CN110386916A - A kind of synthetic method of cyclic sulfates - Google Patents
A kind of synthetic method of cyclic sulfates Download PDFInfo
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- CN110386916A CN110386916A CN201910666737.XA CN201910666737A CN110386916A CN 110386916 A CN110386916 A CN 110386916A CN 201910666737 A CN201910666737 A CN 201910666737A CN 110386916 A CN110386916 A CN 110386916A
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- 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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- C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
- C07D497/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
The invention discloses a kind of synthetic methods of cyclic sulfates, with sulfuric acid and the pre-synthesis sulfuric acid solution of hydrogen peroxide, under the conditions of again existing for organic solvent, metal inorganic compound and the catalyst, sulfuric acid solution is added dropwise and cyclic sulfite carries out catalytic oxidation, after reaction, by filtering out salt slag, stratification, organic layer distillation and concentration, purification are taken, cyclic sulfates fine work is obtained.A kind of synthetic method of cyclic sulfates of the present invention, makees raw material using cheap sulfuric acid and hydrogen peroxide, prepares sulfuric acid solution catalysis oxidation cyclic sulfite, and it is high on the one hand to react mild, easily controllable, reaction conversion ratio；The evaporation capacity of another aspect water is small, and low energy consumption, and the waste water of generation is few, and synthesis technology is more environmentally protective；Ring-type sulfate impurities produced by the present invention are few, with high purity, wide market.
Description
Technical field
The present invention relates to new energy materials synthesis technical field, more particularly to a kind of synthetic method of cyclic sulfates,
It can be used as the additive of lithium-ion battery electrolytes by cyclic sulfates prepared by this method, it can also be used to the centre of pharmaceutical synthesis
Body.
Background technique
As people are to the enhancing of environmental protection consciousness and the progress of science and technology, new green energy technology is increasingly subject to people
Attention, especially lithium ion secondary battery, since it has, such as operating voltage is high, small in size, light weight, energy density
High, the advantages that environmental pollution is small, self discharge is small, service life cycle is long and memory-less effect, receive the pass of battery industry
It infuses and is widely used.A kind of additive of the cyclic sulfates as lithium-ion battery electrolytes, can effectively keep away
Exempt from the decline of lithium ion battery initial capacity, increases initial discharge capacity, improve the charge-discharge performance and cycle-index of battery, change
Kind high/low temperature cycle performance, is that a kind of electrolyte of high-power lithium ion battery especially suitable for ternary system positive electrode adds
Add agent.
There are mainly four types of the synthetic methods for the cyclic sulfates reported at present, be respectively acylated method, method of substitution, addition process and
Oxidizing process.
Acylated method is to prepare cyclic sulfates (Vanhessche with reacting for vicinal diamines by chlorosulfuric acid or vikane
K.P.M., Sharpless K.B., Chem.Eur.J.1997,3,517-522 and CN107629032A), although this method raw material
Cheaply, but reaction yield is low, and corrosivity is strong, causes serious pollution to the environment, and is poorly suited for industrialized production.
Method of substitution is to be typically Bromofume by dihaloethane, and substitution reaction occurs with silver sulfate, is generated cyclic annular
Sulfuric ester and silver bromide (Baker, Wilson and Field, Frederick B., Journal of the Chemical
Society, 86-91,1932), this method yield only has 23%, and using expensive silver salt, cost is too high.
Addition process has two process routes, first is that directly with sulfur trioxide addition reaction occurs for ethylene oxide, directly generates
Cyclic sulfates (Deruelle, Roger et al, Fr.Demande, 2664274,10, Jan., 1992)；Second is that ethylene and three
Sulfur oxide Iodosobenzene effect under occur oxidative addition generate cyclic sulfates (Zefirov N.S.et al,
Zhurnal Organicheskoi Khimii, 22 (2), 450-2,1986), but this two process routes all use high-risk ring
The sulfur trioxide of oxidative ethane or ethylene and high-risk highly corrosive.
There are three ways to oxidizing process is reported at present:
The first is to obtain corresponding cyclic sulfates (Wang P., Chun with hypochlorite oxidation cyclic sulfite
B；Rachakonda S.et al., J.Org.Chem.2009,74,6819-6824), although the strong pole of hypochlorite oxidation
Unstable, especially active o content is low, and wastewater flow rate is big, and the sodium chloride of by-product is difficult to recycle, and can only be used as solid waste
Processing increases environmental protection pressure, and strong to the corrosivity of equipment；On the other hand, the introducing of oxidizer containing chlorine has impurity to increase latent
In risk, product is also increased in the purification difficulty in later period and the use in downstream.
Second is to obtain corresponding cyclic sulfates (Paddon-Jones with sodium periodate oxidation cyclic sulfite
G.C., Mcerulean C.S.P., Hayes P.et al, J.Org.Chem., 2001,66,7487-7695；Shao H.,
Rueter J.k.,Goodman M.,J.Org.Chem.,1998,63,5240-5244；Zhang L.Luo S.,Mi
X.etal., Orangic&Biomolecular Chemistry, 2009,74,6819-6824), on the one hand this method is high iodine
Sour sodium price is extremely expensive, and cost is excessively high, can only cannot achieve industrialization in preparation of the laboratory as reagent；On the other hand
It is that iodo impurity is more in product, affects later period application.
The third be with potassium permanganate oxidation cyclic sulfite obtain corresponding cyclic sulfates (Berridge M.S,
Franceschini M.P., Rosenfeld E.et al, J.Org.Chem., 1990,55,1211-1217), this method is secondary anti-
Ying Duo, yield is low, product purification difficult.
4th kind be using ammonium persulfate-sodium bisulfate oxidation cyclic sulfates (CN103012386A,
CN104744427A), although the method reaction is mild, it is easy to control, oxidant cost is high, and the sulfate amount of by-product is larger.
Summary of the invention
The invention mainly solves the technical problem of providing a kind of synthetic methods of cyclic sulfates, are able to solve existing conjunction
At the above problem existing for method.
In order to solve the above technical problems, one technical scheme adopted by the invention is that: a kind of conjunction of cyclic sulfates is provided
At method, with sulfuric acid and the pre-synthesis sulfuric acid solution of hydrogen peroxide, then in organic solvent, metal inorganic compound and catalyst
Under the conditions of existing, sulfuric acid solution is added dropwise and cyclic sulfite carries out catalytic oxidation, after reaction, through filtering
Desalination slag, stratification take organic layer distillation and concentration, purification, obtain cyclic sulfates fine work.
In a preferred embodiment of the present invention, the molar ratio of hydrogen peroxide is H in the sulfuric acid and hydrogen peroxide2SO4:
H2O2=1~5:1；The process conditions of the synthesis are as follows: synthesis temperature -20~20 DEG C；0.1~10h of generated time.
In a preferred embodiment of the present invention, the mass concentration of the hydrogen peroxide is more than or equal to 10%；The sulfuric acid
The mass concentration of solution is more than or equal to 20%.
In a preferred embodiment of the present invention, the condition of the catalytic oxidation are as follows: reaction temperature -10~50 DEG C,
5~500min of reaction time.
In a preferred embodiment of the present invention, the additional amount of cyclic sulfite is that hydrogen peroxide rubs in the hydrogen peroxide
1/10~1 times of that amount；
The dosage of the metal inorganic compound for institute's metal ion and sulfuric acid in metal inorganic compound equivalent proportion
For 1:0.2~1.0；
The dosage of the catalyst is the 0.01~3% of cyclic sulfite quality；
The mass ratio of the cyclic sulfite and organic solvent is 1:1~30.
In a preferred embodiment of the present invention, the cyclic sulfates include five-membered ring single ring architecture, hexatomic ring monocycle
Structure, multiring structure and spirane structure compound:
Wherein, the structural formula of the five-membered ring single ring architecture compound are as follows:In formula, R1And R2For phase
Same or different H, F and C1~4Alkyl；
The structural formula of the hexatomic ring single ring architecture compound are as follows:In formula, R3、R4And R5For phase
With or not identical H, F, C1~4Alkyl；
The structural formula of the multiring structure compound are as follows:In formula, R6And R7It is identical
Or different H, F, C1~4Alkyl；
The structural formula of the spirane structure compound are as follows:
In a preferred embodiment of the present invention, the metal inorganic compound is potassium sulfate, lithium carbonate, sodium carbonate, carbon
Sour hydrogen sodium, potassium carbonate, saleratus, magnesium carbonate, calcium carbonate, strontium carbonate, zinc carbonate, sodium phosphate, disodium hydrogen phosphate, potassium phosphate,
Dipotassium hydrogen phosphate, lithium borate, Boratex, potassium borate, antifungin, lithium metasilicate, sodium metasilicate, potassium silicate, magnesium silicate, calcium silicates, silicon
Sour aluminium, sodium aluminate, potassium aluminate, magnesium aluminate, magnesia, calcium oxide, zinc oxide, iron oxide, ferrous oxide, aluminium oxide, tin oxide,
One of magnesium hydroxide, calcium hydroxide, aluminium hydroxide, zinc hydroxide or stannic hydroxide or multiple combinations.
In a preferred embodiment of the present invention, the organic solvent is ketone, nitrile, ethers, esters, amides, miaow
The combination of one or more of oxazoline ketone, halogenated hydrocarbon solvent or aromatic hydrocarbon solvent.
In a preferred embodiment of the present invention, the catalyst be water-soluble transition metal salt or its hydrate, it is described
Transition metal salt is platinous chloride, platinum tetrachloride, platinum nitrate, oxalic acid platinum, palladium chloride, palladium acetate, palladium nitrate, palladium sulfate, water
Close rhodium chloride, rhodium nitrate, rhodium sulfate, rhodium acetate, acetylacetone,2,4-pentanedione rhodium, hydrate ruthenium trichloride, nitric acid ruthenium, ruthenium sulfate, acetic acid ruthenium,
Acetylacetone,2,4-pentanedione ruthenium, rhenium trichloride, rhenium pentachloride, osmium dichloride, osmium trichloride, manganese chloride, manganese sulfate, manganese nitrate, manganese acetate, water
Close iridous chloride, acetic acid iridium or acetylacetone,2,4-pentanedione iridium.
In a preferred embodiment of the present invention, the organic solvent is ketone, nitrile, ethers, esters, amides, miaow
One of oxazoline ketone, halogenated hydrocarbon solvent or aromatic hydrocarbon solvent or above combination；Wherein, the organic solvent of ketone
For acetone, butanone, methyl iso-butyl ketone (MIBK) or cyclohexanone；The nitrile organic solvent is acetonitrile or propionitrile；The ethers is organic molten
Agent is tetrahydrofuran, 1,3- dioxolanes, 1,4- dioxane, glycol dimethyl ether, Propylene Glycol Dimethyl Ether, diethylene glycol diformazan
Ether, diethylene glycol diethyl ether or dimethyl ether；The based organic solvent is methyl acetate, ethyl acetate, acetic acid third
Ester, isopropyl acetate, butyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate, dimethyl carbonate, carbonic acid
Diethylester, methyl ethyl carbonate, methyl propyl carbonate or trifluoroethyl methyl carbonic；The amide-type organic solvent is dimethyl methyl
Amide, dimethyl acetamide, diethylformamide or hexamethylphosphoramide；The imidazolone type organic solvent is N, N- bis-
Methylimidazole quinoline ketone；The halogenated hydrocarbon organic solvent is methylene chloride, dichloroethanes or dichloropropane；The arene has
Solvent be benzene,toluene,xylene, fluorobenzene, chlorobenzene, o-difluoro-benzene, m-difluorobenzene, to difluorobenzene, o-dichlorohenzene, m-dichlorobenzene
Or paracide.
The beneficial effects of the present invention are: a kind of synthetic method of cyclic sulfates of the present invention, cheap sulfuric acid and double is used
Oxygen water makees raw material, prepares sulfuric acid solution catalysis oxidation cyclic sulfite, on the one hand reacts mild, easily controllable, reaction
High conversion rate；The evaporation capacity of another aspect water is small, and low energy consumption, and the waste water of generation is few, and synthesis technology is more environmentally protective；The present invention
Ring-type sulfate impurities obtained are few, with high purity, wide market.
Specific embodiment
The preferred embodiments of the present invention will be described in detail below so that advantages and features of the invention can be easier to by
It will be appreciated by those skilled in the art that so as to make a clearer definition of the protection scope of the present invention.
The embodiment of the present invention includes:
Present invention discloses a kind of synthetic methods of cyclic sulfates, molten with sulfuric acid and the pre-synthesis peroxosulphuric of hydrogen peroxide
Liquid, then under the conditions of existing for organic solvent, metal inorganic compound and the catalyst, sulfuric acid solution and cyclic annular sulfurous is added dropwise
Acid esters carries out catalytic oxidation, and after reaction, by filtering out salt slag, stratification takes organic layer distillation and concentration, purification,
Obtain cyclic sulfates fine work；Layer fetch water through evaporative concn, filtering, separation, obtains inorganic salts.Gained inorganic salts can be used as byproduct
Sale.
Specifically, for synthesizing sulfuric acid solution, the mass concentration of the hydrogen peroxide is more than or equal to 10%；The sulphur
The mass concentration of acid solution is more than or equal to 20%；The molar ratio of hydrogen peroxide is H in the sulfuric acid and hydrogen peroxide2SO4:
H2O2=1~5:1；The temperature of the synthesis is -20~20 DEG C；The time of synthesis is 0.1~10 hour.
For catalytic oxidation, the additional amount of the cyclic sulfite is hydrogen peroxide mole in the hydrogen peroxide
1/10~1 times；The dosage of the metal inorganic compound is worked as institute's metal ion in metal inorganic compound and sulfuric acid
Amount is than being 1:0.2~1.0；The dosage of the catalyst is the 0.01~3% of cyclic sulfite quality；The ring-type sulfurous acid
The mass ratio of ester and organic solvent is 1:1~30.
The condition of the catalytic oxidation are as follows: reaction temperature -10~50 DEG C, 5~500min of reaction time；
The cyclic sulfates include five-membered ring single ring architecture, hexatomic ring single ring architecture, multiring structure and spirane structure
Close object:
Wherein, the structural formula of the five-membered ring single ring architecture compound are as follows:In formula, R1And R2For phase
Same or different H, F and C1~4Alkyl；
The structural formula of the hexatomic ring single ring architecture compound are as follows:In formula, R3、R4And R5For phase
With or not identical H, F, C1~4Alkyl；
The structural formula of the multiring structure compound are as follows:In formula, R6And R7It is identical
Or different H, F, C1~4Alkyl；
The structural formula of the spirane structure compound are as follows:
The metal inorganic compound is potassium sulfate, lithium carbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus, carbon
Sour magnesium, calcium carbonate, strontium carbonate, zinc carbonate, sodium phosphate, disodium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, lithium borate, Boratex,
Potassium borate, antifungin, lithium metasilicate, sodium metasilicate, potassium silicate, magnesium silicate, calcium silicates, alumina silicate, sodium aluminate, potassium aluminate, magnesium aluminate,
Magnesia, calcium oxide, zinc oxide, iron oxide, ferrous oxide, aluminium oxide, tin oxide, magnesium hydroxide, calcium hydroxide, hydroxide
One of aluminium, zinc hydroxide or stannic hydroxide or multiple combinations.
The organic solvent is ketone, nitrile, ethers, esters, amides, imidazolone type, halogenated hydrocarbon solvent or virtue
The combination of one or more of fragrant hydrocarbon solvent.
The catalyst is water-soluble transition metal salt or its hydrate, and the transition metal salt is platinous chloride, tetrachloro
Change platinum, platinum nitrate, oxalic acid platinum, palladium chloride, palladium acetate, palladium nitrate, palladium sulfate, rhodium trichloride hydrate, rhodium nitrate, rhodium sulfate,
Rhodium acetate, acetylacetone,2,4-pentanedione rhodium, hydrate ruthenium trichloride, nitric acid ruthenium, ruthenium sulfate, acetic acid ruthenium, acetylacetone,2,4-pentanedione ruthenium, rhenium trichloride, pentachloro-
Change rhenium, osmium dichloride, osmium trichloride, manganese chloride, manganese sulfate, manganese nitrate, manganese acetate, hydrated iridium trichloride, acetic acid iridium or acetyl
Acetone iridium.
The organic solvent is ketone, nitrile, ethers, esters, amides, imidazolone type, halogenated hydrocarbon solvent or virtue
One of fragrant hydrocarbon solvent or above combination；Wherein, the organic solvent of ketone is acetone, butanone, methyl iso-butyl ketone (MIBK)
Or cyclohexanone；The nitrile organic solvent is acetonitrile or propionitrile；The ether organic solvent is tetrahydrofuran, 1,3- dioxy penta
Ring, 1,4- dioxane, glycol dimethyl ether, Propylene Glycol Dimethyl Ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or dipropyl
Glycol dimethyl ether；The based organic solvent be methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate,
Isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first
Propyl ester or trifluoroethyl methyl carbonic；The amide-type organic solvent is dimethylformamide, dimethyl acetamide, diethyl
Formamide or hexamethylphosphoramide；The imidazolone type organic solvent is N, N- dimethyl-imidazolinone；The halogenated hydrocarbons
Class organic solvent is methylene chloride, dichloroethanes or dichloropropane；The arene organic solvent be benzene,toluene,xylene,
Fluorobenzene, chlorobenzene, o-difluoro-benzene, m-difluorobenzene, to difluorobenzene, o-dichlorohenzene, m-dichlorobenzene or paracide.
Embodiment 1
The synthesis of peroxosulphuric
The hydrogenperoxide steam generator 340g that mass concentration is 30% is cooled at 0 DEG C with ice salt bath, quality is slowly added dropwise
Concentration is 98% concentrated sulfuric acid 900g, and control reaction mixture temperature maintains 0~3 DEG C, time for adding 3 hours or so, drips
After continue stirring 2 hours, obtain 1240g sulfuric acid solution, it is spare.
Embodiment 2
The synthesis of peroxosulphuric
The hydrogenperoxide steam generator 510g of mass concentration 20% is cooled at -5 DEG C with ice salt bath, oleum is slowly added dropwise
Sour 600g, control reaction mixture temperature maintain -3~0 DEG C, time for adding 4 hours or so, it is small to continue stirring 5 after dripping
When, 1100g sulfuric acid solution is obtained, it is spare.
Embodiment 3
The synthesis of peroxosulphuric
The hydrogenperoxide steam generator 146g that mass concentration is 70% is cooled at 5 DEG C with ice salt bath, quality is slowly added dropwise
Concentration is 85% concentrated sulfuric acid 690g, and control reaction mixture temperature maintains 5~7 DEG C, time for adding 5 hours or so, drips
After continue stirring 1 hour, obtain 836g sulfuric acid solution, it is spare.
Embodiment 4
The synthesis of sulfuric acid vinyl ester
Pure water 1200g, methylene chloride 600g, potassium carbonate 510g, potassium sulfate 190g, structural formula are sequentially added into reaction flask
ForEthylene sulfite 54g, rhenium trichloride 1.35g, stir simultaneously reaction system is cooled to 0 with ice salt bath
DEG C, then the ready-made sulfuric acid solution 460g of embodiment 1 is added dropwise in reaction system within half an hour, it is kept during being added dropwise
Temperature is at 2~4 DEG C.Continue to stir 30min after dripping, organic layer is separated after filtering, organic layer is first through molecular sieve dehydration, then revolves
Turn to be evaporated to dryness removing methylene chloride, obtaining structural formula isSulfuric acid vinyl ester crude product 46.3g, purity 97.6%.
Crude product obtains the sulfuric acid vinyl ester finished product 42.2g of purity 99.7%, yield 68.1% with recrystallize with dichloromethane 2 times.
Embodiment 5
The synthesis of 4- propyl ethylene sulfite
Pure water 900g, acetonitrile 200g, dichloroethanes 300g, lithium metasilicate 160g, structural formula are sequentially added into reaction flask is4- propyl ethylene sulfite 75g, acetic acid ruthenium 0.75g, stir and by reaction system cryosel
Water-bath cooling is added dropwise in reaction system in 1 hour to 8 DEG C, then by the ready-made sulfuric acid solution 330g of embodiment 2, is added dropwise
8~12 DEG C are maintained the temperature in the process.Continue stirring 1 hour after dripping, organic layer is separated after filtering, organic layer is first through anhydrous
Sodium sulfate, then rotary evaporated to dryness remove acetonitrile and dichloroethanes, and obtaining structural formula is's
4- propyl sulfuric acid vinyl ester crude product 63.1g, purity 98.3%.Crude product is through dichloroethanes dissolution, active carbon decoloring, after secondary filter
It depressurizes rotary evaporation and removes dichloroethanes, obtain the 4- propyl sulfuric acid vinyl ester finished product 60.3g of purity 99.2%, yield
72.6%.
Embodiment 6
The synthesis of dithionic acid vinyl acetate
Sequentially added into reaction flask pure water 1500g, glycol dimethyl ether 200g, dimethyl carbonate 500g, fluorobenzene 300g,
Disodium hydrogen phosphate 730g, structural formula areHydrosulfurous acid vinyl acetate 107g, rhodium sulfate
Reaction system is cooled to 10 DEG C with ice salt bath under stirring by 0.75g, then by the ready-made sulfuric acid solution 350g of embodiment 3
It is added dropwise in reaction system in 2 hours, 10~15 DEG C is maintained the temperature at during being added dropwise.It is small to continue stirring half after dripping
When, organic layer is separated after filtering, organic layer is first dry through anhydrous magnesium sulfate, then rotary evaporated to dryness removes organic solvent, obtains
Structural formula isDithionic acid vinyl acetate crude product 104.3g, purity 96.8%.Crude product carbon
It is recrystallized 3 times after dimethyl phthalate dissolution, obtains the dithionic acid vinyl acetate finished product 96.9g of purity 99.6%, yield 78.8%.
Embodiment 7
The synthesis of 2,4,8,10- tetra- oxa- -3,9- dithia ring [5.5] hendecane -3,3,9,9- tetroxide
Pure water 2000g, dimethylformamide 100g, ethyl propionate 600g, butanone 300g, oxygen are sequentially added into reaction flask
Change calcium 280g, structural formula isTetra- oxa- -3,9- dithia ring [5.5] of 2,4,8,10-
Hendecane 3,9- dioxide 114g, acetic acid iridium 1.7g are stirred and reaction system are cooled to 15 DEG C with ice salt bath, then drip
The peroxosulphuric 620g for adding embodiment 1 to be ready for is added dropwise in reaction system in 1.5 hours, keeps temperature during being added dropwise
At 10~15 DEG C.Continue stirring 1 hour after dripping, organic layer is first separated after filtering, then depressurize rotary evaporated to dryness, removing has
Solvent, obtaining structural formula isTetra- oxa- -3,9- dithia ring [5.5] of 2,4,8,10-
Hendecane -3,3,9,9- tetroxide crude product 105.6g, purity 98.7%.After crude product is dissolved with ethyl propionate plus active carbon is de-
Color, then condensing crystallizing, filtering, vacuum drying obtain the finished product 108.9g of purity 99.7%, yield 83.8%.
A kind of synthetic method of cyclic sulfates of the present invention has the advantages that compared with prior art
1, make raw material using cheap sulfuric acid and hydrogen peroxide, prepare sulfuric acid solution catalysis oxidation cyclic sulfite,
On the one hand it is high to react mild, easily controllable, reaction conversion ratio；Another aspect cost of material is low, and by-product salt recoverable is
By-product sale further reduces the cost, and increases economic benefit；
2, the evaporation capacity of water is small, and low energy consumption, and the waste water of generation is few, and synthesis technology is more environmentally protective；
3, obtained cyclic annular sulfate impurities are few, with high purity, wide market.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of cyclic sulfates, which is characterized in that sulfuric acid and the pre-synthesis sulfuric acid solution of hydrogen peroxide are used,
Under the conditions of again existing for organic solvent, metal inorganic compound and the catalyst, sulfuric acid solution and cyclic annular sulfurous acid is added dropwise
Ester carries out catalytic oxidation, and after reaction, by filtering out salt slag, stratification takes organic layer distillation and concentration, purification, obtains
To cyclic sulfates fine work.
2. the synthetic method of cyclic sulfates according to claim 1, which is characterized in that mistake in the sulfuric acid and hydrogen peroxide
The molar ratio of hydrogen oxide is H2SO4: H2O2=1~5:1；The process conditions of the synthesis are as follows: synthesis temperature -20~20 DEG C；It closes
At 0.1~10h of time.
3. the synthetic method of cyclic sulfates according to claim 2, which is characterized in that the mass concentration of the hydrogen peroxide
For more than or equal to 10%；The mass concentration of the sulfuric acid solution is more than or equal to 20%.
4. the synthetic method of cyclic sulfates according to claim 1, which is characterized in that the item of the catalytic oxidation
Part are as follows: reaction temperature -10~50 DEG C, 5~500min of reaction time.
5. the synthetic method of cyclic sulfates according to claim 1, which is characterized in that the cyclic sulfite adds
Enter 1/10~1 times that amount is hydrogen peroxide mole in the hydrogen peroxide；
The dosage of the metal inorganic compound is that institute's metal ion and the equivalent proportion of sulfuric acid are 1 in metal inorganic compound:
0.2~1.0；
The dosage of the catalyst is the 0.01~3% of cyclic sulfite quality；
The mass ratio of the cyclic sulfite and organic solvent is 1:1~30.
6. the synthetic method of cyclic sulfates according to claim 5, which is characterized in that the cyclic sulfates include five
Member ring single ring architecture, hexatomic ring single ring architecture, multiring structure and spirane structure compound:
Wherein, the structural formula of the five-membered ring single ring architecture compound are as follows:In formula, R1And R2To be identical or
Different H, F and C1~4Alkyl；
The structural formula of the hexatomic ring single ring architecture compound are as follows:In formula, R3、R4And R5To be identical or
Not identical H, F, C1~4Alkyl；
The structural formula of the multiring structure compound are as follows:In formula, R6And R7It is identical or not
Identical H, F, C1~4Alkyl；
The structural formula of the spirane structure compound are as follows:
7. the synthetic method of cyclic sulfates according to claim 5, which is characterized in that the metal inorganic compound is
Potassium sulfate, lithium carbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus, magnesium carbonate, calcium carbonate, strontium carbonate, zinc carbonate, phosphorus
Sour sodium, disodium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, lithium borate, Boratex, potassium borate, antifungin, lithium metasilicate, sodium metasilicate,
Potassium silicate, magnesium silicate, calcium silicates, alumina silicate, sodium aluminate, potassium aluminate, magnesium aluminate, magnesia, calcium oxide, zinc oxide, iron oxide,
One of ferrous oxide, aluminium oxide, tin oxide, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, zinc hydroxide or stannic hydroxide
Or multiple combinations.
8. the synthetic method of cyclic sulfates according to claim 5, which is characterized in that the organic solvent be ketone,
One or more of nitrile, ethers, esters, amides, imidazolone type, halogenated hydrocarbon solvent or aromatic hydrocarbon solvent
Combination.
9. the synthetic method of cyclic sulfates according to claim 5, which is characterized in that the catalyst is water-soluble mistake
Cross metal salt or its hydrate, the transition metal salt be platinous chloride, platinum tetrachloride, platinum nitrate, oxalic acid platinum, palladium chloride,
Palladium acetate, palladium nitrate, palladium sulfate, rhodium trichloride hydrate, rhodium nitrate, rhodium sulfate, rhodium acetate, acetylacetone,2,4-pentanedione rhodium, trichloride hydrate
Ruthenium, nitric acid ruthenium, ruthenium sulfate, acetic acid ruthenium, acetylacetone,2,4-pentanedione ruthenium, rhenium trichloride, rhenium pentachloride, osmium dichloride, osmium trichloride, chlorination
Manganese, manganese sulfate, manganese nitrate, manganese acetate, hydrated iridium trichloride, acetic acid iridium or acetylacetone,2,4-pentanedione iridium.
10. the synthetic method of cyclic sulfates according to claim 5, which is characterized in that the organic solvent be ketone,
One of nitrile, ethers, esters, amides, imidazolone type, halogenated hydrocarbon solvent or aromatic hydrocarbon solvent or above group
It closes；Wherein, the organic solvent of ketone is acetone, butanone, methyl iso-butyl ketone (MIBK) or cyclohexanone；The nitrile organic solvent is second
Nitrile or propionitrile；The ether organic solvent is tetrahydrofuran, 1,3- dioxolanes, 1,4- dioxane, glycol dimethyl ether, third
Glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or dimethyl ether；The based organic solvent is second
Sour methyl esters, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, third
Propyl propionate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate or trifluoroethyl methyl carbonic；The acyl
Amine organic solvent is dimethylformamide, dimethyl acetamide, diethylformamide or hexamethylphosphoramide；The imidazoles
Quinoline organic solvent of ketone is N, N- dimethyl-imidazolinone；The halogenated hydrocarbon organic solvent be methylene chloride, dichloroethanes or
Dichloropropane；The arene organic solvent is benzene,toluene,xylene, fluorobenzene, chlorobenzene, o-difluoro-benzene, m-difluorobenzene, right
Difluorobenzene, o-dichlorohenzene, m-dichlorobenzene or paracide.
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