CHE 321 Exam 2 Form 0 page 1

The first 12 questions are 5 point multiple choice questions and should be answered
by filling in the appropriate bubble for each question.
Questions 13-16 are 10 point short answer questions and should be answered in the
space provided on the front and back of the answer form.
1
H-NMR Chemical Shifts

Infrared Absorption Frequencies

CHE 321 Exam 2 Form 0 page 2
Multiple Choice Questions. 60 points

1. Choose the correct order of acidity for the following compounds (most acidic on right).

O O O
C C C
CH 3 OH CF 3 OH CH 3 NH 2
1 2 3

A. 3<1<2 B. 1<3<2 C. 2<3 <1 D. 3<2<1 E. 1<2<3

2. The pKa values of aspartic acid, a naturally occurring amino acid

are shown to the right. Choose from below, the structure of the pKa = 3.86 pKa = 9.82

major species present at a pH of 7.2. NH3

HO C CH2 CH
O C O
ascorbic acid
pKa values OH
pKa = 2.10

NH 3 NH 2 NH 3 NH 3 NH 2
HO C CH 2 CH HO C CH 2 CH HO C CH 2 CH O C CH 2 CH O C CH 2 CH
O C O O C O O C O O C O O C O
OH OH O O O
A. B. C. D. E.

3. Choose the incorrect statement about the following catalytic hydrogenation.

CH3 CH3
CH3
H2-Pd/C H H
+
H CH3
CH3
CH3 H
major minor

(A) The syn addition of hydrogen gives the cis isomer as the major product.

(B) The minor product occurs as the result of a catalyzed isomerization of the reactant..

(C) The catalyst (Pd/C) speeds up the reaction by stabilizing the major product of the reaction.

(D) The minor trans isomer is actually present as a racemic mixture.

(E) The reduction of 3,3,6,6-tetramethylcyclohexene would be predicted to occur at a slower reaction rate.
CHE 321 Exam 2 Form 0 page 3

4. Choose the incorrect statement about the following acid/base reactions involving propyne and its anion
propynide.
(i) CH3CCH + OH CH3CC + H2O pKa
(ii) CH3CCH + NH2 CH3CC
+ NH3 H2O 16
CH3CCH 25
NH3 34

(A) The equilibrium in equation (i) lies to the left.

(B) The equilibrium in equation (ii) lies to the right.

(C) You can prepare propynide, CH3CC-, salts in NH3. .

(D) Propyne, CH3CCH, is a stronger acid than ammonia, NH3.

(E) In reaction (ii) ammonia, NH3, acts as a base.

5. In addition to 2-butanone, a second product is formed in the following acid-base reaction. Choose the
structure for this second product.

O H O
H H C
H C H C H
C C + H C Br H C C + Br
H H H
H H H H H
acetonate ion methyl bromide 2-butanone

H
C H
H O
H O OH O H OH
H C H C H
H H C C C C H H C H H C H H C H C C
C C C C C C H H
H H H CH 3 H H H H H C H
H H H H H H H H H H
H
(A) (B) (C) (D) (E)

6. Choose the incorrect statement about the following two alkenes.

(i) (ii)

(A) Alkene (i) is more stable than alkene(ii).

(B) Hydrogenation of achiral alkene (i), will give chiral products.

(C) Hydrogenation of chiral alkene, (ii), will give a chiral product.

(D) Hydrogenation of alkene (ii) will yield more heat than will hydrogenation of alkene (i).

(E) The two alkenes (i) and (ii) are configurational isomers.
CHE 321 Exam 2 Form 0 page 4

7. Supposed you carried out the hydroboration of 1-methylcyclopentene:

CH 3
1. BH 3
2. H 2O 2, NaOH
?

Choose the correct answer for the products formed in the above reaction.

H 3C H H 3C H H 3C OH H CH 3 H CH 3
H OH H H OH
OH H H OH H

1. 2. 3. 4. 5.

(A) An equal mixture of 1 and 5.

(B) An equal mixture of 1 and 2
(C) An equal mixture of 2 and 4
(D) An equal mixture of 4 and 5
(E) Compound 3 only

8. The ozonolysis of limonene (oil of lemons) give compound X plus formaldehyde. Choose the correct structure
for X.

CH 3

1. O 3 O

2. (CH 3)2S
X +
H H

H 3C
Limonene

O O O O O
CH 3
H 3C H H 3C H 3C CH 3
CH 3 O H
H O
A. O B. C. O

O O
H3C O
H CH 3
H CH 3 CH 3

O D. O E. O

9. Which one of the following structures would be named, (2Z,4E)-2,4-heptadiene?

A. B. C. D. E.
CHE 321 Exam 2 Form 0 page 5
10. You have a compound of formula C4H8O2. Which structure shown below is consistent with the following IR
spectrum?

OH
O O O O O
O
HO O H O
A. B. C. D. E.

11. You have a compound of formula C4H8O2. Which structure shown below is consistent with the following NMR
spectrum?

OH
O O O O O
O
HO O H O
A. B. C. D. E.
CHE 321 Exam 2 Form 0 page 6

12. Which of the following reactions is incorrect?

HO CH 3 + enantiomer

A
1. Hg(OAc)2
2. BH 4- Br OH
+ enantiomer

Br2/H 2 O E
H CH 3
H 2/Pd-C + enantiomer
B
Br2
H OH
1. BH 3
Br Br
2. H 2O 2, NaOH
D
C + enantiomer

+ enantiomer

The following short answer questions are worth 10 points each.

Draw a curved arrow mechanism for the following reaction.

H 2O
H 2O H
CH 3 H O CH 3 HO CH 3
H 3C H 3C
+ CH 3
H CH 3
CH 3

H 2O

13. Complete the following reactions by supplying the missing reagents.

a.

Br H
Br2

Br H + enantiomer

b.

1. Hg(OAc)2
2. BH 4-

OH + enantiomer
CHE 321 Exam 2 Form 0 page 7

14. Here is an unusual reaction we have not yet discussed in the course. The reaction of ethylene with butadiene
to give cyclohexene.

Here we show the reaction using arrows

Here are the relevant orbitals of butadiene and ethylene.

Specify the symmetry of each of the following molecular orbitals

Butadiene HOMO A or S (circle your choice)

Butadiene LUMO A or S
Ethylene HOMO A or S
Ethylene LUMO A or S

The reaction is allowed by orbital symmetry True or False

CHE 321 Exam 2 Form 0 page 8
16. Compound A is an achiral alkene of formula C8H16. The NMR of A is shown below.

Oxymercuration of A gives a chiral alcohol, X, plus its enantiomer. Hydroboration gives the same products, X,
as does the oxymercuration reaction.

Bromine addition in H2O gives compound, B, and its enantiomer.

Oxidation of A by OsO4 gives an achiral diol, Y.

Ozonolysis of A gives a single compound C, with formula C4H8O. C has the NMR shown below.

B plus enantiomer

1. Hg(OAc)2 Br2 / H 2O
2. BH 4-
1. OsO 4
2. NaHSO 3/H 2O
X A Y
achiral alkene achiral diol
chiral alcohol
C 8H 16
plus enantiomer 1. O 3
2. (CH 3)2S

A
1. BH 3
2. H 2O 2; NaOH
C C 4 H 8O

H H

C8H16 - achiral alkene A

12 H doublet Br H

B
HO H
2 H doublet 2 H multiplet
(many peaks)

H C
C4H8O - ozonolysis product C

6 H doublet

1 H multiplet
1 H doublet (many peaks)

Draw structures for A, B, and C on your answer sheet. (You do not need to give structures for X and Y)