Method for preparing aldehyde or ketone by using photocatalysis to selectively oxidize primary alcohol or secondary alcohol

A secondary alcohol, selectivity technology, applied in the direction of oxidative preparation of carbonyl compounds, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problem of low selectivity, achieve the effect of increasing the reaction rate and wide application range

Active Publication Date: 2009-09-16
INST OF CHEM CHINESE ACAD OF SCI
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Problems solved by technology

[0004] "Journal of the American Chemical Society" 2008, volume 130, page 1568, published the article "Using rutile-type TiO to selectively oxidize aromatic alcoho...

Method used

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  • Method for preparing aldehyde or ketone by using photocatalysis to selectively oxidize primary alcohol or secondary alcohol
  • Method for preparing aldehyde or ketone by using photocatalysis to selectively oxidize primary alcohol or secondary alcohol
  • Method for preparing aldehyde or ketone by using photocatalysis to selectively oxidize primary alcohol or secondary alcohol

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Experimental program
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Embodiment 1

[0034] Preparation of the catalyst: 10 ml of tetrabutyl titanate and a corresponding amount of ethyl silicate (the ratio of Si / Ti atoms is 7%) were added to 300 ml of isopropanol. The solution was kept at 0°C, and distilled water was added dropwise thereto under vigorous stirring. After the tetrabutyl titanate and ethyl silicate were completely hydrolyzed, the white suspension was kept at 80°C for 1 hour. Then centrifugal filtration, the obtained solid was washed three times with ethanol and distilled water respectively. After drying at 100°C, it was calcined at 430°C for 2 hours. Gained sample, take out 0.5g and put in 5ml, 1mol / L HF acid ultrasonic half an hour. Finally, centrifuge filtration to obtain the HF / SiO required for the reaction 2 / TiO 2 Solid-phase catalyst (Si atom in the solid-phase catalyst and Ti atomic number ratio are 7%, and the concentration of HF acid contained on the surface of the solid-phase catalyst is 1×10 -2 mol / g), where TiO 2 Anatase with an...

Embodiment 2

[0052] The preparation method of catalyst is completely with embodiment 1, obtains HF / SiO 2 / TiO 2 solid phase catalyst. where TiO 2 Anatase with an average particle size of 13.5nm, SiO 2 is amorphous.

[0053] Preparation of benzaldehyde: add 25mg of HF / SiO to a 15ml glass reactor 2 / TiO 2 and 1.5ml of carbon tetrachloride, acetonitrile or diethyl ether, and then add 0.1mmol of benzyl alcohol. After 0.1MPa oxygen bubbles for half an hour, it is sealed. Turn on the high-pressure mercury lamp (wavelength 220nm-440nm linear discontinuous spectrum, the wavelength that plays a major role is 220nm-420nm), irradiate the reaction for 4 hours under the condition of uniform stirring, turn off the light source, end the reaction, and measure the reaction by GC-MS things and products. The reaction results are shown in Table 3. The influence of several solvents on the selectivity is not much different. On the influence of reaction rate, carbon tetrachloride organic solvent system...

Embodiment 3

[0061] According to the solid-phase catalyst preparation method part in embodiment 1, the ratio of Si / Ti atomic number is prepared as 17% HF / SiO 2 / TiO 2 solid phase catalyst. The concentration of HF acid contained on the surface of the solid phase catalyst is 1×10 -2 mol / g. where TiO 2 Anatase with an average particle size of 13.5nm, SiO 2 is amorphous.

[0062] The preparation of benzaldehyde: the catalyst selects HF / SiO with a Si / Ti atom number ratio of 12%. 2 / TiO 2 Solid-phase catalyst, other reaction conditions and reaction steps are with the preparation part of benzaldehyde in embodiment 2. After the irradiation reaction for 4 hours, the light source was turned off, the reaction was terminated, and the reactants and products were determined by GC-MS. The conversion rate of benzyl alcohol is 93%, and the selectivity of forming benzaldehyde is 99%.

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Abstract

The invention relates to the technical field of selective oxidation synthesis of photocatalysis, in particular to a method for preparing corresponding aldehyde or ketone by using luminous energy to high-efficiently and high-selectively oxidize primary alcohol or secondary alcohol. In the method of the invention, acid and SiO2 cooperated with modified TiO2 are used as a solid phase catalyst; in an organic solvent, in the presence of stirring and oxygen, illumination is used for oxidizing primary alcohol or secondary alcohol so as to prepare corresponding aldehyde or ketone. In the invention, the selectivities of aldehyde and ketone oxidation generated by oxidizing aromatic alcohol in particular the aromatic alcohol that does not contain ethylenic linkage are more than 95%, and the selectivities of aldehyde and ketone oxidation for saturated chain alcohol are more than 60%; no noble metal catalyst or organic promoter is needed; and acid/SiO2/TiO2 catalyst can be separated and reused. The method of the invention has wide application range, and the reaction is carried out at normal temperature.

Description

technical field [0001] The invention relates to the technical field of photocatalytic selective oxidation synthesis, in particular to a method for preparing corresponding aldehydes or ketones by utilizing light energy to oxidize primary alcohols or secondary alcohols with high efficiency and high selectivity. Background technique [0002] The reaction of alcohol oxidation to aldehyde, because the generated aldehyde can be used as an intermediate in the synthesis reaction, it is a very important basic reaction no matter in the laboratory or in the field of synthetic chemical industry. The industry has been using halogen-containing oxidants such as hypochlorous acid, oxyiodine and other oxidants with polluting by-products, or using heavy metal oxyacids such as permanganate and potassium dichromate. This stoichiometric oxidation reaction is relatively expensive and cannot be reused. As people pay more and more attention to the environment and energy, people began to study the ...

Claims

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Application Information

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IPC IPC(8): C07C45/29C07C47/54C07C47/542C07C47/55C07C47/575C07C47/02C07C49/78C07C49/786C07C49/403C07C49/04B01J21/06B01J21/08B01J27/12B01J27/02B01J27/10B01J31/04
Inventor 赵进才余春王齐马万红陈春城
Owner INST OF CHEM CHINESE ACAD OF SCI
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