CN114075165A - Preparation method of 2, 4-butane sultone - Google Patents
Preparation method of 2, 4-butane sultone Download PDFInfo
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- CN114075165A CN114075165A CN202010836591.1A CN202010836591A CN114075165A CN 114075165 A CN114075165 A CN 114075165A CN 202010836591 A CN202010836591 A CN 202010836591A CN 114075165 A CN114075165 A CN 114075165A
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- butane sultone
- sodium
- aqueous solution
- hydroxybutane
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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 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- RTTNOHLFPFFOCA-UHFFFAOYSA-N 3-hydroxybutane-1-sulfonic acid Chemical compound CC(O)CCS(O)(=O)=O RTTNOHLFPFFOCA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 23
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 23
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 claims abstract description 21
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 21
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 13
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000000061 acid fraction Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 5
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 5
- LSPPRHYSWKZGRZ-UHFFFAOYSA-M sodium;3-hydroxybutane-1-sulfonate Chemical compound [Na+].CC(O)CCS([O-])(=O)=O LSPPRHYSWKZGRZ-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000003729 cation exchange resin Substances 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 11
- 230000020477 pH reduction Effects 0.000 abstract description 8
- 238000010924 continuous production Methods 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 238000006277 sulfonation reaction Methods 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 4
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 3
- -1 3-hydroxybutanesulfonic acid sodium Chemical compound 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007342 radical addition reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KMBRJVMBQNMRDM-UHFFFAOYSA-N 1-hydroxybutane-1-sulfonic acid Chemical compound CCCC(O)S(O)(=O)=O KMBRJVMBQNMRDM-UHFFFAOYSA-N 0.000 description 2
- MDNTXXADGNHVHA-UHFFFAOYSA-N CCCC.[Na] Chemical compound CCCC.[Na] MDNTXXADGNHVHA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- NQAWQSVOOHTLEY-UHFFFAOYSA-N 1-chlorobutane-1-sulfonic acid Chemical compound CCCC(Cl)S(O)(=O)=O NQAWQSVOOHTLEY-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- UFQDKRWQSFLPQY-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-3-ium;chloride Chemical compound Cl.C1CN=CN1 UFQDKRWQSFLPQY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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 relates to a preparation method of 2, 4-butane sultone, which comprises the following steps: A. taking 2-butenol and sodium bisulfite aqueous solution as raw materials, taking sodium nitrate aqueous solution as a catalyst, and heating and carrying out reflux reaction under the stirring condition to obtain a solution containing 3-hydroxybutane sulfonic acid sodium salt; B. acidifying with ion exchange resin, adding a dehydrating agent, distilling under normal pressure to remove water and the dehydrating agent, then distilling under reduced pressure, and collecting 3-hydroxybutanesulfonic acid fraction; C. and (3) continuously flashing, dehydrating and cyclizing the 3-hydroxybutanesulfonic acid concentrated solution under the high-temperature vacuum condition to obtain 2, 4-butanesultone. The method has the advantages of simple process route, mild conditions, cheap and easily-obtained reaction substrates and catalysts, resin acidification, continuous production guarantee, loss and production cost reduction in the intermediate reaction link, simple post-treatment and high target product yield of over 80 percent.
Description
Technical Field
The invention belongs to the field of synthesis of fine chemical intermediates, and particularly relates to a preparation method of 2, 4-butane sultone.
Background
The 2, 4-butane sultone is colorless or yellowish red transparent liquid at normal temperature, has a flash point of 93 ℃, a boiling point of 150 ℃ (1.6kPa), a relative density of 1.31, is insoluble in water, and can be mutually dissolved with various organic solvents. The 2, 4-butane sultone is an organic sulfoalkylation reagent and a fine chemical intermediate with important application prospect, and can be used for synthesizing (gemini) surfactants, photosensitive materials, medical intermediates, color dye sensitizers, daily chemicals and the like. In recent years, 2, 4-butane sultone has been actively used in the fields of synthesis of plating intermediates, lithium ion battery additives, and the like, and particularly, it has been considered important to develop a secondary lithium ion battery additive that exhibits excellent performance.
The existing methods for preparing 2, 4-butane sultone mainly comprise the following steps:
(1) 1, 3-propane sultone and methyl bromide are taken as raw materials, and 2, 4-butane sultone is obtained through one-step reaction under the action of a catalyst butyl lithium, and the defects are that: the reaction condition is harsh, the reaction needs to be carried out under the condition of deep cooling at minus 78 ℃, and the monobromomethane which is a main raw material has serious destructiveness to ozone, is a rejected chemical product at present and has no industrial value;
(2) 1-butylene and sulfur trioxide are used as raw materials, and 2, 4-butane sultone is obtained through one-step reaction under the action of a catalyst butyl lithium, and the defects are as follows: the reaction conditions are harsh, the cryogenic cooling condition at-78 ℃ is also required, and partial 1-butene can generate self-polymerization to generate oligomers in the processes of storage, transportation and reaction, impurities are generated, and the final yield is influenced;
(3) the method takes butylene chloride and sulfur dioxide as initial raw materials, butylene chloride is sulfonated by sulfur dioxide to obtain chlorobutane sulfonic acid, and then dehydrochlorination is carried out to obtain 2, 4-butane sultone through cyclization reaction, and has the disadvantages that the reaction is complex, gas-liquid heterogeneous reaction is involved, the transportation, storage and the like of sulfur dioxide are involved, and the main raw material of butylene chloride belongs to dangerous goods, is highly flammable and strong in corrosivity, can carry out self-polymerization during storage, transportation and reaction, is not suitable for long-term storage, and has lower reaction yield;
(4) crotonaldehyde and sodium bisulfite are taken as initial raw materials, the crotonaldehyde is sulfonated by the sodium bisulfite to obtain aldehyde butane sodium sulfonate, then the aldehyde butane sodium sulfonate is obtained by high-pressure hydrogenation under the catalysis of raney nickel, hydroxybutane sulfonic acid is obtained by an acidification process, and finally the 2, 4-butane sultone is obtained by heating, vacuum dehydration and cyclization, wherein the defects of the method are as follows: the reaction synthesis steps are more, the process is more complex, high-pressure hydrogenation reaction is involved, the danger is higher, the sodium bisulfite can also generate nucleophilic addition reaction with the carbonyl of the crotonaldehyde, partial carbonyl is consumed, the raw material crotonaldehyde is wasted, and the reaction yield is lower;
(5) crotyl alcohol and sodium bisulfite are used as initial raw materials, sulfonation addition reaction is directly carried out under the acidic condition to prepare hydroxybutane sulfonic acid, and then 2, 4-butane sultone is obtained through dehydration, wherein the defects are as follows: the position of the sulfonic acid group is uncertain during sulfonation addition to generate impurities (isomers are generated during addition), the sulfonic acid group is positioned at the position of the carbon No. 3 after partial addition besides the carbon No. 2, and finally the yield of the 2, 4-butane sultone is low; in addition, the use of sulfuric acid for acidification is not convenient for industrial continuous production.
Disclosure of Invention
The invention aims to solve the technical problems of complex reaction steps, harsh reaction conditions, inconvenience in industrial continuous production, low yield caused by impurities generated during sulfonation and the like in the preparation of 2, 4-butane sultone in the prior art.
The technical scheme for solving the technical problems is as follows: a preparation method of 2, 4-butane sultone comprises the following steps:
A. preparation of 3-hydroxybutane sulfonic acid sodium salt: putting 2-butenol (crotyl alcohol) and sodium bisulfite aqueous solution into a reaction vessel, fully mixing, dropwise adding a catalyst sodium nitrate aqueous solution, heating under stirring, carrying out reflux reaction for 3-5 hours, and cooling to room temperature to obtain a solution containing 3-hydroxybutane sulfonic acid sodium salt, wherein the reaction temperature is 70-90 ℃;
B. preparation of 3-hydroxybutanesulfonic acid: acidifying the solution of the 3-hydroxybutane sulfonate in the step A by using ion exchange resin to obtain a crude product of the 3-hydroxybutane sulfonic acid, adding a dehydrating agent, distilling under normal pressure to remove water and the dehydrating agent, then distilling under reduced pressure, and collecting a fraction of the 3-hydroxybutane sulfonic acid;
C. preparation of 2, 4-butane sultone: the 3-hydroxybutanesulfonic acid is continuously flashed, dehydrated and cyclized under the high-temperature vacuum condition to obtain the 2, 4-butanesultone, the reaction temperature is 130-150 ℃, the vacuum degree is 1-10mmHg, and the reaction time is 4-8 hours.
On the basis of the above technical solutions, the present invention may further have the following specific selection or optimal selection.
Specifically, the molar ratio of the 2-butenol to the sodium bisulfite in the A is 1: 1.2-2.0, preferably about 1:1.5, and the mass of sodium nitrate used is 0.5-2.0% of the mass of 2-butenol, more preferably 1.0%.
Specifically, the mass fraction of sodium bisulfite in the sodium bisulfite aqueous solution in A is 15-30 wt%, and 25 wt% is the best; the mass fraction of sodium nitrate in the aqueous solution of sodium nitrate is 20 to 40 wt%, preferably 25 to 30 wt%, and sodium nitrate is understood in a broad sense and represents nitrates such as potassium nitrate and ammonium nitrate having good water solubility.
Specifically, the ion exchange resin in B is a strongly acidic styrene sulfonic cation exchange resin.
Specifically, the vacuum degree of the reduced pressure distillation in the step B is 2-5mmHg, and the fraction at the temperature of 110-115 ℃ collected during the reduced pressure distillation is the 3-hydroxybutanesulfonic acid fraction.
Specifically, the dehydrating agent used in the step B is chlorobenzene, toluene or diethyl ether.
Compared with the prior art, the invention has the beneficial effects that:
(1) the synthetic process route of the invention is simple, the reaction condition is mild and stable, the main reaction substrate and the catalyst are cheap and easily available chemicals, the loss and the production cost of the intermediate reaction link are reduced by adopting a continuous production process, the post-treatment process steps are optimized, the total yield of the obtained 2, 4-butane sultone can reach more than 80 percent, the product purity is high and can reach more than 98.00 percent, the water content is lower than 200ppm, and the acid value (calculated by HF) is lower than 50 ppm.
(2) The 2-butenol (crotyl alcohol) and the sulfonating agent sodium bisulfite have better positioning effect during sulfonation reaction under the action of the catalyst sodium nitrate, reduce the generation of isomer impurities and effectively improve the yield of the 2, 4-butane sultone; meanwhile, sodium nitrate is a cheap and easily available chemical, and is used as a catalyst, so that the cost is low, the reaction speed is high, and the yield is high;
(3) abandons the traditional acidification process of hydrochloric acid and sulfuric acid, adopts strong acid styrene cation exchange resin to carry out acidification, and the resin matrix is provided with sulfonic acid group (-SO)3H) The active group effectively reduces the use amount of inorganic acid and solvent, effectively reduces industrial wastewater, and the resin can be backwashed and regenerated, thereby being beneficial to continuous industrial production;
(4) the refining of the 3-hydroxybutanesulfonic acid is carried out by adopting a dehydrating agent method, and the preliminary fractionation reaction is carried out under normal pressure with the assistance of dehydrating agents such as chlorobenzene, toluene, ether and the like, so that the energy consumption is reduced, and the safety is improved.
Detailed Description
The present invention is described in further detail below with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
For the sake of brevity, the drugs used in the following examples are commercially available products unless otherwise specified, and the methods used are prior art unless otherwise specified.
Example 1
The preparation method of the 2, 4-butane sultone comprises the following steps:
A. putting 2-butenol and a sodium bisulfite aqueous solution (15 wt%) into a reaction vessel, fully mixing, wherein the molar ratio of the 2-butenol to the sodium bisulfite is 1:1.2, dropwise adding a catalyst sodium nitrate aqueous solution (the concentration of sodium nitrate is 40 wt%, and the dosage of sodium nitrate is 0.5% of the mass of the 2-butenol), heating and refluxing under stirring conditions to generate a free radical addition reaction, controlling the reaction temperature to be 70 ℃, the pH value to be 6-7, reacting for 3 hours, and cooling to room temperature after the reaction is finished to obtain an intermediate 3-hydroxybutanesulfonic acid sodium sulfonate solution;
B. adopting an ion exchange process, acidifying the 3-hydroxybutane sulfonate solution in the step A by using styrene cation exchange resin to obtain 3-hydroxybutane sulfonic acid, adding a dehydrating agent chlorobenzene into a crude product of the 3-hydroxybutane sulfonic acid, fractionating and recovering chlorobenzene produced water under the normal pressure condition, then fractionating under reduced pressure under the vacuum degree of 2mmHg, keeping the reflux ratio at 1:1.5, recovering 110-111 ℃ fraction, and removing trace water to obtain 3-hydroxybutane sulfonic acid fraction, wherein the ion exchange acidification process is carried out at normal temperature and normal pressure;
C. distilling the above 3-hydroxybutanesulfonic acid at 135 deg.C under 1-5mmHg, reacting for 4 hr to dehydrate and sulfonate 3-hydroxybutanesulfonic acid to obtain colorless transparent 2, 4-butanesultone (purity 98.85%, yield 80.5%).
Example 2
The preparation method of the 2, 4-butane sultone comprises the following steps:
A. putting 2-butenol and a sodium bisulfite aqueous solution (25 wt%) into a reaction vessel, fully mixing, wherein the molar ratio of the 2-butenol to the sodium bisulfite is 1:1.5, dropwise adding a catalyst sodium nitrate aqueous solution (the concentration of sodium nitrate is 25 wt%, and the dosage of sodium nitrate is 1.0% of the mass of the 2-butenol), heating and refluxing under stirring conditions to generate a free radical addition reaction, controlling the reaction temperature to be 80 ℃, the pH value to be 6-7, reacting for 4 hours, and cooling to room temperature after the reaction is finished to obtain an intermediate 3-hydroxybutanesulfonic acid sodium sulfonate solution;
B. adopting an ion exchange process, acidifying the 3-hydroxybutane sulfonate solution in the step A by using styrene cation exchange resin to obtain 3-hydroxybutane sulfonic acid, adding a dehydrating agent toluene into a 3-hydroxybutane sulfonic acid crude product, fractionating and recovering toluene produced water under the normal pressure condition, then fractionating under the vacuum degree of 3mmHg, keeping the reflux ratio at 1:1.7, recovering 112-113 ℃ fraction, and removing trace water to obtain 3-hydroxybutane sulfonic acid fraction, wherein the ion exchange acidification process is carried out at normal temperature and normal pressure;
C. distilling the above 3-hydroxybutanesulfonic acid under reduced pressure at 140 deg.C and vacuum degree of 2-7mmHg, reacting for 6 hr to dehydrate and sulfonate 3-hydroxybutanesulfonic acid to obtain colorless and transparent 2, 4-butanesultone (purity 98.92%, yield 83.1%).
Example 3
The preparation method of the 2, 4-butane sultone comprises the following steps:
A. putting 2-butenol and a sodium bisulfite aqueous solution (30 wt%) into a reaction vessel, fully mixing, wherein the molar ratio of the 2-butenol to the sodium bisulfite is 1:2.0, dropwise adding a catalyst sodium nitrate aqueous solution (the concentration of sodium nitrate is 30 wt%, and the dosage of sodium nitrate is 2.0% of the mass of the 2-butenol), heating and refluxing under stirring conditions to generate a free radical addition reaction, controlling the reaction temperature to be 90 ℃, the pH value to be 6-7, reacting for 5 hours, and cooling to room temperature after the reaction is finished to obtain an intermediate 3-hydroxybutanesulfonic acid sodium sulfonate solution;
B. adopting an ion exchange process, acidifying the 3-hydroxybutane sulfonate solution in the step A by using styrene cation exchange resin to obtain 3-hydroxybutane sulfonic acid, adding a dehydrating agent diethyl ether into a crude product of the 3-hydroxybutane sulfonic acid, fractionating and recovering diethyl ether produced water under the normal pressure condition, then fractionating under reduced pressure under the vacuum degree of 5mmHg, keeping the reflux ratio at 1:2, recovering 114-115 ℃ fraction, and removing trace water to obtain a 3-hydroxybutane sulfonic acid fraction, wherein the ion exchange acidification process is carried out at normal temperature and normal pressure;
C. distilling the above 3-hydroxybutanesulfonic acid under reduced pressure at 145 deg.C under vacuum degree of 5-10mmHg, reacting for 7 hr to dehydrate and sulfonate 3-hydroxybutanesulfonic acid to obtain colorless and transparent 2, 4-butanesultone (purity 98.50%, yield 81.2%).
Comparative example 1
Compared with example 1, the only difference is that azodiisobutyl imidazoline hydrochloride (AIBI) is used as an initiator in the step A, other reaction conditions and material consumption are kept unchanged except for necessary adaptability adjustment, and colorless and transparent 2, 4-butane sultone is collected, the purity is 98.78%, and the yield is 62.3%.
Comparative example 2
Compared with example 1, the difference is only that Benzoyl Peroxide (BPO) is used as an initiator in the step A, other reaction conditions and the material consumption are kept unchanged except for necessary adaptability adjustment, and the colorless and transparent 2, 4-butane sultone is collected to have the purity of 98.83 percent and the yield of 59.8 percent.
When crotyl alcohol and a sodium bisulfite aqueous solution are used as raw materials and a conventional free radical initiator (such as azobisisobutyrimidazoline hydrochloride or benzoyl peroxide in comparative examples 1 and 2) is used in the prior art, the addition position of a sulfonic acid group is uncertain during sulfonation addition, and a position isomer is easily generated to introduce impurities, so that the yield of the final 2, 4-butane sultone is low and is only about 60%; in the examples 1 to 3, the yield of 2, 4-butane sultone can be improved to more than 80% without using sodium nitrate as a catalyst as a raw material, and the applicant analyzes that the sodium nitrate has a better positioning effect when used as a catalyst to initiate a sulfonation addition reaction, and reduces the generation of isomer impurities.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A preparation method of 2, 4-butane sultone is characterized by comprising the following steps:
A. preparation of 3-hydroxybutane sulfonic acid sodium salt: putting 2-butenol and a sodium bisulfite aqueous solution into a reaction vessel for full mixing, dropwise adding a catalyst sodium nitrate aqueous solution, heating for reflux reaction for 3-5 hours under the condition of stirring, and cooling to room temperature to obtain a solution containing 3-hydroxybutane sulfonic acid sodium salt, wherein the reaction temperature is 70-90 ℃;
B. preparation of 3-hydroxybutanesulfonic acid: acidifying the solution of the 3-hydroxybutane sulfonate in the step A by using ion exchange resin to obtain a crude product of the 3-hydroxybutane sulfonic acid, adding a dehydrating agent, distilling under normal pressure to remove water and the dehydrating agent, then distilling under reduced pressure, and collecting a fraction of the 3-hydroxybutane sulfonic acid;
C. preparation of 2, 4-butane sultone: the 3-hydroxybutanesulfonic acid is continuously flashed, dehydrated and cyclized under the high-temperature vacuum condition to obtain the 2, 4-butanesultone, the reaction temperature is 130-150 ℃, the vacuum degree is 1-10mmHg, and the reaction time is 4-8 hours.
2. The method for preparing 2, 4-butane sultone according to claim 1, wherein the molar ratio of 2-butenol to sodium bisulfite in A is 1:1.2 to 2.0 percent, and the mass of the used sodium nitrate is 0.5 to 2.0 percent of the mass of the 2-butenol.
3. The method according to claim 1, wherein the mass fraction of sodium bisulfite in the aqueous solution of sodium bisulfite in A is 15-30 wt%, and the mass fraction of sodium nitrate in the aqueous solution of sodium nitrate is 20-40 wt%.
4. The method as claimed in claim 1, wherein the degree of vacuum of the reduced pressure distillation in B is 2-5mmHg, and the fraction of 110-115 ℃ is collected during the reduced pressure distillation to obtain the 3-hydroxybutanesulfonic acid fraction.
5. The method for preparing 2, 4-butane sultone according to claim 1, wherein the ion exchange resin in B is a strongly acidic styrene sulfonic cation exchange resin.
6. A process for preparing 2, 4-butane sultone according to any one of claims 1 to 5, wherein the dehydrating agent used in B is chlorobenzene, toluene or diethyl ether.
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