Method for one-step synthesis of diamino decalin by catalytic hydrogenation of dinitro naphthalene

Abstract

The invention relates to a method for one-step synthesis of diamino decalin by catalytic hydrogenation of dinitro naphthalene. The method is characterized in that a non-noble transition metal, namely nickel with catalytic activity is impregnated to different oxides and zeolite molecular sieve frameworks with different bore diameters and different structures in a certain loading ratio through an impregnation method under the situation of ultrasonic assisted vibration to prepare a nickel-loaded oxide or zeolite molecular sieve hydrogenation catalyst; and in a pressure reaction kettle, the load type nickel-based hydrogenation catalyst, dinitro naphthalene and a solvent are added, hydrogen is charged and heated to a certain reaction temperature, and the reaction is performed for a certain period of time for performing catalytic hydrogenation on dinitro naphthalene so as to realize the one-step synthesis of diamino decalin. According to the method disclosed by the invention, the conversion rate of dinitro naphthalene can be significantly improved; and simultaneously, the catalyst has the advantages of low cost, simplicity and convenience in preparation and long service life, and further shows great application prospects.

Description

technical field

[0001] The invention relates to a method for synthesizing diaminodecalin in one step by catalytic hydrogenation of dinitronaphthalene, in particular to a method for synthesizing diaminodecalin in one step by catalytic hydrogenation of dinitronaphthalene with a supported nickel-based hydrogenation catalyst. Background technique

[0002] Hydrogenation of aromatic nitro compounds is a very important unit reaction in dyestuff, medicine and fragrance industry. There have been some reports on the use of homogeneous catalysts to catalyze this reaction, however, these homogeneous catalysts are unstable in air and are not easy to separate and recover from the reactants. In recent years, the use of supported palladium, platinum, rhodium catalysts and Raney nickel catalysts for the hydrogenation of aromatic nitro compounds to aromatic amines has attracted people's attention. The catalysts used are mainly oxides, polymers and activated carbon supported noble metal catal...

Examples

preparation example Construction

[0023] The preparation method of the supported nickel-based hydrogenation catalyst is as follows: Under the condition of ultrasonic assisted oscillation, the active component nickel is loaded on the oxide or zeolite molecular sieve carrier by impregnation method. Generally, the nickel-containing salt solution is first impregnated into the oxide Or on a zeolite molecular sieve carrier, after drying, calcinate at 300-500°C for 3-5h, and then reduce at 250-500°C for 2-4h under a hydrogen atmosphere to obtain a supported nickel-based hydrogenation catalyst.

[0024] For example, take nickel nitrate 0.68 ~ 4.11g (the value here is 5 ~ 30wt% and SiO 2 Calculated from 2.5g, the load is based on the nickel metal load to calculate the amount of metal salt nickel nitrate, the amount of nickel metal is 0.14 ~ 0.83g), dissolved in 100mL of water, and then added 2.5g of SiO under the condition of ultrasonic assisted oscillation 2 , ultrasonically oscillating and impregnating at 70°C for 4h...

Embodiment 1

[0028] In a stirred pressure reactor, add Ni / SiO with a nickel loading mass fraction of 10% 2 Hydrogenation catalyst 100mg, 1,5-dinitronaphthalene 1.0g, tetrahydrofuran 9.0g, replace the air in the reactor with hydrogen three times, then fill in hydrogen to make the reaction pressure of the reactor reach 5.0MPa, start stirring, and the stirring speed is 250r / min, and heat the reaction kettle to make the reaction temperature reach 220°C, supplement and maintain the reaction pressure at 7.5MPa, keep the constant temperature for 6 hours, take out the reaction product, filter the catalyst after cooling, and obtain 1,5-diaminodecalin. Gas chromatography analysis showed that the conversion rate of 1,5-dinitronaphthalene was 99.1%, and the selectivity of 1,5-diaminodecalin was 96.2%.

Embodiment 2

[0030] In a stirred pressure reactor, add nickel loading mass fraction of 5% Ni / SiO 2 Hydrogenation catalyst 100mg, 1,8-dinitronaphthalene 1.0g, tetrahydrofuran 9.0g, replace the air in the reactor with hydrogen three times, then fill in hydrogen to make the reaction pressure of the reactor reach 5.5MPa, start stirring, and the stirring speed is 300r / min, and heat the reaction kettle to make the reaction temperature reach 200°C, replenish and maintain the reaction pressure at 8.0MPa, keep the constant temperature for 4 hours, take out the reaction product, filter the catalyst after cooling, and obtain 1,8-diaminodecalin. Gas chromatography analysis showed that the conversion rate of 1,8-dinitronaphthalene was 99.6%, and the selectivity of 1,8-diaminodecalin was 93.1%.

technical field

[0001] The invention relates to a method for synthesizing diaminodecalin in one step by catalytic hydrogenation of dinitronaphthalene, in particular to a method for synthesizing diaminodecalin in one step by catalytic hydrogenation of dinitronaphthalene with a supported nickel-based hydrogenation catalyst. Background technique

[0002] Hydrogenation of aromatic nitro compounds is a very important unit reaction in dyestuff, medicine and fragrance industry. There have been some reports on the use of homogeneous catalysts to catalyze this reaction, however, these homogeneous catalysts are unstable in air and are not easy to separate and recover from the reactants. In recent years, the use of supported palladium, platinum, rhodium catalysts and Raney nickel catalysts for the hydrogenation of aromatic nitro compounds to aromatic amines has attracted people's attention. The catalysts used are mainly oxides, polymers and activated carbon supported noble metal catal...

Examples

preparation example Construction

[0023] The preparation method of the supported nickel-based hydrogenation catalyst is as follows: Under the condition of ultrasonic assisted oscillation, the active component nickel is loaded on the oxide or zeolite molecular sieve carrier by impregnation method. Generally, the nickel-containing salt solution is first impregnated into the oxide Or on a zeolite molecular sieve carrier, after drying, calcinate at 300-500°C for 3-5h, and then reduce at 250-500°C for 2-4h under a hydrogen atmosphere to obtain a supported nickel-based hydrogenation catalyst.

[0024] For example, take nickel nitrate 0.68 ~ 4.11g (the value here is 5 ~ 30wt% and SiO 2 Calculated from 2.5g, the load is based on the nickel metal load to calculate the amount of metal salt nickel nitrate, the amount of nickel metal is 0.14 ~ 0.83g), dissolved in 100mL of water, and then added 2.5g of SiO under the condition of ultrasonic assisted oscillation 2 , ultrasonically oscillating and impregnating at 70°C for 4h...

Embodiment 1

[0028] In a stirred pressure reactor, add Ni / SiO with a nickel loading mass fraction of 10% 2 Hydrogenation catalyst 100mg, 1,5-dinitronaphthalene 1.0g, tetrahydrofuran 9.0g, replace the air in the reactor with hydrogen three times, then fill in hydrogen to make the reaction pressure of the reactor reach 5.0MPa, start stirring, and the stirring speed is 250r / min, and heat the reaction kettle to make the reaction temperature reach 220°C, supplement and maintain the reaction pressure at 7.5MPa, keep the constant temperature for 6 hours, take out the reaction product, filter the catalyst after cooling, and obtain 1,5-diaminodecalin. Gas chromatography analysis showed that the conversion rate of 1,5-dinitronaphthalene was 99.1%, and the selectivity of 1,5-diaminodecalin was 96.2%.

Embodiment 2

[0030] In a stirred pressure reactor, add nickel loading mass fraction of 5% Ni / SiO 2 Hydrogenation catalyst 100mg, 1,8-dinitronaphthalene 1.0g, tetrahydrofuran 9.0g, replace the air in the reactor with hydrogen three times, then fill in hydrogen to make the reaction pressure of the reactor reach 5.5MPa, start stirring, and the stirring speed is 300r / min, and heat the reaction kettle to make the reaction temperature reach 200°C, replenish and maintain the reaction pressure at 8.0MPa, keep the constant temperature for 4 hours, take out the reaction product, filter the catalyst after cooling, and obtain 1,8-diaminodecalin. Gas chromatography analysis showed that the conversion rate of 1,8-dinitronaphthalene was 99.6%, and the selectivity of 1,8-diaminodecalin was 93.1%.