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14 For the preparation of N-chlorinated amines see: J. Quick and R. Oterson,
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15 CAUTION: twice during this research project we witnessed the violent
decomposition of N-chloro pyrrolidine 2b with generation of heat if kept
neat at a temperature higher than 10 °C. In one instance, a sealed vial of
N-chloro pyrrolidine 2b exploded once removed from the freezer. N-
chloro piperidine 2a is less reactive and more stable. Extreme attention
should be paid when handling N-chlorinated amines and during their
preparation warming should be absolutely avoided.
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17 When compound 6a was treated with a large excess of piperidine, it gave
in full conversion and moderate isolated yield the corresponding aminated
compound 5a, possibly via an SN2 reaction pathway.
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19 This experiment excludes the α-aminated compounds 5a–c forming
exclusively via an SN2 mechanism on the corresponding chlorinated
adducts (ref. 17), rather suggesting that two independent reaction path-
ways give rise to the formation of adducts 5 and 6.
20 W. Adam, M. Ahrweiler, K. Paulini, H. U. Reißig and V. Vörckel, Chem.
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base-mediated quasi-Favorskii rearrangement of the chlorocarbonyl inter-
mediate 6, as suggested by one of the referees.
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12 N-chloro amines have successfully been exploited by the research group
of Jarvo, Miura and others for the direct amination of aromatic and het-
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