Unsaturated Hydrocarbons

• Contain carbon-carbon multiple bonds.

Alkenes C=C double bonds

Alkynes triple bonds
Aromatics benzene rings

Seager & Slabaugh, 2004

Naming Alkenes
• Step 1: Name the longest chain that contains the C=C
bond. Use the IUPAC root and the –ene ending.
• Step 2: Number the longest chain so the C=C bond gets
the lowest number possible.
• Step 3: Locate the C=C bond with the lowest-numbered
carbon.

Seager & Slabaugh, 2004

Examples:
1 2 3 4
CH3-CH=CH-CH3
2-butene

6 5 4 3 2 1
CH3-CH2-CH2-CH=CH-CH3
2-hexene

Seager & Slabaugh, 2004

Naming Alkenes, cont.
• Step 4: Locate and name attached groups.
• Step 5: Combine all the names as you did with alkanes.

Seager & Slabaugh, 2004

The Geometry of Alkenes
• In C=C bonds, sp2 hybrid orbitals are formed by the carbon
atoms, with one electron left in a 2p orbital. A
representation of sp2 hybridization of carbon:
• During hybridization, two of the 2p orbitals mix with the
single 2s orbital to produce three sp2 hybrid orbitals. One
2p orbital is not hybridized and remains unchanged.
• This gives a planar shape for the sp2 bonding orbitals with
the unhybridized p orbital perpendicular to the plane of the
three sp2 hybridized orbitals.
• The planar geometry of the sp2 hybrid orbitals and the
ability of the 2p electron to form a “pi bond” bridge locks
the C=C bond firmly in place.
• Because there is no free rotation about the C=C bond,
geometric isomerism is possible.

Seager & Slabaugh, 2004

Physical Properties of Alkenes
•Similar to alkanes
•Non-polar
•Insoluble in water
•Soluble in non-polar solvents
•Less dense than water

Seager & Slabaugh, 2004

Alkene Reactions
• Alkenes are quite chemically reactive
• Many reactions are addition reactions:
Alkene Reactions, cont.
• Halogenation (addition) reactions produce haloalkanes or
alkylhalides.

Seager & Slabaugh, 2004

Alkene Reactions, cont.
• Hydrogenation (addition) reactions can occur in the
presence of a catalyst (Pt, Pd, or Ni).

The hydrogenation of vegetable oils is an important

commercial process.
Alkene Reactions, cont.
• Unsymmetrical alkene addition reactions follow
Markovnikov’s rule which states that when a molecule of
H-X adds to an alkene, the H predominantly attaches to
the carbon already bonded to the most hydrogens. “The
rich get richer.”

Seager & Slabaugh, 2004

Alkene Reactions, cont.
• Halogenation following Markovnikov’s rule

CH2 = CH – CH3 + HBr  CH3 – CH – CH2

| |
Br H
Alkene Reactions, cont.
• Hydration (addition of water) reactions follow
Markovnikov’s rule:

H2SO4
CH2 = CH – CH3 + H20 —>CH2 – CH – CH2
| |
OH H

This reaction requires an acid catalyst.

Alkene Reactions, cont.
• Addition polymerization – addition reaction between double
bonded compounds.

Seager & Slabaugh, 2004

Polymerization
• Polymers – long chain products made up of repeating
units.
• Monomer – the starting material that becomes the
repeating units of a polymer.
Alkynes
• Ethyne (commonly called acetylene) is the simplest alkyne
and is used as a fuel for torches and in making plastics.
 • Alkynes are named in exactly the same ways as alkenes,
except the ending –yne is used.

Examples:
Benzene
• Aromatic compounds contain the benzene ring.
• Aliphatic compounds don’t contain the benzene ring.
• In benzene, the six p orbital bonding electrons of the sp2
hybridized carbon atoms can move freely around the ring.
• A hybrid orbital view of the benzene structure:
 • This gives rise to two possible benzene structures:

Which are better represented by:

Note: that there is only 1 available bonding site on each

carbon atom!

Seager & Slabaugh, 2004

Naming Benzene Derivatives
• Rule 1: When a single hydrogen attached to the benzene
ring is replaced, the compound can be named as a
derivative of benzene.
Naming Benzene Derivatives, cont.
• Rule 2: Some common names are IUPAC-accepted and
used preferentially.

Seager & Slabaugh, 2004

Naming Benzene Derivatives, cont.
• Rule 3: When the benzene ring is part of a more complex
hydrocarbon, the benzene ring is referred to as a phenyl
group.

Seager & Slabaugh, 2004

Naming Benzene Derivatives, cont.
• Rule 4: When two groups are attached to the benzene
ring, their positions can be designated by the prefixes
ortho (o), meta (m), and para (p).

Seager & Slabaugh, 2004

Naming Benzene Derivatives, cont.
• Rule 5: When two or more groups are attached, their
positions can be indicated by numbering the ring.

Seager & Slabaugh, 2004

Properties of Aromatic Compounds
• Nonpolar
• Insoluble in water
• Aromatic rings are relatively stable chemically and often
remain intact during reactions.

Seager & Slabaugh, 2004

Polycyclic Aromatic Compounds
 Contain two or more fused benzene rings and
are often known to be carcinogenic.

Seager & Slabaugh, 2004