Chemistry 118C

Spring 2011
Final
Tues. June 7, 2011
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.
Name: ________________________________________________________________
Last
First
MI
Student ID. # __________________________________________________________
T.A./ Lab Section: ______________________________________________________

Page #

Points Page # Points

10

11
Total
(265)

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.
A)
1) KCN
Br

2) H3O+, heat
3) PBr3

B)

1) SOCl2

OH

2) (CH3CH2)2CuLi
3) H3O+

O
C)

Heat
OH

NH2

NH2

D)

Br2, NaOH, heat

E)

CN

1) H2, Pd
2) CH3CH2CHO
3) NaBH3CN

Cl
F)

KOH, Pd, PR3

heat

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.
O

1) NaOCH2CH3, CH3CH2OH

OCH2CH3 2) (CH3)2CHCH2CH2Br
3) H2SO4, H2O, heat

G)

CH2OH
H)

O
H
H

HIO4
OH
OH
CH2OH

O
I)

1) CH3CH2CHO, NH3, HCl

2) NaHCO3
NH2
1) NaNO2, HCl, H2O 0oC

J)

NH2 2) CuI

O
K)

O
O

L)

CHO
HO
H
H
OH
CH2OH

1) NaOCH2CH3, CH3CH2OH
2) H3O+

NaBH4, CH3OH

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)

Br2, CH3COOH

NH

N)

H
N

1) DCC
OH

2) NH2CH2COOCH3
3) H2, Pd

O
P2S5, heat

O)
O

P)

H
O

1) NH3, HCN
2) H3O+, heat

NaNO3, heat

Q)
N

Fuming H2SO4

O
R)

NK
O

1) BrCH(CO2CH3)2
2) CH3ONa, CH3OH
3) CH3CH2CH2Br
4) H3O+, heat

4. Mechanisms: (20 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

CH3CH2OH (xs)
OH

H2SO4

What is the name of this general mechanism? ______________________

What functional group is formed in this reaction? ______________________
What is the name of this particular reaction? ______________________
5

5. Synthesis: (40 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 five or less carbons.

H 2N

A)
H

N
B)
S

S
O
O

6. Vocabulary: (25 pts.) Fill in the blanks with the appropriate vocabulary word. If
two words are given circle the correct one.
A) An acyl halide / amide / ester has the most resonance between the leaving
group and the carbonyl, which leads to relatively fast / slow reactions with
nucleophiles.
B) In general the acid (-COOH) proton shows up between 0.5 5.0 / 2.0 2.5 / 3-4
/ 6 8 / 10 13 / 13 - 15 ppm in the 1H NMR and the acid (-COOH) carbon
shows up between 30 45 / 60 80 / 110 125 / 165 180 / 195 210.
C) What functional group gets priority in IUPAC nomenclature? amines /
carboxylic acids / aldehydes / alkenes / phenols.
D) A beta anomer of a carbohydrate always has an R / S stereocenter at the
______________ carbon.
E) Nucleophilic aromatic substitution requires an electron-rich / electron-poor
ring.
F) True / False. The best way to make primary amines is by substituting an alkyl
halide with ammonia.
G) Reducing the carbonyl in a monosaccaride to an alcohol produces a compound
of the ________________ class of modified carbohydrates. Oxidizing a
monosaccaride to a dicarboxylic acid produces a compound of the
_________________ class of modified carbohydrates.
H) True / False. In general heterocyclic amines react like amines and heterocyclic
ethers react like ethers unless theyre aromatic at which point they react like
aromatic compounds.
I) Amino-acids are linked by _______________ bonds to form peptides. If the
peptide has more than __________ amino acid residues its considered to be a
protein.
J) There are two kinds of protein secondary structure ___________________ and
__________________ they are formed by London forces / dipole-dipole / salt
bridges / H-bonds / covalent bonds between atoms in the side / main chain.
K) Adding an electronwithdrawing group onto the ring of a phenol makes the OH a
better / worse acid. This effect is less significant if the group is ortho / meta /
para.
L) In general pyridine is more / less electron rich than benzene and pyrrole is
more / less electron rich than benzene.
M) The polysaccaride _____________________ is a(n) alpha / beta linked
polyglucose that is a structural material for plants. Humans can / cannot digest
this molecule.
7

7. Amino-Acids:
A) Calculate the pI of each of the given amino acids (6 pts)
9.7
2.1

O
H3N

9.5

2.2

9.5

H 3N

H 3N

OH

OH

1.9

O
OH

4.1
10.3

Compound A

NH3

HO

Compound B

Compound C

B) Sketch the structure of compound C from question 7A at the given pH (8 pts)

pH 1

pH 3

pH 7

pH 11

8. Identification: (11 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.
S

N
A

Cl

S
B

HN
J

O
H

S
E

N
S
G

OH

N
K

i)

Which of these compounds are NOT heterocycles? ____________________

ii)

Which of these compounds are aromatic? ____________________________

iii)

Which of the nitrogen containing compounds are bases?

_______________________________.

9. Identification: (25 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.
OH

OH
O

HO
HO

OH

O
OH HO

O
HO

OH

CH2OH
H
HO
H
OH
H
OH
CH2OH

OH
O
OH
n

HO

OH

CHO
H
H
OH
CH2OH

HO

HO
OH

OH

HO

OH
I

HO
H

OH
O

HO
HO

H
OH

HO

O
HO
HO

H
HO
H
H

COOH
OH
H
OH
OH
COOH
L

OH

CH2OH
O
H
HO

OH
H
CH2OH
P

HO

HO
HO

HO

HO
OCH3

OH

OH

OH
OH

HO

HO
HO
H

COOH
H
OH
OH
CH2OH

HO
H
H

OH

OH

HO

OH

J
OH

OH
HO
HO

OH

O
HO

O
OCH3

OH

OH
O

O
HO

OH
M

CH2OH
O
H
N
H
2
OH
OH H
OH
H
OH
O
CH2OH
R

HO
O

CHO
H
CH2OH

N
n

OH
O

HO
HO

OH
S

O
HO

OH

O
OH

OH
O
H
OH

OH

OH

HO

OH
T

i) Which of the above are disaccarides? _____________________________________.

ii) Which of the above monosaccarides are L sugars? __________________________.
iii) Which of the above monosaccarides are ketoses? __________________________.
iv) Which of these are non-reducing due to glycoside bonds? ____________________.
v) Which of the non-monosaccarides are -linked? ____________________________.
vi) Which of the cyclized monosaccarides are furanoses? _______________________.
vii) Which of the above is cellulose:_______, sucrose __________, glucose ________?
viii) Which of the above is/are a deoxy-sugar ________, an amino-sugar _________?

10. Nomenclature: (18 pts.). Give the proper (IUPAC) chemical name or draw the
structure of each of the following compounds.
O
A)

N
H
OH

B)
Br

C)
NH

Br
Br

D)

E)

propyl 3-methylamino-2-ethylcyclopentanecarboxylate

N
H

F)

11. pKa: (10 pts). Match each of these with their pKa given below.
pKas = -4, 2-3, 4-5, 8-10, 9-11, 13, 20, 25, 32, 35-40.
H
N

O
N
H

O
H H

H
O
O

OH

O
O

OH

10

O
N
H

HO
H

NH3