Week 5.

UNSATURATED HYDROCARBONS:  Cycloalkenes with no substituent, no locant number required

ALKENES AND ALKYNES for the double bond
 Cycloalkenes with substituent, carbons in double bond are 1
Unsaturated Hydrocarbons and 2, start numbering clockwise or counterclockwise to give
 Contains only carbon and hydrogen but with multiple bonds lowest numbers possible for substituents
 With double (alkenes) or triple bonds (alkynes)
 Aromatic compounds contain delocalized bonds in a six-
membered ring

Alkenes and Cycloalkenes

 The general formula for alkenes with one double bond is
CnH2n
o Cycloalkenes with one double bond: CnH2n-2  Cycloalkenes with more than one double bond, locant numbers
for double bonds are required
 The carbons in the double bond are sp2 hybridized; trigonal
planar geometry, 120°
 In the double bond, one sigma bond and one pi bond

STRUCTURE OF ALKENES
Nomenclature of Alkenes
 Replace –ane with –ene to reflect the presence of a double
bond
 Longest continuous carbon chain with the double bond is the
parent

Constitutional Isomerism in Alkenes

 Skeletal isomers – different connectivity of carbon atoms

 Positional isomers – same “skeleton” but different position of
 Number starting at the end nearest a double bond
double bond
 Consider the isomers of 1-butene, C4H8
 If double bond is the same distance from each end, begin at the
end nearest a substituent

 Between the locant numbers of the carbons in the double bond,

the lower number becomes the locant number of the double
bond

 For multiple double bond, use –diene, -triene, -tetraene, and so

on.

Nomenclature of Cycloalkenes
 Cis-trans Isomerism in Alkenes
 For substituted alkenes, cis-trans isomerism is only possible if
there are different substituents on each of the carbon atoms of
the double bond
 If the carbon atoms of the parent chain is on the same side, cis
isomer
 If the carbon atoms of the parent chain is on the opposite side,
trans isomer

 No rotation can occur along the double bond so no

interconversion between the cis and trans isomer unless there
is bond breaking

Physical Properties of Alkenes & Cycloalkanes

 Insoluble in water and soluble in
nonpolar solvents since
dominant IMF is dispersion
forces
 Boiling points are quite similar
to that of alkanes with same no.
of C atom; increasing number of
C atoms increases b.p.
Sources and Uses of Alkenes
 Insoluble in water and soluble in nonpolar solvents since
 Catalytic cracking of larger hydrocarbons – subjected to heat dominant IMF is dispersion forces
and pressure
 Boiling points are slightly less than that of alkanes with same
o A mixture of smaller alkenes are produced
no. of C atom; increasing number of C atoms increases b.p.
o Ethene and propene are used as chemical feedstock – for
producing plastics and other organic compounds

 Alkenes are also present in nature

o Ethylene – an important plant hormone; synthetic ethylene is
used to force the ripening of fruits
o Pheromones – used as signaling molecules by insects and
some animals and plant
o Terpenes – organic compounds derived from isoprene units (5
carbon unit)  Melting points for cis isomers are lower than that of trans
isomers because of the bending shape
 Reactions of Alkenes
 Combustion – in the presence of enough oxygen, produces
carbon dioxide, water and heat
o Incomplete combustion also produces carbon monoxide and
soot
o Alkenes are less likely to combust completely than alkanes
because of the higher carbon to hydrogen ration

 Symmetric addition – addition of H2: reduction/ hydrogenation

o Catalyzed by transition metal catalyst such as platinum,
palladium, ruthenium or nickel Polymerization of Alkenes
 Several alkene units (monomers) can combine to form a long
chain (polymers)

 Symmetric addition - addition of Cl2 or Br2: halogenation  n can be as large as 100,000

 Substituted alkenes can also be polymerized

 Example: vinyl chloride to form polyvinyl chloride

 Unsymmetrical addition - addition of HX: hydrohalogenation
o Regioselective; follows the Markovnikov’s rule: H adds
to carbon with more H, X adds to carbon with less H

 Unsymmetrical addition - addition of water: Acid-catalyzed

hydration
o Catalyzed by acid, usually sulfuric acid
o Regioselective; follows the Markovnikov’s rule: H adds
to carbon with more H, OH adds to carbon with less H
 ALKYNES
 General formula: CnH2n-2

 The C atom in triple bond is sp hybridized; bond angle is

180°

NOMENCLATURE OF ALKYNES
 Similar to the nomenclature of alkenes, identify longest
chain with triple bond, use –yne to replace -ane; locant
number for triple bond

ISOMERISM IN ALKYNES
 Constitutional isomerism – skeletal and positional isomers

Physical and Chemical Properties of Alkynes

 Less dense than water (< 1.00 g/mL); nonpolar, dissolves in
nonpolar solvents; can undergo combustion and addition
reactions like alkenes
 C3 to C4 1-alkynes are gaseous at r.t. and > C5 1-alkynes
are liquid
 Alkynes also undergo addition reactions; twice per molecule