CN107629032B - A kind of preparation method of cyclic sulfates - Google Patents
A kind of preparation method of cyclic sulfates Download PDFInfo
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Abstract
The present invention relates to organic synthesis fields, more particularly to a kind of preparation method of cyclic sulfates.The present invention provides a kind of preparation method of cyclic sulfates, and the structural formula of the cyclic sulfates is shown in formula I, under the conditions of including the following steps: Formula II compound existing for the acid binding agent and catalyst, reacts with vikane and prepares compound of formula I.The preparation method reaction step of cyclic sulfates provided by the present invention is short, only can prepare cyclic sulfates with single step reaction, and supplementary material is cheap, and expensive raw material, oxidant is not used.
Description
Technical field
The present invention relates to organic synthesis fields, more particularly to a kind of preparation method of cyclic sulfates.
Background technique
The glycol compound as shown in Formula II obtains cyclic sulfates shown in formula I, this cyclic sulfates through esterification
It is a kind of additive that lithium-ion battery electrolytes using effect can be made more excellent.For example, sulfuric acid vinyl ester (No. CAS:
It can inhibit the decline of battery initial capacity after 1072-53-3) being added into lithium-ion battery electrolytes, increase initial discharge and hold
Amount reduces the expansion of battery after high temperature is placed, improves the charge-discharge performance and cycle-index of battery.Sulfuric acid acrylic ester (No. CAS:
It 1073-05-8) is used for lithium battery electrolytes additive, the cryogenic property of electrolyte can be improved, while carbonic acid third can be prevented
Enester molecule is embedded in graphite electrode.4- methylsulfuric acid vinyl acetate (No. CAS: 5689-83-8) can be used for improving under high-temperature condition
Lithium battery performance.
The cyclic sulfates of open report are largely to be with glycol compound shown in formula II and thionyl chloride at present
Raw material is esterified and is aoxidized what two-step reaction obtained.
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 waste water should be generated, oxidation reaction tune pH value etc. is complicated for operation, post-processes cumbersome.
CN105481826A, Molecules, vol10, nb9, (2005), p1169-1178 are reported with thionyl chloride and second
Glycol is that raw material progress substitution reaction prepares ethylene sulfite, prepares sulfuric acid second using ruthenium trichloride and sodium hypochlorite as oxidant
Enester.US4960904 report is using ruthenium-oxide (IV) dihydrate and sodium hypochlorite as oxidant.What these techniques used
The oxide or ruthenium salt of ruthenium are expensive, cause process costs height, are not suitable for Commercialization application, and sodium hypochlorite preparation itself
Need to generate a large amount of high salt waste water.
Journal of the Chemical Society,Chemical Communications,nb23,(1983),
P1392-1394 is reported in chloroform-aqueous systems, using ruthenic oxide and sodium metaperiodate as oxidant (four oxygen actually generated
Change ruthenium as oxidant) prepare sulfuric acid vinyl ester, yield 72%.This method oxidant is expensive, and production cost is higher.
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 prepares 4- propyl sulfuric acid vinyl ester.
CN106905291A is reported using thionyl chloride and antierythrite as raw material and is carried out addition reaction, then hypochlorous acid is added dropwise
The mixed solution of sodium and catalyst carries out oxidation reaction and prepares 3,3- union II sulfuric acid vinyl ester.
The obvious disadvantage of these methods is:
1, reaction step is long, and manufacturing cost is high, while increasing the complexity of technique and the difficulty of post-processing；
2, the chloride ion content of product is higher, removes the manufacturing cost that chloride ion technical process needs to increase project；
3, product crude product quality is lower, it is more difficult to purify；
4, oxidation reaction uses catalyst of these valuableness of Ruthenium oxide or ruthenium salt, increases supplementary material cost；
5, it requires to contact with water in manufacturing process, and intermediate ethylene sulfite and product sulfuric acid vinyl ester are water-soluble
It is unstable in liquid, easily lead to the reduction of product yield and purity；The technique reported at present requires stringent control system pH value,
Increase the difficulty of industrialized production, is unfavorable for obtaining the product of high-quality high yield；
6, waste water output is more, need to increase cost for wastewater treatment to mitigate environmental protection pressure.
Organic Letters, vol17, nb23, (2015), p5898-5901 are reported with sodium metaperiodate and ruthenic chloride
(III) trihydrate is that oxidant prepares sulfuric acid vinyl ester, and oxidant is expensive, yield 60% is lower.
Tetrahedron Letters, vol27, nb 34, (1986), p3971-3974 report utilize reagent Ethylene is directly translated into their cyclic sulfates.Due to the preparation source of reagent
Itself is difficult, is not suitable for industrialized production.
Australian Journal of Chemistry, 1977, vol.30, p569-578 is reported with 1,2- dibromo
Ethane is that raw material and the silver sulfate back flow reaction in dimethylbenzene prepare sulfuric acid vinyl ester, and the reaction yield is lower, and Bromofume,
Silver sulfate is expensive.
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 sides of cyclic sulfates
Method, 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 cyclic sulfates, described
The structural formula of cyclic sulfates is shown in formula I, includes the following steps: Formula II compound item existing for acid binding agent and catalyst
It under part, is reacted with vikane and prepares compound of formula I, reaction equation is as follows:
Wherein, n is selected from 0,1,2,3 or 4；
R1, R2, R3, R4, R5, R6 be each independently selected from H, C1~C8 alkyl, aryl, C1~C8 alkoxy, halogen or
Sulfuric ester.
In some embodiments of the application, n is selected from 0 or 1.
In some embodiments of the application, R1, R2, R3, R4, R5, R6 are independently selected from H, C1~C4 alkyl, C6
~C18 aryl, C1~C4 alkoxy, chlorine, bromine or cyclic sulfates base.
In some embodiments of the application, the cyclic sulfates base is selected from group as follows:
In some embodiments of the application, R1 is selected from H, methyl or propyl.
In some embodiments of the application, R2~R6 is H.
In some embodiments of the application, the molar ratio of vikane and Formula II compound is 0.7~15:1.
In some embodiments of the application, the molar ratio of vikane and Formula II compound is 0.9~3:1.
In some embodiments of the application, the acid binding agent be selected from organic amine, alkali metal alcoholates, alkali carbonate,
Alkali metal phosphate, alkali metal hydroxide, alkaline earth metal carbonate, alkaline earth metal hydroxide, ammonia, calcium oxide, fluorination
One of potassium or a variety of combinations.
In some embodiments of the application, the acid binding agent is selected from trimethylamine, triethylamine, diisopropyl ethyl amine, pyrrole
Pyridine, 2,6- lutidines, sodium methoxide, sodium ethoxide, potassium tert-butoxide, lithium carbonate, sodium carbonate, potassium carbonate, potassium phosphate, sodium phosphate,
Potassium phosphate,monobasic, disodium-hydrogen, lithium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium carbonate, one in calcium hydroxide
Kind or a variety of combinations.
In some embodiments of the application, the molar ratio of acid binding agent and Formula II compound is 0.5~15:1.
In some embodiments of the application, the molar ratio of acid binding agent and Formula II compound is 1.5~4.5:1.
In some embodiments of the application, the catalyst is selected from tetrabutylammonium chloride, tetrabutylammonium iodide, the tetrabutyl
Ammonium hydroxide, 4-butyl ammonium hydrogen sulfate, tetramethyl ammonium chloride, tetrabutylammonium bromide, tetraethylammonium bromide, 4-phenyl phosphonium bromide,
4-dimethylaminopyridine (DMAP), polyethylene glycol, benzyltriethylammoinium chloride, tetra-n-butyl ammonium fluoride, tricaprylmethyl chlorination
One of ammonium, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide are more
The combination of kind.
In some embodiments of the application, the molar ratio of catalyst and Formula II compound is 0.001~0.2:1.
In some embodiments of the application, the molar ratio of catalyst and Formula II compound is 0.005~0.05:1.
It in some embodiments of the application, is carried out under the conditions of reaction is existing for the water absorbing agent, the water absorbing agent is selected from chlorine
Change calcium, calcium oxide, calcium sulfate, various types molecular sieve, sodium sulphate, magnesium sulfate, aluminium oxide, silica, one in magnesia
Kind or a variety of combinations.
In some embodiments of the application, the molar ratio of water absorbing agent and Formula II compound is 0.1~10:1.
In some embodiments of the application, the molar ratio of water absorbing agent and Formula II compound is 0.2~5:1.
It in some embodiments of the application, is carried out under the conditions of reaction is existing for the reaction dissolvent, the reaction dissolvent choosing
From one of aromatic hydrocarbon solvent, esters solvent, halogenated alkanes solvents, ether solvent, nitrile solvents or a variety of combinations.
In some embodiments of the application, the reaction dissolvent is selected from toluene, dimethylbenzene, ethyl acetate, acetic acid positive third
Ester, dimethyl carbonate, diethyl carbonate, methylene chloride, 1,2- dichloroethanes, tetrahydrofuran, t-butyl methyl ether, dioxy six
One of ring, acetonitrile or a variety of combinations.
In some embodiments of the application, reaction temperature is -20 DEG C~70 DEG C.
In some embodiments of the application, reaction temperature is -10 DEG C~20 DEG C.
In some embodiments of the application, the post-processing of the preparation method of the cyclic sulfates includes the following steps:
After the reaction was completed, product is separated by solid-liquid separation, liquid phase sloughs appropriate solvent, recrystallizes up to the cyclic sulfates.
In some embodiments of the application, during recrystallization, metal ion chela is added in recrystallization solvent
Mixture.
Specific embodiment
Inventor using glycol compound as raw material, under the conditions of existing for the acid binding agent and catalyst with vikane
It carrying out esterification and prepares cyclic sulfates, the preparation method overcomes many defects existing in the prior art,
The present invention is completed on the basis of this.
One aspect of the present invention provides a kind of preparation method of cyclic sulfates, the structural formula of the cyclic sulfates such as formula
Shown in I, under the conditions of including the following steps: Formula II compound existing for the acid binding agent and catalyst, preparation is reacted with vikane
Compound of formula I is obtained, reaction equation is as follows:
In the preparation method of the cyclic sulfates, the n in Formulas I and/or Formula II can be selected from 0,1,2,3 or 4, so as to
To be constituted the cyclic structure of corresponding amount of carbon atom in being formed by compound of formula I, n can preferably be selected from 0 or 1.
In the preparation method of the cyclic sulfates, R1, R2, R3, R4, R5, R6 can be each independently selected from H, C1~
C8 alkyl, aryl, C1~C8 alkoxy, halogen (for example, fluorine, chlorine, bromine, iodine) or sulfate group, can also select each independently
From H, C1~C4 alkyl, C6~C18 aryl, C1~C4 alkoxy, chlorine, bromine or cyclic sulfates base.
In the application, the cyclic sulfates base be can be for exampleEqual groups.
In the application, C1~C8 alkyl can be branch or unbranched, specifically can be including but not limited to
Methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl etc..C1~C4 alkyl can be branch or unbranched
, it specifically can be including but not limited to methyl, ethyl, propyl, butyl etc..
In the application, the aryl be often referred to at least one aromatic rings ring system and without hetero atom (for example,
S, N, P or O etc.) group, C6~C18 aryl can be including but not limited to phenyl, naphthalene, fluorenyl, anthryl etc..
In the application, the moieties of C1~C8 alkoxy can be branch or unbranched, specifically can be
Including but not limited to methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygroup in heptan, octyloxy etc..The C1
The moieties of~C4 alkoxy can be branch or unbranched, specifically can be including but not limited to methoxyl group, ethoxy
Base, propoxyl group, butoxy etc..
In one specific embodiment of the application, the R1 is selected from H, methyl or propyl, and R2~R6 is H.
In the preparation method of the cyclic sulfates, vikane can be with relative to the dosage of Formula II compound according to the molar ratio
It is vikane excess, is also possible to Formula II compound excess, for example, the molar ratio of vikane and Formula II compound can be 0.7
~15:1, it is preferred that vikane can be basic equivalent or excessive relative to the dosage of Formula II compound, for example, sulfonyl
The molar ratio of fluorine and Formula II compound can be 0.9~3:1.Vikane, can be straight in gaseous form when reaction system is added
It connects into reaction system, first vikane can also be dissolved in suitable solvent (usually reaction dissolvent), then entrance is added dropwise
In reaction system.
In the preparation method of the cyclic sulfates, the acid binding agent can be including but not limited to organic amine, alkali metal
Alkoxide, alkali carbonate, alkali metal hydroxide, alkaline earth metal carbonate, alkali metal phosphate, alkaline-earth metal hydroxide
One of object, ammonia, calcium oxide, potassium fluoride etc. or a variety of combinations.The organic amine can be such as trimethylamine, three second
Amine, diisopropyl ethyl amine, pyridine, 2,6- lutidines etc., the alkali metal alcoholates can be such as sodium methoxide, ethyl alcohol
Sodium, potassium tert-butoxide etc., the alkali carbonate are selected from lithium carbonate, sodium carbonate, potassium carbonate etc., and the alkali metal phosphate can be with
It is such as potassium phosphate, sodium phosphate, potassium phosphate,monobasic, disodium-hydrogen, lithium phosphate, the alkali metal hydroxide can be example
Such as lithium hydroxide, sodium hydroxide, potassium hydroxide, the alkaline earth metal carbonate can be such as calcium carbonate, the alkaline earth
Metal hydroxides can be such as calcium hydroxide.In one specific embodiment of the application, the acid binding agent be selected from sodium carbonate,
Calcium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide etc. are preferably embodied in the application one
In example, it is hydroxide, specially lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide etc. that the acid binding agent, which is selected from,.It presses
Acid binding agent described in molar ratio computing can be acid binding agent excess relative to the dosage of Formula II compound, be also possible to Formula II compound mistake
Amount, for example, the molar ratio of acid binding agent and Formula II compound is 0.5~15:1, it is preferred that acid binding agent is relative to Formula II compound
Dosage is excessive, for example, the molar ratio of acid binding agent and Formula II compound is 1.5~4.5.
In the preparation method of the cyclic sulfates, the catalyst can be including but not limited to tetrabutylammonium chloride,
Tetrabutylammonium iodide, tetrabutylammonium hydroxide, 4-butyl ammonium hydrogen sulfate, tetramethyl ammonium chloride, tetrabutylammonium bromide, tetrem bromide
Change ammonium, 4-phenyl phosphonium bromide, 4-dimethylaminopyridine (DMAP), polyethylene glycol, benzyltriethylammoinium chloride, tetra-n-butyl fluorination
Ammonium, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, cetyl trimethyl
One of ammonium bromide etc. or a variety of combinations.In one specific embodiment of the application, the catalyst is selected from tetrabutyl sulfuric acid
Hydrogen ammonium, tetrabutylammonium bromide, tetraethylammonium bromide, 4-phenyl phosphonium bromide, tetra-n-butyl ammonium fluoride, 4-dimethylaminopyridine
(DMAP) etc., in the preferred specific embodiment of the application one, the catalyst be selected from 4-butyl ammonium hydrogen sulfate, polyethylene glycol,
Tetra-n-butyl ammonium fluoride, 4-dimethylaminopyridine (DMAP).The usage amount of the catalyst is usually catalytic amount according to the molar ratio
, for example, the molar ratio of catalyst and Formula II compound can be 0.001~0.2:1, or 0.005~0.05:1.
In the preparation method of the cyclic sulfates, reaction carries out under the conditions of can be existing for the water absorbing agent, this field skill
The type and dosage of suitable water absorbing agent may be selected in art personnel, to reduce the water content or removal reaction system in reaction system
In water.For example, the water absorbing agent can be calcium chloride, calcium oxide, calcium sulfate, various types molecular sieve, sodium sulphate, sulfuric acid
Magnesium, aluminium oxide, silica, magnesia etc., in one specific embodiment of the application, the water absorbing agent is selected from calcium chloride, oxidation
One of calcium, calcium sulfate, sodium sulphate, magnesium sulfate, magnesia etc. or a variety of combinations.For another example the water absorbing agent and Formula II
The molar ratio of compound can be 0.1~10:1, or 0.2~5:1.
In the preparation method of the cyclic sulfates, reaction can carry out under the conditions of solvent-free existing, can also be
It being carried out under the conditions of reaction dissolvent is existing, the type and dosage of suitable reaction dissolvent may be selected in those skilled in the art, thus
It can make the fully dispersed mixing of each component in reaction system, be dissolved in the cyclic sulfates prepared instead
It answers in solvent.The reaction dissolvent can be for example aromatic hydrocarbon solvent, esters solvent, halogenated alkanes solvents, ether solvent,
Nitrile solvents etc., the aromatic hydrocarbon solvent can be such as toluene, dimethylbenzene, and the esters solvent can be such as acetic acid
Ethyl ester, n-propyl acetate, dimethyl carbonate, diethyl carbonate etc., the halogenated alkanes solvents can be such as methylene chloride,
1,2- dichloroethanes etc., the ether solvent can be such as tetrahydrofuran, t-butyl methyl ether, dioxane, the nitrile
Class solvent can be such as acetonitrile.In one specific embodiment of the application, reaction dissolvent be selected from ethyl acetate, methylene chloride,
One of 1,2- dichloroethanes, t-butyl methyl ether, dimethyl carbonate, diethyl carbonate etc. or a variety of combinations.It is described anti-
The dosage of solvent is answered to can be the reaction dissolvent that every 1 mole of compound of formula I uses 0.1L or more, it is preferable to use 0.1~20L is anti-
Answer solvent.
In the preparation method of the cyclic sulfates, the reaction temperature of reaction can be -20 DEG C~70 DEG C, or -
10 DEG C~20 DEG C.Those skilled in the art can according to reaction process adjust the reaction time, for example, can by gas chromatography,
The analysis methods such as nuclear magnetic resonance method carry out following response progress, usually, are disappeared substantially using raw material substrate as the terminal of reaction,
The specific reaction time can be 2 hours hereinafter, being also possible to 2~10 hours.
In the preparation method of the cyclic sulfates, reaction can be carried out in normal pressure system, can also be under enclosed system
It carries out.For this reaction, under enclosed system reaction may advantageously facilitate reaction balance, improve feed stock conversion, thus obtain compared with
In high yield.
In the preparation method of the cyclic sulfates, the post-processing of the preparation method of the cyclic sulfates includes following step
It is rapid: after the reaction was completed, product to be separated by solid-liquid separation, liquid phase sloughs appropriate solvent, recrystallizes up to the cyclic sulfates.This field
The recrystallization solvent that suitable species may be selected in technical staff is used for the purifying of product, and the recrystallization solvent can be such as alkane
Class solvent, aromatic hydrocarbon solvent, esters solvent, halogenated alkanes solvents, ether solvent, alcohols solvent etc., the alkanes are molten
Agent can be such as n-hexane, normal heptane, hexamethylene, and the aromatic hydrocarbon solvent can be such as toluene, dimethylbenzene etc.,
The esters solvent can be such as ethyl acetate, n-propyl acetate, dimethyl carbonate, and the halogenated alkanes solvents can be with
It is such as methylene chloride, 1,2- dichloroethanes etc., the ether solvent can be such as tetrahydrofuran, t-butyl methyl ether, two
Six ring of oxygen etc., the alcohols solvent can be such as ethyl alcohol, methanol.In one specific embodiment of the application, the recrystallization
Solvent is selected from one of n-hexane, normal heptane, methylene chloride, 1,2- dichloroethanes, t-butyl methyl ether, dimethyl carbonate etc.
Or a variety of combination.In last handling process, metal ion chela can also be added in recrystallization solvent during recrystallization
Mixture, so as to avoid the metal ion that may be introduced in reaction product, the metal ion can be such as Na ion, K
Ion etc., the metal ion chelation agent can be crown ether, and the crown ether can be such as 12-crown-4,15- crown- 5,18- crown- 6
One of or combination.
The preparation method reaction step of cyclic sulfates provided by the present invention is short, only can prepare ring with single step reaction
Shape sulfuric ester, and supplementary material is cheap, and expensive raw material, oxidant is not used.In addition, having benefited from technique itself
Superiority is relatively easily purified by products of the present invention, so the chloride ion content of product is extremely low, obtained quality of finished compared with
Height, and almost non-wastewater discharge are conducive to environmental protection.In conclusion the preparation method technique of cyclic sulfates provided herein
Easy to operate, supplementary material cost and manufacturing cost are low, are suitble to industrialization large-scale production.
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 (formula III compound):
In 1000mL reaction flask, ethylene glycol 40g, methylene chloride 400mL, solid potassium hydroxide 108g, tetra-n-butyl is added
Ammonium fluoride 1.7g keeps interior 0~5 DEG C of temperature, sulfuryl fluoride gas 98g is slowly introducing under stirring, reacts 1 hour, it is small to advertise nitrogen 1
When, filtering, filtrate decompression precipitation obtains solid crude product and n-hexane 300mL, 5 0.05g of 15- crown-, 6 0.05g of 18- crown- is added,
Temperature rising reflux dissolution, then is slowly dropped to room temperature, filtering, dry product 54.1g, yield 67.6%.Testing result: GC (%):
> 99.0%；AAS (ppm): Na 0.2, K 3, Fe 0.3, Ca 0.5；IC (ppm): SO4 2-49, F-0.3, Cl-0.1。
Embodiment 2
The preparation of sulfuric acid vinyl ester:
In 1000mL autoclave, ethylene glycol 40g, methyl tertiary butyl ether(MTBE) 250mL, solid sodium hydroxide 59g, sodium sulphate is added
20g, 4-n-butyl ammonium hydrogen sulfate 4.3g keep interior 5~10 DEG C of temperature, sulfuryl fluoride gas 72g, confined reaction are slowly introducing under stirring
1 hour.Reaction terminates to advertise nitrogen 1 hour, filters, filtrate decompression precipitation, obtains solid crude product and methylene chloride 100mL is added,
5 0.05g of 15- crown-, 6 0.05g of 18- crown-, temperature rising reflux dissolution, then are slowly dropped to room temperature, filtering, dry product 65.5g,
Yield 81.8%.Testing result: GC (%): > 99.9%；AAS (ppm): Na 4, K 0.5, Fe 0.4, Ca 0.4；IC
(ppm): SO4 2-55, F-0.5, Cl-0.2。
Embodiment 3
The preparation of 4- methylsulfuric acid vinyl acetate (formula IV compound):
In 1000mL reaction flask, 1,2-PD 50g, acetonitrile 300mL, potassium carbonate 108g, tetrabutylammonium bromide is added
2.1g keeps interior 10~15 DEG C of temperature, sulfuryl fluoride gas 80g is slowly introducing under stirring, reacts 1.5 hours, advertise nitrogen 1 hour,
Filtering, filtrate decompression precipitation obtain solid crude product and methylene chloride 100mL, 5 0.05g of 15- crown-, 6 0.05g of 18- crown- are added,
Temperature rising reflux dissolution, then is slowly dropped to room temperature, filtering, dry product 49.9g, yield 55.0%.Testing result: GC (%):
> 99.9%；AAS (ppm): Na 0.3, K2, Fe 0.5, Ca 0.2；IC (ppm): SO42-89, F-0.5, Cl-0.2.
Embodiment 4
The preparation of 4- propyl sulfuric acid vinyl ester (Formula V compound):
In 1000mL reaction flask, 1,2- pentanediol 67g is added, toluene 600mL, triethylamine 149g, calcium oxide 40g, four just
Butyl ammonium hydrogen sulfate 4.3g keeps interior 0~5 DEG C of temperature, sulfuryl fluoride gas 72g is slowly introducing under stirring, reacts 2 hours, advertise nitrogen
Gas 1 hour, filtering, filtrate decompression precipitation obtained solid crude product and toluene 200mL, 5 0.05g of 15- crown-, 18- crown- is added
60.05g, temperature rising reflux dissolution, then is slowly dropped to room temperature, filtering, dry product 77g, yield 71.9%.Testing result: GC
(%): > 99.9%；AAS (ppm): Na 0.5, K 0.4, Fe 0.6, Ca 0.3；IC (ppm): SO4 2-48, F-0.7, Cl-0.5。
Embodiment 5
The preparation of sulfuric acid acrylic ester (Formula IV compound):
In 1000mL reaction flask, 1,3-PD 50g, acetonitrile 300mL, diisopropyl ethyl amine 212g, sodium sulphate is added
20g, cetyl trimethylammonium bromide 2.4 keep interior 5~10 DEG C of temperature, sulfuryl fluoride gas 80g are slowly introducing under stirring, react
It 1.5 hours, advertises nitrogen 1 hour, filters, filtrate decompression precipitation, obtain solid crude product and toluene 200mL, 15- crown- is added
6 0.05g of 50.05g, 18- crown-, temperature rising reflux dissolution, then is slowly dropped to room temperature, filtering, dry product 61.7g, yield
68.0%.GC (%): > 99.9%；AAS (ppm): Na 0.6, K 0.5, Fe 0.7, Ca 0.2；IC (ppm): SO4 2-68, F-
0.6, Cl-0.3。
Comparative example
The preparation of sulfuric acid vinyl ester:
In 1000mL autoclave, addition ethylene glycol 40g, methyl tertiary butyl ether(MTBE) 250mL, potassium carbonate 108g, holding interior warm 5~
10 DEG C, it is slowly introducing sulfuryl fluoride gas 72g under stirring, confined reaction 1 hour, advertises nitrogen 1 hour, filter, filtrate decompression is de-
It is molten, it obtains solid crude product and methylene chloride 100mL, 5 0.05g of 15- crown-, 6 0.05g of 18- crown- is added, temperature rising reflux dissolves, then
It is slowly dropped to room temperature, filtering, dry product 50.9g, yield 62.4%.Testing result: GC (%): 97.9%；AAS (ppm):
Na 7, K 2, Fe 0.3, Ca 1；IC (ppm): SO4 2-25, F-1, Cl-0.2。
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 (10)
1. a kind of preparation method of cyclic sulfates, the structural formula of the cyclic sulfates is shown in formula I, includes the following steps:
Under the conditions of by Formula II compound existing for the acid binding agent and catalyst, is reacted with vikane and prepare compound of formula I, reaction side
Formula is as follows:
Wherein, n is selected from 0,1,2,3 or 4；
R1, R2, R3, R4, R5, R6 are each independently selected from H, C1~C8 alkyl, C1~C8 alkoxy, halogen；
The molar ratio of vikane and Formula II compound is 0.7~15:1；
The catalyst is selected from tetrabutylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium hydroxide, 4-butyl ammonium hydrogen sulfate, four
Methyl chloride amine, tetrabutylammonium bromide, tetraethylammonium bromide, 4-phenyl phosphonium bromide, 4-dimethylaminopyridine, polyethylene glycol, benzyl
Triethylammonium chloride, tetra-n-butyl ammonium fluoride, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride, myristyl
One of trimethyl ammonium chloride, cetyl trimethylammonium bromide or a variety of combinations；
The acid binding agent is selected from trimethylamine, triethylamine, diisopropyl ethyl amine, pyridine, 2,6- lutidines, sodium methoxide, second
Sodium alkoxide, potassium tert-butoxide, lithium carbonate, sodium carbonate, potassium carbonate, potassium phosphate, sodium phosphate, potassium phosphate,monobasic, disodium-hydrogen, phosphoric acid
One of lithium, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium carbonate, calcium hydroxide or a variety of combinations；
Reaction temperature is -20 DEG C~20 DEG C.
2. the preparation method of cyclic sulfates as described in claim 1, which is characterized in that n is selected from 0 or 1.
3. the preparation method of cyclic sulfates as described in claim 1, which is characterized in that R1, R2, R3, R4, R5, R6 are respectively
It is independent to be selected from H, C1~C4 alkyl, C1~C4 alkoxy, chlorine, bromine.
4. the preparation method of cyclic sulfates as described in claim 1, which is characterized in that R1 is selected from H, methyl or propyl.
5. the preparation method of cyclic sulfates as claimed in claim 4, which is characterized in that R2~R6 is H.
6. the preparation method of cyclic sulfates as described in claim 1, which is characterized in that further include in following technical characteristic
It is one or more:
A1) molar ratio of acid binding agent and Formula II compound is 0.5~15:1；
A2) molar ratio of catalyst and Formula II compound is 0.001~0.2:1；
A3) reaction existing for the water absorbing agent under the conditions of carry out, the water absorbing agent is selected from calcium chloride, calcium oxide, calcium sulfate, molecule
One of sieve, sodium sulphate, magnesium sulfate, aluminium oxide, silica, magnesia or a variety of combinations；
A4) reaction existing for the reaction dissolvent under the conditions of carry out, the reaction dissolvent is selected from aromatic hydrocarbon solvent, ester solvent, halogenated
One of alkane solvent, ether solvents, nitrile solvent or a variety of combinations.
7. the preparation method of cyclic sulfates as claimed in claim 6, which is characterized in that further include in following technical characteristic
It is one or more:
B1) molar ratio of vikane and Formula II compound is 0.9~3:1；
B2) molar ratio of acid binding agent and Formula II compound is 1.5~4.5:1；
B3) molar ratio of catalyst and Formula II compound is 0.005~0.05:1；
B4) molar ratio of water absorbing agent and Formula II compound is 0.1~10:1；
B5) reaction dissolvent be selected from toluene, dimethylbenzene, ethyl acetate, n-propyl acetate, dimethyl carbonate, diethyl carbonate,
One of methylene chloride, 1,2- dichloroethanes, tetrahydrofuran, t-butyl methyl ether, dioxane, acetonitrile or a variety of groups
It closes；
B6) reaction temperature is -10 DEG C~20 DEG C.
8. the preparation method of cyclic sulfates as claimed in claim 7, which is characterized in that water absorbing agent rubs with Formula II compound
You are than being 0.2~5:1.
9. the preparation method of cyclic sulfates as described in claim 1, which is characterized in that the preparation side of the cyclic sulfates
The post-processing of method includes the following steps: that after the reaction was completed, product is separated by solid-liquid separation, and liquid phase sloughs appropriate solvent, recrystallizes to obtain the final product
The cyclic sulfates.
10. the preparation method of cyclic sulfates as described in claim 1, which is characterized in that during recrystallization, in weight
Metal ion chelation agent is added in recrystallisation solvent.
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| CN108822075A (en) * | 2018-07-13 | 2018-11-16 | 山东贵邦药业有限公司 | A kind of sulfuric acid vinyl ester synthesis technology |
| CN109776487B (en) * | 2019-02-26 | 2021-09-24 | 武汉松石科技股份有限公司 | Preparation method of vinyl sulfate |
| CN110590735B (en) * | 2019-09-30 | 2021-07-23 | 江苏国泰超威新材料有限公司 | Preparation method of cyclic sulfate |
| 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 |
| CN111170985B (en) * | 2019-12-27 | 2021-06-01 | 烟台海川化学制品有限公司 | Preparation method of allyl sulfate |
| CN112159388B (en) * | 2020-09-30 | 2022-10-11 | 湖南阿斯达新材料有限公司 | Preparation method of vinyl sulfate derivative |
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