CN102206133A - Preparation method of 4,5,9,10-tetrahydropyrene - Google Patents
Preparation method of 4,5,9,10-tetrahydropyrene Download PDFInfo
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Abstract
The invention relates to a preparation method of 4,5,9,10-tetrahydropyrene. According to the invention, pyrene is treated as a raw material and a supported nanometer noble metal catalyst is used to carry out a selective hydrogenation reaction. Pyrene catalysis hydrogenation is a complex reaction which comprises a consecutive reaction and a parallel reaction simultaneously. The conversion rate of the raw material can achieve 100% and the yield of 4,5,9,10-tetrahydro-pyrene is nearly 90.0% through employing a tanker high pressure reactor and the supported nanometer noble metal under conditions that the temperature is from 20 to 150 DEG C, the pressure is from 0.2 to 8 MPa and the reaction period is from 1.0 to 80.0 h. The method has the prominent characteristics of low catalyst loading amount, good activity, high selectivity, and greatly reduced production cost compared with traditional technologies.
Description
Technical field
The present invention relates to a kind of preparation 4,5,9, the method for 10-tetrahydrochysene pyrene.
Background technology
4,5,9,10-tetrahydrochysene pyrene is a kind of important fine chemicals intermediate, can be used for the synthetic of fluorescence dye and medical research intermediate, as P.Soustek etc.
[1]Utilize 4,5,9, the synthetic fluorescent substance N-of 10-tetrahydrochysene pyrene replaces the amino pyrene of 2-; Vyacheslav etc.
[2]Utilize pyrene shortening product 4,5,9,10-tetrahydrochysene pyrene has synthesized the 2-ethynyl pyrene that is used for the researching DNA molecule modification.
4,5,9, the relevant information of 10-tetrahydrochysene pyrene: white crystal, molecular formula: C
16H
14, molecular weight: 206.3, CAS registration number: 781-17-9, fusing point: 138 ℃.4,5,9, the preparation of 10-tetrahydrochysene pyrene has caused people's attention very early, and it mainly is that selective catalytic hydrogenation by pyrene makes, but relevant report seldom.
Kinya in 1989 etc.
[3]Having delivered with carried noble metal (5%Pd/C, 5%Ru/C, 5%Pt/C, 5%Rh/C) is catalyzer, at 250 ℃, the catalytic hydrogenation reaction of pyrene under the 5MPa condition, wherein principal product is 4 under Pd/C, Ru/C, the Pt/C catalyst system, 5-dihydropyrene and 4,5,9,10-tetrahydrochysene pyrene, but selectivity is not high.Daniel M.Connor in 1999 etc.
[4]Disclosing with 10%Pd/C is catalyzer, and ethyl acetate is a solvent, and the pyrene catalytic hydrogenation reaction is 64～72 hours under 0.28～0.31MPa condition, feed stock conversion 100%, 4,5,9, and the selectivity of 10-tetrahydrochysene pyrene reaches 85%.Vyacheslav in 2008 etc.
[2]Having reported the selective catalytic hydrogenation of pyrene under the 10%Pd/C catalyst system, is solvent with the ethyl acetate, and under 60 ℃, 1.6MPa condition, raw material pyrene and catalyst quality were than 5: 1, reacted feed stock conversion 100%, 4 24 hours, 5,9, the yield of 10-tetrahydrochysene pyrene reaches 76%.All there is a difficult problem in above-mentioned report, and promptly the shortening of pyrene is because consecutive reaction and parallel reactor are carried out simultaneously, and its single selectivity of product is very difficult to be improved and make.
Summary of the invention
Purpose of the present invention just provide a kind of simple and easy, repeatability is good, catalyzer long service life, pyrene shortening preparation 4,5,9 that selectivity is good, the method for 10-tetrahydrochysene pyrene.
Loaded nano noble metal catalyst used in the present invention is known, and its preparation method is at patent CN1970143
[5]And CN1966144
[6]Existing report in (being introduced into as a reference) at this.Being prepared as follows of loaded nano noble metal catalyst: at first be precious metal salt to be added in the aqueous solution that is dissolved with tensio-active agent dissolve.Add reductive agent under the vigorous stirring, obtain the precious metal colloid of tensio-active agent protection after reduction is finished.In precious metal colloid solution, add carrier then and stir, filtration washing, thus make the loaded nano noble metal catalyst of high dispersing, wherein the charge capacity of precious metal is 0.8～2.5%.Adopt high-resolution-ration transmission electric-lens (HRTEM), X-ray powder diffraction (XRD) to characterize the catalyzer of preparation, noble metal granule is evenly dispersed in carrier surface as can be seen from the TEM picture, and the particulate size is 2-4nm; And by precious metal characteristic diffraction peak in the XRD spectra, the median size of calculating noble metal nano particles according to the Sherrer formula is about 3.7nm.
Particularly, the preparation method of high-activity hydrogenation catalyst nano Ru/C comprises the following steps:
At first prepare certain density water phase surfactant mixture, add dissolved ruthenium salts solution in advance then, after constantly stirring mixes it, add reductive agent, after reduction is finished, form tensio-active agent stabilized nano ruthenium colloidal solution, surfactant concentration is 1-500 a times of micelle-forming concentration, and the concentration of reductive agent is 0.001-1mol/L, and reduction temperature is 10-90 ℃, recovery time is 0.1-12 hour, and prepared metal Ru colloidal concentration is 0.0001mol/L-0.1mol/L; With the ruthenium colloidal solution that carrier absorption makes, after adsorption process finishes, filter, it is neutral that washing catalyst to filtrate to solution is, obtain high dispersing, the loaded nano ruthenium catalyst, the load time of carrier is 3 minutes-3 hours.
Particularly, loading type nano Pd/C Preparation of catalysts method comprises the following steps:
At first prepare the stable, aqueous solution of tensio-active agent, add the good palladium salts solution of dissolving in advance then, stirring mixes it, then, add reductive agent at leisure, solution colour becomes brownish black from dark-brown, become dark solution at last, form tensio-active agent stabilized nano palladium colloidal solution, then the palladium colloid that makes with inert support absorption, after adsorption process finishes, filter, washing catalyst no Cl existence to the filtrate obtains the loaded nano palladium catalyst, wherein: surfactant concentration is 1-500 a times of micelle-forming concentration, the concentration of palladium ion is 0.001-0.1mol/L, and the concentration of reductive agent is 0.01-1mol/L, and the needed temperature of reduction reaction is 0-90 ℃, the needed recovery time is 3 minutes-3 hours, and the adsorption time behind the adding carrier is 0.1-12 hour.
The similar aforesaid method of the preparation of other loaded nano noble metal catalysts.
The present invention adopts the loaded nano precious metal as catalyzer by being set out by pyrene, carries out selective catalytic hydrogenation and has realized above-mentioned purpose, and wherein the loaded nano noble metal catalyst is Pt/C, Pd/C and Ru/C.
Therefore, the present invention relates to a kind of preparation 4,5,9, the method of 10-tetrahydrochysene pyrene, this method uses pyrene as raw material, and working load type nano-noble metal catalyst carries out selective hydrogenation preparation 4,5,9,10-tetrahydrochysene pyrene, wherein said loaded nano noble metal catalyst is prepared as follows: at first precious metal salt is added in the aqueous solution that is dissolved with tensio-active agent and dissolve; Add reductive agent under the vigorous stirring, obtain the precious metal colloid of tensio-active agent protection after reduction is finished; In precious metal colloid solution, add carrier then and stir, filtration washing, thus make the loaded nano noble metal catalyst of high dispersing, wherein the charge capacity of precious metal is 0.8～2.5%.
In one embodiment, described being reflected at is selected from ethanol, ethyl acetate, hexanaphthene, hexahydroaniline, perhydronaphthalene, tetrahydrofuran (THF), or carries out ethyl acetate in the solvent in its mixture.
In one embodiment, the mass ratio of solvent and raw material is 2: 1～20: 1.
In one embodiment, the mass ratio of loaded nano noble metal catalyst and raw material is 1: 2～1: 20.
In one embodiment, the temperature of described reaction is 20～150 ℃, is preferably 30～90 ℃.
In one embodiment, the system pressure of described reaction is 0.2～8.0MPa, is preferably 0.4～4.0MPa.
In one embodiment, the time of described reaction is 1.0～80.0 hours, is preferably 2.5～70.0 hours.
In one embodiment, this method comprises the following steps:
Add raw material, solvent, loaded nano noble metal catalyst to container, wherein the mass ratio of solvent and raw material is 2: 1～20: 1, and the mass ratio of loaded nano noble metal catalyst and raw material is 1: 2～1: 20;
Airtight back charges into a certain amount of hydrogen then with nitrogen and hydrogen degasification;
Put into oil bath reaction is heated to 20～150 ℃;
Adjust system pressure and make it reach 0.2～8.0MPa, and under agitation reacted 1.0～80.0 hours.
In one embodiment, wherein said container is a still formula high-pressure reactor.
In one embodiment, wherein used loaded nano noble metal catalyst is loaded nano Pt/C catalyzer, loading type nano Pd/C catalyzer and loaded nano Ru/C catalyzer.
The present invention has the following advantages: catalyst loadings is low, and activity is high and selectivity is good and traditional technology is compared, and greatly reduces production cost.
Embodiment
Below in conjunction with embodiment the present invention is made further exemplary illustration, rather than its scope is limited.
Embodiment 1
In being the still formula high-pressure reactor of 70ml, volume puts into the 2.0g pyrene, the 25ml ethyl acetate, 0.2g1% loading type nano Pd/C catalyzer, respectively replace 3 times with nitrogen and hydrogen airtight back, charges into the hydrogen of 0.2MPa then, and still formula high-pressure reactor is put into oil bath heat temperature raising to 30 ℃, adjust hydrogen valve, make system pressure reach 1.0MPa, after 66.0 hours, reaction is finished.The sampling of cooling back is carried out capillary gas chromatography, transformation efficiency 100%, 4,5,9,10-tetrahydrochysene pyrene yield 89.8%.Specific analytical method: fid detector, OV-101 capillary column (30m * 0.32mm * 0.5 μ m), vaporizer temperature: 280 ℃, detector temperature: 280 ℃, column temperature: 220 ℃, product adopts the HP6890/MSD5793 gas chromatograph-mass spectrometer (GC-MS) to carry out qualitative analysis, main characteristic ion peak is (m/z:206,189,178,165,101,89), with 4,5,9, the standard makings collection of illustrative plates unanimity of 10-tetrahydrochysene pyrene has determined that the hydrogenation product is exactly a target product.
Embodiment 2
In being the still formula high-pressure reactor of 70ml, volume puts into the 2.0g pyrene, the 25ml ethyl acetate, 0.2g2% loading type nano Pd/C catalyzer, respectively replace 3 times with nitrogen and hydrogen airtight back, charges into the hydrogen of 0.2MPa then, and still formula high-pressure reactor is put into oil bath heat temperature raising to 50 ℃, adjust hydrogen valve, make system pressure reach 1.0MPa, after 14.0 hours, reaction is finished.The sampling of cooling back is carried out capillary gas chromatography, transformation efficiency 100%, 4,5,9,10-tetrahydrochysene pyrene yield 89.0%.Concrete quantitatively with analytical procedure is identical with example 1 qualitatively.
Embodiment 3
In being the still formula high-pressure reactor of 70ml, volume puts into the 2.0g pyrene, the 25ml ethyl acetate, 0.2g2% loading type nano Pd/C catalyzer, respectively replace 3 times with nitrogen and hydrogen airtight back, charges into the hydrogen of 0.2MPa then, and still formula high-pressure reactor is put into oil bath heat temperature raising to 70 ℃, adjust hydrogen valve, make system pressure reach 1.0MPa, after 3.0 hours, reaction is finished.The sampling of cooling back is carried out capillary gas chromatography, transformation efficiency 100%, 4,5,9,10-tetrahydrochysene pyrene yield 87.2%.Concrete quantitatively with analytical procedure is identical with example 1 qualitatively.
Embodiment 4
In being the still formula high-pressure reactor of 70ml, volume puts into the 2.0g pyrene, 25ml ethyl acetate, 0.2g
1.5% loading type nano Pd/C catalyzer, respectively replace 3 times with nitrogen and hydrogen airtight back, charges into the hydrogen of 0.1MPa then, still formula high-pressure reactor is put into oil bath heat temperature raising to 50 ℃, adjust hydrogen valve, make system pressure reach 0.4MPa, 22.0 after hour, reaction is finished.The sampling of cooling back is carried out capillary gas chromatography, transformation efficiency 100%, 4,5,9,10-tetrahydrochysene pyrene yield 89.5%.Concrete quantitatively with analytical procedure is identical with example 1 qualitatively.
Embodiment 5
In being the still formula high-pressure reactor of 70ml, volume puts into the 2.0g pyrene, the 25ml ethyl acetate, 0.15g2% loaded nano Ru/C catalyzer, respectively replace 3 times with nitrogen and hydrogen airtight back, charges into the hydrogen of 0.2MPa then, and still formula high-pressure reactor is put into oil bath heat temperature raising to 30 ℃, adjust hydrogen valve, make system pressure reach 1.0MPa, after 22.0 hours, reaction is finished.The sampling of cooling back is carried out capillary gas chromatography, transformation efficiency 100%, 4,5,9,10-tetrahydrochysene pyrene yield 85.5%.Concrete quantitatively with analytical procedure is identical with example 1 qualitatively.
Embodiment 6
In being the still formula high-pressure reactor of 70ml, volume puts into the 2.0g pyrene, the 25ml ethyl acetate, 0.2g1% loaded nano Pt/C catalyzer, respectively replace 3 times with nitrogen and hydrogen airtight back, charges into the hydrogen of 0.1MPa then, and still formula high-pressure reactor is put into oil bath heat temperature raising to 30 ℃, adjust hydrogen valve, make system pressure reach 1.0MPa, after 30.0 hours, reaction is finished.The sampling of cooling back is carried out capillary gas chromatography, transformation efficiency 100%, 4,5,9,10-tetrahydrochysene pyrene yield 88.9%.Concrete quantitatively with analytical procedure is identical with example 1 qualitatively.
Embodiment 7
In being the still formula high-pressure reactor of 70ml, volume puts into the 2.0g pyrene, the 25ml ethyl acetate, 0.2g1% loading type nano Pd/C catalyzer, respectively replace 3 times with nitrogen and hydrogen airtight back, charges into the hydrogen of 0.1MPa then, and still formula high-pressure reactor is put into oil bath heat temperature raising to 30 ℃, adjust hydrogen valve, make system pressure reach 3.0MPa, after 25.0 hours, reaction is finished.The sampling of cooling back is carried out capillary gas chromatography, transformation efficiency 100%, 4,5,9,10-tetrahydrochysene pyrene yield 87.0%.Concrete quantitatively with analytical procedure is identical with example 1 qualitatively.
Embodiment 8
In being the still formula high-pressure reactor of 70ml, volume puts into the 8.0g pyrene, the 25ml ethyl acetate, 0.4g1% loading type nano Pd/C catalyzer, respectively replace 3 times with nitrogen and hydrogen airtight back, charges into the hydrogen of 0.1MPa then, and still formula high-pressure reactor is put into oil bath heat temperature raising to 100 ℃, adjust hydrogen valve, make system pressure reach 6.0MPa, after 4.0 hours, reaction is finished.The sampling of cooling back is carried out capillary gas chromatography, transformation efficiency 100%, 4,5,9,10-tetrahydrochysene pyrene yield 85.1%.Concrete quantitatively with analytical procedure is identical with example 1 qualitatively.
Embodiment 9
In being the still formula high-pressure reactor of 70ml, volume puts into the 4.0g pyrene, the 25ml ethyl acetate, 0.3g1% loading type nano Pd/C catalyzer, respectively replace 3 times with nitrogen and hydrogen airtight back, charges into the hydrogen of 0.1MPa then, and still formula high-pressure reactor is put into oil bath heat temperature raising to 140 ℃, adjust hydrogen valve, make system pressure reach 2.0MPa, after 5.0 hours, reaction is finished.The sampling of cooling back is carried out capillary gas chromatography, transformation efficiency 100%, 4,5,9,10-tetrahydrochysene pyrene yield 84.9%.Concrete quantitatively with analytical procedure is identical with example 1 qualitatively.
Embodiment 10
In being the still formula high-pressure reactor of 70ml, volume puts into the 2.0g pyrene, the 25ml ethyl acetate, 0.8g1% loading type nano Pd/C catalyzer, respectively replace 3 times with nitrogen and hydrogen airtight back, charges into the hydrogen of 0.1MPa then, and still formula high-pressure reactor is put into oil bath heat temperature raising to 30 ℃, adjust hydrogen valve, make system pressure reach 1.0MPa, after 15.0 hours, reaction is finished.The sampling of cooling back is carried out capillary gas chromatography, transformation efficiency 100%, 4,5,9,10-tetrahydrochysene pyrene yield 87.5%.Concrete quantitatively with analytical procedure is identical with example 1 qualitatively.
Embodiment 11
In being the still formula high-pressure reactor of 70ml, volume puts into the 1.5g pyrene, the 25ml ethyl acetate, 0.1g1% loading type nano Pd/C catalyzer, respectively replace 3 times with nitrogen and hydrogen airtight back, charges into the hydrogen of 0.1MPa then, and still formula high-pressure reactor is put into oil bath heat temperature raising to 120 ℃, adjust hydrogen valve, make system pressure reach 5.0MPa, after 3.5 hours, reaction is finished.The sampling of cooling back is carried out capillary gas chromatography, transformation efficiency 100%, 4,5,9,10-tetrahydrochysene pyrene yield 85.2%.Concrete quantitatively with analytical procedure is identical with example 1 qualitatively.
Embodiment 12
In being the still formula high-pressure reactor of 70ml, volume puts into the 2.0g pyrene, the 25ml hexanaphthene, 0.2g 1% loading type nano Pd/C catalyzer, respectively replace 3 times with nitrogen and hydrogen airtight back, charges into the hydrogen of 0.1MPa then, and still formula high-pressure reactor is put into oil bath heat temperature raising to 30 ℃, adjust hydrogen valve, make system pressure reach 1.0MPa, after 55.0 hours, reaction is finished.The sampling of cooling back is carried out capillary gas chromatography, transformation efficiency 100%, 4,5,9,10-tetrahydrochysene pyrene yield 86.6%.Concrete quantitatively with analytical procedure is identical with example 1 qualitatively.
Embodiment 13
In being the still formula high-pressure reactor of 70ml, volume puts into the 2.0g pyrene, the 25ml tetrahydrofuran (THF), 0.2g1% loading type nano Pd/C catalyzer, respectively replace 3 times with nitrogen and hydrogen airtight back, charges into the hydrogen of 0.1MPa then, and still formula high-pressure reactor is put into oil bath heat temperature raising to 30 ℃, adjust hydrogen valve, make system pressure reach 1.0MPa, after 64.0 hours, reaction is finished.The sampling of cooling back is carried out capillary gas chromatography, transformation efficiency 100%, 4,5,9,10-tetrahydrochysene pyrene yield 86.0%.Concrete quantitatively with analytical procedure is identical with example 1 qualitatively.
Reference
[1]P.Soustek，M.Michl，N.Almonasy，O.Machalicky，M.Dvorak，A.Lycka.Dyes?and?Pigments?2008，78，139-147.
[2]Vyacheslav?V.Filichev，Irina?V.Astakhova，Andrei?D.Malakhov，Vladimir?A.Korshun，Erik?B.Pedersen.Chem.Eur.J.2008，14，9968-9980.
[3]Kinya?SAKANISHI，Masato?OHIRA?et?al.Bull.Chem.Soc.Jpn.1989，62：3994-4001.
[4]Daniel?M.Connor，Scott?D.Allen，David?M.Collard，Charles?L.Liotta，David?A.Schiraldi.J.Org.Chem.1999，64，6888-6890.
[5] Lv Lianhai, Guo Fang, Xin Junna etc., the preparation method of a kind of high-activity hydrogenation catalyst nano Ru/C, CN1970143,2007.
[6] Lv Lianhai, Xin Junna, Du Wenqiang etc. a kind ofly prepare the method for loading type nano Pd/C catalyzer, CN1966144,2007. by colloidal solution
Claims (10)
1. one kind prepares 4,5,9, the method for 10-tetrahydrochysene pyrene is characterized in that, this method uses pyrene as raw material, working load type nano-noble metal catalyst carries out selective hydrogenation preparation 4,5,9,10-tetrahydrochysene pyrene, wherein said loaded nano noble metal catalyst is prepared as follows: at first precious metal salt is added in the aqueous solution that is dissolved with tensio-active agent and dissolve; Add reductive agent under the vigorous stirring, obtain the precious metal colloid of tensio-active agent protection after reduction is finished; In precious metal colloid solution, add carrier then and stir, filtration washing, thus make the loaded nano noble metal catalyst of high dispersing, wherein the charge capacity of precious metal is 0.8～2.5%.
2. the described method of claim 1 is characterized in that, described being reflected at is selected from ethanol, ethyl acetate, hexanaphthene, hexahydroaniline, perhydronaphthalene, tetrahydrofuran (THF), or carries out ethyl acetate in the solvent in its mixture.
3. the described method of claim 2 is characterized in that, the mass ratio of solvent and raw material is 2: 1～20: 1.
4. each method is characterized in that in the aforementioned claim, and the mass ratio of loaded nano noble metal catalyst and raw material is 1: 2～1: 20.
5. each method is characterized in that in the aforementioned claim, and the temperature of described reaction is 20～150 ℃, is preferably 30～90 ℃.
6. each method is characterized in that in the aforementioned claim, and the system pressure of described reaction is 0.2～8.0MPa, is preferably 0.4～4.0MPa.
7. each method is characterized in that in the aforementioned claim, and the time of described reaction is 1.0～80.0 hours, is preferably 2.5～70.0 hours.
8. each method is characterized in that in the aforementioned claim, and this method comprises the following steps:
Add raw material, solvent, loaded nano noble metal catalyst to container, wherein the mass ratio of solvent and raw material is 2: 1～20: 1, and the mass ratio of loaded nano noble metal catalyst and raw material is 1: 2～1: 20;
Airtight back charges into a certain amount of hydrogen then with nitrogen and hydrogen degasification;
Put into oil bath reaction is heated to 20～150 ℃;
Adjust system pressure and make it reach 0.2～8.0MPa, and under agitation reacted 1.0～80.0 hours.
9. the method for claim 8, wherein said container is a still formula high-pressure reactor.
10. each method in the aforementioned claim, wherein used loaded nano noble metal catalyst are loaded nano Pt/C catalyzer, loading type nano Pd/C catalyzer and loaded nano Ru/C catalyzer.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966144A (en) * | 2006-09-06 | 2007-05-23 | 大连理工大学 | Method for preparing loading type nano Pd/C catalyst from colloidal solution |
| CN1970143A (en) * | 2006-09-06 | 2007-05-30 | 大连理工大学 | Method for preparing high-activity hydrogenation catalyst nano Ru/C |
-
2010
- 2010-03-29 CN CN2010101403177A patent/CN102206133A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966144A (en) * | 2006-09-06 | 2007-05-23 | 大连理工大学 | Method for preparing loading type nano Pd/C catalyst from colloidal solution |
| CN1970143A (en) * | 2006-09-06 | 2007-05-30 | 大连理工大学 | Method for preparing high-activity hydrogenation catalyst nano Ru/C |
Non-Patent Citations (1)
| Title |
|---|
| VYACHESLAV V.FILICHEV,IRINA V.ASTAKHOVA,ANDREI D.MALAKHOV: "1-，2-，and 4-Ethynylpyrenes in the Strcture of Twisted Intercalating Nucleic Acids:Structure,Thermal Stability,and Fluorescence Relationship", 《CHEM.EUR.J》 * |
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Application publication date: 20111005 |