provides a method for preparing aldehyde / ketone by catalyzing alcohol oxidation with a ferric salt. The method comprises the following steps: mixing a compound shown in a formula (I) of a substrate, a ferric salt catalyst, a cocatalyst TEMPO (tetramethylpiperidinooxy), an amino acid ligand and a solvent; carrying out return flow agitation in an oxygen or air atmosphere for 1 to 60 h; then post-processing a reaction solution to obtain a product, namely a compound shown in a formula (II). According to the method provided by the invention, the ferric acid which is low in cost, easily available and environment-friendly is used as the catalyst; amino acids which are rich in resource, low in cost, easily available and easy to modify in a natural field are used as the ligand; the reaction substrate is high in applicability; first-grade benzyl alcohol, second-grade benzyl alcohol, allyl alcohol, heterocyclic aromatic alcohols and the like can be converted into corresponding aldehyde / ketone at high yield by adopting an oxidation system of the invention.

Description

(1) Technical field [0001] The invention relates to a method for preparing aldehyde / ketone by oxidation of alcohol, in particular to a method using iron salt as a catalyst, TEMPO (2,2,6,6-tetramethylpiperidine-nitrogen-oxide) as a cocatalyst, amino acid A new method for the preparation of aldehydes / ketones by oxidation of alcohols as ligands and oxygen or air as oxidant. (2) Background technology [0002] The selective oxidation of alcohols to the corresponding aldehydes or ketones is a very important class of reactions in organic chemistry and chemical engineering. [Sheldon, R.A. Kochi, J.K. Metal-Catalyzed Oxidation of Organic Compounds, Academic Press, New York, 1981]. This is because aldehydes or ketones are very important intermediates in the synthesis of pesticides, medicines and fragrances, and some aldehydes and ketones are themselves important components of fragrances. The world produces more than 10 carbonyl compounds per year 7 tons, most of which are obtained ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/38C07C47/542C07C47/575C07C47/55C07C47/232C07C45/39C07C49/76C07C49/807C07C49/217C07C253/30C07C255/56C07C201/12C07C205/44C07D333/22C07D213/48
CPCC07C45/38C07C45/39C07C47/232C07C47/542C07C47/55C07C47/575C07C49/217C07C49/76C07C49/807C07C201/12C07C205/44C07C253/30C07C255/56C07D213/48C07D333/22
Inventor 张国富李莎莎丁成荣张贵华谢晓强雷杰
Owner ZHEJIANG UNIV OF TECH
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