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Method for synthesizing ortho-amino aromatic ketone from aromatic carboxylic acid

A technology for amino aromatic ketones and aromatic carboxylic acids, which is applied in the preparation of carboxylic acid nitriles, chemical instruments and methods, and the preparation of organic compounds. It can solve problems such as poor functional group compatibility, harsh reaction conditions, and excessive acylating reagents. Residue, the effect of mild reaction conditions

Active Publication Date: 2019-05-31
NANJING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the above reaction strategies usually require excess acylating reagents and harsh reaction conditions, and the compatibility of functional groups is poor.

Method used

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  • Method for synthesizing ortho-amino aromatic ketone from aromatic carboxylic acid
  • Method for synthesizing ortho-amino aromatic ketone from aromatic carboxylic acid
  • Method for synthesizing ortho-amino aromatic ketone from aromatic carboxylic acid

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Weigh first (55.4mg, 0.2mmol), photocatalyst Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 (2.3mg, 1mol%), K 2 HPO 4 (34.8mg, 0.2mmol, 1.0equiv.), triphenylphosphine (62.9mg, 0.24mmol, 1.2equiv.), added to the reaction tube, pumped through the vacuum line for three times, under argon atmosphere, added 2mL1,4 -Dioxane, and then placed under the irradiation of two 45W blue light lamps, and reacted at room temperature for 8 hours. Dry loading, column chromatography (300-400 mesh chromatography silica gel) to obtain the product 29.0mg, (eluent: petroleum ether-ethyl acetate, 5:1, the same below), yield 74%, 1 H NMR (400MHz, CDCl 3 )δ7.65 -7.62(m, 2H), 7.52(t, J=7.3Hz, 1H), 7.45(dd, J=7.9, 6.4Hz, 3H), 7.31-7.27(m, 1H), 6.74(d ,J=8.3Hz,1H),6.60(t,J=7.6Hz,1H),6.11(s,2H). 13 C NMR (100 MHz, CDCl 3 )δ 199.1, 150.9, 140.1, 134.6, 134.3, 131.1, 129.1, 128.1, 118.2, 117.0, 115.5.

Embodiment 2

[0026] Weigh first (58.2mg, 0.2mmol), photocatalyst Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 (2.3mg, 1mol%), K 2 HPO 4 (34.8mg, 0.2mmol, 1.0equiv.), triphenylphosphine (62.9mg, 0.24mmol, 1.2equiv.), added to the reaction tube, pumped through the vacuum line for three times, under argon atmosphere, added 2mL 1, 4-dioxane, and then placed under the irradiation of two 45W blue light lamps, and reacted at room temperature for 8 hours. Dry loading, column chromatography (300-400 mesh chromatography silica gel) to obtain the product 33.4 mg, 69% yield, 1 H NMR (400MHz, CDCl 3 )δ7.56(d, J=8.0Hz, 2H), 7.46(d, J=8.0Hz, 1H), 7.32-7.25(m, 1H), 6.73(d, J=8.3Hz, 1H), 6.60( t,J=7.6Hz,1H),6.00(s,2H),2.43(s,3H). 13 C NMR (100MHz, CDCl 3 )δ198.9, 150.7, 141.7, 137.2, 134.4, 134.0, 129.5, 128.8, 118.5, 117.0, 115.5, 21.6.

Embodiment 3

[0028] Weigh first (61.4mg, 0.2mmol), photocatalyst Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 (2.3mg, 1mol%), K 2 HPO 4 (34.8mg, 0.2mmol, 1.0equiv.), triphenylphosphine (62.9mg, 0.24mmol, 1.2equiv.), added to the reaction tube, pumped through the vacuum line for three times, under argon atmosphere, added 2mL1,4 -Dioxane, and then placed under the irradiation of two 45W blue light lamps, and reacted at room temperature for 8 hours. Dry loading, column chromatography (300-400 mesh chromatography silica gel) to obtain the product 33.4mg, yield 74%, 1 H NMR (400MHz, CDCl 3)δ7.68(d, J=8.8Hz, 2H), 7.46(d, J=9.5Hz, 1H), 7.29(d, J=8.5Hz, 1H), 6.95(d, J=8.8Hz, 2H) ,6.73(d,J=9.1Hz,1H),6.62(t,J=8.1Hz,1H),5.85(s,2H),3.88(s,3H). 13 C NMR (100MHz, CDCl 3 )δ197.8, 162.3, 150.4, 134.0, 133.7, 132.3, 131.8, 119.0, 117.0, 115.6, 113.4, 55.5.

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Abstract

Disclosed is a method for synthesizing ortho-amino aromatic ketone from aromatic carboxylic acid. The method comprises the steps that with 2-arylsulfonamido aromatic carboxylic acid shown in the description as a raw material and triphenylphosphine as a deoxidizer, under the illumination of blue light, in a 1,4-dioxane solution, under an argon atmosphere, in the presence of the dipotassium hydrogenphosphate, with [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 as a photocatalyst, the ortho-amino aromatic ketone compound is obtained; the structure of the photocatalyst [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 is shown in thedescription.

Description

technical field [0001] The invention relates to a method for preparing o-aminoaromatic ketones from aromatic carboxylic acids. Background technique [0002] As an important organic compound, ketones are widely used in the synthesis of drugs, spices, agrochemicals, etc. [Ref: W.S. Bechara, G. Pelletier, A. Charette, Nat. Chem. 2012, 4, 228]. Among them, o-aminoaromatic ketones are important precursors for the synthesis of heterocyclic aromatic compounds such as quinoline and indole [see: a) B.V.S.Reddy, M.R.Reddy, Y.G.Rao, J.S.Yadav, B.Sridhar, Org. 2013, 15, 464-467; b) G. Bartoli, R. Dalpozzo, M. Nardi, Chem. Soc. Rev. 2014, 43, 4728-4750; c) J. Marco-Contelles, E. Pérez-Mayoral, A. Samadi, M.C.Carreiras, E. Soriano, Chem.Rev.2009,109,2652-2671], is also an important raw material for the synthesis of diazepinones such as clonazepam, alprazolam, etc. [see: J. Spencer, R.P. Rathnam, B.Z. Chowdhry, Future. Med. Chem. 2010, 2, 1441-1449]. One of the important methods for the...

Claims

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Application Information

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IPC IPC(8): C07C221/00C07C225/22C07D277/64C07D213/53C07D333/22C07D311/18C07D307/79C07C227/10C07C229/52C07C253/30C07C255/58
Inventor 谢劲热汗古丽·如孜马俊扬王文亮
Owner NANJING UNIV
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