CN101497597A - Preparation of 1,2-dialkyl-1,2-difluorinated ethylene carbonate - Google Patents
Preparation of 1,2-dialkyl-1,2-difluorinated ethylene carbonate Download PDFInfo
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- CN101497597A CN101497597A CNA2009100085189A CN200910008518A CN101497597A CN 101497597 A CN101497597 A CN 101497597A CN A2009100085189 A CNA2009100085189 A CN A2009100085189A CN 200910008518 A CN200910008518 A CN 200910008518A CN 101497597 A CN101497597 A CN 101497597A
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Abstract
The invention provides a method for manufacturing 1,2-dialkyl-1,2-bi-fluoroethylene carbonate by one procedure, in which carbonyl fluoride is reacted with diketone compound.
Description
Technical field
The present invention relates to make 1 with operation, 2-dialkyl group-1, the method for 2-difluorinated ethylene carbonate, further relate to new 1,2-dialkyl group-1, the cis-isomeride of 2-difluorinated ethylene carbonate and trans-isomer(ide), and their manufacture method.
Background technology
NSC 11801 (=1,3-two oxa-s penta ring-2-ketone) is widely used as the solvent of electrolytic solution for electrochemical device such as secondary cell and electrical condenser.
And, process fluorizated NSC 11801 is owing to the advantage with excellences such as charge and current efficiency receives much concern, known have a difluorinated ethylene carbonate (4,4-two fluoro-1,3-two oxa-s penta ring-2-ketone, 4,5-two fluoro-1,3-two oxa-s penta ring-2-ketone) etc. (patent documentation 1), and proposed to make single fluorinated ethylene carbonate fluorizated manufacture method.
Fluoridize in replacing NSC 11801 (patent documentation 2～3) also on the books, scope general formula has very widely been proposed in the patent documentation 2, also enumerated a large amount of exemplary compounds, but in fact among the embodiment employed fluorinated ethylene carbonate only be single fluorinated ethylene carbonate and difluorinated ethylene carbonate.
In patent documentation 3, put down in writing have the effect that suppress to form dendritic crystal have methyl as substituent fluoro ethyl-carbonate.But in this patent documentation 3, the fluorinated ethylene carbonate of Shi Yonging only is a 1-methyl-2 in fact in an embodiment, and the 2-difluorinated ethylene carbonate is a kind of, and to 1,2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate is record not.
Patent documentation 1: Japanese patent laid-open 2000-344763 communique
Patent documentation 2: the Japanese Patent spy opens the 2007-188873 communique
Patent documentation 3: Japanese patent laid-open 8-306364 communique
Summary of the invention
The object of the present invention is to provide a kind ofly, make 1 with operation, 2-dialkyl group-1, the method for 2-difluorinated ethylene carbonate without NSC 11801.
The invention provides 1 shown in a kind of formula (3), 2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate is characterized in that, makes the dione compounds reaction shown in carbonyl fluoride shown in the formula (1) and the formula (2),
Formula (1):
Formula (2):
In the formula (2), R
1And R
2Identical or different, be and can contain the alkyl that fluorine atom also can have the carbonatoms 1～4 of ehter bond,
Formula (3):
In the formula (3), R
1And R
2Identical with formula (2).
1 of formula (3), 2-dialkyl group-1, the 2-difluorinated ethylene carbonate obtains with the mixture of cis-isomeride and trans-isomer(ide), by to this 1,2-dialkyl group-1, the cis-isomeride of 2-difluorinated ethylene carbonate and the mixture of trans-isomer(ide) carry out fractionation, can emanate and be the cis-1 shown in the formula (3A), 2-dialkyl group-1, the anti-form-1 shown in 2-difluorinated ethylene carbonate and the formula (3B), 2-dialkyl group-1, the 2-difluorinated ethylene carbonate.
Formula (3A):
In the formula, R
1And R
2The same.
Formula (3B):
In the formula, R
1And R
2The same.
Gained cis-1,2-dialkyl group-1,2-difluorinated ethylene carbonate (3A) and anti-form-1,2-dialkyl group-1,2-difluorinated ethylene carbonate (3B) is the novel cpd of not made.
In addition, the invention still further relates to the anti-form-1 shown in a kind of formula (3B), 2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate, it is characterized in that, comprising: make the dione compounds reaction shown in carbonyl compound shown in formula (4a) or the formula (4b) and the formula (2), the anti-form-1 shown in the manufacturing formula (5), 2-dialkyl group-1, the operation of 2-dihalo NSC 11801; Then, in organic solvent, make fluorizating agent and the anti-form-1 that obtains, 2-dialkyl group-1, the operation of 2-dihalo NSC 11801 reaction.
Formula (4a):
Formula (4b):
In formula (4a) and formula (4b), X
1Expression F, Cl or Br, X
2Expression Cl or Br, X
1And X
2Can be the same or different,
Formula (2):
In the formula (2), R
1And R
2Identical or different, be and can contain the alkyl that fluorine atom also can have the carbonatoms 1～4 of ehter bond,
Formula (5):
In the formula (5), X
1, X
2, R
1And R
2It is the same,
Formula (3B):
In the formula (3B), R
1And R
2Identical or different, be and can contain the alkyl that fluorine atom also can have the carbonatoms 1～4 of ehter bond.
The invention effect
Manufacturing method according to the invention can enough operations make 1 with high yield, 2-dialkyl group-1,2-difluorinated ethylene carbonate.
Embodiment
Of the present invention 1,2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate is characterized in that, makes the carbonyl fluoride and the reaction of the dione compounds shown in the formula (2) of formula (1).
Formula (2):
In the formula, R
1And R
2Identical or different, be and can contain the alkyl that fluorine atom also can have the carbonatoms 1～4 of ehter bond.
The carbonyl fluoride of formula (1) is a known compound, for example, can synthesize by making the reaction of fluorizating agent and carbonyl chloride.
As fluorizating agent, except hydrofluoric acid, fluorine gas, the compound shown in the also preferred illustration formula MF (in the formula, M is alkali metal atom or quaternary ammonium cation).MF specifically can enumerate the compound of KF, NaF, CsF, LiF, quaternary ammonium cation and fluorine anion etc.
The dione compounds of formula (2) also is a known compound.R
1And R
2For the alkyl that can have ehter bond of carbonatoms 1～4 or contain fluoroalkyl.The viscosity of considering the gained carbonic ether is low, and the carbonatoms of alkyl is up to 4, is preferably 1～3 especially.R
1And R
2Can be the same or different.
As the alkyl of fluorine-free, for example, can enumerate the following compound of Denging.
CH
3—、 CH
3CH
2—、 CH
3CH
2CH
2—、 CH
3CH
2CH
2CH
2—、
As fluorine-free alkyl, for example, can enumerate the following compound of Denging with ehter bond.CH
3OCH
2—、CH
3OCH
2CH
2—、CH
3CH
2OCH
2—、
CH
3OCH
2CH
2CH
2—、CH
3CH
2OCH
2CH
2—、CH
3CH
2CH
2OCH
2—、
CH
3OCH
2OCH
2—、CH
3OCH
2OCH
2CH
2—、CH
3CH
2OCH
2OCH
2—、
CH
3OCH
2CH
2OCH
2—、
CH
3OCH
2OCH
2OCH
2—、
In addition, as containing fluoroalkyl, for example, can enumerate the following compound of Denging.
CF
3—、HCF
2—、FCH
2—、CF
3CF
2—、CF
3CH
2—、HCF
2CF
2—、
FCH
2CF
2—、CF
3CF
2CH
2—、HCF
2CF
2CH
2—、CF
3CH
2CH
2—、
HCF
2CH
2CH
2—、FCH
2CH
2CH
2—、CF
3CF
2CF
2CF
2—、
CF
3CF
2CF
2CH
2—、HCF
2CF
2CH
2CH
2—、HCF
2CF
2CF
2CF
2—、
CF
3CF
2CH
2CH
2—、CF
3CH
2CH
2CH
2—、
As the fluoroalkyl that contains, for example, can enumerate the following compound of Denging with ehter bond.
CF
3OCH
2—、CF
3CF
2OCH
2—、CF
3OCF
2CH
2—、
CF
3OCF
2—、CF
3OCH
2CH
2—、
CF
3CF
2CH
2OCH
2—、HCF
2CF
2CH
2OCH
2—、
CF
3CH
2OCH
2—、HCF
2CH
2OCH
2—、
HCF
2OCH
2CH
2—
As the concrete example of dione compounds (2), can the following compound of Denging be shown example, but be not limited to this.
Under the existence that is reflected at alkali of carbonyl fluoride (1) and dione compounds (2), in solvent, quantitatively carry out, generate 1,2-dialkyl group-1,2-difluorinated ethylene carbonate.
As alkali, can use mineral alkali, organic bases arbitrarily, particularly except tertiary amines such as pyridine, triethylamine, also preferred primary amine, secondary amine etc.
As solvent, be preferably organic solvent, for example, can methylene dichloride, chloroform, tetrahydrofuran (THF), dimethyl acetamide, dimethyl formamide, glyme kind solvent, acetonitrile, acetone, toluene, ethyl acetate isopolarity solvent etc. be shown example.
Be reflected under 0～40 ℃ of temperature of reaction, normal atmosphere or the pressurized conditions and fully carry out.Wherein, about reaction conditions, can also adopt by carbonyl chloride and dione compounds reaction synthesizing fluoro carbonic acid vinyl acetate reaction conditions (for example, SYNTHETIC COMMUNICATIONS, 23 (6), pp847-853 (1993), or Journal of Fluorine Chemistry, 120, the condition of record among the pp105-110 (2003)).
By manufacture method of the present invention obtain 1,2-dialkyl group-1,2-difluorinated ethylene carbonate are the mixtures of cis-isomeride and trans-isomer(ide).Directly former state is used the additive of this mixture as nonaqueous electrolytic solution, also it can be emanated respectively to using behind cis-isomeride and the trans-isomer(ide).
As by 1,2-dialkyl group-1, the method of the cis-isomeride of 2-difluorinated ethylene carbonate and the mixture of trans-isomer(ide) segregation cis-isomeride and trans-isomer(ide), because 1,2-dialkyl group-1, the boiling point of the cis-isomeride of 2-difluorinated ethylene carbonate and the boiling point of trans-isomer(ide) have very big-difference, and therefore, utilizing the difference of boiling point to carry out fractionation is the most simple and effective method.
The known method that fractionation can adopt easily and utilize for example Oldershaw sieve plate (Oldershaw) or blister-type separator column, concentric(al) circles tubular separator column, revolve fractionators such as banding pattern separator column carries out.
Isolated cis-1,2-dialkyl group-1,2-difluorinated ethylene carbonate are the novel cpd shown in the formula (3A), and anti-form-1,2-dialkyl group-1,2-difluorinated ethylene carbonate are the novel cpd shown in the formula (3B).
(formula 3A):
(formula 3B):
And, as optionally making anti-form-1,2-dialkyl group-1, the method of 2-difluorinated ethylene carbonate has following method, it comprises the dione compounds reaction that makes shown in carbonyl compound shown in formula (4a) or the formula (4b) and the formula (2), anti-form-1 shown in the manufacturing formula (5), 2-dialkyl group-1, the operation of 2-dihalo NSC 11801; Then, in organic solvent, make fluorizating agent and the anti-form-1 that obtains, 2-dialkyl group-1, the operation of 2-dihalo NSC 11801 reaction.
Formula (4a):
Formula (4b):
In formula (4a) and formula (4b), X
1Expression F, Cl or Br, X
2Expression Cl or Br, X
1And X
2Can be the same or different,
Formula (2):
In the formula (2), R
1And R
2Identical or different, be and can contain the alkyl that fluorine atom also can have the carbonatoms 1～4 of ehter bond,
Formula (5):
In the formula (5), X
1, X
2, R
1And R
2The same.
According to this manufacture method, because the size of chlorine atom, bromine atoms and iodine atom is bigger than fluorine atom, therefore, must contain 1 of chlorine atom, bromine atoms and iodine atom, 2-dialkyl group-1, the selection rate of the trans-isomer(ide) of 2-dihalo NSC 11801 (5) increases substantially.By making fluorizating agent and this anti-form-1,2-dialkyl group-1, the reaction of 2-dihalo NSC 11801 is substituted by fluorine atom with halogen atom, can optionally make anti-form-1,2-dialkyl group-1,2-difluorinated ethylene carbonate (purity 99.5%).
As the compound shown in the formula (4a), can enumerate carbonyl fluoride chlorine, carbonyl fluoride bromine, carbonyl fluoride iodine, carbonyl chloride, carbonyl chlorobromide, carbonyl chlorobromide, carbonyl bromide, carbonyl bromide iodine or phosphinylidyne iodine.
As the compound shown in the formula (4b), for example, can enumerate
Deng.
The reaction of leading portion operation can with the same reaction conditions of the reaction of above-mentioned carbonyl fluoride and dione compounds (2) under carry out.And the reaction of back segment operation can be carried out under the condition of the fluoridation in the organic solvent commonly used.Organic solvent is preferably polar solvent, can enumerate the solvent that uses in above-mentioned carbonyl fluoride and dione compounds (2) reaction.Fluorizating agent also can adopt carbonyl chloride is transformed to the fluorizating agent that uses in the reaction of carbonyl fluoride.
These are 1 years old; 2-dialkyl group-1; the cis-isomeride of 2-difluorinated ethylene carbonate, trans-isomer(ide) and both mixtures can be gone up at the electrode (negative or positive electrode) of lithium secondary battery effectively and form stable protective membrane, and be very useful as the additive of nonaqueous electrolytic solution.
Embodiment
Below, enumerate embodiment manufacture method of the present invention is described, but the present invention is not limited to these embodiment.
The employed analytical procedure of following examples is as follows.
(1)NMR
The AC-300 that device: BRUKER produces
Condition determination:
19F-NMR:282MHz (phenylfluoroform=-62.3ppm)
1H-MNR:300MHz (phenylfluoroform=7.51ppm)
(2) Infrared spectroscopy (IR)
The Fourier transform infrared spectrophotometer 1760X that produces with Perkin Elmer company is at room temperature measuring.
Embodiment 1 (1,2-dimethyl-1,2-difluorinated ethylene carbonate synthetic)
Use the SUS system autoclave of 3L to react.Adding formula in reaction vessel
Shown by 2, the 3-dimethyl diketone (300g, 3.48mol), pyridine (138g, 1.74mol), methylene dichloride (1L) and stirring.Then at room temperature, forced with 0.1～0.5MPa
Shown carbonyl fluoride.Affirmation is along with heat release, and temperature is raised to 46.2 ℃.Continue then to add, until confirming that heat release, pressure reduce, reaction process is confirmed with gas-chromatography (GC).Confirm raw material 2, when the 3-dimethyl diketone disappears, finishing reaction.After the reaction, carbonyl fluoride residual in the system is purged, carry out next step aftertreatment then.With the 1L pure water reaction soln is repeatedly cooled off at first, earlier.Gather the organic layer of lower floor then, the HCl solution 1L with 1N cools off once more again, removes residual pyridine thus.After the cooling, use MgSO
4Drying is used the vaporizer concentrated filtrate.At this moment, production
Shown trans-isomer(ide) and formula
Shown cis-isomeride, ratio are trans-isomer(ide): cis-isomeride=76: 24 (mol%).
With refining this enriched material of 5 grades of Oldershaw sieve plates (Oldershawcolumn that Sigma-Alderich company produces).
As a result, obtaining purity is the cut of 35 ℃ (3mmHg) of 99.1% (yield 60%), is trans-isomer(ide), and obtains the cut that purity is 52 ℃ (2mmHg) of 99.6% (yield 20%), is cis-isomeride.
Utilize NMR and IR to study these compounds,, confirm to be respectively 1,2-dimethyl-1, the trans-isomer(ide) of 2-difluorinated ethylene carbonate and cis-isomeride by following appraising datum.
For trans-isomer(ide):
1H-NMR (deuterated acetone): 1.81～2.00 (m:6H)
19F-NMR (deuterated acetone) :-194.7～-194.5 (m:2F)
IR：1853.8cm
-1
For cis-isomeride:
1H-NMR (deuterated acetone): 1.81～2.00 (m:6H)
19F-NMR (deuterated acetone) :-113.9～-112.4 (m:2F)
IR：1853.8cm
-1
Embodiment 2 (1,2-diethyl-1,2-difluorinated ethylene carbonate synthetic)
Use the SUS system autoclave of 3L to react.Adding formula in reaction vessel
Shown by 3, the 4-hexanedione (397g, 3.48mol), pyridine (138g, 1.74mol), methylene dichloride (1L) and stirring.Then at room temperature, forced with 0.1～0.5MPa
Shown carbonyl fluoride.Affirmation is along with heat release, and temperature is raised to 46.2 ℃.Continue then to add, until confirming that heat release, pressure reduce, reaction process is confirmed with GC.Confirm raw material 3, when the 4-hexanedione disappears, finishing reaction.After the reaction, carbonyl fluoride residual in the system is purged, carry out next step aftertreatment then.With the 1L pure water reaction soln is repeatedly cooled off at first, earlier.Gather the organic layer of lower floor then, the HCl solution 1L with 1N cools off once more again, removes residual pyridine.After the cooling, use MgSO
4Drying is used the vaporizer concentrated filtrate.At this moment, production
Shown trans-isomer(ide) and formula
Shown cis-isomeride, ratio are trans-isomer(ide): cis-isomeride=85: 15 (mol%).
With refining this enriched material of 5 grades of Oldershaw sieve plates (Oldershawcolumn that Sigma-Alderich company produces).
As a result, obtaining purity is the cut of 50 ℃ (3mmHg) of 99.1% (yield 70%), is trans-isomer(ide), and obtains the cut that purity is 70 ℃ (2mmHg) of 99.6% (yield 18%), is cis-isomeride.
Utilize NMR and IR to study these compounds,, confirm to be respectively 1,2-diethyl-1, the trans-isomer(ide) of 2-difluorinated ethylene carbonate and cis-isomeride by following appraising datum.
For trans-isomer(ide):
1H-NMR (deuterated acetone): 0.91～0.97 (m:6H), 1.61～1.85 (m:4H)
19F-NMR (deuterated acetone) :-194.7～-194.5 (m:2F)
IR：1853.8cm
-1
For cis-isomeride:
1H-NMR (deuterated acetone): 0.91～0.97 (m:6H), 1.61～1.85 (m:6H)
19F-NMR (deuterated acetone) :-113.9～-112.4 (m:2F)
IR：1853.8cm
-1
Embodiment 3 (anti-form-1,2-dimethyl-1,2-difluorinated ethylene carbonate synthetic)
Use the glass autoclave of 3L to react.Adding formula in reaction vessel
Shown by 2, the 3-dimethyl diketone (300g, 3.48mol), pyridine (138g, 1.74mol), methylene dichloride (500mL) and stirring.Under ice bath, use dropping funnel then, drip and in methylene dichloride (1L), be dissolved with formula
Shown triphosgene (409g, 1.39mol) solution that forms.Affirmation is along with heat release, and temperature is raised to 20 ℃.After dropping about two hours, purge and stir while carry out nitrogen, reaction process is confirmed with GC.Confirm raw material 2, when the 3-dimethyl diketone disappears, finishing reaction.After the reaction, carry out next step aftertreatment.With the 1L pure water reaction soln is repeatedly cooled off at first, earlier.Gather the organic layer of lower floor then, the HCl solution 1L with 1N cools off once more again, removes residual pyridine.After the cooling, use MgSO
4Drying is used the vaporizer concentrated filtrate.At this moment, production optionally
Shown anti-form-1,2-dimethyl-1,2-dichloro-NSC 11801.Then, by distilling refining residue, obtain the anti-form-1 of 150 ℃ of cuts of conduct of purity 99.3% (yield 80%), 2-dimethyl-1,2-dichloro-NSC 11801.
Utilize NMR and IR to study this compound,, confirm as anti-form-1,2-dimethyl-1,2-dichloro-NSC 11801 by following appraising datum.
1H-NMR (deuterated acetone): 1.81～2.00 (m:6H)
IR：1853.8cm
-1
In the glass autoclave of 3L, add this anti-form-1,2-dimethyl-1,2-dichloro-NSC 11801 500g (2.72mol) adds KF189g (3.26mol) and 1L acetonitrile again, reacts under refluxing.Reaction process is confirmed with GC.When confirming that raw material disappears, finish reaction.After reaction finishes, remove by filter the salt of generation, utilize rotatory evaporator from the filtrate of gained, distill, obtain residue (anti-form-1,2-dimethyl-1,2-difluorinated ethylene carbonate) except that desolvating with filtration unit.
With refining this residue of 5 grades of Oldershaw sieve plates (Oldershawcolumn that Sigma-Alderich company produces).
As a result, obtain the trans-isomer(ide) of 35 ℃ of (3mmHg) cuts of conduct of purity 99.3% (yield 80%).
Utilize NMR and IR to study this compound, consistent with the appraising datum of the trans-isomer(ide) of embodiment 1.
Embodiment 4 (have ehter bond and contain difluorinated ethylene carbonate synthetic of fluorine-free alkyl)
Use the SUS system autoclave of 3L to react.Adding formula in reaction vessel
Shown diketone (508g, 3.48mol), pyridine (138g, 1.74mol), methylene dichloride (1L) and stir.Then at room temperature, forced with 0.1～0.5MPa
Shown carbonyl fluoride.Affirmation is along with heat release, and temperature is raised to 46.2 ℃.Continue then to add, until confirming that heat release, pressure reduce, reaction process is confirmed with gas-chromatography (GC).When confirming that the raw material diketone disappears, finish reaction.After the reaction, carbonyl fluoride residual in the system is purged, carry out next step aftertreatment then.With the 1L pure water reaction soln is repeatedly cooled off at first, earlier.Gather the organic layer of lower floor then, the HCl solution 1L with 1N cools off once more again, removes residual pyridine.After the cooling, use MgSO
4Drying is used the vaporizer concentrated filtrate.At this moment, production
Listen trans-isomer(ide) and the formula shown
Shown cis-isomeride, ratio are trans-isomer(ide): cis-isomeride=80: 20 (mol%).
With refining this enriched material of 5 grades of Oldershaw sieve plates (Oldershawcolumn that Sigma-Alderich company produces).
As a result, obtaining purity is the cut of 52 ℃ (3mmHg) of 99.5% (yield 65%), is trans-isomer(ide), and obtains the cut that purity is 68 ℃ (2mmHg) of 99.6% (yield 25%), is cis-isomeride.
Utilize NMR and IR to study these compounds,, confirm to be respectively trans-isomer(ide) and the cis-isomeride that has ehter bond and contain the difluorinated ethylene carbonate of fluorine-free alkyl by following appraising datum.
For trans-isomer(ide):
1H-NMR (deuterated acetone): 3.21～3.24 (s:6H), 3.75～3.78 (m:4H)
19F-NMR (deuterated acetone) :-194.7～-194.5 (m:2F)
IR：1853.8cm
-1
For cis-isomeride:
1H-NMR (deuterated acetone): 3.21～3.24 (s:6H), 3.75～3.78 (m:4H)
19F-NMR (deuterated acetone) :-113.9～-112.4 (m:2F)
IR：1853.8cm
-1
Embodiment 5 (having the synthetic of the difluorinated ethylene carbonate that contains fluoroalkyl)
Use the SUS system autoclave of 3L to react.Adding formula in reaction vessel
Shown diketone (773g, 3.48mol), pyridine (138g, 1.74mol), methylene dichloride (1L) and stir.Then at room temperature, forced with 0.1～0.5MPa
Shown carbonyl fluoride.Affirmation is along with heat release, and temperature is raised to 46.2 ℃.Continue then to add, until confirming that heat release, pressure reduce, reaction process is confirmed with gas-chromatography (GC).When confirming that the raw material diketone disappears, finish reaction.After the reaction, carbonyl fluoride residual in the system is purged, carry out next step aftertreatment then.With the 1L pure water reaction soln is repeatedly cooled off at first, earlier.Gather the organic layer of lower floor then, the HCl solution 1L with 1N cools off once more again, removes residual pyridine.After the cooling, use the MgSO4 drying, use the vaporizer concentrated filtrate.At this moment, production
Shown trans-isomer(ide) and formula
Listen the cis-isomeride that shows, ratio is a trans-isomer(ide): cis-isomeride=70: 30 (mol%).
With refining this enriched material of 5 grades of Oldershaw sieve plates (Oldershawcolumn that Sigma-Alderich company produces).
As a result, obtaining purity is the cut of 40 ℃ (3mmHg) of 99.5% (yield 60%), is trans-isomer(ide), and obtains the cut that purity is 57 ℃ (2mmHg) of 99.6% (yield 20%), is cis-isomeride.
Utilize NMR and IR to study these compounds,, confirm to be respectively trans-isomer(ide) and cis-isomeride with the difluorinated ethylene carbonate that contains fluoroalkyl by following appraising datum.
For trans-isomer(ide):
1H-NMR (deuterated acetone): 2.15～2.25 (m:4H)
19F-NMR (deuterated acetone) :-89.5～-88.4 (t:6F) ,-194.7～-194.5 (m:2F)
IR：18538cm
-1
For cis-isomeride:
1H-NMR (deuterated acetone): 2.15～2.25 (m:4H)
19F-NMR (deuterated acetone) :-89.5～-88.4 (t:6F) ,-113.9～-112.4 (m:2F)
IR：1853.8cm
-1
Embodiment 6 (have ehter bond and have the synthetic of the difluorinated ethylene carbonate that contains fluoroalkyl)
Use the SUS system autoclave of 3L to react.Adding formula in reaction vessel
Shown diketone (981g, 3.48mol), pyridine (138g, 1.74mol), methylene dichloride (1L) and stir.Then at room temperature, forced with 0.1～0.5MPa
Shown carbonyl fluoride.Affirmation is along with heat release, and temperature is raised to 46.2 ℃.Continue then to add, until confirming that heat release, pressure reduce, reaction process is confirmed with gas-chromatography (GC).When confirming that the raw material diketone disappears, finish reaction.After the reaction, carbonyl fluoride residual in the system is purged, carry out next step aftertreatment then.With the 1L pure water reaction soln is repeatedly cooled off at first, earlier.Gather the organic layer of lower floor then, the HCl solution 1L with 1N cools off once more again, removes residual pyridine.After the cooling, use MgSO
4Drying is used the vaporizer concentrated filtrate.At this moment, production
Shown trans-isomer(ide) and formula
Shown cis-isomeride, ratio are trans-isomer(ide): cis-isomeride=85: 15 (mol%).
With refining this enriched material of 5 grades of Oldershaw sieve plates (Oldershawcolumn that Sigma-Alderich company produces).
As a result, obtaining purity is the cut of 55 ℃ (3mmHg) of 99.4% (yield 60%), is trans-isomer(ide), and obtains the cut that purity is 72 ℃ (2mmHg) of 99.6% (yield 20%), is cis-isomeride.
Utilize NMR and IR to study these compounds,, confirm to be respectively trans-isomer(ide) and the cis-isomeride that has ehter bond and have the difluorinated ethylene carbonate that contains fluoroalkyl by following appraising datum.
For trans-isomer(ide):
1H-NMR (deuterated acetone): 3.75～3.78 (m:4H), 3.87～3.89 (q:4H)
19F-NMR (deuterated acetone) :-194.7～-194.5 (m:2F) ,-89.5～-88.4 (t:6F)
IR：1853.8cm
-1
For cis-isomeride:
1H-NMR (deuterated acetone): 3.75～3.78 (m:4H), 3.87～3.89 (q:4H)
19F-NMR (deuterated acetone) :-113.9～-112.4 (m:2F) ,-89.5～-88.4 (t:6F)
IR：1853.8cm
-1。
Claims (8)
1. 1 shown in the formula (3), 2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate is characterized in that, makes the dione compounds reaction shown in carbonyl fluoride shown in the formula (1) and the formula (2),
Formula (1):
Formula (2):
In the formula (2), R
1And R
2Identical or different, be and can contain the alkyl that fluorine atom also can have the carbonatoms 1～4 of ehter bond,
Formula (3):
In the formula (3), R
1And R
2Identical with formula (2).
2. manufacture method as claimed in claim 1 is characterized in that, carbonyl fluoride makes by making the reaction of fluorizating agent and carbonyl chloride.
3. manufacture method as claimed in claim 1 or 2 is characterized in that, 1 of formula (3), and 2-dialkyl group-1,2-difluorinated ethylene carbonate are the mixture of cis-isomeride and trans-isomer(ide).
4. the cis-1 shown in the formula (3A), 2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate is characterized in that, to 1,2-dialkyl group-1, the cis-isomeride of 2-difluorinated ethylene carbonate and the mixture of trans-isomer(ide) carry out fractionation and obtain,
Formula (3A):
In the formula, R
1And R
2Identical or different, be and can contain the alkyl that fluorine atom also can have the carbonatoms 1～4 of ehter bond.
5. the anti-form-1 shown in the formula (3B), 2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate is characterized in that, to 1,2-dialkyl group-1, the cis-isomeride of 2-difluorinated ethylene carbonate and the mixture of trans-isomer(ide) carry out fractionation and obtain,
Formula (3B):
In the formula, R
1And R
2Identical or different, be and can contain the alkyl that fluorine atom also can have the carbonatoms 1～4 of ehter bond.
6. the cis-1 shown in the formula (3A), 2-dialkyl group-1, the 2-difluorinated ethylene carbonate,
Formula (3A):
In the formula, R
1And R
2Identical or different, be and can contain the alkyl that fluorine atom also can have the carbonatoms 1～4 of ehter bond.
7. the anti-form-1 shown in the formula (3B), 2-dialkyl group-1, the 2-difluorinated ethylene carbonate,
Formula (3B):
In the formula, R
1And R
2Identical or different, be and can contain the alkyl that fluorine atom also can have the carbonatoms 1～4 of ehter bond.
8. the anti-form-1 shown in the formula (3B), 2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate is characterized in that, comprising:
Make the dione compounds reaction shown in carbonyl compound shown in formula (4a) or the formula (4b) and the formula (2), the anti-form-1 shown in the manufacturing formula (5), 2-dialkyl group-1, the operation of 2-dihalo NSC 11801; With
Then, in organic solvent, make fluorizating agent and the anti-form-1 that obtains, 2-dialkyl group-1, the operation of 2-dihalo NSC 11801 reaction,
Formula (4a):
Formula (4b):
In formula (4a) and formula (4b), X
1Expression F, Cl or Br, X
2Expression Cl or Br, X
1And X
2Can be the same or different,
Formula (2):
In the formula (2), R
1And R
2Identical or different, be and can contain the alkyl that fluorine atom also can have the carbonatoms 1～4 of ehter bond,
Formula (5):
In the formula (5), X
1, X
2, R
1And R
2It is the same,
Formula (3B):
In the formula (3B), R
1And R
2Identical or different, be and can contain the alkyl that fluorine atom also can have the carbonatoms 1～4 of ehter bond.
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| JP5437622B2 (en) * | 2008-11-27 | 2014-03-12 | 関東電化工業株式会社 | Method for producing fluorine-containing cyclic ester using carbonyl fluoride |
| JP2010260817A (en) * | 2009-05-07 | 2010-11-18 | Daikin Ind Ltd | Method for producing 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one |
| US20140170506A1 (en) * | 2012-12-19 | 2014-06-19 | Panasonic Corporation | Nonaqueous solvent for electricity storage device, nonaqueous electrolytic solution and electricity storage device and lithium secondary battery using the same |
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| JPH08306364A (en) * | 1995-05-09 | 1996-11-22 | Sony Corp | Nonaqueous electrolytic solution and nonaqueous electrolyte battery |
| JP2000344763A (en) * | 1999-06-02 | 2000-12-12 | Kanto Denka Kogyo Co Ltd | Novel fluorine-containing cyclic carbonic ester and its production |
| JP2007188873A (en) * | 2005-12-13 | 2007-07-26 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte secondary battery |
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| US3455954A (en) * | 1966-03-31 | 1969-07-15 | Minnesota Mining & Mfg | Cyclic fluorocarbonates |
| DE2823981A1 (en) * | 1978-06-01 | 1979-12-13 | Hoechst Ag | METHOD FOR PRODUCING CARBONYL DIFLUORIDES |
| JPH05194465A (en) * | 1991-12-27 | 1993-08-03 | Warner Lambert Co | 2-aminomonomethoxycyclohexylamide useful as analgesic |
| US6630527B2 (en) * | 2001-10-19 | 2003-10-07 | General Electric Company | UV stabilized, impact modified polyester/polycarbonate blends, articles, and methods of manufacture thereof |
| FR2861390B1 (en) * | 2003-10-24 | 2006-01-21 | Arkema | STABILIZATION OF TRANS-1,2-DICHLORETHYLENE |
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| JPH08306364A (en) * | 1995-05-09 | 1996-11-22 | Sony Corp | Nonaqueous electrolytic solution and nonaqueous electrolyte battery |
| JP2000344763A (en) * | 1999-06-02 | 2000-12-12 | Kanto Denka Kogyo Co Ltd | Novel fluorine-containing cyclic carbonic ester and its production |
| JP2007188873A (en) * | 2005-12-13 | 2007-07-26 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte secondary battery |
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| CN102735367A (en) * | 2012-07-09 | 2012-10-17 | 深圳市敏杰电子科技有限公司 | Temperature sensor for measuring surface temperature |
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