JP4951250B2 - Imidazole-based compound-palladium complex catalyst and method for producing aromatic olefin compound using the same catalyst - Google Patents
Imidazole-based compound-palladium complex catalyst and method for producing aromatic olefin compound using the same catalyst Download PDFInfo
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Description
本発明は、芳香族オレフィン化合物製造において触媒として有用なイミダゾール系化合物―パラジウム錯体に関する。 The present invention relates to an imidazole compound-palladium complex useful as a catalyst in the production of an aromatic olefin compound.
芳香族オレフィン化合物は、医薬品、農薬、染料、ポリマー原料などに広く使用される有用な化合物であるが、その製造方法としては、パラジウム触媒存在下に、芳香族ハロゲン化合物とビニル化合物を塩基存在下で反応させる溝呂木―ヘック反応が用いられている。 Aromatic olefin compounds are useful compounds that are widely used in pharmaceuticals, agricultural chemicals, dyes, polymer raw materials, etc., but as a method for producing them, aromatic halogen compounds and vinyl compounds are present in the presence of a base in the presence of a palladium catalyst. The Mizorogi-Heck reaction is used.
この反応において、近年、触媒として、P(t−Bt)3等のアルキルホスフィンやアリールホスフィンなどのホスフィン化合物等を配位子としたパラジウム錯体が使用されているが、これらのものは酸化に対して不安定であり、また、ホスフィン配位子と同様に近年よく用いられているカルベン配位子を有する錯体は、合成が複雑である等の問題を有している（Journal of Molecular Catalysis A: Chemical 208(2004) 109−114）。
ハロゲン化パラジウムにイミダゾールが配位したイミダゾール―パラジウム錯体については、その合成方法、構造及び腫瘍細胞に対する活性作用に関する研究について報告されている（Inorganica Chimica Acta,36(1979) 69−77）。
As for the imidazole-palladium complex in which imidazole is coordinated to palladium halide, research has been reported on the synthesis method, structure, and activity on tumor cells (Inorganica Chimica Acta, 36 (1979) 69-77).
本発明は、芳香族ハロゲン化合物とビニル化合物を反応させる芳香族オレフィン化合物の製造において、従来のパラジウム錯体触媒に比し、より簡便に製造でき、かつ、取り扱いの容易で、触媒活性の高い新たなパラジウム錯体触媒を提供するものであり、また、当該触媒を用いた芳香族オレフィン化合物の製造方法を提供することを目的とする。 In the production of an aromatic olefin compound in which an aromatic halogen compound and a vinyl compound are reacted, the present invention can be produced more easily than a conventional palladium complex catalyst, is easy to handle, and has a new catalytic activity. An object of the present invention is to provide a palladium complex catalyst and to provide a method for producing an aromatic olefin compound using the catalyst.
本発明者は、溝呂木―ヘック反応で炭素―炭素結合を構築するパラジウム錯体について鋭意検討した結果、イミダゾール系化合物を配位子とする塩化パラジウム錯体が、その製造方法が容易であり、触媒活性も高く、かつ、安定であり保存等の取扱が容易であることを見出した。
即ち、本発明は、芳香族ハロゲン化合物（II）とビニル化合物（III）を反応して芳香族オレフィン化合物（IV）を製造する反応において、触媒として有用なイミダゾール系化合物−パラジウム錯体触媒（I）を提供する。
更に、本発明は、同触媒の存在下に、芳香族ハロゲン化合物（II）とビニル化合物（III）を反応して芳香族オレフィン化合物（IV）を製造する方法を提供するものである。
As a result of intensive studies on a palladium complex that forms a carbon-carbon bond by the Mizorogi-Heck reaction, the present inventors have found that a palladium chloride complex having an imidazole compound as a ligand is easy to produce and has a catalytic activity. It was found to be high and stable and easy to handle such as storage.
That is, the present invention relates to an imidazole compound-palladium complex catalyst (I) useful as a catalyst in a reaction in which an aromatic halogen compound (II) and a vinyl compound (III) are reacted to produce an aromatic olefin compound (IV). I will provide a.
Furthermore, the present invention provides a method for producing an aromatic olefin compound (IV) by reacting an aromatic halogen compound (II) and a vinyl compound (III) in the presence of the catalyst.
［一般式［I］中、R1及びR2は、それぞれ独立して水素原子、アルキル基、ホルミル基、又は置換又は無置換のアリール基を表し、−A−は、一重結合又は二重結合を表す。 一般式［II］中、R３は、低級アルキル基、ホルミル基、低級アルコキシ基又は低級アルキルカルボニル基を表し、Ｘは、ハロゲン原子を表す。一般式［III］中、R４は、置換又は無置換のアリール基、又は低級アルコキシカルボニル基を表す。］
[In General Formula [I], R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, a formyl group, or a substituted or unsubstituted aryl group, and —A— represents a single bond or a double bond. Represents. In the general formula [II], R 3 represents a lower alkyl group, a formyl group, a lower alkoxy group or a lower alkylcarbonyl group, and X represents a halogen atom. In general formula [III], R 4 represents a substituted or unsubstituted aryl group or a lower alkoxycarbonyl group. ]
本発明のパラジウム錯体触媒は、酸化等に対して安定であり、高い触媒活性を有しており、芳香族ハロゲン化合物とビニル化合物のカップリング反応に触媒として優れた特性を有するものである。 The palladium complex catalyst of the present invention is stable against oxidation and the like, has high catalytic activity, and has excellent characteristics as a catalyst for the coupling reaction of an aromatic halogen compound and a vinyl compound.
本発明のイミダゾール系化合物−パラジウム錯体触媒（I）としては、塩化パラジウムに、無置換或いはメチル等の置換基を有するイミダゾール或いはイミダゾリン化合物が配位したパラジウム錯体が挙げられる。特に、イミダゾリン化合物を配位子とするもの、中でも2位にメチル等の低級アルキル基を有するイミダゾリンを配位子とするパラジウム錯体が高い触媒活性を示し好適である。 Examples of the imidazole compound-palladium complex catalyst (I) of the present invention include a palladium complex in which palladium chloride is coordinated with an imidazole or imidazoline compound having no substituent or a substituent such as methyl. In particular, palladium complexes having an imidazoline compound as a ligand, particularly a palladium complex having an imidazoline having a lower alkyl group such as methyl at the 2-position as a ligand are preferable.
上記一般式［I］において、アルキル基とは、炭素数1から２０のアルキル基を意味するが、炭素数1から５のものが好適である。置換アリール基とは、低級アルキル基、低級アルコキシ基又は低級アルキルカルボニル基で置換されたフェニル基等が好適である。
本明細書において、低級アルキル基、低級アルコキシ基、低級アルキルカルボニル基及び低級アルコキシカルボニル基において、低級とは炭素数１から１０、特に1から５のものを意味する。
本発明のイミダゾール系化合物−パラジウム錯体（I）は、塩化パラジム１モルに対して、２モルのイミダゾール系化合物をＤＭＦ、アセトン、トルエン等の溶媒中で50℃付近で30分から2時間程度反応させた後、生成物を沈殿、又は溶媒を留去することによって製造することができる。
In the above general formula [I], the alkyl group means an alkyl group having 1 to 20 carbon atoms, preferably having 1 to 5 carbon atoms. The substituted aryl group is preferably a phenyl group substituted with a lower alkyl group, a lower alkoxy group or a lower alkylcarbonyl group.
In the present specification, in the lower alkyl group, lower alkoxy group, lower alkylcarbonyl group and lower alkoxycarbonyl group, the lower means one having 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms.
In the imidazole compound-palladium complex (I) of the present invention, 2 mol of imidazole compound is reacted in a solvent such as DMF, acetone, toluene, etc. for 30 minutes to 2 hours in the vicinity of 50 ° C. with respect to 1 mol of paradium chloride. The product can then be prepared by precipitation or by distilling off the solvent.
本発明では、イミダゾール系化合物−パラジウム錯体（I）の存在下、芳香族ハロゲン化合物（II）とビニル化合物（III）を反応させることを特徴とする芳香族オレフィン化合物（IV）の製造方法を提供する。
本反応において使用する芳香族ハロゲン化合物（II）において、Ｘで表されるハロゲンとしては、塩素、臭素、フッ素、沃素が挙げられるが、好ましくは臭素である。
置換基R３としては、メチル等の低級アルキル基、メトキシ等の低級アルコキシ基、アセチル基等の低級アルキルカルボニル基が挙げられる。
本反応に使用するビニル化合物（III）において、Ｒ４としては、フェニル等のアリール基又はメトキシカルボニル基等の低級アルコシキカルボニル基を表す。
The present invention provides a method for producing an aromatic olefin compound (IV), which comprises reacting an aromatic halogen compound (II) with a vinyl compound (III) in the presence of an imidazole compound-palladium complex (I). To do.
In the aromatic halogen compound (II) used in this reaction, examples of the halogen represented by X include chlorine, bromine, fluorine and iodine, with bromine being preferred.
Examples of the substituent R 3 include a lower alkyl group such as methyl, a lower alkoxy group such as methoxy, and a lower alkylcarbonyl group such as acetyl group.
In the vinyl compound (III) used in this reaction, R 4 represents an aryl group such as phenyl or a lower alkoxycarbonyl group such as a methoxycarbonyl group.
本反応においては、通常、芳香族ハロゲン化合物（II）１モルに対してビニル化合物（III）を１モルから2モル程度を使用するが、特にこれに限定されない。
本反応において、使用するイミダゾール系化合物−パラジウム錯体（I）の量は、芳香族ハロゲン化合物（II）に対して、1 mol%〜0.01mol%モルを使用するのが好適である。
本反応は、塩基存在下で実施することが好ましい。塩基の例は、炭酸カルシウム、炭酸セシウム等の無機塩基、トリアルキルアミン、酢酸ナトリウム等の有機塩基である。塩基の量は、芳香族ハロゲン化合物（II）１モルに対して、１〜１０モル、より好適には、２〜３モルを使用してよい。
本反応は、通常、８０〜１４０℃の反応温度で行われるが、好ましくは、120℃付近である。反応時間は、通常1時間から24時間の範囲であるが、これに限定されない。
In this reaction, usually 1 to 2 moles of vinyl compound (III) is used per 1 mole of aromatic halogen compound (II), but the present invention is not particularly limited thereto.
In this reaction, the imidazole compound-palladium complex (I) is preferably used in an amount of 1 mol% to 0.01 mol% mol of the aromatic halogen compound (II).
This reaction is preferably carried out in the presence of a base. Examples of the base are inorganic bases such as calcium carbonate and cesium carbonate, and organic bases such as trialkylamine and sodium acetate. The amount of the base may be 1 to 10 mol, more preferably 2 to 3 mol, per 1 mol of the aromatic halogen compound (II).
This reaction is usually carried out at a reaction temperature of 80 to 140 ° C, preferably around 120 ° C. The reaction time is usually in the range of 1 hour to 24 hours, but is not limited thereto.
本反応は、通常、溶媒、例えば、ＤＭＦ、ＤＭＡ、アセトニトリル、ジオキサン、ＴＨＦ等などの極性溶媒（特に、極性有機溶媒）中で行われるが、無溶媒下での反応も可能である。溶媒を使用する場合、その量は、芳香族ハロゲン化合物（II）１重量部に対して、１００重量部以下、例えば、５〜５０重量部、特に好ましくは、２０〜３０重量部である。 This reaction is usually carried out in a solvent, for example, a polar solvent (particularly a polar organic solvent) such as DMF, DMA, acetonitrile, dioxane, THF, etc., but a reaction without a solvent is also possible. When using a solvent, the quantity is 100 weight part or less with respect to 1 weight part of aromatic halogen compounds (II), for example, 5-50 weight part, Especially preferably, it is 20-30 weight part.
本反応は、通常は、常圧で行うことができるが、これに限定されない。
本反応は、アルゴン等の不活性ガス中で実施することが好ましい。
本反応において添加剤として、ハロゲン化テトラブチルアンモニウム、ハロゲン化リチウム、又はハロゲン化ナトリウム等を使用することが好ましい。添加剤の量は、芳香族ハロゲン化合物（II）１モルに対して、１０モル以下、例えば、０．１〜５モル、特に好ましくは、１〜２モルである。
本発明の反応条件は、上記に説明したものに限定されるものではなく、反応に用いる化合物に応じて条件を適宜変更可能である。
Although this reaction can be normally performed at a normal pressure, it is not limited to this.
This reaction is preferably carried out in an inert gas such as argon.
In this reaction, it is preferable to use tetrabutylammonium halide, lithium halide, sodium halide or the like as an additive. The amount of the additive is 10 mol or less, for example, 0.1 to 5 mol, particularly preferably 1 to 2 mol, per 1 mol of the aromatic halogen compound (II).
The reaction conditions of the present invention are not limited to those described above, and the conditions can be appropriately changed according to the compounds used in the reaction.
以下、実施例により本発明をより具体的に説明するが、本発明の範囲は、これらの実施例のみに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the scope of the present invention is not limited only to these Examples.
実施例 １
イミダゾール―パラジウム錯体1の合成
フラスコに、アルゴン雰囲気下、塩化パラジウム（70.9 mg, 0.4 mmol）、DMF 3 mLを加えた。次いで、反応溶液に、8 mLのアセトンに溶かしたイミダゾール（54.5 mg, 0.8 mmol）を、アルゴン雰囲気下加え50 ℃で攪拌した。粉末状のものが完全に無くなったら(14時間後）、ナスフラスコに移し、真空下加熱することより濃縮、乾燥させた。得られた粉末をアセトンで再結晶すると黄色結晶が得られた。
Example 1
Synthesis of imidazole-palladium complex 1
Palladium chloride (70.9 mg, 0.4 mmol) and 3 mL of DMF were added to the flask under an argon atmosphere. Next, imidazole (54.5 mg, 0.8 mmol) dissolved in 8 mL of acetone was added to the reaction solution under an argon atmosphere and stirred at 50 ° C. When the powder was completely removed (after 14 hours), it was transferred to an eggplant flask and concentrated and dried by heating under vacuum. When the obtained powder was recrystallized with acetone, yellow crystals were obtained.
実施例 ２
２-メチルイミダゾリン―パラジウム錯体2の合成
Synthesis of 2-methylimidazoline-palladium complex 2
以下に得られた化合物２のデーターを示す。
Rf = 0.60 (4:1ethyl acetate-methanol);
mp 181℃ dec.;
IR (KBr): νmax (cm-1) 3297, 2954, 2873, 1616, 1524, 1460, 1415, 1277, 1050, 954, 619, 539;
1H NMR (400 MHz, DMSO-d6)： δ 7.57 (s, 1H), 3.63-3.23 (m, 4H), 2.22 (s, 3H);
13C NMR (100.6 MHz, DMSO-d6)： δ 166.2, 53.5, 42.8, 15.6;
Anal. Calcd for C6H8Cl2N4Pd: C, 27.81; H, 4.67; N, 16.21. Found: C, 27.82; H, 4.56; N, 16.31.
The data of compound 2 obtained are shown below.
R f = 0.60 (4: 1 ethyl acetate-methanol);
mp 181 ° C dec .;
IR (KBr): ν max (cm -1 ) 3297, 2954, 2873, 1616, 1524, 1460, 1415, 1277, 1050, 954, 619, 539;
1 H NMR (400 MHz, DMSO-d 6 ): δ 7.57 (s, 1H), 3.63-3.23 (m, 4H), 2.22 (s, 3H);
13 C NMR (100.6 MHz, DMSO-d 6 ): δ 166.2, 53.5, 42.8, 15.6;
Anal. Calcd for C 6 H 8 Cl 2 N 4 Pd: C, 27.81; H, 4.67; N, 16.21. Found: C, 27.82; H, 4.56; N, 16.31.
実施例 ３
本発明触媒による芳香族オレフィン化合物の製造
フラスコに、炭酸カリウム（552.8 mg, 4 mmol）を加え、真空下加熱し乾燥させた。次いでアルゴン雰囲気下、塩化パラジウム（3.55 mg, 0.01 mmol）、イミダゾール（2.72 mg, 0.02 mmol）、DMF 10 mLを加え、50 ℃で1時間攪拌した。
アルゴン雰囲気下、反応溶液にブロモトルエン（246.1 μL, 2 mmol)、アクリル酸メチル（358.7 μL, 4 mmol）、DMF 1 mLを加え120 ℃で24時間攪拌した。反応終了後、酢酸エチルを用いて、セライトによる減圧濾過を行った後、エバポレーターで酢酸エチルを除去した。エーテルを用いて抽出を行い、有機層を無水硫酸ナトリウムを用いて乾燥した。エバポレーターを用いて溶媒を除いた後、シリカゲルカラムクロマトグラフィーで精製し、目的物を単離した。
Example 3
Production of aromatic olefin compounds by the catalyst of the present invention
Potassium carbonate (552.8 mg, 4 mmol) was added to the flask and heated under vacuum to dry. Then, under an argon atmosphere, palladium chloride (3.55 mg, 0.01 mmol), imidazole (2.72 mg, 0.02 mmol) and 10 mL of DMF were added, and the mixture was stirred at 50 ° C. for 1 hour.
Under an argon atmosphere, bromotoluene (246.1 μL, 2 mmol), methyl acrylate (358.7 μL, 4 mmol) and 1 mL of DMF were added to the reaction solution, and the mixture was stirred at 120 ° C. for 24 hours. After completion of the reaction, vacuum filtration with celite was performed using ethyl acetate, and then the ethyl acetate was removed with an evaporator. Extraction was performed using ether, and the organic layer was dried using anhydrous sodium sulfate. After removing the solvent using an evaporator, the product was purified by silica gel column chromatography to isolate the desired product.
実施例４〜１１
実施例1及び２で製造したパラジウム錯体触媒を用いて、実施例３と同様に反応して、芳香族オレフィン化合物を合成した。
Examples 4-11
Using the palladium complex catalyst produced in Examples 1 and 2, the reaction was carried out in the same manner as in Example 3 to synthesize an aromatic olefin compound.
実施例12
フラスコに、炭酸カリウム（552.8 mg, 4 mmol）を加え、真空下加熱し乾燥させた。次いでアルゴン雰囲気下、塩化パラジウム（3.55 mg, 0.01 mmol）、イミダゾール系化合物（ 0.02 mmol）、DMFを加え、50 ℃で1時間攪拌し、次の式で示されるイミダゾール系化合物―パラジウム錯体を得た。次にこれを用いて、実施例３と同様にして芳香族オレフィン化合物を製造し、下記の収率で目的とする芳香族オレフィン化合物を得た。
Example 12
Potassium carbonate (552.8 mg, 4 mmol) was added to the flask and heated under vacuum to dry. Next, under an argon atmosphere, palladium chloride (3.55 mg, 0.01 mmol), imidazole compound (0.02 mmol), and DMF were added and stirred at 50 ° C. for 1 hour to obtain an imidazole compound-palladium complex represented by the following formula. . Next, using this, the aromatic olefin compound was manufactured like Example 3, and the target aromatic olefin compound was obtained with the following yield.
（ ）内は、目的物の収率を表す。
The value in () represents the yield of the target product.
本発明のパラジウム錯体触媒を用いて製造される芳香族オレフィン化合物は、医薬品、農薬、染料、ポリマー原料などに広く使用される。
The aromatic olefin compound produced using the palladium complex catalyst of the present invention is widely used for pharmaceuticals, agricultural chemicals, dyes, polymer raw materials and the like.
Claims (3)
［式中 R1及びR2は、それぞれ独立して水素原子、アルキル基、ホルミル基、又は置換又は無置換のアリール基を表し、−A−は、一重結合又は二重結合を表す。］ A carbon-carbon coupling catalyst comprising a palladium complex represented by the following general formula.
[Wherein, R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, a formyl group, or a substituted or unsubstituted aryl group, and —A— represents a single bond or a double bond. ]
で表されるパラジウム錯体触媒の存在下、一般式［II］：
で表される芳香族ハロゲン化合物と一般式［III］：
で表されるビニル化合物を反応させることを特徴とする一般式［IV］：
の芳香族オレフィン化合物の製造方法。
［一般式［I］中、R1及びR2は、それぞれ独立して水素原子、アルキル基、ホルミル基、又は置換又は無置換のアリール基を表し、−A−は、一重結合又は二重結合を表す。 一般式［II］中、R３は、低級アルキル基、ホルミル基、低級アルコキシ基又は低級アルキルカルボニル基を表し、Ｘは、ハロゲン原子を表す。一般式［III］中、R４は、置換又は無置換のアリール基、又は低級アルコキシカルボニル基を表す。］ The following general formula [I]:
In the presence of a palladium complex catalyst represented by general formula [II]:
An aromatic halogen compound represented by the general formula [III]:
General formula [IV] characterized by reacting a vinyl compound represented by the formula:
A process for producing an aromatic olefin compound.
[In General Formula [I], R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, a formyl group, or a substituted or unsubstituted aryl group, and —A— represents a single bond or a double bond. Represents. In the general formula [II], R 3 represents a lower alkyl group, a formyl group, a lower alkoxy group or a lower alkylcarbonyl group, and X represents a halogen atom. In general formula [III], R 4 represents a substituted or unsubstituted aryl group or a lower alkoxycarbonyl group. ]
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| DE4447068A1 (en) * | 1994-12-29 | 1996-07-04 | Hoechst Ag | Process for the production of aromatic olefins |
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| DE10128144A1 (en) * | 2001-06-09 | 2002-12-12 | Oxeno Olefinchemie Gmbh | Process for the telomerization of non cyclic olefins having at least two conjugated double bonds or mixtures containing olefins, with nucleophiles comprises use of palladium carbene complexes. |
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