JPS5921879B2 - Novel palladium complex compound and its production method - Google Patents
Novel palladium complex compound and its production methodInfo
- Publication number
- JPS5921879B2 JPS5921879B2 JP4762277A JP4762277A JPS5921879B2 JP S5921879 B2 JPS5921879 B2 JP S5921879B2 JP 4762277 A JP4762277 A JP 4762277A JP 4762277 A JP4762277 A JP 4762277A JP S5921879 B2 JPS5921879 B2 JP S5921879B2
- Authority
- JP
- Japan
- Prior art keywords
- complex compound
- fumaronitrile
- palladium complex
- palladium
- production method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、新規なパラジウム錯化合物に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel palladium complex compound.
詳しくは、オレフィンの配位した新規なパラジウム錯化
合物に関するものである。遷移金属のオレフィン錯化合
物は、有機金属化学の分野において、オレフィンやアセ
チレンなどの重合、付加等各種の反応の触媒として有用
であることが知られている。とくにニッケルでは広く研
究が行われている。しかし、パラジウムや白金のオレフ
ィン錯化合物は殆んど研究が進んでいない。最近ストー
ン等は、パラジウムおよび白金に１・５−シクロオクタ
ジエン、エチレン、ノルボルネンが配位した錯化合物を
単離した〔ケミカルコミュニケーション（Ｃ「ｍ、Ｃｏ
型用ｕｎ、）３頁（１９７５年）および同４４９頁（１
９７５年）ならびにジヤーナルオブケミカルソサエテイ
ダルトントランスアクシヨンズ（ Ｊ、Ｃｈｅｍ、Ｓｏ
ｃ。Specifically, the present invention relates to a novel palladium complex compound coordinated with an olefin. Olefin complex compounds of transition metals are known in the field of organometallic chemistry to be useful as catalysts for various reactions such as polymerization and addition of olefins, acetylene, etc. Particularly extensive research is being conducted on nickel. However, research on olefin complex compounds of palladium and platinum has hardly progressed. Recently, Stone et al. isolated a complex compound in which palladium and platinum are coordinated with 1,5-cyclooctadiene, ethylene, and norbornene [Chemical Communication (C'm, Co
Un, page 3 (1975) and page 449 (1975)
975) and the Journal of Chemical Society Dalton Transactions (J, Chem, So
c.
Ｄａｌｔａ１）２７１頁（１９７７年）参照〕が、これ
らは何れも同一のオレフィン原子が配位した錯化合物で
あるが、このようなパラジウムの錯化合物は大層不安定
で、工業的に使用しうるものではなかつた。本発明者等
は先に、安定なＯ価のパラジウムのオレフィン錯化合物
であるトリス（ジベンジリデンアセトン）ジパラジウム
（ｑの合成に成功し〔ケミカルコミュニケーション（Ｃ
ｈｅｍ、Ｃｏ型用ｕｎ、）１０６５頁１９７０年および
ジヤーナルオブオルガノメタリツクケミストリイ（Ｊ。Dalta 1), p. 271 (1977)], but these are all complex compounds in which the same olefin atom is coordinated, but such palladium complex compounds are extremely unstable and cannot be used industrially. It wasn't. The present inventors previously succeeded in synthesizing tris(dibenzylideneacetone)dipalladium (q), which is a stable O-valent palladium olefin complex compound [chemical communication (C
hem, Co un, ) 1065 pages 1970 and Journal of Organometallic Chemistry (J.
Ｏｒｇａｎｏｍｅｔａｌ、Ｃｈｅｍ、） ６５巻２５３
頁（１９７４年）参照〕たが、さらに鋭意研究を進Ｊ
めた結果本発明に到達した。Organometal, Chem,) Volume 65, 253
(1974)], but further research has been carried out.
As a result, we have arrived at the present invention.
すなわち、本発明の要旨は、一般式（Ｉ）ＰｄＬ２（Ｉ
）
（式中、Ｌはフマロニトリルを表わす。That is, the gist of the present invention is that general formula (I) PdL2(I
) (In the formula, L represents fumaronitrile.
）で示されるパラジウム錯化合物、およびトリス（ジベ
ンジリデンアセトン）ジパラジウム（ｑおよびフマロニ
トリルを反応させることを特徴とする、一般式（１）Ｐ
ｄＬ２（１）
（式中、Ｌはフマロニトリルを表わす。), and tris(dibenzylideneacetone)dipalladium (q) and fumaronitrile, which is characterized by reacting with the general formula (1)P
dL2(1) (wherein, L represents fumaronitrile.
）で示されるパラジウム錯化合物の製造法に存する。) consists in a method for producing a palladium complex compound shown in
以下に本発明を詳細に説明する。本発明に係る化合物＆
ζ ビス（フマロニトリル）パラジウムである。The present invention will be explained in detail below. Compounds according to the present invention &
ζ bis(fumaronitrile) palladium.
本発明に係る化合物は、例えば次のような方法により製
造することができる。The compound according to the present invention can be produced, for example, by the following method.
すなわち、トリス（ジベンジリデンアセトン）ジパラジ
ウムおよびフマロニトリルを反応させる方法が挙げられ
る。トリス（ジベンジリデンアセトン）ジパラジウムお
よびフマロニトリルを反応させるのは、通常不活性溶媒
中で行う。このような不活性溶媒としては、アセトン、
メチルエチルケトン、メチルイソブチルケトン、シクロ
ヘキサノンなどのケトン類、ジクロコメタン、クロロホ
ルム、四塩化炭素、トリクロロエタンなどの・・ロゲン
化炭化水素類、アセトニトリル、プロピオニトリルなど
のニトリル類が好適に使用されるが、場合によつてはペ
ンタン、ヘキサン、シクロヘキサンなどのアルカン類、
ベンゼン、トルエンなどの芳香族化合物またはジエチル
エーテル、ジブチルエーテル等のエーテル化合物が使用
可能である。また、フマロニトリルを溶媒とすることも
できる。That is, a method of reacting tris(dibenzylideneacetone)dipalladium and fumaronitrile can be mentioned. The reaction of tris(dibenzylideneacetone)dipalladium and fumaronitrile is usually carried out in an inert solvent. Such inert solvents include acetone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, logenated hydrocarbons such as dichlorocomethane, chloroform, carbon tetrachloride, and trichloroethane, and nitriles such as acetonitrile and propionitrile are preferably used. Alkanes such as pentane, hexane, and cyclohexane,
Aromatic compounds such as benzene and toluene or ether compounds such as diethyl ether and dibutyl ether can be used. Further, fumaronitrile can also be used as a solvent.
フマロニトリルの量は、通常バラジウムに対し過剰に用
いる。トリス（ジベンジリデンアセトン）ジパラジウム
１モルに対して、通常２〜１００モル、好ましくは２〜
２５モル程度であるのがよい。反応温度毫通常０〜１０
０℃、好ましくは１０〜５０℃程度である。The amount of fumaronitrile is usually used in excess relative to the palladium. Usually 2 to 100 mol, preferably 2 to 100 mol, per 1 mol of tris(dibenzylideneacetone)dipalladium.
The amount is preferably about 25 moles. Reaction temperature usually 0-10
The temperature is about 0°C, preferably about 10 to 50°C.
反応は不活性ガス雰囲気下に行うことが好ましＸ．′ｏ
不活性ガスとしてはヘリウム、アルゴン、窒素などが挙
げられる。The reaction is preferably carried out under an inert gas atmosphere.X. 'o
Examples of the inert gas include helium, argon, and nitrogen.
反応後は、放置するか、必要により濃縮、冷却または貧
溶媒を添加するなど周知の方法により単離、精製するこ
とができる。After the reaction, it can be left to stand, or if necessary, it can be isolated and purified by known methods such as concentration, cooling, or addition of a poor solvent.
本発明に係わるパラジウムの錯化合物は新規なものであ
り、触媒や各種化合物の合成中間体として有用である。The palladium complex compound according to the present invention is novel and is useful as a catalyst or an intermediate for the synthesis of various compounds.
また、本発明に係わる製法によれば、非常に簡便な操作
で、かつ温和な反応条件で本発明に係わる化合物を製造
することができる。以下に実施例および参考例を挙げて
、本発明を更に詳細に説明するが、本発明は、その要旨
を超えない限り、以下の実施例により何等の限定も受け
るものではない。なお、以下の反応はすべてアルゴン雰
囲気下に行つた。Moreover, according to the production method of the present invention, the compound of the present invention can be produced with very simple operations and under mild reaction conditions. EXAMPLES The present invention will be explained in more detail with reference to examples and reference examples below, but the present invention is not limited in any way by the following examples unless the gist of the invention is exceeded. Note that all of the following reactions were performed under an argon atmosphere.
また、赤外吸収（Ｒ）スペクトルはＫＢｒペレツトにし
て、畠恨スペクトルは６０ＭＨｚで測定した。In addition, the infrared absorption (R) spectrum was measured using KBr pellets, and the infrared absorption (R) spectrum was measured at 60 MHz.
収率はモル％、元素分析は重量％で表示した。実施例
１
ビス（フマロニトリル）バラジウムトリス（ジベンジリ
デンアセトン）ジパラジウム（０〔以下（Ｄｂａ）３Ｐ
ｄ２と略す〕（４１３Ｔｆ１９：０．４５１ｍｍ０１）
およびフマロニトリル（１７９Ｗ９；２．２９６ｍｍ０
１）のアセトン（１０ｄ）溶液を、室温で２時間攪拌し
た。The yield was expressed in mol%, and the elemental analysis was expressed in weight%. Example
1 bis(fumaronitrile) palladium tris(dibenzylideneacetone) dipalladium (0 [hereinafter (Dba) 3P
d2] (413Tf19:0.451mm01)
and fumaronitrile (179W9; 2.296mm0
A solution of 1) in acetone (10d) was stirred at room temperature for 2 hours.
溶液の色は、深赤紫色から淡黄色に変化した。Ｐ過によ
り、淡黄色のビス（フマロニトリル）パラジウムの粉末
が１４９Ｗ９（収率６３％）得られた。このものは、ア
セトニトリルを除く殆んどの有機溶媒に難溶性である。
Ｍ．ｐ．８３−８５℃（Ｄｅｃ．）ＩＲスペクトル：２
２３５、２２３０礪−１（ν０Ｊ）元素分析Ｃ８Ｈ４Ｎ
４Ｐｄとしての
使用例 １
ビス（フマロニトリル）パラジウムを触媒としてオレフ
インとアセチレンとの付加反応を行なわせた。The color of the solution changed from deep reddish-purple to light yellow. Powder 149W9 (yield 63%) of pale yellow bis(fumaronitrile) palladium was obtained by P filtration. It is sparingly soluble in most organic solvents except acetonitrile.
M. p. 83-85°C (Dec.) IR spectrum: 2
235, 2230 礪-1 (ν0J) elemental analysis C8H4N
Example of use as 4Pd 1 Addition reaction between olefin and acetylene was carried out using bis(fumaronitrile)palladium as a catalyst.
反応式は次の通りである。容量２０ｍ１の耐圧反応管に
アルゴン雰囲気下、ビス（フマロニトリル）パラジウム
５８．０１ｎｙ（０．２２１ｍｍ０１）を入れ、クロロ
ホルム５ｍ仲に懸濁させた。The reaction formula is as follows. 58.01 ny (0.221 mm01) of bis(fumaronitrile) palladium was placed in a pressure-resistant reaction tube with a capacity of 20 m1 under an argon atmosphere, and suspended in 5 m of chloroform.
１−ヘキセン２．８ｍ１（２２．６ｍｍ０１）を添加し
、室温で撹拌しながら、アセチレンジカルボン酸ジメチ
ル０．２８ｍ１（２．２７ｍｍ０１）を添加した。2.8 ml (22.6 mm 01) of 1-hexene was added, and while stirring at room temperature, 0.28 ml (2.27 mm 01) of dimethyl acetylenedicarboxylate was added.
攪拌を５分間続けると緑褐色の懸濁液が得られた。４０
℃に加熱すると１０分間ほどで濃緑褐色の均一溶液が得
られた。Stirring was continued for 5 minutes, resulting in a greenish-brown suspension. 40
When heated to ℃, a dark greenish brown homogeneous solution was obtained in about 10 minutes.
Claims (1)
Ｏ）およびフマロニトリルを反応させることを特徴とす
る、一般式（ I ）ＰｄＬ＿２（ I ） （式中、Ｌはフマロニトリルを表わす。 ）で示されるパラジウム錯化合物の製造法。[Claims] 1. A palladium complex compound represented by the general formula (I) PdL_2(I) (wherein L represents fumaronitrile). 2 Tris(dibenzylideneacetone)dipalladium (
A method for producing a palladium complex compound represented by the general formula (I) PdL_2(I) (wherein L represents fumaronitrile), which comprises reacting PdL_2(I) and fumaronitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4762277A JPS5921879B2 (en) | 1977-04-25 | 1977-04-25 | Novel palladium complex compound and its production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4762277A JPS5921879B2 (en) | 1977-04-25 | 1977-04-25 | Novel palladium complex compound and its production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53132526A JPS53132526A (en) | 1978-11-18 |
| JPS5921879B2 true JPS5921879B2 (en) | 1984-05-22 |
Family
ID=12780300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4762277A Expired JPS5921879B2 (en) | 1977-04-25 | 1977-04-25 | Novel palladium complex compound and its production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5921879B2 (en) |
-
1977
- 1977-04-25 JP JP4762277A patent/JPS5921879B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53132526A (en) | 1978-11-18 |
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