Assignment 1

Question 1 (20 marks)

CHEM2021 Organic Chemistry:
a) Specify the configuration in each of the examples below, showing working.
Mechanisms and Biomolecules
i) Cl ii)
H
An assignment dealing with stereochemistry and mechanism
(4 marks)
Assignment due: 5:00 pm, Wednesday 15th September 2010
b) Name the following compound, including working to assign configuration.
Where to: Submission box in School of Chemistry Administration Area, Level 1, Dalton
Building (on your left as you come up the stairs). For enquiries, see Anne
O
Ayres.
Submission to someone or somewhere else will result in your assignment not Cl
being marked.

Worth: 40 Marks, 2.5% of total assessment. (4 marks)

Special notes: All assignments must be handwritten. c) Draw the outcome of the following mechanisms.
You must attempt the assignment allocated to you.
(see Assignment Allocation). i) H+ ii)
O O

Penalties: Assignments received after the due date will not be marked, nor will those O O
that have been word processed. Plagiarism will result in a mark of zero, as
OH O
will submitting an assignment without a completed plagiarism declaration or (2 marks)
completing an assignment other than the one allocated to you.
d) Draw mechanisms to explain the following processes.

i) ii) CCl3 CCl3

O NH O NH
Br + Br

(2 marks)

e) Using a mechanism, explain the following being sure to account for any selectivity observed.

Br2 OH Br

H2 O Br OH

major minor
(4 marks)

f) Using a mechanism, predict the outcome of the reaction below, being sure to account for any
selectivity observed.

H I

(4 marks)

Question 2 (20 marks) Assignment 2

a) Each of the following reactions might be explained using two mechanisms. Draw each of the Question 1 (20 marks)
possibilities and explain which is likely to be the actual mechanism. In each case, give at least two
pieces of experimental evidence that might be used to confirm the mechanism that is operating. a) Specify the configuration in each of the examples below, showing working.
(One of these may be stereochemistry, which is deliberately not specified in the cases below.)
i) ii)
i)
t-BuO-K+
Br NO2
(5 marks)
(4 marks)
ii)
b) Draw (2S,3R)-2-amino-3-hydroxybutanoic acid, including working to assign configuration.
Br MeOH O
(4 marks)
(5 marks)
c) Draw the outcome of the following mechanisms.
b) Identify the major product of each of the following reactions. Explain briefly your choice and
suggest the mechanism through which it might be formed. i) ii)
O O O
(Note: There is no need to draw out the mechanism in each case.)
N
i) O H
Br EtOH S
+ O Na SnBu3
heat
(3 marks)
(2 marks)
ii)
Br d) Draw mechanisms to explain the following processes.
NaCN

i) O O ii)
(3 marks) Ph C N O
N
Ph O
c) How would you suggest synthesising the molecule below using a Williamson ether synthesis?
Explain your choice. H H EtO2C CO2Et
E H E H EtO2C CO2Et

O (2 marks)

(4 marks) e) Using a mechanism, explain the following being sure to account for any selectivity observed.

Cl H OH
Crazy Bonus Question (up to 4 bonus marks, total can't pass 40). H3O+
Cl
Cl Cl
Explain why no reaction is observed in the case below.
all 4 stereoisomers
Cl (4 marks)
Cl Cl KOtBu
f) Using a mechanism, predict the outcome of the reaction below, being sure to account for any
heat selectivity observed.
Cl Cl
Cl H3O+

(4 marks)
Question 2 (20 marks) Assignment 3
a) Each of the following reactions might be explained using two mechanisms. Draw each of the Question 1 (20 marks)
possibilities and explain which is likely to be the actual mechanism. In each case, give at least two
pieces of experimental evidence that might be used to confirm the mechanism that is operating. a) Specify the configuration in each of the examples below, showing working.
(One of these may be stereochemistry, which is deliberately not specified in the cases below.)
i) i) H ii)
O
HO CO2H
H NaOH H Ts = S
OTs OH OH
O
(5 marks) (4 marks)

ii) b) Name the following compound, including working to assign configuration.

H2O
Br

(4 marks)
(5 marks)
c) Draw the outcome of the following mechanisms.
b) Identify the major product of each of the following reactions. Explain briefly your choice and
suggest the mechanism through which it might be formed. O
i) ii) O
(Note: There is no need to draw out the mechanism in each case.)
i) EtO OEt
NaSEt
Br NH2 O
(3 marks) B H

ii) (2 marks)
Br
+ OH d) Draw mechanisms to explain the following processes.
(3 marks)
i) ii) OH O
c) How would you suggest synthesising the molecule below using a Williamson ether synthesis? I
Explain your choice. + I I

(2 marks)

O e) Using a mechanism, explain the following being sure to account for any selectivity observed.
(The mechanism for the conversion of triakylborane to alcohol is not required.)

(4 marks) i) BH3
HO OH
+
ii) OH-, H2O2, H2O
Crazy Bonus Question (up to 4 bonus marks, total can't pass 40). major minor
(4 marks)
What is the major product in the following reaction?

Br Br
f) Using a mechanism, predict the outcome of the reaction below, being sure to account for any
excess KOtBu selectivity observed.
Br2

(4 marks)

Question 2 (20 marks) Assignment 4

a) Each of the following reactions might be explained using two mechanisms. Draw each of the Question 1 (20 marks)
possibilities and explain which is likely to be the actual mechanism. In each case, give at least two
pieces of experimental evidence that might be used to confirm the mechanism that is operating. a) Specify the configuration in each of the examples below, showing working.
(One of these may be stereochemistry, which is deliberately not specified in the cases below.)
i) i) CN ii)
NaN3 CO2H
H2N CO2H

Br N3
(4 marks)
(5 marks)
b) Draw (2S,4Z,7R)-7-aminonon-4-en-2-ol, including working to assign configuration.
ii)
H
t-BuO-K+ (4 marks)

Cl c) Draw the outcome of the following mechanisms.

(5 marks)
i) ii) O
b) Identify the major product of each of the following reactions. Explain briefly your choice and
suggest the mechanism through which it might be formed. O
(Note: There is no need to draw out the mechanism in each case.) O
i) Cl

Br O O
low temp
+ O
(3 marks) (2 marks)

d) Draw mechanisms to explain the following processes.

ii)
CH3COOH
i) ii)
Br R R O O
(3 marks) O O
N N
O H O H
O O
c) How would you suggest synthesising the molecule below using a Williamson ether synthesis?
Explain your choice.
O
(2 marks)

e) Using a mechanism, explain the following being sure to account for any selectivity observed.

Br
HBr
(4 marks)

Crazy Bonus Question (up to 4 bonus marks, total can't pass 40). (4 marks)
What is the major product in the following reaction? f) Using a mechanism, predict the outcome of the reaction below, being sure to account for any
selectivity observed.
i) H2O
i) H2 / Lindlar's Cat
Br Br
ii) Na ii) Br2
(4 marks)
Question 2 (20 marks) Assignment 5
a) Each of the following reactions might be explained using two mechanisms. Draw each of the Question 1 (20 marks)
possibilities and explain which is likely to be the actual mechanism. In each case, give at least two
pieces of experimental evidence that might be used to confirm the mechanism that is operating. a) Specify the configuration in each of the examples below, showing working.
(One of these may be stereochemistry, which is deliberately not specified in the cases below.)
i) i) ii) Br Cl
H
MeOH
I F
Cl
(5 marks)
(4 marks)
ii)
I O
b) Name the following compound, including working to assign configuration.
EtOH

CO2H
(5 marks)

b) Identify the major product of each of the following reactions. Explain briefly your choice and (4 marks)
suggest the mechanism through which it might be formed.
(Note: There is no need to draw out the mechanism in each case.) c) Draw the outcome of the following mechanisms.
i)
i) ii) Ph
I O OH
+ O K O
(3 marks) O H

ii) (2 marks)
Ph Cl H 2O
d) Draw mechanisms to explain the following processes.
THF
(3 marks) i) ii)
O O
c) How would you suggest synthesising the molecule below using a Williamson ether synthesis?
+ H3C O
Explain your choice. O H
O

(4 marks)
(2 marks)
Crazy Bonus Question (up to 4 bonus marks, total can't pass 40).
e) Using a mechanism, explain the following being sure to account for any selectivity observed.
Suggest a mechanism for this reaction.
HBr
NH Br2 Br Br
N
major
(4 marks)
Br
f) Using a mechanism, predict the outcome of the reaction below, being sure to account for any
selectivity observed.
Cl2
H2O
(4 marks)

Question 2 (20 marks)

a) Each of the following reactions might be explained using two mechanisms. Draw each of the
possibilities and explain which is likely to be the actual mechanism. In each case, give at least two
pieces of experimental evidence that might be used to confirm the mechanism that is operating.
(One of these may be stereochemistry, which is deliberately not specified in the cases below.)
i)
CH3S-
H Cl H S
H H
(5 marks)

ii)
Br
t-BuO-K+

(5 marks)

b) Identify the major product of each of the following reactions. Explain briefly your choice and
suggest the mechanism through which it might be formed.
(Note: There is no need to draw out the mechanism in each case.)
i)
Br KOH

(3 marks)

ii)
Br KOH

heat
(3 marks)

c) How would you suggest synthesising the molecule below using a Williamson ether synthesis?
Explain your choice.

O
(4 marks)

Crazy Bonus Question (up to 4 bonus marks, total can't pass 40).

Outline the mechanism of these reactions and identify the intermediate and product.

O
CH3I NaOH
NMe2 A B