Dehydrohalogenation of Alkyl Halides

Alkyl halides on heating with a strong base undergo dehydrohalogenation to give

alkenes. The commonly used bases are KOH in C2H5OH, C2H5ONa in C2H5OH and
(CH3)3COK in (CH3)3COH.
 Alkenes - Preparation Methods

What is regioselective and Regiospecific?

A reaction that selectively generates one possible product over another is called
regioselective. That is, a choice of final product exists. Regiospecific reactions are
those reactions where the same choice isn't there. A regiospecific reaction
exclusively gives only one, specific product.
Dehydrohalogenation of Alkyl Halides

Order of reactivity of alkyl halides:

1. R—I > R—Br > R—Cl >> R—F (for a given alkyl group)
2. Tertiary > secondary > primary (for a given halogen)

Regioselectivity and Zaitsev rule: When an alkyl halide has more than one type of
β-hydrogen, more than one alkene product can be formed. For example:
Dehydrohalogenation of Alkyl Halides
Dehydration of Alcohols

When alkanols are heated with a strong acid catalyst such as H2SO4 or H3PO4, they
undergo intramolecular dehydration (elimination of water) to form alkenes.

Ease of dehydration of alcohols: 3° > 2° > 1°

Dehydration of Alcohols
Dehydration of Alcohols

Mechanism
Dehydration of Alcohols

Mechanism
Dehydration of Alcohols

Dehydration of alcohols of low molecular mass can be effected by passing the

vapour of the alcohol over alumina (Al2O3).

The ease of dehydration is 3° > 2° > 1° alcohol.

Dehalogenation of Vicinal Dihalides

Compounds that contain two halogen atoms bonded to adjacent carbons are
called vicinal dihalides (vic dihalides). When vicinal dihalides are heated with zinc
in ethanol or acetic acid they undergo dehalogenation to form alkenes.
Dehalogenation of Vicinal Dihalides

Dehalogenation of vicinal dihalides can be brought about also by heating them

with sodium iodide in acetone.
Kolbe’s Method

Electrolysis of an aqueous solution of potassium succinate liberates ethylene gas

at anode.

Mechanism
Cracking of Alkanes (Industrial Method)

Ethylene, propylene and butylenes are obtained in industrial quantities by thermal

cracking of natural gas (C1–C4 alkanes) and straight-run gasoline (C4–C8 alkanes).
Thermal cracking of ethane at 700°C gives ethylene and hydrogen. Propane on
heating at 700°C gives a mixture of propylene, ethylene and methane.
Catalytic Hydrogenation of Alkynes

Hydrogenation of alkynes in presence of a metal catalyst (Ni, Pd or Pt) normally

gives alkanes. Controlled reduction of alkynes with H2 gas in presence of a
partially deactivated catalyst, such as Lindlar catalyst, gives alkenes.
Birch Reduction

Nonterminal alkynes (internal alkynes) when treated with sodium (or lithium) in
liquid ammonia give trans-alkenes by anti-addition of two hydrogens across the
triple bond.
Reactions of Alkene
Reactions of Alkene

Because the C-C π bond of an alkene is much weaker than a C-C σ bond, the
characteristic reaction of alkenes is addition.
Reactions of Alkene
Reactions of Alkene
Reactions of Alkene
Electrophilic Addition Reaction

Step 1: Attack of the pi bond on the electrophile forms a carbocation.

Step 2: Attack by a nucleophile gives the addition product

Electrophilic Addition Reaction

EXAMPLE: Ionic addition of HBr to but-2-ene

Addition of H-X to Alkenes

Addition of HBr to 2-methylbut-2-ene could lead to either of two products, yet only
one is observed.
Markovnikov’s Rule

A Russian chemist, Vladimir Markovnikov, first showed the orientation of addition of

HBr to alkenes in 1869.

“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.”

MARKOVNIKOV’S RULE (extended): In an electrophilic addition to an

alkene, the electrophile adds in such a way as to generate the most stable
intermediate.
Markovnikov’s Rule
Markovnikov’s Rule
Anti - Markovnikov Addition
Anti Markovnikov’s Addition

Free-Radical Addition of HBr: In 1933, M. S. Kharasch and F. W. Mayo found that

some additions of HBr (but not HCl or HI) to alkenes gave products that were
opposite those expected from Markovnikov’s rule. These anti-Markovnikov reactions
were most likely when the reagents or solvents came from old supplies that had
accumulated peroxides from exposure to the air.
Anti Markovnikov’s Addition

Mechanism
Anti Markovnikov’s Addition

Mechanism
Why the reaction with Markovnikov orientation does not take
place in the presence of peroxides, together with the free-
radical chain reaction?
Anti Markovnikov’s Addition
Acid Catalysed Hydration

An alkene may react with water in the presence of a strongly acidic catalyst to form
an alcohol.

Mechanism
Example Predict the products of the following hydration reactions.

A. 1-methylcyclopentene + dilute acid

B. 2-phenylpropene + dilute acid
C. 1-phenylcyclohexene + dilute acid
Oxymercuration–Demercuration

Many alkenes do not easily undergo hydration in aqueous acid. Some alkenes are
nearly insoluble in aqueous acid, and others undergo side reactions such as
rearrangement, polymerization, or charring under these strongly acidic conditions.
Oxymercuration–Demercuration

Oxymercuration involves an electrophilic attack on the double bond by the positively

charged mercury species. The product is a mercurinium ion, an organometallic
cation containing a three-membered ring.
Example
Example Show the intermediates and products that result from alkoxymercuration –
demercuration of 1-methylcyclopentene, using methanol as the solvent.
Hydroboration of Alkenes

We have seen two methods for hydrating an alkene with Markovnikov orientation.
What if we need to convert an alkene to the anti-Markovnikov alcohol?

H. C. Brown, of Purdue University, discovered that diborane (B2H6) adds to alkenes

with anti-Markovnikov orientation to form alkylboranes, which can be oxidized to give
anti-Markovnikov alcohols.
Hydroboration of Alkenes

We have seen two methods for hydrating an alkene with Markovnikov orientation.
What if we need to convert an alkene to the anti-Markovnikov alcohol?
Hydroboration of Alkenes

Mechanism
Example Propose a mechanism for the following reaction.
 Hydroboration of Alkenes

Stereochemistry The simultaneous addition of boron and hydrogen to the double bond
leads to a syn addition:
Example
Example
Example Outline a method for carrying out the following conversion.
Example Identify end products A, B and C of the following
Example

Schemes A, B and C are

A. simple acid catalysed hydration
B. hydroboronation, mercuration-demercuration, acid-catalysed hydration
C. acid-catalysed hydration, hydroboronation, mercuration-demercuration
D. mercuration-demercuration, acid-catalysed hydration, hydroboronation
Example
Example Rate of dehydration when given compounds are treated with conc. H2SO4 is
Example
Example
Example Suppose you carried out the hydroboration of 1-methylcyclopentene:

Choose the correct answer for the products formed in the above reaction.

A. An equal mixture of 1 and 5 B. An equal mixture of 1 and 2

C. An equal mixture of 2 and 4 D. An equal mixture of 4 and 5
Addition of Halogen

Halogens add to alkenes to form vicinal dihalides.

The addition of bromine to cyclopentene is a stereospecific anti addition.

Addition of Halogen

A halogen molecule (Br2, Cl2, or I2) is electrophilic; a nucleophile can react with a
halogen, displacing a halide ion:
 Addition of Halogen

Mechanism
 Addition of Halogen

Mechanism
Example
Example
Formation of Halohydrins

A halohydrin is an alcohol with a halogen on the adjacent carbon atom. In the

presence of water, halogens add to alkenes to form halohydrins.
Formation of Halohydrins
Addition of carbenes

Methylene (:CH2) is the simplest of the carbenes: uncharged, reactive intermediates

that have a carbon atom with two bonds and two nonbonding electrons.

Carbene is a potent electrophile because it has an unfilled octet. It adds to the

electron-rich pi bond of an alkene to form a cyclopropane.
Addition of carbenes

Heating or photolysis of diazomethane gives nitrogen gas and methylene:

Carbene is also generated from alpha elimination of CHX 3

Addition of carbenes

The products of these cyclopropanations retain any cis or trans stereochemistry of the
reactants.
Epoxidation of Alkenes
An alkene is converted to an epoxide by a peroxyacid, a carboxylic acid that has an
extra oxygen atom in a -O-O- (peroxy) linkage.

The epoxidation of an alkene is clearly an oxidation, because an oxygen atom is

added.
Mechanism

Peroxyacids epoxidize alkenes in a one-step (concerted) process.

The epoxidation of an alkene is clearly an oxidation, because an oxygen atom is

added.
Epoxidation of Alkenes

Peroxyacids epoxidize alkenes in a one-step (concerted) process.

Opening of epoxides

Most epoxides are easily isolated as stable products if the solution is not too acidic.

Any moderately strong acid protonates the epoxide, however. Water attacks the
protonated epoxide, opening the ring and forming a 1,2-diol, commonly called a glycol.
Opening of epoxides
Opening of epoxides
Syn - Dihydroxylation

The two most common reagents for this purpose are osmium tetroxide and potassium
permanganate.
Syn - Dihydroxylation
Syn - Dihydroxylation
Example Which of the following alkanes cannot be produced by Kolbe electrolysis of
sodium or potassium salts of carboxylic acids ?

(A) Methane (B) Ethane (C) Butane (D) Hexane

Example A mixture of two organic compound was treated with sodium metal in ether
solution. Isobutane was obtained as product. The two chlorine compounds are

(A) Methyl chloride and propyl chloride

(B) Methyl chloride and ethyl chloride
(C) Isopropyl chloride and Methyl chloride
(D) Isopropyl chloride and ethyl chloride
Example What is correct order of electrophillic substitution of following alkene ?

(A) II > IV > I > III

(B) IV > III > II > I
(C) III > I > IV > II
(D) I > II > III > IV
Example
Oxidative Cleavage of Alkenes

In a potassium permanganate dihydroxylation, if the solution is warm or acidic or too

concentrated, oxidative cleavage of the glycol may occur.
Oxidative Cleavage of Alkenes

If the molecule contains a terminal =CH2 group, that group is oxidized all the way to
CO2 and water.
Ozonolysis of Alkenes

Ozone (O3) is a high-energy form of oxygen produced when ultraviolet light or an

electrical discharge passes through oxygen gas. Ultraviolet light from the Sun
converts oxygen to ozone in the upper atmosphere.

Like permanganate, ozone cleaves double bonds to give ketones and aldehydes.
However, ozonolysis is milder.
Ozonolysis of Alkenes
Ozonolysis of Alkenes
Ozonolysis of Alkenes
Example
Example
Example
 12th Grade
Friday
Saturday
Sunday

Subjects Timings
Physics 7 PM
Chemistry 8 PM
Mathematics 9 PM
Conjugate Addition

What is special about conjugation?

When p orbitals overlap, the electron density in each of the o bonds is spread out
over a larger volume, thus lowering the energy of the molecule and making it more
stable.
Conjugate Addition

With a conjugated diene, electrophilic addition of one equivalent of HBr affords two
products.
Mechanism

The mechanism of electrophilic addition of HX involves two steps:

● addition of H+ (from HX) to form a resonance-stabilized carbocation

Mechanism

● Nucleophilic attack of X– at either electrophilic end of the carbocation to form

two products.
Example Draw the products of the following reaction.
Kinetic Versus Thermodynamic Products

The amount of 1,2- and 1,4-addition products formed in the electrophilic addition
reactions of buta-1,3-diene, a conjugated diene, depends greatly on the reaction
conditions.
Kinetic Versus Thermodynamic Products
Kinetic Versus Thermodynamic Products
Example
Example
Example
Example
Example
Example A sample of 2,3-dibromo-3-methylpentane is heated with zinc dust. The resulting
product formed is isolated and heated with HI in the presence of phosphorus.
Identify which is the structure that represents the final organic product formed in
the reaction ?
Example Propose a mechanism for the following reaction.
Example
Example Predict the major products of the following reactions, and give the structures of
any intermediates. Include stereochemistry where appropriate.
Example
Example
Example
Example
Example Complete each synthesis by providing the structure of the major product at each
step, including any important stereochemistry.
Example
Example
Example One of the constituents of turpentine is 𝞪 pinene, formula C10H16. The following
scheme (called a “road map”) gives some reactions of 𝞪 pinene. Determine the
structure of 𝞪 pinene and of the reaction products A through E.
Example
Example The total number of alkenes possible by dehydrobromination of 3-bromo-3-
cyclopentylhexane using alcoholic KOH is ___.
Example The maximum number of isomers (including stereoisomers) that are possible on
monochlorination of the following compound, is ___.
Example The number of optically active products obtained from the complete ozonolysis of
the given compound is ___.
Example Match the chemical conversions in Column I with the appropriate reagents in
Column II.
Example Compound(s) that on hydrogenation produce(s) optically inactive compound(s) is
(are)
Example