JPS60237040A - Preparation of perhalogenoalkanoic acid chloride - Google Patents
Preparation of perhalogenoalkanoic acid chlorideInfo
- Publication number
- JPS60237040A JPS60237040A JP9335284A JP9335284A JPS60237040A JP S60237040 A JPS60237040 A JP S60237040A JP 9335284 A JP9335284 A JP 9335284A JP 9335284 A JP9335284 A JP 9335284A JP S60237040 A JPS60237040 A JP S60237040A
- Authority
- JP
- Japan
- Prior art keywords
- halogen
- light
- rccl3
- irradiation
- reaction
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/38—Acyl halides
- C07C53/46—Acyl halides containing halogen outside the carbonyl halide group
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はパーハロゲノアルカン酸クロリドの製法に関す
る。パーハロデフアルカン酸クロリド、例えばトリフル
オロ酢酸クロリドはトリフルオロ酢酸、無水トリフルオ
ロ酢酸の製造原料として有用であり、これらトリフルオ
ロ酢酸等は例えば医農薬中間体、触媒原料として有用で
゛ある。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing perhalogenoalkanoic acid chloride. Perhalodephalanoic acid chloride, such as trifluoroacetic acid chloride, is useful as a raw material for producing trifluoroacetic acid and trifluoroacetic anhydride, and these trifluoroacetic acids are useful, for example, as intermediates for pharmaceuticals and agricultural chemicals, and raw materials for catalysts.
（従来の技術及びその問題点）
パーハロデフアルカン酸クロリドの従来の製造法として
、例えば米国特許第３．Ｈ１２，１３９，３，１６０，
６５９及び３，７２５．４７５号に記載されるように、
発煙硫酸と水銀触媒を使用する方法が知られているが、
毒性の強い水銀を使用する点で望ましくない。米国特許
第３，１５１，０５１号は光の照射下に酸素とＣ１２を
使用する方法を開示するが、反応性が低く実用的ではな
い。米国特許第４，３４０，５４Ｆ！号はＳＯ３又は発
煙硫酸とハロゲン触媒を使用する方法を開示するが、低
温では反応性が低く、実用的には加熱して反応速度を大
トくする必要があるが、その場合には触媒のハロゲンが
製品中に多量に混入するという欠点及び加熱によるエネ
ルギーの損失、危険度の増大という欠点がある。(Prior art and its problems) As a conventional method for producing perhalodephalanoic acid chloride, for example, US Patent No. 3. H12,139,3,160,
659 and 3,725.475,
A method using fuming sulfuric acid and a mercury catalyst is known, but
It is undesirable because it uses highly toxic mercury. US Pat. No. 3,151,051 discloses a method using oxygen and C12 under irradiation with light, but the reactivity is low and it is not practical. U.S. Patent No. 4,340,54F! No. 1 discloses a method using SO3 or fuming sulfuric acid and a halogen catalyst, but the reactivity is low at low temperatures, and in practice it is necessary to increase the reaction rate by heating, but in that case, the catalyst There are disadvantages in that a large amount of halogen is mixed into the product, energy loss due to heating, and increased risk.
（発明の目的）
本発明の目的は低温下であっても反応速度の大きなパー
ハロデノアルカン酸クロリドの製法を提供することにあ
る。(Objective of the Invention) An object of the present invention is to provide a method for producing perhalodenoalkanoyl chloride that exhibits a high reaction rate even at low temperatures.
また本発明の目的はより安全且つ経済的であり、製品純
度の高いパーハロデノアルカン酸クロリドの製法を提供
することにある。Another object of the present invention is to provide a method for producing perhalodenoalkanoyl chloride that is safer, more economical, and has a higher product purity.
（発明の構成） 本発明は式 ＲＣＣＩ。(Structure of the invention) The present invention has the formula RCCI.
（Ｒは水素のすべてがＦまたはＦと他のハロゲンで置換
された炭素数１〜７のアルキル基を示す）で表わされる
１、１．１− ）リクロローパーハロデノアルカンをＳ
Ｏ３又は発煙硫酸と、ハロゲン又はハロゲン化ハロゲン
（Ｃ１，を除く）の存在下且つ光照射下に反応させるこ
とを特徴とするバーハロデノアルカン酸クロリドの製法
に係る。(R represents an alkyl group having 1 to 7 carbon atoms in which all hydrogens are substituted with F or F and another halogen)
The present invention relates to a method for producing barhalodenoalkanoic acid chloride, which is characterized by reacting O3 or fuming sulfuric acid in the presence of a halogen or a halogenated halogen (excluding C1) and under irradiation with light.
本発明において原料のＲＣＣｌ３の好ましい例は次の通
りである。Preferred examples of the raw material RCCl3 in the present invention are as follows.
ＦＣＸ２ＣＣ１３、ＦＣＸ２ＣＸ２ＣＣ１３、ＦＣＸ２
（ＣＸ２）２ＣＣ１３、（ＦＣＸ２）２ＣＸＣＸ、ＣＣ
ｌ３、ＣＦ、１（ＣＩ’２）６ＣＣｌ １、ここでＸは
、Ｆ、ＣＩ、Ｂｒ又は■である。FCX2CC13, FCX2CX2CC13, FCX2
(CX2)2CC13, (FCX2)2CXCX, CC
13, CF, 1(CI'2)6CCl 1, where X is F, CI, Br or ■.
ＳＯ３としては、安定化された５０３（例、サルファン
）等も挙げることができる。発煙硫酸はＳＯ３濃度２０
重量％以上の発煙硫酸が好ま１７い。Examples of SO3 include stabilized 503 (eg, sulfan). Fuming sulfuric acid has an SO3 concentration of 20
Preferably, the amount of fuming sulfuric acid is 17% by weight or more.
ハロゲン又はハロゲン化ハロゲンの例としてはＢｒ２．
Ｔ ２． Ｔ ｅｌ、Ｔ Ｂｒ、ＣＩＲｒ等を挙げる
ことができ、ＣＩ２は殆ど反応を促進しないため望ま３
−
［７くない。光としては紫外線が好ましい。Examples of halogens or halogenated halogens include Br2.
T2. Examples include T el, T Br, CIRr, etc., and CI2 is preferable because it hardly promotes the reaction.
- [Not 7. As the light, ultraviolet rays are preferred.
本発明の反応は上記ＲＣＣＩ、とＳＯ３又は発煙硫酸を
ハロゲン又はハロゲン化ハロゲン（ＣＩ□を除く）の存
在下且つ光の照射下に行う。ＳＯ３又は発煙硫酸中の８
０３量はＲＣＣｌ、の１モルに対して１〜１０モル、好
ましくは２６２〜２．５モル用いるのが良い。ハロゲン
又はハロゲン化ハロゲンはＲＣＣｌ３に対して０．５〜
１０重量％、好ましくは２〜５重量％使用するのが良い
。反応は常温、常圧で進行するが、一般には２０〜６０
℃、好ましくは２５・−３５°Ｃの温度で、大気圧下で
反応を行うのが好ましい。加圧にしでも反応を行うこと
はできる。The reaction of the present invention is carried out between the above RCCI and SO3 or fuming sulfuric acid in the presence of a halogen or a halogenated halogen (excluding CI□) and under irradiation with light. 8 in SO3 or oleum
The amount of 03 used is preferably 1 to 10 mol, preferably 262 to 2.5 mol, per 1 mol of RCCl. Halogen or halogenated halogen is 0.5 to RCCl3
It is advisable to use 10% by weight, preferably 2 to 5% by weight. The reaction proceeds at room temperature and pressure, but generally 20 to 60
Preferably, the reaction is carried out at a temperature of 25°C to -35°C and under atmospheric pressure. The reaction can be carried out even under pressure.
反応により生成した目的物は通常、蒸留等により精製す
ることができ、未反応のＲＣＣｌ３及びＳ０３、ならび
にハロゲン又はハロゲン化ハロゲンは回収して再使用す
ることができる。The target product produced by the reaction can usually be purified by distillation or the like, and unreacted RCCl3 and S03, as well as halogen or halogenated halogen, can be recovered and reused.
（発明の効果）
本発明の方法によれば、低温において高い反応４−
速度でパーハロデノアルカン酸クロリドを製造すること
ができ、得られる目的物への８０３及びハロゲン又はハ
ロゲン化ハロゲンの混入が少なく、しかも安全且つ経済
的に反応を行うことができる。(Effects of the Invention) According to the method of the present invention, perhalodenoalkanoyl chloride can be produced at a high reaction rate at low temperatures, and 803 and halogen or halogenated halogen can be mixed into the obtained target product. The reaction can be carried out safely and economically.
（実施例） 以下に本発明の実施例を挙げて説明する。(Example) Examples of the present invention will be described below.
実施例１
ＣＦ＊ＣＣｌ、（１６，０ｇ）、Ｓ Ｏ、（１６，０ｇ
）及び臭素（Ｂｒ２．１．Ｏｇ）を還流冷却器、撹拌機
、温度計付きの５０ｍ１のフラスコに入れ、ＵＶランプ
照射、撹拌下に内温２０℃で５時間反応させた。冷却器
上部より発生したガスをドライアイス−アセトン冷却の
ガストラップに補集した。この物をガスクロマトグラフ
ィー（Ｇ Ｌ、 Ｃ）により分析したところＣＦ、ＣＯ
Ｃｌを１０．１８ｇ含んでいた。（収率９０．１％）比
較例１
実施例１と同様に内温を２０℃に保ち、ＩＪ ｖランプ
を照射せずに反応を行なったところ、ＣＦ、ＣＯＣＩは
トレース量程度しか検出されなかった。Example 1 CF*CCl, (16,0 g), SO, (16,0 g
) and bromine (Br2.1.Og) were placed in a 50 ml flask equipped with a reflux condenser, a stirrer, and a thermometer, and reacted with UV lamp irradiation and stirring at an internal temperature of 20° C. for 5 hours. Gas generated from the upper part of the cooler was collected in a gas trap cooled by dry ice and acetone. When this substance was analyzed by gas chromatography (GL, C), it was found that CF, CO
It contained 10.18g of Cl. (Yield 90.1%) Comparative Example 1 As in Example 1, the internal temperature was kept at 20°C and the reaction was carried out without irradiation with the IJV lamp, but only trace amounts of CF and COCI were detected. Ta.
実施例２
ＣｌＣＦ２ＣＦ２ＣＯＣｌ（１０，０ｇ）、Ｓ Ｏ、（
１０，０ｇ＞及びＴ ２（１，０ｇ＞を還流冷却器、撹
拌機、温度計付きの５０ｍ１のフラスコに入れ、ＵＶラ
ンプ照射、撹拌下に内温を４０℃として５時間反応させ
た。反応終了後、精留により沸点５４℃で７．１ｇの留
出物を得た。Ｇ Ｌ ＣによりＣｌＣＦ２ＣＦ２ＣＯＣ
ｌと判明した。Example 2 ClCF2CF2COCl (10,0 g), SO, (
10,0 g> and T2 (1,0 g>) were placed in a 50 ml flask equipped with a reflux condenser, a stirrer, and a thermometer, and reacted for 5 hours at an internal temperature of 40° C. under UV lamp irradiation and stirring. Reaction. After completion, 7.1 g of distillate with a boiling point of 54° C. was obtained by rectification.ClCF2CF2COC was obtained by GLC.
It turned out to be l.
（収率９５．０％）
比較例２
ｔ＋Ｖランプを照射せずに実施例２と同様に反応を行っ
たところ、ＣＩＣＦ ２ＣＦ ２ＣＯＣ１の収率は２０
％であった。(Yield 95.0%) Comparative Example 2 When the reaction was carried out in the same manner as in Example 2 without irradiation with a t+V lamp, the yield of CICF 2CF 2COC1 was 20%.
%Met.
（以 上） 特許出願人 ダイキン工業株式会社 代 理 人 弁理士 １）村 巌 ７− リＡ１(that's all) Patent applicant: Daikin Industries, Ltd. Representative Patent Attorney 1) Iwao Mura 7- rear A1
Claims (5)
された炭素数１〜７のアルキル基を示す）で表わされる
４、ｉ、］−）リクロローパーハロゲ／アルカンをＳＯ
３又は発煙硫酸と、ハロゲン又はハロゲン化ハロゲン（
ＣＩ□を除く）の存在下且つ光照射下に反応させること
を特徴とするバーハロデフアルカン酸クロリドの製法。(1) Formula RCCI. (R represents an alkyl group having 1 to 7 carbon atoms in which all hydrogens are replaced with F or F and another halogen)
3 or fuming sulfuric acid and halogen or halogenated halogen (
1. A method for producing varhalodephalanoic acid chloride, which is characterized in that the reaction is carried out in the presence of a compound (excluding CI□) and under irradiation with light.
１Ｔ２．ｒｃｌ、ＩＢｒ又はＣｌＢｒである特許請求の
範囲第１項に記載の製法。(2) Halogen or halogenated halogen is B r 2
1T2. The manufacturing method according to claim 1, which is rcl, IBr or ClBr.
製法。(3) The manufacturing method according to claim 1, wherein the light is ultraviolet light.
ｌ 、に対して０．５−１０重景％使用する特許請求の
範囲第１項に記載の製法。(4) RC (:
1. The manufacturing method according to claim 1, wherein 0.5-10% of the weight of 1 is used.
項に記載の製法。(5) Claim 1 in which the reaction is carried out at 20 to 60"C
The manufacturing method described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9335284A JPS60237040A (en) | 1984-05-09 | 1984-05-09 | Preparation of perhalogenoalkanoic acid chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9335284A JPS60237040A (en) | 1984-05-09 | 1984-05-09 | Preparation of perhalogenoalkanoic acid chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60237040A true JPS60237040A (en) | 1985-11-25 |
Family
ID=14079878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9335284A Pending JPS60237040A (en) | 1984-05-09 | 1984-05-09 | Preparation of perhalogenoalkanoic acid chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60237040A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628559A (en) * | 2013-11-06 | 2015-05-20 | 连云港金康医药科技有限公司 | Ozone oxidation method used for preparing halogenated acetic acid and esters of halogenated acetic acid |
| CN109369385A (en) * | 2018-11-12 | 2019-02-22 | 江山鑫隆化工有限公司 | A kind of preparation method of Trifluoroacetic Acid Ethyl Ester |
-
1984
- 1984-05-09 JP JP9335284A patent/JPS60237040A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628559A (en) * | 2013-11-06 | 2015-05-20 | 连云港金康医药科技有限公司 | Ozone oxidation method used for preparing halogenated acetic acid and esters of halogenated acetic acid |
| CN109369385A (en) * | 2018-11-12 | 2019-02-22 | 江山鑫隆化工有限公司 | A kind of preparation method of Trifluoroacetic Acid Ethyl Ester |
| CN109369385B (en) * | 2018-11-12 | 2021-06-04 | 江山鑫隆化工有限公司 | Preparation method of ethyl trifluoroacetate |
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