Chemistry 118C

Fall 2015
Final
Thursday Dec. 10th, 2015
Instructor: Lievens
This exam contains eleven (11) pages and twelve (12) problems. Please make sure
that your copy contains all eleven (11) pages. If there is a problem, please tell the exam
administrator prior to beginning. Please answer all questions. Remember that UCDavis
Code of Academic Conduct applies to this exam and all other graded work in this class.
Please no calculators, notes, books, models, or other aids and remember to turn off cell
phones.

Name: ________________________________________________________________
Last
First
MI
Student ID. # __________________________________________________________
T.A./ Lab Section: ______________________________________________________

Page #

Points Page # Points

10

11
Total
(295)

1. Reactions: (24 pts). Draw the structure of the expected organic product(s) formed
in the following reactions including correct stereochemistry. If the product is
racemic write both isomers or write racemic. Assume all reagents listed are
present in excess unless otherwise noted. If no reaction occurs, state No
Reaction.
O
A)

Br 2, PBr 3 (cat).
OH

1) (CH 3)2CHCH2CH2Li

CN
B)

2) H 3O+

O
C)

1) DIBAL-H
O

2) H 2O

Br

1) NaN 3

D)

2) Pd, H 2
3) CH 3I (xs)

E)

CHO
1) HCN
HO
H
H
OH
2) Pd-BaSO 4
H
OH
3) H 2O
CH2OH
OH

F)

HO
OH

OH

CH 3CH2OH,
OH

HCl (cat.)

2. Reactions: (24 pts). Draw the structure of the expected organic product(s) formed
in the following reactions including correct stereochemistry. If the product is
racemic write both isomers or write racemic. Assume all reagents listed are
present in excess unless otherwise noted. If no reaction occurs, state No
Reaction.
OH
G)

O
OH

pyridine

OH

1) NH 3, CH 3CH2CH2CHO

H)

(xs)

OH

HO

OCH3

2) HNO 3
3) KOH, H 2O
4) CaO, Heat

NH 2
1) NaNO 2, HCl, H 2O 0oC
I)
2)
N
Cl
1) NaOH, heat, pressure

J)

2) H 3O+
1) CH 3CH2CH2CH2Li
S

2)

K)
3) HgSO 4, CaCO 3, H 2O, CH 3CN

L)

CHO
H
OH
HO
H
H
OH
CH2OH

HNO 3, H 2O

3. Reactions: (24 pts). Draw the structure of the expected organic product(s) formed
in the following reactions including correct stereochemistry. If the product is
racemic write both isomers or write racemic. Assume all reagents listed are
present in excess unless otherwise noted. If no reaction occurs, state No
Reaction.
M)

1) NH 3,
2) HCN

H
O

3) H 2SO 4, H 2O, heat

O
N)

H 3CH2CO

1) NaOCH 2CH 3, CH 3CH2OH

O

OCH2CH 3 2)

3) H 2SO 4, H 2O, heat

Br 2, H 2SO 4, SO 3

O)
N

1) KMnO 4, NaOH, H 2O
P)
2) H 3O+
3)CH3CH2OH, H 2SO 4

Q)

1) NaOCH 2CH 3, CH 3CH2OH

O

OH

2) H 3O+

1) Jones reagent

R)

2)
OH

O
, heat

4. Mechanisms: (25 pts). Show the detailed reaction mechanism for each of the
following reactions. Include the structure of the expected products and all relevant
resonance structures.
O
H

NaOH, S

N R

What is the name of this reaction? __________________________________

What is the pKa of the catalyst? ____________________________________
The organic intermediate is a _________________________ anion.

5. Synthesis: (36 pts). Show how you would carry out the following syntheses.
Include the reagents you would need for each step and the structure of the
intermediate products formed in each step. You may use any inorganic reagents
you need and organic reagents of seven or less carbons.
O
H
N

OH
OH

A)

O
O

B)

Br

A)

B)

C)

D)

E)

F)

G)
H)
I)
J)

K)

6. Vocabulary: (40 pts.) Fill in the blanks with the appropriate vocabulary word. If
two words are given circle the correct one.
The commonly occurring amino-acids used in protein synthesis are D / L amino-acids
they are always / sometimes / never S stereocenters and have the amino group on the
ipso / alpha / beta / other carbon.
In general an amide (CONHR) proton shows up between 0.5 5.0 / 2.0 2.5 / 3-4 / 6
8 / 10 13 in the 1H NMR, and an nitrile (-CN) shows up between 10 35 / 65 85
/ 110 126 / 165 185 / 195 210 ppm in the 13C NMR.
Rank the given functional groups from highest to lowest IUPAC priority:
ester, amine, alkene, alcohol, ether
____________> ____________ > ____________> ____________ > __________
Resonance between the carbonyl and leaving group in carboxylic acid derivatives
increases with large / small atoms as the leaving group due to __________________,
and increases with strongly / weakly electronegative atoms due to
____________________. Increased resonance with the leaving group will increase /
decrease acidity at the enolate position and increase / decrease basicity of the
carbonyl lone pair.
The secondary structure of a protein consists of ________________ and
_______________ structures and is held together by _________________ between
atoms in the side chains / backbone, while tertiary structure is held together
by_________________ between atoms in the side chains / backbone. Both are easily
disrupted by: ________ or ________ or ___________.
Ethyl acetoacetate has a pKa of about ___________ at the _____________, which is
more / less acidic than ethyl propionate. The conjugate base of ethyl acetoacetate
generally adds 1,2- / 1,4- to Michael acceptors and always / sometimes / never
undergoes a Robinson annulation.
Claisen rearrangements occur with an ether that has both an _________ and a
__________ group.
True / False Phenols are stable enols, so can tautomerize to carbonyls as the
intermediates in certain reactions.
True / False Phenols are often made by electrophilic aromatic substitution of benzene
with HO+.
Treatment of aniline with NaNO2, HCl, and H2O initially forms the ______________
functional group, which decomposes to an ______________ functional group that can
be used as a nucleophile / electrophile / reducing agent / base, and which is more /
less stable than the same functional group with an alkyl group instead of an aromatic.
Reaction of a carboxylic acid with alcohol and acid is a ___________________
reaction and uses a _________________ mechanism
7

7. Amino-Acids:
A) Calculate the pI of each of the given amino acids (6 pts)
9.0

2.2

O
H 3N

9.6
H 3N

OH

1.9

9.2
OH
3.7

10.5

Compound A

NH 3

OH

1.8

O
H 3N

OH

HN

N H

Compound C

Compound B

B) Sketch the major form of compound C from question 7A in a solution at the given
pH (8 pts)

pH 1

pH5

pH 8

pH 11

8. Structure: (8 pts) Draw the alpha and beta anomers of the furanose and pyranose
forms of D-fructose in the appropriate blanks.

CH2OH
O
HO
H
H
OH
H
OH
CH2OH

furanose

pyranose

furanose

pyranose

D-fructose

6.2

9. Identification: (47 pts.). Using the letter codes identify the given carbohydrates.
Some letters may be used multiple times some may not be used at all. Indicate all
that apply. Extra incorrect answers will lose points.
OH

OH

O
HO

O
HO

OH

O
OH

CH2OH
H
OH
OH
CH2OH

HO
OH
H
OH H

CHO
H
OH
CH2OH

OH
OH

COOH
OH
OH
OH
COOH

H
H
H

HO

OH
HO
OH
F

OH
O

OCH3

HO
HO

OH
HO

OH OH

OH
O
HO

OH
O

OH
OCH3
OH

O
OH

OH

OH

CH2OH

HO
HO
HO

OH

H
OH

HO
HO

OH

OCH3

J
OH

H
H
H

CHO
OH
H
OH
CH2OH

CH2OH
OH
O

HO
HO

OH

OH

O
HO
H
H

H
H
H
HO

H
OH
OH
CH2OH

COOH
OH
OH
OH
H
CH2OH

HO

CH2OH
OCH3
OH

HO
R

HO
HO

H
O

OH

O
HO

OH

O
OH
OH

HO
H
H
HO

O
HO

OH

OH
P

OH

O
HO

OH

OH

O
OH

HO

O
HO

OH

OH OH

OH

COOH
H
OH
OH
H
CH2OH

Q
OH
O

HO
HO

OH
NH 2

CH2OH
O
H
OH
HO
H
CH2OH

i) Which of the above are disaccharides? _____, ____, _____

ii) Which of the above monosaccharides / modified monosaccharides are L sugars?
______, ______, _____, _____, _____, _____, _____, _____.
iii) Which of the above monosaccharides are ketoses? ____, _____, ____, ____, _____.
iv) Which of the above are non-reducing due to glycoside bonds? ___, ____, ____, ____.
v) Which of the above monosaccharides are -anomers? ____, ____, ____, _____, ____.
v) Which of the non-monosaccharides are -linked? ____, _____, ____.
vi) Which of the cyclized monosaccharides are furanoses? ____, _____, _____.
viii) Which of the above is lactose:______, sucrose ______, glucose _____, ribose ____
cellulose _____, fructose _________.
ix) Which of the above is/are a deoxy-sugar _____, a deoxy-amino sugar ____, an
alditol ________, an aldaric acid _______, an aldonic acid _____, ______?
x) Which of the above is/are a form of energy storage in animals ______, a structural
material ____, non-digestible by humans _____, selectively digestable by humans _____.
9

10. Nomenclature: (12 pts.). Give the proper (IUPAC) chemical name or draw the
structure of each of the following compounds. Include stereochemistry where
appropriate.
O
A) HO
NH 2
O
B)

C)

4-(N,N-dimethylamino)-2-ethylphenol
O
HO

N
H

D)

NH
E)

F)
O

OH

11. pKa: (13 pts). Using the letter codes provided rank the two series of compounds
from best acid to worst acid.
OH

A
best acid

OH

OH

OH

CN

CN

OH

OH

OCH3

>

>

>

>

>

worst acid

NH 3
H
N
H M
best acid

N
N
H

>

N
O
H H

>

>

10

>

N
H

N
H

>

NH 2 S
worst acid

12. Spectroscopy: (20 pts.) The unknown compound A (C16H25NO3) gives the
following proton and carbon NMR spectra. Significant IR peaks were also
observed.
What is compound A?

200

150

100

IR: 3256 (broad), 2947, 1740, 1209 cm -1.

11

50