ALKYL HALIDES AND

ALCOHOLS
 ALKYL HALIDES AND
ALCOHOLS
• Alkyl Halides and Alcohols
• Nomeclature of Alkyl Halides and Alcohols
• Elimination of Alkyl Halides and Alcohols
• Nucleophilic Substitution Reactions of Alkyl
Halides and Alcohols
• Preparation of Grignard Reagents
• Reactions of Alcohols with Active Metals
• Oxidation of Alcohols
 1.5 Alkyl Halides
• Also called haloalkanes or organohalides
• General formula = CnH2n + 1X (n ≥ 1), or R‒ X
X = F, Cl, Br or I
• Functional Group:
C X

• Alkyl halides, when halogen atom bonded to

one of sp3 carbon
• Vinyl halides, when halogen bonded to sp2
carbon
• Aryl halides, when halogen bonded to sp2
carbon atom in aromatic ring
 1.5 Alkyl Halides
Classification of Alkyl Halides
• Methyl bromide – no alkyl group and three atoms
hydrogen
• Primary alkyl halide – one alkyl group and two atoms
hydrogen
• Secondary alkyl halide – two alkyl groups and one
atom hydrogen
• Tertiary alkyl halide – three alkyl groups and no
atom hydrogen
Br Br Br Br
H CH3 CH3 CH3
C C C C
H H H H H CH3 H3C CH3
Methyl bromide Ethyl bromide Isopropyl bromide tert-Butyl bromide

1o 2o 3o
 1.5 Alkyl Halides
Common uses of alkyl halides
•Solvents, e.g: CCl4, CH2Cl2
•Reagents, e.g: preparations of Grignard
reagents
•Anesthetics, e.g: CHCl3, CF3CHClBr
•Freons, e.g: CF2Cl2
•Pesticides e.g: lindane is used in shampoo
Cl Cl
Cl H Cl Cl Cl H
H H Cl Cl
Cl
H Cl Cl H
H Cl Cl Cl Cl
Cl Cl
Cl Cl H
Cl H O Cl Cl H Cl
Cl
Lindane Kepone Chlordane
 Alkyl Halides Nomenclature

• Name as derivative of alkane:

replacing the H atom(s) by halogen atom(s)
• Positions of halogen atoms are indicated by
the number assigned to the C atom to which it
is attached
Br CH3
CH3CH2F H3C C CH3 H3C C Cl
H
CH3
IUPAC Fluoroethane 2-Bromopropane 2-Chloro-2-
name methylpropane
Common Ethyl fluoride Isopropyl bromide tert-Butyl chloride
name
 Alkyl Halides Nomenclature

CH2CH3
I
CH3CH2CH2CH Cl
3-chlorohexane Iodocyclopentane

CH2CH3

Br CHCH CH2CH3

CH2CH2CH3 F

3-bromo-4-ethylheptane 3-fluoro-1,1-dimethylcyclohexane
 Reaction of Alkyl Halides
• Carbon and halogens have different electronegativity.
• Carbon-halogen bonds are polarized.
• The C atom is electron-poor (partial positive charge),
making it somewhat electrophile, it attracts
nucleophiles
• Most reactions of alkyl halides results from breaking
the polar bond. 
C X

Cl l
Br
H H H H
H H
H
H H
 Reaction of Alkyl Halides
• Reactions of haloalkanes include:
1. Elimination
2. Nucleophilic substitution
3. Preparation of Grignard reactions
 1.5 Alkyl Halides
- Elimination
H
C C B- C C + B H + X-
X
• In this case the nucleophile reacts as a base; we
observe elimination reactions.
• A hydrogen is removed from a carbon atom.
• The halogen is removed from the adjacent
carbon.
• Note that the elimination reaction is the reverse
of an addition reaction.
 1.5 Alkyl Halides
- Elimination

The β-hydrogen
is attached to the
β-carbon. H
a-carbon
C C
-carbon Cl The functional
group is attached
to the α-carbon.

Since the β-hydrogen is lost this reaction is

called a β-elimination.
 1.5 Alkyl Halides
Mechanism: The Base Takes The -hydrogen

OH- H
C C C C + H O H + Br-
Br

Bond formation (π bond) and breaking bonds

(C-H and C-X σ bond) take place simultaneously
 1.5 Alkyl Halides
- Elimination
What Happens If There Is More
Than one β-hydrogen?

a
H H ’

C C C
Br
 1.5 Alkyl Halides
Regioselectivity of -Elimination
• Dehydrohalogenation of an alkyl halide is selective in
respect to its direction.
• Elimination in 2-bromobutane leads to the double
bond between C-2 and C-3 more than C-1 and C-2

 ’ 1-Butene Minor product – β’-H

H H H H
H C C C C H
H H H H
CH3CH2O-Na+ H H
H C C C C H Major product
CH3CH2OH is the one with
H H Br H H H H H lowest energy
2-bromobutane H C C C C H
Reactions that can proceed in more than
one direction, but in which one direction is H H
preferred are said to be regioselective 2-Butene Major product - β-H
 1.5 Alkyl Halides
Zaitsev’s Rule for Elimination Reactions
• A reaction is regioselective when it yield
predominantly one constitutional isomer when more
than one is possible.
• Original form Zaitsev’s rule stated that the alkene
formed in greatest amount is the one that corresponds
to removal of the hydrogen from the -carbon having
the fewest hydrogen.
• Previous chapter discussed, the most highly
substituted alkene is the most stable one.
• Reconsider the regioselectivity of -elimination
reactions Zaitsev’s rule restated that the product
formed with the most highly substituted alkene will
predominate.
 1.5 Alkyl Halides
Zaitsev’s Rule for Elimination Reactions

Alkyl halides is heated with a solution of NaOH in

ethanol or KOH in ethanol or in tert-butyl alcohol
under reflux,
Cl
CH3CH2O-K+ +
CH3CH2OH
CH3 CH3 CH3

1-chloro-2-methylcyclohexane 1-methylcyclohexene 3-methylcyclohexene

Major Minor

Br
H3C CH3 H3CH2C H
CH3CH2CCH3 C(CH3)3O-K+
C C + C C
C(CH3)3OH H CH3
CH3 CH3 H
2-bromo-2-methylbutane 2-methyl-2-butene 2-methylbutene
Major Minor
 1.5 Alkyl Halides
Stereoselectivity in -Elimination

A stereoselective reaction is one in which

elimination of alkyl halides can yield two or
more stereoisomeric products, but gives one of
them in greater amounts than any other
Br H3C H H3C CH2CH3
- +
CH3CH2O K
CH3CH2CHCH2CH3 C C + C C
CH3CH2OH
3-bromopentane H CH2CH3 H H
trans-2-pentene cis-2-pentene
major product minor product
 1.5 Alkyl Halides

Exercise 26 : Write the structures of all alkenes from

dehydrohalogenation of each of the following alkyl
halides in the presence of potassium tert butoxide
(CH3)3CO-K+ in tert butyl alcohol (CH3)3COH

(a) 2-Bromo-2,3-dimethylbutane
(b) 1-chloro-2-methylcyclopentane
 1.5 Alkyl Halides
Nucleophilic Substitution
substrate leaving
group
H H
C C Nu- C C + X-
X nucleophile Nu
product

The nucleophile ―displaces‖ the leaving

group.
This is a ―substitution‖ reaction: Nu
substitutes for X (takes its place).
 1.5 Alkyl Halides
Nucleophilic Substitution
The reaction of alkyl halides with hydroxide ion
in aqueous solution is a nucleophilic
substitution reaction. The OH− acts as a
nucleophile, replacing the halogen atom to
form an alcohol
80% Ethanolic
solution
CH3Br + NaOH CH3OH + Br-
Bromomethane at 55oC Methanol

80% Ethanolic
solution
CH3CH2I + NaOH CH3CH2OH + I-
Iodoethane at 55oC Ethanol
 1.5 Alkyl Halides
The SN2 Nucleophilic Substitution
80% Ethanolic
solution
CH3Br + OH- CH3OH + Br-
Bromomethane at 55oC Methanol

The rate of reaction is observed to be directly proportional to

the concentration of both methyl bromide and sodium
hydroxide.
Rate = k[CH3OH][HO-]
First order in each reactant, or second order overall.
The second-order kinetic behavior is mean that the rate-
determining step is bimolecular, that is both hydroxide ion and
methyl bromide are involved at the transition state.
 1.5 Alkyl Halides
The SN2 Nucleophilic Substitution

The symbol given to this mechanism is SN2, standing for

substitution nucleophilic bimolecular.

The SN2 mechanism is a concerted (single-step) process

in which cleavage of the bond between carbon and the
leaving group (the halogen) is assisted by formation of
bond between carbon and the nucleophile.
 1.5 Alkyl Halides
The SN2 Mechanism of Nucleophilic Substitution

H H H
.. .. ..O .. ..O ..
..-
.. .. .. ..

..
..

+ -
..
..

..
..
H O C Br H C Br H C + Br
H H
H H H H
Hydroxide Methyl Transition Methyl Bromide
ion bromide state alcohol ion

The nucleophile attacks carbon from the side opposite

the bond to the leaving group.
This causes an inversion of configuration, much like an
umbrella would flip inside out in a windstorm. This
inversion of configuration known as Walden inversion
( German chemist Paul Walden , who describe the
earliest experiments in 1890s).
 1.5 Alkyl Halides
Steric Effects in SN2 Reactions

The carbon atom in (a) bromomethane is readily accessible

resulting in a fast SN2 reaction. The carbon atoms in (b)
bromoethane (primary), (c) 2-bromopropane (secondary), and (d) 2-
bromo-2-methylpropane (tertiary) are successively more hindered,
resulting in successively slower SN2 reactions.
 1.5 Alkyl Halides
Steric Effects in SN2 Reactions

The more alkyl groups connected to the reacting carbon,

the slower the reaction
 1.5 Alkyl Halides
Relative Reactivity of Halide Leaving Groups in
SN2 Reactions
Among alkyl halides, alkyl iodides undergo nucleophilic
substitution at the fastest rate, alkyl fluorides the
slowest.
 Leaving Group
• RI > RBr > RCl > RF
• The weaker the basicity, the better the leaving
group.
Relative rates of reaction
HO- + RCH2I  RCH2OH + I- 30,000
HO- + RCH2Br  RCH2OH + Br- 10,000
HO- + RCH2Cl  RCH2OH + Cl- 200
HO- + RCH2F  RCH2OH + F- 1
 1.5 Alkyl Halides
Relative Reactivity of Nucleophile in SN2
Reactions
Nucleophile : any species, either neutral or negatively
charged as long as it has an unshared pair of electrons
(Lewis base)
• NH2– > HO– > F–
• Stronger bases are better nucleophiles
• NH3 < H2O < HF
Stronger Weaker
base base
HO– > H2O;
CH3O– > CH3OH
NH2- > NH3
 1.5 Alkyl Halides
Nucleophiles in SN2 Reactions
CH3Br + Nu- CH3Nu + Br-
Bromomethane Product

Nucleophile Product Relative rate

of reaction
H 2O Water CH3OH Methanol 1
NH3 Ammonia CH3NH2 Methylamine 700
Cl- Chloride CH3Cl Chloromethane 1000
HO- Hydroxide CH3OH Methanol 10,000
I- Iodide CH3I Iodomethane 100,000
CN- Cyanide CH3CN Acetonitrile 125,000
 1.5 Alkyl Halides
Solvents in SN2 Reactions

• Protic solvents- those contain an –OH and –NH are

worst for SN2 reaction – decrease the rates
• Polar aprotic solvents are the best for SN2 reaction –
increase the rates
H3C H
H3C C
CH3OH < H2O < S O < N O < CH3CN

H3C CH3
Methanol Water Dimethyl sulfoxide Dimethylformamide Acetonitrile
(DMSO) (DMF)

Solvent reactivity increases

See page 234 - 246
 1.5 Alkyl Halides
Exercise 27 : Which alkyl halide would you expect to be
more reactive in SN2 reaction with a given nucleophile?

OR
Br Cl

Br
OR Br

Br
OR
Br
 1.5 Alkyl Halides
Exercise 28 : Indicate which reaction will occur faster

Br - OH
OH

Br - CN
CN

Br - I
I
 1.5 Alkyl Halides
Exercise 29 : Indicate which reaction will occur faster

KOH
Br H2 O HO

KOH
Br DMSO HO
 1.5 Alkyl Halides
The SN1 Nucleophilic Substitution
• Tertiary alkyl halides involves departure of the leaving
group prior to addition of the nucleophile
• Called an SN1 reaction – occurs in two distinct steps.
80% Ethanolic
CH3 CH3
solution
CH3C Br + NaOH CH3C OH + Br-
CH3 at 55oC CH3
2-bromo-2-methylpropane 2-methyl-2-propanol

See page 234 - 246

 1.5 Alkyl Halides
The SN1 Mechanism of Nucleophilic Substitution
CH3 CH3
slow
+ +
......Br ..
-
Formation of
STEP 1 CH3 C Br CH3 C carbocation
and halide ion
CH3 CH3

CH3 CH3 H Carbocation

.. fast
.. reacts rapidly
STEP 2 CH3 C+ + H ..
2O CH3 C O+
with water
CH3 CH3 H

CH3 H CH3 Another

.. fast molecule
STEP 3 CH3 C O..
+ H ..
2O CH3 C OH
water remove
CH3 H CH3 proton
 1.5 Alkyl Halides
The SN1 Mechanism of Nucleophilic Substitution
The stereochemistry of SN1 Reaction
-two products formed, one with same configuration as the reactant,
another one with inverted configuration
-if the two products formed with equal amount (50 :50), the reaction
is said to be racemization
CH2CH3 CH2CH3 CH2CH3
H2O
C +
H3C H H C CH C
HO 3 H3C H
Br OH
2-bromobutane (R)-2-butanol (S)-2-butanol

CH2CH3
x CH2CH3
H2O C+ H2O
+ +
H2O Br C
H H2O
H3C H3C H
Br- has diffused, H2O can Br- has not diffused, H2O can
See page 234 - 246 attack either side attack to one side
 1.5 Alkyl Halides
Predicting Whether a Substitution is an SN1 or
an SN2 Reaction
Secondary alkyl halides can go either SN1 or SN2?
CH2CH3 CH2CH3 CH2CH3
H2O
SN1 C +
H3C H H C CH C
HO 3 H3C H
Br OH
2-bromobutane (R)-2-butanol (S)-2-butanol
OR
CH2CH3 CH2CH3
OH-
C
SN2 H3C H H C CH
3
Br HO
2-bromobutane (R)-2-butanol

Good nucleophile ; 2-bromobutane will undergo SN2

and vice versa
See page 234 - 246
 1.5 Alkyl Halides
Factors Affecting SN1 Reactions

• Cation stability
• 3o alkyl halide > 2o alkyl halide > 1o alkyl halide.
• Leaving group
• The weaker the bond, the easier to break.
• RI > RBr > RCl > RF
• Nucleophile
• NO EFFECT.
 1.5 Alkyl Halides
Comparison SN2 and SN1

SN2 SN1
One-step mechanism Two-step mechanism
Bimolecular Unimolecular
Inverted configuration Racemate
Reactivity order: Reactivity order:
methyl > 1o > 2o > 3o 3o > 2o > 1o > methyl
(No reaction with 3o) (No reaction with 1o or methyl)
 1.5 Alkyl Halides
Exercise 30 : which alkyl halide would you expect to be
more reactive in an SN1 with a given nucleophile

OR
Br
Br

Br I
OR

OR Cl
Cl
 1.5 Alkyl Halides
Exercise 31 : Which of the following reactions will go SN1
reaction

Br NH3
NH2

NH2-

Br NH2
 1.5 Alkyl Halides
Exercise 32 : Which of the following reactions will go SN1
reaction

Br NaCN NC
H2O

Br NaCN CN
50% CH3CH2OH
 1.5 Alkyl Halides
Exercise 33

Which compound undergo substitution by the SN1

mechanism at the fastest rate?. Write the mechanism
when the compound reacts with H2O
(CH3)2CHCH2CH2CH2Br (CH3)2CHCHBrCH2CH3 (CH3)2CBrCH2CH2CH3

Which compound undergo substitution by the SN2

mechanism at the fastest rate?. Write the mechanism
when the compound reacts with OH-

(CH3)2CHCH2CH2CH2Br (CH3)2CHCHBrCH2CH3 (CH3)2CBrCH2CH2CH3

 1.5 Alkyl Halides
Reaction of Alkyl Halides with Cyanide in Ethanol

•Conversion of alkyl halides into nitrile

•The reagents is potassium cyanide or sodium cyanide
•The conditions of the reaction are the presence of the
medium ethanol and reflux
•It provides to synthesize higher carbon chain by
adding one carbon atom to alkyl halides
•Example bromoethane is undergoes SN2 mechanism
Ethanol
CH3Br + KCN CH3CN + KBr
Reflux
Bromomethane Acetonitrile

Ethanol
CH3CH2I + NaCN CH3CH2CN + NaI
Reflux
Iodoethane Propanenitrile
 1.5 Alkyl Halides
Hydrolysis and Reduction of Nitrile Compounds

Hydrolysis: Conversion of nitrile into carboxylic

acids H O+ 3
CH3CH2CN CH3CH2COOH
Propanenitrile Propanoic acid

Reduction: Conversion of nitrile into amines

1. LiAlH4,ether
CH3CH2CN CH3CH2CH2NH2
2. H2O
Propanenitrile Propanamine
 1.5 Alkyl Halides
Exercise 34 :Draw the structure of compound A, B and C

H3O+ B
NaCN
Br A
50% CH3CH2OH
LiAlH4/H2O
C
 Preparation of Grignard Reagents
• When an alkyl halide reacts with a metal such as Mg,
an organometallic compound, called the grignard
reagent , is produced.
• The reaction must be carried out in the absence of
water. Diethyl ether of THF is often used as the
solvent.
• Product is RMgX – an organometallic compound (alkyl-
metal bond)
– R is alkyl 1°, 2°, 3°
– X = Cl, Br, I
CH3CH2I Mg
CH3CH2MgI
Iodoethane Ether
Ethylmagnesium iodide
Preparation of Grignard
Reagents
 Preparation of Grignard
Reagents
The Grignard reagent is a very strong Lewis base. The
alkyl portion of the molecule can act as a nucleophile. It
reacts rapidly with molecules having acidic H atom
including water, producing an alkane.
δ‒ δ+

CH3CH2MgI H2O CH3CH3 + IMgOH

Ethyl magnesium iodide Ethane

Grignard reagent is primarily used in the synthesis of

alcohols. It reacts with aldehyde or ketone to produce
alcohols of the desired structures. (See: Reactions of
Aldehyde and Ketone)
 1.5 Alkyl Halides
Exercise 35 :Draw the structure of compound A, B and C

Mg
Br A
Ether

CH2CH3
Mg
C B
H3C I Ether
H
Cl
Mg
C
Ether
1.6 ALCOHOL

50
 1.6 Alcohol
• Aliphatic, hydroxy compounds
– Contain hydroxy functional groups (—OH)
• General formula = CnH2n + 1OH (n ≥ 1)
• Considered as derivatives of alkanes with H
atoms replaced
by OH groups.
R—H  R—OH
alkane alcohol
 1.6 Alcohol
• R—OH
• Ethanol = CH3CH2OH
– grain alcohol = fermentation of sugars
in grains
– alcoholic beverages
• proof number = 2x percentage of
alcohol
– gasohol
• Isopropyl alcohol = (CH3)2CHOH
– 2-propanol
– rubbing alcohol
– poisonous
• Methanol = CH3OH
– wood alcohol = thermolysis of wood
– paint solvent
– poisonous
 1.6 Alcohol
Classification of Alcohols
• Based on the number of alkyl groups (R) bonded to
the C atom that carries the -OH group, alcohols are
classified into three types:
• Primary, Secondary, and Tertiary

HO HO HO HO
H CH3 CH3 CH3
C C C C
H H H H H CH3 H3C CH3
Methyl alcohol Ethyl alcohol Isopropyl alcohol tert-Butyl alcohol

1o 2o 3o
 1.6 Alcohol
Alcohols Nomenclature
• Select the longest carbon chain containing OH group
• Derive the parent name by replacing the –e- of the
corressponding alkane with -ol
• Number main chain C atoms from end closest to the
OH group
• Name all substituents present and write the lowest
possible numbers
• List substituents in alphabetical order
• Name as a single word
 1.6 Alcohol
Alcohols Nomenclature
Step 1: Find the parent hydrocarbon chain containing OH
group
Step 2: Number the alkane chain beginning at the end
nearer the OH
6 5 4 3 2 1 1 2 3 4 5 6
CH3CH2CH2CH2CH CH2OH CH3CH2CH2CH2CH CH2OH

CH2CH2CH3 CH2CH2CH3

YES NO
Notice that
Named as hexanol numbering
starts at
alcohol group
 1.6 Alcohol
Alcohols Nomenclature
Step 3: Identify and number the substituents

6 5 4 3 2 1
CH3CH2CH2CH2CH CH2OH Named as hexanol

CH2CH2CH3

Substituent on C-2 , -CH2CH2CH3 , 2-propyl

OH
1 2 3 4 5
CH3CCH2CH2CH3 Named as 2-pentanol

CH3

Substituent on C-2 , -CH3 , 2-methyl

 1.6 Alcohol
Alcohols Nomenclature
Step 3: Identify and number the substituents
If there are two substituents on the same carbon, give both the
same number. There must be as many numbers in the name as there
are substituents . List substituents in alphabetical order
OH OH
6 5 4 3 2 1
6 5 4 3
CH3CH2CH2C CH2CH2 CH3CH2CH2C CH2CH2

2 H3C C CH3
H3C C CH3

1 CH3 CH3

YES NO
Substituent on C-2 , -CH3 , 2,2-dimethyl Substituent on C-2 , -C(CH3)3 , tert-butyl
on C-3, -CH2CH3, 3-ethyl
 1.6 Alcohol
Alcohols Nomenclature
Step 4: Write the name as a single word
OH
6 5 4 3 2 1
CH3CH2CH2CH2CH CH2OH 6 5 4 3
CH3CH2CH2C CH2CH2
CH2CH2CH3 2
H3C C CH3
2-ethylhexanol OH
1 2 3 4 5 1 CH3
CH3CCH2CH2CH3
3-ethyl-2,2-dimethyl-3-hexanol
CH3
2-methyl-2-pentanol
 1.6 Alcohol
Exercise 36 : Write the IUPAC name for the following
compound

OH
OH
 1.6 Alcohol
Exercise 37 :Draw the structural formula for the
following compound
i) 3,5 dimethyl-3-octanol
ii) 4-isopropyl-3-methylcyclohexanol
 1.6 Alcohol
Reaction of Alcohols
1. Nucleophilic substitution:
Conversion of alcohols into alkyl halides

2. Elimination
Conversion of alcohols into alkenes

3. Reaction with active metals

Preparation base for elimination of alkyl halides

4. Oxidation of alcohols
 1.6 Alcohol
Nucleophilic Substitution
Conversion of alcohols into alkyl halides
1. Reaction with hydrogen halides
CH3 CH3
SN1
CH3C OH + HBr CH3C Br + H2O
CH3 CH3
2-methyl-2-propanol 2-bromo-2-methylpropane
Br⁻ acts as a nucleophile, replacing –OH group

2. Reaction with inorganic halides

PCl5 SN2 CH3CH2Cl
CH3CH2OH +
Ethanol Chloroethane
Note: Conversion of an alcohol (primary and secondary) to a
haloalkane can be done by using PCl3, PCl5 or SOCl2 (thionyl
chloride), and PBr3
 1.6 Alcohol
Exercise 38 :Draw the structural formula of A, B and C
for the reaction below

PBr3
i OH A

OH HCl
ii B

SOCl2
OH C
iii
 1.6 Alcohol
Nucleophilic Substitution

Tertiary alcohol react with either HCl or HBr at 0oC by

SN1 mechanisms through a carbocation intermediate

Primary and secondary alcohol are much resistance to

hydrogen halides, however and are the best converted
into halides by treatment with either SOCl2 or PBr3 by
SN2 mechanism.

When alcohols react with SOCl2 at room temperature a

white steamy fumes released
Note: Mechanism for SN2 and SN1 in alcohols reaction, please refer
to alkyl halides
 1.6 Alcohol
Elimination (Dehydration)

• Elimination of water, dehydration requires an acidic

catalyst (sulfuric acid, H2SO4 as a catalyst) to
protonate the hydroxyl group of the alcohol and
convert it to a good leaving group.

• Loss of water, followed by loss of a proton, gives

alkene
 1.6 Alcohol
Elimination (Dehydration)

• The ease of dehydration follows the order:

R R H
R OH > H OH > R OH
R R H

Tertiary alcohols are readily dehydrated with acid

Secondary alcohols need a condition 75% H2SO4, 100oC
Primary alcohols need a condition 95% H2SO4, 150oC
To circumvent the need strong acid, POCl3 in pyridine is
used to dehydrate secondary and tertiary alcohols at
0oC
 1.6 Alcohol
Mechanism of Dehydration
STEP 1 : Protonated the hydroxyl group
H

H
....O H +
H
..O +
H
H
C C C C

STEP 2 : Water leaves, forming a carbocation

H

H ..O +
H H ..O
C C+ +
H
.. H
C C
 1.6 Alcohol
Mechanism of Dehydration

STEP 3 : Loss of a proton gives the alkene

..O H
H ..
C +
C
H H
C C +
H
..
O+
H
 1.6 Alcohol
Mechanism Dehydration of tert-Butyl Alcohol
CH3 H CH3 H
..OH H O+ .. ..
O+ ..
CH3 C .. + CH3 C + H2O ..
H CH3 H
CH3

Protonation of tert-Butyl alcohol tert-Butyloxonium ion

CH3 H CH3
CH3 C ..
O+ C+
..
CH3 +
..
H2O

CH3 H
CH3
Dissociation of tert-Butyloxonium ion tert-Butyl cation

H2C H
..O
CH3 C +
.. H
CH3 C CH2
H
CH3 CH3
Deprotonation of tert-Butyl cation 2-Methylpropene
 1.6 Alcohol
Regioselectivity, Zaitsev’s Rule and
Stereoselectivity
For elimination of 2-pentanol, the regioselectivity and
stereoselectivity will produces 2-pentene as major
product
H3CH2CH2C H

C C

H H
1-Pentene

CH3CH2CH2CHCH3
H3CH2C H H3CH2C CH3
OH
2-pentanol C C + C C

H CH3 H H
trans-2-pentene cis-2-pentene
 1.6 Alcohol
Mechanism Dehydration of 2-Pentanol

STEP 1 : Protonated the 2-pentanol to produce 2-pentyoxonium ion

H H
..O+ H
CH3CH2CH2CCH3 H .. CH3CH2CH2CCH3
....OH H
O+
H .. H
2-pentanol
 1.6 Alcohol
Mechanism Dehydration of 2-Pentanol
STEP 2 and STEP 3 : Water leaves and give carbocation and another
molecule water abstract -hydrogen from adjacent carbon to give alkene
H H H H

CH3CH2CH2CCH3 H3CH2C C C+ C H

O+
.. H H
H
H

H3CH2C H H3CH2C CH3

C C + C C

H CH3 H H
trans-2-pentene cis-2-pentene
 1.6 Alcohol
Mechanism Dehydration of 2-Pentanol
H H H H

CH3CH2CH2CCH3 H3CH2C C C+ C H

O+
.. H H
H
H

H3CH2CH2C H

C C

H H
1-Pentene
 1.6 Alcohol
Rearrangement in Alcohol Dehydration- Hydride
Shift in 1-butanol
H3O+
CH3CH2CH2CH2OH CH3CH2CH CH2 + H3CHC CHCH3

H H H H
.. H O.. + H

CH3CH2CH2C ..O H H CH3CH2CH2C O+.. CH3CH2CH2C+

H H H H
Primary carbocation

H H H H

CH3CH2CH2C+ CH3CH2C C+ CH3CH2C+ C H

H H H H H
Primary carbocation Hydride shift Secondary carbocation
 1.6 Alcohol
Rearrangement in Alcohol Dehydration- Hydride
Shift
..O H

H
..
H
H H3C CH3 H3C H
CH3CH2C+ C H H3CC C+ CH3 C C + C C

H H H H H H H CH3
Secondary carbocation

..O H

H
..
H H H3CH2C H
H
CH3CH2CH2C+ CH3CH2C C+ C C

H H H H H
Primary carbocation
 1.6 Alcohol
Exercise 39 :Draw the structural formula of A, B and C
for the reaction below

H2SO4
i OH A
Heat

OH
H2SO4
ii B
Heat

H2SO4
OH C
iii
Heat
 1.6 Alcohol
Reaction of Alcohols with Active Metals

2 CH3─OH + 2 K  2 CH3O−K+ + H2
potassium methoxide

2 CH3CH2─OH + 2 Na  2 CH3CH2O−Na+ + H2
sodium ethoxide

(CH3)3C-OH + 2 K  (CH3)3CO-K+ + H2
potassium tertbutoxide
These reagents are used to eliminate Alkyl
halide- see alkyl halides
 1.6 Alcohol
Oxidation of Alcohols (Dehydrogenation)
HO O O
CH3 CH3 [O] CH3
C [O] C C
H H -2H H -2H HO
Ethyl alcohol Acetaldehyde Acetic acid
1o

Typical oxidizing agents are:

1. Acidified potassium dichromate (K2Cr2O7)
or chromic acid H2CrO4
2. Acidified potassium permanganate (KMnO4)

Primary alcohols are oxidized either aldehydes or carboxylic

acid
Secondary alcohols are oxidized to ketones
Tertiary alcohols cannot oxidized
 1.6 Alcohol
Oxidation of Alcohols (Dehydrogenation)
For oxidation the alcohols, there must be at least one atom hydrogen
(oxidisable hydrogen)bonded to carbon atom contains the hydroxyl
group.
HO O
CH3 [O] CH3
C C
There is one oxidisable -2H
H CH3 H3C
hydrogen in secondary
alcohols Isopropyl alcohol Propanone

2o

HO
CH3 [O]
There is no oxidisable C No Reaction
hydrogen in tertiary -2H
alcohols
H3C CH3
tert-Butyl alcohol

3o
 1.6 Alcohol
Oxidation of Alcohols (Dehydrogenation)
• Use strong oxidants to oxidize primary alcohols,
directly convert to acid.
• Aldehyde only exist as an intermediate, and further
oxidized rapidly.
• To obtain best yield of aldehydes, use pyridinium
chlorochromate, PCC in dichloromethane
• This reagents suitable for primary alcohols because
the reaction is milder and can perform at lower
temperature.
HO O
CH3 PCC CH3
C C
H H CH2Cl2 H
Ethyl alcohol Acetaldehyde
1o
 1.6 Alcohol
Tests to Distinguish Classes of Alcohols
Two simple lab tests can be used to distinguish between
Primary, secondary and tertiary alcohols:

1. Lucas test:
The alcohols is shaken with a solution of ZnCl2 in
concentrated HCl. (Lucas reagent)
For a 30 alcohol , the solution turns cloudy almost
immediately.
For a 20 alcohol , cloudiness* observed in about 5
minutes.
10 alcohol shows no cloudiness.
*Cloudiness is due to the formation of alkyl halide
 1.6 Alcohol
Tests to Distinguish Classes of Alcohols
OH Cl
ZnCl2/HCl
H3CH2C C CH3 H3CH2C C CH3
CH3 CH3
2,2-butanol 2-Chloro-2-methylbutane
3o alcohol (cloudiness appears immediately)
OH Cl
ZnCl2/HCl
H3CH2CH2C C CH3 H3CH2CH2C C CH3
H H
2-Pentanol 2-Chloropentane
2o alcohol (cloudiness appears in a few minutes)

OH
ZnCl2/HCl
H3CH2CH2CH2C C H NO REACTION

H
1-Pentanol
1o alcohol
 1.6 Alcohol
Tests to Distinguish Classes of Alcohols
2. Oxidation test:
Only 1o and 2o alcohols are oxidised by hot acidified
KMnO4 or hot acidified K2Cr2O7 solution.

1o and 2o alcohols decolourise the KMnO4 solution,

whereas the colour of the K2Cr2O7 solution changes
from orange to green.

No reaction for 3o alcohols.

 Tests to Distinguish Classes of Alcohols
3. Iodoform Test
Iodoform test to distinguish between ethanol from methanol or 2-
propanol from 1-propanol
Ethanol and 2o alcohols with methyl alcohol group
CH3CH2OH -Ethanol
CH3CH(OH)CH3 – Isopropyl alcohol
reacts with iodine in aqueous NaOH to produce pale yellow solid
of iodoform (CHI3).
OH
O
H3C C H + 4I2 + 6NaOH CHI3 (s) + 5I- + 5H2O +
Triiodomethane
H C O-
H (iodoform)
Ethanol yellow precipitate

OH
O
H3C C CH3+ 4I2 + 6NaOH CHI3 (s) + 5I- + 5H2O +
Triiodomethane
H3C C O-
H (iodoform)
2-Propanol yellow precipitate
 1.6 Alcohol
Exercise 40 : Given three type of alcohols. Answer the
following question
OH
OH OH

A B C

i) Which alcohol did not react with KMnO4 solution?

ii) Which alcohol give positive result to Lucas reagents
iii) Which alcohol gives positive result to iodoform test?