7.

Alkenes and Alkynes

7.1. Alkenes
7.1.1. Elements of Unsaturation
 Alkenes are said to be unsaturated because they are
capable of adding hydrogen in the presence of a catalyst.
The product, an alkane, is called saturated because it
cannot react with any more hydrogen.
 Example: C4H8

Elements of Unsaturation with Heteroatoms

 Heteroatoms (hetero, "different") are any atoms other than carbon
and hydrogen. The rule for calculating elements of unsaturation in
hydrocarbons can be extended to include heteroatoms. Let's
consider how the addition of a heteroatom affects the number of
hydrogen atoms in the formula.
 Halogens. Halogens simply substitute for hydrogen atoms in the
molecular formula. The formula C2H6 is saturated, so the formula
C2H4F2 is also saturated. C4H8 has one element of unsaturation,
and C4H5Br3 also has one element of unsaturation. In calculating
the number of elements of unsaturation, simply count halogens as
hydrogen atoms.
 Oxygen. An oxygen atom can be added to the chain without
changing the number of hydrogen atoms or carbon atoms. In
calculating the number of elements of unsaturation, ignore the
oxygen atoms.

 Nitrogen. A nitrogen atom can take the place of a carbon atom in

the chain, but nitrogen is trivalent, having only one additional
hydrogen atom, compared with two hydrogens for each additional
carbon atom. In computing the elements of unsaturation, count
nitrogen as half a carbon atom.
 Example:

7.1.2. Nomenclature of Alkenes

Simple alkenes are named much like alkanes, using
the root name of the longest chain containing the
double bond. The ending is changed from -ane to -
ene. For example, "ethane" becomes “ethene“,
"cyclohexane“ becomes "cyclohexene."
When the chain contains more than
three carbon atoms, a number is used
to give the location of the double
bond. The chain is numbered starting
from the end closest to the double
bond, and the double bond is given
the lower number of its two double-
bonded carbon atoms. Cycloalkenes
are assumed to have the double bond
in the number 1 position.
A compound with two double bonds is a diene. A triene has three double
bonds, and a tetraene has four. Numbers are used to specify the locations of
the double bonds.
 Alkenes as Substituents. Alkenes named as
substituents are called alkenyl groups.
They can be named systematically (ethenyl,
propenyl, etc.), or by common names.
Common alkenyl substituents are the vinyl,
allyl, methylene, and phenyl groups. The
phenyl group (Ph) is different from the others
because it is aromatic and
does not undergo the typical reactions of
alkenes.

Common Names. Most alkenes are

conveniently named by the IUPAC
system, but common names are sometimes
used for the simplest compounds.
7.1.3. Nomenclature of Cis-Trans Isomers
If the bond contains groups on same sides , the alkene is the cis isomer. If the similar
groups are on opposite sides of the bond, the alkene is trans. Not all alkenes are capable
of showing cis-trans isomerism.
If either carbon of the double bond holds two identical groups, the molecule cannot
have cis and trans forms. Following are some cis and trans alkenes and some alkenes
that cannot show cis-trans isomerism.
Physical Properties of Alkenes:
Boiling Points and Densities
 Most physical properties of alkenes are similar to those of the
corresponding alkanes.
 For example, the boiling points of 1-butene, cis-2-butene,
trans-2-butene, and n-butane are all close to 0°C. Also like the
alkanes, alkenes have densities around 0.6 or 0.7 g/cm3. The
boiling points and densities of some representative alkenes are
listed in Table 7-2. The table shows that boiling points of
alkenes increase smoothly with molecular weight.
 As with alkanes, increased branching leads to greater volatility
and lower boiling points. For example, 2-methylpropene
(isobutylene) has a boiling point of -7°C, which is lower than
the boiling point of any of the unbranched butenes.
Physical Properties of Alkenes:
Boiling Points and Densities
Synthesis of Alkenes
Electrophilic Addition to Alkenes
Electrophilic Addition to Alkenes
Orientation of Addition: Markovnikov's Rule
 The proton adds to the end of the double bond that is less
substituted to give the more substituted carbocation (the
more stable carbocation).

 MARKO VNIKO V'S RULE: The addition of a proton

acid to the double bond of an alkene results in a product
with the acid proton bonded to the carbon atom that
already holds the greater number of hydrogen atoms.
Radical Addition of HBr to Unsymmetrical
Alkenes
 Now we must explain the anti-Markovnikov orientation
found in the products of the peroxide-catalyzed reaction.
When the alkene is unsymmetrical, adding the bromine
radical to the secondary end of the double bond forms a
tertiary radical.
 Note that both mechanisms for the addition of HBr to an
alkene (with and without peroxides) follow our extended
statement of Markovnikov's rule: In both cases, the
electrophile adds to the less substituted end of the double
bond to give the more stable carbocation or free radical. In
the ionic reaction, the electrophile is H+. In the peroxide-
catalyzed free-radical reaction, Br· is the electrophile.
 Many students wonder why the reaction with
Markovnikov orientation does not take place in the
presence of peroxides, together with the free-radical chain
reaction. It actually does take place, but the peroxide-
catalyzed reaction is faster.
7.2. Alkynes
 Alkynes are hydrocarbons that contain carbon-carbon
triple bonds. Alkynes are also called acetylenes because
they are derivatives of acetylene, the simplest alkyne.

 A triple bond gives an alkyne four fewer hydrogens than

the corresponding alkane. Its molecular formula is like
that of a molecule with two double bonds: CnH2n-2.
Therefore, the triple bond contributes two elements of
unsaturation (eu)
Nomenclature of Alkynes
 IUPAC Names. The IUPAC nomenclature for alkynes is similar to that
for alkenes. We find the longest continuous chain of carbon atoms that
includes the triple bond and change the -ane ending of the parent alkane
to -yne.
 The chain is numbered from the end closest to the triple bond, and the
position of the triple bond is designated by its lower numbered carbon
atom. Substituents are given numbers to indicate their locations.
 When additional functional groups are present, the suffixes are
combined to produce the compound names of the alkenynes (a
double bond and a triple bond), alkynols (a triple bond and an
alcohol), and so on. The new IUPAC system (placing the
number right before the group) helps to clarify these names.
The IUPAC rules give alkenes and alcohols higher priority than
alkynes, so the numbering begins at the end closer to these
higher-priority groups.
 Common Names. The common names of alkynes
describe them as derivatives of acetylene.
 Most alkynes can be named as a molecule of acetylene
with one or two alkyl substituents. This nomenclature is
like the common nomenclature for ethers, where we name
the two alkyl groups bonded to oxygen.
 Many of an alkyne's chemical properties depend on
whether there is an acetylenic hydrogen (H-C C), that is,
whether the triple bond comes at the end of a carbon
chain. Such an alkyne is called a terminal alkyne or a
terminal acetylene.
 If the triple bond is located somewhere other than the end
of the carbon chain, the alkyne is called an internal alkyne
or an internal acetylene.
Physical Properties of Alkynes
 The physical properties of alkynes (Table 9-1) are similar to those of
alkanes and alkenes of similar molecular weights. Alkynes are
relatively nonpolar and nearly insoluble in water. They are quite
soluble in most organic solvents, including acetone, ether, methylene
chloride, chloroform, and alcohols.
 Acetylene, propyne, and the butynes are gases at room temperature,
just like the corresponding alkanes and alkenes.
Syntheses of Alkynes
Acidity of Alkynes; Formation of Acetylide
Ions
 Terminal alkynes are much more acidic than other
hydrocarbons. Removal of an acetylenic proton forms an
acetylide ion, which plays a central role in alkyne
chemistry. The acidity of an acetylenic hydrogen stems
from the nature of the sp hybrid C-H bond. Table 9-2
shows how the acidity of a C-H bond varies with its
hybridization, increasing with the increasing s character of
the orbitals : sp3 < sp2 < sp. (Remember that a smaller
value of pKa corresponds to a stronger acid.) The
acetylenic proton is about 1019 times as acidic as a vinyl
proton.
Acidity of Alkynes; Formation of Acetylide
Ions
Acidity of Alkynes; Formation of Acetylide
Ions
 Abstraction of an acetylenic proton gives a carbanion that has
the lone pair of electrons in the sp hybrid orbital. Electrons in
this orbital are close to the nucleus, and there is less charge
separation than in carbanions with the lone pair in sp 2 or sp3
hybrid orbitals. Ammonia and alcohols are included for
comparison; note that acetylene can be deprotonated by the
amide -NH2) ion, but not by an alkoxide ion -OR ) .
 Very strong bases (such as sodium amide) deprotonate
terminal acetylenes to form carbanions called acetylide ions
(or alkynide ions). Hydroxide ion and alkoxide ions are not
strong enough bases to deprotonate alkynes. Internal alkynes
do not have acetylenic protons, so they do not react.
Acidity of Alkynes; Formation of Acetylide
Ions
Acidity of Alkynes; Formation of Acetylide
Ions
 Sodium amide is frequently used as the base in forming acetylide
salts. The amide ion -NH2 ) is the conjugate base of ammonia, a compound
that is itself a base. Ammonia is also a very weak acid, however, with Ka =
10-35 (pKa = 35). One of its hydrogens can be reduced by sodium metal to
give the sodium salt of the amide ion, a very strong conjugate base.

 Acetylide ions are strong nucleophiles. In fact, one of the best methods
for synthesizing substituted alkynes is a nucleophilic attack by an
acetylide ion on an unhindered alkyl halide.
Exercises