CN108409708B - A kind of preparation method of sulfuric ester - Google Patents
A kind of preparation method of sulfuric ester Download PDFInfo
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- CN108409708B CN108409708B CN201810107719.3A CN201810107719A CN108409708B CN 108409708 B CN108409708 B CN 108409708B CN 201810107719 A CN201810107719 A CN 201810107719A CN 108409708 B CN108409708 B CN 108409708B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/68—Preparation of metal alcoholates
- C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/28—Metal alcoholates
- C07C31/30—Alkali metal or alkaline earth metal alcoholates
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Abstract
The present invention relates to organic synthesis fields, more particularly to a kind of preparation method of sulfuric ester.Invention provides a kind of preparation method of sulfuric ester, comprising: reacts under the conditions of by Formula II compound existing for the reaction dissolvent with vikane, prepares compound of formula I.The present invention effectively avoids the introducing of water and chloride ion during preparing sulfuric ester, decompose and the high situation of chloride ion content so as to avoid product；In addition, preparation method step of the invention is brief, institute is commercially available general chemical using raw material, and raw material variety is few, and side reaction is few, high income；The method manufacturing cost that the present invention prepares sulfuric ester is low; and recyclable organic solvent is used only in reaction; byproduct of reaction is single inorganic salts solid; it is easily recycled processing; do not generate waste water; it is more favorable for environmental protection, therefore the preparation method of sulfuric ester of the invention is real green, environmental protection and the method for being suitble to industrialization large-scale production.
Description
Technical field
The present invention relates to organic synthesis fields, more particularly to a kind of preparation method of sulfuric ester.
Background technique
The thermal adaptability of extensive use recently as lithium ion battery in electric car field, lithium ion battery is got over
More to attract attention.In China's most area, summer temperature is up to 38 DEG C or so, and to winter then down to -10 DEG C or so,
This proposes acid test to the high temperature performance of battery.Sulfuric acid ester compound has been widely used, especially cyclic annular sulphur
Acid esters compound is more and more used as the novel addition of lithium battery SEI film and lithium electronics electrolyte
Agent, to improve battery high temperature performance.Research shows that cyclic sulfates can restore in the electrolytic solution generates sulfites chemical combination
Object, and this kind of compounds have good thermal stability, therefore can improve the high-temperature stability of lithium battery SEI film, in turn
Improve the high temperature cyclic performance and high-temperature storage performance of battery；The ingredient that SEI film can be optimized simultaneously, reduces the impedance of battery,
Be conducive to improve the low temperature performance of battery.
The preparation method of the cyclic sulfates of open report is largely first with glycol compound and thionyl chloride at present
Reaction obtains corresponding cyclic sulfite, and further oxidation obtains cyclic sulfates.This method common problem
It is to influence product qualities due to being difficult to remove using the chloride ion of thionyl chloride, introducing in reaction process, other oxidation step
Operation and Material Cost are high.
Such as CN106187989 report carries out substitution reaction as raw material using thionyl chloride and ethylene glycol and prepares sulfurous acid ethylene
Ester continues in methylene chloride-water two-phase of sulfur acid iron, is oxidized to sulfuric acid vinyl ester with SODIUM PERCARBONATE.Two step of technique is anti-
A large amount of brine wastes should be generated, Environmental Inputs are at high cost, and product is difficult to purify, and in addition product is easy to decompose in water, make product
Matter is unstable.
And patent CN105481826A still carries out substitution reaction as raw material using thionyl chloride and ethylene glycol and prepares sulfurous acid second
Enester, then sulfuric acid vinyl ester is prepared using ruthenium trichloride and sodium hypochlorite as oxidant.This method, which equally exists, reacts aqueous, waste water
Big problem is measured, in addition oxidising agent is expensive, causes process costs height, is not suitable for Commercialization application.
CN104945368A reports that thionyl chloride and 1,2- pentanediol are that raw material carries out addition reaction, then sodium hypochlorite is added dropwise
Oxidation reaction, which is carried out, with the mixed solution of catalyst ruthenium trichloride or ruthenic oxide prepares 4- propyl sulfuric acid vinyl ester.This method behaviour
Make cumbersome, oxidising agent is expensive, and manufacturing cost is high.
As it can be seen that the prior art provides a variety of methods for preparing sulfuric ester, but all there is, systems unfavorable to product quality
The defects of at high cost, Environmental Inputs are high is made, causes difficulty to the popularization and application of industrial production and product.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of preparation method of sulfuric ester,
For solving the problems of the prior art.
In order to achieve the above objects and other related objects, the present invention provides a kind of preparation method of sulfuric ester, comprising: by formula
It is reacted under the conditions of II compound is existing for the reaction dissolvent with vikane, prepares compound of formula I, the following institute of reaction equation
Show:
Wherein, n is selected from 0,1,2,3 or 4；
M is selected from Li, Na, K；
R1, R2, R3, R4, R5, R6 be each independently selected from H, C1~C4 alkyl, C6~C18 aryl, C1~C4 alkoxy,
Chlorine or bromine.
In some embodiments of the present invention, n is selected from 0 or 1；
In some embodiments of the present invention, M is selected from Na, K.
In some embodiments of the present invention, R1 is selected from H, methyl or propyl.
In some embodiments of the present invention, R2~R6 is hydrogen.
In some embodiments of the present invention, the molar ratio of vikane and Formula II compound is 1~3:1.
In some embodiments of the present invention, the molar ratio of vikane and Formula II compound is 1.2~2:1.
In some embodiments of the present invention, it is molten that the reaction dissolvent that Formula II compound is reacted with vikane is selected from arene
One of agent, esters solvent, halogenated alkanes solvents, ether solvent, nitrile solvents or a variety of combinations.
In some embodiments of the present invention, reaction dissolvent that Formula II compound is reacted with vikane selected from methylene chloride,
Dichloroethanes, ether, methyl tertiary butyl ether(MTBE), glycol dimethyl ether, tetrahydrofuran, methyltetrahydrofuran, acetonitrile, one in propionitrile
Kind or a variety of combinations
In some embodiments of the present invention, the reaction temperature that Formula II compound is reacted with vikane is -70 DEG C~30 DEG C.
In some embodiments of the present invention, the reaction temperature that Formula II compound is reacted with vikane is -30 DEG C~-5 DEG C.
In some embodiments of the present invention, Formula II compound carries out under conditions of closed with reacting for vikane.
In some embodiments of the present invention, by vikane and Formula II compound by amount hybrid reaction.
In some embodiments of the present invention, Formula II compound and vikane react under conditions of gas shield into
Row.
In some embodiments of the present invention, Formula II compound is reacted with vikane in nitrogen and/or inert gas guarantor
It is carried out under conditions of shield.
In some embodiments of the present invention, Formula II compound includes: by reactant with the post-processing of vikane reacted
System's heating, removes the vikane in product, is separated by solid-liquid separation, and liquid phase concentration obtains precipitate.
In some embodiments of the present invention, the post-processing of Formula II compound and vikane reacted further include: will be precipitated
Object recrystallization and/or mashing.
In some embodiments of the present invention, in the recrystallization and/or mashing, metal ion chelation agent is added, it is described
Metal ion chelation agent is selected from crown ether.
In some embodiments of the present invention, Formula II formula III compound system of reacting with alkali species
Standby to obtain, reaction equation is as follows:
Alkali metal element in the alkali species is selected from Li, Na, K.
In some embodiments of the present invention, the alkali species are selected from alkali metal hydroxide, alkali metal alcoholates, alkali
One of metal simple-substance, alkali metal hydride, alkali metal oxide, alkali carbonate or a variety of combinations.
In some embodiments of the present invention, the alkali metal hydroxide is selected from lithium hydroxide, lithium hydroxide one is hydrated
One of object, sodium hydroxide, potassium hydroxide or a variety of combinations.
In some embodiments of the present invention, the alkali metal alcoholates be selected from lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide,
One of sodium ethoxide, potassium ethoxide, isopropyl lithium alkoxide, sodium isopropylate, potassium isopropoxide, potassium tert-butoxide, sodium tert-butoxide or a variety of groups
It closes.
In some embodiments of the present invention, the alkali metal simple substance is selected from one of SODIUM METAL, elemental lithium, simple substance potassium
Or a variety of combination.
In some embodiments of the present invention, the alkali metal oxide is selected from one of sodium oxide molybdena, potassium oxide or more
The combination of kind.
In some embodiments of the present invention, the alkali metal hydride is selected from one of sodium hydrogen, lithium hydrogen or a variety of
Combination.
In some embodiments of the present invention, the alkali carbonate is selected from sodium carbonate, lithium carbonate, potassium carbonate, carbonic acid
One of hydrogen sodium, saleratus or a variety of combinations.
In some embodiments of the present invention, formula III compound and the molar ratio of alkali metal element in alkali species are
0.5~3:1, preferred molar ratio are 0.6~1.5:1；
In some embodiments of the present invention, the reaction temperature that formula III compound is reacted with alkali species is 70-150
℃；
In some embodiments of the present invention, formula III compound and alkali species react existing for the reaction dissolvent
Condition carries out.
In some embodiments of the present invention, the reaction dissolvent that formula III compound is reacted with alkali species is selected from fragrance
Hydrocarbon solvent.
In some embodiments of the present invention, reaction dissolvent that formula III compound is reacted with alkali species selected from toluene,
One of dimethylbenzene, benzene or a variety of combinations.
In some embodiments of the present invention, when alkali species are selected from alkali metal hydroxide, alkali metal alcoholates, alkali gold
When belonging to hydroxide, alkali carbonate, formula III compound is reacted with alkali species, removing body is heated in reaction process
The low boiling point component generated in system；
In some embodiments of the present invention, when alkali species are alkali metal hydride, alkali metal simple substance, by formula
III compound is added in the reaction dissolvent containing alkali species by amount to be reacted.
Specific embodiment
Inventor explores and studies by a large amount of, provides a kind of preparation method of new sulfuric ester, described
Preparation method effectively avoids the introducing of water and chloride ion, and with step is brief, side reaction is few, high income, post-processing letter
The features such as single, is suitble to industrialization large-scale production, completes the present invention on this basis.
One aspect of the present invention provides a kind of preparation method of sulfuric ester, and the chemical structural formula of the sulfuric ester is shown in formula I,
The preparation method of the sulfuric ester, may include: by Formula II compound existing for the reaction dissolvent under the conditions of reacted with vikane,
Compound of formula I is prepared, reaction equation is as follows:
Wherein, n can be selected from 0,1,2,3 or 4；M can be selected from Li, Na, K；R1, R2, R3, R4, R5, R6 can respectively solely
On the spot it is selected from H, C1~C4 alkyl, C6~C18 aryl, C1~C4 alkoxy, chlorine or bromine.C1~C4 alkyl can be for example
Methyl, ethyl, propyl, n-propyl, isopropyl, butyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl etc..C6~C18 virtue
Base can be such as phenyl, naphthalene, fluoranthene base, fluorenyl, tetrahydro naphthyl, indanyl, anthryl.C1~C4 alkoxy can
To be such as methoxyl group, ethyoxyl, propoxyl group, positive propoxy, isopropoxy, butoxy, n-butoxy, isobutoxy, Zhong Ding
Oxygroup, tert-butoxy etc..In a preferred embodiment of the invention, n can be selected from 0 or 1.In another preferred implementation side of the present invention
In formula, M can be selected from Na, K.In another preferred embodiment of the present invention, R1 can be selected from H, methyl or propyl.In the present invention
In another preferred embodiment, R2~R6 can be hydrogen.In another preferred embodiment of the present invention, compound of formula I be can be
Sulfuric acid vinyl ester, 4- methylsulfuric acid vinyl acetate, 4- propyl sulfuric acid vinyl ester, sulfuric acid acrylic ester etc..In another preferred reality of the present invention
It applies in mode, Formula II compound can be ethylene glycol sodium, ethylene glycol potassium, 1,2-PD sodium, 1,2-PD potassium, 1,2- penta 2
Sodium alkoxide, 1,2- pentanediol potassium, 1,3-PD sodium, 1,3-PD potassium etc..
In the preparation method of sulfuric ester provided by the present invention, by the dosage of molar amount vikane relative to Formula II chemical combination
The dosage of object is usually basic equivalent or excessive, for example, the molar ratio of vikane and Formula II compound can be 1~3:
1, it can also be 1.2~2:1.
In the preparation method of sulfuric ester provided by the present invention, Formula II compound is usually reacting molten with reacting for vikane
Condition existing for agent carries out, and those skilled in the art can choose the solvent of suitable species and dosage for Formula II compound and sulphur
The reaction of acyl fluorides, for example, to can be aromatic hydrocarbon solvent, esters molten for the reaction dissolvent in the reacting of Formula II compound and vikane
Agent, halogenated alkanes solvents, ether solvent, nitrile solvents etc.；For another example the fragrance in the reacting of Formula II compound and vikane
Hydrocarbon reaction solvent can be toluene, dimethylbenzene, benzene, chlorobenzene, dichloro-benzenes etc.；For another example Formula II compound and vikane is anti-
Esters solvent in answering can be ethyl acetate, n-propyl acetate, dimethyl carbonate, diethyl carbonate etc.；For another example Formula II
The halogenated alkanes solvents closed in the reacting of object and vikane can be methylene chloride, dichloroethanes etc.；For another example Formula II chemical combination
Ether solvent in the reacting of object and vikane can be ether, methyl tertiary butyl ether(MTBE), glycol dimethyl ether, tetrahydrofuran, first
Base tetrahydrofuran, dioxane etc.；For another example the nitrile solvents in the reacting of Formula II compound and vikane can be acetonitrile,
Propionitrile, n-Butyronitrile etc..In an of the invention preferred embodiment, the reaction dissolvent in the reacting of Formula II compound and vikane can
With selected from halogenated alkanes solvents, ether solvent, nitrile solvents etc., more specifically can be methylene chloride, dichloroethanes, ether,
Methyl tertiary butyl ether(MTBE), glycol dimethyl ether, tetrahydrofuran, methyltetrahydrofuran, acetonitrile, propionitrile etc..
In the preparation method of sulfuric ester provided by the present invention, Formula II compound reacts usually with vikane lower
It is carried out under the conditions of temperature, to guarantee the stabilization of reaction system, for example, reaction temperature can be the temperature condition not higher than room temperature,
It may be -70 DEG C~30 DEG C, or -30 DEG C~-5 DEG C.Those skilled in the art can be according to the factors tune such as reaction process
The whole reaction time, the method for monitoring reaction process should be to those skilled in the art it is known, for example, can pass through
The reaction process of the monitoring such as gas chromatography, liquid chromatography reaction, for another example the reaction time can be 2-10 hours, it can also
Think 2-5 hours.
In the preparation method of sulfuric ester provided by the present invention, Formula II compound can be closed with reacting for vikane
Under the conditions of carry out.When reaction, usually reactant can thereby may be ensured that by vikane and Formula II compound by amount hybrid reaction
The stabilization of system.For example, sulfuryl fluoride gas can be slowly introducing to the mixture being made of Formula II compound and appropriate reaction dissolvent
In system；Formula II compound can also be mixed with appropriate reaction dissolvent, the reaction including vikane and reaction dissolvent is added by amount
In system.
In the preparation method of sulfuric ester provided by the present invention, Formula II compound is usually protected in gas with reacting for vikane
It is carried out under conditions of shield, so as to effectively avoid the gases such as the steam in air from having an impact reaction.Gas shield is provided
The gas of condition usually can be not with the main matter in reaction system (for example, Formula II compound, vikane, Formulas I chemical combination
Object) gas that chemically reacts, for example, it may be nitrogen and/or inert gas etc., for another example the inert gas can be with
It is helium, neon, argon gas, Krypton, xenon etc..
In the preparation method of sulfuric ester provided by the present invention, Formula II compound and the post-processing of vikane reacted can be with
Include: that reaction system heats up, remove the vikane in product, be separated by solid-liquid separation, liquid phase concentration obtains precipitate.It post-processed
Reaction system can be risen to suitable temperature by those skilled in the art in journey, for example, reaction system can be warmed to room temperature, more
Reaction system can specifically be risen to 20~30 DEG C.The sulfonyl in suitable method removal product may be selected in those skilled in the art
Fluorine, it is, for example, possible to use nitrogen and/or inert gas to advertise the vikane in removing system.It is separated by solid-liquid separation in last handling process
Main function be insoluble matter in removing system, used method can be the various this fields such as filtering, filters pressing, centrifugation
Conventional separation methods.In last handling process, the temperature of liquid phase concentration is normally no higher than 60 DEG C, and preferred temperature is no greater than 40
℃.It is concentrated into 0.5~3 times that residual solvent quality is about Formula II compound investment quality, such as residual solvent can be concentrated into
Quality is 1~1.5 times of Formula II compound quality, and product is gradually precipitated after concentration, can be down to and obtain precipitate (acquisition at room temperature
The mode of precipitate can be separation of solid and liquid, and resulting precipitate is usually sulfuric ester crude product).
In the preparation method of sulfuric ester provided by the present invention, the post-processing of the Formula II compound and vikane reacted
It can also include: that precipitate is recrystallized and/or is beaten.Suitable solvent type may be selected for that will analyse in those skilled in the art
Object is recrystallized and/or is beaten out, for example, solvent used in recrystallization and/or pulping process can be such as alkane
Class solvent, aromatic hydrocarbon solvent, esters solvent, halogenated alkanes solvents, ether solvent, alcohols solvent etc.；For another example recrystallization
And/or alkane solvents used in pulping process can be n-hexane, normal heptane, hexamethylene etc.；For another example recrystallization
And/or aromatic hydrocarbon solvent used in pulping process can be such as toluene, dimethylbenzene；For another example recrystallization and/or
Esters solvent used in pulping process can be ethyl acetate, n-propyl acetate, dimethyl carbonate etc.；For another example tie again
Halogenated alkanes solvents used in brilliant and/or pulping process can be methylene chloride, 1,2- dichloroethanes etc.；For another example
Ether solvent used in recrystallization and/or pulping process can be such as ether, ethyl methyl ether, tetrahydrofuran, tert-butyl first
Base ether, dioxane etc.；For another example alcohols solvent used in recrystallization and/or pulping process can be ethyl alcohol, methanol
Deng.Suitable solvent usage may be selected for recrystallizing and/or being beaten precipitate in those skilled in the art, for example, weight
Solvent usage in crystallization and/or pulping process can be 1-10 times of sample to be processed (for example, described precipitate) quality, then
For example, the dosage of solvent can be 4-10 times of sample mass to be processed in recrystallization process, for another example solvent in pulping process
Dosage can be 1-3 times of sample mass to be processed.In a preferred embodiment of the invention, precipitation substance can be added
The methylene chloride of 1~1.5 times of amount carries out one or many mashing.In the recrystallization and/or mashing, suitable gold can be added
Belong to ion chelating agent, so as to avoid introducing metal ion in purified product, the metal ion can be such as Na ion,
K ion etc..During the optional suitable species of those skilled in the art and the metal-chelator of dosage are used to recrystallize and/or be beaten,
For example, the metal ion chelation agent can be crown ether etc., for another example the crown ether can be 12-crown-4,15- crown- 5,18-
One of crown- 6 etc. or a variety of combinations, for another example the dosage of the metal ion chelation agent can be sample (example to be processed
Such as, the precipitate) quality 0.01%~5%, be also possible to the 0.1%~1% of sample mass to be processed.
In the preparation method of sulfuric ester provided by the present invention, the Formula II compound can be by formula III compound and alkali
Metallics reaction prepares, and reaction equation is as follows:
Wherein, in formula III compound the definition of R1-R6, M, n referring to the definition in Formulas I as described above, Formula II compound,
And it is corresponding with the related definition in Formulas I, Formula II compound.
In the preparation method of sulfuric ester provided by the present invention, the alkali species are often referred to include alkali metal element
Substance, for example, the alkali species can be alkali metal hydroxide, alkali metal alcoholates, alkali metal simple substance, metal hydride alkaline
One of object, alkali metal oxide, alkali carbonate etc. or a variety of combinations, the alkali metal element is typically
Li,Na,K.For another example the alkali metal hydroxide can be selected from lithium hydroxide, lithium hydroxide monohydrate sodium hydroxide, hydrogen
One of potassium oxide etc. or a variety of combinations；For another example the alkali metal alcoholates can be selected from lithium methoxide, sodium methoxide, methanol
One in potassium, lithium ethoxide, sodium ethoxide, potassium ethoxide, isopropyl lithium alkoxide, sodium isopropylate, potassium isopropoxide, potassium tert-butoxide, sodium tert-butoxide etc.
Kind or a variety of combinations；For another example the alkali metal simple substance can selected from one of SODIUM METAL, elemental lithium, simple substance potassium etc. or
A variety of combinations；For another example the alkali metal oxide can be selected from one of sodium oxide molybdena, potassium oxide etc. or a variety of groups
It closes；For another example the alkali metal hydride can be selected from one of sodium hydrogen, lithium hydrogen etc. or a variety of combinations；For another example described
Alkali carbonate can be selected from one of sodium carbonate, lithium carbonate, potassium carbonate, sodium bicarbonate, saleratus etc. or a variety of
Combination.The mole of institute's hydroxyl is usually relative to the mole of alkali metal element in alkali species in formula III compound
Basic equivalent or excessive, for example, the molar ratio of alkali metal element can be 0.5 in formula III compound and alkali species
~3:1, or 0.6~1.5:1.
In the preparation method of sulfuric ester provided by the present invention, formula III compound usually exists with reacting for alkali species
It is carried out under the conditions of room temperature to the temperature of solvent refluxing, for example, reaction temperature can be the temperature of room temperature to solvent boiling point, it can also be with
It is 70-150 DEG C.Those skilled in the art can adjust the reaction time according to factors such as reaction process, the method for monitoring reaction process
It should be known to those skilled in the art, for example, can be anti-by monitoring such as gas chromatography, liquid chromatography
The reaction process answered, for another example the reaction time can be 5-30 hours.
In the preparation method of sulfuric ester provided by the present invention, formula III compound usually exists with reacting for alkali species
Condition existing for reaction dissolvent carries out, and those skilled in the art can choose the solvent of suitable species and dosage for formula III
Reacting for object and alkali species is closed, for example, the reaction dissolvent used in the reacting of formula III compound and alkali species can
To be aromatic hydrocarbon solvent, for another example can be toluene, dimethylbenzene, benzene etc..Suitable reaction may be selected in those skilled in the art
Operating method realizes reacting between formula III compound and alkali species.For example, when alkali species are selected from alkali metal hydrogen
It, can be by formula III compound and alkali species whens oxide, alkali metal alcoholates, alkali metal oxide, alkali carbonate etc.
Reaction heats the low boiling point component generated in removal system in reaction process (for example, the water, methanol, ethyl alcohol, different that reaction generates
The components such as propyl alcohol, the tert-butyl alcohol), formula III compound and alkali species react under the conditions of can be existing for the reaction dissolvent into
Row, the presence of solvent can efficiently separating in order to low boiling point component.For another example when alkali species be alkali metal hydride,
When alkali metal simple substance, formula III compound can be added in the reaction dissolvent containing alkali species by amount and be reacted.Example again
Such as, formula III compound and the post-processing of alkali species reacted may include: precipitation after the reaction was completed.
The sulfuric ester product that the preparation method that another aspect of the present invention provides the sulfuric ester prepares.
The present invention effectively avoids the introducing of water and chloride ion during preparing sulfuric ester, so as to avoid product point
Solution and the high situation of chloride ion content；In addition, preparation method step of the invention is brief, institute is commercially available routinize using raw material
Product, and raw material variety is few, side reaction is few, high income；The method manufacturing cost that the present invention prepares sulfuric ester is low, and reaction only makes
With recyclable organic solvent, byproduct of reaction is single inorganic salts solid, is easily recycled processing, does not generate waste water, more sharp
It is real green, environmental protection in the preparation method of environmental protection, therefore sulfuric ester of the invention and is suitble to industrialization large-scale production
Method.
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
It should be clear that in the following example not specifically dated process equipment or device be all made of conventional equipment in the art or
Device.
In addition, it should also be understood that, one or more method and step mentioned in the present invention does not repel before and after the combination step
It can also be inserted into other methods step there may also be other methods step or between these explicitly mentioned steps, unless separately
It is described；It should also be understood that the combination connection relationship between one or more equipment/device mentioned in the present invention is not repelled
The two equipment/devices specifically mentioned before and after the unit equipment/device there may also be other equipment/device or at these it
Between can also be inserted into other equipment/device, unless otherwise indicated.Moreover, unless otherwise indicated, the number of various method steps is only
Identify the convenient tool of various method steps, rather than for the arrangement order of limitation various method steps or limits the enforceable model of the present invention
It encloses, relativeness is altered or modified, and without material changes in technical content, when being also considered as, the present invention is enforceable
Scope.
Embodiment 1
The preparation of sulfuric acid vinyl ester:
200ml toluene, 75g ethylene glycol (1.2mol) and 80g (2mol) hydrogen-oxygen are put into the reaction flask equipped with water segregator
Change sodium, be warming up under reflux temperature and react, observing in water segregator constantly has moisture to distillate.Reaction terminates after 20 hours, by system
Solvent is evaporated to obtain ethylene glycol disodium salt, and weigh 107.3g, for use.
In 1000mL reaction flask, ethylene glycol the disodium salt 106.0g and 500mL of above-mentioned steps preparation are added under nitrogen protection
Methylene chloride keeps Nei Wen -10~10 DEG C to be slowly introducing sulfuryl fluoride gas 148.7g (1.47mol), and insulation reaction 1.5 hours,
It advertises nitrogen 1 hour, filters, depressurize precipitation at 40 DEG C of filtrate, obtain solid crude product and methylene chloride 200mL, 15- crown- 5 is added
0.05g, 18- crown- 6 0.05g, temperature rising reflux 1h, then be slowly dropped to room temperature, filtering, dry off-white powder 91.5g.Detection
As a result: GC (%): 99.0%；Ion concentration Na+(2ppm), K+(0.8ppm), Fe3+(0.5ppm), Cl-(< 1ppm).
Embodiment 2
The preparation of sulfuric acid acrylic ester:
200ml toluene, 1,3-PD 100g (1.31mol) and 110g first are put into the reaction flask equipped with division box
Sodium alkoxide (2.04mol), stirring are warming up to low-boiling-point substance in reflux separation system, and 200ml dichloromethane is added in slow cooling after 15 hours
It is stand-by that alkane is made into sodium salt suspension.
2000mL autoclave, nitrogen displaced air, be added 500ml methylene chloride after, under nitrogen protection keep Nei Wen -10~
0 DEG C is passed through vikane 145.3g, sodium salt suspension is instilled in kettle, insulation reaction 2 hours.It has reacted nitrogen and has advertised system removing
Extra sulfuryl fluoride gas depressurizes precipitation to dry after filtering reaction solution.300ml methyl tertiary butyl ether(MTBE), 15- crown- is added in crude product
6 0.05g of 50.05g, 18- crown-, is stirred at room temperature 1h, dry product 104.7g (two step yields 82.7%) G/C content after filtering
99.9%, sodium ion 0.7ppm, potassium ion 2ppm, chloride ion < 1ppm.
Embodiment 3
The preparation of 4- propyl sulfuric acid vinyl ester:
The suspension that 55g sodium hydrogen (2.3mol) and 200ml tetrahydrofuran are prepared under nitrogen protection, is slowly added dropwise under micro- reflux
The mixed liquor of 1,2- pentanediol 125g (1.2mol) and 200ml tetrahydrofuran constantly has gas to generate discharge system.It is small to stir 10
When after there is no gas generation, it is stand-by to obtain sodium salt suspension.
In nitrogen displacement 2000mL autoclave after air, after 300ml tetrahydrofuran is added under nitrogen protection, Nei Wen-is kept
10~0 DEG C are passed through vikane 151.6g (1.48mol), and sodium salt suspension is continuously added in kettle, and insulation reaction 2 hours.Reaction
Complete nitrogen advertises system and removes extra sulfuryl fluoride gas, and decompression precipitation is to dry after reaction solution filtering.300ml dichloro is added in crude product
Methane, 5 0.1g of 15- crown-, 18- crown- 6 0.1g, return stirring 1h, dry product 162.7g (two step yields after filtering
85.1%) G/C content > 99.9%, sodium ion 6ppm, potassium ion 3ppm, chloride ion < 1ppm.
Embodiment 4
The preparation of sulfuric acid vinyl ester:
200ml toluene, ethylene glycol 80g (1.29mol) and 108g sodium methoxide (2.00mol), stirring are put into reaction flask
It is warming up to reflux, methanol is constantly separated off, is evaporated after 15 hours, residue is transferred into rapidly anhydrous 2000ml autoclave,
800ml methylene chloride is added under nitrogen protection, is cooled to -10~0 DEG C, is slowly introducing vikane 129.0g, led within about 1 hour,
Insulation reaction 2 hours.It has reacted nitrogen to advertise 1 hour, filter, filtrate decompression precipitation is to dry.Crude product addition 250ml n-hexane,
5 0.5g of 15- crown-, 6 0.5g of 18- crown-, is stirred at room temperature 1h, and dry light brown powder solid 100.2g, GC contain after filtering
Amount 99.9%.
Embodiment 5
The preparation of sulfuric acid vinyl ester
200ml dimethylbenzene is put into reaction flask, ethylene glycol 81.2g and 110g potassium hydroxide is stirred to reflux state about
Solvent evaporated after 130-140 DEG C, 20 hours, adds 400ml anhydrous acetonitrile, stirs into uniform suspension.It is close after nitrogen displacement
Suspension is continuously added in the mixed solution being made by 130g vikane and 400ml acetonitrile by closure system, keeps reaction system temperature
- 15~-5 DEG C of degree, adds for about 1 hour, keeps the temperature 1 hour.It reacts end and advertises reaction system with nitrogen, be filtered to remove insoluble matter,
Precipitation is depressurized at 60 DEG C of filtrate to dry, obtained solid the 250ml containing 0.6g 15- crown- 5 and 0.5g 18- crown- 6 just oneself
It is stirred at room temperature in alkane solution 1 hour, filtering, dry off-white powder 106.3g；G/C content > 99.9%, potassium ion 6ppm,
Chloride ion < 1ppm.
In conclusion the present invention effectively overcomes various shortcoming in the prior art and has high industrial utilization value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (12)
1. a kind of preparation method of sulfuric ester, the chemical structural formula of the sulfuric ester are shown in formula I, comprising: by Formula II compound
It is reacted under the conditions of existing for the reaction dissolvent with vikane, prepares compound of formula I, reaction equation is as follows:
Wherein, n is selected from 0,1,2,3 or 4；
M is selected from Li, Na, K；
R1, R2, R3, R4, R5, R6 are each independently selected from H, C1~C4 alkyl, C1~C4 alkoxy, chlorine or bromine；
The molar ratio of vikane and Formula II compound is 1~3:1；
The reaction temperature that Formula II compound is reacted with vikane is -30 DEG C~30 DEG C.
2. the preparation method of sulfuric ester as described in claim 1, which is characterized in that n is selected from 0 or 1；
And/or M is selected from Na, K.
3. the preparation method of sulfuric ester as described in claim 1, which is characterized in that R1 is selected from H, methyl or propyl.
4. the preparation method of sulfuric ester as described in claim 1, which is characterized in that R2~R6 is hydrogen.
5. the preparation method of sulfuric ester as described in claim 1, which is characterized in that further include one in following technical characteristic
Or it is multiple:
A1) reaction dissolvent that Formula II compound is reacted with vikane is selected from aromatic hydrocarbon solvent, ester solvent, halogenated alkane solvents, ether
One of solvent, nitrile solvent or a variety of combinations；
A2) Formula II compound carries out under conditions of closed with reacting for vikane；
A3) by vikane and Formula II compound by amount hybrid reaction；
A4) Formula II compound carries out under conditions of gas shield with reacting for vikane；
A5) Formula II compound includes: that reaction system heats up with the post-processing of vikane reacted, and removes the sulfonyl in product
Fluorine is separated by solid-liquid separation, and liquid phase concentration obtains precipitate.
6. the preparation method of sulfuric ester as claimed in claim 5, which is characterized in that further include one in following technical characteristic
Or it is multiple:
B1) molar ratio of vikane and Formula II compound is 1.2~2:1；
B2) reaction dissolvent that Formula II compound is reacted with vikane is selected from methylene chloride, dichloroethanes, ether, methyl tertbutyl
One of ether, glycol dimethyl ether, tetrahydrofuran, methyltetrahydrofuran, acetonitrile, propionitrile or a variety of combinations；
B3) reaction temperature that Formula II compound is reacted with vikane is -30 DEG C~-5 DEG C；
B4) Formula II compound carries out under conditions of nitrogen and/or inert gas shielding with reacting for vikane；
B5) the post-processing of Formula II compound and vikane reacted further include: precipitate is recrystallized and/or is beaten.
7. the preparation method of sulfuric ester as claimed in claim 6, which is characterized in that in the recrystallization and/or mashing, be added
Metal ion chelation agent, the metal ion chelation agent are selected from crown ether.
8. the preparation method of sulfuric ester as described in claim 1, which is characterized in that the Formula II formula III chemical combination
Object is reacted with alkali species to be prepared, and reaction equation is as follows:
Alkali metal element in the alkali species is selected from Li, Na, K.
9. the preparation method of sulfuric ester as claimed in claim 8, which is characterized in that further include one in following technical characteristic
Or it is multiple:
C1) alkali species are selected from alkali metal hydroxide, alkali metal alcoholates, alkali metal simple substance, alkali metal hydride, alkali
One of metal oxide, alkali carbonate or a variety of combinations；
C2) molar ratio of formula III compound and alkali metal element in alkali species is 0.5~3:1；
C3) reaction temperature that formula III compound is reacted with alkali species is 70-150 DEG C；
C4) formula III compound is carried out with the condition existing for reaction dissolvent of reacting of alkali species.
10. the preparation method of sulfuric ester as claimed in claim 9, which is characterized in that further include one in following technical characteristic
It is a or multiple:
D1) alkali metal hydroxide is in lithium hydroxide, lithium hydroxide monohydrate, sodium hydroxide, potassium hydroxide
One or more combinations；
D2) alkali metal alcoholates be selected from lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, isopropyl lithium alkoxide,
One of sodium isopropylate, potassium isopropoxide, potassium tert-butoxide, sodium tert-butoxide or a variety of combinations；
D3) alkali metal simple substance is selected from one of SODIUM METAL, elemental lithium, simple substance potassium or a variety of combinations；
D4) alkali metal oxide is selected from one of sodium oxide molybdena, potassium oxide or a variety of combinations；
D5) alkali metal hydride is selected from one of sodium hydrogen, lithium hydrogen or a variety of combinations；
D6) alkali carbonate is selected from one of sodium carbonate, lithium carbonate, potassium carbonate, sodium bicarbonate, saleratus or more
The combination of kind；
D7) reaction dissolvent that formula III compound is reacted with alkali species is selected from aromatic hydrocarbon solvent；
D8) when alkali species are selected from alkali metal hydroxide, alkali metal alcoholates, alkali metal oxide, alkali carbonate,
Formula III compound is reacted with alkali species, the low boiling point component generated in removal system is heated in reaction process；
D9) when alkali species are alkali metal hydride, alkali metal simple substance, formula III compound is added by amount containing alkali gold
Belong to and being reacted in the reaction dissolvent of substance.
11. the preparation method of sulfuric ester as claimed in claim 9, which is characterized in that in formula III compound and alkali species
The molar ratio of alkali metal element is 0.6~1.5:1.
12. the preparation method of sulfuric ester as claimed in claim 10, which is characterized in that formula III compound and alkali species
The reaction dissolvent of reaction is selected from one of toluene, dimethylbenzene, benzene or a variety of combinations.
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| CN110818674A (en) * | 2019-11-25 | 2020-02-21 | 九江天赐高新材料有限公司 | Preparation method of vinyl sulfate |
| CN111995615B (en) * | 2020-09-27 | 2021-07-27 | 中节能万润股份有限公司 | Preparation method of cyclic sulfate |
| CN112225719B (en) * | 2020-09-30 | 2022-08-05 | 湖南阿斯达新材料有限公司 | Synthetic method of cyclic sulfate |
| CN112415106A (en) * | 2020-10-27 | 2021-02-26 | 山东海科创新研究院有限公司 | Gas chromatography monitoring method in vinyl sulfate preparation process |
| CN113563302A (en) * | 2021-07-13 | 2021-10-29 | 河北津宏化工有限公司 | Preparation process of vinyl sulfate |
| CN113444066A (en) * | 2021-07-21 | 2021-09-28 | 佳尔科生物科技南通有限公司 | Preparation method of vinyl sulfate |
| KR102638717B1 (en) * | 2021-08-19 | 2024-02-20 | 한인정밀화학(주) | Method for preparing cyclic sulfate-based compound and cyclic sulfate-based compound by the same |
| CN113683592A (en) * | 2021-08-27 | 2021-11-23 | 江苏瀚康新材料有限公司 | Preparation method of ethyl methyl carbonate solution containing ethylene sulfate |
| CN114805290A (en) * | 2022-05-12 | 2022-07-29 | 常德市大度新材料有限公司 | Preparation method of vinyl sulfate |
| CN114805292B (en) * | 2022-05-19 | 2023-06-30 | 浙江大学衢州研究院 | Synthesis method of vinyl sulfate |
| CN115852168A (en) * | 2022-12-22 | 2023-03-28 | 洛阳万基金属钠有限公司 | High-calcium sodium treatment process |
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