CHM 102

CHEMISTRY OF ALCOHOLS
& THEIR REACTIONS
Dr. NELLY A. NDUKWE
 FUNCTIONAL GROUP & BACKGROUND INFORMATION

 Alcohols: R-O-H
 Classification of Alcohols; CH3, 1o, 2o, 3o

 Nomenclature:
Common names: “alkyl alcohol”
IUPAC: parent = longest continuous carbon chain
containing the –OH group.
alkane drop -e, add –ol
prefix locant for –OH (lower number for OH)
 CH3 CH3
CH3CHCH2CHCH3 CH3CCH3
OH OH
4-methyl-2-pentanol tert-butyl alcohol
2-methyl-2-propanol
2o 3o

CH3
HO-CHCH2CH3 CH3CH2CH2-OH

sec-butyl alcohol n-propyl alcohol

2-butanol 1-propanol
2o 1o
Physical properties of alcohols:

 polar + hydrogen bonding

 relatively higher mp/bp
 Solubility in Water. alcohols are soluble in water due to the
hydroxyl grp that forms hydrogen bonds with water molecules.
 The alcohols with smaller hydrocarbon chains are very soluble and
the solubility decreases as the length of the hydrocarbon chain
increases.
 CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2-OH
hydrophobic hydrophilic
 FERMENTATION PROCESS
 Oldest known organic synthesis:
“fermentation” Process
Sugar + yeast  ethyl alcohol + CO2
Grape juice => “wine”
Barley => “beer”
Honey => “mead”
Rice => “sake”

~5-11% ethanol
 FERMENTATION PROCESS

Distillation of fermented beverages to produce “distilled spirits” with a

greater percentage of ethyl alcohol (bp 78.3 oC).
Ethyl alcohol forms a binary azeotrope with water:
95% ethanol + 5% water (bp 78.15oC)

Diluted with water => “vodka” 40% ethyl alcohol in water.

“proof”: when aqueous alcohol is placed on a sample of gunpowder and

ignited, the gunpowder will burn at a minimum concentration of 50%
alcohol. This is called “100-proof”.
(proof = 2 * alcohol percent)
 FERMENTATION PROCESS

Add oil of juniper => gin

Add peat smoke => scotch
Age in a burned barrel => whiskey
Add peppermint => schnapps
Etc.

Ethyl alcohol is a poison. LD50 = ~10g/Kg orally in mice.

Nausea, vomiting, flushing, mental excitement or depression,
drowsiness, impaired perception, loss of coordination, stupor, coma,
death may occur. (intoxication)
 Reaction of Alcohols with Hydrogen Halides

Reaction of alcohols with HX:

R-OH + HX  R-X + H2O
They undergo a nucleophilic substitution reaction to generate
alkyl halides and water
a) HX: Their reactivity order: HI > HBr > HCl >HF
b) ROH: 3o > 2o > 1o > CH3
c) May be acid catalyzed
d) Rearrangements are possible except with most 1o alcohols.
)
 SNI Meachanism occur by the reaction of ter-butyl alcohol and aqueous
hydrochloric acid leading to protonation of alcohol to for oxonium ion (
a Lewis acid-base complex between ( R+) &( H2O.
 Examples of nucleophiles include the halogen anions ( Cl-, CI-, Br-)
hydroxide ion, ( OH-), ammonia (NH3) and water.
 Nucleophiles are electron donors( Lewis bases)
 Electrophiles are electron acceptors, arepositively charged or neutral
species. They include
 hydronium ion ( H3O+), AlCl3, halogen molecules, F2, Cl2, Br2 & I2
CH3CH2CH2CH2-OH + NaBr, H2SO4, heat  CH3CH2CH2CH2-Br
n-butyl alcohol n-butyl bromide
1-butanol 1-bromobutane

CH3 CH 3
CH3C-OH + HCl  CH3C-Cl (room temperature)
CH3 CH 3
tert-butyl alcohol tert-butyl chloride
2-methyl-2-propanol 2-chloro-2-methylpropane

CH3CH2-OH + HI, H+, heat  CH3CH2-I

ethyl alcohol ethyl iodide
ethanol iodoethane
Mechanism of Reaction

CH3-OH and most 1o alcohols react with HX via SN2 mechanism

3o and 2o react with HX via SN1 mechanism

Both mechanisms include an additional, first step, protonation of the

alcohol oxygen:
R-OH + H+  R-OH2+ “oxonium ion”
Whenever an oxygen containing
compound is placed into an acidic
solution, the oxygen will be
protonated, forming an oxonium ion.
Mechanism for reaction of an alcohol with HX:
CH3OH or 1o alcohols:

SN2

1) R-OH + HX R-OH2 + X

RDS
2) X + R-OH2 R-X + H2O
Mechanism for reaction of an alcohol with HX:
2o or 3o alcohols:

SN1

1) R-OH + HX R-OH2 + X

RDS
2) R-OH2 R + H2O

3) R + X R-X
May be catalyzed by acid.

SN2 rate = k [ ROH2+ ] [ X- ]

SN1 rate = k [ ROH2+ ]

Acid protonates the -OH, converting it into a better leaving

group (H2O), increasing the concentration of the oxonium ion,
and increasing the rate of the reaction.
Rearrangements are possible (except with most 1o alcohols):

CH3 CH 3
CH3CHCHCH3 + HBr  CH3CCH2CH3
OH Br

  Br-

CH3 CH3 [1,2-H] CH3

CH3CHCHCH3  CH3CHCHCH3  CH3CCH2CH3
OH2+ + +
2o carbocation 3o carbocation
In the reaction of most 1o alcohols with HX you don't have
to worry about the possibility of rearrangements. The mechanism
is SN2 and does not involve carbocations.

CH3CH2CH2CH2CH2-OH + HBr, H+, heat

1-pentanol
CH3CH2CH2CH2CH2-Br
1-bromopentane
1o alcohol:
No rearrangement, SN2
Most 1o? If large steric requirement…

CH3 CH3
CH3CCH2-OH + HBr  CH3CCH2CH3
CH3 Br
neopentyl alcohol 2-bromo-2-methylbutane

 

CH3 CH3 CH3

CH3CCH2-OH2+  CH3CCH2+  CH3CCH2CH3
CH3 CH3 +
1o carbocation 3o carbocation

[1,2-CH3]
2. With PX3
ROH + PX3  RX

a) PX3 = PCl3, PBr3, P + I2

b) No rearrangements 
c) ROH: CH3 > 1o > 2o

CH3 CH3
CH3CCH2-OH + PBr3  CH3CCH2-Br
CH3 CH3
neopentyl alcohol 2,2-dimethyl-1-bromopropane
4) As acids.

a) With active metals:

ROH + Na  RONa + ½ H2 

b) With bases:
ROH + NaOH  NR!

CH4 < NH3 < ROH < H2O < HF

5. Ester formation.

CH3CH2-OH + CH3CO2H, H+  CH3CO2CH2CH3 + H 2O

CH3CH2-OH + CH3COCl  CH3CO2CH2CH3 + HCl

CH3-OH + CH3SO2Cl  CH3SO3CH3 + HCl

Esters are alkyl “salts” of acids.

 O O
R S Cl + H-O-R R S O-R + HCl
O O

sulfonyl chloride alcohol sulfonate ester

6. Oxidation
Oxidizing agents: KMnO4, K2Cr2O7, CrO3, NaOCl, etc.
Primary alcohols:
CH3CH2CH2-OH + KMnO4, etc.  CH3CH2CO2H
carboxylic acid
Secondary alcohols:
OH O
CH3CH2CHCH3 + K2Cr2O7, etc.  CH3CH2CCH3

ketone
Teriary alcohols:

no reaction.
Primary alcohols can also be oxidized to aldehydes:

CH3CH2CH2-OH + C5H5NHCrO3Cl  CH3CH2CHO

pyridinium chlorochromate aldehyde
or
CH3CH2CH2-OH + K2Cr2O7, special conditions 
 Types of Alcohol Reactions
• Dehydration to alkene
• Oxidation to aldehyde, ketone
• Substitution to form alkyl halide
• Reduction to alkane
• Esterification
• Tosylation
• Williamson synthesis of ether =>

Chapter 11 25
Summary Table

=>
Chapter 11 26
Oxidation States
• Easy for inorganic salts
• CrO42- reduced to Cr2O3
• KMnO4 reduced to MnO2
• Oxidation: loss of H2, gain of O, O2, or X2
• Reduction: gain of H2 or H-, loss of O, O2, or X2
• Neither: gain or loss of H+, H2O, HX
=>

Chapter 11 27
1º, 2º, 3º Carbons

=>
Chapter 11 28
Oxidation of 2° Alcohols
• 2° alcohol becomes a ketone
• Reagent is Na2Cr2O7/H2SO4
• Active reagent probably H2CrO4
• Color change: orange to greenish-blue

OH O
Na2Cr2O7 / H2SO4
CH3CHCH2CH3 CH3CCH2CH3

=>

Chapter 11 29
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
=>
Chapter 11 30
3° Alcohols Don’t Oxidize
• Cannot lose 2 H’s
• Basis for chromic acid test

=>
31
Other Oxidation Reagents
• Collins reagent: Cr2O3 in pyridine
• Jones reagent: chromic acid in acetone
• KMnO4 (strong oxidizer)
• Nitric acid (strong oxidizer)
• CuO, 300°C (industrial dehydrogenation)
• Swern oxidation: dimethylsulfoxide, with oxalyl
chloride and hindered base, oxidizes 2 alcohols to
ketones and 1 alcohols to aldehydes.
=>
Chapter 11 32
Biological Oxidation
• Catalyzed by ADH, alcohol dehydrogenase.
• Oxidizing agent is NAD+, nicotinamide adenine
dinucleotide.
• Ethanol oxidizes to acetaldehyde, then acetic acid,
a normal metabolite.
• Methanol oxidizes to formaldehyde, then formic
acid, more toxic than methanol.
• Ethylene glycol oxidizes to oxalic acid, toxic.
• Treatment for poisoning is excess ethanol.
=>

33
Alcohol as a Nucleophile
H
O
C R X

• ROH is weak nucleophile

• RO- is strong nucleophile
• New O-C bond forms, O-H bond breaks.
=>

34
Alcohol as an Electrophile
• OH- is not a good leaving
group unless it is H
protonated, but most
nucleophiles are strong
bases which would remove
O
H+. + C
• Convert to tosylate (good
leaving group) to react with
strong nucleophile (base) C-Nuc bond forms,
=> C-O bond breaks

35
Reduction of Alcohols
• Dehydrate with conc. H2SO4, then add H2
• Tosylate, 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

36
Reaction with HBr
• -OH of alcohol is protonated
• -OH2+ is good leaving group
• 3° and 2° alcohols react with Br- via S 1
N

• 1° alcohols react via SN2

+ H -
H3O Br
R O H R O H R Br =>

37
 Reaction with HCl
• Chloride is a weaker nucleophile than bromide.
• Add ZnCl2, which bonds strongly with
-OH, to promote the reaction.
• The chloride product is insoluble.
• Lucas test: ZnCl2 in conc. HCl
• 1° alcohols react slowly or not at all.
• 2 alcohols react in 1-5 minutes.
• 3 alcohols react in less than 1 minute.
=>

38
Dehydration Reactions

• Conc. H2SO4 produces alkene

• Carbocation intermediate
• Saytzeff product
• Bimolecular dehydration produces ether
• Low temp, 140°C and below, favors ether
• High temp, 180°C and above, favors alkene
=>

Chapter 11 39
Dehydration Mechanisms
H
OH OH
H2SO4
CH3CHCH3 CH3CHCH3 CH3CHCH3
alcohol
H2O
CH2 CHCH3
+
H3O
CH3OH CH3 OH2 CH3 O CH3
H
CH3OH CH3OCH3
H2O
=>

Chapter 11 40
Esterification Reaction
• Fischer: alcohol + carboxylic acid
• Tosylate esters
• Sulfate esters
• Nitrate esters
• Phosphate esters
=>

Chapter 11 41
Fischer Esterification
• Acid + Alcohol yields Ester + Water
• Sulfuric acid is a catalyst.
• Each step is reversible.

O CH3 + O CH3
H
CH3 C OH + H O CH2CH2CHCH3 CH3C OCH2CH2CHCH3

+ HOH

=>

Chapter 11 42
Tosylate Esters
• Alcohol + p-Toluenesulfonic acid, TsOH
• Acid chloride is actually used, TsCl

O
CH3CH2 O H + HO S CH3
O

O
CH3CH2 O S CH3 =>
O
+ HOH
Chapter 11 43
Sulfate Esters

Alcohol + Sulfuric Acid

O +
O
H
HO S OH + H O CH2CH3 HO S OCH2CH3
O O

O + O
H
CH3CH2O H + HO S OCH2CH3 CH3CH2O S OCH2CH3
O O =>

Chapter 11 44
Nitrate Esters
O +
H O
N OH + H O CH2CH3 N OCH2CH3
O O

CH2 O H CH2 O NO2

CH2 O H + 3 HO NO2 CH2 O NO2
CH2 O H CH2 O NO2

glycerine nitroglycerine =>

Chapter 11 45