Alkenes
1
Outcomes
• summarize the attributes of the carbon-carbon double bond
2
Unsaturated Hydrocarbons
• A hydrocarbon that contains one or more carbon-carbon double or triple bonds
or benzene-like rings.
contains a carbon-carbon double bond
and has the general formula CnH2n
contains a carbon-carbon triple bond
and has the general formula CnH2n-2
contains benzene in the structure
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Structure of Alkenes
• Alkenes can either be a terminal alkene, internal alkene, or cycloalkene.
Structure of Alkenes
• The two carbon atoms of a double bond and the four atoms bonded to them lie in a
plane, with bond angles of approximately 120o.
• The two carbon atoms are sp2 hybridized.
• The double bond is composed of 1 σ bond (overlap of sp2 hybridized orbitals)
and 1 𝛑 bond (interaction of 2p orbitals).
Structure of Alkenes
• Rotation on the double bond is restricted because of the 𝛑 bond.
• Substituents could either be on the same side of the double bond (cis-isomer) or
on the opposite sides of the double bond (trans-isomer).
• The trans-isomer has less steric strain making it more stable than the cis-isomer.
Structure of Alkenes
• The stability of an alkene increases as the number of R groups on the C=C
increases.
• sp2 hybridized carbon atoms are more able to accept electron density and sp3
hybridized carbon atoms are more able to donate electron density.
Outcomes
• calculate the degrees of unsaturation given the chemical formula
• propose possible structures given the chemical formula
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Calculating the Degrees of Unsaturation, ρ
• Aka index of hydrogen deficiency
• Each 𝛑 bond or ring removes two hydrogen atoms from a molecule, and this
introduces one degree of unsaturation.
C – no. of carbon
𝟐 + 𝟐𝐂 + 𝐍 − 𝐇 − 𝐗 N – no. of nitrogen
𝛒= H – no. of hydrogen
𝟐 X – no. of halogens (F, Cl, Br, I)
Example: C5H9Cl
𝟐 + (𝟐 ∗ 𝟓) + 𝟎 − 𝟗 − 𝟏
𝛒= =𝟏
𝟐
Calculating the Degrees of Unsaturation, ρ
C – no. of carbon
𝟐 + 𝟐𝐂 + 𝐍 − 𝐇 − 𝐗 N – no. of nitrogen
𝛒= H – no. of hydrogen
𝟐 X – no. of halogens (F, Cl, Br, I)
Example: C8H14
𝟐 + (𝟐 ∗ 𝟖) + 𝟎 − 𝟏𝟒 − 𝟎
𝛒= =𝟐
𝟐
Outcomes
• give IUPAC names to specific alkenes, including cis-trans or E-Z prefixes,
when applicable
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Nomenclature of Alkene
[Step 1] Find the longest chain that contains both carbon atoms of the double
bond and change the –ane ending to -ene
Nomenclature of Alkene
[Step 1] Find the longest chain that contains both carbon atoms of the double
bond and change the –ane ending to -ene
Nomenclature of Alkene
[Step 2] Number the carbon chain to give the double bond the lower number,
and apply all other rules of nomenclature.
Nomenclature of Cycloalkene
• In naming cycloalkenes, the double bond is located between C1 and C2, and
the “1” is usually omitted in the name. The ring is numbered clockwise or
counterclockwise to give the first substituent the lower number.
Nomenclature of Alkene: cis and trans prefixes
• Applicable only if each carbon in the double bond contains 1 substituent
(hydrogen not included).
Nomenclature of Alkene: E and Z prefixes
• Applicable only if each carbon in the double bond contains 2 different
substituents (including hydrogen)
[Step 1] Divide the double bond in half and assign priorities to the two substituents
on each end of the C=C.
• The atom of highest atomic number
gets the highest priority.
• If the atoms on each end of the C=C
are the same, assign priority based
on the atomic number of the
atoms bonded to these atoms.
One atom of higher atomic number
determines a higher priority.
Nomenclature of Alkene: E and Z prefixes
[Step 2] Assign E or Z based on the location of the two higher priority groups. Add a
locant for the E or Z prefix. The prefix must be enclosed in a parenthesis.
Nomenclature of Alkene: E and Z prefixes
[Step 2] Assign E or Z based on the location of the two higher priority groups. Add a
locant for the E or Z prefix. The prefix must be enclosed in a parenthesis.
Nomenclature of Alkene: Exercise
Nomenclature of Alkene: Exercise
Nomenclature of Alkene: Dienes and Trienes
Contains 2 double bonds Contains 3 double bonds
• Follow the steps in naming the alkenes.
• Change the suffix of the alkane to –adiene for 2 double bonds, -atriene for 3
double bonds and so on.
• Add locant for the position of the double bonds.
Nomenclature of Alkene: Dienes and Trienes
• Follow the steps in naming the alkenes.
• Change the suffix of the alkane to –adiene for 2 double bonds, -atriene for 3
double bonds and so on.
• Add locant for the position of the double bonds.
Nomenclature of Alkene: Dienes and Trienes
Contains 2 double bonds
Note: locant for (E) is no longer specified since
there is only one E or Z in the structure.
• Follow the steps in naming the alkenes.
• Change the suffix of the alkane to –adiene for 2 double bonds, -atriene for 3
double bonds and so on.
• Add locant for the position of the double bonds.
Nomenclature of Alkene: Dienes and Trienes
Contains 3 double bonds
Note: locants for (E) are specified since there
are more than one E or Z in the structure.
• Follow the steps in naming the alkenes.
• Change the suffix of the alkane to –adiene for 2 double bonds, -atriene for 3
double bonds and so on.
• Add locant for the position of the double bonds.
Nomenclature of Alkene: Dienes and Trienes
Note: the trans and cis prefixes correspond to
the locants specified for the double bonds.
In this example, the first trans corresponds to the
double bond at carbon 2 while the second trans
corresponds to the double bond at carbon 4.
Nomenclature of Alkene: Common Names
Outcomes
• rank different isomers of an alkene in order of increasing/ decreasing
boiling points
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Physical Properties of Alkynes
• Soluble with each other and in
non-polar organic solvents.
• Melting points and boiling points increase
• Insoluble in water as the number of carbons increases
because of increased surface area.
• Those that are liquid at room temperature
are less dense than water (<1.0 g/mL).
Physical Properties of Alkenes
• Alkyl groups donates electron density to
the sp2 hybridized C making the sp2
hybridized C partially negative and the
alkyl group partially positive.
• This creates a dipole.
Physical Properties of Alkenes
• In the cis-isomer, the dipoles reinforce each other while, in the trans-isomer,
the dipoles cancel. This makes the cis-isomer more polar.
• Because of being more polar, the cis-isomer has higher BP than the trans-
isomer.
Outcomes
• recall the dehydrohalogenation reactions which are useful in the
preparation of alkenes
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Preparation of Alkenes
• Alkenes can be prepared from alkyl halides and alcohols.
Preparation of Alkenes
• Alkenes can be prepared from alkyl halides and alcohols.
• The base (B:) removes a proton on the β carbon.
• The electron pair in the β C – H bond forms the new π bond between the α and β carbons.
• The electron pair in the C – X bond ends up on halogen, forming :X–.
Preparation of Alkenes
• Alkenes can be prepared from alkyl halides and alcohols.
Outcomes
• outline the general mechanism for electrophilic addition reaction
• apply Markovnikov’s rule in predicting the regiochemistry of the products
from the electrophilic addition of reagents to an unsymmetrical alkene
• give the products when HX, H2O, RO-H, X2, and H2O/X2 reagents add to
the C=C of alkenes
• draw the intermediates from the alkene reactions
• write complete mechanisms for the alkene reactions
• outline the details of the two-step hydroboration-oxidation reaction of
unsymmetrical alkenes
• devise a simple synthesis of some compounds from indicated starting
materials via an alkene as “intermediate”
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Reaction of Alkenes: Introduction to Addition Reaction
• In addition reaction, the 𝛑 bond is broken and two new σ bonds are formed.
• Alkenes are electron-rich, thus, they react with electron-deficient reagents
(electrophiles).
Reaction of Alkenes: Introduction to Addition Reaction
Reaction of Alkenes: Introduction to Addition Reaction
Reaction of Alkenes: Introduction to Addition Reaction
• Break the 𝛑 bond add two new σ bonds. Add H in one σ bond and X on the other σ
bond.
Reaction of Alkenes: Introduction to Addition Reaction
• Break the 𝛑 bond add two new σ bonds. Add H in one σ bond and X on the other σ
bond.
Reaction of Alkenes: Introduction to Addition Reaction
In the addition of HX to an unsymmetrical alkene, the
H atom bonds to the less substituted carbon atom -
that is, the carbon that has more H atoms to begin with
Reaction of Alkenes: Introduction to Addition Reaction
In the addition of HX to an unsymmetrical alkene, the
H atom bonds to the less substituted carbon atom
to form a more stable, more substituted carbocation
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with HCl.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with HCl.
Reaction of Alkenes: Introduction to Addition Reaction
Carbocation rearrangement
can also occur prior to attack
of the nucleophile.
Reaction of Alkenes: Introduction to Addition Reaction
Hydrohalogenation can be syn- or anti-addition.
Reaction of Alkenes: Introduction to Addition Reaction
• Break the 𝛑 bond add two new σ bonds. Add H in one σ bond and OH on the other
σ bond.
Reaction of Alkenes: Introduction to Addition Reaction
• H3O+ in Step 1 comes from the acid.
• H3O+ is regenerated in Step 3
Reaction of Alkenes: Introduction to Addition Reaction
• OH bonds with the more substituted carbon
• Occurs to form a more stable carbocation
• The nucleophilic attack of water can occur
at both sides of the planar carbocation
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with H2O/H2SO4.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with H2O/H2SO4.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with H2O/H2SO4.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with H2O/H2SO4.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with H2O/H2SO4.
Reaction of Alkenes: Introduction to Addition Reaction
• Break the 𝛑 bond add two new σ bonds. Add X in one σ bond and another X on the
other σ bond.
Reaction of Alkenes: Introduction to Addition Reaction
• Electrons in the 𝛑 bond is used to
form a C-X bond. The lone pair of X
is used to form another C-X creating
a bridged halonium ion.
• Bridged halonium ion is strained and
is highly unstable.
• Nucleophilic attack opens the ring
structure and relieves the strain. This
is a back-side attack.
Reaction of Alkenes: Introduction to Addition Reaction
• There is no carbocation formed in the
mechanism.
• The nucleophile attacks at the back side of
the bridged halonium ion.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with Br2.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with Br2.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with Br2.
+
Reaction of Alkenes: Introduction to Addition Reaction
• Break the 𝛑 bond add two new σ bonds. Add X in one σ bond and OH on the other
σ bond.
Reaction of Alkenes: Introduction to Addition Reaction
• Formation of bridged halonium ion.
• Nucleophilic attack opens the ring
structure and relieves the strain. This
is a back-side attack.
• The nucleophile is H2O and not X:-
because of higher concentration.
Reaction of Alkenes: Introduction to Addition Reaction
• N-bromosuccinimide or NBS can be the source of Br2 but Br2/H2O can also be
used to form bromohydrin
Reaction of Alkenes: Introduction to Addition Reaction
• There is no carbocation formed in the
mechanism.
• The nucleophile attacks at the back side of
the bridged halonium ion.
• The more substituted carbon is more able
to accept a partial positive charge (similar
to acidic epoxide ring opening)
Reaction of Alkenes: Introduction to Addition Reaction
• Br is more electronegative than C. This makes the carbons in the ring partially
positive. Because the alkyl groups are electron density donating, the carbon
with more substituents is more able to accept the partial positive charge.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with Cl2/H2O.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with Cl2/H2O.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with
NBS/DMSO,H2O.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with
NBS/DMSO,H2O.
H
H
Reaction of Alkenes: Introduction to Addition Reaction
• Break the 𝛑 bond add two new σ bonds. Add H in one σ bond and OH on the other
σ bond.
Reaction of Alkenes: Introduction to Addition Reaction
A. Hydroboration to form alkylborane is syn addition of
BH3
Reaction of Alkenes: Introduction to Addition Reaction
• With unsymmetrical alkenes, the boron atom bonds to the less substituted C atom.
• The larger boron atom bonds to the less sterically hindered carbon.
Reaction of Alkenes: Introduction to Addition Reaction
• Since H atom is more electronegative than B atom, the B atom is partially positive
while H atom is partially negative. The H atom will bind to the partially positive C
atom (the more substituted C atom).
Reaction of Alkenes: Introduction to Addition Reaction
B. Oxidation of alkylborane using basic hydrogen peroxide (H2O2, OH-)
• OH replaces BH2 with retention of configuration.
Reaction of Alkenes: Introduction to Addition Reaction
• OH bonds with the less substituted carbon
• There is no carbocation formed in the
mechanism.
• Hydroboration occurs via syn addition
while oxidation does not change the
configuration of the molecule.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with
1. BH3/ 2. H2O2,OH-.
Reaction of Alkenes: Introduction to Addition Reaction
Exercise: Draw the products formed when each alkene is treated with
1. BH3/ 2. H2O2,OH-.
Reaction of Alkenes:
• Utilizes a catalyst (Pd, Pt, or Ni) to add H2 to alkene
Reaction of Alkenes:
Reaction of Alkenes:
• Rapid, sequential addition of H2 occurs from the side of the alkene complexed to
the metal surface, resulting in syn addition.
• Less crowded alkene complex more readily to the catalyst surface, resulting in
faster reaction.
Reaction of Alkenes:
Exercise: Draw the products formed when each alkene is treated with H2/Pd.
Reaction of Alkenes:
Exercise: Draw the products formed when each alkene is treated with H2/Pd.
Reaction of Alkenes:
