Name: ________________________
Final
Chem UA 225 Organic Chemistry I
Time: 4:00 pm – 5:50 pm
This exam has nine (9) questions. You can drop two (2)
questions. Please mark the questions you do NOT want to be
graded on THIS title page. If you do not mark any questions on
the title page, we will not grade questions 8 and 9!
All materials will be provided for the exam. You are allowed to
use the chemistry model set. NO personal paper, notes, etc are
allowed during the exam. You can use pen OR pencil.
Question Points Possible Your Score
1 171
2 171
3 171
4 171
5 171
6 171
7 171
8 171
9 171
Assign questions 3
NOT to be graded
on THIS page
Total 1200
1
Question 1
A) Provide line bond structures for each of the following
compounds, CLEARLY indicating stereochemistry wherever
appropriate (15 points each).
i) trans-1-tert-butyl-4-ethylcyclohexane
ii) (3S,6S)-6-isopropyl-3-methyl decane
iii) 2,2-Dibromo-3,3-dichloro-5-5difluoro-6,6-diiodo bicyclo
[2.2.1] heptane
iv) 5-tert-butyl-6,6-dimethyl-3-nonyne
2
B) (21 points) Rank the compounds in order of INCREASING
nucleophile strength from 1 (weakest) to 4 (strongest):
S OH O
C) (10 points each) What are the approx. pKa values (+/- 5) of:
i) Octane
ii) Trimethyl amine
iii) Tartaric acid
iv) Phenol
v) Water
3
D) What is the approx. bond strength (BDE) (in kcal/mol) (+/- 10)
at room temperature (10 points each):
i) a carbon-carbon triple bond
ii) a carbon-hydrogen bond
iii) a carbon-bromine bond
iv) a hydrogen bond in chloroform
4
Question 2
A) (120 points) Iodobenzene dichloride, formed by the reaction of
iodobenzene and chlorine (compound A) is a reagent for the
chlorination of alkane C-H bonds using radical chemistry. Propose
a radical chain mechanism for the chlorination of a typical alkane
RH by iodobenzene dichloride. The overall equation for the reaction
is given below as well as the initiation step.
Cl
I + RH RCl + HCl + I
Cl
A
Initiation:
Cl UV light
I I Cl + Cl
Cl
5
B) (51 points) On the basis of reactivity (tertiary, secondary,
primary) and sterics (which might hinder the approach of the reagent
towards a CH bond) predict the THREE major sites of chlorination
in the steroid molecule below. Describe your reasoning in 2
sentences or less.
CH3
CH3 H
H H
6
Question 3
Provide the missing products and reaction conditions, i.e. fill in the
boxes.
1) TsCl
2) MeONa Me
OH O
1) O3
Br
2) H2O2
HgSO4
H3O+
OH
Me +
OH
H
7
Question 4
A) The structure of Taxol (paclitaxel), a chemotherapy drug for a
number of cancers, is given below. Assign all eleven stereocenters
as R and S:
O O OH
O
O NH O
H O
O O
OH O
OH O O
8
B) The structure below is menthol. Identify all stereocenters.
Natural (-) menthol is the 1R,2S,5R-stereoisomer. Provide a
CLEAR drawing of (-) menthol.
OH
9
Question 5
A) (100 points) 1,2 Diols are converted to carbonyl compounds
when treated with strong acid (called the Pinacol rearrangement).
Draw a step-by-step (curved arrow) mechanism for this reaction.
HO O
CH3 H2SO4
H 3C H 3C
CH3 CH3
H 3C H 3C
OH CH3
10
Question 5
B) (71 points) Draw the MOST STABLE conformation for each of
the following cyclohexanes:
a) Trans-3-methylcyclohexanol
b) Cis-1-methyl-3-(1-methyl ethyl) cyclohexanes
c) Trans-1-ethyl-3-methoxy- cyclohexane
d) Cyclohexanol
11
Question 6
A) (90 points) Lactones, cyclic ester, are prepared by
halolactonization, an addition reaction to an alkene.
Iodolactonization of B forms C. Draw a step-by-step (curved
arrow) mechanism for this reaction.
O
HO O
I 2, NaHCO 3 O
OCH3 OCH3
I
HO
OH
B
C
12
Question 6
B) (81 points) Humulene and a-caryophyllene alcohol are terpene
constituents of carnation extract. The former is converted into the
later by acid-catalyzed hydration in one single step. Draw a step-by-
step (curved arrow) mechanism for this reaction.
H +, H 2O
OH
Humulene a-Caryophyllene alcohol
13
Question 7
You have just been named president of the world famous perfume
company Scents R Us. In your stockroom, you run across a bottle
labeled C10H20O which contains a liquid with a fantastic sweet
aroma that you bet will be the next ‘super perfume’ and will make
you rich. However, you do not have the structure. Elucidate it from
the following information (make sure you include your reasoning):
1
H NMR: d = 0.94 (doublet, J = 7Hz, 3H), 1.63 (singlet, 3H), 1.71
(singlet, 3H), 3.68 (triplet, J = 7Hz, 2H), 5.10 (triplet, J = 6Hz, 1H)
ppm. The other 8 hydrogens have overlapping signals in the range
from d = 1.3-2.2 ppm.
13
C NMR (decoupled): d = 60.7, 125.0, 130.9 ppm. Seven other
signals are upfield of d = 40 ppm.
IR: signals at 1640 and 3350 cm-1
Oxidation with PCC (oxidizes primary alcohols to aldehydes) gives
a compound with the formula C10H18O. Its spectrum has the
following changes:
1
H NMR: signal at 3.68 (triplet, J = 7Hz, 2H) is gone but a new
signal is seen at 9.64 ppm.
13
C NMR (decoupled): signal at 60.7 ppm is gone but you get a new
signal at 202.1 ppm.
IR: loss of signal at 3350 cm-1
Hydrogenation of the original compound gives C10H22O, identical
with that formed on hydrogenation of the natural product geraniol
(see below).
OH
14
Question 7
15
Question 8
Using the starting material on the left as the only source of carbons
in the final product, show how to synthesize the molecule on the
right. You can use any other reagents. You must show all molecules
synthesized along the way and the reagents needed for each step. Do
not show mechanisms! Read these directions again and be sure to
understand them!
A) (51 points)
16
B) (60 points)
O
C) (60 points)
Br
Br
17
Question 9
Predict all the products for the following reactions. Indicate
major/minor products with an appropriate stereochemistry. (No
mechanisms!)
Br 1. Li
1.
2. D2O
1. O3
2.
2. H2O2
Br2
3.
light
KMnO4
4.
H CH3
5. Br K OC(CH3)3
O
O
6. O CH3OH
CH3OH2
Br KCN
7.
DMSO
18
Scrap Paper (will not be graded)
19
Scrap Paper (will not be graded)
20
Here is a Periodic Table and a NMR table:
21
