CN106278984B - 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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- CN106278984B CN106278984B CN201510242404.6A CN201510242404A CN106278984B CN 106278984 B CN106278984 B CN 106278984B CN 201510242404 A CN201510242404 A CN 201510242404A CN 106278984 B CN106278984 B CN 106278984B
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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 present invention provides a kind of preparation methods of N- substituted imides.For this method using aromatic ketone and amine as substrate, air or oxygen is oxygen source, under the action of catalyst, 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, economic, environmental protection is had a good application prospect.
Description
Technical field
The present invention relates to chemical fields, and in particular to a kind of preparation method of N- substituted imides.
Background technique
Acid imide is a kind of important industrial chemicals intermediate, is widely used in the neck such as organic synthesis, pharmacy, macromolecule
Domain has the huge market demand and application value.Traditionally, acid imide synthesis mainly reacts generation with amine by acid anhydrides,
Or different imido Mumm rearrangement reaction preparation.Some new methods, such as oxidation and the acyl of tertiary amine have also been developed in recent years
The carbonylation of amine synthesizes.But some reaction path universalities is poor, can only synthesize limited imide product；What is had is anti-
The approach substrate of answering is not readily available or severe reaction conditions.Inventor provide a kind of synthesis of new N- substituted imides
Method.Using aromatic ketone and organic primary amine as substrate, under liquid phase cryogenic conditions, oxygen or air are oxygen source, efficiently prepare nitrogen and take
The acid imide in generation.
Summary of the invention
The present invention provides a kind of synthetic method of new N- substituted imides, this method uses aromatic ketone and organic primary amine
For substrate, oxygen or air are oxygen source, under the action of catalyst, generate the acid imide that nitrogen replaces；
The aromatic ketone is indone and its aromatic ring substitutive derivative, tetralone and its aromatic ring substitutive derivative, benzo ring
Heptanone and its aromatic ring substitutive derivative.
The substituent group is OCH3、F、Cl、Br、I、NO2、CH3One or more of, the number of substituent group is 1-5
It is a.
The primary amine is aniline and its cyclosubstituted derivative of benzene, Bian amine and its cyclosubstituted derivative of benzene, naphthylamines and its
The cyclosubstituted derivative of naphthalene, the fat primary amine of C1-C18.
Substituent group is OCH in the cyclosubstituted derivative of benzene3、F、Cl、Br、I、NO2、CH3One or more of,
The number of substituent group is 1-5.
Substituent group is OCH in the cyclosubstituted derivative of naphthalene3、F、Cl、Br、I、NO2、CH3One or more of,
The number of substituent group is 1-7.
The molar ratio of aromatic ketone and organic primary amine is 1:1-5.
According to the present invention, use environmental-friendly oxygen or air for oxygen source.The oxygen molecule of three forms wave not living enough, needs
It wants catalyst to carry out activating oxygen and forms active oxygen.The present invention uses transition metal V, Fe, Co, Mn, Cu, Cr, Mo, Ce, Nb, W oxygen
One of compound or metal salt two or more carry out activating oxygen molecule for catalyst.
According to the present invention, catalytic performance is related with the dosage of catalyst, the too low activity that will affect catalysis reaction, dosage mistake
Height will increase the cost of catalyst, it is therefore desirable to select dosage appropriate.In order to guarantee the activity of catalyst, while can reduce again
The molar ratio of catalyst cost, used catalyst and aromatic ketone are as follows: 0.1-30mol%, preferably 1-20mol%.
According to the present invention, reaction effect is related with oxygen pressure, reaction temperature and time, and wherein oxygen partial pressure is 0.1-
2MPa, reaction temperature are 60-180 DEG C, reaction time 1-48h；It is preferred that oxygen partial pressure 0.4-1MPa, reaction temperature 100-160
DEG C, reaction time 6-24h.
According to the present invention, which needs to carry out in a solvent, especially solid aromatic ketone and organic primary amine substrate molecule,
Needing to be dissolved in can be evenly dispersed in solvent, is conducive to the contact with catalyst.It is toluene, chlorine that tertiary amine, which aoxidizes solvent for use,
One of benzene, DMF, normal octane, THF, dioxane, methanol, ethyl alcohol, acetonitrile, DMSO are two or more.Aromatic ketone is in molten
Mass concentration 1-80wt% in agent, preferably 1-40wt%.
Specific embodiment
The following example will be helpful to understand the present invention, but the content of present invention is not limited thereto.
Embodiment 1
By 0.01g MnO2Stainless steel reaction under high pressure is added in catalyst, 0.5mmol 1- indone, 2mmol aniline and 2g chlorobenzene
Kettle, included polytetrafluoroethyllining lining.Using automatic temperature control instrument temperature programming to 100 DEG C of reaction temperature, 0.6MPa oxygen is added, instead
4h is answered, keeps pressure constant in reaction process.Reaction product is analyzed using GC-MS, and pyridyl phthalimide is received
Rate is 85%.
Embodiment 2-23
In addition to catalyst and dosage, pressure, reaction time difference, catalyst activity evaluation are same as Example 1.React item
Part and catalysis reaction result are shown in Table 1.Catalyst and dosage, oxygen pressure, reaction temperature and reaction time pair as can be seen from Table 1
Catalytic effect has an impact.As reaction temperature (embodiment 2 and 3), catalyst amount (embodiment 2 and 5), oxygen pressure (are implemented
Example 3 and 5) and (embodiment 5 and 6) in reaction time increase, yield increase.Catalyst amount increases oxygen pressure and increases, N- benzene
Base phthalimide yield is consequently increased.The oxides such as transition metal V, Fe, Co, Mn, Cu, Cr, Mo, Ce, Nb, W or
Person's metal salt all shows preferable effect.
1 1- indone of table and aniline oxidation prepare pyridyl phthalimide
Embodiment 24-36
In addition to aromatic ketone substrate and solvent usage difference, catalyst activity evaluation is same as Example 1.It reaction condition and urges
Change reaction result and is shown in Table 2.The aromatic ketone that different kinds of aromatic ring replaces can generate corresponding N- substituted imides with aniline.
2 distinct fragrance ketone substrate of table is that substrate synthesizes N- substituted imides with aniline
Embodiment 37-58
In addition to organic primary amine substrate is different, catalyst activity evaluation is same as Example 1.Reaction result is shown in Table 3.Difference has
Machine primary amine can generate corresponding N- substituted imides.
The different organic primary amines of table 3 and 1- indone are substrate synthesizing imide
Inventive substrate wide adaptation range, oxidation efficiency is high, and product yield is high；Using air or oxygen as oxygen source, economical,
Environmental protection has a good application prospect.
Claims (8)
1. a kind of synthetic method of N- substituted imides, it is characterised in that: with one of air or oxygen or two kinds for oxygen
Source, under the action of catalyst, 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 one of metal salt or
It is two or more；
The aromatic ketone is indone and its aromatic ring substitutive derivative, tetralone and its aromatic ring substitutive derivative, benzosuberone
And its one of aromatic ring substitutive derivative or two or more；
Substituent group on the derivative is OCH3、F、Cl、Br、I、NO2、CH3One of or two or more, substituent group
Number is 1-6；
The primary amine is aniline and its cyclosubstituted derivative of benzene, benzylamine and its cyclosubstituted derivative of benzene, naphthylamines and its naphthalene nucleus
Substituted derivative, the fat primary amine of C1-C18；
Substituent group is OCH in the cyclosubstituted derivative of benzene3、F、Cl、Br、I、NO2、CH3One of or two or more；It takes
The number of Dai Ji is 1-5；
Substituent group is OCH in the cyclosubstituted derivative of naphthalene3、F、Cl、Br、I、NO2、CH3One of or two or more；It takes
The number of Dai Ji is 1-7.
2. according to the method described in claim 1, it is characterized by: oxygen source used in the fragrance oxidation of ketones is in air or oxygen
It is one or two kinds of, wherein oxygen partial pressure be 0.1-2MPa, reaction temperature be 60-180 DEG C, reaction time 1-48h.
3. according to the method described in claim 1, it is characterized by:
Oxygen source used in the fragrance oxidation of ketones is one of air or oxygen or two kinds, wherein oxygen partial pressure 0.4-1MPa,
100-160 DEG C of reaction temperature, reaction time 6-24h.
4. according to the method described in claim 1, it is characterized by:
In terms of metal, used catalyst dosage is the 0.1-30mol% of primary amine.
5. according to the method described in claim 1, it is characterized by:
In terms of metal, used catalyst preferable amount is the 1-20mol% of primary amine.
6. according to the method described in claim 1, it is characterized by: solvent for use is toluene, chlorobenzene, N, N- diformamide
(DMF), one of normal octane, tetrahydrofuran (THF), dioxane, methanol, ethyl alcohol, dimethyl sulfoxide (DMSO) or two
Kind or more, the mass concentration 1-80wt% of aromatic ketone and primary amine in solvent.
7. according to the method described in claim 1, it is characterized by:
The preferred 1-40wt% of the mass concentration of the aromatic ketone and primary amine in solvent.
8. according to claim 1,6 or 7 any method, it is characterised in that: the molar ratio of aromatic ketone and amine is 1:1-5.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101139316A (en) * | 2007-10-18 | 2008-03-12 | 北京大学 | Anthraquinone imide compound and method for making same |
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| 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 |
|---|
| 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;Steven D. Wyrick, et al.;《J. Med. Chem.》;19871231;第30卷;第1798-1806页 * |
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