CN107759545A - A kind of method that one kettle way prepares N (5 methyl furfuryl group) P-nethoxyaniline - Google Patents
A kind of method that one kettle way prepares N (5 methyl furfuryl group) P-nethoxyaniline Download PDFInfo
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- CN107759545A CN107759545A CN201711076942.8A CN201711076942A CN107759545A CN 107759545 A CN107759545 A CN 107759545A CN 201711076942 A CN201711076942 A CN 201711076942A CN 107759545 A CN107759545 A CN 107759545A
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Abstract
A kind of preparation method of N (5 methyl furfuryl group) P-nethoxyaniline, comprises the following steps：Multiphase hydrogenation catalyst, 5 methyl furfurals, solvent, P-nethoxyaniline are added in reaction vessel successively, in the hydrogen atmosphere of normal pressure ~ 2.0Mpa pressure, under the reaction temperature of normal temperature ~ 100 DEG C, stirring, react 0.2 ~ 30h, separating catalyst and product.Streamline operation of the present invention, the loss of material that intermediate steps are brought is avoided, realize that resource maximally utilizes；Under suitable process conditions, the reaction time is substantially reduced, reduces production cost, improves production efficiency；Carry out in a mild condition, it is less demanding to production equipment, meet the principle of safety in production.
Description
Technical field
The invention belongs to compound synthesis method field.
Background technology
N- (5- methyl furfuryl group) P-nethoxyaniline（CAS 95124-39-3；C13H15NO2；2-Furanmethanamine,
N-(4-methoxyphenyl)-5-methyl-）With certain bacteria resistance function（Fedor I. Zubkov, Vladimir P.
Zaytsev, Eugeniya V. Nikitina, et al. Tetrahedron, 2011, 9148-9163）, generally by two
Prepared by footwork, that is, first pass through 5 methyl furfural and react to obtain the N- (5- methyl furfuryl group) containing carbon-to-nitrogen double bon with P-nethoxyaniline
P-methoxyphenyl imines, then C=N is reduced by hydroborating reagent and obtains target product N- (5- methyl furfuryl group) to methoxybenzene
Amine, wherein hydroborating reagent include (Zivko Klepo, the Kresimir Jakopcic. such as magnesium/Reduction of methanol system, sodium borohydride
J. Chem. Eng. Data, 1985, 235-237；Fernando D. Suvire, Maximiliano Sortino,
Vladimir V. Kouznetsov, et al. Enriz. Bioorgan. Med. Chem., 2006, 1851-1867；
Igor V. Trushkov,Tatyana A. Nevolina,Vitaly A. Shcherbinin, et al.
Tetrahedron Lett., 2013, 3974-3976).Although existing lot of documents shows the hydroborating reagent energy such as sodium borohydride
Enough successfully reduction C=N also can be easily by aldehyde into C-N, but simultaneously（Or ketone）Carbonyl reduction is into alcohol so that reduction amination process
It need to be carried out in two steps, and the waste of a large amount of expensive hydroborating reagents is caused using the hydroborating reagent of excess.Therefore 5- methyl is sought
The new route that furfural direct-reduction amination obtains N- (5- methyl furfuryl group) P-nethoxyaniline is imperative.In fact, by Pd,
The direct-reduction amination of the metal catalyzed hydrogenations such as Ni, Pt, have been used to industrially prepared (the Shigeo Nishimura. of several amine
Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis,
Wiley, New York, 2001).Wherein Pd/C is most common wide variety of hydro-reduction catalyst, for by C=O
Be formed as new amine compound with amine reduction.It is generally acknowledged that pilot process passes through imines, but it is not required to separate, continues to urge through Pd/C
Change C=N hydrogenations, generate required amine compound (George N. Karageorge, John E. Macor.
Tetrahedron Lett.,2011,5117-5119).But directly gone back with P-nethoxyaniline by being catalyzed 5 methyl furfural
The report that former amination obtains N- (5- methyl furfuryl group) P-nethoxyaniline is more rarely seen.
The content of the invention
The problems such as cost is high, technique is cumbersome, low yield is prepared to solve existing N- (5- methyl furfuryl group) P-nethoxyaniline,
The present invention is provided under a kind of atmosphere of hydrogen, adds heterogeneous catalyst, using simple one kettle way, by 5 methyl furfural and to methoxy
The method that the direct-reduction amination of base aniline prepares N- (5- methyl furfuryl group) P-nethoxyaniline.
The present invention have it is simple, efficiently, industrialization cost is low, is easy to the advantages of industrialization.So far, 5 methyl furfural
Reduction amination is directly catalyzed with P-nethoxyaniline and prepares the research of N- (5- methyl furfuryl group) P-nethoxyaniline foreign language at home
It is not reported in offering, the research is significant.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of N- (5- methyl furfuryl group) P-nethoxyaniline of the present invention, comprises the following steps：Will
Multiphase hydrogenation catalyst, 5 methyl furfural, solvent, P-nethoxyaniline are added in reaction vessel successively, in normal pressure ~ 2.0Mpa pressures
The hydrogen atmosphere of power, under the reaction temperature of normal temperature ~ 100 DEG C, stirring, react 0.2 ~ 30h, separating catalyst and product.
Described multiphase hydrogenation catalyst is support type more than one or both of Ru, Rh, Pd, Pt, Fe or Ni etc.
Catalyst, it is reusable.
Described catalyst amount（Measured by active component）For 0.01 ~ 1 mol% of reaction substrate 5 methyl furfural.
In described reaction, the ratio between amount of material of reaction substrate 5 methyl furfural and P-nethoxyaniline is 1:0.5~1:
1.5。
Described solvent is selected from the conventional organic solvents such as ethanol, ethyl acetate, toluene or benzene；Solvent load is reaction substrate
5 ~ 50 times of cumulative volume.
Compared with prior art, its advantage is the present invention.
（1）The preparation of N- (5- methyl furfuryl group) P-nethoxyaniline of the present invention streamline operation, avoids through one pot of completion
The loss of material that intermediate steps are brought, realizes that resource maximally utilizes.
（2）The preparation of N- (5- methyl furfuryl group) P-nethoxyaniline of the present invention is through one pot of completion, in suitable process conditions
Under, the reaction time is substantially reduced, reduces production cost, improves production efficiency.
（3）The preparation of N- (5- methyl furfuryl group) P-nethoxyaniline of the present invention is carried out in a mild condition, to production equipment
It is less demanding, meet the principle of safety in production.
Brief description of the drawings
Fig. 1 is the gas-chromatography that reaction solution obtained by N- (5- methyl furfuryl group) P-nethoxyaniline process is prepared by embodiment 1
Figure.
Fig. 2 is the mass spectrogram that target product obtained by N- (5- methyl furfuryl group) P-nethoxyaniline process is prepared by embodiment 1.
Fig. 3 is the nuclear-magnetism hydrogen that target product obtained by N- (5- methyl furfuryl group) P-nethoxyaniline process is prepared by embodiment 1
Spectrogram.
Embodiment
With reference to embodiment, the present invention is described in further detail.
It will be understood to those of skill in the art that the following example is merely to illustrate the present invention, and it should not be regarded as limiting this hair
Bright scope.In the examples where no specific technique or condition is specified, according to the technology or condition described by document in the art
Or carried out according to product description.Agents useful for same or the unreceipted production firm person of instrument, it is that can be obtained by buying
Conventional products.
Embodiment 1.
In with magnetic stir bar autoclave, 10mg Pd/C, 500ul 5 methyl furfurals, 20ml are successively added
Ethyl acetate, 0.6783g P-nethoxyaniline, kettle is closed, and with the air in hydrogen metathesis reactor, and ensure to react initial hydrogen
Atmospheric pressure is 1.2Mpa, and autoclave is placed in electric heating cover, is warming up to 90 DEG C, stirring reaction 4h.React laggard promoting the circulation of qi
Analysis of hplc, calculated by area normalization method, substrate 5 methyl furfural, the conversion ratio of P-nethoxyaniline reach respectively
To 96.87%, 88.60%, intermediate product N- (5- methyl furfuryl group) p-methoxyphenyl imines and target product N- (5- first in system
Base furfuryl group) percentage composition of P-nethoxyaniline is respectively 31.04%, 55.10%.
Fig. 1 is the gas-chromatography that the present embodiment prepares reaction solution obtained by N- (5- methyl furfuryl group) P-nethoxyaniline process
Figure.As illustrated, retention time 10.289min corresponds to 5 methyl furfural, 21.233min corresponds to P-nethoxyaniline,
31.178min corresponds to N- (5- methyl furfuryl group) P-nethoxyaniline, and 31.886min corresponds to N- (5- methyl furfuryl group) to methoxybenzene
Base imines.
Fig. 2 is the mass spectrogram that the present embodiment prepares target product obtained by N- (5- methyl furfuryl group) P-nethoxyaniline process.
Fig. 3 is the nucleus magnetic hydrogen spectrum that the present embodiment prepares target product obtained by N- (5- methyl furfuryl group) P-nethoxyaniline process
Figure.
Embodiment 2.
In with magnetic stir bar autoclave, 15mg Pd/C, 500ul 5 methyl furfurals, 20ml are successively added
Ethyl acetate, 0.6781g P-nethoxyaniline, kettle is closed, and with the air in hydrogen metathesis reactor, and ensure to react initial hydrogen
Atmospheric pressure is 0.8Mpa, and autoclave is placed in electric heating cover, is warming up to 70 DEG C, stirring reaction 2h.React laggard promoting the circulation of qi
Analysis of hplc, calculated by area normalization method, substrate 5 methyl furfural, the conversion ratio of P-nethoxyaniline reach respectively
To 94.30%, 87.22%, intermediate product N- (5- methyl furfuryl group) p-methoxyphenyl imines and target product N- (5- first in system
Base furfuryl group) percentage composition of P-nethoxyaniline is respectively 26.70%, 97.10%.
Embodiment 3.
In with magnetic stir bar autoclave, 10mg Pd/C, 500ul 5 methyl furfurals, 20ml are successively added
Ethanol, 0.6779g P-nethoxyaniline, kettle is closed, and with the air in hydrogen metathesis reactor, and ensure to react initial hydrogen pressure
Power is 1.2Mpa, and autoclave is placed in electric heating cover, is warming up to 90 DEG C, stirring reaction 4h.React laggard promoting the circulation of qi phase color
Spectrum analysis, is calculated, substrate 5 methyl furfural, the conversion ratio of P-nethoxyaniline respectively reach by area normalization method
100%th, 91.60%, intermediate product N- (5- methyl furfuryl group) p-methoxyphenyl imines and target product N- (5- methyl chaffs in system
Base) percentage composition of P-nethoxyaniline is respectively 25.44%, 66.15%.
Embodiment 4.
In with magnetic stir bar autoclave, 15mg Pd/C, 500ul 5 methyl furfurals, 20ml are successively added
Ethanol, 0.6782g P-nethoxyaniline, kettle is closed, and with the air in hydrogen metathesis reactor, and ensure to react initial hydrogen pressure
Power is 0.8Mpa, and autoclave is placed in electric heating cover, is warming up to 90 DEG C, stirring reaction 4h.React laggard promoting the circulation of qi phase color
Spectrum analysis, is calculated, substrate 5 methyl furfural, the conversion ratio of P-nethoxyaniline respectively reach by area normalization method
100%th, 92.73%, intermediate product N- (5- methyl furfuryl group) p-methoxyphenyl imines and target product N- (5- methyl chaffs in system
Base) percentage composition of P-nethoxyaniline is respectively 4.13%, 88.60%.
Embodiment 5.
In with magnetic stir bar autoclave, 15mg Pd/C, 500ul 5 methyl furfurals, 20ml are successively added
Ethyl acetate, 0.6781g P-nethoxyaniline, kettle is closed, and with the air in hydrogen metathesis reactor, and ensure to react initial hydrogen
Atmospheric pressure is 1.2Mpa, and autoclave is placed in electric heating cover, is warming up to 70 DEG C, stirring reaction 4h.React laggard promoting the circulation of qi
Analysis of hplc, calculated by area normalization method, substrate 5 methyl furfural, the conversion ratio of P-nethoxyaniline reach respectively
To 98.52%, 92.12%, intermediate product N- (5- methyl furfuryl group) p-methoxyphenyl imines and target product N- (5- first in system
Base furfuryl group) percentage composition of P-nethoxyaniline is respectively 1.42%, 89.44%.
Embodiment 6.
In with magnetic stir bar autoclave, 15mg Pd/C, 500ul 5 methyl furfurals, 20ml are successively added
Ethyl acetate, 0.6773g P-nethoxyaniline, kettle is closed, and with the air in hydrogen metathesis reactor, and ensure to react initial hydrogen
Atmospheric pressure is 1.2Mpa, and autoclave is placed in electric heating cover, is warming up to 90 DEG C, stirring reaction 4h.React laggard promoting the circulation of qi
Analysis of hplc, calculated by area normalization method, substrate 5 methyl furfural, the conversion ratio of P-nethoxyaniline reach respectively
To 99.08%, 92.63%, intermediate product N- (5- methyl furfuryl group) p-methoxyphenyl imines and target product N- (5- first in system
Base furfuryl group) percentage composition of P-nethoxyaniline is respectively 1.60%, 90.24%.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended claim and its waits
Effect thing defines.
Claims (1)
- A kind of 1. preparation method of N- (5- methyl furfuryl group) P-nethoxyaniline, it is characterized in that comprising the following steps：It will be added more Hydrogen catalyst, 5 methyl furfural, solvent, P-nethoxyaniline are added in reaction vessel successively, in the hydrogen of normal pressure ~ 2.0Mpa pressure Gas atmosphere, under the reaction temperature of normal temperature ~ 100 DEG C, stirring, react 0.2 ~ 30h, separating catalyst and product；The multiphase hydrogenation catalyst is more than one or both of Ru, Rh, Pd, Pt, Fe or Ni；Catalyst amount is by activity Component metering is 0.01 ~ 1 mol% of reaction substrate 5 methyl furfural；The ratio between amount of material of reaction substrate 5 methyl furfural and P-nethoxyaniline is 1:0.5~1:1.5；Described solvent is ethanol, ethyl acetate, toluene or benzene；Solvent load is 5 ~ 50 times of reaction substrate cumulative volume.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003038109A2 (en) * | 2001-09-18 | 2003-05-08 | The Board Of Regents Of The University Of Nebraska | Method for the inhibition of methanogenesis |
| CN107001312A (en) * | 2014-12-15 | 2017-08-01 | 有机燃料瑞典公司 | By heterogeneous metal catalytic by aldehydes or ketones synthesizing amide and amine |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003038109A2 (en) * | 2001-09-18 | 2003-05-08 | The Board Of Regents Of The University Of Nebraska | Method for the inhibition of methanogenesis |
| CN107001312A (en) * | 2014-12-15 | 2017-08-01 | 有机燃料瑞典公司 | By heterogeneous metal catalytic by aldehydes or ketones synthesizing amide and amine |
Non-Patent Citations (2)
| Title |
|---|
| IGOR V. TRUSHKOV ET AL.: ""Furan ring opening-pyrrole ring closure. A simple route to 1,2,3,4-tetrahydropyrrolo[1,2-α]pyrazin-3-ones"", 《TETRAHEDRON LETTERS》 * |
| L. HIZARTZIDIS ET AL.: ""Chemoselective flow hydrogenation approaches to isoindole-7-carboxylic acids and 7-oxa-bicyclio [2.2.1]heptanes"", 《RSC ADVANCES》 * |
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