JPS617228A - Preparation of 2-fluoropropanal - Google Patents
Preparation of 2-fluoropropanalInfo
- Publication number
- JPS617228A JPS617228A JP59127592A JP12759284A JPS617228A JP S617228 A JPS617228 A JP S617228A JP 59127592 A JP59127592 A JP 59127592A JP 12759284 A JP12759284 A JP 12759284A JP S617228 A JPS617228 A JP S617228A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- formula
- monofluoroethylene
- rhodium
- expressed
- 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
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は式
％式％（）
で表される２−フルオロプロパナールを製造する方法に
関する。更に詳しくは、本発明は周期表第■族金属触媒
の存在下、式
で表されるモノフルオロエチレンをヒドロホルミル化す
ることにより２−フルオロプロパナールを製造する方法
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2-fluoropropanal having the formula %. More specifically, the present invention relates to a method for producing 2-fluoropropanal by hydroformylating monofluoroethylene represented by the formula in the presence of a metal catalyst from Group I of the periodic table.
本発明によシ得られる２−フルオロプロパナールは種々
の化合物の合成原料として用いることができる。例えば
、酸化することにより得られる２−フルオロプロピオン
酸は除草剤として有用であることが知ちれている（特開
昭５５−４０６０９号参照）。2-fluoropropanal obtained according to the present invention can be used as a raw material for the synthesis of various compounds. For example, 2-fluoropropionic acid obtained by oxidation is known to be useful as a herbicide (see JP-A-55-40609).
従来、２−フルオロプロパナールを製造する方法として
は、２−ブロモプロピオン酸エチルをＫＦでハロゲン交
換し、塩基の存在下にギ酸エチルと反応させ、さらに濃
硫酸中で加熱することにより得る方法が知られているが
ｒ Ｅ 、 Ｅ Ｉｋｉｋ 、 Ｂｕｌ ｌ 。Conventionally, 2-fluoropropanal has been produced by halogen-exchanging ethyl 2-bromopropionate with KF, reacting it with ethyl formate in the presence of a base, and then heating it in concentrated sulfuric acid. Although known, r E, E Ikik, Bull.
Ｓｏｃ、Ｃｈｉｍ、Ｆｒ、、２２５４（１９６４）’）
、工程数も多く全収率も４チと極めて低いものであり、
工業的には採用しがたいものである。Soc, Chim, Fr., 2254 (1964)')
, the number of steps is large and the total yield is extremely low at 4.
It is difficult to adopt it industrially.
本発明者らは、２−フルオロプロパナールの工業的製造
方法を見出すべく鋭意検討した結果、入手容易な触媒を
用い、高収率で２−フルオロプロパナールを製造できる
ことを見出し本発明を完成した。The present inventors conducted intensive studies to find an industrial method for producing 2-fluoropropanal, and as a result, discovered that 2-fluoropropanal can be produced in high yield using an easily available catalyst, and completed the present invention. .
本発明の原料であるモノフルオロエチレンは、アセチレ
ンとＨＦの反応をはじめ多くの方法によシ製造すること
ができ、容易に入手可能な化合物である。Monofluoroethylene, which is the raw material of the present invention, can be produced by many methods including the reaction of acetylene and HF, and is an easily available compound.
本発明は第■族金属触媒の存在下に行うことが必要であ
る。これらの触媒としては例えば、塩化コバルト、酢酸
コバルト、ジコバルトオクタカルボニル、ヒドリドテト
ラカルボニルコバルト等のコバルト系触媒、塩化ロジウ
ム、酢酸ロジウム、テトラロジウムドデカカルボニル、
ヘキサロジウムへキサデカカルボニル、ヒドリドナト２
カルボニルロジウム、ヒドリドカルボニルトリス（トリ
フェニルホスフィン）ロジウム、クロロカルボニルビス
（トリフェニルホスフィン）ロジウム、クロロジカルボ
ニルロジウムニ量体、クロロトリス（トリフェニルホス
フィン）ロジウム等のロジウム系触媒、ジクロロビス（
トリフェニルホスフィン）白金、塩化第一白金カリウム
等の白金系触媒及びこれらの白金系触媒に塩化第一スズ
を添加した触媒、塩化ルテニウム、ルテニウムドデカカ
ルボニル等のルテニウム系触媒等を例示することができ
る。The present invention must be carried out in the presence of a Group I metal catalyst. Examples of these catalysts include cobalt-based catalysts such as cobalt chloride, cobalt acetate, dicobalt octacarbonyl, cobalt hydride tetracarbonyl, rhodium chloride, rhodium acetate, tetrarhodium dodecacarbonyl,
hexalodium hexadecacarbonyl, hydridonato 2
Rhodium-based catalysts such as carbonyl rhodium, hydridocarbonyl tris(triphenylphosphine) rhodium, chlorocarbonyl bis(triphenylphosphine) rhodium, chlorodicarbonyl rhodium dimer, chlorotris(triphenylphosphine) rhodium, dichlorobis(
Examples include platinum-based catalysts such as platinum (triphenylphosphine), platinum-based potassium chloride, catalysts obtained by adding stannous chloride to these platinum-based catalysts, ruthenium-based catalysts such as ruthenium chloride, ruthenium dodecacarbonyl, etc. .
また、これらの触媒に対してニトリル、アミン、ホスフ
ィン、アルシン等を添加して用いても何ら差支えない。Moreover, there is no problem even if nitrile, amine, phosphine, arsine, etc. are added to these catalysts.
さらに、これらの触媒は活性炭、シリカ、アルミナ、有
機重合体等に担持させて使用することもできる。これら
の触媒のうち、活性が高いことからコバルト及びロジウ
ム系触媒の使用が好ましい。触媒の使用量はモノフルオ
ロエチレンに対して通常１０〜１０ モルの範囲で用い
ることができる。Furthermore, these catalysts can also be used supported on activated carbon, silica, alumina, organic polymers, etc. Among these catalysts, cobalt and rhodium catalysts are preferably used because of their high activity. The amount of the catalyst to be used is generally 10 to 10 moles based on monofluoroethylene.
本発明のヒドロホルミル化に於ける一酸化炭素及び水素
は通常常圧乃至３００気圧の圧力をもって系内に導入し
反応を行うことができる。Carbon monoxide and hydrogen in the hydroformylation of the present invention can be generally introduced into the system at a pressure of normal pressure to 300 atmospheres to carry out the reaction.
本発明の実施にあたっては溶媒中でおこなうことが好ま
しく、例えばベンゼン、トルエン、キシレン等の芳香族
系溶媒、テトラヒドロフラン、ジオキサン等のエーテル
系溶媒、メタノール、エタノール等のアルコール系溶媒
、トリエチルアミン、ピリジン等のアミン系溶媒、酢酸
、酢酸エチル等のカルボン酸及びそのエステル等を使用
することができる。The present invention is preferably carried out in a solvent, such as aromatic solvents such as benzene, toluene, and xylene, ether solvents such as tetrahydrofuran and dioxane, alcohol solvents such as methanol and ethanol, and triethylamine and pyridine. Amine solvents, acetic acid, carboxylic acids such as ethyl acetate, esters thereof, etc. can be used.
反応は用いる触媒によっても異なるが、室温乃至３００
°０の範囲で円滑に進行する。The reaction varies depending on the catalyst used, but the reaction temperature ranges from room temperature to 300℃.
Proceeds smoothly within the range of °0.
以下、実施例により本発明を更に詳細に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例Ｉ
ＣＨ，、＝ｃ）ｌＦ＋ＣＯ＋Ｈ２−一→ＣＨ３Ｃ１−ｆ
ＦｃＨ０５０１Ｒ１のオートクレーブにヘキサロジウム
へキサデカカルボ＝ ル（３，６Ｉｎｇ、 ３．３ Ｘ
１０ ｒｔｍｏｌ ）及びトルエン（５Ｗ１１）を
入れ脱気した。フルオロエチレン（４６０ｑ、１０ｍｍ
ｏｌ）を導入した後、−酸化炭素分圧３５気圧及び水素
分圧３５気圧下８０°０で７時間加熱攪拌した。冷却後
常圧にもどし内容物をガスクロマトグラフィーで分析し
たところ２−フルオロプロパナールが９５チの収率で生
成していた。Example I CH,,=c) IF+CO+H2-1→CH3C1-f
Hexarodium hexadecacarboxylic acid (3,6 Ing, 3.3
10 rtmol) and toluene (5W11) were added and degassed. Fluoroethylene (460q, 10mm
ol) was introduced, and the mixture was heated and stirred at 80°0 for 7 hours under a -carbon oxide partial pressure of 35 atm and a hydrogen partial pressure of 35 atm. After cooling, the pressure was returned to normal and the contents were analyzed by gas chromatography, and it was found that 2-fluoropropanal was produced in a yield of 95%.
沸点：５６−５７°Ｏ／７６０ｍｍＨｇ’ｉ−Ｉ ＮＭ
Ｒ（ＣＤＣＩ ３： ＴＭＳ ） ：δ１，４６（ｄ、
ｄ。Boiling point: 56-57°O/760mmHg'i-I NM
R (CDCI 3: TMS): δ1,46 (d,
d.
Ｊ＝２４．０ 、７．２Ｈｚ 、 ３Ｈ） 。J=24.0, 7.2Hz, 3H).
４．９（ｄ、ｑ 、Ｊ＝４９．５ 。4.9 (d, q, J=49.5.
７．２Ｈｚ 、 ＩＨ） 、 ９．８０ （ｄ 。7.2Hz, IH), 9.80 (d.
Ｊ＝６．９Ｈｚ、ＩＨ）。J=6.9Hz, IH).
”Ｆ ＮＭＲ（ＣＤＣｌ２：ＣＦＣＩｓ）：δ −１９
０，８（ｍ。"F NMR (CDCl2:CFCIs): δ -19
0.8 (m.
ＩＦ）。IF).
実施例２〜７
ＣＩ（２＝ＣＨＦ＋ＣＯ＋Ｈ２−一→Ａ１３ＣＨＦＱ（
Ｏ実施例１と同様な操作で反応を行った結果を表１に示
す。Examples 2 to 7 CI(2=CHF+CO+H2-1→A13CHFQ(
The reaction was carried out in the same manner as in Example 1, and the results are shown in Table 1.
怠者例
ＣＨ６Ｃｔ（ＰＧ（Ｏ−一一一今ＣＨ３ＣＨＦＣ００Ｈ
２−フルオログロパナール（８５２ダ、１１．２ｍｍｏ
１ ）の２Ｎ硫酸水溶液（１１，２ｍ７）に過マンガ
ン酸カリウＡ （１，２７ｇ 、 ８．１ｍｍｏｌ ）
を少量ずつ加え１時間４０分攪拌後、３．８Ｎ硫酸（６
，９ｍ／）を加え、次いで亜硫酸水素ナトリウムを反応
溶液が無色になるまで加えた。反応液をエーテルで抽出
し硫酸ナトリウムで乾燥後、減圧下溶媒を留去し、残留
物をガスクロマトグラフィーで分析したところ２−フル
オロプロピオン酸が収率５９％で生成していることがわ
かった。Lazy example CH6Ct(PG(O-111 now CH3CHFC00H
2-fluoroglopanal (852 da, 11.2 mmo
Potassium permanganate A (1.27g, 8.1mmol) in 2N sulfuric acid aqueous solution (11.2m7) of 1)
was added little by little and stirred for 1 hour and 40 minutes, then 3.8N sulfuric acid (6
, 9 m/) was added, and then sodium bisulfite was added until the reaction solution became colorless. The reaction solution was extracted with ether, dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was analyzed by gas chromatography, which revealed that 2-fluoropropionic acid was produced in a yield of 59%. .
Claims (2)
ることを特徴とする、式 Ｈ＿３Ｃ−ＣＨＦ−ＣＨＯ で表される２−フルオロプロパナールの製造方法。(1) In the presence of a metal catalyst from Group VIII of the periodic table, monofluoroethylene expressed by the formula ▲ (numerical formula, chemical formula, table, etc.) is hydroformylated, expressed by the formula H_3C-CHF-CHO. A method for producing 2-fluoropropanal.
許請求の範囲第（１）項に記載の方法。(2) The method according to claim (1), wherein the Group VIII metal is cobalt or rhodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59127592A JPS617228A (en) | 1984-06-22 | 1984-06-22 | Preparation of 2-fluoropropanal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59127592A JPS617228A (en) | 1984-06-22 | 1984-06-22 | Preparation of 2-fluoropropanal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS617228A true JPS617228A (en) | 1986-01-13 |
| JPH0417171B2 JPH0417171B2 (en) | 1992-03-25 |
Family
ID=14963890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59127592A Granted JPS617228A (en) | 1984-06-22 | 1984-06-22 | Preparation of 2-fluoropropanal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS617228A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5195888A (en) * | 1991-08-19 | 1993-03-23 | Praxair Technology, Inc. | Multi-layer fluid curtains for furnace openings |
| WO2016016446A1 (en) * | 2014-07-31 | 2016-02-04 | Sandoz Ag | Process for preparing 2-fluoropropionaldehyde |
-
1984
- 1984-06-22 JP JP59127592A patent/JPS617228A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5195888A (en) * | 1991-08-19 | 1993-03-23 | Praxair Technology, Inc. | Multi-layer fluid curtains for furnace openings |
| WO2016016446A1 (en) * | 2014-07-31 | 2016-02-04 | Sandoz Ag | Process for preparing 2-fluoropropionaldehyde |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0417171B2 (en) | 1992-03-25 |
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