JP3605012B2

JP3605012B2 - Production of ketones by oxidative decomposition of olefins.

Info

Publication number: JP3605012B2
Application number: JP2000243982A
Authority: JP
Inventors: 誠藤田; 隆博楠川; 博一伊藤
Original assignee: Japan Science and Technology Agency; National Institute of Japan Science and Technology Agency
Current assignee: Japan Science and Technology Agency; National Institute of Japan Science and Technology Agency
Priority date: 2000-08-11
Filing date: 2000-08-11
Publication date: 2004-12-22
Anticipated expiration: 2020-08-11
Also published as: WO2002014254A1; JP2002053516A

Description

【０００１】
【発明の属する技術分野】
本発明は、オレフィンの酸化的分解反応を利用した、カルボニル化合物の新規な製造方法に関する。
【０００２】
【従来の技術】
オレフィンを酸化的に分解して対応するカルボニル化合物を製造する方法としては、これまでに、有機溶媒中オゾンを用いて炭素−炭素二重結合を分解してオゾニドを生成させ、次いでこれを還元してケトンにする方法が唯一実際的な方法として知られているのみである。
しかしながら、上記従来法は、有害物質のオゾンを使用することが必須であり、且つ有機溶媒中で反応させなければならないと云う点に問題があり、工業的な方法として実用化されるまでには到っていない。
【０００３】
【発明が解決しようとする課題】
本発明は、オレフィンを酸化的に分解して対応するカルボニル化合物を製造する方法であって、オゾンのような有害物質を使用せず、且つ水媒体中での反応が可能な、簡便且つ効率的な該製造方法を提供することを目的とする。
【０００４】
【課題を解決するための手段】
本発明は、疎水的空間を有する金属錯体の存在下、水媒体中でオレフィン化合物を過酸化水素及び鉄化合物で酸化することを特徴とする、対応するカルボニル化合物の製造法に関する。
【０００５】
本発明で用いられる疎水的空間を有する金属錯体としては、例えば、配位子が実質的に平面構造であって、遷移金属と配位結合を形成することができる電子対を分子中に３個以上有する化合物が挙げられる。
また、遷移金属としては、例えば白金、パラジウム等が挙げられる。
遷移金属と配位結合を形成することができる配位子の電子対としては、例えばピリジン環の窒素原子の電子対が挙げられる。
配位子としては、分子中に遷移金属と配位結合を形成することができる電子対を３乃至６個有する化合物が好ましく、具体的には２，４，６−トリス（４−ピリジル）−１，３，５−トリアジンや２，４，６−トリス（３−ピリジル）−１，３，５−トリアジン等が、より好ましい配位子の例として挙げられる。
本発明で用いられる疎水的空間を有する金属錯体としては、例えばＭ_６Ｌ_４型三次元かご状又はボウル状遷移金属錯体が挙げられる。
本発明で用いられるＭ_６Ｌ_４型三次元かご状遷移金属錯体としては、例えば特開２０００−８６６８３号公報に記載の三次元かご状遷移金属錯体が挙げられる。
本発明で用いられる疎水的空間を有する金属錯体の好ましい具体例としては、例えば下式［１］
【０００６】
【化３】

【０００７】
で示される化合物や、下式［２］
【０００８】
【化４】

【０００９】
で示される化合物が挙げられる。
本発明に係る金属錯体の使用量は、通常オレフィン化合物１モルに対し１〜３０モル％程度、好ましくは３〜２０モル％、より好ましくは５〜１０モル％程度である。
【００１０】
本発明で用いられるオレフィン化合物としては、芳香族基を有するオレフィン化合物が好ましい。
また、本発明で用いられるオレフィン化合物としては、分子の末端に炭素−炭素二重結合を有するオレフィン化合物が好ましい。
本発明で用いられる過酸化水素としては、例えば、通常用いられる濃度約３０％前後の過酸化水素水溶液が挙げられるが、濃度等は特にこれに限定されるものではなく、反応系中において酸化力を発揮し、目的とする酸化反応をスムーズに進行させ得る濃度等であればどのようなものでも良い。
過酸化水素の使用量は、通常オレフィン化合物に対し０．５〜５０当量、好ましくは１〜１０当量、より好ましくは１〜２当量である。
本発明で用いられる鉄化合物としては、一般的にはそのままで酸化力のある３価の鉄化合物が好ましいが、この場合は２価の鉄化合物であっても系中で酸化されて３価になるので、２価の鉄化合物も３価の鉄化合物と同様に使用可能である。
本発明で用いられる鉄化合物の具体例としては、例えば塩化第二（又は第一）鉄、硫酸第二（又は第一）鉄、硝酸第二（又は第一）鉄、リン酸第二（又は第一）鉄等の鉄塩が挙げられる。
鉄化合物の使用量は、通常オレフィン化合物に対し対し１〜５０モル％程度、好ましくは３〜２０モル％程度、より好ましくは５〜１０モル％程度である。
【００１１】
本発明の製造法は、通常、水溶媒中で反応が行われる。
本発明の製造法に於ける反応温度は、通常０〜１００℃位、好ましくは２０〜５０℃位である。反応時間は反応温度やオレフィン化合物の種類、或いは過酸化水素の反応系中に於ける濃度、金属錯体及び３価の鉄塩の使用量等の反応条件により自ずから異なり一概には言えないが、通常２〜４８時間位である。
【００１２】
【実施例】
以下、実施例により本発明をより詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
なお、実施例において使用した錯体１ａは、上記式［１］で示される錯体において、遷移金属がパラジウムであるもの、また、錯体１ｂは、上記式［１］で示される錯体において、遷移金属が白金であるものをそれぞれ表す。
【００１３】
実施例１錯体１ａを用いたアセトフェノンの合成
５ｍＬの試験管に、錯体１ａ（１５．０ｍｇ，０．００５ｍｍｏｌ）及び硝酸鉄・９水和物（２．０ｍｇ，０．００５ｍｍｏｌ）を入れて水（１ｍＬ）で加熱溶解させた。これを水道水で冷やした後、マイクロシリンジでα−メチルスチレン０．００６５ｍＬ（０．０５ｍｍｏｌ）と３４％過酸化水素水０．００５ｍＬ（０．０５ｍｍｏｌ）を順次加えて密閉した後、５０℃で２４時間攪拌した。攪拌反応後、重クロロホルムで抽出し、その^１ＨＮＭＲからアセトフェノンの生成量を定量した（収率６６％）。
【００１４】
実施例２錯体１ｂを用いたアセトフェノンの合成
５ｍＬの試験管に、錯体１ｂ（１７．６ｍｇ，０．００５ｍｍｏｌ）及び硝酸鉄・９水和物（２，２．０ｍｇ，０．００５ｍｍｏｌ）を入れて水（１ｍＬ）で加熱溶解させた。これを水道水で冷やした後、マイクロシリンジでα−メチルスチレン０．００６５ｍＬ（０．０５ｍｍｏｌ）と３４％過酸化水素水０．００５ｍＬ（０．０５ｍｍｏｌ）を順次加えて密閉した後、５０℃で２４時間攪拌した。攪拌反応後、重クロロホルムで抽出し、その^１ＨＮＭＲからアセトフェノンの生成量を定量した（収率１５％）。
【００１５】
比較例１硝酸鉄・９水和物を除いた系でのアセトフェノンの合成
５ｍＬの試験管に、錯体１ａ（１５．０ｍｇ，０．００５ｍｍｏｌ）を入れて水（１ｍＬ）で加熱溶解させた。これを水道水で冷やした後、マイクロシリンジでα−メチルスチレン０．００６５ｍＬ（０．０５ｍｍｏｌ）と３４％過酸化水素水０．００５ｍＬ（０．０５ｍｍｏｌ）を順次加えて密閉した後、５０℃で２４時間攪拌した。攪拌反応後、重クロロホルムで抽出し、その^１ＨＮＭＲからアセトフェノンの生成量を定量した（収率１％）。
【００１６】
比較例２錯体１ａを除いた系でのアセトフェノンの合成
５ｍＬの試験管に、硝酸鉄・９水和物（２．０ｍｇ，０．００５ｍｍｏｌ）を入れて水（１ｍＬ）に溶解させた。これに、マイクロシリンジでα−メチルスチレン０．００６５ｍＬ（０．０５ｍｍｏｌ）と３４％過酸化水素水０．００５ｍＬ（０．０５ｍｍｏｌ）を順次加えて密閉した後、５０℃で２４時間攪拌した。攪拌反応後、重クロロホルムで抽出し、その^１ＨＮＭＲからアセトフェノンの生成量を定量した（収率４％）。
【００１７】
比較例３過酸化水素を除いた系でのアセトフェノンの合成
５ｍＬの試験管に、錯体１ａ（１５．０ｍｇ，０．００５ｍｍｏｌ）及び硝酸鉄・９水和物（２．０ｍｇ，０．００５ｍｍｏｌ）を入れて水（１ｍＬ）で加熱溶解させた。これを水道水で冷やした後、マイクロシリンジでα−メチルスチレン０．００６５ｍＬ（０．０５ｍｍｏｌ）と３４％過酸化水素水０．００５ｍＬ（０．０５ｍｍｏｌ）を順次加えて密閉した後、５０℃で２４時間攪拌した。攪拌反応後、重クロロホルムで抽出し、その^１ＨＮＭＲからアセトフェノンの生成量を定量した（収率１％）。
【００１８】
実施例３錯体１ａを用いた４−メトキシアセトフェノンの合成
５ｍＬの試験管に錯体１ａ（１５．０ｍｇ，０．００５ｍｍｏｌ）及び硝酸鉄・９水和物（２．０ｍｇ，０．００５ｍｍｏｌ）を入れ、水（１ｍＬ）に加熱溶解させて水溶液を調製した。別の試験管に予め４−メトキシ−α−メチルスチレン７．４ｍｇ（０．０５ｍｍｏｌ）を入れておき、これに上で調製した水溶液と３４％過酸化水素水０．００５ｍＬ（０．０５ｍｍｏｌ）を順次加えて密閉した後、５０℃で２４時間攪拌した。攪拌反応後、重クロロホルムで抽出し、その^１ＨＮＭＲから４−メトキシアセトフェノンの生成量を定量した（収率６１％）。
【００１９】
実施例４錯体１ａを用いた４−メチルアセトフェノンの合成
５ｍＬの試験管に、錯体１ａ（１５．０ｍｇ，０．００５ｍｍｏｌ）及び硝酸鉄・９水和物（２．０ｍｇ，０．００５ｍｍｏｌ）を入れて水（１ｍＬ）で加熱溶解させた。これを水道水で冷やした後、マイクロシリンジで４−メチル−α−メチルスチレン０．００６６ｍＬ（０．０５ｍｍｏｌ）と３４％過酸化水素水０．００５ｍＬ（０．０５ｍｍｏｌ）を順次加えて密閉した後、５０℃で２４時間攪拌した。攪拌反応後、重クロロホルムで抽出し、その^１ＨＮＭＲから４−メチルアセトフェノンの生成量を定量した（収率５３％）。
【００２０】
実施例５錯体１ａを用いた４−ニトロアセトフェノンの合成
５ｍＬの試験管に、錯体１ａ（１５．０ｍｇ，０．００５ｍｍｏｌ）及び硝酸鉄・９水和物（２．０ｍｇ，０．００５ｍｍｏｌ）を入れ、水（１ｍＬ）に加熱溶解させて水溶液を調製した。別の試験管に予め４−ニトロ−α−メチルスチレン８．２ｍｇ（０．０５ｍｍｏｌ）を入れておき、これに上で調製した水溶液と３４％過酸化水素水０．００５ｍＬ（０．０５ｍｍｏｌ）を順次加えて密閉した後、、５０℃で２４時間攪拌した。攪拌反応後、重クロロホルムで抽出し、その^１ＨＮＭＲから４−ニトロアセトフェノンの生成量を定量した（収率７５％）。
【００２１】
実施例６錯体１ａを用いたメチル−２−ナフチルケトンの合成
５ｍＬの試験管に、錯体１ａ（１５．０ｍｇ，０．００５ｍｍｏｌ）及び硝酸鉄・９水和物（２．０ｍｇ，０．００５ｍｍｏｌ）を入れ、水（１ｍＬ）に加熱溶解させて水溶液を調製した。別の試験管に予めイソプロペニルナフタレン８．２ｍｇ（０．０５ｍｍｏｌ）を入れておき、これに上で調製した水溶液と３４％過酸化水素水０．００５ｍＬ（０．０５ｍｍｏｌ）を順次加えて密閉した後、５０℃で２４時間攪拌した。攪拌反応後、重クロロホルムで抽出し、その^１ＨＮＭＲからメチル−２−ナフチルケトンの生成量を定量した（収率４０％）。
【００２２】
実施例７錯体１ａを用いたメチル−２−ナフチルケトンの合成（スケールアップ合成）
１００ｍＬの茄子型フラスコにイソプロペニルナフタレン１６８．１ｍｇ（１．０ｍｍｏｌ）を入れ、これに別に調製した錯体１ａ（２９９．３ｍｇ，０．１ｍｍｏｌ）及び硝酸鉄・９水和物（４０．４ｍｇ，０．１ｍｍｏｌ）の水溶液（３０ｍＬ）を加えて１０分間攪拌した。これにマイクロシリンジで３４％過酸化水素水０．１１ｍＬ（１．０ｍｍｏｌ）を加えて密閉した後、５０℃で２４時間攪拌した。攪拌反応後、ヘキサン５０ｍＬ×３、クロロホルム５０ｍＬ×２で抽出し、その抽出液を無水硫酸マグネシウムで乾燥した。乾燥後、これを濃縮し、ＧＰＣで分離してメチル−２−ナフチルケトン（７８．９ｍｇ，収率４７％）を得た。同時に、原料（５２．２ｍｇ）を回収した。
【００２３】
【発明の効果】
オレフィンの酸化的分解（開裂）反応は基本的な合成反応であるが、これまではオゾンを使用しなければならないと云うことと、有機溶媒中での反応と云うことがネックとなっていて、一般に広く行われるまでには到っていなかった。
本発明の方法によれば、オゾンのような有害物質を使用せず、且つ水媒体中での反応が進行するため、工業的な規模での実施も可能であり、今後の進展が大いに期待できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel method for producing a carbonyl compound using an oxidative decomposition reaction of an olefin.
[0002]
[Prior art]
As a method for producing the corresponding carbonyl compound by oxidatively decomposing an olefin, hitherto, an ozonide is produced by decomposing a carbon-carbon double bond using ozone in an organic solvent, and then reducing the ozonide. The only way to make ketones is known to be practical.
However, the above conventional method has a problem in that it is essential to use ozone as a harmful substance, and the reaction must be performed in an organic solvent. Not yet.
[0003]
[Problems to be solved by the invention]
The present invention is a method for producing a corresponding carbonyl compound by oxidatively decomposing an olefin, and does not use a harmful substance such as ozone and can react in an aqueous medium in a simple and efficient manner. It is an object of the present invention to provide such a production method.
[0004]
[Means for Solving the Problems]
The present invention relates to a method for producing a corresponding carbonyl compound, comprising oxidizing an olefin compound with hydrogen peroxide and an iron compound in an aqueous medium in the presence of a metal complex having a hydrophobic space.
[0005]
As the metal complex having a hydrophobic space used in the present invention, for example, a ligand having a substantially planar structure and having three electron pairs in a molecule capable of forming a coordinate bond with a transition metal is used. Compounds having the above are mentioned.
Examples of the transition metal include platinum and palladium.
Examples of the electron pair of a ligand capable of forming a coordinate bond with a transition metal include an electron pair of a nitrogen atom of a pyridine ring.
As the ligand, a compound having 3 to 6 electron pairs capable of forming a coordination bond with a transition metal in the molecule is preferable. Specifically, 2,4,6-tris (4-pyridyl)- 1,3,5-triazine, 2,4,6-tris (3-pyridyl) -1,3,5-triazine and the like are exemplified as more preferable ligands.
Examples of the metal complex having a hydrophobic space used in the present invention include an M ₆ L _4- type three-dimensional cage-like or bowl-like transition metal complex.
The M ₆ L ₄ type three-dimensional cage transition metal complexes used in the present invention include three-dimensional cage transition metal complexes described in, for example, JP 2000-86683.
Preferred specific examples of the metal complex having a hydrophobic space used in the present invention include, for example, the following formula [1]
[0006]
Embedded image

[0007]
A compound represented by the following formula [2]:
[0008]
Embedded image

[0009]
The compound shown by these is mentioned.
The amount of the metal complex according to the present invention to be used is generally about 1 to 30 mol%, preferably 3 to 20 mol%, more preferably about 5 to 10 mol%, per 1 mol of the olefin compound.
[0010]
As the olefin compound used in the present invention, an olefin compound having an aromatic group is preferable.
Further, as the olefin compound used in the present invention, an olefin compound having a carbon-carbon double bond at the terminal of the molecule is preferable.
The hydrogen peroxide used in the present invention includes, for example, a hydrogen peroxide aqueous solution having a concentration of about 30%, which is usually used, but the concentration is not particularly limited thereto. And any concentration may be used as long as the concentration is such that the desired oxidation reaction can proceed smoothly.
The amount of hydrogen peroxide to be used is generally 0.5 to 50 equivalents, preferably 1 to 10 equivalents, more preferably 1 to 2 equivalents to the olefin compound.
As the iron compound used in the present invention, generally, a trivalent iron compound having oxidizing power as it is is preferable. In this case, even a divalent iron compound is oxidized in the system to become trivalent. Therefore, a divalent iron compound can be used in the same manner as a trivalent iron compound.
Specific examples of the iron compound used in the present invention include, for example, ferric (or ferrous) chloride, ferric (or ferrous) sulfate, ferric (or ferrous) nitrate, and ferric (or ferrous) phosphate. First) iron salts such as iron.
The amount of the iron compound to be used is generally about 1 to 50 mol%, preferably about 3 to 20 mol%, more preferably about 5 to 10 mol%, based on the olefin compound.
[0011]
In the production method of the present invention, the reaction is usually performed in an aqueous solvent.
The reaction temperature in the production method of the present invention is usually about 0 to 100 ° C, preferably about 20 to 50 ° C. The reaction time depends on the reaction conditions such as the reaction temperature, the type of the olefin compound, the concentration of hydrogen peroxide in the reaction system, and the amount of the metal complex and the trivalent iron salt used. It takes about 2 to 48 hours.
[0012]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The complex 1a used in the examples is a complex represented by the above formula [1] in which the transition metal is palladium, and the complex 1b is a complex represented by the above formula [1] in which the transition metal is the same. Those that are platinum are represented.
[0013]
Example 1 Synthesis of acetophenone using complex 1a Complex 1a (15.0 mg, 0.005 mmol) and iron nitrate nonahydrate (2.0 mg, 0.005 mmol) were placed in a 5 mL test tube, and water ( (1 mL). After cooling this with tap water, 0.0065 mL (0.05 mmol) of α-methylstyrene and 0.005 mL (0.05 mmol) of 34% aqueous hydrogen peroxide were sequentially added with a microsyringe, and the mixture was sealed. Stirred for 24 hours. After the stirring reaction, the mixture was extracted with deuterated chloroform, and the amount of acetophenone produced was quantified from its ¹ H NMR (66% yield).
[0014]
Example 2 Synthesis of Acetophenone Using Complex 1b Complex 1b (17.6 mg, 0.005 mmol) and iron nitrate nonahydrate (2,2.0 mg, 0.005 mmol) were placed in a 5 mL test tube. The mixture was dissolved by heating with water (1 mL). After cooling this with tap water, 0.0065 mL (0.05 mmol) of α-methylstyrene and 0.005 mL (0.05 mmol) of 34% aqueous hydrogen peroxide were sequentially added with a microsyringe, and the mixture was sealed. Stirred for 24 hours. After the stirring reaction, the mixture was extracted with deuterated chloroform, and the amount of acetophenone produced was quantified from its ¹ H NMR (yield 15%).
[0015]
Comparative Example 1 Synthesis of acetophenone in a system from which iron nitrate 9-hydrate was removed A complex 1a (15.0 mg, 0.005 mmol) was put into a 5 mL test tube, and dissolved by heating with water (1 mL). After cooling this with tap water, 0.0065 mL (0.05 mmol) of α-methylstyrene and 0.005 mL (0.05 mmol) of 34% aqueous hydrogen peroxide were sequentially added with a microsyringe, and the mixture was sealed. Stirred for 24 hours. After the stirring reaction, extraction was performed with heavy chloroform, and the amount of acetophenone produced was quantified from its ¹ H NMR (yield 1%).
[0016]
Comparative Example 2 Synthesis of Acetophenone in a System Excluding Complex 1a Iron nitrate nonahydrate (2.0 mg, 0.005 mmol) was placed in a 5 mL test tube and dissolved in water (1 mL). To this, 0.0065 mL (0.05 mmol) of α-methylstyrene and 0.005 mL (0.05 mmol) of 34% hydrogen peroxide solution were sequentially added with a microsyringe, and the mixture was sealed, followed by stirring at 50 ° C. for 24 hours. After the stirring reaction, extraction was performed with deuterated chloroform, and the amount of acetophenone produced was quantified from its ¹ H NMR (yield 4%).
[0017]
Comparative Example 3 Synthesis of Acetophenone in a System Excluding Hydrogen Peroxide In a 5 mL test tube, complex 1a (15.0 mg, 0.005 mmol) and iron nitrate nonahydrate (2.0 mg, 0.005 mmol) were added. The mixture was added and dissolved by heating with water (1 mL). After cooling this with tap water, 0.0065 mL (0.05 mmol) of α-methylstyrene and 0.005 mL (0.05 mmol) of 34% aqueous hydrogen peroxide were sequentially added with a microsyringe, and the mixture was sealed. Stirred for 24 hours. After the stirring reaction, extraction was performed with heavy chloroform, and the amount of acetophenone produced was quantified from its ¹ H NMR (yield 1%).
[0018]
Example 3 Synthesis of 4-methoxyacetophenone using complex 1a A complex 1a (15.0 mg, 0.005 mmol) and iron nitrate nonahydrate (2.0 mg, 0.005 mmol) were placed in a 5 mL test tube. An aqueous solution was prepared by heating and dissolving in water (1 mL). In a separate test tube, 7.4 mg (0.05 mmol) of 4-methoxy-α-methylstyrene was put in advance, and the aqueous solution prepared above and 0.005 mL (0.05 mmol) of 34% hydrogen peroxide solution were added thereto. After sequentially adding and sealing, the mixture was stirred at 50 ° C. for 24 hours. After the stirring reaction, the mixture was extracted with deuterated chloroform, and the amount of 4-methoxyacetophenone produced was quantified from its ¹ H NMR (61% yield).
[0019]
Example 4 Synthesis of 4-Methylacetophenone Using Complex 1a Complex 5a (15.0 mg, 0.005 mmol) and iron nitrate nonahydrate (2.0 mg, 0.005 mmol) were placed in a 5 mL test tube. And dissolved by heating with water (1 mL). After cooling this with tap water, 0.0066 mL (0.05 mmol) of 4-methyl-α-methylstyrene and 0.005 mL (0.05 mmol) of 34% aqueous hydrogen peroxide were sequentially added with a microsyringe, and the mixture was sealed. And stirred at 50 ° C. for 24 hours. After the stirring reaction, the mixture was extracted with deuterated chloroform, and the amount of 4-methylacetophenone produced was quantified from its ¹ H NMR (yield 53%).
[0020]
Example 5 Synthesis of 4-nitroacetophenone using complex 1a Complex 1a (15.0 mg, 0.005 mmol) and iron nitrate nonahydrate (2.0 mg, 0.005 mmol) were placed in a 5 mL test tube. And dissolved in water (1 mL) by heating to prepare an aqueous solution. In a separate test tube, previously put 8.2 mg (0.05 mmol) of 4-nitro-α-methylstyrene, and add thereto the aqueous solution prepared above and 0.005 mL (0.05 mmol) of 34% hydrogen peroxide solution. After sequentially adding and sealing, the mixture was stirred at 50 ° C. for 24 hours. After the stirring reaction, extraction was performed with deuterated chloroform, and the amount of 4-nitroacetophenone produced was quantified from its ¹ H NMR (yield 75%).
[0021]
Example 6 Synthesis of methyl-2-naphthyl ketone using complex 1a In a 5 mL test tube, complex 1a (15.0 mg, 0.005 mmol) and iron nitrate nonahydrate (2.0 mg, 0.005 mmol) Was dissolved in water (1 mL) by heating to prepare an aqueous solution. Another test tube was previously charged with 8.2 mg (0.05 mmol) of isopropenylnaphthalene, and the aqueous solution prepared above and 0.005 mL (0.05 mmol) of 34% aqueous hydrogen peroxide were sequentially added thereto and sealed. Thereafter, the mixture was stirred at 50 ° C. for 24 hours. After the stirring reaction, extraction was performed with deuterated chloroform, and the amount of methyl-2-naphthyl ketone produced was quantified from its ¹ HNMR (yield 40%).
[0022]
Example 7 Synthesis of methyl-2-naphthyl ketone using complex 1a (scale-up synthesis)
168.1 mg (1.0 mmol) of isopropenylnaphthalene was placed in a 100 mL eggplant-shaped flask, and separately prepared complex 1a (299.3 mg, 0.1 mmol) and iron nitrate nonahydrate (40.4 mg, 0 .1 mmol) (30 mL) and stirred for 10 minutes. 0.11 mL (1.0 mmol) of 34% aqueous hydrogen peroxide was added thereto with a microsyringe, and the mixture was sealed, followed by stirring at 50 ° C. for 24 hours. After the stirring reaction, the mixture was extracted with hexane 50 mL × 3 and chloroform 50 mL × 2, and the extract was dried over anhydrous magnesium sulfate. After drying, this was concentrated and separated by GPC to obtain methyl-2-naphthyl ketone (78.9 mg, yield 47%). At the same time, a raw material (52.2 mg) was recovered.
[0023]
【The invention's effect】
The oxidative decomposition (cleavage) reaction of olefins is a basic synthesis reaction, but the fact that ozone must be used and the reaction in an organic solvent have been a bottleneck so far. It was not yet widely practiced.
According to the method of the present invention, no harmful substance such as ozone is used, and the reaction proceeds in an aqueous medium. Therefore, the method can be carried out on an industrial scale, and great progress can be expected in the future. .

Claims

Three-dimensional cage- or bowl-shaped metal having a hydrophobic space and formed from a compound having at least three electron pairs in a molecule capable of forming a coordinate bond with a transition metal and having a substantially planar structure. A method for producing a corresponding carbonyl compound by oxidatively decomposing an olefin compound with hydrogen peroxide and an iron compound in an aqueous medium in the presence of a complex, wherein the amount of the metal complex used is 1 to 1 mol per 1 mol of the olefin compound. A process for producing a carbonyl compound, which is 30 mol%.

The method according to claim 1, wherein the olefin compound is an olefin compound having an aromatic group.

The production method according to claim 1 or 2, wherein the olefin compound is an olefin compound having a carbon-carbon double bond at a terminal of a molecule.

The method according to claim 3, wherein the transition metal is platinum or palladium.

The method according to claim 3, wherein the electron pair of the ligand capable of forming a coordination bond with the transition metal is an electron pair of a nitrogen atom of a pyridine ring.

The method according to any one of claims 3 to 5, wherein the ligand is a compound having 3 to 6 electron pairs capable of forming a coordinate bond with a transition metal in the molecule.

The method according to claim 6, wherein the ligand is 2,4,6-tris (4-pyridyl) -1,3,5-triazine.

The method according to claim 6, wherein the ligand is 2,4,6-tris (3-pyridyl) -1,3,5-triazine.

A metal complex having a hydrophobic space, process according to claim 1 is a M ₆ L ₄ type three-dimensional cage or bowl-shaped transition metal complex.

The metal complex having a hydrophobic space is represented by the following formula [1]

The production method according to claim 3, which is a compound represented by the formula:

The metal complex having a hydrophobic space is represented by the following formula [2]