Chemistry 303

fall, 2007
FIRST EXAMINATION
7:00 PM, OCTOBER 15TH, 2007
Duration: 2.0 hr
Name________________________KEY____________________________________
Lab TA___________________________________________________________
(if you do not know his/her name, give day of lab sectionnot BJ, Casey, nor David)
This is an "open book" examination; you may use anything that is not alive [or connected to the Web]
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
WRITE SOMETHING
BUT: write legibly! We will not work too hard to decipher sloppy writing.
READ each problem carefully!

Write only in the space provided for each question.

Score:
I___________/11

II___________/14

III___________/18

IV___________/12

V___________/12

VI___________/15

VII___________/08

VIII___________/10

Total:

/100

There are 9 pages in this exam; please check now to be sure you have a complete set.

Pledge:_________________________________________________________________________________

I. (11 pts). Consider the molecules, A, B, C.

CH3

H3C

CH3

A. (03 pts). Write here the list of molecules in order of increasing bp:
__C___ <
lowest

___B__ < __A___

highest

B. (04 pts). Give the single most important reason for the difference in bp for the one with highest bp and the one that is second
highest. Use words and pictures.

CH3

CH3

N
O

CH3

O:
A'

CH3

N:
B'

Dipolar structure A' is a stronger contributor to A than dipolar structure B' is to B, because charges
are localized on atoms with more favorable EN: (-) on O and (+) on N. Therefore,
A is a more polar molecule, stronger dipole-dipole interaction, and higher bp.

C. (04 pts). Give the single most important reason for the difference in bp for the one with second highest bp and the one that is
lowest. Use words and pictures.

CH3

O
O
C

O:
C'

CH3

N:
B'

Dipolar structure B' is a stronger contributor to B than dipolar structure C' is to C. Therefore,
B is a more polar molecule, stronger dipole-dipole interaction, and higher bp. Resonance structure
C' has one fewer bonds than C, and is therefore a small contributor.

II. (14 pts). Consider the molecule M for which the resonance stucture M1 has the connectivity represented below.
(all bonds and non-bonding electrons shown; no net charge)
A. (02 pts) Draw in on the structure all formal charges, clearly showing the location.

H3 C C
a
H3C

Cb CH3

M1
B. (08 pts) Using the arrow formalism, draw three additional good resonance structures for M; label them M2, M3, and M4.
Evaluate the structures and circle the most stable one [if more than one is "best", indicate both]. Explain your choice.

H3C C
a
H3C

Cb CH3

M1

H2C C
a
H3C

H3C C
a
H3C

Cb CH3

M2

Cb CH3

M3

H3C C
a
H3C

Cb CH3

M4

OR:
H3C C
a
H3C

Cb CH3

M1

H3C C
a
H3C

H3C C
a
H3C

Cb CH3

M4

Cb CH3

M3

H2C C
a
H3C

Cb CH3

M2

Both M2 and M3 have one additional bond. The charges are stabilized in the same way in both, so these structures are
not distinguishable in terms of stability.
M1 and M4 have no charges, which is stabilizing, but they also have one fewer bonds which is the dominant factor.

C. (04 pts)

What is the hybridization at Ca?

sp

At Cb?

sp

At N?

sp

What is the geometry about the Ca-N-Cb bonds

sp2
sp

sp

sp

sp

bent

sp

or

(circle best answer)

linear?

III. (18 pts) Consider the acidity of the three molecules, X, Y, and Z.

H 3C
H 3C C H
H 3C X

H 3C
H3C C NO2
H 3C Y

H3C
H3C C NO2
H Z

pKa 56

pKa 42

pKa 10

The NO2 group has

this connectivity:
R

A. (04 pts) There are two types of H in X. Which one is more acidic in the gas phase?
H3C
H3C

H3C
H3C

H3C
X

or

H3C

C
1

B. (05 pts) Draw the best resonance structure of Y in detail, showing

all bonds, non-bonding electrons, and formal charges, if any:

H3C
H 3C

O
C

H3C

C. (04 pts) Draw the conjugate base of Y.

reason for the difference.
H 3C
H3C C NO2
H C Y
H
H

Draw another good resonance structure:

H 3C
H3C

H3C

Why? Draw the conjugate base.

Anion 2 is stabilized by the polarizability of the methyl

groups compared to the Hs in anion 1. This is certainly
clear in the gas phase, but might be more ambiguous in solution
with steric effects on solvation.

CH3

CH3
2

O
N

O
C

This is straight out of

the text, p 495

N
O

Note the difference in pKa for Y compared to X. Explain, with the single most important

H3C
H 3C C
H 2C

NO2

Big dipole from the NO2 group removes electron

density through the sigma bond system, an inductive
stabilization of the nearby negative charge. Molecule
X has no dipole to provide an inductive effect

H+

D. (05 pts) Which is the most acidic H in Z? Answer by drawing the conjugate base of Z showing all bonds, non-bonding electrons,
and formal charges. Draw another good resonance structure of the conjugate base and explain which structure best represents
the molecule.

H 3C
H3C C NO2
H Z

-H+

H 3C
C

N
H3C

Strong inductive effect and strong

resonance delocalization

C
O

H 3C

H3C

O
2

Structure 2 is the best; (-) charge on

O instead of C, same number of bonds.

IV. (12 pts). Molecule G has three quite basic sites. The most basic site has pKa 12 (conj acid), the next has pKa 9 and the
third site has pKa 3.
NH

NH2
O
N

NH2

Considering that ammonia has pKa 9.3, and acetic acid has pKa ca 5:
A. (04 pts) Identify the most basic site in G and explain your choice. Draw the conjugate acid. What is the single most
Important reason for the relatively high basicity?
pKa 9 by analogy with ammonia
N

NH2

N
O

must be pKa 12

NH

NH2

NH2

NH2

O
H

pKa ca 3 by analogy
with acetic acid (inductive effect of -NH3+ group
lowers pKa from 5 to 3)

NH2

NH2

O
N

NH2

NH2

B. (03 pts) Identify the second most basic site in G and explain your choice. Draw the conjugate acid.
pKa 9 by analogy with ammonia
NH

NH2

H+

O
N
O

NH2

NH2
O
N

NH2

O
N

NH2

NH2

NH3
H+

NH2

The second protonation takes place on the first conjugate acid, leading to the dication.

C. (05 pts). Identify the most acidic proton in G, and draw the conjugate base. Explain your choice.
no resonance stabilization for conj base from removal of this H

NH

NH2
O
N
O

-H+
N H
H

NH

NH2

NH

NH3

O
N
O

NH

NH

conj base can allow delocalization of (-) charge over two N. Two equivalent structures,
strong stabilization.

V. (12 pts). Deuterium, the heavy isotope of hydrogen with atomic wt 2, has all the chemical properties of hydrogen and is
sometimes used to detect reactions that are otherwise not easy to assay. For example, if one allows acetophenone (N) to stand in a
solution with H2O as solvent and a small amount of sodium hydroxide, there is no apparent change no matter how one monitors the
solution. However, if one carries out the same test using D2 O as solvent, the acetophenone slowly changes sequentially into new
molecules, first heavier by one mass unit, then two, and finally after long reaction time, a molecule with a molecular weight three units
higher. The new molecule still has exactly the same chromatographic properties (e.g., same position on tlc analysis).
No detectable change

H2O
O

NaOH

N CH3
MW 120

D 2O
NaOD
New molecule, MW 123

A. (04 pts) What is the likely reaction between the base NaOH and acetophenone, N?
O

H
N

MW 120

Resonance stabilized conj base

formed in (unfavorable) equilibrium
with reactant ketone + HO-

+ H2O
C

:OH

C
H

Vanishingly small conc. of conj base at equilibrium (ca 10-5), not readily detectable

B. (08 pts) What happens in D2O, consistent with the observation that new molecules can be detected by monitoring molecular
weight and eventually a product appears with MW higher by 3 units? Write a series of reactions to rationalize this change in
molecular weight under these conditions. Show clearly the role of NaOD. Use the arrow formalism to show electron flow
making/breaking bonds.
O

D-O-D

H
C
MW120

C
H

C
H

MW 121
+

DO-

O
D-O-D

C
H
+ H-O-D

+ DO-

DO:

In D2O solvent (large excess of D2O), the conj base

can return to the acid (ketone) by picking up D+
with high probability
Complete replacement of
all acidic H by D. Remaining
H on benzene ring are not
acidic enough to be replaced
under these conditions.

C
MW 122 H

C
MW 123

D-O-D

C
D

+ H-O-D

VI. (15 pts) The substitution patterns around benzene rings often have substantial and dramatic effects on the pKa of the
molecules. Note that the presence of a trifluoromethyl group makes phenol U significantly more acidic than phenol itself, V. Adding
methyl groups does not have much effect (Cf, W). In a different series, though, comparing X and Y, there is a strong effect due to the
presence of the methyl groups.
H3C

OH

OH

F3C

F3C
U, pKa 9

OH

O2N

O2N

CH3
W, pKa 9

V, pKa 10

H3C

OH

OH

CH3

X, pKa 7.2

Y, pKa 8.2

A. (05 pts) Explain carefully the single most important reason why U is significantly more acidic than V. Show the conjugate base
for each case.

F3C

OH

OH

F3C
negative charge delocalized into the benzene ring, at alternating positions
O
resonance structure showing direct interaction of the strong
electron withdrawing group with the (-) charge, stabilizing
this resonance structure. This is the inductive effect of the CF3 group.

F 3C

B. (05 pts) Similarly, explain carefully why X is more acidic than V.

O

OH
O
O2N

N
O

Strong resonance stabilization

O

O
N

one resonance structure

showing delocalization into
the benzene ring. Two others
not shown.

additional and very good

resonance structure showing
delocalization into the nitro group and
positioning the (-) charge on the oxygen

C. (05 pts) [Tough one!] Explain carefully why the addition of two methyl groups as in Y changes the pKa to a higher value
compared to X.
O
O

N
O

H 3C
O

N
O

CH3

in this structure, all of the atoms are

in the plane of the benzene ring, for
optimum overlap. p orbital on every atom

With the H substituents replaced by methyl groups, there is

severe steric crowding when the nitro group tries to assume a
planar geometry to allow delocalization. Therefore, this resonance
structure is de-stabilized, the nitro group is less effective in
delocalizing the (-) charge, and the acid is less acidic.

VII. (08 pts) Compare the three alcohols here, F, G, and H

H
H

OH

H 3C
H 3C
H 3C

F
C

OH

OH

A. Which is the best H-bond donor? Explain by comparing with each of the other two.
H
H

H F

H 3C
H 3C

O
H

sterically accessible,
polar -O-H bond.
Good H-bond donor

F
C

H 3C

OH

sterically a little less

accessible but probably not
significant at the site of H-bond donation,
polar -O-H bond.
Good H-bond donor

Inductive effect of the CF3 group strongly

enhances the dipole character of the -O-H bond,
makes the H more !+ and a better H-bond donor

B. Which oxygen is the best H-bond acceptor? Explain by comparing with each of the other two

H
H

C O
H
H F

sterically accessible
oxygen, polar -O-H
bond. Good H-bond
acceptor.

H3C
H3C
H3C

OH

sterically less accessible

oxygen, weaker
H-bond acceptor

H !+

F
C

O !-

H
Inductive effect of the CF3 group strongly
enhances the dipole character of the -O-H bond,
makes the O less !- and a poorer H-bond acceptor

VIII. (10 pts) Pick that member of the following pairs which is more basic, draw the conjugate acid, and give the single
most important reason for your choice with a brief explanation. [resonance, inductive, hybridization, steric, other]
A.

CH3

CH3

special hybridization in the 3-membered ring. More "p" character in the ring bonds, and therefore more "s" character in
the external bonds and orbital with lone pair. Therefore the lone pair "feels" a stronger stabilizing interaction with the nucleus
and is less available as a Lewis base.
CH3

1
N

CH3 Normal tertiary amine, sp3 (approximately) hybridization

B.

N
4

N
4

no delocalization possible;
lone pair remains localized;
normal amine base

etc
Extensive delocalization, resonance structures;
lone pair is dispersed, stabilized, and a weaker
Lewis base.

end exam