Chapter 10 Notes

CHAPTER 10
ALKENES
10.1 Structure
Alkenes are unsaturated hydrocarbons (fewer hydrogens attached to carbon than on
an
alkane).
Alkenes have general molecular formula CnH2n.
The simplest alkene is ethene (ethylene).
10.2 Nomenclature
A. Common Names:
Examples
B. IUPAC Nomenclature;
IUPAC rules are similar to those for alkanes but with the terminal ane changed to
ene
for alkenes. To name and locate multiple bonds, the following rules are applied;
Find the longest chain containing double bonds and number so that the carbon
atoms in the double bond have the lowest possible numbers.
The position of the double bonds is indicated by the number of its first carbon
(lower-numbered carbon atom). This number is placed in front of the name of the
compound.
Substituents are named and listed alphabetically.
For more than one double bond, use diene or triene, etc.
Some common names are also used.
Created by Dr. Felix N. Ngassa for CHM 241: Organic Chemistry for Life Sciences
I, GVSU, Fall 2010.
EXAMPLES ON NOMENCLATURE OF ALKENES
C. Cycloalkenes:
Same rules as for alkenes but with the double bond at C1-C2.
Start numbering at the double bond, and number through the double bond to give t
he
substituent the lowest number (example below).
If only one double bond, do not indicate position of double bond with 1 (example
below).
10.3 Cis-Trans Isomerism in Alkenes
Recall cis-trans isomerism in Chapter 8.
Restricted rotation about a double bond leads to cis-trans isomerism.
Cis-Trans isomers are diastereomers and have different physical and chemical
properties.
For example 1,2-dichloroethene exists in two different forms:
Cis isomers are generally less stable due to sterics.
I, GVSU, Fall 2010.
10.4 The E/Z System of Nomenclature
For the designation of tri- and tetrasubstituted alkenes.
Based on the Cahn-Ingold-Prelog rules.
If both higher priority groups are on the same side of the double bond, then the
alkene is
designated Z (together).
If both higher priority groups are on opposite sides then the designation is E (
opposite).
10.5 Physical Properties
Alkenes and alkynes are nonpolar molecules.
Held by weak dispersion forces just like alkanes.
Less dense than H2O.
Insoluble in H2O.
Examples:
10.6 Preparation of Alkenes
Recall from Chapter 8 that alkenes can be prepared from alkyl halides by
dehydrohalogenation using a base (E2 or E1 mechanism).
Recall from Chapter 9 that alkenes can be prepared from alcohols by acid-catalyz
ed
dehydration using H2SO4, H3PO4, TsOH, or POCl3 (E2 or E1 mechanism).
I, GVSU, Fall 2010.
10.7 Naturally Occuring Alkenes (Terpenes)
Found in the oils of plants and flowers and have distinctive odors and flavors.
Contain the isoprene unit (2-methyl-1,3-butadiene).
An isoprene unit contains a head (carbon 1) and a tail (carbon 4).
Terpenes are formed by joining together the tail of one isoprene unit to the hea
d of
another.
Terpenes are classified according to the number of isoprene units they contain.
Monoterpenes: 2 isoprene units (10-carbon substances).
Sesquiterpenes: 3 isoprene units (15-carbon substances).
Diterpenes: 4 isoprene units (20-carbon substances).
Limonene is a simple terpene responsible for the fragrance of oranges.
You should be able to recognize an isoprene unit in a molecule.
10.8 Reactions of Alkenes-An Overview
The carbon-carbon double bond in alkenes contains a s
-bond and a p
-bond and is
electron rich.
Electron rich species (negatively charged atoms, Lewis bases) are called Nucleop
hiles.
Electron deficient species (positively charges species, Lewis acids) are Electro
philes.
In a reaction, the electron arrow goes from the Nucleophile (the attacker) to th
e
Electrophile (the compound being attacked).
The most characteristic reaction of alkenes is Electrophilic Addition Reaction.
I, GVSU, Fall 2010.
A. Addition to the Double Bond:
In addition reactions, the double bond is broken and two new single bonds are fo
rmed.
B. Formation of Addition Polymers:
A second characteristic reaction of alkenes is the formation of chain-growth pol
ymers
by addition of monomers (smallest unit).
The formation of polymers requires the presence of catalysts called initiators.
10.9 Electrophilic Addition
This is the characteristic reaction of alkenes.
Reaction is initiated by attack of an electrophile by a nucleophile (carbon-carb
on double
bond).
We shall consider six electrophilic addition reactions.
A. Addition of hydrogen halides (HCl, HBr, HI), Hydrohalogenation.
B. Addition of H2O in the presence of an acid catalyst, Hydration.
C. Addition of halogens (Cl2 and Br2), Halogenation.
D. Addition of Cl2 and Br2 in the presence of H2O, Halohydrin Formation.
E.
Oxymercuration (Hg(OAc)2 and H2O), and Reduction (NaBH4).
F.
Hydroboration (addition of BH3), and Oxidation (reaction with H2O2 in NaOH).
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A. Addition of Hydrogen Halides:
The addition of hydrogen halides (HCl, HBr, HI) to alkenes gives haloalkanes (al
kyl
halides).
The addition of HX to an alkene is regioselective.
The regioselectivity means that H can only add to one carbon of the double bond.
Markovnikov s rule: in the addition of an unsymmetrical reagent (HX, H2O, ROH) to

an unsymmetrical alkene, hydrogen adds to the carbon of the double-bond that has
the
greater number of hydrogens already bonded to it.
Mechanism:
Mechanism Involving Carbocation Rearrangement:
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B. Addition of H2O (Acid-Catalyzed Hydration):
In the presence of an acid catalyst, H2SO4, H2O adds across the double bond of a
lkenes to
form alcohols.
Addition of H2O is called hydration.
Example:
The reaction follows the Markovnikov s rule.
Mechanism:
C. Addition of Br2 and Cl2 (Halogenation):
Reaction is carried out either with the pure reagents or by mixing them in an in
ert
solvent, such as CCl4 or CH2Cl2.
The addition is stereospecific (forms only one isomer) and occurs by an anti
stereochemistry (bromines add to opposite faces) to form a trans product.
Example:
Mechanism:
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D. Addition of HOCl and HOBr (Halohydrin Formation):
Addition of Br2 or Cl2 to an alkene in the presence of H2O results in the additi
on of OH
and Br, or OH and Cl across the carbon-carbon double bond to give a halohydrin.
The addition is stereospecific (forms only one isomer) and occurs by an anti
stereochemistry to form a trans product.
The addition is also regiospecific: For HOX (HO-X), X adds to the less substitut
ed
carbon via a bridged halonium ion intermediate and OH adds to the more substitute
d
carbon.
NBS (N-bromosuccinimide) in aqueous DMSO can also be used to generate
bromohydrin.
Examples:
E. Oxymercuration-Reduction:
A method for converting an alkene to an alcohol.
The alkene is treated with Hg(OAc)2 in H2O followed by reduction of the resultin
g
product with NaBH4.
Stereochemistry is predominantly Anti.
Oxymercuration occurs without rearrangement because the bridged mercurinium is n
ot a
true carbocation but rather a resonance hybrid.
Examples:
F. Hydroboration-Oxidation:
I, GVSU, Fall 2010.
A method for converting an alkene to an alcohol.
Reaction is both regioselective and stereospecific.
The addition is stereospecific (forms only one isomer) and occurs by a syn
stereochemistry to form a cis product.
An alkene is treated with borane (BH3) to give a trialkyl borane, which is then
oxidized
with alkaline H2O2 to give an alcohol.
Hydroboration-oxidation is an anti-Markovnikov hydration.
Examples:
10.10 Oxidation and Reduction
Recall that oxidation is loss of electrons and reduction is gain of electrons.
Remember the concept of oxidation and reduction by the phrase: LEO the lion says
GER.
Oxidation and reduction reactions are recognized by balancing half reactions
A. Rules for Balancing Oxidation-Reduction Reactions:
Example: For the reactions below, determine if the reaction is oxidation, reduct
ion, or
neither.
B. Recognizing Oxidation-Reduction Reactions in Organic Compounds:
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Oxidation and reduction reactions can be recognized without balancing half react
ions.
Oxidation: increasing bonds to O (gain of O), decreasing bonds to H (loss of H).
Reduction: increasing bonds to H (gain of H), decreasing bonds to O (loss of O).
Example:
10.11 Oxidation of an Alkene to a Glycol (Dihydroxylation)
Glycol: a compound with two hydroxyl groups on adjacent carbons
The reagents for oxidation are either OsO4 or KMnO4.
Oxidation of alkenes is stereospecific involving syn addition (OH groups add on
same
face).
The product is a cis glycol.
(i) Oxidation with OsO4/NaHSO3, H2O
(ii) Oxidation with KMnO4/ H2O, NaOH
10.12. Oxidative Cleavage of a Carbon-Carbon Double Bond
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Oxidative cleavage results in the cleaving of carbon-carbon double bond to give
two
carbonyl (C=O) groups.
The reagents for oxidative cleavage are either O3 (ozone) in the presence of a r
educing
agent (CH3)2S, or KMnO4 in acidic solution.
A. Ozonolysis:
B. Use of KMnO4/H3O+:
The products of the reaction are determined from the following rules;
i. If H is not directly attached to any of the double-bonded carbons, the produc
ts are
ketones.
ii. If one H is present on the double-bonded carbon, then a carboxylic acid is f
ormed.
iii. If two hydrogens are present on one carbon, then CO2 is formed.
10.13 Reduction of the Carbon-Carbon Double Bond
I, GVSU, Fall 2010.
In the presence of a transition metal catalyst, alkenes react with H2 to give al
kanes.
The reaction is called catalytic reduction or catalytic hydrogenation.
Examples of transition metal catalysts used for this reaction are Pt, Pd, Ru, an
d Ni.
Catalytic hydrogenation is stereospecific and proceeds with syn stereochemistry.
The product of catalytic hydrogenation is cis.

Examples:
10.14 Heats of Hydrogenation and Relative Stabilities of Alkenes
The heat of hydrogenation is the heat of reaction with hydrogen to form an alkan
e.
Reduction of an alkene to an alkane is an exothermic process.
Heats of hydrogenation depend on the degree of substitution of the carbon-carbon
double
bond and the stereochemistry.
i.
Heat of hydrogenation decreases in magnitude (less negative) with increasing
substitution.
ii.
Trans isomers are more stable and have a lower heat of hydrogenation, in
magnitude, than cis isomers (lower heat of hydrogenation is compared to be the
least exothermic).
Examples:
10.15 Molecules Containing Stereocenters as Reactants or Products
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The following summarizes reactions that produce chiral compounds.
Stereochemistry of Alkene Type of Addition Product
Cis alkene Anti addition Racemic mixture (R,R; S,S)
Trans alkene Anti addition meso (identical) (R,S; S,R)
Cis alkene Syn addition meso (identical) (R,S; S,R)
Trans alkene Syn addition Racemic mixture (R,R; S,S)
Examples of reactions:
10.16 Chemical Test for Carbon-Carbon Double Bond (Alkenes)
Bromination: Bromine is decolorized in presence of an alkene (red color to color
less).
Alkaline KMnO4: Dark purple color of KMnO4 turns to brown with alkenes.
I, GVSU, Fall 2010.

Chapter 10 Notes

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CHAPTER 10

Markovnikov s rule: in the addition of an unsymmetrical reagent (HX, H2O, ROH) to

Reduction: increasing bonds to H (gain of H), decreasing bonds to O (loss of O).

The product of catalytic hydrogenation is cis.

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