CHEM 234, Spring 2011 FINAL EXAM Ian R.

Gould
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Extra Credit_____/5 Total (incl Extra)________/375+5
H He Interaction Energies, kcal/mol
Li Be B C N O F Ne Eclipsing Gauche
Na Mg Al Si P S Cl Ar H/H ~1.0 Me/Me ~0.9
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr H/Me ~1.4 Et/Me ~0.95

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Me/Me ~2.6 i-Pr/Me ~1.1

Me/Et ~2.9 t-Bu/Me ~2.7
Cs Ba Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
O H C N Infrared Correlation Chart Approximate Coupling
small range usually Constants, J (Hz), for
range of values strong 1
N H C O C H NMR Spectra
broad peak C
C 1600–1660 N
C H O H H H
O C C ~7
C H
3300 C
H 2720–2820 C N
3000– 2 peaks O H H H
3100 C 1680
N H 2200 C C ~10 ~8
OR
C H H
broad with spikes ~3300 1735 H
2850–2960
C CH O 1600
C C ~2 H
O H C
O O H
broad ~3300 2200 ~2
C O H C H
1710 NR2 ~15 H
broad ~3000 1650
C C
(cm-1) 3500 3000 2500 2000 1500 H

amine R NH2 variable and condition NMR Correlation Charts –OCH2– O

alcohol R OH dependent, ca. 2 - 6 δ C CH3
–H2C X
O Aromatic Ar H
–H2C NR2
O C H mainly 8 - 6.5 Alkyl
C CH2 C CH
R C OH 3Y > 2Y > 1Y
11 10 9 8 7 6 5 4 3 2 1 0
(δ, ppm)
220 O 200 180 160 140 120 100 80 60 40 20 0
R C N –OCH2–
R C OH O Alkyl 3Y > 2Y > 1Y
C R2C CR2 RC CR C X

Aromatic C NR2
 CHM 234, Spring 2011, FINAL EXAM - 2- NAME

Question 1 (20 pts.) Provide IUPAC names for the following structures, do not forget to use
E/Z and R/S as appropriate.

1
a) 3 2 CO2H (2S)-hydroxy-3-methylbutanoic acid
4
OH

O Br
b) (2S)-bromo-6-methyloct-(6E)-en-4-one
8 6 4 2
7 5 3 1

Question 2 (20 pts.) Serum creatinine levels are used to measure renal function. Creatinin
exists in several tautomeric forms, two are shown below. Write a curved arrow-pushiung
mechanism that shows how the structure on the left is converted into the one on the right.
Show where all protons come from and go to (no +H+/-H+)
Show all resonance contributors to the intermediate structures
Label the Lewis acid/base and and Bronsted acids/bases as appropriate

LB/BB N H N H
H3O+
N N
N N H
O H O
H
O LA/BA
H H

N H N H N H
N N N
N H N H N H
O O O
H H LA/BA H

O
H H LB/BB
 CHM 234, Spring 2011, FINAL EXAM -3 - NAME
Question 3 (27 pts.) For the following acid/base equilibrium:
a) draw the curved arrows showing bond making/breaking
b) indicate which is the STRONGER and the WEAKER acid and base on each side
c) give a BRIEF explanation for your choice of stronger/weaker that includes the phrase
"energy of the electrons"
H H H H
H H
N H N slower N N
+ H H + H
faster
weaker base weaker acid stronger acid stronger base
larger pKa smaller pKa
equilibrium lies on THIS side
the weaker base has the lower energy electrons, the non-bonding electrons
in A are stabilized by resonance, are this lower in energy
d) Indicate which reaction (left to right or right to left) is faster and which is slower and indicate
on which side the equilibrium lies
e) Draw a PROPERLY labelled reaction energy diagram, indicate the position of the transition
state and include a drawing of the transition state
Energy H H ‡
‡ H
N H N
H

Reaction Coordinate

Question 4 (10 pts.) Indicate which of the following two structures A and B you would expect to
be the stronger Bronsted BASE, and give a brief explanation that includes the term "energy
of the eletrons". Assume that both structures are completely FLAT.

A B

In A the electrons are in an aromatic system and are thus stabilized and lower in nergy,
less reactive, and thus a weaker base, in B the electrons are in an antiaromatic system

Extra Credit Question (5 pts). Which kind of molecule was used in the new Two-Electron
Sensitization Process for Photography that Dr. Gould worked on when at Kodak?

amine ester amide aldehyde

CHM 234, Spring 2011, FINAL EXAM -4- NAME
Question 5. (38 pts.) Give the mechanisms for formation of the "Normal" and the "Conjugate" addition
products in the following reaction.
Show all resonance structures of the intermediates, show where all protons come from and go
to (no +H+/-H+) and label the Lewis/Bonsted acids/bases as appropriate
O O H EtO O H
EtO EtO– +Na/EtOH
+
EtO Conjugate Normal
EtO

EtO H H OEt

O O
EtO O

EtO EtO
b) Both products form with the same exothermicity, draw a reaction energy diagram for both reactions
ON THE SAME DIAGRAM, label the activation energy for the rate determining step for each reaction

EtO O
energy O

EtO
resonance stabilized,
O lower in energy
OH
smaller Ea EtO OH
+ EtO–
EtO
reaction coordinate
c) Under the reaction conditions, the conjugate product will tautomerize back into a ketone, give the
curved arrow-pushing mechanism for this reaction
Show all resonance structures of the intermediates, show where all protons come from and go
to (no +H+/-H+) and label the Lewis/Bonsted acids/bases as appropriate

LA/BA O H OEt LB/BB O

EtO– +Na/EtOH

EtO EtO
O EtO–H O
LA/BA

EtO EtO LB/BB

CHM 234, Spring 2011, FINAL EXAM -5- NAME
Question 6 (64 pts)
Provide the missing products, reagents/conditions or reactants, as required. Do not
forget to include absolute and relative stereochemistry as appropriate unless
otherwise indicated

a) 1. excess CH3I
NH2
2. Ag2O/ H2O
3. heat

1. / H+ cat.
HO O N HO O ignore
H
stereochemistry
b) 2. CH3Br
3. H3O+

H2N OH Ph Cl Ph HN OH
c)
1 equivalent O

NMe2 CO2CH3 NMe2

CO2CH3
d) (±)
heat

1 equivalent
O O O
HO OH O O
e)
O H+ O

H O
H
O HCl cat.
f)
heat H
 -6-
CHM 234, Spring 2011 FINAL EXAM NAME
Question 6, Contd...
Provide the missing products, reagents/conditions or reactants, as required. Do not
forget to include stereochemistry as appropriate.
O O

O OH
g) H3O+
heat
O
O O
OH

H Br H2N CH2 H
1. NaCN
h)
2. LiAlH4
3. H3O+
Question 7 (8 pts) Give a reactants and reagents/conditions that will give the following
structure in a Claisen reaction
O O O
1. Na+ –OMe/MeOH
OMe OMe
O 2. H3O+
O
ignore
+ MeO OMe stereochemistry
excess
Question 8 (12 pts) Give a synthesis of the provided carboxylic acid from malonic ester.
TREAT THIS AS A SYNTHESIS QUESTION. This is a FIVE STEP synthesis, give
reagents/conditions and the intermediate molecules AT EACH STEP.

O O
O
EtO OEt
malonic ester OH

Na+ –OEt/EtOH H3O+ / heat

O O
O O
EtO OEt
EtO OEt
EtBr
EtBr
O O O O
Na+ –OEt/EtOH
EtO OEt EtO OEt
CHEMISTRY 234, Spring 2011 FINAL EXAM -7- NAME
Question 9 (24 pts.) For the cycloaddition reaction below
a) Draw the curved arrow-pushing that describes the bond-making and breaking processes.
Et
Et
Me Δ
+ Me
Pr
Me Pr
Et
Et Me

b) Draw the HOMO and LUMO of the reactants as requested, ON TOP of the structures that
are redrawn below

Et
anti-bonding
Me
Pr
bonding LUMO
Me
HOMO Et

c) Is the cycloaddition reaction shown above allowed or forbidden. Give a BRIEF

explanation that includes the words suprafacial and/or antarafacial as appropriate
this is antarafacial on the cation and suprafacial on the alkene, which is forbidden based on
FMO theory since there is a bonding and an anti-bonding interaction interaction between the
pairs of atoms involved in making the two new sigma bonds

Question 10 (20 pts) Give the mechanism for the following reaction
• AS APROPRIATE, SHOW WHERE ALL PROTONS COMES FROM AND GO TO (no +H+/-H+)
• DRAW ALL RESONANCE CONTRIBUTORS for the intermediates as approriate
• At each INTERMOLECULAR step, INDICATE THE Lewis acid and base (LA or LB) and whether
they are also Bronsted acids and bases (BA or BB) as appropriate
O
O O OH O
+ + O
O OH
LA
LB

O O
LB/BA O
O
O
O H
H O O
LA/BA

O
CHEMISTRY 234, Spring 2011 FINAL EXAM -8- NAME

Question 11 (24 pts.) Give a curved arrow-pushing mechanism for the following reactionShow
where all protons come from and go to (no +H+/-H+)
Show all resonance contributors to the intermediate structures
Label the Lewis acid/base and and Bronsted acids/bases as appropriate

OH
O
H3O+
LB/BB O
H O
H O+ LA/BA
H

OH
O O
O+ H
LA/BA
LB/BB O H O H
H H
O
H
O
LB/BB
OH O H O H

O H O H O H
LB/BB
H
LA/BA O+ H
H
LA/BA
CHM 234, Spring 2011, Final Exam -9- NAME

Question 12 (24 pts) Provided are spectra for a compound with molecular formula C6H12O2

a) Give the degrees of unsaturation 1 degree of unsaturation

________________
b) On the infrared spectrum, indicate the peaks that identify the functional groups in the
molecule (including C(sp3)-H). Indicate BOTH the functional group, and where
appropriate, the specific BOND in the functional group that corresponds to the peak.

3401

H C 1463
2879 1089

sp3 1450
1199
2939
1372
O

1739

c) draw the structure and clearly indicate which hydrogens correspond to which
signals in the proton nmr spectrum (only)

2 peaks here
e
3H a
3H

d c
2H 2H

O d
b b
a CH2 c C CH2 e
O 2H
H3C CH2 CH3
CHM 234, Spring 2011 FINAL EXAM - 10 - NAME
Question 13 (24 pts.) Show how you would make the target componds on the right from the
starting compounds on the left. Show reagents and conditions where appropriate, and the
structures of important intermediate compounds. Do not show any (arrow pushing)
mechanisms. If necessary, you must indicate steps that require separation of isomers
NO2

separate
O isomers

AlCl3 Cl
Cl

O HNO3/H2SO4

Cl2/AlCl3 Cl
Zn/Hg/HCl/H2O

Cl
Question 14 (28 pts) Show how you would make the target componds on the right from the
starting compounds on the left. Show reagents and conditions where appropriate, and the
structures of important intermediate compounds. Do not show any (arrow pushing) mechanisms.
These 2 questions use only reactions from the basic sets that were provided on the class website

a) ignore
stereochemistry

NBS, hν PCC O
Na+ –OH 1. BH3.THF
Br
2. –OH/H2O2
OH

OH

b) Ph
Br

1. BH3.THF OH O
K+ –O-t-Bu 1. PhMgBr
2. –OH/H2O2 PCC
H 2. H3O+
CHM 234, Spring 2011 FINAL EXAM - 11 - NAME

Question 15 (32 pts.) In each case, synthesize the (target) molecules on the right from the
starting molecules the left. this can not be done in one reaction. Give reagents and
conditions and the intermediate molecules at each step. Do not show any mechanisms or
transient intermediates.

a) N

HNMe2/H+
HBr, ROOR H2/Pd/C

O
Br
O H
MgBr 1.
OH
Mg.THF PCC

2. H3O+

H
b)
Br N

O O
O
O

HO
H+
OH Cl

Br
O NH2

O
Na+ –CN
O
CN
O 1. LiAlH4
2. H3O+
O