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MULTIPLE CHOICE.

Choose the one alternative that best completes the statement


or answers the question. (20 marks, 2 marks each)

I. Which is the base peak?

100­
80­

~
if.! 60 ­
C
ID
C 40­
20 ­

10 20 30 40 50
m/z

A) 100
GV C) 45 D) 15 E)44

2) Which of the following characterizes the unusually intense peak of alkyl chlorides in
MS spectrometry?

+ 2 peak C) base peak D) parent peak E) none of the above

3. Which one of the following best represents the predicted approximate chemical
shift and coupling for the hydrogen(s) indicated with the arrow?
o
~...-
A) 1.00 ppm, quartet

B) 2.40 ppm, singlet

(3) .00 ppm, triplet

D) 2.40 ppm, quartet

E) 3.00 ppm, quartet


4 . The IH NMR spectrum of which of the compounds below, all of formula
C7H1202, would consist of two singlets only?
0 0
0 0
)~o o~ ~)

/\
I II III
0 0 0

07~~ ~~
N V

A) III B) IV C)II (£J


E) I

5. Select the structure that is consistent with the formula and spectral data below.
Formula lH NHR Spectrum Infrare,d Spectrum
wHO
. 8 triplet, C1.05 (3H ) 1720 em - 1 (streng)
singlet, 02.13 (3H)
quartet; 02.47 (2H)

B) C)

D) E)

6. How many signals are in the 13C NMR spectrum of the following compound?

OH

A) 4 B)8 C)5 E)3


7. What functional groups are shown in the IR spectrum shown below? The

compound responsible for this spectrum is the principle ingredient in oil of

cloves. This compound is used not only in perfumes and mouthwashes, but also as

an insect attractant and a dental analgesic.

lOD,---------------------------------------------------------------------------,

50

O+-~~~~~~_r~~~~~~~--~~--~~--r_~--~~--~_,~--~~--~_.~
4000 3000 2000 1500 1000 500

A) Alcohol

B) Ketone

C) Aldehyde

D) Ester

E) Carboxylic acid

8. Which cyclization(s) should occur with a decrease in pi-electron energy? i.e. more

stable?

I CH 2 ==CH-CH==CH 2 .. D + H2

A) I E) all of the above

9. Which would be the product of the following reaction sequence?

i) pas
<Q)-k:H ii) benzene, AI at
?
iii) Zn(Hg), HCI

Q-S02--o Q-co2--o Q-CH2--o


II III

o
Q--lLQ
N v
A) IV 8) III C)V D) I E) II

10. What would you expect to be the major product obtained from the following
reaction?

1 equiv. Cl 2 .)

FeCb

(:1

'~I

.: 1
n ill

0::1

'~I

IV V

A) II 8) IV C)V D) I
G

[;/

Name
-------------------------------
Student Number
----------------------
SHORT ANSWER QUESTION

2. Propose structures for compounds X, Y, and Z:

NaCN

The IH NMR spectrum of X gives two signals, a multiplet at 8 7.3 (5H) and a singlet at 0
4.25 (2H); the 680-840 em-I region of IR spectrum of X shows peaks at 690 and 770
em-I. The IH NMR spectrum ofY is similar to that of X : multiplet at 8 7.3 (5H), singlet
at 8 3.7 (2H). The IH NMR spectrum ofZ is shown in a figure below. Integration values
from left to right are 5 :2:2:2. Please show your work for the full mark. (10 marks)

-* 5 ~e (\ ~ Y"V' \2) 'y~~ .( (lJ {\n 9v---e ~~ Ie f'\ .sJ


~. H- C\'\~ \ -£,.r\0 d
tN\. ~ \r"\.(An tAk ~uleJ .

Figure. The 300 MHz IH NMR spectrum of compound Z. Expansion of the signals is
shown in the offset plot.

X: Y:

Name
---------------------------------
Student Number
Answer for question 2 continued:
------------------------

Section II.

Short Answer Questions

Please Provide the Answers on the Answer Sheet.

1. Provide the major organic products of the following reactions . Show only major
products and stereochemistry if necessary. (25 marks)
~~----~------------------.
a) Et

~
~~

I N
#
(2)
~------------------------~

~O-I
O\-\
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _~ (2)
o

6
c)

2. EtOH
o
Q
~______________________~(2)

/6 marks
d)
o)~
-0 ~
JH ~========~
l-h.,L/' I
..
'----_ _ _ _ _ _ _ _ _---.J (2)

I. HOCH 2CH 20H/H 30+ r-----------­


2. LiAIH4/Et20

D~~u\-)

'---_ _ _ _ _ _ _ _ _ _~ (2)

Sk ,'P
' -_ _ _ _ _ _ _ _ _ _--l (3)

g)
o

~
eN 0

' -_ _ _ _ _ _ _ _ _ _ _...-J (2)

h)
I. ~ONa

2 ~ 3
_2._H_ 0_________
+ ..
U
OEt ~I\.~
3. NaOH, H20 , heat
4. H30 +!heat

~_ _ _ _ _ _ _ _ _~ (3)

- -112 marks
Name

Student Number

i) 0 1. LDA 0

2. ~H .­ o UH
3. H2O

i) I-ltJ ~Ur\) N r
~ (2)

.2) MiNv..}~; (€){U),'

j)
0
~H~UI-
Et'o~
OH

0
4) A1,0H~ ~ ~~V~
~ OH
(3)

1. /""-ONa//""-OH
k) 0
~O
0

/'-O)UO~
0
2.

3. HC], H 2 0 , heat
.­ Q o
(3)

0
1)

Br
LDA, THF, _78°C
.- oA
U (2)
1. H30+ cat.
m) 0
2'
V Br

6
0
+

~
-.
CNH
3. H30+

(2)

;t .~ _
~\ d&/' \t- 'l-~ 9 ~vl ~\.cA(\·.\-
~~'" ~ \- C-t.)k..
t."...( \ c.- {'\
')
- -112 marks

Name
Student Number

0 I. NH3 excess

~I
n)
2. LiAIH~
~

3. H2O ~N\'-~

(2)

0)
I I. H 20 2
VN~ ~

1# 2. heat
sk\'p
(2)

p) oCOOH I. acetyl chloride;


Alel 3
.. Stl\P
s

(2)

/6 marks

2. Considering only the shown hydrogens, list the following compounds in order of
decreasing acidity: (5 marks)

I most acidic I
> -sr: > > >

lea>t aac§]
Name
------------------------------
Student Number
---------------------

3. Write a mechanism for the base-catalyzed conversion of D-fructose into 0­


glucose and D-mannose. ( 8 marks)
Name
-----------------------------
Student Number
--------------------
4. Give product(s) and show intermediate products if necessary for each of the following
reactions: (9 marks)

1. HeN
2. H2/PdIBaS04 C 2H sOH/H 3 0+
A + B ~ + Enantiomer of ------I.~ C + D
L-xylose

skip

Name
------------------------------­
Student Number
----------------------
5. Show how each of the following compounds could be synthesized. You may use any
inorganic or organic reagents . Multiple steps may be required. (31 marks)

a) The mandibular glands of queen bees secrete a fluid that contains a remarkable
compound known as "queen substance" . When even an exceedingly small amount
of the queen substance is transferred to worker bees, it inhibits the development of
their ovaries and prevent workers from bearing new queens. Queen substance, a
monocarboxylic acid with the molecular formula CloH1603, has been synthesized
by the following route:
I. CH3Mg1 HA, heat I. 0 3
Cycloheptanone
2. H 30+ 2. Me 20 (reductive workup)

I 0 0
. ~ ,pyridine
MeO OMe
----~ C (C g H I4 0 2 ) .. queen substance (C to H I6 0 3)

Provide structures for the queen substance and compounds A-C.

A: B:

I
~

c: Green substance:

s~ \P (10 marks)
Name
Student Number

b)

(6 marks)

c)
o

(7 marks)
Name" - - - - - - - - - - - - - - - ­
Student Number- - - - - - - - - - ­
d)

""-O~O/
o 0
()OH
iJ }.jV>. 0 fJle, I lUll 0\.-)

i) ~r~~~(-

o
" U ~\ ---~
Ki~O

(~---

't this '') !A ~ (;L b ( I ~N ~~ i"f\ 4'V--r \ ~ l~

C1 ~¥- 'V(\ \t s) 'IJ .s~ f\ (J0-- (8 marks)

s,uf\'€. J,-\,\ W\.~ \Ito S' 1\/\ '\L-\ r , .

Name
-----------------------
Student Number
----------------

6. Propose a mechanism for each of the following reactions. Please show mechanism for
every step and resonance structures wherever it is necessary. (40 marks, 10 each)

a) 1. NaOCH 3 ;CH 30H o


~Br
2. •

'" ~ l ) 3. Hel, H,O, h~l


o
I GOL~\)
1
Name
------------------------
Student Number
------------------
b) Propose initial compounds and a mechanism for the synthesis of the following
compound using a Robinson annulation:
o

7t--. {\0 ~ ~ ?u(\~~D'Lt

+h\~ C/c .. \
Name
-----------------------­
Student Number
-----------------
c)

NHNH 2

HP + N0 2

• . ~
I + ?
~

N02
Name,----::-:-_ _ _ _ __
Student Number- - - - -

d)

o
+ Br2
excess Q o Br
+ HBr