Chemistry 14D

Winter 2014

Exam 1

Page 1

You may use Ph anywhere on this exam where appropriate.

The questions on this page refer to the following incomplete SN2 reaction.

Br

H3C

CH3

Na+ -I

I
I

acetone

CH3

1.

(2) In the appropriate space above draw the reaction mechanism by adding the missing curved arrows.

2.

(3) In the appropriate space above complete the drawing of the transition state.

3.

(2) In the appropriate space above complete the drawing of the product.

4.

(2) Complete the following rate expression for this reaction. Be specific.

5.

(2) In the box draw the molecular structure of acetone. Include all lone pairs and
formal charges.

6.

(3) Fill in the blanks with atoms that make bonds. (Example: ...the LiP bond...) There may be more spaces than

Rate = k

answers. Within the molecular structure of acetone, the ______________ and ______________ bond(s)
decrease(s) whereas the ______________ and ______________ bond(s) enhances(s) .

7.

(2) Circle one or more of the following solvents that would make the reaction even faster then when acetone is
the solvent:
CH3OH
DMF
H 2O
Hexane
None of these

8.

(8) What happens to the rate of the reaction when the following changes are made? Circle one rate effect in each
case. The changes are not cumulative. For example, part (b) ignores the change made in part (a).
(a) Br changed to I

Becomes faster

Becomes slower

No significant rate change

(b) HCBr changed to H3CCBr

Becomes faster

Becomes slower

No significant rate change

(c) I changed to F

Becomes faster

Becomes slower

No significant rate change

(d) Br changed to OH

Becomes faster

Becomes slower

No significant rate change

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Chemistry 14D
9.

Winter 2014

Exam 1

Page 2

(6) Define the following terms using no more than 20 words in each case. Use words only; no pictures or
examples.
(a) Transition state:

(b) Rate-determining step:

10. (2) On the course discussion board was written, All primary alkyl halides
undergo SN2 reactions. If this statement is true write true in the box
Otherwise draw in the box the structure of a primary alkyl halide that violates
this statement.

11. (9) Using the carbocation shown below and methanol as the only reactants in each case, name and illustrate
the three common fates of a carbocation. Include appropriate curved arrows. If the fate can occur in more than
one way, illustrate only the most likely pathway. If a particular fate is not likely to occur, write not likely in
place of its illustration. Do not go beyond a single mechanism step for any of these fates.
Name of carbocation fate: ______________________

Illustration:

Name of carbocation fate: ______________________

Illustration:

Name of carbocation fate: ______________________

Illustration:

12. (2) By changing only one hydrogen atom into a fluorine

atom, redraw the less stable carbocation shown here so
that it is more stable. Make not other changes in the
molecular structure. If this is not possible, write not
possible in the box. (You may add a few words of
explanation for a "not possible" answer if you wish.)
Less stable carbocation

More stable carbocation

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Chemistry 14D

Winter 2014

Exam 1

Page 3

Questions 13 and 14 refer to this SN1 reaction:

Br

H3C
CH3OH

Major product

Minor product

13. (4) In the space above write the major SN1 reaction product in the Major Product box. If a second product
occurs write this in the Minor Product box. If no minor product is produced write a large X in the Minor
Product box.
14. (7) Write the mechanism for the major product. Label the rate-determining step as rds. Do not include
transition states.

15. (4) Rank the stability of the following alkenes by circling one number beneath each. 1 = most stable and 4 =
least stable.
CH2CH3

16. (3) Circle one choice in each set that best describes the alkene in the box.
(a) Cis
(b) E

Trans
Z

(c) Terminal

Cl

Neither

Neither

Internal

Neither
H3 C

17. (6) Examine molecule A, then circle one or more answers in each set.

H3C

OH
Cl

Molecule A
(a) Molecule A can engage in which of the following? SN2

S N1

E2

E1

None of these

(b) The most likely ionization of molecule A gives a carbocation which is:
Methyl

Primary

Secondary

Tertiary

Has resonance

Lacks resonance

(c) If one methyl group of molecule A is changed to Ph, what happens to the rate of ionization?
Becomes faster

Becomes slower

No significant change

It still does not ionize

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Chemistry 14D

Winter 2014

Exam 1

Page 4

18. (7) Here we're going to write an E2 reaction that demonstrates Zaitsev's rule. Draw in the reactants box a
molecule that has exactly five carbon atoms plus any number of atoms of any other elements but no nonzero
formal charges, that when reacted with a strong base follows Zaitsevs Rule and gives a trisubstituted alkene
product. In order to demonstrate Zaitsev's rule, your molecule must give exactly two different elimination
products. In the base box write the base that might be needed for this reaction. In the Zaitsev product box write
the appropriate reaction product.

Reactant

Base

Zaitsev product

Questions 19 and 20 refer to the N-methylation of norepinephrine with S-adenosylmethionine (SAM) to give (after
deprotonation) epinephrine (adrenaline), an SN2 reaction discussed in lecture.
B
A

OH

OH

HO

NH2

R2 S

CH3

HO

HO

H
N
CH3

HO

Norepinephrine

SAM

Epinephrine

19. (8) Complete each sentence by adding no more than 25 words in each case. Be specific, and do not use the
same reason for both.
(a) Methylation occurs at the amine instead of at the OH labeled A because...

(b) Methylation occurs at the amine instead of at the OH labeled B because...

20. (8) In order to verify the norepinephrine/SAM reaction mechanism, the effect of solvent was studied.
(a) Rank the polarity of the solvents by writing the one of following e values in each blank: 80, 25, and 8.
H2O = _______

CH3CH2OH = _______

(b) Circle the solvent(s) that is/are polar and protic: H2O

CH3(CH2)7OH = _______

CH3CH2OH

CH3(CH2)7OH

(c) In the norepinephrine/SAM reaction, circle the one species that receives the greatest increase in stabilization
when the solvent polarity is increased:
Nucleophile

Electrophile

Transition state

(d) In the norepinephrine/SAM reaction, which solvent makes the reaction slowest? Assume that everything
present dissolves completely in any of the solvent choices.
H 2O

CH3CH2OH

CH3(CH2)7OH
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Chemistry 14D

Winter 2014

Exam 1

Page 5

21. (10) Each reaction shown below is likely to occur by one or more of the given mechanism choices. If the
reaction is likely to occur by a particular mechanism, draw the major product formed by that mechanism in the
box above the mechanism name. If the mechanism is unlikely, write an "X" in the box. If no reaction occurs,
write an "X" in each box.
CH3
K+ -OC(CH3)3

(a)

Major product(s)

HOC(CH3)3

Major product:

Mechanism:

S N2

S N1

E2

E1

Major product:

Mechanism:
H

(b)

CH3OH

Major product(s)

OSO2CF3

Major product:

Mechanism:

S N2

S N1

E2

E1

Major product:

Mechanism:

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