JPS6210080A - Fluorine-containing cyclic compound and production thereof - Google Patents
Fluorine-containing cyclic compound and production thereofInfo
- Publication number
- JPS6210080A JPS6210080A JP14857885A JP14857885A JPS6210080A JP S6210080 A JPS6210080 A JP S6210080A JP 14857885 A JP14857885 A JP 14857885A JP 14857885 A JP14857885 A JP 14857885A JP S6210080 A JPS6210080 A JP S6210080A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- cyclic compound
- containing cyclic
- producing
- basic catalyst
- 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、新規含フッ素環式化合物およびその製法に関
する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel fluorine-containing cyclic compound and a method for producing the same.
従来技術
従来、フルオロカーボン鎖に環状エーテル基を有する化
合物については知られていない。フルオロカーボン鎖を
有する化合物はその特異的性質から近年広汎な研究が行
なわれている。その代表的な例は溶剤、界面活性剤、高
分子化学、医薬等にみられる。Prior Art Conventionally, compounds having a cyclic ether group in the fluorocarbon chain have not been known. Compounds having fluorocarbon chains have been extensively studied in recent years due to their specific properties. Typical examples include solvents, surfactants, polymer chemistry, and pharmaceuticals.
一方、ある種の化合物に比較的大きなフッ素を有する基
、例えばパーフルオロアルキル基等を導入するための適
当な導入試剤についてはあまり知られていない。また、
含フッ素高分子物質に関しても主として、含フッ素エチ
レン類の重合による熱可塑性ポリマーが殆んどであって
、その他の含フッ素モノマー類については殆んど知られ
ていない。On the other hand, little is known about suitable introduction reagents for introducing a relatively large fluorine-containing group, such as a perfluoroalkyl group, into certain compounds. Also,
Regarding fluorine-containing polymeric substances, most of them are thermoplastic polymers obtained by polymerizing fluorine-containing ethylenes, and little is known about other fluorine-containing monomers.
発明の目的
本発明は含フッ素アルキル基を他の化合物中に導入する
だめの導入試剤として、あるいは、含フッ素高分子用モ
ノマーとして有用な、新規含フッ素化合物を提供する。OBJECTS OF THE INVENTION The present invention provides a novel fluorine-containing compound useful as a reagent for introducing a fluorine-containing alkyl group into other compounds or as a monomer for a fluorine-containing polymer.
発明の構成
本発明は、一般式 ［■］：
ＣＨｌ
で表わされる含フッ素環式化合物およびその製法に関す
る。Structure of the Invention The present invention relates to a fluorine-containing cyclic compound represented by the general formula [■]: CHl and a method for producing the same.
本発明化合物は非水溶媒中においてペルフルオロ−２−
メチル−２−ペンテンを原料としてこれにブチレングリ
コールを加え塩基性触媒の存在下で０℃〜室温で反応さ
けることによって容易に得られる。The compound of the present invention is perfluoro-2-
It can be easily obtained by using methyl-2-pentene as a raw material, adding butylene glycol to it, and reacting at 0°C to room temperature in the presence of a basic catalyst.
原料として用いられるペルフルオロ−２−メチル−２−
ペンテンは、ヘキサフルオロプロペンを常套の方法によ
り重合して２量体とすることにより得られる。この化合
物の化学構造については日本化学会誌、１９７８、（２
）第２５３〜２５８頁に詳述されている。Perfluoro-2-methyl-2- used as a raw material
Pentene can be obtained by polymerizing hexafluoropropene into a dimer using a conventional method. The chemical structure of this compound is described in Journal of the Chemical Society of Japan, 1978, (2)
), pages 253-258.
ペルフルオロ−２−メチル−２−ペンテンとブチレング
リコールのモル比は曲者１に対し後者０．２〜５ 、特
に！〜２が好ましいが、これらの範囲に限定されること
なく、あらゆるモル比において目的物質が得られる。The molar ratio of perfluoro-2-methyl-2-pentene to butylene glycol is 1 to 0.2 to 5 for the latter, especially! -2 is preferred, but the target substance can be obtained at any molar ratio without being limited to these ranges.
非水溶媒は反応物を溶解し得るものであって、例として
アセトニトリル、Ｎ、Ｎ−ジメチルホルムアミド、Ｔ
ＨＦ 、ジグリム、テトラヒドロピラン、ジメチルカル
ピトール、ジメチルエーテル等が挙げられる。アセトニ
トリル、Ｎ、Ｎ−ジメチルホルムアミド、Ｔ ＨＦ’が
特に好ましい。The non-aqueous solvent is one that can dissolve the reactants, examples being acetonitrile, N,N-dimethylformamide, T
Examples include HF, diglyme, tetrahydropyran, dimethylcarpitol, dimethyl ether, and the like. Particularly preferred are acetonitrile, N,N-dimethylformamide and THF'.
反応に用いる塩基性触媒は脱弗化水素を促進し、生じた
弗化水素を吸収する水溶性のものであればよい。好まし
くはトリエチルアミン、トリメチルアミン、炭酸カリウ
ム、炭酸ナトリウム等が例示される。塩基性触媒は上記
ペルフルオロ−２−メチル−２−ペンテンに対して２〜
１当量、通常はぼ同当量用いるのが好ましい。The basic catalyst used in the reaction may be any water-soluble catalyst that promotes dehydrofluorination and absorbs the generated hydrogen fluoride. Preferred examples include triethylamine, trimethylamine, potassium carbonate, and sodium carbonate. The basic catalyst is 2 to
It is preferred to use 1 equivalent, usually about the same equivalent.
反応は通常常圧で室温、好ましくは０〜２５℃で行なわ
れる。The reaction is usually carried out at normal pressure and room temperature, preferably at 0 to 25°C.
本発明含フッ素環式化合物は７員環ジエーテル化合物で
あって、２位の炭素原子に含フッ素アルキル基が結゛合
している点に特徴がある。即ち、ホルマール型炭素原子
を有し、７員環を構成しているため環歪み等により熱力
学的に不安定となっており、開環による重合または反応
を生じ易くなっている。例えば、アルカリ触媒または酸
触媒により水酸基、カルボキシル基、アミン等の活性水
素を開環反応し、あるいは、それ自体酸触媒等で開環重
合する新たな含フッ素モノマーの重合法が期待される。The fluorine-containing cyclic compound of the present invention is a 7-membered ring diether compound, and is characterized in that a fluorine-containing alkyl group is bonded to the carbon atom at the 2-position. That is, since it has a formal carbon atom and constitutes a 7-membered ring, it is thermodynamically unstable due to ring distortion, etc., and is likely to undergo polymerization or reaction due to ring opening. For example, a new method for polymerizing fluorine-containing monomers is expected in which a ring-opening reaction of active hydrogen such as a hydroxyl group, a carboxyl group, or an amine is carried out using an alkali catalyst or an acid catalyst, or a ring-opening polymerization is performed using an acid catalyst itself.
本発明を実施例により更に詳細に説明する。The present invention will be explained in more detail with reference to Examples.
実施例Ｉ
攪拌機、温度計、還流冷却器および滴下ロートを備えた
１０００ｍ、９フラスコに市販の試薬−級テトラメヂレ
ングリコール（０，５０モル）、トリエチルアミン（０
，５０モル）、アセトニトリル１５０ｍ、９を仕込み、
フラスコを水−水温度に冷却しながらペルフルオロ−２
−メチル−２−ペン°テン（０，５００モル）を徐々に
滴下した。滴下終了後、約８時間攪拌を続け、反応終了
後、希塩酸水溶液で水洗し、さらに水洗を繰返した後、
油分を無水硫酸マグネシウムで乾燥した。乾燥した油分
は分別蒸留にかけ、主生成物を分取し、四塩化炭素から
再結晶し、目的化合物を得た。結晶分を融解させ以下の
条件のガスクロマトグラフィにかけ単一ピークを示すこ
とを確認した。Example I In a 1000 m, 9 flask equipped with a stirrer, thermometer, reflux condenser and addition funnel, commercially available reagent-grade tetramethylene glycol (0,50 mol), triethylamine (0,0
, 50 mol), acetonitrile 150 m, 9,
perfluoro-2 while cooling the flask to water-water temperature.
-Methyl-2-pentene (0,500 mol) was slowly added dropwise. After the dropwise addition was completed, stirring was continued for about 8 hours, and after the reaction was completed, the mixture was washed with dilute aqueous hydrochloric acid solution, and the water washing was repeated.
The oil was dried over anhydrous magnesium sulfate. The dried oil was subjected to fractional distillation, and the main product was separated and recrystallized from carbon tetrachloride to obtain the target compound. The crystalline components were melted and subjected to gas chromatography under the following conditions, and it was confirmed that a single peak was observed.
クロマトグラフィー条件 検出器 ： ＦＩＤ カラム（ステンレス製）：長さ１ｍ。Chromatography conditions Detector: FID Column (stainless steel): length 1m.
充填材５Ｅ−３０ キャリアーガス 二Ｎ。Filler 5E-30 Carrier gas 2N.
インジェクション温度＝２００°Ｃ
展開温度 ： １５０℃
チャート送り速度 ： ２０ｍｍ／ｍｉｎ保持時間
： ０．２５ ｍｉｎ生成物の物性は以下の
通りであった。Injection temperature = 200°C Development temperature: 150°C Chart feeding speed: 20mm/min Holding time
: 0.25 min The physical properties of the product were as follows.
外 観 ：無色結晶（室温）
融 点 ：２６，５〜２７６６℃
赤外吸収スペクトル
ＣＩ基に基づく吸収・・・２９７５．２９００゜２９２
５．２８５０ ｃ＋ｎ−’
ＣＰ ；ｂに基づく吸収−１１００〜１４００ｃｍ−’
１ 、７１ （ｍｕｌｔｉｐｌｅｔ、
４１−１）３．７ ８ （５ｅｐｔｅｔ、
Ｊ Ｉｌｐ”９．ＯＨ２Ｉ ｌ−１）４ ．０
６ （ｍｕｌｔｉｐｌｅｔ、
４ Ｈ）５９．９ （ｄ−
ｔ−ｑ＋ Ｊ、、Ｆ＝９．０Ｈｚ。Appearance: Colorless crystal (room temperature) Melting point: 26.5-2766°C Infrared absorption spectrum Absorption based on CI group...2975.2900°292
5.2850 c+n-'CP; Absorption based on b-1100 to 1400 cm-'
1, 71 (multiplet,
41-1) 3.7 8 (5eptet,
JIlp"9.OH2Il-1)4.0
6 (multiplet,
4 H) 59.9 (d-
t-q+ J,,F=9.0Hz.
Ｊ 〜９．３Ｈｚ、 ＪＦＦ＝２．０）ｌｚ。J~9.3Hz, JFF=2.0)lz.
１’Ｆ
６Ｆ）
８０、１ （５ｅｐｔｅｔ、 ＪＦＦ＝２．ＯＨ２３Ｆ
）１１７ 、０ （ｓｅｐｔｅｔ、 Ｊ ｐｐ−９，３
Ｈｚ ２ Ｆ ）発明の効果
本発明は新規含フッ素環状エーテルを提供する。1'F 6F) 80, 1 (5eptet, JFF=2.OH23F
)117,0 (septet, J pp-9,3
Hz 2 F) Effects of the Invention The present invention provides a novel fluorine-containing cyclic ether.
該環状エーテルは他の化合物中に含フッ素アルキル基を
導入するための導入試剤として、あるいはそれ自体含フ
ッ素樹脂用モノマーとして期待される。The cyclic ether is expected to be used as an introduction agent for introducing a fluorine-containing alkyl group into other compounds, or as a monomer itself for fluorine-containing resins.
Claims (1)
ングリコールを非水溶媒中、塩基性触媒の存在下に反応
させることを特徴とする一般式：▲数式、化学式、表等
があります▼［ I ］ で表わされる含フッ素環式化合物の製法。 ３、非水溶媒がアセトニトリル、Ｎ，Ｎ−ジメチルホル
ムアミド、ＴＨＦである第２項記載の含フッ素環式化合
物の製法。 ４、塩基性触媒がトリエチルアミン、トリメチルアミン
、炭酸カリウムおよび炭酸ナトリウムから選ばれた第２
項記載の含フッ素環式化合物の製法。 ５、反応を０〜２５℃で行なう第２項記載の含フッ素環
式化合物の製法。[Claims] 1. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼A fluorine-containing cyclic compound represented by [I]. 2. General formula characterized by reacting perfluoro-2-methyl-2-pentene and butylene glycol in a non-aqueous solvent in the presence of a basic catalyst: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] A method for producing a fluorine-containing cyclic compound represented by 3. The method for producing a fluorine-containing cyclic compound according to item 2, wherein the nonaqueous solvent is acetonitrile, N,N-dimethylformamide, or THF. 4. The second basic catalyst is selected from triethylamine, trimethylamine, potassium carbonate and sodium carbonate.
A method for producing a fluorine-containing cyclic compound as described in Section 1. 5. The method for producing a fluorine-containing cyclic compound according to item 2, wherein the reaction is carried out at 0 to 25°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14857885A JPS6210080A (en) | 1985-07-06 | 1985-07-06 | Fluorine-containing cyclic compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14857885A JPS6210080A (en) | 1985-07-06 | 1985-07-06 | Fluorine-containing cyclic compound and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6210080A true JPS6210080A (en) | 1987-01-19 |
| JPH0471912B2 JPH0471912B2 (en) | 1992-11-16 |
Family
ID=15455875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14857885A Granted JPS6210080A (en) | 1985-07-06 | 1985-07-06 | Fluorine-containing cyclic compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6210080A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04222153A (en) * | 1990-12-25 | 1992-08-12 | Sharp Corp | Terminal network controller |
-
1985
- 1985-07-06 JP JP14857885A patent/JPS6210080A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04222153A (en) * | 1990-12-25 | 1992-08-12 | Sharp Corp | Terminal network controller |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0471912B2 (en) | 1992-11-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |