JP3438571B2

JP3438571B2 - C70 derivative

Info

Publication number: JP3438571B2
Application number: JP05657198A
Authority: JP
Inventors: 栄一中村; 正也澤村
Original assignee: Mitsubishi Chemical Corp
Current assignee: Mitsubishi Chemical Corp
Priority date: 1998-03-09
Filing date: 1998-03-09
Publication date: 2003-08-18
Anticipated expiration: 2018-03-09
Also published as: JPH11255508A

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は新規なＣ₇₀誘導体、
Ｃ₇₀誘導体からなる新規な配位子および該配位子を含む
金属錯体、ならびにこれらの化合物の製造方法に関する
ものである。TECHNICAL FIELD The present invention relates to a novel C ₇₀ derivative,
The present invention relates to a novel ligand composed of a C ₇₀ derivative, a metal complex containing the ligand, and a method for producing these compounds.

【０００２】[0002]

【従来の技術及び発明が解決しようとする課題】炭素ク
ラスターの代表的な化合物であるフラーレン（Ｃ₆₀）の
η⁵型シクロペンタジエニル配位子およびその金属錯体
はすでに報告されている（Journal of American Chemic
al Society, 118 巻、12850 ページ、1996年）。しか
し、Ｃ₇₀のη⁵型シクロペンタジエニル配位子はについ
ては知られていない。Ｃ₇₀はＣ₆₀にくらべて共役ポリエ
ン系を構築する炭素原子の数がより多いので、Ｃ₇₀やそ
の誘導体の光受容能、電子受容能などの能力はＣ₆₀を基
本骨格とした誘導体をしのぐことが期待される。2. Description of the Related Art η ⁵ type cyclopentadienyl ligands of fullerene (C ₆₀ ) which is a typical compound of carbon clusters and their metal complexes have been reported (Journal). of American Chemic
al Society, 118, 12850, 1996). However, no C ₇₀ η ⁵ -type cyclopentadienyl ligand is known. Since C ₇₀ has more carbon atoms forming a conjugated polyene system than C ₆₀ , the light-accepting ability and electron-accepting ability of C ₇₀ and its derivatives surpass those of C _60- based derivatives. It is expected.

【０００３】[0003]

【発明を解決するための手段】そこで本発明者らはＣ₇₀
のη⁵型シクロペンタジエニル配位子に関する研究を進
めた結果、本発明を完成するに至った。すなわち、本発
明の要旨は、下記の一般式（Ｉ）Therefore, the present inventors have found that C ₇₀
The present invention has been completed as a result of research on the η ⁵ -type cyclopentadienyl ligand. That is, the gist of the present invention is the following general formula (I)

【０００４】[0004]

【化４】 [Chemical 4]

【０００５】（上記の式中、ＲはＣ₁〜Ｃ₁₀のアルキル
基、または置換基を有していてもよいＣ₆〜Ｃ₁₄のアリ
ール基を表す）で表されるＣ₇₀誘導体、下記の一般式
（II）(Wherein R represents a C _{1 to} C ₁₀ alkyl group or a C _{6 to} C ₁₄ aryl group which may have a substituent), and a C ₇₀ derivative represented by the following: General formula (II)

【０００６】[0006]

【化５】 [Chemical 5]

【０００７】（上記の式中、ＲはＣ₁〜Ｃ₁₀のアルキル
基、または置換基を有していてもよいＣ₆〜Ｃ₁₄のアリ
ール基を表す）で表されるシクロペンタジエニドイオン
からなるη⁵型シクロペンタジエニル配位子、上記一般
式（II）のη⁵型シクロペンタジエニル配位子を含む金
属錯体及びこれらの化合物の製造方法に存する。以下、
本発明について詳細に説明する。(Wherein R represents a C ₁ -C ₁₀ alkyl group or a C ₆ -C ₁₄ aryl group which may have a substituent). consisting eta ⁵ type cyclopentadienyl ligand resides in the method for producing a metal complex and these compounds containing eta ⁵ type cyclopentadienyl ligand of the general formula (II). Less than,
The present invention will be described in detail.

【０００８】上記一般式（Ｉ）、（II）および（III)に
おいて、Ｒで定義されるＣ₁〜Ｃ₁₀のアルキル基として
は、メチル基、エチル基、プロピル基、ブチル基、ペン
チル基、ヘキシル基、ヘプチル基、オクチル基、ノニル
基、デシル基等の直鎖状もしくは分岐鎖状のアルキル基
が挙げられる。Ｃ₆〜Ｃ₁₄のアリール基としてはフェニ
ル基、ナフチル基等が挙げられ、かかるアリール基はフ
ッ素原子、塩素原子、臭素原子等のハロゲン原子；メチ
ル基、エチル基、プロピル基、イソプロピル基、ブチル
基、イソブチル基、sec-ブチル基、tert- ブチル基、ペ
ンチル基、イソペンチル基、ネオペンチル基、tert- ペ
ンチル基等のＣ₁〜Ｃ₅のアルキル基；トリフルオロメ
チル基；メトキシ基、エトキシ基、プロポキシ基、イソ
プロポキシ基、ブトキシ基、イソブトシキ基、tert- ブ
トキシ基、ペンチルオキシ基、イソペンチルオキシ基等
のＣ₁〜Ｃ₅のアルコキシ基；メチレンジオキシ基の中
から選ばれる１以上の置換基を有していてもよい。上記
一般式（Ｉ）、（II）および（III)において、Ｒで定義
されるＣ₁〜Ｃ₁₀のアルキル基のより好ましい例として
は、メチル基、エチル基、プロピル基、ブチル基、ペン
チル基等が挙げられる。Ｃ₆〜Ｃ₁₄のアリール基の置換
基の好ましい例としては、フッ素原子、塩素原子、臭素
原子、メチル基、エチル基、プロピル基、イソプロピル
基、トリフルオロメチル基、メトキシ基、エトキシ基、
プロポキシ基、イソプロポキシ基等が挙げられる。上記
一般式（Ｉ）のＣ₇₀誘導体製造に用いるグリニャール試
薬としては、ＲＭｇＣｌ、ＲＭｇＢｒ、ＲＭｇＩ（Ｒは
すでに定義したとおりである）などが挙げられ、このグ
リニャール試薬とハロゲン化銅誘導体を混合することに
より有機銅試薬を調製することができる。ハロゲン化銅
誘導体の具体的な例としては、ＣｕＢｒ・ＳＭｅ₂など
が挙げられる。In the above general formulas (I), (II) and (III), the C ₁ -C ₁₀ alkyl group defined by R is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Examples thereof include linear or branched alkyl groups such as hexyl group, heptyl group, octyl group, nonyl group, and decyl group. Examples of the C _{6 to} C ₁₄ aryl group include a phenyl group and a naphthyl group. Such aryl groups include halogen atoms such as fluorine atom, chlorine atom and bromine atom; methyl group, ethyl group, propyl group, isopropyl group and butyl group. Group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group and other C ₁ -C ₅ alkyl groups; trifluoromethyl group; methoxy group, ethoxy group, Propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group and other C _{1 to} C ₅ alkoxy groups; one or more substitutions selected from methylenedioxy groups It may have a group. In the above general formulas (I), (II) and (III), more preferable examples of the C _{1 to} C ₁₀ alkyl group defined by R are a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. Etc. Preferred examples of the substituent of the C ₆ -C ₁₄ aryl group include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a trifluoromethyl group, a methoxy group, an ethoxy group,
Examples thereof include a propoxy group and an isopropoxy group. Examples of the Grignard reagent used for the production of the C ₇₀ derivative of the above general formula (I) include RMgCl, RMgBr, RMgI (R is as defined above), and the Grignard reagent is mixed with a copper halide derivative. The organic copper reagent can be prepared by Specific examples of the copper halide derivative include CuBr.SMe _{2 and the} like.

【０００９】上記一般式（III)の金属錯体の製造方法に
おいて、上記一般式（I ）のＣ₇₀誘導体に反応させる金
属アルコキシドを構成する金属としては、アルカリ金
属、遷移金属、またはランタノイドなどが挙げられ、金
属アルコキシドを構成するアルコキシドとしてはメトキ
シ基、エトキシ基、プロポキシ基、イソプロポキシ基、
ブトキシ基、イソブトシキ基、tert- ブトキシ基、ペン
チルオキシ基、イソペンチルオキシ基等のＣ₁〜Ｃ₅の
アルコキシ基が挙げられる。金属の好ましい例としては
Ｌｉ、Ｎａ、Ｋ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃ
ｕ、Ｚｎ、Ｚｒ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｄ、Ｒ
ｔ、Ａｕ、Ｈｇ、Ｔｌ、Ｓｍなどが挙げられ、アルコキ
シドとして好ましい例としては、メトキシ基、エトキシ
基、tert- ブトキシ基等が挙げられる。次に本発明の化
合物の製造法について説明する。製造法１上記一般式（Ｉ）で表される化合物の製造法In the method for producing the metal complex of the general formula (III), the metal constituting the metal alkoxide to be reacted with the C ₇₀ derivative of the general formula (I) includes alkali metal, transition metal, lanthanoid and the like. As the alkoxide constituting the metal alkoxide, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group,
Examples thereof include C _{1 to} C ₅ alkoxy groups such as butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group and isopentyloxy group. Preferred examples of the metal are Li, Na, K, Cr, Mn, Fe, Co, Ni, C
u, Zn, Zr, Ru, Rh, Pd, Ag, Cd, R
Examples thereof include t, Au, Hg, Tl and Sm, and preferable examples of the alkoxide include a methoxy group, an ethoxy group and a tert-butoxy group. Next, a method for producing the compound of the present invention will be described. Production Method 1 Production Method of Compound Represented by General Formula (I)

【００１０】[0010]

【化６】 [Chemical 6]

【００１１】上記一般式（Ｉ）で表されるＣ₇₀誘導体の
製造に用いる有機銅試薬は、文献記載の方法（Journal
of American Chemical Society, 99巻、253 ページ、19
77年）に準じて調製することができる。たとえば、ＲＭ
ｇＢｒ（Ｒはすでに定義したとおりである）で表される
グリニャール試薬とＣｕＢｒ・ＳＭｅ₂のようなハロゲ
ン化銅誘導体をテトラヒドロフラン（ＴＨＦ）、ジエチ
ルエーテル等のエーテル系溶媒中で混合することにより
調製することができる。次にＣ₇₀をトルエン、クロルベ
ンゼン、ジクロロベンゼン等の芳香族炭化水素系溶媒に
溶解して−１００〜−３０℃に冷却し、同じ温度に冷却
した５〜５０当量の有機銅試薬を５分〜１時間かけて滴
下した後、同じ温度で３０分〜２４時間撹拌してから昇
温し、−２０〜３０℃で５〜５０時間撹拌すると目的物
の生成がＨＰＬＣ等で確認できる。この反応液にＮＨ₄
Ｃｌ水溶液などを加えて反応を停止してから常法の後処
理を行えば目的物を単離することができる。より好まし
い反応条件としては、−７８℃前後で混合してから同温
度で１時間、さらに１０℃前後で１０〜２４時間撹拌す
ることにより、高収率で目的物を得ることができる。製造法２上記一般式（III)で表される化合物の製造法The organocopper reagent used for the production of the C ₇₀ derivative represented by the above general formula (I) is a method described in the literature (Journal
of American Chemical Society, 99, 253 pages, 19
1977). For example, RM
Prepared by mixing a Grignard reagent represented by gBr (R is as defined above) and a copper halide derivative such as CuBr.SMe ₂ in an ether solvent such as tetrahydrofuran (THF) or diethyl ether. be able to. Next, C ₇₀ was dissolved in an aromatic hydrocarbon solvent such as toluene, chlorobenzene, or dichlorobenzene and cooled to -100 to -30 ° C, and 5 to 50 equivalents of the organic copper reagent cooled to the same temperature was added for 5 minutes. After dropping over 1 hour, the mixture is stirred at the same temperature for 30 minutes to 24 hours, then heated, and stirred at -20 to 30 ° C. for 5 to 50 hours to confirm the formation of the target product by HPLC or the like. NH ₄ was added to this reaction solution.
The desired product can be isolated by adding a Cl aqueous solution or the like to stop the reaction and then carrying out a post-treatment in a conventional manner. As a more preferable reaction condition, the target product can be obtained in high yield by mixing at about -78 ° C and then stirring at the same temperature for 1 hour and further at about 10 ° C for 10 to 24 hours. Production Method 2 Production Method of Compound Represented by General Formula (III)

【００１２】[0012]

【化７】 [Chemical 7]

【００１３】上記製造法１で得られたＣ₇₀誘導体を、Ｔ
ＨＦ、トルエン等の不活性溶媒に溶解または懸濁し、
Ｒ’ＯＭ（Ｒ’はＣ₁〜Ｃ₅のアルキル基を表し、Ｍは
既に定義したとおりである）で表される金属のアルコキ
シドを１当量−２０〜５０℃で加えて撹拌すると、すみ
やかに上記一般式（III)で表される金属錯体が得られ
る。反応の条件としては、２５℃前後で反応させるのが
より好ましい。得られた金属錯体の溶液は、そのまま次
の反応に用いることもできるし、また溶媒を減圧留去す
れば、上記一般式（III)で表される金属錯体を単離する
こともできる。本発明の一般式（II）で表される配位子
および一般式（III)で表される金属錯体は、さまざまな
合成反応の配位子あるいは触媒として用いることができ
る。The C ₇₀ derivative obtained by the above production method 1 was converted to T
Dissolve or suspend in an inert solvent such as HF or toluene,
A metal alkoxide represented by R′OM (R ′ represents a C _{1 to} C ₅ alkyl group, and M is as defined above) is added at 1 equivalent to −20 to 50 ° C., and the mixture is immediately stirred. A metal complex represented by the above general formula (III) is obtained. As a reaction condition, it is more preferable to react at about 25 ° C. The solution of the obtained metal complex can be used as it is in the next reaction, or the solvent can be distilled off under reduced pressure to isolate the metal complex represented by the above general formula (III). The ligand represented by the general formula (II) and the metal complex represented by the general formula (III) of the present invention can be used as a ligand or a catalyst for various synthetic reactions.

【００１４】[0014]

【実施例】以下実施例に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。実施例１Ｃ₇₀（ｐ−ＣＦ₃Ｃ₆Ｈ₄）₃Ｈの製造ｐ−ＣＦ₃Ｃ₆Ｈ₄ ＭｇＢｒの溶液は、ｐ−ＣＦ₃Ｃ
₆Ｈ₄Ｂｒ（０．９３ｍｌ）のテトラヒドロフラン溶液
（８ｍｌ）に、金属マグネシウム（１７３ｍｇ）を加え
て用時調製した。この溶液を２．６８ｍｌ分けとって−
７８℃に冷却し、ＣｕＢｒ・ＳＭｅ₂（３９２ｍｇ）を
加えて有機銅試薬を作成し、これにＣ₇₀（１００ｍｇ）
のオルトジクロロベンゼン（１００ｍｌ）溶液を−７８
℃に冷却して１５分かけて滴下した。得られた溶液を−
７８℃で１時間撹拌してから１０℃まで昇温させてさら
に１０時間撹拌した。塩化アンモニウム水溶液を加えて
反応を停止し、有機層を分離してから水層をトルエンで
３回抽出した。混合した有機層を飽和食塩水で洗浄し、
硫酸ナトリウムのカラムを通して乾燥した。留出液を濃
縮すると粉末が得られ、この粉末をヘキサンで４回洗浄
してから減圧乾燥すると、目的物（１４０ｍｇ）が得ら
れた。収率９６％。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Solution of Example _{_{1 C 70 (p-CF 3}} C 6 H 4) 3 H of manufacturing _{_{_{p-CF 3 C 6 H 4}}} MgBr is, p-CF ₃ C
Metallic magnesium (173 mg) was added to a tetrahydrofuran solution (8 ml) of ₆ H ₄ Br (0.93 ml) to prepare it for use. 2.68 ml aliquot of this solution-
After cooling to 78 ° C., CuBr.SMe ₂ (392 mg) was added to prepare an organocopper reagent, to which C ₇₀ (100 mg) was added.
Ortho-dichlorobenzene (100 ml) solution of -78
It was cooled to 0 ° C. and added dropwise over 15 minutes. The resulting solution-
After stirring at 78 ° C. for 1 hour, the temperature was raised to 10 ° C. and stirring was continued for 10 hours. The reaction was stopped by adding an aqueous solution of ammonium chloride, the organic layer was separated, and then the aqueous layer was extracted with toluene three times. The mixed organic layer was washed with saturated saline,
Dry through a column of sodium sulfate. A powder was obtained by concentrating the distillate, and this powder was washed with hexane four times and then dried under reduced pressure to obtain the desired product (140 mg). Yield 96%.

【００１５】¹ＨＮＭＲ（４００ＭＨｚ、ＣＤＣｌ₃
／ＣＳ₂ 、δ ）：７．９２（ｄ，Ｊ＝６．５０Ｈ
ｚ，ＡｒＨ，２Ｈ），７．８４（ｄ，Ｊ＝６．５０Ｈ
ｚ，ＡｒＨ，２Ｈ），７．７１（ｄ，Ｊ＝６．５０Ｈ
ｚ，ＡｒＨ，２Ｈ），７．６６（ｄ，Ｊ＝６．５０Ｈ
ｚ，ＡｒＨ，２Ｈ），７．５８−７．５２（ｍ，Ａｒ
Ｈ，４Ｈ），４．４０（ｓ，Ｃ７０−Ｈ，１Ｈ）．¹³ Ｃ N M R ( 1 0 0 M H z 、 C D C l₃ / C S₂、
δ) 1 5 9 . 2 6 (1 C ) , 1 5 5 . 0 3 ( 1 C
) , 1 5 4 . 0 7 ( 1 C ) , 1 5 3 . 45 ( 1
C ) , 1 5 2 . 1 9 ( 1 C ) , 1 5 2 . 1 0 (
1 C ) , 1 51 . 9 4 ( 1 C ) , 1 5 0 . 2 6
( 1 C ) , 1 4 9 . 9 1 ( 1 C ) ,1 4 9 . 6 6
( 1 C ) , 1 4 9 . 1 6 ( 2 C ) , 1 4 8 . 9 8
( 2 C) , 1 4 8 . 7 7 ( 1 C ) , 1 4 8 . 5 9
( 2 C ) , 1 4 8 . 3 6( 1 C ) , 1 4 8 . 2 9
( 1 C ) , 1 4 8 . 2 5 ( 1 C ) , 1 4 7 .9 6
( 1 C ) , 1 4 7 . 8 8 ( 1 C ) , 1 4 7 . 8 6
( 1 C ) , 1 47 . 8 1 ( 1 C ) , 1 4 7 . 7 3
( 1 C ) , 1 4 7 . 5 4 ( 1 C ) ,1 4 7 . 2 7
( 1 C ) , 1 4 7 . 0 4 ( 1 C ) , 1 4 7 . 0 2
( 1 C) , 1 4 6 . 6 9 ( 1 C ) , 1 4 6 . 6 6
( 1 C ) , 1 4 6 . 4 9( 1 C ) , 1 4 6 . 2 0
( 1 C ) , 1 4 5 . 9 0 ( 1 C ) , 1 4 5 .7 5
( 1 C ) , 1 4 5 . 4 4 ( 1 C ) , 1 4 5 . 3
8 ( 2 C ) , 14 4 . 9 8 ( 1 C ) , 1 4 4 . 9
4 ( 1 C ) , 1 4 4 . 9 1 ( 1 C ), 1 4 4 .
8 9 ( 1 C ) , 1 4 4 . 7 3 ( 1 C ) , 1 4 4
. 7 1 (1 C ) , 1 4 4 . 5 3 ( 1 C ) , 1 4
4 . 1 2 ( 1 C ) , 1 4 3 . 74 ( 1 C ) , 1 4
3 . 4 0 ( 1 C ) , 1 4 3 . 2 4 ( 1 C ) , 1
43 . 0 6 ( 1 C ) , 1 4 2 . 5 7 ( 1 C ) ,
1 4 2 . 4 3 ( 1 C ) ,1 4 2 . 3 5 ( 1 C ) , 1
4 1 . 9 4 ( 1 C ) , 1 4 0 . 4 3 ( 1C ) ,
1 4 0 . 0 7 ( 1 C ) , 1 3 9 . 4 4 ( 1 C ) ,
1 3 7 . 1 9( 1 C ) , 1 3 3 . 0 5 ( 2 C ) ,
1 3 2 . 8 5 ( 1 C ) , 1 3 1 .8 6 ( 1 C ) ,
1 3 1 . 8 3 ( 1 C ) , 1 3 1 . 6 6 ( 1 C ) ,
13 1 . 5 3 ( 1 C ) , 1 3 0 . 6 1 ( 1 C ) ,
1 2 7 . 5 8 ( 3 C ) ,1 2 7 . 3 1 ( 2 C ) ,
1 2 7 . 2 2 ( 1 C ) , 1 2 6 . 8 6 ( 2C ) ,
1 2 6 . 2 0 ( 1 C ) , 1 2 6 . 0 8 - 1 2 6 . 0
0 ( m , 4 C) , 1 2 5 . 8 4 ( q , J C - F
= 3 . 7 0 H z , 2 C ) , 59 . 5 4 ( 1 C
) , 5 5 . 8 7 ( 1 C ) , 5 5 . 7 2 ( 1 C )
, 55 . 1 7 ( 1 C ) 。 F A B M S m / z
：測定値 1 2 7 6 ( M + ), 8 4 0 ( C 7 0 )
。実施例１と同様の方法により、実施例２〜実施例５
の化合物を製造した。以下その物性値のみを記す。 ¹ H NMR (400 MHz, CDCl ₃
/ CS ₂ , δ: 7.92 (d, J = 6.50H
z, ArH, 2H), 7.84 (d, J = 6.50H
z, ArH, 2H), 7.71 (d, J = 6.50H)
z, ArH, 2H), 7.66 (d, J = 6.50H
z, ArH, 2H), 7.58-7.52 (m, Ar
H, 4H), 4.40 (s, C70-H, 1H). ¹³ C NMR (100 MHz, CDC l ₃ / CS ₂ ,
δ) 1 5 9 .2 6 (1 C), 1 5 5 .0 3 (1 C
), 1 5 4 .0 7 (1 C), 1 5 3 .45 (1
C), 1 5 2 .1 9 (1 C), 1 5 2 .1 0 (
1 C), 1 5 1 .9 4 (1 C), 1 5 0 .2 6
(1 C), 1 4 9 .9 1 (1 C), 1 4 9 .6 6
(1 C), 1 4 9 .1 6 (2 C), 1 4 8 .9 8
(2 C), 1 4 8 .7 7 (1 C), 1 4 8 .5 9
(2 C), 1 4 8 .3 6 (1 C), 1 4 8 .2 9
(1 C), 1 4 8 .2 5 (1 C), 1 4 7 .9 6
(1 C), 1 4 7 .8 8 (1 C), 1 4 7 .8 6
(1 C), 1 47 .8 1 (1 C), 1 4 7 .7 3
(1 C), 1 4 7 .5 4 (1 C), 1 4 7 .2 7
(1 C), 1 4 7 .0 4 (1 C), 1 4 7 .0 2
(1 C), 1 4 6 .6 9 (1 C), 1 4 6 .6 6
(1 C), 1 4 6 .4 9 (1 C), 1 4 6 .2 0
(1 C), 1 4 5 .9 0 (1 C), 1 4 5 .7 5
(1 C), 1 4 5 .4 4 (1 C), 1 4 5 .3
8 (2 C), 14 4.9 9 (1 C), 1 4 4.9
4 (1 C), 1 4 4 .9 1 (1 C), 1 4 4.
8 9 (1 C), 1 4 4 .7 3 (1 C), 1 4 4
.7 1 (1 C), 1 4 4 .5 3 (1 C), 1 4
4 .1 2 (1 C), 1 4 3 .74 (1 C), 1 4
3 .4 0 (1 C), 1 4 3 .2 4 (1 C), 1
43 .0 6 (1 C), 1 4 2 .5 7 (1 C),
1 4 2 .4 3 (1 C), 1 4 2 .3 5 (1 C), 1
4 1 .9 4 (1 C), 1 4 0 .4 3 (1 C),
1 4 0 .0 7 (1 C), 1 3 9 .4 4 (1 C),
1 3 7 .1 9 (1 C), 1 3 3 .0 5 (2 C),
1 3 2 .8 5 (1 C), 1 3 1 .8 6 (1 C),
1 3 1 .8 3 (1 C), 1 3 1 .6 6 (1 C),
13 1 .5 3 (1 C), 1 3 0 .6 1 (1 C),
1 2 7 .5 8 (3 C), 1 2 7 .3 1 (2 C),
1 2 7 .2 2 (1 C), 1 2 6 .8 6 (2C),
1 2 6 .2 0 (1 C), 1 2 6 .0 8-1 2 6 .0
0 (m, 4 C), 1 2 5 .8 4 (q, JC-F
= 3 .7 0 Hz, 2 C), 59 .5 4 (1 C
), 5 5 .8 7 (1 C), 5 5 .7 2 (1 C)
, 55 .17 (1 C). FABMS m / z
: Measured value 1 2 7 6 (M +), 8 4 0 (C 7 0)
. Example 2 to Example 5 were performed in the same manner as in Example 1.
Was prepared. Only the physical properties will be described below.

【００１６】実施例２ C₇₀ Ph₃ Hの製造¹ H N M R ( 4 0 0 M H z 、 C D C l₃ / C
S₂、δ) ：7 . 8 0 - 7 .7 5 ( m , P h H , 2
H ) , 7 . 7 0 - 7 . 6 6 ( m , P h H , 2H ) ,
7 . 5 8 - 7 . 5 2 ( m , A r H , 3 H ) ,
7 . 5 0 - 7 .2 0 ( m , P h H , 8 H )， 4 .
4 1 ( s , 1 H ) 。¹³ C N M R ( 1 0 0 M H z , C D C l₃ / C S₂
、δ) 、1 6 0 . 7 0( 1 C ) , 1 5 5 . 6 7 ( 1
C ) , 1 5 5 . 0 7 ( 1 C ) , 1 5 3 .8 0 ( 1
C ) , 1 5 2 . 6 2 ( 1 C ) , 1 5 3 . 1 4
( 1 C ) , 15 2 . 6 2 ( 1 C ) , 1 5 2 . 1 9
( 1 C ) , 1 5 0 . 1 6 ( 1 C ), 1 4 9 . 8 7
( 1 C ) , 1 4 9 . 5 7 ( 1 C ) , 1 4 9 . 4
2 (1 C ) , 1 4 9 . 3 9 ( 1 C ) , 1 4 9 . 1
7 ( 1 C ) , 1 4 9 . 08 ( 1 C ) , 1 4 8 .
9 5 ( 1 C ) , 1 4 8 . 8 2 ( 1 C ) , 1 48 .
6 8 ( 1 C ) , 1 4 8 . 5 9 ( 1 C ) , 1 4 8
. 3 0 ( 1 C ) ,1 4 8 . 2 1 ( 1 C ) , 1 4 8
. 0 9 ( 1 C ) , 1 4 7 . 9 2 ( 1C ) , 1 4
7 . 8 8 ( 1 C ) , 1 4 7 . 7 7 ( 1 C ) , 1
4 7 . 6 8( 1 C ) , 1 4 7 . 1 8 ( 1 C ) , 1 4
7 . 0 6 ( 1 C ) , 1 4 7. 0 0 ( 1 C ) , 1
4 6 . 6 5 ( 1 C ) , 1 4 6 . 6 1 ( 1 C ) , 14
6 . 4 4 ( 1 C ) , 1 4 6 . 2 3 ( 1 C ) , 1
4 6 . 1 8 ( 1 C ), 1 4 5 . 8 4 ( 1 C ) ,
1 4 5 . 6 4 ( 1 C ) , 1 4 5 . 5 1 ( 1C ) , 1
4 5 . 3 2 ( 1 C ) , 1 4 5 . 0 6 ( 1 C ) ,
1 4 5 . 0 3( 1 C ) , 1 4 4 . 9 2 ( 1 C ) ,
1 4 4 . 8 8 ( 1 C ) , 1 4 4. 7 4 ( 1 C ) ,
1 4 4 . 4 8 ( 1 C ) , 1 4 4 . 1 5 ( 1 C ) ,
1 4 3 . 9 7 ( 1 C ) , 1 4 3 . 4 3 ( 1 C ) ,
1 4 2 . 9 9 ( 1 C) , 1 4 2 . 8 1 ( 1 C ) ,
1 4 2 . 2 1 ( 1 C ) , 1 4 2 . 1 8( 1 C ) ,
1 4 0 . 5 0 ( 1 C ) , 1 4 0 . 4 0 ( 1 C )
, 1 3 9 .5 4 ( 1 C ) , 1 3 9 . 2 0 ( 1 C
) , 1 3 8 . 3 3 ( 1 C ) , 13 6 . 8 7 ( 1
C ) , 1 3 3 . 0 8 ( 1 C ) , 1 3 1 . 9 6 (
1 C ), 1 3 1 . 9 3 ( 1 C ) , 1 3 1 . 8 2
( 1 C ) , 1 3 1 . 7 2 (1 C ) , 1 3 1 . 5 9
( 1 C ) , 1 3 1 . 4 3 ( 1 C ) , 1 3 1 . 41
( 1 C ) , 1 3 0 . 6 5 ( 1 C ) , 1 2 8 . 9
6 ( P h , 2 C ), 1 2 8 . 8 8 ( P h , 2 C
) , 1 2 8 . 7 8 ( P h , 2 C ) ,1 2 8 . 1 6
( 1 C ) , 1 2 8 . 0 4 ( 1 C ) , 1 2 7 . 7
1 ( 1 C) , 1 2 7 . 6 0 ( 1 C ) , 1 2 7 . 4
7 ( P h , 2 C ) , 1 2 7. 2 7 ( 1 C ) ,
1 2 7 . 1 5 ( P h , 2 C ) , 1 2 6 . 7 0( P h
, 2 C ) , 1 2 6 . 4 2 ( 1 C ) , 5 6 . 2 3
( C 6 0 , 1C ) , 5 6 . 1 9 ( C 6 0 , 1C
) , 5 5 . 5 ( C 6 0 , 2 C )。Example 2 Preparation of C ₇₀ Ph ₃ H ¹ HNMR (400 MHz, CDC l ₃ / C
S ₂ , δ): 7.80-7.75 (m, P h H, 2
H), 7 .7 0-7. 6 6 (m, P h H, 2H),
7 5 8-7 5 2 (m, A r H, 3 H),
7 .5 0-7 .2 0 (m, P h H, 8 H), 4.
4 1 (s, 1 H). ¹³ CNMR (100 MHz, CDC l ₃ / CS ₂
, Δ), 1 6 0.7 0 (1 C), 1 5 5 .6 7 (1
C), 1 5 5 .0 7 (1 C), 1 5 3 .8 0 (1
C), 1 5 2 .6 2 (1 C), 1 5 3 .1 4
(1 C), 15 2 .6 2 (1 C), 1 5 2 .1 9
(1 C), 1 5 0 .1 6 (1 C), 1 4 9 .8 7
(1 C), 1 4 9 .5 7 (1 C), 1 4 9 .4
2 (1 C), 1 4 9 .3 9 (1 C), 1 4 9 .1
7 (1 C), 1 4 9 .08 (1 C), 1 4 8.
9 5 (1 C), 1 4 8 .8 2 (1 C), 1 48.
6 8 (1 C), 1 4 8 .5 9 (1 C), 1 4 8
.3 0 (1 C), 1 4 8 .2 1 (1 C), 1 4 8
.0 9 (1 C), 1 4 7 .9 2 (1 C), 1 4
7 8 8 (1 C), 1 4 7 .7 7 (1 C), 1
4 7 .6 8 (1 C), 1 4 7 .1 8 (1 C), 1 4
7.0 6 (1 C), 1 4 7.0 0 (1 C), 1
4 6 .6 5 (1 C), 1 4 6 .6 1 (1 C), 14
6 .4 4 (1 C), 1 4 6 .2 3 (1 C), 1
4 6 .1 8 (1 C), 1 4 5 .8 4 (1 C),
1 4 5 .6 4 (1 C), 1 4 5 .5 1 (1 C), 1
4 5 .3 2 (1 C), 1 4 5 .0 6 (1 C),
1 4 5 .0 3 (1 C), 1 4 4 .9 2 (1 C),
1 4 4. 8 8 (1 C), 1 4 4. 7 4 (1 C),
1 4 4 .4 8 (1 C), 1 4 4 .1 5 (1 C),
1 4 3 .9 7 (1 C), 1 4 3 .4 3 (1 C),
1 4 2 .9 9 (1 C), 1 4 2 .8 1 (1 C),
1 4 2 .2 1 (1 C), 1 4 2 .1 8 (1 C),
1 4 0 .5 0 (1 C), 1 4 0 .4 0 (1 C)
, 1 3 9 .5 4 (1 C), 1 3 9 .2 0 (1 C
), 1 3 8 .3 3 (1 C), 13 6 .8 7 (1
C), 1 3 3 .0 8 (1 C), 1 3 1 .9 6 (
1 C), 1 3 1 .9 3 (1 C), 1 3 1 .8 2
(1 C), 1 3 1 .7 2 (1 C), 1 3 1 .5 9
(1 C), 1 3 1 .4 3 (1 C), 1 3 1 .41
(1 C), 1 3 0 .6 5 (1 C), 1 2 8 .9
6 (P h, 2 C), 1 2 8 .8 8 (P h, 2 C
), 1 2 8 .7 8 (P h, 2 C), 1 2 8 .1 6
(1 C), 1 2 8 .0 4 (1 C), 1 2 7 .7
1 (1 C), 1 2 7 .6 0 (1 C), 1 2 7 .4
7 (P h, 2 C), 1 2 7. 2 7 (1 C),
1 2 7 .1 5 (P h, 2 C), 1 2 6 .7 0 (P h
, 2 C), 1 2 6 .4 2 (1 C), 5 6 .2 3
(C 6 0, 1C), 5 6 .1 9 (C 6 0, 1C
), 5 5.5 (C 60, 2 C).

【００１７】実施例３ C₇₀ ( p - ClC₆ H₄ )₃ Hの製造¹ H N M R ( 5 0 0 M H z 、 C D Cl₃ / C S₂ 、
δ) ：7 . 7 3 ( d,J = 6 . 5 0 H z , A r
H , 2 H ) , 7 . 6 3 ( d , J =6 .5 0 H z
, A r H , 2 H ) , 7 . 5 0 ( d , J =
6 . 50 H z, A r H , 2 H ) , 7 . 3 8 ( d
, J = 6 . 0 0 H z, A rH , 2 H ) , 7
. 2 7 - 7 . 2 1 ( m , A r H x 2 ,4 H )
,4 . 3 4 ( s , C 7 0 H , 1 H )。¹³ C N M R ( 1 2 5 M H z 、C D Cl₃ / C S₂ 、
δ) ：1 6 0 . 2 2( 1 C) , 1 5 5 . 6 0 ( 1 C )
, 1 5 4 . 7 4 ( 1 C ) , 1 5 3. 9 7( 1 C ) ,
1 5 2 . 7 3 ( 1 C ) , 1 5 2 . 5 9 ( 1 C )
, 15 2 . 5 2( 1 C ) , 1 5 0 . 5 3 ( 1 C ) ,
1 5 0 . 2 2 ( 1 C ), 1 4 9. 9 6 ( 1 C ) ,
1 4 9 . 5 0 ( 1 C x 2 ) , 1 4 9 .4 7 (
1 C) , 1 4 9 . 3 4 ( 1 C ) , 1 4 9 . 1 2
( 1 C ) , 1 4 8 . 9 4 (1 C x 2 ) , 1 4 8 .
9 0 ( 1 C ) , 1 4 8 . 6 3 (1 C ) , 14 8 .
5 7 ( 1 C ) , 1 4 8 . 3 4 ( 1 C ) , 1 4 8
. 21 ( 1 C ) ,1 4 8 . 1 3 ( 1 C ) , 1 4 8 .
1 1 ( 1 C ) , 1 4 8. 0 4 ( 1 C) , 1 4 7 . 9
6 ( 1 C ) , 1 4 7 . 5 5 ( 1 C ) ,1 4 7 . 3
6 ( 1C ) , 1 4 7 . 0 1 ( 1 C ) , 1 4 6 . 9
7 ( 1 C ), 1 4 6 . 7 9( 1 C ) , 1 4 6 . 5 3
( 1 C x 2 ) , 1 4 6 . 21 ( 1 C ) , 1 46 .
1 9 ( 1 C ) , 1 4 5 . 7 6 ( 1 C ) , 1 45
. 7 3 ( 1 C ) ,1 4 5 . 6 7 ( 1 C ) , 1 4 5
. 3 1 ( 1 C x2 ) , 1 4 5 . 2 2 (1 C ) , 1
4 5 . 1 2 ( 1 C ) , 1 4 5 . 0 5( 1 C ) , 1 4
4 . 8 5( 1 C ) , 1 4 4 . 3 8 ( 1 C ) , 1 4 4
.2 7 ( 1 C ) , 1 4 3 . 98 ( 1 C ) , 1 4 3
. 6 6 ( 1 C ) , 1 43 . 2 7 ( 1 C ) , 1 4 3.
0 1 ( 1 C ) , 1 2 4 . 6 5 ( 1 C ) ,1 2 4 .
6 1 ( 1 C ) , 1 40 . 8 1 ( 1 C ) , 1 4 0 .
0 5 ( 1C ) , 1 3 9 . 8 1 ( 1 C ) ,1 4 0 . 0
0 ( 1 C ) , 1 3 7 . 3 8( 1 C ) , 1 3 6 . 9
2 ( 1 C ), 1 3 4 . 7 4 ( 1 C ) , 1 3 4. 6
0 ( 1 C ) , 1 3 4 . 1 9 (1 C ) , 1 3 3 . 4
0 ( 1 C x2 ) , 1 3 3 . 2 5 ( 1 C ) , 1
3 2. 2 2 ( 1 C ) , 1 3 2 . 0 2( 1 C ) , 1 3
1 . 8 8 ( 1 C ) , 13 0 . 8 5 ( 1 C ) , 1 3
0. 5 5 ( 1 C ) , 1 2 9 . 5 7 ( A r H ,2 C )
, 1 2 9 . 5 3 ( Ar H , 2 C ) , 1 2 9 . 3
( A r H , 2C ) , 1 2 8 . 9 6 ( A rH , 2 C
) , 1 2 8 . 6 8 ( A r H , 2 C) , 1 2 8 .
2 5 ( A rH , 2 C ) , 1 2 7 . 6 8 ( 1 C ) ,
1 27 . 6 0 ( 1 C ) , 1 26 . 6 3 ( 1 C ) ,
1 2 4 . 6 5 ( 1 C ) ,1 2 4 . 6 1 ( 1 C ) ,5
9 . 6 0 ( 1 C ) , 5 5 . 9 3 ( 1 C ) ,5 5 .
8 1 ( 1 C ), 5 5 . 6 7 ( 1 C ) 。元素分析：
計算値（ C ₈₈ H ₁₃ Cl ₃ ） C 8 9 .8 5 ; H 1 .
1 1 、測定値 C 8 9 . 5 5 ; H 1 .0 2 .Example 3 Preparation of C ₇₀ (p-ClC ₆ H ₄ ) ₃ H ¹ HNMR (500 MHz, CD Cl ₃ / CS ₂ ,
δ): 7.7 3 (d, J = 6.50 H z, A r
H, 2 H), 7 .6 3 (d, J = 6.5 0 H z
, A r H, 2 H), 7 .5 0 (d, J =
6 .50 H z, A r H, 2 H), 7.38 (d
, J = 6.0 0 H z, A rH, 2 H), 7
.2 7-7 .2 1 (m, A r H x 2, 4 H)
, 4 .3 4 (s, C 7 0 H, 1 H). ¹³ CNMR (125 MHz, CD Cl ₃ / CS ₂ ,
δ): 1 60.2 2 (1 C), 1 5 5 6 0 (1 C)
, 1 5 4 .7 4 (1 C), 1 5 3. 9 7 (1 C),
1 5 2 .7 3 (1 C), 1 5 2 .5 9 (1 C)
, 15 2 .5 2 (1 C), 1 5 0 .5 3 (1 C),
1 5 0 .2 2 (1 C), 1 4 9. 9 6 (1 C),
1 4 9 .5 0 (1 C x 2), 1 4 9 .4 7 (
1 C), 1 4 9 .3 4 (1 C), 1 4 9 .1 2
(1 C), 1 4 8 .9 4 (1 C x 2), 1 4 8 ..
9 0 (1 C), 1 4 8 .6 3 (1 C), 14 8.
5 7 (1 C), 1 4 8 .3 4 (1 C), 1 4 8
.21 (1 C), 1 4 8 .1 3 (1 C), 1 4 8.
1 1 (1 C), 1 4 8. 0 4 (1 C), 1 4 7 .9
6 (1 C), 1 4 7 .5 5 (1 C), 1 4 7 .3
6 (1C), 1 4 7 .0 1 (1 C), 1 4 6 .9
7 (1 C), 1 4 6 .7 9 (1 C), 1 4 6 .5 3
(1 C x 2), 1 4 6 .21 (1 C), 1 46.
1 9 (1 C), 1 4 5 .7 6 (1 C), 1 45
.7 3 (1 C), 1 4 5 .6 7 (1 C), 1 4 5
.3 1 (1 C x2), 1 4 5 .2 2 (1 C), 1
4 5 .1 2 (1 C), 1 4 5 .0 5 (1 C), 1 4
4 .8 5 (1 C), 1 4 4 .3 8 (1 C), 1 4 4
.2 7 (1 C), 1 4 3 .98 (1 C), 1 4 3
.6 6 (1 C), 1 43 .2 7 (1 C), 1 4 3.
0 1 (1 C), 1 2 4 .6 5 (1 C), 1 2 4.
6 1 (1 C), 1 40 .8 1 (1 C), 1 4 0.
0 5 (1C), 1 3 9 .8 1 (1 C), 1 4 0 .0
0 (1 C), 1 3 7 .3 8 (1 C), 1 3 6 .9
2 (1 C), 1 3 4 .7 4 (1 C), 1 3 4.6
0 (1 C), 1 3 4 .1 9 (1 C), 1 3 3 .4
0 (1 C x2), 1 3 3 .2 5 (1 C), 1
3 2.2 2 (1 C), 1 3 2 .0 2 (1 C), 1 3
1 .8 8 (1 C), 13 0 .8 5 (1 C), 1 3
0.5 5 (1 C), 1 2 9 .5 7 (A r H, 2 C)
, 1 2 9 .5 3 (Ar H, 2 C), 1 2 9 .3
(A r H, 2C), 1 2 8 .9 6 (A rH, 2 C
), 1 2 8 .6 8 (A r H, 2 C), 1 2 8.
2 5 (A rH, 2 C), 1 2 7 .6 8 (1 C),
1 27 .6 0 (1 C), 1 26 .6 3 (1 C),
1 2 4 .6 5 (1 C), 1 2 4 .6 1 (1 C), 5
9 .6 0 (1 C), 5 5 .9 3 (1 C), 5 5.
8 1 (1 C), 5 5 .6 7 (1 C). Elemental analysis:
Calculated value ( C ₈₈ H ₁₃ Cl ₃ ) C 8 9 .8 5; H 1.
1 1, measured value C 8 9 .5 5; H 1.0 .2

【００１８】実施例４ C₇₀(C₁₀ H₇)₃ H（C₁₀H₇は１
−ナフチル基を表す）の製造¹ H N M R ( 5 0 0 M H z 、C D C l₃ / C S₂
、δ )：9 . 6 5 ( d, J = 8 . 5 4 H z ,
A r H , 1 H ) , 9 . 5 4 ( d , J =9 . 7 7
H z , A r H , 1 H ) , 8 . 9 2 ( d , J
= 8 . 85 H z , A r H , 1 H ) , 8 . 2
6 ( d , J = 7 . 0 2 H z ,A r H , 1 H ) ,
8 . 0 9 ( d , J = 7 . 6 3 H z , A r
H, 1 H ) , 7 . 8 9 - 7 . 4 5 ( m , A
r H , 5 H ) , 7 . 40 ( m , A r H , 1 H )
, 7 . 3 6 ( m , A r H , 1 H ) , 7 .3 0
- 7 . 2 3 ( m , A r H , 7 H ) , 6 . 9 6
( m , A r H, 1 H ) , 6 . 8 6 ( m , A r
H , 1 H ) 4 . 9 0 ( s , C 6 0H , 1 H ) 。¹³ C N M R ( 1 2 5 M H z 、 C D C l₃ / C
S₂、δ) ：1 6 1 . 3 4( 1 C ) , 1 5 8 . 1 6 (
1 C ) , 1 5 7 . 4 3 ( 1 C ) , 1 5 5. 8 3
( 1 C ) , 1 5 4 . 5 1 ( 1 C ) , 1 5 3 . 2 2
( 1 C ) , 15 2 . 6 1 ( 1 C ) , 1 5 0 . 7 9
( 1 C ) , 1 5 0 . 2 6 ( 1 Cx 2 ) , 1 5 0
. 2 0 ( 1 C ) , 1 5 0 . 1 3 ( 1 C ) , 1 4 9
. 95 ( 1 C x 2 ) , 1 4 9 . 6 0 ( 1 C )
, 1 4 9 . 2 6 ( 1 C ), 1 4 9 . 1 9 ( 1 C
) , 1 4 9 . 1 6 ( 1 C ) , 1 4 8 . 5 5 ( 1C
) , 1 4 8 . 3 9 ( 1 C ) , 1 4 8 . 3 5 ( 1
C ) , 1 4 8 . 2 8( 1 C ) , 1 4 7 . 9 4 ( 1
C ) , 1 4 7 . 8 6 ( 1 C ) , 1 4 7. 6 0 ( 1
C ) , 1 4 7 . 4 9 ( 1 C ) , 1 4 7 . 2 6
( 1 C ) ,1 4 7 . 1 8 ( 1 C ) , 1 4 7 . 0 2
( 2 C ) , 1 4 6 . 9 6 ( 1 C) , 1 4 6 . 8 6
( 1 C ) , 1 4 6 . 7 1 ( 1 C ) , 1 4 6 . 6 5
( 1 C ) , 1 4 6 . 2 8 ( 1 C ) , 1 4 6 . 0 9
( 1 C ) , 1 4 5 .9 0 ( 1 C ) , 1 4 5 . 7 3
( 1 C ) , 1 4 5 . 3 6 ( 1 C ) , 14 5 . 3
1 ( 1 C ) , 1 4 5 . 1 7 ( 1 C ) , 1 4 5 .
1 0 ( 1 C ), 1 4 4 . 9 3 ( 1 C x 2 ) ,
1 4 4 . 8 1 ( 1 C ) , 1 4 4 .5 2 ( 1 C ) ,
1 4 4 . 2 0 ( 1 C ) , 1 4 3 . 5 9 ( 1 C )
, 14 3 . 4 5 ( 1 C ) , 1 4 2 . 9 3 ( 1 C
) , 1 4 2 . 0 1 ( 1 C ), 1 4 1 . 8 6 ( 1
C ) , 1 4 1 . 2 6 ( 1 C ) , 1 4 1 . 0 9 (1
C ) , 1 3 9 . 8 6 ( 1 C ) , 1 3 9 . 5 4
( 1 C ) , 1 3 6 . 71 ( 1 C ) , 1 3 5 . 4 0
( 1 C ) , 1 3 4 . 9 3 ( 1 C x 2 ) ,1 3 4 .
8 1 ( 1 C ) , 1 3 4 . 7 5 ( 1 C ) , 1 3 3
. 6 3 ( 1C ) , 1 3 3 . 5 8 ( 1 C x 2 )
, 1 3 2 . 5 6 ( 1 C ) , 1 32 . 4 7 ( 1 C
) , 1 3 2 . 1 9 ( 1 C ) , 1 3 1 . 9 8 ( 1
C ) ,1 3 1 . 5 8 ( 1 C ) , 1 3 0 . 8 4 ( 1
C ) , 1 2 9 . 8 3 ( 1C ) , 1 2 9 . 7 0 ( 1
C ) , 1 2 9 . 5 4 ( 1 C ) , 1 2 9 . 4 8( 1
C ) , 1 2 9 . 4 2 ( 1 C ) , 1 2 9 . 2 1 (
1 C ) , 1 2 8 .9 4 ( 1 C ) , 1 2 8 . 4 3 ( 1
C ) , 1 2 8 . 3 0 ( 1 C ) , 12 8 . 1 5 (
1 C ) , 1 2 7 . 0 3 ( 1 C ) , 1 2 6 . 5 6 (
1 C ) ,1 2 6 . 3 6 ( 1 C ) , 1 2 6 . 3 3 ( 1
C ) , 1 2 6 . 1 9 ( 1C ) , 1 2 5 . 7 6 (
1 C x 2 ) , 1 2 5 . 7 3 ( 1 C ) , 1 25 .
4 7 ( 1 C ) , 1 2 5 . 4 0 ( 1 C ) , 1 2 5
. 1 9 ( 1 C ) ,1 2 5 . 0 0 ( 1 C ) , 1 2 4 .
8 5 ( 1 C ) , 1 2 4 . 6 1 ( 1 C) , 1 2 1 .
4 8 ( 1 C ) , 6 1 . 2 4 ( 1 C ) , 5 7 . 5
8 ( 1C ) , 5 7 . 3 1 ( 1 C ) , 5 4 . 2 2
( 1 C ) .Example 4 C ₇₀ (C ₁₀ H ₇ ) ₃ H (C ₁₀ H ₇ is 1
-Representing a naphthyl group) ¹ HNMR (500 MHz, CDCl ₃ / CS ₂
, Δ): 9.6 5 (d, J = 8.5 4 H z,
A r H, 1 H), 9 .5 4 (d, J = 9. 7 7
H z, A r H, 1 H), 8 .9 2 (d, J
= 8 .85 H z, A r H, 1 H), 8 .2
6 (d, J = 7.0 2 H z, A r H, 1 H),
8 .0 9 (d, J = 7 .6 3 H z, A r
H, 1 H), 7 .8 9-7 .4 5 (m, A
r H, 5 H), 7.40 (m, A r H, 1 H)
, 7 .3 6 (m, A r H, 1 H), 7 .3 0
-7 .2 3 (m, A r H, 7 H), 6.96
(m, A r H, 1 H), 6. 8 6 (m, A r
H, 1 H) 4.90 (s, C 60 H, 1 H). ¹³ CNMR (125 MHz, CDC l ₃ / C
S ₂ , δ): 1 6 1 .3 4 (1 C), 1 5 8 .1 6 (
1 C), 1 5 7 .4 3 (1 C), 1 5 5. 8 3
(1 C), 1 5 4 .5 1 (1 C), 1 5 3 .2 2
(1 C), 15 2 .6 1 (1 C), 1 5 0 .7 9
(1 C), 150 0 .2 6 (1 Cx 2), 150 0
.2 0 (1 C), 1 5 0 .1 3 (1 C), 1 4 9
.95 (1 C x 2), 1 4 9 .6 0 (1 C)
, 1 4 9 .2 6 (1 C), 1 4 9 .1 9 (1 C
), 1 4 9 .1 6 (1 C), 1 4 8 .5 5 (1C
), 1 4 8 .3 9 (1 C), 1 4 8 .3 5 (1
C), 1 4 8 .2 8 (1 C), 1 4 7 .9 4 (1
C), 1 4 7 .8 6 (1 C), 1 4 7. 6 0 (1
C), 1 4 7 .4 9 (1 C), 1 4 7 .2 6
(1 C), 1 4 7 .1 8 (1 C), 1 4 7 .0 2
(2 C), 1 4 6 .9 6 (1 C), 1 4 6 .8 6
(1 C), 1 4 6 .7 1 (1 C), 1 4 6 .6 5
(1 C), 1 4 6 .2 8 (1 C), 1 4 6 .0 9
(1 C), 1 4 5 .9 0 (1 C), 1 4 5 .7 3
(1 C), 1 4 5 .3 6 (1 C), 14 5 .3
1 (1 C), 1 4 5 .1 7 (1 C), 1 4 5.
1 0 (1 C), 1 4 4 .9 3 (1 C x 2),
1 4 4 .8 1 (1 C), 1 4 4.5 2 (1 C),
1 4 4 .2 0 (1 C), 1 4 3 .5 9 (1 C)
, 14 3 .4 5 (1 C), 1 4 2 .9 3 (1 C
), 1 4 2 .0 1 (1 C), 1 4 1 .8 6 (1
C), 1 4 1 .2 6 (1 C), 1 4 1 .0 9 (1
C), 1 3 9 .8 6 (1 C), 1 3 9 .5 4
(1 C), 1 3 6 .71 (1 C), 1 3 5 .4 0
(1 C), 1 3 4 .9 3 (1 C x 2), 1 3 4.
8 1 (1 C), 1 3 4 .7 5 (1 C), 1 3 3
.6 3 (1C), 1 3 3 .5 8 (1 C x 2)
, 1 3 2 .5 6 (1 C), 1 32 .4 7 (1 C
), 1 3 2 .1 9 (1 C), 1 3 1 .9 8 (1
C), 1 3 1 .5 8 (1 C), 1 3 0 .8 4 (1
C), 1 2 9 .8 3 (1C), 1 2 9 .7 0 (1
C), 1 2 9 .5 4 (1 C), 1 2 9 .4 8 (1
C), 1 2 9 .4 2 (1 C), 1 2 9 .2 1 (
1 C), 1 2 8 .9 4 (1 C), 1 2 8 .4 3 (1
C), 1 2 8 .3 0 (1 C), 12 8 .1 5 (
1 C), 1 2 7 .0 3 (1 C), 1 2 6 .5 6 (
1 C), 1 2 6 .3 6 (1 C), 1 2 6 .3 3 (1
C), 1 2 6 .1 9 (1C), 1 2 5 .7 6 (
1 C x 2), 1 2 5 .7 3 (1 C), 1 25.
4 7 (1 C), 1 2 5 .4 0 (1 C), 1 2 5
.1 9 (1 C), 1 2 5 .0 0 (1 C), 1 2 4 ..
8 5 (1 C), 1 2 4 .6 1 (1 C), 1 2 1.
4 8 (1 C), 6 1 .2 4 (1 C), 5 7.5
8 (1C), 5 7 .3 1 (1 C), 5 4 .2 2
(1 C).

【００１９】実施例５ C₇₀Me₃H の製造¹ H N M R ( 4 0 0 M H z 、 C D C l₃ / C
S₂、δ) ：3 . 9 0 ( s, C 7 0 H , 1 H ) ,
2 . 5 2 , ( s , M e , 3 H ) , 2 . 2 7( s ,
M e , 3 H ) , 2 . 1 4 ( s , M e , 3 H
) 。 F A B M S m / z ：測定値 8 8 7 ( M + ) ,
8 4 0 ( C 7 0 ) .Example 5 Preparation of C ₇₀ Me ₃ H ¹ HNMR (400 MHz, CDC l ₃ / C
S ₂ , δ): 3.90 (s, C 7 0 H, 1 H),
2 .5 2, (s, M e, 3 H), 2 .2 7 (s,
M e, 3 H), 2 .1 4 (s, M e, 3 H
). FABMS m / z: Measured value 8 8 7 (M +),
8 40 (C 70).

【００２０】実施例６ K（η⁵-C₇₀Ph₃）の製造 25℃でC₇₀Ph₃H （9 mg）をカリウムtert -ブトキシドの
T H F - d₈ 溶液（0.018 M ）0.5 mlに加え、¹H N
M R を測定した。¹ H N M R ( 4 0 0 M H z , T H F - d₈、δ)
：7 . 8 8 - 7 .8 2 ( m , P h H , 5 H )
, 7 . 2 4 - 7 . 0 8 ( m , P h H, 1 0
H ) 。EXAMPLE 6 Preparation of K (η ⁵ -C ₇₀ Ph ₃ ) C ₇₀ Ph ₃ H (9 mg) at 25 ° C. in potassium tert-butoxide
THF - d ₈ solution (0.018 M) was added to 0.5 ml, ¹ HN
MR was measured. ¹ HNMR (400 MHz, THF-d ₈ , δ)
: 7.8 8-7.8 2 (m, P h H, 5 H)
, 7 .2 4-7 .0 8 (m, P h H, 1 0
H).

【００２１】実施例７ K[η⁵- C₇₀(p - CF₃ C₆H₄
)₃] の製造 25℃でC₇₀(p - CF₃ C₆H₄ )₃H （11 mg ）をカリウム
tert -ブトキシドのTH F - d ₈溶液（0.018 M ）0.5 m
lに加え、¹H 及び¹³C N M Rを測定した。¹ H N M R ( 4 0 0 M H z、 T H F - d₈、δ )：
8 . 0 7 - 8 , 0 5( m , A r H , 6 H ) , 7
. 5 7 - 7 . 5 4 ( m , A r H , 6 H) 。 ¹³C
N M R ( 1 0 0 M H z、 T H F - d₈、δ) ：1
6 6 . 1 8 ,1 6 0 . 5 0 , 1 5 3 . 3 0 , 1 5 1 .
9 9 , 1 5 1 . 0 4 , 1 5 0. 3 2 , 1 4 9 . 7
9 , 1 4 9 . 7 7 , 1 4 9 . 1 7 , 1 4 8 . 8 8
,1 4 8 . 8 2 , 1 4 8 . 4 8 , 1 4 8 . 4 4 ,
1 4 8 . 2 6 , 1 4 7. 1 4 , 1 4 6 . 9 0 , 1 4
6 . 8 1 , 1 4 6 . 3 7 , 1 4 6 . 1 9 ,1 4 6 .
0 7 , 1 4 5 . 7 2 , 1 4 5 . 6 1 , 1 4 5 . 4
3 , 1 4 4. 7 1 , 1 4 2 . 5 3 , 1 4 2 . 2 8 ,
1 3 7 . 8 7 , 1 3 6 . 8 1 ,1 3 4 . 5 4 , 1
3 4 . 4 6 , 1 3 3 . 2 4 , 1 3 2 . 9 2 , 1 3
2. 6 0 , 1 2 9 . 3 6 - 1 2 9 . 2 3 ( m ) , 1
2 8 . 9 3 , 1 2 5 .8 0 - 1 2 5 . 7 7 ( m ) ,
1 2 5 . 6 ( q . J = 2 7 1 . 1 9 ), 1 2
1 . 0 7 , 6 1 . 0 6 , 5 9 . 1 1 .Example 7 K [η ⁵ -C ₇₀ (p -CF ₃ C ₆ H ₄
) ₃ ] at 25 ℃ C ₇₀ (p-CF ₃ C ₆ H ₄ ) ₃ H (11 mg) potassium
tert - butoxide TH F - d ₈ solution (0.018 M) 0.5 m
In addition to l, ¹ H and ¹³ C NMR were measured. ^{1 HNMR (4 0 0 MH z} , THF - d 8, δ):
8 .0 7-8, 0 5 (m, A r H, 6 H), 7
.5 7-7 .5 4 (m, A r H, 6 H). ¹³ C
NMR (1 0 0 MH z, THF - d 8, δ): 1
6 6 .1 8, 1 6 0 .5 0, 1 5 3 .3 0, 1 5 1.
9 9, 1 5 1 .0 4, 1 5 0 .3 2, 1 4 9 .7
9, 1 4 9 .7 7, 1 4 9 .1 7, 1 4 8 .8 8
, 1 4 8 .8 2, 1 4 8 .4 8, 1 4 8 .4 4,
1 4 8 .2 6,, 1 4 7. 1 4, 1 4 6 .9 0, 1 4
6 .8 1, 1 4 6 .3 7, 1 4 6 .1 9, 1 4 6.
0 7,, 1 4 5 .7 2, 1 4 5 .6 1, 1 4 5 .4
3, 1 4 4. 7 1, 1 4 2 .5 3, 1 4 2 .2 8,
1 3 7 .8 7, 1 3 6 .8 1, 1 3 4 .5 4, 1
3 4 .4 6, 1 3 3 .2 4, 1 3 2 .9 2, 1 3
2.6 0, 1 2 9 .3 6-1 2 9 .2 3 (m), 1
2 8 .9 3, 1 2 5 .8 0-1 2 5 .7 7 (m),
1 2 5 .6 (q .J = 2 7 1 .1 9), 1 2
1 .0 7, 6 1 .0 6, 5 9 .1 1 ..

【００２２】実施例８ Tl [η⁵ - C₇₀(p -CF₃C₆H₄)₃]
の製造 C₇₀(p - CF₃C₆ H₄)₃ H（46 mg ）をＴＨＦ（10 ml ）
に溶かし、25℃で遮光下撹拌せずにタリウムエトキシド
（25 ml ）をTHF （75 ml ）に溶かして加えた。２時間
後、溶媒を減圧留去すると目的物が定量的に得られた。¹ H N M R ( 4 0 0 M H z , T H F - d₈、δ )
d 8 . 0 9 - 8 .0 7 ( m , A r H , 6 H )
, 7 . 5 9 - 7 . 5 3 ( m , A r H , 6H )。Example 8 Tl [η ⁵ -C ₇₀ (p -CF ₃ C ₆ H ₄ ) ₃ ]
Preparation of C ₇₀ (p-CF ₃ C ₆ H ₄ ) ₃ H (46 mg) in THF (10 ml)
Was dissolved in THF, and thallium ethoxide (25 ml) was dissolved in THF (75 ml) and added at 25 ° C. under light shielding without stirring. After 2 hours, the solvent was distilled off under reduced pressure to quantitatively obtain the desired product. ¹ HNMR (400 MHz, THF-d ₈ , δ)
d 8.09-8.07 (m, A r H, 6 H)
, 7 .5 9-7. 5 3 (m, A r H, 6H).

【００２３】実施例９ K [η⁵- C₇₀(p - ClC
₆H₄)₃] の製造 25 ℃でC₇₀(p - ClC₆H₄ )₃H （9 mg）をカリウムtert
-ブトキシドのT H F -d₈溶液（0.018 M ）0.5 mlに加
え、¹H 及び¹³C N M R を測定した。¹ H N M R ( 4 0 0 M H z , T H F - d₈、δ)
：7 . 9 2 - 7 . 81 ( m , A r H , 6 H )
, 7 . 2 7 - 7 . 2 4 ( m , A r H , 6H ) 。¹³ C N M R ( 1 0 0 M H z , T H F - d₈、δ)
：1 6 6 . 8 2 , 16 0 . 7 5 , 1 5 3 . 4 8 ,
1 5 2 . 1 1 , 1 5 1 . 1 9 , 1 4 9 . 90 , 1 4
9 . 8 0 , 1 4 9 . 2 9 , 1 4 8 . 9 0 , 1 4 8
. 8 6 , 14 8 . 6 4 , 1 4 8 . 4 7 , 1 4 7 .
3 2 , 1 4 7 . 0 2 , 1 4 6 . 95 , 1 4 6 . 8 2
, 1 4 6 . 7 7 , 1 4 6 . 4 2 , 1 4 6 . 2 8 ,
14 6 . 1 8 , 1 4 5 . 7 9 , 1 4 5 . 6 0 ,
1 4 5 . 5 8 , 1 4 5 . 26 , 1 4 4 . 6 5 , 1 4
2 . 8 4 , 1 4 2 . 5 2 , 1 4 2 . 4 8 , 13 8
. 0 7 , 1 3 6 . 7 8 , 1 3 4 . 9 3 , 1 3 4 .
5 0 , 1 3 3 . 35 , 1 3 3 . 0 2 , 1 3 2 . 9
7 , 1 3 2 . 7 6 , 1 3 2 . 6 5 , 13 0 . 4 1 ,
1 3 0 . 0 9 ( 4 C ) , 1 2 9 . 5 0 , 1 2 8
. 9 8 (6 C ) , 1 2 1 . 4 4 , 6 0 . 0 9 ,
5 8 . 7 9 .Example 9 K [η ⁵ -C ₇₀ (p -ClC
₆ H ₄ ) ₃ ] at 25 ° C C ₇₀ (p-ClC ₆ H ₄ ) ₃ H (9 mg) potassium tert
-Butoxide was added to 0.5 ml of THF-d ₈ solution (0.018 M), and ¹ H and ¹³ C NMR were measured. ¹ HNMR (400 MHz, THF-d ₈ , δ)
: 7 9 2-7 81 (m, A r H, 6 H)
, 7 .2 7-7 .2 4 (m, A r H, 6H). ¹³ CNMR (100 MHz, THF-d ₈ , δ)
: 1 6 6 .8 2, 16 0 .7 5, 1 5 3 .4 8,
1 5 2 .1 1, 1 5 1 .1 9, 1 4 9 .90, 1 4
9 .8 0, 1 4 9 .2 9, 1 4 8 .9 0, 1 4 8
.8 6, 14 8 .6 4, 1 4 8 .4 7, 1 4 7.
3 2, 1 4 7 .0 2, 1 4 6 .95, 1 4 6 .8 2
, 1 4 6 .7 7, 1 4 6 .4 2, 1 4 6 .2 8,
14 6 .1 8, 1 4 5 .7 9, 1 4 5 .6 0,
1 4 5 .5 8, 1 4 5 .26, 1 4 4 .6 5, 1 4
2 .8 4, 1 4 2 .5 2, 1 4 2 .4 8, 13 8
.0 7, 1 3 6 .7 8, 1 3 4 .9 3, 1 3 4 ..
5 0, 1 3 3 .35, 1 3 3 .0 2, 1 3 2 .9
7, 1 3 2 .7 6, 1 3 2 .6 5, 13 0 .4 1,
1 3 0 .0 9 (4 C), 1 2 9 .5 0, 1 2 8
. 9 8 (6 C), 1 2 1 .4 4, 6 0 .0 9,
5 8 .7 9.

【００２４】実施例１０ K (η⁵- C₇₀Me₃ )の製造 25 ℃で C₇₀Me₃H （8 mg）をカリウムtert -ブトキシ
ドのT H F -d₈ 溶液（0.018 M ）0.5 mlに加え、¹H 及
び¹³C N M Rを測定した。¹ H N M R ( 4 0 0 M H z、T H F - d₈、δ) ：2
. 8 6 , ( s , Me , 3 H ) , 1 . 9 7 , (
s , M e , 3 H x 2 ) 。¹³ C N M R ( 1 0 0 M H z 、 T H F - d₈、δ)
：1 6 8 . 8 4 ( C6 0 , 2 C ) , 1 6 2 . 0 4
( C 6 0 , 2 C ) , 1 5 3 . 6 2 ( C 60 , 2 C
) , 1 5 1 . 9 0 ( C 6 0 , 2 C ) , 1 5 1 .
2 0 ( C 60 , 2 C ) , 1 4 9 . 7 7 ( C 6 0 ,
2 C ) , 1 4 9 . 0 9 ( C 6 0, 2 C ) , 1 4
8 . 7 5 ( C 6 0 , 1 C ) , 1 4 8 . 6 3 ( C
6 0, 2 C ) , 1 4 8 . 3 4 ( C 6 0 , 2 C )
, 1 4 8 . 2 9 ( C 6 0, 2 C ) , 1 4 7 . 4
6 ( C 6 0 , 2 C ) , 1 4 7 . 2 8 ( C 6 0,
2 C ) , 1 4 6 . 4 9 ( C 6 0 , 2 C ) , 1 4
6 . 3 6 ( C 6 0, 2 C ) , 1 4 6 . 2 6 ( C
6 0 , 2 C ) , 1 4 6 . 1 7 ( C 6 0, 2 C + 1
C ) , 1 4 5 . 9 8 ( C 6 0 , 2 C ) , 1 4 5
. 8 4 (C 6 0 , 2 C ) , 1 4 5 . 7 0 ( C 6
0 , 2 C ) , 1 4 5 . 4 7 (C 6 0 , 2 C ) ,
1 4 5 . 3 2 ( C 6 0 , 2 C ) , 1 4 3 . 8 0
(C 6 0 , 2 C ) , 1 4 2 . 3 6 ( C 6 0 , 2
C ) , 1 4 2 . 2 7 (C 6 0 , 2 C ) , 1 3 8 .
5 4 ( C 6 0 , 2 C ) , 1 3 5 . 8 4 (C 6 0
, 2 C ) , 1 3 5 . 0 2 ( C 6 0 , 1 C ) , 1
3 3 . 8 6 ( C6 0 , 2 C ) , 1 3 3 . 3 5 (
C 6 0 , 2 C ) , 1 3 3 . 0 9 ( C6 0 , 2 C )
, 1 3 2 . 3 2 ( C 6 0 , 2 C ) , 1 3 0 . 1
7 ( C6 0 , 2 C ) , 1 2 4 . 2 7 ( C 6 0 ,
2 C ) , 5 2 . 9 6 ( C 60 , 1 C ) , 5 2 .
6 7 ( C 6 0 , 2 C ) , 3 3 . 0 7 ( M e , 1
C ) , 3 1 . 7 7 ( M e , 2 C ) .Example 10 Preparation of K (η ⁵ -C ₇₀ Me ₃ ) At 25 ° C., C ₇₀ Me ₃ H (8 mg) was added to 0.5 ml of a solution of potassium tert-butoxide in THF-d ₈ (0.018 M), ¹ H and ¹³ C NMR were measured. ¹ HNMR (400 MHz, THF-d ₈ , δ): 2
.8 6, (s, Me, 3 H), 1 .9 7, (
s, M e, 3 H x 2). ^{13 CNMR (1 0 0 MH z} , THF - d 8, δ)
: 1 6 8 .8 4 (C6 0, 2 C), 1 6 2 .0 4
(C 60, 2 C), 1 5 3 .6 2 (C 60, 2 C
), 1 5 1 .9 0 (C 6 0, 2 C), 1 5 1.
2 0 (C 60, 2 C), 1 4 9 .7 7 (C 6 0,
2 C), 1 4 9 .0 9 (C 60, 2 C), 1 4
8 .75 (C 6 0, 1 C), 1 4 8 .6 3 (C
6 0, 2 C), 1 4 8 .3 4 (C 6 0, 2 C)
, 1 4 8 .2 9 (C 6 0, 2 C), 1 4 7 .4
6 (C 6 0, 2 C), 1 4 7 .2 8 (C 6 0,
2 C), 1 4 6 .4 9 (C 6 0, 2 C), 1 4
6 .3 6 (C 60, 2 C), 1 4 6 .2 6 (C
6 0, 2 C), 1 4 6 .1 7 (C 6 0, 2 C + 1
C), 1 4 5 .9 8 (C 6 0, 2 C), 1 4 5
.8 4 (C 6 0, 2 C), 1 4 5 .7 0 (C 6
0, 2 C), 1 4 5 .4 7 (C 6 0, 2 C),
1 4 5 .3 2 (C 6 0, 2 C), 1 4 3 .8 0
(C 60, 2 C), 1 4 2 .3 6 (C 6 0, 2
C), 1 4 2 .2 7 (C 6 0, 2 C), 1 3 8.
5 4 (C 6 0, 2 C), 1 3 5 .8 4 (C 6 0
, 2 C), 1 3 5 .0 2 (C 6 0, 1 C), 1
3 3 .8 6 (C6 0, 2 C), 1 3 3 .3 5 (
C 6 0, 2 C), 1 3 3 .0 9 (C 6 0, 2 C)
, 1 3 2 .3 2 (C 6 0, 2 C), 1 3 0 .1
7 (C6 0, 2 C), 1 2 4 .2 7 (C 6 0,
2 C), 5 2 .9 6 (C 60, 1 C), 5 2.
6 7 (C 6 0, 2 C), 3 3.0 7 (M e, 1
C), 3 1 .7 7 (M e, 2 C).

【００２５】[0025]

【発明の効果】本発明のＣ₇₀誘導体である配位子および
それを含む金属錯体は、さまざまな合成反応の配位子あ
るいは触媒として用いることができる。INDUSTRIAL APPLICABILITY The ligand which is the C ₇₀ derivative of the present invention and the metal complex containing the same can be used as a ligand or a catalyst for various synthetic reactions.

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.⁷，ＤＢ名) C07C 13/64 C01B 31/02 101 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07C 13/64 C01B 31/02 101 CA (STN) REGISTRY (STN)

Claims

(57)【特許請求の範囲】(57) [Claims]

【請求項１】下記の一般式（Ｉ）【化１】（上記の式中、ＲはＣ₁〜Ｃ₁₀のアルキル基、または置
換基を有していてもよいＣ₆〜Ｃ₁₄のアリール基を表
す）で表されるＣ₇₀誘導体。1. The following general formula (I): (In the above formulas, R represents an aryl group of C ₁ -C alkyl group having ₁₀ or substituent C ₆ which may have a ~C _14,) C ₇₀ derivative represented by the.

【請求項２】下記の一般式（II）【化２】（上記の式中、ＲはＣ₁〜Ｃ₁₀のアルキル基、または置
換基を有していてもよいＣ₆〜Ｃ₁₄のアリール基を表
す）で表されるシクロペンタジエニドイオンからなるη
⁵型シクロペンタジエニル配位子。2. The following general formula (II): (In the above formula, R represents a C _{1 to} C ₁₀ alkyl group or a C _{6 to} C ₁₄ aryl group which may have a substituent), and is composed of a cyclopentadienide ion.
^5- type cyclopentadienyl ligand.

【請求項３】請求項２に記載のη⁵型シクロペンタジ
エニル配位子を含む金属錯体。3. A metal complex containing the η ⁵ type cyclopentadienyl ligand according to claim 2.

【請求項４】下記の一般式（III) 【化３】（上記の式中、ＲはＣ₁〜Ｃ₁₀のアルキル基、または置
換基を有していてもよいＣ₆〜Ｃ₁₄のアリール基を表
し、Ｍは請求項２に記載の式（II）で表される上記シク
ロペンタジエニル配位子以外の配位子を１個または２個
以上有することもある金属原子を表し、該金属原子はア
ルカリ金属、遷移金属及びランタノイドからなる群から
選ばれる）で表される請求項３に記載の金属錯体。4. The following general formula (III): (In the above formula, R represents a C _{1 to} C ₁₀ alkyl group or a C _{6 to} C ₁₄ aryl group which may have a substituent, and M represents the formula (II) according to claim 2. Represents a metal atom which may have one or two or more ligands other than the above cyclopentadienyl ligand, and the metal atom is selected from the group consisting of alkali metals, transition metals and lanthanoids. ) The metal complex according to claim 3, represented by:

【請求項５】金属原子がＬｉ、Ｎａ、Ｋ、Ｃｒ、Ｍ
ｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｚｒ、Ｒｕ、Ｒ
ｈ、Ｐｄ、Ａｇ、Ｃｄ、Ｒｔ、Ａｕ、Ｈｇ、Ｔｌ及びＳ
ｍからなる群から選ばれる請求項４に記載の金属錯体。5. The metal atom is Li, Na, K, Cr or M.
n, Fe, Co, Ni, Cu, Zn, Zr, Ru, R
h, Pd, Ag, Cd, Rt, Au, Hg, Tl and S
The metal complex according to claim 4, which is selected from the group consisting of m.

【請求項６】請求項１に記載のＣ₇₀誘導体の製造法で
あって、Ｃ₇₀に対してグリニャール試薬とハロゲン化銅
誘導体とから調製される有機銅試薬を反応させる工程を
含む方法。6. The method for producing a C ₇₀ derivative according to claim 1, comprising a step of reacting C ₇₀ with an organocopper reagent prepared from a Grignard reagent and a copper halide derivative.

【請求項７】使用するハロゲン化銅誘導体がＣｕＢｒ
・ＳＭｅ₂である請求項６記載の方法。7. The copper halide derivative used is CuBr.
The method according to claim 6, which is SMe ₂ .

【請求項８】請求項３、請求項４、または請求項５に
記載の金属錯体の製造方法であって、請求項１に記載の
Ｃ₇₀誘導体を金属アルコキシドと反応させる工程を含む
方法。8. A method for producing the metal complex according to claim 3, claim 4, or claim 5, which comprises the step of reacting the C ₇₀ derivative according to claim 1 with a metal alkoxide.

【請求項９】金属アルコキシドを構成する金属原子が
Ｌｉ、Ｎａ、Ｋ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃ
ｕ、Ｚｎ、Ｚｒ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｄ、Ｒ
ｔ、Ａｕ、Ｈｇ、Ｔｌ及びＳｍからなる群から選ばれる
請求項８に記載の方法。9. The metal atom constituting the metal alkoxide is Li, Na, K, Cr, Mn, Fe, Co, Ni, C.
u, Zn, Zr, Ru, Rh, Pd, Ag, Cd, R
9. The method of claim 8 selected from the group consisting of t, Au, Hg, Tl and Sm.