CN107417568B - Method for preparing amino aromatic compound by catalytic hydrogenation of nitroaromatic compound - Google Patents

Method for preparing amino aromatic compound by catalytic hydrogenation of nitroaromatic compound Download PDF

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CN107417568B
CN107417568B CN201710381835.XA CN201710381835A CN107417568B CN 107417568 B CN107417568 B CN 107417568B CN 201710381835 A CN201710381835 A CN 201710381835A CN 107417568 B CN107417568 B CN 107417568B
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CN107417568A (en
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孟祥春
贾小安
朱亚西
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Changchun University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B43/00—Formation or introduction of functional groups containing nitrogen
    • C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to a method for preparing amino aromatic compound by selective catalytic transfer hydrogenation of nitroaromatic compound. The method uses non-noble metal Cu-Fe/TiO2Taking hydrazine hydrate as a reducing agent as a catalyst, and catalyzing nitroaromatic compounds such as nitrobenzonitrile, halogenated nitrobenzene, nitrobenzene acetylene and the like to be selectively hydrogenated at the temperature of 80-130 ℃ in an environment-friendly solvent ethanol to prepare corresponding amino aromatic compounds. Cu-Fe/TiO2The hydrogenation of the nitro group has high activity and selectivity. The selectivity of aminobenzonitrile is more than 98 percent, the selectivity of halogenated aniline is more than 98.9 percent, and the selectivity of aminophenylacetylene is more than 81 percent.

Description

Method for preparing amino aromatic compound by catalytic hydrogenation of nitroaromatic compound
Technical Field
The invention relates to a method for preparing an amino aromatic compound by hydrogenation of a nitroaromatic compound. In particular to Cu-Fe/TiO2The method is used as a catalyst for catalyzing the nitroaromatic compound containing an easily reducible group to selectively catalyze, transfer and hydrogenate the nitroaromatic compound in a green solvent ethanol to prepare the aminoaromatic compound.
Background
The amino aromatic compound plays an important role in drug synthesis, dye, insecticide, herbicide and polyurethane production, and is an important intermediate for synthesizing amide, imine, azo compounds, isocyanate, diazonium salt and the like. Wherein the aminobenzonitrile is an important intermediate for synthesizing anti-HIV drugs of itravirine and rilpivirine, and the aminophenylacetylene is an important intermediate for preparing an anti-cancer drug of erlotinib.
In the selective catalytic reduction process of the nitroaromatic compound, the generation and accumulation of toxic and harmful intermediates such as nitrosobenzene, hydroxylamine, azobenzene and the like are often accompanied, and when the nitroaromatic compound contains easy-to-reduce groups such as nitrile group, alkynyl and the like, only the nitroaromatic compound is reducedNitro groups, without hydrogenating these readily reducible groups, remain challenging. Heretofore, catalysts for hydrogenation of nitroaromatic compounds include supported noble metal catalysts such as Au, Pt, Pd, Ru, etc., and non-noble metal catalysts such as Fe, Co, Ni, etc. The Pt catalyst can be modified by phosphide or added with iron salt and vanadium salt to catalyze the hydrogenation of nitroaromatic compounds, so that corresponding amino aromatic compounds can be prepared, but the difficulty of product separation is increased (US 6258982, WO 9813331). In ethanol, Au/TiO2The catalytic nitrobenzonitrile reaction was carried out for 12h with an aminobenzonitrile yield of 90% and an aminobenzonitrile yield of 96% in toluene (Gkizis, Stratakis et al, cat. commu.2013), WO 2007/116111, (Corma, Serna, Science, 2006). Pt/TiO 22The hydrogenation of nitrobenzonitrile was catalyzed in tetrahydrofuran with 98% yield of aminobenzonitrile (Corma, Serna et al, j. Am. chem. soc., 2008)). Pt/FeOxThe monatomic catalyst catalyzes hydrogenation of a plurality of nitroaromatic compounds in toluene, and shows good selectivity, and the yield of the aminobenzonitrile is 88% (Wei, Liu et al., nat. Commun., 2014). Co-Phen/C and Fe-Phen/C catalysts prepared by high-temperature pyrolysis method are used for catalytically synthesizing various arylamines in tetrahydrofuran-water, the yield of aminobenzonitrile is 87%, and the yield of aminophenylacetylene is 75% (DE 102012209634, (Westerhaus, Jagadesesh et al, Nat. chem., 2013), (Jagadesesh, Surkus et al, Science，2013)). The Co @ SiCN catalyst prepared by a high-temperature pyrolysis method is used for catalyzing nitrobenzonitrile to be hydrogenated in an ethanol-water solvent at the H of 5MPa2The reaction was carried out for 15h with an aminobenzonitrile yield of more than 99% (Schwob, Kempe, angelw. chem. int. ed., 2016). Ni/AC prepared by soaking after treating carrier active carbon with concentrated nitric acidoxThe catalyst, selective hydrogenation of p-nitroaromatic compounds, showed excellent hydrogenation performance, nitrobenzonitrile was reacted in toluene for 350min, and the yield of aminobenzonitrile was 95.2% (Ren, Wei et al, chem. Commun., 2017). The Co-Mo-S catalyst catalyzes the selective hydrogenation of nitrobenzene aromatic compounds in toluene, the nitrobenzonitrile reacts for 8 hours at 150 ℃, the yield of the aminobenzonitrile is more than 99 percent, and the nitrobenzonitrileThe aminophenylacetylene reaction was carried out for 12h with an aminophenylacetylene yield of 75% (Sorribes, Liu et al, ACS cat., 2017).
So far, the following problems mainly exist in the process of preparing amino aromatic compound by selectively reducing nitro aromatic compound: (1) most of the catalysts used in the reaction are noble metal catalysts, so the cost is high, and the industrial production is not facilitated. (2) The solvents used in the reaction, such as toluene, tetrahydrofuran, and the like, are mostly toxic and harmful, and are very volatile. (3) Most of the reducing agents used in the above catalytic reaction are H2Requiring the use of high-pressure devices, and H2Is flammable and explosive, and can cause serious safety problems if the operation is not proper. (4) The non-noble metal catalysts such as Co-Phen/C, Fe-Phen/C, Co @ SiCN, Co-Mo-S and the like have low activity and long reaction time; meanwhile, the catalyst has hydrogenation activity on easily reducible groups such as nitrile groups, alkynyl groups and the like, and when reactants are completely converted, the reaction time is continuously prolonged, the yield of a target product is reduced, and the operation difficulty is increased.
Disclosure of Invention
The invention relates to a method for preparing Cu-Fe/TiO from non-noble metal in green solvent ethanol2Is used as a catalyst to realize the selective catalytic transfer hydrogenation of the nitroaromatic compound to prepare the amino aromatic compound.
The technical scheme adopted by the invention is as follows: mixing the solvents of ethanol and Cu-Fe/TiO2Adding a catalyst, a nitroaromatic compound and hydrazine hydrate into a reactor, wherein the mass ratio of a solvent to the nitroaromatic compound is (5-60): 1, the mass ratio of the nitroaromatic compound to the catalyst is (2-50): 1, the molar ratio of the hydrazine hydrate to a reactant is 2-6, screwing the reactor, purging with high-purity nitrogen for 5min at room temperature, exhausting the air in the reactor, heating the reactor to 80-130 ℃, starting stirring, and reacting for 8-120 min to obtain the corresponding amino aromatic compound.
The nitro aromatic compound is as follows: nitrobenzonitrile, nitrobenzene acetylene, chloronitrobenzene, bromonitrobenzene and iodonitrobenzene.
The Cu-Fe/TiO2The catalyst is prepared by the following method: introducing a vector TiO2Adding Cu (NO) to a certain concentration3)2And Fe (NO)3)3Stirring the mixed solution at normal temperature for 5-30 min, performing ultrasonic treatment for 10-60 min, drying the mixture at 60-150 ℃, grinding the mixture into powder, sieving the powder, and calcining the powder for 3-6 h at 250-450 ℃ in a muffle furnace to obtain Cu-Fe/TiO2The catalyst comprises 2-9% of Cu by mass, and the molar ratio of Cu to Fe is 1 (1-15). Before use of the catalyst H2Or H2-N2Reducing the mixed gas at 200-350 ℃ for 1-3 h, and then using the reduced gas in catalytic transfer hydrogenation reaction of the nitroaromatic compound.
The invention has the following advantages:
(1) uses safer hydrazine hydrate as a reducing agent, has low price and wide source compared with the method using flammable and explosive hydrogen as the reducing agent, and has N2Is the only byproduct, avoids the use of high-voltage equipment and is safer to operate.
(2) The ethanol is an environmentally acceptable solvent, and the ethanol is used as a reaction medium, so that the pollution of harmful solvents such as toluene, tetrahydrofuran and the like to the environment is eliminated.
(3) Using non-noble metal Cu-Fe/TiO2The catalyst has low cost. Cu-Fe/TiO2Has high activity and selectivity for catalytic transfer hydrogenation of nitroaromatic compound and high conversion rate of nitrobenzonitrile>Selectivity to aminobenzonitrile at 99%>98 percent; conversion of Nitrophenylacetylene>Selectivity to aminophenylacetylene at 99%>81 percent; conversion of halogenated Nitrobenzene>When the content is 98.5 percent, the selectivity of the halogenated aniline is more than or equal to 98.9 percent.
(4) No additives need to be added to the reaction system.
In conclusion, Cu-Fe/TiO is used2The catalyst is used for catalyzing the nitroaromatic compound in ethanol to prepare the aminoaromatic compound by hydrogenation, and is a high-efficiency, safe, green and environment-friendly process.
Detailed Description
EXAMPLE 1 hydrogenation of nitrobenzonitrile
10mL of ethanol, C, were added to a reactor with a 30mL polytetrafluoroethylene lineru-Fe/TiO250mg of catalyst (Cu mass content 5wt.%, Cu to Fe molar ratio 1: 5), 0.15g of nitrobenzonitrile and 3 equivalents of hydrazine hydrate, Cu-Fe/TiO before reaction2Calcining at 300 deg.C for 4H in a muffle furnace at 230 deg.C in H2And (4) carrying out reduction for 2 h. High purity N at normal temperature2Purging for 5min, removing air in the reactor, preheating the reactor in 120 ℃ oil bath for 20min, starting stirring, and reacting for 8 min. The reaction product was analyzed by gas chromatography. The conversion of nitrobenzonitrile was 99.6% and the selectivity of aminobenzonitrile was 99.2%.
EXAMPLE 2 hydrogenation of nitrobenzonitrile
The reaction temperature was 80 ℃ and the reaction time was 60min, and the other conditions were the same as in example 1. The conversion of nitrobenzonitrile was 99.4% and the selectivity of aminobenzonitrile was 98.1%.
EXAMPLE 3 hydrogenation of nitrobenzonitrile
The reaction time was 60min, the amount of the reactant nitrobenzonitrile used was 0.6g, and the amount of the reducing agent hydrazine hydrate used was 2.25 equivalents, under the same conditions as in example 1. The conversion of nitrobenzonitrile was 99.3% and the selectivity of aminobenzonitrile was 98.2%.
EXAMPLE 4 Nitrophenylacetylene hydrogenation
The amount of the reactant nitrophenylacetylene was 0.15g, the molar ratio of Cu to Fe in the catalyst was 1:10, the reaction time was 20min, and the other conditions were the same as in example 1. The conversion rate of the nitrobenzene acetylene is 99.2 percent, and the selectivity of the aminophenylacetylene is 81.8 percent.
EXAMPLE 5 hydrogenation of chloronitrobenzene
The reaction time was 10min, and the other conditions were the same as in example 1. The conversion rate of chloronitrobenzene is 98.6 percent, the selectivity of chloroaniline is 99.8 percent, and the selectivity of aniline is 0.2 percent.
EXAMPLE 6 hydrogenation of bromonitrobenzene
The reaction time was 10min, and the other conditions were the same as in example 1. The conversion rate of the bromonitrobenzene is 98.8 percent, the selectivity of the bromoaniline is 99.5 percent, and the selectivity of the aniline is 0.5 percent.
Example 7 hydrogenation of iodonitrobenzene
The reaction time was 10min, and the other conditions were the same as in example 1. The conversion rate of iodonitrobenzene is 99%, the selectivity of iodoaniline is 98.9%, and the selectivity of aniline is 1.1%.

Claims (2)

1. The method for preparing the amino aromatic compound by catalytic hydrogenation of the nitroaromatic compound, wherein the nitroaromatic compound is nitrobenzene acetylene, is characterized in that:
10mL of absolute ethanol, Cu-Fe/TiO were added to a reactor with a 30mL polytetrafluoroethylene liner2Catalyst 50mg, 0.15g nitrobenzene acetylene and 3 equivalents hydrazine hydrate, the mass content of Cu in the catalyst is 5wt.%, the molar ratio of Cu to Fe is 1:10, Cu-Fe/TiO before reaction2Calcining at 300 deg.C for 4H in a muffle furnace at 230 deg.C in H2Medium reduction for 2h, and high-purity N at normal temperature2Purging for 5min, exhausting air in the reactor, preheating the reactor in an oil bath at 120 ℃ for 20min, starting stirring, reacting for 20min, and analyzing the reaction product by using gas chromatography, wherein the conversion rate of the nitrobenzene acetylene is 99.2 percent, and the selectivity of the aminophenylacetylene is 81.8 percent.
2. The method for preparing the amino aromatic compound by catalytic hydrogenation of the nitroaromatic compound, wherein the nitroaromatic compound is iodonitrobenzene, is characterized in that:
10mL of absolute ethanol, Cu-Fe/TiO were added to a reactor with a 30mL polytetrafluoroethylene liner2Catalyst 50mg, 0.15g iodonitrobenzene and 3 equivalents hydrazine hydrate, the mass content of Cu in the catalyst is 5wt.%, the molar ratio of Cu to Fe is 1:5, and Cu-Fe/TiO before reaction2Calcining at 300 deg.C for 4H in a muffle furnace at 230 deg.C in H2Medium reduction for 2h, and high-purity N at normal temperature2Purging for 5min, exhausting air in the reactor, preheating the reactor in 120 ℃ oil bath for 20min, starting stirring, reacting for 10min, and analyzing the reaction product by gas chromatography, wherein the conversion rate of the iodonitrobenzene is 99%, the selectivity of the iodoaniline is 98.9%, and the selectivity of the aniline is 1.1%.
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