MC-1 Consider the following species and pick the choice that best describes them.

a. NF
3
b. NH
3
c. HCO
3

d. CH
2
Cl
2


A. none of them is a Bronsted acid
B. two of them are Bronsted acids
C. three of them are Bronsted acids
D. one of them is a Bronsted acid
E. all of them are Bronsted acids



MC-2 Which of the following cyclic compounds are chiral?

H
3
C CH
3
.

Br
CH
3

CH
3
CH
3
H
3
C

CH
3
CH
3

CH
3
Br
.


a b c d e

A. a, d, and e;
B. a, c, and d;
C. a and c;
D. c, d, and e;
E. All.



MC-3 What factors will increase the rate of an S
N
1 reaction

1. Concentration of substrate 2. polar protic solvent 3. bulky nucleophile
4. concentration of nucleophile 5. more substitution at adjacent carbon
6. less basic leaving group

A 1, 2, 6
B 3, 4, 5
C 2, 3, 6
D 1, 4, 5
E 1, 3, 5

MC-4 For a substitution reaction at a secondary carbon, which of the following factors
are likely to cause the reaction to follow the second order rate law?

a. weaker nucleophile b. stronger nucleophile
c. increased concentration of nucleophile d. lower temperature
e. use of a polar protic solvent f) use of a polar aprotic solvent

A a, d, e
B b, f
C b, c, f
D a, d, e
E b, c, e

1X (12 points) Use the data in the table below to answer the following questions.
Show your work for all calculations.

pK
a
acid base
9.81 (CH
3
)
3
NH
+
trimethyl ammonium (CH
3
)
3
N trimethyl amine
10.81 C
2
H
5
NH
3
+
ethyl ammonium C
2
H
5
NH
2
ethyl amine
9.99 C
6
H
5
OH phenol C
6
H
5
O

phenoxide
3.73 HCO
2
H formic acid HCO
2

formate
4.76 CH
3
CO
2
H acetic acid CH
3
CO
2

acetate
4.63 C
6
H
5
NH
3
+
anilinium C
6
H
5
NH
2
aniline
6.37 H
2
CO
3
carbonic acid HCO
3

bicarbonate

A. The strongest acid in the table is _____________________________

B. The strongest base in the table is _____________________________

C. The weakest acid in the table is _____________________________

D. The weakest base in the table is _____________________________

E. The pK of the reaction of phenol with ethyl amine is _________

F. The pK of the reaction of ethyl ammonium with bicarbonate is
_________

G. Acetic acid, CH
3
CO
2
H, can be a Bronsted acid as well as a Bronsted base.
Using structural formulas, write the products of the reaction of acetic acid
with itself, showing the most important contributing structure for each of the
products.



____________________________________________
1Y (12 points) Use the data in the table below to answer the following questions.
Show your work for all calculations.

pK
a
acid base
9.81 (CH
3
)
3
NH
+
trimethyl ammonium (CH
3
)
3
N trimethyl amine
10.81 C
2
H
5
NH
3
+
ethyl ammonium C
2
H
5
NH
2
ethyl amine
9.99 C
6
H
5
OH phenol C
6
H
5
O

phenoxide
3.73 HCO
2
H formic acid HCO
2

formate
4.76 CH
3
CO
2
H acetic acid CH
3
CO
2

acetate
4.63 C
6
H
5
NH
3
+
anilinium C
6
H
5
NH
2
aniline
6.37 H
2
CO
3
carbonic acid HCO
3

bicarbonate

A. The weakest acid in the table is _____________________________

B. The weakest base in the table is _____________________________

C. The strongest acid in the table is _____________________________

D. The strongest base in the table is _____________________________

E. The pK of the reaction of formic acid with ethyl amine is _________

F. The pK of the reaction of ethyl ammonium with phenoxide is _________

G. Propionic acid, CH
3
CH
2
CO
2
H, can be a Bronsted acid as well as a
Bronsted base. Using structural formulas, write the products of the reaction
of propionic acid with itself, showing the most important contributing
structure for each of the products.



____________________________________________
2X (12 points) Part A. Draw a reaction profile for a two-step endothermic reaction in
which the first step is rate determining. Use the given well as your starting point.

Part B. Both ethanol and isopropyl alcohol react with HBr in water. Ethanol
follows a third order rate law and isopropyl alcohol follows a second order rate
law. Write the steps in the mechanism for each of these reactions (curved arrows
are not necessary).

1. Ethanol









2. Isopropyl alcohol









3. In ten words or fewer (only the first ten words you write will be read) explain
the change in mechanism.
2Y (12 points) Part A. Both ethanol and isopropyl alcohol react with HBr in
water. Ethanol follows a third order rate law and isopropyl alcohol follows a
second order rate law. Write the steps in the mechanism for each of these reactions
(curved arrows are not necessary).

1. Ethanol








2. Isopropyl alcohol







3. In ten words or fewer (only the first ten words you write will be read) explain
the change in mechanism.


Part B. Draw a reaction profile for a two-step exothermic reaction in which the first
step is rate determining. Use the given well as your starting point.
3X (10 points) Indicate how many
1
H signals you expect for the following compounds
(disregard splitting, which you have not learned yet). Indicate the intensity ratios of the
strongest to the weakest signal.
I expect to have _____ NMR signals;
intensity ratio: ______ : ______
strongest weakest

I expect to have _____ NMR signals;
intensity ratio: ______ : ______
strongest weakest
I expect to have _____ NMR signals;
intensity ratio: ______ : ______
strongest weakest

I expect to have _____ NMR signals;
intensity ratio: ______ : ______
strongest weakest

I expect to have _____ NMR signals;
intensity ratio: ______ : ______
strongest weakest


3Y (10 points) Indicate how many
1
H signals you expect for the following compounds
(disregard splitting, which you have not learned yet). Indicate the intensity ratios of the
strongest to the weakest signal.

I expect to have _____ NMR signals;
intensity ratio: ______ : ______
strongest weakest

I expect to have _____ NMR signals;
intensity ratio: ______ : ______
strongest weakest

I expect to have _____ NMR signals;
intensity ratio: ______ : ______
strongest weakest

I expect to have _____ NMR signals;
intensity ratio: ______ : ______
strongest weakest

I expect to have _____ NMR signals;
intensity ratio: ______ : ______
strongest weakest


4X (14 points) Consider the free-radical monochlorination of (R)-2-chlorobutane. A)
Draw the products you expect from the reaction at C-1, C-2, and C-3, using dotted-
line/wedge projection. B) Name each product (be sure to include the absolute
configurations of all products in their names). Also indicate whether the products
are optically active (Yes) or inactive (No). If more than one product results from
reaction at a given carbon, circle the product that is formed in higher yield. [There
may be more boxes than products formed]




Name __________________________
Starting material Product from substitution at C-___
Optically active? ___




Name _____________________________ Name ________________________
Product from substitution at C-___ Product from substitution at C-___
Optically active? ___ Optically active? ___



Name _____________________________ Name ________________________
Product from substitution at C-___ Product from substitution at C-___
Optically active? ___ Optically active? ___
4Y (14 points) Consider the free-radical monochlorination of (S)-2-chlorobutane. A)
Draw the products you expect from the reaction at C-1, C-2, and C-3, using dotted-
line/wedge projection. B) Name each product (be sure to include the absolute
configurations of all products in their names). Also indicate whether the products
are optically active (Yes) or inactive (No). If more than one product results from
reaction at a given carbon, circle the product that is formed in higher yield. [There
may be more boxes than products formed]



Name __________________________
Starting material Product from substitution at C-___
Optically active? ___




Name _____________________________ Name ________________________
Product from substitution at C-___ Product from substitution at C-___
Optically active? ___ Optically active? ___



Name _____________________________ Name ________________________
Product from substitution at C-___ Product from substitution at C-___
Optically active? ___ Optically active? ___
5X Part A (6 points) Show a two-step reaction sequence that would transform
cyclohexene into 3-cyanocyclohexene in reasonable yield. Show the reagent(s)
and the reaction conditions on the arrow.





What is the optical rotation of the final product? ____


Part B (3 points) The (!)-enantiomer oI a compound X has a speciIic
rotation oI 25. What rotation would you observe for a solution of 1
g of pure (")-enantiomer X in 2 mL of liquid in a 10 cm cell?


The observed rotation is _________.




Part C (3 points) What is the optical purity of a sample of X with a specific
rotation of +6?


____% optical purity


The _(__)_ enantiomer predominates.


Please NOTE: You must show your calculation clearly to receive credit.


5Y Part A (3 points) The (")-enantiomer oI a compound X has a speciIic
rotation oI 15. What rotation would you observe for a solution of 1 g
of pure (!)-enantiomer X, in 2 mL of liquid in a 10 cm cell.


The observed rotation is _________.



Part B (3 points) What is the optical purity of a sample of X whose specific
rotation is 6?


____% optical purity;



The _(__)_ enantiomer predominates.


Please NOTE: You must show your calculation clearly to receive credit.


Part C (6 points) Show a two-step reaction sequence that would transform
cyclohexene into 3-cyanocyclohexene in reasonable yield. Show the reagent and
the reaction conditions.









CN





What is the optical rotation of the final product? _____
6X (12 points) Using the templates provided, draw the structures of the major product
of each of the following reactions, carried out at room temperature.














6Y (12 points) Using the templates provided, draw the structures of the major
products of the following reactions, carried out at room temperature.

















7X (12 points) Using the templates provided, write a detailed mechanism for the
formation of the major product of the reactions shown. Be sure to include all lone
pairs, electric charges, and to show the movement of electrons with appropriate
curved arrows. If a chiral product is formed, show the stereochemistry of only the
most abundant enantiomer. Use only as many boxes as are needed.

A


B





7Y (12 points) Using the templates provided, write a detailed mechanism for the
formation of the major product of the reactions shown. Be sure to include all lone
pairs, electric charges, and to show the movement of electrons with appropriate
curved arrows. If a chiral product is formed, show the stereochemistry of only the
most abundant enantiomer. Use only as many boxes as are needed.

A


B