CN102701973A - Catalytic synthesis method of methyl cinnamate - Google Patents
Catalytic synthesis method of methyl cinnamate Download PDFInfo
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- CN102701973A CN102701973A CN2012101401306A CN201210140130A CN102701973A CN 102701973 A CN102701973 A CN 102701973A CN 2012101401306 A CN2012101401306 A CN 2012101401306A CN 201210140130 A CN201210140130 A CN 201210140130A CN 102701973 A CN102701973 A CN 102701973A
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- styracin
- deionized water
- methyl cinnamate
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Abstract
The invention relates to a method for preparing methyl cinnamate. Cinnamic acid and methanol are subjected to liquid-solid-phase catalytic esterification reaction under the action of a supported catalyst to prepare the methyl cinnamate. By controlling the reaction technique conditions and purification technique conditions, the product is purified with deionized water at different temperatures, thereby obtaining the high-yield high-purity methyl cinnamate at low cost.
Description
Technical field
The present invention relates to a kind of process for catalytic synthesis of methyl cinnamate, particularly use a kind of loaded catalyst, through the method for the synthetic title product of liquid-solid phase catalytic reaction.
Background technology
Methyl cinnamate is the beta-phenyl methyl acrylate again, has cocoa aroma, is white to faint yellow crystallization or colourless to weak yellow liquid; Fusing point 34-38 ℃, water insoluble, be dissolved in ether; It is a kind of important synthetic perfume; Being mainly used in daily use chemicals and foodstuffs industry, is fixative and the food flavour of using always, also is important organic synthesis raw material simultaneously.
The method of tradition synthesizing cinnamic acid methyl esters is mineral acid (example hydrochloric acid, a sulfuric acid) catalytic esterification method; But this method has side reaction many (like sulfonation, oxidation, addition, carbonizations etc.); Product yield and quality are low, and equipment corrosion is serious, shortcomings such as aftertreatment trouble and waste liquor contamination environment.Therefore, extremely people's concern of novel environment friendly catalyst for esterification reaction at present.Wherein the loading type an acidic catalyst is that active ingredient (like phospho-wolframic acid, phospho-molybdic acid) is loaded on active carrier (like SiO
2, activated carbon, 5A molecular sieve) on, not only can provide reaction needed proton, and increase specific surface area greatly; Improved the acid activity site, so not only overcome the defective of mineral acid in the esterification operation, and reclaimed easily; Can reuse; Efficient is high, and selectivity is good, is one type of desirable catalyst for esterification reaction.
Preparation research to methyl cinnamate mostly concentrates on use differential responses thing at present, and research differential responses mechanism is to the influence of product yield and purity.Substituted benzaldehyde and acetone have been proposed in NaOH solution like CN101323567; Condensation obtains replacing BENZALACETONE; Replacement BENZALACETONE that will obtain then and cupric oxide, iodine, pyridine and alcohol add salt of wormwood again with " one kettle way " reaction, obtain laurate and verivate thereof.CN101774918A has proposed the utilization malonic acid monoester and phenyl aldehyde condensation reaction under amino acid catalytic makes laurate.The present invention adopts simple process, uses styracin and methyl alcohol under the effect of loading type an acidic catalyst, to carry out esterification, improves reaction product yield and purity through control reaction process condition and product purifying technique condition.The present invention proposes following prioritization scheme, has obtained high yield of high purity and lower-cost methyl cinnamate.
Summary of the invention
The objective of the invention is to adopt loading type an acidic catalyst Synthesis of Methyl Cinnamate using, and, under lower cost, obtain the high yield product of high purity, to satisfy the association area needs through control reaction process condition and product purifying technique condition.Mainly comprise the steps:
(1) styracin and methyl alcohol carry out liquid-solid phase catalytic esterification under the loaded catalyst effect, and temperature of reaction is 70-80 ℃, reaction times 3-7h; (2) product with step (1) carries out underpressure distillation, and the water and unreacted methanol to the absence of liq that steam the reaction generation distillate; (3) with the product filtered while hot of step (2), remove loaded catalyst, keep filtrating, and to keep its temperature be 40-50 ℃; (4) in the filtrating of step (3), adding proper quantity of lye to its pH value is 8-9, and the temperature of keeping this solution is 40-50 ℃, and standing demix is removed water, and the reservation oil phase is a product; (5) use this product of deionized water wash with isopyknic 40-50 ℃ of rapid (4) product, standing demix is removed water, and the pH value that repeats this step to solution is 7-7.5;
(6) in the product of step (5), add 5-15 ℃ of deionized water, separate out faint yellow solid, filter, promptly get title product;
The carrier of said loaded catalyst is selected from SiO
2, TiO
2, gac, 5A molecular sieve, γ-Al
2O
3In a kind of, the activity of such catalysts component is selected from phospho-wolframic acid, phospho-molybdic acid, sodium pyrosulfate, SnCl
4In a kind of, the mass ratio of said loaded catalyst and styracin is 0.05-1: 100, the mass ratio of said catalyst activity component and carrier is 5-10: 100.
The mol ratio of said styracin and methyl alcohol is 1: 4-12.
Alkali lye in the said step (4) is selected from K
2CO
3Solution, Na
2C
2O
3A kind of in solution, NaOH solution, the KOH solution, the mass concentration of said alkali lye is 5%-10%.
The volume of the deionized water in the said step (6) is 3 times of step (5) product.
Compared with prior art, innovative point of the present invention is: adopt the loaded catalyst catalytic esterification, catalyzer is more easily separated, and is reusable, simple to operate; The present invention simultaneously successively adopts the deionized water purification of target product of differing temps, has simplified operation steps greatly, has reduced production cost.
Embodiment
Embodiment 1
Get 14.8g styracin, 12.8g methyl alcohol and 0.74g loading type an acidic catalyst respectively and add in the 250ml flask, reflux 3h carries out underpressure distillation then, distillates to absence of liq.Filtered while hot is removed solid catalyst, and keeping liquidus temperature is 43 ℃.In product, drip 6%K
2CO
3Solution, to solution PH be 8.5, keeping solution temperature simultaneously is 43 ℃, standing demix is removed water, with 42 ℃ of deionized water wash products of two volumes, standing demix is removed water, the pH value that repeats this step to solution is 7.Constantly stir 10 ℃ of long-pending deionized waters of adding triploid in product down, separate out faint yellow solid, be methyl cinnamate, yield reaches 86%.
Embodiment 2
Get 14.8g styracin, 25.6g methyl alcohol and 0.85g loading type an acidic catalyst respectively and add in the 250ml flask, reflux 4h carries out underpressure distillation then, distillates to absence of liq.Filtered while hot is removed solid catalyst, and keeping liquidus temperature is 40 ℃.In product, drip 9%K
2CO
3Solution, to solution PH be 8, keeping solution temperature simultaneously is 40 ℃, standing demix is removed water, with 41 ℃ of deionized water wash products of two volumes, standing demix is removed water, the pH value that repeats this step to solution is 7.2.Constantly stir 9 ℃ of long-pending deionized waters of adding triploid in product down, separate out faint yellow solid, be methyl cinnamate, yield reaches 91%.
Embodiment 3
Get 14.8g styracin, 14.6g methyl alcohol and 4.44g loading type an acidic catalyst respectively and add in the 250ml flask, reflux 6h carries out underpressure distillation then, distillates to absence of liq.Filtered while hot is removed solid catalyst, and keeping liquidus temperature is 50 ℃.Dropwise 5 %K in product
2CO
3Solution, to solution PH be 8.2, keeping solution temperature simultaneously is 50 ℃, standing demix is removed water, with 40 ℃ of deionized water wash products of two volumes, standing demix is removed water, the pH value that repeats this step to solution is 7.Constantly stir 5 ℃ of long-pending deionized waters of adding triploid in product down, separate out faint yellow solid, be methyl cinnamate, yield reaches 88%.
Embodiment 4
Get 14.8g styracin, 20.8g methyl alcohol and 1.23g loading type an acidic catalyst respectively and add in the 250ml flask, reflux 5h carries out underpressure distillation then, distillates to absence of liq.Filtered while hot is removed solid catalyst, and keeping liquidus temperature is 45 ℃.Dropwise 5 %K in product
2CO
3Solution, to solution PH be 9, keeping solution temperature simultaneously is 45 ℃, standing demix is removed water, with 44 ℃ of deionized water wash products of two volumes, standing demix is removed water, the pH value that repeats this step to solution is 7.3.Constantly stir 5 ℃ of long-pending deionized waters of adding triploid in product down, separate out faint yellow solid, be methyl cinnamate, yield reaches 86%.
Embodiment 5
Get 14.8g styracin, 12.8g methyl alcohol and 3.44g loading type an acidic catalyst respectively and add in the 250ml flask, reflux 3.5h carries out underpressure distillation then, distillates to absence of liq.Filtered while hot is removed solid catalyst, and keeping liquidus temperature is 40 ℃.In product, drip 10%K
2CO
3Solution, to solution PH be 8.5, keeping solution temperature simultaneously is 40 ℃, standing demix is removed water, with 45 ℃ of deionized water wash products of two volumes, standing demix is removed water, the pH value that repeats this step to solution is 7.5.Constantly stir 8 ℃ of long-pending deionized waters of adding triploid in product down, separate out faint yellow solid, be methyl cinnamate, yield reaches 85%.
Embodiment 6
Get 14.8g styracin, 38.4g methyl alcohol and 2.35g loading type an acidic catalyst respectively and add in the 250ml flask, reflux 4.5h carries out underpressure distillation then, distillates to absence of liq.Filtered while hot is removed solid catalyst, and keeping liquidus temperature is 50 ℃.In product, drip 10%K
2CO
3Solution, to solution PH be 9, keeping solution temperature simultaneously is 50 ℃, standing demix is removed water, with 50 ℃ of deionized water wash products of two volumes, standing demix is removed water, the pH value that repeats this step to solution is 7.5.Constantly stir 10 ℃ of long-pending deionized waters of adding triploid in product down, separate out faint yellow solid, be methyl cinnamate, yield reaches 87%.
Embodiment 7
Get 14.8g styracin, 25.6g methyl alcohol and 2.98g loading type an acidic catalyst respectively and add in the 250ml flask, reflux 5.5h carries out underpressure distillation then, distillates to absence of liq.Filtered while hot is removed solid catalyst, and keeping liquidus temperature is 42 ℃.In product, drip 8%K
2CO
3Solution, to solution PH be 8, keeping solution temperature simultaneously is 42 ℃, standing demix is removed water, with 47 ℃ of deionized water wash products of two volumes, standing demix is removed water, the pH value that repeats this step to solution is 7.Constantly stir 15 ℃ of long-pending deionized waters of adding triploid in product down, separate out faint yellow solid, be methyl cinnamate, yield reaches 90%.
Embodiment 8
Get 14.8g styracin, 38.4g methyl alcohol and 4.00g loading type an acidic catalyst respectively and add in the 250ml flask, reflux 7h carries out underpressure distillation then, distillates to absence of liq.Filtered while hot is removed solid catalyst, and keeping liquidus temperature is 45 ℃.In product, drip 7%K
2CO
3Solution, to solution PH be 8.5, keeping solution temperature simultaneously is 45 ℃, standing demix is removed water, with 45 ℃ of deionized water wash products of two volumes, standing demix is removed water, the pH value that repeats this step to solution is 7.2.Constantly stir 14 ℃ of long-pending deionized waters of adding triploid in product down, separate out faint yellow solid, be methyl cinnamate, yield reaches 85%.
Claims (4)
1. the process for catalytic synthesis of a methyl cinnamate is characterized in that, comprises the steps:
(1) styracin and methyl alcohol carry out liquid-solid phase catalytic esterification under the loaded catalyst effect, and temperature of reaction is 70-80 ℃, reaction times 3-7h;
(2) product with step (1) carries out underpressure distillation, and the water and unreacted methanol to the absence of liq that steam the reaction generation distillate;
(3) with the product filtered while hot of step (2), remove loaded catalyst, keep filtrating, and to keep its temperature be 40-50 ℃;
(4) in the filtrating of step (3), adding proper quantity of lye to its pH value is 8-9, and the temperature of keeping this solution is 40-50 ℃, and standing demix is removed water, and the reservation oil phase is a product;
(5) use this product of deionized water wash with isopyknic 40-50 ℃ of rapid (4) product, standing demix is removed water, and the pH value that repeats this step to solution is 7-7.5;
(6) in the product of step (5), add 5-15 ℃ of deionized water, separate out faint yellow solid, filter, promptly get title product;
The carrier of said loaded catalyst is selected from SiO
2, TiO
2, gac, 5A molecular sieve, γ-Al
2O
3In a kind of, the activity of such catalysts component is selected from phospho-wolframic acid, phospho-molybdic acid, sodium pyrosulfate, SnCl
4In a kind of, the mass ratio of said loaded catalyst and styracin is 0.05-1: 100, the mass ratio of said catalyst activity component and carrier is 5-10: 100.
2. method according to claim 1 is characterized in that, the mol ratio of styracin and methyl alcohol is 1: 4-12.
3. method according to claim 1 is characterized in that, the alkali lye in the said step (4) is selected from K
2CO
3Solution, Na
2C
2O
3A kind of in solution, NaOH solution, the KOH solution, the mass concentration of said alkali lye is 5%-10%.
4. method according to claim 1 is characterized in that, the volume of the deionized water in the said step (6) is 3 times of step (5) product.
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|---|---|---|---|
| CN2012101401306A CN102701973A (en) | 2012-05-08 | 2012-05-08 | Catalytic synthesis method of methyl cinnamate |
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|---|---|---|---|
| CN2012101401306A CN102701973A (en) | 2012-05-08 | 2012-05-08 | Catalytic synthesis method of methyl cinnamate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013679A (en) * | 2012-11-30 | 2013-04-03 | 包头市京瑞新材料有限公司 | Method for synthesizing mixed methyl palmitate and methyl stearate by recycling cerium phosphotungstate catalyst |
| CN115819226A (en) * | 2022-12-08 | 2023-03-21 | 沧州临港丰亚化工有限公司 | Method for synthesizing o-phenyl phenoxyethyl acrylate |
Citations (2)
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|---|---|---|---|---|
| US3392191A (en) * | 1963-03-28 | 1968-07-09 | Monsanto Chemicals | Preparation of acrylic acid esters |
| CN101703940A (en) * | 2009-11-09 | 2010-05-12 | 中国海洋石油总公司 | Method for preparing solid acid catalyst of esterification |
-
2012
- 2012-05-08 CN CN2012101401306A patent/CN102701973A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3392191A (en) * | 1963-03-28 | 1968-07-09 | Monsanto Chemicals | Preparation of acrylic acid esters |
| CN101703940A (en) * | 2009-11-09 | 2010-05-12 | 中国海洋石油总公司 | Method for preparing solid acid catalyst of esterification |
Non-Patent Citations (6)
| Title |
|---|
| 俞善信等: "硫酸氢钠催化合成肉桂酸甲酯", 《香料香精化妆品》 * |
| 唐熏等: "丙烯酸正丁酯合成反应的负载型固体催化剂的研究", 《湖南大学学报》 * |
| 管仕斌等: "硫酸氢钠催化合成肉桂酸酯", 《湖南师范大学自然科学学报》 * |
| 薛萍等: "肉桂酸甲酯绿色合成新工艺的研究", 《中国酿造》 * |
| 靳通收等: "固体超强酸ZrO2/S2O8催化合成肉桂酸甲酯", 《化学研究》 * |
| 黎海妮等: "合成肉桂酸甲酯催化剂研究进展", 《化工生产与技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013679A (en) * | 2012-11-30 | 2013-04-03 | 包头市京瑞新材料有限公司 | Method for synthesizing mixed methyl palmitate and methyl stearate by recycling cerium phosphotungstate catalyst |
| CN115819226A (en) * | 2022-12-08 | 2023-03-21 | 沧州临港丰亚化工有限公司 | Method for synthesizing o-phenyl phenoxyethyl acrylate |
| CN115819226B (en) * | 2022-12-08 | 2023-11-24 | 信诺立兴(沧州渤海新区)化工有限公司 | Method for synthesizing o-phenylphenoxyethyl acrylate |
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Application publication date: 20121003 |