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Method for preparing aromatic acid through oxidation reaction of 1, 2, 3-grade alkyl substituted aromatic compounds under iron catalysis

An oxidation reaction and iron compound technology, which is applied in the preparation of organic compounds, chemical instruments and methods, and preparation of sulfonic acid, can solve the problems of serious pollution and inability to oxidize, and achieve simple operation, mild oxidation conditions, and substrate applicability broad effect

Inactive Publication Date: 2021-08-20
XI AN JIAOTONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The traditional method of synthesizing organic acids is through the oxidation of alcohols or aldehydes, but usually requires the use of some measured amounts of strong oxidants such as potassium permanganate and sodium hypochlorite, and will produce a large amount of inorganic salts and some other oxides after oxidation, which cannot be well Selective oxidation is achieved, and the pollution is serious

Method used

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  • Method for preparing aromatic acid through oxidation reaction of 1, 2, 3-grade alkyl substituted aromatic compounds under iron catalysis
  • Method for preparing aromatic acid through oxidation reaction of 1, 2, 3-grade alkyl substituted aromatic compounds under iron catalysis

Examples

Experimental program
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Effect test

Embodiment 1

[0045] Add the iron catalyst (x 1 mol%), additives (x 2 mol%), toluene (2mmol), anhydrous acetonitrile (4 milliliters), after the addition finishes, stir and dissolve, mix uniformly, place the reaction tube under the light (hv) of wavelength 390nm to irradiate and constantly stir, treat to react after finishing The reaction tube was removed from the light source, the reaction mixture was transferred to a flask, the crude product was obtained by distillation under reduced pressure, and 190.7 mg of benzoic acid was obtained by flash column chromatography with a yield of 78%. The product was a white solid. 1 HNMR (400MHz, CDCl 3 )δ12.25(brs,1H,-COOH),8.15(d,J=7.4Hz,2H,Ar-H),7.63(t,J=7.4Hz,1H,Ar-H),7.49(t,J =7.5Hz,2H,Ar-H). 13 C NMR (101MHz, CDCl 3 )δ172.7, 133.8, 130.2, 129.3, 128.5.

Embodiment 2

[0047] By the method described in Example 1, the difference is that the amount of reagent used is: iron catalyst (x 1 mol%), additives (x 2 mol%), 4-cyanotoluene (46.9 mg, 0.4 mmol), anhydrous acetonitrile (4 ml); the reaction tube was heated to 50° C. to obtain 50.4 mg of 4-cyanobenzoic acid with a yield of 86%. 1 H NMR (400MHz, DMSO-d 6 )δ13.58(s,1H,-COOH),8.07(d,J=8.3Hz,2H,Ar-H),7.97(d,J=8.3Hz,2H,Ar-H). 13 C NMR (101MHz, DMSO-d 6 )δ166.1, 134.8, 132.7, 130.0, 118.2, 115.1.IRν(neat, cm- 1 )3418,2987,1700,1653,1430,1323,1288,1131,768,749.

Embodiment 3

[0049] By the method described in Example 1, the difference is that the amount of reagent used is: iron catalyst (x 1 mol%), additives (x 2 mol%), 4-fluorotoluene (44.1 mg, 44 microliters, 0.4 mmol), anhydrous acetonitrile (4 milliliters); irradiation under the light (hv) of wavelength 350nm, obtain 34.4 milligrams of 4-fluorobenzoic acid, productive rate 61%. 1 H NMR (400MHz, DMSO-d 6 )δ13.07(brs,1H,-COOH),8.00(dd,J 1 =8.7,J 2 =5.7Hz, 2H, Ar-H), 7.31(t, J=8.9Hz, 2H, Ar-H). 13 C NMR (101MHz, DMSO-d 6 )δ166.4,165.0(C-F,d, 1 J C-F =252.5Hz), 132.1(C-F,d, 3 J C-F =9.5Hz), 127.4(C-F,d, 4 J C-F =2.8Hz), 115.7(C-F,d, 2 J C-F =30.3Hz). 19 F NMR (376MHz, DMSO-d 6 )δ-106.9.

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Abstract

The invention relates to a method for preparing aromatic acid through oxidation reaction of 1, 2, 3-grade alkyl substituted aromatic compounds under iron catalysis. The method comprises the following steps: under the action of an iron compound, providing proper temperature and / or light energy, and in the presence of an oxidant and / or an additive, carrying out C-C bond breakage on benzyl positions of aromatic compounds in a solvent to realize selective oxidation so as to obtain a corresponding oxidation compound ketone or acid. According to the invention, C-C bond rupture and oxidation are directly and selectively carried out on the benzyl position of the aromatic compound, so that the method has the advantages of simple reaction, simple operation, mild oxidation condition, high atom economy, high reaction yield, easy separation and purification of the product, suitability for synthesis of benzoic acid derivative compounds, and the like; air can be directly used as an oxidizing agent, so that use of a large amount of heavy metal salt is avoided, and the method is very attractive in industrial production; and the method has very large application potential in the fields of metal catalysis, chemical synthesis and the like by using cheap metal for reaction.

Description

technical field [0001] The invention relates to the technical field of chemical synthesis, in particular to a method for preparing aromatic acids by oxidation reaction of 1, 2 and 3 alkyl substituted aromatic compounds under iron catalysis. The oxidation reaction of C-H, C-C, C-X bond breaking, that is, through toluene or substituted toluene under the promotion of iron catalysts and additives, and under the irradiation of visible light, the oxidation reaction is carried out through oxidants to generate a series of derivatives of benzoic acids with different substituents thing. Background technique [0002] The synthesis of aromatic acids from alkyl-substituted aromatic compounds through deep oxidation of alkyl groups is an important organic transformation in chemical synthesis. Among them, the oxidation of aromatic compounds with 2nd and 3rd grade alkyl substituents involves the breaking of C-C bond. [0003] The cleavage of C-C bonds usually requires noble metal catalysis...

Claims

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Application Information

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IPC IPC(8): C07C51/265C07C253/30C07C255/57C07C63/06C07C63/70C07C303/02C07C309/58C07C201/12C07C205/57C07C65/24C07D213/79C07D333/40C07C63/26C07D307/89C07C63/24C07C63/307
CPCC07C51/265C07C253/30C07C303/02C07C201/12C07D213/79C07D333/40C07D307/89C07C63/06C07C255/57C07C63/70C07C309/58C07C205/57C07C65/24C07C63/26C07C63/24C07C63/307
Inventor 曾荣张国祥
Owner XI AN JIAOTONG UNIV
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