(1) Predict the major product from each reaction. If you expect no reaction, indicate.
O
1)
(a)
O
N
H
OMe
2) CH2=CHCO2Me
then HCl/H2O
NH2
CN
(b)
1) NaNO2, HCl
2) CuCN, KCN
CH3
(c)
CH3
LDA
O
then PhCHO
O
(d)
(e)
OH O
Ph
O
LiMe2Cu
then
CH2=CHCH2Br
O
1) NaN3
Cl
O
HN
OMe
2) MeOH, heat
(f)
O
O
O
KOH, (CH3)2CHCHO
80° C
NH2
CH3I (excess)
(g)
then Ag2O, heat
NaOEt (0.9 eqivalents), heat
(h)
O
O
then CH3CH2I
(2) Which of these two compounds is more basic and why?
O
O
N
CH3
N
CH3
In the first compound, the lone pair on the nitrogen is tied up in resonancce with the carbonyl group
O
O
N
CH3
N
CH3
and is not as available for accepting a proton
(3) Fill in the compounds in the following roadmap (only show the major product for each step)
O
O
O
1) CH2=CHMgBr
2) LDA then PhCH2Br
Ph
CuI
O
3) HOCH2CH2OH,
O
Ph
Ph
TsOH, MgSO4
O
O
4) O3 then Me2S
O
O
5) Ph3P=CHOMe
O
6) HCl, H2O
Ph
O
O
Ph
O
OCH3
C10H20O2
(4) Explain the following observations
O
O
O
EtO
KOH
OEt
O
CO2Et
85%
O
O
KOH
EtO
CO2Et
OEt
O
0%
OH
O
CO2Et
O
CO2Et
KOH
CO2Et
retro-Claisen
no further reaction
(5) Using benzene and ethylacetoacetate, synthesize the following molecule. You may use any
inorganic reagents or organic reagents with 2 carbons or less.
O
CH3
CH3
F
CH3
1) HNO3, H2SO4
2) Ac2O, pyr.
CH3
CH3
NaNO2, HPF6
then 150° C
KOH
AcHN
AlCl3
AcHN
H2N
hot, conc.
F
CO2H
KMnO4
F
O
1) LAH
2) PBr3
CH3Cl
Br
ethylacetoacetate
NaOEt
F
CH3
F
EtO
(6) Give a detailed mechanism for the following reaction
NH2
NaNO2, HCl
N
N
Cl-
see your notes
O
1) NaOEt, MeI
2) KOH, heat
product
(7) Which compound has the most acidic hydrogen and why?
the anion from this molecule is aromatic
H
H
CO2Me
CO2Me
(8) Fill in the compounds in the following roadmap (only show the major product for each step)
Br
O
Mg then CuI
OMe
O
then
1) HNO3, H2SO4
2) H2, Pd-C
OMe
O
O
OMe
1) NaNO2
H2N
OMe
2) Cu2O, H2O
HO
O
1) NaH, EtBr
OH
2) KOH, heat
EtO
H
N
1) SOCl2
2) NaN3
EtO
3) 150° C, CH3NH2
(9) List the reagents (in order) needed to accomplish the following transformations
O
1) LDA, -78° C
2) PhCHO
O
OH
NHMe
O