CHEM 3013 ORGANIC CHEMISTRY I LECTURE NOTES 1

CHAPTER 6
1. The Alkene Functional Group

Alkenes are also called olefins, or unsaturated hydrocarbons, as compared to alkanes which
are referred to as saturated hydrocarbons. In alkenes, there are two or more trivalent carbons with the
presence of one or more carbon-carbon double bonds. They have the general formula CnH2n.

H H
C C
H H
Ethylene (an alkene)

E 2p 2p
N
E
R 2sp2
G mix 2s and
Y 2s two 2p
orbitals

1s 1s

Elemental sp2 Hybridized

Carbon Carbon in Alkenes

π-bond (two 2p orbitals on carbon

H H
σ-bond (1s orbital
on hydrogen and sp2
H H orbital on carbon)

σ-bond (two sp2 orbitals on the carbons

Bonding in Alkenes

a. Bonding in Alkenes

Hybrid orbitals of sp2 and a p orbital combine to form a σ-bond and a π-bond, respectively.
It should be noted that a double bond is actually comprised of two two-electron bonds (σ and π); this
is why double bonds are shorter and stronger than single bonds. The difference between a sp3 hybrid
orbital and a sp2 hybrid orbital is the amount of "s" character (25% vs 33%, respectively); since the
latter has 33% it makes shorter and stronger sigma bonds to the hydrogens.
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b. Cis and Trans Stereoisomerism in Alkenes

The π-bonding in alkenes has substantial consequences when it comes to the conformations of
the alkenes. As you will recall from our discussions about rotation around bonds in ethane and
butane, it is relatively easy to rotate around a sp3-sp3 sigma bond (i.e. 3-5 Kcal/mole barrier height).
Rotation around double bonds requires that the π-bond first be broken (about 50-60 Kcal/mole)
before we can then rotate....this requires very high temperatures and is seldom observed.

This lack of free rotation around a π-bond leads to stereochemical consequences, there now
exists the possibility of two compounds that have the same carbon connectivity, but different 3-D
arrangements of the groups. These are stereoisomers of a specific type called geometric isomers.
When we have an alkene which has at least two identical atoms or groups on the two doubly-bonded
carbons of the alkene we use the same cis and trans formalism we used to define stereoisomers in
cycloalkanes. As shown below, the cis stereoisomers has identical groups on the same side of the
alkene, whereas the trans isomer has identical groups on opposite sides of the alkene.

H H H3C H3C
C C
CH3 CH3 H H
H3C C H3C H3C C H3C
H H H H
trans-2-butene cis-2-butene
(methyls on opposite (methyls on same
side of alkene side of alkene

p orbitals of π-bond are

perpendicular to plane of page;
all C's in plane
BUILD A MODEL!

Very hard to rotate around a double bond; have to break a π-bond

to do so

Stereoisomers of 2-butene

2. Nomenclature in Alkenes

Nomenclature used for alkenes is much like that used for alkanes...except that the ending
changes to ...ene. Thus any compound that ends in ene is an alkene.
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a. Common Names
Some alkenes and alkenyl groups have common names that can be recognized:

Common alkenes

H3C H3C
H3C
CH2 CH2 CH CH2 C CH2 CH CH2 C CH2
H3C CH
CH2

ethylene propylene isobutylene styrene isoprene

alkene substituent groups

H H CH3
CH2 CH2 CH2
CH2

vinyl allyl isoprenyl

Common Alkenes and Substituent groups

b. IUPAC Nomenclature

1. Name the longest chain including the double bond.

2. Drop the ane suffix of the base name and add ene
3. Number from the end nearest the double bond.
4. Complete the name as with alkenes
5. Specify the cis, trans or E,Z stereoisomer isomer if indicated in structure.
6. If more than one double bond exists in the compound, it is named as a diene, triene,

1 3 5 7 7 5 3 1
NOT
2 4 6 6 4 2

trans-3-heptene trans-4-heptene
Correct Incorrect
1 2 2 1
8 3 3 8
NOT
4 4 7
7
6 5 5 6

1,4-cyclooctadiene 1,6-cyclooctadiene
Correct Incorrect

Numbering Alkenes
 4
1 3 5 1
H2C H2C 2 H2C 2
NOT
4 6
3
4
5
Octane cannot be the 2-propyl-1-hexene 2-butyl-1-pentane
principal chain if it Incorrect
does not contain both CORRECT
carbons of the alkene.

Inclusion of the
double bond is more
important than the
longest carbon chain.

1 CH2
CH2 2,3-diethyl-1,3-butadiene
2
CORRECT
3
CH2 4 CH2
NO! see above

Lowest numbering of chain with maximum number of double bonds

CH
CH2
7 6
1 3-allyl-6-vinyl-1,4-cycloheptadiene
5
2 OR
3 4
3-(2-propenyl)-6-allyl-1,4-cycloheptadiene
1 CH2
2 CH CH2
3
Naming alkenes as substituent groups

c. Naming of Stereoisomers, the E/Z Convention

As we have seen, the lack of rotation around the double bond introduces the possibilities of
geometric isomerism. Geometric isomers are different compounds with different chemical and
physical properties.. For example cis-1,2-dibromoethylene has a boiling point of 110˚ whereas the
trans isomer has a boiling point of 129 ˚C. Thus, a nomenclature method for differentiating between
the different isomers is required. When we have at least two identical atoms (or groups) on the two
doubly -bonded carbons, as in the compound 2-pentene (draw the structure, the alkyl groups are
different...but the H's are identical), we can use the cis/trans formalism. But what about a compound
such as 1-bromo-1-chloro-1-propene? The are now four different substituents on the two carbons of 5
the double bond; a new convention is required.

CAHN, INGOLD, PRELOG SEQUENCE RULES FOR E,Z NOMENCLATURE

1. Give the groups on each carbon of a double bond, an order of priority with preference given
to the groups with the heavier atom attached to the double bond.
2. If the first atoms of two groups on a carbon are the same, then the group which has the
heavier atom attached to the first atom has higher priority.
3. If the second atoms are identical, keep moving out along the group until a difference is found.
4. Multiple bonds count as two, three, etc., bonds to the atom attached.
5. If the groups of highest priority are on the same side of the double bond, name the isomer Z
(Zusammen).
6. If the groups of highest priority are on the opposite side of the double bond, name the isomer
E (Entgegen).

high priority high priority high priority low priority

C C C C
low priority low priority low priority high priority
Z (zusammen)....together E (entgegen)....across

The E/Z Nomenclature of Alkene Stereoisomers

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Case 1: 3-chloro-2-pentane

Identical
Compounds
H3C Cl H3C Cl
C C C C
H3C C2H5 H3C C2H5
Exactly the same groups;
therefore E/Z meaningless

Case 2: Z-1-bromo-1-chloro-1-propene

LOW H Cl LOW
C C
HIGH H3C Br HIGH
(at# C > H) (at# Br > Cl)

Case 3: Z-3-propyl-2-heptene
SAME

LOW H CH2CH2CH2 H LOW

C C
HIGH H3C CH2CH2CH2 CH3 HIGH

SAME

E/Z Priority Rules

H X H C C X
C C C C
X X

C C
C C X C C X
C C

E/Z priority assignments of alkenes and alkynes

d. Relative Stabilities of Alkene Geometric Isomers

Trans isomers are more stable than cis isomers because of steric destabilization of the cis
isomer. In 2-butene this destabilization favors the trans isomer by 0.69 Kcal/mole, but in 2,2,6,6-
tetramethyl-3-hexene (draw the structure of both isomers) the trans isomer is favored by 6.3
Kcal/mole. Additional alkyl substituents on the double bond of the alkene stabilizes the
alkene...unless steric effects become too severe.
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CIS TRANS
H
H H H C H
C C H C C H
H
C C H C H
H H
H H
H H
SMALL steric
BIG steric interaction
interaction

Steric destabilization of cis-alkenes

3. Addition of Hydrogen Halides to Alkenes( Electrophilic Addition Reactions )

Polar molecules add across double bonds in a predictable fashion. The electrons in a π-bond
are relatively weakly held by the carbon atoms (π-bond strength ~50-60 Kcal/mole). Thus they are
available to react with a suitable electron-deficient species; alkenes are weak nucleophiles. When this
occurs a new sigma bond is formed, and an electron deficient carbon (a carbocation or carbonium ion)
is formed.

When an alkene reacts with an electrophile ( in the case of a hydrogen halide HX...a proton),
donation of π-electrons from the alkene creates a new C-H bond and an intermediate carbocation
(empty p orbital). This then reacts with a nucleophile ( in the case of hydrogen halides... a halide
anion) to form the observed product.

Alkene Intermediate Product

acting as a The empty p Net addition of
Nucleophile; orbital is now both X and Y to
a source of an electrophile the two ends of
electron density the alkene

C C C C C C
X X Y
NOTE direction
X+ of curved arrows. Y-

Electrophile; An electron rich

an electron poor species (a nucleophile)
species

The basic mechanism of electrophillic addition to alkenes

a. Markovnikov's Rule

Unsymmetrical alkenes often give a highly regioselective reaction (selective addition of an

unsymmetrical reagent to an unsymmetrical alkene). The favored product results from the addition of
the electrophile (proton, in the case of hydrogen halides) to the carbon which has the least alkyl
substitution or greatest hydrogen substitution. This is often referred to as the Markovnikov Rule after 8
a Russian Chemist who first observed this effect in 1869. The rule is often stated as a slogan :
Them that has gets.
Them being carbons bearing the greatest number of hydrogen atoms...and gets being the
proton. Markovnikov's Rule is an empirical rule (based on observations of great numbers of
examples, but it is based on a simple theoretical explanation. Markovnikov's rule favors the product
which passes through the most stable carbocation intermediate.

H
H2C Br-
CH
H2C HBr 2˚ carbocation Br observed
CH product
Br
H2C Br-
CH
H not obtained
1˚ carbocation

Regiochemistry of addition of HBr to an unsymmetrical alkene

b. Carbocation Stability

Overlap between the empty p orbital of a carbonium ion center and the sp3 orbital of an
adjacent alkyl group creates a stabilizing effect. This overlap results in some electron density being
shared with the carbonium ion, somewhat helping the electron deficiency. This phenomenon is called
Hyperconjugation and is a very important concept which will reoccur throughout the course. The
more nearby alkyl groups the greater the effect. Thus the order of stability of carbocations is:
Tertiary > Secondary > Primary > Methyl
Thus in the case of addition of HBr to 1-hexene, the major product is 2-bromohexane (as
predicted by Markovnikov's Rule) because addition of the electrophile to the double bond at the
number one carbon gives the more stable secondary carbocation at the number 2 carbon.
 9
Relative Stability of Carbocations (Carbonium ions).

Tertiary > Secondary > Primary > Methyl

3˚ 2˚ 1˚

H3C H3C H H
CH3 H H H
H3C H3C H3C H

filled
sp3 empty
orbitals p orbital

H
Hyperconjugation between the empty p orbital and
adjacent sigma bonds formed from sp3 orbitals
helps to stabilize the carbocation.

Carbocation stability is caused by hyperconjugation

c. Carbonium Ion Rearrangements

In some cases, an initial carbonium ion intermediate will migrate to a different portion of the
molecule by shifting a nearby alkyl group or hydride. This is done so as to produce a more stable
carbocation. This will give, after trapping by the nucleophile, a rearranged product. The driving
force for all these rearrangements is to form a more stable intermediate carbocation!
(i.e. primary to secondary, secondary to tertiary, etc.)

STEP 1:
Electrophillic Addition
follows Markovnikov Intermediate is a
Rule secondary cation
CH3 H Cl CH3 CH3
H3C H3C H3C
C CH2 C CH3 Cl- C CH3
C CH CH
H3C H3C H3C
H Cl
Note direction of 2-Chloro-3,3-dimethylbutane
STEP 2:
curved arrows. 17% of product mixture
Rearrangement
methyl group
shift......
forms tertiary
carbocation

CH3 Cl CH3
H3C Cl-
C C H H3C C C H
H3C CH3 CH3 CH3

2-chloro-2,3-dimethylbutane
83% of product mixture

Rearrangement of Carbonium Ions

4. Hammond Postulate 10
Certain reactions have their product distributions determined by the rates of a pair of
competitive pathways. Since these reactions do not involve product equilibration, it is the relative
height of the transition states leading to the two products that determines the ratio of the two
products. Pathways with lower barriers will occur faster, hence more of the reactant
will cycle over to this product. These reactions are said to occur under kinetic control.

TS 2

TS 1

E
N
E + HBr
R
G
Y

Br

Br

REACTION COORDINATE

The transition state leading to the secondary carbonium ion (TS 1) will have some of
the structure of this species. This transition state will be lower in energy than the
transition state leading to the primary carbonium ion (TS 2), which has some of the
structure of the less stable primary carbonium ion. Thus the rate at which 2-bromo-
propane will be formed is higher than that for 1-bromopropane; 2-bromopropane will
be the predominate product.

Hammond's Postulate Applied to Alkene Addition