Hydrophilic inorganic porous material, preparation method and application thereof to reaction of selective catalytic aldehyde or ketone and hydroxylamine

Abstract

Provided are a hydrophilic inorganic porous material, a preparation method and application thereof to a reaction of selective catalytic aldehyde or ketone and hydroxylamine. The invention discloses the multifunctional hydrophilic inorganic porous material which is formed by POMs groups having a good oxidation catalysis function and transition metal ions having a lewis acid property. A chemical formula is H110Co4K2O123W19Zn5. A synthetic route is as follows: Co2++POMs-Co-POMs, wherein Co2+ is a transition metal ion, and POM is a sandwich polyacid anion. The multifunctional hydrophilic inorganic porous material serves as a catalyst to be used applied to the reaction of selective catalytic aldehyde or ketone and hydroxylamine. According to the hydrophilic inorganic porous material, through special space limitation provided by an internal duct in the structure of the material and synergistic effects between multiple catalysis loci, control over a catalytic system in dynamics is implemented, and optimal time, conversion rate and highest selectivity of the catalytic reaction are implemented. The catalytic processes are all heterogeneous, cyclic utilization can be implemented through filtering and recycling the catalyst, the catalytic efficiency is not obviously reduced, and thus the multifunctional inorganic porous material provides a scientific basis for development of fine chemical engineering, medicine synthesis, etc. in China.

Description

technical field

[0001] The invention belongs to the technical field of preparation of polyoxometalate chemical materials, and specifically relates to a multifunctional hydrophilic inorganic porous material formed by combining POMs groups with good oxidation and catalytic functions and transition metal ions with Lewis acid properties, The preparation method and its application as a catalyst in selectively catalyzing the reaction of aldehydes or ketones with hydroxylamine. Background technique

[0002] Oxime compounds and amides are very useful pharmaceutical intermediates in industrial applications, and also play a very important role as a bridge in organic conversion. Aldehydes, ketones and hydroxylamine are converted into oximes and amides through oximation, which are indispensable in modern organic synthesis. The key influencing factor in the synthesis process is hydroxylamine, which is due to the fact that hydroxylamine is quite dangerous, explosive, and easy to decompos...

Examples

Embodiment 1

[0025] A kind of hydrophilic inorganic porous material, its chemical formula is: H 110 co 4 K 2 o 123 W 19 Zn 5 .

[0026] The preparation method of the above-mentioned hydrophilic inorganic porous material specifically comprises the following steps:

[0027] 1) Preparation of precursor sandwich polyacid K 12 [WZn 3 (H 2 O) 2 (ZnW 9 o 34 ) 2 ]·46H 2 O: Firstly, prepare Na 12 [WZn 3 (H 2 O) 2 (ZnW 9 o 34 ) 2 ]·46H 2 O; then add KCl solid equal amount to replace Na ion in this solution and convert to K 12 [WZn 3 (H 2 O) 2 (ZnW 9 o 34 ) 2 ]·46H 2 O, this is common knowledge in the art, so it will not be repeated here;

[0028] 2) will K 12 [WZn 3 (H 2 O) 2 (ZnW 9 o 34 ) 2 ]·46H 2 O (60 mg, 0.02 mmol), Co(NO 3 ) 2 ·3H 2 O (40 mg, 0.19 mmol) was added to a mixed solution consisting of 4 mL distilled water and 2 mL methanol, stirred overnight at room temperature, then transferred to a 25 mL polytetrafluoroethylene autoclave at 130 °C for 5 day...

technical field

[0001] The invention belongs to the technical field of preparation of polyoxometalate chemical materials, and specifically relates to a multifunctional hydrophilic inorganic porous material formed by combining POMs groups with good oxidation and catalytic functions and transition metal ions with Lewis acid properties, The preparation method and its application as a catalyst in selectively catalyzing the reaction of aldehydes or ketones with hydroxylamine. Background technique

[0002] Oxime compounds and amides are very useful pharmaceutical intermediates in industrial applications, and also play a very important role as a bridge in organic conversion. Aldehydes, ketones and hydroxylamine are converted into oximes and amides through oximation, which are indispensable in modern organic synthesis. The key influencing factor in the synthesis process is hydroxylamine, which is due to the fact that hydroxylamine is quite dangerous, explosive, and easy to decompos...

Examples

Embodiment 1

[0025] A kind of hydrophilic inorganic porous material, its chemical formula is: H 110 co 4 K 2 o 123 W 19 Zn 5 .

[0026] The preparation method of the above-mentioned hydrophilic inorganic porous material specifically comprises the following steps:

[0027] 1) Preparation of precursor sandwich polyacid K 12 [WZn 3 (H 2 O) 2 (ZnW 9 o 34 ) 2 ]·46H 2 O: Firstly, prepare Na 12 [WZn 3 (H 2 O) 2 (ZnW 9 o 34 ) 2 ]·46H 2 O; then add KCl solid equal amount to replace Na ion in this solution and convert to K 12 [WZn 3 (H 2 O) 2 (ZnW 9 o 34 ) 2 ]·46H 2 O, this is common knowledge in the art, so it will not be repeated here;

[0028] 2) will K 12 [WZn 3 (H 2 O) 2 (ZnW 9 o 34 ) 2 ]·46H 2 O (60 mg, 0.02 mmol), Co(NO 3 ) 2 ·3H 2 O (40 mg, 0.19 mmol) was added to a mixed solution consisting of 4 mL distilled water and 2 mL methanol, stirred overnight at room temperature, then transferred to a 25 mL polytetrafluoroethylene autoclave at 130 °C for 5 day...

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