CHAPTER 4: ALKANES AND CYCLOALKANES
 Hydrocarbons composed of H and C
 Saturated = all single bonds, unsaturated =
presence of multiple bonds
 Besides common names of some compounds (e.g.
formic acid), IUPAC naming system
o Includes parent name (longest carbon
chain), names of substituents, and location
of substituents
 1. Identify parent chain (longest consecutive chain
of carbons)
o If more than one possible, choose one with
most substituents attached
o If parent chain is cyclic, add prefix “cyclo”
o Meth, eth, prop, but, pent, hex, hept, oct,
non, dec, undec, dodec, tridec, tetradec,
pentadec, eicos, triacont, tetracont,
pentacont, hect
 2. Identify and name substituents
o Ring can either be parent chain or
substituent but not both depending on
number of carbons
o For substituents with complex branches:
 Number longest carbon chain
within substituent, starting with
attached to parent
 Name substituent
 Name and number substituent’s
side group
 Common names: isopropyl, sec-
butyl, isobutyl, tert-butyl
o For alkyl groups, add –yl to end of parent
chain name
 3. Number substituents
o 1. If one substituent, number so
substituent has lowest number
o 2. If multiple, number so first substituent
has lowest number
o 3. If tie, then number so second gets
lowest number possible
o 4. If no other tie-breaker, assign lowest
number alphabetically (iso used, tert- and
sec- not used)
o Same rules for cycloalkanes
 4. To assemble, put # and name of substituents
before parent chain in alphabetical order
o Prefix used (di, tri, tetra, etc.) if multiple
identical substituents but not alphabetized
 Bicyclic compounds contain two fused rings
o Prefix “bicyclo” in front of parent name
o Carbons where rings fused are bridgehead
carbons
CONSTITUTIONAL ISOMERS
 Isomers: different structures, same formula
 Constitutional isomers: different connectivity of
atoms
o As number of C increases, number of
constitutional increases
o Impractical, group by functional group (e.g.
primary, secondary, tertiary alcohol) and
then generalize three types of reactivity
 Can test if structures are same two ways:
o Flip molecules in 3D space and rotate
around its single bonds until super-
imposable on other molecule
o See if have same IUPAC name
 Relative stability of isomers can be determined by
measuring heat of combustion
o Products of combustion of hydrocarbons,
water and carbon dioxide, bond strengths
constant. So heat depends on bond
strengths of isomer. Less stable (more
branches) = more bond strength = less heat
of combustion
SOURCES AND USES OF ALKANES
 Various components of petroleum can be
separated by distillation
 Gasoline fraction of crude oil only makes up about
19%, not enough to meet demand
 Gasoline mixture of straight, branched, aromatic
hydrocarbons 5-12 C in size
o Large alkanes can be broken into smaller
by cracking
o Straight chain alkanes can be converted
into branched alkanes and aromatic
compounds through reforming
 After these processes, yield of gasoline is about
47% rather than 19%
NEWMAN PROJECTIONS
 Rotating around sigma bond does not affect bond
in any way (as long as don’t break or weaken)
 Single bond rotations result in conformations,
different 3D shapes
o Can represent with wedge and dash,
sawhorse, or Newman projection (looking
straight down specific C-C bond)
 Dihedral/torsional angle: angle between atoms on
adjacent carbons
 Staggered conformations: atoms on adjacent
carbons maximum separation from each other
  Eclipsed conformations: atoms on adjacent
carbons overlap
 Torsional strain: difference in energy between
higher energy eclipsed and lower energy staggered
o Presence of stabilizing interactions: filled
bonding MO has favorable side-on-side
overlap with empty anti-bonding MO
o E.g. 12 kJ/mol less stable for ethane, 4
kJ/mol per eclipse, 99% of molecules will
be staggered at room temperature
 For propane, barrier to rotation is 14 kJ/mol.
Based on analysis of ethane, then energy cost of H
eclipsing CH3 group is 6 kJ/mol
 For butane, torsional strain shows more variation
o Multiple staggered and eclipsed
conformations and no longer degenerate
o For staggered, gauche conformation 3.8
kJ/mol more energy than anti
 Steric interaction btw methyl
o Highest energy when methyl groups
eclipse  19 kJ/ mol from both torsional
strain and steric interaction
 Know H eclipse is 4 kJ/mol, so CH3--
CH3 eclipse accounts for 11 kJ/mol
CYCLOALKANES
 Ideal bond angles for sp3 carbon is 109.5, so if
cycloalkanes flat, then carbons would experience
angle strain and all C-C bonds would be in eclipsing
rotamers, causing considerable torsional strain
 Combustion data show 6-member ring most stable
size (lowest energy per CH2 group)
 Cyclobutane 27kJ/mol less stable than cyclohexane
per CH2 group
o Angle strain: 88
o Torsional strain: adjacent C-H bonds
neither fully eclipsed nor fully staggered
o Puckered formation has less torsional
strain than flat conformation
 Cyclopentane 5 kJ/mol less stable than
cyclohexane per CH2 group
o Little angle strain: near 109.5
o Slight torsional strain
o Envelope conformation to avoid most of
torsional strain
CYCLOHEXANE
 Can adopt variety of conformations, but chair
(most stable), half chair (least stable), twist boat
(second most stable), boat (second least stable),
twist boat, half-chair, chair
o In chair formation, no angle strain and no
torsional strain (all C-H bonds staggered)
o Other possible conformations have some
amount of angle and/or torsional strain
(combined is ring strain)
 Each C in carbon ring has two substituents: one in
axial position and other in equatorial
o Axial points up and down, alternating
around ring
o Equatorial drawn off ring, run in parallel
lines to chair
 Monosubstituted cyclohexane: two possible chair
conformations: X in equatorial or axial
o Ring flipping rotates all C-C bonds; axial
become equatorial and vice versa
o When X is axial, less stable because causes
steric interactions, or more specifically,
1,3-diaxial interactions (gauche). These
interactions are not present when methyl
group is equatorial
o Larger groups will cause more steric strain
in axial position
 Disubstituted cyclohexane: solid or dashed wedges
represent positioning on ring
o Based on geometry of molecule, make sure
that based on the axial or equatorial
positions at the carbon, the substituent is
either pointing up or down
o Use cis when two groups on same side of
ring and trans when opposite sides
o Each isomer exists as two equilibrating
chairs which spends most time in stable
chair conformation (when two identical
substituents, trans more stable because
can have both in equatorial position)
POLICYCLIC SYSTEMS
 Decalin is two 6-member rings fused together
o Found in many naturally occurring
compounds such as steroids
o Cis or trans based on position of H on the
bridgehead C
 Important structures result when more than one
ring fused together, e.g. camphor and camphene
o Camphor and camphene from evergreens
 Structure of diamond is network of 6-membered
rings fused together in trans position