03 de decembro de 2012
Mecanismos das Reacciéns Orgénicas: Proba Reacciéns Periciclicas
NOME Mote Cohucoc. Qc
1, Pyrolisis of compound 1 at 460 °C gave a diene whose \
(p.m) 6.06 (1H, dd, J = 10.3 and 12.1 Hz), 6.23 (1H, dd, |= 103 ana t+
1= 14.7 Hz) and 7.32 (1H, d,J = 12.1 Hz). Does this agree with the
this diene formed and why does it have that stereochemistry?
R spectrum included 6(H)
631 (1H, d,
re given, How is
DL 460°C, h
ee co ON SPI
AcO
SPh
2. Thioketones, with a C=S bond, are not usually stable. However, this thioketone is quite
stable and undergoes reaction with maleic anhydride to give the product shown. Comment
the mechanism of the reaction and the stereochemistry ofthe product.
9°
Crs “Op
°
3. This unsaturated alcohol (pent-1,7,9-trien-3-ol) is perfectly stable until it is oxidized
with Cr(VI}: it then immediately cyclizes to a single product. Suggest a structure for the
OH
ae oe om
FFTs OoE
4. Bromocyclooctatetraene rearranges to trans-B-bromostyrene. The rate of the
in gyargement is solvent dependent, the first order rate constant increasing from 107.04
in cyclohexane to 103 5 in acetonitrile at 80 °C. In the Presence of lithium iodide, the
Product is trans-B-iodostyrene, although trans-f-bromo styrene is unaffected by lithium
‘odide under the conditions of the reaction. Suggest a mechanism for this rearrangement,