CN114539095A - Preparation method of 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate - Google Patents
Preparation method of 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate Download PDFInfo
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- CN114539095A CN114539095A CN202011356353.7A CN202011356353A CN114539095A CN 114539095 A CN114539095 A CN 114539095A CN 202011356353 A CN202011356353 A CN 202011356353A CN 114539095 A CN114539095 A CN 114539095A
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- Prior art keywords
- vanillin
- cyano
- methoxy
- hydroxy
- phenyl
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- 238000002360 preparation method Methods 0.000 title abstract description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 44
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims abstract description 24
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000012141 vanillin Nutrition 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- -1 4-hydroxy-3-methoxy-phenyl Chemical group 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- IJJJSNBMFDDFBC-UHFFFAOYSA-N 2-cyanoethyl acetate Chemical compound CC(=O)OCCC#N IJJJSNBMFDDFBC-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical group CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- 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
Abstract
The invention provides a preparation method of 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate, which comprises the following steps: reacting vanillin with ethyl cyanoacetate under the catalysis of morpholine to obtain 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate. The method takes a small amount of morpholine as a catalyst, reduces the dosage of ethyl cyanoacetate, has the advantages of quick reaction, simple and convenient operation, high conversion rate, high yield, less byproducts, no need of treatment on waste liquid, repeated utilization and suitability for industrial production and application.
Description
Technical Field
The present invention relates to the field of chemical synthesis. In particular, the invention relates to a preparation method of 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate.
Background
The light stabilizer 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate belongs to a broad-spectrum ultraviolet absorber, the absorption interval can reach 250-400 nm, especially ultraviolet protection in the interval of more than 390nm can be provided, and the light stabilizer can be combined with other stabilizers such as benzotriazole, hydroxybenzophenone and the like to improve the absorption width. Therefore, the use amount is low, the color value is low, other shielding agents are not needed, and the color filter can be used in a wide space such as capsules, sun cream and plastic products.
The synthesis of 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-acrylic acid ethyl ester mainly comprises a method of synthesizing potassium fluoride as a catalyst in absolute ethyl alcohol and a method of refluxing by taking piperidine as a catalyst in toluene. Wherein, the yield of the synthesis in absolute ethyl alcohol is low, the directional conversion rate is low, the product color is red, and the product needs to be separated out by adding large amount of water, so the pollution to the environment is large, and more wastes are generated. The method of refluxing by taking piperidine as a catalyst has the disadvantages of more piperidine dosage, reddish product color, difficult recovery due to small boiling point difference between piperidine and toluene, and waste discharge in the solvent recovery process.
Therefore, the preparation method of 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-acrylic acid ethyl ester still needs to be researched.
Disclosure of Invention
The present invention aims to solve at least to some extent at least one of the technical problems of the prior art. Therefore, the invention provides a preparation method of 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate, which takes a small amount of morpholine as a catalyst, reduces the using amount of ethyl cyanoacetate, has the advantages of rapid reaction, simple and convenient operation, high conversion rate, high yield, less byproducts, no need of treatment on waste liquid, repeated utilization and suitability for industrial production and application.
The invention provides a preparation method of 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate. According to an embodiment of the invention, the method comprises: reacting vanillin with ethyl cyanoacetate under the catalysis of morpholine to obtain 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate.
The inventor finds that the morpholine is used as a catalyst to efficiently catalyze the reaction of vanillin and ethyl cyanoacetate to generate the 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate. And the method has the advantages of small morpholine consumption, quick reaction, simple and convenient operation, single raw material conversion, high conversion rate, high yield, few byproducts, no treatment of waste liquid, repeated utilization and suitability for industrial production and application.
According to an embodiment of the present invention, the above method for preparing ethyl 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-acrylate may further have the following additional technical features:
according to an embodiment of the present invention, the morpholine is 0.01 to 0.3 mass% of the mass of vanillin. The inventor finds that the reaction of vanillin and ethyl cyanoacetate can be efficiently catalyzed to generate the 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate by using a small amount of morpholine, the yield of a target product is high, and a few byproducts are generated. And because less catalyst is used, the residual toxicity of the product is low. In some preferred embodiments, the mass of morpholine is 0.06-0.15 mass%, more preferably 0.09-0.1 mass% of the mass of vanillin.
According to an embodiment of the invention, said vanillin is provided in the form of a vanillin solution having a concentration of 0.2 to 1 g/mL. Under the condition of the concentration, the vanillin can fully react with ethyl cyanoacetate to generate 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate, the yield of the target product is high, and the byproducts are few. In some embodiments, the concentration of the vanillin solution is preferably 0.4 to 0.5 g/mL.
According to an embodiment of the invention, the molar ratio of vanillin to ethyl cyanoacetate is 1: (1-1.2). The inventor finds that the morpholine is used as a catalyst, the dosage of ethyl cyanoacetate can be reduced, under the condition of the molar ratio, vanillin and ethyl cyanoacetate can be fully reacted to generate the 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate, the yield of a target product is high, and the number of byproducts is small.
According to an embodiment of the invention, the method comprises: (1) adding vanillin into solvent, heating to dissolve completely, and adding cyanoethyl acetate and morpholine into the feed liquid; (2) continuously heating to reflux, and keeping reflux and water diversion; (3) when no more water flows out, the feed liquid is cooled, filtered and crystal is collected so as to obtain the 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate. The vanillin, ethyl cyanoacetate and morpholine are refluxed and water-separated in the solvent to complete the reaction, and the target product with bright yellow color (if the color is dark, other impurities are possibly more) can be obtained by simple filtration. The filtrate after filtration contains morpholine, can be directly used for the next reaction without treatment and waste discharge.
According to the embodiment of the invention, in the step (1), the heating temperature is 50-110 ℃; in the step (2), the reflux temperature is 110-120 ℃. The reaction condition is mild, vanillin and ethyl cyanoacetate can be fully reacted to generate the 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate under the catalysis of morpholine, the reaction speed is high, the yield of the target product is high, the number of byproducts is small, the requirement on equipment is low, and the production cost is reduced. In some embodiments, the heating temperature in step (1) is preferably 50 to 60 ℃.
According to the embodiment of the invention, the temperature reduction is to reduce the temperature of the feed liquid to below 20 ℃. Therefore, the target product can be crystallized and precipitated, and the obtained filtrate contains morpholine and can be directly used for the next reaction without treatment and waste discharge. In some preferred embodiments, the temperature is reduced to 10-20 ℃.
According to an embodiment of the invention, the solvent is selected from aromatic hydrocarbons, preferably benzene, toluene or xylene. Thus, each reaction raw material can be dissolved therein.
Has the advantages that:
the method adopts morpholine as a catalyst, the dosage of the catalyst is less, the residual toxicity of the product is less, and simultaneously, the dosage of ethyl cyanoacetate is greatly reduced, and the waste treatment is reduced. The preparation method has the advantages of simple operation, mild reaction conditions, low equipment requirements, high reaction speed, single raw material conversion, high conversion rate, high yield, few byproducts and bright yellow products. After the target product is collected by filtration, the residual filtrate contains morpholine, can be directly used for the next reaction without treatment, loss and waste discharge.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The scheme of the invention will be explained with reference to the following examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
187.5g of vanillin, 660mL of toluene and 0.019g of morpholine are sequentially added into a 3L three-necked bottle, and the mixture is stirred and heated. When the temperature of the system was 60 ℃, 140.8g of ethyl cyanoacetate was added thereto, and the temperature was gradually increased. When the temperature of the system rises to 114-116 ℃, the water diversion under reflux is started. And stopping the reaction until no water is separated out. Cooling to 20 deg.C, separating out, filtering, and drying. The theoretical yield is 304.8g, the actual yield is 285.56g, and the yield is 93.7%.
Example 2
187.5g of vanillin, 660mL of toluene and 0.56g of morpholine are added into a 3L three-necked bottle in sequence, and the mixture is stirred and heated. When the temperature of the system was 60 ℃, 147.11g of ethyl cyanoacetate was added thereto, and the temperature was gradually increased. When the temperature of the system rises to 114-116 ℃, the water diversion under reflux is started. And stopping the reaction until no water is separated out. Cooling to 10 deg.C, separating out, filtering, and drying. The theoretical yield is 304.8g, the actual yield is 293.2g, and the yield is 95.0%.
Comparative example 1
Adding 780mL of absolute ethyl alcohol into a 3L reaction bottle, and starting stirring; 187.5g of vanillin, 161.26g of ethyl cyanoacetate and 33.6g of potassium fluoride are added in sequence; the containers were rinsed with the remaining 60mL of ethanol and poured into the kettle. Slowly raising the temperature after the addition is finished, keeping the temperature for reaction for 2 hours after the internal temperature reaches 60 +/-1 ℃; stopping heating, adding 420mL of deionized water, stirring and cooling to 20 ℃, and standing overnight; filtering with a centrifuge the next day, spin-drying, and leaching with 50% ethanol for 4 times to obtain yellow granule crystal; the filtrate was held using a dedicated barrel. Drying at 50 deg.C or below. Theoretical yield: 304.8g, actual yield: 259.1g, yield 85%.
It can be seen that the yield of the target product obtained by reacting vanillin and ethyl cyanoacetate in anhydrous ethanol using potassium fluoride as a catalyst is lower, the directional conversion is low, and the product color is reddish (evidence of a large number of impurities) compared to examples 1 and 2. The reaction time is long, a large amount of water is needed to separate out the product, the product needs to be leached for many times by ethanol after being filtered, the filtrate cannot be reused, and more waste is generated.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (8)
1. A method for preparing 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-acrylic acid ethyl ester, comprising:
reacting vanillin with ethyl cyanoacetate under the catalysis of morpholine to obtain 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate.
2. The method according to claim 1, wherein the morpholine is present in an amount of 0.01 to 0.3 mass% based on the mass of vanillin.
3. The method according to claim 1, wherein said vanillin is provided in the form of a vanillin solution having a concentration of 0.2 to 1 g/mL.
4. The method according to claim 1, wherein the molar ratio of vanillin to ethyl cyanoacetate is 1: (1-1.2).
5. The method of claim 1, comprising:
(1) adding vanillin into solvent, heating to dissolve completely, and adding cyanoethyl acetate and morpholine into the feed liquid;
(2) continuously heating to reflux, and keeping reflux and water diversion;
(3) when no more water flows out, the feed liquid is cooled, filtered and crystal is collected so as to obtain the 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate.
6. The method according to claim 5, wherein in the step (1), the heating temperature is 50-110 ℃; in the step (2), the reflux temperature is 110-120 ℃.
7. The method of claim 5, wherein the reducing the temperature is reducing the temperature of the feed liquid to below 20 ℃.
8. The process according to claim 5, characterized in that the solvent is selected from aromatic hydrocarbons, preferably benzene, toluene or xylene.
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|---|---|---|---|
| CN202011356353.7A CN114539095A (en) | 2020-11-26 | 2020-11-26 | Preparation method of 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate |
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| CN202011356353.7A CN114539095A (en) | 2020-11-26 | 2020-11-26 | Preparation method of 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate |
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