JPH0699348B2 - Method for producing hexafluoroacetone hydrate - Google Patents
Method for producing hexafluoroacetone hydrateInfo
- Publication number
- JPH0699348B2 JPH0699348B2 JP61181096A JP18109686A JPH0699348B2 JP H0699348 B2 JPH0699348 B2 JP H0699348B2 JP 61181096 A JP61181096 A JP 61181096A JP 18109686 A JP18109686 A JP 18109686A JP H0699348 B2 JPH0699348 B2 JP H0699348B2
- Authority
- JP
- Japan
- Prior art keywords
- hexafluoroacetone hydrate
- hexafluoroacetone
- salt
- hydrate
- hexafluoro
- 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.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、ヘキサフルオロアセトン水和物の製造法に関
する。更に詳しくは、ヘキサフルオロ‐α‐ヒドロキシ
イソブタン酸塩からヘキサフルオロアセトン水和物を製
造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing hexafluoroacetone hydrate. More specifically, it relates to a method for producing hexafluoroacetone hydrate from hexafluoro-α-hydroxyisobutanoate.
ヘキサフルオロアセトンは、合成樹脂、合成ゴムなどの
製造用単量体として、あるいはビスフエノールAFなどの
架橋剤の中間体、医薬、農薬などの中間原料などとして
用いられる。Hexafluoroacetone is used as a monomer for producing synthetic resins and synthetic rubbers, or as an intermediate for crosslinking agents such as bisphenol AF, as an intermediate raw material for pharmaceuticals, agricultural chemicals, and the like.
このような各種の用途を有するヘキサフルオロアセトン
は、従来次のような方法によって製造することが提案さ
れている。Hexafluoroacetone having such various uses has been conventionally proposed to be produced by the following method.
しかしながら、上記の各方法には、次のような欠点がみ
られる。 However, each of the above methods has the following drawbacks.
（１）過マンガン酸カリウムによる酸化反応は、反応が
激しくまた副生する二酸化マンガンが容易には処置でき
ない産業廃棄物となること （２）ヘキサフルオロプロペンより合成されるそのオキ
サイドは高純度のものが得られ難く、従って生成物たる
ヘキサフルオロアセトン中にヘキサフルオロプロペンな
どが混在すること （３）ジチエタンの硝酸酸化では、得られるヘキサフル
オロアセトン水和物中にNO2およびSO2が含まれ、それの
除去に手間がかかること （４）ヘキサクロルアセトンの使用は、合成上塩素が重
量を増加させるだけで効率的ではなく、また有毒な五塩
化アンチモンを必要とし、更に高純度の生成物が得られ
難いこと 〔発明が解決しようとする問題点〕 本発明者らは、かかる欠点がみられるこれらの従来技術
とは全く発想を異にし、それの有効利用が強く求められ
ているオクタフルオロイソブテンまたはそのアルコール
付加物を原料物質として用い、それを一旦ヘキサフルオ
ロ‐α‐ヒドロキシイソブタン酸塩に変換させた後ハロ
ゲンと反応させることにより、目的とするヘキサフルオ
ロアセトン水和物が得られることを見出した。(1) The oxidation reaction by potassium permanganate is vigorous and manganese dioxide produced as a by-product becomes industrial waste that cannot be easily treated. (2) The oxide synthesized from hexafluoropropene has a high purity. It is difficult to obtain, and therefore hexafluoropropene and the like are mixed in the product hexafluoroacetone. (3) In nitric acid oxidation of dithietane, NO 2 and SO 2 are contained in the obtained hexafluoroacetone hydrate, It takes time to remove it. (4) The use of hexachloroacetone is not efficient because chlorine increases the weight due to its synthesis, and it requires toxic antimony pentachloride. Difficult to obtain [Problems to be solved by the invention] The inventors of the present invention have no idea of these prior arts in which such drawbacks are observed. Different from each other, and using octafluoroisobutene or its alcohol adduct as a raw material for which effective utilization thereof is strongly demanded, once converting it into hexafluoro-α-hydroxyisobutanoate, and then reacting with halogen. It was found that the desired hexafluoroacetone hydrate can be obtained.
得られたヘキサフルオロアセトン水和物は、それ自体ポ
リエステル、ポリアミドなどの溶媒として使用できる
が、それの脱水を行う場合には、五酸化リン、濃硫酸、
無水硫酸あるいはモレキュラシーブなどを用いる方法に
よって行うことができるので（特開昭57-81,433号公
報、同59-157,045号公報）、本発明方法はヘキサフルオ
ロアセトンの製造にも通ずるものである。The obtained hexafluoroacetone hydrate can be used as a solvent for polyester, polyamide, etc., but when dehydrating it, phosphorus pentoxide, concentrated sulfuric acid,
The method of the present invention is applicable to the production of hexafluoroacetone since it can be carried out by a method using anhydrous sulfuric acid or molecular sieve (JP-A-57-81,433 and JP-A-59-157,045).
〔問題点を解決するための手段〕 従って、本発明はヘキサフルオロアセトン水和物の製造
法に係り、ヘキサフルオロアセトン水和物の製造は、ヘ
キサフルオロ‐α‐ヒドロキシイソブタン酸の水溶性金
属塩を水溶液の状態でニッケル塩の存在下にハロゲンガ
スと反応させることにより行われる。[Means for Solving Problems] Accordingly, the present invention relates to a method for producing hexafluoroacetone hydrate, and the production of hexafluoroacetone hydrate is accomplished by using a water-soluble metal salt of hexafluoro-α-hydroxyisobutanoic acid. Is reacted with a halogen gas in the presence of a nickel salt in the state of an aqueous solution.
ヘキサフルオロ‐α‐ヒドロキシイソブタン酸（3,3,3-
トリフルオロ‐2-ヒドロキシ‐2-トリフルオロメチルプ
ロピオン酸） （CF3）2C（OH）COOH は、例えばオクタフルオロイソブテンのアルコール付加
物をアルカリ性過酸化水素で酸化し、その後溶媒中で加
水分解することにより合成される（特願昭60-125,242
号）。Hexafluoro-α-hydroxyisobutanoic acid (3,3,3-
Trifluoro-2-hydroxy-2-trifluoromethylpropionic acid) (CF 3 ) 2 C (OH) COOH is used to oxidize, for example, alcohol adducts of octafluoroisobutene with alkaline hydrogen peroxide and then hydrolyze them in a solvent. (Japanese Patent Application No. 60-125,242)
issue).
このヘキサフルオロ‐α‐ヒドロキシイソブタン酸は、
水溶性金属塩、具体的にはナトリウム塩、カリウム塩な
どのアルカリ金属塩あるいはカルシウム塩などのアルカ
リ土類金属塩として本発明方法に用いられる。これらの
金属塩は、一般に上記加水分解に用いられる金属化合物
によって形成され、また必要に応じてこの反応液を酸性
とた後蒸留により酸を分離し、目的金属の水酸化物また
は炭酸塩の水溶液で中和させることにより形成させる。This hexafluoro-α-hydroxyisobutanoic acid is
It is used in the method of the present invention as a water-soluble metal salt, specifically, an alkali metal salt such as sodium salt and potassium salt or an alkaline earth metal salt such as calcium salt. These metal salts are generally formed by a metal compound used for the above hydrolysis, and if necessary, the reaction solution is acidified and then the acid is separated by distillation to obtain an aqueous solution of a hydroxide or carbonate of the target metal. It is formed by neutralizing with.
反応は、水溶性金属塩を約10〜50％の濃度となる水溶液
に調整した後、金属塩に対して約0.01〜1.0モル当量、
好ましくは約0.1〜0.3モル当量のニッケル塩、例えば塩
化ニッケル、酢酸ニッケル、硫酸ニッケルなどを加え、
そこに金属塩に対して約0.5〜５モル当量、好ましくは
約１〜２モル当量の塩素ガスまたは臭素ガスを、室温〜
約80℃、好ましくは約30〜60℃の温度で通すことにより
行われる。In the reaction, the water-soluble metal salt is adjusted to an aqueous solution having a concentration of about 10 to 50%, and then about 0.01 to 1.0 molar equivalent to the metal salt,
Preferably about 0.1 to 0.3 molar equivalents of nickel salt, such as nickel chloride, nickel acetate, nickel sulfate, etc. are added,
About 0.5 to 5 molar equivalents, preferably about 1 to 2 molar equivalents of chlorine gas or bromine gas are added thereto at room temperature to room temperature.
It is carried out by passing at a temperature of about 80 ° C, preferably about 30-60 ° C.
このような条件下で反応が行われた後、反応生成物たる
ヘキサフルオロアセトン水和物は、水に不溶性のエーテ
ル系溶媒、例えばジエチルエーテル、ジイソプロピルエ
ーテルなどによって反応混合物中から抽出され、抽出溶
媒を留去することによって目的物として取得される。After the reaction is performed under such conditions, the reaction product hexafluoroacetone hydrate is extracted from the reaction mixture with a water-insoluble ether solvent such as diethyl ether or diisopropyl ether, and the extraction solvent It is obtained as a target by distilling off.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例１ 冷却器、攪拌装置および温度計を備えた容量100mlのフ
ラスコに、ヘキサフルオロ‐α‐ヒドロキシイソブタン
酸カリウム8.3g（33ミリモル）、水40gおよび塩化ニッ
ケル・6H2O 1.0g（４ミリモル）を仕込み、フラスコ浴
を60℃に加熱しながら、そこに塩素ガス3.5g（49ミリモ
ル）を１時間の間に通じた。Example 1 In a flask having a capacity of 100 ml equipped with a condenser, a stirrer and a thermometer, 8.3 g (33 mmol) of potassium hexafluoro-α-hydroxyisobutanoate, 40 g of water and 1.0 g of nickel chloride 6H 2 O (4 mmol) were added. ) Was charged, and while heating the flask bath to 60 ° C., 3.5 g (49 mmol) of chlorine gas was bubbled into the flask during 1 hour.
この反応混合物について、Fnmr内標法によりヘキサフル
オロアセトン水和物の生成量を測定すると1.1g（収率44
％）の値が得られた。The amount of hexafluoroacetone hydrate produced in this reaction mixture was measured by the Fnmr internal standard method to give 1.1 g (yield 44
%) Values were obtained.
実施例２ 実施例１において、塩化ニッケル・6H2Oの代りに酢酸ニ
ッケル・4H2Oを用いた。In Example 2 Example 1 was repeated using nickel acetate · 4H 2 O in place of nickel chloride · 6H 2 O.
Fnmr内標法によるヘキサフルオロアセトン水和物の生成
量は1.0g（収率42％）であった。The amount of hexafluoroacetone hydrate produced by the Fnmr internal standard method was 1.0 g (yield 42%).
比較例 実施例１において、ニッケル塩を用いないと、反応は殆
んど進行しなかった。Comparative Example In Example 1, unless nickel salt was used, the reaction hardly proceeded.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 31/04 Ｘ 8017−4Ｇ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location B01J 31/04 X 8017-4G
Claims (1)
ン酸の水溶性金属塩を、水溶液の状態でニッケル塩の存
在下にハロゲンガスと反応させることを特徴とするヘキ
サフルオロアセトン水和物の製造法。1. A method for producing hexafluoroacetone hydrate, which comprises reacting a water-soluble metal salt of hexafluoro-α-hydroxyisobutanoic acid with a halogen gas in the presence of a nickel salt in the state of an aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61181096A JPH0699348B2 (en) | 1986-07-31 | 1986-07-31 | Method for producing hexafluoroacetone hydrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61181096A JPH0699348B2 (en) | 1986-07-31 | 1986-07-31 | Method for producing hexafluoroacetone hydrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6335537A JPS6335537A (en) | 1988-02-16 |
| JPH0699348B2 true JPH0699348B2 (en) | 1994-12-07 |
Family
ID=16094761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61181096A Expired - Fee Related JPH0699348B2 (en) | 1986-07-31 | 1986-07-31 | Method for producing hexafluoroacetone hydrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699348B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4396831B2 (en) | 2004-04-19 | 2010-01-13 | ダイキン工業株式会社 | Method for producing fluoroalkyl ketone hydrate |
-
1986
- 1986-07-31 JP JP61181096A patent/JPH0699348B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6335537A (en) | 1988-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0194671B1 (en) | Method for production of 2, 3, 4, 5-tetrafluorobenzoic acid | |
| US7576237B2 (en) | Process for the synthesis of 2,5-Dihydroxyterephthalic acid | |
| JPH0699348B2 (en) | Method for producing hexafluoroacetone hydrate | |
| JP3836518B2 (en) | Method for producing 3-mercaptopropionitrile and 3-mercaptopropionic acid | |
| US4694110A (en) | Process for production of m-phenoxybenzyl alcohol | |
| US2640083A (en) | Manufacture of vanillin and its homologues | |
| JPS6411624B2 (en) | ||
| JP2514368B2 (en) | Method for producing hexafluoroacetone or its hydrate | |
| US4734169A (en) | Process for producing hexafluoroacetone hydrate | |
| JPH08231462A (en) | Perfluoroalkylarboxylic acid fluoride and production of its derivative | |
| JPS6312048B2 (en) | ||
| JPH06234691A (en) | Continuous preparation of aromatic aldehyde | |
| JPH0610158B2 (en) | Method for producing 3-fluorobenzoic acids | |
| JP3164284B2 (en) | Method for producing 2-chloro-4-trifluoromethylbenzal chloride | |
| JP2541882B2 (en) | Method for producing anthranilic acids | |
| JPH0723332B2 (en) | Process for producing 1,3-dichloro-2-propanol | |
| JPH01113336A (en) | Production of alkylphenoxyacetic acid | |
| JP2002088051A (en) | Method for recovering fluoroalkylsulfonic acid | |
| CA1056851A (en) | Process for producing chlorosulfonylbenzoyl chloride | |
| JPS60248640A (en) | Production of benzaldehyde compound | |
| JPH0543504A (en) | Separation of fluoro-substituted benzaldehyde | |
| JPS59157039A (en) | Production of xylylene glycol | |
| JPH06211716A (en) | Production of p-fluorophenol | |
| JPH069478A (en) | Improved production of unsubstituted or substituted benzaldehydes | |
| CN114773186A (en) | Preparation method of 2, 4-dichlorophenoxyacetic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |