CN113444059A - Process for the preparation of 2- (methylsulfonyl) -oxirane and derivatives thereof - Google Patents
Process for the preparation of 2- (methylsulfonyl) -oxirane and derivatives thereof Download PDFInfo
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- CVYAOODREIIGDR-UHFFFAOYSA-N 2-methylsulfonyloxirane Chemical compound CS(=O)(=O)C1CO1 CVYAOODREIIGDR-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 6
- 239000002994 raw material Substances 0.000 claims abstract description 18
- WUIJTQZXUURFQU-UHFFFAOYSA-N 1-methylsulfonylethene Chemical compound CS(=O)(=O)C=C WUIJTQZXUURFQU-UHFFFAOYSA-N 0.000 claims abstract description 14
- WOPDMJYIAAXDMN-UHFFFAOYSA-N Allyl methyl sulfone Chemical compound CS(=O)(=O)CC=C WOPDMJYIAAXDMN-UHFFFAOYSA-N 0.000 claims abstract description 14
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims abstract description 12
- PJIGFUQYPPBSJV-UHFFFAOYSA-N methyl oxiran-2-ylmethanesulfonate Chemical group COS(=O)(=O)CC1CO1 PJIGFUQYPPBSJV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 7
- DUGDVPXCHOVCOS-UHFFFAOYSA-N methyl prop-2-ene-1-sulfonate Chemical compound COS(=O)(=O)CC=C DUGDVPXCHOVCOS-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 16
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- YMLUGIXGNODJEE-UHFFFAOYSA-N 1-chloro-3-methylsulfonylpropane Chemical compound CS(=O)(=O)CCCCl YMLUGIXGNODJEE-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 10
- DKWNYTKOLIZNAX-UHFFFAOYSA-N 1-chloro-2-methylsulfonylethane Chemical compound CS(=O)(=O)CCCl DKWNYTKOLIZNAX-UHFFFAOYSA-N 0.000 claims description 9
- BVXKWTBRQORZNE-UHFFFAOYSA-N 2-(methylsulfonylmethyl)oxirane Chemical group CS(=O)(=O)CC1CO1 BVXKWTBRQORZNE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 6
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 5
- 229910006124 SOCl2 Inorganic materials 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- AAHFRWRQQDVWPX-UHFFFAOYSA-N prop-2-ene-1-sulfonyl chloride Chemical compound ClS(=O)(=O)CC=C AAHFRWRQQDVWPX-UHFFFAOYSA-N 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Substances ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- -1 ethylene oxide group sulfur compound Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/34—Compounds containing oxirane rings with hydrocarbon radicals, substituted by sulphur, selenium or tellurium atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
Abstract
A preparation method of 2- (methylsulfonyl) -ethylene oxide and derivatives thereof belongs to the technical field of synthesis of ethylene oxide derivatives, and comprises the following steps: the raw material is vinyl methyl sulfone or allyl methyl sulfone or methyl allyl sulfonate, the raw material dissolved by the organic solvent is dropwise added into m-chloroperoxybenzoic acid for three times according to the mass ratio of 1:2:4, the adding time is 30min, 25min and 10min respectively, the temperature is increased and the reflux is carried out for 15-30h, the mixture is cooled to the room temperature and filtered, and the product is obtained; when the raw material is vinyl methyl sulfone, the product is 2- (methylsulfonyl) -ethylene oxide; when the raw material is allyl methyl sulfone, the product is methyl-2, 3-epoxypropane sulfonate; when the raw material is methyl allyl sulfonate, the product is methyl-2, 3-epoxypropane sulfonate; the molar ratio of the raw material to the m-chloroperoxybenzoic acid is 1 (1.8-2.4); the preparation method is simple and has high yield.
Description
Technical Field
The invention belongs to the technical field of synthesis of ethylene oxide derivatives, and relates to a preparation method of 2- (methylsulfonyl) -ethylene oxide, in particular to a preparation method of 2- (methylsulfonyl) -ethylene oxide and derivatives thereof.
Background
The sulfur-containing compound containing an oxirane group can be reductively decomposed on the surface of the negative electrode to form a reductive decomposition product, and the reductive decomposition product can form a protective layer on the positive electrode, and such a positive electrode protective layer can suppress the decomposition of the positive electrode and prevent the resistance of the positive electrode from increasing. In addition, the C-C bond of the epoxy ring in the sulfur compound containing an ethylene oxide group is broken at a high temperature, polymerization occurs, and a protective layer can be formed on the surface of the electrode, so that the electrolyte containing the ethylene oxide group sulfur compound can simultaneously improve the cycle life performance and the high temperature stability of a rechargeable lithium battery, and based on this, research on the preparation method of 2- (methylsulfonyl) -ethylene oxide and its derivatives is of great significance in the field of battery electrolytes.
Disclosure of Invention
The invention provides a preparation method of 2- (methylsulfonyl) -oxirane and derivatives thereof for solving the problems, the prepared 2- (methylsulfonyl) -oxirane and derivatives thereof have few by-products and high yield, and the 2- (methylsulfonyl) -oxirane and derivatives thereof can be applied to lithium ion battery electrolyte, so that the performance and the service life of a lithium ion battery can be obviously improved.
The invention adopts the specific technical scheme that: the preparation method of the 2- (methylsulfonyl) -oxirane and the derivative thereof is characterized by comprising the following steps:
(1) dissolving a raw material by using an organic solvent, wherein the raw material is vinyl methyl sulfone or allyl methyl sulfone or methallyl sulfonate;
(2) dividing the raw materials dissolved in the step (1) into three parts according to the mass ratio of 1:2:4, dropwise adding the three parts into m-chloroperoxybenzoic acid for three times, wherein the first addition time is 30min, the second addition time is 25min, the third addition time is 10min, heating and refluxing for 15-30h after the addition is finished, cooling to room temperature, filtering, and drying the filtrate in vacuum to obtain a product;
when the starting material is vinyl methyl sulfone, the product is 2- (methylsulfonyl) -oxirane;
when the starting material is allylmethylsulfone, the product is 2- [ (methylsulfonyl) methyl ] -oxirane;
when the raw material is methyl allyl sulfonate, the product is methyl-2, 3-epoxypropane sulfonate;
the molar ratio of the raw material to the m-chloroperoxybenzoic acid is 1 (1.8-2.4).
Further, the organic solvent is toluene, 1, 2-dichloromethane or methanol.
Further, the vinyl methyl sulfone or allyl methyl sulfone comprises the following preparation steps:
(1) dissolving anhydrous triethylamine in anhydrous ether, and then dropwise adding the anhydrous triethylamine into the reactant I at the temperature of 20-30 ℃ at the speed of 0.5-0.8ml/min while stirring; the reactant I is 1-chloro-2- (methylsulfonyl) ethane or 1-chloro-3-methanesulfonyl-propane;
(2) then adding the reactant II, dropwise adding at the speed of 1-1.2ml/min, and stirring at room temperature for 3-4h after dropwise adding to obtain a product; the reactant II is 1-chloro-2- (methylsulfonyl) ethane or 1-chloro-3-methylsulfonyl-propane;
dissolving 1mol of anhydrous triethylamine in 30-40ml of anhydrous ether; triethylamine, and the molar ratio of the reactant I to the reactant II in the step (1) is 2: 1: 1;
when the raw material is 1-chloro-2- (methylsulfonyl) ethane, the product is vinyl methyl sulfone;
when the starting material is 1-chloro-3-methanesulfonyl-propane, the product is allylmethylsulfone.
Further, the methallyl sulfonate comprises the following preparation steps:
sodium allylsulfonate and toluene are put into a reaction bottle after nitrogen replacement and stirred, and SOCl is dripped into the reaction bottle at the temperature of 12-18 DEG C2After 0.5-1h of dripping, heating to 45 ℃, stirring for reaction for 12h, cooling to room temperature, extracting by diethyl ether, drying, filtering, and concentrating to obtain 2-propylene-1-sulfonyl chloride; the allyl sulfonic acidSodium and SOCl2The molar ratio of (1), (1.3-1.5), SOCl2Volume ratio to toluene (0.4-0.6): 1;
dissolving sodium methoxide by using methanol to obtain a 30% sodium methoxide methanol solution, dissolving 2-propylene-1-sulfonyl chloride by using methanol to obtain a methanol solution of 2-propylene-1-sulfonyl chloride, then dropwise adding the methanol solution of 2-propylene-1-sulfonyl chloride into the sodium methoxide methanol solution at room temperature, dropwise adding at the speed of 1-1.8ml/min, stirring for reaction for 30-45h, extracting by using diethyl ether, carrying out suction filtration, and concentrating to obtain methallyl sulfonate;
the molar ratio of the 2-propylene-1-sulfonyl chloride to the sodium methoxide is 1 (1-1.3), and the dosage of the methanol for dissolving the 2-propylene-1-sulfonyl chloride is as follows: 1g of 2-propene-1-sulfonyl chloride was taken up with 2-3ml of methanol.
The invention has the beneficial effects that: the preparation method is simple, few in byproducts and high in yield, and can be applied to industrialization. Wherein 2-propene-1-sulfonyl chloride has CAS number 14418-84-9; 1-chloro-3-methanesulfonyl-propane, CAS No. 54533-11-8.
Drawings
FIG. 1 is a 1H NMR spectrum of 2- (methylsulfonyl) -oxirane prepared in example 1.
FIG. 2 is a 13C NMR spectrum of 2- (methylsulfonyl) -oxirane prepared in example 1.
FIG. 3 is a 1H NMR spectrum of 2- [ (methylsulfonyl) methyl ] -oxirane prepared in example 2.
FIG. 4 is a 13C NMR spectrum of 2- [ (methylsulfonyl) methyl ] -oxirane prepared in example 2.
FIG. 5 is a 1H NMR spectrum of methyl-2, 3-epoxypropane sulfonate prepared in example 3.
FIG. 6 is a 13C NMR spectrum of methyl-2, 3-epoxypropane sulfonate prepared in example 3.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Preparation of 2- (methylsulfonyl) -oxirane
Dissolving 10.12g of anhydrous triethylamine in 30ml of anhydrous ether, then dropwise adding the anhydrous triethylamine into 7.125g of 1-chloro-2- (methylsulfonyl) ethane at the temperature of 20 ℃, stirring while adding at the speed of 0.5ml/min, then adding 7.125g of 1-chloro-2- (methylsulfonyl) ethane, dropwise adding at the speed of 1ml/min, and stirring at room temperature for 3 hours after dropwise adding to obtain 8.49g of vinyl methyl sulfone;
dissolving vinyl methyl sulfone in 150mL of methanol organic solvent, dropwise adding 4.1g, 8.2g and 16.4g of m-chloroperoxybenzoic acid for three times, wherein the first addition time is 30min, the second addition time is 25min, the third addition time is 10min, heating and refluxing for 24h after the addition is finished, cooling to room temperature, filtering, and drying the filtrate in vacuum to obtain 5.97g of 2- (methylsulfonyl) -ethylene oxide with the yield of 61.2%.
Example 2
Preparation of 2- [ (methylsulfonyl) methyl ] -oxirane
Dissolving 10.12g of anhydrous triethylamine in 40ml of anhydrous ether, then dropwise adding the anhydrous triethylamine into 7.825g of 1-chloro-3-methanesulfonyl-propane at the temperature of 25 ℃, stirring while adding at the speed of 0.8ml/min, then adding 7.825g of 1-chloro-3-methanesulfonyl-propane, dropwise adding at the speed of 1.2ml/min, and stirring for 3 hours at room temperature after dropwise adding to obtain 9.37g of allyl methyl sulfone;
dissolving allyl methyl sulfone in 150mL of methanol organic solvent, dropwise adding 4g, 8g and 16g of m-chloroperoxybenzoic acid for three times, wherein the first addition time is 30min, the second addition time is 25min, the third addition time is 10min, heating and refluxing are carried out for 24h after the addition is finished, cooling to room temperature, filtering, and drying the filtrate in vacuum to obtain 7.08g of 2- [ (methylsulfonyl) methyl ] -ethylene oxide with the yield of 66.7%.
Example 3
Preparation of methyl-2, 3-epoxypropane sulfonate
36.03g of sodium allylsulfonate and 59ml of toluene were put into a reaction flask after replacement with nitrogen gas, stirred, and 23.6ml of SOCl was added dropwise at 12 ℃2After dropping for 1h, heating to 45 ℃, stirring for reaction for 12h, cooling to room temperature, extracting by diethyl ether, drying, filtering, and concentrating to obtain 28.12g of 2-propylene-1-sulfonyl chloride;
dissolving 14.05g of sodium methoxide by using 46.83ml of methanol to obtain a 30% sodium methoxide methanol solution, dissolving 2-propylene-1-sulfonyl chloride by using 56.24ml of methanol to obtain a methanol solution of 2-propylene-1-sulfonyl chloride, then dropwise adding the methanol solution of 2-propylene-1-sulfonyl chloride into the sodium methoxide methanol solution at room temperature, dropwise adding at the speed of 1.8ml/min, stirring for reacting for 45 hours, extracting by diethyl ether, carrying out suction filtration, and concentrating to obtain 23.12g of methallyl sulfonate;
dissolving methallyl sulfonate by 80ml of 1, 2-dichloromethane, dropwise adding 10g, 20g and 40g of m-chloroperoxybenzoic acid for three times, wherein the first addition time is 30min, the second addition time is 25min, the third addition time is 10min, after the addition is finished, heating and refluxing for 15h, cooling to room temperature, filtering, and drying filtrate in vacuum to obtain 16.36g of methyl-2, 3-epoxypropane sulfonate with the yield of 63.3%.
Comparative example 1
Preparation of 2- (methylsulfonyl) -oxirane
Dissolving 10.12g of anhydrous triethylamine in 30ml of anhydrous ether, then dropwise adding the anhydrous triethylamine into 14.25g of 1-chloro-2- (methylsulfonyl) ethane at 20 ℃, stirring while adding, and stirring for 3h at room temperature after dropwise adding to obtain 7.96g of vinyl methyl sulfone;
dissolving vinyl methyl sulfone with 150mL of methanol organic solvent, adding 28.7g of m-chloroperoxybenzoic acid, heating and refluxing for 24h, cooling to room temperature, filtering, and drying the filtrate under vacuum to obtain 4.14g of 2- (methylsulfonyl) -ethylene oxide with the yield of 45.2%.
Comparative example 2
Preparation of 2- [ (methylsulfonyl) methyl ] -oxirane
Dissolving 10.12g of anhydrous triethylamine in 40ml of anhydrous ether, then dropwise adding the anhydrous triethylamine into 15.65g of 1-chloro-3-methanesulfonyl-propane at 25 ℃, stirring while adding, and stirring for 3h at room temperature after dropwise adding to obtain 8.65g of allyl methyl sulfone;
allyl methyl sulfone was dissolved in 150mL of methanol organic solvent, 28g of m-chloroperoxybenzoic acid was added, the mixture was refluxed for 24 hours at elevated temperature, cooled to room temperature, filtered, and the filtrate was dried under vacuum to give 4.95g of 2- [ (methylsulfonyl) methyl ] -oxirane in 50.6% yield.
Comparative example 3
Preparation of methyl-2, 3-epoxypropane sulfonate
36.03g of sodium allylsulfonate and 59ml of toluene were put into a reaction flask after replacement with nitrogen gas, stirred, and 23.6ml of SOCl was added dropwise at 12 ℃2After dripping for 10min, heating to 45 ℃, stirring for reaction for 12h, cooling to room temperature, extracting with diethyl ether, drying, filtering, and concentrating to obtain 26.71g of 2-propylene-1-sulfonyl chloride;
dissolving 13.34g of sodium methoxide by using 44.47ml of methanol to obtain a 30% sodium methoxide methanol solution, dissolving 2-propylene-1-sulfonyl chloride by using 53.42ml of methanol to obtain a methanol solution of 2-propylene-1-sulfonyl chloride, then dropwise adding the methanol solution of 2-propylene-1-sulfonyl chloride into the sodium methoxide methanol solution at room temperature, dropwise adding at the speed of 4ml/min, stirring for reacting for 45 hours, extracting by diethyl ether, carrying out suction filtration, and concentrating to obtain 21.83g of methallyl sulfonate;
the methallyl sulfonate was dissolved in 80ml of 1, 2-dichloromethane, 70g of m-chloroperoxybenzoic acid was added, the mixture was refluxed for 15 hours at elevated temperature, cooled to room temperature, filtered, and the filtrate was dried under vacuum to obtain 13.44g of methyl-2, 3-epoxypropane sulfonate with a yield of 55.1%.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (4)
- A process for the preparation of 2- (methylsulfonyl) -oxirane, or a derivative thereof, comprising the steps of:(1) dissolving a raw material by using an organic solvent, wherein the raw material is vinyl methyl sulfone or allyl methyl sulfone or methallyl sulfonate;(2) dividing the raw materials dissolved in the step (1) into three parts according to the mass ratio of 1:2:4, dropwise adding the three parts into m-chloroperoxybenzoic acid for three times, wherein the first addition time is 30min, the second addition time is 25min, the third addition time is 10min, heating and refluxing for 15-30h after the addition is finished, cooling to room temperature, filtering, and drying the filtrate in vacuum to obtain a product;when the starting material is vinyl methyl sulfone, the product is 2- (methylsulfonyl) -oxirane;when the starting material is allylmethylsulfone, the product is 2- [ (methylsulfonyl) methyl ] -oxirane;when the raw material is methyl allyl sulfonate, the product is methyl-2, 3-epoxypropane sulfonate;the molar ratio of the raw material to the m-chloroperoxybenzoic acid is 1 (1.8-2.4).
- 2. The process for the preparation of 2- (methylsulfonyl) -oxirane or a derivative thereof according to claim 1, wherein the organic solvent is toluene, 1, 2-dichloromethane, or methanol.
- 3. The process for the preparation of 2- (methylsulfonyl) -oxirane or derivatives thereof according to claim 1, wherein the vinyl methyl sulfone or allyl methyl sulfone comprises the following steps:(1) dissolving anhydrous triethylamine in anhydrous ether, and then dropwise adding the anhydrous triethylamine into the reactant I at the temperature of 20-30 ℃ at the speed of 0.5-0.8ml/min while stirring; the reactant I is 1-chloro-2- (methylsulfonyl) ethane or 1-chloro-3-methanesulfonyl-propane;(2) then adding the reactant II, dropwise adding at the speed of 1-1.2ml/min, and stirring at room temperature for 3-4h after dropwise adding to obtain a product; the reactant II is 1-chloro-2- (methylsulfonyl) ethane or 1-chloro-3-methylsulfonyl-propane;dissolving 1mol of anhydrous triethylamine in 30-40ml of anhydrous ether; triethylamine, and the molar ratio of the reactant I to the reactant II in the step (1) is 2: 1: 1;when the raw material is 1-chloro-2- (methylsulfonyl) ethane, the product is vinyl methyl sulfone;when the starting material is 1-chloro-3-methanesulfonyl-propane, the product is allylmethylsulfone.
- 4. The process for the preparation of 2- (methylsulfonyl) -oxirane or a derivative thereof according to claim 1, wherein the methallyl sulfonate comprises the following steps:sodium allylsulfonate and toluene are put into a reaction bottle after nitrogen replacement and stirred, and SOCl is dripped into the reaction bottle at the temperature of 12-18 DEG C2After 0.5-1h of dripping, heating to 45 ℃, stirring for reaction for 12h, cooling to room temperature, extracting by diethyl ether, drying, filtering, and concentrating to obtain 2-propylene-1-sulfonyl chloride; sodium allylsulfonate and SOCl2The molar ratio of (1), (1.3-1.5), SOCl2Volume ratio to toluene (0.4-0.6): 1;dissolving sodium methoxide by using methanol to obtain a 30% sodium methoxide methanol solution, dissolving 2-propylene-1-sulfonyl chloride by using methanol to obtain a methanol solution of 2-propylene-1-sulfonyl chloride, then dropwise adding the methanol solution of 2-propylene-1-sulfonyl chloride into the sodium methoxide methanol solution at room temperature, dropwise adding at the speed of 1-1.8ml/min, stirring for reaction for 30-45h, extracting by using diethyl ether, carrying out suction filtration, and concentrating to obtain methallyl sulfonate;the molar ratio of the 2-propylene-1-sulfonyl chloride to the sodium methoxide is 1 (1-1.3), and the dosage of the methanol for dissolving the 2-propylene-1-sulfonyl chloride is as follows: 1g of 2-propene-1-sulfonyl chloride was taken up with 2-3ml of methanol.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101426823A (en) * | 2006-04-19 | 2009-05-06 | 丰田自动车株式会社 | Vinyl polymer of sulfone group-containing monomer, method for producing the same, polymer electrolyte, polymer electrolyte membrane, andfuel cell |
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2020
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