Oxidation of Polynuclear Aromatic Hydrocarbons with Ceric Ammonium Sulfate: Preparation of Quinones and Lactones

George Balanikas, Nalband Hussain, Amin Shantu, Stephen S. Hecht

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

The oxidation of polynuclear aromatic hydrocarbons with ceric ammonium sulfate (CAS) in sulfuric acid was investigated. Oxidation of benzo[κ]fluoranthene (1) gave a mixture of the 7,12- and 2,3-diones 3 and 4. The 2,3-dione (4) was used as the starting material for a facile synthesis of 2,3-dihydro-2,3-dihydroxybenzo[κ]fluoranthene (5) and the corresponding diol epoxide 6, which are potentially important metabolites of benzo[κ]fluoranthene. In a similar manner, 2,3-dihydro-2,3-dihydroxyfluoranthene (7) and its diol epoxide 8 were prepared from fluoranthene. Oxidation of benzo[b]fluoranthene (2) with CAS did not yield quinones, but instead gave benzo[d]fluoreno[2,1-b]pyran-5,13-dione (9), which was identified by its spectral properties and by reduction with LiAlH4. The lactone 9 formed via initial A-region oxidation of 2. It was not formed from 1-hydroxybenzo- [5]fluoranthene (12), which gave benzo[b]fluoranthene-1,2-dione (13) upon CAS oxidation. CAS oxidation of benzo[a]pyrene (14) gave a mixture of the 1,6- and 3,6-quinones 17 and 18. Treatment of benz[a]anthracene (15) with CAS yielded 7-oxo-12-hydroxy-7,12-dihydrobenz[a]anthracene (19) and the 7,12-quinone 20. Oxidation of chrysene (16) with CAS gave 6H-benzo[d]naphtho[1,2-b]pyran-6-one (21) and the 5,6-quinone 22. The results of this study demonstrate that CAS oxidation is useful for the synthesis of certain PAH quinones or lactones, from polynuclear aromatic hydrocarbons, depending on the ring system.

Original languageEnglish (US)
Pages (from-to)1007-1010
Number of pages4
JournalJournal of Organic Chemistry
Volume53
Issue number5
DOIs
StatePublished - Oct 1 1988

Fingerprint

Quinones
Polycyclic Aromatic Hydrocarbons
Lactones
Oxidation
Pyrans
ceric ammonium sulfate
Benzo(a)pyrene
Epoxy Compounds
Polycyclic aromatic hydrocarbons
Metabolites
fluoranthene

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Balanikas, George ; Hussain, Nalband ; Shantu, Amin ; Hecht, Stephen S. / Oxidation of Polynuclear Aromatic Hydrocarbons with Ceric Ammonium Sulfate : Preparation of Quinones and Lactones. In: Journal of Organic Chemistry. 1988 ; Vol. 53, No. 5. pp. 1007-1010.
@article{aefc16a4c4f94ac099ec54ab571a805e,
title = "Oxidation of Polynuclear Aromatic Hydrocarbons with Ceric Ammonium Sulfate: Preparation of Quinones and Lactones",
abstract = "The oxidation of polynuclear aromatic hydrocarbons with ceric ammonium sulfate (CAS) in sulfuric acid was investigated. Oxidation of benzo[κ]fluoranthene (1) gave a mixture of the 7,12- and 2,3-diones 3 and 4. The 2,3-dione (4) was used as the starting material for a facile synthesis of 2,3-dihydro-2,3-dihydroxybenzo[κ]fluoranthene (5) and the corresponding diol epoxide 6, which are potentially important metabolites of benzo[κ]fluoranthene. In a similar manner, 2,3-dihydro-2,3-dihydroxyfluoranthene (7) and its diol epoxide 8 were prepared from fluoranthene. Oxidation of benzo[b]fluoranthene (2) with CAS did not yield quinones, but instead gave benzo[d]fluoreno[2,1-b]pyran-5,13-dione (9), which was identified by its spectral properties and by reduction with LiAlH4. The lactone 9 formed via initial A-region oxidation of 2. It was not formed from 1-hydroxybenzo- [5]fluoranthene (12), which gave benzo[b]fluoranthene-1,2-dione (13) upon CAS oxidation. CAS oxidation of benzo[a]pyrene (14) gave a mixture of the 1,6- and 3,6-quinones 17 and 18. Treatment of benz[a]anthracene (15) with CAS yielded 7-oxo-12-hydroxy-7,12-dihydrobenz[a]anthracene (19) and the 7,12-quinone 20. Oxidation of chrysene (16) with CAS gave 6H-benzo[d]naphtho[1,2-b]pyran-6-one (21) and the 5,6-quinone 22. The results of this study demonstrate that CAS oxidation is useful for the synthesis of certain PAH quinones or lactones, from polynuclear aromatic hydrocarbons, depending on the ring system.",
author = "George Balanikas and Nalband Hussain and Amin Shantu and Hecht, {Stephen S.}",
year = "1988",
month = "10",
day = "1",
doi = "10.1021/jo00240a013",
language = "English (US)",
volume = "53",
pages = "1007--1010",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "5",

}

Oxidation of Polynuclear Aromatic Hydrocarbons with Ceric Ammonium Sulfate : Preparation of Quinones and Lactones. / Balanikas, George; Hussain, Nalband; Shantu, Amin; Hecht, Stephen S.

In: Journal of Organic Chemistry, Vol. 53, No. 5, 01.10.1988, p. 1007-1010.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Oxidation of Polynuclear Aromatic Hydrocarbons with Ceric Ammonium Sulfate

T2 - Preparation of Quinones and Lactones

AU - Balanikas, George

AU - Hussain, Nalband

AU - Shantu, Amin

AU - Hecht, Stephen S.

PY - 1988/10/1

Y1 - 1988/10/1

N2 - The oxidation of polynuclear aromatic hydrocarbons with ceric ammonium sulfate (CAS) in sulfuric acid was investigated. Oxidation of benzo[κ]fluoranthene (1) gave a mixture of the 7,12- and 2,3-diones 3 and 4. The 2,3-dione (4) was used as the starting material for a facile synthesis of 2,3-dihydro-2,3-dihydroxybenzo[κ]fluoranthene (5) and the corresponding diol epoxide 6, which are potentially important metabolites of benzo[κ]fluoranthene. In a similar manner, 2,3-dihydro-2,3-dihydroxyfluoranthene (7) and its diol epoxide 8 were prepared from fluoranthene. Oxidation of benzo[b]fluoranthene (2) with CAS did not yield quinones, but instead gave benzo[d]fluoreno[2,1-b]pyran-5,13-dione (9), which was identified by its spectral properties and by reduction with LiAlH4. The lactone 9 formed via initial A-region oxidation of 2. It was not formed from 1-hydroxybenzo- [5]fluoranthene (12), which gave benzo[b]fluoranthene-1,2-dione (13) upon CAS oxidation. CAS oxidation of benzo[a]pyrene (14) gave a mixture of the 1,6- and 3,6-quinones 17 and 18. Treatment of benz[a]anthracene (15) with CAS yielded 7-oxo-12-hydroxy-7,12-dihydrobenz[a]anthracene (19) and the 7,12-quinone 20. Oxidation of chrysene (16) with CAS gave 6H-benzo[d]naphtho[1,2-b]pyran-6-one (21) and the 5,6-quinone 22. The results of this study demonstrate that CAS oxidation is useful for the synthesis of certain PAH quinones or lactones, from polynuclear aromatic hydrocarbons, depending on the ring system.

AB - The oxidation of polynuclear aromatic hydrocarbons with ceric ammonium sulfate (CAS) in sulfuric acid was investigated. Oxidation of benzo[κ]fluoranthene (1) gave a mixture of the 7,12- and 2,3-diones 3 and 4. The 2,3-dione (4) was used as the starting material for a facile synthesis of 2,3-dihydro-2,3-dihydroxybenzo[κ]fluoranthene (5) and the corresponding diol epoxide 6, which are potentially important metabolites of benzo[κ]fluoranthene. In a similar manner, 2,3-dihydro-2,3-dihydroxyfluoranthene (7) and its diol epoxide 8 were prepared from fluoranthene. Oxidation of benzo[b]fluoranthene (2) with CAS did not yield quinones, but instead gave benzo[d]fluoreno[2,1-b]pyran-5,13-dione (9), which was identified by its spectral properties and by reduction with LiAlH4. The lactone 9 formed via initial A-region oxidation of 2. It was not formed from 1-hydroxybenzo- [5]fluoranthene (12), which gave benzo[b]fluoranthene-1,2-dione (13) upon CAS oxidation. CAS oxidation of benzo[a]pyrene (14) gave a mixture of the 1,6- and 3,6-quinones 17 and 18. Treatment of benz[a]anthracene (15) with CAS yielded 7-oxo-12-hydroxy-7,12-dihydrobenz[a]anthracene (19) and the 7,12-quinone 20. Oxidation of chrysene (16) with CAS gave 6H-benzo[d]naphtho[1,2-b]pyran-6-one (21) and the 5,6-quinone 22. The results of this study demonstrate that CAS oxidation is useful for the synthesis of certain PAH quinones or lactones, from polynuclear aromatic hydrocarbons, depending on the ring system.

UR - http://www.scopus.com/inward/record.url?scp=0000290949&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000290949&partnerID=8YFLogxK

U2 - 10.1021/jo00240a013

DO - 10.1021/jo00240a013

M3 - Article

AN - SCOPUS:0000290949

VL - 53

SP - 1007

EP - 1010

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 5

ER -