HYDROXY COMPOUNDS

(ALCOHOLS)

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INTRODUCTION
 Alkane with hydroxyl group (–OH)
 General formula for aliphatic alcohol,
CnH2n+1OH
 Aromatic alcohol – phenol (-OH attached
to the benzene rings)

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 INTRODUCTION

OH CH2-OH

CH3CH2-OH

ALIPHATIC ALCOHOL (–OH group attached

directly to the alkyl group)

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INTRODUCTION

OH OH OH
CH3

Br

AROMATIC ALCOHOL (–OH group attached

directly to the aryl group)

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CLASSIFICATION
 Methyl alcohol CH3-OH

 10 Alcohols R-CH2-OH
R
 20 Alcohols R-CH-OH
R
 30 Alcohols R-C-OH
R
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NOMENCLATURE
Structure General name IUPAC name
CH3-OH methyl alcohol methanol
CH3CH2-OH ethyl alcohol ethanol
CH3CH(OH)CH3 isopropyl alcohol 2-propanol

OH cyclohexyl cyclohexanol
alcohol

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Naming the alcohol
1. The suffix ‘–e’ in the alkane parent name is
replaced by ‘–ol’
2. The location of the –OH on the longest chain
is given by the smallest possible number

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IUPAC rules for naming alcohols
1. Determine parent name
2. Give the lowest number to the carbon
bearing the –OH group
3. Identify substituent groups and their position
4. Name the alcohol

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Naming Alcohols, R-O-H:

CH3 CH3
CH3CHCH2CHCH3 CH3CCH2CH2CH3
OH OH
4-methyl-2-pentanol
2-methyl-2-pentanol
2o 3o
CH3
HO-CHCH2CH3 CH3CH2CH2-OH

sec-butyl alcohol n-propyl alcohol

2-butanol 1-propanol
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2o 1o
Naming Alcohols

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For phenol, C attach to the –OH group is C 1

OH OH OH
CH3

CH2CH3 Br

3-ethylphenol 3-bromophenol 2-methylphenol

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Alcohol with 2 hydroxy groups
Structure General name IUPAC name
CH2(OH)CH2-OH
ethylene glycol 1,2-ethanediol
CH3CH(OH)CH2-OH
propylene glycol 1,2-propanediol
HO-CH2CH2CH2-OH trimethylene
1,3-propanediol
glycol
OH-CH2CHCH2-OH
glycerol 1,2,3-propanetriol
OH

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Benzene derivatives with 2 –OH groups are
name as benzenediol

OH OH OH
OH

OH
OH

1,4-benzenediol 1,3-benzenediol 1,2-benzenediol

(hydroquinone) (resorcinol) (catechol)

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 EXCERCISE

1. Name the following compounds using IUPAC nomenclature

(a)
-CH2CH(CH3)CH2-OH

(b)
-OH
NO2

(b)
-OH

Br

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PHYSICAL PROPERTIES
 Most simple alcohols are liquids
 MeOH & EtOH are volatile liquids, b.p.
65oC & 78oC respectively
 Mr , b.p.
 ROH with C > 12 are solids

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PHYSICAL PROPERTIES

 No. of –OH , b.p.

 b.p. ROH > alkane & RX because of H-
bonding
 b.p. ROH straight chain > ROH branch
 b.p. 1o ROH > 2o ROH > 3o ROH

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PHYSICAL PROPERTIES
(ii) Boiling point
 As molecular weight increase, van der Waals
forces increase, boiling point will increase too.

For isomeric alcohol (same molecular

formula)
 increase in boiling point with increasing carbon
number.
 decrease in boiling point with branching.
 boiling point in descending order:-
 1° alcohol  2° alcohol  3° alcohol
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PHYSICAL PROPERTIES (Solubility)

Alcohols and water have the ability to form

inter-molecular H-bonding
Methanol, ethanol & propanol are completely
soluble in water
Solubility decreases with relative Mr because of
the bigger hydrophobic area
Solubility increases with the no. of -OH groups

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PHYSICAL PROPERTIES (Solubility)
δ+
H
δ-
R O
Hydrophilic area
δ- H Hydrogen
O δ+ bonding
H
R OH
H
δ- δ+
R O Hydrophobic area
H
O δ+
H
δ-

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PHYSICAL PROPERTIES (Solubility)
Phenol is not completely soluble in water below
66oC, but completely soluble above this temp.
Phenol is a colourless crystalline solid which is
hygroscopic
4-nitrophenol is more soluble in water than 2-
nitrophenol because can form H-bonding with
water molecules

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PHYSICAL PROPERTIES (Solubility)
2-nitrophenol 4-nitrophenol
δ-
δ- O
δ+ O δ+ O H H
H δ- δ+
O N
δ- O
N
δ+
O
O δ+ δ-
δ- H
Intramolecular H-bonding O δ+
H H
Intermolecular H-bonding
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Acidity of phenol & alcohol

phenol > water > alcohol

 Ethanol, very weak acid & only can react with
strong base such as Na or K to produce a
conjugate base (ethoxide ion)
CH3CH2-OH CH3CH2-O- + H+

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Acidity of phenol & alcohol
 CH3CH2O- is e- richer than OH-, thus H2O
> acidic than CH3CH2OH
 Phenol > acidic than H2O & CH3CH2OH
because phenoxide ion formed is more
stable
 The phenoxide ion formed is stabilised
by resonance effect

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Acidity of phenol & alcohol

O H O -
release proton
+ H+

Phenoxide ion

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Phenoxide ion stability

O - O O O
- -

Oδ-
δ- δ-

δ-
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Example:

OH CH2CH2-OH CH2-OH OH

acidity increase

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 Example:
COOH OH

> > CH CH -OH

3 2
ACIDITY
DECREASE

Na2CO3 KOH K, Na
NaHCO3 NaOH NaH
Weak bases Strong bases Very strong bases

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 EXCERCISE

1. Arrange the following compounds in the order of increasing

boiling point. Explain your answer.
1,2-ethanediol , n-butane , 1-propanol , 1,3-propanediol

2. Predict which of the compound is more soluble in water.

Briefly explain your answer.

(a) propane & 1-propanol

(b) 1-propanol & 1,2-propanediol
(c) 2-propanol & 2-pentanol
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PREPARATION OF ALCOHOLS
1. Fermentation of carbohydrate
-fermentation of sugars by yeast to
form ethanol

C6H12O6 2CH3CH2OH + 2CO2

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PREPARATION OF ALCOHOLS
2.Hydration of Alkenes
follows Markovnikov’s rule

Example:-

CH3CH=CH2 H2O / H2SO4

CH3CH-CH3
OH

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PREPARATION OF ALCOHOLS
Mechanism

CH3CH=CH2 + H+ CH3CH-CH3 2o carbonium

+
●●
●
● OH
-

CH3CH-CH3
●
● OH
●●

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PREPARATION OF ALCOHOLS
3. Hydrolysis of Haloalkanes

RX + OH- (aq) ROH + X-

CH2Cl CH2OH

+ NaOH(aq)

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PREPARATION OF ALCOHOLS
4. Addition of Grignard reagent to
carbonyl compounds

10, 20 & 30 alcohols can be prepared by

addition of Grignard reagent with carbonyl
compounds followed by hydrolysis

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 PREPARATION OF ALCOHOLS

(a) Formation of 1o alcohols (Grignard reagent + methanal)

CH3CH2-MgCl + H2C=O CH3CH2CH2-OMgCl

methanal
H3O+

1o Alcohol CH3CH2CH2-OH
+ Mg(OH)Cl

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 PREPARATION OF ALCOHOLS

(b) Formation of 2o alcohols (Grignard reagent + aldehyde)

CH3 CH3
CH3CH2-MgCl + HC=O CH3CH2CH-OMgCl
ethanal
H3O+

CH3
2o Alcohol CH3CH2CH-OH
+ Mg(OH)Cl
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PREPARATION OF ALCOHOLS
(c) Formation of 3o alcohol (Grignard reagent + ketone)

O O-MgCl
CH3-MgCl + CH3-C-CH3 CH3-C-CH3
propanone CH3

H3O+

O-H
3o Alcohol CH3-C-CH3 + Mg(OH)Cl
CH3
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 EXCERCISE

1. Write the chemical equation for the following reaction:

i. tert-butyl alcohol from an alkene
ii. isopropyl alcohol from an alkyl halide
2. Draw the structure of A, B and C:
i. CH3 O
CH3-C-MgCl + -C-H A

ii. CH3

H2O / H+
-CH=CH-CH3 B + C

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 ALCOHOL REACTIONS
(a) As an acid

In an aqueous solution alcohol reacts as a very weak acid

ROH + H2O RO- + H3O+

Reacts with Na or NaH & form a very strong base

alkoxide ion

CH3CH2OH + Na CH3CH2O-Na+ + 1/2H2

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ALCOHOL REACTIONS
(a) As a base

With the presence of lone pair of e- at the O atom,

alcohol can accept proton from an acid

●● ●●
CH3CH2-O-H
●●
+ HA CH3CH2O+-H + A-
H

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ALCOHOL REACTIONS
(1) Esterification

Alcohol reacts with carboxylic acid under reflux & is

catalysed by mineral acids (H2SO4 or HCl)
General reaction:-

O O
H+,
R-C-OH + R’-OH R-C-OR’ + H-O-H

acid alcohol ester water

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ALCOHOL REACTIONS
(1) Esterification
Example:-

O H+, O
CH3C-OH + CH3-OH CH3C-OCH3 + H-O-H

ethanoic acid methanol methyl ethanoate

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 ALCOHOL REACTIONS
(1) Esterification
Alcohol reacts with acyl chloride to form ester

O O
base
CH3C-Cl + CH3-OH CH3C-OCH3 + HCl

ethanoil chloride methanol methyl ethanoate

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ALCOHOL REACTIONS
(2) Dehydration of alcohol
•Involve formation of carbocation
•Possible of rearrangement

H2SO4(con.)
CH3CH2CH2OH CH3CH=CH2
180 C 0

propanol propene

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ALCOHOL REACTIONS
(3) Formation of haloalkane

•ROH reacts with HX to form RX

•The reaction rates are in the order
HI > HBr > HCl (HF non-reactive)
•Reactivity of alcohols
3o ROH > 2o ROH > 1o ROH > phenol

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 ALCOHOL REACTIONS
Example:-

• ROH + HX RX + H2O

• CH3CH2CH2OH + HBr CH3CH2CH2Br + H2O

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ALCOHOL REACTIONS
(3) Formation of haloalkane
•ROH reacts with PX3, PX5 , SOCl2

General reaction:
(i) 3ROH + PX3 3RX + H3PO3
(ii) ROH + PCl5 RCl + POCl3 + HCl
(iii)ROH + SOCl2 RCl + SO2 + HCl

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ALCOHOL REACTIONS
(4) Oxidation of alcohols

• Common oxidising agents are potassium

permanganate (KMnO4/H+) and potassium
dichromate (K2Cr2O7/H+)
• Oxidation product depends on the class of
alcohol used

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ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol

• 1o R-OH can be oxidised to give an aldehyde.

Further oxidation would give a carboxylic acid

O O
[O] [O]
RCH2OH RC-H RC-OH

1o alcohol aldehyde carboxylic acid

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ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol
Example:-

O O
K2Cr2O7/H
+
K2Cr2O7/H+
CH3CH2OH CH3C-H CH3C-OH + Cr 3+

green
orange

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ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol
• Sarett-Collins reagent is a special oxidation agent
to change a 1o alcohol to an aldehyde
• CrO3 is added to excess pyridine to form
pyridinium chlorochromate (PCC)
O
CH3CH2CH2OH + PCC CH3CH2C-H

propanol propanal

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ALCOHOL REACTIONS
(4) Oxidation of 2o alcohol
• form ketone which cannot be oxidised further
under normal conditions

R R
[O]
R’CH-OH R’C=O + H2O
2o alcohol ketone

CH3 CH3
KMnO4/H+

CH3CH-OH CH3C=O + H2O

2-propanol propanone

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ALCOHOL REACTIONS
(4) Oxidation of 3o alcohol
• Does not undergo oxidation under normal
condition

R
[O]
R’-C-OH no reaction
R’’
3o alcohol

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Chemical test for R-OH
 Lucas test
• Lucas reagent : HCl + ZnCl
(con.) 2

• 3 R-OH + Lucas reagent – reacts

o

immediately to form cloudy haloalkane

• 2o R-OH + Lucas reagent –takes about 5-10
minutes
• 1o R-OH + Lucas reagent – no visible
changes unless heated

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Example: OBSERVATIONS :

CH2OH
HCl / ZnCl2 Does not turn
cloudy

OH
HCl / ZnCl2 Turn cloudy
within 5 minute
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 OBSERVATIONS :
CH3
OH Turn cloudy
HCl / ZnCl2 immediately

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Haloform Reaction
 Methyl carbinol cleavage to give Carboxylic
acids and Haloform
H
X2 , H+
CH 3 C H HCX 3 + H C OH
OH-
OH O

H
X2 , H+
CH 3 C R HCX 3 + R C OH
OH-
OH O
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 IODOFORM TEST

OH
CH3CH2CCH3 + 3I2 base (OH-)
2-butanol
CH3CH2COO- + CHI3↓
yellow precipitate
(iodoform)

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PHENOL
Manufacture of phenol by Cumene process
(a) Friedel-Crafts reaction

CH3-CH-CH3
AlCl3
+ CH3CH=CH2

Isopropylbenzene
(cumene)

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PHENOL
(b) Oxidation of Cumene
O -OH
CH3-CH-CH3
CH3-C-CH3
1200C Cumene
+ O2
hydroperoxide

(c) Decomposition & rearrangement

CH3 O
H2SO4
-C-O-OH -OH + CH3CCH3
CH3

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Phenol reactions
1. Reaction at functional group -OH
(a) Reaction with Na

OH O-Na+

+ Na + ½ H2

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Phenol reactions
1. Reaction at functional group -OH
(b) Reaction with NaOH

OH O-Na+

+ NaOH + H2 O

CH3CH2OH + NaOH no reaction

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 Phenol reactions
2. Electrophilic substitution reactions
(a) Halogenation (Bromination)
-OH is ortho-para director
in Br2, aqueous solution, white precipitate 2,4,6-
tribromophenol will form
OH OH
Br Br
+ 3Br2 / H2O + 3HBr

Br
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 Phenol reactions
2. Electrophilic substitution reactions
(a) Bromination to get monobromination (catalyst:
FeBr3 or CS2)

OH OH OH
Br
CS2
+ Br2 + + HBr
50C
Br

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 Phenol reactions
2. Electrophilic substitution reactions
(b) Nitration
OH OH
Dilute HNO3 NO2
+
Room temp.
OH
NO2

OH
O2N NO2
Concentrated HNO3 Yellow
precipitate
NO2
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 Phenol reactions
3. Esterification
phenol is a weaker nucleophile than alcohol since
the lone pair e- of O atom are delocalised to the
benzene ring
reacts with an acid derivative such as acid chloride
to form an ester
CH3
OH O-C=O
Cl
+ CH3-C=O + Cl-

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 Phenol reactions
4. Identification test for phenols
phenol reacts with aqueous solution of iron (III)
chloride giving a light purple complex

OH OH

+ FeCl3 (aq)
FeCl3
Purple
complex

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 EXERCISE 1

Suggest a chemical test to differentiate the following pairs of

compounds. State the reagents, observations and write
chemical equations involved.

(a) methanol from ethanol

(b) 2-methyl-1-propanol from 2-methyl-2-propanol
(c) cyclohexanol from cyclohexane
(d) phenol from benzyl alcohol
(e) o-methylphenol from 2-methylcyclohexanol

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 EXERCISE 2

Compound A (C4H10O) undergoes oxidation to form compound

B (C4H8O). Oxidation of B gives compound C (C4H8O2).
Reaction of A with hot concentrated sulphuric acid yields
compound D (C4H8). Hydration of D gives compound E
(C4H10O) which cannot be oxidised. A and E are isomeric.
Suggest the structure of A, B, C, D and E. Rasionalise your
answer.

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Common used of alcohol and
phenol
 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)
 Phenol is an important industrial
chemical. Major use is in phenolic resins
for adhesives and plastics.

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Phenols in Medicine
 Many phenols are used as antiseptics and
disinfectants.
OH OH OH

OH OH
CH2CH2CH2CH2CH2CH3

Phenol Resorcinol 4-Hexylresorcinal

(antiseptic) (antiseptic)
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 Derivatives of Phenol
 Compounds of phenol are the active ingredients in the
essential oils of cloves, vanilla, nutmeg, and mint.

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