CN105001192B - ε n-pentyl propionate base ε caprolactones and preparation method thereof - Google Patents
ε n-pentyl propionate base ε caprolactones and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 title claims description 11
- -1 n-pentyl acrylate compound Chemical class 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000003377 acid catalyst Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 claims abstract description 4
- 238000005886 esterification reaction Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical group OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 claims 1
- 239000003205 fragrance Substances 0.000 abstract description 18
- 238000011160 research Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 235000009508 confectionery Nutrition 0.000 abstract description 2
- 235000019991 rice wine Nutrition 0.000 abstract description 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 235000014101 wine Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 5
- 239000000796 flavoring agent Substances 0.000 description 4
- 235000019634 flavors Nutrition 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 125000000422 delta-lactone group Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000457 gamma-lactone group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000003120 macrolide antibiotic agent Substances 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyrane Compounds (AREA)
Abstract
本发明公开了一种ε‑内酯型香料化合物，其结构式如下：。本发明还公开了上述ε‑内酯型香料化合物的制备方法，以酸类化合物和醇类化合物为原料，有机溶剂中通过酸催化剂发生酯化反应，得丙烯酸正戊酯化合物，所得丙烯酸正戊酯化合物再和烯类化合物为原料，在有机溶剂中通过碱催化剂和酸催化剂发生加成和Baeyer‑Villiger氧化反应，最终获得ε‑丙酸正戊酯基‑ε‑己内酯化合物。本发明是一种新型ε‑内酯型带有特征的醇甜米酒的酒香香气的化合物，是国内外对于ε‑内酯型带有特征香气化合物的最新研究成果。
The invention discloses an ε-lactone type fragrance compound, the structural formula of which is as follows: . The invention also discloses a preparation method of the above-mentioned ε-lactone-type fragrance compound, which uses acid compounds and alcohol compounds as raw materials, undergoes an esterification reaction through an acid catalyst in an organic solvent, and obtains n-pentyl acrylate compound, and the obtained n-pentyl acrylate The ester compound and the alkenyl compound are used as raw materials, and the addition and Baeyer-Villiger oxidation reaction occur through a base catalyst and an acid catalyst in an organic solvent, and finally the ε-propionyl n-pentyl-ε-caprolactone compound is obtained. The present invention is a novel ε-lactone type compound with characteristic wine aroma of sweet rice wine, and is the latest research achievement of ε-lactone type compound with characteristic aroma at home and abroad.
Description
技术领域technical field
本发明属于化工领域，尤其涉及一种内酯型香料化合物，具体来说是一种ε-丙酸正戊酯基-ε-己内酯及其制备方法。The invention belongs to the field of chemical industry, and in particular relates to a lactone-type fragrance compound, in particular to ε-n-pentyl propionyl-ε-caprolactone and a preparation method thereof.
背景技术Background technique
内酯型香料化合物普遍存在于自然界中，大部分的内酯型香料化合物可以在自然界中获得，在食品香精和日化香精的调配中用途广泛，既可以作为香精的主香调也可以作为配料。其中的大部分内酯型香料化合物阈值低，在香精配方中用量节省而且香气强烈。国内外对于内酯型香料化合物的研究普遍在：γ-内酯型香料化合物、δ-内酯型香料化合物、大环内酯型香料化合物上。其中γ-内酯型香料呈现明显的果香香气，δ-内酯型香料呈现明显的奶香香气，大环内酯型香料呈现明显的麝香香气，这部分的内酯型香料使用稳定、香气的天然感强，而且它们大部分可以从自然界中获得，但是成本高、产率低。但是目前国内外鲜有对于ε-内酯型香料化合物的研究及其制备，使得ε-内酯型香料化合物在国内外研究和制备中都是空缺。Lactone-type fragrance compounds are ubiquitous in nature, and most of the lactone-type fragrance compounds can be obtained in nature. They are widely used in the formulation of food flavors and daily chemical flavors. They can be used as the main fragrance of flavors or as ingredients . Most of the lactone-type fragrance compounds have a low threshold value, so they are used sparingly in flavor formulations and have a strong aroma. The research on lactone-type fragrance compounds at home and abroad is generally on: γ-lactone-type fragrance compounds, δ-lactone-type fragrance compounds, and macrolide-type fragrance compounds. Among them, the γ-lactone type fragrance presents an obvious fruity aroma, the δ-lactone type fragrance presents an obvious milky aroma, and the macrolide type fragrance presents an obvious musky aroma. This part of the lactone type fragrance is stable in use and fragrant. The natural sense is strong, and most of them can be obtained from nature, but the cost is high and the yield is low. However, there are few researches and preparations on ε-lactone fragrance compounds at home and abroad at present, which makes the research and preparation of ε-lactone fragrance compounds both at home and abroad vacancies.
发明内容Contents of the invention
针对现有技术中的技术问题，本发明提供了一种ε-丙酸正戊酯基-ε-己内酯及其制备方法，所述的这种ε-丙酸正戊酯基-ε-己内酯及其制备方法解决了现有技术中制备ε-内酯型香料化合物困难、成本高、产率低的技术问题。Aiming at the technical problems in the prior art, the present invention provides a kind of ε-n-pentyl propionate-ε-caprolactone and its preparation method, the described ε-n-pentyl propionate-ε- The caprolactone and the preparation method thereof solve the technical problems of difficulty in preparing ε-lactone type fragrance compounds, high cost and low yield in the prior art.
本发明提供了一种ε-丙酸正戊酯基-ε-己内酯，其结构式如下：The present invention provides a kind of ε-n-pentyl propionate group-ε-caprolactone, its structural formula is as follows:
。 .
本发明还提供了上述的ε-丙酸正戊酯基-ε-己内酯的制备方法，包括如下步骤：The present invention also provides the preparation method of the above-mentioned ε-n-pentyl propionate-ε-caprolactone, comprising the steps of:
1)以酸类化合物和醇类化合物为起始原料，在第一有机溶剂中，通过第一酸催化剂酯化，在回流的温度下，反应8-10h，制备得到丙烯酸正戊酯化合物；1) using an acid compound and an alcohol compound as starting materials, in the first organic solvent, through the first acid catalyst esterification, at the temperature of reflux, react for 8-10h, and prepare the n-pentyl acrylate compound;
2)丙烯酸正戊酯化合物和烯类化合物在第二有机溶剂中，通过碱催化剂和第二酸催化2) n-pentyl acrylate compound and alkene compound are in the second organic solvent, catalyzed by the base catalyst and the second acid
剂加成、Baeyer-Villiger氧化，在室温或者低于回流温度、氮气保护下，反应4-8h，制备得到ε-丙酸正戊酯基-ε-己内酯化合物。Reagent addition, Baeyer-Villiger oxidation, at room temperature or below reflux temperature, under nitrogen protection, react for 4-8h to prepare ε-n-pentyl propionate-ε-caprolactone compound.
进一步的，所述的酸类化合物为丙烯酸，所述的醇类化合物为正戊醇，所述的丙烯酸与正戊醇的摩尔比为1.0:1.0~2.0。Further, the acid compound is acrylic acid, the alcohol compound is n-pentanol, and the molar ratio of acrylic acid to n-pentanol is 1.0:1.0-2.0.
进一步的，所述的酸类化合物和醇类化合物的摩尔之和与第一有机溶剂的摩尔比为1.0~1.5：1.0。Further, the molar ratio of the molar sum of the acid compound and the alcohol compound to the first organic solvent is 1.0-1.5:1.0.
进一步的，所述的第一有机溶剂为甲苯。Further, the first organic solvent is toluene.
进一步的，所述的酸类化合物和醇类化合物：第一酸催化剂的摩尔比为10.0~15.0:1.0。Further, the molar ratio of the acid compound and the alcohol compound: the first acid catalyst is 10.0-15.0:1.0.
进一步的，所述第一酸催化剂为对甲苯磺酸。Further, the first acid catalyst is p-toluenesulfonic acid.
进一步的，所述的丙烯酸正戊酯化合物与所述烯类化合物的摩尔比为1.5~2.5:1.0。Further, the molar ratio of the n-pentyl acrylate compound to the vinyl compound is 1.5-2.5:1.0.
进一步的，所述烯类化合物为1-吡咯烷-1-环己烯。Further, the alkene compound is 1-pyrrolidine-1-cyclohexene.
进一步的，所述的丙烯酸正戊酯化合物和烯类化合物与所述的第二有机溶剂的摩尔比为0.05~0.07:1.0。Further, the molar ratio of the n-pentyl acrylate compound and the vinyl compound to the second organic solvent is 0.05-0.07:1.0.
进一步的，所述的第二有机溶剂为二氯甲烷。Further, the second organic solvent is dichloromethane.
进一步的，所述的丙烯酸正戊酯和烯类化合物：碱催化剂的摩尔比为1.9~2.0:1.0。Further, the molar ratio of said n-pentyl acrylate and vinyl compound: base catalyst is 1.9-2.0:1.0.
进一步的，所述碱催化剂为磷酸氢二钠。Further, the alkali catalyst is disodium hydrogen phosphate.
进一步的，所述的丙烯酸正戊酯和烯类化合物：第二酸催化剂的摩尔比为3.5~4.0:1.0。Further, the molar ratio of the n-pentyl acrylate and the vinyl compound: the second acid catalyst is 3.5-4.0:1.0.
进一步的，所述第二酸催化剂为间氯过氧苯甲酸。Further, the second acid catalyst is m-chloroperoxybenzoic acid.
上述一种ε-丙酸正戊酯基-ε-己内酯化合物的合成路线如下：The synthetic route of above-mentioned a kind of ε-propionic acid n-pentyl-ε-caprolactone compound is as follows:
本发明的方法是以酸类化合物和醇类化合物为原料，有机溶剂中通过酸催化剂发生酯化反应，得丙烯酸正戊酯化合物，所得丙烯酸正戊酯化合物再和烯类化合物为原料，在有机溶剂中通过碱催化剂和酸催化剂发生加成和Baeyer-Villiger氧化反应，最终获得ε-丙酸正戊酯基-ε-己内酯化合物。The method of the present invention is to take acid compound and alcohol compound as raw material, and the esterification reaction takes place by acid catalyst in organic solvent, obtains n-pentyl acrylate compound, and the obtained n-pentyl acrylate compound and alkenyl compound are raw materials, in organic solvent Addition and Baeyer-Villiger oxidation reactions occur through base catalyst and acid catalyst in the solvent to finally obtain ε-n-pentyl propionate-ε-caprolactone compound.
本发明和已有技术相比，其技术进步是显著的。本发明提供了一种ε-丙酸正戊酯基-ε-己内酯及合成方法，是一种新型ε-内酯型带有特征的醇甜米酒的酒香香气的化合物，是国内外对于ε-内酯型带有特征香气化合物的最新研究成果。Compared with the prior art, the technical progress of the present invention is remarkable. The invention provides a kind of ε-n-pentyl propionyl-ε-caprolactone and its synthesis method, which is a new type of ε-lactone type compound with characteristic alcohol and sweet rice wine aroma and aroma, and is famous at home and abroad. The latest research results on ε-lactone compounds with characteristic aroma.
附图说明Description of drawings
图1是实施例1中所得的丙烯酸正戊酯的核磁氢谱分析图。Fig. 1 is the proton nuclear magnetic spectrum analysis figure of n-pentyl acrylate gained in embodiment 1.
图2是实施例2中所得的ε-丙酸正戊酯基-ε-己内酯化合物的核磁氢谱分析图。Fig. 2 is the H NMR spectrum analysis diagram of the ε-propionate n-pentyl-ε-caprolactone compound obtained in Example 2.
图3是实施例2中所得的ε-丙酸正戊酯基-ε-己内酯化合物的核磁碳谱分析图。Fig. 3 is the carbon nuclear magnetic spectrum analysis diagram of the ε-n-pentyl propionate-ε-caprolactone compound obtained in Example 2.
具体实施方式detailed description
下面通过具体实施例对本发明进一步阐述，但并不限制本发明。The present invention is further illustrated below by specific examples, but the present invention is not limited.
实施例1Example 1
一种丙烯酸正戊酯化合物的合成方法，具体步骤如下：A kind of synthetic method of n-pentyl acrylate compound, concrete steps are as follows:
在100ml圆底烧瓶中，加入17.32g（0.19mol）的无水甲苯、4.9g（0.01mol）对甲基苯磺酸、7.245g（0.10mol）丙烯酸、11.02g(0.13mol)正戊醇在110℃下磁力搅拌、回流，反应8小时；反应完毕，将反应液冷却至室温，向反应液中加入饱和碳酸氢钠水溶液，用乙酸乙酯萃取有机相，有机相用饱和食盐水洗涤三次，无水硫酸镁干燥，用旋蒸仪旋蒸除去溶剂，产品利用薄层色谱法获得纯品，洗脱剂为PE:EA=8:1，收集纯品最终得透明无色液体12.87ml，产率为94.2%。In a 100ml round bottom flask, add 17.32g (0.19mol) of anhydrous toluene, 4.9g (0.01mol) of p-toluenesulfonic acid, 7.245g (0.10mol) of acrylic acid, 11.02g (0.13mol) of n-pentanol in Magnetic stirring and reflux at 110°C for 8 hours of reaction; after the reaction was completed, the reaction solution was cooled to room temperature, saturated aqueous sodium bicarbonate solution was added to the reaction solution, the organic phase was extracted with ethyl acetate, and the organic phase was washed three times with saturated brine. Anhydrous magnesium sulfate was dried, and the solvent was removed by rotary evaporation with a rotary evaporator. The product was obtained by thin-layer chromatography, and the eluent was PE:EA=8:1. The pure product was collected to finally obtain 12.87ml of transparent and colorless liquid. The rate is 94.2%.
上述所得的透明无色液体通过核磁共振仪器（Bruker AVANCE III 500 MHz）进行氢谱测定，数据如下所示（如图1所示）：The transparent colorless liquid obtained above was subjected to hydrogen spectrum measurement by a nuclear magnetic resonance instrument (Bruker AVANCE III 500 MHz), and the data are as follows (as shown in Figure 1):
1H NMR (501 MHz, CDCl3) δ 6.41 (d, J = 17.3 Hz, 1H), 6.18 – 6.11 (m,1H), 5.83 (d, J = 10.4 Hz, 1H), 4.18 (s, 2H), 1.68 (d, J = 7.0 Hz, 2H), 1.39– 1.35 (m, 4H), 1.28 (t, J = 7.1 Hz, 3H). 1 H NMR (501 MHz, CDCl 3 ) δ 6.41 (d, J = 17.3 Hz, 1H), 6.18 – 6.11 (m,1H), 5.83 (d, J = 10.4 Hz, 1H), 4.18 (s, 2H) , 1.68 (d, J = 7.0 Hz, 2H), 1.39– 1.35 (m, 4H), 1.28 (t, J = 7.1 Hz, 3H).
通过上述所得的透明无色液体核磁共振谱数据分析，结果表明，上述所得的透明无色液体为丙烯酸正戊酯。Through the nuclear magnetic resonance spectrum data analysis of the transparent colorless liquid obtained above, the result shows that the transparent colorless liquid obtained above is n-pentyl acrylate.
实施例2Example 2
上述的一种ε-丙酸正戊酯基-ε-己内酯化合物的合成方法，具体步骤如下：The synthetic method of above-mentioned a kind of ε-propionate n-pentyl-ε-caprolactone compound, concrete steps are as follows:
在50ml三口烧瓶中加入1.42g（0.01mol）磷酸氢二钠固体，氮气置换三次，注入13.25g(0.16mol)二氯甲烷，磁力搅拌下，注入1.85g（0.013mol）丙烯酸正戊酯、0.97g(0.0064mol)1-吡咯烷-1-环己烯，搅拌30分钟后，缓慢注入溶解于13.25g(0.16mol)二氯甲烷的0.86g(0.005mol)间氯过氧苯甲酸溶液，在10分钟内完成，磁力搅拌下，反应4h；反应完毕，将三口烧瓶放入冰水中冷却，向反应液中加入15ml常温饱和碳酸氢钠水溶液洗涤一遍，用30ml饱和硫代硫酸钠水溶液洗涤两遍，用95ml的5%氢氧化钠水溶液洗涤两遍，用50ml蒸馏水洗涤两遍，用二氯甲烷萃取有机相，用80ml饱和氯化钠水溶液洗涤有机相三遍，最后用无水硫酸镁干燥有机相，用旋蒸仪旋蒸除去有机相，产品利用薄层色谱法获得纯品，洗脱剂为PE:EA=8:1，收集纯品最终得白色固体100mg，产率为6.1%。Add 1.42g (0.01mol) of disodium hydrogen phosphate solid into a 50ml three-necked flask, replace with nitrogen three times, inject 13.25g (0.16mol) of dichloromethane, and inject 1.85g (0.013mol) of n-pentyl acrylate, 0.97 g (0.0064mol) 1-pyrrolidine-1-cyclohexene, after stirring for 30 minutes, slowly inject 0.86g (0.005mol) m-chloroperoxybenzoic acid solution dissolved in 13.25g (0.16mol) methylene chloride, in Complete within 10 minutes, under magnetic stirring, react for 4 hours; after the reaction is completed, put the three-neck flask into ice water to cool, add 15ml of normal temperature saturated sodium bicarbonate aqueous solution to the reaction solution to wash once, and wash twice with 30ml saturated sodium thiosulfate aqueous solution , washed twice with 95ml of 5% sodium hydroxide aqueous solution, twice with 50ml of distilled water, extracted the organic phase with dichloromethane, washed three times with 80ml of saturated aqueous sodium chloride solution, and finally dried the organic phase with anhydrous magnesium sulfate. phase, the organic phase was removed by rotary evaporation with a rotary evaporator, and the pure product was obtained by thin-layer chromatography, the eluent was PE:EA=8:1, and the pure product was collected to finally obtain 100 mg of a white solid with a yield of 6.1%.
上述所得的白色固体通过核磁共振仪器（Bruker AVANCE III 500 MHz）进行氢谱测定，数据如下所示（如图2所示）：The white solid obtained above was subjected to hydrogen spectrum determination by nuclear magnetic resonance instrument (Bruker AVANCE III 500 MHz), and the data are as follows (as shown in Figure 2):
1H NMR (501 MHz, CDCl3) δ 4.11 (dt, J = 29.3, 6.7 Hz, 2H), 3.89 (t, J= 5.6 Hz, 1H), 2.54 – 2.28 (m, 4H), 1.89 (d, J = 4.3 Hz, 2H), 1.84 – 1.23 (m,12H), 0.93 (t, J = 6.6 Hz, 3H). 1 H NMR (501 MHz, CDCl 3 ) δ 4.11 (dt, J = 29.3, 6.7 Hz, 2H), 3.89 (t, J = 5.6 Hz, 1H), 2.54 – 2.28 (m, 4H), 1.89 (d, J = 4.3 Hz, 2H), 1.84 – 1.23 (m,12H), 0.93 (t, J = 6.6 Hz, 3H).
上述所得的白色固体通过核磁共振仪器（Bruker AVANCE III 500 MHz）进行碳谱测定，数据如下所示（如图3所示）：The white solid obtained above was subjected to carbon spectrum measurement by a nuclear magnetic resonance instrument (Bruker AVANCE III 500 MHz), and the data are as follows (as shown in Figure 3):
13C NMR (126 MHz, CDCl3) δ 172.94 (s), 172.42 (s), 75.41 (s), 64.64(s), 36.85 (d, J = 7.3 Hz), 33.93 (s), 28.27 (d, J = 3.4 Hz), 28.05 (d, J =3.8 Hz), 23.47 (s), 22.28 (s), 13.90 (s). 13 C NMR (126 MHz, CDCl 3 ) δ 172.94 (s), 172.42 (s), 75.41 (s), 64.64 (s), 36.85 (d, J = 7.3 Hz), 33.93 (s), 28.27 (d, J = 3.4 Hz), 28.05 (d, J = 3.8 Hz), 23.47 (s), 22.28 (s), 13.90 (s).
综上所述，本发明提供了一种ε-丙酸正戊酯基-ε-己内酯化合物的简便合成方法，是一类新型且带有特征的醇甜米酒的酒香香气的ε-内酯型化合物，是国内外对于ε-内酯型带有特征香气化合物的最新研究成果。In summary, the present invention provides a simple synthesis method of ε-n-pentyl propionyl-ε-caprolactone compound, which is a new type of ε- Lactone-type compounds are the latest research results on ε-lactone-type compounds with characteristic aroma at home and abroad.
以上所述内容仅为本发明构思下的基本说明，而依据本发明的技术方案所作的任何等效变换，均应属于本发明的保护范围。The above content is only a basic description of the concept of the present invention, and any equivalent transformation made according to the technical solution of the present invention shall fall within the scope of protection of the present invention.
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