ORGANIC CHEMISTRY (CHM 121)

Lecture 3
 Alkenes
Alkenes are hydrocarbons that contain a carbon–carbon double bond. Tomatoes are shipped
Alkenes play many important roles in biology. For example, ethene green so they arrive
(H2C=CH2), the smallest alkene, is a plant hormone—a compound that unspoiled. Ripening
controls growth and other changes in the plant’s tissues. Among other
things, ethene affects seed germination, flower maturation, and fruit starts when they are
ripening. Many of the flavors and fragrances produced by plants also exposed to ethene.
belong to the alkene family.
 ALKENES
Alkenes are hydrocarbons that contain a C=C M. F. CnH2n

ALKENE NOMENCLATURE
Alkenes IUPAC names by replacing the -ane ending of the
corresponding alkane with -ene.

Alkenes common names by replacing the -ane ending of

the corresponding alkane with -ylene
The longest continuous chain that includes the C=C bond
forms the base name of the alkene
This chain is numbered in the direction that gives the C=C
their lower numbers
The locant of only one of the C=C is specified in the name;
the 2nd C of C=C must follow in sequence

C=C take precedence over R and X in determining the

main C chain and the direction in which it is numbered
 1 CH2
CH3 2 CH
CH3 CH CH2 CH2 CH CH2 CH2 CH3
7 6 5 4 3

6-Methyl-3-n-propylhept-1-ene
or
6-Methyl-3-n-propyl-1-heptene

OH groups outrank the C=C

Compounds that contain both C=C and OH group use the
combined suffix -en + -ol
 Three alkenyl groups vinyl, allyl, and isopropenyl-

Cycloalkenes
 Dienes and Polyenes

* Nomenclature
H H H H H H H H H H H H H
H C C C C H H C C C C H H C C C C C H
H H
1,3-Butadiene 1,2-Butadiene 1,4-Pentadiene
or or or
Buta-1,3-diene Buta-1,2-diene Penta-1,4-diene

H H H H
H C C C C C H CH2 C CH2
Penta-1,2,4-triene Prop-1,2-diene
(Allene)
 ISOMERISM IN ALKENES
Ethylene and Propene only one structure present
Butane has 4 isomers with the same molecular formula C4H8

Constitutional isomer Stereoisomers

Stereoisomers have the same constitution but differ in the

arrangement of their atoms in space
Cis–trans stereoisomerism in alkenes is not possible when
one of the doubly bonded carbons bears two identical
substituents

Neither 1-butene nor 2-methylpropene can have stereoisomers

 THE NOMENCLATURE OF ALKENES
1. The longest continuous chain that contains the functional group (in this case, the carbon– carbon double
bond) is numbered in the direction that gives the functional group suffix the lowest possible number. For
example, 1-butene signifies that the double bond is between the first and second carbons of butene; 2-
hexene signifies that the double bond is between the second and third carbons of hexene.
2. For a compound with two or more double bonds, the “ne” ending of the corresponding alkane is replaced with
“diene,” “triene,” “tetraene,” and so on, depending on the number of double bonds in the parent hydrocarbon.

3. The name of a substituent is stated before the name of the longest continuous chain that contains the functional
group, together with a number to designate the carbon to which the substituent is attached. Notice that if a
compound’s name contains both a functional group suffix and a substituent, the chain is numbered so that the
functional group suffix gets the lowest possible number.
4. If a chain has more than one substituent, the substituents are stated in alphabetical order. Then the appropriate
number is assigned to each substituent.

5- If counting in either direction results in the same number for the functional group suffix, the correct name is the
one containing the lowest substituent number. For example, the compound shown below on the left is a 4-octene
whether the longest continuous chain is numbered from left to right or from right to left. If you number from left to
right, then the substituents are at positions 4 and 7, but if you number from right to left, they are at positions 2 and
5. Of those four substituent numbers, 2 is the lowest, so the compound is named 2,5-dimethyl-4-octene.
6- A number is not needed to denote the position of the double bond in a cyclic alkene because the ring is
always numbered so that the double bond is between carbons 1 and 2. To assign numbers to any
substituents, count around the ring in the direction (clockwise or counterclock
wise) that puts the lowest number into the name.
7- If counting in either direction leads to the same number for the alkene functional group suffix and the
same lowest number or numbers for one or more of the substituents, then ignore those substituents and
choose the direction that gives the lowest number to one of the remaining substituents.
•Methods of preparation of alkenes
1) By dehydration of alcohols Conc. H2SO4 / 80 oC
CH3 CH2 OSO3H

Ethyl hydrogen sulfate

CH3 CH2 OH
170 oC
Ethanol
H3PO4 / 200 oC
CH2 CH2

2) By dehydrohalogenation of allkyl halides

• The elemination of HBr obeys Saytzeff`s rule
alc. KOH
CH3 CH2 CH CH3 CH3 CH CH CH3
- HBr
Br 2-Butene
2-Bromobutane (But-2-ene)
3) By dehalogenation of dihalogenated alkanes
Zn
CH3 CH CH CH3 CH3 CH CH CH3
Br Br - ZnBr2
2-Butene
2,3-Dibromobutane (But-2-ene)

4) By Kolb`s electrolysis
CH2 COOK Electrolysis CH2
+ CO2 + KOH + H2
CH2 COOK + H2O CH2

Potasium succinate
Anode Cathode
 REACTIONS OF ALKENES
ADDITION REACTIONS
The characteristic reaction of alkenes is addition to C=C:

HYDROGENATION OF ALKENES
The hydrogenation of alkenes to yield alkanes
Hydrogenation is the addition of H2 to a multiple bond
An electron-deficient species is called an electrophile. Literally, “electrophile” means “electron loving”
(phile is the Greek suffix for “loving”). An electrophile looks for a pair of electrons. It is easy to recognize
an electrophile—it has either a positive charge, a partial positive charge, or an incomplete octet that can
accept electrons.

An electron-rich species is called a nucleophile. A nucleophile has a pair of electrons it can share.
Nucleophiles and electrophiles attract each other (like negative and positive charges) because nucleophiles
have electrons to share and electrophiles are seeking electrons. Thus, the preceding rule can be restated
as nucleophiles react with electrophiles.
ELECTROPHILIC ADDITION OF HX TO ALKENES
 The reactivity of HX reflects their ability to donate H+
HI is the strongest acid of the HX and reacts with alkenes
at the fastest rate
Mechanism of the electrophilic addition
Alkene can accept H+ from HX to form a carbocation
The reaction is started by the attack of H+ on the e’s C=C
to generate a carbocation as a reactive intermediate
ADDITION OF HX MARKOVNIKOV’S RULE

HX can add to an unsymmetrical alkene (an alkene in

which the two C of the C=C are not equivalently
substituted) in either of two directions
Markovnikov’s rule states that when an unsymmetrically
substituted alkene reacts with HX, the H adds to the C that
has the greater number of H, and the X adds to the C
having fewer H substituents
MECHANISTIC BASIS FOR MARKOVNIKOV’S RULE
Let’s compare the carbocation intermediates for addition
of a HX to an unsymmetrical alkene of the type RCH=CH2
(a) Addition according to Markovnikov’s rule

(b) Addition opposite to Markovnikov’s rule:

The activation energy of 3ry carbocation is less than that
of 2ry carbocation which less than that of 1ry carbocation

3ry C+ more stable than 2ry C+ more stable than 1ry C+

FREE-RADICAL ADDITION OF HBr TO ALKENES

Kharasch concluded that anti-Markovnikov addition

occurred when peroxides (ROOR) were present in the
reaction mixture. This phenomenon called Karasch or
peroxide effect

M- Rule

Anti-M- Rule
The mechanism

(a) Initiation
Step 1: Dissociation of a peroxide into two alkoxy radicals

Step 2: H atom abstraction from HBr by an alkoxy radical

(b) Chain propagation
Step 3: Addition of a bromine atom to the alkene

Step 4: Abstraction of a H atom from HBr by the free

radical formed in step 3
 Br atom adds to the alkene in the direction that produces
the more stable alkyl radical
Addition of Br atom to C-1 gives 2ry alkyl radical

Addition of Br atom to C-2 gives 1ry alkyl radical

 2ry alkyl radical is more stable than 1ry radical
Br therefore adds to C-1 of 1-butene faster than it
adds to C-2
ADDITION OF H2SO4TO ALKENES

M-Rule
Alkyl hydrogen sulfates (R-SO2OH) can be converted to
alcohols by hydrolysis

The mechanism
Step 1: Protonation of the C=C in the direction that leads
to the more stable carbocation
Step 2: Carbocation–anion combination

The overall reaction represented thus:

ADDITION OF X2 TO ALKENES
X2 reacted with alkenes by electrophilic addition
OZONOLYSIS OF ALKENES
Ozone (O3) is the triatomic form of oxygen, neutral but
polar molecule that can be represented thus:

Ozone reacted with alkenes to give ozonide

Ozonides undergo hydrolysis in water to give two carbonyl

(C=O) containing compounds
Two aldehydes, two ketones, or one aldehyde and one
ketone may be formed
Example:
An alkene having the molecular formula C8H16 subjected
to ozonolysis, giving acetone and 2,2-dimethylpropanal
One of the C=C bears 2 CH3; the
other bears H, a tert-butyl group
5
H3C
4 CH3
CH3
Thus, such alkene is: H3C 3 2
2,4,4-trimethyl-2-pentene,
CH3
(CH3)3CCH=C(CH3)2 1
What alkene should
used to synthesize 3-
bromohexane?

2-hexene + HBr -----------> ?????

3-hexene + HBr -----------> ?????