CN102452915B - Preparation method of 3,4-dihydroxy-2,5-hexanedione - Google Patents
Preparation method of 3,4-dihydroxy-2,5-hexanedione Download PDFInfo
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- CN102452915B CN102452915B CN201110133481.XA CN201110133481A CN102452915B CN 102452915 B CN102452915 B CN 102452915B CN 201110133481 A CN201110133481 A CN 201110133481A CN 102452915 B CN102452915 B CN 102452915B
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Abstract
The invention discloses a preparation method of 3,4-dihydroxy-2,5-hexanedione. The preparation method comprises the following step: a compound II (3,4-dihydroxy-2,5-hexanedione) is prepared by carrying out reduction coupling on a compound I in water or alcohol/water under the action of a catalyst with hydrogen as a reductant. The preparation method of the invention has the advantages of easy operation, low cost, small toxicity of adopted reagents, less environmental pollution, and easy realization of the industrialization.
Description
Technical field
The present invention relates to a kind of preparation method of organic compound, be specifically related to a kind of preparation method of 3,4-dihydroxy-2,5-hexanedione
Background technology
3,4-dihydroxy-2,5-hexanedione is a kind of important intermediate of synthetic perfume furanone (having another name called pineapple ketone), and with its synthetic furanone, technique is simple, and cost is low, and fragrance is pure, has represented main flow fragrance and the market of furanone.Its synthetic suitable interest that has caused people.
So far, synthetic 3, the 4-dihydroxy-2,5-hexanedione of bibliographical information synthetic has following several method:
First method is that Firm company of current Switzerland produces the method that furanone uses, and first the method is utilized acetylene to react with acetaldehyde and generated 2,5-dihydroxyl-3-hexin, then at O
3and under the effect of triphenylphosphine, obtain 3,4-dihydroxy-2,5-hexanedione intermediate, then cyclodehydration generates furanone in Sodium phosphate dibasic catalytic molecular.The problem of its existence is the use inconvenience of acetylene and acetaldehyde, in ozonization, will use triphenylphosphine, and the phosphorus-containing wastewater of generation is not easy to process.
Second method is for adding sodium carbonate in the pyruvic aldehyde aqueous solution of reporting in patent WO2006-48795, use formaldehyde and sodium hydrosulfite or V-Brite B reductive coupling in water to obtain 3,4-dihydroxyl-2,5-hexanedione, because the material environmental pollutions such as a large amount of sodium bisulfites, sodium formiate and the remaining sulfocompound that use excessive formaldehyde and sodium hydrosulfite/V-Brite B and reaction to produce are very serious.
The third method is a kind of method that U.S. Pat 3694466 discloses synthetic 3,4-dihydroxy-2,5-hexanedione, take the pyruvic aldehyde aqueous solution as starting raw material, add water or ethanol, under the effect of zinc powder and acetic acid, obtain 3 through reductive coupling, 4-dihydroxy-2,5-hexanedione.Because the usage quantity of zinc powder and acetic acid is quite large, in reaction process, produce the waste water of a large amount of Containing Zinc Chlorides and aqueous acetic acid.
In addition, use pyruvic aldehyde other document for synthetic 3, the 4-dihydroxy-2,5-hexanedione of starting raw material, also major part is all to use zinc powder and rare acetum to impel pyruvic aldehyde generation dimolecular reduction linked reaction to obtain, and all has similar problem.
The 4th kind of process patent US7,321,067/2008 report, the pyruvic aldehyde of use 40% and excessive hydroxyacetone are under the katalysis of zinc acetate, take ethyl acetate as solvent, in 38～40 ℃ of reactions 40 hours, be extracted with ethyl acetate again, obtain 3,4-dihydroxy-2,5-hexanedione with 52% yield.The method reaction times is quite long, and industrial hydroxyacetone price is high, and excessive hydroxyacetone is difficult to reclaim, high expensive.
Lung biopsy is that the people such as Bassignani (J.Org.Chem., 1978,43,4245) report that use Potcrate/perosmic anhydride system oxidation 2,5-dimethyl furan can obtain 3,4-dihydroxy-2,5-hexanedione.Because 2,5-dimethyl furan is expensive, the toxicity of perosmic anhydride, makes it there is no practical value.
Because existing synthetic method is used expensive raw material, or use large raw material, the solvent of toxicity, or use dangerous large reagent, and or use and be difficult to the material recycled, make in suitability for industrialized production building-up process three-waste pollution serious or there is suitable danger.
Summary of the invention
The technical problem to be solved in the present invention is existing 3 in order to overcome, preparation method's Raw of 4-dihydroxy-2,5-hexanedione expensive, or the toxicity of raw material, solvent is large, or the danger of the reagent using is large, is difficult to the defects such as recycling, and provide a kind of 3, the preparation method of 4-dihydroxy-2,5-hexanedione, preparation method of the present invention, raw material is easy to get, catalyzer used can reclaim, and solvent is easily processed, low in the pollution of the environment.
Technical problem to be solved by this invention can be achieved through the following technical solutions:
A kind of preparation method of 3,4-dihydroxy-2,5-hexanedione, it is in solvent, the compound of formula I, under the effect of catalyzer, uses hydrogen as reductive agent process reductive coupling, makes the compound of formula II, the compound of formula II is through suction filtration, concentrated, it is pure 3 that recrystallization can make, 4-dihydroxyl-2,5-hexanedione, concrete reaction formula is as follows:
In a preferred embodiment of the invention, described catalyzer is Raney's nickel, 1～10% palladium/carbon or 1～10% palladium/aluminium sesquioxide.Preferably 5% palladium/carbon.
In a preferred embodiment of the invention, the consumption of described catalyzer is 5%～50% of reaction substrate weight.Preferably 2%～30%.
In a preferred embodiment of the invention, the mass percent concentration of described Compound I is 20～40%, is preferably 35%.
In a preferred embodiment of the invention, described temperature of reaction is 0～50 ℃, is preferably 10～40 ℃, more preferably 25～30 ℃.
Described solvent is water or alcohol/water mixed solvent.In described alcohol/water mixed solvent, the volume ratio of alcohol and water is 3: 1～1: 4.
Described alcohol is one or more the mixing in methyl alcohol, ethanol, Virahol, is preferably ethanol.
Described reductive coupling reaction is to carry out between 3～14 at pH.Be preferably pH=7～8.
Starting raw material pyruvic aldehyde of the present invention, is formed by the oxidation of air high-temperature catalytic by the facile 1,2-PD of industrial appearance.All commercially available obtaining of other raw materials that the present invention relates to and reagent.
The present invention has following positive progressive effect:
1) preparation method's Raney's nickel of the present invention, 1～10% palladium/carbon or 1～10% palladium/aluminium sesquioxide make catalyzer, and these catalyzer filter recyclable, have avoided use O
3the pollution on the environments such as/triphenylphosphine, zinc and aqueous acetic acid or Potcrate/perosmic anhydride system.
2) preparation method of the present invention is take pyruvic aldehyde as raw material, use easy to operate, low price, cost is low.
3) preparation method of the present invention is solvent with water or alcohol/water body, and the toxicity of solvent is little, and aftertreatment is simple, convenient, recyclable recycling, and environmental pollution is little.
4) preparation method's technique of the present invention is simple, to equipment require lowly, easy to operate, be not only applicable to laboratory small-scale production, and applicable industrial mass production.
Embodiment:
Further illustrate the present invention with embodiment below, but the present invention is not limited.
Embodiment 1
In 500mL there-necked flask, adding 100.0g mass percent concentration is 20% pyruvic aldehyde and water (50mL), and the acid-basicity pH3-4 of reaction medium, under nitrogen protection, add 1.0g Raney's nickel catalyst, air in 10 minutes displacement bottles of logical nitrogen, more logical hydrogen exchange nitrogen, it is 0-5 ℃ that ice-water bath maintains reacting liquid temperature, under normal pressure, react 30 hours to till no longer absorbing hydrogen, GC detection reaction is complete, filters, and filtrate extracts by 4x70mL ethyl acetate; Merge extraction liquid, normal pressure is concentrated, obtains 3.6g thickness semisolid, uses ethyl acetate/petroleum ether freezing and crystallizing, and suction filtration, obtains 2.0g3,4-dihydroxy-2,5-hexanedione (white solid), yield 10.0%, m.p89-90 ℃.
Embodiment 2
In 500ml autoclave pressure, adding 100.0g mass percent concentration is 25% pyruvic aldehyde and water (120mL), it is the acid-basicity pH5-6 that 10% sodium carbonate solution is neutralized to reaction medium that machine mixer stirs lower dropping mass percent concentration, under nitrogen protection, add 3g Raney's nickel catalyst, air in 12 minutes displacement bottles of logical nitrogen, logical hydrogen exchange nitrogen again, maintaining reacting liquid temperature is 5-10 ℃, under 0.15MPa pressure, react 15 hours to till no longer absorbing hydrogen, GC detection reaction is complete, filter, filtrate extracts by 4x80mL ethyl acetate; Merge extraction liquid, normal pressure is concentrated, obtains 5.8g thickness semisolid, uses ethyl acetate/petroleum ether freezing and crystallizing, and suction filtration, obtains 3.4g3,4-dihydroxy-2,5-hexanedione (white solid), yield 13.6%, m.p89-90 ℃.
Embodiment 3
In 250mL there-necked flask; adding 100.0g mass percent concentration is 35% pyruvic aldehyde; it is the acid-basicity pH7-8 that 10% sodium carbonate solution is neutralized to reaction medium that electromagnetic mixer stirs lower dropping mass percent concentration, under nitrogen protection, adds 8g Raney's nickel catalyst.Air in 10 minutes displacement bottles of logical nitrogen, more logical hydrogen exchange nitrogen, maintaining reacting liquid temperature is 10-15 ℃, reacts 10 hours to till no longer absorbing hydrogen under normal pressure, and GC detection reaction is complete, filters, and filtrate is with the extraction of 4x90mL ethyl acetate; Merge extraction liquid, normal pressure is concentrated, obtains 12.0g thickness semisolid, uses ethyl acetate/petroleum ether freezing and crystallizing, and suction filtration, obtains 6.5g3,4-dihydroxy-2,5-hexanedione (white solid), yield 18.6%, m.p 89-90 ℃.
Embodiment 4
In 500mL there-necked flask; adding 200.0g mass percent concentration is 35% pyruvic aldehyde; it is the acid-basicity pH7-8 that 10% sodium carbonate solution is neutralized to reaction medium that electromagnetic mixer stirs lower dropping mass percent concentration, under nitrogen protection, adds 12g Raney's nickel catalyst.Air in 12 minutes displacement bottles of logical nitrogen, more logical hydrogen exchange nitrogen, maintaining reacting liquid temperature is 25-35 ℃, reacts 8 hours to till no longer absorbing hydrogen under normal pressure, and GC detection reaction is complete, filters, and filtrate is with the extraction of 4x100mL ethyl acetate; Merge extraction liquid, normal pressure is concentrated, obtains 30.2g thickness semisolid, uses ethyl acetate/petroleum ether freezing and crystallizing, and suction filtration, obtains 17.0g3,4-dihydroxy-2,5-hexanedione (white solid), yield 23.9%, m.p 89-90 ℃.
Embodiment 5
In 1000mL autoclave pressure; adding 200.0g mass percent concentration is 40% pyruvic aldehyde and methanol/water (150mL; methyl alcohol: water=1: 1 (V: V)); it is the acid-basicity pH10-11 that 10% sodium carbonate solution is neutralized to reaction medium that machine mixer stirs lower dropping mass percent concentration; under nitrogen protection, add 2.4g10% palladium/carbon catalyst.Air in 20 minutes displacement bottles of logical nitrogen, more logical hydrogen exchange nitrogen, the temperature that maintains reaction solution is 27-32 ℃, under 0.15MPa pressure, react 6 hours to till no longer absorbing hydrogen, GC detection reaction is complete, filter, filtrate extracts by 4x120mL ethyl acetate; Merge extraction liquid, normal pressure is concentrated, obtains 22.3g thick liquid, uses ethyl acetate/petroleum ether freezing and crystallizing, and suction filtration, obtains 12.0g3,4-dihydroxy-2,5-hexanedione, yield 15.0%, m.p 89-90 ℃.
Embodiment 6
In 1000mL autoclave pressure, adding 300.0g mass percent concentration is 35% pyruvic aldehyde, and the acid-basicity pH 3-4 of reaction medium, under nitrogen protection, adds 2g10% palladium/carbon catalyst.Air in 15 minutes displacement bottles of logical nitrogen, logical hydrogen exchange nitrogen again, the temperature that maintains reaction solution is 15-20 ℃, till under 0.2MPa pressure, reaction extremely no longer absorbs hydrogen, react 4 hours to till no longer absorbing hydrogen, GC detection reaction is complete, filters, and filtrate extracts by 4x150mL ethyl acetate; Merge extraction liquid, normal pressure is concentrated, obtains 40g thick liquid, uses ethyl acetate/petroleum ether freezing and crystallizing, and suction filtration, obtains 17.2g3,4-dihydroxy-2,5-hexanedione, yield 18.8%, m.p 89-90 ℃.
Synthetic example 7
In 1000mL autoclave pressure, adding 200.0g mass percent concentration is 32% pyruvic aldehyde and isopropanol/water (130mL, Virahol: water=3: 1 (V: V)), it is the acid-basicity pH13-14 that 10% sodium carbonate solution is neutralized to reaction medium that machine mixer stirs lower dropping mass percent concentration, under nitrogen protection, add 10% palladium/aluminum trioxide catalyst 12.8g, air in 15 minutes displacement bottles of logical nitrogen, 15 minutes displacement nitrogen of logical hydrogen again, the temperature that maintains reaction solution is 45-50 ℃, under 0.2MPa pressure, react 2.5 hours, till reaction extremely no longer absorbs hydrogen, GC detection reaction is complete, filter, normal pressure is concentrated, filtrate extracts by 4x130ml ethyl acetate, merge extraction liquid, normal pressure is concentrated, obtains 16.7g thick liquid, uses ethyl acetate/petroleum ether freezing and crystallizing, and suction filtration, obtains 7.2g 3,4-dihydroxy-2,5-hexanedione, yield 11.2%, m.p 88-90 ℃.
Synthetic example 8
In 1000ml autoclave pressure, adding 300.0g mass percent concentration is 22% pyruvic aldehyde and ethanol/water (300mL, ethanol: water=1: 4 (V: V)) the acid-basicity pH3-4 of reaction medium, under nitrogen protection, add 1% palladium/carbon catalyst 33g, air in 20 minutes displacement bottles of logical nitrogen, 18 minutes displacement nitrogen of logical hydrogen again, the temperature that maintains reaction solution is 33-37 ℃, under 0.14MPa pressure, reacts 4 hours, till reaction extremely no longer absorbs hydrogen, GC detection reaction is complete, filters, and filtrate extracts by 4x180ml ethyl acetate; Merge extraction liquid, normal pressure is concentrated, obtains 26.5g thick liquid, uses ethyl acetate/petroleum ether freezing and crystallizing, and suction filtration, obtains 13.3g 3,4-dihydroxy-2,5-hexanedione, yield 20.2%, m.p 88-90 ℃.
Synthetic example 9
In 1000ml autoclave pressure, adding 200.0g mass percent concentration is 32% pyruvic aldehyde and ethanol/water (100mL, ethanol: water=2: 1 (V: V)), it is the acid-basicity pH9-10 that 10% sodium carbonate solution is neutralized to reaction medium that machine mixer stirs lower dropping mass percent concentration, under nitrogen protection, add Raney's nickel catalyst 19.2g, air in 13 minutes displacement bottles of logical nitrogen, 12 minutes displacement nitrogen of logical hydrogen again, the temperature that maintains reaction solution is 25-30 ℃, under 0.18MPa pressure, react 15 hours, till reaction extremely no longer absorbs hydrogen, GC detection reaction is complete, filter, filtrate extracts by 4x120ml ethyl acetate, merge extraction liquid, normal pressure is concentrated, obtains 22.1g thick liquid, uses ethyl acetate/petroleum ether freezing and crystallizing, and suction filtration, obtains 11.5g 3,4-dihydroxy-2,5-hexanedione.Yield 18.0%.m.p?88-90℃。
Synthetic example 10
In 1000ml autoclave pressure, adding 200.0g mass percent concentration is 30% pyruvic aldehyde and ethanol/water (60mL, ethanol: water=1: 1 (V: V)), it is the acid-basicity pH7-8 that 10% sodium carbonate solution is neutralized to reaction medium that machine mixer stirs lower dropping mass percent concentration, under nitrogen protection, add 3% palladium/aluminum trioxide catalyst 3.6g, air in 11 minutes displacement bottles of logical nitrogen, 11 minutes displacement nitrogen of logical hydrogen again, the temperature that maintains reaction solution is 16-21 ℃, under 0.11MPa pressure, react 7 hours, till reaction extremely no longer absorbs hydrogen, GC detection reaction is complete, filter, filtrate extracts by 4x120ml ethyl acetate, merge extraction liquid, normal pressure is concentrated, obtains 14.9g thick liquid, uses ethyl acetate/petroleum ether freezing and crystallizing, and suction filtration, obtains 8.6g3,4-dihydroxy-2,5-hexanedione, yield 14.3%, m.p 88-90 ℃.
Claims (9)
1. one kind 3, the preparation method of 4-dihydroxy-2,5-hexanedione, it is characterized in that in solvent, the compound of formula I, under the effect of catalyzer, uses hydrogen as reductive agent process reductive coupling, makes the compound of formula II, the compound of formula II is through suction filtration, concentrated, it is pure 3 that recrystallization can make, 4-dihydroxyl-2,5-hexanedione, concrete reaction formula is as follows:
Described catalyzer is Raney's nickel, 1～10% palladium/carbon or 1～10% palladium/aluminium sesquioxide;
The consumption of described catalyzer is 2%～30% of reaction substrate weight;
The mass percent concentration of described Compound I is 20～40%;
Described temperature of reaction is 0～50 ℃;
Described solvent is water or alcohol/water mixed solvent;
Described reductive coupling reaction is to carry out between 3～14 at pH.
2. preparation method as claimed in claim 1, is characterized in that, described catalyzer is 5% palladium/carbon.
3. preparation method as claimed in claim 1, is characterized in that, the mass percent concentration of described Compound I is 35%.
4. preparation method as claimed in claim 1, is characterized in that, described temperature of reaction is 10～40 ℃.
5. preparation method as claimed in claim 1, is characterized in that, described temperature of reaction is 25～30 ℃.
6. preparation method as claimed in claim 1, is characterized in that, in described alcohol/water mixed solvent, the volume ratio of alcohol and water is 3:1～1:4.
7. preparation method as claimed in claim 1, is characterized in that, described alcohol is one or more the mixing in methyl alcohol, ethanol, Virahol.
8. preparation method as claimed in claim 1, is characterized in that, described alcohol is ethanol.
9. preparation method as claimed in claim 1, is characterized in that, described reductive coupling reaction is to carry out between 7～8 at pH.
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| CN109879742A (en) * | 2019-03-23 | 2019-06-14 | 安徽金禾实业股份有限公司 | A kind of preparation method of 3,4- dihydroxy -2,5- acetyl butyryl |
| CN110845313A (en) * | 2019-09-27 | 2020-02-28 | 厦门欧米克生物科技有限公司 | Continuous preparation method of 3, 4-dihydroxy-2, 5-hexanedione |
| CN115819382A (en) * | 2022-11-16 | 2023-03-21 | 安徽金禾化学材料研究所有限公司 | Method for synthesizing 2, 5-dimethyl-4-hydroxy-3 (2H) -furanone perfume by one-pot method |
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| CN101039895A (en) * | 2004-11-02 | 2007-09-19 | 弗门尼舍有限公司 | A new process for the dimerisation of alkyl glyoxals |
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| CN101039895A (en) * | 2004-11-02 | 2007-09-19 | 弗门尼舍有限公司 | A new process for the dimerisation of alkyl glyoxals |
Non-Patent Citations (2)
| Title |
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| 3, 4-二羟基-2, 5-己二酮的合成研究;杨承鸿等;《合成材料老化与应用》;20011231(第3期);第21－23页 * |
| 杨承鸿等.3, 4-二羟基-2, 5-己二酮的合成研究.《合成材料老化与应用》.2001,(第3期),第21－23页. |
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