CHM301 (ORGANIC CHEMISTRY)

CHAPTER 1: ALCOHOLS
Learning Outcomes

By the end of this chapter, the students should be able to:

 Alcohols vs phenols.
 Classification of alcohols.
 Nomenclature of alcohols and phenols.
 Physical properties of alcohols.
 Preparation of alcohols.
 Reactions of alcohols.
 Tests to distinguish classes of alcohols.
INTRODUCTION
ALCOHOLS VS PHENOLS

ALCOHOL PHENOL
Organic compounds Compounds with hydroxyl
containing hydroxyl (-OH) group bonded directly to
functional groups. an aromatic (benzene)
ring.
R OH OH
CLASSIFICATION OF ALCOHOL
Alcohols are categorized into three classes based on the position of -OH
group on the chain of carbon atoms.

Primary alcohols (1o) Secondary alcohols (2o) Tertiary alcohols (3o)

The carbon which carries the
–OH group is only attached
to one alkyl group.
The carbon which the -OH
group bonded is joined
directly to two alkyl groups,
which may be the same or
different.
The carbon with the -OH
group is bonded directly to
three alkyl groups, which
may be any combination of
same or different.
Classify

CH3 CH3
CH3 CH CH2OH CH3 C OH
CH3

OH OH
CH3 CH CH2CH3
NOMENCLATURE
IUPAC NAME
 Alcohols are named with the suffix –ol to replace –e in alkane.

 Longest carbon chain with –OH group is selected as parent chain.

 Numbering starts from the end closer to –OH group. If double bonds exist in
the
parent chain, the –OH group still has higher priority.
 In cyclic alcohol, the –OH group takes number one position.

 When an OH group is bonded to a ring, the ring is numbered beginning with the OH
group.

 Because the functional group is at C1, the 1 is usually omitted from the name.

 The ring is then numbered in a clockwise or counterclockwise fashion to give the next
substituent the lowest number.
UNSATURATED ALCOHOL
 Hydroxyl group takes precedence. Assign that carbon the lowest number.
 Use alkene or alkyne name.

OH
CH2 CHCH2CHCH3

4-penten-2-ol (old)
pent-4-ene-2-ol (new)
DIOLS

 Two numbers are needed to locate the two -OH groups.

 Use -diol as suffix instead of -ol.

HO OH

1,6-hexanediol
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
COMMON NAMES

 Alcohol can be named as alkyl alcohol.

 Useful only for small alkyl groups.
 Examples:

CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3

isobutyl alcohol sec-butyl alcohol

PHENOL
 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.
OH

3-chlorophenol
OH Cl meta-chlorophenol

4-methylphenol
H3C
para-cresol
PHYSICAL PROPERTIES
BOILING POINT

 The boiling points of alcohols are always higher than that of hydrocarbons
with the same number of carbon atoms.

 The boiling points of the alcohols increase with increasing number of carbon
atoms.

 The existence of intermolecular attractions; hydrogen bonding, dipole-dipole

attraction and van der Waals forces in alcohols results in higher boiling points
than hydrocarbons.

 The presence of oxygen atom in alcohol brings an extra 8 electrons. As a

result, the strength of the van der Waals dispersion forces increases and so
the boiling point.
SOLUBILITY

 Small alcohols are completely water soluble in all proportions.

 However, solubility declines as the number of carbon atom increases.
 Drastic decrease in solubility is apparent for four carbons or more, which
two layers are formed.
 Ethanol is completely soluble in water. The main intermolecular attraction in
either ethanol or water is hydrogen bonds.

Solubility decreases as the

size
of the alkyl group increases.
ACIDITY & BASICITY OF ALCOHOLS

 pKa range: 15.5-18.0 (water: 15.7)

 Acidity decreases as alkyl group increases.
 Halogens increase the acidity.
 Phenol is 100 million times more acidic than cyclohexanol .
PREPARATION OF ALCOHOLS

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ETHANOL –INDUSTRIAL PROCESS

 Industrially, ethanol is prepared by reacting ethene with steam in the

presence of a catalyst, solid silicon dioxide coated with phosphoric (V) acid.
This hydration reaches equilibrium.

H3PO4
CH2=CH2 + H2O(g) CH3CH2OH(g)

 Since only 5% of the ethene is converted into ethanol at each pass through
the reactor, ethanol formed is removed from the equilibrium.
1. GRIGNARD SYNTHESIS
REACTION OF RMgX WITH ALDEHYDES OR KETONES

 A Grignard reagent has a formula RMgX where X is a halogen, and R is an

alkyl or aryl group.

 Grignard reagents are prepared by adding the alkyl halide to small pieces of
magnesium in a flask containing ethoxyethane (diethyl ether).

 The flask is fitted with a reflux condenser, and the mixture is warmed over a
water bath for 20 - 30 minutes.

 The reaction condition must be perfectly dry because Grignard reagents

react with water.
 Br
ether MgBr
+ Mg

Cl MgCl
ether
CH3CHCH2CH3 + Mg CH3CHCH2CH3

CH3C CH2
ether
Br + Mg CH3C CH2
MgBr
REACTION OF RMgX TO FORM ALCOHOL

ether
RX + Mg RMgX
ether
CH3CH2CH2Br + Mg CH3CH2CH2MgBr

Alkylmagnesium halide (Grignard reagent) reacts with carbonyl compound to

yields alkoxide ion, which in turn reacts with acid to produce alcohols.

Alkoxide ion, RO- is a strong base that can easily accept H+ ion.

O H3O+ OH
 RMgX + – C – R – C – + Mg2+ + X- + H2O
 Addition to methanal (formaldehyde) yields primary alcohols.
O H3O+
RMgX + H – C – H R – CH2OH + Mg2+ + X- +H2O

Addition to other aldehydes yields secondary alcohols.

O H3O+ OH
RMgX + R – C – H R – CH – R + Mg2+ + X- + H2O
 
Addition to ketones yields tertiary alcohols.
O H3O+ OH
RMgX + R – C – R R – C – R + Mg2+ + X- + H2O
R
 Reactions are usually performed in diethyl ether followed by H3O+. The
type of reaction is nucleophilic addition reaction which the alkyl group in
Grignard reagent acts as nucleophile. Both aldehydes and ketones react in
the same way at –C=O.
 In the first step, the Grignard reagent attacks the carbon-oxygen double
bond:
O O-MgCl+
CH3CH2MgCl + R-C-H RCHCH2CH3

 Then, dilute acid is added to the alkoxide ion to hydrolyze it to yield

alcohol.

O-MgCl+ H3 O + OH
RCHCH2CH3 RCHCH2CH3
SYNTHESIS OF 1O ALCOHOL

Grignard + formaldehyde 1o 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
SYNTHESIS OF 2O ALCOHOL

Grignard + aldehyde 2o 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
SYNTHESIS OF 3O ALCOHOL

Grignard + ketone 3o alcohol.

CH3 H H3C CH3 CH3

H3C 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
2. HYDROLYSIS OF ALKYL HALIDES
 Alkyl halides, RX can be converted to alcohols using water or hydroxide as
the nucleophile.

 In this nucleophilic substitution reaction, the halogen atom is replaced by an

OH group to yield an alcohol.
H2 O
R-X R-OH
or OH-
 Primary, secondary and tertiary alkyl halides react with OH- to form 1o, 2o
and 3o ROH, respectively.

 The reaction follows either SN1 or SN2 mechanism, which 1o RX usually

through SN2.
 CH3CH2CH2CH2Br + NaOH CH3CHCH2CH2OH + NaBr

CH3CHCH2CH3 + NaOH CH3CHCH2CH3 + NaBr

Br OH
Both of the reactions above occur through SN2 (back side attack)
mechanism but primary RX is more reactive.

Or, as an ionic equation:

CH3CH2CH2CH2Br + OH- CH3CHCH2CH2OH + Br-
 Tertiary RX however undergoes SN1 mechanism and E1, elimination reaction.
Cl H2O, ethanol OH CH3
CH3CCH3 CH3CH3CCH3 + CH3C=CH2
CH3 65OC . CH3
(64%) (36%)
REACTION OF ALCOHOLS

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1. DEHYDRATION

a) Dehydration of alcohols using aluminum oxide as catalyst

When ethanol vapor is passed over heated aluminum oxide powder, Al2O3 the
ethanol is converted to ethene and water vapor.

CH3CH2OH CH2=CH2 + H2O

b) Dehydration of alcohols using an acid catalyst

Upon heating with strong acid, alcohols undergo dehydration to form alkenes.
The type of reaction is 1,2 or b-elimination.

H OH H+
– C – C – C = C + H – OH
heat
 Heating alcohols with strong acids catalysts (H2SO4 or H3PO4), typically
undergo a 1,2-elimination reactions to yield an alkene and water.

 The reaction is called dehydration since H2O is removed. Relative reactivity

order of alcohols: 3o > 2o > 1o

The reaction is regioselectivity according to Zaitsev’s rule

which the major product is usually the more highly
substituted alkene. The alkene formed in the dehydration
also stereoselective which the trans isomer is favorable
over the cis since the trans is more stable.
Dehydration, like dehydrohalogenation, is a  elimination reaction in which
the elements of OH and H are removed from the  and  carbon atoms
respectively.
DEHYDRATION OF ETHANOL

 Since primary alcohol is the least reactive towards dehydration, the harsh
condition is necessary for the dehydration of ethanol which required highly
concentrated H2SO4 and heat to 170oC.

Conc. H2SO4
CH3CH2OH CH2=CH2 + H2O
170oC

 Water is a better leaving group than hydroxide ion, it is appropriate to use

acid-catalysis rather than base-catalysis to achieve such reactions.
Typical acids used for alcohol dehydration are H2SO4 or p-toluene sulfonic
acid (TsOH).

More substituted alcohols dehydrate more easily, giving rise to the following
order of reactivity.
DEHYDRATION – E2 MECHANISM: 1O ALCOHOL
 Initially, protonation occurs to ethanol which one of the lone pairs of
electrons on the oxygen accepts a hydrogen ion from H2SO4.

CH3CH2OH + H2SO4 CH3CH2OH2+ + HSO4-

 Finally, a hydrogen sulfate ion (from the sulfuric acid) pulls off a hydrogen
ion from the protonated ethanol to produce ethane.

CH2 CH2 OH2+ CH2 CH2+ H2O+ H2SO4

HSO4- H
 Dehydration more complex alcohols will lead to the formation of two alkenes
due to the elimination of two possible H atoms next to positively charge C
atom in the carbocation.

 Example: Dehydration of 2-butanol.

Step 1: 2-butanol is protonated by picking up a hydrogen ion from the

H2SO4.
Step 2: Water molecule is eliminated form the protonated alcohol and produces
a carbocation.  

Step 3: Removal of H+ ion by HSO4- to form an alkene.

There are two possible alkenes formed in this dehydration which the removal of
H+ ion from CH3 to the left of positively charged carbon or from CH2 on the
right to form alkene.
1st: If H+ ion is lost from the CH3 group, 1-butene is formed.

 
2nd: If H+ ion is lost from the CH2 group, the product is 2-butene.
ZAITSEV’S RULE
 Based on the Zaitsev’s rule, 2-butene is the major product.

 2-butene exhibits geometric isomerism; cis-2-butene and trans-2-butene.

2. ALKOXIDE FORMATION

The reaction between sodium and ethanol

When a small piece of sodium metal is placed into ethanol, it reacts steadily
to release hydrogen gas and produces a colorless solution of sodium
ethoxide, CH3CH2ONa. Sodium ethoxide is known as an alkoxide. Upon drying,
a white crystal of sodium ethoxide formed.

2CH3CH2OH + 2Na 2CH3CH2O-Na+ + H2

3. HALOGENATION – NUCLEOPHILIC SUBSTITUTION

Reactions with HX (Nucleophilic Substitution)

H – X + – C – OH – C – X + H – OH

 Alcohols react readily with hydrogen halides, HX to yield alkyl halides, RX. 

 The reaction is carried out by passing through gaseous hydrogen halide

into alcohol or heating alcohol with concentrated aqueous acid (HCl, HBr,
HI).

 The reaction is nucleophilic substitution reaction – SN1

 The reaction of alcohols with HX (X = Cl, Br, I) is a general method to
prepare 1°, 2°, and 3° alkyl halides.

 Alcohol relative reactivity order for the halogenation is 3o > 2o > 1o >
methyl.

 Reactivity order of hydrogen halides is HI > HBr > HCl.

 The reaction of alcohols with HCl in the presence of ZnCl2 (catalyst) forms
the basis of the Lucas test for alcohols.
 More substituted alcohols usually react more rapidly with HX:

This order of reactivity can be

rationalized by considering the
reaction mechanisms involved.
The mechanism depends on
the structure of the R group.
REACTION OF 3o ALCOHOL WITH HCl

 3o alcohols react reasonably rapidly with concentrated HCl acid, but for 1o or
2o alcohols the reaction rates are too slow.

 A 3o alcohol such as tert-butanol reacts if it is shaken with concentrated HCl

acid at room temperature. A tertiary haloalkane or alkyl halide is formed.

CH3 CH3
CH3C-OH + HCl CH3C-Cl + H2O
CH3 CH3
REACTION WITH HBr

 Instead of using HBr acid, alcohol is treated with a mixture of NaBr or KBr
and concentrated H2SO4 acid.

 This produces HBr which reacts with the alcohol.

 The mixture is warmed to distill off the bromoalkane (alkyl bromide).

H2 O
CH3CH2CH2CH2OH + HBr CH3CH2CH2CH2Br + H2O
reflux
REACTION WITH HI

When alcohol is treated with NaI or KI and concentrated phosphoric(V) acid,

H3PO4, and the iodoalkane (alkyl iodide) is formed.

CH3CH2CH2OH + HI CH3CH2CH2I + H2O

CH2OH + HI CH2I + H2O

REACTION OF ROH WITH PX3 AND SOCl2

 Primary and secondary alcohols can also be converted to RX using thionyl

chloride, SOCl2 or phosphorous tribromide,PBr3.

 In each case a base is used to neutralize the acidic by-product. Common

bases used are triethylamine (Et3N), or pyridine (C5H5N).

pyridine
– C – OH + PBr3 – C – Br + H3PO3 + HBr

pyridine
– C – OH + PI3 – C – I + H3PO3 + HI

pyridine
– C – OH + SOCl2 – C – Cl + SO2 + HCl

Trimethylamine can also be used as a base

4. OXIDATION

Only 1o and 2o ROH can oxidize using inorganic oxidizing

agents, such as KMnO4, CrO3, and Na2Cr2O7 or by more
selective, expensive reagents.
 Primary alcohols:
CH3CH2CH2-OH + KMnO4  CH3CH2CO2H
carboxylic acid
 Secondary alcohols:

OH
CH3CH2CHCH3 + K2Cr2O7  CH3CH2COCH3

ketone

 Tertiary alcohols: no reaction

PARTIAL OXIDATION TO ALDEHYDE

Oxidation of 1o alcohols with a mild oxidizing agent such as pyridinium

chlorochromate (PCC), C5H5NH+CrO3Cl- in dichloromethane, CH2Cl2 as solvent
yield aldehydes (RCHO).

CH3CH2CH2OH + C5H5NHCrO3Cl  CH3CH2CHO

pyridinium chlorochromate aldehyde

When excess alcohol is treated with Cr2O72- in dilute H2SO4 aldehyde is

also formed.

3CH3CH2CH2OH + Cr2O72- + 8H+  3CH3CH2CHO + 2Cr3+ + 7H2O

COMPLETE OXIDATION TO RCO2H

The equation is simplified as:

Cr2O72-, H+
  RCH2OH RCO2H
H2O, heat 
2o alcohols are oxidized to ketones. When alcohol is treated with chromic
acid, H2CrO4 (in acetone) or potassium dichromate(VI), K2Cr2O7 solution
acidified with dilute H2SO4, and heated, a ketone is formed.

OH oxidation . O
R – CH – R R – C – R
reduction
OH . O
3RCHR + 2H2CrO4 + 6H+ 3RCR + 2Cr3++8H2O
5. ESTERIFICATION

Simple alcohol reacts with carboxylic acid when heated in mineral acid to
form ester. The reaction is reversible, which ester is hydrolyzed in acid into
carboxylic acid.

O H2SO4 O
R – C – OH + ROH R – C – OR + H – OH
Heat or reflux
 
"Lasso" chemistry
O H+ O
R C + H-O-R' R C + H2O
O H O R'

O CH3 O
H+ CH3 + H2O
CH3C + H-O CHCH3 CH3C
O H O CHCH3

acetic acid isopropyl alcohol isopropyl acetate

 Another common esterification method is through the reaction between acyl
and alcohol in the presence of a base such as pyridine, C5H5N.

O O
R – C – Cl + RO - H R – C – OR

acid chloride + alcohol --> ester

O H+ O
R C + H-O-R' R C + HCl
Cl O R'

O CH3 O
H+ CH3 + HCl
CH3C + H-O CHCH3 CH3C
Cl O CHCH3

acetyl chloride isopropyl alcohol isopropyl acetate

CHEMICAL TESTS FOR ALCOHOLS

 Oxidation of alcohols usually used to identify the class of alcohols.

 The reaction is useful because the oxidizing agent is reduced in the process.

 Since the aqueous solutions of the oxidizing agents change color with the
change in oxidation number, we can easily observe the change and be able
to identify whether the test is positive or not.
1. OXIDATION (Test with dichromate solution)
 In the case of a primary or secondary alcohol, the orange solution turns
green, Cr3+ which oxidation number of chromium reduces from +6 to +3.

 The orange color does not change when treated with tertiary alcohol.

 Partial oxidation of primary alcohol to aldehyde;

3CH3CH2CH2OH+Cr2O72- + 8H+ 3CH3CH2CHO+2Cr3 + 7H2O

 Oxidation of primary alcohol to carboxylic acid;

3RCH2OH+2Cr2O72-+16H+ 3RCO2H+4Cr3++11H2O

 Oxidation of secondary alcohol to ketone;  

OH O
3R–CH–R+2H2CrO4 + 6H+ 3R–C–R + 2Cr3+ + 8H2O  
2. SCHIFF TEST (Distinguishing 1o & 2o alcohol)

 A quite reliable test to distinguish between 1o and 2o alcohols is Schiff's test.

 Schiff's reagent is decolorized by passing sulfur dioxide through it.
 In the presence of even small amounts of an aldehyde (from primary alcohol),
it turns bright magenta.

 If the Schiff's reagent quickly turns magenta (reddish purple), an aldehyde is

formed from a primary alcohol.
 If the color does not change, or only a trace of pink color formed within a
minute or so, aldehyde does not formed and the compound is not a primary
alcohol.
 Since the color change when treated with acidified potassium dichromate (VI)
solution, then the compound is a secondary alcohol.
3. LUCAS TEST (Confirmation of 3o alcohol)
 Lucas reagent is a mixture of concentrated hydrochloric acid, HCl and zinc
chloride, ZnCl2.

 Alcohols with less than six carbons are soluble in Lucas reagent.

 A primary alcohol is the least reactive towards Lucas reagent.

 Insoluble alkyl chloride is formed when alcohol is added to Lucas reagent.

 A tertiary alcohol reacts instantaneously with Lucas reagent, a secondary

alcohol reacts within five minutes.
Formation of insoluble alkyl chloride is observed by the
appearance of cloudiness in the solution.
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