CN115353462A - Preparation method of cyanoalkenoic acid ester - Google Patents
Preparation method of cyanoalkenoic acid ester Download PDFInfo
- Publication number
- CN115353462A CN115353462A CN202211014728.0A CN202211014728A CN115353462A CN 115353462 A CN115353462 A CN 115353462A CN 202211014728 A CN202211014728 A CN 202211014728A CN 115353462 A CN115353462 A CN 115353462A
- Authority
- CN
- China
- Prior art keywords
- reaction
- water
- acid
- catalyst
- cyanoalkenoic
- 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.)
- Pending
Links
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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of cyanoalkenoic acid ester. The preparation method comprises the following steps: (1) Reacting raw material mixed liquor of cyanoacetate, carbonyl compound, catalyst and organic solvent at the temperature of 80-140 ℃ to obtain a reaction mixture after reaction; wherein the catalyst comprises a nitrogen-containing basic catalyst and a weak acid, and the weak acid is selected from weak acids with carbon atoms of C3-C8; the organic solvent is selected from water-carrying solvent which can be separated from water; (2) And (3) layering the reaction mixture to obtain an upper layer and a lower layer, and collecting the cyano olefine acid ester from the lower layer. The preparation method provided by the invention realizes the beneficial effects of less by-products, high purity and high product yield through the matching of the raw material system, the specific catalyst, the organic solvent and the process, and has the advantages of simple process, low cost and good actual production economic benefit.
Description
Technical Field
The invention relates to a preparation method of cyanoalkenoic acid ester.
Background
2-cyanoacrylates, especially 2-cyano-3, 3-diarylacrylates, are used as highly effective UV absorbers, mainly in plastics, inks, paints and cosmetics. The main representative industrial products are: octocrylene, 2-cyano-3, 3-diphenylacrylic acid-2-ethylhexyl ester (e.g., bab PARSOL 340 and BASF UV 3039); etorilin, ethyl 2-cyano-3, 3-diphenylacrylate (e.g. BASF UV 3035).
In the prior art, 2-cyanoacrylic esters can be obtained by azeotropic dehydration of cyanoacetic esters with suitable carbonyl compounds in solvents under weakly basic catalysis with knoevenagel condensation (see patent applications US3215724, EP1430023 and DE 14314035). The reaction needs to be carried out at a temperature of 80-140 c, but the reaction rate is slow, so the reaction needs a suitable catalyst, and the catalyst must be removed from the reaction product after the reaction is completed. In addition, when cyanoacetate reacts with carbonyl compounds at 80 to 140 ℃, side reactions occur to form the corresponding amide-based substances, which are difficult to separate from the product, in which case a complicated purification step under a high vacuum degree is required, and the purification process is more complicated particularly when the product is applied to cosmetics.
Patent US5451694 discloses that propionic acid is a water-carrying agent and a catalyst under the conditions of ammonium ion, no organic solvent and a certain vacuum, the reaction time of cyanoacetate and carbonyl compound is shortened to 5 hours, and simultaneously a better yield is achieved, but the process distills out a large amount of propionic acid and water, and the subsequent treatment cost in industrial production is higher.
Patent US5047571 discloses a process for the preparation of 2-cyanoacrylic esters by transesterification of ethyl 2-cyano-3, 3-diphenylacrylate (etoricine) with isooctanol under alkaline conditions. The refining treatment of the octocrilene obtained by the method is simpler, but the old cost of the process is higher due to the small market capacity of the etocrilene, and the route for producing the octocrilene by adopting the method is longer and needs more equipment.
Patent CN1071312C discloses a process for continuously removing the released ammonia gas from the reactor with benzophenone imine and isooctyl cyanoacetate at 20-60 ℃ and 900-100mbar and treating the reaction mixture by falling film evaporator to increase the conversion and remove residual starting materials and other volatiles. The method has the advantages of large equipment investment, no industrial product of required raw materials, easy generation of byproducts and large production control difficulty.
In patent CN110256289A, benzophenone and methyl cyanoacetate are used as raw materials, toluene is used as a water-carrying solvent, ammonium acetate is used as a catalyst, and a cyanoacrylate product is synthesized under the condition that a water separator is adopted to continuously separate water. The method uses low-alcohol, irritant and volatile toluene solvent, and has serious harm to environment, pollution to air, water environment and water source, and chronic poisoning after long-term contact.
Patent CN1046707C discloses a method for obtaining 2-cyanoacrylate by reacting cyanoacetate with benzophenone in polar organic solvent, using ammonium acetate, piperidine and beta-aminopropionic acid and acetate thereof as catalyst under normal pressure and 40-150 deg.C, and optionally adding AlCl 3 、ZrCl 4 Or ZnCl 2 And Lewis acid is used for shortening the reaction time, the treatment process of the process after reaction is complex, and the yield is lower.
Patent CN110981752A discloses that an acidic ionic liquid catalyst grafted by activated carbon is used as a catalyst instead of acetic acid, and cyanoacetate, a carbonyl compound and a solvent are reacted under a refluxing weak alkaline condition to obtain a cyanoacrylate ultraviolet absorbent. The ionic liquid catalyst is easy to recycle, and has the advantages of high product yield, less three wastes and convenient post-treatment. However, the preparation method of the ionic liquid catalyst uses reagents with high toxicity and low flash point, such as tetrahydrofuran, dichloroethane, acetone, acetonitrile and the like, and is difficult to carry out industrial production.
In patent CN101492394A, an anhydride dehydrating agent is added during the reaction of benzophenone, isooctyl cyanoacetate, catalyst and solvent, and it is expected to improve the conversion rate of isooctyl cyanoacetate, so that the reaction becomes irreversible, but in actual conditions, the reaction speed is fast in the initial stage, and the addition of dehydrating agent cannot significantly change the reaction speed, but greatly increases the production cost, and meanwhile, a large amount of low-concentration acid-containing wastewater is generated in the product operation after the washing reaction in industrial production.
Patent CN101589020A discloses a method of reflux reaction of propionic acid and ammonium acetate as catalyst with cyanoacetic ester, carbonyl compound and solvent under vacuum, wherein the content of by-product amide substance in the reaction product is less than 0.5wt%; in the method, the molar ratio of the ammonium catalyst to the carbonyl compound is in the range of 0.6-1.5, and because more ammonium catalysts are used, the ammonium catalysts are heated for a long time in a reactor and decomposed with water to form ammonia gas and acetic acid, or are dehydrated and inactivated to form amide, and a large amount of catalysts are added to bring great trouble to the refining treatment of subsequent products, and simultaneously, the separation of distilled propionic acid, water and acetic acid is difficult to treat industrially, so that the process has low economic benefit.
Therefore, it is highly desirable to provide a method for preparing 2-cyanoacrylate, which has simple process, high product purity, high product yield and good economic benefits.
Disclosure of Invention
The invention aims to overcome the defects that the preparation of 2-cyanoacrylate in the prior art is difficult to realize simultaneously and has simple process, high product purity and high yield, and provides a preparation method of cyanoalkenoic acid ester. The preparation method of the cyanoalkenoic acid ester has the advantages of simple process, high product purity, high product yield and good economic benefit.
The invention solves the technical problems through the following technical scheme:
a method of preparing a cyanoalkenoic acid ester comprising the steps of:
(1) Reacting raw material mixed liquor of cyanoacetate, carbonyl compound, catalyst and organic solvent at the temperature of 80-140 ℃, and obtaining a reaction mixture after reaction;
the reaction is knoevenagel condensation reaction, and the reaction formula is as follows:
CNCH 2 COO-R 1 +R 2 -CO-R 3 →R 2 C(R 3 )＝C(CN)COOR 1
wherein R1, R2, R3 are each independently selected from hydrocarbyl;
wherein the catalyst comprises a basic catalyst containing nitrogen and a weak acid, and the weak acid is selected from weak acids with carbon atoms of C3-C8; the organic solvent is selected from water-carrying solvent which can be separated from water;
(2) And (3) layering the reaction mixture to obtain an upper layer and a lower layer, and collecting the cyano olefine acid ester from the lower layer.
In the present invention, the R1 may be selected from an alkyl group.
In the present invention, R2 and R3 may be independently selected from aromatic hydrocarbon groups, for example, R2 and R3 may be both phenyl groups.
In the present invention, the cyanoalkenoic acid ester may be a cyanoalkenoic acid ester compound conventional in the art, such as a 2-cyanoacrylate compound, such as 2-cyano-3, 3-diaryl acrylate or 2-cyano-3, 3-diphenyl-2-propenoic acid-2-ethylhexyl ester.
In the present invention, the cyanoacetate may be selected from ethyl cyanoacetate or 2-ethylhexyl cyanoacetate.
In the present invention, preferably, the carbonyl compound is benzophenone.
In the present invention, it is preferable that the molar ratio of the cyanoacetate ester to the carbonyl compound is (0.5-2): 1, e.g. (1-1.5): 1.
In the present invention, preferably, the nitrogen-containing basic catalyst is selected from piperidine and/or acetamide.
In the present invention, the weak acid generally refers to an acid that is not completely ionized in a solution. Preferably, the weak acid is selected from propionic acid or caprylic acid.
In the present invention, the molar ratio of the nitrogen-containing basic catalyst to the weak acid is preferably (0.2-0.63) 1, for example 0.2.
In the present invention, the organic solvent is selected from water-carrying solvents, which are organic solvents that can be azeotroped with water and separated from water.
In the present invention, preferably, the organic solvent is selected from heptane or butyl acetate.
In the present invention, preferably, the mass ratio of the catalyst to the total charge amount is (0.02-0.07): 1, e.g. 0.03.
In the present invention, the mass ratio of the organic solvent to the total charge is (0.1-0.5) 1, for example 0.35.
In the present invention, in the step (1), preferably, the reaction is carried out at a temperature of 98 to 140 ℃, for example, 110 ℃ or 126 ℃.
In the present invention, in the step (1), the catalyst may be continuously supplemented during the reaction as is conventional in the art.
In the present invention, in the step (1), it is preferable that water generated by the reaction is removed by dividing water during the reaction. For example by a water trap.
In the present invention, in the step (1), preferably, the reaction is performed under the process of azeotropic reflux water separation.
Wherein, the process of azeotropic reflux water diversion can be conventional in the field, and generally refers to azeotropic reflux and water diversion.
Wherein the reaction can be carried out in a device conventionally used in the art for azeotropic reflux water diversion, such as an azeotropic reflux water diversion reaction kettle, or in a device comprising a flask, a water segregator and a condenser.
Preferably, the azeotropic reflux water diversion process includes the following steps: in the reaction process, an azeotrope condensate is obtained by condensation and is layered into an upper layer solvent and a lower layer aqueous solution, the lower layer aqueous solution is removed, and the upper layer returns to participate in the azeotropic reflux reaction.
The lower aqueous solution is generally an acid-containing aqueous solution, for example, a solution containing a part of the low boiling point catalyst and water produced by the reaction.
Wherein the azeotrope condensate may be collected by a condenser as is conventional in the art.
In the present invention, in the step (1), preferably, the reaction is stopped when the cyanoacetate ester content in the reaction mixture is less than 2 to 10% by weight,% means the mass of the cyanoacetate ester as a percentage of the total mass of the reaction mixture. More preferably, the reaction is stopped when the cyanoacetate content is less than 2 to 3 wt%.
In the present invention, in the step (2), the upper solvent and the lower aqueous solution of the reaction mixture may be obtained by allowing the reaction mixture to separate by standing as is conventional in the art. The upper solvent layer can be recycled according to the routine in the field.
In the present invention, in the step (2), the collection means may employ means conventionally used in the art for collecting products, such as distillation under reduced pressure.
Wherein, the vacuum distillation operation can be the conventional vacuum distillation operation in the field, and the proper temperature and pressure are selected according to the collected products to collect the fractions.
Wherein, preferably, the collecting comprises the following steps: and carrying out reduced pressure distillation on the lower layer of the reaction mixture, and collecting fractions under the conditions of 100-190 ℃ and 0.5-10mmHg to obtain the cyanoalkenoic acid ester.
More preferably, the fraction is collected at a temperature of 120-187 ℃, for example 125 or 130 ℃.
More preferably, a fraction at a pressure of 0.7 to 8mmHg, for example 1 or 4mmHg, is collected.
For example: the fractions were collected under the conditions of "120 ℃ temperature and 4mmHg pressure", "187 ℃ temperature and 0.7mmHg", "125 ℃ temperature and 8mmHg pressure" or "130 ℃ temperature and 1mmHg pressure".
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) The preparation method of the cyanoalkenoic acid ester realizes the beneficial effects of less by-products, high purity and high product yield by matching the raw material system with the specific catalyst, the organic solvent and the process, and has the advantages of simple process, low cost and good actual production economic benefit.
(2) According to the invention, by selecting a specific catalyst and an organic solvent to be matched, the mixed solution after reaction can be simply treated (such as reduced pressure distillation) to obtain a product, and the method is simple to operate and low in cost. The required raw materials are highly safe (e.g., propionic acid is less acidic and less corrosive than acetic acid).
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto.
Example 1
In a four-necked flask with a stirrer and a thermometer, 16.98g (0.15 mol) of ethyl cyanoacetate, 18.82g (0.1 mol) of benzophenone, 1.78g of a catalyst (0.66 g of piperidine and 1.12g of propionic acid) and 20g of heptane were charged, and the reaction temperature was gradually raised to 98 ℃ and refluxed while a lower aqueous solution of the condensate was separated, and the heptane was refluxed into the four-necked flask. Sampling and detecting that the content of ethyl cyanoacetate is less than 3wt%, and terminating the reaction. The reaction mixture in the four-neck flask is kept still for layering, and the upper solution is distilled and recycled (namely, the solvent is recycled). The lower layer is distilled under reduced pressure, the front fraction (raw material) is collected and recycled, the fraction of 120 ℃ and 4mmHg is collected and cooled to obtain 24.9g of white or light yellow powder (the product is 2-cyano-3, 3-diphenyl ethyl acrylate through gas chromatography and standard substance identification), the yield is 89.9 percent, and the purity is 99.5 percent (determined by gas chromatography).
Chromatographic conditions for gas chromatography: chromatographic column DB-5 (30 m × 0.25mm × 0.25 μm), carrier gas He, column flow rate of 1.0mL/min, split flow ratio of 100: 1, column temperature of 40 deg.C for 3min, heating rate of 15 deg.C/min, and column temperature of 280 deg.C for 5min.
Example 2
In a four-necked flask with a stirrer and a thermometer, 39.6g (0.2 mol) of 2-ethylhexyl cyanoacetate, 36.45g (0.2 mol) of benzophenone, 5.10g of a catalyst (1.70 g of acetamide and 3.40g of propionic acid) and 20g of butyl acetate were placed, and a water separator and a condenser were placed to gradually raise the reaction temperature to 110 ℃ for reflux, during which time the lower aqueous solution in the water separator of the condensate was separated and the butyl acetate was returned to the four-necked flask. Sampling to detect that the content of the cyanoacetic acid-2-ethylhexyl ester is less than 2 percent, and terminating the reaction. And (3) standing and layering the reaction mixture in the four-neck flask, and distilling and recycling the upper solution. The lower layer was distilled under reduced pressure, and the front fraction was collected and recycled, and the fraction at 187 ℃ under 0.7mmHg was collected to give 65.7g of a transparent pale yellow viscous oily liquid (identified by gas chromatography and standard substance, 2-cyano-3, 3-diphenyl-2-ethylhexyl acrylate), yield 91.0%, and purity 99.6% (determined by gas chromatography, the determination method was the same as in example 1).
Example 3
In a four-necked flask with a stirrer and a thermometer, 16.98g (0.15 mol) of ethyl cyanoacetate, 28.23g (0.3 mol) of benzophenone, 3.61g of a catalyst (1.37 g of piperidine and 2.24g of propionic acid) and 20g of butyl acetate were placed, a water separator and a condenser were placed, the reaction temperature was gradually raised to 126 ℃ and refluxed, during which time the lower aqueous solution in the condensate water separator was separated and the butyl acetate was returned to the four-necked flask. Sampling and detecting that the content of ethyl cyanoacetate is less than 3wt%, and terminating the reaction. And standing the reaction mixture in the four-neck flask for layering, and distilling and recycling the upper solution. The lower layer is distilled under reduced pressure, the front fraction is collected and recycled, 25.3g of white or light yellow powder (the product is 2-cyano-3, 3-diphenyl ethyl acrylate through gas chromatography and standard identification) is obtained after cooling, the yield is 91.3%, and the purity is 99.4% (gas chromatography determination, the determination method is the same as that in example 1).
Example 4
In a four-necked flask with a stirrer and a thermometer, 39.6g (0.2 mol) of 2-ethylhexyl cyanoacetate, 72.92g (0.4 mol) of benzophenone, 4.08g of a catalyst (1.36 g of acetamide and 2.72g of propionic acid) and 20g of butyl acetate were placed, a water separator and a condenser were placed, the reaction temperature was gradually raised to 126 ℃ and refluxed, during which time the lower aqueous solution in the condensate water separator was separated and butyl acetate was returned to the four-necked flask. Sampling to detect that the content of the cyanoacetic acid-2-ethylhexyl ester is less than 2 percent, and terminating the reaction. And (3) standing and layering the reaction mixture in the four-neck flask, and distilling and recycling the upper solution. The lower layer was distilled under reduced pressure, and the front fraction was collected and recycled, and the fraction at 130 ℃ under 1mmHg was collected to obtain 66.7g of a transparent pale yellow viscous oily liquid (identified by gas chromatography and standard substance, 2-ethylhexyl-2-cyano-3, 3-diphenyl-2-acrylate), yield 92.3%, purity 99.4% (determined by gas chromatography, the determination method was the same as in example 1).
Comparative example 1
In a four-necked flask with a stirrer and a thermometer, 16.98g (0.15 mol) of ethyl cyanoacetate, 18.82g (0.1 mol) of benzophenone, 5.36g of a catalyst (2.68 g of acetic acid, 1.28 g of ammonium acetate, 1.4 g of sodium hydrogencarbonate) and 20g of heptane were charged, a water separator and a condenser were placed, the reaction temperature was gradually raised to 98 ℃ and refluxed, and the lower aqueous solution of the condensate was separated out and the heptane was refluxed into the four-necked flask. Sampling and detecting that the content of ethyl cyanoacetate is less than 3wt%, and terminating the reaction. And standing the reaction mixture in the four-neck flask for layering, and distilling and recycling the upper solution. The lower layer is distilled under reduced pressure, the front fraction is collected and recycled, 23.4g of white or light yellow powder (identified by gas chromatography and standard substance, the product is 2-cyano-3, 3-diphenyl ethyl acrylate) is obtained after cooling, the yield is 84.5%, and the purity is 99.1% (determined by gas chromatography, the determination method is the same as that of example 1).
Comparative example 2
In a four-necked flask equipped with a stirrer and a thermometer, 16.98g (0.15 mol) of ethyl cyanoacetate, 18.82g (0.2 mol) of benzophenone, 1.78g of a catalyst (0.66 g of piperidine and 1.12g of propionic acid) and 20g of toluene were charged, and the mixture was placed in a water separator and a condenser, and the reaction temperature was gradually raised to 110 ℃ and refluxed, and at the same time, the lower aqueous solution of the condensate was separated out, and the toluene was refluxed into the four-necked flask. Sampling and detecting that the content of ethyl cyanoacetate is less than 3wt%, and terminating the reaction. Standing for layering, and distilling and recycling the upper solution. The lower layer is distilled under reduced pressure, the front fraction is collected and recycled, 33.7g of white or light yellow powder (the product is 2-cyano-3, 3-diphenyl ethyl acrylate through the identification of gas chromatography and a standard substance) is obtained after cooling, the yield is 81.3 percent, and the purity is 98.7 percent (the determination method is the same as the determination method of the example 1 through the gas chromatography).
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (10)
1. A preparation method of cyanoalkenoic acid ester is characterized by comprising the following steps:
(1) Reacting raw material mixed liquor of cyanoacetate, carbonyl compound, catalyst and organic solvent at the temperature of 80-140 ℃ to obtain a reaction mixture after reaction;
the reaction is knoevenagel condensation reaction, and the reaction formula is as follows:
CNCH 2 COO-R 1 +R 2 -CO-R 3 →R 2 C(R 3 )＝C(CN)COOR 1
wherein R1, R2, R3 are each independently selected from hydrocarbyl groups;
wherein the catalyst comprises a basic catalyst containing nitrogen and a weak acid, and the weak acid is selected from weak acids with carbon atoms of C3-C8; the organic solvent is selected from water-carrying solvent which can be separated from water;
(2) And (3) layering the reaction mixture to obtain an upper layer and a lower layer, and collecting the cyano olefine acid ester from the lower layer.
2. The method of making a cyanoalkenoic acid ester according to claim 1 wherein said R1 is selected from the group consisting of an alkyl group;
and/or, said R2, R3 are each independently selected from aromatic hydrocarbon groups, such as phenyl;
and/or the cyanoacrylate is 2-cyanoacrylate compound, preferably the 2-cyanoacrylate compound is 2-cyano-3, 3-diaryl acrylate or 2-cyano-3, 3-diphenyl-2-acrylic acid-2-ethylhexyl ester.
3. A process for the preparation of cyanoalkenoic acid esters according to claim 1,
the cyanoacetate is selected from ethyl cyanoacetate or 2-ethylhexyl cyanoacetate;
and/or, the carbonyl compound is benzophenone;
and/or the molar ratio of the cyanoacetate ester to the carbonyl compound is (0.5-2): 1, e.g. (1-1.5): 1.
4. The method of claim 1, wherein the nitrogen-containing basic catalyst is selected from piperidine and/or acetamide.
5. A process for the preparation of a cyanoalkenoic acid ester according to claim 1 wherein said weak acid is selected from propionic acid or octanoic acid.
6. A process for the preparation of cyanoalkenoic acid ester according to claim 1 wherein the molar ratio of said nitrogen-containing basic catalyst to said weak acid is (0.2-0.63) 1, such as 0.2.
7. The method of claim 1, wherein the organic solvent is selected from the group consisting of water-carrying solvents, which are water-azeotropically and water-demixing organic solvents;
preferably, the organic solvent is selected from heptane or butyl acetate.
8. The process for the preparation of a cyanoalkenoic acid ester according to claim 1 wherein the mass ratio of said catalyst to the total charge is (0.02-0.07): 1, e.g. 0.03;
and/or the mass ratio of the organic solvent to the total charge is (0.1-0.5) 1, such as 0.35.
9. A process for the preparation of cyanoalkenoic acid esters according to claim 1,
the reaction in step (1) is carried out at a temperature of 98-140 ℃, for example 110 ℃ or 126 ℃;
and/or, in the step (1), continuously replenishing the catalyst during the reaction;
and/or, in step (1), during the reaction, removing water produced by the reaction by means of water diversion, for example by means of a water separator;
and/or, in the step (1), the reaction is carried out under the process of azeotropic reflux water separation;
wherein, in the step (1), the azeotropic reflux water separation process refers to azeotropic reflux and water separation;
wherein the reaction can be carried out in an azeotropic reflux water diversion reaction kettle or a device comprising a flask, a water knockout drum and a condenser;
preferably, the azeotropic reflux water diversion process includes the following steps: in the process of azeotropic reflux water diversion, azeotrope condensate is obtained through condensation, the azeotrope condensate is layered into an upper layer solvent and a lower layer aqueous solution, the lower layer aqueous solution is removed, and the upper layer returns to participate in the reaction;
wherein the lower layer aqueous solution is generally an acid-containing aqueous solution, for example, a solution containing part of low boiling point catalyst and water generated by the reaction;
wherein the azeotrope condensate may be collected by a condenser conventional in the art;
and/or, in step (1), stopping the reaction when the cyanoacetate ester content in the reaction mixture is less than 2-10wt% means the mass of cyanoacetate ester as a percentage of the total mass of the reaction mixture; more preferably, the reaction is stopped when the cyanoacetate content is less than 2 to 3 wt%.
10. The method for producing a cyanoalkenoic acid ester according to claim 1, wherein in the step (2), the upper solvent and the lower aqueous solution of the reaction mixture are obtained by allowing to stand and separating;
and/or, in the step (2), the collection mode adopts reduced pressure distillation;
wherein, preferably, the collecting comprises the following steps: carrying out reduced pressure distillation on the lower layer of the reaction mixture, and collecting fractions under the conditions of 100-190 ℃ and 0.5-10mmHg to obtain the cyanoalkenoic acid ester;
more preferably, fractions at a temperature of 120-187 ℃, e.g. 125 or 130 ℃;
more preferably, a fraction at a pressure of 0.7 to 8mmHg, for example 1 or 4mmHg is collected;
for example: the fractions were collected under the conditions of "120 ℃ temperature and 4mmHg pressure", "187 ℃ temperature and 0.7mmHg", "125 ℃ temperature and 8mmHg pressure" or "130 ℃ temperature and 1mmHg pressure".
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211014728.0A CN115353462A (en) | 2022-08-23 | 2022-08-23 | Preparation method of cyanoalkenoic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211014728.0A CN115353462A (en) | 2022-08-23 | 2022-08-23 | Preparation method of cyanoalkenoic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115353462A true CN115353462A (en) | 2022-11-18 |
Family
ID=84002908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211014728.0A Pending CN115353462A (en) | 2022-08-23 | 2022-08-23 | Preparation method of cyanoalkenoic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115353462A (en) |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5451694A (en) * | 1993-04-29 | 1995-09-19 | Haarmann & Reimer Gmbh | Process for preparing substituted 2-cyanocinnamic esters |
| US5821380A (en) * | 1994-11-10 | 1998-10-13 | Basf Aktiengesellschaft | 2-cyanoacrylic esters |
| CN101239931A (en) * | 2007-02-08 | 2008-08-13 | 帝斯曼知识产权资产管理有限公司 | Method for producing 2-cyanocinnamate with substituent group |
| CN101492394A (en) * | 2009-02-26 | 2009-07-29 | 南京工业大学 | Method of preparing Octocrilene |
| CN101589020A (en) * | 2007-01-26 | 2009-11-25 | 帝斯曼知识产权资产管理有限公司 | Process for the manufacture of substituted 2-cyano cinnamic esters |
| US20100048937A1 (en) * | 2007-01-26 | 2010-02-25 | Jing Huang | Process for the manufacture of substituted 2-cyano cinnamic esters |
| CN102584625A (en) * | 2011-12-30 | 2012-07-18 | 潍坊滨海石油化工有限公司 | Method for producing 2-cyanoacrylate |
| CN103242197A (en) * | 2013-05-24 | 2013-08-14 | 安徽圣诺贝化学科技有限公司 | Preparation method of ultraviolet absorbent intermediate etocrilene (ETO) |
| CN104672107A (en) * | 2013-11-26 | 2015-06-03 | 杨海中 | A preparing method of ethyl 2-cyano-3,3-diphenylacrylate |
| CN109970603A (en) * | 2018-06-19 | 2019-07-05 | 湖北师范大学 | The microchannel successive reaction synthetic method of ultraviolet light absorber octocrilene |
| CN110256289A (en) * | 2019-07-17 | 2019-09-20 | 威海金威化学工业有限责任公司 | A kind of preparation method of ultraviolet absorbing agent UV-3030 |
| CN110437107A (en) * | 2018-05-03 | 2019-11-12 | 优缔新材料科技(苏州)有限公司 | A kind of propylene ketooxime ester compounds, preparation method and composition |
| CN110981752A (en) * | 2019-12-18 | 2020-04-10 | 利安隆科润(浙江)新材料有限公司 | Preparation method of cyanoacrylate ultraviolet absorbent |
| CN112142757A (en) * | 2020-09-29 | 2020-12-29 | 广东东阳光药业有限公司 | Five-membered nitrogen-containing heteroaryl substituted pyrimidinedione compound and application thereof |
| CN113444017A (en) * | 2020-03-26 | 2021-09-28 | 优禘股份有限公司 | Diphenyl sulfide ether ketone oxime ester compound, preparation method, composition and application |
| CN113754679A (en) * | 2020-09-09 | 2021-12-07 | 广东东阳光药业有限公司 | Substituted pyrimidinediones and their use |
| CN115260059A (en) * | 2022-07-26 | 2022-11-01 | 万华化学集团股份有限公司 | Method for preparing 2-cyano-3,3-ethyl diphenylacrylate |
-
2022
- 2022-08-23 CN CN202211014728.0A patent/CN115353462A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5451694A (en) * | 1993-04-29 | 1995-09-19 | Haarmann & Reimer Gmbh | Process for preparing substituted 2-cyanocinnamic esters |
| US5821380A (en) * | 1994-11-10 | 1998-10-13 | Basf Aktiengesellschaft | 2-cyanoacrylic esters |
| CN101589020A (en) * | 2007-01-26 | 2009-11-25 | 帝斯曼知识产权资产管理有限公司 | Process for the manufacture of substituted 2-cyano cinnamic esters |
| US20100048937A1 (en) * | 2007-01-26 | 2010-02-25 | Jing Huang | Process for the manufacture of substituted 2-cyano cinnamic esters |
| CN101239931A (en) * | 2007-02-08 | 2008-08-13 | 帝斯曼知识产权资产管理有限公司 | Method for producing 2-cyanocinnamate with substituent group |
| CN101492394A (en) * | 2009-02-26 | 2009-07-29 | 南京工业大学 | Method of preparing Octocrilene |
| CN102584625A (en) * | 2011-12-30 | 2012-07-18 | 潍坊滨海石油化工有限公司 | Method for producing 2-cyanoacrylate |
| CN103242197A (en) * | 2013-05-24 | 2013-08-14 | 安徽圣诺贝化学科技有限公司 | Preparation method of ultraviolet absorbent intermediate etocrilene (ETO) |
| CN104672107A (en) * | 2013-11-26 | 2015-06-03 | 杨海中 | A preparing method of ethyl 2-cyano-3,3-diphenylacrylate |
| CN110437107A (en) * | 2018-05-03 | 2019-11-12 | 优缔新材料科技(苏州)有限公司 | A kind of propylene ketooxime ester compounds, preparation method and composition |
| CN109970603A (en) * | 2018-06-19 | 2019-07-05 | 湖北师范大学 | The microchannel successive reaction synthetic method of ultraviolet light absorber octocrilene |
| CN110256289A (en) * | 2019-07-17 | 2019-09-20 | 威海金威化学工业有限责任公司 | A kind of preparation method of ultraviolet absorbing agent UV-3030 |
| CN110981752A (en) * | 2019-12-18 | 2020-04-10 | 利安隆科润(浙江)新材料有限公司 | Preparation method of cyanoacrylate ultraviolet absorbent |
| CN113444017A (en) * | 2020-03-26 | 2021-09-28 | 优禘股份有限公司 | Diphenyl sulfide ether ketone oxime ester compound, preparation method, composition and application |
| CN113754679A (en) * | 2020-09-09 | 2021-12-07 | 广东东阳光药业有限公司 | Substituted pyrimidinediones and their use |
| CN112142757A (en) * | 2020-09-29 | 2020-12-29 | 广东东阳光药业有限公司 | Five-membered nitrogen-containing heteroaryl substituted pyrimidinedione compound and application thereof |
| CN115260059A (en) * | 2022-07-26 | 2022-11-01 | 万华化学集团股份有限公司 | Method for preparing 2-cyano-3,3-ethyl diphenylacrylate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103502198A (en) | Synthesis of methylene malonates using rapid recovery in the presence of a heat transfer agent | |
| CN110981752B (en) | Preparation method of cyanoacrylate ultraviolet light absorber | |
| JP2006315960A (en) | Tricyclodecanediol di(meth)acrylate and method for producing the same | |
| JP3830595B2 (en) | Esterification of (meth) acrylic acid | |
| CN102584625B (en) | Method for producing 2-cyanoacrylate | |
| EP0884300A1 (en) | Process for preparing free alpha-hydroxy acids from ammonium salts thereof | |
| TWI427075B (en) | Process for preparing tetramethylglycolide | |
| CN115353462A (en) | Preparation method of cyanoalkenoic acid ester | |
| JPH06219991A (en) | Production of polyfunctional @(3754/24)meth)acrylate | |
| Garima et al. | Direct sulfonylation of Baylis-Hillman alcohols and diarylmethanols with TosMIC in ionic liquid-[Hmim] HSO4: an unexpected reaction | |
| WO2008103016A1 (en) | Atorvastatin intermediates and method for producing the same | |
| CN101589020A (en) | Process for the manufacture of substituted 2-cyano cinnamic esters | |
| JPH10175919A (en) | Production of tetrahydrobenzyl (meth)acrylate | |
| WO2014178061A2 (en) | A novel process for the preparation of 2-cyano- 3,3- diarylacrylates | |
| JP3051191B2 (en) | Method for producing epoxidized (meth) acrylate compound | |
| JP4831715B2 (en) | Monomer production method | |
| JPH03112949A (en) | Production of dimethylaminoethyl acrylate | |
| JP6003204B2 (en) | Method for producing alkanediol monoglycidyl ether (meth) acrylate | |
| IL199839A (en) | Process for the manufacture of substituted 2-cyano cinnamic esters | |
| JPH0665149A (en) | Production of usable compound from michael reactional adduct of acrylic acid ester | |
| RU2165407C2 (en) | Method of preparing free alpha-hydroxy acids from ammonium slats thereof (variants) | |
| JPH10182580A (en) | Modified production of 2-cyanoacrylate | |
| JPH02193944A (en) | Production of (meth)acrylic acid ester | |
| JPH10175918A (en) | Production of tetrahydrobenzyl (meth)acrylate | |
| JPH02229145A (en) | Production of dimethylaminoethyl acrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |