CN104557533A - Method for catalytic synthesis of acetoin short chain fatty acid ester by using phosphotungstic acid - Google Patents
Method for catalytic synthesis of acetoin short chain fatty acid ester by using phosphotungstic acid Download PDFInfo
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- CN104557533A CN104557533A CN201510036315.6A CN201510036315A CN104557533A CN 104557533 A CN104557533 A CN 104557533A CN 201510036315 A CN201510036315 A CN 201510036315A CN 104557533 A CN104557533 A CN 104557533A
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- acetoin
- acid
- chain fatty
- short chain
- fatty acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for catalytic synthesis of acetoin short chain fatty acid ester by using phosphotungstic acid. The method comprises the following steps: mixing acetoin with various short chain fatty acids including butyric acid, 2-methyl-butyric acid, 3-methyl-butyric acid, valeric acid in a proportion, and performing catalytic reaction at 50 DEG C by using phosphotungstic acid to synthesize various acetoin short chain fatty acid ester type compounds. The method disclosed by the invention has the advantages of mild reaction condition, easily available raw materials, simple step, environment friendliness, low production cost and the like.
Description
Technical field
The invention belongs to organic synthesis field, be specifically related to the method for a kind of catalysis of phosphotungstic acid synthesis acetoin butyric ester, acetoin 2-Methyl Butyric Acid ester, acetoin 3 Methylbutanoic acid ester, acetoin valerate.
Background technology
Acetoin fatty acid ester compound is natural to be present in some special fruit, red wine, vinegar, fresh flowers etc., gives their specific fragrance.Such as, ester derivative containing more a series of acetoin such as acetoin acetic ester, acetoin butyric ester, acetoin capronate, acetoin octanoate in pawpaw is the main aroma-producing substance of a class in pawpaw.Also containing a small amount of acetoin acetic ester and acetoin butyric ester in the banana of some kind.
The main application of acetoin fatty acid ester is in food and drink industry as spices; In addition, some acetoin esters can also be used as the organic solvent of epoxy resin and Vinylite etc.Because acetoin fatty acid ester has significant application value, its synthetic method receives publicity.
The U.S. authorizes patent (the US patent 3 invented by Burton and Wiese in nineteen sixty-eight, 404,176), wherein relate to the synthesis of acetoin acetic ester, method is with 2-butylene, methyl nitrite, acetic acid and diacetyl oxide for raw material, reacts under vitriol oil existence condition.This process Raw 2-butylene is inflammable, easily and air form explosive mixture, heat source and naked light have the danger of combustion explosion, and 2-butylene is heated violent polyreaction may occur; Raw material methyl nitrite facile hydrolysis discharges nitrous acid, is heated and easily decomposes, have the danger of blasting.
The U.S. authorizes again patent (the US patent 4 invented by Zoeller in nineteen ninety, 902,820), wherein also relate to the synthesis of acetoin acetic ester, the method first by concentration be 47% aqueous solution of hydrogen iodide join synthesis of acetyl iodine in diacetyl oxide, in this step, antioxidant Hypophosporous Acid, 50 be added.When after generation acetyliodide, precipitate and cross and filter Hypophosporous Acid, 50, then add 2,3-dimethyl diketone, acetyliodide and 2,3-dimethyl diketone react and generate acetoin acetic ester.In synthesis of acetyl iodine step, due to reaction process very heat release, the necessary extreme care of operation, and reactant is in ice bath.
Shiota is at article " Volatile components of pawpaw fruit (Asimina triloba Dunal.) " (Journal ofAgricultural and Food Chemistry, 39th volume 9 phase, 1991) in report adopt acetoin respectively with the method for diacetyl oxide, butyryl chloride, caproyl chloride, capryl(yl)chloride Reactive Synthesis acetoin fatty acid ester.This reaction is solvent with pentane, adds pyridine, under 5 ~ 10 DEG C of conditions, is added drop-wise in reaction system carefully by diacetyl oxide or acyl chlorides, and reaction terminates rear needs with the remaining pyridine of cuprous sulfate removing.
deng people at article " A deceptive pollination system targeting drosophilids througholfactory mimicry of yeast " (Current Biology, 20th volume 20 phase, 2010) in also adopt acetoin and diacetyl oxide to be Material synthesis acetoin acetic ester, difference is to adopt Amberlyst-15 to be catalyzer, acetoin is added dropwise in diacetyl oxide.There is larger potential safety hazard in the raw material such as diacetyl oxide and acyl chlorides, and also suffer the query of people in environmental pollution etc. in the processes such as preparation, transport, use.
Summary of the invention
In order to overcome now methodical deficiency, the invention provides the method for a kind of catalysis of phosphotungstic acid synthesis acetoin short-chain aliphatic ester, acetoin is reacted under the katalysis of phospho-wolframic acid with the short chain fatty acid such as butyric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, valeric acid respectively, the various ester derivatives of synthesis acetoin.
For achieving the above object, the technical solution used in the present invention is as follows:
A method for catalysis of phosphotungstic acid synthesis acetoin short-chain aliphatic ester, is characterized in that: with acetoin and short chain fatty acid for reaction substrate, add phosphate-tungstic acid, 50 DEG C of constant temperature oscillations react 24 hours, obtain acetoin short-chain aliphatic ester; The mol ratio of described acetoin and short chain fatty acid is 1:2; The add-on of described phosphate-tungstic acid is 5% ~ 6% of acetoin quality; Described short chain fatty acid is any one in butyric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid or valeric acid.
The advantages such as the present invention has reaction conditions gentleness, raw material is easy to get, step simple, environmental friendliness, production cost are low.
Accompanying drawing explanation
Accompanying drawing 1 is the electron ionization ion source mass spectrum of product acetoin butyric ester.
Accompanying drawing 2 is electron ionization ion source mass spectrums of product acetoin 2-Methyl Butyric Acid ester.
Accompanying drawing 3 is electron ionization ion source mass spectrums of product acetoin 3 Methylbutanoic acid ester.
Accompanying drawing 4 is electron ionization ion source mass spectrums of product acetoin valerate.
Embodiment
Below by way of specific embodiment, the technology of the present invention is further illustrated.Should be appreciated that embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
Embodiment 1
In closed glass screw socket bottle, add 0.1798g acetoin (i.e. 3-hydroxy-2-butanone), 1:2 (acetoin: short chain fatty acid) adds butyric acid in molar ratio, adds 0.0100g phospho-wolframic acid.50 DEG C of constant temperature oscillation reactions, hunting speed is 150r/min.24h reacts end, and sampling and recording reaction product concentration by gas-chromatography is 36.44g/L, adopts gas-chromatography-MS identification reaction product to be acetoin butyric ester.
Embodiment 2
With embodiment 1, but replace butyric acid with 2-Methyl Butyric Acid.24h reacts end, and sampling and recording reaction product concentration by gas-chromatography is 10.05g/L, adopts gas-chromatography-MS identification reaction product to be acetoin 2-Methyl Butyric Acid ester.
Embodiment 3
With embodiment 1, but replace butyric acid with 3 Methylbutanoic acid.24h reacts end, and sampling and recording reaction product concentration by gas-chromatography is 13.24g/L, adopts gas-chromatography-MS identification reaction product to be acetoin 3 Methylbutanoic acid ester.
Embodiment 4
With embodiment 1, but replace butyric acid with valeric acid.24h reacts end, and sampling and recording reaction product concentration by gas-chromatography is 30.77g/L, adopts gas-chromatography-MS identification reaction product to be acetoin valerate.
Claims (1)
1. a method for catalysis of phosphotungstic acid synthesis acetoin short-chain aliphatic ester, is characterized in that: with acetoin and short chain fatty acid for reaction substrate, add phosphate-tungstic acid, 50 DEG C of constant temperature oscillations react 24 hours, obtain acetoin short-chain aliphatic ester; The mol ratio of described acetoin and short chain fatty acid is 1:2; The add-on of described phosphate-tungstic acid is 5% ~ 6% of acetoin quality; Described short chain fatty acid is any one in butyric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid or valeric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510036315.6A CN104557533A (en) | 2015-01-22 | 2015-01-22 | Method for catalytic synthesis of acetoin short chain fatty acid ester by using phosphotungstic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510036315.6A CN104557533A (en) | 2015-01-22 | 2015-01-22 | Method for catalytic synthesis of acetoin short chain fatty acid ester by using phosphotungstic acid |
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| CN104557533A true CN104557533A (en) | 2015-04-29 |
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| CN201510036315.6A Pending CN104557533A (en) | 2015-01-22 | 2015-01-22 | Method for catalytic synthesis of acetoin short chain fatty acid ester by using phosphotungstic acid |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005010011A2 (en) * | 2003-07-15 | 2005-02-03 | Xenoport, Inc. | Methods of synthesis of acyloxyalkyl compounds |
| CN1205213C (en) * | 2000-08-10 | 2005-06-08 | 舍林股份公司 | Method for the production of imidazo-[1,2-c] [2,3]-benzodiazepines and intermediates in production thereof |
| CN103145551A (en) * | 2013-03-11 | 2013-06-12 | 北京理工大学 | Application of phosphotungstic acid serving as catalyst in mixed alcohol esterification |
-
2015
- 2015-01-22 CN CN201510036315.6A patent/CN104557533A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205213C (en) * | 2000-08-10 | 2005-06-08 | 舍林股份公司 | Method for the production of imidazo-[1,2-c] [2,3]-benzodiazepines and intermediates in production thereof |
| WO2005010011A2 (en) * | 2003-07-15 | 2005-02-03 | Xenoport, Inc. | Methods of synthesis of acyloxyalkyl compounds |
| CN103145551A (en) * | 2013-03-11 | 2013-06-12 | 北京理工大学 | Application of phosphotungstic acid serving as catalyst in mixed alcohol esterification |
Non-Patent Citations (1)
| Title |
|---|
| HARUYASU SHIOTA: "Volatile components of pawpaw fruit (Asimina triloba Dunal)", 《JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY》 * |
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Application publication date: 20150429 |