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Structural Chemistry

, Volume 28, Issue 2, pp 511–526 | Cite as

Friedel–Crafts acyl rearrangements in the fluoranthene series

  • Tahani Mala’bi
  • Shmuel Cohen
  • Sergey Pogodin
  • Israel Agranat
Original Research

Abstract

Friedel–Crafts monoacylation and diacylation of fluoranthene (FT) gave 3-acetyl-, 8-acetyl-, 3-benzoyl-, 8-benzoyl-, 3-(4-fluorobenzoyl)-, 8-(4-fluorobenzoyl)-, 3,9-diacetyl-, 3,9-dibenzoyl-, and 3,9-bis(4-fluorobenzoyl)fluoranthene (3-AcFT, 8-AcFT, 3-BzFT, 8-BzFT, 3-(4-FBz)FT, 8-(4-FBz)FT, 3,9-Ac2FT, 3,9-Bz2FT, and 3,9-(4-FBz)2FT). The crystal and molecular structures of 8-AcFT, 3,9-Ac2FT, 7,10-Ac2FT, 3-BzFT, 8-BzFT, and 3-(4-FBz)FT were determined by X-ray crystallography. The structures of the fluoranthene derivatives, including 3,9-Ac2FT were verified by 1H-, 13C-, and 19F-NMR spectroscopy. The Friedel–Crafts acyl rearrangements in PPA of the above fluoranthene derivatives were studied at various temperatures and times. The kinetically controlled product 3-AcFT/3-BzFT rearranged to the thermodynamically-controlled product 8-AcFT/8-BzFT, not vice versa. 3,9-Ac2FT, 3,9-Bz2FT, and 3,9-(4-FBz)2FT underwent deacylation in PPA to give 8-AcFT, 8-BzFT, and 8-(4-FBz)FT, respectively. Deacetylation of 3,9-Ac2FT gave also 3-methyl-1H-benzo[cd]fluoranthene (3-MeBcdFT). The rich Friedel–Crafts acylation chemistry in PPA revealed in the fluoranthene series is characterized by regioselectivity. DFT calculations at B3LYP/6-31G(d) supported the regioselectivity including the formation of 3,9-Ac2FT, and the win of kinetic control over thermodynamic control.

Keywords

X-ray crystallography NMR spectroscopy Regioselectivity Deacylation Kinetic control Thermodynamic control PPA DFT 

Supplementary material

11224_2016_894_MOESM1_ESM.doc (600 kb)
ESM 1 (DOC 600 kb)

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Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  1. 1.Organic Chemistry, Institute of ChemistryThe Hebrew University of JerusalemJerusalemIsrael

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