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CN112321421A - Preparation method of 1-acetoxyl-4-chloro-3-methyl-2-butene - Google Patents

Preparation method of 1-acetoxyl-4-chloro-3-methyl-2-butene Download PDF

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CN112321421A
CN112321421A CN202011052333.0A CN202011052333A CN112321421A CN 112321421 A CN112321421 A CN 112321421A CN 202011052333 A CN202011052333 A CN 202011052333A CN 112321421 A CN112321421 A CN 112321421A
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chlorine
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陈凯
陆笑迎
刘建生
杨茂霞
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SUQIAN 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
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/64—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by simultaneous introduction of -OH groups and halogens
    • C07C29/66—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by simultaneous introduction of -OH groups and halogens by addition of hypohalogenous acids, which may be formed in situ, to carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
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    • C07C69/63—Halogen-containing esters of saturated acids

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Abstract

The invention provides a preparation method of 1-acetoxyl-4-chloro-3-methyl-2-butene, which comprises the following steps: carrying out chlorohydrination reaction on isoprene and a chlorine-containing compound, carrying out esterification reaction on a product after the reaction and acetic anhydride, and finally carrying out post-treatment to obtain the 1-acetoxyl-4-chloro-3-methyl-2-butene. The preparation method has mild reaction conditions, higher safety and fewer side reactions generated in the preparation process, improves the overall reaction rate and effectively improves the purity and yield of the product due to the adoption of the strong acid loaded resin as the catalyst, and the chlorine-containing compound and the catalyst in the preparation method are convenient to recycle, so that the preparation cost is reduced, the industrial amplification feasibility is high, and the preparation method also conforms to the production concept of green chemical engineering.

Description

Preparation method of 1-acetoxyl-4-chloro-3-methyl-2-butene
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a novel synthesis method of 1-acetoxyl-4-chloro-3-methyl-2-butene.
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.
In the prior art, two addition products (1, 2-chlorohydrin and 1, 4-chlorohydrin are abbreviated as below) of 1-chloro-2-methyl-3-buten-2-ol and 4-chloro-3-methyl-2-buten-1-ol are obtained by chlorohydrination of isoprene and sodium hypochlorite, and then the two addition products are reacted with acetic anhydride under the catalysis of acid for esterification and rearrangement to obtain 1-acetoxy-4-chloro-3-methyl-2-butene (1, 4-chloro ester).
Patent CN 101041619A reports that the chlorohydrination reaction of isoprene can be carried out by adding calcium hypochlorite solid in a batch manner into an acetic acid aqueous solution and directly carrying out chlorohydrination by utilizing generated active hypochlorous acid; the method is proved by experiments that the yield and the content of the product are not high, and side reactions such as dichloro addition and the like are possibly caused on double bonds of olefin due to the existence of free chlorine and other hetero ions, so that the impurities are increased.
Patent CN 100410230C reports that solid trichloroisocyanuric acid can be added in water in batches for chlorohydrination of isoprene, and the generated active hypochlorous acid is used to directly carry out chlorohydrination, and experiments prove that the product has high purity, low yield, and excessively strong trichloroisocyanuric acid activity, and impurities are easily generated in the reaction process, and the storage conditions are harsh, which is not favorable for industrialization;
patent CN 101475471a reports that solid dichlorohydantoin can be added in water in batches for chlorohydrination of isoprene, and the generated active hypochlorous acid is used to directly carry out chlorohydrination, and experiments prove that the product has high purity and low yield, and the preservation conditions of dichlorohydantoin are harsh and are not beneficial to industrialization;
patent CN 101475471a reports that chlorohydrin product can be esterified with acetic anhydride under p-toluenesulfonic acid catalyst, 1-acetoxy-4-chloro-3-methyl-2-butene; experiments prove that the method has low yield and content of the product and difficult recovery of the catalyst p-toluenesulfonic acid after the reaction is finished, and probably a large amount of tar is generated in the reaction process due to the fact that p-toluenesulfonic acid is not acidic enough and needs to be esterified and translocated at a high temperature.
Therefore, a new green and environment-friendly method for preparing 1-acetoxyl-4-chloro-3-methyl-2-butene, which has the advantages of mild reaction conditions, high reaction rate, good safety and fewer byproducts, is urgently needed.
Disclosure of Invention
Based on the above technical background, the present inventors have made a keen search and, as a result, have found that: isoprene and chlorine-containing compounds are subjected to chlorohydrination reaction, then are subjected to esterification reaction with acetic anhydride, and finally are subjected to post-treatment to obtain the 1-acetoxyl-4-chloro-3-methyl-2-butene. The preparation method of the 1-acetoxyl-4-chloro-3-methyl-2-butene has mild reaction conditions and safer reaction, effectively improves the reaction rate due to the adoption of the strong acid loaded resin as the catalyst, improves the yield and purity of the 1-acetoxyl-4-chloro-3-methyl-2-butene, is convenient for recycling the chlorine-containing compound and the catalyst, reduces the preparation cost, and conforms to the production concept of green chemical industry.
The first aspect of the invention provides a preparation method of 1-acetoxyl-4-chloro-3-methyl-2-butene, which takes isoprene, chlorine-containing compounds and acetic anhydride as raw materials.
Specifically, the preparation method comprises the following steps:
step 1, carrying out chlorohydrination reaction on isoprene and a chlorine-containing compound;
step 2, carrying out esterification reaction on the product 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 1-acetoxy-4-chloro-3-methyl-2-butene obtained by the method for preparing 1-acetoxy-4-chloro-3-methyl-2-butene according to the first aspect of the present invention.
The preparation method of the 1-acetoxyl-4-chloro-3-methyl-2-butene provided by the invention has the following advantages:
(1) the preparation method disclosed by the invention is mild in reaction condition, high in reaction rate and higher in safety;
(2) the preparation method has high yield and few byproducts, and the byproducts can be recycled to the reaction process;
(3) the catalyst used by the preparation method can be recycled, is convenient to recycle, has higher economic value, and conforms to the concept of green chemical industry.
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 invention provides a preparation method of 1-acetoxyl-4-chloro-3-methyl-2-butene, which takes isoprene, chlorine-containing compounds and acetic anhydride as raw materials.
Specifically, the method comprises the following steps:
step 1, carrying out chlorohydrination reaction on isoprene and a chlorine-containing compound;
step 2, carrying out esterification reaction on the product prepared in the step 1 and acetic anhydride;
and 3, carrying out post-treatment to obtain a final product.
This step is specifically described and illustrated below.
Step 1, carrying out chlorohydrination reaction on isoprene and a chlorine-containing compound.
Isoprene and water are placed in a vessel for reaction, and the vessel is preferably a four-mouth bottle, and more preferably a four-mouth bottle equipped with a thermometer and a solid feeding port.
The inventor finds that the yield of the final product can be improved after the polymerization inhibitor is added, probably because the addition of the polymerization inhibitor can avoid the oxidation and polymerization of isoprene, thereby promoting the effective proceeding of the chlorohydrination reaction and further improving the yield of the final product.
The polymerization inhibitor is preferably hydroquinone, and the mass ratio of the isoprene to the hydroquinone is (100-400): 1, preferably (110-350): 1, more preferably (115-348): 1.
preferably, the chlorine-containing compound is added with isoprene, water and a polymerization inhibitor, and then the mixture is added after being fully and uniformly mixed, wherein the mixing is preferably stirring and mixing, and the mixing temperature is 0-30 ℃, and preferably 0-25 ℃. The stirring time is 0.5-1 h, preferably 0.5 h. To ensure that the isoprene, water and polymerization inhibitor are fully mixed.
The chlorine-containing compound is preferably added at a temperature of 0-10 ℃, more preferably at a temperature of 0-5 ℃, and the inventor finds that the addition of the chlorine-containing compound at the temperature can reduce the side reaction between hypochlorous acid generated by the chlorine-containing compound and the product, so that the product has higher purity and yield, and better reaction results can be obtained.
According to the invention, chloramine T can be added in a single portion from the feed port, or gradually or in portions. Preferably, the chloramine T is added gradually, which is beneficial to better control the reaction and simultaneously beneficial to forward progress of the reaction, thereby improving the yield of the product.
In the present invention, the chlorine-containing compound is selected from chlorine-containing compounds capable of reacting to generate hypochlorous acid, preferably, the chlorine-containing compound is selected from one or more of chloramine T, calcium hypochlorite, sodium hypochlorite, dichloroisocyanuric acid and trichloroisocyanuric acid, and more preferably, the chlorine-containing compound is chloramine T. The inventor finds that hypochlorous acid can be generated by reacting chloramine T with water, the yield and the purity of a final product can be effectively improved, the stability of the chloramine T is high, the chloramine T is only reduced by 0.1% after being exposed in air for one year, the chloramine T can be recycled and reused after the reaction is finished, the cost is reduced, the generation of three wastes can be greatly reduced, and the production concept of green chemical industry is met.
The molar ratio of the chlorine-containing compound to isoprene is (1-3): 1, preferably (1-2): 1, more preferably (1-1.5): 1. according to the invention, the molar amount of the chlorine-containing compound is equal to or more than that of the isoprene, so that the isoprene can be completely reacted.
Optionally, a solvent can be added in the invention, and the solvent is selected from one or more organic solvents, preferably one or two of methanol and ethanol. The solvent is optionally added in the present invention because the water added in the present invention can also be used as a solvent.
In the present invention, the molar ratio of water to the chlorine-containing compound should be 1 or more, and the molar ratio of the chlorine-containing compound to water is 1: (1-50); preferably, the molar ratio of water to chlorine-containing compound is greater than 1, and the molar ratio of chlorine-containing compound to water is preferably 1: (1-47). Because chloramine T needs to react with water to generate active hypochlorous acid, and the generated active hypochlorous acid reacts with isoprene, when the molar ratio of chloramine T to water is more than or equal to 1, the reaction can be fully performed, the chloramine T is effectively utilized, and the yield of the finally prepared product is higher.
According to the invention, the chlorohydrination reaction temperature is-5-25 ℃, preferably-5-10 ℃, and more preferably 0-5 ℃. Tests show that the reaction temperature is-5-25 ℃, the chlorohydrination reaction is more favorably carried out, and the reaction product has higher purity and higher yield.
The chlorohydrination reaction time is 0.5-5 h, preferably 0.5-3 h, more preferably 1-3 h, such as 1 h. The reaction time is short, the reaction is insufficient, and the improvement of the product yield is not facilitated. The present inventors have found that the prolonged reaction time is rather detrimental to the improvement of product purity and yield, which may be due to the occurrence of other side reactions.
The chlorohydrination reaction of the present invention can be represented by the following formula (taking chlorine-containing compound as chloramine T as an example):
Figure BDA0002709952690000061
after the reaction is finished, carrying out post-treatment on the reaction product: and (4) carrying out suction filtration, extraction and reduced pressure recovery, wherein the suction filtration is used for removing solids so as to extract the product.
In the present invention, the aqueous layer in the liquid phase obtained after the above-mentioned suction filtration is extracted and incorporated into the organic phase after the extraction is completed. The extracting agent is preferably dichloromethane, the extraction times are 2-5 times, preferably 3 times, the extraction times can influence the yield and the purity of the product prepared in the step 1, the extraction times are too few, and the yield and the purity of the product are low.
Then, the reaction mixture was recovered under reduced pressure to recover the solvent and unreacted isoprene. So as to achieve the purposes of reducing the preparation cost and realizing green production.
The temperature of the decompression recovery is 20-50 ℃, and preferably 20-40 ℃.
The process for the recovery of chloramine-T is represented by the formula:
Figure BDA0002709952690000062
after post-treatment, the product obtained in step 1 of the invention is a mixture of 1-chloro-2-methyl-3-buten-2-ol and 4-chloro-3-methyl-2-buten-1-ol, and the yield of the mixture is over 85 percent, preferably, the yield is 85 to 95 percent. The purity of the mixture is above 85%, preferably, the purity is 87-96%.
And 2, carrying out esterification reaction on the product prepared in the step 1 and acetic anhydride.
Mixing the product prepared in the step 1 with acetic anhydride, wherein the molar ratio of the product prepared in the step 1 to the acetic anhydride is 1: (1 to 3), preferably 1: (1-2), more preferably 1: (1.5-2). In the present invention, the molar amount of acetic anhydride should be greater than or equal to the molar amount of the product obtained in step 1, so as to ensure that the esterification reaction is more fully performed and the product obtained in step 1 is more fully utilized.
The esterification reaction is carried out under the condition of a catalyst, the catalyst is preferably added after the product prepared in the step 1 is mixed with acetic anhydride, the product prepared in the step 1 and the acetic anhydride are stirred and mixed, and the stirring time is 0.5-2 h, preferably 0.5 h.
In the invention, the catalyst is selected from one or more strong acid supported resins, preferably, the catalyst is selected from one or more perchloric acid supported resins, sulfonic acid supported resins and sulfuric acid supported resins, and more preferably, the catalyst is perchloric acid supported resins or sulfonic acid supported resins, such as perchloric acid supported resins. Experiments show that when perchloric acid loaded resin is used as the catalyst, the reaction selectivity is higher, and the purity and the yield of the prepared product are higher.
According to the invention, the mass ratio of the catalyst to the acetic anhydride is 1: (10-30), preferably 1: (15-25), more preferably 1 (20-22). Tests show that the catalyst can obtain a good catalytic effect only by adding a small amount of the catalyst, and particularly when the mass ratio of the catalyst to acetic anhydride is 1: (10-30), the purity and yield of the prepared product are higher.
According to a preferred embodiment of the present invention, the esterification reaction can be represented by the following formula (taking perchloric acid-supported resin as an example):
Figure BDA0002709952690000071
after the catalyst is added, the temperature is raised and the stirring is carried out again, preferably, the temperature is raised to the esterification reaction temperature and the stirring is carried out again.
In the invention, the esterification reaction temperature is 0-100 ℃, preferably 20-60 ℃, more preferably 30-50 ℃, for example 40 ℃. The present inventors have found that the esterification temperature affects the purity and yield of the final product, and that the esterification reaction at a temperature higher than 100 ℃ or lower than 0 ℃ is not favorable for the esterification reaction, and other side reactions may occur, thereby being unfavorable for the improvement of the purity and yield of the final product.
The esterification reaction time is 1-10 h, preferably 3-7 h, more preferably 4-6 h, for example 5 h. The esterification temperature affects the yield and purity of the final product, and if the esterification reaction time is too long, other side reactions may occur, thereby resulting in a decrease in the purity and yield of the final product.
Optionally, the esterification reaction may be carried out in the presence of an organic solvent selected from dichloromethane, dichloroethane, acetonitrile, acetic acid, acetic anhydride, dimethyl sulfoxide, or dimethylformamide.
And 3, carrying out post-treatment to obtain a final product.
And after the esterification reaction is finished and the temperature is reduced, carrying out post-treatment on the esterification reaction, wherein the post-treatment comprises filtering, cleaning and extracting.
And (2) filtering the system after the esterification reaction in the step (2) to obtain resin, cleaning the resin, wherein the cleaning solution is preferably dichloromethane, adding water into a mixture of dichloromethane and the resin, layering, and extracting.
The extracting agent is preferably dichloromethane, and the upper-layer water phase is extracted by the extracting agent for 1-3 times, preferably 2 times. The extraction times can affect the purity and yield of the final product, and the extraction times are too small, so that the purity and yield of the product are low.
After extraction, the lower dichloromethane phase is combined into the organic phase obtained above, then an alkaline aqueous solution is added thereto, the pH of the aqueous phase is adjusted, and the aqueous phase is left to stand, wherein the alkaline aqueous solution is preferably an aqueous sodium hydroxide solution, and more preferably an aqueous sodium hydroxide solution with the mass fraction of 10%. The pH is preferably 6-8, the inventor finds that if the acidity in the system is strong, the product can be degraded in the subsequent treatment process, the yield of the product is not improved, and the product can be prevented from being degraded after the pH is adjusted to 6-8, so that the yield of the product is effectively improved.
Adjusting pH, standing and layering to obtain an organic phase, removing dichloromethane from the organic phase to obtain a crude product of the 1-acetoxyl-4-chloro-3-methyl-2-butene, wherein the removal mode is preferably reduced pressure removal, and more preferably the removal mode is that the temperature of the organic phase is lower than 30 ℃.
The purity of the 1-acetoxyl-4-chloro-3-methyl-2-butene obtained by the post-treatment is more than 90 percent, and the preferred purity is 92 to 95 percent.
In the invention, optionally, the 1-acetoxyl-4-chloro-3-methyl-2-butene prepared in the above way can be rectified, and the rectification can further improve the purity of the product.
The purity of the rectified 1-acetoxyl-4-chloro-3-methyl-2-butene is more than 95 percent, preferably 96 to 98 percent, and the yield can reach 70 to 90 percent, preferably 80 to 90 percent.
The second aspect of the present invention is to provide 1-acetoxy-4-chloro-3-methyl-2-butene obtained by the method for preparing 1-acetoxy-4-chloro-3-methyl-2-butene according to the first aspect of the present invention.
The invention can achieve the following beneficial effects:
(1) according to the invention, chloramine T reacts with water to generate hypochlorous acid for the first time, the hypochlorous acid is prepared by replacing the existing reaction of sodium hypochlorite and the like with an acetic acid aqueous solution, the generation of three wastes is greatly reduced, the stability of chloramine T is high, the chloramine T can be recycled after the reaction is finished, the preparation cost is reduced, and the industrial amplification feasibility is high;
(2) the invention uses the load type ion exchange resin as the catalyst, effectively reduces the preparation reaction temperature, and simultaneously the ion exchange resin can be recycled, and the recycling method is simple and easy, and has higher industrial value;
(3) the method has the advantages of mild reaction conditions, high reaction rate, high safety and less side reactions;
(4) the 1-acetoxyl-4-chloro-3-methyl-2-butene prepared by the method has high purity and yield, the purity can reach more than 90 percent, and the yield is 70 to 90 percent.
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 11-chloro-2-methyl-3-buten-2-ol and 4-chloro-3-methyl-2-buten-1-ol mixture
A1000 ml four-mouth bottle provided with a thermometer and a solid feeding port is placed in an alcohol cold bath, 34.76g (0.50mol) of isoprene with the purity of 98%, 500ml (27.74mol) of water and 0.1g of hydroquinone serving as a polymerization inhibitor are added, the mixture is stirred for 0.5h under the condition of controlling the internal temperature to be 2 ℃ and fully mixed, then chloramine T (30% of available chlorine) with the purity of 96% is added in batches from the feeding port under the condition of controlling the internal temperature to be 2 ℃, 142.28g (0.60mol) is added in total for about 2h, and the addition is completed. The temperature is kept at 2 ℃ for reaction for 1h, the solid is removed by suction filtration, a water layer is extracted for 3 times by 200ml of dichloromethane and then is merged into an organic phase, the organic phase is decompressed at 25 ℃ to recover the solvent and unreacted isoprene to obtain 58.6g of crude product, and gas phase analysis shows that the total content of the product is 95.5 percent, the yield is 93.3 percent, and the product can be directly used for the next reaction. The chlorohydrin pure product can be obtained by rectification.
Example 21-chloro-2-methyl-3-buten-2-ol and 4-chloro-3-methyl-2-buten-1-ol mixture
A1000 ml four-necked flask equipped with a thermometer and a solid feed port was placed in an alcohol cooling bath, 34.76g (0.50mol) of isoprene having a purity of 98%, 500ml (27.74mol) of water, and 0.1g of hydroquinone as a polymerization inhibitor were added, and stirred at 0 ℃ for 0.5 hour for well mixing, and after controlling the internal temperature at 0 ℃, a total of 142.28g (0.60mol) of chloramine T having a purity of 96% (30% available chlorine) was directly added from the feed port. The temperature is kept at 0 ℃ for reaction for 3h, the solid is removed by suction filtration, the water layer is extracted by 200ml of dichloromethane for 3 times and then is merged into an organic phase, the organic phase is decompressed at 25 ℃ to recover the solvent and unreacted isoprene to obtain 57.0g of crude product, and the gas phase analysis shows that the total content of the product is 93.8 percent, the yield is 89.1 percent and the product can be directly used for the next reaction.
Example 31-chloro-2-methyl-3-buten-2-ol and 4-chloro-3-methyl-2-buten-1-ol mixture
A1000 ml four-mouth bottle provided with a thermometer and a solid feeding port is placed in an alcohol cold bath, 34.76g (0.50mol) of isoprene with the purity of 98 percent, 11ml (0.61mol) of water and 500ml of methanol, 0.3g of hydroquinone as a polymerization inhibitor are added, the mixture is stirred for 0.5h under the condition that the internal temperature is controlled at 5 ℃ and fully mixed, then chloramine T with the purity of 96 percent (30 percent of available chlorine) is added in batches from the feeding port under the condition that the internal temperature is controlled at 5 ℃, and 142.28g (0.60mol) is added in total for about 2 h. Keeping the temperature at 5 ℃ for reaction for 1h, filtering to remove solids, extracting a water layer by 300ml of dichloromethane for 3 times, then merging the water layer into an organic phase, decompressing and recovering the solvent, unreacted isoprene and solvent methanol at 30 ℃ of the organic phase, decompressing and distilling to obtain 54.4g of a crude product, wherein the gas phase analysis shows that the total content of the product is 94.7 percent, the yield is 85.9 percent, and the product can be directly used for the next reaction.
Example 41 mixture of chloro-2-methyl-3-buten-2-ol and 4-chloro-3-methyl-2-buten-1-ol
A1000 ml four-mouth bottle provided with a thermometer and a solid feeding port is placed in an alcohol cold bath, 34.76g (0.50mol) of isoprene with the purity of 98%, 500ml (27.74mol) of water and 0.3g of hydroquinone serving as a polymerization inhibitor are added, the mixture is stirred for 0.5h under the condition that the internal temperature is controlled to be 8 ℃ and fully mixed, then chloramine T (30% of available chlorine) with the purity of 96% is added in batches from the feeding port under the condition that the internal temperature is controlled to be 8 ℃, 142.28g (0.60mol) is added in total for about 2h, and the addition is completed. Keeping the temperature at 8 ℃ for reaction for 1h, filtering to remove solids, extracting a water layer by using 200ml of dichloromethane for 3 times, merging the water layer into an organic phase, decompressing and recovering the solvent and unreacted isoprene at the temperature of 25 ℃ of the organic phase to obtain 59.6g of a crude product, wherein the gas phase analysis shows that the total content of the product is 87.1 percent, and the yield is 86.5 percent.
Example 51-acetoxy-4-chloro-3-methyl-2-butene
A500 ml four-necked flask was charged with 62.84g (content: 95.5%, 0.5mol) of the product obtained in example 1 and 83.20g (0.82mol) of acetic anhydride, stirred for 0.5 hour, added with 4g of a perchloric acid-supported resin, and heated to 40 ℃ and stirred. And after 5 hours of reaction, cooling, filtering to obtain resin, washing the resin with dichloromethane, adding 200ml of water layer, extracting the upper aqueous phase twice with 200ml of dichloromethane, extracting the lower dichloromethane phase, adding the lower dichloromethane phase into an organic phase, adjusting the pH value of the organic phase to 7 with 10% sodium hydroxide aqueous solution, standing for layering, and separating the organic phase. The organic phase is decompressed and removed with dichloromethane at 25 ℃ to obtain 75.4g (the content is 93.5%) of crude chloride, and the crude chloride is rectified to obtain 71.5g (the content is 97.1%) of colorless transparent solution, and the yield is 85.7%.
Example 61-acetoxy-4-chloro-3-methyl-2-butene
A500 ml four-necked flask was charged with 62.84g (content: 95.5%, 0.5mol) of the product obtained in example 1 and 83.20g (0.82mol) of acetic anhydride, stirred for 0.5 hour, added with 4g of a perchloric acid-supported resin, and heated to 30 ℃ and stirred. And after 5 hours of reaction, cooling, filtering to obtain resin, washing the resin with dichloromethane, adding 200ml of water layer, extracting the upper aqueous phase twice with 200ml of dichloromethane, extracting the lower dichloromethane phase, adding the lower dichloromethane phase into an organic phase, adjusting the pH value of the aqueous phase to 7.5 with 10% sodium hydroxide aqueous solution, standing for layering, and separating the organic phase. The organic phase was freed from dichloromethane at 28 ℃ under reduced pressure to give 67.9g (92.9% content) of crude chloride, which was rectified to give 62.5g (96.1% content) of a colorless, transparent solution, with a yield of 74.1%.
Example 71-acetoxy-4-chloro-3-methyl-2-butene
A500 ml four-necked flask was charged with 62.84g (content: 95.5%, 0.5mol) of the product obtained in example 1 and 83.20g (0.82mol) of acetic anhydride, stirred for 0.5 hour, added with 4g of a perchloric acid-supported resin, and heated to 50 ℃ and stirred. And after 5 hours of reaction, cooling, filtering to obtain resin, washing the resin with dichloromethane, adding 200ml of water layer, extracting the upper aqueous phase twice with 200ml of dichloromethane, extracting the lower dichloromethane phase, adding the lower dichloromethane phase into an organic phase, adjusting the pH value of the organic phase to 7 with 10% sodium hydroxide aqueous solution, standing for layering, and separating the organic phase. The organic phase is decompressed and removed with dichloromethane at 25 ℃ to obtain 75.4g (the content is 92.8 percent) of crude chloride, and the crude chloride is rectified to obtain 70.4g (the content is 96.5 percent) of colorless transparent solution, and the yield is 83.8 percent.
Example 81-acetoxy-4-chloro-3-methyl-2-butene
62.84g (content: 95.5%, 0.5mol) of the product obtained in example 1 and 83.20g (0.82mol) of acetic anhydride were put into a 500ml four-necked flask, stirred for 0.5 hour, added with 4g of a sulfonic acid-supported resin, and heated to 40 ℃ and stirred. And after 5 hours of reaction, cooling, filtering to obtain resin, washing the resin with dichloromethane, adding 200ml of water layer, extracting the upper aqueous phase twice with 200ml of dichloromethane, extracting the lower dichloromethane phase, adding the lower dichloromethane phase into an organic phase, adjusting the pH value of the organic phase to 7 with 10% sodium hydroxide aqueous solution, standing for layering, and separating the organic phase. The organic phase is decompressed and removed with dichloromethane at 25 ℃ to obtain 76.1g (the content is 92.3%) of crude chloride, and the crude chloride is rectified to obtain 70.5g (the content is 96.7%) of colorless transparent solution, and the yield is 84.2%.
Comparative example
Comparative example 1
A1000 ml four-mouth bottle provided with a thermometer and a solid feeding port is placed in an alcohol cold bath, 34.76g (0.50mol) of isoprene with the purity of 98%, 500ml (27.74mol) of water and 0.1g of hydroquinone serving as a polymerization inhibitor are added, the mixture is stirred for 0.5h under the condition of controlling the internal temperature to be 2 ℃ and fully mixed, then calcium hypochlorite (65% of available chlorine), 131.99g (0.60mol) and 36.77g (0.60mol) of 98% acetic acid are added in batches from the feeding port under the condition of controlling the internal temperature to be 2 ℃, and the addition is completed within about 2 h. The temperature is kept at 2 ℃ for reaction for 1h, the solid is removed by suction filtration, the water layer is extracted by 200ml of dichloromethane for 3 times and then is merged into an organic phase, the organic phase is decompressed and the solvent and the unreacted isoprene are recovered at 25 ℃ to obtain 56.81g of crude product, the gas phase analysis shows that the total content of the product is 75.3 percent, and the yield is 71.3 percent.
Comparative example 2
The procedure of example 5 was repeated except that the product obtained in comparative example 1 was charged into a 500ml four-necked flask, methylene chloride was removed under reduced pressure to give 65.5g (content: 89.7%) of a crude chloride, and the mixture was distilled to give 61.1g (content: 96.2%) of a colorless transparent solution in a yield of 72.6%.
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 1-acetoxyl-4-chloro-3-methyl-2-butene is characterized in that isoprene, a chlorine-containing compound and acetic anhydride are used as raw materials.
2. The method of claim 1, comprising the steps of:
step 1, carrying out chlorohydrination reaction on isoprene and a chlorine-containing compound;
step 2, carrying out esterification reaction on the product prepared in the step 1 and acetic anhydride;
and 3, carrying out post-treatment to obtain a final product.
3. The production method according to claim 2, wherein, in step 1,
the chlorine-containing compound is selected from chlorine-containing compounds capable of reacting to produce hypochlorous acid;
the molar ratio of the chlorine-containing compound to the isoprene is (1-3): 1.
4. The preparation method according to claim 2, wherein in step 1, the chlorine-containing compound is preferably added after adding isoprene, water and a polymerization inhibitor, mixing them uniformly;
the molar ratio of the chlorine-containing compound to the water is 1: (1-50).
5. The production method according to claim 2, wherein, in step 1,
the temperature of the chlorohydrination reaction is-5-25 ℃, and the time of the chlorohydrination reaction is 0.5-5 h.
6. The method according to claim 2, wherein in step 2, the molar ratio of the product obtained in step 1 to acetic anhydride is 1: (1-3);
the esterification reaction is carried out in the presence of a catalyst, and the catalyst is preferably added after the product obtained in step 1 is mixed with acetic anhydride.
7. The preparation method according to claim 2, wherein in the step 2, the catalyst is selected from one or more of strong acid supported resins;
the mass ratio of the catalyst to the acetic anhydride is 1: (10-30).
8. The preparation method according to claim 2, wherein in the step 2, the esterification reaction temperature is 0-100 ℃ and the esterification reaction time is 1-10 h.
9. The method according to claim 2, wherein the post-treatment in step 3 comprises filtration, washing and extraction,
the extraction times are 1-2 times; and adding an alkaline aqueous solution after extraction, and adjusting the pH of the aqueous phase to 6-8.
10. 1-acetoxy-4-chloro-3-methyl-2-butene, characterized in that the 1-acetoxy-4-chloro-3-methyl-2-butene is prepared by the preparation process according to any one of claims 1 to 9.
CN202011052333.0A 2020-09-29 2020-09-29 Preparation method of 1-acetoxyl-4-chloro-3-methyl-2-butene Pending CN112321421A (en)

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