JPH07324048A - Production of chlorohydrin derivative - Google Patents
Production of chlorohydrin derivativeInfo
- Publication number
- JPH07324048A JPH07324048A JP14085294A JP14085294A JPH07324048A JP H07324048 A JPH07324048 A JP H07324048A JP 14085294 A JP14085294 A JP 14085294A JP 14085294 A JP14085294 A JP 14085294A JP H07324048 A JPH07324048 A JP H07324048A
- Authority
- JP
- Japan
- Prior art keywords
- chloroacetaldehyde
- group
- reaction
- formula
- chlorohydrin
- 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
Landscapes
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はクロロヒドリン誘導体の
製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing a chlorohydrin derivative.
【０００２】[0002]
【従来の技術】クロロヒドリン誘導体はオキシラン化合
物の原料となるほか、種々の化合物へ変換される有用な
中間体として重要な化合物である。従来、クロロヒドリ
ン誘導体は二重結合を持つ化合物への次亜塩素酸の付加
反応により合成されていたが、この方法では不安定な次
亜塩素酸を発生させる必要があり、操作が困難である。
また、二重結合を持つ反応基質は限られており、しかも
二重結合をもつ化合物の化学構造上の性質から、重合な
どを起こしやすく取り扱いが難しい。BACKGROUND OF THE INVENTION Chlorohydrin derivatives are important compounds as raw materials for oxirane compounds and also as useful intermediates which are converted into various compounds. Conventionally, chlorohydrin derivatives have been synthesized by the addition reaction of hypochlorous acid to a compound having a double bond, but this method requires the generation of unstable hypochlorous acid, which makes the operation difficult.
In addition, the reaction substrate having a double bond is limited, and due to the chemical structural properties of the compound having a double bond, it is liable to cause polymerization and the like and is difficult to handle.
【０００３】[0003]
【発明が解決しようとする課題】したがって、クロロヒ
ドリン誘導体を得るための取り扱いが容易で簡便な方法
が待たれている。Therefore, an easy and convenient method for obtaining a chlorohydrin derivative has been awaited.
【０００４】[0004]
【課題を解決するための手段】本発明者は、上記観点か
ら鋭意研究の結果、簡便な方法で収率良く種々のクロロ
ヒドリン誘導体を製造する方法を見出し、本発明に至っ
た。すなわち、本発明はクロロアセトアルデヒドと特定
のグリニャール試薬を反応させることを特徴とする一般
式〔１〕で表わされる化合物の製法に関する。As a result of earnest research from the above viewpoint, the present inventor has found a method for producing various chlorohydrin derivatives with a simple method and a high yield, and arrived at the present invention. That is, the present invention relates to a process for producing a compound represented by the general formula [1], which comprises reacting chloroacetaldehyde with a specific Grignard reagent.
【化１】 （式中、Ｒはアリール基、置換基を有するアリール基又
はピリジル基を示す）[Chemical 1] (In the formula, R represents an aryl group, an aryl group having a substituent or a pyridyl group)
【０００５】一般式〔１〕で表わされる化合物の製法は
概略を示すと次のようになる。The outline of the method for producing the compound represented by the general formula [1] is as follows.
【化２】 [Chemical 2]
【０００６】ここで、ＲＭｇＸにおいて、ＸはＣｌ，Ｂ
ｒ，Ｉ等のハロゲン原子を示す。Ｒの具体例としてはフ
ェニル基、２−ピリジル基、３−ピリジル基、４−ピリ
ジル基、１−ナフチル基、２−ナフチル基、２−メチル
−１−ナフチル基、４−メチル−１−ナフチル基、又は
２−フルオロフェニル基、３−フルオロフェニル基、４
−フルオロフェニル基、２−クロロフェニル基、３−ク
ロロフェニル基、４−クロロフェニル基、２−メチルフ
ェニル基、３−メチルフェニル基、４−メチルフェニル
基、２−メトキシフェニル基、３−メトキシフェニル
基、４−メトキシフェニル基、２，３−ジフルオロフェ
ニル基、２，４−ジフルオロフェニル基、２，５−ジフ
ルオロフェニル基、２，６−ジフルオロフェニル基、
３，４−ジフルオロフェニル基、３，５−ジフルオロフ
ェニル基、２，３−ジクロロフェニル基、２，４−ジク
ロロフェニル基、２，５−ジクロロフェニル基、２，６
−ジクロロフェニル基、３，５−ジクロロフェニル基、
２−フルオロ−５−メチルフェニル基、３−フルオロ−
２−メチルフェニル基、３−フルオロ−４−メチルフェ
ニル基、３−フルオロ−６−メチルフェニル基、４−フ
ルオロ−２−メチルフェニル基、４−フルオロ−３−メ
チルフェニル基、３−クロロ−６−メチルフェニル基、
３−フルオロ−４−メトキシフェニル基、３−フルオロ
−６−メトキシフェニル基等のハロゲン原子、メチル
基、メトキシ基が１〜５の位置で置換したフェニル基が
挙げられる。Here, in RMgX, X is Cl, B
A halogen atom such as r or I is shown. Specific examples of R include phenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 1-naphthyl group, 2-naphthyl group, 2-methyl-1-naphthyl group, 4-methyl-1-naphthyl group. Group, or 2-fluorophenyl group, 3-fluorophenyl group, 4
-Fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group,
3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6
-Dichlorophenyl group, 3,5-dichlorophenyl group,
2-fluoro-5-methylphenyl group, 3-fluoro-
2-methylphenyl group, 3-fluoro-4-methylphenyl group, 3-fluoro-6-methylphenyl group, 4-fluoro-2-methylphenyl group, 4-fluoro-3-methylphenyl group, 3-chloro- 6-methylphenyl group,
Examples thereof include a phenyl group in which a halogen atom such as a 3-fluoro-4-methoxyphenyl group and a 3-fluoro-6-methoxyphenyl group, a methyl group, and a methoxy group are substituted at positions 1 to 5.
【０００７】クロロアセトアルデヒドは市販のクロロア
セトアルデヒド水溶液からの蒸留又はクロロアセトアル
デヒド３量体の酸触媒熱分解反応により得られる。ここ
で酸触媒としてはｐ−トルエンスルホン酸、ドデシルベ
ンゼンスルホン酸が用いられ、触媒使用量としては０．
５〜３０％の間で任意に選ばれる。Chloroacetaldehyde can be obtained by distillation from a commercially available aqueous solution of chloroacetaldehyde or by acid-catalyzed thermal decomposition reaction of chloroacetaldehyde trimer. Here, p-toluenesulfonic acid and dodecylbenzenesulfonic acid are used as the acid catalyst, and the amount of the catalyst used is 0.
It is arbitrarily selected between 5 and 30%.
【０００８】また、ＲＭｇＸとクロロアセトアルデヒド
との反応において、溶媒はジエチルエーテル、ジブチル
エーテル、ジメトキシエタン等のエーテル類、テトラヒ
ドロフラン、ジオキサンなどが使用される。反応温度
は、２０〜１００℃の範囲で任意に選ばれ、反応生成物
は、蒸留又はカラムクロマトグラフィ−により精製され
る。In the reaction of RMgX with chloroacetaldehyde, ethers such as diethyl ether, dibutyl ether and dimethoxyethane, tetrahydrofuran, dioxane and the like are used as the solvent. The reaction temperature is arbitrarily selected within the range of 20 to 100 ° C., and the reaction product is purified by distillation or column chromatography.
【０００９】[0009]
【実施例】以下に具体例を例示し、本発明を説明する。EXAMPLES The present invention will be described with reference to specific examples.
【００１０】製造例１ クロロアセトアルデヒド〔３〕
の製造 攪拌機、温度計及び蒸留装置（受器にテトラヒドロフラ
ン７．８ｇをあらかじめ仕込んでおいた。）を備えた１
００ｍｌのフラスコにクロロアセトアルデヒド３量体を
８．７ｇ（０．０４ｍｏｌ）、ドデシルベンゼンスルホ
ン酸０．４ｇを仕込み加熱した。９０℃までの留出物を
取ったところ収率９０％でクロロアセトアルデヒドを得
た。Production Example 1 Chloroacetaldehyde [3]
Of a stirrer, thermometer and distillation apparatus (tetrahydrofuran into a receiver 7.8g I had was charged in advance.) With a 1
A 00 ml flask was charged with 8.7 g (0.04 mol) of chloroacetaldehyde trimer and 0.4 g of dodecylbenzenesulfonic acid and heated. When the distillate up to 90 ° C. was taken, chloroacetaldehyde was obtained with a yield of 90%.
【００１１】製造例２ クロロアセトアルデヒド〔３〕
の製造 攪拌機、温度計及び蒸留装置（受器にテトラヒドロフラ
ン１２．０ｇをあらかじめ仕込んでおいた。）を備えた
１００ｍｌのフラスコに４０％クロロアセトアルデヒド
水溶液５０．０ｇ（０．２５ｍｏｌ）を仕込み、蒸留し
た。沸点８３〜８５℃の留分を取り、収率６０％でクロ
ロアセトアルデヒドを得た。Production Example 2 Chloroacetaldehyde [3]
In a 100 ml flask equipped with a stirrer, a thermometer, and a distillation apparatus (tetrahydrofuran 12.0 g was charged in advance in a receiver), 40% chloroacetaldehyde aqueous solution (50.0 g, 0.25 mol) was charged and distilled. . A fraction having a boiling point of 83 to 85 ° C was taken to obtain chloroacetaldehyde with a yield of 60%.
【００１２】実施例１ クロロヒドリン誘導体〔１〕
（Ｒ＝３−クロロフェニル基）の製造 通常の方法で得た３−クロロフェニルマグネシウムクロ
リド０．１０ｍｏｌを含むテトラヒドロフラン溶液に製
造例１で得たクロロアセトアルデヒド７．８５ｇ（０．
１０ｍｏｌ）のテトラヒドロフラン溶液を５０℃に保ち
ながら滴下した。滴下後、５０℃で１時間攪拌した。反
応終了後、希硫酸で中和した後、溶媒を留去し、ベンゼ
ンで抽出した。減圧下濃縮し、残渣をカラムクロマトグ
ラフィー（２００メッシュのシリカゲル、展開溶媒：ベ
ンゼン）で精製し、収率８０％でクロロヒドリン誘導体
を得た。Example 1 Chlorohydrin derivative [1]
Production of (R = 3-chlorophenyl group) 7.85 g (0.8%) of the chloroacetaldehyde obtained in Production Example 1 was added to a tetrahydrofuran solution containing 0.10 mol of 3-chlorophenylmagnesium chloride obtained by a usual method.
A tetrahydrofuran solution (10 mol) was added dropwise while maintaining the temperature at 50 ° C. After the dropping, the mixture was stirred at 50 ° C. for 1 hour. After completion of the reaction, the reaction mixture was neutralized with diluted sulfuric acid, the solvent was distilled off, and the mixture was extracted with benzene. After concentration under reduced pressure, the residue was purified by column chromatography (200 mesh silica gel, developing solvent: benzene) to obtain a chlorohydrin derivative with a yield of 80%.
【００１３】実施例２ クロロヒドリン誘導体〔１〕
（Ｒ＝フェニル）の製造 通常の方法で得た３−フェニルマグネシウムクロリド
０．１０ｍｏｌを含むテトラヒドロフラン溶液に製造例
２で得たクロロアセトアルデヒド７．８５ｇ（０．１０
ｍｏｌ）のテトラヒドロフラン溶液を５０℃に保ちなが
ら滴下した。滴下後、５０℃で１時間攪拌した。反応終
了後、希硫酸で中和した後、溶媒を留去し、ベンゼンで
抽出した。減圧下濃縮し、残渣をカラムクロマトグラフ
ィー（２００メッシュのシリカゲル、展開溶媒：ベンゼ
ン）で精製し、収率７８％でクロロヒドリン誘導体を得
た。Example 2 Chlorohydrin derivative [1]
Production of (R = phenyl) 7.85 g (0.10) of the chloroacetaldehyde obtained in Production Example 2 was added to a tetrahydrofuran solution containing 0.10 mol of 3-phenylmagnesium chloride obtained by a usual method.
A tetrahydrofuran solution of (mol) was added dropwise while maintaining the temperature at 50 ° C. After the dropping, the mixture was stirred at 50 ° C. for 1 hour. After completion of the reaction, the reaction mixture was neutralized with diluted sulfuric acid, the solvent was distilled off, and the mixture was extracted with benzene. After concentration under reduced pressure, the residue was purified by column chromatography (200 mesh silica gel, developing solvent: benzene) to obtain a chlorohydrin derivative with a yield of 78%.
【００１４】つぎに、実施例１及び実施例２と同様の製
造方法を用いて得られた各種のクロロヒドリン誘導体を
第１表に示す。Next, Table 1 shows various chlorohydrin derivatives obtained by using the same manufacturing method as in Examples 1 and 2.
【表１】 [Table 1]
【００１５】[0015]
【発明の効果】本発明は、取り扱いが容易な原料を用い
たクロロヒドリン誘導体の簡便な製造方法である。INDUSTRIAL APPLICABILITY The present invention is a simple method for producing a chlorohydrin derivative using a raw material that is easy to handle.
Claims (2)
薬を反応させることを特徴とする化学式〔１〕 【化１】 （式中、Ｒはアリール基、置換基を有するアリール基又
はピリジル基を示す）で表わされるクロロヒドリン誘導
体の製造方法。1. A chemical formula [1] comprising reacting chloroacetaldehyde with a Grignard reagent. (In the formula, R represents an aryl group, an aryl group having a substituent or a pyridyl group), and a method for producing the chlorohydrin derivative.
分解反応により得られるクロロアセトアルデヒドを用い
ることを特徴とする特許請求の範囲第１項記載の製造方
法。2. The production method according to claim 1, wherein chloroacetaldehyde obtained by an acid-catalyzed thermal decomposition reaction of a chloroacetaldehyde trimer is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14085294A JPH07324048A (en) | 1994-05-30 | 1994-05-30 | Production of chlorohydrin derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14085294A JPH07324048A (en) | 1994-05-30 | 1994-05-30 | Production of chlorohydrin derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07324048A true JPH07324048A (en) | 1995-12-12 |
Family
ID=15278242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14085294A Pending JPH07324048A (en) | 1994-05-30 | 1994-05-30 | Production of chlorohydrin derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07324048A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627701A (en) * | 2019-11-25 | 2019-12-31 | 凯莱英生命科学技术(天津)有限公司 | Continuous preparation method of 2-aminopyrrole-3-carboxylic acid ethyl ester |
-
1994
- 1994-05-30 JP JP14085294A patent/JPH07324048A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627701A (en) * | 2019-11-25 | 2019-12-31 | 凯莱英生命科学技术(天津)有限公司 | Continuous preparation method of 2-aminopyrrole-3-carboxylic acid ethyl ester |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Effective date: 20040309 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
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