JP4848683B2 - Method for producing high-purity 4-fluoro-1,3-dioxolan-2-one - Google Patents
Method for producing high-purity 4-fluoro-1,3-dioxolan-2-one Download PDFInfo
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 title claims description 83
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 40
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- 238000001556 precipitation Methods 0.000 claims description 36
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 claims description 21
- 235000003270 potassium fluoride Nutrition 0.000 claims description 20
- 239000011698 potassium fluoride Substances 0.000 claims description 20
- 238000000746 purification Methods 0.000 claims description 19
- 238000004821 distillation Methods 0.000 claims description 18
- 238000003682 fluorination reaction Methods 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 5
- MCSBDMFGKYZBTA-UHFFFAOYSA-N 4-fluoro-1,3-dioxolane Chemical compound FC1COCO1 MCSBDMFGKYZBTA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 description 48
- 239000002904 solvent Substances 0.000 description 47
- 229910052801 chlorine Inorganic materials 0.000 description 41
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 40
- 238000000034 method Methods 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 11
- 238000011084 recovery Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012025 fluorinating agent Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Description
本発明は、二次電池用の溶媒や添加剤、医農薬製造用の中間体等に有用な４−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-fluoro-1,3-dioxolan-2-one useful as a solvent or additive for a secondary battery, an intermediate for producing a pharmaceutical or agrochemical, and the like.
４−フルオロ−１，３−ジオキソラン−２−オンはリチウムイオン電池等の二次電池、あるいは電気二重層キャパシタ用の溶媒、添加剤として有望な化合物である。例えば、特許文献１には、該化合物を溶媒として用いたリチウムイオン二次電池が、フッ素置換されていない溶媒を用いた二次電池に比較して、充放電の電流効率が優れ、良好な充放電サイクル特性を示すことが開示されている。 4-Fluoro-1,3-dioxolan-2-one is a promising compound as a solvent and additive for secondary batteries such as lithium ion batteries or electric double layer capacitors. For example, Patent Document 1 discloses that a lithium ion secondary battery using the compound as a solvent has better charge / discharge current efficiency and better chargeability than a secondary battery using a solvent not substituted with fluorine. It is disclosed to exhibit discharge cycle characteristics.
４−フルオロ−１，３−ジオキソラン−２−オンの製造方法としては、次のものが知られている。
［１］４−クロロ−１，３−ジオキソラン−２−オンに、乾燥条件下で等モルのフッ化カリウムを加え反応させ、次いで蒸留する方法（特許文献２）。本方法によれば、７０％以上の収率で４−フルオロ−１，３−ジオキソラン−２−オンが得られると記載されている。
［２］「エチレンカーボネートの融解液か、エチレンカーボネートの無水ＨＦ溶液」に、「Ｆ2ガスまたは、Ｆ2ガスと不活性ガスの混合ガス」を導入し、温度−２０〜１００℃で反応させる方法（特許文献３）。該文献によると、無水ＨＦを過剰に共存させた条件下では比較的高い選択率で目的化合物が得られる。さらに、該反応をアセトニトリル溶媒中で行う方法も知られている（特許文献４）。
[1] A method of reacting 4-chloro-1,3-dioxolan-2-one with equimolar potassium fluoride under dry conditions, followed by distillation (Patent Document 2). According to this method, it is described that 4-fluoro-1,3-dioxolan-2-one can be obtained with a yield of 70% or more.
[2] “F 2 gas or a mixed gas of F 2 gas and inert gas” is introduced into “melt of ethylene carbonate or anhydrous HF solution of ethylene carbonate” and reacted at a temperature of −20 to 100 ° C. Method (Patent Document 3). According to this document, the target compound can be obtained with a relatively high selectivity under the condition where anhydrous HF is excessively present. Furthermore, a method of performing the reaction in an acetonitrile solvent is also known (Patent Document 4).
上記［１］の方法によれば、安価に入手できるフッ化カリウムをフッ素化剤として、高収率で４−フルオロ−１，３−ジオキソラン−２−オンを製造できる。フッ素化剤が固体であるため、操作も比較的容易である。しかしながら、この方法では、原料として４−クロロ−１，３−ジオキソラン−２−オンを使用するために、反応終了後の粗４−フルオロ−１，３−ジオキソラン−２−オン中に、「塩素根」が共存するという問題があった。ここで「塩素根」とは、原料である４−クロロ−１，３−ジオキソラン−２−オン、ならびに副生する塩化水素（ＨＣｌ）、さらには４−クロロ−１，３−ジオキソラン−２−オン中に不純物として共存し得る塩素（Ｃｌ2）など、「塩素原子（Ｃｌ）または塩化物イオン（Ｃｌ-）を含む化学種」を総称する。「塩素根」が残留した４−フルオロ−１，３−ジオキソラン−２−オンを電気デバイス用途に使用すると、電気デバイスのサイクル特性が低下することがある。しかしながら、特許文献２に開示されている、反応後の蒸留精製では「塩素根」を十分に除去することができなかった。また該フッ素化は、反応変換率を完全に１００％にすることは困難で、原料の４−クロロ−１，３−ジオキソラン−２−オンを反応によって完全に消費することも難しい。 According to the method [1], 4-fluoro-1,3-dioxolan-2-one can be produced in high yield using potassium fluoride, which is available at a low cost, as a fluorinating agent. Since the fluorinating agent is a solid, the operation is relatively easy. However, in this method, since 4-chloro-1,3-dioxolan-2-one is used as a raw material, in the crude 4-fluoro-1,3-dioxolan-2-one after completion of the reaction, “chlorine” There was a problem that "roots" coexist. Here, “chlorine root” means 4-chloro-1,3-dioxolan-2-one as a raw material, hydrogen chloride (HCl) as a by-product, and 4-chloro-1,3-dioxolane-2- “Chemical species containing chlorine atoms (Cl) or chloride ions (Cl − )” such as chlorine (Cl 2 ) that can coexist as impurities in the ON are collectively referred to. When 4-fluoro-1,3-dioxolan-2-one in which the “chlorine root” remains is used for an electric device, the cycle characteristics of the electric device may be deteriorated. However, the “chlorine root” cannot be sufficiently removed by distillation purification after the reaction disclosed in Patent Document 2. Further, in the fluorination, it is difficult to make the reaction conversion rate completely 100%, and it is also difficult to completely consume the raw material 4-chloro-1,3-dioxolan-2-one by the reaction.
これに対し、上記［２］の方法は、エチレンカーボネートを、フッ素（Ｆ2）ガスで直接フッ素化するため、「塩素根」が系内に混入する恐れはない。しかしこの方法は、高価なフッ素ガスをフッ素源とするため、経済的には不利である。さらに、この直接的なフッ素化は、元来選択率の低い反応で、目的物の他に、異なる部位がフッ素化を受けた化合物、複数部位がフッ素化を受けた化合物が副生しやすく、系内の不純物プロフィールが複雑になる。選択性を高めるためには、大過剰量のＨＦを共存させて反応を行う必要があり、反応後の精製が煩雑になるという問題があった。 On the other hand, since the method [2] directly fluorinates ethylene carbonate with fluorine (F 2 ) gas, there is no possibility that “chlorine root” is mixed into the system. However, this method is economically disadvantageous because expensive fluorine gas is used as the fluorine source. Furthermore, this direct fluorination is originally a reaction with low selectivity. In addition to the target product, a compound in which different sites have undergone fluorination and a compound in which multiple sites have undergone fluorination are easily produced as by-products. Impurity profile in the system is complicated. In order to increase the selectivity, it is necessary to carry out the reaction in the presence of a large excess of HF, and there is a problem that purification after the reaction becomes complicated.
このように、高純度４−フルオロ−１，３−ジオキソラン−２−オンを製造するための従来の方法は、大規模で製造するためには十分とはいえず、改善が求められていた。 Thus, the conventional method for producing high-purity 4-fluoro-1,3-dioxolan-2-one is not sufficient for producing on a large scale, and improvement has been demanded.
本発明者らは、かかる問題点に鑑み、高純度の４−フルオロ−１，３−ジオキソラン−２−オンを工業的に生産するための方法につき、鋭意検討をした。その結果、粗４−フルオロ−１，３−ジオキソラン−２−オンを、比誘電率が３．５以下である低極性溶媒と接触させて４−フルオロ−１，３−ジオキソラン−２−オンを沈殿化すると、不純物として共存する「塩素根」を、著しく高い効率で除去でき、高純度４−フルオロ−１，３−ジオキソラン−２−オンを製造できるという知見を得た。 In view of such problems, the present inventors have intensively studied a method for industrially producing high-purity 4-fluoro-1,3-dioxolan-2-one. As a result, the crude 4-fluoro-1,3-dioxolan-2-one was brought into contact with a low polarity solvent having a relative dielectric constant of 3.5 or less to give 4-fluoro-1,3-dioxolan-2-one. As a result of the precipitation, it was found that “chlorine roots” coexisting as impurities can be removed with extremely high efficiency, and high-purity 4-fluoro-1,3-dioxolan-2-one can be produced.
本発明において、「４−フルオロ−１，３−ジオキソラン−２−オンの沈殿化」とは、４−フルオロ−１，３−ジオキソラン−２−オンを少量の溶媒（良溶媒）に溶解させ、溶液にした上で、該溶液を、比誘電率が３．５以下である低極性溶媒（本明細書において、「貧溶媒」とも呼ぶ。）と接触させ、４−フルオロ−１，３−ジオキソラン−２−オンを沈殿化させる一連の操作をいう。本操作は「共沈化」とも呼ばれるが、本明細書では「沈殿化」と呼ぶことにする。 In the present invention, “precipitation of 4-fluoro-1,3-dioxolan-2-one” refers to dissolving 4-fluoro-1,3-dioxolan-2-one in a small amount of solvent (good solvent), After making into a solution, the solution is contacted with a low-polarity solvent (also referred to herein as a “poor solvent”) having a relative dielectric constant of 3.5 or less, and 4-fluoro-1,3-dioxolane is obtained. A series of operations for precipitating 2-one. This operation is also referred to as “coprecipitation”, but is referred to herein as “precipitation”.
本発明者らは、該低極性溶媒（貧溶媒）としては、トルエンが特に好ましいことも見出した。 The present inventors have also found that toluene is particularly preferable as the low polarity solvent (poor solvent).
本発明が特にそのメリットを発揮するのは、４−クロロ−１，３−ジオキソラン−２−オンを、フッ化カリウムと、アセトニトリル中、無水条件下で接触させて、粗４−フルオロ−１，３−ジオキソラン−２−オンを製造する場合である。前述のように、本反応は操作が容易であり、選択率、収率も高いというメリットを有する一方で、反応混合物中に「塩素根」が相当量混入する結果となる。しかし上述の沈殿化を行うことにより、この「塩素根」をごく容易に、電気デバイス用途に要求される濃度以下に低減できることとなった。とりわけ、この沈殿化（共沈化）を２回以上行うと「塩素根」低減の効果が著しいことも判明した。 The present invention is particularly advantageous in that 4-chloro-1,3-dioxolan-2-one is brought into contact with potassium fluoride in acetonitrile under anhydrous conditions to give crude 4-fluoro-1, This is the case of producing 3-dioxolan-2-one. As described above, this reaction has the advantages of being easy to operate and having high selectivity and high yield, while resulting in a considerable amount of “chlorine root” being mixed into the reaction mixture. However, by carrying out the above-mentioned precipitation, this “chlorine root” can be reduced very easily to a concentration lower than that required for electric device applications. In particular, it has also been found that the effect of reducing “chlorine roots” is remarkable when this precipitation (coprecipitation) is performed twice or more.
これらの知見の結果、高純度４−フルオロ−１，３−ジオキソラン−２−オンが従来技術に比較して、経済的にも、操作的にも、有利に製造できることとなった。 As a result of these findings, high-purity 4-fluoro-1,3-dioxolan-2-one can be advantageously produced economically and operationally compared to the prior art.
すなわち、本発明は、次の［発明１］〜［発明５］を骨子とする、高純度４−フルオロ−１，３−ジオキソラン−２−オンの製造方法である。 That is, the present invention is a method for producing high-purity 4-fluoro-1,3-dioxolan-2-one based on the following [Invention 1] to [Invention 5 ].
［発明１］次の各工程を含む、高純度４−フルオロ−１，３−ジオキソラン−２−オンの製造方法。
第１工程（フッ素化工程）：４−クロロ−１，３−ジオキソラン−２−オンをフッ化カリウムと、アセトニトリル中、無水条件下で接触させて、粗４−フルオロ−１，３−ジオキソラン−２−オンを得る工程。
第２工程（精製工程）：前記第１工程で得られた粗４−フルオロ−１，３−ジオキソラン−２−オンの溶液を、トルエンと接触させて４−フルオロ−１，３−ジオキソラン−２−オンを沈殿化し、高純度４−フルオロ−１，３−ジオキソラン−２−オンを得る工程。
[Invention 1 ] A process for producing high-purity 4-fluoro-1,3-dioxolan-2-one, comprising the following steps.
First step (fluorination step): 4-chloro-1,3-dioxolan-2-one is contacted with potassium fluoride in acetonitrile under anhydrous conditions to give crude 4-fluoro-1,3-dioxolane- Obtaining 2-one.
Second step (purification step): The solution of the crude 4-fluoro-1,3-dioxolan-2-one obtained in the first step is brought into contact with toluene to give 4-fluoro-1,3-dioxolane-2. -Precipitating the ones to obtain high purity 4-fluoro-1,3-dioxolan-2-one.
［発明２］４−フルオロ−１，３−ジオキソラン−２−オンの沈殿化を５℃以下の温度で行うことを特徴とする、発明１に記載の、高純度４−フルオロ−１，３−ジオキソラン−２−オンの製造方法。 [Invention 2 ] High-purity 4-fluoro-1,3- according to Invention 1 , characterized in that precipitation of 4-fluoro-1,3-dioxolan-2-one is carried out at a temperature of 5 ° C. or lower. A method for producing dioxolan-2-one.
［発明３］４−フルオロ−１，３−ジオキソラン−２−オンの沈殿化を少なくとも２回行うことを特徴とする、発明１又は発明２に記載の、高純度４−フルオロ−１，３−ジオキソラン−２−オンの製造方法。 [Invention 3 ] High-purity 4-fluoro-1,3- according to Invention 1 or Invention 2 , characterized in that precipitation of 4-fluoro-1,3-dioxolan-2-one is performed at least twice. A method for producing dioxolan-2-one.
［発明４］蒸留精製を併せて行うことを特徴とする、発明１乃至発明３の何れかに記載の、高純度４−フルオロ−１，３−ジオキソラン−２−オンの製造方法。 [Invention 4 ] The process for producing high-purity 4-fluoro-1,3-dioxolan-2-one according to any one of Inventions 1 to 3 , wherein distillation purification is performed together.
［発明５］次の各工程を含む、高純度４−フルオロ−１，３−ジオキソラン−２−オンの製造方法。
第１工程（フッ素化工程）：４−クロロ−１，３−ジオキソラン−２−オンをフッ化カリウムと、アセトニトリル中、無水条件下で接触させて、粗４−フルオロ−１，３−ジオキソラン−２−オンを得る工程。
第２工程（精製工程）：前記第１工程で得られた祖４−フルオロ−１，３−ジオキソラン−２−オンの溶液を、５℃以下の温度でトルエンと接触させ４−フルオロ−１，３−ジオキソラン−２−オンを沈殿化する操作を、少なくとも２回行い、併せて蒸留精製を行う工程。
[Invention 5 ] A process for producing high-purity 4-fluoro-1,3-dioxolan-2-one comprising the following steps.
First step (fluorination step): 4-chloro-1,3-dioxolan-2-one is contacted with potassium fluoride in acetonitrile under anhydrous conditions to give crude 4-fluoro-1,3-dioxolane- Obtaining 2-one.
Second step (purification step): The solution of the original 4-fluoro-1,3-dioxolan-2-one obtained in the first step is brought into contact with toluene at a temperature of 5 ° C. or lower to give 4-fluoro-1, A step of performing an operation of precipitating 3-dioxolan-2-one at least twice and performing distillation purification together.
本発明によると、塩素成分を含まない、高純度の４−フルオロ−１，３−ジオキソラン−２−オンを、従来技術よりも効率よく製造できる。とりわけ、安価で入手できる４−クロロ−１，３−ジオキソラン−２−オンをフッ化カリウムによってフッ素化して得られた粗４−フルオロ−１，３−ジオキソラン−２−オンから、不純物として共存する「塩素根」を容易に除去できるため、経済的にも大きなメリットを奏する。 According to the present invention, high-purity 4-fluoro-1,3-dioxolan-2-one containing no chlorine component can be produced more efficiently than in the prior art. In particular, it coexists as an impurity from crude 4-fluoro-1,3-dioxolan-2-one obtained by fluorinating 4-chloro-1,3-dioxolan-2-one, which is available at low cost, with potassium fluoride. Since the “chlorine root” can be easily removed, there is a great economic advantage.
以下、本発明につき、さらに詳細に説明する。まず本発明において、「高純度４−フルオロ−１，３−ジオキソラン−２−オン」とは、「塩素根」の含有量（４−フルオロ−１，３−ジオキソラン−２−オン中の全塩素濃度）が概ね１００ｐｐｍ以下のものを指し、好ましくは５０ｐｐｍ以下のもの、さらに好ましくは２０ｐｐｍ以下のものをいう。本発明の沈殿化は「塩素根」の含量を低減させるのに十分な効果があるため、沈殿化の回数や条件を適宜調整することで、「塩素根」含有量がこれらの条件を満たす「高純度４−フルオロ−１，３−ジオキソラン−２−オン」を容易に製造できる。 Hereinafter, the present invention will be described in more detail. First, in the present invention, “high purity 4-fluoro-1,3-dioxolan-2-one” means the content of “chlorine root” (total chlorine in 4-fluoro-1,3-dioxolan-2-one (Concentration) is generally 100 ppm or less, preferably 50 ppm or less, more preferably 20 ppm or less. Since the precipitation of the present invention has a sufficient effect to reduce the content of “chlorine root”, the content of “chlorine root” satisfies these conditions by appropriately adjusting the number and conditions of precipitation. High purity 4-fluoro-1,3-dioxolan-2-one "can be easily produced.
本発明の沈殿化精製に供する粗４−フルオロ−１，３−ジオキソラン−２−オンとしては、いずれの方法で製造された粗４−フルオロ−１，３−ジオキソラン−２−オンをも用いることができる。しかし「塩素根」を効果的に除去できるという、本発明の精製方法のメリットを生かすためには、安価に入手できる４−クロロ−１，３−ジオキソラン−２−オンを、フッ化カリウムと、アセトニトリル中、無水条件下で接触させて、粗４−フルオロ−１，３−ジオキソラン−２−オンを得ることが好ましい。 As crude 4-fluoro-1,3-dioxolan-2-one used for precipitation purification of the present invention, crude 4-fluoro-1,3-dioxolan-2-one produced by any method should be used. Can do. However, in order to take advantage of the purification method of the present invention that “chlorine roots” can be effectively removed, 4-chloro-1,3-dioxolan-2-one, which is available at low cost, is combined with potassium fluoride , It is preferable to contact in acetonitrile under anhydrous conditions to obtain crude 4-fluoro-1,3-dioxolan-2-one.
そこで本明細書では、４−クロロ−１，３−ジオキソラン−２−オンをフッ化カリウムと反応させて、粗４−フルオロ−１，３−ジオキソラン−２−オンを得る工程を「第１工程」と呼び、引き続いて、この粗４−フルオロ−１，３−ジオキソラン−２−オンを、沈殿化を含む精製操作に付す工程を「第２工程」と呼び、順に説明を加えることにする。 Therefore, in this specification, the step of reacting 4-chloro-1,3-dioxolan-2-one with potassium fluoride to obtain crude 4-fluoro-1,3-dioxolan-2-one is referred to as “first step. The process of subjecting the crude 4-fluoro-1,3-dioxolan-2-one to a purification operation including precipitation will be referred to as a “second process” and will be described in order.
本発明の概要を、下記のスキームにまとめる。 The outline of the present invention is summarized in the following scheme.
まず第１工程について、説明する。第１工程は、４−クロロ−１，３−ジオキソラン−２−オンを、フッ化カリウムと、アセトニトリル中、無水条件下で接触させて、粗４−フルオロ−１，３−ジオキソラン−２−オンを得る工程である。第１工程は、特許文献２に記載された条件にならって実施すればよいが、本発明者らは本工程において有機溶媒を反応溶媒として用いるとさらに有効であることを見出した。ここではその方法、条件を詳しく説明する。 First, the first step will be described. The first step involves contacting 4-chloro-1,3-dioxolan-2-one with potassium fluoride in acetonitrile under anhydrous conditions to give crude 4-fluoro-1,3-dioxolan-2-one. It is the process of obtaining. The first step may be performed according to the conditions described in Patent Document 2, but the present inventors have found that it is more effective to use an organic solvent as a reaction solvent in this step. Here, the method and conditions will be described in detail.
まず、第１工程の原料である４−クロロ−１，３−ジオキソラン−２−オンの製造方法については、特別な制限はないが、エチレンカーボネートをラジカル開始剤の存在下、光照射下、または熱時条件下で、塩素ガス（Ｃｌ2）と反応させることで容易に得ることができ、それが最も経済的である。得られた４−クロロ−１，３−ジオキソラン−２−オンは、通常の有機合成に用いられる精製手段によって、純度を９５％以上に高めた上で反応原料に供することが好ましい。 First, the production method of 4-chloro-1,3-dioxolan-2-one that is a raw material in the first step is not particularly limited, but ethylene carbonate is used in the presence of a radical initiator, under light irradiation, or It can be easily obtained by reacting with chlorine gas (Cl 2 ) under hot conditions, which is the most economical. The obtained 4-chloro-1,3-dioxolan-2-one is preferably used as a reaction raw material after its purity is increased to 95% or more by a purification means used in ordinary organic synthesis.
第１工程における「無水条件」とは、フッ化金属等の試薬として無水の試薬を用い、かつ、脱水溶媒を使用することで達成される。具体的には水分が１００ｐｐｍ以下の条件を言い、５０ｐｐｍ以下がより好ましい。 The “anhydrous condition” in the first step is achieved by using an anhydrous reagent as a reagent such as a metal fluoride and using a dehydrating solvent. Specifically, the condition is that moisture is 100 ppm or less, and 50 ppm or less is more preferable.
第１工程に用いられるフッ化カリウムは、前述のように無水試薬が好ましく、工業的に、しかも安価に入手できる無水フッ化カリウムが特に好ましい。無水フッ化カリウムの形状に特に制限は無いが、スプレードライ品が最も良い結果を与えるので特に好ましい。フッ化カリウムの量は、４−クロロ−１，３−ジオキソラン−２−オン１モルに対して、通常１モル以上用いるが、十分な収率で目的物を得るためには、１〜２モルが好ましく、１〜１．５モルが特に好ましい。２モルを超えて用いると、反応に関与しないフッ化カリウムが増え、経済的に不利となるため、好ましくない。 Potassium fluoride used in the first step, rather preferably anhydrous reagent as described above, industrially, inexpensively anhydrous potassium fluoride available is particularly preferred. Although there is no restriction | limiting in particular in the shape of anhydrous potassium fluoride, since a spray-dried product gives the best result, it is especially preferable. The amount of potassium fluoride is usually 1 mol or more based on 1 mol of 4-chloro-1,3-dioxolan-2-one, but in order to obtain the desired product in sufficient yield, 1 to 2 mol 1 to 1.5 mol is particularly preferable. If it is used in excess of 2 moles, potassium fluoride not involved in the reaction is increased, which is disadvantageous economically.
第１工程の反応は、酸性条件に耐える反応装置を用い、４−クロロ−１，３−ジオキソラン−２−オンとフッ化カリウムをスラリー状にして攪拌しながら接触させると、特に円滑に実施できる。この際、副生物として塩化水素が発生するため、順次パージし、系内から除去することが好ましい。 The reaction in the first step can be carried out particularly smoothly by using a reaction device that can withstand acidic conditions and contacting 4-chloro-1,3-dioxolan-2-one and potassium fluoride in a slurry state while stirring. . At this time, since hydrogen chloride is generated as a by-product, it is preferable to sequentially purge and remove from the system.
第１工程の反応は、溶媒の存在下行う。溶媒としては、フッ化カリウムを溶解させる作用の高い、極性有機溶媒を用いると、特に反応速度が高まり好ましい。具体的には、アセトニトリルである。 The reaction in the first step is performed in the presence of a solvent . As the solvent, it is preferable to use a polar organic solvent having a high action of dissolving potassium fluoride because the reaction rate is particularly increased. Specifically, it is acetonitrile.
第１工程の反応の温度は通常２０℃〜１５０℃であるが、溶媒を用いる場合には２０℃〜使用する溶媒の沸点までである。好ましくは４０℃〜１２０℃、より好ましくは６０℃〜１００℃である。 The temperature of the reaction in the first step is usually 20 ° C. to 150 ° C., but when a solvent is used, it is 20 ° C. to the boiling point of the solvent used. Preferably it is 40 to 120 degreeC, More preferably, it is 60 to 100 degreeC.
第１工程の反応の反応時間に特別な制限はないが、ガスクロマトグラフィー等の手法によって、原料の４−クロロ−１，３−ジオキソラン−２−オンの消費が十分に進み、もはや反応が進行しないことを確認してから終了するのが望ましい。 Although there is no particular limitation on the reaction time of the reaction in the first step, consumption of the raw material 4-chloro-1,3-dioxolan-2-one is sufficiently advanced by the method such as gas chromatography, and the reaction no longer proceeds. It is desirable to finish after confirming that it does not.
続いて、第２工程について説明する。第２工程は精製工程であり、粗４−フルオロ−１，３−ジオキソラン−２−オンの溶液を、トルエンと接触させて４−フルオロ−１，３−ジオキソラン−２−オンを沈殿化する操作によりなる。 Subsequently, the second step will be described. The second step is a purification step, in which a solution of crude 4-fluoro-1,3-dioxolan-2-one is brought into contact with toluene to precipitate 4-fluoro-1,3-dioxolan-2-one. It becomes by.
本発明において「沈殿化」とは、粗４−フルオロ−１，３−ジオキソラン−２−オンを溶解しうる有機溶媒（良溶媒）に粗４−フルオロ−１，３−ジオキソラン−２−オンを溶解させた溶液を、４−フルオロ−１，３−ジオキソラン−２−オンを殆ど溶解しない低極性溶媒（貧溶媒）に、適切な温度において接触させ、４−フルオロ−１，３−ジオキソラン−２−オンを沈殿化させる操作のことをいう。本工程を行うことによって「塩素根」が系内から除去され、高純度４−フルオロ−１，３−ジオキソラン−２−オンを得ることができる。 In the present invention, “precipitation” means that crude 4-fluoro-1,3-dioxolan-2-one is dissolved in an organic solvent (good solvent) that can dissolve crude 4-fluoro-1,3-dioxolan-2-one. The dissolved solution is brought into contact with a low polarity solvent (poor solvent) that hardly dissolves 4-fluoro-1,3-dioxolan-2-one at an appropriate temperature, and 4-fluoro-1,3-dioxolane-2 is obtained. -Refers to the operation of precipitating on. By performing this step, the “chlorine root” is removed from the system, and high-purity 4-fluoro-1,3-dioxolan-2-one can be obtained.
第２工程の沈殿化においては、トルエンを、「低極性溶媒（貧溶媒）」として用いる。トルエンを用いると、「塩素根」を効果的に除去できるだけでなく、沈殿化を通じた回収率もごく高い値となるため、特に好ましい。 In the precipitation in the second step, toluene is used as a “low polarity solvent (poor solvent)”. Toluene is particularly preferable because it not only effectively removes “chlorine roots” but also has a very high recovery rate through precipitation.
この溶媒は、単独で使用する。 This solvent is used alone .
一方、比誘電率が３．５よりも大きい有機溶媒を低極性溶媒（貧溶媒）として用いると、４−フルオロ−１，３−ジオキソラン−２−オンの溶解度が著しく増大し、本工程の沈殿化が難しくなる。 On the other hand, when an organic solvent having a relative dielectric constant larger than 3.5 is used as a low polarity solvent (poor solvent), the solubility of 4-fluoro-1,3-dioxolan-2-one is remarkably increased, and precipitation in this step is performed. It becomes difficult.
トルエンの使用量は、粗４−フルオロ−１，３−ジオキソラン−２−オン１ｇあたり、通常０．５〜２０ｇであり、０．７〜１０ｇが好ましく、１〜５ｇが特に好ましい。 The amount of toluene used is usually 0.5 to 20 g, preferably 0.7 to 10 g, particularly preferably 1 to 5 g, per 1 g of crude 4-fluoro-1,3-dioxolan-2-one.
一方、４−フルオロ−１，３−ジオキソラン−２−オンを予め溶解させるための有機溶媒（良溶媒）としてはアセトニトリル、テトラヒドロフラン、塩化メチレン、クロロホルム、ニトロメタン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、１，３−ジメチル−２−イミダゾリジノンなどが例示できるが、第１工程で使用した溶媒を用いるのが好ましい。 On the other hand, as an organic solvent (good solvent) for dissolving 4-fluoro-1,3-dioxolan-2-one in advance, acetonitrile, tetrahydrofuran, methylene chloride, chloroform, nitromethane, N, N-dimethylformamide, N, N -Dimethylacetamide, 1,3-dimethyl-2-imidazolidinone and the like can be exemplified, but it is preferable to use the solvent used in the first step.
「良溶媒」の使用量は、溶媒に対する４−フルオロ−１，３−ジオキソラン−２−オンの溶解度および粗４−フルオロ−１，３−ジオキソラン−２−オンの純度によって異なるが、粗４−フルオロ−１，３−ジオキソラン−２−オン１ｇあたり、通常０．０１〜２．０ｇであり、０．１ｇ〜１．０ｇが好ましく、０．１５〜０．５ｇが特に好ましい。良溶媒が０．０１ｇ未満であると、４−フルオロ−１，３−ジオキソラン−２−オンが十分に溶解せず、逆に２．０ｇよりも多いと、４−フルオロ−１，３−ジオキソラン−２−オンの回収率が低下するので、何れも好ましくない。 The amount of the “good solvent” used depends on the solubility of 4-fluoro-1,3-dioxolan-2-one in the solvent and the purity of the crude 4-fluoro-1,3-dioxolan-2-one. The amount is usually 0.01 to 2.0 g, preferably 0.1 to 1.0 g, particularly preferably 0.15 to 0.5 g, per 1 g of fluoro-1,3-dioxolan-2-one. If the good solvent is less than 0.01 g, 4-fluoro-1,3-dioxolan-2-one is not sufficiently dissolved, and conversely if it is more than 2.0 g, 4-fluoro-1,3-dioxolane Since the recovery rate of 2-one decreases, neither is preferable.
なお、第２工程（精製工程）を第１工程（フッ素化工程）に引き続いて実施する場合、第１工程で得た粗４−フルオロ−１，３−ジオキソラン−２−オンを、一旦沈殿物として単離し、かかる後に、該沈殿物を良溶媒に溶解した上で、「低極性溶媒」と接触させることもできる。しかし、第１工程の反応混合物を濃縮しても、系内に共存する不純物（副生物のエチレンカーボネート、ビニレンカーボネート、原料の４−クロロ−１，３−ジオキソラン−２−オンなどの不純物など）が「良溶媒」の役割を果たし、４−フルオロ−１，３−ジオキソラン−２−オンを十分に溶解し、溶液状態を呈することが多い（例えば４−フルオロ−１，３−ジオキソラン−２−オンの純度が８５％以下の場合）。この溶液をそのまま、「低極性溶媒」と接触させれば、第２工程の「沈殿化」が達成できる。本方法によれば、別途良溶媒を添加する必要がないため、経済的、操作的に特に好ましい。 When the second step (purification step) is carried out subsequent to the first step (fluorination step), the crude 4-fluoro-1,3-dioxolan-2-one obtained in the first step is once precipitated. The precipitate can be dissolved in a good solvent and then contacted with a “low polarity solvent”. However, even if the reaction mixture of the first step is concentrated, impurities coexisting in the system (impurities such as by-product ethylene carbonate, vinylene carbonate, raw material 4-chloro-1,3-dioxolan-2-one, etc.) Often plays a role of “good solvent” and sufficiently dissolves 4-fluoro-1,3-dioxolan-2-one to take a solution state (for example, 4-fluoro-1,3-dioxolane-2-one). When the ON purity is 85% or less). If this solution is brought into contact with a “low polarity solvent” as it is, “precipitation” in the second step can be achieved. According to this method, since it is not necessary to add a good solvent separately, it is particularly preferable economically and in operation.
「沈殿化」の操作手順に特別な制限はないが、次のように行うことが好ましい。まず、粗４−フルオロ−１，３−ジオキソラン−２−オンの溶液（良溶媒に溶解したもの）を、比誘電率が３．５以下である低極性溶媒（貧溶媒）の中に、徐々に滴下する。このような手順によると、「沈殿化」が特に円滑に起こるため、高純度の４−フルオロ−１，３−ジオキソラン−２−オンを得る上で、特に好適である。 Although there is no special restriction | limiting in the operation procedure of "precipitation", it is preferable to carry out as follows. First, a solution of crude 4-fluoro-1,3-dioxolan-2-one (dissolved in a good solvent) is gradually added into a low polarity solvent (poor solvent) having a relative dielectric constant of 3.5 or less. Dripping into. Such a procedure is particularly suitable for obtaining high-purity 4-fluoro-1,3-dioxolan-2-one because “precipitation” occurs particularly smoothly.
「沈殿化」の行われる温度は、通常、使用される有機溶媒の融点〜３０℃であり、−５０℃〜１０℃が好ましく、−２０℃から５℃がより好ましい。 The temperature at which “precipitation” is performed is usually from the melting point to 30 ° C. of the organic solvent used, preferably −50 ° C. to 10 ° C., more preferably −20 ° C. to 5 ° C.
第２工程の「沈殿化（共沈化）」は１度行うだけであっても、十分大きな「塩素根」除去の効果を示す（実施例を参照）が、２回以上繰り返すと、特に大きな効果を生じる。したがって、要求される「塩素根」含量に応じて、２回以上、「沈殿化」操作を繰り返すことが特に好ましい。 Even if the “precipitation (co-precipitation)” in the second step is performed only once, a sufficiently large “chlorine root” removal effect is shown (see Examples). Produces an effect. Therefore, it is particularly preferred to repeat the “precipitation” operation more than once depending on the required “chlorine root” content.
このような方法で沈殿化した結晶は、その後濾過等の手法により分取することができる。また、低極性溶媒を除いた後、再度融解させて容器外に回収することもできる。回収された高純度４−フルオロ−１，３−ジオキソラン−２−オンの結晶は低極性溶媒（例えば、ｎ−ヘキサン、ｎ−ヘプタン等）で洗浄することができ、その後、減圧脱気するなどの操作により、これらの低極性溶媒を除けば、電気デバイス用に適した４−フルオロ−１，３−ジオキソラン−２−オンの製品として回収することができる。 Crystals precipitated by such a method can then be collected by a technique such as filtration. Further, after removing the low-polarity solvent, it can be melted again and recovered outside the container. The recovered crystals of high-purity 4-fluoro-1,3-dioxolan-2-one can be washed with a low polarity solvent (for example, n-hexane, n-heptane, etc.), and then degassed under reduced pressure. By removing the low-polarity solvent by this operation, it can be recovered as a product of 4-fluoro-1,3-dioxolan-2-one suitable for electric devices.
しかしながら、より安定した品質の４−フルオロ−１，３−ジオキソラン−２−オンを得るためには、上記沈殿化操作と併せて、精密蒸留を行うことが一層好ましい。精密蒸留は、上記沈殿化の前後の何れに行っても良いが、溶媒成分、固形分を除去できるというメリットを活かすため、沈殿化の後（精製の最終段階）に行うのが特に効果的である。精密蒸留は段数２〜１０段程度、還流比３〜１５程度で行うのが好ましい精密蒸留は減圧下で行うのが好ましく、１ｋＰａ〜３ｋＰａが特に好ましい。この圧力下では、４−フルオロ−１，３−ジオキソラン−２−オンは７０℃〜１１０℃で留出してくる。 However, in order to obtain 4-fluoro-1,3-dioxolan-2-one with more stable quality, it is more preferable to perform precision distillation in combination with the precipitation operation. The precision distillation may be performed before or after the above precipitation, but it is particularly effective to perform after the precipitation (final stage of purification) in order to take advantage of the ability to remove the solvent component and solid content. is there. The precision distillation is preferably performed at about 2 to 10 stages and a reflux ratio of about 3 to 15, and the precision distillation is preferably performed under reduced pressure, and 1 kPa to 3 kPa is particularly preferable. Under this pressure, 4-fluoro-1,3-dioxolan-2-one distills at 70-110 ° C.
ただし、精密蒸留それ自体の「塩素根」除去効果は小さい。特に、「塩素根」含量が低いサンプルを蒸留する場合、除去効果は一層小さい。すなわち本発明の対象とする、高純度の高純度４−フルオロ−１，３−ジオキソラン−２−オンを得るためには、沈殿化が必須であり、精密蒸留はそれに付随して行われるべきものである。 However, precision distillation itself has a small “chlorine root” removal effect. In particular, when a sample having a low “chlorine root” content is distilled, the removal effect is even smaller. That is, in order to obtain the high purity 4-fluoro-1,3-dioxolan-2-one, which is the subject of the present invention, precipitation is essential, and precision distillation should be performed accompanying it. It is.
これまでに述べた知見から、本発明は、次の２工程を組み合わせて行うことにより、特に好ましく実施できる。
第１工程（フッ素化工程）：４−クロロ−１，３−ジオキソラン−２−オンをフッ化カリウムと、アセトニトリル中、無水条件下で接触させて、粗４−フルオロ−１，３−ジオキソラン−２−オンを得る工程。
第２工程（精製工程）：前記第１工程で得られた祖４−フルオロ−１，３−ジオキソラン−２−オンの溶液を、５℃以下の温度でトルエンと接触させ４−フルオロ−１，３−ジオキソラン−２−オンを沈殿化する操作を、少なくとも２回行い、併せて蒸留精製を行う工程。
From the knowledge described so far, the present invention can be particularly preferably carried out by combining the following two steps.
First step (fluorination step): 4-chloro-1,3-dioxolan-2-one is contacted with potassium fluoride in acetonitrile under anhydrous conditions to give crude 4-fluoro-1,3-dioxolane- Obtaining 2-one.
Second step (purification step): The solution of the original 4-fluoro-1,3-dioxolan-2-one obtained in the first step is brought into contact with toluene at a temperature of 5 ° C. or lower to give 4-fluoro-1, A step of performing an operation of precipitating 3-dioxolan-2-one at least twice and performing distillation purification together.
［実施例］以下、実施例により、本発明を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 [Examples] The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
なお、組成分析はガスクロマトグラフィーで実施した。ガスクロマトグラフ分析値（％）は、溶媒が残存している場合は溶媒をカットし、下記の数値として算出した。 The composition analysis was performed by gas chromatography. The gas chromatographic analysis value (%) was calculated as the following numerical value after the solvent was cut when the solvent remained.
ガスクロマトグラフ分析値（％）
＝（該当化合物のピーク面積）／（全面積−残留溶媒ピーク面積）×１００
全塩素量（「塩素根」含量）は、フラスコ燃焼法により、反応混合物または４−フルオロ−１，３−ジオキソラン−２−オン中に存在しているＣｌ成分を全てＣｌ-に変換した後、Ｃｌ-イオン濃度を陰イオン液体クロマトグラフィーによって測定し、下記の値として算出した。
Gas chromatographic analysis value (%)
= (Peak area of the compound of interest) / (total area-residual solvent peak area) * 100
The total chlorine content (“chlorine root” content) is obtained by converting all Cl components present in the reaction mixture or 4-fluoro-1,3-dioxolan-2-one into Cl − by flask combustion, The Cl − ion concentration was measured by anion liquid chromatography and calculated as the following value.
全塩素量（ｐｐｍ）：４−フルオロ−１，３−ジオキソラン−２−オン１ｇ中に含まれる塩素原子（Ｃｌ）のグラム数に１０6を乗じた値。 Total chlorine content (ppm): A value obtained by multiplying 10 6 by the number of grams of chlorine atom (Cl) contained in 1 g of 4-fluoro-1,3-dioxolan-2-one.
粗４−フルオロ−１，３−ジオキソラン−２−オンの製造（第１工程）
撹拌機能を備えた１０Ｌの四つ口フラスコに、４−クロロ−１，３−ジオキソラン−２−オン（「Ｃｌ−ＥＣ」と呼ぶ）１１５６ｇ（９．４４ｍｏｌ、１．０当量）とアセトニトリル４．５Ｌ、フッ化カリウム（スプレードライ品）６６０ｇ（１１．４ｍｏｌ、１．２当量）を仕込み、内温８０℃〜８５℃で１１時間攪拌した。反応液を冷却した後、反応で生じた塩化カリウムを濾別し、濾紙上の塩化カリウムはアセトニトリル１．２Ｌで洗浄した。濾液と洗浄液を混合し、濃縮して溶媒を留去し、粗４−フルオロ−１，３−ジオキソラン−２−オン（「Ｆ−ＥＣ」と呼ぶ）を１０００．５ｇ得た。この粗Ｆ−ＥＣを分析したところ、目的とするＦ−ＥＣの含量は８０．５％であり、原料のＣｌ−ＥＣの含量は０．２％。副生物であるビニレンカーボネート（ＶＣ）とエチレンカーボネート（ＥＣ）の含量はそれぞれ１１．９％、５．０％であった。目的とするＦ−ＥＣは２５℃の温度においても液体であった。反応混合物中の全塩素量は４８００ｐｐｍであった。
Production of crude 4-fluoro-1,3-dioxolan-2-one (first step)
In a 10 L four-necked flask equipped with a stirring function, 1156 g (9.44 mol, 1.0 equivalent) of 4-chloro-1,3-dioxolan-2-one (referred to as “Cl-EC”) and acetonitrile 4. 5 L and potassium fluoride (spray-dried product) 660 g (11.4 mol, 1.2 equivalents) were charged, and the mixture was stirred at an internal temperature of 80 ° C. to 85 ° C. for 11 hours. After cooling the reaction solution, potassium chloride generated by the reaction was filtered off, and potassium chloride on the filter paper was washed with 1.2 L of acetonitrile. The filtrate and the washing solution were mixed and concentrated to remove the solvent to obtain 1000.5 g of crude 4-fluoro-1,3-dioxolan-2-one (referred to as “F-EC”). When this crude F-EC was analyzed, the content of the target F-EC was 80.5%, and the content of the raw material Cl-EC was 0.2%. The contents of vinylene carbonate (VC) and ethylene carbonate (EC) as by-products were 11.9% and 5.0%, respectively. The target F-EC was liquid even at a temperature of 25 ° C. The total chlorine content in the reaction mixture was 4800 ppm.
４−フルオロ−１，３−ジオキソラン−２−オンの沈殿化（第２工程）
撹拌機能を備えた５００ｍｌの四つ口フラスコにトルエン２８０ｇを仕込み、５℃まで冷却した。その後、実施例１で得られた粗Ｆ−ＥＣ １００ｇ（全塩素量４８００ｐｐｍ）を撹拌しながら、０℃から５℃に温度を維持したまま滴下した。その後０℃から５℃に温度を維持したまま１時間攪拌した。そして結晶を濾別し、５℃のヘキサンで２回洗浄した後、加熱融解し、液体を回収した。その結果、６６％の回収率でＦ−ＥＣが得られ、Ｆ−ＥＣの純度は９９．３５％、全塩素量は６８ｐｐｍであった。
Precipitation of 4-fluoro-1,3-dioxolan-2-one (second step)
A 500 ml four-necked flask equipped with a stirring function was charged with 280 g of toluene and cooled to 5 ° C. Thereafter, 100 g of crude F-EC obtained in Example 1 (total chlorine amount 4800 ppm) was added dropwise while maintaining the temperature from 0 ° C. to 5 ° C. while stirring. Thereafter, the mixture was stirred for 1 hour while maintaining the temperature from 0 ° C to 5 ° C. The crystals were separated by filtration, washed twice with hexane at 5 ° C., and then melted by heating to recover the liquid. As a result, F-EC was obtained with a recovery rate of 66%, the purity of F-EC was 99.35%, and the total chlorine content was 68 ppm.
４−フルオロ−１，３−ジオキソラン−２−オンの沈殿化（第２工程）
実施例２と同一の装置を用い、溶媒として「トルエン２８０ｇ」の代わりに、「トルエン２５０ｇ」を用いた他は同一の条件で、粗Ｆ−ＥＣ（塩素根含量４８００ｐｐｍ）の沈殿化を行った。その結果、６８％の回収率でＦ−ＥＣが得られ、当該結晶中のＦ−ＥＣの純度は９９．６０％であり、全塩素量は７２ｐｐｍであった。
Precipitation of 4-fluoro-1,3-dioxolan-2-one (second step)
Using the same apparatus as in Example 2, precipitation of crude F-EC (chlorine root content 4800 ppm) was performed under the same conditions except that “toluene 250 g” was used instead of “toluene 280 g” as a solvent. . As a result, F-EC was obtained with a recovery rate of 68%, the purity of F-EC in the crystals was 99.60%, and the total chlorine content was 72 ppm.
４−フルオロ−１，３−ジオキソラン−２−オンの沈殿化（第２工程）
撹拌機能を備えた１００ｍｌの四つ口フラスコにトルエン５０ｇを仕込み、５℃まで冷却した。その後実施例１（第２工程）で得られたＦ−ＥＣ（全塩素量６８ｐｐｍ）２０ｇを撹拌しながら、０℃から５℃に温度を維持したまま滴下した。その後０℃から５℃に温度を維持したまま１時間攪拌した。そして固体を濾別し、５℃のヘキサンで２回洗浄した後、加熱融解し、液体を回収した。その結果、８３％の回収率でＦ−ＥＣが得られ、当該結晶中のＦ−ＥＣの純度は９９．９５％であり、全塩素量は８ｐｐｍであった。
［比較例１］
Precipitation of 4-fluoro-1,3-dioxolan-2-one (second step)
A 100 ml four-necked flask equipped with a stirring function was charged with 50 g of toluene and cooled to 5 ° C. Thereafter, 20 g of F-EC (total chlorine content: 68 ppm) obtained in Example 1 (second step) was added dropwise while maintaining the temperature from 0 ° C to 5 ° C while stirring. Thereafter, the mixture was stirred for 1 hour while maintaining the temperature from 0 ° C to 5 ° C. The solid was separated by filtration, washed twice with hexane at 5 ° C., and then melted by heating to recover the liquid. As a result, F-EC was obtained with a recovery rate of 83%, the purity of F-EC in the crystals was 99.95%, and the total chlorine content was 8 ppm.
[ Comparative Example 1 ]
トルエン／酢酸エチル（３：１）を用いた沈殿化
実施例１（第２工程）と同一の装置を用い、溶媒として「トルエン２８０ｇ」の代わりに、「トルエン２１０ｇ／酢酸エチル７０ｇ」を用いた他は同一の条件で、粗Ｆ−ＥＣ（塩素根含量４８００ｐｐｍ）の沈殿化を行った。その結果、３０％の回収率でＦ−ＥＣが得られ、当該結晶中のＦ−ＥＣの純度は９９．４３％であり、全塩素量は９１ｐｐｍであった。
Precipitation using toluene / ethyl acetate (3: 1) Using the same apparatus as in Example 1 (second step), “toluene 210 g / ethyl acetate 70 g” was used instead of “toluene 280 g” as a solvent. Precipitation of crude F-EC (chlorine root content 4800 ppm) was performed under the same conditions for the others. As a result, F-EC was obtained with a recovery rate of 30%, the purity of F-EC in the crystals was 99.43%, and the total chlorine content was 91 ppm.
このように、「トルエン／酢酸エチル混合溶媒」でも沈殿化は行え、全塩素量は低減できたが、酢酸エチルの極性が相対的に高いことに起因して、回収率が低下した。
［比較例２］
Thus, precipitation was possible even with the “toluene / ethyl acetate mixed solvent”, and the total chlorine amount could be reduced, but the recovery rate was lowered due to the relatively high polarity of ethyl acetate.
[Comparative Example 2 ]
蒸留のみによる精製
実施例１（第１工程）と同様の操作で得られたＦ−ＥＣ（全塩素量４５００ｐｐｍ；Ｆ−ＥＣ：Ｃｌ−ＥＣ：ＶＣ：ＥＣ＝８７．５％：２．１％：５．９％：４．１％）２００ｇを粗蒸留（９４℃〜９９℃／２．５ｋＰａ）して４−フルオロ−１，３−ジオキソラン−２−オン１４８ｇ（回収率７４％）を得た。この蒸留で得られた留分を分析したところ、目的とする４−フルオロ−１，３−ジオキソラン−２−オンの含量は９３．０％であり、４−クロロ−１，３−ジオキソラン−２−オンの含量は０．２％。副生物であるＶＣとＥＣの含量はそれぞれ２．２％、１．９％であった。この留分を４段の蒸留塔を使用し、還流比２〜５で精密蒸留（温度８５〜９０℃、圧力１．８ｋＰａ）して、Ｆ−ＥＣ ９９ｇ（回収率６７％）を得た。このＦ−ＥＣを分析したところ、目的とするＦ−ＥＣの含量は９９．７％であった。全塩素量は１９７ｐｐｍであった。
Purification by distillation only F-EC obtained in the same manner as in Example 1 (first step) (total chlorine amount 4500 ppm; F-EC: Cl-EC: VC: EC = 87.5%: 2.1%) : 5.9%: 4.1%) 200 g was roughly distilled (94 ° C. to 99 ° C./2.5 kPa) to obtain 148 g of 4-fluoro-1,3-dioxolan-2-one (recovery 74%). It was. When the fraction obtained by this distillation was analyzed, the content of the desired 4-fluoro-1,3-dioxolan-2-one was 93.0%, and 4-chloro-1,3-dioxolane-2 -The content of ON is 0.2%. The contents of VC and EC as by-products were 2.2% and 1.9%, respectively. This fraction was subjected to precision distillation (temperature 85 to 90 ° C., pressure 1.8 kPa) at a reflux ratio of 2 to 5 using a four-stage distillation column to obtain 99 g of F-EC (recovery rate 67%). When this F-EC was analyzed, the content of the target F-EC was 99.7%. The total chlorine content was 197 ppm.
得られたＦ−ＥＣに対し、同様の蒸留精製を繰り返し行ったが、全塩素量は１５６ｐｐｍにまでしか低減しなかった。
［比較例３］
The same distillation purification was repeated for the obtained F-EC, but the total chlorine content was reduced only to 156 ppm.
[Comparative Example 3 ]
酢酸エチルを用いた沈殿化
撹拌機能を備えた３００ｍｌの四つ口フラスコに酢酸エチル１４０ｇを仕込み、５℃まで冷却した。その後、実施例１（第１工程）で得られた粗Ｆ−ＥＣ ５０ｇ（全塩素量４８００ｐｐｍ）を撹拌しながら、０℃から５℃に温度を維持したまま滴下した。その後０℃から５℃に温度を維持したまま１時間攪拌したが、結晶を得ることはできなかった。
Precipitation using ethyl acetate Into a 300 ml four-necked flask equipped with a stirring function, 140 g of ethyl acetate was charged and cooled to 5 ° C. Thereafter, 50 g of crude F-EC obtained in Example 1 (first step) (total chlorine amount 4800 ppm) was added dropwise while maintaining the temperature from 0 ° C. to 5 ° C. while stirring. Thereafter, the mixture was stirred for 1 hour while maintaining the temperature from 0 ° C. to 5 ° C., but crystals could not be obtained.
本比較例は、実施例２の１／２の規模で、トルエン（比誘電率２．３８）の代わりに、極性がわずかに大きい酢酸エチル（比誘電率６．０２）を用いて行ったものであるが、沈殿化を効果的に行うことはできなかった。 This comparative example was carried out using ethyl acetate (relative permittivity: 6.02) having a slightly larger polarity in place of toluene (relative permittivity: 2.38) on a scale half that of Example 2. However, precipitation could not be performed effectively.
Claims (5)
第１工程（フッ素化工程）：４−クロロ−１，３−ジオキソラン−２−オンをフッ化カリウムと、アセトニトリル中、無水条件下で接触させて、粗４−フルオロ−１，３−ジオキソラン−２−オンを得る工程。
第２工程（精製工程）：前記第１工程で得られた粗４−フルオロ−１，３−ジオキソラン−２−オンの溶液を、トルエンと接触させて４−フルオロ−１，３−ジオキソラン−２−オンを沈殿化し、高純度４−フルオロ−１，３−ジオキソラン−２−オンを得る工程。 A method for producing high-purity 4-fluoro-1,3-dioxolan-2-one, comprising the following steps.
First step (fluorination step): 4-chloro-1,3-dioxolan-2-one is contacted with potassium fluoride in acetonitrile under anhydrous conditions to give crude 4-fluoro-1,3-dioxolane- Obtaining 2-one.
Second step (purification step): The solution of the crude 4-fluoro-1,3-dioxolan-2-one obtained in the first step is brought into contact with toluene to give 4-fluoro-1,3-dioxolane-2. -Precipitating the ones to obtain high purity 4-fluoro-1,3-dioxolan-2-one.
第１工程（フッ素化工程）：４−クロロ−１，３−ジオキソラン−２−オンをフッ化カリウムと、アセトニトリル中、無水条件下で接触させて、粗４−フルオロ−１，３−ジオキソラン−２−オンを得る工程。
第２工程（精製工程）： 前記第１工程で得られた粗４−フルオロ−１，３−ジオキソラン−２−オンの溶液を、５℃以下の温度でトルエンと接触させ４−フルオロ−１，３−ジオキソラン−２−オンを沈殿化する操作を、少なくとも２回行い、併せて蒸留精製を行う工程。 A method for producing high-purity 4-fluoro-1,3-dioxolan-2-one, comprising the following steps.
First step (fluorination step): 4-chloro-1,3-dioxolan-2-one is contacted with potassium fluoride in acetonitrile under anhydrous conditions to give crude 4-fluoro-1,3-dioxolane- Obtaining 2-one.
Second step (purification step): The solution of the crude 4-fluoro-1,3-dioxolan-2-one obtained in the first step is brought into contact with toluene at a temperature of 5 ° C. or lower to give 4-fluoro-1, A step of performing an operation of precipitating 3-dioxolan-2-one at least twice and performing distillation purification together.
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| WO2018184379A1 (en) * | 2017-04-06 | 2018-10-11 | 多氟多化工股份有限公司 | Preparation method for high purity fluoroethylene carbonate |
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| JP5061635B2 (en) * | 2007-02-15 | 2012-10-31 | ダイキン工業株式会社 | Process for producing 4-fluoro-1,3-dioxolan-2-one |
| CN100558721C (en) * | 2007-06-01 | 2009-11-11 | 张家港市华盛化学有限公司 | Preparation method of fluorinated cyclic carbonate |
| JP5135926B2 (en) * | 2007-07-13 | 2013-02-06 | ダイキン工業株式会社 | Process for producing 4-fluoro-1,3-dioxolan-2-one |
| JP5600876B2 (en) * | 2008-02-28 | 2014-10-08 | ダイキン工業株式会社 | Process for producing 4-fluoro-1,3-dioxolan-2-one |
| JP5358974B2 (en) * | 2008-02-28 | 2013-12-04 | ダイキン工業株式会社 | Method for producing fluorinated 1,3-dioxolan-2-one |
| WO2009118368A1 (en) * | 2008-03-27 | 2009-10-01 | Solvay Fluor Gmbh | Preparation of fluorinated organic carbonates depleted in hf using a specific absorbent |
| CN101676282A (en) * | 2008-09-16 | 2010-03-24 | 中国科学院福建物质结构研究所 | A kind of synthetic method of fluoroethylene carbonate |
| CN101597275B (en) * | 2009-07-16 | 2012-05-30 | 太仓华一化工科技有限公司 | Method for purifying fluoroethylene carbonate |
| KR20120083485A (en) * | 2009-10-21 | 2012-07-25 | 솔베이 플루오르 게엠베하 | Method for the manufacture of fluorinated ethylene carbonates |
| CN102060838A (en) * | 2010-12-31 | 2011-05-18 | 浙江华晶氟化学科技有限公司 | Method for preparing fluoroethylene carbonate |
| HUE060750T2 (en) | 2013-10-02 | 2023-04-28 | Daikin Ind Ltd | Fluorinating agent |
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| EP0931365B1 (en) * | 1996-10-03 | 2000-07-19 | National Research Council Of Canada | Electrolyte comprising fluoro-ethylene carbonate and propylene carbonate, for alkali metal-ion secondary battery |
| JP4531153B2 (en) * | 1999-04-28 | 2010-08-25 | 関東電化工業株式会社 | Process for producing 4-fluoro-1,3-dioxolan-2-one |
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