JPH10120674A - Production of 2-methyl-3-(3,4-methylenedioxyphenyl) acrylic aldehyde - Google Patents
Production of 2-methyl-3-(3,4-methylenedioxyphenyl) acrylic aldehydeInfo
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- JPH10120674A JPH10120674A JP29925596A JP29925596A JPH10120674A JP H10120674 A JPH10120674 A JP H10120674A JP 29925596 A JP29925596 A JP 29925596A JP 29925596 A JP29925596 A JP 29925596A JP H10120674 A JPH10120674 A JP H10120674A
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- reaction
- methylenedioxyphenyl
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、香料物質として知
られている２−メチル−３−（３，４−メチレンジオキ
シフェニル）プロパナール［以下ピペロニルプロパナー
ルという］の合成中間体として有用な２−メチル−３−
（３，４−メチレンジオキシフェニル）アクリルアルデ
ヒド［以下ピペロニリデンプロパナールという］の新規
な製法に関する。[0001] The present invention relates to a synthetic intermediate of 2-methyl-3- (3,4-methylenedioxyphenyl) propanal [hereinafter referred to as piperonylpropanal] which is known as a fragrance substance. Useful 2-methyl-3-
The present invention relates to a novel process for producing (3,4-methylenedioxyphenyl) acrylaldehyde [hereinafter referred to as piperonylidenepropanal].
【０００２】さらに詳しくは、本発明は、ヘリオトロー
プ様の香気を有する香料化合物として使用されている下
記式（Ａ）More specifically, the present invention relates to a compound represented by the following formula (A) which is used as a perfume compound having a heliotrope-like odor.
【０００３】[0003]
【化４】 で表されるピペロニルプロパナールの合成中間体として
有用な下記式（１）Embedded image The following formula (1) useful as a synthetic intermediate of piperonyl propanal represented by
【０００４】[0004]
【化５】 式中、波線はシス体あるいはトランス体を示す、で表さ
れるピペロニリデンプロパナールの新規な製法に関す
る。Embedded image In the formula, a wavy line represents a cis-form or a trans-form, and relates to a novel process for producing piperonylidenepropanal represented by the formula:
【０００５】[0005]
【従来の技術】従来、上記式（１）で表されるピペロニ
リデンプロパナールの合成法に関しては、例えば、下記
反応工程図で示される方法が知られている［Ｊ．Ｏｒ
ｇ．Ｃｈｅｍ．,３９（９），１２４２〜１２４７（１
９７４）］。2. Description of the Related Art Conventionally, as a method for synthesizing piperonylidenepropanal represented by the above formula (1), for example, a method shown in the following reaction process diagram is known [J. Or
g. Chem. , 39 (9), 1242-1247 (1
974)].
【０００６】[0006]
【化６】 Embedded image
【０００７】上記の方法は、オキシ塩化リンとジメチル
ホルムアミドを低温で反応させ、ビルスマイヤー錯体を
調整し、その後、トランス体の上記式（２）の化合物を
加えて７５〜８０℃の温度で反応する第一方法、及び、
さらに高温（スチームバス温度）で反応する第二方法に
より上記式（１）の化合物が合成されている。In the above-mentioned method, phosphorus oxychloride and dimethylformamide are reacted at a low temperature to prepare a Vilsmeier complex, and then a trans-form compound of the above formula (2) is added and the reaction is carried out at a temperature of 75 to 80 ° C. A first method to do, and
The compound of the above formula (1) has been synthesized by a second method of reacting at a higher temperature (steam bath temperature).
【０００８】しかしながら、上記の方法は、上記式
（２）の化合物から上記式（１）の化合物を合成する短
工程の反応であるにもかかわらず、第一方法において
は、上記式（１）の化合物の収率が４８％と低く、ま
た、第二方法においても上記式（１）の化合物の収率は
２３％とさらに低くなり、しかも副生成物である２−メ
チルー３−ジメチルアミノー５、６−メチレンジオキシ
−１−インデンが４７％も生成されており、実用的な方
法とは言い難いなどの解決すべき課題がある。However, the above method is a short-step reaction for synthesizing the compound of the formula (1) from the compound of the formula (2). The yield of the compound of formula (1) is as low as 48% in the second method, and the yield of the compound of formula (1) is as low as 23% in the second method, and the by-product 2-methyl-3-dimethylamino- As much as 47% of 5,6-methylenedioxy-1-indene is produced, and there are problems to be solved, such as being difficult to say as a practical method.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、上記した従
来の製造方法の課題を解決した上記式（１）のピペロニ
リデンプロパナールを好収率で製造する新規な方法を提
供することにある。An object of the present invention is to provide a novel method for producing piperonylidenepropanal of the above formula (1) at a high yield, which solves the above-mentioned problems of the conventional production method. is there.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、上述の従
来の方法における不利益乃至欠点を解決すべく鋭意研究
を行ってきた。その結果、上記式（２）の１−（３、４
−メチレンジオキシフェニル）−１−プロペン［以下、
イソサフロールという］を出発原料として使用し、ホル
ムアミド化合物との混合物中に縮合剤を加え、７０℃以
下の温度で反応することにより、上述の従来技術と比較
して予測もつかない好純度且つ好収率で本発明の上記式
（１）の化合物を短工程の工業的に簡単な操作で有利に
合成できることを見出し、本発明を完成した。The present inventors have intensively studied to solve the disadvantages or disadvantages of the above-mentioned conventional method. As a result, 1- (3,4) in the above equation (2)
-Methylenedioxyphenyl) -1-propene [hereinafter, referred to as
Isosafurol] as a starting material, adding a condensing agent to a mixture with a formamide compound, and reacting at a temperature of 70 ° C. or less, thereby obtaining an unexpectedly high purity and yield compared with the above-mentioned prior art. The present inventors have found that the compound of the formula (1) of the present invention can be advantageously synthesized by a short-step industrially simple operation at a low rate, and have completed the present invention.
【００１１】[0011]
【発明の実施の形態】しかして、本発明によれば、下記
式（２）According to the present invention, the following formula (2)
【００１２】[0012]
【化７】 式中、波線はシス体あるいはトランス体を示す（以下、
同様）、で表されるイソサフロールと下記式（３）Embedded image In the formula, a wavy line indicates a cis form or a trans form (hereinafter, referred to as a cis form or a trans form).
The same), isosafrole represented by the following formula (3)
【００１３】[0013]
【化８】 式中、Ｒ1及びＲ2は同一でも異なってもよく、それぞれ
アルキル基、アリール基あるいは複素環基を示す（以
下、同様）、で表されるホルムアミド化合物中に縮合剤
を加え、７０℃以下の温度で反応させて下記式（１）Embedded image In the formula, R 1 and R 2 may be the same or different and each represents an alkyl group, an aryl group or a heterocyclic group (hereinafter the same), a condensing agent is added to a formamide compound represented by Reaction at the temperature of
【００１４】[0014]
【化９】 式中、波線はシス体あるいはトランス体を示す、で表さ
れるピペロニリデンプロパナールを製造する方法が提供
される。Embedded image In the formula, a wavy line indicates a cis form or a trans form, and a method for producing piperonylidenepropanal represented by the formula:
【００１５】この反応を式で示すと、例えば、下記のよ
うに表すことができる。This reaction can be represented by the following formula, for example.
【００１６】[0016]
【化１０】 Embedded image
【００１７】本発明の上記式（１）のピペロニリデンプ
ロパナールの製造方法を上記反応式に従って、以下にさ
らに詳細に説明する。The process for producing piperonylidenepropanal of the above formula (1) of the present invention will be described in more detail below according to the above reaction formula.
【００１８】出発原料である上記式（２）の化合物は、
例えば、サッサフラス油の主成分である３−（３、４−
メチレンジオキシフェニル）−１−プロペン［以下、サ
フロールという］を水酸化ナトリウム、水酸化カリウム
などの塩基の存在下で異性化することにより容易に入手
することができる。The compound of the above formula (2) as a starting material is
For example, the main component of sassafras oil, 3- (3,4-
It can be easily obtained by isomerizing methylenedioxyphenyl) -1-propene [hereinafter referred to as safrole] in the presence of a base such as sodium hydroxide and potassium hydroxide.
【００１９】上述のようにして得られる上記式（２）の
化合物から本発明の上記式（１）のピペロニリデンプロ
パナールを得るには、例えば、上記式（２）のイソサフ
ロールと上記式（３）のホルムアミド化合物中に縮合剤
を加えて、７０℃以下の温度で反応することにより容易
に行うことができる。In order to obtain piperonylidenepropanal of the above formula (1) of the present invention from the compound of the above formula (2) obtained as described above, for example, isosafrole of the above formula (2) and the above formula It can be easily carried out by adding a condensing agent to the formamide compound of (3) and reacting at a temperature of 70 ° C. or lower.
【００２０】上記反応は、７０℃を越えると副生成物の
２−メチル−３−ジメチルアミノ−５，６−メチレンジ
オキシ−１−インデンの生成量が急激に増加する傾向に
あり、前記式（１）の化合物の収率が低下する。一方、
７０℃以下の場合、副生成物はほとんどみられないが、
反応速度は低下する傾向にある。従って、これらを考慮
して、上記反応は約７０℃〜約５０℃程度の範囲で行う
のが好ましい。In the above reaction, when the temperature exceeds 70 ° C., the amount of by-product 2-methyl-3-dimethylamino-5,6-methylenedioxy-1-indene tends to rapidly increase. The yield of the compound (1) decreases. on the other hand,
When the temperature is 70 ° C. or lower, almost no by-products are observed,
The reaction rate tends to decrease. Therefore, in consideration of these, it is preferable to carry out the above reaction in a range of about 70 ° C to about 50 ° C.
【００２１】また、イソサフロールと上記式（３）のホ
ルムアミド化合物中に縮合剤を滴下して加えることによ
り、反応温度のコントロールが容易となる。The reaction temperature can be easily controlled by adding the condensing agent dropwise to isosafrole and the formamide compound of the above formula (3).
【００２２】反応時間は、反応温度によっても異なる
が、例えば、約２時間〜約６時間程度で十分であるが、
反応温度を７０℃に近い比較的高温範囲の温度を選択す
れば短い反応時間で反応を行うことができ、また、比較
的低い温度範囲を選択すれば長い反応時間が必要になっ
てくる。Although the reaction time varies depending on the reaction temperature, for example, about 2 hours to about 6 hours is sufficient.
If the reaction temperature is selected in a relatively high temperature range close to 70 ° C., the reaction can be performed in a short reaction time, and if a relatively low temperature range is selected, a long reaction time is required.
【００２３】上記反応に用いられる前記式（３）のホル
ムアミド化合物としては、例えば、Ｎ，Ｎ−ジメチルホ
ルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ−メチ
ルホルムアニリド、ホルムアニリド、Ｎ−ホルミルモル
ホリン、Ｎ−フェニルホルムアニリドなどを挙げること
ができる。Examples of the formamide compound of the above formula (3) used in the above reaction include N, N-dimethylformamide, N, N-diethylformamide, N-methylformanilide, formanilide, N-formylmorpholine, -Phenylformanilide and the like.
【００２４】上記反応に使用される前記式（３）のホル
ムアミド化合物の使用量は、例えば、上記式（２）の化
合物１モルに対して約０．５〜約１０モル程度の範囲内
で使用され、より好ましくは、約１〜約５モル程度の範
囲内が適当である。The amount of the formamide compound of the formula (3) used in the above reaction is, for example, within the range of about 0.5 to about 10 mol per 1 mol of the compound of the formula (2). More preferably, the range is about 1 to about 5 mol.
【００２５】上記反応に使用する縮合剤としては、例え
ば、オキシ塩化リン（ＰＯＣｌ3）、ホスゲン（ＣＯＣ
ｌ2）、塩化チオニル（ＳＯＣｌ2）などを挙げることが
できる。これら縮合剤の使用量には特別の制限はなく、
例えば、前記式（２）の化合物１モルに対して、約０．
５〜約３モル程度の範囲内を好ましく例示することがで
きる。Examples of the condensing agent used in the above reaction include phosphorus oxychloride (POCl 3 ), phosgene (COC
l 2 ), thionyl chloride (SOCl 2 ) and the like. There is no particular limitation on the amount of these condensing agents used,
For example, about 0.1 mol per 1 mol of the compound of the formula (2).
A preferred range is about 5 to about 3 moles.
【００２６】反応終了後は常法に従って反応液に水を加
え、ジクロロメタンなどの有機溶媒で抽出して本発明の
前記式（１）の化合物を得ることができる。この粗製の
式（１）の化合物は、再結晶、蒸留などの精製手段を用
いることにより、好収率且つ好純度で容易に合成するこ
とができる。After completion of the reaction, water is added to the reaction solution according to a conventional method, followed by extraction with an organic solvent such as dichloromethane to obtain the compound of the above formula (1) of the present invention. The crude compound of the formula (1) can be easily synthesized in good yield and purity by using purification means such as recrystallization and distillation.
【００２７】[0027]
【実施例】以下に本発明の実施態様につき、実施例及び
参考例を挙げて更に詳細に説明する。EXAMPLES Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples and Reference Examples.
【００２８】参考例１ イソサフロール［式（２）］の合成 サフロールを主成分として含むサッサフラス油６００
ｇ、エチルアルコール５５ｇ及び水酸化カリウム３８ｇ
をフラスコに仕込み、撹拌しながら加熱する。この状態
で約４時間リフラックスして異性化反応を終了する。反
応終了後、エーテル抽出、洗浄、乾燥などの処理をし、
さらに蒸留などの精製手段を用いることにより、純粋な
式（２）のイソサフロール５４５ｇを得た。収率；９１
％。沸点；６３〜７２℃／０．７ｍｍＨｇReference Example 1 Synthesis of isosafrole [formula (2)] Sassafras oil 600 containing safrole as a main component
g, 55 g of ethyl alcohol and 38 g of potassium hydroxide
Is charged into a flask and heated with stirring. In this state, reflux is performed for about 4 hours to complete the isomerization reaction. After the completion of the reaction, ether extraction, washing, drying and other treatments,
Further, 545 g of pure isosafrole of the formula (2) was obtained by using a purification means such as distillation. Yield; 91
%. Boiling point: 63-72 ° C / 0.7mmHg
【００２９】実施例１ ピペロニリデンプロパナール［式（１）］の合成 フラスコにイソサフロール２９０ｇ及びジメチルホルム
アミド４３０ｇを仕込み、撹拌しながら６３℃に加熱し
た。次いで、このフラスコの中に３００ｇのオキシ塩化
リン（ＰＯＣｌ3）を３時間要して滴下する。滴下した
後、更に６３〜６５℃の温度に保ちながら４時間撹拌を
おこない反応を続行した。反応終了後、反応液に水を加
え、ジクロロメタンで抽出し、溶媒を回収後、メタノー
ルで再結晶して式（１）の化合物３０５ｇを得た。収
率；９０％。融点；６３〜６５℃。Example 1 Synthesis of Piperonylidenepropanal [Formula (1)] A flask was charged with 290 g of isosafrole and 430 g of dimethylformamide, and heated to 63 ° C. with stirring. Next, 300 g of phosphorus oxychloride (POCl 3 ) is dropped into the flask over a period of 3 hours. After the dropwise addition, the reaction was continued for 4 hours while maintaining the temperature at 63 to 65 ° C. to continue the reaction. After completion of the reaction, water was added to the reaction solution, extracted with dichloromethane, the solvent was recovered, and then recrystallized from methanol to obtain 305 g of a compound of the formula (1). Yield; 90%. Melting point: 63-65 [deg.] C.
【００３０】実施例２〜１２ 表１に示すような反応条件下で、式（２）のイソサフロ
ールと式（３）のホルムアミド化合物と縮合剤より、実
施例１と同様にして、式（１）のピペロニリデンプロパ
ナールを合成した。Examples 2 to 12 Under the reaction conditions shown in Table 1, the compound of formula (1) was prepared in the same manner as in Example 1 from isosafrole of formula (2), a formamide compound of formula (3) and a condensing agent. ) Was synthesized.
【００３１】この場合の式（２）、式（３）及び縮合剤
のモル比は実施例１と同一である。その結果を表１にま
とめて示す。また、本発明の比較例として７０℃以上で
反応した場合の結果を表２に示す。この場合の式
（２）、式（３）及び縮合剤のモル比も実施例１と同一
である。In this case, the molar ratios of the formulas (2) and (3) and the condensing agent are the same as in Example 1. The results are summarized in Table 1. Table 2 shows the results when the reaction was carried out at 70 ° C. or higher as a comparative example of the present invention. In this case, the molar ratios of the formulas (2) and (3) and the condensing agent are the same as in Example 1.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【表２】 [Table 2]
【００３４】[0034]
【発明の効果】本発明によれば、香料物質として知られ
るピペロニルプロパナールの合成中間体であるピペロニ
リデンプロパナールを好純度且つ好収率で製造する新規
な方法を提供することができる。According to the present invention, it is possible to provide a novel method for producing piperonylidenepropanal, which is a synthetic intermediate of piperonylpropanal known as a fragrance substance, with high purity and high yield. it can.
Claims (1)
れる１−（３，４メチレンジオキシフェニル）−１−プ
ロペンと下記式（３） 【化２】 式中、Ｒ1及びＲ2は同一でも異なってもよく、それぞれ
アルキル基、アリール基あるいは複素環基を示す、で表
されるホルムアミド化合物中に縮合剤を加え、７０℃以
下の温度で反応することを特徴とする下記式（１） 【化３】 式中、波線はシス体あるいはトランス体を示す、で表さ
れる２−メチル−３−（３，４メチレンジオキシフェニ
ル）アクリルアルデヒドの製法。[Claim 1] The following formula (2) In the formula, a wavy line indicates a cis form or a trans form, and 1- (3,4 methylenedioxyphenyl) -1-propene represented by the following formula (3): In the formula, R 1 and R 2 may be the same or different and each represents an alkyl group, an aryl group or a heterocyclic group, and a condensing agent is added to the formamide compound and reacted at a temperature of 70 ° C. or less. Wherein the following formula (1): In the formula, a wavy line indicates a cis-form or a trans-form, wherein 2-methyl-3- (3,4 methylenedioxyphenyl) acrylaldehyde is produced.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29925596A JP3771334B2 (en) | 1996-10-24 | 1996-10-24 | Preparation of 2-methyl-3- (3,4-methylenedioxyphenyl) acrylaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29925596A JP3771334B2 (en) | 1996-10-24 | 1996-10-24 | Preparation of 2-methyl-3- (3,4-methylenedioxyphenyl) acrylaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10120674A true JPH10120674A (en) | 1998-05-12 |
| JP3771334B2 JP3771334B2 (en) | 2006-04-26 |
Family
ID=17870173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29925596A Expired - Fee Related JP3771334B2 (en) | 1996-10-24 | 1996-10-24 | Preparation of 2-methyl-3- (3,4-methylenedioxyphenyl) acrylaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3771334B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005105774A1 (en) * | 2004-04-30 | 2005-11-10 | Endura S.P.A. | Process for the preparation of 3-(3,4-methylenedioxyphenyl)-2-methylpropanal |
| WO2008099882A1 (en) * | 2007-02-15 | 2008-08-21 | Ube Industries, Ltd. | 2-methyl-3-(3,4-methylenedioxyphenyl)propanal, and method for production thereof |
| EP2119714A1 (en) * | 2007-03-07 | 2009-11-18 | Ube Industries, Ltd. | Method of retaining the quality of 2-methyl-3-(3,4-methylenedioxyphenyl)propanal and process for producing the same |
-
1996
- 1996-10-24 JP JP29925596A patent/JP3771334B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005105774A1 (en) * | 2004-04-30 | 2005-11-10 | Endura S.P.A. | Process for the preparation of 3-(3,4-methylenedioxyphenyl)-2-methylpropanal |
| WO2008099882A1 (en) * | 2007-02-15 | 2008-08-21 | Ube Industries, Ltd. | 2-methyl-3-(3,4-methylenedioxyphenyl)propanal, and method for production thereof |
| US8168809B2 (en) | 2007-02-15 | 2012-05-01 | Ube Industries, Ltd. | 2-methyl-3-(3,4-methylenedioxyphenyl)propanal, and method for production thereof |
| EP2562173A1 (en) * | 2007-02-15 | 2013-02-27 | Ube Industries, Ltd. | 2-methyl-3-(3,4.methylenedioxyphenyl) propanal, and method for production thereof |
| JP5446272B2 (en) * | 2007-02-15 | 2014-03-19 | 宇部興産株式会社 | 2-Methyl-3- (3,4-methylenedioxyphenyl) propanal and method for producing the same |
| EP2119714A1 (en) * | 2007-03-07 | 2009-11-18 | Ube Industries, Ltd. | Method of retaining the quality of 2-methyl-3-(3,4-methylenedioxyphenyl)propanal and process for producing the same |
| EP2119714A4 (en) * | 2007-03-07 | 2011-05-25 | Ube Industries | Method of retaining the quality of 2-methyl-3-(3,4-methylenedioxyphenyl)propanal and process for producing the same |
| US8039649B2 (en) | 2007-03-07 | 2011-10-18 | Ube Industries, Ltd. | Method of retaining the quality of 2-methyl-3-(3,4-methylenedioxyphenyl)propanal and process for producing the same |
| US8344166B2 (en) | 2007-03-07 | 2013-01-01 | Ube Industries, Ltd. | Method of retaining the quality of 2-methyl-3-(3,4-methylenedioxyphenyl) propanal and process for producing the same |
| TWI391384B (en) * | 2007-03-07 | 2013-04-01 | Ube Industries | A method for maintaining the quality of 2-methyl-3-(3,4-methylenedioxyphenyl) propanal, and a method for producing the same |
| US8450508B2 (en) | 2007-03-07 | 2013-05-28 | Ube Industries, Ltd. | Method of retaining the quality of 2-methyl-3-(3,4-methylenedioxyphenyl)propanal and process for producing the same |
| JP2013227590A (en) * | 2007-03-07 | 2013-11-07 | Ube Industries Ltd | Method for producing 2-methyl-3-(3,4-methylenedioxyphenyl)propanal composition |
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