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JP5610464B2 - Palladium-containing compound, method for producing the same, and method for producing organic compound using the same - Google Patents
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JP5610464B2 - Palladium-containing compound, method for producing the same, and method for producing organic compound using the same - Google Patents

Palladium-containing compound, method for producing the same, and method for producing organic compound using the same Download PDF

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JP5610464B2
JP5610464B2 JP2010028681A JP2010028681A JP5610464B2 JP 5610464 B2 JP5610464 B2 JP 5610464B2 JP 2010028681 A JP2010028681 A JP 2010028681A JP 2010028681 A JP2010028681 A JP 2010028681A JP 5610464 B2 JP5610464 B2 JP 5610464B2
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韓　立彪
立彪 韓
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National Institute of Advanced Industrial Science and Technology AIST
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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.

J. Dupond; M. Pfeffer著、Palladacycles, Wiley-VCH, 2008By J. Dupond; M. Pfeffer, Palladacycles, Wiley-VCH, 2008 Han らAngew. Chem., Int. Ed. 1998, 37, 4196Han et al. Angew. Chem., Int. Ed. 1998, 37, 4196

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。
（式中のR1―R5は、同じでも異なってもよい水素又は炭化水素置換基である；ｎは1-20である）
〈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。
例えば、一般式（Ｉ）の化合物は、酢酸パラジウムと一般式（IV）のフェニルホスフィン酸を反応させることにより合成する。
〈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。
（式中のR1―R8は、同じでも異なってもよい水素又は炭化水素置換基である；ｍは1-4である）
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）
（式中のR1―R8は、同じでも異なってもよい水素又は炭化水素置換基である；ｍは1-4である）
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。
（式中のR1―R8は、同じでも異なってもよい水素又は炭化水素置換基である；Eは、EHから水素原子Hを除いた残基であり、EHは、15族もしくは16族ヘテロ原子含有水素化合物または末端アセチレンである；ｍは1-4である）
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）
（式中のR1―R8は、同じでも異なってもよい水素又は炭化水素置換基である；Eは、EHから水素原子Hを除いた残基であり、EHは、15族もしくは16族ヘテロ原子含有水素化合物または末端アセチレンである；ｍは1-4である）
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。
（式中のR9、R10は、同じでも異なってもよい水素又は炭化水素置換基である）
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).
(Wherein R 1 -R 5 are the same or different hydrogen or hydrocarbon substituents; n is 1-20)
<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).
For example, the compound of general formula (I) is synthesized by reacting palladium acetate with phenylphosphinic acid of general formula (IV).
<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 .
(Wherein R 1 -R 8 are the same or different hydrogen or hydrocarbon substituents; m is 1-4)
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)
(Wherein R 1 -R 8 are the same or different hydrogen or hydrocarbon substituents; m is 1-4)
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.
(Wherein R 1 to R 8 are the same or different hydrogen or hydrocarbon substituents; E is a residue obtained by removing a hydrogen atom H from EH, and EH is a group 15 or 16 A heteroatom-containing hydrogen compound or terminal acetylene; m is 1-4)
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)
(Wherein R 1 to R 8 are the same or different hydrogen or hydrocarbon substituents; E is a residue obtained by removing a hydrogen atom H from EH, and EH is a group 15 or 16 A heteroatom-containing hydrogen compound or terminal acetylene; m is 1-4)
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).
(Wherein R 9 and R 10 are the same or different hydrogen or hydrocarbon substituents)
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.

実施例１の化合物（一般式（Ｉ）に該当する）のX―線構造解析ORTEP図X-ray structural analysis ORTEP diagram of the compound of Example 1 (corresponding to general formula (I)) 実施例３の化合物（一般式（III）に該当する）のX―線構造解析ORTEP図X-ray structural analysis ORTEP diagram of the compound of Example 3 (corresponding to general formula (III))

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。
融点：174℃（分解）
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.
Melting point: 174 ° C (decomposition)
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
実施例１に示す化合物１（0.2 mmol）とビスジフェニルホスフィノエタン(0.2 mmol)をジクロロエタン中に溶かした。白い沈殿が析出し、窒素下濾過したところ、上記化合物２が66％の収率で得られた。この錯体は新規化合物である。
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)
Compound 1 (0.2 mmol) shown in Example 1 and bisdiphenylphosphinoethane (0.2 mmol) were dissolved in dichloroethane. A white precipitate was deposited and filtered under nitrogen to obtain Compound 2 in 66% yield. This complex is a novel compound.
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
実施例１に示す化合物１(0.5 mmol)とMe2PCH2CH2PMe2 (0.5 mmol)とジフェニルホスフィンオキシド（0.5 mmol）をジクロロホルムに溶かした。再結晶により生成物を精製したところ、上記化合物３が78％の収率で得られた。
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)
Compound 1 (0.5 mmol), Me 2 PCH 2 CH 2 PMe 2 (0.5 mmol) and diphenylphosphine oxide (0.5 mmol) shown in Example 1 were dissolved in dichlorochloroform. When the product was purified by recrystallization, Compound 3 was obtained in a yield of 78%.
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。
実施例５−２１
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。
Example 4
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.
Example 5-21
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。
Example 22
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 (12)

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。
（式中のR1-R5は、同じでも異なってもよい水素又は炭化水素置換基である；ｎは1-20である） A novel palladium compound represented by the following general formula (I).
(Wherein R 1 -R 5 are the same or different hydrogen or hydrocarbon substituents; n is 1-20) 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を特徴とする、請求項１に記載の一般式（Ｉ）の化合物の製造方法。
（式中のR1-R5は、同じでも異なってもよい水素又は炭化水素置換基である） The method for producing a compound of the general formula (I) according to claim 1, wherein the compound of the following general formula (IV) is reacted with PdX 2 (X = halogen, any acid residue).
(Wherein R 1 -R 5 are the same or different hydrogen or hydrocarbon substituents) 請求項１に記載の一般式（Ｉ）の化合物とホスフィン類PR6R7R8とを反応させることを特徴とする、以下の一般式（II）の化合物の製造方法。
（式中のR1-R 5 は、同じでも異なってもよい水素又は炭化水素置換基である；R 6 -R 7 は、同じでも異なってもよい水素又は炭化水素置換基であり、R 8 は、水素又は炭化水素置換基であるか、または、PR 6 R 7 基で置換された炭化水素置換基であり、後者の場合、分子中の２個のホスフィンそれぞれがPdと結合する；ｍは1-4である） A method for producing a compound of the following general formula (II), comprising reacting the compound of the general formula (I) according to claim 1 with phosphines PR 6 R 7 R 8 .
(R 1 -R 5 in the formula, either the same or different is also good hydrogen or a hydrocarbon substituent; R 6 -R 7 are also good hydrogen or hydrocarbon substituents be the same or different, R 8 Is a hydrogen or hydrocarbon substituent or a hydrocarbon substituent substituted with a PR 6 R 7 group, in which case each of the two phosphines in the molecule is bound to Pd; 1-4) PR6R7R8が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）であり、当該分子中の２個のホスフィンそれぞれがPdと結合することを特徴とする、請求項３に記載の方法。 The PR 6 R 7 R 8 is bisdiphenylphosphinoethane (dppe) or bisdiphenylphosphinopropane (dppp ), and each of the two phosphines in the molecule is bonded to Pd. The method described in 1. 一般式（II）
（式中のR1-R 5 は、同じでも異なってもよい水素又は炭化水素置換基である；R 6 -R 7 は、同じでも異なってもよい水素又は炭化水素置換基であり、R 8 は、水素又は炭化水素置換基であるか、または、PR 6 R 7 基で置換された炭化水素置換基であり、後者の場合、分子中の２個のホスフィンそれぞれがPdと結合する；ｍは1-4である）
で表わされる、新規パラジウム化合物。 Formula (II)
(R 1 -R 5 in the formula, either the same or different is also good hydrogen or a hydrocarbon substituent; R 6 -R 7 are also good hydrogen or hydrocarbon substituents be the same or different, R 8 Is a hydrogen or hydrocarbon substituent or a hydrocarbon substituent substituted with a PR 6 R 7 group, in which case each of the two phosphines in the molecule is bound to Pd; 1-4)
A novel palladium compound represented by PR6R7R8が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）であり、当該分子中の２個のホスフィンそれぞれがPdと結合することを特徴とする、請求項５に記載の化合物。 6. PR 6 R 7 R 8 is bisdiphenylphosphinoethane (dppe) or bisdiphenylphosphinopropane (dppp ), and each of the two phosphines in the molecule binds to Pd. Compound described in 1. 請求項５に記載の一般式（II）の化合物と化合物EHとを反応させることを特徴とする、以下の一般式（III）の化合物の製造方法。
（式中のR1-R 5 は、同じでも異なってもよい水素又は炭化水素置換基である；R 6 -R 7 は、同じでも異なってもよい水素又は炭化水素置換基であり、R 8 は、水素又は炭化水素置換基であるか、または、PR 6 R 7 基で置換された炭化水素置換基であり、後者の場合、分子中の２個のホスフィンそれぞれがPdと結合する；ｍは1-4である；Eは、EHから水素原子Hを除いた残基であり、EHは、水素原子が少なくとも１つ結合した５価のリン原子を有する化合物、水素原子が少なくとも１つ結合した２価のイオウ原子を有する化合物または末端アセチレンである） A method for producing a compound of the following general formula (III), comprising reacting the compound of the general formula (II) according to claim 5 with a compound EH.
(R 1 -R 5 in the formula, either the same or different is also good hydrogen or a hydrocarbon substituent; R 6 -R 7 are also good hydrogen or hydrocarbon substituents be the same or different, R 8 Is a hydrogen or hydrocarbon substituent or a hydrocarbon substituent substituted with a PR 6 R 7 group, in which case each of the two phosphines in the molecule is bound to Pd; 1-4 is; E is a residue obtained by removing hydrogen atom H from EH, EH is a compound having a pentavalent phosphorus atom to which at least one hydrogen atom is bonded, and at least one hydrogen atom is bonded Ru compound or terminal acetylene der having a divalent sulfur atom) EHが、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、及び、末端アセチレンから選ばれるいずれか１つであることを特徴とする、請求項７に記載の方法。 EH is 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. 一般式（III）
（式中のR1-R 5 は、同じでも異なってもよい水素又は炭化水素置換基である；R 6 -R 7 は、同じでも異なってもよい水素又は炭化水素置換基であり、R 8 は、水素又は炭化水素置換基であるか、または、PR 6 R 7 基で置換された炭化水素置換基であり、後者の場合、分子中の２個のホスフィンそれぞれがPdと結合する；ｍは1-4である；Eは、EHから水素原子Hを除いた残基であり、EHは、水素原子が少なくとも１つ結合した５価のリン原子を有する化合物、水素原子が少なくとも１つ結合した２価のイオウ原子を有する化合物または末端アセチレンである）
で表わされる、新規パラジウム化合物。 General formula (III)
(R 1 -R 5 in the formula, either the same or different is also good hydrogen or a hydrocarbon substituent; R 6 -R 7 are also good hydrogen or hydrocarbon substituents be the same or different, R 8 Is a hydrogen or hydrocarbon substituent or a hydrocarbon substituent substituted with a PR 6 R 7 group, in which case each of the two phosphines in the molecule is bound to Pd; 1-4 is; E is a residue obtained by removing hydrogen atom H from EH, EH is a compound having a pentavalent phosphorus atom to which at least one hydrogen atom is bonded, and at least one hydrogen atom is bonded Ru compound or terminal acetylene der having a divalent sulfur atom)
A novel palladium compound represented by EHが、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、及び、末端アセチレンから選ばれるいずれか１つであることを特徴とする、請求項９に記載の化合物。 EH is 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 any one selected from terminal acetylene, The compound according to claim 9. 請求項１に記載の一般式（Ｉ）、請求項５に記載の一般式（II）、又は、請求項９に記載の一般式（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を特徴とする、下記の一般式（VI）の化合物の製造方法。
（式中のR9、R10は、同じでも異なってもよい水素又は炭化水素置換基である） A compound represented by the general formula (I) according to claim 1, the general formula (II) according to claim 5, or the compound represented by general formula (III) according to claim 9 is used as a catalyst, and EH and the following general formula ( A process for producing a compound of the following general formula (VI), characterized by reacting with acetylenes of V).
(Wherein R 9 and R 10 are the same or different hydrogen or hydrocarbon substituents) 請求項１に記載の一般式（Ｉ）、請求項５に記載の一般式（II）、又は、請求項９に記載の一般式（III）の化合物を触媒とし、EHと下記の一般式（Ｖ）においてＲ  A compound represented by the general formula (I) according to claim 1, the general formula (II) according to claim 5, or the compound represented by general formula (III) according to claim 9 is used as a catalyst, and EH and the following general formula ( R) in V) 10Ten が水素である末端アセチレン類とをPPh3の存在下で反応させることを特徴とする、下記の一般式（VII）の化合物の製造方法。A process for producing a compound of the following general formula (VII), wherein terminal acetylenes in which is hydrogen is reacted in the presence of PPh3.
（式中のR(R in the formula 99 は、同じでも異なってもよい水素又は炭化水素置換基であり、RAre the same or different hydrogen or hydrocarbon substituents, R 10Ten は水素である）Is hydrogen)
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