RuO4-mediated oxidation of N-benzylated tertiary amines. 3. Behavior of 1,4-dibenzylpiperazine and its oxygenated derivatives

• Autorzy: Horia Petride , Constantin Drăghici , Cristina Florea , Aurica Petride
• Języki publikacji: EN

Abstrakty

EN

1,4-Dibenzylpiperazine (1),-2-piperazinone (7),-2,6-piperazinedione (9), and 1-benzoyl-4-benzylpiperazine (30) were oxidized by RuO4 (generated in situ) by attack at their endocyclic and exocyclic (i.e., benzylic) aminic N-α-C-H bonds to afford various oxygenated derivatives, including acyclic diformamides, benzaldehyde, and benzoic acid. The reaction outcome was complicated by (i) the hydrolysis of diformamides, occurred during the work-up, and (ii) the reaction of benzaldehyde with the hydrolysis-derived amines giving imidazolidines and/or Schiff bases. Benzoic acid resulted from benzaldehyde only. Compounds 7, 30, and 1-benzylpiperazine, but not 9, were transiently formed during the oxidation of 1. In the same reaction conditions, 1,4-dibenzyl-2,3-(or 2,5)-piperazinedione, 1,4-dibenzyl-2,3,6-piperazinetrione, 4-benzyol-1-benzyl-2-piperazinone, and 1,4-dibenzoylpiperazine were inert. The proposed oxidation mechanism involves the formation of endocyclic and exocyclic iminium cations, as well as of cyclic enamines. The latter intermediates probably result by base-induced deprotonation of the iminium cations, provided an N +−β-proton is available. In the case of 1, the cations were trapped with NaCN as the corresponding α-aminonitriles. The statistically corrected regioselectivity (endocyclic/exocyclic) of the RuO4-induced oxidation reaction of 1, 7, and 30 was 1.2–1.3.

Słowa kluczowe

EN

Oxidation; ruthenium tetraoxide; amines; iminium cations; regioselectivity

• Czasopismo: Open Chemistry
• Rocznik: 2006
• Tom: 4
• Numer: 4
• Strony: 674-694

Daty

wydano

2006-12-01

online

2006-12-01

Twórcy

autor

Horia Petride

• “Costin D. Nenitzescu” Center of Organic Chemistry, 050461, Bucharest, P.O. 35, Box 108, Romania,

autor

Constantin Drăghici

• “Costin D. Nenitzescu” Center of Organic Chemistry, 050461, Bucharest, P.O. 35, Box 108, Romania

autor

Cristina Florea

• “Costin D. Nenitzescu” Center of Organic Chemistry, 050461, Bucharest, P.O. 35, Box 108, Romania

autor

Aurica Petride

• “Costin D. Nenitzescu” Center of Organic Chemistry, 050461, Bucharest, P.O. 35, Box 108, Romania

Bibliografia

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Identyfikatory

DOI

10.2478/s11532-006-0039-8