CN109020829A - A method of preparing imine compound - Google Patents
A method of preparing imine compound Download PDFInfo
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- CN109020829A CN109020829A CN201811120393.4A CN201811120393A CN109020829A CN 109020829 A CN109020829 A CN 109020829A CN 201811120393 A CN201811120393 A CN 201811120393A CN 109020829 A CN109020829 A CN 109020829A
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- copper catalyst
- reaction
- aminated compounds
- copper
- imine compound
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (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 method for preparing imine compound, the method, in the case that anaerobic agent there are coupled with copper catalyst catalysis aminated compounds and prepare imines.The present invention in the case that anaerobic agent there are using copper catalyst catalysis amine coupling prepare imines, can effectively solve the problems, such as that imines is easy by peroxidating, meanwhile, the preparation of copper catalyst that this method uses is simple, and efficient stable is cheap.
Description
Technical field
The invention belongs to organic chemical synthesis fields, and in particular to a method of prepare imine compound.
Background technique
Imine compound is very important a kind of organic synthesis intermediate and important nitrogen source, in organic, drug, day
All there is extremely important application in right product and commercial synthesis.
The logical condensation dependent on aldehyde/ketone and amine of the preparation of imines, however, such method usually requires a cumbersome operation
The water in reaction system is removed, is developed to the direction of product with driving a reaction.In recent years, oxidizing process, which prepares imines, becomes one
The effective method of kind, the selective oxidation especially carried out under catalytic condition with oxygen, hydrogen peroxide etc. are widely paid close attention to.Example
As N.Mizuno group reports Ru/Al2O3Can oxygen catalytic oxidation benzylamine, under conditions of 100 DEG C, using benzotrifluoride as molten
Level-one benzylamine is oxidized to nitrile by agent, and second level benzylamine is oxidized to imines.Robert J.Angelici et al. is reported with Au/Al2O3For
Catalyst reacts for 24 hours under the conditions of 100 DEG C in high pure oxygen, obtains imine compound, these methods are usually held more demanding
Oxygen concentration, due to this life of imines have oxidizable characteristic, it is easy to there is the situation of peroxidating, meanwhile, such method
The noble metal catalysts such as the Ru used, Au are expensive.Therefore, it develops in the case of a kind of anaerobic agent exists and is catalyzed amine coupling system
The method of standby imines, which is one, has challenge and the work of important research meaning.
Summary of the invention
It is described the present invention provides a kind of preparation method of imines for defect present in existing imines preparation method
Method in the case that anaerobic agent there are using copper catalyst catalysis amine coupling prepare imines, can effectively solve imines be easy by mistake
The problem of oxidation, meanwhile, the copper catalyst preparation that this method uses is simple, and efficient stable is cheap.
The technical solution of the present invention is as follows:
A method of preparing imine compound, which is characterized in that in the case that anaerobic agent there are with copper catalyst
Catalysis aminated compounds, which couples, prepares imines, and by substrate aminated compounds, solvent, copper catalyst is added in reactor, and nitrogen is protected
Lower temperature reaction is protected, reaction terminates, and imine compound can be obtained in separation；Reaction formula is as follows:
Wherein, copper catalyst Cu/Al2O3, Cu/HT (hydrotalcite), Cu/SiO2, in Cu/HAP (hydroxyapatite) one
Kind；R in aminated compounds is aryl, substituted aryl, any one in heteroaryl；Wherein, aryl is phenyl, naphthalene, anthracene
Any one of base, phenanthryl, heteroaryl are furyl, thienyl, any one in pyridyl group.
As a preferred embodiment, copper catalyst Cu/Al2O3。
As a preferred embodiment, copper catalyst Cu/Al2O3The preparation method comprises the following steps:
(1) aluminum oxide: 500 DEG C of activation 4h of aluminum oxide is activated；
(2) Cu (II)/Al is prepared2O3: in deionized water by copper trifluoromethanesulfcomposite dissolution, then it is added three after activation
Al 2 O, wherein 1h is stirred at room temperature with ammonium hydroxide tune PH to 8 for 1:3 in the weight ratio of copper trifluoromethanesulfcomposite and aluminum oxide,
Filtering, deionized water washing, dry Cu (II)/Al2O3；
(3) Cu/Al is prepared2O3: by obtained Cu (II)/Al2O3180 DEG C of vacuum drying 0.5h of temperature control, are pressed by 180 DEG C of temperature control
Power 1atm is passed through hydrogen reducing 0.5h, and obtaining black powder is Cu/Al2O3。
As a preferred embodiment, the R in aminated compounds is phenyl, and C1-C4 alkyl-substituted phenyl is halogen-substituted
Base, naphthalene, any one in thienyl.
As a preferred embodiment, solvent be one of toluene, paraxylene, ortho-xylene, meta-xylene, chlorobenzene or
It is a variety of.
As a preferred embodiment, reaction temperature is 110-140 DEG C.
The beneficial effects obtained by the present invention are as follows being:
(1) present invention in the case that anaerobic agent exist using copper catalyst be catalyzed amine coupling prepare imines, can effectively solve
The problem of certainly imines is easy by peroxidating.
(2) the copper catalyst preparation that the present invention uses is simple, and efficient stable is cheap.
Specific embodiment
The present invention is clearly and completely described below by specific embodiment, it is clear that described embodiment is only
It is a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiment of this practical invention, the common skill in this field
Art personnel every other embodiment obtained, belongs to protection scope of the present invention.
The preparation of 1 copper catalyst of embodiment
500 DEG C of activation 4h of 50g aluminum oxide are taken, take the activated ammoxidation dichloro of 1.0g that copper trifluoromethanesulfcomposite is added
(II) (3.3mg (1mmol) copper trifluoromethanesulfcomposite is dissolved in 50ml deionized water) in aqueous solution PH to 8.0, is adjusted with ammonium hydroxide,
25 DEG C of stirring 1h, filtering, deionized water wash to obtain solid, and 25 DEG C are dried in vacuum overnight to obtain blue powder, the indigo plant that will be obtained
Then 180 DEG C of vacuum drying 0.5h of color powder temperature control control 180 DEG C of temperature, pressure 1atm, lead to hydrogen reduction 0.5h, obtain black
Powder is Cu/Al2O3Catalyst.Elemental analysis is the results show that Cu/Al2O3The content of middle Cu atom is 4.5wt%, transmission electricity
Mirror image shows that Cu is nano particle.
The preparation of 2 imine compound of embodiment
1mmol benzylamine, copper catalyst (7mol%) as shown in the table, paraxylene 5ml, nitrogen protection are added in reaction flask
Under the conditions of be warming up to 130 DEG C reaction for 24 hours, sample detection, detection method is that 12 n-hexanes are interior target GC method.Experimental result
It is as follows:
| Serial number | Catalyst | Conversion ratio (%) | Selectivity (%) |
| 1 | Cu/Al2O3 | 82 | 97 |
| 2 | Cu/HT (hydrotalcite) | 33 | 93 |
| 3 | Cu/SiO2 | 99 | 76 |
| 4 | Cu/HAP (hydroxyapatite) | 18 | 99 |
Embodiment 3
1mmol benzylamine, the Cu/Al that embodiment 1 is prepared are added in reaction flask2O3(mol%), paraxylene 5ml, nitrogen
130 DEG C of reactions are warming up under the conditions of gas shielded for 24 hours, sample detection, detection method is that 12 n-hexanes are interior target GC method.It is real
It is as follows to test result:
Embodiment 4
1mmol benzylamine, the Cu/Al that embodiment 1 is prepared are added in reaction flask2O3(7mol%), paraxylene 5ml, nitrogen
For 24 hours, sample detection, detection method is that 12 n-hexanes are interior target GC method for temperature reaction under the conditions of gas shielded.Experimental result
It is as follows:
| Serial number | Reaction temperature (DEG C) | Conversion ratio (%) | Selectivity (%) |
| 1 | 110 | 32 | 99 |
| 2 | 130 | 82 | 97 |
| 3 | 140 | 99 | 99 |
Embodiment 5
The aminated compounds substrate of 1mmol structure as shown in the table, the Cu/ that embodiment 1 is prepared are added in reaction flask
Al2O3(7mol%), paraxylene 5ml are warming up to 140 DEG C of reactions, sample detection, detection method ten under the conditions of nitrogen protection
Two n-hexanes are interior target GC method, and reaction terminates, reaction solution is filtered, and filter cake washs (3 × 5mL), K with toluene2CO3It is water-soluble
Liquid washs (3 × 5mL), and filtrate concentration crosses column purification and obtains target product.Experimental result is as follows:
Remarks: separation yield item is that "-" indicates that the target product is not isolated and purified.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, all any modification, equivalent substitution, improvement and etc. be should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of method for preparing imine compound, which is characterized in that in the case that anaerobic agent there are urged with copper catalyst
Change aminated compounds, which couples, prepares imines, and by substrate aminated compounds, solvent, copper catalyst is added in reactor, nitrogen protection
Under the conditions of temperature reaction, reaction terminates, and imine compound can be obtained in separation；Reaction formula is as follows:
Wherein, copper catalyst Cu/Al2O3, Cu/HT (hydrotalcite), Cu/SiO2, one of Cu/HAP (hydroxyapatite)；
R in aminated compounds is aryl, substituted aryl, any one in heteroaryl；Wherein, aryl is phenyl, naphthalene, anthryl, phenanthrene
Any one in base, heteroaryl are furyl, thienyl, any one in pyridyl group.
2. the method as described in claim 1, which is characterized in that copper catalyst Cu/Al2O3。
3. method according to claim 2, which is characterized in that copper catalyst Cu/Al2O3The preparation method comprises the following steps:
(1) aluminum oxide: 500 DEG C of activation 4h of aluminum oxide is activated；
(2) Cu (II)/Al is prepared2O3: in deionized water by copper trifluoromethanesulfcomposite dissolution, three oxidations after activation are then added
Two aluminium, wherein 1h is stirred at room temperature with ammonium hydroxide tune PH to 8 for 1:3 in the weight of copper trifluoromethanesulfcomposite and aluminum oxide, filters, goes
Ion water washing, dry Cu (II)/Al2O3；
(3) Cu/Al is prepared2O3: by obtained Cu (II)/Al2O3180 DEG C of temperature control vacuum drying 0.5h, 180 DEG C of temperature control, pressure
1atm is passed through hydrogen reducing 0.5h, and obtaining black powder is Cu/Al2O3。
4. method according to claim 2, which is characterized in that the R in aminated compounds is phenyl, C1-C4 alkyl substituted benzene
Base, halogen substituted phenyl, naphthalene, any one in thienyl.
5. method as claimed in claim 4, which is characterized in that solvent be toluene, paraxylene, ortho-xylene, meta-xylene,
One of chlorobenzene is a variety of.
6. method as claimed in claim 5, which is characterized in that reaction temperature is 110-140 DEG C.
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| CN201811120393.4A CN109020829B (en) | 2018-09-26 | 2018-09-26 | Method for preparing imine compound |
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| CN201811120393.4A CN109020829B (en) | 2018-09-26 | 2018-09-26 | Method for preparing imine compound |
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| CN109020829B CN109020829B (en) | 2022-12-30 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478759A (en) * | 2014-12-04 | 2015-04-01 | 华东师范大学 | Preparation method for synthesizing imine through photo-catalytic oxidation of amine |
| CN106608839A (en) * | 2015-10-21 | 2017-05-03 | 中国科学院大连化学物理研究所 | Method for synthesizing imine-based structure compound through catalysis of amine |
| CN108097323A (en) * | 2016-11-24 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method that oxidative coupling of primary amine at room temperature prepares imines |
| CN108424373A (en) * | 2018-04-12 | 2018-08-21 | 上海应用技术大学 | A kind of method that primary amine oxidative coupling prepares imine compound |
-
2018
- 2018-09-26 CN CN201811120393.4A patent/CN109020829B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478759A (en) * | 2014-12-04 | 2015-04-01 | 华东师范大学 | Preparation method for synthesizing imine through photo-catalytic oxidation of amine |
| CN106608839A (en) * | 2015-10-21 | 2017-05-03 | 中国科学院大连化学物理研究所 | Method for synthesizing imine-based structure compound through catalysis of amine |
| CN108097323A (en) * | 2016-11-24 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method that oxidative coupling of primary amine at room temperature prepares imines |
| CN108424373A (en) * | 2018-04-12 | 2018-08-21 | 上海应用技术大学 | A kind of method that primary amine oxidative coupling prepares imine compound |
Non-Patent Citations (3)
| Title |
|---|
| AL-HMOUD, LINDA 等: "Reaction pathways over copper and cerium oxide catalysts for direct synthesis of imines from amines under aerobic conditions", 《JOURNAL OF CATALYSIS》 * |
| DAMODARA, DANDU 等: "Copper Nanoparticles from Copper Aluminum Hydrotalcite: An Efficient Catalyst for Acceptor- and Oxidant-Free Dehydrogenation of Amines and Alcohols", 《ADVANCED SYNTHESIS & CATALYSIS》 * |
| JIAQING WANG 等: "Common metal of copper(0) as an efficient catalyst for preparation of nitriles and imines by controlling additives", 《CHEM.COMMUN.》 * |
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