ORGANIC CHEMISTRY

Haloalkanes and Haloarenes

Haloalkanes
Haloalkanes are obtained by the replacement of a hydrogen atom of an alkane by a halogen
atom (F, Cl, Br, I).
(i) Nomenclature
In common system, monohalogen derivatives of alkanes (alkyl halides) are named by adding
the word ‘halide’ to the name of the corresponding alkyl group.
Here, the prefixes n-, iso-, sec-, tert- etc., are used.
In IUPAC system, alkyl halides are named as halosub, stituted hydrocarbons, i.e. haloalkanes.
The names are written by prefixing the word 'halo' to the name of alkane corresponding to the
longest continuous straight carbon chain having the halogen atom, e.g.

CH3CH2CH2Br,

Common name IUPAC name n-propyl bromide 1- iso -propyl chloride

bromopropane
2-chloropropane

(ii) Nature of C—X Bond

Due to the greater electronegativity of halogen atom, the halogen atom in C—X bond acquires
partial negative charge, whereas C-atom acquires partial positive charge.
(iii) Preparation
(a) From alkane and halogen Chloroalkane and bromoalkane can be prepared by the reaction
of alkane with chlorine or bromine in the presence of sunlight or heat. For higher alkanes, a
mixture of1°, 2° and 3° alkyl halide is obtained
(b) From alkene and hydrohalide Halogen acid when treated with alkene undergoes addition
reaction to yield haloalkane. Unsymmetrical alkene follows Markownikoff's rule.

CH3—CH—CH2 + HBr →

Propene 2-bromopropane

(c) From alcohols Most common method forpreparation of haloalkanes is the replacement of —
OH group of an alcohol by required halogen atom.
With phosphorus halides Chloroalkanes can be prepared by the reaction of PCI5 or PCI3.
ROH + PCI5→ RCI + POCI3+HCI
Chloroalkane

3 ROH + PCI3→ 3RCI + H3PO3

With thionyl chloride In the presence of pyridine.

ROH +SOCl2 Pyridine RCI + SO2 ↑ + HCI↑

(d) Preparation by halogen exchange method

Finkelstein reaction Alkyl iodides are often prepared by the reaction of alkyl chlorides/
bromides with Nal in dry acetone. This is called Finkelstein reaction.
R—X + Nal →R—l + NaX (X = [Link])
Swart’s reaction Fluoroalkanes are best prepared by treating alkyl chloride/bromide in the
presence of a metallic fluoride such as AgF,Hg2F2. This is known as Swart’s reaction.

CH3Br + AgF → CH3F + AgBr

Bromomethane Fluoromethane

(e) Borodine-Hunsdiecker reaction

CH3COO– Ag+ + Br2 CCI4 350K CH3Br + CO2+ AgBr

Reflux

(iv) Physical Properties

(a) Alkyl halides are highly combustible.
(b) For the same alkyl group, the boiling point decreases in. the order Rl>RBr>RCI >RF.
As the size of alkyl group decreases, boiling points decreases for the same halogen,
CH3CH2CH2X > CH3CH2X > CH3X
(c) Alkyl halides are slightly solube in water because they do not form H-bonds with water.
(v) Chemical Properties
(a) Nucleophilic Substitution Reactions (SN) Nucleophile attacks at electron deficient sites.
SN reactions are of two types-SN1 and SN2. In SN1 reaction, rate is proportional to the
concentration of alkyl halide and it is ummolecular. While, in SN2 reaction, rate is proportional to
the concentration of both alkyl halide and nucleophile and it is bimolecular.
The order of reactivity of alkyl halides for:
SN1 is 3° >2°> 1° and SN2 is 1° > 2° > 3°
Various nucleophilic substitution reactions are as follows
• Reaction with aqueous NaOH Flaioalkanes react with boiling aqueous alkali, like NaOH or
KOH to qive alcohols.
e.g. C2H5Br + NaOH (aq) → C2HΓOH+ NaBr

Ethyl bromide Ethyl alcohol

• Reaction with water Haloalkanes are hydrolysed to alcohols by boiling water.

RX + H OH → ROH + HX
Alcohol

C2H5Br+ HOH → C2H5OH+HBr

Ethyl bromide Ethyl alcohol

• Reaction with sodium iodide Alkyl chlorides or bromides on treatment with Nal in acetone
undergo halogen exchange to give alkyl iodides.

C2H5CI C2H5l + NaCI

C2H5Br C2H5l + NaBr

This reaction is called Finkelstein reaction.

• Reaction with ammonia (Formation of Amines) Haloalkanes on heating with ethanolic
ammonia under pressure gives primary amine.
The primary amine, thus formed react further with alkyl, halides and gives 2°, 3° amines and
quaternary ammonium salts.

e.g. C2H5Br + NH3 → C2H5NH2+HBr

Ethyl Ethylamine (1° amine)

bromide

C2H5NH2 + C2H5Br → (C2H5)2NH+HBr

Diethylamine

(2° amine)

(C2H5)2NH + C2H5Br → (C2H5)3N+HBr .

Triethylamine

(3° amine)

(C2H5)3N + C2H5Br → [(C2H5)4NrBr-

Tetraethyl ammonium
 bromide (Quaternary salt)

This reaction is called ammonolysis.

• Reaction with potassium cyanide (Formation of cyanides) Haloalkanes on reaction with
alcoholic solution of KCN give alkyl cyanides.

C2H5Br + KCN(alc.) → C2H5CN + KBr

Ethyl bromide Ethyl cyanide

• Reaction with silver cyanide (Formation of isocyanides) Aqueous alcoholic silver cyanide
when heated with haloalkanes, it gives alkyl isocyanides.

C2H5Br + AgCN(ag,alc.) → C2H5NC +AgBr

Ethyl bromide Ethyl isocyanide

• Reaction with potassium nitrite When

haloalkanes are heated with aqueous alcoholic solution of KNO2, alkyl nitrite are produced as
major product.

C2H5Br + K—O—N = 0→
Ethyl bromide Potassium nitrite

C2H5—0—N = O + KBr
Ethyl nitrite Polassiumbromide

•Reaction with silver nitrite When haloalkanes are heated with an ethanolic solution of
AgNO2, nitro alkanes are produced as major product.

• Reaction with silver salt of acids (Formation of ester) Haloalkanes on reaction with an
ethanolic solution of silver salts of a carboxylic acid give esters.

• Reduction Haloalkanes on reduction with LiAIH4 give alkanes.

4C2H5Br + LiAIH4—→ 4C2H6↓ AIBr3 + UBr

Ethane

(b) Elimination Reaction

Haloalkanes having β-hydrogen atom undergoes β-elimination when heated with alcoholic
solution of KOH.
Due to involvement of elimination of β-hydrogen atom, the process is often called β-
elimination.

(c) Reaction with metals Most organic chlorides, bromides and iodides react with certain
metals to give compounds containing carbon metal compounds.
• Action with Mg (Formation of Grignard reagent)

R—X+ Mg Dry ether RMgX

Alkyl (Grignard

halide reagent)

• Action of Na (Wurtz reaction)

R—X + 2Na+ X—R Dry ether R—R + 2NaX

(vi) Uses
• Synthesis of large variety of organic compounds.
• Ethyl chloride is used as a local anaesthetic and as refrigerant.
• Ethyl bromide is used for the preparation of barbiturate drugs.
2. Haloarenes
Haloarenes are obtained by the replacement of a hydrogen atom of an aromatic hydrocarbon by
a halogen atom (F, Cl, Br, I).
(i) Nomenclature
They are named by prefixing ‘halo’ before the name of the aromatic hydrocarbon.
Haloarenes are the common as well as IUPAC names of aryl halides. For dihalogen derivatives,
the prefixes, o-, m-, p- are used in common system but in IUPAC system, the numerals 1,2; 1,3
and 1,4 are used.

(a) (b) (c)

Common and IUPAC names of above figures are given below

Common name IUPAC name

(a) Bromobenzene Bromobenzene

(b) m-dibromobenzene 1,3-dibromobenzene

(c) sym-tribromobenzene 1,3,5-tribromobenzene

(ii) Nature of C—X Bond

In haloarenes, sp2-hybridised carbon of benzene is bonded to halogen and C—X bond is also
polar as in haloalkanes. ,
Also, as lone pairs of electrons of halogen atom are involved in resonance with benzene ring.
So, this C—X bond acquires partial double bond character.
(iii) Preparation
• By halogenation of aromatic hydrocarbons
Haloarenes can be prepared by the halogenation of aromatic hydrocarbons in presence of
FeCI3 as given below

• From benzene diazonium salts

(iv) Physical Properties

(a) These are colourless with pleasant smell, insoluble in water.
(b) Isomeric haloarenes have similar boiling points.
(c) But p-isomers have higher melting point than other two, i.e. meta and ortho because of the
symmetry in p-isomer which occupies crystal structure better than ortho and meta-isomers.
(v) Chemical Properties
• Haloarenes are less reactive than haloaikanes towards nucleophilic substitution reactions, due
to resonance effect, sp2-hybridisation of a bearing halogen atom and instability of phenyl cation.
Under drastic condition, haloarenes undergo nucleophilic substitution reactions are given below.
Some nucleophilic substitution reactions are.
• Substitution by hydroxyl group Chlorobenzene when heated in aq. NaOH solution at 623 K
and 300 atm, phenol is formed. This is known as Dow's process.
The presence of electron withdrawing group (—NO2) at ortho and para positions increases the
reactivity of haloarenes
• Substitution by —NH2 group
Chlorobenzene in presence of strong base such as NaNH2 undergoes nucleophilic substitution
reaction.

Electrophilic Substitution Reactions

Electrophilic substituation reactions of haloarenes yield ortho (minor) and para products (major)
The common electrophilic substitution reactions of haloarenes are depicted as below:
• Halogenation

• Nitration

• Sulphonation

• Friedel-Craft alkylation

• Friedel-Craft acylation
Reaction with metals
* Wurtz-Fittig reaction When aryl halide is heated with alkyl halide with sodium in presence of
dry ether, halogen atom is replaced by alkyl group and alkylarene is formed. The reaction is
called Wurtz-Fittig reaction.

• Fittig reaction
When haloarenes react with sodium in the presence of dry ether, two aryl groups are joined
together and diphenyl is formed. This reaction is called Fitting reaction.

• Addition reaction with Mg

In this reaction, haloarene reacts with Mg then Grignard reagent is formed.

Phenyl magnesium bromide

• Addition with lithium

Bromo and iodo arenes react with lithium metal in the presence of dry ether to form their
corresponding organometallic compounds.

Phenyl lithium bromide

• Reaction with copper powder (Ullmann reaction)

In this reaction, iodobenzene is heated with copper powder in a sealed tube, diphenyl is formed.

(iv) Reduction On reduction of haloarenes, hydrocarbons are formed.

3. Polyhalogen Compounds
(i) Chloroform, (QHCI3) Trichloromethane is the trichloro derivative of methane commonly
known as chloroform.
(a) Preparation
I. From methane Methane reacts with chlorine in the presence of light of form chloroform as
given below

CH4 + Cl2 CH3CI

CH2CI2 CHCI3
Chloroform

II. Partial reduction of carbon tetrachloride

Carbontetrachloride reduced to chloroform as given below

CCI4 +2H CHCI3 + HCI

(b) Physical property Colourless heavy liquid causes temporary unconsciousness

(c) Chemical properties
I. Oxidation When exposed to air and sunlight form highly poisonous gas,carbonyl chloride or
phosgene.
II. Reduction With zinc and hydrochloric acid, it reduces to methylene chloride.
III. Hydrolysis When boiled with aqueous or alcoholic potassium hydroxide, it gets hydrolysed
to give formic acid, which combines with KOH to give potassium formate.
IV. Nitration It may be nitrated by concentrated nitric acid to form chloropicrin.
(d) Uses It is used as anaesthetic, solvent for oils, fats, medicines.
(e) Halfmful effects It affects the CNS. Inhaling at, 900 ppm for a short time cause dizziness,
fatigue and headache. Skin develops sore if immersed directly into the chloroform.
(ii) Iodoform (CHI3)
(a) Preparation (Haloform reaction)
I. From ethanol Iodoform is prepared by ethanol by the following manner

CH3CH2OH + 4I2 + 6NaOH

Ethanol

CHI3 + HCOONa + 5Nal + 5H20

Iodoform Sodium formate

II. From acetone Acetone reacts with l2 and NaOH to form iodoform as given below :

(b) Physical properties

I. It is a pale yellow crystalline solid and insoluble in water.
II. On heating, it decomposes, to give iodine vapour.
(c) Chemical properties
I. Reduction When reduced with red phosphorus and hydroiodic acid, it gives methylene iodide.
II. Hydrolysis Hydrolysis of iodoform can be done as follows

CHU + 3KOH [H—C(OH)3]

(ale.) (Unstable)

III. Dehalogenation Iodoform undergoes

dehalogenation to form ethyne as given below:

CHI3 + 6Ag + CHI3 HC≡CH + 6Agl

Ethyne

IV. Reaction with silver nitrate CHI3 reacts with silver nitrate (ale.) to form yellow ppt. of Agl.

Iodoform + silver nitrate Yellow ppt. of Agl

(ale.)

(d) Uses It is used as an antiseptic due to liberation of iodine.

(iii) Freons
Chlorofluorocarbons compounds of methane and ethane are collectively known as freons.
Freon-12 is one of the most common freons in industrial use.
(a) It is manufactured as,
(b) Uses These are used as refrigerants in refrigerators and air conditioning. These are used as
propellants for aerosols and foams to spray out deodrants, hair creams and insecticides.
(c) Harmful effects Most freons makes its way into the atmosphere where it undergoes
photochemical decomposition and initiate radical chain reactions for depletion of the ozone
layer.
Therefore, the use of freons as propellants and refrigerants has been dranstically discouraged.
(iv) DDT [2,2-bis-.(p-chloropheπyl) -1, 1, 1-trichloroethane] or (p,p'-
dichlorodiphenyltrichloroethane)
• Preparation It can be prepared by reacting chloral with chlorobenzene as given below

• Uses
This white powder is used as insecticide.
It is popularly very effective against anopheles mosquitoes and lices which carry typhus.
Harmful effects
Its use has been restricted as it is toxic, non-biodegradable and highly stable once entred a food
chain.
Alcohols, Phenols and Ethers
1. Alcohols
Hydroxy derivatives of aliphatic hydrocarbons are called alcohols. They possess the general
formula R—OH, where R is an alkyl or substituted alkyl group. These are named by replacing ‘e’
of parent alkane with suffix ‘ol’. The general formula of alcohols is CnH2n+1OH.
(i) Classification of Alcohols
(a) On the basis of no. of —OH groups present in the molecules
(i) Those alcohols which contain one —OH group are called monohydric alcohols, e.g.
CH3OH: C2H5OH etc.
(ii) Those alcohols which contain two —OH groups are called dihydric alcohols. Their general
formula is CnH2n(OH)2 They are also called diols, e.g. 1, 2-ethanediol.
(iii) Those alcohols which contain three hydroxyl groups are called trihydric alcohols. They are
also called triols. e.g. 1, 2, 3-propanetriol.
(b) On the basis of position of —OH group in the carbon chain
(i) The alcohol in which —OH group is attached to r carbon atom is called primary alcohol
e.g. CH3OH,C2H5OH, etc.
(ii) The alcohol in which —OH group is attached to 2° carbon atom is called secondary
alcohol,e.g. 2-propanol.
(iii) The alcohol in which —OH group is attached to 3° carbon atom is called tertiary alcohol.
e.g. 2-methylbutan-2-ol.
(ii) Structure
The structure of an alcohol resembles the structure of water with an alkyl group replacing one of
hydrogen atoms of water.
Both have sp3-hybridised oxygen atoms, but the C—O—H bond angle in methanol is
considerably larger than H—O—H bond angle in water due to the large size of methyl group in
alcohol.
(iii) Methods of Preparation
(a) Hydrolysis of alkyl halide Haloalkanes when treated with aqueous solution of an alkali
(NaOH/KOH) give corresponding alcohols.

R—X + KOH(ag) → R—OH + KX

Haloaikane Alcohol

(b) From Grignard reagent Aldehydes and ketones react with Grignard reagent to form
alcohol.
I. HCHO gives primary alcohols.
II. Aldehyde other than formaldehyde give secondary alcohols.
III. RCOR' gives tertiary alcohols.
(c) From alkenes
• Direct hydration of alkenes Alkenes react with water in the presence of acid as catalyst to
form alcohols.

• Indirect hydration of alkenes In this method, sulphuric acid and alkene react at elevated
temperature and under pressure to form sulphate esters which upon hydrolysis give alcohol.
Hydroboration-oxidation process Diborane reacts with alkenes to give trialkyl boraπes as an
addition product which upon subsequent oxidation by H202 in presence of aq. NaOH give
alcohols.

(d) By the reduction of carboxyl compounds

• Aldehydes and Ketones are reduced to the primary and secondary alcohols respectively.

• Carboxylic acids are reduced to primary alcohols by LiAIH4.

R-COOH R CH2OH

(e) From primary amines Aliphatic primary amines react with nitrous acid to give primary
alcohols.

NaNO2 + HCI HN02 + HCI

R— NH2+ HNO2 R —OH + N2 ↑+ H2O

(iv) Physical properties of alcohols

These are colourless volatile liquids having characteristic alcoholic odour and burning taste.
Alcohols are polar in nature and capable of forming intermolecular hydrogen bonding. Alcohols
are soluble in water.
The solubility of alcohols in water decreases with increase in molecular mass.
The boiling points of alcohols are considerably higher than those of corresponding
hydrocarbons, haloalkanes, ethers etc. due to H-bonding.
(v) Chemical properties of alcohols
(a) Acidic behaviour Alcohols behave as weak acids and isonise to a very small extent as
shown below.

Acidic strength of alcohols is even less than that of water.

(b) Reaction with active metals When an alcohol is treated with sodium or potassium, the O—
H bond gets cleaved and a metal alkoxide is formed with the evolution of hydrogen gas.

2R—OH+ 2Na → 2RŌN+a + H2↑

 Sodium alkoxide

(c) Reaction with metal hydrides Alcohols react with metal hydrides to form metal alkoxides
with the evolution of hydrogen gas.

(d) Reaction with Grignard’s reagent When an alcohol is treated with Grignard’s reagent; the
H-atom of the —OH group of the alcohol combines with the alkyl part of the Grignard's reagent
to give an alkane.

(e) Dehydration Alcohols undergo dehydration when treated with cone. H2SO4 or H3PO4.
The steps involved in this process are:
StepI Protonation of alcohol

StepII Formation of carbocation [slowest step, hence it is a rate determining step]

StepIII Formation of ethene by elimination of a proton

(f) Reaction with PCI3, PCI5 and SOCI2Alcohols react with phosphorus halides (PCI3, PCI5) and
thionyl chloride (SOCI2) to form corresponding haloalkanes.

(g) Reaction with acid chlorides and acid anhydrides

Alcohols react with acid chlorides or acid anhydrides in the presence of bases like pyridine to
form ester. This, reaction is called acylation reaction.
(h) Reaction with hydrogen halides Alcohols reacts with phosphorus halide, PCI3, PCI5 etc.,
to form corresponding haloalkanes.

R ––OH + HX → R-—X + H2O

Haloalkane

(i) Oxidation Primary and secondary alcohols are oxidised by Na2Cr207/K2Cr207 to form
aldehydes and ketones.

Tertiary alcohols when subjected to vigorous oxidation with nitric acid give ketone containing
lesser number of carbon atoms.
(j) Reaction with carboxylic acid (esterification)

(vi) Some Commercially Important Alcohols (a) Methanol (CH3OH)

It is also known as ‘wood spirit’, as it was produced by the destructive distillation of wood.
Preparation (Bosch Process)
Now-a-days, methanol is produced by the catalytic hydrogenation of carbon monoxide at high
pressure and temperature in the presence of ZnO-Cr2O3 catalyst.

CO+2H2 CH3—OH
Methyl alcohol or methanol
(b) Ethanol (C2H5OH)
Preparation
It is obtained commercially by the fermentation of sugar present in molasses, sugarcane or fruits
like grapes.

C12H22O11 + H2O C6H12O6 + C6H12O6

Sucrose Glucose Fructose

C6HI2O6 2C2H5OH +2CO2 ↑

Glucose or Fructose Ethanol

Fermentation takes place in anaerobic conditions, i.e. in the absence of air. Carbon dioxide is
released during fermentation. If air gets into fermentation mixture, the oxygen of air oxidises
ethanol to ethanoic acid which destroys the taste of alcoholic drinks.
(vii) Distinction between Primary, Secondary and Tertiary Alcohols
(i) Lucas Test
A small quantity of unknown alcohol is added to Lucas reagent (anhy. ZnCI 2 + cone. HCI) at
room temperature and the mixture is shaken.
A tertiary alcohol forms turbidity immediately, secondary alcohol forms turbidity within five
minutes and primary alcohol shows no turbidity at room temperature.
(ii) Victor Meyer's Test
The given alcohol is treated with red phosphorus and iodine to convert it into the corresponding
alkyl iodide which is then further treated with AgNO2 to form nitroalkane which is finally treated
with nitrous acid and the resulting solution is made alkaline.
Primary alcohols give blood red colour, secondary alcohols give blue colour and in case of
tertiary alcohols, solution remains colourless.
(viii) Conversion of One Alcohol into Another.
(i) Conversion of a Lower Alcohol into a Higher Alcohol

R—OH Rl RCN
Lower alcohol

R CH2NH2 RCH2OH
Higher alcohol

(ii) Conversion of Higher Alcohol into a Lower Alcohol

RCH2OH RCHO RCOOH

Higher alcohol
(iii) Conversion of Primary Alcohol to a Secondary Alcohol

(iv) Conversion of Secondary Alcohol to a Tertiary Alcohol

(v) Conversion of Primary Alcohol to a Tertiary Alcohol

2. Phenols
Phenols are the hydroxy derivatives of arenes in which one or more —OH groups are directly
attached to the carbon atoms of an aromatic ring.
(i) Preparation of Phenols
(a) Dow's process In this process, phenol is prepared by heating chlorobenzene with 10%
NaOH solution at 623 K under 300 atm followed by hydrolysis.
(b) From sulphonic acids When sodium salts of aromatic sulphonic acids are fused with NaOH
at 573 K followed by acidification, phenols are obtained.

(c) From diazonium salts Diazonium salts are hydrolysed in the presence of dil. H2SO4 to give
phenols.

(d) From cumene This method is used for the commercial preparation of phenol. This reaction
proceed at 150°C in the presence of HBr as a catalyst. The reaction is also called auto
oxidation.

Also, it gives o- and p- phenol sulphonic acids when treated with cone. H2SO4 (sulphonation)

(e) Reaction with zinc dust It gives benzene on heating with Zn dust.

(f) Friedel-Craft’s reaction Phenols undergo Friedel-Craft’s reaction in the presence of

anhydrous AICI3.
(g) Reaction with PCI5The replacement of —OH group of phenol by a halogen atom is quite
difficult and the yield of chlorobenzene is very poor.

(h) Koibe’s reaction Phenoxide ion produced by treating phenol with NaOH is more reactive
than phenol towards electrophilic aromatic substitution. Hence, it undergoes electrophilic
substitution with weak electrophile CO2.

Reimer-Tiemann reaction On treating phenol with CHCI3 (chloroform) in the presence of

sodium hydroxide, a —CHO group is introduced at ortho position of benzene ring. This reaction
is called Reimer-Tiemann reaction. In this 'reaction, electrophile is dichlorocarbene (:CCI2).

(ii) Physical Properties

(a) Phenols are either colourless liquids or colourless crystalline solids with low melting points.
(b) Phenols are slightly soluble in water.
(c) Phenols possess higher boiling points as compared to those of the corresponding aromatic
hydrocarbons and haloarenes.
(iii) Chemical Properties
(a) Acidic character Phenols are more acidic than alcohols, due to more stabilisation of
phenoxide ion formed by delocalisation of negative charge.
Presence of electron withdrawing groups such as —NO2,—CHO, etc, increases acidic strength
of phenol by stabilising phenoxide ion whereas, electron releasing group like —CH3 reduces the
acidic strength of phenol.
(b) Electrophilic aromatic substitution Phenols undergo electrophilic aromatic substitution
reaction readily due to presence of —OH group. It gives 2,4,6-trinitrophenol (or picric acid) when
treated with cone. HN03 (Nitration) and 2,4,6-tribromophenol when treated with Br2/H2O
(Bromination). However, when phenol is treated with Br2 in CS2, it gives o- and p-bromophenol.

(iv) Test for Phenols

(a) Reaction with ferric chloride Unlike alcohols, phenols react with neutral FeCI3 and give
violet coloured water soluble complex [Fe(OC6H5)3]3-
Thus, this reaction is used to distinguish phenol and known as Ferrichloride test.
(b) Coupling reaction (Also dye test) Phenol reacts with diazonium salt to form aro dye but
alcohol does not form azo dye.
(iv) Uses
It is used in perfumery. It is widely used in the manufacture of dyes, plastics etc.
3. Ethers
The substitution of a hydrogen atom in a hydrocarbon (aliphatic/aromatic) by an alkoxy
(OR)/aryloxy (OAr) group yield ethers. These have general formulaCnH2n+2O and are
represented by general structure R—O—R.
(i) Structure of ethers
O-atom in ethers is sp3-hybridised. Ethers have a bent or angular structure. Ethers are dialkyl
derivatives of water or monoalkyl derivatives of alcohols.

(ii) Preparation of aliphatic and aryl ethers (a) From alcohols (By dehydration of 2 moles of
alcohols)

The order of dehydration of alcohols leading to the formation of ethers is

primary alcohol > secondary alcohol > tertiary alcohol
(b) By Williamson’s synthesis from haloalkanes This is one of the best method for the
preparation of ethers.
In this method, alkyl halide is treated with a suitable sodium (or potassium) [Link].

R—O-Na+ + XR → R—0—R + NaX

Sodium alkoxide Alkyl Ether
halide

(c) Reaction of alkyl halides with dry silver oxide When alkyl halide is heated with silver
oxide, symmetrical ether is formed.

(d) From Grignard’s reagent Higher ethers can be prepared by treating α-haloethers with
suitable Grignard’s reagent.

(in) Physical properties of ethers

(a) Boiling points of ethers are much lower than those of [Link].
(b) Solubility Lower ethers (upto three carbon atoms) are soluble in water and their miscibility
with water resembles those of alcohols of the same molecular masses.
(iv) Chemical properties of aliphatic ethers (a) Halogenation When ethers react with Cl2 or
Br2 in dark, substitution takes place mainly at α-C-atonn.

R'CH2—O—R+ Cl2 R'CHCl—O—R+ HCI

Ether Chlaroether

(b) Reaction with peroxides In contact with airor02, ethers form peroxides which are unstable
compounds.

(c) Reaction involving cleavage of C—O bond

• Reaction with halogen acids (HX) In cold, alkyl halide and alcohol are formed.

R—O—R + HX POH + RX
Ether (X = 1 or Br) Alcohol Alkyl halide
e.g. C2H5— O — C2H5 + HI C2H5I + C2H5OH
Diethyl ether lodoethane Ethanol

With excess of halogen acids, 2 molecules of alkyl halides are formed.

R—O—R + 2 HX 2 RX + H2O
Excess

. e.g. C2H5— O —C2H5 + 2HI Δ 2C2H5I+ H20

Excess

Reaction with PCl5Alkyl chlorides are formed by the cleavage of C—O bond.

R—O—R + PCI5 2R— Cl + poci3

Alkyl chloride

(v) Chemical Properties of Aryl Ethers

Aryl ethers undergo electrophilic substitution reaction. These are as follows :
Electrophilic substitution reactions Important electrophilic substitution reactions are as
follows:
(a) Halogenation

(b) Friedel-Craft’s reaction Anisole undergoes Friedel-Craft’s reaction, i.e. the alkyl and acyl
groups are introduced at o-and p-positions by reaction with alkyl and acyl halides in the
presence of anhydrous aluminium chloride (a Lewis acid) as catalyst.
(c) Nitration Anisole reacts with a mixture of concentrated sulphuric acid and nitric acid to yield
a mixture of ortho and para nitroanisole.

(vi) Uses of Ethers

(a) Dimethyl ether is used as a refrigerant and as a solvent at low temperatures.
(b) Used as an industrial solutions for oils, resins, gums, etc.
(c) As an extracting solvent in laboratory and industry because of their almost inert nature and
good dissolving power.
Aldehydes, Ketones and Carboxylic Acids
1. Carbonyl Compounds or Aldehydes and Ketones
The C = O group is known as the carbonyl group and the compounds containing C = O group
are known as carbonyl compounds. In aldehydes, the carbonyl group is bonded to carbon and
hydrogen while in-ketones, it is bonded to two carbon atoms.

Aldehydes and ketones have molecular formula, CnH2nO and are functional isomers of each
other.
Methods of Preparation of Aliphatic
Aldehydes and Ketones (i) From alcohols
(a) By oxidation of alcohol's with K2Cr2O7/ H2SO4 or KMnO4/ KOH.

(b) By catalytic dehydrogenation of alcohols with Cu at573K.

(ii) From alkenes (Ozonolysis) By reductive ozonolysis of alkenes, carbonyl compounds are
formed.
(iii) From alkynes Alkynes on hydration in presence of dil. H2S04 and HgS04 gives
acetaldehyde whereas all other alkynes give ketones.
(iv) From calcium salts of carboxylic acids
(v) From acid chloride Aldehydes can be obtained from acid chlorides by the catalytic
hydrogenation known as Rosenmund’s reduction.

Ketones cannot be prepared by this method. They are prepared by treating acid chlorides with
dimethyl cadmium in the presence of dry ether.
(vi)From nitriles
• Nitriles are also reduced to corresponding imine with stannous chloride in the presence of
hydrochloric acid which on hydrolysis give corresponding aldehydes.

RCN + SnCI2 + HCI → RCH = NH RCHO

Nitrile amine Aldehyde

This reaction is known as Stephen reaction.

• When nitriles reacts with Grignard reagent followed by hydrolysis yields a ketone.

(vii) From esters Esters can also be reduced to aldehydes with DIBAL-H.

Physical Properties of Aldehydes and Ketones

(i) Methanal is a gas while ethanal is a volatile liquid at room temperature.
(ii) Boiling points of aldehydes and ketones are higher than hydrocarbons and ethers of
comparable molecular masses.
(iii) All aldehydes and ketones are fairly soluble in organic solvents like benzene, ether,
methanol, chloroform, etc.
Chemical Properties of Aldehydes and Ketones Nucleophilic addition reactions
Aldehydes and ketones undergo nucleophilic addition reactions. These reactions are catalysed
by both acids and bases.
Some Important Nucleophilic Addition Reactions are
(a) Aldehyde and ketones on reaction with HCN give cyanohydrins. This reaction is slow, so it is
catalysed by a base.
(b) Addition of sodium hydrogen sulphite to aldehydes or ketones results in the formation of an
addition product as follow

(c) Aldehydes and ketones on reaction with Grignard reagent give addition products which upon
hydrolysis with water/dil. mineral acids gives alcohol.

(d) Aldehyde react with one equivalent of monohydric alcohols in the presence of dry HCI gas to
give hemiacetals which on further reaction with 1 more molecule of alcohols give acetals. The
reaction is given: as,

Ketones react with dihydric alcohols to give cyclic ketals.

(e) Nucleophiles such as ammonia and its derivative, H2N—Z add to the carbonyl group of
aldehyde and ketones in presence of weakly acidic medium. The reaction is given as below

[Z = alkyl, aryl, OH, NH2, C6H5NH, NHCONH2, etc.]

(f) Base catalysed reactions
• Aldol condensation Aldehydes and ketones containing a -H atoms undergo aidol
condensation in presence of dilute alkali as catalyst to form β-hydroxy aldehyde aldol) orβ-
hydroxy ketones (ketol).
* Cross-aldol condensation When two different aldehydes or different ketones or one
aldehyde and one ketone each containing α-H atoms, undergo crossed aldol condensation.
e.g.

(g) Cannizzaro’s reaction Aldehydes which do not have α-H atoms undergo self oxidation and
reduction on treatment with cone, alkali.
e.g

(i) Reaction with grignard reagent Aldehydes and ketones on reaction with Grignard reagent
give addition oroducts which upon hydrolysis αive alcohols.

• Oxidation of aldehydes to carboxylic acids

Aldehydes differ from ketones in their oxidation reactions. Aldehydes are easily oxidised to
carboxylic acids containing the same number of carbon atom, because aldehydes contain H-
atom attached to carbonyl group, which can be converted into —OH group without involving
cleavage of any other bond.

RCHO R—COOH

• Oxidation of ketones Unlike aldehydes, ketones do not contain H-atom attached to C=0
group and hence they cannot be oxidised by weak oxidising agent. They are oxidise by strong
oxidising agants, like KMn04, acidified K2Cr204at high temperature.

• Iodoform reaction Aldehyde and ketones having atleast one methyl group linked to carbonyl
carbon atom (methyl ketone) are oxidised by sodium hypohalite to sodium salts of
corresponding carboxylic acids having one carbon atom less than that of carbonyl compound.

• Reduction Aldehydes and ketones can be reduced to a variety of compounds under different
conditions,

(Wolff-kishner reduction)
Uses of Aldehydes and Ketones
(i) Formaldehyde is used as disinfectant and as a germicide, 40% aqueous solution of
formaldehyde is called formalin.
(ii) Formaldehyde is used in the manufacture of bakelite, resin, and other polymers.
(iii) Formaldehyde is used in making urotropine, a medicine for urine infections.
(iv) Paraldehyde is used in medicine as a hypnotic.
(v) Acetone is used as a constituent of liquid nail polish.
Test to Distinguish betweeen Aldehydes and Ketones

Test Aldehydes Ketones

Tollen’s reagent test Give silver mirror No response

Fehling's solution test Give red precipitate No response

Schiffs reagent test Give pink colour No response, (acetone restore

the pink colour but very slowly)

Reaction with LiAIH4 Form primaryalcohols Form secondary alcohols

2. Aromatic Aldehyde or Benzaldehyde (C6H5CHO)

It is commercially known as oil of bitter almonds.
Preparation
From toluene Toluene on oxidation with chromyl chloride, oxidises methyl group to a chromium
complex which on hydrolysis gives corresponding benzaldehyde.

This reaction is known as Etard reaction.

Physical Properties
(i) It is highly refractive liquid.
(ii) It has boiling point of 452 K.
Chemical Properties
(i) Oxidation It gets oxidised to benzoic acid in the presence of dil, HNO3 or alkaline KMnO4.

(ii) Reduction It is reduced to benzyl alcohol.

(iii) Nucleophilic addition reaction (a) With HCN

(iv) Addition of Ammonia and its Derivatives
(a) With ammonia It reacts with NH3 to form complex product called hydrobenzamide.

(b) With ammonia derivatives

[Z =OH, NH2, C6HSNH, 2, 4-DNP, etc.]

(v) Reaction with PCI6Benzal chloride is formed when benzaldehyde reacts with PCI5.

C6HsCHO + PCI5 → C6H5CHCI2 + POCI3

Benzaldehyde Benzal chloride

(vi) Cannizzaro’s reaction When benzaldehyde is heated with strong alkaii solution, it
undergoes simultaneous oxidation and reduction forming salt of benzoic acid and benzyl
alcohol.

2C6H6CHO+ NaOH → C6H5CH2OH + C6H5COONa

Benzaldehyde cone. Benzyl alcohol Sodium benzoate

(vii) Benzoin condensation When two molecules of benzaldehyde are heated with an alcoholic
solution of KCN, they undergoes self condensation to form benzoin.

This reaction is called benzoin condensation.

(viii) Perkin’s reaction When benzaldehyde is heated with aliphatic acid anhydride in presence
of sodium salt of the acid corresponding to the anhydride, they form α, β-unsaturated acid on
hydrolysis.
(ix) Electrophilic substitution reactions — CHO group is deactivating m-directing group.
(a) Halogenation

(b) Nitration

(c) Sulphonation

Uses of Benzaldehyde
(i) As a flavouring essence in perfumery.
(ii) in the manufacture of dyes.
(iii) In the synthesis of cinnamic acid, cinnamaldehyde, etc.
Test to distinguish Between Aliphatic and Aromatic Aldehyde
They can be distinguished by iodoform test. Acetaldehyde gives a yellow precipitate of
iodoform, when heated with iodine in the presence of alkali.
Benzaldehyde does not give iodoform test.
3. Carboxylic Acids

The organic compounds which contain the carboxyl group as the functional group are
knownas car boxylic acids
Preparation of Carboxylic Acids (i) From Oxidation of Primary Alcohols and Aldehydes
Alcohols on oxidation with strong oxidising agent gives aldehyde which on further oxidation
gives carboxylic acids.

PCH2OP RCHO RCOOH

Primary Aldehyde Carboxylic
alcohol acid

(ii) From Hydrolysis of Nitriles

Nitriles are first hydrolysed to amides and then to carboxylic acids in the presence of H+ orOH―
as catalyst.

(iii) From Grignard reagent

Grignard reagent with dry ice(CO2) in etheral solution and on acidification give carboxylic acids.

Physical Properties of Carboxylic Acids

The physical properties of carboxylic acids are described below
(i) Solubility Simple aliphatic carboxylic acids having upto four carbon atoms are miscible in
water because of hydrogen bond formation with water.
(ii) Boiling point As compared to hydrocarbons, aldehydes and ketones, carboxylic acids have
higher boiling points because they have high extent of hydrogen bonding with water due to
which they exists as associated molecules.
(iii) Melting point The melting points of aliphatic carboxylic acids do not show a regular pattern
rather they show oscillation or alteration effect, i.e. melting point of an acid containing even
number of carbon atoms is higher than the next member containing odd number of carbon
atoms.
Chemical Properties of Carboxylic Acids
(i) Acidic nature of carboxylic acids

Greater the extent of ionisation, greater is the strength of the acid.

Presence of an electron donating substituent (+/-effect) decreases the acidic strength of the
carboxylic acid.
Presence of an electron withdrawing substituent (-/ effect) increases the acidic strength of the
carboxylic acid.
Reactions showing acidic character of carboxylic acids (a) Reaction with metals

(b) Reaction with alkalies,

(c) Reaction with carbonates and bicarbonates

(ii) Reaction involving —OH part of the carboxyl group

(a) Formation of acid chlorides Carboxylic acids can be converted into corresponding and
chlorides by- treating with PCI5, PCI3 or SOCI2

(b) Formation of esters When carboxylic acids reacts with alcohols in presence of Cone.
H2S04, esters are formed.

(c) Formation of amides They react with ammoniato form ammonium salts which upon heating
form acid amides.
(d) Formation of acid anhydride Carboxylic acids in presence of strong dehydrating agents
such as P2O5 or H2SO4 give acid anhydrides.

(iii) Decarboxylation of carboxylic acid By electrolysis of aqueous solution of sodium or

potassium salt.

At anode,

2RCOCT → R— R + 2COa + 2e-

Carboxylate Alkane

ion

At cathode.

2H2O 2M++ OH–

2H+ + 2e– -→ H2

This process is known as Kolbe’s electrolysis.

(iv) Halogenation
Carboxylic acids (except formic acid) react with chlorine or bromine in presence of small amount
of red phosphorus gives a- halogenated carboxylic acids.

CH3COOH CH2CICOOH
Acetic Acid Monochloro Acetic acid

CHCI2COOH CCI3COOH
Dichloro acetic acid Trichloro acetic acid

This reaction is called Hell-Volhard-Zelinsky (HVZ) reaction.

(v) Ring substitution reactions in aromatic carboxylic acids
(a) Halogenation
(b) Nitration

(c) Sulphonation

Test For
(i) Formic acid
(a) It gives silver mirror or black precipitate with Tollen’s reagent.
(b) It gives red precpitate with Fehling’s solution
(c) It qives decolourises pink colour of acidified KMn04.
(ii) Acetic acid
(a) It liberates carbon dioxide gas with bicarbonates and carbonates. With ferric chloride, it
produces win red colour.
(b) When warmed with ethyl alcohol and cone. H2S04, a pleasant fruity odour of ethyl acetate is
formed.
(iii) Benzoic Acid
(a) It dissolves in water on boiling but separate out in the for m of white shiring leaflets on
cooling.
(b) It gives buff coloured ppt with FeCI3.
Uses
(i) Formic acid
(a) As an antiseptic.
(b) For dye baths in textiles,
(c) As a coagulating agent in rubber industry.
(ii) Acetic acid
(a) As a solvent for resins, cellulose etc.
(b) In the production of dyes, perfumes, esters, acetone etc,
(c) For the manufacture of cellulose which is used for making packaging materials, varnishes,
rayon etc.
(iii) Benzoic acid
(a) As a food preservative either in the pure form or mostly in the form of sodium benzoate.
(b) As urinary antiseptic in medicine.
(c) In the manufacture of antiseptics and dyes.

(b) 2Ln + 3H2—→ 2LnH3

(c) 2Ln + 3X2—→ 2LnX3

(d) 2 Ln + 6H2O—→ 2Ln(OH)3 + 3H2 ↑

(e) Ln + 2C LnC2

(f) 2Ln + 3S —→ Ln2S3

(g) 2Ln + N2 —→ 2LnN

2. Actinoids or Actinoid Series

These elements follow actinium (Ac) upto lawrencium (Lr) and closely resemble it in physical
and chemical properties. General electronic configuration Actinoids follow the general
electronic configuration of [Rn] 5f1-146 d0-17s2.
Lanthanoid Contraction and its Consequences
On moving from La to Lu in lanthanoid series, the size of atoms and ions decreases regularly.
The 4f-orbitals containing electrons are too diffused to screen the nucleus as effectively as the
more localised inner shell.
Hence, the attraction of the nucleus for the outermost electrons increases steadily with increase
in atomic number. Thus, due to imperfect shielding of 4f-electrons, a contraction in the electron
cloud of 4f-subshell increases. Due to lanthanoid contraction, the basic character of oxides and
hydroxides decreases from La(OH)3 to Lu(OH)3. Zr/Hf; Nb/Ta and Mo/W are almost identical in
size.
Comparison with lanthanides
(a) The decrease in atomic (or ionic) radii in actinoid elements (actinoid contraction) is greater
than lanthanoid contraction because 5 f-electrons have poor shielding effect as compared to 4 f-
electrons.
Therefore, the effect of increased nuclear charge leading to contraction in size is more in case
of actinoid elements.
(b) Actinoids exhibit more number of oxidation states than lanthanoids.
This is due to the fact that 5f, 6d and 7s levels are of comparable energies.
(c) Actinoids have stronger tendency towards complex formation as compare to lanthanoids.
Uses of Lanthanoids and Actinoids
(i) U and Pu are used as fuels in atomic reactors.
(ii) Their salts are used. In medicine, in the treatment of cancer.
(iii) U salts are used in ceramic, glass and textile industry.
(iv) Lanthanoids are useful in the form of their alloys ar compounds, e.g. an alloy containing Mg
and about' misch metal is used in jet engine parts.
(v) Mixed oxides of lanthanoids are used as catalyst petroleum cracking.
Coordination Compounds
1. Double Salts
These are the addition compounds that lose their identity in solution. They exist only in solid
state and have properties same as those of constituent compounds.
2. Coordination Compounds
These are those addition compounds which retain their Identity in solid as well as in aqueous
solution. Their properties are different from their constituents.
3. Some Important Terms Used in Coordination Compounds
(i) Central metal atoms or ions In a coordination entity, the metal atoms or ions with which a
definite number of ligands are attached in a definite geometry are called central metal atoms or
ions.
e.g. Fe2+ ,Cu2+, Ni2+, Pt2+are central metal ions which are also known as Lewis acids
(ii) Ligand It is a charged ion or neutral molecule which is capable of donating a pair of
electrons to the central atom or ion for the formation of a coordinate bond. It is also as known
Lewis base.
Ligands can be classified as :
(a) Monodentate ligands These have only one donor atom which is bound to central metal ion,
e.g. Cl-, NH3, CO, H2O, etc.
(b) Bidentate ligands These ligands can bind through two donor atoms e.g. 1,2-ethanediamine
(en).
(c) Polydentate ligands These have more than two donor atoms in the molecule.
[Link] tetraacetate (EDTA) is a hexadentate ligand.
(d) Chelating ligands The ligands coordinating through two or more donor groups leading to
formation of a ring with metal ion are called chelating ligands and such complexes are chelate
complexes, e.g. [Pt(en)2]CI2.
(e) Ambidentate ligands When a ligand containing two different donor atoms attach to the
central metal atom through any of its donor atoms, is called ambidentate ligand, e.g. NO2, SCN-
ONO-
(iii) Coordination entity (Complex ion) Coordination entity constitutes a central metal atom or
ion attached to a fixed number of ions or molecules which may be positive, negative or neutral.
(iv) Coordination sphere The central atom/ion and the ligands present in the square brackets
are collectively known as coordination sphere.
(v) Coordination number The total number of ligands to which the metal in directly attached is
called coordination number (C.N) e.g. [Co(NH3)6]3+, C.N =6.
(vi) Ionisation sphere The part of the coordination compound which is present outside the
square brackets of coordination sphere is known as ionisation sphere.
(vi) Oxidation state Oxidation state of coordination compound is defined as the charge it would
carry if all the ligands are removed along with the electrons pairs that are shared with central
atom. It is represented by roman numeral in parentheses.
4. Nomenclature of Coordination Compounds
The formula and names adopted for coordination entities are based on the recommendations of
the IUPAC.
Formulae of Mononuclear Coordination Entities
Following rules are applied while writing the formulae :
(i) The central atom is listed first.
(ii) The ligands are then listed in alphabetical order. The placement of a ligand, in the list does
not depend on its charge.
(iii) Polydentate ligands are also listed alphabetically. In case of abbreviated ligand, the first
letter of the abbreviation is used to determine the position of the ligand in the alphabetical order.
(iv) The formula for the entire coordination entity, whether charged or not, is enclosed in square
brackets. When ligands are polyatomic, their formulae are enclosed in parentheses. Ligand
abbreviations are also enclosed in parentheses.
(v) There should be no space between the ligands and the metal within a coordination sphere.
(vi) When the formula of a charged coordination entity is to be written without that of the counter
ion, the charge is indicated outside the square brackets as a right superscript with the number
before the sign.
(vii) The charge of the cation(s) is balanced by the charge of the anion(s).
IUPAC Rules for Naming Complex Compounds
(i) If the counter ions are positively charged (cations), they are named first and if they are
negatively charged (anions) they are named at the end.
(ii) In complex ions, ligands are named first. The number of a particular type of ligand is written
as di for 2, tri for- 3, tetra for 4, penta for 5, hexa for 6 and so on.
If the name of ligand involves numerical prefix such as di, tri, tetra etc. the number, of such
ligands are : bis for 2, tris for 3, tetrakis for [Link] there are more than one type of ligands, their
names are written in alphabetical order. The negative and positive ligands are named by putting
suffix -o and -ium, respectively.
(iii) The oxidation state of central metal ion can be indicated by roman numerals I. II. Ill and IV
etc., in bracket at the end of the name of the complex.
(iv) For cationic and neutral complex, the name is written as it is but for anionic complex, the
name of the central atom ends with 'ate'.
(v) When a ligand coordinates through more than one atom, the point of attachment of the
ligand is indicated by putting the symbol of the atom through which coordination occurs after the
name of ligand.
(vi) For bridging ligand μ followed by hyphen is used before the name of ligand.
(vii) Geometrical isomers are differentiated by cis and trans and optical isomers by (+) and (-)
ord-and l-form. e.g.[Cr(NH3)3(H2O)3] Cl3— triamminetriaquachromium (III) chloride,
[Co(H2NCH2CH2NH2)3] SO4 — tris(ethane-1,2-diammine)cobalt (II) sulphate.
[Ag(NH3)2] [Ag(CN)2]—diamminesilver (I) dicyanoargenfate.
5. Isomerism in Coordination Compounds
Compounds having same molecular formula but different structures are called isomers and this
phenomenon is called isomerism. Coordination compounds show two major types of
isomerism, structural isomerism and stereoisomerism.
(i) Structural Isomerism The coordination compounds having same chemical formula and
chemical bonds but are different due to different structural arrangement.
These are of four types
(a) Ionisation isomerism It is shown by those compounds which have same composition but
give different ions in solution,
e.g. [Co(NH3)5Br] SO4 and [Co(NH3)5(SO4)] Br.
(b) Hydrate isomerism It is shown by the compounds having difference in number of water
molecules present as ligand and as molecules of hydration, e.g. [Cr(H2O)5CI] Cl2H2O and
[Cr(H2O)3]CI3.
(c) Linkage isomerism It is shown by the compounds having ambidentate ligand, e.g.
[Co(NH3)5(NO2)]CI2 and [Co(NH3)5ONO]CI2.
(d) Coordination isomerism It is shown by the compounds when both positive and negative
ions of the compound are complex ions and the two isomers differ in the distribution of ligands
in the cation and the anion, e.g. [Co(CN)6] [Cr(NH3)6]and [Cr(CN)6] [CO(NH3)6].
(ii) Stereoisomerism Coordination compounds having same molecular as well as structural
formulae but different arrangement in three dimensional space around the central atom in the
polyhedral are called stereoisomerism. It is of two types.
(a) Geometrical or cis-transisomerism When two identical ligands occupy adjacent position,
we have c/s-isomer and when they are arranged opposite to each other, we have trans-isomer.
This phenomenon is called geometrical isomerism, e.g. [Co(en)2CI2]+ have two geometrical
isomers as shown below:

(b) Optical isomerism The compounds which do not have a plane of symmetry show optical
isomerism. The isomer which rotates the plane of polarised light to the right is called dextro (d)
rotatory, whereas the isomer which rotates the plane of polarised light to the left is called laevo
(l) rotatory [Co(en)3]3+ has two optical isomers as shown below
6. Werner’s Theory According to Werner' theory, primary valency is tonisable (i.e, species
present outside the coordination sphere is ionisable) whereas secondary valencies are not.
7. Valence Bond Theory (VBT) It was developed by Linus Pauling. It’s various postulates are
atso follows
(i) Central atom/ion makes available required number of empty orbitals.
(ii) These orbitals undergo hybridisation to give same number of hybrid orbitals of equal energy.
These hybridised orbitals are allowed to overlap with ligand orbitals that can donate electron
pairs for bonding, and form strong ligand-metal coordinate covalent bonds.
(iii) Ligands must have one sigma orbital containing lone pair, of electrons.
(iv) During complex formation, the Hund’s rule of maximum multiplicity is followed while, in case
of strong ligands, unpaired electrons get paired.
(v) A complex is paramagnetic if it contains unpaired electrons. If all the electrons are paired,
the complex is diamagnetic in nature.
(vi) The outer orbital (high spin) or inner orbital (low spin) complexes are formed depending
whether outer d-orbitals or inner d-αrbitals are used, e.g. using VBT, formation of inner orbital
complexes [Fe(CN)6]3- and [Co(NH3)6]3+ can be represented as:

Using VBT, formation of outer orbital complex [CoF6]3 can be represented as:

8. Crystal Field Theory It is an electrostatic model which considers the metal-ligand bond to be
ionic arising purely from electrostatic interactions between the metal ion and the ligand.
The main characteristics of CFT are as follows
(i) The metal ion and ligand act as point charges and the interaction is purely electrostatic.
(ii) When ligand approaches free metal ion, all five degenerate (having similar energy) d-orbitals
get split into two groups t2g(dxy,dyz,dzx) and eg (dx 2 −y 2 , dz 2 ).
This type of splitting is called crystal field splitting.
(iii) Due to different orientation, orbitals experience different interaction from ligand. Orbitals
lying in the direction of ligand will have energy more than in the relative energy in the spherical
crystal field.
Whereas orbitals lying in between the ligands will have lower energy. On the approach of
ligands, two sets of d-orbitals having different energies are obtained.
This difference in energies is called crystal field splitting energy (∆oor 10 Dq).
CFSE in Octahedral Field
CFSE = no. of e-s in t2g× -0.4Δo+ no. of e -s ineg × 0.6∆o
CFSE in tetrahedral field = no. of electrons in eg×–0.6∆t + no. of electrons in t2g ×0.4Δt.
(iv) Due to electrical field of ligand, the accommodation of electron in splitted d-orbitals is in
accordance to Hund’s rule.
(v) The crystal field splitting ∆o depends upon the fields produced by the ligands and charge on
the metal ion The increasing order of strength of ligands in spectrochemical series are as
follows
l-< Br-< SCN-< Cl-< S2- < F-< OH-<C2O2-4
< H2O< NCS-<edta4-<NH3<en <CN <C2O2-4<H2O<NCS-<CO
9. High Spin and Low Spin Complex If Δ <P it will be high spin complex and if Δ >P it will be
low spin complex.
where, Δ = crystal field splitting energy, P = energy required for electron pairing in an orbital.
Weak field ligands form high spin complexes while strong field ligands form low spin complexes.
10. Colour of Coordination Compounds According to the crystal field theory, colour of
complexes is due to d-d transitions of electrons.
For example, the complex [Ti(H2O)6]3+ appears violet in colour due to the transition of electron
from t2g level to the eg level (t12ge0g →t02ge1g).
In the absence of ligands crystal field splitting does not occur and hence the substance is
colourless. The compounds can also be colourless in case of paired electrons or no electrons in
d-orbitals.
11. Magnetic Property of Coordination Compounds
Coordination compounds containing unpaired electrons are paramagnetic while coordination
compounds containing all electrons paired are diamagnetic in nature.
Diamagnetic compounds are weakly repelled by magnetic field and paramagnetic compounds
are attracted to applied magnetic field.
12. Stability of Complex Ion It depends on the charge present on central atom, nature of metal
ion, basic nature of ligand, presence of chelate ring and effect of multidentate cyclic ligand.
For the reaction, Ma+ +nLx- [MLn]b+ the equilibrium constant is termed as stability constant
(k).
ML n b +
It is expressed as, k = M a + Lx − n

13. Importance and Uses

(i) Analytical chemistry, qualitative detection and quantitative estimation of metal ions.
(ii) Metallurgy Used in extraction of metal.
(iii) In biological system Haemoglobin (complex of iron), chlorophyll (complex of magnesium).
(iv) In industry As catalyst, in electroplating.
(v) In medicine cis-platin (cis-PtCI2(NH3)2]) used in the treatment of cancer.

ORGANIC CHEMISTRY
Haloalkanes and Haloarenes
Haloalkanes
Haloalkanes are obtained by the replacement of a hydrogen atom of an alkane by a halogen
atom (F, Cl, Br, I).
(i) Nomenclature
In common system, monohalogen derivatives of alkanes (alkyl halides) are named by adding
the word ‘halide’ to the name of the corresponding alkyl group.
Here, the prefixes n-, iso-, sec-, tert- etc., are used.
In IUPAC system, alkyl halides are named as halosub, stituted hydrocarbons, i.e. haloalkanes.
The names are written by prefixing the word 'halo' to the name of alkane corresponding to the
longest continuous straight carbon chain having the halogen atom, e.g.

CH3CH2CH2Br,

Common name IUPAC name n-propyl bromide 1- iso -propyl chloride

bromopropane
2-chloropropane

(ii) Nature of C—X Bond

Due to the greater electronegativity of halogen atom, the halogen atom in C—X bond acquires
partial negative charge, whereas C-atom acquires partial positive charge.
(iii) Preparation
(a) From alkane and halogen Chloroalkane and bromoalkane can be prepared by the reaction
of alkane with chlorine or bromine in the presence of sunlight or heat. For higher alkanes, a
mixture of1°, 2° and 3° alkyl halide is obtained
(b) From alkene and hydrohalide Halogen acid when treated with alkene undergoes addition
reaction to yield haloalkane. Unsymmetrical alkene follows Markownikoff's rule.
CH3—CH—CH2 + HBr →

Propene 2-bromopropane

(c) From alcohols Most common method forpreparation of haloalkanes is the replacement of —
OH group of an alcohol by required halogen atom.
With phosphorus halides Chloroalkanes can be prepared by the reaction of PCI5 or PCI3.

ROH + PCI5→ RCI + POCI3+HCI

Chloroalkane

3 ROH + PCI3→ 3RCI + H3PO3

With thionyl chloride In the presence of pyridine.

ROH +SOCl2 Pyridine RCI + SO2 ↑ + HCI↑

(d) Preparation by halogen exchange method

Finkelstein reaction Alkyl iodides are often prepared by the reaction of alkyl chlorides/
bromides with Nal in dry acetone. This is called Finkelstein reaction.
R—X + Nal →R—l + NaX (X = [Link])
Swart’s reaction Fluoroalkanes are best prepared by treating alkyl chloride/bromide in the
presence of a metallic fluoride such as AgF,Hg2F2. This is known as Swart’s reaction.

CH3Br + AgF → CH3F + AgBr

Bromomethane Fluoromethane

(e) Borodine-Hunsdiecker reaction

CH3COO– Ag+ + Br2 CCI4 350K CH3Br + CO2+ AgBr

Reflux

(iv) Physical Properties

(a) Alkyl halides are highly combustible.
(b) For the same alkyl group, the boiling point decreases in. the order Rl>RBr>RCI >RF.
As the size of alkyl group decreases, boiling points decreases for the same halogen,
CH3CH2CH2X > CH3CH2X > CH3X
(c) Alkyl halides are slightly solube in water because they do not form H-bonds with water.
(v) Chemical Properties
(a) Nucleophilic Substitution Reactions (SN) Nucleophile attacks at electron deficient sites.
SN reactions are of two types-SN1 and SN2. In SN1 reaction, rate is proportional to the
concentration of alkyl halide and it is ummolecular. While, in SN2 reaction, rate is proportional to
the concentration of both alkyl halide and nucleophile and it is bimolecular.
The order of reactivity of alkyl halides for:
SN1 is 3° >2°> 1° and SN2 is 1° > 2° > 3°
Various nucleophilic substitution reactions are as follows
• Reaction with aqueous NaOH Flaioalkanes react with boiling aqueous alkali, like NaOH or
KOH to qive alcohols.

e.g. C2H5Br + NaOH (aq) → C2HΓOH+ NaBr

Ethyl bromide Ethyl alcohol

• Reaction with water Haloalkanes are hydrolysed to alcohols by boiling water.

RX + H OH → ROH + HX
Alcohol

C2H5Br+ HOH → C2H5OH+HBr

Ethyl bromide Ethyl alcohol

• Reaction with sodium iodide Alkyl chlorides or bromides on treatment with Nal in acetone
undergo halogen exchange to give alkyl iodides.

C2H5CI C2H5l + NaCI

C2H5Br C2H5l + NaBr

This reaction is called Finkelstein reaction.

• Reaction with ammonia (Formation of Amines) Haloalkanes on heating with ethanolic
ammonia under pressure gives primary amine.
The primary amine, thus formed react further with alkyl, halides and gives 2°, 3° amines and
quaternary ammonium salts.

e.g. C2H5Br + NH3 → C2H5NH2+HBr

Ethyl Ethylamine (1° amine)

bromide

C2H5NH2 + C2H5Br → (C2H5)2NH+HBr

Diethylamine
(2° amine)
(C2H5)2NH + C2H5Br → (C2H5)3N+HBr .

Triethylamine

(3° amine)

(C2H5)3N + C2H5Br → [(C2H5)4NrBr-

Tetraethyl ammonium

bromide (Quaternary salt)

This reaction is called ammonolysis.

• Reaction with potassium cyanide (Formation of cyanides) Haloalkanes on reaction with
alcoholic solution of KCN give alkyl cyanides.

C2H5Br + KCN(alc.) → C2H5CN + KBr

Ethyl bromide Ethyl cyanide

• Reaction with silver cyanide (Formation of isocyanides) Aqueous alcoholic silver cyanide
when heated with haloalkanes, it gives alkyl isocyanides.

C2H5Br + AgCN(ag,alc.) → C2H5NC +AgBr

Ethyl bromide Ethyl isocyanide

• Reaction with potassium nitrite When

haloalkanes are heated with aqueous alcoholic solution of KNO2, alkyl nitrite are produced as
major product.

C2H5Br + K—O—N = 0→
Ethyl bromide Potassium nitrite

C2H5—0—N = O + KBr
Ethyl nitrite Polassiumbromide

•Reaction with silver nitrite When haloalkanes are heated with an ethanolic solution of
AgNO2, nitro alkanes are produced as major product.

• Reaction with silver salt of acids (Formation of ester) Haloalkanes on reaction with an
ethanolic solution of silver salts of a carboxylic acid give esters.
• Reduction Haloalkanes on reduction with LiAIH4 give alkanes.

4C2H5Br + LiAIH4—→ 4C2H6↓ AIBr3 + UBr

Ethane

(b) Elimination Reaction

Haloalkanes having β-hydrogen atom undergoes β-elimination when heated with alcoholic
solution of KOH.
Due to involvement of elimination of β-hydrogen atom, the process is often called β-
elimination.

(c) Reaction with metals Most organic chlorides, bromides and iodides react with certain
metals to give compounds containing carbon metal compounds.
• Action with Mg (Formation of Grignard reagent)

R—X+ Mg Dry ether RMgX

Alkyl (Grignard

halide reagent)

• Action of Na (Wurtz reaction)

R—X + 2Na+ X—R Dry ether R—R + 2NaX

(vi) Uses
• Synthesis of large variety of organic compounds.
• Ethyl chloride is used as a local anaesthetic and as refrigerant.
• Ethyl bromide is used for the preparation of barbiturate drugs.
2. Haloarenes
Haloarenes are obtained by the replacement of a hydrogen atom of an aromatic hydrocarbon by
a halogen atom (F, Cl, Br, I).
(i) Nomenclature
They are named by prefixing ‘halo’ before the name of the aromatic hydrocarbon.
Haloarenes are the common as well as IUPAC names of aryl halides. For dihalogen derivatives,
the prefixes, o-, m-, p- are used in common system but in IUPAC system, the numerals 1,2; 1,3
and 1,4 are used.
 (a) (b) (c)

Common and IUPAC names of above figures are given below

Common name IUPAC name

(a) Bromobenzene Bromobenzene

(b) m-dibromobenzene 1,3-dibromobenzene

(c) sym-tribromobenzene 1,3,5-tribromobenzene

(ii) Nature of C—X Bond

In haloarenes, sp2-hybridised carbon of benzene is bonded to halogen and C—X bond is also
polar as in haloalkanes. ,
Also, as lone pairs of electrons of halogen atom are involved in resonance with benzene ring.
So, this C—X bond acquires partial double bond character.
(iii) Preparation
• By halogenation of aromatic hydrocarbons
Haloarenes can be prepared by the halogenation of aromatic hydrocarbons in presence of
FeCI3 as given below

• From benzene diazonium salts

(iv) Physical Properties

(a) These are colourless with pleasant smell, insoluble in water.
(b) Isomeric haloarenes have similar boiling points.
(c) But p-isomers have higher melting point than other two, i.e. meta and ortho because of the
symmetry in p-isomer which occupies crystal structure better than ortho and meta-isomers.
(v) Chemical Properties
• Haloarenes are less reactive than haloaikanes towards nucleophilic substitution reactions, due
to resonance effect, sp2-hybridisation of a bearing halogen atom and instability of phenyl cation.
Under drastic condition, haloarenes undergo nucleophilic substitution reactions are given below.
Some nucleophilic substitution reactions are.
• Substitution by hydroxyl group Chlorobenzene when heated in aq. NaOH solution at 623 K
and 300 atm, phenol is formed. This is known as Dow's process.

The presence of electron withdrawing group (—NO2) at ortho and para positions increases the
reactivity of haloarenes
• Substitution by —NH2 group
Chlorobenzene in presence of strong base such as NaNH2 undergoes nucleophilic substitution
reaction.

Electrophilic Substitution Reactions

Electrophilic substituation reactions of haloarenes yield ortho (minor) and para products (major)
The common electrophilic substitution reactions of haloarenes are depicted as below:
• Halogenation

• Nitration

• Sulphonation

• Friedel-Craft alkylation
• Friedel-Craft acylation

Reaction with metals

* Wurtz-Fittig reaction When aryl halide is heated with alkyl halide with sodium in presence of
dry ether, halogen atom is replaced by alkyl group and alkylarene is formed. The reaction is
called Wurtz-Fittig reaction.

• Fittig reaction
When haloarenes react with sodium in the presence of dry ether, two aryl groups are joined
together and diphenyl is formed. This reaction is called Fitting reaction.

• Addition reaction with Mg

In this reaction, haloarene reacts with Mg then Grignard reagent is formed.

Phenyl magnesium bromide

• Addition with lithium
Bromo and iodo arenes react with lithium metal in the presence of dry ether to form their
corresponding organometallic compounds.

Phenyl lithium bromide

• Reaction with copper powder (Ullmann reaction)

In this reaction, iodobenzene is heated with copper powder in a sealed tube, diphenyl is formed.
(iv) Reduction On reduction of haloarenes, hydrocarbons are formed.

3. Polyhalogen Compounds
(i) Chloroform, (QHCI3) Trichloromethane is the trichloro derivative of methane commonly
known as chloroform.
(a) Preparation
I. From methane Methane reacts with chlorine in the presence of light of form chloroform as
given below

CH4 + Cl2 CH3CI

CH2CI2 CHCI3
Chloroform

II. Partial reduction of carbon tetrachloride

Carbontetrachloride reduced to chloroform as given below

CCI4 +2H CHCI3 + HCI

(b) Physical property Colourless heavy liquid causes temporary unconsciousness

(c) Chemical properties
I. Oxidation When exposed to air and sunlight form highly poisonous gas,carbonyl chloride or
phosgene.
II. Reduction With zinc and hydrochloric acid, it reduces to methylene chloride.
III. Hydrolysis When boiled with aqueous or alcoholic potassium hydroxide, it gets hydrolysed
to give formic acid, which combines with KOH to give potassium formate.
IV. Nitration It may be nitrated by concentrated nitric acid to form chloropicrin.
(d) Uses It is used as anaesthetic, solvent for oils, fats, medicines.
(e) Halfmful effects It affects the CNS. Inhaling at, 900 ppm for a short time cause dizziness,
fatigue and headache. Skin develops sore if immersed directly into the chloroform.
(ii) Iodoform (CHI3)
(a) Preparation (Haloform reaction)
I. From ethanol Iodoform is prepared by ethanol by the following manner

CH3CH2OH + 4I2 + 6NaOH

Ethanol
CHI3 + HCOONa + 5Nal + 5H20

Iodoform Sodium formate

II. From acetone Acetone reacts with l2 and NaOH to form iodoform as given below :

(b) Physical properties

I. It is a pale yellow crystalline solid and insoluble in water.
II. On heating, it decomposes, to give iodine vapour.
(c) Chemical properties
I. Reduction When reduced with red phosphorus and hydroiodic acid, it gives methylene iodide.
II. Hydrolysis Hydrolysis of iodoform can be done as follows

CHU + 3KOH [H—C(OH)3]

(ale.) (Unstable)

III. Dehalogenation Iodoform undergoes

dehalogenation to form ethyne as given below:

CHI3 + 6Ag + CHI3 HC≡CH + 6Agl

Ethyne

IV. Reaction with silver nitrate CHI3 reacts with silver nitrate (ale.) to form yellow ppt. of Agl.

Iodoform + silver nitrate Yellow ppt. of Agl

(ale.)

(d) Uses It is used as an antiseptic due to liberation of iodine.

(iii) Freons
Chlorofluorocarbons compounds of methane and ethane are collectively known as freons.
Freon-12 is one of the most common freons in industrial use.
(a) It is manufactured as,
(b) Uses These are used as refrigerants in refrigerators and air conditioning. These are used as
propellants for aerosols and foams to spray out deodrants, hair creams and insecticides.
(c) Harmful effects Most freons makes its way into the atmosphere where it undergoes
photochemical decomposition and initiate radical chain reactions for depletion of the ozone
layer.
Therefore, the use of freons as propellants and refrigerants has been dranstically discouraged.
(iv) DDT [2,2-bis-.(p-chloropheπyl) -1, 1, 1-trichloroethane] or (p,p'-
dichlorodiphenyltrichloroethane)
• Preparation It can be prepared by reacting chloral with chlorobenzene as given below

• Uses
This white powder is used as insecticide.
It is popularly very effective against anopheles mosquitoes and lices which carry typhus.
Harmful effects
Its use has been restricted as it is toxic, non-biodegradable and highly stable once entred a food
chain.
Alcohols, Phenols and Ethers
1. Alcohols
Hydroxy derivatives of aliphatic hydrocarbons are called alcohols. They possess the general
formula R—OH, where R is an alkyl or substituted alkyl group. These are named by replacing ‘e’
of parent alkane with suffix ‘ol’. The general formula of alcohols is CnH2n+1OH.
(i) Classification of Alcohols
(a) On the basis of no. of —OH groups present in the molecules
(i) Those alcohols which contain one —OH group are called monohydric alcohols, e.g.
CH3OH: C2H5OH etc.
(ii) Those alcohols which contain two —OH groups are called dihydric alcohols. Their general
formula is CnH2n(OH)2 They are also called diols, e.g. 1, 2-ethanediol.
(iii) Those alcohols which contain three hydroxyl groups are called trihydric alcohols. They are
also called triols. e.g. 1, 2, 3-propanetriol.
(b) On the basis of position of —OH group in the carbon chain
(i) The alcohol in which —OH group is attached to r carbon atom is called primary alcohol
e.g. CH3OH,C2H5OH, etc.
(ii) The alcohol in which —OH group is attached to 2° carbon atom is called secondary
alcohol,e.g. 2-propanol.
(iii) The alcohol in which —OH group is attached to 3° carbon atom is called tertiary alcohol.
e.g. 2-methylbutan-2-ol.
(ii) Structure
The structure of an alcohol resembles the structure of water with an alkyl group replacing one of
hydrogen atoms of water.
Both have sp3-hybridised oxygen atoms, but the C—O—H bond angle in methanol is
considerably larger than H—O—H bond angle in water due to the large size of methyl group in
alcohol.
(iii) Methods of Preparation
(a) Hydrolysis of alkyl halide Haloalkanes when treated with aqueous solution of an alkali
(NaOH/KOH) give corresponding alcohols.

R—X + KOH(ag) → R—OH + KX

Haloaikane Alcohol

(b) From Grignard reagent Aldehydes and ketones react with Grignard reagent to form
alcohol.
I. HCHO gives primary alcohols.
II. Aldehyde other than formaldehyde give secondary alcohols.
III. RCOR' gives tertiary alcohols.
(c) From alkenes
• Direct hydration of alkenes Alkenes react with water in the presence of acid as catalyst to
form alcohols.

• Indirect hydration of alkenes In this method, sulphuric acid and alkene react at elevated
temperature and under pressure to form sulphate esters which upon hydrolysis give alcohol.
Hydroboration-oxidation process Diborane reacts with alkenes to give trialkyl boraπes as an
addition product which upon subsequent oxidation by H202 in presence of aq. NaOH give
alcohols.

(d) By the reduction of carboxyl compounds

• Aldehydes and Ketones are reduced to the primary and secondary alcohols respectively.

• Carboxylic acids are reduced to primary alcohols by LiAIH4.

R-COOH R CH2OH

(e) From primary amines Aliphatic primary amines react with nitrous acid to give primary
alcohols.

NaNO2 + HCI HN02 + HCI

R— NH2+ HNO2 R —OH + N2 ↑+ H2O

(iv) Physical properties of alcohols

These are colourless volatile liquids having characteristic alcoholic odour and burning taste.
Alcohols are polar in nature and capable of forming intermolecular hydrogen bonding. Alcohols
are soluble in water.
The solubility of alcohols in water decreases with increase in molecular mass.
The boiling points of alcohols are considerably higher than those of corresponding
hydrocarbons, haloalkanes, ethers etc. due to H-bonding.
(v) Chemical properties of alcohols
(a) Acidic behaviour Alcohols behave as weak acids and isonise to a very small extent as
shown below.

Acidic strength of alcohols is even less than that of water.

(b) Reaction with active metals When an alcohol is treated with sodium or potassium, the O—
H bond gets cleaved and a metal alkoxide is formed with the evolution of hydrogen gas.

2R—OH+ 2Na → 2RŌN+a + H2↑

 Sodium alkoxide

(c) Reaction with metal hydrides Alcohols react with metal hydrides to form metal alkoxides
with the evolution of hydrogen gas.

(d) Reaction with Grignard’s reagent When an alcohol is treated with Grignard’s reagent; the
H-atom of the —OH group of the alcohol combines with the alkyl part of the Grignard's reagent
to give an alkane.

(e) Dehydration Alcohols undergo dehydration when treated with cone. H2SO4 or H3PO4.
The steps involved in this process are:
StepI Protonation of alcohol

StepII Formation of carbocation [slowest step, hence it is a rate determining step]

StepIII Formation of ethene by elimination of a proton

(f) Reaction with PCI3, PCI5 and SOCI2Alcohols react with phosphorus halides (PCI3, PCI5) and
thionyl chloride (SOCI2) to form corresponding haloalkanes.

(g) Reaction with acid chlorides and acid anhydrides

Alcohols react with acid chlorides or acid anhydrides in the presence of bases like pyridine to
form ester. This, reaction is called acylation reaction.
(h) Reaction with hydrogen halides Alcohols reacts with phosphorus halide, PCI3, PCI5 etc.,
to form corresponding haloalkanes.

R ––OH + HX → R-—X + H2O

Haloalkane

(i) Oxidation Primary and secondary alcohols are oxidised by Na2Cr207/K2Cr207 to form
aldehydes and ketones.

Tertiary alcohols when subjected to vigorous oxidation with nitric acid give ketone containing
lesser number of carbon atoms.
(j) Reaction with carboxylic acid (esterification)

(vi) Some Commercially Important Alcohols (a) Methanol (CH3OH)

It is also known as ‘wood spirit’, as it was produced by the destructive distillation of wood.
Preparation (Bosch Process)
Now-a-days, methanol is produced by the catalytic hydrogenation of carbon monoxide at high
pressure and temperature in the presence of ZnO-Cr2O3 catalyst.

CO+2H2 CH3—OH
Methyl alcohol or methanol
(b) Ethanol (C2H5OH)
Preparation
It is obtained commercially by the fermentation of sugar present in molasses, sugarcane or fruits
like grapes.

C12H22O11 + H2O C6H12O6 + C6H12O6

Sucrose Glucose Fructose

C6HI2O6 2C2H5OH +2CO2 ↑

Glucose or Fructose Ethanol

Fermentation takes place in anaerobic conditions, i.e. in the absence of air. Carbon dioxide is
released during fermentation. If air gets into fermentation mixture, the oxygen of air oxidises
ethanol to ethanoic acid which destroys the taste of alcoholic drinks.
(vii) Distinction between Primary, Secondary and Tertiary Alcohols
(i) Lucas Test
A small quantity of unknown alcohol is added to Lucas reagent (anhy. ZnCI 2 + cone. HCI) at
room temperature and the mixture is shaken.
A tertiary alcohol forms turbidity immediately, secondary alcohol forms turbidity within five
minutes and primary alcohol shows no turbidity at room temperature.
(ii) Victor Meyer's Test
The given alcohol is treated with red phosphorus and iodine to convert it into the corresponding
alkyl iodide which is then further treated with AgNO2 to form nitroalkane which is finally treated
with nitrous acid and the resulting solution is made alkaline.
Primary alcohols give blood red colour, secondary alcohols give blue colour and in case of
tertiary alcohols, solution remains colourless.
(viii) Conversion of One Alcohol into Another.
(i) Conversion of a Lower Alcohol into a Higher Alcohol

R—OH Rl RCN
Lower alcohol

R CH2NH2 RCH2OH
Higher alcohol

(ii) Conversion of Higher Alcohol into a Lower Alcohol

RCH2OH RCHO RCOOH

Higher alcohol
(iii) Conversion of Primary Alcohol to a Secondary Alcohol

(iv) Conversion of Secondary Alcohol to a Tertiary Alcohol

(v) Conversion of Primary Alcohol to a Tertiary Alcohol

2. Phenols
Phenols are the hydroxy derivatives of arenes in which one or more —OH groups are directly
attached to the carbon atoms of an aromatic ring.
(i) Preparation of Phenols
(a) Dow's process In this process, phenol is prepared by heating chlorobenzene with 10%
NaOH solution at 623 K under 300 atm followed by hydrolysis.
(b) From sulphonic acids When sodium salts of aromatic sulphonic acids are fused with NaOH
at 573 K followed by acidification, phenols are obtained.

(c) From diazonium salts Diazonium salts are hydrolysed in the presence of dil. H2SO4 to give
phenols.

(d) From cumene This method is used for the commercial preparation of phenol. This reaction
proceed at 150°C in the presence of HBr as a catalyst. The reaction is also called auto
oxidation.

Also, it gives o- and p- phenol sulphonic acids when treated with cone. H2SO4 (sulphonation)

(e) Reaction with zinc dust It gives benzene on heating with Zn dust.

(f) Friedel-Craft’s reaction Phenols undergo Friedel-Craft’s reaction in the presence of

anhydrous AICI3.
(g) Reaction with PCI5The replacement of —OH group of phenol by a halogen atom is quite
difficult and the yield of chlorobenzene is very poor.

(h) Koibe’s reaction Phenoxide ion produced by treating phenol with NaOH is more reactive
than phenol towards electrophilic aromatic substitution. Hence, it undergoes electrophilic
substitution with weak electrophile CO2.

Reimer-Tiemann reaction On treating phenol with CHCI3 (chloroform) in the presence of

sodium hydroxide, a —CHO group is introduced at ortho position of benzene ring. This reaction
is called Reimer-Tiemann reaction. In this 'reaction, electrophile is dichlorocarbene (:CCI2).

(ii) Physical Properties

(a) Phenols are either colourless liquids or colourless crystalline solids with low melting points.
(b) Phenols are slightly soluble in water.
(c) Phenols possess higher boiling points as compared to those of the corresponding aromatic
hydrocarbons and haloarenes.
(iii) Chemical Properties
(a) Acidic character Phenols are more acidic than alcohols, due to more stabilisation of
phenoxide ion formed by delocalisation of negative charge.
Presence of electron withdrawing groups such as —NO2,—CHO, etc, increases acidic strength
of phenol by stabilising phenoxide ion whereas, electron releasing group like —CH3 reduces the
acidic strength of phenol.
(b) Electrophilic aromatic substitution Phenols undergo electrophilic aromatic substitution
reaction readily due to presence of —OH group. It gives 2,4,6-trinitrophenol (or picric acid) when
treated with cone. HN03 (Nitration) and 2,4,6-tribromophenol when treated with Br2/H2O
(Bromination). However, when phenol is treated with Br2 in CS2, it gives o- and p-bromophenol.

(iv) Test for Phenols

(a) Reaction with ferric chloride Unlike alcohols, phenols react with neutral FeCI3 and give
violet coloured water soluble complex [Fe(OC6H5)3]3-
Thus, this reaction is used to distinguish phenol and known as Ferrichloride test.
(b) Coupling reaction (Also dye test) Phenol reacts with diazonium salt to form aro dye but
alcohol does not form azo dye.
(iv) Uses
It is used in perfumery. It is widely used in the manufacture of dyes, plastics etc.
3. Ethers
The substitution of a hydrogen atom in a hydrocarbon (aliphatic/aromatic) by an alkoxy
(OR)/aryloxy (OAr) group yield ethers. These have general formulaCnH2n+2O and are
represented by general structure R—O—R.
(i) Structure of ethers
O-atom in ethers is sp3-hybridised. Ethers have a bent or angular structure. Ethers are dialkyl
derivatives of water or monoalkyl derivatives of alcohols.

(ii) Preparation of aliphatic and aryl ethers (a) From alcohols (By dehydration of 2 moles of
alcohols)

The order of dehydration of alcohols leading to the formation of ethers is

primary alcohol > secondary alcohol > tertiary alcohol
(b) By Williamson’s synthesis from haloalkanes This is one of the best method for the
preparation of ethers.
In this method, alkyl halide is treated with a suitable sodium (or potassium) [Link].

R—O-Na+ + XR → R—0—R + NaX

Sodium alkoxide Alkyl Ether
halide

(c) Reaction of alkyl halides with dry silver oxide When alkyl halide is heated with silver
oxide, symmetrical ether is formed.

(d) From Grignard’s reagent Higher ethers can be prepared by treating α-haloethers with
suitable Grignard’s reagent.

(in) Physical properties of ethers

(a) Boiling points of ethers are much lower than those of [Link].
(b) Solubility Lower ethers (upto three carbon atoms) are soluble in water and their miscibility
with water resembles those of alcohols of the same molecular masses.
(iv) Chemical properties of aliphatic ethers (a) Halogenation When ethers react with Cl2 or
Br2 in dark, substitution takes place mainly at α-C-atonn.

R'CH2—O—R+ Cl2 R'CHCl—O—R+ HCI

Ether Chlaroether

(b) Reaction with peroxides In contact with airor02, ethers form peroxides which are unstable
compounds.

(c) Reaction involving cleavage of C—O bond

• Reaction with halogen acids (HX) In cold, alkyl halide and alcohol are formed.

R—O—R + HX POH + RX
Ether (X = 1 or Br) Alcohol Alkyl halide
e.g. C2H5— O — C2H5 + HI C2H5I + C2H5OH
Diethyl ether lodoethane Ethanol

With excess of halogen acids, 2 molecules of alkyl halides are formed.

R—O—R + 2 HX 2 RX + H2O
Excess

. e.g. C2H5— O —C2H5 + 2HI Δ 2C2H5I+ H20

Excess

Reaction with PCl5Alkyl chlorides are formed by the cleavage of C—O bond.

R—O—R + PCI5 2R— Cl + poci3

Alkyl chloride

(v) Chemical Properties of Aryl Ethers

Aryl ethers undergo electrophilic substitution reaction. These are as follows :
Electrophilic substitution reactions Important electrophilic substitution reactions are as
follows:
(a) Halogenation

(b) Friedel-Craft’s reaction Anisole undergoes Friedel-Craft’s reaction, i.e. the alkyl and acyl
groups are introduced at o-and p-positions by reaction with alkyl and acyl halides in the
presence of anhydrous aluminium chloride (a Lewis acid) as catalyst.
(c) Nitration Anisole reacts with a mixture of concentrated sulphuric acid and nitric acid to yield
a mixture of ortho and para nitroanisole.

(vi) Uses of Ethers

(a) Dimethyl ether is used as a refrigerant and as a solvent at low temperatures.
(b) Used as an industrial solutions for oils, resins, gums, etc.
(c) As an extracting solvent in laboratory and industry because of their almost inert nature and
good dissolving power.
Aldehydes, Ketones and Carboxylic Acids
1. Carbonyl Compounds or Aldehydes and Ketones
The C = O group is known as the carbonyl group and the compounds containing C = O group
are known as carbonyl compounds. In aldehydes, the carbonyl group is bonded to carbon and
hydrogen while in-ketones, it is bonded to two carbon atoms.

Aldehydes and ketones have molecular formula, CnH2nO and are functional isomers of each
other.
Methods of Preparation of Aliphatic
Aldehydes and Ketones (i) From alcohols
(a) By oxidation of alcohol's with K2Cr2O7/ H2SO4 or KMnO4/ KOH.

(b) By catalytic dehydrogenation of alcohols with Cu at573K.

(ii) From alkenes (Ozonolysis) By reductive ozonolysis of alkenes, carbonyl compounds are
formed.
(iii) From alkynes Alkynes on hydration in presence of dil. H2S04 and HgS04 gives
acetaldehyde whereas all other alkynes give ketones.
(iv) From calcium salts of carboxylic acids
(v) From acid chloride Aldehydes can be obtained from acid chlorides by the catalytic
hydrogenation known as Rosenmund’s reduction.

Ketones cannot be prepared by this method. They are prepared by treating acid chlorides with
dimethyl cadmium in the presence of dry ether.
(vi)From nitriles
• Nitriles are also reduced to corresponding imine with stannous chloride in the presence of
hydrochloric acid which on hydrolysis give corresponding aldehydes.

RCN + SnCI2 + HCI → RCH = NH RCHO

Nitrile amine Aldehyde

This reaction is known as Stephen reaction.

• When nitriles reacts with Grignard reagent followed by hydrolysis yields a ketone.

(vii) From esters Esters can also be reduced to aldehydes with DIBAL-H.

Physical Properties of Aldehydes and Ketones

(i) Methanal is a gas while ethanal is a volatile liquid at room temperature.
(ii) Boiling points of aldehydes and ketones are higher than hydrocarbons and ethers of
comparable molecular masses.
(iii) All aldehydes and ketones are fairly soluble in organic solvents like benzene, ether,
methanol, chloroform, etc.
Chemical Properties of Aldehydes and Ketones Nucleophilic addition reactions
Aldehydes and ketones undergo nucleophilic addition reactions. These reactions are catalysed
by both acids and bases.
Some Important Nucleophilic Addition Reactions are
(a) Aldehyde and ketones on reaction with HCN give cyanohydrins. This reaction is slow, so it is
catalysed by a base.
(b) Addition of sodium hydrogen sulphite to aldehydes or ketones results in the formation of an
addition product as follow

(c) Aldehydes and ketones on reaction with Grignard reagent give addition products which upon
hydrolysis with water/dil. mineral acids gives alcohol.

(d) Aldehyde react with one equivalent of monohydric alcohols in the presence of dry HCI gas to
give hemiacetals which on further reaction with 1 more molecule of alcohols give acetals. The
reaction is given: as,

Ketones react with dihydric alcohols to give cyclic ketals.

(e) Nucleophiles such as ammonia and its derivative, H2N—Z add to the carbonyl group of
aldehyde and ketones in presence of weakly acidic medium. The reaction is given as below

[Z = alkyl, aryl, OH, NH2, C6H5NH, NHCONH2, etc.]

(f) Base catalysed reactions
• Aldol condensation Aldehydes and ketones containing a -H atoms undergo aidol
condensation in presence of dilute alkali as catalyst to form β-hydroxy aldehyde aldol) orβ-
hydroxy ketones (ketol).
* Cross-aldol condensation When two different aldehydes or different ketones or one
aldehyde and one ketone each containing α-H atoms, undergo crossed aldol condensation.
e.g.

(g) Cannizzaro’s reaction Aldehydes which do not have α-H atoms undergo self oxidation and
reduction on treatment with cone, alkali.
e.g

(i) Reaction with grignard reagent Aldehydes and ketones on reaction with Grignard reagent
give addition oroducts which upon hydrolysis αive alcohols.

• Oxidation of aldehydes to carboxylic acids

Aldehydes differ from ketones in their oxidation reactions. Aldehydes are easily oxidised to
carboxylic acids containing the same number of carbon atom, because aldehydes contain H-
atom attached to carbonyl group, which can be converted into —OH group without involving
cleavage of any other bond.

RCHO R—COOH

• Oxidation of ketones Unlike aldehydes, ketones do not contain H-atom attached to C=0
group and hence they cannot be oxidised by weak oxidising agent. They are oxidise by strong
oxidising agants, like KMn04, acidified K2Cr204at high temperature.

• Iodoform reaction Aldehyde and ketones having atleast one methyl group linked to carbonyl
carbon atom (methyl ketone) are oxidised by sodium hypohalite to sodium salts of
corresponding carboxylic acids having one carbon atom less than that of carbonyl compound.

• Reduction Aldehydes and ketones can be reduced to a variety of compounds under different
conditions,

(Wolff-kishner reduction)
Uses of Aldehydes and Ketones
(i) Formaldehyde is used as disinfectant and as a germicide, 40% aqueous solution of
formaldehyde is called formalin.
(ii) Formaldehyde is used in the manufacture of bakelite, resin, and other polymers.
(iii) Formaldehyde is used in making urotropine, a medicine for urine infections.
(iv) Paraldehyde is used in medicine as a hypnotic.
(v) Acetone is used as a constituent of liquid nail polish.
Test to Distinguish betweeen Aldehydes and Ketones

Test Aldehydes Ketones

Tollen’s reagent test Give silver mirror No response

Fehling's solution test Give red precipitate No response

Schiffs reagent test Give pink colour No response, (acetone restore

the pink colour but very slowly)

Reaction with LiAIH4 Form primaryalcohols Form secondary alcohols

2. Aromatic Aldehyde or Benzaldehyde (C6H5CHO)

It is commercially known as oil of bitter almonds.
Preparation
From toluene Toluene on oxidation with chromyl chloride, oxidises methyl group to a chromium
complex which on hydrolysis gives corresponding benzaldehyde.

This reaction is known as Etard reaction.

Physical Properties
(i) It is highly refractive liquid.
(ii) It has boiling point of 452 K.
Chemical Properties
(i) Oxidation It gets oxidised to benzoic acid in the presence of dil, HNO3 or alkaline KMnO4.

(ii) Reduction It is reduced to benzyl alcohol.

(iii) Nucleophilic addition reaction (a) With HCN

(iv) Addition of Ammonia and its Derivatives
(a) With ammonia It reacts with NH3 to form complex product called hydrobenzamide.

(b) With ammonia derivatives

[Z =OH, NH2, C6HSNH, 2, 4-DNP, etc.]

(v) Reaction with PCI6Benzal chloride is formed when benzaldehyde reacts with PCI5.

C6HsCHO + PCI5 → C6H5CHCI2 + POCI3

Benzaldehyde Benzal chloride

(vi) Cannizzaro’s reaction When benzaldehyde is heated with strong alkaii solution, it
undergoes simultaneous oxidation and reduction forming salt of benzoic acid and benzyl
alcohol.

2C6H6CHO+ NaOH → C6H5CH2OH + C6H5COONa

Benzaldehyde cone. Benzyl alcohol Sodium benzoate

(vii) Benzoin condensation When two molecules of benzaldehyde are heated with an alcoholic
solution of KCN, they undergoes self condensation to form benzoin.

This reaction is called benzoin condensation.

(viii) Perkin’s reaction When benzaldehyde is heated with aliphatic acid anhydride in presence
of sodium salt of the acid corresponding to the anhydride, they form α, β-unsaturated acid on
hydrolysis.
(ix) Electrophilic substitution reactions — CHO group is deactivating m-directing group.
(a) Halogenation

(b) Nitration

(c) Sulphonation

Uses of Benzaldehyde
(i) As a flavouring essence in perfumery.
(ii) in the manufacture of dyes.
(iii) In the synthesis of cinnamic acid, cinnamaldehyde, etc.
Test to distinguish Between Aliphatic and Aromatic Aldehyde
They can be distinguished by iodoform test. Acetaldehyde gives a yellow precipitate of
iodoform, when heated with iodine in the presence of alkali.
Benzaldehyde does not give iodoform test.
3. Carboxylic Acids

The organic compounds which contain the carboxyl group as the functional group are
knownas car boxylic acids
Preparation of Carboxylic Acids (i) From Oxidation of Primary Alcohols and Aldehydes
Alcohols on oxidation with strong oxidising agent gives aldehyde which on further oxidation
gives carboxylic acids.

PCH2OP RCHO RCOOH

Primary Aldehyde Carboxylic
alcohol acid

(ii) From Hydrolysis of Nitriles

Nitriles are first hydrolysed to amides and then to carboxylic acids in the presence of H+ orOH―
as catalyst.

(iii) From Grignard reagent

Grignard reagent with dry ice(CO2) in etheral solution and on acidification give carboxylic acids.

Physical Properties of Carboxylic Acids

The physical properties of carboxylic acids are described below
(i) Solubility Simple aliphatic carboxylic acids having upto four carbon atoms are miscible in
water because of hydrogen bond formation with water.
(ii) Boiling point As compared to hydrocarbons, aldehydes and ketones, carboxylic acids have
higher boiling points because they have high extent of hydrogen bonding with water due to
which they exists as associated molecules.
(iii) Melting point The melting points of aliphatic carboxylic acids do not show a regular pattern
rather they show oscillation or alteration effect, i.e. melting point of an acid containing even
number of carbon atoms is higher than the next member containing odd number of carbon
atoms.
Chemical Properties of Carboxylic Acids
(i) Acidic nature of carboxylic acids

Greater the extent of ionisation, greater is the strength of the acid.

Presence of an electron donating substituent (+/-effect) decreases the acidic strength of the
carboxylic acid.
Presence of an electron withdrawing substituent (-/ effect) increases the acidic strength of the
carboxylic acid.
Reactions showing acidic character of carboxylic acids (a) Reaction with metals

(b) Reaction with alkalies,

(c) Reaction with carbonates and bicarbonates

(ii) Reaction involving —OH part of the carboxyl group

(a) Formation of acid chlorides Carboxylic acids can be converted into corresponding and
chlorides by- treating with PCI5, PCI3 or SOCI2

(b) Formation of esters When carboxylic acids reacts with alcohols in presence of Cone.
H2S04, esters are formed.

(c) Formation of amides They react with ammoniato form ammonium salts which upon heating
form acid amides.
(d) Formation of acid anhydride Carboxylic acids in presence of strong dehydrating agents
such as P2O5 or H2SO4 give acid anhydrides.

(iii) Decarboxylation of carboxylic acid By electrolysis of aqueous solution of sodium or

potassium salt.

At anode,

2RCOCT → R— R + 2COa + 2e-

Carboxylate Alkane

ion

At cathode.

2H2O 2M++ OH–

2H+ + 2e– -→ H2

This process is known as Kolbe’s electrolysis.

(iv) Halogenation
Carboxylic acids (except formic acid) react with chlorine or bromine in presence of small amount
of red phosphorus gives a- halogenated carboxylic acids.

CH3COOH CH2CICOOH
Acetic Acid Monochloro Acetic acid

CHCI2COOH CCI3COOH
Dichloro acetic acid Trichloro acetic acid

This reaction is called Hell-Volhard-Zelinsky (HVZ) reaction.

(v) Ring substitution reactions in aromatic carboxylic acids
(a) Halogenation
(b) Nitration

(c) Sulphonation

Test For
(i) Formic acid
(a) It gives silver mirror or black precipitate with Tollen’s reagent.
(b) It gives red precpitate with Fehling’s solution
(c) It qives decolourises pink colour of acidified KMn04.
(ii) Acetic acid
(a) It liberates carbon dioxide gas with bicarbonates and carbonates. With ferric chloride, it
produces win red colour.
(b) When warmed with ethyl alcohol and cone. H2S04, a pleasant fruity odour of ethyl acetate is
formed.
(iii) Benzoic Acid
(a) It dissolves in water on boiling but separate out in the for m of white shiring leaflets on
cooling.
(b) It gives buff coloured ppt with FeCI3.
Uses
(i) Formic acid
(a) As an antiseptic.
(b) For dye baths in textiles,
(c) As a coagulating agent in rubber industry.
(ii) Acetic acid
(a) As a solvent for resins, cellulose etc.
(b) In the production of dyes, perfumes, esters, acetone etc,
(c) For the manufacture of cellulose which is used for making packaging materials, varnishes,
rayon etc.
(iii) Benzoic acid
(a) As a food preservative either in the pure form or mostly in the form of sodium benzoate.
(b) As urinary antiseptic in medicine.
(c) In the manufacture of antiseptics and dyes.

Haloalkanes and Haloarenes

NCERT INTEXT QUESTIONS

Q. 10.1. Draw the structures of all eight structural isomers that have the molecular formula CsH11Br.
Name eachisomer according to IUPAC system and classify them as primary, secondary or tertiary
bromide. Ans. Eight isomers are possible. Their structures and IUPAC names are given below :

(i) CH3CH2CH2CH2CH2Br (ii) (iii)

1-Bromopentane (1°) 2-Bromopentane (2°) 3-Bromopentane (2°)

(iv) (v) (vi)

1 -Bromo-2-methylbutane (1°) 1 -Bromo-3-methylbutane 2-Bromo-3-methylbutane (2°)

(1°)

(vii) (viii)

1-Bromo-2, 2-dimethylpropane (1°) 2-Bromo-2-methylbutane (3°)

Q. 10.2. Write IUPAC names of the following :

(a) (b) (c) (d)

 (e) (CPSE (f) (CFSI'1 ?,01f :>(> 1

Ans. (a) (b) (c) (d

4-Bromopent-2- 3-Bromo-2- methylbut- 4-Bromo-3-methylpent- 1 -Bromo-2-methylbut-

ene 1-ene 2-ene 2-ene

(e) (f)

1-Bromobut-2-ene 3-Bromo-2-methylpropene

Q. 10.3. Identify all the possible monochloro structural isomers that would be expected to form on
free radical chlorination of (CH3)2CHCE2CH3.

Ans. In the given compound, there are four sets of different types of
hydrogen atoms as shown.
The replacement of any one of the equivalent hydrogens of each set will
give the following four monochloro derivatives.

(i) (ii)

1 -Chloro-2-methylbutane 2-Chloro-2-methylbutane

(iii) (iv)

2-Chloro-3-methylbutane 1-Chloro-3-methylbutane

Q. 10.4. Write the products of the following reactions :

 (i) (ii) CH3—CH2—CH = CH2 + HCl>

(iii) Peroxide
+ HBr →

Ans. (i) Mark addn.

+ HBr →

Phenylethene or 1 -Bromo-1 -phenylethane

Styrene

Mark. addn.
(ii)CH3CH2—CH = CH2 + HCl →

But-1-ene

2-Chlorobutane

(iii)
+ HBr

3-Phenylprop-1 -ene 1 -Bromo-3-phenylpropane

Q. 10.5. Haloalkanes react with KCN to form alkyl cyanides as main product while AgCN forms
isocyanides as the chief product. Explain.
Ans. Refer to pages, 10/25-10/26.
Q. 10.6. In the following pairs of halogen compounds whichis faster undergoing SN2 reaction ?

(i) (ii) (CBSE 2009)

Ans. (i) is a primary alkyl halide while is a secondary alkyl halide,

therefore, reacts faster in a SN2 reaction

than

(iii) Since I ion because of its bigger size and lower electronegativity is a better leaving group than Cl

ion, therefore, reacts faster than in a SN2 reaction.

Q. 10.7. Predict the order of reactivity of the following compounds in SN1 and SN2 reactions :
(i) The four isomeric bromobutanes
(ii)C6HsCH2Br, C6H5CH(C6H5)Br, C6H5CH(CH3)Br, C6HsC(CH3)(C6H5)Br.
Ans. (i) In SN1 reactions, the order of reactivity depends upon the stability of the intermediate
carbocations, therefore, (CH3)3CBr which gives a 3°carbocation, i.e., (CH3)3C+ is the most reactive.
CH3CH2CH(Cl)CH3gives a 2° carbocation, i.e.CH3CH2CHCH3 and hence is less reactive that (CH3)3CBr. Out
of the remaining two 1° alkyl halides, the carbocation (CH3)2CHCH+ is more stable than the carbocation
CH3CH2CH2CH2 due to greater +I-effect of (CH3)2CHCH2- group w.r.t.CH3CH2CH2CH2-group and
hence the alkyl halide, (CH3)2CHCH2Br is more reactive than CH3CH2CH2CH2Br. Thus, the overall
increasing reactivity of the four isomeric bromobutanes towards SN1 reaction follows the order :
CH3CH2CH2CH2Br < (CH3)2CHCH2Br <CH3CH2CH(Br)CH3< (CH3)3CBr The reactivity in SN2 reactions,
however, follows the reverse order, i.e.,
CH3CH2CH2CH2Br > (CH3)2CHCH2Br >CH3CH2CH(Br)CH3> (CH3)3CBr
since the steric hindrance around the electrophilic carbon (i.e. oc-carbon) increases in that order
(ii) Since the reactivity in SN1 reactions increases as the stability of the intermediate carbocation
increases,therefore, (C6H5)C(CH3) (C6H5) Br which gives 3° carbocation, i.e., (C6H5)2 C(CH,) is the most
reactive.
Of the two 2° bromides, the carbocation intermediate derived from C6H5CH(C6H5)Br, i.e., [Link]
more stable as compared to the carbocation C6H5CHCH3 obtained from C6H5CH(CH3)Br because it is
stabilized by two phenyl groups due to resonance. The fourth alkyl bromide, i.e., C6H5CH2Br which gives
the 1° carbocation, i.e., C6H5CH2 is, however, the least reactive. Thus, the overall reactivity of these alkyl
bromides towards SN1 reactions follows the order :
C6H5C(CH3)(C6H5)Br > C6H5CH(C6H5)Br > C6H5CH(CH3)Br > C6H5CH2Br
In SN2reactions, it is the steric hindrance which determines the reactivity. Since a phenyl group is much
bulkier than a methyl group, therefore, C6H5C(CH3)(C6H5) Br is the least reactive followed by
CfiH3CH(CgH3)Br and C6H5CH(CH3)Br while C6H5CH2Br is the most reactive. Thus, the overall reactivity of
these alkyl bromides towards SN2 reactions follows the order :
C6H5CH2Br > C6H5CH(CH3)Br > C6H5CH(C6H5)Br > C6H5C(CH3)(C6H5)Br Q. 10.8. Identify chiral and achiral
molecules in eachof the following pairs of compounds.
 (A) (B)

(i) (ii) til an

(c) CH3— CH2— CH2— CH2— Br

(ii)

Ans. (A) In structure (i),the central carbon atom is attached to four different substituents, i.e.,CH3, Br,
OH and H and hence (i) is a chiral molecule. Since structure (ii) has two identical Br atoms, therefore, it
represents an achiral molecule.
(B) In structure (i), the second carbon atom from left is attached to four different groups, i.e.,CH3, OH, H
and CH2CH2CH3 and hence (i) is a chiral molecule. Since structure (ii) has two identical groups, i.e.,
CH3CH2 on either side of the central carbon atom, therefore, it represents an achiral molecule.
(c) In structure (i), the second carbon atom from left is attached to four different groups, i.e.,CH3, H, Br
and CH,CH3, therefore, structure (i) represents a chiral molecule. Since structure (ii) does not contain an
asymmetric carbon, therefore, it represents an achiral molecule.
Q. 10.9. Although chlorine is an electron-withdrawing group, yet it is ortho-, para-directing in
electrophilic aromatic substitution reactions. Why ?

Ans. -(-Effect of Cl
destabilizes the
intermediate
carbocation

+R-Effect of Cl
stabilizes the
intermediate
 carbocation

Chlorine because of its -I-effect withdraws electrons from the benzene ring and hence tends to
destabilize the intermediate carbocation formed during the electrophilic substitution.
Conversely, the lone pairs of electrons on the chlorine atom stabilize the intermediate carbocation due
to resonance. Since -I-effect of Cl is stronger than its +R-effect, therefore, Cl causes net deactivation.
Further, since resonance effect opposes the inductive effect, it makes deactivation less at o- andp-
positions. Thus, we conclude that in chlorobenzene, reactivity is controlled by the stronger-I-effect while
orientation is controlled by the weaker resonance effect.

NCERT INTEXT unsolved QUESTIONS

Q. 10.1. Write the structures of the following compounds :

(i) 2-Chloro-3-methylpenfane (ii) 1-Chloro-4-ethylcyclohexane
(iii) 4-tert-Butyl-3-iodoheptane
(iv) 1, 4-Dibromobut-2-ene (v) 1-Bromo-4-sec-butyl-2-methylbenzene.

Ans. (i) (ii)

2-Chloro-3-methylpentane 1 -Chloro-4-ethy Icy clohexane

(iii) (tv)

1,4-Dibromobut-2-ene

4-tert- Butyl-3-iodoheptane
 (v)

[Link]-butyl-2-methy1benzene

Q. 10.2. Why is sulphuric acid not used during the reaction of alcohols with KI ?
Ans. H2S04 is an oxidising agent. It oxidises HI produced during the reaction to I2 and
2 KI + H2SO4> 2 KHSO4 + 2 HI ; 2 HI + H2SO4 » H2O + I2 + SO2
thus prevents the reaction between an alcohol and HI to form an alkyl iodide. To overcome this
difficulty, a non-oxidising acid suchas H3P04 is used instead of H2SO4.
∆
CH3CH2—OH + KI + H3P04 CH3CH2—I + kH2PO4 + H2O

Ethanol Iodoethane

Q. 10.3. Write structures of different dihalogen derivatives of propane.

Ans. Four isomeric dihalogen derivatives of propane are formed for eachhalogen. For example,

BrCH2—CH2—CH2Br

1, 3-Dibromopropane

1, 2-Dibromopropane 1, 1-Dibromopropane 2,2-

Dibromopropane

Similarly, we can write four isomeric dihalogen derivatives for other halogens.
Q. 10.4. Among the isomeric alkanes of molecular formula C5H12, identify the one that on
photochemical chlorination yields.
(i) A single monochloride (ii) Three isomeric monochlorides (iii) Four isomeric monochlorides.

Ans. (i) All the H atoms are equivalent. Therefore, replacement of

any one of them will give the same product.

Neopentane

(ii) There are three sets of equivalent hydrogens designated as a,

b and c. The replacement of any one of the equivalent
 hydrogens of eachset will give the same product. Therefore,
n-Pentane
three isomeric monochlorides are possible.

(iii) There are four types of equivalent hydrogens designated as a,

b, c and d. Therefore, four isomeric monochlorides are
possible.

Q. 10.5. Draw the structures of major monohalo products in eachof the following reactions.

(i) + SOCl2 → (CBSE 2009) (ii)

(iii) heat (iv) + HI →

+ HCl →

(CBSE 2009, CBSE (Foreign) 2017) (CBSE 2009 ; CBSE Sample Paper 2017)

(v) CH3CH2Br + Nal → (vi)

+ Br2

Ans. (i) + HCl ↑

+ SOCl2 → + SO2 ↑

Cyclohexanol Chlorocyclohexane

(ii)

4-EthyInitrobenzene 4-( 1 -Bromoethyl)nitrobenzene

Since benzylic radicals are more stable, therefore, benzylic hydrogen is abstracted.
 (iii) heat
+ HCl →

4-Hydroxymethylphenol 4-Chloromethylphenol

Only alcoholic but not phenolic OH groups are replaced by Cl on heating with HCl.

(iv)
+ HI Mark addn.
→

1 -Methylcyclohexene 1 -Iodo-1 -methylcyclohexane

(v) CH3CH3—Br + Nal CH3CH2—I + NaBr

Bromoethane Iodoethane

Iodide ion is a stronger nucleophile and hence it displaces bromide ion. Further, since NaBr is insoluble
while Nal is soluble in dry acetone, therefore, the equilibrium shifts in the forward direction.

(vi)

Cyclohexene 3-Bromocyclohex-1 -ene

In presence of heat and light, allylic bromination occurs to form 3-bromocyclohex-1-ene.

Q. 10.6. Arrange eachset of compounds in order of increasing boiling points.
(i) Bromomethane, bromoform, chloromethane, dibromomethane. (Karnataka CET 2015)
(ii) 1-Chloropropane, isopropyl chloride, 1-chlorobutane.
Ans. (i) For the same alkyl group, boiling point increases with the size of the halogen atom. Therefore,
boiling point of bromomethane is higher than that of chloromethane.
Further, the boiling points increase as the number of halogen atoms increases. Therefore, the boiling
point of bromoform with three Br atoms is the highest, followed by dibromomethane with two Br atoms
while bromomethane with one Br atom is the lowest. Combining all the arguments presented above,
the boiling points of the four compounds discussed above increase in the order :
chloromethane < bromomethane < dibromomethane < bromoform.
{ii) For the same halogen, boiling point increases as the size of the alkyl group increases. Therefore, the
boiling point of 1-chlorobutane is higher than those of 1-chloropropane and isopropyl chloride. Further,
the boiling point decreases as the branching increases, therefore, the boiling point of 1- chloropropane
is higher than that of isopropyl chloride. Combining these two arguments, the boiling points of the three
compounds discussed above increase in the order :
Isopropyl chloride < 1-chloropropane < 1-chlorobutane.
Q. 10.7. Whichalkyl halide from the following pairs would you expect to react more rapidly by SN2
mechanism ? Explain your answer.

(i)

(iii)

Ans. (i)CH3CH2CH2CH2Br is a 1° alkyl halide while CH3CH2—CHBr—CH3 is a 2° alkyl halide. Since there will
be some steric hindrance in 2° alkyl halides than in 1° alkyl halides, therefore, CH3CH2CH2-CH2Br will
react faster than CH3CH2—CHBr—CH3in SN1 reaction.
(ii) CH3CH2—CHBr—CH3 is a 2° alkyl halide while (CH3)3C—Br is 3° alkyl halide. Since due to lesser steric
hindrance, 2° alkyl halides react faster than 3° alkyl halides, therefore, CH3CH2—CHBr—CH3will react
faster than (CH3)3CBr in SN2 reaction.

(iii)

Both I and II are 2° alkyl halides. But in alkyl halide (II), the CH3 group at C2 is closer to the Br atom while
in alkyl halide (I), the CH3 group at C3 is little away from the Br atom. As a result, alkyl halide (I) will
suffer greater steric hindrance than alkyl halide (I). Therefore, (CH3)2CHCH2Br will react faster than
CH3CH2CH(CH3)CH2Br in SN2 reaction.
Q. 10.8. In the following pairs of halogen compounds, whichcompound undergoes faster SN1 reaction ?

(i) and (ii) and

(CBSE 2013) (CBSE 2010)

Ans. The reactivity in SN1 reaction is governed by stability of the intermediate carbocation which an alkyl
halide gives on ionization. Thus,
 (i)

3° Alkyl 3° 2° Alkyl chloride 2° Carbocation

chloride Carbocation (less stable)
(more stable)

Since 3° carbocations are more stable than 2° carbocations, therefore, will react faster
than

in SN1 reaction.

(ii)

2° Alkyl halide 2° Carbocation 10 Alkyl halide 1° Carbocation

(more stable) (less stable)

Since 2° cai rbocations are more le than 1° carbocations, will react

stab: therefore,

faster than in SN1 reaction.

Q. 10.9. Identify A, B, C, D, E, R and R1 in the following :

dry ether H2O

→ A → B

R—Br + Mg dry ether D2O

→ C →
 Na/ether Mg D H2O
→ R1—X → → E

Ans. dry ether H2O

→
→

Cyclohexyl bromide Cyclohexylmag. Cyclohexane

bromide (A) (B)

dry ether D2O

R—Br + Mg → C →

Since D gets attached to the same carbon atom on which MgX was present, therefore,

R—Br = or R = and C =

The third part of the question is wrong because rm-alkyl halides do not undergo Wurtz reaction but
undergo dehydrohalogenation to give alkenes. Thus, R1 = (CH3)3C - and hence D and E are

H2O
Mg →

2-Methylpropene

tert-Butyl tert-Butylmag. 2-Methylpropane (E)

bromide (R1 - Br) bromide (D)

NCERT EXERCISES
Q. 10.1. Name the following halides according to IUPAC system and classify them as alkyl, allyl, benzyl
(prmary, secondary, tertiary), vinyl or aryl halides.
(i)(CH3)2CHCH(Cl)CH3(ii) CH3CH2CH(CH3)CH(C2H5)Cl(iii) CH3CH2C(CH3)2CH2I
(iv) (CH3)3CCH2CH(Br)C6H5 (v) CH3CH(CH3)CH(Br)CH3 (vi) CH3C(C2H5)2CH2Br
(vii) CH3C(Cl)(C2H5)CH2CH3 (viii) CH3CH=C(Cl)CH2CH(CH3)2
(ix)CH3CH=CHC(Br)(CH3)2 (x) p-ClC6H4CH2CH(CH3)2
(xi) m-ClCH2C6H4CH2C(CH3)3(xii) o-Br-C6H4CH(CH3)CH2CH3.
Ans. (i) 2-Chloro-3-methylbutane, 2° alkyl halide, (ii) 3-Chloro-4-methylhexane, 2° alkyl halide
(iii) l-Iodo-2, 2-dimethylbutane, 1° alkyl halide, (iv)1-Bromo-3, 3-dimethyl-1-phenylbutane, 2°benzylic
halide, (v) 2-Bromo-3-methylbutane, 2° alkyl halide, (vi) 1-Bromo-2-ethyl-2-methylbutane, 1° alkyl
halide, (vii) 3-Chloro-3- methylpentane, 3° alkyl halide, (viii) 3-Chloro-5-methylhex-2-ene, vinylic halide
(ix) 4-Bromo-4-methylpent-2-ene, ally lie halide, (x) l-Chloro-4-(2-methylpropyl)benzene, aryl halide
(xi) l-Chloromethyl-3-(2, 2-dimethylpropyl)benzene, 1° benzylic halide,
(xii)1-Bromo-2-(l-methylpropyl)benzene or l-bromo-2-iec-butylbenzene, aryl halide.
Q. 10.2. Give the IUPAC names of the following compounds :
(i) CH3CH(Cl)CH(Br)CH3(ii) CHF2CBrClF (iii)ClCH2C ≡ CCH2Br
(iv) (CCl3)3CCl (v) CH3C(p-ClC6H4)2CH(Br)CH3 (vi) (CH3)3CCH=C(Cl)C6H4I -p
Ans. (i) 2-Bromo-3-chlorobutane (ii) 1-Bromo-1-chloro- 1, 2, 2-trifluoroethane (iii) 1-Bromo-4-chlorobut-
2- yne (iv) 2-(Trichloromethyl)-l, 1, 1, 2, 3, 3, 3-heptachloropropane (v) 2-Bromo-3, 3-Bis (4-chloro-
phenyl)butane (vi) l-Chloro-1-(4-iodophenyl)-3, 3-dimethylbut-1-ene.
Q. 10.3. Write the structures of the following organic halogen compounds :
(i) 2-Chloro-3-methylpentane (ii) p-Bromochlorobenzene
(iii) 1-Chloro-4-ethylcyclohexane (iv) 2-(2-Chlorophenyl)-1-iodooctane
(v) Perfluorobenzene (vi) 4-icri-Butyl-3-iodoheptane
(vii) 1-Bromo-4-sec-butyl-2- methylbenzene (viii) 1, 4-Dibromobut-2-ene.

Ans. (i) (iii)

(ii)

(iv) (v) (vi)

(vii) (viii)

Q. 10.4. Whichof the following has highest dipole moment ? (i) CH2Cl2 (ii) CHCl3 (iii) CCl4
Ans. The three dimensional structures of the three compounds along with the direction of dipole
moment in each of their bonds are given below :

Resultant Resultant

µ = 1-62D µ = 1-03D µ = 0D

CCl4 being symmetrical has zero dipole moment. In CHCl3, the resultant of two C—Cl dipoles is opposed
by the resultant of C—H and C—Cl bonds. Since the latter resultant is expected to be smaller than the
former, therefore, CHCl3 has a finite dipole (1-03 D) moment.
In CH2Cl2, the resultant of two C—Cl dipole moments is reinforced by resultant of two C—H dipoles,
therefore, CH2Cl2 (1-62 D) has a dipole moment higher than that of CHCl3.
Thus, CH2Cl2 has the highest dipole moment.
Q. 10.5. A hydrocarbon CSH10 does not react with chlorine but gives a single monochloro compound,
CsHt,Cl in bright sunlight. Identify the hydrocarbon.
Ans. (i) The hydrocarbon with M.F. C5H10 can be either a cycloalkane or an alkene.
(ii) Since the hydrocarbon does not react with Cl2 in the dark, it cannot be an alkene but must be a
cycloalkane.
(iii) Since the cycloalkane reacts with Cl2 in the presence of bright sunlight, to give a single monochloro
compound, C5H9CI, therefore, all the ten hydrogen atoms of the cycloalkane must be equivalent. Thus,
the cycloalkane is cyclopentane.

No reaction

Cyclopentane (C5H10) Monochloro- cyclopentane

(C5H9CI)

Q. 10.6. Write the isomers of the compound having formula C4H9Br.

4 (4 − 2) + 9 (1 − 2) +1 (1 − 2)
Ans. D.B.E. for C4H9Br = 2
+1=0

Thus, the compound is saturated. It has the following four isomers :

(i) CH3CH2CH2CH2Br (ii) (iii) (iv)

1-Bromobutane 1 -B romo-2-methy
lpropane

2-Bromobutane 2-Broino-2-
methylpropane

Q. 10.7. Write the equations for the preparation of 1-iodobutane from (i) 1-butanol (ii) 1-chlorobutane
(iii) but-1-ene.

Ans. (i) P + I2
CH3CH2CH2CH2OH → CH3CH2CH2CH2I

1-Butanol 1-Iodobutane

(ii)CH3CH2CH2CH2CI CH3CH2CH2CH2I

1-Chlorobutane 1-Iodobutane

(iii) CH3CH2CH = CH2 CH3CH2CH2CH2Br CH3CH2CH2CH2I

But-1-ene 1-Bromobutane 1-Iodobutane

Q. 10.8. What are ambident nucleophiles ? Explain with an example.

Ans. Nucleophiles which can attack through two different sites are called
ambident nucleophiles. For example, cyanide ion is a resonance hybrid
of the following two structures.

It can attack either through carbon to form cyanides or through N to form isocyanides or carbylamines.
Q. 10.9. Whichcompound in eachof the following pairs will react faster in SN2 reaction with OH- ?
(i) CHjBr or CH3I (ii) (CH3)3CCl or CH3Cl. (CBSE 2008)
Ans. (i) Since I- ion is a better leaving group than Br- ion, therefore, Ch3Ireacts faster than CH3Br in SN2
reaction vwith OH- ion.
(ii) On steric grounds, 1° alkyl halides are more reactive than tert-alkyl halides in SN2 reactions.
Therefore,CH3CI will react at a faster rate than (CH3)3CCl in a SN2 reaction with OH- ion.
Q. 10.10. Predict all the alkenes that would be formed by dehydrohalogenation of the following
halides with sodium ethoxide in ethanol and identify the major alkene. (i) 1-Bromo-1-
methylcyclohexane (ii) 2-Chloro-2-methylbutane (iii) 3-Bromo-2, 2, 3-trimethylpentane.
Ans. (i) In 1-bromo-1-methylcyclohexane, the β-hydrogens on either side of the Br atom are equivalent,
therefore, only 1- alkene is formed.

1 -Methylcyclohexene
(ii) 2-Chloro-2-methylbutane has two different sets of equivalent β-hydrogens and hence, in principle,
can give two alkenes (I and II), But according to Saytzeff rule, more highly substituted alkene (II), being
more stable, is the major product.

2-Methylbut-1-ene (I) 2-Methylbut-2-ene (II)

2-Chloro-2-methybutane (Less stable, minor (More stable, major product)

product)

(iii) 3-Bromo-2, 2, 3-trimethylpentane has two different sets of P-hydrogens and hence, in principle, can
give two alkenes (I and II). But according to Saytzeff rule, more highly substituted alkene (II), being more
stable, is the major product.

Q. 10.11. How will you bring about the following conversions ? (i) Ethanol to but-1-yne (ii) Ethane to
bromoethene (iii) Propene to 1-nitropropane (iv) Toluene to benzyl alcohol (v) Propene to propyne
(vi) Ethanol to ethyl fluoride (vii) Bromomethane to propanone (viii) But-1-ene to but-2-ene (ix) 1-
Chlorobutane to n- octane. (Hr. Board 2011) (x) Benzene to biphenyl.

Ans. (i) CH3CH2Oh CH3CH2—Cl

Ethanol Chloroethane (A)

HC = CH + NaNH2 HC = C-Na+ ;A+B → CH3CH2-C = CH + NaCl

Acetylene Sod. acetylide But-1-yne

(B)
 (ii) CH3—CH3 + Br2 CH3CH2—Br CH2 = CH2

Ethane Bromoe Ethene

thane

Br2/CCl4 BrCH2—CH2Br CH2 = CHBr

1, 2- Bromoethene
Dibromoethane

(iii) CH3—CH = CH2 CH3—CH2—CH2Br CH3CH2CH2NO2

Propene 1-Bromopropane 1-Nitropropane

(iV)

(<Side chain
halogénation)
Toluene Benzyl chloride Benzyl alcohol

Br2/CCl4
→

Propene Propyne

1, 2-
Dibromopropane

Alternatively, conversion of 1, 2-dibromopropane to propyne can be carried out simply by heating with
KOH (ale.) but the yield is low. The reason being that 1, 2-dihaloalkanes can be smoothly
dehydrohalogenated to vinyl halides by heating with KOH (ale.), but vinyl halides being less reactive
require a much stronger base such as NaNH2/liq. NH3 for dehydrohalogenation to form alkynes. Both
these steps, can, however, be smoothly carried out simultaneously with NaNH2/liq. NH3.

(vi) CH3CH2Oh CH3CH2—Cl CH3CH2—F

Ethanol Ethyl chloride Ethyl fluoride

 (vii) CH3—Br CH3—CN CH3MgBr/ether

Bromomethane Acetonitrile

-.

Propanone

Alternatively, HC ≡ CH HC = C- Na+ CH3—C = CH

Acetylene Sod. Propyne

acetylide

Propanone

(viii)
CH3CH2CH = CH2 CH3—CH = CH—CH3

But-1-ene But-2-ene

2-Bromobutane (Major product)

(ix) 2 CH3CH2CH2CH2Cl + 2 Na CH3CH2CH2CH2—CH2CH2CH2CH3 + 2 NaCl

1-Chlorobutane n-Octane

ix)

Benzene Bromobenzene Biphenyl

Q. 10.12. Explain why (i) the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride
?
 (CBSE 2010 S ; Hr. Board 2011)
(ii) Alkyl halides, though polar, are immiscible with water ? (CBSE 2010 S ; Hr. Board 2011)
(iii) Grignard reagents should be prepared under anhydrous conditions ?
(Hr. Board 2011 ; CBSE 2010 S, 2011)
Ans. (i) Due to greater s-character, a ,sp2-hybrid carbon is more electronegative than a sp3-hybrid
carbon. Therefore, the sp2-hybrid carbon of C—Cl bond in chlorobenzene has less tendency to release
electrons to Cl than a sp3-hybrid carbon of cyclohexyl chloride.

Cyclohexyl chloride

Chlorobenzene

As a result, the C—Cl bond in chlorobenzene is less polar than in cyclohexyl chloride. In other words, the
magnitude of negative charge, i.e.,δ- is less on Cl atom of chlorobenzene than in cyclohexyl chloride.

Chlorobenzene C-Cl bond has some double C-Cl bond has pure single bond
bond character character

Further, due to delocalization of lone pairs of electrons of the Cl atom over the benzene ring, C—Cl bond
in chlorobenzene acquires some double character while the C—Cl bond in cyclohexyl chloride is a pure
single bond. In other words, C—Cl bond in chlorobenzene is shorter than in cyclohexyl chloride. Since
dipole moment is a product of charge and distance, therefore, chlorobenzene has lower dipole moment
than cyclohexyl chloride due to lower magnitude of-ve charge on the Cl atom and shorter C—Cl
distance.
(ii) Alkyl halides are polar molecules, therefore, their molecules are held together by dipole-dipole
attraction. The molecules of H2O are held together by H-bonds. Since the new forces of attraction
between water and alkyl halide molecules are weaker than the forces of attraction already existing
between alkyl halide-alkyl halide molecules and water- water molecules, therefore, alkyl halides are
immiscible (not soluble) with water.
(iii) Grignard reagents are very reactive. They react with moisture present in the apparatus or the
starting materials, i.e., R—X, Mg and the solvent (ether or THF).

+ H—OH →R - H + Mg(OH)X

Grignard reagent

Therefore, Grignard reagents must be prepared under anhydrous conditions.

Q. 10.13. Give the uses of Freon-12, DDT, carbon tetrachloride and iodoform. (Hr. Board 2011)
Ans. Refer to Art. 10.10.3-10.10.6, pages 10/56-10/59.
Q. 10.14. Write the structure of the major organic product in eachof the following reactions :

(i) CH3CH2CH2Cl + Nal acetone, heat (ii) (CH3)3CBr + KOH ethanol, heat
→ →

(iii) CH3CH(Br)CH2CH3 + NaOH Water (iv) CH3CH2Br + KCN aq. ethanol

→ →

(v) C6H5ONa + C2H5Cl → (vi) CH3CH2CH2Oh + socI2 →

(vii) CH3CH2CH = CH2 + HBr Peroxide (Hr. Board 2011)

→

(viii) CH3CH = C(CH3)2 + HBr →

Ans. (i) CH3CH2CH2Cl + Nal CH3CH2CH2I + NaCl

1-Chloropropane 1-Iodopropane

(ii) (CH3)3CBr + KOH

2-Bromo-2-methyIpropane 2-Methylpropene

(iii)
 2-Bromobutane Butan-2-ol

(iv) CH3CH2—Br + KCN CH3CH2—CN + KBr

Bromoethane Propanenitrile

(v) C6H5O-Na+ + C2H5-Cl C6H5-O-C2H5 + NaCl

Sod. phenoxide Ethyl chloride Phenetole

(vi) CH3CH2CH2Oh + SOCl2 CH3CH2CH2Cl + HCl ↑ + SO2 ↑

Propan-1-ol 1-Chloropropane

(vu) CH3CH2CH = CH2 + HBr CH3CH2CH2CH2Br

But-1-ene 1 -Bromobutane

(viii) [Link].
+ HBr →

2-Methylbut-2-ene

2-Bromo-2-methylbutane

EtOH –H2O
Q. 10.15. Explain the following reaction : n-BuBr + KCN → n-BuCN.

Ans. KCN is a resonance hybrid of the following two contributing structures :

Thus, CN-ion is an ambident nucleophile. Therefore, it can attack the carbon atom of C—Br bond in /i-
BuBr either through C or N. Since C—C bond is stronger than C—N bond, therefore, attack occurs
through C to form n-butyl cyanide
 → CH3CH2CH2CH2CN + KBr

n-Butyl bromide n-Butyl cyanide

Q. 10.16. Arrange the compounds of eachset in order of reactivity towards SN2 displacement :
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane.
(Hr. Board 2011, CBSE 2011)
(ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 2-Bromo-3- methylbutane.
(CBSE 2011)
(iii) 1-Bromobutane, 1-Bromo-2, 2-dimethylpropane, 1-Bromo-2- methylbutane, 1-Bromo-3-
methylbutane. (Hr. Board 2011 ; CBSE 2011)
Ans. The reactivity in SN2 reactions depends upon steric hindrance ; more the steric hindrance slower
the reaction.

(i) CH3CH2CH2CH2CH2—Br

1-Bromopentane (1°)

2-Bromo-2-methylbutane (3°) 2-Bromopentane (2°)

Since due to steric reasons, the order of reactivity in SN2 reactions follows the order : 1° > 2° > 3°,
therefore, order of reactivity of the given alkyl bromides is :
1-Bromopentane > 2-Bromopentane > 2-Bromo-2- methylbutane.

00

1-Bromo-3-methylbutane (1°)

2-Bromo-2-methylbutane (3°) 2-Bromo-3-methylbutane (2°)

Since due to steric reasons, the order of reactivity of alkyl halides in SN2 reactions follows the order : 1° >
2° > 3°, therefore, the order of reactivity of the given alkyl bromides is : 1-Bromo-3-methylbutane (1°)>2-
Bromo-3-methylbutane (2°) > 2-Bromo-2-methyIbutane (3°)

(iii) CH3CH2CH2CH2Br

1-Bromobutane

(1° with no branching)

 1-Bromo-2,2-dimethylpropane (1° with two 3-methyl
groups)

1 -Bromo-2-methylbutane 1 -Bromo-3-methylbutane

(1° with one p-ethyl group) (1° with one methyl group at y-position

Since in case of 1° alkyl halides, steric hindrance increases in the order : n-alkyl halides, alkyl halide with
a substituent at any position other than the P-position, one substituent at the P-position, two
substituents at the P-position, therefore, the reactivity decreases in the same order. Thus, the reactivity
of the given alkyl bromides decreases in the order :
1- Bromobutane>1-Bromo-3-methylbutane >1-Bromo-2- methylbutane > 1 -Bromo-2,
2- dimethylpropane.
Q. 10.17. Out of C6H5CH2Cl and C6H5CHClC6H5whichis more easily hydrolysed by aqueous KOH ? Ans.
C6H5CH2Cl is a 1° aralkyl halide while C6H5CH(Cl) C6H5 is a 2° aralkyl halide.

Ionization C6H5— -C6H5 + Cl-

→

2° carbocation stabilized by
delocalization over two C6H5 rings
1-Chloro-l, 1-diphenylmethane

Ionization C6H5 + Cl-

→

Benzyl chloride 1° carbocation stabilized by

delocalization over one CgH5
ring

In SN1 reactions, the reactivity depends upon the stability of carbocations. Since the carbocation

C6H5 HC6H5 (where the +ve charge is delocalised over two C6H5 rings) derived from C6H5—

CHCl-C6H5 is more stable than the carbocation, C6H5 H2 (where +ve charge is delocalized over
one C6H5 ring) derived from C6H5CH2Cl, therefore, C6H5CHCIC6H5 gets hydrolysed more easily than
C6H5CH2Clunder SN1 conditions.
However, under SN2 conditions, the reactivity depends on steric hindrance, therefore, under SN2
conditions, C6H5CH2Cl (with lesser steric hindrance) gets hydrolysed more easily than
C6H5CHClC6H5.

Q. 10.18. p-Dichlorobenzene has higher melting point and lower solubility than those of o- and m-
[Link]. (CBSE 2013, CBSE Sample Paper '016)
Ans. The p-isomer being more symmetrical fits closely in the crystal lattice and thus has stronger inter-
molecular forces of attraction than those of o- and m-isomers. Since during melting or dissolution, the
crystal lattice breaks, therefore, a larger amount of energy is needed to melt or dissolve the p-isomer
than the corresponding o- and m- isomers. In other words, the melting point of the p-isomer is higher
and its solubility lower than the corresponding o- and m- isomers.
Q. 10.19. How the following conversions can be carried out ?

(i) Propene to propan-1-ol (ii) Ethanol to but-2-yne

(iii) 1-Bromopropane to 2-bromopropane (Hr. Board 2011)

(iv) Toluene to benzyl alcohol (v) Benzene to 4-bromonitrobenzene

(vi) Benzyl alcohol to 2-phenylethanoic acid (vii) Ethanol to propanenitrile

(viii) Aniline to chlorobenzene (ix) 2-Chlorobutane to 3,4-dimethylhexane

(x) 2-Methyl-1-propene to 2-chloro-2-methylpropane (xi) Ethyl chloride to propanoic acid

(xii) But-1-ene to n-butyl iodide (xiii) 2-Chloropropane to 1-propanol

(Hr. Board 2011)

(xiv) Isopropyl alcohol to iodoform (xv) Chlorobenzene to p-nitrophenol

(xvi) 2-Bromopropane to 1-bromopropane (xvii) Chloroethane to butane

(xviii) Benzene to diphenyl (xx) Aniline to phenyl (xix) ferf-Butyl bromide to isobutyl bromide
isocyanide.

Ans. (i) CH3CH = CH2 CH3CH2CH2Br CH3CH2CH2Oh

Propene 1-Bromopropane Propan-1-ol

(ii) CH3CH2Oh P/I2,∆ CH3CH2I CH2 = CH2

 →

Ethanol Iodoethane Ethene

Na+ -C s c- Na+

Disodium acetylide

1, 2-Dibromoethane CH3—C - C—CH3

But-2-yne

(iii) CH3CH2CH2Br CH3CH = CH2 CH3—CHBr—CH3

1-Bromopropane Propene 2-Bromopropane

(iv) For toluene to benzyl alcohol, refer to Ans. to Q. 10.11 (iv), page 10/101.

(v)

Benzene Bromobenzene 4-Bromonitrobenzene

{major isomer)

(vi)

Benzyl Benzyl chloride Benzyl cyanide

alcohol

2-Phenylethanoic acid

(vii) P/I2, ∆
CH3CH2Oh → CH3CH2I CH3CH2CN

Ethanol Iodoethane Propanenitrile

 (viii)

Aniline Benzenediazonium chloride Chlorobenzene

(ix)

2-Chlorobutane 3,4-Dimethylhexane

(X)

2-Methy 1-1 -propene

2-Chloro-2-methylpropane

(xi)
CH3CH2Cl CH3CH2CN CH3CH2COOH

Ethyl chloride Propanenitrile Propanoic acid

(xii)
CH3CH2CH = CH2 CH3CH2CH2CH2Bi

But-1-ene 1-Bromobutane

CH3CH2CH2CH2I

n-Butyi iodide

(xiii) CH3—CH = CH2

Propene
 2-Chloropropane CH3CH2CH2Br CH3ch,CH2Oh

1-Bromopropane 1-Propanol

(xiv) + 4I2+6NaOH CHI3 + CH3COONa + 5 Nal + 5 H2O

Iodoform

Isopropyl alcohol

(xv)

Chlorobenzene p-Chloronitrobenzene
{major isomer)

p-Nitrophenol

(xvi) CH3CH = CH2

Propene

2-Bromopropane CH3—CH2—CH2—Br

1-Bromopropane

(xvii) 2 CH3CH2—Cl + 2Na CH3CH2—CH2CH3 + 2 NaCl

Chloroethane Butane

(xviii) Benzene to diphenyl — Refer to Ans. to Q. 10.11 (x), page 10/101.

(xix)

2-Methyl-1 -
propene
 tert-Butyl bromide

Isobutyl bromide

(xx) + CHCl3 + 3 KOH (ale) + 3 KCl + 3 H2O

Chloroform

Aniline Phenyl isocyanide

Q. 10.20. The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in
presence of alcoholic KOH, alkenes are the major products. Explain why ?
(Hr. Board 2011, 2013)
Ans. In aqueous solution, KOH is almost completely ionized to give OH- ions which being a strong
nucleophile brings about a substitution reaction on alkyl halides to form alcohols. Further in the
aqueous solution, OH- ions are highly solvated (hydrated). This solvation reduces the basic character of
OH- ions which, therefore, fail to abstract a hydrogen from the 3-carbon of the alkyl chloride to form an
alkene.
In contrast, an alcoholic solution of KOH contains alkoxide (RO-) ions which being a much stronger base
than OH- ions preferentially eliminates a molecule of HCl from an alkyl chloride to form alkenes.
Q. 10.21. Primary alkyl halide C4H9Br (a) reacted with alcoholic KOH to give compound (b). Compound
(b) is reacted with HBr to give (c) whichis an isomer of (a). When (a) is reacted with Na metal, it gives a
compound (d), C8H18whichis different from the compound formed when n-butyl bromide is reacted
with sodium. Give the structural formula of (a) and wri e the equations for all the reactions.
Ans. (i) Two primary alkyl halides having the molecular formula, C4H9Br are

CH3CH2CH2CH2Br and

n-Butyl bromide Isobutyl bromide

Thus, compound (a) is either n-butyl bromide or isobutyl bromide.

(ii) Since compound (a) when reacted with Na metal gives a compound (d) with M.F. C8H18 which is
different from the compound obtained when n-butyl bromide is reacted with Na metal, therefore, (a)
must be isobutyl bromide and compound (d) must be 2,5-dimethylhexane.

2 CH3CH2CH2CH2Br + 2 Na CH3CH2CH2CH2CH2CH2CH2CH3

n-Butyl bromide (1°) n-Octane

 Isobutyl bromide (a) (1°) 2,5-Dimethylhexane (d), M.F. C8H18

(iii) If compound (a) is isobutyl bromide then compound (b) whichit gives on treatment with alcoholic
KOH must be 2-methyl-1-propene

Isobutyl chloride (a) 2-Methyl-1-propene (b)

(iv) The compound (b) on treatment with HBr gives compound (c) in accordance with Markovnikov’s
rule. Therefore, compound (c) is terf-butyl bromide which is an isomer of compound (a), i.e., isobutyl
bromide.

2-Methyl-1 -propene

tert-Butyl bromide (c)

(an isomer of compound (a))

Thus, (a) is isobutyl bromide, (b) is 2-methyl-1- propene, (c) is tert-butyl bromide and (d) is 2, 5-
dimethylhexane.
Q. 10.22. What happens when (i) n-butyl chloride is treated with alcoholic KOH. (ii) bromobenzene is
treated with Mg in the presence of dry ether, (iii) chlorobenzene is subjected to hydrolysis,
(iv) ethyl chloride is treated with aqueous KOH. (v) methyl bromide is treated with sodium in presence
of dry ether, (vi) methyl chloride is treated with KCN ?

Ans. (i) CH3CH2—CH2—CH2CI + KOH (ale) CH3CH2—CH = CH2 + KCl + H2O

n-Butyl chloride But-1-ene

(ii)

Bromobenzene Phenylmagnesium bromide

 (iii) ∆
+ NaOH (aq) → No reaction.

Chlorobenzene

(iv) CH3CH2—Cl + KOH (aq) CH3CH2—OH + KCl

Ethyl chloride Ethyl alcohol

(v) CH3—CH3 + 2 NaBr

Methyl bromide Ethane

(vi) CH3—Cl + KCN CH3—CsN + KCl

Methyl chloride Methyl cyanide

Alcohol, Phenol and Ether

NCERT INTEXT UNSOLVED QUESTIONS
Q. 11.1. Classify the following as primary, secondary and tertiary alcohols

(i) (ii) H2C = CH—CH2OH (iii) CH3—CH2—CH2—OH

(iv) (v) (vi)

Ans. Primary alcohols:(i), (ii), (iii); Secondary alcohols:(iv),(v); Tertiary alcohols:(vi). Q. 11.2. Identify
allylic alcohols in the above examples.
Ans. Allylic alcohols:(ii) and (vi).
Q. 11.3. Name the following compounds according to the IUPAC system

(i) (ii)

(CBSE 2008)

(iii) (iv) (v)

Ans. (i) (ii)

3-Chloromethyl-2-isopropylpentan-1 -ol 2, 5-Dimethylhexane-l, 3-diol

(iii) (iv) (v)

3 - Hex-l-en-3-ol 2-Bromo-3-methylbut-2-en-1 -ol

Bromocyclohexanol

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

(i) (ii)

Ans. (i) The part which has been enclosed in box comes from methanal while
the

remaining part comes from the Grignard reagent. Therefore, the

 Grignard reagent should be isopropylmagnesium bromide. Thus,

(i) The part which has been enclosed in box comes from methanal while
the remaining part comes from the Grignard reagent. Therefore, the
Grignard reagent must be cyclohexylmagnesium bromide. Thus,

Methanal Cyclohexylmag
bromide

or

Cyclohexylmethanol

Q. 11.5. Write structures of the products of the following reactions.

CH3—CH = CH2 H2O/H+

(i) →
 (ii) NaBH4

→ (iii)

Ans. (i)

(ii) NaBH4 is a weak reducing agent, it reduces the aldehydes/ketones but not the esters. Thus,

NaBH4

Methyl (2-oxocyclohexyl) ethanoate Methyl (2-hydroxycyclohexyl) ethanoate

(iii) NaBH4 reduces -CHO group to CH2OH. Thus,

NaBH4

2-Methylbutanal 2-Methylbutan-1 -ol

Q. 11.6. Give structures of the products you would expect when each of the following alcohol reacts
with
(a)HCl-ZnCl2 (b) HBr and (c) SOCl2.
(i)Butan-l-ol (ii) 2-Methylbutan-2-ol.
Ans. (a) With HCI-ZnCl2 (Lucas reagent). 2-Methylbutan-2-ol (ii) being a 3° alcohol, reacts with Lucas
reagent to produce turbidity immediately due to the formation of insoluble tert-alkyl chloride while
butan-l-ol (i) being a 1° alcohol does not react with Lucas reagent at room temperature

Anhyd. ZnCl2 + H2O

+ HCl(cone.) →
 2-Methylbutan-2-ol (3°) 2-Chloro-2-
methylbutane (White
turbidity)

CH3CH2CH2CH2—OH + HCl(cone.) Anhyd. ZnCl2 No reaction at room temperature

Butan-l-ol (1°)

(b) Both the alcohols react to produce the corresponding alkyl bromides.

CH3CH2CH2CH2OH + HBr ∆ CH3CH2CH2CH2Br + H2O

Butan-l-ol (1°) 1-Bromobutane

2-Methylbutan-2-ol (3°) 2-Bromo-2-methylbutane

(c) Both the alcohols react to form the corresponding alkyl chlorides.

CH3CH2CH2CH2OH +SOCI2 ∆ CH3CH2CH2CH2CI + SO2↑ + HCl ↑

Butan-l-ol (1°) 1-Chlorobutane

∆ + SO2î + HCl t

2-Methylbutan-2-ol 2-Chloro-2-methylbutane

Q. 11.7. Predict the major product of add-catalysed dehydration of (i) 1-methylcyclohexanol and (ii)
butan-l-ol.
Ans. (i) Acid-catalysed dehydration of 1-methylcyclohexanol can, in principle, give two products, viz., I
and II. But since product (I) is more highly substituted, therefore, according to Saytzeff rule, it is the
major product.

1 -Methylcyclohexanol 1-Methylcyclohexene Methylenecyclohexane (II)

(I) (major product) (minor product)

(ii) Acid-catalysed dehydration of butan-l-ol produces but- 2-ene as the major product and but-l-ene as
the minor product. The reason being that dehydration of alcohols occurs through carbocation
intermediates. Now butan-l-ol being a 1° alcohol upon protonation and elimination of H2O first gives a 1°
carbocation (I) which being less stable rearranges to form the more stable 2° carbocation (II). This can
then lose a proton in two different ways to form either but- 2-ene or but-l-ene.
Since but-2-ene is more stable, therefore, according to Saytzeff rule, this is the major product.

Q. 11.8. Ortho and para-nitrophenols are more acidic than phenol. Draw the resonance structures of
the corresponding phenoxide ions.
Ans. The resonance structures of o- and p nitrophenoxide ions and phenoxide ion are given below:

Resonance structures of o-nitrophenoxide ion

 Resonance structures of p-nitrophenoxide ion

Resonance structures of phenoxide ion

It is evident from the above structures that due to -R-effect of the -NO2 group, o- and p- nitrophenoxide
ions are more stable (because of additional resonance structures, III and IX enclosed in boxes) than
phenoxide ion. As a result, o- and p-nitrophenols are more acidic than phenol.
Q. 11.9. Write the equations involved in the following reactions
(i)Reimer-Tiemann reaction (ii) Kolbe’s reaction.
Ans. Refer to (a) pages 11/41-11/42 and (b) page 11/40.
Q. 11.10. Write the reactions of Williamson synthesis of 2-ethoxy-3-methylpentane starting from
ethanol and 3-methylpentan-2-ol.
Ans. Williamson synthesis is a SN2 reaction, therefore, for the success of any such synthesis, the alkyl
halide should be primary (unhindered or least inhindered). Thus, the alkyl halide should be derived from
ethanol and the alkoxide ion from 3-methylpentan-2-ol. The complete synthesis is as follows:

CH3CH2OH + HBr ∆ CH3CH2 Br + H2O

Ethanol Bromoe thane

+ 2Na + H2

3-Methylpentan-2-ol Sod. 3-methylpent-2-oxide

2-Ethoxy-3-methylpentane
Q. 11.11. Which of the following is an appropriate set of reactants for the preparation of l-methoxy-4-
nitrobenzene and why ?

(i) + CH3ONa (ii) + CH3Br

Ans. (i) Chemically both sets are equally probable. In set (i), the Br atom is activated by the electron-
withdrawing effect of-NO2 group. Therefore, nucleophilic attack by CH3ONa followed by elimination of
NaBr gives the desired ether.
Step 1.

4-Bromonitrobenzene

Stabilized by resonance

Step 2.

1-Methoxy-4- Sod. 4-nitrophenoxide ion

nitrobenzene

In set (ii), nucleophilic attack by 4-nitrophenoxide ion on methyl bromide gives the desired ether.
Conclusion. Since alkyl halides are more reactive than aryl halides in nucleophilic substitution reactions,
therefore, option (ii) is preferred.

Q. 11.12. Predict the products of the following reactions:

(i) CH3—CH2—CH2—O—CH3+ HBr → (ii) + HBr →

(iii) (iv) (CH3)3C—OC2H5 HI .

 →

Ans. (i) Both the alkyl groups attached to the oxygen atom are primary, therefore, attack of Br ion
occurs on the smaller methyl group leading to the formation of propan-l-ol and bromomethane.

CH3—CH2—CH2—O—CH3 + HBr 373 K CH3—CH2—CH2—OH + CH3—Br

n-Propyl methyl ether Propan-l-ol Bromomethane

(ii) Due to resonance, C6H5—O bond has some double bond character and hence is stronger than O—
C2H5 bond. Therefore, the cleavage of the weaker O—C2H5 bond occurs to yield phenol and
bromoethane.

+ HBr 373 K + CH3CH2—Br

Bromoethane

Ethoxybenzene Phenol

(iii) Due to strong +R-effect of the OC2H5 group, it is activating as well as o, p-directing. Therefore,
nitration of ethoxybenzene will give a mixture of 2- and 4-ethoxynitrobenzene in which 4-
ethoxynitrobenzene predominates due to steric hindrance at 2-position in 2-ethoxynitrobenzene.

Ethoxybenzene 4-Ethoxynitrobenzene 2-Ethoxynitrobenzene

(major) (minor)

(iv) Since tert-Butyl carbocation is much more stable than ethyl carbocation, therefore, reaction follows
SN1 mechanism leading to the formation of tert- butyl iodide and ethanol as shown below:

Step 1.

tert-Butyl ethyl ether

Step 2. Fast
 →

tert-Butyl iodide

NCERT EXERCISES
Q. 11.1. Write the IUPAC names of the following compounds:

(i) (ii)

(iii) (iv) HOCH2—CHOH—CH2OH

(v) (vi) (vii) (viii)

(ix) (CBSE 2008) (x) CfiHg—O—C2H5

(xi) C6H5—O—C7H15 (n-) (xii)

Ans. (i) 2, 2, 4-Trimethylpentan-3- (ii) 5-Ethylheptane-2, 4-diol (iii) Butane-2, 3-diol

ol

(iv) Propane-1, 2, 3-triol (v) 2-Methylphenol (vi)4-Methylphenol

(vii)2, 5-Dimethylphenol (viii) 2, 6-Dimethylphenol (ix) 1 -Methoxy-2-methylpropane

(x) Ethoxybenzene (xi) 1-Phenoxyheptane (xii) 2-Ethoxybutane.

Q. 11.2. Write the structures of the compounds whose IUPAC names are as follows:
(i) 2-Methylbutan-2-ol(ii) l-Phenylpropan-2-ol(iii) 3,5-Dimethylhexane-l, 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-l-ol (x) 3-
Chloromethylpentan-l-ol.
 Ans. (i) (ii)

(iii) (iv)

(v) CH3O—CH2CH2CH3 (v/) (vii)

(viii) (ix) (x)

Q. 11.3. (i) Draw the structures of all isomeric alcohols of molecular formula C 5H120 and give their
IUPAC names.
(ii) Classify the isomers of alcohols in questions 1 (i) as primary, secondary and tertiary alcohols. Ans.
Eight isomers are possible. These are:

(a) CH3CH2CH2CH2CH2OH (b) (c)

Pentan -l-ol (1°) Pentan-2-ol (2°) Pentan-3-ol (2°)

(d) (e) (f)

2-Methylbutan-l-ol (1°) 3-Methylbutan-l-ol (1°)

2-Methylbutan-2-ol (3°)

(g) (h)

3-MethyIbutan-2-ol (2°)
 2,2-Dimethylpropan-l-ol (1°)

Q. 11.4. Explain why propanol has higher boiling point than that of the hydrocarbon, butane ?
Ans. The molecules of butane are held together by weak van der Waalsforces of attraction while those
of propanol are held together by stronger intermolecular hydrogen bonding.

Therefore, the b.p. of propanol is much higher than that of butane.

Q. 11.5. Alcohols are comparatively more soluble in water than hydrocarbons of comparable
molecular masses. Explain this fact.(CBSE Sample Paper 2017)
Ans. Alcohols can form H-bonds with water and can also break the H-bonds already existing between
water molecules. Therefore, they are soluble in water.

On the other hand, hydrocarbons can neither form H-bonds with water nor can break the H-bonds
already existing between water molecules and hence are insoluble in water.
Q. 11.6. What is meant by hydroboration-oxidation reaction ? Illustrate with an example.
Ans. The addition of diborane to alkenes to form trialkylboranes followed by their oxidation with
alkaline hydrogen peroxide to form alcohols is called hydroboration-oxidation. For example,

CH3CH = CH2 (BH3)2 CH3CH = CH2 (CH3CH2CH2)2B—H

+ →

Propene Diborane CH3CH = CH2 (CH3CH2CH2)3B

Tri-rc-propylborane

(CH3CH2CH2)3B + 3H2O2 OH-/H2O 3 CH3CH2CH2OH + B (OH)3

Tri-n-propylborane Propan-l-ol Boric acid

The alcohols obtained by this process appear to have been formed by direct addition of water to the
alkene contrary to the Markovnikov’s rule.
Q. 11.7. Give the structures and IUPAC names of monohydric phenols of molecular formula C ?HgO.
Ans. The three isomers are:
 4-Methylphenol or p-Cresol

2-Methylphenol or o- 3-Methylphenol or m-Cresol

Cresol

Q. 11.8. While separating a mixture of ortho- and para-nitrophenols by steam distillation, name the
isomer which will be steam volatile ? Give reasons.
Ans. o-Nitrophenol is steam-volatile due to chelation (intramolecular H-bonding) and hence can be
separated by steam distillation from p-nitrophenol which is not steam volatile because of intermolecular
H- bonding. For structures, refer to page 11/39.
Q. 11.9. Give the equations of reactions of preparation of phenol from cumene.
Ans. Refer to page 11/19.
Q. 11.10. Write chemical reaction for the preparation of phenol from chlorobenzene.
Ans. Refer to pages 11/18-11/19.
Q. 11.11. Write the mechanism of hydration of ethene to form ethanol.
Ans. Direct addition of H2O to ethene in presence of an acid does not occur. Indirectly, ethene is first
passed through cone. H2SO4, when ethyl hydrogen sulphate is formed.
H2SO4→ H+ + -OSO20H

CH3—CH2—OSO2OH

Ethene Ethyl Ethyl hydrogen sulphate

carbocation

Ethyl hydrogen sulphate when boiled with water undergoes hydrolysis to form ethanol.

CH3CH2—OH + H3O+

Ethyl hydrogen sulphate ^H Ethanoi

Q. 11.12. You are given benzene, cone. H2SO4 and NaOH. Write the equations for the preparation of
phenol using these reagents.(Hr. Board 2011)

Ans. C6H6 C6H5SO3H C6H5ONa C6H5OH

 Benzene Benzenesulphonic Sod. Phenol
acid phenoxide

Q. 11.13. Show how will you synthesize

(i)1-phenylethanol from a suitable alkene.
(ii)cyclohexylmethanol using an alkyl halide by an SN2 reaction.
(iii)pentan-l-ol using a suitable alkyl halide ?
Ans. (i) Addition of H2O to ethenylbenzene (or styrene) in presence of dil. H2SO4 gives 1- phenylethanol

Ethenylbenzene or Styrene 1-Phenylethanol

(ii) Hydrolysis of cyclohexylmethyl bromide by aqueous NaOH gives cyclohexylmethanol

+ NaOH + NaBr

Cyclohexylmethyl bromide Cyclohexylmethanol

(iii) Hydrolysis of 1-bromopentane by aqueous NaOH gives pentan-l-ol.

CH3CH2CH2CH2CH2—Br + NaOH (aq) CH3CH2CH2CH2CH2—OH + NaBr

1-Bromopentane Pentan-l-ol

Q. 11.14. Give two reactions that show the acidic nature of phenol. Compare its acidity with that of
ethanol.
(Hr. Board 2011)
Ans. The reactions showing acidic nature of phenol are:
(i) Reaction with sodium. Phenol reacts with active metals like sodium to liberate H2 gas.

+ 2 Na + H2

Phenol Sod. phenoxide

(ii) Reaction with NaOH. Phenol dissolves in NaOH to form sod. phenoxide and water.
 + NaOH + H2O

Sodium Sod. phenoxide

Comparison of acidic character of phenol and ethanol. Phenol is more acidic than ethanol. This is due
to the reason that phenoxide ion left after the loss of a proton from phenol is stabilized by resonance
(Refer to structures, VI to X on page 11/25) while ethoxide ion (left after loss of a proton from ethanol) is
not.
Q. 11.15. Explain why is orffto-nitrophenol more acidic than ori/m-methoxyphenol ?
(Hr. Board 2011; CBSE 2012)
Ans. Due to strong -R and -I-effect of the - NO2 group, electron density in the O—H bond decreases and
hence the loss of a proton becomes easy.

-I-Effect -R-Effect
decreases electron density puts a + ve charge on the phenolic O-atom, facilitates
in« the O—H bond, makes the release of a proton
release of proton easy

Further, after the loss of a proton, the o-nitrophenoxide ion left behind is stabilized by resonance,
thereby making o-nitrophenol a stronger acid.

In contrast, due to +R effect of the OCH3 group, the electron density in the O—H bond increases thereby
making the loss of a proton difficult.

Furthermore, the o-methoxyphenoxide ion left after the loss of a proton is destabilized by resonance
because the two negative charges repel each other thereby making o-methoxyphenol a weaker acid.
Thus, o-nitrophenol is more acidic than o- methoxyphenol.
Q. 11.16. Explain how does -OH group attached to a carbon of benzene ring activate it towards
electrophilic substitution ?(Hr. Board 2011)
Ans. Phenol may be regarded as a resonance hybrid of structures, I-V as shown on page 11/24. As a
result of +R-effect of the OH group, the electron density in the benzene ring increases thereby
facilitating the attack by an electrophile. In other words, presence of OH group, activates the benzene
ring towards electrophilic substitution reactions. Further since the electron density is relatively higher at
the two o- and one p- position, therefore, electrophilic substitution occurs mainly at o- and p-positions.
Q. 11.17. Give equations of the following reactions:
(i)Oxidation of propan-l-ol with alkaline KMnO4 solution (ii) Bromine in CS2 with phenol
(iii)Dilute nitric acid with phenol (iv) Treating phenol with chloroform in presence of aqueousNaOH.

Ans. (i) CH3CH2CH2OH CH3CH2COOK CH3CH2COOH

Propan-l-ol Propanoic acid

(ii)

Phenol o-Bromophenol p-Bromophenol

(iminor product)
(major product)

(iii)

Phenol o-Nitrophenol (major jP-Nitrophenol (minor

product) product)

(iv) H+/H2O

p.

Phenol Salicyladehyde (major

product)

A small amount of p-hydroxybenzaldehyde is also formed.

Q. 11.18. Explain the following with an example: (i) Kolbe’s reaction (ii) Reimer-Tiemann reaction
(iii)Williamson ether synthesis (iv) Unsymmetrical ether.
Ans. (i) Refer to page 11/40. (ii) Refer to pages 11/41-11/42. (iii) Refer to pages 11/50-11/52.
(iv)If the alkyl or aryl groups attached to the oxygen atom are different, ethers are called unsymmetrical
ethers. For example, ethyl methyl ether, methyl phenyl ether, 4-chlorophenyl 4-nitrophenyl ether,
etc. Write the structures of these ethers yourself.
Q. 11.19. Write the mechanism of acid-catalysed dehydration of ethanol to ethene.
(Hr. Board 2011, CBSE 2011)
Ans. Refer to Art. 11.8, page 11/34.
Q. 11.20. How are the following conversions carried out ?
(i) Propene→ propan-2-ol(CBSE 2011)
(ii)Benzyl chloride→ Benzyl alcohol
(iii)Ethylmagnesium chloride→ Propan-l-ol
(iv)Methylmagnesium bromide→ 2- Methylpropan-2-ol.
Ans. (i) Propan-2-ol can be prepared from propene by hydration as shown below:

CH3—CH = CH2 + Cone. H2SO4

Propene

Isopropyl hydrogen sulphate

H2O

Boiling

Propan-2-ol

(ii) + NaOH (aq) Hydrolysis + NaCl

Benzyl chloride Benzyl alcohol

(iii) Dry ether [CH3CH2CH2OMgCl]

Ethylmag. chloride Addition product

Methanal CH3CH2CH2OH + Mg(OH)Cl

 Propan-l-ol

Dry ether

(iv) ►

Methylmag.

Propanone or Acetone bromide

+ Mg(OH)Br

2-Methylpropan-2-ol

Q. 11.21. Name the reagents in the following reactions:

(*) Oxidation of a primary alcohol to a carboxylic acid
(ii) Oxidation of a primary alcohol to an aldehyde(CBSE 2008)
(iii) Bromination of phenol to 2,4, 6-tribromophenol(CBSE 2008)
(iv)Benzyl alcohol to benzoic acid (v) Dehydration of propan-2-ol to propene
(vi) Butan-2-one to butan-2-ol.(CBSE 2008)
Ans. (i) Acidified potassium dichromate or, neutral, acidic or alkaline potassium permanganate (followed
by hydrolysis with dil. H2SO4).
(ii)Pyridinium chlorochromate (PCC), C5H5NH+CrO3Cl- in CH2Cl2
or Pyridinium dichromate (PDC), (C5H5NH)2Cr,𝑂72− in CH2Cl2.
(iii)Aqueous bromine, i.e., Br2/H2O.
(iv)Acidified or alkaline potassium permanganate (followed by hydrolysis with dil. H>SO4).
(v)85% H2SO4 at 440 K.(vi) Ni/H2 or NaBH4 or LiAlH4.
Q. 11.22. Give reason for the higher boiling point of ethanol in comparison to methoxymethane.
Ans. Ethanol undergoes intermolecular H-bonding due to the presence of a hydrogen attached to the
electronegative oxygen atom. As a result, ethanol exists as associated molecules.

Consequently, a large amount of energy is required to break these hydrogen bonds. Therefore, the
boiling point of ethanol is higher than that of methoxymethane which does not form H-bonds.
Q. 11.23. Give the IUPAC names of the following ethers:
(i) (ii) CH3—O—CH2CH2Cl (iii) O2N—C6H4—OCH3(p)

(iv) CH3—CH2—CH2—OCH3 (v) (vi)

Ans. (i) l-Ethoxy-2-methylpropane(ii) 2-Chloro-l-methoxyethane

(iii)4-Nitroanisole(iv) 1-Methoxypropane
(v)4-Ethoxy-1, 1-dimethylcvclohexane (lowest locant rule is followed)
(vi)Ethoxybenzene
Q. 11.24. Write the names of reagents and equations for the preparation of the following ethers by
Williamson synthesis:
(i)1-Propoxypropane(ii) Ethoxybenzene(CBSE 2008)
(iii)2-Methyl-2-methoxypr«pane (CBSE 2008) (iv) 1-Methoxyethane

Ans. CH3CH2CH2—O —CH2CH2CH3+ NaBr

Sodium propoxide 1-Bromopropane 1-Propoxypropane

(ii) + NaBr

Bromoethane

Sod. phenoxide Ethoxybenzene

(iii) NaBr
 Sod. 2-methyl-2-propoxide 2-Methoxy-2-
methylpropane

CH3CH2—O— CH3 + NaBr

Sod. ethoxide Bromomethane 1 -Methoxyethane

Q. 11.25. Illustrate with examples the limitations of Williamson synthesis for the preparation of
certain type of ethers.(Hr. Board 20U)
Ans. Refer to Limitations on pages 11/51-11/52.
Q. 11.26. How is 1-propoxypropane synthesized from propan-l-ol ?
Ans. The following two methods can be used:
(a)Williamson synthesis

(i) 3 CH3CH2CH2OH + PBr3 3 CH3CH2CH9Br + H3PO3

Propan-l-ol 1-Bromopropane

(ii) 2 CH3CH2CH2OH + 2 Na 2 CH3CH2CH2O-Na+ + H2

Propan-l-ol Sod. propoxide

CH3CH2CH2—O—CH2CH2CH3 + NaBr

Sod. propoxide 1-Bromopropane 1 -Propoxypropane

(b) By dehydration of 1-propanol with cone. H2SO4 at 413 K.

1-Propanol

Protonated 1-propanol
 1-Propanol 1 -Propoxypropane

Q. 11.27. Preparation of ethers by acid dehydration of secondary and tertiary alcohols is not a suitable
method. Give reason.
Ans. Acid-catalysed dehydration of 1° alcohols to ethers occurs by SN2 reaction involving nucleophilic
attack by the alcohol molecule on the protonated alcohol molecule.

CH3CH2CH2—O—CH2CH2CH3

Under these conditions, 2° and 3° alcohols, however, give alkenes rather than ethers. The reason being
that due to steric hindrance, nucleophlic attack by the alcohol molecule on the protonated alcohol
molecule does not occur. Instead protonated 2° and 3° alcohols lose a molecule of water to form stable
2° and 3° carbocations. These carbocations prefer to lose a proton to form alkenes rather than
undergoing nucleophilic attack by alcohol molecule to form ethers.

Propan-2-ol Protonated propan- Isopropyl carbocation

2-ol

(2° Alcohol) (2° carbocation)

CH3—CH=CH2

2-Propoxy-2-propane Propene

Similarly, 3° alcohols give alkenes rather than ethers.

(CH3)3C-OH (CH3)3C+

2-Methylpropan-2-ol Protonated tert- Butyl carbocation

(3° Alcohol) 2-methylpropan-2-
ol
 2-Methylprop-1 -ene

2-Methyl 2-(2-methyl- 2- tert- Butyl

propoxy)propane carbocation

Q. 11.28. Write the equation of the reaction of hydrogen iodide with

(i) 1-propoxypropane (ii) methoxybenzene (iii) benzyl ethyl ether

Ans. (i) CH3CH2CH2—O—CH2CH2CH3 CH3CH2CH2—OH + CH3CH2CH2—I

1 -Propoxypropane Propan-l-ol 1-Iodopropane

(ii) HI, 373 K + CH3—I

Iodomethane

Methoxybenzene Phenol

(iii) HI, 373 K C2H5— OH

→ +

Ethanol

Benzyl ethyl ether Benzyl iodide

Q. 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.(Hr. Board 2011)
Ans. Refer to Electrophilic substitution reactions, pages 11/59-11/60.
Q. 11.30. Write the mechanism of the reaction of HI with methoxymethane.
Ans. With equimolar amounts of HI and methoxymethane, a mixture of methyl alcohol and methyl
iodide is formed by the following mechanism:
 Step 1.

Methoxymethane (cone.) Dimethyloxonium ion

Step 2. CH3—I + CH3—OH

Methyl Methyl alcohol

iodide

If, however, excess of HI is used, methyl alcohol formed in step 2 is also converted into methyl iodide by
the following mechanism.

Step 3.

Methyl alcohol Protonated methyl alcohol

Step 4. CH3—I + H2O

Methyl iodide Water

Q. 11,31. Write equations of the following reactions:

(i)Friedel-Crafts reaction—alkylation in anisole
(ii)Nitration of anisole
(MI) Bromination of anisole in ethanoic acid medium
(iv)Friedel-Crafts acetylation of anisole.(CBSE 2011)
Ans. Refer to reactions given on pages 11/59-11/60.
Q. 11.32. Show how would you synthesize the following alcohols from appropriate alkenes ?

(i) (ii) (iii) (iv)

(RE-AIPMT 2015)
Ans. Silice addition and elimination are reverse of each other, therefore, the general strategy is to first
dehydrate a suitable alcohol to give either a single alkene or a mixture of alkenes. If a mixture of alkenes
is possible, then find out which of the alkenes will give the desired alcohol. Please nòte that acid-
catalysed addition of H2O to alkenes occurs in accordance with Markovnikov’s rule.

(i)

1-Methylcyclohexan-l -ol 1 -Methlcyclohexene Methylenecyclohexane

Addition of H2Q to both these alkenes gives the desired alcohol.

(ii)

4-Methylheptan-4-ol 4-Methyihept-3 -ene

Addition of H2Q to 4-methylhept-3-ene in presence of an acid gives the desired alcohol.

+ H-OH

4-Methylhept-3-ene 4-Methylheptan-4-ol

(iii)

Pentan-2-ol Pent-l-ene Pent-2-ene

Now addition of H2O to pent-l-ene gives the desired alcohol.

 + H-OH

Pent-l-ene Pentan-2-ol

However, addition of H2O to pent-2-ene gives a mixture of two alcohols, i.e., pentan-2-ol and pentan-3-
ol.

Pent-2-ene Pentan-2-ol Pentan-3-ol

Thus, the desired alkene is pent-l-ene and not pent-2-ene.

(iv) +

2-Cyclohexylbutan-2-ol 2-Cyclohexylbut- 2- 2-Cyclohexylbut-1 -

2-ene Cyclohexylidenebutane ene

Now addition of H2O to either of the three alkenes in presence of an acid gives the desired alcohol.

+ H+ +H+ or

2-CyclohexyIbut-2- 2- 2-Cyclohexylbut-1 -ene

ene Cyclohexylidenebutane

2-Cyclohexylbutan-2-ol

Thus, the desired alkene is 2-cyclohexylbut-l-en or 2-cyclohexylbut-2-ene or 2-cyclohexylidenebutane.

Q. 11.33. When 3-methylbutan-2-ol is treated with HBr, the following reaction takes place:

HBr
 →

Give a mechanism for this reaction.

Ans. Protonation of the given alcohol followed by loss of water gives a 2° carbocation (I) which being
less stable rearranges by 1, 2- hydride shift to form the more stable 3° carbocation (II). Nucleophilic
attack by Br_ ion on this carbocation (II) gives the final product.

3-Methylbutan-2-ol 2° Carbocation (less

stable)

3° Carbocation 2-Bromo-2-methylbutane
(more stable)

Aldehyde, Ketones and Carboxylic acids

NCERT INTEXT SOLVED QUESTIONS
Q. 12.1. Give names of the reagents to bring about the following transformations.
(i) Hexan-1-ol to hexanal, (ii) Cyciohexanol to cyclohexanone (CBSE 2010)
(iii) p-Fluorotoluene to p-fluorobenzaldehyde, (iv) Ethanenitrile to ethanal, (v) Allyl alcohol to
propenal, and (vi) But-2-ene to ethanal.

Ans. (i) CH3CH2CH2CH2CH2CH2OH CH3CH2CH2CH2CH2CHO

Hexan-l-ol Hexanal

(ii) K2Cr2O7/H2SO4

Cyciohexanol Cyclohexanone
 (iii)

(iv) CH3—C = N

Ethanenitrile Ethanal

(v) CH2 = CHCH2OH CH2 = CH—CHO

Allyl alcohol Prop-2-enal

(vi) CH3CH = CHCH3 2 CH3—CHO

But-2-ene Ethanal

Q. 12.2. Arrange the following compounds in increasing order of their boiling points
CH3CH2CH2CHO, ch3cH2cH2cH2Oh, C2HsOC2H5, ch3cH2cH2cH2ch3.
Ans. The molecular masses of all these compounds are comparable:
CH3CH2CH2CHO (72), CH3CH2CH2CH2OH (74), C2H5—O—C2H5 (74), CH3CH2CH2CH2CH3 (72). Butan-l-ol,
i.e.,CH3CH2CH2CH2OH undergoes extensive mtermolecular H-bonding, therefore, its boiling point is the
highest. Butanal is more polar than ethoxyethane, therefore, dipole-dipole interactions are stronger in
CH3CH2CH2CHO than in C2H5OC2H5 and hence the b.p. of CH3CH2CH2CHO ishigher than that of
C2H5OC2H5. Further, due to the presence of oxygen atom the molecules of C2H5OC2H5 are little less
symmetrical (refer to page 11/52 for explanation) than those of n-pentane. As a result, van der Waals
forces of attraction between molecules of C2H5OC2H5 are slightly lower than those between molecules of
«-pentane. Hence, the b.p. of n-pentane is little higher than that of C2H5OC2H5. Thus, the overall
increasing order of boiling points is:
C2H5OC2H5<CH3CH2CH2CH2CH3<CH3CH2CH2CHO <CH3CH2CH2CH2OH Please note that inN.C.E.R.T. test
book, this order has been wrongly written as:CH3CH2CH2CH2CH3< C2H5OC2H5<CH3CH2CH2CHO
<CH3CH2CH2CH2OH.
Q. 12.3. Would you expect benzaldehyde to be more reactive or less reactive in nucleophilic addition
reactions than propanal ? Explain your answer.
Ans.

Due to weak +I-effect of the ethyl group, the positive charge on the carbon atom of the carbonyl group
in propanal is reduced to small extent. In contrast, in benzaldehyde, the positive charge on the carbon
atom of the carbonyl group is reduced to a greater extent due to stronger +R-effect of the benzene ring.
As a result, the carbon atom of the carbonyl group of benzaldehyde is less electrophilic than carbon
atom of the carbonyl group in propanal and hence benzaldehyde is less reactive than propanal in
nucleophilic addition reactions.
Q. 12.4. An organic compound (A) with molecular formula, CgH80 forms an orange-red precipitate
with 2, 4-DNP reagent and gives yellow precipitate on heating with iodine in the presence of sodium
hydroxide. It neither reduces Tollens’ or Fehling’s reagent, nor does it decolourise bromine water or
Baeyer’s reagent. On drastic oxidation with chromic acid, it gives a carboxylic acid (B) having
molecular formula, C7H6O2. Identify the compounds (A) and (B) and explain the reactions involved.
Ans. Step 1. To determine the structures of compounds (A) and (B).
(?) Since compound (A), M.F. C8H8O forms a 2, 4-DNP, it must be either an aldehyde or a ketone. (a)
Since, it does not reduce Tollens’ reagent or Fehling’s solution, (A) is must be a ketone.
(iii) Since (A) on treatment with I2/NaOH, gives yellow ppt. (iodoform), therefore, it must be a methyl
ketone.
8 (4−2) + 8 (l−2) + l (2−2)
(iv) D.B.E. for C8H8O - +1=5
2

One of the five sites of unsaturation must be due to the keto group, the remaining four may be due to
the presence of a benzene ring. The presence of benzene ring is supported by the observation that it
neither decolourizes bromine water nor Baeyer’s reagent.
(v) Since drastic oxidation of A with chromic acid gives compound (B) with M.F. C7H6O2, therefore, (B)
must be benzoic acid. Further, the formation of benzoic acid suggests that compound (A) is a mono-
substituted benzene derivative.
(vi) Thus, compound (A) has a monosubstituted benzene ring, i.e., a C6H5 ring and CH3CO group. Both
these groups account for the complete M.F. (C6H5 + COCH3 = C8H8O) of compound(A), therefore,
compound (A) is acetophenone or methyl phenyl ketone or 1-phenylethanone.

Acetophenone, M.F. C8H8O.

 (A)

Step 2. To explain all the reactions involved in the question.

Q. 12.5. Write chemical reactions to effect the following transformations:

(i) Butan-1-ol to butanoic acid (Hr. Board 2011 ; CBSE 2012)
(ii) Benzyl alcohol to phenvlethanoic acid (Hr. Board 2011)
(iii) 3-Nitrobromobenzene to 3-nitrobenzoic acid (CBSE 2012)
(iv) 4-Methylacetophenone to benzene-1,4-dicarboxylic acid
(v) Cyclohexene to hexane-1,6-dioic acid (CBSE Sample Paper 2018-19)
(vi) Butanal to butanoic acid.

Ans. (i)CH3CH2CH2CH2OH CH3CH2CH2COOH

Butan-l-ol Butanoic acid

(ii) C6H5CH2OH C6H5CH2Br KCN C6H5CH2CN C6H5CH2COOH

Benzyl alcohol Benzyl Benzyl cyanide Phenylethanoic acid

bromide
 (iv) KMnO4/KOH, ∆

4-Methylacetophenone Dipotassium benzene-1,4-dicarboxylate

Benzene-4-dicarboxylic acid

(Terephthalic acid)

(v)

Cyclohexene Hexane-1, 6-dioic acid (Adipic

acid)

(vi) CH3CH2CH2CHO CH3CH2CH2COONH4 CH3CH2CH2COOH

Butanal Amm. butyrate Butanoic acid

NCERT INTEXTUNSOLVEDQUESTIONS

Q. 12.1. Write the structures of the following compounds

(i) α-Methoxypropionaldehyde(ii) 3-Hydro xybutanal
(iii) 2-HydroxycyclopentanecarbaIdehyde(iv) 4-Oxopentanal
(v) Di-sec-butyl ketone(vi) 4-Fluoroacetophenone. (CBSE 2010 S)
 Ans. (i) (ii)

(iii) (iv)

(v) (vi)

Q. 12.2. Write the structures of products of the following reactions:

(ü) (C6H5CH2 )2Cd + 2 CH3COCI →

(iii) CH3—C 3 CH Hg2+,H2SO4 (iv)

Ans. (i)

Propanoyl
chloride

Propiophenone

(ii)

1 -Phenylpropan-2-one
 (iii) CH3—C 3 CH + H—OH Hg2+, dil.H2SO4 T automerises

Propyne Propanone

(iv)

p-Nitrotoluene

p-N itrobenzald ehy de

Q. 12.3. Arrange the following compounds in increasing order of their boiling points:
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3.
Ans. The molecular masses of all these compounds are comparable:CH3CHO(44), CH3CH2OH(46),
CH3COCH3 (46), CH3CH2CH3 (44). CH3CH2OH undergoes extensive intermolecular H-bonding, therefore, it
exists as an associated molecule and hence its b.p. is the highest (351 K).CH3CHO (p = 2-72 D) is more
polar than CH3OCH3 (p = 118 D), therefore, dipole- dipole interactions are stronger in CH3CHO than in
CH3OCH3 and hence the boiling point of CH3CHO (293 K) is much higher than that of CH3OCH3 (249 K).
Further, molecules of CH3CH2CH3 have only weak van der Waals forces while the molecules of CH3OCH3
have little stronger dipole-dipole interactions and hence the b.p. of CH3OCH3 is higher (249 K) than that
of CH3CH2CH3 (231 K). Thus, the overall increasing order of boiling points
is:CH3CH2CH3<CH3OCH3<CH3CHO <CH3CH2OH.
Q. 12.4. Arrange the following carbonyl compounds in increasing order of their reactivity in
nucleophilic addition reactions.
(i) Ethanal, Propanal. Propanone, Butanone
(ii) Benzaldehyde, p-Tolualdehyde, p- Nitrobenzaldehyde, Acetophenone.

Ans. (i)

Ethanal Propanal Propanone Butanone

As we move from ethanal > propanal > propanone > butanone, the +I-effect of the alkyl
group increases. As a result, electron density on the carbon atom of the carbonyl group progressively
increases and hence attack by the nucleophile becomes slower and slower. Thus, the reactivity increases
in the reverse order, i.e., butanone<propanone < propanal < ethanal
(ii) Acetophenone is a ketone, while all others are aldehydes, therefore, it is the least reactive. In p-
tolualdehyde, there is a CH3 group at the p-position w.r.t. to the carbonyl group, which increases the
electron density on the carbon of the carbonyl group by hyperconjugation effect thereby making it less
reactive than benzaldehyde.

On the other hand, in p-nitrobenzaldehyde, the NO2 group is a powerful electron-withdrawing group. It
withdraws electrons, both by inductive and resonance effect thereby decreasing the electron-density on
the carbon atom of the carbonyl group. This facilitates the attack of the nucleophile and hence makes it
more reactive than benzaldehyde

Therefore, the overall reactivity increases in the order:

acetophenone < p-tolualdehyde < benzaldehyde < p- nitrobenzaldehyde
Q. 12.5. Predict the products of the following reactions:

(i) + HO—NH2 H+ (ii)

(CBSE Sample Paper 2018-19)

(iii) R—CH = CH—CHO + H+

(iv) + CH3CH2NH2 H+

Ans. (i) (ii)

(iii) NH2 attached to NH is more nucleophilic than NH2 attached to C = O group, therefore, reaction
occurs through NH2 attached to NH to give the corresponding semicarbozone, i.e.,
 R—CH = CH—CH NNHCONH2 > R—CH = CH—CH = NNHCONH2 + H2Q

(iv) H+

Q. 12.6. Give the IUPAC names of the following compounds:

(i) PhCH2CH2COOH (ii) (CH3)2C = CHCOOH

(iii) (iv)

Ans. (i) 3-Phenylpropanoic acid (ii) 3-Methylbut-2-enoic acid (iii) 2-Methylcyclopentanecarboxylic acid
(iv) 2,4, 6-Tnnitrobenzoic acid or 2, 4, 6-Trinitrobenzenecarboxylic acid.
Q. 12.7. Show how each of the following compounds could be converted to benzoic acid
(i) Ethylbenzene (CBSE 2010 ; Hr. Board 2011
(ii) Acetophenone (iii) Bromobenzene (iv) Phenyethene (Styrene).
(CBSE 2008 ; Hr. Board 2011)

H3O+

Ans. (i)

Ethylbenzene Pot. benzoate Benzoic acid

H3O+

(ii)

Acetophenone Pot. benzoate Benzoic acid

 Alternatively, h3o+

Acetophenone Sod. benzoate Benzoic acid

(iii)

Bromobenzene Phenylmag.
bromide

Benzoic acid

(iv) HCOO-K+ H3O+

Pot. formate

Phenylethene or Pot. benzoate

Styrene
+ HCOOH

Methanoic acid

Benzoic acid

Q. 12.8. Which acid of each pair shown here would you expect to be stronger ?
(i) CH3CO2H or FCH2CO2H (ii) FCH2CO2H or ClCH2CO2H (CBSE 2013)
(iii) FCH2CH2CH2CO2H or CH3—CHF—CH2CO2H

(iv)
 Ans. (i)

+I-effect of CH3 group increases the -I-effect of F decreases

electron density in the O-H bond the electron density in
+I-effect destabilizes -I-effect stabilizes
thereby making the release of a the O-H bond thereby
the carboxylate ion by the carboxylate ion
proton difficult making the release of a
intensifying the -ve by dispersing the -ve
proton easier
charge charge

Thus, due to lesser electron density in the O—H bond and greater stability of FCH2COO ion over CH3COO-
ion, FCH2COOH is a stronger acid than CH3COOH.
(ii) Due to much stronger -I-effect of F over Cl, the FCH2COO ion is much more stable than ClCH2COO- ion
and hence FCH2COOH is a stronger acid than ClCH2COOH.

(iii)

4-Fluorobutanoic acid 3-Fluorobutanoic acid

Inductive effect decreases with distance, therefore, -I-effect of F is somewhat stronger in 3-fluoro-
butanoic acid than in 4-fluorobutanoic acid. In other words, Cl I—CHF—CH2COO ion is somewhat more
stable than FCH2CH2CH2COO- ion and hence Clf ClIFCH2COOH is a stronger acid than FCH2CH2CH2COOH.

(iv)

CF3 has a strong -I-effect. CH3 has a weak +I-effect.

It stabilizes the carboxylate ion by dispersing the - It destabilizes the carboxylate ion by
ve charge. intensifying the -ve carge.

Therefore, due to greater stability of F3C—C6H4—COO-(p) ion over CH3—CgH4COO (p) ion, F3C—C6H4—
COOH (p) is a much stronger acid thanCH3—C6H4—COOH (p).
NCERT EXERCISES
Q. 12.1. What is meant by the following terms ? Give an example in each case.
(i) Cyanohydrin (ii) Acetal (HP Board 2013) (iii) Semicarbazone (iv) Aldol (v) Hemiacetal
(vi) Oxime (vii) Ketal (viii) Inline (ix) 2, 4-DNP derivative (x) Schiff’s base.
Ans. (i) gem-Hydroxynitriles, i.e., compounds possessing hydroxyl and cyano groups on the same carbon
atom are called cyanohydrins. These are produced by addition of HCN to aldehydes or ketones in weakly
basic medium.
 pH 9-10

Cyanohydrins are useful synthetic reagents because they are used to prepare α-hydroxyacids. For
example.

Acetaldehyde Acetaldehyde Lactic acid

cyanohydrin or a-Hydroxypropionic acid

(ii) gew-Dialkoxyalkanes in which the two alkoxy groups are present on the terminal carbon atom are
called acetals. These are produced by the action of an aldehyde with two equivalents of a monohydnc
alcohol in presence of dry HCl gas.

Acetaldehyde Ethyl alcohol Acetaldehyde diethyl acetal

These are easily hydrolysed by dilute mineral acids to regenerate the original aldehydes. Therefore,
these are used for the protection of aldehyde group in organic synthesis.
(iii) Semicarbazones are derivatives of aldehydes and ketones and are produced by the action of
semicarbazide on them in weakly acidic medium.

NNHCONH2 + H2O

Acetone Semicarbazide Acetone semicarbazone

These are used for identification and characterization of aldehydes and ketones.
(iv) Aldols are (3-hydroxyaldehydes or ketones and are produced by the condensation of two molecules
of the same or one molecule each of two different aldehydes or ketones in presence of a dilute aqueous
base. For example,

Dil. NaOH
 β-Hydroxybutyraldehyde (An aldol)

Acetaldehyde (two molecules)

Ba(OH)2

Acetone (two molecules)

Diacetone alcohol (A ketol but usually

called aldol)

(v) α-Alkoxyalcohols are called hemiacetals. These are produced by addition of one molecule of a
monohydric alcohol to an aldehvde in nresence of drv HCl cas.

Ethanal Methyl alcohol 1 -Hydroxy-1 -methoxy ethane (A hemiacetal)

(yi) Oximes are produced when aldehydes or ketones react with hydroxylamine in weakly acidic
medium.

pH 3.5 + H2O

Ethanal Hydroxylamine Acetaldoxime

(vii) gem-ulaiKoxyaixanes in wmcn me two aixoxy groups are present on me same caroon within the
chain are called ketals. These are produced when a ketone is heated with ethylene glycol in presence of
dry HCl gas or p-toluenesulphonic acid (PTS)

Acetone Ethylene glycol Acetone ethylene ketal

These are easily hydrolysed by dilute mineral acids to regenerate the original ketones. Therefore, ketals
are used for protection of keto groups in organic synthesis.

(yiii) Compounds containing group are called imines. These are produced when
aldehydes and ketones react with ammonia and its derivatives.
 + H2O

Imine

Aldehyde/ketone Ammonia derivative

Z = H, Alkyl, aryl, -NH, -OH, -NHC6H5, -NHCONH2, etc.

(ix) 2,4-Dimtrophenylhydrazones (i.e.,2,4-DNP derivatives) are produced when aldehydes or ketones
react with 2, 4-dimtrophenylhydrazine in weakly acidic medium.

Acetone 2, 4- Acetone 2,4-dinitrophenylhydrazone

Dinitrophenylhydrazine

2, 4-DNP derivatives are used for identification and characterisation of aldehydes and ketones (×)
Aldehydes and ketones react with primary aliphatic or aromatic amines in presence of trace of an acid to
form azomethines or Schiff’s bases. Schiff’s bases may also be regarded as imines.

R—CH = N—R' + H2O

Schiff’s base

Aldehyde 1° Amine

eg-, ch3ch = ncH2ch3 + H2O

Ethylideneethanamine

Ethanal Ethanamine

C6H5CH=NC6H5 + H2O

Benzaldehyde Aniline Benzylideneaniline

Q. 12.2. Name the following compounds according to IUPAC system of nomenclature

(i) CH3CH(CH3)CH2CH2CHO (U) CH3CH2COCH(C2H5>CH2CH2Cl
(iii) CH,CH = CHCHO (iv) CH3COCH,COCH3 (v) CH3CH(CH,)CH2C(CH3),COCH,
(vi) (CH3)3CCH2COOH (vii) OHCC6H4CHO-p
Ans. (i)4-Methylpentanal (ii)6-Chloro-4-ethylhexan-3-one (iii)But-2-en-1 -al
(iv)Pentane-2, 4-dione (v) 3, 3, 5-Trimethylhexan-2-one (vi)3, 3-Dimethylbutanoic acid
(vii) Benzene-1, 4-dicarbaldehyde
Q. 12.3. Draw the structures of the following compounds:
(i) 3-Methylbutanal (it)/i-Nitropropiophenone (iii)/»-Methylbenzaldehyde
(iv) 4-Methylpent-3-en-2-one (v) 4-Chloropentan-2-one (CBSE 2008)
(vi) 3-Bromo-4-phenylpentanoic acid (vii) /^/»'-Dihydroxybenzophenone
(viii) Hex-2-en-4-ynoic acid

(v) (vi)

Ans. (i) (ii)

(iii) (iv)

(vii) (viii)

Q. 12.4. Write the IUPAC names of the following ketones and aldehydes. Wherever possible, give also
common names.
(i) CH3CO(CH2)4CH3(ii) CH3CH2CHBrCH2CH(CH3)CHO
(iii) CH3(CH2)sCHO(iv) Ph—CH = CH—CHO (CBSE 2012)

(v) (CBSE 2010) (vi) PhCOPh

Ans. IUPAC name Common name

(i) Heptan-2-one Methyl n-pentyl ketone

(ii) 4-Bromo-2-methylhexanal y-Bromo-a-methylcaproaldehyde

(iii) Heptanal —

(iv) 3 -Phenylprop-2-enal (3-Phenylacrolem

(v) Cyclopentanecarbaldehyde Cyclopentanecarbaldehyde

(vi) Diphenylmethanone Benzophenone

Q. [Link] structures of the following derivatives:

(i) The 2, 4-dinitrophenylhydrazone of benzaldehyde
(ii) Cyclopropanone oxime
(iii) Acetaldehydedimethyl acetal(iv) The semicarbazone of cyclobutanone
(v) The ethylene ketal of hexan-3-one(vi) The methyl hemiacetal of formaldehyde.

Ans. (i) (ii) (iii)

(iv) (v) (VO

Q. 12.6. Predict the products formed when cyclohexanecarbaldehyde reacts with following reagents:
(i) PhMgBr and then H3O+ (ii) Tollens’ reagent (iii) Semicarbazide and weak acid (iv) Excess ethanol and
acid (v) Zinc amalgam and dilute hydrochloric acid.

Ans. (i)
 Cyclohexane Cyclohexylphenylcarbinol
carbaldehyde

(ii) + 2 [Ag(NH3)2]+ + 3 OH- + 2Agl + 4NH3 + 2H2O

Silver

Cyclohexane Tollens’ reagent Cyclohexane- mirror

carboxylate ion
carbaldehyde

(iii) + H2O

Semicarbazide

Cyclohexane Cyclohexanecarbaldehyde
carbaldehyde semicarbazone

(iv) Dry HCl gas

Cyclohexane Ethanol (excess) Cyclohexanecarbaldehyde diethyl acetal

carbaldehyde

(v)

Cyclohexane Methylcyclohexane
carbaldehyde

Q. 12.7. Which of the following compounds will undergo aldol condensation, which the Cannizzaro
reaction and which neither ? Write the structures of the expected products of aldol condensation and
Cannizzaro reaction.
(i) Methanal (ii) 2-Methylpentanal (iii) Benzaldehyde (iv) Benzophenone
(v) Cyclohexanone (vi) 1-Phenylpropanone (vii) Phcnylacetaldehvde (viii)Butan-1-ol
(ix) 2, 2-Dimethylbutanal.
Ans. I. 2-Methylpentanal (ii), cyclohexanone (v), 1-phenylpropanone (vi), and phenylacetaldehyde (vii)
contain one or more α-hydrogens and hence undergoaldol condensation. The reactions and the
structures of the expected products are given below:

(ii)

2-Methylpentanal 3-Hydroxy-2,4-dimethyl-2-propylheptanal

(v)

Cyclohexanone 2-( 1 -Hydroxy-1 -cyclohexyl)cyclohexan-1 -one

(vi)

1-
Phenylpropanone

3-Hydroxy-2-methyl-1, 3-diphenylpentan-1 -
one

(vii)

Phenylacetaldehyde 3-Hydroxy-2, 4-diphenylbutanal

II. Methanal (i), benzaldehyde (iii) and 2, 2-dimethylbutanal (ix) do not contain α-hydrogen and hence
undergoCannizzaro reaction. The reactions and the structures of the expected products are given
below:

(i) 2HCHO CH3OH + HCOONa

Methanal Methanol Sod.

 methanoate

(ii)

Benzaldehyde Benzyl alcohol Sod. benzoate

(ix)

2,2-Dimethylbutanal 2,2-Dimethylbutan-l-ol Sod. 2,2-dimethylbutanoate

III. Benzophenone (iv) is a ketone having no α-hydrogen/s while butan-l-ol (viii) is an alcohol. Both of
these neither undergo aldol condensation nor Cannizzaro reaction.
Q. 12.8. How will you convert ethanal into the following compounds ?
(i) Butane-1,3-diol(Hr. Board 2011)(ii)But-2-enal (Hr. Board 2011; CBSE 2011) (ii) But-2-enoic acid.

Ans. (i) 2 CH3CHO

Ethanal 3-Hydroxybutanal

Butane-1, 3-diol

(ii) 2 CH3CHO CH3—CH = CH—CHO

Ethanal 3-Hydroxybutanal But-2-enal

(iii)CH3CHO CH3CH = CHCHO CH3CH = CHCO2H

Ethanal But-2-enal But-2-enoic acid

Q. 12.9. Write structural formulas and names of four possible aldol condensation products from
propanal and butanal. In each case, indicate which aldehyde acts as nucleophile and which as
electrophile.
Ans. (i) Propanal as nucleophile as well as electrophile.

CH3CH2CHO + CH3CH2CHO

Propanal Propanal 3 -Hydroxy-2-methylpentanal

(Electrophile) (Nucleophile)

(ii) Propanal as electrophile and butanal as nucleophile.

CH3CH2CHO + CH3CH2CH2CHO

Propanal Butanal 2-Ethyl-3-hydroxypentanal

(Electrophile) (Nucleophile)

(,Hi) Butanal as electrophile and propanal as nucleophile

CH3CH2CH2CHO + CH3CH2CHO

Butanal Propanal 3-Hydroxy-2-methylhexanal

(Electrophile) (Nucleophile)

(iv) Butanal both as nucleophile as well as an electrophile

CH3CH2CH2CHO + CH3CH2CH2CHO →

Butanal Butanal 2-Ethyl-3-hydroxyhexanal

(Electrophile) (Nucleophile)

Q. 12.10. An organic compound with the molecular formula C^HjqO forms 2, 4-DNP dervative, reduces
Tollens’ reagent and undergoes Cannizzaro reaction. On vigorous oxidation, it gives 1, 2-
benzcncdicarboxylic acid. Identify the compound.
Ans. (i) Since the given compound with M.F. C9H10O forms a 2, 4-DNP denvative and reduces Tollens’
reagent, it must an aldehyde.
(ii) Since it undergoes Cannizzaro reaction, therefore, CHO group is directly attached to the benzene
ring.
(iii) Since on vigorous oxidation, it gives 1, 2-benzenedicarboxylic acid, therefore, it must be an ortho-
substituted benzaldehyde. The only o-substituted aromatic aldehyde having M.F. C9H10O is 2-
ethylbenzaldehvde All the reactions can now be explained on the basis of this structure.

Q. 12.11. Anorganic compound A (molecular formula CgH16O2) was hydrolysed with dilute sulphuric
acid to give a carboxylic acid (B) and an alcohol (C). Oxidation of (C) with chromic acid produced
(B). (C) on dehydration gives but-2-ene as the major product. Write equations for the reactions
involved. (CBSE 2009, 2010)
Ans. (i) Since the organic compound (A) with M.F. CgH16O2 upon hydrolysis with dil. H2SO4 gives
carboxylic acid (B) and the alcohol (C), therefore, (A) must be an ester. Further, since oxidation of (C)
with chromic acid produces the acid (B), therefore, both the carboxylic acid (B) and the alcohol (C) must
contain the same number of carbon atoms.
(ii) Since ester (A) contains eight carbon atoms, therefore, both the carboxylic acid (B) and the alcohol
(C) must contain four carbon atoms each.
(iii) Since the alcohol (C) on dehydration gives but-l-ene, therefore, (C) must be a straight chain alcohol,
i.e., butan-l-ol
(iv) If (C) is butan-l-ol, then the acid (B) which it gives on oxidation must be butanoic acid and the ester
(A) must be butyl butanoate.
(v) The relevant equations for all the reactions involved may be explained as follows:

CH3CH2CH2CH2OH

Butyl butanoate (A) Butanoic acid (B) Butan-l-ol (C)

(M.F. = C8H16O2)

ch3cH2cH2cH2Oh ch3ch=chch3
 Butanoic acid (B) Butan-l-ol (C) But-2-ene

Q. 12.12. Arrange the following compounds in increasing order of their property as indicated:
(i) Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone (reactivity towards HCN).
(CBSE 2012)
(ii) CH,CH,CH(Br)COOH, CH,CH(Br)CH,COOH, (CH,),CHCOOH, CH3CH,CH2COOH (acid strength). (CBSE
2008, 2009, 2012)
(iii) Benzoic acid, 4-Nitrobenzoic acid, 3, 4-Dinitrobenzoic acid, 4-Methoxybenzoic acid (acid
strength). (CBSE 2009, 2012) Ans. (i) The reactivity towards HCN addition decreases as the +1-effect of
the alkyl group/s increases and/ or the steric hindrance to the nucleophilic attack by CN at the carbonyl
carbon increases. Thus, the reactivity decreases in the order:

Acetaldehyde Acetone

tart-Butyl methyl Di-tert-butyl ketone

ketone

+ I-effect mcreases

Steric hindrance increases

Reactivity towards HCN addition c lecreases

In other words, reactivity increases in the reverse order, i.e.,

Di-tert-butyl ketone < tert-Butyl methyl ketone < Acetone < Acetaldehyde.
(ii) We know that +I-eifect decreases while -I-effect increases the acid strength of carboxylic acids. Since
+I-effect of isopropyl group is more than that of n-propyl group, therefore, (CH3)2CHCOOH is a weaker
acid than CH3CH2CH2COOH.
Further since -I-effect decreases with distance, therefore, CH3CH2CH(Br)COOH is a stronger acid than
CH3CH(Br)CH2COOH. Thus, the overall acid strength increases in the order:
 < CH3CH2CH2—COOH <

<

(lii) Since electron-donating groups decrease the acid strength, therefore, 4-methoxybenzoic acid is a
weaker acid than benzoic acid.
Further since electron-withdrawing groups increase the acid strength, therefore, both 4-nitrobenzoic
acid and 3, 4-dinitrobenzoic acids are stronger acids than benzoic acid. Further due to the presence of
an additional NO2 group at /«-position w.r.t. COOH group, 3, 4-dmitrobenzoic acid is a little stronger acid
than 4-nitrobenzoic acid. Thus, the overall acid strength increases in the order:4-Methoxybenzoic acid <
Benzoic acid < 4-Nitrobenzoic acid < 3, 4-Dinitrobenzoic acid.
Q. 12.13. Give simple chemical tests to distinguish between the following pairs of compounds:
(i) Propanal and propanone (Raj. Board 2011; Hr. Board 2011,2013 ; CBSE, 2008,2011,2012,2016)
(ii) Acetophenone and benzophenone (CBSE 2009, 2011}
(iii) Phenol and benzoic acid (CBSE 2012, 2013)
(iv) Benzoic acid and ethyl benzoate (CBSE 2009, 2011)
(v) Pentan-2-one and pentan-3-one (CBSE 2012, 2013)
(vi) Benzaldehyde and acetophenone (CBSE 2011, 2012)
(vii) Ethanal and propanal (Hr. Board 2013 ; CBSE 2009, 2013)
Ans. Refer to Appendix 2.
(i) Distinction 30, page A/37 (ii) Distinction 40, page A/41
(iii) Distinction 42, pages A/42-A/43 (iv) Distinction 48, page A/45
(v) Distinction 38, page A/41 (vi) Distinction 39, page A/41
(vii) Distinction 27, page A/36.
Q. 12.14. How will you prepare the following compounds from benzene ? You may use any inorganic
reagent and any organic reagent having not more than one carbon atom.
(i) Methyl benzoate (Hr. Board 2011) (ii) /n-Nitrobenzoic acid (Hr. Board 2011)
(iii) p- Nitrobenzoic acid and (Hr. Board 2011) (iv) Phenylacetic acid
(v) p-Nitrobenzaldehyde

Ans. (i)
 Benzene Bromo- Phenylmag. Benzoic acid
benzene bromide

Methyl benzoate

(ii) As in (i) above

Benzene Benzoic acid m-Nitrobenzoic acid

(iii)

Benzene Toluene o-Nitrotoluene

(liquid)
p-
Nitrotoluene (minor product)
(solid)
(major
product)

p-Nitrotoluene p-Nitrobenzoic acid

(iv) As in (iii) above

 Benzene Toluene Benzyl
bromide

Benzyl cyanide Phenylacetic acid

(v)

Benzene

P- p-Ni
Nitrotoluene trobenzaldehyde

Q. 12.15. How will you bring about the following conversions in not more than two steps ?
(i) Propanone to Propene
(ii) Benzoic acid to Benzaldehyde
(iii) Ethanol to 3-HydroxybutanaI (Hr. Board 2011)
(iv) Benzene to w-Nitroacetophenone
(v) Benzaldehyde to benzophenone
(vi) Bromobenzene to 1-Phenylethanol (CBSE 2009)
(vii) Benzaldehyde to 3-Phenylpropan-1-ol
(viii) Benzaldehyde to a-Hydroxyphenylacetic acid (ix) Benzoic acid to m-Nitrobenzyl alcohol.
Ans. Refer to Appendix 3, (i) conversion 29, page A/60, (ii) conversion 24, page A/73, (iii)conversion 28,
page A/60, (iv)conversion 12, pageA/71, (v) conversion 3, page A/75, (vi) conversion 33, page
A/74,(vii) conversion 27, page A/73, (viii) conversion 30, page A/74, (ix) conversion 37, page A/83.
Q. 12.16. Describe the following: (i) Acetylation (ii) Cannizzaro reaction (iii) Crossed aldol
condensation
(iv) Decarboxylation.
Ans. Refer to Appendix 1. (i) reaction 1, page A/l (ii) reaction 6, pages A/4-A/5 (iii) reaction 2, page A/3
(iv) reaction 12, pages A/7-A/8.
Q. 12.17. Complete each synthesis by giving missing starting material, reagent or products
(i) (CBSE 2008)

(ii) (CBSE 2011)

(iii) C6HSCHO H2NCONHNH2

(v) [Ag(NH3)2]+

(iv)

(vi) NaCN/HCl (vii) C6HsCHO + CH3CB3CHO dii. NaOH

(viii) CH3COCH2COOC2H5 (ix) CrO3

(x) (x)

(CBSE 2008, 2011) (CBSE 2008)

Ans. (i) Side chain is oxidised to -COOH

 Ethylbenzene Pot. benzoate Benzoic acid

(ii)

Phthalic acid Phthaloyl chloride

(iii) More nucleophilic NH2NH part of H2NlSlHCONH2 reacts to form semicarbazone.

C6H5CHO + H2NNHCONH2 C6H5CH = NNHCONH2 + H2O

Benzaldehyde Semicarbazide Benzaldehyde semicarbazone

(iv)

Benzene Benzoyl chloride Benzophenone

(v) Only aldehydes are oxidised by Tollens’ reagent

. 4-Oxocyclohexanecarbaldehyde 4-Oxocylohexanecarboxylate anion

(vi) Cyanoitydrm formation occurs at the aldehyde group

2-Formylbenzoic acid 2-[l-Hydroxycyanomethyl] benzoic acid

(vii)

Benzaldehyde Propanal 2-Methyl-3-phenylprop-2-enal

(viii) Only keto group is reduced by NaBH4

Ethyl 3-oxobutanoate Ethyl 3-hydroxybutanoate

(ix)

Cyclohexanol Cyclohexanone

(x)

Methylenecyelohexane

Cyclohexanecarbaldehyde

(xi)

Cyclohexylidenecyclohexane Cyclohexanone

Q. 12.18. Give plausible explanation for each of the following: (7) Cyclohexanone forms cyanohydrin
in good yield but 2, 2,6-trimethylcyclohexanone does not. (ii)There are two - NH2 groups in
semicarbazide. However, only one is involved in the formation of scmicarbazone. (iii) During the
preparation of esters from a carboxylic acid and an alcohol in the presence of an acid catalyst, the
water or the ester formed should be removed as soon as it is formed.

Ans. (i)
 Cyclohexanone Cyclohexanone cyanohydrin

2, 2, 6-Trimethyl cyclohexanone

Because of the presence of three methyl [Link] a- positions w. r. t. the C = O group, the nucleophilic
attack by the CN- ion does not occur due to steric hindrance. Since there is no such steric hindrance in
cyclohexanone, therefore, nucleophilic attack by the CN- ion occurs readily and hence cyclohexanone
cyanohydrin is obtained in good yield.

(ii)

Semicarbazide

Although semicarbazide has two -NH2 groups but one of them (re. which is directly attached to C = O) is
involved in resonance as shown above. As a result, electron density on this NH2 group decreases and
hence it does not act as a nucleophile. In contrast, the lone pair of electrons on the other NH2 group (i.e.
attached to NH) is not involved in resonance and hence is available for nucleophilic attack on the C = O
group of aldehydes and ketones.
(iii) The formation of esters from a carboxylic acid and an alcohol in presence of an acid catalyst is a
reversible reaction.

RCOOH + R'OH RCOOR' + H2O

Carboxylic acid Alcohol Ester

To shift the equilibrium in the forward direction, the water or the ester formed should be removed as
fast as it is formed.
Q. 12.19. An organic compound contains 69-77% carbon, 11-63% hydrogen and rest oxygen. The
molecular mass of the compound is 86. It does not reduce Tollens’ reagent but forms an addition
compound with sodium hydrogen sulphite and gives positive iodoform test. On vigorous oxidation, it
gives ethanoic acid and propanoic acid. Write the possible structure of the compound.
(CBSE 2008, 2009 ; Assam Board 2017)
Ans. Step 1. To find out the molecular formula of the compound.
% C = 69-77% ; % H = 11 -63%
∴% 0= 100- (69-77 + 11-63) = 18-6%
69−77 11−63 18−6
C:H: O = : = = 5-88: 11-63: 1-16 = 5: 10: 1
12 1 16

.-. The E.F. of the given compound is C5H10O

E.F. mass = 5 x 12 + 10 x 1 + 1 x 16 = 86 Since, Mol. mass = 86 (given)
86
m.f. = C5H10O ×86 = C5H10O
* Thus, molecular formula of the given compound = CsH10O.
Step 2. To determine the structure of the compound
(i) Since the given compound forms sodium hydrogen sulphite addition product, therefore, it must be
either an aldehyde or methyl ketone.
(ii) Since the compound does not reduce Tollens’ reagent, therefore, it cannot be an aldehyde and hence
it must be a methyl ketone.
(iii) Since the compound gives positive iodoform test, therefore, the given compound is a methyl ketone.
(iv) Since the given compound on vigorous oxidation gives a mixture of ethanoic acid and propanoic

acid, therefore, the methyl ketone is pentan-2-one, i.e.,

Pentan-2-one (M.F. C5H10O)

Step 3. To explain the reactions involved in the given question.

Pentan-2-one Sod. hydrogen sulphite addition product

+ 3 I2 + 4 NaOH CHl3 + CH3CH2CH2COONa

Pentan-2-one Iodoform Sod. butanoate

(yellow ppt.
)

+ 3 Nal + 3 H2O
CH3COOH + CH3CH2COOH