CN102060816A - Synthesis method of gamma-nonalactone - Google Patents
Synthesis method of gamma-nonalactone Download PDFInfo
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- CN102060816A CN102060816A CN 201010622048 CN201010622048A CN102060816A CN 102060816 A CN102060816 A CN 102060816A CN 201010622048 CN201010622048 CN 201010622048 CN 201010622048 A CN201010622048 A CN 201010622048A CN 102060816 A CN102060816 A CN 102060816A
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- vinylformic acid
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- hexyl alcohol
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Abstract
The invention relates to a synthesis method of gamma-nonalactone, comprising the following steps of: adding 3/4 dosage of n-hexanol and a catalyst to a heating reactor, stirring and heating to 170-190 DEG C; mixing the remained n-hexanol with an initiator and acrylic acid, and then dripping the mixture into the heating reactor at the speed of 3-10mL/h; and after all materials are added, reflowing for 5-15h by the heating reactor provided with a water segregator, wherein a given amount of driers is added to the water segregator. In the invention, the given amount of driers is added to the water segregator such that water generated during the reaction is easy to remove from the system; therefore, the charging speed and the reaction speed are increased, the side reaction is avoided as far as possible, and the yield of products is improved at the same time; in addition, the driers can be recycled so that the production cost is reduced.
Description
Technical field
The present invention relates to a kind of synthetic method of γ-Ren Neizhi.
Background technology
γ-Ren Neizhi is called γ-amyl group butyrolactone again, commodity prunolide by name or Shi Baquan, having the fragrance of intensive coconut, cream, star anise, Radix Glycyrrhizae and peach etc., is one of lactone spices of using always, is generally used for preparing the essence of coconut, milk and butterfat etc.
At present, the γ-Ren Neizhi spices on the market mainly comes from chemosynthesis.The chemical synthesis process of γ-Ren Neizhi has multiple, comparatively traditional method as utilization 7-hydroxyl pelargonic acid and the hot altogether dehydration preparation of sulfuric acid γ-Ren Neizhi; With α-heptene and acetic acid is raw material, and high price acetate such as cerium, vanadium or manganese acetate (+3 valency) prepare γ-Ren Neizhi as oxygenant; With beta, gamma-nonenoic acid is that raw material passes through the synthetic γ-Ren Neizhi of acid catalysis cyclization; With n-hexyl alcohol and acrylic acid derivative is that raw material passes through free radical addition prepared in reaction γ-Ren Neizhi etc.
The method of patent report is that raw material passes through free radical addition prepared in reaction γ-Ren Neizhi with n-hexyl alcohol and vinylformic acid mostly at present, reported that as Japanese Patent JP08231525 with n-hexyl alcohol and water-containing acrylic acid (acrylic acid content is 80%) be raw material, by free radical addition synthetic γ-Ren Neizhi under about 4atm high pressure, this patent institute reported method is higher to the equipment requirement of withstand voltage, equipment cost and running cost are higher, and have certain risk.Japanese Patent JP2002338563 has reported that with n-hexyl alcohol and vinylformic acid be raw material, method by free radical addition synthetic γ-Ren Neizhi under normal pressure, this patent institute reported method needs one to overlap the water that complex apparatus comparatively is beneficial to generate in the reaction process and in time discharge from system, and production process is comparatively complicated, thereby this patent institute reported method equipment cost and running cost are also higher.
The analysis found that, be that raw material is a kind of comparatively ideal method for preparing γ-Ren Neizhi by free radical addition prepared in reaction target product with n-hexyl alcohol and vinylformic acid, but the water that generates in the reaction process is difficult to discharge from system.This is because this is reflected under the comparatively high temps and carries out (170-190 ℃), under this temperature, as adopt common water trap to dewater, raw material n-hexyl alcohol, vinylformic acid and water byproduct will enter water trap simultaneously, and vinylformic acid and water are miscible, will cause raw material propylene acid to be run off when dewatering, product yield will descend significantly.
Summary of the invention
Is the defective that be difficult to dewater of raw material by the method for free radical addition prepared in reaction γ-Ren Neizhi in order to solve of the prior art with n-hexyl alcohol and vinylformic acid, the method that the purpose of this invention is to provide a kind of γ-Ren Neizhi, it is by adding the defective that a certain amount of siccative solves prior art in water trap.
Specifically, method of the present invention may further comprise the steps:
A) but n-hexyl alcohol and the catalyzer with 3/4 consumption joins in the reactor heating, stirs and be heated to 170-190 ℃;
B) but will remaining just several pure and mild initiators and vinylformic acid be added drop-wise in the reactor heating after mixing, rate of addition is 3-10mL/ hour;
C) after material finishes, but refluxed 5-15 hour by the water trap of reactor heating outfit,
Wherein, described catalyzer is boric acid or zinc bromide, described initiator is ditertiary butyl peroxide or dibenzoyl peroxide, described just a little alcohol and acrylic acid mol ratio are 5-8: 1, the mol ratio of described vinylformic acid and described initiator is 5-20: 1, the mol ratio of described vinylformic acid and described catalyzer is 20-40: 1, be added with a certain amount of siccative in the described water trap.Described heatable reactor can be a flask.
The method of above-mentioned synthetic γ-Ren Neizhi, wherein said siccative are Calcium Chloride Powder Anhydrous or sewage sodium sulfate or anhydrous magnesium sulfate.
The method of above-mentioned synthetic γ-Ren Neizhi, the mol ratio of described vinylformic acid and described siccative are 1: 1-10.
The present invention is by adding a certain amount of siccative in water trap, thereby makes the water that generates in the reaction process be easy to remove from system, thereby improves feed rate and speed of response, hinders side reaction as far as possible and takes place, and improves product yield simultaneously; In addition, siccative can be recycled, thereby reduces production costs.
Embodiment
Following embodiment is in order to further describe the present invention, but the present invention is not limited to these embodiment.That is to say that though this specification sheets is not put down in writing one by one to the component and the content of all siccative, this can not be understood that not have the component and the content of record just can not realize the present invention.
In addition, in the following embodiments, productive rate is to be that benchmark calculates with acrylic acid molar weight.
Productive rate=(product gram number/molecular weight product)/acrylic acid molar weight * 100%
Embodiment 1: add 174mL n-hexyl alcohol and 1.4g zinc bromide in the 500mL there-necked flask of constant pressure funnel, thermometer, water trap and prolong is housed, adds the 15g anhydrous sodium sulphate in the water trap and fill with n-hexyl alcohol.With heat collecting type magnetic stirring apparatus heated and stirred, behind the temperature-stable to 180 ℃, begin to drip the mixture of forming by 52mL n-hexyl alcohol, 5mL ditertiary butyl peroxide and 17.8mL vinylformic acid, rate of addition is 3mL/h.Raw mix keeps 180 ℃ of temperature after dripping and finishing, and finishes reaction behind the backflow 12h, and productive rate is 75.35%.
Claims (3)
1. the synthetic method of a γ-Ren Neizhi may further comprise the steps:
A) but n-hexyl alcohol and the catalyzer with 3/4 consumption joins in the reactor heating, stirs and be heated to 170～190 ℃;
B) but will remaining n-hexyl alcohol and initiator and vinylformic acid be added drop-wise in the reactor heating after mixing, rate of addition is 3～10 milliliters/hour;
C) after material finishes, but the reactor heating backflow by being equipped with water trap 5-15 hour,
Wherein, described catalyzer is boric acid or zinc bromide, described initiator is ditertiary butyl peroxide or dibenzoyl peroxide, described n-hexyl alcohol and acrylic acid mol ratio are 5-8: 1, the mol ratio of described vinylformic acid and described initiator is 5-20: 1, the mol ratio of described vinylformic acid and described catalyzer is 20-40: 1, be added with a certain amount of siccative in the described water trap.
2. synthetic method according to claim 1 is characterized in that: described siccative is Calcium Chloride Powder Anhydrous or anhydrous sodium sulphate or anhydrous magnesium sulfate.
3. synthetic method according to claim 2 is characterized in that: the mol ratio of described vinylformic acid and described siccative is 1: 1～10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010622048 CN102060816A (en) | 2010-12-31 | 2010-12-31 | Synthesis method of gamma-nonalactone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010622048 CN102060816A (en) | 2010-12-31 | 2010-12-31 | Synthesis method of gamma-nonalactone |
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| CN102060816A true CN102060816A (en) | 2011-05-18 |
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| CN 201010622048 Pending CN102060816A (en) | 2010-12-31 | 2010-12-31 | Synthesis method of gamma-nonalactone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617522A (en) * | 2012-01-11 | 2012-08-01 | 厦门大学 | Method for synthesis of gamma-nonyl lactone |
| CN112341408A (en) * | 2020-11-24 | 2021-02-09 | 江苏宏邦化工科技有限公司 | Preparation method of coconut aldehyde |
| CN115417841A (en) * | 2022-08-30 | 2022-12-02 | 安徽华业香料股份有限公司 | High-yield synthesis method of coconut aldehyde |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735180A (en) * | 2009-12-24 | 2010-06-16 | 北京北大正元科技有限公司 | Method for synthesizing gamma-lactone and perfume processing method thereof |
-
2010
- 2010-12-31 CN CN 201010622048 patent/CN102060816A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735180A (en) * | 2009-12-24 | 2010-06-16 | 北京北大正元科技有限公司 | Method for synthesizing gamma-lactone and perfume processing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《化学世界》 19871231 吴立成 gamma-壬内酯gamma-癸内酯gamma-十一内酯的合成 492-495 1-3 , 第11期 2 * |
| 《安徽大学学报(自然科学版)》 19960630 张悠金等 gamma-壬内酯的合成 85-8 1-3 第20卷, 第2期 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617522A (en) * | 2012-01-11 | 2012-08-01 | 厦门大学 | Method for synthesis of gamma-nonyl lactone |
| CN102617522B (en) * | 2012-01-11 | 2014-10-08 | 厦门大学 | Method for synthesis of gamma-nonyl lactone |
| CN112341408A (en) * | 2020-11-24 | 2021-02-09 | 江苏宏邦化工科技有限公司 | Preparation method of coconut aldehyde |
| CN112341408B (en) * | 2020-11-24 | 2023-03-31 | 江苏宏邦化工科技有限公司 | Preparation method of coconut aldehyde |
| CN115417841A (en) * | 2022-08-30 | 2022-12-02 | 安徽华业香料股份有限公司 | High-yield synthesis method of coconut aldehyde |
| CN115417841B (en) * | 2022-08-30 | 2024-02-09 | 安徽华业香料股份有限公司 | Synthesis method of cocoanut aldehyde |
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Application publication date: 20110518 |