JPS60116650A - Production of halogenated vinyl ether - Google Patents
Production of halogenated vinyl etherInfo
- Publication number
- JPS60116650A JPS60116650A JP22333783A JP22333783A JPS60116650A JP S60116650 A JPS60116650 A JP S60116650A JP 22333783 A JP22333783 A JP 22333783A JP 22333783 A JP22333783 A JP 22333783A JP S60116650 A JPS60116650 A JP S60116650A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl ether
- halogen
- base
- raw material
- reaction product
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、ハロゲン化ビニルエーテル類の新規″な製法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing halogenated vinyl ethers.
ハロゲン化ビニルエーテル類は1例えば医薬。Halogenated vinyl ethers are used in pharmaceuticals, for example.
農薬などの原料として有用な化合物であり、以前からそ
の製法について種々提案がなされている。It is a compound that is useful as a raw material for agricultural chemicals, and various proposals have been made for its production.
例えばケミカルアブストラクトの第50巻。For example, Volume 50 of Chemical Abstracts.
2428hには、α−クロル−β、β−ジメトキシプロ
ピオン酸を塩化チオニルで処理し、ハロゲン化ビニルエ
ーテル類の一種であるα−クロル−β−メトキシアクリ
ル酸を製造する方法につき、提′案がなされている。No. 2428h proposed a method for producing α-chloro-β-methoxyacrylic acid, a type of halogenated vinyl ether, by treating α-chloro-β,β-dimethoxypropionic acid with thionyl chloride. ing.
本発明者らは、ハロゲン化ビニルエーテル類の工業的に
有利な製法を開発することを目的とし。The present inventors aimed to develop an industrially advantageous method for producing halogenated vinyl ethers.
鋭意研究を行った。その結果、安価にしかも容易に入手
できるビニルエーテル類とハロゲンを反応させた後9反
応生成物を塩基で処理すればその目的が達成されること
、すなわちハロゲン化ビニルエーテル類を極めて容易に
製造できることを見い出した。I conducted extensive research. As a result, they discovered that the objective could be achieved by reacting inexpensive and easily available vinyl ethers with a halogen and then treating the reaction product with a base, that is, halogenated vinyl ethers could be produced extremely easily. Ta.
本発明における原料であるビニルエーテル類ハ。Vinyl ethers which are raw materials in the present invention c.
一般式R’0CR= 0H−Yで示すことができる。It can be represented by the general formula R'0CR=0H-Y.
該式においてR1はメチル、エチル、n−プロピル+i
−7’ロビル、n−ブチル+ 17’チル。In this formula, R1 is methyl, ethyl, n-propyl+i
-7' lovil, n-butyl + 17' thyl.
5ee−ブチル、tert−ブチル、n−ペンチル、n
−ヘキシル、n−ヘプチル、n−オクチルなどの如き炭
素数1〜8を有するアルキル基を挙げることができる。5ee-butyl, tert-butyl, n-pentyl, n
Mention may be made of alkyl groups having 1 to 8 carbon atoms such as -hexyl, n-heptyl, n-octyl and the like.
これらのアルキル基には1反応を阻害しない置換基9例
えばアルコキシ基、ハロゲン原子などの置換基を有する
こともできる。また式中Yは+’−ON基または−00
OR2基(ただしR2は。These alkyl groups can also have substituents 9 such as alkoxy groups and halogen atoms that do not inhibit the reaction. In the formula, Y is +'-ON group or -00
OR2 group (however, R2 is.
前記R1に定義したアルキル基から選択される。)を示
す。It is selected from the alkyl groups defined for R1 above. ) is shown.
また本発明で使用に供されるハロゲンとしては。Further, the halogen that can be used in the present invention includes:
特に塩素および臭素が好ましい。Particularly preferred are chlorine and bromine.
これらビニルエーテル類(1)とハロゲン(It) ト
の反応は1次式に従って進行し、(■)で示されるジハ
ロゲン化物が反応生成物として得られるものと推定され
る。It is presumed that the reaction between vinyl ethers (1) and halogen (It) proceeds according to a linear equation, and a dihalide represented by (■) is obtained as a reaction product.
X
R1oaH= 0H−y+x2−□ Rtoaaca
−y(I) (ff) [有])
該反応は1通常溶媒中で行われる。溶媒としては、ヘキ
サン、シクロヘキサン、石油エーテル。X R1oaH= 0H-y+x2-□ Rtoaaca
-y(I) (ff) The reaction is usually carried out in a solvent. Solvents include hexane, cyclohexane, and petroleum ether.
ベンゼン、トルエンなどの炭化水素類、あるいは四塩化
炭素、クロロホルム、塩化メチレン、ジクロロエタンな
どのハロゲン化炭化水素類、さらにはジオキサン、テト
ラヒドロフランなどの非プロトン性の溶媒が好ましい。Preferred are hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and dichloroethane, and further aprotic solvents such as dioxane and tetrahydrofuran.
ハロゲンは、通常、ビニルエーテル類ト等モル以上、好
ましくはビニルエーテル類1モルに対して1〜10モル
使用される。その供給方法には特段の制限はないが、ガ
ス状あるいは液状のハロゲンを直接反応液中に送り込む
こともでき、また反応溶媒と同じ溶媒に溶かしたハロゲ
ン溶液を反応液中に送り込むこともできる。The halogen is usually used in an amount equal to or more than the same mole as the vinyl ether, preferably 1 to 10 moles per mole of the vinyl ether. There are no particular restrictions on the method of supplying the halogen, but gaseous or liquid halogen can be directly introduced into the reaction solution, or a halogen solution dissolved in the same solvent as the reaction solvent can also be introduced into the reaction solution.
まだ該反応は2反応系が液状を保持する温度下で行うこ
とができるが2反応効率からみて80℃以下の温度、好
ましくは一10〜30℃の温度で行うことが望ましい。The reaction can be carried out at a temperature at which the two reaction systems remain liquid, but from the viewpoint of the efficiency of the two reactions, it is desirable to carry out the reaction at a temperature below 80°C, preferably at a temperature of -10 to 30°C.
次いで、得られたジハロゲン化物を塩基で処理すること
により、(■)式で示される目的物であるハロゲン化ビ
ニルエーテル類を合成することができる・ エ
ROCH=O,−Y
(IV)
(ただし式中R,XおよびYは前記と同一の意味を有す
る。)
該処理は、前記反応終了後の系に直接塩基を加えて行う
こともできるが、前記反応終了後の系から溶媒、未反応
の原料などを除去した残留物を溶媒に溶かし、その溶液
に塩基を加えて行うこともできる。その処理操作は、室
温〜加熱還流の温度下に行うことができる。Next, by treating the obtained dihalide with a base, the target halogenated vinyl ethers represented by the formula (■) can be synthesized.ROCH=O, -Y (IV) (where the formula R, It can also be carried out by dissolving the residue from which raw materials have been removed in a solvent and adding a base to the solution. The treatment operation can be carried out at a temperature ranging from room temperature to heating to reflux.
使用に供される塩基としては、酢酸ナトリウム。The base that can be used is sodium acetate.
酢酸カリウム、プロピオン酸ナトリウムなどの低級飽和
脂肪酸のアルカリ金属塩、炭酸す) IJウム。Alkali metal salts of lower saturated fatty acids such as potassium acetate, sodium propionate, carbonate) IJum.
炭酸カリウム、炭酸リチウム、炭酸水素ナトリウム、炭
酸水素カリウムなどの炭酸のアルカリ金属塩、さらには
トリエチルアミン、トリメチルアミン、ピリジン、モル
ホリンなどの有機塩基などが挙げられる。これら塩基は
、ビニルエーテル類1モルに対して0.5モル以上、好
ましくは1〜10モル用いられる。Examples include alkali metal salts of carbonic acid such as potassium carbonate, lithium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate, and organic bases such as triethylamine, trimethylamine, pyridine, and morpholine. These bases are used in an amount of 0.5 mol or more, preferably 1 to 10 mol, per mol of the vinyl ether.
処理後、目的物のハロゲン化ビニルエーテル類は2通常
の操作1例えば減圧蒸留、溶媒抽出などの操作を適宜施
すことによって、単離精製することができる。After the treatment, the target halogenated vinyl ether can be isolated and purified by appropriately performing two conventional operations such as distillation under reduced pressure and solvent extraction.
次に1本発明の実施例を挙げる。Next, an example of the present invention will be described.
実施例1
滴下ロート、還流冷却器、温度計を備えた25wt1の
三角フラスコに、ビニルエーテル類としてβ−メトキシ
アクリロニトリル4.20fおよび四塩化炭素10m/
を仕込んだ。外部を氷−水バスで冷却し、攪拌下に臭素
2.56mJを反応温度が10℃を越えないようにゆっ
くり滴下した後、さらに30分間攪拌を行った。次いで
酢酸ナトリウム4,52を添加し、1時間加熱還流した
後、冷却し、沈殿物をF去した。F液を減圧蒸留し四塩
化炭素。Example 1 Into a 25wt1 Erlenmeyer flask equipped with a dropping funnel, a reflux condenser, and a thermometer, 4.20f of β-methoxyacrylonitrile and 10m/ml of carbon tetrachloride were added as vinyl ethers.
I prepared it. The outside was cooled with an ice-water bath, and while stirring, 2.56 mJ of bromine was slowly added dropwise so that the reaction temperature did not exceed 10°C, followed by further stirring for 30 minutes. Next, 4,52 ml of sodium acetate was added, and after heating under reflux for 1 hour, the mixture was cooled and the precipitate was removed with F. Distill F solution under reduced pressure to obtain carbon tetrachloride.
酢酸を留去し黄色の液体を得た。該黄色の液体をさらに
減圧蒸留し、シスおよびトランスのα−ブロモ−β−メ
トキシアクリロニトリルの混合物である無色の液体6.
51を得た。Acetic acid was distilled off to obtain a yellow liquid. The yellow liquid was further distilled under reduced pressure to obtain a colorless liquid which is a mixture of cis and trans α-bromo-β-methoxyacrylonitrile6.
I got 51.
実施例2
四塩化炭素に代えてジオキサンを溶媒として用いた他は
、実施例1と同様の操作で実験を行った。Example 2 An experiment was conducted in the same manner as in Example 1, except that dioxane was used as a solvent instead of carbon tetrachloride.
その結果、シスおよびトランスの混合α−プロモーβ−
メトキシアクリロニトリル6.11を得た。As a result, a mixed cis and trans α-promo β-
6.11 ml of methoxyacrylonitrile was obtained.
実施例6・
実施例1と同様の操作によってβ−メトキシアクリロニ
) IJルと臭素との反応を行った後、炭酸ナトリウム
5.01を添加し、室温で10分間攪拌を行った。これ
以降の操作は実施例1と同様に行い、シスおよびトラン
スの混合α−ブロモ−β−メトキシアクリロニトリル4
.6fを得た。Example 6 After reacting β-methoxyacryloni (IJ) with bromine in the same manner as in Example 1, 5.0 liters of sodium carbonate was added, and the mixture was stirred at room temperature for 10 minutes. The subsequent operations were carried out in the same manner as in Example 1, and cis and trans mixed α-bromo-β-methoxyacrylonitrile 4
.. I got 6f.
実施例4
吹き込み管、温度計を備えた50m1三角フラスコに、
β−メトキシアクリロニトリル4.2Ofおよび四塩化
炭素20m/を仕込んだ。外部を氷−水バスで冷却し、
攪拌下に塩素ガスを10分間7t/hrの速度で通気し
た後、50分間攪拌を行った。四塩化炭素および未反応
の塩素を減圧下で留去した後、残留物に四塩化炭素20
罰を加えて。Example 4 In a 50 ml Erlenmeyer flask equipped with a blow tube and a thermometer,
4.2 Of of β-methoxyacrylonitrile and 20 m/m of carbon tetrachloride were charged. Cool the outside with an ice-water bath,
While stirring, chlorine gas was passed through at a rate of 7 t/hr for 10 minutes, followed by stirring for 50 minutes. After distilling off carbon tetrachloride and unreacted chlorine under reduced pressure, 20% of carbon tetrachloride was added to the residue.
Add punishment.
溶解させた。次いで、酢酸ナトリウム4.51を添加し
、1時間加熱還流した後、冷却、沈殿物を炉去した。戸
液を減圧蒸留し、シスおよびトランスの混合α−クロル
−β−メトキシアクリロニトリル2.51i+を得た。Dissolved. Next, 4.5 liters of sodium acetate was added, and after heating under reflux for 1 hour, the mixture was cooled and the precipitate was removed from the oven. The solution was distilled under reduced pressure to obtain 2.51i+ of mixed cis and trans α-chloro-β-methoxyacrylonitrile.
実施例5
ビニルエーテル類として、β−n−ブトキシアクリロニ
トリル6.331を用いた他は、実施例1と同様の操作
で実験を行った。その結果、シスおよびトランスの混合
α−ブロモ−β−n−ブトキシアクリロニトリルが7.
12得られた。Example 5 An experiment was carried out in the same manner as in Example 1, except that β-n-butoxyacrylonitrile 6.331 was used as the vinyl ether. As a result, mixed cis and trans α-bromo-β-n-butoxyacrylonitrile was obtained with 7.
12 were obtained.
実施例6
ビニルエーテル類として、β−メトキシアクリル酸メチ
ル5.BOfを用いた他は、実施例1と同様の操作で実
験を行った。その結果、シスおよびトランスの混合α−
プロモーβ−メトキシアクリル酸メチル7.21を得た
。Example 6 As vinyl ethers, methyl β-methoxyacrylate5. The experiment was conducted in the same manner as in Example 1, except that BOf was used. As a result, a mixture of cis and trans α-
Promo methyl β-methoxyacrylate 7.21 was obtained.
実施例7
実施例1と同様の操作でβ−メトキシアクリロニトリル
と臭素との反応を行った後、トリエチルアミン6.0f
tを塩化メチレン10rILlに溶かした溶液を添加し
、室温で1時間攪拌した。これ以降の操作は、実施例1
と同様に行い、5.91のシスおよびトランスの混合α
−ブロモ−β−メトキシアクリロニトリルが得られた。Example 7 After reacting β-methoxyacrylonitrile with bromine in the same manner as in Example 1, triethylamine 6.0f
A solution of t dissolved in 10 rILl of methylene chloride was added, and the mixture was stirred at room temperature for 1 hour. The subsequent operations are as follows: Example 1
5.91 cis and trans mixture α
-Bromo-β-methoxyacrylonitrile was obtained.
特許出願人 宇部興産株式会社Patent applicant Ube Industries Co., Ltd.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22333783A JPS60116650A (en) | 1983-11-29 | 1983-11-29 | Production of halogenated vinyl ether |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22333783A JPS60116650A (en) | 1983-11-29 | 1983-11-29 | Production of halogenated vinyl ether |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60116650A true JPS60116650A (en) | 1985-06-24 |
JPH0350740B2 JPH0350740B2 (en) | 1991-08-02 |
Family
ID=16796573
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP22333783A Granted JPS60116650A (en) | 1983-11-29 | 1983-11-29 | Production of halogenated vinyl ether |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60116650A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2703992A1 (en) * | 1993-04-15 | 1994-10-21 | Roussel Uclaf | New process for the preparation of ss-alkoxyacrylic acid |
WO1994024085A1 (en) * | 1993-04-15 | 1994-10-27 | Roussel Uclaf | NOVEL METHOD FOR PREPARING β-ALKOXY ACRYLIC ACID |
-
1983
- 1983-11-29 JP JP22333783A patent/JPS60116650A/en active Granted
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2703992A1 (en) * | 1993-04-15 | 1994-10-21 | Roussel Uclaf | New process for the preparation of ss-alkoxyacrylic acid |
WO1994024085A1 (en) * | 1993-04-15 | 1994-10-27 | Roussel Uclaf | NOVEL METHOD FOR PREPARING β-ALKOXY ACRYLIC ACID |
US5744635A (en) * | 1993-04-15 | 1998-04-28 | Roussel Uclaf | Preparation process for beta-alkoxy acrylic acid |
Also Published As
Publication number | Publication date |
---|---|
JPH0350740B2 (en) | 1991-08-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6949668B2 (en) | Process for producing 5-(3-cyanophenyl)-3-formylbenzoic acid compound | |
JP3085722B2 (en) | Method for producing alkylene carbonate | |
JPS6330448A (en) | Manufacture of chlorocarboxylic acid chloride | |
JPS61158947A (en) | Optically active 2-(4-hydroxyphenoxy)propionic acid | |
JPS60116650A (en) | Production of halogenated vinyl ether | |
JPH0128015B2 (en) | ||
JP2622887B2 (en) | Isoxazole derivative and method for producing the same | |
JP2003335735A (en) | Method for producing perfluoroisopropylanilines | |
JPS6112649A (en) | Preparation of aromatic carboxylic acid ester | |
US5202454A (en) | Process for the manufacture of 1-bromoalkyl hydrocarbyl carbonates | |
JPH0352839A (en) | Production of p-or m-tert-butoxybenzaldehyde | |
JP3509421B2 (en) | Method for producing diaryl carbonate | |
CN117683003A (en) | New process for synthesizing englitjing intermediate | |
JP2952344B2 (en) | Method for producing orthocarbonates | |
JP3482786B2 (en) | Preparation of diaryl carbonate | |
WO2000059860A1 (en) | Process for the preparation of vitamin a, intermediates, and process for the preparation of the intermediates | |
JPS60116648A (en) | Production of halogenated acetal | |
KR100593629B1 (en) | Method for preparing acid chloride using triphosgene | |
JPH0369336B2 (en) | ||
SU1625866A1 (en) | Method of producing 5-chloropentanoic acid | |
JP2022110339A (en) | METHOD FOR PRODUCING α-(MERCAPTOMETHYL) ACRYLATE | |
KR100593643B1 (en) | Method for preparing acid chloride using diphosgene | |
JPH01311066A (en) | Production of bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate | |
JPH0327338A (en) | Production of bis(2-hydroxyhexafluoro-2-propyl)-benzene derivative | |
JPS61502332A (en) | 5-Halo-4H-1,3-dioxin-4-one compounds, α-haloacetoacetic esters produced from these compounds, and methods for their production |