CN106588752B - The preparation method of one kind 1,2- bis- (4- piperidyl)-ethane - Google Patents
The preparation method of one kind 1,2- bis- (4- piperidyl)-ethane Download PDFInfo
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- CN106588752B CN106588752B CN201611117611.XA CN201611117611A CN106588752B CN 106588752 B CN106588752 B CN 106588752B CN 201611117611 A CN201611117611 A CN 201611117611A CN 106588752 B CN106588752 B CN 106588752B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The preparation method of one kind 1,2- bis- (4- piperidyl)-ethane.It is related to chemical industry synthesis field, more particularly to the preparation method of one kind 1,2- bis- (4- piperidyl)-ethane.It is at low cost and be avoided that the preparation method of 1, the 2- bis- of catalyst poisoning (4- piperidyl)-ethane to provide a kind of catalyst.The solvent is methanol, ethyl acetate, dimethylformamide, acetic acid, one or more kinds of mixed liquors in N-Methyl pyrrolidone.The catalyst is Pd-Pt/C composite catalyst, and wherein Pt-Pd is 5~1:1~5 in mass ratio, and Pt-Pd content of metal is 1-10%.The concentration of 1,2- bis- (4- the pyridyl group)-ethylene is 1-8mol/L.The concentration of 1,2- bis- (4- the pyridyl group)-ethylene is 3-5mol/L.It is filled with H2Pressure is 3.5-4.5Mpa in kettle.The reaction temperature is 70-110 DEG C.The present invention may be reused, and reduce production cost.
Description
Technical field
The present invention relates to chemical industry synthesis fields, more particularly to the preparation method of one kind 1,2- bis- (4- piperidyl)-ethane.
Background technique
1,2- bis- (4- piperidyl)-ethane is a kind of important fine-chemical intermediate, is widely used in new material
Preparation, due to its unique structure, is of great significance in terms of polyimides preparation.1,2- bis- (4- piperidyl)-ethane
The method of preparation, tradition report is 1,2- bis- (4- pyridyl group)-ethylene, is reacted under 150 atmospheric pressure of Raney's nickel catalyst.
Or with Pt, PtO2For catalyst, catalysis reaction, the catalyst is at high cost, and catalyst is easy poisoning, this is primarily due to 1,
The strong coordination of nitrogen-atoms, makes it be easy to be trapped in catalyst surface and make in catalyst in 2- bis- (4- piperidyl)-ethane
Poison.For this purpose, needing good exploitation selectivity, active height and stable catalyst system.
Summary of the invention
The present invention is in view of the above problems, to provide a kind of catalyst at low cost and be avoided that 1, the 2- bis- of catalyst poisoning
The preparation method of (4- piperidyl)-ethane.
The technical scheme is that including the following steps:
1) solvent, catalyst, 1,2- bis- (4- pyridyl group)-ethylene, sealing autoclave, are quantitatively adding in autoclave；
2) N alternately, is used to the autoclave of sealing2And H2Carry out at least 3 gas reactor displacements；
3), it is filled with H2, until in kettle pressure be 2-6MPa, material in kettle is stirred, set kettle interior reaction temperature as
It 60-120 DEG C, begins to warm up；When temperature rises to setting value, start timing, keep 30-150min, reaction terminates；
4), autoclave is cooled to immediately to 10-30 DEG C, be vented H2, material in kettle is filtered, catalyst, filter are removed
Liquid is concentrated to get 1,2- bis- (4- piperidyl)-ethane.
The solvent is methanol, ethyl acetate, dimethylformamide, acetic acid, a kind of in N-Methyl pyrrolidone or two
Kind or more mixed liquor.
The catalyst is Pd-Pt/C composite catalyst, and wherein Pt-Pd is 5~1:1~5, Pt-Pd metal in mass ratio
Load capacity is 1-10%.
The concentration of 1,2- bis- (4- the pyridyl group)-ethylene is 1-8mol/L.
The concentration of 1,2- bis- (4- the pyridyl group)-ethylene is 3-5mol/L.
It is filled with H2Pressure is 3.5-4.5Mpa in kettle.
The reaction temperature is 70-110 DEG C.
Reaction process of the invention is as follows:
The present invention uses Pd-Pt/C composite catalyst, using cheap hydrogen as raw material, to 1,2- bis- (4- pyridyl group)-second
Alkene carries out catalytic hydrogenation, prepares 1,2- bis- (4- piperidyl)-ethane, overcomes and prepare 1,2- bis- (4- piperidyl) in the prior art
The problems such as yield is low in ethane reaction, at high cost, and side reaction is more.
It has the advantages that and 1) is with methanol, ethyl acetate, dimethylformamide, acetic acid, N-Methyl pyrrolidone
Solvent, for other solvents, the above solvent has good chemical stability and thermal stability, in addition, also having choosing
The advantages that selecting property is high, corrosivity is small, Yi Huishou, on reaction process of the present invention substantially without influence；2) the reaction required temperature and pressure
Power is lower, energy saving；3) reaction yield is high, and the time is short, improves conversion ratio and product purity；4) used in reaction process to urge
Agent preparation is simple, may be reused, reduces production cost；5) post-reaction treatment is simple, can be realized and urges by filtering
Qualified products can be obtained in the separation of agent, concentration.
Specific embodiment
The present invention is illustrated below with reference to embodiment.
Embodiment 1
Composite catalyst [Pd-Pt (5:1)]/C, 1mol/L of methanol, mass fraction 1% is quantitatively adding in autoclave
1,2- bis- (4- pyridyl group)-ethylene, sealing autoclave alternately use N2And H2Displacement 3 times, is filled with H2, until pressure in autoclave
For 2Mpa, reaction temperature is set as 60 DEG C, constant temperature oil bath is put into and begins to warm up and stir.When temperature rises to 60 DEG C, continue anti-
30min is answered, after reaction, autoclave is cooled to 30 DEG C, is vented H2Afterwards, it filters, removes catalyst, filtrate is concentrated to get production
Product 1,2- bis- (4- piperidyl)-ethane, yield 82%.
Embodiment 2
1, the 2- bis- of ethyl acetate, mass fraction 5% [Pd-Pt (1:1)]/C, 4mol/L is quantitatively adding in autoclave
(4- pyridyl group)-ethylene, sealing autoclave alternately use N2And H2Displacement 3 times, is filled with H2, until pressure is 4MPa in autoclave,
Reaction temperature is set as 70 DEG C, constant temperature oil bath is put into and begins to warm up.When temperature rises to 70 DEG C, sustained response 60min, reaction knot
Autoclave is cooled to 10 DEG C, is vented H by Shu Hou2Afterwards, it filters, removes catalyst, filtrate concentration distillation obtains product 1,2- bis-
(4- piperidyl)-ethane, yield 98%.
Embodiment 3
Be quantitatively adding in autoclave dimethylformamide, mass fraction 10% [Pd-Pt (1:5)]/C, 8mol/L 1,
2- bis- (4- pyridyl group)-ethylene, sealing autoclave alternately use N2And H2Displacement 3 times, is filled with the H of 6MPa2, setting reaction temperature
Degree is 85 DEG C, is put into constant temperature oil bath and begins to warm up.When temperature rises to 85 DEG C, 80min is reacted, after reaction, by autoclave
20 DEG C are cooled to, H is vented2Afterwards, it filters, removes catalyst, filtrate concentration distillation obtains product 1,2- bis- (4- piperidyl)-second
Alkane, yield 91%.
Embodiment 4
Be quantitatively adding in autoclave methanol, ethyl acetate, dimethylformamide, mass fraction 5% [Pd-Pt (1:5)]/
C, 1 3mol/L, 2- bis- (4- pyridyl group)-ethylene, sealing autoclave alternately use N2And H2Displacement 3 times, is filled with H2, until high pressure
Pressure is 3.5MPa in kettle, sets reaction temperature as 95 DEG C, is put into constant temperature oil bath and begins to warm up.When temperature rises to 95 DEG C, hold
Autoclave is cooled to 25 DEG C, is vented H by continuous reaction 100min after reaction2Afterwards, it filters, removes catalyst, filtrate concentration
Distillation obtains product 1,2- bis- (4- piperidyl)-ethane, yield 93%.
Embodiment 5
Be quantitatively adding in autoclave N-Methyl pyrrolidone, mass fraction 3% [Pd-Pt (1:4)]/C, 5mol/L 1,
2- bis- (4- pyridyl group)-ethylene, sealing autoclave alternately use N2And H2Displacement 3 times, is filled with H2, until pressure is in autoclave
4.5MPa setting reaction temperature as 110 DEG C, it is put into constant temperature oil bath and begins to warm up.When temperature rises to 110 DEG C, sustained response
Autoclave is cooled to 15 DEG C, is vented H by 120min after reaction2Afterwards, it filters, removes catalyst, filtrate concentration is distilled
To product 1,2- bis- (4- piperidyl)-ethane, yield 88%.
Embodiment 6
Dimethylformamide, acetic acid, mass fraction 7% [Pd-Pt (4:1)]/C, 4mol/L are quantitatively adding in autoclave
1,2- bis- (4- pyridyl group)-ethylene, sealing autoclave, alternately use N2And H2Displacement 3 times, is filled with H2, until autoclave internal pressure
Power is 4MPa, sets reaction temperature as 120 DEG C, is put into constant temperature oil bath and begins to warm up.When temperature rises to 120 DEG C, sustained response
Autoclave is cooled to 12 DEG C, is vented H by 150min after reaction2Afterwards, it filters, removes catalyst, filtrate concentration is distilled
To product 1,2- bis- (4- piperidyl)-ethane, yield 91%.
Claims (6)
1. one kind 1, the preparation method of 2- bis- (4- piperidyl)-ethane, include the following steps:
1) solvent, catalyst, 1,2- bis- (4- pyridyl group)-ethylene, sealing autoclave, are quantitatively adding in autoclave；
2) N2 and H2, is alternately used to carry out at least 3 gas reactor displacements to the autoclave of sealing；
3) it, is filled with H2, until pressure is 2-6MPa in kettle, material in kettle is stirred, sets kettle interior reaction temperature as 60-120
DEG C, it begins to warm up；When temperature rises to setting value, start timing, keep 30-150min, reaction terminates；
4), autoclave is cooled to immediately to 10-30 DEG C, be vented H2, material in kettle is filtered, removes catalyst, filtrate is dense
Contracting obtains 1,2- bis- (4- piperidyl)-ethane,
It is characterized in that, the catalyst is Pd-Pt/C composite catalyst, wherein Pt-Pd is 5~1:1~5, Pt- in mass ratio
Pd content of metal is 1-10%.
2. a kind of preparation method of 1,2- bis- (4- piperidyl)-ethane according to claim 1, which is characterized in that described
Solvent is methanol, ethyl acetate, dimethylformamide, acetic acid, one or more kinds of mixing in N-Methyl pyrrolidone
Liquid.
3. a kind of preparation method of 1,2- bis- (4- piperidyl)-ethane according to claim 1, which is characterized in that described
The concentration of 1,2- bis- (4- pyridyl group)-ethylene is 1-8mol/L.
4. a kind of preparation method of 1,2- bis- (4- piperidyl)-ethane according to claim 3, which is characterized in that described
The concentration of 1,2- bis- (4- pyridyl group)-ethylene is 3-5mol/L.
5. a kind of preparation method of 1,2- bis- (4- piperidyl)-ethane according to claim 1, which is characterized in that be filled with
Pressure is 3.5-4.5Mpa in H2 to kettle.
6. a kind of preparation method of 1,2- bis- (4- piperidyl)-ethane according to claim 1, which is characterized in that described
Reaction temperature is 70-110 DEG C.
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| CH518936A (en) * | 1967-01-30 | 1972-02-15 | Ciba Geigy Ag | Process for the preparation of new basic substituted bis-piperidylalkanes |
| JP2003346574A (en) * | 2002-05-24 | 2003-12-05 | Mitsubishi Paper Mills Ltd | Silver salt/amine composite |
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Non-Patent Citations (1)
| Title |
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| Action of Sulfur on Certain Pyridine and Quinoline Derivatives. I. Action of Sulfur on 4-Picoline;Thayer, HI，等;《Journal of the American Chemical Society》;19480731;第70卷(第7期);第2330-2333页 |
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