PH 122 [PH106]

Organic Chemistry I
Instructor: D. Parmena, ([email protected])
Department of Chemistry, Faculty of Natural and Applied Sciences
SOPH
― 23Linda moyo wako kwa uangalifu wote,
maana humo zatoka chemchemi za uhai.

24Tenga mbali nawe lugha potovu;

wala midomo yako isitamke maneno

madanganyifu.
Methali 4: 23-24, BHN

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ALKENES
CnH2n

General Overview
Nomenclature
Physical Properties

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 An alcohol Alkane from
RCH2CH2OH petroleum oil

•Al2O3 at 400 oC or
•Exess conc. H2SO4, 170 oC or ‗CRACKING‘ IS USED
•H2PO4(l) (this is better) INDUSTRIALLY. Alkane
vapour is passed over a
heated catalyst e.g.
SiO2 + Al2O3

Sources of Alkenes
A secondary
bromoalkane
KOH in ethanol

RCH CH2
RCHCH An alkene
RCHCH33
Br
Br

(This reaction gives a fair yield with a

2o halogenoalkane, a good yield with a
3o halogenoalkane and a very poor yield
with a 1o halogenoalkane)
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Alkenes: Overview

▪ Alkenes are hydrocarbons that contain a carbon-carbon double bond.

▪ They are homologous series of aliphatic hydrocarbons that formed by a
carbon-carbon double bond (C=C) having two pairs of shared electrons.
▪ The double bond and in a molecule plays an import mark for chemical
properties even if the molecule is complicated.
▪ The number of hydrogen atoms in an alkene is double the number of carbon
atoms and can it be represented by the formula CnH2n.
▫ For example, the molecular formula of ethene is C2H4, while for propene
it is C3H6.
▪ Alkenes are called unsaturated hydrocarbons because the double bond can
open to allow them to take up more hydrogen atoms or other species.

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Hybridization of Alkenes

Trigonal planar
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Nomenclature of Alkenes

▪ Step 1. Identify and name the longest continuous chain of C atoms which
contains the double bond(s) (#C + -ene).
▪ Step 2. Number the longest chain so that the C‘s joined by the double bond have
the lowest numbers possible. If the double bond has the same position starting
from either end, use the positions of the substituents to determine beginning of
the chain.
▪ Step 3. Locate the double bond by the lower numbered carbon atom joined by
the double bond (e.g., 1-butene).
▪ Step 4. Locate and name attached groups.
▪ Step 5. Combine the names for the attached groups and the longest chain into
the name.

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Nomenclature of Alkenes …

▪ If there is more than one double bond:

 a counting prefix (di-, tri-, tetra-, etc.) is placed immediately
in front of the suffix -ene to indicate the number of double
bonds (diene, triene, tetraene, etc.).
 Usually, an ―a‖ is placed before the counting prefix to make
pronunciation easier (e.g., butadiene).
 The starting position of each double bond is indicated by the
lower number, separated by commas (e.g., 1,3-butadiene).
 For cycloalkenes, the ring is named as cyclo- + #C + -ene; one of
the carbons of the double bond must be numbered ―1.‖

1-methylcyclobuta-1,3-diene
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Nomenclature of Alkenes

1. Provide acceptable IUPAC names for 2. Provide acceptable IUPAC names for
the following molecules: (ignore the following molecules:
geometric isomerism) 1. CH2=CH-CH=CH2
1. CH3CH2CH=CH2
2. CH3CH2CH=C(CH3)CH2CH3
2. CH3CH2CH=CHCH3

3. (CH3)2CHCH=CHCH3 3.

4.
4.

5.
5.

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Nomenclature of Alkenes …

▪ Because free rotation is not possible around double bonds, there are
two different forms of geometric isomers of each other:
 The prefix cis- is used when the two arms of the longest
chain are on the same side of the double bond;
 the prefix trans- is used when they are on opposite sides of
the double bond.
▪ Geometric isomers can have drastically different chemical and
physical properties

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Dipole moment in alkenes (C=C)

▪ Alkyl group releasing electrons to the doubly-

bonded carbon.
▪ Since this polarity is not canceled by a
corresponding polarity in the opposite direction, it
gives a net dipole moment to the molecule

▪ In cis-2-butene with one methyl and one hydrogen

on each side of the molecule, the bond moments
should cancel out.
▪ Because of its higher polarity the cis-isomer is
generally the higher boiling of a pair; because of
its lower symmetry it fits into a crystalline lattice
more poorly, and thus generally has the lower
melting point. 11
Dipole moment in alkenes (C=C)

The differences in polarity, and hence the differences in melting point and boiling
point, are greater for alkenes that contain elements whose electronegativities
differ widely from that of carbon.

Question: Would cis-2,3-dichloro-2-butene have a larger or smaller dipole moment

than cis-1,2-dichloroethene? 12
Instability of cis-isomers
The order of stability is
The greater enthalpy of cis isomers can be
trans-2-butene > cis-2-butene > 1-butene.
attributed to strain caused by the crowding
of two alkyl groups on the same side of
the double bond.
The different amount of heat evolved is
related to different stabilities

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Nomenclature of Alkenes: Problems

1. Draw structural formulas for the 2. Draw structural formulas for

following molecules: Assess the the following molecules:
structure and correct the name a) cis-2-pentene
where necessary by giving a b) trans-3-methyl-3-hexene:
salient reason. (c)
a) 2-methyl-2-butene
b) 2-methyl-3-pentene
c) 4-ethyl-3-hexene
d) 2,3,4-trimethyl-1,3-pentadiene
(d)
e) 5-ethyl-1,3-cyclopentadiene

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Physical properties of Alkenes

Many of the physical properties of alkenes are similar to

those of alkanes.
▪ Alkenes are nonpolar compounds. (insoluble in water,
but soluble in nonpolar solvents)
▪ They are less dense than water.
▪ Range of physical states:
– ≤ 4 C's — gases
– 5 - 17 C's — liquids
– ≥ 18 C's — solids
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Some Important Alkenes

H H ▪ Used in the manufacture of the plastic polyethylene. The release of

ethylene stimulates the beginning of the ripening process in many plants;
H H
some plants can be picked while unripe (when they are less fragile), and
exposed to ethylene gas to cause ripening once they reach their destination
Ethylene

H CH3 ▪ Propylene (propene), produced in the cracking of petroleum; used in the

H H manufacture of the plastic polypropylene.

Propene

H Cl
▪ Chloroethene, a carcinogenic gas manufactured from ethylene; used in the
manufacture of the plastic polyvinyl chloride (PVC).
H H
Chloroethene

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Some Important Uses of Alkenes in Pharmaceuticals

▪ Propylene glycol which is an alkene is used as a N

O

solvent in many pharmaceuticals, including oral,

injectable and topical formulations, such as for Cl N
diazepam and lorazepam which are insoluble in water.
▪ Alkenes are the raw materials for the manufacture of
chemicals like alcohols, aldehydes etc. diazepam

▪ Alkenes are also used as general anesthesia. H

N
O

▪ Ethene is a plant hormone which controls growth, seed OH

germination and fruit development. Cl N

▫ Therefore, ethene is used for artificial ripening of

fruits, flower maturation, etc. lorazepam
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Terpenes and Essential Oils

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Terpenes and Essential Oils

Terpenes are a diverse group of

molecules which are biologically
synthesized from isoprene units.
They are found in many plants,
and often have distinctive flavors
and aromas. They are often
components of essential oils, so
named because they have a
characteristic “essence” or
fragrance.
Many of these molecules are
components of common foods and
perfumes.
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The Chemistry of Vision

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The Chemistry of Vision
H ▪In the rod and cone cells in the retina of the eye,
H retinal in rhodopsin is found ―at rest‖ in the cis-
H
form.
cis-retinal
O
▪When it absorbs a photon (hν) of light, one of the
h π- bonds is broken, causing the molecule to rotate
Sun light Enzymatic reaction and lock into the trans form, which has a
completely different shape.
H H ▪This starts a long chain of chemical processes
which eventually results in a visual image in the
O
brain.
H
trans-retinal ▪The transretinal molecule is then twisted back
into the cis form by another enzyme.
When you look directly at a very bright light, the ―afterimage‖ that you see in front of your eyes is
the result of a large amount of cis-retinal having been transformed into trans-retinal all at once; the
enzymes take a little bit of time to go through and ―reset‖ all of these molecules 21
Reactions of Alkenes
▪ Chemical Properties
▪ Addition reaction
▫ Halogenation
▫ Hydrogenation
▫ Addition of acid
▫ Hydration
▫ Polymerization
▪ Preparation of alkene
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―

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Chemical properties of Alkenes

Alkenes are unsaturated compounds, which makes them highly reactive.

Most of these chemical reactions occur at the Carbon-Carbon double
bonds.
This makes alkenes far more reactive than alkanes.
 Alkenes undergo three types of main reactions, which are as follows
Addition Reactions
Addition of Hydrogen
Addition of Halogens
Addition of Water
Addition of Halides
Oxidation Reactions
Combustion Reaction
Oxidation by KMnO4 24
―

25
―

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Addition Reactions
Addition of Hydrogen:
In the presence of nickel or platinum alkenes will react to add to its molecular chain one
diatomic molecule of hydrogen (dihydrogen).
And in this process, they become alkanes due to the rearrangement of atoms.

R' R R' H H
R H2
C C + H H R'' C C R''' H H
Pt Pt
"R R''' H H (Z)-but-2-ene butane
H H
H2
-OC(O)(CH2)5CH=CH(CH2)5CH3 -OC(O)(CH2)5C C(CH2)5CH3
Pt
vegetable oil Cooking fat H H

The reaction only takes place in the presence of a metal catalyst (usually Pt or Pd).
This same process is used to produce hydrogenated vegetable oils such as
margarine and shortening. 27
Since the common catalysts used are insoluble metals such as palladium in the form Pd-C, platinum in the
form PtO2, and nickel in the form Ra-Ni; the H-H bond in H2 cleaves, and each hydrogen attaches to the metal
catalyst surface, forming metal-hydrogen bonds. The metal catalyst also absorbs the alkene onto its surface.

https://courses.lumenlearning.com/suny-potsdam-organicchemistry2/chapter/19-4-reduction-of-alkenes-and-alkynes/ 28
Problem
▪ Recently, scientists have become
increasingly worried about the presence
of unnatural fatty acids found in
margarine and other food products
made from partially hydrogenized oils.
Discuss

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Addition Reactions

Addition of Halogens: (e.g Cl2 and Br2 )

 Halogens will react with alkenes to form vicinal dihalides. From the halogens,
iodine will not react with alkenes.
 But Bromine reacts with alkenes and will attach at the unsaturated site.
 The reaction is used to as proof of unsaturation.

C2H4(g) + Br2 (aq) → C2H4Br2 (aq)

Approximately 10 million tons of 1,2-dichloroethane are manufactured each year

in the United States by the reaction of ethylene with chlorine.
The process is the first step in making PVC [poly(vinyl chloride)] plastics.
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Addition of Halogens…
  Polarization of Br2 by a double bond
Br Br
R R Br R
Br
H H H
The reaction is carried out simply by R R R
mixing together the two reactants,
usually in an inert solvent like carbon
tetrachloride. Br
The distortion of the electron R R
distribution in one molecule caused by Br Br
H H
another molecule is called R R
polarization. Br
i.e. the alkene has polarized the
halogen molecule, Br2. Br
The dense electron cloud of the C=C tends to repel the similarly charged electron cloud of the halogen molecule; this repulsion
makes, the halogen atom that is nearer the double bond relatively positive and its partner relatively negative.
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Addition of Halogens…
Addition of Halogens in Cycloakenes

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Addition of Halogens…

Halohydrin formation
▪ The addition of chlorine or
bromine in the presence of
water can yield compounds
containing halogen and
hydroxyl groups on
adjacent carbon atoms.
▪ These compounds are
commonly referred to as
halohydrins. Under proper
conditions, they can be
made the major products.

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Addition of Halogens…
Halohydrin formation
When an alkene is reacted bromine in aqueous solution (rather than CCl4), the major product is
a halohydrin (halo alcohol).

  R R
Br
Br Br Br
H R
R H R Br
R O H
H
R H2O
H H acid-base R OH
H2O
+ BrH
Br
Example:

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Addition Reactions
Addition of Water:
▪ According to the Markovnikov rule, water will react with an alkene to form
alcohols. Alkenes don‘t react with pure water, but in the presence of a strong acid
catalyst such as sulfuric acid.
▪ Markovnikov rule, the hydrogen will attach at the double bond to the atom with
more hydrogen atoms attached
▪ An –H from water adds to one carbon, and an –OH adds to the other.

CH2=CH2 + H2O → CH3CH2OH.

For example, nearly 300 million gallons of ethyl alcohol (ethanol) are produced
each year in the United States by the acid-catalyzed addition of water to ethylene: 35
Addition Reactions
Addition of Water under sulfuric acid: Mechanism
▪ Electrons density in the double bond of alkene is high. Therefore this double bond
can attack positively charged parts such as H+ δ-OSO3H. Molecule is a polarized
molecule such as Hδ+ and Oδ-. Hδ+ is attacked by double bond of alkene. Meanwhile
H-O bond is braked in the H2SO4 molecule. Then a carbocation is formed. That
carbocation is attacked by O- in the -OSO3H. Then H2O is hydrolyzed and H2SO4 is
released again. Hence H2SO4 is behaved as an catalyst.
H H H
C CH2 C CH2 C CH2
H
HO3SO H
H OSO3H OSO3H H2O

H
C CH3
OH 36
Addition Reactions
Acid addition:
▪ If the alkene is unsymmetrical, there are two possible products in this kind of
reaction:

The major product of the reaction is

predicted using Markonikov’s Rule:

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Addition Reactions

▪ Markovnikov's rule replaced by a more general rule: electrophilic addition to a

carbon-carbon double bond involves the intermediate formation of the more
stable carbonium ion.
▪ Stability of carboniumions 3 > 2  > 1  > CH3+

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Addition Reactions
Rearrangement of carbonium ions

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Alkenes: Problems

1. Show the products of the reaction 2. The reaction of 2-pentene with in

of 2-butene with the following: the presence of H2O yields a
mixture of two alcohol products.
Draw their structures.
a) H2 and Pd
b) Br2 3. Draw the structure of the alcohol
c) H2O/H2SO4 catalyst you would expect to obtain by
acid-catalyzed reaction of the
following cyclic alkene with H2O:

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Problems
Complete these reactions

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ASSIGNMENT 1

Write short search ( up to two pages) on the

importance on alkyl halides and alkenes on
Medicinal and Pharmaceutical industries.
[It could be on natural sources or synthetics.]

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HOME WORK

1. With examples ranging industrial applications to

commercialization write short notes on
Polymerization
2. Write short notes about dimerization, use the
following reaction to proceed.

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