CN110734374B - Preparation method of high-yield 2-methyl-4-acetoxyl-2-butenal - Google Patents

Preparation method of high-yield 2-methyl-4-acetoxyl-2-butenal Download PDF

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CN110734374B
CN110734374B CN201810803347.8A CN201810803347A CN110734374B CN 110734374 B CN110734374 B CN 110734374B CN 201810803347 A CN201810803347 A CN 201810803347A CN 110734374 B CN110734374 B CN 110734374B
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CN110734374A (en
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周立山
戚聿新
吕强三
于大伟
鞠立柱
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Xinfa Pharmaceutical Co Ltd
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    • 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
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Abstract

The invention provides a preparation method of high-yield 2-methyl-4-acetoxyl-2-butenal (I). the invention utilizes 2, 5-dihydrofuran (II) and synthesis gas as raw materials, prepares 3-formyl tetrahydrofuran (III) through hydroformylation reaction under the action of a catalyst, then reacts with an acetylation reagent under the action of the catalyst to prepare 2-formyl-4-acetoxyl-1-butene (IV), and then obtains the 2-methyl-4-acetoxyl-2-butenal (I) through double bond isomerization under the action of the catalyst. The method has the advantages of cheap and easily obtained raw materials and low cost; the process flow is short, the reaction is easy to realize, the operation is safe and simple, the waste water generation amount is small, and the method is green and environment-friendly; the reaction intermediate product is stable, the reaction activity is proper, the reaction selectivity is high, the side reaction is less, the yield is high, and the method is suitable for industrial production.

Description

Preparation method of high-yield 2-methyl-4-acetoxyl-2-butenal
Technical Field
The invention relates to a preparation method of high-yield 2-methyl-4-acetoxyl-2-butenal, belonging to the technical field of medical chemistry.
Background
2-methyl-4-acetoxy-2-butenal (I) is a key intermediate for preparing vitamin A acetate and various carotenoids, and has the following structural formula:
Figure BDA0001737614340000011
the synthesis method of 2-methyl-4-acetoxyl-2-butenal is summarized as follows according to the difference of the used main raw materials and the involved unit reactions:
1. 1, 1-dimethoxy acetone method
US4256878 and US5453547 take 1, 1-dimethoxyacetone as raw material, acetylize to obtain 3-methyl-3-hydroxy-4, 4-dimethoxy-1-butyne, selectively hydrogenate with hydrogen to obtain 3-methyl-3-hydroxy-4, 4-dimethoxy-1-butene, esterify with acetic anhydride to obtain 3-methyl-3-acetoxy-4, 4-dimethoxy-1-butene, double bond isomerize under the action of Cu catalyst to obtain 2-methyl-4-acetoxy-1, 1-dimethoxy-2-butene, hydrolyze to remove acetal protecting group to prepare 2-methyl-4-acetoxy-2-butenal, the reaction sequence is depicted as scheme 1 below.
Figure BDA0001737614340000012
Chinese patent document CN102311339A utilizes grignard reagent condensation and acetyl esterification of 1, 1-dimethoxyacetone and vinyl bromide or vinyl chloride to obtain 3-methyl-3-acetoxy-4, 4-dimethoxy-1-butene, which undergoes hydrolysis reaction to obtain 2-methyl-2-acetoxy-3-butene-1-aldehyde, and then undergoes rearrangement reaction under the catalytic action of palladium catalyst or cuprous chloride to obtain 2-methyl-4-acetoxy-2-butenal, the total yield of the last two steps is 73.7-78.1%, and the reaction process is described as the following synthetic route 2.
Figure BDA0001737614340000021
The 1, 1-dimethoxyacetone used as the raw material of the 1, 1-dimethoxyacetone method has high price, is not easy to obtain and has high cost; the tertiary alcohol intermediate 3-methyl-3-hydroxy-4, 4-dimethoxy-1-butene in the synthetic route 1 has low reaction activity, low selectivity of esterification reaction with acetic anhydride and low yield; the synthesis route 2 needs to prepare a Grignard reagent, has high operation requirement and large wastewater amount; in conclusion, the 1, 1-dimethoxyacetone method is not suitable for industrial application.
2. Ethylene oxide process
U.S. Pat. No. 4,487,3362 describes the following synthetic scheme 3, in which ethylene oxide is used as a raw material, and acetic acid is subjected to a ring-opening reaction to obtain 2-acetoxyethanol, and then the 2-acetoxyethanol is oxidized by oxygen under the action of a silver catalyst to prepare 2-acetoxyacetaldehyde, and then the 2-acetoxyacetaldehyde and propionaldehyde are subjected to an aldol condensation reaction to prepare 2-methyl-4-acetoxy-2-butenal.
Figure BDA0001737614340000022
In the synthetic route 3, under the action of a silver catalyst, oxygen is used for oxidizing 2-acetoxyl ethanol to prepare 2-acetoxyl acetaldehyde, so that the reaction selectivity is poor, more side reactions are caused by further oxidation, and the 2-acetoxyl acetaldehyde has poor stability, is difficult to store and has poor operability; in addition, the aldol condensation reaction has more self-condensation side reactions of propionaldehyde, is difficult to separate and purify and is not beneficial to industrial application.
Chinese patent document CN103467287A describes the following synthetic scheme 4 as a reaction process, in which ethylene oxide is used as a raw material, and undergoes a substitution reaction with acrolein under the catalysis of a phosphine reagent to obtain 2-formyl-4-hydroxy-1-butene, and then undergoes an esterification reaction with an acetylation reagent to obtain 2-formyl-4-acetoxy-1-butene, and then undergoes palladium-catalyzed double bond isomerization to obtain 2-methyl-4-acetoxy-2-butenal, with a total yield of 40.2%.
Figure BDA0001737614340000023
Figure BDA0001737614340000031
In the synthetic route 4, a large amount of phosphine reagent catalyst is needed for the reaction of ethylene oxide and acrolein, the cost is high, the toxicity is high, the smell is large, the operation environment is poor, and the industrial production is not facilitated.
3. Isoprene process
U.S. patent documents US4175204 and US5424478, which describe the following synthetic scheme 5, use isoprene as a raw material, and obtain a mixture of 3-methyl-3-hydroxy-4-chloro-1-butene and 1-chloro-2-methyl-4-hydroxy-2-butene through addition reaction with sodium hypochlorite, then prepare 1-chloro-2-methyl-4-acetoxy-2-butene through esterification with acetic anhydride, and then obtain 2-methyl-4-acetoxy-2-butenal through oxidation with DMSO.
Figure BDA0001737614340000032
The synthetic route 5 has the advantages of large solvent demand, large wastewater quantity, lower DMSO oxidation yield, large odor of the byproduct, larger air pollution, poor repeatability, and generation of a large amount of wastewater, and is not beneficial to green and environment-friendly production.
Chinese patent document CN103012131A uses isoprene as raw material, and reacts with tert-butyl hypochlorite and acetic acid to obtain a mixture of 3-methyl-3-acetoxyl-4-chloro-1-butene and 1-chloro-2-methyl-4-hydroxy-2-butene, then the mixture is esterified with acetic anhydride to prepare 1-chloro-2-methyl-4-acetoxyl-2-butene, the 1-formyloxy-2-methyl-4-acetoxyl-2-butene is obtained by substitution reaction with potassium formate, 1-hydroxy-2-methyl-4-acetoxyl-2-butene is obtained by selective hydrolysis of formate, and then 2-methyl-4-acetoxyl-2-butenal is obtained by TEMPO catalytic oxygen oxidation, the overall yield was 70.5% and the reaction procedure is depicted as scheme 6 below.
Figure BDA0001737614340000033
The synthetic route 6 has long steps, complex operation, large amount of waste water and is not beneficial to environmental protection.
4. 1, 4-butenediol process
U.S. Pat. No. 4,4124619 uses 1, 4-butylene glycol as raw material, and is esterified with acetic anhydride to obtain 1, 4-diacetoxy-2-butene, which is then reacted with synthesis gas (CO, H2) under high pressure in the presence of rhodium catalyst to obtain 2-formyl-1, 4-diacetoxy butane, then the acetic acid is removed under acidic condition to obtain 2-formyl-4-acetoxy-1-butene, and the double bond isomerization is catalyzed by palladium to obtain 2-methyl-4-acetoxy-2-butenal, and the reaction process is described as the following synthetic route 7.
Figure BDA0001737614340000041
Although the synthetic route 7 has high atom economy, the 1, 4-diacetoxy-2-butene used in the hydroformylation reaction contains two ester functional groups, the substrate activity is low, a special ligand is required, the pressure in the reaction process is high (the pressure is 130-150 atm), the equipment requirement is high, and the method is not suitable for industrial simple and convenient operation.
In conclusion, the research and optimization of the green industrial preparation route of the 2-methyl-4-acetoxyl-2-butenal have important significance for the green production of products such as vitamin A acetate, various carotenoids and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of 2-methyl-4-acetoxyl-2-butenal with high yield. The method has the advantages of cheap and easily obtained raw materials and low cost; the process flow is short, the reaction is easy to realize, the operation is safe and simple, the waste water production amount is small, and the method is green and environment-friendly; the reaction intermediate product is stable, the reaction activity is proper, the reaction selectivity is high, the side reaction is less, the yield is high, and the method is suitable for industrial production.
Description of terms:
a compound of formula II: 2, 5-dihydrofuran (II);
a compound of formula III: 3-formyl tetrahydrofuran (iii);
a compound of formula IV: 2-formyl-4-acetoxy-1-butene (iv); ac in the structural formula represents acetyl;
a compound of formula I: 2-methyl-4-acetoxyl-2-butenal (I).
In the specification, the compound numbers are completely consistent with the structural formula numbers, have the same reference relationship, and are based on the structural formula of the compound.
The technical scheme of the invention is as follows:
a method for preparing 2-methyl-4-acetoxyl-2-butenal (I) comprises the following steps:
(1) preparing a compound of formula iii by subjecting a compound of formula ii and synthesis gas to a hydroformylation reaction;
Figure BDA0001737614340000042
(2) preparing a compound of formula iv by reacting a compound of formula iii with an acetylating agent;
Figure BDA0001737614340000051
(3) 2-methyl-4-acetoxy-2-butenal (I) is prepared by double bond isomerization of the compound of formula IV.
Preferably, according to the invention, in step (1), the hydroformylation of the compound of formula II and synthesis gas is carried out in solvent A, under the action of a rhodium-based catalyst or a rhodium-based catalyst and a cocatalyst.
Preferably, the solvent A is one or the combination of more than two of toluene, xylene, benzene, n-hexane, cyclohexane, n-heptane or petroleum ether with the boiling range of 60-90 ℃; the mass ratio of the solvent A to the compound shown in the formula II is (0-15) to 1; further preferably, the mass ratio of the solvent A to the compound of the formula II is (2-8): 1.
Preferably, the rhodium-based catalyst is one or a combination of two or more of tris (triphenylphosphine) carbonyl rhodium hydride, dicarbonyl (acetylacetone) rhodium, dicarbonyl rhodium chloride and tris (triphenylphosphine) rhodium chloride; the mass of the rhodium catalyst is 0.002-5.0% of that of the compound in the formula II; more preferably, the mass of the rhodium-based catalyst is 0.005-1.5% of the mass of the compound of formula II; most preferably, the mass of the rhodium-based catalyst is 0.5 to 1% of the mass of the compound of formula II.
Preferably, the cocatalyst is a trialkyl phosphine or triaryl phosphine, preferably triphenylphosphine or tributylphosphine; the mass of the cocatalyst is 0.02-5.0% of the mass of the compound of the formula II; further preferably, the mass of the cocatalyst is 0.05-1.5% of the mass of the compound of formula II; most preferably, the mass of the cocatalyst is 0.5-1% of the mass of the compound of formula II.
According to a preferred embodiment of the present invention, the synthesis gas in step (1) comprises CO and H as the main components2CO and H2The volume ratio of (1: 1) and the pressure of the synthesis gas in the system is 0.5-20.0 MPa; preferably, the pressure of the synthesis gas in the system is 2.0-10.0 MPa.
Preferably, according to the invention, in step (1), the hydroformylation reaction temperature is 40 to 150 ℃; preferably, the hydroformylation reaction temperature is 70-110 ℃. The hydroformylation reaction time is 2 to 10 hours; preferably, the hydroformylation reaction time is 4 to 7 hours.
Preferably, according to the invention, in step (2), the reaction of the compound of formula III with the acetylating agent is carried out in solvent B, under the action of catalyst C.
Preferably, the solvent B is one or the combination of more than two of toluene, xylene, benzene, n-hexane, cyclohexane, n-heptane or petroleum ether with the boiling range of 60-90 ℃; the mass ratio of the solvent B to the compound shown in the formula III is (2-15) to 1; further preferably, the mass ratio of the solvent B to the compound of the formula III is (3-10): 1.
Preferably, the catalyst C is one or the combination of more than two of benzene sulfonic acid, p-methyl benzene sulfonic acid, methyl sulfonic acid or concentrated sulfuric acid with the mass concentration of 70-98%; the mass of the catalyst C is 0.02-2.0% of that of the compound shown in the formula III; further preferably, the mass of catalyst C is 0.1-1.0% of the mass of the compound of formula III.
Preferably, in step (2), the acetylation reagent is acetic acid, and the water content of the acetic acid is 0.1-0.5 wt%; the molar ratio of the acetylation reagent to the compound of formula III is (1.0-3.2): 1; preferably, the molar ratio of the acetylating agent to the compound of formula III is (1.3-2.0): 1.
Preferably, according to the invention, in step (2), the reaction temperature of the compound of formula III and the acetylating agent is 60-140 ℃; preferably, the reaction temperature of the compound of formula III and the acetylating agent is 100-120 ℃. The reaction time of the compound shown in the formula III and the acetylation reagent is 1-10 hours; preferably, the reaction time of the compound of formula III and the acetylating agent is from 3 to 6 hours.
According to a preferred embodiment of the invention, in step (3), the double bond isomerization of the compound of formula IV is carried out in a solvent D in the presence of hydrogen, in the presence of a catalyst E and of a poisoning agent.
Preferably, the solvent D is toluene or xylene; the mass ratio of the solvent D to the compound shown in the formula IV is (1-10) to 1; further preferably, the mass ratio of the solvent D to the compound of the formula IV is (2-5): 1.
Preferably, before introducing the hydrogen into the system, the inert gas is introduced to the system until the pressure of the system is 5.0-5.2MPa, and then the hydrogen is introduced to the system until the pressure of the system is 5.5-6.0 MPa. The purpose of introducing hydrogen is as follows: because the isomerization process involves hydrogenation of carbon-carbon double bonds and dehydrogenation of carbon-carbon single bonds, equilibrium is eventually reached, resulting in isomerization of the carbon-carbon double bonds to between the 2, 3-position carbon atoms; the hydrogen amount is not too large, and a poisoning agent tetramethyl thiourea is needed to avoid the hydrogenation of carbon-carbon double bonds in the target product.
Preferably, the catalyst E is palladium carbon with the mass content of palladium being 5%; the mass of the catalyst E is 1.0-10.0% of that of the compound shown in the formula IV; further preferably, the mass of the catalyst E is 1.0 to 4.0% of the mass of the compound of formula IV.
Preferably, the poisoning agent is a thiol, thioether, or thiourea derivative; further preferably, the thiol has the formula CnH2n+1SH (4 ≦ n ≦ 12), preferably butylmercaptan or octylmercaptan; the thioether has the general formula CnH2n+1SCmH2m+1(4 ≦ n ≦ 12, 4 ≦ m ≦ 12, n and m are the same or different), preferably butyl sulfide or di-n-octyl sulfide; the thiourea derivative is tetramethyl thiourea.
Preferably, the mass of the poisoning agent is 1.0-10.0% of the mass of the catalyst E; more preferably, the mass of the poisoning agent is 2.0 to 5.0% of the mass of the catalyst E.
Preferably, according to the invention, in the step (3), the double bond isomerization reaction temperature is 60-140 ℃; preferably, the double bond isomerization reaction temperature is 90-110 ℃. The double bond isomerization reaction time is 3-10 hours; preferably, the double bond isomerization reaction time is 5 to 8 hours.
The present invention is depicted as scheme 8 below:
Figure BDA0001737614340000061
the invention has the technical characteristics and beneficial effects that:
1. the invention provides a preparation method of 2-methyl-4-acetoxyl-2-butenal (I), which comprises the steps of preparing 3-formyl tetrahydrofuran (III) by hydroformylation reaction of 2, 5-dihydrofuran (II) and synthesis gas under the action of a catalyst, then preparing 2-formyl-4-acetoxyl-1-butene (IV) by reaction of the 3-formyl tetrahydrofuran (III) and an acetylation reagent under the action of the catalyst, and then obtaining 2-methyl-4-acetoxyl-2-butenal (I) by double bond isomerization under the action of the catalyst.
2. The method has the advantages of cheap and easily obtained raw materials and low cost; the method is simple and short in process flow, and the target product can be prepared only by 3 steps; the reaction does not need high pressure, the reaction is easy to realize, the operation is safe and simple, the waste water generation amount in the reaction process is small, and the method is green and environment-friendly; the reaction intermediate has good stability and proper reaction activity, does not need special coordination, the used raw material 2, 5-dihydrofuran does not contain carbonyl functional groups, the complexation of carbonyl and rhodium catalysts is avoided, the target hydroformylation reaction is easy to carry out, and the used rhodium catalysts have small dosage, low reaction pressure and easy operation; the method has the advantages of high atom economy, high reaction selectivity, less side reaction, high yield and total yield of 90 percent, and is suitable for green industrial production.
3. The 3-formyl tetrahydrofuran (III) and the acetylation reagent are subjected to esterification reaction under the action of a catalyst and a trace amount of water (provided by the acetylation reagent) to obtain the 2-formyl-1, 4-diacetyloxybutane, and a molecule of acetic acid of the intermediate is easily removed to generate the 2-formyl-4-acetoxyl-1-butene (IV), so that the reaction is promoted to be carried out.
4. The raw material 2, 5-dihydrofuran used in the invention has high stability, does not contain carbonyl functional groups which are easy to complex with a hydroformylation reaction catalyst, and the hydroformylation reaction is easy to operate, the reaction pressure is low, and the obtained 3-formyl tetrahydrofuran has high selectivity and high yield; then, under the action of trace water and a catalyst, the 2-formyl-4-acetoxyl-1-butene is prepared by the reaction of an acetylation reagent, so that the stability of the product is ensured, and the hydrolysis is reduced; finally, under the action of a catalyst, obtaining 2-methyl-4-acetoxyl-2-butenal through double bond isomerization and rectification separation, and recovering unreacted 2-formyl-4-acetoxyl-1-butene for the next batch of isomerization reaction; the method has the advantages of appropriate reaction activity, easy reaction, specific selectivity, guaranteed stability of raw materials and products, and guarantee of high yield and high purity of target products.
Drawings
FIG. 1 is a gas chromatogram of 2-methyl-4-acetoxy-2-butenal (I) prepared in example 5.
FIG. 2 is a nuclear magnetic spectrum of 2-methyl-4-acetoxy-2-butenal (I) prepared in example 5.
Detailed Description
The present invention is described in detail below with reference to examples, but the present invention is not limited thereto.
The raw materials and reagents used in the examples are all commercially available products.
In the examples, "%" is a mass percentage unless otherwise specified.
The yields in the examples are all molar yields.
Example 1: preparation of 3-formyltetrahydrofuran (III)
Adding 70.0 g (1.0 mol) of 2, 5-dihydrofuran (II), 140 g of toluene, 0.5 g of tris (triphenylphosphine) carbonyl rhodium hydride and 0.5 g of triphenylphosphine into a 500 ml stainless steel autoclave with a stirring thermometer, sealing the autoclave, replacing the gas in the autoclave with nitrogen for 3 times, and then introducing a synthesis gas CO/H2(volume ratio 1:1), keeping the pressure of the synthesis gas at 4.0-5.0MPa, starting stirring, heating to 90-95 ℃, reacting for 4 hours, cooling, replacing for 3 times with nitrogen, removing the reaction liquid, washing the reaction kettle with 30 g of toluene, filtering to remove the catalyst, distilling the filtrate to recover the toluene, and distilling under reduced pressure (80-90 ℃/1-2mmHg) to obtain 94.6 g of 3-formyl tetrahydrofuran (III), wherein the yield is 94.6% and the gas phase purity is 99.7%.
Example 2: preparation of 3-formyltetrahydrofuran (III)
To a 500 ml stainless steel autoclave equipped with a stirrer and a thermometer, 70.0 g (1.0 mol) of 2, 5-dihydrofuran (II), 180 g of toluene, 0.5 g of tris (triphenylphosphine) rhodium chloride, 0.6 g of triphenylphosphine, and the mixture was sealedThe pressure kettle is used for replacing gas in the kettle for 3 times by nitrogen, and then synthetic gas CO/H is introduced2(volume ratio 1:1), keeping the pressure of the synthesis gas at 5.0-6.0MPa, starting stirring, heating to 100-105 ℃, reacting for 4 hours, cooling, replacing for 3 times with nitrogen, removing the reaction liquid, washing the reaction kettle with 30 g of toluene, filtering to remove the catalyst, distilling the filtrate to recover the toluene, and distilling under reduced pressure (80-90 ℃/1-2mmHg) to obtain 93.8 g of 3-formyl tetrahydrofuran (III), wherein the yield is 93.8 percent and the gas phase purity is 99.6 percent.
Example 3: preparation of 2-formyl-4-acetoxy-1-butene (IV)
Into a 500 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser were charged 200 g of toluene, 50.0 g (0.5 mol) of 3-formyltetrahydrofuran (III) prepared in example 1, 48.0 g (0.8 mol) of acetic acid, 0.20 g of p-toluenesulfonic acid, and the reaction was stirred at 110 ℃ and 112 ℃ for 5 hours. Cooling to 20-25 deg.c, changing into distillation system, distilling to recover toluene and excess acetic acid, then changing into high vacuum reduced pressure distillation (85-100 deg.c/1-2 mmHg) to obtain 68.5 g 2-formyl-4-acetoxy-1-butene (iv), yield is 96.5%, gas phase purity is 99.3%.
Example 4: preparation of 2-formyl-4-acetoxy-1-butene (IV)
Into a 500 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser were charged 200 g of toluene, 50.0 g (0.5 mol) of 3-formyltetrahydrofuran (III) prepared in example 2, 48.0 g (0.8 mol) of acetic acid, 0.15 g of benzenesulfonic acid, and the reaction was stirred at 100 ℃ and 105 ℃ for 6 hours. The reaction mixture was cooled to 20 to 25 ℃ and the distillation system was changed to recover toluene and excess acetic acid by distillation, followed by high vacuum distillation under reduced pressure (85-100 ℃ C./1-2 mmHg) to give 67.9 g of 2-formyl-4-acetoxy-1-butene (IV) in 95.6% yield and 99.2% purity in the vapor phase.
Example 5: preparation of 2-methyl-4-acetoxyl-2-butenal (I)
71.0 g (0.5 mol) of 2-formyl-4-acetoxyl-1-butene (IV) prepared by the method of example 3, 150 g of toluene, 1.2 g of 5wt% palladium carbon, 0.04 g of tetramethylthiourea are added into a 500 ml stainless steel autoclave connected with a stirring thermometer, the pressure kettle is sealed, the gas in the autoclave is replaced by nitrogen for 3 times, the temperature is increased to 105 ℃ of 100- -acetoxy-2-butenal (I) in a yield of 98.6% (based on the compound IV participating in the reaction).
Fig. 1 is a gas chromatogram of the product obtained in this example, and it can be seen from fig. 1 that the gas purity of the product obtained in this example is 98.9%.
The nuclear magnetic spectrum of the product obtained in this example is shown in fig. 2, and the nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3):δppm
1.76(s,3H),2.09(s,3H),4.86-4.88(d,2H),6.45-6.49(t,1H),9.42(s,1H)，
as can be seen from the above, the product obtained by the invention is the target product 2-methyl-4-acetoxyl-2-butenal (I).
Example 6: preparation of 2-methyl-4-acetoxyl-2-butenal (I)
71.0 g (0.5 mol) of 2-formyl-4-acetoxyl-1-butene (IV) prepared by the method of example 4, 150 g of toluene, 1.2 g of 5wt% palladium carbon and 0.04 g of di-n-octyl sulfide are added into a 500 ml stainless steel autoclave connected with a stirring thermometer, the pressure kettle is sealed, the gas in the autoclave is replaced by nitrogen for 3 times, the temperature is increased to 105 ℃ of 100- Acetoxy-2-butenal (I) in 97.0% yield (based on the compound IV participating in the reaction) and 98.8% purity in the gas phase.
Comparative example 1: preparation of 3-formyltetrahydrofuran (III)
Adding 70.0 g (1.0 mol) of 2, 5-dihydrofuran (II), 140 g of toluene and 0.5 g of tris (triphenylphosphine) carbonyl rhodium hydride into a 500 ml stainless steel autoclave with a stirring thermometer, sealing the autoclave, replacing the gas in the autoclave with nitrogen for 3 times, and then introducing a synthesis gas CO/H2(volume ratio 1:1), keeping the pressure of the synthesis gas at 4.0-5.0MPa, starting stirring, heating to 90-95 ℃, reacting for 5 hours, cooling, replacing 3 times with nitrogen, removing the reaction liquid, washing the reaction kettle with 30 g of toluene, filtering to remove the catalyst, distilling the filtrate to recover toluene and the raw material 2, 5-dihydrofuran, and distilling under reduced pressure (80-90 ℃/1-2mmHg) to obtain 62.3 g of 3-formyltetrahydrofuran (III), wherein the yield is 62.3 percent and the gas phase purity is 97.2 percent.
The comparative example 1 shows that the addition of the cocatalyst is beneficial to ensuring the stability of the main catalyst, reducing the decomposition of the main catalyst and facilitating the reaction.
Comparative example 2: preparation of 2-methyl-4-acetoxyl-2-butenal (I)
71.0 g (0.5 mol) of 2-formyl-4-acetoxyl-1-butene (IV) prepared by the method of example 3, 150 g of toluene, 1.2 g of 5wt% palladium carbon are added into a 500 ml stainless steel autoclave connected with a stirring thermometer, the pressure kettle is sealed, the gas in the kettle is replaced by nitrogen for 3 times, the temperature is increased to 100-, then introducing hydrogen until the pressure in the kettle is 6.5-7.0MPa, stirring and reacting for 6 hours at the internal temperature of 100-, cooling, replacing 3 times with nitrogen, removing reaction liquid, washing the reaction kettle with 30 g of toluene, filtering to remove the catalyst, distilling the filtrate to recover the toluene, rectification under reduced pressure (75-105 ℃ C./1-2 mmHg) gave 72 g of 2-methyl-4-acetoxyn-butyraldehyde.
The comparative example 2 shows that the appropriate hydrogen introduction amount and the addition of the poisoning agent tetramethylthiourea and the like are beneficial to avoiding the conversion of the carbon-carbon double bond hydrogenation into the saturated carbon-carbon single bond.

Claims (12)

1. A preparation method of 2-methyl-4-acetoxyl-2-butenal (I) comprises the following steps:
(1) preparing a compound of formula iii by subjecting a compound of formula ii and synthesis gas to a hydroformylation reaction;
the hydroformylation reaction of the compound shown in the formula II and synthesis gas is carried out in a solvent A under the action of a rhodium catalyst and a cocatalyst; the rhodium catalyst is one or the combination of more than two of tris (triphenylphosphine) carbonyl rhodium hydride, dicarbonyl (acetylacetone) rhodium, dicarbonyl rhodium chloride or tris (triphenylphosphine) rhodium chloride; the cocatalyst is trialkyl phosphine or triaryl phosphine;
Figure 702034DEST_PATH_IMAGE001
Ⅱ Ⅲ
(2) preparing a compound of formula iv by reacting a compound of formula iii with an acetylating agent;
the reaction of the compound of formula III and an acetylation reagent is carried out in a solvent B under the action of a catalyst C; the acetylation reagent is acetic acid; the mass of the catalyst C is 0.02-2.0% of that of the compound shown in the formula III; the catalyst C is one or the combination of more than two of benzene sulfonic acid, p-methyl benzene sulfonic acid or methyl sulfonic acid;
Figure 747350DEST_PATH_IMAGE002
Ⅳ
(3) preparing 2-methyl-4-acetoxy-2-butenal (I) by double bond isomerization of the compound of formula IV;
Figure 408139DEST_PATH_IMAGE003
Ⅰ
the double bond isomerization of the compound shown in the formula IV is carried out in a solvent D in the presence of hydrogen under the action of a catalyst E and a poisoning agent; the catalyst E is palladium carbon with the mass content of palladium being 5 percent; the poisoning agent is mercaptan, thioether or tetramethyl thiourea; before introducing hydrogen into the system, firstly introducing inert gas until the pressure of the system is 5.0-5.2MPa, and then introducing hydrogen until the pressure of the system is 5.5-6.0 MPa.
2. The process for the preparation of 2-methyl-4-acetoxy-2-butenal (i) according to claim 1, wherein the step (1) comprises one or more of the following conditions:
a. the solvent A is one or the combination of more than two of toluene, xylene, benzene, normal hexane, cyclohexane, normal heptane or petroleum ether with the boiling range of 60-90 ℃; the mass ratio of the solvent A to the compound shown in the formula II is (2-8) to 1;
b. the mass of the rhodium catalyst is 0.002-5.0% of that of the compound in the formula II;
c. the cocatalyst is triphenylphosphine or tributylphosphine; the mass of the cocatalyst is 0.02-5.0% of the mass of the compound of the formula II.
3. The process for the preparation of 2-methyl-4-acetoxy-2-butenal (i) according to claim 2, comprising one or more of the following conditions:
a. the mass of the rhodium catalyst is 0.005-1.5% of that of the compound shown in the formula II;
b. the mass of the cocatalyst is 0.05-1.5% of the mass of the compound of the formula II.
4. The process for the preparation of 2-methyl-4-acetoxy-2-butenal (i) according to claim 1, wherein the step (1) comprises one or more of the following conditions:
a. the main components of the synthesis gas are CO and H2CO and H2The volume ratio of (1: 1) and the pressure of the synthesis gas in the system is 0.5-20.0 MPa;
b. the hydroformylation reaction temperature is 90-110 ℃.
5. The process for producing 2-methyl-4-acetoxy-2-butenal (I) according to claim 4, wherein the pressure of the synthesis gas in the system is from 2.0 to 10.0 MPa.
6. The process for the preparation of 2-methyl-4-acetoxy-2-butenal (i) according to claim 1, wherein the step (2) comprises one or more of the following conditions:
a. the solvent B is one or the combination of more than two of toluene, xylene, benzene, normal hexane, cyclohexane, normal heptane or petroleum ether with the boiling range of 60-90 ℃; the mass ratio of the solvent B to the compound shown in the formula III is (2-15) to 1;
b. the mass of the catalyst C is 0.1 to 1.0 percent of the mass of the compound shown in the formula III.
7. The process for producing 2-methyl-4-acetoxy-2-butenal (I) according to claim 6, wherein the mass ratio of the solvent B to the compound of the formula III is (3-10): 1.
8. The process for the preparation of 2-methyl-4-acetoxy-2-butenal (i) according to claim 1, wherein the step (2) comprises one or more of the following conditions:
a. the water content of the acetic acid is 0.1-0.5 wt%; the molar ratio of the acetylation reagent to the compound of formula III is (1.0-3.2): 1;
b. the reaction temperature of the compound of the formula III and the acetylation reagent is 100-120 ℃.
9. The process for the preparation of 2-methyl-4-acetoxy-2-butenal (i) according to claim 8, wherein the molar ratio of the acetylating agent to the compound of formula iii is (1.3-2.0): 1.
10. The process for the preparation of 2-methyl-4-acetoxy-2-butenal (i) according to claim 1, wherein the step (3) comprises one or more of the following conditions:
a. the solvent D is toluene or xylene; the mass ratio of the solvent D to the compound shown in the formula IV is (1-10) to 1;
b. the mass of the catalyst E is 1.0-10.0% of that of the compound shown in the formula IV;
c. the thiol has the formula CnH2n+1SH, 4 ≦ n ≦ 12; the thioethers have the general formula CnH2n+1SCmH2m+14 < n < 12, 4 < m < 12, n and m being the same or different;
d. the mass of the poisoning agent is 1.0-10.0% of that of the catalyst E.
11. The process for the preparation of 2-methyl-4-acetoxy-2-butenal (i) according to claim 10, comprising one or more of the following conditions:
a. the mass ratio of the solvent D to the compound shown in the formula IV is (2-5) to 1;
b. the mass of the catalyst E is 1.0-4.0% of that of the compound shown in the formula IV;
c. the mercaptan is butanethiol or octanethiol; the thioether is butyl thioether or di-n-octyl thioether;
d. the mass of the poisoning agent is 2.0-5.0% of the mass of the catalyst E.
12. The process for producing 2-methyl-4-acetoxy-2-butenal (I) according to claim 1, wherein the double bond isomerization reaction temperature in the step (3) is 90 to 110 ℃.
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