O + O

O 1) NaOEt/EtOH ∆, H3O
CO2Et
CO2Et
2) -CO2
Br
-EtOH

PBr3, Br2 Br NH3 Br

O O O

OH Br NH2

O O 1) Me2CuLi O
SOCl2
OH 2) H3O+
Cl CH3

H O
N
O + N 1) H
, H CN
H H +
-H2O 2) ∆, H3O
COOH

1) NaOH, I2 1) NaH
O
2) H3O+ 2) CH3I
OH OCH3

3) BH3

O
O O O
+
OEt 1) NaOEt, EtOH ∆, H3O
OEt OEt
2) H3O
+ -CO2
O -EtOH
List all the ways you can think of to make the following compounds.

O
1. Mg, ether
Br
OR H3O+ (or HO-), heat 2. CO2
3. H3O+
O 1. Mg, ether
CN H3O+ (or HO-), heat
OH 2. H2CO (formaldehyde)
3. H3O+
R
OH Br
Jones'
KMnO4, H3O+ HO- (SN2)

Br
KCN
Cl OH
SOCl2
CN
2 NH3 O
O
(see above)
NH2
SOCl2, heat
O

Draw a detailed mechanism for the Claisen condensation between two molecules of ethyl
phenylacetate. Clearly indicate which steps are reversible and which are essentially
irreversible.

Step 1:
OCH2CH3
OEt O
- EtOH O
H OCH2CH3
OCH2CH3
OCH2CH3
O OCH2CH3
O
O

OEt
O O
- EtOH O O
H
OCH2CH3
essentially OCH2CH3
irreversible

H3O+
Step 2

O O

OCH2CH3
 Draw detailed mechanisms for the following reactions:

O
CO2Et 1) NaOEt/EtOH
2
CO2Et 2) H3O+, heat
O
Part 1: CO2Et O O
EtO OEt
CO2Et -EtOH EtO2C OEt

H CO2Et EtO2C OEt EtO CO2Et - EtO

O O
O
CO2Et EtO2C OEt
EtO2C
O CO2Et
O OEt
O
O OEt EtO2C
EtO EtO2C
O
OEt OEt
O - EtO O
O CO2Et
O O
Part 2:
H H
O O OH
O O EtO O
EtO EtO O2H
H2O OH2
OEt OEt
O H2O O O OEt
O O OH
H H
H OH
H2O H EtO O
O
O O HO OH
O
O HO O OEt
OH O H
OH OH H
H O O -2 EtOH
HO -2 CO2 O
-2 H3O O
O H2O H
O tautomerization
 O

O O
NaOEt/EtOH - HO
O

O O
H OH
O
EtO
O
O O

O
O O
O
EtO H
H
EtO
O

O O O O
O
O
H
HO O
O EtO EtO
Draw a detailed mechanism for the following reaction:

O MgBr
1) BrMg
OH
O OH
+
2) H3O
H OH2
MgBr
BrMg

MgBr
O H OH2
O

MgBr MgBr
MgBr O
BrMg O
O
O MgBr

Propose efficient synthetic routes for the following transformations

O
Br Br
?
O O

OEt

1) Br2, CH3COOH
NaOEt 2) pyridine
EtOH

O
O O
H3O+, heat
OEt
 Br ? CN

Mg, ether
SOCl2, heat

MgBr CONH2
CO2H COCl
1)CO2 2 NH3
+ SOCl2
2) H3O

Treatment of the tertiary halide directly with

-
CN will lead to complications with elimination.
O

Br2/FeBr3 ? (H3C)2N 2 equ. (CH3)2NH

Cl NO2
O
CH3Cl/AlCl3
Cl

Cl NO2
HNO3/H2SO4
O SOCl2
Br KMnO4, heat
Cl2/FeCl3 HO

NO2 Cl NO2 Cl NO2

1) Mg, ether
HNO3/H2SO4
2) CO2
Br Br
3) H3O+

NO2 Cl NO2
Cl2/FeCl3