Republic of the Philippines

Laguna State Polytechnic University

Province of Laguna

College of Teacher Education

Alkenes and Alkynes

Nomenclature
Physical Properties
Preparations
Reactions
Group 2

Argente, Ann Sherina C.

Cabrera, Lizette S.
De Leon, Arizza Mae P.
Idian, Raquel P.
Villarin, Aira Mae M.
BSED 3F- Biological Science

Dr. Maria Eva E. Diongco

Instructor
 Republic of the Philippines
Laguna State Polytechnic University
Province of Laguna

College of Teacher Education

Dr. Maria Eva E. Diongco

Instructor
STRUCTURE OF ALKENES
 Alkenes are a class of hydrocarbons which is unsaturated compounds
with at least one carbon-to-carbon double bond.
 It is used to describe alkenes is olefins.
 Alkenes are more reactive than alkanes due to the presence of the
double bond.
 They are contain one or more C=C double bond somewhere in their
structures.
 General Formulas:
non-cyclic alkenes cyclic alkenes
CnH2n CnH2n-2

NOMENCLATURE OF ALKENES
1. Determine the stem name by selecting the longest possible straight
chain containing the C=C double bond and use the ending ‘-ene’
2. Number the parent chain so as to include both carbon atoms of the
double bond, and begin numbering with the end of the chain nearer the
C=C double bond
3. Designate the position of the C = C double bond by using the
number of the first atom of the double bond

4. Designate the positions of the substituent's by using the numbers

obtained by application of rule 2.
Examples

5. Indicated number of double bonds by prefixes (ene, diene, triene,

tetraene).

2- ethyl -1-pentene

1,4-pentadiene

6. If two identical groups are present on the same side of the C=C double
bond, the compound is designated as cis; if they are on opposite sides,
the compound is designated as trans.
Examples
Example
Give the IUPAC names for the following alkenes:

(a)

(b)

Answers
a) trans-3,4-dichlorohept-3-ene

b) cis-3,4-dimethyloct-3-ene

PHYSICAL PROPERTIES OF ALKENES

 Alkenes are non polar compounds.
 Insoluble in water.
 Soluble in non polar organic solvents.
 They are less dense than water.
Range of physical states

≤ 4 C's are gases

5 - 17 C's are liquids
≥ 18 C's are solids

 The alkenes has a boiling point which is a small number of degrees

lower than the corresponding alkanes.
 Name Formula Boiling Melting Density
point point (°C) at 20 °C
(°C) (g cm-3)

Ethene CH2 = CH2 -104 -169 —

Propene CH3CH = CH2 -47.7 -185 0.514

But-1-ene CH3CH2CH = CH2 -6.3 -185 0.595

Pent-1-ene CH3(CH2)2CH = 30 -165 0.641

CH2

Hex-1-ene CH3(CH2)2CH = 62.9 -140 0.673

CH2

cis-But-2-ene CH3CH = CHCH3 4 -139 0.621

(cis)

trans-But-2-ene CH3CH = CHCH3 1 -106 0.604

(trans)

2-Methylbut-1- CH3CH3C(CH3) = 31 -138 0.650

ene CH2

PREPARATION OF ALKENES
Dehydrohalogenation
It is the elimination of a hydrogen halide molecule from a haloalkane in
presence of KOH in alcohol

Examples
Dehydrohalogenation of 2° and 3° haloalkanes can take place in more than
one way and a mixture of alkenes is formed

alc. KOH
CH3CH2CHClCH3  CH3CH = CHCH3 + CH3CH2CH = CH2
heat
2-chlorobutane But-2-ene But-1-ene
(80%) (20%)

Note: the more highly substituted alkene is formed as major product

Saytzeff s Rule: In every instance in which more than one alkene can be
formed, the major product is the alkene with the most alkyl substituents
attached on the double bonded carbon.

CH CH CH
3 3
Br 3

+ KOH EtOH +
H
∆ 1-methyl cyclohexene 3 -methyl cyclohexene
Major Minor

Dehalogenation
Vicinal tetrahaloalkanes can be dehalogenated with zinc metal in an
organometallic reaction to form alkynes.
Substitution
Larger alkynes can be generated by reacting an alkyl halide with an acetylide
ion, which is generated from a shorter alkyne.

Dehydration (Alcohol)
It is the removal of a water molecule from a reactant molecule, in the
presence of Mineral acids (H2SO4, H3PO4)

Addition Reaction
Hydrogenation
The hydrogenation of alkynes using Lindlar’s catalyst produces alkenes.
To prevent further hydrogenation of the alkenes formed to alkanes
REACTION OF ALKENES
 Alkenes are more reactive than alkanes
 Reason: presence of the C=C double bond
 Alkenes undergo addition reactions and the reactions are
exothermic
 π-bonds weaker than σ-bonds

Electrophilic Addition Reaction

Addition of Hydrogen Bromide
Addition of hydrogen bromide to C = C double bond yields a bromoalkene

Examples
Propene reacts with HBr to give 2-bromopropane (major product) and 1-
bromopropane (minor product)

The formation of two possible products can be explained by the reaction

mechanism.

Markownikoff’s rule states that in the addition of HX to an unsymmetrical

alkene, the hydrogen atom adds to the carbon atom of the carbon-carbon
double bond that already has the greater number of hydrogen atoms.

2-bromopropane is the major product because the more stable secondary

carbocation is formed in the first step
 Addition of Bromine
Alkenes react rapidly with Br2 in 1,1,1-trichloroethane at room
temperature and in the absence of light

The behavior of alkenes towards Br2 in CH3CCl3 is useful test for the
presence of carbon-carbon multiple bonds

Add Br2 in The reddish

CH3CCl3 to brown colour of
Br2 is
excess
alkene decolourized

Addition of Bromine water

In an aqueous solution of Br2, the following equilibrium exists

HOBr HBr + Br2 + H2O

Bromic(I) acid

The bromine atom bears a partial positive charge while the oxygen atom
bears a partial negative charge ∵ oxygen is more electronegative than
bromine
When Bromic(I) acid reacts with alkenes, bromohydrin is formed

Addition of Sulphuric Acid

Alkenes react with cold and concentrated H2SO4 to form alkyl
hydrogensulphates

The large bulky –OSO3H group makes the alkyl hydrogen sulphate very
unstable. Two possible further reactions take place:
1. Regeneration of alkenes
2. Production of alcohols

Catalytic Hydrogenation
In the presence of metal catalysts (e.g. Pt, Pd or Ni), H2 is added to each
atom of C = C double bond to form an alkane

Addition of Hydration
Only one product is possible from the addition of H2O in presence of acids as
catalysts to symmetrical alkenes such as ethene and cyclohexene.

Symmetrical akenes
A A A A
+ H2O
H A A
A A H OH
OH
H CH3
+ H2 O
H3C
H
However, addition reactions to unsymmetrical alkenes will result in the
formation of Markovonikov’s product preferentially.

Unsymmetrical akenes
H

H OH
CH3 + H2O
CH3
POLYMERIZATION
Polymers: Compounds that consist of very large molecules made up of
many repeating units
Monomer: Each repeating unit
Polymerization: The reaction by which monomers are joined together
Addition polymerization: alkene monomers are joined together without the
elimination of small molecules
Addition polymer: The polymer produced by addition polymerization
STRUCTURE OF ALKYNES

o Alkynes are molecules that incorporate a CC triple bond

o An alkyne has the general molecular formula CnH2n-2, giving it four
fewer hydrogens than the maximum possible for the number of carbons
present.
o Acetylene is the simplest alkynes
o It is used in blow torches and as a precursor for the synthesis of more
complex alkynes
o More than 1000 different alkynes natural products have been isolated

NOMENCLATURE OF ALKYNES

1. Identify and name the substituents.

2. Identify the parent chain, which should include the CC triple bond
3. Assign a locant (and prefix if necessary) to each substituent giving the
CC triple bond the lowest number possible
The locant is ONE number, NOT two. Although the triple bond bridges
carbons 2 and 3, the locant is the lower of those two numbers
4. In addition to the IUPAC naming system, chemists often use common
names that are derived from the common parent name acetylene

PHYSICAL PROPERTIES OF ALKYNES

The physical properties of alkynes are very similar to those of the alkenes.
o Alkynes are generally nonpolar molecules with little solubility in polar
solvents, such as water.
o Solubility in nonpolar solvents, such as ether and acetone, is extensive.
o The single‐bonded carbon atoms, which are sp 3 hybridized
o The resulting asymmetrical electron distribution in the bond between
such carbon atoms results in the generation of a dipole moment.

PREPARATIONS OF ALKYNES

The preparations of alkynes are very similar to those of the alkenes. The
main preparative reactions involve the elimination of groups or ions from
molecules, resulting in the formation of π bonds.
 Dehydrohalogenation
o The loss of a hydrogen atom and a halogen atom from adjacent alkane
carbon atoms leads to the formation of an alkene.
o The loss of additional hydrogen and halogen atoms from the double‐
bonded carbon atoms leads to alkyne formation
o The halogen atoms may be located on the same carbon (a geminal
dihalide) or on adjacent carbons (a vicinal dihalide).

Dehalogenation
o Vicinal tetrahaloalkanes can be dehalogenated with zinc metal in an
organometallic reaction to form alkynes

Substitution

o Larger alkynes can be generated by reacting an alkyl halide with an

acetylide ion, which is generated from a shorter alkyne.

o Because acetylide ions are bases, elimination reactions can occur,

leading to the formation of an alkene from the alkyl halide.
o Because substitution and elimination reactions proceed through the
formation of a common intermediate, these two types of reactions
always occur simultaneously

Ethyne (acetylene) preparation

o Ethyne, which is commonly called acetylene, is the simplest alkyne.

o Historically, it was prepared by reacting calcium carbide with water.

o Today, ethyne is normally prepared by the pyrolysis of methane.

o In this procedure, a stream of methane gas is briefly heated to 1500°C
in an airless chamber.
 o Air must be excluded from the reaction or oxidation (combustion) will
occur.

REACTIONS OF ALKYNES

Addition Reaction
o Like alkenes, alkynes undergo addition reactions because they contain
relatively weak π bonds.
o Two sequential reactions can take place: addition of one equivalent of
reagent forms an alkene, which can then add a second equivalent of
reagent to yield a product having four new bonds.

Hydrogen halides
Alkynes undergo hydrohalogenation the addition of hydrogen halides, HX (X
= Cl, Br, I).

Two equivalents of HX are usually used: addition of one mole forms a vinyl
halide, which then reacts with a second mole of HX to form a geminal
dihalide.

Electrophilic addition

Electrophilic addition of HX to alkynes is slower than electrophilic addition of

HX to alkenes, even though alkynes are more polarizable and have more
loosely held π electrons than alkenes.

Markovnikov addition in step [3] places the H on the terminal carbon to form
the more substituted carbocation A, rather than the less substituted
carbocation B.
Carbocation A is stabilized by resonance, but B is not.

o Two resonance structures can be drawn for carbocation A, but only

one Lewis structure can be drawn for carbocation B.

Addition of Halogen

Halogens X2 (X = Cl or Br) add to alkynes just as they do to alkenes.

Addition of one mole of X2 forms a trans dihalide, which can then react with a
second mole of X2 to yield a tetrahalide

Addition of Water
o In the presence of strong acid or Hg2+ catalyst, the elements of H2O add
to the triple bond, but the initial addition product, an enol, is unstable and
rearranges to a product containing a carbonyl group— that is, a C=O.
o A carbonyl compound having two alkyl groups bonded to the C=O carbon
is called a ketone.

Hydroboration—Oxidation
• Hydroboration—oxidation is a two-step reaction sequence that
converts an alkyne to a carbonyl compound.
• Hydroboration—oxidation of an internal alkyne forms a ketone.
 • Hydroboration of a terminal alkyne adds BH2 to the less substituted,
terminal carbon.
• After oxidation to the enol, tautomerization yields an aldehyde, a
carbonyl compound having a hydrogen atom bonded to the carbonyl
carbon.

Acetylide anions
Because sp hybridized C—H bonds are more acidic than sp2 and sp3
hybridized C—H bonds, terminal alkynes are readily deprotonated with strong
base in a BrØnsted-Lowry acid-base reaction. The resulting ion is called the
acetylide ion.

o Acetylide anions react with unhindered alkyl halides to yield products of

nucleophilic substitution.
o Because acetylides are strong nucleophiles, the mechanism of substitution
is SN2, and thus the reaction is fastest with CH3X and 10 alkyl halides.