WO2012020701A1 - Process for preparing hexafluoroacetone monohydrate - Google Patents
Process for preparing hexafluoroacetone monohydrate Download PDFInfo
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- WO2012020701A1 WO2012020701A1 PCT/JP2011/067927 JP2011067927W WO2012020701A1 WO 2012020701 A1 WO2012020701 A1 WO 2012020701A1 JP 2011067927 W JP2011067927 W JP 2011067927W WO 2012020701 A1 WO2012020701 A1 WO 2012020701A1
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- hexafluoroacetone
- water
- monohydrate
- organic solvent
- hydrate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/86—Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
Definitions
- the present invention relates to a process for producing hexafluoroacetone monohydrate (1,1,1,3,3,3-hexafluoropropane-2-diol), and more particularly to solid hexafluoroacetone monohydrate.
- the present invention relates to a method for manufacturing a product.
- Hexafluoroacetone is an important compound as a pharmaceutical intermediate or various reaction raw materials. Hexafluoroacetone is industrially produced by epoxidation of hexafluoropropene followed by isomerization, hexachloroacetone obtained by chlorinating acetone with hydrogen fluoride using a chromium activated carbon supported catalyst, etc. Manufactured. Since hexafluoroacetone is a gas having a boiling point of ⁇ 28 ° C. at atmospheric pressure, hexafluoroacetone trihydrate, which can be handled as a constant boiling point composition at 106 ° C., is used as a raw material for many reactions or used for storage.
- hexafluoroacetone monohydrate may be required depending on reaction conditions, target product and other reasons. It has been reported that hexafluoroacetone monohydrate can introduce, for example, a hexafluoroisopropanol group into the 5-position of uracil (Non-patent Document 1).
- Hexafluoroacetone monohydrate is a crystal having a gem-diol structure with a melting point of 46 ° C. and decomposes simultaneously with melting to disproportionate to hexafluoroacetone and hexafluoroacetone trihydrate (Patent Document 1). It is a compound that is very difficult to handle because it deliquesces immediately with moisture in the air even at low temperatures.
- Patent Document 1 describes that hexafluoroacetone monohydrate can be obtained by absorbing hexafluoroacetone in two stages into water charged in a container in two stages. It is also described that the solid contains a little hexafluoroacetone and water and is slightly moist, and its melting point is 40 ° C., which is lower than the literature value of 46 ° C. The solid hexafluoroacetone monohydrate obtained by this method reduces the stability of hexafluoroacetone monohydrate, which is inherently deliquescent, with water adhering to the solid surface, making it extremely difficult to use. ing.
- the present invention provides a method for producing a hexafluoroacetone monohydrate solid that is easy to handle because it has low deliquescence and high stability.
- the present inventors have made hexafluoroacetone monohydrate (1,1,1,3,3) substantially free of water from aqueous solutions containing hydrates such as hexafluoroacetone or hexafluoroacetone trihydrate. , 3-hexafluoropropane-2-diol), the hexafluoroacetone monohydrate was precipitated as a solid when the molar ratio of hexafluoroacetone to water was adjusted in the presence of an organic solvent. By separating this from the liquid, it was found that hexafluoroacetone monohydrate without water adhering to the surface was obtained, and the present invention was achieved.
- the present invention is as follows.
- [Invention 1] A method for producing hexafluoroacetone monohydrate, in which water or hexafluoroacetone hydrate coexists with an organic solvent, and the number of moles of water present in the system (hexafluoroacetone hydrate is converted to hexafluoroacetone hydrate).
- Invention 2 The method for producing hexafluoroacetone monohydrate according to Invention 1, wherein the organic solvent is an aliphatic hydrocarbon or a halogenated aliphatic hydrocarbon.
- the organic solvent is one or more organic solvents selected from n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane, carbon tetrachloride, chloroform, dichloromethane and 1,2-dichloroethane.
- a method for producing hexafluoroacetone monohydrate is one or more organic solvents selected from n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane, carbon tetrachloride, chloroform, dichloromethane and 1,2-dichloroethane.
- the second step includes the step of filtering and obtaining the solid hexafluoroacetone monohydrate contained in the contents formed in the system in the first step. Manufacturing method.
- invention 5 The method for producing hexafluoroacetone monohydrate according to inventions 1 to 4, wherein the second step includes a step of distilling off the organic solvent from the contents formed in the system in the first step.
- solid hexafluoroacetone monohydrate can be obtained from a hydrate such as hexafluoroacetone trihydrate without using a special desiccant or dehydrating agent. Furthermore, since the obtained solid hexafluoroacetone monohydrate has substantially no water adhering to the surface, it has an effect of being easy to handle with little deliquescence.
- hexafluoroacetone may be represented as “HFA”, hexafluoroacetone monohydrate as “HFA ⁇ W”, and hexafluoroacetone trihydrate as “HFA ⁇ 3W”.
- hexafluoroacetone hydrate is a general term for compounds obtained by hydrating hexafluoroacetone, and refers to a hydrate that does not limit the number of hydration or an aqueous solution thereof. “HFA ⁇ 3W” It is a concept that includes
- the present invention introduces hexafluoroacetone into a system in which water or hexafluoroacetone hydrate coexists with an organic solvent so that the number of moles of water present in the system is substantially equal to the number of moles of hexafluoroacetone. Then, it is a manufacturing method of hexafluoroacetone monohydrate including the process of removing an organic solvent.
- the number of moles of water present in the system refers to the total number of moles of water and free water produced when hexafluoroacetone hydrate is decomposed into hexafluoroacetone and water
- Free water refers to water that is not contained in the molecule of hexafluoroacetone hydrate.
- a system in which water or hexafluoroacetone hydrate coexists with an organic solvent can be prepared by mixing an organic solvent and hexafluoroacetone, or water and hexafluoroacetone hydrate.
- This system is liquid phase and may be homogeneous or heterogeneous.
- the hexafluoroacetone hydrate the hydration number is not particularly limited and may be an aqueous solution, but it is preferable to use hexafluoroacetone trihydrate. Hexafluoroacetone hydrate can also be used in combination with water.
- Hexafluoroacetone trihydrate is a dihydrate of hexafluoroacetone monohydrate, which is a gem-diol produced by the reaction of hexafluoroacetone and water (herein the dihydrate 2 Is a chemical substance represented by the following formula, and is a stable liquid having the highest azeotropic composition (boiling point 106 ° C.).
- hexafluoroacetone monohydrate is a solid with a melting point (46 ° C.), but decomposes above the melting point and disproportionates into anhydrous hexafluoroacetone and hexafluoroacetone trihydrate (patent) Reference 1).
- organic solvent examples include aromatic compounds, ether compounds, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons (halogen solvents) that are liquid at room temperature (about 25 ° C.).
- the aromatic compound is not particularly limited and may be any of monocyclic, ring aggregate, and condensed polycyclic, but monocyclic benzene or a hydrogen atom of benzene is a halogen atom, an alkyl group, a fluoroalkyl group, or the like Compounds substituted with are preferred.
- Examples of such compounds include benzene, toluene, xylene, ethylbenzene, chlorobenzene, benzotrifluoride, 2,4-dichlorobenzotrifluoride, o-, m- or p-bistrifluoromethylbenzene.
- Examples of the ether compound include chain ethers such as dimethyl ether, diethyl ether, isopropyl ether, ethyl isopropyl ether, butyl methyl ether, and ethyl butyl ether, and cyclic ethers such as tetrahydrofuran, pyran, and dioxane.
- the aliphatic hydrocarbon examples include n-pentane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane and cycloheptane.
- the halogen solvent is a compound in which a hydrogen atom of an aliphatic hydrocarbon is substituted with a halogen atom, an alkyl group, a fluoroalkyl group or the like, and includes carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, cis-1,2 -Dichloroethylene, trans-1,2-dichloroethylene, 1,1,2-trichloroethane and the like.
- aliphatic hydrocarbons and halogenated aliphatic hydrocarbons are preferable.
- aliphatic solvents such as aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, cyclopentane, and cyclohexane
- halogen solvents such as carbon tetrachloride, chloroform, dichloromethane, and 1,2-dichloroethane are preferable.
- halogen solvents such as carbon tetrachloride, chloroform, dichloromethane, and 1,2-dichloroethane are preferable.
- the concentration of water or water in the system in which hexafluoroacetone hydrate coexists with the organic solvent may be determined arbitrarily, but usually hexafluoroacetone (assuming that hexafluoroacetone hydrate is decomposed into water and hexafluoroacetone) Hexafluoroacetone in this case) 1 to 1000 parts by weight of organic solvent per 1 part by weight, preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight. If the amount is less than 1 part by mass, the entire reaction system becomes a lump containing unreacted water, which is difficult to handle. If the amount exceeds 1000 parts by weight, the removal of the solvent is complicated and the throughput is not preferable.
- the hexafluoroacetone monohydrate according to the present invention is a mixture of an aqueous solution containing hexafluoroacetone hydrate, for example, hexafluoroacetone trihydrate or hexafluoroacetone and an organic solvent, with water in the system (additional water and Free water) and equimolar hexafluoroacetone can be added to obtain a solution dissolved in an organic solvent or precipitated.
- Hexafluoroacetone is introduced as follows.
- the hexafluoroacetone preferably has a molar ratio of hexafluoroacetone (hexafluoroacetone to be introduced) / water (total amount of added water and free water) of substantially 1, but is usually 1 to 1.2. That's fine. Considering operational loss, etc., a slight excess may be allowed. However, when hexafluoroacetone is excessive, it is not preferable because it will be unreacted to be washed away. Since the hydrate remains in the organic solvent solution, it is not preferable.
- the liquid portion in the system When introducing hexafluoroacetone into the system, it is preferable to heat the liquid portion in the system at 20 ° C. or higher and below the boiling temperature of the liquid. This is because a sufficient reaction rate cannot be obtained at a low temperature.
- the temperature of the reaction system increases as the reaction proceeds and decreases with the completion of the reaction. Therefore, although the temperature in the system varies depending on the type of organic solvent, it is usually set to a boiling point (106 ° C.) or less of hexafluoroacetone trihydrate. In order to precipitate hexafluoroacetone monohydrate, it is necessary to carry out at a melting point (46 ° C.) or lower, so at least 46 ° C.
- the lower limit temperature during the reaction is not particularly limited, but may be at least the melting point of the solvent, may be ⁇ 40 ° C. or more, and is advantageously 0 ° C. or more.
- hexafluoroacetone monohydrate is formed in the system in which hexafluoroacetone is introduced, and the amount exceeding the solubility is precipitated as a solid.
- the temperature of the system can be cooled to promote precipitation, or the amount of precipitation can be increased.
- This solid can be recovered by filtration or decantation and dried. Drying is preferably performed at a melting point (46 ° C.) or lower, and for this purpose, it is preferably performed under reduced pressure.
- a portion of hexafluoroacetone monohydrate was precipitated and filtered and dried as described above.
- a solid can be obtained.
- the solid can also be recovered by distilling off all of the organic solvent from the reaction system to precipitate hexafluoroacetone monohydrate.
- hexafluoroacetone monohydrate may be dissolved in the remaining liquid (mother liquor) from which the solid has been separated by means such as filtration.
- Acetone hydrate and hexafluoroacetone can be introduced to precipitate hexafluoroacetone monohydrate.
- a predetermined amount of hexafluoroacetone trihydrate and an organic solvent are introduced into a closed reaction vessel equipped with a stirrer and a gas inlet.
- the inside of the reaction vessel may be separated into two layers, but in that case, stirring is preferable.
- the temperature of the solution in the system rises, so stirring is performed while cooling from the outside, and the molar ratio of hexafluoroacetone (hexafluoroacetone to be introduced) and water (added water and free water) is 1:
- the amount of hexafluoroacetone that becomes 1 is gradually introduced from the gas inlet of the reaction vessel.
- the reaction is completed when the introduction of a predetermined amount of hexafluoroacetone is completed and the reaction solution temperature is lowered and the pressure is lowered.
- a homogeneous solution or a solution in which a white solid is precipitated is obtained in the reaction vessel.
- the reaction solution may be cooled to promote precipitation.
- the contents of the reaction vessel are taken out, the precipitated solid is separated from the liquid phase, and then the solution is volatilized at a temperature below the melting point using a rotary evaporator or the like to obtain hexafluoroacetone monohydrate crystals.
- This treatment is preferably performed under reduced pressure.
- the reaction apparatus is not particularly limited, but is preferably a pressure vessel or a vessel equipped with a condenser, and preferably a stirrer.
- a pressure vessel or a vessel equipped with a condenser, and preferably a stirrer.
- a material of the apparatus stainless steel, nickel alloy steel, glass, fluororesin, carbon, polyethylene, or a material lined or clad with these materials can be used.
- Example 1 It is equipped with a stirrer, dry ice / acetone cooling reflux, thermometer, gas inlet, and the opening of the reflux is a glass 200 mL four-neck reactor closed with a balloon. Chloroform: 148 g, hexafluoroacetone Hydrate (HFA ⁇ 3W): 22 g (0.1 mol) is added, the outside is ice-cooled, and hexafluoroacetone (HFA): 32 g (0.2 mol) is kept at an internal temperature of 25 ° C. from the gas inlet. The reaction was terminated by introducing 1 hour. After completion of the reaction, crystals were collected from the slurry by filtration and dried under reduced pressure with an evaporator to obtain 21 g of white needle crystals (yield 32%).
- HFA ⁇ 3W hexafluoroacetone Hydrate
- HFA hexafluoroacetone
- the recovered white needle-like crystals were measured by NMR (13C, H, F) and FT-IR, and found to be hexafluoroacetone monohydrate (1,1,1,3,3,3-hexafluoropropane-2-diol. ) And other components were not recognized. Further, hexafluoroacetone contained in the crystal was measured by neutralization titration, and the water content was measured with a Karl Fischer moisture measuring device. As a result, the molar ratio of hexafluoroacetone to water was 1: 1.
- Example 2 It is equipped with a stirrer, dry ice / acetone cooling reflux, thermometer, gas inlet, and the opening of the reflux is a 200 mL four-necked reactor with a balloon closed system.
- the recovered white needle-like crystals were measured by NMR (13C, H, F) and FT-IR, and found to be hexafluoroacetone monohydrate (1,1,1,3,3,3-hexafluoropropane-2-diol. ) And other components were not recognized. Further, hexafluoroacetone contained in the crystal was measured by neutralization titration, and the water content was measured with a Karl Fischer moisture measuring device. As a result, the molar ratio of hexafluoroacetone to water was 1: 1.
- Example 3 It is equipped with a stirrer, dry ice / acetone cooling reflux, thermometer, gas inlet, and the opening of the reflux is a glass 200 ml four-necked reactor closed with a balloon.
- the recovered white needle-like crystals were measured by NMR (13C, H, F) and FT-IR, and found to be hexafluoroacetone monohydrate (1,1,1,3,3,3-hexafluoropropane-2-diol. ) And other components were not recognized. Further, hexafluoroacetone contained in the crystal was measured by neutralization titration, and the water content was measured with a Karl Fischer moisture measuring device. As a result, the molar ratio of hexafluoroacetone to water was 1: 1.
- solid hexafluoro which is easy to handle and has low deliquescence from hydrates such as hexafluoroacetone trihydrate without using a special desiccant or dehydrating agent.
- Acetone monohydrate can be obtained.
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Abstract
This process comprises: a first step of introducing hexa- fluoroacetone into a coexistent system where water or a hexafluoroacetone hydrate coexists with an organic solvent so as to make the molar amount of water present in the coexistent system (the total amount of both free water and water formed when the hexafluoroacetone hydrate is decomposed into hexafluoroacetone and water) substantially equal to the molar amount of hexafluoroacetone present therein; and a second step of recovering solid hexafluoroacetone monohydrate from the contents formed in the system in the first step. According to the process, solid hexafluoroacetone monohydrate which exhibits low deliquescence and high stability and therefore is easily handleable can be prepared without using a special drying or dehydrating agent.
Description
本発明は、ヘキサフルオロアセトン一水和物（１，１，１，３，３，３－ヘキサフルオロプロパン－２－ジオール）を製造する方法に関し、より詳しくは、固体のヘキサフルオロアセトン一水和物を製造する方法に関する。
The present invention relates to a process for producing hexafluoroacetone monohydrate (1,1,1,3,3,3-hexafluoropropane-2-diol), and more particularly to solid hexafluoroacetone monohydrate. The present invention relates to a method for manufacturing a product.
ヘキサフルオロアセトンは、医薬品中間体または各種の反応原料として重要な化合物である。ヘキサフルオロアセトンは、工業的にはヘキサフルオロプロペンのエポキシ化とそれに続く異性化による方法、アセトンを塩素化して得られるヘキサクロロアセトンをクロム活性炭担持触媒等によりフッ化水素で置換フッ素化する方法などで製造される。ヘキサフルオロアセトンは大気圧で沸点が－２８℃の気体であることから、１０６℃の定沸点組成物として取り扱えるヘキサフルオロアセトン三水和物が多くの反応の原料として使用され、あるいは保存に供される。しかしながら、反応条件、目的物その他の理由によってヘキサフルオロアセトン一水和物が要求される場合がある。ヘキサフルオロアセトン一水和物は、例えば、ウラシルの５位へヘキサフルオロイソプロパノール基を導入できることが報告されている（非特許文献１）。
Hexafluoroacetone is an important compound as a pharmaceutical intermediate or various reaction raw materials. Hexafluoroacetone is industrially produced by epoxidation of hexafluoropropene followed by isomerization, hexachloroacetone obtained by chlorinating acetone with hydrogen fluoride using a chromium activated carbon supported catalyst, etc. Manufactured. Since hexafluoroacetone is a gas having a boiling point of −28 ° C. at atmospheric pressure, hexafluoroacetone trihydrate, which can be handled as a constant boiling point composition at 106 ° C., is used as a raw material for many reactions or used for storage. The However, hexafluoroacetone monohydrate may be required depending on reaction conditions, target product and other reasons. It has been reported that hexafluoroacetone monohydrate can introduce, for example, a hexafluoroisopropanol group into the 5-position of uracil (Non-patent Document 1).
ヘキサフルオロアセトン一水和物はｇｅｍ－ジオールの構造をもつ融点４６℃の結晶で融解と同時に分解してヘキサフルオロアセトンとヘキサフルオロアセトン三水和物に不均化する（特許文献１）上に、低温でも空気中の水分で直ちに潮解するため、非常に取り扱いの困難な化合物である。
Hexafluoroacetone monohydrate is a crystal having a gem-diol structure with a melting point of 46 ° C. and decomposes simultaneously with melting to disproportionate to hexafluoroacetone and hexafluoroacetone trihydrate (Patent Document 1). It is a compound that is very difficult to handle because it deliquesces immediately with moisture in the air even at low temperatures.
特許文献１には、容器に仕込んだ水へヘキサフルオロアセトンを二段階に分けて吸収させると針状白色結晶のヘキサフルオロアセトン一水和物が得られることが記載されているが、得られた固体は若干のヘキサフルオロアセトンと水を含んでやや湿っており、融点が４０℃と文献値の４６℃と比較して低いことも記載されている。この方法で得られる固体状のヘキサフルオロアセトン一水和物は、固体表面に水が付着しており元来潮解性であるヘキサフルオロアセトン一水和物の安定性を低下させ著しく使用を困難にしている。
Patent Document 1 describes that hexafluoroacetone monohydrate can be obtained by absorbing hexafluoroacetone in two stages into water charged in a container in two stages. It is also described that the solid contains a little hexafluoroacetone and water and is slightly moist, and its melting point is 40 ° C., which is lower than the literature value of 46 ° C. The solid hexafluoroacetone monohydrate obtained by this method reduces the stability of hexafluoroacetone monohydrate, which is inherently deliquescent, with water adhering to the solid surface, making it extremely difficult to use. ing.
そこで、本発明では、潮解性が低く安定性が高いことから取り扱いの容易なヘキサフルオロアセトン一水和物の固体を製造する方法を提供する。
Therefore, the present invention provides a method for producing a hexafluoroacetone monohydrate solid that is easy to handle because it has low deliquescence and high stability.
本発明者らは、ヘキサフルオロアセトンまたはヘキサフルオロアセトン三水和物などの水和物を含む水溶液から実質的に水を含まないヘキサフルオロアセトン一水和物（１，１，１，３，３，３－ヘキサフルオロプロパン－２－ジオール）を製造する方法について検討したところ、ヘキサフルオロアセトンと水のモル比を有機溶媒の存在下に調節するとヘキサフルオロアセトン一水和物が固体として析出し、これを液体から分離することで表面に水の付着しないヘキサフルオロアセトン一水和物が得られることを見出し、本発明に至った。
The present inventors have made hexafluoroacetone monohydrate (1,1,1,3,3) substantially free of water from aqueous solutions containing hydrates such as hexafluoroacetone or hexafluoroacetone trihydrate. , 3-hexafluoropropane-2-diol), the hexafluoroacetone monohydrate was precipitated as a solid when the molar ratio of hexafluoroacetone to water was adjusted in the presence of an organic solvent. By separating this from the liquid, it was found that hexafluoroacetone monohydrate without water adhering to the surface was obtained, and the present invention was achieved.
すなわち、本発明は、次の通りである。
That is, the present invention is as follows.
［発明１］
ヘキサフルオロアセトン一水和物の製造方法であって、水またはヘキサフルオロアセトン水和物が有機溶媒と共存する系に、系中に存在する水のモル数（ヘキサフルオロアセトン水和物をヘキサフルオロアセトンと水に分解したとする場合に生成する水とフリーの水との合計モル数）とヘキサフルオロアセトンのモル数が実質上等しくなるようにヘキサフルオロアセトンを導入する第一工程と、第一工程で系内に形成された内容物から固体のヘキサフルオロアセトン一水和物を取得する第二工程と、を含むヘキサフルオロアセトン一水和物の製造方法。 [Invention 1]
A method for producing hexafluoroacetone monohydrate, in which water or hexafluoroacetone hydrate coexists with an organic solvent, and the number of moles of water present in the system (hexafluoroacetone hydrate is converted to hexafluoroacetone hydrate). A first step of introducing hexafluoroacetone so that the number of moles of hexafluoroacetone is substantially equal to the total number of moles of water and free water produced when it is decomposed into acetone and water; A second step of obtaining solid hexafluoroacetone monohydrate from the contents formed in the system in the step, and a method for producing hexafluoroacetone monohydrate.
ヘキサフルオロアセトン一水和物の製造方法であって、水またはヘキサフルオロアセトン水和物が有機溶媒と共存する系に、系中に存在する水のモル数（ヘキサフルオロアセトン水和物をヘキサフルオロアセトンと水に分解したとする場合に生成する水とフリーの水との合計モル数）とヘキサフルオロアセトンのモル数が実質上等しくなるようにヘキサフルオロアセトンを導入する第一工程と、第一工程で系内に形成された内容物から固体のヘキサフルオロアセトン一水和物を取得する第二工程と、を含むヘキサフルオロアセトン一水和物の製造方法。 [Invention 1]
A method for producing hexafluoroacetone monohydrate, in which water or hexafluoroacetone hydrate coexists with an organic solvent, and the number of moles of water present in the system (hexafluoroacetone hydrate is converted to hexafluoroacetone hydrate). A first step of introducing hexafluoroacetone so that the number of moles of hexafluoroacetone is substantially equal to the total number of moles of water and free water produced when it is decomposed into acetone and water; A second step of obtaining solid hexafluoroacetone monohydrate from the contents formed in the system in the step, and a method for producing hexafluoroacetone monohydrate.
［発明２］
有機溶媒が、脂肪族炭化水素またはハロゲン化脂肪族炭化水素である、発明１のヘキサフルオロアセトン一水和物の製造方法。 [Invention 2]
The method for producing hexafluoroacetone monohydrate according to Invention 1, wherein the organic solvent is an aliphatic hydrocarbon or a halogenated aliphatic hydrocarbon.
有機溶媒が、脂肪族炭化水素またはハロゲン化脂肪族炭化水素である、発明１のヘキサフルオロアセトン一水和物の製造方法。 [Invention 2]
The method for producing hexafluoroacetone monohydrate according to Invention 1, wherein the organic solvent is an aliphatic hydrocarbon or a halogenated aliphatic hydrocarbon.
［発明３］
有機溶媒が、ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタン、シクロペンタン、シクロヘキサン、四塩化炭素、クロロホルム、ジクロロメタンおよび１，２－ジクロロエタンから選ばれた１種以上の有機溶媒である、発明２のヘキサフルオロアセトン一水和物の製造方法。 [Invention 3]
The organic solvent is one or more organic solvents selected from n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane, carbon tetrachloride, chloroform, dichloromethane and 1,2-dichloroethane. A method for producing hexafluoroacetone monohydrate.
有機溶媒が、ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタン、シクロペンタン、シクロヘキサン、四塩化炭素、クロロホルム、ジクロロメタンおよび１，２－ジクロロエタンから選ばれた１種以上の有機溶媒である、発明２のヘキサフルオロアセトン一水和物の製造方法。 [Invention 3]
The organic solvent is one or more organic solvents selected from n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane, carbon tetrachloride, chloroform, dichloromethane and 1,2-dichloroethane. A method for producing hexafluoroacetone monohydrate.
［発明４］
第二工程が、第一工程で系内に形成された内容物に含まれる固体のヘキサフルオロアセトン一水和物を濾過して取得する工程を含む、発明１～３のヘキサフルオロアセトン一水和物の製造方法。 [Invention 4]
The second step includes the step of filtering and obtaining the solid hexafluoroacetone monohydrate contained in the contents formed in the system in the first step. Manufacturing method.
第二工程が、第一工程で系内に形成された内容物に含まれる固体のヘキサフルオロアセトン一水和物を濾過して取得する工程を含む、発明１～３のヘキサフルオロアセトン一水和物の製造方法。 [Invention 4]
The second step includes the step of filtering and obtaining the solid hexafluoroacetone monohydrate contained in the contents formed in the system in the first step. Manufacturing method.
［発明５］
第二工程が、第一工程で系内に形成された内容物から有機溶媒を留去する工程を含む、発明１～４のヘキサフルオロアセトン一水和物の製造方法。 [Invention 5]
The method for producing hexafluoroacetone monohydrate according to inventions 1 to 4, wherein the second step includes a step of distilling off the organic solvent from the contents formed in the system in the first step.
第二工程が、第一工程で系内に形成された内容物から有機溶媒を留去する工程を含む、発明１～４のヘキサフルオロアセトン一水和物の製造方法。 [Invention 5]
The method for producing hexafluoroacetone monohydrate according to inventions 1 to 4, wherein the second step includes a step of distilling off the organic solvent from the contents formed in the system in the first step.
本発明の製造方法によると、特別な乾燥剤または脱水剤を用いることなくヘキサフルオロアセトン三水和物等の水和物から固体のヘキサフルオロアセトン一水和物を得ることができる。さらに、得られた固体のヘキサフルオロアセトン一水和物は表面に実質的に水が付着しないことから潮解性が少なく取り扱いが容易であるという効果を奏する。
According to the production method of the present invention, solid hexafluoroacetone monohydrate can be obtained from a hydrate such as hexafluoroacetone trihydrate without using a special desiccant or dehydrating agent. Furthermore, since the obtained solid hexafluoroacetone monohydrate has substantially no water adhering to the surface, it has an effect of being easy to handle with little deliquescence.
以下、本発明を詳細に説明する。尚、本明細書において、ヘキサフルオロアセトンを「ＨＦＡ」、ヘキサフルオロアセトン一水和物を「ＨＦＡ・Ｗ」、ヘキサフルオロアセトン三水和物を「ＨＦＡ・３Ｗ」と表すことがある。また、本明細書において、ヘキサフルオロアセトン水和物はヘキサフルオロアセトンを水和して得られる化合物の総称であり、水和数を限定しない水和物またはその水溶液をいい、「ＨＦＡ・３Ｗ」を含む概念である。
Hereinafter, the present invention will be described in detail. In this specification, hexafluoroacetone may be represented as “HFA”, hexafluoroacetone monohydrate as “HFA · W”, and hexafluoroacetone trihydrate as “HFA · 3W”. In addition, in this specification, hexafluoroacetone hydrate is a general term for compounds obtained by hydrating hexafluoroacetone, and refers to a hydrate that does not limit the number of hydration or an aqueous solution thereof. “HFA · 3W” It is a concept that includes
本発明は、水またはヘキサフルオロアセトン水和物が有機溶媒と共存する系に、系中に存在する水のモル数とヘキサフルオロアセトンのモル数が実質上等しくなるようにヘキサフルオロアセトンを導入し、次いで、有機溶媒を除去する工程を含むヘキサフルオロアセトン一水和物の製造方法である。ここに、「系中に存在する水のモル数」は、ヘキサフルオロアセトン水和物をヘキサフルオロアセトンと水に分解したとする場合に生成する水とフリーの水との合計モル数をいい、「フリーの水」はヘキサフルオロアセトン水和物の分子中に含まれない水をいう。
The present invention introduces hexafluoroacetone into a system in which water or hexafluoroacetone hydrate coexists with an organic solvent so that the number of moles of water present in the system is substantially equal to the number of moles of hexafluoroacetone. Then, it is a manufacturing method of hexafluoroacetone monohydrate including the process of removing an organic solvent. Here, "the number of moles of water present in the system" refers to the total number of moles of water and free water produced when hexafluoroacetone hydrate is decomposed into hexafluoroacetone and water, “Free water” refers to water that is not contained in the molecule of hexafluoroacetone hydrate.
水またはヘキサフルオロアセトン水和物が有機溶媒と共存する系は、有機溶媒とヘキサフルオロアセトン、または水とヘキサフルオロアセトン水和物を混合することで調製できる。この系は液相であって、均一系または不均一系であってもよい。ヘキサフルオロアセトン水和物としては、水和数は特に限定されず、水溶液であってよいが、ヘキサフルオロアセトン三水和物を使用することが好ましい。ヘキサフルオロアセトン水和物はさらに水と併せて使用することもできる。
A system in which water or hexafluoroacetone hydrate coexists with an organic solvent can be prepared by mixing an organic solvent and hexafluoroacetone, or water and hexafluoroacetone hydrate. This system is liquid phase and may be homogeneous or heterogeneous. As the hexafluoroacetone hydrate, the hydration number is not particularly limited and may be an aqueous solution, but it is preferable to use hexafluoroacetone trihydrate. Hexafluoroacetone hydrate can also be used in combination with water.
ヘキサフルオロアセトン三水和物は、ヘキサフルオロアセトンと水が反応して生成したｇｅｍ－ジオールであるヘキサフルオロアセトン一水和物の２水和物（本明細書で、この２水和物の２に相当する水を「付加水」という。）であって、下式で表される化学物質であり、最高共沸組成（沸点１０６℃）を持つ安定した液体である。
Hexafluoroacetone trihydrate is a dihydrate of hexafluoroacetone monohydrate, which is a gem-diol produced by the reaction of hexafluoroacetone and water (herein the dihydrate 2 Is a chemical substance represented by the following formula, and is a stable liquid having the highest azeotropic composition (boiling point 106 ° C.).
これに対し、ヘキサフルオロアセトン一水和物は、融点（４６℃）の固体であるが、融点以上では分解して無水のヘキサフルオロアセトンとヘキサフルオロアセトン三水和物に不均化する（特許文献１）。
On the other hand, hexafluoroacetone monohydrate is a solid with a melting point (46 ° C.), but decomposes above the melting point and disproportionates into anhydrous hexafluoroacetone and hexafluoroacetone trihydrate (patent) Reference 1).
有機溶媒としては、常温（約２５℃）で液体である芳香族化合物、エーテル化合物、脂肪族炭化水素、ハロゲン化脂肪族炭化水素（ハロゲン系溶媒）などが挙げられる。芳香族化合物としては、特に限定されず、単環式、環集合式、縮合多環式の何れでもよいが、単環式のベンゼンまたはベンゼンの水素原子がハロゲン原子、アルキル基、フルオロアルキル基などで置換した化合物が好ましい。そのような化合物としては、ベンゼン、トルエン、キシレン、エチルベンゼン、クロロベンゼン、ベンゾトリフルオライド、２，４－ジクロロベンゾトリフルオライド、ｏ－、ｍ－またはｐ－ビストリフルオロメチルベンゼンなどがあげられる。エーテル化合物としては、ジメチルエーテル、ジエチルエーテル、イソプロピルエーテル、エチルイソプロピルエーテル、ブチルメチルエーテル、エチルブチルエーテルなどの鎖式のエーテル、テトラヒドロフラン、ピラン、ジオキサンなどの環状エーテルが挙げられる。脂肪族炭化水素としては、ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタン、ｎ－オクタン、シクロペンタン、シクロヘキサン、シクロヘプタンなどが挙げられる。ハロゲン系溶媒としては、脂肪族炭化水素の水素原子がハロゲン原子、アルキル基、フルオロアルキル基などで置換した化合物であり、四塩化炭素、クロロホルム、ジクロロメタン、１，２－ジクロロエタン、シス－１，２－ジクロロエチレン、トランス－１，２－ジクロロエチレン、１，１，２－トリクロロエタンなどが挙げられる。有機溶媒としては、脂肪族炭化水素、ハロゲン化脂肪族炭化水素が好ましい。具体的には、ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタン、シクロペンタン、シクロヘキサンなどの脂肪族炭化水素、四塩化炭素、クロロホルム、ジクロロメタン、１，２－ジクロロエタンなどのハロゲン系溶媒が好ましい有機溶媒として挙げられる。
Examples of the organic solvent include aromatic compounds, ether compounds, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons (halogen solvents) that are liquid at room temperature (about 25 ° C.). The aromatic compound is not particularly limited and may be any of monocyclic, ring aggregate, and condensed polycyclic, but monocyclic benzene or a hydrogen atom of benzene is a halogen atom, an alkyl group, a fluoroalkyl group, or the like Compounds substituted with are preferred. Examples of such compounds include benzene, toluene, xylene, ethylbenzene, chlorobenzene, benzotrifluoride, 2,4-dichlorobenzotrifluoride, o-, m- or p-bistrifluoromethylbenzene. Examples of the ether compound include chain ethers such as dimethyl ether, diethyl ether, isopropyl ether, ethyl isopropyl ether, butyl methyl ether, and ethyl butyl ether, and cyclic ethers such as tetrahydrofuran, pyran, and dioxane. Examples of the aliphatic hydrocarbon include n-pentane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane and cycloheptane. The halogen solvent is a compound in which a hydrogen atom of an aliphatic hydrocarbon is substituted with a halogen atom, an alkyl group, a fluoroalkyl group or the like, and includes carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, cis-1,2 -Dichloroethylene, trans-1,2-dichloroethylene, 1,1,2-trichloroethane and the like. As the organic solvent, aliphatic hydrocarbons and halogenated aliphatic hydrocarbons are preferable. Specifically, aliphatic solvents such as aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, cyclopentane, and cyclohexane, and halogen solvents such as carbon tetrachloride, chloroform, dichloromethane, and 1,2-dichloroethane are preferable. As mentioned.
水またはヘキサフルオロアセトン水和物が有機溶媒と共存する系中の水の濃度は任意に決めればよいが、通常ヘキサフルオロアセトン（ヘキサフルオロアセトン水和物を水とヘキサフルオロアセトンに分解したとする場合のヘキサフルオロアセトン、をいう。）１質量部に対し有機溶媒１～１０００質量部であり、５～１００質量部が好ましく、１０～５０質量部がより好ましい。１質量部未満では反応系の全体が未反応の水を含む塊状となって取り扱いに困難を来たし、１０００重量部を越えると溶媒の除去が煩雑でありかつスループットが低下するので好ましくない。
The concentration of water or water in the system in which hexafluoroacetone hydrate coexists with the organic solvent may be determined arbitrarily, but usually hexafluoroacetone (assuming that hexafluoroacetone hydrate is decomposed into water and hexafluoroacetone) Hexafluoroacetone in this case) 1 to 1000 parts by weight of organic solvent per 1 part by weight, preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight. If the amount is less than 1 part by mass, the entire reaction system becomes a lump containing unreacted water, which is difficult to handle. If the amount exceeds 1000 parts by weight, the removal of the solvent is complicated and the throughput is not preferable.
本発明にかかるヘキサフルオロアセトン一水和物は、ヘキサフルオロアセトン水和物、例えばヘキサフルオロアセトン三水和物またはヘキサフルオロアセトンを含む水溶液と有機溶媒からなる混合物へ系内の水（付加水とフリーの水）と等モルのヘキサフルオロアセトンを添加することで有機溶媒に溶解した状態でまたは析出した状態で得ることができる。
The hexafluoroacetone monohydrate according to the present invention is a mixture of an aqueous solution containing hexafluoroacetone hydrate, for example, hexafluoroacetone trihydrate or hexafluoroacetone and an organic solvent, with water in the system (additional water and Free water) and equimolar hexafluoroacetone can be added to obtain a solution dissolved in an organic solvent or precipitated.
水またはヘキサフルオロアセトン水和物が有機溶媒と共存する系を調製し、そこへ系中に存在する水のモル数とヘキサフルオロアセトンおよびヘキサフルオロアセトン水和物の合計モル数が実質上等しくなるようにヘキサフルオロアセトンを導入する。ヘキサフルオロアセトンは、ヘキサフルオロアセトン（導入するヘキサフルオロアセトン）／水（付加水とフリーの水の合計）のモル比を実質的に１とするのが好ましいが、通常１～１．２とすればよい。操作上のロス等を考慮して若干の過剰量は許容してよいが、ヘキサフルオロアセトンが過剰の場合、未反応のまま流失するので好ましくなく、不足する場合、フリーの水またはヘキサフルオロアセトン三水和物が有機溶媒溶液中に残存するので好ましくない。
A system in which water or hexafluoroacetone hydrate coexists with an organic solvent is prepared, and the number of moles of water present in the system is substantially equal to the total number of moles of hexafluoroacetone and hexafluoroacetone hydrate. Hexafluoroacetone is introduced as follows. The hexafluoroacetone preferably has a molar ratio of hexafluoroacetone (hexafluoroacetone to be introduced) / water (total amount of added water and free water) of substantially 1, but is usually 1 to 1.2. That's fine. Considering operational loss, etc., a slight excess may be allowed. However, when hexafluoroacetone is excessive, it is not preferable because it will be unreacted to be washed away. Since the hydrate remains in the organic solvent solution, it is not preferable.
系内にヘキサフルオロアセトンを導入する際は、系内にある液体部分を２０℃以上で液体の沸騰温度以下に加温しておくことが好ましい。低温においては十分な反応速度が得られないからである。温度制御しない場合、反応が進むに従い反応系の温度は上昇し、反応の完了と共に低下する。したがって、系内の温度は、有機溶媒の種類によって異なるが通常ヘキサフルオロアセトン三水和物の沸点（１０６℃）以下とする。また、ヘキサフルオロアセトン一水和物を析出させるには融点（４６℃）以下で行う必要があるので、少なくとも固体を有機溶媒から分離する際には４６℃以下とする。反応に際しての下限温度は、特に限定されないが溶媒の融点以上であればよく、－４０℃以上とすればよく、０℃以上とするのが操作上有利である。
When introducing hexafluoroacetone into the system, it is preferable to heat the liquid portion in the system at 20 ° C. or higher and below the boiling temperature of the liquid. This is because a sufficient reaction rate cannot be obtained at a low temperature. When the temperature is not controlled, the temperature of the reaction system increases as the reaction proceeds and decreases with the completion of the reaction. Therefore, although the temperature in the system varies depending on the type of organic solvent, it is usually set to a boiling point (106 ° C.) or less of hexafluoroacetone trihydrate. In order to precipitate hexafluoroacetone monohydrate, it is necessary to carry out at a melting point (46 ° C.) or lower, so at least 46 ° C. or lower is required when separating a solid from an organic solvent. The lower limit temperature during the reaction is not particularly limited, but may be at least the melting point of the solvent, may be −40 ° C. or more, and is advantageously 0 ° C. or more.
前記に従いヘキサフルオロアセトンが導入された系にはヘキサフルオロアセトン一水和物が生成し、溶解度を超える量は固体として析出する。この際、系の温度を冷却して析出を促進し、または析出量の増大を図ることができる。この固体は、ろ過またはデカンテーションで回収することができ、乾燥させることができる。乾燥は融点（４６℃）以下で行うことが好ましく、そのためには減圧下で行うのが好ましい。また、ヘキサフルオロアセトン一水和物が生成した系の全体を減圧して溶媒を留去することにより、一部のヘキサフルオロアセトン一水和物を析出させ、前記のようにろ過乾燥することで固体を得ることができる。さらに、反応系から有機溶媒の全部を留去してヘキサフルオロアセトン一水和物を析出させて固体を回収することもできる。
According to the above, hexafluoroacetone monohydrate is formed in the system in which hexafluoroacetone is introduced, and the amount exceeding the solubility is precipitated as a solid. At this time, the temperature of the system can be cooled to promote precipitation, or the amount of precipitation can be increased. This solid can be recovered by filtration or decantation and dried. Drying is preferably performed at a melting point (46 ° C.) or lower, and for this purpose, it is preferably performed under reduced pressure. In addition, by reducing the pressure of the entire system in which hexafluoroacetone monohydrate was formed and distilling off the solvent, a portion of hexafluoroacetone monohydrate was precipitated and filtered and dried as described above. A solid can be obtained. Furthermore, the solid can also be recovered by distilling off all of the organic solvent from the reaction system to precipitate hexafluoroacetone monohydrate.
このようにして得られた固体のヘキサフルオロアセトン一水和物は、溶媒を用いずに水とヘキサフルオロアセトンを１：１の比率で接触させて得られる場合には固体の表面に水が付着しているのに対し、表面に水を持たないという特徴がある。
When the solid hexafluoroacetone monohydrate thus obtained is obtained by contacting water and hexafluoroacetone at a ratio of 1: 1 without using a solvent, water adheres to the surface of the solid. In contrast, the surface has no water.
ろ過等の手段で固体を分離した残りの液（母液）には、使用する有機溶媒の種類によりヘキサフルオロアセトン一水和物が溶解している場合があるが、この母液に再度水またはヘキサフルオロアセトン水和物とヘキサフルオロアセトンを導入して、ヘキサフルオロアセトン一水和物の析出をさせることができる。
Depending on the type of organic solvent used, hexafluoroacetone monohydrate may be dissolved in the remaining liquid (mother liquor) from which the solid has been separated by means such as filtration. Acetone hydrate and hexafluoroacetone can be introduced to precipitate hexafluoroacetone monohydrate.
本発明の処理手順の例を説明する。攪拌装置およびガス導入口を備えた密閉反応容器に所定量のヘキサフルオロアセトン三水和物と有機溶媒を導入する。静止状態では反応容器内はニ層に分離していることもあるがその際は攪拌するのが好ましい。
An example of the processing procedure of the present invention will be described. A predetermined amount of hexafluoroacetone trihydrate and an organic solvent are introduced into a closed reaction vessel equipped with a stirrer and a gas inlet. In the stationary state, the inside of the reaction vessel may be separated into two layers, but in that case, stirring is preferable.
急速に反応が進むと系中の溶液が昇温するので、外部から冷却しながら攪拌し、ヘキサフルオロアセトン（導入するヘキサフルオロアセトン）と水（付加水とフリーの水）のモル比が１：１になる量のヘキサフルオロアセトンを徐々に反応容器のガス導入口から導入する。この時、開口部が気相部であっても液相部であってもヘキサフルオロアセトン一水和物の析出によりガス導入口の閉塞が起こらないよう留意する。所定量のヘキサフルオロアセトンの導入が完了し反応液温が低下し圧力が低下した時点で反応終了とする。反応容器中には、均一な溶液または白色固体の析出した溶液が得られる。反応溶液を冷却して析出を促進させてもよい。この反応容器の内容物を取り出し、析出した固体を液相から分離してからロータリーエバポレータなどを用いて融点以下の温度で溶液を揮発させてヘキサフルオロアセトン一水和物の結晶を得る。この処理は減圧下で行うことが好ましい。
As the reaction proceeds rapidly, the temperature of the solution in the system rises, so stirring is performed while cooling from the outside, and the molar ratio of hexafluoroacetone (hexafluoroacetone to be introduced) and water (added water and free water) is 1: The amount of hexafluoroacetone that becomes 1 is gradually introduced from the gas inlet of the reaction vessel. At this time, care should be taken not to block the gas inlet due to the precipitation of hexafluoroacetone monohydrate regardless of whether the opening is a gas phase portion or a liquid phase portion. The reaction is completed when the introduction of a predetermined amount of hexafluoroacetone is completed and the reaction solution temperature is lowered and the pressure is lowered. A homogeneous solution or a solution in which a white solid is precipitated is obtained in the reaction vessel. The reaction solution may be cooled to promote precipitation. The contents of the reaction vessel are taken out, the precipitated solid is separated from the liquid phase, and then the solution is volatilized at a temperature below the melting point using a rotary evaporator or the like to obtain hexafluoroacetone monohydrate crystals. This treatment is preferably performed under reduced pressure.
反応装置は、特に限定されないが、耐圧容器または凝縮器を備えた容器が好ましく、攪拌器を備えるのが好ましい。装置の材質は、ステンレス鋼、ニッケル合金鋼、ガラス、フッ素樹脂、炭素、ポリエチレンまたはこれらの材質でライニングされもしくはクラッドされた材料が使用できる。
The reaction apparatus is not particularly limited, but is preferably a pressure vessel or a vessel equipped with a condenser, and preferably a stirrer. As the material of the apparatus, stainless steel, nickel alloy steel, glass, fluororesin, carbon, polyethylene, or a material lined or clad with these materials can be used.
以下に、実施例により本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
［実施例１］
攪拌装置、ドライアイス／アセトン冷却還流器、温度計、ガス導入口を備え、還流器の開口部は風船で閉鎖系としたガラス製の２００ｍＬ四つ口反応装置にクロロホルム：１４８ｇ、ヘキサフルオロアセトン三水和物（ＨＦＡ・３Ｗ）：２２ｇ（０．１モル）を入れ、外部を氷冷してガス導入口からヘキサフルオロアセトン（ＨＦＡ）：３２ｇ（０．２モル）を内温２５℃に保ちながら１時間をかけて導入し、反応を終了させた。反応終了後、スラリーから結晶を濾別回収し、エバポレーターで減圧乾燥して、白色針状結晶２１ｇを得た（収率３２％）。 [Example 1]
It is equipped with a stirrer, dry ice / acetone cooling reflux, thermometer, gas inlet, and the opening of the reflux is a glass 200 mL four-neck reactor closed with a balloon. Chloroform: 148 g, hexafluoroacetone Hydrate (HFA · 3W): 22 g (0.1 mol) is added, the outside is ice-cooled, and hexafluoroacetone (HFA): 32 g (0.2 mol) is kept at an internal temperature of 25 ° C. from the gas inlet. The reaction was terminated by introducing 1 hour. After completion of the reaction, crystals were collected from the slurry by filtration and dried under reduced pressure with an evaporator to obtain 21 g of white needle crystals (yield 32%).
攪拌装置、ドライアイス／アセトン冷却還流器、温度計、ガス導入口を備え、還流器の開口部は風船で閉鎖系としたガラス製の２００ｍＬ四つ口反応装置にクロロホルム：１４８ｇ、ヘキサフルオロアセトン三水和物（ＨＦＡ・３Ｗ）：２２ｇ（０．１モル）を入れ、外部を氷冷してガス導入口からヘキサフルオロアセトン（ＨＦＡ）：３２ｇ（０．２モル）を内温２５℃に保ちながら１時間をかけて導入し、反応を終了させた。反応終了後、スラリーから結晶を濾別回収し、エバポレーターで減圧乾燥して、白色針状結晶２１ｇを得た（収率３２％）。 [Example 1]
It is equipped with a stirrer, dry ice / acetone cooling reflux, thermometer, gas inlet, and the opening of the reflux is a glass 200 mL four-neck reactor closed with a balloon. Chloroform: 148 g, hexafluoroacetone Hydrate (HFA · 3W): 22 g (0.1 mol) is added, the outside is ice-cooled, and hexafluoroacetone (HFA): 32 g (0.2 mol) is kept at an internal temperature of 25 ° C. from the gas inlet. The reaction was terminated by introducing 1 hour. After completion of the reaction, crystals were collected from the slurry by filtration and dried under reduced pressure with an evaporator to obtain 21 g of white needle crystals (yield 32%).
回収した白色針状結晶についてＮＭＲ（１３Ｃ、Ｈ、Ｆ）およびＦＴ－ＩＲ測定したところ、ヘキサフルオロアセトン一水和物（１，１，１，３，３，３－ヘキサフルオロプロパン－２－ジオール）と同定され、その他の成分は認められなかった。また、結晶に含まれるヘキサフルオロアセトンを中和滴定で測定し、水分をカールフィッシャ水分測定装置で測定したところ、ヘキサフルオロアセトンと水のモル比は１：１であった。
The recovered white needle-like crystals were measured by NMR (13C, H, F) and FT-IR, and found to be hexafluoroacetone monohydrate (1,1,1,3,3,3-hexafluoropropane-2-diol. ) And other components were not recognized. Further, hexafluoroacetone contained in the crystal was measured by neutralization titration, and the water content was measured with a Karl Fischer moisture measuring device. As a result, the molar ratio of hexafluoroacetone to water was 1: 1.
［実施例２］
攪拌装置、ドライアイス／アセトン冷却還流器、温度計、ガス導入口を備え、還流器の開口部は風船で閉鎖系としたガラス製の２００ｍＬ四つ口反応装置にクロロホルム：２００ｇ、ノルマルヘキサン：８９ｇ、ヘキサフルオロアセトン三水和物（ＨＦＡ・３Ｗ）：２２ｇ（０．１モル）を入れ、外部を氷冷してガス導入口からヘキサフルオロアセトン（ＨＦＡ）：３２ｇ（０．２モル）を内温２５℃に保ちながら１時間をかけて導入し、反応を終了させた。反応終了後、スラリーから結晶を濾別回収し、エバポレーターで減圧乾燥して、白色針状結晶３１ｇを得た（収率５５％）。 [Example 2]
It is equipped with a stirrer, dry ice / acetone cooling reflux, thermometer, gas inlet, and the opening of the reflux is a 200 mL four-necked reactor with a balloon closed system. Chloroform: 200 g, normal hexane: 89 g Hexafluoroacetone trihydrate (HFA · 3W): 22 g (0.1 mol) was added, the outside was ice-cooled, and hexafluoroacetone (HFA): 32 g (0.2 mol) was added from the gas inlet. It was introduced over 1 hour while maintaining the temperature at 25 ° C. to complete the reaction. After completion of the reaction, crystals were collected from the slurry by filtration and dried under reduced pressure with an evaporator to obtain 31 g of white needle crystals (yield 55%).
攪拌装置、ドライアイス／アセトン冷却還流器、温度計、ガス導入口を備え、還流器の開口部は風船で閉鎖系としたガラス製の２００ｍＬ四つ口反応装置にクロロホルム：２００ｇ、ノルマルヘキサン：８９ｇ、ヘキサフルオロアセトン三水和物（ＨＦＡ・３Ｗ）：２２ｇ（０．１モル）を入れ、外部を氷冷してガス導入口からヘキサフルオロアセトン（ＨＦＡ）：３２ｇ（０．２モル）を内温２５℃に保ちながら１時間をかけて導入し、反応を終了させた。反応終了後、スラリーから結晶を濾別回収し、エバポレーターで減圧乾燥して、白色針状結晶３１ｇを得た（収率５５％）。 [Example 2]
It is equipped with a stirrer, dry ice / acetone cooling reflux, thermometer, gas inlet, and the opening of the reflux is a 200 mL four-necked reactor with a balloon closed system. Chloroform: 200 g, normal hexane: 89 g Hexafluoroacetone trihydrate (HFA · 3W): 22 g (0.1 mol) was added, the outside was ice-cooled, and hexafluoroacetone (HFA): 32 g (0.2 mol) was added from the gas inlet. It was introduced over 1 hour while maintaining the temperature at 25 ° C. to complete the reaction. After completion of the reaction, crystals were collected from the slurry by filtration and dried under reduced pressure with an evaporator to obtain 31 g of white needle crystals (yield 55%).
回収した白色針状結晶についてＮＭＲ（１３Ｃ、Ｈ、Ｆ）およびＦＴ－ＩＲ測定したところ、ヘキサフルオロアセトン一水和物（１，１，１，３，３，３－ヘキサフルオロプロパン－２－ジオール）と同定され、その他の成分は認められなかった。また、結晶に含まれるヘキサフルオロアセトンを中和滴定で測定し、水分をカールフィッシャ水分測定装置で測定したところ、ヘキサフルオロアセトンと水のモル比は１：１であった。
The recovered white needle-like crystals were measured by NMR (13C, H, F) and FT-IR, and found to be hexafluoroacetone monohydrate (1,1,1,3,3,3-hexafluoropropane-2-diol. ) And other components were not recognized. Further, hexafluoroacetone contained in the crystal was measured by neutralization titration, and the water content was measured with a Karl Fischer moisture measuring device. As a result, the molar ratio of hexafluoroacetone to water was 1: 1.
［実施例３］
攪拌装置、ドライアイス／アセトン冷却還流器、温度計、ガス導入口を備え、還流器の開口部は風船で閉鎖系としたガラス製の２００ｍＬ四つ口反応装置にノルマルヘキサン：１７８ｇ、ヘキサフルオロアセトン三水和物（ＨＦＡ・３Ｗ）：２２ｇ（０．１モル）を入れ、外部を氷冷してガス導入口からヘキサフルオロアセトン（ＨＦＡ）：３２ｇ（０．２モル）を内温２５℃に保ちながら１時間をかけて導入し、反応を終了させた。反応終了後、スラリーから結晶を濾別回収し、エバポレーターで減圧乾燥して、白色針状結晶４９ｇを得た（収率８７％）。 [Example 3]
It is equipped with a stirrer, dry ice / acetone cooling reflux, thermometer, gas inlet, and the opening of the reflux is a glass 200 ml four-necked reactor closed with a balloon. Normal hexane: 178 g, hexafluoroacetone Trihydrate (HFA · 3W): 22 g (0.1 mol) was added, the outside was ice-cooled, and hexafluoroacetone (HFA): 32 g (0.2 mol) was brought to an internal temperature of 25 ° C. from the gas inlet. It was introduced over 1 hour while maintaining the reaction to complete the reaction. After completion of the reaction, crystals were collected from the slurry by filtration and dried under reduced pressure with an evaporator to obtain 49 g of white needle crystals (yield 87%).
攪拌装置、ドライアイス／アセトン冷却還流器、温度計、ガス導入口を備え、還流器の開口部は風船で閉鎖系としたガラス製の２００ｍＬ四つ口反応装置にノルマルヘキサン：１７８ｇ、ヘキサフルオロアセトン三水和物（ＨＦＡ・３Ｗ）：２２ｇ（０．１モル）を入れ、外部を氷冷してガス導入口からヘキサフルオロアセトン（ＨＦＡ）：３２ｇ（０．２モル）を内温２５℃に保ちながら１時間をかけて導入し、反応を終了させた。反応終了後、スラリーから結晶を濾別回収し、エバポレーターで減圧乾燥して、白色針状結晶４９ｇを得た（収率８７％）。 [Example 3]
It is equipped with a stirrer, dry ice / acetone cooling reflux, thermometer, gas inlet, and the opening of the reflux is a glass 200 ml four-necked reactor closed with a balloon. Normal hexane: 178 g, hexafluoroacetone Trihydrate (HFA · 3W): 22 g (0.1 mol) was added, the outside was ice-cooled, and hexafluoroacetone (HFA): 32 g (0.2 mol) was brought to an internal temperature of 25 ° C. from the gas inlet. It was introduced over 1 hour while maintaining the reaction to complete the reaction. After completion of the reaction, crystals were collected from the slurry by filtration and dried under reduced pressure with an evaporator to obtain 49 g of white needle crystals (yield 87%).
回収した白色針状結晶についてＮＭＲ（１３Ｃ、Ｈ、Ｆ）およびＦＴ－ＩＲ測定したところ、ヘキサフルオロアセトン一水和物（１，１，１，３，３，３－ヘキサフルオロプロパン－２－ジオール）と同定され、その他の成分は認められなかった。また、結晶に含まれるヘキサフルオロアセトンを中和滴定で測定し、水分をカールフィッシャ水分測定装置で測定したところ、ヘキサフルオロアセトンと水のモル比は１：１であった。
The recovered white needle-like crystals were measured by NMR (13C, H, F) and FT-IR, and found to be hexafluoroacetone monohydrate (1,1,1,3,3,3-hexafluoropropane-2-diol. ) And other components were not recognized. Further, hexafluoroacetone contained in the crystal was measured by neutralization titration, and the water content was measured with a Karl Fischer moisture measuring device. As a result, the molar ratio of hexafluoroacetone to water was 1: 1.
［比較例１］
攪拌装置、ドライアイス／アセトン冷却還流器、温度計、ガス導入口を備え、還流器の開口部は風船で閉鎖系としたガラス製の２００ｍｌ四つ口反応装置にヘキサフルオロアセトン三水和物（ＨＦＡ・３Ｗ）：４４ｇ（０．２モル）を入れ、外部を氷冷しながらガス導入口からヘキサフルオロアセトン（ＨＦＡ）：６６ｇ（０．４モル）をゆっくり導入した。内温は２５℃を保った。このとき冷却還流器ではＨＦＡ還流がみられ、反応器の内容物には針状結晶が生じ、その後全体が塊状となって攪拌ができなくなったので、ＨＦＡの導入を５０ｇ（０．３モル）で中止し、反応器内部の未反応ＨＦＡをパージし、反応器を開放し、内容物の固体を取り出した。この固体は湿った状態であった。 [Comparative Example 1]
It is equipped with a stirrer, dry ice / acetone cooled reflux, thermometer, gas inlet, and the opening of the reflux is a glass 200 ml four-neck reactor closed with a balloon. HFA · 3W): 44 g (0.2 mol) was added, and hexafluoroacetone (HFA): 66 g (0.4 mol) was slowly introduced from the gas inlet while the outside was ice-cooled. The internal temperature was kept at 25 ° C. At this time, HFA reflux was observed in the cooling reflux, and needle-like crystals were formed in the contents of the reactor, and then the whole became agglomerated and could not be stirred. Therefore, 50 g (0.3 mol) of HFA was introduced. Was stopped, the reactor was purged with unreacted HFA, the reactor was opened, and the solid content was removed. This solid was moist.
攪拌装置、ドライアイス／アセトン冷却還流器、温度計、ガス導入口を備え、還流器の開口部は風船で閉鎖系としたガラス製の２００ｍｌ四つ口反応装置にヘキサフルオロアセトン三水和物（ＨＦＡ・３Ｗ）：４４ｇ（０．２モル）を入れ、外部を氷冷しながらガス導入口からヘキサフルオロアセトン（ＨＦＡ）：６６ｇ（０．４モル）をゆっくり導入した。内温は２５℃を保った。このとき冷却還流器ではＨＦＡ還流がみられ、反応器の内容物には針状結晶が生じ、その後全体が塊状となって攪拌ができなくなったので、ＨＦＡの導入を５０ｇ（０．３モル）で中止し、反応器内部の未反応ＨＦＡをパージし、反応器を開放し、内容物の固体を取り出した。この固体は湿った状態であった。 [Comparative Example 1]
It is equipped with a stirrer, dry ice / acetone cooled reflux, thermometer, gas inlet, and the opening of the reflux is a glass 200 ml four-neck reactor closed with a balloon. HFA · 3W): 44 g (0.2 mol) was added, and hexafluoroacetone (HFA): 66 g (0.4 mol) was slowly introduced from the gas inlet while the outside was ice-cooled. The internal temperature was kept at 25 ° C. At this time, HFA reflux was observed in the cooling reflux, and needle-like crystals were formed in the contents of the reactor, and then the whole became agglomerated and could not be stirred. Therefore, 50 g (0.3 mol) of HFA was introduced. Was stopped, the reactor was purged with unreacted HFA, the reactor was opened, and the solid content was removed. This solid was moist.
上述の通り、本発明の製造方法では、特別な乾燥剤または脱水剤を用いることなく、ヘキサフルオロアセトン三水和物等の水和物から、潮解性が少なく取り扱いが容易である固体のヘキサフルオロアセトン一水和物を得ることができる。
As described above, in the production method of the present invention, solid hexafluoro which is easy to handle and has low deliquescence from hydrates such as hexafluoroacetone trihydrate without using a special desiccant or dehydrating agent. Acetone monohydrate can be obtained.
以上、本発明の実施形態について説明したが、本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、以下の実施形態に対し適宜変更、改良可能であることはいうまでもない。
Although the embodiments of the present invention have been described above, it is needless to say that the following embodiments can be appropriately changed and improved based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Absent.
Claims (5)
- ヘキサフルオロアセトン一水和物の製造方法であって、水またはヘキサフルオロアセトン水和物が有機溶媒と共存する系に、系中に存在する水のモル数（ヘキサフルオロアセトン水和物をヘキサフルオロアセトンと水に分解したとする場合に生成する水とフリーの水との合計モル数）とヘキサフルオロアセトンのモル数が実質上等しくなるようにヘキサフルオロアセトンを導入する第一工程と、第一工程で系内に形成された内容物から固体のヘキサフルオロアセトン一水和物を取得する第二工程と、を含むヘキサフルオロアセトン一水和物の製造方法。 A method for producing hexafluoroacetone monohydrate, in which water or hexafluoroacetone hydrate coexists with an organic solvent, and the number of moles of water present in the system (hexafluoroacetone hydrate is converted to hexafluoroacetone hydrate). A first step of introducing hexafluoroacetone so that the number of moles of hexafluoroacetone is substantially equal to the total number of moles of water and free water produced when it is decomposed into acetone and water; A second step of obtaining solid hexafluoroacetone monohydrate from the contents formed in the system in the step, and a method for producing hexafluoroacetone monohydrate.
- 有機溶媒が、脂肪族炭化水素またはハロゲン化脂肪族炭化水素である、請求項１に記載のヘキサフルオロアセトン一水和物の製造方法。 The method for producing hexafluoroacetone monohydrate according to claim 1, wherein the organic solvent is an aliphatic hydrocarbon or a halogenated aliphatic hydrocarbon.
- 有機溶媒が、ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタン、シクロペンタン、シクロヘキサン、四塩化炭素、クロロホルム、ジクロロメタンおよび１，２－ジクロロエタンから選ばれた１種以上の有機溶媒である、請求項２に記載のヘキサフルオロアセトン一水和物の製造方法。 3. The organic solvent is one or more organic solvents selected from n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane, carbon tetrachloride, chloroform, dichloromethane and 1,2-dichloroethane. A process for producing hexafluoroacetone monohydrate as described in 1. above.
- 第二工程が、第一工程で系内に形成された内容物に含まれる固体のヘキサフルオロアセトン一水和物を濾過して取得する工程を含む、請求項１～３のいずれか１項に記載のヘキサフルオロアセトン一水和物の製造方法。 The process according to any one of claims 1 to 3, wherein the second step includes a step of filtering and obtaining solid hexafluoroacetone monohydrate contained in the contents formed in the system in the first step. The manufacturing method of the hexafluoroacetone monohydrate of description.
- 第二工程が、第一工程で系内に形成された内容物から有機溶媒を留去する工程を含む、請求項１～４のいずれか１項に記載のヘキサフルオロアセトン一水和物の製造方法。 The production of hexafluoroacetone monohydrate according to any one of claims 1 to 4, wherein the second step includes a step of distilling off the organic solvent from the contents formed in the system in the first step. Method.
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|---|---|---|---|---|
| JPS59181235A (en) * | 1983-03-30 | 1984-10-15 | Central Glass Co Ltd | Production of carbonyl compounds |
| JPS59204149A (en) * | 1983-04-30 | 1984-11-19 | Central Glass Co Ltd | Method for purifying hexafluoroacetone hydrate |
| JPS6137748A (en) * | 1984-07-18 | 1986-02-22 | ソシエテ アトケム | Manufacture of pure hydrate of furol and hexafuroloacetone from hemiacetal |
| JPH01203339A (en) * | 1988-02-05 | 1989-08-16 | Nippon Mektron Ltd | Production of hexafluoroacetone or hydrate thereof |
| WO2009028584A1 (en) * | 2007-08-29 | 2009-03-05 | Central Glass Company, Limited | Process for dehydration of hexafluoroacetone hydrate |
| WO2011021491A1 (en) * | 2009-08-18 | 2011-02-24 | セントラル硝子株式会社 | Process for preparation of hexafluoroacetone monohydrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59204142A (en) * | 1983-04-28 | 1984-11-19 | Nippon Mektron Ltd | Production of hexafluoroisopropyl alcohol |
| JPS6069047A (en) * | 1983-09-27 | 1985-04-19 | Central Glass Co Ltd | Production of 1,1,1,3,3,3-hexafluoropropan-2-ol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59181235A (en) * | 1983-03-30 | 1984-10-15 | Central Glass Co Ltd | Production of carbonyl compounds |
| JPS59204149A (en) * | 1983-04-30 | 1984-11-19 | Central Glass Co Ltd | Method for purifying hexafluoroacetone hydrate |
| JPS6137748A (en) * | 1984-07-18 | 1986-02-22 | ソシエテ アトケム | Manufacture of pure hydrate of furol and hexafuroloacetone from hemiacetal |
| JPH01203339A (en) * | 1988-02-05 | 1989-08-16 | Nippon Mektron Ltd | Production of hexafluoroacetone or hydrate thereof |
| WO2009028584A1 (en) * | 2007-08-29 | 2009-03-05 | Central Glass Company, Limited | Process for dehydration of hexafluoroacetone hydrate |
| WO2011021491A1 (en) * | 2009-08-18 | 2011-02-24 | セントラル硝子株式会社 | Process for preparation of hexafluoroacetone monohydrate |
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