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Tufts University Summer 2013

Chem 52 - Organic Chemistry II
Practice Exam 1A

I. Multiple Choice I (13 questions, 2 pts each, 26 pts overall)

1. The IUPAC name for diisobutylacetylene is
A) 2,7-Dimethyl-4-octene
B) 2,7-Dimethyl-4-octyne
C) 3,6-Dimethyl-4-octyne
D) 2,5-Diethyl-3-hexyne
E) 2,2,5,5-Tetramethyl-3-hexyne


2. Regarding the use of potassium tert-butoxide as a base in E2 reactions, it is incorrect to
state that:
A) it favors E2 reactions over competing S
N
2 reactions.
B) it will form, predominantly, the more stable alkene.
C) it tends to give the anti-Zaitsev, i.e., Hofmann, product.
D) it is more reactive in dimethyl sulfoxide than it is in tert-butyl alcohol.
E) this base is more effective than ethoxide ion, because it (KO-t-Bu) is the more basic
of the two.


3. What is the major product of the reaction:

A) I
B) II
C) III
D) IV
E) Both III and IV


i) BH
3
, THF
ii) H
2
O
2
,NaOH
CH
3
CH
3
OH
OH
CH
3
I II III IV
CH
3
OH
?
+
enantiomer
+
enantiomer

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4. Which reaction sequence would convert cis-2-butene to trans-2-butene?
A) Br
2
/CCl
4
; then 2 NaNH
2
; then H
2
/Ni
2
B(P-2)
B) Br
2
/CCl
4
; then 2 NaNH
2
; then Li/liq. NH
3

C) H
3
O
+
, heat; then cold dilute KMnO
4

D) HBr; then NaNH
2
; then H
2
, Pt
E) None of these


5. Cyclohexene reacts with bromine to yield 1,2-dibromocyclohexane. Molecules of the
product would:
A) be a racemic form and, in their most stable conformation, they would have both bromine
atoms equatorial.
B) be a racemic form and, in their most stable conformation, they would have one bromine
atom equatorial and one axial.
C) be a meso compound and, in its most stable conformation, it would have both bromine
atoms equatorial.
D) be a meso compound and, in its most stable conformation, it would have one bromine
atom equatorial and one axial.
E) be a pair of diastereomers and, in their most stable conformation, one would have the
bromines equatorial and axial, and the other would have the bromines equatorial and
equatorial.


6. Compound X has the molecular formula C
6
H
10
. X decolorizes bromine in carbon
tetrachloride. X also shows IR absorption at about 3300 cm
-1
. When treated with
excess hydrogen and a nickel catalyst, X yields 2-methylpentane. The most likely
structure for X is:
A)

B)

C)

D)

E)




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7. Which of the following species is not a resonance form of the following species?

A)

B)

C)

D)

E)



8. Which statement is/are true about alkynide anions?
A) They are weak bases and weak nucleophiles.
B) The carbon atom that bears a negative charge is sp
3
hybridized.
C) With a tertiary alkyl halide, an alkynide anion will act as a nucleophile to produce high
yield of an alkylation product.
D) All of the statements are true.
E) None of the above is true.


9. Which of these dienes can undergo the Diels-Alder reaction?
A)

B)

C)

D)

E) All of the above can undergo the Diels-Alder reaction.


O
O
O
O
O
O

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10. Free radicals can be produced by:
A) use of high temperatures.
B) irradiation with light.
C) reaction of a molecule with another free radical.
D) both A) and B).
E) all of A), B) and C).


11. Which of the reactions listed below would be exothermic?
A) CH
3
CH
3
2CH
3

B) CH
3
+ CH
4
CH
4
+ CH
3

C) 2(CH
3
)
2
CH (CH
3
)
2
CHCH(CH
3
)
2

D) H + (CH
3
)
3
CH (CH
3
)
3
CH + H
E) None of the above


12. Which would be the best synthesis?


A)

B)

C)

D)

E)



13. The reaction of 1-butene with HBr in the presence of peroxides yields 1-bromobutane.
The mechanism for the reaction involves:
A) attack on the alkene by a Br
+
ion.
B) attack on the alkene by a H
+
ion.
C) attack on the alkene by a bromine atom, Br.
D) attack on the alkene by a hydrogen atom, H.
E) isomerization of the 2-bromobutane produced initially.


CH
2
CHCH
3
?
CH
2
CHCH
2
Cl
Br Br
Propene
Br
2
, CCl
4
Cl
2
, h
Propene
Cl
2
, 400
o
C Br
2
, CCl
4
Br
2
, h
Propene
HCl
Propene
Cl
2
, CCl
4
NBS, CCl
4
Propene
Cl
2
, CCl
4
NBS, CCl
4

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II. NMR (4 pts)

What is the structure of the compound in the following
1
H-NMR spectrum with the
molecular formula C
6
H
12
? Relative integration is shown.

A)

B)

C)

D)

E)




0 1 2 3 4 5 6 7 8
PPM
2
1
3
6

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III. Spectroscopy (8 pts)
An unknown compound, Y, has the formula C
6
H
4
Cl
2
O. Elucidate the structure of Y by
scrutinizing its IR,
1
H NMR and
13
C NMR spectra, shown below.


Note: the triplet in the
13
C NMR spectrum at 82 ppm is due to the solvent, CDCl
3



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IV. Reactions (14 pts)

A. (10 pts) Draw the major product(s) after each arrow in the following reactions.
Clearly depict stereochemistry where appropriate.

i)
cold conc. H
2
SO
4



ii)
1. O
3
2. Me
2
S



iii) CH
3
CH
2
CH
2
CH
3
+ Br
2
(UV radiation)
excess



iv)
HI (1 equivalent)
+40
o
C





B. (4 pts) Provide reagents for the following transformations.


Br
CH
3 O
+ CO
2






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V. Mechanisms (14 pts)
Provide a detailed mechanism (with electron flow arrows) for the following reactions.
Clearly show the final product formed. (If you cannot predict the mechanism, there will be partial
credit for showing correct products). If several products may form, only show the major one.

a) (6 pts) H
2
C=C(CH
3
)
2
+ HF














b) (8 pts) Radical polymerization of CH
3
CH=CH
2
initiated by peroxide H
2
O
2









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VI. Radical Reactions (10 pts)

Using bond dissociation energies, calculate the heats of the two possible reactions of the isopropyl
radical, (CH
3
)
2
CH with HBr leading to the abstraction of either H or Br atom.
Draw the energy diagram for these two reactions.
Which of them is more likely to occur?




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VII. Synthesis and Nomenclature (12 pts)

a) (6 pts) Propose a method for the stereoselective synthesis of the following molecule.
from
HO OH
(racemic)
and
Cl
CO
3
H
and any inorganic
reagents














a) (3 pts) Propose a one-step method for the stereoselective synthesis of the following molecule.

F F
starting from
molecules with
four carbon atoms
or less








b) (3 pts) Name this molecule using the R,S system and IUPAC nomenclature.

F F




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VIII. Open Response (12 pts)

1. (2 pts) Draw the structure of (Z)-1-bromo-2-chloropropene





2. (2 pts) What monomer should be used to prepare -(CH
2
-CH=CH-CH
2
)
n
-?






3. (2 pts) Give one example of a catalyst that can be used for the hydrogenation of alkynes to
alkanes.





4. (2 pts) How will the reaction products of the addition of HCl to propene differ in the absence and
presence of peroxides?






5. (2 pts) What simple text can be done to distinguish between 1,3-pentadiene and 1,4-pentadiene,
other than running a proton NMR spectrum?






6. (2 pts) Draw two resonance structures for the allyl cation. Show all carbon and hydrogen atoms.