CN104478737A - Synthetic method for preparing primary arylamine by utilizing ammonia water as raw material - Google Patents

Synthetic method for preparing primary arylamine by utilizing ammonia water as raw material Download PDF

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CN104478737A
CN104478737A CN201410676178.8A CN201410676178A CN104478737A CN 104478737 A CN104478737 A CN 104478737A CN 201410676178 A CN201410676178 A CN 201410676178A CN 104478737 A CN104478737 A CN 104478737A
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synthetic method
reaction
aryl
ammoniacal liquor
catalyzer
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CN104478737B (en
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陈定奔
吴家守
黄凌
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Taizhou University
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Taizhou University
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    • 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

Abstract

The invention relates to a synthetic method for preparing primary arylamine by utilizing ammonia water as a raw material and in particular relates to a synthetic method for preparing primary arylamine through reaction among an aryl bromide, an aryl chloride and ammonia water. The method is characterized by using an aryl halide and ammonia water as the raw materials and a ferrite as a catalyst in a solvent and adopting microwave heating to react under the condition that no inorganic bases or ligands are adopted, thus obtaining the primary arylamine product. The method has the advantages that use of the ligands and the inorganic bases is avoided; the catalyst can be recycled; the method is simple and convenient to operate and is efficient.

Description

A kind of ammoniacal liquor that utilizes prepares the synthetic method of aryl primary amine for raw material
Technical field
The present invention relates to a kind of take ammoniacal liquor as the synthetic method of waste aryl primary amine, and particularly aryl bromo-derivative, aryl chloride complex and ammoniacal liquor react the synthetic method preparing aryl primary amine.
Background technology
Arylamine and derivative thereof are widely used in industrial circle (Lawrence, Amines:Synthesis, the Properties and Application such as medicine, agricultural chemicals, material, dyestuff; Cambridge University Press:Cambridge, 2004).The industrial important method preparing aryl primary amine, one is by nitro substituted aryl compound generation metal catalyzed hydrogenation reduction reaction; Two is by aryl halides or phenol, under high temperature or high pressure, nucleophilic substitution aminating reaction occurs.The transition metal-catalyzed C-N linked reaction of development in recent years prepares arylamine, is more and more subject to people and pays close attention to.Because it compares with traditional substitution reaction, avoid High Temperature High Pressure, and applicable different halides synthesizes various arylamine.In metal catalyzed coupling reaction, palladium catalyst has very important status, is that development is very fast, the obvious catalyzer of advantage.But metallic palladium is costly, also often need to use expensive Phosphine ligands, and due to palladium catalyst active, the halogeno-benzene of its catalysis and the reaction of ammonia, the product obtained, except primary amine, also easily obtains the by product such as secondary amine, tertiary amine (Shen, Q.; Hartwig, J.F.J.Am.Chem.Soc.2006,128,10028.Surry, D.S.; Buchwald, S.L.J.Am.Chem.Soc.2007,129,10354.).Inexpensively, after since Buchwald and horse, greatly seminar reduces temperature of reaction after introducing part to reaction system, copper catalysis Ullmman linked reaction obtains great development to copper metal.In recent years, copper catalysis halogeno-benzene and ammonia source (ammonia, ammoniacal liquor, ammonium chloride etc.) generation linked reaction generate arylamine and also achieve progress (Zeng, X.; Huang, W.; Qiu, Y.; Jiang, S.Org.Biomol.Chem.2011,9,8224.Xu, H.J.; Liang, Y.-F.; Cai, Z.-Y.; Qi, H.-X.; Yang, C.-Y.; Feng, Y.-S.J.Org.Chem.2011,76,2296.Xia, N.; Taillefer, M.Angew.Chem.Int.Ed.2009,48,337.Wang, D.; Cai, Q.; Ding, K.Adv.Synth.Catal.2009,351,1722.Kim, J.; Chang, S.Chem.Commun.2008,3052.), but often the amount ratio palladium of copper catalyst wants large, and reaction system also needs to add part, adds equivalent alkali, sometimes also will use expensive aryl iodide for thing as reactant, these further limit its application.But, ammoniacal liquor, as a kind of raw material be cheaply easy to get, if can search out suitable recyclable recycling catalyst, also can solve aryl chloride complex and ammoniacal liquor and to react generation aryl primary amine, this will be also industry or laboratory, provide a kind of method of useful synthesis aryl primary amine.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of take ammoniacal liquor as the synthetic method of waste aryl primary amine, and particularly aryl bromo-derivative, aryl chloride complex and ammoniacal liquor react the synthetic method preparing aryl primary amine.The method is avoided using part and mineral alkali, and catalyzer energy circulation and stress uses, easy and simple to handle, efficient.
For achieving the above object, the technical solution used in the present invention is as follows:
Taking ammoniacal liquor as a synthetic method for waste aryl primary amine, with aryl halides and ammoniacal liquor for raw material, is catalyzer with wustite in a solvent, adopts microwave heating, reacting, obtaining aryl primary amine product when not adding any mineral alkali and part.
Concrete reaction formula is as follows:
Wherein, X is selected from Br or Cl, and R is hydrogen atom, supplied for electronic or electron-withdrawing substituent, and R can be selected from methyl, methoxyl group, cyano group, nitro, carboxyl.
Preferably, the molar ratio of aryl halides and ammoniacal liquor is 1:1-1:20.
Preferably, the consumption of catalyzer is the 1-20% of aryl halides and ammoniacal liquor total mass.
Preferably, described wustite is selected from CuFe 2o 4, NiFe 2o 4, CoFe 2o 4in one or more.Wustite is a class magnetic particle catalyzer, has magnetic, can carry out repeatedly recycling use.
Preferably, described solvent is ammonia ethylene glycol, wherein ammoniacal liquor: the mass ratio of ethylene glycol is 1:1-1:10.
Preferably, microwave radiation temperature of reaction is 50-150 DEG C.
Preferably, the reaction times is 5-24 hour.
It should be noted that, of the present invention when not adding any mineral alkali and part, represent that reaction does not need to add corresponding alkali, as salt of wormwood, cesium carbonate, potassiumphosphate, sodium ethylate, potassium tert.-butoxide etc., and do not need to add corresponding part, as 1,10-phenanthroline, L-proline, Tetramethyl Ethylene Diamine etc.
The invention provides a kind of method utilizing recyclable magnetic catalyst catalysis and carry out microwave radiation heating Reactive Synthesis aryl primary amine, the method is avoided using part and mineral alkali, and catalyzer energy circulation and stress uses, and easy and simple to handle, efficient, reaction yield reaches 95%.
Accompanying drawing explanation
The recovery of Fig. 1 magneticmetal catalyzer.
The catalysis of Fig. 2 catalyst recirculation and isolated yield figure.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but protection scope of the present invention is not limited to this.
In embodiment 1:Schlenk reaction tubes, add bromobenzene (1mmol), strong aqua (1mL), CuFe 2o 4(12mg, 0.05mmol) and ethylene glycol (1mL).Reaction tubes seals, and under air atmosphere, under microwave radiation, is heated to 50-120 DEG C, reacts 15 hours.After reaction terminates, leave standstill, catalyzer can be adsorbed on magneton, and reaction solution clarification catalyst-free suspends; Reaction solution is extracted with ethyl acetate three times, and organic layer uses saturated common salt water washing three times again, organic layer through anhydrous sodium sulfate drying, concentrating under reduced pressure.Utilize column chromatography for separation to purify, obtain product aniline, productive rate 95%.Its structural characterization data are as follows: 1h NMR (400MHz, CDCl 3): δ 7.08-7.12 (m, 2H), 6.71-6.75 (m, 1H), 6.58-6.62 (m, 2H), 3.55 (s, br, 2H). 13c NMR: δ 146.6,129.4,118.6,115.2.
In embodiment 2:Schlenk reaction tubes, add 2-bromopyridine (1mmol), strong aqua (1mL), CuFe 2o 4(12mg, 0.05mmol) and ethylene glycol (1mL).Reaction tubes seals, and under air atmosphere, under microwave radiation, is heated to 50-120 DEG C, reacts 15 hours.After reaction terminates, leave standstill, catalyzer can be adsorbed on magneton, and reaction solution clarification catalyst-free suspends; Reaction solution is extracted with ethyl acetate three times, and organic layer uses saturated common salt water washing three times again, organic layer through anhydrous sodium sulfate drying, concentrating under reduced pressure.Utilize column chromatography for separation to purify, obtain product aniline, productive rate 86%.Its structural characterization data are as follows: 1h NMR (400MHz, CDCl 3): 7.97-7.99 (m, 1H), 7.31-7.35 (m, 1H), 6.53-6.56 (m, 1H), 6.40-6.42 (m, 1H), 4.47 (br, 2H). 13c NMR (100MHz, CDCl 3): 158.9,147.8,138.0,113.4,108.4.
In embodiment 3:Schlenk reaction tubes, add para-bromoanisole (1mmol), strong aqua (1mL), CuFe 2o 4(12mg, 0.05mmol) and ethylene glycol (1mL).Reaction tubes seals, and under air atmosphere, under microwave radiation, is heated to 50-120 DEG C, reacts 15 hours.After reaction terminates, leave standstill, catalyzer can be adsorbed on magneton, and reaction solution clarification catalyst-free suspends; Reaction solution is extracted with ethyl acetate three times, and organic layer uses saturated common salt water washing three times again, organic layer through anhydrous sodium sulfate drying, concentrating under reduced pressure.Utilize column chromatography for separation to purify, obtain product aniline, productive rate 90%.Its structural characterization data are as follows: 1h NMR (400MHz, CDCl 3):
6.65-6.68(m,2H),6.57-6.60(m,2H),3.67(s,3H). 13C NMR(100MHz,CDCl 3):。
In embodiment 4:Schlenk reaction tubes, add Nitrobromobenzene (1mmol), strong aqua (1mL), CuFe 2o 4(12mg, 0.05mmol) and ethylene glycol (1mL).Reaction tubes seals, and under air atmosphere, under microwave radiation, is heated to 50-120 DEG C, reacts 15 hours.After reaction terminates, leave standstill, catalyzer can be adsorbed on magneton, and reaction solution clarification catalyst-free suspends; Reaction solution is extracted with ethyl acetate three times, and organic layer uses saturated common salt water washing three times again, organic layer through anhydrous sodium sulfate drying, concentrating under reduced pressure.Utilize column chromatography for separation to purify, obtain product aniline, productive rate 87%.Its structural characterization data are as follows: 1h NMR (400MHz, CDCl 3): 8.09 (d, J=8Hz, 2H), 6.63 (d, J=8Hz, 2H), 4.47 (br, 2H). 13c NMR (100MHz, CDCl 3): 153.8,138.5,126.4,113.4.
In embodiment 5:Schlenk reaction tubes, add chlorobenzene (1mmol), strong aqua (1mL), CuFe 2o 4(12mg, 0.05mmol) and ethylene glycol (1mL).Reaction tubes seals, and under air atmosphere, under microwave radiation, is heated to 80-150 DEG C, reacts 15 hours.After reaction terminates, leave standstill, catalyzer can be adsorbed on magneton, and reaction solution clarification catalyst-free suspends; Reaction solution is extracted with ethyl acetate three times, and organic layer uses saturated common salt water washing three times again, organic layer through anhydrous sodium sulfate drying, concentrating under reduced pressure.Utilize column chromatography for separation to purify, obtain product aniline, productive rate 87%.Its structural characterization data are as follows: 1h NMR (400MHz, CDCl 3): δ 7.08-7.12 (m, 2H), 6.71-6.75 (m, 1H), 6.58-6.62 (m, 2H), 3.55 (s, br, 2H). 13c NMR: δ 146.6,129.4,118.6,115.2.
In embodiment 6:Schlenk reaction tubes, add nitro-chlorobenzene (1mmol), strong aqua (1mL), CuFe 2o 4(12mg, 0.05mmol) and ethylene glycol (1mL).Reaction tubes seals, and under air atmosphere, under microwave radiation, is heated to 80-150 DEG C, reacts 15 hours.After reaction terminates, leave standstill, catalyzer can be adsorbed on magneton, and reaction solution clarification catalyst-free suspends; Reaction solution is extracted with ethyl acetate three times, and organic layer uses saturated common salt water washing three times again, organic layer through anhydrous sodium sulfate drying, concentrating under reduced pressure.Utilize column chromatography for separation to purify, obtain product aniline, productive rate 83%.Its structural characterization data are as follows: 1h NMR (400MHz, CDCl 3): 8.09 (d, J=8Hz, 2H), 6.63 (d, J=8Hz, 2H), 4.47 (br, 2H). 13c NMR (100MHz, CDCl 3): 153.8,138.5,126.4,113.4.
In embodiment 7:Schlenk reaction tubes, add 2-bromopyridine (1mmol), strong aqua (1mL), CoFe 2o 4(11mg, 0.05mmol) and ethylene glycol (1mL).Reaction tubes seals, and under air atmosphere, under microwave radiation, is heated to 50-120 DEG C, reacts 15 hours.After reaction terminates, leave standstill, catalyzer can be adsorbed on magneton, and reaction solution clarification catalyst-free suspends; Reaction solution is extracted with ethyl acetate three times, and organic layer uses saturated common salt water washing three times again, organic layer through anhydrous sodium sulfate drying, concentrating under reduced pressure.Utilize column chromatography for separation to purify, obtain product aniline, productive rate 82%.Its structural characterization data are as follows: 1h NMR (400MHz, CDCl 3): 7.97-7.99 (m, 1H), 7.31-7.35 (m, 1H), 6.53-6.56 (m, 1H), 6.40-6.42 (m, 1H), 4.47 (br, 2H). 13c NMR (100MHz, CDCl 3): 158.9,147.8,138.0,113.4,108.4.
In embodiment 8:Schlenk reaction tubes, add 2-bromopyridine (1mmol), strong aqua (1mL), NiFe 2o 4(11mg, 0.05mmol) and ethylene glycol (1mL).Reaction tubes seals, and under air atmosphere, under microwave radiation, is heated to 50-120 DEG C, reacts 15 hours.After reaction terminates, leave standstill, catalyzer can be adsorbed on magneton, and reaction solution clarification catalyst-free suspends; Reaction solution is extracted with ethyl acetate three times, and organic layer uses saturated common salt water washing three times again, organic layer through anhydrous sodium sulfate drying, concentrating under reduced pressure.Utilize column chromatography for separation to purify, obtain product aniline, productive rate 85%.Its structural characterization data are as follows: 1h NMR (400MHz, CDCl 3): 7.97-7.99 (m, 1H), 7.31-7.35 (m, 1H), 6.53-6.56 (m, 1H), 6.40-6.42 (m, 1H), 4.47 (br, 2H). 13c NMR (100MHz, CDCl 3): 158.9,147.8,138.0,113.4,108.4.
(bromobenzene is raw material to the test of catalyst recovery number of times, CuFe 2o 4for catalyzer)
Recycling: adsorb magneton with external magnet, by the reaction solution in pipe to going out, stay magneton and catalyzer in pipe, use distilled water, EA, washes of absolute alcohol catalyzer successively, then dry in baking oven, for lower secondary response, do 10 recycling catalyst productivity ratios comparatively, specifically see Fig. 2, visible, after catalyst regeneration, catalytic efficiency does not significantly reduce, favorable reproducibility.
It will be recognized by those skilled in the art, under the prerequisite not departing from protection scope of the present invention, various amendment, change and combination can be carried out to above-mentioned embodiment, and think that this amendment, change and combination are within the scope of originality thought.

Claims (8)

1. be a synthetic method for waste aryl primary amine with ammoniacal liquor, it is characterized in that, with aryl halides and ammoniacal liquor for raw material, be catalyzer in a solvent with wustite, adopt microwave heating, reacting when not adding any mineral alkali and part, obtaining aryl primary amine product.
2. synthetic method according to claim 1, is characterized in that, the molar ratio of aryl halides and ammoniacal liquor is 1:1-1:20.
3. synthetic method according to claim 1, is characterized in that, the consumption of catalyzer is the 1-20% of aryl halides and ammoniacal liquor total mass.
4. synthetic method according to claim 1, is characterized in that, described wustite is selected from CuFe 2o 4, NiFe 2o 4, CoFe 2o 4in one or more, and they are the recyclable catalyzer of a class magnetic.
5. synthetic method according to claim 1, is characterized in that, described solvent is ammonia ethylene glycol.
6. synthetic method according to claim 4, is characterized in that, ammoniacal liquor: the mass ratio of ethylene glycol is 1:1-1:10.
7. synthetic method according to claim 1, is characterized in that, microwave radiation temperature of reaction is 50-150 DEG C.
8. synthetic method according to claim 1, is characterized in that, the reaction times is 5-24 hour.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104926663A (en) * 2015-05-28 2015-09-23 国药集团化学试剂有限公司 Preparation method for high-purity aniline containing trace nitrocompound
CN106316852A (en) * 2015-06-17 2017-01-11 中国石油化工股份有限公司 Method for one-step catalytic synthesis of diphenyl carbonate from carbon dioxide and phenol
CN109896961A (en) * 2019-04-24 2019-06-18 江苏扬农化工集团有限公司 A kind of preparation method of p-phenylenediamine
CN114773136A (en) * 2022-04-02 2022-07-22 陕西师范大学 Method for synthesizing arylamine

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CN101717369A (en) * 2009-11-23 2010-06-02 四川大学 Method for preparing arylamine by catalysis in aqueous phase
CN102146008A (en) * 2011-01-18 2011-08-10 陕西师范大学 Organic solvent-free synthesis method of aromatic amine compounds
CN103396362A (en) * 2013-08-21 2013-11-20 郑州西格玛化工有限公司 Method for preparing 9-oxo-10(9H)-acridineacetic acid

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US5925790A (en) * 1997-03-13 1999-07-20 Uniroyal Chemical Company, Inc. Preparation of substituted aromatic amines
CN101121668A (en) * 2007-09-28 2008-02-13 中北大学 Method of synthesizing 4,4'-dimethyltrianiline
CN101717369A (en) * 2009-11-23 2010-06-02 四川大学 Method for preparing arylamine by catalysis in aqueous phase
CN102146008A (en) * 2011-01-18 2011-08-10 陕西师范大学 Organic solvent-free synthesis method of aromatic amine compounds
CN103396362A (en) * 2013-08-21 2013-11-20 郑州西格玛化工有限公司 Method for preparing 9-oxo-10(9H)-acridineacetic acid

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104926663A (en) * 2015-05-28 2015-09-23 国药集团化学试剂有限公司 Preparation method for high-purity aniline containing trace nitrocompound
CN106316852A (en) * 2015-06-17 2017-01-11 中国石油化工股份有限公司 Method for one-step catalytic synthesis of diphenyl carbonate from carbon dioxide and phenol
CN109896961A (en) * 2019-04-24 2019-06-18 江苏扬农化工集团有限公司 A kind of preparation method of p-phenylenediamine
CN114773136A (en) * 2022-04-02 2022-07-22 陕西师范大学 Method for synthesizing arylamine
CN114773136B (en) * 2022-04-02 2023-06-16 陕西师范大学 Method for synthesizing aromatic amine

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