CN101497597B - Preparation of 1,2-dialkyl-1,2-difluorinated ethylene carbonate - Google Patents

Preparation of 1,2-dialkyl-1,2-difluorinated ethylene carbonate Download PDF

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CN101497597B
CN101497597B CN200910008518.9A CN200910008518A CN101497597B CN 101497597 B CN101497597 B CN 101497597B CN 200910008518 A CN200910008518 A CN 200910008518A CN 101497597 B CN101497597 B CN 101497597B
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ethylene carbonate
cis
ide
isomer
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CN101497597A (en
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高明天
山内昭佳
谷明范
坂田英郎
中泽瞳
贺川米基璐
中园葵
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Daikin Industries Ltd
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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

1,2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate
Technical field
The present invention relates to manufacture 1,2-dialkyl group-1 with operation, 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-dioxa penta ring-2-ketone) is widely used as the solvent of the electrolytic solution for electrochemical device such as secondary cell and electrical condenser.
And, through the NSC 11801 of fluoridizing, owing to thering is the advantage of the excellences such as charge/discharge cycle characteristics and current efficiency, receive much concern, known have a difluorinated ethylene carbonate (4,4-bis-fluoro-1,3-dioxa penta ring-2-ketone, 4,5-bis-is fluoro-1,3-dioxa penta ring-2-ketone) etc. (patent documentation 1), and manufacture method that single fluorinated ethylene carbonate is fluoridized has been proposed.
Fluoridize in replacing NSC 11801 also (patent documentation 2～3) on the books, scope general formula very has widely been proposed in patent documentation 2, also enumerated a large amount of exemplary compounds, but the fluorinated ethylene carbonate in fact using in embodiment is only single fluorinated ethylene carbonate and difluorinated ethylene carbonate.
In patent documentation 3, recorded have suppress to form dendritic crystal effect there is methyl as substituent fluoro ethyl-carbonate.But in this patent documentation 3, the fluorinated ethylene carbonate using in fact is in an embodiment only 1-methyl-2,2-difluorinated ethylene carbonate is a kind of, and to 1,2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate is not recorded.
Patent documentation 1: Japanese patent laid-open 2000-344763 communique
Patent documentation 2: Japanese Patent Laid-Open 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 without NSC 11801, with operation, manufacture 1,2-dialkyl group-1, the method for 2-difluorinated ethylene carbonate.
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, the carbonyl fluoride shown in formula (1) is reacted with the dione compounds shown in formula (2),
Formula (1):
Formula (2):
In 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 formula (3), R 1and R 2identical with formula (2).
1 of formula (3), 2-dialkyl group-1,2-difluorinated ethylene carbonate obtains with the mixture of cis-isomeride and trans-isomer(ide), by 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 as cis-1 shown in formula (3A), 2-dialkyl group-1, the anti-form-1 shown in 2-difluorinated ethylene carbonate and formula (3B), 2-dialkyl group-1,2-difluorinated ethylene carbonate.
Formula (3A):
In formula, R 1and R 2the same.
Formula (3B):
In 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 manufactured.
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: the carbonyl compound shown in formula (4a) or formula (4b) is reacted, the anti-form-1 shown in manufacture formula (5) with the dione compounds shown in formula (2), 2-dialkyl group-1, the operation of 2-dihalo NSC 11801; Then, in organic solvent, make fluorizating agent and the anti-form-1 obtaining, 2-dialkyl group-1, the operation of 2-dihalo NSC 11801 reaction.
Formula (4a):
Formula (4b):
In formula (4a) and formula (4b), X 1represent F, Cl or Br, X 2represent Cl or Br, X 1and X 2can be the same or different,
Formula (2):
In 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 formula (5), X 1, X 2, R 1and R 2it is the same,
Formula (3B):
In 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.
Invention effect
Manufacturing method according to the invention, can enough operations manufacture 1,2-dialkyl group-1,2-difluorinated ethylene carbonate with high yield.
Embodiment
Of the present invention 1,2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate, is characterized in that, the carbonyl fluoride of formula (1) is reacted with the dione compounds shown in formula (2).
Formula (2):
In 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 known compound, for example, and can be by making fluorizating agent react and synthesize with carbonyl chloride.
As fluorizating agent, except hydrofluoric acid, fluorine gas, the compound shown in preferred illustration formula MF (in formula, M is alkali metal atom or quaternary ammonium cation) also.MF specifically can enumerate the compound of KF, NaF, CsF, LiF, quaternary ammonium cation and fluorine anion etc.
The dione compounds of formula (2) is also known compound.R 1and R 2for the alkyl can with ehter bond of carbonatoms 1～4 or containing fluoroalkyl.The viscosity of considering gained carbonic ether is low, and the carbonatoms of alkyl is up to 4, is particularly preferably 1～3.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 the fluorine-free alkyl with ehter bond, for example, can enumerate the following compound of Denging.
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 with ehter bond, for example, can enumerate the following compound of Denging.
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 exemplify the following compound of Denging, but be not limited to this.
Carbonyl fluoride (1) reacts under the existence of alkali with dione compounds (2), in solvent, quantitatively carries out, and generates 1,2-dialkyl group-1,2-difluorinated ethylene carbonate.
As alkali, can use mineral alkali, organic bases arbitrarily, particularly except the tertiary amines such as pyridine, triethylamine, also preferred primary amine, secondary amine etc.
As solvent, be preferably organic solvent, for example, can exemplify methylene dichloride, chloroform, tetrahydrofuran (THF), dimethyl acetamide, dimethyl formamide, glyme kind solvent, acetonitrile, acetone, toluene, ethyl acetate isopolarity solvent etc.
Reaction is fully carried out under 0～40 ℃ of temperature of reaction, normal atmosphere or pressurized conditions.Wherein, about reaction conditions, can also adopt by carbonyl chloride, react synthesizing fluoro carbonic acid vinyl acetate with dione compounds reaction conditions (for example, SYNTHETIC COMMUNICATIONS, 23 (6), pp847-853 (1993), or Journal of Fluorine Chemistry, the condition of recording in 120, pp105-110 (2003)).
By manufacture method of the present invention, obtained 1,2-dialkyl group-1,2-difluorinated ethylene carbonate is the mixture of cis-isomeride and trans-isomer(ide).Directly former state is used this mixture as the additive of nonaqueous electrolytic solution, also it can be emanated respectively as using after cis-isomeride and 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.
Fractionation can adopt to utilize such as Oldershaw sieve plate (Oldershaw) or blister-type separator column, concentric(al) circles tubular separator column, the known method that revolves the fractionators such as banding pattern separator column easily to be carried out.
Isolated cis-1,2-dialkyl group-1,2-difluorinated ethylene carbonate is the novel cpd shown in formula (3A), and anti-form-1,2-dialkyl group-1,2-difluorinated ethylene carbonate is the novel cpd shown in formula (3B).
(formula 3A):
(formula 3B):
And, as optionally manufacturing anti-form-1,2-dialkyl group-1, the method of 2-difluorinated ethylene carbonate has following method, it comprises makes the carbonyl compound shown in formula (4a) or formula (4b) react with the dione compounds shown in formula (2), anti-form-1 shown in manufacture 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 obtaining, 2-dialkyl group-1, the operation of 2-dihalo NSC 11801 reaction.
Formula (4a):
Formula (4b):
In formula (4a) and formula (4b), X 1represent F, Cl or Br, X 2represent Cl or Br, X 1and X 2can be the same or different,
Formula (2):
In 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 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 larger 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 by halogen atom, can optionally manufacture anti-form-1,2-dialkyl group-1,2-difluorinated ethylene carbonate (purity 99.5%).
As the compound shown in 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 formula (4b), for example, can enumerate
shown triphosgene,
or
deng.
The reaction of leading portion operation can carried out with under the same reaction conditions of reacting of above-mentioned carbonyl fluoride and dione compounds (2).And the reaction of back segment operation can be in conventional organic solvent the condition of fluoridation under carry out.Organic solvent is preferably polar solvent, can enumerate the solvent that above-mentioned carbonyl fluoride is used in reacting with dione compounds (2).Fluorizating agent also can adopt carbonyl chloride is transformed to the fluorizating agent using 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 form stable protective membrane effectively on the electrode (negative or positive electrode) of lithium secondary battery, 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 analytical procedure that following examples are used 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 producing with Perkin Elmer company is at room temperature measuring.
Embodiment 1 (1,2-dimethyl-1,2-difluorinated ethylene carbonate synthetic)
Use the SUS autoclave processed of 3L to react.In reaction vessel, add formula shown by 2,3-dimethyl diketone (300g, 3.48mol), pyridine (138g, 1.74mol), methylene dichloride (1L) also stir.Then at room temperature, forced with 0.1～0.5MPa shown carbonyl fluoride.Confirmation is along with heat release, and temperature is raised to 46.2 ℃.Then continue to add, until cannot confirm heat release, pressure decreased, gas-chromatography for reaction process (GC) is confirmed.Confirm raw material 2, when 3-dimethyl diketone disappears, finishing reaction.After reaction, carbonyl fluoride residual in system is purged, then carry out next step aftertreatment.First, first with 1L pure water, to reaction soln, carry out repeatedly cooling.Then gather the organic layer of lower floor, then with the HCl solution 1L of 1N, again carry out coolingly, remove thus residual pyridine.After cooling, use MgSO 4dry, use vaporizer concentrated filtrate.Now, production shown trans-isomer(ide) and formula shown cis-isomeride, ratio is 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, by following appraising datum, confirm to be respectively 1,2-dimethyl-1, the trans-isomer(ide) of 2-difluorinated ethylene carbonate and cis-isomeride.
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 autoclave processed of 3L to react.In reaction vessel, add formula shown by 3,4-hexanedione (397g, 3.48mol), pyridine (138g, 1.74mol), methylene dichloride (1L) also stir.Then at room temperature, forced with 0.1～0.5MPa shown carbonyl fluoride.Confirmation is along with heat release, and temperature is raised to 46.2 ℃.Then continue to add, until cannot confirm heat release, pressure decreased, reaction process is confirmed with GC.Confirm raw material 3, when 4-hexanedione disappears, finishing reaction.After reaction, carbonyl fluoride residual in system is purged, then carry out next step aftertreatment.First, first with 1L pure water, to reaction soln, carry out repeatedly cooling.Then gather the organic layer of lower floor, then with the HCl solution 1L of 1N, again carry out coolingly, remove residual pyridine.After cooling, use MgSO 4dry, use vaporizer concentrated filtrate.Now, production shown trans-isomer(ide) and formula shown cis-isomeride, ratio is 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, by following appraising datum, confirm to be respectively 1,2-diethyl-1, the trans-isomer(ide) of 2-difluorinated ethylene carbonate and cis-isomeride.
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 processed of 3L to react.In reaction vessel, add formula shown by 2,3-dimethyl diketone (300g, 3.48mol), pyridine (138g, 1.74mol), methylene dichloride (500mL) also stir.Then under ice bath, use dropping funnel, drip and be dissolved with formula in methylene dichloride (1L) shown triphosgene (409g, 1.39mol) and the solution that forms.Confirmation is along with heat release, and temperature is raised to 20 ℃.After dropping approximately two hours, while carry out nitrogen, purge and stir, reaction process is confirmed with GC.Confirm raw material 2, when 3-dimethyl diketone disappears, finishing reaction.After reaction, carry out next step aftertreatment.First, first with 1L pure water, to reaction soln, carry out repeatedly cooling.Then gather the organic layer of lower floor, then with the HCl solution 1L of 1N, again carry out coolingly, remove residual pyridine.After cooling, use MgSO 4dry, use vaporizer concentrated filtrate.Now, 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, by following appraising datum, confirm as anti-form-1,2-dimethyl-1,2-dichloro-NSC 11801.
1h-NMR (deuterated acetone): 1.81～2.00 (m:6H)
IR：1853.8cm -1
In the glass autoclave processed of 3L, add this anti-form-1,2-dimethyl-1,2-dichloro-NSC 11801 500g (2.72mol), then add KF189g (3.26mol) and 1L acetonitrile, under refluxing, react.Reaction process is confirmed with GC.When confirming that raw material disappears, finish reaction.After reaction finishes, with filtration unit, remove by filter the salt of generation, utilize rotatory evaporator from the filtrate of gained, to distill except desolventizing, obtain residue (anti-form-1,2-dimethyl-1,2-difluorinated ethylene carbonate).
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 (synthesizing of the difluorinated ethylene carbonate that there is ehter bond and contain fluorine-free alkyl)
Use the SUS autoclave processed of 3L to react.In reaction vessel, add formula shown diketone (508g, 3.48mol), pyridine (138g, 1.74mol), methylene dichloride (1L) also stir.Then at room temperature, forced with 0.1～0.5MPa shown carbonyl fluoride.Confirmation is along with heat release, and temperature is raised to 46.2 ℃.Then continue to add, until cannot confirm heat release, pressure decreased, gas-chromatography for reaction process (GC) is confirmed.When confirming that raw material diketone disappears, finish reaction.After reaction, carbonyl fluoride residual in system is purged, then carry out next step aftertreatment.First, first with 1L pure water, to reaction soln, carry out repeatedly cooling.Then gather the organic layer of lower floor, then with the HCl solution 1L of 1N, again carry out coolingly, remove residual pyridine.After cooling, use MgSO 4dry, use vaporizer concentrated filtrate.Now, production shown trans-isomer(ide) and formula shown cis-isomeride, ratio is 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, by following appraising datum, confirm to be respectively trans-isomer(ide) and the cis-isomeride of the difluorinated ethylene carbonate that there is ehter bond and contain fluorine-free alkyl.
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 (have containing the difluorinated ethylene carbonate of fluoroalkyl synthetic)
Use the SUS autoclave processed of 3L to react.In reaction vessel, add formula shown diketone (773g, 3.48mol), pyridine (138g, 1.74mol), methylene dichloride (1L) also stir.Then at room temperature, forced with 0.1～0.5MPa shown carbonyl fluoride.Confirmation is along with heat release, and temperature is raised to 46.2 ℃.Then continue to add, until cannot confirm heat release, pressure decreased, gas-chromatography for reaction process (GC) is confirmed.When confirming that raw material diketone disappears, finish reaction.After reaction, carbonyl fluoride residual in system is purged, then carry out next step aftertreatment.First, first with 1L pure water, to reaction soln, carry out repeatedly cooling.Then gather the organic layer of lower floor, then with the HCl solution 1L of 1N, again carry out coolingly, remove residual pyridine.After cooling, use MgSO 4dry, use vaporizer concentrated filtrate.Now, production shown trans-isomer(ide) and formula shown cis-isomeride, ratio is 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, by following appraising datum, confirm to be respectively trans-isomer(ide) and the cis-isomeride having containing the difluorinated ethylene carbonate of fluoroalkyl.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：1853.8cm -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 (there is ehter bond and there is synthetic containing the difluorinated ethylene carbonate of fluoroalkyl)
Use the SUS autoclave processed of 3L to react.In reaction vessel, add formula shown diketone (981g, 3.48mol), pyridine (138g, 1.74mol), methylene dichloride (1L) also stir.Then at room temperature, forced with 0.1～0.5MPa shown carbonyl fluoride.Confirmation is along with heat release, and temperature is raised to 46.2 ℃.Then continue to add, until cannot confirm heat release, pressure decreased, gas-chromatography for reaction process (GC) is confirmed.When confirming that raw material diketone disappears, finish reaction.After reaction, carbonyl fluoride residual in system is purged, then carry out next step aftertreatment.First, first with 1L pure water, to reaction soln, carry out repeatedly cooling.Then gather the organic layer of lower floor, then with the HCl solution 1L of 1N, again carry out coolingly, remove residual pyridine.After cooling, use MgSO 4dry, use vaporizer concentrated filtrate.Now, production shown trans-isomer(ide) and formula shown cis-isomeride, ratio is 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, by following appraising datum, confirm to be respectively to there is ehter bond and there is trans-isomer(ide) and the cis-isomeride containing the difluorinated ethylene carbonate of fluoroalkyl.
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 (5)

1. 1 shown in a formula (3), 2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate, is characterized in that, the carbonyl fluoride shown in formula (1) is reacted with the dione compounds shown in formula (2),
In 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,
In formula (3), R 1and R 2identical with formula (2).
2. manufacture method as claimed in claim 1, is characterized in that, carbonyl fluoride is by making fluorizating agent react and make with 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 is the mixture of cis-isomeride and trans-isomer(ide).
4. cis-1 shown in a formula (3A), 2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate, it is characterized in that, in manufacture method claimed in claim 1, further 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
In 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 a formula (3B), 2-dialkyl group-1, the manufacture method of 2-difluorinated ethylene carbonate, it is characterized in that, in manufacture method claimed in claim 1, further 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
In 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.
CN200910008518.9A 2008-01-29 2009-01-23 Preparation of 1,2-dialkyl-1,2-difluorinated ethylene carbonate Active CN101497597B (en)

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