CN111675613A - Preparation method of 4-acetoxyl-2-methyl-2-butenal - Google Patents
Preparation method of 4-acetoxyl-2-methyl-2-butenal Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/297—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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Abstract
The invention provides a preparation method of a vitamin A intermediate 4-acetoxyl-2-methyl-2-butenal. The method comprises the following steps: (1) 3-methyl-1, 2-epoxybutane is subjected to ring opening under the action of alkaline acetate to generate 2-hydroxy-3-methyl butyl acetate; (2) dehydrating the 2-hydroxy-3-methyl butyl acetate to obtain 3-methyl-2-butyl acetate; (3) the 3-methyl-2-acetic acid butenyl ester is selectively oxidized by one step to obtain 4-acetoxyl group-2-methyl-2-butenal. The method takes 3-methyl-1, 2-butylene oxide as a starting material, has short reaction synthetic route, high atom economy and simple operation, and is an industrially preferred synthetic route.
Description
Technical Field
The invention belongs to the field of chemical intermediate synthesis, and particularly relates to a preparation method of a vitamin A intermediate 4-acetoxyl-2-methyl-2-butenal.
Background
4-acetoxyl-2-methyl-2-butenal (hereinafter referred to as "five-carbon aldehyde") is an important intermediate for synthesizing vitamin A. Due to the importance of the pentanal in the vitamin A synthesis industry, the synthesis process of the pentanal has been a research hotspot for a long time.
US patent application 5453547 discloses a synthetic route for the preparation of pentanal starting from dimethoxyacetone, the reaction formula is as follows: reacting dimethoxyacetone with acetylene and hydrogen to generate a compound 2, reacting the compound 2 with acetic anhydride to generate a compound 3, isomerizing the compound 3 under the action of a Cu catalyst to obtain a compound 4, and hydrolyzing the compound 4 to finally obtain the pentanal. The disadvantages of the route are that the process route is long, the yield is low, and the total yield of the route is 35-45%.
U.S. patent application No. 5424478 discloses a synthetic route to make a five-carbon aldehyde starting from isoprene. Isoprene and sodium hypochlorite are added to obtain two configurational addition products, the cis-isomer is esterified under the action of acetic anhydride to obtain a compound 8, and then dimethyl sulfoxide (DMSO) is used as an oxidant to prepare the pentanal. The method can generate a large amount of waste water in the production process, and the pollution is serious. The synthetic route is as follows:
U.S. patent application US4873362 describes a process for the preparation of pentanal from ethylene oxide. According to the method, ethylene oxide is used as a raw material, after the ring opening addition of the ethylene oxide and acetic acid, a compound 11 is prepared, the compound 11 is subjected to an oxidation reaction with oxygen under the catalysis of Ag to generate an intermediate 12, and the intermediate 12 is subjected to a condensation reaction with propionaldehyde to obtain the pentanal. The intermediate 12 of this process is extremely unstable and the selectivity of the condensation reaction with propionaldehyde is difficult to control. The process route is shown as the following formula:
chinese patent application CN103467287A discloses a synthetic route for preparing five-carbon aldehyde using ethylene oxide and acrolein as starting materials. According to the method, acrolein and ethylene oxide are used as initial raw materials, and are reacted under the action of an organic phosphine reagent to generate a compound 15, the compound is further acetylated to obtain an intermediate 16, and hydroisomerization is carried out under the action of a Pd catalyst to obtain the pentanal. In the route, a large amount of expensive organic phosphine reagent and palladium metal catalyst are consumed, and the yield of the intermediate 16 for generating the pentanal is low and is only 51%. The synthesis process is as follows:
the above methods have disadvantages and various problems in industrial scale-up, and therefore, it is necessary to develop a novel process for synthesizing 4-acetoxy-2-methyl-2-butenal.
Disclosure of Invention
The invention aims to provide a novel route for synthesizing 4-acetoxyl-2-methyl-2-butenal (pentanal), which has the advantages of short reaction synthetic route, high reaction yield, simple operation, stable and easily separated intermediate and small environmental pollution.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method of preparing 4-acetoxy-2-methyl-2-butenal (pentanal) comprising the steps of:
a preparation method of 4-acetoxyl-2-methyl-2-butenal comprises the following steps:
(1) the 3-methyl-1, 2-epoxybutane is subjected to ring opening under the action of alkaline acetate to generate 2-hydroxy-3-methyl butyl acetate (I), and the structural formula is shown as the formula (I);
(2) dehydrating the 2-hydroxy-3-methyl butyl acetate to obtain 3-methyl-2-acetic acid butenyl ester (II), wherein the structural formula is shown as the formula (II);
(3) the 3-methyl-2-butenoic acid ester uses selenium dioxide loaded by metal modified silica gel as an oxidant, and 4-acetoxyl group-2-methyl-2-butenal (III) is obtained through one-step selective oxidation reaction, and the structure is shown as the formula (III):
the selenium dioxide loaded on the silica gel can effectively improve the oxidation selectivity of allylic methyl, and the silica gel can greatly improve the loading rate of the selenium dioxide through metal modification.
As a preferred embodiment, a method for preparing 4-acetoxy-2-methyl-2-butenal, comprising the steps of:
(1) adding a certain amount of alkaline acetate and 3-methyl-1, 2-epoxybutane into an organic solvent, reacting for a period of time at a certain temperature, and separating to obtain 2-hydroxy-3-methyl butyl acetate;
(2) adding 2-hydroxy-3-methyl butyl acetate into a simple distillation device filled with a certain amount of concentrated sulfuric acid, continuously extracting 3-methyl-2-butyl acetate generated in the reaction process under the heating condition, and reacting until no product is extracted;
(3) adding a certain amount of 3-methyl-2-butenolide acetate and selenium dioxide loaded on metal modified silica gel as an oxidant into an organic solvent, reacting for a period of time at a certain temperature, and separating to obtain 4-acetoxyl-2-methyl-2-butenal.
The synthetic route is shown as the following formula:
in the invention, the alkaline acetate in the step (1) is selected from one of sodium acetate and potassium acetate, preferably sodium acetate; the molar ratio of acetate to 3-methyl-1, 2-epoxybutane is (1.5-5) to 1, preferably (2-3): 1.
in the present invention, step (1) needs to be performed in an organic solvent selected from one or more of methanol, ethanol, acetonitrile, n-hexane, toluene, dichloroethane and dimethyl sulfoxide, preferably ethanol; the dosage ratio of the solvent to the 3-methyl-1, 2-epoxybutane is (0.5-5) L: 1mol, preferably (1-2) L: 1 mol.
In the invention, the reaction temperature in the step (1) is 30-80 ℃, preferably 50-60 ℃; the reaction time is 4-10h, preferably 6-8 h.
In the invention, the dehydration reaction of the 2-hydroxy-3-methyl butyl acetate in the step (2) is carried out in concentrated sulfuric acid, and the dosage ratio of the concentrated sulfuric acid to the 2-hydroxy-3-methyl butyl acetate is (0.5-2) L: 1mol, preferably (1-1.5) L: 1 mol.
In the invention, the dehydration reaction temperature in the step (2) is 160-200 ℃, preferably 170-180 ℃; the reaction time was varied until no product was formed and the pressure was atmospheric (101.3 kPaA).
In the invention, the oxidation of 3-methyl-2-butenolide in the step (3) uses selenium dioxide loaded by metal modified silica gel as an oxidant, and the mass ratio of the oxidant to the 3-methyl-2-butenolide is (0.5-5): 1, preferably (2-3): 1.
in the present invention, the oxidation reaction in step (3) needs to be carried out in an organic solvent, the organic solvent is one or more selected from the group consisting of toluene, xylene, tetrahydrofuran, dioxane, acetonitrile and dimethyl sulfoxide, and toluene is preferred; the dosage ratio of the solvent to the 3-methyl-2-butenolide acetate is (0.5-2) L: 1mol, preferably (1-1.5) L: 1 mol.
In the invention, the reaction temperature of the oxidation reaction in the step (3) is 50-120 ℃, and preferably 70-100 ℃; the reaction time is 6-12h, preferably 8-10 h.
In the invention, the preparation method of the metal modified silica gel loaded selenium dioxide comprises the following steps:
s1: pretreatment of silica gel: after soaking the silica gel in dilute nitric acid, washing and drying to obtain deionized silica gel;
s2: modification of metal ions: adding the deionized silica gel into an aqueous solution of a metal modifier, adjusting the pH value, reacting at a certain temperature, and washing and drying a solid after the reaction to obtain the metal modified silica gel;
s3: selenium dioxide loading: adding selenium dioxide and metal modified silica gel into an organic solvent, reacting for a period of time at a certain temperature, filtering and drying the solid to obtain the selenium dioxide loaded on the metal modified silica gel.
In the invention, the silica gel in the step S1 needs to be soaked by dilute nitric acid, and the concentration of the dilute nitric acid is (0.5-3) mol/L, preferably (1-1.5) mol/L; the ratio of the dosage of the dilute nitric acid to the dosage of the silica gel is (1-5) mL: 1g, preferably (2-3) mL: 1g of a compound; the soaking time is 0.5-3h, preferably 1-1.5 h.
In the invention, the solid obtained in the step S1 is washed to be neutral after being filtered, and is dried at the temperature of 100-150 ℃, preferably at the temperature of 120-130 ℃; the drying time is 3-10h, preferably 5-8 h.
In the present invention, the metal modifier in step S2 is selected from one or more of chlorides, nitrates or sulfates of iron, aluminum, magnesium, cobalt, copper, manganese or nickel, preferably copper chloride; the mass ratio of the metal modifier to the silica gel is (0.1-2): 1, preferably (0.5-1): 1.
in the present invention, the modification process described in step S2 requires adding ammonia water to adjust pH, the ammonia water concentration is 2 to 6mol/L, preferably 4 to 5mol/L, and the pH adjustment range is 9 to 12, preferably pH 10.
In the invention, the modification process in the step S2 is carried out in an aqueous solution of metal salt, and the mass ratio of the metal salt to the water is (0.1-2): 1, preferably (0.5-1.5): 1; the reaction temperature is 50-90 ℃, preferably 60-80 ℃; the reaction time is 1-5h, preferably 2-3 h.
In the invention, the solid obtained in the step S2 is washed to be neutral after being filtered, and is dried at the temperature of 100-150 ℃, preferably at the temperature of 120-130 ℃; the drying time is 3-10h, preferably 5-8 h.
In the invention, the silica gel after the metal modification in the step S3 is continuously loaded with selenium dioxide, the loading process is carried out in a solvent, the solvent is selected from one or more of water, methanol, ethanol, acetone, benzene and toluene, and ethanol is preferred; the amount of solvent and silica gel used was (2-6) mL: 1g, preferably (3-5) mL: 1g of the total weight of the composition.
In the invention, the mass ratio of the selenium dioxide and the metal modified silica gel in the step S3 is (0.1-1): 1, preferably (0.3-0.6): 1.
in the invention, the loading temperature of the selenium dioxide in the step S3 is 50-100 ℃, and preferably 70-80 ℃; the time is 5-10h, preferably 6-8 h.
In the invention, the solid obtained in the step S3 is washed to be neutral after being filtered, and is dried at the temperature of 100-150 ℃, preferably at the temperature of 120-130 ℃; the drying time is 3-10h, preferably 5-8 h.
The invention has the positive effects that:
(1) the reaction steps are few, the raw materials and auxiliary materials are simple and easy to obtain, the use of expensive phosphine catalysts and noble metal catalysts is avoided in the reaction process, and the reaction cost is greatly reduced;
(2) the reaction process is simple to operate, the intermediate is stable and easy to separate, no waste water is generated, and the method is environment-friendly;
(3) the synthesis route is short, the total yield is high, and the total yield of the route can reach over 75 percent and is far higher than that of the prior art by about 60 percent when the 3-methyl-1, 2-epoxybutane is taken as the starting raw material.
Detailed Description
The technical solutions of the present invention are further described below, but not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the scope of the technical solutions of the present invention.
Gas chromatographic analysis: the chromatographic type is as follows: agilent WAX 1701.42249; carrier gas: high-purity nitrogen; sample introduction mode: an autosampler; nitrogen flow rate: 64.5 ml/min; vaporization chamber temperature: 280 ℃; split-flow sample introduction, split-flow ratio: 1: 40; sample introduction amount: 0.2 μ l; the column flow rate was 1.5 ml/min; column temperature: first-order temperature programming, wherein the initial temperature is 100 ℃, the temperature is kept for 2 minutes, then the temperature is raised to 230 ℃ at the speed of 15 ℃/min, and the temperature is kept for 15 minutes; the total running time is 25.67 min; the temperature of the detector is 300 ℃; and (4) selecting an external standard method for quantification.
NMR analysis: nuclear magnetic resonance data (1H 400MHz,13C100 MHz) were measured by a Varian 400NMR spectrometer, the dissolution reagent was CDCl3。
Some of the reagent specifications and sources in the examples and comparative examples
Example 1
(1) Preparation of 2-hydroxy-3-methyl butyl acetate: in a 3L reactor were charged 86.07g (1.0mol) of 3-methyl-1, 2-epoxybutane and0.5L of absolute ethyl alcohol, then 123.05g (1.5mol) of sodium acetate are added, stirring is started, the rotating speed is set to be 800rpm, the temperature is increased to 80 ℃, and the reaction is carried out for 6 hours. After the reaction is finished, ethanol is recovered under reduced pressure, mother liquor is rectified by a packed tower with 20 theoretical plates under the condition of 1kPa to remove the reaction liquid of the solvent, the reflux ratio is 3:1, 73-75 ℃ fractions at the tower top are collected to obtain 144.32g of 2-hydroxy-3-methyl butyl acetate, the content of the 2-hydroxy-3-methyl butyl acetate is 99.1 percent by gas chromatography analysis, and the yield is 97.9 percent. The nuclear magnetic analysis data are:1H NMR(CDCl3)：5.02-5.00(d,2H),3.80-3.75(m,1H),3.22-3.19(m,1H),2.21(s,3H),1.91-1.88(m,1H)，0.85-0.80(m,6H)；13C NMR(100MHz,C6D6)：170.3,78.5,66.9,30.2,20.3,15.5。
(2) preparing 3-methyl-2-butenyl acetate:
500mL of concentrated sulfuric acid and 146.09g (1.0mol) of 3-methyl-2-butenolide acetate are added into a 3L glass three-neck flask, then a simple distillation device is arranged, the reaction pressure is normal pressure (103.2kPaA), the oil bath temperature is set to be 160 ℃, the generated 3-methyl-2-butenolide acetate is continuously collected in the reaction process, and the tower top temperature (namely the temperature measured by a thermometer right above the simple distillation device) is 153-plus 155 ℃. When the temperature at the top of the tower is more than 155 ℃, the reaction is stopped to obtain 125.08g of 3-methyl-2-butenolide acetate. The content of 3-methyl-2-butenyl acetate in the sample was 98.2% by gas chromatography, and the yield was 95.9%. The nuclear magnetic analysis data are:1H NMR(CDCl3)：5.39-5.35(t,1H),4.45-4.40(d,2H),2.25(s,3H)1.88(s,3H),1.73(s,3H)；13CNMR(100MHz,C6D6)：170.3,140.5,120.9,66.9,30.2,20.3,15.5。
(3) preparation of 4-acetoxy-2-methyl-2-butenal:
preparing a catalyst:
1) preparation of deionized silica gel: 5L of prepared 0.5mol/L dilute nitric acid is added into a 10L reaction kettle, then 1000g of silica gel is added, and the mixture is stirred for 3 hours at room temperature. And (3) filtering after the reaction is finished, washing the solid to be neutral by deionized water, then putting the solid into an oven to be dried for 10 hours at 100 ℃ to obtain deionized silica gel, and grinding for later use.
2) Modification of silica gel metal: adding 1000g of deionized water and 100g of copper chloride into a 5L reaction kettle, stirring to dissolve, adding 1000g of ground deionized silica gel, heating to 90 ℃, dropwise adding 2mol/L ammonia water, adjusting the reaction pH to 9, and continuously reacting at 90 ℃ for 2 hours. And after the reaction is finished, cooling the reaction liquid to room temperature, filtering the solid, washing the solid with deionized water to be neutral, then putting the solid into an oven to dry the solid for 10 hours at 100 ℃ to obtain the metal modified silica gel, and grinding the metal modified silica gel for later use.
3) Selenium dioxide loading: 2L of absolute ethyl alcohol and 1000g of metal modified silica gel are added into a 5L reaction kettle, the temperature is raised to 70 ℃ under stirring, 100g of selenium dioxide is added, and the reaction is continued for 6 hours at 70 ℃. And after the reaction is finished, cooling the reaction liquid to room temperature, filtering the solid, washing the solid with deionized water to be neutral, then putting the solid into an oven to dry the solid for 10 hours at 100 ℃ to obtain the oxidant-modified silica gel-loaded selenium dioxide, and grinding the selenium dioxide for later use.
And (3) oxidation reaction:
0.5L of acetonitrile and 128.08g (1.0mol) of 3-methyl-2-butenolide acetate are added into a 3L reaction kettle, 64.04g of prepared oxidant is added after uniform stirring, the reaction temperature is raised to 120 ℃, and the reaction lasts for 8 hours. Recovering acetonitrile under reduced pressure, rectifying the mother liquor by a packed tower with 20 theoretical plates under the condition of 1kPa to remove the reaction liquid of the solvent, wherein the reflux ratio is 5:1, collecting the fraction at 80-82 ℃ at the top of the tower to obtain 138.91g of 4-acetoxyl-2-methyl-2-butenal, and the content of the 4-acetoxyl-2-methyl-2-butenal is 99.2 percent through gas chromatography analysis, and the yield is 97.0 percent. The nuclear magnetic analysis data are:1H NMR(400MHz,CDCl3)9.46(s,1H),6.52-6.48(m,1H),4.90(d,J＝6.0Hz,2H),2.13(s,3H),1.80(d,J＝1.1Hz,3H)；13C NMR(100MHz,CDCl3)：196.5,147.2,142.3,70.4,45.0,21.2,18.3。
example 2
(1) Preparation of 2-hydroxy-3-methyl butyl acetate:
86.07g (1.0mol) of 3-methyl-1, 2-epoxybutane and 1L of absolute ethyl alcohol are added into a 3L reaction kettle, then 195.96g (2.0mol) of potassium acetate are added, the stirring is started, the rotating speed is set at 800rpm, the temperature is increased to 60 ℃, and the reaction is carried out for 8 hours. After the reaction is finished, ethanol is recovered under reduced pressure, mother liquor is rectified by a packed tower with 20 theoretical plates under the condition of 1kPa to remove the reaction liquid of the solvent, the reflux ratio is 3:1, the fraction at 73-75 ℃ at the top of the tower is collected to obtain 144.75g of 2-hydroxy-3-methyl butyl acetate, the content of the 2-hydroxy-3-methyl butyl acetate is 98.1 percent by gas chromatography analysis, and the yield is 97.2 percent.
(2) Preparing 3-methyl-2-butenyl acetate:
1000mL of concentrated sulfuric acid and 146.09g (1.0mol) of 3-methyl-2-butenolide acetate are added into a 3L glass three-neck flask, then a simple distillation device is arranged, the reaction pressure is normal pressure (103.2kPaA), the oil bath temperature is set to be 170 ℃, the generated 3-methyl-2-butenolide acetate is continuously collected in the reaction process, and the tower top temperature is 153-155 ℃. When the temperature at the top of the tower is more than 155 ℃, the reaction is stopped to obtain 123.28g of 3-methyl-2-butenolide acetate. The content of 3-methyl-2-butenyl acetate by gas chromatographic analysis of a sample is 98.8 percent, and the yield is 95.1 percent.
(3) Preparation of 4-acetoxy-2-methyl-2-butenal:
preparing a catalyst:
1) preparation of deionized silica gel: A10L reaction kettle is added with 3L of prepared 1.0mol/L dilute nitric acid, then 1000g of silica gel is added, and the mixture is stirred for 1.5h at room temperature. And (3) filtering after the reaction is finished, washing the solid to be neutral by deionized water, then putting the solid into an oven to be dried for 8 hours at 120 ℃ to obtain deionized silica gel, and grinding for later use.
2) Modification of silica gel metal: adding 1000g of deionized water and 500g of copper chloride into a 5L reaction kettle, stirring to dissolve, adding 1000g of ground deionized silica gel, heating to 90 ℃, dropwise adding 4mol/L ammonia water, adjusting the reaction pH to 10, and continuously reacting at 60 ℃ for 5 hours. And after the reaction is finished, cooling the reaction liquid to room temperature, filtering the solid, washing the solid with deionized water to be neutral, then putting the solid into an oven to dry the solid for 8 hours at 120 ℃ to obtain the metal modified silica gel, and grinding the metal modified silica gel for later use.
3) Selenium dioxide loading: adding 3L of absolute ethyl alcohol and 1000g of metal modified silica gel into a 5L reaction kettle, heating to 80 ℃ under stirring, adding 300g of selenium dioxide, and continuously reacting at 80 ℃ for 8 hours. And after the reaction is finished, cooling the reaction liquid to room temperature, filtering the solid, washing the solid with deionized water to be neutral, then putting the solid into an oven to dry for 8 hours at 120 ℃ to obtain the oxidant-modified silica gel-loaded selenium dioxide, and grinding the selenium dioxide for later use.
And (3) oxidation reaction:
adding 128.08g (1.0mol) of toluene and 3-methyl-2-butenolide acetate 1L into a reaction kettle 3L, stirring uniformly, adding 256.16g of prepared oxidant, heating to 100 ℃ for reaction, and reacting for 10 hours. Recovering toluene under reduced pressure, rectifying the mother liquor with a packed tower with 20 theoretical plates under 1kPa to remove the reaction liquid after the solvent, wherein the reflux ratio is 5:1, collecting the fraction at 80-82 ℃ at the top of the tower to obtain 134.33g of 4-acetoxyl-2-methyl-2-butenal, and the content of the 4-acetoxyl-2-methyl-2-butenal is 99.3 percent through gas chromatography analysis, wherein the yield is 93.9 percent.
Example 3
(1) Preparation of 2-hydroxy-3-methyl butyl acetate:
86.07g (1.0mol) of 3-methyl-1, 2-epoxybutane and 2L of acetonitrile are added into a 3L reaction kettle, then 246.09g (3.0mol) of sodium acetate are added, the stirring is started, the rotation speed is set to 800rpm, the temperature is increased to 60 ℃, and the reaction is carried out for 4 hours. After the reaction is finished, recovering acetonitrile under reduced pressure, rectifying the mother liquor by using a packed tower with 20 theoretical plates under the condition of 1kPa to remove the reaction liquid of the solvent, wherein the reflux ratio is 3:1, collecting the fraction at 73-75 ℃ at the top of the tower to obtain 144.01g of 2-hydroxy-3-methyl butyl acetate, and the content of the 2-hydroxy-3-methyl butyl acetate is 98.3 percent and the yield is 96.9 percent by gas chromatography analysis.
(2) Preparing 3-methyl-2-butenyl acetate:
1500mL of concentrated sulfuric acid and 146.09g (1.0mol) of 3-methyl-2-butenolide acetate are added into a 3L glass three-neck flask, then a simple distillation device is arranged, the reaction pressure is normal pressure (103.2kPaA), the oil bath temperature is set to be 180 ℃, the generated 3-methyl-2-butenolide acetate is continuously collected in the reaction process, and the tower top temperature is 153-155 ℃. When the temperature at the top of the tower is more than 155 ℃, the reaction is stopped to obtain 127.82g of 3-methyl-2-butenolide acetate. The content of 3-methyl-2-butenyl acetate by gas chromatographic analysis of a sample is 98.2 percent, and the yield is 98.0 percent.
(3) Preparation of 4-acetoxy-2-methyl-2-butenal:
preparing a catalyst:
1) preparation of deionized silica gel: 2L of prepared 1.5mol/L dilute nitric acid is added into a 5L reaction kettle, then 1000g of silica gel is added, and the mixture is stirred for 1 hour at room temperature. And (3) filtering after the reaction is finished, washing the solid to be neutral by deionized water, then putting the solid into an oven to be dried for 5 hours at 130 ℃ to obtain deionized silica gel, and grinding for later use.
2) Modification of silica gel metal: adding 1000g of deionized water and 1000g of ferric chloride into a 5L reaction kettle, stirring to dissolve, adding 1000g of ground deionized silica gel, heating to 90 ℃, dropwise adding 5mol/L ammonia water, adjusting the reaction pH to 12, and continuously reacting at 80 ℃ for 3 hours. And after the reaction is finished, cooling the reaction liquid to room temperature, filtering the solid, washing the solid with deionized water to be neutral, then putting the solid into an oven to dry the solid for 5 hours at the temperature of 130 ℃ to obtain the metal modified silica gel, and grinding the metal modified silica gel for later use.
3) Selenium dioxide loading: 5L of anhydrous methanol and 1000g of metal modified silica gel are added into a 10L reaction kettle, the temperature is raised to 50 ℃ under stirring, 600g of selenium dioxide is added, and the reaction is continued for 10 hours at 50 ℃. And after the reaction is finished, cooling the reaction liquid to room temperature, filtering the solid, washing the solid with deionized water to be neutral, then putting the solid into a drying oven to be dried for 5 hours at 130 ℃ to obtain the oxidant-modified silica gel-loaded selenium dioxide, and grinding the selenium dioxide for later use.
And (3) oxidation reaction:
adding 1.5L of acetonitrile and 128.08g (1.0mol) of 3-methyl-2-butenolide acetate into a 3L reaction kettle, stirring uniformly, adding 384.24g of prepared oxidant, reacting and heating to 70 ℃, and reacting for 6 hours. Recovering acetonitrile under reduced pressure, rectifying the mother liquor by a packed tower with 20 theoretical plates under the condition of 1kPa to remove the reaction liquid of the solvent, wherein the reflux ratio is 5:1, collecting the fraction at 80-82 ℃ at the top of the tower to obtain 132.04g of 4-acetoxyl-2-methyl-2-butenal, and the content of the 4-acetoxyl-2-methyl-2-butenal is 99.2 percent and the yield is 92.2 percent by gas chromatographic analysis.
Example 4
(1) Preparation of 2-hydroxy-3-methyl butyl acetate:
86.07g (1.0mol) of 3-methyl-1, 2-epoxybutane and 5L of absolute ethyl alcohol are added into a 10L reaction kettle, then 410.15g (5.0mol) of sodium acetate are added, the stirring is started, the rotating speed is set at 800rpm, the temperature is increased to 30 ℃, and the reaction is carried out for 10 hours. After the reaction is finished, ethanol is recovered under reduced pressure, mother liquor is rectified by a packed tower with 20 theoretical plates under the condition of 1kPa to remove the reaction liquid of the solvent, the reflux ratio is 3:1, 73-75 ℃ fractions at the tower top are collected to obtain 140.28g of 2-hydroxy-3-methyl butyl acetate, the content of the 2-hydroxy-3-methyl butyl acetate is 98.1 percent by gas chromatography analysis, and the yield is 94.2 percent.
(2) Preparing 3-methyl-2-butenyl acetate:
2000mL of concentrated sulfuric acid and 146.09g (1.0mol) of 3-methyl-2-butenolide acetate are added into a 5L glass three-neck flask, then a simple distillation device is arranged, the reaction pressure is normal pressure (103.2kPaA), the oil bath temperature is set to be 160 ℃, the generated 3-methyl-2-butenolide acetate is continuously collected in the reaction process, and the tower top temperature is 153-155 ℃. When the temperature at the top of the tower is more than 155 ℃, the reaction is stopped to obtain 127.17g of 3-methyl-2-butenolide acetate. The content of the 3-methyl-2-butenyl acetate is 98.9 percent and the yield is 98.2 percent by the gas chromatographic analysis of a sample.
(3) Preparation of 4-acetoxy-2-methyl-2-butenal:
preparing a catalyst:
1) preparation of deionized silica gel: 1L of prepared 3.0mol/L dilute nitric acid is added into a 3L reaction kettle, then 1000g of silica gel is added, and the mixture is stirred for 0.5h at room temperature. And (3) filtering after the reaction is finished, washing the solid to be neutral by deionized water, then putting the solid into an oven to be dried for 3 hours at the temperature of 150 ℃ to obtain deionized silica gel, and grinding for later use.
2) Modification of silica gel metal: adding 1000g of deionized water and 2000g of copper nitrate into a 5L reaction kettle, stirring to dissolve, adding 1000g of ground deionized silica gel, heating to 50 ℃, dropwise adding 4mol/L ammonia water, adjusting the reaction pH to 10, and continuously reacting at 50 ℃ for 5 hours. And after the reaction is finished, cooling the reaction liquid to room temperature, filtering the solid, washing the solid with deionized water to be neutral, then putting the solid into an oven to dry the solid for 3 hours at the temperature of 150 ℃ to obtain the metal modified silica gel, and grinding the metal modified silica gel for later use.
3) Selenium dioxide loading: 6L of absolute ethyl alcohol and 1000g of metal modified silica gel are added into a 10L reaction kettle, the temperature is raised to 100 ℃ under stirring, 1000g of selenium dioxide is added, and the reaction is continued for 5 hours at 100 ℃. And after the reaction is finished, cooling the reaction liquid to room temperature, filtering the solid, washing the solid with deionized water to be neutral, then putting the solid into an oven to dry the solid for 3 hours at the temperature of 150 ℃ to obtain the oxidant-modified silica gel-loaded selenium dioxide, and grinding the selenium dioxide for later use.
And (3) oxidation reaction:
2.0L of acetonitrile and 128.08g (1.0mol) of 3-methyl-2-butenolide acetate are added into a 5L reaction kettle, 640.4g of prepared oxidant is added after uniform stirring, the reaction temperature is raised to 50 ℃, and the reaction is carried out for 12 hours. Recovering acetonitrile under reduced pressure, rectifying the mother liquor by a packed tower with 20 theoretical plates under the condition of 1kPa to remove the reaction liquid of the solvent, wherein the reflux ratio is 5:1, collecting the fraction at 80-82 ℃ at the top of the tower to obtain 137.20g of 4-acetoxyl-2-methyl-2-butenal, and the content of the 4-acetoxyl-2-methyl-2-butenal is 99.3 percent and the yield is 95.9 percent by gas chromatographic analysis.
Example 5
(1) Preparation of 2-hydroxy-3-methyl butyl acetate:
86.07g (1.0mol) of 3-methyl-1, 2-epoxybutane and 0.75L of acetonitrile are added into a 3L reaction kettle, then 176.36g (1.8mol) of potassium acetate are added, the stirring is started, the rotation speed is set to 800rpm, the temperature is increased to 80 ℃, and the reaction is carried out for 6 h. After the reaction is finished, recovering acetonitrile under reduced pressure, rectifying the mother liquor by using a packed tower with 20 theoretical plates under the condition of 1kPa to remove the reaction liquid of the solvent, wherein the reflux ratio is 3:1, collecting the fraction at 73-75 ℃ at the top of the tower to obtain 141.20g of 2-hydroxy-3-methyl butyl acetate, and the content of the 2-hydroxy-3-methyl butyl acetate is 98.5 percent and the yield is 95.2 percent by gas chromatographic analysis.
(2) Preparing 3-methyl-2-butenyl acetate:
1000mL of concentrated sulfuric acid and 146.09g (1.0mol) of 3-methyl-2-butenolide acetate are added into a 3L glass three-neck flask, then a simple distillation device is arranged, the reaction pressure is normal pressure (103.2kPaA), the oil bath temperature is set to be 160 ℃, the generated 3-methyl-2-butenolide acetate is continuously collected in the reaction process, and the tower top temperature is 153-155 ℃. When the temperature at the top of the tower is more than 155 ℃, the reaction is stopped to obtain 124.32g of 3-methyl-2-butenolide acetate. The content of the 3-methyl-2-butenyl acetate is 98.8 percent and the yield is 96.0 percent by the gas chromatographic analysis of a sample.
(3) Preparation of 4-acetoxy-2-methyl-2-butenal:
preparing a catalyst:
1) preparation of deionized silica gel: 2.5L of the prepared 2.0mol/L dilute nitric acid was added to a 5L reaction kettle, followed by addition of 1000g of silica gel and stirring at room temperature for 2 h. And (3) filtering after the reaction is finished, washing the solid to be neutral by deionized water, then putting the solid into an oven to be dried for 5 hours at the temperature of 150 ℃ to obtain deionized silica gel, and grinding for later use.
2) Modification of silica gel metal: adding 1000g of deionized water and 300g of magnesium chloride into a 5L reaction kettle, stirring to dissolve, adding 1000g of ground deionized silica gel, heating to 70 ℃, dropwise adding 6mol/L ammonia water, adjusting the reaction pH to 10, and continuously reacting at 70 ℃ for 4 hours. And after the reaction is finished, cooling the reaction liquid to room temperature, filtering the solid, washing the solid with deionized water to be neutral, then putting the solid into an oven to dry the solid for 5 hours at the temperature of 150 ℃ to obtain the metal modified silica gel, and grinding the metal modified silica gel for later use.
3) Selenium dioxide loading: 4L of toluene and 1000g of metal modified silica gel are added into a 10L reaction kettle, the temperature is raised to 70 ℃ under stirring, 500g of selenium dioxide is added, and the reaction is continued for 7 hours at 70 ℃. And after the reaction is finished, cooling the reaction liquid to room temperature, filtering the solid, washing the solid with deionized water to be neutral, then putting the solid into an oven to dry the solid for 5 hours at the temperature of 150 ℃ to obtain the oxidant-modified silica gel-loaded selenium dioxide, and grinding the selenium dioxide for later use.
And (3) oxidation reaction:
0.75L of acetonitrile and 128.08g (1.0mol) of 3-methyl-2-butenolide acetate are added into a 3L reaction kettle, 128.08g of prepared oxidant is added after uniform stirring, the reaction temperature is raised to 120 ℃, and the reaction lasts for 8 hours. Recovering acetonitrile under reduced pressure, rectifying the mother liquor by a packed tower with 20 theoretical plates under the condition of 1kPa to remove the reaction liquid of the solvent, wherein the reflux ratio is 5:1, collecting the fraction at 80-82 ℃ at the top of the tower to obtain 133.50g of 2-hydroxy-3-methyl butyl acetate, and the content of the 2-hydroxy-3-methyl butyl acetate is 99.6 percent by gas chromatographic analysis, and the yield is 93.6 percent.
Example 6
(1) Preparation of 2-hydroxy-3-methyl butyl acetate:
86.07g (1.0mol) of 3-methyl-1, 2-epoxybutane and 3L of acetonitrile are added into a 3L reaction kettle, then 139.45g (1.7mol) of sodium acetate are added, stirring is started, the rotating speed is set to 800rpm, the temperature is increased to 80 ℃, and the reaction is carried out for 9 h. After the reaction is finished, recovering acetonitrile under reduced pressure, rectifying the mother liquor by using a packed tower with 20 theoretical plates under the condition of 1kPa to remove the reaction liquid of the solvent, wherein the reflux ratio is 3:1, collecting the fraction at 73-75 ℃ at the top of the tower to obtain 143.58g of 2-hydroxy-3-methyl butyl acetate, and the content of the 2-hydroxy-3-methyl butyl acetate is 98.9 percent and the yield is 97.2 percent by gas chromatographic analysis.
(2) Preparing 3-methyl-2-butenyl acetate:
1200mL of concentrated sulfuric acid and 146.09g (1.0mol) of 3-methyl-2-butenolide acetate are added into a 3L glass three-neck flask, then a simple distillation device is arranged, the reaction pressure is normal pressure (103.2kPaA), the oil bath temperature is set to be 200 ℃, the generated 3-methyl-2-butenolide acetate is continuously collected in the reaction process, and the tower top temperature is 153-155 ℃. When the temperature at the top of the tower is more than 155 ℃, the reaction is stopped to obtain 123.43g of 3-methyl-2-butenolide acetate. The content of 3-methyl-2-butenyl acetate was 96.5% and the yield was 93.0% by gas chromatography.
(3) Preparation of 4-acetoxy-2-methyl-2-butenal:
preparing a catalyst:
1) preparation of deionized silica gel: 2.5L of prepared 2.0mol/L dilute nitric acid is added into a 5L reaction kettle, then 1000g of silica gel is added, and the mixture is stirred for 3 hours at room temperature. And (3) filtering after the reaction is finished, washing the solid to be neutral by deionized water, then putting the solid into an oven to be dried for 6 hours at 140 ℃ to obtain deionized silica gel, and grinding for later use.
2) Modification of silica gel metal: 1000g of deionized water and 1500g of magnesium sulfate are added into a 5L reaction kettle, stirred to be dissolved, 1000g of ground deionized silica gel is added, the temperature is raised to 80 ℃, 4mol/L ammonia water is added dropwise, the reaction pH is adjusted to 10, and the reaction is continued at 80 ℃ for 4 hours. And after the reaction is finished, cooling the reaction liquid to room temperature, filtering the solid, washing the solid with deionized water to be neutral, then putting the solid into an oven to dry the solid for 6 hours at 140 ℃ to obtain the metal modified silica gel, and grinding the metal modified silica gel for later use.
3) Selenium dioxide loading: 2.5L of absolute ethyl alcohol and 1000g of metal modified silica gel are added into a 5L reaction kettle, the temperature is raised to 90 ℃ under stirring, 800g of selenium dioxide is added, and the reaction is continued for 7 hours at 90 ℃. And after the reaction is finished, cooling the reaction liquid to room temperature, filtering the solid, washing the solid with deionized water to be neutral, then putting the solid into an oven to dry the solid for 6 hours at 140 ℃ to obtain the oxidant-modified silica gel-loaded selenium dioxide, and grinding the selenium dioxide for later use.
And (3) oxidation reaction:
1.25L of toluene and 128.08g (1.0mol) of 3-methyl-2-butenolide acetate are added into a 3L reaction kettle, 512.32g of prepared oxidant is added after uniform stirring, the reaction temperature is raised to 110 ℃, and the reaction is carried out for 11 hours. Recovering toluene under reduced pressure, rectifying the mother liquor with a packed tower with 20 theoretical plates under 1kPa to remove the reaction liquid after the solvent, wherein the reflux ratio is 5:1, collecting the fraction at 80-82 ℃ at the top of the tower to obtain 137.57g of 4-acetoxyl group-2-methyl-2-butenal, and the content of the 4-acetoxyl group-2-methyl-2-butenal is 98.2 percent and the yield is 95.1 percent by gas chromatographic analysis.
Comparative example 1
The steps and the process similar to those of the example 1 are adopted, but the step (1) takes dioxane as a solvent, so that the reaction selectivity and the product yield are greatly reduced; in the step (3), selenium dioxide is directly used as an oxidant, so that the reaction selectivity and the product yield are greatly reduced.
(1) Preparation of 2-hydroxy-3-methyl butyl acetate:
8.07g (1.0mol) of 3-methyl-1, 2-epoxybutane and 0.5L of dioxane are added into a 3L reaction kettle, then 123.05g (1.5mol) of sodium acetate are added, stirring is started, the rotation speed is set to 800rpm, the temperature is increased to 80 ℃, and the reaction is carried out for 6 hours. After the reaction is finished, the dichloroethane is recovered under reduced pressure, the mother liquor is rectified by a packed tower with 20 theoretical plates to remove the reaction liquor after the solvent under the condition of 1kPa at the reflux ratio of 3:1, the fraction at 73-75 ℃ at the top of the tower is collected to obtain 77.25g of 2-hydroxy-3-methyl butyl acetate, the content of the 2-hydroxy-3-methyl butyl acetate is 98.9 percent by gas chromatographic analysis, and the yield is 52.3 percent.
(2) Preparing 3-methyl-2-butenyl acetate:
500mL of concentrated sulfuric acid and 146.09g (1.0mol) of 3-methyl-2-butenolide acetate are added into a 3L glass three-neck flask, then a simple distillation device is arranged, the reaction pressure is normal pressure (103.2kPaA), the oil bath temperature is set to be 160 ℃, the generated 3-methyl-2-butenolide acetate is continuously collected in the reaction process, and the tower top temperature is 153-155 ℃. When the temperature at the top of the tower is more than 155 ℃, the reaction is stopped to obtain 125.99g of 3-methyl-2-butenolide acetate. The content of the 3-methyl-2-butenyl acetate is 98.2 percent and the yield is 96.6 percent by the gas chromatographic analysis of a sample.
(3) Preparation of 4-acetoxy-2-methyl-2-butenal:
0.5L of acetonitrile and 128.08g (1.0mol) of 3-methyl-2-butenolide acetate are added into a 3L reaction kettle, 223.82g of selenium dioxide is added after uniform stirring, the reaction temperature is raised to 120 ℃, and the reaction lasts for 8 hours. Recovering acetonitrile under reduced pressure, rectifying the mother liquor by a packed tower with 20 theoretical plates under the condition of 1kPa to remove the reaction liquid of the solvent, wherein the reflux ratio is 5:1, collecting the fraction at 80-82 ℃ at the top of the tower to obtain 18.53g of 4-acetoxyl-2-methyl-2-butenal, and the content of the 4-acetoxyl-2-methyl-2-butenal is 96.6 percent through gas chromatographic analysis, and the yield is 12.9 percent.
Claims (13)
1. A preparation method of 4-acetoxyl-2-methyl-2-butenal comprises the following steps:
(1) 3-methyl-1, 2-epoxybutane is subjected to ring opening under the action of alkaline acetate to generate 2-hydroxy-3-methyl butyl acetate;
(2) dehydrating the 2-hydroxy-3-methyl butyl acetate to obtain 3-methyl-2-butyl acetate;
(3) the 3-methyl-2-butenoic acid ester uses selenium dioxide loaded by metal modified silica gel as an oxidant, and 4-acetoxyl group-2-methyl-2-butenal is obtained through one-step selective oxidation.
2. The preparation method according to claim 1, wherein the basic acetate in step (1) is selected from one of sodium acetate and potassium acetate, preferably sodium acetate; the molar ratio of acetate to 3-methyl-1, 2-epoxybutane is (1.5-5) to 1, preferably (2-3): 1.
3. the production method according to claim 1 or 2, characterized in that step (1) is carried out in an organic solvent selected from one or more of methanol, ethanol, acetonitrile, n-hexane, toluene, dichloroethane and dimethylsulfoxide, preferably ethanol; the dosage ratio of the solvent to the 3-methyl-1, 2-epoxybutane is (0.5-5) L: 1mol, preferably (1-2) L: 1 mol.
4. The process according to any one of claims 1 to 3, wherein the reaction temperature in step (1) is 30 to 80 ℃, preferably 50 to 60 ℃; the reaction time is 4-10h, preferably 6-8 h.
5. The production method according to any one of claims 1 to 4, wherein the dehydration reaction of butyl 2-hydroxy-3-methylacetate in the step (2) is carried out in concentrated sulfuric acid, and the ratio of the amount of concentrated sulfuric acid to butyl 2-hydroxy-3-methylacetate is (0.5 to 2) L: 1mol, preferably (1-1.5) L: 1 mol.
6. The method according to any one of claims 1 to 5, wherein the dehydration reaction temperature in step (2) is 160-200 ℃, preferably 170-180 ℃.
7. The preparation method according to any one of claims 1 to 6, wherein the modified metal in the selenium dioxide loaded on the oxidant metal-modified silica gel in the step (3) is selected from one or more of iron, aluminum, magnesium, cobalt, copper, manganese and nickel, and the mass ratio of the oxidant to the 3-methyl-2-butenyl acetate is (0.5-5): 1, preferably (2-3): 1.
8. the method of any one of claims 1-7, wherein the preparation of the metal-modified silica gel-supported selenium dioxide comprises the steps of:
s1: pretreatment of silica gel: after soaking the silica gel in dilute nitric acid, washing and drying to obtain deionized silica gel;
s2: modification of metal ions: adding deionized silica gel into an aqueous solution of a metal modifier, adjusting the pH to 9-12, reacting at a certain temperature, and washing and drying a solid after the reaction to obtain the metal modified silica gel;
s3: selenium dioxide loading: adding selenium dioxide and metal modified silica gel into an organic solvent, reacting for a period of time at a certain temperature, filtering, washing and drying the solid to obtain the selenium dioxide loaded on the metal modified silica gel.
9. The method according to claim 8, wherein the dilute nitric acid concentration in S1 is (0.5-3) mol/L, preferably (1-1.5) mol/L; the ratio of the nitric acid dosage to the silica gel dosage is (1-5) mL: 1g, preferably (2-3) mL: 1g of a compound; soaking for 0.5-3h, preferably 1-1.5 h;
and/or, washing the solid in S1 to be neutral by using deionized water, and drying at 100-150 ℃, preferably at 120-130 ℃; the drying time is 3-10h, preferably 5-8 h.
10. The method according to claim 8 or 9, wherein the metal modifier in S2 is selected from one or more of chlorides, nitrates or sulfates of iron, aluminum, magnesium, cobalt, copper, manganese or nickel, preferably copper chloride; the mass ratio of the metal modifier to the deionized silica gel is (0.1-2): 1, preferably (0.5-1): 1;
and/or the modification process in S2 is carried out in an aqueous solution of metal salt, and the mass ratio of the metal modifier to water is (0.1-2): 1, preferably (0.5-1.5): 1; the reaction temperature is 50-90 ℃, preferably 60-80 ℃; the reaction time is 1-5h, preferably 2-3 h;
and/or, in the modification process in S2, ammonia water is added to adjust the pH, and the concentration of the ammonia water is 2-6mol/L, preferably 4-5 mol/L;
and/or, drying at 100-150 ℃ in S2, preferably at 120-130 ℃; the drying time is 3-10h, preferably 5-8 h.
11. The method according to any one of claims 8 to 10, wherein the solvent in S3 is selected from one or more of water, methanol, ethanol, acetone, benzene, and toluene, preferably ethanol; the amount of solvent and silica gel used was (2-6) mL: 1g, preferably (3-5) mL: 1g of a compound;
and/or the mass ratio of the selenium dioxide to the modified silica gel in S3 is (0.1-1): 1, preferably (0.3-0.6): 1.
and/or the loading temperature of the selenium dioxide in S3 is 50-100 ℃, preferably 70-80 ℃; the time is 5 to 10 hours, preferably 6 to 8 hours;
and/or, S3 is dried at 100-150 ℃, preferably at 120-130 ℃; the drying time is 3-10h, preferably 5-8 h.
12. The production method according to any one of claims 1 to 11, wherein the oxidation reaction in step (3) is carried out in an organic solvent selected from one or more of toluene, xylene, tetrahydrofuran, dioxane, acetonitrile and dimethyl sulfoxide, preferably toluene; the dosage ratio of the solvent to the 3-methyl-2-butenolide acetate is (0.5-2) L: 1mol, preferably (1-1.5) L: 1 mol.
13. The method according to any one of claims 1 to 12, wherein the oxidation in step (3) is carried out at a reaction temperature of 50 to 120 ℃, preferably 70 to 100 ℃; the reaction time is 6-12h, preferably 8-10 h.
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