JPH11158096A - Production of alcohols - Google Patents
Production of alcoholsInfo
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- JPH11158096A JPH11158096A JP32569497A JP32569497A JPH11158096A JP H11158096 A JPH11158096 A JP H11158096A JP 32569497 A JP32569497 A JP 32569497A JP 32569497 A JP32569497 A JP 32569497A JP H11158096 A JPH11158096 A JP H11158096A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アルコール類の製
法に関する。詳しくは、グリニア試薬とパラホルムアル
デヒドとの反応により医薬および農薬の中間体として有
用なアルコール類を製造する方法に関する。[0001] The present invention relates to a method for producing alcohols. More specifically, the present invention relates to a method for producing alcohols useful as intermediates of medicines and agricultural chemicals by reacting a Grignard reagent with paraformaldehyde.
【０００２】[0002]
【従来の技術】医薬および農薬の中間体として有用なα
−ヒドロキシメチルスチレン誘導体の製造法として、特
開平９−３０９９８号には、α−ハロゲノスチレン誘導
体とマグネシウムの反応により生成するグリニア試薬と
パラホルムアルデヒドを反応させる方法が提案されてい
る。2. Description of the Related Art α useful as an intermediate of pharmaceuticals and pesticides
As a method for producing a -hydroxymethylstyrene derivative, Japanese Patent Application Laid-Open No. 9-30998 proposes a method in which a Grignard reagent produced by the reaction of an α-halogenostyrene derivative with magnesium is reacted with paraformaldehyde.
【０００３】[0003]
【発明が解決しようとする課題】而して、この方法は、
得られた反応液からα−ヒドロキシメチルスチレン誘導
体を蒸留により分離しようとすると、生成物がスチレン
骨格を有するため、蒸留時に重合し、収率が低下するた
め、工業的に有利な製造方法とは言えなかった。本発明
は、かかる事情に鑑み成されたものであって、α−ハロ
ゲノスチレン誘導体のグリニア試薬とパラホルムアルデ
ヒドの反応液から、α−ヒドロキシメチルスチレン誘導
体を収率良く製造する方法を提供することを目的とす
る。SUMMARY OF THE INVENTION
If an attempt is made to separate the α-hydroxymethylstyrene derivative from the obtained reaction solution by distillation, since the product has a styrene skeleton, it is polymerized during distillation, and the yield is reduced. I could not say it. The present invention has been made in view of such circumstances, and it is an object of the present invention to provide a method for producing an α-hydroxymethylstyrene derivative from a reaction solution of a Grignard reagent of an α-halogenostyrene derivative and paraformaldehyde with high yield. Aim.
【０００４】[0004]
【課題を解決するための手段】本発明者らは上記課題を
解決するために鋭意検討した結果、α−ハロゲノスチレ
ン誘導体のグリニア試薬とパラホルムアルデヒドとの反
応物を加水分解後、アルカリ洗浄を行ってから蒸留を行
うことによって、蒸留時の重合を大幅に低減できること
を見いだし、本発明を完成するに至った。即ち、本発明
の要旨は、下記一般式（１）Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. It has been found that by performing distillation after that, polymerization during distillation can be greatly reduced, and the present invention has been completed. That is, the gist of the present invention is represented by the following general formula (1)
【０００５】[0005]
【化３】 （式中、Ｘはハロゲン原子を示し、Ａは電子吸引基で置
換されていてもよいベンゼン環を示す。）で表されるα
−ハロゲノスチレン誘導体とマグネシウムの反応により
得られるグリニア試薬とパラホルムアルデヒドを反応さ
せ、次いで酸性水溶液を加えた後の反応液を、 水相と有機相に分液する第１分離工程、 第１分離工程で得られた有機相を、アルカリ水溶液で
洗浄し、液のｐＨをアルカリ性に調整した後、水相と有
機相に分液する第２分離工程、 第２分離工程で得られた有機相を蒸留することを特徴
とする下記一般式（２）Embedded image (In the formula, X represents a halogen atom, and A represents a benzene ring which may be substituted with an electron-withdrawing group.)
A first separation step in which a Grignard reagent obtained by the reaction of a halogenostyrene derivative and magnesium is reacted with paraformaldehyde, and then the reaction solution after the addition of the acidic aqueous solution is separated into an aqueous phase and an organic phase; Washing the organic phase obtained in the above with an aqueous alkali solution, adjusting the pH of the solution to alkaline, and then separating the aqueous phase and the organic phase, and distilling the organic phase obtained in the second separation step The following general formula (2):
【０００６】[0006]
【化４】 （式中、ＸおよびＡは一般式（１）と同一の意義を有
す。）で表されるアルコール類の製造方法に存する。Embedded image (Wherein X and A have the same meaning as in the general formula (1)).
【０００７】[0007]
【発明の実施の形態】以下、本発明の好ましい実施態様
について説明する。上記一般式（１）において、Ａは置
換基として、電子吸引基を有していてもよい。電子吸引
基としては、メチル基、エチル基等のアルキル基、フッ
素原子、塩素原子、ヨウ素原子等のハロゲン原子、トリ
フルオロメチル基、ニトロ基、シアノ基等が挙げられ
る。Ａは好ましくは無置換のベンゼン環、あるいはハロ
ゲン原子により置換されたベンゼン環である。Ｘはハロ
ゲン原子を示し、臭素原子、ヨウ素原子が特に好まし
い。DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below. In the general formula (1), A may have an electron withdrawing group as a substituent. Examples of the electron-withdrawing group include an alkyl group such as a methyl group and an ethyl group, a halogen atom such as a fluorine atom, a chlorine atom, and an iodine atom, a trifluoromethyl group, a nitro group, and a cyano group. A is preferably an unsubstituted benzene ring or a benzene ring substituted by a halogen atom. X represents a halogen atom, and a bromine atom and an iodine atom are particularly preferred.
【０００８】本発明方法で、一般式（１）で表されるα
−ハロゲノスチレン誘導体とマグネシウムとを反応させ
て、グリニア試薬を調製する方法は常法に従って行われ
る。即ち、一般式（１）で表されるα−ハロゲノスチレ
ン誘導体を溶媒とマグネシウムの混合物中に徐々に滴下
し、５〜１００℃、好ましくは１０〜７０℃で反応さ
せ、添加終了後、更に５分〜３時間反応を続行して、グ
リニア反応を完結させる。反応の際、反応を進行させる
ために少量のヨウ素等を添加してもよい。反応に使用す
る溶媒としては、ジエチルエーテル、テトラヒドロフラ
ン、ジブチルエーテル等のエーテル系溶媒あるいは上記
エーテル系溶媒とベンゼン、トルエン、キシレン等の芳
香族炭化水素の混合溶媒が挙げられる。溶媒の使用量は
一般式（１）のα−ハロゲノスチレン誘導体に対して１
〜１２倍（容量）、好ましくは１〜８倍である。In the method of the present invention, α represented by the general formula (1)
A method for preparing a Grignard reagent by reacting a halogenostyrene derivative with magnesium is carried out according to a conventional method. That is, the α-halogenostyrene derivative represented by the general formula (1) is gradually dropped into a mixture of a solvent and magnesium, and reacted at 5 to 100 ° C, preferably 10 to 70 ° C. Continue the reaction for minutes to 3 hours to complete the Grignard reaction. During the reaction, a small amount of iodine or the like may be added to advance the reaction. Examples of the solvent used in the reaction include ether solvents such as diethyl ether, tetrahydrofuran, and dibutyl ether, or mixed solvents of the above ether solvents and aromatic hydrocarbons such as benzene, toluene, and xylene. The amount of the solvent used is 1 to the α-halogenostyrene derivative of the general formula (1).
１２12 times (capacity), preferably 1 to 8 times.
【０００９】次いで得られたグリニア試薬をパラホルム
アルデヒドと反応させる。この反応により、下式（３）
で示されるα−ヒドロキシメチルスチレン誘導体のハロ
ゲノマグネシウム複合体が生成する。Next, the obtained Grignard reagent is reacted with paraformaldehyde. By this reaction, the following formula (3)
A halogeno magnesium complex of an α-hydroxymethylstyrene derivative represented by the formula (1) is produced.
【化５】 （式中、Ｘ及びＡは一般式（１）と同一の意義を有
す。）Embedded image (In the formula, X and A have the same meaning as in the general formula (1).)
【００１０】パラホルムアルデヒドの使用量は、一般式
（１）で表されるα−ハロゲノスチレン誘導体に対し
て、５０〜３００当量、好ましくは８０〜１５０当量で
ある。この反応はグリニア試薬を含む反応液にパラホル
ムアルデヒドを添加するか、あるいはパラホルムアルデ
ヒドを溶媒に懸濁させて、グリニア試薬を含む反応液を
添加して行うことができる。パラホルムアルデヒドを懸
濁する際の溶媒としては、上記グリニア試薬調製で使用
する溶媒およびベンゼン、トルエン、キシレン等の芳香
族炭化水素系溶媒が挙げられ、溶媒使用量は一般式
（１）のα−ハロゲノスチレン誘導体に対して１〜１２
倍（容量）、好ましくは１〜８倍である。反応は、−１
０〜１００℃、好ましくは２０℃〜７０℃の温度で、１
５分〜１０時間、好ましくは３０分〜５時間行われる。The amount of paraformaldehyde used is 50 to 300 equivalents, preferably 80 to 150 equivalents, based on the α-halogenostyrene derivative represented by the general formula (1). This reaction can be carried out by adding paraformaldehyde to a reaction solution containing a Grignard reagent or by suspending paraformaldehyde in a solvent and adding a reaction solution containing a Grignard reagent. Examples of the solvent for suspending paraformaldehyde include a solvent used in the above-mentioned Grignard reagent preparation and an aromatic hydrocarbon solvent such as benzene, toluene and xylene. The amount of the solvent used is α- of the general formula (1). 1 to 12 with respect to the halogenostyrene derivative
Times (capacity), preferably 1 to 8 times. The reaction is -1
At a temperature of 0-100 ° C, preferably 20-70 ° C,
The reaction is performed for 5 minutes to 10 hours, preferably for 30 minutes to 5 hours.
【００１１】反応終了後、反応液に酸性水溶液を添加
し、中間体として生成する前記（３）式のα−ヒドロキ
シメチルスチレン誘導体のハロゲノマグネシウム複合体
を加水分解して、目的とする一般式（２）のα−ヒドロ
キシメチルスチレン誘導体が生成する。加水分解は通常
０〜７０℃、好ましくは５〜５０℃の温度範囲で行わ
れ、反応時間は５分〜５時間、好ましくは３０分〜２時
間である。酸性水溶液としては、塩酸水溶液、硫酸水溶
液、塩化アンモニウム水溶液等が使用される。加水分解
終了後は、分液によって水相と一般式（２）で表される
アルコール類を含む有機相を分離する（第１分離工
程）。After completion of the reaction, an acidic aqueous solution is added to the reaction solution to hydrolyze the halogenomagnesium complex of the α-hydroxymethylstyrene derivative of the formula (3), which is formed as an intermediate, to obtain the desired compound of the general formula (3) The α-hydroxymethylstyrene derivative of 2) is produced. The hydrolysis is usually performed at a temperature in the range of 0 to 70 ° C, preferably 5 to 50 ° C, and the reaction time is 5 minutes to 5 hours, preferably 30 minutes to 2 hours. As the acidic aqueous solution, an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, an aqueous ammonium chloride solution, or the like is used. After completion of the hydrolysis, an aqueous phase and an organic phase containing an alcohol represented by the general formula (2) are separated by liquid separation (first separation step).
【００１２】次いで、得られた有機相に、アルカリ水溶
液を加えて、通常０〜７０℃、好ましくは５℃〜５０℃
の範囲で攪拌し該有機相のｐＨを７以上、好ましくはｐ
Ｈ１０〜１３の範囲のアルカリ性に調整すると共にアル
カリ水溶液により洗浄する。使用するアルカリとしては
水酸化ナトリウム、水酸化カリウム、アンモニア等が挙
げられる。次いで分液によって、水相と一般式（２）で
表されるアルコール類を含む有機相を分離する（第２分
離工程）。さらに、必要あれば、第２分離工程で得られ
た有機相に水を添加、攪拌して有機相を洗浄し、ｐＨを
６〜９に調整した後、再度分液して一般式（２）で表さ
れるアルコール類を含む有機相を分取する。有機相の水
洗浄は、必要に応じ繰り返し行っても良い。最後に該有
機相を濃縮、蒸留して一般式（２）で表されるアルコー
ル類を精製し、分取する。蒸留は減圧下で行うことが好
ましく、一般式（２）で表されるアルコール類が熱的に
不安定な場合には薄膜蒸留等の方法を採ることもでき
る。Next, an aqueous alkaline solution is added to the obtained organic phase, and the mixture is usually added at 0 to 70 ° C., preferably at 5 to 50 ° C.
And the pH of the organic phase is adjusted to 7 or more, preferably p
It is adjusted to an alkalinity in the range of H10 to H13 and washed with an aqueous alkali solution. Examples of the alkali used include sodium hydroxide, potassium hydroxide, and ammonia. Next, an aqueous phase and an organic phase containing an alcohol represented by the general formula (2) are separated by liquid separation (second separation step). Further, if necessary, water is added to the organic phase obtained in the second separation step, the organic phase is washed by stirring, the pH is adjusted to 6 to 9, and the liquid is separated again to obtain the compound represented by the general formula (2) An organic phase containing an alcohol represented by the formula (1) is collected. Washing of the organic phase with water may be repeated as necessary. Finally, the organic phase is concentrated and distilled to purify and fractionate the alcohol represented by the general formula (2). The distillation is preferably carried out under reduced pressure. When the alcohol represented by the general formula (2) is thermally unstable, a method such as thin film distillation can be employed.
【００１３】[0013]
【実施例】以下、本発明を実施例についてさらに詳細に
説明するが、本発明はその要旨を越えない限り、以下の
実施例に限定されるものではない。なお、実施例中、
「％」は「重量％」を示す。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. In the examples,
“%” Indicates “% by weight”.
【００１４】実施例１ フラスコに窒素雰囲気下、マグネシウム３．６９ｇ
（０．１５ｍｏｌ）、テトラヒドロフラン（ＴＨＦ）３
０ｍｌ、トルエン３０ｍｌ、ヨウ素０．０６ｇを加え
て、水浴で冷却下攪拌を行いながら、３０℃で３−クロ
ロ−α−ブロモスチレン３０ｇ（０．１４ｍｏｌ）をＴ
ＨＦ１５ｍｌとトルエン１５ｍｌに溶解した液を３０分
かけて滴下する。さらに１時間反応を行って、グリニア
反応を完結させた。次いで、反応液を濾過して液中のマ
グネシウムを除去した。パラホルムアルデヒド４．５６
ｇ（０．１５ｍｏｌ）をＴＨＦ３０ｍｌとトルエン３０
ｍｌに懸濁させた液に、マグネシウムを除去したグリニ
ア反応液を３０℃で２時間かけて滴下し、さらに２時間
反応を行って、反応を完結させた。反応終了後、４０℃
以下で単蒸留を行い、ＴＨＦを一部留去した。次いで、
反応液に２５℃で、３規定塩酸水溶液を１２０ｍｌ加え
て攪拌した後、分液して有機相１１０ｍｌを分取した。
この有機相に１％ＮａＯＨ水溶液を１２０ｍｌ添加して
ｐＨを約１２に調整し、１時間攪拌後、分液により有機
相１１０ｍｌを分取した。次いで、水１２０ｍｌを添加
し、攪拌洗浄した後分液する操作を２回行って有機相を
分取した。反応収率は７０％（対３−クロロ−α−ブロ
モスチレン）であった。得られた有機相を１１０℃、
０．１ｍｍＨｇの条件で単蒸留を行ったところ、反応で
生成していた３−クロロ−α−ヒドロキシメチルスチレ
ンはほとんど重合しないで回収できた。蒸留前後での回
収率は約９６％（留出９０％、釜残６％）であった。Example 1 3.69 g of magnesium was placed in a flask under a nitrogen atmosphere.
(0.15 mol), tetrahydrofuran (THF) 3
0 ml, 30 ml of toluene and 0.06 g of iodine were added, and 30 g (0.14 mol) of 3-chloro-α-bromostyrene was added at 30 ° C. while stirring under cooling in a water bath.
A solution dissolved in 15 ml of HF and 15 ml of toluene is added dropwise over 30 minutes. The reaction was further performed for 1 hour to complete the Grignard reaction. Next, the reaction solution was filtered to remove magnesium in the solution. Paraformaldehyde 4.56
g (0.15 mol) in 30 ml of THF and 30 ml of toluene
The Grignard reaction solution from which magnesium had been removed was added dropwise at 30 ° C. over 2 hours to the liquid suspended in ml, and the reaction was further carried out for 2 hours to complete the reaction. After the reaction, 40 ° C
Simple distillation was performed below, and part of THF was distilled off. Then
120 ml of a 3N aqueous hydrochloric acid solution was added to the reaction solution at 25 ° C., and the mixture was stirred and then separated to collect 110 ml of an organic phase.
To this organic phase, 120 ml of a 1% aqueous NaOH solution was added to adjust the pH to about 12, and after stirring for 1 hour, 110 ml of the organic phase was separated by liquid separation. Next, 120 ml of water was added, the operation of separating with stirring and washing was performed twice, and the organic phase was separated. The reaction yield was 70% (vs. 3-chloro-α-bromostyrene). 110 ° C.
When simple distillation was performed under the condition of 0.1 mmHg, 3-chloro-α-hydroxymethylstyrene produced by the reaction could be recovered almost without polymerization. The recovery before and after distillation was about 96% (distillation 90%, bottom 6%).
【００１５】比較例１ 実施例１と同様に反応、加水分解、分液して、３−クロ
ロ−α−ヒドロキシルメチルスチレンを含む反応液（有
機相）を得た。該有機相を水洗した後、１１０℃、０．
１ｍｍＨｇの条件で単蒸留を行ったところ、反応で生成
していた３−クロロ−α−ヒドロキシメチルスチレンの
約３０％が重合して高分子量化していた。Comparative Example 1 The reaction, hydrolysis and liquid separation were carried out in the same manner as in Example 1 to obtain a reaction solution (organic phase) containing 3-chloro-α-hydroxylmethylstyrene. After the organic phase was washed with water, it was dried at 110 ° C., at 0.
When simple distillation was performed under the conditions of 1 mmHg, about 30% of 3-chloro-α-hydroxymethylstyrene produced by the reaction was polymerized to have a high molecular weight.
【００１６】[0016]
【発明の効果】本発明によれば、医薬および農薬の中間
体として有用なアルコール類を蒸留によって精製する際
の重合による収率の低下を大幅に低減でき、蒸留収率を
向上できるので、工業的価値は非常に大きい。Industrial Applicability According to the present invention, it is possible to greatly reduce the decrease in yield due to polymerization in the purification of alcohols useful as intermediates of pharmaceuticals and agricultural chemicals by distillation, and to improve the distillation yield. The target value is very large.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 河村 茂徳 北九州市八幡西区黒崎城石１番１号 三菱 化学株式会社黒崎事業所内 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Shigenori Kawamura 1-1 Kurosaki Castle Stone, Yawatanishi-ku, Kitakyushu City Inside the Mitsubishi Chemical Corporation Kurosaki Office
Claims (2)
換されていてもよいベンゼン環を示す。）で表されるα
−ハロゲノスチレン誘導体とマグネシウムの反応により
得られるグリニア試薬とパラホルムアルデヒドを反応さ
せ、次いで酸性水溶液を加えた後の反応液を、 水相と有機相に分液する第１分離工程、 第１分離工程で得られた有機相を、アルカリ水溶液で
洗浄し、液のｐＨをアルカリ性に調整した後、水相と有
機相に分液する第２分離工程、 第２分離工程で得られた有機相を蒸留することを特徴
とする下記一般式（２） 【化２】 （式中、ＸおよびＡは一般式（１）と同一の意義を有
す。）で表されるアルコール類の製造方法。[Claim 1] The following general formula (1) (In the formula, X represents a halogen atom, and A represents a benzene ring which may be substituted with an electron-withdrawing group.)
A first separation step in which a Grignard reagent obtained by the reaction of a halogenostyrene derivative and magnesium is reacted with paraformaldehyde, and then the reaction solution after the addition of the acidic aqueous solution is separated into an aqueous phase and an organic phase; Washing the organic phase obtained in the above with an aqueous alkali solution, adjusting the pH of the solution to alkaline, and then separating the aqueous phase and the organic phase, and distilling the organic phase obtained in the second separation step The following general formula (2): (Wherein X and A have the same meaning as in formula (1)).
洗浄した後蒸留することを特徴とする請求項１記載のア
ルコールの製造方法。2. The method according to claim 1, wherein the organic phase obtained in the second separation step is washed with water and then distilled.
Priority Applications (1)
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| JP32569497A JP3779452B2 (en) | 1997-11-27 | 1997-11-27 | Method for producing alcohols |
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| JP32569497A JP3779452B2 (en) | 1997-11-27 | 1997-11-27 | Method for producing alcohols |
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| JPH11158096A true JPH11158096A (en) | 1999-06-15 |
| JP3779452B2 JP3779452B2 (en) | 2006-05-31 |
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| JP32569497A Expired - Fee Related JP3779452B2 (en) | 1997-11-27 | 1997-11-27 | Method for producing alcohols |
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