CEM 351, Fall 2007

Midterm Exam 1
Friday, September 28, 2007
1:50 – 2:40 p.m.
Room 138, Chemistry
Name (print) L. T. N. Swers
Signature
Student #

...
Section Number (2 pts extra credit)

Grade?

...
1.(20 pts.)
2.(20 pts.)
3.(20 pts.)
4.(20 pts.)
5.(20 pts.)
6.(20 pts.)
TOTAL (100 pts.)

Score

Note: Answer any 5 questions for a total score of 100 pts. Be sure to look over
all the questions first before beginning the exam, and indicate which five
questions are to be graded by checking the corresponding box.

Recitation Day and Time Instructors: Room

1. T 9:10-10:00 a.m. Alex Predeus 85
2. M 10:20-11:10 a.m. Alex Predeus 281
3. T 10:20-11:10 a.m. Karrie Manes 85
4. Th 10:20-11:10 a.m. Kostas Rampalokos 287
5. T 10:20-11:10 a.m. Alex Predeus 283
6. T 11:30-12:20 p.m. Kostas Rampalakos 283
7. Th 11:30 - 12:20 Kostas Rampalakos 85
8. M 4:10-5:00 p.m. Karrie Manes 110
9. W 4:10-5:00 p.m. Karrie Manes 110
1. (20 pts)
(a) (3 pts each) Form acceptable Lewis structures for the following uncharged
compounds by adding the necessary nonbonding electrons and multiple bonds:

H O

O C O N C
H H

Carbon Dioxide Formamide

(b) (3 pts each) Assign formal charges as necessary to the atoms in the following Lewis
structures.

O H H O

H O C H N C C

O H H O
Bicarbonate Glycine (an amino acid)

(c) (4 pts) A full description of bicarbonate (above) requires two main resonance
structures. The one you completed was one; draw the other one:

H O C

(d) (4 pts) Shown below is another commonly published representation of Glycine. Is this
a valid resonance structure of the version in (b)? Please circle your answer and explain.

Yes No

H O

H N C C

H H O H
Explanation: Resonance structures are related only by moving electrons/bonds around, not
atoms. This structure has atoms in different places than the one above; instead of the charged
H3N+- and -COO– groups as above, it has H2N- and -COOH, both neutral groups.

2
2. (20 pts) Consider the five Newman projections below.
H3 C H H3 C H3C H H3C H3 C H

H H H 3C H

H H 3C H
H3C H H3C H H3C H H3 C H H3 C CH3
CH3 H H
CH3 H

A B C D E

(a) (2 pts) All of these diagrams depict compounds of formula __ C5H12 ___________.
(b) (4 pts) Structure _ E _ represents a compound different from the other four. This
compound’s IUPAC name is _______________ 2,2-dimethylpropane _________.
(c) (2 pts) The other four depict (IUPAC name):___ 2-methylbutane _____________.

Of the four in (c),…

(d) (2 pts) …which two structures represent staggered conformations? _ B _ and _ D _.

(e) (2 pts) …which two structures represent energy maxima (high points) on the torsional
potential energy surface? _ A _ and _ C _.

(f) (4 pts) For two of the above structures there are additional conformations of equal energy.
Which ones are they? _ B _ and _ C _. Draw their same-energy conformations by
completing the Newman projections, labeled F and G below.
H3C H3C CH3

H CH3

H
H3 C H H3C H
H
H

F G

(g) (4 pts) In the box below, take structure A to be at 0˚ and sketch the rotational potential
energy diagram, placing structures A-G (except for the misfit) in your picture.
A

E G
N C
E
R A
G F
Y B
D D

-180˚ -120˚ -60˚ 0˚ 60˚ 120˚ 180˚

3
3. (20 pts)
(a) (12 pts) Draw structures to represent the following IUPAC names

(i) 2-chloro-2-fluoroethanol
F
HO
Cl

(ii) 1,1,2-trimethylcyclopentane

5 1
4 2
3

(iii) 3,3-diethylpentane

(b) (2 pts) Which of the compounds in (a) has no dipole? Please circle your answer

(i) (ii) (iii)

Note: based on symmetry, compound ii’s dipole is small but finite.

(c) (3 pts) Why don’t we have to give a number to show the hydroxy group position in
compound (i), a substituted alcohol?

Explanation:
With only two carbons to choose from, the –OH group defines the numbering.

(d) (3 pts) Why don’t we have to indicate cis or trans in describing (ii), a cycloalkane?

Explanation:
With two methyls at C-1, the “top” and “bottom” face substituents are the same, so
“cis” or “trans” are meaningless to describe the compound (though one could refer to
the cis- and trans- methyls relative to the methyl at C-2).

4
4. (20 pts) Structural analysis by spectroscopy
(a) (3 pts each) For each pair of compounds in the grid below, propose a spectroscopic method to
tell them apart, and explain what you would look for with the suggested method.

Compounds Method & Explanation

O MS of left cpd would see easy losses of t-Bu
O (57) but much less of CH3 (15), whereas CH3,
A CH3CH2O losses dominate for cpd at right.
1H NMR would see left cpd as three singlets,

right at singlet + ethyl pattern.

O IR of right cpd would show carbonyl (C=O)

and CH3 bands missing in left case.
B O
1H NMR of left cpd would be three multiplets

integrating to 2:4:4, right cpd = ethyl pattern.

UV-vis spectrum of conjugated diene at right

would absorb at ca. 225-230 nm; left cpd's
C isolated alkenes would be <190 nm and weak.
1H NMR & IR would show left's terminal

alkenes. IR would show right's methyl groups.

Chemical shifts in 1H or especially 13C NMR
would distinguish--Cl is more electronegative
D Br Cl than Br. C-Hal stretch in IR would also work,
but they're weak bands. And MS obviously
would be different--different elements.

(b) (8 pts) Below are 1H NMR and IR spectra for some MSU students’ favorite substance of
abuse (ethanol). Please identify the key features that confirm this structure—i.e., assign the three
NMR peaks to the sites in the molecule, explain their splitting patterns, and predict their
respective integrals. Similarly, identify at least three features of the IR spectrum that support the
structural assignment.
b--CH2 quartet, split
1H NMR by H's of CH3 grp c; b c--CH3 triplet,
shifted to high freq. HH split by H's of
by attached OH; CH2 group b;
Integral = 2 H Integral = 3
a--OH peak,
broadened by
HO c
a
H-bonds and HH
fast exchange;
Integral = 1

5 4 3 2 1 0
PPM
1450-1380 sh

CO str 1300-1000
CH str 3000-2800 sh

CH2, CH3 bnd

OH str 3600-3300 br

IR

(Note: this peak is in

C=O region, but too
broad; impurity?)

5
5. Consider the following equilibrium constant values (from Bruice, Table 2.10, p. 112) for
interconversions between the two chair conformations of substituted cyclohexanes.
R K(eq/ax) !G(eq/ax) (kcal/mol)
H 1 0
R
CH3 18 1.7
CH2CH3 21 1.8
R
CH(CH3)2 35 2.1
A B C(CH3)3 4800 5.0

a. (3 pts) In which structure above is R axial? (Circle your choice): A B

b. (6 pts) Use the templates below to construct Newman projections of the three ethyl rotation
energy minima as viewed down the CH3CH2–CH(CH2)5 (i.e. ethyl-cyclohexyl) bond in
ethylcyclohexane (the cyclohexane ring is already shown).

Higher Higher Higher

Lower CH3 Lower H Lower H

H H H3C H H CH3
H H H

c. (6 pts) Rank the three conformations in part (b) higher or lower in energy (two are the same)
by circling the correct word for each.

d. (5 pts) The equilibrium constants in part (a) translate into the energy differences shown at
right (from the relationship ∆G = -RTln K; ∆G = “Gibbs free energy difference”). Along the way
from R = CH3 to R = C(CH3)3, the methyl, ethyl, and isopropyl groups have axial-equatorial ∆G
values (1.7, 1.8, 2.1) within 0.4 kcal/mol—hardly different. But the next jump, to the t-butyl
group, raises the ∆G up to 5 kcal/mol! Explain, using careful drawings on the templates below
and a few carefully chosen words, why this last methyl replacement makes a difference so much
bigger than the others. (Hint: how would the conformations you produced in part (b) be affected
by chair-chair flipping of the cyclohexane part?)

!G = +5 kcal/mol

If all CCC angles were

H
tetrahedral and torsions
H H staggered, these H's
H3C H would be nearly on top
H3C
H of each other in space.
Unlike the ethyl story above,
the t-butyl's methyl bumping Here’s a model from a
can't be relieved by rotating more complete simulation,
here to move methyls out showing how the ring has
from under ring. flattened to relieve H-H
bumping

6
 b a
6. (20 pts) More on structural analyses based on spectroscopies: c
(a) (8 pts) For each compound below, circle and label (with a,b,c…
as in the example at right) the groups of equivalent 1H sites. If
it’s helpful, feel free to add H’s as appropriate to the structures.

f
(i) (ii) d c (iii) (iv) a OH e
d H CH3
a c b a a b cO
b b (careful!)
a c H
d H c CH3
b d

(b) (6 pts) Only one of the above compounds would show simple singlets (i.e. unsplit
peaks) in its 1H NMR spectrum. Redraw the compound and point out the site(s)
responsible.
OH
H CH3 These methyl groups
have no neighboring
H H's so their NMR
H CH3 peaks are singlets

(c) (6 pts) Compounds (iii) and (iv) in part (a) are isomers. Could you tell them apart by
IR spectroscopy? How? Identify at least two spectroscopic differences you could
easily see. (Assume the strained cyclopropane ring doesn’t do anything special.)

Cyclopropanol (same as (b) answer) should show:

(a) Alcohol bands:
a. broad OH stretch ca. 3600-3300 cm-1
b. C-O stretch near 1300-1000 cm-1
(b) Methyl group bending bands:
a. 1385-1365 along with general C-H 1450-1420