CHAPTER 6

ALCOHOLS AND ETHER

BWK10303 ORGANIC CHEMISTRY 1
SEMESTER I SESSION 2023/2024
CHM. DR. SALIZA BINTI ASMAN
Outline
1. Alcohols
2. Structure, nomenclature and physical properties
3. Preparation
4. Reactions
5. Ether
6. Structure, nomenclature and physical properties
7. Preparation and reactions
8. Simple chemical test of alcohols and ether
Alcohols

Petronas Methanol Labuan

The plant currently produces 660,000

tonnes of methanol per year, using
some 55 million standard cubic feet of
gas per day as feedstock
 Alcohols
▪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
 Structure of Alcohols
Aliphatic, hydroxy compounds
◦ Contain hydroxy functional groups (—OH)
General formula = CnH2n + 1OH (n ≥ 1)
Considered one H atoms replaced by OH groups.

OH OH OH
C C C C

Alcohols, when OH group Enol, when OH group bonded Phenol, when OH group bonded to
bonded to one of sp3 carbon to sp2 carbon sp2 carbon atom in benzene or
aromatic ring
 Structure 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
Structure of Alcohols
 Structure of Alcohols
Glycols

• 1, 2 diols (vicinal diols) are called glycols.

• Common names for glycols use the name of the alkene from which they were
made.
CH2CH2 CH2CH2CH3
OH OH OH OH
1,2-ethanediol 1,2-propanediol
ethylene glycol propylene glycol
Nomenclature of Alcohols
▪Select the longest carbon chain containing OH group
▪Derive the parent name by replacing the –e- of the corresponding
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
 Nomenclature of Alcohols
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 numbering
Named as hexanol starts at alcohol group
Nomenclature of Alcohols
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

Nomenclature of Alcohols
Step 3: Identify and number the substituents
i. If there are two substituents on the same carbon, give both the same number.
ii. There must be as many numbers in the name as there are substituents.
iii. List substituents in alphabetical order
OH OH
6 6 5 4 3 2 1
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
Nomenclature of Alcohols
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
Nomenclature of Alcohols
Unsaturated alcohols
▪ Priority goes to the hydroxyl group; assign that carbon the lowest number.
▪ Use alkene or alkyne name.

OH
CH2 CHCH2CHCH3
4-penten-2-ol (pent-4-ene-2-ol)
Nomenclature of Alcohols
Hydroxy Substituent
▪ When -OH is part of a higher priority class of compound, it is named as
hydroxy.

▪ Example:
Nomenclature of Alcohols
Common Names
▪ Alcohol can be named alkyl alcohol.
▪ Useful only for small alkyl groups.

▪ Example:
Nomenclature of Alcohols
Naming Diols
▪ Two numbers are needed to locate the two –OH groups.
▪ Use –diol as suffix instead of -ol.

▪ 1,2 diols (vicinal diols) are called glycols.

▪ Common names for glycols use the name of the alkene from which they
were made.
Nomenclature of Alcohols
Naming Phenols
▪ −OH group is assumed to be on carbon 1
▪ For common names of disubstituted phenols, use ortho- for 1,2; meta- for
1,3; and para- for 1,4.
▪ Methyl phenols are cresols.
 Physical properties of Alcohols
Boiling point
▪ Unusually high boiling points due to hydrogen bonding between molecules.
▪ Small alcohols are miscible in water, but solubility decreases as the size of the alkyl group
increases;
▪ Alkyl group is hydrophobic because alkyl groups are non-polar due to almost similar
electronegativity of carbon and hydrogen, and water is a polar solvent. Due to this alkyl
groups are not soluble in water as they are non-polar which makes them hydrophobic in
nature.
▪ B.p. increases as the number of C atoms increases.
▪ Reason: larger surface area of alkyl group, creates more Van der Waals forces, thus requires
more energy to boil off.
▪ B.p. decreases as branching increases.
▪ Reason: smaller surface area, smaller Van der Waals forces.
 Physical properties of Alcohols
Boiling point
Physical properties of Alcohols

Intermolecular forces involved:

a) hydrogen bonding
b) dipole-dipole attractions

In increasing order:

Propane < dimethyl ether < ethanol

Physical properties of Alcohols
Solubility in Water

Solubility decreases as the size

of the alkyl group increases.
Questions
1. Write the IUPAC name for the following compound

2. Draw the structural formula for the following compound

i. C3H8O iii. C3H6O
ii. C4H10O iv. C3H4O
3 Questions

4
 Preparation of alcohols
Oxymercuration-Demercuration
✅Markovnikov product formed
✅Anti addition of H-OH
(https://www.chem.ucla.edu/~harding/IGOC/S/syn_addition.html)

✅No rearrangements

▪ Reagent is mercury(II) acetate which dissociates slightly to form +Hg(OAc) in H2O.

▪ +Hg(OAc) is the electrophile, will be attacked by the π bond.
 Preparation of alcohols

▪ The intermediate is a cyclic mercurinium ion, a three-membered ring with a positive charge.
▪ Water approaches the mercurinium ion from the side opposite the ring (anti addition).
▪ Water adds to the more substituted carbon to form the Markovnikov product.
 Preparation of alcohols

*Sodium borohydride (NaBH4), a reducing agent, replaces the mercury with hydrogen.
 Preparation of alcohols
Hydroboration-Oxidation
✅Anti-Markovnikov product formed
✅Syn addition of H-OH

❖ Borane, BH3, adds a hydrogen to the most substituted carbon in the double bond.
❖ The alkylborane is then oxidized to the alcohol which is the anti-Markovnikov product.

*Syn: indicates that both H and OH are present on the same side of the double bond.
*Anti: indicates that H and OH are present on the opposite sides of the double bond.
Preparation of alcohols
 Preparation of alcohols
Preparation of Glycols
👉🏽 Hydroxylation of alkenes
❖ osmium tetroxide, hydrogen peroxide
❖ cold, dilute, basic potassium permanganate (Baeyer Test) - for alkene
 Preparation of alcohols
Reduction of Carbonyl Group
❖ Reduction of aldehyde yields 10 alcohol.
❖ Reduction of ketone yields 20 alcohol.
❖ Reagents:
a) Sodium borohydride, NaBH4
b) Lithium aluminum hydride, LiAlH4
c) Raney nickel
Preparation of alcohols
Sodium Borohydride (NaBH4)
▪ Hydride ion, Hˉ, attacks the carbonyl carbon, forming an alkoxide ion.
▪ Then the alkoxide ion is protonated by dilute acid.
▪ Only reacts with carbonyl of aldehyde or ketone, not with carbonyls of esters or
carboxylic acids.

O H O H O H
C C + C
H H3O
H H H
Preparation of alcohols
Lithium Aluminium Hydride (LiAlH4)
▪ Stronger reducing agent than sodium borohydride, but dangerous to work with.
▪ Converts esters and acids to 10 alcohols.
▪ LiAlH4 reduces more stable compounds which are resistant to reduction.

O H O H
C C
OCH3 LAH
H
H3O+

*Comparison of Reducing Agents

Preparation of alcohols
Catalytic Hydrogenation
• Add H2 with Raney nickel catalyst.
• Also reduces any C=C bonds.

OH O OH

NaBH4 H2, Raney Ni

Preparation of alcohols
Reaction with Carbonyl
▪ R:ˉ attacks the partially positive carbon in the carbonyl.
▪ The intermediate is an alkoxide ion.
▪ Addition of water or dilute acid protonates the alkoxide to produce an alcohol.
 Preparation of alcohols
Organometallic Reagents
❖ Carbon is bonded to a metal (Mg or Li).
❖ Carbon is nucleophilic (partially negative).
❖ It will attack a partially positive carbon:
a) C - X
b) C = O
❖ A new carbon-carbon bond forms.
❖ Formula R-Li (reacts like R:- +Li)
❖ Can be produced from alkyl, vinyl, or aryl halides, just like Grignard reagents (R-Mg-X).
❖ Ether not necessary, wide variety of solvents can be used.
 Preparation of alcohols
Grignard Reagents
❖ Formula R-Mg-X (reacts like R:- +MgX)
❖ Stabilized by anhydrous ether
❖ Iodides most reactive
❖ May be formed from any halide: primary, secondary, tertiary, vinyl, aryl
Preparation of alcohols
Example of Grignard Reagents
Br
ether MgBr
+ Mg

Cl MgCl
CH3CHCH2CH3 ether
+ Mg CH3CHCH2CH3

CH3C CH2
ether
Br + Mg CH3C CH2
MgBr
Preparation of alcohols
Synthesis of 1° Alcohols

*Grignard + formaldehyde yields a primary alcohol with one additional carbon.

CH3 H H CH3 H
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H
H H H

CH3 H
HOH
CH3 CH CH2 CH2 C O H
H
Preparation of alcohols
Synthesis of 2° Alcohols

*Grignard + aldehyde yields a secondary alcohol.

CH3 H H3C CH3 CH3
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H
H H H

CH3 CH3
HOH
CH3 CH CH2 CH2 C O H
H
Preparation of alcohols
Synthesis of 3° Alcohols

*Grignard + ketone yields a tertiary alcohol.

CH3 H H3C CH3 CH3

H3 C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H3C
H H CH3

CH3 CH3
HOH
CH3 CH CH2 CH2 C O H
CH3
 Preparation of alcohols
Grignard Reactions with Acid Chlorides and Esters
❖ Reaction with two moles of Grignard reagent produces a tertiary alcohol with two
identical alkyl groups.
❖ Reaction with one mole of Grignard reagent produces a ketone intermediate, which
reacts with the second mole of Grignard reagent.
Preparation of alcohols
Preparation of alcohols
Grignard Reagent + Ethylene Oxide
❖ Epoxides are unusually reactive ethers.
❖ Product is a 10 alcohol with 2 additional carbons.

O MgBr
O
CH2 CH2
MgBr + CH2 CH2

HOH
O H
CH2CH2
 Preparation of alcohols
Preparation of Phenols
1. Alkali fusion of sodium benzenesulfonate (1890)

SO3 , H2SO4 NaOH

SO 3H ONa+
350o C
( sulfonation ) (fusion)

HCl

NaCl +
OH
 Preparation of alcohols
Preparation of Phenols
2. Process cumene (isopropyl benzene)
CH3
CH3CH CH2
CH
H2SO4
CH3
(cumene)

O2

CH3
H3O+ CH3
COOH
OH + C O
CH3
CH3

*CH3CH=CH2 + H2SO4ˉ ➝ CH3CHCH3

Preparation of alcohols
 Preparation of alcohols
Preparation of Phenols
3. Hydrolysis of Chlorobenzene (DOW process)

350o
C
Cl + 2 NaOH ONa
150 atm

HCl

OH
Reaction of alcohols
👉🏽Nucleophilic substitution: Conversion of alcohols into alkyl halides
👉🏽 Elimination: Conversion of alcohols into alkenes
👉🏽 Reaction with active metals : Preparation base for elimination of alkyl
halides
 Reaction of alcohols
Nucleophilic substitution of alcohols
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
*Conversion of an alcohol (primary and secondary) to a haloalkane can be done by using
PCl3, PCl5 or SOCl2 (thionyl chloride), and PBr3
 Reaction of alcohols
Nucleophilic substitution of alcohols

❖ 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
Reaction of alcohols
Reaction with HBr
❖ -OH of alcohol is protonated
❖ -OH2+ is good leaving group
❖ 3° and 2° alcohols react with Brˉ via SN1
❖ 1° alcohols react via SN2
Reaction of alcohols
Limitation of HX reactions
❖ HI does not react
❖ Poor yields of 1° and 2° chlorides
❖ May get alkene instead of alkyl halide
❖ Carbocation intermediate may rearrange.
Reactions with Phosphorus Halides (P-X)
❖ Good yields with 1° and 2° alcohols
❖ PCl3 for alkyl chloride (but SOCl2 better)
❖ PBr3 for alkyl bromide
❖ P and I2 for alkyl iodide (PI3 not stable)
 Reaction of alcohols
1° alcohols react via SN2

3° and 2° alcohols react with Brˉ via SN1

Reaction of alcohols
Nucleophilic substitution of alcohols

❖ Nucleophilic substitution on an alkyl halide, RX

Reaction of alcohols

❖ Hydration of alkenes, Water in Acid Solution, H2O/H+

Reaction of alcohols
Question
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
 Reaction of alcohols
Elimination of alcohols
❖ Elimination of water or dehydration requires an acidic catalyst (sulfuric acid,
H2SO4 or phosphoric acid, H3PO4 as a catalyst) to protonate the hydroxyl group
of the alcohol and convert it to a good leaving group (H-O-H).
❖ Loss of water, followed by loss of a proton, formed carbocation as intermediate,
protic solvent removes adjacent H⁺, gives alkene
❖ The ease of dehydration follows the order (follow Zaitsev’s rule) :

R R H
R OH > H OH > R OH
R R H
 Reaction of alcohols
Elimination of alcohols
❖Tertiary alcohols are readily dehydrated with acid
❖Secondary alcohols need a condition 75% H2SO4, 100oC
❖Primary alcohols need a condition 95% H2SO4, 150oC
❖To overcome the need of strong acid, POCl3 in pyridine is used to dehydrate
secondary and tertiary alcohols at 0ºC
❖Concentrated H2SO4 produces alkene
❖Bimolecular dehydration produces ether
❖Low temp, 140ºC and below, favors ether
❖High temp, 180ºC and above, favors alkene
Reaction of alcohols
Mechanism of dehydration
 Reaction of alcohols
CH3 H CH3 H
..OH H O+ .. ..
O+ ..
CH3 C .. + CH3 C + H2O ..
H CH3 H
CH3

Mechanism of Protonation of tert-Butyl alcohol tert-Butyloxonium ion

dehydration of CH3 H CH3

..
tert-butyl CH3 C ..
O+ CH3 C + + H ..
2O

alcohol 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
 Reaction of alcohols
Regioselectivity, Zaitsev’s rule and stereoselectivity
*For elimination of 2-pentanol, H3CH2CH2C H
the regioselectivity and stereoselectivity C C
will produce 2-pentene as a major product
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
 Reaction of alcohols
Mechanism dehydration of 2-pentanol
H H
STEP 1 : Protonated the 2-pentanol to
..O+ H
produce 2-pentyoxonium ion
CH3CH2CH2CCH3 H .. CH3CH2CH2CCH3
....OH H +

H
H ..O H H H H
2-pentanol
CH3CH2CH2CCH3 H3CH2C C C+ C H

O+
.. H H
H
H

H3CH2C H H3CH2C CH3

STEP 2 and STEP 3 : Water leaves and
give carbocation and another molecule C C + C C
water abstract -hydrogen from
H CH3 H H
adjacent carbon to give alkene
trans-2-pentene cis-2-pentene
Reaction of alcohols
Rearrangement in alcohol dehydration – hydride shift in 1-
butanol
H3O+
CH3CH2CH2CH2OH CH3CH2CH CH2 + H3CHC CHCH3

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

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
Reaction of alcohols
Rearrangement in alcohol dehydration – hydride shift in 1-
butanol
..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
H H3CH2C H
CH3CH2CH2C+ CH3CH2C C+ C C

H H H H H
Primary carbocation
 Reaction of alcohols
Rearrangement to form more stable carbocation
1,2-Hydride Shift

https://byjus.com/chemistry/hydride-shift/#5
Reaction of alcohols
Rearrangement to form more stable carbocation
1,2-Methyl Shift
Reaction of alcohols
Rearrangement to form more stable carbocation
Ring Expansion
 Reaction of alcohols
Oxidation of alcohols
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:

i. Acidified potassium dichromate, K2Cr2O7 or chromic acid, H2CrO4
ii. Acidified potassium permanganate, KMnO4
❖ Primary alcohols are oxidized by either aldehydes or carboxylic acid
❖ Secondary alcohols are oxidized to ketones
❖ Tertiary alcohols cannot be oxidized
Reaction of alcohols
Oxidation of alcohols
❖ Use strong oxidants to oxidize primary alcohols, and directly convert to acid.
❖ Aldehyde only exists as an intermediate, and further oxidized rapidly.
❖ To obtain the best yield of aldehydes, use pyridinium chlorochromate, PCC in
dichloromethane
❖ These reagents are suitable for primary alcohols because the reaction is milder and
can perform at lower temperatures.
HO O
CH3 PCC CH3
C C
H H CH2Cl2 H
Ethyl alcohol Acetaldehyde
1o
Reaction of alcohols
Oxidation of alcohols

*For oxidation of the alcohols,

there must be at least one
atom of hydrogen (oxidisable
hydrogen) bonded to a carbon
atom containing the hydroxyl
group.
Reaction of alcohols
Reduction of alcohols
❖ Dehydrate with conc. H2SO4, then add H2
❖ Tosylate with TsCl then reduce with LiAlH4

OH
H2SO4 H2
CH3CHCH3 CH2 CHCH3 CH3CH2CH3
Pt
alcohol alkene alkane

OH OTs
TsCl LiAlH4
CH3CHCH3 CH3CHCH3 CH3CH2CH3
alcohol tosylate alkane
Reaction of alcohols
Reaction of alcohols
Question
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
Reaction of alcohols
Fischer Esterification
❖ Acid + Alcohol yields Ester + Water
❖ Sulfuric acid is a catalyst.
❖ Each step is reversible.
Reaction of alcohols
 Reaction of alcohols
Formation of Alkoxide Ions
❖ React methanol and ethanol with sodium metal

❖ React with base

Reaction of alcohols
Formation of Alkoxide Ions

❖ ROH + Na (or NaH) yields sodium alkoxide

❖ ROˉ + 1° alkyl halide yields ether (Williamson ether synthesis)
 Reaction of alcohols
Reactions of Phenols
❖ Reduction by catalytic hydrogenation at 300ºC
❖ Electrophilic Aromatic Substitution (o, p-director)
-Reaction with bromin water obtains 2,4,6-tribromophenol
❖ Reaction to the hydroxyl groups
a) formation of phenoxide ions
b) esterification of phenol
- phenol + NaOH….+ acyl chloride phenol + acids/H⁺,heat
a) formation of ether
- phenol + alkyl halide
Reaction of alcohols
Formation of Phenoxide Ions
❖ Phenol reacts with hydroxide ions to form phenoxide ions

O H O
+ OH
+ HOH
pKa = 15.7
pKa = 10
Reaction of alcohols
Formation of Phenoxide Ions

Phenoxide ion is more stable; delocalization of the –ve charge via resonance
around the benzene ring make it stable; hence increase the acidity
*Phenol is 100 million times more acidic than cyclohexanol
 Reaction of alcohols
Reduction of phenols

Oxidations of phenols – different from alcohol

Reaction of alcohols
Formation of salts
 Reaction of alcohols
Esterification reaction of phenols

O
ONa O C CH3
O
+ CH3C + NaCl
Cl

Formation of ether

ONa O CH2CH3

+ CH3CH2 Cl + NaCl
 Reaction of alcohols
Test 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 3º alcohol , the solution turns cloudy almost immediately.
❖For a 2º alcohol , cloudiness* observed in about 5 minutes.
❖1º alcohol shows no cloudiness.

*Cloudiness is due to the formation of alkyl halide

Reaction of alcohols
Test 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
 Reaction of alcohols
Test 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 decolourised the KMnO4 solution, whereas the colour of the
K2Cr2O7 solution changes from orange to green.

❖ No reaction for 3o alcohols.

Reaction of alcohols
Oxidation of 1° Alcohols
❖ 1° alcohol to aldehyde to carboxylic acid
❖ Difficult to stop at aldehyde
❖ Use pyridinium chlorochromate (PCC) to limit the oxidation.
❖ PCC can also be used to oxidize 2° alcohols to ketones.

OH N H CrO3Cl O
CH3CH2CH2CH2 CH3CH2CH2CH
Reaction of alcohols
Oxidation of 2° Alcohols
❖ 2° alcohol becomes a ketone
❖ Reagent is; sodium dichromate, Na2Cr2O7/H2SO4
❖ Color change: orange to greenish-blue

OH O
Na2Cr2O7 / H2SO4
CH3CHCH2CH3 CH3CCH2CH3

3° Alcohols Don’t Oxidize

❖ Cannot lose 2 H’s
❖ Basis for chromic acid test
Reaction of alcohols
Other Oxidation Reagents
❖ Collins reagent: CrO3 in pyridine
❖ Jones reagent: chromic acid in acetone
❖ KMnO4 (strong oxidizer)
❖ Nitric acid (strong oxidizer)
❖ CuO, 300°C (industrial dehydrogenation)
Reaction of alcohols
Test 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
Question
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?