UNIVERSITY OF THE WEST INDIES - CAVE HILL SEMESTER 1, 2018-2019

CHEM2705 INTERMEDIATE ORGANIC CHEMISTRY Dr. J. BADENOCK

CARBANION CHEMISTRY AND C-C BOND FORMATION - TUTORIAL SHEET #8 ANSWERS

1. Circle all the acidic hydrogens (pKa <25) in the following molecules.

O O O O O
H CH3
i. ii. H C CH3 iii. CH3 iv. H3C
H3C CH3 3 O H3C H
H H H
CH3 H CH3
NO -hydrogens
2. Write resonance structures for the following anions.

O O O

i. CH2 CH2 CH2

O O O O O O
ii.

CO2Me CO2Me CO2Me

iii. N N N
C C

O O
CO2Me CO2Me
OMe OMe
N N N N
C C C

3. Describe experimental conditions that would be best suited for the efficient synthesis of the
following compounds.

I I I I O
CO2CH3
i. ii. Cl iii.
Br
O

xs. I2, 1. PBr3, Br2

Cl2, HCl
xs. NaOH 2. CH3OH

H H H H O
H CO2H

O Br
UNIVERSITY OF THE WEST INDIES - CAVE HILL SEMESTER 1, 2018-2019
CHEM2705 INTERMEDIATE ORGANIC CHEMISTRY Dr. J. BADENOCK

4. Explain using mechanisms why the following bromoketone forms different bicyclic compounds
under different reaction conditions.

O CH3O O N
O CH3
H
H Li+
LDA, THF NaOCH3, CH3OH,
o o
-78 C Br 25 C

O O O O
H
H H

Br Br Br Br
disubstituted alkene tetrasubstituted alkene
Kinetic enolate Thermodynamic enolate
Formed fastest with bulky base at lower To
More stable enolate formed at higher To with
smaller base.

5. The bicyclic ketone shown below does not undergo aldol self-condensation even though it
possesses two -hydrogen atoms. Explain.

O O

H H
X 1 mark
H

The first step of an aldol condensation is enolate formation. The ketone shown here does
not enolize because double bond at the bridgehead of a small bicyclic ring system are too
strained to form. Since the bicyclic ketone does not enolize, it doesn’t undergo aldol
condensation.

6. Show, giving reactants, reagents and conditions, how you would prepare each of the following
compounds using an Aldol condensation.

CHO CHO CHO

H 
 
O
i.    + H
H H
HO H H
NaOH, EtOH

O H O OH O O
  H
ii.   CH3 + H
H
H H
NaOH, EtOH

UNIVERSITY OF THE WEST INDIES - CAVE HILL SEMESTER 1, 2018-2019
CHEM2705 INTERMEDIATE ORGANIC CHEMISTRY Dr. J. BADENOCK

H
  OH
H H
iii. O
  H 
CHO CHO CHO
NaOH, EtOH

CH3 CH3 CH3
iv.
O O O
 
  H  O H
H HO  H H H

NaOH, EtOH


7. Give the likely products for each of the following reactions.

ClH Cl Cl
Cl HClHClHCl ClHCl
ClH Cl ClH ClH Cl Cl ClH
i. Cl Cl Cl LDA, THF Cl Cl Cl Cl
Cl H Cl + Cl H Cl
H then H , H2O
Cl Cl HCl Cl
Cl
O Cl
O
ii. 2 NaOH, H2O
H H

H
O OH O
H3C NaOH, H2O
iii. CHO H H
+ H
CH3 cannot dehydrate since H3C CH3
no more -hydrogens
O
O
CH3 NaOH, H2O CH3
iv. H
O 

O O

v. NaOH, H2O

O
O
O NaOH, H2O C C
vi. 2 Me CHO + H H
H3C CH3  Me
Me
UNIVERSITY OF THE WEST INDIES - CAVE HILL SEMESTER 1, 2018-2019
CHEM2705 INTERMEDIATE ORGANIC CHEMISTRY Dr. J. BADENOCK

O NaOH, EtOH
vii. O + O
H 

8. Formulate a detailed mechanism for each of the reactions shown below.

+
H
Br
O N + +
O
H , H2O
H H
i
H CH3 H

OH H2O H
O
N
H CH3 H H

+
H
HO N
H
HO NH
H CH3
H2O
H

H2O N H+
H
O N
H CH3 H2O
H
H

Br

N N N
H
H C H CH2 H
H2 H2O
ENAMINE
H2O
UNIVERSITY OF THE WEST INDIES - CAVE HILL SEMESTER 1, 2018-2019
CHEM2705 INTERMEDIATE ORGANIC CHEMISTRY Dr. J. BADENOCK
O
O O O
NaOH, EtOH Ph Ph
ii. +
Ph Ph
Ph Ph
H Ph Ph
OH

O O
Ph Ph
Ph Ph
Ph Ph
Ph
Ph OH
O O

O
O H OH
Ph Ph Ph Ph
Ph
Ph Ph
Ph OH
HO H O O

O
H
O Ph Ph
OH H
Ph
Ph
Ph Ph O Ph
Ph
H OH
HO O

OH
O O H O
Ph Ph Ph
Ph Ph Ph
Ph Ph Ph
Ph
HO O Ph O Ph O
UNIVERSITY OF THE WEST INDIES - CAVE HILL SEMESTER 1, 2018-2019
CHEM2705 INTERMEDIATE ORGANIC CHEMISTRY Dr. J. BADENOCK

HO O
O
H H
iii. O 1. NaOH, EtOH
H
2.  H3C CH3
H3C CH3

O O
O HO H
H

H3C CH3 H3C CH3

E1cB
MECHANISM

EtO H O O
1/2 O H HO H
H OH
H3C CH3 H3C CH3