CN101265167A - Process for preparing a-methyl cinnamaldehyde - Google Patents
Process for preparing a-methyl cinnamaldehyde Download PDFInfo
- Publication number
- CN101265167A CN101265167A CNA2008100475503A CN200810047550A CN101265167A CN 101265167 A CN101265167 A CN 101265167A CN A2008100475503 A CNA2008100475503 A CN A2008100475503A CN 200810047550 A CN200810047550 A CN 200810047550A CN 101265167 A CN101265167 A CN 101265167A
- Authority
- CN
- China
- Prior art keywords
- cinnamic acid
- methyl
- aldehyde
- temperature
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- VLUMOWNVWOXZAU-VQHVLOKHSA-N (e)-2-methyl-3-phenylprop-2-enal Chemical compound O=CC(/C)=C/C1=CC=CC=C1 VLUMOWNVWOXZAU-VQHVLOKHSA-N 0.000 title 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- -1 phenyl aldehyde Chemical class 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 2
- XNCRUNXWPDJHGV-BQYQJAHWSA-N (e)-2-methyl-3-phenylprop-2-enoic acid Chemical compound OC(=O)C(/C)=C/C1=CC=CC=C1 XNCRUNXWPDJHGV-BQYQJAHWSA-N 0.000 abstract 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method of preparing a-methyl cinnamic acid. The method comprises the following steps: A. sodium hydroxide is added into methanol water solution, mixed round to be well-proportioned and then the temperature is reduced; B. benzaldehyde and water are dissolved in the methanol water solution and then n-propylaldehyde is dropped in after mixing round; C. the time for dropping the n-propylaldehyde is from 5 hours to 8 hours, the temperature is maintained between 15 DEG C and 25 DEG C in reaction process, the a-methyl cinnamic acid produce is obtained after water washing, neutralization and separation; D. the a-methyl cinnamic acid produce is decompressed again and the finished product of the a-methyl cinnamic acid is collected. The method of preparing the a-methyl cinnamic acid has the advantages that the method is simple; the operation is convenient; the cost of materials is low and the yield rate is high; and no pollution is caused to the environment. The method extremely adapts to the industrialization production. The yield rate of a-methyl cinnamic acid production is high to 82.4 percent.
Description
Technical field
The invention belongs to chemical field, more specifically relate to a kind of preparation method of a-methyl phenylacrolein., it is applied to prepare spice essence and cooperates cinnamic aldehyde to use mainly as fixative. also can be used for the fruit flavouring food flavor(ing) by trace.
Background technology
A-methyl phenylacrolein chemical name is an a-methylbenzene propenal, is a kind of important fine-chemical intermediate, is widely used in the production of products such as medicine, spices.Preparation a-methyl phenylacrolein has following several method at present: be raw material with phenyl aldehyde and positive propionic aldehyde 1,, KF/Al2O3 is a catalyzer, and polyoxyethylene glycol is a phase transition solution, synthetic α-Jia Jirouguiquan, yield 78.9%.This method synthetic a-methyl phenylacrolein yield height, technology is fairly simple, but the Preparation of catalysts more complicated that is to use, and price is expensive, and environment is had any pollution, and recovery process is loaded down with trivial details.2, be raw material with phenyl aldehyde and positive propionic aldehyde, ethanol is made solvent, and PEG400, PEG600 are the synthetic α-Jia Jirouguiquan of phase transition, yield 54.2%, and the negative reaction of this method synthetic α-Jia Jirouguiquan is many, and product separation is purified difficult; 3, be raw material with phenyl aldehyde and positive propionic aldehyde, ethanol is made solvent, TBAB is a phase-transfer catalyst, synthetic α-Jia Jirouguiquan under alkaline medium condition, yield 59.7%, this method synthetic α-Jia Jirouguiquan synthesis technique is simple, but the raw material reaction transformation efficiency is low, and negative reaction is many and cause product yield on the low side.
Summary of the invention
The objective of the invention is to be to provide a kind of preparation method of a-methyl phenylacrolein, this method uses phenyl aldehyde and positive propionic aldehyde in alkaline medium, the method that with the methanol in water is solvent is synthesized α-Jia Jirouguiquan, method is simple, easy to operate, raw materials cost is cheap, and the yield height, also pollution-free to environment, be very suitable for suitability for industrialized production.
To achieve these goals, the present invention the steps include: by the following technical solutions
A, in 40 or 50 or 60% methanol aqueous solution, press water in the methanol aqueous solution quality 1 or 3 or 6 or 8 or 10% add sodium hydroxide, it is molten entirely to be stirred to sodium hydroxide, is cooled to 15-25 ℃;
B, be 1 with the methanol aqueous solution of phenyl aldehyde and 40-60% in mass ratio: the ratio of 2-3 is dissolved in the methanol aqueous solution of 40-60%, in reactor, stirs 0.5 hour.Temperature remains on 15-25 ℃ and drips positive propionic aldehyde; Phenyl aldehyde is 1 with the mol ratio of positive propionic aldehyde: 0.8-1.2;
C, the time that drips positive propionic aldehyde are 5 or 6 or 7 or 8 hours, and temperature remains on 15 or 18 or 22 or 25 ℃ of reactions 1 hour, positive propionic aldehyde dropwise after washing, neutralization separate a-methyl phenylacrolein raw product.
D, with a-methyl phenylacrolein raw product under decompression-0.097--0.1Mpa condition, temperature is controlled at 88 or 92 or 96 or 102 or 106 or 110 or 114 ℃ and collects unreacted phenyl aldehyde, and temperature is controlled at 142 or 145 or 148 or 152 or 156 or 160 or 164 or 170 ℃ and collects a-methyl phenylacrolein finished product.
The inventive method is easily gone, and technology is simple, and production cost is low, and is pollution-free, stable and reliable product quality, and raw material is easy to get, and producing a-methyl phenylacrolein yield can be up to 82.4% (in phenyl aldehyde).
Embodiment
Embodiment 1
Get in the methanol aqueous solution that 10g sodium hydroxide is dissolved in 200g40%, being stirred to sodium hydroxide dissolves fully, add 100g (0.943mol) phenyl aldehyde, stirred 0.5 hour, controlled temperature drips positive propionic aldehyde 43.77g (0.754mol) at 16 or 19 or 23 or 25 ℃, the dropping time is 5 or 6 or 7 or 8 hours, positive propionic aldehyde dropwises after washing, neutralization, separate a-methyl phenylacrolein raw product.Under-0.097Mpa condition, collect 112 or 113 or 114 ℃ of cuts and get phenyl aldehyde 20g, collect 164 or 165 or 166 or 167 or 168 ℃ of cuts and get a-methyl phenylacrolein finished product 87.16g, yield 79.1%.
Embodiment 2
Get in the methanol aqueous solution that 6g sodium hydroxide is dissolved in 200g50%, being stirred to sodium hydroxide dissolves fully, add 100g (0.943mol) phenyl aldehyde, stirred 0.5 hour, controlled temperature drips positive propionic aldehyde 52g (0.896mol) at 15 or 17 or 21 or 24 ℃, the dropping time is 5 or 6 or 7 or 8 hours, positive propionic aldehyde dropwises after washing, neutralization, separate a-methyl phenylacrolein raw product.Under-0.098Mpa condition, collect 95 or 96 or 97 or 98 ℃ of cuts and get phenyl aldehyde 24.2g, collect 155 or 156 or 157 or 158 ℃ of cuts and get a-methyl phenylacrolein finished product 87.07g, yield 83.4%.
Embodiment 3
Get in the methanol aqueous solution that 4g sodium hydroxide is dissolved in 200g60%, being stirred to sodium hydroxide dissolves fully, add 100g (0.943mol) phenyl aldehyde, stirred 0.5 hour, controlled temperature drips positive propionic aldehyde 60.16g (1.037mol) at 15 or 20 or 21 or 25 ℃, the dropping time is 5 or 6 or 7 or 8 hours, positive propionic aldehyde dropwises after washing, neutralization, separate a-methyl phenylacrolein raw product.Under-0.099Mpa condition, collect 92 or 93 or 94 or 95 ℃ of cuts and get phenyl aldehyde 18.4g, collect 148 or 149 or 150 or 151 or 152 ℃ of cuts and get a-methyl phenylacrolein finished product 91.94g, yield 81.8%.
Embodiment 4
Get in the methanol aqueous solution that 1g sodium hydroxide is dissolved in 200g45%, being stirred to sodium hydroxide dissolves fully, add 100g (0.943mol) phenyl aldehyde, stirred 0.5 hour, controlled temperature drips positive propionic aldehyde 65.6g (1.132mol) at 15 or 18 or 22 or 25 ℃, the dropping time is 5 or 6 or 7 or 8 hours, positive propionic aldehyde dropwises after washing, neutralization, separate a-methyl phenylacrolein raw product.Under-0.1Mpa condition, collect 88 or 89 or 90 or 91 ℃ of cuts and get phenyl aldehyde 20.3g, collect 142 or 143 or 144 or 145 ℃ of cuts and get a-methyl phenylacrolein finished product 89.68g, yield 81.7%.
Claims (1)
1, a kind of preparation method of a-methyl phenylacrolein the steps include:
A, in the methanol aqueous solution of 40-60%, the amount of pressing the quality 1-10% of water in the methanol aqueous solution adds sodium hydroxide, it is molten entirely to be stirred to sodium hydroxide, and is cooled to 15-25 ℃;
B, be 1 with phenyl aldehyde and 40-60% methanol aqueous solution in mass ratio: the ratio of 2-3 is dissolved in the methanol aqueous solution of 40-60%, in reactor, stir after 0.5 hour, temperature is controlled at 15-25 ℃ and drips positive propionic aldehyde, and phenyl aldehyde is 1 with the mol ratio of positive propionic aldehyde: 0.8-1.2;
C, the time that drips positive propionic aldehyde are 5-8 hour, and temperature keeps 15-25 ℃ of reaction 1 hour, positive propionic aldehyde dropwise after washing, neutralization separate a-methyl phenylacrolein goods;
D, with a-methyl phenylacrolein goods under decompression-0.097--0.1Mpa condition, temperature is controlled at 88-114 ℃ and collects unreacted phenyl aldehyde, temperature is controlled at 142-170 ℃ and collects a-methyl phenylacrolein finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810047550A CN100595182C (en) | 2008-04-30 | 2008-04-30 | Process for preparing alpha-methyl cinnamaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810047550A CN100595182C (en) | 2008-04-30 | 2008-04-30 | Process for preparing alpha-methyl cinnamaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101265167A true CN101265167A (en) | 2008-09-17 |
| CN100595182C CN100595182C (en) | 2010-03-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810047550A Expired - Fee Related CN100595182C (en) | 2008-04-30 | 2008-04-30 | Process for preparing alpha-methyl cinnamaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100595182C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085213A (en) * | 2015-08-21 | 2015-11-25 | 应城市武瀚有机材料有限公司 | Refining method of high-purity trans-Alpha-methylcinnamaldehyde |
| JP6449507B1 (en) * | 2017-12-12 | 2019-01-09 | 花王株式会社 | Method for producing α, β-unsaturated aldehyde |
-
2008
- 2008-04-30 CN CN200810047550A patent/CN100595182C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085213A (en) * | 2015-08-21 | 2015-11-25 | 应城市武瀚有机材料有限公司 | Refining method of high-purity trans-Alpha-methylcinnamaldehyde |
| CN105085213B (en) * | 2015-08-21 | 2018-09-18 | 应城市武瀚有机材料有限公司 | A kind of process for purification of the trans- α-methylcinnamaldehyde of high-purity |
| JP6449507B1 (en) * | 2017-12-12 | 2019-01-09 | 花王株式会社 | Method for producing α, β-unsaturated aldehyde |
| WO2019116608A1 (en) * | 2017-12-12 | 2019-06-20 | 花王株式会社 | METHOD FOR PRODUCING α,β-UNSATURATED ALDEHYDE |
| US10981853B2 (en) | 2017-12-12 | 2021-04-20 | Kao Corporation | Method for preparing α,β-unsaturated aldehyde |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100595182C (en) | 2010-03-24 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
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Owner name: HUBEI YUANCHENG PHARMACEUTICAL CO., LTD. Free format text: FORMER OWNER: WUHAN HEZHONG BIO-CHEMICAL MANUFATURE CO., LTD. Effective date: 20111107 |
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Free format text: CORRECT: ADDRESS; FROM: 430064 WUHAN, HUBEI PROVINCE TO: 432100 XIAOGAN, HUBEI PROVINCE |
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Effective date of registration: 20111107 Address after: 432100, Hubei province Xiaogan City Industrial Park Road Patentee after: Hubei Yuancheng Pharmaceutical Co., Ltd. Address before: 430064, No. 201, 1000 street, Wuchang District, Hubei, Wuhan (No. 496, Zhongshan Road) Patentee before: Wuhan Hezhong Bio-chemical Manufature Co., Ltd. |
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| C56 | Change in the name or address of the patentee |
Owner name: HUBEI YUANCHENG SAICHUANG TECHNOLOGY CO., LTD. Free format text: FORMER NAME: HUBEI YUANCHENG PHARMACEUTICAL CO., LTD. |
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Address after: 430207, No. 28, Golden Road, Golden Industrial Park, Zheng Jie street, Jiangxia District, Hubei, Wuhan Patentee after: HUBEI YUANCHENG PHARMACEUTICAL CO., LTD. Address before: 432100, Hubei province Xiaogan City Industrial Park Road Patentee before: Hubei Yuancheng Pharmaceutical Co., Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100324 Termination date: 20160430 |