Hku Organic Chemistry 2 Final Exams

THE DIVERSITY OF HONG KONG
DEPARTMENT OF CHEMISTRY
CHEM3441B Organic Chemistry II

2:30 pm - 5 :30 pm
May 23, 2016 (Monday)
Only approved calculators as announced by the Examinations Secreta1y can be used in this examination. It is
candidates' responsibility to ensure that their calculator operates satisfactorily. and candidates must record the
name and type of the calculator used on the front page ofthe examination script.
Answer ALL questions in Section A in RED answer book. (Total 30 marks)

Question 1 ( 16 marks)
Answer ALL questions in Section Bin BLUE answer book. (Total 70 marks)
Question 3 (24 marks)
Page 1of8
Section A (Total 30 marks)

Answer ALL questions in this section in the RED answer book.
1.
(a) Describe what type of energy excitation of molecules can be caused by the
absorption of IR and UV-Vis, and NMR, respectively.
(3 marks)
(b) In the IR spectrum of compound A, there is an absorption band of C=C
stretching with intermediate intensity, while in the IR spectrum of compound B,
the intensity of absorption band of C=C stretching is very weak. Explain the
reason for such difference.
(2 marks)
(c) The UV -Vis spectrum A shows an absorption maxima at 228 nm, while
spectrum B shows an absorption maxima at 296 nm. Identify which spectrum
belongs to C and which belongs to D, and explain your answer.
~~
c
D
(2 marks)
(d) Assume that chemically equivalent protons show identical signals while
chemically non-equivalent ones show different signals. For the following
1
molecules E to H, how many sets of signals should be observed in their HNMR spectra? Label all protons in each molecule with numbers, so that the
protons that give the same NMR signals are labeled with the same number, and
the protons that give different signals are labeled with different numbers.
H 3 C~CI
Cl__J\CHo
or;r
~N
ll.)
N
H
(6 marks)
Page 2 of 8
(e) For the compound shown below, determine the structures of the ions indicated
by the m/z values. Draw a fragmentation mechanism that accounts for the
formation of the fragmentation ions. Fragmentation ion at m/z = 43 (base peak
in spectrum), 57 and 58.
m.w.
=100
(3 marks)
(a) Please analyze the following 1H-NMR spectrum by assigning all the signals to
the corresponding protons in the given structure. Explain their splitting
patterns.
2.
[" --------------- -- -
ya~
expansion
expansion
_________ JL_!L_ _ _____
,___ll l_
ln_t!!gral
1.0~2_ _
--
--expan-s-ionl
I
expansion
.1l1J_ __
--- - ---,1,0~=0-~-----------,-- ---- -----.-- _1,23 ___

5
4
3
PPM
: :, _______
~_ _ _6_ . ~5___
2
1
'_ i
------
(5 marks)
Page 3 of 8
(b) Based on the following spectroscopic data of an unknown compound with

molecular formula C9Hs04, (i) determine the chemical structure of this
compound; (ii) assign all the signals in the IH-NMR spectrum; (iii) assign the
two absorption bands in the IR spectrum at 1766 cm-I and 1685 cm-I, explain
your answer.
IR Specinlm
1766
(K8r.d!r>(;)
4000
3000
'"'"
1200
2000
1 1600
V (cm )
100
Mass Spectrum
138
eo
60
'.i
800
43
Arn.:t;x 235nrn (Jog 10 s 4.tl
A.~nu~ .2.65 hm (log 10 c 3,0 i
40
""'
20
UV Spectrum
!!fll~'e"nl
ii
40
; '91harml
120
80
160
200
24-0
200
mle
1:J.c
NMR Spec1rum
'
(tC:to MHz. COCl 1 s::dub:m)
DEPT
pto:lo!I. de.::aupled
200
'H
CH?. CH~t CHt
4'1>:1
11
II
II
160
120
80
40
-0 (ppm)
NMRSpooirum
{400 MHz, .COCI ~ Sl)lution)
:;f.'lllCh~rige~
__.....____
11.tO
10.{)
iMS
L..L-......~_._--'~-'----''----'-~'----'-~'----'-~'---'-~'--_._~~-'-~..___,_~....___,__
5
4
8
7
6
3
2
0
10
9
o(ppml
(9 marks)
Page 4 of8
Section B (Total 70 marks)

Answer ALL questions in this section in the BLUE answer book.
3.
Provide the missing reagents, reaction conditions or structures of the major

products (denoted by the letters I to D for each of the following transformations.
EtOH
(a)
HOAc
J.
(b)
--=----
~OH ~~HOL
(c)
0
11
(d)
(e)
H3C~OEt
~OEt
i) NaOEt, EtOH
0
Br2 (excess)
CH3C02H
I
(24 marks)
Page 5 of 8
4.
(a) Benzyne is a highly reactive molecule that 1s produced as a short-lived

intermediate in certain organic reactions.
benzyne
i) Would you expect benzyne to be aromatic? Explain your answer.

ii) Why is benzyne so reactive?
iii) Show one reaction that involves a benzyne intermediate.
(5 marks)
(b) Arrange the following compounds in order of increasing acidity. Explain your
answer.
6'H QH 'H SOH

//
OH
CN
Y.
i::
(5 marks)
(c) Compound AA is converted to compound BB on treatment with sodium

ethoxide in ethanol; however, no reaction occurs when compound CC is
subjected to the same conditions. Provide an explanation for this observation.
cO
H
cO
BB
~
~
NOE<, EK>H
NaOEt, EtOH
No reaction
cc
(4 marks)
Page 6 of 8
5.
Propose a reasonable mechanism for each of the following transformations. Show

clearly the structures of all intermediates and electron flow.
(a)
(b)
CH2(C02Et)z
NaOEt, EtOH
H,C~N-CH,
(c)
CH,OH
(d)
~
0
O
+ NaOCH3
OCH3
+ NaCl
~
(16 marks)
Page 7of8
6.
Provide a synthetic route for each of the target molecules below, starting from the
given starting materials. More than one step may be necessary. Use any readily
available substrates, reagents and solvents.
(a)
HzN-O-C02H
from
(a sunscreen agent)
(b)
from
(c)
(d)
from
OH
from
OH
H3C~CH3
(16 marks)
-END OF PAPER-
Page 8 ofS

CHEM3441C Organic Chemistry II

2:30 pm - 5:30 pm
Only approved calculators as announced by the Examinations Secretmy can be used in this examination. It is
candidates' responsibility to ensure that their calculator operates satisfactorily, and candidates must record the
name and type of the calculator used on the front page of the examination script.
Answer ALL questions. (Total 100 marks)

Page 1of6

1.

products (denoted by the letters A to M) for each of the following transformations.
Show the stereochemistry where necessary.
(a)
N -N,,
II
N
H N/-'--N/
2
EtOH
HOAc
(b)
-<-o-<02H_L -<-o-<N
OH
(c)
_!:L.. - < - o - < H O __!.....
(PhCH 2)zCuli
(d)
(e)
~OE!
i) NaOEt, EtOH
Br2 (excess)
CH3C02H
Page 2 of6
(f)
OH
(26 marks)
2.
(a)
Benzyne is a highly reactive molecule that is produced as a short-lived

intermediate in certain organic reactions.
benzyne
(i)
Would you expect benzyne to be aromatic? Explain your answer.
(ii) Why is benzyne so reactive?
(iii) Show one reaction that involves a benzyne intermediate.
(6 marks)
(b)
Arrange the following compounds in order of increasing acidity. Explain

your answer.
(6 marks)
(c)
Write a reasonable mechanism for the following transformation.
i) excess MeMgBr, THF

ii) H30+
(4 marks)
Page 3 of 6
(d)
Each of the following reactions does not provide a satisfactory yield of the
desired product.
(i)
(ii)
Suggest why the reaction fails;

Suggest how the reagents should be changed or conditions modified to
give a good yield of the desired product from the san1e starting
material.
i) CH3MgBr
i) LiAIH 4
ii) H30+
ii) H30+
(6 marks)
(e)
Compound R is converted to compound . on treatment with sodium

ethoxide in ethanol; however, no reaction occurs when compound I is
subjected to the same conditions. Provide an explanation for this
observation.
d:)
H
cO
..
NeOE" EK>H
NaOEt, EtOH
No reaction
I
(4 marks)
Page 4 of 6
3.

(a)
(b)
(o"f o
Hz1so
ulH
HCI
CH2(C02Et)z
NaOEt, EtOH
(c)
(d)
(e)
~
0
0
+ NaOCH3
OCH3
v>6
:::::.._
+NaCl
HOAc
0- N
H3C-10-CH3
(f)
(24 marks)
Page 5 of 6
4.
(a)
from
o-CH3
(a sunscreen agent)
(b)
from
(c)
from
OH
(d)
from
OH
H3C~CH3
(e)
(f)
H 3 C~CN
from
(24 marks)
- END OF PAPER-
Page 6 of 6

CHEM3441 Organic Chemistry II

December 23, 2015 (Wednesday)
9:30 am - 12:30 pm
Only approved calculators as announced by the Examinations Secretary can be used in this examination. It is
name and type of the calculator used on the front page of the exa1nination script.

Question I (26 marks)
Question 4 (IO marks)
Page 1 of7

1.

(a)
~
Ph)!__N_)
(b)
CCl 4 , reflux
NC~N~CN
HCHO, NaCNBH 3
MeOH,MeCN
COCI
(c)
Ph~
(d)
~Br
(e)
E
THF, -50 C to rt
toluene, -78 C
(f)
~
0
Page 2 of7
(g)
(h)
uYPh
.!::!.
UCN
~o
NaOH
(i)
~~
_1_)_ex_c_es_s_M_e_I_ _,..
2) Ag 20, H20, heat
i) KOH
G)
0
2 [)-cHO
(k)
Meo-0--0-Me
JS
ii) H3o
S03
(26marks)
2.
(a)
The mechanism of the following transformation (~ to Q) has been studied by

labeling one of the oxygen atoms in~. as shown below, with 18 0 isotope. Suggest
two possible mechanisms for this transformation, and predict the corresponding
oxygen (a: and /J) isotope labeling patterns of the products Q, respectively.
Meo
BOH
~O~-/; CHO
MeoAf
OMe
Na OH
li
(6 marks)
Page 3
of7
(b)
For the following two reactions,
r.
r.
i) Give the structures of major products and Q.

ii) Explain the following observations: is much more soluble in aqueous
sodium hydroxide than Q, but it is much less volatile than Q.
~
~
~OH
vv
(c)
(6 marks)
For each pair of compounds below, predict which compound is the stronger
acid, and give your explanation.
(i)
(ii)
0
OH
OH
N02
OMe
.!.!.
(iii)
H3C~CH3
H3CO~OCH3
Y.
(iv)
(12 marks)
Page 4 of7
3.

0
(a)
EtO)lOEt , NaH
rYMe
0 C to reflux
llAo.,.lo
llAOH
(b)
OMe
MeO
OMe
Meo
NaNH2
f"
,..__
(c)
C02Et
<0
Br
CHO
(d)
NH3, -78 C
EtO~OEt
OH
~Cl
HO
OMe
,.::;
C02Et
0
, benzene, reflux
then, HCI, H20, reflux
,.::;
(f)
(e)
OMe
i) NaOEt, EtOH
ii)
Ll
KCN, 18-crown-6
cone. HCI
MeCN, reflux
H20
'QH
0
(24marks)
Page 5 of7
4.
Each of the following reactions does not provide a satisfactory yield of the desired
product.
(i) Suggest why the reaction fails;
(ii) Suggest how the reagents should be changed or conditions modified to
give a good yield of the desired product from the same starting material.
(a)
1) LDA, THF, -78 C
2) CH3CH2I, THF, 0 C
(b)
(10 marks)
Page 6 of7
5.
(a)
(b)
from
CH3
OH
from
OH
DBr
(YCH3
(c)
from
HO
HO
(d)
from
(16 marks)
- END OF PAPER-
Page 7 of7

CHEM2403 Intermediate Organic Chemistry

9:30 am - 12:30 pm
May 20, 2015 (Wednesday)
Only approved calculators as announced by the Exaniinations Secretary can be used in this examination. It is
candidates' responsibility to ensure that their calculator operates satisj'actorily, and candidates niust record the
na1ne and type of the calculator used on the front page of the exaniination script.

Page 1of7
1.

Show the stereochemistry where necessary.
(a)
)Csr
(b)
(c)
(d)
~
~cl
+ Br2
1) LDNTHF, -78 C
2) CH3I
(e)
100 C
Page 2 of7
~OMe (2 equiv)
(f)
NaOMe
E
Me OH
(g)
(h)
!:!
M\ _ / \ _ __/Me
1) Br2 , NaOH
Me}-N~b
2) H30+
(i)
Co)
benzene
N
H
heat
Br
0
II
~OEt
b
EtOH
NaOH
(26 marks)
Page 3 of7
2.
(a)
Picric acid is exceptionally acidic (pKa = 0.38). Explain.
OH
02N~N02
picric acid
N02
(3 marks)
(b)
Which of the following molecules (N and 0) will not undergo

decarboxylation upon heating? Explain your answer.
HOjA
o--'
r(\
::t:
o:;
(3 marks)
(c)
For each of the following compounds, indicate if it is aromatic or not.

Explain your answers.
H
H, /N, ,..,H
8
8
I
H'_,N,~/N,H
H
B
(6 marks)
(d)
Rank the basicity of the following compounds. Explain your answer.
Q
H
0
N
N
H
I
(6 marks)
Page 4 of 7
3.
product
(i) Suggest why the reaction fails;
give a good yield of the desired product from the same starting material.
(a)
no
MeMgBr
Meo~
THF
OMe
(b)
HO-o-NH2
2)
><
n
Meo~
Me
><
H0-0-N=N-0
(c)
(d)
eo~
(16marks)
Page 5 of7
4.

(a)
"'go,Y
0
t-BuOK
THF
OH
EtO
OEt
KOH, EtOH
(b)
OH
i. Mel;
ii. Ag 2 0, HzO;
iii. heat
(c)
~2
(d)
OH
(e)
n.
(f)
H3C~H
Z'...NACH
I
CH3
(24marks)
Page 6 of7
5.
(a)
<j)H
~NH2
from
~CHO
(b)
from
(c)
EtO~OEt
(d)
Me\'N)lMe
Me
H
from
(16 marks)
-END OF PAPER-
Page 7 of7


2:30 pm- 5:30 pm
Only approved calculators as announced by the Exan1inations Secretary can be used in this examination. It is
nan1e and type of the calculator used on the front page of the examination script.

Page 1 of7

1.
Provide the missing reagents, reaction conditions or structures of major products

(denoted by the letters A to !J for each of the following transformations. Show
the stereochemistry where necessary.
(a)
CrOH
Br
(b)
NaOMe
MeOH
(c)
cc?
H2NNH 2, KOH
ethylene glycol
heat
(d)
(oi(YC02Me
O~CHO
(e)
nOH
Me
(f)
NH
0Me
A 0 Jl Me
Me
2
(1 equiv)
CH 2Cl 2, room temperature
E
Et20
C02Me
Me
Me
Page 2 of 7
Me
OH
OMe OH
(g)
H2C"-
NaBH4
0
MeOH
NaH (excess)
C 6H5CH 2Br (excess)
!:!
Et20
OMe
(h)
MeO~Me
I -""
Me
Me
(i)
(j)
(le)
heat
(24 marks)
Page 3 of7
2.
(a)
Compounds Mand!'.!: are reported to possess higher aromatic stabilization energies

than the essentially non-aromatic compound 0, while compound E. is anti-aromatic.
Explain the different properties ofM-f..
BH
L
Q
(8 marks)
(b)
The Fries rearrangement is a rearrangement reaction of a phenyl ester, e.g.
Q, to a hydroxyaryl ketone, e.g. R, in the presence of Lewis acid, e.g. Al Cb.

It involves the same acylium intennediate as that for the Friedel-Craft
acylation reaction. Suggest a mechanism for the transformation of Q to R,
as shown below.
UF
l~~OH
Me
B
(4 marks)
(c)
Rank the reactivity of benzene @.), chlorobenzene (!) and pyridine N-oxide
ill) towards bromination reaction under the Br2/FeBr3 condition. Explain

your choice.
oe
Cl
6
I
0
.!.!.
(4 marks)
(d)
Rank the reactivity of the following esters towards alkaline hydrolysis and
explain your answer.
(4 marks)
Page 4 of 7
3.
product.
(i)
Suggest why the reaction fails;
give a good yield of the desired product from the same stating material.
Ho-Q-co2H
(b)
><
VNH2
NaBH 4
EtOH
><'
~CHO
><
B
19/ ----
0
(d)
LiAIH4
THF
(16marks)
Page 5 of 7
4.

clearly structures of all intermediates and electron flow.
(a)
NaOEt
EtOH
CHO
Na OH
(b)
co
,..;
NH2
quinoline
(Friedlander synthesis)
(c)
(d)
0
():)
(e)
'
Me
(f)
Meo~
Me OH
l_A"J
0
MeO~O
llAOH
(24marks)
Page 6 of7
5.
(a)
11
Br
,,.;;:;
from
Br
(b)
from
(c)
(d)
from
EtO~OEt
from
(16 marks)
- END OF PAPER-
Page 7 of7
THE UIVERSITY OF HONG KONG


9:30am- 12:30 pm
Answer ALL questions. (Total lOO marks)

1.

(denoted by the letters A to M) for each of the following transformations. Show
the stereochemistry where necessary.
i) PhMgBr
(a)
iil H,o
,,
AcO OAc
OMe
(b)
MeO~OH
('yi;-OAc
V'\{0
0
1,-:;;
Me
OMe
0~
eO~
1,-:;;
(c)
Me
i) 190-200 'C;
ii) K2 C0 3 , PhCH 2 Br
OCH 2 Ph
(d)
~C02 Et
NC~
i) LiAIH 4 (excess), THF, 0 C

ii) H20
i) LOA, THF, -78
oc;
Meo{-- 0 )
CJON~''''t(
"'\OMe
OH OMe
(e)
y ":
~
(f)
i) H2so NaN0 2
(g)
ii) Cu 20, Cu(N0 3),, H20
Me Me
(h)
'f--o
~co2Me
MgBr
CH 2CI2, -78
(j)
oc
"'
(i)
(iBu),AJH
THF, -78
oc
MePPh 3 Br, BuLl
THF, 0 oc
i) Mg, Et2 0
POCI3
(26 marks)
2.
(i)
The pK, values of histidine are 1.77, 6.10 and 9.18.
~~OH_.-pK.=1.77
pK.=6.10
~ ~~{J}
~H3+
histidine
--.._ pK8
=9.18
(a) Explain the difference in pK, values.

(b) Draw the major form of histidine at pH 7.4.
(4 marks)
(ii)
Pyrro le undergoes electrop hilic aromatic substitution under much milder

conditions than benzene.
Br2
HQ
But not
Br
(a) Explain why pyrrole reacts more readily than benzene.

(b) Explain why the substitution occurs at the 2-position rather than 3position.
(6 marks)
(iii) Answer the following questions concerning the two-step reaction shown
below.
1
-N-H-3.-H-:0-.-6-0-"C-[
df,]
0
NH3
ci'NH2
y
(a) Draw the mechanism for the two-step process.
(b) Explain why Y reacts with NH3 rather than H 20 or
reaction mixture.
0~ present
in the
(8 marks)
(iv) The following reaction does not provide a satisfactory yield of the desired
product. Suggest why the reaction fails and how the reagents should be
changed or conditions modified to give a good yield of the desired product.
0
Mg
~OCH3
~OCH3
(4 marks)
(v)
Show mechanism and explain why the following bromoketone forms

different bicyclic compounds under different reaction conditions.
NaOCH 3, CH 30H
~
-78 C
(4 marks)
3.

(a)
~N02
Et0 2CqC02EI
NaCH(C0 2Et),
DMF,heat
OCH3
""
N02
1.&
OCH3
7'Yo
(b)
Me
CH3
ou)
KOH, MeOH
CH3
(c)
H3CXCH3
0
H3o
~CH3
CH 2COOH
+
H3C
y__
CH3
(d)
~0
'
ii) NaOH, EtOAc
~0
11
11
i) Br2
~oAo
N(CH3),
(e)
(f)
i) CH3I
H3C~OEt
~6
ii) KOH
iii)
H3o
COOH
i) NaOEt, EtOH
ii) H3 o, heat
+ C0 2 + EtOH
YcH3
C02Et
(24 marks)
4.
Me
"' Q
)..._,9
(a)
Cl
from
N02
(b)
YBr
~
Me
from
Q
Me
(c)
(d)
y{
from
and
(e)
(f)
HO~
./'-._
Ph/
,CHO
'-./
from
0
11
0
11
EIO~OEI
Ph~
(24 marks)
-END OF PAPER-
THE UNIVERSITY OF HONG KONG


May 15, 2012 (Tuesday)
9:30 am-12:30 pm
Only approved calculators as announced by the Exanzinations Secretary can be used in this examination. It is
candidates ' responsibility to ensure that their calculator operates satisfactorily, and candidates 1nust record the
nan1e and type of the calculator used on the front page of the examination script.

I.
Provide the missing reagents, reaction conditions or structures of major products (denoted
by the letters A to ~ for each of the following transformations. Show the stereochemistry
where necessary.
i)oD
(a)
(b)
CJ~CI
DMF
(c)
(d)
(e)
Na 2 S (1 equiv)
Oo
N
H
i) EtMgBr (excess)
(f)
!::!
ii) H3o+
~N~
vu
(g)
ether
i) CH 31, K2C03
,!
ii) Ag20 I H20
IS
iii)~
~OH
(h)
-Q-so2c1
pyridine
~N3
NaN3
.b
1M
~N(CH3h
~NH2
(28 marks)
2.
(a)
2-Chloro-2-methylpropane and chlorotrimethylsilane can both react with NaOEt to

give different type of products.
NaOEt
heat
Compound
2-chloro-2-methylpropane
Ck ,CH3
~i-cH3
CH3
NaOEt
heat
Compound
chlorotrimethylsilane
i)
ii)
Draw the structures of compound X and compound Y.

Briefly explain their difference in chemistry.
(6 marks)
(b)
Rank the following compounds in order of increasing acidity and give explanation for
your answer.
(5 marks)
3.
Choose the compound within each group that meets the indicated criterion, and explain
your choice.
(a)
The compound that reacts with alcoholic KOH to liberate fluoride ion.
or
(b)
The compound that cannot be prepared by a Williamson ether synthesis.
Q
(c)
or
OEt
or
.&
The compound that gives two products when it reacts with KNH 2 in liquid ammonia.
or
(9 marks)
4
4.
The following reactions do not provide a satisfactory yield of the desired products. Suggest
(i) why the reaction fails and (ii) how the reagents should be changed or conditions
modified to give good yields of the desired products.
i) NaOEt
(a)
(b)
ii) CH 3CH2Br
iii) H3 o+, heat
HO
"
-0_\
NH2
i) NaN02 I HCI I H20
ii)
H0-0-N=N-0
\-/;
(8 marks)
5.
Propose a reasonable mechanism for each of the following transformations. Show clearly
the structures of all intermediates and electron flow.
(a)
i) NaOH, H20, MeOH
ii) HCI
(b)
i) 1-BuOK
(c)
(d)
H~N~CH3
0
H+
Ph
>=<
N02
(e)
"::,._ 0
0
COzl-Bu
(f)
MeO~
H+ H 01s
'
(24 marks)
6.
Provide a synthetic route for each of the target molecules below, starting from the given
starting materials. More than one step may be necessary. Use any readily available
substrates, reagents and solvents.
(a)
HO-o-NHCOCH3
from
(Acetaminophen or Paracetamol)
6
0
(b)
from
(c)
Br~Br
lr
Br
from
O~
,,,,
(d)
(e)
~H
~
from
from
and
0-0H
(20 marks)
- END OF PAPER-
.,


9:30am -12:30 pm
Only approved calculators as announced by the Examinations Secretary can be used in this examination.
It is candidates' responsibility to ensure that their calculator operates satisfactorily, and candidates must
record the name and type ofthe calculator used on the front page of the examination script.

1.

(denoted by letters A toN) for each of the following transformations.
(a)
H2 NNH 2
KOH, DMSO
p
0
(b)
1) CH 3MgBr, ether
~ " _s_o_c_1~2~
~NE!2
(c)
2) H30+
HO
pyridine
N0 2
(d)
PhCH2NH2
Et OH
(e)
(f)
(g)
!:!
.b
(h)
(28 marks)
2.
(a)
Indicate whether o. or Ob is more basic in the compound shown below, and

provide a rationale for your decision.
aO=b
0
(4 marks)
3
(b)
Calicene has a large dipole moment. Briefly explain why.
Calicene
(4 marks)
(c)
The spectral data for compound X are shown below. Propose a structure for
compound X. Give your reasons.
Formula: C7H140
IR: 1715 cm- 1
1
HNMR:
12H
2H
11
10
'
5'
pp m
KSP-OQ-203
(6 marks)
(d)
Arrange the following compounds in order of increasing basicity, and briefly

explain your answer using both words and resonance structures.
o-NH NC-o-NH2
2
(6 marks)
(e)
The following reaction failed to give the desired product. Explain why, and
suggest an alternative scheme to carry out the transformation starting from the
same substrate. More than one step may be needed.
1) Mg, Et20
2) C02
x~~H
3) H,o
(4 marks)
3.

(a)
(b)
~~Cl
0
Ph~Ph
)l
I( 'Ph
Ph.
KOH
EtOH
Ph~ Ph
)-!( Ph
Ph
l l
NaH
-...:::::
(c)
HO
J
0
(d)
Ph~Ph
)___!(
Ph
Ph
Ph
Ph
1 ) LiN'O
(e)
(f)
DCH3
H3C
CH 3
C)CCH3
0
Ph
H3C
2) 0co2CH
3
cat H+
Br2
C02CH3
H
CH3
cxS"
0
Ph
(24 marks)
4.
given starting materials. More than one step may be required. Show sufficient
details of the conditions of each reaction step. You may use any readily available
reagents and additional starting materials as needed.
(a)
02N-Q-NH2
from
Br
(b)
H3C~ CH3
0
from
(c)
(d)
~
6H
I
from
H3 C)l.__)l.OEt
(e)
(f)
from
~Ph
from
-END OF PAPER-
(24 marks)
'/~
THE UNIVERSIT OF HONG KONG

'
DEPARTMENT
bF CHEMISTRY

May 12,2010 (Wednesday)
2:30pm-5:30pm
-
Answer ALL
1.
questio~s.
Draw the structures of the major products
(Total lOO marks)
lA-;[ in the following reactions.
1) HgS04 , MeOH
(a)
.....
2) NaBH4
(b)
1) LiN(iPr)z, -78 C
(c)
..I
(d)
~C02CH3
toluene, -78 C
II
1) excess Me I
(e)
(f)
~OH
Cr03
.E
2
\
(g)
(h)
(i)
~COCI
Pyridine
___
.,...~
HOJNH2
~ OMe (2equiv)
,...
NaOMe
,....
(20 marks)
2.
(a)
Explain why the neutral molecule pentalene 1s polar but why its dianion
nonpolar.
pentalene
IS
pentalene dianion
(5 marks)
(b)
Arrange the following carbonyl compounds in the ease of forming enol tautomer
in aqueous medium, and explain your answer concisely.
11
6 6
Ill
IV
(4 marks)
3.
(a)
Explain the experimental results that benzene does not undergo electrophilic
addition in the absence of Lewis acid catalyst. However, electrophilic bromination
to alkene is an efficient process.
I
Br
()
Br-Br
-c
Br-Br
a
,.
a
Br
Br
)( ,..
Br-Br
H
H
Br
Br
H
(4 marks)
(b)
Friedel-Crafts alkylation and acylation reactions are essential methods to

synthesize substituted aromatic compounds. Industrial synthesis of ibuprofen, a
pain-reliever, involves Friedel-Crafts reaction to prepare isobutylbenzene
intermediate.
yOI
COOH
Isobutyl benzene
lbuprofen
However, attempts to prepare isobutylbenzene

by Friedel-Crafts alkylation of
I
benzene lead to the formation of undesired tert-butylbenzene as major product.
I
1
Cl~
AICI3
~,.. l)
(i)
Suggest a reasonable mechanism for this undesired reaction, showing all

necessary electron flows and structures of intermediate.
(ii)
Suggest an alternative synthltic route, using Friedel-Crafts acylation, to

prepare isobutylbenzene from penzene.
(iii) According to (ii), explain concisely why Friedel-Crafts acylation is more

selective than the alkylation reaction.
(7 marks)
4.
Design a concise multi-step synthesis for each of the following target compounds using
indicated starting materials and any other readily available reagents.
OH
(a)
(}
0
from
Br
(b)
6:'p~
from
SH
(c)
(d)
(e)
?H
from
V
0
c6
oo5
from
from
and
Go
0
any compounds of Q.carbon
~.orle..as.
from
(f)
y
0
(g)
from
and
CHO
Br
(h)
or-0--\
from
(32 marks)
-----------~--------------------------------------
J
5.
Suggest a reasonable mechanism for each of the following transformations. Give

structures of all intermediates and clear dectron flows.
(a)
~NH
0
eH)
qc
coo1 lit)
(b)
"c:=c-coocH3
140
1c
!
(c)
0
Br~P(C 6 Hsh
1~
Br8
2 equiv tBuOK
~
2) C5HsCHO
~C6Hs
(d)
(e)
OEt
11
_.....C, ,....,C02Et
H3C
C
(2 equiv) +
H2
CD
HtH
NH 3
..
Et02CX:XC02Et
I I
H3C
N
H
CH3
(f)
(g)
) BrJCOOC2HJ
I
2) H30+
I
!
NaOH
H20
COOC 2H5
-oo
(28 marks)
-END OF PAPERI

May 6, 2009 (Wednesday)
2:30pm-5:30pm
Candidates may use any self-contained, silent, battery-operated and pocket-sized calculator. The calculator
should have numeral-display facilities only and should be used only for the purposes of calculation. It is the
candidate's responsibility to ensure that his/her calculator operates satisfactorily.
Candidates must record the name and type oftheir calculators on the front page oftheir examination scripts.
1.
Provide the missing reagents and reaction conditions for each of the following
transformations. More than one reaction may be necessary for each transformation.
(a)
(b)
~C02H__!___ ~OH
_.!_ ~CHO
(20 marks)
2.
(a)
Indicate the most acidic proton in vitamin C and briefly explain your answer.
Vitamin C
(5 marks)
(b)
3-Chlorocyclopropene, on treatment with AgBF4 , gives a precipitate of AgCl and

a stable solution of a product that shows a single 1H NMR absorption at o 11.04
ppm. What is a likely structure for the product, and what is its relation to Hiickel's
rule?
HYCI
3-Chlorocyclopropene
(5 marks)
(c)
Contrast the location of 18 0 in the products of the following two reactions, and
provide a mechanism for each reaction.
(i)
(ii)
~0/
1aow
~0)(
H+
1BoH2
(5 marks)
(d)
Ethyl p-nitrobenzoate is more reactive towards nucleophilic acyl substitution than

ethyl p-methoxybenzoate. Explain this reactivity difference using both words and
structures.
CH30--Q--t<
OEt
Ethyl p-nitrobenzoate
Ethyl p-methoxybenzoate
(5 marks)
3.

(a)
0~
0
aq. HBr
Br~
heat
(b)
HCI
..
H
trace H+
(c)
(d)
H~N~
0
a
0
(e)
CH,
PhCH,DCH,
1) LiN[CH(CH3hl2. THF
(Xcoo~
()<CH,
2) PhCH 2Br
CH2Ph
90%
(f)
N2+
Jo
CC)) -
Ll
10%
(g)
H)lH
H+ catalyst
7;
0~0
(28 marks)
4.
Provide a synthetic route for each of the target molecules below, starting from the given
starting materials. More than one step may be required. Show sufficient details of the
conditions of each reaction step. You may use any readily available reagents and
additional starting materials as needed.
(a)
~OEI
from
(b)
H,N~
from
t.__,_NH2
0
CH 3
CH3
(c)
CH3CH2+NH2
CH3
6:CHa
from
CH3
(d)
from
Ph
(e)
BryBr
10
from
Br
(h)
from
(f)
(g)
CH 3CH 2+Br
~OH
from
OH
and
('yBr
from
HO~
-END OF PAPER-
(32 marks)

2:30pm-5:30pm
Candidates must record the name and type of their calculators on the front page of their examination scripts.
Answer questions 1-6 in the RED covered answer book.
1.
The oxidation of cycloheptatriene gives a carbocation, A.
H)
~
~
H--0
A
o0
Tropone
(a)
Draw the molecular orbital diagram of A, using the polygon and circle method to
estimate the relative energies of the orbitals. Label the molecular orbitals.
(b)
Is A aromatic or not? Justify your conclusion ONLY on the basis of the

molecular orbital diagram in part (a).
(c)
Cycloheptatriene is easily converted into another compound, tropone (ID.

Tropone has a much greater dipole moment (J..l = 4.17 D) than typical ketones
(cycloheptanone has J..l = 3.04 D). Also, tropone is unusually basic. Explain both
of these observations about tropone by considering its structure and stabilization.
(10 marks)
2.
Propose concise syntheses of the following molecules from the given starting materials,
and any other readily available solvents and reagents, providing enough detail about the
reactions used. More than one step is necessary, thus show clearly each intermediate at
the end of each reaction.
(a)
from
(b)
from cyclopentadiene as the only source of carbon
(c)
from benzene
(10 marks)
3.
The intermediate obtained from the electrophilic addition of benzene

Wheland intermediate.
IS
called a
(a)
Draw the Wheland intermediate in the electrophilic bromination of benzene.
(b)
Which intermediate is more stable: the Wheland intermediate in the bromination

of benzene or the intermediate in the electrophilic bromination of an alkene?
Justify your answer.
(c)
The bromination of benzene occurs only in the presence of a catalyst. Based on

your answer in (b), explain why the bromination of benzene does not proceed as
readily or as quickly compared to the bromination of an alkene. Use an energy
diagram to help explain your answer.
(5 marks)
4.
(a)
Arrange the following compounds in the ease of hydrate (gem-diol) formation in

aqueous medium, and explain your answer concisely.
A
I
II
Ill
IV
(5 marks)
(b)
Write a reasonable mechanism for the following transformation.
1) excess MeMgBr, THF

~
(4 marks)
5.
The following reactions are not high-yielding for the desired products.
(i)
ether
(ii)
aqueous H2 S04
Acetone
For each reaction,

(a)
explain clearly why it is not efficient to furnish the desired product;
(b)
suggest an alternative synthetic method (i.e. reagents and reaction conditions) that
can produce the desired target compound in good yields, starting from the given
precursors.
(8 marks)
6.
Draw the structures of the major products AA-DD in the following reactions.
(a)
------------~~
AA
DMSO
(b)
0~
.ij
250C
=13C-Iabelling
(c)
Br
~
s
(d)
1\
Ph-S S-Ph
---------------~
DD
(8 marks)
Answer guestions 7-10 in the BLUE covered answer book.

7.
Provide correct product(s) and/or outcomes in the following reactions.

(a)
Q-oH
<)-coc1
pyridine
(b)
(CH 3)2CuLi
CH3CH2COCI
(c)
FF
ether
qH
NaOH
C2H50H
Cl
HH
GG
an intermediate
(d)
0
HN(CH3)2
NaBH 3CN
!!
CH30H
(e)
QH
(f)
o-CHO
CH3c-o
NaOH
ethanol
KK
NaOC 2H5 , C 2H50H

0
LL
6C02C2H5
(g)
&
CH 3
1) HN02, H2S04
MM
2) Nal
(18 marks)
6
8.
Provide the m1ss1ng reagents and reaction conditions for each of the following
(a)
(b)
(c)
(d)
c..j)
H 3 C~
H3C
N
H
H3
H3C
N
H
(e)
0
11
CH3CCH2CH2CH3
CH3CH2CH2COOH
(f)
(12 marks)
9.
Write a reasonable mechanism for each of the following transformations.
(a)
heat
(b)
(8 marks)
10.
Provide a reasonable synthetic route for each of the following compounds. You must
use the indicated materials below, plus any other readily available reagents. More than
one step may be required.
(a)
from
(b)
from
(c)
from
(12 marks)
-END OF PAPER-

9:30am- 12:30 pm

Answer questions 1 - 3 in the RED covered answer book.
1.
Provide major products and/or outcomes in the following reactions, showing

stereochemistry in your structures when necessary.
excess H2 , Pd/C
Heat
~OTs
~OCH 3
heat
PH
HO
(KS0 3 hNO
47
POCI3
G
pyridine
OH
C)<
Cr0 3
HBr
!:!
H2S04 , acetone
~MgBr
ether
ou
,,,,b
excess CH 3CH 2Mg8r
H30+
cat. H2S0 4
SOCI 2
0""~
CH2CI 2
ethanol
!:
ether
excess
OH
H30+
MgCI
THF
~CH3
S03, H2S04
N02
Br
0
Cl
~Cl
Q
AICI 3
cY'o~
h-
LiAIH 4
OCH 3
ether
H30+
(18 marks)
2.
(a)
Write a detailed mechanism for the reaction below, showing clearly electron flow
and the structure of any intermediates.
strong base
Cl
(b)
Compounds and T below are individually treated with base. Both compounds
are deprotonated at the methyl groups to generate carbanions. Draw the product
of each deprotonation reaction, and consider the stability of each product by
drawing their resonance structures.
Base
Base
I
Which compound, or T, do you think is more acidic, i.e. more easily
deprotonated? Justify your answer based on the structures you have drawn.
(10 marks)
3.
Provide synthetic routes for the synthesis of the target molecules below. More than one
step may be required. Show sufficient detail of the conditions of each reaction. You
may use any readily available reagents and starting materials.
COOH
PABA
(active ingredient in some sunscreens)
HO~
~OH
0
(12 marks)
Answer questions 4- 8 in the BLUE covered answer book.

4.
Arrange the following compounds in order of increasing reactivity toward nucleophilic

attack, and briefly explain your answer.
~OMe
~
11
~H
IV
Ill
(5 marks)
5.
Provide the missing reagents and reaction conditions for each of the following
0
~OMe
d
A{oMe
0
MeO~
HO~
eO~
(5 marks)
6.
Draw the structures of the major products AA-LL in the following reactions.
H2N~OH
~COOH
AA
pyridine
Q
H
cc
H+ catalyst
1. Mel (excess), K2C0 3
2. Ag20, H20
3. heat
~OEt
0
Q-cN
HO~OH
H+ catalyst
toluene, -78 C
1. PhMgBr
THF
Q-oH
(22 marks)
7.
(a)
NaOMe
Me OH
(b)
~COO Et
~Br
(c)
~NH 2
Et OH
cO
COOEt
Ph
COO Et
(d)
1. LiAIH 4 , ether
2. H20
(16 marks)
8.
Suggest a short synthesis for each of the following compounds from the indicated
starting materials and any other reagents.
(a)
~OH
OH
from
(b)
if
0
fro1n
(c)
from
(12 marks)
-END OF PAPER-

May 20, 2006 (Saturday)
2:30pm-5:30pm

Answer questions 1 - 4 in the RED covered answer book.
I.
Provide correct product(s) and/or outcomes in the following reactions, showing

stereochemistry in your structure where necessary.
(a)
NBS
(b)
OH
6
(d)
1. NaH, THF
(e)
MgBr
()
1. ether ,.
2. H 3o+
(f)
1. Hg(02 CCF 3) 2 , (CH3 ) 3 COH
2. NaBH 4
(g)
(h)
(i)
()H
(12 marks)
2.
Provide high-yielding syntheses of the following compounds from the given starting
materials. You may use any other necessary substrates and reagents. Provide sufficient
details regarding the reaction conditions and intermediates.
0
(a)
Benzene or toluene _ _ _........,.
(b)
0
Br
OH
(c)
1,3 -cyclohexadiene - - - - - - .
OH
(14 marks)
3.
(a)
Draw the molecular orbital (MO) diagram of 1,3-cyclobutadiene, using the

polygon and circle method to estimate the relative energies of the orbitals. Label
the orbitals.
(b)
Is cyclobutadiene aromatic or not? Justify your conclusion on the basis of the

above MO diagram.
(c)
On the basis of the MO diagram, would it be easy to remove one electron from
1,3-cyclobutadiene? Would it be easy to remove two electrons? Why, or why not?
(8 marks)
4.
(a)
Propose a structure for an alcohol of formula C7H80 that has the following 1H
NMR spectrum, obtained in CDCb.
5H
2H
1H
t-----------.J 11.....__ _ _ _
11
-.---J,...___ _ _ _ . - - - - - - ;
10
HSP-03-658
pp m
(b)
How would you expect the 1H NMR spectrum to change if it were obtained in
D20, and why?
(c)
Most ethers react when heated with HX, but diphenyl ether is inert to cleavage by
HI or HBr. Explain this observation using mechanistic arguments.
o- 0-o~
HX
no reaction
(6 marks)
Answer questions 5 - 8 in the BLUE covered answer book.
5.
(a)
Consider the structures below to answer the following questions.
affi
c{OH
0
11
C-H
(b)
11
H3C/ . . . ._ CH;- "'- CH
Ill
11
(i)
(ii)
11
Indicate the most acidic hydrogen(s) in each of the molecules.

Rank the molecules above in order of increasing acidity (least acidic to most
acidic).
(5 marks)
Rank the following compounds in the order of increasing basicity and give your
explanation.
(3 marks)
6.
starting materials and any other necessary reagents.
Br
Br
(a)
from
Br
(b)
UXCH3
H
from
0
urOH
0
from
(c)
EtO~OEt
(12 marks)
7.
Draw the structures for the major products AA-KK in the following reactions.
1. CH 31 (excess)
K2C03
(a)
oCt
LiAIH 4
AA
BB
2. Ag20 I H20
3.
(0) +A
0
(b)
N
H
(c)
(d)
~OH
benzene
cc
0
BrJOEt
~NH2
PCC
..
(CH 3C0) 20
(e)
DD
then H3o+
JJ
NaOH, H 20
QCOOH
OH
CH30H
KK
HCI
(f)
(g)
~COOH
OCHO
NH 2NH 2, KOH
~~
heat
VCH2CN
#
5o/o NaOEt, EtOH
MM
heat
(24 marks)
8.
(a)
(b)
~3
1) NaOCH 3/MeOH
H3COOC~
2) CH3COOH
(c)
(d)
H~~~CH3
0
(16 marks)
-END OF PAPER-


2:30 pm- 5:30 pm
Candidates must record the name and type oftheir calculators on the front page of their examination scripts.

Answerguestions 1 - 4 in the RED covered answer book.
1.
The following reactions DO NOT proceed efficiently to give good yields ofthe desired
products.
(a)
(1) PBr3 , diethyl ether
x~
(b)
For each reaction:

(i)
State concisely why this reaction does not give the desired product;
(ii)
Show what compound would result if these reactions were carried out as shown,
and
(iii) Propose alternative reagents, reactions and/or reaction conditions to obtain good
yields of the desired products starting from the SAME given substrates.
(8 marks)
2.
Propose structures of the major product(s) of the following reactions, represented by the
letters A to G. Show stereochemistry where necessary.
1) add 1M NaOH
0~
-Q-o
~-cl
diethyl ether
2) separate aqueous
and ether phases
A in ether
3) each phase is
acidified
in water
Cl
MeO~
~I
,AICI3
~NH
0~
Cui
~OH
0
<r
THF
(14 marks)
3.
Propose reasonable, high-yielding syntheses of the following compounds from the

given starting materials. You may use any other solvents or reagents as necessary.
Show the conditions for each reaction, and all intermediates in detail. More than one
step is required.
0
(a)
~OH
BrAY
from
NH2
8s,~1
: : :. .
(b)
(c)
from benzene
OCH3
from 1-methyl-1-cyclohexanol
OH
(12 marks)
4.
Write reasonable mechanisms for the following reactions. Show clearly the structures
of all intermediates and electron flow.
(a)
OOH
ifoH
H2 Cr0 4
H2 0
(b)
Cl
Cl 2
FeCI 3
NaNH 2
~
(6 marks)
Answer questions 5 - 9 in the BLUE covered answer book.

5.
Refer to the table of pKa of some arylammonium ions below to answer the following
questions:
v-Q-AA,
y
pKa
-H
4.63
1.74
6.15
-C:=N
-NH2
(a)
Based on the pK8 for their corresponding ammonium ions, which arylamine above
is the strongest base?
(b)
Explain the difference in acidity between p-cyanoanilinium ion and paminoanilinium ion.
(6 marks)
6.
Provide the mtssmg reagents and reaction conditions for each of the following
transformations. More than one reaction may be necessary.
Br-CHCH3
HOOC-CHCH3
(a)
...
(b)
...
f.,~OH
...
~eH,
h
...
~
0
(8 marks)
7.
(a)
1. Br2, PBr3
H3C)lOH
CH3CH20H
AA
2.H20
HCI
BB
NaCN
cc
(b)
1. Br2, CH 3COOH
DD
2. pyridine, heat
H3C~
(c)
(d)
Et02C
NaOEt
.E.E
C02Et
Q=o
EtOH
~NH,
FF
(CH3C0)20
(e)
(f)
H2N-o-CH3
(i-Pr)2AIH
~C02CH3
p
p
GG
pyridine
toluene, -78 C
!:!!:!
..
(g)
Br2, H20
(CaH 5),-CHCH 3
+
JJ
THF
(h)
n-BuNH 2
.!S.!S
EtCH
(18 marks)
6
8.
Outline a reasonable mechanism for each of the following transformations.
(a)
(o)CcH,
0
(b)
(c)
Ph
Br2
Q-c N
0
cO><SBr
cat. H+
Ph
NH2
~MgBr
o
I
vc~
~
H~H
NaOEt
EtOH
(d)
(16 marks)
9.
from
(a)
(b)
from
(c)
from
(12 marks)
-END OF PAPER-

9:30am- 12:30 pm

Answerguestions 1-4 in the RED covered answer book..
1.
Write the structure(s) of the product(s) for each of the reactions below. Be sure to
indicate any relevant stereochemistry.
(a)
CH3CH2CH2Cl
AlCl3
(b)
11
c......_
H
(c)
KCN
HCN
()
(C 6H 5) 3P--C(CH 3)z
THF
2
(d)
(e)
(f)
(g)
OCl
ether
.
0
NaOCH2CH3
H
(h)
(i)
ether
(k)
0
c6
pH 4.5, Heat
(22 marks)
3
2.
(a)
Cyclobutadiene is an extremely unstable compound whose isolation is impossible

even at the lowest temperatures routinely accessible in the organic laboratory.
However, free cyclobutadienes almost surely occur in some reactions as
intermediates. In fact, extremely facile Diels-Alder reactions have been used to
recognize cyclobutadiene as an intermediate. Write the structure of the DietsAlder product you would expect to isolate from the following reaction.
(3 marks)
(b) Aniline reacts with nitrous acid, HN02, to yield a stable diazonium salt A. This
diazonium salt undergoes electrophilic aromatic substitution with activated
aromatic rings to yield brightly colored azo compounds such as C that are widely
used as dyes.
Write a detailed mechanism for the reaction that synthesizes C from A and B, and
show all electron flow with arrows and show all intermediates and resonance
structures.
+
A
o-N=N-o-N(CH3h +HCl
c
(4 marks)
3.
(a)
For the two molecules below, write complete Lewis structures showing all
electrons belonging to each atom. Determine whether each of these molecules is
aromatic or not, and explain your reasoning.
(i)
(ii)
f'
oJ
OH
6
0
(6 marks)
(b)
The 1H NMR spectrum of [14]annulene at -60C shows two signals, one at 0 ppm
and one at 7.6 ppm. What would you expect the integration of the areas of the
two signals to be, ie. how many protons correspond to the signal at 7.6 ppm, and
how many protons correspond to the signal at 0 ppm? Explain your reasoning,
using diagrams if necessary.
[14]amlUlene
(3 marks)
4.
Provide concise syntheses for the target molecules, starting from the given substrates.
More than one step may be necessary. Use any readily available substrates, reagents
and solvents.
(a)
(b)
(c)
(12 marks)
Answer questions 5-8 in the BLUE covered answer book.
5.
(a)
CO
N
'H
(b)
(c)
~Cl
ll ..N~Cl
NaOCH 3
(1 equiv)
1) LiAIH 4 (excess), ether
(d)
EE
(e)
1) CH 3 1 (excess), K2 C03
(f)
2) Ag20 I H20
(g)
Br~Br
y
Br
(20 marks)
6.
(a)
Arrange the following compounds in the order of increasing basicity and briefly
o-N=>
N
H
(3 marks)
(b)
Arrange the following compounds in the order of increasing acidity and briefly
(3 marks)
7.
(a)
cx:H,+
~CH3
dio
NaOEt
EtOH
CH 3
crBr
(b)
(c)
yi5
0
Li
0
0
C02 Et
NaOEt
Et OH
p
0
(12 marks)
8.
0
(a)
(b)
tBuO
-Q-A
NH
CH 3
from
O~N~
c60H H
~
OH
from
.0
(c)
F-o-N02
c6
and
~r
.0
VNU
H I
/?
from
~OH
(only source of carbon

allowed)
(12 marks)
-END OF PAPER-

6:30pm-9:30pm
Candidates may use any se(f~contained, silent, battery-operated and pocket-sized calculator. The calculator
should have numeral-di.\play fad lilies only and should be used only for the purposes of calculation. It is the
candidate's responsihility to ensure that his/her calculator operates satisfactorily.

1.
The reactions below DO NOT give good yields of the desired products.
reaction:
For each
(i)
State concisely why these reactions do not give the desired products;
(ii)
Draw the products that would result if these reactions were carried out as shown,
and
(iii) Propose alternative reagents, reactions, and/or reaction conditions which generate
good yields of the desired products starting from the SAME given substrates.
(a)
11
11
2. AICI3, H3C-C-O-C-CH3
(b)
(6 111arks)
2.
Provide the structures of the MAJOR products denoted by the letters A to 0 in the
following reactions. Assume that there is an appropriate workup after every reaction.
Show clearly the STEREOCHEMISTRY of each product where applicable.
(a)
A
Benzene, heat
(b)
(c)
-~
)-~AI,H
ether
reflux
(d)
1. Mg, ether
(e)
anhydrous HCI, CH 3 0H
(f)
fuming sulfuric acid

H
(g)
!
Heat
(h)
CHO
I
0
(i)
CO=o
NaOH
.b
3
Br
(j)
/~Cl
()
AICI 3
OCH 3
---
(k)
/"'~
cat. DCI
0
0 2 0, 18 hours
(24 marks)
3.
ANSWER TWO OUT OF TI-IE FOLLOWING THREE (a, b, c) QUESTIONS.
(a)
Using diagran1s and chernical structures, explain why nitrobenzene directs

clcctrophilic substitution to the meta positions. Show why substitution at the
ortho positions is unfavoured. Use the bromination of nitrobenzene to illustrate
your answer.
(b)
Using the "polygon and circle" method, show the relative energies and electron
occupation of the n1olecular orbitals of planar cyclooctatetraene, and explain why
it is a non-ar01natic compound.
(c)
For the reaction,
1M HCI
p
(i)
Write the structure of the intermediate compound, P and show the

mcchanisrn by which it is fonned.
(ii)
Show a n1echanisn1 by which the acidic hydrolysis of P converts it to

aldehyde Q.
(8 marks)
4.
ANSWER TWO OUT OF THE FOLLOWING THREE (a, b, c) QUESTIONS.

(a)
(i)
Write a detailed mechanism for the reaction below by showing electron

flow, all intennediates and all steps clearly.
if
(b)
(c)
NaOH
work up
+
excess 12
(ii)
If the substrate were ethyl cyclohexyl ketone instead of methyl cyclohexyl

ketone, would carbon-carbon bond cleavage occur? Why or why not?
(i)

flow, all intermediates and all steps clearly.
(ii)
If the reaction were done instead with a chromium oxidant such as PCC in
dichloromethane, the alcohol would be oxidized to an aldehyde, not an acid.
Explain concisely why the oxidation stops at the aldehyde stage using PCC.
(i)

flow, all intermediates and all steps clearly.
6
(ii)
+~
2. Heat
CQ
If 1,3-cyclopentanedione were used as the substrate instead of

cyclopentanone under the same reaction conditions, what would be the
product?
(iii) Would you expect the reaction using 1,3 -cyclopentanedione to occur at a
faster or slower rate? Why?
(12 marks)

5.
(a)
heat
0
(b)
(c)
BB
NaOEt, EtOH
130 C
(d)
Sn/HCI
(c)
EE
1) HCl, NaN0 2, 0-5 C

2) CuBr, 100 C
(f)
GG
1) BuLi
(g)
2)
~Br
(20 marks)
6.
(a)
Picric acid is exceptionally acidic (pKa
0.38). Explain why.
OH
02N*N02
I~
.b
picric acid
N02
(b)
(3 marks)
Indicate the most basic site in the following molecule and briefly explain your
answer.
(3 marks)
7.
Outline a reasonable mechanis1n for each of the following transformations.
(a)
(b)
NaNH2
NH 3 (liq.)
(c)
..
NaOEt
(12 marks)
8.
Suggest a short synthesis for each of the following con1pounds from the indicated
starting n1aterials and any other reagents.
(a)
~~02
~
Cl
frotn
N0 2
(b)
o-z
6
0
from
~COO Et
(c)
fron1
and PhCH 2NH 2
(12 marks)
-END OF PAPER-

27 May 2002 (Monday)
9:30am- 12:30 pm
candidate's responsihility to ensure that his/her calculator operates satisfactorily.

1.
Provide the structures of the major products A to ~ in the following reactions. Show
clearly the stereochemistry of the products where applicable.
~0~
(a)
(b)
(~"//'"' PPh
(d)
heat
(c)
8
Br
1. ~Li
2.
/"'~~
(f)
/~/lH
heat
E
(6 marks)
2.
Draw detailed, reasonable mechanisms for the following reactions.
0
(a)
refluxing benzene
1\
HN
0
\__/
o~cb
0
(b)
(c)
eO
~OH
~H
NaOH, H2 0
ea~~)
.._.._~
acetone
(10 marks)
3.
Determine whether the following compounds are aromatic or non-aromatic. Provide

sufficient reasoning for your conclusions. For each compound, outline the chemical
and spectroscopic properties that you would expect based on your conclusion about its
aromaticity.
(a)
(b)
(6 marks)
4.
ANSWER FOUR OUT OF THE FOLLOWING FIVE QUESTIONS.

The reactions below DO NOT give good yields of the desired products.
question:
For each
(i)
state concisely WHY these reactions do not give the desired products,
(ii)
what are the products that would result if these reactions were carried out as
shown, and
(iii) propose alternative reagents, reactions and/or reaction conditions to obtain good
yields of the desired products starting from the given substrates.
0
(a)
~H
VI
!\
2.
(b)
1 equivalent LiAIH 4
;\
ether
(c)
~Cl
V
;\
(d)
NaOH,
Br2
~Br
;\
(e)
~
I
;\
THF
(12 marks)
5.
ANSWER FOUR OUT OF THE FOLLOWING FIVE QUESTIONS.

Design efficient syntheses of the following compounds starting fron1 the given
substrates. You may use any other reagents as necessary. If more than one step is
required, provide the structures of the intermediates after each reaction step.
(a)
from
(b)
from
ethyl benzene
(c)
from
(d)
from
(e)
from
(16 marks)
6.
Each of the following reactions gives a single product In good yield. Draw the
structures for the products G- 0.
(a)
1.
(b)
OJ
1. SOCI 2,
tl
OH
2. LiAI[OC(CH 3 )bH
-78C
(c)
1\
02N--Q-F
\_/
NH
(1 equiv.)
(d)
(X>
N
H
1. excess CH 3 1
2. Ag 20, H20
3.
(e)
CNH
PhCHO I H+
!S
NaBH 3CN
(f)
coo- (Ca 2+/2)
HtOH
HO
OH
OH
CH 20H
Fe(OAc)3
b
30% H202
6
(g)
()=a
(h)
(i)
(18 marks)
7.

(a)
NaOH I Br2
~NH 2
H2 0
~NH 2
(b)
QBr
h-
Br
(Ph
1. n-Buli
2.
a=o
N
::-.N\
Ph
(c)
0
~
0
(12 marks)
7
8.
Propose reasonable syntheses of each of the following compounds from the given
starting materials and any necessary organic or inorganic reagents.
(a)
~from
(b)
OH
HO~Q
HO~ OH
OH
(8 marks)
9.
Suggest suitable reagents (i- xii) for each step in the following synthesis.
(a)
~NH2
ii
______
ii_i__~
iv
o-~
(b)
OH
~H
OAc
o+CN
vi
~NHAc
vii
(c)
H3CO~OCH3
viii
ix
04:CH3
(d)
DOH
J0Br
Br
xi
xii
J00H
OH
(12 marks)
-END OF PAPER-


May 29, 200 I (Tuesday)
9 30 am- 12.30 pm
Cand1date1 lllllf' 111e any \elf-contmned 1ilent, ballery-operated and pocl..et-sl=ed calculator The ca/cula/01
~hould have m1me1 al-d11plal' facllilie.\ only and 5hould be used only for the pw poses of calculallon It 1s !he
candidate '.1 re11W1111hiluy 10 emu re that hHihet calculator operates sa/isfactot t!v
Cam/idate\ 111111t 1 eco1 d the name and type of theu calculato1 ~ on !he ji 0111 page of theu e.\amuw/1011 5CI 1pls

Answcrquestions 1-3 in RED covered answer book and
qucstiom 4-8 in BLUE covered answer book
Pwvide the structures of the maJor products ,& to m the followmg reactions. Show
clearly the stereochemistry of the products where applicable.
HCI
NaCN
(a)
A
-
H:20
~MgBr
(b)
-8
d1ethyl ether
c-
0
catalytic Os0 4
(c)
catalytic H2S04
-E
CeHe
(d)
excess
L1AIH 4
0
F
d1ethyl ether
(14 marks)
Choose TWO of the followmg three questiOns to answer. For each questiOn, give a
detailed mechanism for the reaction shown in (i). Then give a concise answer to the
quest10n(s) in (i1)
(a)
(i)
benzene
reflux
( ii)
(b)
Why is the enamine
>--
r-\
N~
not formed?
0
(1)
OH
OH
acetone
HO
HO
(ii) Why is 1t that only one of the hydroxyl groups 1s ox1d1zed

1n th1s react1on?
(c)
(1)
0
NaOCH 3
/Jt'"
-
CH 3 0H
'~~
NaOCH 3 , CH 3 0H
0
.... '-._
//", ',
f',)~)<o
heat
(11)
What is the name of this overall sequence of reactions?

What factors account for the success of the final aldol
react1on between two ketones?
(10 marks)
3
3
The six reactiOns proposed below DO NOT give good yields of the desired products
For any four of the reactiOns.
(i)
(n)
state concisely m pomt form WHY the reaction does not give the desired
products, INCLUDING what products would result If these reactiOns were carried
out as shown, and
propose alternative reagents, reactions and/or reactiOn conditions to obtam good
ytelds of the desired products startmg from the given substrate
(a)
THF
(b)
(c)
/
THF
(d)
(e)
(f)
C)
()
OH
Br
NaOCH 2CH 2CH 3
CH3CH2CH20H
CH 3CH 2 MgBr
catalytic H2 S04
diethyl ether
heat
/0,~
GJ
(16 marks)
From each set of compounds, Identify the most acidic proton(s).
(a)
~/COOH
~../ COOH
(b)
/"I
/"I
/"I
:-...
Cl
MeO
COOH
(c)
COOH
COOH
~/COOH
/"I
::-...
(d)
(e)
(n-BuhNH
R-~-CH2-g-OCH2CH3
(f)
(6 marks)
Each of the followmg reaction5 g1ves a smgle product m good yield Draw the structure
fm the product~!!-~
0
1) LOA
(a)
-H
I-
(b)
--OH
(c)
--...-OH
OH
1) NH 20H
(d)
2) Ac 20/Et 3 N
(excess)
(c)
L
-
0
1) HCI, EtOH, b.
(f)
+
2) NaOH, H 2 0
M
-
Cl
HN:J
(g)
-N
(14 marks)
Give the structures of products Q-I m the followmg synthetic schemes.

HCI
-0
(a)
CuBr
____..
-Q
0
1) EtOH/H+
1) SOCI 2
(b)
2) 2 eq NH 3
-u
-5
1) Me I (excess)
NaHC0 3 (excess)
V
-
( 16 marks)
Outlme a reasonable mechamsm for each of the followmg reactions.
0
11
Ph-C-0-H
(a)
0
N
(b)
(c)
NH 3 (hq)
(12 marks)
P1eparc each of the followmg compounds from the given startmg matenals and any
ncccs~ar y morgamc reagents.
f10m
(a)
0
(h)
from
and
NaOEt
v
+
_....NH 3
(c)
.____.
>--CH 2-CH,
coo-
f10m
(12 marks)
-END OF PAPER-

BACHELOR OF SCIENCE: FINAL EXAMINATION
Chemistry CHEM2402 Intermediate Organic Chemistry
May 26, 2000 (Friday)
2:30 pm - 5:30 pm
Candidates may use any self-contained. silent. battery-operated and pocket-sized calculator. The calculator
should have numeral-display facilities only and should be used only for the purposes of calculation. it IS the
Candidates must record the name and type oftheir calculators on the front page of their examination scripts.

Answer questions (1-2) in RED covered answer book and
questions (3-7) in BLUE covered answer book
1.
(a)
Propose reasonable syntheses for TWO of the following molecules from the given
starting materials and any other substrates and reagents.
~OH
from
any alcohol and alkyl halide
from
from
(8 marks)
(b)
Draw detailed mechanisms for the following transformations:

0
HO~
OH
benzene, reflu x
p-toluenesulfonic acid (catalyst)
benzene, reflu x
(8 marks)
..
2.
Draw the structures of the products (A -1), showing stereochemistry where applicable:
(a)
(b)
CIUC03H
'6
~I
LiAIH 4
f!
ether
CH2CI2
cYH
(i) H2C=CH CH 2CH 2Mg8r
(ii) aqueous workup
pyridinium
chlorochromate
Os04 (catalyst)
Q
t-BuOOH
CH2CI2
(c)
OH
HI04
f. and G
HO
(d)
11
--<Jo
CH 3 CH 2CH 2- Mg8r
CH3C-C1
.!::!.
ether
(e)
CY'
(f)
CH2CI2
pyridine
a~H
NH
J
benzene. reflux
NaOH
H20
CH3CH20H
.!S
.b
HCI
(24 marks)
3.
(a)
Label the most acidic proton in each of the following molecules. Give a brief
explanation of your choice.
11
H3N -CH-C-OH
I
CH 3
HOt~:::H
yo
HO
OH
(3 marks)
(b)
Rank the basicity of the following compounds. Give a brief explanation.
~5
N
H
(3 marks)
4.
Each ofthe following reactions gives a single product in good yield. Draw the structure
for the products (M - ).
(a)
1) Fe, HCl
Br-Q-ON02
2) Of1
(b)
2) CuCN
l) Mel (excess)
MeOH, heat
0
l) NaN0 2, H2S04
160 oc
HO
(c)
HO~q
NaBH4
HO~OH
Me OH
OH
(d)
Me0H
Me
1)
Q
H
2) CH3CH2Br
3) H 30+
(e)
(14 marks)
5.
Suggest suitable reagents (i- x) for each step in the following syntheses.
(a)
CX
OH
OH
(i)
H~H
oAH
(ii)
(iv)
(b)
(v)
(vi)
(c)
OMe
(viii)
(d)
OMe
Me,S~H
-.
(ix)
OMe
NH2
Me,S~CN
NH 2
Me,S~C02 H
(15 marks)
6.
Outline a plausible mechanism for each of the following reactions.
(a)
Me,, Q
Me~
. ui-Bu
t-Bu
HSD
spontaneous
(b)
PhH
Ph ~ Ph
(c)
Ph
OH""
Ph~ Ph
0
(d)
C(Br
.
(e)
0
0
Mg
THF
MeO~
(15 marks)
.,
7
7.
Propose a synthetic scheme for each of the following compounds from the given
starting materials and any necessary organic or inorganic reagents.
(a)
from
(b)
from
D
0
(c)
Ph
from
and
Ph
( l 0 marks)
-END OF PAPER-

Hku Organic Chemistry 2 Final Exams

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THE DIVERSITY OF HONG KONG

CHEM3441B Organic Chemistry II

May 23, 2016 (Monday)

Answer ALL questions in Section A in RED answer book. (Total 30 marks)

Section A (Total 30 marks)

_________ JL_!L_ _ _____

--- - ---,1,0~=0-~-----------,-- ---- -----.-- _1,23 ___

(b) Based on the following spectroscopic data of an unknown compound with

Arn.:t;x 235nrn (Jog 10 s 4.tl

A.~nu~ .2.65 hm (log 10 c 3,0 i

(tC:to MHz. COCl 1 s::dub:m)

CH?. CH~t CHt

{400 MHz, .COCI ~ Sl)lution)

Section B (Total 70 marks)

Provide the missing reagents, reaction conditions or structures of the major

(a) Benzyne is a highly reactive molecule that 1s produced as a short-lived

i) Would you expect benzyne to be aromatic? Explain your answer.

6'H QH 'H SOH

(c) Compound AA is converted to compound BB on treatment with sodium

Propose a reasonable mechanism for each of the following transformations. Show

THE DIVERSITY OF HONG KONG

CHEM3441C Organic Chemistry II

Answer ALL questions. (Total 100 marks)

Answer ALL questions. (Total 100 marks)

Provide the missing reagents, reaction conditions or structures of the major

_!:L.. - < - o - < H O __!.....

Benzyne is a highly reactive molecule that is produced as a short-lived

Arrange the following compounds in order of increasing acidity. Explain

Write a reasonable mechanism for the following transformation.

i) excess MeMgBr, THF

Suggest why the reaction fails;

Compound R is converted to compound . on treatment with sodium

Propose a reasonable mechanism for each of the following transformations. Show

THE DIVERSITY OF HONG KONG

CHEM3441 Organic Chemistry II

Answer ALL questions. (Total 100 marks)

Answer ALL questions. (Total 100 marks)

Provide the missing reagents, reaction conditions or structures of the major

2) Ag 20, H20, heat

The mechanism of the following transformation (~ to Q) has been studied by

For the following two reactions,

i) Give the structures of major products and Q.

Propose a reasonable mechanism for each of the following transformations. Show

then, HCI, H20, reflux

1) LDA, THF, -78 C

THE DIVERSITY OF HONG KONG

CHEM2403 Intermediate Organic Chemistry

May 20, 2015 (Wednesday)

Answer ALL questions. (Total 100 marks)

Answer ALL questions. (Total 100 marks)

Provide the missing reagents, reaction conditions or structures of the major

Picric acid is exceptionally acidic (pKa = 0.38). Explain.

Which of the following molecules (N and 0) will not undergo

For each of the following compounds, indicate if it is aromatic or not.

Rank the basicity of the following compounds. Explain your answer.

Propose a reasonable mechanism for each of the following transformations. Show

THE DIVERSITY OF HONG KONG

CHEM2403 Intermediate Organic Chemistry

2:30 pm- 5:30 pm

Answer ALL questions. (Total 100 marks)

Answer ALL questions. (Total 100 marks)

Provide the missing reagents, reaction conditions or structures of major products

CH 2Cl 2, room temperature