JP2011162503A - Palladium-containing compound, process for producing the same and process for producing organic compound using the same - Google Patents
Palladium-containing compound, process for producing the same and process for producing organic compound using the same Download PDFInfo
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Abstract
Description
本発明は、含パラジウム化合物及びそれの製造方法とこれを用いる含ヘテロ原子置換アルケンないしアセチレン化合物の製造に関するものである。 The present invention relates to a palladium-containing compound, a method for producing the same, and production of a heteroatom-substituted alkene or acetylene compound using the same.
パラジウム化合物は工業触媒として広く利用されている。その代表的な例としてテトラトリフェニルホスフィンパラジウムやビストリフェニルホスインジクロロパラジウムなどがある。 Palladium compounds are widely used as industrial catalysts. Typical examples include tetratriphenylphosphine palladium and bistriphenylphosphine dichloropalladium.
構造の違うパラジウム化合物が異なる触媒機能を示すため、より効率のよい触媒を求めて、パラジウム化合物の合成が盛んに行われている。特に近年、ベンゼン環にパラジウムが結合したパラダサイクロと呼ばれているものは、普通のパラジウム化合物に比べ、高い触媒活性を示すことが報告され、注目されている(非特許文献1)。 Since palladium compounds having different structures exhibit different catalytic functions, palladium compounds have been actively synthesized in search of more efficient catalysts. In particular, in recent years, what is called a paradacyclo in which palladium is bonded to a benzene ring has been reported to have a higher catalytic activity than ordinary palladium compounds, and has attracted attention (Non-Patent Document 1).
パラジウム触媒を用いる付加反応にホスフィン酸が影響して、異なる選択性で生成物を与えることは知られている(非特許文献2)。従って、同一分子内にホスフィン酸基とパラジウムを併せ持つパラジウム化合物は、最大相乗効果が期待され、これまでの化合物と異なる触媒機能を示すことが期待されるが、このような化合物については、合成法が開発されておらず、今までにまったく知られていない化合物群である。 It is known that phosphinic acid affects an addition reaction using a palladium catalyst to give a product with different selectivity (Non-patent Document 2). Therefore, a palladium compound having both a phosphinic acid group and palladium in the same molecule is expected to have the maximum synergistic effect, and is expected to show a different catalytic function from the conventional compounds. Is a group of compounds that have not been developed and are not known at all.
本発明は、分子内にホスフィン酸基とパラジウムを併せ持つ新規な化合物とその合成法を開発し、これを用いて新たな有機化合物を合成する方法を提供することを目的としてなされたものである。 An object of the present invention is to develop a novel compound having both a phosphinic acid group and palladium in the molecule and a synthesis method thereof, and to provide a method of synthesizing a new organic compound using the compound.
本発明者らは、酢酸パラジウムとフェニルホスフィン酸の研究を行う過程において、偶然にこの二種類の化合物の混合溶液から沈殿が析出することを見出した。得られた沈殿をNMRやX-線結晶解析により構造を解析したところ、これまで知られていない同一分子内にホスフィン酸基とパラジウムを併せ持つ化合物であることが分かり、この知見に基づいて本発明をなすに至った。 The inventors of the present invention have found that a precipitate is deposited from a mixed solution of these two kinds of compounds by chance in the course of studying palladium acetate and phenylphosphinic acid. When the structure of the obtained precipitate was analyzed by NMR or X-ray crystallography, it was found to be a compound having both a phosphinic acid group and palladium in the same molecule that has not been known so far. It came to make.
すなわち、本発明は、分子内にホスフィン酸基とパラジウムを併せ持つ新規な化合物とその合成法を開発し、これを用いてアセチレン類化合物に置換基を付加ないし導入し、効率よく、置換アルケン化合物ないし置換アセチレン化合物を合成する方法を提供するものである。 That is, the present invention has developed a novel compound having a phosphinic acid group and palladium in the molecule and a method for synthesizing the compound, and using this compound, a substituent is added to or introduced into an acetylene compound, thereby efficiently replacing the substituted alkene compound or A method for synthesizing a substituted acetylene compound is provided.
具体的には、本出願は、以下の発明を提供する。
〈1〉以下の一般式(I)であらわされる新規なパラジウム化合物。
〈2〉以下の一般式(IV)の化合物とPdX2(X = ハロゲン、任意の酸残基)とを反応させることによる、一般式(I)の化合物の製造法。
〈3〉一般式(I)の化合物とホスフィン類PR6R7R8とを反応させることによる、以下の一般式(II)の化合物の製造法。
ここで、PR6R7R8の具体例としては、トリメチルホスフィン、トリエチルホスフィン、トリフェニルホスフィン(PPh3)、ジフェニルメチルホスフィン、ビスジフェニルホスフィノエタン(dppe)、ビスジフェニルホスフィノプロパン(dppp)などがあげられる。
PR6R7R8としてdppe,dpppなどの1分子中にホスフィンを2個有する化合物を用いる場合は、当該2個のホスフィンそれぞれがPdと結合する。
〈4〉一般式(II)
で表わされる、新規パラジウム化合物。
〈5〉一般式(II)の化合物と化合物EHとを反応させることによる、以下の一般式(III)の化合物の製造方法。
ここで、EHとしては、(炭化水素)2P(O)H、(炭化水素-O-)2P(O)H、(炭化水素)(炭化水素-O-)P(O)H、炭化水素-SH、(炭化水素-O-)4PH、末端アセチレンなどが挙げられ、具体例としては、Ph2P(O)H, (MeO)2P(O)H, (EtO)2P(O)H, (PhO)2P(O)H, Ph(EtO)P(O)H, PhSH, (pinacolato)P(O)H, (pinacolato)2PHや、末端アセチレンが挙げられる。
〈6〉一般式(III)
で表わされる、新規パラジウム化合物。
〈7〉一般式(I)、(II)又は(III)の化合物を触媒とし、EHと下記の一般式(V)のアセチレン類とを反応させることによる、下記の一般式(VI)の化合物又は下記の一般式(VII)の化合物の製造方法。
ここで、R9、R10の代表例としては、水素、フェニル、オクチルなどが挙げられる。
Specifically, the present application provides the following inventions.
<1> A novel palladium compound represented by the following general formula (I).
<2> A process for producing a compound of the general formula (I) by reacting a compound of the following general formula (IV) with PdX 2 (X = halogen, any acid residue).
<3> A process for producing a compound of the following general formula (II) by reacting a compound of general formula (I) with phosphines PR 6 R 7 R 8 .
Here, as specific examples of PR 6 R 7 R 8 , trimethylphosphine, triethylphosphine, triphenylphosphine (PPh 3 ), diphenylmethylphosphine, bisdiphenylphosphinoethane (dppe), bisdiphenylphosphinopropane (dppp) Etc.
When a compound having two phosphines in one molecule such as dppe or dppp is used as PR 6 R 7 R 8 , each of the two phosphines binds to Pd.
<4> General formula (II)
A novel palladium compound represented by
<5> A method for producing a compound of the following general formula (III) by reacting a compound of the general formula (II) with a compound EH.
Here, as EH, (hydrocarbon) 2 P (O) H, (hydrocarbon-O-) 2 P (O) H, (hydrocarbon) (hydrocarbon-O-) P (O) H, carbonization Hydrogen-SH, (hydrocarbon-O-) 4 PH, terminal acetylene, etc. are mentioned. Specific examples include Ph 2 P (O) H, (MeO) 2 P (O) H, (EtO) 2 P ( O) H, (PhO) 2 P (O) H, Ph (EtO) P (O) H, PhSH, (pinacolato) P (O) H, (pinacolato) 2 PH, and terminal acetylene.
<6> General formula (III)
A novel palladium compound represented by
<7> A compound of the following general formula (VI) obtained by reacting EH with an acetylene of the following general formula (V) using the compound of the general formula (I), (II) or (III) as a catalyst: Or the manufacturing method of the compound of the following general formula (VII).
Here, representative examples of R 9 and R 10 include hydrogen, phenyl, octyl and the like.
本発明により、分子内にホスフィン酸基とパラジウムを併せ持つ新規なパラジウム化合物が提供される。当該化合物を用いることにより、アルキン化合物に置換基を付加ないし導入し、効率よく、置換アルケン化合物ないし置換アルキン化合物を合成することができる。 The present invention provides a novel palladium compound having both a phosphinic acid group and palladium in the molecule. By using the compound, a substituent can be added to or introduced into the alkyne compound, and a substituted alkene compound or a substituted alkyne compound can be efficiently synthesized.
以下、本発明を実施例によりさらに具体的に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
実施例1
一般式(I)の化合物の合成例
Pd(OAc)2 (5 mmol)とPh2P(O)OH(7.5 mmol)をTHFに溶かし、窒素下加熱することにより、茶色沈殿が生じた。沈殿を濾過し乾燥させることにより、1.38グラム(収率86%)の茶色固体が得られた。
構造は、以下の分析データにより決定した。
NMRデータ:1H NMR: δ 8.11-8.07 (m, 2H), 7.61-7.58 (m, 1H), 7.55-7.52 (m, 2H), 6.69-65 (m, 1H), 6.63-6.59 (m, 1H), 6.40-6.37 (m, 1H), 6.34-6.32 (m, 1H). 31P NMR: δ 70.6. Anal. Calcd. for C12H9O2PPd: C, 44.68; H, 2.81. Found: C, 45.08; H, 2.73.
また、構造はX―線構造解析によっても確認された。図1のORTEP図に示すように、この化合物は固体の状態で6量体として存在する。
Example 1
Synthesis examples of compounds of general formula (I)
Pd (OAc) 2 (5 mmol) and Ph 2 P (O) OH (7.5 mmol) were dissolved in THF and heated under nitrogen to form a brown precipitate. The precipitate was filtered and dried to give 1.38 grams (86% yield) brown solid.
The structure was determined by the following analytical data.
NMR data: 1H NMR: δ 8.11-8.07 (m, 2H), 7.61-7.58 (m, 1H), 7.55-7.52 (m, 2H), 6.69-65 (m, 1H), 6.63-6.59 (m, 1H ), 6.40-6.37 (m, 1H), 6.34-6.32 (m, 1H) .31P NMR: δ 70.6. Anal. Calcd. For C12H9O2PPd: C, 44.68; H, 2.81. Found: C, 45.08; H, 2.73 .
The structure was also confirmed by X-ray structural analysis. As shown in the ORTEP diagram of FIG. 1, this compound exists as a hexamer in a solid state.
実施例2
一般式(II)の化合物の合成例
融点Dec. 168 ℃. 1H NMR (CD2Cl2): δ 7.99-7.58 (m, 9H), 7.56-6.99 (m, 17H), 6.87-6.84 (m, 1H), 6.61-6.54 (m, 2H), 2.62-2.37 (m, 2H), 2.34-2.21 (m, 1H), 2.16-2.02 (m, 1H). 31P NMR (CD2Cl2): δ 61.3 (dd, JP-P = 29.4 Hz, JP-P = 7.4 Hz, 1P), 47.2 (dd, JP-P = 33.1 Hz, JP-P = 7.4 Hz, 1P), 38.2 (dd, JP-P = 33.1 Hz, JP-P = 29.4 Hz, 1P).
Example 2
Synthesis example of compounds of general formula (II)
Melting point Dec. 168 ° C. 1H NMR (CD 2 Cl 2 ): δ 7.99-7.58 (m, 9H), 7.56-6.99 (m, 17H), 6.87-6.84 (m, 1H), 6.61-6.54 (m, 2H ), 2.62-2.37 (m, 2H), 2.34-2.21 (m, 1H), 2.16-2.02 (m, 1H) .31P NMR (CD2Cl2): δ 61.3 (dd, JP-P = 29.4 Hz, JP-P = 7.4 Hz, 1P), 47.2 (dd, JP-P = 33.1 Hz, JP-P = 7.4 Hz, 1P), 38.2 (dd, JP-P = 33.1 Hz, JP-P = 29.4 Hz, 1P).
実施例3
一般式(III)の化合物の合成例
31P NMR (CD2Cl2): δ 71.9 (ddd, JP-P = 447.0 Hz, JP-P = 34.4 Hz, JP-P = 7.6 Hz, 1P), 32.1 (dd, JP-P = 447.0 Hz, JP-P = 26.8 Hz, 1P), 23.5 (dd, JP-P = 9.6 Hz, JP-P = 11.5 Hz, 1P), 20.3 (ddd, JP-P = 36.3 Hz, JP-P = 26.7 Hz, JP-P = 11.5 Hz, 1P).
構造は、さらにX-線結晶解析より確認された(図2結晶のORTEP図)。
Example 3
Synthesis example of compound of general formula (III)
31P NMR (CD2Cl2): δ 71.9 (ddd, JP-P = 447.0 Hz, JP-P = 34.4 Hz, JP-P = 7.6 Hz, 1P), 32.1 (dd, JP-P = 447.0 Hz, JP-P = 26.8 Hz, 1P), 23.5 (dd, JP-P = 9.6 Hz, JP-P = 11.5 Hz, 1P), 20.3 (ddd, JP-P = 36.3 Hz, JP-P = 26.7 Hz, JP-P = 11.5 Hz, 1P).
The structure was further confirmed by X-ray crystallography (ORTEP diagram of the crystal in Fig. 2).
実施例4
化合物1を触媒として用いた付加反応:一般式(VI)の化合物の合成例
化合物1(0.005 mmol), dppp(0.005mmol),Ph2P(O)H (0.1mmol), 1-オクチン(0.1mmol)の混合物をトルエンに溶かして70℃で3時間加熱した。生成物をシリカゲルカラムより単離した。付加物が93%の収率で得られた。
同様の操作により、付加物の合成を行った。結果は、以下の表1にまとめた。
これらの付加反応は、以下の反応式で示すとおりのものであり、表1に示すとおり、1モルのE-Hと1モルのアルキン化合物とを、0.05モルの化合物1と0.05モルの化合物Lの存在下、表1に示す温度で、表1に示す時間、加熱することにより、Eが付加したアルケン化合物が、いずれも表1に示す高収率で生成する。
表1中、a〜gは以下に示す化合物E-Hを意味し、a’〜c’は以下に示すアルキン化合物(当該式中、左側がR1であり、右側がR2である)を意味する。
Addition reaction using compound 1 as catalyst: Synthesis example of compound of general formula (VI) Compound 1 (0.005 mmol), dppp (0.005 mmol), Ph 2 P (O) H (0.1 mmol), 1-octyne (0.1 mmol) was dissolved in toluene and heated at 70 ° C. for 3 hours. The product was isolated from a silica gel column. The adduct was obtained in 93% yield.
The adduct was synthesized by the same operation. The results are summarized in Table 1 below.
These addition reactions are as shown in the following reaction formula. As shown in Table 1, 1 mol of EH and 1 mol of an alkyne compound are mixed with 0.05 mol of compound 1 and 0.05 mol of compound 1. By heating at the temperature shown in Table 1 for the time shown in Table 1 in the presence of Compound L, all of the alkene compounds to which E has been added are produced in the high yield shown in Table 1.
In Table 1, a to g represent the following compound EH, and a ′ to c ′ represent the following alkyne compound (wherein the left side is R 1 and the right side is R 2 ). .
実施例22
化合物1を触媒として用いた置換反応:一般式(VII)の化合物の合成例
実施例1の化合物1(0.005mmol), PPh3 (0.01 mmol), Ph2P(O)H (20.2 mg)と1-オクチン(0.1mmol),メチルアクリレート(0.4mmol)の混合物をトルエンに溶かし、70℃で一夜加熱した。カップリング生成物が64%の収率で得られた。
Substitution reaction using compound 1 as catalyst: Synthesis example of compound of general formula (VII) Compound 1 of Example 1 (0.005 mmol), PPh 3 (0.01 mmol), Ph 2 P (O) H (20.2 mg) A mixture of 1-octyne (0.1 mmol) and methyl acrylate (0.4 mmol) was dissolved in toluene and heated at 70 ° C. overnight. The coupling product was obtained with a yield of 64%.
Claims (11)
で表わされる、新規パラジウム化合物。 Formula (II)
A novel palladium compound represented by
で表わされる、新規パラジウム化合物。 General formula (III)
A novel palladium compound represented by
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JP2007063168A (en) * | 2005-08-30 | 2007-03-15 | National Institute Of Advanced Industrial & Technology | New bisphosphinoyl compound, method for producing the same and medicine comprising the same as active ingredient |
JP2007137850A (en) * | 2005-11-22 | 2007-06-07 | National Institute Of Advanced Industrial & Technology | Phosphorous compound and method for producing the same |
JP2012507478A (en) * | 2008-11-06 | 2012-03-29 | クラリアント・ファイナンス・(ビーブイアイ)・リミテッド | Process for the production of dialkylphosphinic acids, -esters and -salts using vinyl compounds and their use |
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JP2007063168A (en) * | 2005-08-30 | 2007-03-15 | National Institute Of Advanced Industrial & Technology | New bisphosphinoyl compound, method for producing the same and medicine comprising the same as active ingredient |
JP2007137850A (en) * | 2005-11-22 | 2007-06-07 | National Institute Of Advanced Industrial & Technology | Phosphorous compound and method for producing the same |
JP2012507478A (en) * | 2008-11-06 | 2012-03-29 | クラリアント・ファイナンス・(ビーブイアイ)・リミテッド | Process for the production of dialkylphosphinic acids, -esters and -salts using vinyl compounds and their use |
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