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Method for preparing aryl ketone

A technology of aryl ketone and aryl boronic acid, which is applied in the field of catalysis, can solve the problems of complex reaction system, unfavorable practical application, and high price, and achieve the effects of simple post-processing, wide application range, and improved utilization efficiency

Active Publication Date: 2011-08-17
铜陵市官作文化有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the substrates are limited to salicylaldehyde and its derivatives, and cannot react with other types of aldehydes. At the same time, palladium is used as a catalyst, which is expensive and toxic. At the same time, copper salts are also added as cocatalysts to make the reaction system become more complex. complex, not conducive to practical application

Method used

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  • Method for preparing aryl ketone
  • Method for preparing aryl ketone
  • Method for preparing aryl ketone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028]

[0029] [Ru(CO) 3 Cl 2 ] 2 (2.5 mmol%), t-Bu 3 P.HBF 4 (10 mmol %), compound 1a (1 mmol, 106 mg), 2a (2 mmol, 304 mg), K 3 PO 4 .3H 2 O (2 mmol, 532 mg), Toluene (5 mL), H 2 O (0.5 mL), t -BuCOMe (2 mmol, 200 mg). Then the system was heated in an oil bath at 100°C in an argon atmosphere for about 24 hours, the solvent was adsorbed by silica gel and vacuum spin-dried, and the oxidation product 3a was obtained by simple column chromatography with a yield of 91%. The following test data confirmed that the target product was obtained; 1 H NMR (CDCl 3 , 400 MHz): δ = 7.83 (d, J = 8.8 Hz, 2H), 7.75 (d, J = 7.5 Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 7.5 Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H), 3.87 (s, 3H): δ = 195.5, 163.1, 138.2, 132.5, 131.8, 130.0, 129.6, 128.1, 113.5, 55.4; MS (C 14 h 12 o 2 ): 212; IR (KBr, cm -1 ): ν 1650.

[0030]

Embodiment 2

[0032]

[0033] [Ru(cymene)Cl 2 ] 2 (2.5 mmol%), Cy 3 P.HBF 4 (10 mmol %), compound 1b (1 mmol, 124 mg), 2a (2 mmol, 304 mg), K 3 PO 4 .3H 2 O (2 mmol, 532 mg), Toluene (5 mL), H 2 O (0.5 mL), t -BuCOMe (2 mmol, 200 mg). Then the system was heated in an oil bath at 100°C in an argon atmosphere for about 24 hours, the silica gel was adsorbed and the solvent was vacuum spin-dried, and the oxidation product 3b was obtained by simple column chromatography with a yield of 85%. The following test data confirmed that the target product was obtained; 1 H NMR (CDCl 3 , 400 MHz): δ = 7.81-7.77 (m, 4H), 7.16-7.12 (m, 2H), 6.96 (d, J=8.8, 2H), 3.88 (s, 3H); 13 C NMR (CDCl 3 , 75 MHz): δ = 194.0, 166.2, 163.7, 163.1, 134.3, 134.3, 132.3, 132.2, 132.1, 129.8, 115.3, 115.1 113.5, 55.4; MS (C 14 h 11 FO 2 ): 230; IR (KBr, cm -1 ): ν 1641.

Embodiment 3

[0035]

[0036] The reaction flask was filled with RuH in sequence 2 (CO)PPh 3 (2.5 mmol%), Cy 3 P (10 mmol %), compound 1c (1 mmol, 184 mg), 2a (2 mmol, 304 mg), K 3 PO 4 .3H 2 O (2 mmol, 532 mg), Toluene (5 mL), H 2 O (0.5 mL), t -BuCOMe (2 mmol, 200 mg). Then the system was heated in an oil bath at 100°C in an argon atmosphere for about 24 hours, the solvent was adsorbed by silica gel and vacuum spin-dried, and the oxidation product 3c was obtained by simple column chromatography with a yield of 82%. The following test data confirmed that the target product was obtained; 1 H NMR (CDCl 3 , 400 MHz): δ = 7.79 (d, J=8.5, 1H), 7.62 (s, 1H), 6.96 (d, J=8.5, 1H), 3.89 (s, 3H); 13 C NMR (CDCl 3 , 100 MHz): δ = 194.3, 163.3, 136.9, 132.4, 131.4, 131.2, 129.6, 126.8, 113.6, 55.5; MS (C 14 h 11 BrO 2 ): 290, 294; IR (KBr, cm -1 ): ν 1639.

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Abstract

The invention relates to the field of catalysis, in particular to a method for preparing aryl ketone through reacting aldehyde with aryl boric acid under the catalysis of a ruthenium catalyst. In the method, an organic phosphide is used as a ligand, potassium phosphate is used as alkali, pinacolone or acetone is used as an additive, toluene or / and water is (are) used as a solvent(s), aldehyde and aryl boric acid which are used as reaction substrates react at 95-100 DEG C for 10-24h in the presence of a ruthenium compound used as a catalyst to prepare aryl ketone, wherein the catalyst is one of [Ru(cymene)Cl2]2, [Ru(CO)3Cl2]2, RuH2(CO)PPh3, Ru2(OAc)4, [Ru(benzene)Cl2]2, Ru(S-BINAP)Cl2 or Ru3(CO)12. In the invention, the used catalyst has relatively low price and low toxicity, thereby reducing the preparation cost and being more environmentally friendly.

Description

technical field [0001] The invention relates to the field of catalysis, in particular to a method for preparing aryl ketones by catalyzing aldehydes and aryl boronic acids with a ruthenium catalyst. Background technique [0002] Aryl ketones are a very important class of organic compounds, which are not only included in a variety of physiologically active natural products, but also widely used in the synthesis of other heterocyclic compounds. As a classic method for preparing aryl ketones, Friedel-Crafts acylation has the disadvantages of large amount of catalyst, harsh reaction conditions, difficult post-treatment, poor regioselectivity, narrow substrate range, and difficult preparation and storage of acid chlorides as reaction reagents. For economic and environmental considerations, it is necessary to find a more economical, green and mild method for preparing aryl ketones. The method of catalytic hydrocarbon activation to prepare aryl ketones can undoubtedly solve some o...

Claims

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Application Information

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IPC IPC(8): C07C225/22C07C201/12C07C68/06C07D307/46C07C221/00C07C309/73C07C205/45C07D317/54C07C255/56C07C49/813C07C303/30C07C253/30C07C45/68C07C69/96C07C49/84C07B41/06C07D333/22
Inventor 万小兵李宏徐元时二波姜丹妮陈继君
Owner 铜陵市官作文化有限公司
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