5-Alcohol, Phenol & Ether

Chemistry by sandeep sir
Alcohol, Phenol and Ether

Adolph Wilhelm Hermann Kolbe
Born 27 September 1818
Died 25 November 1884
Nationality Germany
Field Chemistry
Known for Kolbe’s electrolysis and

reaction
Kolbe (1818 – 1884) was born in Elliehausen, Germany.
In 1865, it was believed that organic and inorganic compounds are independent from each other, and
that organic compounds could be created only by living organisms. Kolbe believed that organic
compounds could be derived from inorganic ones, directly or indirectly, by substitution processes. He
validated his theory by converting carbon disulfide, in several steps, to acetic acid (1843-45).
Introducing a modified idea of structural radicals, he contributed to the establishment of structural
theory. He also predicted the existence of secondary and tertiary alcohols.
He worked on the electrolysis of the salts of fatty and other acids (Kolbe electrolysis) and prepared
salicylic acid, a building block of aspirin in a process called Kolbe synthesis or Kolbe-Schmitt reaction.
With Edward Frankland he found that nitriles can be hydrolyzed to the corresponding acids.
B-211 tilak nagar -1-

6.1 Alcohol
Alcohols are compounds in which a hydroxyl (– OH) group is attached to saturated carbon atom.
Functional
group
C OH R − OH
General formula
The hydroxyl group is the functional group of alcohols. Alcohols containing one hydroxyl
group are called Monohydric Alcohols. Alcohols with two, three or more hydroxyl groups are
known as Dihydric Alcohols, Trihydric Alcohols, and Polyhydric Alcohols respectively. For
example,
C H 2 − OH
|
C H 2 − OH C H 2 − OH
| C H 2 − OH
|
CH 2 − OH |
CH 2 − OH
CH 2 − OH
CH 3CH 2 − OH Monohydric
Di
(Two OH group) Monohydric Trihydric
(One OH group) (Two OH group) (Three OH group)
(Monohydric)
Monohydric alcohols contain one –OH group attached to saturated carbon. They many be
represented as (R–OH)
Primary (1°) Secondary (2°) and Tertiary (3°) Alcohols
Monohydric alcohols are classified as primary (1°) secondary (2°), or tertiary (3°), depending
upon whether the –OH group is attached to a primary, a secondary, or a tertiary carbon.
Primary Secondary Tertiary
H carbon R′ carbon R′ carbon
R C OH R C OH R C OH
H H R′′
Primary alcohol Secondary alcohol Tertiary alcohol
6.2 Structure
Let us consider methyl alcohol (CH3OH) for illustrating the orbital make up of alcohols. In methyl
alcohol both oxygen and carbon are sp3 hybridized. Two of the sp3 orbitals of oxygen are
completely filled and cannot take part in bond formation. The C–O bond in methyl alcohol is
formed by overlap of an sp3 orbital of carbon and sp3 orbital of carbon and an sp3 orbital of
oxygen. The O–H bond is formed by overlap of an sp3 orbital of oxygen and s orbital of hydrogen.
The C–O–H bond angle is 105°. It is less than the normal tetrahedral angle. This is because the
two completely filled sp3 orbital of oxygen repel each other. This results in reduction of the bond
angle.

Nomenclature
Alcohols are named by three systems:
Common system
In this system alcohols (R–OH) are named as Alkyl Alcohols. The alkyl group attached to the –OH
group is named and ‘alcohol’ is added as a separate word. For example,
As we go higher in the series, it becomes necessary to indicate whether a particular alcohol is

primary (1°), secondary (2°), or tertiary (3°). The prefix secondary is abbreviated as sec. The prefix
tertiary is abbreviated as tert-or t-. For example,
Carbinol System
In this system alcohols are considered as derivatives of methyl alcohol which is called Carbinol.
The alkyl group attached to the carbon carrying the –OH group are named in alphabetic order.
Then the suffix-Carbinol is added. For example,
6.3 IUPAC System

In this system alcohols are named as Alkanols. The IUPAC rules are
(a) Select the longest continuous carbon chain containing the –OH group
(b) Change the name of the alkane corresponding to his chain by dropping the ending -e and
adding the suffix -ol.
(c) Number the chain so as to give the carbon carrying the –OH roup, the lowest possible
number. The position of the –OH group is indicated by this number.

(d) Indicate the positions of other substituents or multiple bonds by number
The example given below show how these rules are used
6.4 Grignard Synthesis

When a solution of an alkyl halide in dry ethyl ether, (C2H5)2O, is allowed to stand over turnings
of metallic magnesium, a vigorous reaction takes place. The solution turns cloudy, begins to boil
and the magnesium metal gradually disappears. The resulting solution is know as Grignard
reagent. It is one of the most useful and versatile reagents known to the organic chemists.
Dry ether
RX + Mg  → RMgX
Alkyl halide Alkyl magnesium halide
The Grignard reagent has the general formula RMgX, and the general name alkyl magnesium
halide. The carbon-magnesium bond is covalent but highly polar, with carbon pulling away
electrons from electropositive magnesium but the magnesium-halogen bond is essentially ionic,
Θ ⊗
R MgX .
Since magnesium becomes bonded to the same carbon that previously held halogen, the alkyl
group remains intact during the preparation of the reagent. Thus, n-propyl chloride yields n-
propyl magnesium chloride and isopropyl chloride yields isopropyl magnesium chloride.
Dryether
CH3 CH2 CH2 CI + Mg  → CH 2 CH 2 CH2 MgCI
n − Pr opyl chloride n − Pr opyl magnesium chloride
( CH3 ) CHCI + Mg 

Dry ether
→ ( CH3 )2 CHMgCI
Isopropyl chloride Isopropyl magnesium chloride
The grignard reagent belongs to a class of compounds called organometallic compounds, in

which carbon is bonded to a metal like lithium, potassium, sodium, zinc, mercury, lead, thallium
or to almost any metal know. Each kind of organometallic compound has its own set of properties
and its particular uses depend on these. But whatever the metal, it is less electronegative than
carbon and the carbon-metal bond is always highly polar. Although the organicg group is not a
full-fledged carbonion but has considerable carbanionic characters. Thus, organometallic
compounds can serve as a source of carbon bearing negative charge.
The Grinard reagent has the formula RMgX and is prepared by the reaction of metallic
magnesium with the appropriate organic halide. This halide can be alkyl (°, 2°, 3°), alylic, aryl
alkyl (e.g. benzyl), or aryl (phenyl) or substituted phenyl. The halogen maybe –Cl, −Br or −I, (Aryl
magnesium chlorides must be made in the cyclic ether tetrahydrofuran instead of ethyl ether).
Aldehydes and ketones resemble each other closely in most of their reactions. The carbonyl group

is also unsaturated and like the carbon-carbon bond, it also undergoes addition. One of the
typical reaction is cis addition of the Grignard reagent.
The electrons of the carbonyl double bond hold together atoms of different electronegativity,
thus, the electrons are not equally shared, the mobile π-cloud is pulled strongly towares the more
electronegative atom, oxygen. The addition of an unsymmetrical reagent happens such that the
nucleophilic (basic) portion attaches itself to carbon and the electrophilic (acidic) portion attaches
itself to oxygen.
The carbon-magnesium bond of the Grignard reagent is a highly polar bond, carbon being
negative relative to electropositive magnesium. When Grignard reagent is added to carbonyl
compounds, the organic group attaches to carbon and magnesium to oxygen.
OH2
C=O + R: MgX C-OMgX C-OH + Mg(OH)X
R R
An alcohol
Mg2+ + X +H2O
The product is a magnesium salt of the weakly acidic alcohol and is easily converted into the
alcohol by the addition of the stronger acid, water. The Mg(OH)X thus formed is a gelatinous
material, which forms coating over carbonyl compound, thus dilute mineral acid (HCI, H2SO4) is
commonly used instead of water, so that water-soluble magnesium salts are formed.
Products of the Grignard Synthesis
The type of alcohol that is obtained from a Grignard synthesis depends upon the type of
carbonyl compound used. Formaldehyde (HCHO) yields primary alcohols, other aldehydes
(RCHO) yield secondary alcohols and ketones (R2CO) yield tertiary alcohols.
The number of hydrogens attached to the carbonyl carbon defines the carbonyl compound as
formaldehyde, higher aldehydes or ketone. The carbonyl carbonyl carbon is the one that finally
bears the OH group in the product and the number of hydrogen defines the alchol as primary,
secondary, or tertiary.
Grignard reagents react with aldehydes or ketones to form an addition compound which on
hydrolysis with dilute acid gives the corresponding alcohols.
Primary alcohols are obtained by treating a Grignard reagent with formaldehyde or ethylene
oxide.

Secondary alcohols are obtained by treating a Grignard reagent with aldehydes other than
formaldehyde
Tertiary alcohols are obtained by treating Grignard reagents with ketones.
Exceptional Behaviour of Grignard Reagent

Sometimes, Grignard reagent does not react with compounds containing functional group
normally capable of undergoing reaction. Generally, branching of the carbon chain near the
functional group prevents the reaction. For example, methyl magnesium bromide of iodide does
not react with hexamethyl acetone (CH3)3CCOC(CH3)3. It has also been found that if Grignard
reagent contains large alkyl groups, reaction may be prevented. For example, isopropyl methyl
acetone reacts with methyl magnesium iodide but not with t-butyl magnesium iodide. In other
cases, abnormal reaction may take place. For example, when isopropyl magnesium bromide is
added to di-isopropyl ketone, the expected tertiary alcohol is not formed, instead the secondary
alcohol, di-isopropyl carbinol is obtained resulting from the reduction of the ketone.
( CH ) CHMgBr
( CH 3 )2 CHCOCH ( CH 3 )2 3 2
→ ( CH 3 ) 2 CHCH ( OH ) CH ( CH 3 )2 + CH 3 CH = CH 2
α, β -unsaturated carbonyl compounds adds on Grigard reagents at the 1, 2 or 1, 4-position.
1, 2-addition:
R3
R3 -MgX
R1 -CH=CH-C=O R -CH=CH-C-OMgX
R R
R3
R1 -CH=CH-C-OH
R

1, 4-addition:
R 3 −MgX
R1 − CH = CH − C = O → R1 − CH − CH = C − OMgX
| | |
R3 R 2
R3
+
↓H3O
2 tautomerizes R1 -CH-CH=C-O-H 2
R1 -CH=CH2-C-R
R3 O R3 R2
[enol]
The reaction of dihalides of the type Br(CH2)n Br with magnesium depends on the value of n.
For n = 1, no Grignard reagent is formed. For example,
C H C H 
| 2 | 2
Mg
ether
| 2 |
Mg
→ CH2 = CH2 ,CH2 − C H − C H2 
ether
→ >
Br Br Br Br
When n ≥ 4, the Grignard reagent can be possible made with dibromo compound i.e,
Br(CH2)nBr.j
6.5 Methods of Preparation of Alcohols

Alcohols are prepared by the following methods:
Hydrolysis of Alkyl Halides
Alkyl halides react with aqueous sodium hydroxide to form alcohols.
Hydration of Alkenes
Reacts with sulphuric acid to produce alkyl hydrogen sulphate (Markovnikov rule is followed).
Alkyl hydrogen sulphates on hydrolysis give alcohols. For example,
The overall result of the above reactions appears to be Markovnikov addition of H2O
(Hydration to a double bond.

Hydroboration-Oxidation of Alkenes
Alkenes react with diborance to form trialkyl boranes, which upon treatment with alkaline
H2O2 give alcohols via anti–Markownikoff’s addition of water.
THF H2O2/OH
C=C + (BH3)2 C C C C + B(OH)3
H BH2 H OH
Alkyl borane Anti-Markownikoff
addition of H2O
For example,
(i)(BH3)2 (ii)H2O2, OH
CH3 H
CH3 H OH
1-Methylcyclopentene 2-Methyl-1-cyclopentanol
Syn-addition
CH3 CH3
(i)(BH2)2(ii)H2O2, OH
CH3 C CH=CH2 CH3 C CH2CH2OH
CH 3 CH 3
3, 3-Dimethyl-1-butene 3, 3-Dimethyl-1-butene
(i) Hydroboration-oxidation of non-terminal alkynes leads to the formation of ketones. For

example,
OH
( )
| −
| 3 RCH2COR
3RC ≡ CR 
BH 3
THF
→ RCH = C R B 
H 2 O 2 / OH
→ 3R − C H = C − R
3
(ii) Non-catalytic hydrogenation: Hydroboration-oxidatin can be used to reduce double bonds in

alkene without using molecular hydrogen and a transition metal catalyst. For example,
Me 2 C = CHMe 
BH 3
THF (
→ Me 2 CH − CHMe B 
3CH 3 COOH
|
)
→ 3Me 2 CH − CH 2 Me
3
Hydrolysis of Esters
Alcohols may be prepared by base or acid-catalysed hydrolysis of ester.
Reduction of Aldehydes and Ketones

Aldehydes and ketones can be reduced with H2/Ni or lithium aluminium hydride to form the
corresponding alcohols. Aldehydes give primary alcohols. Ketones give secondary alcohols.

Fermentation of Carbohydrates
Some alcohols can be prepared by fermentation of starches and sugars under the influence of
suitable micro-organisms. For example.
6.6 Properties
Physical
1. Lower alcohols are colourless, toxic liquids. They have a characteristic smell
2. Boiling points of alcohols increase regularly with the increase in the number of carbon atoms.
3. Among isomeric alcohols, as branching increases the boiling points decrease. For example,
4. Boiling points of alcohols are much higher than those of the corresponding alkanes.
Explanation: The O–H bond of alcohols is highly polar because oxygen is electronegative.
The oxygen carries a partial negative charge (δ-). The hydrogen carries a partial positive
charge (δ+). The polarity of the O–H bond gives rise to forces of attraction between a partially
positive hydrogen in one alcohol molecule and partially negative oxygen in another alcohol
molecule. These forces of attraction are referred to as Hydrogen Bonding. The reason that
alcohol have higher boiling points is that a great deal of energy (in the form of heat is
required to overcome these attractive forces.
Alkanes, which have no –OH group, do not undergo hydrogen bonding. Therefore, their
boiling poins are low.
5. Lower alcohols (C1 to C3) are completely soluble in water. As we go higher in the series, the
water solubility falls rapidly.
Explanation: A compound that forms hydrogen bonds between its own molecules can also
form hydrogen bonds with water. These alcohol-water hydrogen bonds are the cause of high
solubility of lower alcohols in water. In higher alcohols, the nonpolar alkyl group becomes
more important. They have less tendency to form hydrogen bonds with water rand hence are
less soluble.

Chemical Properties
Alcohols are reactive compounds. They are attacked by polar or ionic reagents. This is because:
1. The C–O and O–H bonds of the alcohols are polar since oxygen is highly electronegative.
2. They oxygen atoms of alcohols is an electron-rich centre because it has two unhshared pairs
of electrons.
6.7 Alcohols undergo the following general reactions

Reaction with Active Metals
Alcohols react with sodium or potassium to form alkoxides with the liberation of hydrogen gas.
The above reaction shows that alcohols are acidic in nature. The reason for this is that the O–
H bond in alcohols is polar and allows the release of the hydrogen atom as proton (H+). However,
alcohols are weaker acids (Ka = 10–16 to 10–18) than water. This is because the alkyl groups in
alcohols have a +I effect. They release electrons towards the oxygen atom so that it becomes
negatively charged. This negative charge on oxygen makes the release of the positive proton more
difficult.
Tertiary alcohols are less acidic than secondary alcohols. The secondary alcohols are less
acidic than primary alcohols. This is because the +I effect would be maximum in tertiary alcohols,
as they contain three alkyl groups attached to the carbon bearing the –OH group.
Alcohols are not acidic enough to react with aqueous NaOH or KOH.
R – OH + NaOH → No reaction.

6.8 Reaction with Phosphorus Halides
Alcohols react with phosphorus penthahalides (PX5) and phosphorus trihalides (PX3) to form
alkyl halides.
(i)
(ii)
Reaction with Thionyl Chloride

Alcohols reaction with thionyl chloride (SOCl2) to form alkyl chlorides.
Reaction with Hydrogen Halides

Alcohols react with hydrogen (HX) to form the corresponding alkyl halides
where HX = HI, HBr, HCl.
In general, tertiary alcohols react rapidly with hydrogen halides; secondary alcohols react
somewhat slower; and primary alcohols, even more slowly. The order of reactivity of hydrogen
halides is HI > HBr > HCl. HCl reacts only in the presence of a catalyst (anhydrous (ZnCl2). No
catalyst is required in the case of HBr or HI.
Mechanism. Primary alcohols react with hydrogen halides by an SN1 mechanism. The
mechanism of the reaction between ethyl alcohol (1° alcohols) and hydrogen bromide is described
below
Step-1 Protonation of ethyl alcohol
Step-2 Nucleophile (Br–) attacks the carbon holding the protonated hydroxyl group to form
ethyl bromide.

Primary and secondary alcohols react with hydrogen halides by an SN2 mechanism.
Reaction with Nitric Acid
Alcohols react with nitric acid to form alkyl nitrates. For example,
Reaction with Sulphuric Acid

The reaction of alcohols with sulphuric acid is very sensitive to reaction conditions. For example
(i) When ethyl alcohol is treated with concentrated sulphuric acid at room temperature, ethyl
hydrogen sulphate is produced.
(ii) Dehydration of Alcohols to Alkenes. When ethyl alcohol is treated with concentrated
sulphuric acid at 170°C, ethylene is formed. Notice that only one alcohol molecule is involved
in the reaction.
Mechanism. The mechanism of the above reaction involves the following steps:
Step-1 Protonation of the alcohol molecule.
Step-2 Elimination of water molecule from the protonated alcohol gives a stable carbonium
ion.
Step-3 Carbonium ion loses a proton to give the alkene.
The ease of dehydration of alcohols follows the order 3° > 2° > 1° which is also the order of
stability of the carbonium ions.
Dehydration of secondary and tertiary alcohols containing four or more carbon atoms gives a
mixture of mixture of two alkenes. For example,

The alkene produced in greater abundance is indicated by Saytzeff Rule. It states that the
alkene performed preferentially is the one containing the higher number of alkyl groups.
Therefore, in the solve example, 2-butene is the major product.
(i) Dehydration of Alcohols to Ethers. When excess of ethyl alcohol is treated with concentrated
nitric acid at 140°C, diethyl ether is formed. Notice that two alcohol molecules are involved in
the
Mechanism. The mechanism of the above reaction involves the following steps:
Step-1 Protonation of the alcohol molecule
Step-2 Elimination of water molecule from the protonated alcohol gives a stable carbonium
ion.
Step-3 Carbonium ion attacks another alcohols molecule to form an oxonium ion.
Step-4 Oxonium ion loses a proton to form an ether
Dehydration of alcohols to ethers or alkenes can also be brought about by passing the
vapours of the alcohol over heated alumina catalyst. For example,

Reaction with Carboxylic Acids

Alcohols react with carboxylic acids to form esters. Concentrated sulphuric acid is used as
catalyst. The reaction is reversible and can be shifted in the forward direction by removing water
as soon as it is formed.
The reaction between an alcohol and a carboxylic acid to form an ester is called Esterification.
Reaction with Acid Halides and Acid Anhydrides
Alcohols react with acid halides and acid anhydrides to form esters.
Reduction
Alcohols undergo reduction with concentrated hydriodic acid and red phosphorus to produce
alkanes.
Oxidation
Alcohols can be oxidised. The nature of the product depends on the type of alcohol and the
conditions of the reaction. Most widely used oxidising agents are KMnO4 + H2SO4 or Na2Cr2O7 +
H2SO4. Oxidation of alcohols can be used to distinguish between primary secondary and
tertiary alcohols.
Primary alcohols are first oxidised to aldehydes and then to acids.

Notice that the acid and the alcohol contains the same number of carbon atoms. The reaction
can be stopped at the aldehyde stage by removing it from the oxidising medium as it is formed
(e.g., by distillation).
Secondary alcohols are oxidised to the corresponding ketones.
Further oxidation under very drastic conditions breaks up the ketone molecule, producing
carboxylic acids containing fewer carbon atoms per molecule.
Tertiary alcohols are stable oxidation under normal conditions
Under drastic conditions, tertiary alcohols give ketones and acids, each containing less
carbons than the alcohols.
Reaction with the Hot Copper; Dehydrogenation
Different types of alcohols give different products when their vapours are passed over copper
gauze at 300°C.
Primary alcohols lose hydrogen and give an aldehyde.
Secondary alcohols lose hydrogen and yield a ketone.
Tertiary alcohols are not dehydrogenated but lose a molecule of water to give alkenes.
Haloform Reactions
The structural feature essential in the compound to show haloform reaction is that any of the
following moieties should be present in the molecule attached to some electron-withdrawing
group or electron donating group by + I only.

or any other grouping that can be converted to any of the above moieties. The mechanism of
the reaction can be outlined as
The reaction has 3 important steps. Step I is the oxidation, caused by mild oxidizing agent
(hypo halite ion). The second step is base-promoted halogenation and the third step is cleavage of
C-C bond.
Some of the compounds with responds positively to iodoform test are
6.9 Cleavage of 1, 2 – Glycos

Lead tetraacetate or periodic acid are commonly used for the cleavage of 1, 2-glycols. The former
reagent is used in anhydrous solvent, whereas the later in organic solvent. Periodic acid is more
selective and readily cleaves 1, 2-glycols at room temperature. But cleavage of an α-hydroxy
ketone or acid by this reagent even at higher temperature is slow. Lead tetraacetate, however,
oxidizes α - hydroxyketone or acid as well as 1, 2-glycols more easily. This is explained on the
basis of a five-membered cyclic intermediate.

C O O C O
I OH Pb(OAc)2
C O O C O
C O+ C O C O+ C O
A 1, 2-glycol need not necessarily be cis to undergo cleavage with lead tetraacetate. For instance,
trans-9, 10–decalindiol undergoes cleavage to cyclodecane –1, 6–dione.
6.10 Test for an – OH Group

The following three tests may be used to detect the presence of an –OH group in organic
compound. For these tests, take the liquid compound or a solution of the solid compound in an
inert solvent such as dry ether or benzene.
1. Add to it small pieces of Sodium metal. If bubbles of hydrogen gas are given off the compound
contains an – OH group.
2R − OH + 2Na → 2R − ONa + H 2 ↑
2. Add to it Phosphorus pentachloride. If the mixture becomes warm with evolution of HCl gas,
the given compound contains an –OH group.
R − OH + PCl5 → R − Cl + POCl3 + HCl ↑
3. Add Acetyl chloride or Benzoyl chloride to the substance. The separation of an oily layer of the
ester and evolution of HCl gas indicates the presence of an – OH group. It may be noted that
if the compound was taken in an organic solvent, the oily ester may dissolving it and thus
limiting the test to the evolution of HCl gas only.
How to Distinguish Between 1°, 2° and 3° alcohols?

The following tests are used to distinguish between primary, secondary and tertiary alcohols.
1. Lucas Test. In the test, alcohols are treated with a solution of HCl and zinc chloride (Lucas
reagent) to form alkyl halide. Zinc chloride serves as a catalyst.
ZnCl2
R − OH + HCl  → R − Cl + H 2 O
Alcohol Alkyl halide
The three types of alcohols undergo this reaction at different rates. Tertiary alcohols react
with Lucas reagent very rapidly. Secondary alcohols react somewhat slower. Primary alcohols
react with Lucas reagent even more slowly.
In practice, the Lcucas test is carried out as follows: An alcohol is mixed, at room temperature,
with concentrated HCl and ZnCl2. The alkyl chloride, which is formed, is insoluble in the
medium. It causes the solution to become cloudy before it separates as a distinct layer.
(a) With Tertiary alcohols cloudness appears immediately.
(b) With Secondary alcohols cloudiness appears in 5 minutes.
(c) With Primary alcohols the solution remains clear. This is because primary alcohols do
not react with Lucas reagent at room temperature. High temperatures are needed.

2. Victor Meyer;s Test. In this test, the following steps are involved,
(i) Alcohol is reacted with conc. HI or red phosphorous and iodine to form corresponding
alkyl iodide.
(ii) Alkyl iodide is then treated wth slver nitrite when corresponding nitroalkanes is formed.
(iii) Nitro alkane is treated with nitrous acid (NaNO2 + H2SO4) and the solution is made
alkaline by addition of excess of excess of caustic soda.
Primary Secondary Tertiary
RCH2OH R2CHOH R3CHOH
HI HI HI
RCH2I R2CHI R3CI
AgNI2 AgNI2 AgNI2
RCH2NO2 R2CHNO2 R3CNO2
HNO2 HNO2 HNO2
RC−NO2 R2C−NO2 No reaction
NaOH
NOH N=O
Nitrolic acid Nitrolic acid Colourless
NaOH NaOH
Blood red colour Blue colour
3. Dichromate Test. This test is based on the fact that different types of alcohols give different
products on oxidation. The alcohol is treated at room temperature with sodium dichromate in
sulphuric acid (orange solution). Identification of the products gives us information
regarding the type of the alcohol.

(a) Primary alcohols give a carboxylic acid containing the same number of carbons. There
will be a change in colour of the solution from orange to green.
(b) Secondary alcohols give a ketone containing the same number of carbons. There will be a
change in colour of the solution from orange to green.
(c) Tertiary alcohols do not react under these conditions. Solution will remain orange.
4 Glycerol, 1,2,3-Propanetriol, HOCH2 – CH(OH)–CH2OH. Glycerol or 1,2,3-propanetriol is
the most important trihydric alcohol. It was formerly known as Glycerine. Glycerol is found in
all natural fats and oils as glyceryl ester of long -chain carboxylic acids.
Manufacture. Gycerol is manufactured:
From Fats and Oils
Natural oils and fats are triester of glycerol and long-chain carboxylic acid (mainly palmitic,
steric, and oleic acids). On hydrolysis with alkali, the fats and oils produce glycerol and the salts
of the long-chain acids which are called soaps.
In the above equation, R is 9 to 17 carbons. The hydrolysis of fats and oils is carried originally
for soap manufacture, and glycerol is obtained as a by-product. This is still a commercial source
of glycerol.
Glycerol from Soap Manufacture. In soap manufacture, the fat is hydrolysed by boiling with
alkali.
Reaction with PCl5
Glycerol reacts with PCl5 to form glyceryl trichloride. All these –OH groups are replaced by Cl
atoms
Reaction with Hydrogen Iodide

Glycerol reacts with hydrogen iodide in two ways:
(a) When glycerol is warmed with a small amount of hydrogen iodide, it gives 1,2,3-
triiodopropane. This is unstable and splits out a molecule of iodine to yield allyl iodide.

(b) When glycerol is heated with a large amount of hydrogen iodide, allyl iodide first
produced as above is reduced to propene. In the presence of excess hydrogen iodide,
propene adds a molecule of hydrogen iodide to give 2-iodopropane (sopropyl iodide).
The addition takes placed according to the Markovnikov rule.
Reaction with Oxalic Acid

Glycerol reacts with oxalic acid in two ways:
(a) At 110°C glycerol reacts with oxalic acid to form glycerol monoformate.
Glycerol monoformate on hydrolysis gives formic acid and glycerol is regenerated.
(b) At 260°C glycerol reacts with oxalic acid to form allyl alcohol.
Reaction with Acetyl Chloride

Glycerol reacts with acetyl chloride (or acetic anhydride) to form glycerol triacetate
Oxidation
The two primary alcohol groups in glycerol are capable of being oxidised to the aldehyde and
then the carboxyl group. The secondary alcohol group can be oxidised to the carbonyl group.

Thus glycerol can give rise to a variety of oxidation products depending on the nature of the
oxidising agent.
6.11 Phenol
Phenols are compounds containing an —OH group attached directly to an aromatic ring. Like
alcohols, they may be monohydric or polydric according to the number of —OH groups that they
contain. Phenols are usually named by common system or as derivatives of the parents phenol
(C6H5OH).
Examples are
Compounds which contain an —OH group in a side-chain attached to an aromatic ring are
not phenols. They are called Aromatic Alcohols.
Examples are
Phenol, Hydroxybenzene, C6H5OH.

Phenol is the simplest and most important member of the series.
Preparation, Phenol is obtained by the following methods:
From Chlorobenzene (Dow Process)
This involves the hydrolysis of chlorobenzene with aqueous NaOH at high temperature and
pressure followed by treatment with dilute HCl.
Cl +
O Na OH
+ NaOH 623 K dil. HCl

 →
300 atm
This process was first introduced in 1928 by the Dow Chemical Company of U.S.A.

From Cumene
This involves air oxidation of cumene (Isopropylbenzene) followed by treatment with dilute HCl.
The above Cumene. Process accounts for 80% of the total world production of phenol. The
success of this method is due to the availability of benzene and propene from petroleum and to
the formation of acetone, a valuable by product.
From Sodium Benzenesulphonate
This involves fusion of sodium benzenesulphonate with solid NaOH at 300°C followed by
treatment with dilute HCl.
From Benzenediazonium Salts

This reaction can be performed easily in the laboratory and simply requires warming a solution of
benzenediazonium chloride, prepared from aniline, on a water bath at 50°C.
The phenol is recovered by steam distillation and extracted with diethyl ether.
Physical Properties of Phenols

(1) Most puire phenols are colourless liquids or solids, although they are often found to contain a
red tint owing to the presence of oxidation products.
(2) Phenols have a characteristic ‘Carbolic’ odour, which in case of phenol itself is highly toxic.
(3) The boiling points of phenols are higher than aliphatic alcohols of comparable molecular
weights. This is due to stronger intermolecular hydrogen bonding in phenols relative to
alcohols.
The introduction of a hydroxy group into an already substituted aromatic ring, especially in
the para position to methyl, halogen, or nitro group, produces a marked increase in the
boiling point. The effect on nitrophenol is shown below:

The greater volatility of the ortho isomer is due to intermolecular hydrogen bonding where
higher boiling point of he para isomer is due to intermolecular hydrogen bonding.
Also, p-nitrophenol is more soluble in water than o-nitrophenol. This is because p-nitrophenol
can associate with itself and also with water molecules. o-Nitrophenol cannot form
intermolecular hydrogen bonds.
The low solubility and higher volatility of o-nitrophenol enables it to be easily separated from
p-nitrophenol by steam distillation.
6.12 Properties (Chemical)

The reactions of phenol are the reactions of the —OH group and the benzene ring.
Reaction of –OH Group
Formation of salts.
Phenol is acidic. It reacts with sodium hydroxide or sodium metal to form salts.

Phenol is weaker acid than carboxylic acids. It does not react with sodium carbonate or
bicarbonate.
Formation of Esters
Phenol reacts with acid chlorides (or acid anhydrides) in aqueous alkali solution to give phenyl
esters. The alkali first forms the phenoxide ion which then reacts with the acid chloride.
The reaction of phenol with benzoyl chloride is known as Schotten-Baumann reaction.

Formation of Ethers
(a) Phenol reacts with alkyl halides in alkali solution to form phenyl ethers. The alkali first
forms the phenoxide ion which then reacts with the alkyl halide.

(b) Phenol reacts with dimethyl sulphate in alkali solution to form anisole (Methyl phenyl
ether).
Reaction with Zinc Dust

When phenol is distilled with zinc dust, low yield of benzene is obtained.
6.13 Reactions of Benzene Ring

Phenol undergoes electrophilic substitution reactions much readily as compared to benzene ring.
The reaction conditions used for monosubstitution in benzene give trisubstituted with phenol. By
moderating the reaction conditions, however, we can obtain the monosubstitution product.
Remember that the –OH group in phenol is an o, p-director and activator.
Halogenation
Phenol reacts with bromine water (aqueous bromine) to give precipitate of 2, 4, 6-tribromophenol.
Chlorine reacts in the same way.
If the reaction is carried in CS2 or CCl4 (nonpolar solvents), a mixture of o- and p-bromophenol is
formed.
Nitration
Phenol reacts with dilute nitric acid to give a mixture of o- and p-nitrophenol.

With concentrated nitric acid, picric acid is formed.
Nitrosation
Phenol reacts with nitrous acid (obtained from NaNO2/HCl at 5°C) to form p-nitrosophenol
exclusively.
p-Nitrosophenol on oxidation with dilute nitric acid gives p-nitrophenol exclusively.
Illustrations
Illustration 1
Explain why prhenols do not undergo substitution of the –OH group like alcohols?
Solution
The C–O bond in phenols has some double bond character due to resonance and hence cannot be
easily cleaved by a nucleophile.
Illustration 2
Of the two dydroxy organic compounds ROH and R’OH, the first one is basic and the other is
acidic in behaviour. How is R different from R’?
Solution
When R = alkyl, ROH behaves as a Lewis base when R’ = anyl R’OH behaves as a Bronsted acid.
Illustration 3
Phenol has smaller dipole moment than methanol. ]

Or Why are dipole moments of phenols smaller than dipole moments of alcohols.
Solution
Due to electron-withdrawing effect of the benzene ring, the C–O bond in phenol is less polar but
in case of methanol due to electron-donating effect of CH3 group, C–O bond is more polar.
Illustration 4
Name the phenol with molecular formula C7H8O which on treatment with Br2 water readily gives
a precipitate of C7H5OBr3.
Solution
m-Cresol.
Practice Exercise
1. Name the reagents in the following reactions:

(i) Oxidation of a primary alcohol to a carboxylic acid
(ii) Oxidation of a primary alcohol to an aldehyde
(iii) Bromination of phenol to 2, 4, 6-tribromophenol ]
(iv) Benzyl alcohol to benzoic acid
(v) Butan-2-one to butan-2-ol.
Answers
1. (i) Acidified potassium dichromate or, neutral, acidic or alkaline potassium permanganate.
(ii) PCC
(iii) Aqueous bromine
(iv) Acidified or alkaline potassium permanganate
(v) Conc. H2SO4 at 433-443 K or 85% phosphoric acid at 443 K.
6.14 Sulphonation
When phenol is treated with concentrated sulphuric acid at 20°C, o-phenolsulphonic acid is the
main product. At 100°C, p-phenolsulphonic acid is the main product.

Reimer-Tiemann Reaction
This involves the treatment of phenol with chloroform in aqueous sodium hydroxide solution
followed by acid hydrolysis. Salicylaldehyde is formed. If carbon tetrachloride is used in place of
chloroform, salixylic acid is formed.
The Reimer-Tiemann reaction is also given by other phenols and introduces –CHO group in
the ortho position.
Mechanism
In the above reaction, chloroform first reacts with sodium hydroxide to produce
dichlorocarbene.
The electron-deficient dichloricarbene then reacts with sodiumphenoxide to form a dihalide.

This is then hydrolysed to form the aldehyde.
Kolbe Reaction
This involves the treatment of sodium phenoxide with carbon dioxide at 125°C under 6
atmospheres of pressure followed by acid-hydrolysis. Salicylic acid is formed.

Mechanism
The phenoxide carbanion adds to the electrophilic carbon of carbon dioxide. Three steps are
involved:
The Kolbe reaction is also given by other phenols and introduces COOH group in the ortho
position. This reaction is also called Kolbe-Schmidt reaction.
Gatterman Reaction
This involves the treatment of phenol with a mixture of hydrogen cyanide and hydrogen chloride
in the presence of aluminium chloride catalyst. Salicylaldehyde is formed.
Fries Rearrangement
The phenol is first related with acetic anhydride in the presence aqueous sodium hydrazide to
give phenyl acetate. The ester is then heated with aluminium chloride catalyst when the acyl
group migrates from the phenolic oxygen to an ortho or para position of the ring. The product is a
mixture of o- and p-hydroxyacetophenone.
The fries rearrangement is also given by other phenols and introduces –COR group in the
ortho and / or para positions.
Reaction with Benzenediazonium Chloride.
Phenol couples with benzenediazonium chloride in an alkanline solution to form h-
hydroxyazobenzene (a dye).

Reaction with Phthalic Anhydride
Phenol reacts with phthalic anhydride in the presence of sulphuric acid to form phenolphthalein.

Reaction with Formaldehyde
When phenol is treated with an alkaline solution of form aldehyde, a mixture of o- and p-
hydroxybenzyl alcohol is formed.
If the reaction is carried at high temperature and in excess of form aldehyde, hard
thermosetting plastic Bakelite is formed.
Oxidation
Phenol undergoes oxidation with air or chromic acid to form p-benzoquinone.
Catalytic Hydrogenation
Phenol on catalytic hydrogenation gives cyclohexanol. A mixture of its vapour and hydrogen is
passed over nickel catalyst at 160°C.
ETHER
Ethers are compounds in which is bonded to two alkyl substituents. If the alkyl substituents are
identical, the ether is symmetrical or simple ether.
R —O—R R — O — R′
A symmetrical or simple ether An unsymmetrical or mixed ether
The groups R and R' can be alkyl or aryl. When both the R groups are alkyl, they are called alkyl
ether and when at least one of the R group is an aryl, they are called aryl ethers.
6.15 IUPAC Nomenclature of Ethers

The common name of ether is obtained by citing the names of the two alkyl substituents in
alphabetical order, followed by the word “ether”. The smallest ether is almost always named by
their common names.
CH 3OCH 2 CH 3 CH3CH 2 OCH 2 CH3
ethyl methyl ether diethyl ether

CH3
|
CH3 C HO C HCH 2 CH3
|
CH 3
CH3CH2CH2 – O
sec − butyl isopropyl ether cyclohexyl n-propyl ether
The IUPAC system names ether as an alkane that contains an alkoxy substituent. The alkyl part
with greater number of carbon atoms is named as alkane while the other alkyl part is named as
alkoxy by removing the “yl” from the name of the alkyl substituent and adding “oxy”. For
example, CH3O– is called methoxy, CH3CH2O– is called ethoxy. CH 3 C H − O − is called
|
CH3
isopropoxy, CH3CH 2 C H − O − is called sec-butoxy and (CH3)3C – O – is called tert-butoxy. Thus,
|
CH3
IUPAC name for ether is alkoxyalkane.
6.16 General Methods of Preparation of Ethers

Intermolecular Dehydration of Alcohols
When alcohols are treated with H2SO4or H3PO4at 140°C, a molecule of water is eliminated from
two alcohol molecules to give ether. This reaction is called intermolecular dehydration of
alcohols. Alcohols on dehydration intramolecularly, give alkene. Thus, dehydration of alcohols to
ether can be achieved by controlling the reaction conditions i.e. reaction is carried out at low
temperature (it should not increase beyond 140°C). Alcohol should be taken in excess. When the
dehydration is carried out above 140°C, it leads to elimination forming an alkene.
conc. H2SO4.
conc. H 2SO 4
R − O − H + H − O − R  → R − O − R + H2O
∆ , 140ºC
Dehydration of alcohols to ether is useful for the preparation of symmetrical ethers only. If we try
to prepare unsymmetrical ether using a combination of two alcohols (ROH & R'OH), it leads to
the formation of a mixture of three ethers (R–O–R, R–O–R' and R'–O–R').
Dehydration of alcohols to ether is an example of nucleophilic substitution. A protonated alcohol
molecule acts as substrate and the second alcohol molecule act as nucleophile. The reaction

can proceed by SN1 or SN2 process. Primary alcohols react by SN2 process and secondary &
tertiary alcohols undergo reaction by SN1 process.
Dehydration of alcohols can also be achieved by passing vapours of ethyl alcohol over heated
Al2O3 at 250°C.
Al2O3
C 2 H 5 OH + HOC 2 H 5  → C2 H 5 − O − C 2 H5 + H 2 O
250ºC
Intermolecular Dehydration of Alcohols

When an alkoxide is treated with an alkyl halide, ether is produced. The method was developed
by Williamson and is useful for the preparation of symmetrical as well as unsymmetrical ethers.
where R' can be same as or different from R.

The alkoxide can be prepared by the action of alcohols with sodium or potassium
→ RO − K + +
RO − H + K  1
2 H2 ↑
This reaction involves SN2 mechanism, with alkoxide ion acting as nucleophile and alkyl
halide as the substrate. The complete mechanism follows as
For ether to be obtained as major product, reaction should follow substitution and
minimize elimination reaction. This can be achieved by taking only methyl halides or 1° halides
with lesser branching near the reaction site.
But if we take 2° and 3° alkyl halides, which have more tendency to undergo elimination,
will give very less yield of ethers.
Suppose, we want to prepare ethyl tert-butyl ether. There are two possible routes to
prepare it.

Route (A) is more suitable to prepare given ether as the alkyl halide involved in this route
is a primary one while in route (B), the halide being a 3°, it will lead to elimination reaction
forming an alkene, 2-methyl propene.
Alkoxymercuration-demercuration
In overall alkoxymercuration-demercuration reaction, ROH is added to the double bond. The
reaction do not involve any carbocation as intermediate, so it is free from rearrangement and also
involves syn addition, which is in accordance to Markownikoff’s rule.
Alkenes react with mercuric acetate in the presence of alcohol to give alkoxymercurial compound,
which on demercuration bv NaBH4 gives ethers.
General Physical Properties of Ethers
Diethyl ether is a highly volatile liquid, used as a solvent, as an anesthetic and in the preparation
of Grignard reagents.
Boiling point of ethers is less than that of the corresponding alcohols (of similar molar mass) due
to absence of hydrogen bonding. The solubility of ethers in water is comparable to that of the
alcohols as both are able to form hydrogen bond with water. The hybridization of oxygen atom in
ether is sp3, so the shape of an ether molecule is angular or bent with bond angle of 110°. The
bond angle is greater than the normal bond angle in a tetrahedron with lone pairs, as repulsion
between the bulkier alkyl groups is dominant over the lone pair repulsion.
Ether molecules are polar and they have a small net dipole moment. The net dipole
moment of diethyl ether is 1.18 D.

General Chemical Reactions of Ethers
Ethers are quite unreactive compounds as ether linkage is very stable towards bases, oxidising
agents and reducing agents. Ethers can be easily cleaved in the presence of acids. Few of the
common reactions of ether are as follows:
Salt Formation
When ethers are treated with cold concentrated inorganic acids, these form oxonium salts. The
reaction between ether and acid is a Lewis acid-base type interaction.
Cleavage by heating with acids

Ethers on reaction with acids (HX) in presence of heat undergoes cleavage to form an alkyl halide
and an alcohol. Alcohol on further reaction with HX gives second molecule of alkyl halide.
R − O − R ′ + H + X 
→ R − X + R ′ − OH
R ′ − OH + H − X 
→ R ′ − X + H 2O
HI is more reactive towards ether than HBr and HBr is more reactive than HCl.
Mechanism
In the first step, ether is portonated by HX to give protonated ether. In the second step,
halide ion acts as nucleophile and attacks protonated ether to undergo cleavage. This step is
favoured because the leaving group (alcohol) is weakly basic.
H
.. |
Step I. R − O : − R ′ + H − X   R − O− R ′ + X′
⊕
protonated ether
Step II.
Reaction in second step can take the direction of SN1 or SN2 pathway, depending upon the
conditions employed and the structure of ether. When both the alkyl groups are methyl or 1º, it
will follow SN2 reaction and when atleast one of the alkyl group is 3º, the reaction follows SN1

pathway. For all other cases, it can undergo SN1 or SN2 pathway, depending, depending upon the
reaction conditions.
For example
There are two IUPAC approved ways to name epoxides. According to one metho,d the
three-membered oxygen containing ring is called “oxirane”, with oxygen atom occupying 1-
position. Thus, propylene oxide is called 2-methyl oxirane. Alternatively, an epoxide can also be
named as a alkane, with “epoxy” substituent and the numbers of the carbons to which the oxygen
is attached immediately proceeding the alkane name.
Preparation of Epoxides
Epoxide can be prepared by the oxidation of alkene using peroxy acids.
The reaction is referred as epoxidation and we have already discussed its mechanism in
the lesson alkenes. Three membered cyclic ethers can also be prepared by internal SN2 reaction of
a chlorohydrin.
Reactions of Epoxides
As three membered epoxide ring is highly strained, so they are highly susceptible to ring cleavage
in order to get relieve from the strain. Thus, epoxides can be cleaved by acids as well as by bases.

Acid-Catalysed Cleavage of Epoxides
In the first step, protonation takes place to give protonated epoxide. This is then attacked
by H2O (a poor nucleophile) to undergo ring opening at room temperature, which finally loses H+
to give ethylene glycol.
Base-catalysed cleavage of epoxides
Here, the nucleophile attacks epoxide ring and cleave it, which then abstracts a proton
from the solvent (or from the acid added after the reaction is over) to give ethylene glycol. When
a nucleophile attacks an unprotonated epoxide, the reaction is a pure SN2 and thus nucleophile
attacks the less hindered carbon.
In case of unsymmetrical epoxides, for instance, propylene oxide, the acid-catalysed
cleavage proceeds as follows :
In this case, after the protonation step, nucleophile attacks at the more substituted carbon
because the leaving group (alcohol) is better one and the nucleophile (H2O) is poor one. Thus,
leaving group starts leaving before the nucleophile attacks or in other words, bond breaking is
more than bond making in the transition state. As the carbon-oxygen bond breaks faster, a partial
positive charge develops on the carbon that is losing its share of the oxygen’s electrons and

protonated epoxide breaks preferentially in the direction that puts the partial positive charge on
the more substituted carbon because the positive charge is more stable here due to +I effect of
methyl group. Thus, we can say that the reaction proceeds by SN2 pathway with considerable SN1
characteristics in it. The reaction is neither pure SN1 (because a carbocation is not fully formed)
nor pure SN2 (because leaving group begins to depart before the compound is attacked by the
nucleophile).
In propylene oxide, base-catalysed cleavage proceed as follows:
Since, this reaction is a pure SN2 reaction, so nucleophile attacks at the less substituted
carbon to undergo ring opening. The alcohol-alkoxide ion then takes up a proton from the solvent
to give find product.
The product of acid -catalysed cleavage and base-catalysed cleavage of propylene oxide
are different because they are enantiomers having similar values of optical rotation but with
different sign.
Illustrations
Illustration 5
Account for the 14C-labeled product from the following reaction,
Solution
This is not a direct Williamson reaction. Instead the reaction is initiated by an SN2 displacement by
CH3O– on the less substituted 14C of the epoxide, giving an intermediate alkoxide ion. The O–
then acts as a nucleophile (neighboring group participation) to displace Cl– by a second SN2
reaction, forming the product.
Illustration 6
Which of the following decreasing order is correct in Williamson synthesis of the compounds?

Br Br
(I) (II)
CI
(III) (IV)
Solution
CH 2 = CH − CH 2 − Br > CH 3 CH 2 CH 2 − Br > CH 3 CH 2 − CI > ( CH 3 )3 C − Br
(allylic and 1°), (1° and C − Br bond), (1° and C − CI bond), (3°)
Illustration 7
The order of reactivity of the following towards electrophic substituting reaction is
OH OCH3 CF3 CH3
(I) (II) (III) (IV)

Solution
Electron releasing effect in decreasing order:
−OH > −OCH 3 > −CH 3 > −CF3
Hence order C6 H 5 OH > C6 H 5 OCH 3 > C6 H 5 − CH 3 > C 6 H 5 CF3
Illustration 8
Sodium t-butoxide on treatment with ethyl bromide gives:
Solution
From Williamson’s synthesis.
Illustration 9
The product Z of the following series of reactions is
CH3
( i ) Hg ( OAc )
( i ) Na
CH3 CH2 CH = CH2  → Y  →Z
2
( ii ) NaBH 4 ( ii ) CH 2 Br
Solution
CH3
( i )Hg ( OAc )
CH3 CH2 CH = CH2  →
2
( ii ) NaBH 4
CH3
( i ) Na
CH3CH2 C CH3 
( ii ) CH 3 Br
→
OH

CH3
CH3 CH2 C CH3
OCH3
Practice Exercise
2. 2-Phenylethanol may be prepared by the reaction of phenyl magnesium chloride with
3. An organic compound of molecular formula C4H10O does not react with sodium. With excess of HI, it
gives only one type of alkyl halide. The compound is
4. Epichlorohydrin is
5. It is advised to store ether in brown bottles with the addition of a small quantity of ethanol. Explain
Answers
CH2
C6H5-MgCI+ O
2.
CH2
Na
3. CH3 CH2 O CH2CH3 No reaction
Cone.HI CH CH I+CH CH OH
3 2 3 2
Cone.HI CH CH I+H O
3 2 2
O
1 2 3
CH2-CH-CH2-CI
4.
3-Chloro-1,2-epoxypropane
5. Sun light effect is reduced due to brown colour of the bottle and hence chances of peroxide
formation are reduced to great extent.
6.17 Aryl Ethers

Phenols are converted into alkyl aryl ethers by reaction in alkaline solution with alkyl halides. For
the preparation of aryl methyl ethers, dimethyl sulfate, (CH3)2SO4 is frequently used instead of
more expensive methyl halides. For example

The second method is a better method to prepare anisole because methyl sulphonates
(mesylates) are better leaving group than Br, which causes faster substitutions. Secondly, with
respect to CH3Br, dimethyl sulphate is less expensive, so economically, (CH3)2SO4 is better to
cause methylation of phenol.
The mechanism of the above reaction can be outlined as follows. In alkaline solutions,
phenol exist as phenoxide ion which acts as nucleophile and attacks the alkyl halide (or the
dialkyl sulfate) and displaces halide ion (or sulfate ion).
The above reaction is familiar Williamson’s synthesis, which can even be used for the
preparation of unsymmetrical ethers like alkyl ethers.
Since phenoxides are prepared from phenols and since alkyl halides are conveniently
prepared from alcohols, alkyl aryl ethers (like dialkyl ethers) are ultimately synthesized from two
hydroxy compounds.
Aryl halides cannot be used in the Williamson’s synthesis because of their low reactivity
towards nucleophilic substitution. For the preparation of any alkyl aryl ether, there can be two
combinations of reactants, but one combination can usually be ruled out. For example,
*****

Miscellaneous Problems
Objective Type
Example 1
Which of the following product is formed on acid catalysed hydration of 2-phenyl propene?Solution
(a) 1-phenyl-2-propanol (b) 1-phenyl-1-propanol
(c) 1-phenyl-3-propanol (d) 2-phenyl-2-propanol
Solution
Addition of water to 2-phenyl propene follows Markownikoff’s rule.
∴ Ans. (d)
Example 2
Which of the following is the best reagent to convert cyclohexanol to cyclohexene?

(a) Concentrated H3PO4 (b) Concentrated HCl
(c) Concentrated HBr (d) Concentrated HCl + anhydrous ZnCl2
Solution
Cl– and Br– are better nucleophiles than H2O, so with concentrated HCl and concentrated HBr, the
corresponding chloride and bromide would have been formed. But phosphate is a very poor nucleophile
because of its bulkier size and would be used effectively for causing elimination only.
∴ Ans. (a)
Example 3
The product of the reaction between
MgBr + (H3C)3COH → ?
OH
(a) (b)
CH3 CH3
C − CH3 O − C − CH3
(c) (d)
CH3 CH3
Solution
Grignard reagent with any compound containing active hydrogen will form a hydrocarbon.
∴ Ans. (a)

Example 4
H3 C H CH3
on hydrolysis in presence of aqueous acetone gives
CH3O NO2
H Cl CH3
H3C H CH3 H3 C H CH3
(K) : MeO NO2 ; (L) : MeO NO2
H OH CH3 OH H CH3
CH3 H CH3
(M) : MeO NO2
H CH3 OH
(a) (K) and (L) (b) (K) only
(c) (K) and (M) (d) (M) only
Solution
The rection follows partly SN1 and partly SN2 mechanism in aqueous acetone. In SN1 mechanism, the 2°
carbocaton formed due to the loss of Cl– undergoes rearrangement forming more stable benzylic
carbocation containing –OCH3 group at the p-position. Therefore, products (K) and (L) would be formed.
∴ Ans. (a)
Example 5
Which of these reagenets will form n-propionic acid from ?
(a) NaOH + I2, H+ (b) Fehling’s solution
+
(c) NaOH + NaI, H (d) Tollen’s reagent
Solution
O
|| (i) NaOH + I2
CH3 − C− CH 2 CH3 + I2 
+ → CHI3 ↓ + HOOCCH 2 CH3
(ii) H
( Iodoform reaction ) ( n − propionic acid )
∴ Ans. (a)
Example 6
What is the major product of the following reaction?
O
NaBH 4
→
CH OH
?
3
CO2H
OH OH
(a) (b)
CH2OH CO2H
O OH
(c) (d)
CH2OH CO2CH3
Solution
Sodium borohydride is a mild reducing agent. It can reduce only aldehydes and ketones to alcohols but
cannot reduce carboxylic acids.

∴ Ans. (b)
Example 7
Which of the ester shown, after reduction with LiAlH4 will yield two molecules of only a single alcohol?
(a) CH3CH2CO2CHCH3 (b) C6H5CO2C6H5
(c) C6H5 – CO2 – CH2C6H5 (d) HCO2C2H5
Solution
Lithium aluminium hydride reduces an ester (RCOOR') to a mixture of two alcohols i.e., RCH2OH and
R'OH. In the given problem both the alcohols are same. Therefore, the ester must be of the type
RCOOCH2R.
O
||
LiAlH
C6 H5 − C− OCH 2 C6 H5 
4
→ 2C6 H5 CH 2 OH
∴ Ans. (c)
Example 8
Heating a particular ether with HBr yielded a single organic product. Which of the following conclusions
may be reached?
(a) The reactant was a methyl ether
(b) The reactant was a symmetrical ether
(c) The reactant was a cyclic ether
(d) Both (2) and (3) may be correct
Solution
An unknown ether reacts with excess of HBr to yield a single product. This implies that the ether must be
either symmetrical or cyclic.

R − O − R + H − Br → R − Br + R − OH
R − O − H + H − Br → R − Br + H 2 O
(i)
R − O − R + 2H − Br → 2R − Br + H 2 O
O Br Br
(ii) + 2HBr + H2 O
∴ Ans. (d)
Example 9
What reactant gives the product shown on heating with anhydrous AlCl3?
O
H3C C OH
O O
(a) H 3C O C (b) H3C C O

O
(c) H3 C C OH (d) H3C OH
C CH3
O
O
Solution
Phenyl esters of alip(hatic or aromatic carboxyic acids when heated with anhydrous AlCl3 undergo Fries
rearrangement. The given product can be obtained from
O − CO CH3 OH
AlCl3
∆
CO CH3
∴ Ans. (b)
Example 10
What are the products of the following reaction?

1. Excess HBr
OCH2CH2OH ?+?
2. Heat
(a) p – Br – C6H4 – OCH2CH2OH (b) Ph – Br + BrCH2CH2OH
(c) Ph – Br + BrCH2CH2Br (d) Ph – OH + BrCH2CH2Br
Solution
O − CH2CH2OH OH
HBr
+ Br − CH2CH2 − OH
∆
HBr
Br – CH2CH2 – OH → Br – CH2CH2 – Br + H2O
∴ Ans. (d)
Subjective Type
Example 1
Al2O3 (i) HI Al2O3 (i) B2 H 6
(A)  → (B)  → (C)  → (B)  → (A)
250ºC (ii) AgOH 150ºC (ii) H 2O 2 , OH −
In the above reactions scheme (A) and (C) are isomers. (B) has a formula of C5H10, which can also be
obtained from the product of the reactions of CH3CH2Br and (CH3)2CO. Give structures of (A), (B) and (C).
Solution
(A) (CH3)2CHCHOHCH3, (B) (CH3)2C=CHCH3 (C) (CH3)2C(OH)CH2CH3
Example 2
Arrange the increasing/decreasing order
(a) Reactivity towards halogen acid (HX).
(i) CH3CH2OH (ii) (CH3)2CHOH (iii) (CH3)3COH

(b) Reactivity with sodium metal
1ºalcohol (ii) 2º alcohol (iii) 3º alcohol
(c) Boiling points
(i) CH3CH2CH2CH2OH (ii) CH3CH2CH2CH2CH3
(iii) C6H5OH
(d) Basicity :
(i) H 2O (ii) OH– (iii) CH3–O
(e) Acidity :
(i) H 2O (ii) C2H5OH (iii) C6H5COOH
(f) Acidity :
(i) Phenol (ii) p-cresol (iii) p-nitrophenol (iv) ethanol
Solution
(a) (iii) > (ii) > (i) (b) (i) > (ii) > (iii) (c) (i) > (iii) > (ii) (d) (iii) > (ii) > (i)
(e) (iii) > (ii) > (i) (f) (iii) > (i) > (ii) > (iv)
Example 3
A compound D (C8H10O) upon treatment with alkaline solution of iodine gives a yellow precipitate. The
filtrate on acidification gives a white solid E (C7H6O2). Write the structures of D and E and explain the
formation of E.
Solution
(D) C6H5CHOHCH3 (E) : C6H5COOH
Example 4
A compound (A) reacts with thionyl chloride to give a compound (B). (B) reacts with magnesium to form a
Grignard reagent with a treated with acetone and the product is hydrolysed to give 2-methyl-2-butanol.
What are structural formulae of (A) & (B).
Solution
(A) CH3CH2OH; (B) CH3CH2Cl
Example 5
3, 3-Dimethyl-butan-2-ol loses a molecule of water in the presence of concentrated sulphuric acid to give
tetramethylethylene as a major product. Suggest a suitable mechanism.
Solution
(i) H+
(CH3)3C . CHOH . CH3 (CH3)3C.CH+ . CH3
(ii) – H2O
(CH3)2C = C(CH3)2 – H+
(CH3)2C+CH(CH3)2
Example 6

Give the structure of the major organic products formed 3-ethyl-2-pentene under each of the follwing
reaction conditions.
(a) HBr in the presence of peroxide
(b) Br2/H2O
(c) Hg(OAc)2/H2O; NaBH4
Solution
Br
|
HBr
(a) (CH 3 CH2 )2 C = CHCH3 →
H O
(CH3 − CH2 )2 − CH − CH− CH 3
2 2
OH
|
Br2 / H 2O
(b) (CH 3 .CH 2 )2 C = CH − CH 3 → (CH 3 .CH2 )2 C − CH− CH 3
|
Br
Hg(OAc) / H O
(c) (CH3 .CH2 )2 C = CH − CH3 
2
NaBH
2
→ (C2 H5 )3 C.OH
4
Example 7
Identify the ethers that are cleaved with excess conc. HI to yield (a) (CH3)3Cl and CH3CH2CH2I, (b)
cyclohexyl and methyl iodides and (c) (CH2)5I.
Solution
Place an O atom between the C’s bonded to I’s. (a) (CH3)3COCH3CH2CH3 (b) cyclohexyl and methyl iodides
and (c) The presence of two I’s in the same product indicates a cyclic ether, i.e., tetrahydropyran.
Example 8
(a) Why are ethers such as Et2O used as solvents for (i) BF3 and (ii) RMgBr? (b) Compare the Lewis
basicities of tetrahydrofuran, diethyl ether and di-isopropyl ether and give your reasoning.
Solution
(a) Because of their unshared e–1s, ethers are also Lewis bases capable of reacting with Lewis acids such as
BF3 and RMgBr to form coordinate covalent bonds.
+
(i) Et 2 O + BF3 
→ Et 2 O BF3
R
..
(ii) 2Et 2 O + RMgBr 
→ Et 2 O Mg OEt 2
..
Br
Note that two molecules of ether coordinate tetrahedrally with one Mg2+.
(b) In addition to the amount of electron density on the nucleophilic site, steric affects also influence
basicities. The greater the steric hindrance encountered in the formation of the coordinate bond, the weaker
is the Lewis basicity. In tetrahydrofuran, the R groups (the sides of the ring) are “tied back” leaving a very
exposed O atom free to serve as a basic site. The 2° R groups in di-isopropyl ether furnish more steric
hindrance than do the 1° ethyl groups in ethyl ether. The order of decreasing Lewis basicity is thus
tetrahtdrofuran > ethyl ether > i-propyl ether.
*****

Exercise - I
General Type (Fill in the blanks/ True or False/ Assertion & Reason )
True/False
1. The reaction of methyl magnesium iodide with acetone followed by hydrolysis gives secondary
butanol.
2. Ethyl alcohol reacts with aqueous sodium hydroxide to form sodium ethoxide.
3. The favourable temperature for alcoholic fermentation of glucose to ethyl alcohol is 30 − 35°C.
4. Methyl alcohol gives iodoform test.
5. Acid Catalyzed dehydration of alcohols is easiest in tertiary alcohols.
6. Dehydration of alcohols in vapour phase in presence of alumina (AI2O3) results is saytzeff
rearranged alkene.
7. Vicinal diols (1, 2-diols) on acid catalyzed dydration form ketones or aldehydes as major products.
8. Tertiary alcohols have fastest rate of esterification.
Fill in the Blanks

1. An …………. diol has two hydroxyl groups on ………… carbon atoms.
2. CO combines with hydrogen when heated to 300°C in presence of a catalyst (ZnO + Cr2O3) to
give………
CH 3 MgBr
...........
3. CH 3 CHO  → …………..  → CH3CHOHCH3.
4. The enzyme that converts glucose to ethyl alcohol is ………………
Assertion and Reason

In each of the following questions two statements are given one labeled as the Assertion (A) and the other
labeled as the Reason (R). Examine these statements carefully and mark the correct choice as per following
instructions.
(a) If both A and R are true and R is the correct explanation of A.
(b) If both A and R are true but R is not the correct explanation of A
(c) If A is true but R is false.
(d) If A is false but R is true.
(e) Both A and R are false.
1. A: Phenol undergoes Kolbe’s reaction whereas ethanol does not.
R: Phenoxide ion is more basic than ethoxide ion.
2. A: The dehydration of alcohols by conc. H2SO4 involves the formation of carbocation
R: The protonated alcohol molecule loses water molecule in the second step.
3. A: Phenol is strongly acidic than ethanol.
R: Pehnoxide ion is more stabilized by resonance than ethoxide ion.

4. A: p-Nitrophenol has a higher melting point than o-nitrophenol.
R: o-Nitrophenol exhibits intermolecular hydrogen bonding.
5. A: The major product obtained on nitration of phenol with dilute nitric acid is nitrophenol.
R: o-NItrophenol exhibits intermolecular hydrogen bonding, while p-nitrophenol exhibits intra
hydrogen bonding.
6. A: The excess of Na left after the preparation of dry solvents (like dry ether) is destroyed by alcohol.
R: The alcohol reacts with sodium to form sodium alkoxide and hydrogen.
7. A: Phenol forms 2, 4, 6-tribromophenol on treatment with excess bromine water.
R: 2, 4, 6-Tribromophenol is less soluble in water than phenol.
8. A: Phenol and alcohol can be distinguished by NaOH.
R: Alcohol is a very weak acid as compared to phenol.
9. A: Secondary alcohol reacts faster with sodium than primary alcohol.
R: O – H bond in secondary alcohol is less polar than that of primary alcohol.
10. A: o-Phenol sulphonic acid on heating at 100°C changes to p-phenol sulphonic acid.
R: Sulphonation of phenol is a reversible process.
*****

Exercise - II
Objective Type (Only One Choice Correct)
Level - I
1. Ethylene glycol undergoes oxidation with hot acidic KMnO4 to form
(a) Formic acid (b) Formaldehyde (c) Acetic acid (d) Acetaldehyde
2. Glycerol on warming with a small amount of hydriodic acid gets converted to
(a) Propene (b) 3-Iodopropene (c) 1,3-Diiodopropane (d) 2-Iodopropane
3. When glycerol is treated with a mixture of concentrated HNO3 + H2SO4, it forms
(a) Nitroethane (b) 1-Nitropropane (c) Nitroglycerine (d) 2-Nitropropane
4. Compound (A) reacts with sodium metal to form one mole of H2. The compound (A) can be
(a) CH3CH2CH = CH2 (b) HOCH2CH2CH2CH2OH
(c) CH2 = CH – CH = CH2 (d) CH3CH2CH2CH2OH
5. Ethers are
(a) Lewis acids (b) Neutral
(c) Lewis bases (d) Cannot be predicted
6. In Reimer-Tiemann reaction which of the following species are involved as intermediate
O OH O–
H OH
CHCl
CHCl CHCl2
I. CCl2– II.
2
III. IV.
OH
(a) I and II (b) II and III (c) III and IV (d) I and IV
Calculated
x
Quantity
7. Glycerol + HI x and y are
Excess
(a) Allyl iodide and propene (b) Both are allyliodide
(c) Allyliodide and 2-Iodopropane (d) Both are 2-Iodopropane
8. The most unlikely representation of rasonance of p-Nitrophenoxide ion is
–
O + O–
N=O O– O –
O O +
+ +
N
N=O
N
(a) (b) (c) (d) –
– –
O O O O
9. Among the following compounds the strongest acid is
(a) HC ≡ CH (b) C6H6 (c) C2H6 (d) CH3OH
10. The reaction of CH3 – CH = CH — — OH with HBr gives

Br
(a) CH3 – CH Br CH2 — — OH (b) CH3 CH2CH — — OH

Br
(c) CH3 – CHBrCH 2 — — Br (d) CH3 CH2CH — — Br
11. Which of the following compounds gives most stable carbocation an dehydration ?
CH3
|
(a) CH3 − C− OH (b) CH 3 − C H − CH 2 OH
| |
CH3 CH 3
(c) CH3 − CH − CH 2 − CH3 (d) CH3CH2CH2CH2OH

|
OH
12. The order of reactivity of following alcohols
CH3 CH3
CH3
CH3
I. OH II F III. IV.
F OH OH Ph OH
towards conc. HCl is
(a) I > II > III > IV (b) I > III > II > IV (c) IV > III > II > I (d) IV > III > I > II
13. Which one of the following reactions will yield 2-propanol ? Choose the correct reactions
+ (i) CH3MgI
I. H
CH 2 = CH − CH 3 + H 2 O → II. CH3CHO  →
(ii) H 2O
(i) C2 H5MgI
III. CH 2 O 
→ IV. CH 2 = CH − CH 2 
4
→ Neutral KMnO
(ii) H 2O
(a) I and II (b) II and III (c) I and III (d) II and IV
OH OH
− CHO
OH / 343K
14. + CHCl3  → the electrophile attacking the ring is
(a) CHCl3 (b) CHCl2 (c) :CCl2 (d) COCl2

OH
15. CS2
+ Br2 / H 2 O  → x. x is
low temperature
(a) O-Bromophenol (b) O-and p-Bromophenol

(c) p-Bromo phenol (d) 2, 4, 6-Tribronophenol
16. In, CH3CH2OH, the bond that undergoes heterolytic cleavage most readily is
(a) C–C (b) C – O (c) C – H (d) O – H
17. For dehydration of the alcohols
OH
OH
I. II. III. OH
IV.
OH
the order of reactivity is
(a) III > II > IV > I (b) I > II > III > IV (c) IV > II > III > I (d) II > IV > I > III
CH3
Cold. CrO3 / CH3COOH
18.  → x.  → y . x and y are
alk. KMnO4

CH3 CH3 CH3 CH3
(a) OH and OH (b) OH and O–
OH O OH O
CH3 CH3
OH and
(c) OH (d) None of the above formed
OH
19. Alcohols are
(a) Less acidic than phenols (b) Less acidic than carboxytic acids
(c) Less acidic even than water (d) All the above are correct
20. Schotten Bauman reaction is
(a) Phenol + Benzyl chloride 
NaOH
→ Phenyl benzoate
− HCl
(b) Sodium phenate + methyl iodide  → Anisole
(c) Phenol + Chloroform 
NaOH
→ Salicylaldehyde
(d) Benzene diazonium chlorie + Phenol 
→ β-Hydroxyazobenzene
21. Vinyl carbinol is
(a) HO – CH2CH = CH2 (b) CH3C(OH) = CH2
(c) CH3 – CH = CH – OH (d) CH3C(CH2OH) = CH2
22. A compound is soluble in conc. H2SO4, it does not decolourise bromine in carbon tetrachloride but is
oxidized by chromic anhydride in aqueous sulphuric acid within two seconds, turning orange
solution to blue, green and then opaque. The original compound is
(a) primary alcohol (b) tertiary alcohol (c) alkene (d) ether
23. Absolute alcohol (100% alcohol) is prepared by distilling rectified spirit over
(a) Na (b) CaCl2 (c) Mg (d) Mg(OC2H5)2
24. 3 moles of ethanol react with one mole of phosphorus tribromide to form 3 moles of bromoethane and
one mole of X. Which of the following is X?
(a) H3PO4 (b) H3PO2 (c) HPO3 (d) H3PO3
25. Order of Esterification of alcohols is
(a) 3° > 2° > 1° (b) 2° > 3° > 1° (c) 1° > 2° > 3° (d) None of these
Level - II
26. What is the major product obtained when phenol is treated with chloroform and aqueous alkali?
OH
OH
CHO
(a) (b)
CHO
OH
COOH
(c) HO CHO (d)
27. An organic compound A reacts with methyl magnesium iodide to form an addition product which on
hydrolysis forms the compound B. Compound B gives blue colour salt in Victor Meyer’s test. The
compounds A and B are respectively.

(a) Acetaldehyde, tertiary butyl alcohol (b) Acetaldehyde, ethyl alcohol
(c) Acetaldehyde, isopropyl alcohol (d) Acetone, isopropyl alcohol
28. The compound ‘A’ when treated with methyl alcohol and few drops of H2SO4 gave smell of
wintergreen. The compound ‘A’ is
(a) Succinic acid (b) Salicylic acid (c) Tartaric acid (d) Oxalic acid
29. In the synthesis of glycerol from propene, the steps involved are
(a) Glycerol β-chlorohydrin and allyl chloride
(b) Glyceryl trichloride and glycerol α-chlorohydrin
(c) Allyl alcohol and glycerol β-chlorohydrin
(d) Allyl alcohol and monosodium glycerolate
30. Organic acid without a carboxylic acid group is
(a) ascorbic acid (b) vinegar (c) oxalic acid (d) picric acid
31. When phenol is treated with CHCl3 and NaOH the product formed is
(a) benzaldehyde (b) salicylaldehyde (c) salicylic acid (d) benzoic acid
32. n-Propyl alchol and isopropyl alcohol can be chemically distinguished by which reagent
(a) PCl5 (b) reduction
(c) oxidation with potassium dichromate (d) ozonolysis
33. The most reactive nucleophile among the cfollowing is
(a) CH3O– (b) C6H5O¯ (c) (CH3)3CHO¯ (d) (CH3)3CO¯
34. Which of the following orders of a cid strength is correct?
(a) RCOOH > ROH > HOH > HC ≡ CH (b) RCOOH > HOH > ROH > HC ≡ CH
(c) RCOOH > HOH > HC ≡ CH> ROH (d) RCOOH > HC ≡ CH > HOH > ROH
35. During dehydration of alcohols to alkenes by heating with conc. H2SO4, the initial step is
(a) formation of an ester (b) protonation of alcohol molecule
(c) formationof crbocation (d) elimination of water
PBr3
CH3 – CH – CH3 (X)
36.
OH
O
Mg/ether CH2 – CH2 H2O

(Y)
The final product is

(a) CH 3 − CH − CH 2 CH 2 OH (b) CH 3 − O − CH − CH 2 − CH 3
| |
CH3 CH3
(c) CH 3 − CH − O − CH 2 − CH 3 (d) None of these

|
CH3
37. Propan-1-ol can be prepared from propene by

(a) H2O/H2SO4 (b) Hg(OAc)2/H2O followed by NaBH4
(c) B2H6 followed by H2O2 (d) CH3CO2H/H2SO4
38. Which of the following combinations can be used to synthesis isopropyl alcohol?

(a) CH3MgI and CH3COCH3 (b) CH3MgI and C2H5OH
(c) CH3MgI and CH3COOC2H5 (d) CH3MgI and HCOOC2H5
39. Which is more acidic?
(a) o-cresol (b) p-nitrophenol (c) Phenol (d) m-cresol
40. The most suitable reagent for the conversion of RCH2OH 
→ RCHO is
(a) KMnO4 (b) K2Cr2O7
(c) CrO3 (d) PCC (pyridine chloro chromate)
41. The product X is
OH
1 K2CO3
X
2 CH3I
CH2OH
OH OCH3
(a) (b)
CH2OCH3 CH2OH
CH3 OCH3
(c) (d)
CH2OH CH2OCH3
42. The only alcohol that can be prepared by the indirect hydration of alkene is
(a) ethyl alcohol (b) propyl alcohol
(c) isobutyl alcohol (d) methyl alcohol
43. When alcohol reacts with concentrated H2SO4 intermediate compound formed is
(a) carbonium ion (b) alkoxy ion
(c) alkyl hydrogen sulphate (d) noneof these
44. Carbolic acid is
(a) C6H5CHO (b) C6H6 (c) C6H5COOH (d) C6H5OH
45. Salicylic acid is prepared from phenol by
(a) Relimer Tiemann reaction (b) Kolbe’s reaction
(c) Kolbe-electrolysis reaction (d) None of these
46. Lucas test is done for
(a) alkyl halides (b) alcohols (c) acids (d) aldehydes
47. p-Cresol reacts with chloroform in alkaline medium to give the compound X which adds hydrogen
cyanide to form, the compound Y. The latter on acidic hydrolysis gives chiral carboxylic acid. The
structure of the carboxylic acid is

CH3 CH3
CH(OH)COOH CH2COOH
(a) (b)
OH OH
CH3 CH3
(c) (d)
CH(OH)COH CH2COOH
OH OH
48. Which one of the following compounds is most acidic?
OH
(a) Cl – CH2 – CH2 – OH (b)
OH OH
(c) (d)
NO2 CH3
49. The best reagent to convert pent-34-en-2-ol into pent-3-in-2-on is
(a) Acidic permanganate (b) Acidic dichromate
(c) Chromic anhydride in glacial acetic acid (d) Pyridinium chloro-chromate
50. The compound used to manufacture phenol is
(a) Glycerol (b) Cumene (c) Crown ether (d) Lactic acid
*****

Exercise - III
Objective Type (More than One Choice Correct)
1. Reason for excessive solubility of alcohol in water is due to
(a) Covalent bond (b) Toxic bond
(c) Hydrogen bonding with water (d) Dipole-dipole interaction with water
2. Which gives the red or violet colour with FeCl3

(a) Salol (b) Aspirin
(c) Picric acid (d) P-hydroxy Azo zenzene
3. Which of the following reactions are used in the preparation of alcohols?

LiAlH
(a) C2 H 5 Br + aq. KOH 
→ (b) (CH 3 ) 2 C = O 
4
→
C
||
Na / EtOH
(c) CH 3 − C − OCH3  → (d) CH 3CH 2 Cl 
2
→ H O
4. Which of the following groups will increase the basicity of phenol ?

(a) – NH2 (b) – CH3 (c) – NO2 (d) None of these
5. Which of the following statements are correct ?

(a) When phenol vapour is passed over Zn dust, benzene is produced
(b) The phenolic –OH group is ortho-and para-directing
(c) o-Nitrophenol has a lower boiling point than p-nitrophenol
(d) Phenol is more acidic than o-cresol.
6. Glycerol changes to acrolein in the presence of

(a) Conc. H2SO4 (b) Anhy. ZnCl2 (c) KHSO4 (d) Anhy. CaCl2
7. Which of the following are less acidic than phenol?

(a) H2O (b) o-Cresol (c) p-Nitrophenol (d) o-Nitrophenol
8. Alcohols may act as

(a) Oxidising agent (b) Reducing agent (c) Lewis base (d) Bronsted acid

9. The compound which are used for denaturation of ethyl alcohol are
(a) Naphtha (b) CH3OH (c) Pyridine (d) Anhyd. CaCl2
10. The – OH group in alcohols may be replaced by Cl if we use

(a) Cl2 (b) SOCl2 (c) PCl5 (d) P + Cl2
11. Grignard reagents give alkanes with

(a) Phenol (b) Ether (c) Alcohol (d) Water
12. The best reagents for the ring alkylation of phenol are
(a) C2H5Cl and anhy. AlCl3 (b) CH3CH = CH2 and H2SO4
(c) (CH3)2CHOH and H2SO4 (d) CH3CH = CH2 and HF
13. Phenols can be converted into salicyclic acid using

(a) CCl4 and alkali at 340 K (b) CO2 and alkali under pressure
(c) HCOOH and conc. H2SO4 (d) CHCl3 and alkali at 340 K
14. Which of the following will give characteristic colour with ferric chloride?
(a) Allyl alcohol (b) Benzyl alcohol (c) Phenol (d) Vinyl alcohol
15. Which of the following will dissolve in aqueous Na2CO3?

(a) Phenol (b) 2,4,6-Trimethylphenol
(c) 2,4,6 –Trinitrophenol (d) 2,4-Dinitrophenol
16. Which of the following will give characteristic colour with FeCl3?
OH O
(a) (b)
O
CHO O O
|| ||
(c) (d) CH 3 − C− CH 2 − C− OH
17. Alkylation of phenoxide anion with allyl chloride gives

(a) Phenyl allyl ether (b) p-Allyl phenol
(c) o-Allyl phenol (d) m-Allyl phenol

18. Phenol is less acidic than
(a) Acetic acid (b) p-Methoxyphenol (c) p-Nitrophenol (d) Ethanol
19. When phenol is treated with CHCl3 and NaOH followed by acidification, salicyladehyde is obtained.
Which of the following species are involved in the above mentioned reaction as intermediates?
O OH
H CHCl2
(I) (II)
CCl2
O O
H CHCl2
(III) (IV)
CHCl
OH
(a) Catalytic reduction of carbon monoxide in the presence of ZnO – Cr2O3
(b) by reacting methane with steam at 900°C with a nickel catalyst
(c) by reducing formaldehyde with lithium aluminium hydride
(d) by reacting formaldehyde with aqueous sodium hydroxide solution
*****

Exercise - IV
Comprehensive/ Matching Type
Passage – 1
A research scholar synthesised alcohol by hydration of 1-butane. He was unaware of the fact that the vessel
he used had some coating of a metal, and in addition to alcohol (b.p. 100ºC) he also got a compound (X). X
(b.p. 80ºC) forms bisulphite compound as well as 2, 4-dinitrophenylhydroazone. He however was
successful in the separation, based on physical and chemical properties. Read the above technical report
and answer the following questions.
1. Which alcohol does research scholar want to synthesize and what is the other product.
(a) CH 3 CH 2 CH 2 CH 2 OH, CH 3CH 2 CH 2 CHO (b) CH 3 CH 2 C HCH 3 , CH 3CH 2 C CH 3
| ||
OH O
(c) CH 3CH 2 CH 2 CH 2 OH, CH 3CH 2 C HCH 3 (d) CH 3CH 2 CH 2 CH 2 OH, CH 3CH 2 CH = CH 2
|
OH
2. Based on the chemical tests of the side product formed, coated metal is
(a) Zn (b) Ag (c) Hg (d) Cu
3. He also got yellow precipitate on heating with NaOH/I2. This yellow precipitate is due to
(a) Alcohol, and side product both (b) Side product only
(c) Alcohol only (d) None of these
4. Carbonyl compound can be converted into required alcohol by

(a) Clemmensen reduction (b) Wolf-Kischner reduction
(c) LiAlH4 (d) All of these
Passage – 2
An organic compound (A) has 76.6% C, 6.38% H its vapour density is 47. It gives characteristic colours with
FeCl3 solution. (A) when treated with CO2 and NaOH at 140ºC under pressure gives compound (B).
The compound (B) on acidification gives a compound (C).
The compound (C) reacts with Acetyl chloride to give compound (D) which is well known pain-killer.
Answer the following questions based on the above comprehension.
1. Which one of the following correct empirical formula of compound is

(a) C 6H 5O (b) C7H7O2 (c) C6H6O (d) C3H8O2
2. Molecular mass of the compound is

(a) 96 (b) 90 (c) 100 (d) 94
3. The compound (A) is

(a) Phenol (b) Salicylic acid (c) Aspirin (d) None of these

4. The compound (B) will be
(a) Phenol (b) Salol (c) Sodium Salicylate (d) Sodium Phenoate
5. The compound (D) in the above is

(a) Aspirin (b) Salol (c) Salicylic acid (d) None of these
Passage – 3
Alcohols are prepared by various methods Griganard reagents give a variety of alcohols. Carbonyl
compounds and acids are also easily reduced to alcohol.
Depending upon the stereospecific and regiospecific/selective requirements, alkenes are also hydrated to
alcohols by (i) dil H2SO4 (i) oxymercuration demercuration and (iii) by hydroboration oxidation.
1. Which of the following reactions will give primary chiral alcohol as major organic product?
+
(A) CH 3 MgBr + C 2 H 5 N 
H3O
→
H O / OH
(B) CH 3 − C = CH 2 + BH 3 / THF → →
2 2
|
CH 2 CH3
dil H PO
(C) CH 3 − C = CH 2 
3 4
→
|
CH2 CH 3
H
Hg(OAC)2.H2O NaBH4
(D) C2H5 – C = C – D
C2H5
2. Which of the following reactions will give 2° chiral alcohol as one or more of major organic products.
O
H H3O⊕
D O2 H3 O⊕ CH3Mgl + H - C - O CH - C2H5
(A) MgBr (B) (excess)
CH3 CH3
H
O
H3O⊕
Mg+Br CH2-CH2
(C) (D) None
CH3
3. Which of the following reduction methods is not suitable for preparing an alcohol?
(A) CH 3 COOC2 H 5 + NaBH 4 → (B) CH 3 COOC 2 H 5 + Na / EtOH →
(C) CH 3 CH 2 COCI + LiAIH 4 → (D) CH 3 COOH + H 2 
Ni
→
Passage – 4
Regioselectivity is observed in many reactions of alkyl halides, alcohols of alkenes. Regioselectivity means
that if there are two or more possible isomeric products then that structural isomers is the major product
which is more stable. The product may be stereospecific also (i.e. a particular stereoisomeric product may
predominate depending upon the stereochemistry of reaction).

1. In which of the following reaction, regioselectivity can be observed.
CH3 CH3
CH3 C CH2 CI alc.KOH CH3 C CH3 alc.KOH

(A) (B)
H CI
CH3 CH3
CH3 C CH2 CH3 alc.KOH CH3 C CH2 CI alc.KOH
(C) (D)
CI CI
2. Which of the following correctly shows major product.

(A) CH 3 − CH = CH 2  → CH 3 − CH 2 − CH 2 − OD
2 4 2 D SO / D O
|
D
CH3 CH3
!
H2O/H
CH3 C CH2 CH3 C CH3
(B)
OH
CH3 CH3 CH3 CH3
HBr
Ph – C = C – CH3 Ph – C – C – CH3
(C)
H Br
OH
H2SO4+H2O
(D)
3. In which of the following reactions, the stereochemistry of the product has been correctly shown.
Me Me
SOCI2
C OH CI C H
CH3H P+I2 CH3H
(A) (B) Ph
OH CH3 I CH3 H Ph
Me Me
SOCI2/Pyridine CH3 H CH3 Br
C OH C CI Br!
(C) (D) H3C H OH (conc. KBr) CH3 H H
Ph Ph
H H H H H H
Matching Type Questions

1. Column I Column II
(a) Fries rearrangement (p) Resorcinol + Phthalic acid →
Conc
H SO
Flurescein
2 4
AlCl 3
(b) Elbs persulphate oxidation (q) Phenyl ethanoate → p-hydroxy acetophenone
∆
(r) Phenol  → Quinol

K S O
(c) Coupling reaction 2 2 8
(d) Phthalein reaction (s) Phenol+Benzene diazonium chloride→p-hydroxy azobenzene

(a) (a-q), (b-r), (c-s), (d-p) (b) (a-q), (b-r), (c-p), (d-s)
(c) (a-s), (b-p), (c-r), (d-q) (d) (a-p), (b-r), (c-s), (d-q)
(a) Oil of winter green (p) Phenyl salicylate
(b) Salol (q) Methyl slicylate
(c) p-Hydroxy acetanilide (r) Aspirin
(d) Acetyl salicylic acid (s) Paracetamol
(a) (a-s), (b-r), (c-p), (d-q) (b) (a-q), (b-p), (c-s), (d-r)
(c) (a-s), (b-p), (c-r), (d-q) (d) (a-p), (b-r), (c-s), (d-q)
(a) Phenol + neutral FeCl3 (p) No reaction
(b) Phenol + Br2(aq) (q) Violet colour
(c) Phenol + NaHCO3 (r) White ppt.
(d) Picric acid + NaHCO3 (s) CO2 gas is evolved
(a) (a-s), (b-r), (c-p), (d-q) (b) (a-q), (b-r), (c-p), (d-s)
(c) (a-q), (b-r), (c-p), (d-s) (d) (a-p), (b-r), (c-s), (d-q)
*****

Exercise - V
Subjective Type
1. Compound (A) gives positive Lucas test in five minutes. When 6.0 g of (A) is treated with sodium
meal, 1120 ml of hydrogen is evolved at STP. Assuming (A) to contain one atom of oxygen per
molecule, write structure of (A). Compound (A) when treated with PBr3 gives (B) which when
treated with benzene in presence of anhydrous aluminium chloride gives (C). What are (A) (B) and
(C) ?
2. A straight chain organic compound C4H10O4 yields on acetylation (B) of molecular formula
C12H18O8. How many hydroxyl groups are present in compound ? Also write structures of (A) and
(B).
3. An organic compound (A) composed of C, H and O gives characteristic colour with ceric ammonium
nitrate. Treatment of (A) with PCl5 gives (B) which reacts with KCn to form (C). The reduction of (C)
with warm Na/C2H5OH produces (D) which on heating gives (E) with evolution of ammonia.
Pyridine is obtained on treatment of (E) with nitrobenzene. Give structures of (A) to (E) with proper
reasoning.
4. An ester A (C4H8O2), on treatment with excess methyl magnesium chloride followed by acification,
gives an alcohol B as the sole organic product. Alcohol B, on oxidation with NaOCl followed by
acidification, gives acetic acid. Deduce the structures of A and B. Show the reaction involved.
5. Dipole moment of methanol is higher than that of phenol. Why ?
6. Unlike phenols, alcohols are easily protonated. Explain.
7. Alcohols react with halogen acids or phosphorus halides to form haloalkenes but phenol does not
form halobenzenes. Explain.
8. Arrange the following substances in the decreasing acidic nature. Phenol, Picric acid, p-Cresol, m-
Cresol, 2, 4-Dinitrophenol, p-Nitrophenol, m-Nitrophenol.
9. Nitro group deactivates the aromatic ring towards electrophilic substitution and yet it activates the
aryl halides towards nucleophilic substitution ? Give reason.
10. Di-tert-butyl ether cannot be made by Williamson’s synthesis. Explain why ?
*****

Exercise - VI
IIT-JEE Problems
1. Give the structure of the compound, C(C4H8) which when treated with H2O/H2SO4 gives C4H10O
which cannot be resolved into optical isomers.
2. Predict the major product of the following reaction:

C 6 H 6 + ( CH 3 )2 CHCH 2 OH →
H 2 SO 4
3. 3, 3-Dimethylbutan – 2-ol loses a molecule of water int eh presence of concentrated sulphuric acid to
given tetramethylethylene as a major product. Suggest a suitable mechanism.
4. Give the structures of the major organic product when 3-ethylpent-2-ene is reacted with
Hg(OAc)2/H2O, NaBH4.
5. Complete the following giving the structure of the principal organic product.
( COOH )2 + ( CH 2 OH )2 + conc.H 2 so 4 
→ F.
6. Acid catalysed dehydration of t-butanol is faster than that of n-butanol. Give reasons in one or two
sentences.
*****

Answers
Exercise - I
True/False
1. False 2. False 3. True 4. False
5. True 6. False 7. True 8. False
Fill in the Blanks
1. Alkane, different 2. methyl alcohol
3. (CH3)2CHOMgBr, H2O/H+ 4. zymase
Assertion Reason
1. (c) 2. (a) 3. (a) 4. (c) 5. (e)
6. (a) 7. (b) 8. (a) 9. (d) 10. (a)
Exercise - II
Only One Option is correct
Level-I
1. (b) 2. (c) 3. (d) 4. (b) 5. (b)
6. (b) 7. (b) 8. (c) 9. (d) 10. (b)
11. (a) 12. (c) 13. (a) 14. (c) 15. (c)
16. (d) 17. (c) 18. (a) 19. (c) 20. (a)
21. (a) 22. (a) 23. (d) 24. (d) 25. (c)
Level-II
26. (a) 27. (c) 28. (b) 29. (c) 30. (d)
31. (b) 32. (c) 33. (a) 34. (b) 35. (b)
36. (a) 37. (c) 38. (d) 39. (b) 40. (d)
41. (b) 42. (a) 43. (a) 44. (d) 45. (b)
46. (b) 47. (c) 48. (c) 49. (d) 50. (b)

Exercise - III
More than one option may be correct
1. (c, d) 2. (a, c, d) 3. (a,, b, c) 4. (a, c, d) 5. (a, b, c, d)
6. (a, b, c) 7. (a, b) 8. (c, d) 9. (b, c) 10. (b, c, d)
11. (a, c, d) 12. (b, c, d) 13. (a, b) 14. (c, d) 15. (c, d)
16. (a, c, d) 17. (a, c) 18. (a, c) 19. (a, d)
Exercise - IV
Passage Type Questions
Passage I
1. (b) 2. (d) 3. (a) 4. (c)
Passage II
1. (c) 2. (d) 3. (a) 4. (c) 5. (a)
Passage – 3
1 (b) 2. (b) 3. (a)
Passage – 4
1. (c) 2. (b) 3. (b)
Matching Type Questions
1. (a) 2. (b) 3. (c)
Exercise - V
Subjective Type
1. (A) : CH3CHOHCH3, (B) CH3CHbRCH3, (C) C6H5CH(CH3)2
CH2 CH CH CH2
C H2 C H C H C H2
2. (A) | | | | (B) OOCCH3 OOCCH3 OOCCH 3 OOCCH3
OH OH OH OH
CH2OH
:H2C
3. (A) CH2OH (B) :ClCH2CH2CH2Cl (C) CH2CNCH2CH2CN
CH2CH2NH 2 CH2CH2
:H2C :H2C NH
(D) CH2CH2NH 2 (E) CH2CH2
4. (A) : HCOOCH (CH3)2; (B) : (CH3)2CHOH
5. Due to electron withdrawing effect of phenyl group, the C-O bond in phenol is less polar, whereas
in case of methanol, the methyl group has electron repelling effect and hence C-O bond in it is more
polar.
6. In phenols, the lone pairs of electrons on the oxygen atom are delocalised over the benzene ring due
to resonance andare not available for protonation. In contrast, in alcohols the lone pair of electrons

on the oxygen atom are localised due to the absence of resonance and hence are easily available for
protonation.
7. The C-O bond in phenols have some double bond character due to resonance and hence cannot be
easily cleaved by X– ions in the presence of halogen acids or phosphorus halides to form
halobenzenes. In contrast, the C-O bond in alcohols is a pure single bond and hence can be easily
cleaved by X– ions in presence of halogen acids of phosphorus halides to form haloalkanes.
8. The decreasing of acidic nature is : Picric acid > 2, 4-Dinitrophenol > p-Nitrophenol > m-
Nitrophenol > Phenol > m-Cresol > p-Cresol
9. The nitro (–NO2) group is an electron withdrawing group due to –I effect and it decativates the
ring. Therefore, the electrophilic, substitution takes place with difficulty, but it activates the aryl
halide towards nucleophilic substitution because it stabilises the carbanion (formed by the attack of
the nucleophile on the benzene ring) by the dispersal of negative charge.
10. For the preparation of di-tert-butyl ether by Williamson’s synthesis, tert-butyl bromide and sodium
tert-butoxide. tert-butyl bromide being tertiary (3º) alkyl halide prefers to undergo elimination
rather than substitution, hence the product obtained is isobutylene rather than diethyl ether.
Exercise - VI
IIT-JEE Problems
1. C = 2-methylpropene.
2. C 6 H 5 C ( CH 3 )3
4. ( CH 3 CH 2 )3 COH
5. Ethylene glycol being an alcohol reacts with oxalic acid in presence of conc. H2SO4 to form ethylene
oxalate (F).
6. Acid-catalysed dehydration of alcohols occurs through the intermediate formation of stable
carbocations.
*****

5-Alcohol, Phenol &amp; Ether

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5-Alcohol, Phenol &amp; Ether

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Chemistry by sandeep sir

Alcohol, Phenol and Ether

Born 27 September 1818

Died 25 November 1884

Known for Kolbe’s electrolysis and

Kolbe (1818 – 1884) was born in Elliehausen, Germany.

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As we go higher in the series, it becomes necessary to indicate whether a particular alcohol is

6.3 IUPAC System

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6.4 Grignard Synthesis

( CH3 ) CHCI + Mg 

The grignard reagent belongs to a class of compounds called organometallic compounds, in

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Tertiary alcohols are obtained by treating Grignard reagents with ketones.

Exceptional Behaviour of Grignard Reagent

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6.5 Methods of Preparation of Alcohols

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(i) Hydroboration-oxidation of non-terminal alkynes leads to the formation of ketones. For

(ii) Non-catalytic hydrogenation: Hydroboration-oxidatin can be used to reduce double bonds in

Reduction of Aldehydes and Ketones

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6.7 Alcohols undergo the following general reactions

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Reaction with Thionyl Chloride

Reaction with Hydrogen Halides

where HX = HI, HBr, HCl.

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Reaction with Sulphuric Acid

Step-3 Carbonium ion loses a proton to give the alkene.

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Step-4 Oxonium ion loses a proton to form an ether

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Reaction with Carboxylic Acids

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Secondary alcohols lose hydrogen and yield a ketone.

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Some of the compounds with responds positively to iodoform test are

6.9 Cleavage of 1, 2 – Glycos

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6.10 Test for an – OH Group

How to Distinguish Between 1°, 2° and 3° alcohols?

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Reaction with Hydrogen Iodide

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Reaction with Oxalic Acid

Glycerol monoformate on hydrolysis gives formic acid and glycerol is regenerated.

Reaction with Acetyl Chloride

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Phenol, Hydroxybenzene, C6H5OH.

+ NaOH 623 K dil. HCl

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From Benzenediazonium Salts

Physical Properties of Phenols

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6.12 Properties (Chemical)

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The reaction of phenol with benzoyl chloride is known as Schotten-Baumann reaction.

5-Alcohol, Phenol & Ether

5-Alcohol, Phenol & Ether