REPLACEMENT

NOMENCLATURE OF
HETEROCYCLES

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 Replacement Nomenclature of Heterocycles
• The replacement system of nomenclature is based on the
premise that heterocyclic compounds are derived by
replacing a carbon in carbocyclic compounds with a
heteroatom.
• Therefore the rules of replacement nomenclature are
similar to those applied for naming carbocyclic
compounds.
• The heterocyclic systems commonly named based on
replacement nomenclature are:
 Monocyclic heterocycles
 Spiroheterocycles
 Bridged heterocycles
• We shall illustrate this sense of nomenclature for
monocyclic heterocycles and spiroheterocycles. 2
 Replacement Nomenclature
Rules for Monocyclic Heterocycles
• In replacement nomenclature, the heterocycle's name is
derived by adding the name of the carbocycle to a prefix
that denotes the heteroatom.
• The parent name of the heterocycle is the name of the
carbocycle obtained by replacing the heteroatom(s) in
the heterocycle with CH2, CH or C based on the valence
of heteroatom(s) and applying the IUPAC rules.
• The prefixes, "aza", "oxa", and "thia" are used for a
nitrogen, an oxygen and a sulfur ring atom, respectively.
• The parent heterocyclic ring is numbered starting from
the more prior heteroatom in a direction that assigns
other heteroatoms the lowest possible number. 3
 Replacement Nomenclature
Monocyclic Heterocycles
• Below are some of the nitrogen heterocycles we have
previously named using the Hantzsch-Widman
nomenclature. See their names based on replacement
nomenclature.

• Below are some of the simple oxygen heterocycles

based on the replacement nomenclature and their
Hantzsch-Widman names.

• Note that these names are acceptable IUPAC names. 4

 Replacement Nomenclature
Substituted Monocyclic Heterocycles
• For saturated substituted nitrogen heterocycles, the
location of the substituent is determined by assigning
the heteroatom the lowest possible number.

• For more complex monocyclic heterocycles with

multiple heteroatoms, the sequence and numbering of
the heteroatoms follow the rules of systematic
nomenclature. 5
 Replacement Nomenclature
Worked Examples
• Name the following heterocycles using replacement
nomenclature

• Note that the prior heteroatom takes precedence in the

numbering and numbering proceeds in the direction that
gives the other heteroatoms the lowest locant.. 6
 Replacement Nomenclature
Spiroheterocycles
• Spiroheterocycles have two rings fused at a common
point and the common atom which is quaternary is
designated as a spiro atom.
• Spiroheterocycles are classified according to the number
of spiro atoms as monospiro-, dispiro-, trispiro- ring
systems.
• Spiroheterocycles are prevalent in nature and many
serve important biological functions as pheromones of
diverse insect species.

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 Replacement Nomenclature
Spiroheterocycles
• The parent name of spiroheterocycles with one spiro
atom is derived by prefixing spiro to the name of an
alkane with the same number of carbon atoms.
• The number of atoms in each ring is indicated with
arabic numbers separated by a full stop and enclosed in
a square bracket in ascending order and are placed
between spiro prefix and the name of the hydrocarbon.
• The heteroatoms are indicated by their prefixes
preceded by their positions.

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 Replacement Nomenclature
Spiroheterocycles
• The numbering in the spiroheterocycle starts from the
ring atom of the smaller ring (if rings are of unequal
size) attached to the spiro atom and proceeds first
around the smaller ring and then around the larger ring
through the spiro atom.
• The numbering is irrespective of whether the larger ring
contains the heteroatom. The heteroatoms are assigned
the lowest possible number locants.

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 Replacement Nomenclature
Spiroheterocycles
• The heterocyclic ring is preferred over the carbocyclic
ring of the same size. If both rings are heterocyclic of
equal size, preference in numbering is given to the ring
with the heteroatom of higher preference.
• If unsaturation is present in a ring, the numbering
remains the same but the direction around the ring is
such that the multiple bond is given as low a number as
possible. However, the heteroatom is preferred over the
multiple bond.

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 Practice Questions
Nomenclature of Heterocycles
Provide the names of the following heterocycles based on
replacement nomenclature.

Draw the structures corresponding to the following

replacement names.
(i) Oxacyclohexa-2,4-diene
(ii) 1-thia-3-azapent-3-ene 13