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
1 Cites 5 Cited by

AI-Extracted 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 syste...
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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.

Application Domain

Organic compound preparationCarbonyl compound preparation

Technology Topic

KetonePropargyl alcohol +8

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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

Examples

  • Experimental program(10)

Example Embodiment

[0017] Example 1. Investigation of reaction conditions
[0018] First, we used 1,3-diphenyl-2-propyn-1-ol to produce 1,3-diphenyl-2-yn-1-acetone as a model reaction to investigate the reaction conditions.
[0019] The results are shown in Table 1.
[0020] Table 1 Investigation of reaction conditions
[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 methylene chloride (30ml). The product is 1,3-diphenyl-2-yne-1-propanone, a pale 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 )δ86.8, 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] Table 1 shows that DDQ, nitric acid, and oxygen play a vital role in the progress of the oxidation reaction and are indispensable. The oxygen pressure is high, the reaction is fast, and the result is good. This may be because the oxygen pressure is high, and the solubility of oxygen in the liquid is large, which is beneficial to the reaction. The oxygen pressure is low. Better reaction results can be obtained by prolonging the reaction time. The oxygen pressure is determined to be 0.2~0.5MPa.

Example Embodiment

[0025] Example 2. The influence of different solvents on the reaction
[0026] Table 2 The influence of solvent on the reaction
[0027]
[0028] Note: The reaction conditions are 0.1mol 1,3-diphenyl-2-propyn-1-ol oxidation, 0.01mol DDQ, 0.04mol 98% nitric acid, 0.3Mpa O 2 , 25℃, 15h.
[0029] It can be seen from Table 2 that when dichloromethane, dichloroethane, chloroform and ethyl acetate are used as solvents, the yield of the product 1,3-diphenyl-2-yne-1-acetone is higher, which is environmentally friendly and convenient. The treatment considers dichloromethane and ethyl acetate as preferred solvents.

Example Embodiment

[0030] Example 3. Oxidation of 1-phenyl-2-propyn-1-ol
[0031]
[0032] Add 13.2g (100mmol) 1-phenyl-2-propyn-1-ol and 2.72g (9.8mmol) DDQ to 30mL of dichloromethane solvent, cool with an ice water bath, and slowly add 1.15g ( 18mmol) nitric acid, inject 0.2MPa oxygen, react at 25°C for 18h, slowly release the pressure, add NaOH aqueous solution to neutralize, extract with dichloromethane, wash with water, dry, and evaporate the solvent. The obtained mixture was separated by column to obtain 9.8 g (yield: 75%) of 1-phenyl-2-propyn-1-one. Yellow solid, melting point 42.5-43.5℃; 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 )δ 80.2, 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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