CN109438325A - A kind of method of ring valeryl imines catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles - Google Patents
A kind of method of ring valeryl imines catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles Download PDFInfo
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- CN109438325A CN109438325A CN201811482538.5A CN201811482538A CN109438325A CN 109438325 A CN109438325 A CN 109438325A CN 201811482538 A CN201811482538 A CN 201811482538A CN 109438325 A CN109438325 A CN 109438325A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/52—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring condensed with a ring other than six-membered
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Abstract
A kind of method that the present invention discloses catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles.Method of the invention is the PtV/ γ-Al using ring valeryl imines as raw material2O3For catalyst, octahydro pentamethylene [C] pyrroles is synthesized through catalytic hydrogenation.Its technical solution is as follows: by PtV/ γ-Al2O3Catalyst, ring valeryl imines, solvent dimethyl ether are added in autoclave, and the hydrogen of 3-10MPa is filled with into autoclave, and temperature of reactor is 80-150 DEG C, react 10-24 hours, with the yield of gas chromatographic analysis tracking octahydro pentamethylene [C] pyrroles.In method of the invention, PtV/ γ-Al2O3Method for preparing catalyst is simple；Using environmentally friendly, pollution-free, the easily operated control of method of catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles, the high income of octahydro pentamethylene [C] pyrroles is easy to industrialized production.
Description
Technical field
The present invention relates to the synthetic methods of important medicine intermediate octahydro pentamethylene [C] pyrroles a kind of, are Specifically
One kind is using ring valeryl imines as raw material, PtV/ γ-Al2O3For catalyst, synthesize octahydro pentamethylene [C] pyrroles's through catalytic hydrogenation
Method.
Technical background
Octahydro pentamethylene [C] pyrroles is a kind of important medicine intermediate, is mainly used to the pass of synthesis treatment hepatitis C
Key drug telavi (Telaprevir) and the drug gliclazide (Gliclazide) for treating diabetes, octahydro pentamethylene
[C] pyrroles has biggish demand in medical industry, extensive to synthesize octahydro pentamethylene using environmental protection, economic method
[C] pyrroles has great significance.
The synthetic method of octahydro pentamethylene [C] pyrroles of reporting is using LiAlH4It is restored in tetrahydrofuran solution
Ring valeryl imines (Griot et al., Helvetica ChimicaActa, 42,1959,67-72), octahydro pentamethylene [C] pyrrole
The yield coughed up is up to 51%；Chinese patent (CN201310627653.8) discloses a kind of using NaBH4For reducing agent, ZnCl2For
Promotor, the method that ring valeryl imines synthesis octahydro pentamethylene [C] pyrroles is restored in appropriate solvent.In above two method,
Reducing agent LiAlH used in the former4It is a kind of chemical reagent that chance water easily acutely decomposes, uses synthesis octahydro ring fairly large
When pentane [C] pyrroles, there are very important security risks, meanwhile, there is relatively large harmful waste water to discharge；Used in the latter
NaBH4/ZnCl2Reduction system is also easy to produce a large amount of boracic, waste water containing Zn Cr coating in actual industrial production, do not meet environmental protection,
Green Chemistry requirement.
Catalytic hydrogenation method has the characteristics that environmentally protective since hydrogenation byproduct is mainly water.Document
(ChemCatChem, 6 (9), 2014,2621-2625) report a kind of using Rh6(CO)16/Mo(CO)6For catalyst,
Under the hydrogen reaction pressure of 10MPa, the method for catalysis ring valeryl imines hydrogenation synthesis octahydro pentamethylene [C] pyrroles.But this method
Employed in metal carbonyl complex be more toxic, to the health of direct labor have larger harm, and molecular state
Rh6(CO)16、Mo(CO)6It is easy to run off in catalysis reaction.
Summary of the invention
The purpose of the present invention is: for existing using ring valeryl imines as the method for Material synthesis octahydro pentamethylene [C] pyrroles
The shortcomings that and the method for more environmentally protective, efficient, economic catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles a kind of is provided
(being shown below).It is a further object of the present invention to provide PtV/ γ-Al in above-mentioned catalytic hydrogenation method2O3For the system of catalyst
Preparation Method.
Technical problem to solve of the invention adopts the following technical scheme that
A kind of method of catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles, by PtV/ γ-Al2O3Catalyst, ring valeryl are sub-
Amine, solvent dimethyl ether are added in autoclave, and high pressure hydrogen is filled with into autoclave, set temperature of reactor, use gas
The yield of analysis of hplc tracking octahydro pentamethylene [C] pyrroles.
The catalytic hydrogenation reaction carries out in a high pressure reaction kettle.
The Hydrogen Vapor Pressure is 3-10MPa.
The reaction temperature is 80-150 DEG C, reaction time 10-24 hour.
PtV/ γ-Al used in the catalytic hydrogenation method2O3Catalyst, specifically the preparation method is as follows: to impregnate legal system
Standby PtV/ γ-Al2O3Catalyst, by a certain amount of catalyst carrier (with γ-Al2O3For) be immersed in and matched by certain mass
In the chloroplatinic acid of configuration, the mixed solution of ammonium metavanadate, abundant adsorptive；Sample after dipping is placed in tubular type Muffle furnace
It is warming up to 500-800 DEG C, 3-5 hours are roasted in hydrogen reducing atmosphere to get PtV/ γ-Al is arrived2O3Catalyst.
PtV/ γ-the Al of the preparation2O3The mass ratio of each component is Pt:V: γ-Al in catalyst2O3=0.01-0.8:
0.01-0.015:1.
In the method for preparing catalyst, catalyst carrier can be γ-Al2O3, diatomite, active carbon, hydrotalcite, two
Silicon oxide molecular sieve etc..
In the method for preparing catalyst, reducing atmosphere VH2: VN2=1:9, reduction throughput are 20 ml/mins.
Advantage of the invention:
1, designed preparation and the PtV/ γ-Al used in the present invention2O3Catalyst mainly uses simple infusion process, roasting
Reduction method preparation is burnt, the preparation method of catalyst is simple, cost is relatively low.
2, using ring valeryl imines as raw material, hydrogen is reducing agent, through PtV/ γ-Al2O3The synthesis of catalyst Hydrogenation
Octahydro pentamethylene [C] pyrroles, discharges without poisonous waste in reaction process, and the catalytic hydrogenation method is more environmentally protective.
3, the method for catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles provided in the present invention, it is easy to operate, easily-controllable
System, is easy to industrial amplification production.
Specific embodiment
Embodiment 1
A kind of method of catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles, firstly, by chloroplatinic acid, ammonium metavanadate, γ-
Al2O3, distilled water by following element mass ratioes be added reactor in, Pt:V: γ-Al2O3: H2O=0.02:0.03:1:100,
Magnetic agitation keeps its scattered adsorption uniform at room temperature, then removes moisture by evaporation, obtained solid sample is placed in tubular type horse
Not in furnace, at 550 DEG C, the reducing atmosphere (V of 20 ml/minsH2: VN2=1:9) in roasting 5 hours to get arrive PtV/ γ-
Al2O3Catalyst.By the PtV/ γ-Al of above-mentioned preparation2O31L high is added in catalyst 1g, 30g ring valeryl imines, 500mL dimethyl ether
It presses in reaction kettle, with hydrogen atmospheric replacement 3 times, is re-filled with 5MPa hydrogen, reaction kettle is warming up to 100 DEG C, is catalyzed under stirring
Hydrogenation reaction in reaction process, with the reduction of Hydrogen Vapor Pressure, continues to add hydrogen into reactor maintaining reaction pressure 5MPa
It is constant, it is 36.8% with the yield of gas chromatographic analysis octahydro pentamethylene [C] pyrroles.
Embodiment 2
A kind of method of catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles, firstly, by chloroplatinic acid, ammonium metavanadate, γ-
Al2O3, distilled water by following element mass ratioes be added reactor in, Pt:V: γ-Al2O3: H2O=0.04:0.07:1:100,
Magnetic agitation keeps its scattered adsorption uniform at room temperature, then removes moisture by evaporation, obtained solid sample is placed in tubular type horse
Not in furnace, at 600 DEG C, the reducing atmosphere (V of 20 ml/minsH2: VN2=1:9) in roasting 3 hours to get arrive PtV/ γ-
Al2O3Catalyst.By the PtV/ γ-Al of above-mentioned preparation2O31L high is added in catalyst 1g, 30g ring valeryl imines, 500mL dimethyl ether
It presses in reaction kettle, with hydrogen atmospheric replacement 3 times, is re-filled with 7MPa hydrogen, reaction kettle is warming up to 120 DEG C, is catalyzed under stirring
Hydrogenation reaction in reaction process, with the reduction of Hydrogen Vapor Pressure, continues to add hydrogen into reactor maintaining reaction pressure not
Become, is 65.3% with the yield of gas chromatographic analysis octahydro pentamethylene [C] pyrroles.
Embodiment 3
A kind of method of catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles, firstly, by chloroplatinic acid, ammonium metavanadate, γ-
Al2O3, distilled water by following element mass ratioes be added reactor in, Pt:V: γ-Al2O3: H2O=0.06:0.08:1:100,
Magnetic agitation keeps its scattered adsorption uniform at room temperature, then removes moisture by evaporation, obtained solid sample is placed in tubular type horse
Not in furnace, at 650 DEG C, the reducing atmosphere (V of 20 ml/minsH2: VN2=1:9) in roasting 4 hours to get arrive PtV/ γ-
Al2O3Catalyst.By the PtV/ γ-Al of above-mentioned preparation2O31L high is added in catalyst 1g, 30g ring valeryl imines, 500mL dimethyl ether
It presses in reaction kettle, with hydrogen atmospheric replacement 3 times, is re-filled with 8MPa hydrogen, reaction kettle is warming up to 130 DEG C, is catalyzed under stirring
Hydrogenation reaction in reaction process, with the reduction of Hydrogen Vapor Pressure, continues to add hydrogen into reactor maintaining reaction pressure not
Become, is 72.7% with the yield of gas chromatographic analysis octahydro pentamethylene [C] pyrroles.
Embodiment 4
A kind of method of catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles, firstly, by chloroplatinic acid, ammonium metavanadate, γ-
Al2O3, distilled water by following element mass ratioes be added reactor in, Pt:V: γ-Al2O3: H2O=0.07:0.09:1:100,
Magnetic agitation keeps its scattered adsorption uniform at room temperature, then removes moisture by evaporation, obtained solid sample is placed in tubular type horse
Not in furnace, at 600 DEG C, the reducing atmosphere (V of 20 ml/minsH2: VN2=1:9) in roasting 5 hours to get arrive PtV/ γ-
Al2O3Catalyst.By the PtV/ γ-Al of above-mentioned preparation2O31L high is added in catalyst 1g, 30g ring valeryl imines, 500mL dimethyl ether
It presses in reaction kettle, with hydrogen atmospheric replacement 3 times, is re-filled with 8MPa hydrogen, reaction kettle is warming up to 150 DEG C, is catalyzed under stirring
Hydrogenation reaction in reaction process, with the reduction of Hydrogen Vapor Pressure, continues to add hydrogen into reactor maintaining reaction pressure not
Become, is 80.4% with the yield of gas chromatographic analysis octahydro pentamethylene [C] pyrroles.
Embodiment 5
A kind of method of catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles, firstly, by chloroplatinic acid, ammonium metavanadate, γ-
Al2O3, distilled water by following element mass ratioes be added reactor in, Pt:V: γ-Al2O3: H2O=0.08:0.07:1:100,
Magnetic agitation keeps its scattered adsorption uniform at room temperature, then removes moisture by evaporation, obtained solid sample is placed in tubular type horse
Not in furnace, at 650 DEG C, the reducing atmosphere (V of 20 ml/minsH2: VN2=1:9) in roasting 5 hours to get arrive PtV/ γ-
Al2O3Catalyst.By the PtV/ γ-Al of above-mentioned preparation2O31L high is added in catalyst 1g, 30g ring valeryl imines, 500mL dimethyl ether
It presses in reaction kettle, with hydrogen atmospheric replacement 3 times, is re-filled with 9MPa hydrogen, reaction kettle is warming up to 150 DEG C, is catalyzed under stirring
Hydrogenation reaction in reaction process, with the reduction of Hydrogen Vapor Pressure, continues to add hydrogen into reactor maintaining reaction pressure not
Become, is 86.4% with the yield of gas chromatographic analysis octahydro pentamethylene [C] pyrroles.
Claims (8)
1. a kind of method of catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles.It is characterized by: by PtV/ γ-Al2O3Catalyst,
Ring valeryl imines, dimethyl ether etc. are added in autoclave, and in high pressure hydrogen atmosphere, catalytic hydrogenation synthesizes octahydro pentamethylene
[C] pyrroles.
2. the method for catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles according to claim 1, it is characterised in that: PtV/
γ-Al2O3The preparation method of catalyst is will to impregnate the γ-Al for being adsorbed with chloroplatinic acid, ammonium metavanadate2O3It is placed in tubular type Muffle furnace
In be warming up in 500-800 DEG C of reducing atmosphere and roast 3-5 hours to get to PtV/ γ-Al2O3Catalyst.
3. the method for catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles according to claim 1 or 2, it is characterised in that:
Tubular type Muffle furnace roasting preparation PtV/ γ-Al2O3When catalyst, reducing atmosphere VH2: VN2=1:9, reduction throughput are 20 millis
Liter/min.
4. the method for catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles according to claim 1 or 2, it is characterised in that:
PtV/γ-Al2O3The mass ratio of each component is Pt:V: γ-Al in catalyst2O3=0.01-0.8:0.01-0.015:1.
5. the method for catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles according to claim 1, it is characterised in that: catalysis
Hydrogenation reaction carries out in a high pressure reaction kettle, and temperature of reaction kettle is 80-150 DEG C.
6. the method for catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles according to claim 1, it is characterised in that: high pressure
The pressure of hydrogen is 3-10MPa in reaction kettle.
7. the method for catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles according to claim 1, it is characterised in that: reaction
The solvent of system is dimethyl ether.
8. the method for catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles according to claim 1, it is characterised in that: utilize
The yield of gas-chromatography or gas chromatograph-mass spectrometer analysis detection octahydro pentamethylene [C] pyrroles, yield may be up to 86.4%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039127A (en) * | 2010-12-20 | 2011-05-04 | 昆明理工大学 | Method for preparing catalyst of alpha/gamma-Al2O3-loaded nano-precious metal particles |
| CN103601666A (en) * | 2013-11-28 | 2014-02-26 | 遵义医学院 | Preparation method of octahydrocyclopentane[C]pyrrole |
| CN103848719A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院大连化学物理研究所 | Method for preparing 1,5-pentanediol via selective hydrogenolysis of tetrahydrofurfuryl alcohol |
| CN106582634A (en) * | 2016-11-16 | 2017-04-26 | 盘锦格林凯默科技有限公司 | Highly active ruthenium-carbon catalyst modified by transition metal atoms and preparation method thereof |
-
2018
- 2018-12-05 CN CN201811482538.5A patent/CN109438325A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039127A (en) * | 2010-12-20 | 2011-05-04 | 昆明理工大学 | Method for preparing catalyst of alpha/gamma-Al2O3-loaded nano-precious metal particles |
| CN103848719A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院大连化学物理研究所 | Method for preparing 1,5-pentanediol via selective hydrogenolysis of tetrahydrofurfuryl alcohol |
| CN103601666A (en) * | 2013-11-28 | 2014-02-26 | 遵义医学院 | Preparation method of octahydrocyclopentane[C]pyrrole |
| CN106582634A (en) * | 2016-11-16 | 2017-04-26 | 盘锦格林凯默科技有限公司 | Highly active ruthenium-carbon catalyst modified by transition metal atoms and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ANNA M. MAJ等: "Efficient Catalytic Hydrogenation of N-Unsubstituted Cyclic Imides to Cyclic Amines", 《CHEMCATCHEM》 * |
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Application publication date: 20190308 |