JPH0381233A - Production of polyfluoroalkene - Google Patents
Production of polyfluoroalkeneInfo
- Publication number
- JPH0381233A JPH0381233A JP21713789A JP21713789A JPH0381233A JP H0381233 A JPH0381233 A JP H0381233A JP 21713789 A JP21713789 A JP 21713789A JP 21713789 A JP21713789 A JP 21713789A JP H0381233 A JPH0381233 A JP H0381233A
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- formula
- methyl
- perfluoro
- compound
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000126 substance Substances 0.000 claims abstract 3
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 abstract description 6
- FAEGGADNHFKDQX-UHFFFAOYSA-N 1,1,1,3,4,4,5,5,5-nonafluoro-2-(trifluoromethyl)pent-2-ene Chemical compound FC(F)(F)C(C(F)(F)F)=C(F)C(F)(F)C(F)(F)F FAEGGADNHFKDQX-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001516 alkali metal iodide Inorganic materials 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012770 industrial material Substances 0.000 abstract description 4
- 239000002798 polar solvent Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical group 0.000 abstract 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 5
- -1 perfluoro-2-methyl-2-pentyl Chemical group 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
この発明は、優れた耐熱性や撥水撥油性等の特性を有す
る工業用素材の原料として有用なポリフルオロアルケン
の製法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to a method for producing polyfluoroalkenes useful as raw materials for industrial materials having properties such as excellent heat resistance and water and oil repellency.
従来の技術
ポリフルオロアルケンは優れた耐熱性や撥水撥油性等の
特性を有する工業用素材の原料として有用な含フツ素化
合物である。この種の含フツ素化合物、例えばＣＦ ３
ＣＦ ｐｃ Ｆ ｔｃ（ＣＦ ３）ｚＣＨｔＣＨ＝ＣＨ
，は、ペルフルオロ−２−メチル−２−ペンチルカルバ
ニオンとハロゲン化アリルとの反応によって製造するこ
とができるしドゥモフスキ−（Ｗ、 Ｄｍｏｗｓｋｉ）
ら、ジャーナル・オブ・フルオライン・ケミストリー（
Ｊｏｕｒｎａｌ ｏｒ ＦｌｕｏｒｉｎｅＣｈｅｍｉｓ
ｔｒｙ）、第３６巻（１９８７年）、第３８５頁〜第３
９４頁参照コ。しかしながら、この製造法においては、
臭化アリルやヨウ化アリル等に比べて一般に取扱い易く
低コストの塩化アリルを使用した場合の生成物の収率が
極端に悪いという難点がある。BACKGROUND OF THE INVENTION Polyfluoroalkenes are fluorine-containing compounds useful as raw materials for industrial materials that have excellent heat resistance, water and oil repellency, and other properties. This type of fluorine-containing compound, such as CF3
CF pc F tc (CF 3)zCHtCH=CH
, can be prepared by the reaction of perfluoro-2-methyl-2-pentyl carbanion with allyl halide and can be prepared by Dumowski (W, Dmowski)
et al., Journal of Fluorine Chemistry (
Journal or FluorineChemis
try), Volume 36 (1987), Pages 385-3
See page 94. However, in this manufacturing method,
When using allyl chloride, which is generally easier to handle and cheaper than allyl bromide, allyl iodide, etc., the yield of the product is extremely low.
発明が解決しようとする課題
この発明はこのような問題点を解決し、塩化アリルを含
む塩化アリル誘導体を使用した場合にも十分な収率でポ
リフルオロアルケンを製造できる方法を提供するために
なされたものである。Problems to be Solved by the Invention The present invention has been made in order to solve these problems and provide a method that can produce polyfluoroalkenes in sufficient yield even when allyl chloride derivatives containing allyl chloride are used. It is something that
課題を解決するための手段
即ち本発明は、一般式（ＩＩ）：
（式中、Ｘはハロゲン原子を示し、Ｒｌ、 Ｒｔおよび
Ｒ８は各々独立に水素原子、ハロゲン原子または炭素原
子数１〜２０のアルキル基を示す）で表わされるハロゲ
ン化アリル誘導体およびペルフルオロ−２−メチル−２
−ペンテンニド し ｈを
アルカリ金属のフッ化物およびヨウ化物の存在下におい
て、非プロトン性極性溶媒中で反応させることを特徴と
する一般式（■）：
ＣＦ。Means for solving the problem, that is, the present invention is based on the general formula (II): (wherein, ) and perfluoro-2-methyl-2
General formula (■): CF, characterized in that -pentenide is reacted in an aprotic polar solvent in the presence of an alkali metal fluoride and iodide.
（式中、Ｒ１、Ｒ９およびＲ３は前記と同意義である） で表わされるポリフルオロアルケンの製広に関する。(In the formula, R1, R9 and R3 have the same meanings as above) This invention relates to the production of polyfluoroalkenes represented by
一般式（ｎ）において、Ｘはハロゲン原子、好ましくは
塩素原子を示し、Ｒ７、Ｒ１およびＲ３は各々独立に水
素原子、ハロゲン原子または炭素原子数１〜２０、好ま
しくは１〜２のアルキル基を示す。In the general formula (n), show.
アルカリ金属のフッ化物としてはＫＦ、Ｎａｐ。KF and Nap are examples of alkali metal fluorides.
ＲｂＰおよびＣｓＦが例示されるが、ＫＦが好ましく、
また、ヨウ化物としてはに！、ＮａＩ、ＲｂＩおよびＣ
ｓｌが例示されるが、Ｋｒが好ましい。Examples include RbP and CsF, but KF is preferred;
Also, as an iodide! , NaI, RbI and C
sl is exemplified, but Kr is preferred.
非プロトン性極性溶媒としてはへキサメチルリン酸トリ
アミド、ジメチルスルホキシド、Ｎ、Ｎジメチルアセト
アミド、Ｎ−メチルピロリドン、Ｎ、Ｎ−ジメチルホル
ムアミド等が例示されるが、Ｎ、Ｎ−ジメチルアセトア
ミドおよびＮ、Ｎ−ジメチルホルムアミドが好ましい。Examples of the aprotic polar solvent include hexamethylphosphoric acid triamide, dimethyl sulfoxide, N,N dimethylacetamide, N-methylpyrrolidone, N,N-dimethylformamide, etc., and N,N-dimethylacetamide and N,N- Dimethylformamide is preferred.
上記の反応は、通常は常圧下において、室温〜６０℃で
おこなう。The above reaction is usually carried out at room temperature to 60°C under normal pressure.
上記のハロゲン化アリル誘導体、ペルフルオロ２−メチ
ル−２−ペンテン、アルカリ金属のフッ化物およびアル
カリ金属のヨウ化物の反応割合は特に限定的ではないが
、通常はハロゲン化アリル誘導体１モルあたり、ペルフ
ルオロ−２−メチル−２−ペンテン１〜２モル、アルカ
リ金属のフッ化物１〜２モルおよびアルカリ金属のヨウ
化物０゜０１〜０．１モルである。The reaction ratio of the above-mentioned allyl halide derivative, perfluoro-2-methyl-2-pentene, alkali metal fluoride, and alkali metal iodide is not particularly limited, but usually per mol of allyl halide derivative, perfluoro-2-methyl-2-pentene, 1 to 2 moles of 2-methyl-2-pentene, 1 to 2 moles of alkali metal fluoride, and 0.01 to 0.1 mole of alkali metal iodide.
以下、本発明を実施例によって説明する。Hereinafter, the present invention will be explained by examples.
実施例１
撹拌器、還流器、加熱装置および温度計を備えた反応容
器内にペルフルオロ−２−メチル−２−ペンテン３６（
１（１，２モル）、塩化アリル７６゜８２９（１，０モ
ル）およびＮ、Ｎ−ジメチルアセトアミドｌＱを入れ、
次いで十分に乾燥したＫＦ１１６ｇ（２，０モル）およ
びＫ Ｉ ３３．２０ｇ（０，２モル）を加え、撹拌下
、６０℃で１５時間反応をおこなった。Example 1 Perfluoro-2-methyl-2-pentene 36 (
1 (1,2 mol), allyl chloride 76°829 (1,0 mol) and N,N-dimethylacetamide lQ,
Next, 116 g (2.0 mol) of sufficiently dried KF and 33.20 g (0.2 mol) of K I were added, and the reaction was carried out at 60° C. for 15 hours with stirring.
反応混合物を亜硫酸ナトリウム水溶液および水を用いて
洗浄した後、脱水、濃縮および蒸留の各処理を付すこと
によって化合物（Ｉ ａＸｂ、ｐ、 １０１〜１０７℃
）をｓ ９５．３９９得た（収率５４％）。After washing the reaction mixture with an aqueous sodium sulfite solution and water, the compound (I aXb, p, 101-107 °C
) was obtained for s 95.399 (yield 54%).
Ｆ ｓ 化合物（Ｉ ａ）の物性を以下に示す。Fs The physical properties of compound (Ia) are shown below.
外観：淡黄色透明液体
ｂｐ：１０９〜１１０℃
’Ｈ−ＮＭＲ：δ（ｐｐｍ）
２．９０（２Ｈ，ｄ、Ｊ＝７）、５．１付近（ＩＩ−１
，ｍ）５．３付近（ＩＩ−１，ｓ）、５．５〜６．２（
ｌＨ，ｍ）”Ｆ−ＮＭＲ： δ（ｐｐｍ）たたし内部標
準ＣＦＣ（！ｓで、高磁場側を正とした。Appearance: pale yellow transparent liquid bp: 109-110°C 'H-NMR: δ (ppm) 2.90 (2H, d, J = 7), around 5.1 (II-1
, m) around 5.3 (II-1, s), 5.5 to 6.2 (
lH,m)"F-NMR: δ (ppm) + internal standard CFC (!s, with the high magnetic field side set as positive.
６３．５（６Ｆ）、８０．０（３Ｆ）、１０６．０（２
Ｆ）、１２２．０（２Ｆ）
ＩＲ： １４７０（Ｃ＝ＣＨ，）、１４００〜１２０
０（Ｃ−Ｆ）（ｃｃ→
発明の効果
この発明によれば、優れた耐熱性や撥水撥油性等の特性
を有する工業用素材の原料として有用なポリフルオロア
ルケンを、塩化アリル誘導体を使用した場合にも好収率
で得ることができる。63.5 (6F), 80.0 (3F), 106.0 (2
F), 122.0 (2F) IR: 1470 (C=CH,), 1400-120
0(C-F)(cc→ Effects of the Invention According to the present invention, polyfluoroalkenes useful as raw materials for industrial materials having properties such as excellent heat resistance and water/oil repellency are produced using allyl chloride derivatives. It can also be obtained in good yield.
Claims (1)
びＲ＿３は各々独立に水素原子、ハロゲン原子または炭
素原子数１〜２０のアルキル基を示す）で表わされるハ
ロゲン化アリル誘導体およびペルフルオロ−２−メチル
−２−ペンテンをアルカリ金属のフッ化物およびヨウ化
物の存在下において、非プロトン性極性溶媒中で反応さ
せることを特徴とする一般式（ I ）： ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１、Ｒ＿２およびＲ＿３は前記と同意義で
ある） で表わされるポリフルオロアルケンの製法。[Claims] 1. General formula (II): ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, X represents a halogen atom, and R_1, R_2 and R_3 each independently represent a hydrogen atom, An aprotic polar General formula (I) characterized by reaction in a solvent: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (wherein R_1, R_2 and R_3 have the same meanings as above) Production method of fluoroalkenes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21713789A JPH0381233A (en) | 1989-08-23 | 1989-08-23 | Production of polyfluoroalkene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21713789A JPH0381233A (en) | 1989-08-23 | 1989-08-23 | Production of polyfluoroalkene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0381233A true JPH0381233A (en) | 1991-04-05 |
Family
ID=16699435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21713789A Pending JPH0381233A (en) | 1989-08-23 | 1989-08-23 | Production of polyfluoroalkene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0381233A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5387728A (en) * | 1992-08-27 | 1995-02-07 | Hoechst Aktiengesellschaft | Process for the preparation of hexafluoropropene dimers having a high proportion of perfluoro-(4-methyl-2-pentene) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57150625A (en) * | 1981-03-14 | 1982-09-17 | Daikin Ind Ltd | Perfluoroalkyl group-substituted olefin compound and its preparation |
-
1989
- 1989-08-23 JP JP21713789A patent/JPH0381233A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57150625A (en) * | 1981-03-14 | 1982-09-17 | Daikin Ind Ltd | Perfluoroalkyl group-substituted olefin compound and its preparation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5387728A (en) * | 1992-08-27 | 1995-02-07 | Hoechst Aktiengesellschaft | Process for the preparation of hexafluoropropene dimers having a high proportion of perfluoro-(4-methyl-2-pentene) |
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