CN112321426A - Preparation of 4-acyloxy-2-methyl-2-butenal by catalytic oxidation method - Google Patents

Preparation of 4-acyloxy-2-methyl-2-butenal by catalytic oxidation method Download PDF

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CN112321426A
CN112321426A CN202011052341.5A CN202011052341A CN112321426A CN 112321426 A CN112321426 A CN 112321426A CN 202011052341 A CN202011052341 A CN 202011052341A CN 112321426 A CN112321426 A CN 112321426A
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butenal
acyloxy
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CN112321426B (en
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陈凯
郑文龙
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Ma'anshan Kesi Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/881—Molybdenum and iron
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Abstract

The invention provides a preparation method of 4-acyloxy-2-methyl-2-butenal, which comprises the following steps: firstly, preparing raw materials, then reacting the raw materials with the substances prepared in the step 1, and finally carrying out post-treatment to obtain the 4-acyloxy-2-methyl-2-butenal. The preparation method of the 4-acyloxy-2-methyl-2-butenal is simple in process and mild in reaction conditions, is carried out in the presence of a catalyst, has good catalytic activity and excellent stability and durability, can obtain a product with higher yield by using the catalyst, is low in preparation cost, generates less waste salt and waste water in the preparation process, accords with the green chemical concept, and is high in industrial amplification feasibility.

Description

Preparation of 4-acyloxy-2-methyl-2-butenal by catalytic oxidation method
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for preparing 4-acyloxy-2-methyl-2-butenal by a catalytic oxidation method.
Background
Chloro (halo) isoamylene acetate is an important intermediate for synthesizing products such as medicines (hypolipidemic drugs, hypoglycemic drugs, vitamin A, vitamin E and the like), perfumes (citronellal, lavender alcohol and the like), pigments (cherry red, orange red, dark blue, orange and the like) and the like.
The oxidation product of chloroisopentene acetate, 4-acyloxy-2-methyl-2-butenal (hereinafter referred to as C5 aldehyde ester), is an important intermediate for preparing compounds such as vitamin A ester (acetate, propionate and palmitate), and in the prior art, the following two oxidation methods are mainly used:
DMSO Oxidation (Kornblum oxidation)
The method has the advantages of low yield of 40-50%, dimethyl sulfide needing to be recovered, pungent smell, poor reaction repeatability, certain toxicity of a used reagent DMSO, generation of a large amount of waste water in the post-treatment process and environmental friendliness.
Figure BDA0002709950910000011
2. Urotropine oxidation (Sommelet reaction)
The method is suitable for oxidizing the benzyl halide compound into aldehyde, the yield is 70-80%, and for the aliphatic halogenated hydrocarbon compound, the yield is generally only 20%, so that the method is not high in synthesis yield, large in industrial three wastes and not beneficial to environmental protection.
Figure BDA0002709950910000012
Therefore, a method for preparing 4-acyloxy-2-methyl-2-butenal with less wastewater and waste salt, environmental protection and higher yield is urgently needed to be provided.
Disclosure of Invention
Based on the above technical background, the present inventors have made a keen search and, as a result, have found that: the method comprises the steps of preparing raw materials, and preparing a catalyst, wherein the catalyst is Anderson type polyoxometallate taking Fe as a center, and then the catalyst is used as the catalyst, and chlorine ester is used as the raw material to prepare the C5 aldehyde ester. The preparation method of the 4-acyloxy-2-methyl-2-butenal has the advantages of simple process, mild reaction conditions, good catalytic activity of the catalyst taking Fe as the center, low cost, excellent stability and durability, low preparation cost, less waste salt and waste water generated in the preparation process, accordance with the green chemical concept and high industrial amplification feasibility, and the product with higher yield can be obtained by using the catalyst as the catalyst.
The first aspect of the present invention provides a method for preparing 4-acyloxy-2-methyl-2-butenal, comprising the steps of:
step 1, preparing raw materials;
step 2, carrying out reaction by using the substance prepared in the step 1;
and 3, carrying out post-treatment to obtain a final product.
The second aspect of the present invention is to provide 4-acyloxy-2-methyl-2-butenal obtained by the method for producing 4-acyloxy-2-methyl-2-butenal according to the first aspect of the present invention.
The preparation method of 4-acyloxy-2-methyl-2-butenal and the 4-acyloxy-2-methyl-2-butenal prepared by the method have the following advantages:
(1) the preparation method of the 4-acyloxy-2-methyl-2-butenal has the advantages of low preparation cost, less waste water and waste salt generated in the preparation process, and accordance with the green chemical concept;
(2) the preparation method of the 4-acyloxy-2-methyl-2-butenal has mild reaction conditions;
(3) the preparation method of the 4-acyloxy-2-methyl-2-butenal adopts the oxometallate with iron as the center as the catalyst, and has good catalytic activity, excellent stability and durability;
(4) the preparation method of the 4-acyloxy-2-methyl-2-butenal has high product yield and industrial amplification value.
Detailed Description
The present invention will be described in detail below, and features and advantages of the present invention will become more apparent and apparent with reference to the following description.
The first aspect of the present invention provides a method for producing 4-acyloxy-2-methyl-2-butenal, comprising the steps of:
step 1, preparing raw materials;
step 2, carrying out reaction by using the substance prepared in the step 1;
and 3, carrying out post-treatment to obtain a final product.
This step is specifically described and illustrated below.
Step 1, preparing raw materials.
The raw materials comprise acetonitrile aqueous solution and C5 chloro-ester, and in the invention, the acetonitrile aqueous solution is used as a solvent, the inventor finds that a reaction system of a single solvent is heterogeneous, and the catalytic effect is poor, which is probably because the solubility of the catalyst is poor in the heterogeneous solvent, the reaction conversion rate is low, the acetonitrile aqueous solution is used as the solvent to enable the reaction system to be homogeneous, the solubility of the catalyst in the solvent is good, the catalytic effect is obviously improved, and further the product yield is improved.
When the mass ratio of acetonitrile to water is 1: (0.5 to 2), preferably 1: 1. The catalyst has better solubility in the solvent and better catalytic effect.
In the invention, the C5 chloro ester is selected from one or more of chloro acetate, chloro propionate, chloro palmitate, tert-butyl chloroacetate, isopropyl chloroformate, ethyl trichloroacetate, n-butyl chloroacetate and isobutyl chloroacetate; preferably, the C5 chloro ester is selected from one or more of chloro acetate, chloro propionate, chloro palmitate, tert-butyl chloroacetate and isobutyl chloroacetate; more preferably, the C5 chlorine ester is selected from one or more of chlorine acetate, chlorine propionate and chlorine palmitate.
According to a preferred embodiment of the present invention, step 1 further comprises the preparation of a catalyst. According to the invention, the catalyst is preferably an Anderson-type polyoxometalate, which is a condensed acid formed by condensing an inorganic oxoacid. The compound is mainly an inorganic metal-oxygen cluster compound with special structure and property formed by connecting early transition metal elements through oxygen. The Anderson type polyoxometallate has the advantages of mild catalytic conditions, high yield and selectivity and the like. The inventor finds that the catalyst is used as the catalyst in the invention, and the defects of pollution, difficult catalyst recovery and complicated post-treatment of the traditional acid-base catalysis are avoided. And the catalyst is used for preparing the aldehyde ester, so that the preparation efficiency and the yield of the aldehyde ester can be effectively improved.
According to a further preferred embodiment of the present invention, the catalyst is prepared by:
step 1-1, adding a compound containing an element A into inorganic oxyacid for reaction;
and step 1-2, carrying out post-treatment after the reaction is finished to obtain the catalyst.
In the present invention, the element a is a metal element, preferably selected from copper, iron, cobalt, nickel, or zinc, and more preferably an element Fe.
The inventor finds that when the element A is the element Fe, the catalyst is the Anderson type polyoxometallate taking Fe as the center, the Fe is cheaper, and the cost of the catalyst prepared by taking the Fe as the center is lower, and simultaneously, the inventor finds that the Anderson type polyoxometallate taking the Fe as the center can effectively improve the yield of the product and generates less waste water and waste salt in the preparation process of the 4-acyloxy-2-methyl-2-butenal.
In step 1-1, the element a-containing compound is selected from one of an element a-containing oxide, an inorganic salt and a hydroxide, preferably, the element a-containing compound is selected from one of ferric oxide, ferroferric oxide, ferric sulfate, ferrous sulfate and ferric hydroxide, and more preferably, the element a-containing compound is selected from ferric sulfate or ferrous sulfate.
The inorganic oxyacid is selected from ammonium molybdate, sodium molybdate, potassium molybdate, ammonium tungstate or sodium tungstate, preferably the inorganic oxyacid is selected from ammonium molybdate, sodium molybdate or sodium tungstate, more preferably the inorganic oxyacid is selected from ammonium molybdate.
The mass ratio of the compound containing the element A to the inorganic oxyacid is 1: (2-6), preferably, the mass ratio of the compound containing the element A to the inorganic oxyacid is 1: (2.5-5), and more preferably, the mass ratio of the compound containing the element A to the inorganic oxyacid is 1: (3-4.5). Tests show that when the mass ratio of the compound containing the element A to the inorganic oxyacid is 1: (2-6), the prepared catalyst has higher yield.
Before the reaction, the inorganic oxoacid is dissolved in a solvent, preferably water, and in the present invention, the amount of the solvent to be added is not particularly limited as long as the inorganic oxoacid can be completely dissolved. The mass ratio of the solvent to the inorganic oxyacid is preferably (15-20): 1, more preferably 16: 1.
Before adding the compound containing the element A, the inorganic oxyacid dissolved in the solvent needs to be heated, wherein the heating temperature is 80-120 ℃, preferably 90-110 ℃, and more preferably 100 ℃. The purpose of the heating is to clear the inorganic oxo acid dissolved in the solvent.
The element a-containing compound is dissolved in a solvent, which is preferably water, and the amount of the solvent to be added is not particularly limited as long as the iron-containing compound can be completely dissolved. The mass ratio of the solvent to the A element-containing compound is preferably (2-6): 1, more preferably (3-5): 1.
the addition mode of the compound containing the element A is preferably dropwise, and the dropwise addition can enable reactants to be in a starvation state all the time, further contributes to forward reaction and is beneficial to improvement of product yield.
The reaction is preferably carried out while stirring, and more preferably, the reaction is carried out after the addition of the element a-containing compound is completed, so that the stirring is more favorable for the reaction, and further contributes to the improvement of the product yield. The reaction temperature is 80-120 ℃, preferably 90-110 ℃, and more preferably 100 ℃. The stirring time is 0.5-5 h, preferably 1-3 h, and more preferably 1-2 h. Experiments show that the reaction temperature is 80-120 ℃, the stirring time is 0.5-5 h, the reaction is facilitated, and the catalyst yield is higher.
In step 1-2, the post-treatment comprises filtration, precipitation and drying. After the reaction was completed, filtration was performed to remove insoluble substances.
The precipitation mode is preferably standing or low-temperature stirring, and standing is carried out at room temperature for 1-5 days; the low-temperature stirring is carried out at 1-10 ℃, preferably 5-10 ℃, the solid precipitation can be accelerated by stirring, and the stirring time is 2-5 hours, preferably 4 hours. More preferably, the precipitation mode is standing, and tests show that the yield of the catalyst prepared by the standing mode is higher.
And (3) filtering after standing or stirring is finished, collecting precipitated solid, and recrystallizing the collected solid in deionized water at 70-90 ℃, preferably 80 ℃. And (4) recrystallizing for 1-3 times, wherein the aim of recrystallization is to purify the prepared product.
Drying is carried out after recrystallization, the drying preferably being vacuum drying.
Weighing the prepared catalyst, C5 chlorine ester and acetonitrile in water, and placing the catalyst, the chlorine ester and the acetonitrile in a container, wherein the mass ratio of the catalyst to the acetonitrile is 1: (5-50): (5-30), preferably, the mass ratio of the catalyst, the chlorine ester and the acetonitrile is 1: (5-40): (5-28), and more preferably, the mass ratio of the catalyst to the C5 chlorine ester to the acetonitrile is 1: (9-33): (7-26). The inventor finds that the addition amount of the catalyst can influence the yield of the finally prepared product, and when the mass ratio of the catalyst, the C5 chlorine ester and the acetonitrile is 1: (5-50): (5-30), the yield of 4-acyloxy-2-methyl-2-butenal is the highest.
And 2, carrying out reaction by using the substance prepared in the step 1.
Weighing the catalyst prepared in the step 1, the chloro-ester and the acetonitrile aqueous solution, placing the catalyst, the chloro-ester and the acetonitrile aqueous solution in a container, heating and reacting, wherein the container is preferably a four-mouth bottle.
Figure BDA0002709950910000071
The reaction is further added with an oxidizing agent, and in the invention, the oxidizing agent is selected from oxygen, hydrogen peroxide, tert-butyl peroxide or air, preferably oxygen or air, and more preferably oxygen. It has been found that when the oxidant is oxygen, the highest yield of product is obtained.
The reaction temperature is 50-90 ℃, preferably 60-80 ℃, more preferably 70-80 ℃, for example 75 ℃. The reaction time is 3-10 h, preferably 5-8 h, and more preferably 6-7 h.
The reaction temperature can influence the reaction rate and the product yield, and the inventor finds that when the reaction temperature is 50-90 ℃, the catalytic activity of the catalyst is the highest, the product can be obtained at a high yield on the premise of high preparation efficiency, and particularly, when the reaction temperature is 75 ℃, the product yield is high. The reaction time is adapted to the reaction temperature, when the reaction time is 3-10 hours, the reaction is completely carried out, and the product yield is high.
According to the invention, the reaction is preferably carried out under stirring, the stirring mode is preferably mechanical stirring, the stirring can further accelerate the reaction process and improve the preparation efficiency, and meanwhile, the reaction raw materials are fully mixed, so that the yield is improved.
And 3, carrying out post-treatment to obtain a final product.
The post-treatment of the invention comprises filtration, extraction, drying and desolventizing. After the reaction is finished, filtering, extracting, drying and desolventizing are carried out in sequence.
The filtration is preferably performed after the reaction is finished and the temperature is reduced, more preferably after the temperature is reduced to 15-25 ℃, for example, after the temperature is reduced to 20 ℃.
In the invention, the filtered filter residue is used for recovering the catalyst, and the recovered catalyst can be used for the next preparation, thereby not only reducing the cost, but also conforming to the green chemical concept. And collecting the filtrate and extracting.
The collected filtrate is added with an extracting agent for extraction, and the extracting agent is preferably ethyl acetate.
The extraction is preferably performed 1 to 5 times, and more preferably 3 times. When the extraction is carried out for 3 times, the yield of the product prepared by the preparation method is highest, and the preparation process is simplified.
After the extraction is finished, all organic phases are combined and dried, and the drying is preferably performed by adding anhydrous sodium sulfate. After the organic phase is dried, the subsequent desolventizing is more favorably carried out.
According to the invention, the desolventizing is preferably carried out under reduced pressure, and the C5 aldehyde ester is obtained after the desolventizing. The yield of the C5 aldehyde ester prepared by the preparation method can reach 80-90%.
The second aspect of the present invention is to provide 4-acyloxy-2-methyl-2-butenal obtained by the method for producing 4-acyloxy-2-methyl-2-butenal according to the first aspect of the present invention.
The invention has the following beneficial effects:
(1) the preparation method of the 4-acyloxy-2-methyl-2-butenal adopts Anderson type polyoxometallate taking Fe as a center as a catalyst, and has the advantages of low cost, good catalytic activity, mild catalytic conditions, excellent stability and durability and the like;
(2) the preparation method of the 4-acyloxy-2-methyl-2-butenal disclosed by the invention has the advantages that less waste water and waste salt are generated in the preparation process, and the catalyst can be recycled, so that the preparation method conforms to the concept of green chemical industry;
(3) the preparation method of the 4-acyloxy-2-methyl-2-butenal has the advantages of low preparation cost, simple preparation process and high industrial amplification feasibility;
(4) the product yield of the preparation method of the 4-acyloxy-2-methyl-2-butenal is high and can reach 80-90%.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
Example 1 catalyst preparation
500mL four-necked flask, 18.73g (NH)4)6Mo7O24·4H2O (15mmol) was dissolved in 299.60g of deionized water by heating to 100 ℃. Simultaneously weighing Fe2(SO4)3(11.5mmol) was dissolved in 23.30g of deionized water and slowly added dropwise to boiling (NH)4)6Mo7O24The solution was stirred thoroughly for 1h after dropping. After the reaction, insoluble matter was filtered, the filtrate was allowed to stand at room temperature for two days, a yellowish white solid was precipitated, the solid was collected by filtration, recrystallized twice in deionized water at 80 ℃ and dried under vacuum to obtain 13.69g of a white solid (11.4mmol, hereinafter referred to as an iron catalyst) in a yield of 98.7%. (NH)4)3[FeMo6O18(OH)6]·7H2O。IR:3165(νas NH,m),1640.57(δOH m),1400.95(δNH,s),946.05(νMo＝O,vs),845.10(νMo＝O,vs),649.37(νMo-O-Mo,vs),574.83(νMo-O-Mo,w)cm-1。
Example 2 catalyst preparation
A2000 mL four-necked flask was charged with 62.42g (NH)4)6Mo7O24·4H2O (50mmol) was dissolved in 998.67g of deionized water by heating to 100 ℃. Then 18.36gFe was weighed2(SO4)3(45.5mmol) was dissolved in 55.08g of deionized water and slowly added dropwise to boiling (NH)4)6Mo7O24The solution was stirred thoroughly for 1.5h after dropping. After the reaction, insoluble matter was filtered, the filtrate was stirred at 5 ℃ for 4 hours, a yellowish white solid precipitated, the solid was collected by filtration, recrystallized twice in 80 ℃ deionized water, and dried under vacuum to give 54.08g of a white solid iron catalyst (45mmol) with a yield of 99.0%.
Example 3
A500 mL four-necked flask was charged with 6.01g of the iron catalyst (5mmol) obtained in example 1, 87.42g of chloroacetate (0.5mol), 78.68g of acetonitrile and 78.68g of water, and the mixture was stirred at 70 ℃ for 6 hours under an oxygen atmosphere. After the reaction is finished, the temperature is reduced to 20 ℃, the catalyst is recovered from filter residues, the organic phase is collected by separating filtrate, and 39.34g of ethyl acetate is added into the water phase for extraction for three times. All organic phases were combined, dried over anhydrous sodium sulfate, and desolventized under reduced pressure to give 61.27g of crude C5 carboxaldehyde acetate with a yield of 86.2%.
Example 4
A1000 mL four-necked flask was charged with 27.04g of the iron catalyst (23mmol) obtained in example 1, 262.27g of chloroacetate (1.5mol), 209.82g of acetonitrile and 209.82g of water, and the mixture was heated to 75 ℃ under an oxygen atmosphere and stirred for 7 hours. After the reaction is finished, the temperature is reduced to 25 ℃, the catalyst is recovered from filter residues, the organic phase is collected by separating filtrate, and 104.91g of ethyl acetate is added into the water phase for extraction for three times. All organic phases were combined, dried over anhydrous sodium sulfate and desolventized under reduced pressure to obtain 189.77g of crude C5 aldehyde acetate with 89.0% yield.
Example 5
A500 mL four-necked flask was charged with 4.81g of the iron catalyst (4mmol) obtained in example 2, 75.97g of chloropropionate (0.4mol), 53.18g of acetonitrile and 53.18g of water, and the mixture was heated to 70 ℃ under an oxygen atmosphere and stirred for 7 hours. After the reaction is finished, the temperature is reduced to 20 ℃, the catalyst is recovered from filter residues, the organic phase is collected by separating filtrate, and 26.59g of ethyl acetate is added into the water phase for extraction for three times. All the organic phases were combined, dried over anhydrous sodium sulfate, and desolventized under reduced pressure to give 52.66g of crude C5 aldehyde propionate in 84.3% yield.
Example 6
A1000 mL four-necked flask was charged with 8.41g of the iron catalyst (7mmol) obtained in example 2, 270.21g of chloropalmitate (0.7mol), 216.17g of acetonitrile and 216.17g of water, and the mixture was heated to 75 ℃ under an oxygen atmosphere and stirred for 6 hours. After the reaction is finished, the temperature is reduced to 20 ℃, the catalyst is recovered from filter residues, the organic phase is collected by separating filtrate, and 108.08g of ethyl acetate is added into the water phase for extraction for three times. All the organic phases are combined, dried by anhydrous sodium sulfate and desolventized under reduced pressure to obtain 203.80g of crude C5 aldehyde palmitate with the yield of 86.0 percent.
Comparative example
Comparative example 1 copper catalyst preparation
1000mL four-necked flask, 37.45g (NH) was added4)6Mo7O24·4H2O (30mmol) was dissolved in 561.75g of deionized water by heating to 100 ℃. Simultaneously weighing CuSO4(43.4mmol) was dissolved in 139.91g of deionized water and slowly added dropwise to boiling (NH)4)6Mo7O24After dropping, the solution was stirred sufficiently for 1 hour, the reaction was stopped, insoluble matter was filtered, the filtrate was allowed to stand at room temperature for two days, a blue solid was precipitated, the solid was collected by filtration and dried under vacuum to obtain 51.70g of a product (26.4mmol, hereinafter referred to as a copper catalyst) in a yield of 60.8%.
(NH4)4[CuMo6O18(OH)6]·5H2O。IR:1631.65(δOH m),1400.56(δNH,s),931.62(νMo＝O,vs),897.66(νMo＝O,vs),640.18(νMo-O-Mo,vs),577.68(νMo-O-Mo,w)cm-1。
Comparative example 2
A1000 mL four-necked flask was charged with 27.04g of the copper catalyst obtained in comparative example 1, 262.27g of chloroacetate (1.5mol), 209.82g of acetonitrile and 209.82g of water, and the mixture was stirred at 75 ℃ for 7 hours under an oxygen atmosphere. After the reaction is finished, the temperature is reduced to 25 ℃, the catalyst is recovered from filter residues, the organic phase is collected by separating filtrate, and 104.91g of ethyl acetate is added into the water phase for extraction for three times. All organic phases were combined, dried over anhydrous sodium sulfate and desolventized under reduced pressure to obtain 149.26g of crude C5 aldehyde acetate with a yield of 75%.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. A preparation method of 4-acyloxy-2-methyl-2-butenal is characterized by comprising the following steps:
step 1, preparing raw materials;
step 2, carrying out reaction by using the substance prepared in the step 1;
and 3, carrying out post-treatment to obtain a final product.
2. The production method according to claim 1, wherein in step 1, the starting materials comprise an aqueous acetonitrile solution and C5 chloro ester;
the C5 chloro ester is selected from one or more of chloro acetate, chloro propionate, chloro palmitate, tert-butyl chloroacetate, isopropyl chloroformate, ethyl trichloroacetate, n-butyl chloroacetate and isobutyl chloroacetate.
3. The production method according to claim 2, wherein, in step 1,
the preparation of the raw materials also comprises the preparation of a catalyst;
the catalyst is preferably an Anderson type polyoxometallate;
more preferably, the catalyst is prepared by the steps of:
step 1-1, adding a compound containing an element A into inorganic oxyacid for reaction;
and step 1-2, carrying out post-treatment after the reaction is finished to obtain the catalyst.
4. The production method according to claim 3, wherein, in step 1-1,
the element A is a metal element, preferably selected from iron, copper, cobalt, nickel or zinc, and more preferably an element Fe.
5. The production method according to claim 4, wherein, in step 1-1,
the A element-containing compound is selected from one of an A element-containing oxide, an inorganic salt and a hydroxide;
the inorganic oxyacid is selected from ammonium molybdate, sodium molybdate, potassium molybdate, ammonium tungstate or sodium tungstate.
6. The production method according to claim 3, wherein, in step 1-1,
the mass ratio of the compound containing the element A to the inorganic oxyacid is 1: (2-6);
the reaction temperature is 80-120 ℃, the reaction is carried out under stirring, and the stirring time is 0.5-5 h.
7. The production method according to claim 3, wherein in step 1, the prepared catalyst, the chloro ester and the aqueous acetonitrile solution are weighed and placed in a vessel;
the mass ratio of the catalyst to the C5 chloro ester to the acetonitrile is 1: (5-50): (5-30);
the mass ratio of acetonitrile to water is 1: (0.5-2).
8. The production method according to claim 1, wherein, in step 2,
the reaction temperature is 50-90 ℃, and the reaction time is 3-10 h.
9. The production method according to claim 1, wherein, in step 3,
the post-treatment comprises filtration, extraction, drying and desolventizing;
adding an extracting agent into the filtrate for extraction, wherein the extracting agent is preferably ethyl acetate;
drying is preferably carried out by adding anhydrous sodium sulfate.
10. 4-acyloxy-2-methyl-2-butenal, characterized in that the 4-acyloxy-2-methyl-2-butenal is produced by the production method according to any one of claims 1 to 9.
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