Synthesis of Fjord Region Diol Epoxides as Potential Ultimate Carcinogens of Dibenzo[a,l]pyrene

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Abstract

Dibenzo [a,l]pyrene (DB[a,l]P) is one of the strongest polynuclear aromatic hydrocarbon carcinogens known. This paper describes the synthesis of potential ultimate carcinogens of DB[a,l]P: anti- and syn-11,12-dihydroxy-13,14-epoxy-11,12,13,14-tetrahydroDB[a,l]P (DB-[a,l]P-11,12-diol-13,14-epoxides). The method employed is also useful for the preparation of key intermediates for the synthesis of 11,12-dihydroxy-13,14-epoxy-11,12,13,14-tetrahydrobenzo-[g]chrysene (BgC-11,12-diol-13,14-epoxide). Photochemical cyclization of the appropriately substituted phenanthrylphenylethylenes provided 9-carbomethoxy-11-methoxyBgC (4) and 11-methoxyBgC (3). The former was converted by reduction, oxidation, one-carbon chain extension, and cyclization to 11-methoxy DB[a,l]P (7). Compounds 3 and 7 were converted by hydrolysis and oxidation to BgC-11,12-dione (10) and DB[a,l]P-11,12-dione (11), respectively. The diones are the precursors for the synthesis of the corresponding diol epoxides, anti- and syn-DB-[a,l] P-11,12-diol-13,14-epoxides 13 and 14 were prepared in 38% and 55% yields, respectively, from 11. Both diol epoxides had predominantly pseudodiequatorial hydroxyl groups, as seen in other sterically hindered diol epoxides.

Original languageEnglish (US)
Pages (from-to)125-129
Number of pages5
JournalChemical research in toxicology
Volume7
Issue number2
DOIs
StatePublished - Mar 1 1994

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Estuaries
Epoxy Compounds
Carcinogens
Cyclization
Oxidation
Polycyclic Aromatic Hydrocarbons
Hydroxyl Radical
dibenzo(a,l)pyrene
Hydrolysis
Carbon
P 11

All Science Journal Classification (ASJC) codes

  • Toxicology

Cite this

@article{15d086abfb624d6d8934647e244d3f98,
title = "Synthesis of Fjord Region Diol Epoxides as Potential Ultimate Carcinogens of Dibenzo[a,l]pyrene",
abstract = "Dibenzo [a,l]pyrene (DB[a,l]P) is one of the strongest polynuclear aromatic hydrocarbon carcinogens known. This paper describes the synthesis of potential ultimate carcinogens of DB[a,l]P: anti- and syn-11,12-dihydroxy-13,14-epoxy-11,12,13,14-tetrahydroDB[a,l]P (DB-[a,l]P-11,12-diol-13,14-epoxides). The method employed is also useful for the preparation of key intermediates for the synthesis of 11,12-dihydroxy-13,14-epoxy-11,12,13,14-tetrahydrobenzo-[g]chrysene (BgC-11,12-diol-13,14-epoxide). Photochemical cyclization of the appropriately substituted phenanthrylphenylethylenes provided 9-carbomethoxy-11-methoxyBgC (4) and 11-methoxyBgC (3). The former was converted by reduction, oxidation, one-carbon chain extension, and cyclization to 11-methoxy DB[a,l]P (7). Compounds 3 and 7 were converted by hydrolysis and oxidation to BgC-11,12-dione (10) and DB[a,l]P-11,12-dione (11), respectively. The diones are the precursors for the synthesis of the corresponding diol epoxides, anti- and syn-DB-[a,l] P-11,12-diol-13,14-epoxides 13 and 14 were prepared in 38{\%} and 55{\%} yields, respectively, from 11. Both diol epoxides had predominantly pseudodiequatorial hydroxyl groups, as seen in other sterically hindered diol epoxides.",
author = "Jacek Krzeminski and Lin, {Jyh ming} and Shantu Amin and Hecht, {Stephen S.}",
year = "1994",
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Synthesis of Fjord Region Diol Epoxides as Potential Ultimate Carcinogens of Dibenzo[a,l]pyrene. / Krzeminski, Jacek; Lin, Jyh ming; Amin, Shantu; Hecht, Stephen S.

In: Chemical research in toxicology, Vol. 7, No. 2, 01.03.1994, p. 125-129.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis of Fjord Region Diol Epoxides as Potential Ultimate Carcinogens of Dibenzo[a,l]pyrene

AU - Krzeminski, Jacek

AU - Lin, Jyh ming

AU - Amin, Shantu

AU - Hecht, Stephen S.

PY - 1994/3/1

Y1 - 1994/3/1

N2 - Dibenzo [a,l]pyrene (DB[a,l]P) is one of the strongest polynuclear aromatic hydrocarbon carcinogens known. This paper describes the synthesis of potential ultimate carcinogens of DB[a,l]P: anti- and syn-11,12-dihydroxy-13,14-epoxy-11,12,13,14-tetrahydroDB[a,l]P (DB-[a,l]P-11,12-diol-13,14-epoxides). The method employed is also useful for the preparation of key intermediates for the synthesis of 11,12-dihydroxy-13,14-epoxy-11,12,13,14-tetrahydrobenzo-[g]chrysene (BgC-11,12-diol-13,14-epoxide). Photochemical cyclization of the appropriately substituted phenanthrylphenylethylenes provided 9-carbomethoxy-11-methoxyBgC (4) and 11-methoxyBgC (3). The former was converted by reduction, oxidation, one-carbon chain extension, and cyclization to 11-methoxy DB[a,l]P (7). Compounds 3 and 7 were converted by hydrolysis and oxidation to BgC-11,12-dione (10) and DB[a,l]P-11,12-dione (11), respectively. The diones are the precursors for the synthesis of the corresponding diol epoxides, anti- and syn-DB-[a,l] P-11,12-diol-13,14-epoxides 13 and 14 were prepared in 38% and 55% yields, respectively, from 11. Both diol epoxides had predominantly pseudodiequatorial hydroxyl groups, as seen in other sterically hindered diol epoxides.

AB - Dibenzo [a,l]pyrene (DB[a,l]P) is one of the strongest polynuclear aromatic hydrocarbon carcinogens known. This paper describes the synthesis of potential ultimate carcinogens of DB[a,l]P: anti- and syn-11,12-dihydroxy-13,14-epoxy-11,12,13,14-tetrahydroDB[a,l]P (DB-[a,l]P-11,12-diol-13,14-epoxides). The method employed is also useful for the preparation of key intermediates for the synthesis of 11,12-dihydroxy-13,14-epoxy-11,12,13,14-tetrahydrobenzo-[g]chrysene (BgC-11,12-diol-13,14-epoxide). Photochemical cyclization of the appropriately substituted phenanthrylphenylethylenes provided 9-carbomethoxy-11-methoxyBgC (4) and 11-methoxyBgC (3). The former was converted by reduction, oxidation, one-carbon chain extension, and cyclization to 11-methoxy DB[a,l]P (7). Compounds 3 and 7 were converted by hydrolysis and oxidation to BgC-11,12-dione (10) and DB[a,l]P-11,12-dione (11), respectively. The diones are the precursors for the synthesis of the corresponding diol epoxides, anti- and syn-DB-[a,l] P-11,12-diol-13,14-epoxides 13 and 14 were prepared in 38% and 55% yields, respectively, from 11. Both diol epoxides had predominantly pseudodiequatorial hydroxyl groups, as seen in other sterically hindered diol epoxides.

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