Krisman
REFERENCE GUIDE
FOR MEDICINAL &
ORGANIC CHEMISTRY
QUESTIONS & ANSWERS
2009-2010
Manan H. Shroff
www.pharmacyexam.com
Krisman
REFERENCE GUIDE
FOR MEDICINAL &
ORGANIC CHEMISTRY
QUESTIONS & ANSWERS
2009-2010
www.pharmacyexam.com
Krisman
This reference guide is not intended as a substitute for the advice of a physician. Students
or readers must consult their physician about any existing problem. Do not use any information
in this reference guide for any kind of self-treatment. Do not administer any dose of mentioned
drugs in this reference guide without consulting your physician. This is only a review guide for
preparation for the Foreign Pharmacy Licensing board exam.
The author of this reference guide is not responsible for any kind of misinterpreted, incorrect or
misleading information or any typographical errors in this guide. Any doubtful or questionable
answers should be checked in other available reference sources.
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Krisman
REFERENCE GUIDE
FOR MEDICINAL &
ORGANIC CHEMISTRY
QUESTIONS & ANSWERS
2009-2010
Manan H. Shroff
www.pharmacyexam.com
Krisman
Preface:
Reference Guide For Medicinal and Organic Chemistry - Questions and Answers is
specifically written for students preparing for the FPGEE and Canadian Evaluating Exams. It has
500 questions with answers and complete explanations. Recently, the exam puts more emphasis
on graph- and structure-based questions, therefore an effort was made to include all of these
topics in a review guide.
Each answer is explained thoroughly to refresh your memory on specific topics. Please do
not go through only the questions and answers. Try to understand and learn the answers explanations. It is the best way to get the most out of this review guide.
I hope my efforts will help you to pass your key exam. I wish you the very best of luck,
and any questions or comments are always welcome.
Manan Shroff
www.pharmacyexam.com
Krisman
TABLE OF CONTENTS
SECTION-I
QUESTIONS
SECTION-II
ANSWERS
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87
Krisman
3.
Which of the following is falsely presented?
a.
a.
CH4
b.
CH4
Cl
Be
Cl
1800
F
b.
c.
..
O
c.
CH4
CH3Br + HBr
I2
d.
CH4
CH3I + HI
4.
Which of the following statements is
true about the following chart?
H
C
d.
CH3Cl + HCl
Br2
1800
CH3F + HF
Cl2
F
1200
F2
H
H
109.50
2.
Which of the following molecules has
the largest dipole?
a.
Cl
C
b.
Cl
Cl
a.
The temperature is a measure of the
average kinetic energy.
Cl
Cl
c.
b.
Kinetic energy of the moving molecules
is not the source of the energy needed for
reaction.
c.
The number of molecules with a particular kinetic energy is greatest for an energy
near the average and decreases as the energy
becomes larger or smaller than the average.
d.
O
H
d.
The size and weight of the particles are
characteristic of each reaction and cannot be
changed.
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a.
b.
c.
d.
It is an endothermic reaction.
The b-portion is called activation energy.
The a-portion is the energy given off.
It is an exothermic reaction.
Krisman
c.
d.
8.
a.
b.
c.
d.
3
4
7
1
9.
Which of the following is an isotope of
hydrogen?
6.
On a following graphical presentation,
identify the activation energy for a reaction.
10.
Which of the following statements are
TRUE about the following graphical presentation?
a.
b.
c.
d.
W
X
Y
Z
7.
From the graph of question 6, one can
say that:
a.
b.
Z = exothermic energy
Z-Y = exothermic energy
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Krisman
12.
a.
b.
c.
d.
760 o
100 o
20 o
80 o
II.
The H-bond formation is the strongest
in H2Te.
III.
The increase of the boiling point of a
compound is directly proportional to its
molecular mass.
a.
b.
c.
d.
I only
I and II only
II and III only
All
11.
Which of the following statements are
TRUE about the relationship between kinetic
energy and number of molecules?
13.
Which of the following pentane structures has the lowest boiling point?
a.
b.
I.
As the temperature of a gas increases,
its kinetic energy is increased.
c.
d.
a.
b.
c.
d.
CH3
CH3
II.
Temperature increases a measure of the
average kinetic energy of the particles.
III.
The average kinetic energy of molecules
is found at the peak of the curve.
CH3
I only
I and II only
II and III only
All
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CH4
2.
CH3CH3
3.
CH3CH2CH3
Krisman
3.
4.
CH3
4.
CH3
CH3
CH3
a.
b.
c.
d.
1>2>3>4
4>3>1>2
2>4>3>1
1>4>3>2
15.
Which of the following compounds
represents a pair of diastereomers?
a.
b.
c.
d.
1 and 3
2 and 4
3 and 2
4 only
1.
I
SO3H
1.
(Chloroiodomethanesulfonic acid)
H
2.
CH3
CH3
Cl
Isopropyl chloride
2.
H
3.
CH3
COOH
OH
(Lactic acid)
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10
19.
How many enantiomers are possible for
2,3-Dichloropentane?
H
CH3
4.
Krisman
C2H5
Cl
Cl
(sec-Butyl chloride)
a.
b.
c.
d.
2,3-Dichloropentane
1
2
3
4
a.
b.
c.
d.
17.
What is the complete name for the optically active compound listed below?
a.
b.
c.
d.
Cl
1
3
4
5
20.
Which of the following is (R)-3hexanol?
(+)-Bromochloroiodomethane
(S)-Bromochloroiodomethane
(R)-Bromochloroiodomethane
(RS)-Bromochloroiodomethane
18.
In the following compound what would
be the correct configuration sequence of atoms
attached to the chiral carbon?
H
CH3CH
C2H5
CH3 Cl
3-chloro-2-methylpentane
a.
b.
c.
d.
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a.
b.
c.
d.
fig-1
fig-2
fig-3
fig-4
11
23.
Which of the following compounds
represents a pair of enantiomers?
a.
b.
c.
d.
a.
b.
c.
d.
I and IV
II and III
III and I
II and IV
22.
Which of the following compounds is
(S)-4-bromo-1-methylcyclohexene?
Krisman
X and Y
X and Q
Z and Y
Z and R
24.
Pure (R)-2-pentanol has a specific rotation of -10.50 degrees. You have purified a
sample that has a calculated specific rotation of
-2.625 degrees. What can you conclude about
this sample?
a.
b.
c.
d.
25.
Which of the following is classified as
a meso- compound?
a.
b.
c.
d.
I
II
III
IV
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12
Krisman
28.
Which of the following C8H16 isomers
is thermodynamically most stable?
a.
b.
c.
d.
i
ii
iii
iv
26.
How many stereoisomers of
(CH3)2CHCH=CHCH2CH(OH)CH2Br are possible?
a.
b.
c.
d.
5
4
2
0
27.
A C7H14O optically active alcohol (3,3Dimethylcyclopentanol) is oxidized by Jones
reagent to an optically inactive (achiral) ketone.
What is the correct structural formula for this
compound?
a.
b.
c.
d.
R
S
T
U
29.
How many stereoisomers are possible
for the following compound?
a.
b.
c.
d.
2
4
8
10
30.
Which of the following compounds has
the highest boiling point?
a.
b.
c.
d.
a.
b.
c.
d.
CH3CH2CH2CH2CH3
CH3CH2OH
CH3Cl
NH4
1
2
3
4
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13
OH
HO
a.
b.
c.
d.
Krisman
Imidazoline
Imidazole
Thienopyridine
Benzofuran
OH
OH
OH
Gluconic acid
a.
C7H13O8
b.
C6H12O7
c.
C5H12O9
d.
C6H12O10
H
N
NH
NH
O
Compound A
Compound B
H
N
NH
COOH
H
C
Compound C
Compound D
a.
b.
c.
d.
COOH
Fumaric acid
a.
b.
c.
d.
Ascorbic acid
Lactic acid
Formic acid
Maleic acid
Cl
N
C
OH
NH2
Compound A
Compound B
Compound C
Compound D
CH2
CH2
CH2
PO3H2
a.
b.
c.
d.
+
PO3H Na
Hypertension
Diabetes
Osteoporosis
Aluminum toxication
COOCH3
Clopidogrel
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51
Krisman
I.
II.
III.
Acetaminophen
Phenacetin
Acetanilide
a.
b.
c.
d.
I only
I and II only
II and III only
All
235.
COOH
O
C
Ketoprofen
a.
b.
c.
d.
Ether
Ester
Ketone
Phenol
CO-NH2
OH
a.
b.
c.
d.
C3H7
O
N
C3H7
COOH
Probenecid
CH2
CH2
OCH3
Nabumetone
a.
b.
c.
d.
naphthalene
phenanthrene
pentacene
benzopyrene
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CH3
I.
Uricosuric activity decreases with the
substitution of methyl groups.
II.
Renal clearance of the compound decreases with substitution of methyl groups.
III.
The reabsorption of uric acid in proximal tubules increases with substitution of methyl groups.
a.
b.
c.
d.
I only
I and II only
II and III only
All
52
Krisman
NH
S
NH
N
H
a.
b.
c.
d.
O
COOH
Penicillin
a.
b.
c.
d.
N
CH3
N
CH2
CH2
OH
a.
b.
c.
d.
pyridine
pyrazole
imidazole
pyrrole
241.
N
O
a.
The aromatic ring that is directly attached to the side-chain carbonyl and both ortho
positions should be substituted by methoxy
groups.
a.
b.
c.
d.
CH3
MAO
COMT
Xanthine oxidase
Dihydro folate reductase
NO2
CH3
cyclic ketone
cyclic amide
cyclic ester
cyclic amine
b.
The aromatic ring that is directly attached to the side-chain carbonyl and ortho and
para positions should be substituted by methoxy
groups.
c.
The aromatic ring that is directly attached to the side-chain carbonyl and meta and
para positions should be substituted by methoxy
groups.
d.
A methylene between the aromatic ring
and carbonyl group of side chain.
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53
Krisman
H
OCH3
OH
CH CH2
N
O
COOH
a.
b.
c.
d.
NH
CH
An MAO inhibitor
A xanthine oxidase inhibitor
A 5-alpha azo reductase inhibitor
A beta-lactamase inhibitor
CH3
a.
b.
c.
d.
CH3
CH3
Quinoline
Isoquinoline
Pyridazole
Indole
O
S
NH2
Primaquine
O
COOH
a.
b.
c.
d.
Hydralazine
Sulfonamide
Clavulanic acid
Finasteride
H
Thiabendazole
a.
b.
c.
d.
CH2 O
NH2
NH
NH
Legionnaires disease
Pneumocystis carinii pneumonia
Parkinsons disease
Travellers diarrhea
NH2
I.
II.
III.
Benzimidazole
Thiazole
Isothiazole
a.
b.
c.
d.
I only
I and II only
II and III only
All
cytosine deaminase
?
N
H
Flucytos ine
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54
Griseofulvin
Capsofungin
5-Fluorouracil
Micafungin
a.
b.
c.
d.
a.
b.
c.
d.
CH
(CH2)8-COOH
Krisman
4-pyridine-1-ethylthiocarbomide
3-ethyl carbothiamidine
2-ethylpyridine-4-carbothioamide
2-ethyl-4-thioamide
Oleic acid
Undecylenic acid
Arachidic acid
Stearic acid
OH
NH2
p-aminosalicylic acid
a.
b.
c.
d.
Isoniazid
Nicotinamide
Pyrazinamide
Rifampin
a.
b.
c.
d.
C2H5
NH CH2 CH2
NH
CH2OH
C2H5
a.
b.
c.
d.
CH
255. Discoloration of pink, red or brownishblack of the sputum, tears and urine has been
reported with Clofazimine. What is the name
of the organic compound in Clofazimine that is
responsible for this?
Cl
Rifabutin
Ethambutol
Isoniazid
Ethionamide
CH3
Streptomycin
Sulfonamide
Isoniazid
Ethambutol
CH
NH
CH3
Cl
Clofazimine
NH2
C2H5
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a.
b.
c.
d.
Chlorobenzene
Para-aminochlorobenzene
Dibenzopyrazine
2-aminopropane
55
Sulfamethoxazole
Rifampin
Dapsone
Thalidomide
a.
b.
c.
d.
Krisman
I only
I and II only
II and III only
All
257. The principal side effect of the compound shown below is:
Pt
Cl
NH3
NH3
a.
b.
c.
d.
Cl
Cardiac toxicity
Severe nausea and vomiting
Respiratory failure
Severe rash
a.
b.
c.
d.
Sodium bicarbonate
Mesna
Sodium thiosulfate
Aluminum phosphate
I.
II.
III.
a.
b.
c.
d.
Cl
Cisplatin
Pt
NH3
Cl
NH3
Cyclophosphamide
Ifosfamide
Streptomycin
I only
I and II only
II and III only
All
CH2
Mesna
CHO
(Acrolein)
a.
b.
c.
d.
CH3CH2CHO
CH3CH2SHCHO
CHOCH2CH2SCH2CH2SO3CH3CH2CH2SHCHCOO-
Procarbazine
Carmustine
Thiotepa
Ifosfamide
II.
Saline or mannitol diuretics should be
used continuously throughout the therapy.
III.
Prolonged dialysis shall be used to
minimize cisplatin induced nephrotoxicity.
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56
Krisman
NH2
CH2
CH2
CO-CH3
NH
Serotonin
OH
Acetaminophen
214. (b) Sulfamethoxazole is a sulfonamide bacteriostatic antibiotic. It is most often used as part
of a synergistic combination with trimethoprim
in co-trimoxazole, which is also known as
Bactrim or Septra. Sulfonamides are structural
analogs and competitive antagonists of paraaminobenzoic acid (PABA). It is indicated for
the treatment of UTI, otitis media, acute exacerbations of chronic bronchitis in adults,
shigellosis, pneumocystis carinii pneumonia or
PCP and travellers diarrhea in adults.
N
O
NH
S
CH3
CH3
HO
N
NH2
CH2
OH
Sulfamethoxazole
CH2
OH
213. (a) Serotonin (5-hydroxytryptamine, or 5HT) is a monoamine neurotransmitter synthesized in serotonergic neurons in the central
nervous system (CNS) and enterochromaffin
cells in the gastrointestinal tract of animals inwww.pharmacyexam.com
Imidazoline
Imidazole
Krisman
OH
OH
CH3
OH
Resorcinol
Phenol
OH
OH
C3H7
H
O
m-Cresol
OH
CH3
p-Cresol
Benzyl alcohol
COOH
COOH
Propylthiouracil
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CH2
Imidazolidine
CH3
O-Cres ol
217. (c) Propylthiouracil (PTU) or 6-N-Propylthiouracil is a drug used to treat hyperthyroidism by decreasing the amount of thyroid hormone produced by the thyroid gland. It is used
in hyperthyroidism, including Graves disease.
It has a risk of causing agranulocytosis as a side
effect. It is a propyl derivative of thiouracil.
OH
Phthalic acid
(pKa = 2.9)
Benzoic acid
(pKa = 4.2)
221. (c) The chemical properties of the toluidines are quite similar to those of aniline. Due
to the amino group bonded to the aromatic ring,
the toluidines are weakly basic. At room temperature and pressure, ortho- and meta-toluidines are viscous liquids, but para-toluidine is
a flaky solid. This can be explained by the fact
that the p-toluidine molecules are more symmetrical and fit into a crystalline structure more
easily.
139
NH2
NH2
CH3
CH3
(o-toluidine)
(m-toluidine)
-23 C
-30 C
CH3
(p-toluidine)
+43 C
CH2
NH2
HO
Tyramine
223. (a) Butyric acid, also known under the systematic name butanoic acid, is a carboxylic acid
with the structural formula CH 3CH 2CH 2COOH.
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Krisman
CH
CH2
NH2
Propenamine
(pKa = 10.7)
CH2
Aniline
(pKa = 4.6)
NH2
C2H5
C2H5
NH
Benzylamine
Diethylamine
(pKa = 9.3)
(pKa = 11)
140
COOH
CH2
COOH
CH2
OH
Krisman
OH
OH
OH C
OH
OH
Citric acid
H2CO3
CO2
OH
(2-hydroxypropanoic acid)
Lactic acid
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C
OH
Gluconic acid
COOH
C
H
H
Maleic acid
R1
R2
Bisphosphonate
Naphthalene
Phenanthrene
Benzopyrene
OH
NH2
CH2
Krisman
CH2
CH2
PO3H2
+
PO3H Na
Aledronate sodium
234. (c) II and III only. The metabolism of acetanilide, acetaminophen and phenacetin is
shown in figure 11.13, page 143. Both acetanilide and phenacetin are metabolized to
acetaminophen. However, both also undergo hydrolysis to form aniline or to hydroxyaniline
derivatives that are directly responsible for
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Pentacene
142
Acetanilide
Krisman
NHCOCH3
NHCOCH3
OH
OC2H5
Acetaminophen
Phenacetin
N COCH3
NH2
methemoglobinemia,
hemolytic anemia
O
N-acetyliminoquinone
toxic metabolite
methemoglobinemia,
hemolytic anemia
Glutathione
NHCOCH3
glutathione
OH
non-toxic metabolite
Metabolis m of acetaminophen, phenacetin and acetanilide
Fig: 11.13
CH3 CH2
Thienopyridine
NH
O
Thiazolidinedione
Fig: 11.30
CH2
(1-Butene)
S
CH
CH
CH3
(2-Butene)
Fig: 11.31
(two alkyl groups )
[Saytzeff rule]
Fig: 11.32
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143
Krisman
N
NH
N
H
Imidazole
Pyrazole
N
H
Pyrrole
Pyridine
O
Beta lactam ring
fused to thiazolidine
N
NH
N
N
H
Allopurinol
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144
OCH3
R=
CH2-
OCH3
addition of methylene group
(beta-lactamse sensitive penicillin)
O
R C
NH
CH3
CH3
N
O
COOH
Penicillin
R = Electron-Withdrawing Group
Krisman
NH
S
CH3
CH3
N
O
COOH
Penicillin
OCH3
R=
OCH3
N
N
Isoquinoline
Quinoline
H
Benzimidazole
Thiazole
N
S
Is othiazole
Krisman
146
Krisman
NH2
N
phenazine or dibenzopyrazine
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4,4'-Diaminodiphenylsulfone
(Dapsone)
147
CH2
N
CH2
CH2
N
CH2
N
CH2
CH2
Thiotepa
CH2
N
CH2
CH2
N
CH2
N
CH2
CH2
Triethylenephosphoramide
(active metabolite of Thiotepa)
Krisman
NH3
NH3
Pt
Cl
+
Na
O
O
S
Na
O
Krisman
Pt
Cl
2 NaCl
Cisplatin
NH3
NH3
Sodium thiosulfate
S2O3
S2O3
+
+
Na
Na
water soluble
Fig: 11.14
CH
CH2 +
CHO
CH2 CH2
SO3
SH
(Mesna)
(Acrolein)
SO3
CHO
Fig: 11.15
Anthracyclines
NADPH reductase
O:
superoxide dismutase
+2
Cu
Catalase
H2O + O2
H2O2
Fe
+2
.OH + OH
+ Fe
+3
Cytotoxic
hydroxy
free radical
Fig: 11.16
(formation of cytotoxic free radicals by anthracyclenes)
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149
Krisman
NH2
N
HN
NH2
N
H
Adenine (6-aminopurine)
NH2
NH2 CH3
CH
NH2
N
H
Guanine
CH3
HN
N
H
Cytosine
N
H
Thymine (5-methyluracil)
O
HN
Amantadine
Rimantadine
N
H
Uracil
270. (a) Cidofovir (Vistide) is a synthetic acyclic pyrimidine nucleotide analogue of cytosine.
Cytosine is one of the five main bases found in
DNA and RNA. It is a pyrimidine derivative,
with a heterocyclic aromatic ring and two substituents attached (an amine group at position 4
and a keto group at position 2). The nucleoside
of cytosine is cytidine. Three nucleobases found
in nucleic acids (cytosine, thymine, and uracil)
are pyrimidine derivatives:
NH2
N
Cytosine
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CH3
HN
N
H
N
H
Thymine (5-methyluracil)
HN
N
H
Uracil
150
Krisman
NH2
CH3 COO
N
CH2
CH
CH3 COO
CH2 CH2
CH2
Famciclovir
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Hydrolys is
Oxidation
O
N
HN
NH2
HO
N
CH2
CH
CH2 CH2
CH2
HO
Penciclovir
O
N
HN
NH2
HO
HO
N
CH2
CH
CH2
CH2
Ganciclovir
Krisman
Acid derivatives:
(1) Carboxylic acids
O
R
OH
O
very electron rich
..
NH2
Amide
(2) Esters
O
R
OH
C
O
Carboxylic acid
(3) Amides
OR
..
NH2
O
(4) Acid halides
O
(5) Anhydride
O-CO-R
..
NH2
Amide
+
NH2
The most stable
acid-derivative
R
(Fig: 11.21)
of metabolic wastes such as urea, uric acid,
dissolved salts such as sodium chloride, and
dissolved organic compounds. Albumin is a
serum protein that cannot be filtered by the kidneys; and hence is not found in normal adult
urine.
417. (c) In organic chemistry, keto-enol tautomerism refers to a chemical equilibrium between
a keto form (a ketone) and an enol (an aldehyde
form). The enol and keto forms are said to be
tautomers of each other. The interconversion of
the two forms involves the movement of a
proton and the shifting of bonding electrons;
hence, the isomerism qualifies as tautomerism.
181
Acetone Isomers:
O
CH3
OH
CH3
CH3
Keto form
CH2
Enol form
168000
MW of fat
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Krisman
Krisman
O
CH2
O
R1
CH2
O
CH
R2
3 KOH
CH
O
CH2
R1
OH
OK
O
OH
R2
OH
CH2
OK
R3
R3
Glycerol
Fat or Oil
(Triglycerides)
OK
Soap
(Potassium salts of
long-chain fatty acids)
Fig: 11.22
stream have been linked to atherosclerosis, and
by extension, the risk of heart disease and stroke.
According to the American Heart Association,
the normal range for serum triglycerides is less
than 160 mg/dL.
424. (b) When a high proportion of saturated
fatty acids is used to manufacture the soap, the
resultant soap would be defined as hard soap.
In contrast when the soap is manufactured by
using a high proportion of unsaturated fatty
acids, it yields soft soap.
425. (b) I and II only. Soaps are potassium or
sodium salts of fatty acids.
426. (b) I and II only. Saponification (alkaline
hydrolysis) of a fat yields soaps (sodium or
potassium salts of fatty acids) and propane1,2,3-triol (also known as glycerol or glycerine).
427. (c) In chemistry, a base is most commonly
thought of as an aqueous substance that can
accept protons. A base is also often referred to
as an alkali (only if OH- ions are involved).
Alternate definitions of bases include electron
pair donors (Lewis), as sources of hydroxide
anions (Arrhenius) and can be thought of as any
chemical compound that, when dissolved in
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..
H
..
R
High-electron
density
N H
Ammonia
Aliphatic amine
183
..
..
N
CH3
CH3
absence of H-atom
to form H-bond
CH3
Trimethylamine
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Krisman
R3
Reduction
NH
C
R1
CH
R2
R1
R2
Amine
Imine
433. (c) Amines are normally prepared by heating an alkyl halide with alcoholic ammonia. In
the above reaction, tertiary amine or 3o amine
known as trimethylamine has been obtained.
CH3
CH3
CH3
Trimethyl amine
184
O
C
NH2
..
O
C
Krisman
HOOC
H
NH2
HOOC
*
C NH2
Glycine
CH3
Alanine
(optically inactive)
(optically active)
+
NH3
Zwitterion
HOOC
H
NH2
HOOC
CH2
NH2
CH3
CH3 CH
CH3
Phenylalanine
Valine
(optically active)
(optically active)
(Fig: 11.23)
such as water but insoluble in non-polar solvents such as alkane, benzene and ethanol. Their
aqueous solutions are neutral to litmus test due
to formation of zwitterions.
438. (c) A peptide bond is a chemical bond
formed between two molecules (preferably
amino acids) when the carboxyl group of one
amino acid reacts with the amino group of the
other amino acid, thereby releasing a molecule
of water (H2O). This is a dehydration reaction.
The resulting CO-NH bond is called a peptide
bond, and the resulting molecule is a dipeptide.
The four-atom functional group -C(=O)NH- is
called an amide group or (in the context of
proteins) a peptide group. Polypeptides and
proteins are chains of amino acids held together
by these peptide bonds. A peptide bond can be
broken by amide hydrolysis (the adding of
water).
439. (a) Proteins are large organic compounds
made of amino acids arranged in a linear chain
and joined together by peptide bonds between
the carboxyl and amino groups of adjacent
185
Krisman
442. (d) In organic chemistry, keto-enol tautomerism refers to a chemical equilibrium between
a keto form (a ketone) and an enol (an aldehyde) form. The enol and keto forms are said to
be tautomers of each other. The interconversion
of the two forms involves the movement of a
proton and the shifting of bonding electrons;
hence, the isomerism qualifies as tautomerism.
OH
OH
N
OH
HO
NO2
NO2
N
H
2,6,8-Trihydroxypurine
(Uric acid)
NO2
2,4,6 Trinitrophenol
(Picric acid)
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186
weak oxidizing
agent
COOH
(CHOH)4
(CHOH)4
CH2OH
CH2OH
Glucose
Gluconic acid
strong oxidizing
agent
COOH
(CHOH)4
(CHOH)4
CH2OH
COOH
Glucose
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448. (c) II and III only. A glucose solution fermented in the presence of the enzyme zymase
in anaerobic condition would yield ethanol and
carbon dioxide.
Zymase
C6H12O6
2C2H5OH + 2CO2
Ethanol
Glucose
CH2OH
Reducing
agent
(CHOH)4
(CHOH)4
CH2OH
CH2OH
Sorbitol
Glucose
(D-Glucitol)
OH
OH
OH
HO
Glucaric acid
Krisman
OH
OH
Sorbitol
OH
OH
OH
HO
OH
OH
Mannitol
Fig: 11.35
450. (a) I only. A disaccharide is a sugar composed of two monosaccharides. It is formed
when two monosaccharides are joined together
and a molecule of water is removed. The hydrolysis of maltose would yield two molecules
187
Krisman
OH
N
Oxidation
H
N
OH
HO
2,6,8-Trihydroxypurine
(Uric acid)
H
N
O
NH C
NH2
COOH
O
NH2 C
N
H
NH C
Allantoin
Hydrolysis
N
H
N
H
Urea
NH2
NH2 +
CHO
O
+ NH2 C
Glyoxylic acid
NH2
Urea
Allantoin
(Fig:11.24)
of glucose. The hydrolysis of sucrose would
yield a molecule of glucose and fructose
whereas the hydrolysis of lactose would yield
glucose and galactose.
451. (b) Raffinose is a trisaccharide composed
of three saccharides called galactose, fructose,
and glucose. It can be found in beans, cabbage,
brussel sprouts, broccoli, asparagus, other vegetables, and whole grains.
452. (b) Common table sugar or sucrose is
classified as a disaccharide. Upon hydrolysis it
yields one molecule of glucose and one molecule of fructose.
453. (c) The solution of -glucose has a specific rotation of 112o, whereas the solution of
-glucose has the specific rotation 19o. When
either -glucose or -glucose is dissolved in
water and allowed to stand, a gradual change in
specific rotation occurs. The specific rotation
of -glucose falls from 112o whereas the specific rotation of -glucose rises from 19o until a
constant value of 53o is achieved. This change
in optical rotation of a solution of either glucose or -glucose until a constant value is
obtained is called mutarotation.
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CH3
CH3
CH3
Krisman
SO2 NH2
Sulfanilamide
NH2
SO3 H
Sulfanilic acid
NO2
CH3
NO2
o-Nitrotoluene
m-Nitrotoluene
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NO2
p-Nitrotoluene
SO3H
p-Toluenesulfonic acid
SO3 H
Benzenesulfonic acid
189
Krisman
NH
CH2
3HCO
Capsaicin
C
O
O
o-Nitrophenol
NO2
p-Nitrophenol
Krisman
CH2
OH
LiAlH4
Reduction
Benzaldehyde
Benzyl alcohol
191
OH
Krisman
CHO
COOH
OH
dilute HNO3
OH
Oxidation
Resorcinol
Catechol
Benzaldehyde
OH
Benzoic acid
OH
OH
HO
HO
Quinol
Pyrogallol
OH
HO
OH
Phloroglucinol
(Fig:11.25)
475. (b) Salicylaldehyde, or 2hydroxybenzaldehyde, is the chemical compound with the formula C6H4CHO-2-OH. This
colorless oily liquid has a bitter almond odor at
a higher concentration and a characteristic buckwheat aroma at a lower concentration. Salicylaldehyde is a key precursor to a variety of
chelating agents, some of which are
commercially important. It can be prepared from
phenol and chloroform by heating with sodium
hydroxide. It forms intramolecular hydrogen
bonding. This also explains why salicylaldehyde
has a low water solubility because the -OH
group of salicylaldehyde is tied up with the CHO group by forming intramolecular
hydrogen bonding that prevents hydrogen bond
formation of salicylaldehyde with water
molecules.
O
H
Intramolecularhydrogen bond
O
CHO
CH3
Zn (Hg) / HCl
Salicylaldehyde
(2-Hydroxybenzaldehyde)
Reduction
Benzaldehyde
Toluene
CH3
Oxidation
Acetophenone
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COOH
Benzoic acid
192
CH3
CH2CH3
Zn (Hg) / HCl
Reduction
Acetophenone
Ethyl benzene
478. (c) o-Benzoquinone, also known as oquinone, can be prepared by the oxidation of
catechol in the presence of silver oxide.
OH
O
OH
Silver oxide
Oxidation
o-Benzoquinone
Catechol
CHO
HNO3 / H2SO4
NO2
Benzaldehyde
m-Nitrobenzaldehyde
480. (b) Tollens' reagent is an ammoniacal silver nitrate (Ag(NH3)2OH) solution. It was
named after Bernhard
Tollens.
The
diamminesilver complex (Ag(NH3)2OH) is an
oxidizing agent, which is itself reduced to silver metal, which in a clean glass reaction vessel forms a "silver mirror." This feature is used
as a test for aldehydes, which are oxidized to
carboxylic acids. It should be noted that the actual oxidation product is the carboxylate ion,
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Krisman
Methyl ketone
Acetaldehyde
Ethanol
Secondary alcohol
193
An aldehyde + Ag(NH3)2OH
Krisman
A carboxylate ion
Silver Mirror
Ammoniacal silver
nitrate solution
A ketone
No reaction
Ag(NH3)2OH
Ammoniacal silver
nitrate solution
(Fig: 11.26)
Iodoform Tests:
O
I2 / NaOH
CH3 C CH3
Iodoform
Acetone
O
I2 / NaOH
No reaction
(since no methyl gp)
CH3CH2 C CH2CH3
Diethyl ketone
O
H
CHI3
I2 / NaOH
C CH3
CHI3
Iodoform
Acetaldehyde
O
CH3 CH2 OH
Ethanol
I2 / NaOH
C CH3
Acetaldehyde
CH3 CH CH3
OH
CH3 C CH3
Acetone
(Secondary alcohol)
CHI3
Iodoform
I2 / NaOH
CHI3
Iodoform
(Fig: 11.27)
This is because ethanol is subsequently oxidized
to acetaldehyde and secondary alcohols are oxidized to methyl ketones under the condition
used for the test. The test is also used to distinguish ethanol from methanol since the latter one
does not give a positive iodoform test. The test
is also used to distinguish methyl ketone from
other ketones, (fig: 11.27).
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482. (b) With an alkaline solution of iodine, acetaldehyde forms yellow precipitates of iodoform whereas formaldehyde does not react.
483. (d) Fehling's solution is a solution used to
distinguish aldehyde from the ketone functional
groups, although ketose monosaccharides (such
as fructose) will also test positive, due to con194
Cu(OH)2
H
R
NaOH
Aldehyde
COONa + Cu 2O
red
precipitates
484. (d) All. Ketones (except alpha-hydroxy ketones) do not react with Tollens reagent,
Fehlings solution and Benedicts solution.
These tests help in distinguishing aldehydes
from ketones.
485. (c) When -naphthol reacts with ammonia in the presence of ammonium bisulfite, it
yields 1-Naphthylamine or -naphthylamine.
OH
CH3
COOH
KMnO4
[O]
COOH
CH3
Phthalic acid
(o-Phthalic acid)
o-Xylene
Other Isomers:
COOH
COOH
COOH
Isophthalic acid
(m-Phthalic acid)
COOH
Terephthalic acid
(p-Phthalic acid)
487. (b) Anthracene is a solid polycyclic aromatic hydrocarbon consisting of three fused
benzene rings derived from coal-tar. Anthracene
is used in the artificial production of the red dye
alizarin. It is also used in wood preservatives,
insecticides, and coating materials.
NH2
Anthracene
NH3
Naphthol
Krisman
NH4HSO3
Naphthylamine
486. (c) Phthalic acid (benzene-1,2-dicarboxylic acid) is an aromatic dicarboxylic acid, with
the formula C6H4(COOH)2. It is an isomer of
isophthalic acid and terephthalic acid. Phthalic
acid is used mainly in the form of the anhydride to produce other chemicals such as dyes,
perfumes, saccharin, phthalates and many others.
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Phenanthrene
195
CHO
Furfural
CH
CH
Acetylene
CH3 CH CH2
OH OH
H2O (cold)
Propylene glycol
H2SO4
CH3 CH CH2
Propene
H2O
CH3 CH CH3
OH
2-Propanol
CH3
CH3
Ethane
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KMnO4
O
Furan
H2 / Ni
CH3 CH CH2
Propene
(Propylene)
Krisman
CH3 CH CH2
Propene
H2 / Ni
493. (a) The Williamson ether synthesis was developed by Alexander Williamson in 1850.
Typically it involves the reaction of an alkoxide
ion with a primary alkyl halide via an SN2
reaction. This reaction is important in the history
of organic chemistry because it helped prove
the structure of ethers. For example, the reaction
of ethyl chloride with sodium ethoxide will yield
diethyl ether, (fig: 11.29, page 197).
494. (b) Baeyers test is used to detect the
presence of a double bond. Baeyer's reagent,
named after the German organic chemist Adolf
von Baeyer, is used in organic chemistry as a
qualitative test for the presence of unsaturation,
such as double bonds. The bromine test is also
able to determine the presence of unsaturation.
196
Krisman
600C
CH3 CH2 CH2 CH3
n-Butane
(Fig: 11.28)
CH3 CH2 Cl
Ethyl chloride
+
+ CH CH O Na
3
2
Sodium ethoxide
NaCl
(Fig: 11.29)
KMnO4
H2O
CH3 CH CH2
Propylene glycol
O
NaOH
2H
CH3 OH + H
Formaldehyde
(No hydrogen)
H
H
Methanol
C OH
Formic acid
( hydrogen)
O
C
NaOH
No reaction
H
Acetaldehyde
197
CH3 CO Cl
AlCl3
Benzene
CH3
HCl
Acetophenone
Krisman
orbitals allow cyclic delocalization of electrons. There are few important criteria to be remembered to determine whether the compound
is aromatic or non-aromatic.
1.
2.
3.
In order for a compound to be an aromatic, these three rules must be followed. Lets
discuss benzene and cycloheptatriene to get a
better idea.
Benzene
Cycloheptatriene
Krisman
500. (c) Gasoline is a complex mixture of hydrocarbons. The branched-chain alkanes give a
relatively smooth performance when burnt in
the internal combustion engine of motor cars,
hence they are excellent fuels for cars. In contrast, normal alkanes detonate and cause knocking of the engine, and are bad fuels. The knock
property of various gasolines is stated in terms
of octane number or octane rating. Isooctane,
which has no tendency to knock, is assigned an
octane number of 100 and heptane, which
causes great knocking, is assigned the octane
number 0.
The octane number of a particular gasoline is the percentage of isooctane in a mixture
of isooctane and heptane, which gives
equivalent knock performances. For example,
the knock performance of an unknown sample
of a gasoline is found to be the same as that of a
mixture of 65% isooctane and 35% of heptane.
The unknown compound should have an octane
number of 65.
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199