Syntheses, Solid State Structures and Photochemistry of α,ω-Bis-[(1,8-dichloroanthracen-10-yl)dimethylsilyl]alkanes

^‡ These authors contributed equally to this work.

Abstract

Starting from 10-bromo-1,8-dichloroanthracene, a series of 1,8-dichlorinated anthracene derivatives, flexibly bridged in position 10 by –Me₂Si– and –Me₂Si–(CH₂) _n –SiMe₂– linker units, were synthesised. The linked anthracenes were generated by converting (1,8-dichloroanthracen-10-yl)lithium with chlorosilanes in salt-elimination reactions. The bichromophors were tested in UV light induced photo reactions. None of the new compounds yielded any intra- or intermolecular photoproduct. All α,ω-(dimethylsilyl)alkane-linked bisanthracenes decomposed to give 1,8-dichloro-9-hydroxyanthracen-10(9H)-one in the presence of oxygen. A completely different behaviour was shown by the bisanthracenyldimethylsilane, undergoing a 9,10:3′,4′-photocyclomerisation reaction. The new compounds were characterised by NMR spectroscopy, mass spectrometry and in most cases by X-ray diffraction studies.

Key words

anthracenes - salt metathesis reactions - solid-state structures - photocyclomerisation - oxygenation

• References


Examples for organic applications:
• 1a Toyota S. Goichi M. Kotani M. Angew. Chem. Int. Ed. 2004; 43: 2248 ; Angew. Chem. 2004, 116, 2298
• 1b Tsuya T. Iritani K. Tahara K. Tobe Y. Iwanaga T. Toyota S. Chem. Eur. J. 2015; 21: 5520
• 1c Fudickar W. Linker T. J. Am. Chem. Soc. 2012; 134: 15071
• 1d Fudickar W. Linker T. J. Org. Chem. 2017; 82: 9258

Examples of organometallic applications, for example:
• 2a Katz HE. J. Org. Chem. 1989; 54: 2179
• 2b Li Y. Köse ME. Schanze KS. J. Phys. Chem. B 2013; 117: 9025
• 2c Chmiel J. Neumann B. Stammler H.-G. Mitzel NW. Chem. Eur. J. 2010; 16: 11906
• 2d Lamm J.-H. Niermeier P. Mix A. Chmiel J. Neumann B. Stammler H.-G. Mitzel NW. Angew. Chem. Int. Ed. 2014; 53: 7938; Angew. Chem. 2014, 126, 8072
• 3a Bouas-Laurent H. Castellan A. Desvergne J.-P. Pure Appl. Chem. 1980; 52: 2633
• 3b Desvergne J.-P. Bouas-Laurent H. J. Chem. Soc., Chem. Comm. 1978; 403
• 4 Lamm J.-H. Niermeier P. Körte LA. Neumann B. Stammler H.-G. Mitzel NW. Synthesis 2018; 50: 2009
• 5 Becker H.-D. Chem. Rev. 1993; 93: 145
• 6 Lamm J.-H. Vishnevskiy YuV. Ziemann E. Kinder TA. Neumann B. Stammler H.-G. Mitzel NW. Eur. J. Inorg. Chem. 2014; 941
• 7 Cordero B. Gómez V. Platero-Prats AE. Revés M. Echeverría J. Cremades E. Barragán F. Alvarez S. Dalton Trans. 2008; 2832
• 8a Desvergne J.-P. Bitit N. Pillot J.-P. Bouas-Laurent H. J. Chem. Res. 1989; 146
• 8b Felix G. Lapouyade R. Bouas-Laurent H. Clin B. Tetrahedron Lett. 1976; 26: 2277
• 8c Desvergne J.-P. Bitit N. Castellan A. Webb M. Bouas-Laurent H. J. Chem. Soc., Perkin Trans. 2 1988; 1885
• 9 Klaper M. Wessig P. Linker T. Chem. Commun. 2016; 52: 1210
• 10 Karama U. Sultan MA. Ghabour HA. Fun HK. Warad IKh. Z. Kristallogr. - New Cryst. Struct. 2013; 228: 405
• 11 Daney M. Vanucci C. Desvergne J.-P. Castellan A. Bouas-Laurent H. Tetrahedron Lett. 1985; 26: 1505
• 12 Becker H.-D. Skelton BW. White AH. Aust. J. Chem. 1989; 42: 1869
• 13 Hine J. Brown JA. Zalkow LH. Gardner WE. Hine M. J. Am. Chem. Soc. 1955; 77: 594
• 14a Chmiel J. Heesemann I. Mix A. Neumann B. Stammler H.-G. Mitzel NW. Eur. J. Org. Chem. 2010; 3897
• 14b Lamm J.-H. Vishnevskiy YuV. Ziemann E. Neumann B. Stammler H.-G. Mitzel NW. ChemistryOpen 2018; 7: 111

Examples for 9,10:1′,2′-photocyclomers:
• 15a Becker H.-D. Hansen L. Andersson K. J. Org. Chem. 1986; 51: 2956
• 15b Sakurai H. Sakamoto K. Nakamura A. Kira M. Chem. Lett. 1985; 497
• 15c Nishimae Y. Kurata H. Oda M. Angew. Chem. Int. Ed. 2004; 43: 4947 ; Angew. Chem. 2004, 116, 5055
• 16 Becker H.-D. Skelton BW. White AH. Aust. J. Chem. 1991; 44: 181
• 17 Toyama H. Nakamura M. Nakamura M. Matsumoto Y. Nakagomi M. Hashimoto Y. Bioorg. Med. Chem. 2014; 22: 1948
• 18 Sheldrick GM. Acta Crystallogr., Sect. C 2015; 71: 3
• 19 CCDC 1824699 (2), 1824700 (3), 1824701 (4), 1003188 (5), 1824702 (7), 1824703 (8), 1003186 (9), 1003187 (10), 1003190 (11), 1824704 (12) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.