JP2001206883A - Method for producing 3,4-methylenedioxymandelic acid - Google Patents
Method for producing 3,4-methylenedioxymandelic acidInfo
- Publication number
- JP2001206883A JP2001206883A JP2000304530A JP2000304530A JP2001206883A JP 2001206883 A JP2001206883 A JP 2001206883A JP 2000304530 A JP2000304530 A JP 2000304530A JP 2000304530 A JP2000304530 A JP 2000304530A JP 2001206883 A JP2001206883 A JP 2001206883A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- reaction
- methylenedioxybenzene
- methylenedioxymandelic
- producing
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、１，２−メチレン
ジオキシベンゼンから３，４−メチレンジオキシマンデ
ル酸を製造する方法に関するものである。３，４−メチ
レンジオキシマンデル酸は、医薬、農薬等の合成原料や
一般化粧品香料として用いられるヘリオトロピンの原料
として有用な化合物である。TECHNICAL FIELD The present invention relates to a method for producing 3,4-methylenedioxymandelic acid from 1,2-methylenedioxybenzene. 3,4-Methylenedioxymandelic acid is a compound useful as a raw material for heliotropin used as a synthetic raw material for medicines, agricultural chemicals and the like, and as a general cosmetic flavor.
【０００２】[0002]
【従来の技術】硫酸やリン酸等の強酸の存在下、１，２
−メチレンジオキシベンゼンとグリオキシル酸を反応さ
せて３，４−メチレンジオキシマンデル酸を製造する方
法は既に知られている（例えば、特開昭５４−９５５７
３号公報，Ｐｅｒｆｕｍｅ＆Ｆｌａｖｏｕｒｉｓｔ，１
４，１３（１９８９））。しかしながら、上記の方法に
おいては、生成する３，４−メチレンジオキシマンデル
酸が本反応系では不溶性であるために結晶として析出し
てしまい、反応の進行と共に反応液は高粘度化又は固化
し攪拌が極めて困難となってしまっていた。更に、本反
応は発熱反応であるため、反応液が高粘度化又は固化し
てしまうと、反応液全体の冷却が困難となってしまい、
部分的に液温が上昇して副生成物が生じ３，４−メチレ
ンジオキシマンデル酸の選択率が低下してしまうという
問題があった。特に、その現象は、反応のスケールをア
ップさせた際に顕著に現われた。また、特開昭５４−９
５５７３号公報には、反応は好ましくは溶剤なしで行う
が、必要ならば、蟻酸又は酢酸等の添加が反応に有利な
影響を及ぼすことが記載されている。しかしながら、そ
の具体的な添加量については何ら記載されていなかっ
た。そこで我々が本反応について鋭意検討を行ったとこ
ろ、意外にも、３，４−メチレンジオキシマンデル酸の
生成速度や選択率は、１，２−メチレンジオキシベンゼ
ンに対する有機酸の添加量に大きく影響されること、そ
して有機酸の最適な添加量が存在することを見出した。2. Description of the Related Art In the presence of a strong acid such as sulfuric acid or phosphoric acid, 1,2
A method for producing 3,4-methylenedioxymandelic acid by reacting -methylenedioxybenzene with glyoxylic acid is already known (for example, Japanese Patent Application Laid-Open No. 54-9557).
No. 3, Perfume & Flavorist, 1
4, 13 (1989)). However, in the above-mentioned method, the generated 3,4-methylenedioxymandelic acid is insoluble in the present reaction system and precipitates as crystals, and as the reaction proceeds, the reaction solution becomes highly viscous or solidified and stirred. Had become extremely difficult. Furthermore, since this reaction is an exothermic reaction, if the reaction solution is increased in viscosity or solidified, it becomes difficult to cool the entire reaction solution,
There was a problem that the liquid temperature was partially increased to produce by-products and the selectivity of 3,4-methylenedioxymandelic acid was reduced. In particular, the phenomenon became remarkable when the scale of the reaction was increased. Also, Japanese Patent Application Laid-Open No. 54-9 / 1979
No. 5,573, describes that the reaction is preferably carried out without solvent, but if necessary the addition of formic acid or acetic acid or the like has a beneficial effect on the reaction. However, there is no description about the specific addition amount. Therefore, when we conducted intensive studies on the present reaction, surprisingly, the production rate and selectivity of 3,4-methylenedioxymandelic acid were significantly larger than the amount of organic acid added to 1,2-methylenedioxybenzene. It was found that it was affected and that there was an optimal amount of organic acid added.
【０００３】[0003]
【発明が解決しようとする課題】本発明の課題は、即
ち、１，２−メチレンジオキシベンゼンとグリオキシル
酸を反応させて、高選択率で３，４−メチレンジオキシ
マンデル酸を製造することが出来、更には、反応のスケ
ールをアップさせた際にも適用出来得る、工業的に好適
な３，４−メチレンジオキシマンデル酸の製造法を提供
するものである。An object of the present invention is to produce 3,4-methylenedioxymandelic acid with high selectivity by reacting 1,2-methylenedioxybenzene with glyoxylic acid. Further, the present invention provides an industrially suitable method for producing 3,4-methylenedioxymandelic acid, which can be applied even when the scale of the reaction is increased.
【０００４】[0004]
【課題を解決するための手段】本発明の目的は、強酸の
存在下、１，２−メチレンジオキシベンゼンとグリオキ
シル酸を反応させて３，４−メチレンジオキシマンデル
酸を製造する方法において、有機酸を１，２−メチレン
ジオキシベンゼン１ｋｇに対して１００〜１２００ｍｌ
存在させることを特徴とする、３，４−メチレンジオキ
シマンデル酸の製造法によって解決される。An object of the present invention is to provide a method for producing 3,4-methylenedioxymandelic acid by reacting 1,2-methylenedioxybenzene with glyoxylic acid in the presence of a strong acid. 100-1200 ml of organic acid per 1 kg of 1,2-methylenedioxybenzene
The problem is solved by a process for producing 3,4-methylenedioxymandelic acid, characterized by being present.
【０００５】[0005]
【発明の実施の形態】本発明の反応において使用する強
酸としては、好ましくは硫酸、リン酸等の無機酸類、更
に好ましくは硫酸が使用される。また、これら強酸は、
７０重量％以上の水溶液を使用することが好ましい。そ
の使用量は、１，２−メチレンジオキシベンゼン１ｍｏ
ｌに対して好ましくは０．５０〜３．００ｍｏｌ、更に
好ましくは１．００〜２．５０ｍｏｌである。BEST MODE FOR CARRYING OUT THE INVENTION As the strong acid used in the reaction of the present invention, preferably used are inorganic acids such as sulfuric acid and phosphoric acid, more preferably sulfuric acid. Also, these strong acids
It is preferable to use an aqueous solution of 70% by weight or more. The amount used is 1 mol of 1,2-methylenedioxybenzene.
It is preferably from 0.50 to 3.00 mol, more preferably from 1.00 to 2.50 mol, based on 1.
【０００６】本発明の反応において使用するグリオキシ
ル酸としては、固体（一水和物）でも４０重量％以上の
水溶液でも使用することが出来る。その使用量は、１，
２−メチレンジオキシベンゼン１ｍｏｌに対して好まし
くは０．８〜２．０ｍｏｌ、更に好ましくは１．０〜
１．５ｍｏｌである。The glyoxylic acid used in the reaction of the present invention may be a solid (monohydrate) or an aqueous solution of 40% by weight or more. Its usage is 1,
0.8 to 2.0 mol, preferably 1.0 to 2.0 mol, per 1 mol of 2-methylenedioxybenzene.
1.5 mol.
【０００７】本発明の反応において使用する有機酸とし
ては、酸性条件において安定で反応を阻害しないもので
あれば特に限定されず、例えば、蟻酸、酢酸、プロピオ
ン酸、ｎ−酪酸、イソ酪酸、ｎ−吉草酸等の脂肪族カル
ボン酸類；トリフルオロ酢酸、ジクロロ酢酸等のハロゲ
ン化脂肪族カルボン酸類が挙げられるが、好ましくは脂
肪族カルボン酸類、更に好ましくは酢酸が使用される。
これら有機酸は、単独又は二種以上を混合して使用して
も良い。The organic acid used in the reaction of the present invention is not particularly limited as long as it is stable under acidic conditions and does not inhibit the reaction. For example, formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-butyric acid, Aliphatic carboxylic acids such as valeric acid; halogenated aliphatic carboxylic acids such as trifluoroacetic acid and dichloroacetic acid, and the like, preferably aliphatic carboxylic acids, and more preferably acetic acid.
These organic acids may be used alone or in combination of two or more.
【０００８】前記有機酸の使用量は、１，２−メチレン
ジオキシベンゼン１ｋｇに対して好ましくは１００〜１
２００ｍｌ、更に好ましくは１００〜１０００ｍｌ、特
に好ましくは１００〜５００ｍｌである。使用量が１０
０ｍｌよりも少ないと、反応液の攪拌性が非常に悪くな
るために、部分的に液温が上昇して副生成物が生じ目的
物の選択率が低下してしまうという問題があり、又、１
２００ｍｌよりも多いと、反応速度が極めて遅くなり、
反応に長時間を有してしまうと共に、目的物の選択率が
低下してしまうという問題があった。The amount of the organic acid to be used is preferably 100 to 1 with respect to 1 kg of 1,2-methylenedioxybenzene.
The volume is 200 ml, more preferably 100 to 1000 ml, particularly preferably 100 to 500 ml. 10 used
If the amount is less than 0 ml, the stirring property of the reaction solution becomes very poor, so that there is a problem that the temperature of the solution is partially increased, by-products are generated, and the selectivity of the target product is reduced. 1
If the amount is more than 200 ml, the reaction speed becomes extremely slow,
There is a problem that the reaction takes a long time and the selectivity of the target decreases.
【０００９】本発明の反応は、例えば、窒素又はアルゴ
ン等の不活性ガスの雰囲気にて、１，２−メチレンジオ
キシベンゼン及び有機酸（１，２−メチレンジオキシベ
ンゼン１ｋｇに対して１００〜１２００ｍｌ）の混合液
に、グリオキシル酸と強酸を添加する等の方法によって
行われる。その際の反応温度は好ましくは−２０〜１０
℃、更に好ましくは−１０〜５℃である。また、反応
は、通常、常圧下で行うが、必要ならば加圧又は減圧下
で行っても良い。In the reaction of the present invention, for example, 1,2-methylenedioxybenzene and an organic acid (100 to 1 kg of 1,2-methylenedioxybenzene are reacted in an atmosphere of an inert gas such as nitrogen or argon). (1200 ml) to the mixed solution of glyoxylic acid and a strong acid. The reaction temperature at that time is preferably -20 to 10
° C, more preferably -10 to 5 ° C. The reaction is usually performed under normal pressure, but may be performed under increased or reduced pressure, if necessary.
【００１０】また得られた生成物は、例えば、反応終了
後に適当な量の塩基を加えて中和した後に適当な溶媒に
よって抽出され、カラムクロマトグラフィー、蒸留、再
結晶等の一般的な方法によって分離精製される。The obtained product is neutralized by adding an appropriate amount of a base after the completion of the reaction, extracted with an appropriate solvent, and subjected to a general method such as column chromatography, distillation and recrystallization. It is separated and purified.
【００１１】[0011]
【実施例】次に、実施例を挙げて本発明を具体的に説明
するが、本発明の範囲はこれらに限定されるものではな
い。なお、生成した３，４−メチレンジオキシマンデル
酸の選択率は、消費した１，２−メチレンジオキシベン
ゼン基準（モル換算）で算出した。EXAMPLES Next, the present invention will be described specifically with reference to examples, but the scope of the present invention is not limited to these examples. The selectivity of the generated 3,4-methylenedioxymandelic acid was calculated on the basis of the consumed 1,2-methylenedioxybenzene (in terms of mol).
【００１２】実施例１ 内容積５００ｍｌの平底セパラブルフラスコに、窒素雰
囲気下、１，２−メチレンジオキシベンゼン５０．０ｇ
（０．４０９ｍｏｌ）及び酢酸２０ｍｌ（１，２−メチ
レンジオキシベンゼンに対する酢酸の使用量は４００ｍ
ｌ／ｋｇ）を加えた後、攪拌しながら０℃まで冷却し
た。次いで、４０重量％グリオキシル酸水溶液８３．４
ｇ（０．４５１ｍｏｌ）と９６重量％硫酸８５．８ｇ
（０．８４０ｍｏｌ）との混合液を滴下した後、０℃で
９時間攪拌した。なお、反応途中の攪拌はスムーズに行
えた。その後、２８重量％アンモニア水１０２．０ｇ
（１．６７７ｍｏｌ）をゆるやかに添加して中和した。
次いで、２−ブタノン１００ｍｌを加えて６０℃まで加
熱し、生成した３，４−メチレンジオキシマンデル酸を
２−ブタノン層（有機層）に抽出した。高速液体クロマ
トグラフィーにより有機層を分析したところ、１，２−
メチレンジオキシベンゼンの転化率は９５％であり、
３，４−メチレンジオキシマンデル酸の選択率は９１％
であった。Example 1 50.0 g of 1,2-methylenedioxybenzene was placed in a 500 ml flat bottom separable flask under a nitrogen atmosphere.
(0.409 mol) and 20 ml of acetic acid (the amount of acetic acid used is 400 m for 1,2-methylenedioxybenzene).
1 / kg) and then cooled to 0 ° C. with stirring. Then, 83.4% by weight aqueous solution of glyoxylic acid 83.4.
g (0.451 mol) and 85.8 g of 96% by weight sulfuric acid
(0.840 mol), and the mixture was stirred at 0 ° C. for 9 hours. The stirring during the reaction was performed smoothly. Then, 102.0 g of 28% by weight ammonia water
(1.677 mol) was added slowly to neutralize.
Next, 100 ml of 2-butanone was added and heated to 60 ° C., and the generated 3,4-methylenedioxymandelic acid was extracted into a 2-butanone layer (organic layer). When the organic layer was analyzed by high performance liquid chromatography, 1,2-
The conversion of methylenedioxybenzene is 95%,
Selectivity for 3,4-methylenedioxymandelic acid is 91%
Met.
【００１３】実施例２ 内容積５００ｍｌの平底セパラブルフラスコに、窒素雰
囲気下、１，２−メチレンジオキシベンゼン５０．０ｇ
（０．４０９ｍｏｌ）及び酢酸２０ｍｌ（１，２−メチ
レンジオキシベンゼンに対する酢酸の使用量は４００ｍ
ｌ／ｋｇ）を加えた後、攪拌しながら０℃まで冷却し
た。次いで、４５重量％グリオキシル酸水溶液７５．２
１ｇ（０．４５７ｍｏｌ）と９６重量％硫酸６８．８５
ｇ（０．６７４ｍｏｌ）との混合液を滴下した後、０℃
で２３時間攪拌した。なお、反応途中の攪拌はスムーズ
に行えた。その後、２８重量％アンモニア水８２．１ｇ
（１．３５０ｍｏｌ）をゆるやかに添加して中和した。
次いで、２−ブタノン２００ｍｌを加えて６０℃まで加
熱し、生成した３，４−メチレンジオキシマンデル酸を
２−ブタノン層（有機層）に抽出した。高速液体クロマ
トグラフィーにより有機層を分析したところ、１，２−
メチレンジオキシベンゼンの転化率は９７％であり、
３，４−メチレンジオキシマンデル酸の選択率は９０％
であった。Example 2 50.0 g of 1,2-methylenedioxybenzene was placed in a 500 ml flat bottom separable flask under a nitrogen atmosphere.
(0.409 mol) and 20 ml of acetic acid (the amount of acetic acid used is 400 m for 1,2-methylenedioxybenzene)
1 / kg) and then cooled to 0 ° C. with stirring. Next, a 75% by weight aqueous solution of glyoxylic acid 75.2 was used.
1 g (0.457 mol) and 68.85% by weight of 96% by weight sulfuric acid
g (0.674 mol), and then dropped at 0 ° C.
For 23 hours. The stirring during the reaction was performed smoothly. Then, 82.1 g of 28% by weight ammonia water
(1.350 mol) was added slowly to neutralize.
Next, 200 ml of 2-butanone was added and the mixture was heated to 60 ° C., and the generated 3,4-methylenedioxymandelic acid was extracted into a 2-butanone layer (organic layer). When the organic layer was analyzed by high performance liquid chromatography, 1,2-
The conversion of methylenedioxybenzene is 97%,
90% selectivity for 3,4-methylenedioxymandelic acid
Met.
【００１４】実施例３〜７及び比較例１〜２ 実施例１において、１，２−メチレンジオキシベンゼン
に対する酢酸の使用量、反応温度及び反応時間を変えた
こと以外は、実施例１と同様に反応を行った。結果を表
１に示す。Examples 3 to 7 and Comparative Examples 1 and 2 The same procedure as in Example 1 was carried out except that the amount of acetic acid, the reaction temperature and the reaction time were changed with respect to 1,2-methylenedioxybenzene. The reaction was performed. Table 1 shows the results.
【００１５】[0015]
【表１】 ＊：１，２−メチレンジオキシベンゼンに対する酢酸の
使用量 ＭＤＢ：１，２−メチレンジオキシベンゼン ＭＤＭＡ：３，４−メチレンジオキシマンデル酸[Table 1] *: Amount of acetic acid used for 1,2-methylenedioxybenzene MDB: 1,2-methylenedioxybenzene MDMA: 3,4-methylenedioxymandelic acid
【００１６】[0016]
【発明の効果】本発明により、１，２−メチレンジオキ
シベンゼンとグリオキシル酸を反応させて、高選択率で
３，４−メチレンジオキシマンデル酸を製造することが
出来、更には、反応のスケールをアップさせた際にも適
用出来得る、工業的に好適な３，４−メチレンジオキシ
マンデル酸の製造法を提供することが出来る。According to the present invention, 3,4-methylenedioxymandelic acid can be produced at a high selectivity by reacting 1,2-methylenedioxybenzene with glyoxylic acid. An industrially suitable method for producing 3,4-methylenedioxymandelic acid, which can be applied even when the scale is increased, can be provided.
Claims (3)
ベンゼンとグリオキシル酸を反応させて３，４−メチレ
ンジオキシマンデル酸を製造する方法において、有機酸
を１，２−メチレンジオキシベンゼン１ｋｇに対して１
００〜１２００ｍｌ存在させることを特徴とする、３，
４−メチレンジオキシマンデル酸の製造法。1. A method for producing 3,4-methylenedioxymandelic acid by reacting 1,2-methylenedioxybenzene with glyoxylic acid in the presence of a strong acid, wherein the organic acid is 1,2-methylenedioxybenzene. 1 for 1 kg of benzene
3, characterized in that it is present in an amount of
A method for producing 4-methylenedioxymandelic acid.
シベンゼン１ｍｏｌに対して０．５０〜３．００ｍｏｌ
である請求項１記載の３，４−メチレンジオキシマンデ
ル酸の製造法。2. A strong acid is used in an amount of 0.50 to 3.00 mol per 1 mol of 1,2-methylenedioxybenzene.
The method for producing 3,4-methylenedioxymandelic acid according to claim 1, wherein
メチレンジオキシマンデル酸の製造法。3. The method according to claim 1, wherein the strong acid is sulfuric acid.
A method for producing methylenedioxymandelic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000304530A JP2001206883A (en) | 1999-11-16 | 2000-10-04 | Method for producing 3,4-methylenedioxymandelic acid |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32611699 | 1999-11-16 | ||
| JP11-326116 | 1999-11-16 | ||
| JP2000304530A JP2001206883A (en) | 1999-11-16 | 2000-10-04 | Method for producing 3,4-methylenedioxymandelic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001206883A true JP2001206883A (en) | 2001-07-31 |
Family
ID=26572080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000304530A Pending JP2001206883A (en) | 1999-11-16 | 2000-10-04 | Method for producing 3,4-methylenedioxymandelic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001206883A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2830861A1 (en) * | 2001-10-15 | 2003-04-18 | Rhodia Chimie Sa | Production of alkoxymandelic acids, e.g. intermediates for alkoxyaromatic aldehydes, comprises reacting alkoxyaromatic compound with glyoxylic acid in presence of strong protonic acid |
| CN110684008A (en) * | 2018-07-04 | 2020-01-14 | 天津大学 | Method and device for synthesizing 3, 4-methylenedioxymandelic acid by emulsification process |
| CN110862369A (en) * | 2018-08-28 | 2020-03-06 | 淄博泰典新材料有限公司 | Method and device for synthesizing 3, 4-methylenedioxymandelic acid by improved emulsification |
| CN110862370A (en) * | 2018-08-28 | 2020-03-06 | 淄博泰典新材料有限公司 | Method and device for synthesizing 3, 4-methylenedioxymandelic acid by enhanced emulsification |
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2000
- 2000-10-04 JP JP2000304530A patent/JP2001206883A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2830861A1 (en) * | 2001-10-15 | 2003-04-18 | Rhodia Chimie Sa | Production of alkoxymandelic acids, e.g. intermediates for alkoxyaromatic aldehydes, comprises reacting alkoxyaromatic compound with glyoxylic acid in presence of strong protonic acid |
| CN110684008A (en) * | 2018-07-04 | 2020-01-14 | 天津大学 | Method and device for synthesizing 3, 4-methylenedioxymandelic acid by emulsification process |
| CN110684008B (en) * | 2018-07-04 | 2023-01-20 | 天津大学 | Method and device for synthesizing 3, 4-methylenedioxymandelic acid by emulsification process |
| CN110862369A (en) * | 2018-08-28 | 2020-03-06 | 淄博泰典新材料有限公司 | Method and device for synthesizing 3, 4-methylenedioxymandelic acid by improved emulsification |
| CN110862370A (en) * | 2018-08-28 | 2020-03-06 | 淄博泰典新材料有限公司 | Method and device for synthesizing 3, 4-methylenedioxymandelic acid by enhanced emulsification |
| CN110862370B (en) * | 2018-08-28 | 2023-09-08 | 山东天大泰泽环保科技有限公司 | Method and device for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by enhancing emulsification |
| CN110862369B (en) * | 2018-08-28 | 2023-09-08 | 山东天大泰泽环保科技有限公司 | Method and device for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by improved emulsification |
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