John E.

McMurry

www.cengage.com/chemistry/mcmurry

Chapter 4
Alkenes

Credits to Paul D. Adams • University of Arkansas

Alkene - Hydrocarbon With Carbon-
Carbon Double Bond General Chemistry 2

 Also called an olefin but alkene is better name

 Hydrocarbon that contains a C-C double bond
 Includes many naturally occurring materials
 Flavors, fragrances, vitamins
Why this Chapter?
General Chemistry 2

 C=C double bonds are present in most organic and

biological molecules

 To examine consequences of alkene stereoisomerism

 To focus on an important alkene reaction: electrophilic

addition
4.1 Industrial Preparation and Use
of Alkenes General Chemistry 2

 Ethylene and propylene are important organic

chemicals produced
Thermal Cracking Method
General Chemistry 2

 The method used by industries to produce ethylene,

propylene and butene.
 Thermal cracking takes place without catalyst at very
high temperatures.
4.2 Calculating Degree of
Unsaturation
 Relates molecular formula to possible structures
 Degree of unsaturation will tell you the number of multiple bonds and/or rings.
 Formula for a saturated acyclic compound (alkane) is C nH2n+2
 Alkene has fewer hydrogens than an alkane with the same number of carbons —C nH2n because of
double bond
 Each ring or multiple bond corresponds to loss of 2 H's from the alkane C nH2n+2 formula.
Example: C6H10
General Chemistry 2

 Saturated formula would be C6H14

 therefore 4 H's are not present in C6H10.
 Thus, this has two degrees of unsaturation, can be:
 Two double bonds
 or triple bond
 or two rings
 or ring and double bond
Degree of Unsaturation With Other
Elements General Chemistry 2

1. Organohalogens (where X is F, Cl, Br, I)

 Halogen replaces hydrogen, so add no. of halogens
and H together to get equivalent hydrocarbon formula.
 E.g. C4H6Br2 and C4H8 have one degree of
unsaturation
Degree of Unsaturation
(Continued) General Chemistry 2

2. Organooxygen compounds (C,H,O) – Oxygen forms

2 bonds
 these don't affect the formula of equivalent
hydrocarbons
 Ignore no. of O in calculating degree of
unsaturation
 E.g. C5H8O and C5H8 have 2 degrees of
unsaturation.
Degree of Unsaturation
(Continued) General Chemistry 2

3. Organonitrogen compounds (C, H, N)

 Nitrogen has three bonds
 So if it connects where H was, it adds a connection point
 Subtract no. of N from the no. of H to get equivalent
degree of unsaturation in hydrocarbon
Summary - Degree of Unsaturation
General Chemistry 2

 Count no. of pairs of H's below CnH2n+2

 Add number of halogens to number of H's (X
equivalent to H)
 Ignore oxygens (oxygen links H)
 Subtract number of nitrogens from the number
of hydrogens.
4.3 Naming Alkenes
General Chemistry 2

 Step 1: Name the parent hydrocarbon

 Step 2: Number the carbons in chain so that double bond

carbons have lowest possible numbers. If double bond is same
distance from both ends, then start at the end nearer to the 1st
branch point.
Naming Alkenes (Continued)
General Chemistry 2

Step 3: Write the full name- Number substituents

according to: 1) Position in chain; 2) Alphabetically

Rings have “cyclo” prefix

Many Alkenes Are Known by
Common Names
Cis-Trans Isomerism in Alkenes

 Rotation of  bond is prohibitive

 This prevents rotation about a carbon-carbon double bond
(unlike a carbon-carbon single bond).
 Since bond rotation can’t occur, two isomers can’t
spontaneously interconvert, so both isomers are different
compounds.
Cis-Trans Isomerism in Alkenes
(Continued)

 Presence of a carbon-carbon double bond can create two

possible structures:
 cis isomer - two similar groups on same side of the double
bond
 trans isomer - similar groups on opposite sides
 Each carbon must have two different groups for these isomers
to occur
Cis-Trans Isomerism in Alkenes
(Continued)
 Cis-Trans Isomerization requires that end groups
differ in pairs
4.5 Sequence Rules: E,Z Designation

 Cis-Trans naming system discussed thus far only

works with disubstituted alkenes

 Tri- and Tetra substituted double bonds require

more general method to describe double bond
geometry.

 This method is called E,Z system.

 Sequence Rules: E,Z Designation
(Continued): Nomenclature
General Chemistry 2

 Priority rules of Cahn,

Ingold, and Prelog
 Compare where
higher priority
groups (i.e. higher
atomic no.) are with
respect to bond and
designate as prefix
 E -entgegen,
opposite sides
 Z - zusammen,
together on the same
side (on “ze zame
zide”)
Alkene Stereochemistry and the E,Z
Designation (Continued): Cahn-Ingold-Prelog
Rules General Chemistry 2

RULE 1
 Must rank atoms that are connected at comparison
point
 Higher atomic number gets higher priority
 Br > Cl > S > P > O > N > C > H
Alkene Stereochemistry and the E,Z
Designation (Continued): Cahn-Ingold-Prelog
Rules General Chemistry 2

RULE 2
 If atomic numbers are the same, compare at next connection
point at same distance until something has higher atomic
number
 Do not combine – always compare
Alkene Stereochemistry and the E,Z
Designation (Continued): Cahn-Ingold-Prelog
Rules General Chemistry 2

RULE 3
 Multiple-bonded atoms are equivalent to the same number of
single-bonded atoms
 Substituent is drawn with connections shown and no double or
triple bonds
 Added atoms are valued with 0 ligands themselves
4.6 Stability of Alkenes
General Chemistry 2

 Cis alkenes are less stable than trans alkenes because of steric
strain
 Compare heat given off on hydrogenation: Ho
 Less stable isomer is higher in energy
 And gives off more heat
 tetrasubstituted > trisubstituted > disubstituted >
monosusbtituted (from most stable to least stable, i.e., more
stable ones gives off lesser heat))
Stability of Alkenes (Continued):
Comparing Stabilities of Alkenes General Chemistry 2

 Evaluate heat given off when C=C is converted to C-C

 More stable alkene gives off less heat
 trans-Butene generates 5 kJ less heat than cis-butene
 4.7 Electrophilic Addition of
Alkenes General Chemistry 2

 General reaction
mechanism of
electrophilic addition
 Attack on electrophile
(such as HBr) by
bond of alkene
 Produces carbocation
and bromide ion
 Carbocation is an
electrophile, reacting
with nucleophilic
bromide ion
Electrophilic Addition of Alkenes
(Continued) General Chemistry 2

 The reaction is successful with HCl and with HI as

well as HBr
 HI is generated from KI and phosphoric acid
4.8 Orientation of Electrophilic Additions:
Markovnikov’s Rule General Chemistry 2

 In an unsymmetrical alkene, HX reagents can add in two different

ways, but one way is preferred over the other.
 If one orientation is sole product, the reaction is
regioselective/regiospecific.
 Markovnikov observed in the 19th century that in the addition of HX
to alkene, the H attaches to the carbon with more H’s and X
attaches to the other end (to the one with more alkyl substituents)
 This is Markovnikov’s rule
Example of Markovnikov’s Rule
General Chemistry 2

 Addition of HCl to 2-methylpropene

 Regiospecific – one product forms where two are possible
 If both ends have similar substitution, then not regiospecific
4.8 Preparation of Alkenes: Elimination
Reactions General Chemistry 2

 Alkenes are commonly made by:

 elimination of HX from alkyl halide
(dehydrohalogenation)
 Uses heat and KOH
 elimination of H-OH from an alcohol (dehydration)
 requires strong acids (sulfuric acid, 50 ºC)
4.9 Addition of Halogens to
Alkenes General Chemistry 2

 Bromine and chlorine add to alkenes to give 1,2-dihaloalkanes,

an industrially important process.
 F2 is too reactive and I2 does not add
 Cl2 reacts as Cl+ Cl-
 Br2 is similar

CH2Cl2
Addition of Br2 to Cyclopentene
General Chemistry 2

 Addition is exclusively trans

Mechanism of Bromine Addition
General Chemistry 2

 Br+ adds to an alkene producing a cyclic ion

 Bromonium ion, bromine shares charge with carbon
 Gives trans addition
Bromonium Ion Mechanism
 Electrophilic addition of
bromine to give a cation is
followed by cyclization to give
a bromonium ion
 This bromoniun ion is a
reactive electrophile and
bromide ion is a good
nucleophile
The Reality of Bromonium Ions
General Chemistry 2

 Bromonium ions were postulated more than 60 years ago to

explain the stereochemical course of the addition (to give the
trans-dibromide from a cyclic alkene)
 Olah showed that bromonium ions are stable in liquid SO2
with SbF5 and can be studied directly
4.10 Hydration of Alkenes: Addition of
H2O by Oxymercuration General Chemistry 2

 Hydration of an alkene is the addition of H-OH to give

an alcohol
 Acid catalysts are used in high temperature industrial
processes: ethylene is converted to ethanol
Oxymercuration Intermediates
General Chemistry 2

 For laboratory-scale hydration of an alkene

 Use mercuric acetate in THF followed by sodium
borohydride
 Markovnikov orientation
 via mercurinium ion
4.11 Reduction of Alkenes:
Hydrogenation General Chemistry 2

 Addition of H-H across C=C

 Reduction in general is addition of H2 or its equivalent
 Requires Pt or Pd as powders on carbon and H2
 Hydrogen is first adsorbed on catalyst
 Reaction is heterogeneous (process is not in solution)
Hydrogen Addition - Selectivity
General Chemistry 2

 Selective for C=C. No reaction with C=O, C=N

 Polyunsaturated liquid oils become solids
 If one side is blocked, hydrogen adds to other
Mechanism of Catalytic
Hydrogenation General Chemistry 2

 Addition of H-H is
syn because both H
add to the double
bond from the same
catalyst surface.
Attention!!
General Chemistry 2

Please source for exercises about alkenes (and

other topics covered in the syllabus) from any
organic chemistry textbooks, not necessarily
limited to the McMurry textbook alone. How
questions can ask about the alkene topic is very
variable, which is impossible to be covered just
by having Self-test Problems alone at the end
of these lecture slides. Be resourceful and
hardworking, and your efforts will pay off.
Remember: You reap what you sow.

40