CN102702146A - Method for preparing 2-nonylene-gamma-lactone simply, conveniently and practically - Google Patents
Method for preparing 2-nonylene-gamma-lactone simply, conveniently and practically Download PDFInfo
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- CN102702146A CN102702146A CN2012101733373A CN201210173337A CN102702146A CN 102702146 A CN102702146 A CN 102702146A CN 2012101733373 A CN2012101733373 A CN 2012101733373A CN 201210173337 A CN201210173337 A CN 201210173337A CN 102702146 A CN102702146 A CN 102702146A
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Abstract
The invention relates to a method for preparing 2-nonylene-gamma-lactone shown as a structural formula (I). The method comprises the following steps of: 1, oxidizing 2-nonenoic acid by using 30 percent hydrogen peroxide in a formic acid solution to obtain 3-hydroxyl-gamma-nonalactone serving as an intermediate, wherein the yield is 85.6 percent; and 2, reacting the 3-hydroxyl-gamma-nonalactone with methylsulfonyl chloride in a dichloromethane solution to form ester mesylate, and removing the ester mesylate under the action of triethylamine to obtain the 2-nonylene-gamma-lactone, wherein the yield is 88.0 percent.
Description
The present invention relates to a kind of preparation method of simple and practical 2-nonene-gamma lactone.
2-nonene-gamma lactone is natural to be present in the odor component of multiple food and plant milk extract, and like beef/vegetable soup, sunflower seed oil, noodles, watermelon, potato chips, lard, mushroom, fried potato, Flower of Beltleaf Primrose, flue-cured tobacco etc., it is fragrant and fragrant and sweet to have a coconut.This compound has passed through the safety evaluation of U.S. FEMA (Flavour and Extract Manufacturers ' Association) tissue in 2005, be published in the 22nd batch of flavouring agent safe list, and FEMA number is 4188.α, β-unsaturated gamma lactone is the structural unit of the natural product of many biologically actives, a lot of bibliographical informations have been arranged its compound method, some representative compound methods are following in recent years.With vinylformic acid is that raw material makes 3-p-toluenesulfonyl vinylformic acid, under the effect of butyllithium and aldehyde reaction, under the effect of alkali, eliminates reaction then and obtaining the substituted α of 4-alkyl, β-unsaturated gamma lactone; With the propenal is that raw material makes 3-p-toluenesulfonyl propionic aldehyde dimethyl acetal, under the effect of butyllithium and aldehyde reaction, then through peroxo-, eliminate reaction and obtain product; Oxidation also can be converted into the substituted α of 4-alkyl, β-unsaturated gamma lactone to the substituted 2,3 dihydro furan of 4-alkyl through singlet oxygen; Acrylic acid replacement allyl alcohol ester is at RuCl
2Katalysis under carry out the alkene replacement(metathesis)reaction and can obtain the substituted α of 4-alkyl, β-unsaturated gamma lactone; (E)-and 3-alkane olefin(e) acid and the electrophilic reagent effect that contains selenium, addition and elimination two-step reaction through treating different things alike can obtain the substituted α of 4-alkyl, β-unsaturated gamma lactone.All there is defective in various degree in these methods, and, reaction raw materials long like route is difficult for obtaining, reagent is expensive, productive rate is low or the like, therefore easy and simple to handle, high yield and cheaply the preparation method of 2-nonene-gamma lactone still remain further to be explored.
The preparation method who the purpose of this invention is to provide a kind of simple and practical 2-nonene-gamma lactone.It is characterized in that with (E)-3-nonenoic acid be starting raw material, carry out oxidation, the midbody that ring closure reaction obtains 3-hydroxyl-γ-Ren Neizhi takes place simultaneously, eliminate reaction through methanesulfonates then and obtain title product with ydrogen peroxide 50.The first step reaction is that (E)-3-nonenoic acid is used hydrogen peroxide oxidation in formic acid solution, obtains the midbody of 3-hydroxyl-γ-Ren Neizhi, productive rate 85.6%; The reaction of second step is 3-hydroxyl-γ-Ren Neizhi and methylsulfonyl chloride reaction in the solution of methylene dichloride, and the methanesulfonates of formation is eliminated reaction, obtains 2-nonene-gamma lactone, productive rate 88.0%.The friendly green oxidation agent hydrogen peroxide of environment for use carries out oxidation among the preparation method of the present invention, has that raw material is easy to get, easy and simple to handle and advantage that productive rate is high.Reaction formula is following:
The present invention relates to the preparation method of a kind of structure suc as formula the 2-nonene-gamma lactone shown in (I):
Its main process is: in four-hole boiling flask, add formic acid, 30% ydrogen peroxide 50, stir, drip the 2-nonenoic acid, the control rate of addition makes system temperature maintain certain limit.Dropwise the afterreaction certain hour, underpressure distillation obtains midbody 3-hydroxyl-γ-Ren Neizhi then; 3-hydroxyl-the γ-Ren Neizhi that obtains reacts with methylsulfonyl chloride in dichloromethane solution, and the first sulphur ester of formation is eliminated under the triethylamine effect, promptly gets 2-nonene-gamma lactone, productive rate 88.0%.
The structure of 2-nonene-gamma lactone for preparing in the inventive method and important midbody is all confirmed through nucleus magnetic resonance or mass spectrum.After analytical results is attached to embodiment.
Embodiment
(1) preparation of 3-hydroxyl-γ-Ren Neizhi
In the 250mL four-hole boiling flask that TM, magnetic agitation, constant pressure funnel are housed; Add 88% formic acid 100mL (2.28mol), 30% ydrogen peroxide 50 35mL (0.35mol); Stir 10min, drip 2-nonenoic acid 25.5g (0.16mol), the control rate of addition; Make system temperature maintain 20 ℃～40 ℃, about 40min dropwises.40 ℃ of isothermal reactions, reaction 5h finishes then.Reaction mixture cools off with ice bath, and the NaOH solution of Dropwise 35 % is neutralized to pH 9.With extracted with diethyl ether (80mL * 3), merge organic phase, with saturated common salt water washing (50mL * 3), anhydrous magnesium sulfate drying.Revolve to steam and remove ether, the cut of 114 ℃ of-118 ℃/0.5KPa is collected in the resistates underpressure distillation, obtains 3-hydroxyl-γ-Ren Neizhi 23.55g, and productive rate is 85.6%.
1HNMR(CDCl
3)δ0.89(t，J＝6.9Hz，3H，Me)，1.33-1.86(m，8H，H-C(1′)～C(4′))，2.53(dd，J＝18.0，3.7Hz，1H，H-C(2))，2.76(dd，J＝18.0，6.6Hz，1H，H-C(2))，4.34(m，1H，H-C(3))，4.45(m，1H，H-C(4))。
13CNMR(CDCl
3)δ13.8(C(5′))，22.3(C(4′))，24.7(C(2′))，31.3((C(3′))，32.8(C(1′))，37.5(C(2))，71.2(C(3))，88.4(C(4))，176.4(C(1))。
(2) preparation of 2-nonene-gamma lactone
In the 250mL four-hole boiling flask that TM, magnetic agitation and constant pressure funnel are housed; Add 3-hydroxyl-γ-Ren Neizhi 24g (0.14mol), methylene dichloride 100mL and triethylamine 44mL (0.315mol), stir, drip methylsulfonyl chloride 16mL (0.21mol) down at 0 ℃; The control rate of addition; Make system temperature in 0 ℃～5 ℃, about 1h dropwises, and is warming up to 25 ℃ of reactions.Reaction finishes postcooling, with saturated common salt water washing (50mL * 3), anhydrous magnesium sulfate drying.Revolve to steam and remove methylene dichloride,, collect the cut of 104 ℃ of-106 ℃/0.4kPa, get product 19g, productive rate 88.0% the residuum underpressure distillation.
1HNMR(CDCl
3)δ0.89(t，J＝6.9Hz，3H，Me)，1.31-1.33(m，4H，H-C(3′)～C(4′))，1.46(m，2H，H-C(2′))，1.65-1.77(m，2H，H-C(1′))，5.03(m，1H，H-C(4))，6.11(dd，J＝5.7，1.5Hz，1H，H-C(2))，7.45(d，J＝5.7，2.0Hz，1H，H-C(3))。
13CNMR(CDCl
3)δ13.5(C(5′))，22.0(C(4′))，24.2(C(2′))，31.0((C(3′))，32.7(C(1′))，83.1(C(4))，120.9(C(2))，156.2(C(3))，172.9(C(1))(cf.Ref.17).GC/MS(EI)m/z?154(4，M
+)，125(72)，84(100)，83(19)，55(15)。
Claims (1)
1. the preparation method of a simple and practical 2-nonene-gamma lactone; It is characterized in that with (E)-3-nonenoic acid be starting raw material, carry out oxidation, the midbody that ring closure reaction obtains 3-hydroxyl-γ-Ren Neizhi takes place simultaneously with ydrogen peroxide 50; Eliminate reaction through methanesulfonates then and obtain title product; The first step reaction is that (E)-3-nonenoic acid is used hydrogen peroxide oxidation in formic acid solution, obtains the midbody of 3-hydroxyl-γ-Ren Neizhi, productive rate 85.6%; The reaction of second step is 3-hydroxyl-γ-Ren Neizhi and methylsulfonyl chloride reaction in the solution of methylene dichloride, and the methanesulfonates of formation is eliminated reaction, obtains 2-nonene-gamma lactone, productive rate 88.0%, and reaction formula is following:
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108383812A (en) * | 2018-04-25 | 2018-08-10 | 北京工商大学 | A kind of α, the preparation method of β-unsaturation-gamma lactone |
| CN113620913A (en) * | 2021-07-26 | 2021-11-09 | 安徽华业香料股份有限公司 | Method for synthesizing gamma-nonene lactone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687046A (en) * | 2005-04-12 | 2005-10-26 | 厦门大学 | Method for preparing (S)-3-hydroxy group-gamma-butyrolactone |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687046A (en) * | 2005-04-12 | 2005-10-26 | 厦门大学 | Method for preparing (S)-3-hydroxy group-gamma-butyrolactone |
Non-Patent Citations (3)
| Title |
|---|
| 《日用化学工业》 20100630 肖阳等 手性香料化合物gamma-内酯的不对称合成 194-198 1 第40卷, 第3期 * |
| XIN CHEN, ET AL.: "One-step and non-catalytic intramolecular redox reactions of conjugated all E-dienals to non-conjugated Z-enoic acids in subcritical water", 《THE JOURNAL OF SUPERCRITICAL FLUIDS》 * |
| 肖阳等: "手性香料化合物γ-内酯的不对称合成", 《日用化学工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108383812A (en) * | 2018-04-25 | 2018-08-10 | 北京工商大学 | A kind of α, the preparation method of β-unsaturation-gamma lactone |
| CN113620913A (en) * | 2021-07-26 | 2021-11-09 | 安徽华业香料股份有限公司 | Method for synthesizing gamma-nonene lactone |
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Application publication date: 20121003 |