CN103420832A - Preparing method of cis-3-Hexenyl caproate - Google Patents
Preparing method of cis-3-Hexenyl caproate Download PDFInfo
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- CN103420832A CN103420832A CN2013103968081A CN201310396808A CN103420832A CN 103420832 A CN103420832 A CN 103420832A CN 2013103968081 A CN2013103968081 A CN 2013103968081A CN 201310396808 A CN201310396808 A CN 201310396808A CN 103420832 A CN103420832 A CN 103420832A
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Abstract
The invention discloses a preparing method of cis-3-Hexenyl caproate. According to the preparing method, an esterification reaction is carried out with a main exchange group of a pre-processed solid catalyst as cation exchange resin of a sulponic group (-SO3H). The temperature is 132-155 DEG C, the reaction lasts for 1h-3h until no water flows out, backflow is carried out for 3-4h, then liquid is collected, the mass ratio of caproic acid to leaf alcohol to the catalyst is 2-3:1.5-2.5:0.2-0.5, after the reaction is finished, the liquid is cooled to be at the indoor temperature, pH of the collected liquid is adjusted to be 7-8 through anhydrous sodium carbonate, resin is removed through filtering, filtered liquor is transferred into a distillation flask, pressure reducing and fractional distillation are firstly carried out, then pressure reducing and distillation are carried out, cut fraction of -0.098 MPa-0.1MPa at the temperature of 120-124 DEG C is collected and products are obtained. The method is convenient to operate, the quantity of byproducts is small, the catalyst is low in cost, easy to obtain and capable of being repeatedly used, requirements for production equipment are low, and the preparing method is suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of caproic acid leaf-alcohol ester, be specifically related to the preparation method of the Zeo-karb synthesizing hexanoic acid leaf-alcohol ester that the main cation exchange groups of a kind of employing solid catalyst is sulfonic group (SO3H).
Background technology
Along with the development of national economy, people's lives progressively have and simply having adequate food and clothingly turn to fairly well-offly, and for the development of perfume industry product provides a wide large market, especially natural perfume enjoys favor.But, because natural animal-plant spices often is subject to the factors such as the restriction of natural condition and processing, be subject to certain impact on kind quantity and quality product.The innovation of essence and the raising of quality also more and more rely on new synthetic perfume kind.Because synthetic perfume is not subject to the restriction of natural condition, steady quality, the large I of industrial scale is arranged by people oneself, and the price of product is also than natural source considerably cheaper.Therefore, development and the new synthetic perfume of developing development also seem more and more important.Particularly along with modern science research and analysis state of the art improves constantly separable and dissects main fragrant composition and the structure thereof in natural perfume, thereby developed by chemical synthesis process.Both the natural perfume deficiency can be solved, Financial cost can be lowered again.
Caproic acid leaf-alcohol ester is to have sweet fruital, and apple-pears sample fragrance naturally is present in pineapple, melon, and apple, pears, passion fruit, in flower of Chinese Narcissus.Can be used for the allotment of apple, the certain kind of berries, tropical fruit essence.
Usually esterification adopts the vitriol oil, hydrochloric acid or sulfonic acid as catalyzer more, although they are cheap and easy to get, serious to equipment corrosion, and produces a large amount of side reaction products.
Summary of the invention
In order to solve the defect existed in prior art, the purpose of this invention is to provide a kind of preparation method of caproic acid leaf-alcohol ester, the method reaction times is short, productive rate is high.
The objective of the invention is to be achieved through the following technical solutions:
A kind of preparation method of caproic acid leaf-alcohol ester is characterized in that: the esterification of carrying out under the condition that the method is catalyzer by caproic acid and leaf-alcohol at storng-acid cation exchange resin, specific as follows:
1) take the Zeo-karb that the main cation exchange groups of pretreated solid catalyst is sulfonic group (SO3H), temperature is 132～155 ℃, and reaction 1h-3h, till anhydrous separating;
2) continue backflow 3-4h, collect liquid; Caproic acid wherein. leaf-alcohol. the mass ratio of catalyzer is 2-3:1.5-2.5:0.2-0.5;
3) reacted, be cooled to room temperature, regulating collection liquid pH with anhydrous sodium carbonate is 7～8, remove by filter resin (recycling), filtrate is transferred in distilling flask, and first vacuum fractionation of decaptitating (is mainly leaf-alcohol, recycle), underpressure distillation again, collection-0.098Mpa-0.1Mpa, the cut of 120～124 ℃ is product.
In the present invention, described caproic acid. leaf-alcohol. the mass ratio of catalyzer is 2.3:2:0.29.Liquid boiling in bottle, when condenser has the backflow drop to drip, regulate thermal source and make return velocity normal, 2 of per seconds; Continue to be heated to reflux, minute water, temperature is 132～155 ℃, reaction 1h-3h, till anhydrous separating, continues backflow 3-4h, collects liquid.The pre-treatment of solid catalyst is: catalyzer soaks through persulfuric acid, after filtration, with ammonium molybdate solution, soaks again; In baking oven, dry, then calcination under 400-700 degree celsius temperature again; Pulverize the catalyzer that obtains having greater activity intensity after taking out.
Wherein, the esterification that caproic acid and leaf-alcohol carry out under catalyst action adopts the reflux dewatering type, and under agitation carries out.
The present invention has the following advantages compared to existing technology: esterification adopts the vitriol oil, hydrochloric acid or sulfonic acid as catalyzer more usually, although they are cheap and easy to get, serious to equipment corrosion, and produces a large amount of side reaction products.The present invention is usingd storng-acid cation exchange resin as catalyzer synthesizing hexanoic acid leaf-alcohol ester.Easy to operate, by product is few, and catalyzer is cheap and easy to get and reusable.Greatly shortened the reaction times, and the yield of the product prepared, purity are all higher.And preparation technology of the present invention is simple, the operational condition gentleness, low to the production unit requirement, be applicable to carrying out scale operation.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
1. the pre-treatment of solid catalyst: catalyzer soaks 24h through 75mL 1mol/l sulfuric acid, after filtration, soaks 24h-48h with 10 ml 0.5Lmol/l ammonium molybdate solutions again.Dry 2h in baking oven, then calcination 3h under 400-700 degree celsius temperature again.Pulverize the catalyzer that obtains having greater activity intensity after taking out.
2. add the 116g caproic acid in 500 mL round-bottomed flasks, the 100g leaf-alcohol, then add the storng-acid cation exchange resin of 14.5g through anticipating, several zeolites (the zeolite effect: the gasification center prevents bumping).
3. load onto water trap and spherical reflux condensing tube, open cold water.
4. liquid boiling in bottle, when condenser has the backflow drop to drip, regulate thermal source and make return velocity normal.Continue to be heated to reflux, minute water, temperature is 135 ℃, reaction 1h, till anhydrous separating, continues backflow 4h, collects liquid.
5. reacted, be cooled to room temperature, regulating pH with anhydrous sodium carbonate is 8, remove by filter resin (recycling), filtrate is transferred in distilling flask, and first decompression divides the son of decaptitating (to be mainly leaf-alcohol, recycle), decompression is heated up in a steamer again, collects-0. 098MPa-0.1Mpa, and the cut of 120～124 ℃ is product.Content 99.5%, yield 91.5%.
?Embodiment 2
1. the pre-treatment of solid catalyst: catalyzer soaks 30h through 80mL 1mol/l sulfuric acid, after filtration, soaks 20h with 10 ml 0.5Lmol/l ammonium molybdate solutions again.Dry 4h in baking oven, then calcination 5h under 400-700 degree celsius temperature again.Pulverize the catalyzer that obtains having greater activity intensity after taking out.
2. add the 116g caproic acid in 500 mL round-bottomed flasks, the 100g leaf-alcohol, then add the storng-acid cation exchange resin of 15g through anticipating, and several zeolites, the zeolite effect: the gasification center prevents bumping.
3. load onto water trap and spherical reflux condensing tube, open cold water.
4. liquid boiling in bottle, when condenser has the backflow drop to drip, regulate thermal source and make return velocity normal.Continue to be heated to reflux, minute water, temperature is 150 ℃, reaction 2h, till anhydrous separating, continues backflow 3h, collects liquid.
5. reacted, be cooled to room temperature, regulating pH with anhydrous sodium carbonate is 7, removes by filter resin (recycling), and filtrate is transferred in distilling flask, first decompression divides the son of decaptitating (to be mainly leaf-alcohol, recycle), then decompression heats up in a steamer, and collects-0. 098MPa-0.1Mpa, the cut of 120～124 ℃ is product. content 98.3%, yield 90.1%.
The caproic acid leaf-alcohol ester that aforesaid method obtains, should be in the allotment of apple, the certain kind of berries, tropical fruit essence as raw material.
The present invention has adopted storng-acid cation exchange resin as catalyzer synthesizing hexanoic acid leaf-alcohol ester.Easy to operate, by product is few, and catalyzer is cheap and easy to get and reusable; And greatly shortened the reaction times, and the yield of the product prepared, purity are all higher.And preparation technology of the present invention is simple, the operational condition gentleness, low to the production unit requirement, be applicable to carrying out scale operation.
Claims (4)
1. the preparation method of a caproic acid leaf-alcohol ester is characterized in that: under the condition that the method is catalyzer by caproic acid and leaf-alcohol at storng-acid cation exchange resin, prepares, specific as follows:
1), with pretreated solid catalyst exchange resin, the main cation exchange groups of solid catalyst is sulfonic positively charged ion; Temperature is 132～155 ℃, and reaction 1h-3h, till anhydrous separating;
2) continue backflow 3-4h, collect liquid; Wherein the mass ratio of caproic acid, leaf-alcohol, catalyzer is 2-3:1.5-2.5:0.2-0.5;
3) reacted, be cooled to room temperature, regulating collection liquid pH with anhydrous sodium carbonate is 7～8, remove by filter resin, filtrate is transferred in distilling flask, first vacuum fractionation of decaptitating, underpressure distillation again, collection-0.098Mpa-0.1Mpa, the cut of 120～124 ℃ is product.
2. the preparation method of caproic acid leaf-alcohol ester according to claim 1, is characterized in that: described caproic acid. leaf-alcohol. and the mass ratio of catalyzer is 2.3:2:0.29.
3. the preparation method of caproic acid leaf-alcohol ester according to claim 1 is characterized in that: liquid boiling in bottle, and when condenser has the backflow drop to drip, regulate thermal source and make return velocity normal, 2 of per seconds; Continue to be heated to reflux, minute water, temperature is 132～155 ℃, reaction 1h-3h, till anhydrous separating, continues backflow 3-4h, collects liquid.
4. the preparation method of caproic acid leaf-alcohol ester according to claim 1, it is characterized in that: the pre-treatment of solid catalyst is: catalyzer soaks through persulfuric acid, after filtration, with ammonium molybdate solution, soaks again; In baking oven, dry, then calcination under 400-700 degree celsius temperature again; Pulverize the catalyzer that obtains having greater activity intensity after taking out.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557526A (en) * | 2014-11-27 | 2015-04-29 | 浙江金科过氧化物股份有限公司 | Method for preparing ortho-methylcyclohexyl acetate under solvent-free conditions |
| CN111807957A (en) * | 2020-07-02 | 2020-10-23 | 深圳飞扬兴业科技有限公司 | Synthetic method of geranyl acetate |
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| CN1250043A (en) * | 1998-10-05 | 2000-04-12 | 中国科学院福建物质结构研究所 | Resin catalysis to synthesize folic acetate |
| CN1872835A (en) * | 2006-06-29 | 2006-12-06 | 天津市施普乐农药技术发展有限公司 | Method for preparing lignocaine ethyl ester caproic acid by catalyzing cation exchange resin in type of sulfonic acid |
| US20080028670A1 (en) * | 2006-08-02 | 2008-02-07 | General Electric Company | Silicone additives for compatalizing organic compounds with wax mixtures |
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2013
- 2013-09-04 CN CN2013103968081A patent/CN103420832A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250043A (en) * | 1998-10-05 | 2000-04-12 | 中国科学院福建物质结构研究所 | Resin catalysis to synthesize folic acetate |
| CN1872835A (en) * | 2006-06-29 | 2006-12-06 | 天津市施普乐农药技术发展有限公司 | Method for preparing lignocaine ethyl ester caproic acid by catalyzing cation exchange resin in type of sulfonic acid |
| US20080028670A1 (en) * | 2006-08-02 | 2008-02-07 | General Electric Company | Silicone additives for compatalizing organic compounds with wax mixtures |
Non-Patent Citations (3)
| Title |
|---|
| MUHAMMAD LIAQUAT: "Optimized synthesis of (Z)-3-hexen-1-yl caproate using germinated rapeseed lipase in organic solvent", 《JOURNAL OF MOLECULAR CATALYSIS B: ENZYMATIC》, vol. 68, 31 December 2011 (2011-12-31), pages 59 - 65, XP029051981, DOI: doi:10.1016/j.molcatb.2010.09.011 * |
| 王新培等: "己酸叶酯合成", 《精细化工》, vol. 7, no. 6, 31 December 1990 (1990-12-31), pages 1 - 2 * |
| 葛洪玉等: "磺酸树脂催化合成联苯乙酸乙酯", 《淮海工学院学报(自然科学版)》, vol. 13, no. 3, 30 September 2004 (2004-09-30), pages 46 - 48 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557526A (en) * | 2014-11-27 | 2015-04-29 | 浙江金科过氧化物股份有限公司 | Method for preparing ortho-methylcyclohexyl acetate under solvent-free conditions |
| CN111807957A (en) * | 2020-07-02 | 2020-10-23 | 深圳飞扬兴业科技有限公司 | Synthetic method of geranyl acetate |
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Application publication date: 20131204 |