Naming Organic Compounds

The increasingly large number of organic compounds identified with each passing day, together with the fact that many
of these compounds are isomers of other compounds, requires that a systematic nomenclature system be developed.
Just as each distinct compound has a unique molecular structure which can be designated by a structural formula, each
compound must be given a characteristic and unique name.
As organic chemistry grew and developed, many compounds were given trivial names, which are now commonly used
and recognized. Some examples are:

Name           Methane        Butane       Acetone         Toluene         Acetylene        Ethyl Alcohol

Formula         CH4             C4H10     CH3COCH3      CH3C6H5          C2H2               C2H5OH

Such common names often have their origin in the history of the science and the natural sources of
specific compounds, but the relationship of these names to each other is arbitrary, and no rational or
systematic principles underlay their assignments.

The IUPAC Systematic Approach to Nomenclature

A rational nomenclature system should do at least two things.

First, it should indicate how the carbon atoms of a given compound are bonded together in a characteristic
lattice of chains and rings.

Second, it should identify and locate any functional groups present in the compound. Since hydrogen is such a
common component of organic compounds, its amount and locations can be assumed from the tetravalency of
carbon, and need not be specified in most cases.

The IUPAC nomenclature system is a set of logical rules devised and used by organic chemists to
circumvent problems caused by arbitrary nomenclature. Knowing these rules and given a structural formula,
one should be able to write a unique name for every distinct compound. Likewise, given a IUPAC name, one
should be able  to write a structural formula.

In general, an IUPAC name will have three essential features:

• A root or base indicating a major chain or ring of carbon atoms found in the molecular structure.
• A suffix or other element(s) designating functional groups that may be present in the compound.
• Names of substituent groups, other than hydrogen, that complete the molecular structure.

As an introduction to the IUPAC nomenclature system, we shall first consider compounds that have no
specific functional groups. Such compounds are composed only of carbon and hydrogen atoms bonded
together by sigma bonds (all carbons are sp3 hybridized).

Alkanes
Hydrocarbons having no double or triple bond functional groups are classified as alkanes or
cycloalkanes, depending on whether the carbon atoms of the molecule are arranged only in chains or also in
rings. Although these hydrocarbons have no functional groups, they constitute the framework on which
functional groups are located in other classes of compounds, and provide an ideal starting point for studying
and naming organic compounds. The alkanes and cycloalkanes are also members of a larger class of
compounds referred to as aliphatic. Simply put, aliphatic compounds are compounds that do not incorporate
any aromatic rings in their molecular structure.

The following table lists the IUPAC names assigned to simple continuous-chain alkanes from C-1 to C-10.
A common "ane" suffix identifies these compounds as alkanes. Longer chain alkanes are well known, and their
names may be found in many reference and text books. The names methane through decane should
be memorized, since they constitute the root of many IUPAC names. Fortunately, common numerical prefixes
are used in naming chains of five or more carbon atoms.

Examples of Simple Unbranched Alkanes

Some important behavior trends and terminologies:

(i) The formulas and structures of these alkanes increase uniformly by a CH2 increment.
(ii) A uniform variation of this kind in a series of compounds is called homologous.
(iii) These formulas all fit the CnH2n+2 rule. This is also the highest possible H/C ratio for a stable hydrocarbon.
(iv) Since the H/C ratio in these compounds is at a maximum, we call them saturated (with hydrogen).

Beginning with butane (C4H10), and becoming more numerous with larger alkanes, we note the existence of alkane
isomers. For example, there are five C6H14 isomers, shown below as abbreviated line formulas (A through E):
Although these distinct compounds all have the same molecular formula, only one (A) can be
called hexane. How then are we to name the others?

For the above isomers of hexane the IUPAC names are: (B) 2-methylpentane (C) 3-
methylpentane (D) 2,2- dimethylbutane (E) 2,3-dimethylbutane

The IUPAC system requires first that we have names for simple unbranched chains, as noted
above, and second that we have names for simple alkyl groups that may be attached to the
chains. Examples of some common alkyl groups are given in the following table. Note that the
"ane" suffix is replaced by "yl" in naming groups. The symbol R is used to designate a generic
(unspecified) alkyl group.

IUPAC Rules for Alkane Nomenclature

1. Find and name the longest continuous carbon chain.
2. Identify and name groups attached to this chain.
3. Number the chain consecutively, starting at the end nearest a substituent group.
4. Designate the location of each substituent group by an appropriate number and name.
5. Assemble the name, listing groups in alphabetical order using the full name (e.g. cyclopropyl before isobutyl).

The prefixes di, tri, tetra etc., used to designate several groups of the same kind, are not considered when
alphabetizing. Halogen substituents are easily accommodated, using the names: fluoro (F-), chloro (Cl-), bromo (Br-)
and iodo (I-). For example, (CH3)2CHCH2CH2Br would be named 1-bromo-3-methylbutane. If the halogen is bonded to a
simple alkyl group an alternative "alkyl halide" name may be used. Thus, C2H5Cl may be named chloroethane (no
locator number is needed for a two carbon chain) or ethyl chloride. Halogenated alkyl substituents such as
bromomethyl, BrCH2–, and trichloromethyl, CCl3–, may be listed and are alphabetized according to their full names.

Practice Problems
Illustration 1. CH3(CH2)2CH(CH3)CH2CH3

When viewing a condensed formula of this kind, one must recognize that parentheses are used both
to identify repeating units, such as the two methylene groups on the left side, and substituents, such
as the methyl group on the right side. This formula is elaborated and named as follows:

The condensed formula is expanded on the left. By inspection, the longest chain is seen to consist of
six carbons, so the root name of this compound will be hexane. A single methyl substituent (colored
red) is present, so this compound is a methylhexane. The location of the methyl group must be
specified, since there are two possible isomers of this kind. Note that if the methyl group were
located at the end of the chain, the longest chain would have seven carbons and the root name
would be heptane not hexane. To locate the substituent the hexane chain must be numbered
consecutively, starting from the end nearest a substituent. In this case it is the right end of the chain,
and the methyl group is located on carbon #3. The IUPAC name is thus: 3-methylhexane

Illustration 2. (CH3)2C(C2H5)2

Again, the condensed formula is expanded on the left, the longest chain is identified (five carbons)
and substituents are located and named. Because of the symmetrical substitution pattern, it does not
matter at which end of the chain the numbering begins.
When two or more identical substituents are present in a molecule, a numerical prefix (di, tri, tetra etc.) is used to
designate their number. However, each substituent must be given an identifying location number. Thus, the above
compound is correctly named: 3,3-dimethylpentane. Note that the isomer (CH3)2CHCH2CH(CH3)2 would be named 2,4-
dimethylpentane.

Illustration 3. (CH3)2CHCH2CH(C2H5)C(CH3)3

This example illustrates some sub-rules of the IUPAC system that must be used in complex cases. The expanded and line
formulas are shown below.
Sub-Rules for IUPAC Nomenclature
1. If there are two or more longest chains of equal length, the one having the largest number of substituents is chosen.
2. If both ends of the root chain have equidistant substituents:
      (i) begin numbering at the end nearest a third substituent, if one is present.
      (ii) begin numbering at the end nearest the first cited group (alphabetical order).

In this case several six-carbon chains can be identified. Some (colored blue) are identical in that they
have the same number, kind and location of substituents. The IUPAC name derived from these chains
will not change. Some (colored magenta) differ in the number, kind and location of substituents, and
will result in a different name. From rule 1 above the blue chain is chosen, and it will be numbered
from the right hand end by application of rule (i). Remembering the alphabetical priority, we assign
the following IUPAC name: 3-ethyl2,2,5-trimethylhexane.
 
Illustration 4.

The following are additional examples of more complex structures and their names. The formula on
the right shows how a complex substituent may be given a supplementary numbering. In such cases
the full substituent name is displayed within parenthesis and is alphabetized including numerical
prefixes such as 'di'.
Cycloalkanes
Cycloalkanes have one or more rings of carbon atoms. The simplest examples of this class consist of
a single, unsubstituted carbon ring, and these form a homologous series similar to the unbranched
alkanes. The IUPAC names of the first five members of this series are given in the following table.
The last (yellow shaded) column gives the general formula for a cycloalkane of any size. If a simple
unbranched alkane is converted to a cycloalkane two hydrogen atoms, one from each end of the
chain, must be lost. Hence the general formula for a cycloalkane composed of n carbons is CnH2n.
Although a cycloalkane has two fewer hydrogens than the equivalent alkane, each carbon is bonded
to four other atoms so such compounds are still considered to be saturated with hydrogen.

Examples of Simple Cycloalkanes

Substituted cycloalkanes are named in a fashion very similar to that used for naming branched
alkanes. The chief difference in the rules and procedures occurs in the numbering system. Since all
the carbons of a ring are equivalent (a ring has no ends like a chain does), the numbering starts at a
substituted ring atom.
 
IUPAC Rules for Cycloalkane Nomenclature
1. For a monosubstituted cycloalkane the ring supplies the root name (table above) and the
substituent group is named as usual. A location number is unnecessary.
2. If the alkyl substituent is large and/or complex, the ring may be named as a substituent group on
an alkane.
3. If two different substituents are present on the ring, they are listed in alphabetical order, and the
first cited substituent is assigned to carbon #1. The numbering of ring carbons then continues in a
direction (clockwise or counter-clockwise) that affords the second substituent the lower possible
location number.
4. If several substituents are present on the ring, they are listed in alphabetical order.  Location
numbers are assigned to the substituents so that one of them is at carbon #1 and the other locations
have the lowest possible numbers, counting in either a clockwise or counter-clockwise direction.
5. The name is assembled, listing groups in alphabetical order and giving each group (if there are
two or more) a location number. The prefixes di, tri, tetra etc., used to designate several groups of
the same kind, are not considered when alphabetizing.

Small rings, such as three and four membered rings, have significant angle strain resulting from the
distortion of the sp3 carbon bond angles from the ideal 109.5º to 60º and 90º respectively. This
angle strain often enhances the chemical reactivity of such compounds, leading to ring cleavage
products. It is also important to recognize that, with the exception of cyclopropane, cycloalkyl rings
are not planar (flat).

Examples

The following two cases provide examples of monosubstituted cycloalkanes.

In the first case, on the left, we see a seven-carbon ring bearing a C4H9 substituent group. Earlier
this substituent was identified as the tert-butyl group, so a name based on the cycloheptane root is
easily written. In the second case, on the right, a four-carbon ring is attached to a branched six-
carbon alkyl group. This C6H13 group could be named "isohexyl", but a better approach is to name
this compound as a disubstituted pentane. The four-membered ring substituent is called a cyclobutyl
group.

More highly substituted cycloalkanes are named in a similar fashion, but care must be taken in
numbering the ring.

In the example on the left, there are three substituents on the six-membered ring and two are on the
same carbon. The disubstituted carbon becomes #1 because the total locator numbers are thereby
kept to a minimum. The ethyl substituent is then located on carbon #3 (counter-clockwise
numbering), not #5 (clockwise numbering). Alphabetical listing of the substituents then leads to the
name "3-ethyl-1,1-dimethylcyclohexane", being careful to assign a locator number to each
substituent. Note that if only one methyl substituent was present, the alphabetical citation rule would
assign the ethyl group to carbon #1 and the methyl to #3. The second example, on the left, has five
substituents, and the numbering is assigned so that the first, second and third arbitrarily chosen
substituents have the lowest possible numbers (1,1 & 2 in this case).

There’s a little bit of hand waving going on here because stereochemistry is not being accounted
for. These just illustrate the hand waiving I alluded to. We will discuss an alternative system in class
which specifies the absolute configuration of substituted carbon atoms may also be used. This
system, known as the Cahn-Ingold-Prelog rules, uses and elaborates the priority rules developed
earlier (E and Z system – discussed in text and class). Below is for illustration, we will usually avoid
cis and trans (gets round the problem of name a reference group).

When one substituent and one hydrogen atom are attached at each of more than two positions of
a monocycle, the steric relations of the substituents may be expressed by first identifying a reference
substituent (labeled r) followed by a hyphen and the substituent locator number and name. The
relative configuration of other substituents are then reported as cis (c) or trans (t) to the reference
substituent.
When two different substituents are attached at the same position of a monocycle, then the lowest-
numbered substituent named as a suffix is selected as reference group. If none of the substituents is named
as a suffix, then that substituent of the pair of substituents having the lowest number, and which is preferred
by the sequence rule, is chosen as the reference group. The relationship of the sequence-rule-preferred
substituent at geminally substituted positions, relative to the reference group, is cited as c- or t-, as
appropriate.

Alkenes & Alkynes

Alkenes and alkynes are hydrocarbons which respectively have carbon-carbon double bond and carbon-carbon
triple bond functional groups. The molecular formulas of these unsaturated hydrocarbons reflect the multiple
bonding of the functional groups:

Alkane R–CH2–CH2–R CnH2n+2 This is the maximum H/C ratio for a given number of carbon atoms.
Alkene R–CH=CH–R CnH2n Each double bond reduces the number of hydrogen atoms by 2.
Alkyne  R–C≡C–R CnH2n-2 Each triple bond reduces the number of hydrogen atoms by 4.

As noted earlier in the Analysis of Molecular Formulas section, the molecular formula of a
hydrocarbon provides information about the possible structural types it may represent. For example, consider
compounds having the formula C5H8. The formula of the five-carbon alkane pentane is C5H12 so the
difference in hydrogen content is 4. This difference suggests such compounds may have a triple bond, two
double bonds, a ring plus a double bond, or two rings. Some examples are shown here, and there are at least
fourteen others!

IUPAC Rules for Alkene and Cycloalkene Nomenclature

1. The ene suffix (ending) indicates an alkene or cycloalkene.
2. The longest chain chosen for the root name must include both carbon atoms of the double bond.
3. The root chain must be numbered from the end nearest a double bond carbon atom. If the double
bond is in the center of the chain, the nearest substituent rule is used to determine the end where
numbering starts.
4. The smaller of the two numbers designating the carbon atoms of the double bond is used as the
double bond locator. If more than one double bond is present the compound is named as a diene,
triene or equivalent prefix indicating the number of double bonds, and each double bond is assigned
a locator number.
5. In cycloalkenes the double bond carbons are assigned ring locations #1 and #2. Which of the two
is #1 may be determined by the nearest substituent rule.
6. Substituent groups containing double bonds are:
                                       H2C=CH– Vinyl group
                                       H2C=CH–CH2– Allyl group
 
IUPAC Rules for Alkyne Nomenclature
1. The yne suffix (ending) indicates an alkyne or cycloalkyne.
2. The longest chain chosen for the root name must include both carbon atoms of the triple bond.
3. The root chain must be numbered from the end nearest a triple bond carbon atom. If the triple
bond is in the center of the chain, the nearest substituent rule is used to determine the end where
numbering starts.
4. The smaller of the two numbers designating the carbon atoms of the triple bond is used as the
triple bond locator.
5. If several multiple bonds are present, each must be assigned a locator number. Double bonds
precede triple bonds in the IUPAC name, but the chain is numbered from the end nearest a multiple
bond, regardless of its nature.
6. Because the triple bond is linear, it can only be accommodated in rings larger than ten carbons. In
simple cycloalkynes the triple bond carbons are assigned ring locations #1 and #2. Which of the two
is #1 may be determined by the nearest substituent rule.
7. Substituent groups containing triple bonds are:
                              HC≡C– Ethynyl group
                              HC≡CH–CH2– Propargyl group
Examples
Illustration 1 (CH3)2C=CHCH2C(CH3)3                                                           
 Illustration 2 (CH3CH2CH2)2C=CH2

Both these compounds have double bonds, making them alkenes. In example (1) the longest chain
consists of six carbons, so the root name of this compound will be hexene. Three methyl substituents
(colored red) are present. Numbering the six-carbon chain begins at the end nearest the double bond
(the left end), so the methyl groups are located on carbons 2 & 5. The IUPAC name is therefore:
2,5,5-trimethyl-2-hexene.
In example (2) the longest chain incorporating both carbon atoms of the double bond has a length of
five. There is a seven-carbon chain, but it contains only one of the double bond carbon atoms.
Consequently, the root name of this compound will be pentene. There is a propyl substituent on the
inside double bond carbon atom (#2), so the IUPAC name is: 2-propyl-1-pentene.

Illustration 3 (C2H5)2C=CHCH(CH3)2                                      
Illustration 4 CH2=C(CH3)CH(CH3)C(C2H5)=CH2

The next two examples illustrate additional features of chain numbering. As customary, the root
chain is colored blue and substituents are red
The double bond in example (3) is located in the center of a six-carbon chain. The double bond
would therefore have a locator number of 3 regardless of the end chosen to begin numbering. The
right hand end is selected because it gives the lowest first-substituent number (2 for the methyl as
compared with 3 for the ethyl if numbering were started from the left). The IUPAC name is assigned
as shown.
Example (4) is a diene (two double bonds). Both double bonds must be contained in the longest
chain, which is therefore five- rather than six-carbons in length. The second and fourth carbons of
this 1,4-pentadiene are both substituted, so the numbering begins at the end nearest the
alphabetically first-cited substituent (the ethyl group).
These examples include rings of carbon atoms as well as some carbon-carbon triple bonds. Example
(6) is best named as an alkyne bearing a cyclobutyl substituent. Example (7) is simply a ten-
membered ring containing both a double and a triple bond. The double bond is cited first in the
IUPAC name, so numbering begins with those two carbons in the direction that gives the triple bond
carbons the lowest locator numbers.
Because of the linear geometry of a triple bond, a-ten membered ring is the smallest ring in which
this functional group is easily accommodated. Example (8) is a cyclooctatriene (three double bonds in
an eight-membered ring). The numbering must begin with one of the end carbons of the conjugated
diene moiety (adjacent double bonds), because in this way the double bond carbon atoms are
assigned the smallest possible locator numbers (1, 2, 3, 4, 6 & 7). Of the two ways in which this can
be done, we choose the one that gives the vinyl substituent the lower number.
The last three examples, (9), (10) & (11), illustrate some fine points of the nomenclature rules.

Sub-Rules for IUPAC Nomenclature

The root chain is that which contains the maximum number of multiple bonds.
• If more than one such chain is found, the longest is chosen as the root.
• If the chains have equal length the one with the most double bonds is chosen.
The first two acyclic cases are branched chains containing several multiple bonds. Example (9)
has two possible seven-carbon chains, each having three multiple bonds. The one selected has
three double bonds and the triple bond becomes a substituent group. In example (10) we find
a six-carbon chain containing two double bonds, and a seven-carbon chain with a double and a
triple bond. The latter becomes the root chain and the second double bond is a vinyl
substituent on that chain. The last example (11) shows that in numbering a cycloalkene one
must first consider substituents on the double bond in assigning sites #1 and #2. Here the
double bond carbon atom to which the ethyl group is attached becomes #1 and the other
carbon of the double bond is necessarily carbon #2. Sometimes this results in other
substituents having high locator numbers, as does bromine in this case.