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Chemistry 303,

fall, 2006

SECOND EXAMINATION
7:00 PM, NOVEMBER 13th, 2006
Duration: 2.0 hr
Name____________________________________________________________
Lab TA__________________________________________________________
(if you do not know his/her name, give day of lab section. NOT Shawn nor Bill)
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-WRITE SOMETHING [and WRITE CLEARLY!]
Write only in the space provided for each question.
Score:
P2______/17

p3_______/12

p4_______/13

p5_______/15

p6_______/11

p7_______/15

p8_______/12

p9_______/11

Total: _________/106
There are 9 pages in this exam. The separate Data Supplement contains: a table of nuclear spin for common
nuclei, a table of abundance of common isotopes, and a series of spectral data for Problem V. Turn in only the
exam.
If you are using a resonance argument in your answer, draw the relevant resonance structures.
Be aware that in Problem V, you may "purchase" the unknown structure (A) for an 7-point penalty. Go to the
front and request the structure of the proctor and he/she will deduct the appropriate points.
Please be aware that a small number of students will be taking the exam at different times up until the afternoon
on Tuesday. It would be well not to discuss the exam until after that time.

PLEDGE:_______________________________________________________________

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I. (23 pts). Consider the following molecules, A-D and their corresponding spectroscopic properties.
Respond to each question by drawing the molecule that fits the data and explaining carefully why you chose it.
It will help to refer carefully to structural details.
O
A

SCH3

Br
H

Br

A. (3 pts) Which molecule will have the longest wavelength UV peak [!max]?

B. (2 pts) Which molecule will have the highest M+1 peak in the mass spectrum (relative to the molecular
ion)?

C. (3 pts) Which molecule will have the highest M+2 peak in the mass spectrum (relative to the molecular
ion)?

D. (3 pts) Which molecule will show a nonet (nine peak multiplet) for one H in the proton NMR spectrum
(assuming perfectly first order and all J values = 7 Hz).

E. (3 pts) Which molecule will show a peak furthest downfield (deshielded, to the left) in the proton NMR?

continued

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O
A

SCH3

Br
H

Br

F. (3 pts) Which molecule will show the highest energy stretching vibration in the IR?

G. (3 pts) Which molecule will show the largest number of peaks in the broad band decoupled C-13 NMR
spectrum? How many peaks?

_________________________________________________________________________________________
II. (06 pts) Consider this H NMR spectrum, and the three possible structures adjacent.

Of the three structures, which two can be eliminated by the NMR data? Explain carefully.

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III. (13 pts) Consider the molecule, C.
A. (2 pts) On the structure here, put in all the hydrogens,
and label sets of equivalent hydrogens as Ha, Hb, Hc, etc.
B. (08 pts) For each set, give the approximate chemical shift,
area, and the pattern (s, d, t, quart, quintet, sextet, etc)
you expect.
Explain any multiplets by stating clearly which H are coupled
to the one you are observing.

H
Cl

Ha

________________________________________________________________________________________
Hb

_______________________________________________________________________________________
Hc

________________________________________________________________________________________
Hd

________________________________________________________________________________________
C. (03 pts) How many peaks would you expect in the broad band decoupled C-13 NMR spectrum?
Explain with reference to the structure.

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IV. (15 pts). Consider the following three pairs of molecules. You may use H NMR, C-13 NMR,
IR, or mass spec to differentiate the structures, but you may use a technique only once on this page. Pick a form
of spectroscopy for each, and point out the single clearest difference between the compounds by that form of
spectroscopy.
A.

_____________________________________________________________________________________
CN

B.
NC

Cl
Cl

______________________________________________________________________________________
C.
e

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V. (38 pts) Consider the spectral data given for compound A in the data sheets.
A. (2 pts) What heteroatoms are definitely NOT present based on the mass spectrum?
Br____

Cl____

I____

F____

S____

B. (2 pts) From the mass spectrum, give an estimate of the number of carbon atoms in A.
C. (2 pts) From the UV data, conjugated pi bonds are:
Definitely present

Definitely absent

Cannot tell

D. (5 pts) From the infrared spectrum in the region 1500-4000 cm-1 alone, which of the following functional
groups can be ruled out? Circle those that are ruled out and explain in one sentence how you came to that
conclusion.
1. C=O

________________________________________________________________________________
2. RC!CH

__________________________________________________________________________________
3. C=C

__________________________________________________________________________________
4. C!N

__________________________________________________________________________________
5. O-H

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E. (12 pts) Consider the H NMR spectrum.
For each group of equivalent protons, list:
Chemical shift (in ppm) and approx. pattern (e.g., singlet, doublet, triplet, quartet, quintet, sextet, etc)
Give the approx coupling constant from the following ranges: 1-2 Hz, 6-8 Hz, 18-20 Hz.
chemical shift

pattern

coupling constant

1. _________________________________________________
2. _________________________________________________
3. _________________________________________________
4. _________________________________________________
5. _________________________________________________
6. _________________________________________________

F. (3 pts). Consider the C-13 NMR spectrum. (ignore the CDCl3 peaks)
1. How many non-equivalent carbons are in the molecule?

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2. Note the letters (q, d, s) indicating that the peaks are quartets, doublets, or singlets in the coupled
spectrum.
a. How many peaks corresponding to methyl groups are there?
One___

Two____ Three____ Four _____ Other_____ Cannot tell______

b. How many peaks corresponding to methylene groups (-CH2-) are there?

One___

Two____ Three____ Four _____ Other_____ Cannot tell______

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G. (12 pts) Draw LARGE here the structure of A (4 pts) which best fits the spectral data, showing
all of the H atoms. (If you do not have confidence in a unique structure, you may get partial credit by drawing
parts of a molecule that are consistent with the spectral data and explain OR you may proceed to the front of
the room and ask for the structure of A. The preceptor will mark your paper with -7 pts and give you the
structure so you can proceed.) Be sure to indiate clearly which structue or piece(s) of structure you wish to
have graded.
1. (2 pts) On your structure. Identify groups of equivalent H by labeling them Ha for one type,
Hb for a different type, Hc , Hd , He and so on.
2. (2 pts) Label each group with the corresponding chemical shift from the H NMR spectrum.
3. (2 pts) Use the additivity table to calculate the chemical shift expected for each group of equivalent H
attached to sp3 carbons. Show your work.
4. (2 pts) Give the pattern for each group of equivalent protons (s, d, t, quartet, quintet, sextet, etc) and
explain why you chose that pattern for each (i.e., what are they coupled to?).

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VI. (11 pts). We have begun to talk about the relative size
of substituents in controlling conformations of molecules.
Table I suggests the relative sizes of various substituents compared to H.
A. (6 pts) Draw the three more stable staggered
Newman projections for Y on the diagrams below.
Your projections should be drawn looking along the
bold bond as indicated by the arrow.

Substituent

Relative
Steric Size
zero
small
medium
large
larger

-H
-F
-Cl
-CH3
-CH2CH3

F
H

C
Cl

C
Y

H
CH3

B. (3 pts) Which conformation that you drew above has the lowest energy? Why? Please discuss all of the
factors that led you to your decision. That is, identify all elements of torsional strain for each conformer,
and any special effects for this particular molecule.

C. (2 pts) Draw the least stable (highest energy) conformer for Y, considering any orientation about the bond
indicated. Explain the factors that led to your decision.

End exam