INTRODUCTION TO ORGANIC CHEMISTRY II

CHEM 224

UNIT EXAMINATION #1

STUDENT NAME (PRINT CLEARLY): ANSWER KEY

DO NOT OPEN THIS BOOKLET UNTIL YOU ARE INSTRUCTED

TO BEGIN
(THERE ARE 51 POINTS AVAILABLE IN THIS EXAM. A
MAXIMUM OF 50 WILL BE AWARDED)

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Question 1 Chapter 15: Conjugated Systems, Orbital Symmetry, Ultraviolet
Spectroscopy (17 points).

(a) Among a series of isomeric trienes, the more negative the ∆Η° of the hydrogenation
reaction of a given triene, the stable it is relative to the others in the isomeric
series.

(b) What is the hybridization of the central carbon of allene (1,2-propadiene)?

A) sp
B) sp2
C) sp3
D) p
E) none of the above

(c) What descriptive term is applied to the type of diene represented by 2,4-hexadiene?

A) conjugated diene
B) cumulated diene
C) isolated diene
D) alkynyl diene
E) none of the above

(d) Draw a representation of the highest occupied π MO of 1,3-butadiene in the ground

state.
ANSWER:

(e) How many nodes, other than the node coincident with the molecular plane, are found
in the highest energy π MO of 1,3-butadiene?

A) 0
Β) 1
C) 2
D) 3
E) none of these

(f) When the relative energies of the s-cis and s-trans conformers of 1,3-butadiene are
compared, one finds:

A) that the s-cis conformer is lower in energy than the s-trans.

B) that the s-trans conformer is lower in energy than the s-cis.
C) that the two conformers are of equal energy.

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Question 1 continued

(g) Provide the structure of the major product which results from 1,2-addition of HBr to
the diene shown below:

ANSWER:

(h) Draw the structure of the major organic product which results when the diene shown
below is treated with HBr at 40°C.
CH3
ANSWER:

CH3
(i) What is the major organic product that results when cycloheptene is irradiated in the
presence of N-bromosuccinimide?

A) 1-bromocycloheptene.
B) 2-bromocycloheptene.
C) 1,2-dibromocycloheptene.
D) 3-bromocycloheptene.
E) 4-bromocycloheptene.

(j) In the allyl radical, which π molecular orbital is singly occupied?

A) The bonding π molecular orbital.

Β) The nonbonding π molecular orbital.
C) The antibonding π molecular orbital.
D) None of these.

(k) Provide the structure of the major organic product in each of the following Diels-
Alder reactions (be careful to show stereochemistry where important):
O
H3C heat
+

CO2CH3 heat
+

H3CO O heat
+ CH3

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Question 1 continued

(l) Draw structures for compounds A, B, and C in the scheme shown below.

CHO
NaOEt, EtOH, ∆ CH2=CHCO2H 1) O3
NBS, hν
A C D
(Et = C2H5) 2) (CH3)2S HO2C CHO

ANSWER: A: C: D:

(m) In the UV-visible spectrum of (E)-1,3,5-hexatriene, the lowest energy absorption

corresponds to:

A) A σ to π transition.
B) A σ to π* transition.
C) A π to σ∗ transition.
D) A σ to σ* transition.
E) A π to π* transition.

Question 2 begins on the next page.

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Question 2. Chapter 16: Aromatic Compounds. (19 points)

In Kekulé’s time, cyclohexane was unknown, and there was no proof that benzene must
be a six-membered ring. Determination of the structure relied largely on the known
numbers of monosubstituted and disubstituted benzenes, together with the knowledge
that benzene did not react like a normal alkene. There was a raging controversy over the
structure of benzene, principally between Ladenberg and Kekulé, each of whom thought
his structure was the correct one. A third structure was that proposed by Dewar. The
Kekulé, Ladenberg, and Dewar structures are shown below (all have the formula C6H6).

Kekulé structure
Ladenberg structure Dewar structure
(localized double bonds)

(a) For each structure, draw all the possible different monobrominated derivatives
(C6H5Br) that would result from randomly substituting one hydrogen with a bromine:

(b) Benzene was known to have only one monobromo derivative. For each structure that
has only one monobromo derivative, draw all the possible dibromo derivatives (bear in
mind that, in Kekulé’s time, resonance theory was unknown, and the double bonds in the
Kekulé structure were presumed to be fixed):

(c) Benzene was known to have only one monobromo derivative and three dibromo
derivatives. Moreover, it gave negative chemical tests for an alkene. Based on these
observations, which is the most likely structure for benzene?

Question 2 is continued on the next page.

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Question 2 continued

(d) What factors would make the structure you suggested in part (c) relatively unstable, in
contrast to the known stability of real benzene?

(e) Label each of the following molecules as aromatic, non-aromatic, or antiaromatic:

H H
-
+

(not planar)

(f) In the proton NMR, in what region of the spectrum does one typically observe
hydrogens bound to the aromatic ring (δ scale)?

A) 1.0-1.5 ppm
B) 2.0-3.0 ppm
C) 4.5-5.5 ppm
D) 7.0-8.0 ppm
E) 9.0-10.0 ppm

(g) In the UV-visible spectra of the following compounds, in which does λmax appear at
the longest wavelength?

A) 3-phenylpropene
Β) 1-phenylpropene
C) benzene
D) n-octylbenzene
E) isopropylbenzene

Question 3 begins on the next page

Question 3 Chapter 17: Reactions of Aromatic Compounds. (15 points)

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(a) Draw the structure(s) of the major organic product(s) you would expect to obtain from
each of the following reactions.
NO2
Br2, FeBr3

Br
HNO3, H2SO4

1) CH3COCl, AlCl3

2) Clemmensen
reduction

NHCOCH3
HNO3, H2SO4

CH3

CH3
NaNH2, liquid NH3

Cl

CH3
NO2
KMnO4

CH=CH2 HCl

CH3

CH(CH3)2
Br2, light

Question 3 is continued on the next page

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Question 3 continued

(b) Choose the correct order of reactivity of the following compounds with respect to
their rates of SN1 reaction with water.

CO2CH3 NHCOCH3 CO2CH3 CH3

CH2Br
CH2Br CH2Br CH2Br
C
A B D

A) A>B>C>D
B) B>A>C>D
C) B>D>C>A
D) C>A>B>D
E) D>B>C>A

(c) Draw the four major resonance structures of the sigma complex intermediate in the
reaction of anisole with HNO3/H2SO4 to yield p-nitroanisole:
OCH3 OCH3
HNO3/H2SO4

NO2

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THIS SECTION IS FOR GRADING USE ONLY
Points earned:

Question 1 17
Question 2 19
Question 3 15
TOTAL (THERE ARE 51 POINTS AVAILABLE IN
THIS EXAM. A MAXIMUM OF 50 WILL BE
AWARDED.)

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