Halo alkanes and Halo aerenes

1. Classification based on no of halogen atom

Mono: - RX, di - , tri 1, 2, 3 tri halo propane

2. Classification of mono substituted haloalkane sp
3
-> 1
0
, 2
0
, 3
0

Allylic -> CH
2
=CH-CH
2
X, Benzylic Benzylic chloride 1-phenyl
Chloro methane
3. sp
2
Vinylic CH
3
CH=CX , arylic C
6
H
5
X
4. Nomenclature:-


o-, m-, p- dichloro Benzene






5. Preparation of alkyl halide: - (i) from alcohol

(ii) From Hydrocarbon: - Free radicle/ Electrophilic substitution/ sandmeyers
reaction/ alkene
(a) Free radicle

(b)Electrophilic Substitution


(c)Sandmeyers reaction




(d) Form alkene Markonikovs rule CH
3
CH=CH
2
+ HI -----> CH
3
-CHI-CH
3

(iii) Halogen exchange method Finkelstein

Swarts RCl/Br + AgF/H
2
F
2
/CoF
2
/SbF
3
-------> RF + - - - -
6. Properties:- (i) RCl Colourless & RBr/RI coloured when exposed to light
(ii) b.p. RI > RBr > RCl > RF (due to molar mass) b.p. decreases on branching
m.p increases on branching m.p of p- > ortho due to crystal lattice
(iii) Insoluble in water due to no hydrogen bonding.
(iv) Nucleophilic substitution reaction: - When strong nucleophile replaces weaker
nucleophile is called nucleophilic substitution reaction.
RX + NaOH/HOH/NaOR/NaI/NH
3
-------> ROH/ROH/R-O-R/RI/RNH
2

RX + KCN/AgCN/KNO/AgNO
2
/RCOOAg/LiAlH
4
---------> RCN/RNC/R-ONO/RNO
2
/
RCOOR/RH
KCN form RCN while AgCN form RNC since KCN is ionic which provide CN but
AgCN is covalent, therefore e
-
pair on N easily donated.
(v) Elimination reaction: - When RX react with alc. KOH form alkene
CH
3
CH
2
Cl + alc.KOH ------> CH
2
=CH
2
+ KCl
Saytzeff rule: - When assymetric alkylhalide react with alc.KOH form alkene
major product is (which has more alkyl gp)


(vi) Reaction with metal: - Alkyl halide reacts with metal to form organo-metallic
compound. I
st
such compound was formed by Victor Grignard called Grignard
reagent.
RX + Mg ----dry ether-------> RMgX which is very reactive. React with
moisture to form alkane
RMgX + H
2
O ---> RH + Mg(OH)X
(vii) Wurtz reaction: - 2RX + Na ----dry ether----> R-R + 2NaX
Fittig reaction 2C
6
H
5
X + 2Na ----> C
6
H
5
-C
6
H
5
+ 2NaX
Wurtz fittig reaction: - C
6
H
5
X + RX + 2Na -----> C
6
H
5
R + 2NaX
8. Chemical reactions of Haloarenes: - (i) Nucleophilic substitution reaction
(ii) Electrophilic substitution reaction
(iii) Reaction with metal
(i) Nucleophilic substitution reaction: - Halo arenes doesnot give since
(a) C-Cl is strong partial = bond (169pm but in RX C-Cl = 177pm)
(b) phenyl cation is unstable due to resonance
But under drastic condition (or in presence of e
-
withdrawing gp NO
2
) give













(ii) Electrophilic substitution reaction: - give O, -P compound
(a) Halogenation



(b) Nitration


(c) Sulphonation



(d) Friedel Craft alkylation/ acylation





(iii) Reaction with metal Fittig/ Wurtz Fittig reaction

9. Polyhalogen compounds
(a) Dichloromethane CH
2
Cl:- used as solvent in paint remover/metal cleaning
drugs but harmful to central nervous system.
(b) Chloroform CHCl
3
:- used as solvent for fats, alkaloids, I
2
in Freon R-22,
anaesthatics. Damage liver, react with O
2
to form poisonous gas phosgene
CHCl
3
+ O
2
-----light-------> 2COCl
2
+ 2HCl (Carbonylchloride)
Therefore, stored in dark, full bottle (Since no air)
(c) Iodoform CHI
3
:- used as anaesthatic but give foul odour of I
2

(d) Carbon tetrachloride CCl
4
:- used as solvent, refrigerant, propellant, fire
extinguisher but exposure causes liver cancer, nausea, vomiting, coma.
(e) Freons chlorofluoro carbon CF
2
Cl
2
:- Used as propellents refrigerator, air
conditioning, upset ozone layer.
(f) D.D.T p,p-dichloro,diphenyl trichloro ethane
Paul muller was awarded noble prize on it
Used against mosquito and lice
Highly toxic to fish
10. Mechanism of nucleophilic substitution reaction:- Stronger nucleophile
replace weaker nucleophile in alkyl halide is called nucleophilic substitution
reaction. Reaction proceed through two mechanism
(a) S
N
2 mechanism : - (i) rate depend on conc. Of two reactant (2 order)
(ii) Reaction proceed through single step. Breaking of bond and incoming
nucleophile take place simultaneously.
(iii) Due to steric effect reactivity 1
0
>2
0
>3
0
/ RI > RBr > RCl > RF
(iv) Product has inverted configuration as compared to reactant
:Nu attach on opposite side of halide


(b) S
N
1 mechanism (i) Rate depend on conc. of one reactant (Ist order)
(ii) Reaction proceed in two step formation of cation then cation react with
nucleophile
(iii) Reactivity 3
0
>2
0
>1
0
/ RI > RBr > RCl > RF
(iv) Give Product as recemic mixture. Since carbocation formed in slow step
Therefore, :Nu may attach to either side ( may same configuration or inverted to
reactant)
(v) Require polar protic solvent (H
2
O, ROH, RCOOH)
(vi) (CH
3
)
3
-X ----slow---> (CH
3
)
3
C
+
+ X
-
(CH
3
)
3
C
+
+ :Nu --> (CH
3
)
3
C-Nu:
(Produce E)
(vii) Allylic (CH
2
=CH-CH
2
X) & benzylic show high reactivity in S
N
1

11. Stereochemical aspect of nucleophilic substitution reaction
(i) Plane polarised light Light obtained through nicol prism (Calcite ore CaCO
3
) is
called plane polarised light.
(ii) Optical activity :- When plane plorised light is passed through certain
compound it rotated to right direction called dextro (d,+) and if rotated to left
direction called leavo(l,-). These compounds are called optically active and the
phenomenon is called optical activity.
(iii) Asymmetric centre :- If all four substituent attached with C-atom are different
then it is called asymmetric C-atom.
Assymetry is responsible for optical activity.
(iv) Chirality :- The objects which form non superimposable image on their mirror
image is called chiral and the property is called chirality. Eg p, q, butane 2-ol, 2,3
dihydroxy propanal
(v) Achirality :- Objects which form superimposable image on their mirror image is
called achiral and the property is called achirality. Eg. Propan-2-ol
(vi) Enantiomers: - Optical active isomers are called enantiomers (d and l)
(vii) Recemic mixture: - Mixture of two enantiomers (d and l) in equal proportion
have zero optical rotation is called racemic mixture (dl of +-) and the process is
called recemisation.
(viii) Retention: - Retention of configuration is, preservation of integrity of spatial
arrangement of bond to asymmetric centre, during chemical reaction i.e product
have same configuration.


(ix) Inversion: - If bond broken and configuration change during reaction is called
inversion.