JPH0662459B2 - Process for producing 2-trifluoromethyl-3,3,3-trifluoropropene - Google Patents
Process for producing 2-trifluoromethyl-3,3,3-trifluoropropeneInfo
- Publication number
- JPH0662459B2 JPH0662459B2 JP5229886A JP5229886A JPH0662459B2 JP H0662459 B2 JPH0662459 B2 JP H0662459B2 JP 5229886 A JP5229886 A JP 5229886A JP 5229886 A JP5229886 A JP 5229886A JP H0662459 B2 JPH0662459 B2 JP H0662459B2
- Authority
- JP
- Japan
- Prior art keywords
- trifluoromethyl
- trifluoropropene
- mmol
- formaldehyde
- producing
- 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、２−トリフルオロメチル−３，３，３−トリ
フルオロプロペンの製法に関する。TECHNICAL FIELD The present invention relates to a method for producing 2-trifluoromethyl-3,3,3-trifluoropropene.
２−トリフルオロメチル−３，３，３−トリフルオロプ
ロペンは、ビニリデンフルオライドの共単量体として耐
熱性のきわめて優れたビニリデンフルオライド／２−ト
リフルオロメチル−３，３，３−トリフルオロプロペン
交互共重合体を与えることができ（特公昭５９−２８２
１０号公報参照）、さらにエチレン／テトラフルオロエ
チレン共重合体の改質用単量体といて共重合体に少量添
加することにより該重合体の物性を著しく改善すること
ができる（特公昭５９−２５８０６号公報参照）ことが
知られており、重合体の単量体としてきわめて有用な化
合物である。2-Trifluoromethyl-3,3,3-trifluoropropene is a vinylidene fluoride / 2-trifluoromethyl-3,3,3-trifluoro which has excellent heat resistance as a comonomer of vinylidene fluoride. Propene alternating copolymer can be provided (Japanese Patent Publication No. 59-282).
No. 10), and by adding a small amount of an ethylene / tetrafluoroethylene copolymer modifying monomer to the copolymer, the physical properties of the polymer can be remarkably improved (Japanese Patent Publication No. 59-59-59). 25806), and is a very useful compound as a polymer monomer.
従来、２−トリフルオロメチル−３，３，３−トリフル
オロプロペンの製法としては、ヘキサフルオロアセトン
と無水酢酸またはケテンとの共熱分解が知られている
（特公昭５８−３５１６８号参照）。しかし、この製法
は、原料であるヘキサフルオロアセトンが非常に高価な
化合物であり、またその熱分解に激しい条件を必要とす
るなど、工業的な製法としては数々の欠点を有してい
る。Conventionally, as a method for producing 2-trifluoromethyl-3,3,3-trifluoropropene, co-pyrolysis of hexafluoroacetone and acetic anhydride or ketene has been known (see Japanese Patent Publication No. 58-35168). However, this manufacturing method has a number of drawbacks as an industrial manufacturing method such that hexafluoroacetone as a raw material is a very expensive compound and its thermal decomposition requires severe conditions.
また、オクタフルオロイソブチル低級アルキルエーテル
を脱フッ化水素してヘプタフルオロイソブテニル低級ア
ルキルエーテルを得、これを還元してヘキサフルオロイ
ソブチル低級アルキルエーテルとし、これを更に硫酸エ
ステル化して硫酸（ヘキサフルオロイソブチル）低級ア
ルキルエステルを得、次いでこれを塩基で処理して２−
トリフルオロメチル−３，３，３−トリフルオロプロペ
ンを得る製法が知られている（特公昭５７−６１３３号
公報参照）。この製法も、工程数が多く、従って、試
薬、設備、時間を多く必要とするなど工業的には満足し
うるものではない。Further, octafluoroisobutyl lower alkyl ether is dehydrofluorinated to obtain heptafluoroisobutenyl lower alkyl ether, which is reduced to hexafluoroisobutyl lower alkyl ether, which is further sulfuric acid esterified to form sulfuric acid (hexafluoro Isobutyl) lower alkyl ester is obtained which is then treated with base to give 2-
A production method for obtaining trifluoromethyl-3,3,3-trifluoropropene is known (see Japanese Patent Publication No. 57-6133). This manufacturing method also has a large number of steps, and therefore requires a large amount of reagents, equipment, and time, and is not industrially satisfactory.
本発明の目的は、２−トリフルオロメチル−３，３，３
−トリフルオロプロペンを容易に、低価格でかつ工業的
規模で得る方法を提供することにある。The object of the present invention is 2-trifluoromethyl-3,3,3
-To provide a method for obtaining trifluoropropene easily, at low cost and on an industrial scale.
本発明の要旨は、２−トリフルオロメチル−３，３，３
−トリフルオロプロパン酸メチルをアミンの存在下、ホ
ルムアルデヒドと反応させることを特徴とする２−トリ
フルオロメチル−３，３，３−トリフルオロプロペンの
製法に存する。The gist of the present invention is 2-trifluoromethyl-3,3,3.
-A method for producing 2-trifluoromethyl-3,3,3-trifluoropropene, which comprises reacting methyl trifluoropropanoate with formaldehyde in the presence of an amine.
本発明によれば、２−トリフルオロメチル−３，３，３
−トリフルオロプロパン酸メチルをアミンの存在下、ホ
ルムアルデヒドと反応させることにより、脱ＣＯ2及び
脱ＣＨ3ＯＨして容易に２−トリフルオロメチル−３，
３，３−トリフルオロプロペンへと導かれる。According to the invention, 2-trifluoromethyl-3,3,3
By reacting methyl trifluoropropanoate with formaldehyde in the presence of an amine to easily remove CO 2 and CH 3 OH to give 2-trifluoromethyl-3,
Guided to 3,3-trifluoropropene.
本発明の原料である２−トリフルオロメチル−３，３，
３−トリフルオロプロパン酸メチルは、例えば、１−メ
トキシ−１，１−ジフルオロ−２−トリフルオロメチル
−３，３，３−トリフルオロプロパンを加水分解するこ
とにより得られる。2-trifluoromethyl-3,3, which is the raw material of the present invention
Methyl 3-trifluoropropanoate can be obtained, for example, by hydrolyzing 1-methoxy-1,1-difluoro-2-trifluoromethyl-3,3,3-trifluoropropane.
ホルムアルデヒドは、ホルマリン、パラホルムアルデヒ
ド、トリオキサン、ポリオキシメチレン等の形で供給す
ることができる。Formaldehyde can be supplied in the form of formalin, paraformaldehyde, trioxane, polyoxymethylene and the like.
２−トリフルオロメチル−３，３，３−トリフルオロプ
ロパン酸メチルとホルムアルデヒド（前記ホルマリン等
はホルムアルデヒドのモル数に換算）の仕込みモル比
は、：１〜１：１０、好ましくは、１：１〜１：５であ
る。The charging molar ratio of methyl 2-trifluoromethyl-3,3,3-trifluoropropanoate and formaldehyde (the formalin and the like are converted to the number of moles of formaldehyde) is: 1 to 1:10, preferably 1: 1. ~ 1: 5.
本発明に使用されるアミンの例としては、トリエチルア
ミン、トリプロピルアミン、トリブチルアミン、ピリジ
ン、ピコリン、テトラメチルエチレンジアミン、ジアザ
ビシクロウンデセン、ジエチルアミン、ジブチルアミ
ン、プロピルアミン、ブチルアミン、エチレンジアミン
等をあげることができる。Examples of amines used in the present invention include triethylamine, tripropylamine, tributylamine, pyridine, picoline, tetramethylethylenediamine, diazabicycloundecene, diethylamine, dibutylamine, propylamine, butylamine, ethylenediamine and the like. You can
アミンの使用量は、通常２−トリフルオロメチル−３，
３，３−トリフルオロプロパン酸メチル１モルに対し
て、１〜５０モル、好ましくは１〜２０モルである。The amount of amine used is usually 2-trifluoromethyl-3,
The amount is 1 to 50 mol, preferably 1 to 20 mol, per 1 mol of methyl 3,3-trifluoropropanoate.
反応温度は、３０〜２００℃、好ましくは、５０〜１５
０℃であり、反応時間は、０．５〜１０時間、好ましく
は、１〜５時間である。The reaction temperature is 30 to 200 ° C., preferably 50 to 15
It is 0 ° C., and the reaction time is 0.5 to 10 hours, preferably 1 to 5 hours.
以下、本発明を実施例により更に具体的に説明する。 Hereinafter, the present invention will be described more specifically by way of examples.
実施例１ コンデンサー、適下漏斗及び温度計を備えた１００ｍｌ
四つ口フラスコ中に、トリブチルアミン２０．０ｇ（１
０８ミリモル）、パラホルムアルデヒド１．２ｇ（ホル
ムアルデヒド換算で３９ミリモル）を入れ、系内２０℃
で２−トリフルオロメチル−３，３，３−トリフルオロ
プロパン酸メチル４．２ｇ（２０ミリモル）を適下し
た。Example 1 100 ml equipped with condenser, suitable funnel and thermometer
In a four-necked flask, 20.0 g (1
08 mmol) and 1.2 g of paraformaldehyde (39 mmol in terms of formaldehyde) were added, and the system was kept at 20 ° C.
Then, 4.2 g (20 mmol) of methyl 2-trifluoromethyl-3,3,3-trifluoropropanoate was appropriately applied.
適下終了後、系内９０℃に加温し、３時間撹拌下反応さ
せた。コンデンサー上部から出てきたガスをアルカリ洗
浄、アルミナ乾燥後蒸留し、２−トリフルオロメチル−
３，３，３−トリフルオロプロペン１．６１ｇ（収率４
９．１％）を得た。沸点１４℃。After completion of the appropriate temperature, the system was heated to 90 ° C. and reacted for 3 hours with stirring. The gas discharged from the upper part of the condenser is washed with alkali, dried on alumina, and then distilled to give 2-trifluoromethyl-
1.63 g of 3,3,3-trifluoropropene (yield 4
9.1%) was obtained. Boiling point 14 ° C.
実施例２ コンデンサー、適下漏斗及び温度計を備えた１００ｍｌ
四つ口フラスコ中に、ピリジン１５．０ｇ（１９０ミリ
モル）、パラホルムアルデヒド１．２ｇ（ホルムアルデ
ヒド換算で３９ミリモル）を入れ、系内２０℃で２−ト
リフルオロメチル−３，３，３−トリフルオロプロパン
酸メチル４．２ｇ（２０ミリモル）を適下した。Example 2 100 ml equipped with condenser, suitable funnel and thermometer
In a four-necked flask, 15.0 g (190 mmol) of pyridine and 1.2 g of paraformaldehyde (39 mmol in terms of formaldehyde) were placed, and 2-trifluoromethyl-3,3,3-trifluoro at 20 ° C. in the system. 4.2 g (20 mmol) of methyl propanoate were applied.
適下終了後、系内９０℃に加温し、３時間撹拌下反応さ
せた。コンデンサー上部から出てきたガスをアルカリ洗
浄、アルミナ乾燥後蒸留し、２−トリフルオロメチル−
３，３，３−トリフルオロプロペン０．９３ｇ（収率２
８．４％）を得た。After completion of the appropriate temperature, the system was heated to 90 ° C. and reacted for 3 hours with stirring. The gas discharged from the upper part of the condenser is washed with alkali, dried on alumina, and then distilled to give 2-trifluoromethyl-
0.93 g of 3,3,3-trifluoropropene (yield 2
8.4%).
実施例３ コンデンサー、適下漏斗及び温度計を備えた１００ｍｌ
四つ口フラスコ中に、ジエチルアミン１８．５ｇ（２５
３ミリモル）、パラホルムアルデヒド１．２ｇ（ホルム
アルデヒド換算で３９ミリモル）を入れ、系内２０℃で
２−トリフルオロメチル−３，３，３−トリフルオロプ
ロパン酸メチル４．２ｇ（２０ミリモル）を適下した。Example 3 100 ml equipped with condenser, lower funnel and thermometer
In a four-necked flask, 18.5 g of diethylamine (25
3 mmol) and 1.2 g of paraformaldehyde (39 mmol in terms of formaldehyde) were added, and 4.2 g (20 mmol) of methyl 2-trifluoromethyl-3,3,3-trifluoropropanoate was added at 20 ° C. in the system. Defeated
適下終了後、系内８０℃に加温し、３時間撹拌下反応さ
せた。コンデンサー上部から出てきたガスをアルカリ洗
浄、アルミナ乾燥後蒸留し、２−トリフルオロメチル−
３，３，３−トリフルオロプロペン０．８０ｇ（収率２
４．４％）を得た。After completion of the appropriate temperature, the system was heated to 80 ° C. and reacted for 3 hours with stirring. The gas discharged from the upper part of the condenser is washed with alkali, dried on alumina, and then distilled to give 2-trifluoromethyl-
0.83 g of 3,3,3-trifluoropropene (yield 2
4.4%) was obtained.
本発明の製法によれば、２−トリフルオロメチル−３，
３，３−トリフルオロプロペンを容易かつ安価に得るこ
とができる。According to the production method of the present invention, 2-trifluoromethyl-3,
3,3-trifluoropropene can be obtained easily and inexpensively.
Claims (1)
リフルオロプロパン酸メチルをアミンの存在下、ホルム
アルデヒドと反応させることを特徴とする２−トリフル
オロメチル−３，３，３−トリフルオロプロペンの製
法。1. Methyl 2-trifluoromethyl-3,3,3-trifluoropropanoate is reacted with formaldehyde in the presence of an amine, 2-trifluoromethyl-3,3,3-tri. Fluoropropene manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5229886A JPH0662459B2 (en) | 1986-03-10 | 1986-03-10 | Process for producing 2-trifluoromethyl-3,3,3-trifluoropropene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5229886A JPH0662459B2 (en) | 1986-03-10 | 1986-03-10 | Process for producing 2-trifluoromethyl-3,3,3-trifluoropropene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62252735A JPS62252735A (en) | 1987-11-04 |
| JPH0662459B2 true JPH0662459B2 (en) | 1994-08-17 |
Family
ID=12910886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5229886A Expired - Fee Related JPH0662459B2 (en) | 1986-03-10 | 1986-03-10 | Process for producing 2-trifluoromethyl-3,3,3-trifluoropropene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0662459B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011116B (en) * | 2017-03-28 | 2020-11-13 | 巨化集团技术中心 | Preparation method of hexafluoroisobutylene |
-
1986
- 1986-03-10 JP JP5229886A patent/JPH0662459B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62252735A (en) | 1987-11-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |