CN108840852A - A kind of preparation method of methane-disulfonic acid methylene ester - Google Patents
A kind of preparation method of methane-disulfonic acid methylene ester Download PDFInfo
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- CN108840852A CN108840852A CN201810914342.2A CN201810914342A CN108840852A CN 108840852 A CN108840852 A CN 108840852A CN 201810914342 A CN201810914342 A CN 201810914342A CN 108840852 A CN108840852 A CN 108840852A
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- C07—ORGANIC CHEMISTRY
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- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
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Abstract
The invention discloses a kind of preparation method of methane-disulfonic acid methylene ester, which includes sulfonating reaction and dehydration condensation, and the sulfonating reaction is to carry out sulfonating reaction with Loprazolam and sulfonating agent to obtain methylene-disulfonic acid；The dehydration condensation is that the methylene-disulfonic acid prepared with sulfonating reaction and formaldehyde compounds dissolve in organic solvent, in the presence of dehydrating agent, it carries out dehydration condensation and generates methane-disulfonic acid methylene ester crude product, resulting methane-disulfonic acid methylene ester crude product is added to the water washing, dries up to methane-disulfonic acid methylene ester fine work.A kind of preparation method of methane-disulfonic acid methylene ester of the present invention has been abandoned traditional using methylene-disulfonic acid sodium as raw material, and by precipitating, acidification is dehydrated the method for obtaining intermediate methylene-disulfonic acid.Directly adopt Loprazolam it is sulfonated after obtain methylene-disulfonic acid, simple production process of the present invention, atom utilization is high, and the three wastes are few, high income.
Description
Technical field
The present invention relates to organic-matter chemical synthetic method field, especially a kind of preparation side of methane-disulfonic acid methylene ester
Method.
Background technique
Methane-disulfonic acid methylene ester is a kind of chemicals English that appearance is white or off-white color crystal or crystalline powder
Title 1,5,2,4-dioxadithiane-2,2,4,4-tetraoxide.Abbreviation MMDS, molecular formula C2H4O6S2, No. CAS
99591-74-9, structural formula are：
Methane-disulfonic acid methylene ester (MMDS) is a kind of important medicine intermediate and electronic chemical product, is added to MMDS's
Battery has good high temperature cyclic performance.The power battery of positive electrode is done suitable for power battery, especially LiMn2O4,
MMDS can prevent the Mn melted out under high temperature to be adsorbed on negative terminal surface, it is suppressed that and impedance rise effectively increases cycle period characteristic,
Its cycle life can be greatly increased, furthermore MMDS also acts as the pharmaceutical preparation of leukaemia etc. in treatment animal.
Methane-disulfonic acid methylene ester is mainly following preparation method in the prior art：
It uses methylene-disulfonic acid sodium for raw material, is reacted with barium chloride and generate methylene-disulfonic acid barium, then be acidified by sulfuric acid,
Obtain the aqueous solution of methylene-disulfonic acid.Again by the aqueous solution high temperature dehydration of methylene-disulfonic acid, two sulphur of solid methylene is obtained
Acid.By resulting solid methylene-disulfonic acid solid and phosphorus pentoxide, polyformaldehyde reaction, product MMDS is finally obtained.
When above-mentioned technique produces, the three wastes of generation are more, and energy consumption is high and complex steps, final yield are also low.It is unfavorable for work
Skill metaplasia produces and environmentally protective theory, therefore develops a kind of easy to operate, high income, and the few technique of the three wastes of generation has very much must
It wants.
Summary of the invention
The defects of in view of the prior art, a kind of preparation method of methane-disulfonic acid methylene ester is provided.
The present invention is realized by following proposal：
A kind of preparation method of methane-disulfonic acid methylene ester, the preparation method include sulfonating reaction and dehydration condensation,
The sulfonating reaction is to carry out sulfonating reaction with Loprazolam and sulfonating agent to obtain methylene-disulfonic acid；The dehydration condensation
It is that the methylene-disulfonic acid prepared with sulfonating reaction and formaldehyde compounds dissolve in organic solvent, in the presence of dehydrating agent,
It carries out dehydration condensation and generates methane-disulfonic acid methylene ester crude product, resulting methane-disulfonic acid methylene ester crude product is added to the water
Washing is dried up to methane-disulfonic acid methylene ester fine work.
The sulfonating agent is one or more of the concentrated sulfuric acid, oleum, chlorosulfonic acid, sulfur trioxide, sulfamic acid
Mixture.
The formaldehyde compounds be one of formaldehyde gas, paraformaldehyde, metaformaldehyde, four polyformaldehyde, dimethoxym ethane or
Several mixtures.
The dehydrating agent is one of phosphorus pentoxide, solid phosgene, thionyl chloride, the concentrated sulfuric acid, phosphorus trichloride or several
Kind mixture.
The organic solvent is sulfolane, in ethyl acetate, dichloroethanes, methylene chloride, glycol dimethyl ether, acetic anhydride
One or more of mixtures.The mass ratio of Loprazolam and organic solvent is 1:5~1:50.
In the sulfonating reaction, the molar ratio of Loprazolam and sulfonating agent is 1:1~1:10, reaction temperature be 50 DEG C~
200 DEG C, the reaction time be 1~for 24 hours, reaction pressure be 0.1Mpa~10Mpa.
In the dehydration condensation, the molar ratio of methylene-disulfonic acid and formaldehyde object is 1:1~1:10, two sulphur of methylene
The molar ratio of acid and dehydrating agent is 1:0.4~1:4, reaction temperature is 80 DEG C~140 DEG C, and the reaction time is 2~12h, reaction pressure
Power is 0.1Mpa~10Mpa.
Beneficial effects of the present invention are：
A kind of preparation method of methane-disulfonic acid methylene ester of the present invention abandoned it is traditional with methylene-disulfonic acid sodium for original
Material, by precipitating, acidification is dehydrated the method for obtaining intermediate methylene-disulfonic acid.Directly adopt Loprazolam it is sulfonated after
To methylene-disulfonic acid, simple production process of the present invention, atom utilization is high, and the three wastes are few, high income.
Specific embodiment
The preferred embodiment of the invention is further illustrated below：
A kind of preparation method of methane-disulfonic acid methylene ester, the preparation method include sulfonating reaction and dehydration condensation,
The sulfonating reaction is to carry out sulfonating reaction with Loprazolam and sulfonating agent to obtain methylene-disulfonic acid；The dehydration condensation
It is that the methylene-disulfonic acid prepared with sulfonating reaction and formaldehyde compounds dissolve in organic solvent, in the presence of dehydrating agent,
It carries out dehydration condensation and generates methane-disulfonic acid methylene ester crude product, resulting methane-disulfonic acid methylene ester crude product is added to the water
Washing is dried up to methane-disulfonic acid methylene ester fine work.
The sulfonating agent is one or more of the concentrated sulfuric acid, oleum, chlorosulfonic acid, sulfur trioxide, sulfamic acid
Mixture.
The formaldehyde compounds be one of formaldehyde gas, paraformaldehyde, metaformaldehyde, four polyformaldehyde, dimethoxym ethane or
Several mixtures.
The dehydrating agent is one of phosphorus pentoxide, solid phosgene, thionyl chloride, the concentrated sulfuric acid, phosphorus trichloride or several
Kind mixture.
The organic solvent is sulfolane, in ethyl acetate, dichloroethanes, methylene chloride, glycol dimethyl ether, acetic anhydride
One or more of mixtures.The mass ratio of Loprazolam and organic solvent is 1:5~1:50.
In the sulfonating reaction, the molar ratio of Loprazolam and sulfonating agent is 1:1~1:10, reaction temperature be 50 DEG C~
200 DEG C, the reaction time be 1~for 24 hours, reaction pressure be 0.1Mpa~10Mpa.
In the dehydration condensation, the molar ratio of methylene-disulfonic acid and formaldehyde object is 1:1~1:10, two sulphur of methylene
The molar ratio of acid and dehydrating agent is 1:0.4~1:4, reaction temperature is 80 DEG C~140 DEG C, and the reaction time is 2~12h, reaction pressure
Power is 0.1Mpa~10Mpa.
The application is further elaborated below with reference to specific embodiment.
Embodiment 1
At room temperature, equipped with stirring, the first of 48g (0.5mol) is added in the four-hole bottle of dropping funel for thermometer, condenser
Alkyl sulfonic acid opens stirring, and the sulfur trioxide liquid of 40g (0.5mol) is added dropwise, and it is 25 DEG C -35 DEG C that temperature in controlling in the process, which is added dropwise,
Time for adding is controlled in 3-4h.110 DEG C are warming up to after completion of dropwise addition, reflux heat preservation 6h, reaction terminates, and system is thick liquid
Body, nmr analysis are methylene-disulfonic acid.System is down to room temperature, and the sulfolane of 300g is added, and stirs 0.5h, system dissolved clarification.It takes
The paraformaldehyde of 16.5g (0.55mol) and the phosphorus pentoxide of 35.5g (0.25mol) are added in there-necked flask, open stirring, body
System is uniformly dispersed, and is warming up to 110 DEG C, keeps the temperature 8h.Reaction end system is rufous liquid, and reaction solution is poured into 100g ice water
(0-5 DEG C of water temperature) stirs 0.5h, filters, and 50 DEG C of decompression dryings obtain white fine work 76.5g, yield 81.4%.Nuclear magnetic spectrum
For1H-NMR(400MHz,CD3CN)δ(ppm)：5.33 (s, 2H), 6.00 (s, 2H).
Embodiment 2
At room temperature, equipped with stirring, the first of 48g (0.5mol) is added in the four-hole bottle of dropping funel for thermometer, condenser
Alkyl sulfonic acid opens stirring, and the chlorosulfonic acid of 58g (0.5mol) is added dropwise, controlled during being added dropwise in temperature be 25 DEG C -35 DEG C, when dropwise addition
Between control in 3-4h.It is warming up to 110 DEG C, reflux heat preservation 6h after completion of dropwise addition, has hcl reaction generation, tail gas in reaction process
It is absorbed with lye.Reaction terminates, and system is viscous liquid, and nmr analysis is methylene-disulfonic acid.System is down to room temperature, is added
The glycol dimethyl ether of 300g stirs 0.5h, system dissolved clarification.Take the metaformaldehyde and 89.1g of 16.5g (0.55mol)
The solid phosgene of (0.3mol) is added in there-necked flask, opens stirring, and system is uniformly dispersed, and is warming up to 90 DEG C, keeps the temperature 12h.Reaction
End system is brown liquid, and reaction solution is poured into 100g ice water (0-5 DEG C of water temperature), stirs 0.5h, is filtered, and 50 DEG C of decompressions are dried
It is dry, obtain white fine work 81g, yield 86.17%.Nuclear magnetic spectrum is1H-NMR(400MHz,CD3CN)δ(ppm)：5.33 (s,
2H), 6.00 (s, 2H).
Embodiment 3
At room temperature, equipped with stirring, the first of 48g (0.5mol) is added in the autoclave of dropping funel for thermometer, condenser
Alkyl sulfonic acid opens stirring, is warming up to 180 DEG C, the sulfur trioxide gas of 40g (0.5mol) is passed through, after being passed through sulfur trioxide.
1h is kept the temperature, is cooled to room temperature, system is chip solid, and nmr analysis is methylene-disulfonic acid.The ethyl acetate of 300g is added, stirs
0.5h is mixed, methylene-disulfonic acid is dispersed in system at sand-like.Take four polyformaldehyde and 65.45g of 16.5g (0.55mol)
The thionyl chloride of (0.55mol) is added in there-necked flask, opens stirring, and system is uniformly dispersed, and is warming up to 80 DEG C, keeps the temperature 15h.Instead
Tail gas is absorbed with lye during answering, and reaction end system is yellow liquid, and reaction solution is poured into 100g ice water (water temperature 0-5
DEG C), 0.5h is stirred, is filtered, 50 DEG C of decompression dryings obtain white fine work 73.54g, yield 78.23%.Nuclear magnetic spectrum is1H-
NMR(400MHz,CD3CN)δ(ppm)：5.33 (s, 2H), 6.00 (s, 2H).
Embodiment 4
At room temperature, equipped with stirring, the first of 48g (0.5mol) is added in the four-hole bottle of dropping funel for thermometer, condenser
Alkyl sulfonic acid opens stirring, and the sulfamic acid of 48.5g (0.5mol) is added dropwise, and it is 25 DEG C -35 DEG C that temperature in controlling in the process, which is added dropwise, drips
Control is in 3-4h between added-time.150 DEG C, reflux heat preservation 3h are warming up to after completion of dropwise addition,.Reaction terminates, and system is viscous liquid,
Nmr analysis is methylene-disulfonic acid.System is down to room temperature, and the acetic anhydride of 300g is added, and stirs 0.5h, system dissolved clarification.It takes
The multistage formaldehyde of 16.5g (0.55mol) and the phosphorus trichloride of 123.6g (0.9mol) are added in there-necked flask, open stirring, system
It is uniformly dispersed, is warming up to 120 DEG C, keep the temperature 5h.Reaction end system is brown liquid, and reaction solution is poured into (water in 100g ice water
Warm 0-5 DEG C), 0.5h is stirred, is filtered, 50 DEG C of decompression dryings obtain white fine work 83.4g, yield 88.72%.Nuclear magnetic spectrum is1H-NMR(400MHz,CD3CN)δ(ppm)：5.33 (s, 2H), 6.00 (s, 2H).
The preparation method of the application is former with raw material Loprazolam cheap and easy to get, sulfonating agent, formaldehyde compounds, dehydrating agent
Material, prepares methane-disulfonic acid methylene ester, the preparation method of the application is easy to operate, high income, and the three wastes of generation are few, greatly
Reduced production cost.
Although having done more detailed elaboration to technical solution of the present invention and having enumerated, it should be understood that for ability
For field technique personnel, modifications to the embodiments described above may be made or uses equivalent alternative solution, this is to those skilled in the art
It is it is clear that these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the present invention for member
Claimed range.
Claims (7)
1. a kind of preparation method of methane-disulfonic acid methylene ester, which is characterized in that the preparation method includes sulfonating reaction and dehydration
Condensation reaction, the sulfonating reaction are to carry out sulfonating reaction with Loprazolam and sulfonating agent to obtain methylene-disulfonic acid；It is described de-
Water condensation reaction is that the methylene-disulfonic acid prepared with sulfonating reaction and formaldehyde compounds dissolve in organic solvent, in dehydrating agent
In the presence of, it carries out dehydration condensation and generates methane-disulfonic acid methylene ester crude product, resulting methane-disulfonic acid methylene ester is thick
Product are added to the water washing, dry up to methane-disulfonic acid methylene ester fine work.
2. a kind of preparation method of methane-disulfonic acid methylene ester according to claim 1, it is characterised in that：The sulfonating agent
For the mixture of one or more of the concentrated sulfuric acid, oleum, chlorosulfonic acid, sulfur trioxide, sulfamic acid.
3. a kind of preparation method of methane-disulfonic acid methylene ester according to claim 1, it is characterised in that：The formolation
Conjunction object is the mixture of one or more of formaldehyde gas, paraformaldehyde, metaformaldehyde, four polyformaldehyde, dimethoxym ethane.
4. a kind of preparation method of methane-disulfonic acid methylene ester according to claim 1, it is characterised in that：The dehydrating agent
For one or more of phosphorus pentoxide, solid phosgene, thionyl chloride, the concentrated sulfuric acid, phosphorus trichloride mixture.
5. a kind of preparation method of methane-disulfonic acid methylene ester according to claim 1, it is characterised in that：It is described organic molten
Agent is the mixing of one or more of sulfolane, ethyl acetate, dichloroethanes, methylene chloride, glycol dimethyl ether, acetic anhydride
Object,
The mass ratio of Loprazolam and organic solvent is 1:5~1:50.
6. a kind of preparation method of methane-disulfonic acid methylene ester according to claim 1, it is characterised in that：The sulfonation is anti-
The molar ratio of Ying Zhong, Loprazolam and sulfonating agent is 1:1~1:10, reaction temperature be 50 DEG C ~ 200 DEG C, the reaction time be 1 ~ for 24 hours,
Reaction pressure is 0.1Mpa ~ 10Mpa.
7. a kind of preparation method of methane-disulfonic acid methylene ester according to claim 1, it is characterised in that：The dehydration contracting
It closes in reaction, the molar ratio of methylene-disulfonic acid and formaldehyde object is 1:1~1:10, the molar ratio of methylene-disulfonic acid and dehydrating agent
It is 1:0.4~1:4, reaction temperature is 80 DEG C ~ 140 DEG C, and the reaction time is 2 ~ 12h, and reaction pressure is 0.1Mpa ~ 10Mpa.
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Cited By (10)
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| CN110724122A (en) * | 2019-11-08 | 2020-01-24 | 湖南阿斯达新材料有限公司 | Preparation method of methylene methanedisulfonate |
| CN111072626A (en) * | 2019-12-24 | 2020-04-28 | 湖南阿斯达新材料有限公司 | Preparation method of cyclic methylene disulfonate compound |
| CN111153887A (en) * | 2020-01-20 | 2020-05-15 | 荣成青木高新材料股份有限公司 | Synthesis method of methylene methanedisulfonate |
| WO2021015219A1 (en) * | 2019-07-23 | 2021-01-28 | 住友精化株式会社 | Method for producing methylene disulfonate compound |
| WO2021161944A1 (en) * | 2020-02-14 | 2021-08-19 | 住友精化株式会社 | Method for producing alkane disulfonic acid compound |
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| WO2021161942A1 (en) * | 2020-02-14 | 2021-08-19 | 住友精化株式会社 | Method for producing alkanedisulfonic acid compound |
| CN113801092A (en) * | 2021-09-29 | 2021-12-17 | 深圳市研一新材料有限责任公司 | Methylene methanedisulfonate and preparation method thereof |
| CN113896706A (en) * | 2021-09-16 | 2022-01-07 | 苏州亚科科技股份有限公司 | Preparation method and application of methylene methanedisulfonate |
| CN116768845A (en) * | 2023-08-22 | 2023-09-19 | 江苏华盛锂电材料股份有限公司 | Preparation method of methylene methane disulfonate |
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| CN114144406A (en) * | 2019-07-23 | 2022-03-04 | 住友精化株式会社 | Method for producing methylene disulfonate compound |
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| WO2021161944A1 (en) * | 2020-02-14 | 2021-08-19 | 住友精化株式会社 | Method for producing alkane disulfonic acid compound |
| CN115052858A (en) * | 2020-02-14 | 2022-09-13 | 住友精化株式会社 | Method for producing alkanedisulfonic acid compound |
| CN115066415A (en) * | 2020-02-14 | 2022-09-16 | 住友精化株式会社 | Method for producing alkanedisulfonic acid compound |
| CN115066421A (en) * | 2020-02-14 | 2022-09-16 | 住友精化株式会社 | Method for producing methylene disulfonate compound |
| WO2021161943A1 (en) * | 2020-02-14 | 2021-08-19 | 住友精化株式会社 | Method for producing methylene disulfonate compound |
| WO2021161942A1 (en) * | 2020-02-14 | 2021-08-19 | 住友精化株式会社 | Method for producing alkanedisulfonic acid compound |
| EP4105199A4 (en) * | 2020-02-14 | 2024-03-13 | Sumitomo Seika Chemicals | Method for producing alkane disulfonic acid compound |
| CN113896706A (en) * | 2021-09-16 | 2022-01-07 | 苏州亚科科技股份有限公司 | Preparation method and application of methylene methanedisulfonate |
| CN113896706B (en) * | 2021-09-16 | 2024-06-07 | 苏州亚科科技股份有限公司 | Preparation method and application of methylene methane disulfonate |
| CN113801092A (en) * | 2021-09-29 | 2021-12-17 | 深圳市研一新材料有限责任公司 | Methylene methanedisulfonate and preparation method thereof |
| CN113801092B (en) * | 2021-09-29 | 2023-01-10 | 深圳市研一新材料有限责任公司 | Methylene methanedisulfonate and preparation method thereof |
| CN116768845A (en) * | 2023-08-22 | 2023-09-19 | 江苏华盛锂电材料股份有限公司 | Preparation method of methylene methane disulfonate |
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