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Method for preparing acetylenic ketone through oxidizing propargyl alcohol

A technology for preparing propargyl alcohol and acetylenic ketone, which is applied in the field of catalytic oxidation, can solve problems such as troublesome post-processing and pollution, and achieve the effects of easy product, simple operation and mild reaction conditions.

Inactive Publication Date: 2014-06-25
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] The purpose of the present invention is to overcome the post-processing troubles and pollution problems in the above-mentioned oxidation system, and provide a new method for preparing acetylene ketone by DDQ catalytic oxidation of propargyl alcohol with molecular oxygen as the oxygen source

Method used

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  • Method for preparing acetylenic ketone through oxidizing propargyl alcohol
  • Method for preparing acetylenic ketone through oxidizing propargyl alcohol
  • Method for preparing acetylenic ketone through oxidizing propargyl alcohol

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0017] Embodiment 1, the investigation of reaction conditions

[0018] First, we investigated the reaction conditions by taking the oxidation of 1,3-diphenyl-2-propyn-1-ol to 1,3-diphenyl-2-yne-1-propanone as a model reaction.

[0019] The results are shown in Table 1.

[0020] The investigation of table 1 reaction condition

[0021]

[0022]

[0023] Note: The reaction temperature is 25°C, the substrate is 1,3-diphenyl-2-propyn-1-ol, and the organic solvent is dichloromethane (30ml). The product is 1,3-diphenyl-2-yne-1-propanone, light yellow solid, 1 H NMR (300MHz, CDCl 3 )δ7.56-7.43(m,5H),7.72-7.62(m,3H),8.26-8.22(m,2H), 13 CNMR (100.6MHz, CDCl 3 )δ 86.8, 93.0, 119.9, 128.5, 128.6, 129.4, 130.7, 132.9, 134.0, 136.7, 177.8. IR(KBr,cm -1 ): 3063, 2955, 2921, 2851, 2198 (C≡C), 1727 (C=O).

[0024] It can be seen from Table 1 that DDQ, nitric acid, and oxygen play a vital role in the oxidation reaction and are indispensable. The oxygen pressure is high, the react...

Embodiment 2

[0025] Embodiment 2, the influence of different solvents on reaction

[0026] The influence of table 2 solvent on reaction

[0027]

[0028] Note: The reaction conditions are 0.1mol 1,3-diphenyl-2-propyn-1-ol oxidation, 0.01mol DDQ, 0.04mol98% nitric acid, 0.3Mpa O 2 ,25°C, 15h.

[0029] As can be seen from Table 2, when methylene dichloride, ethylene dichloride, chloroform and ethyl acetate were solvents, the yield of product 1,3-diphenyl-2-alkyne-1-propanone was higher, from the perspective of environmental protection and convenience Handling Considerations Dichloromethane and ethyl acetate are the preferred solvents.

Embodiment 3

[0030] Embodiment 3, 1-phenyl-2-propyn-1-alcohol oxidation

[0031]

[0032] Add 13.2g (100mmol) 1-phenyl-2-propyn-1-ol, 2.72g (9.8mmol) DDQ into 30mL of dichloromethane solvent, cool with an ice-water bath, and slowly add 1.15g ( 18mmol) of nitric acid, fed with 0.2MPa of oxygen, reacted at 25°C for 18h, slowly released the pressure, added NaOH aqueous solution to neutralize, extracted with dichloromethane, washed with water, dried, and evaporated the solvent. The resulting mixture was subjected to column separation to obtain 9.8 g (yield: 75%) of 1-phenyl-2-propyn-1-one. Melting point of yellow solid is 42.5-43.5°C; 1 H NMR (300MHz, CDCl 3 )δ3.45(s,1H),7.49(t,J=7.4Hz,2H),7.63(t,J=7.4Hz,1H),8.16(d,J=7.4Hz,2H). 13 C NMR (100.6MHz, CDCl 3 ) δ80.2, 80.7, 128.7, 129.6, 134.5, 136.1, 177.3. IR(KBr,cm -1 ): 3311(-C≡H), 3045, 2109(C≡C), 1666(C=O).

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PUM

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Abstract

The invention provides a method for preparing acetylenic ketone through oxidizing propargyl alcohol. The method comprises the following steps: in a liquid phase, taking 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) as the catalyst, nitric acid as the co-catalyst, and oxygen gas as the oxidant, and oxidizing propargyl alcohol in an organic solvent so as to produce acetylenic ketone. The method has the advantages of mild conditions, convenient operation, no metal, and little pollution, and is a green and environment-friendly novel method for preparing ketone through oxidizing alcohol with a non-metal catalyst.

Description

technical field [0001] The invention relates to the field of catalytic oxidation, in particular to a method for preparing acetylene ketone by catalytic oxidation of propargyl alcohol. Background technique [0002] Alkyne ketone (ynone), its structure is shown in formula 1. Alkyne ketone compounds have special conjugated structural units, which are an important class of organic synthesis intermediates and are widely used in organic synthesis. [0003] [0004] Formula 1 [0005] At present, the synthesis methods of acetylenone compounds mainly include: 1) acylation reaction of quantitative alkynyl metal reagent with acid chloride and acid anhydride; 2) acylation reaction of terminal alkyne catalyzed by palladium; 3) oxidation reaction of propargyl alcohol; 4) transition Metal-catalyzed α-CH of non-terminal alkynes 2 oxidation reaction. Among them, the oxidation of propargyl alcohol to acetylene ketone is of great research significance due to the easy availability of ra...

Claims

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Application Information

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IPC IPC(8): C07C45/39C07C49/796C07C49/794C07C49/84C07C49/557C07C49/207
CPCC07C45/39C07C2601/14C07C49/794C07C49/796C07C49/84C07C49/557C07C49/207
Inventor 高爽李军王连月
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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