CN117142437A - Preparation method of sulfuryl fluoride - Google Patents

Preparation method of sulfuryl fluoride Download PDF

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Publication number
CN117142437A
CN117142437A CN202211191311.1A CN202211191311A CN117142437A CN 117142437 A CN117142437 A CN 117142437A CN 202211191311 A CN202211191311 A CN 202211191311A CN 117142437 A CN117142437 A CN 117142437A
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fluoride
reaction
sulfonamide
sulfuryl
water
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梁鹏强
周云斌
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Inner Mongolia Tuwei New Material Technology Co ltd
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Inner Mongolia Tuwei New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/45—Compounds containing sulfur and halogen, with or without oxygen
    • C01B17/4561—Compounds containing sulfur, halogen and oxygen only
    • C01B17/4576—Sulfuryl fluoride (SO2F2)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a preparation method of sulfuryl fluoride, which comprises the following steps: (1) forming a sulfonamide by reacting a sulfuryl chloride with a secondary amine; (2) purifying sulfonamide and collecting amine hydrochloride; (3) reacting sulfonamide and fluoride salt to generate sulfuryl fluoride; (4) recovering the secondary amine. The preparation method of sulfuryl fluoride has the advantages of simple synthesis method, low reaction temperature, simple operation, low equipment requirement, high synthesis efficiency, no byproducts, and suitability for industrial scale-up production by taking water as a solvent.

Description

Preparation method of sulfuryl fluoride
Technical Field
The invention relates to a preparation method of sulfuryl fluoride, in particular to a method for preparing sulfuryl fluoride with high purity, green and high efficiency.
Background
Sulfuryl fluoride having chemical formula SO 2 F 2 The fumigant is colorless and odorless gas at room temperature, is a common fumigant in industry, and has wide sources, low price and low cost. Sulfuryl fluoride is the simplest and cheapest method for preparing fluorosulfonic acid compounds in the presence of alkali.
In recent years, sharpless et al report that using "S-F" click chemistry, sulfuryl fluoride is used for efficiently synthesizing a series of sulfonic acid and other and yellow amide compounds, and has great application value in the fields of pharmacy and new materials. The method is applied to phenol deoxidization fluorination reaction in medicine, and the oxalyl diether is used as a precursor to prepare aryl fluorosulfonate, a stable fluorosulfuric acid acylating reagent, metal-catalyzed boric acid coupling reaction and metal-catalyzed C-N bond coupling reaction.
In the field of high polymer materials, sulfuryl fluoride is an important raw material for synthesizing polysulfate materials. The polysulfate is a novel polymer material, and is synthesized by using a front click chemistry technology and a green, environment-friendly and high-efficiency mode. The polysulfate material has excellent comprehensive performance, good thermal stability, excellent mechanical property, good dimensional stability, excellent chemical corrosion resistance and low dielectric constant. And has excellent performance on water treatment films. However, the prior polysulfate materials have lower high-temperature property, low transparency and poor flame retardance.
The prior reported preparation method of sulfuryl fluoride takes sulfur dioxide or sulfuryl chloride as a sulfur source, fluoride salt as a raw material, the reaction needs high temperature and high pressure conditions, a special catalyst is needed, the cost of the catalyst is too high, and the catalyst is difficult to recycle. The method has the advantages of harsh reaction conditions, complex operation, higher requirements on equipment, low yield, by-product generation, high energy consumption, more three wastes, environment friendliness and complex operation, and needs separation operation such as gas washing or rectification.
Therefore, there is a need to provide a method for preparing sulfuryl fluoride which is simple to operate and has low requirements on equipment.
Disclosure of Invention
The invention aims to provide a preparation method of sulfuryl fluoride, which has the advantages of simple operation, low requirement on equipment, more flexible and safe equipment selection and use, no side reaction, easy control of reaction speed, high product purity and suitability for industrial production and amplification by taking water as a solvent.
In order to achieve the above object, the present invention provides a method for preparing sulfuryl fluoride, comprising the steps of:
(1) Sulfonamide is formed by the reaction of sulfuryl chloride and a secondary amine: dissolving secondary amine in an organic solvent to obtain an organic solution of the secondary amine, slowly dripping sulfuryl chloride into the organic solution of the secondary amine at a low temperature, stirring and reacting to generate amine hydrochloride and sulfonamide, filtering the amine hydrochloride, and recovering the organic solvent to obtain sulfonamide;
(2) Purifying sulfonamide: pulping and washing the sulfonamide by using purified water, filtering an aqueous phase, and drying to obtain purified sulfonamide;
(3) The sulfonamide reacts with the fluoride salt to form sulfuryl fluoride: heating the purified sulfonamide and water in water bath, slowly dropwise adding an aqueous solution of fluoride salt under stirring, and reacting to obtain sulfuryl fluoride;
(4) Recovering the secondary amine: dissolving the amine hydrochloride in the step (1) by using the filtered water phase in the step (2), adding inorganic alkali for neutralization, and extracting the water phase by using an extractant to recover the secondary amine.
In one embodiment, in step (1), the secondary amine is in the form of a closed ring, a heterocyclic ring, or a linear chain selected from the following structures:
wherein n is an integer of 1 or more; r, R 1 、R 2 The same or different, are each independently selected from hydrogen, halogen, carbonyl, carboxyl, nitro, aliphatic or aromatic hydrocarbons; y is a heteroatom selected from C, S, O or N.
In one embodiment, in step (1), the organic solvent is at least one of dichloromethane, dichloroethane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, toluene, ethanol, methanol, epoxyhexa-ne, chloroform, diethyl ether, petroleum ether, wherein dichloromethane is preferred.
In one embodiment, in step (1), the reaction is carried out at a temperature of from-20℃to 15℃for a period of from 8 to 16 hours.
In one embodiment, in step (1), the molar ratio of secondary amine to sulfuryl chloride is: 4:1 to 5.5:1, preferably 4.5:1.
In one embodiment, in step (4), the inorganic base is at least one of sodium carbonate, sodium bicarbonate, lithium carbonate, potassium bicarbonate, sodium hydroxide, calcium oxide, magnesium oxide, calcium hydroxide, and potassium hydroxide.
In one embodiment, in step (3), the fluoride salt is at least one of sodium fluoride, potassium fluoride, sodium bifluoride, potassium bifluoride, hydrogen fluoride, ammonium fluoride, and triethylamine trifluoride.
In one embodiment, in step (3), the molar ratio of fluoride salt to sulfuryl chloride is from 2:1 to 4.5:1, preferably 2.5:1.
In one embodiment, in step (3), the mass fraction of fluoride salt in the aqueous solution of fluoride salt is 10% to 50%, with 15% being preferred.
In one embodiment, in step (3), the reaction temperature is from-5 ℃ to 90 ℃ for a period of from 4 to 10 hours.
In one embodiment, in step (3), a catalyst is further added to the reaction, wherein the catalyst is at least one of formic acid, acetic acid, trifluoroacetic acid, hydrofluoric acid aqueous solution, trifluoromethanesulfonic acid, sulfuric acid, aluminum trichloride, ferric trichloride and zinc chloride.
In one embodiment, in step (3), the molar ratio of catalyst to sulfonamide is from 0 to 5.0, with 4.0 being preferred.
In one embodiment, in step (3), the mass ratio of sulfonamide to water is from 1:1.5 to 1:5.
In one embodiment, in step (4), the extractant is at least one of dichlorohexane, toluene, ethyl acetate, chloroform, diethyl ether.
The preparation method of sulfuryl fluoride has the advantages of simple and easily obtained raw materials, reusable raw material secondary amine, low reaction temperature, easy control of reaction, no byproducts, flexible selective synthesis operation of equipment, safer and more environment-friendly reaction process and no waste gas generation, and water is selected as a reaction solvent.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of sulfonyl dipyrrole of example 1.
FIG. 2 is a nuclear magnetic resonance spectrum of sulfonyl dipyrazole of example 2.
FIG. 3 is a nuclear magnetic resonance spectrum of sulfonyl dioxazolidine of example 3.
FIG. 4 is a nuclear magnetic resonance spectrum of sulfonyldiimidazole of example 4.
FIG. 5 is a nuclear magnetic resonance spectrum of the sulfonyl dipiperidine of example 5.
FIG. 6 is a nuclear magnetic resonance spectrum of sulfonylbis (dihydropyridine) of example 6.
FIG. 7 is a nuclear magnetic resonance spectrum of sulfonyldimethylimidazole of example 7.
FIG. 8 is a nuclear magnetic resonance spectrum of example 8 sulfonyl bis (diethylamine).
FIG. 9 is a nuclear magnetic resonance spectrum of the sulfonyl bisbenzimidazole of example 9.
FIG. 10 is a gas spectrum of sulfuryl fluoride gas according to national standard GB/T38211-2019.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
Example 1:
preparation of sulfonyl dipyrrole:
the reaction scheme for the sulfonyl dipyrrole is as follows:
adding 11.7kg of pyrrole into a 100L enamel reaction kettle, adding 35L of dichloromethane, starting stirring, introducing chilled water into a kettle jacket, cooling to-20 ℃, adding 5kg of sulfuryl chloride and 35L of dichloromethane into a dripping tank, slowly dripping after the kettle temperature is reduced, dripping for 4 hours, replacing the chilled water with tap water after dripping is completed, stirring, discharging a reaction solution after reaction for 8 hours, centrifuging and filtering by a centrifuge, collecting 7.7kg of solid-phase pyrrole hydrochloride, and separating a solvent and a product from filtrate by evaporation; the product sulfonyldipyrrole was slurried with pure water, filtered off the aqueous phase, dried for further use, and 6.5kg of sulfonyldipyrrole salt was collected in a yield of 90% and a purity of 99.5%.
Preparation of sulfuryl fluoride gas:
the reaction route of sulfuryl fluoride is as follows:
2kg of sulfonyl dipyrrole salt is added into a 10L tetrafluoro lining reaction kettle, 3L of pure water solution is added, a kettle body jacket is heated to 50 ℃ through hot water, 1kg of hydrogen fluoride water solution (the mass fraction of the hydrogen fluoride water solution is 40%) is added into a dropwise adding tank, the hydrogen fluoride water solution is slowly added dropwise for reaction for 6 hours, a gas compression pump is arranged at a gas outlet, the sulfonyl fluoride gas is collected in a compressed mode, the mass of the obtained sulfonyl fluoride gas is 0.98kg, and the yield is 95%.
Recovery of pyrrole:
adding 7.7kg of pyrrole hydrochloride into an enamel reaction kettle, adding 20L of deionized water, adding 4kg of sodium carbonate aqueous solution, stirring for reaction for 6 hours, mixing with the water phase obtained after pulping and filtering of the sulfonyl dipyrrole after the reaction is finished, evaporating the water phase until solid is separated out, washing by using ethyl acetate, collecting an organic phase, separating pyrrole by rectification, collecting 5.8kg of pyrrole, and recovering the pyrrole with the recovery rate of 90%.
Example 2:
preparation of sulfonyldipyrazole:
the reaction scheme for the sulfonyl dipyrazole is as follows:
adding 11.7kg of pyrazole into a 100L enamel reaction kettle, adding 35L of dichloromethane, starting stirring, introducing chilled water into a kettle jacket, cooling to-2 ℃, adding 5kg of sulfuryl chloride and 35L of dichloromethane into a dripping tank, slowly dripping after the kettle temperature is reduced, dripping for 4 hours, replacing the chilled water with tap water after dripping is completed, stirring, discharging a reaction solution after reaction for 8 hours, filtering by a centrifugal machine, collecting solid phase pyrazole hydrochloride, separating a solvent and a product by evaporating a filtrate; the product sulfonyldipyrazole was slurried with pure water, filtered off the aqueous phase, dried for further use, and 6.0kg of sulfonyldipyrazole salt was collected in a yield of 82% and a purity of 99.2%.
Preparation of sulfuryl fluoride gas:
the reaction route of sulfuryl fluoride is as follows:
2kg of sulfonyl dipyrazole salt and 3L of pure water solution and 0.4kg of trifluoroacetic acid are added into a 10L tetrafluoro lining reaction kettle, a kettle body jacket is heated to 30 ℃ through hot water, 1.45kg of potassium fluoride aqueous solution (the mass fraction of the potassium fluoride aqueous solution is 30%) is added into a dropwise adding tank, the potassium fluoride aqueous solution is slowly added dropwise, and sulfuryl fluoride gas is compressed and collected at a gas outlet through a gas compression pump.
Recovery of pyrazole:
adding 8.2kg of pyrazole hydrochloride into an enamel reaction kettle, adding 30L of deionized water, adding 4.5kg of sodium carbonate aqueous solution, stirring for reaction for 6 hours, mixing with the water phase obtained after pulping and filtering of sulfonyl dipyrazole after the reaction is finished, evaporating the water phase until solid is separated out, washing by using ethyl acetate, collecting an organic phase, separating pyrazole by rectification, collecting pyrrole 6kg, and recovering the pyrrole with the recovery rate of 90%.
Example 3:
preparation of sulfonyldioxazolidines:
the reaction scheme for sulfonyldioxazolidines is as follows:
adding 12.5kg of oxazolidine into 100L of ceramic reaction, adding 35L of dichloromethane, starting stirring, introducing chilled water into a kettle jacket, cooling to-15 ℃, adding 5kg of sulfuryl chloride and 35L of dichloromethane into a dropping tank, slowly dropping after the kettle temperature is reduced, dropwise adding for 4 hours, replacing the chilled water with tap water after the dropwise adding is completed, stirring, discharging a reaction solution after the reaction is 5 hours, filtering by a centrifugal machine, collecting solid-phase oxazolidine hydrochloride, and separating a solvent and a product from filtrate by evaporating; the product, sulfodioxazolidine, was slurried with pure water, the aqueous phase was filtered and dried for use, 6kg of sulfonyldioxazolidine was collected in a yield of 78% and a purity of 99.5%.
Preparation of sulfuryl fluoride gas:
the reaction route of sulfuryl fluoride is as follows:
2kg of sulfonyl dioxane salt and 3L of pure water solution are added into a 10L tetrafluoro lining reaction kettle, a kettle body jacket is heated to 20 ℃ through hot water, 1.2kg of hydrogen fluoride aqueous solution (the mass fraction of the hydrogen fluoride aqueous solution is 40%) is added into a dropwise adding tank, the hydrogen fluoride aqueous solution is slowly added dropwise, and a gas compression pump is used for compressing and collecting sulfuryl fluoride gas at a gas outlet.
Recovery of oxazolidine:
7.8kg of pyrazole hydrochloride is added into an enamel reaction kettle, 30L of deionized water is added, 5kg of sodium carbonate aqueous solution is added, stirring reaction is carried out for 10 hours, after the reaction is finished, the mixture is mixed with water phase obtained after pulping and filtering of sulfonyl dioxane, the water phase is evaporated until solid is separated out, ethyl acetate is used for washing, an organic phase is collected, the oxazolidine is separated through rectification, 6kg of oxazolidine is collected, and the recovery rate is 80%.
Example 4:
preparation of sulfonyldiimidazole:
the reaction scheme of the sulfonyl diimidazole is as follows:
124kg of imidazole is added into a 1t reaction kettle, 400kg of 1, 2-dichloroethane is added, stirring is started, the kettle body is cooled to minus 5 ℃ by using a jacket, 60kg of sulfuryl chloride and 200kg of 1, 2-dichloroethane are added into a dripping tank, after the temperature of the kettle body is reduced, the sulfuryl chloride is slowly dripped, the dripping time is 1h, the kettle body is stopped from being cooled after the dripping is completed, the reaction is continued for 10h, the reaction liquid is discharged, imidazole hydrochloride is filtered out by a centrifuge, 47kg of solid-phase imidazole hydrochloride is collected, the product sulfonyldiimidazole is separated from filtrate in a rectification mode, the sulfonyldiimidazole is pulped by using water, the mixture is filtered and dried, 88kg of sulfonyldiimidazole is collected, and the yield is 95% and the purity is 99.5%.
Preparation of sulfuryl fluoride gas:
the reaction route of sulfuryl fluoride is as follows:
88kg of diimidazole sulfonate is added into a 1000L-lined tetrafluoro reaction kettle, 50kg of water is added, a kettle jacket is heated to 30 ℃ through water, 45kg of hydrofluoric acid aqueous solution (the mass fraction of the hydrofluoric acid aqueous solution is 40%) is added into a dropwise adding tank, the aqueous solution of hydrofluor acid is slowly dripped to control the reaction rate, the reaction is carried out for 8 hours, sulfuryl fluoride gas is collected through a gas compression pump at a gas outlet, the mass of the obtained sulfuryl fluoride gas is 45kg, the yield is 98%, and the purity is 99.5%.
Imidazole recovery:
adding 47kg of imidazole hydrochloride into a reaction kettle, adding 50kg of purified water, adding 24kg of sodium carbonate, stirring for 8 hours, mixing with the water phase obtained after pulping and filtering of sulfonyldiimidazole after the reaction is finished, evaporating until solid is separated out from the system, washing with ethanol, collecting liquid phase, separating imidazole by rectification, collecting imidazole 60kg, and obtaining the yield of 90%.
Collecting the aqueous solution obtained in the preparation of sulfuryl fluoride gas, adding sodium carbonate for neutralization, evaporating aqueous phase after the neutralization is completed, filtering inorganic salt, concentrating and rectifying the aqueous phase to finally obtain rectified imidazole, wherein the mass of the imidazole is 60kg, and the recovery rate is 98%.
Example 5:
preparation of sulfonyldipiperidine:
the reaction scheme for the sulfonyldipiperidines is as follows:
100kg of piperidine is added into a 1t reaction kettle, 400kg of 1, 2-dichloroethane is added, stirring is started, the kettle body is cooled to minus 10 ℃ by using a jacket, 50kg of sulfuryl chloride and 200kg of 1, 2-dichloroethane are added into a dripping tank, after the temperature of the kettle body is reduced, the sulfuryl chloride is slowly dripped, the dripping time is 5h, the kettle body is stopped from being cooled after the dripping is completed, the reaction is continued for 10h, the reaction liquid is discharged, piperidine hydrochloride is filtered out by a centrifuge, 55kg of solid-phase piperidine hydrochloride is collected, the product sulfonyl dipiperidine is separated from filtrate in a rectification mode, the sulfonyl dipiperidine is pulped by using water, the mixture is filtered and dried, and 68kg of sulfonyl dipiperidine is collected, the yield is 85%, and the purity is 99.5%.
Preparation of sulfuryl fluoride gas:
the reaction route of sulfuryl fluoride is as follows:
60kg of sulfonyl dipiperidine salt is added into a 1000L-lined tetrafluoro reaction kettle, 50kg of water is added, a kettle jacket is heated to 30 ℃ through water, 40kg of hydrofluoric acid aqueous solution (the mass fraction of the hydrofluoric acid aqueous solution is 50%) is added into a dropwise adding tank, the aqueous solution of hydrofluoride acid is slowly dripped to control the reaction rate, the reaction is carried out for 10 hours, the sulfonyl fluoride gas is collected through a gas compression pump at a gas outlet, the mass of the obtained sulfonyl fluoride gas is 30kg, the yield is 88%, and the purity is 99.5%.
Piperidine recovery:
adding 55kg of imidazole hydrochloride into a reaction kettle, adding 50kg of purified water, adding 30kg of sodium carbonate, stirring for 8 hours, mixing with the water phase obtained after pulping and filtering of the sulfonyldipiperidine after the reaction is finished, evaporating until solid is separated out from the system, washing with ethanol, collecting liquid phase, separating piperidine by rectification, collecting 50kg of piperidine, and obtaining the yield of 80%.
Collecting the aqueous solution obtained in the preparation of sulfuryl fluoride gas, adding sodium carbonate for neutralization, evaporating aqueous phase after the neutralization is completed, filtering inorganic salt, concentrating and rectifying the aqueous phase to finally obtain rectified piperidine, wherein the mass of the piperidine is 40kg, and the recovery rate is 70%.
Example 6:
preparation of sulfonylbis (dihydropyridine):
the reaction scheme for sulfonylbis (dihydropyridines) is as follows:
90kg of dihydropyridine is added into a 1t reaction kettle, 300kg of chloroform is added, stirring is started, the kettle body is cooled to 0 ℃ by using a jacket, 400kg of sulfuryl chloride is added into a dripping tank, 100kg of chloroform is added, after the kettle body temperature is reduced, the sulfuryl chloride is slowly dripped, the dripping time is 2h, the kettle body is stopped to be cooled after the dripping is finished, the reaction is continued for 2h, the reaction liquid is discharged, dihydropyridine hydrochloride is filtered out by a centrifuge, 50kg of solid-phase dihydropyridine hydrochloride is collected, the product sulfonyl bis (dihydropyridine) is separated from the filtrate in a rectification mode, the sulfonyl bis (dihydropyridine) is pulped by using water, and is filtered and dried, 50kg of sulfonyl bis (dihydropyridine) is collected, and the yield is 75%, and the purity is 99.5%.
Preparation of sulfuryl fluoride gas:
the reaction route of sulfuryl fluoride is as follows:
50kg of sulfonyl di (dihydropyridine) salt is added into a 1000L-lined tetrafluoro reaction kettle, 50kg of water is added, a kettle body jacket is heated to 60 ℃ through water, 80kg of hydrofluoric acid aqueous solution (the mass percent of the hydrofluoric acid aqueous solution is 10%) is added into a dropwise adding tank, the hydro-fluoro acid aqueous solution is slowly dripped to control the reaction rate, the reaction is carried out for 10 hours, the sulfuryl fluoride gas is collected through a gas compression pump at a gas outlet, the mass of the obtained sulfuryl fluoride gas is 20kg, the yield is 78%, and the purity is 99.5%.
And (3) recovering dihydropyridine:
adding 45kg of imidazole hydrochloride into a reaction kettle, adding 50kg of purified water, adding 20kg of calcium oxide, stirring for 8 hours, mixing with water phase obtained after pulping and filtering of sulfonyl di (dihydropyridine) after the reaction is finished, evaporating until solid is separated out from the system, washing with ethanol, collecting liquid phase, separating dihydropyridine by rectification, collecting 40kg of dihydropyridine, and obtaining the yield of 90%.
Collecting the aqueous solution obtained in the preparation of sulfuryl fluoride gas, adding calcium oxide for neutralization, evaporating aqueous phase after the neutralization is completed, filtering inorganic salt, concentrating and rectifying the aqueous phase to finally obtain the rectified dihydropyridine, wherein the mass of the dihydropyridine is 30kg, and the recovery rate is 70%.
Example 7:
preparation of sulfonyl dimethyl imidazole:
the reaction route of the sulfonyl dimethyl imidazole is as follows:
90kg of methylimidazole is added into a 1t reaction kettle, 300kg of methanol is added, stirring is started, the kettle body is cooled to minus 20 ℃ by using a jacket, 40kg of sulfuryl chloride is added into a dripping tank, 100kg of methanol is added, after the kettle body temperature is reduced, the sulfuryl chloride is slowly dripped, the dripping time is 8h, cooling of the kettle body is stopped after the dripping is finished, the reaction is continued for 8h, the reaction solution is discharged, hydrochloride is filtered out by a centrifuge, 60kg of solid-phase methylimidazole hydrochloride is collected, the filtrate is separated into a product of sulfonyldimethylimidazole by a rectification mode, the sulfonyldimethylimidazole is pulped by using water, filtered and dried, 50kg of sulfonyldimethylimidazole is collected, and the yield is 85% and the purity is 99.5%.
Preparation of sulfuryl fluoride gas:
the reaction route of sulfuryl fluoride is as follows:
50kg of sulfonyl dimethyl imidazole salt is added into a 1000L-lined tetrafluoro reaction kettle, 50kg of water is added, a kettle body jacket is heated to 50 ℃ through water, 40kg of hydrofluoric acid aqueous solution (the mass fraction of the hydrofluoric acid aqueous solution is 50%) is added into a dropwise adding tank, the aqueous solution of hydrofluoride acid is slowly dripped to control the reaction rate, the reaction is carried out for 5 hours, the sulfuryl fluoride gas is collected at a gas outlet through a gas compression pump, the mass of the obtained sulfuryl fluoride gas is 40kg, the yield is 88%, and the purity is 99.5%.
Recovering methylimidazole:
60kg of methylimidazole hydrochloride is added into a reaction kettle, 50kg of purified water is added, 20kg of potassium carbonate is added, stirring is carried out for 8 hours, after the reaction is finished, the mixture is mixed with water phase obtained after pulping and filtering of sulfonyldimethyl imidazole, the mixture is evaporated until solid is separated out from the system, ethanol is used for washing, liquid phase is collected, methylimidazole is separated through rectification, 40kg of methylimidazole is collected, and the yield is 90%.
Collecting the aqueous solution obtained in the preparation of sulfuryl fluoride gas, adding potassium carbonate for neutralization, evaporating aqueous phase after the neutralization is completed, filtering inorganic salt, concentrating and rectifying the aqueous phase to finally obtain rectified methylimidazole, wherein the mass of the methylimidazole is 30kg, and the recovery rate is 80%.
Example 8:
preparation of sulfonylbis (diethylamine):
the reaction scheme for sulfonylbis (diethylamine) is as follows:
100kg of diethylamine is added into a 1t reaction kettle, 400kg of 1, 2-dichloroethane is added, stirring is started, the kettle body is cooled to minus 5 ℃ by using a jacket, 60kg of sulfuryl chloride and 200kg of 1, 2-dichloroethane are added into a dripping tank, after the temperature of the kettle body is reduced, the sulfuryl chloride is slowly dripped, the dripping time is 1h, the kettle body is stopped from being cooled after the dripping is completed, the reaction is continued for 10h, the reaction liquid is discharged, the diethylamine hydrochloride is filtered out by a centrifuge, 47kg of solid-phase diethylamine hydrochloride is collected, the product of the sulfuryl di (diethylamine) is separated from the filtrate by a rectification mode, pulping treatment is performed on the sulfuryl di (diethylamine) by using water, 88kg of the sulfuryl di (diethylamine) is filtered and dried, and the yield is 95%, and the purity is 99.5%.
Preparation of sulfuryl fluoride gas:
the reaction route of sulfuryl fluoride is as follows:
88kg of sulfonic acid di (diethyl amine) salt is added into a 1000L-lined tetrafluoro reaction kettle, 50kg of water is added, a kettle body jacket is heated to 30 ℃ through water, 45kg of hydrofluoric acid aqueous solution (the mass fraction of the hydrofluoric acid aqueous solution is 40%) is added into a dropwise adding tank, the aqueous solution of hydrofluoride is slowly dripped to control the reaction rate, the reaction is carried out for 8 hours, sulfuryl fluoride gas is collected through a gas compression pump at a gas outlet, the mass of the obtained sulfuryl fluoride gas is 45kg, the yield is 98%, and the purity is 99.5%.
Recovery of diethylamine:
adding 47kg of imidazole hydrochloride into a reaction kettle, adding 50kg of purified water, adding 24kg of sodium carbonate, stirring for 8 hours, mixing with water phase obtained by pulping and filtering sulfonyldi (diethyl amine) after the reaction is finished, evaporating until solid is separated out from the system, washing with ethanol, collecting liquid phase, separating diethyl amine by rectification, collecting 60kg of diethyl amine, and obtaining the yield of 90%.
Collecting the aqueous solution obtained in the preparation of the sulfuryl fluoride gas, adding sodium carbonate for neutralization, evaporating the aqueous phase after the neutralization is completed, filtering inorganic salt, concentrating and rectifying the aqueous phase to finally obtain the rectified diethyl amine, wherein the mass of the diethyl amine is 60kg, and the recovery rate is 98%.
Example 9:
preparation of sulfonylbisbenzimidazoles:
the reaction scheme of the sulfonyl bisbenzimidazole is as follows:
100kg of benzimidazole is added into a 1t reaction kettle, 400kg of 1, 2-dichloroethane is added, stirring is started, the kettle body is cooled to 5 ℃ by using a jacket, 58kg of sulfuryl chloride and 200kg of 1, 2-dichloroethane are added into a dripping tank, after the temperature of the kettle body is reduced, the sulfuryl chloride is slowly dripped, the dripping time is 1h, the kettle body is stopped from being cooled after the dripping is completed, the reaction is continued for 10h, the reaction liquid is discharged, benzimidazole hydrochloride is filtered out by a centrifuge, 66kg of solid-phase benzimidazole hydrochloride is collected, the product of sulfonyl bisbenzimidazole is separated from the filtrate in a rectification mode, the sulfonyl bisbenzimidazole is pulped by using water, filtered and dried, 128kg of sulfonyl benzimidazole is collected, and the yield is 95% and the purity is 99.5%.
Preparation of sulfuryl fluoride gas:
the reaction route of sulfuryl fluoride is as follows:
128kg of sulfobenzimidazole salt is added into a 1000L-lined tetrafluoro reaction kettle, 100kg of water is added, a kettle jacket is heated to 80 ℃ through water, 45kg of hydrofluoric acid aqueous solution (the mass fraction of the hydrofluoric acid aqueous solution is 50%) is added into a dropwise adding tank, the hydro-fluoric acid aqueous solution is slowly dripped to control the reaction rate, the reaction is carried out for 8 hours, sulfuryl fluoride gas is collected through a gas compression pump at a gas outlet, the mass of the obtained sulfuryl fluoride gas is 45kg, the yield is 98%, and the purity is 99.5%.
Benzimidazole recovery:
66kg of imidazole hydrochloride is added into a reaction kettle, 50kg of purified water is added, 24kg of sodium carbonate is added, stirring is carried out for 8 hours, after the reaction is finished, the mixture is mixed with water phase obtained after pulping and filtering of the sulfonyl bisbenzimidazole, the mixture is evaporated until solid in the system is separated out, ethanol is used for washing, liquid phase is collected, benzimidazole is separated through rectification, 60kg of benzimidazole is collected, and the yield is 90%.
Collecting the aqueous solution obtained in the preparation of sulfuryl fluoride gas, adding sodium carbonate for neutralization, evaporating aqueous phase after the neutralization is completed, filtering inorganic salt, concentrating and rectifying the aqueous phase to finally obtain the rectified benzimidazole, wherein the mass of the benzimidazole is 35kg, and the recovery rate is 98%.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (11)

1. The preparation method of sulfuryl fluoride is characterized by comprising the following steps:
(1) Sulfonamide is formed by the reaction of sulfuryl chloride and a secondary amine: dissolving secondary amine in an organic solvent to obtain an organic solution of the secondary amine, slowly dripping sulfuryl chloride into the organic solution of the secondary amine at a low temperature, stirring and reacting to generate amine hydrochloride and sulfonamide, filtering the amine hydrochloride, and recovering the organic solvent to obtain sulfonamide;
(2) Purifying sulfonamide: pulping and washing the sulfonamide by using purified water, filtering an aqueous phase, and drying to obtain purified sulfonamide;
(3) The sulfonamide reacts with the fluoride salt to form sulfuryl fluoride: heating the purified sulfonamide and water in water bath, slowly dropwise adding an aqueous solution of fluoride salt under stirring, and reacting to obtain sulfuryl fluoride;
(4) Recovering the secondary amine: dissolving the amine hydrochloride in the step (1) by using the filtered water phase in the step (2), adding inorganic alkali for neutralization, and extracting the water phase by using an extractant to recover the secondary amine.
2. The process according to claim 1, wherein in step (1), the secondary amine is in the form of a ring closed, heterocyclic or linear chain selected from the following structures:
wherein n is an integer of 1 or more; r, R 1 、R 2 The same or different, are each independently selected from hydrogen, halogen, carbonyl, carboxyl, nitro, aliphatic or aromatic hydrocarbons; y is heteroAn atom selected from C, S, O or N.
3. The method according to claim 1, wherein in the step (1), the organic solvent is at least one of dichloromethane, dichloroethane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, toluene, ethanol, methanol, epoxyhexane, chloroform, diethyl ether, and petroleum ether.
4. The process according to claim 1, wherein in step (1), the reaction is carried out at a temperature of-20 ℃ to 15 ℃ for a time of 8 to 16 hours.
5. The process according to claim 1, wherein in step (1), the molar ratio of secondary amine to sulfuryl chloride is: 4:1-5.5:1.
6. The method according to claim 1, wherein in the step (3), the fluoride salt is at least one of sodium fluoride, potassium fluoride, sodium bifluoride, potassium bifluoride, hydrogen fluoride, ammonium fluoride, and triethylamine trifluoride.
7. The preparation method according to claim 1, wherein in the step (3), the mass ratio of the sulfonamide to the water is 1:1.5-1:5, the molar ratio of the fluoride salt to the sulfuryl chloride is 2:1-4.5:1, and the mass fraction of the fluoride salt in the aqueous solution of the fluoride salt is 10% -50%.
8. The process according to claim 1, wherein in step (3), the reaction temperature is from-5 ℃ to 90 ℃ for a period of 4 to 10 hours.
9. The method according to claim 1, wherein in the step (3), a catalyst is further added, and the catalyst is at least one of formic acid, acetic acid, trifluoroacetic acid, hydrofluoric acid aqueous solution, trifluoromethanesulfonic acid, sulfuric acid, aluminum trichloride, ferric trichloride, and zinc chloride.
10. The process according to claim 9, wherein in step (3), the molar ratio of catalyst to sulfonamide is 0 to 5.0.
11. The method according to claim 1, wherein in the step (4), the inorganic base is at least one of sodium carbonate, sodium bicarbonate, lithium carbonate, potassium bicarbonate, sodium hydroxide, calcium oxide, magnesium oxide, calcium hydroxide, and potassium hydroxide; in the step (4), the extractant is at least one of dichlorohexane, toluene, ethyl acetate, chloroform and diethyl ether.
CN202211191311.1A 2022-09-28 2022-09-28 Preparation method of sulfuryl fluoride Pending CN117142437A (en)

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