--KEY--Chemistry 108B Exam #1-Winter 2015--KEY-The reaction of bromo acetophenone with sodium borohydride, NaBH4, was expected to give

halohydrin
1-phenyl-2-bromoethanol. However, the actual product isolated was phenyloxirane. Propose a mechanism and
a BRIEF theoretical justification to explain this experimental result.

:O :

:OH

H
H

NaBH4

Br

McMurry, problem 18.60

:O :

Br

Bromo acetophenone

1-Phenyl-2-bromoethanol
expected product: NOT formed

Phenyloxirane
actual product formed

The initial reduction product gives the halohydrin 1-phenyl-2-bromoethanol. However, since no
H3O(+) is present in the reaction mixture, the 1-phenyl-2-bromoethoxide intermediate formed
after initial reduction with NaBH4 can't be neutralized to the OH and instead undergoes an
intramolecular SN2 reaction to form the epoxide, phenyloxirane, that is the actual product isolated.
:O :

:O :
H

:O:

:H(-)
NaBH4

C
Br

Br

Bromo acetophenone

Phenyloxirane
actual product formed

1-phenyl-2-bromoethoxide

6.) The SN2 reaction of (dibromomethyl)benzene with NaOH yields benzaldehyde rather than the expected
:

(dihydroxymomethyl)benzene. Use a mechanism and your brilliant analytical skills to explain this experimental
result.

McMurry, problem 19.49

:OH(-)

H
C

Br

Br
(Dibromomethyl)benzene

Na(+)OH(-) , 25 C

H
Benzaldehyde
ONLY product formed

Mechs 4@
Expl 3@

OH
OH

(Dihydroxymomethyl)benzene
EXPECTED product; NOT formed

-H2O

:OH(-)

H
Gem-Diol
unstable intermediate

O:

H
H

Br

: :

: :

: :

OH

O
H

The (dibromomethyl)benzene undergoes two SN2 reactions with OH(-) to form a gem-diol
product. Gem-diols are unstable and rapidly undergo loss of water to form the corresponding
ketone or aldehyde. In this case, the aldehyde formed is benzaldehyde, the only product
isolated.