Molecular Rearrangements. XI. The Deamination of 1,1-Diphenyl-2-amino-1-propanol¹

Abstract

Vol. 79 perchlorate ion is not nucleophilic, this imine probably reacts almost entirely by SnI in dilute perchloric acid. 1,2-Iminoethane probably reacts only by Sn2. The other imines would react by a combination of SnI and Sn2. The relative rates of these acid-catalyzed hydrations of imines can be accounted for on the basis of a transition from SnI to Sn2 mechanism as in the case of epoxides24 and the assumption that reaction is predominantly Sn2 at a primary carbon atom, a mixture of SnI and Sn2 at a secondary carbon atom and predominantly SnI at a tertiary carbon atom.

The mass spectra of some methyl norbornyl chlorides

“…The lifetime of an ion in the ion source of a mass spectrometer is long by comparison with the lifetime of an organic cation in solution. 16 Howe and Williams quote 1 to 5 psec for residence in the ion source and 15 p e c for travel from the source to collector slit for an ion of m/e 100 in the AEI MS-9 spectrometer at 8 kV accelerating voltage. '…”

EFFETS STÉRÉOÉLECTRONIQUES DANS LA DÉSAMINATION NITREUSE DES tert-BUTYL-4 AMINOMÉTHYL-1 CYCLOHEXANOLS cis ET trans

“…De cette fason, les migrations seraient contr6li.e~ par la conformation de moindre energie de la molecule. Cependant, Collins e t ses collaborateurs ont, dans la skrie des diaryl-propanolamines e t diaryl-propylamines, propose un ion carbonium classique comme intermediaire donnant directement naissance aux produits de la rCaction (18,23,24). Cette theorie, tout en kcartant les possibilites d'avoir des ions carboniums pontes et de l'assistance de la part de groupes voisins dans l'etape intermediaire de la rbaction, ne refute cependant pas 1'idCe de l'ion diazonium e t du mecanisme pull-push de Streitwieser (17)…”

“…On isole un solide blanc qui aprks lavage Q l'ether pour enlever les neutres donne 710 mg (67.8%) du melange des chlorhydrates des deux amino-alcools cis IIb e t trans IIa. Aprks deux recristallisations dans un melange mkthanol-Cther on isole 251 mg (23 Les pics correspondant aux 6poxydes cis VIII e t trans VII ont kt6 repi.rCs en ajoutant le mClange des epoxydes VIII e t VII prCparC plus haut en (1.21) au m6lange de ditsamination. 11 n'y a pas d'inconvknient Q ajouter le n~Clange des Cpoxydes cis e t trans, car il est peu rCsolu sur la colonne utilisbe.…”

Treasures old and new: what we can learn regarding the macrocyclic problem from past and present efforts in natural product total synthesis

“…On the one hand, the presence of the biaryl moiety in Haouamine suggested that Baran's synthesis could have been discussed aer Nicolaou's Diazonamide synthesis in which the installation of the biaryl was achieved by a single electron oxidation/reduction. On the other hand, Baran's solution to the problem of the strained biaryl moiety within Haouamine involved such an ingenious use of Diels Alder chemistry, that it seemed appropriate to discuss this innovation aer Schreiber's 91 exhilarating Diels Alder accomplishment. 90 Haouamine A is a structurally unique alkaloid.…”