CN101602663B - Method for synthesizing (E)-2-hexenoic acid - Google Patents
Method for synthesizing (E)-2-hexenoic acid Download PDFInfo
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- CN101602663B CN101602663B CN2009100672722A CN200910067272A CN101602663B CN 101602663 B CN101602663 B CN 101602663B CN 2009100672722 A CN2009100672722 A CN 2009100672722A CN 200910067272 A CN200910067272 A CN 200910067272A CN 101602663 B CN101602663 B CN 101602663B
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Abstract
The invention provides a method for synthesizing (E)-2-hexenoic acid. The method comprises the following steps: using ethyl malonate as a raw material, and performing Knovenagel reaction, hydrolysis and decarboxylation on the ethyl malonate in a water phase to synthesize the (E)-2-hexenoic acid. Aiming at problems of strict reaction condition, serious side reaction, low yield and usage of a toxic reagent in the prior method for synthesizing the (E)-2-hexenoic acid, the method uses water as a reaction medium to realize clean and environment-friendly production without pollution, and has accessible raw materials with low cost, mild reaction condition, simple operation and easy industrialization. The synthesis method has few side reactions, and yield up to 75 to 85 percent.
Description
Technical field
The present invention provides a kind of method of synthetic (E)-2-hexenoic acid.
Background technology
(E)-and the 2-hexenoic acid is commonly called as butylene fork acetic acid, has special grease fragrance, is the carboxylic-acid safe edible synthetic perfume that FDA announces, and FEMA number is 3169, also is that Food Additives Used in China is used hygienic standard GB2760
Allow the edible synthetic perfume of use in-86 appendix, the commodity English name of sale is trans-2-Hexenoic acid (anti--the 2-hexenoic acid), and its structural formula is following:
(E)-the 2-hexenoic acid can be used for the allotment of apple, banana, caramel type essence, can be used for having the spices preparation of food, beverage and the daily chemical products of fruital gas simultaneously.(E)-and the 2-hexenoic acid has sweet berry fragrance, and smell is lasting, is generally believed to be suitable for the allotment food flavour.In recent years, because fruital gas more and more receives people's favor, thereby market in great demand to (E)-2-hexenoic acid.(E)-the 2-hexenoic acid become the important a member in the synthetic perfume family.
(E)-2-hexenoic acid compound method of reported in literature is a lot; From at present existing reported in literature; Main through Perkin reaction (J.Chem.Soc.1877.31 388), halogenating reaction (Org.Syn.1973.53.123-7) and Knovenagel-Dobner reaction (Ber.1898.31.2596; Ann.1988.242,265) three kinds of methods are synthetic.Wherein halogenating reaction exists the shortcoming that raw material is not easy to obtain, productive rate is lower; Perkin reaction exists temperature of reaction height, the time is long and productive rate is low shortcoming, utilizes the method for synthetic (the E)-2-hexenoic acid of Perkin reaction to be eliminated; Knovenagel-Dobner reactive applications scope is wide; Aliphatics and aromatic aldehyde ketone all are suitable for; Can make catalyzer with weak base or its salt, avoid self condensation of aldehyde ketone, simple to operate; Productive rate is higher than the Perkin reaction, and nearly all producer utilizes synthetic (the E)-2-hexenoic acid of Knovenagel-Dobner reaction.But with regard to the synthetic technology of (E)-2-hexenoic acid; How to reduce polymerization ofathe reactants, improve product yield, simplify synthesis technique; Abandon the use of toxic reagent benzene in the Knovenagel-Dobner method or pyridine, exploitation (E)-2-hexenoic acid new cleanproduction process has most important theories research and practical application meaning.
Summary of the invention
The objective of the invention is to severe reaction conditions in the compound method of existing (E)-2-hexenoic acid, side reaction is serious, productive rate is low, noxious solvent uses problem, provide that a kind of reaction conditions is gentle, side reaction is few, yield is high, the environment-friendly type novel method of synthetic (the E)-2-of water hexenoic acid.
The preparing method's of (E)-2-hexenoic acid involved in the present invention step and condition are following:
The structural formula of described (E)-2-hexenoic acid compound is represented as follows:
At aqueous phase, through phase-transfer catalyst, through Knovenagel reaction, hydrolysis, the synthetic title product (E) of decarboxylation-2-hexenoic acid, reaction equation is following by ethyl malonate and butyraldehyde-n for (E)-2-hexenoic acid involved in the present invention:
In the reactor drum that reflux condensing tube and whisking appliance are housed by 10～100: 1.0: 1.0～1.2: 0.03～0.1 molar ratio adds entry, ethyl malonate, butyraldehyde-n and catalyzer successively, stirs under the reaction mixture room temperature 9.0～15.0 hours, is warming up to 40～60 ℃ afterwards; Continue to stir 4.0～6.0 hours, be warmed up to 80～90 ℃ then, continue to stir nuclear reaction 1～3 hour; Add massfraction and be 5%～20% alkali lye, stirring and refluxing 0.5～1.0 hour adds massfraction and is 5%～20% acid solution acidifying then; Stirring and refluxing 0.5～1.0 hour; Stopped reaction, underpressure distillation obtains (E)-2-hexenoic acid.Between the productive rate apparent 70～85%, see embodiment for details.
Catalyzer used in the reaction is: TBAB (Tetrabutyl amonium bromide), TEBA (triethyl benzyl ammonia chloride), the two octadecyl Dimethyl Ammonium of bromination, cetyl trimethylammonium bromide, tetrabutylammonium chloride or benzyl trimethyl ammonium chloride;
Alkali used in the reaction is: sodium hydroxide, Pottasium Hydroxide or calcium hydroxide;
Acid used in the reaction is: hydrochloric acid or sulfuric acid;
Solvent for use is in the reaction: water.
Beneficial effect: the method that the invention provides a kind of synthetic (E)-2-hexenoic acid.This method is raw material with the ethyl malonate, synthesizes (E)-2-hexenoic acid at aqueous phase through Knovenagel reaction, hydrolysis, decarboxylation.To severe reaction conditions, problems such as side reaction is serious, productive rate is low, toxic reagent use in the compound method of existing (E)-2-hexenoic acid; Make water do reaction medium; Realize free of contamination clean environment firendly production, raw material is easy to get and is cheap, and reaction conditions is gentle; Simple to operate, be easy to industriallization.This compound method side reaction is few, and productive rate is up to 75-85%.
Embodiment
Embodiment 1
In the reaction flask that reflux condensing tube, whisking appliance are housed, add 10 milliliters of entry, ethyl malonate 5.0 mmoles, butyraldehyde-n 5.0 mmoles and catalyzer TBAB 0.15 mmole, reaction mixture stirred 12 hours down for 25 ℃, was warming up to 60 ℃ afterwards; Continue to stir 6.0 hours, be warmed up to 90 ℃ then, continue to stir 2 hours; Add massfraction then and be 10% sodium hydroxide solution, stirring and refluxing 0.5 hour adds massfraction and is 10% hcl acidifying then; Stirring and refluxing 0.5 hour, stopped reaction, underpressure distillation, vacuum-drying; Obtain (E)-2-hexenoic acid 0.485 gram, productive rate 85%.
Reaction equation is following:
The data characterization of hexenoic acid:
Mp：125～127℃/2.66KPa
1H?NMR(500MHz，CDCl
3，25℃)δ＝0.87(3H)，1.41(2H)，2.14(2H)，5.76(2H)，6.80(1H)，12.14(1H).
13C?NMR(125MHz，CDCl
3，25℃)δ＝15.4，25.3，36.9，120.1，150.8，171.5.
Ultimate analysis: theoretical value (C
6H
10O
2): C, 53.91; H, 10.18.
Measured value: C, 54.52; H, 9.43.
Embodiment 2
The consumption of butyraldehyde-n is 0.48 mmole, and other operational conditions are all identical with embodiment 1, and the productive rate that obtains (E)-2-hexenoic acid is 82%, 124～125 ℃/2.66KPa.
Embodiment 3
The consumption of butyraldehyde-n is outside 0.52 mmole, and other operational conditions are all identical with embodiment 1, and the productive rate that obtains (E)-2-hexenoic acid is 80%, 125～126 ℃/2.66KPa.
Embodiment 4
25 ℃ of following churning time are 8 hours, and other operational conditions are all identical with embodiment 1, productive rate: 70%, 125～127 ℃/2.66KPa.
Embodiment 5
25 ℃ of following churning time are 15 hours, and other operational conditions are all identical with embodiment 1, and obtaining (E)-2-hexenoic acid productive rate is 85%, 123～125 ℃/2.66KPa.
Embodiment 6
Catalyzer is TEBA, and other operational conditions are all identical with embodiment 1, and obtaining (E)-2-hexenoic acid productive rate is 83%, 123～125 ℃/2.66KPa.
Embodiment 7
Catalyzer is a cetyl trimethylammonium bromide, and other operational conditions are all identical with embodiment 1, and obtaining (E)-2-hexenoic acid productive rate is 83%, 124～126 ℃/2.66KPa.
Embodiment 8
Catalyzer is the two octadecyl Dimethyl Ammonium of bromination, and other operational conditions are all identical with embodiment 1, and obtaining (E)-2-hexenoic acid productive rate is 75%, 125～126 ℃/2.66KPa.
Embodiment 9
Catalyzer is a tetrabutylammonium chloride, and other operational conditions are all identical with embodiment 1, and obtaining (E)-2-hexenoic acid productive rate is 84%, 125～126 ℃/2.66KPa.
Embodiment 10
Catalyzer is a benzyl trimethyl ammonium chloride, and other operational conditions are all identical with embodiment 1, and obtaining (E)-2-hexenoic acid productive rate is 78%, 126～128 ℃/2.66KPa.
Embodiment 11
In the reaction flask that reflux condensing tube, whisking appliance are housed, add 10 milliliters of entry, ethyl malonate 5.0 mmoles, butyraldehyde-n 5.0 mmoles and catalyzer TBAB 0.15 mmole, reaction mixture stirred 12 hours down for 25 ℃, was warming up to 60 ℃ afterwards; Continue to stir 6.0 hours, be warmed up to 90 ℃ then, continue to stir 2 hours; Add massfraction then and be 20% aqua calcis, stirring and refluxing 0.5 hour adds massfraction and is 20% hcl acidifying then; Stirring and refluxing 0.5 hour, underpressure distillation, (E)-2-hexenoic acid compound 0.48 gram that obtains; Productive rate is 84%, 122～125 ℃/2.66KPa.
Embodiment 12
Adding massfraction is 20% Pottasium Hydroxide, and outside the stirring and refluxing 1.0 hours, other operational conditions are all identical with embodiment 7, and obtaining (E)-2-hexenoic acid productive rate is 80%, 125～127 ℃/2.66KPa.
Embodiment 13
90 ℃ of following stirring and refluxing 3.0 hours, other operational conditions were all identical with embodiment 7, and obtaining (E)-2-hexenoic acid productive rate is 79%, 124～126 ℃/2.66KPa.
Embodiment 14
After adding hydrochloric acid, stirring and refluxing 1.0 hours, other operational conditions are all identical with embodiment 7, and obtaining (E)-2-hexenoic acid productive rate is 80%, 125～127 ℃/2.66KPa.
Embodiment 15
After adding sulfuric acid, stirring and refluxing 0.5 hour, other operational conditions are all identical with embodiment 7, and obtaining (E)-2-hexenoic acid productive rate is 80%, 126～127 ℃/2.66KPa.
Claims (1)
1. the compound method of (E)-2-hexenoic acid, the structural formula of described (E)-2-hexenoic acid does
It is characterized in that step and condition are following: in the reactor drum that reflux condensing tube and whisking appliance are housed by 10～100: 1.0: 1.0～1.2: 0.03～0.1 molar ratio adds entry, ethyl malonate, butyraldehyde-n and catalyzer successively, stirs under the reaction mixture room temperature 9.0～15.0 hours, is warming up to 40～60 ℃ afterwards; Continue to stir 4.0～6.0 hours; Be warmed up to 80～90 ℃ then, continue to stir and reacted 1～3 hour, the adding massfraction is 5%～20% alkali lye; Stirring and refluxing 0.5～1.0 hour; Add massfraction then and be 5%～20% acid solution acidifying, stirring and refluxing 0.5～1.0 hour, stopped reaction; Underpressure distillation obtains (E)-2-hexenoic acid;
Described catalyzer is: Tetrabutyl amonium bromide, triethyl benzyl ammonia chloride, the two octadecyl Dimethyl Ammonium of bromination, cetyl trimethylammonium bromide, tetrabutylammonium chloride or benzyl trimethyl ammonium chloride; Described alkali is: sodium hydroxide, Pottasium Hydroxide or calcium hydroxide; Described acid is: hydrochloric acid or sulfuric acid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838474A (en) * | 2012-09-25 | 2012-12-26 | 天宁香料（江苏）有限公司 | Synthesis method for trans-3-hexenoic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109105478A (en) * | 2018-09-12 | 2019-01-01 | 河南工业大学 | A kind of fruit and vegetable fresh-keeping agent and its application containing trans- -2- hexenoic acid |
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Non-Patent Citations (3)
| Title |
|---|
| A. V. Lebedev.Competitive Formation of β-Amino Acids, Propenoic,and Ylidenemalonic Acids by the Rodionov Reaction from Malonic Acid, Aldehydes, and Ammonium Acetate in Alcoholic Medium.《Russian Journal of General Chemistry》.2005,第75卷(第7期),1177-1186. * |
| Fujiwara.Condensation of aldehydes with malonic acid.《Nippon Kagaku Zasshi》.1961,第82卷1400-1403. * |
| 韩巧 等.γ-己内酯的合成研究.《郑州大学学报(自然科学版)》.1999,第31卷(第2期),88-90. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838474A (en) * | 2012-09-25 | 2012-12-26 | 天宁香料（江苏）有限公司 | Synthesis method for trans-3-hexenoic acid |
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Owner name: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS + Free format text: FORMER OWNER: CHANGCHUN INST. OF APPLIED CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20140207 |
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Effective date of registration: 20140207 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |
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