Alkenes:

Structure and
Nomenclature
Unsaturated Hydrocarbons
Unsaturated hydrocarbon: contains one or more
carbon-carbon double or triple bonds
Alkene: contains a carbon-carbon double bond
and has the general formula CnH2n
H H
C C
H H
Ethylene
(an alkene)

Alkyne:
contains a carbon-carbon triple bond
and has the general formula CnH2n-2
H-C C-H
Acetylene
(an alkyne) .
Unsaturated Hydrocarbons

H H
C C
H C C H C6 H5 - Ph-
C C
H H
Benzene Alternative rep res entations
for th e ph enyl grou p
Structure of Alkenes
A double bond consists of
one sigma bond formed by the overlap of sp2 hybrid
orbitals and one pi bond formed by the overlap of
parallel 2p orbitals
the two carbon atoms of a double bond and the four
atoms bonded to them lie in a plane, with bond angles
of approximately 120
Elements of Unsaturation

Unsaturation: A structural element that

decreases the number of hydrogens in the
molecule by two.
Double bonds and rings are elements of
unsaturation.
To calculate: Find number of hydrogens if they
were saturated, subtract the actual number of
hydrogens, then divide by 2.

5
Example: Calculate the Unsaturations for a
Compound with Formula C5H8.

First calculate the number of hydrogen atoms for a

saturated compound with five carbons:
(2 x C) + 2
(2 x 5) + 2 = 12

Now subtract from this number the actual number of

hydrogen atoms in the formula and divide by 2:
12 8 = 4 = 2 unsaturations
2 2
The compound has two unsaturations, they can be two
double bonds, two rings, or one double bond and one ring.

Chapter 7 6
Elements of Unsaturation: Heteroatoms
Halogens replace hydrogen atoms in hydrocarbons, so
when calculating unsaturations, count halides as
hydrogen atoms.
Oxygen does not change the C:H ratio, so ignore oxygen
in the formula.
Nitrogen is trivalent, so it acts like half a carbon. Add the
number of nitrogen atoms when calculating
unsaturations.

Chapter 7 7
Example: Calculate the Unsaturations for a
Compound with Formula C4H7Br.

First calculate the number of hydrogens for a saturated

compound with four carbons:
(2 x C) + 2 + N
(2 x 4) + 2 = 10

Now subtract from this number the actual number of

hydrogens in the formula and divide by 2. Remember to
count halides as hydrogens:
10 8 = 2 = 1 unsaturation
2 2

8
Example: Calculate the Unsaturations for a
Compound with Formula C6H7N.

First calculate the number of hydrogens for a saturated

compound with six carbons. Add the number of nitrogens:
(2 x C) + 2 + N
(2 x 6) + 2 + 1 = 15

Now subtract from this number the actual number of

hydrogens in the formula and divide by 2:
15 7 = 8 = 4 unsaturations
2 2

9
Index of Hydrogen Deficiency
Problem: isopentyl acetate has a molecular formula of
C7H14O2. Calculate its IHD O
reference hydrocarbon C7H16
O
IHD = (16-14)/2 = 1 Isopentyl acetate

Problem: calculate the IHD for niacin, molecular formula

C6H6N2O O

reference hydrocarbon C6H16 N H2

IHD = (16 - 6)/2 = 5 N
Niacin
IUPAC Nomenclature
1. Number the longest chain of carbon atoms that
contains the double bond in the direction that gives
the carbons of the double bond the lowest numbers
2. Locate the double bond by the number of its first
carbon
3. Name substituents
4. Number the carbon, locate and name substituents,
locate the double bond, and name the main chain

6 4 2 6 4 2 4 2
5 3 1 5 3 1 5 3 1

1-Hexene 4-Methyl-1-hexen e 2-Eth yl-4-methyl-1-pen tene

IUPAC and New IUPAC
Ring Nomenclature
In a ring, the double bond is assumed to
be between Carbon 1 and Carbon 2.
CH3
3
1
CH3 2

2
1

1-methylcyclopentene 3-methylcyclopentene
Common Names
Despite the precision and universal acceptance
of IUPAC nomenclature, some alkenes,
particularly low-molecular-weight ones, are
known almost exclusively by their common
names CH 3
CH2 = CH2 CH3 CH= CH 2 CH3 C= CH2
IUPAC: Ethene Propene 2-Methylpropene
Common: Ethylene Propylene Isobutylene
Common Names
the common names methylene, vinyl, and allyl are
often used to show the presence of the following
alkenyl groups

Alk enyl Common IUPA C N ame

Grou p N ame Example (Common name)

CH 2= Methylene H2 C Methylidenecyclopen tane

(Methylenecyclopentan e)
Methylidene

CH 2=CH- Vin yl CH2 =CH Eth enylcyclop entane

Eth enyl (Vin ylcyclopen tane)

CH 2=CHCH 2 Allyl CH 2 =CHCH2 3-Propenylcyclopentane

(Allylcyclopentane)
3-Propenyl
Cis,Trans Isomerism in Alkenes
Cis,trans isomers: isomers that have the same
connectivity but a different arrangement of their
atoms in space due to the presence of either a
ring or a carbon-carbon double bond
H H H CH3
C C C C
H3 C CH3 H3 C H
cis -2-Buten e t rans-2-Butene
mp -139C, bp 4C mp -106C, b p 1C
Cis,Trans Isomerism
trans-cyclooctene is the smallest trans cyclooctene
that has been prepared in pure form and is stable at
room temperature
the cis isomer is 38 kJ (9.1 kcal)/mol more stable than
the trans isomer
the trans isomer is chiral even though it has no chiral
center

trans- Cyclooctene
(a pair of enantiomers)
The Cis,Trans System
Configurationis determined by the orientation of
atoms of the main chain

H CH2 CH3 H CH3

2 3
C C C C
1 4
CH3 CH H H3 C CH( CH3 ) 2
trans
2 -3-Hexene cis -3,4-D imethyl-2-penten e
E-Z Nomenclature

Use the CahnIngoldPrelog rules to

assign priorities to groups attached to
each carbon in the double bond.
If high priority groups are on the same
side, the name is Z (for zusammen).
If high priority groups are on opposite
sides, the name is E (for entgegen).
Example
Assign priority to the
substituents according
to their atomic number
(1 is highest priority).
1
2 If the highest priority
groups are on opposite
sides, the isomer is E.
1 2 If the highest priority
groups are on the same
E-1-bromo-1-chloropropene side, the isomer is Z.
The E,Z System
Example: name each alkene and specify its configuration
by the E,Z system

Cl
(a) (b)

Cl
Cl
(c) (d)
Br
Dienes, Trienes, and Polyenes
For alkenes containing two or more double
bonds, change the infix -en- to -adien-, -atrien-,
etc.
those containing several double bonds are often
referred more generally as polyenes
following are three dienes

1,4-Pentadiene 2-Methyl-1,3-butadiene 1,3-Cyclopentadiene

(Isoprene)
Dienes, Trienes, and Polyenes
for alkenes with n double bonds, each of which can
show cis,trans isomerism, 2n stereoisomers are
possible

1
2 3 2
4 5 4
6 7
(2E,4E)-2,4-Heptadien e (2E,4Z)-2,4-Hep tadiene

2 2
4 4

(2Z,4E)-2,4-Heptad iene (2Z,4Z)-2,4-Hep tadiene

Dienes, Trienes, and Polyenes
vitamin A, a biologically important compound for
which a number of cis,trans isomers is possible
there are four double bonds about which cis,trans
isomerism is possible, for 24 = 16 stereoisomers

CH2 OH

V itamin A (retinol)
Physical Properties of Alkenes
Low boiling points, increasing with mass.
Branched alkenes have lower boiling points.
Less dense than water.
Slightly polar:
Pi bond is polarizable, so instantaneous dipoledipole
interactions occur.
Alkyl groups are electron-donating toward the pi bond,
so may have a small dipole moment.
Commercial Uses of Ethylene
Commercial Uses of Propylene

=>
Chapter 7 27
Polarity and Dipole Moments of Alkenes

Cis alkenes have a greater dipole moment than trans

alkenes, so they will be slightly polar.
The boiling point of cis alkenes will be higher than the trans
alkenes.

Chapter 7 28
Terpenes
Terpene: a compound whose carbon skeleton
can be divided into two or more units identical
with the carbon skeleton of isoprene
head 2 4 tail
1 3

2-Methyl-1,3-butadiene
(Isoprene)
Terpenes
Myrcene, C10H16, a component of bayberry wax
and oils of bay and verbena

Menthol, from peppermint

OH
Terpenes
-Pinene, from turpentine
camphor, from the camphor tree

O
Fatty Acids
the four most abundant fatty acids
COOH Stearic acid (18:0)
(mp 70C)
COOH Oleic acid (18;1)
(mp 16C)

COOH Linoleic acid (18:2)

(mp-5C)

COOH Lin olen ic acid (18:3)

(mp -11C)