Chapter 2

Alkanes and
cycloalkanes
 2.1 Classes of Hydrocarbon
 Hydrocarbon:only hydrogen and carbon
 Only carbon-carbon single bonds:saturated

H H
CH2 CH2
H C H CH3 C CH3
 Contain carbon-carbon
H H multiple
CH2 CH2
bonds:
unsaturated

H
CH3 C CH C CH3 CH CH
 Alkane:carbon
H
atoms
CH3
bonded
CH2 CHin
2
chains
 2.1 Classes of Hydrocarbon
 Cycloalkanes:carbon atoms bonded to
form a ring
 Acyclic: not cyclic-a chain of carbon
atoms
 Heteroatoms: not carbon and hydrogen
 Heterocyclic compounds:one or more
heteroatoms on ring
 2.2 Alkanes
 Normal alkanes:continuous chain of carbon
atoms
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH3
octane(a normal alkane)
 Branched alkanes:carbon atoms bonded to more
than two other carbon atoms
CH3 CH2 CH2 CH3 CH3 CH CH3
 General molecular formula:CCH
nH
butane(normal)isobutane(branched)
3 2n+2

 Homologous series:C4H10 and C5H12 Different

CH2 number,a repeating unit
 Classification of Carbon Atoms
 2.2 Alkanes
 Primary carbon atom-bonded only one
other carbon atom
 Secondary carbon atom-bonded two other
carbon atoms
 Tertiary carbon atom-bonded three other
carbon atoms
 Quaternary carbon atom-bonded four
other carbon atoms
 Designated by the symbols 1º, 2º, 3º, 4º
2.2 Alkanes
 2.3 Nomenclature of Alkane
 Alkyl group:lost one hydrogen atom
H H
H C H removing H gives H C or CH3
H H
methane methyl group
H H H H
H C C H removing H gives H C C or CH3CH2
H H H H
 Alkane ending—ane
ethane ethyl group
 Alkyl ending—yl
 Name:prefix—parent—suffix
 2.3 Nomenclature of Alkane
 The IUPAC rules for naming alkanes
 Longest,continuous,chain of carbon
CH2 CH3
CH3 CH2 CH CH3 parent:5 carbons not 4

 Large number of branch points

CH2 CH3
parent:6 carbons,2 branches
CH3 CH CH CH2 CH2 CH3
methyl and ethyl(correct)
CH3
CH2 CH3
parent:6 carbons,1 branche
CH3 CH CH CH2 CH2 CH3
three-carbon alkyl
CH3
 2.3 Nomenclature of Alkane
 Number the carbon,end of the chain,near
the first branch
CH2 CH3
2 3
CH3 CH CH2 CH CH2 CH3
4 5 6
CH3

 Equal first branch,near the second

branch CH2 CH3 CH3
8 7 carbon 2=carbon 7
CH3 CH CH2 CH2 CH CH2 CH CH3 second branch:ethyl
6 5 4 3 2 1
CH3
 2.3 Nomenclature of Alkane
 Number—hyphen—name of alkyl—
hyphen—name of alkyl+parent
name,alphabetical order
CH2 CH3
1 2 3 4-ethyl-2-methylhexane
CH3 CH CH2 CH CH2 CH3
4 5 6 not 2-methyl-4-ethyl
CH3

 Di-(2),tri-(3),tetra-(4) ,same type alkyl

 Location number,seperated by commas
1 2 3 4 5 6
CH3 CH CH2 CH CH2 CH3 2,4-dimethylhexane
CH3 CH3
 2.3 Nomenclature of Alkane
 Prefixes di-,tri-,tetra- won’t change the
alphabetical order
CH2 CH3
1 2 3
CH3 CH2 CH CH2 C CH2 CH2 CH3 5-ethyl-3,5-dimethyloctane
4 5 6 7 8 not 3,5-dimethyl-5-ethyloctane
CH3 CH3

 Name of alkyl groups

CH3 CH2 CH2 CH3 CH
propyl CH3
(normal propyl) isopropyl
2.3 Nomenclature of Alkane
CH3 CH2 CH2 CH2 CH3 CH2 CH
CH3
butyl sec-butyl
CH3
CH3 CH CH2 CH3 C
CH3 CH3
iso-butyl tert-butyl

CH3 CH CH3 CH CH2

CH3 CH3
isopropyl iso-butyl
1-methylethyl 2-methylpropyl IUPAC name
4-isopropylheptane = 4-(1-methylethyl)heptane
 2.4 Conformations of Alkanes
 About steric structure
 Differ in the positions of hydrogen atoms
 Comes from the constant rotation around
carbon-carbon σ bond
 Distance of hydrogen atoms,bonding
electrons
 Staggered:the farthest away from each
other,
lowest energy
Extreme Conformations of Ethane
 
Name of Wedge-Hatched Sawhorse Newman
Conformer Bond Structure Structure Projection

                                                                                                                                                                                                                                                    

                        
 2.4 Conformations of Alkanes
 Eclipsed:the closest,highest energy
 Skew:middle of staggered and eclipsed
 Nemman projection formulas
H
H front atom
H

back atom
H H
H
Newman projection of staggered ethane conformation
HH

H H
H
Newman projection of eclipsed ethane conformation
Bond Repulsions in Ethane

             
 2.4 Conformations of Alkanes
 Conformations of butane
CH3 CH3
H CH3
H H

H H H H
CH3 H
anti conformation gauche conformation

 Steric strain:repulsion of electron clouds

 Four Conformers of Butane

                                                                                                                                                                                                                                           

                                                
 2.5 Cycloalkanes
 Contain only carbon-carbon single bond
 Saturated hydrocarbons, CnH2n ,single ring

cyclopropane cyclobutane cyclopentane cyclohexane

 Geometric isomerism

cis isomer trans isomer

H H One methyl group
CH3 is aboveH
the plane
CH3 CH3
Both methyl groups H CH3 One methyl group
are below the plane is below the plane
 2.5 Cycloalkanes
 Different spatial arrangements
 Nomenclature of cycloalkanes
 Prefix cyclo-
 Lower number of substituents
Cl
Br

2 1 6
3 5
Cl Cl CH3CH2 4
ethylcyclopentane isopropylcyclobutane 1,1,4-trichlorocycloctane trans-1-bromo-3-ethylcyclohexane
 2.6 Conformations of
cycloalkanes
 Six-membered ring of cyclohexane
 Not planar,puckered conformation,
 all C—H bonds on neighboring carbon
atoms:staggered
 Chair conformation of cyclohexane
 H position:axial and equatorial
 Ring flip:the axial and equatorial positions
interchanged
2.6 Conformations of cycloalkane
2.6 Conformations of cycloalkane
 2.6 Conformations of
cycloalkanes
 Substituted chair conformation
 Methylcyclohexane:a equatorial methyl is
more stable than an axial methyl group
 Steric strain between the methyl group
and the axial hydrogen atoms at the C-3
and C-5 atoms
CH3 equatorial
axial
H ring flip CH3

5% 95% H
 2.6 Conformations of
cycloalkanes
 Steric strain:bulk of groups,distance of
groups
 Equatorial position:long distance
 Axial position:short distance
 2.7 Physical properties of
saturated hydrocarbon
 Less dense than water
 Not polar,weak London force
 Not soluble in water,a polar substance
 The boiling points of the normal alkanes
increase with increasing molecular weight
 Branching alkane:lower boiling point
 2.8 Oxidatin of alkanes and
cycloalkanes
 Stable for oxidation
 Need extreme conditions
CH4 + O2 CO2 + H2O
 2.9 Halogenation of saturated
hydrocarbons
 Condition: high temperature or presence
of light
 Substitution: a halogen atom in place of a
hydrogen atom
CH4 + Cl2 CH3Cl + HCl
chloromethane
(methyl chloride)

 One and more substituted products

2.9 Halogenation of saturated
hydrocarbons
difficult to control the reaction
CH3Cl + Cl2 CH2Cl2 + HCl
dichloromethane
(methylene chloride)
CH2Cl2 + Cl2 CHCl3 + HCl
trichloromethane
(chloroform)
CHCl3 + Cl2 CCl4 + HCl
tetrachloromethane
(carbon tetrachloride)
 2.9 Halogenation of saturated
hydrocarbon
 Chlorine atom:so reactive,not seclective in
its substitution for hydrogen atoms
 Bromine atom:not so reactive,more
seclective
 Reactivitity:3°>2°>1°
 2-methylpropane
37% 2-chloro-2-methylpropane
63% 1 -chloro-2-methylpropane
99% 2-bromo-2-methylpropane
 2.9 Halogenation of saturated
hydrocarbons
CH3 CH3 CH3
CH3 C CH3 + Cl2 CH3 C CH3 + CH3 C CH2Cl + HCl
H Cl H
2-chloro-2-methylpropane (37%) 1-dhloro-2-methylpropane(63%)
CH3 CH3
CH3 C CH3 + Br2 CH3 C CH3 + HBr
H Br
2-bromo-2-methylpropane(99%)

 Mechanism of chlorination
 Homolytic bond cleavage—radical
 Radical:with single electron,electron
deficient and highly reactive
 2.9 Halogenation of saturated
hydrocarbon
 Initial step
step 1 Cl Cl Cl + Cl

 Propagation steps
step 2 CH3 H + Cl CH3 + H Cl
step 3 CH3 + Cl Cl CH3 Cl + Cl
 2.9 Halogenation of satureted
hydrocarbon
 Chain-terminating steps

Cl + Cl Cl Cl
CH3 + CH3 CH3 CH3
CH3 + Cl CH3 Cl
3.10 Nomenclature of haloalkane
 Low molecular weight:name of
alkyl+halide
CH3 CH3
CH3 CH2 Br CH3 CH F CH3 C Cl
CH3
ethyl bromide isopropyl floride tert-butyl chloride

 IUPAC rules
 Similar to alkane
3.10 Nomenclature of haloalkane
 Lowest number of substitutent:regardless
of the kind of substituents
CH3 CH3
CH3 CH CH CH2 CH3 CH3 CH2 CH CH CH3
1 2 3 4 5 5 4 3 2 1
Cl Br
3-chloro-2-methylpentane 2-bromo-3-methylpentane

 Prefixes di-,tri-,etc show more same type

halogen atoms
Cl Cl Br Br
CH3 CH CH CH2 CH3 CH3 CH2 CH C CH2 CH3
1 2 3 4 5 6 5 4 3 2 1
Br
2,3-dichloropentane 3,3,4-tribromohexane
3.10 Nomenclature of haloalkane
 Alphabetical order:listed in molecule name
and number the substituents
Br CH3 Br CH3
Cl CH CH CH2 CH CH3 CH3 CH CH2 CH CH3
1 2 3 4 5 1 2 3 4 5
2-bromo-1-chloro-4-methylpentane 2-bromo-4-methylpentane

 Halocycloalkanes:numbered from the

carbon atom bearing the halogen
atom,lowest number
2
Br 1 3 CH3

5 4
cis-1-bromo-3-methylcyclopentane