JP2701455B2 - Novel fluorine-containing compound, its production method and use - Google Patents
Novel fluorine-containing compound, its production method and useInfo
- Publication number
- JP2701455B2 JP2701455B2 JP12868289A JP12868289A JP2701455B2 JP 2701455 B2 JP2701455 B2 JP 2701455B2 JP 12868289 A JP12868289 A JP 12868289A JP 12868289 A JP12868289 A JP 12868289A JP 2701455 B2 JP2701455 B2 JP 2701455B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- compound
- containing compound
- production method
- compound represented
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、新規含フッ素化合物、その製造方法及びそ
れを用いたCF2＝CFOCF2CF2CF＝CF2の製造方法に関する
ものである。Description: TECHNICAL FIELD The present invention relates to a novel fluorine-containing compound, a method for producing the same, and a method for producing CF 2 = CFOCF 2 CF 2 CF = CF 2 using the compound.
［従来の技術］ 本発明のCF2ClCFClOCF2CF2CFClCF2Cl（1,2,6,7−テト
ラクロロ−1,1,2,4,4,5,5,6,7,7−デカフルオロ−３−
オキサヘプテン）は文献未載の新規化合物であり、二種
類の反応性の異なる二重結合を有する化合物（CF2＝CFO
CF2CF2CF＝CF2,1,1,2,4,4,5,5,6,7,7−デカフルオロ−
３−オキサ−1,6−ヘプタジエン）の前駆体となり得
る。[Prior Art] CF 2 ClCFClOCF 2 CF 2 CFClCF 2 Cl (1,2,6,7-tetrachloro-1,1,2,4,4,5,5,6,7,7-deca of the present invention) Fluoro-3-
Oxaheptene) is a novel compound that has not been published in the literature, and a compound having two types of double bonds having different reactivities (CF 2 = CFO)
CF 2 CF 2 CF = CF 2 , 1,1,2,4,4,5,5,6,7,7-decafluoro-
3-oxa-1,6-heptadiene).
［発明の解決しようとする問題点］ 従来知られていたCF2＝CFOCF2CF2CF＝CF2の合成方法
は、文献記載の（J.Org.Chem.,34,1841（1969））ジカ
ルボン酸のジカリウム塩の熱分解によるものであった。
しかしこの方法では、蒸留等により分離不可能な異性体
CF2＝CFOCF2CF＝CFCF3を副生成物として生ずるために高
純度のものは得られなかった。[Problems to be Solved by the Invention] A conventionally known method for synthesizing CF 2 = CFOCF 2 CF 2 CF = CF 2 is described in (J. Org. Chem., 34 , 1841 (1969)) This was due to the thermal decomposition of the dipotassium salt of the acid.
However, in this method, isomers that cannot be separated by distillation or the like
Since CF 2 = CFOCF 2 CF = CFCF 3 is produced as a by-product, high purity was not obtained.
［問題点を解決するための手段］ かくして本発明は、第一に、一般式CF2X1CFX2OCF2CF2
CFY1CF2Y2（式中、X1,X2,Y1,及びY2は同一または相異な
り、フッ素を除くハロゲンから選ばれる原子。）で表さ
れる含フッ素化合物を提供する。第二に、一般式CF2Y1C
FY2CF2CF2OFで表される化合物と一般式CFX1＝CFX2で表
される化合物を反応させることを特徴とする上記含フッ
素化合物の製造方法を提供する。第三に、上記含フッ素
化合物と脱ハロゲン化剤とを反応させて脱ハロゲン化さ
せることを特徴とする式CF2＝CFOCF2CF2CF＝CF2で表さ
れる化合物の製造方法を提供する。[Means for Solving the Problems] Thus, the present invention firstly provides a compound of the general formula CF 2 X 1 CFX 2 OCF 2 CF 2
Provided is a fluorine-containing compound represented by CFY 1 CF 2 Y 2 (wherein X 1 , X 2 , Y 1 and Y 2 are the same or different and are atoms selected from halogen except fluorine). Second, the general formula CF 2 Y 1 C
The present invention provides a method for producing the above-mentioned fluorine-containing compound, which comprises reacting a compound represented by FY 2 CF 2 CF 2 OF with a compound represented by the general formula CFX 1 = CFX 2 . Third, there is provided a method for producing a compound represented by the formula CF 2 = CFOCF 2 CF 2 CF = CF 2 , wherein the compound is dehalogenated by reacting the fluorine-containing compound with a dehalogenating agent. .
本発明の新規含フッ素化合物は、例えば次のように合
成することが出来る。The novel fluorine-containing compound of the present invention can be synthesized, for example, as follows.
即ち、一塩化ヨウ素とトリフルオロクロロエチレンを
低温下反応させた後、ラジカル開始剤存在下、テトラフ
ルオロエチレンを反応させ、発煙硫酸（H2SO4・SO3）で
酸化する。フルオロオキシハロ化合物に変換した後、ハ
ロゲン化オレフィンと反応させる合成法である。また、
この化合物を亜鉛等の脱ハロゲン化剤と反応させること
により含フッ素モノマーを得ることが出来る。 That is, after reacting iodine monochloride and trifluorochloroethylene at a low temperature, tetrafluoroethylene is reacted in the presence of a radical initiator and oxidized with fuming sulfuric acid (H 2 SO 4 .SO 3 ). This is a synthesis method in which the compound is converted into a fluorooxyhalo compound and then reacted with a halogenated olefin. Also,
By reacting this compound with a dehalogenating agent such as zinc, a fluorine-containing monomer can be obtained.
一塩化ヨウ素とトリフルオロクロロエチレンとの反応
は文献記載の（J.Am.Chem.Soc.,83,2495（1961））の方
法で、低温下、反応させることにより選択的にCF2ClCFC
lI（ａ）が生成する。First reaction with iodine monochloride and trifluorochloroethylene are described in the literature (J.Am.Chem.Soc., 83, 2495 ( 1961)) by the method of selectively CF 2 ClCFC by low temperature, the reaction
lI (a) is generated.
（ａ）とテトラフルオロエチレンとの反応は、過酸化
物、アゾ化合物等のラジカル開始剤の存在下、通常は20
〜150℃、好ましくは60〜100℃でテトラフルオロエチレ
ンを10気圧以下、好ましくは５気圧以下に保ちながら行
うことによりCF2ClCFClCF2CF2I（ｂ）を得ることが出来
る。The reaction between (a) and tetrafluoroethylene is carried out usually in the presence of a radical initiator such as a peroxide or an azo compound.
CF 2 ClCFClCF 2 CF 2 I (b) can be obtained by carrying out tetrafluoroethylene at 10 to 150 ° C., preferably 60 to 100 ° C., while maintaining the pressure at 10 atm or less, preferably 5 atm or less.
（ｂ）の酸化反応は、例えば発煙硫酸にて行うことが
出来る。発煙硫酸の濃度は任意に選ばれる。反応温度
は、発煙硫酸の濃度により異なるが、例えば60％の時
は、40〜100℃好ましくは60〜80℃である。The oxidation reaction (b) can be performed, for example, with fuming sulfuric acid. The concentration of fuming sulfuric acid is arbitrarily selected. The reaction temperature varies depending on the concentration of fuming sulfuric acid.
（ｄ）のフルオロオキシハロ化合物は、任意の公知法
に従って特にイタリア特許願第19,847A/85に開示される
方法に従って得ることが出来る。The fluorooxyhalo compound of (d) can be obtained according to any known method, in particular according to the method disclosed in Italian Patent Application No. 19,847A / 85.
本発明の新規含フッ素化合物（ｅ）は、（ｄ）とハロ
ゲン化オレフィンとを例えば気相中に於て５気圧以下、
−80〜50℃で反応させることによって得ることが出来
る。The novel fluorinated compound (e) of the present invention comprises (d) and a halogenated olefin, for example, in a gaseous phase at 5 atm or less,
It can be obtained by reacting at -80 to 50 ° C.
更に、（ｅ）は極性溶媒中、亜鉛等の脱ハロゲン化剤
を用いて脱ハロゲン化反応をさせることにより、含フッ
素モノマー（ｆ）を得ることが出来る。この反応におけ
る溶媒は、例えばジグライム、1,4−ジオキサン、メタ
ノール等が好ましく使用される。また、脱ハロゲン化剤
としては、亜鉛の他にナトリウム、マグネシウム、ス
ズ、銅、鉄、水銀等が挙げられるが、反応速度及び価格
の点から亜鉛が好ましく使用される。また、脱ハロゲン
化剤のモル比は、（ｅ）の４〜12倍、好ましくは６〜８
倍である。さらに反応温度は20〜150℃、好ましくは30
〜100℃である。Further, (e) is subjected to a dehalogenation reaction using a dehalogenating agent such as zinc in a polar solvent, whereby a fluorine-containing monomer (f) can be obtained. As the solvent in this reaction, for example, diglyme, 1,4-dioxane, methanol and the like are preferably used. Examples of the dehalogenating agent include sodium, magnesium, tin, copper, iron, mercury and the like in addition to zinc. Zinc is preferably used from the viewpoint of reaction rate and cost. The molar ratio of the dehalogenating agent is 4 to 12 times, preferably 6 to 8 times, that of (e).
It is twice. Further, the reaction temperature is 20 to 150 ° C., preferably 30
~ 100 ° C.
［実施例］ 実施例1. 内径8mmで1000mmの金属製反応器を−30℃に冷却し、C
F2ClCFClCF2CF2OFが10％のCF2ClCFClCF2CF2OF/N2混合ガ
スを導入し、さらにCFCl＝CFClが20％のCFCl＝CFCl/CF3
Cl混合ガスを反応器の途中より混合させる。それぞれの
流量は16NL/h、8NL/hに調製する。反応混合ガスは、−
８℃に冷却して凝縮させる。[Examples] Example 1. A metal reactor having an inner diameter of 8 mm and a diameter of 1000 mm was cooled to −30 ° C.
A mixed gas of CF 2 ClCFClCF 2 CF 2 OF / N 2 containing 10% of F 2 ClCFClCF 2 CF 2 OF was introduced, and CFCl = CFCl / CF 3 containing 20% of CFCl = CFCl.
A Cl mixed gas is mixed in the middle of the reactor. Each flow rate is adjusted to 16NL / h and 8NL / h. The reaction mixture gas is-
Cool to 8 ° C. and condense.
10時間の反応の後、凝縮物を蒸留することによりCF2C
lCFClCF2CF2OCFClCF2Clを60g（20％収率）得た。After 10 hours of reaction, the CF 2 C
The lCFClCF 2 CF 2 OCFClCF 2 Cl to give 60 g (20% yield).
b.p.90℃/50mmHg19 F−NMR（δppm,CFCl3基準,CDCl3溶媒中） −64.0（2F,CF2CFClCF2 Cl），−71.0（2F,OCFClCF2 C
l），−77,0（1F,OCFCl），−82.0（2F,OCF2 ），−118.
3（2F,OCF2CF2），−131.3（1F,CF2 CFClCF2Cl） 元素分析測定結果;F:45.50％,C:17.21％ （計算値;F:45.25％,C:17.16％） 実施例2. 攪拌機、還流コンデンサー、滴下ロートを備えた2000
mlの四ツ口フラスコに亜鉛440g（6.73mol）、1,4−ジオ
キサン900mlを入れ90℃にする。そこへCF2ClCFClCF2CF2
OCFClCF2Cl 353g（0.84mol）をゆっくり滴下する。滴下
終了後２時間還流熟成する。蒸留により生成物を抜き出
した後、精留により純粋なCF2＝CFCF2CF2OCF＝CF2を192
g（82％収率）得た。bp 90 ° C./50 mmHg 19 F-NMR (δ ppm, CFCl 3 standard, in CDCl 3 solvent) −64.0 (2F, CF 2 CFCl CF 2 Cl), −71.0 (2F, OCFCl CF 2 C
l), - 77,0 (1F, OCFCl), - 82.0 (2F, O CF 2), - 118.
3 (2F, OCF 2 CF 2 ), -131.3 (1 F, CF 2 CF ClCF 2 Cl) Elemental analysis measurement results; F: 45.50%, C: 17.21% (calculated values; F: 45.25%, C: 17.16%) Example 2. 2000 equipped with stirrer, reflux condenser and dropping funnel
440 g (6.73 mol) of zinc and 900 ml of 1,4-dioxane are placed in a four-necked four-neck flask and heated to 90 ° C. There CF 2 ClCFClCF 2 CF 2
353 g (0.84 mol) of OCFClCF 2 Cl is slowly added dropwise. After completion of the dropwise addition, the mixture is reflux-aged for 2 hours. After extracting the product by distillation, pure CF 2 = CFCF 2 CF 2 OCF = CF 2
g (82% yield).
Claims (5)
素を除くハロゲンから選ばれる原子。） で表される含フッ素化合物。[Claim 1] The general formula CF 2 X 1 CFX 2 OCF 2 CF 2 CFY 1 CF 2 Y 2 (wherein X 1 , X 2 , Y 1 and Y 2 are the same or different and are different from halogen except fluorine) Selected atom.) A fluorine-containing compound represented by the formula:
求項１の含フッ素化合物。 2. The fluorine-containing compound according to claim 1, wherein all of X 1 , X 2 , Y 1 and Y 2 are chlorine atoms.
物と一般式CFX1＝CFX2で表される化合物を反応させるこ
とを特徴とする請求項１の含フッ素化合物の製造方法。3. The fluorine-containing compound according to claim 1, wherein the compound represented by the general formula CF 2 Y 1 CFY 2 CF 2 CF 2 OF is reacted with the compound represented by the general formula CFX 1 = CFX 2. A method for producing a compound.
求項３の製造方法。4. The method according to claim 3, wherein all of X 1 , X 2 , Y 1 and Y 2 are chlorine atoms.
ロゲン化剤とを反応させて脱ハロゲン化させることを特
徴とする 式CF2＝CFOCF2CF2CF＝CF2で表される化合物の製造方
法。5. A compound represented by the formula CF 2 = CFOCF 2 CF 2 CF = CF 2 , wherein the fluorine-containing compound according to claim 1 or 2 is reacted with a dehalogenating agent to dehalogenate the compound. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12868289A JP2701455B2 (en) | 1989-05-24 | 1989-05-24 | Novel fluorine-containing compound, its production method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12868289A JP2701455B2 (en) | 1989-05-24 | 1989-05-24 | Novel fluorine-containing compound, its production method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02311436A JPH02311436A (en) | 1990-12-27 |
| JP2701455B2 true JP2701455B2 (en) | 1998-01-21 |
Family
ID=14990827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12868289A Expired - Fee Related JP2701455B2 (en) | 1989-05-24 | 1989-05-24 | Novel fluorine-containing compound, its production method and use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2701455B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101125168B1 (en) * | 2004-01-29 | 2012-03-20 | 솔베이 솔렉시스 에스.피.에이. | Process for preparing fluorohalogenethers |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001302725A (en) | 2000-04-26 | 2001-10-31 | Asahi Glass Co Ltd | Fluorine-containing diene, its manufacturing method and its polymer |
| ITMI20020198A1 (en) * | 2002-02-05 | 2003-08-05 | Ausimont Spa | (PER) haloethers |
-
1989
- 1989-05-24 JP JP12868289A patent/JP2701455B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101125168B1 (en) * | 2004-01-29 | 2012-03-20 | 솔베이 솔렉시스 에스.피.에이. | Process for preparing fluorohalogenethers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02311436A (en) | 1990-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3572077B2 (en) | Method for producing perfluoroalkyl iodides | |
| US7795477B2 (en) | Process for preparing fluorohalogenethers | |
| JP3438905B2 (en) | Method for producing 2-perfluoroalkylethyl alcohols | |
| KR840001980B1 (en) | Process for the preparation of acid fluorides and resulting monomers | |
| US6388139B1 (en) | Production of perfluoro (alkyl vinyl) ethers | |
| JP2701454B2 (en) | New fluorinated compounds, their production methods and applications | |
| JP2701455B2 (en) | Novel fluorine-containing compound, its production method and use | |
| JP5158366B2 (en) | Method for producing hydrogen-containing fluoroolefin compound | |
| KR101125168B1 (en) | Process for preparing fluorohalogenethers | |
| JP2001114710A (en) | Method for producing hexafluorobutadiene | |
| JPH01143843A (en) | Novel fluorine-containing compound and production thereof | |
| JPH0747556B2 (en) | Method for producing fluorine-containing ether compound | |
| JP2004002302A (en) | (per)haloethers and method for producing the same | |
| FR2489309A1 (en) | PROCESS FOR PREPARING DIFLUOROHALOGENOACETYL FLUORIDES FROM POLYFLUOROETHYLENE | |
| JPS6340773B2 (en) | ||
| KR101125167B1 (en) | Process for preparing fluorohalogenethers | |
| JP4684402B2 (en) | Method for producing perfluoroalkadiene | |
| JP2004018429A (en) | Method for manufacturing fluorine-containing fluorosulfonylalkyl vinyl ether | |
| JPH0673023A (en) | Production of 5-(trifluoromethyl)uracil and 2,4- dichloro-5-trichloromethylpyrimidine and 2,4-difluoro- 5-trifluoromethylpyridine as new compounds | |
| JP2794788B2 (en) | Allyl trifluoroacrylate and method for producing the same | |
| JP2503941B2 (en) | New fluorinated compound | |
| JPH1192446A (en) | Sulfonimide and its production | |
| JPS61122234A (en) | Perchlorofluorinated hydrocarbon and manufacture | |
| JP3135660B2 (en) | Method for producing perfluoro-oxyaziridine | |
| JPH0317830B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081003 Year of fee payment: 11 |
|
| LAPS | Cancellation because of no payment of annual fees |