ALKENES U

OLEFINS
 CHARACTERISTICS:
• Alkenes are hydrocarbons that have a carbon-carbon double bond in their
molecule, and that is why they are called unsaturated .
• The generic formula is C n H 2n. This general formula is fulfilled in alkenes
that have a single double bond in their structure.
• The double bond can be considered
the functional group of alkenes and
determines their chemical properties.
• The simplest alkene is ethene or
ethylene .
• As with other organic compounds,
some alkenes are still known by their
non-systematic names, in which case
the systematic ending -ene is
replaced by -ylene , as is the case
with ethene , which is sometimes
called ethylene , or propene by
propylene . Cyclic alkenes are called
cycloalkenes .
Electronic structure: the π bond
• The double bond has two components: the σ
and the π. The two carbon atoms that share
the bond are sp 2 hybridized,
• When these sp 2 orbitals combine, the shared
electrons form a π bond, located between both
carbons.
 In lace C

• The formation of the pi bond can be seen (dotted line); which is formed by the overlap of
the two 2p orbitals perpendicular to the plane of the molecule. In this type of bond the
electrons are delocalized around the carbons, above and below the molecular
plane.

• Sp 2 orbitals have the same shape as sp 3 orbitals but are smaller. Therefore the double
bond is shorter (1.34 Å) than the single bond (1.53-1.54 Å).

Nomenclature
The rules for naming unsaturated
 hydrocarbons are similar to those used for
alkanes, only it is necessary to add some
other rules for naming and placing double
bonds:
• 1. – Carbon-carbon double bonds are
designated by the ending ene : if more than
one double bond is present, the ending will be
diene, triene, and so on.
• 2. – The basic name of the compound is
determined by selecting the longest chain that
contains the double bond(s).
• 3. – The carbons of the chain are
numbered so that the two atoms of
the double bond are included and
start at the closest end of said bond.
 The location of the double bond is
designated by the number of the first
atom of the bond as a prefix.
• 4. – The positions of the substituent
groups are indicated by the number of
the atom to which they are attached.
 CH;C-CHCH3 '
CH,CH,CH,

CH-CH2CHCH CH,CH
 ISOMERIA
f of structural chain • of
position. of function

stereoisomery
geometric
shallow
optics
Stereoisomerism occurs in
compounds that have the
same structure but are
different in the spatial
distribution of their atoms.
• One of the forms of stereoisomerism is
geometric isomerism .
• Geometric isomerism from a mechanical
point of view is generally due to the fact that
free rotation around the axis of the double
bond is not possible.
• It is characteristic of substances that have a
c=c double bond .

RULER:
• In order for it to occur in
compounds with a double
bond, the substituents on
each of the carbons
involved in the double bond
must be different. That is,
none of the carbons
involved in the double bond
have the same two
substituents.
 For example, there are two 2 butenes:

Figure 6.1.

Both •H s are The CH 3 are,

a1 mi5m lade: cs on opposite sides: trans
• Geometric isomers (cis-
trans) are stereoisomers
because they differ only in
the spatial arrangement of
 the groups.
• They have different physical
properties (e.g. eb., f., etc.).
• Instead of cis-trans, the
letters Z, E can be used.
• The letter Z is used if the
highest priority substituents
on each carbon are on the
same side of the double
bond. The letter E indicates
that they are on opposite
sides.
Which of the following alkenes have geometric isomerism?
Give the structural formulas and names of the isomers.
ANSWERS:
(a) There are no geometric isomers, since one of the Cs of the double bond supports
two equal groups (C2H5).
(b) There are no geometric isomers; a double bond C has two Hs.
(c)It has geometric isomers because each C of the double bond has two different
substituents:
(d)It has two geometric isomers because one of the double bonds has two different
substituents: H,C CH=CH, H

cis- 0 (Z)-1-Iodine-2-pentene trans- or (E) 1-Iodine-2-pentene

)C=C
)C=C H h h
(Z)-1,3-Pentadiene (cis)
CH=CH,
(e) Both double bonds meet the condition to have geometric isomerism.
2,4Heptadiene has four diastereomers:
H,C

CH,CH

cis, cis or (Z, Z) runs. ¿Li ti (E, Z)

CH,CH
cis, tran or (Z, E) frog, trans 0 (E, E)

Note that the prefixes cis and trans and the letters Z, E appear in the same order
in which the double bonds are numbered.

(f) Now there are only three isomers, since

the cistrans and transcis geometries are
identical.
 ci, ch-2,4- Hexadiene 0 cis, tran-24 Hexadiene or frans, franr2,4-Hexadiene 0
(Z, Z}2,4-Hexadiene (Z,E)2,4-Hexadiene (E, E}24-Hexadiene
• Give the structural formulas and systematic
names of all isomers of pentene, including
stereoisomers.
 Physical properties of alkenes
The presence of the double bond slightly
modifies the
physical properties of alkenes versus alkanes.
1. Natural state : At room temperature and 1
atmosphere of pressure, ethene to butane ( C4H8 )
are gases. From C5 to C18 are liquids and from
C19 onwards are solids.
2. Solubility : As non-polar or very slightly polar
compounds, they are insoluble in water, but quite
soluble in non-polar liquids such as benzene, ether,
chloroform.
1. Boiling points : They increase with the increase in the number of carbons.
 The branches lower the boiling point.
2. Melting point : They also increase as the number of carbon atoms
increases.
3. Density : They have densities less than 1 g/cc and as the size of the alkene
increases, the density increases.
6. The greater the number of alkyl groups linked to the carbons of the
double bond (the more substituted the double bond is), the
greater the stability of the alkene .
 Chemical properties
Addition Reactions: They are the most common in compounds that have carbon-
carbon double bonds.
Symmetric agent :

Asymmetric agent :
 Reaction
Guy L 14

Catalytic hydrogenation \ / H2
)e Ck Catalyst 9F
(Pt.Pd or Ni) II
xi
Halogenation (X = Cl, Br)
\ 7 x, 11
AP x

Hydrohalogenation (X = Cl, Br, I) (markovnikov)

11
N/ HX -------DC---------------
C=c ---------------------------• 1।
/X

. . _L .
Hydration (markovnikov) c=c( -------------—--------- 1C
/ \ H2S04 DC
1 HOUR
ALKENE USES
Af &FE d praem Pa mzere E Jso s bparz eE•ca •es

bags, bottles.
toys

Botellaus, «eletergemte-
HrEícuIes mmelcieadles

Fomeprfices discs, Delc tlas, aast 3 c LJ 1« s of

artificial leather C izl , m am gers

Fibers {Oren, P1iler)

Tyflon, heat resistant films

r etrfl uoro eti Ie ii o

 • The most important use of alkenes is as raw
material for the production of plastics
(polyethylene = fibers, molds, wrappers)
• ETHYLENE: It is a colorless, tasteless gas
with a light odor whose formula is CH2=CH2
• It is used in the ripening of green fruits such as
pineapples, tomatoes, mangoes, bananas, etc.
• In ancient times it was used as an anesthetic
and in the manufacture of mustard gas.
• Polyethylene and propylene are obtained from the polymerization of
ethylene and propylene respectively, which are used in the manufacture of
articles such as: disposable bottles,
 returnables, jugs, bags, chairs, tables, toys among others.
• Nonene, when combined with phenol, forms noniphenol, which is the base
of some hair shampoos.
Insects expel very small amounts of unsaturated substances called pheromones, which they
use to communicate with other members of their species. Some pheromones indicate danger
or are a call to defend oneself, others constitute a trail or are sexual attractants. The bioactivity
of many of these substances depends on the cis or trans configuration of the double bond in
the molecule.
Currently these substances are being used as sexual attractants to trap and eliminate insects,
such as the African bee, termite, weevil, moth, etc.

CH, h
CH,(CH2)7 ,(CH2)2CHa
cH
h
= H'PH
C=C

c=C
H' PCH,(CH,)CH,OH Sexual attractant for moths
Fly sexual attractant
domestic female
domestic female

CH—CH -CK CHa(CH2) 12H

2ge
Ic=
H YES NO,

Danger sign for ants Defense signal for termites