Fundamental concepts

of organic reaction
mechanisms
Organic reactions take place by the attack of a reagent on a compound (substrate) to
give the products. During these reactions, substrate provides at least one C atom for
the formation of a new bond. It is always an organic molecule. The bonds of substrate
are cleaved into fragments called reaction intermediates which are transitory and
immediately react with other species present, leading to the formation of new bond. It
can be represented as
Reagent
Substrate -------+ [Reaction intermediate] ➔ Products
The logical sequencing of steps involved in cleavage of a bond and formation of a new
bond leading to the formation of final products called reaction mechanism. It tells us
how reactants are transformed into products.
Information provided by an organic reaction mechanism
(i) Bond cleavage in substrate and bond formation in product.
(ii) Individual steps involved in the chemical process.

X~Y~ Z+W
(iii) Reaction intermediates formed during the reaction.
(iv) Energetics and relative rate of each step.

~ Bond cle_
avage (fission)
~lie V in covalent bond
JIMi cleav (f'
~tova) age 1ssion)
:L entbond The organic reactions begin with the breakage of covalent bond. There are following
"tents two possible ways by which a covalent bond can be broken.
;~tion·
!~. liltennediates Homolytic cleavage or symmetrical fission
:"(trollic d'
.~otg~ !Splacements When a covalent borid between two elements break in such a way that each atom
'lrries clllolecules
of org . takes away its own electron of ~hared pair, the cleavage is called homolytic and the
anic reactions phenomenon is called homolysis.
I
•
~~
C
....... ---- -~ .1~· '-.. ; ... - ~
"' -
p-· ~J .
Chapter 19 : Fundamental concepts of organic reaction mechanism s 0 3
60 OBJECTIVE CHEMISTRY Vol. 1
The favourable factors for heterolysis are
The reaction of an electrophile with a nucleophile is the
(i) This type of '.issi~n usually takes place Wh ophileS . same as the reaction of a Lewis acid with a Lewis base
The species generated after homolysis are called free
bond is polansed 1.e. a polar covalent b en the Nude hile means nucleus loving. It is an electron
and is termed as Lewis acid-base association reaction.
radicals. . . II ul ond. .,, rd nucleothp t attacks on electron deficient areas.
This poIansat1on usua y res ts due to th v,O ecies a As a result of this association reaction, each atom in the
CfiirCH3 Light/heat ➔ CH3 +CH3 difference -i n electronega tivities of the atoe ·' . rich P
5
egatively charged ions, e.g. ff,cr ' Br- ' n- , product completes its octet and completion of the octet
e.g. be n
the bonds. Thus, greater the difference b ms fol'llting 'j'hese ca.D olecules with the tendency to donate electron provides the major driving force for this type of Lewis
rnv:;"rNH2 Light/heat ➔ CH3 +NH2 electronega tivities, stronger the tendencyetween
of th
eutral rn •• .. •• •• acid-base reaction.
. all e honi or JI ·s bases, e.g. NH3, RNH2 , ROH, R SH, etc.
•• ••
to break heterolyt1c y. . LeW1 The formation of a chemical bond is described by a "flow"
In the equations, arrows with half of an arrow-hea~ is pail, 1.e.
used to show the movement of a single electron (F1shook (ii) Presence of polar solvents and low temp of electrons from the electron donor (Lewis base) to the
favours heterolysis. erature electron acceptor (Lewis acid). This "electron-flow" is
notation). The free radical generated contains a high .
energy unpaired electron called odd electron. It is the
Ambiphiles indicated by a curved arrow drawn from the electron
[ecules that behave like both electrophile and
same electron which was present in covalent bond. Application fbelllO bile are calle d amb'1philes. Generally an organic source to the electron acceptor.
Heterolytic cleavag_e takes pl~ce in p~esence of polar
:.7· f
The factors which favour homolysis are . . a mu1tip
nucIeopund containmg . 1e bond between' carbon and
covalent b_ond. V ar1ous orgaruc reactions are initiated b . electron source • •F• •
(0 Zero or small difference in electronegativity cornpo . t t b'1 hi!
between two atoms (elements) of covalent bond this cleavage. These reactions are called as polar reacJ0 a rnore electronegat ive a om ac as an am p e. •• I
,s+- ~ ,s+- ~ --➔ F
:F-B-F
favours homolysis.
Some of the examples of polar organic reactions are 11l
H"-
AC-9.· CH3-C=N -
0
:F.
••
1 •
B-F:
I
••
•• •• I
(iO Presence of non-polar solvents such as CCl4 , CS 2,
favours homolysis.
(i) Electrophili c addition reactions of alkenes and
alkynes. H~ T I I
Electrophilic Nucleophilic
: : :. . r F
Newly formed bond
Electrophilic Nucleophilic electron deficient atom
(iiz1 Reactions taking place in gaseous phase favours (ii) Electrophili c aromatic substitution . part part part part
homolysis. (iiz) SN 1and SN 2 reactions. Table 19.1 Electrophil es,nucleoph iles and ambiphiles
(iv) Presence of peroxide, UV light, high temperature (iv) El and E2 reactions. Nucleophilicity and basicity
(~ 500° C), electricity and free radical initiators, i.e. Charged
Nucleophilicity and basicitY are interrelated terms but rhey a re
Neutral
pre existing free radicals also favours homolysis. me m e e e fundamentally different Basicicy is a measure of how readily an
so,, BeCI2, BF3, AJC1 3, FeCl3 , H, X (Cl, Br, I, halonium), H3 0
., ., atom donaces its electron pair co a procon whereas nucleophilicitY
Application
As we know homolysis usually requires the bond to be
non-polar. Various organic reactions are initiated by
~ Reagents
,'WCl,>C= 0, :ccl 2 (carbene)
:N-COOC 2 H5 (nitrene)
(hydronium), N 0, (nitronium), N 0
..
(nitrosoniwn), .,
is defined as the ability of the nucleophile to displace the similar
group from the substance.
• If the nucleop hilic atoms are from the same period of the
periodic table, then the basicity and nucleophilicicy follow the
C6 H5 N2 (diazonium), CH3
homolytic bond cleavage. These are known as non-polar
The species or compound which attacks on a substrate (carbocation) same order as shown below,
reactions. Some of the important examples of non-polar
reaction are molecule and bring about a chemical change is called a e ee e e ee e.g
NH,, H,O, ROH, RNH 2, R 2NH, NH, H, CN. OH,RNH, R,N, N3 , H,0 < NH 3
reagent. A reagent may be an organic or inorganic R,N. ROR, H2S e e e ,e e 9
CH.PH~ H,0 < CH[:0, <CH.p
9
~ QH
9
(0 substitution reactions of alkanes.
molecule or a part of them, e.g. Na OH, Na in liqui~ NH 3,
. [ ."' l
RO,.OC00,RCOCH2,S , HS
Increasing base strength
(i0 anti-Markownikoff's addition to alkenes. RMgX etc. These are generally involved in a reacuon increasing nucleophile strength
(iiz1 allylic substitution in alkenes. through either homolysis, or heterolysis. k ROH, HOH, RPH,, • Nucleophile strength increases while basic srrengrh
_,;, ·• ~ H 30 or H-t-H decreases down a column of the periodic table (in solve nts
(iv) formation of benzene hexachloride from benzene. Through homolysis, free radicals are formed which wor as Electrophile chat can have hydrogen bond, such as wate r and alcoh ols).
Nucleophile
attacking species for free radical reaction. f
db ht ro/ysis o a e.g. e e
Heterolytic cleavage or .
Th e two attacking species that are forme ~ e e RO<RS
NucI~ophiles attack electrophile s during the course of the
asymmetrical fission reagent are given in Table 19.1. reaction. R3 N<R 3 P
e e a e
In this cleavage a covalent bond between two elements F <Cl <13r < I
breaks in such away that both the electrons of the shared Electrophiles . electron I~ . I
pair are taken away by one of the bonded atoms. The · . It 1s an -c: + E+ - -C-E Increasing nucleophile strength
Word 'electrophiles' means electron lovm~- h areas, These I I . decreasing base strength
phenomenon of such a fission is called heterolysis. deficient species that attacks on electron f c + Br+, etc,
1 Sreric bulh decreases nucleophilicity.
Heterolytic fission is usually indicated by a curved arrow
(..,.-----.,_ r,,) with its head pointed towards shared pair
include positively charged species e.g. H ' f
1 'utral he
Nucleophile Electrophile
H
I
CH 3
I
acceptor, e.g. The electrophiles can be seen in the form O l}(N" 1") etc, 'f Hf:-C-0
9 < H0
9
· es " eJec uon R-~ -R-0-H
molecules also, e.g :cR 2(carbenes), mtr~n acids or Nu,1,0; ; ~ + H+ EB
e.g. /
CH
Stronger nucleophlle
weaner base
ALJ3.._ A+ +B- f\B.._ A- +B+ best example of such molecules are Lewi, Electropbile
H H 3
-- ---- ---- ---~ /
BeClz,
(Bis more electronegativ e) (A is more electronegative ) pair acceptors. I I wea~er nucteo phile
stronger base
(z} The central atom has incomplete octet, e.g. H-N!-➔ B-H
Heterolytic fission results in the formation of a cation and
an anion. These can be called carbocation and
• •• II ~BH3
Nucleophile Electrophile
- I I
B~3, ZnC12 , AJX3, FeX3, CH3, CX2· . l d d-subshe' H H
carbanion respectively if carbon is present and acquire (iz) They can have expanded octet or unfil e
(+) ve or(-) ve charge.
e.g. SnC1 4 , SiC1 4 , PC1 5 , IF7 , etc.
60 OBJECTIVE CHEMISTRY Vol. 1
Chapter 19 : Fundamental concepts of organic reaction mechanisms 0 5
positive char .
Sol. Electrophiles .They have
Reactions of free radical
~ Reaction intermediates
f n+) ge or 1n
octet (or duplet m case o n . They acce ·t conip1
Example 19.1 Using cwved arrow notation, show the formation . calld
" h species PeIeqron.p11.e
e nucleophile Free radicals are short lived, highly reactive species, as
from electron-nc
of reactive intemiediates when the following covalent bonds ,, F s. ¾s
they readily collide with other molecule to pair up
undergo hetero/ytic cleavage.
(a) CH - SCH3
3
(b) CH3CN
..
: F; B
• • ; x.

~~: I
F-BI [f - - Octet of B is inco~ 1
" Pete 1

3/ .
fhe s,Pecies
produced after the cleavage of bonds are call d
•
jnterrnediates.
. are short lived and
Th ese species e
their unpaired electron.
Some of the reactions in which free radicals are involved
(c) CH3 - Cu ••~• F reicll 011 t·ve and hence cannot be isolated. are
Sol. (a) Electronegativity of SCH3 is larger than that of CH3- . I reac I
Thus, electron pair (forming bond) is transferred to SCH3 Cl wgh Y . •nterrnediates are as follows • Halogenation of alkanes
:ci: '[1ie tyP,ca 1r • Addition of HBr to alkenes in presence of peroxide
0. e e • •
:cl: Al
X •
I
Cl-Al [f - - Octet o
f
Al
.
incomplete • Polymerisation of alkenes
CH3 : SCH3 CH3 + SCH3 IS
--i
Carbocation Anion
• • • X
:~1 : I free radicals .
Cl or group of atoms with an odd or unpaired electron is
(b) Electronegativity of CN > CH3 0 An : 0: free radical. It is formed by the homolysis. These are Carbocation
0. e e I call_ ally neutral and very reactive species. Carbon containing chemical species bearing a positive
CH3 : CN - - i CH3 + CN. 0- Se [ - Sulphur carries positive charge due to eJeetIIC ' charge on carbon atom and carry six electrons in its
Carbocation Anion are electron deficient because the central C atom has
I resonance thus, electrophile. valence shell is called carbocation.
(c) Electronegativity of CH > Cu ~e\even electrons. Carbon free radicals are planar chemical
n 90
3 e 0 yi·es i e sp 2-hybridised. Their unhybriclised orbital They are sp 2-hybridised with trigonal planar in shape.
• e
CH3 , Cu --i CH 3 +Cu
Carbanion
9
:B~ Octet of Br is incomplete spec , · •
contains an odd electron.
;'""•,- Empty p-orbital
e
CH3- C= 0 Octet of carbon is incomplete and carbcn ''\: ··· y.7nhybridised orbital
Example 19.Z Classify the following into nucleophiles and carries positive charge : "-~ ~ -- ~--.".'i_~ ~dd electron : Di~ ,y-hybri~ carbon
electrophiles. e/o e
e N( O N0 2 Octet of rtitrogen is incomplete thus electrophile.
C2H50e, l /u'<--;,;:hybrid C-atom
HS,BF3, AI0 3,
(CH3)3N:, S0 3, Brei, Nucleophiles They are rich in electrons or/and carry Types of carbocation
e e e negative charge The carbocations are classified into three types which
CH 3-C=O, : NH 2, N0 2 e Types of carbon free radical are primary (I 0 ), secondary (2°) and tertiary (3°)
C2H50-, (CH3hN:, : NH2 Free fl\dicals of carbon are classified as primary (1°), carbocations, i.e.
Check Point 19] "" 1 .. ;,. J •• •••• •

secondary (2°) and tertiary (3°), i.e.

CH3 CH 2

H
I
CH3 -C·

CH3
CH 3 - C•
I
H
CH 3 - C
I
le
CH3
I
CH3-C e. CH 3 -C
I ,

CH3
le
I
I CH 3
1. Which of the following statements or information is not
conveyed by an organic reaction mechanism?
6. Which of the following organic reaction is not initiated by Ethyl free radical I CH3
H
Is<>propyl
H
Tertiary butyl
hemolytic bond cleavage? 1· CH 3 Ethyl c.arbocation carbocation carbocation
(a) Reaction intermediate involved in the reaction Tertiary butyl free (I' )
12'1 (3°)
(a) Substitution reactions of alkanes Jso-propyl free radical radical (3°)
(b) Energetics of every step (20)
(c) Relative rates of every step (b) Electrophilic addition reactions·
(d) Exothermic and endothermic reactions (c) Allylic substitution in alkenes
Relative stabilities of free radicals
Relative stabilities of carbocation
(d) Formation of benzene hexachloride
2. Which of the following solvent is not suitable for homolysis? (i) The number of alkyl groups attached to the
(a) CC1 4 (b) CS2 (c)" CHpH (d) None of these 7. Which among the following.is not an electrophile? Ii) Total number of alkyl groups attached to the centr~ central C-atom decides the relative stabilities of
3. The factors which does not favour hemolytic fission is (a) ~Hs (b) ~H3 (c) BF3 (d) S03 Catom carrying the odd electron decides the relative alkyl carbocation. The more alkyl gro~ps
(a) Large difference in electronegativity -NO 2 out ol st abi!ity of free radicals. attached, the more stable it is
(b) Presence of non-polar solvents 8. Choose the electrophile generated from HO
The more alkyl groups bonded to the electron deficient H H
(c) Gaseous phase reactions the options given H8 0rd R H
(d) presence of peroxide (a) He (b) NOe (c) NOf ·
3
(d) O C, th e more stable is the radical. The overall er of
I I I H-C.,
I
4. Select the incorrect statement. 'I8s relative stability is as follows: > R-C > R-Cm >
0
(a) Homolytic fission results in the formation of free radicals.
9· Which one of the following series contain electrophl
only? R H H H
R-C'
I I I
(b) Heterolytic fission results in the formation of · I H
Lewis acid and Lewis base. (a) AIC1 3, S0 3, N0 2
Ell
(b) H2O, S03, H3
0' I I I I. R R H
Methyl carbocation
(Least ,t,ble)
(c) Completion of the octet provides a major driving force for the Ell R-C' >R-C' >R-C' > H-C J0 carbocation
(Most st,ble)
Lewis acid-base reaction.
(d) Steric bulky group increases nucleophilicity.
(c) NH 3 , H20, AICl 3 (d) H20, Cl, NH3
ttogiven
I I I I (W The stability of aryl carbocations increases with
10 S · .
· elect the incorrect comparison with respec R R H H
5. Which of the following is not an example of polar organic 3' radical Methyl radical the number of phenyl groups.
reactions? nucleophiles? (. !Most stable) (Least stable)
(a) SN 1 reactions (a) (CH3lJCOe <OH" 10Sirni! l the greater (C H 1JC+ > (C 6 H5 ) 2 Clf' > (C 6 H5 ) ~
6 5
(b) Free radical reactions is ar Y, the more phenyl groups there are,
(b) H20 < NH 3
(c) Electrophilic aromatic substitution ·, the stabil'1sation.
(c) R09 < RSe
(d) Electrophilic addition reaction
(d) R3P < R3N (C5H5)3 c > (C5Hsl2 cH> c6Hs c:H2
 ~
1'!"· ~ L::;F, ,.. -
,r_.,_
Chapter 19 · F d . (s73
60 OBJECTIVE CHEMISTRY Vol. 1
The favourable factors for heterolysis are

· un arnental concepts of organic reaction mechanisms ~

hileS The reaction of an electrophile with a nucleophile is the
( i) This type of fission usually takes pl
The species generated after homolysis are called free . d. I ace Wh
bond is po1anse 1.e. a po ar covalent ho den the ,,
NucleOP bile means nucleus loving. It is an electron same as the reaction of a Lewis acid with a Lewis base
radicals. . . 11 n d nucleothp t attacks on electron deficient areas. and is termed as Lewis acid-base association reaction.
This po lansat10n usua y results due t ·· · '{/of ecieS a As a result of this association reaction, each atom in the
Light/heat ➔ CH +CH3 th
gatively charged ions, e.g. If, er, Br - D-
O
~ n CH e
difference -i n electronegativities of th atolllsf 1 ~ch sp
e.g. CH3 - 3 3 e be ne ' ' product completes its octet and completion of the octet
the bonds. Thus, greater the differen b ol!ning fhese caJl lecules with the tendency to donate electron provides the major driving force for this type of Lewis
NH
CH"';v'" Light/heat ➔ CH3 +NH2 electronegativities, stronger the tend;:c _etween ; utral JJlO •• •• •• ••
acid-base reaction.
2
to break heterolytically. Y of the ~ or ne . bases, e.g. NH3 , RNH2, ROH, R SH, etc.
. Lewis •• ..
In the equations, arrows with half of an arrow-hea~ is pail• 1.e. The formation of a chemical bond is described by a "flow''
used to show the movement of a single electron (F1shook (ii) Presence of polar solvents and low tern of electrons from the electron donor (Lewis base) to the
favours heterolysis. perature
notation). The free radical generated contains a high electron acceptor (Lewis acid). This "electron-flow" is
energy unpaired electron called odd electron. It is the ArnbiphileS . indicated by a curved arrow drawn from the electron
Application Jecules that behave like both electrophile and
same electron which was present in covalent bond.
The factors which favour homolysis are
(1) Zero or small difference in electronegativity
between two atoms (elements) of covalent bond

Heterolytic cleavage takes place in presence of polar

covalent b_ond. Various or?anic reactions are initiated by
this cleavage. These react10ns are called as polar reacti
Some of the examples of polar organic reactions are ons.

Thelrno hi!e are called ambiphiles. Generally, an organic

0uceop . . amul.
und contalillng tip Ie b ond between carbon and
· a t om act as an amb"1phil e.
coznJ>O electronegative
aznore
H°"'- oi- f." oi- o

source to the electron acceptor.

··71 . .
t
electron source •• •F• •• [ F
I
f
~c=r
H
0
favours homolysis. : F. I} - F: - : F - B- F
(ii) Presence of non-polar solvents such as C0 4 , C5 2 , (i) Electrophilic addition reactions of alkenes and
CH3-C==N:
•• • I • •• •• I
favours homolysis. alky nes. I I
Electrophilic Nucleophilic
•~• . F
(ii!) Reactions taking place in gaseous phase favours (ii) Electrophilic aromatic substitution. Electrophilic Nucleophilic
part part electron deficient atom Newly formed bond
part part
homolysis. (iii) SN land SN 2 reactions.
(iv) Presence of peroxide, UV light, high temperature Table 19.1 Electrophiles, nucleophiles and ambiphiles
(2! 500° C), electricity and free radical initiators, i.e. (iv) El and E2 reactions. Nudeophilicity and basicity
Charged
pre existing free radicals also favours homolysis. Neutral NucleophilicitY and basicitY are interrelated terms but they are
EBEBEBEBEB EB Fundamentally different Basiocy is a measure of how readily an
~
S03,Be02, BF3,AICl3 ,FeCl 3 , H,X (Ci Br, I, halonium), H3 0
Application .\COCl,>C= 0 , : (carbene)
CCl 2 El> El>
atom donates its electron pair to a proton whereas nucleophilicity
As we know homolysis usually requires the bond to be
non-polar. Various organic reactions are initiated by
Reagents :N-COOC2 H5 (nitrene)
(hydronium), N 0, (nitronium), N 0
(nitrosonium),
is defined as the abilitY of the nucleophile to displace the similar
group li'om the substance.
., El> • If rhe nucleophilic atoms are li'om the same period of the
homolytic bond cleavage. These are known as non-polar C H N (diazonium), CH3
6 5 2 periodic table, then the basicity and nucleophilicity foll ow the
reactions. Some of the important examples of non-polar The species or compound which attacks on a substrate (carbocation) same order as shown below,
reaction are molecule and bring about a chemical change is called a e ee e e ee e.g.
reagent. A reagent may be an organic or inorganic NH3, H20, ROH, RNH2, R 2 NH, NH3 H,CN,OH,RNH, R,N, N3,
( z) substitution reactions of alkanes. R,IU«)R, H,S H,0 < NH 3
9 9
molecule or a part of them, e.g. NaOH, Na in liqui~ NH3, e e e ,e e 8
CHpH= H,0 < CH:f:0 2 <CH:f:> •OH
l
(ii) anti-MarkownikofPs addition to alkenes. RO,RCOO, RCOCH 2 ,S , HS
RMgX etc. These are generally involved in a reaction Increasing base strength
(iii) allylic substitution in alkenes. increasing nucleophile strength
through either homolysis, or heterolysis. k ROH, HOH, RPH,,
(iv) formation of benzene hexachloride from benzene. • Nucleophile strength increases while basic strength
Through homolysis, free radicals are formed which wor a.I / ""'--. H3 0.. or !'. H
[ H-i- decreases down a column of the periodic table (in solven ts
{ N0<leophile Electrophile
attacking species for free radical reaction. that can have hydrogen bond, such as wa ter and alcohols).
Heterolytic cleavage or Th e two attacking species that are forme d b!Y Ize
tero/ysis o o
e.g. e e
asymmetrical fission reagent are given in Table 19. 1. Nucleophil es attack electrophiles during the course of the RO<RS
,~
reaction.
In this cleavage a covalent bond between two elements R3 N<R 3 P
breaks in such away that both the electrons of the shared e e e e
pair are taken away by one of the bonded atoms. The
Electrophiles . an e1ectr00 I F<Cl <Br < I
phenomenon of such a fission is called heterolysis. Word 'electrophiles' means electron Iovin · g: It 1s
h areas, 'fhese -c: + E+ - -C-E Increasing nucleophl\e strength
Heterolytic fission is usually indicated by a curved arrow ~eficient species that attacks on electron ; 1ccl+, Br+, etc, I I decreasing base strength
l'lucleophile
Electrophile ·steric bulh decreases nucleophilicity.
( ~ ~ ) with its head pointed towards shared pair mclude positively charged species e.g. H 'f qizutral fhe H
acceptor, e.g. The electrophiles can be seen in the form O (N R), etc- CH3
molecules also, e.g :CR 2(carbenes), nitr~~:~ids or elect!00
I I
AL1---tA++B- f\B---tA-+B+ •--o-H
n •~ + H+ -
R-0-H e.g. HJ:--C-0
8 < H0
9
best example of such molecules are Lewi Nucleophile Electr ophile al I Stronger nucleophlle
(Bis more electronegative) (A is more electronegative) aeClv H H CH3 weaher base
-
pair acceptors.
Heterolytic fission results in the formation of a cation and (
z,, The central atom has incomplet;. 0 ctet, e.g. I I weaher nucleophile
an anion. These can be called carbocation and
~BH3
H- N :-➔ B- H stronger base
carbanion respectively if carbon is present and acquire •
B,l-I3, ZnC1 2 , AIX3 , FeX3 , CH3, CX2 • . d d-sub5hel1, Nucleophile El ectrophile I I
(+) ve or (-) ve charge. (ii) They can have expanded octet or unfi 11 e H H
e.g. SnC1 4 , SiC1 4 , PCJ 5 , IF7 , etc.
 r;.,
60 OBJECTIVE CHEMISTRY Vol. 1
Chapter 19 : F nd
u amental concepts of organic reacti'on mechanisms ~3

The favourable factors for heterolysis are

The species generated after homolysis are called free The reaction of an electrophile with a nucleophile is the
· (i) This ~ype of tissi~n usually takes place cieophiles . same as the reaction of a Lewis acid with a Lewis base
radicals. bond 1s polarised 1.e. a polar covalent b When lhe NU ucleophile means nucleus lovmg. It is an electron
0
nd. word 11 • s that attacks on electron deficient areas and is termed as Lewis acid-base association reaction .
This polarisation usually result d
e.g. ~CH3 Light/ heat ➔ CH3+CH3 . bspecie . As a result of this association reaction, each atom in the
difference 4n electronegativitie: 0 ~;hto the nc be negatively charged ions, e.g. ff Br - 0 - er product completes its octet and completion of the octet
the bonds. 1:h~~• greater the difference atollls foflli,
C~NH2 Light/ heat ) CH3+NH2 fhese c: molecules with the tendency to do~ate ,elec:ron' provides the major driving force for this type of Lewis
electronegativ1t1es, stronger the t nd e between"i orreutr •• .. •• ••
In the equations, arrows with half of an arrow-head is to break heterolytically. e ency of the ilir.J acid-base reaction.
. . Lewis bases, e.g. NH3, RNH 2 , ROH, R SH, etc.
used to show the movement of a single electron (Fishook pair, i.e. •• •• The formation of a chemical bond is described by a "flow"
(ii) Presence of polar solvents and low t
notation). The free radical generated contains a l:righ favours heterolysis. emperature of electrons from the electron donor (Lewis base) to the
energy unpaired electron called odd electron. It is the electron acceptor (Lewis acid). This "electron-flow" is
same electron wl:rich was present in covalent bond.
Arnbiphiles indicated by a curved arrow drawn from the electron
Application 'fhemolecules that behave _lik: both electrophile and
The factors which favour homolysis are nucleophile are called amb1philes. Generally, an organic source to the electron acceptor.
Heterolytic cleavag_e takes place in presence

T •• f
Zero or small difference in electronegativity
(!) co_valent b.ond. Various organic reactions are ~f_p_olar compound containing a multiple bond between carbon and
between two atoms (elements) of covalent bond this cleavage. These reactions are call d lllltlated by · amore electronegative atom act as an ambiphile. el:Trource
.. I
favours homolysis. Some of the examples of polar org . e as_ polar reactioni
H"' o+
7
. .. amc reactrons are §: o+ o :F, B-F: ---➔ : F-BF -F
(ii) Presence of non-polar solvents such as CO 4 CS .. .. I
(i) Electroph1hc addition reactions of alk .. I
favours homolysis. ' 2•
alkynes. enes and H_JC=r CHrr=r :F:
[
F
(iiz) hReactil·o~ taking place in gaseous phase favours
(ii) Electrophilic aromatic substitution. Electrophilic Nucleophilic Electrophilic Nucleophilic
omoysIS. part part part electron deficient atom Newly formed bond
part
(iv) Presence of peroxide lN Ii ht, 1.., (iiz) SN land SN 2 reactions.
(> 5000 C) I . . ' g rngh temperature
(iv) El and E2 reactions. Table 19.1 Electrophiles,nucleo philes and ambiphiles
p-;e exism:gefr:~~:N'C:d !tfradical initiators, i.e. Nucleophilicity and baslcity
o avours homolysis. Charged
Neutral Nucleophilicity and basicicy are ,merrelated term s but they are

~ Reagents
Application e E9 EB EB e e fundamentally different Bas,rny is a measure of how readily an
. so,, BeCl2, BF3, Al el3, F eCl 3 , 1-1,X(Cl,Br, I, h~onium), H3 O a, atom donates its electron pa1r co a proton whereas nucleophillcity
As we know homolysis usual! RCOCl,>C= 0, :ee12 (carbene)
non-polar. Various organic r Y ~eqwres ~: ~ond to be is denned as the abil1cy of the nucleoph,le to displace the sim,lar
(hydronium), N 0., (nitronium). N 0
homo~ytic bond cleavage. Th:::ti:i::ie lilltiated by :fi-cooc,H5 (nitrene) group from the substance
(nitrosonium),
own as non-polar a, a, , If the nucleoph,lic aroms are from the same period oft he
reactions. Some of the . e6 H 5 N2 (diazonium), C H3 periodic table, then th e basicicy and nucleoph,lic,ty follow the
reaction are unportant examples of non-polar The species o
molecule and r c_ompound which attacks on a substrate (carbocation) same order as shown below,
(i) substitution reactions of alkan reagent. A r bnng about a chemical change is called a e ee e e e e eg.
mole ul eagent may be an organic or inorgamc ~ ,ROH,O, ROH, RNH 2 , R 2NH , N H2 1-1, eN, OH,RNH, R,,N, N3, H,O <NH3
~'.i) anti-Markownikoff's addition t:s~en R,H,S 9 6 0
RM~ e or a part of them, e.g. NaOH, Na in liquid NH3,
J,
29 9
HS CHJ)H = H,0 < CHJ".0, <CHp -oH
(,_,iJ allylic substitution in alkenes. es. Rg, RC0g,RC~ H2,S ,
througt:lt~;ese are ge~erally involve_d in a reaction 1ncreas1ng basesuength
(1v) formation of benzene he hi . homolys1s, or heterolys1s. R" increasing nucleophale srrengch
xac onde from benzene. Thro h

Heterolytic cleavage or
atta i?
homolysis, free radicals are formed which work
free radical reaction.
35 ?~~HOH, RPH, ,
Nucleophile Electrophile
• Nucleophile strength increases whale bas,c strength
decrea ses down a column of the penod,c table 1,n solvent s
[hat can have hydrogen bond. such as w ater and alcoho ls)
Thec mg species for
asymmetrical fission reageti;:t atta:king species that are farmed by hetero/ysis of a e.g. e e
In this cleavage a covalent bond are given in Table l 9. I. Nucieopl11·1es attack electrophiles during the course of th e
reaction_
RO<RS
br~aks in such away that both th betjeen two elements R3 N <R 3 P
a e e e
pair are taken away by one of the e ectrons of the shared Electrophiles I F <C l <Br < I
phenome~on of such a fission is e bonded atoms. The Word 'electro h"J , · . eJeclron _ I.~
Heterolytic fission is usual] . d_called heterolysis deficient s'p ~ 1 es mearu electron loving. It JS an These y• + E+ - C-E Increasing nucleophlle st rengc t,

( ~ ,.,,..----.,.J with its head 3'. 1Il icated by a curved. include posi:~:s that attacks on electron ;ich :rea\ etc, Nucleophile
I decreasing base s.1re ngtt,

acceptor, e.g. pomted towards shared pa:rrow

The electro h" ly charged species e.g. H , Cl , Br i' r----.__
Electrophile
H
·steric bulh decreases nucleophillrny

A ~ - A+ + B - f"\
molecules J
Iles can be seen in the form of llllutra IC ,yhe
R--- ·~ ------,. I
CHa
6
best exampl so/ .g :CR2(carbenes), nitrenes (NR),6~e~1ro1t + H J".-1 - o e < H0
(Bis more electronegative) (~::;~,~ A- + n+ Nu,1~ ; ~ H+ - R- 0-H eg I Stronger nucleophl/e
pair accepto;s~ such molecules are Lewi, acids or 1
Elec trop hile Hm H wea her base
CH 3
!eter_olytic fission results in the form c~ronegative)
~
at1on of a catio weaher nucteoph 1le
aruon. These can be

(+) ve or(-) ve charge.

called
carbanion respectively if carb car~ocation and
on is present
n and
and acquire
(i) The central

(i1)
BH
Tb:•
atom has incomplete octet, e.g.
ZnCl2, AIX3, FeX3, CH3, CX2-
aeCli•

bs1tcll,
Nu,
1
3
Cophlle
+ BH 3
Electrophile
- H-N:-➔ B-H
I I
I I
l su on gerbase

e.g. ~~~r ha~e expanded octet or unfilled d-SU H H

4 ' SiCl4,PCI 5 , IF7 , etc.
 60 OBJECTIVE CHEMISTRY Vol. l Chapter
19
: Fu nd amental concepts of organic reaction mechanisms 05
Sol. Electrophiles They have positive charge or .
Example 19.1 Using cwved arrow notatwn,
. show the formation
of reactive intem1ediates when the following cova en
I t bonds
1
octet (or duplet_in case _of tt+). They acce -1 el ncornp1~,
from elec~r~n-nch sp;c1es called nucleopfue/ctron.p~~ 3l Reaction intermediates Reactions of free radical
Free radicals are short lived, highly reactive species, as
undergo heterolytic cleavage.
.. if.: I
(a) CH3- SCH3
(c) CH3 - Cu
(b) CH3CN
:f.; A Fj [ f--- B
Octet of is inco111plet 3/ . reduced after the cleavage of bonds are called
'[he spee17;t~rmedia tes. These species are short lived and
they readily collide with other molecule to pair up
their unpaired electron.

Sol. (a) Electronegativity of SCH3 is larger _than t

th ofdC~3SCH
Thus, electron pair (forming bond) 1s trans erre 3
:.J:: F e
~•cuo;active and hence cannot be isolated. Some of the reactions in which free radicals are involved
are
:ci: Cl highlY . I intermediates are as follows • Halagenation of alkanes
r,. EB 9
:ci:Ai I ')1ietyP'ca
CH3 : SCH3 ----+ CH3 + sc_H3 Cl-11 [f - - - Octet of Al is inco111pleie • Addition of HBr to alkenes in presence of peroxide
Carbocation Anion
·· :ci: Cl
Free radicals • Polymerisation of alkenes
(b) Electronegativity of CN > CH3 atom or group _of ato~s with an odd or unpaire~ electron is
0
r,. EB 9 . An free radical. It 1s formed by the homolys1s. These are Carbocation
CH3 : CN ----+ CH3 + CN I calledcallas neutral and very reactive species ..
Carhocalion Anion 0 - SEB [ f - - Sulphur carries positive charge due to electn Y Carbon containing chemical species bearing a positive
/ resonance thus, electrophile. e are electron deficient because t~e central C atom has charge on carbon atom and carry six electrons in its
(c) Electronegativity of CH3 > Cu
n e
90 ~ \ even electrons. Carbon free radicals are planar chemical valence shell is called carbocation.
CH3 : Cu----+ CH3 +Cue •• e
:pe~ies, i.e sp 2-hybridised. Their unhybridised orbital . 2
Carbanion :~_r Octet of Br is incomplete They are sp -hybridised with trigonal planar in shape.

:~s~
EB contains an odd electron. , ···-.,-Empty p-orbital
into nucleophiles and CH3- C= 0 Octet of carbon is incomplete and carbon
Example 19.2 Classify the following
electrophiles.
e
N
e(o e
O N 02
carries positive charge

Octet of nitrogen is incomplete thus electrophile.

! <a~ .0
''\,:· ·- ~nhybridised orbital
_v,i~ -~ddelectron
~-hybri~ = ~n
HS,BF3, AIC1 3, C2H50 9 ,
[ /t ) ~ ~-hybrid C-atom
(CH3)3N:, S0 3, Bre,
Nucleophiles They are rich in electrons or/and carry
EB
CH3-C=O, :NH 2,
e EB
N0 2
negative charge Types of carbocation
C2H50-, (CH3)3N:, : NH2
Types of carbon free radical The carbocations are classified into three types which
are primary (I 0 ) , secondary (2°) and tertiary (3°)

l9J) · .....
0
Free ra.dicals of carbon are classified as primary (I ),
secondary (2°) and tertiary (3°), i.e. carbocations, i.e.
Check Point H
I
13 H
le
CH 3
Ie
1. Which of the following _statements or information is not CH3 CH2 CH3 -C• CH3- r• CH3- / CH 3 - /
conveyed by an organic reaction mechanism? 6. Which of the following organic reaction is not initiated by
hemolytic bond cleavage?
Ethyl free radical I H CH 3
(a) Reaction intermediate involved in the reactio~ 1° CH 3 CH3 Jso-propy l Te rtiary buty l
(b) Energetrcs of every step (a) Substitution reactions of alkanes Jso-propyl free radical Tertiary butyl free
Ethyl can ~)ation
carboc.:1t ion carboc.'11ion
(c) Relative rates of every step (b) Electrophilic addition reactions · radical (3°) (2°) (3•)
(20)
(d) Exothermic and endothermic reactions (c) Allylic substitution in alkenes
2. Which of the following solvent is not suitable f h .
(a) CCI• (b) CS2 (c) CH30 H (di°~o~~~;~~~:
(d) Formation of benzene hexachloride
7- Which among the following. is not an electrophile?
Relative stabilities of free radicals Relative stabilities of carbocation
3. The factors whrch does not favour hemolytic fission i e IQ Total number of alkyl groups attached to the centr~ (i) The number of alkyl groups attached to_t~~
(a) large drfference rn electronegativity
(b) Presence of non-polar solvents
s (a) ~ Hs (b) CH3 (c) BF3 (d) S03
8· Choose the electrophile generated from HO----N0 2 out
01 ~t?~ carrying the odd e lectron decides th e relative
bihty of free radicals. .
central C-atom decides the relative J tap1ht1es of
alkyl carbocation. The more alkyl groups
(c) Gaseous phase reactions attached , the more stable it is
(d) presence of peroxide the options given H'3 ~he rnore alkyl groups bonded to the electron defic1~nt
4. Select the incorrect statement. (a) H"' (b) NOf (c) NOf · (d) O . 0rd er
0
H H H
•/he more stable is the radical. The overall R
(a) Homolytic fission results in the formar 9 • Which one of the following series contain electrophrleS re ative stability is as follows: I I I I
(b) t1:!~~orc:~
:~~~~::u~~s~ the form~~~i~;ee radi~s. only?
R H H H R-C" > R-Ce > R-C"' > H-C"'
I
(a) AIC1 3, S0 3, ~o 2 (b) H20, S0 3, H30' I I I. I I I
(c) fi;:~::~'.1ii~s:~e~~;f~irovides a major driving force for the I R R H H
(d) Steric bulky group increases nucleoph;r ·ty (c) NHa, H20, AIC1 3 (d) H20, Cl, NH3 R-c- >R-C" >R-c' > H-C J"orboc:ltion
Mc thylcarboc:1t ion
(Least stable )
5
. ;Z~~~~~~~he following is not an examp1e'~'f polar organic
10• Select the incorrect comparison with respect to given I I I I (Moststnble)

nucleophiles? R R H · H (ii) The stability of aryl carbocations increases with

(a) SN 1 reactions 3o rad· Methyl radical
(a) (CHa)aCOe < OH" lit) . !Most,t~bl ~) (Least stable) the number of phenyl groups.
(b) Free radical reactions ·e the greater
(c) Electrophilic aromatic substitution (b) H20 < NH S1111n I (C6H5) 3C+ > (C5H5)2CW > (C 5H5)CH;
(d) Electrophilic addition reaction
3 . is th ar Y, the more phenyl groups there a1 '
(c) RO9 <Rse
' e st abiJisation ,
(d) R3P <R3N
(c6HsJ3 c> (C5Hsl2 CH> c6Hs CH2
60 OBJECTIVE CHEMISTRY Vol. 1 Chapter
19
: Fu nd amental concepts of organic reaction mechani
sms 07
Thes~ alkyl groups destabili se the carbanion
(iii) The group which delocalises the positive
charge
negative charge on the central C-atom
by releas· benes are very reactive species with a
of carbocatio n increases the stability of H H · ingtlie (in C!dencY to gain ~lectrons : thu_s behaving as
electron Nitrenes
carbocation.
e.g.
H-C e
I I
> R-c e > R-c e
f R
I
:ncient species hke_ Lewis ~c1ds or electrophi
.. '[hese can be ~ategonse_d as smglet and triplet
les. Neutral monovale nt nitrogen species .in which nitrogen
two unshared pair of electrons with a monovale
has
nt atom or

(111) carbenes. Their propertie s and structures

are group attached is called nitrenes_
R-CH ~CH2 - R-CH-C H=CH2 I I I > R--c• ·
tabulated as below . (!) These are produced by thermolys is of azides.
(ally! cation)
Methyl car~anion H R I Triplet carbenes (ii) Nitrenes obey Hund's rule.
the 3° ,.,b! ~carbenes
(iv) Bulky groups attached to the C-atom stabilises (Most stable) (iii) There are two types of nitrenes, Le. singlet nitrene
returning to :e':i~tc~!: dunshared electrons
carbocatio n that prevents the C-atom If the central C-atom is surround ed by th l !tesssiabi:1 ~ u n s h a r e d electrons and triplet nitrene.
3
the sp state. withdraw ing groups, then carbanio n get e e :c~ron are Paired Empty

(i) The stability of aromatic carbanio s s~a thsed.

r,-: unhybridised ,------=:::::-,(jr,Unhybridised
1 1 orbitals Y~..._ Q;}~+
Reactions of carbocation }"ith the
~V ___: orbital ~C with I electron ✓N
z 0
1

Carbocati on are electron deficient species and act

Lewis acid. They react rapidly with Lewis bases
can donate the electron pair to achieve a stable
as
that
octet of
number of phenyl groups bonded ;:: ~re~;,s
charged C-atom (on the basis of res onance
(C6H5) 3 C e > (C6H5)2 C e > C6H CH•
n~g~tively
effect)
.
)io C <]Qsp2-hy brid orbital

~ l e and resembles
with 2 unbonded
electrons
(J(3
More stable and act as a free
Triplet
nitrene
(More stable)

electrons. · . diradical
(ii) The state of ~}'.bridis ation decides the r:lati:e ,,rbocauon
Arynes
x --c-I z
. Have two w:tpaired electrons,
electrone gahvity of the C atom A th 2
one in each of sp and a
-c+/ + the hybridise d state increases ilie s e s-character
of ~::go~ ~~~~~~::is ;da have
A formal carbon-ca rbon triple bond containin g aromatic
' more stable is the p-orbital.
"-
Carbocation
Anion
CLewisacid) I anion. an empty p-orbital.
The triplet state of the carbene
molecule is called aryne. The best known example
is benzyne.
CLewisacid)
= CHe > CH3-CH; Id) Decomposition of diazometha ne
> CH2
Some of the important reactions are as follows :
• Electroph ilic addition in alkenes
• Electroph ilic addition in alkynes
CH: c e

(50% s -character)
sp 2
(33.3 % s-character )

(iii) Stabili~ o~ carbanio n is also governed by

aromat1sat10n. e.g.
the
3
(25% s-fharacter)
~.
by heat or light generates the
singletcarbene.
e
CH2-N==N:
hvor
~
can be produced by a special
photochemi cal reaction using a
photosensitiser.

EH2-~= N: ~
Cl@:
In benzyne, an additional it-bond is formed between
two
photosensitise r
two
CH2+N2 neighbour ing C-atorns by sideways overlappi ng of
Carbanion
~L )-W =0 .
CH2+N, of
sp2 -orbitals. The new bond orbital lies along with side
Singlet
Triplet
n cloud
.
Carbon containing chemical species be anng - .
H 136' the ring and has little interactio n with the it-electro
a negative ng
charge on carbon atom d . le) H ~ H
~H lying above and below the ring. This sideways overlappi
v~ence s_h~ll is called c:b=_e t:/:~tro ns in its Reactions of carbanlon Aromatic 112pm 103 pm is weak and thus, makes be nzy ne more reactive.

19:P ··················· ··· ········· ·· ···· ··········

sp -hy bndISed and trigonal pyramidal in shape. ~banio ~ are electron rich species and act as
Lewis bases.
a proto~ (H')
p-orbital with or ::~:adily reac~ ~th Lewis acids. They seek
one electron pair
ybridised electron ;~_r positive center to which they can
donate its
Check Point
H H )- I • (c) Jn ~ H5 , Ihere is sharing of eight electrons among five
bonds.
H
-9:I r""'o+{
0

+ H-X - -9-H +:X 1• Geometry of methyl free radical is

(a) pyramidal (b) planar (c) tetrahedral (d) linear (d)~ H3 , CH3 ~ H2 are called carbanium Ions based
Types of carbanion Some of th e important reactions are as fallows
2· Which among the following has maximum stability? on IUPAC nomenclature.
(b) (CH 3h C s. Most stable carbocaJio n is
L~e carbocatio n, carbanions are also cl . . as
primary (1 o), secondary (20) and . ass1fied • Aldo! condensa tion • Claisen Schmidt reaction (a) CH2 =CHCH 2
(c) (CH3 )2 CH (d) CH 3 CH 2
.. ( b ) o <1>
tertiary (3 ° ) ca.rbon • Perkin reaction (a) CH2=CH
atom respective ly, i.e. • Benzoin cond ensation
3 n?
' Which among the following is not a primary carbocatio
0
• Wittig reaction

e r 3 CjH3 3

CH3-CH 2 CH3 Carbenes CH

(a)CH 3 -t-~H 2 (b) f _' ~H2
Erhylcarbanion - -~H CH3-~- CH3 •
The neutral div I d' g 6. Which of the following ca~bocation is m~st stable?
OO) ~6.:;:f.;~
Relative stabilities of carbanions
(2 0) TertiarybutyJ
carbanion (Jo)
non-bond ·
pairs
are called
a ent carbon species in which two
mg e1ectrons are present along with two hon
carbenes
(z) They are obt · d · the photolysi s of either
10

1iown
() r3
CH 3

c CHJ-<1>- CHa (d) CH3-yH -CH2

. 7_
(a) c H CH 2 (b) (CH3bC

Which
6 5
(c) (CH 3 )2 CH (d) CH 3 CH 2

of the following statements for carbanlon Is correct?

2
(a) 11 ls sp -hybridised
I . diaz h ame by
The number of alkyl or as s ~ (b) It ls trigonal planar I~ shape
be!o:~et ane (CH2N2) or ketene (CH 2 =C=O)
charged C-atom helps in7ecfJtup s direct!~ attached
of alkyl carbanion s. ng the relative
to
stabilities
(~
(a) a:th e Incorrect statement .
3 Is called carbonlum Ion.
(c) It carry six electrons 1n its valence shell
(d) None of Ihe above
CH2= N=N~ :ctt 2 ~CH2 =C""o th radical.
Diazornethan e -CO J(etene
-N 2 (b) In~ H3 , carbon Is more electron deficient than at a
 .&0 OBJECTIVE CHEMISTRY Vol. 1
Chapter 19 : Fundamental concepts of organic reaction mechanisms 0g
10. Which of the following statements ab e and possesses hig~ electron density. Electron CH3-CH0CH 2
incorrect?
Electropbileaddcd CH3 -CH-CH2
8. The correct stability order for carbanion is out arynes iSJ chafg. g groups make this electron density ever 3 2 1 Electrophileremoved
(a) 3• > 2° > 1 (b) 1° < 2° > 3° (a) Benzyne is an example of aryne are r~lea;;(destabilises carbanion) while electron with
(c) 3° < 2° < 1• (b) The sideways overlapping in aryne ·
In this, there is also (+ n effect of -CH 3 group
(d) 2° > 1° > 3 high . groups reduce the electron density (stabilise
9. Which of the following method is used to obtain carbenes? (c) In aryne, an additional 1t-bond is fo:::~ong which causes 7t-electron transfer from C 2 to C1-
dfa:::i~n). The c_arbocation an_d_ alkyl radical are
(a) Photolysis of diazomelhane ne1ghbourrng C-atoms by sideways between IWo car n deficient that are stab1hsed by electron (ii) Negative eiectromeric effect When 1t-electrons
sp 2 -orbitals overlapping Of two
(b) Photolysis of kelene transfer takes place from carbon to more
(c) Heterolysis of carbon tetrachloride (d) Both (b) and (c) are incorrect ;!~;:S~ng groups and destabilised by electron electronegative atom (0, N, S) joined by multiple
(d) Both (a) and (b) withdrawing groups. bonds, it is called negative eiectromeric effect
W , ,: a • • I ~ ,i

carbanion CH H (denoted by -E)

H H

4' Electronic displacements

3
I I I I Electrophile added e e,

(- I) effect decreases as one goes cH -C 0 <CH3-C 0 <CH3-C 0 < H-C 0 )cfa E!ectrophile removed> C-O
(electron-attrac ting) as shown belo:w: fromgroupx
3
I I I I
:V in organic molecules carbon charge is negligible. dafter third
CH3
3° carbanion
CH3 H H
Methyl anion
·(Most stable)
-C~
E!ectrophile added

Electrophile removed >

e
C=N
0

C1<o+) > C2<oo+)>C 3(ooo+) . (Least stable)

These displacement effects are necessary for organic Some of the -/ effect producing gro .
reaction mechanisms as after learning these displacement ord:r of+ their inductive effect are ups m decreasing Radical
(CH JJC° 0
> (CH3)2CH > CH3CH; > CH;
lnductomeric effect
effects one can easily estimate the site of reagent attack Most3stable The inductomeric effect may be defined as the increase in
Least stable
and behaviour of substrate molecule during the reaction. R3N >NH3 >N02> CN >S03H>CHO> CO> inductive effect which is brought out by the approach of
earbocation charged attacking species. It is also a temporary effect.
These electronic displacements either take place under the COOH > COCI > COOR > CONH2 > F >CI> (CH ) C+ > (CH 3 ) 2 Cfr > CH3CWi >
33 ai; Usually (- n effect is increased by the approach. of a
~fluence of an atom present in the molecule or under the Br >I >OH> OR>NH2 > C6Hs >H M~tstable Least stable
:!1c~::;_e of an attacking reagent during the course of . Due to -I effect (electron withdrawing riature).these (ii) Basic strength of amines Aliphatic amines act as
negatively charge<). ion while + I effect is increased by the
approach of a positively charged ion, e.g. - I-effect of
groups decrease electron density, hence Lewis bases on account of the presence of lone pair of
-N0 groups get enhanced temporarily by the approach
These displacements can be studied under following headings - basic nature is decreased electrons on N atom. More the availability of the lone 2
of hydroxyl ion to the hydrogen atom which is ultimately
- acidic nature is increased pair of N atom, more stronger the base is. Electron
Inductive effect (/-effect) (ii) Positive inductive effect (+I) This is due to the releasing groups increase the basic strength of removed as water.
H
This effect is defined as " olarit . presence of an electron releasing group (Y) within
nitrogeneous bases while electron withdrawing groups H, I -a
due to the presence of a :Olar b:n~~~duced m a molecule decrease the basic strength of nitrogeneous bases. HO+ HT-Cl --> HO·· ·-;,\:·· ·Cl __, HO-CH 3
polar bond. This in turn develops negative charge on
The inductive effect depends on ~h I th~ ~arbon chain. In other words, the permanent NH 3 < RNH 2 < R 2 NH < R 3N H H H
the substituent. It is transmitted
weakens as the distance b tw
tht
e ect~onegativity of
ough sigma bonds and
~hiftmg of sigma electrons toward the carbon chain It is a time dependent effect. Therefore, it aids the
is due to an atom or group is called +I effect. · \ · Electromeric effect (£-effect) ' reaction but never inhibits it.
~he adjacent bond and may be ]~ft
1s a permanent effect.
:::r
reactive centre increases. ~~e':iithe subst_ituent and the
IS greatest for
Y farther away. It
e.g.
ooo- oo- o- o+
C -+- C -+-C-+- Y
The electromeric effect can be defined as "polarity
produced in a multiple bonded molecule as a reagent Mesomeric effect (M-effect)
approaches it". It is defined as "polarity produced in a molecule due to
(+ I) effect also decreases as we go away from group conjugation~. It is a permanent effect.
Types of inductive effect y (electron-releas ing) as shown below Some characteristics are as follows
The induction produced b th (I) This effect is a temporary effect it is seen only when a
electron attracting or elec;on ::iola~ bond can be either C1(8-) > C 2 (88-) > C 3 (881H conjugation
. reagent approaches a multiple bonded molecule.
hydrogen. On the same basis theet5~ng :'ith respect to !
~ome 0 the + I effect producing groups in
(u) It is seen due to 1t-electron cloud as the attacking
The conjugation or conjugative bond signifies the partial ·1t -bon_d
in organic compounds. It is seen In those cases where 1t-bond 1s
be categorised into following\ n ucti:e effect can also ecreasmg order of inductive effect are
(i) Negative inductive effe:; ~ategones'.
p~esi_mce of an electron attr;ct~ This is due to the
-o- > - coo- > tertiary alkyl group;,
secondary alkyl group > primary alkyl group
reagent always attacks this exposed electron
cloud first.
present along with another 1t-bo~d, charge, odd electron'. or lone
pair of electron. For conjugation It Is must that rhese entitles are
separated by only a single bond.
w1thm the polar bond. This in t; groups/atom (X) > -CH3 >H The result of conjugation is seen as improper bond length and

~~:
~Y_Pes of electromeric effect
charge on the carbon chain In tr develops positive
permanent shifting of . . o er words, the to :I
effect (electron releasing naturet~~;e
g ps mcreases electron density. Hence, (') effect can be of following two types
Us
unpredictable extra stability In _1he molecule. Benzene 1s the best
example of this partial 11-bon_
,
d1ng.
carbon chain is due to 5;!ma electrons away from the 1 Positive
Conjugation berween
nature decreases while acidic nature increases, electromeric effect When 1t-electro~s 11bond]
effect, e.g. atom or group is called -I ~;t~sfer takes place from carbon to c_a~bon (as in CH -CH-CH-CH2
Ap _P 1·,cation
. of inductive effect ele nes, alkynes etc.), it is called pos1t1ve ,
2
Con jugation berween
ctromeric effect (denoted by +El- e.g., [ " bor:and lone pair
(1) Relative stability of carbanions radicals a11d
~:;i:~cations The +ve or -ve cha;ge or ':l~ct~o;y Cij
2
4tt 2
Electrophlle add•~ ~H 2 _c;H2 CH2 - CH-£\,e
d t~ncy of C intermediate can be stabilise gative Electrophile removed
re ucmg their charges. The carbanion C has ne
 1
Chapter 19 : Fundamental concepts of organic reaction mechanisms (';
~81
1
6~ OBJECTIVE CHEMISTRY Vol.

Decreasing order for + M power of ro

o- >NH2 >OH>OR>NHAc> aJ~ Upsare Resonance energy
e,g. . said to have following canonical forms
(CH3 > 1° > 2° > 3 °) > phenyl grou s yl groups (OC021s - - + + The resonance hybrid is always more stable than any one
(ii) Negative mesomeric effect (-M)PA O""'c=O~ 0 -C=O ~O=c-o- of its canonical form. Heat of hydrogenation of resonance
said to have -M-effect when the dir gr?up or ato .
electron displa~ement is towards suc~hon of li\i
away from conJugate system). Such group (but
electron withdrawing. groups are
(iOBenze 01 -O'S:::::, .
ne may be represented by following structures

::::::,.__ . #
hybrid is abnormally high,
e.g. the observed heat of hydrogenation of
C6H6 (= -49.8 kcaVmol) is greater than the calculated
value (= -85.8 kcaVmol) of the heat of hydrogenation of its

O 0
j e.g. Due to electron withdrawing
atom following structures are pos:ht;:;e of oxygen
Kekulestructures
In both the above examples the actual structure of
most stable structure.
The difference in heat of hydrogenation, i.e.
Heat of hydrogenation - Heat of hydrogenation
Due to mesomeric effect terminal carbon is almost as
positive as the first carbon. This is quite different from
~ (~ e oe
CO or benzene is more stable than either of the
stn:ctures described.
(observed) (calculated)
I

o=
inductive effect due to which charge decreases as one H2C-CH-C-H f - 7 H 2 C-CH-
-C-H is called the resonance energy, which is assumed to be the
energy gained when a molecule acquires resonance hybrid
moves away from the source. Conditions for resonance
(0 The arrangement of atoms are identical or almost formula.
H2C=CH-CH:CCH2 - H2C~~H-CH2
same in every formula.
-
e
H2 C-CH=CH-CH 2
e
~? (iij The energy content of all the canonical forms is
Types of resonating structures
(no effect on charge intensity; same at c 2 and c 4 ) nearly the same. There are two types of resonating structures
(iii) Each canonical form has the same number of (i) Isovalent resonating structures The structures in
Types of mesomeric effect unpaired electrons. which the number of bonds in different contributing
(iv) All the atoms in a molecule taking part in resonance structures are same, e.g.
On the basis ?f el~ctron withdrawing or electron donatin
: : e of coniugation, this effect can be of following tw/ should be present in same plane. o o0 t."
(i) Positive mesomeric effect (+M) A . Stability of canonical forms Hj/49 - H-1n=0 == H_J~ 6-
:!~ to sh~w + M-effect when the d!~~~:~tom is
displacement away from it.
~ecreasing order for (- M) power of groups are
.
WAmong all the canonical forms, the form without
1
(ii) Heterovalent resonating structures The structures
Suc:on is NH3>NO2>CX3 >CN>SO 3H charges will be the most stable one.
th ~oups have lone-pair of electrons and 1 in which the number of bonds in different
e pair for conjugation with ' re ease > CHO> CO> COOH > COCl > COOR> CONHi (iij Among the charged forms, the structure in which contributing structures are different.
(conjugated) system. an attached unsaturated maximum number of covalent bonds present is the

: 1::~::o:~f ::::( eifect ~xtends the degree of

molecule due to th - ve c arge imparted to the
E e process of conjugation
xamples executing + M-effect are
Resonance , ·;l) ll~ most stable. The structure with less charge
separation of opposite charge and more dispersal of
e.g. ,..--:::--,. (;:,
CH 2 = CH-CH= CH 2 -
. ~=
';:'11en a single Lewis dot structure is unable to explain all
=e~ies of a compound, two or more sµuctures, call~1
orucal forms or resonating structures are drawn
charge is more stable than the others. Such as

CH2 ~cHDCH2 ~c H2-CH=CH-~ H2

I Ell
CH 2-CH = CH-CH 2
II
e

(a) HiC~CH~ca.f'NH 2 explain all the properties of that compound. Then the actual I. e Ell

e struct~re of the compound is said to be in between these II - CH 2 -CH = CH-CH 2

-H2C-CH=CH-C H- <'±l ~anomcal _forms and is called the resonance hybrid of ese
th CH 2 = CH= CH= CH2 IO
(b) H2Cd=CH.fa'• e e -NH2 -orms. This phenomenon is called resonance, e.g. benzene I Resonance hybrid
.. •+-+ H2C-CH=e1 is a resonance hybrid of following two canonical forrns, Applications
l:tthe given example, I and II are canonical structure. The
The + M-effect of halogen atom i .
10~5-10 6 nu:cture is more stable due to presence of maximum
The various applications of resonance are

a-(J3-~6
aryl h~i?.e explains their low rea~ti:i~;.l halide and (i) Determines the stability ·of some free radicals,
due toe: of covalent bonds and structure II is less stable .
.Cl. eci: ecj• 2 ..,,"4
5==~
2::::,._14 V li\ore to!:rge separation, therefore structure I contributes
carbocations and carbanions.
)) . 3 3 Resonance e.g. rds resonance hybrid.
(ii) Determines the low reactivity of aryl and vinyl
I I 4 4 2 4 4 3 II hybrid halide.
Resonance contributors (iii) Determines the acidic nature of carboxylic acid and

.. Ce :,sonance contributors are shown with a double-headtd CB2~ ~ H 2 ~ ~H 2-Cll=CH2 =" explain the greater stability and less nucleophilicity
of carboxylate ion (OCOO-).
=
-f)-O
str::~::p;ating them. It also indicates that the ac;:e Allyt carbocati~n . U. CH2 CH= CH2
1 Stabilisation of carboxylate ion occurs by
resonance ;:n:~ewhere between the s~ucture::ai St Resonance hybrid delocalisation of its negative charge.
electron dist .b l~utors. They do not depict anY ance s IUcture I
hybrid is al n ution and are imaginary. The realso;0 rJllS, tability and ll both are identical hence, have same
ways stable than any of its canonic d
and contribute towards resonance hybd .
 6~ OBJECTIVE CHEMISTRY Vol. 1 Chapter
19
: Fundamental concepts of organic reaction mechanisms 0 3

bT
1 1 t'on is possible in
Structural necessity for hypercon· , tion of hyperconjugatioli
Greater reson~ce st a ;;~ ared with the . Following are the structural requirements for h ~Ugation
But the stabilities of the above benzy l was found to
carboxylate an'.~n when f un£ssociated carboxyhc APP1 1ca .. s of carbocations and free radicals be
resonance stab1hsat10n o (i) Compound should have at least one !>fercon· bihtle .
(i) Stll loW of :::!cctron density from the adjacent
acid molecule. of either alkene, alkyl carbocation or .:fk -;y . The f J-1 bond (through hyperconjugation) helps in
D>C>B>A
The observed stabilities are explained by the
(ii) a-carbon with respect to sp 2 -hybrid c ~ e1C-- . g the positive charge of c+ of carbocation. hyperconjugation effect.
have at least one hydrogen. More the :;~ shouJd dispersi~is type of overlap stabilises the
bonds attached t~ the unsaturated system er 0fB--,:
will be the orgamc compound. ' rnore Stahle
fle~~~~tion. Thus, more the number of CH3 groups Me-@-----bi 2 (more stable)
carded to positively ch:rrge~ C ?f carbo_cation, the
boD is the hyperconJugative mteract10n. Hence, (Four hyperconjugative structures)
e.g. the elect:o~ donating nature of a meth
1
toluene can s1m1larly be explained on the: ..groupm
.
gr::~:;is the stabilisation of the cation.
hyper.c onjugation by drawing the followin asis of
hyperconjugative structures g
~ the stabilities of carbocations is in the order
.. 30> 20 > Io > CH3
SinJilarly, Me-!i\=T
~&-!2
H H H H Similarly, one can also account for the stability of H
(iv) Determines the basic character of aromatic amines. (Three hyperconjugative structures)
The basic strength of aromatic amines is increased
I Ell Ie Ell I I , 1' HI free radicals
H-C-H H CJ:"H H C-H HG)C-H Hm c~ Me
by using +R effect substituents as they disperse the
positive charge on the N atom and stabilise the
anilinium ion while substituents with -R effect
decrease the basic strength of aromatic amines as
they destabilise anilinium ions.
6-6-Q~-<O~~ Me 3 C(3 ~) > Me2 CH(2°) > MeCH2 (1°) >Me
(il) Stabilities of benzyl carboc~tion According to : I
effect, stabilities of the followmg benzyl carbocat10n
and Me-).~
l'=f''
H
(Two hyperconjugative structure)
~2

Decreasing order of basic strength Types of hyperconjugation Me 3e--@---<!H 2 > Me2CH-~2 > Me
There are following two types of hyperconjugation
(i) Sacrificial hyperconjugation Sacrificial
(A) (B)
G) Me-l-o-
I -
~ ~H2
hyperconjugation involves the attachment of alkyl MeCH2-@---<!H2 > M ~ H 2
Me
group to double bond or triple bond, e.g. · · (no hyperconjugative structure, least sta ble)
(0 (D)
H H
I I · ti effect A more substituted alkene is more stable
(v) Explains the acidic nature of acetylene H-C-C =C - or H-C-C == C- (iii) Stability of alkenes Can be determined by hyperconJ~~ b~~ds at ~-carbon to the unsaturated system, greater
H-atoms. i I I :,, th_en the less substituted one.Greater the number of C the h erconjugation effect. e.g.
"H . H H , will be the hyperconjugative structures and thus , greater YP
Hyperconjugation Here, hyperconjugati;n involves a sort of sacri(iceofa H CH3

~t is a generalised stabilising permanent interaction. It

bond as
H H
H
,I I I
H-C-CH=C, CH3 -C-CH=C
H
< , CH3 -
I
c;:-CH=C ( , CH3-<;:-CH=C<
1·
I
i:J-1
,-r-
mvolves delocalisation of cr-electrons of the (C-H)
I I ;-; I
I I I CH3 3
~ H-C =
bond of an alkyl group directly attached to an atom with
: unshared p--orbital._The cr-e_lectrons of (C-H) bond of H-1_31'~}- H H
No hy perconjugation due to
alkyl group enter mto partial conjugation with the H W Maximum hyperconjugation (Stability) abse nce_of H-'.11om, at a - C
;:~~~-unsaturated system or with the unshared Number of bonds Number of bonds (iv) C- du~ to three H-atoms at a-C s stem gets shorter because of hyperconJugauo n.
-shown = 9 shown = 8 C smgle bond attached to unsaturated Y
H

r-< ~ -y=y-c<
h =c
-y-c H e
(ii) lsovalen~ h~erconjugation Isov~~ent . onds, i;t11yl
hyperconJugat10n involves no sacrifice of b
radicals have the same number of real bond s as
the
H
IJ.
H-c-ce:escH~
t"_ H-C=C= CH f - )
I
e
.. " ..

Here, the hydrogen atom carries the ..

classical structure. I H
there is no bond between the h d positive charge but H H W H H artial character and hence, shortened.
atom. For this reason, resonanc: :rog{:1 and t?e carbon I .I . I . In this given example, the CH3 -C bond has some p
called no-bond resonance or anchi!t- type.IS also H~c- c+ ~ H- C =CH· ·· ••'•
~::~~~ristic is seen in carbocations, f:~ce ~~:::t:~Jhis
I I I I
H H H H
(!) (II)
Number of bonds in both the cases = 6
6~ OBJECTIVE CHEMISTRY Vol.
1 Chapter
19
: Fu nd amental concepts of organic reaction mechanism s 05
hv ••

~'~:~:~&~: :~,~~:~~::~,:
yV",
°' °' Step I Unitiation) Cl- Cl --+ Cl + Cl
19.~ ·· ·· ··· ··· · ·· ·· ··
I' II z,
,: ~ • ,:: "i I l'l .,. i; R :p I' t, •

ll•Dlt

Check Point Step II (Propagation) CH3CH~ + Cl - - + CHi:H2 + HCl

• yV", •
11. Which among the following will not show+ CH3CH2 + Cl-Cl-- CH3CH2Cl + Cl
1. Inductive effect involves (a) -N02 . (b) - X Mettecn.
(a) displacement of er-electrons (d) -OR organ1~ on the nature of the substrate and the attacking These both steps U and II) are repeated in a loop
(c) -NH 2
(b) delocalisation of it-electrons depe
nd111!ost of them procee~ through the following wise manner until one of the substrate is finished .
(c) delocalisation of er-electrons 12. Low reactivity of vinyl chloride and chlo b Disappearance of one of the substrate leads to
ro enzeneisdue ~ reagents s of organic reactions
(d) displacement of it-electrons (a) positive mesomeric effect general type termination of reaction via following steps
2. Which effect is not reversible? (b) negative mesomeric effect
(a) Inductive (c) greater electronegativity of chlorine
substitution reactions Step ID (Termination) 6':'ci - , Cl 2
(d) lower electronegativity of chlorine
(b) Electromeric
(c) -Seth (a) and (b) substitution reaction, one atom ~r group of atoms in a
rnh-1';":a _ , CH3CH2Cl
13. Resonance structures of a molecule can t
(d) None of the above (a) identical arrangement of atoms no have !olecule is replaced by another smtable atom or groups of CHJC:H~"ctt2CH3 ~ CH3CH2CH2CH3
3. Which of the following statements are correct? (b) nearly the same energy content
atoms, CH CH + c:JiJCHz Disproportionation
(a) + I effect stabilises a carbocation (c) the same number of unpaired electrons The product obtained as a result of substitution is called
3 2
(b) + I effect stabilises a carbanion (d) identical bonding CH2= Cr½+ CH3-CH:i
(c) _I effect stabilises a carbocation th ubstitution product and the new atom or group of
14. Which of the following has +R (resonance) effect? • The reactivity order of the halogens for free radical
(d) _I effect destabilises a carbanion at:;s which enters th~ molecule is called a substituent.
(a) -CN (b) -CHO (c) -NH2 (d) -No substitution reaction is F2 > Cl 2 > Br2 > 12
4. Which of the following has -/ (Inductive effect)? e.g. R-CH 3 + X 2 ~ R-CH 2X + HX The more reactive a species, the less selective it will be
9 (b) . -o- 15. In wh~ch of the following molecules, the substituent d '
(a) ---;-COO
exert its resonance effect? lleS llli Here RCH 2X is the substitution product and Xis i.e. Cl 2 is more reactive but less selective while
(c) -NR3 (d) None of these substituent. The replaced atom is hydrogen. Br 2 is less reactive but more selective.
(a) C 6H5 NH 2 (b) C 6H5 NH
3 • The rate-detennin ing step in halogenation of an alkane
5. Which of the following groups exert the maximum (c) C 6 H5 0H (d) C 6 H5CI is abstraction of a hydrogen atom by halogen radical.
+/ effect?
16. Which is not the resonance structure of aniline? Types of substitu tion reactions • For a given halogen, abstraction of H is in the following
(a) (CH3JaC - (b) CH3CH -
(c) CH3 - (d) (CH3)2CH-
8
NH2 eNH2 On the basis of intermediat e species formed within the order allylic~ 3° > benzy lic ~ 2° > 1° (CH 3 ) > vinylic
reaction, substitution reaction can further be classified into • In order to yield the maximum amount of the
6· Which group decreases acidic nature of phenol? _(b)6e
(b) ~02
(a)6e three-categorie s. monochlorina ted product (R- Cl), a radical substitution
(a) -gH3
reaction should be carried out in the presence of excess
II
(c) -CCH3 (d) -CH
7. Which of the following shows the corre 0rd
the basic strength in benzene medium~!
II
.
er of decreasing
(c{)
<IINH2

(d)o <IINH2 Free radical substitut ion

~ubstitution reactions brought about by free radical
mtermediates are called free radical substitution , e.g.
halogenation of alkanes. Alkanes react with Cl 2 or Br2 to
of alkane (R - H) which ensures that there is a greater
probability of the halogen radical colliding with a
molecule of alkane than with a molecule of alkyl h alide.

(a) CH3NH2 > (CH3JaN > (CH ) NH> NH 17. Which of !he following carbocation is least stable? • form alkyl chlorides or bromides. These reactions take free radical reactions in cyclic compounds
(b) (CH3)2NH>NH3>(CH) ~2>CH NH3 (a) CsHsCH2 (b) p-NO 2-C 6H,-CH, place only at high temperature s or in presence of light. Cyclic compounds undergo the same reactions as the
(c) (CH3)2NH> (CH3JaN> ~~ >CH3NH2

8.
{d) _(CH3JaN> (CH3)2NH> CH:NH 2 : NH:
ir'.i~~~~. not the correct representation of the it-electron
0.
(c) P-CH 30-C 6 H4 -CHi (d) p -CI-C 6H4 -CH2
18. Maximum hyperconjuga tion is observed in
e.g., CH4 + Clz or ;;o K CH3Cl + HCI
non-cyclic compounds.

Q+Cl2
QCI + HCI

{a) CH3CH=CH2 {b) c0 (a) Q--cH=C H2 (b) Q-cH=C H2 CH2 =CHCH 3 + NBS - CH 2=CHCH2Br
~ . 2 ~HCH2CH3 0

{c) CH3CH==CHCN (d) CHJCH2CH QH (c) (CH;bC-CH =CH2 (d) Q - c H3

~ + HBr
9
• ~~~:~~~e~~~I~;!:;· which effect is a temporary eff:ct?
(b) Inductive effect
(c) Electromeric effect
(d) Hyperconjugation
19· Which of the following molecule/ion cannot be s labiliSad bY
hyperconjuga tion?
(a) CH3CH=CH 2 (b) (CH 3JaC--CH2
ll,,,, Nils (N-b,=n succinimide)

It is a source of Br free radical. O Q

O+Br2

+NBS c~,
9sfu
"/ + HBr

10. Which effect aids the reaction but n . . . (c) (CH3)2 CH 2 (d) CH 3CH2 Mechanism
ever inhibit the reaction? However, cyclopropene or cyclobutene undergo _
(a) Inductive effect 20 C......_lib d'1 al
· The CH3 - group in propene exerts electrophilic additi_on reactions as they are alkene. It 1s due
(b) lnductomeric effect hydro /n~ is replaced by C-X bond in free ra ~ free
(c) Mesomeric effect
(d) Resonance
(a) hyperconjugation (b) +/effect
(d) Both (a) and (b)
!.
1•dic nation. These reactions takes place thr0 u~ to strain in small nngs.
Br~
(c) -/ effect SUhs~~n~erm ediates and also known as h~m~lytic _...., Br
O+Br2
generate~•on reaction as halogen free radical is
from homolysis _process, Cl
CH3CH3 + Cl2 - CH3CH2Cl + H
 \ 0
60 OBJECTIVE CHEMISTRY Vo l. 1
I Chapte r
19
: Fundam ental concep ts of organic
reactio n mecha nisms 1

Mechanism
n halid shift in nucleo philic substitution Bimolecular nucleophilic
. . b •t ut'on
1 reactio These reactio ns are visible in 3° alkyl
1,1e111Y1
Electroph1hc su st, . . • db
which are m1t1ate r due to followi ng ~o f a~ts
es and alco1io1s CH3
. substitution reaction (SN2)
. . . tion . I are involve d in the
The substitution reactwns tro hilic substitu (i) Steric crowdm g, 1.e. over crowdi
ng of alk ever, ;rcHr- 'j=-CH 2CI is.the substrat
e then the product
When substrate and nucleop hile both
istic of aromati c as bimole cular (2).
electrophiles are called. eJec pharacter pr;;egrouPs rate-determinin g step, then this is called
around the central carbon atom which

e=~o•.~~ ~ 0•
CH3
reactions. These react10ns are c HOVI
n, indicat ed as SN 2.
attack .
nts back
CH 3 CH 3 nucleophilic (N) substitu tion (S) reactio
C-ato ROH+ X-
(ii} Decrea sed(+} ve <;harge on central
0

HQ + J group of a lky l groups a ttached

. As a !
due to
forrned is CH3 6H
tH3
CH as
-1-cH 2CH3 instead ofCH 3-J:-<:H 2 3
e.g. R-X +0H -
Rate oc [R-X] [Ofr]
bond for;ul~, . .
sim~lta neous bond breaka ge ~d
is 2• or atron ts n~ =methyl or 1° alkyl group.
possibl e. Also when alk!l halide 30 . ,mrrned in the reaction can undergo
rearrangement to Here, R
3• c b 'there 4 attacti of nucleophile. on state, i. e .
increas ed electro n density at 2° or ,arboGat~~tabie ·carboca tion before This reaction involves the formati on of transiti ion is the
Mechanism phile is not possibl e. ar on and CH CH
state format
attack of necleo give rnor 3
I 3 an interme diate stage. This transiti on
The reaction involves following steps g two steps · CHa 51 I + Rearrangement slowest step hence, acts as a rate determ
ining step. Here,
n of So reactio n modifi es itself into followin 2 CH,,- ~CH,CH3 substra te and
Step I Release of an electrophile and formatio
3 1.2-methy lshift both
Step I CH3 cH,2-CH 2CI* CH f-CH the rate of reaction is determ ined by
Nu"catalyst complex e I= . + Be CH, These reaction s are visible in primar y
Step I (CH 3lJCBr SI I nucleophile.
-
CH3Cl + AICJ3 - AICI~ + CH3 ow H3C~ CH3 r CH.,'- - - - ~ - - - - - - - - - alkyl halides and alcohols.
step H
Step II Attack of electrophile on benzene
and formation Here, the cleavag e of R-X is a slow Mechanism
· ence,
of resonance-stabilised cr-complex. used as the rate determ ining step.

OH
VioH e'eJ A CH 3 - Step II
+ O H ~ (CH3}3COH
Qrder of reactivity
!nSN1 reac t 1·on the
order of relativ e reactiv ity of RX is
It is a one step process that involve s
the change ~
concent ration of both substra te (RX) and
.
nucleo phile with

O
e :?" CH3
:'>.e Slow
+CH3 ------,. CH3 ---.. Step II .H3C CH3 IX identical) time.
4
can be racemisation
ally! or benzyl > 3° > 2° > 1° > CH 3
X
Back H )H . H
+Cl 0
(Carbocation-an arenium ion) • As a result of SN 1r eaction , there Increas ing reactivity ~~i -Slow CJ y-- HO-~~
H 0 ··•· ....H H
utane having chiral OH + H1 H -~,, as,
and invers ion. When (-)-2-b romo-b
~ H as H 20 such that-~!
~H ceritre is treated w ith low [OI-r] Benzylic and allylic halides underg o
S Nl reactio n because
--. Ve CH3 =~ Transitio n Inversion
Nucleophile
CH3 is obtaine d. There is due to the resonance.
reactio n is followe d, (+)-2-b utanol of the stability of their carboc ations substrate
in optical activity is
cr-complex also loss in optical activit y. This loss Here, the incoming nucleophile interac
ts wi~ alkyl .halide
s in equal amounts by OC~ 2+C l-
Step III Loss of H+ from cr-complex
to form end product due to format ion of d- and 1- isomer OCH 2Cl SN !
causing the carbon- halide bond to break
while formm g a
SN 1reactio n. • • es .takes place
new carbon 'OH' bond. These two process

V ~ fu_!'
~ CH3 and no establis hed
~H Benzyl chloride simultaneously in a single step
CH3 ~ ( J +F
•~9 .) • H 3
CH 0H OCH 20CH 3 + H+
intermediate is formed.
In slow step, equal particip ation of substra
te and
.
nucleop h1les

Step IV Release of catalyst from Nu

- catalyst complex Br y• l ru . dicates rate depend ency on both the molecu les.
~ ca_rbon ~tom under
AICl 3 + HCI 2 3 CH2vnJ :s this happens the configu ration of
AIC!f + He -
usually
/rCH CH II (-)
CH2 = CHCH2Br ~ CH2 = CH ;H2 + Br_ attack inverts in case of compou nds
with chiral carbon
The .cat~yst used in these reactions are ,
CH3 away.
CH3 Ally! bromide while the leaving group is pushed
Lewis acid and other electron deficient
H-p- oH as Walde n s
That's why this process is also called
compou nds. HO~H ~ CH2 = CHCH2 0H + H+
CH2~J inversion.
Nucleophilic substitution reactions CH2CH3
H retention (+) inversion Vinylic halides (CH2 ·= CHX) and aryl
halides

When a subst!tut(o~ reaction starts by

the initial attack
of a n_ucl~oph1le, It .tS called as a nucleo
substitution reaction.
philic .
front side of the carboc ation. In back
which is the sid~ of t~e carbon fr~m
backside a~~t!
Nucleo philic reagen t attack s both (I) side attac I ; ng
wh~ch !hee:;ned
1
.l 0-x) du not unde<gu S, I reaction due to
SNl VsS,.2
Both the reaction procedur~s discuss
compared on following basis.
ed above can be
.
'.'1'e faster 1~ more
are tw ration 18 ;here can inSlabuity of their carboc ations. (i) Polarity of solvent SN 1 reactio ns
These ar': .usual(y written as SN. There gro~p departed (in this case) configu P!ace, I g a negativ e
nucleoph1lrc substitution reactions
o types of
but in fr~nt ~ttack (II), invers ion
takes ill olar solvents. SN 2 reactio n involvm
m equ\ to solv~nt and that
be racem1sation if d- and l- are formed pP 0 : 1t~e c~cH~ : - CH2-;-- CH = X ~ucleophile is slower in mor~ p~lar
m more
Unimolecular nucleophilic substitution (S
1) red on the side 0 involving a neutral nucleoph1le 1s faster
exl!
A_ttack is prefer
O=
amoun ts.
When rate of substitution de ends
of the substrate, then it is said
nucleophilic (N} substitut' (S) to be. the
N
on the c.oncen tration
.un1molecular (1}
where leaving group Br- exists
hence mixtur
is ~referr ed, e is not
since,
purely
it shield£ t attack
this case rod soflle
?assage of nucleo phile for attack . (In racemic an
en is
~- ·.
\-=-7t}.· --
polar solvent. ·
.. H-bonding in solven t In
(u)
additio n to these
the ability of certain solvent s to form
.
polarit y

JOn reaction, mdicate d as S 1 optical activity exists}.3 . . • · der b ds with. the nucleo phile also affects
the
!f)l is sa effects,
R-X ~ Re +X~ N •
Jhu. s,
th
e reactio n of an alkyl halide in whic~ haloftwo Ille, then relativ e reactiv ity 1s m or hydrog en on
0nd 0 ? ration as
0
- rate of th.e SN 2 reaction .
carbocation e? to chiralit y centre leads to the formatI R-I>R -Br> R-Cl> R-F
confi~verted
Rate oc [R-X] :~ereoi so~ers : one with the same relative th Increas ing reactivity
and the other with e in
co~fi:~ ~~~n~y l halide
 \
6~ OBJECTIVE CHEMISTRY Vol. 1 I Chapter
19
: Fu nd amental concepts of organic reaction mechanisms 09
d rotic solvents and JI Loss of the leaving group to reform the aromatic ring.
Such solvents are terme as_ p nitro en or oxygen.
1 Effects of No effect on rate
~Cl _
Step IT Br- attacks 0) to form (Il) a trans-product
have a hydrogen bondmg with
H20, ROH, RCOOH are some examp es
of protic nucleophile
Effect of carbon
structure
Tertiary > secondary
resonance stabilisation
Stefl

w
)ve
~Nu
w~ +ct
8
H3C ~
)c-c< + :B~:
9
---, H-C-Br
r 3

;~:~;otshiles, especially smaller anionic ones, are .

strong!: hydrogen bonded to the solvent molecules m
of Re important H B~~ H •• Br-6-H

protic solvents. .
Hydrogen bonding makes these nucleophiles Jess reactive
Stereochemistry Racemisation (possible
excess inversion) Inversion
Ad
dition reactions . .
hich involve combmat10n between two reacting
(I) &3
Trans-product
because the solvent molecules block the approach of the
electrophile. . .
Effect of solvent Favoured by polar

Competing
solvents
Elimination,
~~~::d by •Protic Reactions w give a single molecule as a product are called
iJ10Iec_uies toactions. This type of reaction is a characteristic Bromine and chlorine are the two halogens used most
(ID

Elimination
Aprotic solvents (like acetone), which do not form reaction rearrangement ,ddi110:;;ounds containing double or triple bonds. In frequently in halogen addition. Because fluorine is so
hydrogen bonding with the nucleophile, increases the of the c .on a group add to an unsaturated system. reactive that it not only adds to the double bond but also
reactivity of the nucleophile and are especially favourable Nature of leaving group In both cases thesereacU , rapidly replaces all the hydrogens with fluorines. Iodine
group is easily replaced by stronger nu;1:-0WMaker leaving adds to alkenes at low temperature, but most di-iodides are
for Sr; 2 reactions because they do not have hydrogen
bonded to nitrogen or oxygen. If acid is weak, its conjugate base is weak :d ~-
leaving group. is a better
e.g'>cf c< + X2 - )T--~-f unstable and decomposes to the alkene and 12 at room
temperature. ·
X X
Table 19.2 lists some common solvents in order of
decreasing "ionising power" (or ability to stabilise ions)
Acid H20 < CH3COOH <HF< HCJ < HBr <HI -c~c- + "
X2 -
)
x c~c <x----)x-7-7-x
x;
a I" I CH 2 = CH 2 + F2 - CH 2
I
- CH 2
I
~ CF3 - CF3

Table 19.2 Sornecommon solvents

for substitution reaction
Base
Leaving nature
Oir >CH3C00- >F- >C!-->Br .. >r
ov- < CH3 coo- < p-- <Cl-< Br .. < r )c=:O + HCN -
~,
>r'-"• X X
CH _ CH
2-
F
I Room temperature CH _ CH
z+ z 2 2
F

I I
Name Structure
different I OH I I
Trifluoroaceticacid 0
II Aromatic nucleophilic Inert solvents such as C0 4 and CH 2 0 2 are used for
CF3COH
These are polar, protic Types of addition reactions halogen additions because these solvents dissolve both
Acetic acid 0 solvents. They are quite substitution (ArSN) reaction These reactions can be further classified into three categories halogens and alkenes.
II good as stabilising ions and
Und~r ordinary conditions, nucleophilic substitution
CH3 COH are especially favourable
react10ns are not possible on benzene, since the Electrophilic addition reactions Addition of hydrogen halide
Water H:,0 for Si, I reactions, although
they can also be used for 0
In these reactions, initiation starts with the electrophilic When H--X approaches toward an alkene the generalised
Methanol displacement of H (very strong base and poor leaving
CH3OH Si, 2 reactions with equation can be seen as
group) is very difficult. , part of reagent, e.g. alkenes and alkynes etc.,
favourable substrates.
Ethanol This can occur only if an oxidant can convert H 0 to HP
H2C = CH 2 + HX - CH 3 CH2X
CH3CH2OH Addition of halogens
Th~ reaction is possible with Ar X and ArOTs, (aromatic · When Cl 2 or Br 2 approaches towards alkene or alkyne,
CH 3 CH = CH 2 + HX - H 3 C?HCH 3 + CH 3 ~~~2X
These aprotic solvents
0 are still relatively polar, halides and tosylate). Both (- X) and (- OTs) are good leaving
Dimethyl sulphoxide II then addition products are formed via the formation of X
(DMSO) • CH3 S CH3 so that they can dissolve groups, especially when electron withdrawing group, such as Predominant
both the nucleophile and cyclic bromonium ion intermediate, e.g. (Major)
0 the substrate. They are (- N?2) and (-C==N), are present at o- and p- to the
reacting C-atom. · CH2 = CH 2 + B r - B r ~ CH2 - Br Mechanism
II
~::ryl fonnamide HC N(CH3 ) 2
especially favourable for
Si, 2 reactions because
. nucleophiles are more ~ Br OH
Alkene Bromine I
CH 2 -Br
The addition of HX on the unsaturated system takes place
in two steps I I
reactive in these solvents , / + __ Slow H C C v--
Acetone w than protic ones.
'y NO, ,,,::';:,.~~NO, ••:::f."'·~ These type of addition reaction can follow polar (ionic)' Step I )C =C '-.,. +HX - -I-Ell"-+,,
CH3CCH3 mechanism. (Carbocation) "-
Electron-deficient carbon
Table 19 3 Surnin f di . N02 N0
2
N02 Mechanism
. ary o re:!~!:on between SN 1 and SN 2 In this step, electrophilic H+ is added to alkene in
Mechanism Siep I There is formation of cyclic bromonium ion (I) a slow manner. This is the rate determining step
when Br attacks 1t-electrons. hence, reaction is called electrophilic addition
Step I Addition of the nucleophile (: Nu - ) to form a carballi~'
Mechanism
Two-step H3 c"'- /CH 3 (AE) reaction.
R-L---. R"'---,•
t~t d/'ICI H/C=C"'-
H
+Br2 -
CH .. a Step II x-- attacks carbocation at electron deficient carbon

M
~u
-:K::--
in-eti-.c-, - - - - R-Nu I ?' Cl --- ~ H3C "-c--c/ 3+ :~,r: resulting to the product as
w ~ -w 0-. e wu•g
e•• t/tllC H/ \ /~ "-H I I I I
..-- 1,-f
Br
(I) H-,-~-+X-- - H-y-y-
, Resonance stabilised carbon W
A cyclic bromonium ion is a species th at contains a
bromine bonded to two carbon atoms as shown
above.
X
 6, OBJECTIVE CHEMISTRY Vol. 1 Chapter 19 :
Fu nd amental concepts of organic reaction mechanisms
{ ;,
~91

We explain the formation of Y by i2

' ·hydrid
Reactivity of HX with alkene is in the order
HF « HC! < HBr < ill
f3 eshift. Mecna111s;e cyanide !on formed by ionisation of HCN . Mechanism
step I Chain-initiating step (0 - O) bond in peroxide is
The hydrogen halides H-F, H-CI, H-Br and H-I . H3CCCH=CH2 + HBr ~ ?,!a Stefl I the nucleoph1le. 1s
weak and is easily broken homolytically in ,
undergo addition on carbon-carbon double bonds to give
products called alkyl halides. H-F is extremely hazardous
J ~s.;Br. lf3C~liClfa ff-CN +OW - H20 + :cN
Cyanide ion
presence of light or heat to form a radical (RO)
which in turn removes a hydrogen atom from HBr
CH \'F~ Ii Stefl O cNe attacks on C-atom of carbonyl group.
and is avoided wherever possible. Addition of HBr and HI 3 2' giving Br• radical.
are faster than that of HC] hence; preferred.
The product formation for asymmetrical alkenes via this
I
H3C~CH2CH3
3' carbocation
j
car~

Br·
c.o: ·o·e
•I• . la'.)~
V
OR Homolytic
UV
2ID
Free radical
mechanism can be predicted with the help of
(more stable than 2°) Ula •hilt) II
C
e N ...-- - C -
+.·c
Markownikoffs rule.
lV l IDH + B;

Markownikoffs rule
1~ ~
Ia CN
iI + ar
Free radical

This rule is used to predict the.major and minor products

when an asymmetrical reagent is added to an asymmetrical
13 H3CCClfC1i
II
BBr
3
Step III The negatively charged oxygen-(an alkoxide ion) is
a relatively strong base an~ is protonated by either Step II Chain-propagating step Br radical attacks on the
alkene. The rule says that in such cases "the positive part H3C?CH2CH3 water or HCN to complete the addition.
Minor(X)
it-bond of the alkene to form a bromine-carbon
of reagent goes to that C-atom which contain more number
of hydrogens or negative part of reagent goes to the
Br •o•e OH bond. Bromine radical can join to any of the
sp 2 -hybridised carbons of the alkene to form
Major(Y)
·1·~ n I
C-atom that contains lesser number of hydrogens."
e.g.
Ht=\-
H goes here
CH2CH3
X goes here
Benzylic carbocation
- ~ ~-J.
(o- I is more stable than
· -C-
I
+H-CN-

CN CN
- C - + :CN
I
e
primary or secondary free radicals as shown
below
.r--. n (\
Br + 0!2 =0!0!3 --+ BrOl;t:HOl3
. .
. Sterle hinderance plays an important role in
H3CCH,C'c::f½~
alkyl hence, if alkyl and phenyl gr
is preference in 1, 2-shift is given ~~p~are attached, then product formation. As the size of the group . n~ (2°frceradical)
H~ slow alkyl group. P enyl group than attached to the· carbonyl carbon increases, van der ~ 0 !3 --+•Ol2cr0l3
CH3-CH2 -CI-I 2
+
H3CCHCH 3
Addition to conjugated dienes
Waals' repulsions in the corresponding addition
compounds become more important.
Br
{!°free radical)
Lessstablecation More stable cation 3
BriF~ Br-1Fast ~~odnjugated diene, such as buta 1,3-diene, ·re;;dis' witha
2
Due to change in hybridisation (from sp to sp ),
Since, stability of 2° free radical is greater than
CH3CH2CH2Br occur at702unt of electr_o?hilic reagent, then .addition can bond angle decreases, repulsion inc_reases and I O free radical, hence formed predominantly.
Minor product 7
H3C HCH3
Br
shown bel~w or 1, 4 pos1t10n of the conjugated system as hence, free energy increases. Thus, increase in
attac?ed group size decrease the reaction. Step m Chain-terminating step Alkyl radical that is
3 4 3 formed removes a hydrogen atom from another
Major product I 2 sp2 -hybridised h b · dised
molecule of HBr to produce alkyl halide and
The above product justT . CH2 =CH-CH=CH 2
of stability of carbocati:~c:1;~ocan be given on the basis
• Stabil"ty f
I
. wn.
o carbocat1ons is in order· 30 > 20
hence, there may be 1 2_h . ·
o
> I > CH3 f2 -CH=CH-CH2
/ Bula- I, 3-cliene

CH2=CH-~-r2
1 -•wr;FP.'I bromine radical as
BrCHiCHCH 3 + H:Br - BrCH 2 CH 2 CH 3 +Br
This step is re{leated till one of the substrate is
1,2-phenyl shift lead· ' ydride or 1,2-methyl or
to more stable carbocation. Shift is
Br I · Br Br CN finisheil. As 2° free radical is formed
in order : mg predominantly hence, it is involved in predominant
I, 4-adclition product Br I, 2-adclition product
Reactivity of carbonyl comppunds for nucleophilic addition product formation.
ff~~dride) < CHj (methyl) < C6H5 (phenyl) Note Among halogen acids the reaction is true for HBr only. HCI and HF do not
In io~is!n~ solvents 1, 4 -addition predominateYwhereas in HCHO > CH3ClIO > CH3COCH3
form freeradicaleasilydue tolargerbond·energy,hence peroxideeffect
I r,, non-iomsmg solvents 1,2-addition product predominates.
3 CH3
~ee radical addition reaction . is not observed in such cases. Whereas HI with minimum bond energy is
H3CCHCH = CH2 +HB I Nucleophilic addition reactions ~r~ a~dit_ion of HBr to alkenes in the presence of light or
veryreactiveand insteadformsl 2•
r - H3 CCHCHCH
I 3 In these reacf •
1
111Tc
1
l'h· Xi
e IS called as free radical addition reactions. HI--+ H•i--+ 1,

Minor(X)
Br
part of rea enwns, mitiati~n- occur with the nucleop
carbon
I
g t. These add1t10n readily takes place on 0f t
by type of reaction takes place opposite to that predicted
uneve~y c;_mp~unds, nitriles etc., due to the presence ~rox~drkownikoff's rule. It is also called as Kharash
1
Elimination reactions
1stri uted electron cloud, · e effect.
fH3 • e.g. In elimination reactions, two groups on adjacent atoms or
same atom are lost and a double bond is formed. Thus, the
+ H3CfCH2 CH2CH3 product of an elimination reaction is an alkene or alkyne
pH 9-10 I (multiple bond). It is just opposite to addition reactions.
Br ~ - C-CN
Major(YJ
I
OH
 6~ OBJECTIVE CHEMISTRY Vol. 1 Chapter 19 : Fundamental c (';,.
. oncepts of organic reaction mechanisms ~3

simultaneously. Due to the formatio 1

This reaction is given by the compou~ds ':hich have a this mechanism is comparable with tof transitio ff' (ZaJtseV) rule (lli}'El-CB Reaction
2 st "~tte S ...es an idea of major and minor prod .
Primary alkyl halide and alcohols p rnecha,/18 •te
nucleophile as leaving group, i.e. X, 0 R N2, H20+, etc.
mechanism. roceed via 1:2 lll,
}" ..le g1 • .bl
fitiS ru'aJl<ene products are poss1 e. 1:his rule says that
uct in case : 1CB ~ a two step process. Here, CB stands for conjugate
These reactions are generally endothermic and take place asE;, First step involves the fast reversible removal of a
of iw:obstituted ~ene forms the maJor product (stabilised
on heating. Moreover, these are very common in alcohols · Mechanism pr_oton from the ~- carbon atom by the base with the
1110:yperconjugauon). ~::ati~~ of a car_banio~. Second step is slow and the rate
and alkyl halides. bY Me Me Me rminmg step m which carbanion (conjugate base)
I eMe~Mel ejects the leaving group to give alkene.
Types of elimination reactions t,1evi'Me + OH - 7' Me + ~
There are following two types of elimination reactions
Br (Major) (Minor)CH2 Mechanism
More stabilised by hyperconjugation Step!
a-Elimination reactions Transition state (9 hyper conjugative structures) H3C~CH3 ~ H3C ~ PJ
When loss of two atoms or groups occur from the same H~re, _L is the leaving group or nucleophile The rate determining step depends on the concentration of H3C'l') £"CH3 ~ HJC rc-1>:tI3
atom of the substrate molecule, then reaction is called It rs brmolecular since, substrate and b . . onlY one reactant . . . Base(Be) Step II (A)
a-elimination reaction, e.g. base catalysed th_e ~ate _d etermining step. We call it E~[t·e involved in
ehmmat10n] reaction. Reactivity and stability order. slow H3C>=<Cl¼
dehydrohalogenation of chloroform to form dichloro imolecuiar
carbene.
, benzylic '" 3 ° allylic > 2° benzylic "' 2° allylic "' 3 ° > 10 ~ H3C Q¼
E2 proc:ss does not proceed through an inte . . ~nzylic '" 1° allylic > 2° > 1° > vinyl
er-H'O carbocation and th: rate of this reaction is le:ediate Because step I (deprotonation) is fast and reversible, the
HO + ryCCl2 - :CCl2 + H20 + Cl- the degree of substitution • Io, 20 or 30 _ affected by --- Increasing reactivity and stability reaction rate is controlled by how fast the leaving group is
Cl Dichlorocarbene leaving group. at the central lost from the carbanion (II) (conjugate base). The loss of L-
/deal conditions for El mechanism are
P- elimination reactions Rate of cleavage of C-Xbond is in order:
( 1Highly substituted carbon atom for the carbocation
1
from (A) in step (II) is rate determining step and is
unimolecular.
When loss of two atoms or groups occur from the adjacent I >Br>Cl> F center, such as tertiary carbon atom.
FasteSI Slowest
ato1:15 ?f th;
substrate molecule, then reaction is called
(iO Use of polar solvents which can stabilise the Addition-elimination reactions
!3-elimination reactions, e.g. acid-catalysed dehydration (ii) Unimolecular (E1) elimination resulting carbocation in addition to stabilising a polar The reaction that involves addition of two molecules with
of alcohols and base-catalysed dehydrohalogenati f
alkyl halides. on o !I eli~i~ation is a two-step reaction. Firstly, heterolytic transition state involved in the heterolytic bond elimination of smaller molecule like H;o is called addition
ra::oJiation_ 0 ~ alkyl halide occurs, which is a slow and cleavage. elimination reaction. These type of reactions are
• Acid-catalysed dehydration of alcohols b etermmmg step. Then, abstraction of proton through (iiO In El reaction, the intermediate is carbocation commonly found in carbonyl compounds that are discussed
H- CH _CH .idH Cone. tti50 4 ah ase occur from a carbon adjacent to the positively and thus there can be rearrangement Oeading
2 below:
2-.....::::.2.,J - C H2=CH2+H 20 c _arged carbon atom. Due to the formation of carbocation to more stable carbocation) before proton is
Ethanol Ethene this mechanism is comparable with Si. I mechanism. This is lost as Nucleophilic addition reaction followed by
usually seen in tertiary alkyl halides and alcohols due to elimination of HP- addition of ammonia
• Base-catalysed dehydrohalogenation of alkyl hard
~ 1a the steric hinderance. IH3 derivatives
Ho· H-~H -CaH r-,.B KOH(a!cJ H3C-C-CHCH CH30H Aldehydes and ketones react with a number of ammonia
~ 2 - r ~
Mechanism . ·1 I 3 +KOH derivatives such as hydroxylamine (NH20H), hydrazine
Ethyl bromide
4 step I Generation of carbocation CH3Cl
CHz = CHz + KBr + H O CH3 (NHzNHz), phenylhydrazine@-NHNH 2 and
CH3
~
CH3 CH 3
The 13-elimination reaction can Ethene_ 2 j Step! I + Br· 3° I 2° I semicarbazide (NH2 CONHNH2) in weakly acidic medium,
depending on the type of cleav proc~ed vza three pathways CH3-C-Br ~ CH -C@ HJC-C-cHCH Rearrangement
These are age O two cr-bonds. I~ 31 Leavingg,"'P
(I eJ 3 in carbocation
H3C~ICH3
e.g.
CH3 CH3 CH3 CH3 'C=O + HzNOH ..!:t... )c=N-OH
: B~olecular (E2) elimination 20 carbocation 3° carbocation / Hydroxyl omine Oximc
• Ununolecular (EI) elimination This step being slow is the rate determining step~ (more stable)
El - CB elimination.
depends only on the concentration of o'ne re~ctan · 'C=O + H2N·NH2 ..!:t._, )c=N-NH2
step II Ab5tracti~n of proton by base
/ Hydrazine Hydrazone
(i) Bimolecular (E2) ellm·
E2 elim· . .
~ation is a concerted
.
mation reaction
abstraction of proton from th ;e-step process in which CH3-C@
CH
I 3
~OH
Step II
~cH
CI-13
I o'
_c+flJ
r
H3C-C-ctt -CH
I -
CH3
I
H3C-C=r.....cH3
'C=O + H2N•NHPh
/ Phenyl hydrazine
~) c=N·NHPh
Phenyl hydrazonc

removal of x- from th e - C atom by base and

e <X - C atom take place.
t\l .. 2 3 I CH3
z
CH3
Major product /
.
'C=O + H2N·NHCONH2 -=-+/C=N·NHCONH2
Semicarbazide
H+ '-.
Semicarbazone '
. CH2-H c!-12 Minor product
6~ OBJECTIVE CHEMISTRY Vol. 1
. '
The generalised mechanism ,or 9
below
Chapter 19 : F nd
ms
u amental concepts of organic reaction mechanis
b
In these reactions , pH of medium must
iven reactions are given
about 3.5, i.e. the medium must be w ake
control! n?
WJ1ich is not the resonanc e structure of a carbocatio
to protonate the carbonyl group. e ly acidic ~d lo
10
otd~ " "' H (b)
OH N02
14· Most stable alkene is
(a) CH2 = CH2 (b) CH CH = CH2
3

>c=~>cd ~ >y-§- H~t§ -H

/r(N02
Rearrangement reactions (d) H3C\c= c / CH3

OHI
(a)v Ell /,9 (c) H3C" C=CH2

N, H3C / H:iC / "-CH3

U ··f"H N-H
I U sually in organic reactions , the function

>c0n•
/ I -~on~
/ H+

§<:H
H substrate undergoe s a structura l change
w~ 0up of the
1
f ~v<ll ~
H
N02 (d)
Ell
N02 1
5. The dehydration of n-butanol with acid gives
(a) a mixture of 1-and-2-butene in equal amount
_u_cl_eo....,phi'""·1,,---ic-ad-;-cd;::-1ti;--:- . out affett~
the carbon skeleton of the molecule , While
1
_N (b) but-1-ene as the major product involving primary
likely to
. h of the following alkyl halides would be most

1-H
elimination
-H20/
•• reactions , atoms, groups, double bond O
migrate within the molecule . Such typer 0
f in ?ther or/
~:c1io~a1 gro: 5, :~ca rearranged product under SN 1 conditions?
carbocation as the intermediate
(c) but-2-ene as the major product involving a
>n .. I called rearrang ement reaction s.
eactions are proton shift to form a more stable secondaiy

~
+"1 (b) ~ r carbocation
>c =N<---> C =N-H_ ._ C-N,-H (a)
(d) but-2-ene as the major product involving a hydride
I -W I r
shift to form a more stable secondary carbocation
~ Br 16. E2 reaction is called
(d) X Br
(c) (a) ~elimination
(b) 1,2-elimination
Table 19.4 Some rearrangement reaction s 6
_Which type of addition reaction gives more stable (c) Both (a) and (b)
product? (d) None of the above
S.No. Reaction Rearrange ment reactions ---
(a) 1,2-addition (b) 1,4-addition 17. Dehydration of alcohol usually goes by
I. Rearrangement by acyl nitrene (d) None of these (a) E1 mechanism

'Aw--Oy ~
Hofmann-bromamide rearrangement, Lossen rearrangem
ent, 0 --- (c) Both (a) and (b)
(b) E2 mechanism
Cunius rearrangement, Claisen-Schmidt rearrangement R R'-N=C =07 7, If the product of the above reaction is (c) E1 CB mechansm
R
H O H20 CH3?HCH=C HCH 2 CH 3 then addition is (d) St,2 '.11echanism

R~2 Br CH3

0
+C02i (a) 2,5-addition
(c) 1,4-addition
(b) 1,2-addition
(d) None of these 18. PhCHiCH 2CH3
I
~A
t-BuO H
11~0v •• 8. Which is not observed in nucteophilic addition reaction? OTs
R--eJ... ~~x - O=C=N -R
(a) Bond angle decreases and repulsion increases Predominant A is
~ Alkyl isocyanate
(b) Bond angle and repulsion decreases
2. Rearrangement to electron deficient oxygen (c) Both repul sion and free energy increases
?H3
Baeyer-Villiger oxidation 0
II (d) Repulsion increases and hybridisatio n changes (a) PhCH=?C H2CH3 (b) PhCH2C= CHCH3
R'-.,__
R'/0 + R'--C-0 --0-H - RCOOK + R'COOH 9. Nucleophilic addition will be maximum in CH3
(a) HCHO (b) C 6H5CHO
3
· Rearrangem ent of phenol derivatives (d) CH3COCH 3 (c) PhCH2?HC = CH2 (d) None is correct
(c) CH3CHO
Claisen rearrangement
is called
lO. The addition of HBr in the presence of peroxides CH3

4. Pinacol-pinacolone rearrangement
(a) free radical addition reaction 19. Carbanion (A) loses a leaving group to form alkene.
lb) nucleophilic addition reaction Which is/are correct statemenl(s)?
(c) electrophilic addition reaction CH3 H3C ~ CH3
fl (d) _Both (a) and (b)
· Which reagent will not give peroxide effect?
H3C
)r-< + Base ~ h L CH3
(d) in all cases H3C H L CH3 I H3C (A)
(a) HF (b) HCI (c) HI
12
' Select the correct statement (s) . - Lo H3C \___/ CH3
to larger
(a) HCi and HF do not form free radical easily due

Check Point 19.~ ...... ...... ...... ...... ...... _. _ (b) ~and-energy
1
With a minimum bond energy is very reactive
. ~
H~C:
I \ CH3
( ) and instead forms t2 (a) It IS E1-CB type (b) It is E2 type
1. Following ion is called (~) ~:th (a) and (b) (c) 11 s E1 type
1
(d) None of lhese
H 2 xide
• Select the incorrect statement (s) . 20_ In El-CB reaction ,
intermediate is

(a)
(b)
a-complex
carbonium ion
e
O CH3 (a) Si. 1 reactions also take place with some ellminat1on
(b) Si. 2 reactions with chiral compound s give racemlc
(c) Si. 1 reaction is faster In more polar solvents
(d) All of the above are incorrect statements
rn
l~tura
!J, In the ne of the above
rn addition of HBr to propane in presence of pero
st
la~~ a_b1e free radical form ed is
(c) ,H3CHCH3
•
(b) BrCH 2 CHCH3
·
H C'--.!i!
(a) ac/c.;H
Ha
H3°'-._~ c(CHa
(b) HaC/ - I Br
CH3
(d) H3C'c-cH < CH3
(c) arenium ion 3 CH2CH2CH3 (d) CH2CH CH3 ..
(c) CH3CH2CHCH3 . H C/ '- CH
(d) Both (a) and (c) • Cone. HN03 forms NOt in presence of I 3 3
(a) cone. H2so. (b) Fe Br
(c) FeBr3 (d) AICl3
 • Temporary n-electron
~
• Organicreaclionstakeplacelhroughtheformalion
Fast Track
(hap~er
electrophilelscalled
ofreaclivecarboninlermediateswh1chcanbe • 11:-electronshilt in co
• freeradicafsfikeC~ mesomeric effect 0
• carbocationfii~H3
• carbanionlikeCH3 REVISION • When several structur
contribute the truest

e><erc1ses
• carbene(singlelandtriplet) no one can be said lo
FUNDAMENTAL CONCEPTS OF molecule is referre
• radical ion
ORGANIC REACTION MECHANISM the phenomenon is
• Homolyticfissionresullsintheformalionoffree
radicals. • Electron-release by ai°ky; g .
Stability order of free radicals is unsaturated group is called hyperconjugatlon, and therer~~P attaciJ!dlo
■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ a ■ ■ ■ ■ ■ ■
H-alom at a-carbon wrt (C = C) bond. OUld be aI l¾ite ll
• a: 11 II D II

CH 2 = CH-CH 2 andCJi 5 CH 2 >3' >2' >10 ,CH3

(Resonance stabilised) CH3 -CH =C~ (Max.)>-CH2 -CH=Cfii >
• Helerolytic fission resulls in the formation of carbocations or carbanions (from R
-CH -CH = CH2> -~-CH
-t') depending on the electronegativily of R> Yor Y> R.
• Reagentscanbe / I (Mint~\ Al Taking it together
- electrophile (Lewis acid, electron-deficient) Types of reactions
(i) Substitution reactions
J (Assorted questions of the chapter for advanced level practice) . .
- nucleophiles (Lewis base, electron-rich) 7. In which of the following ways does the hydride ion
(ii) Addition reactions When CH 3 CJ undergoes hornolytic bond-fission
-ambiphiles (having nucleophilic and electrophilic siles) tend to function? (b) A nucleophile
(iii) Elimination reactions 1, (a) carbon undergoes a geometric change from tetrahedral
• Free radicals are planar chemical species, i.e. sp2-hybridised. (a) An electrophile (d) An acid
(iv) Addition- Elimination reactions to planar 3 2
(c) A free radical
• Radicals ions can be formed by addition or removal of an eleclron. (b) hybridisation changes from sp to sp

6
(v) Rearrangementreactions 8. Most stable free radical is
• Stability order for radicals PhiC > PhiH > PhC~ > Allyl (c) Both of these takes place CH
• Nucleophlllc substitution starts by the initial attack of anucle<)phile.11 (d) None of the above takes place
> 3°> 2' > 1'> vinyl> HG== C proceeds via SN 1 (unimolecular nucleophilic substitution) and,SN2' 3
'" · 2, Select the correct staterne~t (s) about carbene.

Clo
(bimolecular nucleophilic substitution)
• Carbocations are sp2-hybridised and trigonal planar in shape. They can be (a) It is obtained by photolysis of d1azomethane
(a) • \
formed by the heterolytic fission or by addition of aproton to an unsaturated • SN1 reaction 1° < 2° < 3° alkyl halides/benzyl halide or ketene .
system.

3
e
Stabifityof carbocationCJi 5 C~ >3°>2° > 1°,CH 3
e

• Carbanions are sp -hybridised and trigonal pyramidal in shape. They can be

formed by heterolysis of covalent bond, treatment of 'a - Hcontaining
• SN2 reaction 1°> 2°> 3° alkyl halides/benzyl halide
5ti1or5ti2 R-F <R-Cl <R-Br <R-1
• When there is chiral carbon (C-X) in alkyl halide, there can be 'in~~(Ojl 17/
Sti 2 reaction and racemisation by ~ 1reaction. • ,
(b) It can be inserted into alkene fonrung

cycloalkane .
(c) It can exist in singlet or tnplet state
(d) All of the above statements are true .
(c) \
cP' \
(d)o
e ~
• Electrophilic addition Al mulliple (C = C), (C == C) bonds. , . _.:, 3, Which of the following is incorrect representation?
aldehydes having a-hydrogen with OH ions by the addition of anions to alkenes
andalkynes.
- Markownikotrs rule is followed when there is aaddition ol HXto · ' ·
~ ~ >1° >2° >3° unsymmetrical alkenes. (a) H2C = O • (b) HzC-0 al
is
Stability of carbanion 9. Most stable radic
- Intermediates are carbocations which may undergo 1,2-hydride or (b) CH2=CHCH2
• Carbenes can exist as singlet or triplet and are obtained by photolysis of 1,2-alkyl shilt to attain more stability. ,. . ., (a) CH2 =CH
diazomelhane (C~ = N2) or kelene (CHi = C= 0).
• Electronic displacements in acovalent bond
• fnductiveeffect(Perrnanenleffect)
- There can be 1,2-addition or 1,4-addition at conjugated di~e5;,
- In presence of peroxide, addition is against Markow~iko(fs,rule . '.
(c)Q-rn2 (d ) O C H3

~~'"~{A
• Electromeric effect (Temporary effect) • Nucleophlllc addition At carbonyl carbon (C = 0) gr nitrlle car~~n 4, The order for ease of heterolysis of following t-butyl
• lnductomeric effect (Temporary effect) . (-C==NJ 1eavln'; 'gr~plsi compounds is 10. Potential energy of th~ tertiary carbocation is
0
• Mesomeric effect (Permanent effect) • Elimination E1 reaction is favoured in compounds in which hthal produciS (Cl-! 3 ) 3 C-OH; (CH 3 hC-OAc; (CH3)~-
secondary or tertiary carbon with carbocation inlermedlale, ~uc oceed Jhrough 1 II
• Resonance (Permanent effect)
are more substituted alkenes (Saytzeff). E2 reaction does not pr (a)I<II<!II (b} ID < ll < l
• Hyperconjugalion (Permanent effect) carbocation intermediate and order is
(c) I < m< II (d) 11 <I < III
• Permanent polarity as a result of electron-displacement (due to electronegalivity 3° > 2° > 1° alkyl halide d react with
difference) along a carbon-chain is called lnductlve..ffect. 5 \In_ ction?
• Less substituted product is Hofmann product. lnlermedlal, '"nich of the following cornpoun scan
- Negative inductive effect (-I) is due to electron-attracting groups and th the Lewis base a- in a Lewis acid-base re~ .
positive inductive effect(+/) is due to electron-repelling groups. • Sic reaction lakes place in benzene nucleus with a-complex as e s double (c} mr (d) 3
(a) CH4 (b) AlCl3
• Rearrangement reactions are the reactions In which atom, group ' Reaction coordinate
6
bond or functional group mlgrare within the molecule. · Which one of the following C-H bo nds is lhe (b) Only B
Weakest for hornolytic fission? H H (a) Only A (d) Any of A, B, C
la) Cl-13 - H (b) (C6H5)C 2 - (c) Only C
(c) C6 H5 - H (d} (C 6 H5)3C - H
 \
60 OBJECTIVE CHEMISTRY Vol. 1
Chapter 19 : Fundamental concepts of organic reaction mechanisms
0g
17• Ionic species are sta~ilised by the dis e the correct statement(s).
o fission in two different Which of the followmg carboxylate i~n ~saJ of ch,. 29. Which of the following produc~s the best electrophile?
11. Covalent bond can under!ntation involving a 5elect roup activates benzen~ nucleus for attack of
ways. The correct repres stable? [ Is the lli""!e, 23• (a) --~i;p1iile at or_tho and para-sites
. [NCERT Exemplar] H" H3 C "
heterolytic fission of CH3-Br is 0 Nce11l' Ost eleNfl group activates benzene nucleus for attack of (a) H/C=O+R '--l (b) H / C=O+W- -t
II o el•~,~ (b) ;ctr;phile at ortho and para-sites
(a) CH~Br - c!H3 + Bra (al CH3- c - o - (bl Cl-ca II th (a) and (b) . H3C'\.
0 2-C-..o- (c) JlO of the above (c) /C = 0 + ff' --l (d) None of these
(b) CH3fBr - c!H3 + Bra
o d) rJone H3C
lJ · ( ·ch does not contain conjugate system?
(c) CH3fBr - af3 + Bra, (cJF-CH2- c - o - (dl F"'-ca II 30. The addition of HCI to an alkene proceeds in two
(d) CH?4r - CH3+Br
12. Stability order of ...... is in order
18. Which of the following has maximum stab· .
energy as a result of resonance? ihsation
·
F-'/ -C.-.0· z.4, WJii
(a)
cH-COOH
cB2""
(d)o
(b) CH2=CHCHO steps. The first step is the attack of W ion to
:::: C=C; portion which can be shown as

J-t~c( J>'=c<
O C~2 , CH3CHi:H2, (CH3}JC, CH2=CH oa 0 (a) (b) i-t

6
N
11 0
. urn hyperconjuga tion is observed in
II ill . 2s,MaJOlll
I (a) I: (b) v C - o
(d) All of these are possible
(a) N<II<III<I
(cl I < II< III < N

the following cations?

(b) IV<II<I <III
(d) N < I< III< II
13. What is the correct order of decreasing stability of
[NCERT Exemplar]
(c) CH 2= CHCH2
a

19. Increasing order of pKa values (pKa = -log K,)of

(a)
O CH=CH2 (b) OCH=C H2 31. Following step is
CH3CH3 + Cl' -
(a) chain initiation
,
CH3CH2 + HCI
(b) chain propagation
(c) (CHJ)JC-CH= CH2 (d) O C H3 (c) chain termination (d) chain disproportionation
e H 20, CH30Hand C 6 H 5 0His
CH3 -CH-CH3 (a) H20 < CH30H < C5H50H (b) CH30H < H 0 <C H0H
2 6 5
32. CHi:H2 disproportionates to
I (c) C6 H50H < H 20 < CH30H (d) C6 H50H < CH 0H <Ho _Following carbocation changes to more stable
3 2
26 (a) CH2=Cfl 2 and Cfl3Cfl3
carbocation (b) Cfl2= CH2 and Cfl3CH2CH2Cfl3
20. Which of the following comparison is not correct?
(c) CH3CH3
(a) O O H > CH30H (acidic nature) (d) Cfl2= CH2
(a)II >I > ill (b)II >ill>I
(c)ill>I >II (d)I>II>ill 33. Which of the following statements concerning E2
14. In the following reaction, (b) O N H2 > CH3NH2 (basic nature) (b)OCH3 reactions of alkyl halide is true?
(a)OCH 2 (a) The rate of an E2 reaction depends only on the
(CH3 ) 3 Ce +H2 0 - concentration of alkyl halide
I II (c) o i H 2 > cHlH)2 (stability) (b) The rate of an E2 reaction depends on the
(a) I is a Lewis acid and II is a Lewis base (d)eoCH 2 concentration of the base
( c ) o - C H3 (c) The C-H bond and the C -X bond (X = halogen) are
(b) I is a Lewis base and II is a Lewis acid 0 0
(c) Both are Lewis acids
(d) o ~ O H > CH 3~0H (acidic nature) 27, Ethynic hydrogen is released most easily in (d) ~~~:~0 ~:e:;~::::;y react faster than aryl halide
(d) Both are Lewis bases
15. In which of the following compounds the carbon
marked with asterisk is expected to have greatest
positive charge? [NCERT Exemplar]
21. In the following compound which hydrogen is most
acidic?
(a) G-c ==CH (b) 02N--O-C S=CH
34
_ In the following free radical substitution reaction,
CH3CH2CH2CH3 + Br2 ~
(a) enantiomer R is formed (b) enantiomer S is formed
(a)*CH3-CH2-Cl (b) *CH3-CHz-M g•cr (c) Both R and s are formed (d) None of these
(c) *CH3- CH2-Br (d) *CH3- GHz- CH3
Thinking process When a more electronegative atom is attached to
,g;~"]a
6[HYH
( c ) ~ ==CH 35. Dehydrobromin ation (-HBr) of the following in
increasing order is
carbon,thesharedpairofelectronmovestowardmoreelectronegative
2a, Electrophilic addition reactions proceed in two steps. Br
-
atom. Carbonhaslesselectrondens,tyandgainspartialpositivecharge.
16. Select the incorrect statement.
o-¾ The first step involves the addition of an d ~ ~Br
(d) Ii ~lectrophile. Name the type of intermediate fo'.me ~ Br
(a) Electr~n-withdrawing inductive effect of the carbonyl (a) ex (b) 13 (c) 'Y II
in the first step of the following addition reaction. ill
group m_ - _co_OH group weakens the 0-H bond and
22. Select the incorrect statement.
:v~~:h:rusat1 on of a carboxylic acid compared with (a) .Branching at the electron-deficient carbon 5
trongly l-!3C-Hc = CH 2 + H+ - ? (a) I <Il <ill
stabilises carbocations . 1•is fof!ll 311~ ~ ~: carbanion (b) ID <II <I
(b) Inductiv~_effect of the chlorine destabilises the acid (b) Greater the stability of carbocation, easie~~ the heal 0 (c) , carbocation (c) I= II<ill
and stabilises the conjugate base 2
(c) Greater the stability of carbocation, sm er I (d) I O carbocation (d) ID d= II
(c) Aniline is a weaker base than ammonia formation carbanion
(d) Phenol is a weaker acid than water . eater the [!eat o
(d) Greater the stability of carbocatton, gr
formation
 Chapter 19 : Fund G,
7~ OBJECTIVE CHEMISTRY Vol. amental concepts of organic reaction mechanisms (!_01
41. Consider the following reaction,
0I
-,ediate electrophile in the following reaction is
5

r<OH ~ K ,~
6 111te1w 1. Which compound undergoes nucleophilic substitution
~
.
✓,p
36. In the following reaction;
I 2 3 4 sHCH+HBr- 4• + (CH3)3CCH2Cl with NaCN at the fastest rate?
CH CH=CHCH=C 3 CHCH (al Br~ ( b )
3 CH3CHCH2CH= 3
Br ~
I Which response contains all the
correct
(c ) B r ~
Br 5
taternen~ (d) Br~
about this process?
addition is called (d) None of these
(b) t ,2-addition I. Dehydration
(a) 2,3-addition II. Carbon skeleton migration
(d) 4,5-addition
(c) 1,4-addition 52. Increasing order of the following for SE reaction is
m. E2 mechanism 'fy the following reactions,
37. 1,2 or 1,4-addition can take place_~t rv. Formation of most stable carbocation forms 47,Class1 CH3
00{30
(a)O MQ (a) Both I and ill.
(c) I, II and IV
(b) I, II and m
(d) I, III and IV
42. In which case product formed is identical in th ·
i.
r'tl
v!'3
I

CH3
-
CCH2 Br + C2Hs O -
I
(a) l <II<II!
I II
O C O OH

ill
(b) III < ll < I

0 absence or presence of peroxide? e (c) II < ill <I (d) I < III< II
0
(b) CH3CH=CHQ-I
CH3
(a) CH3 CH= CH 2
(c) (d) All of these 3 I Q
II' CI-l 3cCH 2 Br + C 2 H 5 0H -
1 53. ~ Q ~A;Ais
(c) o - C H 3 (d) O c H ~CH2
38. Select the alkene (s) in which addition of HX is 0
CH3
strictly regiospecific:
43. Out of the following E 1 reaction is favoured in whicl (b) l : Sr,2,II:Sr,1
rYiCH3 (a)!: Sr,1,II: ~2 (b) ~ O H
~ case? (c) Both SN 1 (d) Both Sr,2
II. OH OH
I. OCH=CHCH3
alkyl halides for
· ) oCHCI
(b 43, Increasing order of the following
,.. SN! reaction is CH3CJ(I), CH3,CH3(II), (c) ~OH (d l ~ o
(YH2 CH3
ill. CH3CH=CH2 IV. ~ Cl 54. Which of the following alkyl halides can undergo SN I
(CH3) 3CCI(ill) reaction?
(a) Only I (b) Both I and II
(a) ! < II< III (b) II< I < III
(c) I, II and ill (d) II, ill and IV
39. Select the correct statement(s) for the following
44. Which -one of the following undergoes 1,4-addition
with CH3SK (in ethanol)?
(c) lll<I < II (d) I < III< II

49, Which among the following has least free energy?

I.Q-c1
reaction.
H3 C

> C=O + HCN -

H3 C
) c-CN
H I
(a)u ~CH2
(b)
6
0

/
CH3

(a> l) ~E fu) (Y
V
III. CH? =CHCI
(a) Both I and II
IV. CH 2 =CHCH 2 1
(b) Both 11 and m
(d) Bot h II and IV

,,,¢
(c) Both I and ill
H , 0
OH in order of increasing SN I
~ 55 _ Arrange these compounds

C)C: ex:
(a) Addition takes place at the carbonyl carbon and thus, 0
z reaction rate
addition is regioselective

"' ¢
(b) A chiral carbon is produced and racemic mixture is formed (d) CH3
(c) ·eeometry of the reactant is different from that of the
product (d) Ph+Br ~Br
(d) All of the above statements are true CH3
I
40. Addition of HCI to 3,3-dirnethyl but-1-ene yields two th
45. Which H is abstracted most easily from e given
SO, CH2"=CHCH undergoes free radical subst itution CH3
products, one of which has a rearranged carbon
skeleton. Which of the following cations are
molecule?
ii Using NBS. P;oduct formed is CH3+ Br ~Cl
intermediates in that reaction? ,,,----..._ (a) CH3CH-CHBr (b) CH3CHCH2 CH3
IV
EB
(CH3) 3 CCHCH 2Cl,
EB H .H CH3 - I I III
(CH3 ) 3CCHCH3 Br Br (b) I < II < III < IV
I II (a) IV<Il<III<I (d) IV< I < II < Ill
EB EB f ' I ,CH3 (c) CH2=CHCH 2Br (d} CH2=jCH3 (c) IV <I< III <il
(CH3)2 r(CH3)2

Cl
(CH 3 ) 2CCH(CH3 ) 2
Hl
Ya Br
III IV
{a) Both I and II (b) Both I and III (a) ex (bl j3
k) Both II and III (d) Both II and IV (c) y (d) o
 1§) OBJECTIVE CHEMISTRY Vol. 1 Chapter 19 : Fu nd amental concepts of organic reaction mechanisms 03
6 2. Which reacts fastest with cone. HCl?

56. H
t
CH3 ~ Product (butan-2-ol)
Cl
2CHJ
(a) 0' -
CH2CH20H (b) 0-'
-- 7licli3
68·
. er the following reaction,
consld

!3~
Na0!-1, 5N2 H -t
Ph
Q H,O, Si,!
~A
Possible products can be

?83
TH3 I. CH3COCH2CH3
d- O)j Me
~l ~~~~~~: ::
~acemic mixture (c) CH3,-0H (d) CH2 =C1-Icli20B for!Ilation of A proceed w_ith _racemisation. 613
(c) Product is d J. forJllation of B proceed with mversion. A and B can respectively
(d) None is correct CH3
JI. ct the correct statement. (a) Both I and II (b) Both II and I
57 CH3CHCH=CH2 + HBr----tA 63. Acidic n a ture of CH30H(I), CH SH(I!) Sele d II both are correct · (c) II in both cases (d) I in both cases
. I CH
3
NH2 (III) is in order
3 and (a) ~y I is correct 73. Increasing values of dissociation constant Ka of
CH3 (b) nl n, is correct
(a) III < II < I (b) ID < I < II CH3COOH (D, HCOOH (m and C 6 H 5 COOH(ill) are
A (predominant) is (c) O y f the above is correct (a) I < II < III (b) III < II < I (c) I < ill < II (d) II < ill < I
(b) cH3yHCH2CH2Br
(c) I < II < III (d) II < I < m (d) None o
(a) CH3THfHCH3 74. What is the decreasing order of strength of the bases
H3C Br CH3
64. Basic nature of H 30+, H20 and Oir is in order
69
GB = CHCH2CH= CH2 - NBS
A, A 01-f",NH;:, HC==C- andCH3 - CH;?
Br (a) H 3 ~ + < H 2 0 < OH: (b) H 2 0 < O!r <l-! o• 3
' (m:st stable) is (a) CH3 CHz > Nlf:i > HC == C- > Off
(d) None is correct (c) OH < H 20 < H30 (d) Off = H3o+ ;, !! o (a) GHz= cHfH cH = CH2 (b) HC== C- > CTl3CHz > Nlf:i > Off
(c) CHiCH2CH3 2
I e e e e Br (c) mr > Nlf:i > HC== C- > CH3CH2
CH3 65. CH 3, NH 2, 0 Hand Fin increasing pKb values are (d) Nlf:i > HC== C- > Olr > CH3 CH:i
(b) cHz =cHCH = CHCH2Br
- + e e e e
58. CH CHCHCH
3 3
5N2• c,HsONa product (ether); ether is (a) CH3 < NH2 < OH < F =
(c) cH2 CHCH2CH "'."'CHBr
EB
75. Electrophile N0 2 attacks the following
e e e e (d) None of the above 1s correct
I I EB e

00 0 6
H3C Br (b) F < OH < NH 2 <CH3
. Which of the following shows SN 1 reaction most
e e e e 70
?C2Hs (c) OH < NH 2 < CH3 < F readily?
(a) CH3fH-fHCH3 (b) CH3ycH2CH3 (d) None of these correct
CH3 OC2Hs CH3 66. Stability of following alkenes in the increasing order
r7f{CI
ill IV
(c) Both ~e correct (d) None is correct is (a)~
CH3CH=CHCH3 CH3r=rCH3 In which cases N0 2 will be at meta-position?
59. Which one of the following exhibit all the effects,
(a) Both II and IV (b) I, II and ill
namely inductive, mesomeric and hyperconjugative? H3C CH3 (c) Both II and III (d) Only I
(a) CH30 (b) CH 3CH = CH2 I II
76. CH3CH2CH = CH 2 +tBuOCI ---t Products;
(c) CH3CH= CH wCH3 (d) CH2 = CH - CH= CH2 CH39=CH2 CH39=CHCH3
0 CH3 CH3 ~Br
V
.
(a) CH3 r
Product (s) is/are
CH= CH,

,so,:, ¢
60. Which of the following is dehy drated to a maxi~um rn IV 71. + CH30H --+ A; A(predominant A) is

:77:cH (a) l < IIl < N < II

(c) IV < III < II < I
(b) I < ll < III < N
(d) II < III < N <I
0
(c) Both (a) and (b) are correct (d) None of these

&OCH, .,"O"' 77 • Increasing order of basic nature of

67. &CH,OH (i) K2 C03

(ii)CH3l
A; A is
(a) NH3(J), CH3NH2(II) and O - N H 2 (III) is

OH (a) III < II< I (b) I < II < Ill

(c)A &OCH,
if
(c) III= II < I (d) III < I < I~ . .
_ Dehy dration of the following in increasmg order 1s
( d ) ~ C H3 (c) 78
(d)
UOH
UOH 0-"'" 0-"" y°" 9-°"
61. Basi~ strength of CH= C (I); CH2 = CH(II) and I II

L CH3CH2(ID) will be in order

(a) I < II < ill

(cl ffi < Ud

(b)II < ill < I
(d) ill<l < II
(a) I< II < III < IV
(c) J < III < IV < II
(b) II<III < IV<i .
(d) I < IV< II < III
 Chapter 19 : F nd
u amental concepts of organic reaction mechanisms
r::r,
~ 5
7~ OBJECTIVE CHEMISTRY Vol. 1

79. Consider the following haloalkanes, CH3

- -. - -c»g
85. Leaving tendency of the followin i

d , CH3COO , OH , CH3 f
ncreasingo
" · _ 1dii \ frofll
~
OH
f the following alcohols cannot be pr
g0. wJliC::noaJkene?
V
epare
d

(b)/----..,......OH
9 4. In the following case

R-CN-H ~ R--CN + H'

CH36-a - 3,Jlo'
CHJCH2CH2CH2CI, CHJCH2f8CHJ, I I II ill IV •~- (al l ,,.....__ pK0 is maximum when R is
Cl (';H3
11 ~ (c)
~ OH (d)~OH
(a) H (b) NH2 (c) CN {d) CH3
1
(a) VI < V < III < II < IV < I (b) I < n < In
. II s 2 reactio: is (c) I < III < V < II < IV < VI (d) cannot be ~,"/ <V<IV consider the following compounds. 95. Select the formula or statement representing the
Increasing tendency for SN I and N d~lded major product(s) of the following reaction,
(A) ~I: Idl<ill (B) SN2: fildl<l 86. Pairs of related chemical species are . 91, CI-1 cH 2 0H, II. CH 3 CH 2 0H
Which pair is not related through re given be!o\>/ I, I 2 Br,_ /H - +
Coose the correct option. ' . CH3CH20K
(a) A and B both are correct (b) Only A is correct (a) CH3COCH2COOC 2H 5, CH3C(0H)= ;~ance? . f H.,...-'C-C --.,, CH
CH3CH20H

<
(c) Only Bis correct (d) Both are incorrect O oe OOc21i5 H3C' \ 3
CH2CH3

a ex ,
CH 3 CHOH,
CH2Br . (b) CH3-C ( , CH3-C I JJ1. I
BO. ~ products. Expected products are 08 o F

c/\e
E9
Which one of the following is the correct order of
A. rY, B. C aCH20Et
(c)
eo
/'¾,0 ' acidic strength for the compounds given above?

,~()" 6
0
V OEt
(a)IV>III>I>II
(b)JI>l>IV>III
Select the correct alternates. (c) n > IV > I > III
(a) A, B, and C (b) A, and C (d) m
> I > IV > II
(c) B, and C (d) A, and B
e 2. Arrange the following alcohols in order of decreasing
81. 0- CH20H on dehydration with cone. H2S04 forms 87. Acid catalysed dehydration reaction of
2-methyl-1-butanol yields which one of the following:
9
reactivity (fastest -
with 85% H 2S0 4.
slowest) toward dehydration
(d)· Both (a) and (b) in approximately equal amounts
predominantly (a) 2-methyl but-1-ene (b) 2-methyl but-2-ene 96. From each of the following pairs select the
(c) A mixture of (a) and (b) (d) None of these compound that will react faster with sodium iodide
(a) O C H 2 (b) o-CH3 (CH3 ) 2 CHCH 2 CH 2 OH in acetone:
88. Which of the following pairs are correctly-matched I 2-chloropropane 2-bromopropane
for the number of monochlorinated prC?<Jucts OH
I II
( c ) O C H3 (d) o-CH3
(ignoring stereoisomers) obtained from the listed I 1-bromobutane 2-bromobutane
isomeric hexanes? (CH3 ) 2 CH CHCH 3
m ill IV
?H3 CH3 Number of monochlorinated (a) ll >III> I (b) I>III>Il
Isomer products (a) Both I and III (b) Both I and IV
82. CH3~CH2CH3 ~ CH3{CH2CH3 (I) (c)Il>I>III (d) I>II>ill
(c) Both JI and III {d) Both II and IV
SN
_I_._2,"'---3-..c:.dim=·:..:ceth=>y~l--=-bu=tan=e_ _ _ _ _T_w_o_ _-,-- 93, Which one of the following compounds undergoes
OH 97. Provide a sequence of reactions to carry out the
_ II_. _2'-
,2....c
-dim =' =-eth
= y"-"1--=-b=
utan
= e _ _ _ _ _'Thr
_ e•- - predominantly SN 2 reaction with aqueous NaOH in
?H3 followingochange:CH3
01, ill. 2-methyl pentane Fi~ polar aprotic solvents? CXCH3
E2 ' CH3C = CHCH3 (Il)
Select the ~orrect answer using the code given below, OH->
Which is predominant? (a) CH3a-QcH2Br
(a) Only I (a) I, II and III (b) Both I and ll ' OH
(b) OnlyII
(c) Both of these (d) None of these (c) Both II and III (d) Both I and ill
83. Relative stabilities of the following b . . 89. Major product of the following reaction,is (b) 02N-0-cH2Br
be in the order car ocations will
E9 E9 E9
(b) cone. H2S04 ~
l!.
C~3 CH3BCH2 CH2~H3 (c) Q-ctt2Br
: : ~:~:1
cone. H 2S0 4 Hg(OOCCH3 l2
(b) C<B<A
(c) ~
(d) C>A>B
cone. H2SO 4 MnO~ , OH-
34. Which one of the following will . ~ ,OH (d) lI2N-0-cH2Br
but-1-ene as the onl alk give 2-methyl (d) ~
(a)~
KOC(CH3 ) 3 in dime~yl s:;h:~~=~tment with
(a) l-bromo-2-methylb tan (b) • .
2
(c) 2-bromo-2-methylbu~ ~ (d) -methy! butan-1-ol (c)~ (d) None of these
0
2-methyl butan-2-ol
~OH
a
7, OBJECTIVE CHEMISTRY Vol. 1

104 . Which of th; following statements is/are

Chapter 19 : F nd

the following rule is applied in this rea t· ? .

u amental concepts of organic reaction mechanisms

wJ,iCh o f Ale, KOH c IOn. li5.- Which of the following intermediates is formed in
(a) CH3CH2 S is a:tronger base and rnore nu correct?
110· the given reaction?
98. The reaction, ,
C = CH2 +Br ~ (CH3)2
CH Br C than CH CH20
3 cleophil;,
cH13rCfI 2 CH3 -
=
cfl3Crl cl-I CHCH3 _major product
2 . ~Cl~
~CH3)2 le of a - step in a radical chain reaction. (b) CH3CH2S6 is a stron_g er base and less nuc 1· crI 3 = CHCH 2CH3 minor product
1s an exarnp (b) Termination CH CH 0 6 · ll• ~ann's rule 0 2N A /
leophil;, '¾
/;! :~:.~::on 3 2
af2

V" ,
(d) Heterolytic cleavage (a) ~arasch effect

"· F~"" c,I;CH,oN:~

(c) CH3CH2S6 is a weaker base and less nucleo ...
CH CH 0 6
3 2
(d) CH3CH2 S6 is a weaker base and rnore
1
Ph Uc~
·
(b) 5aytzeffs rule
;~ r,{arkownikoffs rule :
·ch one of the following undergoes~ reaction
(b)
0 2N O
e nucleophiJi 111, : NaCN' at the slowest rate? Cl
than CH3CH20 (d}
'
the major product is formed by . Br~ (b)Br ~ 0 2N
(a) Sr,1 reaction (b) Sr,2 reac_t1on 105. Which of the following phrases are .not (a) 0

(c) El reaction (d) E2 reaction associated with SN 1 reaction? correctly 116. Consider the following species.
e1 ,
H~~~
p I. Rearrangemen t is possible.
II. Rate is affected by solvent polarity.
(c)Br~
(d)Br~
1. Q-oe
100. Alkene + Cl2 ___,
H3C
In the above reaction alkene is
CH3 ID. J!::t: r:~e~e micleophile is impo~t in
112
. consider the following four carbonyl compounds 0
II e
(a) Z-but-2-ene (b) E-but-2-ene IV. ~~:;~tivity series is: tertiary > secondary , 1.Q-eHO II. 0 2N V 8 0 III. OW IV. CH 3 CO
(c) Z-but-1 -ene (d) E-but-1-ene
V. Proceeds with complete inversion of configuration V. CH 3 S 6
101. Consider the following statements concerning the
effect of trifluoromethyl group, -CF3, on an Select the correct alternate from the above
Ill, H c - Q - - c H O
3
IV. 0 2N-CHz-CHO
~!~ ~=c~~~~~
i~ s;ri~~n;{ n°Jct~;&i7f1~; ~~
electrophilic aromatic substitution: statement. aqueous solution?
Which one of the following is the correct sequence
I. The CF3 group will activate the ring. (a) Both ID and V (b) II, ill and V (a) V > III > I > IV > II (b} IV > n > Ill > I > V
of decreasing order of reactivity towards nucleophilic (c) V > II > I > IV > III (d} IV > ill > II > I > V
II. The CF group will deactivate the ring. (c) Only V (d) Only III
3 addition reaction of the above compounds?
ID. The CF3 group "'.ill be a meta directing. 106. Which of the following resonance structures is not a 117. The reaction is described as
IV. The CF3 group will be an ortho, para directing. (a) III > I > II > IV (b) IV > II > I > ill
·contributor to the cyclohexadie nyl cation H H
(c) II > IV > I > III (d) IV > ill > II > I
Which of these statements are correct? CH,(CH.ls ) t - B r ~ Ho-t ( (CH2},CH3
(carbocation CJ complex) intermediate in the nitration 113. Consider the given resonating structures of formic
(a) Both I and III H3C CH3
(b) Both I and IV of benzene?
(c) Both II and III acid (a) SE2 (b} Sr,! (c) Sr,2 (d} ~0

Ct
(d) Both II and IV

O t
N~2 118. The increasing order of stability of the following free
102. Rank the following in order of decreasing rate of
solvolysis with aqueous ethanol (fastest - slowest) <a) I fu)
=w =·1=
H-C-OH H-C=OH H-C-OHH -C-OH
l radicals is
(a) (CH )z CH < (CH 3h C < (C6H5}2 CH < (C6H 5}3 C
✓
,::::,
EB I + Ill -IV 3
(b) (C H h C > (C H5)z CH > (CH3)2 C > (CH 3 h C H
The most stable one fs 6 5 6
(a) Only IV (b) Only III (c) (C H )z C H < (C6H5)3 C < (CH 3}3 C < (CH3)2 CH
(c) Only II 6 5
(d) Only I
I II
(c) : ~
/ VEB (&Noooof"" "
(ill are contributors) 114• Predominant product in the following
(d) (CH )z C H < (CH3h C < (C 6H5h C < (C6H5 }z CH
3

u~
III
addition
(a) II > I > III (b) I > II > III (c) II > III > I (d) I > III > Il reaction is 119. The electrophile involved in the sulphona tion of
103. Major organic pro_duct formed from the followin
107• In a ring substitution of C 6 H 5 Z, the main product benzene is
sequence of ·reactions is g
obtained is meta. Here, the group Z is
3
(a) so; (bl so~- (c) tt;o (d) S0 3
(a) -COOH (bJ -Cl (c) -NH2 (d) -Cll 120. In electrophilic aromatic substitution reaction, the
~ ~ NaOCH2CH3

cJC:,
(i) B, H,; lOS. Among the following, which is least acidic? nitro group is meta-directing because it
light CH3CH20H (ii) H20 2, Oir (a) decreases electron density at ortho and para-positions

(b)oXCI
(a) Phenol (b) o-cresol
V Br (c) . ~nitrophenol (d) p-cWorophenol (b) cjecreases electron density at meta-position
(a)/\
109 · pound W (c) increases electron density at meta- position
• SN 2 reaction at asymmetric carbon of a corn (d) increases electron density at ortho and para -positions
OH always gives which one of the following?
121. Which of the following species does not exert a
(c) >-< OH
(a) An enantiomer of the substrate
~; A p~oduct with opposite optical rotation
A IIllXture of cliastereomers v
k) ~ C l
. (d)u ~
Cl
resonance effect?
(a) c 6HJlli2 (b) C6H5NH3 (c) C6H50H (d) C6HsCl
(d) A single stereoisomer
 Chapter 19 : F nd t:;,
(?!!9
u amental concepts of organic reaction mechanisms
7~ OBJECTIVE CHEMISTRY Vol. 1

, · entrance special_ format qu est·ions

127. Addition of Br2 t o O' -CH=Ci-I _
- -Clj3(,\) , a) Medical
122. Coonsiderth f o l l e w ~ O C i l l ~ o• H g1v~
Br...._y
r--hl'
;CH3 . Br tJ
and 'L_ ; I-I 1 rtiOO &, reason 8 · Asserti~n (A) 2-bromobutane on~ 1 reaction gives

N
H
0~ I N ~ u ~
N
IV
3
PJ-i
(Bl
Br H

Select the correct statements.

pi( !\Ci-I
(Q Br 3
Asse
r::e
/~ the
tions that follow two statements (Assertion d
given. Statement II (Reaso~) is purported ~n be
Reason /anation for Statement I (A ssertwn). Study both the
!:::~
a racerruc mixture as a product.
0
: (R) Carbocation is the intermediate of ~ 1

·
• Assertion (A) ~ 2 reaction takes place with
ill 9
I (a) B is predominant when A is trans d . the e;ents carefully and then mark your answers, according
What is the correct order of their basicity ? w~en A is c_is . an C1s Pretlolliinq :::e codes given below. retention of configuration of chiral carbon.
(a) I > ill > II > JV (b) IV > II > ill > I (b) B 1s predommant when A is cis and c-·15 k ur answer as Reason (R) Rate of ~ 2 reaction depends on the
(c) I > ill > JV > II (d) IV > II > I > ill when A is trans ,Pred~lllin.nt Mar {:,th (A) and (R) are true and (R) is the correct explanation concentration of the substrate and nucleophile.
(c) Both are correct statements {al of{A), l0. Assertion (A ) Dehydrobromination of 1-bromo-2-
123. Which of the following will be easily nitrated?
(d) None of the above are correct statements ' (A) and (R) are true but (R) is not the correct th l
/bi., Both

6
CH N02 explanation of (A). me Y propane is called 1,2-or J3-elimination.

(,) 6 0 3

01 (cl CH, NO,

124. The structure of the major product formed in the

<<
128. Identify the principal organic product-of the

following r e a ~ F + NaSCHJ---,i ,,,

i:
{cl (A) is trUe but (R) false.
{di (Al is false but (R} ,s true.
, Assertion (A) A tertiary carbocation is more stable
1 than a secondary carbocation which is more stable
Reason (R) Elimination involves two groups (or
atoms) on adjacent carbon atoms.
11 · Assertion (A) ~ 1reaction of 2-chloro-
3, 3-dimethylbutane with NaOH gives
0 2N ~ B r than a primary carbocation. 2,3-dimethyl butan-2-ol as the major product.
Reason (R) The inductive effects operate through Reason (R) Intermediate is a secondary carbocation
follewiag - ~ d ;;::; (a) f7'YF sigma bonds and decrease rapidly with increase in which undergoes 1,2-methyl shift giving more stable
CH3S ~ B r distance between the substituent and the reaction site. tertiary carbocation.
2. Assertion (A) Energy of resonance hybrid is equal to
I Matching type questions

"'YCN
the average of energies of all canonical forms.
(b) ~Cl Reason (R) Resonance hybrid cannot be presented by 12. Match the intermediates given in Column I with

o:H a single structure. their probable structure in Column II.

NC~

(,)yCI '"YCN
CN I
129.
8
OH n-Bu
f ( Et
Me ~ 3. Assertion (A) Hyperconjugation results in the
stabilisation of carbocation by delocalising the positive
charge.
Reason (R) Hyperconjugation produces some
additional bonding between the electron-deficient
Column I
A. Free ra<lical
B. Carbocation
C. C,rbanion
1.
2.
3.
Column II
Trigonal planar
Pyramida l
Linear
The structure of the major product formed in the
CN I carbon and the adjace nt carbon. 13. Match the following columns.
following reaction is
125. ~ich of the following would react most readil 4• Assertion (A) Benzoic acid is stronger than acetic Column 11
with nucleophiles? Y (a) Me~ Column I (Re, ctio n) (Ty pe)
acid.
(a) Cl (b) Cl (c) Cl (d) (¥Me :eason (R) Acetate ion is a weaker base than
- -- - - -- - -- - --
8
A. CHJGl=CH, + HCI --+ Gl, rH CH,

(a)y() (b) (c)0

UOCH3y (d ) V
~CH3 (c) ~ .

130. Consider the following statements:

enzoate ion.
S, Assertion (A) Ortho-hydroxy benzoic acid is much
;lore acidic than be n zoic acid.
B CHJCH =CH, , HBr
· -
~Cl-l,1CH CH
Cl

2 2 Dr
2, Dipolar
nddlt lon

N02
does not undergo SN reacti~n beason (R) Anion formed from ortho-hy droxy
Cl

126. Consider the following compounds.

when treated with C2H50
6
enzoic acid is stabilised by hydrogen bonding. f
C. (CHJ)2 CH,OH
Anhydrou:\ ZnCl2
cone. HCI
3. Etcc1rop h lllc
ndd l1i on
r because ' :ssertion (A) Phe nol turns blue litmus red. H
r
'? "? '"9
(CH3 ) 2 C 1·12Cl·l3
ac~~~:~ (R) Phenol ionises to give proton and thus,

What is the correct seque f Br

I. Br- is a poor leaving group.
II. The geometry of the molecule does not perJ!l
formation of carbocation at bridge head, mil
1
ii

III. The geometry of the molecule does n~; ;81:e~d,

7' Asserf
111 nature.

~ Y amme.
. .
illeth i1°n_ (A) Aniline is more basic than
_ _____ __':I~- -
D. GI,= CH 2 + CH2N , --+ c rt
~ N
--
4. Frc<- r:ttlk.1.I
add ition

given above in decre . ncedo the compounds backside attack by c 2 H 5 O- at the br'. ~re correct? /1ason (R) Lone -pair on N-atom in aniline is
reactivity? asmg or er of their SN l e ocalised.
Which of the statement given above is1j
(a) i>Jl>IIJ (a) Both I and I! (bl Both JI and I
(b) I > Ill > I!
(c) Il > ffi > I (c) Only I! (d) Only III
(d) Ill > I, II
 Chapter 19 : F ~ 711
undamental concepts of organic reaction mechanisms ~
7~ OBJECTIVE CHEMISTRY Vol. 1

17. M atch the terms mentioned in Co!u

terms in Column II. rnn I With the' Medical e~tranc~ gallerg
Column I
Y JJect/on of questions asked m NEET various medical entrance exams)

6~ A. Carbocation I. Cyclohexane and _ (CO owing reactions,

2 1 for the foll H B + KOH--t 6. Consider the following compounds, [AIPMT 2015]
B. Nucleophile 2. Conjug~tion of electr~exen, 1, Cf1 3 cH2C z r

A
6
Q<e,;;ru,J
+NaNH2~- ""-
"" M<, J. Free radical
_ _ _ _ _ _ __a----=.
dj_ac_en_t .:._
c. Hyperconjtigation
po:.::
bond with empty
si-:_l.ivel:c~:;:Pre,.~o~
ns of c.__

3. sp2-hybridised carbon . carbon

i>-orbital IVIthen%
(i)

(ii)
8 3c
y Br
CH3
CH 3 CH = CH 2 + KBr + H20

+KOH------>
·
H3C

OH
CH3
+KBr y
CH°7-
?13

CH
I
3
CH-o fh
Ph-----f-Ph ~ H 3

II
•

III

~
0 0
E. sp-hybridisation 5. !fe:i::!hat can receive a P~r of (iii) 0 + Br 2 - CXBBrr
[NEET-I 2016]
hyperconjugation occurs in
(a) Only I (b) Only II (cl Only Ill (d) I and II

C. CH
3
gCH, gOCH,CH 3
~~t::CH,09
3. Carbocation F. Electrophile
.ch of the followin~ stat~~ents i~ correct? . ...
~ ) is elimination react10n, (11) 1s substitution and (m) is
1. Which of tRe,
following is the most correct electron
displacement for a nucleophilic reaction to take
0 0 ( addition reaction . . .. . . . . place? ., [AIPMT 20151
II II (i) is elimination, (1_1} and (~_1} are subs_t1tut10n re_acl.!ons
CH3 CCHCOCH,CH3 18. Match the following columns. (b) C) is substitution, (11) and (111) are-addit10n react10ns ➔ ~ = c~:..L21
1 Column I
!~\ (;) and (ii) are elimination reaction and (iii) is addition
(a) H3C
H
( b l ~ filc-~:.Lcl
H

D. CH3 -CH= CH2 + HBr ;:~~:CH,Ilr 4. Carbene (Reaction) Cohunnn

(Type)
reaction (c) H3C _;t,-q~~l (d) H3C ➔ ~q-~~C l
_The pair of electron in _the gi_ven c~banion,
2
5. Benzyne A. (CH3Ja CCH2 ? H CH3 r-butoxide, t,. I. Nu~leophilic
CH C=C-, is present m which orb1tals?[NEET-I 2016]
3
(a) sp3 (b) sp 2 (c) sp (d) 2p
8. Which of the following is not the product of
addition
~?
15. Match the following columns. Br
3. In the given reaction, [NEET-11 2016]
dehydration of [AIPMT Re-exam 2015]
Column I (Reaction) Column II (Directing influence)
.,
A. -N H3 1. o, p-directing due to resonance
Anhy drous ZnCl2 /conc. HCI
t,.
O+O½P
fu)%
B. -CCl3 E2
2. m-directing due to inductive effect (CH3)2 ?CH2CH3 (a)~ (b)~
C. -CH3
D. -NH2
3. o, 1rdirecting due to hyperconjugation
4. m-directing due to reverse
hyperconjugati~n.
Q

S,.l
(a)~u
TheftYis

(c)~
~
(dl\_)

16. Match the following columns. (dlgn,:,"I 9. Which of the following order of acidic strength is not

Column I ·(Reaction)

A. CH3f HCH = CH2 + HBr --'--, I.

Column II
(Most stable
intermediate)
EB
D. C6 H5CHO + HCN Ba(CN) 2 C6 H5 rcN 4. , S.. 2
'''½) ,:," I
~
correct?
(a) c H3 . CH2 . CH COOH > CH 3
b
·

Cl
er·
Cl-1 2 ·
[Guj. CET 2015)
COOi-i

CH3f HCHCH3 OH ,-
> CH, · CH, · Cl-1 2 • COOi-i

crf"
CH3 4. Which among the given molecules can exhib~\ .
B. CH3fHCH2CH20H+ H,-50 4
CH
3
--. 2.
CH3
CH3

?
EB
CH2 CH3
CH3
19. Match the ions given in Column I with th eir nature
Ou<om©? CU:: 20161
Cl
(b) CJ • C. COOi-i > Cl2 · CH2 · COOH
3
(c) H· COOH> CH:iCOOH > C6H,COOH
given in Column II. . ~ I II III (d) CH3COOI-I > Cl-12 . CH2. COOH> (CH3)3 Cl-I· COOi-i
(a) Only III (b) Both I and III
_ _c_ol_u_m_n_I _ _ _ _ _c_ o_Iu_m
_~ A "d catalysed hy dration of alke ne is an e xa mple of
(c) Both I and II (d) Both II and III 10. Cl [Kerala (Med) 2015]
I. Stable due to resonance nd
_A_. _c_H_3 -_ ?
·_:-
_~_H
_-_c_H_J_ _ _ _ __ _ _ _ 5• !n which of the following compounds th~ bo c-:;-d (a) free radical substitution (b) nucleophil'.c sub~~itution
B F -cEB 2. Destabilised due to ionisation shall give most stable carbocati~~pMT 2015] (c) nucleophile substituti~n (d) clectroph1hc add . .ion

~ H3C ". H3C, Cl

(e) electrophilic subst1tut1on
CH-3 Which one of the following undergo nitration
(a) H3C /CH-Cl (b) H3C/C;:::-CH3 .
I . 11. eaction most readily? . [~erala (Med) 2015]
C. CH 3-c 9 3 Stabilised by . 1 H". r Aceto henone (b) Benzonttnl_e
I · hyperconjugauoi
::: Benzaidehyde (d) Benzoic acid
;=/H-Cl
CH3 . ~;i;, 1
(c)v (e) Benzene

~
 10 OBJECTIVE CHEMISTRY Vol. 1 Chapter 19 : F d /,7113
un amental concepts of organic reaction mechanisms ~

18. Assertion (A) Ally! and benzyJ c b

. length of the bond as
12. The correct order of de~re:;:~nfollowing structures is more stable than propyl carbocatj ar 0 cations
on. <re nowing reaction, 31. Which of the following is the most reactive towards
indicated by the arrow m [WB JEE 2014] Reason (R) Electron releasing gro IA.111.fs r11e fo
zS, H CH3 electrophilic reagent? [CBSE AIPMT 2011)
carbocation. up st abilises 20 11

)l )l+ +~+
0
(a) Both A and R are correct and R is th
explanation of A e correq
I I
C - C- CH 3
Alcoholic
-K-OH-,--H --KB4r .
- -0,-
(a) CXCH3.. (b) (X1 CH3
+t I +\1 t III (b) Both A and R are correct but R is Crl3 -I I 2
CH 20H ::::,,,.. OCH3

(a) I> II> Ill

(b) II> I> III
explanation of A
(c) A is correct but R is incorrect
not the correct cI-J3 X
(c)
CH3 CXCH3
(c)III>II>I (d) I> III> II

13 Which one is most reactive towards nucleophilic

(d) Both A and R are incorrect_
c
CH3
I
= C-CH3 is an example of
CX OH
(d)

NHCOCH3

· addition reaction?
19. Among the following carbocations Ph c+ 013-1 32. Which one is a nucleophilic substitution reaction
[CBSE AIPMT]
CHO ~COCH3 PhCH2 CH2 CH+Ph (II), Ph 2 CH CH; (~), CB 2Me(n, among the following? [CBSE AIPMT 20111
(a)©f (bJl9
2
Ph 2 C(Me) CHf (IV) the order of stability is
CH3
(a) a-eliminat!on
[AMU 20121
(a) CH3CHO + HCN - CH3CH(OH)CN

(b) ~-elimination .. (b) CH3 -CH=CH2 +H20 ~ CH3-r-CH3

CHO CHO (a) N >II> I> III (b) l>II>m>A;"8JEE20121 (c) Hofmann elimmat10n
(c) II> I> N > III OH
(d) I> N>ffi>II (d) None of the above (c) RCHO +R' MgX - R -CH-R'

'"~ {ill~ 20. Amo~g the following com_p~un~s the one that is Which one of the following undergoes SN2 6H
CH3 N0 2
reactive toward electroph1hc mtration most 26• reaction faster?
[AMU 2012]
(d) CH3 - CH2 -
F3
CH- CH2 Br + NH3 --+
(a) benzoic acid (b) nitrobe!~::: AIPMT 201 21
14. An incorrect statement with respect to SN! and SN2
(c) toluen.e (d) benzene
(a)VJH--Cl (b) O r H 3
13
vi
mechanisms for alkyl halide is [KCET 2014]
CH3 CH3 CH 3 -CH2 - CH- CH;iNll2
(a) a strong m1cleophile in an aprotic solvent increases the 21. Con~ider the reaction,
rate or favours Sr, 2 reaction
(b) competing reaction for Sr,2 reaction is rearrangement
RCHO + NH2NH2 ~ RCH = N-NH2. (c)VHP _(d) 33. Which will undergo fastest ~ 2 substitution reaction
(c) Sr,1 reactions can be catalysed by some Lewis acids What type of reaction is it? [CBSE AIPMT 20121 when treated with NaOH? [DUMET 2011]
(d) a weak nucleophile and a protic solvent increases the (a) Electrophilic addition elimination reaction CH3 CH3
27 _Formic acid is a stronger acid than acetic acid. This I I
rate of Sr, I reaction
15. The boiling points of four saturated hydrocarbons are
(b) Free radical addition elimination reaction
(c) Electrophilic substitution elimination reaction
can be explained using
(a) +M-effect (b) -I-effect
[KCET 20 11] (a) H5C2 -?- Br (b) CH3- 1 - Br

given below which boiling point suggests maximum (d) Nucleophilic addition elimination reaction (c) +I-effect · (d) -M-effect H CH3
number of carbon atoms in its molecule? [AIIMS 2014]
(a) -162° C
(c) -0.5° C
(b) -88.6° C
22. Which of the following does not show SN 2 reaction?
[AIIMS2012I
28. Most stable carbocation is [DUMET
2011
1 1
(c)H-1- r
<;:
3

B
1
(d) H-<;:-CH2-CH2-CH3
I
(d) -42.2° C
)c= CH-X
wQA) '"o'"Q.
(a) Vinylic halide
C2Hs Br
16. The most likely protonation site in the following
(b) Ally! ·chloride CH2 = CHCH2 0 Whi h one of the following alkylbromides und_ergoes
molecule is [WBJEE 20l4]
(c) Chlorobenzene 34
• tc apid solvolysis in methanol solution to give

(a)C- I
>O
. 8 7
(d) All of the above
23. Which of the following applies in the reaction?
CH3CHBrCH2CH3 ~ ? [AIIMS 20121
29. Which one of the nitrogen atoms in
0
:~:e:ponding methyl ether?
H3C "-c=CH-CH20CH3
H3C /
[DUMET 2011]

(c)C-3
(b)C- 2
I. CH3CH=;: CHCH 3 major product
II I ophiJic?
H!N- ~ - C - ~ 2 is the most nuc e [KCET. 2011] H
(d)C- 6
= CHCH2 CH3 minor product
(d)y
17. The radical is aromatic because it has II. CH2 (a) >=! / CH2"'-Br (b) )-yar
[NEET 2013]
Only ill
(a)
{a) Hofmann's rule (b) Saytzeff's rule

O-cH
I (b) Only I
(c) Kharasch effect (d) Markownikoff's rue
2 (c) Only II t n nucleophilic (c) ~ B r
24 • Under identical conditions, SN 1 reaction will oc~~o!21 (d) All three nitrogen atoms are equally 5 ro g
(a) 6p-orb'.tals and 6 unpaired electrons most efficient with [WJIJE centres Br
(b) 7p-orb1tals and 6 unpaired electrons (a) tert-butyl chloride 30 Wh· . . t rmediate in the
(c) 7p-orbitals and 7 unpaired electrons · r 1~h one of the following is ~ m ee resence of d that does not undergo hydrolysis by
(b) 1-chJorobutane eaction of benzene with CH3Cl m th p [KCET 2011] 35. The compo~ . [Kerala CEE 2011]
(d) 6p-orbitals and 7 unpaired electrons
{c) 2-methyl-1-chJoropropane anhydrous AlC1 ? +
SN I mecharusm l~l (b) C6HsCl

0
(d) 2-chlorobutane 3 (a) CH2 =CH°i:~2 (d) C6 H 5CH(CH3 )Cl
(c) C6 Hs 2
(a) ct (b) CH3 (c) CH; (d) (e) C6HsCH(C6HslCI