CN109705157A - Cyano phosphate compounds and its preparation method and application - Google Patents
Cyano phosphate compounds and its preparation method and application Download PDFInfo
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- CN109705157A CN109705157A CN201811621722.3A CN201811621722A CN109705157A CN 109705157 A CN109705157 A CN 109705157A CN 201811621722 A CN201811621722 A CN 201811621722A CN 109705157 A CN109705157 A CN 109705157A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses cyano phosphate compounds and its preparation method and application.The cyano phosphate compounds are structure shown in formula (I), the electrolysis additive of the cyano phosphate compounds as lithium ion battery, it is remarkably improved the room temperature and high-temperature storage performance of lithium ion secondary battery, solve battery under room temperature or hot conditions in long term storage caused by capacity attenuation, flatulence the problems such asIn formula (I), R1For C1‑8Alkyl or C1‑8Alkenyl, R2The C replaced for cyano or cyano1‑8Alkyl.
Description
Technical field
The present invention relates to organic chemistry fileds, in particular to cyano phosphate compounds and its preparation method and application.
Background technique
In recent years, with the failure of the Global Oil energy and the development of new energy technology, applied on automobile power
Lithium ion battery technology rapidly develops, while also to the performance of lithium ion secondary battery, more stringent requirements are proposed.Due to country
Subsidy policy and energy density are linked up with, work long hours to meet electric car, high course continuation mileage, can high and low temperature environment just
It is often used, quickly-chargeable and the requirement with the long life, needing to develop has higher energy density, superior
The lithium ion secondary battery of high temperature circulation, storage performance and low temperature high rate performance.
Dintrile base class compound (such as succinonitrile, adiponitrile etc.) and phosphate compounds (such as three (trimethyl silicanes
Alkane) phosphate, triethyl phosphate etc.), as the common film for additive of lithium-ion battery electrolytes, it can significantly improve lithium
The service life of ion secondary battery, this kind of compound have broad application prospects in lithium-ion battery electrolytes.However, existing
Lithium-ion battery electrolytes additive still have much room for improvement.
Summary of the invention
In view of this, the present invention is directed to propose a kind of cyano phosphate compounds and its preparation method and application.The cyanogen
Electrolysis additive of the base phosphate compounds as lithium ion battery, be remarkably improved lithium ion secondary battery room temperature and
High-temperature storage performance, solve battery under room temperature or hot conditions in long term storage caused by capacity attenuation, flatulence the problems such as.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
According to an aspect of the present invention, the invention proposes a kind of compounds.According to an embodiment of the invention, describedization
Conjunction object is structure shown in formula (I),
In formula (I), R1For C1-8Alkyl or C1-8Alkenyl, R2The C replaced for cyano or cyano1-8Alkyl.
Compared with the existing technology, the electrolyte of the above embodiment of the present invention has the advantage that
Phosphorus oxygen double bond in compound shown in formula (I) has lone pair electrons, is a kind of lewis base, can be in anode
Material surface reacts to form protective film, to improve the high-temperature behavior of lithium ion battery.In addition, in compound shown in formula (I)
With metal ion complex reaction can occur for cyano (- CN), reduce metal ion activity, so that the side reaction in battery is reduced,
Gas is produced when improving battery performance, and battery high-temperature being inhibited to store.As a result, by using the compound as additive application in lithium from
In sub- secondary cell electrolyte, it is remarkably improved the room temperature and high-temperature storage performance of lithium ion secondary battery, solves battery in room
Under temperature or hot conditions in long term storage caused by capacity attenuation, flatulence the problems such as.
Further, the compound has the structure of one of:
According to another aspect of the present invention, the invention proposes a kind of methods of compound for preparing above-described embodiment.Root
According to the embodiment of the present invention, this method comprises: (1) is under the effect of the catalyst, compound and hypophosphorous acid shown in formula (a) are
It is contacted in one organic solvent, obtains compound shown in formula (b)；(2) in the presence of alkali, make compound shown in the formula (b) with
Compound shown in formula (c) contacts in a second organic solvent, obtains the compound of above-described embodiment,
In formula (a), formula (b) and formula (c), R1For C1-8Alkyl or C1-8Alkenyl, R2The C replaced for cyano or cyano1-8Alkyl.
In the method according to an embodiment of the present invention for preparing the compound, the cyanylation agent using severe toxicity is not needed, it is former
Material is easy to get and inexpensively, while this method step is short, mild condition, and post-processing approach is simple, and product purity is high.
Further, the catalyst is metallic catalyst, include in the metallic catalyst selected from nickel, copper, platinum, palladium and
At least one of gold.
Further, the catalyst includes being selected from NiCl2、NiBr2、NiI2、Ni/SiO2、PdCl2、CuCl2In at least
One of.
Further, first organic solvent includes sub- selected from benzene, toluene, n-hexane, petroleum ether, acetonitrile and dimethyl
At least one of sulfone.
Further, the molar ratio of compound shown in the formula (a) and the hypophosphorous acid is (2~4): 1.
Further, in step (1), the contact carries out 3~36h at 20~160 DEG C and completes.
Further, in step (1), the contact carries out under atmosphere of inert gases.
Further, step (1) further comprises: (1-1) under the effect of the catalyst, compound shown in formula (a) with
Hypophosphorous acid contacts in the first organic solvent；Step (1-1) products therefrom is successively extracted and is purified by (1-2), obtains formula
(b) compound shown in.
Further, the alkali be potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide and sodium tert-butoxide at least it
One.
Further, second organic solvent includes selecting acetone, acetonitrile, water, dimethyl sulfoxide and N, N- dimethyl methyl
At least one of amide.
Further, compound shown in the formula (b), compound and the alkali shown in the formula (c) molar ratio be 1:
(1~3): (2~6).
Further, in step (2), the contact carries out 30~60min at 20~120 DEG C and completes.
Further, step (2) further comprises:
(2-1) in the presence of alkali, compound shown in compound shown in formula (b) and formula (c) is in a second organic solvent
Contact；
Step (2-1) products therefrom is successively extracted and is purified by (2-2), obtains the compound of above-described embodiment.
Further, using at least one of ether, petroleum ether, toluene, ethyl acetate and methylene chloride as extraction
Agent carries out the extraction.
In accordance with a further aspect of the present invention, the invention proposes a kind of electrolyte.According to an embodiment of the invention, the electrolysis
Liquid includes: lithium salts, solvent；And the compound of above-described embodiment.Electrolyte of the invention is by using compound shown in formula (I)
As additive, it is a kind of lewis base that the phosphorus oxygen double bond in compound shown in formula (I), which has lone pair electrons, can be in anode
Material surface reacts to form protective film, to improve the high-temperature behavior of lithium ion battery.In addition, in compound shown in formula (I)
With metal ion complex reaction can occur for cyano (- CN), reduce metal ion activity, so that the side reaction in battery is reduced,
Gas is produced when improving battery performance, and battery high-temperature being inhibited to store.As a result, by the way that the electrolyte is applied to lithium ion secondary battery
In, it is remarkably improved the room temperature and high-temperature storage performance of lithium ion secondary battery, it is long under room temperature or hot conditions to solve battery
The problems such as capacity attenuation, flatulence caused by phase storage.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include at least one this feature.
Inventor has found that existing lithium ion secondary battery is in room temperature or high temperature in the research to lithium ion secondary battery
Under the conditions of, phenomena such as capacity attenuation, flatulence are easy to appear in long-term storing process.By further investigation, this is mainly inventor
Since anode used in the lithium-ion-power cell that is commercialized at present mostly uses the tertiary cathode material of high nickel content
(LiNi0.6Co0.2Mn0.2O2, LiNi0.8Co0.1Mn0.1O2), structural instability, metal ion hold this positive electrode at high temperature
Easily dissolution, the Ni of high price4+It is easy that oxidation reaction occurs with electrolyte, leads to degradation of cell performance.
In consideration of it, in one aspect of the invention.The invention proposes a kind of compounds.According to an embodiment of the invention,
The compound is structure shown in formula (I),
In formula (I), R1For C1-8Alkyl or C1-8Alkenyl, R2The C replaced for cyano or cyano1-8Alkyl.
It should be noted that above-mentioned C1-8Alkyl and C1-8Alkenyl is also possible to either linear alkyl (straight chained alkyl)
Branch or cyclic alkyl；Above-mentioned C1-8Alkenyl is also possible to branch or cyclic alkyl either linear alkenyl (straight-chain alkenyl).
Phosphorus oxygen double bond in compound shown in formula (I) has lone pair electrons, is a kind of lewis base, can be in anode
Material surface reacts to form protective film, to improve the high-temperature behavior of lithium ion battery.In addition, in compound shown in formula (I)
With metal ion complex reaction can occur for cyano (- CN), reduce metal ion activity, so that the side reaction in battery is reduced,
Gas is produced when improving battery performance, and battery high-temperature being inhibited to store.As a result, by using the compound as additive application in lithium from
In sub- secondary cell electrolyte, it is remarkably improved the room temperature and high-temperature storage performance of lithium ion secondary battery, solves battery in room
Under temperature or hot conditions in long term storage caused by capacity attenuation, flatulence the problems such as.
Preferred embodiment in accordance with the present invention, above compound have the structure of one of:
Inventor is by the way that the further preferred of compound structure shown in formula (I), discovery is using as shown in formula (1)~(4)
Additive of the compound as electrolyte, can be further improved the room temperature and high-temperature storage performance of lithium ion secondary battery,
Further advantageously account for battery under room temperature or hot conditions in long term storage caused by capacity attenuation, flatulence the problems such as.
In another aspect of this invention, the invention proposes a kind of methods of compound for preparing above-described embodiment.According to
The embodiment of the present invention, this method comprises: (1) is under the effect of the catalyst, compound and hypophosphorous acid shown in formula (a) are first
It is contacted in organic solvent, obtains compound shown in formula (b)；(2) in the presence of alkali, compound shown in formula (b) and formula (c) institute
Show that compound contacts in a second organic solvent, obtain the compound of above-described embodiment,
In formula (a), formula (b) and formula (c), R1For C1- 8 alkyl or C1- 8 alkenyls, R2The C replaced for cyano or cyano1- 8 alkane
Base.
In the method according to an embodiment of the present invention for preparing the compound, the cyanylation agent using severe toxicity is not needed, it is former
Material is easy to get and inexpensively, while this method step is short, mild condition, and post-processing approach is simple, and product purity is high.
The method of prepare compound according to an embodiment of the present invention is described in detail further below.
(1) under the effect of the catalyst, compound shown in formula (a) contacts in the first organic solvent with hypophosphorous acid, obtains
To compound shown in formula (b).Specifically, in the step, the R containing cyano2- OH takes with hypophosphorous acid under the action of catalyst
Generation reaction, obtains the phosphate compound (compound shown in formula (b)) containing cyano.With R in the reaction2- OH is as cyanalation
Reagent, avoids the use of hypertoxic inorganic cyanide, and raw material is easy to get and inexpensively.
According to a particular embodiment of the invention, the hypophosphorous acid that the mass fraction of commercialization is 50% can be used in the step,
And the part water removed by way of vacuumizing in 50% hypophosphorous acid before using in some embodiments can be by 50% time
Phosphoric acid vacuumizes concentration 1h.In addition, inventor has found in an experiment, there is water generation in the reaction, it can be by water segregator by system
In water remove, so as to promote reaction to positive reaction direction carry out.
According to an embodiment of the invention, above-mentioned catalyst is metallic catalyst, may include in the metallic catalyst selected from nickel,
At least one of copper, platinum, palladium and gold.It can further improve the yield of compound shown in formula (b) as a result,.
According to a particular embodiment of the invention, catalyst includes being selected from NiCl2、NiBr2、NiI2、Ni/SiO2、PdCl2、
CuCl2At least one of.It can further improve the yield of compound shown in formula (b) as a result,.
According to an embodiment of the invention, the first organic solvent includes being selected from benzene, toluene, n-hexane, petroleum ether, acetonitrile and two
At least one of methyl sulfoxide.Compound and hypophosphorous acid shown in formula (a) have good dissolubility in above-mentioned solvent, use
Above-mentioned solvent can be further improved the yield of compound shown in formula (b) as the first organic solvent.
According to an embodiment of the invention, the molar ratio of compound and hypophosphorous acid shown in formula (a) can be (2~4): 1.Invention
People has found in an experiment, and by increasing the inventory of compound shown in formula (a), compound shown in formula (a) is in excess in hypophosphorous acid,
It can be further improved the conversion ratio of hypophosphorous acid, promote reaction to carry out to the direction of positive reaction, keep hypophosphorous acid anti-as much as possible
Compound shown in formula (b) should be obtained, and compound shown in excessive (a) is easy to remove by post-processing, it will not be to product
Separation brings inconvenience.If the dosage of compound shown in formula (a) is too low, the production of compound shown in product formula (b) can be significantly reduced
Rate, and a large amount of residues of hypophosphorous acid are difficult to handle.
According to an embodiment of the invention, contact of the compound shown in formula (a) with hypophosphorous acid can be 20~160 in step (1)
3~36h is carried out at DEG C to complete.In some embodiments, reaction temperature is room temperature to 160 DEG C.Preferably, reaction temperature 110
~130 DEG C, the reaction time be not less than for 24 hours, such as 24 hours, 27h, 30h, 33h or 36h.It can further improve product formula as a result,
(b) yield of compound shown in.
According to an embodiment of the invention, contact of the compound shown in formula (a) with hypophosphorous acid can under atmosphere of inert gases into
Row, such as nitrogen or argon atmosphere.It can further improve the yield of compound shown in product formula (b) as a result,.
According to an embodiment of the invention, in step (1), the feeding mode of compound and hypophosphorous acid shown in formula (a) not by
Especially limitation.Specific example according to the present invention can first put into hypophosphorous acid, compound shown in formula (a) and the into reactor
One organic solvent, and it is heated to reflux 2~4h under atmosphere of inert gases, then add catalyst；It can also be first to reactor
Middle investment hypophosphorous acid, catalyst and the first organic solvent, and it is heated to reflux 2~4h under atmosphere of inert gases, then add
Compound shown in formula (a).Inventor has found that the time needed for above two feeding mode reaction is different, and yield has in an experiment
It is distinguished, but is differed unobvious, it may be possible to since the reaction mechanism of raw material in two kinds of feeding modes is different.
According to an embodiment of the invention, step (1) may further include: (1-1) under the effect of the catalyst, formula
(a) compound shown in contacts in the first organic solvent with hypophosphorous acid；(1-2) successively extracts step (1-1) products therefrom
It takes and purifies, obtain compound shown in formula (b).Specifically, ether, petroleum ether, toluene, ethyl acetate and dichloromethane can be used
At least one of alkane extracts step (1-1) products therefrom as extractant, and passes through the purifying to extraction organic phase
It obtains compound shown in formula (b), such as can have first with desiccant (such as anhydrous sodium sulfate, anhydrous magnesium sulfate) to extraction
Machine is mutually dried, then obtains compound shown in formula (b) by the common way of purification in this field (such as column chromatography, distillation etc.).
In some embodiments, it is also possible to first remove at least part solvent in product, and it is dried using desiccant.
(2) in the presence of alkali, make compound shown in compound shown in the formula (b) and formula (c) in the second organic solvent
Middle contact obtains the compound (compound shown in formula (I)) of above-described embodiment.In the step, in the presence of alkali, formula (b) institute
Show that compound can remove the hydrogen atom being connected directly with phosphorus atoms, and then compound shown in formula (c) (idoalkane) reacts production
(I) compound shown in.
According to an embodiment of the invention, above-mentioned alkali can be potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide and tertiary fourth
At least one of sodium alkoxide.The alkalinity of above-mentioned alkali is suitable for that can be effectively removed direct with phosphorus atoms in compound shown in formula (b)
Connected hydrogen atom, and there is certain dissolubility in a second organic solvent, so as to further increase formula (I) shownization
Close the yield of object.
According to an embodiment of the invention, above-mentioned second organic solvent may include selecting acetone, acetonitrile, water, dimethyl sulfoxide
At least one of with N,N-dimethylformamide.Compound and alkali shown in formula (b) have good dissolution in above-mentioned solvent
Property, using above-mentioned solvent as the second organic solvent, it can be further improved the yield of compound shown in formula (I).
According to an embodiment of the invention, the molar ratio of compound shown in compound, formula (c) shown in formula (b) and alkali is 1:(1
~3): (2~6).In some embodiments, if the inventory of compound shown in formula (b) is 1 equivalent, compound shown in formula (c)
Inventory is about 1~3 equivalent, and the inventory of alkali is 2~6 equivalents.By using chemical combination shown in equivalent or slightly excessive formula (c)
Object can be further improved the yield of compound shown in formula (I)；By using excessive alkali, foot can be provided for reaction system
Enough strong alkaline environments, in order to the progress of the reaction of compound shown in compound shown in formula (b) and formula (c), and excessive alkali is very
It is easy to remove by post-processing, will not bring inconvenience to the separation of product.
According to an embodiment of the invention, in step (2), compound shown in compound, formula (c) shown in formula (b) and alkali are connect
Touching carries out 30~60min at 20~120 DEG C and completes.In some embodiments, reaction temperature is room temperature to 120 DEG C.Preferably,
Reaction temperature is 20~60 DEG C or room temperature is to 60 DEG C.It can further improve the yield of compound shown in product formula (I) as a result,.
According to an embodiment of the invention, in step (2), the throwing of compound shown in compound, formula (c) shown in formula (b) and alkali
Material mode is not particularly restricted.Specific example according to the present invention can first put into hypophosphorous acid, formula (a) institute into reactor
Show compound and the first organic solvent, and be heated to reflux 2~4h under atmosphere of inert gases, then adds catalyst；It can also
Hypophosphorous acid, catalyst and the first organic solvent are put into reactor with elder generation, and it is heated to reflux under atmosphere of inert gases 2~
Then 4h adds compound shown in formula (a).Inventor has found in an experiment, when needed for above two feeding mode reaction
Between different, yield different from, but differ unobvious, it may be possible to since the reaction mechanism of raw material in two kinds of feeding modes is different.
According to an embodiment of the invention, step (2) can further include: (2-1) in the presence of alkali, formula (b)
Shown compound contacts in a second organic solvent with compound shown in formula (c)；(2-2) by step (2-1) products therefrom successively
It is extracted and is purified, obtain the compound of above-described embodiment.Specifically, ether, petroleum ether, toluene, acetic acid second can be used
At least one of ester and methylene chloride extract step (2-1) products therefrom as extractant, and by having to extraction
The purifying of machine phase obtains compound shown in formula (I), such as can be first with desiccant (such as anhydrous sodium sulfate, anhydrous magnesium sulfate
Deng) extraction organic phase is dried, then formula (I) is obtained by the common way of purification in this field (such as column chromatography, distillation)
Shown compound.In some embodiments, it is also possible to first remove at least part solvent in product, and carried out using desiccant
It is dry.
It should be noted that being equally applicable to the prepare compound described previously for feature and advantage described in compound
Method, this is no longer going to repeat them.
In another aspect of the invention, the invention proposes a kind of electrolyte.According to an embodiment of the invention, the electrolyte
It include: lithium salts, solvent；And the compound of above-described embodiment.Electrolyte of the invention is made by using compound shown in formula (I)
For additive, it is a kind of lewis base that the phosphorus oxygen double bond in compound shown in formula (I), which has lone pair electrons, can be in positive material
Material surface reacts to form protective film, to improve the high-temperature behavior of lithium ion battery.In addition, the cyanogen in compound shown in formula (I)
With metal ion complex reaction can occur for base (- CN), reduce metal ion activity and mention to reduce the side reaction in battery
High battery performance, and while inhibiting battery high-temperature to store, produces gas.As a result, by the way that the electrolyte is applied to lithium ion secondary battery
In, it is remarkably improved the room temperature and high-temperature storage performance of lithium ion secondary battery, it is long under room temperature or hot conditions to solve battery
The problems such as capacity attenuation, flatulence caused by phase storage.
It should be noted that described previously for compound, prepare compound method described in feature and advantage it is equally suitable
For the electrolyte, this is no longer going to repeat them.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
(1) 645mg (3mol) 3- hydroxypropionitrile is slowly added dropwise to (wherein, it is dense to shift to an earlier date vacuum for hypophosphorous acid to hypophosphorous acid is filled
Contracting) reaction flask in, and reaction flask is connected to a point water distillation reception pipe.Then 50mL toluene solution is added, is filled with nitrogen 5min,
In 110 DEG C of return stirring 4h, until system becomes homogeneously, Dehydrated nickel chloride catalyst 15mg will to be added after system cooling
(0.15mol), is filled with nitrogen and continues to be heated at reflux and obtain the solution containing two (propionitrile base) phosphate cpds for 24 hours.It will be resulting
The solution of two (propionitrile base) phosphate cpds carries out extraction and is concentrated to get saturated solution, and then chromatographic purifying crystallizes to obtain dinitrile
The solid product of phosphate compound.
(2) two (propionitrile base) phosphate cpd obtained in step (1) and iodomethane are subjected to methylation reaction.Specifically
, 30mL acetone and 10mL distilled water are first added into reactor.Then 717mg (5.2mmol) potassium carbonate is added, temperature is cold
But to 0 DEG C, then two (propionitrile base) phosphate cpd obtained in step (1) is added in reactor, is then added
554mg (4mmol) iodomethane.Then slowly restore to room temperature reaction to terminate.After completion of the reaction, reaction product is added to ice water
In.Then ethyl acetate is added into reaction system, separates organic phase (product methyl-two (third with separatory funnel after being sufficiently stirred
Itrile group) phosphate compounds are extracted in organic phase), organic phase is washed 2~3 times with ice water, rotary evaporation removal has
Then column chromatographic purifying obtains crude product methyl-two (propionitrile base) phosphate compound 1200mg (total recovery 64%) to solvent.
Embodiment 2
Two (propionitrile base) phosphate compounds are prepared according to method substantially the same manner as Example 1, difference is, step
(2) in, iodomethane is replaced with into iodoethane, feed ratio and reaction condition are same as Example 1.Finally obtain product ethyl-two
(propionitrile base) phosphate 1300mg (total recovery 65%).
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of compound, which is characterized in that the compound is structure shown in formula (I),
In formula (I), R1For C1-8Alkyl or C1-8Alkenyl, R2The C replaced for cyano or cyano1-8Alkyl.
2. compound according to claim 1, which is characterized in that the compound has the structure of one of:
3. a kind of method for preparing compound of any of claims 1 or 2 characterized by comprising
(1) under the effect of the catalyst, compound shown in formula (a) contacts in the first organic solvent with hypophosphorous acid, obtains formula
(b) compound shown in；
(2) in the presence of alkali, compound shown in the formula (b) is connect in a second organic solvent with compound shown in formula (c)
Touching, obtains compound of any of claims 1 or 2,
In formula (a), formula (b) and formula (c), R1For C1-8Alkyl or C1-8Alkenyl, R2The C replaced for cyano or cyano1-8Alkyl.
4. according to the method described in claim 3, it is characterized in that, the catalyst is metallic catalyst, the metal catalytic
It include selected from least one of nickel, copper, platinum, palladium and gold in agent；
Optionally, the catalyst includes being selected from NiCl2、NiBr2、NiI2、Ni/SiO2、PdCl2、CuCl2At least one of；
Optionally, first organic solvent includes in benzene, toluene, n-hexane, petroleum ether, acetonitrile and dimethyl sulfoxide
At least one.
5. according to the method described in claim 3, it is characterized in that, compound shown in the formula (a) and the hypophosphorous acid rub
You are than being (2~4): 1.
6. according to the method described in claim 3, it is characterized in that, the alkali is potassium carbonate, potassium hydroxide, sodium carbonate, hydrogen-oxygen
Change at least one of sodium and sodium tert-butoxide；
Optionally, second organic solvent includes selecting in acetone, acetonitrile, water, dimethyl sulfoxide and n,N-Dimethylformamide
At least one of.
7. according to the method described in claim 3, it is characterized in that, compound shown in the formula (b), formula (c) shownization
The molar ratio for closing object and the alkali is 1:(1~3): (2~6).
8. according to the method described in claim 3, it is characterized in that, the contact carries out at 20~120 DEG C in step (2)
30~60min is completed.
9. according to the method described in claim 3, it is characterized in that, step (1) further comprises:
(1-1) under the effect of the catalyst, compound shown in formula (a) contacts in the first organic solvent with hypophosphorous acid；
Step (1-1) products therefrom is successively extracted and is purified by (1-2), obtains compound shown in formula (b)；
Optionally, step (2) further comprises:
(2-1) in the presence of alkali, compound shown in formula (b) contacts in a second organic solvent with compound shown in formula (c)；
Step (2-1) products therefrom is successively extracted and is purified by (2-2), obtains compound of any of claims 1 or 2；
Optionally, it is carried out using at least one of ether, petroleum ether, toluene, ethyl acetate and methylene chloride as extractant
The extraction.
10. a kind of electrolyte characterized by comprising
Lithium salts, solvent；And
Compound of any of claims 1 or 2.
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Cited By (2)
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| CN112448033A (en) * | 2019-09-05 | 2021-03-05 | 杉杉新材料（衢州）有限公司 | High-voltage lithium ion battery electrolyte and long-cycle-life high-voltage lithium ion battery |
| CN112442166A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Reactive flame retardant and preparation method and application thereof |
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| CN102386441A (en) * | 2011-10-21 | 2012-03-21 | 厦门大学 | Double-functional lithium battery electrolyte additive and preparation method thereof |
| US20140303394A1 (en) * | 2013-04-05 | 2014-10-09 | Texas Christian University | Synthesis of H-Phosphonate Intermediates and Their Use in Preparing the Herbicide Glyphosate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112442166A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Reactive flame retardant and preparation method and application thereof |
| CN112448033A (en) * | 2019-09-05 | 2021-03-05 | 杉杉新材料（衢州）有限公司 | High-voltage lithium ion battery electrolyte and long-cycle-life high-voltage lithium ion battery |
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