Alkenes

Hydrocarbons that contain a carbon-carbon

double bond.
General formula of : C
n
H
2n
AC-C double bond consists of one sigma and
one pi bond.
A double bond is stronger than a single
covalent bond and also shorter with an average
bond length of 133 pm.



Alkenes
Rotation about the C-C bond is restricted
because it involves breaking the pi bond which
requires a large amount of energy.



Isomerism in Alkenes
Structural Isomerism
There are two or more different structural
formulae that you can draw for each molecular
formula.


Isomerism in Alkenes
Cis-transIsomerism
The lack of rotation in the C-C double bond in
alkenes gives rise to two sides in the double bond
resulting in cis-trans isomerism in disubstituted
alkenes.
Disubstituted means that two substituents other
than hydrogen are bonded to the double-bond
carbons.



Isomerism in Alkenes
Cis-transIsomerism
Interconversion of cis and trans alkene isomers
doesnt occur spontaneously but it can be brought
about by treating the alkene with a strong acid
catalyst.



Isomerism in Alkenes
Cis-transIsomerism
Cis alkenes are less stable than their trans isomers
because of steric interference between the large
substituents on the same side of the double bond.

Isomerism in Alkenes
E,ZDesignation
A method used for describing double bond
geometry. This is used with trisubstituted and
tetrasubstituted alkenes.
Trisubstituted means three
substituents other than hydrogen
on the double bond.
Tetrasubstituted means four
substituents other than hydrogen
on the double bond.



Isomerism in Alkenes
E,ZDesignation
Substituents must be ranked according to the
Cahn-Ingold-Prelogrules.
If the higher-ranked groups on each carbon are on
opposite sides of the double bond, the alkene is
said to have E stereochemistry, for the German
entgegen, meaningopposite.
If the higher-ranked groups are on the same side,
the alkene has Z stereochemistry, for the German
zusammen, meaningtogether.



Isomerism in Alkenes
E,ZDesignation:Cahn-Ingold-PrelogRules
Rule 1: Considering the double-bond carbons
separately, look at the atoms directly attached to
each carbon and rank them according to atomic
number.
Atomic
#
35 17 16 15 8 7 6 (2) (1)
Higher
ranking
Br Cl S P O N C
2
H
1
H


Isomerism in Alkenes
E,ZDesignation:Cahn-Ingold-PrelogRules
Rule 2: If a decision cant be reached by ranking
the first atoms in the substituents, look at the
second, third, or fourth atoms away from the
double bonds until the first difference is found.
Rule 3: Multiple-bonded atoms are equivalent to
the same number of single-bonded atoms.



Isomerism in Alkenes
E,ZDesignation:Cahn-Ingold-PrelogRules
Lower
priority
Lower
priority
Higher
priority
Higher
priority
Z designation



Isomerism in Alkenes
E,ZDesignation:Cahn-Ingold-PrelogRules
Lower
priority
Lower
priority
Higher
priority
Higher
priority
E designation


Physical Properties of Alkenes
As the number of carbon atoms increases in an
alkene, the boilingpoint also increases.
Alkene has a boiling point which is a small
number of degrees lower than the
correspondingalkane.
Linear alkenes of approximately five to sixteen
carbons are liquids, and higher alkenes are waxy
solids.
Alkenes are virtually insoluble in water, but
dissolve in organic solvents.


Kinds of Organic Reactions
Addition Reactions occur when two
reactants add together to form a single new
product with no atoms left over.


Kinds of Organic Reactions
EliminationReactions occur when a single
organic reactant splits into two products, often
with formation of a small molecule such as
H
2
O.

Kinds of Organic Reactions
Substitution Reactions occur when two
reactants exchange parts to give two new
products.


Kinds of Organic Reactions
Rearrangement Reactions occur when a
single organic reactant undergoes a
reorganization of bonds and atoms to yield a
single isomeric product.



Reaction Mechanism
It describes what takes place at each stage of a
chemical transformation- which bonds are
broken and in what order, which bonds are
formed and in what order, and what the relative
rates of the steps are.
All chemical reactions involve bond-breaking
in the reactant molecules and bondmaking in
the product molecules, which means that the
electrons in those bonds must move about and
reorganize.

Reaction Mechanism
Waysforacovalent two-electronbondtobreak:
HomolyticCleavage when a bond break in
an electronically symmetrical way so that one
electron remains with each product fragment.


Reaction Mechanism
Waysforacovalent two-electronbondtobreak:
HeteroticCleavage when a bond break in an
electronically unsymmetrical way so that both
electrons remain with one product fragment,
leavingthe other fragment with a vacant orbital.


Reaction Mechanism
Waysforacovalent two-electronbondtoform:
Symmetrical bond-making
Unsymmetrical bond-making
A
+
+ B:
-
AB

Reaction Mechanism
Radical Reactions processes that involve
symmetrical bond-breakingand bond-making.
Freeradical a neutral chemical species that
contains an odd number of electrons and thus
has a single, unpaired electron in one of its
orbitals.
Polar Reactions processes that involve
unsymmetrical bond breaking and bond-
making.


Reaction Mechanism: Polar Reactions
More common reaction type in both organic and
biological chemistry.
Occurs when an electron-rich site in one
molecule react with electron-poor sites in another
molecule or even within the same molecule.
Bonds are made when an electron-rich atom
shares a pair of electrons with an electron-poor
atom.
Bonds are broken when one atomleaves with both
electron s fromthe former bond.


Reaction Mechanism: Polar Reactions
Nucleophile
A substance that is nucleus loving and thus
attracted to a positive charge.
Has a negatively polarized, electron-rich atom,
and can form a bond by donating an electron pair
to a positivelypolarized, electron-poor atom.
Can be either neutral or negatively charged and
usuallyhave lone pairs of electrons.



Reaction Mechanism: Polar Reactions
Nucleophile


Reaction Mechanism: Polar Reactions
Electrophile
A substance that is electron loving and thus
attracted to a negative charge.
Has a positively polarized, electron-poor atom,
and can form a bond by accepting an electron pair
froma nucleophile.
Can be either neutral or positivelycharged.


Reaction Mechanism: Polar Reactions
Electrophile

Mechanism of the Addition of HCl to Ethene
An example of a general polar reaction type known
as electrophilicadditionreaction.


Energy Diagram of the
Addition of HCl to Ethene

Energy Diagram
It is a graph that shows the progress of a chemical
reaction against the total energy of the system. It
indicates the following:
Transition State represents the highest-energy
structure involved in a step of a reaction and cant
be isolated or directlyobserved. It is imagined to be
a kind of activated complex of the two reactants.
Activation Energy the minimum energy
needed to initiate a chemical reaction. It is the
energy difference between the reactants and the
transition state.

Energy Diagram
Reaction Intermediate is a molecular
entity that is formed from the reactants (or
preceding intermediates) and reacts further to
give the directly observed products of a chemical
reaction.

Energy Diagram
ExothermicReaction is a chemical reaction
that releases energy.
EndothermicReaction is a chemical reaction
that absorbs energy.

Catalysis
Catalyst is
a substance
that increases
the rate of a
chemical
transformatio
n by providing
an alternative
mechanism.