CN108178728A - It is a kind of double（2- aminoisobutyric bases）The synthetic method of amine - Google Patents
It is a kind of double（2- aminoisobutyric bases）The synthetic method of amine Download PDFInfo
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- CN108178728A CN108178728A CN201711378504.7A CN201711378504A CN108178728A CN 108178728 A CN108178728 A CN 108178728A CN 201711378504 A CN201711378504 A CN 201711378504A CN 108178728 A CN108178728 A CN 108178728A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to a kind of synthetic method of bis- (2 aminoisobutyric base) amine, this method catalyzes and synthesizes bis- (2 aminoisobutyric base) amine under hydrogen atmosphere, includes the following steps using 2 aminoisobutanols and aminating agent as raw material：(1) 2 aminoisobutanols, aminating agent and catalyst are added in autoclave；(2) a certain amount of hydrogen is passed through, reaction 6h~15h is carried out under the conditions of 160 DEG C~200 DEG C；(3) Filtration of catalyst after reaction obtains the sterling of bis- (2 aminoisobutyric base) amine after reaction solution rectifying.Using this method, building-up process cleaning, easy to operate, single step reaction can obtain target product, suitable for prepare with scale.
Description
Technical field
The invention belongs to organic amines to synthesize field, and in particular to a kind of synthetic method of bis- (2- aminoisobutyrics base) amine.
Background technology
Bis- (2- aminoisobutyrics base) amine belong to extraordinary amine compound, are a kind of important organic synthesis intermediates, extensively
It is general to be applied to the fields such as drug, pesticide, surfactant.In recent years, the compound of the class formation low volatility paint in and
Agent field gets more and more people's extensive concerning.
At present, the synthetic method of bis- (2- aminoisobutyrics base) amine is reported both at home and abroad few.United States Patent (USP) US2011/
A kind of synthetic method of bis- (2- aminoisobutyrics base) amine is reported in 0151615 A1.This method is on the basis that foreign literature is reported
On be partly improved, using nitropropane, formaldehyde and azanol as starting material, synthesize bis- (2- nitros isobutyl group) aminations first
Close object, then it is hydrogenated under an atmosphere of hydrogen be obtained by the reaction target product, two step total recoverys are 43.2%.This method is with nitropropane
For starting material, but nitropropane property is unstable, and inflammable and explosive, process safety is relatively low；Reaction experience dinitro compound
Two steps of synthesis and hydrogenation reaction, hydrogenation process be up to 5 days, there are problems that step is more, time-consuming.
Invention content
The technical problems to be solved by the invention are pacified aiming at the unstable technique brought of raw material existing for existing method
Full property is relatively low and the shortcomings of synthesis step is more, time-consuming, provides that one kind is clean to be easy to industrialized bis- (2- aminoisobutyrics
Base) amine synthetic method.
In order to solve the above technical problems, the present invention adopts the following technical scheme that, using 2- aminoisobutanols and aminating agent as original
Material, bis- (2- aminoisobutyrics base) amine are catalyzed and synthesized under hydrogen atmosphere, are included the following steps：
(1) 2- aminoisobutanols, aminating agent and catalyst are added in autoclave, the aminating agent for liquefied ammonia, 1,
2- diaminopropanes, catalyst be through in Cr, Cu, Sn it is a kind of it is metal-modified after Ni metallic catalysts, the use of modified metal
Measure 0.1%~2% for Ni amount of metal；
(2) hydrogen is passed through to reactor pressure to 0~5MPa, is warming up to 160 DEG C~200 DEG C reaction 6h~15h；
(3) Filtration of catalyst after reaction obtains the sterling of bis- (2- aminoisobutyrics base) amine after reaction solution rectifying.
The structural formula of bis- (the 2- aminoisobutyrics base) amine of target product is as follows：
Preferred technical solution is that the dosage of modified metal is the 0.1% of Ni amount of metal in the Ni metallic catalysts
~1.2%；When aminating agent is 1,2- diaminopropanes, reaction can not also add in 2- aminoisobutanols and can obtain bis- (2-
Aminoisobutyric base) amine；The initial pressure for being passed through amount to the reaction kettle of hydrogen is 0.5~4MPa.
Compared with prior art, the present invention it has the following advantages that：
(1) synthesis process cleans, and single step reaction can obtain target product, and the prior art needs two-step reaction；
(2) raw material 2- aminoisobutanols toxicity is low, and performance is stablized, and the prior art uses nitropropane as raw material, technique
Safety is relatively low；
(3) when aminating agent is liquefied ammonia, reaction can be with 1, the 2- diaminopropanes of coproduction high added value.
Specific embodiment
The present invention is described in further detail below by specific embodiment, but protection scope of the present invention and is not only limited
In this.
Embodiment 1
By the 2- aminoisobutanols of 200g, 7.0g Ni catalyst is added in autoclave, after the air in hydrogen displacement kettle
It vacuumizes, is passed through 86g liquefied ammonia, continue to be passed through hydrogen to 3MPa, be warming up to 190 DEG C, react 7h.Reaction solution is cooled down after reaction
To room temperature, filtering reacting liquid recycling catalyst.On the basis of consuming Unit Weight 2- aminoisobutanols, conversion ratio 52.6% is double
(2- aminoisobutyrics base) amine selectivity 25.3%, 1,2- diaminopropanes selectivity 67.8%.
Embodiment 2
By the 2- aminoisobutanols of 200g, 10.0g Ni catalyst is added in autoclave, the air in hydrogen displacement kettle
After vacuumize, be passed through 95g liquefied ammonia, continue to be passed through hydrogen to 4MPa, be warming up to 185 DEG C, react 10h.Cooling is anti-after reaction
Liquid is answered to room temperature, filtering reacting liquid recycling catalyst.On the basis of consuming Unit Weight 2- aminoisobutanols, conversion ratio
61.6%, bis- (2- aminoisobutyrics base) amine selectivity 32.4%, 1,2- diaminopropanes selectivity 58.6%.
Embodiment 3
By 1, the 2- diaminopropanes of 200g, 10.0g Ni catalyst is added in autoclave, and kettle vacuumizes, and is passed through hydrogen
To 3.5MPa, 190 DEG C are warming up to, reacts 8h.Cooling reaction solution to room temperature, filtering reacting liquid recycles catalyst after reaction.
To consume Unit Weight 1, on the basis of 2- diaminopropanes, conversion ratio 12.6%, bis- (2- aminoisobutyrics base) amine selectivity
74.3%.
Embodiment 4
By the 2- aminoisobutanols of 40g, 1, the 2- diaminopropanes of 160g, 8.0g Ni catalyst is added in autoclave,
Kettle vacuumizes, and is passed through hydrogen to 3.5MPa, is warming up to 190 DEG C, reacts 6h.Cooling reaction solution is filtered to room temperature after reaction
Reaction solution recycles catalyst.On the basis of consuming Unit Weight 2- aminoisobutanols and 1,2- diaminopropanes, conversion ratio
21.5%, bis- (2- aminoisobutyrics base) amine selectivity 76.9%.
Embodiment 5
By the 2- aminoisobutanols of 40g, 1, the 2- diaminopropanes of 160g, 8.0g Ni catalyst is added in autoclave,
Kettle vacuumizes, and reaction system is not passed through hydrogen additionally, is warming up to 190 DEG C, reacts 7h.Reaction solution is cooled down after reaction to room
Temperature, filtering reacting liquid recycling catalyst.To consume Unit Weight 1, on the basis of 2- diaminopropanes, conversion ratio 11.2%, bis- (2-
Aminoisobutyric base) amine selectivity 61.7%.
Embodiment 6
The reaction solution that embodiment 2 obtains is subjected to rectifying and obtains bis- (2- aminoisobutyrics base) amine, purity 99.0% obtains
The nuclear-magnetism characterize data of bis- (2- aminoisobutyrics base) amine products is as follows：
1HNMR(CDCl3):1.09(-CH3), 1.34 (- NH ,-NH2), 2.47 (- CH2)；
13CNMR(CDCl3):28.66(-CH3), 49.99 (- C), 63.10 (- CH2)。
Claims (4)
1. a kind of synthetic method of bis- (2- aminoisobutyrics base) amine, using 2- aminoisobutanols and aminating agent as raw material, in hydrogen item
Bis- (2- aminoisobutyrics base) amine are catalyzed and synthesized under part, are included the following steps：
(1) 2- aminoisobutanols, aminating agent and catalyst are added in autoclave, the aminating agent is liquefied ammonia or 1,2- bis-
Aminopropane, catalyst be through in Cr, Cu, Sn it is a kind of it is metal-modified after Ni metallic catalysts, the dosage of modified metal is
The 0.1%~2% of Ni amount of metal；
(2) hydrogen is passed through to reactor pressure to 0~5MPa, is warming up to 160 DEG C~200 DEG C reaction 6h~15h；
(3) Filtration of catalyst after reaction obtains the sterling of bis- (2- aminoisobutyrics base) amine after reaction solution rectifying.
2. the synthetic method of bis- (2- aminoisobutyrics base) amine according to claim 1, it is characterised in that the Ni metals
Catalyst, the dosage of modified metal are the 0.1%~1.2% of Ni amount of metal.
3. the synthetic method of bis- (2- aminoisobutyrics base) amine according to claim 1, it is characterised in that aminating agent 1,2-
Diaminopropanes, reaction are added without 2- aminoisobutanols and can obtain bis- (2- aminoisobutyrics base) amine.
4. the synthetic method of bis- (2- aminoisobutyrics base) amine according to claim 1, it is characterised in that be passed through the amount of hydrogen
Initial pressure to reaction kettle is 0.5~4MPa.
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| CN201711378504.7A CN108178728A (en) | 2017-12-19 | 2017-12-19 | It is a kind of double（2- aminoisobutyric bases）The synthetic method of amine |
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| CN201711378504.7A CN108178728A (en) | 2017-12-19 | 2017-12-19 | It is a kind of double（2- aminoisobutyric bases）The synthetic method of amine |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106810454A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of method for preparing hexamethylene diamine |
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2017
- 2017-12-19 CN CN201711378504.7A patent/CN108178728A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106810454A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of method for preparing hexamethylene diamine |
Non-Patent Citations (1)
| Title |
|---|
| WEIQIANG WANG等: "Reductive Amination of 2-Amino-2-methyl-1-propanol and Ammonia to Produce 2-Methyl-1,2-propanediamine over Raney Nickel Catalyst", 《CHEMISTRYSELECT》 * |
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Application publication date: 20180619 |