CN105732446B - Method for preparing intermediate bis(2-chloroethylsulfonyl) methane of bis(vinyl sulphone) methane - Google Patents
Method for preparing intermediate bis(2-chloroethylsulfonyl) methane of bis(vinyl sulphone) methane Download PDFInfo
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- CN105732446B CN105732446B CN201610083723.1A CN201610083723A CN105732446B CN 105732446 B CN105732446 B CN 105732446B CN 201610083723 A CN201610083723 A CN 201610083723A CN 105732446 B CN105732446 B CN 105732446B
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- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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Abstract
The invention relates to the field of organic chemical synthesis, in particular to a method for preparing high-purity bis(2-chloroethylsulfonyl) methane, and provides a method for preparing an intermediate bis(2-chloroethylsulfonyl) methane of bis(vinyl sulphone) methane.The method comprises the following steps that methanedisulfonyl dichloride and ethylene are adopted as raw materials, and under catalyzing of a lewis acid catalyst, reacting is carried out to generate bis(2-chloroethylsulfonyl) methane.According to the method for preparing bis(2-chloroethylsulfonyl) methane, methanedisulfonyl dichloride and ethylene are adopted as the raw materials, and bis(2-chloroethylsulfonyl) methane is obtained under the catalytic action of lewis acid or lewis acid load on a carrier.Compared with an existing production route, according to the method, the reaction steps are reduced, the production period is shortened, operation is easy, various poisonous and harmful reagents and reagents unfriendly to the environment are abandoned, environment friendliness is achieved, and a synthetic route with wide industrial prospects is achieved.
Description
Technical field
The present invention relates to organic chemical synthesis field, double (the 2- chloroethyls sulfuryl) methane of more particularly to a kind of high-purity
Preparation method.
Background technology
As image technology is in the quick emergence in the whole world, to the city of the photosensitive materials such as liquid crystal, toner, developer and image drum
Field demand is still in continuous ascendant trend.Double (vinyl sulfone) methane are the new photosensitive colour developing auxiliary agents of a class, and its chemical property is lived
Sprinkle, easy natural degradation, or use microbial degradation, environment will not be polluted.According to the literature, it is widely used at present
Synthetic route is following (US20050148798)：
According to this production line, intermediate double (2- chloroethyls sulfuryl) methane of double (vinyl sulfone) methane will be passed through successively
Condensation reaction, oxidation reaction and the step of chlorination reaction three is crossed to be obtained.Generally require to use the oxidants such as hydrogen peroxide in the oxidation reaction,
Than relatively hazardous in production, be not suitable for heavy industrialization.In chlorination reaction, it is necessary to the chlorination reagent used have POCl3,
Thionyl chloride, phosgene, triphosgene etc..Contain substantial amounts of accessory substance polyphosphoric acid in the product that these chlorination reagents have, it is necessary to use two
Planting Solvent Extract methods treatment can just obtain product；What is had is serious to equipment corrosion；Some chlorination reagents have severe toxicity in itself；Have
Substantial amounts of phosphorous or sulfur-containing waste water is produced, it is difficult to process, pollution problem is serious, environmental problem is protruded, and does not only result in and is produced into
This is greatly improved, and the extensive industrialization of synthetic route also is difficult to realize.
The content of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of double (vinyl sulfone) methane
The preparation method of intermediate double (2- chloroethyls sulfuryl) methane, for solving the problems of the prior art.It is provided by the present invention
The preparation method of double (2- chloroethyls sulfuryl) methane is compared with existing synthetic route, shortens reactions steps and production cycle,
And it is simple to operate, it is a synthetic route with extensive industrial prospect.
In order to achieve the above objects and other related objects, first aspect present invention provides a kind of double (2- chloroethyls sulfuryl) first
The preparation method of alkane, comprises the following steps：
With methane disulfonic acid chloride (compound of formula I) and ethene as raw material, under the catalysis of lewis acid catalyst, reaction life
(2- chloroethyls sulfuryl) methane (Formula II compound) in pairs, reaction equation is as follows：
Preferably, mol ratio >=2 of the ethene and methane disulfonic acid chloride (compound of formula I) usage amount.
It is furthermore preferred that the ethene is 2.0~5.0 with the mol ratio of methane disulfonic acid chloride (compound of formula I) usage amount：1.
It is further preferred that the mol ratio of the ethene and methane disulfonic acid chloride (compound of formula I) usage amount for 2.0~
3.0：1.
Ethene intake does not influence significantly more than 5.0 times of the amount of methane disulfonic acid chloride material on reaction yield, but
It is to waste ethene；Ethene intake is less than 2.0 times of the amount of methane disulfonic acid chloride material, and reaction is incomplete.
Specifically, the lewis acid catalyst can be used alone and (not being carried in catalyst carrier, being directly added into
In reaction system), it is also possible to it is carried in catalyst carrier and uses.The catalyst carrier can be applied to for this area is various
The catalyst carrier of lewis acid catalyst, specific adoptable catalyst carrier is included but is not limited to：Macromolecule carrier, it is such as poly-
Styrene, polyvinyl chloride, polyethylene glycol, sulfonate resin etc.；Inorganic carrier, such as atlapulgite, aluminum oxide, silica.
Preferably, the lewis acid is selected from alchlor, ferric trichloride, butter of tin, zinc chloride, magnesium chloride, chlorination
One or more in copper of combination.
Those skilled in the art can be according to reaction system and the species of catalyst, the consumption of appropriate adjustment catalyst.It is preferred that
, the methane disulfonic acid chloride (compound of formula I) is 1 with the mass ratio of lewis acid catalyst：0.05-3.It is furthermore preferred that institute
It is 1 that methane disulfonic acid chloride (compound of formula I) is stated with the mass ratio of lewis acid catalyst：0.2-1.2.
Preferably, the reaction is carried out in organic solvent, and the organic solvent is chloralkane.It is furthermore preferred that described
Organic solvent is selected from dichloromethane, chloroform, carbon tetrachloride, chloroethanes, 1,2- dichloroethanes, n-propyl chloride, 2 cbloropropane isopropyl chloride, 1,2-
Dichloropropane, 1,3- dichloropropanes, 1,1,1- trichloroethanes, 1-chlorobutane, Sec-Butyl Chloride, 1- chloro-2-methyls propane, 2- are chloro-
One or more in the chlorohydrocarbons such as 2- methylpropanes, 1,2- dichloroetane, 2,3- dichloroetane, 1-chloropentane, 2- chloropentanes
Combination.
Those skilled in the art can implement according to inventory and the consumption of the suitable organic solvent of determination in the present invention one
In example, the consumption of the organic solvent is 50-1000ml/100g methane disulfonic acid chlorides.
Preferably, the reaction temperature of the reaction is -10~150 DEG C.
Those skilled in the art can determine the reaction time according to the process of reaction, and the various suitable inspections in this area can be used
Survey method monitors reaction process.In an embodiment of the present invention, with liquid chromatogram tracking and monitoring reaction process, reaction to methane two
Sulfonic acid chloride surplus≤1% (on the basis of methane disulfonic acid chloride inventory).
Preferably, the post-processing approach of reaction is：Add water and be quenched, gained organic phase precipitation removes appropriate organic solvent, drop
Temperature separates out solid, and separation of solid and liquid, solid formation are drying to obtain product；It is furthermore preferred that after adding water and being quenched, first by reaction solution solid-liquid point
From, then separate acquisition organic phase.
Or, by reaction solution separation of solid and liquid, filtrate adds water and is quenched, gained organic phase precipitation removes appropriate organic solvent, cooling
Solid is separated out, separation of solid and liquid, solid formation are drying to obtain product.In an embodiment of the present invention, the removal of organic phase precipitation is organic molten
The amount of agent is organic solvent 10%-95% in organic phase.
It is furthermore preferred that adding water when being quenched, those skilled in the art can determine add water according to the amount of catalyst in reaction system
Amount (suitable), preferred amount of water is 2-10 times (mass ratio) of catalyst amount.
Second aspect present invention provides the preparation method of described double (2- chloroethyls sulfuryl) methane in double (2- chloroethyl sulfones
Base) methane and double (vinyl sulfone) methane preparation fields purposes.
The preparation method of double (2- chloroethyls sulfuryl) methane provided by the present invention is with methane disulfonic acid chloride and ethene as former
Material, it is anti-in -10~150 DEG C in organic solvent under lewis acid or the lewis acidic catalytic action being supported on carrier
Should be complete, product can obtain double (2- chloroethyls sulfuryl) methane by being quenched, filtering, distilling one step of the operation such as precipitation.
Further synthesize double (vinyl sulfone) methane.Compared with existing production line, the method not only shortens reactions steps and life
It is the product cycle, simple to operate, and abandoned various poisonous and harmfuls, to the disagreeableness reagent of environment, environmental protection, being one has
The synthetic route of extensive industrial prospect.
Specific embodiment
Embodiments of the present invention are illustrated below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages of the invention and effect easily.The present invention can also be by specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
It should be clear that process equipment not specific dated in the following example or device using conventional equipment in the art or
Device.
In addition, it is to be understood that one or more method and steps mentioned in the present invention do not repel before and after the combination step
Can also there is other method step or other method step can also be inserted between the step of these are specifically mentioned, unless separately
It is described；It should also be understood that the combination annexation between one or more the equipment/devices mentioned in the present invention is not repelled
Can also exist before and after the unit equipment/device other equipment/device or two equipment/devices specifically mentioning at these it
Between can also insert other equipment/device, unless otherwise indicated.And, unless otherwise indicated, the numbering of various method steps is only
Differentiate the convenient tool of various method steps, rather than to limit the ordering of various method steps or limiting enforceable model of the invention
Enclose, being altered or modified for its relativeness is of the invention enforceable when being also considered as in the case of without essence change technology contents
Category.
In embodiment, raw material (methane disulfonic acid chloride) surplus in reaction system with liquid chromatogram tracking and monitoring, its color
Spectral condition is specific as follows：
The series liquid chromatographs of Agilent 1100 (including 1312A Bin pump, 1315B DAD detectors)
Chromatographic column：YMC-Triant C18 150*4.6mm.I.D.；S-5um,12nm
Solvent：Methyl alcohol (HPLC grades)
Pure water
Operation condition of chromatogram：
Detection wavelength：210nm (full wavelength scanner, the wavelength is this material maximum absorption wavelength)
Column temperature：30℃
Sample size：10ul
Flow velocity：1.0ml/min
Mobile phase A：Pure water Mobile phase B：Methyl alcohol
Operation program：Mobile phase A：Mobile phase B=10：90 isocratic operation 20min
Embodiment 1
In the there-necked flask of the band equipped with thermometer of 1000ml, 0.5mol methane disulfonic acid chloride 106.5g and tri-chlorination are added
Iron 81.0g (0.5mol), dichloromethane 250ml, interior temperature is kept for -5~-10 DEG C, leads to 2.1mol ethene.Finish, stirring reaction is extremely
Raw material (methane disulfonic acid chloride)≤1%.Post processing：Add water and be quenched (150ml water), filtering removal ferric trichloride liquid phase through extraction,
Divide the operating procedures such as liquid, drying, collect organic phase, steam 80% dichloromethane, cooling separates out white solid, and filtering is dry.
Dry product：80g, Yield：81.5%.HPLC：99.6%.1H NMR(400Hz,DMSO-d6)δ5.26(2H,s),4.02(4H,t,J
=6.8Hz), 4.02 (4H, t, J=6.8Hz)
Embodiment 2-6
In embodiment 2-6, methane disulfonic acid chloride, ethene, the species of catalyst, the usage amount of catalyst, the species of solvent,
As shown in table 1, other reaction conditions are in the same manner as in Example 1 for usage amount, the reaction temperature of solvent.The yield of product and contain
Measurer body is as shown in table 1.
Table 1
Embodiment 7
In the there-necked flask of the band equipped with thermometer of 1000ml, 0.5mol methane disulfonic acid chloride 106.5g and magnesium chloride are added
14.67g (0.154mol), 1,2- dichloroethanes 100ml, interior temperature is kept for -5~-10 DEG C, leads to 1.1mol ethene.Finish, stirring is anti-
Should be to raw material (methane disulfonic acid chloride)≤1%.Post processing：Add water and be quenched (600ml water), filtering removal magnesium chloride simultaneously separates acquisition
Organic phase, steams 50%1,2- dichloroethanes, and cooling separates out white solid, and filtering is dried.Yield and purity with embodiment 1
Result is close.
Embodiment 8
In the there-necked flask of the band equipped with thermometer of 2000ml, 0.5mol methane disulfonic acid chloride 106.5g and zinc chloride are added
The chloro- 2 methylpropane 600ml of 122.7g (0.9mol), 2-, interior temperature is kept for -5~-10 DEG C, leads to 1.5mol ethene.Finish, stirring is anti-
Should be to raw material (methane disulfonic acid chloride)≤1%.Post processing：Filtering removal zinc chloride, adds water and (450ml water) is quenched and acquisition is separated
Organic phase, steams chloro- 2 methylpropanes of 75%2-, and cooling separates out white solid, and filtering is dried.Yield and purity are and embodiment
1 result is close.
Embodiment 9
In the there-necked flask of the band equipped with thermometer of 1000ml, 0.5mol methane disulfonic acid chloride 106.5g and copper chloride are added
85.2g (0.5mol), carbon tetrachloride 200ml, interior temperature is kept for -5~-10 DEG C, leads to 1.5mol ethene.Finish, stirring reaction to original
Material (methane disulfonic acid chloride)≤1%.Post processing：Filtering removal copper chloride, adding water (250ml water) to be quenched and separates obtains organic
Phase, steams 90% carbon tetrachloride, and cooling separates out white solid, and filtering is dried.Yield and purity are close with the result of embodiment 1.
In sum, the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
The personage for knowing this technology all can carry out modifications and changes under without prejudice to spirit and scope of the invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as
Into all equivalent modifications or change, should be covered by claim of the invention.
Claims (9)
1. a kind of preparation method of double (2- chloroethyls sulfuryl) methane, comprises the following steps：
With methane disulfonic acid chloride and ethene as raw material, under the catalysis of lewis acid catalyst, double (the 2- chloroethyl sulfones of reaction generation
Base) methane, reaction equation is as follows：
The ethene is 2.0~5.0 with the mol ratio of methane disulfonic acid chloride usage amount：1；
The methane disulfonic acid chloride is 1 with the mass ratio of lewis acid catalyst：0.05-3.
2. the as claimed in claim 1 a kind of double preparation method of (2- chloroethyls sulfuryl) methane, it is characterised in that the ethene
It is 2.0~3.0 with the mol ratio of methane disulfonic acid chloride usage amount：1.
3. the as claimed in claim 1 a kind of double preparation method of (2- chloroethyls sulfuryl) methane, it is characterised in that the Louis
This acid catalyst is not carried in catalyst carrier when using.
4. the as claimed in claim 1 a kind of double preparation method of (2- chloroethyls sulfuryl) methane, it is characterised in that the Louis
This acid catalyst is carried in catalyst carrier and uses.
5. the as claimed in claim 1 a kind of double preparation method of (2- chloroethyls sulfuryl) methane, it is characterised in that the Louis
Combination of this acid selected from one or more in alchlor, ferric trichloride, butter of tin, zinc chloride, magnesium chloride, copper chloride.
6. the as claimed in claim 1 a kind of double preparation method of (2- chloroethyls sulfuryl) methane, it is characterised in that the methane
Disulfonic acid chloride is 1 with the mass ratio of lewis acid catalyst：0.2-1.2.
7. the preparation method of (2- chloroethyls sulfuryl) methane as claimed in claim 1 a kind of double, it is characterised in that reaction is having
Carried out in machine solvent, the organic solvent is chloralkane.
8. the preparation method of (2- chloroethyls sulfuryl) methane as claimed in claim 7 a kind of double, it is characterised in that described organic
Solvent be selected from dichloromethane, chloroform, carbon tetrachloride, chloroethanes, 1,2- dichloroethanes, n-propyl chloride, 2 cbloropropane isopropyl chloride, 1,2- bis-
Chloropropane, 1,3- dichloropropanes, 1,1,1- trichloroethanes, 1-chlorobutane, Sec-Butyl Chloride, 1- chloro-2-methyls propane, the chloro- 2- of 2-
One or more in methylpropane, 1,2- dichloroetane, 2,3- dichloroetane, 1-chloropentane, 2- chloropentanes of combination.
9. the preparation method of (2- chloroethyls sulfuryl) methane as claimed in claim 1 a kind of double, it is characterised in that reaction it is anti-
It is -10~150 DEG C to answer temperature.
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| CN201610083723.1A CN105732446B (en) | 2016-02-05 | 2016-02-05 | Method for preparing intermediate bis(2-chloroethylsulfonyl) methane of bis(vinyl sulphone) methane |
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| CN201610083723.1A CN105732446B (en) | 2016-02-05 | 2016-02-05 | Method for preparing intermediate bis(2-chloroethylsulfonyl) methane of bis(vinyl sulphone) methane |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1363046A (en) * | 1963-07-16 | 1964-06-05 | Basf Ag | Vinylsulfone production process |
| EP0640589A1 (en) * | 1993-08-30 | 1995-03-01 | Eastman Kodak Company | Process for manufacturing compounds containing two or more vinyl sulfone groups |
| JP2000072741A (en) * | 1998-08-28 | 2000-03-07 | Konica Corp | Production of halogen compound |
| CN101016258A (en) * | 2007-02-14 | 2007-08-15 | 浙江工业大学 | Method of synthesizing bis(2-chlorethylsulfuryl)methane compound |
| CN104311465A (en) * | 2014-10-11 | 2015-01-28 | 大连理工大学 | Omega-vinylsulphonyl disulfide compound as well as preparation method and application thereof |
-
2016
- 2016-02-05 CN CN201610083723.1A patent/CN105732446B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1363046A (en) * | 1963-07-16 | 1964-06-05 | Basf Ag | Vinylsulfone production process |
| EP0640589A1 (en) * | 1993-08-30 | 1995-03-01 | Eastman Kodak Company | Process for manufacturing compounds containing two or more vinyl sulfone groups |
| JP2000072741A (en) * | 1998-08-28 | 2000-03-07 | Konica Corp | Production of halogen compound |
| CN101016258A (en) * | 2007-02-14 | 2007-08-15 | 浙江工业大学 | Method of synthesizing bis(2-chlorethylsulfuryl)methane compound |
| CN104311465A (en) * | 2014-10-11 | 2015-01-28 | 大连理工大学 | Omega-vinylsulphonyl disulfide compound as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| A new method for the synthesis of tetrahydrothiophene-S,S-dioxide derivatives: the Michael ring closure reaction between halomethyl (E)-β-styryl sulfones and CH-acids;Victor A. Vasin 等;《Journal of Sulfur Chemistry》;20070201;第26卷(第2期);第139-144页 * |
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Denomination of invention: Preparation method of bis (2-chloroethyl sulfonyl) methane, an intermediate of bis (vinyl sulfone) methane Effective date of registration: 20221121 Granted publication date: 20170524 Pledgee: Industrial Bank Co.,Ltd. Shanghai Pudong Sub branch Pledgor: SHANGHAI BETTERSYN BIOTECH CO.,LTD. Registration number: Y2022310000328 |
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