WO2010128634A1 - Process for producing 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one - Google Patents

Process for producing 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one Download PDF

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WO2010128634A1
WO2010128634A1 PCT/JP2010/057448 JP2010057448W WO2010128634A1 WO 2010128634 A1 WO2010128634 A1 WO 2010128634A1 JP 2010057448 W JP2010057448 W JP 2010057448W WO 2010128634 A1 WO2010128634 A1 WO 2010128634A1
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dioxolan
dialkyl
difluoro
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昭佳 山内
明天 高
明範 谷
真裕 冨田
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ダイキン工業株式会社
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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
    • C07D317/40—Vinylene carbonate; Substituted vinylene carbonates

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  • the present invention relates to a method for producing 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one.
  • fluorinated ethylene carbonate has attracted attention because of its excellent charge / discharge cycle characteristics and current efficiency.
  • Difluoroethylene carbonate (4,4-difluoro-1,3-dioxolan-2-one, 4,5-difluoro -1,3-dioxolan-2-one) is known (Patent Document 1), and a production method for fluorinating monofluoroethylene carbonate has been proposed.
  • Patent Documents 2 to 3 Fluorination is also described for substituted ethylene carbonate (Patent Documents 2 to 3).
  • Patent Document 2 proposes a very wide range of general formulas, and many exemplified compounds are listed. The only fluorinated ethylene carbonates used in the examples are monofluoroethylene carbonate and difluoroethylene carbonate.
  • Patent Document 3 describes fluoroethylene carbonate having a methyl group as a substituent as having an effect of suppressing the formation of dendrites.
  • reaction product obtained by the reaction of carbonyl difluoride and the diketone compound is a mixture of trans-isomer and cis-isomer, and these isomers are separated by fractional distillation.
  • the trans-form when used in an electrolytic solution, is particularly preferred because the compound has good stability and low viscosity. If the trans-form can be directly synthesized, the number of treatment steps can be reduced, which is advantageous in terms of cost.
  • the present invention relates to formula (2): (Wherein R 1 and R 2 are the same or different, and both of which may have a fluorine atom or have an ether bond, an alkyl group having 1 to 4 carbon atoms) 4,5 Formula (1) characterized by reacting a fluorinating agent with -dialkyl-1,3-dioxolan-2-one-4,5-ene: (Wherein R 1 and R 2 are the same as those in formula (2)), and relates to a process for producing 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one.
  • fluorinating agent fluorine gas is preferable because it is advantageous in that post-treatment is easy.
  • a novel production method of 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one can be provided, and further, a trans-isomer can be selectively synthesized. .
  • Formula (2) which is a starting material in the production method of the present invention: (Wherein R 1 and R 2 are the same or different, and both of which may have a fluorine atom or have an ether bond, an alkyl group having 1 to 4 carbon atoms)
  • 4,5 -Dialkyl-1,3-dioxolan-2-one-4,5-ene is a known compound described in, for example, JP-A-62-253983, and can be produced, for example, by the following method.
  • any inorganic base or organic base can be used, but in particular, tertiary amines such as dimethylpyridine, dimethylaniline, pyridine, triethylamine, etc., primary amines, secondary amines, and the like are preferable.
  • the solvent is preferably an organic solvent, and examples thereof include polar solvents such as dichloromethane, chloroform, tetrahydrofuran, dimethylacetamide, dimethylformamide, glyme solvents, acetonitrile, acetone, toluene, and ethyl acetate.
  • polar solvents such as dichloromethane, chloroform, tetrahydrofuran, dimethylacetamide, dimethylformamide, glyme solvents, acetonitrile, acetone, toluene, and ethyl acetate.
  • the reaction proceeds sufficiently at a reaction temperature of 0 to 40 ° C. under atmospheric pressure or pressurized conditions.
  • the reaction conditions for synthesizing fluorinated ethylene carbonate for example, the conditions described in SYNTHETIC COMMUNICATIONS, 23 (6), pp847-853 (1993) or Journal of Fluorine Chemistry, 120, pp105-110 (2003)). ) Can also be adopted.
  • 4,5-dialkyl-1,3-dioxolan-2-one-4,5-ene then desorbs 4,5-dialkyl-5-chloro-1,3-dioxolan-2-one in the presence of a base. It can be produced by HCl formation.
  • condition for the deHCl reaction for example, a condition of heating in the presence of the above-mentioned base (for example, at 160 ° C. for 3 hours) can be employed (see JP-A-62-253983).
  • R 1 and R 2 are an alkyl group or a fluorine-containing alkyl group which may have an ether bond having 1 to 4 carbon atoms.
  • the carbon number of the alkyl group is from the low viscosity of the resulting carbonate to 4 and in particular 1 to 3.
  • R 1 and R 2 may be the same or different.
  • non-fluorinated alkyl groups examples include: Etc.
  • non-fluorinated alkyl groups having an ether bond examples include: Etc.
  • fluorine-containing alkyl group examples include Etc.
  • fluorine-containing alkyl group having an ether bond for example Etc.
  • Preferred examples of the fluorinating agent to be reacted with the starting material (2) include compounds represented by the formula: MF (wherein M is an alkali metal atom or a quaternary ammonium cation) in addition to hydrofluoric acid and fluorine gas.
  • M is an alkali metal atom or a quaternary ammonium cation
  • Specific examples of MF include compounds of KF, NaF, CsF, LiF, quaternary ammonium cations and fluoroanions.
  • fluorine gas is preferred because it is advantageous in that post-treatment is simple.
  • the fluorine gas may be diluted with an inert gas such as nitrogen gas.
  • the fluorination reaction is preferably performed in an organic solvent.
  • organic solvent include dichloromethane, chloroform, tetrahydrofuran, dimethylacetamide, dimethylformamide, glyme solvents, polar solvents such as acetonitrile, acetone, toluene, and ethyl acetate.
  • the reaction temperature may be in the range of -20 to 0 ° C.
  • the feature of the production method of the present invention is the formula (1): (Wherein R 1 and R 2 are the same as those in the formula (2)), as a 4-5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one represented by the formula (1A): (Wherein R 1 and R 2 are the same or different, both of which may have a fluorine atom or may have an ether bond and an alkyl group having 1 to 4 carbon atoms) trans-4 , 5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one with high yield and high selectivity (trans-isomer selectivity: 70 to 90%, more preferably 80 to 90%, especially 85 to 90%).
  • the purity of the trans-isomer can be improved to 99.5 GC% (gel chromatographic purity) or higher by subjecting the resulting product containing the trans-isomer to the fractional distillation. .
  • 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one represented by the formula (1) particularly trans-4,5-dialkyl-4,5-difluoro represented by the formula (1A) -1,3-Dioxolan-2-one has an effect of forming a stable protective film on the electrode (positive electrode or negative electrode) of a lithium secondary battery, and is useful as an additive for a nonaqueous electrolytic solution.
  • reaction mixture was quenched with 400 mL of 1N hydrochloric acid, subsequently washed with 200 mL of 1N hydrochloric acid, and further washed with 200 mL of pure water.
  • the obtained organic layer containing 4,5-dimethyl-5-chloro-1,3-dioxolan-2-one was dried using magnesium sulfate, filtered, and then concentrated under reduced pressure using an evaporator. The concentrated solution was heated and stirred at 160 ° C.
  • Example 1 (Production of 4,5-dimethyl-4,5-difluoro-1,3-dioxolan-2-one)
  • a 500 mL nickel autoclave 114 g of 4,5-dimethyl-1,3-dioxolan-2-one-4,5-ene produced in the same manner as in Reference Example 1, 1,1,2-trichloro-1, 200 mL of 2,2-trifluoroethane (hereinafter abbreviated as R-113) was added and stirred, and cooled to -20 ° C.
  • An alumina packed tower was connected to the gas outlet of the autoclave, and a trap filled with a sodium hydroxide / sodium sulfite aqueous solution was connected.
  • This reaction product solution was concentrated under reduced pressure using an evaporator, and then distilled under reduced pressure (10 to 11 mmHg, solution temperature 55 ° C.) using a 10-stage Oldershaw to find trans-4,5-dimethyl-4,5-difluoro. 122 g (yield 80%, purity 99.7 GC%) of 1,3-dioxolan-2-one was obtained.
  • reaction mixture was quenched with 300 mL of 1N hydrochloric acid, subsequently washed with 150 mL of 1N hydrochloric acid, and further washed with 150 mL of pure water.
  • the obtained organic layer containing 4,5-diethyl-5-chloro-1,3-dioxolan-2-one was dried using magnesium sulfate, filtered, and concentrated under reduced pressure using an evaporator. The concentrated solution is heated and stirred at 160 ° C.
  • Example 2 (Production of 4,5-diethyl-4,5-difluoro-1,3-dioxolan-2-one)
  • a 500 mL nickel autoclave 142 g of 4,5-diethyl-1,3-dioxolan-2-one-4,5-ene produced in the same manner as in Reference Example 2 and 200 mL of R-113 were placed and stirred. Cooled to -20 ° C.
  • An alumina packed tower was connected to the gas outlet of the autoclave, and a trap filled with a sodium hydroxide / sodium sulfite aqueous solution was connected.
  • This reaction product solution was concentrated under reduced pressure using an evaporator, and then distilled under reduced pressure (10 to 11 mmHg, solution temperature 67 ° C.) using a 10-stage Oldershaw to find trans-4,5-diethyl-4,5-difluoro. 146 g (yield 81%, purity 99.6 GC%) of 1,3-dioxolan-2-one was obtained.

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Abstract

A novel process for producing a 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one, characterized by reacting a 4,5-dialkyl-1,3-dioxolan-2-on-4,5-ene with a fluorinating agent.

Description

４，５－ジアルキル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンの製造法Process for producing 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one
　本発明は、４，５－ジアルキル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンの製造方法に関する。 The present invention relates to a method for producing 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one.
　エチレンカーボネート（＝１，３－ジオキソラン－２－オン）は、二次電池やキャパシタなどの電気化学デバイスに用いる電解液の溶媒として汎用されている。 Ethylene carbonate (= 1,3-dioxolan-2-one) is widely used as a solvent for electrolytic solutions used in electrochemical devices such as secondary batteries and capacitors.
　さらに充放電サイクル特性や電流効率などに優れる点からフッ素化されたエチレンカーボネートが注目されており、ジフルオロエチレンカーボネート（４，４－ジフルオロ－１，３－ジオキソラン－２－オン、４，５－ジフルオロ－１，３－ジオキソラン－２－オン）などが知られており（特許文献１）、モノフルオロエチレンカーボネートをフッ素化する製造法が提案されている。 Further, fluorinated ethylene carbonate has attracted attention because of its excellent charge / discharge cycle characteristics and current efficiency. Difluoroethylene carbonate (4,4-difluoro-1,3-dioxolan-2-one, 4,5-difluoro -1,3-dioxolan-2-one) is known (Patent Document 1), and a production method for fluorinating monofluoroethylene carbonate has been proposed.
　フッ素化は置換エチレンカーボネートについても記載されており（特許文献２～３）、特許文献２には非常に広範囲の一般式が提案されており、その例示化合物も多数列挙されているが、実際に実施例で使用されているフッ素化エチレンカーボネートはモノフルオロエチレンカーボネートおよびジフルオロエチレンカーボネートだけである。 Fluorination is also described for substituted ethylene carbonate (Patent Documents 2 to 3). Patent Document 2 proposes a very wide range of general formulas, and many exemplified compounds are listed. The only fluorinated ethylene carbonates used in the examples are monofluoroethylene carbonate and difluoroethylene carbonate.
　特許文献３には、デンドライトの形成を抑制する効果があるとして、置換基としてメチル基を有するフルオロエチレンカーボネートが記載されている。しかし、この特許文献３でも実施例で実際に使用されているフッ素化エチレンカーボネートは１－メチル－２，２－ジフルオロエチレンカーボネート（＝４，４－ジフルオロ－５－メチル－１，３－ジオキソラン－２－オン）１つだけであり、またジアルキル体の製造法については記載されていない。 Patent Document 3 describes fluoroethylene carbonate having a methyl group as a substituent as having an effect of suppressing the formation of dendrites. However, in this Patent Document 3, the fluorinated ethylene carbonate actually used in the examples is 1-methyl-2,2-difluoroethylene carbonate (= 4,4-difluoro-5-methyl-1,3-dioxolane- 2-one) There is only one, and there is no description of a method for producing dialkyl compounds.
特開２０００－３４４７６３号公報JP 2000-344863 A 特開２００７－１８８８７３号公報JP 2007-188873 A 特開平８－３０６３６４号公報JP-A-8-306364
　ところで二フッ化カルボニルとジケトン化合物の反応で得られる反応生成物はtrans－体とcis－体の混合物であり、これらの異性体は分別蒸留で分けている。 Incidentally, the reaction product obtained by the reaction of carbonyl difluoride and the diketone compound is a mixture of trans-isomer and cis-isomer, and these isomers are separated by fractional distillation.
　また、電解液に用いる場合、trans－体が化合物の安定性がよく、粘性も低い点から特に好ましく、trans－体を直接合成できれば、処理工程を少なくでき、コスト面で有利となる。 In addition, when used in an electrolytic solution, the trans-form is particularly preferred because the compound has good stability and low viscosity. If the trans-form can be directly synthesized, the number of treatment steps can be reduced, which is advantageous in terms of cost.
　本発明は、式（２）：
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｒ1およびＲ2は同じかまたは異なり、いずれもフッ素原子を有していてもよくエーテル結合を有していてもよい炭素数１～４のアルキル基）で示される４，５－ジアルキル－１，３－ジオキソラン－２－オン－４，５－エンにフッ素化剤を反応させることを特徴とする式（１）：
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ1およびＲ2は式（２）と同じ）で示される４，５－ジアルキル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンの製造法に関する。 The present invention relates to formula (2):
Figure JPOXMLDOC01-appb-C000004
 (Wherein R 1 and R 2 are the same or different, and both of which may have a fluorine atom or have an ether bond, an alkyl group having 1 to 4 carbon atoms) 4,5 Formula (1) characterized by reacting a fluorinating agent with -dialkyl-1,3-dioxolan-2-one-4,5-ene:
Figure JPOXMLDOC01-appb-C000005
 (Wherein R 1 and R 2 are the same as those in formula (2)), and relates to a process for producing 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one.
　本発明によれば、式（１Ａ）：
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ1およびＲ2は同じかまたは異なり、いずれもフッ素原子を有していてもよくエーテル結合を有していてもよい炭素数１～４のアルキル基）で示されるtrans－４，５－ジアルキル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンを高収率で選択的に合成することができる。 According to the invention, the formula (1A):
Figure JPOXMLDOC01-appb-C000006
 (Wherein R 1 and R 2 are the same or different, both of which may have a fluorine atom or may have an ether bond and an alkyl group having 1 to 4 carbon atoms) trans-4 , 5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one can be selectively synthesized in high yield.
　フッ素化剤としては、フッ素ガスが後処理が簡単である点で有利であることから好ましい。 As the fluorinating agent, fluorine gas is preferable because it is advantageous in that post-treatment is easy.
　本発明の製造方法によれば、４，５－ジアルキル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンの新規な製造方法を提供でき、さらにはtrans－体を選択的に合成できる。 According to the production method of the present invention, a novel production method of 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one can be provided, and further, a trans-isomer can be selectively synthesized. .
　本発明の製造方法における出発物質である式（２）：
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｒ1およびＲ2は同じかまたは異なり、いずれもフッ素原子を有していてもよくエーテル結合を有していてもよい炭素数１～４のアルキル基）で示される４，５－ジアルキル－１，３－ジオキソラン－２－オン－４，５－エンは、たとえば特開昭６２－５３９８３号公報に記載されている公知化合物であり、たとえばつぎの方法で製造できる。 Formula (2) which is a starting material in the production method of the present invention:
Figure JPOXMLDOC01-appb-C000007
 (Wherein R 1 and R 2 are the same or different, and both of which may have a fluorine atom or have an ether bond, an alkyl group having 1 to 4 carbon atoms) 4,5 -Dialkyl-1,3-dioxolan-2-one-4,5-ene is a known compound described in, for example, JP-A-62-253983, and can be produced, for example, by the following method.
　式（３ａ）：
Figure JPOXMLDOC01-appb-C000008
 で示される二塩化カルボニル（ホスゲン）、または式（３ｂ）：
Figure JPOXMLDOC01-appb-C000009
 で示されるトリクロロメチルクロロホルメート(トリホスゲン)と、式（４）：
Figure JPOXMLDOC01-appb-C000010
 （式中、Ｒ1およびＲ2は式（２）と同じ）で示される化合物を塩基の存在下に反応させて式（５）：
Figure JPOXMLDOC01-appb-C000011
 （式中、Ｒ1およびＲ2は式（２）と同じ）で示される４，５－ジアルキル－５－クロロ－１，３－ジオキソラン－２－オンを合成する。 Formula (3a):
Figure JPOXMLDOC01-appb-C000008
 Or carbonyl dichloride (phosgene) represented by formula (3b):
Figure JPOXMLDOC01-appb-C000009
 And trichloromethyl chloroformate (triphosgene) represented by formula (4):
Figure JPOXMLDOC01-appb-C000010
 (Wherein R 1 and R 2 are the same as those in formula (2)), the compound represented by formula (5)
Figure JPOXMLDOC01-appb-C000011
 (Wherein R 1 and R 2 are the same as those in the formula (2)), 4,5-dialkyl-5-chloro-1,3-dioxolan-2-one is synthesized.
　この反応は塩基の存在下に溶媒中で定量的に進行する。 This reaction proceeds quantitatively in a solvent in the presence of a base.
　塩基としては任意の無機塩基、有機塩基が使用できるが、特にジメチルピリジン、ジメチルアニリン、ピリジン、トリエチルアミンなどの３級アミンのほか、１級アミン、２級アミンなどが好ましい。 As the base, any inorganic base or organic base can be used, but in particular, tertiary amines such as dimethylpyridine, dimethylaniline, pyridine, triethylamine, etc., primary amines, secondary amines, and the like are preferable.
　溶媒としては有機溶媒が好ましく、たとえばジクロロメタン、クロロホルム、テトラヒドロフラン、ジメチルアセトアミド、ジメチルホルムアミド、グライム系溶媒、アセトニトリル、アセトン、トルエン、酢酸エチルなどの極性溶媒などが例示できる。 The solvent is preferably an organic solvent, and examples thereof include polar solvents such as dichloromethane, chloroform, tetrahydrofuran, dimethylacetamide, dimethylformamide, glyme solvents, acetonitrile, acetone, toluene, and ethyl acetate.
　反応は、反応温度０～４０℃で、大気圧または加圧条件下で充分に進行する。なお、反応条件については、フッ素化エチレンカーボネートを合成する反応条件（たとえばSYNTHETIC COMMUNICATIONS,23(6),pp847-853(1993)またはJournal of Fluorine Chemistry,120,pp105-110(2003)に記載の条件）も採用できる。 The reaction proceeds sufficiently at a reaction temperature of 0 to 40 ° C. under atmospheric pressure or pressurized conditions. Regarding the reaction conditions, the reaction conditions for synthesizing fluorinated ethylene carbonate (for example, the conditions described in SYNTHETIC COMMUNICATIONS, 23 (6), pp847-853 (1993) or Journal of Fluorine Chemistry, 120, pp105-110 (2003)). ) Can also be adopted.
　４，５－ジアルキル－１，３－ジオキソラン－２－オン－４，５－エンは、ついで４，５－ジアルキル－５－クロロ－１，３－ジオキソラン－２－オンを塩基の存在下に脱ＨＣｌ化することにより製造できる。 4,5-dialkyl-1,3-dioxolan-2-one-4,5-ene then desorbs 4,5-dialkyl-5-chloro-1,3-dioxolan-2-one in the presence of a base. It can be produced by HCl formation.
　脱ＨＣｌ反応の条件としては、たとえば上記の塩基の存在下に加熱（たとえば１６０℃にて３時間）するといった条件が採用できる（特開昭６２－５３９８３号公報参照）。 As a condition for the deHCl reaction, for example, a condition of heating in the presence of the above-mentioned base (for example, at 160 ° C. for 3 hours) can be employed (see JP-A-62-253983).
　本発明において、Ｒ1およびＲ2は炭素数１～４のエーテル結合を有していてもよいアルキル基または含フッ素アルキル基である。アルキル基の炭素数は得られるカーボネートの粘性が低い点から４まで、特に１～３である。Ｒ1およびＲ2は同じでも異なっていてもよい。 In the present invention, R 1 and R 2 are an alkyl group or a fluorine-containing alkyl group which may have an ether bond having 1 to 4 carbon atoms. The carbon number of the alkyl group is from the low viscosity of the resulting carbonate to 4 and in particular 1 to 3. R 1 and R 2 may be the same or different.
　非フッ素系のアルキル基としては、たとえば、
などがあげられる。 Examples of non-fluorinated alkyl groups include:
Etc.
　エーテル結合を有する非フッ素系のアルキル基としては、たとえば
Figure JPOXMLDOC01-appb-C000013
 などがあげられる。 Examples of non-fluorinated alkyl groups having an ether bond include:
Figure JPOXMLDOC01-appb-C000013
 Etc.
　また、含フッ素アルキル基としては、たとえば
Figure JPOXMLDOC01-appb-C000014
 などがあげられる。 Examples of the fluorine-containing alkyl group include
Figure JPOXMLDOC01-appb-C000014
 Etc.
　エーテル結合を有する含フッ素アルキル基としては、たとえば
Figure JPOXMLDOC01-appb-C000015
 などがあげられる。 As the fluorine-containing alkyl group having an ether bond, for example
Figure JPOXMLDOC01-appb-C000015
 Etc.
　出発物質（２）と反応させるフッ素化剤としては、フッ酸、フッ素ガスのほか、式：ＭＦ（式中、Ｍはアルカリ金属原子または４級アンモニウムカチオン）で示される化合物が好ましく例示できる。ＭＦは具体的には、ＫＦ、ＮａＦ、ＣｓＦ、ＬｉＦ、４級アンモニウムカチオンとフルオロアニオンとの化合物などがあげられる。これらのうち、後処理が簡単である点で有利なことからフッ素ガスが好ましい。フッ素ガスは窒素ガスなどの不活性ガスで希釈して用いてもよい。 Preferred examples of the fluorinating agent to be reacted with the starting material (2) include compounds represented by the formula: MF (wherein M is an alkali metal atom or a quaternary ammonium cation) in addition to hydrofluoric acid and fluorine gas. Specific examples of MF include compounds of KF, NaF, CsF, LiF, quaternary ammonium cations and fluoroanions. Of these, fluorine gas is preferred because it is advantageous in that post-treatment is simple. The fluorine gas may be diluted with an inert gas such as nitrogen gas.
　フッ素化反応は、有機溶媒中で行うことが好ましい。有機溶媒としては、たとえばジクロロメタン、クロロホルム、テトラヒドロフラン、ジメチルアセトアミド、ジメチルホルムアミド、グライム系溶媒、アセトニトリル、アセトン、トルエン、酢酸エチルなどの極性溶媒などが例示できる。 The fluorination reaction is preferably performed in an organic solvent. Examples of the organic solvent include dichloromethane, chloroform, tetrahydrofuran, dimethylacetamide, dimethylformamide, glyme solvents, polar solvents such as acetonitrile, acetone, toluene, and ethyl acetate.
　反応温度は－２０～０℃の範囲でよい。 The reaction temperature may be in the range of -20 to 0 ° C.
　本発明の製造方法の特徴は、式（１）：
Figure JPOXMLDOC01-appb-C000016
 （式中、Ｒ1およびＲ2は式（２）と同じ）で示される４，５－ジアルキル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンとして、式（１Ａ）：
Figure JPOXMLDOC01-appb-C000017
 （式中、Ｒ1およびＲ2は同じかまたは異なり、いずれもフッ素原子を有していてもよくエーテル結合を有していてもよい炭素数１～４のアルキル基）で示されるtrans－４，５－ジアルキル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンが高収率で高選択率（trans－体選択率：７０～９０％、さらには８０～９０％、特に８５～９０％）に合成できることである。 The feature of the production method of the present invention is the formula (1):
Figure JPOXMLDOC01-appb-C000016
 (Wherein R 1 and R 2 are the same as those in the formula (2)), as a 4-5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one represented by the formula (1A):
Figure JPOXMLDOC01-appb-C000017
 (Wherein R 1 and R 2 are the same or different, both of which may have a fluorine atom or may have an ether bond and an alkyl group having 1 to 4 carbon atoms) trans-4 , 5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one with high yield and high selectivity (trans-isomer selectivity: 70 to 90%, more preferably 80 to 90%, especially 85 to 90%).
　またさらに、得られた高選択率でtrans－体を含む生成物を分別蒸留に供することにより、trans－体の純度を９９．５ＧＣ％（ゲルクロマロトグラフィ純度）以上にまで向上させることができる。 Furthermore, the purity of the trans-isomer can be improved to 99.5 GC% (gel chromatographic purity) or higher by subjecting the resulting product containing the trans-isomer to the fractional distillation. .
　式（１）で示される４，５－ジアルキル－４，５－ジフルオロ－１，３－ジオキソラン－２－オン、特に式（１Ａ）で示されるtrans－４，５－ジアルキル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンは、リチウム二次電池の電極（正極または負極）に安定な保護被膜を形成させる効果を有しており、非水電解液の添加剤として有用である。 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one represented by the formula (1), particularly trans-4,5-dialkyl-4,5-difluoro represented by the formula (1A) -1,3-Dioxolan-2-one has an effect of forming a stable protective film on the electrode (positive electrode or negative electrode) of a lithium secondary battery, and is useful as an additive for a nonaqueous electrolytic solution.
　つぎに実施例をあげて本発明の製造法を説明するが、本発明はこれらの実施例に限定されるものではない。 Next, the production method of the present invention will be described with reference to examples, but the present invention is not limited to these examples.
　以下の実施例で使用した分析方法はつぎのものである。 The analysis method used in the following examples is as follows.
（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）
　1Ｈ－ＭＮＲ：３００ＭＨｚ（トリフルオロメチルベンゼン＝７．５１ｐｐｍ） (1) NMR
Equipment: AC-300 manufactured by BRUKER
Measurement condition:
19 F-NMR: 282 MHz (trifluoromethylbenzene = -62.3 ppm)
1 H-MNR: 300 MHz (trifluoromethylbenzene = 7.51 ppm)
（２）trans－体の選択率（％）
　19Ｆ－ＮＭＲのデータから、trans－体とcis－体の積分値の比率によって決定する。 (2) Trans-isomer selectivity (%)
From 19 F-NMR data is determined by the ratio of integral value of trans- body and cis- body.
（３）trans－体の純度（ＧＣ％）
　ガスクロマトグラフィ（ＧＣ）により測定する。 (3) Trans-isomer purity (GC%)
Measured by gas chromatography (GC).
装置：（株）島津製作所製のＧＣ－１７Ａ
カラム：ＤＢ６２４（Ｌｅｎｇｔｈ６０、Ｉ.Ｄ　０．３２、Ｆｉｌｍ１．８μｍ）
測定条件：１００℃で５分間保持後、１０℃／分で２３０℃に昇温 Equipment: GC-17A manufactured by Shimadzu Corporation
Column: DB624 (Length 60, ID 0.32, Film 1.8 μm)
Measurement conditions: After holding at 100 ° C. for 5 minutes, the temperature is raised to 230 ° C. at 10 ° C./min.
参考例１（４，５－ジメチル－１，３－ジオキソラン－２－オン－４，５－エンの合成）
　３－ヒドロキシ－２－ブタノン５０ｇを窒素雰囲気下に９５℃に加熱し、１時間撹拌した。室温に冷却後、７５ｍＬのジクロロメタンと５３．９ｇのピリジンを加えた。反応溶液が１０℃を超えないようにしながらトリホスゲン／ジクロロメタン溶液（６７．５ｇ／１２５ｍＬ）を滴下した後、室温で１時間撹拌した。反応終了後、１Ｎ塩酸４００ｍＬを用いてクエンチし、つづいて１Ｎ塩酸２００ｍＬで洗浄し、さらに純水２００ｍＬで洗浄した。得られた４，５－ジメチル－５－クロロ－１，３－ジオキソラン－２－オンを含む有機層を硫酸マグネシウムを用いて乾燥し、ろ別後、エバポレータにて減圧濃縮した。濃縮液を１６０℃で３時間加熱撹拌して脱ＨＣｌ化した後、室温に冷却し、ヘキサンを２００ｍＬ加えて再結晶させ、４，５－ジメチル－１，３－ジオキソラン－２－オン－４，５－エンを６８．４ｇ得た（収率８０％、純度９７ＧＣ％）。 Reference Example 1 (Synthesis of 4,5-dimethyl-1,3-dioxolan-2-one-4,5-ene)
50 g of 3-hydroxy-2-butanone was heated to 95 ° C. under a nitrogen atmosphere and stirred for 1 hour. After cooling to room temperature, 75 mL dichloromethane and 53.9 g pyridine were added. A triphosgene / dichloromethane solution (67.5 g / 125 mL) was added dropwise so that the reaction solution did not exceed 10 ° C., and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction mixture was quenched with 400 mL of 1N hydrochloric acid, subsequently washed with 200 mL of 1N hydrochloric acid, and further washed with 200 mL of pure water. The obtained organic layer containing 4,5-dimethyl-5-chloro-1,3-dioxolan-2-one was dried using magnesium sulfate, filtered, and then concentrated under reduced pressure using an evaporator. The concentrated solution was heated and stirred at 160 ° C. for 3 hours to dehydrochlorinate, cooled to room temperature, recrystallized by adding 200 mL of hexane, 4,5-dimethyl-1,3-dioxolan-2-one-4, 68.4 g of 5-ene was obtained (yield 80%, purity 97 GC%).
実施例１（４，５－ジメチル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンの製造）
　５００ｍＬのニッケル製オートクレーブに、参考例１と同様にして製造した４，５－ジメチル－１，３－ジオキソラン－２－オン－４，５－エンを１１４ｇ、１，１，２－トリクロロ－１，２，２－トリフルオロエタン（以下、Ｒ－１１３と略す）を２００ｍＬ入れて撹拌し、－２０℃に冷却した。オートクレーブのガス出口にはアルミナ充填塔を接続し、さらに水酸化ナトリウム／亜硫酸ナトリウム水溶液を充填したトラップを接続した。窒素ガスを１時間吹き込んだ後、窒素ガスで２０容量％に希釈したフッ素ガスを流速６．０Ｌ／ｈで１１．２時間吹き込んだ。さらに窒素ガスを１時間吹き込んだ時点で反応生成液を19Ｆ－ＮＭＲで定量したところ、目的物である４，５－ジメチル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンの生成が確認され、そのtrans－体の選択率は８８％であった。 Example 1 (Production of 4,5-dimethyl-4,5-difluoro-1,3-dioxolan-2-one)
In a 500 mL nickel autoclave, 114 g of 4,5-dimethyl-1,3-dioxolan-2-one-4,5-ene produced in the same manner as in Reference Example 1, 1,1,2-trichloro-1, 200 mL of 2,2-trifluoroethane (hereinafter abbreviated as R-113) was added and stirred, and cooled to -20 ° C. An alumina packed tower was connected to the gas outlet of the autoclave, and a trap filled with a sodium hydroxide / sodium sulfite aqueous solution was connected. After nitrogen gas was blown for 1 hour, fluorine gas diluted to 20% by volume with nitrogen gas was blown for 11.2 hours at a flow rate of 6.0 L / h. Further, when nitrogen gas was blown in for 1 hour, the reaction product solution was quantified by 19 F-NMR. As a result, formation of 4,5-dimethyl-4,5-difluoro-1,3-dioxolan-2-one as the target product was obtained. The trans-isomer selectivity was 88%.
　この反応生成液をエバポレータで減圧下に濃縮し、つづいて１０段のオルダーショーを用いて減圧蒸留（１０～１１ｍｍＨｇ、溶液温度５５℃）したところ、trans－４，５－ジメチル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンを１２２ｇ（収率８０％、純度９９．７ＧＣ％）得た。 This reaction product solution was concentrated under reduced pressure using an evaporator, and then distilled under reduced pressure (10 to 11 mmHg, solution temperature 55 ° C.) using a 10-stage Oldershaw to find trans-4,5-dimethyl-4,5-difluoro. 122 g (yield 80%, purity 99.7 GC%) of 1,3-dioxolan-2-one was obtained.
参考例２（４，５－ジエチル－１，３－ジオキソラン－２－オン－４，５－エンの合成）
　４－ヒドロキシ－３－ブタノン５０ｇを窒素雰囲気下に９５℃に加熱し、１時間撹拌した。室温に冷却後、５０ｍＬのジクロロメタンと４０．９ｇのピリジンを加えた。反応溶液が１０℃を超えないようにしながらトリホスゲン／ジクロロメタン溶液（５１．１ｇ／１００ｍＬ）を滴下した後、室温で１時間撹拌した。反応終了後、１Ｎ塩酸３００ｍＬを用いてクエンチし、つづいて１Ｎ塩酸１５０ｍＬで洗浄し、さらに純水１５０ｍＬで洗浄した。得られた４，５－ジエチル－５－クロロ－１，３－ジオキソラン－２－オンを含む有機層を硫酸マグネシウムを用いて乾燥し、ろ別後、エバポレータにて減圧濃縮した。濃縮液を１６０℃で３時間加熱撹拌して脱ＨＣｌ化した後、室温に冷却し、ヘキサンを２００ｍＬ加えて再結晶させ、４，５－ジエチル－１，３－ジオキソラン－２－オン－４，５－エンを４７．７ｇ得た（収率７８％、純度９８ＧＣ％）。 Reference Example 2 (Synthesis of 4,5-diethyl-1,3-dioxolan-2-one-4,5-ene)
50 g of 4-hydroxy-3-butanone was heated to 95 ° C. under a nitrogen atmosphere and stirred for 1 hour. After cooling to room temperature, 50 mL dichloromethane and 40.9 g pyridine were added. A triphosgene / dichloromethane solution (51.1 g / 100 mL) was added dropwise so that the reaction solution did not exceed 10 ° C., and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction mixture was quenched with 300 mL of 1N hydrochloric acid, subsequently washed with 150 mL of 1N hydrochloric acid, and further washed with 150 mL of pure water. The obtained organic layer containing 4,5-diethyl-5-chloro-1,3-dioxolan-2-one was dried using magnesium sulfate, filtered, and concentrated under reduced pressure using an evaporator. The concentrated solution is heated and stirred at 160 ° C. for 3 hours to dehydrochlorinate, cooled to room temperature, recrystallized by adding 200 mL of hexane, 4,5-diethyl-1,3-dioxolan-2-one-4, 47.7 g of 5-ene was obtained (yield 78%, purity 98 GC%).
実施例２（４，５－ジエチル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンの製造）
　５００ｍＬのニッケル製オートクレーブに、参考例２と同様にして製造した４，５－ジエチル－１，３－ジオキソラン－２－オン－４，５－エンを１４２ｇ、Ｒ－１１３を２００ｍＬ入れて撹拌し、－２０℃に冷却した。オートクレーブのガス出口にはアルミナ充填塔を接続し、さらに水酸化ナトリウム／亜硫酸ナトリウム水溶液を充填したトラップを接続した。窒素ガスを１時間吹き込んだ後、窒素ガスで２０容量％に希釈したフッ素ガスを流速６．０Ｌ／ｈで１１．２時間吹き込んだ。さらに窒素ガスを１時間吹き込んだ時点で反応生成液を19Ｆ－ＮＭＲで定量したところ、目的物である４，５－ジエチル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンの生成が確認され、そのtrans－体の選択率は８５％であった。 Example 2 (Production of 4,5-diethyl-4,5-difluoro-1,3-dioxolan-2-one)
In a 500 mL nickel autoclave, 142 g of 4,5-diethyl-1,3-dioxolan-2-one-4,5-ene produced in the same manner as in Reference Example 2 and 200 mL of R-113 were placed and stirred. Cooled to -20 ° C. An alumina packed tower was connected to the gas outlet of the autoclave, and a trap filled with a sodium hydroxide / sodium sulfite aqueous solution was connected. After nitrogen gas was blown for 1 hour, fluorine gas diluted to 20% by volume with nitrogen gas was blown for 11.2 hours at a flow rate of 6.0 L / h. Further, when nitrogen gas was blown in for 1 hour, the reaction product solution was quantified by 19 F-NMR. As a result, the desired product 4,5-diethyl-4,5-difluoro-1,3-dioxolan-2-one was produced. The trans-isomer selectivity was 85%.
　この反応生成液をエバポレータで減圧下に濃縮し、つづいて１０段のオルダーショーを用いて減圧蒸留（１０～１１ｍｍＨｇ、溶液温度６７℃）したところ、trans－４，５－ジエチル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンを１４６ｇ（収率８１％、純度９９．６ＧＣ％）得た。 This reaction product solution was concentrated under reduced pressure using an evaporator, and then distilled under reduced pressure (10 to 11 mmHg, solution temperature 67 ° C.) using a 10-stage Oldershaw to find trans-4,5-diethyl-4,5-difluoro. 146 g (yield 81%, purity 99.6 GC%) of 1,3-dioxolan-2-one was obtained.

Claims (3)

  1. 　式（２）：
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１およびＲ２は同じかまたは異なり、いずれもフッ素原子を有していてもよくエーテル結合を有していてもよい炭素数１～４のアルキル基）で示される４，５－ジアルキル－１，３－ジオキソラン－２－オン－４，５－エンにフッ素化剤を反応させることを特徴とする式（１）：
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ１およびＲ２は式（２）と同じ）で示される４，５－ジアルキル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンの製造法。     Formula (2):
    Figure JPOXMLDOC01-appb-C000001
     (Wherein, R 1 and R 2 are the same or different and both have a fluorine atom and may have an ether bond, an alkyl group having 1 to 4 carbon atoms) 4,5 Formula (1) characterized by reacting a fluorinating agent with -dialkyl-1,3-dioxolan-2-one-4,5-ene:
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 1 and R 2 are the same as those in formula (2)), a method for producing 4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one.
  2. 　式（１）の４，５－ジアルキル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンが式（１Ａ）：
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ１およびＲ２は同じかまたは異なり、いずれもフッ素原子を有していてもよくエーテル結合を有していてもよい炭素数１～４のアルキル基）で示されるtrans－４，５－ジアルキル－４，５－ジフルオロ－１，３－ジオキソラン－２－オンである請求項１記載の製造方法。     4,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one of formula (1) is represented by formula (1A):
    Figure JPOXMLDOC01-appb-C000003
     (Wherein R 1 and R 2 are the same or different, both of which may have a fluorine atom or may have an ether bond and an alkyl group having 1 to 4 carbon atoms) trans-4 The production method according to claim 1, which is 1,5-dialkyl-4,5-difluoro-1,3-dioxolan-2-one.
  3. 　フッ素化剤が、フッ素ガスである請求項１または２記載の製造方法。 The method according to claim 1 or 2, wherein the fluorinating agent is fluorine gas.
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