Chapter 6

6.1 Calculate the degree of the unsaturation in the following hydrocarbons:

(a) C8H14;
(b) C5H6
(c) C12H20
(d) C20H32
(e) C40H56
Solution:
(a)=2
(b)=3
(c)=3
(d)=5
(e)=13
6.2 Calculate the degree of the unsaturation in the following formula, and the draw as many structures
as you can for each:
(a) C4H5;
(b) C4H6;
(c) C3H4;
Solution:
(a)=1

H2
C

H2C

C
H

H3C

C
H

C
H

H2C

CH3

CH3

CH3

CH3
(b)=2

H2C

C
H

CH3

H2C

C
H

C
H

CH2

HC

H2
C

CH3

H3C

CH3

(c)=2

HC

CH3

H2 C

CH2

6.3 Calculate the degree of unsaturation in the following formulas:

(1) C6H5N 5
(2) C6H5NO2 5
(3) C8H9Cl3

(4) C9H10Br2

(5) C10H12N2O3 6
(6) C20H32ClN 5
6.4 Give the IUPAC name for the following compounds:
(1)

3,4,4-trimethyl-1-pentene
(2)

3-methyl-3-hexene
(3)

4,7-dimethyl-2,5-octadiene
6.5 Draw structures corresponding to the following IUPAC names:
(a)2-Methyl-1,5-hexadiene

(b)3-Ethyl-2,2-dimethyl-3-heptene

(c)2,3,3-Trimethyl-1,4,6-octatriene (d)3,4-diisopropyl-2,5-dimethyl-3-hexene
(e)4-tert-Butyl-2-methylheptane
Solution:

CH3
H3C
H2
C

H2C

H2
C

C
H

CH2

CH3

(a)

CH3

CH2

H2
C

C
H

CH3

(b)

H3 C

CH3
CH

CH3
H 2C

(c)

CH3

CH3

H3C
C
H

C
H

C
H

CH3

C
H

CH3

H
C

CH3

(d)

CH3
C

C
H

CH3

CH
H3 C

CH3

CH3
H3C

H2
C

C
H

H3C

H
C

H2
C

CH3

CH3

CH3

(e)

6.6 Name the following cycloalkenes:

CH3

CH3

CH3

CH3 (b)

(a)
Solution:

CH(CH3)2

(c)

(a) 1,2-Dimethyl-cyclohexene
(b) 4,4-Dimethyl-cycloheptene
(c) 3-Isopropyl-cyclopentene
6.7 Which of the following compounds can exist as pairs of cis-trans isomers? Draw each cis-trans pair,
and indicate the geometry of each isomer.
CH2
(b) (H3C)2C
(a) H3CHC
CHCH3
(d) (H3C)2C
(c) H3CH2CHC
(e) ClHC

(f) BrHC

CHCl

CHCH3
C(CH3)CH2CH3

CHCl

Solution:
(c)

H3CH2C
C
cis:

H3CH2C

CH3

H
C

C
H

trans:

C
CH3

(e)

Cl

Cl
C

Cl

cis: H
(f)
Br

trans: H

Cl

Cl

Br

cis: H

trans:

Cl

6.8 Name the following alkenes, including the cis or trans designation:
H

CH3
H3C
CH

CH

(a)

CH3
C

H3C

H3C

HC
H

CH2

(b)

CH2

C
H

H3C

Solution:
(a) cis-4,5-Dimethyl-2-hexene
(b) trans-6-Methyl-3-heptene
6.9 Which member in each of the following sets has higher priority?
(a) H or Br
(d) NH2 or OH

(b) Cl or Br
(e) CH2OH or CH3

(c) CH3 or CH2CH3

(f) CH2OH or CH=O

Solution:
(a) Br
(b) Br
(c) CH2CH3
(d) OH
(e) CH2OH
(f) CH=O
6.10 Rank the following sets of substituents in order of Cahn-Ingold-Prelog priorities.
(a) CH3, -OH, -H, Cl
(b) CH3, CH2CH3, -CH=CH2
(c) CO2H, -CH2OH, -CN, -CH2NH2
(d) CH2CH3, -CCH, -CN, -CH2OCH3
Solution: (From High to low)
(a) Cl, -OH, CH3, -H
(b) -CH=CH2, CH2CH3, CH3
(c) CO2H, -CH2OH, -CN, -CH2NH2
(d) -CH2OCH3, -CN, -CCH, CH2CH3

CH3

6.11 Assign E or Z configuration to the following alkenes:

Solution:
H3C

CH2OH

Cl

H3CH2C

CH2CH3

Cl

H3CO

CH2CH2CH3

H3 C

CO2H

CN

H3 C

CH2NH2

CH2 OH

6.12 Assign stereochemistry to the following alkene, and convert the drawing into a skeletal structure:
Solution:

COOCH3

CH2OH

Z
6.13

Name the following alkenes, and tell which compounds in each of the following pairs are more
stable:

(a)

H2C

CHCH2CH3

CH3

or
H2C

1-butene

CCH3

2-methyl-1-propene

2-methyl-1-propene is more stable because it is more substituents.

(b)

H
C

CH2CH2CH3

or

H3C

H3C

CH2CH2 CH3

trans-2-hexene

cis-2-hexene
trans-2-hexene is more stable because it is trans isomer.
(c)
CH3

CH3

or

3-methyl-1-cyclohexene

1-methyl-1-cyclohexene

1-methyl-1-cyclohexene is more stable because the carbon has only sp2-sp2 bonds while the other
has sp2-sp3 bonds.
Predict the products of the following reactions:

6.14

HCl

(a)

Cl
H3C

H2C
C

(b)

CH3

CH

Br

HBr

CH3

H3C

(c)

CH3CH2CH2CH

CH2

H3PO4
KI
Br

CH2

CH3

HBr

(d)
6.15 What alkenes would you start with to prepare the following alkyl halides?
(a) Bromocyclopentane
(b) 1-Ethyl-1-iodocyclohexane
(c)

Br
CH3CH2 CHCH2CH2CH3

Solution:
(a) Cyclopentene
(b) 1-Ethylcyclohexene
CHCH2CH3
(c) H3CH2CHC
6.16 Show the structures of carboations you would expect in the following reactions:
(a)

CH3

CH3
H3CH2CC

+ BrH

CHCHCH3

(b)

CHCH3

HI

Solution:
(a)
CH3
H3CH2CC

CH3
CH2CH2CH3

(b)

CH2CH3 +

6.17 Draw a skeletal structure of the following carbocation. Identify it as primary, secondary, or tertiary,
and identify the hydrogen atoms that are involved in hyperconjugation in the conformation shown.
CH3
CH3
H

C
H

CH3

Solution:

It is secondary carbocation.
Only the methyl-group CH that is parallel to the carbocation p orbital can show
hyperconjugation.
6.18 What about the second step in the electrophilic addition of HCl to an alkenethe reaction of
chloride ion with the carbocation intermediate? Is this step exergonic or endergonic? Does the
transition state for this second step resemble the reactant (carbocation) or product (alkyl chloride)?
Make a rough drawing of what the transition-state structure might look like.
Solution: This step is exergonic. The transition state for this second step resemble carbocation.

Br
H

R
C

R
R
transition state

Intermediate

Product

6.19 On treatment with HBr, vinylcyclohexane undergoes addition and rearrangement to yield
1-bromo-1-ethylcyclohexane. Using curved arrows, propose a mechanism to account for this
result.
Solution:
CH3

Br

Br

vinylcyclohexane

CH3
C

CH2CH3

Br
Br

6.20 Name the following alkenes, and convert each drawing into a skeletal structure.

(a)

(b)

2,4,5-trimethyl-2-hexene

1-ethyl-3,3-dimethyl-1-cyclohexene
6.21. Assign stereochemistry (E or Z) to each of the following alkenes, and convert each drawing into a
skeletal structure:

(a)

(b)

SOLUTION:

(a)

(b)
Cl

O
HO

6.22. The following carbocation is an intermediate in the electrophilic addition reaction of HCl with
two different alkenes. Identify both, and tell which C

H bonds in the carbocation are

aligned for maximum hyperconjugation with the vacant p orbital on the positively charged
carbon.

SOLUTION:

3
6.23 Calculate the degree of unsaturation in the following formulas, and draw five possible for each:
(a) C10H16

(b)

C8H8O

(c) C7H10Cl2

(d) C10H16O2 (e) C5H9NO2 (f) C8H10ClNO

Solution
a)

It has 3 unsaturation degrees.

Possible structures:
b) It has 5 unsaturation degrees.
Possible structures:
O

OH
O

OH

OH

c)

It has 2 unsaturation degrees.

Cl

Cl

Cl
Cl

Cl

Cl

Cl

Cl

Cl

Possible structures:

Cl

d) It has 3 unsaturation degrees.

OH
OH

OH

OH

OH
OH
HO

Possible structures:
e)

HO

it has 2 unsaturation degrees.

OH

OH

OH
OH

OH

Possible structures:
f)

OH

H
OH

OH

OH

N
H

OH

HO

OH

N
H

it has 4 unsaturation degrees.

OH

OH

OH

N
H

H
OH

OH

Possible structures:

6.24 A compound of formula C10H14 undergoes catalytic hydrogenation but absorbs only 2 molar
equivalents of hydrogen. How many rings does the compound have?
Solution:
It has 4 unsaturation degrees. Two of them are rings.
6.25 A compound of formula C12H13N contains two rings. How many molar equivalents of hydrogen
does it absorb if all the remaining unsaturations are double bonds?
Solution:
C12H13N=C12H12
Degree of Unsaturation:

(12 2 + 2 12)
=7
2

It can absorb 7-2=5 molar equivalents of hydrogen.

6.26 Name the following alkenes:
H3 C
H

CHCH2CH3
C

(a)

H3 C

C
H

CH2CH3

CH3

CH3CHCH2CH2CH

CH3

(b)

C
H

CH2CH3

(c)

H2C

CCH2CH3
H
CH3

H2C

CH3
C

CHCHCH

(d)

CH3
H
H3C

C
C

(e)

H3CH2CH2C

(f)

H2C

H
C
CH3

C
CH3

CHCH3

Solution:
(a).trans-4-Methyl-2-hexene or (E)-4-Methyl-2-hexene
(b).cis-4-Ethyl-7-methyl-2-octene or (Z)-4-Ethyl-7-methyl-2-octene
(c).2-Ethyl-1-butene
(d).trans-3,4-Dimethyl-1,5-heptadiene or (E)-3,4-Dimethyl-1,5-heptadiene
(e).(2-cis,4-trans)-4,5-Dimethyl-2,4-octadiene or (2Z,4E)-4,5-Dimethyl-2,4-octadiene
(f).1,2-Butadiene
6.27 Ocimene is a triene found in the essential oils of many plants. What is its IUPAC name, including
stereochemistry?
Solution:

(3E)3,7-dimethyl-octa-1,3,6-triene
6.28 -Farnesene is a constituent of the natural wax found on apples. What is its IUPAC
name, including stereochemistry?
Solution:

-Farnesene

(3E,6E)3,7,11-trimethyl-dodeca-1,3,6,10-tetraene

6.29 Draw structures corresponding to the following systematic names:

(a) (4E)-2,4-Dimethyl-1,4-hexadiene
H2
C

H
C

C
H

H3C

Solution: H3C

CH3

(b) cis-3,3-Dimethyl-4-propyl-1,5-octadiene
H3C
CH3
H
H
H
C
C
C
C2H5

CH

C
H

C3H7 H
Solution:
(c) 4-Methyl-1,2-pentadiene

CH3

H
C

C
CH

H
C
H

Solution:

CH3

(d) (3E,5Z)-2,6-Dimethyl-1,3,5,7-octatetraene.
H
H
H

C
C

CH3
C
C

Solution: H

H
C

CH3

(e) 3-Butyl-2-heptene
C4H9
H

C4H9
Solution: H3C
(f) trans-2,2,5,5-Tetramethyl-3-hexene
H3C

CH3

H
C
H3C

Solution:
6.30

H3C

Menthene,

CH3
H

CH3

hydrocarbon

found

in

mint

plants,

has

the

systematic

name

1-isopropyl-4-methylcyclohexhene. Draw its structure.

Solution:
6.31 Draw and name the 6 pentene isomers, C5H10, including E, Z isomers.

1-Pentene

(Z)-2-Pentene

(E)-2-Pentene

2-M ethyl-1-butene

2-M ethyl-2-butene

3-M ethyl-1-butene

6.32 Draw and name the 17 hexene isomers, C6H12, including E, Z isomers.

1-Hexene

(E)-2-Hexene

(Z)-2-Hexene

(E)-3-Hexene

(Z)-3-Hexene

2-M ethyl-1-pantene

2-M ethyl-2-pantene

(E)-4-M ethyl-2-pantene

4-M ethyl-1-pantene

3-M ethyl-1-pantene

(E)-3-M ethyl-2-pantene

(Z)-3-M ethyl-2-pantene

2,3-Dim ethyl-1-butene

(Z)-4-M ethyl-2-pantene

2-Ethyl-1-butene

3,3-Dim ethyl-1-butene

2,3-Dim ethyl-2-butene

6.33 trans-2-Butene is more stable than cis-2-butene by only 4 KJ/mol, but trans-2, 2, 5,
5-tetramethyl-3-hexene is more stable than cis-2, 2, 5, 5-tetrameethyl-3-hexene by 39 KJ/mol.
Explain.
ohydrog

Alkene
(KJ/mol)

(kcal/mol)

cis-2-butene

-119.7

-28.6

trans-2-Butene

-115.5

-27.6

cis-2, 2, 5, 5-tetrameethyl-3-hexene

-151.5

-36.2

trans-2,2,5,5-tetrameethyl-3-hexene

-112.6

-26.9

Solution: Between cis-2-butene and trans-2-Butene, the cis-2-butene has steric strain, so the
trans-2-Butene is more stable. But the steric strain is not large, the difference between them
is not very large. And the cis-2, 2, 5, 5-tetrameethyl-3-hexene has large steric strain, so the

difference

between

cis-2,

2,

5,

5-tetrameethyl-3-hexene

and

trans-2,

2,

5,

5-tetrameethyl-3-hexene is larger.
6.34 Cyclodecene can exist in both cis and trans forms, but cyclohexene cannot. Explain.(Making
molecular models is helpful.)
Solution: the cyclodecene can be

But the cyclohexene can only be:

6.35 Normally, a trans alkene is more stable than its cis isomer. trans-Cyclooctene, however, is less
stable than cis-cyclooctene by 38.5 kJ/mol. Explain.
Build models of the two cyclooctenes and notice that the large amount of torsional strain in
trns-cyclooctene relative to cis-cyclooctene. This strain causes the trans isomer ot be of higher
energy.
6.36 Trans-Cyclooctene is less stable than cis-cyclooctene by 38.5 kJ/mol, but trans-cyclononene is less
stable than cis-cyclononene by only 12.2 kJ/mol. Explain.
trans-Cyclononene has more carbon than trans-Cyclooctene, and the ring is bigger, so the
steric strain is smaller.
6.37 Allene(1.2-propadiene), H 2C

CH 2 ,has two adjacent double bonds. What kind of

hybridization must the central carbon have? Sketch the bonding orbitals in allene. What shape
do you predict for allene.
Solution:
The central carbon is sp hybridized.
The bonding orbitals in allene is showed as follow:

H
H
H

H
H

H
H

C
H

The structure of allene is showed as follow:

H
H
H

C
H

6.38 The heat of hydrogenation for allene(Problem 6.37) to yield propaneis -298 kJ/mol, and the heat

of hydrogenation for a typical monosubsituted alkene such as propene is -126kJ/mol. Is allene

more or less stable then you might except for diene? Explain.
Solution:
Less stable. Because allene give out more heat than diene in hydrogenation which means that it
contains more energy.
6.39 Predict the major product in each of the following reactions:
(a)
CH3

CH3CH2CH

CH3

CCH2CH3

HCl

CH3CH2CH2 CCH2CH3
Cl

(b)

HBr
Br

1-Ethylcyclopentene
(c)
CH3

HI

CH3

CH3CCH2 CCH2 CH3

CH3

2,2,4-Trimethyl-3-hexene
(d)
Cl

1,6-Heptadiene

Cl

2HCl

(e)
CH3

CH3

HBr

6.40 Predict the major product from addition of HBr to each of following alkenes:
(a)

Br

CH3

CH2

Br

HBr

(b)
Br

HBr

(c)
CH3
H3CHC

HBr

CHCHCH3

Br

6.41 Rank the following sets of substituents in order of priority according to the Cahn-Ingold-Prelog
sequence rules:
CH3,
(a)

OCH3,

C O 2H,

Solution: 1.

H.

CH3, 4.

COOH
COOH , 4.

H,

OCH3, 2.

Solution: 1.

Br, 3.

I, 2.

Solution: 1.
OH ,
(b)
(c)

H,

Br,

OH ,

3.

CO2CH3,
CO2CH3, 2.

CH3

CH 2 OH ,

C O 2 H 3.

H.

CH3.

CH 2 OH , 4.

CH3,

(d)

CH2CH3,

CH 2CH 2OH ,

CCH3

C
H

(e)

C
H

Solution:

CH 2Br ,

Solution: 1.
(f)

CH2

1.

CH2

CN,
2.

CH2OCH3 ,

CN, 3.

CH2CH3,
2.

CH3.

CH2CH3, 4.

CH 2CH 2OH , 3.

CCH3, 2.

Solution: 1.

CH 2Br

CH 2NH 2,

C
H

CH 2NH 2, 4.

CH2OCH3,
CH 2 OH ,

CH2CH3.
6.42 Assign E or Z configuration to each of the following alkenes:

3.

CH2

CH 2 OH
C
H

CH2

4.

HOH2C

CH3

HOOC

Z
C

(a)

H3 C

(b)

NC

CH3

Cl

OCH3

H3CO2C

HC

E
C

(c)

H3CH2C

(d)

CH2OH

CH2

HO2C

CH2CH3

6.43 Name the following cycloalkenes:

CH3

(b)

(c)

(e)

(d)

(f)

Solution: (a) 3-Methyl-1-cyclohexene

(b) 2,3-Dimethyl-1-cyclopentene
(c) 1-Ethyl-1,3-cyclobutadiene
(d) 1,2-Dimethyl-1,4-cyclohexadiene
(e) 5-Methyl-1,3-cyclohexadiene
(g) 1,5- cyclooctadiene
6.44 Which of the following E,Z designations are correct, and which are incorrect?
H3C

CO2H
C

C
Z

Br

NC

H
Z

(c)

CH2NHCH3

CH3
C

(d)

(H3C)2NH2C

HOH2C

Br
C

(e) H

CH2CH(CH3) 2
E

(b)

CH2NH2
C

(f)

H3COH2C

C
CH2CH3
CO2H

C
Z

CH2

H3C

(a)

CH2CH
C

C
COCH3

Solution: (a) correct

(b) Correct
(c) incorrect, it should be E
(d) correct
(e) Doesnt show E / Z isomerism.
(f) correct
6.45 tert-Butyl esters [RCO2C(CH3)3] are converted into carboxylic acids (RCO2H) by reaction with

trifluoroacetic acid, a reaction useful in protein synthesis (see Section 26.10). Assign E,Z
designation to the double bonds of both reactant and product in the following scheme, and explain
why there is an apparent change of double-bond stereochemistry:
O
O
C OCH3
C OCH3
H
H
CF3CO2H
C C
C C
C OH
C OC(CH3 )3
H3C
H3C
O
O
O

Solution: The reactant is Z designation, while the product is E designation. Because

receives higher priority than

C OC(CH3)3

C OCH3 , while

C OCH3 receives higher priority than

C OH, and in the reaction

C OH substitute for

C OC(CH3)3.

6.46 Use the bond dissociation energies in Table 5.4 to calculate H0 for the reaction of ethylene with
HCl, HBr, and HI. Which reaction is most favorable?
H2C

CH2

235 KJ / mol

H2C

CH2

CH2

235 KJ / mol

Cl

Br

H2
C

420 KJ / mol

366 KJ / mol
+

H2
C

420 KJ / mol

432 KJ / mol

235 KJ / mol

H2C

H2
C

420 KJ / mol

298 KJ / mol

H2
C

Cl

H o = -91 KJ / mol

338 KJ / mol
H2
C

Br

H o = -104 KJ / mol

285 KJ / mol
H2
C

H o = -109 KJ / mol

222 KJ / mol

6.47: Each of the following carboncations can rearrange to a more stable ion. Propose structure for the
likely rearranges for the likely rearrangement product.

(a)

Solution: (a)

(b)

(c)

(b)

(c)

6.48 Addition of HCl to 1-isopropyl-cyclohexane yields a rearranged product. Propose a mechanism,

showing the structures of the intermediates and using curved arrows to indicate electron flow in
each step.
Cl

ClH

Solution:
H

Cl

H
(E)

Cl

Cl

Cl

6.49

Addition

of

HCl

to

1-isopropenyl-1-methylcyclopentane

yields

1-chloro-1,

2,

2-trimethylcyclohexane. Propose a mechanism, showing the structures of the intermediates and

using curved arrows to indicate electron flow in each step.
Cl
CH3

Cl

CH3
CH3
CH3

Solution:
CH3

CH3
CH3

+
CH3

Cl

CH3

Cl

CH3
CH3

CH3
Cl

6.50 Vinylcyclopropane reacts with HBr to yield a rearranged alkyl bromide. Follow the flow of
electrons as represented by the curved arrows, show the structure of the carbocation intermediate
in brackets, and show the structure of the final product.

Br

Br
?

?
Solution:
H

Br

Br

Br

6.51: Calculate the degree of unsaturation in each of the following formulas.

Solution:
C27H46O

D=5

(b) C14H9Cl5

D=8

(c)

C20H34O5

D=4

(d)

C8H10N4O2 D=6

(e)

C21H28O5

D=8

(f)

C17H23 NO3

D=7

(a)

6.52: Is the rearrangement exergonic or endergonic? Draw the transition state.

Solution: It is a exergonic.
State
H3 C
H
H3C

CH2

6.53 Draw a reaction energy diagram for the addition of HBr to 1-pentene. Let one curve on your
diagram show the formation of 1-bromopentane product and another curve on the same diagram
show the formation of 2-bromopentane product. Label the postions for all reactants, intermediates,
and products. Which curve has higher-energy carbocation intermediate? Which curve has the
higher-energy first transition state?
Solution:
H2
C
Br

H2
C
C
H2

CH3
C
H2

Br
H3C

C
H

H2
C

H2
C

CH3

The vertical axial presents energy, and the horizontal one shows the progress of the reaction.
The red one stands for 2-bromopentane, and the blue one stands for 1-bromopentane.
The blue one has higher-energy cabocation intermediate and the higher-energy first transition state.
6.54 Make sketches of the transition state structures involved in the reaction of HBr with 1-pentene
(Problem 6.53). Tell whether each structure resembles reactant or product.
Solution:
The first one is for forming 1-bromopentane, and the second one is for forming 2-bromopentane.


Br
Br

H
H

H
R

H
H

Br
Br

R
H

Each structure resembles carbocation.

6.55 Aromatic compounds such as benzene react with alkyl chlorides in the presence of AlCl3 catalyst
to yield alkylbenzenes. The reaction occurs through a carbocation intermediate, formed by
reaction of the alkyl chloride with AlCl3 (RCl+ AlCl3

R+AlCl4-). How can you

explain the observation that reaction of benzene with 1-chloropropane yields isopropylbenzene as
the major product?

AlCl3

H3CH2CH2C Cl

Solution:

H
AlCl3

H3CH2CH2C Cl

AlCl4

H C C CH3
H H

H3C CH

CH3

AlCl4
AlCl3

HCl

6.56 Alkenes can be converted into alcohols by acid-catalyzed addition of water. Assuming that
Markonikovs rule is valid, predict the major product from each of the following alkenes.

CH3
(a)

H3CH2CC CH2
CH2

(b)

CH3
(c)

H3C C CH2CH CH2

H

Solution:

CH3

CH3

H3CH2CC CH2

H2O

H3CH2C C CH3

(a)

OH
CH2
H 2O

OH

(b)

CH3
H3 C C CH2CH CH2
H
(c)

H 2O

H
(H3C)2H2C C CH3
OH

6.57 Reaction of 2,3-dimethyl-1-butene with HBr leads to an alkyl bromide C6H13Br. On treatment of
this alkyl bromide with KOH in methanol, elimination of HBr occurs and a hydrocarbon that is
isomeric with the starting alkene is formed. What is the structure of this hydrocarbon, and how do

you think is formed from the alkyl bormide?

Solution:

Br

H2C

CH3

CH3

C
H

CH3

H3C

CH3

CH3

C
H

CH3

H3C

Br

CH3

CH3

Br

CH3

OH

H3C

CH3

CH3

CH3