WO2009107449A1 - フッ素化1,3-ジオキソラン-2-オンの製造方法 - Google Patents
フッ素化1,3-ジオキソラン-2-オンの製造方法 Download PDFInfo
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- WO2009107449A1 WO2009107449A1 PCT/JP2009/051590 JP2009051590W WO2009107449A1 WO 2009107449 A1 WO2009107449 A1 WO 2009107449A1 JP 2009051590 W JP2009051590 W JP 2009051590W WO 2009107449 A1 WO2009107449 A1 WO 2009107449A1
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- hydrofluoric acid
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- addition salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/42—Halogen atoms or nitro radicals
Definitions
- the present invention relates to a method for producing fluorinated 1,3-dioxolan-2-one.
- Fluorinated 1,3-dioxolan-2-one represented by 4-fluoro-1,3-dioxolan-2-one (hereinafter sometimes referred to as “F-EC”) (hereinafter referred to as “fluorinated EC”) Is sometimes attracting attention as a solvent for an electrolytic solution used in an electrochemical device such as a secondary battery or a capacitor because of its excellent charge / discharge cycle characteristics and current efficiency.
- F-EC Fluorinated 1,3-dioxolan-2-one represented by 4-fluoro-1,3-dioxolan-2-one
- Patent Document 1 discloses that a lithium ion secondary battery using this compound as a solvent has excellent charge / discharge efficiency and good charge / discharge compared with a secondary battery using a solvent not substituted with fluorine. It is disclosed to exhibit cycle characteristics.
- fluorinated EC As a manufacturing method of this fluorinated EC, (1) A method in which 1,3-dioxolan-2-one is used as a starting material and fluorinated directly with fluorine gas; (2) As a fluorinating agent, a halogen (Cl, Br or I) 1,3-dioxolan-2-one (hereinafter referred to as “halogenated EC”) using an approximately equal amount of metal fluoride may be used. This does not include the target “fluorinated EC. The same applies hereinafter.” Methods are known in which halogen atoms (Cl, Br, or I) are substituted with fluorine atoms (Patent Documents 2 to 4).
- Patent Document 2 4-chloro-1,3-dioxolan-2-one (hereinafter sometimes referred to as “Cl-EC”) and potassium fluoride are mixed and reacted to yield F-EC in a yield of 70%.
- Cl-EC 4-chloro-1,3-dioxolan-2-one
- potassium fluoride potassium fluoride
- Patent Documents 3 and 4 Cl-EC and potassium fluoride are reacted in acetonitrile at 80 to 85 ° C. for 11 hours using 1.2 equivalents of potassium fluoride, and the starting material Cl-EC is converted. A crude product of F-EC is obtained with a yield of 87.5% (if recrystallized, F-EC can be collected in 85% of the crude product).
- JP-A-62-290072 International Publication No. 98/150424 Pamphlet Japanese Patent Laid-Open No. 2007-8826 JP 2007-8825 A
- the present invention provides a method for producing fluorinated EC in a short time while maintaining a high yield by a liquid-liquid reaction in a production method in which halogenated EC is used as a starting material and fluorinated with a fluorinating agent.
- the purpose is to do.
- the present invention In an organic solvent, the formula (1): Wherein X 1 , X 2 , X 3 and X 4 are the same or different and all are H, CH 3 , Cl, Br, I or CR 3 (at least one of R is Cl, Br or I And the rest are H. However, at least one of X 1 to X 4 is Cl, Br, I or CR 3 )
- the present invention relates to a process for producing fluorinated 1,3-dioxolan-2-one comprising a fluorination step (A) in which a hydrofluoric acid addition salt of an amine is reacted with the 1,3-dioxolan-2-one derivative represented by formula (1).
- the molar ratio n of hydrofluoric acid to amine in the hydrofluoric acid addition salt of amine is preferably 1 to 10 from the viewpoint of high reactivity.
- the molar ratio m of hydrofluoric acid addition salt of amine to 1 mol of Cl, Br and / or I atom is 0.5-4. Is preferable from the viewpoint of high reactivity.
- hydrofluoric acid addition salt of amine Formula (2): (Wherein R 1 , R 2 and R 3 are the same or different, and all are H or an alkyl group having 1 to 4 carbon atoms; n is 1 to 10), or formula (3): (Wherein R 4 is a nitrogen-containing aromatic ring having 4 to 5 carbon atoms including —N ⁇ or —NH—; n is 1 to 10) Is preferable from the viewpoint of good solubility in an aprotic solvent, and in particular, from the viewpoint of good reactivity of the substitution reaction, in formulas (2) and (3), n is 1 to 3, Is preferably a compound having a value in the range of 1 to 2.
- the organic solvent is preferably an aprotic solvent from the viewpoint of improving nucleophilicity.
- the organic solvent is preferably a nitrile solvent, a cyclic ether solvent, a chain ether solvent, an ester solvent, a chain carbonate solvent, a ketone solvent or an amide solvent.
- step (C) of treating with an antacid is included because halogen roots represented by chlorine roots can be reduced.
- halogenated EC in a production method in which halogenated EC is used as a starting material and this is fluorinated with a fluorinating agent, a high yield is obtained in a liquid-liquid reaction by using an amine hydrofluoric acid addition salt as the fluorinating agent Fluorinated EC can be produced in a short time while maintaining the above.
- the halogenated EC is reacted with a hydrofluoric acid addition salt of an amine in the step (A) of fluorinating the halogenated EC represented by the formula (1) in an organic solvent.
- the starting halogenated EC is represented by the formula (1): Wherein X 1 , X 2 , X 3 and X 4 are the same or different and all are H, CH 3 , Cl, Br, I or CR 3 (at least one of R is Cl, Br or I And the rest are H. However, at least one of X 1 to X 4 is Cl, Br, I or CR 3 ) It is a compound shown by these.
- X is preferably Cl because it can be chlorinated using Cl 2 when it is synthesized in large quantities and can be produced at low cost.
- the following are preferable from the viewpoint of good stability of the compound.
- halogenated EC is fluorinated with an amine hydrofluoric acid addition salt. Therefore, a process such as a solid removal process is not necessary in that no solid is used.
- the amine hydrofluoric acid addition salt to be used is preferably soluble in an organic solvent from the viewpoint of the uniformity and smoothness of the reaction.
- the compounds represented by the following formulas (2) and (3) are preferable from the viewpoint of good solubility in an aprotic solvent.
- R 1 , R 2 and R 3 are the same or different and all are H or an alkyl group having 1 to 4 carbon atoms; n is 1 to 10, preferably 1 to 5
- This amine hydrofluoric acid addition salt (2) is preferred because it can be produced at low cost and can be produced by selecting the value of n.
- trimethylamine n hydrofluoric acid addition salt triethylamine n hydrofluoric acid addition salt, tripropylamine n hydrofluoric acid addition salt, triisopropylamine n hydrofluoric acid addition salt, tributylamine n hydrofluoric acid addition salt, triisobutylamine n hydrofluoric acid addition salt.
- Acid addition salt tri-t-butylamine n hydrofluoric acid addition salt, dimethylamine n hydrofluoric acid addition salt, diethylamine n hydrofluoric acid addition salt, dipropylamine n hydrofluoric acid addition salt, diisopropylamine n hydrofluoric acid addition salt, dibutylamine n hydrofluoric acid Acid addition salt, diisobutylamine n hydrofluoric acid addition salt, di-t-butylamine n hydrofluoric acid addition salt, methylamine n hydrofluoric acid addition salt, ethylamine n hydrofluoric acid addition salt, propylamine n hydrofluoric acid addition salt, isopropylamine n hydrofluoric acid Addition salt, butylamine n hydrofluoric acid addition salt, isobutylamine n hydrofluoric acid addition salt, t
- Such as butylamine n hydrofluoric acid addition salt (n is 1-10) can be mentioned.
- R 4 is a nitrogen-containing aromatic ring having 4 to 5 carbon atoms including —N ⁇ or —NH—; n is 1 to 10, preferably 1 to 5)
- This amine hydrofluoric acid addition salt (3) is preferable because it has higher nucleophilicity than the compound of formula (2).
- n of hydrofluoric acid to amine in the hydrofluoric acid addition salt of amine is not particularly limited, but is preferably 1 to 10.
- n is less than 1, vinylene carbonate may be generated instead of the target fluorinated EC, and when it exceeds 10, the reactivity of fluorination may be reduced.
- n has a value in the range of 1 to 3, more preferably in the range of 1 to 2.5 because of high fluorination reactivity and high selectivity for fluorine substitution of halogen atoms (Cl, Br, I). preferable.
- hydrofluoric acid molar ratio n of hydrofluoric acid to amine (hereinafter sometimes referred to as “hydrofluoric acid molar ratio n”) in the hydrofluoric acid addition salt of amine can be adjusted, for example, by the following method.
- the amine used in combination with the amine hydrofluoric acid addition salt may be the same as or different from the amine constituting the amine hydrofluoric acid addition salt, but the same one is preferred from the viewpoint of high fluorination reactivity.
- amine to be used in combination include the amine moiety compounds exemplified in the above-mentioned amine hydrofluoric acid addition salt.
- the amine hydrofluoric acid addition salt and the amine may be added to the reaction system after the amine hydrofluoric acid addition salt and the amine are mixed in advance, or one of them may be added to the reaction system and the other may be added. .
- the reaction of the halogenated EC and the amine hydrofluoric acid addition salt in the reaction step of the present invention is performed in an organic solvent. Since the reactivity is lowered in the presence of water, it is desirable to carry out in a substantially anhydrous state.
- Fluorination reaction in the presence of amine by hydrofluoric acid of halogen atoms in the starting halogenated EC proceeds in an equimolar ratio.
- the molar ratio m between the halogenated EC and the amine of the amine hydrofluoric acid addition salt also affects the fluorination reaction. This is because when the molar ratio of amine to halogenated EC is within a certain range, the halogen atoms (Cl, Br, I) of the halogenated EC are activated so as to easily undergo a fluorination reaction with hydrofluoric acid. It is.
- the amine molar ratio m is preferably 0.5 to 4 from the viewpoint of good reaction activity of halogenated EC. Furthermore, 1.0 or more, preferably 1.5 or more, more preferably 2.0 or more, still more preferably 2.1 or more is used.
- the upper limit of the amine molar ratio m is not particularly limited, but is about 4 for economic reasons.
- the organic solvent for example, nitromethane, nitrobenzene, chloroform, dichloromethane, toluene and any organic solvent can be used.
- an aprotic organic solvent is preferable from the viewpoint of improving nucleophilicity.
- the aprotic organic solvent include nitrile solvents, cyclic ether solvents, chain ether solvents, ester solvents, chain carbonate solvents, ketone solvents, and amide solvents. These may be used alone or in combination of two or more.
- Nitrile solvents such as acetonitrile and benzonitrile; cyclic ether solvents such as tetrahydrofuran and 1,4-dioxane; chain ether solvents such as diglyme and triglyme; ester solvents such as methyl acetate and acetic acid Ethyl, butyl acetate, ⁇ -butyrolactone, etc .; chain carbonate solvents such as dimethyl carbonate and diethyl carbonate; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone; amide solvents such as dimethylformamide, N— Examples include methyl pyrrolidone.
- a water-insoluble solvent is preferable.
- methyl acetate, ethyl acetate, butyl acetate, dimethyl carbonate, diethyl carbonate, methyl ethyl ketone, acetone, and methyl isobutyl ketone are preferable.
- the concentration of the starting halogenated EC in the organic solvent can be in a wide range, but is preferably 5% by weight or more, and more preferably 20% by weight or more from the viewpoint of easy control of the reaction.
- the upper limit is preferably 60% by weight, more preferably 50% by weight.
- the reaction temperature is preferably 30 ° C. or higher, more preferably 50 ° C. or higher from the viewpoint of ease of handling.
- the upper limit is the boiling point of the organic solvent used.
- the reaction proceeds faster than the reaction in the conventional production method, and with the same yield, the reaction is completed in half or less of the conventional reaction time.
- the yield is 80 to 85%, which is equal to or higher than the conventional one.
- reaction product mixture obtained in the reaction step is subjected to an intermediate treatment step as necessary, and then purified fluorinated EC is obtained in the rectification step (B).
- an Oldershaw type column perforated plate type
- a plate type column bubble bell type or the like
- the distillation temperature is preferably 50 to 200 ° C.
- the antacid treatment step (C) for removing the halogen radical existing in the reaction system by contacting with the antacid through the production method of the present invention, and the organic before the rectification step (B).
- steps are optional, but can be appropriately performed before, after or during the fluorination step (A) and the rectification step (B).
- the antacid treatment step (C) is a step of removing halogen radicals present in the reaction system with an antacid, and becomes an obstacle when using fluorinated EC as a solvent for a non-aqueous electrolyte, for example. Since the halogen root can be removed with high efficiency, before step (A), in step (A), after step (A), before step (B), in step (B) and after step (B).
- the step (C) of treating with an antacid is preferably performed at least once.
- halogen roots can be removed with high efficiency, and the halogen radicals remaining in the final product (purified F-EC) can be reduced to 10 ppm or less, further 1 ppm or less, particularly 0.1 ppm or less.
- the “halogen radical” means hydrogen chloride (HCl) or chlorine (Cl 2 ) by-produced in the fluorination reaction, and further, a halogen ion (Cl ⁇ ,) present as an impurity in the starting halogenated EC. Br ⁇ , I ⁇ ), etc .; fluorine ions (F ⁇ ), fluorine (F 2 ), hydrogen fluoride (HF), etc. derived from amine hydrofluoric acid addition salts; derived from impurities that are by-products of the fluorination reaction fluorine ions (F -) refers to such.
- the halogen radical does not include unreacted halogenated EC and the target fluorinated EC.
- a compound having a function of adsorbing and reacting halogen radicals is effective.
- Examples of the compound having a function of adsorbing halogen roots include metal compounds and inorganic porous materials.
- the metal compound is preferably an alkali metal or alkaline earth metal oxide, hydroxide, carboxylate, carbonate, bicarbonate, silicate, phosphate, phosphite, borate, etc.
- An oxide of a group IVa metal of the periodic table, a basic carboxylate, a basic carbonate, a basic sulfate, a tribasic sulfate, a basic phosphite, and the like can be used.
- Such metal compounds include magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, Magnesium carbonate, calcium carbonate, barium carbonate, calcium silicate, potassium acetate, calcium acetate, calcium stearate, zinc stearate, calcium phosphite, iron oxide, tin oxide, red lead, white lead, dibasic lead phthalate, dibasic Examples thereof include lead carbonate and aluminum hydroxide.
- inorganic porous material for example, silica, natural zeolite, synthetic zeolite, alumina, molecular sieve (3A, 4A, 5A, 13X, etc.), various hydrotalcites, various commercially available porous antacids, etc. are used. be able to.
- commercially available porous antacids include inorganic porous bodies made of amorphous silica / alumina gel (Secard made by Shinagawa Kasei Co., Ltd., trade name), hydrate porous bodies containing aluminum and iron ( An example is Alfemite manufactured by Mizusawa Chemical Co., Ltd. (trade name).
- antacids may be used alone or in combination of two or more.
- alkaline earth metal oxides, alkaline earth metal hydrogen carbonates, alkaline earth metal phosphates, alkaline earth metal carboxylic acids in particular, can suppress the decomposition of fluorinated EC.
- Low nucleophilicity such as salt, alkali metal hydrogen carbonate, alkali metal phosphate, alkali metal carboxylate, silicon oxide, aluminum oxide, silicon aluminum composite oxide, or two or more of these Antacids are preferred.
- Particularly preferred antacids are trisodium phosphate, sodium acetate, potassium acetate, potassium hydrogen carbonate, antacid porous materials, silicon oxide, aluminum oxide, silicon aluminum composite oxide, or these Two or more kinds of porous materials are preferable.
- the antacid treatment step (C) comprises the following steps (1) to (6), specifically, before step (A), during step (A), after step (A), and after step (B) Before, during step (B) and after step (B).
- fluorination step (A) In the fluorination step (A), in addition to chlorine radicals in the starting material, fluorine (F 2 ), hydrogen fluoride (HF), fluorine ions derived from fluorinating agents (fluorine gas, hydrofluoric acid, MF, etc.) In addition to (F ⁇ ) and the like, there are fluorine ions derived from impurities which are by-products of the fluorination reaction, so these halogen radicals are removed.
- fluorine (F 2 ) in addition to chlorine radicals in the starting material, fluorine (F 2 ), hydrogen fluoride (HF), fluorine ions derived from fluorinating agents (fluorine gas, hydrofluoric acid, MF, etc.)
- fluorine ions derived from impurities which are by-products of the fluorination reaction, so these halogen radicals are removed.
- the halogen root similar to the above (3) is present. Because they are present, these halogen roots are removed. As described above, in the distillation (rectification), it is difficult to remove chlorine radicals (Cl ⁇ , HCl, Cl 2 etc.) and fluorine radicals (F ⁇ , HF, F 2 etc.).
- the antacid treatment is performed in at least one of these stages (1) to (6).
- an antacid treatment is performed after the rectification step (B)
- impurities may be mixed in. Therefore, it is desirable that the antacid treatment be performed at stages (1) to (5) as much as possible.
- the antacid treatment is: (I) starting material, reaction product, residue after removal of organic solvent, antacid is added to the fraction after rectification and thoroughly mixed; (II) starting material, reaction A method in which the product solution, the residue after removal of the organic solvent, and the fraction after rectification are passed through a column filled with an antacid; and further, (III) distillation is performed before step (B) or during rectification. And / or a method of filling a rectification column with an antacid.
- the treatment temperature in these cases is usually about room temperature to 130 ° C., preferably about room temperature to 100 ° C.
- the temperature is preferably about 40 to 100 ° C. If the treatment temperature is too high, decomposition of the halogenated EC of the starting material and the fluorinated EC that is the target product may be caused.
- the treatment time is usually about 3 to 5 hours.
- a particularly desirable method is the method (III) because it is easy to scale up.
- the amount of antacid used depends on various conditions such as the type of halogenated EC or fluorinated EC to be treated, the type of antacid used, the residual amount of halogen radicals, the content of the polyfluoro compound, etc. Although it cannot be generally specified, it is usually preferable to set the amount to about 1 to 50 parts by mass, preferably about 1 to 10 parts by mass with respect to 100 parts by mass of halogenated EC or fluorinated EC. From the point, it is more preferable.
- the starting material (halogenated EC) is treated in advance before the fluorination step (A). It is preferable.
- the antacid treatment step (C) after the fluorination step (A) and before the rectification step (B) because halogen roots can be minimized.
- the antacid treatment step (C) during the rectification step (B) (that is, at the same time) because it is easy to scale up.
- the F-EC thus obtained has a high purity (99% or more, further 99.5% or more), and the content of impurities such as halogen radicals is reduced to less than 1 ppm. As a result, coloration with time does not occur, and the inhibiting factor is removed as a solvent for the electrolytic solution.
- the antacid treatment step (C) and the rectification step (B) may be repeated.
- the organic solvent is distilled off from the filtrate at 70 to 90 ° C. using, for example, a rotary evaporator to obtain crude F-EC.
- the solid content removal step (E) is a necessary step when the antacid treatment step (C) is performed, and is generated in the reaction step in the conventional method using a metal fluoride as a fluorinating agent. This is different from the filtration step of removing the solid matter to be filtered.
- the hydrofluoric acid addition salt of amine is dissolved in an organic solvent, so that filtration treatment after the fluorination reaction is unnecessary.
- cleaning is performed at 0 to 50 ° C. using, for example, pure water or ultrapure water.
- Example 1 Fluorination reaction using amine hydrofluoric acid addition salt of formula (2)
- Triethylamine trifluoride addition salt (3.2 g: 19.6 mmol), triethylamine (1.3 g: 12.8 mmol), ethyl acetate (5 ml) and acetonitrile (1 ml) were added to a 30 ml three-necked flask equipped with a reflux condenser.
- Hydrofluoric acid molar ratio n 1.8
- This was charged with 4-chloro-1,3-dioxolan-2-one (Cl-EC. 2.0 g: 16.3 mmol, amine molar ratio m 2), and subjected to fluorination reaction at a reaction temperature of 80 ° C. over 1 hour. I did it.
- the obtained organic layer was analyzed by gas chromatography (GC), gas chromatography / mass spectrometry (GC / MS) and 19 F-NMR.
- GC gas chromatography
- MS gas chromatography / mass spectrometry
- F-EC 4-fluoro-1, 3-Dioxolan-2-one
- Example 2 the amount of triethylamine trifluoride addition salt and triethylamine, the type and amount of organic solvent, the reaction temperature, and the reaction time were changed as shown in Table 1, and F-EC was changed in the same manner as in Example 1.
- Example 15 F-EC was produced in the same manner as in Example 1 except that triethylamine was not used in Example 1.
- the obtained organic layer was subjected to gas chromatography (GC) and gas chromatography / mass spectrometry (GC / MS).
- GC gas chromatography
- MS gas chromatography / mass spectrometry
- 19 F-NMR analysis to examine Cl-EC conversion and F-EC selectivity. The results are shown in Table 1.
- the molar ratio n of hydrofluoric acid is 1.0 to 2.5, and further 1.0 to 2.0 under the condition that the reactivity of fluorination is particularly high.
- Example 16-21 In Example 1, the amount of the reactant used was scaled up 10 times, and the amount ratio of triethylamine trifluoride addition salt and triethylamine was changed as shown in Table 2, and the same procedure as in Example 1 was repeated.
- -EC was prepared, and the obtained organic layer was analyzed by gas chromatography (GC), gas chromatography / mass spectrometry (GC / MS) and 19 F-NMR, and the conversion of Cl-EC and the F-EC The selectivity was examined. The results are shown in Table 2.
- the obtained organic layer was analyzed by gas chromatography (GC), gas chromatography / mass spectrometry (GC / MS) and 19 F-NMR. As a result, the conversion rate of Cl-EC was 90%, and the selectivity of F-EC was It was produced at 80%.
- Example 23 A fluorination reaction was carried out in the same manner as in Example 1 except that 1.99 g (20.1 mmol) of pyridine monohydrofluoric acid addition salt was used instead of triethylamine trihydrofluoric acid addition salt, and triethylamine was not used (hydrofluoric acid).
- Molar ratio n 1.0.
- Amine molar ratio m 1.2).
- the obtained organic layer was analyzed by gas chromatography (GC), gas chromatography / mass spectrometry (GC / MS) and 19 F-NMR. As a result, the conversion of Cl-EC was 85%, and F-EC was selectivity. It was produced at 80%.
- GC gas chromatography
- MS gas chromatography / mass spectrometry
- Comparative Example 1 (using potassium fluoride) A reflux tube was attached to the top of a 3 L glass three-necked flask equipped with a stirrer, 355 g (6.12 mol) of spray-dried potassium fluoride was added, and water was removed by flame drying while stirring under vacuum. Thereafter, 1.3 L of acetonitrile and 500 g (4.08 mol) of Cl-EC treated with an antacid were added and stirred using a syringe. The fluorination reaction was carried out at a reaction temperature of 85 ° C. for 6 hours, and then neutralized with sodium bicarbonate.
- Example 25 In Example 20, the reactant used was scaled up 25 times, and the following antacid treatment step (C) and solid content removal step (E) were performed in advance on Cl-EC as a starting material.
- Antacid treatment process 100 g of amorphous silica / alumina gel (Secard KW manufactured by Shinagawa Kasei Co., Ltd., neutral silica gel, trade name) was added to Cl-EC as a starting material, and the mixture was stirred at room temperature for 2 hours.
- amorphous silica / alumina gel (Secard KW manufactured by Shinagawa Kasei Co., Ltd., neutral silica gel, trade name) was added to Cl-EC as a starting material, and the mixture was stirred at room temperature for 2 hours.
- Solid removal step (E) Thereafter, an antacid (amorphous silica / alumina gel) and the like were filtered.
- An F-EC-containing organic layer was obtained in the same manner as in Example 20 except that Cl-EC treated with an antacid was used.
- the obtained organic layer was analyzed by gas chromatography (GC), gas chromatography / mass spectrometry (GC / MS) and 19 F-NMR. As a result, the conversion of Cl-EC was 99%, and F-EC was selectivity. It was produced at 90%.
- GC gas chromatography
- MS gas chromatography / mass spectrometry
- Organic solvent removal step (D) The organic solvent (ethyl acetate) was distilled off from the obtained filtrate using an evaporator.
- Rectification process (B) The residue was subjected to rectification using a Ligrew tube, and colorless and transparent F-EC was obtained as a fraction at 74 ° C. (1 mmHg) with a yield of 65% and a GC purity of 99.8%.
- Metal ion analysis The concentration of metal ions (Al, Fe, Ca, K, Mg, Na, Ni, Zn) is measured using an emission spectroscopic analyzer SPS3000 ICP (detection limit: 10 ppb) manufactured by Seiko Instruments Inc. To do.
- Example 26 The organic layer obtained in the same manner as in the fluorination step (A) of Example 25 was subjected to the next step.
- Antacid treatment process 100 g of amorphous silica / alumina gel (Secard KW manufactured by Shinagawa Kasei Co., Ltd., neutral silica gel, trade name) was added to the resulting organic layer, and the mixture was stirred at room temperature for 2 hours.
- amorphous silica / alumina gel (Secard KW manufactured by Shinagawa Kasei Co., Ltd., neutral silica gel, trade name) was added to the resulting organic layer, and the mixture was stirred at room temperature for 2 hours.
- Solid removal step (E) Subsequently, an antacid (amorphous silica / alumina gel) was filtered.
- Organic solvent removal step (D) The organic solvent (ethyl acetate) was distilled off from the obtained filtrate using an evaporator.
- Rectification process (B) The residue was subjected to rectification using a Ligrew tube, and colorless and transparent F-EC was obtained as a fraction at 74 ° C. (1 mmHg) with a yield of 64% and a GC purity of 99.7%.
- Example 27 The organic layer obtained in the same manner as in the fluorination step (A) of Example 25 was subjected to the next step.
- Organic solvent removal step (D) The organic solvent (ethyl acetate) was distilled off from the obtained reaction product solution using an evaporator.
- Rectification process (B) + antacid treatment process (C) The residue was subjected to rectification using a distillation column packed with amorphous silica-alumina gel (Secard KW manufactured by Shinagawa Kasei Co., Ltd., neutral silica gel, trade name), and the residue was distilled at 74 ° C. (1 mmHg). As a fraction, colorless and transparent F-EC was obtained with a yield of 65% and a GC purity of 99.8%.
- amorphous silica-alumina gel Secard KW manufactured by Shinagawa Kasei Co., Ltd., neutral silica gel, trade name
- Example 28 The organic layer obtained in the same manner as in the fluorination step (A) of Example 25 was subjected to the next step.
- Organic solvent removal step (D) The organic solvent (ethyl acetate) was distilled off from the obtained reaction product solution using an evaporator.
- Rectification process (B) The residue was subjected to rectification using a Ligrew tube, and colorless and transparent F-EC was obtained as a fraction at 74 ° C. (1 mmHg).
- Antacid treatment process To the obtained F-EC fraction, 100 g of amorphous silica / alumina gel was added and stirred at room temperature for 2 hours.
- Solid removal step (E) From the obtained antacid-treated F-EC, amorphous silica / alumina gel was removed by filtration to obtain purified F-EC with a yield of 70% and a GC purity of 99.8%.
- Example 1 The organic layer obtained in Example 25 was subjected to an organic solvent removal step and a rectification step in the same manner as in Example 28 except that the antacid treatment step and the solid content removal step were not carried out, and purified F-EC was obtained with a yield of 50% and a GC purity of 99.5%.
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Abstract
Description
(1)1,3-ジオキソラン-2-オンを出発物質とし、フッ素ガスで直接フッ素化する方法、
(2)フッ素化剤として、ほぼ等量の金属フッ化物を用いてハロゲン(Cl、BrまたはI)化1,3-ジオキソラン-2-オン(以下、「ハロゲン化EC」ということもあるが、これには目的物である「フッ素化EC」は含まれない。以下同様)のハロゲン原子(Cl、BrまたはI)をフッ素原子で置換する方法
が知られている(特許文献2~4)。
有機溶媒中にて、式(1):
で示される1,3-ジオキソラン-2-オン誘導体にアミンのフッ酸付加塩を反応させるフッ素化工程(A)を含むフッ素化1,3-ジオキソラン-2-オンの製造方法に関する。
式(2):
式(3):
で示される化合物が、非プロトン性溶媒への溶解性が良好な点から好ましく、特に、置換反応の反応性が良好な点から式(2)および(3)において、nが1~3、さらには1~2の範囲の値である化合物が好ましい。
で示される化合物である。
たとえば、n=3のアミンのフッ酸付加塩1モルとn=1のアミンのフッ酸付加塩1モルを混合してn=2[=(3×1+1×1)/2]のアミンのフッ酸付加塩とする。
たとえば、n=3のアミンのフッ酸付加塩1モルとアミン1モルを混合してn=1.5[=(3×1)/2]のアミンのフッ酸付加塩とする。
たとえば有機溶剤にアミン1モルを溶解させた溶液にフッ酸2モルを混合してn=2のアミンのフッ酸付加塩をその場で調製する。
すなわち出発原料であるハロゲン化ECを制酸剤で処理する。出発原料であるハロゲン化ECには、合成の過程で生ずる塩素根(Cl-、HCl、Cl2など)が存在するので、これらのハロゲン根を除去する。
フッ素化工程(A)中では、出発原料中の塩素根に加えて、フッ素化剤(フッ素ガス、フッ酸、MFなど)に由来するフッ素(F2)、フッ化水素(HF)、フッ素イオン(F-)などのほか、フッ素化反応の副生物である不純物由来のフッ素イオンなどが存在するので、これらのハロゲン根を除去する。
フッ素化工程(A)で得られる反応生成物中には、上記(2)と同様なハロゲン根が存在するので、これらのハロゲン根を除去する。
フッ素化工程(A)で得られた反応生成物に対して精留工程(B)の前に、有機溶媒の除去(蒸留)や、既に制酸剤処理が少なくとも1回行われていた場合は制酸剤の除去(ろ過)処理が行われることがある。
精留工程(B)中では、不純物が分解して生ずるハロゲン根が存在するので、これらのハロゲン根を除去する。
精留工程(B)の後には、精留による加熱や減圧により蒸発または留去されるもの以外のハロゲン根が存在するので、これらのハロゲン根を除去する。
(1)NMR
装置:BRUKER製のAC-300
測定条件:
19F-NMR:282MHz(トリフルオロメチルベンゼン=-62.3ppm)
(2)ガスクロマトグラフィ(GC)
装置:島津製作所製のGC-17A
カラム:DB624(J&Wサイエンティフィック社製)
測定条件:100℃→5分間保持→10℃/分で昇温→230℃
(3)ガスクロマトグラフィ/質量分析(GC/MS)
装置:PERKIN ELMER社製のClaus500
測定条件:100℃→5分間保持→10℃/分で昇温→230℃
リフラックスコンデンサーを備えた30mlの3口フラスコにトリエチルアミン3フッ酸付加塩(3.2g:19.6mmol)、トリエチルアミン(1.3g:12.8mmol)、酢酸エチル(5ml)およびアセトニトリル(1ml)を加えた(フッ酸モル比n=1.8)。これに4-クロロ-1,3-ジオキソラン-2-オン(Cl-EC。2.0g:16.3mmol。アミンモル比m=2)を仕込み、反応温度80℃で1時間かけてフッ素化反応を行なった。
実施例1において、トリエチルアミン3フッ酸付加塩とトリエチルアミンの量、有機溶媒の種類と量、反応温度、反応時間を表1に示すように変更した以外は実施例1と同様にしてF-ECの製造を行い、得られた有機層をガスクロマトグラフィ(GC)、ガスクロマトグラフィ/質量分析(GC/MS)および19F-NMRで分析して、Cl-ECの転化率とF-ECの選択率を調べた。結果を表1に示す。
実施例1において、トリエチルアミンを使用しなかったほかは実施例1と同様にしてF-ECの製造を行い、得られた有機層をガスクロマトグラフィ(GC)、ガスクロマトグラフィ/質量分析(GC/MS)および19F-NMRで分析して、Cl-ECの転化率とF-ECの選択率を調べた。結果を表1に示す。
実施例1において、使用する反応物質の量を10倍にスケールアップし、またトリエチルアミン3フッ酸付加塩とトリエチルアミンの量比を表2に示すとおりに変更したほかは実施例1と同様にしてF-ECの製造を行い、得られた有機層をガスクロマトグラフィ(GC)、ガスクロマトグラフィ/質量分析(GC/MS)および19F-NMRで分析して、Cl-ECの転化率とF-ECの選択率を調べた。結果を表2に示す。
トリエチルアミン3フッ酸付加塩に代えて、イソプロピルアミン1フッ酸付加塩を1.5g(20.1mmol)用い、トリエチルアミンを使用しなかったほかは実施例1と同様にフッ素化反応を実施した(フッ酸モル比n=1.0。アミンモル比m=1.2)。
トリエチルアミン3フッ酸付加塩に代えて、ピリジン1フッ酸付加塩を1.99g(20.1mmol)用い、トリエチルアミンを使用しなかったほかは実施例1と同様にフッ素化反応を実施した(フッ酸モル比n=1.0。アミンモル比m=1.2)。
リフラックスコンデンサーを備えた30mlの3口フラスコにトリエチルアミン3フッ酸付加塩(2.3g:14.3mmol)、酢酸エチル(10ml)、トリエチルアミン(2.51g:24.78mmol)を加えた(フッ酸モル比n=1.1)。これに4,5-ジメチル-4,5-ジクロロ-1,3-ジオキソラン-2-オン(3.00g:16.3mmol。アミンモル比m=2.4)を仕込み、反応温度80℃で1時間かけてフッ素化反応を行なった後、重炭酸水素ナトリウムを用いて中和した。
撹拌装置を備えた3Lのガラス製3口フラスコの上部に還流管を取り付け、スプレードライのフッ化カリウム355g(6.12mol)を加え真空下で攪拌しながらフレームドライにより水分を除去した。その後シリンジを用いてアセトニトリル1.3L、制酸剤処理されたCl-EC500g(4.08mol)を加えて攪拌した。反応温度85℃で6時間かけてフッ素化反応を行なった後、重炭酸水素ナトリウムを用いて中和した。
実施例20において、使用する反応物質を25倍にスケールアップし、出発原料であるCl-ECについて、つぎの制酸剤処理工程(C)および固形分除去工程(E)を事前に施した。
出発原料であるCl-ECに非晶質性シリカ・アルミナゲル(品川化成(株)製のセカードKW。中性シリカゲル。商品名)100gを加えて室温下で2時間撹拌した。
その後、制酸剤(非晶質性シリカ・アルミナゲル)などをろ過した。
得られたろ液からエバポレーターを用いて有機溶媒(酢酸エチル)を留去した。
残留物をリグリュー管を用いて精留に供し、74℃(1mmHg)の留分として無色透明なF-ECを収率65%、GC純度99.8%で得た。
室温下で一日保管して着色の有無を目視で判定する。
○:着色が認められなかった。
×:着色が認められた。
装置として、(株)島津製作所製のイオンクロマトグラフィーHIC-20A SUPER(検出限界:1ppm)を用いて陰イオン(Cl-、F-、I-、NO2、NO3、PO4、SO4)の濃度を測定する。
装置として、セイコーインスツルメント(株)製の発光分光分析装置SPS3000 ICP(検出限界:10ppb)を用いて金属イオン(Al、Fe、Ca、K、Mg、Na、Ni、Zn)の濃度を測定する。
装置として、リトマス試験紙を用いて精留後のF-ECのpHを調べる。
実施例25のフッ素化工程(A)と同様にして得られた有機層をつぎの工程に供した。
得られた有機層に非晶質性シリカ・アルミナゲル(品川化成(株)製のセカードKW。中性シリカゲル。商品名)100gを加えて室温下で2時間撹拌した。
ついで制酸剤(非晶質性シリカ・アルミナゲル)などをろ過した。
得られたろ液からエバポレーターを用いて有機溶媒(酢酸エチル)を留去した。
残留物をリグリュー管を用いて精留に供し、74℃(1mmHg)の留分として無色透明なF-ECを収率64%、GC純度99.7%で得た。
実施例25のフッ素化工程(A)と同様にして得られた有機層をつぎの工程に供した。
得られた反応生成液からエバポレーターを用いて有機溶媒(酢酸エチル)を留去した。
非晶質性シリカ・アルミナゲル(品川化成(株)製のセカードKW。中性シリカゲル。商品名)が充填された蒸留塔を用いて残留物を精留に供し、74℃(1mmHg)の留分として無色透明なF-ECを収率65%、GC純度99.8%で得た。
実施例25のフッ素化工程(A)と同様にして得られた有機層をつぎの工程に供した。
得られた反応生成液からエバポレーターを用いて有機溶媒(酢酸エチル)を留去した。
残留物をリグリュー管を用いて精留に供し、74℃(1mmHg)の留分として無色透明なF-ECを得た。
得られたF-EC留分に非晶質性シリカ・アルミナゲル100gを添加し、室温下に2時間攪拌した。
得られた制酸剤処理F-ECから、ろ過により非晶質性シリカ・アルミナゲルを除去し、精製F-ECを収率70%、GC純度99.8%で得た。
実施例25で得られた有機層について、制酸剤処理工程および固形分除去工程を実施しなかったほかは実施例28と同様にして有機溶媒除去工程および精留工程を行って精製F-ECを収率50%、GC純度99.5%で得た。
Claims (9)
- 前記アミンのフッ酸付加塩におけるアミンに対するフッ酸のモル比nが1~10である請求項1記載の製造方法。
- 前記式(1)の1,3-ジオキソラン-2-オン誘導体におけるCl、Brおよび/またはI原子1モルに対するアミンのフッ酸付加塩のモル比mが0.5~4である請求項1または2記載の製造方法。
- 式(2)および(3)において、nが1~3の範囲の値である請求項4記載の製造方法。
- 有機溶媒が、非プロトン性溶媒である請求項1~5のいずれかに記載の製造方法。
- 有機溶媒が、ニトリル系溶媒、環状エーテル系溶媒、鎖状エーテル系溶媒、エステル系溶媒、鎖状カーボネート系溶媒、ケトン系溶媒またはアミド系溶媒である請求項1~6のいずれかに記載の製造方法。
- フッ素化1,3-ジオキソラン-2-オンを精留する精留工程(B)を含む請求項1~7のいずれかに記載の製造方法。
- 制酸剤で処理する工程(C)を含むことを特徴とする請求項1~8のいずれかに記載の製造方法。
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Cited By (3)
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WO2011048053A1 (en) | 2009-10-21 | 2011-04-28 | Solvay Fluor Gmbh | Method for the manufacture of fluorinated ethylene carbonates |
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62290072A (ja) * | 1986-06-09 | 1987-12-16 | Matsushita Electric Ind Co Ltd | 有機電解質二次電池 |
JPH08268918A (ja) * | 1995-02-28 | 1996-10-15 | Rhone Poulenc Chim | フルオロ誘導体の合成方法 |
JP2001501355A (ja) * | 1996-10-03 | 2001-01-30 | ナショナル リサーチ カウンシル オブ カナダ | アルカリ金属イオン二次電池用の、フルオロエチレンカーボネート及びプロピレンカーボネートを含む電解質 |
JP2002338518A (ja) * | 2001-05-16 | 2002-11-27 | Chisso Corp | 酸フッ化物誘導体およびそれを含む液晶組成物 |
WO2005037818A1 (ja) * | 2003-10-16 | 2005-04-28 | Asahi Glass Company, Limited | 新規な含フッ素ジオキソラン化合物、および新規な含フッ素重合体 |
JP2007008826A (ja) * | 2005-06-28 | 2007-01-18 | Central Glass Co Ltd | 高純度の4−フルオロ−1,3−ジオキソラン−2−オンの製造方法 |
JP2007008825A (ja) * | 2005-06-28 | 2007-01-18 | Central Glass Co Ltd | 高純度の4−フルオロ−1,3−ジオキソラン−2−オンの製造方法 |
JP2008195691A (ja) * | 2007-02-15 | 2008-08-28 | Daikin Ind Ltd | 4−フルオロ−1,3−ジオキソラン−2−オンの製造法 |
JP2009019019A (ja) * | 2007-07-13 | 2009-01-29 | Daikin Ind Ltd | 4−フルオロ−1,3−ジオキソラン−2−オンの製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6632368B2 (en) * | 2000-02-23 | 2003-10-14 | Marc Blachman | Process for removing fluorides from fluids |
US7592486B2 (en) | 2004-09-16 | 2009-09-22 | Board Of Regents Of The University Of Nebraska | Anhydrous fluoride salts and reagents and methods for their production |
CN101210005B (zh) * | 2006-12-30 | 2012-07-25 | 张家港市国泰华荣化工新材料有限公司 | 一种氟代碳酸乙烯酯的制备方法 |
-
2008
- 2008-02-28 JP JP2008048674A patent/JP5358974B2/ja active Active
-
2009
- 2009-01-30 WO PCT/JP2009/051590 patent/WO2009107449A1/ja active Application Filing
- 2009-01-30 US US12/920,092 patent/US9067907B2/en active Active
- 2009-01-30 CN CN200980106666.2A patent/CN101959874B/zh active Active
- 2009-01-30 KR KR1020107018750A patent/KR101248717B1/ko not_active IP Right Cessation
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62290072A (ja) * | 1986-06-09 | 1987-12-16 | Matsushita Electric Ind Co Ltd | 有機電解質二次電池 |
JPH08268918A (ja) * | 1995-02-28 | 1996-10-15 | Rhone Poulenc Chim | フルオロ誘導体の合成方法 |
JP2001501355A (ja) * | 1996-10-03 | 2001-01-30 | ナショナル リサーチ カウンシル オブ カナダ | アルカリ金属イオン二次電池用の、フルオロエチレンカーボネート及びプロピレンカーボネートを含む電解質 |
JP2002338518A (ja) * | 2001-05-16 | 2002-11-27 | Chisso Corp | 酸フッ化物誘導体およびそれを含む液晶組成物 |
WO2005037818A1 (ja) * | 2003-10-16 | 2005-04-28 | Asahi Glass Company, Limited | 新規な含フッ素ジオキソラン化合物、および新規な含フッ素重合体 |
JP2007008826A (ja) * | 2005-06-28 | 2007-01-18 | Central Glass Co Ltd | 高純度の4−フルオロ−1,3−ジオキソラン−2−オンの製造方法 |
JP2007008825A (ja) * | 2005-06-28 | 2007-01-18 | Central Glass Co Ltd | 高純度の4−フルオロ−1,3−ジオキソラン−2−オンの製造方法 |
JP2008195691A (ja) * | 2007-02-15 | 2008-08-28 | Daikin Ind Ltd | 4−フルオロ−1,3−ジオキソラン−2−オンの製造法 |
JP2009019019A (ja) * | 2007-07-13 | 2009-01-29 | Daikin Ind Ltd | 4−フルオロ−1,3−ジオキソラン−2−オンの製造方法 |
Non-Patent Citations (1)
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011048053A1 (en) | 2009-10-21 | 2011-04-28 | Solvay Fluor Gmbh | Method for the manufacture of fluorinated ethylene carbonates |
CN102596930A (zh) * | 2009-10-21 | 2012-07-18 | 苏威氟有限公司 | 用于制造氟化碳酸亚乙酯的方法 |
CN101774923B (zh) * | 2010-01-26 | 2013-06-12 | 太仓中化环保化工有限公司 | 一种氟代碳酸乙烯酯的制备方法 |
CN102060839A (zh) * | 2010-12-31 | 2011-05-18 | 上海康鹏化学有限公司 | 氟代碳酸乙烯酯的制备方法 |
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