Resonance

- Often more than one equivalent Lewis structure can be written for a molecule or ion, resonance theory
states that whenever a molecule or ion can be represented with more than one Lewis structure that differ
only in the position of electrons, two things will be true:
o None of the resonance structures are a realistic representation for the molecule since none of
the structures will exhibit the complete physical or chemical property of the substance
o The actual molecule is better represented by a resonance hybrid of all the structures
 Resonance structures, therefore, are only hypothetical structures for the actual
molecule and therefore cannot be isolated; no single contributor adequately represents
the molecule
 Resonance structures are drawn with a double-headed arrow to indicate that they are
hypothetical

- Resonance Structures
o Things to Remember
 Curved arrows are used to show the movement of bonding and unshared electrons
 A double barbed curved arrow shows the movement of two electrons;
 A curved arrow originates at the location of the electrons and point to where those
electrons will be drawn in the resonance structure
 The new formula is drawn to show the result of the electron shift(s). It should be a
proper Lewis structure and have appropriate formal charges.

o Rules for Writing Resonance

1. In resonance structures, only the electrons are allowed to move; the positions of the nuclei
of the atoms remain the same in all structures. When we move electrons, we move only
those in multiple bonds and those of nonbonding electron pairs

2. All the resonance structures must be proper Lewis structures

3. The energy of the resonance hybrid is lower than the energy of any contributing structure.
Resonance stabilizes a molecule, especially when the resonance structures are equivalent.
 This is referred to as resonance stabilization. If the resonance structures are equivalent,
resonance stabilization is large

4. The more stable a structure is, the greater is its contribution to the hybrid

o Deciding which Resonance Structure contributes more to the hybrid

 The more covalent bonds a structure has, the more stable it is. Hence, it contributes more to
the hybrid structure

 Charge separation decreases stability ; it takes energy to separate opposite charges and
therefore a structure with separate charges is less stable
 Structures in which all atoms have a complete valence shell are more stable

Acid-Base Reactions

- Bronsted-Lowry Acid-Base = involves the transfer of protons

o Bronsted-Lowry Acid = proton donor; Bronsted-Lowry Base = proton acceptor
 Conjugate Base = molecule or ion formed when an acid loses its proton
 Conjugate Acid = molecule or ion formed when a base accepts a proton
o The extent to which an acid transfers its protons to a base is a measure of its strength as an acid;
acid strength is a measure of the percentage of ionization and NOT concentration

- Lewis Acid-Base
o Lewis Acid = electron pair acceptor; Lewis Base = electron pair donor
 Lewis acid-base theory includes all of the Bronsted-Lowry acid-base reactions
 Any electron-deficient atom can acts as a Lewis Acid
o In Lewis acid-base theory, the attraction of oppositely charged species is fundamental to
reactivity
- Heterolysis of Carbon Bonds
o Heterolysis of a bond to a carbon atom can lead to either of two ions: one with a positive charge
on the carbon atom and one with a negative charge on the carbon atom
 Carbocations = ions with a positively charged carbon atom; they are electron deficient
and act as Lewis acids. Most carbocations are short-lived and highly reactive, occurring
as intermediates in some organic reactions. Carbocations react immediately with Lewis
bases to achieve a stable octet of electrons
 Carbanions = ions with a negatively charged carbon atom; they are electron rich and act
as Lewis bases
 o Carbocations, being electron-seeking reagents, are also called electrophiles
 All Lewis acids are electrophiles
 Carbon atoms that are electron poor due to bond polarity, but are not carbocations, can
also be electrophiles
o Carbanions seek a proton or some positive center with which they can donate their electron pair
and neutralize their negative charge, hence they are also called nucleophiles
 Nucleophiles are Lewis bases that seek a positive center
- Strength of Acids and Bases
o Acid strength is characterized in terms of acidity constant ( K a ) or p K a
 Since the reaction in an aqueous solution of a weak acid is an equilibrium, it can be
described with an expression for the equilibrium constant (K).
K [ H 2 O]=¿ ¿
We can rewrite the expression for the equilibrium constant in terms of a new constant,
the acidity constant K a ; rewriting the expression for any hypothetical acid dissolved in
water such that:
−¿¿

HA + H 2 O⇋ H 3 O +¿+ A ¿

K a =¿ ¿
 A large value for K a means the acid is a strong acid and a small value of K a
means the acid is a weak acid
 The acidity constant K a is usually expressed as its negative logarithm p K a, which is
analogous to the expression of hydronium ion concentration pH
p K a=−log K a
 There is an inverse relationship between the magnitude of p K a and strength
of an acid. The larger the p K a value, the weaker the acid

o Base strength is characterized based on acid strength. The stronger the acid, the weaker the
conjugate base; the larger the p K a value of the conjugate acid, the stronger is the base

- Relationship of Structure and Acidity

o The strength of a Bronsted-Lowry acid depends in the extent to which a proton can be separated
from it and transferred to a base. Removing a proton involves breaking a bond to the proton and
making a conjugate base more electrically negative
  The bond strength to the proton
decreases as we move down a group
on the periodic table, resulting to
increasing acidity
 Acidity increases from left to right in a
given period from the periodic table.
As electronegativity increases, it
affects the polarity of the bond to the
proton and it affects the stability of
the anion that forms the proton lost
o Effect of Hybridization
o Energy Change
- Acidity of Carboxylic acids (Organic Acids)
o Resonance Effect
 Delocalization of the negative charge is possible in a carboxylate ion, permitting the
formation of resonance structures that induce resonance stabilization.
 The resonance structures of the carboxylate distributed the negative charge on both
oxygen atoms, stabilizing the charge – this is a delocalization effect by resonance; charge
delocalization is a stabilizing factor since the energy for formation of the anion becomes
lower
o Inductive Effects = polarization of the bonds that results from an intrinsic electron-attracting
ability of an atom that is transmitted through space and through the bonds of the molecule;
electronic effects transmitted through bonds.
 The inductive effect can be electron donating or electron withdrawing.
 Inductive effects weaken as the distance from the group increases
- Steric Effect
Alkanes and Cycloalkanes: Conformation and Reactivity

Sources of Alkanes

- Primary source of alkanes is petroleum, a complex mixture of organic compounds which are mostly
alkanes and aromatic compounds; also contains small amounts of O-, N-, and S- containing compounds
o Some molecules of petroleum are of biological origin, originating from the accumulation of dead
microorganism at the sea floor and entombed by sedimentary rock, transforming into oil by heat
from the Earth’s core
- Hydrocarbons are also found in outer space; asteroids and comets contain a variety of them, and the
atmospheres of some planets are also rich in some hydrocarbons

Shapes of Alkanes

- A tetrahedral orientation is the general rule for carbon atoms of alkanes and cycloalkanes
- Unbranched alkanes = chain of hydrocarbons where each C atom within the chain is bonded to no more
than two other C atoms; contains only primary and secondary carbon atoms
- Branched alkanes = chain of hydrocarbons where a C atom within the chain is bonded to more than two
other C atoms
o Constitutional isomers = compounds with the same molecular formula but have their atoms
connected in a different order and structure
 Constitutional isomers have different physical properties
 Number of constitutional isomers increase as the number of C atoms increases

Physical Properties of Alkanes and Cycloalkanes

- Homologue series = a series of compounds where each succeeding member differs by a constant unit;
members of a homologue series are called as homologues
o At standard state, C H 4 −C 4 H 10 are gases, C 5 H 12−C 17 H 36 are liquids and unbranched
alkanes with 18 and more C atoms are solids
- Boiling point
o Boiling point of the unbranched alkanes increase with
increasing molecular weight in the homologue series of
unbranched alkanes; but branching of the alkane lowers
the boiling point
 In unbranched alkanes, as molecular weight
increases, so does molecular size and molecular
surface area, which increases the forces
between the molecules, requiring more energy
to reach the boiling point
 Chain branching makes molecules more
compact, reducing surface area and the forces
between the molecules, lowering the boiling point
- Melting Point
o There is an alteration between an even-numbered alkane
to an odd-number alkane, and by plotting them on
separate curves, increasing melting point is observed
with increasing molecular weight
 Even-numbered alkane chains pack more closely
in the crystalline state, and as a result, attractive
forces between individual chains are greater and
melting points are higher
- Cycloalkanes have higher boiling points and melting points than
their open-chain counterparts
 - Density
o Alkanes and cycloalkanes are the least dense of all organic compounds, with densities
considerably less than that of water
- Solubility
o Alkanes and cycloalkanes are almost insoluble in water because of their low polarity and inability
to form hydrogen bonds; liquid alkanes and cycloalkanes are soluble in one another, generally
dissolving in solvents of low polarity

Sigma Bonds and Bond Rotation

- Two groups bonded by a single bond can undergo rotation about that bond with respect to each other
o Conformations = temporary molecular shapes that result from bond rotations; each possible
structure is called a conformer
o Conformational analysis = analysis of the energy changes that occur as a molecule undergoes
rotations about single bonds
- Newman Projections
o How to Draw Newman Projections
 Imagine taking a view from one atom directly along a selected
bond axis to the next atom

 The front carbon and its other bonds are represented as

 The back carbon and its bonds are represented as

o The staggered conformation of a molecule is the conformation where the
atoms bonded to the carbons at each end of the C-C bond are as far apart as possible; the
dihedral angle between the bonds is 180°

o The eclipsed conformation of a molecule is the conformation where the atoms bonded to the
carbons at each end of the C-C bond are directly opposed to one another; the dihedral angle
between the bonds is 0°

- How to do Conformational Analysis

o Small changes in the dihedral angle between C-H bonds could lead to an infinite number of
conformations; however, these conformations are not equally stable, and it is known that the
staggered conformation is the most stable since it has the lowest potential energy
 The stability of staggered conformations relates mainly to steric repulsion between
bonding pairs of electrons; the staggered conformation allows the maximum separation
of electrons in the C-H bonds, minimizing of steric repulsions, while in the eclipsed
conformation, electron clouds from the C-H bonds are closer and repel one another
 Hyperconjugation, which involves overlap between filled and unfilled sigma bonds, help
stabilize the staggered conformation
 o Ethane
 In ethane, the energy difference between its
two conformations is 12 kJ/mol, this is called
the torsional barrier of the single bond; due to
this barrier, some molecules will have their
atoms in staggered conformations while others
with more energy will assume an eclipse
conformation
 A single molecule of ethane will spend most of
its time in the staggered conformation but many
times in a second, it may acquire enough energy
to form the eclipsed conformation.
 Considering a large number of ethane
molecules, at any given moment, most of the
molecules will be in staggered conformations
o Butane
 The factors involved in barriers to bond rotation are
called torsional strain which include steric
hindrance, repulsive interactions between electron
clouds of the bonded groups
 Torsional strain results from steric hindrance
between the terminal methyl groups and the
hydrogen atoms and between two methyl groups
 The anti conformation does not have
torsional strain from steric hindrance
because the groups are staggered and the
methyl groups are far apart, making it the
most stable
 The methyl groups in the gauche
conformation are close enough to each other that they repel one another,
causing the gauche conformation to have more energy than the anti
conformation
 The eclipsed conformations
representing the maximum
energy, have repulsive dispersions
forces that arise from the eclipsed
methyl and hydrogen plus the
large repulsive dispersion force
between the eclipsed methyl
groups, which has the greatest
energy of all
o Stereoisomers = same molecular formula and
connectivity but different atom arrangements in three-dimensional space
o Conformational stereoisomers = related to one another by bond rotations

Stability of Cycloalkanes: Ring Strain

- Not all cycloalkanes have the same relative stability, this is due to the ring strain of the structure which is
comprised of angle strain and torsional strain
o Angle strain = deviation from ideal bond angles caused by inherent structural constraints
o Torsional strain = result of repulsive dispersion forces that cannot be relieved due to restricted
conformational mobility
 - Ring strain of Cyclopropane
o In cyclopropane the internal
angles are 60° , departing by
about 49.5° from tetrahedral
bond angle
o Angle strain exists because the sp 3
orbitals of the C-C bonds cannot
overlap as effectively as they do in
alkanes, with the bonds often being described as “bent”
o Since the C-C bonds are weaker, the molecule has greater potential energy, therefore, less stable
o Angle strain is not the sole reason for most of the ring strain; since cyclopropane is planar, the C-
H bonds of the ring are eclipsed, and the molecule has torsional strain from repulsive dispersion
forces as well
- Ring strain of Cyclobutane
o The internal angles of cyclobutane are 88° , departing by
about 21° from the ideal bond angle; the cyclobutane ring
is not planar but “slightly folded.”
o If the ring was planar there would be less angle strain, but
the torsional strain would be larger because all C-H bonds
would be eclipsed; by slightly bending, the ring is able to
relieve more of its torsional strain
- Ring strain of Cyclopentane
o The internal angles of a cyclopentane are 108 ° , very
close to the tetrahedral bond angle; if the ring were
planar, it would have very little angle strain, but
planarity would cause all the C-H bonds to eclipse and
induce a large torsional strain
o Therefore, cyclopentane assumes a slightly bent
conformation where one or two atoms of the ring are
out of the plane, relieving some torsional train
o The slight twisting of C-C bonds can occur with little changes in energy and causes the atoms to
move in-and-out the plane, resulting to being flexible and shifting conformation constantly

Conformations of Cyclohexane: Chair and Boat

- Cyclohexane is one of the more stable cycloalkanes; its most stable conformation is its chair conformation
due to the absence of angle or torsional strain
o In chair conformation, all the C-C bond
angles are 109.5° , making them free of angle
and torsional strain
o All the bonds are perfectly staggered, with
the H atoms maximally separated at opposite
corners of the ring, when viewed along any
C-C bond
- By partial rotation about the carbon-carbon single bonds, the chair conformation can assume the boat
conformation; the boat conformation has no angle strain but it does have torsional strain
o When viewed down the C-C bond axes along
either side, the C-H bonds are found to be
eclipsed which causes torsional strain
 o The H atoms on C1 and C4 of the boat conformation are also close enough to cause van der
Waals repulsion which causes the “flagpole” interaction; torsional strain and flagpole interactions
cause the boat conformation to have higher energy i.e., less stable
- Although the chair conformation is more stable, it is also much more rigid compared to the boat
conformation; the boat conformation can flex to a new form, the twist configuration, and relieve some of
its torsional strain and flagpole interactions
o The twist conformation has lower
energy than the boat conformation
but it is not as stable as the chair
conformation
o The stability gained by flexing is
insufficient to cause the twist
configuration to be more stable than
the chair configuration
- The energy barriers between the three
conformations are low enough to make
separation of the conformers impossible at
room temperature
- Because of the greater stability of the chair,
more than 99% of the cyclohexane is estimated
to be in chair conformation

Axial and Equatorial Hydrogen Groups

- The chair confirmation of cyclohexane has two distinct orientations for the bonds that project from the
ring
o Axial bonds = perpendicular to the plane of the ring with their orientation (up or down)
alternating from one carbon to the next
o Equatorial bonds = extend from the perimeter of the ring and alternate
from slightly up to slightly down from one carbon to the next
o When a cyclohexane ring undergoes chair-chair conformational change
(ring flip) all the axial bonds become equatorial, and all equatorial
bonds become axial
- How to Draw Conformational Structures
o Equatorial bonds are parallel to ring
bonds that are one bond away from
either direction; Axial bonds are in
vertical orientations.
o When a vertex of bonds in the ring
points up, the axial bond at that
position is also up and the equatorial
bond at the same carbon is slightly
down. When a vertex of ring bonds is down, the axial bond at that position is also down, and the
equatorial bond is slightly up
- Conformational Analysis of Methyl Cyclohexane
o Has two possible chair conformations: one with
the methyl group occupying an axial position
and one with the methyl group occupying an
equatorial position; both interconvert through
the bond rotations that constitute a ring flip
 o The most stable conformation for a monosubstituted cyclohexane ring is the conformation
where the substituent is equatorial
 When the substituent methyl group is axial, it is so close to the two axial hydrogens on
the same side of the ring that dispersion forces between them are repulsive; this steric
strain between an axial group and an axial hydrogen is called a 1,3-diaxial interaction
- 1,3-Diaxial Interactions of a t-Butyl Group
o Strain caused by 1,3-diaxial interactions is more pronounced in cyclohexane derivatives with
larger alkyl substituents; the conformation with
the t-butyl group at equatorial is more stable than
the axial form and the large energy difference
between the two conformations mean that at
room temperature, 99.99% of the t-
butylcyclohexane molecules have the t–butyl
group at an equatorial position

Disubstituted Cycloalkanes: Cis-Trans Isomerism

- Presence of two substituents on different carbons of a cycloalkane allows for the possibility of cis-trans
isomerism; cis-trans isomerism are also stereoisomers since they differ from each other only in the
arrangement of the atoms in space
o Cis = substituents are on the same side of the ring; Trans = substituents are on opposite sides of
the ring
o Cis and trans isomers cannot be interconverted
without breaking C-C bonds, as a result they can be
separated and kept indefinitely

Radical Formation

- Radicals = free radicals; intermediates possessing unpaired electrons

o Heterolysis

o Homolysis

- Production of Radicals
o Energy in the form of heat or light must be supplied to cause homolysis of covalent bonds

- Reactions
o Almost all small radicals are short-lived, highly reactive species
o When radicals collide with other molecules, they tend to react in a way that leads to pairing of
their unpaired electrons
 Abstracting = to abstract an atom means to
remove an atom by homolytic bond
cleavage as the atom forms a bond with
another radical
  A halogen atom may induce hydrogen abstraction on an alkane – the halogen
atom gains an electron from an H-atom of the alkane that pairs with its
electron; the other product of this reaction is another radical
o Radicals can also react by combining with a compound containing a multiple bond to produce a
new radical, which goes on to react further

Homolytic Bond Dissociation

- When atoms combine to form molecules, energy is released as covalent bonds form, causing the
molecules of the products to have lower enthalpy than the separate atoms
o When atoms combine, heat is produced: the reaction, therefore, is exothermic ( ∆ H o =−¿)

o Energy is required to break the covalent bonds of an atom: the reaction, therefore, is
endothermic (∆ H o =+¿)

 Homolytic bond dissociation energy (∆ D H o ) = the energy required to break covalent

bonds through homolysis
- Using ∆ D H o to determine relative stabilities of radicals
o ∆ D H o provides a convenient way of estimating the relative stabilities of radicals
 While both reactions may begin
with the same alkane and produce
an alkyl radical and a hydrogen
atom, they differ in the amount of
energy required and in the type of
carbon radical produced
o Alkyl radicals are classified as 1 ° , 2 ° ,∨3 °
based on the carbon atom that has the unpaired electron; the order of stability of alkyl radicals is

the same as for carbocations

o Although alkyl radicals are uncharged, the carbon that bears the unpaired electron is electron
deficient; therefore, alkyl groups attached to the electron deficient carbon provide a stabilizing
effect through hyperconjugation and the more alkyl groups bonded, the more stable the radical

Reactions of Alkanes with Halogens

- Alkanes react with halogens to produce alkyl halides by radical halogenation

o Radical halogenation = halogen atom replaces one or more of the hydrogen atoms of the alkane,
and the corresponding hydrogen halide is formed as a by-product. Only F, Cl, and Br react this
way with alkanes
- Multiple Halogen Substitution
o One complication of alkane halogenation is that multiple substitutions almost always occurs
unless there is an excess of the alkane

 At the outset, the only compounds present in the mixture are the alkane and the
halogen and the only reaction that can take place is the production of chloromethane
and hydrogen chloride

 As the reaction proceeds, the concentration of chloromethane increases, and a second

substitution begins to occur – chloromethane reacts with chlorine to produce
dichloromethane

 The dichloromethane produced can then react to form trichloromethane which

eventually reacts to form tetrachloromethane; each time a substitution of –Cl for –H
occurs, a molecule of H–Cl is produced
- Lack of Chlorine Selectivity
o Chlorination of higher alkanes gives a mixture of isomeric monochlorinated products as well as
highly halogenated products
o Chlorine is relatively unselective – it does not discriminate among the different types of hydrogen
atoms in the alkane

 Since alkane chlorination usually yields a complex mixture of products, it is not useful as
a synthetic method for the preparation of a specific alkyl chloride
o An exception is the halogenation of an alkane or cycloalkane whose hydrogens are all equivalent
(homotopic); homotopic hydrogen = hydrogen atoms that on replacement by another group (Cl)
yield the same compound
Chlorination of Methane: Reaction Mechanism

- This reaction is promoted by heat or light and the light-promoted reaction is highly efficient
- Chain reaction = a type of sequential, stepwise mechanism in which each step generates the reactive
intermediate that causes the next cycle of the reaction to occur
o The first step involves the dissociation of a chlorine molecule, by heat or light, into two highly
reactive chlorine atoms; the first step is called the chain-initiating step

o The second step involves hydrogen abstraction by a chlorine atom; the second and third step are
called the chain-propagating steps where one radical generates another

o In the third step, the highly reactive methyl radical reacts with diatomic chlorine by abstracting a
chlorine atom which results in the formation of chloromethane and a chlorine atom

o The chlorine atom produced in the third step can attack another methane and cause a repetition
of the process multiple times; each repetition of the third step produces a molecule of
chloromethane
o Chain-terminating steps are steps that use up one or both reactive intermediates; the continuous
replacement of intermediates used up by the chain-terminating steps requires continuous
irradiation
Halogenation of Higher Alkanes

- Higher alkanes also react with the same

kind of chain mechanisms
- Chlorination of most alkanes with more
than two carbon atoms give a mixture of
isomeric monochlorinated and highly
chlorinated products
o There is a correlation between
reactivity of different hydrogen
atoms and the type of hydrogen
atom (1 ° , 2 °, 3 ° ) being
replaced.
 By order of decreasing
reactivity: 3 ° > 2 ° > 1 °
o The relative reactivities of the hydrogen atoms in a chlorination reaction can be accounted for by
their homolytic bond dissociation energies
 Breaking a tertiary C–H bond requires the least energy and breaking a primary C–H bond
requires the most energy
 Since hydrogen-abstraction determines the location or orientation of the chlorination,
the activation energy for abstracting a tertiary hydrogen is expected to be less than that
of a primary hydrogen atom
o However, the difference in rates of the different hydrogen atoms is not large since chlorine does
not discriminate among the hydrogen atoms

Bromine Selectivity

- Bromine is generally less reactive towards alkanes than chlorine and more selective in the site of attack
when it does react
- Bromination is selective for substitution where the most stable radical intermediate can be formed

Fluorine Selectivity

- Fluorine, being more reactive than chlorine, is even less selective than chlorine
- Since the activation energy for the abstraction of any type of hydrogen by a fluorine atom is low, there is
very little difference at which type of hydrogen reacts with fluorine
- Reactions of alkanes with fluorine gives the distribution of products expected if all the hydrogen atoms of
an alkane were equally reactive

Other Important Radical Reactions

- Combustion of Alkanes
o When alkanes react with oxygen, a complex series of reactions take place which ultimately
converts the alkane to carbon dioxide and water
  Product of the second chain-propagating step is R-OOH, an alkyl hydroperoxide; the
oxygen-oxygen bond of an alkyl hydroperoxide is quite weak and can beak and produce
radicals that can initiate other chains

Alkenes and Alkynes: Stereochemistry and Reactivity

Physical Properties of Alkenes and Alkynes

- Alkenes are hydrocarbons whose molecules contain a carbon-carbon double bond; also called as olefins
- Alkynes are hydrocarbons whose molecules contain a carbon-carbon triple bond; also called acetylenes
- Alkenes and alkynes have physical properties similar to their corresponding alkanes
o Alkenes and alkynes up to four carbons are gases at room temperature; higher numbered
alkenes and alkynes are liquids at room temperature
o Relatively nonpolar and dissolve in nonpolar solvents; slightly soluble in water
o Have densities that are lower than water

(E)-(Z) System Configuration

- Using the Cahn-Ingold-Prelog Convention, this system applies to alkene diastereomers of all types;
characteristically used for trisubstituted or tetrasubstituted alkenes
- Examine the two groups attached to one carbon atom of the double bond and decide which has higher
Cahn-Ingold-Prelog priority; do this for both carbon atoms of the double bond
o Priority is first assigned based on the atomic number of the atom directly attached to the carbon
– the higher the atomic, number, higher the priority; in the case of isotopes, the isotope of
greater atomic mass has higher priority
o When priority cannot be assigned based on the atomic number of the atoms directly attached,
the next set of atoms in the unassigned groups are examined until a decision can be made
o Groups with multiple bonds are assigned priorities as if both atoms were duplicated or triplicated
- Compare the group of higher priority on one carbon atom with the group of higher priority on the other
carbon atom
o If the two high priority groups are on the same side of the double bond, the alkene is designated
as (Z) or zusammen
o If the two high priority groups are on opposite sides of the double bond, the alkene is designated
as (E) or entgegen

Relative Stabilities of Alkenes

- Cis and trans isomers of alkenes do not have the same stability; strain
caused by crowding of two alkyl groups on the same side of the double
bond make cis isomers generally less stable
- A quantitative measure of alkene stability can be obtained by
comparing the heats of hydrogenation of a family of alkenes that
become the same alkane product upon hydrogenation
o Hydrogenation is the addition of hydrogen; heat of
hydrogenation is the enthalpy change involve in the
reaction
o The trans isomer is more stable than the cis isomer
because less energy is released when the trans isomer is
converted into an alkane via hydrogenation
 - The greater the number of attached alkyl groups, or the more highly substituted the carbon atoms of the
double bond, the greater is the alkene’s stability

Cycloalkenes

- The rings of cycloalkenes containing fewer than six carbons exist only in the cis form; introducing a trans
double bond in something would introduce strain that is greater than what the atoms can accommodate
- Trans conformations of cycloalkenes with higher number of carbon atoms are large enough to
accommodate the geometry required to be stable

Synthesis of Alkenes: Elimination Reactions

- Elimination reactions are the most important means for synthesizing

alkenes; in elimination reactions, fragments of the molecule are
eliminated from adjacent atoms of the reactant which leads to the
creation of a multiple bond
- Example of elimination reactions used for alkene synthesis are dehydrohalogenation of alkyl halides and
dehydration of alcohols

Dehydrohalogenation

- Alkene synthesis via the elimination of HX from

adjacent atoms of an alkyl halide; heating the alkyl
halide with a strong base causes the reaction to take
place
- In these elimination reactions, there is a leaving group and an attacking Lewis base
that possesses an electron pair
- The carbon atom that bears the leaving group (the halogen) is called the alpha (α)
carbon and any carbons adjacent to it is a beta (β) carbon; a hydrogen attached to
the beta carbon is called a beta (β) hydrogen
- Since the hydrogen atom eliminated in dehydrohalogenation is from a β carbon, the
reaction is often called β eliminations or 1,2 eliminations
- Various strong bases can be used for dehydrohalogenation: potassium hydroxide dissolved in ethanol,
conjugate base of alcohols such as sodium ethoxide, or potassium tert-butoxide
- Elimination occurs in several mechanisms and with alkyl halides, two important mechanisms occur: the E2
reaction and E1 reaction

E2 Reaction

- In an E2 mechanism, a base removes a

β hydrogen from the β carbon as the
double bond forms and the leaving
group departs from the α carbon
- Since the reaction rate depends on the
concentration of the reactants, the
reaction is first order in each reactant
and second order overall (
Rate=k [ alkyl halide ][ base ])
 o The rate-determining step must involve both the alkyl halide and the base; thus, the reaction
must be bimolecular; this type of elimination is an E2 reaction
- The orientation of the β hydrogen and the leaving group are not arbitrary; a conformation where they are
all in the same plane is required

- Zaitsev’s Rule
o If a small base is used, the major product of the
reaction will be the more highly substituted
alkene since it will be the most stable; when an
elimination reaction occurs, it gives the more
stable, highly substituted alkene
- Hoffman’s Rule
o Carrying out dehydrohalogenation with a bulky
base favors the formation of the less substituted
alkene; when an elimination reaction occurs, it
yields the less substituted alkene
- The atoms involved in the transition state of an E2 reaction must be coplanar; the requirement for
coplanarity arises from a need of proper orbital overlapping in the developing π bond
o The anti coplanar conformation is the preferred transition state due to it being staggered
o The syn coplanar transition state occurs only in rigid molecules that are unable to assume anti
arrangement, the syn coplanar is transition state is an eclipsed projection

E1 Reaction

- Some elimination reactions follow a pathway that

exhibit first-order kinetics, which are called E1
reactions; this elimination reaction compete with
substitution reactions
- The initial step for both substitution and elimination
pathways is the formation of a tert-butyl cation as a
common intermediate; this is the slowest step in
both reactions, thus, both reaction exhibit first-
order kinetics and are unimolecular
- Whether an elimination or a substitution takes
place depends on the next step:
o If a solvent molecule acts as a base and
removes one of the β hydrogen atoms, it
will be an elimination reaction

o If a solvent molecule as a nucleophile at

the positive carbon atom of the tert-butyl
cation, it will be a substitution reaction

- In the synthesis of an alkene by dehydrohalogenation, it is generally best to favor an E2 mechanism since

an E1 mechanism would produce variable results

Determining whether Elimination or Substitution is favored

 - SN2 and E2 = both are favored by high concentrations of a strong nucleophile or strong base; when a
hydrogen is attacked, it is an elimination, but if the carbon is attacked, it is substitution
o Primary substrates = when the substrate is a primary halide and the base is strong and
unhindered, substitution is highly favored because the base can easily approach the α carbon
o Secondary substrates = with secondary halides, a strong base favors elimination because the
steric hindrance in the substrate makes substitution difficult
o Tertiary substrates = with tertiary halides, steric hindrance prevents SN2 from taking place and
elimination becomes highly favored, especially with higher temperatures
o Temperature = increasing reaction temperature favors elimination over substitution due to
elimination being entropically-favorable
o Size of the Base or Nucleophile = a bulky base/nucleophile inhibits substitution reactions, allowing
elimination reactions to take precedence; an unhindered base/nucleophile reacts primarily by
substitution −¿ ¿
−¿,RO ¿
o Basicity and Polarizability = using a strong, slightly polarizable base (OH −¿, NH 2 ¿
) tends to
increase the likelihood of an elimination reaction; using a weak, highly polarizable basic ion
(halogen, acetate, or RS ions) increases the likelihood for substitution
- SN1 vs E1
o Tertiary halides = since both reactions proceed through a formation of a common intermediate,
the two types respond in similar ways to factors affecting reactivities
 E1 reactions are favored with substrates that can form stable carbocations; they are also
favored using poor nucleophiles and are generally favored using polar solvents
 It is difficult to influence the relative partition of SN1 and E1 products since the free
energy of activation for either reactions proceeding from the carbocation is very small
 In most unimolecular reactions, SN1 is favored over E1 reactions, especially at low
temperatures; in general, substitution reactions of tertiary halides do not find wide use
as a synthetic method since such halides undergo eliminations much too easily

Alcohol Dehydration

- Most alcohols undergo dehydration (loss of water) to form an alkene when heated with a strong acid, like
sulfuric acid and phosphoric acid
- Alcohol dehydration follows an E1 mechanism with secondary and tertiary alcohols, primary alcohols
follow an E2 mechanism or undergo rearrangement
- The temperature and concentration of acid required to dehydrate an alcohol depends in the structure of
the alcohol substrate
o Primary alcohols are the most difficult to dehydrate, requiring high acid concentration and high
temperatures

o Secondary alcohols usually dehydrate under milder conditions

o Tertiary alcohols are easily dehydrated that relatively mild conditions can be used

o The relative ease with which alcohol undergoes dehydration:

 This behavior is related to the relative stabilities of carbocations

- Some primary and secondary alcohols also undergo rearrangements of their carbon skeletons during
dehydration; this reaction involves the migration of a methyl group from one carbon to the next to form a
more stable carbocation

- Mechanism for Dehydration of Secondary and Tertiary Alcohols: E1 reaction

o In an acid-base reaction, a proton is rapidly transferred from the acid to one of the unshared
electron pairs of the alcohol and the alcohol becomes protonated

o The presence of the positive charge on the oxygen of the protonated alcohol weakens all the
bonds of the oxygen, causing the carbon-oxygen bond to break and a molecule of water to leave

 The carbon-oxygen bond breaks heterolytically: the bonding electrons depart with the
water molecule and leaves the carbocation
o The water molecule removes a proton from the β carbon of the carbocation, resulting to the
formation of a hydronium ion and an alkene

o In the dehydration of secondary and

tertiary alcohols, carbocation formation is
the slowest step; the first and third steps
only involve simple acid-base proton
transfers, but the second step involves the
loss of water which makes it a highly
endergonic process, making it the rate
determining step
 Carbocation formation is what
determines the reactivity of the
alcohol towards dehydration; the
more stable the carbocation, the
easier dehydration occurs
 - Mechanism for Dehydration of Primary Alcohols: E2 reaction
o Dehydration of primary alcohols proceed through an E2 mechanism because the primary
carbocation required for dehydration
by E1 is relatively unstable
o Similarly, the primary alcohol is
protonated like that in an E1
mechanism
o With the protonated hydroxyl group
as the leaving group, a Lewis base in
the reaction mixture removes a β
hydrogen simultaneously with the
formation of the alkene double bond
and the departure of the protonated
hydroxyl group (water

Carbocation Stability and Occurrence of Molecular Arrangements

- Rearrangements during Dehydration of Secondary Alcohols

o The rearrangement occurs after
carbocation formation, where the less
stable secondary carbocation
rearranges to a more stable tertiary
carbocation
o Rearrangement occurs through the
migration of an alkyl group from the
carbon adjacent to the one with the
positive charge; the alkyl group migrates
with its electron pairs (alkanide shift)
o After migration is complete, the carbon atom the alkyl anion left has become the carbocation,
neutralizing the former; when a group migrates from one carbon to an adjacent one, the
rearrangement is called a 1,2 shift
o The final step of the reaction is the removal of a proton from the new carbocation by a Lewis
base in the reaction mixture, and the formation of an alkene; however, this step can occur in two
ways
 The more favored product is dictated by the stability of the alkene being formed; the
more stable alkene is the major product because it has lower energy
- Rearrangement after Dehydration of a Primary Alcohol
 o The alkene produced initially from a
primary alcohol arises by an E2
mechanism
o However, an alkene can accept a
proton to generate a carbocation in
a process that is the reverse of the
deprotonation step in the E1
mechanism for alcohol dehydration
 A terminal alkene does this
by using its π electrons to
bond a proton at the
terminal carbon, and a
carbocation forms at the
second carbon of the chain
o Since this carbocation is internal to
the chain, it will be secondary or
tertiary depending on the substrate; various processes may occur from the carbocation but
under high temperature conditions, the principal products will be alkenes

Acidity of Terminal Alkynes

- Hydrogen bonded to the carbon of a terminal alkyne (acetylenic hydrogen) is considerably more acidic
than those bonded to carbons of an alkene or alkane; the order of basicity od opposite of their relative
acidity

- Terminal alkynes are more acidic than ammonia but are less acidic than alcohols and water

Terminal Alkyne Conversion to Nucleophiles for carbon-carbon Bond Formation

- The acetylenic proton of a terminal alkyne cane be removed with a strong base to produce an alkynide
anion; alkynide anions are useful nucleophiles for carbon-carbon bond forming reactions with primary
alkyl halides or other primary substrates

o The alkynide anion acts as a nucleophile and displaces the halide ion from the primary alkyl
halide – an SN2 reaction

- Primary alkyl halides should be used in the alkylation of alkynide anions to prevent competition by
elimination
 o Use of a secondary or tertiary substrate causes E2 elimination instead of substitution because the
alkynide is a strong base as well as a good nucleophile
- Preparation of the alkynide anion involves simple Bronsted-Lowry acid-base chemistry; the hydrogen of a
terminal alkyne is weakly acidic and with a strong base, it can be removed
- The alkynide anion formed is a Lewis base with which the alkyl halide reacts as a Lewis acid; the alkynide
anion can thus be called a nucleophile because of the negative charge concentrated at its terminal carbon,
making it seek a positive charge
- The alkyl halide can be called an electrophile because of the partial positive charge at the carbon bearing
the halogen, making it seek a negative charge

Hydrogenation of Alkenes

- Alkenes react with hydrogen in the presence of metal catalysts to add one H atom to each carbon atom of
the double bond
o Hydrogenation reactions that involve insoluble platinum,
palladium, or nickel catalysts proceed by heterogenous catalysis
because the catalyst is not soluble in the reaction mixture
o Hydrogenation reactions that involve soluble catalysts occur by
homogenous catalysis, typical catalysts include
rhodium and ruthenium complexes that bear various
phosphorus and other ligands; Wilkinson’s catalyst ( Rh [ ( C6 H 5 )3 P ]3 Cl ) is a well-known
homogenous hydrogenation catalyst
- Catalytic hydrogenation reactions are a type of addition reaction, which are also a type of reduction; this
leads to a distinction between compounds that are saturated and unsaturated
o Saturated compounds = contain only carbon-carbon single bonds, contain the maximum number
of hydrogen atoms; Unsaturated compounds = contains carbon-carbon multiple bonds, contain
fewer than the maximum number of hydrogen atoms
o Unsaturated compounds can be reduced to saturated compounds by catalytic hydrogenation
- Catalytic hydrogenation of alkenes is a syn addition reaction

Syn and Anti Additions

- A syn addition places parts of the adding reagent on the same side or face of the reactant

- An anti addition places the parts of the adding reagent on the opposite face of the reactant

Hydrogenation of Alkynes

- Depending on the conditions and the catalyst, one or two molar equivalents of hydrogen will be added to
a carbon-carbon triple bond
o When a platinum catalyst is used, the alkyne generally reacts with two molar equivalents of
hydrogen to give an alkane
- Hydrogenation of an alkyne to an alkene can be
accomplished by using special catalysts or reagents that also allow the preparation of either E/Z alkenes
from disubstituted alkynes
- Syn Hydrogen Addition: cis-Alkenes
 o A heterogenous catalyst that permits hydrogenation of an alkyne
to an alkene is the P-2 catalyst, nickel-bromide compound; it can
be prepared by reduction of nickel acetate with sodium
borohydride
o Hydrogenation of alkynes using the P-2 catalyst causes a syn addition of hydrogen; the alkene
formed from an internal alkyne has the Z or cis configuration

o Other specially conditioned catalyst can be sued to prepare cis-alkenes from disubstituted
alkynes; metallic palladium deposited on calcium carbonate can be used after it has been
conditioned with lead acetate and quinoline – this special catalyst is known as Lindlar’s catalyst

- Anti Hydrogen Addition: trans-Alkenes

o Anti addition of hydrogen to the triple bond of alkynes occurs when they are treated with lithium
or sodium metal in ammonia or ethylamine at low temperatures; this reaction, called a dissolving
metal reduction, takes place in solution, and produces an E or trans-alkane

Addition Reaction of Alkenes and Alkynes

- Addition reactions bond new groups to each end of an

alkene or alkyne; involves the donation of an electron
pair from one end of an alkene or alkyne π bond to an
electrophile, followed by bonding of a nucleophile at
the other end
- Addition reactions occur based on several factors:
o π electrons present an exposed region od electron density in a molecule that is above and below
the σ bonding framework, making the π electrons more available for reactions
o Electrophiles are attracted to the exposed electron density of π bonds
o π electrons are higher energy than σ electrons and π bonds are weaker than σ bonds so reactions
that convert π bonds into σ bonds are energetically favorable since it lowers the energy of the
system
- Electrophiles seek electrons, they are attracted to sites of negative charges; Nucleophiles are electron
donors, they are attracted to sites of positive charge
o Electrophiles include Bronsted-Lowry Acids, neutral reagents, and Lewis acids; metal ions that
contain vacant orbitals can also act as electrophiles
o Halide ions and water molecules are common nucleophiles

Electrophilic Addition of Hydrogen Halides to Alkenes

- Hydrogen halides react as electrophiles with alkenes

forms a bond between the hydrogen and one of the
carbons, forming a carbocation and a halide ion; the
halide ion then acts as a nucleophile, donating an
electron pair to the carbocation
 - These addition reactions are carried out by dissolving the hydrogen halide in a solvent, such as acetic acid
or dichloromethane, or by bubbling gaseous hydrogen halide directly into the alkene
- The order of reactivity of the hydrogen halides: HI > HBr > HCl> HF
o HCl reacts so slowly that the reaction is not used as a preparative method, unless the alkene is
highly substituted; while HBr adds readily, its reaction may follow an alternate course
- Markovnikov’s Rule
o In the ionic addition of an unsymmetrical reagent to a double bond, the positive portion of the
adding reagent attaches itself to a carbon atom of the double to yield the more stable
carbocation as an intermediate
o Addition of the electrophile determines the overall orientation of the addition, because it occurs
before the addition of the nucleophile portion of the adding reagent
- Markovnikov Addition of Hydrogen Halides to Alkenes
o In the addition of a hydrogen halide to an alkene, the hydrogen atom adds to the carbon atom of
the double bond that already has the greater number of H atoms
o Markovnikov additions are reactions that illustrate Markovnikov’s rule; the addition of a
hydrogen halide to an alkene is a Markovnikov addition
 The rate determining step in a
Markovnikov addition is the protonation
of a carbon in a double bond by a
hydrogen halide to form a carbocation;
this step is highly endergonic and take
place slowly
 The stabilization of the carbocation with
a halide is an exergonic step that take
place very rapidly
o If the alkene that undergoes addition of a
hydrogen halide is an unsymmetrical alkene, the
rate-determining step could form two different
carbocations; only one of the two carbocations has
greater stability, and it accounts for the prediction of
the addition by Markovnikov’s rule
 The more stable the carbocation
predominates because it is formed faster
 Rearrangements invariably occur when the carbocation initially formed can rearrange to
a more stable carbocation
o Regioselective reactions are reactions that can yield two or more constitutional isomers but only
produces the predominant one; Markovnikov addition of hydrogen halide to alkenes is an
example
o Anti-Markovnikov Addition of HBr in the presence of Peroxides
 When alkenes are treated with HBr in the presence of peroxides, an anti-Markovnikov
addition occurs where the hydrogen atom becomes attached to the carbon with the
fewer hydrogen atoms; only occurs exclusively when HBr is in the presence of peroxides
 This anti-Markovnikov addition occurs by a radical mechanism, not by ionic mechanism

Stereochemistry of the Ionic Addition to an Alkene

- The product of an ionic addition on an alkene can

exist as a pair of enantiomers but no enantiomer
exists in a greater amount than the other
 - The carbocation formed in addition is trigonal planar and is achiral – has a plane of symmetry; when the
halide ion reacts with the achiral carbocation, the reaction is equally likely at either face, leading to the
two enantiomers occurring at the same rate and producing a racemic mixture

Addition of Water to Alkenes: Acid-Catalyzed Hydration

- Acid-catalyzed hydration of an alkene is a

method for the preparation of low-molecular-
weight alcohols; acids commonly used to
catalyze the hydration are dilute aqueous
sulfuric acid and phosphoric acid
- These reactions are usually regioselective and
the addition of water to the double bond
follows Markovnikov’s rule
o Since the reactions follow
Markovnikov’s rule, acid-catalyzed
alkene hydration des not yield primary
alcohols except in the special case of ethene hydration
- The mechanism for alcohol dehydration is simply the reverse of the mechanism for alcohol dehydration
o The rate-determining step in the hydration mechanism is the formation of the carbocation; it is
also the step that accounts for the Markovnikov regiochemistry of the addition of water to the
double bond
- Alkene hydration or alcohol dehydration are reactions in which the products are governed by the position
of an equilibrium
o In alcohol dehydration, it is best to use a concentrated acid so that water concentration is low
o In alkene hydration, it is best to use dilute acid so that water concentration is high
- One complication associated with alkene hydration is the occurrence of arrangements; because the
reaction involves the formation of a carbocation, the carbocation initially formed invariably rearranges to
a more stable one if possible

Alcohols from Alkenes though Oxymercuration-Demercuration: Markovnikov Addition

- Oxymercuration-demercuration is a two-step method that allows for the synthesis of alcohols from
alkenes that avoids rearrangement
- Alkenes react with mercuric acetate in a mixture
of tetrahydrofuran (THF) and water to produce
(hydroxyalkyl)mercury compounds which can be
reduced to alcohols with sodium borohydride
- In oxymercuration, water and mercuric acetate
add to the double bond; then in demercuration,
sodium borohydride reduces the
acetoxymercury group and replaces it with
hydrogen
o Both steps can be carried out in the same vessel and both reactions take place very rapidly at
room temperature or below; the overall reaction gives alcohols in very high yields (>90%)
- Oxymercuration-demercuration is also highly regioselective
o The net orientation of the addition of
the water elements, -H and -OH, is in
accordance with Markovnikov’s rule
- Rearrangements of the carbon skeleton seldom
occur in oxymercuration-demercuration
 - Central to the mechanism of
oxymercuration is an electrophilic attack by
the mercury species at the less substituted
carbon of the double bond and the
formation of a bridged intermediate
o The mercury-bridged carbocations
(mercurinium) retain much of the
positive charge on the mercury,
leaving only a small positive charge
on the carbon; this charge is large
enough to account for the
Markovnikov addition but too
small to allow for carbon skeleton
rearrangement
- Although the attack by water on the
mercurinium leads to the anti addition of
the hydroxyl and mercury groups, the
reaction that replaces the mercury with
hydrogen is not stereocontrolled but likely
involves radicals

Alcohols from Alkenes through Hydroboration-Oxidation: Anti-Markovnikov Syn Hydration

- The anti-Markovnikov hydration of a double

bond can be achieved by using diborane or a
solution of borane in tetrahydrofuran (THF); the
indirect addition of water involves two steps:
hydroboration (addition of a boron and hydrogen to the double bond) then oxidation and hydrolysis of the
alkylborane to an alcohol and boric acid
- Hydroboration-oxidation takes place with syn stereochemistry as well as anti-Markovnikov regiochemistry

Hydroboration: Alkylborane Synthesis

- When diborane is introduced to THF, it reacts to form a Lewis acid-base complex of borane and THF (
BH 3 THF ); these reactions are usually carried out in ether solvents
- When a terminal alkene is
treated with BH 3 THF , the
boron hydride adds
successively to the double
bonds of the three
molecules of the alkene to
form a trialkylborane
o In each addition step, the boron atom becomes attached to the less substituted carbon atom of
the double bond and a hydrogen atom is transferred from the boron to the other carbon
o Hydroboration is regioselective and it is anti-Markovnikov – the hydrogen atom becomes
attached to the carbon with fewer carbon atoms
o The observed anti-Markovnikov addition of boron seems to result from steric factors – the bulky
boron-containing group can approach the less substituted carbon atom more easily
- The addition of borane begins with a donation of π electrons from the double bond to the vacant p-orbital
of borane, then this
complex passes through a
 four-atom transition state in which the boron atom is partially bonded to the less substituted carbon and
one hydrogen is partially bonded to the other carbon; as the transition state is approached, the electrons
shift in the direction of the boron, away from the more substituted carbon of the double bond which
develops a partial positive charge on the more substituted carbon
o Since the carbon bears an electron-releasing alkyl group, it can accommodate the positive
charge, thus electronic factors favoring the anti-Markovnikov addition of the boron
o Both steric and electronic factors account for the anti-Markovnikov addition
- The transition state for hydroboration requires that the boron and hydrogen add to the same face (syn) of
the double bond

Oxidation and Hydrolysis of Alkylboranes

- The alkylboranes produced in

hydroboration are oxidized and
hydrolyzed to alcohols by the
addition of hydrogen peroxide in an
aqueous base
- The oxidation and hydrolysis take
place with retention of
configuration at the carbon initially
bearing the boron and bearing the
hydroxyl
- Oxidation begins with the addition
of a hydroperoxide anion to the
trivalent boron atom which forms an unstable intermediate that has a formal charge on the boron;
migration of an alkyl group from the boron to the adjacent oxygen neutralizes the charged boron and
displaces a hydroxide anion – the alkyl migration takes place with retention of configuration at the
migrating carbon
- The steps are repeated until all the alkyl groups have become attached to oxygen atoms, resulting in a
trialkyl borate ester which undergoes basic hydrolysis to produce three molecules of the alcohol and an
inorganic borate anion
- Since the net result of hydroboration-oxidation is an anti-Markovnikov addition of water to an alkene, it
gives a method of alcohol synthesis that cannot be normally obtained through acid-catalyzed hydration or
oxymercuration-demercuration
- Hydroboration-oxidation reactions are stereospecific and if chiral centers are formed, their configuration
depends on the stereochemistry of the starting alkene

Electrophilic Addition of Bromine and Chlorine to Alkenes

- Alkenes react rapidly with bromine and chlorine in nonnucleophilic solvents to form vicinal dihalides; the
addition of halogens is an anti addition to the double bond
- A mechanism that explains the anti addition is that the halogen molecule transfers an atom to the alkene
to form a cyclic halonium ion
and a halogen ion; the halogen
ion attacks the back side of
either carbons of the halonium
ion (an SN2 process) to open the
ring and produce a vicinal dihalide – the attack occurs from the side opposite of the halonium ion since it
would be unhindered in that direction
o Similar to bridged mercurinium ion, the halonium ion does not necessarily have symmetrical
charge distribution at its two carbon atoms; if one of the carbons is more highly substituted, it
will be able to stabilize the positive charge better and bear a greater fraction of the positive
charge
Halohydrin Formation

- When the halogenation of an alkene is

carried out in aqueous solution, the major
product will a halohydrin or a halo alcohol;
the molecules of water react with the
halonium intermediate as the nucleophile
since it is in high concentration
o Since water is the nucleophile in
halohydrin formation, it attacks
one of the carbons of the
halonium ion and produces a
protonated halohydrin – losing the water, produces the halohydrin itself
- If the alkene is unsymmetrical, the halogen ends up on the carbon with the greater number of hydrogen
atoms
o The more highly substituted carbon bears the greater positive charge because it resembles the
more stable carbocation; consequently, water attacks this atom preferentially

Oxidation of Alkenes: Syn 1,2-dihydroxylation

- Osmium tetroxide is widely used to synthesize 1,2-diols or

glycols; potassium permanganate can also be used but since it
is a stronger oxidizing agent, it is prone to cleaving the diol
through further oxidation

- The mechanism involves a cyclic intermediate that

results in the syn addition of the oxygen atoms; after
the formation of the cyclic intermediate, cleavage at
the oxygen-metal bonds takes place without altering
the stereochemistry of the two new carbon-oxygen
bonds

Oxidative Cleavage of Alkenes

- Alkenes undergo oxidative cleavage with ozone or hot potassium permanganate; potassium
permanganate is used when strong oxidation is needed while ozone is used when mild oxidation is
needed
- With Hot Potassium permanganate
o Potassium permanganate oxidatively
cleaves the double bond of an alkene; the
cleavage is believed to occur via a cyclic
intermediate
o Alkenes with monosubstituted carbon
atoms are oxidatively cleaved to salts of
carboxylic acids; Disubstituted alkene
carbons are oxidatively cleaved to ketones; Unsubstituted alkene carbons are oxidized to carbon
dioxide
- With Ozone
o Ozonolysis consists of bubbling ozone into a very cold solution of the alkene in dichloromethane,
followed by treatment of the solution
with dimethyl sulfide or zinc and acetic
acid
 o The overall process results in alkene cleavage at the double bond, with each carbon of the double
bond becoming doubly bonded to an oxygen atom

Electrophilic Addition of Bromine and Chlorine to Alkynes

- Alkynes show the same kind of addition reactions

with chlorine and bromine that alkenes do; with
alkynes, the addition may occur once or twice
depending on the number of molar equivalents of
halogen employed
- Addition of one molar equivalent of chlorine or
bromine generally results in anti addition and yields
a trans-dihaloalkene

Addition of Hydrogen Halides to Alkynes

- Alkynes react with one molar equivalent of hydrogen

chloride or hydrogen bromide to form haloalkenes, with
two molar equivalents to form geminal dihalides
- Both additions are regioselective and follow
Markovnikov’s rule: the hydrogen halide becomes
attached to the carbon atom that has the greater
number of hydrogen atoms