CN113563166B - Synthesis method of vanillyl alcohol ether - Google Patents
Synthesis method of vanillyl alcohol ether Download PDFInfo
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- CN113563166B CN113563166B CN202110995545.0A CN202110995545A CN113563166B CN 113563166 B CN113563166 B CN 113563166B CN 202110995545 A CN202110995545 A CN 202110995545A CN 113563166 B CN113563166 B CN 113563166B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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Abstract
The embodiment of the invention provides a synthesis method of vanillyl alcohol ether, belonging to the technical field of fine chemical engineering. The synthesis method of the invention comprises the following steps: dissolving vanillin in a solvent, stirring uniformly, adding a metal complex hydride and an alkylating reagent into the solvent, reacting for 3-4 hours at 30-40 ℃ to obtain a vanillyl alcohol ether solution, and separating and purifying the vanillyl alcohol ether solution to obtain the vanillyl alcohol ether. The synthesis method adopts a one-pot method to prepare the vanillyl alcohol ether, has the advantages of simple operation, mild reaction condition, easy control of the reaction process, low production cost and less three wastes, and the vanillyl alcohol ether prepared by the synthesis method has high yield and high purity and is easy to realize industrial production.
Description
The application is a divisional application of China patent application filed in 2019, 4 months and 24 days, with application number of 201910331904.5 and the invention of 'a synthesis method of vanillyl alcohol ether'.
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a synthesis method of vanillyl alcohol ether.
Background
The vanillyl alcohol ether is an oil-soluble thermosensor, can quickly generate mild and durable heat source effect after acting on skin, and can effectively stimulate subcutaneous fat metabolism and promote blood circulation. The vanillyl alcohol ether is similar to most thermal agents in structure, but has low irritation, high thermal degree and long thermal time compared with other thermal agents, can obtain strong thermal sensation at extremely low dosage, is stable and safe in property, has pleasant vanilla taste, can be compounded with most of cosmetic ingredients, and is more and more favored by the cosmetic industry, and particularly, the vanillyl butyl ether is most widely applied in the fields of foods, cosmetics and the like. However, in recent years, there have been few reports on the synthesis of vanillyl butyl ether. The synthesis of vanillyl butyl ether is mainly obtained by dehydration condensation of vanillyl alcohol and n-butanol under an acidic catalyst, but the yield of the method is low mainly due to water generated by the reactionCan inhibit the etherification reaction, and the acid catalyst such as AlCl 3 、FeCl 3 Is easy to hydrolyze in the presence of water and loses catalytic effect. The solid acid catalyst obtained by solidifying some acid catalysts on molecular sieves and other materials is reported to improve the yield of the system, but the catalyst is not easy to obtain, is difficult to prepare and has high cost, is difficult to apply to large-scale production, and takes the vanillyl alcohol as a raw material to cause high cost.
Therefore, it is necessary to develop a synthesis method of vanillyl alcohol ether with simple operation, mild reaction conditions, effectively improved yield and low cost.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a synthesis method of the vanillyl alcohol ether, which adopts a one-pot method to prepare the vanillyl alcohol ether, has the advantages of simple operation, mild reaction condition, easily controlled reaction process, low production cost and less three wastes, and the vanillyl alcohol ether prepared by the synthesis method has high yield and high purity, and is easy to realize industrial production.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for synthesizing vanillyl alcohol ether, the method comprising the steps of: dissolving vanillin in a solvent, stirring uniformly, adding a metal complex hydride and an alkylating reagent into the solvent, and reacting for 3-4 hours at 30-40 ℃ to obtain a vanillin alcohol ether solution.
As a preferred embodiment of the present invention, the molar ratio of vanillin, metal complex hydride, alkylating agent is 1:0.8 to 1.2:1 to 1.5.
As a preferred embodiment of the present invention, the molar ratio of vanillin to solvent is 3 to 6:1.
in a preferred embodiment of the present invention, the solvent is one or a mixture of two or more of methanol, ethanol, propanol, n-butanol, ethyl acetate, and methylene chloride.
In a preferred embodiment of the present invention, the metal complex hydride is one or a mixture of two or more of potassium borohydride, sodium borohydride, lithium aluminum hydride, sodium thioborohydride, and sodium cyanoborohydride.
In a preferred embodiment of the present invention, the alkylating agent is one or a mixture of two or more of ethyl chloride, ethyl bromide, butyl chloride, butyl bromide, chloro-n-hexane, methanol, ethanol, isopropanol and n-butanol.
As a preferred embodiment of the present invention, the vanillin is vanillin or ethyl vanillin.
As a preferred embodiment of the present invention, the solvent is ethyl acetate and the metal complex hydride is potassium borohydride; the molar ratio of vanillin to metal complex hydride to alkylating agent is 1:0.8:1.2.
as a preferred embodiment of the invention, the synthesis method of the invention further comprises the steps of separating and purifying the vanillyl alcohol ether solution, and the synthesis method specifically comprises the following steps: filtering the vanillyl alcohol ether solution, and vacuum rectifying the filtrate to obtain the vanillyl alcohol ether.
As a preferred embodiment of the invention, the temperature of the vacuum rectification is 140-180 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the synthesis method of the invention uses vanillin as a raw material, uses metal complex hydride as a reducing agent and uses halogenated alkane or alcohol as an alkylating agent, and uses an oxidation product of the metal complex hydride as an alkaline catalyst, and adopts a one-pot method to prepare the vanillin ether.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
A method for synthesizing vanillyl alcohol ether, the method comprising the steps of: dissolving vanillin in a solvent, uniformly stirring, adding a metal complex hydride and an alkylating reagent into the solvent, and reacting for 3-4 hours at 30-40 ℃ to obtain a vanillin alcohol ether solution; filtering the vanillyl alcohol ether solution, washing filter residues, mixing the washing solution with the filtrate, and then carrying out vacuum rectification at 140-180 ℃ to obtain the vanillyl alcohol ether.
In the above synthesis method, the molar ratio of vanillin, metal complex hydride and alkylating agent is 1:0.8 to 1.2:1 to 1.5, preferably the molar ratio is vanillin, metal complex hydride, alkylating agent = 1:0.8:1.2. the mol ratio of vanillin to solvent is 3-6: 1. the solvent is one or more of methanol, ethanol, propanol, n-butanol, ethyl acetate and dichloromethane, preferably ethyl acetate. The metal complex hydride is one or more than two of potassium borohydride, sodium borohydride, lithium aluminum hydride, sodium thioborohydride and sodium cyanoborohydride, preferably potassium borohydride. The alkylating reagent is one or the mixture of more than two of chloroethane, bromoethane, chlorobutane, bromobutane, chloro-n-hexane, methanol, ethanol, isopropanol or n-butanol. The vanillin is vanillin or ethyl vanillin.
Example 1: preparation of vanillyl butyl ether
100.00g of vanillin was dissolved in 231.65g of ethyl acetate, stirred and dissolved, 28.36g of potassium borohydride and 90.06g of bromobutane were added, and the mixture was reacted at 30 to 40℃for 4 hours. Cooling to room temperature, filtering to remove solid in the reaction liquid, washing filter residues, taking the washing liquid and the filtrate, and taking the mixed liquid for reduced pressure distillation to obtain a colorless liquid crude product. Vacuum rectifying at 165 deg.c to obtain vanillyl butyl ether 131.57g in the yield of 95.20% and purity over 99%.
Example 2: preparation of vanillyl butyl ether
100.00g of vanillin was dissolved in 231.65g of ethyl acetate, stirred and dissolved, 28.36g of potassium borohydride and 108.07g of bromobutane were added, and the mixture was reacted at 30 to 40℃for 3 hours. Cooling to normal temperature, filtering to remove solid in the reaction liquid, washing filter residues, taking the washing liquid and the filtrate, and taking the mixed liquid for reduced pressure distillation to obtain a colorless liquid crude product. Vacuum rectifying at 165 deg.c to obtain 135.62g of vanillyl butyl ether with yield of 98.13% and purity over 99%.
This embodiment differs from embodiment 1 in that: the reaction time was 3 hours, and the molar ratio of vanillin to bromobutane was 1:1.2, the remainder being the same as in example 1.
Example 3: preparation of vanillyl butyl ether
100.00g of vanillin was dissolved in 231.65g of ethyl acetate, stirred and dissolved, 28.36g of potassium borohydride and 60.85g of chlorobutane were added, and the mixture was reacted at 30 to 40℃for 4 hours. Cooling to normal temperature, filtering to remove solid in the reaction liquid, washing filter residues, taking the washing liquid and the filtrate, and taking the mixed liquid for reduced pressure distillation to obtain a colorless liquid crude product. Vacuum rectifying at 165 deg.c to obtain 125.09g of vanillyl butyl ether with 90.51% yield and purity over 99%.
This embodiment differs from embodiment 1 in that: the alkylating agent was chlorobutane and the remainder was the same as in example 1.
Example 4: preparation of vanillyl diethyl ether
100.00g of vanillin was dissolved in 223.29g of methylene chloride, stirred and dissolved, 28.36g of potassium borohydride and 85.94g of bromoethane were added, and the mixture was reacted at 30 to 40℃for 3 hours. Cooling to normal temperature, filtering to remove solid in the reaction liquid, washing filter residues, taking the washing liquid and the filtrate, and taking the mixed liquid for reduced pressure distillation to obtain a colorless liquid crude product. Vacuum rectifying at 165 deg.c to obtain 115.23g of vanillyl diethyl ether with 96.21% yield and purity over 99%.
This embodiment differs from embodiment 2 in that: the reaction solvent is methylene dichloride, the alkylating reagent is bromoethane, and the material ratio, the reaction temperature, the reaction time and the like of the rest are the same as those of the example 2.
Example 5: preparation of vanillyl diethyl ether
100.00g of vanillin was dissolved in 136.27g of ethanol, and 86.65g of sodium borohydride was added thereto with stirring to react at 30 to 40℃for 4 hours. Cooling to normal temperature, filtering to remove solid in the reaction liquid, washing filter residues, taking the washing liquid and the filtrate, and taking the mixed liquid for reduced pressure distillation to obtain a colorless liquid crude product. Vacuum rectifying at 165 deg.c to obtain 116.02g of vanillyl diethyl ether with yield of 96.87% and purity over 99%.
This embodiment differs from embodiment 4 in that: the reaction solvent is ethanol, and the mol ratio of the solvent is vanillin: ethanol=1:3, the alkylating agent is ethanol, the molar ratio is vanillin: ethanol=1:1.5, the metal complex hydride is sodium thioborohydride, the molar ratio is vanillin: sodium thioborohydride=1:1, the reaction time was 4 hours, and the rest was the same as in example 4.
Example 6: preparation of vanillyl diethyl ether
100.00g of vanillin was dissolved in 90.84g of ethanol, and 86.65g of sodium borohydride was added thereto with stirring, followed by reaction of 63.61g of ethyl chloride at 30 to 40℃for 4 hours. Cooling to room temperature, filtering to remove solid in the reaction liquid, washing filter residues, taking the washing liquid and the filtrate, and taking the mixed liquid for reduced pressure distillation to obtain a colorless liquid crude product. Vacuum rectifying at 165 deg.c to obtain 118.05g of vanillyl diethyl ether with 98.56% yield and purity over 99%.
This embodiment differs from embodiment 5 in that: the alkylating agent was ethyl chloride, the remainder being the same as in example 5.
Example 7: preparation of vanillyl isopropyl ether
100.00g of vanillin was dissolved in 165.80g of isopropanol, and then stirred and dissolved, 29.94g of lithium aluminum hydride was added thereto, followed by reaction at 30 to 40℃for 4 hours. Cooling to room temperature, filtering to remove solid in the reaction liquid, washing filter residues, taking the washing liquid and the filtrate, and taking the mixed liquid for reduced pressure distillation to obtain a colorless liquid crude product. Vacuum rectifying at 165 deg.c to obtain vanillyl isopropyl ether 132.36g in 94.89% yield and purity over 99%.
This embodiment differs from embodiment 5 in that: the reaction solvent is isopropanol, the alkylating agent is isopropanol, and the molar ratio is vanillin: isopropanol=1:1.2, the metal complex hydride is lithium aluminum hydride, the molar ratio is vanillin: lithium aluminum hydride=1:1.2, and the rest is the same as in example 5.
Comparative example 1: preparation of vanillyl diethyl ether
100.00g of vanillyl alcohol is dissolved in 179.29g of ethanol, stirred and dissolved, 12.99g of ferric trichloride hexahydrate is added, and the mixture is reacted for 12 hours at 60-70 ℃. Cooling to room temperature, filtering to remove solid in the reaction liquid, washing filter residues, taking the washing liquid and the filtrate, and taking the mixed liquid for reduced pressure distillation to obtain a yellow liquid crude product. Washing with 100g of water, separating the liquid, taking an organic phase, and rectifying in vacuum at 165 ℃ to obtain 77.07g of vanillyl diethyl ether, wherein the yield is 65.21%, and the purity is more than 98%.
Compared with the preparation method provided by the invention, the preparation method has the advantages of high raw material cost, higher reaction temperature, long reaction time and low yield.
Comparative example 2: preparation of vanillyl butyl ether
100.00g of vanillin is dissolved in 243.59g of n-butanol, stirred and dissolved, 2.97g of metal catalyst Pb-C is added, 1.8MPa of hydrogen is filled, the reaction is carried out for 8 hours at the temperature of 60-70 ℃, the vanillin is detected to be completely reacted, the heating is stopped, the metal catalyst Pb-C is filtered and recovered after the reaction liquid is cooled, the filtrate is added into a reaction tank, 14.87g of aluminum trichloride is added, and the temperature is raised to 60-70 ℃ for reaction for 12 hours. Cooling to room temperature, filtering to remove solid in the reaction liquid, washing filter residues, taking the washing liquid and the filtrate, and taking the mixed liquid for reduced pressure distillation to obtain a colorless liquid crude product. Washing with 100g of water, separating the liquid, and vacuum rectifying the organic phase at 165 ℃ to obtain 94.74g of vanillyl butyl ether, wherein the yield is 68.55%, and the purity is more than 98%.
The comparative example uses vanillin with low price as raw material and AlCl 3 The catalyst is an acidic catalyst, but the vanillyl butyl ether can be synthesized through two steps of reduction and etherification, and the reduction needs pressurized catalytic hydrogenation.
In conclusion, compared with the preparation method in the prior art, the synthesis method provided by the invention has the advantages of simple preparation steps, mild reaction conditions, easily controlled reaction process, low production cost, less three wastes, and the vanillyl alcohol ether prepared by the synthesis method provided by the invention has the advantages of high yield, high purity, easiness in realizing industrial production, higher economic benefit and excellent popularization and application values in the fields of medicines, foods, cosmetics and the like.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (5)
1. A synthesis method of vanillyl alcohol ether is characterized in that: the synthesis method comprises the following steps: dissolving vanillin in a solvent, uniformly stirring, adding a metal complex hydride and an alkylating reagent into the solvent, and reacting for 3-4 hours at the temperature of 30-40 ℃ to obtain a vanillin ether solution, wherein the solvent is one or a mixture of more than two of methanol, ethanol, isopropanol and n-butanol; the metal complex hydride is one or the mixture of more than two of potassium borohydride, sodium borohydride, lithium aluminum hydride, sodium thioborohydride and sodium cyanoborohydride; the alkylating reagent is one or the mixture of more than two of chloroethane, bromoethane, chlorobutane, bromobutane, chloro-n-hexane, methanol, ethanol, isopropanol or n-butanol.
2. The method for synthesizing vanillyl alcohol ether according to claim 1, wherein: the molar ratio of vanillin to metal complex hydride to alkylating agent is 1:0.8 to 1.2:1 to 1.5.
3. The method for synthesizing vanillyl alcohol ether according to claim 1, wherein: the vanillin is vanillin or ethyl vanillin.
4. The method for synthesizing vanillyl alcohol ether according to claim 1, wherein: the method also comprises the steps of separating and purifying the vanillyl alcohol ether solution, and specifically comprises the following steps: filtering the vanillyl alcohol ether solution, and vacuum rectifying the filtrate to obtain the vanillyl alcohol ether.
5. The method for synthesizing vanillyl alcohol ether according to claim 4, wherein: the temperature of the vacuum rectification is 140-180 ℃.
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