Chapter 14

14.1 Allene, H2C=C=CH2, has a heat of hydrogenation of -298KJ/mol (-71.3 kcal/mol). Rank a
conjugated diene, a nonconjugated diene, and an allene in order of stability.
Solution:

Stability

-298KJ/mol least stable

H2C C CH2

H2
H2C C C C CH2 -253KJ/mol
H H

H2C C C CH2 -236KJ/mol most stable

H H
14.2 Give the structures of both 1,2 and 1,4 adducts resulting from reaction of 1 equivalent of HCl with
1,3-petadiene.
Solution:
1st

H
H2C C C CH CH3 H Cl H3C C C CH CH3
H H H

H
H2C C C CH CH3 H Cl H2C C C CH2 CH3
H H H

2nd
H
H3C C C CH CH3 H3C C C CH CH3
H H H

H
H2C C C CH2 CH3 H2C C C CH2 CH3
H H H

Therefore, the adducts are:

H
H3C C C C CH3 4-Chloro-pent-2-ene
H H

Cl

H2
H2C C C C CH3 1-Chloro-pent-2-ene
H H

Cl

H H2
H2C C C C CH3 3-Chloro-pent-1-ene
H

Cl

14.3 Look at the possible carbocation intermediates produced during addition of HCl to 1,3-pentadiene
(Problem 14.2),and predict which 1,2 adduct predominates. Which 1,4 addition adduct
predominates?
Solutions
Cl

is the predominate adduct

14.4 Give the structure of both 1,2 and 1,4 adduct resulting from reaction of 1 equivalent of HBr with
the following substance?
Solutions:
The reaction carries out as follows:
 CH3

CH3

CH3 CH3

CH3 CH3

CH3 CH3
Br

CH3 CH3
Br

Red stands for Br atom, green stands for hydrogen atoms and black stands for carbon atoms.

is the structure of

CH3
Br

CH3
 is the structure of
CH3

CH3
Br
14.5 The 1,2 adduct and the 1,4 adduct formed by reaction of HBr with 1,3-butadiene are in
equilibrium at 40℃. Propose a mechanism by which the interconversion of products takes place.
(See Section 11.6)
Solution:
HBr H
H2C C C CH2 H3C C C CH2 + H2C C C CH3
H H H H H

Br Br

1,2 adduct 1,4 adduct

H H+
H3C C C CH2 H3C C C CH2 + BrH
H H

Br

H2C C C CH3 +H2C C C CH3 + Br

H H H H

Br

14.6 Why do you suppose 1,4 adducts of 1,3-butadiene are generally more stable than 1,2 adducts?
Solution:
According to Zaitsev’s rule, the intermediate of the 1,4 adduct is more stable than the 1,2 adduct, so 1,4
adducts of 1,3-butadiene are generally more stable than 1,2 adducts.

14.7 Predict the product of the following Diels-Alder reaction:

 O

H C OCH3

+ C C

H3C H
Solution:
O
O
H
C OCH3 C OCH3
H
+ C C

H3C H H
CH3

14.8 Which of the following alkenes would you expect to be good Diels-Alder dienophiles?

O O

(a)H2C CHCCl (b)H2C CHCH2CH2COCH3 (c)

O O

(d) (e)
Solution:
(a),(d)

14.9 Which of the following dienes have an s-cis conformation, and which have an s-trans
conformation? Of the s-trans dienes, which can readily rotate to s-cis?

(b) (c)
(a)

Solution:
(a) has an s-cis conformation, (b) and (c) have an s-trans conformation, and (c) rotate to s-cis.

14.10 Predict the product of the following Diels-Alder reaction:

 + →?
Solution:
The product is:
CH3

H CO2CH3
H CO2CH3

14.11 Draw a segment of the polymer that might be prepared from 2-phenyl-1, 3-butadiene.

C6H5

*
*

14.12 Show the mechanism of the acid-catalyzed polymerization of 1, 3-butadiene.

The progress goes on and product polymers.

14.13 Calculate the energy range of electromagnetic radiation in the UV region of the spectrum
from 200 to 400 nm. Recall the equation.
E=NAhc/λ=(1.20*10-4kJ/mol)/λ（m）
Solution: E1=1.20*10-4 /200(nm)=600kJ
 E2=1.20*10-4 /400(nm)=300kJ
The energy range of UV is 300~600kJ/mol

14.14 How does the energy you calculated in Problem 14.13 for UV radiation compare with the
values calculated previously for IR and NMR spectroscopy?
Solution: The energy range of IR is 4.8~48kJ/mol;
NMR required about 8.0*10-5kJ/mol.
So the energy for UV is greater than IR and NMR.

14.15 A knowledge of molar absorptivities is particularly important in biochemistry where UV

spectroscopy can provide an extremely sensitive method of analysis. For example, imagine that
you wanted to determine the concentration of vitamin A in a sample. If pure vitamin A has
λmax=325(ε= 50,000), what is the vitamin A concentration in a sample whose absorbance at 325
nm is A=0.735 in a cell with a path length of 1.00 cm?
Solution: C=A/(ε*l)=1.47×10-5 mol/L

14.16 Which of the following compounds would you expect to show ultraviolet absorption in the 200
to 400 nm range?
H 2C C C N
(a) 1,4-cyclohexadiene (b) 1,3-cyclohexadiene (c) H

CH3
CO 2H
N
(d) OCOCH3 (e) O (f) H
Solution: b, c, d, e, f

14.17 Write the structure of all possible adducts of the following diene with 1 equivalent of HCl.
Solution:
All possible adducts as follow:
Cl Cl

H Cl H Cl

14.18 Write the product of the Diels-Alder reaction of the following diene with 3-buten-2-one,
H2C=CHCOCH3. Make sure you show the full stereochemistry of the reaction product.

Solution:

H H

H O

H3C

14.19 The following diene does not undergo Diels-Alder reactions. Explain.
Solution: Because the ends of the diene partner are too far apart and steric strain between the two
methyl group prevents the molecule from adopting s-cis geometry.
 CH3
CH3

14.20 Which of the following molecules are conjugated? Circle the conjugated part in each.

(a) not conjugated

H2 C

(b) H2 C conjugated

H2C C C N
(c) H conjugated

O O

C O CH3 C O CH3

(d) conjugated
CH3

C
CH2

(e) not conjugated

H

H
C
CH2
C
CH2

(f) conjugated 0

14.21 Give IUPAC names for the following compounds:

CH3

(a) CH3CH CCH CHCH3

(b) H2 C CHCH CHCH CHCH3
(c) CH3 CH C CHCH CHCH3
CH3 CH CCH CH2

(d) CH2CH2CH3
Solution:
(a) 3-methyl-2,4-hexadiene
(b) 1,3,5-heptatriene
(c) 2,3,5-heptatriene
(d) 3-propyl-1,3-pentadiene

14.22 What product(s) would you expect from 1,3-cyclohexadiene with each of the following?
(a) 1 mol Br2 in CH2Cl2
(b) O3 followed by Zn
(c) 1 mol HCl in ether
(d) 1 mol DCl in ether
(e) 3-Buten-2-one(H2C=CHCOCH3)
(f) Excess OsO4, followed by NaHSO3
Solution:
(a)
Br Br

Br
CH2Cl2
+ Br2 +

Br
(b)
O O
O3
HC CH + CHOCH2CH2CHO
Zn

(c)
 Cl

Ether
+ HCl

(d)
Cl Cl

D
Ether
+ DCl +

D
(e)
O

C
+ H2C CHCOCH3 CH3

(f)
OH

HO
OsO4

NaHSO3
HO

OH

14.23 Draw and name the six possible diene isomers of formula C5H8.Which of the six are conjugated
dienes?
Solution:
 1,3-Pentadiene

1,4-pentadiene

2-methyl-1,3-butadiene

2,3-pentadiene

2-methyl-1,3-butadiene

1,2-pentadiene

14.24. Treatment of 3,4-dibromohexane with strong base leads to loss of 2 equivalents of HBr and
formation of a product with formula C6H10. Three products are possible. Name each of the three, and
13
tell how you would use C NMR spectroscopy to help identify them. How would you use UV
spectroscopy?
Solution:
The three products:

2,4-hexadiene

2,3-hexadiene

3-hexyne

The way to identify:

1. Use of 13C NMR Spectroscopy:
2,4-Hexadiene has 1 sp3 carbon resonance in the 20 to 50 δ range and 2
sp2-carbon resonances in the 100 to 150 δrange.
 2,3-hexadiene has 3 sp3-carbon resonances in the 20 to 50 δ range and 3
sp2-carbon resonances in the 100 to 150 δ range.
3-hexyne has 2 sp3-carbon resonances in the 20 to 50 δ range and one signal
between 65-85 ppm assigned to SP hybridized carbon.

2. Use of UV spectroscopy:
2,3-hexadiene has a shorter λmax than 2,4-hexadiene and 3-hexyne hasn’t
absorption.

14.25 Electrophilic addition of Br2 to isoprene (2-methy-1.3-butadiene) yields the following product
mixture:

Br2 CH2Br
CH2Br
BrH2C BrH2C
Br
Br
21% 76%
3%
Of the 1,2 and 1,4-additon products, explain why 3,4-dibromo-3-methyl-1-butene (21%)
predominates over 3,4-dibromo-2-methyl-1-butene (3%).
Solution:

2 4
1 3 For the methyl group is an electron pushing group. So the density of electron on C1
and C2 are bigger the electron density on C3 and C4. So, as an electrophile, the Br2 is more likely to
add to C1 and C2.

14.26 Propose a structure for a conjugated diene that gives the same product from both 1,2 and 1,4
addition of HBr.
Solution:

can be the conjugated diene the give the same product.

14.27 Draw the possible products resulting from addition of 1 equivalent of HCl to
1-phenyl-1,3-butadiene. Which would you expect to predominate, and why?
CH CH CH CH2

1-Phenyl-1,3-butadiene
Solution:
 Cl

Cl

Cl

Cl

10.28 2,3-Di-tert-butyl-1,3-butadiene does not undergo Diels-Alder reactions. Explain.

(H3C)3C CH2
C

C
(H3C)3C CH2 2,3-Di-tert-butyl-1,3-butadiene
Solution:
Because of the bulk of the tert-butyl, the C-C bond has the s-trans relationship.

This structure forbids the Diels-Alder reactions.

14.29 Diene polymers contain occasional vinyl branches along the chain. How do you think these
branches might arise?
H2C C C CH2 CH2CH CHCH2CH2 CHCH2CH CHCH2
H H
C CH2
H
A vinyl branch
Solution: The presence of a vinyl branch is because of the occurring of 1,2-addition.
14.30 Tires whose sidewalls are made of natural rubber tend to crack and weather rapidly in areas
around cities where high levels of ozone and other industrial pollutants are found. Explain.
Solution: Because natural rubber is the polymer of isoprene containing carbon double bonds, which can
be oxidized by ozone, causing the polymer to be decomposed, as a result tires tend to crack and
weather rapidly in areas where high levels of ozone are found.

14.31 Would you expect allene, H2C C CH2, to show a UV absorption in the 200 to 400 nm
range? Explain.
Solution: No I wouldn’t expect it. Because the molecular is not conjugated π electron system.

14.32: Which of the following compounds would you expect to have a πÆπ* UV absorption in the 200
to 400 nm range?

(a) (b) (c)

CH2 (H3C)2C C O

N
A ketene
Pyridine
Solution: (b)

14.33 Predict the products of the following Diels-Alder reactions:

CHO
(a)
+

CHO
O

(b)
+ O

O O

O
O
O

(c)

O
+

O
O
14.34 Show the structure, including stereochemistry, of the product from the following Diels-Alder
Reaction
O
H
C OCH 3
COOCH3

+ H
H COOCH3
H 3CO C

14.35 How can you account for the fact that cis-1, 3-pentadiene is much less reactive than trans-1,
3-pentadiene in the Diels-Alder reaction?
Solution: When cis-1,3-pentadiene rotates to the s-cis conformation, a steric interaction occurs between
the methyl group protons and a hydrogen on C1. Since it’s more difficulty for
cis-1,3-pentadiene to assume the s-cis conformation, it is less reactive in D-A reaction.
H H H
H

H H H
H

CH3 H

H H3C

cis-1,3-pentadiene trans-1,3-pentadiene

14.36 Would you expect a conjugated diyne such as 1, 3-butadiyne to undergo Diels-Alder reaction
with a dienophile? Explain.
Solution: it is hard to take place this reaction. First, the diyne is linear structure, the two ends are too far
apart just like trans-1, 3-butadiene. Second, suppose it can react, the product will be

, they are so reactive that they are hardly exist.

14.37 Reaction of isoprene (2-mehtyl-1,3-butadiene ) with ethyl propenoate gives a mixture of two
Diels-Alder adducts. Show the structures of each, and explain why a mixture is formed.
 COOCH2CH3

COOCH2CH3

COOCH2CH3

For isoprene both the 1,4 carbons are partial negative, and for ethyl propenoate the
terminal carbon connected with double bond are partial positive. So we get two products.

14.38 Rank the following dienophile in order of their expected reactivity in the Diels-Alder
reaction. Explain.
N N

C C
1 C C

C C

N N

2 H2C C CHO
H

4 H2C C CH3
H
Reactivity 1>2>4>3.The Diels-Alder cycloaddition reaction occurs most rapidly and in
highest yield if the dienophile has an electron withdrawing substituent group. So the
dienophile with the stronger electron withdrawing will be more reactive.

14.39 Cyclopentadiene is very reactive in Diels-Alder cycloaddition reactions, but 1,3-cyclohexadiene

is less reactive and 1,3-cycloheptadiene is nearly inert. Explain. (Molecular models are helpful)
Solution:
The structures of the three cyclodiene are showed as follow:
In the reaction process, the dienophile need to overcome the repulsion of steric strain, as we know that
the more methylene groups the cyclodiene has, the more steric strain it contains. So the reactivity of
cyclodiene is in the given order.

14.40 How would you use Dies-Alder cycloaddition reactions to prepare the following product? Show
the starting diene and dienophile in each case.
O

O H

CN
(a). O (b).
O

(c). O (d). CO2 CH3

Solution:
O

O CN

(a). O (b).
O

CO2CH3

(c). O (d).

14.41 Aldrin, a chlorinated insecticide now banned for use in the United States, can be made by
Diels-Alder reaction of hexachloro-1, 3-cyclopentadiene with norbornadiene. What is the
structure of aldrin?

Norbornadiene
Solution:
Cl Cl

Cl Cl
Cl
Cl Cl

+
Cl
Cl Cl
Cl

Cl

hexachloro-1, 3-cyclopentadiene norbornadiene

aldrin

14.42 Norbornadiene (Problem 14.41) can be prepared by reaction of chloroethylene with

cyclopentadiene, followed by treatment of the product with sodium ethoxide. Write out the
overall scheme, and identify the two kinds of reactions.
Solution:

H H H

(1) + H
The Diels-Alder
cycloaddition reaction
H
H Cl
Cl

(2) H sodium ethoxide

The E2 reaction
H

Cl

H Na+
+ -O + OH + NaCl
H

Cl

14.43 We’ve seen that the Diels-Alder cycloaddition reaction is a one-step, pericyclic process that
occurs through a cyclic transition state. Propose a mechanism for the following reaction:

Heat
+ H2C CH2

Solution:
 + H2C CH2

14.44 Propose a mechanism to explain the following reaction (see Problem 14.43):
CO2CH3
CO2CH3
O C
Heat
+ + CO2
C
O CO2CH3
CO2CH3
α-Pyrone

Solution:
CO2CH3 CO2CH3
CO2CH3

C C
O + CO2
+ + CO2
C C
CO2CH3
O
CO2CH3 CO2CH3

14.45 The triene shown below reacts with two equivalents of maleic anhydride to yield C17H16O6 as
product. Predict a structure for the product.
O

+ 2 O C17H16O6

O
O
O
O
O

+ 2 O

O O
O
Solution: O
14.46 The following ultraviolet absorption maxima have measured:
Λmax(nm)
1,3-Butadiene 217
2-Methyl-1,3-butadiene 220
1,3-pentadiene 223
2,3-Dimethyl-1,3-butadiene 226
2,4-Hexadiene 227
2,4-Dimethyl-1,3-pentadiene 232
2,5-Dimethyl-2,4-hexadiene 240
What conclusion can you draw about the effect of alkyl substitution on UV absorption maxima?
 Approximately what effect does each added alkyl group have?
Solution: 1)When alkyl substitution is added to dienes, the UV absorption wavelength maxima will be
longer.
2)The alkyl group added to the edge of the dienes make the wavelength maxima increase
more than the alkyl group added to the middle of the dienes.
The more alkyl group added to dienes, the longer the wave length maxima will be.

14.47 1,3,5-Hexatriene has λmax=258nm. In light of your answer to Problem 14.46, approximately
where would you expect 2, 3-dimethyl-1, 3, 5-hexatriene to absorb? Explain.
Solution: According to the figures of Problem 14.46: 1,3-Butadiene hasλmax=217nm, while
2,3-Dimethyl-1,3-butadiene hasλmax=226nm, so I would expect 2, 3-dimethyl-1,3,5-hexatriene
to absorb atλmax=267nm.

14.48 ß-Ocimene is a pleasant-smelling hydrocarbon found in the leaves of certain herbs. It has the
molecular formula C10H16 and exhibits a UV absorption maximum at 232 nm. On
hydrogenation with a palladium catalyst, 2,6-dimethyl-octane is obtained. Ozonolysis of
ß-Ocimene, followed by treatment with zinc and acetic acid, produces four fragments: acetone,
formaldehyde, pyruvaldehyde, and malonaldehyde:
O O O O O
O H2
H3C C CH3 HC H H3C C CH H C C CH

Acetone Formaldehyde Pyruvaldehyde Malonaldehyde

(a) How many double bonds does ß-Ocimene have?
(b) Is ß-Ocimene conjugated or nonconjugated?
(c) Propose a structure for ß-Ocimene.
(d) Formulate the reactions, showing starting material and products.
Solution: (a) ß-Ocimene has three double bonds.
(b) ß-Ocimene is conjugated.
H2
H3C C C C C C C CH2
H H H
CH3
(c) CH3

(d)

H2 palladium H H2 H2 H2 H2 H
H3C C C C C C C CH2 + 3H2 H3C C C C C C C CH3
H H H catalyst
CH3 CH3
CH3 CH3

O O O O O
H2 1.O3 O
H2
C CH + H3C C CH3
H3C C C C C C C CH2
H H H 2.Zn/H3O+ H C H + H3C C CH + H C
CH3
CH3

14.49 Myrcene, C10H16, is found in oil of bay leaves and is isomeric with B-ocimene (see Problem
14.48). It show an ultraviolet absorption at 226 nm and can be catalytically hydrogenated to yield
2,6-dimethyloctane. On ozonolysis followed by zinc/acetic acid treatment, myrcene yields
 O

O O
formaldehyde, acetone, and 2-oxopentanedial: 2-oxopentanedial

Propose a structure for myrcene, and formulate the reaction, showing starting material and products.

Solution: mycrcene
O
O O
O

O O

O O

O O

O O
O O two same steps

O O

O
O O
O O
O
Zn/H2O
O
O + +

O O O O O
O

14.50 Addition of HCl to 1-methyloxycyclohexene yields 1-chloro-1-methoxycyclohexane as the sole

product. Why is none of the other regioisomer formed?
Cl
O
O

HCl

Solution: Because the interaction intermediate is more stable than the other one:
Cl
O O

, so there is only one product , and no other regioisomer formed.

14.51 Hydrocarbon A, C10H14, has a UV absorption at λmax = 236 nm and gives hydrocarbon B, C10H18,
on catalytic hydrogenation. Ozonolysis of A followed by zinc/acetic acid treatment yields the
following diketo dialdehyde:
O O O O

HC CH2CH2CH2 C C CH2CH2CH2 CH
(a) Propose two possible structures for A.

Solution: One is and the other is .

(b) Hydrocarbon A reacts with maleic anhydride to yield a Diels-Alder adduct. Which of your
structures for A is correct?
Solution: The left one is correct.
(c) Formulate the reactions showing starting material and products.

H2

catalyst
Solution:
O3 O O O O

Zn/H3O HC CH2CH2CH2 C C CH2CH2CH2 CH

O
O

+ O
O

O
O

14.52 Adiponitrile, a starting material used in the manufacture of nylon, can be prepared in three steps
from 1,3-butadiene. How would you carry out this synthesis?

H 3 STEPS
H 2C C C CH2 N CCH2 CH2CH2CH2C N
H
Solution:

Br H2 Br CN
1,4 addition NaCN
Br2
Br CH3CN
Br CN
14-53 Ergosterol, (C28H44O), λmax=282nm and molar absorption ε=11,900.What is the concentration of
it in a solution whose absorbance A=0.065 with a sample l=1.oocm.
Solution:
ε=A/C×l
so C=A/ε×l=5.462.
14.54 Cyclopentadiene polymerizes slowly at room temperature to yield a polymer that has no double
bonds. On heating, the polymer breaks down to regenerate cyclopentadiene. Propose a structure
for the product.
Solution:

14.55 Dimethyl butynediocte undergoes a Diels-Alder reaction with (2E, 4E)-hexadiene. Show the
structure and stereochemistry of the product.
O O
H3C O C C C C O CH3 Dimethyl butynedioate
Solution:
The product of Dimethyl butynedioate undergoes a Diels-Alder reaction with (2E, 4E)-hexadiene.
O
C O CH3

C O CH3
O

14.56 Dimethyl butynedioate also undergoes a Diels-Alder reaction with (2E,4Z)-hexadiene, but the
stereochemistry of the product is different from that of the (2E,4E) isomer. Explain.
Solution: The reaction with (2E,4Z)-hexadiene can be written as follows:
 O O O

O
+
O

O O
O
and with the (2E,4E) isomer can be written as follows:
O O O

O
+
O

O O
O
Because their s-Cis conformations are different, the products are different.

14.57 How would you carry out the following synthesis (more than one step is required)? What

stereochemical relationship between the CO2CH3 group attached to the cyclohexane ring and

the CHO groups would your synthesis produce?

Solution：

CHO
CH2
Bnzene 1.O3
+ CHO
Heat 2+
HC 2.Zn /H3O+
C O

CO2CH3 CO2CH3
O CH3
endo
flip

CHO

OHC

H3CO2C

Obviously the group CO2CH3 and the red CHO are cis, however , CO2CH3 and green CHO are

trans.
14.58 The double bond of an enamine (alkene+amine) is much more nucleophilic than a typical alkene
double bond. Assuming that the nitrogen atom in an enamine is sp2-hybridized, draw an orbital
picture of an enamine, and explain why the double bond is electron-rich.
 C R
C An enamine
N

R
Solution:

R
N

R the carbon atom and nitrogen atom are all sp2-hybridized, so the p
orbitals will form a π34 conjugated system, the electrons are delocalized, it will surely lower the
system’s energy and make the electron cloud between the carbon-carbon more rich, so it looks as if the
double bond of an enamine (alkene+amine) is much more nucleophilic than a typical alkene double
bond.

14.59 Benzene has an ultraviolet absorption at λmax = 204nm, and para-toluidine hasλmax = 235nm. How
do you account for this difference?

H3C NH 2

Benzene para-toluidine

Solution:

H3C NH2
H3C NH2 H3C NH2

H3C NH2

Because CH3― and NH2― are electro-donating groups, and

The NH2― group enlarges the conjugation system, so it’s ultraviolet absorption becomes lager than
benzene.

14.60 Phenol, a weak acid with pKa=10.0, has a UV absorption at λmax=210nm in the ethanol solution.
When dilute NaOH is added, the absorption increases toλmax=235nm. Explain.
 OH

Phenol
Solution:
O

When NaOH is added, it reacts with phenol to yield phenol anion . And the conjugation of O-C in
phenol anion is stronger than it in phenol, so theλmax becomes a little longer.