JPH11255508A - C70 derivative - Google Patents
C70 derivativeInfo
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- JPH11255508A JPH11255508A JP10056571A JP5657198A JPH11255508A JP H11255508 A JPH11255508 A JP H11255508A JP 10056571 A JP10056571 A JP 10056571A JP 5657198 A JP5657198 A JP 5657198A JP H11255508 A JPH11255508 A JP H11255508A
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Abstract
Description
【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。The present invention relates to a novel C70 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。BACKGROUND OF THE INVENTION Invention is to Solve] eta 5 type cyclopentadienyl ligand and its metal complexes of fullerene is a representative compound of carbon cluster (C 60) has already been reported (Journal of American Chemic
al Society, 118, 12850, 1996). However, eta 5-inch cyclopentadienyl ligand of C 70 is not known about. Since C 70 has a larger number of carbon atoms constituting a conjugated polyene system than C 60 , the ability of C 70 and its derivatives, such as photoacceptability and electron acceptability, exceeds that 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）Accordingly, the present inventors have developed C70.
A result of our study on the eta 5 type cyclopentadienyl ligand, thereby completing the present invention. That is, the gist of the present invention is represented by the following general formula (I)
【０００４】[0004]
【化４】 Embedded image
【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）[0005] (In the above formulas, R represents an aryl group of C 1 -C alkyl group having 10 or substituent C 6 optionally having -C 14,) C 70 derivative represented by the following General formula (II) of
【０００６】[0006]
【化５】 Embedded image
【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 includes 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 a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. The C 6 -C 14 aryl group includes a phenyl group, a naphthyl group and the like, and the aryl group is a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. A C 1 -C 5 alkyl group such as a group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group; trifluoromethyl group; methoxy group, ethoxy group, A C 1 -C 5 alkoxy group such as a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, an isopentyloxy group; and at least one substitution selected from a methylenedioxy group It may have a group. In the above general formulas (I), (II) and (III), more preferred examples of the C 1 -C 10 alkyl group defined by R include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. And the like. 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,
And a propoxy group and an isopropoxy group. Examples of the Grignard reagent used in the production of the C 70 derivative represented by the general formula (I) include RMgCl, RMgBr, and RMgI (R is as defined above). The Grignard reagent is mixed with a copper halide derivative. Thus, an organic copper reagent can be prepared. Specific examples of the copper halide derivative include CuBr.SMe 2 .
【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 represented by the general formula (III), the metal constituting the metal alkoxide to be reacted with the C 70 derivative represented by the general formula (I) includes an alkali metal, a transition metal, or a lanthanoid. The alkoxide constituting the metal alkoxide is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group,
Butoxy group, Isobutoshiki group, tert- butoxy group, a pentyloxy group, an alkoxy group of C 1 -C 5, such as iso-pentyl group. Preferred examples of the metal include Li, Na, K, Cr, Mn, Fe, Co, Ni, and C.
u, Zn, Zr, Ru, Rh, Pd, Ag, Cd, R
Examples include t, Au, Hg, Tl, and Sm. Preferred 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】 Embedded image
【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 producing the C 70 derivative represented by the above general formula (I) can be prepared by a method described in the literature (Journal
of American Chemical Society, 99, 253, 19
77 years). For example, RM
It is 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) and diethyl ether. be able to. Then toluene C 70, chlorobenzene, and dissolved in an aromatic hydrocarbon solvent dichlorobenzene was cooled to -100 to-30 ° C., 5 minutes and the organic copper reagent 5-50 equivalents cooled to the same temperature After the dropwise addition 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, and the production of the desired product can be confirmed by HPLC or the like. NH 4 was added to this reaction solution.
If the reaction is stopped by adding an aqueous solution of Cl or the like and then post-treatment is carried out by a conventional method, the desired product can be isolated. As a more preferable reaction condition, the desired 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】 Embedded image
【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 in the above-mentioned production method 1 is converted to T
Dissolved or suspended in an inert solvent such as HF or toluene,
R'OM (R 'represents an alkyl group of C 1 -C 5, M already is as defined) and stirred by adding a metal alkoxide represented by one equivalent -20 to 50 ° C., quickly The metal complex represented by the general formula (III) is obtained. More preferably, the reaction is carried out at about 25 ° C. The obtained solution of the metal complex can be used for the next reaction as it is, or the metal complex represented by the general formula (III) can be isolated by distilling off the solvent under reduced pressure. 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１ Ｃ70（ｐ−ＣＦ3 Ｃ6 Ｈ4 ）3 Ｈの製造 ｐ−ＣＦ3 Ｃ6 Ｈ4 ＭｇＢｒの溶液は、ｐ−ＣＦ3 Ｃ
6 Ｈ4 Ｂｒ（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
To a solution of 6 H 4 Br (0.93 ml) in tetrahydrofuran (8 ml), magnesium metal (173 mg) was added to prepare at the time of use. Divide 2.68 ml 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 was -78.
C. and the solution was added dropwise over 15 minutes. The resulting solution is
The mixture was stirred at 78 ° C for 1 hour, heated to 10 ° C, and further stirred for 10 hours. An aqueous ammonium chloride solution was added to stop the reaction, the organic layer was separated, and the aqueous layer was extracted three times with toluene. Wash the combined organic layers with saturated saline,
Dry through a column of sodium sulfate. A powder was obtained by concentrating the distillate, and the powder was washed four times with hexane and dried under reduced pressure to obtain the desired product (140 mg). 96% yield.
【００１５】1Ｈ ＮＭＲ（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, CDCl 3 / CS 2 ,
δ) 15.9.26 (1 C), 15.5.03 (1 C
), 155.4.07 (1 C), 153.4.45 (1
C), 15 2 .19 (1 C), 15 2 .10 (
1 C), 159.194 (1 C), 150.0.26
(1 C), 14 9. 9 1 (1 C), 14 9.
(1 C), 14 9. 16 (2 C), 14 8.
(2 C), 14.8.77 (1 C), 14.8.59
(2C), 14.8.36 (1C), 14.8.29
(1 C), 1 48.25 (1 C), 1 47.9.
(1 C), 1 4 7. 8 8 (1 C), 1 4 7. 8 6
(1 C), 147.8 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.
(1 C), 14.5.90 (1 C), 14.5.75
(1 C), 1 4 5.
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
3.40 (1 C), 1 4 3 .2 4 (1 C), 1
43.06 (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),
14 0 .07 (1 C), 1 39.4. 4 4 (1 C),
1 3 7. 19 (1 C), 1 3 3 .05 (2 C),
1 3 2.85 (1 C), 1 3 1.86 (1 C),
1 3 1 .8 3 (1 C), 1 3 1 .6 6 (1 C),
13 1 .53 (1 C), 13 .06 .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 26.20 (1 C), 12.6.08-1 26.0
0 (m, 4 C), 1 2 5 .8 4 (q, JC-F
= 3.70 Hz, 2C), 59.54 (1C
), 55.87 (1C), 55.72 (1C)
, 55.17 (1C). FABMS m / z
: Measured value 1 2 7 6 (M +), 8 4 0 (C 7 0)
. Example 2 to Example 5 by the same method as in Example 1.
Was prepared. Hereinafter, only the physical property values will be described.
【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 H NMR (400 MHz, CDCl 3 / C
S 2 , δ): 7.80-7.75 (m, PhH, 2
H), 7.70-7.6 6 (m, P h H, 2H),
7.5 8-7.5 2 (m, Ar H, 3 H),
7.5-7.20 (m, PhH, 8H), 4.
4 1 (s, 1H). 13 CNMR (1 0 0 MH z , CDC l 3 / CS 2
, Δ), 160.70 (1C), 15.5.67 (1
C), 15.5.07 (1 C), 153.8.0 (1
C), 1 5 2 .6 2 (1 C), 1 5 3 .1 4
(1 C), 15 2 .6 2 (1 C), 15 2.
(1 C), 150 .16 (1 C), 14.9 .8 7
(1 C), 14 9. 5 7 (1 C), 14 9.
2 (1 C), 14 9. 3 9 (1 C), 14 9.
7 (1 C), 14 9 .08 (1 C), 1 48.
9 5 (1 C), 1 48. 8 2 (1 C), 1 48.
6 8 (1 C), 1 4 8 .5 9 (1 C), 1 4 8
30 (1 C), 1 48. 2 1 (1 C), 1 48
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
47.68 (1 C), 1 47.18 (1 C), 1 4
7.06 (1C), 14.70 (1C), 1
46.6.5 (1C), 1 46.6.1 (1C), 14
6.44 (1 C), 1 4 6. 2 3 (1 C), 1
46.18 (1C), 14.5.84 (1C),
1 4 5.5. 6 4 (1 C), 1 4 5.5 .5 1 (1C), 1
45.32 (1 C), 1 45.06 (1 C),
14.5.03 (1C), 14.4.92 (1C),
1 4 4 .8 8 (1 C), 1 4 4.74 (1 C),
1 4 4 .4 8 (1 C), 1 4 4 .1 5 (1 C),
1 4 3 .97 7 (1 C), 1 4 3 .4 3 (1 C),
1 4 2 .9 9 (1 C), 1 4 2 .8 1 (1 C),
14 2 .2 1 (1 C), 14 2 .18 (1 C),
140.0.5 (1 C), 140.04 (1 C)
, 139.5.4 (1 C), 139.2.20 (1 C
), 13 8 .33 (1 C), 13 6 .8 7 (1
C), 1 3 3 .08 (1 C), 1 3 1 .9 6 (
1 C), 1 3 1 .9 3 (1 C), 1 3 1.1.8 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), 130. 6 5 (1 C), 1 28.9.
6 (Ph, 2C), 1 28.8.8 8 (Ph, 2C
), 1 28.78 (P h, 2 C), 1 28.16
(1 C), 1 28.0 .4 (1 C), 1 27.7.
1 (1 C), 1 2 7. 6 0 (1 C), 1 2 7. 4
7 (P h, 2 C), 1 2 7.27 (1 C),
1 27.15 (Ph, 2C), 12.6.70 (Ph
, 2 C), 1 2 6. 4 2 (1 C), 5 6. 2 3
(C60, 1C), 56.19 (C60, 1C
), 55. 5 (C60, 2C).
【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 C l3 / 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 r H , 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 C l3 / 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 48 . 9 4 ( 1 C x 2 )
, 1 4 8 . 9 0 ( 1 C ) , 1 4 8 . 6 3 (1 C
) , 1 4 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 ( 1 C ) , 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 4 6 . 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 . 9 8 ( 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 4 0 . 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 ) , 1 3 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 , 2 C ) , 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 2 7 . 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（ C888 H13 C13 ） 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 H NMR (500 MHz, CDCl 3 / CS 2
, Δ): 7.73 (d, J = 6.50 Hz,
A r H, 2 H), 7.63 (d, J = 6.50
H z, Ar H, 2 H), 7.5 0 (d, J
= 6.50 Hz, ArH, 2H), 7.3
8 (d, J = 6.0 .0 Hz, A r H, 2 H
), 7.2 7-7.2 1 (m, Ar H x
2, 4H), 4.34 (s, C70H, 1H). 13 CNMR (1 2 5 MH z , CDC l 3 / CS 2
, Δ): 160.22 (1C), 155.6.0 (1
C), 1 5 4. 7 4 (1 C), 1 5 3.97 7 (1
C), 15 2 .73 (1 C), 15 2 .5 9
(1 C), 15 2 .5 2 (1 C), 10.5. 5 3
(1 C), 150 .2 2 (1 C), 14 9.
(1 C), 1 49.5 .5 0 (1 C x 2), 1 4
9.47 (1 C), 1 4 9. 3 4 (1 C), 1
49.12 (1C), 148.94 (1C x 2)
, 14.8.90 (1 C), 14.8.63 (1 C
), 1 48.5.7 (1 C), 14.8.3 4 (1
C), 14.8.21 (1 C), 14.8.1 3 (
1 C), 1 4 8 .1 1 (1 C), 1 48.0.04 (1
C), 1 4 7. 9 6 (1 C), 1 4 7.
(1 C), 1 4 7. 3 6 (1 C), 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 4 6.
5.76 (1 C), 145.7 (1 C), 1 4
5.6.7 (1C), 14.5.31 (1Cx2),
1 4 5 .2 2 (1 C), 1 4 5 .1 2 (1 C)
, 14.5.05 (1C), 14.4.85 (1C),
14.4.38 (1C), 14.4.27 (1C),
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 24.6.5 (1 C), 1 24.6.1 (1 C)
, 140.0.81 (1C), 140.0.05 (1C
), 13.9.81 (1C), 140.0.0.0 (1
C), 1 37.38 (1 C), 1 36.92 (1
C), 1 3 4 .7 4 (1 C), 1 3 4.60 (1
C), 1 3 4 .1 9 (1 C), 1 3 3 .4 0
(1 C x2), 13 3 .25 (1 C), 13 2.
2 2 (1 C), 1 3 2. 0 2 (1 C), 1 3 1.
8 8 (1 C), 13 0 .85 (1 C), 13 0.
5 5 (1 C), 1 2 9 .5 7 (A r H, 2 C)
, 19.5. 3 (Ar H, 2 C), 19.3.
(A rH, 2 C), 1 2.8. 9 6 (A rH, 2 C
), 1 28.68 (Ar H, 2 C), 1 28.
25 (A rH, 2 C), 1 27.68 (1 C)
, 12.7.60 (1 C), 12.6 .3 (1 C
), 1 2 4.65 (1 C), 1 2 4 .6 1 (1
C), 59.60 (1 C), 55.93 (1 C)
, 55.81 (1C), 55.67 (1C)
. Calcd (C 88 8 H 13 C 13 ) C 8 9 .8
5; H1.11; measured value C89.55; H1
. 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
- preparation 1 HNMR (5 0 0 MH z the naphthyl group), CDC l 3 / CS 2
, Δ): 9.65 (d, J = 8.54 Hz,
A r H, 1 H), 9.5 4 (d, J = 9.7 7 7
H z, Ar H, 1 H), 8.92 (d, J
= 8.85Hz, ArH, 1H), 8.2
6 (d, J = 7.0 .2 Hz, Ar H, 1 H),
8.09 (d, J = 7.6 3 Hz, Ar
H, 1 H), 7.89-7.44 (m, A
r H, 5 H), 7.40 (m, A r H, 1 H)
, 7.36 (m, ArH, 1H), 7.30
-7.2 3 (m, Ar H, 7 H), 6.96
(m, Ar H, 1 H), 6.86 (m, Ar
H, 1H) 4.90 (s, C60H, 1H). 13 CNMR (1 2 5 MH z , 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), 15 4 .5 1 (1 C), 15 3.
(1 C), 15 2 .61 (1 C), 150 .7. 9
(1 C), 150 .0.26 (1 Cx 2), 150
20 (1 C), 15 0. 13 (1 C), 14 9
95 (1 C x 2), 14.9 .6 0 (1 C)
, 14.9.26 (1C), 14.9.19 (1C)
), 14.9.16 (1 C), 14.5.5.5 (1C
), 14.8.3 9 (1 C), 14.8.3 5 (1
C), 1 48.28 (1 C), 1 47.9.4 (1
C), 1 47.86 (1 C), 1 47.60 (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
(1C), 14.5.90 (1C), 14.5.73
(1 C), 14 5. 3 6 (1 C), 14 5. 3
1 (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),
14.4.20 (1C), 14.4.59 (1C)
, 14 3 .4 5 (1 C), 1 4 2 .9 3 (1 C
), 1 4 2 .01 (1 C), 1 4 1 .8 6 (1
C), 1 4 1 .2 6 (1 C), 1 4 1 .0 9 (1
C), 13.9.86 (1 C), 13.9.54
(1 C), 13 6 .71 (1 C), 13 5 .40
(1 C), 13 4 .93 (1 C x 2), 13 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), 12.99.83 (1C), 12.99.70 (1
C), 1 29.5 .4 (1 C), 1 29.4 .8 (1
C), 1 29.2. 4 2 (1 C), 1 29.2.
1 C), 1 28.9.4 (1 C), 1 28.4. 3 (1
C), 128.30 (1 C), 128.15 (
1 C), 12.7.03 (1 C), 1 26.5 .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.
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 25.0 .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 H NMR (400 MHz, CDCl 3 / C
S 2, δ):. 3 9 0 (s, C 7 0 H, 1 H),
2.5 2, (s, Me, 3 H), 2.27 (s,
M e, 3 H), 2.14 (s, M e, 3 H
). FABMS m / z: measured value 8 8 7 (M +),
8 4 0 (C 7 0).
【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 ) 。[0020] Example 6 K at producing 25 ℃ C 70 Ph 3 H ( 9 mg) of potassium tert of (η 5 -C 70 Ph 3) - butoxide
THF - d 8 solution (0.018 M) was added to 0.5 ml, 1 HN
MR was measured. 1 HNMR (4 0 0 MH z , THF - d 8, δ)
: 7.88-7.82 (m, PhH, 5H)
, 7.2 4-7.0 .8 (m, P h H, 10
H).
【００２１】実施例７ K[η5 - C70 (p - CF3 C6 H4
)3 ] の製造 25℃でC70 (p - CF3 C6 H4 )3 H （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 ] Production of C 70 (p-CF 3 C 6 H 4 ) 3 H (11 mg) at 25 ° C. with 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):
8.07-8, 05 (m, ArH, 6H), 7
5 7-7.5 4 (m, ArH, 6H). 13 C
NMR (1 0 0 MH z, THF - d 8, δ): 1
66.18,16.0.5,15.3.3,30,15.
9 9, 1 5 1 .04, 1 5 0. 3 2, 1 4 9. 7
9, 14 9 .77 7, 14 9 .17, 14 8 .88 8
, 1 4 8.8 2, 1 4 8 .8, 1 4 8 .8 4,
1 48.26, 1 47.14, 1 46.90, 14
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
2.60, 1 29.3.6-1 29.2.23 (m), 1
28.93, 1 25.80-1 25.77 (m),
1 2 5.6 (q .J = 2 7 1 .1 9), 1 2
1.07, 6 1.06, 59.1.
【００２２】実施例８ Tl [η5 - C70(p -CF3C6H4)3]
の製造 C70(p - CF3 C6 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 ]
Production of C 70 (p-CF 3 C 6 H 4 ) 3 H (46 mg) in THF (10 ml)
And thallium ethoxide (25 ml) dissolved in THF (75 ml) was added without stirring at 25 ° C under light shielding. After 2 hours, the solvent was distilled off under reduced pressure to obtain the desired product quantitatively. 1 HNMR (4 0 0 MH z , THF - d 8, δ)
d 8.09-8.07 (m, ArH, 6H)
, 7.59-7.53 (m, ArH, 6H).
【００２３】実施例９ K [η5 - C70 (p - ClC
6H4)3 ] の製造 25 ℃でC70(p - ClC6H4 )3 H （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] C 70 in the manufacture 25 ° C. of (p - ClC 6 H 4) 3 potassium H (9 mg) tert
- THF -d 8 solution (0.018 M) butoxide was added to 0.5 ml, was determined by 1 H and 13 CNMR. 1 HNMR (4 0 0 MH z , THF - d 8, δ)
： 7.92-7.81 (m, ArH, 6H)
, 7.2 7-7.2 4 (m, ArH, 6H). 13 CNMR (1 0 0 MH z , THF - d 8, δ)
: 166.82, 160.75, 153.48,
1 5 2 .1 1, 1 5 1 .1 9, 1 4 9 .90, 1 4
9.80, 14.9.29, 14.8.90, 14.8
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
, 14.66.77, 14.66.22, 14.68.28,
14 6. 18, 1 4 5 .7 9, 1 4 5 .6 0,
14.5.58, 14.5.26, 14.4.65, 14
2.8 4, 1 4 2 .5 2, 1 4 2 .48, 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,
130.0.09 (4C), 129.5.50, 128
9 8 (6 C), 1 2 1 .4 4, 6 .0 9,
5 8.7.9
【００２４】実施例１０ K (η5 - C70Me3 )の製造 25 ℃で C70Me3 H （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 Production 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 potassium tert-butoxide solution in THF-d 8 (0.018 M). 1 H and 13 C NMR were measured. 1 HNMR (4 0 0 MH z , THF - d 8, δ): 2
8 6, (s, Me, 3 H), 1.97, (
s, Me, 3Hx2). 13 CNMR (1 0 0 MH z , THF - d 8, δ)
: 168.84 (C60, 2C), 162.04
(C60, 2C), 153.6.2 (C60, 2C
), 15 1 .90 (C 60, 2 C), 15 1.
20 (C60, 2C), 14.9.77 (C60,
2 C), 1 4 9 .09 (C 60, 2 C), 1 4
8.75 (C60, 1C), 14.8.63 (C
6 0, 2 C), 1 48. 3 4 (C 60, 2 C)
, 14.8.29 (C60, 2C), 14.7.4
6 (C 60, 2 C), 1 47.28 (C 60,
2 C), 1 4 6 .4 9 (C 60, 2 C), 1 4
6.36 (C60, 2C), 14.6.26 (C
6 0, 2 C), 1 46 .1 7 (C 60, 2 C + 1
C), 1 4 5. 9 8 (C 60, 2 C), 1 4 5
8 4 (C 60, 2 C), 1 45 .70 (C 6
0, 2 C), 1 45 .47 (C 60, 2 C),
14.5.32 (C60, 2C), 13.4.80
(C 60, 2 C), 1 42 .36 (C 60, 2
C), 1 4 2 .2 7 (C 60, 2 C), 1 3 8.
5 4 (C60, 2C), 13.5.84 (C60
, 2 C), 1 35 .0 2 (C 60, 1 C), 1
33.86 (C60, 2C), 13.3.35 (
C 60, 2 C), 13.3.09 (C60, 2 C)
, 1 3 2 .3 2 (C 60, 2 C), 1 30.1
7 (C6 0, 2 C), 1 2 4 .2 7 (C 60,
9 6 (C 60, 1 C), 5 2.
6 7 (C 60, 2 C), 33.07 (Me, 1
C), 31.77 (Me, 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。The ligand of the present invention, which is a C 70 derivative, and a metal complex containing the same can be used as a ligand or a catalyst in various synthetic reactions.
Claims (9)
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. A compound represented by 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.
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): (Wherein R represents a C 1 -C 10 alkyl group or a C 6 -C 14 aryl group which may have a substituent), η comprising a cyclopentadienide ion represented by the formula:
Type 5 cyclopentadienyl ligand.
エニル配位子を含む金属錯体。3. A metal complex comprising the η 5 type cyclopentadienyl ligand according to claim 2.
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 -C 10 alkyl group or a C 6 -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-mentioned cyclopentadienyl ligand, wherein the metal atom is selected from the group consisting of alkali metals, transition metals and lanthanoids The metal complex according to claim 3, which is represented by:
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 method according to claim 1, wherein the metal atom is Li, Na, K, Cr, 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.
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 organic copper reagent prepared from a Grignard reagent and a copper halide derivative.
・ＳＭｅ2 である請求項６記載の方法。7. The copper halide derivative used is CuBr.
· SMe 2 The method of claim 6 wherein.
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. The method of claim 3, a method for producing a metal complex according to claim 4 or claim 5, comprising the step of reacting a metal alkoxide of C 70 derivative according to claim 1.
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 method according to claim 9, wherein the metal atoms constituting the metal alkoxide are Li, Na, K, Cr, Mn, Fe, Co, Ni, C
u, Zn, Zr, Ru, Rh, Pd, Ag, Cd, R
9. The method according to claim 8, wherein the method is selected from the group consisting of t, Au, Hg, Tl and Sm.
Priority Applications (1)
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|---|---|---|---|
| JP05657198A JP3438571B2 (en) | 1998-03-09 | 1998-03-09 | C70 derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05657198A JP3438571B2 (en) | 1998-03-09 | 1998-03-09 | C70 derivative |
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| Publication Number | Publication Date |
|---|---|
| JPH11255508A true JPH11255508A (en) | 1999-09-21 |
| JP3438571B2 JP3438571B2 (en) | 2003-08-18 |
Family
ID=13030840
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|---|---|---|---|
| JP05657198A Expired - Lifetime JP3438571B2 (en) | 1998-03-09 | 1998-03-09 | C70 derivative |
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| Country | Link |
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