CN117088842A - Synthesis method of 2, 4-butane sultone - Google Patents
Synthesis method of 2, 4-butane sultone Download PDFInfo
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- CN117088842A CN117088842A CN202311066004.5A CN202311066004A CN117088842A CN 117088842 A CN117088842 A CN 117088842A CN 202311066004 A CN202311066004 A CN 202311066004A CN 117088842 A CN117088842 A CN 117088842A
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- butane sultone
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- butane
- butanediol
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- VWEYDBUEGDKEHC-UHFFFAOYSA-N 3-methyloxathiolane 2,2-dioxide Chemical compound CC1CCOS1(=O)=O VWEYDBUEGDKEHC-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 235000019437 butane-1,3-diol Nutrition 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 230000018044 dehydration Effects 0.000 claims abstract description 13
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 9
- RTTNOHLFPFFOCA-UHFFFAOYSA-N 3-hydroxybutane-1-sulfonic acid Chemical compound CC(O)CCS(O)(=O)=O RTTNOHLFPFFOCA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 238000011033 desalting Methods 0.000 claims abstract description 7
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- 230000020477 pH reduction Effects 0.000 claims abstract description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- 238000006277 sulfonation reaction Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000002000 Electrolyte additive Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- -1 4-butyl Chemical group 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 6
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 5
- UTBUFLARLRSVFF-UHFFFAOYSA-N 3-chlorobutan-1-ol Chemical compound CC(Cl)CCO UTBUFLARLRSVFF-UHFFFAOYSA-N 0.000 description 5
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 5
- BYCGYBXZYBOLMP-UHFFFAOYSA-N C(C)(CC)O.[Na] Chemical compound C(C)(CC)O.[Na] BYCGYBXZYBOLMP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- KMBRJVMBQNMRDM-UHFFFAOYSA-N 1-hydroxybutane-1-sulfonic acid Chemical compound CCCC(O)S(O)(=O)=O KMBRJVMBQNMRDM-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- HXHGULXINZUGJX-UHFFFAOYSA-N 4-chlorobutanol Chemical compound OCCCCCl HXHGULXINZUGJX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- LSPPRHYSWKZGRZ-UHFFFAOYSA-M sodium;3-hydroxybutane-1-sulfonate Chemical compound [Na+].CC(O)CCS([O-])(=O)=O LSPPRHYSWKZGRZ-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N 1-butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/04—Five-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of electrolyte additives and organic synthesis, and discloses a synthesis method of 2, 4-butane sultone. The synthesis method comprises the following steps: (1) Adding 1, 3-butanediol, a sulfonating reagent and an iodized salt catalyst into water, stirring and dissolving uniformly, regulating the pH of the system to be acidic, heating to 50-100 ℃, stirring and reacting to obtain a 3-hydroxy butane sulfonate solution; (2) And (3) sequentially carrying out concentration, acidification, desalting and dehydration cyclization on the 3-hydroxybutanesulfonate solution obtained in the step (1) to obtain the 2, 4-butane sultone. The synthesis method of the invention adopts the reaction of 1, 3-butanediol and a sulfonating reagent in the next step of the catalysis of iodized salt to obtain the 3-hydroxybutanesulfonate solution, and then the 3-hydroxybutanesulfonate solution is acidified, dehydrated and cyclized to obtain the 2, 4-butane sultone, and the synthesis method has the advantages of wide raw material sources, mild reaction conditions, less byproducts, high product quality and low cost.
Description
Technical Field
The invention belongs to the technical field of electrolyte additives and organic synthesis, and particularly relates to a synthesis method of 2, 4-butane sultone.
Background
With the continuous development of new energy automobiles, higher requirements are put forward on the performance of lithium ion batteries. 2, 4-butane sultone (2, 4-BS) as an electrolyte additive for lithium ion batteries shows unique properties, and can effectively improve electrochemical properties of lithium ion batteries, so that the 2, 4-butane sultone has been widely paid attention.
At present, the synthesis of 2,4-BS mainly comprises the following methods:
1) 1, 3-butanediol is chloridized to obtain 3-chloro-1-butanol, and then is sulfonated, acidified and dehydrated to obtain 2,4-BS (such as the methods disclosed in patent CN114805288 and CN 114181190A). The method adopts 3-chloro-1-butanol to carry out sulfonation reaction, has higher reaction activity and mild reaction conditions, but adopts 1, 3-butanediol to carry out chlorination reaction to prepare 3-chloro-1-butanol, the reaction needs to be carried out under the condition of a specific catalyst, and the chlorination reaction can generate a large number of products with two hydroxyl groups replaced, and cannot be cyclized to obtain a target product in the subsequent process, so that the product yield is influenced.
2) The reaction of 1,3-PS with a methylating agent under sodium hydrogen catalysis gives 2,4-BS (as disclosed in patent CN 112961139A). The method has simple reaction steps, but the catalyst sodium hydrogen is extremely easy to react with water to release extremely flammable gas, is not easy to store and is not suitable for industrial production.
3) Crotyl alcohol (2-butenol) and sodium bisulphite are sulfonated in the presence of peroxide, and then are acidified and dehydrated to obtain 2,4-BS (as disclosed in patent CN102807552A, CN 114075165A). The method has simple reaction steps, but the crotyl alcohol has high price and high production cost (the market price of the crotyl alcohol is about 1800 yuan/kg in hundred kg, and the ton level is about 800 yuan/kg).
4) The crotonaldehyde and sodium bisulphite are sulfonated firstly in the presence of peroxide, and then hydrogenation reduction, acidification and dehydration are carried out to obtain 2,4-BS (Huang Dangmu, etc. 2, 4-butyl sultone is synthesized, chinese academy of sciences Fujian Material Structure institute, chemical journal 1996-10 (7)). The method has the advantages of simple and easily obtained raw materials, relatively low price and about 20-30 yuan/kg of market price, but high-pressure hydrogenation reaction is involved, the danger is high, aldehyde groups can react with sodium bisulphite, and the reaction yield is low.
5) The reaction of 1-butene with sulfur trioxide gives 2,4-BS (MB Smith etc. Lithium aluminum hydride-aluminum hydride reduction ofsuperior.10.1021/jo00314 a 022.1981). The method has simple reaction steps, but needs to react at the temperature of-78 ℃ deeply, has strict reaction conditions, and is difficult for industrial production.
Patent CN 109293625A discloses a method for synthesizing high-purity 1, 4-butane sultone, which is obtained by adopting 4-chlorobutanol and sodium sulfite solution to react in potassium iodide and alcohol solvent as catalysts. But the sulfonation reaction sites and the activity of the 4-chlorobutanol and the 3-chloro-1-butanol or the 1, 3-butanediol are obviously different, and the product structure and the reaction conditions are obviously different from the synthesis of the 2, 4-butane sultone.
Therefore, it is urgent to find a method for synthesizing 2, 4-butane sultone, which has low raw material cost and simple reaction steps and is suitable for industrial production.
Disclosure of Invention
Aiming at the problems of high raw material price, complex reaction steps, harsh reaction conditions, inconvenient industrial production and the like in the prior art, the invention aims to provide a method for synthesizing 2, 4-butane sultone. The synthesis method of the invention adopts the reaction of 1, 3-butanediol and a sulfonating reagent in the next step of the catalysis of iodized salt to obtain the 3-hydroxybutanesulfonate solution, and then the 3-hydroxybutanesulfonate solution is acidified, dehydrated and cyclized to obtain the 2, 4-butane sultone, and the synthesis method has the advantages of wide raw material sources, mild reaction conditions, less byproducts, high product quality and low cost.
The invention aims at realizing the following technical scheme:
a method for synthesizing 2, 4-butane sultone comprises the following steps:
(1) Adding 1, 3-butanediol, a sulfonating reagent and an iodized salt catalyst into water, stirring and dissolving uniformly, regulating the pH of the system to be acidic, heating to 50-100 ℃, stirring and reacting to obtain a 3-hydroxy butane sulfonate solution;
(2) And (3) sequentially carrying out concentration, acidification, desalting and dehydration cyclization on the 3-hydroxybutanesulfonate solution obtained in the step (1) to obtain the 2, 4-butane sultone.
Further, the sulfonating agent in step (1) is sulfite or bisulfite. Sodium sulfite or sodium bisulfite is preferred.
Further preferably, the molar ratio of the 1, 3-butanediol to the sulfonating agent is 0.5 to 2.0.
Further, the iodized salt catalyst in the step (1) is NaI or KI.
Further preferably, the addition amount of the iodized salt catalyst is 0.1 to 10% by mass of 1, 3-butanediol.
Further, the step (1) of adjusting the pH of the system to be acidic means that the pH of the system is adjusted to be 2-6.
Further, the stirring reaction time in the step (1) is 2-24 hours.
Further, the concentration in the step (2) means dehydration by distillation under reduced pressure until the reaction liquid becomes turbid.
Further, the acidifying and desalting steps in the step (2) are as follows: adding concentrated hydrochloric acid for acidification, adding ethanol, stirring, filtering and desalting.
Further, the step of the dehydration cyclization reaction in the step (2) is as follows: concentrating by reduced pressure distillation, and then flash evaporating, dehydrating and cyclizing at 110-120 ℃ under vacuum condition.
Further, the 2, 4-butane sultone obtained in the step (2) is further distilled at 130-150 ℃ to obtain a crude product of the 2, 4-butane sultone, and then the crude product is rectified to obtain a purified product of the 2, 4-butane sultone.
The principle of the invention is as follows: the iodized salt catalyst adopted by the invention, such as NaI or KI, forms HI under the acidic condition, and can well activate the alcoholic hydroxyl; meanwhile, iodine ions can be used as a strong nucleophile to carry out nucleophilic substitution with 1, 3-butanediol under the acidic condition to generate 3-iodine-1-butanol, and in addition, the iodine ions are easy leaving groups, so that the iodine ions can be easily substituted to obtain 3-hydroxybutanesulfonic acid salt in the presence of a nucleophile such as sulfite ions.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with the method that 1, 3-butanediol is chlorinated to obtain an intermediate product 3-chloro-1-butanol, and then sulfonation reaction is carried out, the method adopts iodized salt such as NaI or KI and the like as a catalyst, takes 1, 3-butanediol as a reaction raw material, has stronger iodide ion pertinence, is easier to generate secondary substitutes and is easy to leave, a chlorinated product can be directly used as a reaction intermediate to react with a sulfonation reagent, the chlorination reaction steps and byproducts are reduced, the one-step reaction of the 1, 3-butanediol and the sulfonation reagent is realized, the reaction efficiency is higher, and the product yield and quality are high.
(2) The invention adopts 1, 3-butanediol as the sulfonation reaction raw material, the market price is about 40 yuan/kg, compared with the raw materials such as crotyl alcohol and the like used in the prior art, the price is low and easy to obtain, and compared with the crotonaldehyde raw material, the price is equivalent, but the 1, 3-butanediol can be directly used without pre-advanced high-pressure hydrogenation reduction, the process is simpler and easy to operate, the safety is high, the equipment requirement and the production energy consumption are lower, and the invention has industrial value.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of sodium 3-hydroxybutanesulfonate, an intermediate product obtained in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
The synthetic method of the 2, 4-butane sultone comprises the following steps:
(1) 150mL of deionized water and 31.2g of sodium bisulfite are added into a three-neck flask, a small amount of hydrochloric acid is added, the pH is regulated to 4, after the mixture is stirred to be clear, 0.27g of NaI and 27.0g of 1, 3-butanediol are sequentially added, the temperature is raised to 100 ℃ and the mixture is stirred to reflux for 3 hours, and a sodium 3-hydroxybutanesulfonate solution is obtained. And carrying out nuclear magnetism identification on the obtained 3-hydroxy butane sodium sulfonate solution, wherein the obtained spectrogram is shown in figure 1. As shown in the figure, the spectrogram is basically consistent with the nuclear magnetic hydrogen spectrum of the 3-hydroxy butane sodium sulfonate simulated by chemdraw except the leftmost solvent peak, so that the 3-hydroxy butane sodium sulfonate solution prepared by the scheme does not contain chloridized products or disubstituted products and the like;
the reaction formula involved in this step is as follows:
(2) And (3) distilling and dehydrating the 3-hydroxy butane sodium sulfonate solution obtained in the step (1) under reduced pressure until the reaction solution is turbid, cooling to room temperature, adding 100g of concentrated hydrochloric acid and 100g of ethanol, stirring at room temperature for reaction for 3 hours to separate out sodium chloride solid, filtering, distilling and dehydrating the filtrate under reduced pressure by a water pump, heating to 110-120 ℃ under the vacuum degree of 800Pa for cyclization reaction, heating to 130-150 ℃ for distillation after no bubble generation to obtain a crude product of 2, 4-butane sultone, and rectifying to obtain the 2, 4-butane sultone.
The reaction formula involved in this step is as follows:
the 2, 4-butane sultone obtained in this example was found to have a purity of 99.6%, a water content of 153ppm, an acid value (calculated as HF) of 43ppm and a yield of 74.2%.
Example 2
The synthetic method of the 2, 4-butane sultone comprises the following steps:
(1) 200mL of deionized water and 45.4g of sodium sulfite are added into a three-neck flask, a small amount of hydrochloric acid is added, the pH is regulated to 6, after the mixture is stirred to be clear, 2.7g of NaI and 27.0g of 1, 3-butanediol are sequentially added, the temperature is raised to 70 ℃, and the mixture is stirred and refluxed for 12 hours, so that a 3-sodium hydroxybutanesulfonate solution is obtained.
(2) And (3) carrying out reduced pressure distillation and dehydration on the 3-hydroxybutanesulfonic acid sodium solution obtained in the step (1) until the reaction solution is turbid, cooling to room temperature, adding 100g of concentrated hydrochloric acid and 100g of ethanol, stirring at room temperature for reaction for 3 hours, filtering, carrying out reduced pressure distillation and dehydration on the filtrate by a water pump, heating to 110-120 ℃ under the vacuum degree of 800Pa, carrying out cyclization reaction until no bubbles are generated, heating to 130-150 ℃ and distilling to obtain a 2, 4-butane sultone crude product, and rectifying to obtain the 2, 4-butane sultone.
The 2, 4-butane sultone obtained in this example was found to have a purity of 99.6%, a moisture content of 161ppm, an acid value (in terms of HF) of 41ppm and a yield of 71.3%.
Example 3
The synthetic method of the 2, 4-butane sultone comprises the following steps:
(1) 200mL of deionized water and 45.4g of sodium sulfite are added into a three-neck flask, a small amount of hydrochloric acid is added, the pH is regulated to 6, after the mixture is stirred to be clear, 2.0gKI and 27.0g of 1, 3-butanediol are sequentially added, the temperature is raised to 70 ℃, and the mixture is stirred and refluxed for 12 hours, so that a 3-sodium hydroxybutanesulfonate solution is obtained.
(2) And (3) carrying out reduced pressure distillation and dehydration on the 3-hydroxybutanesulfonic acid sodium solution obtained in the step (1) until the reaction solution is turbid, cooling to room temperature, adding 100g of concentrated hydrochloric acid and 100g of ethanol, stirring at room temperature for reaction for 3 hours, filtering, carrying out reduced pressure distillation and dehydration on the filtrate by a water pump, heating to 110-120 ℃ under the vacuum degree of 800Pa, carrying out cyclization reaction until no bubbles are generated, heating to 130-150 ℃ and distilling to obtain a 2, 4-butane sultone crude product, and rectifying to obtain the 2, 4-butane sultone.
The 2, 4-butane sultone obtained in this example was found to have a purity of 99.5%, a moisture content of 156ppm, an acid value (in terms of HF) of 42ppm and a yield of 72.1%.
Example 4
The synthetic method of the 2, 4-butane sultone comprises the following steps:
(1) 150mL of deionized water and 31.2g of sodium bisulfite are added into a three-neck flask, a small amount of hydrochloric acid is added, the pH is regulated to 2, after the mixture is stirred to be clear, 1.0gKI and 40.5g of 1, 3-butanediol are sequentially added, the temperature is raised to 50 ℃ and the mixture is stirred and reacted for 24 hours, so that a 3-sodium hydroxybutanesulfonate solution is obtained.
(2) And (3) carrying out reduced pressure distillation and dehydration on the 3-hydroxybutanesulfonic acid sodium solution obtained in the step (1) until the reaction solution is turbid, cooling to room temperature, adding 100g of concentrated hydrochloric acid and 100g of ethanol, stirring at room temperature for reaction for 3 hours, filtering, carrying out reduced pressure distillation and dehydration on the filtrate by a water pump, heating to 110-120 ℃ under the vacuum degree of 800Pa, carrying out cyclization reaction until no bubbles are generated, heating to 130-150 ℃ and distilling to obtain a 2, 4-butane sultone crude product, and rectifying to obtain the 2, 4-butane sultone.
The 2, 4-butane sultone obtained in this example was found to have a purity of 99.6%, a moisture content of 159ppm, an acid value (calculated as HF) of 41ppm and a yield of 71.5%.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The synthesis method of the 2, 4-butane sultone is characterized by comprising the following steps:
(1) Adding 1, 3-butanediol, a sulfonating reagent and an iodized salt catalyst into water, stirring and dissolving uniformly, regulating the pH of the system to be acidic, heating to 50-100 ℃, stirring and reacting to obtain a 3-hydroxy butane sulfonate solution;
(2) And (3) sequentially carrying out concentration, acidification, desalting and dehydration cyclization on the 3-hydroxybutanesulfonate solution obtained in the step (1) to obtain the 2, 4-butane sultone.
2. The method for synthesizing 2, 4-butane sultone according to claim 1, wherein said sulfonation reagent in the step (1) is sulfite or bisulfite.
3. The method for synthesizing 2, 4-butane sultone according to claim 2, wherein the molar ratio of 1, 3-butanediol to sulfonation reagent is 0.5-2.0.
4. The method of claim 1, wherein the iodinated salt catalyst in step (1) is NaI or KI.
5. The method for synthesizing 2, 4-butane sultone according to claim 4, wherein the addition amount of the iodized salt catalyst is 0.1% -10% by mass of 1, 3-butanediol.
6. The method for synthesizing 2, 4-butane sultone according to claim 1, wherein the step (1) of adjusting the pH of the system to be acidic means adjusting the pH of the system to 2 to 6; the stirring reaction time is 2-24 h.
7. The method for synthesizing 2, 4-butane sultone according to claim 1, wherein said concentration in step (2) means dehydration by distillation under reduced pressure until the reaction solution becomes turbid.
8. The method for synthesizing 2, 4-butane sultone according to claim 1, wherein the step of acidifying and desalting in the step (2) is as follows: adding concentrated hydrochloric acid for acidification, adding ethanol, stirring, filtering and desalting.
9. The method for synthesizing 2, 4-butane sultone according to claim 1, wherein the step of the dehydrative ring closure reaction in the step (2) is: concentrating by reduced pressure distillation, and then flash evaporating, dehydrating and cyclizing at 110-120 ℃ under vacuum condition.
10. The method for synthesizing 2, 4-butane sultone according to claim 1, wherein the 2, 4-butane sultone obtained in the step (2) is further distilled at 130-150 ℃ to obtain a crude 2, 4-butane sultone, and then distilled to obtain a purified 2, 4-butane sultone product.
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