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Method for synthesizing alpha-alkyl ketone under catalysis of iridium

A synthesis method and technology of alkyl ketones are applied in the field of synthesis of α-alkyl ketones to achieve the effect of broad development prospects

Inactive Publication Date: 2017-03-08
NANJING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] However, the use of these known transition metal catalysts to catalyze the α-alkylation of ketones still requires the use of N 2 It is carried out under the protection of a large amount of inorganic strong base, especially KOH

Method used

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  • Method for synthesizing alpha-alkyl ketone under catalysis of iridium
  • Method for synthesizing alpha-alkyl ketone under catalysis of iridium
  • Method for synthesizing alpha-alkyl ketone under catalysis of iridium

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Example 1: 1,3-diphenyl-1-propanone

[0025] 1,3-diphenylpropan-1-one

[0026]

[0027] Acetophenone (60mg, 0.5mmol), cat.[Ir] (5.4mg, 0.005mmol, 1mol%), cesium carbonate (33mg, 0.2mmol, 0.2equiv.), benzyl alcohol (64mg, 0.6mmol) and tert Pentanol (1 ml) was sequentially added to a 5 mL round bottom flask. The reaction mixture was refluxed in air for 12 hours and then cooled to room temperature. Rotary evaporation removes solvent, then obtains pure target compound by column chromatography (developing solvent: sherwood oil / ethyl acetate), productive rate: 92%

[0028] 1 H NMR (500MHz, CDCl 3 )δ7.96(d, J=7.2Hz, 2H, ArH), 7.55(t, J=6.9Hz, 1H, ArH), 7.45(t, J=6.9Hz, 2H, ArH), 7.34-7.23(m ,4H,ArH),7.20(t,J=6.7Hz,1H,ArH),3.30(t,J=7.3Hz,2H,CH 2 ), 3.07(t, J=7.3Hz, 2H, CH 2 ); 13 C NMR (125MHz, CDCl 3 )δ 199.2, 141.3, 136.9, 133.0, 128.6, 128.5, 128.4, 128.0, 126.1, 40.4, 30.1.

Embodiment 2

[0029] Example 2: 3-(4-fluorophenyl)-1-phenyl-1-propanone

[0030] 3-(4-fluorophenyl)-1-phenylpropan-1-one

[0031]

[0032] Acetophenone (60mg, 0.5mmol), cat.[Ir] (5.4mg, 0.005mmol, 1.0mol%), cesium carbonate (33mg, 0.1mmol, 0.2equiv.), 4-fluorobenzyl alcohol (76mg, 0.6 mmol) and tert-amyl alcohol (1 ml) were sequentially added to a 5 mL round bottom flask. The reaction mixture was refluxed in air for 12 hours and then cooled to room temperature. Rotary evaporation removes solvent, then obtains pure target compound by column chromatography (developing solvent: sherwood oil / ethyl acetate), productive rate: 86%

[0033] 1 H NMR (500MHz, CDCl 3 )δ7.95(d, J=7.2Hz 2H, ArH), 7.56(t, J=7.4Hz, 1H, ArH), 7.46(t, J=7.7Hz, 2H, ArH), 7.20(dd, J 1 =8.5Hz and 5.6Hz,2H,ArH),6.97(t,J=8.7Hz,2H,ArH),3.28(t,J=7.6Hz,2H,CH 2 ), 3.05(t, J=7.6Hz, 2H, CH 2 ); 13 C NMR (125MHz, CDCl 3 )δ199.0,161.4(d,J C-F =242.5Hz), 136.8, 136.7, 133.1, 129.8 (d, J C-F =7.6Hz), 128.6, 128.0, 115.2 (d, ...

Embodiment 3

[0034] Example 3: 3-(4-chlorophenyl)-1-phenyl-1-propanone

[0035] 3-(4-chlorophenyl)-1-phenylpropan-1-one

[0036]

[0037]Acetophenone (60mg, 1mmol), cat.[Ir] (5.4mg, 0.005mmol, 1.0mol%), cesium carbonate (33mg, 0.1mmol, 0.2equiv.), 4-chlorobenzyl alcohol (86mg, 0.6mmol ) and tert-amyl alcohol (1 mL) were sequentially added to a 5 mL round bottom flask. The reaction mixture was refluxed in air for 12 hours and then cooled to room temperature. Rotary evaporation removes solvent, then obtains pure target compound by column chromatography (developing solvent: sherwood oil / ethyl acetate), productive rate: 82%

[0038] 1 H NMR (500MHz, CDCl 3 )δ7.95(d, J=7.2Hz, 2H, ArH), 7.56(t, J=7.4Hz, 1H, ArH), 7.46(t, J=7.7Hz, 2H, ArH), 7.21(dd, J 1 =8.5Hz and 5.5Hz,2H,ArH),6.97(t,J=7.8Hz,2H,ArH),3.28(t,J=7.6Hz,2H,CH 2 ), 3.05(t, J=7.5Hz, 2H, CH 2 ); 13 C NMR (125MHz, CDCl 3 )δ198.8, 139.7, 136.7, 133.1, 131.8, 129.8, 128.6, 128.5, 128.1, 40.2, 29.2.

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Abstract

The invention discloses a method for synthesizing alpha-alkyl ketone under catalysis of iridium. The method comprises steps as follows: ketone, an alcohol compound, a iridium complex catalyst, alkali and a solvent, namely, tert-amyl alcohol are added to a reaction container, the reaction mixture is subjected to a reflux reaction in the air and cooled to the room temperature after the reaction ends, a solvent is removed through rotary evaporation, and a target compound is obtained through column separation. A tridentate iridium complex with an N^C^N ligand is used, all that is required is to add 0.2 equivalents of carbonate during the reaction in the air, the reaction takes only 10-12 h, and remarkable advantages are shown. Therefore, the reaction meets the green chemistry requirement, and broad development prospect is realized.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis chemistry, and in particular relates to a method for synthesizing α-alkyl ketones. Background technique [0002] α-Alkyl ketones are a very important class of compounds, exhibiting a wide range of physiological and pharmacological activities. For example, such compounds are used as reversible ketoheterocyclic inhibitors of fatty acid amide hydrolase (OL-135), inhibitors of thyroid receptor coactivator binding, orally bioavailable phthalazinone bradykinin B1 receptors, body antagonists and 5-HT 7 receptor ligands, etc. (a) D. L. Boger, H. Miyauchi, W. Du, C. Hardouin, R. A. Fecik, H. Cheng, I. Hwang, M. P. Hedrick, D. Leung, O. Acevedo, C. R. W. W.L.Jorgensen, B.F.Cravatt, J.Med.Chem.2005,48,1849-1856; b) J.Y.Hwang, L.A.Arnold, F.Zhu, A.Kosinski, T.J.Mangano, V.Setola, B.L.Roth, R.K.Guy, J. .Med.Chem.2009, 52, 3892-3901; c) K.Biswas, T.A.N.Peterkin, M.C.Bryan, L.Arik, S.G.Lehto, H.Su...

Claims

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Application Information

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IPC IPC(8): C07C45/71C07C49/784C07C49/813C07C49/84C07C49/788C07F17/02C07D333/22
CPCC07C45/71C07D333/22C07F17/02C07C49/784C07C49/813C07C49/84C07C49/788
Inventor 刘鹏程陆磊李峰
Owner NANJING UNIV OF SCI & TECH
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