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Alcohols and Phenols

Name

Functional Group
Structure

Example Compound

Official Name of Example


(Common Name)
Formal Name Ending

alcohol

methanol
(methyl alcohol)
-ol endings

phenol

phenol
(phenol)
-ol endings

Alcohols
A hydroxyl group is a hydrogen bonded to an oxygen that is covalently bonded to
the rest of the molecule. Just as with alkenes, alkynes, and ketones, the location of
the hydroxyl group is made by numbering the molecule such that the hydroxyl
group has the lowest number possible.

is 2-pentanol
Alcohols are subdivided by examining the carbon to which the hydroxyl group is
bonded. If this carbon is bonded to one other carbon atom, it is a primary (1 o)
alcohol. If this carbon is bonded to two other carbons, it is a secondary (2 o) alcohol.
If it is bonded to three other carbons, it is a tertiary (3 o) alcohol.

is 1o

is 2o

is 3o
Phenols
When the hydroxyl group is bonded directly to a benzene ring, the compound is
classified as a phenol. Naming phenols can be done in many ways.

is resorcinol.

Phenol, also known as carbolic acid, is an organic compound with the formula C6H5OH. It is a
white crystalline solid that is volatile. The molecule consists of a phenyl group (-C6H5) bonded to
a hydroxyl group (-OH). It is mildly acidic, but requires careful handling due to its propensity to cause
burns.
Phenol was first extracted from coal tar, but today is produced on a large scale (about 7 billion
kg/year) from petroleum. It is an important industrial commodity as a precursor to many materials and
useful compounds.[4] Its major uses involve its conversion to plastics or related materials. Phenol and
its chemical derivatives are key for
building polycarbonates, epoxies, Bakelite, nylon,detergents, herbicides such as phenoxy herbicides,
and numerous pharmaceutical drugs.

What is the difference between phenols and alcohols?


a. phenols are alcohols with aromatic rings
b. phenol has no hydroxyl group
c. phenols are not alcohols
d. none of the above
One thing is the difference in functional group.
Another is their reactivity.
The last major difference and it is related to the above is their
physical properties.
O-CHEM the only good chemisty.

In organic chemistry, phenols, sometimes called phenolics, are a


class of chemical compounds consisting of a hydroxyl group (-OH)
bonded directly to an aromatic hydrocarbon group. The simplest
of the class is phenol (C6H5OH).
This article is about the chemistry term. For the beverage, see
Alcoholic beverage. For other uses, see Alcohol (disambiguation).
Functional group of an alcohol molecule. The carbon atom is
bound to hydrogen atoms and may bind to other carbon atom(s)
to form a carbon chain. Methanol, an alcohol with a single carbon
atom, is pictured. Ethanol, which is drinking alcohol, has two
carbon atoms.In chemistry, an alcohol is any organic compound in

which a hydroxyl group (-OH) is bound to a carbon atom of an


alkyl or substituted alkyl group. The general formula for a simple
acyclic alcohol is CnH2n+1OH. In common terms, the word
alcohol refers to ethanol, the type of alcohol found in alcoholic
beverages.

Aldehydes, Ketones, Quinones and Derivatives


(See also oximes, azines etc. under Nitrogen)
Quick move to entries starting with the letters C, D, H, K, Q or X.

acetals:*
Compounds having the structure R C(OR') (R' not equal to H) and thus diethers of
geminal diols. Originally, the term was confined to derivatives of aldehydes (one R
= H), but now it applies equally to derivatives ofketones (neither R = H). NOC
Rule C-331, GNOC Recom. R-5.6.4.1. Mixed acetals have different R' groups. See
also acetonides, ketals. Cf. acylals, hemiacetals.
2

acyloins:*
-Hydroxy ketones, RCH(OH)C(=O)R. NOC Rule C-333. So named from the fact
that they are formally derived from reductive coupling of carboxylic acyl groups.
See also ketones.
aldehydes:*
Compounds RC(=O)H, in which a carbonyl group is bonded to one hydrogen atom
and to one R group. NOC Rule C-301.1.
carbonyl compounds:
1. Compounds containing the carbonyl group, C=O. The term is commonly used in
the restricted sense of aldehydes and ketones, although it actually
includes carboxylic acids and derivatives. See under oxo compounds.
2. Metal carbonyls, in which carbon monoxide is a formal ligand.
diosphenols:
Cyclic -diketones, which exist predominantly in an enolic form.
dypnones:

1,3-Diphenylbut-2-en-1-one [PhC(=O)CH=C(CH )Ph] and its ring-substituted


derivatives.
3

hemiacetals:*
Compounds having the general formula R C(OH)OR' (R' not equal to H). NOC
Rule C-331.4. GNOC Recom. R-5.6.4.2. See also lactols, hemiketals.
2

hemiketals:*
Hemiacetals having the structure R C(OH)OR (R not equal to H), derived
from ketones by formal addition of an alcohol to the carbonyl group. This term,
once abandoned (NOC Rule C-331.4, footnote) has been reinstated as a subclass
of hemiacetals. GNOC Recom. R-5.6.4.2.
2

ketals:*
Acetals derived from ketones by replacement of the oxo group by two
hydrocarbyloxy groups: R C(OR) (R not equal to H). This term, once abandoned
(NOC Rule C-333.1), has been reinstated (GNOC Recom. R-5.6.4.1) as a subclass
of acetals.
2

ketenes:*
Compounds in which a carbonyl group is connected by a double bond to
an alkylidene group: R C=C=O. NOC Rule C-321.
2

keto: see under oxo compounds.


ketones:*
Compounds in which a carbonyl group is bonded to two carbon atoms: R C=O
(neither R may be H). NOC Rule C-311.1. Note: Compounds of structure such as
R SiC(=O)R are not ketones but acyl derivatives of substituted silanes.
2

quinhydrones:
Molecular complexes of one equivalent amount of a quinone with one equivalent
amount of the corresponding hydroquinone.

quinomethanes:
Methylidenecyclohexadienones and dimethylidenecyclohexadienes, formally
derived from quinones by replacement of one or both of the quinone oxygens by
methylidene groups. (The diradical, triplet state of quinodimethanes can also be
called o- or p-xylylenes).
p-quinomethane,

p-quinodimethane

quinomethides/quinone methides: Undesirable names for quinomethanes.


quinones:*
Compounds having a fully conjugated cyclic dione structure, such as that of
benzoquinones, derived from aromatic compounds by conversion of an even
number of -CH= groups into -C(=O)- groups with any necessary rearrangement of
double bonds (polycyclic and heterocyclic analogues are included). NOC Rule C317.
p-benzoquinone
xylylenes: See under quinomethanes.

11. Alcohols, Phenols and


Ethers
Alcohols, phenols and ethers are the basic compounds for the formation of
detergents, antiseptics and fragrances, respectively.
You have learnt that substitution of one or more hydrogen atom(s) from a
hydrocarbon by another atom or a group of atoms result in the formation of
an entirely new compound having altogether different properties and
applications. Alcohols and phenols are formed when a hydrogen atom in a
hydrocarbon, aliphatic and aromatic respectively, is replaced by OH group.
These classes of compounds find wide applications in industry as well as in
day-to-day life. For instance, have you ever noticed that ordinary spirit used
for polishing wooden furniture is chiefly a compound containing hydroxyl
group, ethanol. The sugar we eat, the cotton used for fabrics, the paper we
use for writing, are all made up of compounds containing OH groups. Just
think of life without paper; no note-books, books, news- papers, currency
notes, cheques, certificates, etc. The magazines carrying beautiful
photographs and interesting stories would disappear from our life. It would
have been really a different world.
An alcohol contains one or more hydroxyl (OH) group(s) directly attached to
carbon atom(s), of an aliphatic system (CH OH) while a phenol contains OH
group(s) directly attached to carbon atom(s) of an aromatic system (C H OH).
3

The subsitution of a hydrogen atom in a hydrocarbon by an alkoxy or aryloxy


group (RO/ArO) yields another class of compounds known as ethers, for
example, CH OCH (dimethyl ether). You may also visualise ethers as
compounds formed by substituting the hydrogen atom of hydroxyl group of
an alcohol or phenol by an alkyl or aryl group.
In this unit, we shall discuss the chemistry of three classes of compounds,
namely alcohols, phenols and ethers.
3

11.1 Classification
The classification of compounds makes their study systematic and hence
simpler. Therefore, let us first learn how are alcohols, phenols and ethers
classified?
11.1.1 Mono, Di, Tri or Polyhydric Compounds
Alcohols and phenols may be classified as mono, di, tri- or polyhydric
compounds depending on whether they contain one, two, three or many

hydroxyl groups respectively in their structures as given below:

Monohydric alcohols may be further classified according to the hybridisation


of the carbon atom to which the hydroxyl group is attached.
(i) Compounds containing C OH bond: In this class of alcohols, the OH
group is attached to an sp hybridised carbon atom of an alkyl group. They
are further classified as follows:
sp

Primary, secondary and tertiary alcohols: In these three types of alcohols, the
OH group is attached to primary, secondary and tertiary carbon atom,
respectively as depicted below:

Allylic alcohols: In these alcohols, the OH group is attached to a


sp hybridised carbon next to the carbon-carbon double bond, that is to an
allylic carbon. For example
3

Benzylic alcohols: In these alcohols, the OH group is attached to a sp


hybridised carbon atom next to an aromatic ring. For example
3

Allylic and benzylic alcohols may be primary, secondary or tertiary.


(ii) Compounds containing C OH bond: These alcohols contain OH
group bonded to a carbon-carbon double bond i.e., to a vinylic carbon or to
an aryl carbon. These alcohols are also known as vinylic alcohols.
2
sp

11.1.2 Ethers
Ethers are classified as simple or symmetrical, if the alkyl or aryl groups
attached to the oxygen atom are the same, and mixed or unsymmetrical, if
the two groups are different. Diethyl ether, C H OC H , is a symmetrical ether
whereas C H OCH and C H OC H are unsymmetrical ethers.
2

Intext Questions
11.1 Classify the following as primary, secondary and tertiary alcohols:
11.2 Identify allylic alcohols in the above examples.
11.2 Nomenclature
(a) Alcohols: The common name of an alcohol is derived from the common
name of the alkyl group and adding the word alcohol to it. For example,
CH OH is methyl alcohol.
According to IUPAC system (Unit 12, Class XI), the name of an alcohol is
derived from the name of the alkane from which the alcohol is derived, by
substituting e of alkane with the suffix ol. The position of substituents are
indicated by numerals. For this, the longest carbon chain (parent chain) is
numbered starting at the end nearest to the hydroxyl group. The positions of
the OH group and other substituents are indicated by using the numbers of
carbon atoms to which these are attached. For naming polyhydric alcohols,
the e of alkane is retained and the ending ol is added. The number of OH
3

groups is indicated by adding the multiplicative prefix, di, tri, etc., before ol.
The positions of OH groups are indicated by appropriate locants e.g., HO
CH CH OH is named as ethane1, 2-diol. Table 11.1 gives common and
IUPAC names of a few alcohols as examples.
2

COMPOUND

COMMON NAME

I U PAC N A M E

CH -OH

Methyl alcohol

Methanol

n-Propyl alcohol

propan-1-ol

Isopropyl alcohol

propan-2-ol

n-Butyl alcohol

Butan-1-ol

sec-Butyl alcohol

Butan-2-ol

Isobutyl alcohol

2-methylpropane-1-ol

tert-Butyl alcohol

2-Methylpropan-2-ol

Glycerol

Propane-1,2,2-triol

CH -CH -CH -OH


3

CH -CH -CH -CH -OH


3

Table 11.1: Common and IUPAC Names of Some Alcohols


Cyclic alcohols are named using the prefix cyclo and considering the OH
group attached to C1.

(b) Phenols: The simplest hydroxy derivative of benzene is phenol. It is its


common name and also an accepted IUPAC name. As structure of phenol
involves a benzene ring, in its substituted compounds the terms ortho (1,2disubstituted), meta (1,3-disubstituted) and para (1,4-disubstituted) are often
used in the common names.

Dihydroxy derivatives of benzene are known as 1, 2-, 1, 3- and 1, 4benzenediol.

(c) Ethers: Common names of ethers are derived from the names of alkyl/aryl
groups written as separate words in alphabetical order and adding the word
ether at the end. For example, CH OC H is ethylmethyl ether. If both the
alkyl groups are the same, the prefix di is added before the alkyl group. For
example, C H OC H is diethyl ether.
According to IUPAC system of nomenclature, ethers are regarded as
hydrocarbon derivatives in which a hydrogen atom is replaced by an OR or
OAr group, where R and Ar represent alkyl and aryl groups, respectively. The
larger (R) group is chosen as the parent hydrocarbon. The names of a few
ethers are given as examples in Table 11.2.
3

COMPOUND

COMMON NAME

I U PAC N A M E

CH OCH

Dimethyl ether

Methoxymethane

Diethyl ether

Ethoxyethane

C H OC H
2

CH OCH CH CH

Methyl n-propyl
ether

C H OCH

Methylphenyl ether Methoxybenzene


(Anisole)
(Anisole)

Ethylphenyl
ether(Phenetole)

C H OCH CH
6

C H O(CH ) -CH
6

Ethoxybenzene

Heptylphenyl ether 1-phenoxyheptane

CH -O-CH -CH -OCH

1-Methoxypropane

Methyl isopropyl
ether

2-Methoxypropane

Phenylisopentyl
ether

3Methylbutoxybenzene

1,2-Dimethoxyethne

2-Ethoxy-1,1dimethylcyclohexane

Table 11.2: Common and IUPAC Names of Some Ethers


Example 11.1
Give IUPAC names of the following compounds:

Solution
(i) 4-Chloro-2,3-dimethylpentan-1-ol
(ii) 2-Ethoxypropane
(iii) 2,6-Dimethylphenol
(iv) 1-Ethoxy-2-nitrocyclohexane

Intext Question
11.3 Name the following compounds according to IUPAC system.

11.3 Structure of Functional Groups


In alcohols, the oxygen of the OH group is attached to carbon by a sigma
( ) bond formed by the overlap of a sp hybridised orbital of carbon with a
sp hybridised orbital of oxygen. Fig. 11.1 depicts structural aspects of
methanol, phenol and methoxymethane.
3

The bond angle


in alcohols is slightly less than the tetrahedral angle
(109-28). It is due to the repulsion between the unshared electron pairs of
oxygen. In phenols, the OH group is attached to sp hybridised carbon of an
aromatic ring. The carbon oxygen bond length (136 pm) in phenol is slightly
less than that in methanol. This is due to (i) partial double bond character on
account of the conjugation of unshared electron pair of oxygen with the
aromatic ring (Section 11.4.4) and (ii) sp hybridised state of carbon to which
oxygen is attached.
In ethers, the four electron pairs, i.e., the two bond pairs and two lone pairs
of electrons on oxygen are arranged approximately in a tetrahedral
arrangement. The bond angle is slightly greater than the tetrahedral angle
due to the repulsive interaction between the two bulky (R) groups. The CO
bond length (141 pm) is almost the same as in alcohols.
2

11.4 Alcohols and Phenols

11.4.1 Preparation of Alcohols


Alcohols are prepared by the following methods:
1. From alkenes
(i) By acid catalysed hydration: Alkenes react with water in the presence of
acid as catalyst to form alcohols. In case of unsymmetrical alkenes, the
addition reaction takes place in accordance with Markovnikovs rule (Unit 13,
Class XI).

Mechanism
The mechanism of the reaction involves the following three steps:
Step 1: Protonation of alkene to form carbocation by electrophilic attack of
HO .
HO + H HO
3
2

(ii) By hydroborationoxidation: Diborane (BH ) reacts with alkenes to give


trialkyl boranes as addition product. This is oxidised to alcohol by hydrogen
3

peroxide in the presence of aqueous sodium hydroxide.

The addition of borane to the double bond takes place in such a manner that
the boron atom gets attached to the sp carbon carrying greater number of
hydrogen atoms. The alcohol so formed looks as if it has been formed by the
addition of water to the alkene in a way opposite to the Markovnikovs rule. In
this reaction, alcohol is obtained in excellent yield.
2

2. From carbonyl compounds


(i) By reduction of aldehydes and ketones: Aldehydes and ketones are
reduced to the corresponding alcohols by addition of hydrogen in the
presence of catalysts (catalytic hydrogenation). The usual catalyst is a finely
divided metal such as platinum, palladium or nickel. It is also prepared by
treating aldehydes and ketones with sodium borohydride (NaBH ) or lithium
aluminium hydride (LiAlH ). Aldehydes yield primary alcohols whereas
ketones give secondary alcohols.
4

(ii) By reduction of carboxylic acids and esters: Carboxylic acidsv are reduced
to primary alcohols in excellent yields by lithium aluminium hydride, a strong
reducing agent.

However, LiAlH is an expensive reagent, and therefore, used for preparing


special chemicals only. Commercially, acids are reduced to alcohols by
converting them to the esters (Section 11.4.4), followed by their reduction
using hydrogen in the presence of catalyst (catalytic hydrogenation).
4

3. From Grignard reagents


Alcohols are produced by the reaction of Grignard reagents (Unit 10, Class
XII) with aldehydes and ketones.
The first step of the reaction is the nucleophilic addition of Grignard reagent
to the carbonyl group to form an adduct. Hydrolysis of the adduct yields an
alcohol.

The overall reactions using different aldehydes and ketones are as follows:

You will notice that the reaction produces a primary alcohol with methanal, a
secondary alcohol with other aldehydes and tertiary alcohol with ketones.
Example 11.2
Give the structures and IUPAC names of the products expected from the
following reactions:
(a) Catalytic reduction of butanal.
(b) Hydration of propene in the presence of dilute sulphuric acid.
(c) Reaction of propanone with methylmagnesium bromide followed by
hydrolysis.
Solution

11.4.2 Preparation of Phenols


Phenol, also known as carbolic acid, was first isolated in the early nineteenth
century from coal tar. Nowadays, phenol is commercially produced
synthetically. In the laboratory, phenols are prepared from benzene
derivatives by any of the following methods:
1. From haloarenes
Chlorobenzene is fused with NaOH at 623K and 320 atmospheric pressure.
Phenol is obtained by acidification of sodium phenoxide so produced (Unit 10,
Class XII).

2. From benzenesulphonic acid


Benzene is sulphonated with oleum and benzene sulphonic acid so formed is
converted to sodium phenoxide on heating with molten sodium hydroxide.
Acidification of the sodium salt gives phenol.

3. From diazonium salts


A diazonium salt is formed by treating an aromatic primary amine with
nitrous acid (NaNO + HCl) at 273-278 K. Diazonium salts are hydrolysed to
phenols by warming with water or by treating with dilute acids (Unit 13, Class
XII).
2

4. From cumene
Phenol is manufactured from the hydrocarbon, cumene. Cumene
(isopropylbenzene) is oxidised in the presence of air to cumene
hydroperoxide. It is converted to phenol and acetone by treating it with dilute
acid. Acetone, a by-product of this reaction, is also obtained in large

quantities by this method.

Intext Questions
11.4 Show how are the following alcohols prepared by the reaction of a
suitable Grignard reagent on methanal ?

11.5 Write structures of the products of the following reactions:

11.4.3 Physical Properties


Alcohols and phenols consist of two parts, an alkyl/aryl group and a hydroxyl
group. The properties of alcohols and phenols are chiefly due to the hydroxyl
group. The nature of alkyl and aryl groups simply modify these properties.
Boiling Points
The boiling points of alcohols and phenols increase with increase in the
number of carbon atoms (increase in van der Waals forces). In alcohols, the
boiling points decrease with increase of branching in carbon chain (because
of decrease in van der Waals forces with decrease in surface area).

The OH group in alcohols and phenols is involved in intermolecular hydrogen


bonding as shown below:

It is interesting to note that boiling points of alcohols and phenols are higher
in comparison to other classes of compounds, namely hydrocarbons, ethers,
haloalkanes and haloarenes of comparable molecular masses. For example,
ethanol and propane have comparable molecular masses but their boiling
points differ widely. The boiling point of methoxymethane is intermediate of
the two boiling points.

The high boiling points of alcohols are mainly due to the presence of
intermolecular hydrogen bonding in them which is lacking in ethers and
hydrocarbons.
Solubility
Solubility of alcohols and phenols in water is due to their ability to form
hydrogen bonds with water molecules as shown. The solubility decreases with
increase in size of alkyl/aryl (hydro- phobic) groups. Several of the lower
molecular mass alcohols are miscible with water in all proportions.

Example 11.4.4 Arrange the following sets of compounds in order of their


increasing boiling points:
(a) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan-1-ol, methanol.
(b) Pentan-1-ol, n-butane, pentanal, ethoxyethane.
Solution
(a) Methanol, ethanol, propan-1-ol, butan-2-ol, butan-1-ol, pentan-1-ol.
(b) n-Butane, ethoxyethane, pentanal and pentan-1-ol.
11.4.4 Chemical Reactions
Alcohols are versatile compounds. They react both as nucleophiles and
electrophiles. The bond between OH is broken when alcohols react as
nucleophiles.

(ii) The bond between CO is broken when they react as electrophiles.


Protonated alcohols react in this manner.

Based on the cleavage of OH and CO bonds, the reactions of alcohols and


phenols may be divided into two groups:
(a) Reactions involving cleavage of OH bond
1. Acidity of alcohols and phenols
(i) Reaction with metals: Alcohols and phenols react with active metals such
as sodium, potassium and aluminium to yield corresponding

alkoxides/phenoxides and hydrogen.

In addition to this, phenols react with aqueous sodium hydroxide to form


sodium phenoxides.

The above reactions show that alcohols and phenols are acidic in nature. In
fact, alcohols and phenols are Brnsted acids i.e., they can donate a proton to
a stronger base (B:).
(ii) Acidity of alcohols: The acidic character of alcohols is due to the polar
nature of OH bond. An electron-releasing group (CH , C H ) increases
electron density on oxygen tending to decrease the polarity of O-H bond. This
decreases the acid strength. For this reason, the acid strength of alcohols
decreases in the following order:
3

Alcohols are, however, weaker acids than water. This can be illustrated by the
reaction of water with an alkoxide.

This reaction shows that water is a better proton donor (i.e., stronger acid)
than alcohol. Also, in the above reaction, we note that an alkoxide ion is a
better proton acceptor than hydroxide ion, which suggests that alkoxides are
stronger bases (sodium ethoxide is a stronger base than sodium hydroxide).
Alcohols act as Bronsted bases as well. It is due to the presence of unshared
electron pairs on oxygen, which makes them proton acceptors.
(iii) Acidity of phenols: The reactions of phenol with metals (e.g., sodium,
aluminium) and sodium hydroxide indicate its acidic nature. The hydroxyl
group, in phenol is directly attached to the sp hybridised carbon of benzene
ring which acts as an electron withdrawing group. Due to this, the charge
distribution in phenol molecule, as depicted in its resonance structures,
causes the oxygen of OH group to be positive.
2

The reaction of phenol with aqueous sodium hydroxide indicates that phenols
are stronger acids than alcohols and water. Let us examine how a compound
in which hydroxyl group attached to an aromatic ring is more acidic than the
one in which hydroxyl group is attached to an alkyl group.
The ionisation of an alcohol and a phenol takes place as follows:

Due to the higher electronegativity of sp hybridised carbon of phenol to


which OH is attached, electron density decreases on oxygen. This increases
the polarity of OH bond and results in an increase in ionisation of phenols
than that of alcohols. Now let us examine the stabilities of alkoxide and
phenoxide ions. In alkoxide ion, the negative charge is localised on oxygen

while in phenoxide ion, the charge is delocalised. The delocalisation of


negative charge (structures I-V) makes phenoxide ion more stable and
favours the ionisation of phenol. Although there is also charge delocalisation
in phenol, its resonance structures have charge separation due to which the
phenol molecule is less stable than phenoxide ion.

In substituted phenols, the presence of electron withdrawing groups such as


nitro group, enhances the acidic strength of phenol. This effect is more
pronounced when such a group is present at ortho and para positions. It is
due to the effective delocalisation of negative charge in phenoxide ion. On
the other hand, electron releasing groups, such as alkyl groups, in general, do
not favour the formation of phenoxide ion resulting in decrease in acid
strength. Cresols, for example, are less acidic than phenol.

COMPOUND

FORMULA

o-Nitrophenol

o-O N-C H -OH

7.2

m-Nitrophenol

o-O N-C H -OH

8.3

Phenol

C H -oH

10.0

o-Cresol

o-CH -C H - OH

10.2

m-Cresol

m-CH C H -OH

10.1

p-Cresol

p-CH -C H -OH

10.2

Ethanol

C H OH

15.9

PKA

Table 11.3: pK Values of some Phenols and Ethanol


a

From the above data, you will note that phenol is million times more acidic
than ethanol.

Example 11.4
Arrange the following compounds in increasing order of their acid strength:
Propan-1-ol, 2,4,6-trinitrophenol, 3-nitrophenol, 3,5-dinitrophenol,phenol, 4methylphenol.
Solution
Propan-1-ol, 4-methylphenol, phenol, 3-nitrophenol, 3,5-dinitrophenol,2,4, 6trinitrophenol.
2. Esterification
Alcohols and phenols react with carboxylic acids, acid chlorides and acid
anhydrides to form esters.

The reaction with carboxylic acid and acid anhydride is carried out in the
presence of a small amount of concentrated sulphuric acid. The reaction is
reversible, and therefore, water is removed as soon as it is formed. The
reaction with acid chloride is carried out in the presence of a base (pyridine)
so as to neutralise HCl which is formed during the reaction. It shifts the
equilibrium to the right hand side. The introduction of acetyl (CH CO) group in
alcohols or phenols is known as acetylation. Acetylation of salicylic acid
produces aspirin.
3

(b) Reactions involving cleavage of carbon oxygen (CO) bond in alcohols


The reactions involving cleavage of CO bond take place only in alcohols.
Phenols show this type of reaction only with zinc.
1. Reaction with hydrogen halides: Alcohols react with hydrogen halides to
form alkyl halides (Refer Unit 10, Class XII).
ROH + HX RX + H O
The difference in reactivity of three classes of alcohols with HCl distinguishes
them from one another (Lucas test). Alcohols are soluble in Lucas reagent
(conc. HCl and ZnCl ) while their halides are immiscible and produce turbidity
in solution. In case of tertiary alcohols, turbidity is produced immediately as
2

they form the halides easily. Primary alcohols do not produce turbidity at
room temperature.
2. Reaction with phosphorus trihalides: Alcohols are converted to alkyl
bromides by reaction with phosphorus tribromide (Refer Unit 10, Class XII).
3. Dehydration: Alcohols undergo dehydration (removal of a molecule of
water) to form alkenes on treating with a protic acid e.g., concentrated
H SO or H PO , or catalysts such as anhydrous zinc chloride or alumina (Unit
13, Class XI).
2

Ethanol undergoes dehydration by heating it with concentrated H SO at 443


K.
2

Secondary and tertiary alcohols are dehydrated under milder conditions. For
example

Thus, the relative ease of dehydration of alcohols follows the following order:
Tertiary > Secondary > Primary
The mechanism of dehydration of ethanol involves the following steps:
Mechanism
Step 1: Formation of protonated alcohol.

Step 2: Formation of carbocation: It is the slowest step and hence, the rate
determining step of the reaction.

Step 3: Formation of ethene by elimination of a proton.

The acid used in step 1 is released in step 3. To drive the equilibrium to the
right, ethene is removed as it is formed.
4. Oxidation: Oxidation of alcohols involves the formation of a carbonoxygen double bond with cleavage of an O-H and C-H bonds.

Such a cleavage and formation of bonds occur in oxidation reactions. These


are also known as dehydrogenation reactions as these involve loss of
dihydrogen from an alcohol molecule. Depending on the oxidising agent used,
a primary alcohol is oxidised to an aldehyde which in turn is oxidised to a
carboxylic acid.

Strong oxidising agents such as acidified potassium permanganate are used


for getting carboxylic acids from alcohols directly. CrO in anhydrous medium
is used as the oxidising agent for the isolation of aldehydes.
3

A better reagent for oxidation of primary alcohols to aldehydes in good yield


is pyridinium chlorochromate (PCC), a complex of chromium trioxide with

pyridine and HCl.

Secondary alcohols are oxidised to ketones by chromic anhyride (CrO ).


3

Tertiary alcohols do not undergo oxidation reaction. Under strong reaction


conditions such as strong oxidising agents (KMnO ) and elevated
temperatures, cleavage of various C-C bonds takes place and a mixture of
carboxylic acids containing lesser number of carbon atoms is formed.
4

When the vapours of a primary or a secondary alcohol are passed over


heated copper at 573 K, dehydrogenation takes place and an aldehyde or a
ketone is formed while tertiaryalcohols undergo dehydration.
Biological oxidation of methanol and ethanol in the body produces the
corresponding aldehyde followed by the acid. At times the alcoholics, by
mistake, drink ethanol, mixed with methanol also called denatured alcohol. In
the body, methanol is oxidised first to methanal and then to methanoic acid,
which may cause blindness and death. A methanol poisoned patient is
treated by giving intravenous infusions of diluted ethanol. The enzyme
responsible for oxidation of aldehyde (HCHO) to acid is swamped allowing
time for kidneys to excrete methanol.

(c) Reactions of phenols


Following reactions are shown by phenols only.
1. Electrophilic aromatic substitution
In phenols, the reactions that take place on the aromatic ring are electrophilic
substitution reactions (Unit 13, Class XI). The OH group attached to the
benzene ring activates it towards electrophilic substitution. Also, it directs the
incoming group to ortho and para positions in the ring as these positions

become electron rich due to the resonance effect caused by OH group. The
resonance structures are shown under acidity of phenols.
Common electrophilic aromatic substitution reactions taking place in phenol
are as follows:
(i) Nitration: With dilute nitric acid at low temperature (298 K), phenol
yields a mixture of ortho and para nitrophenols.

The ortho and para isomers can be separated by steam distillation. oNitrophenol is steam volatile due to intramolecular hydrogen bonding while pnitrophenol is less volatile due to intermolecular hydrogen bonding which
causes the association of molecules.

With concentrated nitric acid, phenol is converted to 2,4,6-trinitrophenol. The


product is commonly known as picric acid. The yield of the reaction product is
poor.

Nowadays picric acid is prepared by treating phenol first with concentrated


sulphuric acid which converts it to phenol-2,4-disulphonic acid, and then with
concentrated nitric acid to get 2,4,6-trinitrophenol. Can you write the
equations of the reactions involved?

(ii) Halogenation: On treating phenol with bromine, different reaction


products are formed under different experimental conditions.
(a) When the reaction is carried out in solvents of low polarity such as
CHCl or CS and at low temperature, monobromophenols are formed.
The usual halogenation of benzene takes place in the presence of a Lewis
acid, such as FeBr3 (Unit 10, Class XII), which polarises the halogen molecule.
In case of phenol, the polarisation of bromine molecule takes place even in
the absence of Lewis acid. It is due to the highly activating effect of OH
group attached to the benzene ring.
3

(b) When phenol is treated with bromine water, 2,4,6-tribromophenol is


formed as white precipitate.

Example 11.5 Write the structures of the major products expected from the
following reactions:
(a) Mononitration of 3-methylphenol
(b) Dinitration of 3-methylphenol
(c) Mononitration of phenyl methanoate.
Solution
The combined influence of OH and CH groups determine the position of the
incoming group.
3

2. Kolbes reaction
Phenoxide ion generated by treating phenol with sodium hydroxide is even

more reactive than phenol towards electrophilic aromatic substitution. Hence,


it undergoes electrophilic substitution with carbon dioxide, a weak
electrophile. Ortho hydroxybenzoic acid is formed as the main reaction
product.

3. Reimer-Tiemann reaction
On treating phenol with chloroform in the presence of sodium hydroxide, a
CHO group is introduced at ortho position of benzene ring. This reaction is
known as Reimer Tiemann reaction.
The intermediate substituted benzal chloride is hydrolysed in the presence of
alkali to produce salicylaldehyde

4. Reaction of phenol with zinc dust


Phenol is converted to benzene on heating with zinc dust.

5. Oxidation
Oxidation of phenol with chromic acid produces a conjugated diketone known
as benzoquinone. In the presence of air, phenols are slowly oxidised to dark
coloured mixtures containing quinones.

Intext Question
11.6 Give structures of the products you would expect when each of the
following alcohol reacts with (a) HCl ZnCl (b) HBr and (c) SOCl .
(i) Butan-1-ol
(ii) 2-Methylbutan-2-ol
11.7 Predict the major product of acid catalysed dehydration of
(i) 1-methylcyclohexanol and
(ii) butan-1-ol
11.8 Ortho and para nitrophenols are more acidic than phenol. Draw the
resonance structures of the corresponding phenoxide ions.
11.9 Write the equations involved in the following reactions:
(i) Reimer Tiemann reaction
(ii) Kolbes reaction
2

11.5 Some Commercially Important Alcohols


Methanol and ethanol are among the two commercially important alcohols.
1. Methanol
Methanol, CH OH, also known as wood spirit, was produced by destructive
distillation of wood. Today, most of the methanol is produced by catalytic
hydrogenation of carbon monoxide at high pressure and temperature and in
the presence of ZnO Cr O catalyst.
3

Methanol is a colourless liquid and boils at 337 K. It is highly poisonous in


nature. Ingestion of even small quantities of methanol can cause blindness
and large quantities causes even death. Methanol is used as a solvent in
paints, varnishes and chiefly for making formaldehyde.
2. Ethanol
Ethanol, C H OH, is obtained commercially by fermentation, the oldest
method is from sugars. The sugar in molasses, sugarcane or fruits such as
grapes is converted to glucose and fructose, (both of which have the formula
C H O ), in the presence of an enzyme, invertase. Glucose and fructose
undergo fermentation in the presence of another enzyme, zymase, which is
found in yeast.
2

12

In wine making, grapes are the source of sugars and yeast. As grapes ripen,
the quantity of sugar increases and yeast grows on the outer skin. When

grapes are crushed, sugar and the enzyme come in contact and fermentation
starts. Fermentation takes place in anaerobic conditions i.e. in absence of air.
Carbon dioxide is released during fermentation.
The action of zymase is inhibited once the percentage of alcohol formed
exceeds 14 percent. If air gets into fermentation mixture, the oxygen of air
oxidises ethanol to ethanoic acid which in turn destroys the taste of alcoholic
drinks.
Ethanol is a colourless liquid with boiling point 351 K. It is used as a solvent in
paint industry and in the preparation of a number of carbon compounds. The
commercial alcohol is made unfit for drinking by mixing in it some copper
sulphate (to give it a colour) and pyridine (a foul smelling liquid). It is known
as denaturation of alcohol.
Nowadays, large quantities of ethanol are obtained by hydration of ethene
(Section 11.4).
11.6 Ethers
11.6.1 Preparation of Ethers
1. By dehydration of alcohols
Alcohols undergo dehydration in the presence of protic acids (H SO , H PO ).
The formation of the reaction product, alkene or ether depends on the
reaction conditions. For example, ethanol is dehydrated to ethene in the
presence of sulphuric acid at 443 K. At 413 K, ethoxyethane is the main
product.
2

The formation of ether is a nucleophilic bimolecular reaction (SN ) involving


the attack of alcohol molecule on a protonated alcohol, as indicated below:
2

Acidic dehydration of alcohols, to give an alkene is also associated with


substitution reaction to give an ether.
The method is suitable for the preparation of ethers having primary alkyl
groups only. The alkyl group should be unhindered and the temperature be
kept low. Otherwise the reaction favours the formation of alkene. The reaction
follows S 1 pathway when the alcohol is secondary or tertiary about which
you will learn in higher classes. However, the dehydration of secondary and
tertiary alcohols to give corresponding ethers is unsuccessful as elimination
competes over substitution and as a consequence, alkenes are easily formed.
N

Can you explain why is bimolecular dehydration not appropriate for the
preparation of ethyl methyl ether?
2. Williamson synthesis
It is an important laboratory method for the preparation of symmetrical and
unsymmetrical ethers. In this method, an alkyl halide is allowed to react with
sodium alkoxide.

Ethers containing substituted alkyl groups (secondary or tertiary) may also be


prepared by this method. The reaction involves S 2 attack of an alkoxide ion
on primary alkyl halide.
N

Better results are obtained if the alkyl halide is primary. In case of secondary
and tertiary alkyl halides, elimination competes over substitution. If a tertiary
alkyl halide is used, an alkene is the only reaction product and no ether is
formed. For example, the reaction of CH ONa with (CH ) CBr gives exclusively
3

2-methylpropene.

It is because alkoxides are not only nucleophiles but strong bases as well.
They react with alkyl halides leading to elimination reactions.
Example 11.6 The following is not an appropriate reaction for the
preparation of t-butyl ethyl ether.

(i) What would be the major product of this reaction ?


(ii) Write a suitable reaction for the preparation of t-butylethyl ether.
Solution
(i) The major product of the given reaction is 2-methylprop-1-ene. It is
because sodium ethoxide is a strong nucleophile as well as a strong base.
Thus elimination reaction predominates over substitution.
Phenols are also converted to ethers by this method. In this, phenol is used
as the phenoxide moiety.

Phenols are also converted to ethers by this method. In this, phenol is used
as the phenoxide moiety.

11.6.2 Physical Properties


The C-O bonds in ethers are polar and thus, ethers have a net dipole
moment. The weak polarity of ethers do not appreciably affect their boiling
points which are comparable to those of the alkanes of comparable molecular
masses but are much lower than the boiling points of alcohols as shown in

the following cases:

The large difference in boiling points of alcohols and ethers is due to the
presence of hydrogen bonding in alcohols.
The miscibility of ethers with water resembles those of alcohols of the same
molecular mass. Both ethoxyethane and butan-1-ol are miscible to almost the
same extent i.e., 7.5 and 9 g per 100 mL water, respectively while pentane is
essentially immiscible with water. Can you explain this observation ? This is
due to the fact that just like alcohols, oxygen of ether can also form hydrogen
bonds with water molecule as shown:

11.6.3 Chemical Reactions


1. Cleavage of CO bond in ethers
Ethers are the least reactive of the functional groups. The cleavage of C-O
bond in ethers takes place under drastic conditions with excess of hydrogen
halides. The reaction of dialkyl ether gives two alkyl halide molecules.
R-O-R + HX → RX + R-OH
R-OH + HX → R-X + H O
2

Alkyl aryl ethers are cleaved at the alkyl-oxygen bond due to the more stable
aryl-oxygen bond. The reaction yields phenol and alkyl halide.

Ethers with two different alkyl groups are also cleaved in the same manner.
R-O-R + HX -> R- X + R -OH
The order of reactivity of hydrogen halides is as follows:
HI > HBr > HCl. The cleavage of ethers takes place with concentrated HI or
HBr at high temperature.
The reaction of an ether with concentrated HI starts with protonation of ether
molecule.

Step 1:

The reaction takes place with HBr or HI because these reagents are
sufficiently acidic.
Step 2:
Iodide is a good nucleophile. It attacks the least substituted carbon of the
oxonium ion formed in step 1 and displaces an alcohol molecule by S 2
mechanism. Thus, in the cleavage of mixed ethers with two different alkyl
groups, the alcohol and alkyl iodide formed, depend on the nature of alkyl
groups. When primary or secondary alkyl groups are present, it is the lower
alkyl group that forms alkyl iodide (S 2 reaction).
N

When HI is in excess and the reaction is carried out at high temperature,


ethanol reacts with another molecule of HI and is converted to ethyl iodide.
Step 3:

However, when one of the alkyl group is a tertiary group, the halide formed is
a tertiary halide.

It is because in step 2 of the reaction, the departure of leaving group (HO


CH ) creates a more stable carbocation [(CH ) C ], and the reaction follows S 1
3

mechanism.

In case of anisole, methylphenyl oxonium ion,


is formed by
protonation of ether. The bond between OCH is weaker than the bond
between OC H because the carbon of phenyl 2 group is sp hybridised and
there is a partial double bond character.
3

Therefore the attack by I ion breaks OCH bond to form CH I. Phenols do not
react further to give halides because the sp hybridised carbon of phenol
cannot undergo nucleophilic substitution reaction needed for conversion to
the halide.
3

Example 11.7
Give the major products that are formed by heating each of the following
ethers with HI.

Solution

2. Electrophilic substitution
The alkoxy group (-OR) is ortho, para directing and activates the aromatic
ring towards electrophilic substitution in the same way as in phenol.

(i) Halogenation: Phenylalkyl ethers undergo usual halogenation in the


benzene ring, e.g., anisole undergoes bromination with bromine in ethanoic
acid even in the absence of iron (III) bromide catalyst. It is due to the
activation of benzene ring by the methoxy group. Para isomer is obtained in
90% yield.

(ii) Friedel-Crafts reaction: Anisole undergoes Friedel-Crafts reaction, i.e.,


the alkyl and acyl groups are introduced at ortho and para positions by
reaction with alkyl halide and acyl halide in the presence of anhydrous

aluminium chloride (a Lewis acid) as catalyst.

(iii) Nitration: Anisole reacts with a mixture of concentrated sulphuric and


nitric acids to yield a mixture of ortho and para nitroanisole.

Intext Questions
11.10 Write the reactions of Williamson synthesis of 2-ethoxy-3methylpentane starting from ethanol and 3-methylpentan-2-ol.
11.11 Which of the following is an appropriate set of reactants for the
preparation of 1-methoxy-4-nitrobenzene and why?

11.12 Predict the products of the following reactions:

Summary
Alcohols and phenols are classified (i) on the basis of the number of hydroxyl
groups and (ii) according to the hybridisation of the carbon atom, sp or sp to
which the OH group is attached. Ethers are classified on the basis of groups
attached to the oxygen atom.
Alcohols may be prepared (1) by hydration of alkenes (i) in presence of an
acid and (ii) by hydroboration-oxidation reaction (2) from carbonyl
compounds by (i) catalytic reduction and (ii) the action of Grignard reagents.
Phenols may be prepared by (1) substitution of (i) halogen atom in
haloarenes and (ii) sulphonic acid group in aryl sulphonic acids, by OH group
(2) by hydrolysis of diazonium salts and (3) industrially from cumene.
Alcohols are higher boiling than other classes of compounds, namely
hydrocarbons, ethers and haloalkanes of comparable molecular masses. The
ability of alcohols, phenols and ethers to form intermolecular hydrogen
bonding with water makes them soluble in it.
Alcohols and phenols are acidic in nature. Electron withdrawing groups in
phenol increase its acidic strength and electron releasing groups decrease it.
Alcohols undergo nucleophilic substitution with hydrogen halides to yield alkyl
halides. Dehydration of alcohols gives alkenes. On oxidation, primary alcohols
yield aldehydes with mild oxidising agents and carboxylic acids with strong
oxidising agents while secondary alcohols yield ketones. Tertiary alcohols are
resistant to oxidation.
The presence of OH group in phenols activates the aromatic ring towards
electrophilic substitution and directs the incoming group to ortho and para
positions due to resonance effect. Reimer-Tiemann reaction of phenol yields
salicylaldehyde. In presence of sodium hydroxide, phenol generates
phenoxide ion which is even more reactive than phenol. Thus, in alkaline
medium, phenol undergoes Kolbes reaction.
Ethers may be prepared by (i) dehydration of alcohols and (ii) Williamson
synthesis. The boiling points of ethers resemble those of alkanes while their
solubility is comparable to those of alcohols having same molecular mass.
The CO bond in ethers can be cleaved by hydrogen halides. In electrophilic
3

substitution, the alkoxy group activates the aromatic ring and directs the
incoming group to ortho and para positions.
Execrises
11.1 Write IUPAC names of the following compounds:

11.2 Write structures of the compounds whose IUPAC names are as follows:
(i) 2-Methylbutan-2-ol
(ii) 1-Phenylpropan-2-ol
(iii) 3,5-Dimethylhexane 1, 3, 5-triol
(iv) 2,3 Diethylphenol
(v) 1 Ethoxypropane
(vi) 2-Ethoxy-3-methylpentane
(vii) Cyclohexylmethanol
(viii) 3-Cyclohexylpentan-3-ol
(ix) Cyclopent-3-en-1-ol
(x) 3-Chloromethylpentan-1-ol.
11.3 (i) Draw the structures of all isomeric alcohols of molecular formula
C H O and give their IUPAC names.
(ii) Classify the isomers of alcohols in question
5

12

11.3 (i) as primary, secondary and tertiary alcohols.


11.4 Explain why propanol has higher boiling point than that of the
hydrocarbon, butane?

11.5 Alcohols are comparatively more soluble in water than hydrocarbons of


comparable molecular masses. Explain this fact.
11.6 What is meant by hydroboration-oxidation reaction? Illustrate it with an
example.
11.7 Give the structures and IUPAC names of monohydric phenols of
molecular formula, C H O.
7

11.8 While separating a mixture of ortho and para nitrophenols by steam


distillation, name the isomer which will be steam volatile. Give reason.
11.9 Give the equations of reactions for the preparation of phenol from
cumene.
11.10 Write chemical reaction for the preparation of phenol from
chlorobenzene.
11.11 Write the mechanism of hydration of ethene to yield ethanol.
11.12 You are given benzene, conc. H SO and NaOH. Write the equations for
the preparation of phenol using these reagents.
2

11.13 Show how will you synthesise:


(i) 1-phenylethanol from a suitable alkene.
(ii) cyclohexylmethanol using an alkyl halide by an S 2 reaction.
(iii) pentan-1-ol using a suitable alkyl halide?
N

11.14 Give two reactions that show the acidic nature of phenol. Compare
acidity of phenol with that of ethanol.
11.15 Explain why is ortho nitrophenol more acidic than ortho methoxyphenol
?
11.16 Explain how does the OH group attached to a carbon of benzene ring
activate it towards electrophilic substitution?
11.17 Give equations of the following reactions:
(i) Oxidation of propan-1-ol with alkaline KMnO solution.
(ii) Bromine in CS with phenol.
(iii) Dilute HNO with phenol.
(iv) Treating phenol wih chloroform in presence of aqueous NaOH.
4

11.18 Explain the following with an example.


(i) Kolbes reaction.
(ii) Reimer -Tiemann reaction.

(iii) Williamson ether synthesis.


(iv) Unsymmetrical ether.
11.19 Write the mechanism of acid dehydration of ethanol to yield ethene.
11.20 How are the following conversions carried out?
(i) Propene Propan-2-ol.
(ii) Benzyl chloride Benzyl alcohol.
(iii) Ethyl magnesium chloride Propan-1-ol.
(iv) Methyl magnesium bromide 2-Methylpropan-2-ol.
11.21 Name the reagents used in the following reactions:
(i) Oxidation of a primary alcohol to carboxylic acid.
(ii) Oxidation of a primary alcohol to aldehyde.
(iii) Bromination of phenol to 2,4,6-tribromophenol.
(iv) Benzyl alcohol to benzoic acid.
(v) Dehydration of propan-2-ol to propene.
(vi) Butan-2-one to butan-2-ol.
11.22 Give reason for the higher boiling point of ethanol in comparison to
methoxymethane.
11.23 Give IUPAC names of the following ethers:

11.24 Write the names of reagents and equations for the preparation of the
following ethers by Williamsons synthesis:
(i) 1-Propoxypropane
(ii) Ethoxybenzene
(iii) 2-Methoxy-2-methylpropane
(iv) 1-Methoxyethane
11.25 Illustrate with examples the limitations of Williamson synthesis for the
preparation of certain types of ethers.
11.26 How is 1-propoxypropane synthesised from propan-1-ol? Write
mechanism of this reaction.

11.27 Preparation of ethers by acid dehydration of secondary or tertiary


alcohols is not a suitable method. Give reason.
11.28 Write the equation of the reaction of hydrogen iodide with:
(i) 1-propoxypropane (ii) methoxybenzene and (iii) benzyl ethyl ether.
11.29 Explain the fact that in aryl alkyl ethers (i) the alkoxy group activates
the benzene ring towards electrophilic substitution and (ii) it directs the
incoming substituents to ortho and para positions in benzene ring.
11.30 Write the mechanism of the reaction of HI with methoxymethane.
11.31 Write equations of the following reactions:
(i) Friedel-Crafts reaction alkylation of anisole.
(ii) Nitration of anisole.
(iii) Bromination of anisole in ethanoic acid medium.
(iv) Friedel-Crafts acetylation of anisole.
11.32 Show how would you synthesise the following alcohols from
appropriate alkenes?

11.33 When 3-methylbutan-2-ol is treated with HBr, the following reaction


takes place:

Give a mechanism for this reaction.


(Hint : The secondary carbocation formed in step II rearranges to a more
stable tertiary carbocation by a hydride ion shift from 3rd carbon atom.
Answers to Some Intext Questions
11.1 Primary alcohols
(i), (ii), (iii)
Secondary alcohols
(iv) and (v)
Tertiary alcohols
(vi)

11.2 Allylic alcohols

(ii) and (vi)

11.3 (i) 3-Chloromethyl-2-isopropylpentan-1-ol


(ii) 2, 5-Dimethylhexane-1,3-diol
(iii) 3-Bromocyclohexanol
(iv) Hex-1-en-3-ol
(v) 2-Bromo-3-methylbut-2-en-1-ol

11.7
(i) 1-Methylcyclohexene
(ii) A Mixture of but-1-ene and but-2-ene. But-1-ene is the major product
formed due to rearrangement to give secondary carbocation.

11.10
11.11 (ii)

Some Useful Links


http://www.freelance-teacher.com/videos.htm
I. Multiple Choice Questions (Type-I)
1. Monochlorination of toluene in sunlight followed by hydrolysis with aq.
NaOH yields.
(i) o-Cresol
(ii) m-Cresol
(iii) 2, 4-Dihydroxytoluene
(iv) Benzyl alcohol
2. How many alcohols with molecular formula C4H10O are chiral in nature?
(i) 1
(ii) 2
(iii) 3
(iv) 4
3. What is the correct order of reactivity of alcohols in the following reaction?

(i) 1 > 2 > 3


(ii) 1 < 2 > 3
(iii) 3 > 2 > 1
(iv) 3 > 1 > 2
4. CH CH OH can be converted into CH CHO by ______________.
3

(i) catalytic hydrogenation


(ii) treatment with LiAlH
(iii) treatment with pyridinium chlorochromate
(iv) treatment with KMnO
4

5. The process of converting alkyl halides into alcohols involves_____________.


(i) addition reaction
(ii) substitution reaction
(iii) dehydrohalogenation reaction
(iv) rearrangement reaction
6. Which of the following compounds is aromatic alcohol?

(i) A, B, C, D
(ii) A, D
(iii) B, C
(iv) A
7. Give IUPAC name of the compound given below.

(i) 2-Chloro-5-hydroxyhexane
(ii) 2-Hydroxy-5-chlorohexane
(iii) 5-Chlorohexan-2-ol
(iv) 2-Chlorohexan-5-ol
8. IUPAC name of m-cresol is ___________.
(i) 3-methylphenol
(ii) 3-chlorophenol
(iii) 3-methoxyphenol
(iv) benzene-1,3-diol

9. IUPAC name of the compound


(i) 1-methoxy-1-methylethane
(ii) 2-methoxy-2-methylethane
(iii) 2-methoxypropane
(iv) isopropylmethyl ether

is ______________.

10. Which of the following species can act as the strongest base?
(i) OH
(ii) OR
(iii) O C H

11. Which of the following compounds will react with sodium hydroxide
solution in water?
(i) C H OH
(ii) C H CH OH
(iii) (CH ) COH
(iv) C H OH
6

12. Phenol is less acidic than ______________.


(i) ethanol
(ii) o-nitrophenol
(iii) o-methylphenol
(iv) o-methoxyphenol
13. Which of the following is most acidic?
(i) Benzyl alcohol
(ii) Cyclohexanol
(iii) Phenol
(iv) m-Chlorophenol
14. Mark the correct order of decreasing acid strength of the following
compounds.

(i) e > d > b > a > c


(ii) b > d > a > c > e

(iii) d > e > c > b > a


(iv) e > d > c > b > a
15. Mark the correct increasing order of reactivity of the following compounds
with HBr/HCl.

(i) a < b < c


(ii) b < a < c
(iii) b < c < a
(iv) c < b < a
16. Arrange the following compounds in increasing order of boiling point.
Propan-1-ol, butan-1-ol, butan-2-ol, pentan-1-ol
(i) Propan-1-ol, butan-2-ol, butan-1-ol, pentan-1-ol
(ii) Propan-1-ol, butan-1-ol, butan-2-ol, pentan-1-ol
(iii) Pentan-1-ol, butan-2-ol, butan-1-ol, propan-1-ol
(iv) Pentan-1-ol, butan-1-ol, butan-2-ol, propan-1-ol
II. Multiple Choice Questions (Type-II)
Note : In the following questions two or more options may be correct.
17. Which of the following are used to convert RCHO into RCH OH?
2

(i) H /Pd
(ii) LiAlH
(iii) NaBH
(iv) Reaction with RMgX followed by hydrolysis
2

18. Which of the following reactions will yield phenol?

19. Which of the following reagents can be used to oxidise primary alcohols
to aldehydes?
(i) CrO in anhydrous medium.
(ii) KMnO in acidic medium.
(iii) Pyridinium chlorochromate.
(iv) Heat in the presence of Cu at 573K.
3

20. Phenol can be distinguished from ethanol by the reactions with _________.
(i) Br /water
(ii) Na
(iii) Neutral FeCl
(iv) All the above
2

21. Which of the following are benzylic alcohols?


(i) C H CH CH OH
(ii) C H CH OH
6

III. Short Answer Type


22. What is the structure and IUPAC name of glycerol?
23. Write the IUPAC name of the following compounds.

24. Write the IUPAC name of the compound given below.

25. Name the factors responsible for the solubility of alcohols in water.
26. What is denatured alcohol?
27. Suggest a reagent for the following conversion.

28. Out of 2-chloroethanol and ethanol which is more acidic and why?
29. Suggest a reagent for conversion of ethanol to ethanal.
30. Suggest a reagent for conversion of ethanol to ethanoic acid.
31. Out of o-nitrophenol and p-nitrophenol, which is more volatile? Explain.
32. Out of o-nitrophenol and o-cresol which is more acidic?
33. When phenol is treated with bromine water, white precipitate is obtained.
Give the structure and the name of the compound formed.
34. Arrange the following compounds in increasing order of acidity and give a
suitable explanation.
Phenol, o-nitrophenol, o-cresol
35. Alcohols react with active metals e.g. Na, K etc. to give corresponding
alkoxides. Write down the decreasing order of reactivity of sodium metal
towards primary, secondary and tertiary alcohols.
36. What happens when benzene diazonium chloride is heated with water?
37. Arrange the following compounds in decreasing order of acidity.
H O, ROH,
2

38. Name the enzymes and write the reactions involved in the preparation of
ethanol from sucrose by fermentation.
39. How can propan-2-one be converted into tert- butyl alcohol?
40. Write the structures of the isomers of alcohols with molecular formula
C H O. Which of these exhibits optical activity?
4

10

41. Explain why is OH group in phenols more strongly held as compared to


OH group in alcohols.
42. Explain why nucleophilic substitution reactions are not very common in
phenols.
43. Preparation of alcohols from alkenes involves the electrophilic attack on
alkene carbon atom. Explain its mechanism.
44. Explain why is

nonpolar while ROR is polar.

45. Why is the reactivity of all the three classes of alcohols with conc. HCl and
ZnCl (Lucas reagent) different?
46. Write steps to carry out the conversion of phenol to aspirin.
47. Nitration is an example of aromatic electrophilic substitution and its rate
depends upon the group already present in the benzene ring. Out of benzene
and phenol, which one is more easily nitrated and why?
48. In Kolbes reaction, instead of phenol, phenoxide ion is treated with
carbon dioxide. Why?
49. Dipole moment of phenol is smaller than that of methanol. Why?
50. Ethers can be prepared by Williamson synthesis in which an alkyl halide is
reacted with sodium alkoxide. Di-tert-butyl ether cant be prepared by this
method. Explain.
51. Why is the COH bond angle in alcohols slightly less than the
tetrahedral angle whereas the COC bond angle in ether is slightly
greater?
52. Explain why low molecular mass alcohols are soluble in water.
53. Explain why p-nitrophenol is more acidic than phenol.
54. Explain why alcohols and ethers of comparable molecular mass have
different boiling points?
55. The carbon-oxygen bond in phenol is slightly stronger than that in
methanol. Why?
56. Arrange water, ethanol and phenol in increasing order of acidity and give
reason for your answer.
2

IV. Matching Type


Note : Match the items of Column I and Column II in the following questions.
57. Match the structures of the compounds given in Column I with the name
of the compounds given in Column II.

58. Match the starting materials given in Column I with the products formed
by these (Column II) in the reaction with HI.

59. Match the items of column I with items of column II.


Column I

(i)

Antifreeze used in car engine

Column II
Neutral ferric
(a) chloride

(ii)

Solvent used in perfumes

(b) Glycerol

(iii)

Starting material for picric acid

(c) Methanol

(iv)

Wood spirit

(d) Phenol

(v)

Reagent used for detection of phenolic


group

(e) Ethleneglycol

(vi)

By product of soap industry used in


cosmetics

(f)

Ethanol

60. Match the items of column I with items of column II.


Column I

(i)

(ii)

Column II

Methanol

(a Conversion of phenol to o)
hydroxysalicylic acid

Kolbes reaction

(b
)
Ethyl alcohol

(iii) Williamsons synthesis

(c
)

Conversion of phenol to
salicylaldehyde

Conversion of 2 alcohol to (d
(iv) ketone
)
Wood spirit

(v) Reimer-Tiemann reaction

(e
)
Heated copper at 573K

(vi) Fermentation

Reaction of alkyl halide with sodium


(f) alkoxide

V. Assertion and Reason Type


Note : In the following questions a statement of assertion followed by a
statement of reason is given. Choose the correct answer out of the following
choices.
(i) Assertion and reason both are correct and reason is correct explanation of
assertion.

(ii) Assertion and reason both are wrong statements.


(iii) Assertion is correct statement but reason is wrong statement.
(iv) Assertion is wrong statement but reason is correct statement.
(v) Both assertion and reason are correct statements but reason is not correct
explanation of assertion.
61. Assertion : Addition reaction of water to but-1-ene in acidic medium yields
butan-1-ol
Reason : Addition of water in acidic medium proceeds through the formation
of primary carbocation.
62. Assertion : p-nitrophenol is more acidic than phenol.
Reason : Nitro group helps in the stabilisation of the phenoxide ion by
dispersal of negative charge due to resonance.

63. Assertion : IUPAC name of the compound


is 2-Ethoxy-2-methylethane.
Reason : In IUPAC nomenclature, ether is regarded as hydrocarbon derivative
in which a hydrogen atom is replaced by OR or OAr group [where R =
alkyl group and Ar = aryl group]
64. Assertion : Bond angle in ethers is slightly less than the tetrahedral angle.
Reason : There is a repulsion between the two bulky (R) groups.
65. Assertion : Boiling points of alcohols and ethers are high.
Reason : They can form intermolecular hydrogen-bonding.
66. Assertion : Like bromination of benzene, bromination of phenol is also
carried out in the presence of Lewis acid.
Reason : Lewis acid polarises the bromine molecule.
67. Assertion : o-Nitrophenol is less soluble in water than the m- and pisomers.
Reason : m- and p- Nitrophenols exist as associated molecules.
68. Assertion : Ethanol is a weaker acid than phenol.
Reason : Sodium ethoxide may be prepared by the reaction of ethanol with
aqueous NaOH.
69. Assertion : Phenol forms 2, 4, 6 tribromophenol on treatment with Br in
carbon disulphide at 273K.
Reason : Bromine polarises in carbon disulphide.
2

70. Assertion : Phenols give o- and p-nitrophenol on nitration with conc.


HNO and H SO mixture.
Reason : OH group in phenol is o, p directing.
3

VI. Long Answer Type


71. Write the mechanism of the reaction of HI with methoxybenzene.
72. (a) Name the starting material used in the industrial preparation of
phenol.
(b) Write complete reaction for the bromination of phenol in aqueous and non
aqueous medium.
(c) Explain why Lewis acid is not required in bromination of phenol?
73. How can phenol be converted to aspirin?
74. Explain a process in which a biocatalyst is used in industrial preparation
of a compound known to you.
ANSWERS
I. Multiple Choice Questions (Type-I)
1. (iv) 2. (i) 3. (iii) 4. (iii) 5. (ii) 6. (iii)
7. (iii) 8. (i) 9. (iii) 10. (ii) 11. (i) 12. (ii)
13. (iv) 14. (ii) 15. (iii) 16. (i)
II. Multiple Choice Questions (Type-II)
17. (i), (ii), (iii) 18. (i), (ii), (iii) 19. (i), (iii), (iv) 20. (i), (iii)
21. (ii), (iii)
III. Short Answer Type
22.

; Propane-1,2,3-triol
23. (A) 3-Ethyl-5-methylhexane-2,4-diol, (B) 1-Methoxy-3-nitrocyclohexane
24. 3-Methylpent-2-ene-1,2-diol
25. (i) Hydrogen bonding (ii) Size of alkyl/aryl group.
26. Alcohol is made unfit for drinking by mixing some copper sulphate and
pyridine in it. This is called denatured alcohol.
27. CrO , pyridine and HCl. (Pyridinium chlorochromate)
28. 2-Chloroethanol, due to I effect of chlorine atom.
29. CrO , Pyridine and HCl (Pyridinium chlorochromate)
3

30. Any strong oxidising agent e.g., acidified KMnO or K Cr O .


31. Ortho nitrophenol, [Hint : intramolecular hydrogen bonding in onitrophenol and intermolecular hydrogen bonding in p-nitrophenol.]
32. o-Nitrophenol, [Hint : CH group is electron releasing]
4

33.

34. Increasing order of acidity :


o-cresol < phenol < o-nitrophenol
[Hint : In substituted phenols, the presence of electron withdrawing
groups, enhance the acidic strength of phenol whereas, electron releasing
groups decrease the acidic strength of phenol.]
35. Decreasing order of reactivity of sodium metal is :
1 > 2 > 3
36. [Hint : It gives phenol]
37. [Hint : H O > ROH > HC CH]
38. See NCERT textbook for Class XII
39. [Hint : Using Grignard reagent]
40. See NCERT textbook for Class XII
41. See NCERT textbook for Class XII
42. See NCERT textbook for Class XII
43. See NCERT textbook for Class XII
44. See NCERT textbook for Class XII
45. An alcohol reacts with conc. HCl and ZnCl (Lucas reagent) to give
carbocation. More stable is the carbocation, faster is the reaction.
2

46.

47. Phenol is more easily nitrated than benzene as the presence of OH


group in phenol increases the electron density at ortho and para positions in
benzene ring by +R effect. The nitration, being an electrophilic substitution
reaction is more facile where the electron density is more.
48. Phenoxide ion is more reactive than phenol towards electrophilic aromatic
substitution and hence undergoes electrophilic substitution with
carbondioxide which is a weak electrophile.
49. In phenol, CO bond is less polar due to electron-withdrawing effect of
benzene ring whereas in methanol, CO bond is more polar due to
electronreleasing effect of CH group.
50. In tert-butyl halides, elimination is favoured over substitution, so alkene is
the only reaction product and ether is not formed.
3

51. See NCERT textbook for Class XII.


52. See NCERT textbook for Class XII.
53. See NCERT textbook for Class XII.
54. See NCERT textbook for Class XII.
55. This is due to the fact that
(i) In phenol, conjugation of unshared electron pair over oxygen with aromatic
ring results in partial double bond character in carbonoxygen bond.
(ii) In phenol, oxygen is attached to a sp hybridised carbon atom while in
methanol, it is attached to a sp hyrbidised carbon atom. The bond formed
2

between oxygen and sp hybridised carbon is more stable than that formed
between oxygen and sp hybridised carbon.
2
3

56. Increasing order of acidity is ethanol < water < phenol. The phenoxide
ion obtained after the removal of a proton is stabilised by resonance whereas
the ethoxide ion obtained after the removal of a proton is destabilised by +I
effect of C H group. Therefore phenol is stronger acid than ethanol. On the
other hand ethanol is weaker acid than water because electron releasing
C H group in ethanol inreases the electron density on oxygen and hence the
polarity of OH bond in ethanol decreases which results in the decreasing
acidic strength. Hence acidic strength increases in the order given above.
2

IV. Matching Type


57.
58.
59.
60.

(i) (d), (ii) (c), (iii) (f), (iv) (a); (v) (g), (vi) (b)
(i) (d), (ii) (e), (iii) (b), (iv) (a)
(i)(e), (ii)(f), (iii)(d), (iv)(c), (v)(a), (vi)(b)
(i) (d), (ii) (a), (iii) (f), (iv) (e); (v) (c), (vi) (b)

V. Assertion and Reason Type


61. (ii) 62. (i) 63. (iv) 64. (iv) 65. (ii) 66. (iv)
67. (v) 68. (iii) 69. (ii) 70. (iv)
VI. Long Answer Type
71.
72.
73.
74.

Consult
Consult
Consult
Consult

NCERT
NCERT
NCERT
NCERT

textbook
textbook
textbook
textbook

for
for
for
for

Class
Class
Class
Class

XII.
XII.
XII.
XII.

26 THOUGHTS ON 11. ALCOHOLS, PHENOLS AND ETHERS

Themes > Science > Chemistry > Organic Chemistry > Determination of
Structure > Organic Compound Identification Using Infrared Spectroscopy

Description
This exercise is intended to familiarize you with the identification of functional groups
in organic compounds using infrared spectra. Before you can use this technique, you
need to have an introduction to infrared spectroscopy and to what an IR spectrum is.
Infrared spectroscopy deals with the interaction of infrared light with matter. The
energy of an infrared photon can be calculated using the Planck energy relation.

E = hn
where h = 6.6 x 10-34 joule second and n = frequency of the photon. This
shows that high energy photons have high frequency.

The frequency, n, and speed of light, c, are related through the relation

c = ln
where c = 3.0 x 108 meter/second and l = wavelength for the light

These two equations can be used to identify a common spectroscopic unit


calledwavenumber, , which is the reciprocal of the wavelength.

E = hn = h c

= wavenumber =

; E = hn = h c ;

has units of (cm-1)

You can see that both frequency and wavenumber are directly proportional to
energy.
Molecules are flexible, moving collections of atoms. The atoms in a molecule are
constantly oscillating around average positions. Bond lengths and bond angles are
continuously changing due to this vibration. A molecule absorbs infrared radiation
when the vibration of the atoms in the molecule produces an oscillating electric field

with the same frequency as the frequency of incident IR "light".


All of the motions can be described in terms of two types of molecular vibrations.
One type of vibration, a stretch, produces a change of bond length. A stretch is a
rhythmic movement along the line between the atoms so that the interatomic
distance is either increasing or decreasing.

The second type of


vibration, a bend, results in a change in bond angle. These are also sometimes
called scissoring, rocking, or "wig wag" motions.

Each of these two main types of vibration can have variations. A stretch can be
symmetric or asymmetric. Bending can occur in the plane of the molecule or out of
plane; it can be scissoring, like blades of a pair of scissors, or rocking, where two
atoms move in the same direction.
Different stretching and bending vibrations can be visualized by considering the
CH2 group in hydrocarbons. The arrows indicate the direction of motion. The
stretching motions require more energy than the bending ones.

Note the high wavenumber (high energy) required to produce these motions.
The bending motions are sometimes described as wagging or scissoring motions.

You can see that the lower wavenumber values are consistent with lower energy to
cause these vibrations.
A molecule absorbs a unique set of IR light frequencies. Its IR spectrum is often

likened to a person's fingerprints. These frequencies match the natural vibrational


modes of the molecule. A molecule absorbs only those frequencies of IR light that
match vibrations that cause a change in the dipole moment of the molecule. Bonds
in symmetric N2 and H2 molecules do not absorb IR because stretching does not
change the dipole moment, and bending cannot occur with only 2 atoms in the
molecule. Any individual bond in an organic molecule with symmetric structures and
identical groups at each end of the bond will not absorb in the IR range. For
example, in ethane, the bond between the carbon atoms does not absorb IR
because there is a methyl group at each end of the bond. The C-H bonds within the
methyl groups do absorb.
In a complicated molecule many fundamental vibrations are possible, but not all are
observed. Some motions do not change the dipole moment for the molecule; some
are so much alike that they coalesce into one band.
Even though an IR spectrum is characteristic for an entire molecule, there are
certain groups of atoms in a molecule that give rise to absorption bands at or near
the same wavenumber, ,
(frequency) regardless of the rest of the structure of the molecule. These persistent
characteristic bands enable you to identify major structural features of the molecule
after a quick inspection of the spectrum and the use of a correlation table. The
correlation table is a listing of functional groups and their characteristic absorption
frequencies.
The infrared spectrum for a molecule is a graphical display. It shows the frequencies
of IR radiation absorbed and the % of the incident light that passes through the
molecule without being absorbed. The spectrum has two regions.
The fingerprint region is unique for a molecule and the functional group region is
similar for molecules with the same functional groups.

The nonlinear horizontal axis has units of wavenumbers. Each wavenumber value
matches a particular frequency of infrared light. The vertical axis shows %
transmitted light. At each frequency the % transmitted light is 100% for light that
passes through the molecule with no interactions; it has a low value when the IR
radiation interacts and excites the vibrations in the molecule.
A portion of the spectrum where % transmittance drops to a low value then rises
back to near 100% is called a "band". A band is associated with a particular vibration
within the molecule. The width of a band is described as broad or narrow based on
how large a range of frequencies it covers. The efficiencies for the different
vibrations determine how "intense" or strong the absorption bands are. A band is
described as strong, medium, or weak depending on its depth.
In the hexane spectrum below the band for the CH stretch is strong and that for the
CH bend is medium. The alkane, hexane (C6H14) gives an IR spectrum that has

relatively few bands because there are only CH bonds that can stretch or bend.
There are bands for CH stretches at about 3000 cm -1. The CH2 bend band appears
at approximately 1450 cm-1 and the CH3 bend at about 1400 cm-1. The spectrum also
shows that shapes of bands can

differ.

Procedure
Every molecule will have its own characteristic spectrum. The bands that appear
depend on the types of bonds and the structure of the molecule. Study the sample
spectra below, noting similarities and differences, and relate these to structure and
bonding within the molecules.
The spectrum for the alkene, 1-hexene, C6H12, has few strong absorption bands. The
spectrum has the various CH stretch bands that all hydrocarbons show near 3000
cm-1. There is a weak alkene CH stretch above 3000 cm -1. This comes from the
C&emdash;H bonds on carbons 1 and 2, the two carbons that are held together by
the double bond. The strong CH stretch bands below 3000 cm -1 come from carbonhydrogen bonds in the CH2and CH3 groups. There is an out-of-plane CH bend for the
alkene in the range 1000-650 cm-1. There is also an alkene CC double bond stretch
at about 1650 cm-1 .

The spectrum for cyclohexene, (C6H10) also has few strong bands. The main band is
a strong CH stretch from the CH2 groups at about 3000 cm-1. The CH stretch for the
alkene CH is, as always, to the left of 3000 cm -1. The CH2 bend appears at about
1450 cm-1. The other weaker bands in the range 1000-650 cm -1 are for the out of
plane CH bending . There is a very weak alkene CC double bond stretch at about
1650 cm-1.

The IR spectrum for benzene, C6H6, has only four prominent bands because it is a

very symmetric molecule. Every carbon has a single bond to a hydrogen. Each
carbon is bonded to two other carbons and the carbon-carbon bonds are alike for all
six carbons. The molecule is planar. The aromatic CH stretch appears at 3100-3000
cm-1 There are aromatic CC stretch bands (for the carbon-carbon bonds in the
aromatic ring) at about 1500 cm-1. Two bands are caused by bending motions
involving carbon-hydrogen bonds. The bands for CH bends appear at approximately
1000 cm-1 for the in-plane bends and at about 675 cm -1for the out-of-plane bend.

The IR spectrum for the alcohol, ethanol (CH3CH2OH), is more complicated. It has a
CH stretch, an OH stretch, a CO stretch and various bending vibrations. The
important point to learn here is that no matter what alcohol molecule you deal with,
the OH stretch will appear as a broad band at approximately 3300-3500 cm -1.
Likewise the CH stretch still appears at about 3000 cm -1.

The spectrum for the aldehyde, octanal (CH3(CH2)6CHO), is shown here. The most
important features of the spectrum are carbonyl CO stretch near 1700 cm -1 and the
CH stretch at about 3000 cm-1. If you see an IR spectrum with an intense strong
band near 1700 cm-1 and the compound contains oxygen, the molecule most likely
contains a carbonyl group,

The spectrum for the ketone, 2-pentanone, appears below. It also has a

characteristic carbonyl band at 1700 cm-1. The CH stretch still appears at about 3000
cm-1, and the CH2 bend shows up at approximately 1400 cm-1. You can see the
strong carbonyl CO stretch at approximately 1700 cm -1. You can also see that this
spectrum is different from the spectrum for octanal. At this point in your study of IR
spectroscopy, you can't tell which compound is an aldehyde and which is a ketone.
You can tell that both octanal and a 2-pentanone contain C-H bonds and a carbonyl
group.

Carboxylic acids have spectra that are even more involved. They typically have three
bands caused by bonds in the COOH functional group. The band near 1700 cm -1 is
due to the CO double bond. The broad band centered in the range 2700-3300 cm 1
is caused by the presence of the OH and a band near 1400 cm -1 comes from the
CO single bond . The spectrum for the carboxylic acid, diphenylacetic acid, appears
below. Although the aromatic CH bands complicate the spectrum, you can still see
the broad OH stretch between 2700-3300 cm -1. It overlaps the CH stretch which
appears near 3000 cm-1. A strong carbonyl CO stretch band exists near 1700 cm -1.
The CO single bond stretch shows up near 1200 cm -1.

The spectrum for 1-bromobutane, C4H9Br, is shown here. This is relatively simple
because there are only CH single bonds and the CBr bond. The CH stretch still
appears at about 3000 cm-1. The CH2 bend shows up near 1400 cm-1, and you can
see the CBr stretch band at approximately 700 cm -1.

IR spectra can be used to identify molecules by recording the spectrum for an


unknown and comparing this to a library or data base of spectra of known
compounds. Computerized spectra data bases and digitized spectra are used
routinely in this way in research, medicine, criminology, and a number of other fields.
In this exercise you will try to identify the outstanding bands characteristic of certain
bonds and functional groups in the spectra you examine. You are certainly not
expected to identifyall the absorption bands in each IR spectrum at this point in your

work.

When you analyze the spectra, it is easier if you follow a series of steps in
examining each spectrum.

1. Look first for the carbonyl C::O band. Look for a strong band at 1820-1660 cm-1.
This band is usually the most intense absorption band in a spectrum. It will have a
medium width. If you see the carbonyl band, look for other bands associated with
functional groups that contain the carbonyl by going to step 2. If no C::O band is
present, check for alcohols and go to step 3.

2. If a C::O is present you want to determine if it is part of an acid, an ester, or an


aldehyde or ketone. At this time you may not be able to distinguish aldehyde from
ketone and you will not be asked to do so.

ACID

Look for indications that an O-H is also present. It has a


broad absorption near 3300-2500 cm-1. This actually will
overlap the C-H stretch. There will also be a C-O single bond
band near 1100-1300 cm-1. Look for the carbonyl band near
1725-1700 cm-1.

ESTER

Look for C-O absorption of medium intensity near 1300-1000


cm-1. There will be no O-H band.

ALDEHYDE

Look for aldehyde type C-H absorption bands. These are


two weak absorptions to the right of the C-H stretch near
2850 cm-1 and 2750 cm-1 and are caused by the C-H bond
that is part of the CHO aldehyde functional group. Look for
the carbonyl band around 1740-1720 cm-1.

KETONE

The weak aldehyde CH absorption bands will be absent.


Look for the carbonyl CO band around 1725-1705 cm -1.

3. If no carbonyl band appears in the spectrum, look for an alcohol O-H band.

ALCOHOL

Look for the broad OH band near 3600-3300 cm -1 and a


C-O absorption band near 1300-1000 cm-1.

4. If no carbonyl bands and no O-H bands are in the spectrum, check for double
bonds, C::C, from an aromatic or an alkene.

ALKENE

Look for weak absorption near 1650 cm-1 for a double


bond. There will be a CH stretch band near 3000 cm-1.

AROMATIC

Look for the benzene, C::C, double bonds which


appear as medium to strong absorptions in the region
1650-1450 cm-1. The CH stretch band is much weaker
than in alkenes.

5. If
none of
the
previous

groups can be identified, you may have an alkane.

ALKANE

The main absorption will be the C-H stretch near 3000


cm-1. The spectrum will be simple with another band
near 1450 cm-1.

6. If the
spectrum still cannot be assigned you may have an alkyl bromide.

ALKYL
BROMIDE

Look for the C-H stretch and a relatively simple


spectrum with an absorption to the right of 667 cm -1.

Qualitative Analysis of Functional Groups

In this experiment you will learn about how organic substances can be classified
according to the functional groups they contain. You will then examine the
physical and chemical properties of a number of unknown compounds in order to
determine their identity.
The experiment is composed of four parts (background, prelab, experiment,
postlab) that should be completed in the order listed below.

It would be very time consuming to perform all of the chemical tests on each of the
unknowns you have been assigned. Fortunately, a flow chart can be devised to help
simplify the process. Following the flow chart will help you identify which class of
compound your unknown belongs to. If there is more than one possibility among
the unknowns, you will have to use solubility and boiling point data as well.

Continue and check out an example.