Orsanic Reaction Mechanism-Il

Types of Reaction Mechanism-

There are 2 types of mechanism by which an organic reactions may proceed:-
1. Free Radical Mechanism- In this type of mechanism, the reaction proceeds
via free radicals which are formed as a result of hemolytic bond fission. This
fype of mechanism is favoured in- (a) Gaseous state; (b) Non-polar solvents;
(c) Presence of radiations like Ultra-Violet rays, diffused sunlight, etc; & (d)
Presence of organic peroxides.

2. Ionic or Polar Mechanism- In this type of mechanism, the reaction

proceeds by ionic species like electrophiles or nucleophiles which attack on
the polar substrate molecule forming carbonium ions or carbanions. This
type of mechanism is favoured in- (a) Liquid state; (b) Polar solvents like
acids or bases; (c)" EEction displacement effects in the substrate; & (ci)
Absence of organic peroxides.

Types of Organic Reactions & their Mechanism-

A. Substitution Reactions
B. Addition Reactions
C. Elimination Reactions
D. Molecular Rearrangement Reactions

These are discussed in detail as follows:-

 Y
ar
5
,

These reactions involve transfer of an atom or a group from one side tp another
within a rnolecule to give a new molecular structure. In these reactions, nothing is
added or eliminated from the molecule.

Examples of lVlolecular Rearrangement Reactions-

t . r (.t.1.-e_-L
f!>*o-lu, :I n-**. -
o
44 ut *At,&),
ttl ct-cflr ^ct+=c*,. cHJ*cH:cH*c5
*Ba*.r,-e--
b e-&^. 2

e^) qL^., A/Al

rii,

J}{ 'cN, -' Lil, *cH, -, H) ? -'*3

C4_cH*Cu.
d i'-
CHs
rn- dri( ".-
-tro d.-6,*
 22

2. EzReactions- Ez stands for bimolecular elimination reactions. The reactions

are of second order.
Example- Dehydration of Primary alcohol by concentrated IIzSO.r

g,rr.rNroH H'rorct"*"/), / clr= cNz- * u, P

ldon-i7-o'c-
'tw -
"frrl-"-4""r*J "i, ^ ^"
Lfls^o-
WJ"D
Mechanism of E2 reaction- It involves the formation of a transition state as
shown below:-
a. Protonation of alcohol to form oxonium ion-

- cN,- o;s{9 O i<:'--) \/a *

i<,i i::
cHr cy3- cr/2 -
." \l_l
etr/oz",ru_I t-t . r^,,.-dr
&V r/,,uJ5;*ul
b. Dissociation & simultaneous loss of proton resulting in the loss of
rvater molecule and formation of alkene-

')e
H/ ,\_J+ @{*}-
,
cu,e$1u-"X::*':';;:'
\ A/ t+'(+, o+)
- ou
fr il*r$#':H"1- r. nf#
o, n. r E x a m p,. aroge n at ion (r em ov ar

of hVdroren halide i.e. HX)Aoil alkyl halide rvith alcoholic alkali

|
,*;,*- rU *N,a t,ta,,
-c u -CHs 1*;_)
- '-v'-' '
CH:
f -\nf v4
Z-d* o,-e
MechanisT
c'+.?j< q-4")- c H.-cur cN,> ct-/*r,*oln 4 o tt
.*hr/d-r d-r.2 -+ b-v7 t ..-.
r\ r__ 2 -d*u_o
f.rrfa <
k* *R -+ ko,,
 27

C. Elimination Reactions
These are the reactions in which atoms or groups are removed generally from two
adjacent carbon atoms in the substrate. This leads to the formation of carbon-
carbon multiple bond. Hence, elimination reactions convert a saturated compound
into unsaturated compound. These are reverse of addition reactions.
Depending upon the mechanism by which elimination reactions may proceed, they
are further classified into 2 types:-

1. Er Reactions- E1 stands for unimolecular elimination reactions. The reaction

are of first order.
Example - Dehydration(removal of water) of tertiary or secondary
alcohols by dilute H2S04 Hrr6v (J;1./ cAl. r
C A/' :- :ctr' +'l- o
)t-CNs -l7ya--'+
.ri]J-i,{-1/i,al(r')
or, "; )'
fo..{-
/
2-:Ur"/c '!--{*
Mechanism bf E1 reaction- It involves following steps:-
a. Protonation of alcohol to form protonated alcohol containing an
oxonium ion- -------\ -r. t t t -]-
l'.,*, ?.(;c,e"gi,j-u* r r -f ,*p:
!,
r'*r.*k/ t-i' *.',-i, o,-i!l-:tr;if*l(!*k)
G,, L e

b. Dissociation of protonated alcohol resulting in the loss of a rvater

molecule from.protonated alcohol to form a carbonium ion-
cvrjr ,c\<i s,4"
, G*)rr* * .?'{!,
oAol-Jvr-,b"-
fr.e{^",{J.-l* LJ )
I "G"d"
"*{& ^ 3*&/
c. Loss of proton from carbonium ion to form alkene-
CHt>*
Vi<i--])L.,.
\.- /
* u*'i(:
Qv, o+/
/ t*-t/ r./ea{- (4"""^ /
Lr'*f..q&-
 L]

Mechanism- It involves 3 steps:-

a. Generation of Nucleophite- It is done by heterolysis of the attacking
molecule. (Electrophile is also generated simultaneously) ...-

H !?N > H+- */- ciic^'y)

Heq"T
G")
b. Attack of Nucleophile on carbonyl carbon to from an intermediate oxy-
;
{L + il -) tt\
anion- -,,
"'\ ;<:-2 ,/o
cH: e1 ,-c:1-
(*y
o.- loo r' )
c. Attack of Electrophile on the oxy-anion to give the final product-
cu:r- }.<-_}+ cH, -oN
!"!\./
1u -l H' \
(H-r -'t{.* -eSl c& ---.\c^, t

s. pr.!il{ilfi.i.aoi,io, Reactions- rhese *'r#;ot*ig* k*tl

initiated by an electrophile. These reactions are generally given by alkenes and
alkynes which contain carbon-carbon double and triple bonds respectively.
Example- Addition of I{Br to alkenes- 2 cases may arise depending upon
rvhether the alkene is symmetrical or unsymmetrical:-
i. Addition of HBr to ethene(symmetrical alkene)- Only one product
tn Bf,:T:/L!,c=c,-r,*Hax-+ c#r- f ^,.)
/!t l--{, ;"--/ \ d
t,rlo.^-p
( {lLr,.-) [ r,c = cAre + ns* --s fo, *u;t J r'"(-f,"*/
Mechanism- It involves 3 steps:- f."- B^_o
a. Generation of Electrophile- It is done by heterolysis"ii-.
of the attacking
molecule. (Nucleophile is also generated simultaneously)
p'*C)^ Hetu%&'')
, H+ t /i..
(t*) C,J{, )
b. Attack of Electrophile on carbon-carbon double bond to form an
intermediate carbocation-
,d',Z5. -#J-,
Nt C Jt ff + ---- ttt4t iL,,,
-
cHr)\ f"*L or" ^

' 4^ 'r / r*L*-

Nr{:cU, +-
\\ ---=----/,' -/-/ H-l ' Hsc*Cgt
Hn*,1-..
__) '3L' "''2 J
I

e{r}/ ca.r. [o c*-dr.-

6r-{u.. Ji-d
 18

c. Attack o.f Nucleophile on the c-arbocation to form the final product-

L L-
,F/.
-#/i .-H- t ,') ----) ,,,^f-c+, lp^*."1a1
tt O^J.,'f )
ii.
Hr c
-
Addition
*._:r-_--r-'
of
H:
HBr to propene(unsymmetrical--
J
Two
c
alkene)- products,
are formed:- fq
I
CHJ*cs*Cg)
t+. e/+--o
CHt C tt: CL/L'*HBr. / ct+-<--

-
P-xe 7 e F<'-
(',y-"--,An"l Jlr,*-) - c Llz
- f ,,
l- lr,o,-o lJrf u -.3\
The major product is decided by a rule known as Markownikoff s rule given by a
Russian chemist who after studying a large number of addition reactions gave a
rule which was helpful in de'ciding the major product in cases of addition of an
unsymmetrical molecule like FIBr to unsymmetrical alkenes like propene.

Markorvnikoffls rule(or Nlarkorvnokov's rule):- This rule states thaf rn case of

addition of an unsymmetrical molecule like HBr, HI, HCl, etc.to an u-nsymmetrical
alkene or unsymmetrical alkyne, the negative paft of the addendum(adding
molecule) adds to that carbon of the carbon-carbon double or triple bond u,hich
contains lesser number of hydrogen atoms.
An addition which follows MarkownikofPs rule is termed as Markownikoffs
addition.

CAl - c tJ = c t-/z *Uc^ ---+ CH: cl-J* ca-

/u-e7. -- lr
2-d-,..2r*^--
' (\/t/^" e-r/ )
H*lh *-;A.ry '
C% -cH-.c&. + ^//^
YS ta * ct/z
- r,r,
8.",
1- Lo >-s f-t-o7 r,-*- (*i -*/*o tL._ f)
 19

Mechanism of Markownikoffs Addition- It involves ionic mechanism and

consists of 3 stePs:-
a. Generation of Electrophile- It is done by heterolysis of the attacking
molecule. (Nucleophile is also generated simultaneously)

rn trcty+s,l_)
H B-.'..-- H+ t- 8,,,
;
(trt') cnJ)
b. Attack of Electrophile on carbon-carbon double bond to form an
intermediate carbocation- In this two carbocations are formed out of which
one is more stable than the others.
4-
CH}
-
cH?cffi\*+
*)
--> CHS*cH-
2'cax
CH>
/'**i"Cfa)
P:-+7 e'u<-- Le do
".-So'.I
(f*.tu.l,_-J.r_l[
d-\ Hs - h?.
CH>*cH=ctJz 7*-:H+- > e
'*6t*1 /".* 6*"od\ * (ln "{l/, )
f>-a7 t '-+-
( f'rAr. -'-J s"* )
c. Attack of Nucleophile on the carbocation to give the final product-
cu,- f"Gdf tr"v/ c\* l, -rr,
Z'"G^fo"J'* : ^ LNtl z- L.cs-To^ rz
6**:,tlt)-t;r-,rJ .;#T*:-{;:
* (tr, +-k---\ ., CHt Ckt*
cHj {,f +- f;" 5r:'
ru":,*k"*l.rr*r/
-
u'") --4
d;lrxffitD
' Not.- in ,ro.-ul eonditious, alrvays Markorvnikoffls rule followed. This rule
is
is also followed in case of addition of HCI & HI.
 20

Anti-Markownikoff Addition or Peroxide effect or Kharash effect- In presence

of an organic peroxide like benzoyl peroxide[(C6H5CO)zOr], the addition of F{Br to
unsymmetrical alkenes like propene takes place contrary to the Markownikoff s
rule. This type of addition which is anti to Markownikoff rule is known as Anti-
Markownikoff addition. It was first observed by M.S. Kharash & F.R. Mayo,
hence, also termed as Kharash effect. Also this takes place in presence of an
organic peroxide, hence, also termed as peroxide effect.
g*-rrn, A C tl *eHz ^ ,c A/.'2
Ptro x,\6-r- t
L* * co)-o. -1*l,.o* F.,\ / o Le--' Yt "?'
, ^. s- Ly)
Ps-

cH: -ct-+= cNz *

@
H&", ^

P-o1s a-J ,1,'f*' CH\- l.Fr._C/'/)

^' JI
f*' j^
2-t.,-o;"r"./il';#)
Mechanism of Anti-Markownikoff addition- Peroxide effect proceeds via fi'ee
radical mechanism as giverr below:- i o", M^*,4",> ' , ,?' .
(e,t
-'!' -" ;€Yie. - /-, "rffi, Q
srL- iq
Y Be^'y Aee-eo'"'1;r*{
- 0t*r*/Fuorlo&.
d:d:_,\.*\eo, k, 4 cil.'t_
,Jrnuy^r_c>;p. ^/o^-&*i-" ? rl ,L/. * ,^
or^i"Sx)J,i--( v- 'n,3,lr^r*r*; zCoaA -
' Cr H, A'-
Ar- - cn* '
-J, l:.--<(
u;s\ r - tt *
+ .^^
'^l
q, cva - e{}", * Br, *T+.> c'r -"',, "1 '"-;u,f
f=.,I-r.-rl '"!o -
<u--&^f^ a -) s A1

Note- Markownikoff addition happens with HBr, HCI & HI but Anti-
Markownikoff s addition happens only with HBr and not rvith HCI or Hl. I is
because H-Cl bond being stronger(Bond energy: 430.5 KJ/mol) than H-Br
bond(Bond energy: 363.7 KJ/mol), is not broken by the free radicals, whereas
the H-I bond is weaker(Bond energy: 296.8 KJ/mol) than H-Br bond is easily
broken by free radicals but the iodine free radicals so generated combine
together to form iodine molecules instead of adding to the double bond.

cts\ cu * (u, + fud clr:,Cu - cN, + '."l

s,
B! "-' Ar-
T|fq>
z- r:r3r^,r,* / Xlm*-)
Err^u;rJ, ,ri,:'*L,r. )
-"'^
1-

H-trI "I;-'') cHJ-c/-/t

E' r-..,1 l*t-4lJ' p
cH:- iu*qu, + -Cila
p! *8-
l'6.l.;a*cP*!A<
z'Ft-.r.roJ l*-L,l ( ^.*'r'c"r(fa'] C Hirra*"d-"f .
 12

c. Friedel-Craft alkylation-
Cry ca

AT)t, --)
lJ Ct-t
). /)
':,--
' n,il(*-{".oy'r -
V
tt" ^.
,+
4" r.-o-ra ., */i1r..
Ba J +,).o
"o4 r
(+r**-r(l- / ( t'ro---A^u--o-*- )
d. Friedel-Craft acylation-
H

+ n*ar--)
(gr
/\,,,t
A.Vl tr (to"../io- )
$y'n**
8 a-ra---"--
-l
Z\q + c\co . lu
] 'b4cecHr n*Q!ryo->fii*,=
V.ft'#.,-[f)-____>
in the
Note- The sigma complex above cases is non-aromatic i.e. when it is
formed, the ring loses its aromatic character.

) Abstraction of proton from the sigma ,complex to give the final product-
The proton(H*) is removed by the nucleophile generated above.The ring
again acquires its aromatic character.

a. Halogenation of benzene-

+Hu * r.<,
lr.rr,.(A-*,-*/L )

@T-> F/sor,-
N 02 (d.l) '

-ug:;":^/r""
-li"*-o-L ,-o.Lr
C
"f - 4*. **f'r)
 L5

l. Free Radical Addition Reactions- These are the addition reactions which
proceed by free radicals.
Example- Addition of Cl2e H2e etc to alkenes in vapour phase or in
presence of ultraviolet radiations-

^* NN'c*ctt
2I
b, c= c Fle *^_Q, --*---+
' I
z

E &Le-t
CIq' ,. cr- CL
cl,'cA_{on^* .*Lo, ^

Mechanism- It involves 3 stePs:-

Ho"-.q+'rx
a. chain initiation
MA , _d_ * i
'-- c-ffiJrJ-
b. chain propagati ou,rsp/,r. + Li 3$i,, f * iu,
,',
f iu, + O:;rI9i: s* ftL j &
C,- JL
chain
'' T:lt";
- 'r-! *&
r,I'v N,'Jc -. cHa
J"
2. Nucleophilic Addition Reactions- These are the addition reactions which are
initiated by a nucleophile. These reactions are generally given by carbonyl
compounds which contain carbonyl group (ilC:O group).
Example- Addition of HCN to acetone-

.&\ to'a, gN
ta(
/
C
= e + Hcru \t-
'uj
--)
A.r{ou
'ur/
1..,(.c
f,u-o ,&I'--
 15

meta directing groups(ring deactivating groups)- The groups which direct the
incoming group to meta position are called as meta directing groups. Let us take an

It is clear from the above structures that nitro group reduces electron density at
ortho and para positions. The electron density of o- and p- positions is relatively
less than the m- position. Thus an incoming electrophile attacks at meta position.
Also the -NOz group deactivates the ring for an electrophile attack by reducing the
electron densify on the ring hence also called as ring deactivating group. It may
also be noted that the -I effect of -NOz group fuither reduces the electron density
on the ring thereby making the furlher substitution even more difficult. Other
examples of such groups are -CN, -CHO, -COOH, -COOR, -SO3H , Cl, etc.

B. Addition Reactions
These are the reactions in which the attacking molecule adds up to the substrate
without elimination of any atom or group. These reactions are mainly given by
unsaturated organic compounds like alkenes, alkynes, carbonyl compounds, etc.
These reactions convert unsaturated compounds into saturated compounds.

Depending upon the mechanism by which addition reactions may proceed, they are
further classified into 3 types:-
 L4

ortho and para directing groups(ring activating groups)- The groups which
direct the incoming group to ortho and para positions are called as ortho and para
directing groups. Let us take an example of directive influence of phenolic(-OH)

i*;o{
f-
OH group, the electron density is more on ortho and para positions. Hence, an
incoming electrophile attacks at ortho and para positions. Hence the substitutions
mainly take place at these positions. However, it may be noted that -I effect of -
OH group also operates due to which the electron density on ortho and para
positions gets reduced. But Tesonance effect being more powerful predominates
over inductive effect and overall the electron density increases at these positions.
Also -OH group activates the ring for an electrophile attack hence it is also called
ring activating group. Other such groups are -NHz , -NHCOCH3 , -OCHr , -CH:
etc.
Note 1: Generally ortho-para:directing groups have a lone pair of electrons.
But methyt group is an exception. It is ortho-para directing due to
+
"[n::Tjugationf':[:*"'-f cilt fi^rr. H-cHt i?u,
o
Note
\1t -'nrnrrr,. tr'O=
;,
2t ortho-para directing groups are generally ring acth",#\tr&o{
halogens, although being ortho-para directors are ring deactivators because in
their case 2 opposing forces are working. A halogen substituent is electron-
releasing by resonance but electron-withdrawing because of its high
electronegativity(Inductive Effect). The Inductive Effect dominates the
resonance effect and the net result is that ring is less liable to an electrophile
attack.
 13

c. Friedel-Craft alkylation- CHS

,1,,#-fu':Q-:jc'l;''ug
d. Friedel-Craft acylation-

ffi*f;-n q;'*,:K:fn
;.1
6u"-l'i"*4v) Mlql -- /r>roo,n, *Ftu-ist5t
* nlh{'*u *o o,, H,/, r. u 0., ,afL' o,i,i ons are
".
n
^V#;Y.#;;;(ft p

equivalent positions i.e. any position can be numbered as 1. The first substitution
can occur at any position. It is shown as follows:-
I

, ./r\r 2 t
cD\
;v't I

But after a substituent gets attached at any position in the benzene ring, that
position has to be given number 1. Now the two positions adjacent to the
substituent are known as ortho-(o-) positions(position 2 &. 6).The two positions
adjacent to the two ortho positions are known as meta(nz-) positions(3 & 5) and the

Directive influence of a functional group in monosubstituted benzene- When

monosubstituted benzene is subjected to further substitution, three possible
disubstituted products are formed but in unequal amounts. Two types of behaviour
are observed. Either ortho and para products or meta product is predominantly
formed. It has been obsenred that this behavior depends on the nature of the
substituent already present in the benzene ring. This is known as directive
influence of substituents. These are explained below:-
 A. Substitution Reactions
These are the reactions in which an atom or a group attached to a carbon atom in a
substrate is replaced by a new atom or a group. Hence, there is no change in the
structure of the initial organic compound.
Depending upon the mechanism by which a substitution reactions may proceed,
they are further classified into 3 fypes:-
1. Free Radical Substitution Reactions- These are the substitution reactions
which proceed by free radicals.
Example- Halogenation of methane in presence of diffused sunlight or
ultraviolet rays. It occurs in following steps:-
CHo + Cl2.+ CH3CI + HCl
ri'A+,
'J';:irffn.*;['
r*tL -*
"A-l<r--c+
e--

cH3cl * cl2--+ cH2cl2 + HCI

d)ch.l*:-o ,'-.*l o ^-
ch f1.]ri,r,
d
). e-kl*; J^* .

cH2cl2 + cl2---+ cHCl3 + HCl

fr-. ;a Plo* n-.'{l-o L e-
o>. CAy'ex {^,-

cHCl3 + clz;if,fJl.*. rro^--

-;'tA;tf-;i"t.e
Mechanism- rhe uuorlrh,lA radicat mechanism in
which a chain reaction occurs which involves following 3 steps:-
(i) Chain Initiation Step- In this step, free radicals are generated by
homolysis. In case of above reaction, Cl-Cl bond is weaker than C-C
or C-H bond and hence, is the easiest to break.

aa
Cl-CI CI+CI
Lk.lat-i-c- />-e. -o-J i.nk
(ii) Chain Propagation Step- In this step, free radicals generated in the
initiation step take the reaction in the forward reaction by attacking
new molecules and generate new free radicals. In case of above
 reaction, the chlorine free radicals attack the methane molecule and
cause the homolysis of C-H bond to generate methyl free radicals.

t *-"'!^,ir
+ CI-#CH3 '
A
(a) CH4 + H-Cl
l:i*'i"'
The methyl free radicals thus obtained attack second molecule of
chlorine to form CH3-CI with the generation of another chlorine
free radical by homolysis of Cl-Cl bond.

(b) cH: + cl-cl --------t cll3-cl + cl

*i;:f'
The chlorine & methyl free radicals generated above repeat steps
(a) & (b) respectively and thereby set up a chain reaction. The
propagation steps (a) & (b) are those which directly give principal
products,'bufnlany other propagation steps are possible and may
occur. Such steps given below explain how more highly
halogenated products are formed.

ol,r--a
(c) CH3CI + Cl- > CH2CI + HCI
tAte
(d) cH2cl + cl-cl -----)cH2ci2 + cl
(e) cl' + cH2cl2 JI_> Crlct, + HCt
oAt'o
(0 cHCl2 + Cl-Cl --------) CHCI3 + Cl
a hr c :'
(g) cl + cHCl3 cc13 + HCl
o hv- a
(h) cc13 + cl-cl ------) ccl4 +
cl
Note: In each propagation step, a new free radical is generated.
 (iiD Chain Termination Step- In this step, two'free radicals combine to
form a molecule. This happens when the reactant molecules have been
consumed and no molecules are left to be attacked by the free
radicals. The possible chain terminating steps are:-

frf
(a) Cl + Cl -' Cl-Cl
oa
(b) CH3 + CHr -+ CH3-CH3

(c) CH3 + Ci---, CH3-CI

The above step helps us to understand the reason for the formation of
ethane as a byproduct in the chlorination of methane.

n\

2. Nucleophilic Substitution Reactions- These are the substitution which are

initiated by a nucleophile. They are denoted as Sp reactions. (S stands for
substitution and N for nucleophile). They are further divided into following
2 types:-
(i) S*' Reactions- It is the first orcler unimolecular nucleophilic
substitution.
Example- Aqueous hydrolysis of tertiary allqfl halide.
R. A- i .
,\
+ M*Ou ("y) _-->r+ o Ft +N^x
A. -
' ,/
c-X ^'/ - R
b't*t. Jty'LJ;h ."ul*LJ
Kinetics of Reaction- The rate of the S1.ir reaction depends upon the
SNI
concentration of only the substrate and not on the concentration of
nucleophile. Mathematically,
Rate cr [Substrate]
or Rate: k [Substrate]
The above experimental rate law indicates that the order of Spl reaction
must be one i.e. it is first order reaction.
Mechanism of Syl reaction- It involves 2 steps:-

Step I : Ionization of allryl halide- This involves ionization of alkyl

halide i.e. breaking of C-X bond in heterolytic manner. This step is slow
and hence, r:ate determining step, because the ease with which the Syl
substitution occurs will depend on the ease with which C-X bond
undergoes ionization to form the carbonium ion.

f,>
ir/
4 5-i:-.,y')o
S-l* u-,
- /? r\.'J-
''" -./-
A'
;
1-X
cc'*6e c o-d\ *
The formation of the product i.e. attack of nucleophile will depend upon
the stability of the carbonium ion. Greater the stability, faster will be the
attack of the nucloophile and hence, the reaction depends mainly upon
the formation of carbonium ion and that is *hy, this step is the rate
determining step.

Step 2 : Attack of nucleophile qXr the carbonium ion- As soon as the

carbonium ion is formed , it is at once attacked by the nucleophile(OH')
to form the final product. _ ,

+ aH5
A\ +1--> 4r
R.)c' '/ A^-c*oH
ir' (w,.1,^4',t-) R-/
i "J.oL*,
.,t* u#
C P,ro
Because of the opposite charges, the nucleophile attack is instantaneous
and hence, this step is very fast and consequently does not determine the
rate of the reaction.
Stereochemistry of Spl reaction- In the first step of SNI reaction, tertiary alkyl
halide ionizes to give tertiary carbocation and therefore, ,p3 geometry changes into
,p'g.o-.try. As shown below:-
R,
f' e,*rtv r^al;'l-l
d
. /* '/ n
Vo-
c- x
I
+x
tr.,-/ \0, Rrt \4,
S p3 l.,J d-,.;J rr"-J co;-[,rn sftry{,iJ,l./ oo.J,
^ *i*l ,o"o^f p-*t;'lJ
The carbonium ion is planar and hence, there is an equal possibility for the
nucleophile to attack from either side(phase) with equal possibility of inversion
and retention of the original configuration i.e. attack from the front of the
carbonium ion will result in complete retention of the original configuration and
attack from the back will fesfrlt in complete inversion of the original configuration
as shown below:-
f,*' N" F^, -f
R1 A'il*t Af* ,l.
s,luw
I \
C-C9 L.ov-iro h'^; ^
Gcl<-- +cL
Rr'/ \= p-'/'.- , \ 83
Bo.A Atk./,. f,^r-y' ,q {*.4
I^vt>l ir ^ /2t{.t'*Yr-

,f,
." r/"-'u
G"tJ -rrn g,.y, J) N r:"4, J
Therefore, if the alkyl halide is optically active, the product would not be ilptically
active but it will be a 1:1 mixture called racemic mixture which would be optically
inactive due to external compensation.
Energy profile diagram of Spr reaction- It can be seen from the above discussion
that the S5l reaction proceeds via an intermediate i.e. carbonium ion. The energy of
this carbonium ion lies at minima on the potential energy curve. The whole
reaction will have two transition states, one for the conversion of reactant into
carbonium ion and the other for the change of carbonium ion into the product.
Therefore, the stereochemistry of SNr reaction is more complicated than that of 51'12
reaction. The energy profile diagram of Syr reaction is given below:-

t?t
/?.--{fu^ c..^lr--{- -+
Ji* I+to.^ci t:o ^ * (d1- ; ^ Sp a p.o-"d'* ,-
(ii) SN2 Reaction- It is the second order bimolecular nucleophilic substitution
reaction.
Example- Aqueous hydrolysis of piimary allryl halide

CHt->( * Ma*oFt -----J Ct-trou '/-Mu/

L" J ty) rJ;h loJr" L J
Kinetics of SN2 reaction- Experimentally it has been established that the rate of
S*' reaction depends upon the concentration of both the substrate and the
nucleophile. Mathematically,
Rate u, [Substrate] [Nucleophile]
or
Rate:k[Substrate][Nucleophile]
The above rate law indigates that the order of the Sy2 reaction must be two i.e. it is
second order reaction.
Mechanism, Stereochemistry & Energy profile diagram of SN2 reaction- It is
one step reaction which involves simultaneous breaking and formation of the bond.
Ingold suggested a transition state in which the attacking nucleophile becomes
partially bonded to the carbon of the substrate before X- ion has become
completely detached from the carbon of the substrate. In other words OH- ion
collides with the C-X bond from the back and not from the front because both X-
and OH- are electron-rich and maximum repulsion occurs between them. When
such a collision has sufficient energy, C-X bond is broken and C-OH bond is
formed. In the transition state, the OH- and X- lie perpendicular to the plane in
which carbon and 3 hydrogen atoms are present. This is depicted in the following
figure:-
H

C
I
x
,a
oH r- CU
d-
oa
t_! d-
X
ac

H,/ \ l-) tr/ \

lUytJr "L t"I Eo^*ilir^ St' S.

H
oH +- k-
-l
w,/-H
L.

r.;*{._J Pto J"#

In the transition state, OH- has pafiial negative charge($) because it starts to share
its lone pair of electrons with the central carbon atom and at the same time X starts
developing a partial negative charge$) because it starts removing the bond pair of
electrons from the central carbon atom.

When the C-OH bond is completely formed, then the C-X bond is cornpletely
broken. The energy needed for the formation of C-OH bond is supplied by the
energy released by the breaking of C-X bond.
In the final product, the nucleophile(OH-) attaches to the central carbon atom in a
direction opposite to that of X- i.e. inversion of configuration takes place. The
transition state aan be represented graphically by following energy profile
diagram:- r c;n*--R
f^ df s-\
L XJ
1 JL**"; {;u.
"dL

F""TJ
I

O"| o^. Eo*ri{ir^ -c{*& }^ {a >-.o-c*ie^

From the above discussisn "of the stereochemistry of Sr..r2 reaction, it rnay be
concluded that if optically active alkyl halide is hydrolysed by water, the product
will also be optically active with opposite sign of rotation.

3. Electrophilic Substitution Reactions- These are the substitution reaction

which are initiated by an electrophile. They are denoted as Ss reactions(S stands
for substitution and E stands for electrophile). These are rare in aiiphatic
compounds but most common in aromatic compounds. They are further divided
into following 2 types - :

(i) Sr' Reaction- It is first order unimolecular electrophilic substitution reaction.

These are very rare in aliphatic compounds.
Example-Decarboxylation of silver salt of carboxylic acid by bromine. t

o-ai^ Y"fu"4""'> , Bi + Bf
B*
ilo
-------? g c- i '- ; * oJn
i,.1"- :J;^t
f ""*6s */r. o-crot

,? f:
I )':
"^-\
R:c
'r3 I ;
"
I
,ts, B* > R,c-B*.#- Coz

oJn */n^ $
t\
 10

(iD S.' Reaction- It is the second order bimolecular blectrophilic substitution

reaction. These are given by benzene and its derivatives;
Examples-
a. Halogenation of benzene- Reaction is canied in presence of a Lewis acid like
FeX3.
c/_
R&,
+ d',
8."r..---
p,zsLa_
b. Nitration of -)
benzene- It is done by nitrating mixture consisting of
concentrated nitric acid and concentrated sulphuric acid.

,/\ l-t-t ov fto*r. )

fC) + H"'% ----t---'
0 rnr.*
[o-cJ
,g^.':
c. Friedel-Craft alkylation- This reaction is used to introduce an alkyl group in
the benzene ring. The reaction is carried in presence of a Lewis acid like

Alx3.
A'lcg
+ cHsa
0
AZct-
>

i l,^,,
/Y.fr,
-r- H Cl_

(r*(-(.*. )
 L1

Mechanism of Ss2 reactions- It includes 3 steps-

t. Generation of Electrophile- It is done by heteroJysis of the attacking
molecule.
(Nucleophile is also generated simultaneously)

a. Hal ogenation of berygs=__

' C-jrtc'(,
c)-Q
,if#i,L",L)
b. Nitration of benzene- "*l'f
Gk$,.rtL1 Ui I
1..r)
H Nos + z FL roq * r,,#3* -* *- o,. J
tii:{rn*
(3
;o o

c. Friedel-Craft alkylation- Ce *
) )
' C Hr c-r- + A.l cL -----___\ .n
+* *r (t
qft -
* n-t or-
d. Friedel-Craft acylation- D
R coct f Al c(r
44 dr-- 6u)
, ^t
i ----)L
-L
*.
.(,ng ?-:v-tpx)^(pv,)
Cylf. ,
C F6 co cr + At c-\ ,-72fl::'-:J-*
thd benzene riffio foim-reionahid
2. Attack ofI Electrophile on thri :t^4-t c{o.- Y

stabilized carbocation(sigma complex)-

a. Halogenation of benzene-

+ >t
+CAl6,.o.ls*,
c-L
vA
d t.ri.---.- (a+)
b. Nitration of benzene-

f g. ep -..-
l3 0'"=$=e
(.d'li J .*.(
da". -o r- c€ s ,- ,rv^* ,\rr.
@.'-F./ "
(-r* -1.:..o r__*$" )