Regiochemistry of the photostimulated reaction of the phthalimide anion with 1-iodoadamantane and tert-butylmercury chloride by the S(RN)1 mechanism

Manuel Bajo Maquieira; Alicia B Peñéñory; Roberto A Rossi

doi:10.1021/jo010756w

Regiochemistry of the photostimulated reaction of the phthalimide anion with 1-iodoadamantane and tert-butylmercury chloride by the S(RN)1 mechanism

J Org Chem. 2002 Feb 8;67(3):1012-5. doi: 10.1021/jo010756w.

Authors

Manuel Bajo Maquieira¹, Alicia B Peñéñory, Roberto A Rossi

Affiliation

¹ INFIQC, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, 5000 Córdoba, Argentina.

PMID: 11856054
DOI: 10.1021/jo010756w

Abstract

The photostimulated reaction of the phthalimide anion (1) with 1-iodoadamantane (2) gave 3-(1-adamantyl) phthalimide (3) (12%) and 4-(1-adamantyl) phthalimide (4) (45%), together with the reduction product adamantane (AdH) (21%). The lack of reaction in the dark and inhibition of the photoinduced reaction by p-dinitrobenzene, 1,4-cyclohexadiene, and di-tert-butylnitroxide indicated that 1 reacts with 2 by an S(RN)1 mechanism. Formation of products 3 and 4 occurs with distonic radical anions as intermediates. The photoinduced reaction of anion 1 with tert-butylmercury chloride (10) affords 4-tert-butylphthalimide (11) as a unique product. By competition experiments toward 1, 1-iodoadamantane was found to be ca. 10 times more reactive than tert-butylmercury chloride.