Diazadioxa[8]circulenes: Planar Antiaromatic Cyclooctatetraenes

被引：81

作者：

Hensel, Thomas ^{[1
]}

Trpcevski, Denis ^{[1
]}

Lind, Christopher ^{[1
]}

Grosjean, Remi ^{[1
]}

Hammershoj, Peter ^{[1
]}

Nielsen, Christian B. ^{[1
]}

Brock-Nannestad, Theis ^{[1
]}

Nielsen, Bjarne E. ^{[1
]}

Schau-Magnussen, Magnus ^{[1
]}

Minaev, Boris ^{[2
]}

Baryshnikov, Gleb V. ^{[2
]}

Pittelkow, Michael ^{[1
]}

机构：

[1] Univ Copenhagen, Dept Chem, DK-2100 Copenhagen O, Denmark

[2] Bohdan Khmelnytsky Natl Univ, UA-18031 Cherkassy, Ukraine

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2013年 / 19卷 / 50期

关键词：

aromaticity; density functional calculations; electrochemistry; fluorescence; heterocycles; AROMATICITY;

D O I：

10.1002/chem.201303194

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

In this paper we describe a new class of antiaromatic planar cyclooctatetraenes: the diazadioxa[8]circulenes. The synthesis was achieved by means of a new acid-mediated oxidative dimerization of 3,6-dihydroxycarbazoles to yield the diazadioxa[8]circulenes in high yields. The synthetic protocol appears to be general, and is a one-pot transformation in which two CC bonds and two CO bonds are formed with the loss of two molecules of water. We also present a detailed characterization of the optical and electrochemical properties of this new class of stable planar cyclooctatetraenes. The properties of the diazadioxa[8]circulenes are compared with the properties of isoelectronic tetraoxa[8]circulenes and azatrioxa[8]circulenes. We discuss the antiaromatic nature of the planar central cyclooctatetraene moiety. The antiaromatic nature of the planar cyclooctatetraenes was studied by using computational methods (NICS calculations), and these calculations reveal that the central eight-membered ring has antiaromatic character.

引用

页码：17097 / 17102

页数：6

共 30 条

[1]

[Anonymous], 2011, ANGEW CHEM

[2]

[Anonymous], 2006, ANGEW CHEM

[3]

Arnbjerg J, 2007, J PHYS CHEM A, V111, P5756, DOI 10.1021/jp0711971

[4]

BERG JE, 1977, TETRAHEDRON LETT, P1831

[5] ANTIAROMATICITY [J].

BRESLOW, R .

ACCOUNTS OF CHEMICAL RESEARCH, 1973, 6 (12) :393-398

[6] Tetra-tert-butyltetraoxa[8]circulene and Its Unusual Aggregation Behaviour [J].

Brock-Nannestad, Theis ;

Nielsen, Christian B. ;

Schau-Magnussen, Magnus ;

Hammershoj, Peter ;

Reenberg, Theis K. ;

Petersen, Asger B. ;

Trpcevski, Denis ;

Pittelkow, Michael .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2011, 2011 (31) :6320-6325

[7] Critical analysis of the local aromaticity concept in polyaromatic hydrocarbons [J].

Bultinck, Patrick .

FARADAY DISCUSSIONS, 2007, 135 :347-365

[8] The larger N-heteroacenes [J].

Bunz, Uwe H. F. .

PURE AND APPLIED CHEMISTRY, 2010, 82 (04) :953-968

[9] Electron-Accepting 6,12-Diethynylindeno[1,2-b]fluorenes: Synthesis, Crystal Structures, and Photophysical Properties [J].

Chase, Daniel T. ;

Fix, Aaron G. ;

Rose, Bradley D. ;

Weber, Christopher D. ;

Nobusue, Shunpei ;

Stockwell, Chelsea E. ;

Zakharov, Lev N. ;

Lonergan, Mark C. ;

Haley, Michael M. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (47) :11103-11106

[10] Indeno[1,2-b]fluorenes: Fully Conjugated Antiaromatic Analogues of Acenes [J].

Chase, Daniel T. ;

Rose, Bradley D. ;

McClintock, Sean P. ;

Zakharov, Lev N. ;

Haley, Michael M. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (05) :1127-1130

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