Radical cations of benzo[α]pyrene and 6-substituted derivatives: reaction with nucleophiles and DNA

D. E. Stack Eppley Institute for Research in Cancer, University of Nebraska Medical Center, 600 South 42nd Street, Omaha, NE, 68198-6805, USA

P. Cremonesi Eppley Institute for Research in Cancer, University of Nebraska Medical Center, 600 South 42nd Street, Omaha, NE, 68198-6805, USA

A. Hanson Eppley Institute for Research in Cancer, University of Nebraska Medical Center, 600 South 42nd Street, Omaha, NE, 68198-6805, USA

E. G. Rogan Eppley Institute for Research in Cancer, University of Nebraska Medical Center, 600 South 42nd Street, Omaha, NE, 68198-6805, USA

E. L. Cavalieri Eppley Institute for Research in Cancer, University of Nebraska Medical Center, 600 South 42nd Street, Omaha, NE, 68198-6805, USA

Abstract

1. Oxidation of benzo[α]pyrene (BP) by I₂ in the presence of AgClO₄ in benzene generates the BP⁺ ClO₄⁻ · AgI complex. This same method was used to produce radical cations from 6-FBP, 6-ClBP, 6-BrBP and 6-CH₃BP.

2. Reaction of the BP, 6-FBP, 6-ClBP and 6-BrBP radical cation perchlorates with H₂O produced BP 1,6-, 3,6- and 6,12- dione, whereas 6-CH₃BP^.+ ClO₄⁻ · AgI yielded 6-CH₂OHBP.

3. When BP^.+ ClO₄⁻ · AgI and 6-FBP^.+ ClO₄⁻ · AgI were reacted with NaOAc in H₂O/CH₃CN (9:1), 6-OAcBP was formed, in addition to the quinones. In the case of 6-ClBP^.+ ClO₄⁻ · AgI, a small amount of 1-OAc-6-ClBP and 3-OAc-6-ClBP was formed in addition to the diones, whereas for 6-BrBP and 6-CH₃BP the reaction products were BP diones and 6-CH₂OHBP respectively.

4. These results confirm the localization of charge in the BP^.+ at C-6, followed by C-1 and C-3.

5. The reaction of BP with NOBF₄ in CH₂Cl₂ produced BP^.+ BF₄⁻, radical cation free of complexation with inorganic salts.

6. Reaction of BP^.+ BF₄ with DNA produced the depurinating adducts BP-6-C8Gua, BP-6-C8dGua and BP-6-N7Gua.

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Radical cations of benzo[α]pyrene and 6-substituted derivatives: reaction with nucleophiles and DNA

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Radical cations of benzo[α]pyrene and 6-substituted derivatives: reaction with nucleophiles and DNA

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