Halogen Derivatives

Alkyl Halide & Aryl Halide

LECTURE NOTES ALKYL HALIDE & ARYL HALIDE

INTRODUCTION
Compounds derived from hydrocarbons by replacement of one or more H-atoms by corresponding
number of halogen atoms are known as halogen derivatives.
I. CLASSIFICATION
On the basis of nature of hydrocarbon from which they are obtained, helogen derivatives can be
classified as :

Halogen Derivatives
Alkyl halides Alkenyl halide Alkynyl halide Aryl halide
Mono halides Di-halides Tri-halides Tetra halides
Primary halide Secondary halide Tertiary halide
(i) Alkyl halides : Halogen derivative of alkanes.

D:\TEACHING NOTES-2016-17\CHEMISTRY\OC\FINAL\Hydrogen derivatives (Alkyl Halide , Aryl Halide)\Hydrogen derivatives (Alkyl Halide , Aryl Halide).p65
(ii) Alkenyl halides : Halogen derivative of alkenes.

(iii) Alkynyl halides : Halogen derivative of alkynes
(iv) Aryl halides : Halogen derivative of arenes (aromatic)
Alkyl halides can be further classified on the basis of number of halogen atoms introduced in
alkane molecule.
(1) Mono halides : They are obtained by replacement of one hydrogen atom by one halogen atom in
alkane.
General formula CnH2n+1X
Example : CH3Cl Methyl chloride (Chloro methane)
CH3CH 2Br Ethyl bromide (Bromo ethane)
(2) Dihalides : They are obtained by replacement of two hydrogen atom by two halogen atom in
alkane molecule. The two halogen atoms may be on same cabon atom, known as geminal dihalides,
if two halogen atoms are at adjacent carbon atoms they are known as vicinal dihalides.
General formula CnH2nX 2
Example : CH 2X 2 Methylene dihalide
CH2X Ethylene dihalide or Vicinal dihalide
CH2X
CH3
Ethylidene dihalide or geminal dihalide
CHX2
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(3) Trihalides : They are obtained by replacement of three hydrogen atom by three halogen atom in
alkane.
General formula - CnH2n-1X3.
Example : CHX3 Trihalo methane or haloform
(4) Tetra halide and Perhalo compounds : They are obtained by replacement of four hydrogen
atom by four halogen atom in alkane.
General formula CnH2n–2X4 (tetra halide).
Example : CH4 ¾¾® CX4 (Per halo methane)
C2H6 ¾¾® C2X6 (Per halo ethane)
II. MONO HALIDES

These are classified on the basis of nature of C-atom carrying the halogen atom.
(1) Primary halide or 10 alkyl halides : Halogen atom attached with a primary or 10 C-atom.
Example : CH3—X Halo methane or methylhalide
CH3—CH2—X Halo ethane or ethyl halide
CH3—CH2—CH2—X 1-Halo propane or n-propyl halide
(2) Secondary or 20 alkyl halides : Halogen atom linked with 20 C-atom.
Example : CH3 CH CH3 2-halo propane

or
Iso propyl halide
X
2-halo butane
CH3 CH CH2 CH3 or
Sec. butyl halide
X
(3) Tertiary halide or 30 alkyl halide : halogen atom linked with 30 C-atom.
CH3
Example : CH3 C X (tertiary butyl halide)

CH3
III. TYPES OF SOLVENT
Solvent can be classified as :-
Solvent
Non polar Polar
Polar protic Polar aprotic
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(i) Polar Solvent : Polar solvent has some overall dipole moment. They are of two types
(1) Polar protic solvent : Solvents in which H atom is directly attched with highly
electronegative atom. Polar protic solvents are capable of forming intermolecular hydrogen
bonding.
In polar protic solvents cation are solvated by ion dipole interaction while an anion is
solvated by hydrogen bonding. Polar protic solvent can give H+
Example : H2O, C2H5OH, CH3COOH etc.,
Polar protic solvent can solvate both cation as well as anion. Cations are solvated by ion
dipole interaction with H2O while anions are solvated by hydrogen bonding with H2O.
Solvation of NaCl in H2O can be explained as
O
H H
d+
H Od– H H d+
H
d– d– d+
O Na+ O H Cl H d+
–
H d+
Od– H O H Hd+
O
d+
H H –
Cl is solvated by
+
Na is solvated by ion-dipole H-bonding with H2O
interaction with H 2O
(2) Polar aprotic Solvents : These are the solvents in which H is not attached with highly
electro negative atom. These solvents can not give H+
Examples :
O
O O O
CH3 CH3 P
H3 C S CH3 H C N CH 3 C N (CH3)2N N(CH3)2
CH3 CH 3 N(CH3)2
DMSO DMF DMA Hexamethylphosphoric
(Dimethyl sulphoxide) (Dimethyl formamide) (Dimethyl acetamide) triamide (HMPA)
Polar aprotic solvent can solvate cation very well, while anion is not solvated. When a
salt is added then cation is trapped by ion dipole interaction, while Br– is not well solvated
H3 C CH3
O
S H3C
O CH3 S
H3 C O d– CH3
S CH3
d– d– –
S O Na+ O S CH3 Br
CH 3
H3 C CH3 H 3C
O d–
S
S
S O
O CH
H3 C CH3 H 3C 3
Na+ is solvated by ion dipole Br– surrounded by solvent but not

interaction with DMSO well solvated by DMSO
(ii) Non Polar solvents : These solvent has overall zero dipole moment.
Examples : CCl4 , Benzene etc.,
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Some Common examples of solvents :

SOLVENTS POLAR PROTIC POLAR APROTIC
1. H2 O P –
2. CH 3CH 2OH P –
3. H–COOH P –
4. CH3–COOH P –
5. NH 3 P –
6. × P
7. × P
8. × P
9. × P
IV. ELECTROPHILES & NUCLEOPHILES

(i) Electrophile : An electrophile is a positively charged species or neutral molecule with electron
deficient center. Electrophiles can act as Lewis acids.
Electrophiles are of following type :
(1) Positively charged electrophiles
H+, Br+, Cl+, I+, NO2+, R3C+, NO+ etc
(2) Neutral Electrophiles : In these electrophiles central atom has an incomplete octect and
atleast one vacant orbital
SO3, BF3, AlCl3, ZnCl2, FeCl3, RCOCl, (RCO)2O
(ii) Nucleophiles : It is an electron rich species which has atleast one lone pair of electrons.
Nucleophile can be neutral or negativetely charged. Nucleophile is always a lewis base.
– – – –
Example : CN , OH , Br , I , NH3 , H2O
Nucleophile are of following types :
(1) Negatively charged nucleophiles :
O
– – – – – – – –
Example : H, OH , O – R, CH3 , X, SH, R – S, NO2, R – C– O– , etc
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(2) Neutral nucleophiles : In these nucleophiles central atom has complete octet and atleast
one lone pair of electron
Example : R – NH2 , NH3 , NH 2–NH 2 , H – O – H R – O – H , R – O – R ,
H – S– H, R – S– H , R – S– R , PH3 , N ,
Organic compounds containing carbon-carbon double bonds can also behave as

nucleophile.
CH2 = CH2, , CH2 = CH– CH= CH2, etc
(3) Ambident Nucleophile : Species having two nucleophilic sides, but only one can donate
lone pair of electron at a time, known as ambident nucleophile.
– –
C º N , O – N = O, etc
V. NUCLEOPHILICITY & BASICITY

Nucleophiliticy is defined as the tendency of any species to give electron pair to an electron
deficient center, while basicity is the ability of the species to remove H+ ion, from an acid
Example : Consider a species B– ,
(i) It functions as a nucleophile is given as
B– + C C + L (L - Leaving group)
–
L B
(ii) It functions as base is indicated as

– B– H + A–
B+H –A
The nucleophilicity is determined by the kinetics of the reaction, which is reflected by its
rate constant (k) while basicity is determined by the equilibrium constant, which is reflected
by its Kb.
Criteria for Nucleophilicity : The factors which increases electron density at donor atom
increases nucleophilicity.
The more polarisable donar atom is a better nucleophile. Therefore, large size of donor atom
increases nucleophilicity.
Effect of the solvent : In polar protic solvent large nucleophiles are good, and the nucleophilicity
of halide ions follows the order as :
– – – –
F < Cl < Br <I
In DMSO, the relative order of nucleophilicity of halide ions is given as
– – – –
F > Cl > Br > I
Also basic strength of halides follows the same order in DMSO but in polar protic solvent like
H2O they follow the reverse order of nucleophilicity.
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This effect is related to the strength of the interaction between nucleophile and solvent mol-
ecules of polar protic solvent forms hydrogen bond to nucleophiles in the following manner :
Relative nucleophilicity in polar protic solvent
> > > > > > > H2O
>
HO¯ > H2O

NH2¯ > NH3
CF3SO3¯ < PhCOO¯ < PhO¯ < RO¯
Steric effects on nucleophilicity
(Stronger base, yet weaker nucleophile cannot approach the carbon atom so easily.)
(Weaker base, yet stronger nucleophile)
Periodicity : Nucleophilicity decreases from left to right in a period and basicity also decreases.
CH3- > NH 2- > OH - > F -

In a group, nucleophilicity increases from top to bottom due to increases in size of donor atom,
but basicity decreases from top to bottom.
Acid strength : HI > HBr > HCl > HF
– – – –
Basic strength : F > Cl > Br >I
– – – –
Nucleophilicity : F < Cl < Br <I
It is the tendency to donate electron pair to ion.
(a) (b)
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NUCLEOPHILICITY vs BASICITY
Nucleophilicity Basicity Remarks
1. CH3¯>NH2¯>OH¯>F¯ CH3¯>NH2¯>OH¯>F¯ If donor atoms belong to

same period, nuclephilicity
and basicity order is same
2. SiH3¯>PH2¯>SH¯>Cl¯ SiH3¯>PH2¯>SH¯>Cl¯ ––//––

3. F¯< Cl¯ < Br¯ < I¯ F¯> Cl¯ > Br¯ > I¯ In a group nucleophilicity
increases while basicity
decreases. on moving top to
bottom.
4. OH¯ < SH¯ OH¯ > SH¯ ––//––
5. RO¯ < RS¯ RO¯ > RS¯ ––//––
VI. LEAVING GROUP ABILITY / NUCLEOFUGALITY

Good leaving groups are those that become the most stable ion after they leave, because leaving
group generally leave as a negative ion, so those leaving group are good, which stabilise negative
charge most effectively and weak base do this best, so weaker is the base better is the leaving
group.
– The leaving group should have lower bond energy with carbon.
– Negative charge should be more stable either by dispersal or delocalization.
Strongly basic ions rarely act as leaving group ®
(strong base / poor leaving group)
(It is not a leaving group)
Order of leaving ability of some groups

O O
+ +
(1) R – N º N > R – O – R' > R – O – S– C4F9 > R – O – S – CF 3 >
O O
O O
+
(2) R – O – S– O Br > R – O – S O CH3 >
O O
O O
(3)
O O
O
(4) R – O – C– CH3 > R – O – H > R – O – R > R – H
where group attached with R is a leaving group

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(5) CH3¯ < NH2¯ < OH¯ < F¯
(6) R–COO¯ > PhO¯ > HO¯ > RO¯
(7) –
SH > –OH
ILLUSTRATION :
(1) Ambident nucleophiles are ?
O
NO–2 , NH2 – CH2 – C – O– , OH
(a) (b) (c)
Solution. (a), (b)
(2) Which among the following species is an ambident nucleophile :

(A) Ethene (B) Benzene
(C) Cyanide ion (D) Acetone

Solution. (C) Cyanide ion is an ambident nucleophile
(3) A nucleophile is :
(A) electron-rich species

(B) electron-deficient species
(C) a Lewis acid

(D) Positively charged species
Solution. (A) A nucleophile is electron-rich species
(4) Which is not a nucleophile –

(A) NH3 (B) R—O—R (C) BF 3 (D) HOH
Solution. (C) BF3

GOLDEN KEY POINT -1
(1) Nucleophilicity depends on the nature of solvent.
(2) Anions are better nucleophile than their neutral molecule.

(3) Nucleophilicity increases if adjacent atom of nucleophilic side has lone pair, because lone pairs
repels each other. Example NH2–NH2 .
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BEGINNER'S BOX -1
(1) Which of the following is electron deficient ?
(A) PH3 (B) (BH3)2 (C) (SiH3)2 (D) (CH3)2
(2) Heterolytic fission of a covalent bond can form :
(A) Free redical (B) both carbocation and carbanion
(C) only carbocation (D) only carbanion
(3) Which behaves both as a nucleophile and electrophile ?
(A) CH 3NH2 (B) CH3OH (C) CH3CN (D) CH3Cl
(4). In the reaction of phenol with CHCl3 and aqueous NaOH at 70º, the electrophile attacking the
ring is :
(A) CHCl3 (B) CHCl2 (C) :CCl2 (D) COCl2
(5). Which of the following has the highest nuclephilicity ?
(A) F– (B) OH– (C) CH3 – (D) NH2 –
(6). Arrange the following nucleophiles in the order of their nucleophilic strength :
(A) OH– > CH3COO– > CH3O– > C6H5O– (B) CH3COO– > C6H5O– < CH3O– < OH–
(C) C6H5O– < CH3COO– < CH3O– < OH– (D) CH3COO– < C6H5O– < OH– < CH3O–
(7). Among the following, the strongest nucleophile is :
(A) C2H5 SH– (B) CH3COO– (C) CH3 NH2 (D) NCCH2 –
(8) Which of the following site (numbered) will behave as best nucleophile
(A) 2 (B) 3 (C) 1 (D) 5

(9) Which of the following will behave as a best leaving group
(A) F– (B) Cl– (C) Br– (D) I–
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CARBOCATION
Different reaction shown by carbocation
(i) Rearrangement
(ii) Combination
(iii) Elimination
REARRANGEMENT
(i) Less stable carbocation rearrange itself into more stable carbocation.
Stability must attain in each step.
Stability of T.S. (Transition state)
–
3C–2e bond
Z
Z Z
d+ (increase) d (decrease)
+
C C
Ex.1 + +
C C C C
14 TS
Note :
(i) Its a example of 1, 2 shift.
(ii) 3-MCTS (membered cyclic transition state) involve
(iii) Migrating order (when different atom / group attached to one carbon)
(a) –H > –Ar > – R
(b) –H > –D > –T
OMe OMe
(c) > > > >
OMe Me Cl
p-anisyl p-tolyl
(d) –3° > –2°> –1° > Me
(e) –CH2CH2CH2CH3 > –CH2CH2CH3 > –CH2CH3 > –CH3
(iv) Bulkier group migrate first
Q. Carbocation No. of 1-2 shift Most stable
1. 1(H) +
+
2. 1(Me)
+ +
+
3. 2(H,H) +
4. 1(H) +
+
+
5. 1(Et)
+
+
6. 2(H) +
O O
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O
7. + X X
8. 1(Et) +
+
9. + 1(Iso-p) +
+
10. 3(H,Et, H)
+ +
p-tolyl
Ph-shift
Ph C CH2 Ph
p-tolyl
+ Q
11. Ph C CH2
Ph p-tolyl
Ph C CH2 p-tolyl
P X-shift
Ph
R
Q >> R >> P
* If after shift, carbocation stabilized by back bonding then migratory apptitude will be
stictly followed.
* If no such phenomena then form most stable carbocation
Ph Ph
+ Ph
Me Ph
12. + +
O Me O O
Ph Ph
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RING EXPANSION :
It is also an example of 1, 2 shift.
On ring expansion strain get released
1.
2.
3.
No Ring expansion takes place only 1, 2 H shift
OH
OH OH
4.
RING CONTRACTION :
+
1
2
1. +
OH OH
+
2. +
OH OH
+
3.
+
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ANTI GROUP MIGRATION

p-tolyl
SbCl5 Ph
Ph C CH2 Cl C CH2 p-tolyl
Ph
Ph
+
s vacnat
*
s(f) + H
Ph C C H Ph C C H
1.
Ph +Cl Ph H
–
Sb Cl5 (Arenium ion)
Ph
C CH2 p-tolyl
Ph
H H
OH
+
NaNO2 + HCl
OH OH
2. H H
+
NH2 N2
Carbocation involved in combination reaction (with I– as nucleophile ):

I
+ – –
(a) Nu (I )
(b) + +
I
(c) +
+
I I
I I
+
+
(d)
Carbocation involved in elimination reaction :

(a) + Base
(b)
+
(c)
+ + +
Saytzeff alkene Hoffman alkene
(d) + +
Saytzeff Hoffmann
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Saytzeff product : The product with the most highly substituted double bond will predominate.
This rule is called the saytzeff or zaitsev rule.
Hoffmann product : Bulky bases can also accomplish dehydrohalogenations that do not fol-
low the saytzeff rule. Due to steric hindrance, a bulky base abstracts a less hindered proton,
often that leads to formation of least substituted product, called the Hoffmann product.
REACTION INVOLVING CARBOCATION AS AN INTERMEDIATE

1. DIAZOTIZATION
NaNO2/HCl + –N2 H2O

R–NH2 R–N=N R–N º N R+ R–OH
or
HNO2 CAN
or (Cerric ammonium nitrate)
NOCl Tilden reagent
Red colour
H2O
R–OH (Major when NaNO2/HCl or HNO 2)
Cl–
R–Cl (Major when NOCl is taken)
+
R NO2 –
R–NO2
O–N=O
R–ONO
D
alkene
Mechanism :
NaNO2 + HCl ¾¾® HNO2 + NaCl
O O
+ + H +
H H+
HO–N N–O N=O NºO+
H
H
+ + –H+
R–NH2 + NºO R–N–N=O R–NH–N=O R–N=N–OH
H
H2O + –N2 + + –H+
ROH R R–N=N R–NºN R–N=N–OH2+
Note :(i) NO+ is attacking electrophile

(ii) Carbocation involved during the reaction as an intermediate
(iii) Rearrangement takes place if possible
(iv) Alkyl diazonium salt is highly unstable.
NH2 OH
(1) NaNO2/HCl
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(v) Aryl diazolization salt is stable only at (0-5°)

+
NH2 Nº N
NaNO2/HCl Cl–
(2)
(0-5°)C
NH2 OH
(3) NaNO2/HCl
Boil
(vi) In case of secondary amine yellow oily liquid (N-nitroso amine) is obtained.
R R
NaNO2/HCl
N–H N–N=O
R R
–N2 + H–O–H *
NaNO2/HCl
(1)
NH2 +
N2 OH
+
NH2 Nº N + OH
(2) NaNO2/HCl –N2 H–O–H
DEHYDRATION OF ALCOHOL :
Alcohol on dehydration gives alkene as the major product.
Conc. H2SO4
CH3–CH2–OH D
CH2= CH2
Mechanism:
H + –
H+ + –HOH HSO4
CH3–CH2–OH CH3–CH2–O CH3–CH2 CH2= CH2
H
Note:
1. Reaction involve E1(unimolecular elimination) mechanism.
2. Endothermic Reaction
3. Carbocation involve as an intermediate
4. Rearrangement takes place if possible
5. Higher temperature is required for dehydration.
6. For dehydration following catalyst can be used
Ex.Conc. H2SO4, H3PO4, KHSO4 etc.
7. Two or more than two types of alkene can be obtained (Saytzeff and Hoffmann)
8. Usually Saytzeff alkene dominates over Hoffmann alkene.
9. Rate : r = k[R–OH2+]
10. Unimolecular reaction.
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ENERGY PROFILE DIAGRAM FOR DEHYDRATION OF ALCOHOL

+
R OH2
(bond breaking)
PE +d H
R–O +d
H R
Alkene
R–OH
+
R–OH2
Reaction co-ordinate
Temperature variation for dehydration of CH3–CH2–OH
H Rate determining step

+ r.d.s
CH3–CH2–O–H + H CH2–CH2 –H2O
+
OH2
+
CH3–CH2
–OSO H
CH3–CH2–OSO3H 3
(Combination) 110°
–OSO3H + CH3–CH2–O–H
CH3–CH2–O–CH2–CH3 CH3–CH2–O–CH2–CH3
–H3SO4 140°
(Combination) H
CH2=CH2 + H2SO 4 160°

(Elimination)
* In RDS, two different components are involved ( CH 3 - CH 2 - OH 2+ & O -SO3H )
CH3
conc. H2SO4
Ex.1 CH3 C OH
H2SO4+D
CH3 or H+, D
H
+ –
H r.d.s OS3H 1
Sol. OH OH2 H(E )
¯
+ Eelimination
OH2
molecularity-1
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Complete the following reaction and draw and energy profile diagram
OH
1. conc.H2SO4
OH +OH
2
conc.H2SO4 r.d.s Å fast
Ans. –
OSO3H
(E1 mechanism)
+
R OH2
(bond breaking)
PE +d H
R–O +d
H R
Akene
R–OH
+
R–OH2
conc.H2SO4
2.
OH
Ans.
H+/D
–
r.d.s OSO3H +
+ +
(I) (II) (III)
OH OH2+
(E1 mechanism)
R OH2+
PE +d H
R–O +d P
H R+ R
Q
R–OH
ROH2+
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conc.H2SO4
3.
OH
Ans.
H+/D r.d.s 1, 2 H
+ +
+
(I) (II)
OH OH2+
(E1 mechanism)
R OH2+
+d H
PE R–O +d P
H R+ Q
R–OH
ROH2+
Ph
Ph conc.H2SO4
4.
OH
Ph H+/D Ph r.d.s Ph Ph
Ans. Ph Ph Ph + Ph +
(I) Ph Ph
OH OH2
+ (E1 mechanism) (II)
R OH2+
+d H
PE R–O +d Q
H R+ P
R–OH
ROH2+
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OH
conc.H2SO4
5.
+
OH OH 2
conc.H2SO4 + –
OSO3H
Ans. r.d.s
(E1)
R OH2+
+d H
PE R–O +d
R+ Alkene
H
R–OH
ROH2+
OH conc.H2SO4
6.
+
OH2
–
Ans. OH conc.H2SO4 r.d.s + OSO3H
+
1
(E ) (I) (II)
R OH 2+
+d H
R–O +d R+
H R+1 (I)
R–OH (II)
+
ROH2
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conc.H2SO4
conc.H2SO4
7. 8. OH
OH
+ OH
conc.H2SO4 conc.H2SO4
9. 10.
O
OH conc.H2SO4
conc.H2SO4
11. 12.
OH
O
OH
13. 14.
OH
OH
OH OH conc.H2SO4
conc.H2SO4
15. 16.
OH
OH
17. 18.
OH OH
H2SO4
19. OH conc.H2SO4 20. OH
D
OH H2SO4 OH
21. 22. H+
D D
+
OH
OH H H
+
23. 24.
low temp. low temp.
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PINACOLE
Pinacolone rearrangement
CH3 CH3 CH3 CH3
H2SO4
H3C – C – C – CH3 CH3 – C – C
D
OH OH CH3 O
Mechanism
CH3 CH3 CH3 CH3 CH3 CH3

+
H
H3C – C – C – CH3 H3C – C – C – CH3 H3C – C – C+– CH3
+
OH OH OH O H2 OH
1,2-methyl shift
CH3 CH3 CH3

–H
+ +
CH3 – C – C H3C – C – C – CH3
CH3 O OH CH3
H+
1. OH D
OH
2.
OH OH
3.
OH OH
Ph Ph
H+, D
4. Ph CH3
OH OH
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Ph Ph
H,D
+
5. CH3 CH3
OH OH
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H+ , D
6.
OH OH
OH
H+, D
7.
OH
OH
H+ , D
8.
OH
Ph Ph
H,D
+
9. P-tolyl P-anisyl
OH OH
Semi-pinacole rearrangement (Damjanov's Reaction)
1. SbCl5
OH Cl
2. SbCl5l
AgNO3, AlCl3
OH Cl
Ph
SbI5
3.
AgNO3, AlCl3
OH I
OH
Cl
SbCl5
4. OH
+ AgNO3, AlCl3
I
SbCl5l
5. AgNO3, AlCl3
OH
I
SbCl5l
6. AgNO3, AlCl3
OH
I
SbCl5l
7. AgNO3, AlCl3
OH
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NH2
NaNO2/HCl
8.
OH
H,D
+
9.
OH
OH
SbCl5l + OH
SbCl5l +
10. Cl– Cl–
Cl OH
OH
ELECTROPHILIC ADDITION REACTION
Case-I (i) When cationic part doesn't have unshared electron pair. Classical carbocation involved in
the reaction.
X Y
H2O or CCl4
C C + X Y or Cs2O, CH2, Cl2 –C–C–
or CHCl3
Mechanism :
C r.d.s. +
C C C
–Y–
X+d –
X Y
Y –d X
(Ist approach)
+
C C
X Y Y X
C C , C C , C C , C C
X Y X Y
Note : (i) Electrophilic addition takes place
(ii) carbocation intermediate is involved
(iii) rearrangement possible
(iii) step-I (attack of E+, formation of carbocation)
(iv) X-Y may or may not be vicinal
(vi) Both syn & anti addition possible
(vii) Rate µ Nucleophilicity of alkene
µ Stability of carbocation Priority
µ stability 1of alkene
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MARKONIKOV'S RULE
According to this rule, –ve part of attacking regent attacks at that doubly bonded C which has
min. no. of H atoms during electrophilic addition.
Advanced Defination : The –ve part of attackery reagent attacks at that doubly bounded carbon
atom which form more stable carbocation.
* Not applicable in symmetric alkene.
Br
(a) HBr
HBr Br
(b)
Br
(c) HBr
Br
(d) HBr
HBr
(e)
Br
Case-II :
When cationic part contain unshares e pair. i.e. Non classical carbocation is involved.
Mechanism:
C X
C Y–
C C + C C
X X
Y
non-classic
carbocation (NCC)
Y Y X X
C
C C C C C C
C Y
X Y
X
identical
identical
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X–Y X+ Y–
HCl H+ Cl–
HBr H+ Br–
HI H+ I–
DI D+ I–
H2SO 4 H+ OSO3H –
H2O/H+ H+ H2 O
ROH/H+ H+ ROH
CH3COOH/H+ H+ CH 3COOH
Br2/CCl4 Br+ Br–
Cl2/CS2 Cl+ Cl–
Br2/H2O Br+ H2O/Br–
(Br2 water in brine) Br+ Br–, Cl–, H2O
HOCl Cl+ H–O–H
HOBr Br+ H–O–H
+
NOCl NO Cl–
IN3 I+ N3-
For case (II)
Note :
(i) Electrophilic addition reaction
(ii) NCC intermediate is involved

(iii) No rearrangement possible
(iv) step-I (attack of E+, formation of NCC)
(v) X, Y are always at vicinal position
(vi) Only anti addition possible.
(vii) Rate of reaction µ Nucleophilicity
µ Stability of cation (NCC)
1
µ
stability of alkene
Reactions involving NCC
1. Addition of X2 :
X
C C + X2 C C
X
Note:
(i) NCC intermediate / no rearrangement / anti addition
(ii) Order of rate of reaction for X2:
F2 >> Cl2 > Br2 >> I2
explosive Cs2 CCl4/ allow
CH2Cl2/ reaction
CHCl3
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TEST OF UNSATURATION
Br
CCl4
C C + Br2 C C
H2O
Br
(Reddish brown) (Colourless)
* (–) Br2/H2O test
(–) Br2/H2O test
(+) Br2/H2O test
Br2
CCl4 Br2
1. . 2. CCl4
Br2
H 2O
Br2 Br2
3. CCl4 4. CCl4
Br2 Br2
5. 6. CCl4
CCl4
Br2 Br2
7. CCl4 8.
CCl4
Br2 Br2
9. HC º CH excess 10. CH3–CºCH excess
* Stereochemistry Involved During Addition of X2

Br2 Br2
1. CCl4
2. CCl4
Br2 Br2
3. CCl4 4. CCl4
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IODOLACTONIZATION
Note: Formation of five membered ring can be considered as norm for iodolactonization
OH (i) I2
1. (ii) NaHCO3
O
Mechanism:
+I
OH I2 OH I–
NaHCO3
–NaI
–H2O
O O –CO2
+I I
O O
O O
O
2. (i) I2
OH (ii) NaHCO3
COOH
(i) I2
3. (ii) NaHCO3
(i) I2
(ii) NaHCO3
4.
COOH
Addition of R–OH/R–COOH/R–SH/H2S
R
O
ROH, H+
O
+
R–COOH, H O R
SR
1. RSH, H+
SH
+
H2S, H
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Et-OH
2. H+ + Et
O O O O
O
CH3 C
OH O
3. H
+
+ +
O O O O CH3 O O CH3
C
OH
REACTION WITH DIL. H2SO4
Reverse of dehydration of alcohol.
dil. H 2SO4 / dil. H 2SO4 /
1. CH2=CH2 ¾¾¾¾
(or) H3 O+
¾ ® 2. ¾¾¾¾
(or) H O+
3
¾ ®

3. ¾¾¾¾
(or) H O+
¾ ® 4. ¾¾¾¾
(or) H O+
¾ ®
3 3

5. ¾¾¾¾
(or) H O+
¾ ® 6. ¾¾¾¾
(or) H O+
¾ ®
3 3
Ph
dil. H 2SO4 /
7. CH2=C=CH2 ¾¾¾¾
(or) H3 O+
¾ ® CH3 C CH3
O
HYDRATION OF ALKYNE (KUCHEROOV'S REACTION)
Alkyne are hydrolyced in presence of Hg+2 salt (sulphate and acetate) as a catalyst.
HC º CH ¾¾
® Aldehyde
RC º CH ¾¾
® ketone
RC º CR' ¾¾
® Both ketones are possible
1% HgSO4
1. HC º CH ¾¾¾¾¾
80% HgSO4
®
Mechanism:
+
CH CH OH2 OH
OH2 H
+ OH
HC º CH ¾¾¾
® Hg 2+
CH2 CH ¾¾¾ ® CH2 CH –Hg+2 CH 3 C
- H+
Hg+2 + H
Hg Hg +
NCC
1% HgSO4
2. ¾¾¾¾¾
80% HgSO
®
4
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REACTION WITH CONC. H2SO4

Since –OSO3H is large, so it gives H2SO4 addition on alkene of type CH2=CH2 / R–CH=CH2/
R–CH=CH–R.
But dimerization of alkene is abserved with alkene of types:
R R R
Type: C CH2 C C
R R H
conc. H2 SO4
1. ¾¾¾¾¾ ® OSO3H
conc. H 2SO 4
2. ¾¾¾¾¾ ®
conc. H 2SO 4
3. ¾¾¾¾¾ ®
Mechanism:
H2SO4 + +
H H
OSO3H
–H 2SO 4
* Sytzeff Hoffmann
* Stable Less stable

* TCP (Minor) KCP (Major)
as Tert-butyl hinders
the –OSO3H taking H+
4. Mechanism:
H2SO4
D
(i) conc. H2SO4

5. (ii) H3O
+
OH from H2SO4
Hydrolysis of S-O due to the fact that it is partial p-bond
(i) conc. H2SO4
(ii) H3O
+
OH from H2SO4
OSO3H O
O S OH H 3O +
OH + H2SO3
H O
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Note:
(i) Allylic halo alkane on HX addition always involve NCC.
(ii) Addition of HI on alkene is highly reversible vicinal iodide aren't stable gives back alkene
and I2.
C C C C + I2
I I
Br
+ HBr +
(iii)
Br
(P) (Q)
Addition of HX on alkene is carried out in low O2 atmosphere. The O2 present in atmosphere
takes a part of e– density of alkene as changes to peroxide. The peroxide present creates the
(Q) by anti markonikov reaction.
Attack by intramolecular Nu– site:

NH
Br2
1.
I2
2. ONa
NOCl
3. HOCl
Br2/water
brine
4.
NaCl
5. dil H 2SO4
OH
(i) Hg(OAc)2 , H2O

(ii) NaBH4 , OH–
OH
(i) BH3–THF OH
–
(ii) H2O 2/OH
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OXEMERCURATION, DEMERCURATION
Mechanism:
HgOAC
OH
OH2 NaBH4
Hg–OAc Hg+
Ph Ph OH
OAc OAc
Reaction:
HgOAC
Hg(OAC)2 NaBH4
H2O
OH OH
Note:
(i) NCC involved
(ii) No rearrangement
(iii) OM is anti
(iv) OMDM overall is syn and anti both
(v) Product of OMDM can be obtained by H2O addition in Marconikoff rule without
rearrangement.
In final step, no clear justification can be given Expt. shows both syn and anti Þ planar
addition Þ carbocation or free radical
rearrangement
\ so, radical is most probable mechanism.
Hg(OAC)2 Hg(OAC)2
1. H2O 2. H2O
Hg(OAC)2 (i) Hg(OAC)2 , RSH

3. H2O 4. (ii) NaBH4
Hydroboration Oxidation (HBO)
CH3 CH
H CH H
BH - THF
3. CH3–CH=CH2 ¾¾¾¾
or B H
® 3
2 6
B CH
H CH CH CH3
CH
CH3
* H-form BH3 or (CH3–CH–CH2)3B
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Oxidation:
H2O2 / NaOH
CH3 CH CH2 B 3CH3 CH CH2
H 3 H OH
Note :
(i) syn addition
(ii) Product can be obtained by assuming H2O addition on same alkene by anti-Markonikov's
addition.
(iii) In case of sterically crowded alkene mono/di alkyl borane is obtained as a product.
BH3
1. THF BH2 BH
H
B
BH3
2. THF
BH
Mechanism:
Hydroboration
CH3 CH CH2
H BH2
3CH3 CH CH2 B CH3 CH CH2 B
H H 3
H
B H
O+
Oxidation :
- -
(H 2 O 2 + O H ¾¾
® O - OH + H 2 O)
R B O
-
R3 B + O - OH ¾¾
® R O H
(1,2 shift)
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R OR
– –
–2O–OH OH
B B
R OR OR OR
OR OR
–
OR
B B
OR O H RO OH
OR
OR
–
2OH –3
B + ROH 3ROH + BO3
–
RO O
H H
(i) BH3 / THF OD
3. (ii) D2O2 /OD
–
BH2
D D
(i) BD3 / THF OH
4. (ii) H2O2 /OH
–
2
BD2
D
D
(i) BD3 / THF OD
5. (ii) D2O2 /OD
–
2
BD2
(i) BH3 / THF
6. (ii) H2O2 /OH – BH2 OH
H
KCP V TCP:
(i) KCP Þ Kinetically controlled product
Þ Product which is quickly formed
Þ Product formed by lowest activation energy
(ii) TCP Þ Thermodynamically controlled product
Þ Most stable
(iii) KCP and TCP may be same.
(v) 1, 2 product is always KCP because of proximity factor (closeness)
H
Br
Closer, proximity is high
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JEE-Chemistry
(vi) At low temp. (–80ºC), KCP is major as the energy barrier is low
(vii) At high temp.(35ºC), TCP is major because at high temp, reaction are reversible. 1-2
product has less energy barrier so quickly reverts but while going back (R®product), the
reverssibility of reaction is still high, so it prefers the high energy barrier where reversibility
factor is low. So, TCP forms
1-2 product 1, 4 product
HBr –80º C
35º C
HBr –80º C
35º C
D) The nature of the leaving group :

Weaker bases are good leaving groups. A good leaving group always stabilise the transition state
and lowers its free energy of activation and there by increases the rate of the reaction. Order of
leaving ability of halide ion F¯ < Cl¯ < Br¯ < I¯
Better is the leaving group, more will be rate of SN2 reacton
(ii). Unimolecular nucleophilic substitution reaction (SN1) :
Mechanism : SN1 in alkyl halides
H O +acetone
¾¾2 ¾ ¾ ¾
¾® + HBr (3° alkyl halide)
Nucleophilic substitution involves two step process

First step : Slow step involves ionisation to form carbocation. It is a rate determining step
R – L ¾® R+ + L– (Slow)
Ionisation is always assisted by the solvent since energy necessary to break the bond is largely
recovered by solvantion of R+ and L–
Second step : Attack of nucleophile on carbocation to result into product, it is a fast step
R+ + Nu –
¾® R–Nu (fast)
(1) Characteristics of SN1 reactions :

(A) It is unimolecular, two step process.
(B) Carbocation intermediate is formed so rearrangement is possible in SN1 reaction.
34
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Rate µ [Alkyl halide]1

Rate = K [Alkyl halide]1
Rate of SN1 reaction is independent of concentration and reactivity of nucleophile, i.e.,
It is first order reaction
rate
rate
[Alkyl halide] [Nucleophile]
(2). Energetics of the SN1
TS (1)
TS (1)
(3). Stereochemistry of SN1 reactions ® In the SN1 mechanism, the carbocation intermediate is sp2
hybridized and planar, A nucleophile can attack on the carbocation from either face, if reactant is
chiral than after attack of nucleophile, from both faces, both enantiomers are fomed as the product,
which is called racemisation.
Mechanism of racemisation (SN1) ®
CH OH / Ag+
¾¾ ¾
3
¾¾
¾® (carbocation rearrangement)
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If enantiomers are formed in equal amounts then reaction is said to proceed with complete
racemisation. In the case of complete racemisation no optical acivity is detected in the mixture.
However, in practice the expected complete racemisation is rarely observed. The products usually
consists of more inversion product than retention product.
In most of the case the product has usually of 5-20 % inverted product and 80-95% racemised
species. Thus reaction proceed with partial racemisation and some inversion. This may be
explained by considering that the attack by a nucleophile occurs before the leaving groups has
completely departed from the neighbourhood of the carbocation, thus, to a certain extent the
leaving group sheilds the front side of the carbocation from attack. Consequently, the backside
attack is preferred to some extent resulting in the inversion of configuration.
R' R R' R R'
R C X C +X –
C + X–
R'' R'' R''
lone pair Free ions
front side of carbocation is blocked both faces of carbocation are free
Nu– Nu–
can attack from can attack from
back only and back
R R' R'
Nu C R' R C Nu + Nu C R
R'' R'' R''
Inversion Product Racemic mixture
The more stable is the carbocation, the greater is the proportion of racemisation. This is because
in such cases the leaving group gets time to leave neighbourhood of the carbocation before the
attack by a nucleophile occurs, thus, there is almost equal facility for attack from either side of the
carbocation plane leading to a greater degree of racemisation. In solvolysis reaction, more nucleo-
philic is solvent, greater is the proportion of inversion. For example
(+) C6H5 – CH – Cl 80% acetone + 20% water 98 % racemisation
(less proportion of inversion)
CH3
100 % water 80 % racemisation

(+) C6H5 – CH – Cl
(greater proportion of inversion)
CH3
(5) Formation of rearranged products : Since formation of carbocation takes place in SN1 reaction
hence rearrangement of carbocation is possible to form more stable product.
The driving force responsible for carbocation rearrangement is formation of more stable carbocation.
(A) Carbocation rearrangement by (1, 2) Shifting of H, alkyl, aryl, bond
¾¾¾¾¾
1, 2 hydride shift
®
36
E
¾¾¾¾¾
1, 2 methylshift
®
¾¾¾¾¾
1, 2 phenylshift
®
CH2 = CH – CH2 – ¾¾® CH2 = CH – – CH3
¾¾®
(B) Carbocation rearrangement by Ring expansion

(1) Ring expansion or contraction release angle strain in the ring. Hence it can be observe in following
manner :
(a) C4 ® C5 (b) C5 ® C6 (c) C7 ® C6
(2) < (Stability order)

(3) (i) º
x (Angle strain)
(ii) º
(iii) ¾¾®
One very stable carbocation reported is cyclopropylmethyl carbocation. This unique stabilisation is
seen in this case of three member ring only.
(more stable than Benzyl)
cyclopropyl methyl carbocation
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(C) Carbocation rearrangement by Ring contraction

Whenever strained ring such as 4 membered or 7 membered has +ve charge on ring atom contraction
may take place.
+
¾¾® ; ¾¾® ; ¾¾® +
(6) Factors affecting reactivity in SN1 reactions :

(A) Effect of substrate structure : Since rds involves formation of carbocation hence all the factors
which affect stability of carbocation, will also affect rate of SN1 reactions.
Decreasing order of reactivity of some substrates in SN1 reactions
Ar3CX > Ar2CHX > R3CX > ArCH2X > CH2 = CH – CH2 – X > R2CHX > RCH2X
(a) Unsaturation at the a-carbon: In such cases SN1 reactions are highly unfavoured because
unsaturation at a carbon creates partial double bond character in C–X bond. That’s why vinyl
halides and aryl halides do not give SN1 reactions.
(b) Unsaturation at the b -carbon: In such cases SN1 reactions are highly favoured because
formed carbocation is resonance stabilised
(c) Presence of heteroatom at a-carbon: If heteroatom is present at a position then it can

stabilize formed carbocation by direct lone pair donation
a + –
CH3 – CH2 – O – CH2 – X ® CH3 – CH2 – O– CH 2 + X
(Excellent substrate)
+
CH3 –CH2 – O = CH2
Highly stable because all atoms
has its complete octet
38
E
+ –
CH3 – CH2 – NH – CH2 – X ® CH3 – CH2 – NH– CH2 + X
(Excellent substrate)
+
CH3 –CH 2 – NH = CH2
Highly stable because all atoms
has its complete octet
(d) Presence of carbonyl group on b-carbon : carbonyl group at b carbon destabilizes carbocation,
that’s why in such cases SN1 is not possible.
(e) Substitution effect : Greater is the number of alkyl group at C+ , more will be stability of
formed carbocation. Hence rate of reaction will be faster
(B) Effect of Solvent : Greater is the ionising ability of the solvent more will be rate of SN1.
Because to solvate cations and anions so effectively the use of a polar protic solvent will greatly
increase the rate of ionisation of an alkyl halide in any SN1 reaction. It does this because solvation
stabilises the transition state leading to the intermediate carbocation and halide ion more than it
does the reactant, thus the energy of activation is lower.
R–X (Solvolysis)
Solvated ions
Table - : Dielectric constants (Î) and ionisation rates of t-Butylchloride in common solvents
Solvent Î Relative rate
H2O 80 8000
CH3OH 33 1000
C2H5OH 24 200
(CH3)2CO 21 1
CH3CO2H 6 –
(C) Effect of leaving group ; In the SN1 reaction the leaving group begins to acquire a negative charge
as the transition state is reached. Stabilisation of this developing negative charge at the leaving
group stabilises the transition state and this lowers the free energy of activation and there by
increases the rate of reaction. Leaving ability of halogen is F¯ < Cl¯ < Br¯ < I¯
Hence greater is the leaving power of leaving group, more will be reactivity of substrate towards
SN1.
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(D) Effect of the attacking nucleophile : RDS does not involve nucleophile or its nucleophilicity.
Hence rate of SN1 reactions are unaffected by the concentration and nature of the nucleophile.
Hence neither nucleophile nor its nucleophilicity has any effect on rate of SN1.
Weak, neutral, mostly solvents (protic) itself functions as nucleophiles in SN1 reaction. So SN1
reaction are termed as solvolysis reaction.
water ® hydrolysis ; C2H5OH ® ethanolysis
CH3COOH ® acetolysis ; NH3 ® ammonolysis
Some SN reactions of alkyl halide ®

–
Nu + R – X ® Nu – R + X
–
KEY POINT
(1) When base is weak but strongly nucleophilic toward carbon, then E2/SN2 ratio is low but in the
presence of strong base the E2/SN2 ratio increases.
(2) Rate of reaction increases as temperature increases. Thus the E2/SN2 ratio will increase with the
increasing temperature.
EXAMPLES
1. The elimination of HX from an alkyl halide forms an alkene. The order of the elimination
reaction is -
(A) 3º halide > 2º halides > 1º halides (B) 1º halide > 2º halides >3º halides
(C) 1º halide = 2º halides > 3º halides (D) 2º halide > 1º halides > 3º halides
2. A strong solution of alcoholic alkali will preferentially promote alkyl halide into an alkene by-
(A) Addition (B) Elimination (C) Polymerisation (D) Substitution
3. In the following reaction
CH 3 CH2CHBrCH3 + (CH3 )3COK ¾® the major product is-
(A) CH3CH2CHCH3 (B) CH3CH2CHCH3

OC(CH3)3 OH
(C) CH3CH2CH=CH2 (D) CH 3CH=CHCH3

4. The ease of dehydrohalogenation with alcoholic KOH in case of chloroethane (I),
2-chloropropane(II), 2-chloro- 2-methylpropane (III) is of the order -
(A) III > II > I (B) I > II > III (C) II > I > III (D) I > III > II
40
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VIII. NUCLEOPHILIC SUBSTITUTION REACTION (SN)

Nature of C – X bond
Since halogen atoms are more electronagtive than carbon, the carbon halogen bond or alkyl halide
is polarised, the carbon atom bears a partial positive charge whereas the halogen atom bears a
partial negative charge.
d+ d-
C–X
Replacement (displacement) of an atom or group by an other atom or group in molecule is known

as substitution reaction. If substitution reaction is brought about by a nucleophile then it is known
as nucleophilic substitution reaction. Generally substitution takes place at sp3 carbon.
R–L + Nu– ¾¾® R – Nu + L– (L – leaving group)
Nucleophilic substitution reactions can be classified as following :
Nucleophilic substitutions reactions
SN2 SN1 SNGP SN i

(i). Bimolecular nucleophilic substitution reaction (SN2)
Nucleophilic substitution in which incoming group replaces leaving group in one step only.
Reaction does not involve formation of any intermediate.
SN2 Reaction of Alkyl halide :
R – X + Nu– ® R – Nu + X–
Mechanism :
¾¾® +
(1) Characteristics of SN2 reactions

(A). Nucleophile attacks on the substrate from just opposite side to the leaving group.
(B) Hybridisation of the cation at which substitution occurs changes from sp3 to sp2 in the
transition state
(C) It is bimolecular, one step concerted process
rate µ [alkyl halide] [nucleophile]
rate = k[alkyl halide] [nucleophile]
(D) Transition state has following structure
H
d– d+ d
–
Nu C Lg
H H
(Pentacordinated carbon
in sp2 hybridised state)
Bond with nucleophile and leaving group are relatively long and weak in transition state
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(2) Energetics of the reaction :
Figure : A free energy diagrams for SN2 reaction

No intermediates are formed in SN2 reaction, the reaction proceeds through the formation of an
unstable arrangment of atoms or group called transition state.
(3). The stereochemistry of SN2 reactions ® In SN2 mechanism the nucleophile attacks from the
back side, that is from the side directly opposite to the leaving group. This mode of attack causes
an inversion of configuration at the carbon atom that is the target of nucleophilic attack. This
inversion is also known as Walden inversion.
L L
Inversion
¾¾ ¾ ¾¾®
It is always not necessary that absolute configuration will change. Absolute configuration
will invert when both incoming nucleophile and leaving group have same priority according to
C.I.P rule
(4) Factor's affecting the rate of SN2 reaction
Number of factors affect the relative rate of SN2 reaction, the most important factors are
(A) Effect of substrate structure
(a) Alkyl groups at the a and b carbons : Since SN2 reaction are very sensitive to steric
hinderance, hence if alkyl groups are present at a and b carbon, then they will increase steric
crowding that leads to decrement in rate of reaction.
Reactivity order towards SN2 reaction
CH3 – X > 1° alkyl halide > 2° alkyl halide >> 3° alkyl halide (unreactive)
The important reason behind this order of reactivity is a steric effect. Very large and bulky
groups can often hinder the formation of the required transition state and crowding raises the
energy of the transition state and slows down reaction.
Relative rate of reactions of alkyl halide in SN2 reaction.
42
E
Substituent Compound Relative rate

Methyl CH3X 30
1° CH3CH2X 1
2° (CH3)2CHX 0.02
Neopentyl (CH3)3CCH2X 0.00001
3° (CH3)3CX ~0
(b) Presence of unsaturation on b carbons : Presence of unsaturation on b carbon in primary
alkyl halide increases rate of SN2 , that’s why allyl halide and benzyl halides are good substrate
for SN2
(c) Presence of hetero atom on a carbon : Lone pair present on hetero atom stabilizes transition
state by delocalization. Hence rate of reaction increases.
(d) Presence of carbonyl group at b carbon : Presence of carbonyl group at a -carbon makes
a substrate favourable for SN2 reactions it is due to p-orbitals on carbonyl group are parallel to
the p-orbital in SN2 transition state. In such cases reaction will be exceptionally faster A
comparison of rate of relations towards SN2
O
CH3 – X CH2 = CH – CH2 – X C6H5 – CH2 – X CH3 – O – CH2 – X C6H5– C–CH 2X
200 79 200 920 105
O X
O X R
R
R–C–C + Nu –
R– C– C
R
R
Nu
[Transition state]
Stabilisation of the transition
state by p-orbital of the CO group
(B) Concentration and reactivity of the nucleophile
(i) Since nucleophile is involved in expression of rate of S N2. Hence on increasing concentration
of nucleophile, rate of SN2 increases.
(ii) As nucleophilicity of nucleophile increases rate of SN2 reaction increases.
(iii) Anionic nucleophiles mostly give SN2 reaction
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(C) The effect of the solvent : Polar aprotic solvent have crowded positive centre, so they do not
solvate the anion appreciably therefore the rate of SN2 reactions increased when they are carried
out in polar aprotic solvent.
Solvent Dielectric Constant Relative Rate
CH3 OH 32.6 1
DMSO 48.9 1300
N, N -Dimethyl -formamide 37.5 2800
Acetonitrile 36.7 5000
X. PREPARATION OF ALKYL HALIDE
(i). By direct halogenation of alkanes :
R - H ¾¾¾
X 2 / hv
® R - X + HX
Reactivity of above reaction with respect to type of hydrogen to be replaced follows given order
Tertiary hydrogen > Secondary hydrogen > Primary hydrogen
As far as the reactivity of halogen is concerned, F2 is most reactive while I2 is least reactive. Infact,
reaction with I2 is reversible and is carried out in the presence of some oxidising agents like HIO3,
HNO3 etc. to oxidise HI into I2.
44
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(ii). By the addition of H—X on alkenes :
Alkyl chlorides, bromides and iodides can be prepared by treating an alkene with corresponding
halogen acid (HCl, HBr or HI). The addition of these compounds to alkene takes place according to
Markownikov’s rule. The reaction proceeds by electrophilic addition of H+ to give more stable
carbocation followed by attack of X–.
Å -
CH 3 - CH = CH 2 ¾¾®
HX
CH 3 - C H - CH 3 ¾¾
X
® CH 3 - C H - CH 3
(2° carbocation ) |
X
Anti-Markownikov addition of HBr can be achieved, if the reaction is carried out in presence of
peroxides (H2O2 or benzoyl peroxide or di-tert-butyl peroxide). Addition of HBr to alkenes in the
presence of peroxide follows free radical mechanism.
· ·
CH 3 - CH = CH 2 ¾¾¾HBr
¾
Peroxide
® CH3 - C H - CH 2 - Br ¾¾ ¾
HBr
® CH 3 - CH 2 - CH 2 Br + Br
(2° radical)
(iii). By Alcohols :
(a) By the action of hydrogen halides :
H–X
Example : R—CH2—OH ¾¾¾¾
ZnCl2
® RCH2—X
Mechanism :
.. H+ Å –H2O Å X1
R CH2 OH R CH2 O H ¾¾¾® R CH2 ¾¾¾® R CH2 X
(H—X)
H
(unstable) (Product)
In this reaction intermidiate carbocation is formed so rearrangement ( H – shifting or CH3– shifting) can take place.
ZnCl2 act as dehydrating agent and absorbs H2O from the reaction so good yield of halide is obtained. Also it generates
H+ from HCl.
Å
HCl + ZnCl2 ¾¾¾® ZnCl1
3 + H
Reactivity order for alcohol :
Reactivity µ stability of intermediate carbocation , so reactivity order : Tert. alc. > Sec. alc. > Pri. alc.
Reactivity order of H—X is :HI > HBr > HCl
HI is maximum reactive so it reacts readily with 1°, 2° and 3° alcohols.
R—OH +HI ¾¾® R—I + H2O
HCl and also 1° alcohol are less reactive so ZnCl2 or some amount of H2SO4 is needed to increase the reactivity.
Example : CH3—CH2—OH+HCl ¾¾¾¾
2ZnCl
® CH3—CH2—Cl
At normal condition :
CH3—CH2—OH + HCl ¾¾¾¾¾¾® ×(no reaction)
E 45
JEE-Chemistry
Note : HCl + ZnCl2 is called as lucas reagent, alchol gives turbidity with lucas reagent.
Reactivity towards lucas reagent (difference in 1°, 2° and 3° alcohol).
1° alcohol 2° alcohol 3° alcohol
Time to in 30 min. in 5 min. in 1 min.
give turbidity
(b) By the action of phosphorus halides :
R - OH + PCl 5 ¾¾
® R - Cl + POCl 3 + HCl
3R - OH + PCl 3 ¾¾
® 3R - Cl + H 3 PO 3
3R - OH + PBr3 ¾¾
® 3R - Br + H 3PO 3
3R - OH + PI 3 ¾¾
® 3R - I + H 3 PO 3
Phosphorous halides are prepared by treating red phosphorous and halogen. The advantage of
using phosphorous halides is that the reaction does not involve carbocation intermediate so, it is
free from rearrangement.
PBr3 and PI3 are less stable, thus for bromides and Iodides, ( P + Br2) Or ( P + I2) mixture is
used.
Mechanism for Reaction with phosphorus trihalides
3R – OH + PX3 3R – X + H3PO3
Step : 1
Step : 2 RCH2X+ HOPX2
The mechanism for the reaction involves attack of the alcohol group on the phosphorus atom,
displacing a halide ion and forming a protonated alkyl dihalophosphite
In second step a halide ion acts as nucleophile to displace HOPX2, a good leaving group due
to the electronegative atoms bonded to the phosphorus.
CH 3 CH 3
| |
Example PBr
CH 3 – CH 2 – CH – CH 2 – OH ¾¾ ¾
3
® CH 3 – CH 2 – CH – CH 2 – Br
2 - Methyl - 1 - bu tan ol 2 - Methyl - 1 - bromobutane
46
E
Example CH3 CH2OH P + I2 CH3 CH2 I

¾¾ ¾¾ ®
Ethyl alcohol Ethyl iodide
Example
(c) By reaction with thionyl chloride - (Darzen's reaction) :

R - OH + SOCl2 ¾¾¾®
Pyridine
R - Cl + SO 2 +HCl
The usefulness of this method is that there is not side product, which has to be separated. The
side products are gaseous, which escape from the reaction mixture and HCl, which forms a salt
with the base (pyridine), named pyridinium chloride (C5H5N+Cl–). The product alkyl chloride
has a configuration inverted with respect to the reactant alcohol (if it is chiral) in the presence of
pyridine base. In absence of a base and polar solvent, the chiral alcohol gives alkyl chloride
with retention of configuration.
Williamson Ether Synthesis:
Formation of ether by reaction between alkoxide (R–OX) with substrate.
Alkyl Halide Reaction
2
(SN mechanism)
RONa + RX ¾¾¾¾¾¾ ®R - O- R
RONa + R'–X
R–O–R'
R'ONa + R–X
ArONa + R–X
Ar–O–R
R–ONa + Ar–X
Note: (i) It follows SN2 mechanism
(ii) For Williamson ether synthesis reaction
R–X
1º 2º 3º Bridge Aryl, Vinl

2
E (100%) No No
2 reaction reaction
E
2
SN
Alkene Ether
(Ma) (Mi)
E 47
JEE-Chemistry
1. CH 3ONa + CH 3 X ¾¾
® CH 3O + CH 3X
H H
CH3O –
O
H X CH3O H
H H
2. CH3–ONa + X ¾¾
®
O– + X O
3. CH3–ONa + X
X O
O– +
Cl NaOH
4.
OH
Cl NaOH
O–
O
Cl
5.
Hs
S
–
Cl
S
OH
6.
Cl
O– O
Cl
SH SH
S
7.
Cl Cl
48
E
NaN3
CH2Ph (I) CH2Ph (II)

TsCl EtONa
Me–CH–OH Me–CH–OTs
Et–OH
(a = +33°) (a = +33.1°) aq. K2CO3
(X)
CH2Ph
Me–CH–OEt
(a = –19.9°)
CH2Ph (III) PhCH2 (IV) CH2Ph

Na Metal CH3CH2Br
Me–CH–OH Me–CH–ONa Me–CH–OEt
(a = +33º)
This reaction process SN2 reaction involves bond inversion. In the first step SNAE (a =
+23.5°) where TsCl makes OH as a leaving group and chiral centre is not disturbed. Simi-
larly in III, chiral centre is not touched as well as in IV and (X) behaves as a nucleophile.
Only in II, SN2 mechanisam takes places which causes bond inversion and thus the product
of II which is the inantious of the product of reaction IV has opp signs of angles of rotation.
CLEAVAGE OF ETHER
Reaction of ROR with HI :
(i) R - O - R ¾¾¾
NaOH
® No reaction.
Hence ethers are stable in basic medium
(ii) R–O–R + conc. HI ¾® R–OH + RI
or
cold HI
(iii) R–O–R + conc. HI (excess) ¾® 2RI + H2O
or
Hot HI
(iv) R–O–R + conc. ¾® RI + R'I + H2O
or
Hot HI
(v) Ar–O–R Ar–OH + RI
Cold HI or conc. HI
Hot HI or conc. HI (excess)

Ar–OH + RI
as Ar–X can't be forms by SN and SN on Ar–O
1 2
(vi) R–O–R + conc. HI ¾® R–I + R'OH

R–O–R + conc. HI ¾® R'I + R'OH
1. O HI
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O HI OH + I
HI
2. O
HI HI I +
O O OH
HI
3. O
HI
O + OH
I
4. HI
Ph–O–CH3
HI
Ph–O–CH3 Ph–OH–CH3I
HI
5. Ph–O–Ph No reaction
SN1/SN2 can't take place in –Ph group.
HI
6. Ph–O– No reaction
SN1/SN2 can't occur at smaller bridgehead.
HI
7. O No reaction
SN1/SN2 can't occur at smaller bridgehead.
HI
8. O
18
OH I
HI
O +
18
O Hot HI
9.
Cold HI
(i) Ph – O – CH 3 ¾¾¾
cold HI
® Ph - OH + CH 3I
(ii) Ph – O – CH 3 ¾¾¾
hot HI
® Ph - OH + CH 3I
Hot HI
10. Cold HI
O
O–H
(i) OH
I
I
(ii) O–H
OH2
I I
50
E
HI
11. No reaction
O
SN /SN2 can't take place at Ph.
1
H
O
HI
No reaction
HYDROLYSIS OF ETHER
1. R - O - R ¾¾¾¾®
NaOH / H 2O
No reaction.
+
2. R - O - R ¾¾¾¾¾
H / H 2O
(or) dil.H 2SO 4
® 2ROH
H 2 O + H + ¾¾
® OH - + H 2
+
3. R - O - R ¾¾¾¾¾
H / H 2O
(or) dil.H 2SO 4
® R – OH + R 'OH
Note : (i) SN1 mechanism.
18 H2O
4. O CH3
+ 18
O CH3 + CH 3OH
18
H OH
O
18 H2O
5.
+
H 18
O OH
18 H 2O
+ CH3OH
H2O
6. O
18
H
18
O OH + OH
18
H2O
7. O No reaction as can't appear on benzen or bridgehead.
H2O
8. O No reaction
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O
OH–/H2O
+d +d R–C
9. (a) R–CºN O
H,H,H O
H+/H2O
OH, OH, OH R–C
OH
O
OH–/H2O +
+ R–NH3 + R–C
(b) R–NºC O
O
H+/H2O +
R–C + R–NH3
OH
VII. ELIMINATION REACTIONS

In elimination reaction two atoms or groups (YZ) are removed from the substrate and generally
resulting into formation of p bond.
| |
E limination
-C-C- ¾¾ ¾ ¾ ¾¾®
- YZ
| |
Y Z
Elimination can be of following types :
(1) a-elimination : When two groups or atoms are lost from the same carbon it is known as
a elmination. It gives a carbene (or nitrene). This is also called 1–1 elimination.
¾®
(2) b -Elimination : When two groups or atoms are lost from adjacent atoms so that a new p bond
is formed. This is also called 1–2 elimination.
¾®
Based on mechanism, elimination Reactions can be classified as following :
Elimination Reaction
E2 E1 E1CB Ei
Elimination Unimolecular Elimination Elimination
Reaction with Elimination conjugate base internal
molecularity = 2 Reaction Reaction Reaction
52
E
(i). Bimolecular elimination reaction (E2) :

Dehydrohalogenation is the elimination of a hydrogen and a halogen from an alkyl halide to form
an alkene.
Example : CH 3CH2Cl ¾¾¾¾
Alc.KOH
® CH2 = CH2
Reagent Used :
(i) alcoholic solution of KOH or EtO¯/EtOH (ii) NaNH2 (iii) t-BuO¯ K + in t-BuOH
Mechanism :
TS
Free Energy
¾¾® ¾¾® + BH CH3CH2Cl CH2= CH2
Progress of reaction
(1) Characteristics of E2 reaction :

(i) This is a single step, bimolecular reaction and follows a concerted mechanism.
(ii) It is a second order reaction and the kinetics of the reaction can be given as
Rate µ [R – X] [Base] ; Rate = k [R – X] [ ]

(iii) Rearrangment is not possible, since carbocation is not formed.
(iv) The orientation of proton & leaving group should be antiperiplanar, i.e., they should be anti
to each other or at the angle of 180 to each other.
(v) Reactivity order for alkyl halide towards E2 reaction is given as
R – I > R – Br > R – Cl > R – F
(vi) Positional orientation of elimination ® In most E2 eliminations where there are two or more
possible elimination products.
(2) Formation of saytzeff product : The product with the most highly substituted double bond
will predominate. This rule is called the saytzeff or zaitsev rule.
Example :
CH3
(i) +
(major)
(ii) +
E 53
JEE-Chemistry
(iii)
(3) Formation of the Hoffmann product

Bulky bases can also accomplish dehydrohalogenations that do not follow the saytzeff rule. Due
to steric hindrance, a bulky base abstracts a less hindered proton, often that leads to formation of
least substituted product, called the Hoffmann product.
H CH3
| |
CH3 - C - C - CH2 +
| | |
H Br H
Bulky base :
(CH3CH2)3N:
Triethylamine
Example : Dehydrohalogenation of 2-bromo-2-methylbutane can yield two products.
54
E
(4) Stereo Chemistry of E2 reactions :

E2 reaction is an example of anti-elimination in which both H and leaving group are antiperiplanar
to each other.
The E2 is stereospecific because it normally goes through an anti periplanar transition state. The
sterio specific products are alkene. Formation of product in E2 can be explained as following :
Example :
Base
H CH3
Ph Ph
Ph H
Ph H
Û Û = = Ph Ph
Ph CH3 Ph
H CH3 CH3 H
Br H
Br
(5) Factors affecting E2 reactions :

(A) Structure of substrate : Branching at a and b carbon increase rate of E2 reaction. As number
of substituents increase stability of transition state increases. Hence order of reactivity of alkyl
halides towards E2 reaction is 3º > 2º > 1º
(B) Nature of leaving group : Better is the leaving group higher is the rate of E2 reaction
(C) Strength of the base : Since RDS involves base hence increase in basic strength of increase
rate of E2.
(D) Nature of solvent : The yield of the product formation in E2 reaction increases with decrease
in solvent polarity.
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(ii). Unimolecular Elimination Reaction (E1) : Proton and leaving group depart in two different step.
First step : - Slow step involves ionisation to form carbocation
Second step : Abstraction of proton
Mechanism :
Step 1 :
Step 2 : + B–H
(1) Characteristics of E1 reaction :

(A) It is unimolecular, two step process.
(B) It is a first order reaction.
Rate µ [Alkylhalide]1
Rate = k [Alkylhalide]1
(C) Reaction intermediate is carbocation, so rearrangment is possible
(D) In the second step, a base abstracts a proton from the carbon atom adjacent to the carbocation,
and forms alkene.
(2) Energetics of E1 reaction :
Example :
CH3
|
CH3 - CH2 - C - CH3 ¾¾® +
|
Br
56
E
E1 Reaction of Alcohol :
Dehydration requires an acidic catalyst to protonate the hydroxyl group of the alcohol and convert
it to a good leaving group. Loss of water, followed by loss of proton, gives the alkene. An
equilibrium is established between reactants and products. For E1 mechanism reagents are
(i) H3 PO4/ D (ii) H2SO4 / 160º
| | | |
acid
- C - C - ¾¾ ¾® - C = C - + H2O (Rearrangement may occur)
| |
H OH
Mechanism :
Step 1 :
Step 2 :
slow

+
Step 3 +
In first step, an acid-base reaction occurs, as a proton rapidly transferred from the acid to one of
the unshared electon pairs of oxygen atom of the alcohol.
In second step the carbon oxygen bond breaks. The leaving group is molecule of water :
Finally,in third step the carbocation transfers a proton to a molecule of water. The results in the
formation of a hydronium ion and an alkene.
Reactivity order of ROH : 3° alcohol > 2° alcohol > 1° alcohol
Example
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JEE-Chemistry
CH2
CH2OH
Conc.H2 SO 4
Example ¾¾ ¾¾¾ ¾¾® +
D
(I)
Minor
Migration
H Å
Example H
¾¾
Å
¾® of bond
¾¾ ¾¾¾® ¾¾¾®
(4) Factors Affecting E1 Elimination Reactions :

(A) Structure of Substrate : Since rate determining step involves formation of carbocation hence
order of reactivity will be 3º > 2º > 1º alkyl halide. Alkyl and aryl substitutions on a and
b -carbons with respect to the leaving group increase the rate of E1 reactions. As the strain
increases the yield of the E1 product increases.
(B) Strength and concentration of the base : Since E1 reactions do not usually required any
base in rds on increasing the strength and concentration of the base have nothing to do with
rate of reaction
(C) Nature of the leaving group : Better is the leaving group more easier will be formation of
carbocation.
(D) Nature of solvent : Greater is the polarity of solvent, more will be rate of E1
(E) Temperature : With rise in temperature E1/SN1 ratio rises, as in the elimination process.
(iii). Elimination Internal (Ei) or Pyrolytic Syn-Elimination
These elimination reaction occur through formation of cyclic transition state involving only one
molecule of substrate. These elimination reactions occur within a small family of compounds.
Like acetates, amine oxides sulphoxides, xanthates etc.
Example :
(1) Pyrolysis of esters
H H H H H
Me H H
Me H
500ºC
O O + MeCO2H
H Me
HO C C
Me O Me H
6-membered
cyclic TS
58
E
(2) Cope’s reaction :

H H H H H
Ar H Ar H H
+ 150º d +
NMe2 H + Me 2NOH
d– NMe
H O –
O Ar
6-membered H
cyclic TS
Both of the above reactions take place through formation of 5/6 membered cyclic TS and rate is
found to be Rate = k[Substrate]. The reactions are possible because the leaving groups are lying
in the same plane and on the same side.The elimination process have synthetic utility in producing
terminal unrearranged alkene. The above elimination is thus steroselective.
(iv). Unimolecular conjugate base reaction (E1 cB Reaction) :

In the E1 cB, H leaves first and then the X. This is a two step process, the intermediate is a
carbanion.
Mechanism :
H
| |
Step 1 : -C-C- X (conjugate base)
| |
Step 2 : ¾¾® –C = C –
| |
First step consists of the removal of a proton, , by a base generating a carbanion

In second step carbanion looses a leaving group to form alkene
Condition : For E1 cB, (i) substrate must be containing acidic hydrogens and (ii) poor leaving
groups.
(i) ¾®
B
(ii) H
H2C – CH2 – F ®CH2 = CH2
H2C – CH 2 – F
(iii) ¾® R2C = O +
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ILLUSTRATION :
60º rotation
H C6H5 H
C6 H 5
C6H 5 H
H Br H Br –
Br EtO C6H5
(5) H Û Br
Û C6H 5 Br
H Br
C6 H 5 Br
(orient H , Br anti to C6H5 H
C6H 5 C6H 5
each other)
Erythro
C6H5 Br
Al2O3 (i) HI Al2O3 (i) B2H6

(6) (A) . (B) (C) (B) (ii) H2O2, OH– (A)
250° (ii) AgOH 150°C
(A) and (C) are isomers. (B) has a formula of C5H10 which can also be obtained from the
product of reactions of CH3CH2MgBr and acetone. Identify (A), (B), and (C).
Solution : (B) [M.F = C5H10] can be obtained as
CH2CH3 CH3
H+
CH3CH2MgBr + CH3CCH3 CH3CCH3 C2H5 — C — CH3
O OMgBr OH
D
CH3CH = C(CH3)2
(B)
Since (B) is formed by heating (A) with Al2O3, (A) must be an alcohol. Moreover, (A) and (C) are
isomers. Hence
CH3
(A) is CH3CH — CHCH 3 ; (B) is CH3 CH = C — CH3 ; (C) is CH3 — C — CH2CH3
CH3 OH CH3 OH
60
E
FREE RADICALS :
(i) Trivalent
(ii) Incomplete octed
(iii) Odd electron species
(iv) Highly unstable
(v) Highly reactive
(vi) B.P. = 3
(vii) U.P. = 1
(viii) L.P. = 0
(ix) L.P. = 0
(x) MM = 3
(xi) Spin moment = 2|s| + 1 = 2
(xii) Doublet intermediate
(xiii) Paramagnetic
(xiv) sp2 hybrid, (sp3 when surrounded by E.N. atom)
(xv) Formes by hommolytic fission
(xvi) Formed in gas phase/non-polar solvent
(xvii) Trigonal planar
(xix) Can be approached from both side. (***)
* Halogen radical are responsible for ozone layer depletion
Stability :
Ph3C > Ph2CH2 > PhCH2 > CH2–CH=CH2 > 3° > 2° > 1°
CH3 > CH2=CH2 >
THERMAL DECOMPOSITION :
Radical can be generated by heating.
D
1. Cl—Cl 2Cl
2. D
CH3–O–O–CH3 2CH3O
CH3–C–C–CH3 D 2CH3–C D 2CH3–C + CO
3.
O O O
PHOTOLYSIS :
Usually photons of UV light are used because they have sufficient energy & even can break
strongest bond of organic compound. We use photon energy for initiation (generation of radical).
hn
4. CH3–C–O–O–C–CH3 2CH3–C + O
O O O
hn
5. N=N + N2
hn
6. O–Cl O + Cl
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BY METAL OR METAL ION :
7. Na + Cl + NaCl
8. Na + Br + LiBr
+2
9. + V + V+3
OH O
10. (i) NaOH
(ii) K3[Fe(CN)6]
BY RADICAL :
O
11. R–C R + CO2
O
Br + Br
12.
(excess) Kinetically forward path
13. Br + HBr +
(excess) (thermodynamically stable)
14. RO + HBr ROH + Br

REACTION SHOWN BY RADICAL :
(i) Combination / dimerization
(ii) Elimination / disproportion
(iii) Rearrangement
1. COMBINATION :
1
rate of combination µ
Steric crowding
1. R + Cl R–Cl or R + Cl2 R–Cl + Cl
2. + Br2
+ Br
Br
3. 14 + Br2
14 14 + Br2 14
Br2 + Br2
14
62
E
E
9.
8.
7.
6.
5.
4.
H
H
Me
Me
Br
Br
Br
Br
Et
Et
Br
Br
+ Br2
+ Br2
+ Br2
+ Br2
+ Cl
Br2
+ Cl2
+ HBr
HBr
–Br
Br
Br
H
Br
Me
+
H
–Br
Cl
Et
Br
Br
Br
Br
Br
63
+ Img.
+ Br
JEE-Chemistry
In inert medium :
10.
+
11.
12.
2. Elimination : Very poor yield due to steric crowding.
CH3 CH3
13. CH3–C–CH3 + CH2–C–CH3 +
14.
+ +
Cl
(Major)
Note : Ph–CH2 , CH3 donor undergo disportion.

15. CH3–CH2
CH3–CH2 + CH3–CH2 CH3–CH3 + CH3=CH2
16. CH3–CH2 + CH3–CH2–CH2
+ +
Free radical method is
very good for obtaining + + +
odd numbered alkanes.
The underlined are MAJOR
17. CH3–CH 2 + CH3

+ CH3 CH4 + + + +
18.
+ 14 + + CH2=C=CH2
64
E
19. 14
14 14
14 + 14 14 14
12
14
+ 14 + 14 + CH2=C=CH2
Cl
20. Na
Et2O
Cl
+ Na + + +
Cl
Na
21. Et2O
14
Cl
+ Na + + +
14 14 14 14 14 14 14
(3 more products
by resonance)
Ph Ph Ph
22. Ph3Cl C CPh3 + C
Ph Ph Ph
(Major) (Major)
Ph3C–CPh3
PINACOLE FORMATION :
When Carbonyl are treated with amalgamated magnessium, vicinal diols are obtained as a product
followed by hydrolysis.
O OH OH
(i) Mg Hg
C
(ii) H2O
R1 R2 R1 R2 R1 R2
Mg
–
O O O–
Mechn : Mg
C C C
2R2 R1 R1 R2 R2 R1
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O– O–
OH OH
HOH
C C
– Mg(OH)2
R1 R2 R1 R2 R1 R2 R1 R2
No. of Pinacole
If R1 = R2, 1
R1 ¹ R2, 3
1. CH3 C CH (i) HgSO4/H2SO4
(ii) Mg – Hg
(iii) H2O
(iv) H+/D
CH3 C CH3 O– + O– O
O – –
O O O O
2. PH C CH (i) HCl (excess)

(ii) Aq. NaOH
(iii) Mg – Hg
(iv) H2O
(v) Conc. H2SO4
Cl OH
HCl excess Aq.
PH C CH PH C CH3 Ph C CH3
NaOH
Cl OH
Mg.Hg
PH C CH3 2Ph C CH3
–
O O
O– Ph
O –
O– CH3
C + C
CH3 + img.
C Ph C –
Ph CH3 Ph CH3O
Ph Ph
CH3 OH OH CH3 conc. H2SO4

+ + Img
CH3 OH CH3 OH
Ph Ph
66
E
CH3
Ph
Ph O
WURTZ REACTION :
In this reaction, alkyl halide is treated with sodium metal in dry ether condition so that hydrocarbon
alkane is obtained as product.
Mechanisam : R - Cl ¾¾¾ ®R - R
Na
Et 2O
r.d.s.
Free radical : 2Na + 2RCl 2R + 2NaCl R–R
r.d.s.
Ionic mechanism : 2Na + R–Cl R Na + NaCl R Na
r.d.s.
R Na + R–Cl R–R
Note : (i) Free radical and carbanion both are intermediate.

(ii) Order of rate of reaction : RI > RBr > RCl
(iii) CH4 can't be obtained
(iv) Odd 'C' alkanes not obtained (poor yield)
(v) Dry ether condition required or else Na can take H+ from OH in water, alcohol.
·
1. CH 3 - Cl ¾¾¾
Na
Et 2O
® CH 3 - Cl ¾¾
® C H 3 ¾¾
® CH 3 - CH 3
Na
2. Cl Et2O
Na
Cl Et2O
Cl Na
3. Et2O
Cl Na
Et2O
Me
Na
4. H Cl Et2O
D
Me Me
Me Me
Na
H Cl Et2O H D
H D H D
D + Enantiomers
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JEE-Chemistry
Na
5. CH3–CH–Cl Et2O
D
Me
Me
CH3–CHD + CH3CHD H D + Enantiomers
H D
Me
Na
6. H D Et2O
CH2Cl
Me Me Me
H D H D H D
CH2Cl CH2 CH2
CH2
D H
Me
7. Cl Cl Na
Et2O
Cl Cl Na
Et2O
Cl Na
8. Cl Et2O
Cl Na
Cl Et2O
9. Cl - (CH 2 ) 5 - Cl ¾¾¾
Na
Et 2O
®
Na
Cl Cl Et2O
10. Cl - (CH 2 ) 6 - Cl ¾¾¾

Na
Et 2O
®
Na
Cl–(CH2)6–Cl Et2O
Na
11. Cl (CH2)7 Cl Et2O
Cl (CH2)7 Cl (CH2)n (polymerization)
It undergoes polymarization as after seven carbon the terminals are for & ring is unstable.
68
E
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16.
15.
14.
13.
12.
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Na
Cl
Cl
Et2O
Na
Et2O
Na
Et2O
Na
Et2O
Na
Et2O
69
JEE-Chemistry
Cl
Na
17. Et2O
Cl
Cl
Cl
Cl
Na
18. Et2O
Cl
Cl
Cl
no double bond as it will
become antiaromatic
Cl
Na
19. Et2O
Cl
Cl
Cl
Cl
Cl Na
20. Cl Et2O
Cl
Cl
Cl
Cl
Cl
Cl Na
21. Et2O
Cl + +
Minor
Na
22. CH3–Cl + CH3–CH2–Cl Et2O
Na
CH3 + CH3CH2 CH4 + CH3–CH2 + +
Et2O
70
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23. Which compound can be obtained in good yield with single reactant in Wurtz reaction ?
(i) CH4 – XX
(ii) – XX
(iii) 2Cl Cl
(iv) 2 Cl
Cl
(v)
Cl
Cl
(vi)
Cl
(vii) XXX
Cl
(viii) Cl
(ix) XX
Cl
Cl
(x)
(xi) X X
Na
24. Ph3Cl
Et2O
Ph
Na C CPh3
Ph3Cl Et2O Ph
(Major)
14 Cl Na
25. Et2O
14 Cl Na 14
14 14
Et2O
14 +
14
14
14
14
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26. 2CHCl3 + 6Ag ¾® HCºCH + 6AgCl
Remove Cl, from radical, form bond
27. R–CCl3 + Ag ¾®
Cl
R C Cl + Ag R–CºC–R
Cl
Fitting Reaction (Aryl Halide) :
Cl
Na/Et2O
28. D
Cl Cl
Na/Et2O
29. D + Diastereo
Wurtz-Fitting Reaction (Alkyl-Aryl) :

Cl
Na/Et2O
30. + RCl D R
Ullmann Reaction :
I
Cu
31. D
I I
Cu
32. D
Frankland Reaction :
33. CH 3 - Br ¾¾¾
Zn
Dust
® CH 3 - CH 3
Br
Zn
34. dust
Br
Br
Zn
dust
Br
72
E
KOLBE'S ELECTROLYSIS :
O
R–C
ONa
2RCOONa ¾® R–R + 2CO2 + 2NaOH + H2

Mechanism :
O O
2R–C 2R–C + 2e–
O O
O
Anode : 2R–C 2R + 2CO2
O
R+R R–R
Cathode : 2HOH + e– H2 + 2OH
* pH increases as reaction proceeds because NaOH is formed.
1. aq. CH3–COONa ¾¾¾¾¾¾

Kolbe's electrolysis
® CH3–CH3
2. aq. CH3–CH2–COONa ¾¾¾¾¾¾ Kolbe's electrolysis
®
COONa
3. aq. ¾¾¾¾¾¾
® CH2 = CH2
COONa
COONa
4. aq. ¾¾¾¾¾¾
®
COONa
COONa
5. aq. ¾¾¾¾¾¾
® HCºCH
COONa
COONa
6. aq. ¾¾¾¾¾¾
® HCºCH
NaOOC
COONa
7. aq. ¾¾¾¾¾¾
®
NaOOC
E 73
JEE-Chemistry
COONa
8. ¾¾¾¾¾¾
®
aq. COONa
CH2–COONa
9. CH2–SO3Na ¾¾¾¾¾¾
® CH2=CH2 + CO2 + SO3
(aq.) at anode
DCOONa ¾¾¾¾¾¾ ® No. of moles of gases at anode & cathode

10.
(aq.)
1 eq.
O
K.E.
Hint : 2D–C–ONa D2 + CO2 + H2
Anode Cathode
1/2 D2 1/2 H2
CO2
1. Borodine hunsdiecker reaction.

Overall reaction
R CCl4
C OAg + Br2 R-Br + CO2 + AgBr
O O
+ AgBr
Mechanisam : R C OAg+ Br Br R C O Br
O
O
R C
Non polar
R C solvent O + Br
OBr
O
R C R + CO2
O R Br + Br
Br2
R O
R C
OBr R Br + R C O
O
(i) Radical intermediate is involved
(ii) Degradation (Carbon length reduces) reaction.
(iii) Reaction is BIRNBORN SIMONINI Reaction. If I2 is taken instead of Br2, ester is formed.
O Br2
1. CH3 C CCl CH3Br
OAg 4
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Me Me
Me
2. i) AgOH +
H COOH H Br H Br
ii) Br2/CCl4 D D
D
3. 14 COOH " Br + Br
14
14
COOH Br
4. "
O O
5. (i) AgOH
CH3–C–OAg CH3–C–OCH3
(ii) I2/CCl4
Anti - Markovnikov Effect:
(Peroxide effect/ Kharesch effect)
Br
n
CH3–CH–CH3 (Ionic Add )
CH3 CH CH2 (Markonikov)
CH3–CH2–CH2
Br
(Radical Addn). (Anti Markonikov)

Note : -
(i) Each radical mechanisam involved involved 3 steps:
(a) initiation (b) Propagation (c) Termination
(ii) Each propagation step must be exothermic for spontanienty of the reaction.
(iii) Bond energy data :
C – F > C –Cl > C – Br > C – I
H – F > H – Cl > H – Br > H – I
(iv) Radical intermediate involved
(v) Only HBr (Out of all HX) show peroxide effect.
(vi) HCl, HI show ionic addition even in presence of peroxide.
(vii) Peroxide are called as radical generator because – O – O – bond is weak and can readily cleaves.
(viii) For HCl & HI, during peroxide :
P1 P2
HBr DH < O DH < O
HCl DH < O DH > O
HI DH > O DH < O
ROOR
CH CH CH + HX
3 2 CH CH CH X
3 2 2
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·
Mechanisam : Inititation : hn
R - O - OR ¾¾ ® 2R O
·
® ROH + X ·
RO + HX ¾¾
·
Propagation : X + CH 3 - CH = CH 2 ¾¾
® CH3 - C H - C H 2 P1
· |
X
Step 1 :
X=F , DH < O
X = Cl , DH < O
X = Br , DH < O
X=I , DH > O
Step 2 : CH3 CH CH2+ HX CH3 CH2 CH2 + X P2
X X
X=F , DH > O
X = Cl , DH > O
X = Br , DH < O
X=I , DH < O
Termination : X · + X · ¾¾
® X2
Complete the following reaction
1. HBr
HBr
ROOR
HI
ROOR
(i) + Br
(ii) HBr
+ Br Br
ROOR
HI Show ionic
(iii) + I
ROOR in penxide condn.
HBr
2. HBr, ROOR
HI,ROOR
(i)
Br
+
HBr ring exp + 1,2 H shift
–
76
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HBr Br
(ii) + Br
ROOR
I
+
HI Ring exp + 1,2 H–shift
(iii)
ROOR +
3. "
"
"
–
HBr 1,2 H shift
(i)
Br
HBr Br
(ii) Br
ROOR
–
HI 1,2 H shift
(iii) ROOR
I
4. Ph "
"
Br
+ *
(i) HBr
Ph Ph
Br
Br
(ii) HBr Ph *
Ph + Br
ROOR
I
+ *
(iii) HI –
Ph Ph +I
ROOR
BrCCl3
5.
ROOR
® Br · + CCl·3
BrCCl3 ¾¾
More stale
Br
CCl3
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ICBr3
6.
ROOR
® I· + CBr3·
ICBr3 ¾¾
Br
CBr3
CCl4
7.
ROOR
® Cl· + CCl3·
CCl 4 ¾¾
Cl
CCl3
*
8. CHCl3
ROOR
CHCl3 H + CCl3
Cl
CHCl2
check the answer***
Free Radical Substitution :-

One radical substite another one, then it is called as free radical substitution. Such type of reaction
can be carried out by using NBS (N-Bromosucinimide)
(i) Preparation of NBS
NH3 can also be released

but as H2O present H2O is
released first
O O O O
+
OH NH3 ONH4 D NH2 D

OH excess +
NH2 N–H
ONH4 –H2O –NH3
O O (Amino salt of O succinamide O

(Succinic Acid) succinic acid)
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O O O
KOH – Br – Br
N–H N N Br
O O O
(Succinimide) (N - Bromo
Succinide)
(iii) NBS oxidizes 1° & 2° alcohols

R CH2 OH NBS , RCH = 0
R CH2 OH , R2 H = 0
(iv) It can oxidize alkene with allylic or benzylic sites by brominating it.
Br
NBS
Br
O O
*
+ N Br N H+
O O
(v) Pure NBS is inert.

(vi) Impure NBS is used.
(vii) NBS usually contain impurity of HBr & Br2 in trace.
(viii) NBS is a source of bromine & supply is in small installement.
Br
1. CH3 CH CH2 + NBS
Mechn : Let us consider Br2 as impurity.
(i) hv
Br2 2Br
(ii) Br + + HBr
O O
–d+d
(iii) N Br + HBr N H + Br2
O O
Acid base type Reaction
Br
(iv) + Br2
E 79
4.
3.
2.
JEE-Chemistry
NBS
*
Br
Br
+
+
+
+
+
Br
(4)
+
+
*
Br
(9)
Total no. Products
+
+
+
80
Br
Br
*
Br
(3)
+
same structure take anyone out of two
*
Br
+
Br*
E
5.
+ + +
Br
* + + +
*
Br Br Br
(6)
1. PHOTOHALOGENATION
The reaction of halogen with an alkane in the presence of ultraviolet (UV) light/sunlight hn or heat
leads to the formation of a haloalkane (akyl halide). For example Flourination, Chlorination,
Bromination, Iodination
Free radical mechanism is involved during the reaction.

Different steps involve in free radical mechanism are :
(a) Free radical initiation
(b) Free radical propagation
(c) Free radical termination
Overall reaction
R H + X2 R X + HX
Mechanism:
(i) Initiation :
hn
X 2 ¾¾ ® 2X ·
(ii) Propagation :
·
X° + RH ¾¾¾
r.d.s
® R + HX
R· + X2 ¾¾ ® RXX+· + X·
(iii) Termination : R · + R· ¾¾
® R2
X · + X · ¾¾
® X2
Note :
(i) Reaction involve free radical as an intermediate
(ii) Order of rate of reaction of RH (alkane)
3· > 2· > 1·
(iii) Order of rate of reaction for X2 :
F2 >>>> Cl2 > Br2 >> I2
(iv) Kinetic isotopic effect is present
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JEE-Chemistry
(v) Involve free radical substitution
(vi) Chain reaction occur
(vii) Reaction can be slow down by adding S2, O2 etc. known as free raoical SCAVENGER.
R · + O2 ¾¾
® R — O — O·
(A) Flourination :
Highly explosive and highly exothermic
CH4 + 2F2 ¾¾ ® C(black) + 4HE
(B) Chlorination :
(i) Highly explosive and exothermic like flourination and C(black) is obtained in bright sunlight
CH4 + 2Cl2 ¾¾¾ B.S.L
® Cblack + 4HCl
(ii) Chlorination can be carried out in diffused sunlight.
CH4 + Cl2 ¾¾ hv
® CH3Cl + CH2Cl2 + CHCl3 + CCl4
Mechanism :
® 2Cl·
Cl 2 ¾¾
Cl· + CH 4 ¾¾
® CH ·3 + HCl
CCl·3 + Cl 2 ¾¾
® CH 3Cl + Cl ·
·
Cl· + CH 3 Cl ¾¾
® C H 2 Cl + HCl
·
® CH 2 Cl 2 + Cl·
C H 2Cl + Cl 2 ¾¾
·
Cl · + CH 2 Cl 2 ¾¾
® C H 2Cl + HCl
·
® CHCl 3 + Cl ·
C HCl + Cl 2 ¾¾
·
Cl · + CHCl 3 ¾¾
® C Cl3 + HCl
·
® CCl 4 + Cl ·
C Cl 3 + Cl2 ¾¾
(ix) Monohalogenation can be carried out in presence of excess R – H
(a) CH4 + Cl2 ¾¾

hv
® CH3Cl + HCl
(excess)
(b) CH4 + Cl2 ¾¾

hv
® CCl4 + HCl
(excess)
Cl Cl
(c) C2H6 + Cl2 ¾¾ hv
® Cl Cl + 6HCl
(excess)
Cl Cl
(x) Chlorination is highly reaction & less selective
(C) Bromination :
(i) It is less reactive & more selective then clorination
(ii) Bromination is slighlty reversible
(iii) Reducing tendency order of HX.
HI > HBr > HCl > HF
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Bromination Reaction :
CH4 + Br2
CH3Br + HBr
(D) Iodination :
It is highly reversible and it can be carried out only is presence of oxidizing agent like HNO3, HIO3
etc.
Iodination Reaction :
CH4 + I2 ¾¾
® CH3I + HI
5HI + HIO3 ¾¾® 3I2 + 3H2O
(i) Conversion :
Br
1. Br
Br
2. Br
Br Br
3. Br
Br
4. Br
Br
5. Br Br
Br Br
6. Br Br
Br Br
Br
7.
Br Br
Br
Br
Br Br
8.
Br
Br
Br
Br
9. Br Cl
Br
10. I
Br
1. Br Alc KOH HBr
Br Br2
2. Alc KOH Br
ROOR
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Br
Br
3. Alc KOH Br2 Br
25°C
Br
4. Alc KOH NBS Br
Br Br Br
5. Alc KOH NBS Br HBr, ROOR
Br
Br Br Br
6. Alc KOH NBS Br Br2
25°C
Br
Br Br2
Br
Alc KOH Br Alc KOH
7.
NaNH2
Br
Br Br2/CCl4
Excess
Br Br
Br
8. Alc KOH NBS Br
Br2
Br Br
Br
NaNH2 Alc Br Br
Br
KOH
Br
Alc KOH NCS Cl
9.
Br2/
CCl4
Br
Br Cl
Br HI
10. Alc KOH BH3THF OH I
H2O2/OH
1 1
# Reactivity µ µ
Stability Selectivity
* Relative yield = Rel reactivity × Probability factor
* Rel reactivity of chlorinann towards 1°, 2° , 3° H :
H ® 1°: 2° : 3° = 1 : 3.8 : 4.5
84
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* For Brominaln 1° : 2° : 3° = 1 : 80 : 1600 at 100°C
* Selectivity towards chlorination & bromination
For Chlorination
Cl.....H C Cl
X + C–H
Br R + HX
Tetraheral T.S
For bromination
Br
Br2 is more stable hence less reactive & more selective as compared to Cl . So, the T.S. of
Br + C H R + HX is planar whereas it is tetrahedral in case of Cl. (By Hammond’s

postulates)
At any temp T. The following observations are made
Cl
hn Cl
+ Cl2 +
2x = 56 (56%) (44%)
6 44
hn Cl
+ Cl2 +
y 33.5 Cl
= (33.5%) (66.5%)
9 66.5
Que. Now calculate% yield of products of mono chlorination at same temp T
(i) Cl2 Assuming relative reactivity be

hn 1:x:y
Cl2
(ii) From above reaction
hn x = 3.8
y = 4.5
E 85
JEE-Chemistry
Cl2
(iii)
hn
* Assuming relativity reactivity be 1 : x : y
* Above reactions x = 3.8 and y = 4.5
Cl Cl
Cl2 + + +
hn
(i) Cl Cl
a b c d
Let total H Be H., n = 12
6 1 2 3
a= ·1 , b = ·y , c= ·x , d = ·1
n n n n
6 3.8 9 3
a= ,b= b= , c= , d=
n n n n
% a = 27.2% c = 40.5%
b = 18.8% d = 13.5%
Cl2
(ii) hn Cl +
Cl
6 4 15.2
a = ·1 b= ·x=
n n n
% yield of the products : a » 29% , b » 71%
Cl
Cl2 + Cl +
(iii) hn
Cl
9 3 6
a = ·1 b= · 4.5 c= ·3.8
n n n
9 13.5 22.8
= = =
n n n
% yield of the products : a » 20.5% , b » 29% , c » 51.5%
86
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Halogen Derivatives

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Alkyl Halide & Aryl Halide

LECTURE NOTES ALKYL HALIDE & ARYL HALIDE

Alkyl halides Alkenyl halide Alkynyl halide Aryl halide

Mono halides Di-halides Tri-halides Tetra halides

Primary halide Secondary halide Tertiary halide

(i) Alkyl halides : Halogen derivative of alkanes.

(ii) Alkenyl halides : Halogen derivative of alkenes.

II. MONO HALIDES

Example : CH3 CH CH3 2-halo propane

Example : CH3 C X (tertiary butyl halide)

Non polar Polar

Polar protic Polar aprotic

Na+ is solvated by ion dipole Br– surrounded by solvent but not

Some Common examples of solvents :

IV. ELECTROPHILES & NUCLEOPHILES

Organic compounds containing carbon-carbon double bonds can also behave as

CH2 = CH2, , CH2 = CH– CH= CH2, etc

V. NUCLEOPHILICITY & BASICITY

(ii) It functions as base is indicated as

Relative nucleophilicity in polar protic solvent

> > > > > > > H2O

HO¯ > H2O

(Weaker base, yet stronger nucleophile)

CH3- > NH 2- > OH - > F -

1. CH3¯>NH2¯>OH¯>F¯ CH3¯>NH2¯>OH¯>F¯ If donor atoms belong to

2. SiH3¯>PH2¯>SH¯>Cl¯ SiH3¯>PH2¯>SH¯>Cl¯ ––//––

4. OH¯ < SH¯ OH¯ > SH¯ ––//––

5. RO¯ < RS¯ RO¯ > RS¯ ––//––

VI. LEAVING GROUP ABILITY / NUCLEOFUGALITY

Order of leaving ability of some groups

where group attached with R is a leaving group

(5) CH3¯ < NH2¯ < OH¯ < F¯

(6) R–COO¯ > PhO¯ > HO¯ > RO¯

Solution. (a), (b)

(2) Which among the following species is an ambident nucleophile :

(C) Cyanide ion (D) Acetone

(A) electron-rich species

(C) a Lewis acid

Solution. (A) A nucleophile is electron-rich species

(4) Which is not a nucleophile –

Solution. (C) BF3

(1) Nucleophilicity depends on the nature of solvent.

(2) Anions are better nucleophile than their neutral molecule.

(A) 2 (B) 3 (C) 1 (D) 5

ANTI GROUP MIGRATION

Carbocation involved in combination reaction (with I– as nucleophile ):

Carbocation involved in elimination reaction :

REACTION INVOLVING CARBOCATION AS AN INTERMEDIATE

NaNO2/HCl + –N2 H2O

Note :(i) NO+ is attacking electrophile

(v) Aryl diazolization salt is stable only at (0-5°)

ENERGY PROFILE DIAGRAM FOR DEHYDRATION OF ALCOHOL

H Rate determining step

CH2=CH2 + H2SO 4 160°

CH3 CH3 CH3 CH3 CH3 CH3

CH3 CH3 CH3

Semi-pinacole rearrangement (Damjanov's Reaction)

(ii) NCC intermediate is involved

* (–) Br2/H2O test