CN106278984A - A kind of synthetic method of N-substituted imides - Google Patents
A kind of synthetic method of N-substituted imides Download PDFInfo
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- CN106278984A CN106278984A CN201510242404.6A CN201510242404A CN106278984A CN 106278984 A CN106278984 A CN 106278984A CN 201510242404 A CN201510242404 A CN 201510242404A CN 106278984 A CN106278984 A CN 106278984A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
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Abstract
The invention provides the preparation method of a kind of N-substituted imides.The method is with aromatic ketone and amine as substrate, and air or oxygen is oxygen source, under catalyst action, under liquid-phase condition, generates cyclic imide.The method mild condition, oxidation efficiency is high, and product yield is high；Using air or oxygen as oxygen source, economy, environmental protection, there is good application prospect.
Description
Technical field
The present invention relates to chemical field, be specifically related to the preparation method of a kind of N-substituted imides.
Background technology
Acid imide is a kind of important industrial chemicals intermediate, is widely used in organic synthesis, pharmacy, high score
The fields such as son, have the huge market demand and using value.Traditionally, acid imide synthesis is mainly passed through
Anhydride and amine react generation, or prepared by different imido Mumm rearrangement reaction.Have also been developed in recent years
The oxidation of new method, such as tertiary amine and the carbonylation synthesis of amide.But some reaction paths are pervasive
Property is poor, can only synthesize limited imide product；Some reaction path substrates are not readily available, or instead
Answer condition harsh.Inventor provide the synthetic method of a kind of new N-substituted imides.With aromatic ketone and having
Machine primary amine is substrate, and under liquid phase cryogenic conditions, oxygen or air are oxygen source, efficiently prepare the substituted acyl of nitrogen
Imines.
Summary of the invention
The invention provides the synthetic method of a kind of new N-substituted imides, the method uses aromatic ketone and has
Machine primary amine be substrate, oxygen or air be oxygen source, under catalyst action, generate the substituted acid imide of nitrogen；
Described aromatic ketone is indone and aromatic ring substitutive derivative thereof, 1,2,3,4-Tetrahydrooxonaphthalene and aromatic ring substitutive derivative thereof,
Benzosuberone and aromatic ring substitutive derivative thereof.
Described substituent group is OCH3、F、Cl、Br、I、NO2、CH3In one or more, substituent group
Number is 1-5.
Described primary amine is aniline and the substituted derivant of phenyl ring thereof, Bian amine and the substituted derivant of phenyl ring, naphthalene
Amine and the substituted derivant of naphthalene nucleus, the fat primary amine of C1-C18.
In the substituted derivant of described phenyl ring, substituent group is OCH3、F、Cl、Br、I、NO2、CH3In one
Or multiple, the number of substituent group is 1-5.
In the substituted derivant of described naphthalene nucleus, substituent group is OCH3、F、Cl、Br、I、NO2、CH3In one
Or multiple, the number of substituent group is 1-7.
Aromatic ketone is 1:1-5 with the mol ratio of organic primary amine.
According to the present invention, using eco-friendly oxygen or air is oxygen source.The oxygen molecule of three forms is the most alive
Ripple, needs catalyst to carry out activating oxygen and forms active oxygen.The present invention use transition metal V, Fe, Co, Mn,
More than the one or two kinds of in Cu, Cr, Mo, Ce, Nb, W oxide or slaine live for catalyst
Change oxygen molecule.
According to the present invention, catalytic performance is relevant with the consumption of catalyst, the too low activity that can affect catalytic reaction,
The too high cost that can increase catalyst of consumption, it is therefore desirable to select suitable consumption.In order to ensure catalyst
Activity, can reduce again catalyst cost simultaneously, and used catalyst with the mol ratio of aromatic ketone is: 0.1-30mol%,
Preferably 1-20mol%.
According to the present invention, reaction effect is relevant with oxygen pressure, reaction temperature and time, wherein oxygen partial pressure
For 0.1-2MPa, reaction temperature is 60-180 DEG C, and the response time is 1-48h；Preferably oxygen partial pressure 0.4-1
MPa, reaction temperature 100-160 DEG C, response time 6-24h.
According to the present invention, this reaction needs to carry out in a solvent, particularly at the bottom of solid aromatic ketone and organic primary amine
Thing molecule, needing to be dissolved in can be dispersed in solvent, is conducive to and the contacting of catalyst.Tertiary amine oxygen
Change solvent for use be toluene, chlorobenzene, DMF, normal octane, THF, dioxane, methanol, ethanol, acetonitrile,
More than the one or two kinds of in DMSO.Aromatic ketone mass concentration 1-80wt% in solvent, preferably 1-40
Wt%.
Detailed description of the invention
The following example will assist in and understands the present invention, but present invention is not limited thereto.
Embodiment 1
By 0.01g MnO2Catalyst, 0.5mmol 1-indone, 2mmol aniline and 2g chlorobenzene add not
Rust steel autoclave, included polytetrafluoroethyllining lining.Use automatic temperature control instrument temperature programming to reaction temperature
100 DEG C, add 0.6MPa oxygen, react 4h, course of reaction keeps pressure constant.Product makes
Being analyzed with GC-MS, pyridyl phthalimide yield is 85%.
Embodiment 2-23
Except catalyst and consumption, pressure, response time difference, catalyst activity is evaluated same as in Example 1.
Reaction condition and catalytic reaction the results are shown in Table 1.Catalyst and consumption, oxygen pressure, anti-as can be seen from Table 1
Answer temperature and response time that catalytic effect is had an impact.Along with reaction temperature (embodiment 2 and 3), catalyst
Consumption (embodiment 2 and 5), oxygen pressure (embodiment 3 and 5) and (embodiment 5 and 6) in response time
Increasing, yield increases.Catalyst amount increases oxygen pressure and increases, N-phenylphthalimide yield
It is consequently increased.The oxides such as transition metal V, Fe, Co, Mn, Cu, Cr, Mo, Ce, Nb, W or
Slaine, all shows preferable effect.
Pyridyl phthalimide is prepared in table 1 1-indone and aniline oxidation
Embodiment 24-36
Except aromatic ketone substrate is different with solvent load, catalyst activity is evaluated same as in Example 1.Reaction bar
Part and catalytic reaction the results are shown in Table 2.The substituted aromatic ketone of different kinds of aromatic ring can generate corresponding N-with aniline
Substituted imides.
Table 2 distinct fragrance ketone substrate and aniline are that substrate synthesizes N-substituted imides
Embodiment 37-58
Except organic primary amine substrate is different, catalyst activity is evaluated same as in Example 1.Reaction result is shown in Table 3.
Different organic primary amine can generate corresponding N-substituted imides.
The different organic primary amine of table 3 is substrate synthesizing imide with 1-indone
Inventive substrate wide accommodation, oxidation efficiency is high, and product yield is high；Using air or oxygen as oxygen
Source, economy, environmental protection, there is good application prospect.
Claims (7)
1. the synthetic method of a N-substituted imides, it is characterised in that: with the one in air or oxygen or
Person two kinds is oxygen source, and under catalyst action, aromatic ketone and primary amine react and generate N-substituted imides；
Catalyst be transition metal V, Fe, Co, Mn, Cu, Cr, Mo, Ce, Nb, W oxide or
More than the one or two kinds of in slaine.
Method the most according to claim 1, it is characterised in that: described aromatic ketone oxidation oxygen source used is
One or two kinds of in air or oxygen, wherein oxygen partial pressure is 0.1-2MPa, and reaction temperature is 60-180
DEG C, the response time is 1-48h；
Preferably oxygen partial pressure 0.4-1MPa, reaction temperature 100-160 DEG C, response time 6-24h.
Method the most according to claim 1, it is characterised in that:
In terms of metal, used catalyst consumption is the 0.1-30mol% of primary amine, preferably 1-20mol%.
Method the most according to claim 1, it is characterised in that: solvent for use is toluene, chlorobenzene, N, N-
Diformamide (DMF), normal octane, oxolane (THF), dioxane, methanol, ethanol, dimethyl
More than the one or two kinds of in sulfoxide (DMSO), aromatic ketone and primary amine mass concentration 1-80 in solvent
Wt%, preferably 1-40wt%.
5. according to the method described in claim 1 or 4, it is characterised in that: aromatic ketone with the mol ratio of amine is
1:1-5。
Method the most according to claim 1, it is characterised in that: described aromatic ketone is indone and aromatic ring thereof
Substitutive derivative, 1,2,3,4-Tetrahydrooxonaphthalene and aromatic ring substitutive derivative thereof, benzosuberone and aromatic ring substitutive derivative thereof
In one or two kinds of more than；
Substituent group in described derivant is OCH3、F、Cl、Br、I、NO2、CH3In one or 2 kinds
Above, the number of substituent group is 1-6.
Method the most according to claim 1, it is characterised in that: described primary amine is aniline and phenyl ring takes
The derivant in generation, Bian amine and the substituted derivant of phenyl ring thereof, naphthylamines and the substituted derivant of naphthalene nucleus, C1-C18
Fat primary amine；
In the substituted derivant of described phenyl ring, substituent group is OCH3、F、Cl、Br、I、NO2、CH3In one
Or two or more；The number of substituent group is 1-5；
In the substituted derivant of described naphthalene nucleus, substituent group is OCH3、F、Cl、Br、I、NO2、CH3In one
Or two or more；The number of substituent group is 1-7.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510242404.6A CN106278984B (en) | 2015-05-13 | 2015-05-13 | A kind of synthetic method of N- substituted imides |
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| CN201510242404.6A CN106278984B (en) | 2015-05-13 | 2015-05-13 | A kind of synthetic method of N- substituted imides |
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| CN106278984A true CN106278984A (en) | 2017-01-04 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139316A (en) * | 2007-10-18 | 2008-03-12 | 北京大学 | Anthraquinone imide compound and method for making same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139316A (en) * | 2007-10-18 | 2008-03-12 | 北京大学 | Anthraquinone imide compound and method for making same |
Non-Patent Citations (1)
| Title |
|---|
| STEVEN D. WYRICK, ET AL.: "Effects of [(N-Alkyl-1,3-dioxo-lH,3H-isoindolin-5-yl)oxy]alkanoic Acids, [(N-Alkyl-l-oxo-1H,3H-isoindolin-5-y1)oxy]butanoic Acids, and Related Derivatives on Chloride Influx in Primary Astroglial Cultures", 《J. MED. CHEM.》 * |
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Granted publication date: 20190329 |