TOP > 外国特許検索 > Cyclopolyarylene metal complex

Cyclopolyarylene metal complex コモンズ

外国特許コード F160008687
整理番号 NU-641
掲載日 2016年3月1日
出願国 アメリカ合衆国
出願番号 201514969601
公報番号 20160168179
出願日 平成27年12月15日(2015.12.15)
公報発行日 平成28年6月16日(2016.6.16)
優先権データ
  • 特願2014-253322 (2014.12.15) JP
発明の名称 (英語) Cyclopolyarylene metal complex コモンズ
発明の概要(英語) If a method for directly functionalizing cycloparaphenylene compounds is developed, such a method is expected to be applied to any cycloparaphenylene compound, thus theoretically enabling introduction of a functional group into all cycloparaphenylene compounds.
Therefore, a primary object of the present invention is to provide a method for easily functionalizing cycloparaphenylene compounds directly.
A cyclopolyarylene metal complex in which a metal tricarbonyl is coordinated to one benzene ring of a cyclopolyarylene compound is provided.
The cyclopolyarylene metal complex is obtained by using a production method comprising the step of reacting a cyclopolyarylene compound with a metal compound represented by the following formula: M(CO)3Ym, wherein M is a metal atom; Y is the same or different, and each represents a ligand; and m is an integer of 1 to 3.
従来技術、競合技術の概要(英語) BACKGROUND ART
[0002] Previously known nanostructures containing carbon atoms include carbon nanotubes made of a cylindrically rolled two-dimensional graphene sheet, cyclic carbon nanotubes containing such carbon nanotubes, and the like.
[0003] Carbon nanotubes have extremely high mechanical strength and high temperature resistance, and efficiently discharge electrons when voltage is applied.
With these advantageous properties, carbon nanotubes are expected to be applied in various fields, including chemistry, electronics, and life sciences.
[0004] Known methods of producing carbon nanotubes include arc discharge, laser furnaces, chemical vapor deposition, and the like.
However, these methods have a disadvantage in that they can only produce mixtures of carbon nanotubes with various diameters and lengths.
[0005] As a replacement for tubular nanostructures such as carbon nanotubes with a certain length derived from a continuous linkage of carbon atoms, recent studies have focused attention on cyclic nanostructures.
For example, cycloparaphenylene (CPP) is a simple and beautiful molecule in which benzenes are linked at the para-positions to form a circle.
Recent studies have revealed that cycloparaphenylene has a significantly distinctive structure and nature.
In particular, since CPP has various diameters depending on the number of benzene rings it contains, and thus has various natures, if CPP is selectively produced, it has the potential to produce carbon nanotubes with various diameters.
Therefore, the thoroughly selective production of CPP having different numbers of benzene rings has been desired.
However, although a method for obtaining CPP as a mixture is known, the selective synthesis of CPP has been successful in only a few cases.
[0006] The present inventors succeeded in the synthesis of various cycloparaphenylene compounds through a method using a cyclic cycloparaphenylene precursor that contains a cyclohexane ring as a flexural portion (for example, Patent Literature 1 and 2, and Non-patent Literature 1).
[0007] However, although cycloparaphenylene compounds have a significantly distinctive structure and nature as described above, the introduction of a new function by adding a functional group to these compounds has not been developed.
Since cycloparaphenylene compounds are highly symmetrical molecules and have many equivalent reaction sites (for example, [12]CPP, which has 12 benzene rings, has 48 equivalent reaction sites), it is difficult to introduce a desired number of functional groups at desired positions.
[0008] Nevertheless, synthesis of functionalized cycloparaphenylene compounds has the potential to lead to synthesis of various unique compounds, such as dimers of cycloparaphenylene compounds.
Thus, there is a need for a method to introduce a desired number of functional groups into desired portions of a cycloparaphenylene compound.
[0009] In such a situation, only a method for newly synthesizing cyclic compounds using functional-group-containing monomers (bottom-up method) is known (for example, Patent Literature 3 and Non-patent Literature 2).

CITATION LIST

Patent Literature
[0010] PTL 1: WO2011/099588
[0011] PTL 2: WO2011/111719
[0012] PTL 3: WO2013/133386

Non-Patent Literature
[0013] NPL 1: Takaba, H.; Omachi, H.; Yamamoto, Y.; Bouffard, J.; Itami, K. Angew. Chem. Int. Ed. 2009, 48, 6112
[0014] NPL 2: Ishii Y.; Matsuura S.; Segawa Y.; Itami K. Org. Lett. 2014, 16, 2174

特許請求の範囲(英語) [claim1]
1. A cyclopolyarylene metal complex in which a metal tricarbonyl is coordinated to one benzene ring of a cyclopolyarylene compound.
[claim2]
2. The cyclopolyarylene metal complex according to claim 1, wherein the cyclopolyarylene compound is a cyclic compound in which at least one member selected from the group consisting of bivalent aromatic hydrocarbon groups and derivative groups thereof are continuously bonded.
[claim3]
3. The cyclopolyarylene metal complex according to claim 1, wherein the metal constituting the metal tricarbonyl is chromium, molybdenum, tungsten, iron, ruthenium, osmium, manganese, or rhenium.
[claim4]
4. A method for producing the cyclopolyarylene metal complex according to claim 1, the method comprising the step of (I) reacting a cyclopolyarylene compound with a metal compound represented by Formula (2):
M(CO)3Ym,
wherein M is a metal atom; Y is the same or different, and each represents a ligand; m is an integer of 1 to 3.
[claim5]
5. The method according to claim 4, wherein the step (I) is performed in the presence of an ether solvent or a hydrocarbon solvent.
[claim6]
6. A metal-substituted cyclopolyarylene compound in which a metal atom is bonded to one carbon atom of one benzene ring of a cyclopolyarylene compound.
[claim7]
7. The metal-substituted cyclopolyarylene compound according to claim 6, wherein the metal atom is an alkali metal atom.
[claim8]
8. A method for producing a metal-substituted cyclopolyarylene compound, the method comprising the step of (II) reacting the cyclopolyarylene metal complex according to claim 1 with a metal compound.
[claim9]
9. The method according to claim 8, wherein the metal compound is an alkali metal compound.
[claim10]
10. The method according to claim 8, wherein the metal compound is an alkyllithium.
[claim11]
11. A functional-group-containing cyclopolyarylene compound in which a boronic acid group or an ester thereof, a silyl group, a carboxy group or an ester thereof, or a formyl group is bonded to one carbon atom of one benzene ring of a cyclopolyarylene compound.
[claim12]
12. A method for producing a functional-group-containing cyclopolyarylene compound, the method comprising the step of (III) reacting the metal-substituted cyclopolyarylene compound according to claim 6 with an electrophile.
[claim13]
13. The cyclopolyarylene metal complex according to claim 2, wherein the metal constituting the metal tricarbonyl is chromium, molybdenum, tungsten, iron, ruthenium, osmium, manganese, or rhenium.
  • 発明者/出願人(英語)
  • ITAMI KENICHIRO
  • SEGAWA YASUTOMO
  • KUBOTA NATSUMI
  • NAGOYA UNIVERSITY
国際特許分類(IPC)
米国特許分類/主・副
  • 556/60
  • 556/478
  • 556/489
  • 560/102
  • 568/6
名古屋大学の公開特許情報を掲載しています。ご関心のある案件がございましたら、下記まで電子メールでご連絡ください。

PAGE TOP

close
close
close
close
close
close