JP2004262843A - Method for carrying out underwater direct allylation reaction of allyl alcohol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for carrying out underwater direct allylation reaction of an allyl alcohol without carrying out preparation of ester, etc., or using a base in stoichiometric quantities. <P>SOLUTION: The method for carrying out underwater direct allylation reaction of an allyl alcohol comprises reacting the allyl alcohol represented by formula (I) (wherein R<SP>1</SP>and R<SP>2</SP>are each the same or different and they are each a hydrogen atom or a hydrocarbon group which may be a substituent group) with a nucleophilic agent represented by formula (II) (wherein W<SP>1</SP>and W<SP>2</SP>are each an electron-attracting group which may be the same or different; R<SP>3</SP>is a hydrocarbon group which may have a substituent group) in the presence of a catalytic system containing a Pd compound or a Pd complex, a triarylphosphine and a carboxylic acid represented by the formula (III): R<SP>4</SP>CO<SB>2</SB>H (R<SP>4</SP>is a hydrocarbon group which may have a substituent group) in water. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００１１】
（ただし、Ｒ^１およびＲ^２は同一または別異に水素原子または置換基を有していてもよい炭化水素基である）
で表されるアリルアルコールと、次式（ＩＩ）
【００１２】
【化５】

【００１３】
（ただし、Ｗ^１およびＷ^２は同一または別異に電子吸引基であり、Ｒ^３は置換基を有していてもよい炭化水素基である）
で表される求核剤を、Ｐｄ化合物もしくは錯体とトリアリールホスフィンと次式（ＩＩＩ）
Ｒ^４ＣＯ_２Ｈ （ＩＩＩ）
（ただし、Ｒ^４は置換基を有していてもよい炭化水素基である）
で表されるカルボン酸を含有する触媒系の存在下、水中で反応させることを特徴とするアリルアルコールの水中直接アリル化反応方法を提供する。
【００１４】
また、この出願の発明は、第２には、Ｒ^４ＣＯ_２Ｈが次式（ＩＶ）
【００１５】
【化６】

【００１６】
で表されるアダマンタンカルボン酸、または次式（Ｖ）
ＣＨ_３（ＣＨ_２）_１０ＣＯ_２Ｈ （Ｖ）
で表される１−ラウリル酸のいずれかである前記のアリルアルコールの水中直接アリル化反応方法を提供する。
【００１７】
この出願の発明は、第３にはＰｄの濃度が求核剤に対して０．５〜５ ｍｏｌ％である前記いずれかのアリルアルコールの水中直接アリル化反応方法を、第４には、Ｒ^４ＣＯ_２Ｈの濃度が求核剤に対して５〜２０ ｍｏｌ％である前記いずれかのアリルアルコールの水中直接アリル化反応方法を、また、第５には、反応を過熱還流下で行う前記いずれかのアリルアルコールの水中直接アリル化反応方法を提供する。
【００１８】
そして、この出願は、第６には、Ｐｄ化合物もしくは錯体とトリアリールホスフィンと次式（ＩＩＩ）
Ｒ^４ＣＯ_２Ｈ （ＩＩＩ）
（ただし、Ｒ^４は置換基を有していてもよい炭化水素基である）
で表されるカルボン酸を含有してなることを特徴とするアリルアルコールの水中直接アリル化反応用触媒をも提供する。
【００１９】
【発明の実施の形態】
この出願の発明者らは、Ｐｄ化合物もしくは錯体とトリアリールホスフィンと次式（ＩＩＩ）
Ｒ^４ＣＯ_２Ｈ （ＩＩＩ）
（ただし、Ｒ^４は置換基を有していてもよい炭化水素基である）
で表されるカルボン酸を含有してなる触媒系の共存下で次式（Ｉ）
【００２０】
【化７】

【００２１】
（ただし、Ｒ^１およびＲ^２は同一または別異に水素原子または置換基を有していてもよい炭化水素基である）
で表されるアリルアルコールと、次式（ＩＩ）
【００２２】
【化８】

【００２３】
（ただし、Ｗ^１およびＷ^２は同一または別異に電子吸引基であり、Ｒ^３は置換基を有していてもよい炭化水素基である）
で表される求核剤を反応させることにより、水中での直接アリル化が進行し、次式（ＶＩ）のアリル化体
【００２４】
【化９】

【００２５】
が得られることを見出し、本願発明に至ったものである。
【００２６】
このようなＰｄ化合物もしくは錯体とトリアリールホスフィンとカルボン酸の組み合わせからなる水中直接アリル化反応用触媒は、水中において有効に作用し、Ｐｄ化合物もしくは錯体とトリアリールホスフィンのみからなる触媒系を用いた場合と比較して格段に高い収率で生成物であるアリル化体を与える。しかし、後述の実施例にも示されるとおり、この触媒系を有機溶媒中で使用した場合には、同様のアリル化反応はほとんど進行しない。
【００２７】
この出願の発明の水中直接アリル化反応方法は、どのようなアリルアルコールに対しても適用できるものである。すなわち、前記式（Ｉ）におけるＲ^１およびＲ^２は、同一または別異に水素原子または置換基を有していてもよい各種の炭化水素基から選択される。具体的に、Ｒ^１およびＲ^２としては、メチル、エチル、ｎ−プロピル、ｉ−プロピル等のアルキル基、フェニル、トルイル、アントラセニル等のアリール基、およびこれらの炭化水素基にハロゲン、アミノ、シアノ等がさらに結合した置換基が例示される。
【００２８】
また、求核剤は、同一または別異の二つの電子吸引基Ｗ^１およびＷ^２に挟まれたＣＨ基を有する式（ＩＩ）のものであればよく、このとき電子吸引基Ｗ^１、Ｗ^２、およびＲ^３はどのようなものであってもよい。
【００２９】
この出願の発明の水中直接アリル化反応方法は、前期のとおり、Ｐｄ化合物もしくは錯体とトリアリールホスフィンＰＡｒ_３とカルボン酸Ｒ^４ＣＯ_２Ｈの存在下で行われるものであるが、Ｐｄ化合物やＰｄ錯体としては、Ｐｄ（ｄｂａ）_２（ただし、ｄｂａ＝ジベンジリデンアセトン）やＰｄ（ＯＡｃ）_２（ただし、Ａｃ＝アセチル）が例示される。これらはトリフェニルホスフィン等のトリアリールホスフィンＰＡｒ_３と錯形成するものである。また、Ｐｄ化合物やＰｄ錯体とＰＡｒ_３を共存させる代わりにパラジウムのテトラキス（トリアリールホスフィン）パラジウム錯体を用いてもよい。
【００３０】
この出願の発明において触媒系を構成するカルボン酸としては各種のものが例示される。具体的には、Ｒ^４としてＣ_１〜_２０のアルキル基やシクロアルキル基、アリール基、さらには、ハロゲン、Ｎ、Ｏ、Ｓ等を有する置換基が結合したアルキル基等が挙げられる。中でもラウリルカルボン酸（ＣＨ_３（ＣＨ_２）_１０ＣＯ_２Ｈ）とアダマンタンカルボン酸（１−ＡｄＣＯ_２Ｈ）を添加した場合には、高い収率で生成物が得られ、好ましい。
【００３１】
さらに、この出願の発明のアリルアルコールの水中直接アリル化反応方法では、触媒系の濃度、すなわち、Ｐｄ化合物または錯体、ＰＡｒ_３、およびカルボン酸の濃度はとくに限定されず、例えば求核剤１ ｍｏｌに対して０．００１〜１ ｍｏｌ（０．１ ｍｏｌ％〜１００ ｍｏｌ％）とすることができる。好ましくは、Ｐｄの濃度を求核剤に対して０．５〜５ ｍｏｌ％、カルボン酸の濃度を求核剤に対して５〜２０ ｍｏｌ％とする。このような条件下で反応を行った場合には、９０ ％以上の高い収率でアリル化体が得られ、好ましい。
【００３２】
また、この出願の発明のアリルアルコールの水中直接アリル化反応方法において、反応温度や反応時間等の条件もとくに限定されない。反応温度としては、７０〜１００℃が適用できるが、中でも過熱還流下で反応を行った場合には、短い反応時間でも高い収率でアリル化体が得られ、好ましい。
【００３３】
以下、実施例を示し、この発明の実施の形態についてさらに詳しく説明する。もちろん、この発明は以下の例に限定されるものではなく、細部については様々な態様が可能であることは言うまでもない。
【００３４】
【実施例】
以下の実施例において、各試薬は次のとおりに入手した。
【００３５】
（ａ）東京化成工業（株）より購入
化合物ａ１（ｃｉｎｎａｎｙｌ ａｌｃｏｈｏｌ）、化合物ｂ１（ｄｉｂｅｎｚｏｙｌｍｅｔｈａｎｅ）、Ｐｄ（ＰＰｈ_３）_４（ｔｅｔｒａｋｉｓ（ｔｒｉｐｈｅｎｙｌｐｈｏｓｐｈｉｎｅ）ｐａｌｌａｄｉｕｍ）、４−ＯｃｔＣ_６Ｈ_４ＣＯ_２Ｈ（４−ｏｃｔｙｌｂｅｎｚｏｉｃ ａｃｉｄ）、１−ＡｄＣＯ２Ｈ（１−ａｄａｍａｎｔａｎｅｃａｒｂｏｘｙｌｉｃ ａｃｉｄ）、Ｐｈ_２ＣＨＣＯ_２Ｈ（ｄｉｐｈｅｎｙｌａｃｅｔｉｃ ａｃｉｄ）、ＰｈＯＣＨ_２ＣＯ_２Ｈ（ｐｈｅｎｏｘｙａｃｅｔｉｃ ａｃｉｄ）、４−ＮＯ_２Ｃ_６Ｈ_４ＯＨ（４−ｎｉｔｒｏｐｈｅｎｏｌ）、２−Ｆ−４−ＮＯ_２Ｃ_６Ｈ_３ＯＨ（２−ｆｌｕｏｒｏ−４−ｎｉｔｒｏｐｈｅｎｏｌ）、Ｃ_６Ｆ_５ＯＨ（ｐｅｎｔａｆｌｕｏｒｏｐｈｅｎｏｌ）、化合物ｂ（表３反応３）（ｅｔｈｙｌ ２−ｏｘｏｃｙｃｌｏｐｅｎｔａｎｅｃａｒｂｏｘｙｌａｔｅ）、化合物ｂ（表３反応５（２−ｐｈｅｎｙｌｓｕｌｆｏｎｙｌａｃｅｔｏｐｈｅｎｏｎｅ）、化合物ａ（表３反応６）（ａｌｌｙｌ ａｌｃｏｈｏｌ）、化合物ａ（表３反応７）（ｔｒａｎｓ−２−ｈｅｘｅｎ−１−ｏｌ）
（ｂ） 関東化学（株）より購入
ＣＨ_３（ＣＨ_２）_１０ＣＯ_２Ｈ（ｌａｕｒｉｃ ａｃｉｄ）、ＰｈＣＯ_２Ｈ（ｂｅｎｚｏｉｃ ａｃｉｄ）、ＣＨ_３ＣＯ_２Ｈ（ａｃｅｔｉｃ ａｃｉｄ）
（ｃ）文献（Ｓｍｉｔｈ， Ａ． Ｂ．， ＩＩＩ； Ｌｅｖｅｎｂｅｒｇ， Ｐ． Ａ． Ｓｙｎｔｈｅｓｉｓ １９８１， ５６７）に従い合成
化合物ｂ（表３反応２）（ｅｔｈｙｌ ２−ｂｅｎｚｏｙｌｐｒｏｐｉｏｎａｔｅ）
（ｄ）シグマアルドリッチジャパン（株）より購入
化合物ｂ（表３反応４）（ｅｔｈｙｌ ２−ｎｉｔｒｏｐｒｏｐｉｏｎａｔｅ）
＜実施例１＞
反応式（Ａ）にしたがってシンナミルアルコールのアリル化反応を行った。
【００３６】
【化１０】

【００３７】
また、反応は次の表１に示した各条件で行った。
【００３８】
【表１】

【００３９】
触媒として一般にアリル位置換反応に用いられるＰｄ（ＰＰｈ_３）_４を用いた場合、７０℃において３０分で反応を停止させると、反応は殆ど進行しておらず、僅かな量の生成物しか得られなかった（反応１）。
【００４０】
また、ラウリル酸を触媒と下場合には、反応は全く進行しなかった（反応２）。
【００４１】
一方、Ｐｄ（ＰＰｈ_３）_４に添加剤としてラウリル酸を加えた場合には、収率が劇的に向上した（反応３）。さらに、各種のカルボン酸でも収率の改善が見られた。これより、Ｐｄ（ＰＰｈ_３）_４とカルボン酸を共存させることにより、水中でのアリル化反応が進行することが確認された。
＜比較例１＞
次の反応式（Ｂ）に従い、実施例１で検討した反応をトルエンおよび１，４−ジオキサン中で行った。結果を表２に示した。
【００４２】
【表２】

【００４３】
各々の反応の収率は、１ ％および３ ％であった。これより、本願発明の直接アリル化反応用触媒は、水中でのみ機能するものであり、トルエンや１，４−ジオキサン等の有機溶媒中ではアリル化反応が進行しないことが明らかになった。
＜実施例２＞
Ｐｄ（ＰＰｈ_３）_４と１−ＡｄＣＯ_２Ｈからなる触媒系を用いて、反応式（Ｃ）に従い各種の求核剤によるアリルアルコールの直接アリル化反応を行った。
【００４４】
結果を表３に示した。
【００４５】
【表３】

【００４６】
表３より、本願発明のアリルアルコールの水中直接アリル化反応方法は、各種のアリルアルコールおよび求核剤に対して有効であることが確認された。
【００４７】
【発明の効果】
以上詳しく説明したとおり、この発明によって、水中でアリルアルコールを直接アリル化するための方法が提供される。この発明の水中直接アリル化反応方法では、安価で環境負荷の低い水を反応溶媒として使用できるため、反応コストの削減や環境保全が期待できる。さらに、一般的な有機合成反応のように溶媒、基質、触媒等の乾燥（脱水、蒸留など）を行う必要がないため、反応工程の短縮が可能となり、有用性が高い。[0001]
TECHNICAL FIELD OF THE INVENTION
The invention of this application relates to a method for directly allylating allyl alcohol in water. More specifically, the invention of this application relates to a direct allylation reaction of allyl alcohol in water, which does not require the preparation of an ester or a carbonate or a stoichiometric amount of a base and the only by-product is water, and a catalyst therefor. It is.
[0002]
[Prior art and its problems]
In recent years, attention has been paid to water as an inexpensive and safe medium in consideration of the environment and human body. Also in organic synthesis, if water can be used instead of the conventionally used organic solvent, it can be said that there is a great advantage from the viewpoint of cost reduction and environmental conservation. Further, in conducting the reaction in water, drying of the solvent, the substrate, the catalyst, and the like is not required, which leads to shortening of the reaction process. Further, by using water that has completely different properties from other solvents as a solvent, there is a high possibility that a new reaction chemistry can be developed.
[0003]
Among various carbon-carbon bond formation reactions, the allylation reaction using a π-allyl transition metal species as a key intermediate, particularly the allylic substitution reaction catalyzed by a palladium complex, is one of the very important reactions in synthetic chemistry. And various catalyst systems have been reported.
[0004]
However, most of the allylation reactions use a combination of an allyl ester and a stoichiometric amount of a base or an allylated carbonate as a nucleophile, and the reaction tends to be complicated. On the other hand, if allyl alcohol can be used directly in the allylation reaction, there is no need to prepare an ester or carbonate, and no stoichiometric amount of base is required, so that the reaction process can be simplified and the atomic efficiency can be increased. it is conceivable that.
[0005]
Direct allylation reactions of allyl alcohols using a Pd catalyst have been reported so far (Non-Patent Documents 1 to 8). Further, direct allylation reactions of allyl alcohols using a catalyst other than Pd are also known (Non-Patent Documents 9 to 10).
[0006]
However, all of these reactions require a stoichiometric amount of an activator, which is carried out in an organic solvent (or in the absence of solvent) at a high temperature for a long time (for example, Non-Patent Document 11). Had. Although a catalyst that effectively works with a catalytic amount is also known (Non-Patent Document 12), no Pd catalyst that enables a direct allylation reaction of allyl alcohol in an aqueous solvent has been known. That is the fact.
[0007]
If such a direct allylation reaction of allyl alcohols can be carried out in an aqueous solvent, it is useful as an energy-saving and chemical-saving synthesis reaction process cell.
[0008]
[Non-patent document 1]
Atkins, K .; E. FIG. Walker, W .; E. FIG. Manyik, R .; M. Tetrahedron Lett. 1970, 3821
[Non-patent document 2]
Haudegond, J.A. P. Chauvin, Y .; Commeleuc, D .; J. Org. Chem. 1979, 44, 3063
[Non-Patent Document 3]
Bergbreiter, D.M. E. FIG. Weatherford, D .; A. J. Chem. Soc. Chem. Commun. 1989, 883
[Non-patent document 4]
Bergbreiter, D.M. E. FIG. Weatherford, D .; A. J. Org. Chem. 1989, 54, 2726
[Non-Patent Document 5]
Shimizu, I .; Toyoda, M .; Terashima, T .; Oshima, M .; Hasegawa, H .; Synlett 1992, 301
[Non-Patent Document 6]
Sakakibara, M .; Ogawa, A .; Tetrahedron Lett. 1994, 43, 8013
[Non-Patent Document 7]
Bricout, H .; Carpentier, J .; -F. Mortreux, A .; J. Mol. Catal. A: Chem. 1998, 136, 243
[Non-Patent Document 8]
Ozawa, F .; Okamoto, H .; Kawagishi, S .; Yamamoto, S .; Minami, T .; Yoshifuji, M .; J. Am. Chem. Soc. 2002, 124, 10968
[Non-Patent Document 9]
Mukhopadhyay, M .; Iqbal, J .; Tetrahedron Lett. 1995, 36, 6761
[Non-Patent Document 10]
Takeuchi, R .; Kahio, M .; Angew. Chem. , Int. Ed. Engl. 1997, 36, 263
[Non-Patent Document 11]
Lu, X. Jiang, X .; Tao, X .; J. Organomet. Chem. 1998, 344, 109
[Non-Patent Document 12]
Lu, X. Lu, L .; Sun, J .; , J. et al. Mol. Catal. 1987, 41, 245
Therefore, the invention of this application has been made in view of the circumstances as described above, and solves the problems of the prior art.Allyl alcohol can be used without preparing an ester or the like or using a stoichiometric amount of a base. It is an object of the present invention to provide a method for performing an allylation reaction directly in water.
[0009]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the invention of this application firstly provides the following formula (I)
[0010]
Embedded image

[0011]
(However, R ¹ and R ² are the same or different and are a hydrogen atom or a hydrocarbon group which may have a substituent)
An allyl alcohol represented by the following formula (II):
[0012]
Embedded image

[0013]
(W ¹ and W ² are the same or different and are electron withdrawing groups, and R ³ is a hydrocarbon group which may have a substituent.)
A nucleophilic agent represented by the formula (III):
R ⁴ CO ₂ H (III)
(However, R ⁴ is a hydrocarbon group which may have a substituent.)
Wherein the reaction is carried out in water in the presence of a carboxylic acid-containing catalyst system represented by the formula:
[0014]
The invention of this application, the first _^2, R 4 CO 2 H The following formula (IV)
[0015]
Embedded image

[0016]
An adamantanecarboxylic acid represented by the following formula (V):
CH ₃ (CH ₂ ) ₁₀ CO ₂ H (V)
A direct allylation reaction in water of the above allyl alcohol which is any one of 1-lauric acid represented by the formula:
[0017]
Thirdly, the invention of this application relates to a method for direct allylation of allyl alcohol in water, wherein the concentration of Pd is 0.5 to 5 mol% with respect to the nucleophile, and fourthly, R ^{4 The} method for direct allylation of allyl alcohol in water, wherein the concentration of CO ₂ H is 5 to 20 mol% with respect to the nucleophile, and fifthly, the reaction is carried out under superheated reflux. A method for direct allylation of any allyl alcohol in water is provided.
[0018]
The present application is based on the sixth application that a Pd compound or complex, a triarylphosphine and a compound represented by the following formula (III):
R ⁴ CO ₂ H (III)
(However, R ⁴ is a hydrocarbon group which may have a substituent.)
And a catalyst for direct allylation reaction of allyl alcohol in water, characterized by comprising a carboxylic acid represented by the formula:
[0019]
BEST MODE FOR CARRYING OUT THE INVENTION
The inventors of the present application disclose a Pd compound or complex, a triarylphosphine and a compound represented by the following formula (III):
R ⁴ CO ₂ H (III)
(However, R ⁴ is a hydrocarbon group which may have a substituent.)
In the presence of a catalyst system containing a carboxylic acid represented by the following formula (I):
[0020]
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[0021]
(However, R ¹ and R ² are the same or different and are a hydrogen atom or a hydrocarbon group which may have a substituent)
An allyl alcohol represented by the following formula (II):
[0022]
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[0023]
(W ¹ and W ² are the same or different and are electron withdrawing groups, and R ³ is a hydrocarbon group which may have a substituent.)
By reacting the nucleophile represented by the formula (1), direct allylation in water proceeds, and the allylic form of the following formula (VI)
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[0025]
Are obtained, and the present invention has been accomplished.
[0026]
Such a catalyst for direct allylation reaction in water comprising a combination of a Pd compound or complex, a triarylphosphine and a carboxylic acid works effectively in water, and uses a catalyst system comprising only a Pd compound or a complex and a triarylphosphine. The product allylated product is obtained in a much higher yield than in the case. However, when this catalyst system is used in an organic solvent, a similar allylation reaction hardly proceeds, as shown in Examples described later.
[0027]
The method for direct allylation in water of the invention of this application can be applied to any allyl alcohol. That is, R ¹ and R ² in the formula (I) are selected from the same or different hydrogen atoms or various hydrocarbon groups which may have a substituent. Specifically, as R ¹ and R ² , an alkyl group such as methyl, ethyl, n-propyl, i-propyl, an aryl group such as phenyl, toluyl, anthracenyl and the like, and a halogen, amino, cyano, etc. And the like.
[0028]
The nucleophile may be any one of the formula (II) having a CH group sandwiched between two identical or different electron-withdrawing groups W ¹ and W ^2. At this time, the electron-withdrawing groups W ¹ and W 2 ² and R ³ may be any.
[0029]
The direct allylation reaction in water of the invention of this application is carried out in the presence of a Pd compound or complex, a triarylphosphine PAr ₃ and a carboxylic acid R ⁴ CO ₂ H, as described above, but the Pd compound or Pd Examples of the complex include Pd (dba) ₂ (where dba = dibenzylideneacetone) and Pd (OAc) ₂ (where Ac = acetyl). These are intended to complexing with triarylphosphine PAr _3, such as triphenylphosphine. It is also possible using palladium tetrakis (triarylphosphine) palladium complex instead coexist Pd compounds or Pd complex and PAr _3.
[0030]
Various carboxylic acids constituting the catalyst system in the invention of this application are exemplified. Specifically, the alkyl group or cycloalkyl group of C ₁ ~ ₂₀ as R ^4, the aryl group, and further, halogen, N, O, alkyl group or the like substituent group is bonded have the S and the like. Above all, when lauryl carboxylic acid (CH ₃ (CH ₂ ) ₁₀ CO ₂ H) and adamantane carboxylic acid (1-AdCO ₂ H) are added, a product is obtained in a high yield, which is preferable.
[0031]
Furthermore, in the method for direct allylation of allyl alcohol in water according to the invention of the present application, the concentration of the catalyst system, that is, the concentration of the Pd compound or complex, PAr ₃ , and the carboxylic acid is not particularly limited. 0.001 mol to 1 mol (0.1 mol% to 100 mol%). Preferably, the concentration of Pd is 0.5 to 5 mol% with respect to the nucleophile, and the concentration of the carboxylic acid is 5 to 20 mol% with respect to the nucleophile. When the reaction is carried out under such conditions, an allylated product is obtained in a high yield of 90% or more, which is preferable.
[0032]
In the method for direct allylation of allyl alcohol in water according to the invention of the present application, conditions such as reaction temperature and reaction time are not particularly limited. As the reaction temperature, 70 to 100 ° C. can be applied. In particular, when the reaction is carried out under superheated reflux, an allylic compound can be obtained in a high yield even with a short reaction time, which is preferable.
[0033]
Hereinafter, examples will be shown, and embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail.
[0034]
【Example】
In the following examples, each reagent was obtained as follows.
[0035]
(A) by Tokyo Chemical Industry Co., purchased from compounds a1 (cinnanyl alcohol), compound _{b1 (dibenzoylmethane), Pd (PPh} 3) 4 (tetrakis (triphenylphosphine) palladium), 4-OctC 6 H 4 CO 2 H (4- _{octylbenzoic acid), 1-AdCO2H (} 1-adamantanecarboxylic acid), Ph 2 CHCO 2 H (diphenylacetic acid), PhOCH 2 CO 2 H (phenoxyacetic acid), 4-NO 2 C 6 H 4 OH (4-nitrophenol), 2 _{-F-4-NO 2 C 6} H 3 OH (2-fluoro-4-nitrophenol), C 6 F 5 OH (pen afluorophenol, compound b (Table 3 reaction 3) (ethyl 2-oxocyclopentanecarboxylate), compound b (Table 3 reaction 5 (2-phenylsulfonylacetophenone), compound a (Table 3 reaction 6) (allyl alcohol3), compound a 7) (trans-2-hexen-1-ol)
(B) Purchased from Kanto Chemical Co., Ltd. CH ₃ (CH ₂ ) ₁₀ CO ₂ H (lauric acid), PhCO ₂ H (benzoic acid), CH ₃ CO ₂ H (acetic acid)
(C) Synthetic compound b (Table 3 reaction 2) according to literature (Smith, AB, III; Levenberg, PA Synthesis 1981, 567) (ethyl 2-benzoylpropionate)
(D) Compound b (Table 3 Reaction 4) purchased from Sigma-Aldrich Japan Co., Ltd. (ethyl 2-nitropropionate)
<Example 1>
An allylation reaction of cinnamyl alcohol was performed according to the reaction formula (A).
[0036]
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[0037]
The reaction was performed under the conditions shown in Table 1 below.
[0038]
[Table 1]

[0039]
When Pd (PPh ₃ ) _4, which is generally used for an allyl substitution reaction, is used as a catalyst, when the reaction is stopped at 70 ° C. for 30 minutes, the reaction hardly progresses, and only a small amount of product is obtained. No (reaction 1).
[0040]
When lauric acid was used as a catalyst, the reaction did not proceed at all (reaction 2).
[0041]
On the other hand, when lauric acid was added as an additive to Pd (PPh ₃ ) ₄ , the yield was dramatically improved (Reaction 3). Furthermore, various carboxylic acids also showed improved yields. From this, it was confirmed that coexistence of Pd (PPh ₃ ) ₄ and a carboxylic acid promoted an allylation reaction in water.
<Comparative Example 1>
According to the following reaction formula (B), the reaction studied in Example 1 was performed in toluene and 1,4-dioxane. The results are shown in Table 2.
[0042]
[Table 2]

[0043]
The yield of each reaction was 1% and 3%. This revealed that the direct allylation reaction catalyst of the present invention functions only in water, and that the allylation reaction does not proceed in an organic solvent such as toluene or 1,4-dioxane.
<Example 2>
Using a catalyst system consisting of Pd (PPh ₃ ) ₄ and 1-AdCO ₂ H, direct allylation of allyl alcohol with various nucleophiles was carried out according to the reaction formula (C).
[0044]
The results are shown in Table 3.
[0045]
[Table 3]

[0046]
From Table 3, it was confirmed that the method of direct allylation of allyl alcohol in water of the present invention is effective for various allyl alcohols and nucleophiles.
[0047]
【The invention's effect】
As described in detail above, the present invention provides a method for directly allylating allyl alcohol in water. In the method of direct allylation in water in water of the present invention, inexpensive and low-impact water can be used as a reaction solvent, so that reduction in reaction cost and environmental conservation can be expected. Furthermore, since there is no need to dry (dehydrate, distill, etc.) the solvent, substrate, catalyst, etc. as in a general organic synthesis reaction, the reaction steps can be shortened and the utility is high.

Claims (6)

The following formula (I)

(However, R ¹ and R ² are the same or different and are a hydrogen atom or a hydrocarbon group which may have a substituent)
An allyl alcohol represented by the following formula (II):

(W ¹ and W ² are the same or different and are electron withdrawing groups, and R ³ is a hydrocarbon group which may have a substituent.)
A nucleophilic agent represented by the formula (III):
R ⁴ CO ₂ H (III)
(However, R ⁴ is a hydrocarbon group which may have a substituent.)
Wherein the reaction is carried out in water in the presence of a catalyst system containing a carboxylic acid represented by the formula: R ⁴ CO ₂ H is represented by the following formula (IV)

An adamantanecarboxylic acid represented by the following formula (V):
CH ₃ (CH ₂ ) ₁₀ CO ₂ H (V)
The direct allylation reaction of allyl alcohol in water according to claim 1, which is any of 1-lauric acid represented by the formula: 3. The method according to claim 1, wherein the concentration of Pd is 0.5 to 5 mol% with respect to the nucleophile. ^{4. The} direct allylation reaction of allyl alcohol in water according to claim 1, wherein the concentration of R ⁴ CO ₂ H is 5 to 20 mol% based on the nucleophile. 5. The direct allylation reaction of allyl alcohol in water according to claim 1, wherein the reaction is carried out under superheated reflux. A catalyst system for directly allylating allyl alcohol in water, comprising a Pd compound or complex, a triarylphosphine, and the following formula (III)
R ⁴ CO ₂ H (III)
(However, R ⁴ is a hydrocarbon group which may have a substituent.)
A catalyst for direct allylation reaction of allyl alcohol in water, which comprises a carboxylic acid represented by the formula: