CN104860824A - Method for preparing pyruvate through catalyzing oxygen to oxidize lactate - Google Patents
Method for preparing pyruvate through catalyzing oxygen to oxidize lactate Download PDFInfo
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- CN104860824A CN104860824A CN201410062853.8A CN201410062853A CN104860824A CN 104860824 A CN104860824 A CN 104860824A CN 201410062853 A CN201410062853 A CN 201410062853A CN 104860824 A CN104860824 A CN 104860824A
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- lactate
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- pyruvate
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- pyruvic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
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Abstract
A method for preparing pyruvate through catalyzing oxygen to oxidize lactate is provided; according to the method, with a manganese compound as a catalyst and oxygen as an oxidant, lactate is catalyzed for efficient selective oxidation to obtain pyruvate. The process directly adopts oxygen as the oxidant, the reaction conditions are mild, the selectivity of the product pyruvate is good, and the method has important application prospects.
Description
Technical field
The present invention relates to a kind of preparation method of chemical, particularly relate to a kind of method that oxygen catalytic oxidation lactate prepares pyruvate, specifically, the method take manganic compound as catalyzer, oxygen is oxygenant, and direct oxygen catalytic oxidation lactate prepares pyruvate.
Background technology
Pyruvate is important fine chemicals and organic synthesis intermediate, can be widely used in the industries such as medicine, agricultural chemicals, food, spices and makeup.
The route of current synthesizing pyruvate comprises tartrate conversion method and lactate oxidation style etc.Tartrate dewaters, decarboxylation legal system is low for the product yield of pyruvate, and production cost is high, and environmental pollution is serious.Prepare pyruvate by lactate oxidation to be considered to the most effective approach and to receive much concern; But prepare pyruvate by lactate oxidation and mainly adopt KMnO
4in oxygenant, the oxygenant of this method consumption metering, cost is higher, produces a large amount of waste residue, contaminate environment.Development catalytic oxidation, is particularly the catalytic oxidation of oxygen source with molecular oxygen, has significant advantage.US4229590 discloses and utilizes crystalline state silver catalyzed oxidation lactate to prepare pyruvate, but catalyzer is precious metal, and temperature of reaction needs at high temperature to carry out (450-700 DEG C), and the yield of pyruvate lower (65-75%).At present prepared in the method for pyruvate by lactate, or need oxidant stoichiometry, or adopt noble metal catalyst under the high temperature conditions.Therefore, development in a mild condition, be oxygenant with molecular oxygen, catalytic selectivity Oxidation of Lactic ester prepares the significant and application prospect of the method for pyruvate.
The invention provides a kind of method that oxygen catalytic oxidation lactate prepares pyruvate, the method take manganic compound as catalyzer, and oxygen is oxygenant, and Direct Catalytic Oxidation lactate prepares pyruvate.This method is directly catalyzer with base metal, and cheap and easy to get, oxygen is oxygenant, green safety, and reaction conditions is gentle, therefore, has good development prospect.
Summary of the invention
The object of the present invention is to provide a kind of oxygen catalytic oxidation lactate to prepare the method for pyruvate, the method take manganic compound as catalyzer, and oxygen is oxygenant, realizes lactate efficiently catalyzing and oxidizing in a mild condition and prepares pyruvate.
In the present invention, oxygen catalytic oxidation lactate prepares the acid esters of raw dairy described in pyruvate, it can be methyl lactate, ethyl lactate, lactic acid n-propyl ester, one or two or more kinds in the secondary butyl ester of isopropyl lactate, n-butyl lactate, isobutyl lactate and lactic acid, reaction product pyruvate is one or two or more kinds in corresponding with the raw material secondary butyl ester of Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, pyruvic acid n-propyl, pyruvic acid isopropyl ester, the positive butyl ester of pyruvic acid, pyruvic acid isobutyl ester and pyruvic acid.
In the present invention, oxygen catalytic oxidation lactate prepares pyruvate used catalyst is manganic compound, comprises one or two or more kinds in manganous sulfate, manganous nitrate, manganous carbonate, manganous acetate (II), manganous acetate (III), Manganous chloride tetrahydrate, manganese sulfide, manganese monoxide, Manganse Dioxide, manganic oxide, trimanganese tetroxide, manganous oxalate, manganese acetylacetonate (II), manganese acetylacetonate (III), manganese citrate.The consumption of catalyzer manganic compound, counts the 0.5-20.0mol% of raw dairy acid esters with metal, when catalyst levels is 1.0-5.0mol%, the selectivity of product acetone acid esters is higher.
The oxygenant of catalyzed oxidation lactate provided by the present invention adopts oxygen, requires that in reaction process, oxygen pressure is 0.1-2.0MPa, preferred 0.5-1.5MPa; Temperature of reaction is 40-160 DEG C, and optimal reaction temperature is 60-120 DEG C; Reaction times is 4-20h, preferred 6-12h.
In the present invention, the reaction of oxygen catalytic oxidation lactate is carried out in organic solvent, reaction system solvent for use is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, acetic acid, acetonitrile, methyl acetate, ethyl acetate, diacetyl oxide, dimethyl sulfoxide (DMSO), tetramethylene sulfone, N, one or two or more kinds in dinethylformamide, Isosorbide-5-Nitrae-dioxane.
The key step that oxygen catalytic oxidation lactate provided by the invention prepares pyruvate is as follows:
Add a certain amount of substrate lactate, catalyzer manganic compound and solvent in a kettle., after replacement of oxygen gas reactor several times, be filled with a certain pressure between oxygen pressure to 0.1-2.0MPa, be heated to a certain temperature between 40-160 DEG C, maintain a certain reaction times between 4-20h.After question response terminates, reactor is cooled to room temperature, sampling analysis product, adopt Gas chromatographyMass spectrometry to product qualitative analysis, gas-chromatography carries out quantitative analysis to product.
Compared with prior art, the present invention has following features:
(1) the invention provides the method that oxygen catalytic oxidation lactate prepares pyruvate, catalyzer is non-precious metal catalyst, cheap and easy to get, and reaction conditions is gentle.
(2) oxygenant is oxygen, abundance, green safety.
With embodiment in detail the present invention is described in detail below.
Formula 1 oxygen catalytic oxidation lactate prepares the product of pyruvate
Embodiment
Embodiment 1: by 2.5mmol (0.26g) methyl lactate, 2.5mol% manganese acetylacetonate (III) is (in metal, relative to raw dairy acid esters), 2mL methyl alcohol, join in reactor, capping still, be filled with oxygen to 0.5MPa, be warming up to 100 DEG C under continuous stirring, and maintain 10h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature.Sample by gas chromatograph-mass spectrometer and HP-5 chromatogram column analysis product composition, mainly Pyruvic Acid Methyl ester, also detects the by products such as a small amount of methyl acetate (as shown in Equation 1) simultaneously, by gas-chromatography to reaction product quantitative analysis.The selectivity calculating Pyruvic Acid Methyl ester in product in conjunction with gas chromatographic analysis result is 92.1%.
Embodiment 2: by 2.5mmol (0.30g) ethyl lactate, 2mol% manganous acetate (II) (in metal, relative to raw dairy acid esters), 2mL ethanol, joins in reactor, capping still, be filled with oxygen to 1.0MPa, be warming up to 80 DEG C under constantly stirring, and maintain 8h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, be cooled to room.According to the methods analyst product in embodiment 1, the selectivity obtaining Pyruvic Acid Ethyl ester is 87.9%.
Embodiment 3: by 2.5mmol (0.33g) lactic acid n-propyl ester, 3mol% manganous sulfate (in metal, relative to raw dairy acid esters), 2mL tetramethylene sulfone, joins in reactor, capping still, be filled with oxygen to 1.5MPa, be warming up to 120 DEG C under constantly stirring, and maintain 8h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature, according to the methods analyst product in embodiment 1, the selectivity obtaining pyruvic acid n-propyl is 54.6%.
Embodiment 4: by 2.5mmol (0.37g) n-butyl lactate, 2.5mol% manganic oxide is (in metal, relative to raw dairy acid esters), 2mL dimethyl sulfoxide (DMSO), join in reactor, capping still, be filled with oxygen to 0.8MPa, be warming up to 110 DEG C under continuous stirring, and maintain 12h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature, according to the methods analyst product in embodiment 1, the selectivity obtaining the positive butyl ester of pyruvic acid is 57.8%.
Embodiment 5: by 2.5mmol (0.33g) isopropyl lactate, 1.5mol% manganous nitrate (in metal, relative to raw dairy acid esters), 2mL1,4-dioxane, joins in reactor, capping still, be filled with oxygen to 0.6MPa, be warming up to 100 DEG C under constantly stirring, and maintain 6h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature, according to the methods analyst product in embodiment 1, the selectivity obtaining pyruvic acid isopropyl ester is 53.3%.
Embodiment 6: by 2.5mmol (0.33g) isopropyl lactate, 1.5mol% trimanganese tetroxide is (in metal, relative to raw dairy acid esters), 2mL1,4-dioxane, joins in reactor, capping still, be filled with oxygen to 0.8MPa, be warming up to 100 DEG C under constantly stirring, and maintain 6h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature, according to the methods analyst product in embodiment 1, the selectivity obtaining pyruvic acid isopropyl ester is 41.6%.
Embodiment 7: by 2.5mmol (0.37g) isobutyl lactate, 1.5mol% manganous acetate (III) (in metal, relative to raw dairy acid esters), 2mL isopropylcarbinol, joins in reactor, capping still, be filled with oxygen to 0.5MPa, be warming up to 80 DEG C under constantly stirring, and maintain 10h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature, according to the methods analyst product in embodiment 1, the selectivity obtaining pyruvic acid isobutyl ester is 78.5%.
Embodiment 8: by 2.5mmol (0.26g) methyl lactate, 2mol% manganese citrate (in metal, relative to raw dairy acid esters), 2mL diacetyl oxide, joins in reactor, capping still, be filled with oxygen to 0.8MPa, be warming up to 120 DEG C under constantly stirring, and maintain 12h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature, according to the methods analyst product in embodiment 1, the selectivity obtaining Pyruvic Acid Methyl ester is 89.7%.
Embodiment 9: by 2.5mmol (0.30g) ethyl lactate, 3.5mol% manganese acetylacetonate (II) is (in metal, relative to raw dairy acid esters), 2mL acetonitrile, join in reactor, capping still, be filled with oxygen to 0.6MPa, be warming up to 100 DEG C under continuous stirring, and maintain 10h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature, according to the methods analyst product in embodiment 1, the selectivity obtaining Pyruvic Acid Ethyl ester is 75.3%.
Embodiment 10: by secondary for 2.5mmol (0.37g) lactic acid butyl ester, 2.5mol% manganous oxalate (in metal, relative to raw dairy acid esters), 2mL sec-butyl alcohol, joins in reactor, capping still, be filled with oxygen to 0.5MPa, be warming up to 60 DEG C under constantly stirring, and maintain 12h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature, according to the methods analyst product in embodiment 1, the selectivity obtaining the secondary butyl ester of pyruvic acid is 69.6%.
Embodiment 11: by 25mmol (2.6g) methyl lactate, 2.5mol% manganese acetylacetonate (II) is (in metal, relative to raw dairy acid esters), 20mL methyl alcohol, join in reactor, capping still, be filled with oxygen to 1.0MPa, be warming up to 110 DEG C under continuous stirring, and maintain 10h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature, according to the methods analyst product in embodiment 1, the selectivity obtaining Pyruvic Acid Methyl ester is 84.2%.
Embodiment 12: by 25mmol (3.0g) ethyl lactate, 1.5mol% manganous acetate (II) (in metal, relative to raw dairy acid esters), 20mL ethanol, joins in reactor, capping still, be filled with oxygen to 1.5MPa, be warming up to 100 DEG C under constantly stirring, and maintain 12h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature, according to the methods analyst product in embodiment 1, the selectivity obtaining Pyruvic Acid Ethyl ester is 80.7%.
Embodiment 13: by 250mmol (33g) isopropyl lactate, 3mol% manganous oxalate (in metal, relative to raw dairy acid esters), 200mL acetonitrile, joins in reactor, capping still, be filled with oxygen to 0.5MPa, be warming up to 80 DEG C under constantly stirring, and maintain 8h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature, according to the methods analyst product in embodiment 1, the selectivity obtaining pyruvic acid isopropyl ester is 73.5%.
Embodiment 14: by 250mmol (37g) n-butyl lactate, 5mol% manganese acetylacetonate (III) is (in metal, relative to raw dairy acid esters), 200mL propyl carbinol, join in reactor, capping still, be filled with oxygen to 0.6MPa, be warming up to 100 DEG C under continuous stirring, and maintain 6h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature, according to the methods analyst product in embodiment 1, the selectivity obtaining the positive butyl ester of pyruvic acid is 78.4%.
Embodiment 15: by 250mmol (37g) isobutyl lactate, 5mol% manganous acetate (III) (in metal, relative to raw dairy acid esters), 200mL isopropylcarbinol, joins in reactor, capping still, be filled with oxygen to 0.5MPa, be warming up to 60 DEG C under constantly stirring, and maintain 12h.As oxygen pressure declines in reaction process, supplemental oxygen is to original pressure.After reaction terminates, cool to room temperature, according to the methods analyst product in embodiment 1, the selectivity obtaining pyruvic acid isobutyl ester is 68.9%.
The above; be only some embodiments of the present invention; but protection scope of the present invention is not limited in this; also not because the precedence of each embodiment causes any restriction to the present invention; anyly be familiar with person skilled in the art of the present invention in the technical scope that the present invention reports; can carry out easily changing or replacing, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention is not limited only to above embodiment, should be as the criterion with the protection domain of claim.
Claims (6)
1. oxygen catalytic oxidation lactate prepares a method for pyruvate, it is characterized in that: take oxygen as oxygenant, and manganic compound is catalyzer, and direct oxygen catalytic oxidation lactate prepares pyruvate.
2. in accordance with the method for claim 1, it is characterized in that: described lactate is methyl lactate, ethyl lactate, lactic acid n-propyl ester, one or two or more kinds in the secondary butyl ester of isopropyl lactate, n-butyl lactate, isobutyl lactate and lactic acid; Reaction product pyruvate is one or two or more kinds in the secondary butyl ester of Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, pyruvic acid n-propyl, pyruvic acid isopropyl ester, the positive butyl ester of pyruvic acid, pyruvic acid isobutyl ester and the pyruvic acid corresponding with raw material.
3. in accordance with the method for claim 1, it is characterized in that: it is manganic compound that oxygen catalytic oxidation lactate prepares pyruvate used catalyst, comprise one or two or more kinds in manganous sulfate, manganous nitrate, manganous carbonate, manganous acetate (II), manganous acetate (III), Manganous chloride tetrahydrate, manganese sulfide, manganese monoxide, Manganse Dioxide, manganic oxide, trimanganese tetroxide, manganous oxalate, manganese acetylacetonate (II), manganese acetylacetonate (III), manganese citrate.
4., according to the method described in claim 1 and 3, it is characterized in that: oxygen catalytic oxidation lactate prepares the consumption of pyruvate catalyzer manganic compound, count the 0.5-20.0mol% of raw dairy acid esters with metal, preferred 1.0-5.0mol%.
5. in accordance with the method for claim 1, it is characterized in that: catalyzed oxidation lactate directly adopts oxygen to be oxygenant, require that in reaction process, oxygen pressure is 0.1-2.0MPa, preferred 0.5-1.5MPa; Temperature of reaction is 40-160 DEG C, preferred 60-120 DEG C; Reaction times is 4-20h, preferred 6-12h.
6. in accordance with the method for claim 1, it is characterized in that: the reaction of oxygen catalytic oxidation lactate is carried out in organic solvent, reaction system solvent for use is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, acetic acid, acetonitrile, methyl acetate, ethyl acetate, diacetyl oxide, dimethyl sulfoxide (DMSO), tetramethylene sulfone, N, one or two or more kinds in dinethylformamide, Isosorbide-5-Nitrae-dioxane.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106111173A (en) * | 2016-06-28 | 2016-11-16 | 厦门市净屋环保科技有限公司 | A kind of for being prepared the catalyst of pyruvate by lactate and preparing the method for pyruvate |
| CN106928059A (en) * | 2017-03-23 | 2017-07-07 | 南京师范大学 | A kind of catalysis oxidation synthesizes the method for ethyl pyruvate |
| CN107915628A (en) * | 2017-12-15 | 2018-04-17 | 朱友富 | A kind of green synthesis process of pyruvate |
| CN111825643A (en) * | 2019-04-15 | 2020-10-27 | 中国科学院大连化学物理研究所 | Preparation method of 2, 5-dicyanofuran |
| CN113198492A (en) * | 2021-05-12 | 2021-08-03 | 郑州大学 | Catalyst for preparing pyruvate by photocatalytic oxidation of lactate and method thereof |
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| JPH05255189A (en) * | 1992-03-13 | 1993-10-05 | Honsyu Kagaku Kogyo Kk | Production of alpha-keto acid ester |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106111173A (en) * | 2016-06-28 | 2016-11-16 | 厦门市净屋环保科技有限公司 | A kind of for being prepared the catalyst of pyruvate by lactate and preparing the method for pyruvate |
| CN106111173B (en) * | 2016-06-28 | 2017-09-01 | 厦门市净屋环保科技有限公司 | A kind of method for preparing pyruvate |
| CN106928059A (en) * | 2017-03-23 | 2017-07-07 | 南京师范大学 | A kind of catalysis oxidation synthesizes the method for ethyl pyruvate |
| CN107915628A (en) * | 2017-12-15 | 2018-04-17 | 朱友富 | A kind of green synthesis process of pyruvate |
| CN111825643A (en) * | 2019-04-15 | 2020-10-27 | 中国科学院大连化学物理研究所 | Preparation method of 2, 5-dicyanofuran |
| CN113198492A (en) * | 2021-05-12 | 2021-08-03 | 郑州大学 | Catalyst for preparing pyruvate by photocatalytic oxidation of lactate and method thereof |
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Application publication date: 20150826 |