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Organic Chemistry Text Book (CHEM 3401 and 3402)

4.1 Alkane Introduction and Nomenclature

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 underly 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).


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 

Name Molecular
Isomers   Name Molecular
methane CH4 CH4 1   hexane C6H14 CH3(CH2)4CH3 5
ethane C2H6 CH3CH3 1   heptane C7H16 CH3(CH2)5CH3 9
propane C3H8 CH3CH2CH3 1   octane C8H18 CH3(CH2)6CH3 18
butane C4H10 CH3CH2CH2CH3 2   nonane C9H20 CH3(CH2)7CH3 35
pentane C5H12 CH3(CH2)3CH3 3   decane C10H22 CH3(CH2)8CH3 75


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?

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.

Group   CH3–   C2H5–   CH3CH2CH2–   (CH3)2CH–   CH3CH2CH2CH2–   (CH3)2CHCH2–   CH3CH2CH(CH3)–   (CH3)3C–   R– 
Name   Methyl  Ethyl  Propyl  Isopropyl  Butyl  Isobutyl  sec-Butyl  tert-Butyl    Alkyl  


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.


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

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.


      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 

Name  Cyclopropane Cyclobutane Cyclopentane Cyclohexane Cycloheptane Cycloalkane
C3H6 C4H8 C5H10 C6H12 C7H14 CnH2n


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.


For examples of how these rules are used in naming substituted cycloalkanes   .

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). The three dimensional shapes assumed by the common rings (especially cyclohexane and larger rings) are described and discussed in the Conformational Analysis Section.


Hydrocarbons having more than one ring are common, and are referred to as bicyclic (two rings), tricyclic (three rings) and in general, polycyclic compounds. The molecular formulas of such compounds have H/C ratios that decrease with the number of rings. In general, for a hydrocarbon composed of n carbon atoms associated with m rings the formula is: CnH(2n + 2 - 2m). The structural relationship of rings in a polycyclic compound can vary. They may be separate and independent, or they may share one or two common atoms. Some examples of these possible arrangements are shown in the following table.


Examples of Isomeric C8H14 Bicycloalkanes 

Isolated Rings Spiro Rings Fused Rings Bridged Rings
No common atoms One common atom One common bond Two common atoms