1

Chemistry 303
Fall, 2007
Final Examination
1:30 pm January 17th, 2008
Duration: 3.0 hr
NOTE: An additional 30 min will be allowed for completion of the course evaluation forms by those who
have not done it.
Name________________________________________________
Lab TA_______________________________________________ (not David, Casey, nor BJ)
This is an open book examination; you may use anything that is not alive.
Note: if you do not know the complete or specific answer, give a partial or general answer
We love to give partial credit.
If there seems to be more than one good answer, explain your thinking.
If you invoke resonance delocalization as part of your answer, draw the relevant resonance structures.
If you draw a chair cyclohexane, be sure to orient the bonds carefully.
If you do not know a structure and need to write a mechanism, write a general mechanism for partial
credit.
USE THE ARROW FORMALISM CAREFULLY FOR ALL MECHANISMS
BE SURE TO INCLUDE ALL FORMAL CHARGES

p2______/30

p3.______/16

p4.______/14

p5._______/14

p6._____ _/20

p7.______/12

p8.______/10

p9._______/14

p10._______/18

p11._______/12

p12.______/18

p13_______/14

p14_______/08

Total: ___________/200
There are 14 pages in this exam; please check now to be sure you have a complete set.

Pledge:_____________________________________________________________________________

2
I. (30 pts). Warm up with old stuff Consider the molecule below, which is produced by a
marine sponge. Lets analyze its bonding and reactivity. Write clear answers; explain any ambiguity
briefly. Do not forget the hydrogens. Label the features as requested; use an arrow to locate your label.

Br
O
O

1.
2.
3.
4.
5.
6.
7.

Which is the weakest sigma bond in the molecule (you may need your BDE tables)? Label it (a).
Which is the strongest C-C single (sigma; not part of pi) bond in the molecule? Label it (b).
Which is the strongest C-H bond in the molecule? Label it (c).
Which is the weakest pi bond? Label it (d).
Which carbon will be most reactive in an SN2 mechanism? Label it (e) and point with an arrow.
Which group or groups is (are) responsible for the !max at 230 nm in the UV spectrum? Circle it.
Which H attached to an sp3 carbon is most deshielded (downfield, to the left) in the 1H NMR
spectrum? Draw it in and label it (f).
8. Which H or group of H is most shielded (upfield, to the right)? Draw it in and label it (g)
9. Which is the shortest C-C bond in the molecule? Label it (h).
10. Which is the shortest C-C single (not part of double or triple) bond in the molecule? Label it (i).
11. Identify one group that will show a
characteristic peak in the IR spectrum.
Draw the group here and give the approx.
position (in cm-1) of the peak here:_______________________________________________
12. Identify a second group that will show a
characteristic peak in the IR spectrum.
Draw the group here and give the approx.
position (in cm-1) of the peak here:_______________________________________________
13. Which H is relatively acidic due to resonance stabilization of the conjugate base? Label it (j) and
explain here.

14. How many stereogenic centers are there in the molecule?

Circle best answer.
15. Which is the most polarized bond in the molecule? Label it (k).

6 7

other

3
II. (16 pts). Consider the E2 reaction of structure A.

H
Br

Br

H
Me
Me

E2

B
A

A. (6 pts). Draw here the structure of A using the chair representation.

Then write the mechanism for the most likely E2 reaction from A using a base. Show the product
structure carefully.

B. (5 pts). Obviously, two Br and several H could be involved in the E2 process, yet only one H and one
Br are in the favored mechanism. Explain, based on your structure and mechanism.

C. (5 pts). The E2 mechanism is often in competition with an SN2 reaction. Considering the list of
reagents here, circle the one most likely to favor the E2 process. Put a square around the second best
choice, and give at least two reasons why your first choice is better than the next best one.
O

NH2

4
III. (28 pts). For each of the following pairs of reactions, pick that member of the pair that will
proceed with the highest rate. Give the single most likely product from that reaction. Give the single
most important reason for the difference in rates.
A. (7 pts).
F3C

CH3

F3C

CF3

H-Br

H-Br

C4H4BrF3

C4HBrF6

B. (7 pts).
O
Cl

NaI
DMSO
solvent

LiBr
Cl

DMSO
solvent

Continued

5
C. (7 pts).
Br2

Br2

D. (7 pts).
NaSMe
I

DMSO
(solvent)

NaSMe
I

DMSO
(solvent)

dibromide

dibromide

6
IV. (20 pts). The reaction of V with catalytic sulfuric acid in THF leads to a mixture of
hydrocarbon isomers, with molecular formua C10H12 , mainly the structures W, X, and Y. Note that the
ratio of W:X:Y changes as the reaction is allowed to continue: at the early stages, almost no Y is
detected, but at long reaction time, Y is nearly the exclusive product. Compounds W and X show UVmax
typical of a simple benzene ring while the !max for Y is shifted to longer wavelength.
H2SO4
OH

THF

V
W

X (E/Z mix)

Y (E/Z mix)

A. (06 pts). Give the most likely structures for W, X, and Y in the boxes above.
B. (06 pts). Write a mechanism for the formation of W and X.

C. (06 pts). Write a mechanism for the formation of Y.

D. (02 pts). Give an explanation as to why Y becomes the predominant product at longer reaction time.

7
V. (12 pts). From time to time, we have mentioned orbital interactions in controlling reaction
rates. For SN2 reactions, the dominant interaction is HOMO of the nucleophile and LUMO of the
electrophile.
A. (6 pts). Write the mechanism for the reaction of ammonia with methyl iodide. What is the
HOMO and what is the LUMO?

B. (6 pts). It is an interesting fact that hydrazine (G) is a much stronger nucleophile than
ammonia, in the SN2 reactions. The orbital interaction argument is usually used to explain this. What is
the argument? It will be useful to draw a simple MO diagram, showing orbital interactions and relative
energy levels for the non-bonding electrons.
NH3
ammonia

H2N

NH2
G

VI. (10 pts). HCN and the trimethylammonium ion [(CH3)3NH+] have about the same pKa (ca
9-10). However, cyanide anion is a much poorer leaving group than trimethylamine. Why? In your
answer it would be good to include two main features that generally contribute to a good leaving group,
and then identify which of those is the main parameter responsible for the difference here.
H-N(CH3)3 and H-CN have the same pKa

Nu:

Nu:

+ H3C

H3C

N(CH3)3

CN

fast

very
slow

Nu-CH3 + :N(CH3)3

Nu-CH3 + CN

9
VII. (14 pts). Note that treatment of W with mCPBA gives X, a single stereoisomer, and then
treatment of X with hydroxide anion produces one product, Z. From the spectral data, possible structures
for Z are isomers a-d.
CH3
mCPBA*
H

HO
H2O

= mCPBA
O

OH

Cl

CH3

OH

CH3

OH

CH3

OH

CH3

OH

Possible Z:

H a

OH

H
b

OH

H
c

OH

H
d

OH

A. (4 pts). Based on your knowledge of mechanism and reactivity, which is most likely structure for X?
Please draw it in the box labeled X.
B. (4 pts). Based on your knowledge of mechanism and reactivity, which is most likely structure for Z?
Please draw it in the box labeled Z.
C. (6 pts). Justify your choice by writing a detailed mechanism for conversion of X to Z. Include with
your mechanism a reason why your choice for Z forms selectively instead of one of the other isomers.

10
VIII. (18 pts). We have not emphasized doing organic synthesis yet, but this requires
nothing more than recognizing the standard reactions (one or several steps) that connect a starting
material with a synthesis target. Proper sequencing of steps can lead to contrasting structures. For
example, consider the conversion of 1-bromo-2-methylpropane selectively into M.
Suggest how you might convert 1-bromo-2-methylpropane to M, through a series of one or more
intermediate molecules. Draw the series with an arrow connecting one to the next, and above the arrow
draw the reagents that will bring about this conversion. You may choose any of the reagents we
discussed in class. Shorter sequences are better.
Possibly useful reagents: HBr, AgNO3, NaH, BH3, HOOH, LDA, NaI, RCO3H, HCl, NaBr, MeI, H2O
Me
Me

Br

H
H
H
1-bromo-2-methylpropane

Me
Me

OH

Br

H
M

IX. (12 pts). When (S)-2-bromopentane ( ["]D +34o ) is mixed with sodium bromide in
ethyl alcohol solution, the 1H NMR spectrum of the solution remains constant with time. However,
monitoring the solution by optical rotation shows that the rotation slowly decreases and eventually
reaches zero. If the amount of sodium bromide is doubled, the rate of decrease of the optical rotation is
doubled, but, again, the NMR spectrum remains constant.

11

A. (08 pts). Write a reaction mechanism here that accounts for these observations (you need not
draw transition states). Draw the structure of (S)-2-bromopentane precisely.

B. (04 pts). Explain how your mechanism is consistent with the gradual decrease in optical
rotation for the solution while the NMR spectrum remains constant.

12
X. (18 pts). Radical reactions can be quite useful in making complex system under carefully
controlled conditions. For example, compound K is converted to L under the conditions shown. The
peroxide initiator reacts with the tin-hydride (nBu3SnH) to give a tin radical that starts things off.
Note the products that are formed, and write your best mechanism to account for them using
proper arrows.
O
+
Br

Initiation:

nBu3SnH

RO-OR
heat

nBu3Sn H + RO

RO-H + nBu3Sn

+ nBu3SnBr
O
L

13
XI. (22 pts). Alcohols will generally react very rapidly with alkenes that bear an oxygen
substituent, (e.g., G) in the presence of a catalytic amount of an acid to give an adduct, H. Structure H
shows simple spectral data (Data Supplement). You can determine the structure of H either by predicting
the mechansim of the reaction or by interpreting the spectral data.

OH

H2SO4

+
O
G

(catalyst)

[H]

C10H22O2

A. (10 pts). Draw the structure for H and write the best mechanism for its formation. Be sure to show
the catalytic role for the acid.

B. (4 pts). Is your structure consistent with the number of peaks in the proton decoupled 13C NMR
spectrum shown in the Data Sheets? Explain.

C. (5 pts). Draw your product again here and give the approximate 1H NMR chemical shift
positions in ppm for each set of equivalent protons, using the peak positions from the spectrum in the
Data Sheets.

14

D. (3 pts). Why does the presence of the oxygen substituent in G accelerate the reaction, compared to a
carbon atom in the same position? Explain with words and pictures in terms of mechanism.

END EXAM
See you in two weeks or so