Die photolyse konfigurations-isomerer cyclobutanon-derivate

Mechanism of the chlorination of anilines and related aromatic amines. Involvement of nitrenium ions

“…In view of the excellent pseudo-first-order rates obtained for9 and 10 in buffered ethanol, the observations for the unbuffered solvolyses indicated that a change of mechanism was occurring. Clearly, the solvolysis of 9 and 10 could be acid catalyzed, while the solvolysis of[5][6][7][8] was not sensitive to small amounts of acid. Orthochlorinated products were obtained from 9 and 10 in 99 and 96% yields, respectively, under the unbuffered conditions.…”

Photochemical ring expansion of cyclic ketones via cyclic oxacarbenes

“…Accounts of Chemical Research sion reactions occur in the case of monocyclic cyclobutanones, together with decarbonylation and cycloelimination reactions. These processes are illustrated by the photoconversion of cyclobutanone (12) itself to compounds 13-15 10 As in the case of 1, lactone formation can occur in the presence of air.9…”

“…28 and 32), fails to lead to ring expansion in the case of cyclohexanone. [10][11][12][13][14][15][16][17][18][19][20][21][22] O O 82 83…”

“…In the case of cyclobutanone (12), Turro and Southam9 have obtained evidence that the acetal 13 is derived from the oxacarbene 89 rather than the vinyl ether 90 by carrying out the irradiation in CH3OD, when they observed exclusive deuterium incorporation at C-2 as in 91.…”