- Deamination Reactions. 35. Decomposition of 5-Norbornene-2-diazonium Ions. Derivatives of Bicyclohept-2-ene
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Photolysis of 5-norbornen-2-one tosylhydrazone (4) in aqueous sodium hydroxide afforded 4percent of 3-norpinen-2-ol (3) in addition to 5-norbornen-2-ol (5, 10percent) and nortricyclanol (6, 86percent). 3 arises from 5-norbornene-2endo-diazonium ions (2) as shown by the nitrous acid deamination of the epimeric amines 1 and 7. 3-Norpinen-2-one (12) was isolated by oxidation of the deamination products followed by preparative g.l.c. 3 and 12 were synthesized independently from norpinan-2-one (9) via sulfenylation and sulfoxide pyrolysis.The norbornene -> norpinene rearrangement is slightly enhanced by 1-OCH3.The deamination of 1-methoxy-5-norbornen-2endo-amine (14) produced 10percent of 12, as compared to 5.6percent of 3 from 1.
- Kirmse, Wolfgang,Knoepfel, Norbert,Loosen, Karin,Siegfried, Rainer,Wroblowsky, Heinz-Juergen
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p. 1187 - 1191
(2007/10/02)
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- Protonated cyclopropanes in α-aminoketone deamination
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Deamination of 2-amino-4,4-dideuterio-6,6-dimethylcyclohexanone, 2-exo-amino- and 2-endo-amino-norbornane-3-one, 2-diazo-norbornan-3-one, 2-exo-amino-5,6-exo-dideuterionorbornan-3-one and the corresponding 5,6-endo-dideuterio isomer has been studied.The nature of the products, the deuterium location in them, and the high retention of steric identity in the carbocations are interpreted in terms of ?-bond participation leading to corner- and edge-protonated cyclopropanes as reaction intermediates.Results with other destabilized carbocations are correlated.
- Edwards, Oliver E.,Dixon, John,Elder, John W.,Kolt, Ralph J.,Lesage, Maurice
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p. 2096 - 2115
(2007/10/02)
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