CN107098786A - A kind of preparation method of aromatic amine compounds - Google Patents
A kind of preparation method of aromatic amine compounds Download PDFInfo
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- CN107098786A CN107098786A CN201710337985.0A CN201710337985A CN107098786A CN 107098786 A CN107098786 A CN 107098786A CN 201710337985 A CN201710337985 A CN 201710337985A CN 107098786 A CN107098786 A CN 107098786A
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- 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
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- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
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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
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Abstract
The present invention relates to pharmaceutical-chemical intermediate and related chemistry technical field, a kind of preparation method of aromatic amine compounds comprises the following steps：(1), nitro substituted aromatic compound, nanometer porous metal catalyst and solvent are added in reactor, hydrogen, heating stirring is passed through；(2) after, reaction terminates, the reaction solution that step (1) is obtained carries out removal of solvent under reduced pressure, then obtains target product aromatic amine compounds by column chromatography.Compared with the prior art, the present invention can be compared with playing its unique catalytic activity using nanoporous palladium catalyst under temperate condition, can conveniently it be recycled as catalyst, simple filtration cleaning can be reused again, the catalyst structure is stable, catalytic activity is high, recycling repeatedly has not yet to see catalytic activity and substantially reduced, and possibility is provided for its realization industrialization.
Description
Technical field
The present invention relates to a kind of preparation method of aromatic amine compounds, belong to pharmaceutical-chemical intermediate and related chemistry technology
Field.
Background technology
Aromatic amine compounds are the important intermediate of the chemical products such as sulfa drugs, organic azo dyestuff, its preparation side
Method is mainly reduced by the selective catalytic hydrogenation of aromatic nitro compound.
The restoring method of nitro has sodium sulfide reducing method, metal dust (iron powder, zinc powder etc.) salt using equivalent on aromatic ring
Sour reducing process, electrochemical reducing and transition metal-catalyzed hydrogenation method etc..Sodium sulfide reducing method produces a large amount of sulfur-containing waste waters, increases
Plus post-processing cost；A large amount of metal waste residues are not only produced using metal dust (iron powder, zinc powder etc.) hydrochloric acid reducing process of equivalent,
And produce a large amount of acid-base waste fluids, do not meet current environment-friendly theory, in industry substantially without；Electrochemical reducing is needed
Special electrochemical apparatus is wanted, its energy resource consumption is very big；Transition metal-catalyzed hydrogenation method mainly has homogeneously and heterogeneous catalysis, its
Metal ion residual is had in middle homogeneous catalytic hydrogenation product；Heterogeneous catalysis hydrogenation is most of to utilize load type metal nanometer
Grain catalyst, influences the factor of such catalyst effect complex, mainly including catalyst activity component, auxiliary agent, load
The influence factor such as body and different restoring method.Palladium catalyst has very high catalytic activity, therefore industry in catalysis nitro reduction
Upper reduction nitro application it is most be palladium catalyst, reported in spite of the catalysis nitro reduction of many palladium nanoparticles, but most of
Palladium nanoparticles are more by the Auxiliary support such as part or carrier, and recycling needs to extract reaction solution, divides the processing such as liquid, than
It is cumbersome, and metal oxide or the palladium nanoparticles supported by part are supported on, after repeatedly recycling, it may occur that because
The reunion of metal nanoparticle and deactivation phenomenom.
The content of the invention
In order to overcome the deficiencies in the prior art, it is an object of the present invention to provide a kind of preparation side of aromatic amine compounds
Method.This method uses nano porous palladium (PdNPore) catalyst, and nano porous palladium can be unique compared with it is played under temperate condition
Catalytic activity, can conveniently be recycled as catalyst, and simple filtration cleaning can be reused again, and the catalyst structure is steady
Fixed, catalytic activity is high, and recycling repeatedly has not yet to see catalytic activity and substantially reduced.
In order to realize foregoing invention purpose, solving oneself has problem present in technology, and the present invention is adopted the technical scheme that：
A kind of preparation method of aromatic amine compounds, it is characterised in that：By raw material of nitro substituted aromatic compound, nano porous metal
It is hydrogen source for catalyst, hydrogen, selective hydrogenation prepares aromatic amine compounds, and reaction scheme is as follows：
Wherein, R1One kind in hydrogen, acetyl group, amino, ethoxy acetyl, cyano ethyl or benzoyl；
R2One kind in hydrogen, acetyl group, amino, ethoxy acetyl, cyano ethyl or benzoyl；
The nitro substituted aromatic compound is selected from 4- nitro-acetophenones, 4- nitroanilines, 4- ethyl nitrobenzoates, 3-
One kind in nitrobenzene ethane nitrile or 4- nitro benzophenones；
The solvent is selected from methanol, toluene, hexamethylene, dichloromethane, N,N-dimethylformamide, the tert-butyl alcohol, acetic acid second
One kind in ester, glycol dimethyl ether, acetone or alcohol；
The nanometer porous metal catalyst is selected from nanoporous palladium catalyst；
A kind of preparation method of aromatic amine compounds, specifically includes following steps：
Step 1, by nitro substituted aromatic compound, nanometer porous metal catalyst and solvent add reactor in, be passed through
Stress control is controlled at 35 DEG C~115 DEG C in 2~22bar hydrogen, heating stirring, reaction temperature, and the reaction time is controlled in 5h
~50h, the molar concentration of the nitro substituted aromatic compound in a solvent is 0.01~1.0mmol/mL, nitro substituted aroma
Compound and the mol ratio of catalyst are 1:0.01~1.0；
After step 2, reaction terminate, the reaction solution that step 1 is obtained carries out removal of solvent under reduced pressure, then is obtained by column chromatography
Target product aromatic amine compounds.
Present invention has the advantages that：A kind of preparation method of aromatic amine compounds, specifically includes following steps：Step 1, general
Nitro substituted aromatic compound, nanometer porous metal catalyst and solvent are added in reactor, are passed through hydrogen, heating stirring；
After step 2, reaction terminate, the reaction solution that step 1 is obtained carries out removal of solvent under reduced pressure, then obtains target product by column chromatography
Aromatic amine compounds.The nanoporous palladium catalyst that the present invention is used is the nano porous palladium prepared by the de- alloyage of chemistry
(Nanoporous palladium catalyzed silicon-based one-pot cross-coupling reaction
Of aryl iodides with organosilanes.Catal.Sci.Technol., 2014,4,1734-1737), it is not required to
Extra ligand or carrier are wanted, microcosmic upper in special 3 D pore canal pattern, average channel diameter 30nm or so, special construction to receive
Rice porous palladium possesses bigger serface in itself；In catalysis C-C generations (A nanostructured skeleton catalyst:
Suzuki-coupling with a reusable and sustainable nanoporous metallic glass Pd-
Catalyst.Chem.Commun., 2011,47,5985-5987.) and catalytic oxidation (Nanoporous palladium
catalyzed silicon-based one-pot cross-coupling reaction of aryl iodides with
Organosilanes.Catal.Sci.Technol., 2014,4,1734-1737) etc. shown efficient catalytic performance and
The features such as being easily recycled.Nano porous palladium can be used as catalyst compared with its unique catalytic activity is played under temperate condition
Can conveniently it recycle, simple filtration cleaning can be reused again, the catalyst structure is stable, catalytic activity is high, repeats
Substantially reduced using repeatedly catalytic activity is had not yet to see.Hydrogen is cleaning, cheap go back original reagent, and hydrogen does hydrogen source, nanoporous
Palladium does catalyst reduction nitro report and not met.Under equal conditions, compared with existing custom catalystses, what the present invention was obtained
Target product selectivity is high, and highest selectively can reach 99%, as shown in Table 1 below, catalyst favorable reproducibility, and reuse many
Secondary catalytic effect is not substantially reduced, and possibility is provided for its realization industrialization.
Brief description of the drawings
Fig. 1 is 4- aminoacetophenones in embodiment 1,2,31H nuclear magnetic spectrograms.
Fig. 2 is 4- amino anilines in embodiment 4,5,61H nuclear magnetic spectrograms.
Fig. 3 is PABA ethyl ester in embodiment 7,8,91H nuclear magnetic spectrograms.
Fig. 4 is 3- aminopheny-lacetonitriles in embodiment 10,11,121H nuclear magnetic spectrograms.
Fig. 5 is 4- aminobenzophenones in embodiment 13,14,151H nuclear magnetic spectrograms.
Embodiment
With reference to embodiment, the invention will be further described.
The preparation of embodiment 1,4- aminoacetophenones
By nano porous metal palladium catalyst (1.6mg, 0.015mmol), methanol (3mL) and 4- nitro-acetophenones
(49.55mg, 0.3mmol) is added in reactor, is passed through hydrogen (2bar), and heating stirring, reaction temperature is controlled at 50 DEG C, instead
Time control is answered in 20h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) 4- amino is obtained
Acetophenone 38.9mg, yield 96%.
Light yellow solid：1H NMR(CDCl3,400MHz)δ:7.79 (d, J=8.4Hz, 2H), 6.63 (d, J=8.4Hz,
2H),4.29(s,2H),2.49(s,3H).
The preparation of embodiment 2,4- aminoacetophenones
By nano porous metal palladium catalyst (3.2mg, 0.03mmol), toluene (3mL) and 4- nitro-acetophenones
(49.55mg, 0.3mmol) is added in reactor, is passed through hydrogen (6bar), and heating stirring, reaction temperature is controlled at 70 DEG C, instead
Time control is answered in 17h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) 4- amino is obtained
Acetophenone 38.9mg, yield 96%.
Light yellow solid：1H NMR(CDCl3,400MHz)δ:7.79 (d, J=8.4Hz, 2H), 6.63 (d, J=8.4Hz,
2H),4.29(s,2H),2.49(s,3H).
The preparation of embodiment 3,4- aminoacetophenones
By nano porous metal palladium catalyst (9.6mg, 0.09mmol), hexamethylene (3mL) and 4- nitro-acetophenones
(49.55mg, 0.3mmol) is added in reactor, is passed through hydrogen (9bar), and heating stirring, reaction temperature is controlled at 100 DEG C,
Reaction time is controlled in 36h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) 4- ammonia is obtained
Benzoylformaldoxime 38.9mg, yield 96%.
Light yellow solid：1H NMR(CDCl3,400MHz)δ:7.79 (d, J=8.4Hz, 2H), 6.63 (d, J=8.4Hz,
2H),4.29(s,2H),2.49(s,3H).
The preparation of embodiment 4,4- amino anilines
By nano porous metal palladium catalyst (3.2mg, 0.03mmol), methanol (1mL) and 4- nitroanilines (41.44mg,
0.3mmol) it is added in reactor, is passed through hydrogen (10bar), heating stirring, reaction temperature is controlled in 70 DEG C, reaction time control
System is in 22h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) 4- amino anilines are obtained
29.8mg, yield 92%.
Light yellow liquid：1H NMR(DMSO,400MHz)δ:6.36(s,4H),4.18(s,4H).
The preparation of embodiment 5,4- amino anilines
By nano porous metal palladium catalyst (4.8mg, 0.045mmol), dichloromethane (1mL) and 4- nitroanilines
(41.44mg, 0.3mmol) is added in reactor, is passed through hydrogen (3bar), and heating stirring, reaction temperature is controlled at 90 DEG C, instead
Time control is answered in 40h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) 4- amino is obtained
Aniline 29.8mg, yield 92%.
Light yellow liquid：1H NMR(DMSO,400MHz)δ6.36(s,4H),4.18(s,4H).
The preparation of embodiment 6,4- amino anilines
By nano porous metal palladium catalyst (16.0mg, 0.15mmol), N,N-dimethylformamide (1mL) and 4- nitros
Aniline (41.44mg, 0.3mmol) is added in reactor, is passed through hydrogen (15bar), and heating stirring, reaction temperature is controlled 80
DEG C, the reaction time is controlled in 32h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) obtain
4- amino aniline 29.8mg, yield 92%.
Light yellow liquid：1H NMR(DMSO,400MHz)δ6.36(s,4H),4.18(s,4H).
The preparation of embodiment 7, PABA ethyl ester
By nano porous metal palladium catalyst (3.2mg, 0.03mmol), toluene (1mL) and 4- ethyl nitrobenzoates
(58.55mg, 0.3mmol) is added in reactor, is passed through hydrogen (10bar), and heating stirring, reaction temperature is controlled at 70 DEG C,
Reaction time is controlled in 22h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) 4- ammonia is obtained
Yl benzoic acid ethyl ester 44.6mg, yield 90%.
Light yellow solid：1H NMR(CDCl3, 400MHz) and δ 7.85 (d, J=8.5Hz, 2H), 6.63 (d, J=8.5Hz,
2H), (t, J=7.1Hz, the 3H) of 4.31 (d, J=7.1Hz, 2H), 4.11 (s, 2H), 1.36
The preparation of embodiment 8, PABA ethyl ester
By nano porous metal palladium catalyst (6.4mg, 0.06mmol), the tert-butyl alcohol (3mL) and 4- ethyl nitrobenzoates
(58.55mg, 0.3mmol) is added in reactor, is passed through hydrogen (15bar), and heating stirring, reaction temperature is controlled at 40 DEG C,
Reaction time is controlled in 46h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) 4- ammonia is obtained
Yl benzoic acid ethyl ester 44.6mg, yield 90%.
Light yellow solid：1H NMR(CDCl3, 400MHz) and δ 7.85 (d, J=8.5Hz, 2H), 6.63 (d, J=8.5Hz,
2H), (t, J=7.1Hz, the 3H) of 4.31 (d, J=7.1Hz, 2H), 4.11 (s, 2H), 1.36
The preparation of embodiment 9, PABA ethyl ester
By nano porous metal palladium catalyst (9.6mg, 0.09mmol), ethyl acetate (4mL) and 4- nitrobenzoic acid second
Ester (58.55mg, 0.3mmol) is added in reactor, is passed through hydrogen (20bar), and heating stirring, reaction temperature is controlled 80
DEG C, the reaction time is controlled in 23h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) obtain
PABA ethyl ester 44.6mg, yield 90%.
Light yellow solid：1H NMR(CDCl3,400MHz)δ:7.85 (d, J=8.5Hz, 2H), 6.63 (d, J=8.5Hz,
2H), (t, J=7.1Hz, the 3H) of 4.31 (d, J=7.1Hz, 2H), 4.11 (s, 2H), 1.36
The preparation of embodiment 10,3- aminopheny-lacetonitriles
By nano porous metal palladium catalyst (3.2mg, 0.03mmol), glycol dimethyl ether (3mL) and 3- nitrobenzene second
Nitrile (48.65mg, 0.3mmol) is added in reactor, is passed through hydrogen (16bar), and heating stirring, reaction temperature is controlled 100
DEG C, the reaction time is controlled in 35h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) obtain
3- aminopheny-lacetonitrile 35.7mg, yield 90%.
Light yellow solid：1H NMR(400MHz,CDCl3) δ 7.12 (t, J=7.7Hz, 1H), 6.63 (dd, J=17.3,
7.7Hz,3H),3.73(s,2H),3.63(s,2H).
The preparation of embodiment 11,3- aminopheny-lacetonitriles
By nano porous metal palladium catalyst (4.8mg, 0.045mmol), acetone (1mL) and 3- nitrobenzene ethane nitriles
(48.65mg, 0.3mmol) is added in reactor, is passed through hydrogen (6bar), and heating stirring, reaction temperature is controlled at 90 DEG C, instead
Time control is answered in 30h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) 3- amino is obtained
Benzene acetonitrile 35.7mg, yield 90%.
Light yellow solid：1H NMR(400MHz,CDCl3) δ 7.12 (t, J=7.7Hz, 1H), 6.63 (dd, J=17.3,
7.7Hz,3H),3.73(s,2H),3.63(s,2H).
The preparation of embodiment 12,3- aminopheny-lacetonitriles
By nano porous metal palladium catalyst (9.6mg, 0.09mmol), toluene (5mL) and 3- nitrobenzene ethane nitriles
(48.65mg, 0.3mmol) is added in reactor, is passed through hydrogen (12bar), and heating stirring, reaction temperature is controlled at 80 DEG C,
Reaction time is controlled in 22h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) 3- ammonia is obtained
Base benzene acetonitrile 35.7mg, yield 90%.
Light yellow solid：1H NMR(400MHz,CDCl3) δ 7.12 (t, J=7.7Hz, 1H), 6.63 (dd, J=17.3,
7.7Hz,3H),3.73(s,2H),3.63(s,2H).
The preparation of embodiment 13,4- aminobenzophenones
By nano porous metal palladium catalyst (3.2mg, 0.03mmol), ethanol (1mL) and 4- nitro benzophenones
(68.17mg, 0.3mmol) is added in reactor, is passed through hydrogen (10bar), and heating stirring, reaction temperature is controlled at 60 DEG C,
Reaction time is controlled in 10h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) 4- ammonia is obtained
Base benzophenone 54.4mg, yield 92%.
Yellow solid：1H NMR(500MHz,CDCl3) δ 7.26 (t, J=7.9Hz, 2H), 6.99 (t, J=7.3Hz, 1H),
(s, the 2H) of 6.92 (d, J=8.0Hz, 2H), 6.86 (d, J=8.6Hz, 2H), 6.64 (d, J=8.6Hz, 2H), 3.51
The preparation of embodiment 14,4- aminobenzophenones
By nano porous metal palladium catalyst (9.6mg, 0.09mmol), the tert-butyl alcohol (3mL) and 4- nitro benzophenones
(68.17mg, 0.3mmol) is added in reactor, is passed through hydrogen (9bar), and heating stirring, reaction temperature is controlled at 110 DEG C,
Reaction time is controlled in 19h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) 4- ammonia is obtained
Base benzophenone 54.4mg, yield 92%.
Yellow solid：1H NMR(500MHz,CDCl3) δ 7.26 (t, J=7.9Hz, 2H), 6.99 (t, J=7.3Hz, 1H),
(s, the 2H) of 6.92 (d, J=8.0Hz, 2H), 6.86 (d, J=8.6Hz, 2H), 6.64 (d, J=8.6Hz, 2H), 3.51
The preparation of embodiment 15,4- aminobenzophenones
By nano porous metal palladium catalyst (16.0mg, 0.15mmol), hexamethylene (4mL) and 4- nitro benzophenones
(68.17mg, 0.3mmol) is added in reactor, is passed through hydrogen (10bar), and heating stirring, reaction temperature is controlled at 70 DEG C,
Reaction time is controlled in 32h, column chromatography (silica gel, 200-300 mesh；Solvent, petroleum ether：Ethyl acetate=10:1) 4- ammonia is obtained
Base benzophenone 54.4mg, yield 92%.
Yellow solid：1H NMR(500MHz,CDCl3) δ 7.26 (t, J=7.9Hz, 2H), 6.99 (t, J=7.3Hz, 1H),
(s, the 2H) of 6.92 (d, J=8.0Hz, 2H), 6.86 (d, J=8.6Hz, 2H), 6.64 (d, J=8.6Hz, 2H), 3.51
Table 1
Claims (1)
1. a kind of preparation method of aromatic amine compounds, it is characterised in that：By raw material of nitro substituted aromatic compound, nanometer it is many
Mesoporous metal is that catalyst, hydrogen are hydrogen source, and selective hydrogenation prepares aromatic amine compounds, and reaction scheme is as follows：
Wherein, R1One kind in hydrogen, acetyl group, amino, ethoxy acetyl, cyano ethyl or benzoyl；
R2One kind in hydrogen, acetyl group, amino, ethoxy acetyl, cyano ethyl or benzoyl；
The nitro substituted aromatic compound is selected from 4- nitro-acetophenones, 4- nitroanilines, 4- ethyl nitrobenzoates, 3- nitros
One kind in benzene acetonitrile or 4- nitro benzophenones；
The solvent is selected from methanol, toluene, hexamethylene, dichloromethane, N,N-dimethylformamide, the tert-butyl alcohol, ethyl acetate, second
One kind in glycol dimethyl ether, acetone or alcohol；
The nanometer porous metal catalyst is selected from nanoporous palladium catalyst；
A kind of preparation method of aromatic amine compounds, specifically includes following steps：
Step 1, by nitro substituted aromatic compound, nanometer porous metal catalyst and solvent add reactor in, be passed through pressure
Control the hydrogen in 2~22bar, heating stirring, reaction temperature control at 35 DEG C~115 DEG C, reaction time control 5h~
50h, the molar concentration of the nitro substituted aromatic compound in a solvent is 0.01~1.0mmol/mL, nitro substituted aromatic
The mol ratio of compound and catalyst is 1:0.01~1.0；
After step 2, reaction terminate, the reaction solution that step 1 is obtained carries out removal of solvent under reduced pressure, then obtains target by column chromatography
Product aromatic amine compounds.
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| CN107814760B (en) * | 2017-10-10 | 2020-07-24 | 大连理工大学 | Preparation method and application of metal organic cage-shaped compound for preparing aniline by catalytic reduction of nitrobenzene |
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