JP2000063316A - Purification of dihalotrifluoroacetone - Google Patents
Purification of dihalotrifluoroacetoneInfo
- Publication number
- JP2000063316A JP2000063316A JP10234104A JP23410498A JP2000063316A JP 2000063316 A JP2000063316 A JP 2000063316A JP 10234104 A JP10234104 A JP 10234104A JP 23410498 A JP23410498 A JP 23410498A JP 2000063316 A JP2000063316 A JP 2000063316A
- Authority
- JP
- Japan
- Prior art keywords
- derivative
- dihalotrifluoroacetone
- formula
- boiling point
- dichloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、医農薬中間体とし
て有用なジハロトリフルオロアセトン誘導体の精製方法
に関する。TECHNICAL FIELD The present invention relates to a method for purifying a dihalotrifluoroacetone derivative useful as an intermediate for medicines and agricultural chemicals.
【０００２】[0002]
【従来の技術および発明が解決しようとする課題】下記
一般式（１）で示されるジハロトリフルオロアセトン誘
導体は、トリフルオロメチル基をもつ医農薬の重要中間
体として知られている（例えば特開平９−３２３９７７
号公報参照）。一般式（１）で示されるジハロトリフル
オロアセトン誘導体は、製造過程において該化合物の異
性体等の副生物が通常混入するが、これらジハロトリフ
ルオロアセトン誘導体は低沸点であり、また副生物との
沸点差も小さいため(１，１−ジクロロ−３，３，３−
トリフルオロアセトンの沸点は、７５−７６℃、１，１
−ジブロモ−３，３，３−トリフルオロアセトンの沸点
は１１１−１１３℃)、蒸留で精製するのは困難であっ
た。BACKGROUND OF THE INVENTION The dihalotrifluoroacetone derivative represented by the following general formula (1) is known as an important intermediate for medical and agricultural chemicals having a trifluoromethyl group (for example, Kaihei 9-323977
(See the official gazette). The dihalotrifluoroacetone derivative represented by the general formula (1) is usually mixed with by-products such as isomers of the compound during the production process, but these dihalotrifluoroacetone derivatives have a low boiling point and are by-products. Since the boiling point difference with is small (1,1-dichloro-3,3,3-
The boiling point of trifluoroacetone is 75-76 ° C, 1,1
The boiling point of -dibromo-3,3,3-trifluoroacetone was 111-113 ° C), and it was difficult to purify it by distillation.
【０００３】[0003]
【課題を解決するための手段】本発明者らは、ジハロト
リフルオロアセトン誘導体（１）の精製方法について鋭
意検討した結果、ジハロトリフルオロアセトン誘導体
（１）を、より沸点の高い誘導体へ変換し、蒸留にて精
製した後、再びトリフルオロアセトン誘導体へと戻すこ
とで効率よく精製でき、延いては製品中の不純物を減ら
すことができることを見出し、本発明に至った。すなわ
ち本発明は、一般式（１）
（式中、 Ｘはフッ素以外のハロゲン原子を示す。）で
示されるジハロトリフルオロアセトン誘導体と水とを反
応させ、一般式（２）
（式中、Ｘは前記と同じ意味を表わし、ｎは０〜４の整
数を示す。）で示されるジハロトリフルオロプロパンジ
オール誘導体またはその水和体に変換後、蒸留して得ら
れた一般式（２）で示されるジハロトリフルオロプロパ
ンジオール誘導体またはその水和体を脱水することを特
徴とする一般式（１）で示されるジハロトリフルオロア
セトン誘導体の精製方法を提供するものである。Means for Solving the Problems As a result of diligent studies on the method for purifying the dihalotrifluoroacetone derivative (1), the present inventors changed the dihalotrifluoroacetone derivative (1) to a derivative having a higher boiling point. The present invention has been found out that the conversion can be performed, the product can be purified by distillation, and then the product can be efficiently purified again by returning to the trifluoroacetone derivative, which in turn can reduce impurities in the product. That is, the present invention has the general formula (1) (In the formula, X represents a halogen atom other than fluorine.) The dihalotrifluoroacetone derivative represented by general formula (2) is reacted with water. (In the formula, X has the same meaning as described above, and n represents an integer of 0 to 4.) A general compound obtained by converting the dihalotrifluoropropanediol derivative or its hydrate and then distilling it. The present invention provides a method for purifying a dihalotrifluoroacetone derivative represented by the general formula (1), which comprises dehydrating the dihalotrifluoropropanediol derivative represented by the formula (2) or a hydrate thereof. .
【０００４】[0004]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明で用いられるジハロトリフルオロアセトン誘導体
（１）において、Ｘはフッ素以外のハロゲン原子を示
す。ここで、フッ素以外のハロゲン原子としては、塩
素、臭素、ヨウ素原子が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the dihalotrifluoroacetone derivative (1) used in the present invention, X represents a halogen atom other than fluorine. Here, examples of halogen atoms other than fluorine include chlorine, bromine, and iodine atoms.
【０００５】ジハロトリフルオロアセトン誘導体（１）
の具体的化合物としては、１，１−ジクロロ−３，３，
３−トリフルオロアセトン、１，１−ジブロモ−３，
３，３−トリフルオロアセトン、１，１−ジヨード−
３，３，３−トリフルオロアセトン等が挙げられる。Dihalotrifluoroacetone derivative (1)
Specific compounds of 1,1-dichloro-3,3,
3-trifluoroacetone, 1,1-dibromo-3,
3,3-trifluoroacetone, 1,1-diiodo-
3,3,3-trifluoroacetone and the like can be mentioned.
【０００６】ジハロトリフルオロプロパンジオール誘導
体（２）は、水とジハロトリフルオロアセトン誘導体
（１）を反応させることにより得ることができる。水の
使用量はジハロトリフルオロアセトン誘導体（１）に対
し、通常０．５から１００重量倍、好ましくは１から２
０重量倍程度である。反応温度は通常２０℃から１００
℃程度、好ましくは４０℃から８０℃程度である。反応
終了後はそのまま蒸留操作に付すが、有機溶媒にて抽出
処理し、得られた有機層を濃縮した後蒸留することもで
きる。The dihalotrifluoropropanediol derivative (2) can be obtained by reacting water with the dihalotrifluoroacetone derivative (1). The amount of water used is usually 0.5 to 100 times by weight, preferably 1 to 2 times the dihalotrifluoroacetone derivative (1).
It is about 0 times the weight. Reaction temperature is usually 20 ° C to 100
C., preferably about 40 to 80.degree. After completion of the reaction, it is directly subjected to a distillation operation, but it is also possible to carry out an extraction treatment with an organic solvent, concentrate the obtained organic layer, and then distill it.
【０００７】かかる反応により得られたジハロトリフル
オロプロパンジオール誘導体（２）は、蒸留により精製
することができるが、蒸留は常圧もしくは減圧下にて実
施することができる。The dihalotrifluoropropanediol derivative (2) obtained by such a reaction can be purified by distillation, which can be carried out under normal pressure or reduced pressure.
【０００８】かかる反応により得られるジハロトリフル
オロアセトン誘導体（２）の具体的化合物としては、
１，１−ジクロロ−３，３，３−トリフルオロ−２，２
−プロパンジオール、１，１−ジブロモ−３，３，３−
トリフルオロ−２，２−プロパンジオール、１，１−ジ
ヨード−３，３，３−トリフルオロ−２，２−プロパン
ジオール等が挙げられる。Specific compounds of the dihalotrifluoroacetone derivative (2) obtained by the above reaction include:
1,1-dichloro-3,3,3-trifluoro-2,2
-Propanediol, 1,1-dibromo-3,3,3-
Examples thereof include trifluoro-2,2-propanediol and 1,1-diiodo-3,3,3-trifluoro-2,2-propanediol.
【０００９】蒸留により精製したジハロトリフルオロプ
ロパンジオール誘導体（２）は、酸性条件下脱水するこ
とでジハロトリフルオロアセトン誘導体（１）へ戻すこ
とができる。また、次工程が水溶媒での反応であれば、
ジハロトリフルオロアセトン誘導体（１）へ戻さずに、
ジハロトリフルオロプロパンジオール誘導体（２）のま
ま用いることもできる。The dihalotrifluoropropanediol derivative (2) purified by distillation can be returned to the dihalotrifluoroacetone derivative (1) by dehydration under acidic conditions. Also, if the next step is a reaction in a water solvent,
Without returning to the dihalotrifluoroacetone derivative (1),
The dihalotrifluoropropanediol derivative (2) can be used as it is.
【００１０】ジハロトリフルオロプロパンジオール誘導
体（２）を脱水するために使用される酸としては、具体
的には、塩酸、硫酸等の無機酸、ｐ−トルエンスルホン
酸等の有機酸、酸性イオン交換樹脂等が挙げられる。酸
の使用量は、ジハロトリフルオロプロパンジオール誘導
体（２）に対して通常０．００５から５モル倍、好まし
くは０．０１から２モル倍程度である。Specific examples of the acid used for dehydrating the dihalotrifluoropropanediol derivative (2) include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as p-toluenesulfonic acid, and acidic ions. Examples include exchange resins. The amount of the acid used is usually about 0.005 to 5 mol times, preferably about 0.01 to 2 mol times based on the dihalotrifluoropropanediol derivative (2).
【００１１】かかる反応は通常無溶媒で実施されるが、
反応に影響を与えない溶媒であれば、その溶媒下にて実
施してもよい。用いることのできる有機溶媒としては、
ベンゼン、トルエン、ヘキサン等の炭化水素系溶媒、テ
トラヒドロフラン、ジメトキシエタン、メチル−ｔ−ブ
チルエーテル等のエーテル系溶媒、クロロホルム、ジク
ロロメタン、モノクロロベンゼン等のハロゲン系溶媒、
アセトン、メチルイソブチルケトン等のケトン系溶媒等
が挙げられる。有機溶媒の使用量は、ジハロトリフルオ
ロプロパンジオール誘導体（２）に対し通常０．５から
５０重量倍、好ましくは１から２０重量倍程度である。
反応温度は通常０℃から溶媒の沸点程度、好ましくは１
０℃から溶媒の沸点程度である。Although such a reaction is usually carried out without a solvent,
If the solvent does not affect the reaction, the reaction may be carried out in that solvent. As the organic solvent that can be used,
Hydrocarbon-based solvents such as benzene, toluene and hexane, ether-based solvents such as tetrahydrofuran, dimethoxyethane and methyl-t-butyl ether, halogen-based solvents such as chloroform, dichloromethane and monochlorobenzene,
Examples of the solvent include ketone solvents such as acetone and methyl isobutyl ketone. The amount of the organic solvent used is usually about 0.5 to 50 times by weight, preferably about 1 to 20 times by weight based on the dihalotrifluoropropanediol derivative (2).
The reaction temperature is usually 0 ° C to the boiling point of the solvent, preferably 1
It is from 0 ° C. to the boiling point of the solvent.
【００１２】かかる反応においては、生成する水を共沸
脱水、脱水剤の添加等の方法により反応系中から除去し
ながら行うことが好ましい。反応終了後は通常の方法、
例えば水を加えた後、有機溶媒を用いて抽出処理し、得
られた有機層を濃縮することで、目的とするジハロトリ
フルオロアセトン誘導体（１）を得ることができる。In such a reaction, it is preferable to remove the produced water from the reaction system by a method such as azeotropic dehydration or addition of a dehydrating agent. After the reaction is completed, the usual method,
For example, after adding water, extraction treatment is performed using an organic solvent, and the obtained organic layer is concentrated to obtain the desired dihalotrifluoroacetone derivative (1).
【００１３】このようにして得られたジハロトリフルオ
ロアセトン誘導体（１）は、水中ｐＨ１２以下で加水分
解した後、一般式（３）
（ 式中Ｙ1は水素原子またはハロゲン原子を示し、Ｙ2
はハロゲン原子を示す。）で示されるヒドラジン誘導
体、もしくはその鉱酸との塩と反応させることにより一
般式（４）
（ 式中Ｙ1、Ｙ2は前記と同じ意味を表わす。）で示さ
れる農薬中間体として有用なヒドラジノン誘導体（特開
平９−３２３９７７号公報参照）を得ることができる。The dihalotrifluoroacetone derivative (1) thus obtained is hydrolyzed in water at a pH of 12 or less, and then the general formula (3) is obtained. (In the formula, Y 1 represents a hydrogen atom or a halogen atom, and Y 2
Represents a halogen atom. ) By reacting with a hydrazine derivative represented by (In the formula, Y 1 and Y 2 have the same meanings as described above.) A hydrazinone derivative useful as an agrochemical intermediate (see JP-A-9-323977) can be obtained.
【００１４】[0014]
【発明の効果】本発明によれば、通常精製が困難であっ
たジハロトリフルオロアセトン誘導体を効率よく精製す
ることができる。INDUSTRIAL APPLICABILITY According to the present invention, a dihalotrifluoroacetone derivative, which was usually difficult to purify, can be efficiently purified.
【００１５】[0015]
【実施例】以下、実施例をあげて、本発明をさらに詳し
く説明するが、本発明は、これらに限定されるものでは
ない。The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.
【００１６】（実施例１）１，１−ジクロロ−３，３，
３−トリフルオロアセトン９．０５ｇ(含量９０％)を水
２７．１５ｇに懸濁させ、７０℃で３時間攪拌した。そ
の後、減圧下蒸留することで１，１−ジクロロ−３，
３，３−トリフルオロ−２，２−プロパンジオール９．
１４ｇを得た。（含量９１％）
沸点：１０１〜１０３℃（１５０ｍｍHg）
１３Ｃ ＮＭＲ（６７．８ＭＨｚ，ＣＤＣｌ３）
δ７１．５７（ｓ）、９３．３９（ｑ、J＝３１．７H
z）,１２１．６３（ｑ、J＝２８９．３Hz）
得られた１，１−ジクロロ−３，３，３−トリフルオロ
−２，２−プロパンジオールをトルエン２８．３５ｇに
溶解し、９８％硫酸を０．０５ｇ加え、共沸脱水しなが
ら３時間加熱した。その後室温まで冷却し、ジエチルエ
ーテル１５ｇを加え、水１０ｇで洗浄した。有機層を分
離し、無水硫酸マグネシウムで乾燥、濃縮することで
１，１−ジクロロ−３，３，３−トリフルオロアセトン
７．８２ｇを得た。（含量９５％）(Example 1) 1,1-dichloro-3,3,3
3-Trifluoroacetone (9.05 g, content 90%) was suspended in water (27.15 g), and the mixture was stirred at 70 ° C. for 3 hours. Then, by distillation under reduced pressure, 1,1-dichloro-3,
3,3-trifluoro-2,2-propanediol 9.
14 g were obtained. (Content 91%) Boiling point: 101 to 103 ° C. (150 mmHg) 13 C NMR (67.8 MHz, CDCl 3) δ71.57 (s), 93.39 (q, J = 31.7 H)
z), 121.63 (q, J = 289.3 Hz) The obtained 1,1-dichloro-3,3,3-trifluoro-2,2-propanediol was dissolved in 28.35 g of toluene to give 98%. 0.05 g of sulfuric acid was added, and the mixture was heated for 3 hours while azeotropically dehydrating. Thereafter, the mixture was cooled to room temperature, 15 g of diethyl ether was added, and the mixture was washed with 10 g of water. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated to obtain 7.82 g of 1,1-dichloro-3,3,3-trifluoroacetone. (Content 95%)
【００１７】（実施例２）１，１−ジブロモ−３，３，
３−トリフルオロアセトン１３．３４ｇ（含量９１％）
を水４０．３５ｇに懸濁させ、７０℃で３時間攪拌し
た。その後、減圧下蒸留することで１，１−ジブロモ−
３，３，３−トリフルオロ−２，２−プロパンジオール
１３．０９ｇを得た。（含量９３％）
沸点：１２１〜１２５℃（１００ｍｍＨｇ）
１Ｈ ＮＭＲ（２７０ＭＨｚ，ＤＭＳＯ−ｄ６）
δ６．０６（ｓ，１Ｈ），７．９２（ｓ，２Ｈ）
１３Ｃ ＮＭＲ（６７．８ＭＨｚ，ＤＭＳＯ−ｄ６）
δ３９．５０（ｓ）、９２．６０（ｑ、J＝２９．３H
z）,１２２．２０（ｑ、J＝２９７．１Hz）
得られた１，１−ジブロモ−３，３，３−トリフルオロ
−２，２−プロパンジオールをトルエン３８．８５ｇに
溶解し、９８％硫酸を０．０５ｇ加え、共沸脱水しなが
ら３時間加熱した。その後室温まで冷却し、ジエチルエ
ーテル２０ｇを加え、水１５ｇで洗浄した。有機層を分
離し、無水硫酸マグネシウムで乾燥、濃縮することで
１，１−ジブロモ−３，３，３−トリフルオロアセトン
１１．７７ｇを得た。（含量９５％）(Example 2) 1,1-dibromo-3,3,3
13.34 g of 3-trifluoroacetone (content 91%)
Was suspended in 40.35 g of water and stirred at 70 ° C. for 3 hours. Then, by distillation under reduced pressure, 1,1-dibromo-
13.09 g of 3,3,3-trifluoro-2,2-propanediol was obtained. (Content 93%) Boiling point: 121 to 125 ° C (100 mmHg) 1H NMR (270 MHz, DMSO-d6) δ 6.06 (s, 1H), 7.92 (s, 2H) 13C NMR (67.8 MHz, DMSO-d6). ) Δ39.50 (s), 92.60 (q, J = 29.3H)
z), 122.20 (q, J = 297.1 Hz) The obtained 1,1-dibromo-3,3,3-trifluoro-2,2-propanediol was dissolved in 38.85 g of toluene to give 98%. 0.05 g of sulfuric acid was added, and the mixture was heated for 3 hours while azeotropically dehydrating. Thereafter, the mixture was cooled to room temperature, 20 g of diethyl ether was added, and the mixture was washed with 15 g of water. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated to obtain 11.77 g of 1,1-dibromo-3,3,3-trifluoroacetone. (Content 95%)
【手続補正書】[Procedure amendment]
【提出日】平成１０年１１月２６日（１９９８．１１．
２６）[Submission Date] November 26, 1998 (1998.11.
26)
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項１[Name of item to be corrected] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００３[Name of item to be corrected] 0003
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００３】[0003]
【課題を解決するための手段】本発明者らは、ジハロト
リフルオロアセトン誘導体（１）の精製方法について鋭
意検討した結果、ジハロトリフルオロアセトン誘導体
（１）を、より沸点の高い誘導体へ変換し、蒸留にて精
製した後、再びトリフルオロアセトン誘導体へと戻すこ
とで効率よく精製でき、延いては製品中の不純物を減ら
すことができることを見出し、本発明に至った。すなわ
ち本発明は、一般式（１）
（式中、 Ｘはフッ素以外のハロゲン原子を示す。）で
示されるジハロトリフルオロアセトン誘導体と水とを反
応させ、一般式（２）
（式中、Ｘは前記と同じ意味を表わす。）で示されるジ
ハロトリフルオロプロパンジオール誘導体またはその水
和体に変換後、蒸留して得られた一般式（２）で示され
るジハロトリフルオロプロパンジオール誘導体またはそ
の水和体を脱水することを特徴とする一般式（１）で示
されるジハロトリフルオロアセトン誘導体の精製方法を
提供するものである。Means for Solving the Problems As a result of diligent studies on the method for purifying the dihalotrifluoroacetone derivative (1), the present inventors changed the dihalotrifluoroacetone derivative (1) to a derivative having a higher boiling point. The present invention has been found out that the conversion can be performed, the product can be purified by distillation, and then the product can be efficiently purified again by returning to the trifluoroacetone derivative, which in turn can reduce impurities in the product. That is, the present invention has the general formula (1) (In the formula, X represents a halogen atom other than fluorine.) The dihalotrifluoroacetone derivative represented by general formula (2) is reacted with water. (In the formula, X has the same meaning as described above.) The dihalotrifluoropropanediol derivative represented by the formula (2) is obtained by converting the dihalotrifluoropropanediol derivative or a hydrate thereof. The present invention provides a method for purifying a dihalotrifluoroacetone derivative represented by the general formula (1), which comprises dehydrating a fluoropropanediol derivative or a hydrate thereof.
Claims (2)
示されるジハロトリフルオロアセトン誘導体と水とを反
応させ、一般式（２） （式中、Ｘは前記と同じ意味を表わし、ｎは０〜４の整
数を示す。）で示されるジハロトリフルオロプロパンジ
オール誘導体またはその水和体に変換後、蒸留して得ら
れた一般式（２）で示されるジハロトリフルオロプロパ
ンジオール誘導体またはその水和体を脱水することを特
徴とする一般式（１）で示されるジハロトリフルオロア
セトン誘導体の精製方法。1. A general formula (1) (In the formula, X represents a halogen atom other than fluorine.) The dihalotrifluoroacetone derivative represented by general formula (2) is reacted with water. (In the formula, X has the same meaning as described above, and n represents an integer of 0 to 4.) A general compound obtained by converting the dihalotrifluoropropanediol derivative or its hydrate and then distilling it. A method for purifying a dihalotrifluoroacetone derivative represented by the general formula (1), which comprises dehydrating the dihalotrifluoropropanediol derivative represented by the formula (2) or a hydrate thereof.
塩素または臭素原子である請求項１に記載のジハロトリ
フルオロアセトン誘導体の精製方法。2. The method for purifying a dihalotrifluoroacetone derivative according to claim 1, wherein in the general formulas (1) and (2), X is a chlorine or bromine atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23410498A JP4221782B2 (en) | 1998-08-20 | 1998-08-20 | Method for purifying dihalotrifluoroacetone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23410498A JP4221782B2 (en) | 1998-08-20 | 1998-08-20 | Method for purifying dihalotrifluoroacetone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000063316A true JP2000063316A (en) | 2000-02-29 |
| JP4221782B2 JP4221782B2 (en) | 2009-02-12 |
Family
ID=16965703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23410498A Expired - Fee Related JP4221782B2 (en) | 1998-08-20 | 1998-08-20 | Method for purifying dihalotrifluoroacetone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4221782B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
1998
- 1998-08-20 JP JP23410498A patent/JP4221782B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4221782B2 (en) | 2009-02-12 |
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