Organic Chemistry
Lecture 3: Alkenes
Contents:
Alkenes:
Structure
Naming
Isomerism
Physical and Chemical Properties
Polymerization
Synthesis
Aromatic Hydrocarbons
University of Technology-
Petroleum Technology Dept Ass.Prof. Rana A.Azeez
What are Alkenes (Olefins)
The Alkenes Series
Alkene Nomenclature (Naming)
2-hexene
3-butyl-2,4-hexadiene
1. Parent chain = longest chain that includes the double bond(s)
2. The double bonds have priority and must have the lowest number(s)
possible
3. The first C atom in the C=C bond indicates the double bond’s location
(or number in naming)
4. Name, number, & alphabetize substituents as usual
5. Replace –ane ending with –ene ending
– Two double bonds: -diene; three double bonds: -triene
6. Put double bond number in front of entire root name
(i.e. 2-pentene indicates the double bond starts on carbon 2)
7. Cyclic alkenes: number the atoms in the ring starting with the double
bond
Nomenclature of Alkenes
5
Naming Practice
4-ethyl-3,5-dimethyl-2-heptene 2,4-hexadiene
4-isopropyl-3,5-dimethyl-
3,4-dimethyl-1,3-pentadiene
1,3,5-heptatriene
STRUCTURAL ISOMERISM IN ALKENES
Different structures are possible due to...
Different positions for the double bond
pent-1-ene pent-2-ene
Branching
3-methybut-1-ene
GEOMETRICAL ISOMERISM IN ALKENES
• an example of stereoisomerism
• found in some, but not all, alkenes
• occurs due to the RESTRICTED ROTATION OF C=C bonds
• get two forms....
CIS TRANS
Groups/atoms are on the Groups/atoms are on OPPOSITE
SAME SIDE of the double bond SIDES across the double bond
Isomers - have different physical properties - e.g. boiling points, density
- have similar chemical properties - in most cases
Cis-trans isomerism in alkenes
• Substituents will stay on the same or opposite sides of the double
bond (no C=C bond rotation)
H3C CH3 H3C H
H
C C
H
X H
C C
CH3
cis- 2-butene trans- 2-butene
(same side) (opposite sides)
• For cis-trans isomerism, each C in the double bond must have 2
different substituents attached (i.e. a C and a H, etc.)
• Determining cis or trans: follow the parent chain through the double
bond
trans 3-methyl-2-heptene
Example:
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Important Common Names
Ethylene Propylene
H H H H
C C C C
H H H CH3
i.e. polyethylene = plastic bags i.e. polypropylene = milk jugs
Vinyl (branch) Allyl (branch)
HC CH2 HC CH2
R CH2
cl
i.e. diallyllysergamide
i.e. polyvinyl chloride = PVC pipe
= derivative of LSD
Arranging many double bonds
• Cumulated
C=C double bonds all in a row: C=C=C=C
• Conjugated
Single and double bonds alternate: −C=C−C=C−C=C−
• Isolated
>1 single bond between double bonds: −C=C−C−C=C−C−C=C−
Lycopene
11 conjugated double bonds
2 isolated double bonds
PHYSICAL PROPERTIES OF ALKENES
Boiling point trends are similar to those shown in alkanes
increases as they get more carbon atoms in their formula
more atoms = greater intermolecular Van der Waals’ forces
greater intermolecular force = more energy to separate molecules
greater energy required = higher boiling point
the lower members are gases at room temperature and pressure
cyclohexene C6H10 is a liquid
for isomers, greater branching = lower boiling point
C2H4 (- 104 °C) C3H6 (- 48°C) ....... C6H10 (83°C)
Melting point general increase with molecular mass
the trend is not as regular as that for boiling point.
Solubility alkenes are non-polar so are immiscible (don’t mix with) with water
miscible with most organic solvents.
ELECTROPHILIC ADDITION OF BROMINE
TEST FOR UNSATURATION
The addition of bromine dissolved in tetrachloromethane (CCl 4) or water (known
as bromine water) is used as a test for unsaturation. If the reddish-brown colour is
removed from the bromine solution, the substance possesses a C=C bond.
A PLACE A SOLUTION OF BROMINE
IN A TEST TUBE
B ADD THE HYDROCARBON TO BE
TESTED AND SHAKE
C IF THE BROWN COLOUR
DISAPPEARS THEN THE
HYDROCARBON IS AN ALKENE
A B C
Because the bromine adds to the alkene, it no longer exists as
molecular bromine and the typical red-brown colour disappears
CHEMICAL PROPERTIES OF ALKENES
Reactions of Alkenes
• Alkanes – substitution reactions
– R-H + A-B R-A + H-B
– R = “residue”, a generic alkyl group
• Alkenes – addition reactions
C C + A-B C C
A B
Thermodynamics:
Hrxn = bonds broken – bonds formed
= ( bond + bond) – ( bond + bond)
Exothermic reaction
Alkene Addition Reactions
C C + A-B C C
A B
• Hydrohalogenation (+ HX) A-B
(addition of H-X, X =halogen)
H-F, H-Cl, H-Br, H-I
• Hydration (+ H2O) Markovnikov’s
(addition of H2O) rule
H-OH
• Halogenation (+ X2) Br-Br, Cl-Cl, F-F
Br-Br, Cl-Cl, F-F
H-H
• Hydrogenation (H2/Pt)
(addition of H2) Cis/trans with rings
Markovnikov’s Rule
• Consider the reaction
H H H H H H
C C + H Cl H C C CH3 H C C CH3
H CH3 Cl H H Cl
1-propene 1-chloropropane 2-chloropropane
• Two products are possible
• Experimentally, only 2-chloropropane is formed
Markovnikov’s Rule:
The alkene carbon with the most H atoms gets the H
•Hydrohalogenation (H-X), hydration (H2O) of alkenes
Vladimir
Markovnikov Why? Look at the reaction mechanism to find out...
Mechanism of Hydrohalogenation
Step 1: Alkene electrons attack H+, forming a carbocation
H Cl carbocation
H H H H
H H
C C H C C or C C H + Cl
CH3 H
H CH3 H CH3
Step 2: Cl- nucleophile forms bond with carbocation
H H H H H
H
H C C Cl
CH3 H C C CH3 H C C CH3
H
H Cl Cl H
The carbocation formed in step 1 determines the final product
Hydrohalogenation
Predict the product of the following hydrohalogenation reaction
Br
+ HBr
Anti-Markovnikov Product
Remember: OR
Markovnikov’s rule says
that the H (from HBr) will
bond to the alkene C with Br
the most H’s
Markovnikov Product
Hydrohalogenation
Determine any reactant(s) that could yield the given product
of the following hydrohalogenation reaction
Br
+ HBr
3-methyl-1-hexene Only possible reactant for this product
+ HBr
Br
trans-3-methyl-2-hexene Major product using M’s rule
Hydrohalogenation
Determine any reactant(s) that could yield the given product of
the following hydrohalogenation reaction
+ HBr
Br
trans-3-methyl-2-hexene
All three reactants could give this
product
3-methyl-3-hexene 2-ethyl-1-pentene
Hydration
Predict the product of the following hydration reaction
OH
+ H2O
Anti-Markovnikov Product
OR
Remember:
Markovnikov’s rule says
that the H (from H2O) will OH
bond to the alkene C with
the most H’s
Markovnikov Product
Mechanism of Hydration (R + H2O)
Step 1: bond attacks electrophilic H+ catalyst forming carbocation
H H
H H H
H C C Most stable carbocation
C C CH3
H
H CH3
Step 2: Nucleophilic H2O attacks carbocation, forming oxonium ion
H H
H H
H
H C C O H C C CH3
CH3
H H H O oxonium ion
H H
Step 3: Oxonium ion loses a proton, regenerating H+ catalyst
H H
H H
H C C CH3
H C C CH3 + H
H O
H H H OH Markovnikov product
Mechanism of Halogen Addition (R + X2)
Step 1: Br2 is polarized by electrons, Br+ attaches to alkene
H3 C CH3
H3C CH3 +
Br Br
Br
Br
bromonium ion
intermediate
Step 2: Br+ blocks access to one face of the alkene
Br- adds to the other face (anti addition)
Br
CH3 Br
H3C CH3
Br Br CH3
trans isomer is the only product
Halogenation
Br
+ Br2
Br
Trans isomer
Br
+ Br2 Br
The Br’s will add to opposite sides of a RING (anti addition)
The Br’s will be forced into a trans conformation ALWAYS
Halogenation
Determine any reactant(s) that could yield the given product of
the following halogenation reaction
Br
+ Br2
Br
trans-3,5-dimethyl-2-heptene
Only one possible reactant in this case
Hydrogenation
• Occurs in the presence of a metal catalyst (like Pt)
+ H2/Pt
cis isomer
+ H2/Pt
Both H’s will add to the same side of a RING (syn addition)
If branches are present, they will be forced into a cis conformation
Hydrogenation of alkenes
+ H2/Pt
vegetable oils
unsaturated saturated
Contains double bonds Contains NO double bonds
Oxidation Reactions of Alkenes
Because alkenes are hydrocarbons, they undergo complete
combustion reactions with oxygen at high temperatures to produce
carbon dioxide and water.
Unsaturated hydrocarbons can also be partially oxidized under
relatively mild conditions.
For example, potassium permanganate, KMnO4(aq), is added to an
alkene (or alkyne), the purple color of KMnO4 fades and a brown
precipitate of manganese dioxide forms .
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Example:
Aromatic Hydrocarbons
Aromatic hydrocarbons usually contain benzene rings: six-membered rings
of carbon atoms with alternating carbon–carbon single and carbon–carbon
double bonds.
The electronic structure of benzene can be represented by resonance
formulas (?).
For benzene. This electronic structure can also be described using
molecular orbitals. In this description, molecular orbitals encompass the
entire carbon-atom ring, and the electrons are said to be delocalized.
Delocalization of electrons means that the double bonds in benzene do not
behave as isolated double bonds.
Aromatic Hydrocarbons
Aromatic compounds are found everywhere.
The term aromatic implies that compounds that contain a benzene
ring have aromas, and this is indeed the case.
Flavoring agents that can be synthesized in the laboratory or found in
nature include the flavor and aroma of cinnamon, cinnamaldehyde,
and the wintergreen flavor of candies and gum, methyl salicylate.
Benzene rings also exist in the pain relievers acetylsalicylic acid
(aspirin), acetaminophen (Tylenol), and the illegal drug mescaline.
Polymerization of Alkenes
• Polymer: a large molecule made by linking together small
repeat units called monomers
• Polymerization mechanism: radical chain reaction
Monomer Polymer
CH2 CH2 CH2 CH2 CH2 CH2
n
ethene
polyethylene
(ethylene)
H H
C C CH CH2 CH CH2
n
CH3 H CH3 CH3
propene
(propylene) polypropylene
POLYMERISATION OF ALKENES
PROBLEMS WITH POLYMERS
Although polymers derived from alkenes are invaluable to modern society, their
disposal creates widespread problems.
• they are unreactive to most chemicals and bacteria (non-biodegradable)
• if they are just discarded they add to the landfill problem
recycling high cost of collection and re-processing
burn waste saves on landfill sites and produces energy
toxic fumes (HCl) can be removed from burning chlorinated polymers
feedstock use the waste for the production of useful organic compounds
new technology can convert waste into hydrocarbons
hydrocarbons can then be turned back into polymers.
PREPARATION OF ALKENES
FROM HALOGENOALKANES - Elimination
Reagent Alcoholic sodium (or potassium) hydroxide
Conditions Reflux in alcoholic solution
Product Alkene
Mechanism Elimination
Equation
C3H7Br + NaOH(alc) ——> C3H6 + H 2O + NaBr
FROM ALCOHOLS - Dehydration
Reagent Conc. sulphuric acid or conc. phosphoric acid (H3PO4)
Conditions Reflux
Product Alkene
Mechanism Dehydration (elimination of water)
Equation C2H5OH(l) ——> CH2=CH2(g) + H2O(l)
Alkynes CnH2n-2
Contents :
• Structure
• Naming
• Physical and Chemical Properties
• Reactions and preparation of Alkynes
C 2H 2 H:C:::C:H H—C C—H sp => linear, 180o
acetylene
ethyne
C 3H 4 CH3CCH methylacetylene
propyne
Alkynes Naming Practice
3,4-dimethyl-1-pentyne 2-methyl-3-hexyne
3-methyl-1-pentyne 2,5-dimethyl-3-hexyne
Properties of Alkynes
Reactions of Alkynes
Reactions Summary of alkynes:
1. addition of H2 (reduction)
2. addition of X2
3. addition of HX
4. addition of H2O, H+
Hydrohalogenation of Alkynes
Predict the product of the following hydrohalogenation reaction
+ 2HBr ?
1-pentyne
Break the reaction into two steps, adding 1 HBr each time to the multiple bond
Br
+ HBr
Br Br Br
+ HBr
Final Product
Markovnikov’s rule still applies…
Hydration of Alkynes
Predict the product of the following hydration reaction
+ 2H2O ?
3,3-dimethyl-1-butyne
Break the reaction into two steps, adding H2O each time to the multiple bond
+ H2O
OH
+ H2O
OH HO OH
Markovnikov’s rule still applies… Final Product
Halogenation of Alkynes
Predict the product of the following halogenation reaction
+ 2Br2 ?
3,3-dimethyl-1-butyne
Break the reaction into two steps, adding Br2 each time to the multiple bond
+ Br2
Br
Br
Br
+ Br2
Br Br
Br Br Br
Final Product
Hydrogenation of Alkynes
Predict the product of the following hydrogenation reaction
+ 2H2 ?
3,3-dimethyl-1-butyne
This reaction will simply turn the alkyne to an alkene, and then to an alkane
+ H2
+ H2
Final Product
Alkyne Reaction Practice
Cl
1. + 2HCl →
Cl
HO OH
2. + 2H2O →
Br Br
3. + 2Br2 →
Br Br
4. + 2H2 →
5. Cl Cl
+ 2HCl →
Cl Cl
AND
Preparation of Alkynes
General methods are similar to those used for preparation of alkenes.
1-Dehydrogenation of Tetra halides
Preparation of Alkynes
2. From metallic acetylides
