NEET - ug

NATIONAL TESTING AGENCY

Chemistry
Organic Chemistry
 NEET - UG
S.NO. CONTENT Page
No.

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3. 41
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8. 207
9. 219
 CHAPTER

1 Haloalkanes and Haloarenes

CHAPTER OUTLINE
 Haloalkanes  CCl4 Or Pyrene (Carbon-tetra-Chloride)
 Teflon (– CF2 – CF2 –)n  Chlorobenzene

HALOALKANES D. Tetrahalides (𝐂𝐗 𝟒 or 𝐂𝐗 𝟐 𝐘𝟐 )

 Haloalkanes are the halogen derivatives of  Tetrahalides are the tetra-halogen
derivatives of alkanes.
hydrocarbons, and their structure is
On the basis of Nature of C-X Bond
determined by the number of hydrogen
(i) Compounds containing sp3 hybridised C − X
atoms they contain.
bond
Classification (a) Alkyl halides or halo alkanes
RCH2 X R 2 CHX R 3 CX
On the basis of No. of Halogen Atoms
1∘ 2∘ 3∘
A. Monohalides (R-X) (b) Allylic halides: Halogen atom is linked to
 As alkyl halides, monohalides are the an sp3 hybridised carbon atom which has
monohalogen derivatives of alkanes with a C = C bond attached to it.
the general formula 𝐂𝐧 𝐇𝟐𝐧+𝟏 𝐗.
 R − X may be of three types:
1. Primary – R − CH2 X
2. Secondary – R2 . CH.X (c) Benzylic halides: The tetrahedral carbon
3. Tertiary – R3 . C.X involved in C − X bond is linked to an
B. Dihalides (𝐂𝐧 𝐇𝟐𝐧 𝐗 𝟐 ) aromatic ring.
 Dihalides are alkanes' di-halogen
derivatives and come in geminal and
vicinal forms.
(ii) Compounds containing sp2 hybridised C − X
bond
(a) Vinylic halides
 The halogen atom is linked to the C=C
bond's sp2 hybridised carbon atom.
Example:
BrCH2 − CH2 − CH2 − CH2 Br
1, 4-dibromobutane (b) Aryl Halides
C. Trihalides (𝐂𝐧 𝐇𝟐𝐧−𝟏 𝐗 𝟑 ) or haloforms  Halogen atom is linked to the carbon
(CHX3) atom of the benzene ring.
 Trihalides are alkane-derived tri-halogen
compounds.

1
Monohalides  The function of ZnCl2 is make cleavage of
 Haloalkanes are monohalides; for instance, −C − O– bond by co-ordination with O-
the IUPAC name for C2H5Br is bromoethane. atom.
 These molecules may exhibit chain, position, Bromoalkanes
and optical isomerisms. C2H5OH + KBr + H2SO4  C2H5Br + KHSO4 + H2O

Methods of preparation
Facts to Remember
By direct halogenation of alkanes
Conc. n H2 SO4 must not be used in case of
R  H  X  X  hv
R  X  HX
s∘ , 𝑡 o , and neo alcohols as they undergo
Example:
dehydration with it.
CH4  Cl2  hv
CH3Cl  CH2Cl2  CHCl3  CCl4
CH3 3 C  CH2OH  HBr 
or 520650K H SO
2
4

 The reactivity order is

F2 > Cl2 > Br2 > I2
R3CH  R2CH2  RCH3  CH4
t s p
From alcohols
 R − OH + PCl5 ⟶ R − Cl + POCl3 + HCl
 3R – OH + PCl3  3R – Cl + H3PO3
 R  OH  SOCl2 
Pyridine
R  Cl  SO2  HCl
Iodoalkanes
It is called Darzen's process. Here, pyridine is
used to reflux gaseous by-products. CH3CH2OH 
KI/H2 SO4
 CH3CH2I  KHSO4  H2O
 R  H  SO2Cl2  R  Cl  HCl  SO2 CH3  CH2OH  HI 
H3PO4
 CH3  CH2I  H2O
Pyridine

Here, Pyridine also reacts with HCl C2H5OH  KI  H3PO4 

 C2H5I  KH2PO4  H2O
Here 57% HI can also be used in place of KI.
Reaction of 𝑅 − 𝑂𝐻 with 𝑃 + 𝐼2 or 𝐵𝑟2
6R − OH + 2P + 3I2 ⟶ 6R − I + 2H3 PO3
By Groove's method 6C2 H5 OH + 2P + 3Br2 ⟶ 6C2 H5 Br + H3 PO3
 R  OH  HX 
Anhy. ZnCl2
R  X  H2O OR
3C2 H5 OH + PBr3 ⟶ 3C2 H5 Br + H3 PO3

 R  OH 
H 
R   H2O
R  OH2  By finkelstein reaction It is specially used for iodo
alkanes preparation using SN 2 mechanism.
R  X  SN1

R X
fast CH3 − CH2 Br + NaI ⟶ CH3 CH2 I + NaBr
 
X  As NaCl, NaBr are insoluble in Acetone so they
 or R  OH2  R  X  H2O SN 2

Slow
are removed by filteration.
 The order of reactivity of HX with alcohols is
Fluoroalkane
HI > HBr > HCl CH3 Cl + AgF ⟶ CH3 F + AgCl
 The order of reactivity of alcohols towards 2CH3 Cl + Hg 2 F2 ⟶ 2CH3 F + Hg 2 Cl2
HX is tertiary (𝐭) > secondary (𝐬) > primary 3CH3 Cl + AsF3 ⟶ 3CH3 F + AsCl3
(𝐩). This reaction is called Swart reaction.
Example: Borodine-Hunsdiecker reaction: It is used
 CH3 3 C  OH  HCl 
  CH3 3 C  Cl  H2O mainly for preparing bromoalkanes from silver
Tert. butyl alcohol Tert. butyl chloride
salts of acids:
 In case of tertiary alcohols, the reaction may CCl4
take place even in the absence of ZnCl2 . RCOOAg + X2 ⟶ R − X + CO2 + AgX

2
 Follows a free radical mechanism and Like in alkanes branching also decrease B.P.
reduces one C atom number.
 The yield of R − X decreases: 𝟏∘ > 𝟐∘ > 𝟑∘ .
 In case of iodine, an ester is formed and the
reaction is called Birnbaum-Simonini reaction.
 The trend followed for the dipole moment of
2RCOOAg + I2 ⟶ R − COOR + 2CO2 + 2Ag 2 I
various compounds is 𝐑𝐂𝐥 > 𝐑𝐅 > 𝐑𝐁𝐫 > 𝐑𝐈
From ethers
CH3 Cl > CH3 F > CH3 Br > CH3 I
R − O − R + PCl5 ⟶ 2R − Cl + POCl3
R − O − R′ + PCl5 ⟶ R − Cl + R′ − Cl + POCl3 𝜇 → 1.86D 1.847D 1.83D 1.636D
From alkenes: HX reacts with alkenes in  The stability of compounds vary in the
accordance with Markovnikov's or following sequence as bond length increases
anti- Markovnikov's to produce haloalkanes in and bond energy decreases.
the following manner: RF > RBr > RCl > RI
 According to Markovnikov's rule:- Solubility
Br  These are less soluble in water because less
|
energy is released when new attractions are
CH3  CH2  CH2  HBr 
CH3  CH  CH3
established between the haloalkane and the
In the event that the carbocation formed is less
mater molecules, because these new
stable, a one-time rearrangement via 1,2-shift of
attractions are not as strong as the original
hydride or methyl is performed.
H-bonds in water.
Example:
 Their solubility in organic solvents is quite
good due to interactions that are nearly
identical.
1
 Solubilities 
Mol. wt.
CH3 X > C2 H5 X > C3 H7 X > C4 H9 X
Chemical properties of monohalides

 According to Anti-Markovnikov's rule:-  Since the C  X is polar, these are reactive
CH3  CH  CH2  HBr 
Benzoylperoxide
 compounds.
CH3  CH2  CH2Br  The reactivity order is as follows:
From primary amines RI > RBr > RCl
R  NH2  NOCl 
R  Cl  N2  H2O R 3 CX > R 2 CHX > RCH2 X
Nitrosyl CH3 X > C2 H5 HX > C3 H7 X > ⋯.
chloride
Nucleophilic substitution reactions: Alkyl
Physical properties of monohalides halides undergo nucleophilic substitution
 Lower members (CH3 X, C2 H5 X) are reactions as:
colourless gases, whereas higher members  
R  X  Z R  Z  X 
(C18 and higher) are colorless liquids. Strong
 The boiling point and density of a substance nucleophile
increase as its molecular weight increases. This reactions occurs by either SN1 or SN2
C4 H9 Cl > C3 H7 Cl > C2 H5 Cl > CH3 Cl mechanism.
RI > RBr > RCl > RF …

3
Examples: Dehydrohalogenation: It involves 𝛼, 𝛽-
 R  X  R  OH  HX
Aq. KOH
elimination following E1 and E2 mechanisms.
 R  X 
AgOH
R  OH  AgX Here, the following, α,β-elimination reaction
takes place:
 R  X 
Alc. KCN
R  CN  KX
R − CN is the major product as KCN being  In the case of t∘and s∘ halides, elimination
ionic, provides CN − ions. Therefore, the predominates over substitution, whereas
attack occurs from the carbon atom side. substitution predominates in the case of p∘
halides. In addition to high temperature and
 R  X  
AgCN
R  NC  AgX
solvent polarity, the strength of the base also
The major product is R − NC as AgCN being
favours elimination over substitution.
covalent cannot furnish CN − ions. Therefore,
the attack occurs from nitrogen atom (lp e-
side) to give R − NC.

 R  X 
AgNO2
R  NO2  AgX
Nitroalkane

 R  X  
KNO2
R  O  N  O  KX
Alkyl nitrite

 R  X 
NaN3
R  N3  NaX
Azides

 R  X  
NASH
R  SH  NaX
Thiols
 R  X 
R'COOAg
R'COOH  AgX
 R  X 
R'ONa
R' O  R  NaX Saytzeff's Rule
The above reaction is called Williamson According to Saytzeff's rule, the removal of β-
synthesis (Method to prepare all kind of H-atoms from β-carbon atoms with a greater
ethers. (R − X must be p∘ or s° halide). number of alkyl groups results in the
R  X  R'SNa
R' S  R  NaX formation of a more stable alkene.
 C2H5OH/H2O
Thioether
Example:
 R  X R  S  R  2NaX
Na2S
CH3  CH  CH2  CH3 
KOH
 CH3  CH  CH  CH3
 R  X C6H6
C6H5  R  HX | But 2  ene major
Anhyd. AlCl3
Cl
The above reaction is called Friedel-Crafts CH2  CH  CH2  CH3
reaction. minor

R  X 
R  OH
Moist Ag2O

2R  X  Ag2O 
R  O  R  2AgX

Dry Ether In the case of a fluoro-alkane or other s o halide
 R  X  NaC  CR' 
R  C  C  R' NaX reacting with a very strong base, such as
Alkyne (CH3 )3 COK or C2 H5 ONa, the predominant
X R
R  X 
NH3
HX
R  NH2 
HX
 product (Alkene) is determined by the
p Hoffmann Rule. According to this theory, 𝜷-H-
atom is eliminated from 𝜷-C-atom with less H-
atom or less acidic 𝜷-H-atom, resulting in less
stable alkene.

4
 
Dihalides
CH3  CH  CH2  CH3 KOH
Always
 CH2  CH CH2  CH3
Hoffmann Major
| Gem or geminal halide or alkylidene halides
F 
CH3  CH  CH  CH3
Minor

 CH 
CH3  CH  CH2  CH3   CH2  CH  CH2  CH3
3 3 COK

| Major
Methods of preparation of geminal halides
X  1. From aldehyde or ketone
CH3  CH  CH  CH3
Minor

Reaction with Metals

(a) Reaction with Na (Wurtz reaction)
R  X  2Na  X  R 
Dry ether
R  R  2NaX
(b) Reaction with Zn (Frankland reaction)

R  X  Zn  X  R R  R  ZnX 2
2. From alkyne
(c) Reaction with Mg
R  X  Mg 
Dry ether
R  Mg  X
Grignard reagent

R may be CH3 , C2 H5 , C6 H5 etc.

Reactivity order for R − MgX can be given as
R − I > R − Br > R − Cl
CH3 X > C2 H5 X > C3 H7 X >
 Alkene is the main product of R 3 CX only in
the case of iodide.
 Here, ether molecules coordinate with ether
as crystallisation ether.
(d) Reaction with lead sodium alloy Chemical properties of geminal halides
4C2H5Br  4Pb Na   C2H5 4 Pb  4NaBr  3Pb (Alkylidene halides)
Tetraethyl lead These are less reactive than alkyl halides
 Tetraethyl lead (TEL) is an anti-knocking because the presence of a single X-atom (E.W.G)
substance used in petrol to avoid knocking. makes the replacement of additional X-atoms
(e) Reaction with lithium slightly hard.
R  X  2Li 
Ether
R  Li  LiX 1. Reaction with alcoholic KOH
Reduction
R  X  2[H] 
Li AlH4
or Zn/HCl
R  H  HX
R  X  2HI 
Red P
R  H  LiX

Heating effect 2. Reaction with aqueous KOH

560C
R  CH2  CH2  R  CH  CH2  HX Here, R-CHO, R-CO-R are formed

Isomerination

5
3. Reaction with KCN
3.

Trihalides or Haloforms (𝐂𝐇𝐗 𝟑 )

Chloroform (𝐂𝐇𝐂𝐥𝟑 )
 Chloroform was discovered by Justus von
Liebig and named by Jean-Baptiste Dumas.
4.  Its anaesthetic nature was discovered by
James Young Simpson.
Vic or vicinal dihalide or alkylene halides Methods of preparation
1. From chloral
Δ
CCl3 CHO + NaOH ⟶ CHCl3 + HCOONa
2. From ethyl alcohol or acetone
Methods of preparation of vicinal dihalides Ethyl alcohol or acetone reacts with
1. From diols like glycol bleaching powder to give chloroform:
CH2Br CH2Br
3| 3H3PO3   3|  3H3PO3
CH2Br CH2Br
CH2OH 
2HCl
2H2O
 CH2Cl
| |
CH2OH CH2Cl
2. From alkenes
CH2 Br CH2Br
||  |  |
CH2 Br CH2Br

Chemical properties of vicinal dihalides

1. Reaction with KOH
CH2  Cl 3. From CCl4

| 2KOH  HC  CH  H2O  2KCl
Ethanol CCl4  2[H] 
Fe/H2O
 CHCl3  HCl
CH2  Cl
4. From chloral hydrate
CH2Br CH2OH

|  2KOH  |
CH2Br CH2OH
Glycerol  Chloral hydrate is stable due to
2. Reaction with KCN intramolecular hydrogen bonding in it
(butterfly-like structure).

5. Haloform reaction
(A) It is given by >C = O having –COCH3 group.
For example,

6
  This substance is insoluble in water, but
soluble in organic solvents. Additionally, it
is a useful solvent for lipids, resins, etc.
CHBr3
 It is a colourless liquid and its boiling point
is 149.5∘ C.
CHI3
 It occurs as yellow, hexagonal plate like
crystats.
 Its melting point is 119∘ C.
 It can be used as an antiseptic (due to the
 CH3CHO is the only aldehyde to show the liberation of free I2 ).
reaction.
Test of Purity of CHCl3
For example,
No precipitate is produced when chloroform
and silver nitrate react. Due to the fact that
CHCl3 is covalent, it cannot provide Cl-ions.
Chemical properties of chloroform (𝐂𝐇𝐂𝐥𝟑 )
1. Nitration
 CH3CHO + 3I2 + 4NaOH CHI3  + HCOONa +
CHCl3  HO  NO2 
CCl3 .NO2  H2O
3NaX + 3H2O
Chloropicrin (insecticide)
 CH3COCH3 + 3I2 + 4NaOH  CHI3  +
 It is used in the manufacture of tear gas
CH3COONa + 3NaX + 3H2O
[C6 H5 COCH2 Cl], phenacyl chloride.
(B) Alcohol having CH3  CH  OH group shows 2. Reduction
| 6[H]Zn  H2O
CHCl3   CH4  3HCl
haloform reaction.
CHCl3   CH2Cl2  HCl
2[H]Zn/HCl

Example:
CHCl3  4(H)  Zn
CH3Cl  2HCl
alc. HCl

3. Oxidation
1
CHCl3  O2 
hv
 COCl2  HCl
2 Phosgene
(poisonous)
 To prevent oxidation or the formation of
phosgene, chloroform is stored in a dark,
completely filled, securely sealed bottle with
a small amount of ethyl alcohol (a negative
For example, catalyst).
CH3 – CH2 – OH + 4I2 + 6NaOH  CHI3  +  Phosgene is converted to non-poisonous
HCOONa + 5NaX diethyl carbonate by ethyl alcohol.
CHCl3
 It is a colourless liquid with sweet smell.
 Its boiling point is 61∘ C.

7
4. Reaction with hot NaOH 𝐂𝐂𝐈𝟒 OR PYRENE (Carbon Tetra-Chloride)
Cl
|
Cl  C  Cl
|
Cl
5. Reaction with hot C2H5ONa
 Tetrahedral structure
 sp3 hybridization
 Bond angle 109∘ 28 ′
 𝜇 is zero
6. Carbylamine reaction: It is a test of primary
amine. Here, the primary amine reacts with Methods of preparation
chloroform and base KOH, to give bad 1. CH4  4Cl2 
hv
CCl4
4HCl

smelling isocyanide as follows: 2. CH4  4Cl2 

hv
CCl4
4HCl

R – NH2 + CHCl3 + 3KOH  R – NC + 3KCl + 3H2O 3. CS2  2S2Cl2 

 CCl4  6'S'
 Here, the reaction intermediate is: CCl2 , that 
4. C3H8  9Cl2 
70 100 atm
CCl4  C2Cl6  8HCl
is, dichlorocarbene. Solid
 If ethylamine is taken, the product formed is Physical properties of pyrene
ethyl isocyanide.  It is a poisonous, colourless, noncombustible
C2H5NH2 + CHCl3 + 3KOH  C2H5NH + 3KCl + liquid with a boiling point of 350K.
3H2O  It is insoluble in water but soluble in organic
 If aniline is taken, the product formed is solvents and is an excellent fat, oil, and
phenylisocyanide. paraffin solvent.
C6H5NH2 + CHCl3 + 3KOH  C6H5NC + 3KCl + Chemical properties of pyrene
3H2O 1. Reaction with steam
7. Reaction with Ag powder CCl4  H2O
500C under high pressure
COCl2  2HCl

CHX3  6Ag  CHX3  C2H2  6AgX 2. Hydrolysis
8. Reimer-Tiemann reaction: CCl4  
Boiling KOH
C  OH4 
2H2O
CO
Here reaction inter mediate is: CCl2. 3. Reaction with HF
CCl4  2HF 
SbF5
 CF2Cl2  2HCl
Freon
 Freon-12 is used in refrigerators and air
conditioners as a refrigerant.
4. Reaction with phenol

9. Reaction with acetone

 Chloretone is used in hypnotic medicines.

8
Uses of CCl4: From benzene diazonium chloride or Sand
(i) As a solvent for oils, fats, Resins etc. Mayer's reaction
(ii) Under the pyrene it is used as a fire
extinguisher.
Teflon (– CF2 – CF2 –)n Gatterman reaction
 Teflon is a polymer of tetrafluoroethylene.
 It is a thermoplastic that is chemically inert
and used for electrical insulation and gasket
Physical properties of Chlorobenzene
materials.
800C
 It is a colourless liquid with a pleasant odour
CHCl3 
SbF3
CHF2Cl 
HCl
CF2  CF2
HF
and a boiling point of 132∘ C.
  CF2  CF2  n
nCF2  CF2   It is heavier than water and insoluble in it.
Tetrafluoroethylene Teflon
Chemical properties of Chlorobenzene
Chlorobenzene Due to benzene ring
Methods of preparation  The Cl-atom present in the ring renders the
ring inactive, but it is both o- and p-directing.
Electrophilic substitution occurs at a slower
rate than benzene.
Here, the electron (e–) density increases at the o
From benzene
and p positions due to resonance, but the -X
atom tends to withdraw electrons from the
benzene ring due to the -I effect. It indicates that
the rate of electrophilic substitution decreases
due to ring deactivation.
cannot be obtained by direct

iodination as not only the reaction is reversible

but also HI being a reductant can reduce

into Benzene. But if strong oxidants like  Halogenation

HNO3, HgO are used the reaction is possible as

they oxidise HI into I2.

cannot be obtained as F is highly

reactive and the reaction is violent also.

 Commercial method or Raschig method  Nitration

From alcohol

9
 Sulphonation  Substitution by-OH group

 Friedel Crafts Alkylation

 Acylation

When a strong Electron Withdrawing Group

(E.W.G) group, such as -NO2, is present at the o,
Here para product is major in all these cases. p position, the substitution of -X becomes
considerably easier and a reaction takes place.
Reactions due to chlorine
 Reactivity of chlorine atom in chlorobenzene
Cl-atom in chlorobenzene is much less reactive
than R-X because C-Cl bond in chlorobenzene
has a double bond character and is resonance
stabilised, requiring more energy to break a
double bond than a single bond.

sp3
In while in R  CH2  X it means  Substitution by NH2 group

in haloarenes C − X bond length is shorten than

in haloalkanes which is 169 and 177PM
respectively. It also decreases reactivity in

haloarenes. Here is very less stable so

SN1 reaction does not occur. The attack of e− rich

Nu− is also inhibited by higher e density at
arenes.

10
This reaction proceeds with Benzine Uses and Effects of Polyhalogen Compounds
on Environment and Human Health
formation. (i) Chloroform
 It is used primarily in the production of
 Substitution by CN group
the R-22 Freon refrigerant and as a
solvent for lipids, alkaloids, iodine, etc.
 Substitution by –OR group  It results in dizziness, headache, and
fatigue.
 Chronic chloroform exposure can
 Reaction with magnesium result in liver and kidney injury.
(ii) Iodoform
 It is primarily employed as an
antiseptic because it releases free
 Wurtz Fittig Reaction iodine.
 However, it is no longer used due to its
foul odour.
 Fittig reaction
(iii) Freon
 Freon is used as a refrigerant in
refrigerators and air conditioning
units.
 However, its use has been
discontinued because it depletes the
 Ullmann reaction
ozone layer.
(iv) DDT
 DDT, a popular pesticide consisting of
an off-white crystalline substance, is
exceedingly toxic to fish.
 Reaction with chloral  It is not swiftly metabolised by
DDT is produced when chloral is heated with animals; instead, it is deposited and
chlorobenzene in the presence of retained in fatty tissues.
concentrated H2SO4 (p, p-dichlorodiphenyl  Since its residues are non-
trichloroethane). Due to the fact that both biodegradable, they accumulate in the
Cl-atoms are linked to the benzene ring, it is environment and are toxic to
not biodegradable. mammals, etc.
(v) Carbon tetrachloride
 CCl4 or carbon tetrachloride is
primarily employed in the synthesis of
chloroflourocarbons.
 It may induce human liver cancer.
 It may result in migraines, nausea, and
nerve injury.
 It may contribute to the depletion of
the ozone layer.

11
(vi) Benzene Hexachloride (B.H.C)
12. The order of chemical reactivity of alkyl
 It is commonly called as Gammexene
halides is
or 𝛾-Lindane or 6,6,6[C6 H6 Cl6 ]. RI > RBr > RCl
It is a popular pesticide for killing of 13. The order of reactivity of an alkyl halides
Thermites (white ants) from soil. is
Tertiary > Secondary > Primary
Facts to Remember This is due to the inductive effect of alkyl
1. As a treatment for hookworms, CCl4 is groups, which increases the polarity of
used as a medication. the C-X bond, making it more reactive.
2. CFCl3 is freon-11, while CF4 is freon-14, 14. Despite their higher positive ionisation
CF3Cl is freon-13 and CF2Cl2 is freon-12. energy, it has been observed that the
presence of bulky groups in primary
3. Perfluorocarbons have a standard
halides causes steric hindrance and
chemical formula- C𝑛 F2n+2.
makes them less reactive towards the
C6H14  14F2 
573K, COF2
C6 F14  14HF SN2 mechanism.
4. Halothane (CF3CHClBr) is employed as The reactivity follows the order CH3 X >
an inhalational anaesthetic. C2 H5 X > C3 H7 X.
5. Chloretone is a substance that induces 15. Antiseptic action of CHI3 is due to the
hypnosis or sleep. liberation free I2 .
6. Westron is composed of 16. Perfluoro carbons (PFCs) have a general
formula Cn H2n+2
tetrachloroethane while Westrosol is  573K
C7H16  16F2 
Vapour Phase N2C0F2
 C7F16  16HF
trichloroethylene. Perfluoro heptane
 CHCl2  These substances are odourless, non-
|  Westron polar, stable, and non-toxic. They are
 CHCl 
 2 resistant to U.V and other types of
 CCl2  radiation, so they do not deplete the U3
 ||  Westrosol layer. They can be utilised as lubricants,
 CHCl 
  in skin-care medications, in medical
7. The boiling point have the following diagnosis, etc.
order: 17. Halogen derivatives of aromatic
Alkyl iodides > alkyl bromides > alkyl hydrocarbons with a halogen atom in
chlorides > alkyl fluorides the side chain are known as aryl alkyl
halides or aralkyl halides.
R − I > R − Br > R − Cl > R − F
Examples: Ar − CH2 − X.
8. The volatility has the following order:
18. Bond strength and stability decreases as
R − Cl > R − Br > R − I
R − F > R − Cl > R − Br > R − I
9. Dipole moment has the following order: 19. The relative nucleophilicity order for
CH3 Cl > CH3 F > CH3 Br > CH3 I SN 1 Reaction:
10. The order of the boiling points in a RS̅ > C̅N > I̅ > R − O̅>O ̅H
group of isomeric alkyl halides is 20. The leaving group tendency for SN 2
Primary > Secondary > Tertiary Reaction:
11. The order of the densities of alkyl p  CF3C6H5SO3  p  CH3C6H4 SO3  I  Br 
Tf Ts
halides is
 Cl  H O  F  CH3COO  NR3  R  O
  
R − I > R − Br > R − Cl > R − F 3

CH3 Cl < CH2 Cl2 < CHCl3 < CCl4  R2N  NH2

12
 (R) : Reactivity depends upon the
21. Decreasing order of Reactivity of
Nucleophilic Substitution Reaction: nature of the nucleophile and the
solvent.
5. (A) : Isopropyl chloride is more reactive
than CH3 Br in SN2 reactions.
(R) : SN2 reactions are always
accompanied by inversion of
configuration.
6. (A) : o-dichloro benzene has higher
metlting point than p-dichloro-
benzene.
22. R-Br and R-I cannot be derived using (R) : Stronger the Van der Waal's forces
Dorzen's approach since SOBr2 is
of attraction, higher is the melting
unstable and SOI2 does not exist.
point.
NEET AND AIIMS ESSENTIALS 7. (A) : Addition of Br2 to cis-but-2-ene is
stereoselective.
In the following questions, two statements
Assertion (A) and Reason (R) are given. Mark (R) : SN2 reactions are stereospecific as
(a) if 𝐴 and 𝑅 both are correct and 𝑅 is the well as stereoselective.
correct explanation of 𝐴 8. (A) : SN2 reaction of an optically
(b) if 𝐴 and 𝑅 both are correct but 𝑅 is not the activealkyl halide with an aqueous
correct explanation of 𝐴 solution of KOH gives an alcohol
(c) 𝐴 is true but 𝑅 is false with opposite sign of rotation.
(d) A is false but 𝑅 is true (R) : SN2 reactions proceed with
(e) A and R both are false inversion of configuration.
1. (A) : The effect of electron withdrawing 9. (A) : Benzyl chloride is more reactive
group at ortho and para position than p-chlorotoluene towards
increases the reactivity of aqueous NaOH.
haloarenes but at meta position (R) : The C − Cl bond in benzyl chloride
(R) : As at meta position negative charge is more polar than C − Cl bond in p-
can not be stabilized by such a chlorotoluene.
group in any resonating structure 10. (A) : Tertiary haloalkanes are more
2. (A) : Alkyl iodides darken on standing. reactive than primary haloalkanes
(R) : Alkyl iodides are prepared by
towards elimination reactions.
Finkelstein reation.
(R) : The +I-effect of the alkyl gropus
3. (A) : 2-chloro-3-methylbutane on
weakens the C − X bond.
treatment with alcoholic potash
11. (A) : Rate of reaction is dependent only
gives 2-methyl-butene-2 as major
on the concentration of
product.
nucloephile in SN1 reactions.
(R) : The reaction occurs according to
(R) : Polar solvent favours SN1 reaction.
Saytzeff rule.
4. (A) : Primary benzylic halides are more 12. (A) : The carbon halogen bond in an aryl
reactive than primary alkyl halides halide is shorter than the carbon
towards SN1 reactions. halogen bond in an alkyl halide.

13
 (R) : A bond formed of an sp3 orbital (R) : Front side attack of nucleophile is
should be shorter than the hindered due to the presence of
corresponding bond involving an leaving group in the vicinity.
sp2 orbital. 15. (A) : Bromobenzene upon reaction with
13. (A) : SN2 reaction of CH3 − Br is faster in Br2 /Fe gives 1, 4-dibromobenzene
DMSO than in H2 O. as the major product.
(R) : DMSO has greater capability to (R) : In bromobenzene, the inductive
solvate nucleophile. effect of the bromo group is more
14. (A) : In SN1 mechanism, the product dominant than the mesomeric
with inversion of configuration is effect in directing the incoming
obtained in higher amount electrophile.
compared to the product with the
retention of configuration.

ANSWER KEY

1. (a) 2. (c) 3. (a) 4. (b) 5. (d) 6. (d) 7. (b) 8. (a) 9. (a) 10. (b)
11. (d) 12. (c) 13. (c) 14. (a) 15. (c)

14
 CHAPTER

2 Alcohols, Phenols and Ethers

CHAPTER OUTLINE
 Alcohols  Ethyl Glycol
 Glycerol or Glycerine  Phenols
 Ethers (R–O–R)  Epoxy Ethers

ALCOHOLS
 Alcohols are hydroxy derivatives of alkanes or alkyl derivatives of water obtained by replacing one
or more H atoms by –OH group.
 General formula of the alcohol is 𝐑 − 𝐎𝐇.
Types of Alcohols
Monohydric alcohols Dihydric alcohols Trihydric alcohols
Alcohols with only one −OH Alcohols that have two-OH groups. Alcohols having three −OH
group with their general groups
formula Cn H2n+1 OH
Types of Monohydric Alcohol Example: Example:
(a) Primary alcohol (1°) Glycol, Propan 1, 2 diol
RCH2OH
Example: CH3 OH methyl
alcohol (Methanol)
(b) Secondary alcohol (2°)
R2CHOH
Example: (CH3 )2 CHOH
isopropyl alcohol (Propan-
2-ol)
(c) Tertiary alcohol (3°) R3C.OH
Example: (CH3 )3 COH −
tertiary butyl alcohol (2-
methyl-propan-2-ol)

Nomenclature of Alcohols  Replace 'e' in the name of alkane with ‘ol’ to

 The common names of alcohols are derived form the IUPAC name for alcohols. Thus, it is
by adding the word alcohol to the common an alkanol, such as
name of the alkyl group, such as CH3OH for CH3 – CH2 – CH2OH Propanol
methyl alcohol or methanol. CH3  CH  CH3 Propan-2-ol
|
OH

15