CN110483307A - A kind of preparation method of aromatic amine compounds - Google Patents

A kind of preparation method of aromatic amine compounds Download PDF

Info

Publication number
CN110483307A
CN110483307A CN201910759614.0A CN201910759614A CN110483307A CN 110483307 A CN110483307 A CN 110483307A CN 201910759614 A CN201910759614 A CN 201910759614A CN 110483307 A CN110483307 A CN 110483307A
Authority
CN
China
Prior art keywords
palladium
aromatic amine
amine compounds
silver
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201910759614.0A
Other languages
Chinese (zh)
Inventor
李志文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong First Medical University and Shandong Academy of Medical Sciences
Original Assignee
Shandong First Medical University and Shandong Academy of Medical Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong First Medical University and Shandong Academy of Medical Sciences filed Critical Shandong First Medical University and Shandong Academy of Medical Sciences
Priority to CN201910759614.0A priority Critical patent/CN110483307A/en
Publication of CN110483307A publication Critical patent/CN110483307A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07C209/325—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 reduction by other means than indicated in C07C209/34 or C07C209/36
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • 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 discloses a kind of preparation methods of aromatic amine compounds, and steps are as follows: (1) organosilan and aromatic nitro compound being added into alcohols solvent, nano porous palladium silver alloy catalyst is added, in 20~80 DEG C of 1~3h of reaction；(2) method for utilizing column chromatography for separation, purified product obtain corresponding aromatic diaminodithiol compound.This method uses heterogeneous palladium-silver catalyst, can in normal pressure, realize under room temperature and go back original aromatic nitro compound and prepare aromatic amine compounds；Using nano porous palladium silver alloy catalyst, the hydrogen transfer reaction that aromatic amine compounds are prepared using the hydrogen that silane oxidation generates is realized, while the catalyst performance is more stable, can reuse, to reduce costs；The preparation method has high-activity high-selectivity, and yield is high, and yield avoids the problem of traditional preparation methods need the harshness reaction condition such as high temperature or high pressure up to 95%.

Description

A kind of preparation method of aromatic amine compounds
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of preparation method of aromatic amine compounds.
Background technique
Aromatic amine compounds are a kind of particularly important industrial chemicals, are widely used in functional material, bio-pharmaceutical, surpass The numerous areas such as molecular chemistry.The currently used method for preparing aromatic amine compounds is nitro compound reducing, using each Reducing agent is planted to go back original aromatic nitro compound, so that nitro is converted to amido, to obtain aromatic amine compounds.Wherein most often The method used be using sodium borohydride as reducing agent reaction (J.Sun, Y.Fu, G.He, X.Sun, X.Wang, Catal.Sci.Technol.,2014,4,1742；H.Wei,Y.Lu,Chem.Asian J.,2012,7,680；Q.An,M.Yu, Y.Zhang,W.Ma,J.Guo,C.Wang,J.Phys.Chem.C,2012,116,22432).Other reducing agents such as hydrazine hydrate (P.L.Gkizis,M.Stratakis,I.N.Lykakis,Catal.Commun.,2013,36,48；Y.Lu,H.Zhu,W.Li, B.Hu, S.Yu, J.Mater.Chem.A, 2013,1,3783) it equally can be with nitro compound reducing.However, this kind of reaction exists The big problem of reducing agent consumption, simultaneous reactions condition is harsher, and there may be a variety of toxic pairs during the reaction Product.Using hydrogen as reducing agent nitro compound reducing prepare aromatic amine compounds (T.Mitsudome, Y.Mikami, M.Matoba,T.Mizugaki,K.Jitsukawa,K.Kaneda,Angew.Chem.Int.Ed.,2012,51,136； T.Mitsudome,M.Matoba,T.Mizugaki,K.Jitsukawa,K.Kaneda,Chem.Eur.J.,2013,19, 5255) method generally requires high temperature and pressure although of reduced contamination, is equally unfavorable for producing.
The reduction that organic compound is realized using hydrogen transfer reaction, is the hot spot studied at present.It is being reacted using hydrogen donor The activation hydrogen generated in the process participates in hydrogenation reaction as hydrogen source, avoids the height that may be needed during activation hydrogen Temperature, high pressure make reaction be expected to carry out under relatively mild conditions, realize green preparation, have environmental protection, atom economy, safety Efficient feature.However many problems are still had in this kind of system: system selection is unreasonable, is not that any dehydrogenation reaction is all suitable Hydrogen transfer reaction is closed, dehydrogenation product can not utilize, and will cause waste, and pollution reaction system；Reaction condition is complicated harsh, in order to Guarantee that reaction is gone on smoothly, need higher temperature, each analog assistant is added, causes the selectivity of reaction to reduce, uncertainty increases Add, limits the application of hydrogen transfer reaction.
Summary of the invention
Aiming at the problem that current aromatic amine compounds exist during the preparation process, the present invention provides a kind of more using nanometer The method that hole palladium-based catalyst uses hydrogen migration to prepare aromatic amine compounds.Method provided by the invention uses silane oxidation mistake The hydrogen generated in journey is as reducing agent, and nano porous palladium metal alkyl materials catalyst, the catalyst stability is good, and is easy to divide From recoverable improves the service life and products collection efficiency of catalyst.Technical scheme is as follows:
A kind of preparation method of aromatic amine compounds, steps are as follows:
(1) organosilan and aromatic nitro compound are added into alcohols solvent, the catalysis of nanoporous palladium-silver is added Agent, in 20~80 DEG C of 1~3h of reaction；
(2) method for utilizing column chromatography for separation, purified product obtain corresponding aromatic diaminodithiol compound.
Preferably, the aromatic amine compounds are selected from but not limited to aniline, amino-phenol, para-aminotoluene and aminobenzene Nitrile.
Preferably, the nitro compound is selected from but not limited to nitrobenzene, p-nitrophenol, para-nitrotoluene and to nitro Cyanophenyl.
Preferably, alcohols solvent described in is selected from methanol, ethyl alcohol and isopropanol, more preferable methanol.
Preferably, the organosilan is selected from dimethylphenylsilaneand, triethylsilane, diphenylmethylsilane, three second All kinds of organosilans such as oxysilane, more preferable triethylsilane.
Preferably, palladium in the nano porous palladium silver alloy catalyst: silver atoms number ratio is 1:4~4:1.
Preferably, the nano porous palladium silver alloy catalyst is prepared as follows to obtain: taking aluminium: palladium-silver atom number Than the aluminium palladium-silver for 75:25, wherein palladium: silver atoms number ratio is 1:4~4:1, is placed in the NaOH aqueous solution of 10%wt, Corrosion to bubble-free is emerged, and is washed 3~6 times, dry to get nano porous palladium silver alloy catalyst (np-PdAg).
It is furthermore preferred that aluminium in the aluminium palladium-silver: palladium: silver-colored atom number ratio is 75:12.5:12.5, is received Meter Duo Kong palladium-silver (1:1).
Preferably, the range of reaction temperature is 20~50 DEG C；It is furthermore preferred that reaction temperature is room temperature.
Preferably, the mole dosage ratio of the nanoporous palladium-silver and aromatic nitro compound is 1:(10~25)；
Preferably, the mole dosage of the organosilan and alcohol volume ratio are 5:(3~10) mol/L；
Preferably, the molar ratio of the organosilan and aromatic nitro compound is 5:(0.1~1).
The purification of aromatic amine compounds can be method well known to those skilled in the art in the step (2), preferably Method of purification are as follows: merge organic phase after the mixed solution obtained after reaction is added to the water and is extracted with dichloromethane, then It is dry with anhydrous sodium sulfate, by the isolated aromatic amine chemical combination of residue silica gel column chromatography after vacuum distillation removal solvent Object, silica gel column chromatography separation eluent used is preferably petroleum ether, methylene chloride.
Preferably, the eluent proportion is petroleum ether: methylene chloride=10:1.
Beneficial effects of the present invention:
1, the present invention provides a kind of preparation method of novel aromatic aminated compounds, and this method is closed using heterogeneous palladium-silver Au catalyst, can in normal pressure, realize under room temperature and go back original aromatic nitro compound and prepare aromatic amine compounds.
2, the preparation method utilizes nano porous palladium silver alloy catalyst, realizes and is prepared using the hydrogen that silane oxidation generates The hydrogen transfer reaction of aromatic amine compounds, while the catalyst performance is more stable, can reuse, to reduce into This.
3, the preparation method has high-activity high-selectivity, and yield is high, and yield avoids traditional preparation up to 95% Method needs the problem of harshness reaction condition such as high temperature or high pressure.
Detailed description of the invention
The Figure of description for constituting a part of the invention is used to provide further understanding of the present invention, and of the invention shows Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of product aniline prepared by the embodiment of the present invention 1.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of product para-aminophenol prepared by the embodiment of the present invention 7.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of product para-aminotoluene prepared by the embodiment of the present invention 8.
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of product p-aminophenyl nitrile prepared by the embodiment of the present invention 9.
Fig. 5 is the scanning electron microscope of nanoporous palladium-silver (1:1) used in 1-9 of the embodiment of the present invention Figure.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the present invention.Unless another It indicates, all technical and scientific terms used herein has usual with general technical staff of the technical field of the invention The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root According to exemplary embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singular Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
Raw materials used in embodiment is conventional reagent, commercial products；Device therefor is conventional equipment.
Nano porous palladium silver alloy catalyst used in embodiment is to be prepared as follows to obtain:
Take aluminium: palladium: silver atoms number is placed in the NaOH aqueous solution of 10%wt than the palladium aluminium alloy for 75:12.5:12.5 In, corrosion to bubble-free is emerged, and is washed 3~6 times, dry to get nano porous palladium silver alloy catalyst (1:1).Nanoporous Silver palladium alloy 5~20nm of aperture size, 10~25nm of hole wall size.Nanoporous palladium-silver (1:1) Scanning Electron microscope Figure is as shown in Figure 5.
Take aluminium: palladium: silver atoms number is placed in the NaOH aqueous solution of 10%wt than the palladium aluminium alloy for 75:20:5, corrosion It emerges, washes 3~6 times to bubble-free, it is dry to get nano porous palladium silver alloy catalyst (4:1).
Take aluminium: palladium: silver atoms number is placed in the NaOH aqueous solution of 10%wt than the palladium aluminium alloy for 75:5:20, corrosion It emerges, washes 3~6 times to bubble-free, it is dry to get nano porous palladium silver alloy catalyst (1:4).
Embodiment 1
A kind of preparation method of aniline, steps are as follows:
(1) 1mmol nitrobenzene, 5mmol dimethylphenylsilaneand are added in 3mL methanol, 0.1mmol nanometers of addition is more Hole palladium-silver catalyst (1:1), reacts 1h at room temperature；
Or 2.5mmol nitrobenzene, 10mmol dimethylphenylsilaneand are added in 3mL methanol, 0.1mmol is added and receives Rice porous palladium silver alloy catalyst (1:1), reacts 3h at room temperature；
(2) water is added into the mixed solution obtained after reaction and merges organic phase after being extracted with dichloromethane, then uses Anhydrous sodium sulfate is dry, by the isolated product of residue silica gel column chromatography, eluent proportion after vacuum distillation removal solvent Preferably petroleum ether: methylene chloride=10:1.
Product aniline, yield are followed successively by 95%, 90%, and hydrogen nuclear magnetic resonance spectrogram is as shown in Figure 1, reaction equation is as follows:
Embodiment 2
A kind of preparation method of aniline, steps are as follows:
(1) 1mmol nitrobenzene, 5mmol dimethylphenylsilaneand are added in 3mL ethyl alcohol, 0.1mmol nanometers of addition is more Hole palladium-silver catalyst (1:1), reacts 1.5h at room temperature；
Alternatively, 1mmol nitrobenzene, 5mmol dimethylphenylsilaneand are added in 10mL ethyl alcohol, 0.1mmol is added and receives Rice porous palladium silver alloy catalyst (1:1), reacts 1.5h at room temperature；
(2) water is added into the mixed solution obtained after reaction and merges organic phase after being extracted with dichloromethane, then uses Anhydrous sodium sulfate is dry, by the isolated product of residue silica gel column chromatography, eluent proportion after vacuum distillation removal solvent Preferably petroleum ether: methylene chloride=10:1.
Product aniline, yield are followed successively by 93%, 90%, and reaction equation is as follows:
Embodiment 3
A kind of preparation method of aniline, steps are as follows:
(1) 1mmol nitrobenzene, 5mmol dimethylphenylsilaneand are added in 3mL isopropanol, are added 0.1mmol nanometers Porous palladium silver alloy catalyst (1:1), reacts 2h at room temperature；
(2) water is added into the mixed solution obtained after reaction and merges organic phase after being extracted with dichloromethane, then uses Anhydrous sodium sulfate is dry, by the isolated product of residue silica gel column chromatography, eluent proportion after vacuum distillation removal solvent Preferably petroleum ether: methylene chloride=10:1.
Product aniline, yield 68%, reaction equation is as follows:
Embodiment 4
A kind of preparation method of aniline, steps are as follows:
(1) 1mmol nitrobenzene, 5mmol triethylsilane are added in 3mL methanol, 0.1mmol nano porous palladium is added Silver alloy catalyst (1:1), reacts 1h at room temperature；
Alternatively, 0.1mmol nitrobenzene, 5mmol triethylsilane are added in 3mL methanol, 0.1mmol nanometers of addition is more Hole palladium-silver catalyst (1:1), reacts 1h at room temperature；
(2) water is added into the mixed solution obtained after reaction and merges organic phase after being extracted with dichloromethane, then uses Anhydrous sodium sulfate is dry, by the isolated product of residue silica gel column chromatography, eluent proportion after vacuum distillation removal solvent Preferably petroleum ether: methylene chloride=10:1.
Product aniline, yield are followed successively by 95%, 96%, and reaction equation is as follows:
Embodiment 5
A kind of preparation method of aniline, steps are as follows:
(1) 1mmol nitrobenzene, 5mmol diphenylmethylsilane are added in 3mL methanol, 0.1mmol nanometers of addition is more Hole palladium-silver catalyst (1:1), reacts 1.5h at room temperature；
1mmol nitrobenzene, 5mmol diphenylmethylsilane are added in 3mL methanol, 0.1mmol nanoporous is added Palladium-silver catalyst (1:1) reacts 1.5h at 50 DEG C；
(2) water is added into the mixed solution obtained after reaction and merges organic phase after being extracted with dichloromethane, then uses Anhydrous sodium sulfate is dry, by the isolated product of residue silica gel column chromatography, eluent proportion after vacuum distillation removal solvent Preferably petroleum ether: methylene chloride=10:1.
Product aniline, yield are followed successively by 90%, 95%, and reaction equation is as follows:
Embodiment 6
A kind of preparation method of aniline, steps are as follows:
(1) 1mmol nitrobenzene, 5mmol triethoxysilane are added in 3mL methanol, 0.1mmol nanoporous is added Palladium-silver catalyst (1:1), reacts 2h at room temperature；
(2) water is added into the mixed solution obtained after reaction and merges organic phase after being extracted with dichloromethane, then uses Anhydrous sodium sulfate is dry, by the isolated product of residue silica gel column chromatography, eluent proportion after vacuum distillation removal solvent Preferably petroleum ether: methylene chloride=10:1.
Product aniline, yield 55%, reaction equation is as follows:
Embodiment 7
A kind of preparation method of para-aminophenol, steps are as follows:
(1) 1mmol p-nitrophenol, 5mmol triethylsilane are added in 3mL methanol, 0.1mmol nanometers of addition is more Hole palladium-silver catalyst (1:1), reacts 2h at room temperature；
(2) water is added into the mixed solution obtained after reaction and merges organic phase after being extracted with dichloromethane, then uses Anhydrous sodium sulfate is dry, by the isolated product of residue silica gel column chromatography, eluent proportion after vacuum distillation removal solvent Preferably petroleum ether: methylene chloride=10:1.
Product para-aminophenol, yield 80%, hydrogen nuclear magnetic resonance spectrogram is as shown in Fig. 2, reaction equation is as follows:
Embodiment 8
A kind of preparation method of para-aminotoluene, steps are as follows:
(1) 1mmol para-nitrotoluene, 5mmol triethylsilane are added in 3mL methanol, 0.1mmol nanometers of addition is more Hole palladium-silver catalyst (1:1), reacts 2h at room temperature；
(2) water is added into the mixed solution obtained after reaction and merges organic phase after being extracted with dichloromethane, then uses Anhydrous sodium sulfate is dry, by the isolated product of residue silica gel column chromatography, eluent proportion after vacuum distillation removal solvent Preferably petroleum ether: methylene chloride=10:1.
Product para-aminotoluene, yield 95%, hydrogen nuclear magnetic resonance spectrogram is as shown in figure 3, reaction equation is as follows:
Embodiment 9
A kind of preparation method of p-aminophenyl nitrile, steps are as follows:
(1) 1mmol p-nitrophenyl nitrile, 5mmol triethylsilane are added in 3mL methanol, 0.1mmol nanometers of addition is more Hole palladium-silver catalyst (1:1), reacts 2h at room temperature；
(2) water is added into the mixed solution obtained after reaction and merges organic phase after being extracted with dichloromethane, then uses Anhydrous sodium sulfate is dry, by the isolated product of residue silica gel column chromatography, eluent proportion after vacuum distillation removal solvent Preferably petroleum ether: methylene chloride=10:1.
Product p-aminophenyl nitrile, yield 95%, hydrogen nuclear magnetic resonance spectrogram is as shown in figure 4, reaction equation is as follows:
Embodiment 10
A kind of preparation method of aniline, steps are as follows:
(1) 2mmol nitrobenzene, 5mmol triethylsilane are added in 3mL methanol, 0.1mmol nano porous palladium is added Silver alloy catalyst (1:1), reacts 2h at room temperature；
2mmol nitrobenzene, 5mmol triethylsilane are added in 3mL methanol, 0.1mmol nanoporous palladium-silver is added Alloy catalyst (4:1), reacts 2h at room temperature；
2mmol nitrobenzene, 5mmol triethylsilane are added in 3mL methanol, 0.1mmol nanoporous palladium-silver is added Alloy catalyst (1:4), reacts 2h at room temperature；
2mmol nitrobenzene, 5mmol triethylsilane are added in 3mL methanol, 0.1mmol nano porous palladium is added and urges Agent reacts 2h at room temperature；
(2) water is added into the mixed solution obtained after reaction and merges organic phase after being extracted with dichloromethane, then uses Anhydrous sodium sulfate is dry, by the isolated product of residue silica gel column chromatography, eluent proportion after vacuum distillation removal solvent Preferably petroleum ether: methylene chloride=10:1.
Product aniline, yield are followed successively by 95%, 90%, 80%, 90%, and reaction equation is as follows:
Embodiment 11
A kind of preparation method of aniline, steps are as follows:
(1) 1mmol nitrobenzene, 5mmol triethylsilane are added in 3mL methanol, 0.1mmol nano porous palladium is added Silver alloy catalyst (1:1), reacts 1h at room temperature；
(2) water is added into the mixed solution obtained after reaction and merges organic phase after being extracted with dichloromethane, then uses Anhydrous sodium sulfate is dry, by the isolated product of residue silica gel column chromatography, eluent proportion after vacuum distillation removal solvent Preferably petroleum ether: methylene chloride=10:1.
(3) after ethyl acetate and water cleaning, repeat the above steps catalyst (1), (2), is repeated 9 times altogether.
Product aniline, for each yield 95% or more, reaction equation is as follows:
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of preparation method of aromatic amine compounds, which is characterized in that steps are as follows:
(1) organosilan and aromatic nitro compound are added into alcohols solvent, nano porous palladium silver alloy catalyst, In is added 20~80 DEG C of 1~3h of reaction；
(2) method for utilizing column chromatography for separation, purified product obtain corresponding aromatic diaminodithiol compound.
2. a kind of preparation method of aromatic amine compounds according to claim 1, which is characterized in that the aromatic amine Compound is selected from but not limited to aniline, amino-phenol, para-aminotoluene and aminobenzonitrile；The nitro compound is selected from but unlimited In nitrobenzene, p-nitrophenol, para-nitrotoluene and p-nitrophenyl nitrile.
3. a kind of preparation method of aromatic amine compounds according to claim 1, which is characterized in that the alcohols solvent Selected from methanol, ethyl alcohol and isopropanol, more preferable methanol.
4. a kind of preparation method of aromatic amine compounds according to claim 1, which is characterized in that the organosilan Selected from dimethylphenylsilaneand, triethylsilane, diphenylmethylsilane and triethoxysilane, more preferable triethylsilane.
5. a kind of preparation method of aromatic amine compounds according to claim 1, which is characterized in that the nanoporous Palladium in palladium-silver catalyst: silver atoms number ratio is 1:4~4:1.
6. a kind of preparation method of aromatic amine compounds according to claim 5, which is characterized in that the nanoporous Palladium-silver catalyst is prepared as follows to obtain: take aluminium: palladium-silver atom number is placed in than the aluminium palladium-silver for 75:25 In the NaOH aqueous solution of 10%wt, corrosion to bubble-free is emerged, and is washed 3~6 times, and drying is urged to get nanoporous palladium-silver Agent (np-PdAg).
7. a kind of preparation method of aromatic amine compounds according to claim 6, which is characterized in that the aluminium palladium-silver Aluminum in Alloy: palladium: silver-colored atom number ratio is 75:12.5:12.5, obtains nanoporous palladium-silver (1:1).
8. a kind of preparation method of aromatic amine compounds according to claim 1, which is characterized in that the reaction temperature Range is 20~50 DEG C；It is furthermore preferred that reaction temperature is room temperature.
9. a kind of preparation method of aromatic amine compounds according to claim 1, which is characterized in that the nanoporous The mole dosage of palladium-silver and aromatic nitro compound ratio is 1:(10~25)；
The mole dosage and alcohol volume ratio of the organosilan are 5:(3~10) mol/L；
The molar ratio of the organosilan and aromatic nitro compound is 5:(0.1~1).
10. a kind of preparation method of aromatic amine compounds according to claim 1, which is characterized in that the step (2) The method of purification of middle aromatic amine compounds are as follows: after the mixed solution obtained after reaction is added to the water and is extracted with dichloromethane Merge organic phase, it is then dry with anhydrous sodium sulfate, residue is separated with silica gel column chromatography after vacuum distillation removal solvent To aromatic amine compounds, silica gel column chromatography separation eluent used is petroleum ether: methylene chloride (10:1).
CN201910759614.0A 2019-08-16 2019-08-16 A kind of preparation method of aromatic amine compounds Withdrawn CN110483307A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910759614.0A CN110483307A (en) 2019-08-16 2019-08-16 A kind of preparation method of aromatic amine compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910759614.0A CN110483307A (en) 2019-08-16 2019-08-16 A kind of preparation method of aromatic amine compounds

Publications (1)

Publication Number Publication Date
CN110483307A true CN110483307A (en) 2019-11-22

Family

ID=68551563

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910759614.0A Withdrawn CN110483307A (en) 2019-08-16 2019-08-16 A kind of preparation method of aromatic amine compounds

Country Status (1)

Country Link
CN (1) CN110483307A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115232013A (en) * 2022-08-26 2022-10-25 郑州药领医药科技有限公司 Preparation method of aromatic amine compound

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115232013A (en) * 2022-08-26 2022-10-25 郑州药领医药科技有限公司 Preparation method of aromatic amine compound
CN115232013B (en) * 2022-08-26 2023-12-01 郑州药领医药科技有限公司 Preparation method of aromatic amine compound

Similar Documents

Publication Publication Date Title
CN110368982A (en) Non-noble metal nano cluster catalyst and preparation method and application are stablized in Silicalite-1 molecular sieve pore passage confinement
CN103570553B (en) A kind of method preparing N-substitutional amine-group compound by catalytic alkylation
CN106914267B (en) A kind of nitrogen co-doped mesoporous carbon of iron and its preparation method and application
JPS6383050A (en) Manufacture of substituted aromatic amine
CN110483585A (en) A kind of preparation method and applications of the organic cage compound of metal of adjustable high-efficient selective catalytic reduction nitrobenzaldehyde
CN106513028B (en) A kind of catalyst and preparation method thereof and the application in reduction nitro compound
CN104876807A (en) Synthesis process of hydroxybenzene ether (III)
CN110483307A (en) A kind of preparation method of aromatic amine compounds
CN101914036B (en) Method for preparing azobenzene derivatives
CN103709061A (en) Photochemistry method for synthesizing imine or oxime by using alcohol and amine in one pot
WO2018016270A1 (en) Method for producing guerbet alcohol
CN113024385B (en) Preparation method of 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl
Keshipour et al. Reduction of nitroaromatics to amines with cellulose supported bimetallic Pd/Co nanoparticles
JPH02238A (en) Optically active hydroxybenzylamine derivative, intermediate thereof and production thereof
CN109096126A (en) A kind of deuterium-labeled D9The synthetic method of clenobuterol hydrochloride
CN112321557A (en) Preparation method of Jiale musk
CN111995525A (en) Preparation method of arylamine compound
CN104230635A (en) Preparation method of ethylbenzene from acetophenone hydrogenation
CN109369448A (en) A kind of method that bimetal composite oxide catalyzes and synthesizes azobenzene compound
CN110054582A (en) A kind of preparation method of 3- amino-N- ethyl carbazole
CN108997158A (en) A method of realizing that disubstituted amide and diphenylmethanone are coupled
CN110452129A (en) A kind of preparation method of N- substituted aroma amine compound
CN109678655B (en) Application of nickel-iron hydrotalcite catalyst in preparation of benzyl alcohol
CN105498829B (en) A kind of aromatization of methanol catalyst and its preparation method and application
CN104668577B (en) A kind of nickel micro-and nano-particles and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20191122