CN104974047A - Method for preparing aminostyrene through catalytic hydrogenation of nitrostyrene - Google Patents
Method for preparing aminostyrene through catalytic hydrogenation of nitrostyrene Download PDFInfo
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- CN104974047A CN104974047A CN201410131356.9A CN201410131356A CN104974047A CN 104974047 A CN104974047 A CN 104974047A CN 201410131356 A CN201410131356 A CN 201410131356A CN 104974047 A CN104974047 A CN 104974047A
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- nitrostyrolene
- aminostyryl
- sno
- aminostyrene
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Abstract
The invention relates to a method for preparing aminostyrene through catalytic hydrogenation of nitrostyrene. According to the method, in environment-friendly solvents H2O, ethanol, n-heptane, H2O-ethanol or H2O-n-heptane, nitrostyrene is catalyzed by Pt/SnO2-Sb2O3 serving as a catalyst to have hydrogenation reaction at 35-120 DEG C to prepare aminostyrene. Pt/SnO2-Sb2O3 has high selectivity in generation of aminostyrene; in H2O, ethanol and n-heptane, the selectivity for aminostyrene is respectively greater than 97%, greater than 95% and greater than 96%; the reaction rate in H2O is highest and the yield of aminostyrene is greater than 97%; no accumulation of harmful intermediates such as phenyl hydroxylamine is generated in the reaction process; since Pt/SnO2-Sb2O3 almost has no catalytic activity for hydrogenation of aminostyrene, the yield of aminostyrene does not decrease when time goes by after the reactants are completely converted.
Description
Technical field
The present invention relates to the method that nitrostyrolene shortening prepares aminostyryl.Be specifically related to Pt/SnO
2-Sb
2o
3for catalyzer, at green solvent H
2o, ethanol, normal heptane, H
2o-ethanol or H
2in O-n-heptane system, the method for aminostyryl is prepared in the selective hydrogenation of catalysis nitrostyrolene.
Background technology
Aminostyryl is the one of aromatic amine compounds, is the intermediate producing the important Chemicals such as medicine, stablizer, sterilant, Insecticides (tech) & Herbicides (tech).
Nitrostyrolene shortening is the effective ways preparing aminostyryl.In nitrostyrolene molecule, nitro and vinyl group, all easily by hydrogenating reduction, are researched and developed and are had greater activity to nitro hydrogenation and have more SA catalyzer to vinyl group hydrogenation, are the keys improving aminostyryl yield.In addition, hydrogenation process should manage the accumulation avoiding harmful intermediates such as generation phenylhydroxyamine.At present, the catalyzer for this reaction has: CoS
3, Co
3o
4, Fe
2o
3deng the metal catalyst such as compound and Au, Ag, Pt.In methyl alcohol, with CoS
3catalysis 50g nitrostyrolene hydrogenation 5h, obtain 37g aminostyryl, molar yield is 92.6%(US4051177).The weak point that this catalyzer exists is, in hydrogenation process, produces sulfur byproduct species, reduces quality product, and limit the recycling of solvent.In addition, produce the sulfocompound of the high volatilities such as hydrogen sulfide in reaction process, this may cause serious safety problem when large-scale industry is combined to.CN1149287A disclose with the supporting Pt of Pb modification be catalyzer, molysite is promotor, quaternary amine alkali for promotor altogether, the method for preparation containing the substituent aromatic amine compound of unsaturated C-C.The noble metal catalysts such as Pt are modified through phosphorus compound, also can catalyzing aromatic hydrocarbon nitro-compound hydrogenation, prepare the multiple aromatic amine compounds such as aminostyryl, the compound of vanadium or iron is added in reaction system, effectively can suppress the accumulation (US6258982, WO9813331) of harmful intermediate phenylhydroxyamine.Two kinds of methods of above-mentioned use Pt catalyzer, need to add the additional materials such as the compound of molysite, vanadium and phosphorus in reaction system, the separating difficulty of this complicacy increase operated and product.Au/TiO is adopted in toluene
2, Au/Fe
2o
3, or Ag/Al is adopted in tetrahydrofuran (THF)
2o
3catalysis nitrostyrolene hydrogenation, does not need any additive, and reaction process does not have the accumulation of phenylhydroxyamine, the yield of aminostyryl can reach 94% ~ 96%(WO2007116111, (Corma, Serna, Science, 2006), JP2011036748, (Shimizu, Miyamoto et al., J. Catal., 2010)).With TiO
2, Fe
2o
3with the metal catalyst such as activated carbon supported 5%Ni, 0.2%Pt, 1%Ru, after 450 DEG C of reduction, catalysis nitrostyrolene hydrogenation in toluene, the yield of aminostyryl is 70% ~ 94%.Improve content of metal, catalyst selectivity will be caused to reduce, such as, with 0.2%Pt/TiO
2for catalyzer, the yield of aminostyryl is 92%; According to 2%Pt/TiO
2, yield is down to 55%(WO2009071727, (Corma, Serna et al., J. Am. Chem. Soc., 2008)).By Co prepared by high temperature thermal decomposition method
3o
4and Fe
2o
3catalyzer, in tetrahydrofuran (THF) or tetrahydrofuran (THF)-water solvent, 110 ~ 120 DEG C can catalyze and synthesize the multiple aromatic amine compound (DE102012209634 comprising aminostyryl, (Westerhaus, Jagadeesh et al., Nat. Chem., 2013), (Jagadeesh, Surkus et al., Science
,2013)).
At present, there is following subject matter for aminostyryl in Hydrogenation: (1) reaction is many to be carried out in the poisonous and harmful such as toluene, tetrahydrofuran (THF), volatile organic solvent.(2) above-mentioned CoS
3, Co
3o
4, Fe
2o
3and the catalyzer such as Au, Ag, activity is lower, the temperature (110 ~ 160 DEG C) that reaction needed is higher and longer time.(3) method disclosed in WO2009071727, the method at the strong interaction modified metal center between the metal namely utilizing high temperature reduction to produce and carrier, have following deficiency: after high temperature reduction, catalyst activity significantly declines; In addition, content of metal is lower, if improve content of metal, catalyst selectivity will be caused obviously to decline.(4) catalyzer such as above-mentioned Au, Ag, p-aminophenyl ethene C=C key hydrogenation has activity, therefore, after reactant transforms completely, continue to extend the reaction times, the aminostyryl of generation is by further hydrocracking, cause its yield to reduce, which increase in production difficulty ((Shimizu, the Miyamoto et al. controlling to react, J. Catal., 2010), (Shimizu, Miyamoto et al., J. Phys. Chem. C, 2009)).
Summary of the invention
The present invention relates at green solvent H
2o, environment acceptable solvent ethanol, normal heptane, H
2o-ethanol or H
2in O-normal heptane, with Pt/SnO
2-Sb
2o
3for catalyzer, the method for aminostyryl is prepared in the selective hydrogenation of catalysis nitrostyrolene.
The technical solution used in the present invention is: by solvent (water, ethanol, normal heptane, water-ethanol or water-normal heptane), nitrostyrolene, Pt/SnO
2-Sb
2o
3catalyzer adds in reactor, the mass ratio of solvent and nitrostyrolene is (0.5 ~ 50): 1, the mass ratio of nitrostyrolene and catalyzer is (1 ~ 100): 1, in catalyzer, the mass content of Pt is 0.1 ~ 3%, tightens reactor, purges 5min under room temperature with high pure nitrogen, get rid of the air in reactor, then reactor is heated to 35 ~ 120 DEG C, preferably 50 ~ 90 DEG C, is filled with 0.1 ~ 8MPa H
2, preferably 0.5 ~ 4MPa H
2, open and stir, reaction 5 ~ 240min, obtains aminostyryl.
Described nitrostyrolene is 3-nitrostyrolene and 4-nitrostyrolene.
Described Pt/SnO
2-Sb
2o
3catalyzer is adopted and is prepared with the following method: by the SnCl of certain proportioning
4, SbCl
3hydrochloric acid mixed solution, drop in polyvinyl alcohol water solution with ammoniacal liquor, adjust ph is 3.5 simultaneously, obtained SnO
2-Sb
2o
3presoma compound precipitates, by this compound after 80 ~ 150 DEG C of dryings, grinding powder, in retort furnace 500 ~ 800 DEG C calcining 3 ~ 6h, obtain carrier S nO
2-Sb
2o
3, wherein the mol ratio of Sb and Sn is (0 ~ 0.2): 1; Adopt equi-volume impregnating or excessive dipping-ultrasonic method by H
2ptCl
6or Pt (NH
3)
4cl
2be loaded to SnO
2-Sb
2o
3on, in catalyzer, the mass content of Pt is 0.1% ~ 3%; When adopting excessive dipping-ultrasonic method, by SnO
2-Sb
2o
3powder pours the excessive H of volume into
2ptCl
6or Pt (NH
3)
4cl
2in solution, by ultrasonic for these slurries 30min, then 50 DEG C of stirred in water bath, until thick taking-up; After 80 ~ 120 DEG C of dryings, 350 ~ 500 DEG C of calcining 3 ~ 6h, use H
2or H
2-N
2gas mixture at 200 ~ 250 DEG C of reductase 12 h, for reaction.
Tool of the present invention has the following advantages: (1) H
2o is green solvent, and ethanol and normal heptane are environment acceptable solvents, adopts H
2o, ethanol, normal heptane are reaction medium, reduce the hazardous solvent such as toluene, tetrahydrofuran (THF) pollution on the environment.Adopt H
2o-ethanol or H
2o-normal heptane is solvent, can reduce the consumption of ethanol and normal heptane further.
(2) Pt/SnO
2-Sb
2o
3to nitro hydrogenation, there is greater activity, and to vinyl double bond hydrogenation catalytically inactive, therefore can generate aminostyryl by catalysis nitrostyrolene high-selective and hydrogenating, the most highly selective >97% of aminostyryl; After reactant transforms completely, even if continue to extend the reaction times, the yield of aminostyryl declines hardly, it reduces in large-scale production the difficulty controlling to react.
(3) in catalyzer, the charge capacity of Pt can change at relative broad range, increases the charge capacity of Pt, the selectivity of aminostyryl can not be made to reduce.
(4) without the need to carrying out modification to catalyzer, do not need to add any additive in reaction system yet.
(5) reaction process does not have the accumulation of harmful intermediates such as phenylhydroxyamine, nitroso compound, azo-compound.
In sum, Pt/SnO is adopted
2-Sb
2o
3catalyzer, at H
2o, ethanol, normal heptane, H
2o-ethanol or H
2in O-normal heptane, catalysis nitrostyrolene Hydrogenation is for aminostyryl, is the technological process of a kind of efficient, safety and environmental protection.
Embodiment
Embodiment 1 3-nitrostyrolene hydrogenation
5mL H is added in 50mL autoclave
2catalyst Pt/the SnO of O, 0.25g 3-nitrostyrolene, 0.15g reduction
2-Sb
2o
3, the mass content of Pt be 0.5%, Sb and Sn mol ratio be 0.1:1, adopt equi-volume impregnating supporting Pt, reaction procatalyst is at H
2in 250 DEG C of reductase 12 h.Tighten reactor, under room temperature, use high-purity N
2purge 5min, get rid of the air in reactor.Reactor, in 50 DEG C of water bath with thermostatic control preheating 15min, is filled with 4MPa H
2, open and stir, reaction 3h.Cooled by reactor, reaction product extracts through toluene, uses gas chromatographic analysis.Nitrostyrolene transformation efficiency is 96.7%, and aminostyryl selectivity is 98.1%.
Embodiment 2 3-nitrostyrolene hydrogenation
The mass content of Pt is 1.0%, and the reaction times is 2h, and other condition is with embodiment 1.Nitrostyrolene transformation efficiency is 98.2%, and aminostyryl selectivity is 98.4%.
Embodiment 3
Reaction times is 4h, and catalyzer and other conditions are with embodiment 2.Nitrostyrolene transformation efficiency is 100%, and aminostyryl selectivity is 97.3%.
From embodiment 2 and embodiment 3, extend the reaction times, aminostyryl selectivity is almost constant, shows Pt/SnO
2-Sb
2o
3almost catalytic activity is not had to target product aminostyryl hydrogenation.
Embodiment 4 3-nitrostyrolene hydrogenation
The mass content of Pt is 2.0%, and the reaction times is 1h, and other conditions are with embodiment 1.Nitrostyrolene transformation efficiency is 91.7%, and aminostyryl selectivity is 98.1%.
Embodiment 5 3-nitrostyrolene hydrogenation
Catalyst Pt/SnO
2-Sb
2o
3adopt excessive dipping-ultrasonic method preparation, the mass content of Pt is 0.5%, and other condition is with embodiment 1.Nitrostyrolene transformation efficiency is 100%, and aminostyryl selectivity is 97.6%.
Embodiment 6 3-nitrostyrolene hydrogenation
Solvent is 5mL normal heptane, and catalyzer and other conditions are with embodiment 1, and reaction product uses gas chromatographic analysis after alcohol dilution.Nitrostyrolene transformation efficiency is 82.4%, and aminostyryl selectivity is 96.3%.
Embodiment 7 4-nitrostyrolene hydrogenation
Catalyst Pt/the SnO of 5mL ethanol, 0.25g 4-nitrostyrolene, 0.15g reduction is added in 50mL autoclave
2-Sb
2o
3, catalyzer and other condition are with embodiment 1, and reaction product uses gas chromatographic analysis after alcohol dilution.Nitrostyrolene transformation efficiency is 97.6%, and aminostyryl selectivity is 95.6%.
Embodiment 8 3-nitrostyrolene hydrogenation
Solvent is 5mL H
2o-normal heptane, H
2the volume ratio of O and normal heptane is 1:1, catalyst Pt/SnO
2-Sb
2o
3adopt the preparation of excessive dipping-ultrasonic method, the mass content of Pt be 0.5%, Sb and Sn mol ratio be 0.025:1, the reaction times is 2h, and other condition is with embodiment 1.Nitrostyrolene transformation efficiency is 90.4%, and aminostyryl selectivity is 97.4%.
Embodiment 9 3-nitrostyrolene hydrogenation
Temperature of reaction is 120 DEG C, H
2pressure is 1 MPa, and the reaction times is 50min, and catalyzer and other condition are with embodiment 1.Nitrostyrolene transformation efficiency is 100%, and aminostyryl selectivity is 94.7%.
Claims (7)
1. nitrostyrolene shortening prepares the method for aminostyryl, it is characterized in that, by solvent, nitrostyrolene, catalyst Pt/SnO
2-Sb
2o
3add in reactor, the mass ratio of solvent and nitrostyrolene is (0.5 ~ 50): 1, the mass ratio of nitrostyrolene and catalyzer is (1 ~ 100): 1, tighten reactor, 5min is purged with high pure nitrogen under room temperature, get rid of the air in reactor, then reactor is heated to 35 ~ 120 DEG C, is filled with 0.1 ~ 8MPa H
2, open and stir, reaction 5 ~ 240min;
Described nitrostyrolene is 3-nitrostyrolene and 4-nitrostyrolene;
Described solvent is one of the following: H
2the H of O, ethanol, normal heptane, arbitrary proportion
2the H of O-alcohol mixture, arbitrary proportion
2o-normal heptane mixture;
Described catalyzer is Pt/SnO
2-Sb
2o
3, the mass content of Pt be 0.1 ~ 3%, Sb and Sn mol ratio be (0 ~ 0.2): 1.
2. prepare the method for aminostyryl according to nitrostyrolene shortening according to claim 1, it is characterized in that, the carrier of described catalyzer is the SnO prepared by coprecipitation method
2-Sb
2o
3, the mol ratio of Sb and Sn is (0 ~ 0.2): 1.
3. prepare the method for aminostyryl according to nitrostyrolene hydrogenation catalyst according to claim 1, it is characterized in that, described catalyst Pt/SnO
2-Sb
2o
3, the mass content of Pt is 0.1% ~ 3%.
4. prepare the method for aminostyryl according to nitrostyrolene shortening according to claim 1, it is characterized in that, described catalyst Pt/SnO
2-Sb
2o
3at 350 ~ 500 DEG C of calcining 3 ~ 6h.
5. prepare the method for aminostyryl according to nitrostyrolene shortening according to claim 1, it is characterized in that, described catalyst Pt/SnO
2-Sb
2o
3use H
2or H
2-N
2gas mixture is at 200 ~ 250 DEG C of reductase 12 h.
6. prepare the method for aminostyryl according to nitrostyrolene shortening according to claim 1, it is characterized in that, described solvent is H
2the H of O, ethanol, normal heptane, arbitrary proportion
2the H of O-alcohol mixture or arbitrary proportion
2o-normal heptane mixture.
7. prepare the method for aminostyryl according to nitrostyrolene shortening according to claim 1, it is characterized in that, described reactor Heating temperature is 35 ~ 120 DEG C, preferably 50 ~ 90 DEG C.
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| RU2485094C1 (en) * | 2012-06-07 | 2013-06-20 | Федеральное государственное бюджетное учреждение науки Институт высокомолекулярных соединений Российской академии наук | Method of producing 4-aminostyrene |
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| CN106810628A (en) * | 2016-11-28 | 2017-06-09 | 佛山市尚好门窗有限责任公司 | A kind of preparation method of polynitrobenzene ethene |
| CN107216255A (en) * | 2017-05-26 | 2017-09-29 | 长春工业大学 | A kind of nitrobenzene acetylene Hydrogenation for amino phenylacetylene method |
| CN107216255B (en) * | 2017-05-26 | 2021-06-15 | 长春工业大学 | Method for preparing aminophenylacetylene by hydrogenation of nitrophenylacetylene |
| CN112403460A (en) * | 2019-08-23 | 2021-02-26 | 中国科学院大连化学物理研究所 | Platinum catalyst based on metal-carrier strong interaction and preparation and application thereof |
| CN112403460B (en) * | 2019-08-23 | 2022-05-06 | 中国科学院大连化学物理研究所 | Platinum catalyst based on metal-carrier strong interaction and preparation and application thereof |
| CN113135824A (en) * | 2021-03-05 | 2021-07-20 | 内蒙古大学 | Catalyst process for preparing aminostyrene by high-selectivity hydrogenation of nitrostyrene |
| CN115869955A (en) * | 2022-11-28 | 2023-03-31 | 东南大学 | Co-based multi-phase magnetic catalyst and preparation and application thereof |
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