184 CHAPTER 4 Alkanes and Cycloalkanes

4.13 Drawing the More Stable Chair Conformation of Polysubstituted Cyclohexanes

STEP 1 Using a numbering system, STEP 2 Using the information STEP 3 Assess the energy cost of
determine the location and configuration from step 1, draw both chair each axial group.
of each substituent. conformations.
Ethyl is at C-1 7.6
Et 8.0
and is UP
Et kJ/mol Et kJ/mol Me
Cl
Me Cl
Me Me Et
1
2 Me Cl 2.0
Methyl is at C-2
5 3 kJ/mol
4 and is UP Et Total energy cost
Cl =8.0 kJ/mol Total energy cost
Cl
Chlorine is at C-5 =9.6 kJ/mol
and is DOWN Lower energy

Try Problems 4.334.35, 4.53, 4.55, 4.57, 4.61, 4.69

Practice Problems Note: Most of the Problems are available within

WileyPLUS, an online teaching and learning solution.

4.39 Identify the name of the parent for each of the following 4.42 For each of the following pairs of compounds, identify
compounds: whether the compounds are constitutional isomers or different
representations of the same compound:

(a)
(a) (b)

(b)

(c) (d)

4.40 Each of the structures in the previous problem has one

or more substituents connected to the parent.
(a) Identify the name of each substituent in 4.39a. (c)
(b) Identify the common name and the IUPAC name of the
complex substituent in 4.39b. 4.43 Use a Newman projection to draw the most stable con-
(c) Identify the name of each substituent in 4.39c. formation of 3-methylpentane, looking down the C2!C3 bond.
(d) Identify the common name and the IUPAC name of the
complex substituent in 4.39d. 4.44 Identify which of the following compounds is expected
to have the larger heat of combustion:
4.41 What is the systematic name for each of the following
compounds:

4.45 Draw each of the following compounds:

(a) 2,2,4-Trimethylpentane
(a) (b) (b) 1,2,3,4-Tetramethylcycloheptane
(c) 2,2,4,4-Tetraethylbicyclo[1.1.0]butane

4.46 Sketch an energy diagram that shows a conformational

analysis of 2,2-dimethylpropane. Does the shape of this energy
diagram more closely resemble the shape of the energy dia-
(c) (d) gram for ethane or for butane?

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 Practice Problems 185

4.47 What are the relative energy levels of the three stag-
gered conformations of 2,3-dimethylbutane when looking
down the C2!C3 bond?
4.48 Draw the ring flip for each of the following compounds:
4.53 Menthol, isolated from various mint oils,
is used in the treatment of minor throat irritation.
Draw both chair conformations of menthol, and
indicate which conformation is lower in energy.
OH

Cl
Menthol
OH
OH 4.54 Draw both chair conformations for each of the follow-
OH ing compounds. In each case, identify the more stable chair
(a) Cl (b) (c) Cl conformation:
(a) Methylcyclohexane
4.49 For each of the following pairs of compounds, identify
the compound that would have the higher heat of combustion: (b) trans-1,2-Diisopropylcyclohexane
(c) cis-1,3-Diisopropylcyclohexane
(d) trans-1,4-Diisopropylcyclohexane

(a) 4.55 For each of the following pairs of compounds, deter-

mine which compound is more stable (you may find it helpful to
draw out the chair conformations):

(b)

(a)
(c)

(d) (b)

4.50 Draw a relative energy diagram showing the conforma-

tional analysis of 1,2-dichloroethane. Clearly label all staggered
conformations and all eclipsed conformations with the corre- (c)
sponding Newman projections.

4.51 Assign IUPAC names for each of the following com-

(d)
pounds:

H H H 4.56 Draw a Newman projection of the following compound,

H H H CH3 as viewed from the angle indicated.

H H H
(a) CH3 (b) H H
Cl Br
CH3 CH3
H H
Cl Br
H H OH
(c) H (d) CH3
HO
4.57 Glucose (a sugar) is produced by O
4.52 The barrier to rotation of bromoethane is 15 kJ/mol. photosynthesis and is used by cells to
Based on this information, determine the energy cost associ- store energy. Draw the most stable con-
HO OH
ated with the eclipsing interaction between a bromine atom formation of glucose:
and a hydrogen atom. OH
Glucose

klein_c04_136-187hr3.indd 185 10/29/10 9:47 AM

 186 CHAPTER 4 Alkanes and Cycloalkanes

4.58 Sketch an energy diagram showing the conformational secondary messengers in eukaryotic cells. Draw the more stable
analysis of 2,2,3,3-tetramethylbutane. Use Table 4.6 to deter- chair conformation of myo-inositol.
mine the energy difference between staggered and eclipsed
conformations of this compound. OH
HO OH
4.59 Rank the following conformations in order of increasing
energy:
HO OH
Br
Br
H Br H OH
H Br
H H
4.62 Below is the numbered skeleton of trans-decalin:
H HH
9 1 3
10 2
Br
Br Br 7 5
H H H 8 6 4
H
H H
Identify whether each of the following substituents would be
HH Br
in an equatorial position or an axial position:
(a) A group at the C-2 position, pointing UP
4.60 Consider the following two conformations of 2,3-dimeth- (b) A group at the C-3 position, pointing DOWN
ylbutane. For each of these conformations, use Table 4.6 to (c) A group at the C-4 position, pointing DOWN
determine the total energy cost associated with all torsional
(d) A group at the C-7 position, pointing DOWN
strain and steric strain.
(e) A group at the C-8 position, pointing UP
CH3 (f) A group at the C-9 position, pointing UP
CH3
H CH3 H3C CH3
H 4.63 Propylene is produced by cracking petroleum and is a
H CH3 very useful precursor in the production of many useful poly-
(a) CH3 (b) H CH3 mers. Propylene has one constitutional isomer. Draw that iso-
mer, and identify its systematic name.
4.61 myo-Inositol is a polyol (a compound containing many
OH groups) that serves as the structural basis for a number of
Propylene

Integrated Problems
4.64 trans-1,3-Dichlorocyclobutane has a measurable dipole 4.66 For each pair of compounds below, determine whether
moment. Explain why the individual dipole moments of the they are identical compounds, constitutional isomers, stereo-
C!Cl bonds do not cancel each other to produce a zero net isomers, or different conformations of the same compound:
dipole moment. CH2CH3
H CH3 H3C CH3
Cl Cl
H CH2CH3 H CH2CH3
trans-1,3-Dichlorocyclobutane (a) H H

4.65 Do you expect cyclohexene to adopt a chair conforma-

tion? Why or why not? Explain.
(b)

Cyclohexene (c)

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 Challenge Problems 187

H CH3
H CH3

H H
(h) H H
(d)
CH3 CH3
CH3 CH3 H H H CH3 H3C CH3

H CH3 H H
(i) CH3 CH3
CH3 CH3
(e) H H CH3 CH3
H CH3 H CH3
CH3 CH3 H CH3
H CH3 H3C H
(j) CH3 CH3
CH3 H
(f) H H

(k)

(g) (l)

Challenge Problems
4.67 Consider the structures of cis-1,2-dimethylcyclopro- 4.69 Consider the following tetra-substituted cyclohexane:
pane and trans-1,2-dimethylcyclopropane: OH

(a) Which compound would you expect to be more stable? Cl

Explain your choice.
(b) Predict the difference in energy between these two
compounds.
4.68 If we compare the sizes of the halogens, we find that
they increase in size from fluorine to iodine. Nevertheless, fluo-
roethane, chloroethane, bromoethane, and iodoethane all have
very similar barriers to rotation about the C!C bond. Can you
offer a possible explanation?
(a) Draw both chair conformations of this compound.
(b) Determine which conformation is more stable.
(c) At equilibrium, would you expect the compound to
spend more than 95% of its time in the more stable chair
conformation?
4.70 Consider the structures of cis-decalin and trans-decalin:
H H

barrier to rotation H
compound (kj / mol)
H
Fluoroethane 13.8
cis-Decalin trans-Decalin
Chloroethane 15.5
(a) Which of these compounds would you expect to be more
Bromoethane 15.5
stable?
Iodoethane 13.4
(b) One of these two compounds is incapable of ring flipping.
Identify it and explain your choice.

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