CN101195592A - Production method of methyl chloride sulphur ester compounds - Google Patents
Production method of methyl chloride sulphur ester compounds Download PDFInfo
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- CN101195592A CN101195592A CNA2007100444125A CN200710044412A CN101195592A CN 101195592 A CN101195592 A CN 101195592A CN A2007100444125 A CNA2007100444125 A CN A2007100444125A CN 200710044412 A CN200710044412 A CN 200710044412A CN 101195592 A CN101195592 A CN 101195592A
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Abstract
The invention provides a preparation method of methyl chlorosulfuric acid ester compound, which comprises processing addition reaction on liquid sulfur trioxide and carrene, using carbonate, carbonic ester as diethyl carbonate containing saturated hydrocarbon, borate and boric acid ester as butyl borate containing saturated hydrocarbon as catalyst, controlling the reaction condition of each step, removing over sulfur trioxide and sulfuric acid generated via absorbing humidity, from sodium acid carbonate water solution, layering and drying upper organic layer, depressurizing and distilling to obtain chloromethyl chlorosulfonic acid ester and methyl dichloro sulfonate. The whole reaction is mild, with high yield, easy industrialization, little three-waste, and simple process.
Description
Technical field
The present invention relates to a kind of preparation method of methyl chloride sulphur acid esters compound, but generate the industrialized process for preparing of methyl chloride sulphur acid esters compound more specifically to sulfan and methylene dichloride generation addition reaction.
Background technology
The methyl chloride sulphur acid esters compound comprises chloromethyl chlorsulfonic acid ester and methyl dichloro sulphonate, is the electrolytic solution of the important organic synthesis intermediate of a class and a kind of new and effective, safe lithium cell.
U.S. Pat 4649209 has been reported the synthetic method of utilizing sulphur trioxide and synthetic chloromethyl chlorsulfonic acid ester of methylene dichloride and methyl dichloro sulphonate, but owing in reaction process, not using effective catalyzer to cause long reaction time, the yield of methyl dichloro sulphonate has only 37.3%, adopts solid to feed intake in addition in the technology and makes industrialization have difficulties.And another piece document (NicholasP.Power, Donald Bethell, Org.Biomol.Chem., 2004 (2), though 1554-1562) method of utilizing sulphur trioxide and synthetic chloromethyl chlorsulfonic acid ester of methylene dichloride and methyl dichloro sulphonate of report has been used catalyzer, not quite reasonable in the reaction conditions control, cause product yield very low, material loss is big, and the three wastes are many, is not suitable for industrialization.
Since the special property of sulphur trioxide, transportation, working conditions harshness, and also reaction is violent in sulfonation process, has limited its utilization in synthetic and industrialization; Methylene dichloride is commonly considered as the good solvent of sulfan in the general knowledge in addition, has ignored the essence of its reaction, so domesticly seldom it is studied; In fact sulfan and methylene dichloride reaction generally is difficult to carry out or deferred reaction, allow reaction need certain conditions and catalyzer fast or thoroughly, China does not also have the preparation method of the relevant relevant methyl chloride sulphur acid esters compound of bibliographical information at present.
Summary of the invention
Purpose of the present invention is for providing the preparation method of a kind of yield height, methyl chloride sulphur acid esters compound that purity is high, but makes the entire reaction course industrialization.
The method for preparing the methyl chloride sulphur acid esters compound provided by the invention by sulfan and methylene dichloride generation addition reaction, and adopts appropriate catalyst, prepares the methyl chloride sulphur ester compound by controlling each elementary reaction condition.Its step is as follows:
1) under-50～40 ℃ condition, at catalyst carbon hydrochlorate, the carbonic ether that contains saturated hydrocarbyl, borate, contain in the presence of the boric acid ester of saturated hydrocarbyl, sulfan and methylene dichloride reaction 1～24 hour, the mixture of generation chloromethyl chlorsulfonic acid ester and methyl dichloro sulphonate
2) yellow soda ash or aqueous sodium carbonate are dropped into above-mentioned steps 1) in the mixture of gained, remove the sulfuric acid that excessive sulphur trioxide and moisture absorption produce, reaction is proceeded;
3) sodium bicarbonate or sodium bicarbonate aqueous solution are put into above-mentioned steps 2) in the mixture of gained, remove the sulfuric acid that excessive sulphur trioxide and moisture absorption produce fully, standing demix, getting dry the removing of upper strata organic layer desolvates, underpressure distillation obtains chloromethyl chlorsulfonic acid ester and methyl dichloro sulphonate respectively.
In the step 1), in the presence of catalyzer, make sulfan (I) and methylene dichloride (II) reaction, catalyzer joins in methylene dichloride or the sulfan, (I) can carry out containing solvent or do not contain under the solvent with (II) reaction, solvent is that saturated halohydrocarbon or other can dissolve the organic solvent of sulphur trioxide, for example: methylene dichloride, chloroform, tetracol phenixin, tetrafluoro-methane, benzene, pyridine etc., the usage quantity of solvent is 0～10 times of methylene chloride volume.
Described catalyzer comprises that carbonate and diethyl carbonate etc. contain the boric acid ester that the carbonic ether of saturated hydrocarbyl, borate and tributyl borate etc. contain saturated hydrocarbyl.
Reactant (I) and mol ratio (II) are between 1～3: 1, and be good with 2: 1, the used ratio of catalyzer can adjusted in a big way, and preferred weight is 0.5～5% of the methylene dichloride charging capacity.Compound (I) and preferred-10～30 ℃ of (II) temperature of reaction, preferred 1～5h of reaction times, the concrete time is according to character, catalyst consumption and the solvent types of temperature of reaction, batch weight, reactant and consumption and different.
Step 2) in, the consumption of yellow soda ash is 1.5～5% of a sulphur trioxide charging capacity, soaking time between 0.1～5h, preferred 1h.
The consumption of sodium bicarbonate is advisable with the sulfuric acid of removing excessive sulphur trioxide and moisture absorption generation fully in the step 3), surveys the potential of hydrogen of water, and control PH is 7～8.
Sodium bicarbonate of the present invention or yellow soda ash all can be made into the aqueous solution and use.
According to the present invention, also above-mentioned preparation method's step can be divided into for two steps to finish: make (I) and (II) mol ratio less than 1, by above-mentioned steps 1), 2), 3) obtain CMCS, CMCS continues to obtain MBCS with the sulfan reaction then.
Beneficial effect of the present invention:
The present invention utilizes appropriate catalyst to make sulfan and methylene dichloride generation addition reaction, generates chloromethyl chlorsulfonic acid ester and methyl dichloro sulphonate, makes that reaction conditions is warmer to be closed, and yield improves.Sulfan is used in reaction simultaneously, is easier to industrialization, and the few and easy processing of the three wastes has alleviated pollution.
Embodiment
Below by embodiment the present invention is further specified, but embodiment does not limit protection scope of the present invention.
Embodiment 1:
In the airtight system of drying, the 0.8g diethyl carbonate is joined in the 51g methylene dichloride, at room temperature dropwise drip the 88g sulfan then, about insulation 5h; Yellow soda ash 2g is joined in the system, continue to stir 1h; Slowly drip saturated aqueous solution of sodium bicarbonate, the pH value that makes reaction system is 7, stirs after 10 minutes static layering; Get upper strata organic layer drying and distilling, obtain two sections cut: CMCS (62～64 ℃/24mmHg, 33g, theoretical yield 33%) and MBCS (110～112 ℃/24mmHg, 80g, theoretical yield 54%).
Embodiment 2:
In the airtight system of drying, the 2g tributyl borate is joined in the 220g methylene dichloride, at room temperature dropwise drip the 200g sulfan then, about insulation 1h; Yellow soda ash 10g is joined in the system, continue to stir 1h; Slowly drip saturated aqueous solution of sodium bicarbonate 300g to pH value be 8, stir after 10 minutes static layering; Get upper strata organic layer drying and distilling, obtain: CMCS (62～64 ℃/24mmHg, 80g, theoretical yield 81%).
Embodiment 3:
In the airtight system of drying, the 5g trimethyl borate is joined among the 330g CMCS, under 0 ℃, dropwise drip the 165g sulfan then, about insulation 1h; Slowly drip sodium bicarbonate aqueous solution (10%) 300g to pH value be 7, stir after 10 minutes static layering; Get upper strata organic layer drying and distilling, obtain: MBCS (110～112 ℃/24mmHg, 235g, theoretical yield 48%).
Embodiment 4:
In the airtight system of drying, 1.8g yellow soda ash is joined in the 51g methylene dichloride, under-20 ℃, dropwise drip the 92g sulfan then, about insulation 12h; Yellow soda ash 2g is joined in the system, continue to stir 5h; Slowly dripping saturated aqueous solution of sodium bicarbonate 50g to PH is 7.5, stirs after 10 minutes static layering; Get upper strata organic layer drying and distilling, obtain two sections cut: CMCS (62-64 ℃/24mmHg, 31g, theoretical yield 31%) and MBCS (110～112 ℃/24mmHg, 52g, theoretical yield 35%).
Embodiment 5:
In the airtight system of drying, the 1.5g potassium borate is joined in the 51g methylene dichloride, under 30 ℃, dropwise drip the mixed solution of 80g sulfan and 80g tetracol phenixin then, about insulation 1h; Yellow soda ash 2g is joined in the system, continue to stir 2h; Slowly drip saturated aqueous solution of sodium bicarbonate 50g to pH value be 7, stir after 10 minutes static layering; Get upper strata organic layer drying and distilling, obtain two sections cut: CMCS (62～64 ℃/24mmHg, 42g, theoretical yield 42%) and MBCS (110～112 ℃/24mmHg, 65g, theoretical yield 44%).
Comparative Examples (according to U.S. Pat 4649209 described experiments):
In the airtight system of drying, add the 510g methylene dichloride, in 65 minutes, dropwise drip the 480g sulfan then, insulation is at 25-28 ℃; Yellow soda ash 20g is joined in the system, continue to stir 1h; Slowly add sodium bicarbonate 47g, stir after 10 minutes, under anhydrous condition, filter, filtrate distillation, obtain two sections cut: CMCS (62～64 ℃/24mmHg, 512g, theoretical yield 51.8%) and MBCS (110～112 ℃/24mmHg, 212g, theoretical yield 28.8%).This shows that preparation method's yield of methyl chloride sulphur acid esters compound of the present invention improves, the reaction conditions gentleness is more conducive to suitability for industrialized production.
Claims (9)
1. the preparation method of a methyl chloride sulphur acid esters compound comprises the steps:
1) under-50～40 ℃ condition, at catalyst carbon hydrochlorate, the carbonic ether that contains saturated hydrocarbyl, borate or contain in the presence of the boric acid ester of saturated hydrocarbyl, sulfan and methylene dichloride reaction 1～24 hour, generate chloromethyl chlorsulfonic acid ester, or the mixture of chloromethyl chlorsulfonic acid ester and methyl dichloro sulphonate
2) yellow soda ash or aqueous sodium carbonate are dropped in the mixture of step 1) gained, remove the sulfuric acid that excessive sulphur trioxide and moisture absorption produce, reaction is proceeded;
3) sodium bicarbonate or sodium bicarbonate aqueous solution are put into step 2) in the mixture of gained, remove the sulfuric acid that excessive sulphur trioxide and moisture absorption produce fully, standing demix is got dry the removing of upper strata organic layer and is desolvated, underpressure distillation obtains chloromethyl chlorsulfonic acid ester and methyl dichloro sulphonate respectively;
4) when the mol ratio of sulfan in the step 1) and methylene dichloride less than 1 the time, above-mentioned steps 1), 2), 3) product of gained only is chloromethyl chlorsulfonic acid ester, the chloromethyl chlorsulfonic acid ester of gained continues to obtain the methyl dichloro sulphonate with the sulphur trioxide reaction.
2. the preparation method of methyl chloride sulphur acid esters compound according to claim 1 is characterized in that, step 1) is carried out containing under solvent or the not solvent-laden condition, and described solvent is that saturated halohydrocarbon or other can dissolve the organic solvent of sulphur trioxide.
3. the preparation method of the methyl chloride sulphur acid esters compound of stating according to claim 2 is characterized in that described solvent is methylene dichloride, chloroform, tetracol phenixin, tetrafluoro-methane, benzene or pyridine.
4. the preparation method of methyl chloride sulphur acid esters compound according to claim 1 is characterized in that, the usage quantity of catalyzer is that its weight is in 0.5～5% of methylene dichloride charging capacity in the step 1).
5. the preparation method of methyl chloride sulphur acid esters compound according to claim 1 is characterized in that, (I) and mol ratio (II) are 1～3: 1 in the step 1).
6. the preparation method of methyl chloride sulphur acid esters compound according to claim 6 is characterized in that, (I) and mol ratio (II) are 2: 1 in the step 1).
7. the preparation method of methyl chloride sulphur acid esters compound according to claim 1 is characterized in that, in the step 1), temperature of reaction is-10～30 ℃, and the reaction times is 1～5 hour.
8. the preparation method of methyl chloride sulphur acid esters compound according to claim 1 is characterized in that step 2) in, the consumption of yellow soda ash is 1.5～5% of a sulphur trioxide charging capacity, soaking time is 0.1～5 hour.
9. the preparation method of methyl chloride sulphur acid esters compound according to claim 1 is characterized in that, the consumption of sodium bicarbonate is to be 7～8 to control by the PH that regulates water in the step 3).
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| CNA2007100444125A CN101195592A (en) | 2007-07-31 | 2007-07-31 | Production method of methyl chloride sulphur ester compounds |
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| CNA2007100444125A CN101195592A (en) | 2007-07-31 | 2007-07-31 | Production method of methyl chloride sulphur ester compounds |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107986995A (en) * | 2017-12-08 | 2018-05-04 | 和夏化学(太仓)有限公司 | A kind of preparation method of methyl dichloro sulphonic acid ester |
| CN113164864A (en) * | 2018-12-06 | 2021-07-23 | 格里洛工厂股份有限公司 | Process for recycling or disposing of halogenated hydrocarbons |
-
2007
- 2007-07-31 CN CNA2007100444125A patent/CN101195592A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107986995A (en) * | 2017-12-08 | 2018-05-04 | 和夏化学(太仓)有限公司 | A kind of preparation method of methyl dichloro sulphonic acid ester |
| CN113164864A (en) * | 2018-12-06 | 2021-07-23 | 格里洛工厂股份有限公司 | Process for recycling or disposing of halogenated hydrocarbons |
| CN113164864B (en) * | 2018-12-06 | 2024-03-19 | 格里洛工厂股份有限公司 | Process for recycling or disposal of halogenated hydrocarbons |
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Open date: 20080611 |