CHAPTER 11

Alkenes; Infrared Spectroscopy and

Mass Spectroscopy
Naming the Alkenes 11-1
Alkenes are characterized by the presence of a double bond.
The general formula of an alkene is C
n
H
2n
, the same as for a
cycloalkane.
Common nomenclature for alkenes replaces the corresponding
alkane suffix ane with -ylene.
IUPAC nomenclature replaces the alkane suffix ane with ene
(ethene, propene, etc.).
Rules for naming alkenes:
Rule 1: Find the longest chain that includes both carbons of
the double bond.
Rule 2: Indicate the location of the double bond in the main
chain by number starting at the end of the chain closest to the
double bond.
The two double bond carbons in cycloalkenes are
numbered 1 and 2.
Alkenes with the same formula but differing in the location
of the double bond are called double-bond isomers.
A 1-alkene is referred to as a terminal alkene; the others
are called internal.
Rule 3: Add substituents and their positions as prefixes to the
alkene stem.
If the stem is symmetric, begin from the end giving the
first substituent the lowest possible number.
Rule 4: Identify any cis/trans stereoisomers. These are
examples of diastereomers, or stereoisomers that are not
mirror images of each other.
In cycloalkenes, trans isomers are stable only for the larger ring
sizes.
Rule 5: Use the IUPAC E,Z system when cis/trans labels are
not applicable (3 or 4 different substituents attached to the
double-bond carbons).
Apply the sequence rules devised for R,S substituent
priorities to the two groups on each double-bond carbon.
If the two groups of highest priority are on opposite sides
of the double bond, the molecule is an E isomer. If they
are on the same side of the double bond, the molecule is a
Z isomer.
Rule 6: Give the hydroxy functional group precedence over
the double bond in numbering a chain.
Alcohols containing double bonds are named alkenols. The
stem incorporating both functions is numbered to give the
OH carbon the lowest possible assignment.
The last e and alkene is dropped in naming alkenols.
Rule 7: Substituents containing a double bond are named
alkenyl.
The numbering of a substituent chain containing a double bond
begins at the point of attachment to the basic stem.
Structure and Bonding in Ethene: The Pi Bond 11-2
The double bond consists of sigma and pi
components.
Ethene is planar. It contains two trigonal carbon atoms having
bond angles close to 120
o
.
The hybridization of the carbon atoms is best described as sp
2
.
The three sp
2
orbital on each carbon form bonds to two
hydrogen atoms and to the other carbon atom.
The remaining unhybridized p orbital on each carbon overlap to
form a bond. The electron density of the bond is equally
distributed above and below the plane of the molecule.
The pi bond in ethene is relatively weak.
The overlap of the two sp
2
orbitals to form the bond connecting
the two carbon atoms is much greater than the overlap of the two
p orbitals to form the bond.
As a consequence, the bond contributes more to the double
bond strength than does the bond.
The relative energies of the bonding and antibonding and
orbitals can be summarized:
Thermal isomerization allows us to measure the
strength of the pi bond.
Thermal isomerization involves the interconversion of the cis form
and the trans form of a double bond at high temperature.
During the isomerization process, the bond between the two
carbon atoms is broken and the p orbitals on the two carbon
atoms become perpendicular to each other (transition state).
The activation energy for this process is roughly the same as the
contribution to the double-bond energy.
The measured activation energy for this process is about 65 kcal
mol
-1
. The total energy of the ethene double bond is 173 kcal mol
-
1
, which means the bond energy must be about 108 kcal mol
-1
.
The alkenyl hydrogens are more tightly held in alkenes than the
C-H bonds in the corresponding alkanes. As a result, addition to
the weaker bond characterizes the reactivity of alkenes in
radical reactions, rather than hydrogen abstraction.
Physical Properties of Alkenes 11-3
The boiling points of alkenes are very similar to the corresponding
alkanes.
The melting points of alkenes are lower than those of the
corresponding alkanes.
The presence of a trans double bond lowers the melting point
slightly, while the presence of a cis double bond lowers the
melting point significantly more.
The effect of a double bond on melting point is due to the
disruption of packing of molecules in the crystal lattice
compared to the packing of saturated molecules.
Cis double bonds often exhibit weak dipolar character. The degree
of s orbital character in a sp
2
carbon is larger than in an sp
3

carbon (alkane) which makes the sp
2
carbon a weak electron
withdrawing group.
Trans double bonds, on the other hand, generally have little
dipolar nature since the dipoles involved oppose each other.
The electron-attracting character of the sp
2
carbon also accounts
for the increased acidity of the alkenyl hydrogen, compared to its
saturated counterpart.
Ethene is still a very poor source of protons compared to alcohols
or carboxylic acids.
Nuclear Magnetic Resonance of Alkenes 11-4
The pi electrons exert a deshielding effect on
alkenyl hydrogens.
The proton NMR spectra of trans-2,2,5,5-tetramethyl-3-hexene
shows only two peaks. The methyl protons and alkenyl protons
are too far from each other to produce detectable coupling.
The resonance of the allenyl
protons at 5.30 ppm is typical
of hydrogens bound to alkenyl
carbons.
Terminal alkenyl hydrogens
(RRC=CH
2
) resonate at 4.6
5.0 ppm. Internal alkenyl
hydrogens (RCH=CHR)
resonate at 5.25.7 ppm
The deshielding for alkenyl hydrogens has two causes.
Less important is the electron withdrawing effect of the sp
2

hybridized carbon.
More important is the effect of the external magnetic field on
the cloud of electrons. The electrons are forced to assume
a circular motion when the magnetic field is perpendicular to
the double bond axis.
The circular motion of the electrons induces a second
magnetic field which reinforces the external field.
Cis coupling through the double bond is different
from trans.
Unsymmetrically substituted double bonds lead to non-equivalent
alkenyl hydrogens which leads to spin-spin coupling.
Within a set of cis/trans isomers, the coupling constant for the
trans isomer, J, is always larger than for the cis isomer.
Coupling between hydrogens on adjacent carbons is called vicinal.
Coupling between hydrogens on the same carbon is called
geminal and is usually small in alkenes.
Coupling to neighboring alkyl hydrogens (allylic) and 1,4- or long-
range coupling is also possible, which may produce complicated
spectral patterns.
Further coupling leads to more complex spectra.
In 3,3-dimethyl-1-butene H
a
resonates at 5.86 ppm in the form of
a doublet with two relatively large coupling constants (J
ab
=18 Hz,
J
ac
=10.5 Hz). H
b
and H
c
also absorb as doubles due to their
coupling to H
a
and their mutual coupling (J
bc
= 1.5 Hz).
In 1-pentene, there is additional coupling to the attached alkyl
group. In addition, the double bond causes a slight deshielding of
the allylic CH
2
group.
The coupling between the allylic hydrogens and the neighboring
alkenyl hydrogen is about the same as the coupling with the two
CH
2
hydrogens on the other side.
As a result, the multiplet for the allylic CH
2
group appears as a
quartet.
Alkenyl carbons are deshielded in
13
C NMR.
Relative to alkanes, corresponding alkene carbons absorb at
about 100 ppm lower field.
Infrared Spectroscopy 11-5
IR spectroscopy measures the vibrational excitation of atoms
around the bonds that connect them.
The positions of the absorption lines are related to the types of
functional groups present.
The IR spectrum as a whole is unique for each individual
substance.
Absorption of infrared light causes molecular
vibrations.
The infrared region is range of the electromagnetic spectrum just
below visible light. Absorption of light of this wavelength causes
vibrational excitation of the bonds in a molecule.
Middle infrared light (~2.5-16.7 m, or 600-4000 cm
-1)
has
energies from 1 to 10 kcal mol
-1
and is most useful to the
chemist.
Hookes law relates the parameters affecting the vibrational
frequency of two weights connected by a spring.
The vibrational frequency of two atoms connected by a bond is
also accurately described by Hookes law:
However, the infrared spectrum of a molecule is significantly more
complex than the vibrational frequencies of all of the bonds
present.
Various bending motions, and combinations of stretching and
bending are also excited by IR radiation, which leads to
complicated patterns.
Fortunately, the vibrational bands of many functional groups
appear at characteristic wavenumbers, and the entire IR spectrum
of a given compound is unique and can be distinguished from that
of any other substance.
Functional groups have typical infrared
absorptions.
Compare the IR spectra of pentane and hexane:
Above 1500 cm
-1
the C-H stretching absorptions typical of alkanes
can be seen.
Since no function groups are present, no absorptions are seen in
the region from 28403000 cm
-1
.
Below 1500 cm
-1
, the fingerprint region, C-C stretching and C-C
and C-H bending motions absorb to give complicated patterns.
All saturated hydrocarbons show peaks at 1460, 1380, and 730
cm
-1.

Now compare hexane to 1-hexene:
An additional peak at 3080 cm
-1
can be seen which is due to the
stronger C
sp2
-H bond.
The C=C stretching band should appear between 1620 and 1680
cm
-1
and is seen at 1640 cm
-1
.
The two signals at 915 and 995 cm
-1
are characteristic of a
terminal alkene.
Several other strong bending modes are characteristic for the
substitution patterns in alkenes:
The O-H stretching absorption is the most characteristic band in
the IR spectra of alcohols. This appears as a broad band over the
range 32003650 cm
-1
. This is due to hydrogen bonding.
Dry, dilute alcohols show a sharp narrow band in the range 3620
3650 cm
-1
.

Haloalkane C-X stretching frequencies are too low (<800 cm
-1
) to
be useful for characterization.
Degree of Unsaturation: Another Aid to
Identifying Molecular Structure
11-6
Knowledge of the degree of unsaturation, defined as the numbers
of rings and bonds present in a molecule, is useful information
when determining the structure of a compound.
A fully saturated hydrocarbon will have 2n+2 hydrogen atoms for
every n carbon atom.
Consider the compounds in the class C
5
H
8
. This compound is 4
hydrogens short of being saturated, so its degree of unsaturation
is 4/2 = 2.
All molecules having this formula must have a combination of
rings and bonds adding up to 2.
The presence of heteroatoms may affect the calculation.
The presence of a halogen atom decreases the number of
hydrogens by one.
The presence of a nitrogen atom increases the number of
hydrogens by one.
The presence of oxygen or sulfur does not affect the number
of hydrogens.
To determine the degree of unsaturation:
Step 1: H
sat
= 2n
C
+ 2 n
X
+ n
N

Step 2: Degree of unsaturation = (H
sat
H
actual
)/2
Catalytic Hydrogenation of Alkenes: Relative
Stability of Double Bonds
11-7
Hydrogen gas and an alkene will react when mixed in the
presence of a catalyst such as platinum or palladium.
Two hydrogen atoms are added to the alkene in a reaction called
hydrogenation, which is very exothermic.
The heat released is called the heat of hydrogenation and has a
typical value of about -30 kcal mol
-1
per double bond.
The heat of hydrogenation is a measure of stability.
The relative stabilities of related alkenes can be determined by
measuring their heats of combustion.
The thermodynamic stability of the butenes increases in the
order: 1-butene < cis-2-butene < trans-2-butene.
Highly substituted alkenes are most stable; trans
isomers are more stable than cis.
The relative stability of the alkenes increases with increasing
substitution (hyperconjugation), and trans isomers are usually
more stable than cis isomers (crowding).
An exception to this stability rule is in medium-ring and smaller
cycloalkenes. The trans isomers of cycloalkenes are much more
strained than are the corresponding cis isomers.
The smallest isolated simple trans cycloalkene is trans-
cyclooctene which is 9.2 kcal mol
-1
less stable than the cis isomer
is very twisted.
Preparation of Alkenes from Haloalkenes and Alkyl
Sulfonates: Bimolecular Elimination Revisited
11-8
Two approaches to the synthesis of alkenes are elimination
reactions and the dehydration of alcohols.
Regioselectivity in E2 reactions depends on the
base.
Haloalkanes (or alkyl sulfonates) in the presence of strong base
can undergo elimination of HX with the simultaneous formation of
a C=C double bond.
In the cases where the hydrogen atom can be removed from
more than one carbon atom in the structure, the regioselectivity
of the reaction can be controlled to a limited extent.
Consider the dehydrobromination of 2-bromo-2-methylbutane.
Elimination of HBr proceeds through attack by
the base on one of the neighboring hydrogens
situated anti to the leaving group.
The transition state leading to 2-methyl-2-
butene is slightly more stabilized than the one
leading to 2-methyl-1-butene.
The more stable product is formed faster
because the structure of the transition state
resembles that of the products.
Elimination reactions that lead to the more highly substituted
alkene are said to follow the Saytzev rule.
The double bond preferentially forms between the carbon that
contained the leaving group and the most highly substituted
adjacent carbon that bears a hydrogen.
When a more hindered base is used, more of the
thermodynamically less favored terminal alkene is generated.
Removal of a secondary hydrogen (C3 in the starting bromide) is
sterically more difficult than abstracting a more exposed methyl
hydrogen when a hindered base is used.
The transition state leading to the more stable product is
increased in energy by steric interference with the bulky base.
An E2 reaction that generates the thermodynamically less favored
isomer is said to follow the Hofmann rule.
E2 reactions often favor trans over cis.
The E2 reaction can lead to cis/trans alkene mixtures, in some
cases with selectivity.
This and related reactions appear to be controlled by the relative
thermodynamic stabilities of the products. The more stable trans
double bond is formed preferentially.
Complete selectivity is rare in E2 reactions, however.
Some E2 processes are stereospecific.
The preferred transition state of elimination places the proton to
be removed and the leaving group anti with respect to each other.
When Z or E isomers are
possible, stereospecific
reactions may occur.
Preparation of Alkenes by Dehydration of Alcohols 11-9
When alcohols are treated
with mineral acid at
elevated temperatures,
dehydration (E1 or E2)
occurs, resulting in alkene
formation.
As the hydroxy
bearing carbon
becomes more
substituted, the
ease of
elimination of
water increases.
Secondary and tertiary alcohols dehydrate by an E1 mechanism.
The protonated hydroxy forms an alkyloxonium ion providing
a good leaving group: water.
Loss of water forms a secondary or tertiary carbocation.
Deprotonation forms the alkene.
Carbocation side reactions (hydrogen shifts, alkyl shifts, etc.)
are possible.
The thermodynamically most stable alkene or alkene mixture
usually results from unimolecular dehydration in the presence of
acid.
Whenever possible, the most highly substituted system is
generated.
Trans-substituted alkenes predominate if there is a choice.
Treatment of primary alcohols with mineral acids at high
temperatures also leads to alkenes.
The reaction of propanol yields propene.
The reaction proceeds by protonation of the alcohol, followed by
attack by HSO
4
-
or another alcohol molecule (E2 reaction) to remove
a proton from one carbon atom and water from the other.
Important Concepts 11
1. Alkenes Unsaturated molecules
IUPAC names are derived from the longest chain
containing the double bond as the stem.
Double bond isomers: terminal, internal, cis, and
trans
Tri- and tetra-substituted alkenes are named
according to the E,Z system.
2. Double Bond Consists of a bond and a bond
bond: overlap of two sp
2
hybrid lobes on carbon
bond: overlap of two remaining p orbitals
bond E (~65 kcal/mol); bond E (~108 kcal/mol)
Important Concepts 11
3. Alkene Properties
Flat, sp
2
hybridization
Dipoles possible
Alkenyl hydrogen is relatively acidic.
4. NMR
Alkenyl hydrogens and carbons appear at low field:

1
H ( = 4.6 - 5.7 ppm);
13
C ( = 100 -140 ppm)
J
trans
> J
cis
; j
geminal
very small; J
allylic
variable, small.
5. IR Measures vibration excitation
1-10 kcal/mol (2.5-16.7 m; 600-4000 cm
-1
)
Characteristic peaks for stretching, bending and
other vibrational modes
Fingerprint region (<1500 cm
-1
)
Important Concepts 11
6. Alkane IR
C-H Stretching: 2840 to 3000 cm
-1

C=C Stretching: 1620 to 1680 cm
-1

Alkenyl C-H Stretching: ~3100 cm
-1
Bending Modes: below 1500 cm
-1

Alcohols: Broad O-H stretch: between 3200 and
3650 cm
-1

7. Degree of Unsaturation Number of rings +
number of bonds:
Degree of unsaturation = (H
sat
H
actual
)/2
H
sat
= 2n
C
+ 2 N
X
+ N
N
(disregard oxygen and
sulfur)
Important Concepts 11
8. Heats of Hydrogenation indicate relative
stability of isomeric alkenes.
Stability decreases with decreasing substitution.
Trans isomers are more stable than cis.
9. Eliminations of Haloalkanes (and other
alkyl derivatives)
Follow the Sayzex rule (non-bulky base, internal
alkene formation) or the Hofmann rule (bulky base,
terminal alkene formation).
Trans alkene products predominate over cis.
Elimination is stereospecific (dictated by the anti
transition state).
Important Concepts 11
10. Dehydration of Alcohols Dehydration in the
presence of strong acid results in a mixture of products
(major constituent is the most stable alkene).