CN107311970B - Method for preparing 4-hydroxy-6-methyltetrahydro-2-pyrone - Google Patents
Method for preparing 4-hydroxy-6-methyltetrahydro-2-pyrone Download PDFInfo
- Publication number
- CN107311970B CN107311970B CN201710597479.5A CN201710597479A CN107311970B CN 107311970 B CN107311970 B CN 107311970B CN 201710597479 A CN201710597479 A CN 201710597479A CN 107311970 B CN107311970 B CN 107311970B
- Authority
- CN
- China
- Prior art keywords
- hydroxy
- methyltetrahydro
- pyrone
- preparing
- noble metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- KKZQBMBBMJKIRQ-UHFFFAOYSA-N (4S,6S)-3,4,5,6-Tetrahydro-4-hydroxy-6-methyl-2H-pyran-2-one Chemical compound CC1CC(O)CC(=O)O1 KKZQBMBBMJKIRQ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 150000002596 lactones Chemical class 0.000 claims abstract description 11
- 239000000852 hydrogen donor Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- -1 alcohol compound Chemical class 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 238000006276 transfer reaction Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- NSYSSMYQPLSPOD-UHFFFAOYSA-N triacetate lactone Chemical compound CC1=CC(O)=CC(=O)O1 NSYSSMYQPLSPOD-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002105 nanoparticle Substances 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 claims 2
- 239000000243 solution Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000037353 metabolic pathway Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- ZQBVUULQVWCGDQ-UHFFFAOYSA-N propan-1-ol;propan-2-ol Chemical compound CCCO.CC(C)O ZQBVUULQVWCGDQ-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/30—Oxygen atoms, e.g. delta-lactones
-
- 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
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 4-hydroxy-6-methyltetrahydro-2-pyrone, which comprises the following steps: mixing a triacetyl lactone raw material and an alcohol compound with a hydrogen donor, adding the mixture into a closed high-pressure reaction kettle, and carrying out hydrogen transfer reaction for 0.5-48h under the conditions that the nitrogen pressure is 1-12MPa, the reaction temperature is room temperature-150 ℃ and a catalyst exists to obtain the 4-hydroxy-6-methyltetrahydro-2-pyrone, wherein the catalyst is non-noble metal nano-particles. The method does not need to use noble metal, has low cost, is easy to separate, can be repeatedly used, has a simple reaction system, and is easy to industrialize.
Description
Technical Field
The invention particularly relates to a method for preparing 4-hydroxy-6-methyl tetrahydropyranone.
Background
Biomass is the only renewable organic carbon resource and an ideal candidate for replacing petroleum-derived fuels and chemicals. Therefore, the organic carbon resource in the biomass is fully utilized, and a new route and a new method for preparing fuel and chemicals by biomass conversion are developed, so that the method becomes a research hotspot in the fields of new energy and new materials. The microbial platform molecules provide a new opportunity for the conversion of carbohydrates into commercial chemicals, the microbial platform molecules are products of a single microbial metabolic pathway and have flexible and controllable functional groups, and the chemical catalytic upgrading can convert the platform molecules into various terminal products to replace the existing petrochemical products. Triacetyl lactone (4-hydroxy-6-methyl-2-pyrone, Triacetic acid lactone) is a new generation platform molecule from microorganisms, can be derived from nature (plants and microorganisms), can be synthesized by acetic acid, is considered as a bridge compound linking biocatalysis and chemical catalysis, and is helpful for overcoming the defects of preparing a bio-based high-value chemical product by a single chemical method or a single biological method by researching efficient conversion and utilization of the triacetyl lactone. The triacetolactone can be converted into various commercially valuable chemical intermediates and end products through catalytic upgrading. The first step of the conversion of the triacetyl lactone is catalytic hydrogenation, and the problem exists at present that the triacetyl lactone is easy to degrade in aqueous solution, and the hydrogenation step needs to use n-butyl alcohol as a solvent, hydrogen as a hydrogen source and noble metal as a catalyst.
Disclosure of Invention
The invention mainly aims to provide a method for preparing 4-hydroxy-6-methyltetrahydro-2-pyrone so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
mixing a triacetyl lactone raw material and an alcohol compound with a hydrogen donor, adding the mixture into a closed high-pressure reaction kettle, and carrying out hydrogen transfer reaction for 0.5-48h under the conditions that the nitrogen pressure is 1-12MPa, the reaction temperature is room temperature-150 ℃ and a catalyst exists to obtain the 4-hydroxy-6-methyltetrahydro-2-pyrone, wherein the catalyst is non-noble metal nano-particles.
Further, the alcohol compound comprises primary alcohol and secondary alcohol, wherein the primary alcohol is methanol, ethanol, n-propanol, n-butanol, n-pentanol or cyclohexanol, and the secondary alcohol is isopropanol, isobutanol or sec-butanol.
Furthermore, the ratio of the alcohol compound to the triacetyl lactone is 5-50 mL: 1 g.
Further, the non-noble metal comprises one or more of nickel, cobalt and copper.
Furthermore, the dosage ratio of the non-noble metal nano-particle catalyst to the triacetic acid lactone is 0.03-2.0 g: 1 g.
Further, the method also comprises the steps of recovering and recycling the non-noble metal nano-particle catalyst; the catalyst recovery method comprises the steps of centrifugal separation, washing and drying.
Compared with the prior art, the invention has the advantages that: the alcohol compound in the hydrogen transfer reaction is used as a solvent and a hydrogen source, no additional hydrogen source is needed, and the used catalyst is a common easily-obtained non-noble metal, so that the cost is low, and the catalyst can be recycled. Compared with the prior art, the process of the invention does not need additional hydrogen, and is simple and safe to operate.
Drawings
FIG. 1 is a graph showing the results of HPLC analysis of the product of example 1.
Detailed Description
The technical solutions of the present invention will be described in detail below with reference to several embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Examples 1 to 4:
this example provides the preparation of different metal nanoparticles, and experiments for the catalytic hydrogen transfer of triacetolactone to produce 4-hydroxy-6-methyltetrahydro-2-pyrone:
preparing nickel nano particles: 0.1g of nickel nitrate was dissolved in 4mL of water, and the solution was added dropwise to a mixture of 40mL of ethylene glycol and 40mL of water, ultrasonically dispersed for 30min, 16mL of an aqueous sodium borohydride solution (0.01g/mL) was added dropwise to the solution, stirred at room temperature for 8 hours, filtered, and vacuum-dried at 80 ℃ for 24 hours.
Preparing cobalt nanoparticles: 0.1g of cobalt nitrate was dissolved in 4mL of water, and the solution was added dropwise to a mixture of 40mL of ethylene glycol and 40mL of water, ultrasonically dispersed for 30min, 16mL of an aqueous sodium borohydride solution (0.01g/mL) was added dropwise to the solution, stirred at room temperature for 8 hours, filtered, and vacuum-dried at 80 ℃ for 24 hours.
Preparing copper nanoparticles: 0.1g of copper nitrate was dissolved in 4mL of water, and the solution was added dropwise to a mixture of 40mL of ethylene glycol and 40mL of water, ultrasonically dispersed for 30min, 16mL of an aqueous sodium borohydride solution (0.01g/mL) was added dropwise to the solution, stirred at room temperature for 8 hours, filtered, and vacuum-dried at 80 ℃ for 24 hours.
Preparing nickel-cobalt bimetallic nanoparticles: 0.05g of nickel nitrate and 0.05g of cobalt nitrate were dissolved in 4mL of water, and the solution was added dropwise to a mixture of 40mL of ethylene glycol and 40mL of water, ultrasonically dispersed for 30min, 16mL of an aqueous sodium borohydride solution (0.01g/mL) was added dropwise to the solution, stirred at room temperature for 8 hours, filtered, and vacuum-dried at 80 ℃ for 24 hours.
Adding the prepared metal nanoparticles into a high-pressure reaction kettle, adding 0.25g of triacetyl lactone and 5mL of isopropanol (serving as a hydrogen donor and a reaction solvent), sealing, replacing five times with nitrogen, introducing 0.1MPa of nitrogen, reacting for 10 hours at 50 ℃, and analyzing and quantifying the composition of products after the reaction is finished by using high performance liquid chromatography. Specific results are shown in table 1:
TABLE 1 catalysis results of different catalysts
Examples 5 to 10:
this example provides an experiment of hydrogenation of triacetolactone to produce 4-hydroxy-6-methyltetrahydro-2-pyrone using various alcohol compounds as hydrogen donors:
adding 0.02g of nickel nanoparticles into a high-pressure reaction kettle, adding 0.25g of triacetyl lactone and 5mL of different alcohol compounds (serving as a hydrogen donor and a reaction solvent), sealing, replacing five times with nitrogen, introducing 0.1MPa of nitrogen, reacting for 10 hours at 50 ℃, and analyzing and quantifying the composition of products after the reaction is finished by using high performance liquid chromatography. Specific results are shown in table 2:
TABLE 2 catalysis results when different alcohols were used as hydrogen donors
| Examples | Different alcohols | Conversion (%) | Selectivity (%) | Yield (%) |
| 5 | N-propanol | 40 | 70 | 24 |
| 6 | N-butanol | 50 | 54 | 27 |
| 7 | N-pentanol | 48 | 31 | 15 |
| 8 | Cyclohexanol | 45 | 44 | 20 |
| 9 | Sec-butyl alcohol | 52 | 65 | 34 |
| 10 | Isopropanol (I-propanol) | 100 | 89 | 89 |
Examples 11 to 13:
this example provides experiments for the hydrogenation of triacetolactone to produce 4-hydroxy-6-methyltetrahydro-2-pyrone at different reaction temperatures:
adding 0.02g of nickel nanoparticles into a high-pressure reaction kettle, adding 0.25g of triacetyl lactone and 5mL of different alcohol compounds (serving as a hydrogen donor and a reaction solvent), sealing, replacing five times with nitrogen, introducing 0.1MPa of nitrogen, reacting for 10 hours at different temperatures, and analyzing and quantifying the composition of products after the reaction is finished by using high performance liquid chromatography. Specific results are shown in table 3:
TABLE 3 catalytic results at different temperatures
| Examples | Temperature (. degree.C.) | Conversion (%) | Selectivity (%) | Yield (%) |
| 11 | 50 | 100 | 89 | 89 |
| 12 | 75 | 100 | 90 | 90 |
| 13 | 100 | 100 | 75 | 75 |
Examples 14 to 17:
the reaction conditions used in this experiment were the same as those in example 1, except that the step of recovering and reusing the catalyst was added.
The recycling and reusing steps are as follows: after the reaction, the catalyst was centrifuged, the supernatant was decanted, the precipitate was washed three times with ethanol, dried under vacuum at 80 ℃ for the next reaction, and the results of the repeated use test are shown in table 4:
TABLE 4 catalyst recovery, catalyst results for reuse
| Examples | Number of times of recycling | Conversion (%) | Selectivity (%) | Yield (%) |
| 14 | 1 | 100 | 89 | 89 |
| 15 | 5 | 100 | 88 | 88 |
| 16 | 10 | 100 | 88 | 88 |
| 17 | 20 | 100 | 85 | 85 |
With the adoption of the above contents, it can be proved that the preparation of 4-hydroxy-6-methyltetrahydro-2-pyrone by hydrogen transfer of triacetic acid lactone under the catalysis of non-noble metal nanoparticles does not need additional hydrogen and noble metal catalysts, the cost is low, and the catalysts can be recycled.
It should be understood that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and that various modifications and changes can be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A process for preparing 4-hydroxy-6-methyltetrahydro-2-pyrone comprising the steps of:
mixing a triacetyl lactone raw material and an alcohol compound with a hydrogen donor, adding the mixture into a closed high-pressure reaction kettle, and carrying out hydrogen transfer reaction for 0.5-48h under the conditions that the nitrogen pressure is 0.1MPa, the reaction temperature is 50-75 ℃ and a catalyst exists to obtain 4-hydroxy-6-methyltetrahydro-2-pyrone, wherein the catalyst is non-noble metal nano-particles;
the alcohol compound with the hydrogen donor is isopropanol;
the non-noble metal nanoparticles are nickel nanoparticles, cobalt nanoparticles or cobalt-nickel bimetallic nanoparticles.
2. The process for preparing 4-hydroxy-6-methyltetrahydro-2-pyrone according to claim 1, characterized in that: the ratio of the alcohol compound to the triacetic acid lactone is 5-50 mL: 1g of the total weight of the composition.
3. The process for preparing 4-hydroxy-6-methyltetrahydro-2-pyrone according to claim 1, characterized in that: the non-noble metal nanoparticles are cobalt-nickel bimetallic nanoparticles.
4. The process for preparing 4-hydroxy-6-methyltetrahydro-2-pyrone according to claim 1, characterized in that: the dosage ratio of the non-noble metal nano-particle catalyst to the triacetic acid lactone is 0.03-2.0 g: 1g of the total weight of the composition.
5. The process for preparing 4-hydroxy-6-methyltetrahydro-2-pyrone according to claim 1, characterized in that: also comprises the steps of recovering and recycling the non-noble metal nano-particle catalyst; the catalyst recovery method comprises centrifugal separation, washing and drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710597479.5A CN107311970B (en) | 2017-07-20 | 2017-07-20 | Method for preparing 4-hydroxy-6-methyltetrahydro-2-pyrone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710597479.5A CN107311970B (en) | 2017-07-20 | 2017-07-20 | Method for preparing 4-hydroxy-6-methyltetrahydro-2-pyrone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107311970A CN107311970A (en) | 2017-11-03 |
| CN107311970B true CN107311970B (en) | 2020-01-24 |
Family
ID=60178119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710597479.5A Active CN107311970B (en) | 2017-07-20 | 2017-07-20 | Method for preparing 4-hydroxy-6-methyltetrahydro-2-pyrone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107311970B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315947A (en) * | 1998-07-06 | 2001-10-03 | 伊斯曼化学公司 | Preparation of tocopherols |
| US20120116119A1 (en) * | 2010-11-10 | 2012-05-10 | Dumesic James A | Production of 2,4-hexadienoic acid and 1,3-pentadiene from 6-methyl-5,6-dihydro-2-pyrone |
| CN104945282A (en) * | 2015-05-10 | 2015-09-30 | 洪志 | Ultrasonic-accelerated catalytic transfer hydrogenation reduction method of 4-chloro-alpha-(2-chloro-4-(hydroxyimino)-5-methyl-2,5-phenylidene)benzyl cyanide |
-
2017
- 2017-07-20 CN CN201710597479.5A patent/CN107311970B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315947A (en) * | 1998-07-06 | 2001-10-03 | 伊斯曼化学公司 | Preparation of tocopherols |
| US20120116119A1 (en) * | 2010-11-10 | 2012-05-10 | Dumesic James A | Production of 2,4-hexadienoic acid and 1,3-pentadiene from 6-methyl-5,6-dihydro-2-pyrone |
| CN104945282A (en) * | 2015-05-10 | 2015-09-30 | 洪志 | Ultrasonic-accelerated catalytic transfer hydrogenation reduction method of 4-chloro-alpha-(2-chloro-4-(hydroxyimino)-5-methyl-2,5-phenylidene)benzyl cyanide |
Non-Patent Citations (2)
| Title |
|---|
| Model Studies Towards the Synthesis of Aplysiatoxin Spiro-conformational Control in the Reactivity of C2-oxidized Spiroketals;David A. Stolze et al;《Tetrahedron Letters》;19911231;第32卷(第33期);第4081-4084页 * |
| Triacetic acid lactone as a potential biorenewable platform chemical;Mei Chia et al;《Green Chem.》;20120501;第14卷;第1850-1853页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107311970A (en) | 2017-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107159270B (en) | A kind of magnetism hydrogenation deoxidation catalyst and its preparation method and application | |
| WO2019041583A1 (en) | Method for preparing p-hydroxycinnamate by using ionic liquid to catalyze lignin | |
| CN106215953B (en) | The synthesis of controllable number of plies molybdenum sulfide and its application in fragrant phenol and ethers reaction | |
| CN101885978A (en) | Method for directly producing alkane fuel by lignin | |
| CN107935816B (en) | Method for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol | |
| CN110354886A (en) | A kind of nitrogen-doped carbon nickel-loaded cobalt dual-metal nanocatalyst, preparation method and application | |
| CN113117688A (en) | MOF precursor molybdenum-nickel catalyst, preparation method thereof and application thereof in lignin degradation | |
| JP2017533907A (en) | Mild catalytic reduction of C—O and C═O bonds using a reusable catalyst system | |
| CN114177930A (en) | Method for catalyzing lignin hydrogenation depolymerization by molecular sieve supported ruthenium-nickel catalyst | |
| WO2019062286A1 (en) | Lignin depolymerization method | |
| EP3101000A1 (en) | Hydrogenation reaction method | |
| CN109704902B (en) | Ionic liquid catalytic deoxidation method in lignin derivative hydrodeoxygenation process | |
| CN107311970B (en) | Method for preparing 4-hydroxy-6-methyltetrahydro-2-pyrone | |
| CN104387340A (en) | Method for preparing N-methyl piperazine and catalyst of N-methyl piperazine | |
| CN104829559A (en) | Method of preparing Nu-valerolactone from methyl levulinate | |
| US10315977B1 (en) | Method of preparing N-butyric acid by using poly-3-hydroxybutyrate | |
| CN114213214B (en) | Method for preparing fatty alcohol by catalyzing fatty acid under mild condition | |
| CN103055870A (en) | Nickel/copper catalyst and preparation method thereof, and method for directly preparing 1,2-hexanediol from cellulosan by using nickel/copper catalyst | |
| CN112441927B (en) | Pt-ReOx/TiO2Method for preparing aniline by selective catalytic conversion of lignin | |
| CN114377718A (en) | Nickel-copper bimetallic catalyst and preparation method and application thereof | |
| CN109678655B (en) | Application of nickel-iron hydrotalcite catalyst in preparation of benzyl alcohol | |
| CN109694364A (en) | Zirconium oxycarbonate ultralow temperature is catalyzed furfural to the method for furfuryl alcohol | |
| CN112892539A (en) | Method for coupling hydrogenolysis of lignin by heterogeneous catalyst and homogeneous catalyst | |
| CN112441888A (en) | Pd-ReOx/CeO2Method for preparing nitrogen-containing aromatic compound by catalyzing lignin ammoniation reaction | |
| CN109438398A (en) | A method of gamma-valerolactone is prepared by levulic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211115 Address after: 730000 No. 18, Tianshui Middle Road, Lanzhou City, Gansu Province Patentee after: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Address before: 215123 building 08, Northwest District, Suzhou nano City, No. 99, Jinjihu Avenue, Suzhou Industrial Park, Jiangsu Province Patentee before: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Suzhou Research Institute |