Reversible Friedel-Crafts acylations of anthracene: Rearrangements of acetylanthracenes

Tahani Mala'bi; Sergey Pogodin; Israel Agranat

doi:10.2174/157017809787893118

Reversible Friedel-Crafts acylations of anthracene: Rearrangements of acetylanthracenes

Tahani Mala'bi, Sergey Pogodin, Israel Agranat^*

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

Treatment of 1-acetylanthracene (1-AcAN) and 9-acetylanthracene (9-AcAN) with PPA at 80-120 °C leads to the nearly complete conversion of these isomers into 2-acetylanthracene (2-AcAN), an illustration of the Agranat-Gore rearrangement of polycyclic aromatic ketones (PAKs). Ab initio MP2/6-31(d) calculations predict the following order of stabilities: for O-complexes: 9-AcAN>1-AcAN>2-AcAN; for ketones: 2-AcAN>1-AcAN>9-AcAN; for O-protonated ketones: 2-AcAN>1-AcAN>9-AcAN. Thus, 9-AcAN is the kinetically controlled product, whereas 2-AcAN is the thermodynamically controlled product. No reverse rearrangements of 2-AcAN to either 9-AcAN or 1-AcAN and of 1-AcAN to 9-AcAN were observed. The results strengthen the pattern of reversibility in Friedel-Crafts acylations of PAHs.

Original language	English
Pages (from-to)	237-241
Number of pages	5
Journal	Letters in Organic Chemistry
Volume	6
Issue number	3
DOIs	https://doi.org/10.2174/157017809787893118
State	Published - Apr 2009

Keywords

Ab initio calculations
Agranat-Gore rearrangement
Deacylation
Friedel-Crafts acetylation
Overcrowding
PPA

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title = "Reversible Friedel-Crafts acylations of anthracene: Rearrangements of acetylanthracenes",

abstract = "Treatment of 1-acetylanthracene (1-AcAN) and 9-acetylanthracene (9-AcAN) with PPA at 80-120 °C leads to the nearly complete conversion of these isomers into 2-acetylanthracene (2-AcAN), an illustration of the Agranat-Gore rearrangement of polycyclic aromatic ketones (PAKs). Ab initio MP2/6-31(d) calculations predict the following order of stabilities: for O-complexes: 9-AcAN>1-AcAN>2-AcAN; for ketones: 2-AcAN>1-AcAN>9-AcAN; for O-protonated ketones: 2-AcAN>1-AcAN>9-AcAN. Thus, 9-AcAN is the kinetically controlled product, whereas 2-AcAN is the thermodynamically controlled product. No reverse rearrangements of 2-AcAN to either 9-AcAN or 1-AcAN and of 1-AcAN to 9-AcAN were observed. The results strengthen the pattern of reversibility in Friedel-Crafts acylations of PAHs.",

keywords = "Ab initio calculations, Agranat-Gore rearrangement, Deacylation, Friedel-Crafts acetylation, Overcrowding, PPA",

author = "Tahani Mala'bi and Sergey Pogodin and Israel Agranat",

year = "2009",

month = apr,

doi = "10.2174/157017809787893118",

language = "אנגלית",

volume = "6",

pages = "237--241",

journal = "Letters in Organic Chemistry",

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T1 - Reversible Friedel-Crafts acylations of anthracene

T2 - Rearrangements of acetylanthracenes

AU - Mala'bi, Tahani

AU - Pogodin, Sergey

AU - Agranat, Israel

PY - 2009/4

Y1 - 2009/4

N2 - Treatment of 1-acetylanthracene (1-AcAN) and 9-acetylanthracene (9-AcAN) with PPA at 80-120 °C leads to the nearly complete conversion of these isomers into 2-acetylanthracene (2-AcAN), an illustration of the Agranat-Gore rearrangement of polycyclic aromatic ketones (PAKs). Ab initio MP2/6-31(d) calculations predict the following order of stabilities: for O-complexes: 9-AcAN>1-AcAN>2-AcAN; for ketones: 2-AcAN>1-AcAN>9-AcAN; for O-protonated ketones: 2-AcAN>1-AcAN>9-AcAN. Thus, 9-AcAN is the kinetically controlled product, whereas 2-AcAN is the thermodynamically controlled product. No reverse rearrangements of 2-AcAN to either 9-AcAN or 1-AcAN and of 1-AcAN to 9-AcAN were observed. The results strengthen the pattern of reversibility in Friedel-Crafts acylations of PAHs.

AB - Treatment of 1-acetylanthracene (1-AcAN) and 9-acetylanthracene (9-AcAN) with PPA at 80-120 °C leads to the nearly complete conversion of these isomers into 2-acetylanthracene (2-AcAN), an illustration of the Agranat-Gore rearrangement of polycyclic aromatic ketones (PAKs). Ab initio MP2/6-31(d) calculations predict the following order of stabilities: for O-complexes: 9-AcAN>1-AcAN>2-AcAN; for ketones: 2-AcAN>1-AcAN>9-AcAN; for O-protonated ketones: 2-AcAN>1-AcAN>9-AcAN. Thus, 9-AcAN is the kinetically controlled product, whereas 2-AcAN is the thermodynamically controlled product. No reverse rearrangements of 2-AcAN to either 9-AcAN or 1-AcAN and of 1-AcAN to 9-AcAN were observed. The results strengthen the pattern of reversibility in Friedel-Crafts acylations of PAHs.

KW - Ab initio calculations

KW - Agranat-Gore rearrangement

KW - Deacylation

KW - Friedel-Crafts acetylation

KW - Overcrowding

KW - PPA

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Reversible Friedel-Crafts acylations of anthracene: Rearrangements of acetylanthracenes

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