PROBLEM SETS.

QUESTIONS AND ANSWERS

Chapter 1
1.1 A famous scientists of the 20th century was Linus Pauling who received two
Nobel prizes during his life. Look up a biography of Pauling and list his most
notable contributions to science.
Ans. Linus Pauling (1901-1994) made many advancements in the
understanding of chemical bonds and published in 1939 a classic book entitled, The
Nature of the Chemical Bond. Pauling received his first Nobel Prize in 1954 for
work on the structure of proteins. Pauling received a Nobel Peace Prize in 1962 for
his opposition to testing nuclear devices in the atmosphere. Pauling was a strong
advocate for taking large doses of Vitamin C to combat colds and cancer, and he
wrote several books on the subject, Vitamin C and the Common Cold (1970),
Cancer and Vitamin C (1979) and How to Live Longer and Feel Better (1986).
1.2 Sections 1.2a shows the electronic configuration for the 2nd row elements. a)
Show the electronic configuration for the third row elements. b)Common ions in
the 3rd row are Na+1 , Mg+2 , Al+3 ,Si+4 , P+5 , S-2, Cl -1 . What characteristic of
their electronic configurations do these ions share that accounts for their stability?
ans. a)
Element (atomic number)
Electron Configuration
Na (11)
Mg (12)
Al (13)
Si (14)
P (15)
S (16)
Cl (17)
Ar (18)

1s2, 2s2, 2p6 3s1

1s2, 2s2, 2p6 3s2
1s2, 2s2, 2p6 3s23p1
1s2, 2s2, 2p6 3s23p2
1s2, 2s2, 2p6 3s23p3
1s2, 2s2, 2p6 3s23p4
1s2, 2s2, 2p6 3s23p5
1s2, 2s2, 2p6 3s23p6

b) The ions Na+1 , Mg+2 , Al+3 ,Si+4 , P+5 result from loss of electrons from the
neutral element to give the stable electronic configuration of He, 1s2, 2s2, 2p6.
Both S-2 and Cl-1 result from the neutral element accepting electrons to give the
stable configuration of Ar, 1s2, 2s2, 2p6 3s23p6.
1.3 The dipole moment (_) of a molecule is the vector sum of the dipole moments
of the individual bonds. In some cases these sums cancel each other while in other

380 Problem Sets

cases they enhance each other. Given the bond moments of H-C (0.4) and C-Cl
(1.5), predict the dipole moment, and thus the polarity, of CH3Cl, CH2Cl2, CHCl3
and CCl4.
ans.
Cl

Cl

1.5

1.5
0.4

H 0.4

1.5
Cl

> CHCl3 > CH2 Cl2 >

0.4
H

= 1.85 Debuy

1.5

Cl 1.5

Cl

=0

Cl's cancel each other

H and Cl are additive
1.4 For the compounds below write the complete structure and designate the
bonding in each bond.
a) ethane, CH3CH3
ans.
a) ethane

Csp3
H

C
H

b) propene, CH3CH=CH2 c) propyne, CH3 C=CH

Hs

b) propene
Csp3 Hs

H
C

H
Csp3 Csp3

Csp2

H
C
H
C
H
Csp2
H

Csp3 Csp2
H
C

Csp2 Hs

H
Cp Cp

c) propyne
Csp3
H
H

Hs

Csp Csp
C

H
Csp3

H Csp

Hs

2 Cp Cp
Csp

1.5 Hydrogen bonds in alcohols and carboxylic acids have a bond strength of 8-10
kcal/mole. The energy required to break these bonds explains the higher by of

Problem Sets 381

hydrogen bonded substances. a) Use a chemical handbook to find the boiling
points of the following compounds to see the effect of hydrogen bonding on the
boiling point.
CH3CH2OCH 2CH3 versus CH3CH2CH2CH2OH versus CH3CH2COOH
b) What are the molecular weights for these compounds and how does the
molecular weight affect the bp in them?
ans
a)
CH3CH2OCH 2CH3
CH3CH2CH2CH2OH
CH 3CH2COOH
bp 35 oC
bp 114 oC
bp 141 oCb) all have a
molecular weight of 74. Thus van der Waals attractions due to size are the
same.Bp differences attributed to polar attractions and hydrogen bonding.
1.6 Expand the structures below to show all atoms and unshared electron pairs.
a)

b)

OCH3

(CH3)3CCH=CCH3
COOH

O
OC-CH3

c)

d)
FCCl3
Freon-11

aspirin
ans

382 Problem Sets

H
H

a)

b)

O C

C
H

H
H

H
H
H

H C

H
H
C
H

O
C

H
H

C
C

d)

O
H

H C

H
c)

O
C
C
C

Cl

H
O

C
C
O

Cl

Cl

1.7
ans. Many sites are available for all areas of chemistry. Look at the home
pages for the Department of Chemistry, Northern Illinois University and for
the University of Florida.

Chapter 2
2.1. Write the alkyl substituent names for ethane, octane, cyclohexane and the
structures,
CH3
CH3
,
, CH CHCH CHCH
CH3 CHCH 2 CH3
CH3 CHCH 2 CH2 CH2
3
2
3
ans.
name the alkane, remove the ane, add yl
ethane; ethyl
octane; octyl (there are several positions for
attachment of octyl)
cyclohexane; cyclohexyl

Problem Sets 383

CH3 CHCH 2 CH3 ; 1-methylpropyl

CH3
CH3 CHCH 2 CH2 CH2

; 4-methylpentyl

CH3
CH3 CHCH 2 CHCH 3 ;

4-methyl-2-pentyl-

2.2. Write balanced equations for the complete combustion of propane and
methylcyclopentane.
Complete combustion means oxidation to carbon dioxide and water.
CH3 CH2 CH3 +

3 CO2 +

5 O2

4 H2 O

CH3
+

6 CO2 +

9 O2

6 H2 O
,

2.3. Draw and name all of the structural isomers of a)pentane and b) hexane.
Ans.
C
C
C C C
a)

n-pentane

2-methylbutane

C
2,2-dimethylpropane

(Hydrogens not shown)

b) n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane

(you draw the structures, show all hydrogens)
2.4.Write structures, formulas, and formula weights for the following.
a) 3-isopropylnonane b) cyclopropylcyclohexane c) sec-butylcyclopentane
ans.

384 Problem Sets

a)

c)

b)

C12H26 170
(not 3-ethyl-2-methyl-nonane)
C9H16 124

C9H18 126

2.5. Provide names for each compound below.

a)

CH3

CH3
b) CH3
CH3CHCH2CH=CHCCH3

c)

CH2CH2CH3
ans
a) 1-methylcyclohexene
b) 2,6,6-trimethyl 4-nonene
not 5-nonene
c) 6-methyl- 2-heptene
2.6. Write structures that correspond to the names given.
a) 1,2-pentadiene
b) 3-bromocyclopentene
c) 3,3-dichloro-1-pentyne
d) cyclohexylethyne
ans.
a)
b)
CH3CH2CH=C=CH2
Br
c)

Cl

d)
CH3CH2CC=CH
C CH
Cl
2.7. Show the products from the reaction of 2-methy-2-butene with a) H2 / Pt, b)
hot KMnO 4, c) HBr-peroxide, d) HBr (no peroxide), e) Br2, f) O3 / Zn
ans.

Problem Sets 385

a)

H H

d)

b)

e)
O + CH3COOH

c)

Br H

O + CH3CHO

H Br

.
2.8. Both Vitamin D and Cortisone contain significant hydrocarbon portions of
their structure. Find their structures in a reference book (Merck Index) and list the
function groups present in each molecule.
ans.
O
OH
H3C
CH3
O
CH3
CH3
OH
CH3
CH3
Vitamin D3

HO

contains:
Hydroxyl (alcohol)
three alkenes as a conjugated triene

Cortisone
contains:
carbonyl (ketone)
alkene (conjugated)
two hydroxyl (alcohol)

Chapter 3
3.1 Name the two alkenes below and show the alkene configuration by a) cis-trans
rules and b) E, Z rules.
ans

386 Problem Sets

Br

CH2 CH3
C=C

Cl
F
E-1-bromo-1-chloro-2-fluoropropene

cis-2,4,6-trimethyl-3-heptene

a) longest chain is cis

a) no good cis or trans
determination
b) isopropyl and sec-butyl groups
have higher priority and are on the
b)Br and F have higher priorities
same side Z
and are opposite, E-isomer
Z-isomer
3.2 Draw structures for trans-1,3-dibromo- and trans-1,4-dibromocyclohexane and
examine the axial-equitorial relationships of the bromine atoms.
ans.
trans-1,3-dibromocyclohexane
trans-1.4-dibromocyclohexane
Br

Br

e
Br

a Br
Large substituent, Br, prefers equitorial position.
3.3 Humulene is a triene found in hops. Label bonds a, b, and c by both cis-trans
and E-Z rules. If two methyl groups are replaced by Br atoms then the compound
on the right occurs. Label the a, b, and c bonds in the dibromo compound also by
cis-trans and EZ rules. How did the Br affect the nomenclature?
ans.
humulene
Br
CH3
a

a
b
H3 C

c CH3

CH3
a - trans or E
b - trans or E
c - trans or E

b
H3 C

c Br

CH3
a - trans for hydrocarbon, but Z
isomer Br has higher priority
than C
b - trans or E
c - trans for hydrocarbon, but
Z isomer.

The Br atoms changed the priority in the nomenclature for a and c.

Problem Sets 387

3.4 Tertiary butyl groups are so large that they will not occupy an axial position in a
cyclohexane ring. Draw structures for a) cis-1-tert-butyl-4-methylcyclohexane and
b) cis-1,4-di-tert-butylcyclohexane and determine the structural changes.
ans.
In a the tert-butyl group occupies an axial position and the methyl
occupies an axial position. But in b one tert-butyl group would be
required to occupy an axial position which is just energetically too
high. Thus the ring changes from a chair conformation to a twist
conformation to accomodate the two tert-butyl groups.
a
CH3

CH3

CH3
C CH3
CH3

CH3
CH3 C
C CH3
CH3
CH3
trans-1-tert-butyl-4-methylcyclohexane
trans-1,4-di-tert-butylcyclohexane
twist conformation of the cyclohexane ring
3.5 a) Draw Newman projections for the staggered conformations of 1-fluoro-2chloroethane. b) Draw Newman projections for all of the conformations of 1,2dichloroethane.
ans.
Cl
Cl
Cl
F
F
a)
F

b)

staggered
Cl

Cl

Cl
Cl

Cl

Cl

staggered

Cl

Cl

Cl

Cl
Cl

Cl
eclipsed

388 Problem Sets

3.6 Draw the structure for the more stable conformation of
a) isopropylcyclohexane
b) cis-1,2-dimethylcyclohexane
c) 1-fluoro-1-bromocyclohexane
d) trans-1,2-dichlorocyclohexane
ans.
CH3
a)
b)
CH(CH 3 )2
CH3
d)

c)

Cl

Br

Cl

3.7 Identify the stereogenic center in each compound below and draw with a dottedline wedge structure the R isomer.
ans.
COOH
Cl
a)
b)
H
H2 N
c)

CH3
CH2 CH2 CH3

H
H3 C

Cl

d)

CH2 CH3

H3 C

CH2 CH2 CH3

3.8 The compounds below are all well-know compounds with important biological
activity. The S enantiomer is the active substance in each case. Draw the S isomer
for each compound.
ans.

Problem Sets 389

COOH
a)

b)
HO

OH

H
N

CH3

(CH3 )2 CHCH 2

HO
(-)-epinephrine
adrenaline

(-)-ibuprofin
c)

COOH
H
OH

H3 C

(+)-lactic acid

Chapter 4
4.1 Many primary sources contain a historical background on Kekule. Write a brief
biography about him.
ans. Taken from Britannica
Kekule von Stradonitz, August (1929 - 1896) born in Darmstadt, Germany is
described as a chemist who laid the groundwork for the modern structural theory in
organic chemistry. In 1858 he showed that carbon is tetravalent and could form
long chains. "One night in 1865 Kekule dreamed of the benzene molecule as a
snake biting its tail while in whirling motion. From that vision his concept of the
six-carbon benzene ring was born".
Factual dream or not, Kekule started much of the early theory of organic
chemistry.
4.2. Determine, according to Huckel's rule, which compounds below are aromatic.
ans.
Aromatic compound must be cyclic, planar and contain 4n + 2 electrons
Compounds that are cyclic, planar and contain 4n electrons are called antiaromatic,
a particularly unstable system.
a)

b)

c)
+

2e, aromatic

4e, antiaromatic

6e, aromatic

390 Problem Sets

e)

d)

4e, antiaromatic
f)

6e, aromatic
g)

8e not planar
not aromatic

[18]-annulene
18e, aromatic
4.3 Draw the ground state resonance structures for a) aniline, and b) benzaldehyde.
What is the purpose of writing these resonance structures?
ans.
a) aniline
NH 2

+
NH 2

+
NH 2

+
NH 2

b) benzaldehyde
O

C-H

C-H

C-H

C-H

+
The purpose of writing resonance structures is to get a better understanding
of the true electronic structure of a compound when one structure alone is
inadequate. Resonance shows that the ring in aniline contains some negative charge
and would thus react readily with electrophiles at the ortho and para positions.
Resonance in benzaldehyde shows that the ring is deficient in electrons and thus
would not readily react with electrophiles.

Problem Sets 391

4.4 Draw structures that correspond to each name below.
a) meta-nitroacetophenone b) o-dichlorobenzene c) 2,5-difluorotoluene
c) p-isopropylaniline
e) 3-chloro-5-nitrophenol
ans,
CH3
a)
O
b) Cl
c)
F
Cl
NO 2
CH3
F
d) NH 2

CH(CH 3 )2

NH 2

e)

NO 2

Cl

4.5 Give systematic names for the compounds below.

a)
b) SO 3 H
Cl
Br
Br

c)
Cl

d) COOH

CH2 CH3

e)

OCH 3

Cl

ans.
a) m-dibromobenzene
b) o-chlorobenzenesulfonic acid
c) 1,2,4-trichlorobenzene
d) p-ethylbenzoic acid
e) 3-chloro-5-fluoroanisole
4.6 Complete the following reactions.
a) nitration of p-dimethylbenzene (called p-xylene)
b) acylation of acetanilide
c) bromination of 3-fluorophenol
d) sulfonation of o-nitroanisole
e) chlorination of 2,4-dibromophenol

Cl
Cl

392 Problem Sets

ans.
CH3

CH3
HNO3 / H2SO4

a)
CH3

CH3

O
CH3CCl
NHCCH 3

b)

OH
Br2 / Fe

c)
F

F
Br

d)

O
NHCCH 3

O
CH3 C

AlCl 3

OH

NO 2

OCH 3
NO 2 SO3 / H2SO4

OCH 3
NO 2
SO 3 H

OH
e)

OH
Br Cl 2 / Fe Cl

Br

Br

Br
4.7 Draw structures for the substituents below and label them as ring activators or
ring deactivators, and show their directing influence.
a) nitrob) acetyl c) hydroxy d) amino e) sulfonic acid f) formyl g) carboxy h)
methyl i) phenyl j) halogen
ans.
Activator
Deactivators
os / p directors
m directors
CH3 (methyl)
O
NH 2 (amino)
CH (formyl)
OH (hydroxy)

Note that halogens are

deactivators, but are o /p
directors

SO 3 H (sulfonic acid)
COOH (carboxy)
O
CH3 C (acetyl)
NO 2 (nitro)
F, Cl, Br, I (halogen)
o/p directors

Problem Sets 393

4.8 The reactions below require more than one step. Show how you would
complete the sequences.
ans.
CH3
1) I2 / HNO 3

a)

CH3

NO 2

NO 2

2) HNO3 / H2 SO 4
heat
CH3
b)

I
CH3

1) SO 3

Cl

2) Cl2 / Fe
SO 3 H

Br
c)

1) HNO3 / H2 SO 4
2) Br2 / FeBr3
Cl

d)

NO 2

1) Cl2 / Fe
2) HNO3 / H2 SO 4

NO 2

Chapter 5
a) 1-bromoheptane b) allyl chloride c) 3-chlorohexane d) 2-iodo-2-methylbutanef)
3-chlorocyclohexene e)benzyl bromide (bromomethylbenzene) f)1-bromo-4isopropylbenene.
ans.

394 Problem Sets

a) CH3CH2CH2CH2CH2CH2CH2Br
Cl
b)
allylic

primary

Cl
CH2Br
benzylic

and primary

Cl
c)

f)

secondary
CH3

d)

allylic
and secondary

e)

CH3CCH2CH3

CH(CH3)2

g)

tertiary

aromatic
Br
I
5.2 Use compounds a-g above in the two reactions reaction with cyanide ion (SN2
conditions).
ans.
CN

a) CH3CH2CH2CH2CH2CH2CH2Br

primary

R-CN

CN

CN

Cl

b)

and primary
allylic
Cl

c)

secondary

CH3

d)

CH3CCH2CH3

tertiary

CN

CN

minor

CN

no SN2
minor

I
CN

e)

allylic and secondary

CN

Cl
CH2Br

f)

benzylic

CH(CH3)2

g)
Br

aromatic

CN

minor

CH2CN

CN
no reaction with aromatic halides

Problem Sets 395

5.3 Use the compounds from a-g above in reactions with acetone and water solution
(SN1 and E1 conditions).
ans.
a) CH3CH2CH2CH2CH2CH2CH2Br
Cl

b)
Cl

CH3
tertiary

CH3CCH2CH3

OH

CH3

H2O

more than
in part a

CH3CCH2CH3
OH equal amounts

I
e)

allylic and secondary

H2O
OH

Cl
CH2Br

f)

No SN1 or E1 reaction

OH

H2O

secondary

H2O

H2O

allylic and primary

c)

d)

primary

benzylic

CH(CH3)2

g)

H2O

H2O

20 %

CH2OH

no reaction with aromatic halides

aromatic

Br

5.4 Use the compounds from a-g above in reactions with conc hydroxide (SN2 and
E2 conditions).
ans.
a) CH3CH2CH2CH2CH2CH2CH2Br
primary
Cl
b)
OH
allylic and primary
Cl
c)
OH
secondary
d)

CH3
CH3CCH2CH3

tertiary

OH

OH

R-OH
OH

OH

50%

no SN2

I
e)

f)
g)
Br

allylic and secondary

Cl
CH2Br

OH
OH

benzylic

CH(CH3)2

OH

OH

CH2OH

20 %

no reaction with aromatic halides

aromatic

5.5 What would happen with the substrate below on reaction with 1) CH3S-, b)
methoxide, and c) water, and d) CH3NH 2 ?
ans.

396 Problem Sets

H2O

CH3S CH3O CH3NH2

H3 C

H3 C

H3 C

HO S N1

I
ICH 2

E2 products
CH3XCH2

NR
a little first order
rearrangement

S N2

5.6 Complete each reaction below as required.

ans.
CH3 O
H

a)

CH3
CH3 CH2

CH3 O

CH3
CH2 CH3

b)
Br

t-Bu

t-Bu
SCH 3

t-Bu must be equitorial-ring is fixed

CH3 S
c)

CH3

CH3

CH3 CCH2 -Br

CH3

OCH 3
d)
Ph
CH3 CH2

no 10 carbocation, but
easy rearrangement to
30 carbocation

CH3 CCH2 CH3

+

Cl

CH3 OH
H

E1

SN 1

Ph

H
CH2 CH3

OCH 3
PhCHCH 2 CH3
racemic

S
5.7 Show and label the Hofmann and Saytzeff E1 products from the carbocations
below.
ans.

Problem Sets 397

+
Hofmann

Saytzeff
+
Saytzeff

Hofmann

Chapter 6
6.1 a) Provide structures for the names given, and b) provide names for the
structures given.
a) names: 2,3-dichloro-2,4-dimethylpentane; 2-chloro-2-pentene; 1-chloro3-fluoronaphthalene; 5-bromo-1.3-cyclohexadiene.
b) structures.
ans.
Cl
Cl
a)
Br
2-chloro-2-pentene

Cl Cl
2,3-dichloro-2,4-dimethylpentane
b)
I
t-Bu

5-bromo-1,3-cyclohexadiene

Cl
PhCHCH2CH3 Br
1-chloro-1-phenylproane

trans-1-iodo-4-t-butylcyclohexane

F
1-chloro-3-fluoronaphthalene

CH3
Cl2CBr2
dibromodichloromethane

Br
trans-1,2-dibromo-1-methylcyclohexane

6.2 a) Show and provide names for all of the free radical monochlorination
products with 3-methylpentane, and 2,2-dimethylpropane. b) Show the propagation
step for the monochlorination of cyclohexane. c) Show the major product from the
reaction of ethyl benzene with NBS and peroxide.
ans.

398 Problem Sets

a)

Cl

CH3

Cl
CH3

CH2Cl

CH3

1-chloro-

3-chloro-3-methylpentane

1-chloro-2,2-dimethylpropane

Cl

Cl
1-chloro-2-ethylbutane

2-chloro
b)

+ HCl

Cl

Cl
+

+ Cl2
c)

Cl

Br
CH3

6.3 Show the a) Markovnikov addition and b) the anti-Markovnikov products for
addition to the alkenes below.
ans.
Markovnikov

Br

H
Br H

Br

Anti-Markovnikov

H Br
Br

Br

H
6.4 Give the structures of the Grignard reagents obtained from reaction of each
halide with Mg in ether, and show the reaction product for reaction of the Grignard
reagent with acetaldehyde (CH3CH=O) and acid.
ans.

Problem Sets 399

Br

CH3

Br
CH3
CH3CBr
CH3

CH3

Mg BrMg
Mg

MgBr
CH3
CH3CMgBr

Mg

CH3

1)CH3CH=O HOCH2
2) H+
1)CH3CH=O

CH3

CH2OH

2) H+

CH3
CH3C-CH2OH
CH3

1)CH3CH=O
2) H+

6.5 Give the final product for each sequence below.

ans.
a)

CH2OH

1) SOCl2
CH2CN

2) NaCN

CH3
Br

b)

1) Mg
2) (CH3)2C=O
3) H+

c)

OH
CH3
H

1) KOH
I
2) CH2I2 , Zn-Cu
Br

d)

H
Br

1) CH3CCl, AlCl3
2) CH3CH2MgBr /
H+
HO

CH2CH3
CH3

6.6 Show the product and mechanism for the reactions below.
stereochemistry.
ans.

Include the

400 Problem Sets

Br2

a)

Br

Br
+

Br

Br
b)

CH3C CH

Cl2

Cl
Cl

CH3C CH
+

CH3C CH

Cl
Cl
6.7 Show the most important resonance structure for each compound below that
accounts for the orientation in electrophilic substitution. How does the relative
reactivity of these compounds compare with benzene.
ans.
+
+
X
X
Y
H
ground state

intermediate

Halogen deactivates the ring, thus lower reactivity than benzene.

Halogen directs to the ortho and para positions.
6.8 2,4-D is an important insecticide. Find its structure from any source and
suggest a synthesis of it from a phenolic compound (chapter 7) in the SN2 process.
ans.
OH BrCH2COOH
NaOH

Cl
Cl

Cl

OCH2COOH

Cl
2,4-D
2,4-dichlorophenoxyacetic acid

Chapter 7
7.1 Provide IUPAC names for the structures a - d, and provide structures for e - h.
ans.

Problem Sets 401

OH
CF3 CH2 CHCH 3

OH

b) 4,4,4-trifluoro-2-butanol

a) 4-methyl-2-pentanol
CH3

CH3

OH
OH

CH3

OH

c) trans-4-tert-butylcyclohexanol
OH
Cl

d) trans-1,2-cyclohexandiol

OH
CH3
H3 C

Cl

e) 3-chloro-3-methylcyclopentanol

f) 6-chloro-5-methyl-4-hexen-3-ol

CH(CH 3 )2

CH3 OH

HO

CH3 CH2 CCH2 CHCH 2 Br

CH3

CH3
g) 2-isopropyl-5-methylphenol

h) 1-bromo-4,4-dimethyl-2-hexanol

(also known as thymol

from oil of thyme)
7.2 Classify the alcohols in problem 7.1 as primary, secondary, tertiary, allylic,
phenolic.
ans. All of the alcohols are secondary alcohols except g which is phenolic.
Compound f is secondary and allylic.
7.3 Show the product for the reactions of a - f with hydroxide.
ans.
CH2
O
c)
e)
a) NR
b) CH3 CH2 CH2 OH

CH3 C

CH3
f) NR
d) NR
7.4 Give the products for the reactions of each substrate below with PhMgBr /
H3O+ , meta-chloroperoxybenzoic acid (MCPBA), and HI.

402 Problem Sets

ans.
substrate
CH3CH2CH2OH

OCH 3

+
PhMgBr / H 3O

MCPBA

CH3CH2CH2OH

NR

CH3CH2CH2I

PhCH 2CH2OH

NR

CH3CH2I

NR

NR

HI

OH
CH3I

O
CH3CH=CHCH 3

CH3CH-CHCH3

NR

CH3CH2CHCH3

I
OH

OH

NR

NR

PhH

7.5 a) Reaction of methane thiol with iodine gives a new compound, C2H6S2, that
is a hamster sex attractant. What is the structure? b) Allylin, sect 7.4g, reacts with
NaBH4, to give a thiol. What is the thiol?
ans.
a)

I2

CH3 SH

CH3 SSCH 3

b)
S

NaBH4

Allylin

7.6 Use an alkoxide and an alkyl halide to prepare the ethers below.
ans.
a)
b) CH3 O
O
Br

CH3

CH3 Br

Can not use aryl halide nor tertiary halide

7.7 Provide structures for the reaction products A - H below.
ans.

Problem Sets 403

HO

CH2 CH3

Br

CH2 CH3
B

A
CH3 CH2 CH2 CH2 Br
E

CH3

CH3

OH C

O D

CH3 CH2 CH2 CH2 O-tert-Bu

(Williamson ether synthesis)
OH
OH

Chapter 8
8.1 Provide the IUPAC names of the compounds in part (a), and provide the
structures for the compounds in part (b).
ans.
a)
O
F
(CH3)3C-C
CHO
O
2-methyl-3-butenal
tert-butyl p-fluorophenyl ketone
3-methyl-4-penten-2-one
OH

Cl

CHO
CHO

O
Cl

4-hydroxy-4-phenylbutanal

2,5-dichlorocyclohexanone

cyclobutanecarboxaldehyde

404 Problem Sets

b)
Br

O
Br

1,3-dibromopropanone

O
PhCH2CCH2Ph
dibenzyl ketone

1,4-cyclohexandione
CH3CH2

CHO

CHO

E-3,7-dimethyl-2,6-octadienal (citral)

m-ethylbenzaldehyde

NNH2
cyclopentanone hydrazone
8.2 Complete each preparation.
ans.
K2 CrO4
a)
OH
H2 SO 4

O
CH3 CCl

b) CH3 O

AlCl3

c) CH3 CH2 CH2 CH2 OH

e)

1) O3
2) Zn

O
f) CH3 CH2 CH=CHCOCH3
8.3 Complete each reaction.
ans.

Friedel-Crafts

OO
ClC-CCl
CrO3
H2 SO 4

OH

O
CCH3

CH3 O

CH3 SCH 3

d)

Brckmann

CH3 CH2 CH2 CH=O

Swern

O
O

Jones

oxonolysis

CH3
CH3 CHCH 2 AlH
O
2
CH3 CH2 CH=CHCH
-78 0 C
DIBAL

Problem Sets 405

a)

b)

O
CH

NaBH4

OH
O

HOCH 2 CH2 OH
H

HN
c)

O
H

d)

CH3 CH2 CH2 CH=O

e)

Ph3 P+ CH2

HCN
O
O

f) Ph
g)

CH3 CH2 CH2 CH=CH 2

Ph

HO
1) CH3 MgBr
+
2) H3 O
NH 2 NH 2

HO
Ph

O
CCH3 KOH

CN

CH3
Ph
CH2 CH3

8.4 Provide structures for A - D reagents to complete the synthesis below.

ans.
A Zn(Hg) B 1) Mg
HCl
2) CH3CHO / H+
C CrO3
H2SO4

D NaC=CH / H3O+

8.5 Draw the enol and enolate forms for the compounds below
ans.
O
OH
O

CH3CH2CHO CH3CH=CHOH
enol

CH3CHCHO
enolate

406 Problem Sets

8.6 Show the structures for products A - F.
ans.
OH
B
A
CH=NHOH C

OH

O
D

NNHPh
CH2Br

CH2
8.7 Give the structure for A - F in the sequence below.
ans.
O

O
O

Br
A

O
D

O
Br E
Br

CH2
Br
Br

Br
Br

Chapter 9
9.1 Draw the correct structure corresponding to the names given below.
a) 4-octenoic acid b) m-nitrobenzoic acid c) 5-hydroxypentanoic acid
d) isobutyric acid e) benzoyl chloride f) malonic acid
g) N,N-dimethylpropanamide h) methyl salicylate
i) diethyl succinate j) 4-cyanophenylacetonitrile k) trifluoroacetic acid
ans.

Problem Sets 407

a) CH3 (CH2 )2 CH=CHCH2 CH2 COOH

b) NO 2

COOH

O
g) CH3 CH2 C-N(CH 3 )2
O
C-OCH 3
h)

c) HOCH 2 CH2 CH2 CH2 COOH

d)

i)

CH3

CH2 COOCH 2 CH3

CH2 CN
j)

COOH
CH3

OH
CH2 COOCH 2 CH3

O
C-Cl

NC

e)
k) CF3 COOH

f) CH2 (COOH)2

9.2 Give correct IUPAC names for the compounds below.

a) 4,5-dibromoheptanoic acid
c) 2-chloroproanoic acid
e) succinic anhydride

b) 1,2-benzenedicarboxylic acid
phthalic acid
d) N,N-dimethylcyclopetenecarboxamide
f) 6-fluoro-1-naphthoic acid

9.3 Provide structures for the reagents or products A - D.

ans.
A

C 1) CO2 2) H +

B
O

COO
O
D

+ CH3OH

E 1) KMnO4 2) H+

O
9.4 Give the product for each substrate with the reagents shown.
ans.

408 Problem Sets

CH3 CH2 CH2 CH2 COOH
a) LIAlH4

CH3 CH2 CH2 CH2 CH2 OH

b) SOCl2

CH3 CH2 CH2 CH2 COCl

c) Pb(OAc)4
KCl

CH3 CH2 CH2 CH2 CH2 Cl

O

d) CH3 Li / H + CH3 CH2 CH2 CH2 CCH3

COOH
Br

COOH

a) Br2 - Fe
b) 1) SOCl2
2) PhH - AlCl3
c) CH3 OH - H +

O
C

COOCH 3
CH2 Br

d) 1) LiAlH4
2) PBr3

9.5 The Kreb's cycle begins with the addition of acetyl-CoA to oxaloacetate
followed by a series of isomerizations, oxidations and a 1,4-addition reaction. What
is meant by a 1,4-addition?
ans
Some carbonyl systems contain a C=C double bond adjacent to the
carbonyl, and are known as ,-unsaturated carbonyl systems. When numbered
from the carbonyl oxygen, there are four atoms in the system as shown below.
Nucleophiles, such as water, add to these systems at the 4-position. The mechanism
involves all four atoms and thus it is called a 1,4-addition reaction.
O1
Nu

R-CH=CH-C-O
4
3
2

O1
Nu
R-CHCH 2 -C-O
4
3
2

Problem Sets 409

9.6 Give the reaction product obtained from the reaction of PhMgBr / H+ (excess
if needed) with each compound below.
ans.
a) CH3 CH2 COOH
b) CH3 CH2 COCH 3 c) CH3 CH2 COOCH 3
OH
OH
CH3 CH2 COO + MgBrCH3 CH2 C Ph
CH3 CH2 CCH3
Ph
Ph
d) CH3 CH2 COCl e) CH3 CH2 CON(CH 3 )2 f) CH3 CH2 CN
OH
O
CH3 CH2 COPh
CH3 CH2 C Ph
CH3 CH2 CPh
Ph
9.7 Provide the structures of A - G in the synthesis below. What is the name of the
final compound?
ans.
Br
OH
CN
OH
O
A

B
O
OH

C
O

Cl
O
G
indanone

F
E
9.8 Give the IUPAC names for A-F above.
ans.
A) 2-phenylethanoic acid
B) 2-phenylethanol
C) 1-bromo-2-phenylethane D) 3-phenylpropanonitrile
E) 3-phenylpropanoic acid F) 3-phenylpropanoyl chloride G) indanone
starting material name is 1-phenyl-2-propanone

CHAPTER 10
10.1 Provide both the common and IUPAC names for the compounds below.
ans.

410 Problem Sets

a) CH3 CHCH 2 CH3
NH 2

sec-butylamine
2-aminobutane
2-propanamine

c) CH3 NHCH(CH3 )2

CH3

b)

N
CH3
dimethylcyclopentylamine
dimethylaminocyclopentane
N,N-dimethylcyclopentanamine

isopropylmethylamine
2-methylaminopropane

e) CH3

CH2 CH3

N-methyl-2-propanamine
d) (CH3 CH2 )2 NH
diethylamine
ethylaminoethane
N-ethylethanamine

Cl
N-ethyl-N-methyl-m-chloroaniline
m-(N-ethyl-N-methylamino)-chlorobenzene
N-ethyl-N-methyl-m-chlorobenzenamine

10.2 Give structures corresponding to the names below.

ans.
Br
CH3
CH3 CH2 NHCH 2 CH2 CH3
N
b) N-ethyl-1-propanamine
CH3
a) 1-(dimethylamino)-3-bromocyclopentane
(CH3 )2 CHCH 2 NH 2
c) isobutylamine

CH2 CH3

CH2 CH3

CH3 NH[CH(CH3 )2 ]2
e) diisopropylmethylamine

NO 2
d) N,N-diethyl-p-nitrobenzenamine

10.3 Give the correct product for each reaction.

ans.

Problem Sets 411

NH3

a) CH3CH2CH2Br

+
(CH3CH2CH2)4N Br

Gabriel Synthesis

b) CH3CH2CH2Br
NO2

CH3CH2CH2NH2
NH2

Sn / HCl

c)
Cl

Cl

O
CH2CH2C-NHCH3
LiAlH4

d)

e)

CH2CH2CH2-NHCH3

NH3 , H2

NH2

Pd

10.4 Provide correct structures for A, B, C below.

ans.
+
N
CH3

+
N

Br
CH3

CH3

OH
CH3

N
CH3

CH3
C

10.5 Give the correct structures for A - F.

ans.
O
NHAc CH3-C-

NH2
A

CH3CH2

NHAc

NHAc
C
+
N2 Cl

CH3CH2

E
CH3CH2

CN
F

10.6 Three opium derived highly addictive pain-relieving drugs are morphine,
heroin and cocaine. The general structure is shown below. Find from any organic
source book the structures of the R and R1 groups to determine the similarities of
the compounds.
ans.

412 Problem Sets

R1O

OR

Morphine R = R1 =H
heroin R = R1 = OAc

codeine R = CH3
H
R1 = H
CH3 N
all three compounds have very similar structures
10.7 Complete the following synthetic procedures by using aromatic diazonium salt
intermediates.
ans.
NO2
NO2
a)

HNO3

I2

H2SO4

HNO3

N2+

NH2

NaNO2

HBF4

HCl , O 0C

I
b)
CH2O

heat

CH O
HNO3 2

Sn

H2SO4
CH2O

Sn
HCl

CH2O

NO2 HCl

NH2

CuCN CH2O

NaNO2
HCl , O 0C

H3O+ CH2O

N2+

CN

COOH

c)

CH3

HNO3

CH3

Sn

H2SO4

CH3

CuCN

HCl

CH3

H3O+

CN

HOOC
COOH

NaNO2
HCl , O 0C

NH2

NO2

N2+
KMnO4

CH3

CH3
COOH

Problem Sets 413

Chapter 11
11.1 Show the enolates obtained from a) acetone, b) acetophenone,
c) cyclohexanone, d) methyl 2-cyclopentanonecarboxylate, e) diethyl malonate
ans.
O
O
O
O
O
b)
c)
a)
d)
CH3
O
e)

CH3 CH2 O2 C CH

CO2 CH2 CH3

enolate anions are anions apha to a carbonyl function

11.2 Show the aldol or crossed-aldol product in each reaction.
ans.
O
O
H
CH3
a)
b)
HO
CH2
CH3
Ph
CH3
O
d)
CH3 CH2 CHCHO
c)
CH3

CH3 CH2 CH2 CHOH

OH

11.3 Show the correct structures for the products A - F.

ans.
O
O
O
CH3C-CH-CO2C2H5 CH3C-CH2 CH3C-CH-CO2C2H5
CH3
CH3
C
B
A
O
O
O
CO2CH3
CO2CH3
CH3C-CH-CO2C2H5
CH3C-CH-CO2C2H5
Ph
F
E O
D
11.4 Complete the structures for A - F below. Label the names of the processes.

414 Problem Sets

ans.
O
Reformatsky

HO

CH2CO2Et
H

BrCH2CO2Et
Zn

B
N

Michael O
CN

2) H3O+

CO2CH3
LDA

CN
E

CN

CHCO2Et

NC

CN

HN
H+
enamine

CH3

CN

CHCO2Et

CH3

Robinson

CO2CH3

11.5 Make a list of the carbon-carbon bond forming reactions found a) in this
chapter, and b) in all of the previous chapters. You should also give an example of
each reaction.
ans.
a) This chapter: Aldol and crossed aldol condensations, Claisen and crossed
Claisen condensations, Dieckmann reaction, Robinson reaction, Reformatsky
reaction, Enamine alkylation, Michael Reaction, Diels-Alder reaction, enolate
alkylation (ethyl acetoacetate and diethyl malonate). b) Other chapters:
Grignard (organometallic) reactions with carbonyl and carbon dioxide, FriedelCrafts acylation and alkylation, Vilsmeier reaction, Wittig reaction, SN2 reactions
with acetylide and cyanide nucleophiles, addition of HCN to carbonyl, carbocation
rearrangement. There are also many other carbon-carbon bond forming reactions
not given in this book. Examples are not listed here, that is the student's job. Most
of the other reactions found so far are functional groups modification reactions.
The combination of carbon-carbon bond forming reactions and functional group
modifications are the backbone of organic synthesis once a good synthetic plan is
achieved.
11.6 Complete the Diels-Alder reactions with complete regio and stereoselectivity.
ans.

Problem Sets 415

a)

H
O

CH3 O
c)

O
O
endo product
exo product
H
only product O
not formed H
The Diels-Alder reaction gives only
endo products (H's up).
Ph
b)
d)
CN
Ph's cis
CH3
CN trans
Ph
11.7 Analyze the synthesis of the compound below.
ans.
O
O
O
CH3
CH
3
CH3
+
O
CO2CH2CH3
CH
3
CH3
O O

ortho product
only
O
OCH 3
para product
only

O
Br

CH3

CH3CH2O

Chapter 12
12.1 What is the configuration of the stereogenic center in nicotine. Show the
priorities.
ans.
4
1
HN
H
S-configuration
2
3
nicotine
N
12.2 Draw resonance structures to show the electrophilic substitution at the 2 and
3-positions of thiophene.
Explain why thiophene undergoes electrophilic
substitution in the 2-position.
ans.

416 Problem Sets

2-substitution
+
+

3-substitution
E

S
+

2-substitution is
preferred as the
charge is extended
further

S
+
12.3 Show resonance structures for electrophilic substitution in pyridine in the 3position. Compare with substitution in the 2-position.
ans.
3-position substitution
+
E
E
E
+
E
S

+ N

2-position substitution
+

E+
N
+

+
N

3-substitution does not put a positive charge on a divalent nitrogen

atom, but 2 substitution does. Pyridine is deactivated and gives
electrophilic substitution with extreme conditions.
12.4 Complete the following reactions.
a)
Br2
S

S
c)

HNO3

HCl

b)

+
N
H

Br
N
d)

Cl

Br2

Br
N
N
O
O
H
H
12.5 How many stereogenic centers in quinine? What is the configuration of the
alcohol carbon atom?
ans.

Problem Sets 417

*
*
N
H *
*
OH

CH3O

S-configuration
quinine -4 stereogenic centers

12.6 The nitrogen heterocycles pyridine, imidazole and pyrimidine all react at the
nitrogen atom with acid to form a quaternary salt, but pyrrole does not. Explain.
ans.
N
N
pyridine

N
pyrimidine

N
N
H
imidazole

H N
N
H
pyrrole

All of these heterocycles are 6 electron aromatic

systems, but only pyrrole needs its nitrogen electrons
to have 6 electrons. Thus pyrrole has no non-bonding
electrons available for reaction with acid. Pyrrole is not
basic, but the others are.
12.7 Histidine and histamine contain a structural unit found in many compounds
that affect the central nervous system. Identify that unit.
ans.
HOOC
N
N
NH 2
NH 2
N
ArCH2 CH2 NR2
N
H
H
arylethylamine
histidine
histamine
The unit is the -aryl ethyl amine unit. The aromatic ring can heterocyclic or
hydrocarbon. Morphine, quinine and many other compounds also contains the
unit.
12.8 The pyrimidine components found in nucleosides have important keto-enol
equilibrium. Show the equilibrium with thymine.
ans.

418 Problem Sets

O
HN
O

N
H
keto

OH
CH3

CH3

N
HO

N
enol

thymine

Chapter 13
13.1 Write the structure of a fat, soap, steroid, terpene and prostaglandin.
ans.
All of these structures can be found throughout the chapter.
13.2 Show the saponification products of castor oil, but first find the structure of
castor from another book.
ans.
O
OCR
O
O
OH
Z
RCOCH2CHCH2OCR
R = CH3(CH2)5CHCH2CH=CH(CH2)7COOH
also minor amounts of other acids
castor oil
NaOH

OH
HOCH2CHCH2OH
glycerol

OH
Z
CH3(CH2)5CHCH2CH=CH(CH2)7COOH
ricinoleic acid

13.3 Show the major components of a soap and a detergent.

ans.
+
COO Na
soap
+
SO3 Na

detergent
(Ca2+ salts are water soluble)
13.4 Write the structure of prostaglandin E2. How many stereogenic centers are
present? What are the configurations of the two alkene units? What are the
absolute configurations of the alcohol carbons?
ans.

Problem Sets 419

O

prostaglandin E2

H
Z
*
E
H
* *
H *
HO S H
S OH

COOH

Four stereogenic centers. 5-ene is Z; 12-ene is E.

10-hydroxyis S; 14-hydroxy is S
13.5 Predict products of the following reactions.
ans.
CH3 O
a)

b)
HO
CH3

CH3

CH3

c)

O
O CCH3

CH3
CH3
13.6 Identify the isoprene units in citronellal (Ch. 8), citrenellol (Ch. 7),
and geraniol (Ch. 7)
ans.
HO

HO

Geraniol

Citronellol
O
H
Citronellal

Chapter 14
14.1 Give an example of a) a tetrose b) an aldopentose c) a D-sugar d) epimers.

420 Problem Sets

ans.
CH O
H C H
a)

H C OH b)
CH2OH
tetrose

CHO
H

c) a and b

OH
d)

OH

OH

CH2OH
A D-pentose
aldopentose

H
H

CHO
OH
OH
CH2OH

CHO
HO H
H OH
CH2OH

D-(-)-erythrose D-(-)-threose
epimers at C-2

14.2 Show the carbohydrates derived by one carbon extension through the KillianiFischer synthesis from: a) D-(-)ribose, b) D-(-)-arabinose, c) D-(+)-xylose, and c)
D-(-)-lyxose.
ans.
D-(-)-ribose
D-(-)-arabinose
CHO
CHO
H OH HO H
H OH
H OH
H OH
H OH
H OH
H OH
CH2OH
CH2OH
D-(+)-allose
D-(+)-altrose

CHO
CHO
H OH HO H
HO H
HO H
H OH
H OH
H OH
H OH
CH2OH
CH2OH

D-(+)-xylose

D-(+)-glucose
D-(+)-mannose
D-(-)-lyxose

CHO
CHO
H OH HO H
H OH
H OH
HO H
HO H
H OH
H OH
CH2OH
CH2OH
D-(-)-gulose
D-(-)-idose

CHO
CHO
H OH
HO H
HO H
HO H
HO H
HO H
H OH
H OH
CH2OH
CH2OH
D-(+)-galactose
D-(-)-talose

14.3 What is the relationship between D-glucose and D-mannose? Draw Haworth
and conformational structures of D-mannose (found in problem 14.2 answer).
ans.

Problem Sets 421

glucose and mannose are epimers at C-2
6CH OH
2
OH CH2OH
5 O
O
HO
1
4
HO
OH
OH OH
-anomer
HO 3
2
HO
Haworth projection

Conformational

D-(+)-mannose
14.4 Complete the reactions below.
ans.
H
CHO
H
1) Ph3P=CHCO2CH3
CH=CHCO2CH3
a)
O
O
2) H3O+
HO OH
H3C CH3
CHO
HO H
HNO3
b) HO H
HO H
H OH
CH2OH

COOH
HO H
HO H
HO H
H OH
COOH

CHO
c) HO

CH2OH
H

1) NaBH4
2) H+

CH2OH

HO

CH2OH

14.5 Show the conformational structure for the methyl _-glycoside from Dgalactose (problem 14.2)
ans.
CHO
OH
H
OH
CH2OH
O
HO H
HO
H
HO
H
OH
OH
CH2OH
OCH3
D-(+)-galactose

methyl -D-galactopyranoside

14.6 What is the configuration of the glycoside bond in a)maltose, b) lactose,

c) cellobiose and d) sucrose.

422 Problem Sets

ans.
a) alpha, b) beta, c) beta, d) alpha and beta
14.7 Write a mechanism for the conversion of glucose to maltose.
ans.
CH2OH
CH2OH
O
H+
O
HO
HO
OH
HO
HO
OH
OH
glucose unit
CH2OH
HO
HO

HO
+

OH
-H+

CH2OH
HO
HO

CH2OH

+
OH2

O
OH

HO
OH

O
OH

maltose

O
HO

CH2OH

O
OH

OH
14.8 Which polysaccharide would you expect makes up the grasshopper's skin?
ans.
Chitin

Chapter 15
15.1 What are the distinguishing features of the natural amino acids?
ans.
COOH The R group detemines the overall polarity of the molecule,
and the structure and functon of the protein it is in.
H2N
H
L-amino acid
R
S-configuration
15.2 Show a synthesis of leucine by using the Gabriel method. What are some of
the shortcomings of the method? Would the Gabriel be suitable to prepare Ile?
ans.

Problem Sets 423

O

CO2C2H5

N CH
CO2C2H5
O
H3O+heat
-CO2

O R
NaOCH2CH3

N C

CO2C2H5

CO2C2H5
CH3CHCH2I
O
CH3
CH3CH2CHCH3
CH2CH(CH3)2
NH2-CH-COOH
NH2-CH-COOH
Ile
Leu

The Gabriel metod involves SN2 substitution and therefore

is subject to steric effects. Ile attempts would give much E2
reaction. Also, a racemic mixture would be produced.
15.3 Write structures for a) Phe-Gly, b) Gly-Leu-Lys, c)Nutrasweet.
ans.
O
O
a)
NH2-CH-C-NH-CH-C-OH
CH2Ph

Phe-Gly
O
O

CH2CH2CH2CH2NH2
O

b)
NH2-CH-C-NH-CH-C-NH-CH-C-OH
H

CH2CH(CH3)2
Gly-Leu-Lys
CH2Ph
O
O
c)
NH2-CH-C-NH-CH-C-OCH3
CH2COOH
Asp-Phe Methyl ester, Nutrasweet

15.4 If the N-terminal end of a protein contained Ser, what would be the structure
obtained by analysis with Sanger's reagent?
ans.
NO2
O
O2N

NHCHC OH
CH2OH

15.5 A peptide gave the following peptide fragments on partial hydrolysis. What is
the structure of the original peptide? Trp-Gly, Val-Ala, Pro-Leu-Val, Gly-Pro-Leu
ans.

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Trp-Gly
Gly-Pro-Leu
Pro-Leu-Val
Val-Ala
Trp-Gly-Pro-Leu-Val-Ala
15.6
What are the three classifications of proteins, and what are their
characteristics?
ans
Fibrous proteins--insoluble proteins found in collagens (tissue), elastins
(tendons) and keratins (hair)
Globular proteins--soluble proteins such as albumins (egg white), globulin
(blood), histines (tissue) and protamines (in nucleic acids).
conjugated proteins--combined with other molecules such as glycoproteins
(bound with carbohydrates) and lipoproteins (bound with lipids).
15.7 What is meant in protein chemistry by a) primary structure, b) secondary
structure, c) tertiary structure, and d) quaternary structure?
ans.
a) primary structure refers to the sequence of amino acids.
b) secondary structure refers to the shape of the sequence such as helix
or -pleated sheet.
c)tertiary structure refers to folding of the protein.
d) quaternary structure refers to interactions between two or more proteins.
15.7 What are the basic components of the mechanism of enzyme catalysis?
ans.
Enzymes use molecular recognition for very specific reactions with
substrates. Thus the substrate recognizes (or the enzyme recognizes) the
particularly fit and interaction with a substrate. The two components form a
complex called the enzyme-substrate complex. A reaction takes place in the
complex at an extremely fast rate to produce the products and the free enzyme. The
enzyme is available to catalyze more reactions with the same substrate. Coenzymes
fit with certain enzymes by molecular recognition and the pair is required to catalyze
reactions with their particular substrate.

Problem Sets 425

15.8 Find from another source the reason for insulin not functioning properly with
cells in type-2 diabetics?
ans. Once you find out, propose a solution Many diabetic people would
appreciate your cure.

16.6 Problem Set

16.1 The first step in the metabolism of glucose (glycolysis) involves the formation
of the glucose 6-phosphate shown in this chapter. The next step is the conversion
of glucose-6-phosphate by an enzyme and ATP to fructose 1,6-diphosphate. Show
the structure of fructose 1,6-diphosphate.
ans.
O
HO P-O
O3PO
O OH OPO3
O HO
ATP
ADP
HO
OH
HO
OH
H OH
enzyme
H
H
OH
-D-fructose-1,6-diphosphate

-D-glucose-6-phosphate

16.2 The oxidation of ethanol by NAD+ is stereospecific. Only the pro-R

hydrogen atom is removed. Which hydrogen atom is the pro-R hydrogen?
ans.
Ethanol has two hydrogen atoms and thus has no stereogenic center. If you
were to replace a hydrogen with deuterium then a stereogenic center would be
present. You replace a hydrogen with a deuterium and determine the absolute
configuration. If the configuration of the stereogenic center is R, then the H that
was replaced is pro-R.
OH
CH3

pro-R
H
CH3
H
pro-S

OH

OH
D

H
CH3
S

16.3 Show a crossed Claisen reaction between benzaldehyde and acetyl-CoA. Do

you expect this to be a significant biological reaction?
ans.

426 Problem Sets

O

OH

enzyme

CH2COO
SCo-A

CH3

Not very significent. No benzaldehyde in biological systems,

and if it were there an enzyme specific for the reaction would
be necessary.
16.4 The decarboxylation of acetoacetic acid produces acetone and carbon dioxide
is lost. The decarboxylation of biotin does not release carbon dioxide but instead
uses the carbon dioxide in a synthetic step to produce oxaloacetate. Have you seen
any organic reactions that use the carbon dioxide lost from acetoacetic acid (or
malonic acid) use in a coupled synthetic step?
ans.
There appears to be no similar organic reactions. The CO2 produced from
acetoacetic acid decarboxylation could be bubbled into a Grignard reagent, but dryice is a better source of carbon dioxide.
16.5 Show the analogous mechanism between decarboxylation of a _-ketoacid and
the thiamine decarboxylation of pyruvate.
ans
O
O

C CH
3
OH

C CH
3
OH
O
CH3

N
S

CH3

C
C CH3
OH

C CH3
OH

16.6 Another biological reagent is vitamin B6 which displays activity through

pyridoxal phosphate as shown in chapter 15. Show the structure of pyridoxal
phosphate and explain its function.
Pyridoxal phosphate functions to accept the amino group of amino acids in
the metabolic conversion of the amine to a carbonyl group.
O
HC
-2
OH
O PO
3

+
CH3
N
H
pyridoxal phosphate

Problem Sets 427

Chapter 17
17.1 Show structures of the deoxynucleosides and nucleotides derived from A, C,
and 5FU.
ans.
O
F
NH2
HN
N
N
O N
O-PO2O
N
O
N
O-PO2O
O
HO
HO
5-fluoro-2'-deoxyturidine monophosphate
2'-deoxyadenosine monophosphate (dAMP)
NH2
N
O N
O-PO2O
O
2'-deoxycytidine monophosphate (dCMP)
HO
Nucleotides. Nucleosides are without the PO317.2 If a RNA strand contained repeating units of AUA, what would be the
structure of the protein synthesized?
ans.
Ile-Ile-Ile--------- (poly-Ile)
17.3 Consider the sequence of bases in a DNA segment. (5 end) A-C-C-G-T-A-CG-G-T-A-T (3 end). What would be the base sequence in a new RNA strand, and
what would be the protein that the new RNA would produce?
ans.
5-ACCGTACGGTAT-3 DNA
3-UGCCAUGCCAUA-5 RNA 3 TO 5
5-AUACCGUACCGU-3 RNA 5 TO 3
Ile Pro Tyr Gly

protein

17.4 Classify the bases, A, T, U, C, G as pyrimidine or purine type.

ans.
A-purine, T-pyrimidine, U-pyrimidine, C-purine, G-purine

428 Problem Sets

17.5 9--D-ribofuranosylpurine is found in mushrooms. What is its structure?
ans.
N
HO

N
N

HO
OH
17.6 Allopurinol is a drug used to reduce the formation of uric acid, a metabolic
product from purine bases, and prevent a disease called gout. Suggest a mechanism
for the action of allopurinol.
O
OH
H
N
NH
N
O
N
N
N
N O
N
H
H
allopurinol
uric acid
ans.
The N-N bond of allopurinol cannot be converted to a carbonyl group and
thus inhibits the enzyme responsible for conversion of purines into uric acid.

Chapter 18
18.1 Find in another book source or on the internet a short biography of Paul
Ehrlich.
ans.
Paul Ehrlich was born in Prussia in 1854 (d1915 German. He had little
formal training in his early years, but earned a degree in Medicine from the
University of Leipzig. He served as a professor at the University of Berlin. He
discovered an effective drug for the treatment of syphilis and made many
contributions to the field of immunology. He receive a Nobel Prize in Medicine
jointly with Dr. I. I. Mechnikov in 1908.
18.2 Many different chemical compounds are effective antibacterial agents. How
can such a diverse range of structures accomplish this?
ans.
Bacterial cells are much simpler than human cells and often must synthesize
many of its own required ingredients. Antibacterials of various structures can work
to inhibit the enzyme catalyzed processes for the preparation of the ingredients.

Problem Sets 429

Other agents work by breaking down the fragile bacterial cell wall or by disrupting
the cell membrane. Inhibition of protein and nucleic acid synthesis are other modes
of actions for antibacterial substances. Thus many paths are available for killing
bacterial cells and many chemical structures can participate as antibacterial agents.
18.3 What are prodrugs?
ans.
Chemicals that are taken as treatments of disease but are not the active agent
responsible for the desired effects. Biochemical transformations convert the
prodrugs into the active drug. Aspirin, o-acetylbenzoic acid, is a prodrug as it is
enzymatically converted into the active drug, salicylic acid.
18.4 What structural unit is found in penicillin and cephalosporin antibiotics?
ans.

The -lactam ring system, and

the free acid function.

COOH
18.5 In addition to the -phenethyl amine unit found in the opiates, what other
structural features affect the potency of opium drugs?
ans.
In the theory of drug-protein interactions, the opiate receptor
has three binding sites. The amine binding site, the phenol
binding site, and the site for the other side of the molecule.
The beta-phenethyl amine structure shapes the molecules for
optimal binding of the three structural units.
CH3
N
O OH
OH

Morphine

18.6 The accidental finding of drug activity is very important in drug therapy. How
could nitroglycerine be found to be a heart stimulant.
ans.
Nitroglycerine as discovered by the workers in the explosives industry who
experienced severe headaches on exposure to nitroglycerin. Studies found that

430 Problem Sets

nitroglycerin dilated blood vessels in the heart. Isoamylnitrite and other organic
nitrites have similar heart simulating effects, being discovered by workers handling
the chemicals.
18.7 What is a common structural feature of anti-viral drugs?
ans.
Very few effective anti-viral drugs are known, but most have purine or
pyrimidine ring systems that are capable of forming nucleosides and incorporating
into the DNA or RNA of a virus.
18.8 If possible search the internet for molecular modeling. Or obtain use of a
chemistry modeling program such as Chem D. Draw structures of the drugs in
section 18.6 and observe their 3D shapes. Try to model a protein and show its
interaction with a drug.
ans.
No particular answer, this involve computer experimentation.
18.9 What structural unit is found in many hormones, anti-inflammatory agents,
and reproductive drugs.
ans.
The steroid nucleus. This could indicate that the protein receptors for the
three agents are similar in structure.

Chapter 19
19.1 List the types of radiation, infrared, ultraviolet, and radio in order of increasing
energy. (most energetic last). Which frequency is associated with NMR
spectroscopy.
ans.
radio < infrared < ultraviolet Radio frequencies are used in NMR
spectroscopy.
19.2 If the frequency difference between an observed NMR peak versus TMS is
200 MHz, what is the chemical shift in __ppm on a spectrometer operating at 100
MHz. What is TMS and its purpose? What kind of peak is likely being observed
if it occurs as a singlet?
ans.
The chemical shift = 200/100 = 2 ppm. TMS stands for tetramethylsilane,
(CH3)4Si, and its frequency is set by the operator of the spectrometer at 0 MHz.
All other peaks are referenced to the TMS peak, which occurs at higher field than
most other peaks.

Problem Sets 431

The peak being observed is in the alkane region and as a singlet is likely to
be a methyl.
19.3 Predict the chemical shifts and spin-spin coupling spectrum for
(CH3)2CHOCH 2CH3.
ans.
The methyls of the isopropyl would occur around 1.5 ppm and be observed
as a doublet because of splitting from the neighboring CH. The CH of the isopropyl
would be observed around 3 ppm and would be split into a septet (seven peaks)
because of the 6 neighboring methyl protons. The methyl of the ethyl group would
occur around 1.5 ppm and would be seen as a triplet because of splitting with the
neighboring CH2. The CH2 of the ethyl would occur around 2 ppm and be
observed as a quartet because of the neighboring methyl group.
19.4 A compound, C5H10O, gives the Ir and NMR spectra shown below. What is
the structure of the compound?
ans.
The compound is 2-pentanone. The ir shows a strong C=O, and the NMR
show a methyl singlet and three separate multiplets for the propyl side of the ketone.
19.5 The mass spectrum of aspirin is shown below. Identify the origins of the
peaks listed.
ans.
180 is the molecular ion (molecular mass); 139 is the molecular ion minus a
radical C2HO from the ester group; 120 is the loss of the elements of CO2 and
CH4.
19.6 The 13C NMR and Ir spectra of C 2H3N are shown below. What is this
simple compound. What is the large Ir peak?
ans.
The compound is acetonitrile, CH3CN. The Ir shows the CN peak at 2100
cm-1 , and the CN and CH3 groups as singlets in the carbon NMR
spectrum.

432 Problem Sets