Solution Found!
The existence of the NIH shift was established by
Chapter 11, Problem 32P(choose chapter or problem)
The existence of the \(\mathrm{NIH}\) shift was established by determining the major product obtained from
rearrangement of the following arene oxide, in which a hydrogen has been replaced by a deuterium.
a. What would be the major product if the \(\mathrm{NIH}\) shift occurs? (Hint: A \(\mathrm{C} ━ \mathrm{H}\) bond is easier to break than a \(\mathrm{C} ━ \mathrm{D}\) bond.)
b. What would be the major product if the carbocation forms phenol by losing a proton, rather
than by going through the \(\mathrm{NIH}\) shift?
Equation Transcription:
NIH
C ━ H
C ━ D
Text Transcription:
NIH
C ━ H
C ━ D
Questions & Answers
QUESTION:
The existence of the \(\mathrm{NIH}\) shift was established by determining the major product obtained from
rearrangement of the following arene oxide, in which a hydrogen has been replaced by a deuterium.
a. What would be the major product if the \(\mathrm{NIH}\) shift occurs? (Hint: A \(\mathrm{C} ━ \mathrm{H}\) bond is easier to break than a \(\mathrm{C} ━ \mathrm{D}\) bond.)
b. What would be the major product if the carbocation forms phenol by losing a proton, rather
than by going through the \(\mathrm{NIH}\) shift?
Equation Transcription:
NIH
C ━ H
C ━ D
Text Transcription:
NIH
C ━ H
C ━ D
ANSWER:Solution 32P
(a)
Protonation of the epoxide gives an oxonium ion and then bond between carbon and oxygen breaks to form a carbocation. Then 1,2-hydride shift occurs and next the base abstracts the proton and forms the major product. Thus, the reaction is shown as follows: