3.

Organic Compounds:
Alkanes and Cycloalkanes
 Classification of Organic Compounds
 Organic compounds are classified into different types based
on the kinds of functional groups present in its structure
 A functional group is an atom or groups of atoms that
determine the types of chemical reactions that the compound
participates in.
 For example, the double bonds in simple and complex
alkenes react with bromine in the same way

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Types of Functional Groups: Multiple
Carbon–Carbon Bonds
 Alkenes have a
C=C double bond
 Alkynes have a
CC triple bond
 In Arenes or
aromatic
hydrocarbons, the
functional group is
the benzene ring

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Functional Groups with Carbon Singly Bonded
to an Electronegative Atom
 Alkyl halide: C bonded to halogen (C-X)
 Alcohol: C (part of aliphatic group) bonded O of a
hydroxyl group (C-OH)
 Phenol: C (part of aromatic group) bonded O of a
hydroxyl group (C-OH)
 Ether: Two C’s bonded to the same O (C-O-C)
 Amine: C bonded to N (C-N)
 Thiol: C bonded to SH group (C-SH)
 Thioether: Two C’s bonded to same S (C-S-C)
 Bonds are polar, with partial positive charge on C (+)
and partial negative charge () on electronegative atom

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Groups with a Carbon–Oxygen Double Bond
(Carbonyl Groups)
 Aldehyde: one hydrogen bonded to C=O
 Ketone: two C’s bonded to the C=O
 Carboxylic acid: OH bonded to the C=O
 Ester: C-O bonded to the C=O
 Amide: C-N bonded to the C=O
 Acid chloride: Cl bonded to the C=O
 Carbonyl C has partial positive charge (+)
 Carbonyl O has partial negative charge (-).

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3.2 Alkanes and Alkane Isomers
 Alkanes: Compounds with C-C single bonds and C-H bonds only (no
functional groups)
 The general molecular formula of an alkane with n C atoms is CnH2n+2
 When n  4, more than one structural formula can be drawn for the same
molecular formula, CnH2n+2
 Compounds with the same molecular formula but with different structural
formulas are called structural isomers or constitutional isomers.
 Structural isomers have different physical properties (Boiling points, melting
points, densities etc.)
 Alkanes are called saturated hydrocarbons because they are saturated
with hydrogen (no more can be added
 Alkanes, Alkenes, Alkynes, Cycloalkanes, Cycloalkenes and Cycloalkynes
are also classified as aliphatic hydrocarbons

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 Alkane Isomers
 CH4 = methane, C2H6 = ethane, C3H8= propane
 Isomers of alkanes are of 2 types: straight chain or normal
alkanes and branched chain alkanes.
 Straight-chain or normal alkanes have all n C atoms attached
in a single connected chain. That is, no C atom is attached to
more than 2 other C atoms. For any alkane with n  4, there is
only one straight chain isomer.
 Branched-chain alkanes have one or more C atoms
connected to 3 or 4 other C atoms. C4H10 has one branched
isomer. For all alkanes with n > 4, there are more than one
branched isomers.

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 Examples of Constitutional Isomers
 Compounds other than alkanes can be constitutional isomers of
one another
 They must have the same molecular formula to be isomers

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 Condensed Structures of Alkanes
 We can represent an alkane in a brief form or in many types of
extended form
 A condensed structure does not show bonds but lists atoms,
such as
 CH3CH2CH3 (propane)
 CH3C(CH3)2CH3 (IUPAC: 2,2-dimethylpropane; common:
neopentane)

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Names of Small Hydrocarbons
No. of Carbons Formula Name (CnH2n+2)
1 Methane CH4
2 Ethane C2H 6
3 Propane C3H 8
4 Butane C4H10
5 Pentane C5H12
6 Hexane C6H14
7 Heptane C7H16
8 Octane C8H18
9 Nonane C9H20
10 Decane
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3.3 Alkyl Groups
 Alkyl group – remove one H from an alkane
(a part of a structure)
 General abbreviation “R” (for Radical, an
incomplete species or the “rest” of the
molecule)
 Name: replace -ane ending of alkane with -yl
ending
 CH3 is “methyl” (from methane)
 CH2CH3 is “ethyl” from ethane
 See Table 3.4 for a list
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Types of Alkyl groups
 Classified by the connection site (See Figure 3.3)
 a carbon at the end of a chain (primary alkyl group)
 a carbon in the middle of a chain (secondary alkyl
group)
 a carbon with three carbons attached to it (tertiary alkyl
group)

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 3.4 Naming Branched Alkanes
 Find the longest continuous chain of C atoms. This is the parent
chain. Name the parent chain
 Number the C atoms in the parent chain starting from the end
closest to a substituent
 Substituents are atoms (Cl, Br, I) or groups of atoms (examples:
alkyl groups, OH, carbonyl group, amino group) that have
replaced H’s
 Specify the number(s) of the C atom(s) to which the substituent(s)
is(are) attached to and the name(s). Letters and numbers are
separated by hyphens
 List the substituents in alphabetical order before the parent name.
 When there are more than 1 substituent of the same type, use
prefixes di, tri, tetra etc. to specify the number of each type. The
location of each substituent (even when they are identical and
attached to the same C) should be specified.
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•If two different longest chains are possible, choose the one with the more
substituents as the parent chain
•If two different substituents are equidistant from either end, chose to number
from that end that is closer to the substituent that is alphabetically first.

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 Drawing Branched Isomers
Drawing structural isomers for alkanes with n≥4 C atoms:
Start with parent straight chain with n≥3.
Replacing any H attached to a secondary C with a
methyl group will result in a branched isomer with n+1 C atoms.
Replacing any H attached to either of the two primary C atoms of
a straight chain alkane will only yield the corresponding straight
chain alkane with n+1 C atoms.
When drawing isomers, replacing any of the H on symmetrically
positioned C atoms with the same alkyl group will yield the same
isomer.
Verify by naming your isomers.
If the names of two isomers are the same, they are identical.

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 3.5 Properties of Alkanes
 Alkanes undergo substitution reactions and combustion
reactions (alkane + O2 → CO2(g) + H2O)
 In substitution reactions, H’s are replaced by other atoms.
 For example,alkanes react with Cl2 in the presence of
light to replace H’s with Cl’s.
 The boiling points & melting points of alkanes increase
with increasing chain length.
 Among the structural isomers of an alkane, the less
branched the alkane, higher its boiling point, melting
point.

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 3.6 Cycloalkanes
 Cycloalkanes are alkanes that have carbon atoms attached to form a
ring
 In simple cycloalkanes, all n C atoms are attached to form a ring. The
general molecular formula of a cycloalkane with n C atoms is C nH2n
 The condensed structural formula of a simple cycloalkane with n C
atoms is a regular polygon with n vertices
 The boiling points of cycloalkanes also increases with increase in ring
size.
 Cycloalkanes exhibit structural isomerism. A cycloalkane has the
same general formula as an alkene with the same number of C atoms
and 1 double bond.
 In addition, any cycloalkane with more than 3 C atoms will also have
cyclic structural isomers

cyclobutane cyclohexane
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cyclopropane cyclopentane
Complex Cycloalkanes
 Naturally occurring materials contain cycloalkane structures
 Examples: chrysanthemic acid (cyclopropane), prostaglandins
(cyclopentane), steroids (cyclohexanes and cyclopentane)

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 3.7 Naming SubstitutedCycloalkanes
 Count the number of carbon atoms in the ring and the number of C atoms in the
largest substituent chain. If the number of carbon atoms in the ring is equal to
or greater than the number in the substituent chain, the compound is named as
an alkyl-substituted cycloalkane. Otherwise, if the number of C atoms is greater
in the alkyl chain, the compound is named as a cycloalkyl-substituted alkane
 There is no need to number the ring if there is only 1 substituent.
 When there are more than 1 substituent, the ring has to be numbered. For an
alkyl- or halo-substituted cycloalkane, start at a point of attachment as C1 and
number the substituents on the ring so that the second substituent has as low a
number as possible.
 Number the substituents and write the name

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 3.8 Cis-Trans Isomerism in Cycloalkanes
 Stereoisomers have the same molecular formula, the same
connectivity but different 3-D orientations of substituents.
 The rotation about C-C bonds in cycloalkanes is limited which results
in stereo isomerism when there are 2 or more substituents.
 Rings have two “faces” and the relative positions of two different
substituents will result in different stereoisomers.
 In disubstituted cycloalkanes, the isomer with both substituents on
the same side is called the cis isomer and the isomer with
substituents on opposite sides is called the trans isomer.
 For example, consider the 2 stereoisomers of 1,2-dimethyl-
cyclopropane . Cis-1,2-dimethylcyclopropane has both methyl
substituents on the same side. Trans-1,2-dimethycyclopropane has
the methyls on opposite sides of the ring

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Structural Isomers & Stereoisomers

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 Naming Bicycloalkanes & Spiroalkanes
1. A bicycloalkane consists of 2 rings that share 2 C atoms. The two shared C
atoms are called ‘bridgehead C’s’. There are 3 paths or ‘bridges’ that
connect these two bridgehead C’s.
2. The parent name of a bicycloalkane is that of an unbranched alkane having
the same number of carbons with a prefix bicyclo.
3. Begin numbering at one of the two "bridgehead" carbons. Proceed around
the longest bridge to the 2nd bridgehead, then around the next longest
bridge and then finally around the shortest bridge.
4. If the one or more  substituents are present, start numbering from the
bridgehead which results in the first substituent on the larger bridge
having a smaller number.
5. The length of a ‘bridge’ = number of C in that bridge between the bridgehead
C’s and not including the bridgehead C’s.
6. The lengths of the bridges are specified within square brackets between the
word bicyclo and the parent name. The lengths are written in descending
order and separated by periods. For example, bicyclo[4.2.1]nonane has 9
C atoms two of which are bridgehead C’s and therefore common to all 3
bridges. The 3 bridges have 4 C, 2C and 1 C respectively.
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 Naming Spiroalkanes
1. A spiroalkane consists of 2 rings that share 1 C atom.
2. The parent name of a spiroalkane is that of an unbranched alkane having the same
number of carbons with a prefix spiro.
3. Count the C’s in the smaller ring and the C’s in the larger ring to determine the bridge
lengths. Do not include the shared C in determining the bridge lengths.
4. If substituents are present on the ring, numbering of the rings starts in the small
ring on the C next to the shared C, passes round this ring and through the shared
C into the larger ring. The numbering goes round the two rings in the direction which
produces the lowest numbers in each ring..
5. The lengths of the bridges are specified within square brackets between the word
spiro and the parent name.
6. The lengths are written in ascending order and separated by periods. For
example, spiro[3.4]octane has 8 C atoms one of which is a bridgehead C and
therefore common to both rings. The 2 bridges have 3 Cand 4 C respectively.
Check the following site for problems:
http://www.chem.ucalgary.ca/courses/351/orgnom/alkanes/alkanes-08.html

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