JP2005239620A - Method for producing 1-acetoxy-3-(3,4-methylenedioxyphenyl)propene derivative - Google Patents
Method for producing 1-acetoxy-3-(3,4-methylenedioxyphenyl)propene derivative Download PDFInfo
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Abstract
Description
本発明は、香料、医薬品、農薬、有機合成薬品の中間体として有用である１−アセトキシ−３−（３，４−メチレンジオキシフェニル）プロペン誘導体の製造に関する。特に前記式（１）においてＲ１が水素原子であり、Ｒ２がメチル基である１−アセトキシ−３−（３，４−メチレンジオキシフェニル）プロペン誘導体は、加水分解により香料として有用な２−ホルミル−３−（３，４−メチレンジオキシフェニル）プロパン（非特許文献１）に誘導することが出来る。 The present invention relates to the production of 1-acetoxy-3- (3,4-methylenedioxyphenyl) propene derivatives that are useful as intermediates for fragrances, pharmaceuticals, agricultural chemicals, and organic synthetic chemicals. In particular, the 1-acetoxy-3- (3,4-methylenedioxyphenyl) propene derivative in which R 1 is a hydrogen atom and R 2 is a methyl group in the formula (1) is useful as a fragrance by hydrolysis. -Formyl-3- (3,4-methylenedioxyphenyl) propane (Non-patent Document 1).
本発明の１−アセトキシ−３−（３，４−メチレンジオキシフェニル）プロペン誘導体は新規な化合物である。この主骨格である１−アセトキシ−３−フェニルプロペン誘導体の合成法としては、例えば、非許文献２に、ｏ−ジメトキシベンゼンとアルケニリデンジアセテートとを、三フッ化ホウ素エーテル錯体で活性化した四塩化チタンの存在下に反応させて、１−アセトキシ−３−（３，４−ジメトキシフェニル）プロペンを合成する方法が開示されている。また、特許文献１にも、イソブチルベンゼンを同様に反応させて１−アセトキシ−３−（３，４−イソブチルフェニル）プロペンを合成する方法が開示されている。しかし、同反応を１，２−メチレンジオキシベンゼンに適応した場合、三フッ化ホウ素エーテル錯体で活性化した四塩化チタンにより１，２−メチレンジオキシベンゼンの分解反応が進行し、目的物の収率は４３．１％と不充分であった（比較例１）。
更に１，２−メチレンジオキシベンゼンの分解を防ぐためにアルケニリデンジアセテート １モルに対し、０．１モルの四塩化チタンを用いて反応を試みたが１−アセトキシ−３−（３，４−メチレンジオキシフェニル）プロペンの収率は９．８％であった（比較例２）。
The 1-acetoxy-3- (3,4-methylenedioxyphenyl) propene derivative of the present invention is a novel compound. As a method for synthesizing this main skeleton 1-acetoxy-3-phenylpropene derivative, for example, in Non-Patent Document 2, o-dimethoxybenzene and alkenylidene diacetate were activated with a boron trifluoride ether complex. A method of synthesizing 1-acetoxy-3- (3,4-dimethoxyphenyl) propene by reacting in the presence of titanium tetrachloride is disclosed. Patent Document 1 also discloses a method of synthesizing 1-acetoxy-3- (3,4-isobutylphenyl) propene by reacting isobutylbenzene in the same manner. However, when this reaction is applied to 1,2-methylenedioxybenzene, the decomposition reaction of 1,2-methylenedioxybenzene proceeds by titanium tetrachloride activated with boron trifluoride ether complex, The yield was inadequate at 43.1% (Comparative Example 1).
Furthermore, in order to prevent decomposition of 1,2-methylenedioxybenzene, an attempt was made to react with 1 mol of alkenylidene diacetate using 0.1 mol of titanium tetrachloride, but 1-acetoxy-3- (3,4- The yield of methylenedioxyphenyl) propene was 9.8% (Comparative Example 2).
特許文献２には、ｔ−ブチルベンゼンとメタクロレインとアセチルクロライドを化学量論量のルイス酸存在下に反応させて１−アセトキシ−２−メチル−３−（４−ｔ−ブチルフェニル）プロペンを合成する方法が開示されているが、四塩化チタンを用いた場合は収率が４６．２％、三フッ化ホウ素エーテル錯体を用いた場合は収率２．３％であり、何れも収率が非常に低かった。
本発明の課題は、香料、医薬品、農薬、有機合成薬品の中間体として有用である新規１−アセトキシ−３−（３，４−メチレンジオキシフェニル）プロペン誘導体を簡便な方法によって、１，２−メチレンジオキシベンゼンから収率良く得る、工業的に好適な製法を提供することである。 An object of the present invention is to produce a novel 1-acetoxy-3- (3,4-methylenedioxyphenyl) propene derivative, which is useful as an intermediate for fragrances, pharmaceuticals, agricultural chemicals and organic synthetic chemicals, by a simple method. -To provide an industrially suitable production method obtained from methylenedioxybenzene in good yield.
本発明者らは、前記の課題を解決するために検討した結果、新規な１−アセトキシ−３−（３，４−メチレンジオキシフェニル）プロペン誘導体の製法を見出し、本発明を完成した。
即ち、本発明は次の通りである。
As a result of investigations to solve the above problems, the present inventors have found a method for producing a novel 1-acetoxy-3- (3,4-methylenedioxyphenyl) propene derivative and completed the present invention.
That is, the present invention is as follows.
硫酸及び／又はスルホン酸の存在下、下式(１)で示される１，２−メチレンジオキシベンゼンと 1,2-methylenedioxybenzene represented by the following formula (1) in the presence of sulfuric acid and / or sulfonic acid
下式(２)で示されるアルケニリデンジアセテートを反応させることを特徴とする It is characterized by reacting an alkenylidene diacetate represented by the following formula (2)
（式中、ＡｃＯはアセトキシ基を表わし、Ｒ１及びＲ２は水素原子又は炭素原子数１〜１０のアルキル基を表わし、互いに結合して環を形成しても良い。また、本化合物は、立体異性体を含む。） (In the formula, AcO represents an acetoxy group, R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and may combine with each other to form a ring. Including stereoisomers.)
下式（３）で表わされる１−アセトキシ−３−（３，４−メチレンジオキシフェニル）プロペン誘導体の製造法に関するものである。 The present invention relates to a method for producing a 1-acetoxy-3- (3,4-methylenedioxyphenyl) propene derivative represented by the following formula (3).
（式中、ＡｃＯ、Ｒ１及びＲ２は前記と同義である。また、本化合物は、立体異性体を含む。） (In the formula, AcO, R 1 and R 2 have the same meanings as described above. In addition, this compound includes stereoisomers.)
本発明により、香料、医薬品、農薬、有機合成薬品の中間体として有用である新規１−アセトキシ−３−（３，４−メチレンジオキシフェニル）プロペン誘導体を簡便な方法によって、１，２−メチレンジオキシベンゼンから収率良く得る、工業的に好適な製法を提供することができる。 According to the present invention, a novel 1-acetoxy-3- (3,4-methylenedioxyphenyl) propene derivative, which is useful as an intermediate for fragrances, pharmaceuticals, agricultural chemicals, and organic synthetic chemicals, can be obtained by a simple method. An industrially suitable production method obtained with good yield from dioxybenzene can be provided.
以下、本発明について詳細に説明する。
本発明の前記式（３）で表わされる１−アセトキシ−３−（３，４−メチレンジオキシフェニル）プロペン誘導体の製造は、硫酸及び／又はスルホン酸の存在下、１，２−メチレンジオキシベンゼンと前記の一般式（２）で示されるアルケニリデンジアセテートを反応させることにより行うことが出来る。
なお、本発明は、反応を妨げない限り、その他化合物を添加することが出来るが、四塩化チタンは使用されない。
Hereinafter, the present invention will be described in detail.
The 1-acetoxy-3- (3,4-methylenedioxyphenyl) propene derivative represented by the above formula (3) of the present invention is produced in the presence of sulfuric acid and / or sulfonic acid in the presence of 1,2-methylenedioxy. The reaction can be carried out by reacting benzene with the alkenylidene diacetate represented by the general formula (2).
In the present invention, other compounds can be added as long as the reaction is not hindered, but titanium tetrachloride is not used.
前記式（３）で表わされる１−アセトキシ−３−（３，４−メチレンジオキシフェニル）プロペン誘導体において、Ｒ１及びＲ２は水素原子又は炭素原子数１〜１０のアルキル基を表わし、互いに結合して環を形成しても良い。また、本化合物は、立体異性体を含む。 In the 1-acetoxy-3- (3,4-methylenedioxyphenyl) propene derivative represented by the formula (3), R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, They may combine to form a ring. Moreover, this compound contains a stereoisomer.
ここで、炭素原子数１〜１０のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基などが挙げられるが、好ましくはメチル基である。なお、これらの基は各種異性体を含む。また、Ｒ３とＲ４が互いに結合して出来る環としては、シクロペンタン環、シクロヘキサン環などが挙げられるが、好ましくはシクロヘキサン環である。 Here, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. A methyl group is preferred. These groups include various isomers. Examples of the ring formed by combining R 3 and R 4 with each other include a cyclopentane ring and a cyclohexane ring, with a cyclohexane ring being preferred.
本発明の１，２−メチレンジオキシベンゼンは、市販のものを使用することが出来る。 As the 1,2-methylenedioxybenzene of the present invention, a commercially available product can be used.
本発明で用いられる前記式（２）で表わされるアルケニリデンジアセテートは、市販のものを使用することが出来るが、例えば特許文献１に記載の方法に従い、α，β−不飽和アルデヒドと無水酢酸から調製することも出来る。なお、本化合物は、立体異性体を含む。 As the alkenylidene diacetate represented by the formula (2) used in the present invention, a commercially available product can be used. For example, according to the method described in Patent Document 1, an α, β-unsaturated aldehyde and acetic anhydride are used. Can also be prepared. In addition, this compound contains a stereoisomer.
前記式（２）で表わされるアルケニリデンジアセテートにおいて、Ｒ１及びＲ２は、前記式（３）に記載されたＲ１及びＲ２と同義である。 In alkenyl Niri diacetate represented by the formula (2), R 1 and R 2 have the same meanings as R 1 and R 2 as described in Formula (3).
ここで、炭素原子数１〜１０のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基などが挙げられるが、好ましくはメチル基である。なお、これらの基は各種異性体を含む。また、Ｒ３とＲ４が互いに結合して出来る環としては、シクロペンタン環、シクロヘキサン環などが挙げられるが、好ましくはシクロヘキサン環である。 Here, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. A methyl group is preferred. These groups include various isomers. Examples of the ring formed by combining R 3 and R 4 with each other include a cyclopentane ring and a cyclohexane ring, with a cyclohexane ring being preferred.
アルケニリデンジアセテートの調製に用いられるα，β−不飽和アルデヒドとしては、アクロレイン、メタクロレイン、クロトンアルデヒド、α，β−ジメチルアクロレイン、α−エチルアクロレイン、β−エチルアクロレイン、β−プロピルアクロレイン、α−シクロヘキシルアクロレインなどが挙げられるが、好ましくはアクロレイン、メタクロレイン、クロトンアルデヒドであり、更に好ましくはメタクロレインである。 Examples of α, β-unsaturated aldehyde used for the preparation of alkenylidene diacetate include acrolein, methacrolein, crotonaldehyde, α, β-dimethylacrolein, α-ethylacrolein, β-ethylacrolein, β-propylacrolein, α -Cyclohexyl acrolein and the like can be mentioned, and acrolein, methacrolein and crotonaldehyde are preferable, and methacrolein is more preferable.
本発明で用いられるのメチレンジオキシベンゼンの使用量は、アルケニリデンジアセテート １モルに対して１〜５０モルであり、好ましくは１〜２０モルである。 The amount of methylenedioxybenzene used in the present invention is 1 to 50 mol, preferably 1 to 20 mol, per 1 mol of alkenylidene diacetate.
本発明で用いられる硫酸及び／又はスルホン酸としては、硫酸、メタンスルホン酸、エタンスルホン酸、エタンジスルホン酸、ベンゼンスルホン酸、ベンゼンジスルホン酸、トルエンスルホン酸、ナフタレンスルホン酸、ナフタレンジスルホン酸等が挙げられ、これらの中では硫酸、メタンスルホン酸、トルエンスルホン酸好ましい。これら化合物は市販のものを使用することが出来る。またこれら化合物は水を含んでも良く、その場合、濃度８５〜１００重量％であることが好ましい。 Examples of sulfuric acid and / or sulfonic acid used in the present invention include sulfuric acid, methanesulfonic acid, ethanesulfonic acid, ethanedisulfonic acid, benzenesulfonic acid, benzenedisulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, and the like. Of these, sulfuric acid, methanesulfonic acid, and toluenesulfonic acid are preferred. Commercially available compounds can be used. These compounds may contain water, and in that case, the concentration is preferably 85 to 100% by weight.
前記硫酸及び／又はスルホン酸の使用量は、アルケニリデンジアセテート １モルに対して１モル以下であり、好ましくは０．０１〜１．０モルである。この範囲より使用量が少ないと反応が２４時間では完結せず、多いと過剰量のハロゲン化ホウ素を分解・廃棄するなど煩雑な操作が必要であり工業的なスケールでは適さない。 The usage-amount of the said sulfuric acid and / or sulfonic acid is 1 mol or less with respect to 1 mol of alkenylidene diacetates, Preferably it is 0.01-1.0 mol. If the amount used is less than this range, the reaction is not completed in 24 hours. If the amount is too large, complicated operations such as decomposition and disposal of an excessive amount of boron halide are required, which is not suitable on an industrial scale.
本発明の１−アセトキシ−３−（３，４−メチレンジオキシフェニル）プロペン誘導体の合成反応は、溶媒を使用して行っても良いが、好ましくは無溶媒である。 The synthesis reaction of the 1-acetoxy-3- (3,4-methylenedioxyphenyl) propene derivative of the present invention may be performed using a solvent, but is preferably solventless.
反応温度は反応にあずかる原料物質の種類によって異なるが、−１０〜１５０℃であり、好ましくは０〜１００℃である。 The reaction temperature varies depending on the type of the starting material involved in the reaction, but is −10 to 150 ° C., preferably 0 to 100 ° C.
反応時間は、前記の濃度、温度によって変化するが０．５〜２４時間である。 The reaction time varies depending on the concentration and temperature, but is 0.5 to 24 hours.
この反応は、通常、アルゴン、窒素などの不活性ガス雰囲気、或はこれらガス気流下で行われる。また、用いられる反応圧は通常、常圧である。 This reaction is usually performed in an inert gas atmosphere such as argon or nitrogen, or in a gas stream of these gases. The reaction pressure used is usually atmospheric pressure.
合成された１−アセトキシ−３−（３，４−メチレンジオキシフェニル）プロペン誘導体は、反応終了後、抽出、濃縮、ロ過などの通常の後処理を行い、必要に応じて蒸留、再結晶、各種クロマトグラフィーなどの公知の手段で適宣精製することができる。 The synthesized 1-acetoxy-3- (3,4-methylenedioxyphenyl) propene derivative is subjected to usual post-treatments such as extraction, concentration and filtration after completion of the reaction, followed by distillation and recrystallization as necessary. It can be appropriately purified by known means such as various chromatographies.
以下に本発明の代表的な実施例を示す。
実施例１
アルゴン雰囲気下、２０℃にて、２５ｍｌのフラスコに１，２−メチレンジオキシベンゼン（３．４２ｇ，２８．０ｍｍｏｌ）と９１．７重量％の３，３−ジアセトキシ−２−メチルプロペン（１．０６ｇ，５．７ｍｍｏｌ）を加え、更に、この混合溶液に９８重量％硫酸（６７ｍｇ，０．７ｍｍｏｌ）を加えた。この混合溶液を２３℃にて２時間攪拌した。反応終了後、反応液に酢酸エチル（５０ｍｌ）を加えて、反応液中に遊離した有機層を水（５０ｍｌ）で３回洗浄した後、無水硫酸ナトリウムにて乾燥し、更に、ろ過して得られた母液の溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー（展開溶媒：酢酸エチル／ｎ−ヘキサン＝１／７（ｖ／ｖ））にて精製することにより、目的物である１−アセトキシ−２−メチル−３−（３，４−メチレンジオキシフェニル）プロペンを白色結晶として０．７２ｇ得た。単離収率は３，３−ジアセトキシ−２−メチルプロペン基準で５５％であった。
以下に１−アセトキシ−２−メチル−３−（３，４−メチレンジオキシフェニル）プロペンの物性値を示す。
The following are typical examples of the present invention.
Example 1
1,20 methylenedioxybenzene (3.42 g, 28.0 mmol) and 91.7 wt% 3,3-diacetoxy-2-methylpropene (1. 06 g, 5.7 mmol) was added, and 98 wt% sulfuric acid (67 mg, 0.7 mmol) was further added to the mixed solution. The mixed solution was stirred at 23 ° C. for 2 hours. After completion of the reaction, ethyl acetate (50 ml) was added to the reaction solution, and the organic layer released in the reaction solution was washed three times with water (50 ml), dried over anhydrous sodium sulfate, and further filtered. The solvent of the mother liquor obtained was distilled off. The obtained residue is purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/7 (v / v)) to give 1-acetoxy-2-methyl-3- 0.73 g of (3,4-methylenedioxyphenyl) propene was obtained as white crystals. The isolated yield was 55% based on 3,3-diacetoxy-2-methylpropene.
The physical property values of 1-acetoxy-2-methyl-3- (3,4-methylenedioxyphenyl) propene are shown below.
１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３）δ＝１．５９（３Ｈ，ｄ，Ｊ＝１．５Ｈｚ）、２．１５（３Ｈ，ｓ）、３．１７（２Ｈ，ｓ）、５．９２（２Ｈ，ｓ）、６．６３（１Ｈ，ｄｄ，Ｊ＝７．８Ｈｚ，Ｊ＝１．５Ｈｚ）、６．６７（１Ｈ，ｄ，Ｊ＝１．５Ｈｚ）、６．７２（１Ｈ，ｄ，Ｊ＝７．８Ｈｚ）、７．０２（１Ｈ，ｑ，Ｊ＝１．５Ｈｚ） 1 H-NMR (300 MHz, CDCl 3 ) δ = 1.59 (3H, d, J = 1.5 Hz), 2.15 (3H, s), 3.17 (2H, s), 5.92 (2H , S), 6.63 (1H, dd, J = 7.8 Hz, J = 1.5 Hz), 6.67 (1H, d, J = 1.5 Hz), 6.72 (1H, d, J = 7.8 Hz), 7.02 (1H, q, J = 1.5 Hz)
元素分析：
Ｃ（％） Ｈ（％）
Ｃ１３Ｈ１４Ｏ４としての予想値 ６６．６６ ６．０２
測定値 ６６．７１ ６．１６
Elemental analysis:
C (%) H (%)
Expected value for C 13 H 14 O 4 66.66 6.02
Measurement 66.71 6.16
実施例２
アルゴン雰囲気下、２０℃にて、２５ｍｌのフラスコに１，２−メチレンジオキシベンゼン（３．４２ｇ，２８．０ｍｍｏｌ）と９１．７重量％の３，３−ジアセトキシ−２−メチルプロペン（１．０６ｇ，５．７ｍｍｏｌ）を加え、更に、この混合溶液に９８重量％硫酸（６７ｍｇ，０．７ｍｍｏｌ）を加えた。内温２３℃で２時間攪拌した後、反応終了後、反応液にアセトニトリル（１００ｍｌ）を加えて、高速液体クロマトグラフィーにて定量分析を行った。その結果、目的化合物である１−アセトキシ−２−メチル−３−（３，４−メチレンジオキシフェニル）プロペンの収率（３，３−ジアセトキシ−２−メチルプロペン基準）は６１．５％であった。なお、同反応液には原料である１，２−メチレンジオキシベンゼンが２．９４ｇ含まれていた。
Example 2
1,20 methylenedioxybenzene (3.42 g, 28.0 mmol) and 91.7 wt% 3,3-diacetoxy-2-methylpropene (1. 06 g, 5.7 mmol) was added, and 98 wt% sulfuric acid (67 mg, 0.7 mmol) was further added to the mixed solution. After stirring for 2 hours at an internal temperature of 23 ° C., acetonitrile (100 ml) was added to the reaction solution after completion of the reaction, and quantitative analysis was performed by high performance liquid chromatography. As a result, the yield of the target compound 1-acetoxy-2-methyl-3- (3,4-methylenedioxyphenyl) propene (based on 3,3-diacetoxy-2-methylpropene) was 61.5%. there were. The reaction solution contained 2.94 g of 1,2-methylenedioxybenzene as a raw material.
比較例１
アルゴン雰囲気下、２０℃、２５ｍｌの３ッ口フラスコに四塩化チタン（１．２８ｇ，６．７ｍｍｏｌ）、三フッ化ホウ素エーテル錯体（０．０１７ｇ，０．１２ｍｍｏｌ）を加えた。この混合溶液に、８〜１２℃にて１，２−メチレンジオキシベンゼン（３．２７ｇ，２６．８ｍｍｏｌ）を６０分かけて滴下し、次いで、３，３−ジアセトキシ−２−メチルプロペン（０．７４５ｇ，６．１ｍｍｏｌ）と１，２−メチレンジオキシベンゼン（０．７５ｇ，６．１ｍｍｏｌ）の混合物を１５分かけて滴下した。内温８〜１０℃で３０分攪拌し、濃度６ｍｏｌ／Ｌ（リットル）の塩酸（１０ｍｌ）及びジクロロメタン（１０ｍｌ）を加えて３０分攪拌した。反応終了後、不溶物をろ別し、得られたろ液をジクロロメタンにて抽出した。抽出で得られた有機層を水洗し、飽和食塩水で洗浄した後、無水硫酸ナトリウムで乾燥して、ろ過した。得られた母液を濃縮して粗生成物３．１６ｇを得た。この租生成物を高速液体クロマトグラフィーにて定量分析を行った結果、目的化合物である１−アセトキシ−２−メチル−３−（３，４−メチレンジオキシフェニル）プロペンの収率（３，３−ジアセトキシ−２−メチルプロペン基準）は４３．１％であった。なお、同粗生成物には原料である１，２−メチレンジオキシベンゼンが１．４０ｇ含まれていた。
Comparative Example 1
Under an argon atmosphere, titanium tetrachloride (1.28 g, 6.7 mmol) and boron trifluoride ether complex (0.017 g, 0.12 mmol) were added to a 25 ml three-necked flask at 20 ° C. To this mixed solution, 1,2-methylenedioxybenzene (3.27 g, 26.8 mmol) was added dropwise at 8-12 ° C. over 60 minutes, and then 3,3-diacetoxy-2-methylpropene (0 .745 g, 6.1 mmol) and 1,2-methylenedioxybenzene (0.75 g, 6.1 mmol) were added dropwise over 15 minutes. The mixture was stirred at an internal temperature of 8 to 10 ° C. for 30 minutes, hydrochloric acid (10 ml) having a concentration of 6 mol / L (liter) and dichloromethane (10 ml) were added, and the mixture was stirred for 30 minutes. After completion of the reaction, insoluble matters were filtered off, and the obtained filtrate was extracted with dichloromethane. The organic layer obtained by extraction was washed with water, washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. The obtained mother liquor was concentrated to obtain 3.16 g of a crude product. As a result of quantitative analysis of the product by high performance liquid chromatography, the yield of the target compound 1-acetoxy-2-methyl-3- (3,4-methylenedioxyphenyl) propene (3, 3 -Based on diacetoxy-2-methylpropene) was 43.1%. The crude product contained 1.40 g of 1,2-methylenedioxybenzene as a raw material.
比較例２
アルゴン雰囲気下、２０℃にて、２５ｍｌの３ッ口フラスコに四塩化チタン（０．１０ｇ，０．５ｍｍｏｌ）を加えた後、４〜５℃にて３，３−ジアセトキシ−２−メチルプロペン（０．９４ｇ，５．０ｍｍｏｌ）を加え、更に１，２−メチレンジオキシベンゼン（６．１１ｇ，５０．０ｍｍｏｌ）を滴下した。この反応混合物を２３℃に昇温した後、２時間攪拌した。反応終了後、反応液にエタノール２０ｇを加えて、高速液体クロマトグラフィーにて定量分析を行った。その結果、目的化合物である１−アセトキシ−２−メチル−３−（３，４−メチレンジオキシフェニル）プロペンの収率（３，３−ジアセトキシ−２−メチルプロペン基準）は９．８％であった。
なお、同反応液には原料である１，２−メチレンジオキシベンゼンが６．０４ｇ含まれていた。
Comparative Example 2
Titanium tetrachloride (0.10 g, 0.5 mmol) was added to a 25 ml three-necked flask at 20 ° C. under an argon atmosphere, and then 3,3-diacetoxy-2-methylpropene (4-5 ° C.) 0.94 g, 5.0 mmol) was added, and 1,2-methylenedioxybenzene (6.11 g, 50.0 mmol) was further added dropwise. The reaction mixture was heated to 23 ° C. and stirred for 2 hours. After completion of the reaction, 20 g of ethanol was added to the reaction solution, and quantitative analysis was performed by high performance liquid chromatography. As a result, the yield of the target compound 1-acetoxy-2-methyl-3- (3,4-methylenedioxyphenyl) propene (based on 3,3-diacetoxy-2-methylpropene) was 9.8%. there were.
The reaction solution contained 6.04 g of 1,2-methylenedioxybenzene as a raw material.
Claims (2)
下式(３)で表わされる１−アセトキシ−３−（３，４−メチレンジオキシフェニル）プロペン誘導体の製造法。
A method for producing a 1-acetoxy-3- (3,4-methylenedioxyphenyl) propene derivative represented by the following formula (3):
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2008059841A1 (en) * | 2006-11-13 | 2008-05-22 | Ube Industries, Ltd. | Process for production of 1-acyloxy-3-(3,4- methylenedioxyphenyl)-1-propene compound |
| WO2008099882A1 (en) * | 2007-02-15 | 2008-08-21 | Ube Industries, Ltd. | 2-methyl-3-(3,4-methylenedioxyphenyl)propanal, and method for production thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008059841A1 (en) * | 2006-11-13 | 2008-05-22 | Ube Industries, Ltd. | Process for production of 1-acyloxy-3-(3,4- methylenedioxyphenyl)-1-propene compound |
| 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 |
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