CN102211988A - Preparation method of edible spice compound 3-hydroxy-2-pentanone - Google Patents
Preparation method of edible spice compound 3-hydroxy-2-pentanone Download PDFInfo
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- CN102211988A CN102211988A CN2011100860235A CN201110086023A CN102211988A CN 102211988 A CN102211988 A CN 102211988A CN 2011100860235 A CN2011100860235 A CN 2011100860235A CN 201110086023 A CN201110086023 A CN 201110086023A CN 102211988 A CN102211988 A CN 102211988A
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Abstract
The invention relates to a preparation method of an edible spice compound 3-hydroxy-2-pentanone. The formula (I) is the structure of the 3-hydroxy-2-pentanone. The preparation method comprises the following main processes of: sequentially adding 2-pentanone, hexamethyl disilazane (HMDS) and trimethyliodosilane into a reaction flask under the protection of nitrogen by using dried n-hexane as a solvent, and performing reduced pressure distillation to obtain 2-pentanone-2-trimethylsilylether after the reaction is finished; and performing epoxidation on the obtained silyl enol ether in dichloromethane by using meta-chloroperbenzoic acid, performing acidification and open loop treatment, and finally performing column chromatography separation and purification to obtain the 3-hydroxy-2-pentanone.
Description
The present invention relates to a kind of preparation method of flavoring compounds 3-hydroxyl-2 pentanone.
3-hydroxyl-2 pentanone is natural to be present in the fragrant composition of volatility of materials such as cheese, durian, honey, grape wine, coffee, Coconut Juice, soybean paste, tea, butter, aloe and fresh water blue-green algae, and its FEMA number is 3550, and it is fragrant and sweet to have roasted corn, butter and caramel.The preparation method of the 3-hydroxyl-2 pentanone of bibliographical information has two kinds, a kind of method be J ü rgen report with acetaldehyde and 1, the 3-dimercaptopropane is a raw material, at first obtains 1, the 3-dithiane, then under the effect of n-Butyl Lithium with propionic aldehyde reaction, the product HgCl that obtains
2/ HgO hydrolysis obtains 3-hydroxyl-2 pentanone, and the shortcoming of the maximum of this route is to adopt the very strong reagent HgCl of toxicity
2And HgO; Another kind method be beam the Beginning of Winter etc. people's report be raw material with acetaldehyde and propionic aldehyde, by 3-ethyl-4-methyl-5-(2-hydroxyethyl)-1, the catalytic cross-coupling reaction of 3-thiazole bromine salt obtains the mixture that various carbon chain lengths are five acyloin, wherein the mass percent of 3-hydroxyl-2 pentanone is 18.3%, the defective of this route is the product complexity, and productive rate is low.
The novel method that the purpose of this invention is to provide a kind of 3-of preparation hydroxyl-2 pentanone, preparation method of the present invention have advantage easy and simple to handle, that side reaction is few and productive rate is high.It is characterized in that with the 2 pentanone being starting raw material, obtain product through enolization, epoxidation and acidifying open loop three-step reaction, the first step reaction is that 2 pentanone at first obtains 2-2-pentenyl trimethylsilyl ethers with the Iodotrimethylsilane reaction under alkaline condition; The reaction of second step is the metachloroperbenzoic acid oxidation of 2-2-pentenyl trimethylsilyl ethers, obtains epoxide intermediates; Three-step reaction is that epoxide intermediates open loop under the effect of acid obtains 3-hydroxyl-2 pentanone, and reaction formula is as follows:
The present invention relates to the method for preparation formula (I) 3-hydroxyl-2 pentanone flavor compounds.
(I) 3-hydroxyl-2 pentanone
Its main process is: under nitrogen protection, make solvent with the exsiccant normal hexane, add 2 pentanone successively in reaction flask, hmds (HMDS) and Iodotrimethylsilane, after reaction finished, extraction was dry, concentrate, obtain 2-2-pentenyl trimethylsilyl ethers by underpressure distillation then; In methylene dichloride, add resulting silyl enol ether, add metachloroperbenzoic acid in batches, reaction 3-6h, after reaction finishes, extraction; Add HCl-MeOH solution in extraction liquid, stir 15-45min, after reaction finished, extraction was dry, concentrated, and purifying by column chromatography for separation at last obtains 3-hydroxyl-2 pentanone.
The structure of the 3-hydroxyl-2 pentanone for preparing in the inventive method is confirmed by nucleus magnetic resonance and mass spectrum.After analytical results is attached to embodiment.
Embodiment 1
In four-hole boiling flask, and the adding 2 pentanone (1.72g, 20mmol), normal hexane (120mL), logical nitrogen protection, adding hmds (HMDS) (3.9g, 24mmol).Behind the stirring at room 10min, flask is moved in the low temperature bath, continue to stir, the question response mixture is reduced to-20 ℃, and (4.4g 22mmol), reacts 10min to add Iodotrimethylsilane.Rise to room temperature, stir 2h, the back adds triethylamine (2.2g, 22mmol) stirring 15min then.After reaction finishes, reaction mixture is poured in the frozen water, and n-hexane extraction (3 * 60mL), merge organic phase, saturated common salt water washing, anhydrous magnesium sulfate drying.Underpressure distillation, the cut of 42-44 ℃/5.25KPa of collection is 2-2-pentenyl trimethylsilyl ethers, productive rate about 72%.
Product passes through
1HNMR and mass spectrum are confirmed.
1HNMR (CDCl
3), δ: 0.16 and 0.18 (s, 9H), 0.90 (m, 3H), 1.73 and 1.70 (d, 3H), 1.97 (m, 2H), 4.40 and 4.64 (td, 1H).
13CNMR(CDCl
3)，δ：2.4，14.4，18.7，22.6，110.9，145.8.GC/MS(EI)：m/z?158(M
+)。
(0.32g 2mmol) joins in the reaction flask with the 50mL methylene dichloride, adds the 3mmol metachloroperbenzoic acid under-25 ℃ in batches, reacts 5h down at-25 ℃ with 2-2-pentenyl trimethylsilyl ethers.At room temperature add the 3mmol triethylamine then, stir 15min, extremely neutral with the pH value of rare sodium hydrogen carbonate solution conditioned reaction mixture, tell organic phase, water dichloromethane extraction three times.Merge organic phase, and adding HCl-MeOH solution (6mol/L, 20mL), reflux 30min, with saturated sodium bicarbonate neutralization, separatory, salt is washed, the organic phase anhydrous Na
2SO
4After the drying, filter, concentrate, final product is by column chromatography for separation (silicagel column, V (sherwood oil)/V (ethyl acetate)=8: 1 wash-outs), and obtaining colourless liquid is 3-hydroxyl-2 pentanone, productive rate 78%.
Product structure passes through
1HNMR and mass spectrum are confirmed.
1HNMR(CDCl
3)，δ：0.94(t，3H)，1.62(m，1H)，1.92(m，1H)，2.19(s，3H)，3.47(d，1H)，4.16(t×d，1H)。MS(EI)，m/z：102(M
+)。
Embodiment 2
In four-hole boiling flask, and the adding 2 pentanone (1.72g, 20mmol), normal hexane (120mL), logical nitrogen protection, adding hmds (HMDS) (3.9g, 24mmol).Behind the stirring at room 20min, flask is moved in the low temperature bath, continue to stir, the question response mixture is reduced to-20 ℃, and (4.4g 22mmol), reacts 10min to add Iodotrimethylsilane.Rise to room temperature, stir 3h, the back adds triethylamine (2.2g, 22mmol) stirring 15min then.After reaction finishes, reaction mixture is poured in the frozen water, and petroleum ether extraction (3 * 60mL), merge organic phase, saturated common salt water washing, anhydrous magnesium sulfate drying.Underpressure distillation, the cut of 42-44 ℃/5.25KPa of collection is 2-2-pentenyl trimethylsilyl ethers, productive rate about 70%.
(0.32g 2mmol) joins in the reaction flask with the 50mL methylene dichloride, adds the 3mmol metachloroperbenzoic acid under 0 ℃ in batches, reacts 3h down at-25 ℃ with 2-2-pentenyl trimethylsilyl ethers.At room temperature add the 3mmol triethylamine then, stir 25min, extremely neutral with the pH value of rare sodium hydrogen carbonate solution conditioned reaction mixture, tell organic phase, water dichloromethane extraction three times.Merge organic phase, and adding HCl-MeOH solution (6mol/L, 20mL), reflux 15min, with saturated sodium bicarbonate neutralization, separatory, salt is washed, the organic phase anhydrous Na
2SO
4After the drying, filter, concentrate, final product is by column chromatography for separation (silicagel column, V (sherwood oil)/V (ethyl acetate)=8: 1 wash-outs), and obtaining colourless liquid is 3-hydroxyl-2 pentanone, productive rate 71%.
Product structure passes through
1HNMR and mass spectrum are confirmed, gained
1HNMR is identical with example 1 gained data with mass-spectrometric data.
Embodiment 3
In four-hole boiling flask, and the adding 2 pentanone (1.72g, 20mmol), normal hexane (120mL), logical nitrogen protection, adding hmds (HMDS) (3.9g, 24mmol).Behind the stirring at room 20min, flask is moved in the low temperature bath, continue to stir, the question response mixture is reduced to 0 ℃, and (4.4g 22mmol), reacts 15min to add Iodotrimethylsilane.Rise to room temperature, stir 4h, the back adds triethylamine (2.2g, 22mmol) stirring 15min then.After reaction finishes, reaction mixture is poured in the frozen water, and petroleum ether extraction (3 * 60mL), merge organic phase, saturated common salt water washing, anhydrous magnesium sulfate drying.Underpressure distillation, the cut of 42-44 ℃/5.25KPa of collection is 2-2-pentenyl trimethylsilyl ethers, productive rate about 67%.
(0.32g 2mmol) joins in the reaction flask with the 50mL methylene dichloride, adds the 3mmol metachloroperbenzoic acid under-25 ℃ in batches, reacts 6h down at-25 ℃ with 2-2-pentenyl trimethylsilyl ethers.At room temperature add the 3mmol triethylamine then, stir 15min, extremely neutral with the pH value of rare sodium hydrogen carbonate solution conditioned reaction mixture, tell organic phase, water dichloromethane extraction three times.Merge organic phase, and adding HCl-MeOH solution (6mol/L, 20mL), reflux 45min, with saturated sodium bicarbonate neutralization, separatory, salt is washed, the organic phase anhydrous Na
2SO
4After the drying, filter, concentrate, final product is by column chromatography for separation (silicagel column, V (sherwood oil)/V (ethyl acetate)=8: 1 wash-outs), and obtaining colourless liquid is 3-hydroxyl-2 pentanone, productive rate 72%.
Product structure passes through
1HNMR and mass spectrum are confirmed, gained
1HNMR is identical with example 1 gained data with mass-spectrometric data.
Claims (2)
1. the preparation method of flavoring compounds 3-hydroxyl-2 pentanone, it is characterized in that: be starting raw material with the 2 pentanone, obtain product through enolization, epoxidation and acidifying open loop three-step reaction, the first step reaction is that 2 pentanone at first obtains 2-2-pentenyl trimethylsilyl ethers with the Iodotrimethylsilane reaction under alkaline condition; The reaction of second step is the metachloroperbenzoic acid oxidation of 2-2-pentenyl trimethylsilyl ethers, obtains epoxide intermediates; Three-step reaction is that epoxide intermediates open loop under the effect of acid obtains 3-hydroxyl-2 pentanone.Reaction formula is as follows:
2. a kind of preparation structural formula according to claim 1 is suc as formula the method for the 3-hydroxyl-2 pentanone flavor compounds shown in (I).
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| CN101798296A (en) * | 2010-03-12 | 2010-08-11 | 北京工商大学 | Method for preparing alpha-(2-methyl-3-furanthio)one flavor compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798296A (en) * | 2010-03-12 | 2010-08-11 | 北京工商大学 | Method for preparing alpha-(2-methyl-3-furanthio)one flavor compounds |
Non-Patent Citations (3)
| Title |
|---|
| R.D.MILLER ET AL.: "The facile Silylation of Aldehydes and Ketones using Trimethylsilyl Iodide:An Exceptionally Simple Procedure for the Generation of Thermodynamically Equilibrated Trimethylsilyenol Ethers", 《SYNTHESIS》 * |
| 吴华彬 等: "三甲基卤硅烷在有机合成上的应用", 《江西大学学报（社会科学版）》 * |
| 皮士卿 等: "虾青素的合成", 《有机化学》 * |
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Application publication date: 20111012 |