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 3rd edition Singh 3rd edition
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Conceptual Problems in

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Conceptual Problems in
D. K. Singh
Conceptual Problems in Organic Chemistry 3/e covers all the essential concepts of for Engineering and Medical Entrance Examinations
organic chemistry through 2750 multiple-choice questions (MCQs) given in the book.
The MCQs have been designed in a manner to facilitate quick learning. The current
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Size :172x235mm Spine : 19mm ISBN : 9789332517561 Title Sub Title Edition Authors / Editors Name With CD Red Band Territory line URL Price mQuest
 Conceptual Problems
in Organic Chemistry
[For Engineering and Medical Entrance Examinations]

Third Edition

D. K. Singh

FM.indd 1 11/13/2013 3:00:07 PM

 Copyright © 2014 Dorling Kindersley (India) Pvt. Ltd

Published by Pearson India Education Services Pvt. Ltd, CIN: U72200TN2005PTC057128,

formerly known as TutorVista Global Pvt. Ltd, licensee of Pearson Education in South Asia.

No part of this eBook may be used or reproduced in any manner whatsoever without the
publisher’s prior written consent.

This eBook may or may not include all assets that were part of the print version. The publisher
reserves the right to remove any material in this eBook at any time.

ISBN 978-933-251-756-1
eISBN 978-933-258-207-1

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Uttar Pradesh, India.
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www.pearson.co.in, Email: companysecretary.india@pearson.com

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 To my mother, for her immense
love, patience and support

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 This page is intentionally left blank.

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 Contents

Foreword vii
Preface to the Third Edition ix
About the Author x

Chapter 1 Hybridization, Resonance and Aromaticity 1 – 28

Hybridization
Resonance
Aromaticity

Chapter 2 Isomerism 29 – 100

Structural Isomerism
Geometrical Isomerism
Optical Isomerism
Conformational Isomerism

Chapter 3 Substituent Effects, Reactive Intermediates, 101 – 168

Acid-base and Electrophiles/Nucleophiles
Substituent Effects
Reactive Intermediates
Acid-base
Electrophiles/Nucleophiles

Chapter 4 Reaction Mechanism 169 – 234

Nucleophilic Substitutions
Elimination Reactions
Electrophilic Addition Reactions
Nucleophilic Addition Reactions
Electrophilic Aromatic Substitutions
Nucleophilic Aromatic Substitutions

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 vi n Contents

Chapter 5 Alkanes, Alkenes and Alkynes 235 – 320

Alkanes
Alkenes
Alkynes

Chapter 6 Alkyl Halides and Alcohols 321 – 410

Alkyl Halides
Alcohols

Chapter 7 Carbonyl Compounds, Ethers and Amines 411 – 468

Aldehydes/Ketones
Carboxylic Acids and their Derivatives
Amines
Ethers

Chapter 8 Aromatic Compounds 469 – 498

Aromatic Compounds

Chapter 9 Bio-molecules 499 – 518

Carbohydrates
Amino Acids
Peptides

FM.indd 6 11/13/2013 3:00:07 PM

 Foreword

Chemistry is an ever-expanding branch of science that is based on well-established concepts.

Most of the concepts are widely accepted and are often experimentally verified. Organic
chemistry in particular deals with covalently linked carbon compounds. The stability of
an organic compound in terms of its internal energy and rate of formation/decomposition
can be predicted based on various physical concepts. A fair understanding of the possible
involvement of intermediates and transient species and the kind of interaction among two
or more reactants would enable us to propose a feasible reaction pathway.
Organic chemists have in their arsenal a plethora of reagents and conditions to carry
out various synthetic transformations. Whether or not a reagent is suitable for a specific
transformation can be predicted only through clear understanding of its reactivity. Man has
developed various concepts on reactivity and selectivity by looking at mother nature. Her
ability to generate numerous biomolecules that are indispensable to create and sustain life
on earth has been a true inspiration to man. He cleverly applied those concepts in science
and in everyday life.
Dr Singh has developed an invaluable resource based on concepts in organic chemistry
for the benefit of students who are keen to learn more and prepare themselves for competi-
tive examinations by intense problem solving. Enormous efforts have been expended for
framing this extensive collection of single choice questions. Dr Singh took extraordinary
care to ensure that questions with different levels of difficulty are included in order to keep
the students of all levels interested in the subject. This unique collection of diverse ques-
tions enables the students to examine their own comprehension, conceptual understanding,
logical and analytical thinking as well as time management skills. This book is far superior
to many other national level competitive examination guides. The coverage of the subject
is so exhaustive that the students would find every question a learning experience and say
good bye to many guide books/question banks that contain monotonous questions. This is
primarily due to Dr Singh’s penchant for physical organic chemistry. He is well aware that
understanding of theoretical, mechanistic and stereochemical concepts in organic chemistry
is absolutely necessary to logically tackle even synthetic puzzles.

FM.indd 7 11/13/2013 3:00:07 PM

 viii n Foreword

I am certain that a student who succeeds in answering most of Dr Singh’s questions

will be one of the top ranking students in the national level competitive examinations for
undergraduate admission. I consider this book as an outstanding aid and recommend it
wholeheartedly to those aspiring for admission to leading higher education institutions.
This book would be an excellent reference book for postgraduate students and teachers
as well.

Irishi N.N. Namboothiri 15 March 2013

Professor
Department of Chemistry
Indian Institute of Technology Bombay
Mumbai 400 076

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 Preface to the Third Edition

Organic Chemistry is not a formative science. It requires an interest in the nature and
reaction of molecules. In other words, realization is the best way to learn organic chemistry
because most of the problems are based on application of concepts. Therefore, students
should have a clear concept of the subject and then learn to apply those concepts in solving
problems. While formulating and designing the questions for this book, I had to consider
all angles of each topic included in the syllabus. This book effectively catalyses the process
of learning the subject. In fact, questions are designed to encourage students to learn more
and more of Organic Chemistry. The third edition has been updated and now includes
three new chapters on carbonyl compounds, etheres and amines, aromatic compounds and
biomolecules. I am sure students will find this useful.
I extend my sincere thanks to Mr. Mohammad Ashfaq for his valuable feedback and
suggestions.
I will appreciate your invaluable suggestions and feedback to improve future editions
of this book.

D. K. Singh

FM.indd 9 5/5/2014 1:08:32 PM

 About the Author
Devendra Kaumar Singh trains students appearing for the medical and engineering entrance
examinations in an institute in Patna. He did his post-graduation from the B R Ambedkar Bihar
University in Muzaffarpur, Bihar, and received his doctorate in 1991 from the Indian Institute of
Science Bangalore, under the supervision of Professor S. N. Balasubrahmanyam. Following this,
he worked as a post-doctoral fellow first with Professor Uday Maitra in the same institute for two
years (1991–1993), and then with Professor R. C. Corcoran in the University of Wyoming, USA, for
one year (1993–1994).
Dr Singh’s research interest lies in the area of Physical Organic Chemistry. He has published
three research papers in the Bulletin of the Chemical Society of Japan, Indian Journal of Chemistry and
the Journal of Organic Chemistry, respectively.

FM.indd 10 11/19/2013 12:44:17 PM

Chapter

1
Hybridization,
Resonance and
Aromaticity
This page is intentionally left blank.
 Question Bank
1. For exhibiting tetravalency, carbon atoms
have to be excited. Now, which of the fol-
lowing statements is true?
a Excitation occurs before bonding
b Bonding occurs before excitation
c Both bonding and excitation occur
simultaneously
d Two bonds are formed first, then exci-
tation occurs followed by formation of
another two bonds
2. Bond formation is
a always exothermic
b always endothermic
c neither exothermic nor endothermic
d sometimes exothermic and sometimes
endothermic
3. Which of the following statements is true
about bonding and excitation?
a Energy required for excitation of car-
bon atoms (96 Kcal/mol) is less than
energy released in bonding
b Energy required for excitation is more
than energy released in bonding
c Energy required for excitation is equal
to the energy released in bonding
d None of these
4. Which of the following statements is true
about hybridization?
a Only those atomic orbitals can be hy-
bridized which do not differ much in
shape.
b Only those atomic orbitals can be hy-
bridized which do not differ much in
energy.
c Only those atomic orbitals can be hy-
bridized which do not differ much in
size.
d Only those atomic orbitals can be hy-
bridized which do not differ much in
overlap integrals.
5. Which of the following statements is true
about hybridization?
a Hybridization generates new set of
atomic orbitals identical in shape but
not in size and energy.
b Hybridization generates new set of
atomic obitals identical in size but not
in shape and energy.
c Hybridization generates new set of
atomic obitals indentical in energy but
not in shape and size.
d Hybridization generates new set of
atomic orbitals indentical in shape, size
and energy.
6. Which of the following statements is true
about hybridization?
a Hybrid orbitals frequently undergo
linear overlaps making sigma bonds.
b Hybrid orbitals frequently undergo
lateral overlaps making π-bonds. In
other words, there are several com-
pounds in which π-bonds are formed
using hybrid orbitals.
c Hybrid orbitals are molecular orbit-
als.
d A hybrid orbital bigger in size makes
shorter bond.
7. In 2sp hybridization, 2s-orbital can be
mixed with
a Only 2p
x
b Only 2py
c Only 2p
z
d Any one of 2px, 2py and 2pz
8. In 2sp2 orbital, character of 2pz orbital will
be
a always 33.33%
b always 0%
c always 66.66%
d either 33.33 % or 0 %
4 n Conceptual Problems in Organic Chemistry

9. In 2sp3 orbital a bond energy is more

a characters of 2p , 2p and 2p orbitals
x y z b bond energy is less
are equal to each other but less than c magnitude of ovelap is very less
that of 2s-orbital d none of these
b characters of 2px, 2py and 2pz orbitals
are equal to each other but more than 15. Which of the following orders is correct
that of 2s
for electronegativity?
c characters of 2s, 2p , 2p and 2p orbit-
x y z a sp3C > sp2C > spC
als are equal to each other
b spC > sp2C > sp3C
d characters of 2px, 2py and 2pz are not
c sp2C > spC > sp3C
equal to each other
d sp3C > spC >sp2C
10. Which of the following statements about
the energy of hybrid orbitals resulting 16. In which of the following compounds,
from mixing of 2s and 2p orbitals is C has used sp2 orbital in making C–O
true? bond?
a E2p > Esp3 > Esp2 > Esp > E2s OH OH
b Esp3 > Esp2 > Esp > E2p > E2s a b
c E2p > Esp > Esp2 > Esp3 >E2s
d E2p > Esp > E2s > Esp2 > Esp3 OH OH
c d
11. Which of the following statements about
the size of hybrid orbitals resulting from
mixing of 2s and 2p orbitals is true? 17. The orbitals used by C in forming C-H and
a 2s > 2p > sp3 > sp2 > sp
C-Cl bonds of CH2Cl2 are
b 2p > 2s > sp3 > sp2 > sp
a four sp orbitals b four sp2 orbitals
c 2p > sp3 > sp2 > sp >2s
c four sp3 orbitals d none of these
d sp3 > sp2 > sp > 2p > 2s

18. CH2 = CH - CN
12. Shapes of sp3, sp2 and sp orbitals are like
3 2 1
a b
Cl-C2 bond of this molecule is formed
by
a sp3-sp2 overlap b sp2-sp3 overlap
c d c sp2-sp overlap d sp2-sp2 overlap

19.
13. Which of following statements about
overlap integrals of the various orbitals is
true?
a 2p > 2s > 2sp3 > 2sp2 > 2sp
b 2p > 2sp3 > 2sp2 > 2sp > 2s
c 2p > 2sp > 2sp2 > 2sp3 > 2s
d 2sp3 > 2sp2 > 2sp > 2p > 2s
14. Energy content of a molecule will be less
if
O
In this molecule, there are two C-O bonds.
Which of the following statements is true
about these bonds?
a Both C-O bonds are formed by sp3-sp3
overlaps
b Both C-O bonds are formed by sp2-sp2
overlaps
 Hybridization, Resonance and Aromaticity n 5

c One C-O bond is formed by sp2-sp3 23. CH2 = C = C = CH2

overlap while the other C-O bond is Which of the following structures is most
formed by sp3-sp3 overlap appropriate for this molecule?
d Both C-O bonds are formed by sp2-sp3 H H
overlaps a C=C=C=C
H H
20. NH H H H
C b C=C=C=C
O H H
In this molecule, H H
a both C-N bonds are formed by sp2-sp2 c C=C=C=C
overlaps H H
b one C-N bond is formed by sp2-sp2 H H
overlap while the other by sp 2-sp 3 d C=C=C=C
overlap H H
c both C-N bonds are formed by sp2-sp3
overlaps 24. Which of the following compounds has
d both C-N bonds are formed by sp2-sp2
maximum number of sp-hybridized C-
overlaps
atoms?
a (CN)
21. CH2 = C = CH2 2

In this molecule (allene) b CH ≡ C–CN

a all three C-atoms are sp2 hybridized c HC ≡ C–CH –CH = C = C = CH
2 2
b both terminal C-atoms are sp2 hybrid- d CH2 = C = CH–CN
ized while central C-atom is sp-hybrid-
ized 25. CH3–O–CH = CH2
c both terminal C-atoms are sp-hybrid- Oxygen atom of this molecule is
ized while central C-atom is sp2 hy- a sp3 hybridized
bridized b sp2 hybridized
d none of these c sp-hybridized
d unhybridized
22. CH2 = C = CH2
Which of the following structures is most
26. CH3
appropriate for this molecule? C=O
H H CH3
a C=C=C Oxygen atom of this molecule is
H H
a sp3-hybridized
H H
b sp2-hybridized
b C=C=C
H c sp-hybridized
H
d unhybridized
H H
c C=C=C
27. CH3 – C ≡ N
H H
H H Nitrogen atom of this molecule is
a sp3-hybridized b sp2-hybridized
d C=C=C
H H c sp-hybridized d unhybridized
6 n Conceptual Problems in Organic Chemistry

28. In which of the following molecules, all

atoms are coplanar?
a

a b

CH3 CH3

CH3 CN b
c C=C d
CH3 CN

CH3 CH3
29. In which of the following molecules, –NO2 CH3
group is not coplanar with phenyl ring? CH3

c
a
N
O O
CH3
CH3 CH3 CH3

N
CH3 CH3
O O d
CH3 CH3

c
I I
N 31. In which of the following molecules, all
O O atoms are not coplanar?

a
d O
O
N=O
O
O b

30. In which of the following molecules both

phenyl rings are not coplanar?
 Hybridization, Resonance and Aromaticity n 7

c d HC ≡ CH > >

O 36. Which of the following orders of bond

energy is correct?
d a C–C > N–N > O–O
b O–O > N–N > C–C
c N–N > C–C > O–O
O
d C–C > O–O > N–N
32. In which of the following molecules, all
bond angles are not similar? 37. 1 2 3 4
CHO I CH2 = CH–CH = CH2
a b 1 2 3 4
II CH3–CH2–CH2–CH3
1 2 3 4
c d
III CH2 = CH–CH2–CH3
1 2 3 4
33. Which of the following is the correct order IV CH2 = CH–C = CH
of bond angles? Which of the following is the correct order
a NH > H O > CH of C2-C3 bond length?
3 2 4
b H2O > NH3 > CH4 a II > I > III > IV b II > III > I > IV
c CH > NH > H O c III > I > IV > II d IV > I > III > II
4 3 2
d CH4 > H2O > NH3
38. CH3CN CH3CHO CH3-CH3
34. Which of the following is the correct order I II III
of bond angles? Which of the following is the correct order
a +
NH4 > H3O + > H2O of C–C bond length among these com-
+ pounds?
b H3O + > NH4 > H2O a I > II > III b III > II > I
+ c III > I > II d II > I > III
c H O > H O + > NH4
2 3
+ 39. H l1 H
d NH4 > H2O > H3O +
C=C=C
35. Which of the following order of bond H l2 H
angles is correct? Which of the following is the correct order
of spatial distances l1 and l 2?
a > > HC ≡ CH a l =l b l1 > l2
1 2
c l <l d l2 = 2l1
1 2

b HC ≡ CH > 40. H l1 H
>
C=C=C=C
H l2 H
c > > HC ≡ CH Which of the following is the correct order
of spatial distances l1 and l2?
8 n Conceptual Problems in Organic Chemistry

a l=l b l1 >l2 a the resonance hybrid

1 2
c l<l b the canonical structures
d l2 = 2l1
1 2 c sometimes resonance hybrid and some-
41. Resonance involves times canonical structures
a change in the positions of atoms d none of these
b change in the positions of both σ and
46. A resonance hybrid is the one which is
π electrons
c change in the positions of only π elec- contributed by
a all canonical structures
trons b only the least stable canonical struc-
d change in the positions of only σ elec-
ture
trons c only the most stable canonical struc-
ture
42. CH3 – CH = O d none of these
I
CH2 = CH – OH 47. In the resonance hybrid
II a all canonical structures contribute
+ – equally
CH3 – CH – O b more stable canonical structure con-
III tributes more than less stable canonical
Among these, which are canonical struc- structure
tures? c more stable canonical structure con-
a I and II b I and III tributes less than less stable canonical
c II and III d all structure
d there is no contribution of any canoni-
43. CH 2 = CH – CH = CH2 cal structure
I
– +
CH2 – CH = CH – CH2 48. Delocalization of electrons increases mo-
II lecular stability because
+ – a electrons-nuclei attraction increases
CH2 – CH = CH – CH2 b electrons-electrons repulsion increas-
III
es
Among these which are canonical struc- c potential energy of the molecule in-
tures? creases
a I and II b I and III d potential energy of the molecule re-
c II and III d all of these mains unaffected
44. Which of the following statements is
49. Resonance energy is
true? a equal to the energy of resonance hy-
a Resonance is an intermolecular pro-
brid
cess b equal to the energy of most stable ca-
b Canonical structures are imaginary nonical structure
c Canonical structures are real c equal to the energy of least stable ca-
d A canonical structure explains all fea- nonical structure
tures of a molecule d equal to the difference in energies of
the most stable canonical structure and
45. For a resonating molecule, real structure
resonance hybrid
is
 Hybridization, Resonance and Aromaticity n 9

50. Resonance energy is a I b II

a stored in the molecule c III d none of these
b released by the molecule
c neither stored nor released by the mol- 55. A canonical structure will be more stable
ecule if
d sometimes stored and sometimes re- a it has more number of π-bonds than if
leased by the molecule it has less number of π-bonds
b it has charge separation than if it has
51. All canonical structures of a molecule no charge separation
a must have different number of un- c it has greater length of charge sepa-
paired electrons ration than if it has lower length of
b must have different number of paired charge-separation
electrons d it has positive charge on more electro-
c must be always equivalent negative atom than if it has positive
d need not be always equivalent but they charge on less electronegative atom
should not differ much in stability
56. Which of the following statements is true
+ – – + about the contributions of canonical struc-
52. CH2 = O CH2 – O CH2 – O tures in the resonance hybrid?
I II III a A charge-separated canonical structure
Which of these structures is practically contributes more than a canonical
not a valid canonical structure of formal- structure without charge-separation
dehyde? b A canonical structure with less number
a I b II of π bonds contributes more than a
c III d none of these canonical structure with more number
of π bonds
+ c A canonical structure with negative
53. CH2 = CH – CH = CH – NH3
I charge on less electronegative atom
+ – + contributes more than a canonical
CH2 – CH = CH – CH – NH3 structure with negative charge on more
II electronegative atom
+ d contribution of a charge-separated
CH2 – CH = CH – CH = NH3
III canonical structure will be more in a
Which of these structures is not a valid polar solvent than in a non-polar sol-
canonical structure? vent
a I b II O
57.
c III d none of these
I C
54. – H OH
+ O
CH3 – N I –
O O
+ O II C
CH3 – N – II +
O H OH
O
CH3 – N III O–
O
Which of these structures is not a valid III C
+
canonical structure of nitromethane? H OH
10 n Conceptual Problems in Organic Chemistry

Among these canonical structures, the The correct order of stability among these
correct order of stability is canonical structures is
a I > II > III b III > II > I a I > III > II b III > I > II
c I > III > II d II > I > III c II > III > I d II > I > III
58. O
61. –
I O NH
C
–
H O
I H H

O–
II C O NH
+ –
H O C
II H – H
O–
–
III C O NH
H O C
Among these canonical structures, the III H H
correct order of stability is The correct order of stability among these
a I > II > III b II > I > III
canonical structures is
c I = III > II d II > I ≡ III
a I > II > III b I > III > II
59. I CH2 = CH – CH = O c II > I > III d III > I > II

+ – 62.
II CH2 = CH – CH – O I
N
+ –
III CH2 – CH = CH – O
The correct order of stability among these
II
canonical structures is
a III > II > I b II > III > I
+ N
–
c I > III > II d I > II > III

60. O +

I C – III
H CH2 N–

O–
II C – IV
+ +
H CH2 N
–
O–
III C
V
H CH2
N
 Hybridization, Resonance and Aromaticity n 11

Among these canonical structures of pyri- 65. 4 3

dine, the correct order of stability is
5 2
a (I = V) > (II = IV) > III N
1
b (II = IV) > (I = V) > III H
c (I = V) > III > (II = IV) In pyrrole-electron density is maximum
d III > (II = IV) > (I = V) on
a 2 and 3 b 3 and 4
63. 4 c 2 and 4 d 2 and 5
5 3
66. O
6 N 2 I
1
In pyridine electron density is maximum N
on H
a 2 and 6 b 3 and 5
c 4 d 3 and 4
O+
64. II
I N N –
H H
–
O –
II N III
+
H N+
H
The least stable canonical structure among
– these is
III N a I
+
H b II
c III
d all are equally stable
– 67.
IV N O O
+ +
H
II
– +
I
+
V N O
+
H III
Among these canonical structures of pyr-
The most stable canonical structure among
role, the correct order of stability is
a (III = IV) > (II = V) > I
these is
a I
b I > (II = V) > (III = IV)
b II
c I > (III = IV) > (II = V)
c III
d (II = V) > (III = V) > I
d all are equally stable
12 n Conceptual Problems in Organic Chemistry

68. 3 2 72. m o O
p N
m o O
+1
In this cation, π electron density is more In nitrobenzene, π-electron density is
on maximum on
a ortho positions b meta positions
a C1
c para position d none of these
b C2
c C3 73. Which of the following compounds has
d π-electron-density is same on each C- maximum electron density in ring?
atom. NO2 OH

69. 2 a b
3
–
1 – –
4 O COO
5 c d
In this anion, π-electron-density is maxi-
mum on
a C1
b C2 and C5 74.
c C3 and C4
d same on each C-atom Which of following statements is true
about this compound (biphenyl)?
O O O a Both rings act as π donors
b Both rings act as π acceptors
70. H - C - H H - C - OH H - C - NH2 c One ring acts as π donor while the other
I II III as π-acceptor
Which of these compounds has maximum d Resonance does not occur between
π-electron-density on the carbonylic oxy- both rings
gen?
a I b II 75. I CH2 = CH – CH = CH – OCH3
c III d Same in all
– +
m o II CH2 – CH = CH – CH = OCH3
71.
p OH
m o – +
III CH2 = CH – CH – CH – OCH3
In phenol, π-electron-density is maximum
on –
+
a ortho and meta positions IV CH2 = CH – CH – CH – OCH3
b ortho and para positions Among these canonical structures which
c meta and para positions one is least stable?
a I b II
d none of these
c III d IV
 Hybridization, Resonance and Aromaticity n 13

76. I CH2 = CH – CH = O a - CH = O b - CO NH2

O
+ –

=
c - NH - C - H d - NO2
II CH2 – CH = CH – O
81. Which of the following groups act as π-
+ – acceptor in resonance?
III CH2 – CH – CH = O
O O

=
– a -O-C-R b - C - OR
+
IV CH2 – CH – CH = O O

=
Among these canonical structures, which c - NH - C - H d - NH2
one is least stable?
a I b II 82. Which of the following groups can act
c III d IV either as a π-donor or a π-acceptor depend-
ing upon situation?
77. 4 a - ph b -OH
3 c - CH=O d - NO2
1
2 83. Which of the following groups can act
In this molecule, π-electron-density is more either as a π-donor or as a π-acceptor de-
on pending upon situation?
a C1 and C3 b C2 and C4 a - NO b -NO2
c C2 and C3 d C1 and C4 c -O-N=O d - NH2

84. Which of the following group cannot par-

4 3 2 1
78. CH2 = CH—C = CH2 ticipate in resonance with any group?
| + +
a - CH2 b - NH3
OCH3
In this molecule, π-electron density is O
=

maximum on c -N+ -O– d - NO

a C1 b C2
c C3 d C4 85. CH3COOH CH3COONa CH3CONH2
I II III
79. Resonance energy will be more if Among these compounds, the correct
a Canonical structures have charge sepa-
order of resonance energy is
ration than if canonical structures have a I > II > III b III > II > I
no charge separation c II > III > I d II > I > III
b Molecule is nonaromatic than if mol-
ecule is aromatic 86. –
c Canonical structures are equivalent I HN = CH – NH
–
than if canonical structures are non II O = CH – NH
equivalent
d π-bonds are nonconjugted than if π- III O = CH – OH
bonds are conjugated Among these species, the correct order of
resonance energy is
a I > II > III b II > I > III
80. Which of the following groups acts as π-
c III > I > II d III > II > I
donor in resonance?
14 n Conceptual Problems in Organic Chemistry

–
87. O O 91. +
CH2 = CH – OH CH2 – CH = OH
I II
I II Which of the following statements is true
about this resonating system?
O O a Contribution of II is more than that of
I in resonance hybrid
b Contribution of I is increased by a polar
III IV solvent
Among these compounds, which one has c Contribution of II is increased by a
maximum resonance energy? polar solvent
a I b II d Relative contributions of I and II are
c III d IV
independent of solvent
88. I CH3COOH
92. I CH2 = CH – CH = CH – CH =CH2
II CH3CONH2
III CH3COF
Among these compounds, the correct + –
II CH2 = CH – CH – CH = CH – CH2
order of resonance energy is
a I > II > III b III > II > I
c II > III > I d II > I > III + –
III CH2 – CH = CH – CH = CH – CH2
89. Among these three canonical structures,
OCH3
I (though more are possible) what would be
their relative contribution in the hybrid?
a I > II > III b III > II > I
c I > III > II d III > I > II
OCH3
II
93. CH2 = CH – OCH3
OCH3
III – +
I CH2 – CH = OCH3
Among these compounds the correct order
of resonance energy is CH3
a III > I > II b II > I > III
CH2 = CH – N
c I > II > III
CH3
d III > II > I
– + CH3
90. II CH2 – CH = N
I II
CH3
Which of the following statements is true
about the contribution of I and II in respec-
III tive resonance hybrids?
Among these compounds, the correct a I contributes more than II
order of resonance energy is b II contributes more than I
a I > II > III b II > I > III c Both I and II contribute equally
c III > I > II d I > III > II d none of these
 Hybridization, Resonance and Aromaticity n 15

94. Heat of hydrogenation of cyclohexene 99. CH3 CH3

is –28.6 kcal/mol and that of benzene is
–49.8 kcal/mol. Then resonance energy I
of benzene will be
a 46 kcal/mol b 39 kcal/mol CH3
c 36 kcal/mol d 30 kcal/mol CH3 CH2
95. Diene Heat of Hydrogenation II
CH2 = CH-CH=CH-CH3 –54.1 kcal/mol
I CH3
CH3-CH=C=CH-CH3 –70.5 kcal/mol CH2 CH2
II
CH2=CH-CH2-CH=CH2 –60.2 kcal/mol III
III
Examine these dienes and their heat of
CH2
hydrogenations. Now, what will be the
stability order among these dienes? The heats of hydrogenation of these com-
a I > II > III b II > III > I pounds will be in the order as
a I > II > III b III > II > I
c I > III > II d II > I > III
c II > III > I d II > I > III

96. Heat of hydrogenation of CH3-CH=CH2 is

100. 1
–30 kcal/mol and resonance energy of 1,3-
2
butadiene is 3 kcal/mol. What will be the
heat of hydrogenation of 1,3-butadiene? I 3
a –63 kcal/mol b –57 kcal/mol 4
(c) –27 kcal/mol d –54 kcal/mol
1
97. 2
II
3
4
I II III
Among these compounds, the order of 1
heats of hydrogenation is 2
a I > II > III b III > II > I III 3
c II > I > III d II > III > I 4
Examine these canonical structures of
98. naphthalene. Now, which of the following
statements is true about C1-C2 and C2-C3
bond lengths?
I II a Both bonds are of same length
b C1-C2 bond is longer than C2-C3
bond
III c C2-C3 bond is longer than C1-C2
Among these compounds, the order of bond
heats of hydrogenation is d It is not possible to judge the bond
a II > III > I b III > II > I length because given structures are
c I > II > III d II > I > III tautomers
16 n Conceptual Problems in Organic Chemistry

101. O N I 104. Which of the following compounds has

2 2 NO2
3 1 longest C-O bond?
O O
4 6 a b
5
NO2
O
Which of the following statements is true O
about this molecule? c d
a C5-N bond is longer than C1-N and
C3-N bonds
b C5-N bond is shorter than C1-N bond 105. CH3O - CH = CH - NO2
and latter is shorter than C3-N bonds I
c C1-N and C3-N bonds are of same CH3O - CH = CH2
II
length but longer than C5-N bond
CH2 = CH2
d All three C-N bonds are of same
III
length Which of the following orders of C-C
bond lengths is correct among these com-
102. 2 pounds?
1 3 a I > II > III b III > II > I
c II > I > III d III > I > II
4
Which of the following statements is true 106. Among the following compounds, the
about this molecule? correct order of C-C bond length is
a C1-C2 and C3-C4 bonds are of same a C H >CH >CH >CH
2 6 2 4 6 6 2 2
length b C2H6 > C6H6 > C2H4 > C2H2
b C1-C2 bond is shorter than C3-C4 c CH >CH >CH >CH
2 4 2 6 2 2 6 6
bond d C2H6 > C2H4 > C2H2 > C6H6
c C1-C2 bond is longer than C3-C4 (C6H6 is benzene)
bond
107. Among the following compounds, C1-C2
d C1-C2 and C2-C3 bonds are of same
bond is shortest in
length 2
1 C ≡ CH
103. NH2 NH2 a

I II 2
1 C = CH2
b
COOCH3
NH2
2
1 CH2 – CH3
III c

The correct order of C-N bond length 2

among these compounds is 1 C ≡ CH
a I > II > III b III > II > I d
c III > I > II d II > I > III
 Hybridization, Resonance and Aromaticity n 17

108. H2O2 O3 O2 113. CH3 CH3 CH3 CH3

N N
Among these molecules, the correct order CH3 CH3
of O-O bond length is
a H O >O >O
2 2 3 2
b O2 > O3 > H2O2 CH3
CH3
c O >HO >O
3 2 2 2 I II
d O3 > O2 > H2O2

CH3 CH3
109. Which of the following species does not N
have all C-O bonds of same length?
a HCOO – b CO3 2–
c CO d HCOOH
2
III
110. Among these compounds, the correct
Cl
order of ring-N-bond length is
I
a III > I > II b III > II > I
II Cl
c I > III > II d II > III > I

114. Among the following compounds which

one has longest C-O bond?
III Cl IV Cl O O
Among these compounds, which one has
a C b C
shortest C-Cl bond?
a I b II H H H F
c III d IV O O
c C d
C
111. OH OH OH H NH2 H OH
115. H - O - C = N H-N=C=O
(Cyanic acid) ( Isocyanic acid)
NO2 Loss of proton from these two acids pro-
NO2 duces
I II III a same anion
Among these compounds, the correct b different anions
order of C-O bond length is c same cation
a II > I > III b I > II > III d different cations
c III > II > I d III > I > II
116. I CH2 = CH – CH – CH3
112. Which of the following compounds do not
Br
have all C-C bonds of same length?
II CH2 – CH = CH – CH3
a b
Br
Ionization of these compounds produces
–
– Br and
c + d a same anion b different anions
c same cation d different cations
18 n Conceptual Problems in Organic Chemistry

117. + OH The π-electron density on the carbonylic

CH3 oxygen is maximum in which of these
I CH3 – C – N compounds?
CH3 a I b II
c III d same in all
OH
CH3
II CH3 – C – N
+ 121. Which of the following systems is the cor-
CH3 rect proposition given by kekule regarding
OH the structure of benzene?
+ CH3
III CH3 – C = N a
CH3
The stability order of these canonical
structures is b
a I > II > III b III > I > II
c I > III > II d II > III > I
– c
118. +
CH2 = CH – OCH3 CH2 – CH = OCH3
I II d
On moving from gas phase to water as
solvent, the contribution of II in the reso-
nance hybrid
a increases 122. Which of the following systems is the cor-
b decreases rect proposition given by Huckel regard-
c remains constant ing the structure of benzene?
d this question is not valid
a
119. O

In this compound, how many sites are

– c
available for the attack of CH 3O ?
a 1 b 2
c 3 d 4 d

120. O
I CH3 – C – NH – CH2 –Ph 123. Which of the following statements is not
correct about aromaticity?
a Aromaticity is born out of resonance
O
b All resonating molecules are aromat-
II CH3 – C – NH – Ph ic
c To be aromatic resonance energy
O should be high
d Only cyclic molecules may be aro-
III CH3 – C – NH NO2
matic
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 Fig. 293.—Coregonus oxyrhynchus.

Fig. 294.—Head of Coregonus

oxyrhynchus.
The majority of the species, of which more than forty are known,
are lacustrine species; and comparatively few are subject to
periodical migrations to the sea, like Salmo. They are confined to the
northern parts of temperate Europe, Asia, and North America. Their
distribution is local, but sometimes three and more species are found
in the same lake. They abound in every lake and river of the northern
parts of North America, and are known by the name of “White-fish.”
They are of vital importance to some tribes of the native population.
The European C. oxyrhynchus is as much a marine as a freshwater
species. In the British Islands several small species occur, viz. C.
clupeoides, the “Gwyniad,” “Schelly,” or “Powen” from the great
lakes; C. vandesius, the “Vendace” of Lochmaben; and C. pollan, the
“Pollan” of the Irish lakes. The latter is brought in quantities to Belfast
market during the season, that is, at the time when it rises from the
depths of Lough Neagh to deposit its spawn near the shore.
Thomson says that in September 1834 some 17,000 were taken
there at three or four draughts of the net. Some of the species of the
continent of Europe and America attain to a much larger size than
the British species, viz. to a length of two feet.

Fig. 295.—Coregonus clupeoides.

Thymallus.—Principally distinguished from Coregonus by its long
many-rayed dorsal fin.
“Graylings”—five species, inhabiting clear streams of the north of
Europe, Asia, and North America. The best known are the “Poisson
bleu” of the Canadian voyageurs (Th. signifer), and the European
Grayling (T. vulgaris).
Salanx.—Body elongate, compressed, naked or covered with
small, exceedingly fine, deciduous scales. Head elongate and much
depressed, terminating in a long, flat, pointed snout. Eye small. Cleft
of the mouth wide; jaws and palatine bones with conical teeth, some
of the intermaxillaries and mandibles being enlarged; no teeth on the
vomer; tongue with a single series of curved teeth. Dorsal fin placed
far behind the ventrals, but in front of the anal; anal long; adipose fin
small; caudal forked. Pseudobranchiæ well developed; air-bladder
none. The entire alimentary canal straight, without bend; pyloric
appendages none. Ova small.
 This small, transparent, or whitish fish (S. chinensis) is well
known at Canton and other places of the coast of China as “White-
bait,” and considered a delicacy. It is evidently a fish which lives at a
considerable depth in the sea, and approaches the coast only at
certain seasons.
Finally, this family is represented in the deep sea by three
genera, Argentina, Microstoma, and Bathylagus, of which the two
former live at moderate depths, and have been known for a long
time, whilst the last was discovered during the “Challenger”
expedition in the Atlantic and Antarctic Oceans at depths of 1950
and 2040 fathoms. As Argentina is sometimes found in the North
Atlantic, and even near the British coasts, we give its principal
characters.
Argentina.—Scales rather large; cleft of the mouth small;
intermaxillaries and maxillaries very short, not extending to below the
orbit. Eye large. Jaws without teeth; an arched series of minute teeth
across the head of the vomer and on the fore part of the palatines;
tongue armed with a series of small curved teeth on each side. Dorsal
fin short, in advance of the ventrals; caudal deeply forked.
Pseudobranchiæ well developed. Pyloric appendages in moderate
numbers. Ova small.
Four species are known, of which A. silus and A. hebridica have
been found occasionally on the North British, and, more frequently,
on the Norwegian coast. The other species are from the
Mediterranean. Attaining to a length of 18 inches.

Sixteenth Family—Percopsidæ.
Body covered with ctenoid scales; head naked. Margin of the
upper jaw formed by the intermaxillaries only; opercular apparatus
complete. Barbels none. Gill-openings wide. Adipose fin present.
One genus and species only (Percopsis guttatus); interesting as
having the general characters of Salmonoids, but the mouth and
scales of a Percoid. Freshwaters of the northern United States.
 Seventeenth Family—Haplochitonidæ.
Body naked or scaly (cycloid). Margin of the upper jaw formed by
the intermaxillary; opercular apparatus complete. Barbels none. Gill-
opening wide; pseudobranchiæ. Air-bladder simple. Adipose fin
present. Ovaries laminated; the eggs fall into the cavity of the
abdomen, there being no oviduct. Pyloric appendages none.

Fig. 296.—Prototroctes oxyrhynchus, New Zealand.

Freshwater-fishes which represent the Salmonoids in the
southern hemisphere. Two genera only are known. Haplochiton (Fig.
104, p. 250) abundant in lakes and the streams falling into the Straits
of Magelhæn and in the rivers of Chile and the Falkland Islands. It
has the general appearance of a Trout, but is naked. Prototroctes,
with the habit of a Coregonus, scaly, and provided with minute teeth;
one species (P. maræna) is common in South Australia, the other (P.
oxyrhynchus) in New Zealand. The settlers in these colonies call
them Grayling; the Maori name of the second species is
“Upokororo.”

Eighteenth Family—Gonorhynchidæ.
Head and body entirely covered with spiny scales; mouth with
barbels. Margin of the upper jaw formed by the intermaxillary, which,
although short, is continued downwards as a thick lip, situated in
front of the maxillary. Adipose fin none; the dorsal fin is opposite to
the ventrals, and short, like the anal. Stomach simple, without blind
sac; pyloric appendages in small number. Pseudobranchiæ; air-
bladder absent. Gill-openings narrow.

Fig. 297.—Gonorhynchus greyi.

Fig. 298.—Scale of
Gonorhynchus greyi.
One genus and species only (Gonorhynchus greyi) is known; it is
a semi-pelagic fish, not very rare off the Cape of Good Hope, and in
the Australian and Japanese seas. From 12 to 18 inches long. The
colonists in New Zealand name it “Sand-eel,” as it frequents bays
with sandy bottom. It is eaten.

Nineteenth Family—Hyodontidæ.
Body covered with cycloid scales; head naked; barbels none.
Margin of the upper jaw formed by the intermaxillaries mesially, and
by the maxillaries laterally, the latter being articulated to the end of
the former. Opercular apparatus complete. Adipose fin none; the
dorsal fin belongs to the caudal portion of the vertebral column.
Stomach horseshoe-shaped, without blind sac; intestine short; one
pyloric appendage. Pseudobranchiæ none; air-bladder simple. Gill-
openings wide. The ova fall into the abdominal cavity before
exclusion.
 One genus and species only (Hyodon tergisus) is known,
generally called “Moon-eye.” It is abundant in the western streams
and great lakes of North America. From 12 to 18 inches long.

Twentieth Family—Pantodontidæ.
Body covered with large cycloid scales; sides of the head
osseous. Margin of the upper jaw formed by the single intermaxillary
mesially, and by the maxillaries laterally. The dorsal fin belongs to
the caudal portion of the vertebral column, is short, opposite and
similar to the anal. Gill-openings wide; gill-covers consisting of a
præoperculum and operculum only. Branchiostegals numerous.
Pseudobranchiæ none; air-bladder simple. Stomach without coecal
sac; one pyloric appendage. Sexual organs with a duct.
A small freshwater-fish (Pantodon buchholzi), singularly alike to a
Cyprinodont, from the west coast of Africa.

Twenty-first Family—Osteoglossidæ.
Body covered with large hard scales, composed of pieces like
mosaic. Head scaleless; its integuments nearly entirely replaced by
bone; lateral line composed of wide openings of the mucus-duct.
Margin of the upper jaw formed by the intermaxillaries mesially, and
by the maxillaries laterally. The dorsal fin belongs to the caudal
portion of the vertebral column, is opposite and very similar to the
anal fin; both approximate to the rounded caudal (with which they
are abnormally confluent). Gill-openings wide; pseudobranchiæ
none; air-bladder simple or cellular. Stomach without coecal sac;
pyloric appendages two.
Large freshwater-fishes of the tropics, whose singular
geographical distribution has been noticed above (p. 223).
Osteoglossum.—Cleft of the mouth very wide, oblique, with the
lower jaw prominent. A pair of barbels at the lower jaw. Abdomen
trenchant. Bands of rasp-like teeth on the vomer, palatine and
pterygoid bones, on the tongue and hyoid. Pectoral fins elongate.
 O. bicirrhosum from Brazil and Guyana, O. formosum from
Borneo and Sumatra, O. leichardti from Queensland.
Arapaima.—Cleft of the mouth wide, with the lower jaw prominent;
barbels none. Abdomen rounded. Jaws with an outer series of small
conical teeth; broad bands of rasp-like teeth on the vomer, palatines,
pterygoids, sphenoid, os linguale, and hyoid. Pectoral fins of moderate
length.

Fig. 299.—Arapaima gigas.

The largest freshwater Teleostean known, exceeding a length of
15 feet and a weight of 400 pounds. It is common in the large rivers
of Brazil and the Guyanas, and esteemed as an article of food.
When salted it is exported in large quantities from the inland fisheries
to the seaports.
Heterotis.—Cleft of the mouth rather small, with the jaws
subequal; barbels none. A single series of small teeth in the jaws;
pterygoids and hyoid with a patch of small conical teeth; none on the
vomer or palatines.
This fish (H. niloticus), which is not uncommon in the Upper Nile
and the West African rivers, exhibits several anatomical peculiarities.
The fourth branchial arch supports a spiral accessory organ, the
function of which is still unexplained. The air-bladder is cellular, and
the stomach consists of a membranous and a muscular portion.

Twenty-Second Family—Clupeidæ.
Body covered with scales; head naked; barbels none. Abdomen
frequently compressed into a serrated edge. Margin of the upper jaw
formed by the intermaxillaries mesially, and by the maxillaries
laterally; maxillaries composed of at least three movable pieces.
Opercular apparatus complete. Adipose fin none. Dorsal not
elongate; anal sometimes very long. Stomach with a blind sac;
pyloric appendages numerous. Gill-apparatus much developed, the
gill-openings being generally very wide. Pseudobranchiæ generally
present. Air-bladder more or less simple.
The family of “Herrings” is probably unsurpassed by any other in
the number of individuals, although others comprise a much greater
variety of species. The Herrings are principally coast-fishes, or, at
least, do not go far from the shore; none belong to the deep-sea
fauna; scarcely any have pelagic habits, but many enter or live in
fresh waters communicating with the sea. They are spread over all
the temperate and tropical zones. Fossil remains of Herrings are
numerous, but the pertinence of some of the genera to this family is
open to serious doubts, as the remains are too fragmentary to allow
of determining whether they belong to Salmonoids or Clupeoids.
Therefore, Agassiz comprised both families in one—Halecidæ. Many
of the remains belong to recent genera, which are readily
recognised, as Clupea, Engraulis and Chanos, principally from the
schists of Glaris and Licata, from Monte Bolca and the Lebanon.
Others, like Thrissopater, from the Gault at Folkestone, Leptosomus,
Opisthopteryx, Spaniodon, from the chalk and tertiary formations,
can be readily associated with recent genera. But the majority do not
show an apparent affinity to the present fauna. Thus, Halec from the
chalk of Bohemia, Platinx and Coelogaster from Monte Bolca,
Rhinellus from Monte Bolca and Mount Lebanon, Scombroclupea,
with finlets behind the anal, from the Lebanon and Comen, and
Crossognathus from tertiary Swiss formations, allied to Megalops,
Spathodactylus from the same locality, and Chirocentrites from
Mount Lebanon, etc. Finally, a genus recently discovered in tertiary
formations of Northern Italy, Hemitrichas, has been classed with the
Clupeoids, from which, however, it differs by having two short dorsal
fins, so that it must be considered, without doubt, to be the
representative of a distinct family.
Engraulis (including Cetengraulis).—Scales large or of
moderate size. Snout more or less conical, projecting beyond the
lower jaw. Teeth small or rudimentary. Intermaxillaries very small,
hidden; maxillary long, attached to the cheek by a scarcely distensible
 membrane. Anal fin of moderate or great length. Branchiostegals
short, from nine to fourteen in number.
Not less than forty-three different species of “Anchovies” are
known from temperate and tropical seas. They exhibit marked
differences in the length of their maxillary bone, which sometimes
does not reach the gill-opening, whilst in other species it extends far
beyond it; and in the number of their anal rays, which varies from 20
to 80. Some have the upper pectoral ray prolonged into a filament,
thus leading towards the succeeding genus, Coilia. The majority are
recognised, besides, by their peculiar structure, by a broad silvery,
lateral band, similar to that observed in the Atherines. The most
celebrated Anchovy is E. encrasicholus, very plentiful in the
Mediterranean, but rarely wandering northwards. It is the species
which, preserved in salt, is exported to all parts of the world,
although similarly lucrative fisheries of Anchovies might be
established in Tasmania where the same species occurs, in Chile,
China, Japan, California, at Buenos Ayres, each of which countries
possesses Anchovies by no means inferior to the Mediterranean
species.
Coilia.—Body terminating in a long tapering tail. Scales of
moderate size. Snout and jaws as in Engraulis. Anal fin exceedingly
long, confluent with the caudal. The two or three upper pectoral rays
are much prolonged, and their branches form four, six, or seven
filaments.

Fig. 300.—Coilia clupeoides.

Ten species from Indian and Chinese seas.

 Chatoëssus.—Body compressed; abdomen serrated. Scales of
moderate size. Snout obtuse, or obtusely conical, more or less
projecting beyond the cleft of the mouth, which is narrow, more or less
transverse. Maxillary joined to the ethmoid, its upper portion being
behind the intermaxillary. Teeth none. Anal fin rather long; dorsal
opposite to the ventrals, or to the space between ventrals and anal.
Gill-membranes entirely separate; branchial arches forming two
angles, one pointing forward and the other backwards; the fourth
branchial arch with an accessory organ; branchiostegals of moderate
length, five or six in number.
Ten species from the coasts, brackish and fresh waters of Central
America (one species ranges to New York), Australia, the East
Indies, and Japan.
Clupea.—Body compressed, with the abdomen serrated, the
serrature extending forwards to the thorax. Scales of moderate or
large, rarely of small size. Upper jaw not projecting beyond the lower.
Cleft of the mouth of moderate width. Teeth, if present, rudimentary
and deciduous. Anal fin of moderate extent, with less than thirty rays;
dorsal fin opposite to the ventrals. Caudal forked.
This genus comprises more than sixty different species, the
geographical distribution of which coincides with that of the family.
The majority are of greater or less utility to man, but a few tropical
species (C. thrissa, C. venenosa, and others) acquire, probably from
their food, highly poisonous properties, so as to endanger the life of
persons eating them. The most noteworthy species are—
1. C. harengus (the “Herring”).—It is readily recognised by having
an ovate patch of very small teeth on the vomer. D. 17–20. A. 16–18.
L. lat. 53–59. Vert. 56. Gill-cover smooth, without radiating ridges. It
inhabits, in incredible numbers, the German Ocean, the northern
parts of the Atlantic, and the seas north of Asia. The Herring of the
Atlantic coasts of North America is identical with that of Europe. A
second species has been supposed to exist on the British coast (C.
leachii), but it comprises only individuals of a smaller size, the
produce of an early or late spawn. Also the so-called “White-bait” is
not a distinct species, but consists chiefly of the fry or the young of
herrings, and is obtained “in perfection” at localities where these
small fishes find an abundance of food, as in the estuary of the
Thames.
[Separate accounts on the Herring may be found in Cuvier and
Valenciennes, “Hist. nat. des Poissons,” vol. xx.; J. M. Mitchell, “The
Herring, its Natural History and National Importance,” Edinb. 1864,
8vo; P. Neucrantz, “De Harengo,” Lübeck, 1654; J. S. Dodd, “Essay
towards a Natural History of the Herring,” Lond. 1768, 8vo; Bock,
“Versuch einer vollstændigen Natur-und Handels-Geschichte des
Hærings,” Königsberg, 1769, 8vo.]
2. C. mirabilis.—The Herring of the North Pacific.
3. C. sprattus.—The “Sprat.” Without vomerine teeth. D. 15–18.
A. 17–20. L. lat. 47–48. Vert. 47–49. Gill-cover, smooth, without
radiating ridges. Abundant on the Atlantic coasts of Europe.
4. C. thrissa.—One of the most common West Indian fishes,
distinguished by the last dorsal ray being prolonged into a filament.
Hyrtl has discovered a small accessory branchial organ in this
species.
5. C. alosa.—The “Shad” or “Allice Shad,” with very fine and long
gill-rakers, from 60 to 80 on the horizontal part of the outer branchial
arch, and with one or more black lateral blotches. Coasts of Europe,
ascending rivers.
6. C. finta.—The “Shad” or “Twaite Shad,” with stout osseous gill-
rakers, from 21 to 27 on the horizontal part of the outer branchial
arch, and spotted like the preceding species. Coasts of Europe,
ascending rivers, and found in abundance in the Nile.
7. C. menhaden.—The “Mossbanker,” common on the Atlantic
coasts of the United States. The economic value of this fish is
surpassed in America only by that of the Gadoids, and derived
chiefly from its use as bait for other fishes, and from the oil extracted
from it, the annual yield of the latter exceeding that of the whale
(from American Fisheries). The refuse of the oil factories supplies a
material of much value for artificial manures.
[See G. Brown Goode, “The Natural and Economical History of the
American Menhaden,” in U.S. Commission of Fish and Fisheries, Part
V., Washington, 1879, 8vo.]
 8. C. sapidissima.—The American Shad, abundant, and an
important food-fish on the Atlantic coasts of North America. Spawns
in fresh water.
9. C. mattowocca.—The “Gaspereau” or “Ale-wife,” common on
the Atlantic coasts of North America, ascending into freshwater in
early spring, and spawning in ponds and lakes.
10. C. pilchardus.—The “Pilchard” or the “Sardine,” equally
abundant in the British Channel, on the coast of Portugal, and in the
Mediterranean, and readily recognised by radiating ridges on the
operculum, descending towards the sub-operculum.
11. C. sagax.—Representing the Pilchard in the Pacific, and
found in equally large shoals on the coasts of California, Chile, New
Zealand, and Japan.
12. C. toli.—The subject of a very extensive fishery on the coast
of Sumatra for the sake of its roes, which are salted and exported to
China, the dried fish themselves being sent into the interior of the
island. The fish is called “Trubu” by the Malays, about 18 inches
long, and it is said that between fourteen and fifteen millions are
caught annually.
13. C. scombrina.—The “Oil-Sardine” of the eastern coast of the
Indian Peninsula.

Other, but less important genera of Clupeoids with serrated

abdomen, are Clupeoides, Pellonula, Clupeichthys, Pellona,
Pristigaster, and Chirocentrodon (these three last with very small or
without any ventral fins).
Albula.—Body oblong, moderately compressed; abdomen flat.
Scales of moderate size, adherent; lateral line distinct. Eyes covered
with a broad annular adipose membrane. Snout pointed, the upper
jaw projecting beyond the lower. Mouth inferior, of moderate width,
with villiform teeth; intermaxillary juxtaposed to the upper anterior
edge of the maxillary. Dorsal fin opposite to the ventrals; anal fin
 shorter than dorsal. Gill-membranes entirely separate, with numerous
branchiostegals.
One species only (A. conorhynchus), ranging over all tropical and
sub-tropical seas, and very common in many localities near the
coasts. It grows to a length of from two to three feet, and is not
valued as food.
Elops.—Body rather elongate, moderately compressed; abdomen
flat. Scales small, adherent; lateral line distinct. A narrow osseous
lamella, attached to the mandibulary symphysis, covers the part
between the mandibles. Snout pointed; mouth wide, anterior;
intermaxillary short, maxillary forming the lateral part of the mouth.
Bands of villiform teeth in the jaws, on the vomer, palatine and
pterygoid bones, on the tongue, and on the base of the skull. Dorsal
fin opposite to ventrals; anal rather shorter than dorsal. Gill-
membranes entirely separate, with very numerous branchiostegals.
Two species, of which one, E. saurus, is, like the preceding fish,
spread over all tropical and sub-tropical seas; it exceeds a length of
three feet, and is not esteemed as food.

Fig. 301.—Elops saurus.

Megalops.—Body oblong, compressed, abdomen flat. Scales
large, adherent; lateral line distinct. A narrow osseous lamella,
attached to the mandibulary symphysis, between the mandibles.
Snout obtusely conical; mouth anterior, lower jaw prominent;
intermaxillary short; maxillary forming the lateral part of the mouth.
Bands of villiform teeth in the jaws, on the vomer, palatine and
pterygoid bones, on the tongue and on the base of the skull. Dorsal fin
opposite to, or immediately behind, the ventrals; anal rather larger
 than dorsal. Gill-membranes entirely separate, with numerous
branchiostegals. Pseudobranchiæ none.
Two species, one belonging to the Indo-Pacific (M. cyprinoides),
the other to the Atlantic (M. thrissoides); they are the largest fishes of
this family, exceeding a length of five feet, and excellent eating.
Young specimens enter freely fresh waters.
Chanos.—Body oblong, compressed; abdomen flat. Scales small,
striated, adherent; lateral line distinct. Snout depressed; mouth small,
anterior, transverse, the lower jaw with a small symphysial tubercle.
Intermaxillary in juxtaposition to the upper anterior edge of maxillary.
Teeth none. Dorsal fin opposite to the ventrals; anal small, shorter
than dorsal; caudal deeply forked. Gill-membranes entirely united
below, and free from the isthmus. Branchiostegals four, long. An
accessory branchial organ in a cavity behind the gill-cavity proper. Air-
bladder divided by a constriction into an anterior and posterior portion.
Mucous membrane of the œsophagus raised in a spiral fold. Intestine
with many convolutions.
Two species from the Indo-Pacific, of which Ch. salmoneus is
extremely common; it enters fresh waters, and exceeds a length of
four feet; its flesh is highly esteemed. The accessory branchial organ
and the skeleton have been described by Müller, “Bau und Grenzen
der Ganoiden,” p. 75; and by Hyrtl, “Denkschr. Ak. Wiss. Wien.” xxi.
1883, p. 1.

Fig. 302.—Chanos salmoneus.

 The remaining genera belonging to this family are Spratelloides,
Dussumieria, and Etrumeus, which together form a small group,
distinguished by an anterior and lateral mouth, by the upper jaw not
overlapping the lower, by a rounded abdomen, and by lacking the
gular plate of some of the preceding genera.

Twenty-third Family—Bathythrissidæ.
Body oblong, with rounded abdomen, covered with cycloid
scales; head naked; barbels none. Margin of the upper jaw formed
by the intermaxillaries mesially, and by the maxillaries laterally.
Opercular apparatus complete. Adipose fin none; dorsal fin much
elongate, many rayed; anal fin short. Stomach with a blind sac;
pyloric appendages numerous. Gill-apparatus well developed;
pseudobranchiæ; gill-openings wide; an air-bladder. Ova very small;
ovaries without duct.
One genus and species only (Bathythrissa dorsalis) from deep
water (350 fathoms) off the coast of Japan. This remarkable fish has
the appearance of a Coregonus, and attains to a length of two feet.
Nothing is known of its osteology, but possibly a fossil genus from
the Gyps of Montmartre; Notæus, which has also a long dorsal fin,
may prove to belong to the same family.

Twenty-fourth Family—Chirocentridæ.
Body covered with thin, deciduous scales; barbels none. Margin
of the upper jaw formed by the intermaxillaries mesially, and by the
maxillaries laterally, both bones being firmly united, in juxtaposition.
Opercular apparatus complete. Adipose fin none; the dorsal fin
belongs to the caudal portion of the vertebral column. Stomach with
a blind sac; intestine short, the mucous membrane forming a spiral
fold; pyloric appendages none. Pseudobranchiæ none; air-bladder
incompletely divided into cells; gill-opening wide.
One genus and species only (Chirocentrus dorab) is known,
which is common in the Indian Ocean, and attains to a length of
about three feet; it is not esteemed as food. Remains of fishes
similar to Chirocentrus are found in the marl slates of Padang, in
Sumatra.

Twenty-fifth Family—Alepocephalidæ.
Body with or without scales; head naked; barbels none. Margin of
the upper jaw formed by the intermaxillaries and maxillaries, the
former being placed along the upper anterior edge of the latter.
Opercular apparatus complete. Adipose fin none; the dorsal fin
belongs to the caudal portion of the vertebral column. Stomach
curved, without blind sac; pyloric appendages in moderate number.
Pseudobranchiæ; air-bladder absent. Gill-openings very wide.
Before the voyage of the “Challenger” one species only of this
family was known, Alepocephalus rostratus, a rare fish from the
Mediterranean; now, four genera with seven species are known, and
there is no doubt that this family is one of the most characteristic,
and will prove to be one of the most generally distributed forms, of
the deep-sea. Their vertical range varies between 345
(Xenodermichthys) and 2150 (Bathytroctes) fathoms. They approach
the Salmonoids, but lack invariably the adipose fin. Their dentition is
very feeble; their eye large; bones thin. Coloration black.
 Alepocephalus has thin cycloid scales; a mouth of moderate
width, and no teeth on the maxillary.
Bathytroctes has cycloid scales, a wide mouth, and teeth on the
maxillary as well as intermaxillary.
Platytroctes has small keeled scales and no ventrals.
Xenodermichthys with fine nodules instead of scales.

Twenty-sixth Family—Notopteridæ.
Head and body scaly; barbels none. Margin of the upper jaw
formed by the intermaxillaries mesially, and by the maxillaries
laterally. Opercular apparatus incomplete. Tail prolonged, tapering.
Adipose fin none. Dorsal short, belonging to the caudal portion of the
vertebral column; anal very long. Stomach without blind sac; two
pyloric appendages. Pseudobranchiae none; air-bladder present,
divided in the interior. The ova fall into the cavity of the abdomen
before exclusion. On each side a parieto-mastoid cavity leading into
the interior of the skull.
One genus only (Notopterus) with five species which inhabit fresh
waters of the East Indies and West Africa. Well-preserved remains of
this genus occur in the marl slates of Padang, in Sumatra. Their air-
bladder is divided into several compartments, and terminates in two
horns anteriorly and posteriorly, the anterior horns being in direct
connection with the auditory organ.

Twenty-seventh Family—Halosauridæ.
Body covered with cycloid scales; head scaly; barbels none.
Margin of the upper jaw formed by the intermaxillaries mesially, and
by the maxillaries laterally. Opercular apparatus incomplete. Adipose
fin none. The short dorsal belongs to the abdominal part of the
vertebral column; anal very long. Stomach with a blind sac; intestine
short; pyloric appendages in moderate number. Pseudobranchiæ
none. Air-bladder large, simple; gill-openings wide. Ovaries closed.
 The only genus belonging to this family was discovered by the
Madeiran ichthyologist Johnson, in 1863; but since then the
naturalists of the “Challenger” expedition have added four other
species, showing that this type is a deep-sea form and widely
distributed; the specimens were dredged in depths varying from 560
to 2750 fathoms.

Twenty-eighth Family—Hoplopleuridæ.
Body generally with four series of subtriangular scutes, and with
intermediate scale-like smaller ones. One (?) dorsal only; head long,
with the jaws produced.
Extinct; developed in the chalk and extending into tertiary
formations: Dercetis (with the upper jaw longest), Leptotrachelus,
Pelargorhynchus, Plinthophorus, Saurorhamphus (with the lower jaw
longest), Eurypholis; Ischyrocephalus (?). The latter genus, from
cretaceous formations of Westphalia, is said to have two dorsal fins.

Twenty-ninth Family—Gymnotidæ.
Head scaleless; barbels none. Body elongate, eel-shaped.
Margin of the upper jaw formed in the middle by the intermaxillaries,
and laterally by the maxillaries. Dorsal fin absent or reduced to an
adipose strip; caudal generally absent, the tail terminating in a point.
Anal fin exceedingly long. Ventrals none. Extremity of the tapering
tail capable of being reproduced. Vent situated at, or at a short
distance behind, the throat. Humeral arch attached to the skull. Ribs
well developed. Gill-openings rather narrow. Air-bladder present,
double. Stomach with a cæcal sac and pyloric appendages. Ovaries
with oviducts.
Eel-like freshwater fishes from Tropical America.
Sternarchus.—Tail terminating in a distinct small caudal fin.
Teeth small. A rudimentary dorsal fin is indicated by an adipose band
fitting into a groove on the back of the tail; it is easily detached, so as
 to appear as a thong-like appendage fixed in front. Branchiostegals
four.
Eight species, some have the snout compressed and of
moderate length, like St. Bonapartii from the River Amazons; others
have it produced into a long tube, as St. oxyrhynchus from the
Essequibo.
Rhamphichthys.—Caudal fin none; teeth none; no trace of a
dorsal fin. No free orbital margin.
Six species, of which, again, some have a tubiform snout, whilst
in the others it is short.
Sternopygus.—Caudal fin none; no trace of a dorsal fin. Both
jaws with small villiform teeth; similar teeth on each side of the palate.
Body scaly.

Four species, very common, and growing to a length of 30

inches.
Carapus.—Caudal fin none; no trace of a dorsal fin. A series of
conical teeth in each jaw. Anterior nostrils, wide in the upper lip. Body
scaly.

One species (C. fasciatus) extremely common, and found all over
tropical America, east of the Andes, from 18 to 24 inches long.
Gymnotus.—Caudal and dorsal fins absent; anal extending to the
end of the tail. Scales none. Teeth conical, in a single series. Eyes
exceedingly small.

The “Electric Eel” is the most powerful of electric fishes, growing

to a length of six feet, and extremely abundant in certain localities of
Brazil and the Guyanas. The electric organ consists of two pairs of
longitudinal bodies, situated immediately below the skin, above the
muscles; one pair on the back of the tail, and the other pair along the
anal fin. Each fasciculus is composed of flat partitions or septa, with
transverse divisions between them. The outer edge of the septa
appear in nearly parallel lines in the direction of the longitudinal axis
of the body, and consist of thin membranes, which are easily torn;
they serve the same purpose as the columns in the analogous organ
of the Torpedo, making the walls or abutments for the perpendicular
and transverse dissepiments, which are exceedingly numerous, and
so closely aggregated as to seem almost in contact. The minute
prismatic cells, intercepted between these two sorts of plates,
contain a gelatinous matter; the septa are about one-thirtieth of an
inch from each other, and one inch in length contains a series of 240
cells, giving an enormous surface to the electric organs. The whole
apparatus is supplied with more than 200 nerves, which are the
continuations of the rami anteriores of the spinal nerves. In their
course they give out branches to the muscles of the back, and to the
skin of the animal. In the Gymnotus, as in the Torpedo, the nerves
supplying the electric organs are much larger than those bestowed
on any part for the purposes of sensation or movement.
The graphic description by Humboldt of the capture of Electric
Eels by horses driven into the water, which would receive the electric
discharges and thus exhaust the fishes, seems to rest either on the
imagination of some person who told it to the great traveller or on
some isolated incident. Recent travellers have not been able to verify
it even in the same parts of the country where the practice was said
to exist.

Thirtieth Family—Symbranchidæ.
Body elongate, naked or covered with minute scales; barbels
none. Margin of the upper jaw formed by the intermaxillaries only,
the well developed maxillaries lying behind and parallel to them.
Paired fins none. Vertical fins rudimentary, reduced to more or less
distinct cutaneous folds. Vent situated at a, great distance behind the
head. Ribs present. Gill-openings confluent into one slit situated on
the ventral surface. Air-bladder none. Stomach without cæcal sac or
pyloric appendages. Ovaries with oviducts.
The fishes of this family consist of freshwater-fishes from tropical
America and Asia, which, however, enter also brackish water; and of
a truly marine genus from Australia.
Amphipnous.—Vent in the posterior half of the body, which is
covered with minute scales longitudinally arranged.