CN116693385A - Cinnamic acid cinnamate catalytic synthesis and preparation method thereof - Google Patents
Cinnamic acid cinnamate catalytic synthesis and preparation method thereof Download PDFInfo
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- CN116693385A CN116693385A CN202210786382.XA CN202210786382A CN116693385A CN 116693385 A CN116693385 A CN 116693385A CN 202210786382 A CN202210786382 A CN 202210786382A CN 116693385 A CN116693385 A CN 116693385A
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- CN
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- Prior art keywords
- cinnamate
- preparation
- catalytic synthesis
- product
- crude product
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- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 23
- 229940114081 cinnamate Drugs 0.000 title claims abstract description 22
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 title claims abstract description 7
- 229930016911 cinnamic acid Natural products 0.000 title claims abstract description 7
- 235000013985 cinnamic acid Nutrition 0.000 title claims abstract description 7
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 25
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims abstract description 22
- 239000012043 crude product Substances 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 13
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 claims abstract description 11
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims abstract description 11
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 238000005057 refrigeration Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 6
- NQBWNECTZUOWID-UHFFFAOYSA-N (E)-cinnamyl (E)-cinnamate Natural products C=1C=CC=CC=1C=CC(=O)OCC=CC1=CC=CC=C1 NQBWNECTZUOWID-UHFFFAOYSA-N 0.000 description 5
- NQBWNECTZUOWID-MZXMXVKLSA-N Cinnamyl cinnamate Chemical compound C=1C=CC=CC=1/C=C/C(=O)OC\C=C\C1=CC=CC=C1 NQBWNECTZUOWID-MZXMXVKLSA-N 0.000 description 5
- KLTVSWGXIAYTHO-UHFFFAOYSA-N 1-Octen-3-one Chemical compound CCCCCC(=O)C=C KLTVSWGXIAYTHO-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004321 preservation Methods 0.000 description 3
- 239000001636 3-phenylprop-2-enyl 3-phenylprop-2-enoate Substances 0.000 description 2
- 244000242564 Osmanthus fragrans Species 0.000 description 2
- 235000019083 Osmanthus fragrans Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 240000000513 Santalum album Species 0.000 description 1
- 235000008632 Santalum album Nutrition 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of organic synthesis, and provides a cinnamic acid cinnamate catalytic synthesis and a preparation method thereof, comprising the following steps: ethyl cinnamate and cinnamyl alcohol are used as raw materials, and an alkaline substance A is used as a catalyst to carry out transesterification reaction; step two: carrying out reduced pressure distillation on the product obtained in the step one to obtain a crude product; step three: dissolving the crude product obtained in the second step in a certain amount of organic solvent B, and removing a part of solvent B; step four: and (3) carrying out suction filtration on the product obtained in the step (III), and carrying out vacuum drying on the obtained solid to obtain the product. According to the preparation method, ethyl cinnamate and cinnamyl alcohol are used as raw materials, an alkaline substance A is used as a catalyst, transesterification is carried out, the next treatment is carried out, the obtained product is subjected to reduced pressure distillation, the obtained crude product is dissolved in a certain amount of organic solvent B, a part of solvent B is removed, the product is subjected to suction filtration, the obtained solid is subjected to vacuum drying, and the product obtained in the process is high in yield and reliable in product quality.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a catalytic synthesis method of cinnamate and a preparation method thereof.
Background
The cinnamic acid cinnamyl ester is colorless or white crystal, is mild in sweet osmanthus and soft in fragrance, is flower fragrance, has a certain spicy fragrance, is heavy and durable in fragrance and stable in property, is suitable for heavy sweet osmanthus fragrance type in the preparation of daily chemical essence, can also be used for decoration and fragrance fixation of sandalwood type, has large market demand, but the cinnamic acid cinnamyl ester on the market is low in preparation yield and low in product quality at present, and the catalytic synthesis and the preparation method of the cinnamic acid cinnamyl ester are provided.
Disclosure of Invention
In order to solve the technical problems, the invention provides a catalytic synthesis method of cinnamyl cinnamate and a preparation method thereof, which are achieved by the following specific technical means:
the invention adopts the following technical scheme for realizing the technical purpose: a cinnamic acid cinnamate catalytic synthesis and a preparation method thereof comprise the following steps of
Step one: taking ethyl cinnamate and cinnamyl alcohol as raw materials, taking an alkaline substance A as a catalyst, performing transesterification, filtering or not, and performing the next treatment;
step two: carrying out reduced pressure distillation on the product obtained in the step one to obtain a crude product;
step three: dissolving the crude product obtained in the second step in a certain amount of organic solvent B, removing a part of solvent B, and putting the crude product into refrigeration equipment for refrigeration;
step four: and (3) carrying out suction filtration on the product obtained in the step (III), and carrying out vacuum drying on the obtained solid to obtain the product.
Preferably, the alkaline substance A in the first step is any one or any combination of sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate and the like, including but not limited to different types and different combination ratios thereof.
Preferably, the ratio of the ethyl cinnamate to the cinnamyl alcohol in the first step is 1.0-1.5:1, and the amount of the alkaline substance A is 0.01-0.2 times of the amount of the 1-octen-3-one substance.
Preferably, the reaction temperature of the first step is 50-150 ℃.
Preferably, after no more byproducts are separated out in the first step, the reaction is carried out for 8 to 10 hours in a heat preservation way
Preferably, the solid in the system is removed by filtration after the reaction in the first step, and the catalyst solid may not be filtered.
Preferably, the crude product is obtained by reduced pressure distillation in the second step.
Advantageous effects
Compared with the prior art, the invention provides the catalytic synthesis and the preparation method of the cinnamic acid cinnamate, which have the following beneficial effects:
1. according to the catalytic synthesis method of the cinnamyl cinnamate and the preparation method thereof, ethyl cinnamate and cinnamyl alcohol are used as raw materials, an alkaline substance A is used as a catalyst, transesterification reaction is carried out, filtering or no filtering is carried out, next treatment is carried out, the obtained product is subjected to reduced pressure distillation to obtain a crude product, the obtained crude product is dissolved in a certain amount of organic solvent B, a part of solvent B is removed, the obtained product is placed in refrigeration equipment for refrigeration, the product is subjected to suction filtration, and the obtained solid is subjected to vacuum drying to obtain the product.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A cinnamic acid cinnamate catalytic synthesis and a preparation method thereof comprise the following steps of
Step one: taking ethyl cinnamate and cinnamyl alcohol as raw materials, taking an alkaline substance A as a catalyst, performing transesterification, filtering or not, and performing the next treatment;
step two: carrying out reduced pressure distillation on the product obtained in the step one to obtain a crude product;
step three: dissolving the crude product obtained in the second step in a certain amount of organic solvent B, removing a part of solvent B, and putting the crude product into refrigeration equipment for refrigeration;
step four: filtering the product obtained in the third step, and vacuum drying the obtained solid to obtain the product
Further, the alkaline substance a in the first step is any one or any combination of sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate and the like, including but not limited to different types and different combination ratios thereof.
Further, the ratio of the ethyl cinnamate to the cinnamyl alcohol in the first step is 1.0-1.5:1, and the amount of the alkaline substance A is 0.01-0.2 times of the amount of the 1-octen-3-one substance.
Further, the reaction temperature of the first step is 50-150 ℃.
Further, after no more byproducts are separated out in the first step, the reaction is carried out for 8 to 10 hours at a constant temperature
Further, the catalyst solid may not be filtered out after the completion of the reaction in the first step.
Further, the crude product is obtained by reduced pressure distillation in the second step.
The invention is further described by way of examples below:
example 1
S1, adding 99g of ethyl cinnamate, 63g of cinnamyl alcohol and 2g of heated potassium carbonate into a four-mouth bottle with a stirring device, heating to 100 ℃ until no more ethanol exists, and then carrying out heat preservation reaction for 8 hours.
S2, cooling, and distilling under reduced pressure to obtain a crude product of cinnamate, 105g.
S3, dissolving the crude product obtained in the step S2 in 50 milliliters of ethyl acetate, and putting the obtained product into a freezer for freezing after the obtained product is uniformly dissolved.
S4, filtering, and drying the obtained white solid in vacuum to obtain 85 g of product with the content of 98.12% and the yield of 68%.
Example 2
S1, adding 199g of ethyl cinnamate, 130g of cinnamyl alcohol and 2g of cesium carbonate into a four-mouth bottle with a stirring device, heating to 100 ℃ until no more ethanol exists, and then carrying out heat preservation reaction for 8 hours.
S2, cooling, and distilling under reduced pressure to obtain 205g of crude cinnamate.
S3, dissolving the crude product obtained in the step S2 in 100 milliliters of ethyl acetate, and putting the mixture into a freezer for freezing after the mixture is uniformly dissolved.
S4, filtering, and vacuum drying the obtained white solid to obtain 216 g of product with the content of 98.23% and the yield of 87%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A cinnamic acid cinnamate catalytic synthesis and a preparation method thereof are characterized in that: comprises the following steps of
Step one: taking ethyl cinnamate and cinnamyl alcohol as raw materials, taking an alkaline substance A as a catalyst, performing transesterification, filtering or not, and performing the next treatment;
step two: carrying out reduced pressure distillation on the product obtained in the step one to obtain a crude product;
step three: dissolving the crude product obtained in the second step in a certain amount of organic solvent B, removing a part of solvent B, and putting the crude product into refrigeration equipment for refrigeration;
step four: and (3) carrying out suction filtration on the product obtained in the step (III), and carrying out vacuum drying on the obtained solid to obtain the product.
2. The catalytic synthesis and preparation method of cinnamate according to claim 1, wherein the catalytic synthesis and preparation method of cinnamate are characterized in that: the alkaline substance A in the first step is any one or any combination of sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate and the like, including but not limited to different types and different combination ratios thereof.
3. The catalytic synthesis and preparation method of cinnamate according to claim 1, wherein the catalytic synthesis and preparation method of cinnamate are characterized in that: the ratio of the ethyl cinnamate to the cinnamyl alcohol in the first step is 1.0-1.5:1, and the amount of the alkaline substance A is 0.01-0.2 times of the amount of the 1-octene-3-ketone substance.
4. The catalytic synthesis and preparation method of cinnamate according to claim 1, wherein the catalytic synthesis and preparation method of cinnamate are characterized in that: the reaction temperature of the first step is 50-150 ℃.
5. The catalytic synthesis and preparation method of cinnamate according to claim 1, wherein the catalytic synthesis and preparation method of cinnamate are characterized in that: and in the first step, after no more byproducts are separated out, the reaction is carried out for 8 to 10 hours at the temperature.
6. The catalytic synthesis and preparation method of cinnamate according to claim 1, wherein the catalytic synthesis and preparation method of cinnamate are characterized in that: after the reaction in the first step is finished, the solid in the system is removed by filtration, and the catalyst solid can be removed by filtration.
7. The catalytic synthesis and preparation method of cinnamate according to claim 1, wherein the catalytic synthesis and preparation method of cinnamate are characterized in that: and in the second step, the crude product is obtained through reduced pressure distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210786382.XA CN116693385A (en) | 2022-07-04 | 2022-07-04 | Cinnamic acid cinnamate catalytic synthesis and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210786382.XA CN116693385A (en) | 2022-07-04 | 2022-07-04 | Cinnamic acid cinnamate catalytic synthesis and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116693385A true CN116693385A (en) | 2023-09-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210786382.XA Pending CN116693385A (en) | 2022-07-04 | 2022-07-04 | Cinnamic acid cinnamate catalytic synthesis and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116693385A (en) |
-
2022
- 2022-07-04 CN CN202210786382.XA patent/CN116693385A/en active Pending
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