A method for preparing an aminophenylacetylene by hydrogenation of a nitrophenylacetylene

Abstract

The present application relates to a method for preparing amino phenyl acetylene by selectively hydrogenating nitro phenyl acetylene. The method uses MoO3 / TiO2 catalyst, anhydrous ethanol as solvent and hydrazine hydrate as hydrogen source to catalyze hydrogenation of nitro phenyl acetylene at 30-80 DEG C to prepare amino phenyl acetylene. When nitro phenyl acetylene is completely converted, the selectivity of amino phenyl acetylene can reach 99.6%, and the selectivity of amino phenyl acetylene is basically unchanged by continuing to extend the reaction time.

Description

TECHNICAL FIELD

[0001] The application relates to a method for preparing an aminophenylacetylene by catalytically hydrogenating a nitrophenylacetylene. BACKGROUND

[0002] The aminophenylacetylene is an important intermediate for synthesizing drugs, materials, dyes, pigments and the like, and has important applications in the fields of organic synthesis, medicine, materials and life science research and the like. For example, the 3-aminophenylacetylene is an important intermediate for synthesizing an effective anticancer drug, erlotinib hydrochloride; the aminophenylacetylene is also an important intermediate for synthesizing high-grade resins in the fields of aviation, aerospace and military.

[0003] The catalytic hydrogenation of the nitrophenylacetylene is a relatively clean process for preparing the aminophenylacetylene. The nitrophenylacetylene contains both a nitro group and an acetylene group which are two easily reduced groups. Due to the high activity of the acetylene group, it is challenging to hydrogenate the nitro group while the acetylene group is not hydrogenated. The catalyst which has high activity for hydrogenating the nitro group and is inert for hydrogenating the acetylene group is the key to improving the selectivity of the aminophenylacetylene.

[0004] The research progress of the noble metal catalyst for catalyzing the hydrogenation of the nitrophenylacetylene to prepare the aminophenylacetylene is as follows. The catalyst is used to catalyze the hydrogenation of the nitrophenylacetylene in toluene with H2 as the hydrogen source, and the conversion rate of the nitrophenylacetylene is 98.9% and the selectivity of the 4-aminophenylacetylene is 90.1% after the reaction of the 4-nitrophenylacetylene at 40 DEG C for about 6 h (Corma, et al., J. Am. Chem. Soc., 2008). 0.2 wt% Pt / TiO2 The catalyst is used to catalyze the hydrogenation of the nitrophenylacetylene in ethanol with H2 as the hydrogen source, and the conversion rate of the nitrophenylacetylene is 100% and the selectivity of the 4-aminophenylacetylene is 87.9% after the reaction of the 4-nitrophenylacetylene at 50 DEG C under 4 MPa H2 (CN 107216255 B). Pt-Zn / SnO2-Sb2O3 The catalyst is used to catalyze the hydrogenation of the nitrophenylacetylene in toluene with CO and H2O as the hydrogen source, and the conversion rate of the nitrophenylacetylene is 100% and the selectivity of the 4-aminophenylacetylene reaches 99.9% after the reaction of the 4-nitrophenylacetylene for 4 h (Lili Lin, et al., Nat. Nanotech., 2019). 0.25%Pt / α-MoC The catalyst is used to catalyze the hydrogenation of the nitrophenylacetylene in DMF with HCOONH4 as the hydrogen source, and the conversion rate of the nitrophenylacetylene is 100% and the selectivity of the 4-aminophenylacetylene is 92% after the reaction of the 4-nitrophenylacetylene at 60 DEG C for 3 h (Yonggang Feng, et al., J. Am. Chem. Soc., 2020). PdCd 1.13 The catalyst is used to catalyze the hydrogenation of the nitrophenylacetylene in DMF with HCOONH4 as the hydrogen source, and the conversion rate of the nitrophenylacetylene is 100% and the selectivity of the 4-aminophenylacetylene is 92% after the reaction of the 4-nitrophenylacetylene at 60 DEG C for 3 h (Yonggang Feng, et al., J. Am. Chem. Soc., 2020). PtZn / HNCNTCatalyst, ammonia borane as hydrogen source, 4-nitrophenylacetylene in a mixture of ethanol and water at 40℃ for 4 h, nearly complete conversion, 4-aminophenylacetylene selectivity of 99% (Aijuan Han, et al., Nat. Commun., 2019).

[0005] Due to the scarcity of precious metal resources, replacing precious metal catalysts with non-precious metal catalysts can significantly reduce catalyst costs. With CoS x Catalyze 3-nitrophenylacetylene hydrogenation, 108℃ in H2 for 45 min, 3-aminophenylacetylene yield 86% (Anatoli Onopchenko, et al., J. Org. Chem., 1979). The process has the disadvantages of desulfurization, solvent recovery difficulty and environmental pollution. The catalyst prepared by high temperature pyrolysis 3 wt% Co / C catalysis 4-nitrophenylacetylene hydrogenation, tetrahydrofuran as solvent, 110℃ and 5 MPa H2 for 4 h, 4-aminophenylacetylene yield 88% (Felix A. Westerhaus, et al., Nat. Chem., 2013). Mix Fe(OAc)2, 1,10-phenanthroline and carbon powder, calcine at 800℃ to obtain Fe-phen / C Catalyst, tetrahydrofuran as solvent, hydrazine hydrate as hydrogen source, Fe-phen / C Catalyze 4-nitrophenylacetylene at 100℃ for 10 h, 4-nitrophenylacetylene conversion rate is 100%, 4-aminophenylacetylene selectivity is 96% (Rajenahally V. Jagadeesh, et al., Chem. Commun., 2011); In addition, with tetrahydrofuran and water as solvent, at 105℃ and 50 bar H2, Fe-phen / C Catalyze 4-nitrophenylacetylene for 26 h, 4-aminophenylacetylene yield 75% (Rajenahally V. Jagadeesh, et al., Science, 2013). Fe2O3-CeO2 / TiO2 as catalyst, anhydrous ethanol as solvent, hydrazine hydrate as hydrogen source, catalyze nitrophenylacetylene hydrogenation to prepare aminophenylacetylene at 80-150℃, 4-nitrophenylacetylene conversion rate is 100%, 4-aminophenylacetylene selectivity is 94.8% (CN 202211173806.1).

[0006] There are still the following problems in the use of non-precious metal catalysts to catalyze nitrophenylacetylene hydrogenation: (1) Most of them react in toxic and volatile organic solvents such as toluene and tetrahydrofuran. (2) The activity of the catalyst is low, the reaction time is too long or the reaction temperature is too high. (3) The preparation conditions of some catalysts are harsh. SUMMARY

[0007] The application relates to a method for preparing aminophenylacetylene by selectively hydrogenating nitrophenylacetylene with MoO3 / TiO2 as a catalyst, ethanol as a green solvent and hydrazine hydrate as a hydrogen source.

[0008] The technical scheme adopted by the application is as follows: anhydrous ethanol, nitrophenylacetylene, a catalyst MoO3 / TiO2 and an 80% hydrazine hydrate solution are added into a reaction kettle, the mass ratio of the anhydrous ethanol to the nitrophenylacetylene is (20-120):1, the mass ratio of the nitrophenylacetylene to the catalyst is (1-20):1, and the molar ratio of the N2H4.H2O to the nitrophenylacetylene is (2-5):1, the reaction kettle is tightly screwed, then the reaction kettle is purged with high-purity nitrogen for 5 min, the reaction kettle is preheated at 30-80 DEG C for 20 min, stirring is started, and the reaction is carried out for a certain time until the conversion rate reaches 100%.

[0009] The nitrophenylacetylene is 4-nitrophenylacetylene and 3-nitrophenylacetylene.

[0010] The MoO3 / TiO2 catalyst is prepared by the following method: an excessive amount of an ammonium molybdate solution with a certain concentration is impregnated on TiO2 powder, the sample is dried at 60 DEG C for 12 h, is ground, is sieved, and is calcined at 300-600 DEG C in a muffle furnace for 2-5 h to obtain the catalyst MoO3 / TiO2, wherein the mass content of MoO3 is 4-10%.

[0011] The application has the following advantages:

[0012] (1) The anhydrous ethanol is used as the solvent, and the use of toxic solvents such as toluene and tetrahydrofuran is avoided.

[0013] (2) The catalyst has high activity and high selectivity for hydrogenation of the nitrophenylacetylene, and the selectivity of 4-amino phenylacetylene can be up to 99.6%. The selectivity of 4-amino phenylacetylene does not substantially decrease by prolonging the reaction time, and the difficulty in controlling the reaction in large-scale production is reduced.

[0014] In summary, the MoO3 / TiO2 catalyst, the anhydrous ethanol as the solvent and the hydrazine hydrate as the hydrogen source are used to catalyze the hydrogenation of the nitrophenylacetylene to prepare the aminophenylacetylene, and the method is a relatively green and environment-friendly high-efficiency method. DETAILED DESCRIPTION

[0015] Example 1 Catalyst preparation and hydrogenation of 4-nitrophenylacetylene

[0016] A certain concentration of ammonium molybdate solution was prepared, ammonium molybdate was loaded on TiO2(P25) by excess impregnation method, after drying at 60 ℃ for 12 h, grinding, screening, calcination at 500 ℃ in muffle furnace for 3 h in air atmosphere, 4.43 wt% MoO3 / TiO2 catalyst was obtained.

[0017] In a 30 mL high-pressure reaction kettle with polytetrafluoroethylene lining, 10 mL of anhydrous ethanol, 0.5 mmol of 4-nitrophenylacetylene, 2 mmol of N2H4·H2O (80% mass fraction of hydrazine hydrate) and 0.05 g of the catalyst were added. The reaction kettle was tightly closed, purged with high-purity nitrogen for 5 min at room temperature, then preheated in a 80 ℃ water bath for 20 min, and the stirring was turned on. The reaction time was 10 min and 30 min, respectively, and the reaction products were analyzed by gas chromatography. The conversion rate of 4-nitrophenylacetylene was 100% and the selectivity of 4-aminophenylacetylene was 99.1% after 10 min of reaction. The conversion rate of 4-nitrophenylacetylene was 100% and the selectivity of 4-aminophenylacetylene was 99.5% after 30 min of reaction.

[0018] Example 2 Hydrogenation of 4-nitrophenylacetylene

[0019] The catalyst was the same as in Example 1, the catalyst dosage was 0.0125 g, the reaction time was 2.5 min and 10 min, respectively, and the other conditions were the same as in Example 1. The conversion rate of 4-nitrophenylacetylene was 100% and the selectivity of 4-aminophenylacetylene was 98.7% after 2.5 min of reaction. The conversion rate was 100% and the selectivity of 4-aminophenylacetylene was 98.9% after 10 min of reaction.

[0020] Example 3 Hydrogenation of 4-nitrophenylacetylene

[0021] The catalyst with a reaction time of 10 min in Example 2 was washed with anhydrous ethanol and centrifuged 4 times, and then directly used for reaction. The reaction time was 10 min, and the other conditions were the same as in Example 2. The conversion rate of 4-nitrophenylacetylene was 100% and the selectivity of 4-aminophenylacetylene was 96%.

[0022] Example 4 Hydrogenation of 4-nitrophenylacetylene

[0023] The catalyst was the same as in Example 1. The amount of anhydrous ethanol was 5 mL, the catalyst dosage was 0.0125 g, the reaction time was 1.5 min, and the other reaction conditions were the same as in Example 1. The conversion rate of 4-nitrophenylacetylene was 100% and the selectivity of 4-aminophenylacetylene was 98.7%.

[0024] Example 5 Hydrogenation of 4-nitrophenylacetylene

[0025] The catalyst is the same as in Example 1. The catalyst dosage is 0.0125 g, the reaction temperature is 30°C, the reaction time is 11.5 h, and the other conditions are the same as in Example 1. The conversion of 4-nitrophenylacetylene is 100%, and the selectivity of 4-aminophenylacetylene is 98.6%.

[0026] Example 6 Hydrogenation of 4-nitrophenylacetylene

[0027] The support is TiO2(Nanjing Haitai Nano HTTi-01), the catalyst calcination temperature is 400°C for 3 h, and the other preparation conditions are the same as in Example 1.

[0028] The catalyst dosage is 0.0125 g, the reaction time is 10 min, and the other reaction conditions are the same as in Example 1. The conversion of 4-nitrophenylacetylene is 100%, and the selectivity of 4-aminophenylacetylene is 98%.

[0029] Comparative Example 1 Hydrogenation of 4-nitrophenylacetylene

[0030] The support is neutral Al2O3, the catalyst calcination temperature is 400°C for 3 h, and the other preparation conditions are the same as in Example 1.

[0031] The catalyst dosage is 0.0125 g, the reaction time is 10 min, and the other reaction conditions are the same as in Example 1. The conversion of 4-nitrophenylacetylene is 8.8%, and the selectivity of 4-aminophenylacetylene is 33.5%.

[0032] Comparative Example 2 Hydrogenation of 4-nitrophenylacetylene

[0033] The support is γ-Al2O3, the catalyst calcination temperature is 400°C for 3 h, and the other preparation conditions are the same as in Example 1.

[0034] The catalyst dosage is 0.0125 g, the reaction time is 10 min, and the other reaction conditions are the same as in Example 1. The conversion of 4-nitrophenylacetylene is 11.2%, and the selectivity of 4-aminophenylacetylene is 35.7%.

[0035] Comparative Example 3 Hydrogenation of 4-nitrophenylacetylene

[0036] The support is SiO2, the catalyst calcination temperature is 400°C for 3 h, and the other preparation conditions are the same as in Example 1.

[0037] The catalyst dosage is 0.0125 g, the reaction time is 10 min, and the other reaction conditions are the same as in Example 1. The conversion of 4-nitrophenylacetylene is 13.9%, and the selectivity of 4-aminophenylacetylene is 44.8%.

[0038] Example 7 Hydrogenation of 4-nitrophenylacetylene

[0039] The MoO3content in the catalyst was 7.32 wt%, and other preparation conditions were the same as in Example 1.

[0040] The catalyst dosage was 0.0053 g, the anhydrous ethanol dosage was 5 mL, the reaction time was 5 min, and other conditions were the same as in Example 1. The conversion rate of 4-nitrophenylacetylene was 100%, and the selectivity of 4-aminophenylacetylene was 97.6%.

[0041] Example 8 Hydrogenation of 4-nitrophenylacetylene

[0042] The MoO3content in the catalyst was 10 wt%, and other preparation conditions were the same as in Example 1.

[0043] The reaction time was 10 min, and other conditions were the same as in Example 1. The conversion rate of 4-nitrophenylacetylene was 100%, and the selectivity of 4-aminophenylacetylene was 99.6%.

[0044] Example 9 Hydrogenation of 3-nitrophenylacetylene

[0045] The catalyst was calcined at 400°C for 3 h, and other preparation conditions were the same as in Example 1.

[0046] The catalyst dosage was 0.0125 g, the reactant was 0.5 mmol of 3-nitrophenylacetylene, the reaction time was 10 min, and other conditions were the same as in Example 1. The conversion rate of 3-nitrophenylacetylene was 100%, and the selectivity of 3-aminophenylacetylene was 98.3%.

Claims

1. A process for the hydrogenation of a nitrophenylacetylene to an aminophenylacetylene, characterized in that, The MoO3 / TiO2 catalyst is used, anhydrous ethanol is used as a solvent, and hydrazine hydrate is used as a hydrogen source to catalyze hydrogenation of nitrophenyl acetylene at 30-80 DEG C to prepare aminophenyl acetylene; The MoO3 / TiO2 catalyst contains 4-10% of MoO3 by mass; The nitrophenyl acetylene is 4-nitrophenyl acetylene and 3-nitrophenyl acetylene; The MoO3 / TiO2 catalyst contains 4-10% of MoO3 by mass; 2. A process for the hydrogenation of a nitrophenylacetylene to an aminophenylacetylene according to claim 1, characterized in that, The MoO3 / TiO2 catalyst contains 4-10% of MoO3 by mass;