JP2708845B2 - Method for producing propane having difluoromethylene group - Google Patents
Method for producing propane having difluoromethylene groupInfo
- Publication number
- JP2708845B2 JP2708845B2 JP1023741A JP2374189A JP2708845B2 JP 2708845 B2 JP2708845 B2 JP 2708845B2 JP 1023741 A JP1023741 A JP 1023741A JP 2374189 A JP2374189 A JP 2374189A JP 2708845 B2 JP2708845 B2 JP 2708845B2
- Authority
- JP
- Japan
- Prior art keywords
- propane
- reaction
- difluoromethylene group
- difluoropropane
- trichloro
- 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］ 本発明はジフルオロメチレン基を有するプロパンの製
造法に関するものである。The present invention relates to a method for producing propane having a difluoromethylene group.
ジフルオロメチレン基を有するプロパンは従来から用
いられてきたフロン類と同様に発泡剤、冷媒、洗浄剤等
の用途が期待される。Propane having a difluoromethylene group is expected to be used as a foaming agent, a refrigerant, a cleaning agent, and the like, similarly to conventionally used fluorocarbons.
［従来の技術及び発明が解決しようとする課題］ 従来知られているジフルオロメチレン基を有するプロ
パンの合成ルートとしては、例えば、テトラフルオロエ
チレンとメタノールとから2,2,3,3−テトラフルオロプ
ロパノールとし、次にこれと塩化スルフリルとを反応さ
せクロロスルホン酸エステルとした後、これをアルカリ
金属塩化物と反応させることにより１−クロロ−2,2,3,
3−テトラフルオロプロパンを合成する方法にあるよう
に多段の工程を必要とするため、収率の向上が困難であ
り工業的生産に適さないという欠点を有している。[Problems to be Solved by the Prior Art and the Invention] Conventionally known synthesis routes for propane having a difluoromethylene group include, for example, 2,2,3,3-tetrafluoropropanol from tetrafluoroethylene and methanol. Then, this was reacted with sulfuryl chloride to give a chlorosulfonic acid ester, which was then reacted with an alkali metal chloride to give 1-chloro-2,2,3,
As in the method for synthesizing 3-tetrafluoropropane, a multi-step process is required, so that it is difficult to improve the yield and is not suitable for industrial production.
［課題を解決するための手段］ 本発明は下記一般式（１）で表されるジハロゲノメチ
レン基を有するプロパン（以下、化合物Ａという）をア
ンチモンのハロゲン化物よりなる触媒の存在下、液相で
フッ化水素によりフッ素化することを特徴とする下記一
般式（２）で表されるジフルオロメチレン基を有するプ
ロパン（以下、化合物Ｂという）の製造法である。[Means for Solving the Problems] In the present invention, a propane having a dihalogenomethylene group represented by the following general formula (1) (hereinafter referred to as compound A) is prepared in a liquid phase in the presence of a catalyst comprising a halide of antimony. And producing a propane having a difluoromethylene group represented by the following general formula (2) (hereinafter referred to as compound B).
C3H3Cl5-mFm ・・・（１） C3H3Cl5-nFn ・・・（２） （式中、ｍ、ｎは０≦ｍ≦２、２≦ｎ≦５、ｍ＜ｎを満
足する整数） 本反応においてはアンチモンのハロゲン化物、例えば
五フッ化アンチモン、五塩化アンチモン、二塩化三フッ
化アンチモンおよび二臭化三フッ化アンチモン等よりな
るフッ素化触媒が使用可能である。C 3 H 3 Cl 5-m F m (1) C 3 H 3 Cl 5-n F n (2) (where m and n are 0 ≦ m ≦ 2, 2 ≦ n ≦ 5, an integer satisfying m <n) In this reaction, a fluorination catalyst comprising an antimony halide such as antimony pentafluoride, antimony pentachloride, antimony trichloride and antimony tribromide is used. Can be used.
フッ素化反応は液相中常圧もしくは加圧下で、０〜20
0℃、特に好ましくは常温〜150℃の温度範囲で行なうこ
とが適当である。The fluorination reaction is carried out at normal pressure or under pressure in the liquid phase, from 0 to 20.
It is appropriate to carry out the reaction at 0 ° C., particularly preferably at a temperature in the range of ordinary temperature to 150 ° C.
本発明において反応は通常無溶媒で行うが、溶媒を用
いてもよく、この場合に用いられる溶媒は、原料である
プロパン類を溶かし込み、さらに溶媒自身が原料よりフ
ッ素化されにくいものであれば特に限定されない。反応
圧（ゲージ圧）は通常０〜10kg/cm2で行うのが適当であ
り、溶媒を用いる場合は溶媒の種類等によっても異な
る。In the present invention, the reaction is usually carried out without a solvent, but a solvent may be used.The solvent used in this case dissolves the propane as a raw material, and if the solvent itself is less fluorinated than the raw material. There is no particular limitation. The reaction pressure (gauge pressure) is usually appropriate to be 0 to 10 kg / cm 2 , and when a solvent is used, it varies depending on the type of the solvent and the like.
フッ化水素は反応前にあらかじめ仕込んでおいてもか
まわないが、反応時液相へ吹き込む法が好適である。Hydrogen fluoride may be charged before the reaction, but a method of blowing it into the liquid phase during the reaction is preferred.
原料に用いる化合物Ａとしては、1,1,2,2,3−ペンタ
クロロプロパン（Ｒ−240aa）、1,1,1,2,2−ペンタクロ
ロプロパン（Ｒ−240ab）、1,1,2,3−テトラクロロ−２
−フルオロプロパン（Ｒ−241ba）、1,1,1,2−テトラク
ロロ−２−フルオロプロパン（Ｒ−241bb）、1,1,3−ト
リクロロ−2,2−ジフルオロプロパン（Ｒ−242ca）、1,
1,1−トリクロロ−2,2−ジフルオロプロパン（Ｒ−242c
b）等があげられるが、これらはいずれも公知の化合物
である。Compound A used as a raw material includes 1,1,2,2,3-pentachloropropane (R-240aa), 1,1,1,2,2-pentachloropropane (R-240ab), 1,1,2, 3-tetrachloro-2
-Fluoropropane (R-241ba), 1,1,1,2-tetrachloro-2-fluoropropane (R-241bb), 1,1,3-trichloro-2,2-difluoropropane (R-242ca), 1,
1,1-trichloro-2,2-difluoropropane (R-242c
b) and the like, all of which are known compounds.
反応により生成する化合物Ｂとしては、1,1,3−トリ
クロロ−2,2−ジフルオロプロパン（Ｒ−242ca）、1,1,
1−トリクロロ−2,2−ジフルオロプロパン（Ｒ−242c
b）、1,3−ジクロロ−1,2,2−トリフルオロプロパン
（Ｒ−243ca）、1,1−ジクロロ−2,2,3−トリフルオロ
プロパン（Ｒ−243cb）、1,1−ジクロロ−1,2,2−トリ
フルオロプロパン（Ｒ−243cc）、１−クロロ−2,2,3,3
−テトラフルオロプロパン（Ｒ−244ca）、１−クロロ
−1,1,2,2−テトラフルオロプロパン（Ｒ−244cc）、1,
1,1,2,2−ペンタフルオロプロパン（Ｒ−245cb）があげ
られ、これは慣用の方法、例えば、分別蒸留等により分
離し得る。Compound B produced by the reaction includes 1,1,3-trichloro-2,2-difluoropropane (R-242ca), 1,1,
1-trichloro-2,2-difluoropropane (R-242c
b), 1,3-dichloro-1,2,2-trifluoropropane (R-243ca), 1,1-dichloro-2,2,3-trifluoropropane (R-243cb), 1,1-dichloro -1,2,2-trifluoropropane (R-243cc), 1-chloro-2,2,3,3
-Tetrafluoropropane (R-244ca), 1-chloro-1,1,2,2-tetrafluoropropane (R-244cc),
1,1,2,2-pentafluoropropane (R-245cb), which can be separated by a conventional method such as fractional distillation.
［実施例］ 以下、本発明の実施例を示す。EXAMPLES Examples of the present invention will be described below.
実施例 １ 内容積１リットルのハステロイＣ製オートクレーブ
に、1,1,2,2,3−ペンタクロロプロパン（CHCl2CCl2CH2C
l:R−240aa）の500g、五塩化アンチモンの50gを入れ
て、フッ化水素を50g/時の割合で３時間供給しながら、
100℃まで昇温した後、更にフッ化水素を50g/時の割合
で３時間供給した。この状態で20時間、反応温度を保持
して反応させた。反応物は−78℃に冷却したトラップに
捕集した。捕集物の酸分を除去した後の組成をガスクロ
マトグラフィー及び19F−NMRを用いて分析した結果、ジ
フルオロメチレン基を有するCHF2CF2CH2Cl（Ｒ−244c
a）、CHClFCF2CH2Cl（Ｒ−243ca）、およびCHCl2CF2CH2
Cl（Ｒ−242ca）などの他にCHF2CClFCH2Cl（Ｒ−243b
a）、CHClFCClFCH2Cl（Ｒ−242ba）、CHCl2CClFCH2Cl
（Ｒ−241ba）、CHClFCCl2CH2Cl（Ｒ−241aa）等の２個
以上のフッ素原子を有する240番台フロンが生成する事
を確認した。主な成績を表１に示す。Example 1 1,1,2,2,3-pentachloropropane (CHCl 2 CCl 2 CH 2 C) was placed in an autoclave made of Hastelloy C having an internal volume of 1 liter.
l: R-240aa) 500 g of antimony pentachloride and 50 g of hydrogen fluoride are supplied at a rate of 50 g / hour for 3 hours.
After the temperature was raised to 100 ° C., hydrogen fluoride was further supplied at a rate of 50 g / hour for 3 hours. In this state, the reaction was carried out for 20 hours while maintaining the reaction temperature. The reaction was collected in a trap cooled to -78 ° C. As a result of analyzing the composition of the collected matter after removing the acid component by gas chromatography and 19 F-NMR, CHF 2 CF 2 CH 2 Cl having a difluoromethylene group (R-244c
a), CHClFCF 2 CH 2 Cl (R-243ca), and CHCl 2 CF 2 CH 2
In addition to Cl (R-242ca) and the like, CHF 2 CClFCH 2 Cl (R-243b)
a), CHClFCClFCH 2 Cl (R -242ba), CHCl 2 CClFCH 2 Cl
(R-241ba), 240-CFCs having two or more fluorine atoms such as CHClFCCl 2 CH 2 Cl (R-241aa) were confirmed to be formed. Table 1 shows the main results.
実施例２ 1,1,2,2,3−ペンタクロロプロパン（Ｒ−240aa）のか
わりに1,1,1−トリクロロ−2,2−ジフルオロプロパン
（Ｒ−242cb）の500gを、反応温度を110℃とする他は実
施例１と同様の条件で反応を行なった。その結果を表２
に示す。 Example 2 Instead of 1,1,2,2,3-pentachloropropane (R-240aa), 500 g of 1,1,1-trichloro-2,2-difluoropropane (R-242cb) was added at a reaction temperature of 110 g. The reaction was carried out under the same conditions as in Example 1 except that the temperature was changed to ° C. Table 2 shows the results.
Shown in
［発明の効果］ 本発明は、化合物Ａを原料としてフッ素化触媒の存在
下に液相でフッ化水素と反応させることにより、効率的
に化合物Ｂを製造し得るという効果を有する。 [Effect of the Invention] The present invention has an effect that compound B can be efficiently produced by reacting compound A as a raw material with hydrogen fluoride in a liquid phase in the presence of a fluorination catalyst.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭53−95904（ＪＰ，Ａ) 特開 昭52−103392（ＪＰ，Ａ) 特開 平２−117627（ＪＰ，Ａ) 特公 昭39−10310（ＪＰ，Ｂ１) ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-53-95904 (JP, A) JP-A-52-103392 (JP, A) JP-A-2-117627 (JP, A) 10310 (JP, B1)
Claims (2)
チレン基を有するプロパンをアンチモンのハロゲン化物
よりなる触媒の存在下、液相でフッ化水素によりフッ素
化することを特徴とする下記一般式（２）で表されるジ
フルオロメチレン基を有するプロパンの製造法。 C3H3Cl5-mFm ・・・（１） C3H3Cl5-nFn ・・・（２） （式中、ｍ、ｎは０≦ｍ≦２、２≦ｎ≦５、ｍ＜ｎを満
足する整数）1. A method according to claim 1, wherein propane having a dihalogenomethylene group represented by the following general formula (1) is fluorinated with hydrogen fluoride in a liquid phase in the presence of a catalyst comprising a halide of antimony. A method for producing propane having a difluoromethylene group represented by the general formula (2). C 3 H 3 Cl 5-m F m (1) C 3 H 3 Cl 5-n F n (2) (where m and n are 0 ≦ m ≦ 2, 2 ≦ n ≦ 5, an integer satisfying m <n)
ン基を有するプロパンが1,1,2,2,3−ペンタクロロプロ
パン、1,1,1,2,2−ペンタクロロプロパン、1,1,2,3−テ
トラクロロ−２−フルオロプロパン、1,1,1,2−テトラ
クロロ−２−フルオロプロパン、1,1,3−トリクロロ−
2,2−ジフルオロプロパンまたは1,1,1−トリクロロ−2,
2−ジフルオロプロパンである請求項１に記載の製造
法。2. The propane having a dihalogenomethylene group represented by the general formula (1) is 1,1,2,2,3-pentachloropropane, 1,1,1,2,2-pentachloropropane, 1,2,3-tetrachloro-2-fluoropropane, 1,1,1,2-tetrachloro-2-fluoropropane, 1,1,3-trichloro-
2,2-difluoropropane or 1,1,1-trichloro-2,
The method according to claim 1, which is 2-difluoropropane.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1023741A JP2708845B2 (en) | 1989-02-03 | 1989-02-03 | Method for producing propane having difluoromethylene group |
| PCT/JP1990/000123 WO1990008754A2 (en) | 1989-02-02 | 1990-02-01 | Process for producing a 2,2-difluoropropane |
| EP90902684A EP0407622B1 (en) | 1989-02-02 | 1990-02-01 | Process for producing a 2,2-difluoropropane |
| CA002026565A CA2026565C (en) | 1989-02-02 | 1990-02-01 | Process for producing a 2,2-difluoropropane |
| DE69029290T DE69029290T2 (en) | 1989-02-02 | 1990-02-01 | METHOD FOR PRODUCING A 2,2-DIFLUOR PROPANE |
| US07/885,250 US5264639A (en) | 1989-02-02 | 1992-05-20 | Process for producing a 2,2-difluoropropane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1023741A JP2708845B2 (en) | 1989-02-03 | 1989-02-03 | Method for producing propane having difluoromethylene group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02204437A JPH02204437A (en) | 1990-08-14 |
| JP2708845B2 true JP2708845B2 (en) | 1998-02-04 |
Family
ID=12118734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1023741A Expired - Fee Related JP2708845B2 (en) | 1989-02-02 | 1989-02-03 | Method for producing propane having difluoromethylene group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2708845B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9102579B2 (en) * | 2004-04-29 | 2015-08-11 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| CN103193584B (en) * | 2006-01-03 | 2015-07-01 | 霍尼韦尔国际公司 | Method for producing fluorinated organic compounds |
| EP2546223B1 (en) * | 2006-01-03 | 2016-08-10 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| WO2011135416A1 (en) * | 2010-04-26 | 2011-11-03 | Arkema France | Process for the manufacture of 2-chloro-3, 3, 3-trifluoropropene (hcfo 1233xf) by liquid phase fluorination of pentachloropropane |
| EP2640681B1 (en) * | 2010-11-15 | 2017-10-18 | Arkema France | Process for the manufacture of 2-chloro-3,3,3-trifluoropropene (hcfo 1233xf) by liquid phase fluorination of pentachloropropane |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52103392A (en) * | 1976-02-26 | 1977-08-30 | Daikin Ind Ltd | Fluorination catalyst for haloganated hydrocarbon |
| DE2701310A1 (en) * | 1977-01-14 | 1978-07-20 | Bayer Ag | PROCESS FOR THE PREPARATION OF 1,1,1-TRIFLUORO-2-CHLORAETHANE |
| EP0425540B1 (en) * | 1988-06-23 | 1994-08-17 | E.I. Du Pont De Nemours And Company | Catalyzed hydrofluorination process |
-
1989
- 1989-02-03 JP JP1023741A patent/JP2708845B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02204437A (en) | 1990-08-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |