CN115433082A - Synthetic method of cinnamic acid - Google Patents
Synthetic method of cinnamic acid Download PDFInfo
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- CN115433082A CN115433082A CN202210974233.6A CN202210974233A CN115433082A CN 115433082 A CN115433082 A CN 115433082A CN 202210974233 A CN202210974233 A CN 202210974233A CN 115433082 A CN115433082 A CN 115433082A
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- cinnamic acid
- benzaldehyde
- acid according
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- synthesizing cinnamic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
Abstract
The invention discloses a method for synthesizing cinnamic acid, which comprises the steps of mixing and stirring benzaldehyde and acetic acid, adding Lewis acid, dropwise adding organic base, keeping the reaction temperature at 10-40 ℃, reacting for 1-24 h, adding water for quenching, filtering and drying to obtain cinnamic acid; the invention is a solvent-free reaction, has mild condition and simple operation and high yield.
Description
Technical Field
The invention belongs to the technical field of medicines, and particularly relates to a synthetic method of cinnamic acid.
Background
Cinnamic acid is an important organic synthetic raw material and is mainly used in the aspects of essences, spices, food additives, pharmaceutical industry, beauty, pesticides and the like.
The existing main synthetic method of cinnamic acid such as Perkin method requires high temperature reaction, generally the yield is not high, the Knoevenagel method also requires heating reaction, and the used raw materials such as malonic acid, pyridine and the like are expensive. The existing main synthetic methods of the cinnamic acid mainly comprise: the method comprises the steps of a Perkin synthesis method; the benzaldehyde 2 acetone method; the method of the anhydrous sodium acetate of the benylidene dichloro-2. The methods or procedures are long, the temperature is high, the energy consumption is high, and the yield is low; or more byproducts, difficult separation and purification and serious pollution. Method for oxidizing cinnamaldehyde to cinnamic acid by H 2 O 2 (the concentration requirement is 90 to 100 percent of dangerous goods) NaClO 2 Oxidizing by using inorganic oxide as oxidantLarge amounts of organic solvents such as propionitrile and benzene are needed, which pollutes the environment and is not beneficial to industrialization.
Disclosure of Invention
In order to solve the problems, the invention discloses a new method for synthesizing cinnamic acid, which has the advantages of simple and convenient operation, high yield, mild reaction conditions and good industrialization prospect.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the synthesis method of the cinnamic acid comprises the following steps: adding benzaldehyde and acetic acid into a reactor, mixing and stirring, adding Lewis acid, adding organic base, stirring for reaction, quenching with water, filtering, leaching and drying to obtain the cinnamic acid.
Further, the lewis acid is one or more of titanium tetrachloride, titanium tetraisopropoxide, aluminum trichloride, ferric trichloride, boron trichloride, zinc chloride, indium chloride, zirconium chloride, copper chloride and tin chloride, and preferably, the lewis acid is titanium tetrachloride.
Further, the organic base is one or more of triethylamine, diisopropylethylamine, tripropylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene, pyridine, 2,6-lutidine, and 2,4,6-collidine, preferably the organic base is triethylamine.
Further, the molar ratio of the acetic acid to the benzaldehyde is 1-1.5: 1, preferably, the molar ratio of acetic acid to benzaldehyde is 1.2:1.
further, the molar ratio of the Lewis acid to the benzaldehyde is 2-3: 1, preferably, the molar ratio of the Lewis acid to the benzaldehyde is 2.1:1.
further, the molar ratio of the organic base to the benzaldehyde is 2-4: 1, preferably, the molar ratio of the organic base to benzaldehyde is 2.5:1.
further, the temperature of the reaction is 10-40 ℃, preferably 20-30 ℃.
Further, the reaction time is 1 to 20 hours, and preferably, the reaction time is 3 to 4 hours.
Compared with the prior art, the invention has the beneficial effects that:
the method has the advantages of simple operation, mild reaction conditions, high yield, environment-friendly and economical solvent-free reaction, and good industrialization prospect, and the product can be obtained by filtering, leaching and drying after the post-treatment and water quenching.
Drawings
Figure 1 is an HPLC diagram of the product cinnamic acid of example 1;
figure 2 is the mass spectrum (negative mode) of the product cinnamic acid of example 1;
figure 3 is the nuclear magnetic resonance hydrogen spectrum of the product cinnamic acid of example 1.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
Example 1
Adding 10 g of benzaldehyde into a reactor, stirring, adding 6.8 g of acetic acid, dropwise adding 37.44 g of titanium tetrachloride, dropwise adding 23.78 g of triethylamine, keeping the temperature at 20-25 ℃, continuing to react for 4 hours, dropwise adding 300 ml of water under an ice bath, stirring for 30 minutes, filtering, leaching with water for three times, each time for 100 ml, and drying by blowing at 60-65 ℃ until the weight is constant to obtain 13.2 g of white solid, wherein the yield is 94.78%. Purity 99.63% (220 nm, FIG. 1). LC-MS [ 147 ] M-1] - (FIG. 2); 1 H NMR(400MHz,DMSO-d 6 ) δ 12.39 (s, 1H), 7.73-7.65 (m, 2H), 7.60 (d, J =16.0hz, 1h), 7.48-7.38 (m, 3H), 6.54 (d, J =16.0hz, 1h) (fig. 3).
Example 2
Adding 10 g of benzaldehyde into a reactor, stirring, adding 8.47 g of acetic acid, dropwise adding 44.57 g of titanium tetrachloride, dropwise adding 28.54 g of triethylamine, keeping the temperature at 15-20 ℃, continuing to react for 3 hours, dropwise adding 400 ml of water under an ice bath, stirring for 40 minutes, filtering, leaching with water for three times, each time washing with 100 ml of water, and drying by air blowing at 60-65 ℃ until the weight is constant to obtain 12.77 g of white solid with the yield of 91.7%.
Example 3
Adding 10 g of benzaldehyde into a reactor, stirring, adding 5.64 g of acetic acid, dropwise adding 35.66 g of titanium tetrachloride, dropwise adding 19 g of triethylamine, keeping the temperature at 10-15 ℃, continuing to react for 1 hour, dropwise adding 300 ml of water under ice bath, stirring for 30 minutes, filtering, leaching with water for three times, each time for 100 ml, and carrying out forced air drying at 60-65 ℃ until the weight is constant to obtain 7.1 g of white solid with the yield of 51%.
Example 4
Adding 10 g of benzaldehyde into a reactor, stirring, adding 8.47 g of acetic acid, dropwise adding 53.5 g of titanium tetrachloride, dropwise adding 38 g of triethylamine, keeping the temperature at 35-40 ℃, continuing to react for 20 hours, dropwise adding 300 ml of water under ice bath, stirring for 30 minutes, filtering, leaching with water for three times, each time for 100 ml, and carrying out forced air drying at 60-65 ℃ until the weight is constant to obtain 11 g of white solid with the yield of 79%.
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.
Claims (8)
1. A method for synthesizing cinnamic acid is characterized by comprising the following steps:
under the condition of stirring, mixing benzaldehyde and acetic acid, adding Lewis acid and organic base, adding water for quenching after the reaction is finished, filtering, leaching and drying to obtain the cinnamic acid.
2. The method for synthesizing cinnamic acid according to claim 1, wherein the molar ratio of acetic acid to benzaldehyde is 1-1.5: 1.
3. the method for synthesizing cinnamic acid according to claim 1, wherein the molar ratio of the Lewis acid to the benzaldehyde is 2-3: 1.
4. the method for synthesizing cinnamic acid according to claim 1, wherein the molar ratio of the organic base to the benzaldehyde is 2-4: 1.
5. the method for synthesizing cinnamic acid according to claim 1, wherein the lewis acid is one or more of titanium tetrachloride, titanium tetraisopropoxide, aluminum trichloride, ferric trichloride, boron trichloride, zinc chloride, indium chloride, zirconium chloride, copper chloride and tin chloride.
6. The method for synthesizing cinnamic acid according to claim 1, wherein the organic base is one or more of triethylamine, diisopropylethylamine, tripropylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene, pyridine, 2,6-lutidine, and 2,4,6-collidine.
7. The method for synthesizing cinnamic acid according to claim 1, wherein the reaction temperature is 10-40 ℃.
8. The method for synthesizing cinnamic acid according to claim 1, wherein the reaction time is 1-20 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210974233.6A CN115433082A (en) | 2022-08-15 | 2022-08-15 | Synthetic method of cinnamic acid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210974233.6A CN115433082A (en) | 2022-08-15 | 2022-08-15 | Synthetic method of cinnamic acid |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6150938A (en) * | 1984-08-20 | 1986-03-13 | Mitsui Toatsu Chem Inc | Production of cinnamic acid or cinnamic ester |
| CN102633624A (en) * | 2012-03-22 | 2012-08-15 | 湖北远成药业有限公司 | Method for preparing methylcinnamic acid |
| CN106831415A (en) * | 2016-12-28 | 2017-06-13 | 广州星业科技股份有限公司 | A kind of preparation method and application of p-methoxycinnamic acid ester |
| CN109096091A (en) * | 2018-08-27 | 2018-12-28 | 上海华堇生物技术有限责任公司 | The preparation method of cinnamic acid |
-
2022
- 2022-08-15 CN CN202210974233.6A patent/CN115433082A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6150938A (en) * | 1984-08-20 | 1986-03-13 | Mitsui Toatsu Chem Inc | Production of cinnamic acid or cinnamic ester |
| CN102633624A (en) * | 2012-03-22 | 2012-08-15 | 湖北远成药业有限公司 | Method for preparing methylcinnamic acid |
| CN106831415A (en) * | 2016-12-28 | 2017-06-13 | 广州星业科技股份有限公司 | A kind of preparation method and application of p-methoxycinnamic acid ester |
| CN109096091A (en) * | 2018-08-27 | 2018-12-28 | 上海华堇生物技术有限责任公司 | The preparation method of cinnamic acid |
Non-Patent Citations (1)
| Title |
|---|
| JOHN KALLIKAT AUGUSTINE 等: "TiCl4-mediated olefination of aldehydes with acetic acid and alkylacetates: a stereoselective approach to (E)- α, β-unsaturated carboxylic acids and esters", TETRAHEDRON LETTERS, vol. 55, pages 3503 * |
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