8.5 Nomenclature of Organic Compounds

Organic chemistry deals with millions of compounds. In order to clearly identify them, a systematic method of naming has been developed and is known as the IUPAC (International Union of Pure and Applied Chemistry) system of nomenclature. In this systematic nomenclature, the names are correlated with the structure such that the reader or listener can deduce the structure from the name.

Before the IUPAC system of nomenclature, however, organic compounds were assigned names based on their origin or certain properties. For instance, citric acid is named so because it is found in citrus fruits and the acid found in red ant is named formic acid since the Latin word for ant is formica. These names are traditional and are considered as trivial or common names. Some common names are followed even today. For example, Buckminsterfullerene is a common name given to the newly discovered \(\mathrm{C}_{60}\) cluster (a form of carbon) noting its structural similarity to the geodesic domes popularised by the famous architect R. Buckminster Fuller. Common names are useful and in many cases indispensable, particularly when the alternative systematic names are lengthy and complicated. Common names of some organic compounds are given in Table 8.1.

The IUPAC System of Nomenclature

A systematic name of an organic compound is generally derived by identifying the parent hydrocarbon and the functional group(s) attached to it. See the example given below.

By further using prefixes and suffixes, the parent name can be modified to obtain the actual name. Compounds containing carbon and hydrogen only are called hydrocarbons. A hydrocarbon is termed saturated if it contains only carbon-carbon single bonds. The IUPAC name for a homologous series of such compounds is alkane. Paraffin (Latin: little affinity) was the earlier name given to these compounds. Unsaturated hydrocarbons are those, which contain at least one carbon-carbon double or triple bond.

IUPAC Nomenclature of Alkanes

Straight chain hydrocarbons: The names of such compounds are based on their chain structure, and end with suffix ‘-ane’ and carry a prefix indicating the number of carbon atoms present in the chain (except from \(\mathrm{CH}_4\) to \(\mathrm{C}_4 \mathrm{H}_{10}\), where the prefixes are derived from trivial names). The IUPAC names of some straight chain saturated hydrocarbons are given in Table 8.2. The alkanes in Table 8.2 differ from each other by merely the number of \(-\mathrm{CH}_2\) groups in the chain. They are homologues of alkane series.

Branched chain hydrocarbons: In a branched chain compound small chains of carbon atoms are attached at one or more carbon atoms of the parent chain. The small carbon chains (branches) are called alkyl groups. For example:

In order to name such compounds, the names of alkyl groups are prefixed to the name of parent alkane. An alkyl group is derived from a saturated hydrocarbon by removing a hydrogen atom from carbon. Thus, \(\mathrm{CH}_4\) becomes \(-\mathrm{CH}_3\) and is called methyl group. An alkyl group is named by substituting ‘ \(y l\) ‘ for ‘ane‘ in the corresponding alkane. Some alkyl groups are listed in Table 8.3.

Abbreviations are used for some alkyl groups. For example, methyl is abbreviated as Me, ethyl as Et, propyl as Pr and butyl as Bu. The alkyl groups can be branched also. Thus, propyl and butyl groups can have branched structures as shown below.

Common branched groups have specific trivial names. For example, the propyl groups can either be n-propyl group or isopropyl group. The branched butyl groups are called sec-butyl, isobutyl and tert-butyl group. We also encounter the structural unit, \(-\mathrm{CH}_2 \mathrm{C}\left(\mathrm{CH}_3\right)_3\), which is called neopentyl group.

Nomenclature of branched chain alkanes: We encounter a number of branched chain alkanes. The rules for naming them are given below.

1. First of all, the longest carbon chain in the molecule is identified. In the example (I) given below, the longest chain has nine carbons and it is considered as the parent or root chain. Selection of parent chain as shown in (II) is not correct because it has only eight carbons.

2. The carbon atoms of the parent chain are numbered to identify the parent alkane and to locate the positions of the carbon atoms at which branching takes place due to the substitution of alkyl group in place of hydrogen atoms. The numbering is done in such a way that the branched carbon atoms get the lowest possible numbers. Thus, the numbering in the above example should be from left to right (branching at carbon atoms 2 and 6) and not from right to left (giving numbers 4 and 8 to the carbon atoms at which branches are attached).

3. The names of alkyl groups attached as a branch are then prefixed to the name of the parent alkane and position of the substituents is indicated by the appropriate numbers. If different alkyl groups are present, they are listed in alphabetical order. Thus, name for the compound shown above is: 6-ethyl-2methylnonane. [Note: the numbers are separated from the groups by hyphens and there is no break between methyl and nonane.]

4. If two or more identical substituent groups are present then the numbers are separated by commas. The names of identical substituents are not repeated, instead prefixes such as di (for 2), tri (for 3), tetra (for 4), penta (for 5), hexa (for 6 ) etc. are used. While writing the name of the substituents in alphabetical order, these prefixes, however, are not considered. Thus, the following compounds are named as:

5. If the two substituents are found in equivalent positions, the lower number is given to the one coming first in the alphabetical listing. Thus, the following compound is 3-ethyl-6-methyloctane and not 6-ethyl-3-methyloctane.

6. The branched alkyl groups can be named by following the above mentioned procedures. However, the carbon atom of the branch that attaches to the root alkane is numbered 1 as exemplified below.

The name of such branched chain alkyl group is placed in parenthesis while naming the compound. While writing the trivial names of substituents’ in alphabetical order, the prefixes iso– and neo- are considered to be the part of the fundamental name of alkyl group. The prefixes sec- and tert- are not considered to be the part of the fundamental name. The use of iso and related common prefixes for naming alkyl groups is also allowed by the IUPAC nomenclature as long as these are not further substituted. In multi-substituted compounds, the following rules may also be remembered:

• If there happens to be two chains of equal size, then that chain is to be selected which contains more number of side chains.
• After selection of the chain, numbering is to be done from the end closer to the substituent.

Cyclic Compounds: A saturated monocyclic compound is named by prefixing ‘cyclo‘ to the corresponding straight chain alkane. If side chains are present, then the rules given above are applied. Names of some cyclic compounds are given below.

Example 8.7: Structures and IUPAC names of some hydrocarbons are given below. Explain why the names given in the parentheses are incorrect.

Answer: (a) Lowest locant number, 2,5,6 is lower than 3,5,7, (b) substituents are in equivalent position; lower number is given to the one that comes first in the name according to alphabetical order.

Nomenclature of Organic Compounds having Functional Group(s)

A functional group, as defined earlier, is an atom or a group of atoms bonded together in a unique manner which is usually the site of chemical reactivity in an organic molecule. Compounds having the same functional group undergo similar reactions. For example, \(\mathrm{CH}_3 \mathrm{OH}, \mathrm{CH}_3 \mathrm{CH}_2 \mathrm{OH}\), and \(\left(\mathrm{CH}_3\right)_2 \mathrm{CHOH}-\) all having – \(\mathrm{OH}\) functional group liberate hydrogen on reaction with sodium metal. The presence of functional groups enables systematisation of organic compounds into different classes. Examples of some functional groups with their prefixes and suffixes along with some examples of organic compounds possessing these are given in Table 8.4.

First of all, the functional group present in the molecule is identified which determines the choice of appropriate suffix. The longest chain of carbon atoms containing the functional group is numbered in such a way that the functional group is attached at the carbon atom possessing lowest possible number in the chain. By using the suffix as given in Table 8.4, the name of the compound is arrived at.

In the case of polyfunctional compounds, one of the functional groups is chosen as the principal functional group and the compound is then named on that basis. The remaining functional groups, which are subordinate functional groups, are named as substituents using the appropriate prefixes. The choice of principal functional group is made on the basis of order of preference. The order of decreasing priority for some functional groups is:
\(-\mathrm{COOH},-\mathrm{SO}_3 \mathrm{H},-\mathrm{COOR} \text { (R=alkyl group), COCl, }\) \(-\mathrm{CONH}_2,-\mathrm{CN},-\mathrm{HC}=\mathrm{O},>\mathrm{C}=\mathrm{O},-\mathrm{OH},-\mathrm{NH}_2,>\mathrm{C}=\mathrm{C}<, \quad-\mathrm{C} \equiv \mathrm{C}-.\)

The \(-\mathrm{R}, \mathrm{C}_6 \mathrm{H}_5{ }{-}\), halogens \((\mathrm{F}, \mathrm{Cl}, \mathrm{Br}, \mathrm{I}),-\mathrm{NO}_2\), alkoxy (-OR) etc. are always prefix substituents. Thus, a compound containing both an alcohol and a keto group is named as hydroxyalkanone since the keto group is preferred to the hydroxyl group.

For example, \(\mathrm{HOCH}_2\left(\mathrm{CH}_2\right)_3 \mathrm{CH}_2 \mathrm{COCH}_3\) will be named as 7-hydroxyheptan-2-one and not as 2-oxoheptan-7-ol. Similarly, \(\mathrm{BrCH}_2 \mathrm{CH}=\mathrm{CH}_2\) is named as 3-bromoprop-1-ene and not 1-bromoprop-2-ene.

If more than one functional group of the same type are present, their number is indicated by adding di, tri, etc. before the class suffix. In such cases the full name of the parent alkane is written before the class suffix. For example \(\mathrm{CH}_2(\mathrm{OH}) \mathrm{CH}_2(\mathrm{OH})\) is named as ethane-1,2-diol. However, the ending – ne of the parent alkane is dropped in the case of compounds having more than one double or triple bond; for example, \(\mathrm{CH}_2=\mathrm{CH}-\mathrm{CH}=\mathrm{CH}_2\) is named as buta-1,3-diene.

Example 8.8: Write the IUPAC names of the compounds i-iv from their given structures.

Answer:

• The functional group present is an alcohol \((\mathrm{OH})\). Hence the suffix is ‘ \(-\mathrm{ol}\) ‘.
• The longest chain containing \(-\mathrm{OH}\) has eight carbon atoms. Hence the corresponding saturated hydrocarbon is octane.
• The \(-\mathrm{OH}\) is on carbon atom 3 . In addition, a methyl group is attached at \(6^{\text {th }}\) carbon.
  Hence, the systematic name of this compound is 6-Methyloctan-3-ol.

(ii)

Answer: The functional group present is ketone \((>\mathrm{C}=\mathrm{O})\), hence suffix ‘-one’. Presence of two keto groups is indicated by ‘di’, hence suffix becomes ‘dione’. The two keto groups are at carbons 2 and 4 . The longest chain contains 6 carbon atoms, hence, parent hydrocarbon is hexane. Thus, the systematic name is Hexane-2,4-dione.

(iii)

Answer: Here, two functional groups namely ketone and carboxylic acid are present. The principal functional group is the carboxylic acid group; hence the parent chain will be suffixed with ‘oic’ acid. Numbering of the chain starts from carbon of – \(\mathrm{COOH}\) functional group. The keto group in the chain at carbon 5 is indicated by ‘oxo’. The longest chain including the principal functional group has 6 carbon atoms; hence the parent hydrocarbon is hexane. The compound is, therefore, named as 5-Oxohexanoic acid.

(iv) 

The two \(\mathrm{C}=\mathrm{C}\) functional groups are present at carbon atoms 1 and 3 , while the \(\mathrm{C} \equiv \mathrm{C}\) functional group is present at carbon 5 . These groups are indicated by suffixes ‘diene’ and ‘yne’ respectively. The longest chain containing the functional groups has 6 carbon atoms; hence the parent hydrocarbon is hexane. The name of compound, therefore, is Hexa-1,3dien-5-yne.

Example 8.9: Derive the structure of (i) 2-Chlorohexane, (ii) Pent-4-en-2-ol, (iii) 3- Nitrocyclohexene, (iv) Cyclohex-2-en-1-ol, (v) 6-Hydroxyheptanal.

Answer: (i) ‘hexane’ indicates the presence of 6 carbon atoms in the chain. The functional group chloro is present at carbon 2. Hence, the structure of the compound is \(\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{CH}(\mathrm{Cl}) \mathrm{CH}_3\).

(ii) ‘pent’ indicates that parent hydrocarbon contains 5 carbon atoms in the chain. ‘en’ and ‘ol’ correspond to the functional groups \(\mathrm{C}=\mathrm{C}\) and \(-\mathrm{OH}\) at carbon atoms 4 and 2 respectively. Thus, the structure is
\(
\mathrm{CH}_2=\mathrm{CHCH}_2 \mathrm{CH}(\mathrm{OH}) \mathrm{CH}_3 \text {. }
\)

(iii) Six membered ring containing a carbon-carbon double bond is implied by cyclohexene, which is numbered as shown in (I). The prefix 3-nitro means that a nitro group is present on \(\mathrm{C}-3\). Thus, complete structural formula of the compound is (II). Double bond is suffixed functional group whereas \(\mathrm{NO}_2\) is prefixed functional group therefore double bond gets preference over \(-\mathrm{NO}_2\) group:

(iv) ‘1-ol’ means that a \(-\mathrm{OH}\) group is present at \(\mathrm{C}-1 . \mathrm{OH}\) is suffixed functional group and gets preference over \(\mathrm{C}=\mathrm{C}\) bond. Thus the structure is as shown in (II):

(v) ‘heptanal’ indicates the compound to be an aldehyde containing 7 carbon atoms in the parent chain. The ‘ 6 -hydroxy’ indicates that – \(\mathrm{OH}\) group is present at carbon 6 . Thus, the structural formula of the compound is: \(\mathrm{CH}_3 \mathrm{CH}(\mathrm{OH})\) \(\mathrm{CH}_2 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{CHO}\). Carbon atom of \(\mathrm{CHO}\) group is included while numbering the carbon chain.

Nomenclature of Substituted Benzene Compounds

For IUPAC nomenclature of substituted benzene compounds, the substituent is placed as prefix to the word benzene as shown in the following examples. However, common names (written in bracket below) of many substituted benzene compounds are also universally used. 

If benzene ring is disubstituted, the position of substituents is defined by numbering the carbon atoms of the ring such that the substituents are located at the lowest numbers possible. For example, the compound(b) is named as 1,3-dibromobenzene and not as 1,5-dibromobenzene.

In the trivial system of nomenclature the terms ortho \((o)\), meta \((\mathrm{m})\) and para \((p)\) are used as prefixes to indicate the relative positions 1,\(2 ; 1,3\) and 1,4 respectively. Thus, 1,3-dibromobenzene (b) is named as m-dibromobenzene (meta is abbreviated as \(\mathrm{m}\)-) and the other isomers of dibromobenzene 1,2-(a) and 1,4-(c), are named as ortho (or just \(o\)-) and para (or just \(p\)-)-dibromobenzene, respectively.

For tri – or higher substituted benzene derivatives, these prefixes cannot be used and the compounds are named by identifying substituent positions on the ring by following the lowest locant rule. In some cases, common name of benzene derivatives is taken as the base compound.

Substituent of the base compound is assigned number 1 and then the direction of numbering is chosen such that the next substituent gets the lowest number. The substituents appear in the name in alphabetical order. Some examples are given below.

When a benzene ring is attached to an alkane with a functional group, it is considered as substituent, instead of a parent. The name for benzene as substituent is phenyl \(\left(\mathrm{C}_6 \mathrm{H}_5-\right.\), also abbreviated as \(\mathrm{Ph}\) ).

Example 8.10: Write the structural formula of:
(a) o-Ethylanisole, (b) p-Nitroaniline,
(c) 2,3-Dibromo-1-phenylpentane,
(d) 4-Ethyl-1-fluoro-2-nitrobenzene.

Answer: