Chemistry 14C Lecture 2
Spring 2013
Exam 1
Page 1
OK to use "Ph" anywhere on this exam where appropriate.
Exceeding the specified word limit on an answer will result in a point deduction for that answer.
O
H
Questions 15 concern orotic acid, a substance claimed to be an "ergogentic aid to
exercise" (i.e., a performance enhancer) for athletes and bodybuilders. It is a biological
precursor to RNA and DNA pyrimidines, and is found in high concentration in cow's
milk.
N
HO
N
O
Orotic acid
O
H
H
1.
2.
(3) Circle each atom of orotic acid that has a p orbital.
C
C
H
N
(8) In the boxes below draw two additional resonance contributors for orotic acid. Make your contributors as
significant as possible. Less significant contributors will earn less significant credit. Include all lone pairs and
formal charges.
O
H
N
HO
N
O
Contributor A
3.
Contributor B
Contributor C
(8) Complete each statement by circling "more significant", "equally significant as", or "less significant", as
appropriate. If you circle "equally significant as" you are done with this part. If you circle "more significant" or
"less significant" complete the statement by adding no more than ten words in each space. Use different
reasons for parts (a) and (b).
(a) Contributor A is more significant / equally significant as / less significant than contributor B because
contributor A....
...whereas contributor B...
(b) Contributor B is more significant / equally significant as / less significant than contributor C because
contributor B....
...whereas contributor C...
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Chemistry 14C Lecture 2
4.
Spring 2013
Exam 1
Page 2
(4) Write one number in each blank to complete this statement. The resonance hybrid constructed from all
possible significant orotic acid resonance contributors has __________ atoms with + or charges, and
_____________ atoms which are part of partial pi bonds.
5.
(12) Now let's decide if orotic acid is aromatic. Complete each statement by writing a number in the blank, or
circling "yes" or "no", as appropriate.
(a) Do all of the orotic atoms that you circled in question 1 lie in the same plane when the molecule is in its
lowest energy conformation? Yes
No
(b) Orotic acid has __________ pi electrons.
(c) Orotic acid has ___________ atoms with open valence shells.
(d) Does orotic acid have a closed loop of p orbitals? Yes
(e) Does orotic acid obey Hckel's rule? Yes
(f) Is orotic acid aromatic? Yes
No
No
No
N
N
O
Questions 6 12 concern carnosine, an antioxidant dipeptide. Carnosine
found in muscle and brain tissues more than other tissues in the body.
OH
H2 N
N
H
Carnosine
6.
(3) Write the names of all functional groups in carnosine that are not part of a ring.
7.
(18) Complete each statement by writing one number in each blank.
(a) Carnosine contains _________ sp3 atoms, _________ sp2 atoms, and _________ sp atoms.
(b) Carnosine has _________ lone pairs. Of these lone pairs, _________ are delocalized by resonance.
(c) Carnosine has _________ conjugated atoms.
(d) Carnosine has _________ sp3 stereocenters, _________ enantiomers, and ________ diastereomers.
8.
(2) Rank the electronegativity of the elements in carnosine by writing one element in each blank. Write each
element only once. If there is a tie, write more than one element in the blank. It is possible that some of the
blanks might not be used.
Most electronegative ________ > ________ > ________ > ________ > ________ Least electronegative
9.
(2) Circle the most polar bond in carnosine: NH
NC
CC
C=O
C=N
OH
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Chemistry 14C Lecture 2
Spring 2013
Exam 1
Page 3
N
N
10. (2) Add wedges and hydrogen atoms as necessary to
complete this drawing of carnosine so that all sp3
stereocenters have an S configuration.
OH
H2 N
N
H
11. (6) For each molecule below, circle one or more words or phrases that best describe its relationship with
carnosine.
N
Constitutional isomer
N
(a)
H2N
Configurational isomer
OH
O
Enantiomer
N
H
Constitutional isomer
N
Enantiomer
N
H
Constitutional isomer
N
(c)
Enantiomer
N
H
Stereoisomer
Diastereomer
Meso compound
Identical
Conformational isomer
Configurational isomer
O
H3 N
Stereoisomer
Diastereomer
Meso compound
Identical
Conformational isomer
Configurational isomer
OH
H2N
Stereoisomer
Diastereomer
Meso compound
(b)
Conformational isomer
Identical
Viola sororia and other species of violets are prized for their bright colors and delicate aromas. Three molecules
responsible for the subtle fragrance of violets are -ionone, -ionone, and -ionone.
Question 14
Viola sororia
Question 14
-Ionone
-Ionone
Question 14
-Ionone
12. (2) Complete this sentence by writing a number in the blank. The ionone isomer that has the most conjugated
atoms has _________ conjugated atoms.
13. (2) Circle the ionone isomer that has the greatest number of atoms that lie in the same plane when this molecule
is in its most stable conformation. Circle more than one isomer if there is a tie.
-Ionone
-Ionone
-Ionone
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Chemistry 14C Lecture 2
Spring 2013
Exam 1
Page 4
14. (2) Circle the ionone isomer that has the greatest barrier to rotation around the indicated bond. Circle more than
one isomer if there is a tie.
-Ionone
-Ionone
-Ionone
15. (2) Circle the ionone isomer that can absorb the lowest energy photon. Circle more than one isomer if there is a
tie.
-Ionone
-Ionone
-Ionone
16. (2) It has been suggested that all three ionone isomers are derived from a single biochemical reaction involving
loss of a pyrophosphate group (OPP). In the reaction product list below circle the ionone isomer that is expected
to be the major product.
O
OPP
Lose OPP
-Ionone
-Ionone
-Ionone
Many plants, including violets, owe their bright colors to a series of plant pigments called anthocyanins. These
molecules are ubiquitous; it is estimated that plants around the world make 109 tons of these molecules per year.
Anthoxanithins are also present, but these molecules are generally colorless.
Roses are red, and violets are blue. If you've studied hard you'll know about these molecules too.
OH
HO
OH
HO
OH
OH
HO
HO
An anthocyanidin
An anthoxanithin
17. (2) Circle all the aromatic molecules.
-Ionone
-Ionone
-Ionone
Anthocyanidin
Anthoxanithin
18. (4) Anthocyanidins are red, blue, or violet, but ionones are colorless.
(a) Which differences in molecular structure contribute to this fact? Circle all that apply.
Conjugation
Resonance
Number of pi electrons
HOMO-LUMO gap
(b) Circle the molecule that is more stable: An ionone
Aromaticity
Pi electron energies
An anthocyanidin
Cannot determine from color
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Chemistry 14C Lecture 2
Spring 2013
Exam 1
Page 5
OH
HO
In a plant an anthocyanidin can be bonded with a carbohydrate
to form an anthocyanin. The questions on this exam page
concern the example anthocyanin shown here.
HO
O
OH
OH
O
OH
HO
An anthocyanin
19. (2) Circle the name of the saccharide present in the example anthocyanin:
Allose
Galactose
Glucose
Maltose
Ribose
Sucrose
Starch
20. (8) Circle one word in each set.
(a) The anomeric carbon of the carbohydrate portion of the example anthocyanin is:
(b) The carbohydrate in the example anthocyanin is: Aldose
Ketose
(c) The carbohydrate in the example anthocyanin is: Triose
Tetrose
(d) The example anthocyanin contains: An acetal A hemiacetal
Pentose
Hexose
An acetal and a hemiacetal
None of these
21. (6) Complete this sentence by writing one number in each blank. The example anthocyanin has _________
anomeric carbons. Among these anomeric carbons, _________ are fixed as either or , and _________ exist
as an / mixture.
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