UNIT-1

Chapter. .1
CLASSIFICATION,
NOMENCLATURE AND ISOMERISM
" LEARNINGOBJECTIVES 4
Ater reoding this chapter, students should be able to understand:
Classification of Organic compounds
Introducion
Open chain or Acycic compounds or Aliphatic compounds
Closed chain or Cyclic compounds
Heterocyclic compounds
Trivial or Common names
Monocyclic Heterocyclic Compounds
Bicyclic HeterocyclicCompounds
Classitication of Organic Compounds based onFuncional Groups
Nomenclature of Organic compounds
IUPAC System of Nomenclature
IUPAC Nomenclature of Unsaturcted Hydrocarbons
IUPAC Nomenclature for Monofunctional Compounds
IUPAC Nomenclature for Polyfunctional Compounds
IUPAC Nomenclature for Alicyclic (Cyclic) Compounds
IUPAC Nomenclature for Heterocyclic Compounds [known as Systematic (Hantzsch
Widman) Nomenclature system]
Nomenclature of Fused Systems
" Nomenclature of Benzofused Compounds
Isomerism
" Introduction
Structural isomerism
Chain isomerism
Position isomerism
Funcional group isomerism
Metamerism
Toutomerism
 Pharmaceutlcal Organlc Chemlstry -I 1.2 Classlficatlon, Nomenclature andt
11CLASsIFICATION OF ORGANIC COMPOUNDS
1.1.1 Introductlon
19omerin,
An organic compound is any chemical substance that contains carbon. AI
organisms are based on organic compounds. The organic compounds are classifiedthe
main types. intoIi,tar,
Organlc Compounds

Open chain or Aliphatic compounds wA Cycliccompounds

Conpounds containing straight o Compounds containing closeC
Oranched chains of carbon atorn gsystem.
aong with hydrogen atoms and
LNCiOna groupS

CNDCcic compounis oerocIc compounds

nese compounds contain These compounds contain carbon in
ont carbon ing systet stern along with one of mOre than. Cr
atom cther than carbon

Aieclic counoUnd AEQnatic compoust oeroalicyclic compounda

nese Compouns a ese compounds are
CiC Dut having Simia Ose. compounds
ENnd aromatic copounds ychc and having hetero
properties as that o ollowing Huckel rule aton as a part o rina
aiphatic compounds.

Cyclopropane Cyclobutane Cycopentane Benzene 1H-Pyrole Pyridine H

Tetra Piperidine
hydrofuran
Carbocyclic
aromatic Heterocyclic
aromatic

(1) Open chain or Acyclic

compounds or Aliphatic compounds: The open chain or
acyclic compounds are those in which
or branched manner in such a carbon atoms are linked to each other either in
way that the molecule is having linear
compounds are also called aliphatic compounds. open chain structure. These
e.g. (a) CH - CHa ethane, (b) CH¡
-CH2 - CH2 - CH, butane
 Pharmaceutical Organic Chemistry - 1.3 Classiticatlon, Nomenclature and lsomerlsm
(2) Closed chain or Cyclic compounds: The closed chain or cyclic compounds are
those organic compounds which have closed chain of atoms. These compounds are further
lassified into:
(a) Homocyclic or carbocyclic compounds
() Heterocyclic compounds
(a) Homocyclic compounds: The homocycic compounds are those in which the ring
structure is made up of only carbon atoms.
These compounds are further classified into:
0 Aromatic compounds and
() Alicyclic compounds
(0 Aromaticcompounds: Those compounds containing one or more benzene rings in
their structure are classified as aromatic or benzenoid compounds. Most of these compounds
have pleasant odour (Greek: Aroma -sweet smell).
Table 1.1
Sr. No. Aromatic Rings Examples
1. Monocyclic aromatic ring

Benzene
2. Polycyclic aromatic rings

Naphthalene Anthracene
() Alicyclic compounds: Cyclic compounds with ring structure containing only carbon
atoms are called alicyclic or carbocyclic compounds. Though these compounds possess a ring
structure, they behave more like. aliphatic compounds.
e.g.

Cyclopropane Cyclobutane Gyclopentane

(b) Heterocyclic compounds (Non-benzenoid aromatic): Cyclic compounds in which
the ring atoms are made up of hetero atoms like nitrogen, oxygen and sulphur in addition to
carbon atoms are called heterocyclic compounds. The above compounds are aromatic non
benzenoid compounds.
e.g.

1H-Pyrrole Furan Thophene Pyridine

Pharmaceutical Organic Chemistry -I 1.4 Classlflcation, Nomenclature and lsomerlsr.
1.1.2 Classificatlon of Heterocycllc Compounds
Trivialor Common Names
Trivial names of heterocyclic nomenclature are preferred. Some compounds of this kind
are as shown below,

H
H
Ethylene
oxide
Ethylene
Imine
Trimethylene
oxlde
Furan Tetrahydro Pyrrole Pyrrolidine

Pyran Pyridine Piperidine Imidazole Thiazole Morpholine Pyrimidine

According to ring component these are classified into three types:
Heterocyclic compounds

Bicyclic Polycyclic
Monocyclic (Two rings (More than
(One ring structure) fused with two rings
each other) fused together)

Five Six
Three Four membered
membered membered membered
heterocycles heterocycles
heterocycles heterocycles
() Monocyclic Heterocyclic Compounds:
() Three membered rings: These rings are having two carbon atoms and one hetero
atom. For example,

N S

Oxirane Aziridine Thiirane

(i) Four membered rings: These rings are having three carbon atoms and one hetero
atom. These rings are less stable due to strain. For example,
NH

Oxetane Azetidine Thietane

(i) Five membered rings: These rings are having four cartbon atoms and one
hetero
atom. For example,
 Pharmaceutical Organlc Chemistry-| 1.5
Clasiicatlon, Nomenclature and lsomerism

Tetrahydrofuran Pyrroldine Tetrahydro

thlophene 1H-Pyrrole Thiophene Furan
i) Six memberedNon-aromatlc Aromatic
rings: These rings are having five carbon
atom. For example, atoms and one hetero

H
Tetrahydro Piperidine Tetrahydro Pyridine
2H-pyran 2H-Pyran 24-Thíopyran
2H-thiopyran
Bicyclic Heterocyclic Compounds:
These rings are having two ring systems, in which at least one ring is
For example, having heteroatom.

H
Quinoline Isoquinoline 1H-ndole
(m) Polycyclic Heterocyclic Compounds:
These rings are having more than two ring systems, in which at least one ring is having
hetero atom. For example,
H

o9H-Carbazole Acridine
1.1.3 Homologous Serles
Organic compounds having similar structure and functional groups, are known as
homologous compounds and this series is known as homologous series.
Characteristicsof Homologous series:
Homologous series have the following characteristics:
3 Ail the members of a series contain same elements and the same functional groups.
* All the members of a homologous series can be represented by ageneral formula.
9 Allthe members of a homologous series can be prepared by similar methods.
Allthe members of a homologous series usually undergo similar chemical reactions.
Successive members in a series differ by a -CH2 group.
9 The physical propeties of members of a homologous series vary in a regular way down
the series. For example, boiling point, melting point and density of the alkane series vary
in a regular way with increasing number of carbon atoms.
Pharmaceutlcal Organic Chemistry -! 1.6 Classiflcation, Nomenclature and
Table 1.2
lsomer.
Sr. Name of Series General 1-Homologous Series I-Homologous Serie.
Formula
No.
1 Alkane C,H2n+2 CHa CHy-CH
2 Alkene C,Han CH, = CH2 CH,=CH-CH
HC = CH HC= C-CH
3. |Alkyne CiHzn-2
4. Halo alkane CaHaneX CH- X CH, -CH,-X
Alcohol CH3 - OH CH - CH,-OH
5.
6. Ether CaHzn+20 CHg - O- CH CH, -0- CH - CH,
CH3 - CHO CH, - CH, - CHO
7. Aldehyde
8. Ketone CHz0 H;C-C- CH3 H2
HC-C-CCHg

9.Carboxylic acid CHnO CH, - COOH CHg - CHCOOH

10. Ester CH - CO0- CH, CH3- C00 - CH2 - CHa

1.14Cassificatlon of Organic Compounds based on Functonal Groups

The atom or group of atoms that define the structure of a particular family of organ:
compounds, also responsible for physicochemical properties, is called as functional group.
The concept of functional group would help us in the following ways:
It serves as a basis for nomenclature of orgaFic compounds.
It serves as a basis for classification of organic compounds. Compounds havin;
similar functional group behave likewise, ie. having similar properties.
It is the site of chemical reactivity in a molecule.
Table 1.3

Functional group Class names Name-clues Examples

Carbon-halogen |Halogen -X Halogeno Chloromethane
bonds |compounds CH-CI
-F Fluoro
|1-bromobutane
-CI Chloro |CH,CH,CH,CHy-Br
-Br Bromo
|lodo
 Pharmaceutical Orgenle Chemistry - 1.7 Classfoatlon, Momencletur and leomerlam

Punctlonal group Class names Name-clue Examples

|Carbon-oxygen Hydroxyl -OH Mydroxy -ol Ethanol
|bonds |compound CHCH,-OH
(alcohols) Hydroxy Hydronyethanoic
acid

Ether C-0-C Ethers -oxy Ethoryethane

CHCH,OCHCH,
Carbonyl -Co- Carbonyl
compounds:
Ketones -one
Propanone
2-propanone
|Aldehydes CH, - C- CH

-CHO -al
|1-Ethanal
CH;CH,CHo
Carboxyl -COOH Carboxylic acids -oic acid Propanoic acid
CH,CH,COOH
Ester -COOR Esters Alkyl -oate Ethylethanoate
CH,COOCH,CH,
Acyl halide -COX Acyl halides -oyl halide Ethanoyl chloride
Amide -CONH, Amides -amide Ethanamide
Acid anhydride Acid anhydrides -oic anhydride Ethanoic anhydride
|(-cO)0
Carbon-nitrogen Amino -NH2 Primary amines Ethylamine
bonds
-NHR Secondary -amine Diethylamine
Jamines Amino
-NR2 Tertiary amines Trimethylamine
Cyano -CN Nitriles |-nitrile Ethanenitrile
Nitro -NO2 Nitro Nitro Nitroethane
Jcompounds
Phermaceutical Organie Chemistry -l Classiflcaton, Nomenclature and lsomr,
cOMPOUNDS
12 NOMENCLATURE OF ORGANIC
Already there are infinitely large compounds existing and a large number of
compounds being synthesized every day Every compound requires a specific and un
name so that it can be recognized all over the world by that name. Each compound ha
specific structure and is designated by structural fomula, so every compound must be a
a characteristic and unique name
In the starting organic compounds are classified on the basis of trlvial name in t
ystem,compounds are cassified on the basis of source from which they are obtained 8
this system was not universally accepted, hence a new system was introduced, ie TUeA
system
Table 1.4
Sc. Organic Source Trivial Name
Na. Compound
1 CHe Formed in Marsh places Marsh gas
2 CHOH From Barley Grain alcohol
3 CH,COOH From acetum (Vinegar) Vinegar
(COOH2 From oxalis plant Oxalic acid
5 CHCH,CH,COOH From butter Butyric acid
CH,OH By destructive distillation of wood Methyl spirit
7. NH,CONH From urine Urea
8 H From Malunm (Apple) Maleic acid
HO - C- COOH

HC - COOH
Malic acid
9. HC- COOH From Citron (Lemon) Citric acid
HO -coOH
Ha
-t-cooH
Citric acid
10.
HC -C- coOH From Lactum (Milk) Lactic acid

Lactic acid
11 HCOOH
In case of isomers, Formica (Red ants) Formic acid
lkanes will
have the prefixes n-,
following iso- and neo-, which are
used a
(C) The use of prefx n-:
continuous chain of C-atoms. The prefix n is used to denote an alkane
N-stands for normai or straight chain. which contai
CH;CH;n-hexane
CHCH;CH;CHs
 Pharmaceutlcal Organic Chemistry 1.9 Classiflcatlon, Nomenclature and lsomerlsm
(b) The use of prefix lso-: The prefix -iso is used to denote an alkane, having methy!
group attached to the second last carbon of chain.
CH, CH;
H3C - C- CH,
IH H H2
HC - C- C-C- C - CHy
H H
Iso-butane Iso-hexane
(c) The use of preftx neo-: The prefix neo is used to denote an alkane
having two
methyl groups attached to the second last carbon of the chain.
CH CHg

HC -C- C - CH3 H3CC- C - C - CH3

CH3 CH,
neo-hexane neo-heptane
131UPAC SYSTEM OF NONENCLATUR:
IUPAC (International Union of Pure and Applied Chemistry) is a systematic nomenclature
system of organic compounds and used universally. The aim of the IUPAC System of
nomenclature is to establish an international standard of naming compounds to facilitate
communication. The goal of the system is to give each structure a unique and unambiguous
name, and to correlate each name with a unique and unambiguous structure.
Secondary prefix +Primary prefix+ Root word + Primary suffix +Secondary suffix

It represents thel It is used It represents It represents |It represents

substituents or incyclic number of carbon saturation or the main
branches compoundsatoms in selected|unsaturationin functional
(cycio) carbon chain carbon chain group

14RLES OF NOMENCLATURE
1.4.1 IUPAC Nomenclature of Saturated Hydrocarbon
Rule 1: Longest chain rule: Select the longest chain of carbon chain.
4ÇH H H
H,0 ¢-C-C-CH,
3 2 1
6CH,
esSy 7CH
8CH,
 Classiflcatlon, Nomenclature and
Pharmaceutical Organlc Chemistry -! 1.10
Isomeria
is numbered from the.
Rule 2: Lowest Number: Selected principle carbon chain
where substituent or multiple bond or functional group is nearer (owest possible number,
Priority oder: Functional group >Double bond >Triple bond >Substituent
5 4 H, 4 H
| 3
CH2 5
Correct
Wrong
are present, the
Rule 3: Lowest Sum Number: In case if more than one substituent function:
multiple bonds and
choose the chain having maximum number of substituents,
groups.
Priority order: Functional group > Multiple bond >Substituent
CH, CH,

CHg CHg
Correct
Wrong
Rule 4: Use of prefixes di, tri etc.: If the compound contains more than one similar alky
groups, their positions are indicated separately and an appropriate numerical prefix di, tri
tetra etc., is attached to the name of the substituent. The positions of the substituents are
separated by commas. However, the numerical prefixes such as di, tri etc., are not considered
for the alphabetical order. For example:
ÇH, ÇHy
1
CH,
2,2,3 -trimethylpentane 2,3 -dimethylpentane
Rule 5: If two different alkyl groups are located at the equivalent positions, ther
numbering in the carbon chain is done in such a way that the alkyl group which comes first
in alphabetic order gets the lower position.

C- - -C
CH,
3-ethyl -2,3 -dimethylpentane
Rule 6: If acompound has two or more chains of the same length, then principle chain is
selected in such a way that greater number of substituents work as prefix.

H4 5 6
4- ethyl - 3-methyl hexane
3-ethy-2-methyl hexane
Wrong Correct
 Pharmaceutical Organle Chemlstry-| 1.11 Classificaton, Nomenclature and lsomerism
Pule 8: Some of the functional groups always work as prefix. For example.
f the molecule contains more than one dissimilar functional group, then numbering of
he narent chain is done in such a way that the functional group of higher priority gets the
lower number. The order of priority of various groups for the sake of numbering is given in
the following Table 1.5.
Table 1.5
Sr. Functional Group Prefx Sr. No. Functional Group Prefix
No.
1 -X halo 5 -OR alkoxy
2 -NH2 amino 6 -CN cyano
3 -NH imino 7 -NO nitroso
4 -R alkyl 8 -NO nitro
Word Root: The word root is the basic carbon skeleton. It depends on the number of
carbons present in the parent chain, which contains functional group. The following are
IUPAC WOrd roots.
Table 1.6
Sr. No. Word root Number of carbons Structure
1 Meth 1C CH, -
2 Eth 2C CH3CH2 UNI
3 Prop 3C CH;CH,CH¡ ACCESSION
NO. VEA
4 But 4C CH3CH,CH,CH, -
5 Pent 5C CH;CH,CHCH,CH2 - CIBRAR

6 Hex 36C CH;CH,CHCH,CH,CH2 -

7 Hept 7C CH;CH,CH;CH,CH,CH,CH,
8 Oct 8C CH,CH;CH,CH;CH,CH;CH,CH, -
Non 9C CH;CH,CHCH,CH,CH,CH,CH;CH -
10 Dec 10C CH;CH,CH;CH,CH,CH,CHCH,CH,CH, -
11 Heptadec tow t 17C
CH;CH(CH)13CHCH3
12 Octadec 18C CH;CHCH2h4CH,CHs
13 Nonadec 19C CH;CH,(CHa)hsCH,CHy
14 Icos 20C CH,CH,(CHTh6CH;CHg
 Classiflication, Nomencature. and I
Pharmaceutcal Organlc Chemistry -1
1.12 Isomer,
Nomernclature of Unsaturated Mydrocarbon
14.2 IUPAC group (i.e. double bond or tr.
having the functional
Select the longest chain of carbon
bond).
so that the double or triple
bond get the lowe
Start the numbering in such a way,
number.
double bond the suffix '-ene' is added in the longest carte
" In the nomenclature of
numbered.
chain, in which the double bond is lowest
nomenclature of triple bond, the suffix 'yne' is added in the longe
Similarly, in the
numbered.
carbon chain, in which the triple bond is lowest
Table 1.7

Suffix Example
Nature of the compound
-ane
Methane
For saturated compounds
For unsaturated compounds
one double bond -ene Ethene

two double bonds -adiene buta-1,3-diene

three double bonds -atriene hexa-1,3,5-triene
one triple bond -yne Ethyne
two triple bonds -adiyne penta-1,4-diyne
14.3 1UPAC Nomenclature for Monofunctional Compounds
For the nomendlature of monofunctional group, the rules are as following:
Select the longest chain of carbon having the functional group.
Start numbering in such a way, so that the functional groups get the lowest number.
The functional group is added in the parent chain hydrocarbon by removing the termin:
'e'.
As reported earlier, some of the functional groups will be always treated as substituent
hence they willbe written as 'prefix' with the parent name.
Other substituents are numbered according to alphabetical order.
14.4 IUPAC Nomenclature for Polyfunctlonal Compounds
Organic compounds having two or more functional groups are called as polytunctio
compounds. While doing the nomenclature, by IUPAC system of polyfunctional compour0
one of the functional groups is taken as key functional
group, even as remaining funcic
groups are treated as substituents. The priority of functional groups are as
following.
 Pharmaceutlcal COrganie Chemistry -1 1.13 Classiflcation, Nomenclature and Isomerism
Table 1.8
Sr. No. Functional Class Suffbx Prefbx
Group
1 -COOH Carboxylic acid -oic acid carboxy
2 -SO;H Sulphonic acid -sulphonic acid
3 Acid anhydride -oic anhydride

4 -COOR Ester -oate

5 -COX Acid halide -oyl halide
6 -CONH, Acid amide -amide carbanoyl
-CN Nitrile -nitrile cyno
8 -NC Isonitrile -isonitrile
9 -CHO Aldehyde -al aldo, formyl, oxo
10 -C=0 Ketone -one keto, oxo
a 11 -OH Alcohol -ol hydroxy
12 -SH Thio -thiol mercapto
-NH2 Amino -amine amino
13
14 Alkene -ene

15 Alkyne -yne
gn16X Halide halo
Nitro nitro
17 -NO2
18 -OR Ether alkoxy
19 -R Alkyl alkyl
"fluoro-,
Substitutive naming of halogen compounds are formed by adding the prefixes
"chloro-" "bromo"- or "iodo"- to the name of the parent compound.
Groups which may be named only as prefixes
Formula Prefix
-F fluoro
-CI chloro
-Br bromo
-I iodo
-OR alkoxy
-NO nitro
-N=N azo

R alkyl
CotH; pheny
 Classflcatlon, Nomenclature and
Pharmaceutlcal Organic Chemlstry -l 1.14

CI
Isomerlar,
Br CI

CI
C

C
5-bromo-2-chiorooctane 3,4,7- trlchlorononane 3-chlorohexane

" If there is achoice between the two halides for numbering, alphabetical order is followe:
For example,
-Br
CI - C
F Br

1-chloro3-fAuoro-5 1-bromo-3 2-bromo-3

iodocyclohexane fluorocyclohexane chlorobutane

While doing nomenclature of polyfunctional compounds the following rules are followed:
Select the key functional group and the parent chain having maximum number of
functional groups.
Start the numberingfrom the end, so that the key functional group is nearer and should
be lowest numbered.
The key functional group has been added in the parent chain hydrocarbon by removing
the terminal 'e.
Other substituents added as prefix in alphabetical order.
As already discussed some of the functional groups are always treating as
substituents,
hence they are written as 'prefix' with the parent name.
If acompound is having both double bond and triple bond, then the
numbering will be
carried out using lowest number rule. If both were given the same
number, then
preference be given to double bond and such compounds are named as
will
alkynes.
Arrangement of Prefixes
The prefixes such as di, tri etc. are not
considered in alphabetical order. Other
substituents are arranged alphabetically.
Ifthe two substituents are having same
position, then the lowest number is given to the
substituent in alphabetical order.
 Pharmaceutcal Organlc Chemistry - 1.15 Classitlcatlon, Nomenclature and lsomerlam
As IUPAC Nomenclature for Allcycllc (Cyclle) Compounds

Cyclic compounds

Homocyclic compounds Heterocyclic compounds

(Alicyclic compounds) Compounds containing ng
Compounds containing ring. and are made up of carbon
made up of carbons atoms along with some other
only OH atoms like 0, N, S

Aromatlc Non-aromatic
Benzene Cyclohexanol

H
Cyclopentadiene Pyrrole Furan 4H Pyrrole Tetrahydro furan

Rule-1: Name of monocyclic, saturated hydrocarbons are formed by attaching the prefix
"ycdo to the names of acyclic, saturated hydrocarbon with same number of carbons.

Cyclopentane Cyclopropane Cyclohexane Cyclooctane

Rule-2: Name of unsaturated monocyclic hydrocarbons (with no side groups) is formed
by substituting "-ene", "-yne", "-adiene", "-atriene", "-adiyne" etc. for "ane" in the name of
corresponding cycloalkane e.g.

Cyclohexene 1,3-Cyclohexadlene 1,4-Cyclohexadlene 3-methylcyclohexene

Rule-3: If a straight chain substituent attached to monocycic hydrocarbon has greater

number of carbon in the main chain then the cyclic ring becomes substituent as

1cyclopropyl-3-othy-2,4-dimethylhexane 1-cyclopentyl-3-ethyl-1,4-pentadlene
Pharmaceutlcal OrganlcChemlstry -! 1.16 Classiflcatlon, Nomenclature and
SubstBtuted Aromatic Hydrocarbons
lsomerls
Following names for substituted monocyclic aromatic hydrocarbons are retained.

Toluene Cumene Benzene m-xylene

Styrene p-xylene Cymene

Rule-1: Other monocyclic substituted hydrocarbons are named as derivatives of benzen:
or one of the compounds listed above. However, if the substituent introduced into such :
compound is identical with already present in that compound, then the substitute:
compound is named as derivatives of benzene as

1-methyl-3-vinyi benzene 1,4-divinyl benzene

Rule-2: The positions of substituents are indicated by numbers except o-(ortho
m-(meta), p-(para) may be used in place of 1, 2-, 1, 3-, and 1, 4- respectively, when only tw
substituents are present. The lowest possible number given to the substituent coming first ir
alphabetical order except that when names are based on those of the compounds mentionec
in the beginning of section-E.

1,2-dimethyl-3-propyl benzene 3,5-dlethyl toluene 1-ethyl-4-pentyl benzene

146 IUPAC Nomenclature for Heterocyclic Compounds
[Known as Systematic (Hantzsch-WIdman) Nomenclature System]
Heterocyclic compounds are organic compounds that contain ring structure containing
atoms other than carbon such as oxygen, nitrogen, sulphur as a part of ring. They can be
aromatic or non-aromatic compounds. For example, pyridine, pyridimine, pyrrole etc. are
aromatic, while ethylene dioxide, gama lactones are non-aromatic compounds.
The Hantzsch-Widman system provides a more systematic method of naming
heterocyclic compounds that is not dependent on prior carbocyclic names. According to
IUPAC system of nomenclature, heterocyciccompounds are divided into three parts:
Astem that indicates the ring size.
A
prefix that describes the hetero atom.
Asuffix that indicates the degree of unsaturation.
 Pharmaceutical Organlc Chemistry-| 1.17
Classilcatlon, Nomenclature andlsomerlgm
Table 1.9: Stem, Prefixes and Suffixes used in the heterocyclic system
Sr. No. Hetero atom Valence Prefix
2 Oxa
N 3 Aza
S 2 Thia
Se 2 Selena
Te 2 Tellura
3
Phospha
As 3 Arsa
Si 4 Sila
Ge 4 Germa
Table 1.10: Stem, Prefixes and Suffixes used in the heterocyclic system
Stze Stem Nitrogenous ring Non-nitrogenous ring Partly Saturated
No. of the Saturated| Unsaturated Saturated Unsaturated
ing
1 3 iridine irine -irane irene
2 4 ef -etidine -ate etane ate
3 5 olidine -ole olane ole (dithydro)
4 6 in -ine -ane -in (di or tetrahydro)
5 7 ep epine epane -epine (dior tetrahydro)
6 -ocine 0cane ocine (di, tetra, or hexahydro)
In the numbering of heterocyclic the hetero atoms are always given number 1.
" f more than one hetero atom is present in the ring then they are according to priority.
The order of priority is as following:
Oxygen >Sulphur > Nitrogen
When a ring is having more than one hetero atom, then they should be numbered
according to lowest sum rule.
" All the substituents are arranged in alphalbetical order.
For example:

Common name: Ethylene oxide

(a) Systematic name: Oxa + irane = Oxirane
K Common name: Furans n8
(b) Systematic name: Oxa + ole = Oxole
 (1)
azetidine
name: 1,
therefore ByThe starting This
omitted
Part Part
Rules Pharmaceutical
Chemistry-I
Organic
combining ring 1-Generally
ring 1 for
the is
numberingto Suffix Systematic
= (e)
4-membered give contains Prefix
vowel the
1, = the
2-oxaza, Indicate =
prefix
on 1.NameIndicate name
the and O Nomenclature:
the Priority
and and ring Pionity
the consists Systematic
Pyrimidine
Common
name: Systematic
Piperidine
Common
name:Systematic
Common
Pyrrole
name:
end N the
suffix, fully hetero
at N Oxa O size
of Aza Thia S. Prefx type
thesaturated O (3,
prefix of name: name:
first tw o atom, 4, oftwo name:
heteroatom 5,
partvowelssuffix is N S Suffix ...) parts.
Two H H 1.18
where
1, Az Thi at at
should of Aza 1
ended is 2-0xa ring 1"
O Saturation
Ring
Size (N, at position position Classiflcation,
etidine.?
be up has 0, 1, Nomenclature
Isomerism
aza, 3
dropped. S) positions
together buthigher Aza
+
Aza
+

the + +
This priority + inane ole=
(1, first ine
gives 2 = = 1H
oxaza vowel than [1, 1H
3] =
the - Azole and
must N. diazine Azinane
correetidine Hence
be

unsaturated
maximally
ring.
indicated Rules " (3)
The ThusPerhydro
azine. byThe
followed the
By It is considered
this The In
(2)stugtg
aibi-tns Pharmaceutical
for
ring
dropped).tt
combining
correct
5-membered,
fully numbering this
position the gives
by fully ring
H-Oxole full is
numbers partial4H-pyran Aziridine
Oxirane 6-membered, name the as
of name there Organic
the combined prefix
nitrogen as: wil
unsaturation is prefixes start are Chemistry
and Azine perhydroazine. 1, 1
namethe offuly unsaturated (oxa) one
2, from
-Azepine italic or 5-0xadiazole. and prefixes and
oxygen -
carbon Perhydro
azine
Oxetane
saturated oxygen
capital the two
in
heterocyclic suffix ring as atoms
nitrogens
atoms diazole Oxole fuly 1, (0)
H 1,3 with with 1.19
H
and 2,and
(e.g. unsaturated and
4H-Pyran which thiazole Azolldine
Oxolane N 2 5-oxadiaza
(N)
prefix. dropping the two as
1H, 1.3 prefix two Classification,
compounds suffix
nitrogens
2H, bear 1,4
Tetrahydro
nitrogen
2
6-membered the is (note diaza.
athiazole etc.) extra oxazine H

appropriate ole. that (N) Nomenciature

atoms.
followed
hydrogen 1,3
are
Azole
diazine H the at
ring positions Hence
a
by vowels, in and
atoms
must be nitrogen
with
the oxa oxygen isomerlsm
2
we isand
name
get not is
5,
of
 Classiflcatlon, Nomenclature and
Pharmaceutical Organic Chemistry-l 1.20
lsomerlsm Pharmaceutlcal Organlc Chemistry-|
are used if two or three or four atome 1.21
Classiflcation, Nomenclsture and lsomerlsm
The words dihydro, or trihydro, or tetrahydro
indicate the position of saturated atome eg
saturated. These words preceded by numbers
corresponding fully unsaturated Hantzsch-Widm.
Benzene
14-Diazabenzene
low as possible and folowed by the
name.
Cyclopentadiene Oxacyclopenta-2,4-diene

Cyclopentadiene
2,3-Dihydrooxole 1-Oxa-3-azacyclopenta-2,4-iene
1,4-Dihydroazine 2.3,4,5
1,2-Dihydroazine Tetrahydroazine
Cyclopropane Oxacyclopropane
Isomers have the same 9t9rion
molecular formula, but
diter in the postion of
abrano3V Cyclopropene Oxazacyclopropene
the double bond
Cyclopentadiene 1-Thia-2-azacyclopenta-2,4-diene
In case of partialy unsaturated rings ie. rings contain one or more double bonds are
given special Hantzsch-Widman suffixes as in Table 1.10 and the double bond is specified as Cyclohexane
A, A, A, etc, which indicates the position of double bond between 1 and 2, 2 and 3, and 1-0xa4-azacyclohexane
H
3 and 4 atoms respectively.
Hence the IUPAC name is written as A + Prefix + special sutx, where
Wnere
x = location of the
a
double bond. Naphthalene 2-Azanaphthalene
For example: 3
3 1.4.7 Nomenclature of Fused Systems
Fusion: This term is used to describe the process of joining two separate rings with the
maximum number of noncumulative double bonds via two atoms and one common
bond.
&Atotine `Oxetene -Azoline `Oxolene
Ortho-fused rings are those rings that have ony two common atoms and one bond,
for example: naphthalene.
sis ANH

ee &4,3-Thlazoline 1,3-Diazollnesut Naphthalene

Ortho-and peri-fused rings: These rings are found in apolycyclic compound with a ring
that is ortho- fused to different sides of two other rings that are themselves ortho-fused
Replacement Nomenclature System: together (i.e. there are three common atoms between the first ring and the other two).
o In this type of system, the heterocycle's nomenclature is done by using the
Polycyclic compounds incorporating one heterocyclic ring or fused heterocyclic system
corresponding cyclic name. The elemental prefix for the heteroatom is introduced. For fused to benzene are known as benzoheterocycles.
example: Also bicyclic compounds with two fused heterocyclic rings are well known.
Both types can be named according to certain rules.
 Classification, Nomenclature and Isom,,
1.22
Chemistry- I Pharmaceutlcal Qrganic Chemistry-|
Pharmaceutical Organic three benzen
1.23 Classification, Nomenclature and lsomerism
being composed of
1H-phenalene is considered as
For example: two. (3) In this structure, pyridine ring is attached with the benzene ring. The point of
ortho-peri-fused to the other attachment is [c]. Hence the structure is written as.
each is

Benzo[c]pyridine
1H-Phenalene Isoquinoline

Fused Compounds 1.4.9 Nomenclatuere of Bridged Bicyclic Hydrocarbons

14.8Nomenclature of Benzo heterocylic systs
one heterocyclic ring or fusedheterocyclic syste. Saturated bicyclic systems having two or more atoms in common are named by prefixing
Polycyclic compounds incorporating
benzoheteroycles. The naming of fused
"bicyclo' to the name of the parent compound.
fused to benzene are known as two monohete
with another heterocyclic ring or
composed of bernzoheterocycles fused the second is conside The cyclic parent hydrocarbon system containing the same total number of carbon atoms
one system as the base and
cyclic units is based upon considering membered and six membered rings are as followi in the skeleton.
The base system for five
as substituent. Pyrido from Pyridine, Pyrimido from Pyrimid The number of carbon atoms in each of the three bridges, connecting the two tertiary
Furo from Furan, Imidazo from Imidazole, and Chrom:
Pyrazino from Pyrazine
Thieno from Thiophene, Pyridazino from Pyridazine, carbon atoms is indicated in parentheses, in descending order and arabic numerals are
from Chromene. The rules are as following. used to indicate the number of carbon atoms and the numbers are separated by full
1 Prefix: the word benzo stops.
position of fusion
2 Letter in square brackets: indicating the The bicycic system is numbered starting with one of the tertiary bridging cabon and
3 Name of heterocyclic ring: (commonor IUPAC name). proceeding through longest bridge to the second bridging carbon continuing back to the
heterocyclic ring (the connected bond take le:
Name = Benzo [letter] name of first bridging carbon through the second longest chain.
(a, b, c.)
sites,which are written as a, b, c,d and e Numbering is completed by numbering the shortest bridge beginning with the atom
For exanple: In furan, there are 5 connecting
4 C3 next to the first bridging carbon.

(1) In this structure, furan ring is attached with the benzene ring. The point
attachment is [b]. Hence the structure is written as, Bicyclo 2,2,1] Bicyclo [3,2,2]
heptane nonane

soMEL
Introduction
Benzo[b]oxole
saThe compounds which has same molecular formula but have different physical or
Benzofuran
enzen ring. The poin:
(2) In this structure, pyrrole ring is attached with the benzene
attachment is [b]. Hence the structure is written as, chemical property due to different structure, are known as isomers and the phenomenon is
known as Isomerism. As isomers are having same formula, but they differ in their physical or
b
chemical properties, this is due to their different modes of arrangement of atoms within the
H molecule. Isomerism is classified into two types:
e2t Benzo[bJazoleiot s 2bnuanov
1H-Indole
gnos bomsin d n t o
 1.24
Classification, Nomenclature and lsomeri.
Pharmaceutical Organic Chemistry -1 Isomerism Pharmaceutlcal Organic Chemistry- 1.25 Classification, Nomenclature and lsomerism
3. Posltion lsomerism
Structural isomers have the same carbon skeleton and belong to the same homoiogous
Stereo Isomerism
Structural Isomerism
ceries, but differ in the position of the functional group.
Chain Isomerism Example 1:Structural isomers for chloropropane, CzHCI.
Ring Chain Isomerism Geometrical
Optical
Isomerism Hyc-a H,c--CH,
Isomerism
Position Isomerism
1-Chloropropane 2-Chioropropane
Functional Isomerism
1- chloropropane is having B.P. 46.6°C 2- chkoropropane is having B.P. 35°C
Meta Isomerism

Tautomerism 4. Functional group isomerism

1.5.1Structural isomerism atoms attached in The structural isomers have the same molecular formula but belong to different
same molecular formula have their
If the compounds with the structural isomers of homologous series, i.e. they differ in the nature of the functional group.
different structures and are said to be
different orders, they have Example 1: Alcohols and ethers.e.g. Formula CzHs.
each other.
Structural isomers containing the same functional group agi Methoxymethane is an ether and exists as a gas that has been used as an aerosol
1 hain isomerism propellant and a refrigerant. Ethanol is an alcohol and exist as a liquid that is used as a
but differ in the order in which the carbon
Chain isomers have the same moleqular formula solvent and in alcoholic beverages.
atoms are bonded to each other. CH,-0-CH, CHy-CHy-OH
Ecample 1: Structural isomers for CH10 n-Ethanoi is having B.P. 78°C
CHs Methoxymethane is having B.P. - 25°C|
HycH
--cH,
cbidt Example 2: Aldehydes and ketones, e.g. CgHs0.
n-Butane Iso-Butanae r CH-CH-CHO
Iso-Butane is haing B.P. 12°C Propanal Propanone
Butane having B.P. 0°C
Propanal is having B.P. 48°C Propanone is having B.P. 56°C
Example 2: Structural isomers for C_H12
CH,
HyC - Hyc--cH% Example 3: Carboxylic acids and esters,e.g. CaHO2.
H

nPentane Iso-Pentane
cHs
Neo-Petane OH

Propanoic acid Methyl ethanoate

n-Pentane is having B.P. 36°C Lso-Perntane is having B.P. 28°C |Neo-Pentane is having B.P. 9.5°C Propanoic acid is having B.P. 141.2°C Methyl ethanoate is having B.P. 56.9°C
2. Ring chain isomerism
This type of isomerism is shown by the compounds having same number of carbon
atoms but differ in their linking pattern. For example: Ethyl methanoate
H
Ethyl methanoate is having B.P. 54°C
H,- -H, 5. Metamerism
1Butene Cyclobutane
Due to unequal distribution of carbon atoms on both sides of functional group, this type
1-Butene is having B.P.-9.5°C Cyclobutane is having B.P.12.5°C| of isomerism occurs. Same homologous series compounds show this type of isomerism.
 1110. 9. 8 7. 6. 5. EXERCISE
4 3 2
() CH
(Name
a) - keto
ExplainWhatCompounds?
WriteWhat How Write WriteWriteWrite equilibrium
Give Tautomerism: 6.
CH,-CH, form For This (2)
the do (1) For
exarmple:
metamerism detail in is IUPAC the inthe inthe example: Ethers Pharmaceutical
Chemistry-!
Organic
following isomerism?you detail detail approximately is Amines
Hantzsch-Widman, classification
classification with a Dietryl
mean
structural system special having
the Etty each Dietylamine is
the acetoacetate
fomEthyl
Keto ether having
alkyl with by
2CH tautomerism? Classify IUPAC
isclassificationof acetoacetateother. type molecular
Dietyl
ether
groups: used 93% is diethylaminemolecular
examples.isomerism of Ethyl having
system of (93%) of
them organic organic having
56°cB.P
for acetoacetate and formula
IUPAC functional B.P.
with th e the has formula
with of 34.6°C
nomenclature compounds.
compounds
compounds.
heterocyclic
nomenclature. enol two
CH;CH2(b) 2 nomenclature
suitable CiHho.
examples.
is approximately isomerism,
form6%.forms CaHyN.
having
example. Methyl 1.26
based B.P. at
of for roonm Methylpropylamine
acetoacetate
180.8C Etyl in propyl
fused
heterocyclic on (6%)tEnol
fom which
OH
temperature, Methyi
propyi
ether Classification,
functional ether methylpropylanine
systems
the
-oCHs having
is
isomers is
compounds.
and groups. having
the Nomenclatureand
B.P.
benzofused mixture
are B.P.
38.9°C
62°C
in
containe dynami.
lsomeriS
4. 3.
CHHnCaH2n-2
(e) ChH2n+2
() (a) The (e)2, (c)2,
-dimethylcyclopentane 2.
5-dimethylcyclopentane
1,4-dimethylcyclopentane (a) Select (d3,
) (c) (a)1, 1.
2,4-dimethylhexane
13-trimethylpentane Select (e) (c) (a)
general 3-methyl-3-propylheptane
4-ethyl-4-methyloctane
5-methy-5-ethyloctane QUESTIONS
MULTIPLE
CHOICE
Select
14 13. Pharmaceutical
Chemistry-|
Organic
the 12.
5-dimethylhexane the
correct HC=CHCH,CH,CONH,
the (c)
(CH3)>CHCH,CH,COCI (Write
a)2-propenal
(c) (Write
a) -NOzArrange
(c)
formula Correct (a)OH
Correct 2,
the 2, the
IUPAC 4-trimethylpentene
for IUPAC IUPAC structural the
IUPAC
noncyclic following
name system
namefor name
for
formula
alkenes for for groups
the
for
following the according
is
following 1.27
CnHn+2(d)CHHzn(b)
3-dimethylcyclopentane
(d)2, (b)1,
6..

(e1-ethyl-1,
)
3-dimethylbutane (b) S-methyl-5-propylheptane
3-methyi-3-propyloctane () (b) (CH,CH2)CHCN
CHCH,CH(CH)CN (d) (b)
2-propanone(d) (b)
2-chloro-2-methylpropene
compounds -C(dI) (b) to
COOH
3, their
Classification,
3-dimethylcyclopentane 5, compounds
5-trimethylpentane functional

Nomenclature
group

priority
and
-
Isomerism
 Classlflcatlon, Nomenclature and
Pharmaceutical Organlc Chemistry -I
1.28 lsome Pharmaceutical Organlc Chemistry-| 1.29 Classiication, Nomenclature and lsomerism
compound given below is
5. The correct name for the 11.Para-xylene is the same as
(a) 1,2-dimethylbenzene (b) 1,3-diethylbenzene
(b) 2-ethyl-1-propene (O 1,3-dimethylbenzene (d) 1, 4-diethylbenzene
(a) 2-methyl-1-butene (e) 1, 4-dimethylbenzene
(d) 3-methyl-2-butene
() 2-ethy-1-pentane 12. Which of the following formula represents an alkene?
(a) CH,CH,CH, (b) CH;CH3
(e) pentene () CHCH,CHCH, (d) CH,CH,CI
6. Selec the best name for..... (e) CHCH
13. What is the name of the following compound?
Br

(b) 4-ethyl-trans-3-octene
(a) 4-ethyl-cis-3-octene HO
() 4-buty-cis-3-hexene
(d) 5-ethyl-trans-5-octene
(e) 5-ethyl-cis-5-octene B
(a) 1,3-dibromophenol (b) 2, 5-dibromophenol
7. Name the following compound: (c) 2, 6-dibromophenol (d) m-dibromophenol
(e) o-dibromophenol
14. Which one of the following is a secondary alcohol?
(b) 6-ethyl-3-methylcyclohexene (a) CHCH,OH (b) CH0H
(a) 6-ethyl-4-methylcyclohexene
(d) 6-ethyl-4-methylcyclohex-1-ene (c) CH;CH(OH)CH, (d) (CH)C,OH
(c) 3-ethyl-5-methylcyclohexene (e) none of these
(e) 6,4-dialkylcycohexene 15. Select the IUPAC name for (CHa)CHCH(OH)CH;C(CH3)3.
8. What is the IUPAC name of the following compound? (a) 2, 5, 5-trimethyl-3-hexanol (b) 1,1,4, 4-pentamethyibutanol
(c) 1, 1-dimethyl isopentanol () 2, 5-dimethy-4-hexanol
(e) none of these
16. Which is not a physical property of alcohols or phenols?
(a) Phenols are generally only slightly soluble in water.
(a) 2,6-diethyl-3-nonyne (b) 2, 5-diethyl-3-nonyne ie (b) The solubilities of normal primary alcohols in water decrease with increasing
() 3,7-dimethyl-S-nonyne (d) 3, 7-dimethyl-4-nonyne molecular weight.
(e) 2,6-diethyl-3-heptyne (c) The hydroxyl group of an alcohol is nonpolar.
9. The following chemical structure represents a molecule of what molecular formula? (a) Due to hydrogen bonding, boiling points of alcohols are much higher than those of
ÇH corresponding alkanes.
o(e) Boiling points of normal primary alcohols increase with increasing molecular weight.
17. Give the IUPAC name of this compound: CH30CH,CH3
(a) dimethyl ether (b) methoxyethane
(c) methyl ethyl oxide (d) propyl ether
(a) CaHo (b) CaHs (e) none of the above
(c) CGHs (d) CgHh20o 18. Select the IUPAC name for the compound below.
(e) Cas
10. How many actual double bonds does the benzene ring possess?
(a) None, carbon-carbon bonds in benzene are
(b) 1double bond delocalized around the ring HO

(c) 2double bonds

(d) 3double bonds
(a) 2, 4-dimethylpentanoic acid (b) 1,1,3-trimethylbutanoic acid
(e) 4 double bonds (C) 1-hydroxy-2, 4-dimethylpentanone (d) 2-carboxyisohexane
(e) none of these
 Pharmaceutcal Organic Chemistry -| 1.30 Classiflcation, , Nomenclature and
Isome¡r
19.Select the best name for .....
CI

HO
(a) m-chlorobenzoic acid (b) o-chlorobenzaldehyde
(c) p-chlorobenzoate (d) m-chlorosalicylic acid
(e) none of these
20. The compound given below is called

(a) butyl acetate (b) ethyi pentanoate

() propyl pentanoate (d) ethyl butanoate
(e) butylethanoate
21. The compound illustrated below is called

(a) acetamide (b) formyl acetamide

() dimethyl acetate (d) N, N-dimethylfornmamide
(e) dimethylamine
22. Which of the folowing is a type of structural isomerism?
(a) functional group isomerism (b) chain isomerism
() position isomerism (d) all of them
23. The compounds which have same molecular formula but they are different in the
structural formula are called as .....
(a) position isomers (b) molecular isomers
(c) structural isomers (d) optical isomers
24. If the position of functional group is different in its isomers then this isomerism is calle
as...

(a) functional group isomerism (b) position isomerism

(c) chain isomerism (d) all of them
25. Total number of isomers of CoHiy are....
(a) 4 (b) 5
(c) 6 (d) 7
26. Which of the following hydrocarbons does not have isomers?
(a) CcHs4 (b) CGHio
() CaHs (d) CaHg