Haloalkanes and Haloarenes

St 8

Haloalkanes alkyl halides I e

Cnhznt.X or RX X F C Brit

malignant on the ban't no 9 X atom I fluorides don't

Dihaloalkans Trihaloalkans behave like
Ch X Ch X chlorides bromides
q
d x In x iodides
due to more
dry X
Tetrahaloalleans infuse and
CHXz absence d orbital
Haloform of
CCly
Clarification on the ban's
of type of Sp Carbon
Primary i Secondary 2 Tertiary 30

R Ch X R
ga
X R E
R E
Mt
benzylic Benzylic

Egon 1 cha
Isp 11 X
CE 20
in x
k Tf I I x 30

tt
 ttattached
www.ytwwk to benzene ring
directly

iita
microsoft.se
t E I
t
As
IUPAC naming of haloalkanes haloarenes

Inane

CIlupacnam cy
as Isopropylchloride 2 chloropropane

Ce Isobutyl chloride i charo2 methyl

propane
ng Eth as

capon ce vinylchloride chloroethene

Br
m dibromobenzene 1,3 dibromobenzene
y
It sym tribromobenzene 113,5 tribromobenzene
or
 Hz CHI d
gem dihalide
Ethylene dichloride 1,2 dichloroethane
Lic area

EE By Allyl bromide 3 Bromopropere

seebutylbromide 2 chlorobutane
cry ay ay ay
Br
1 Bromo2,2dimethyl
propane
Br neopentylbromide
Cy Ihsan

cizic Br tert butylbromide 2 Bromo 2 methyl

propane

Is
I chloro 2 methylbenzene
IIa O chlorotoluene
2 Torotoluene
a
2 Benzylchloride chlorophenylmethane
I
dichloromethane
Chalk methylenechloride
trichloromethane
Chu chloroform
tribromomethane
CHA Bromoform
Che Iodoform thiodomethane
tetrachleromethane
Cdg Carbontetrachloride
Q Iupac names

Im
o
n Br u
cry cry cry

h
Ii Br
ok n Br
O
n
m
H

4 Bromopent Zone 3 bromo 2 methylbut l eve

Bromo 2 methylbut 2 ene
4 Bromo 3 methylpent Zone 101
I Bromobut Zone 3 Bromo 2 methylpropene

Nature C X bond
of

Since down the group size of x atom

increases the c x bond length will
increase as well
The bond is polarised towards X atom

Kimisite
 Order of dipole moment
c d C F R Br S C L
Cdue to larger bondlength
Q forthe compound Chia cyber Chef and CBF
the correct order c halogen bandlengthis

chef C Chal BBC CBI

JEEZI aye c as Brc one const
Casf c azz coz Brc Gza
ayee c Mbr C CBFC CBI

Prepqtiffromataty
i
general
R oh
regalitywithtix
hX
age RX t 420 30 20 i alcohols

GROVE'S PROCESS LUCAS REAGENT HA 2nd

Snl leads to carbocation formation

mechanism

hence rearrangement possible

In case active alcohol it leads
of optically
to racemisation

R on t Na Br t tyson RBs Manson

i tho
 I 3 R OH PX I 3R X t Hypos

x Cl Br
red P
I R on f R X
x By Iz

Y R oh t Pag R a Pods tha

CI DARZEN'S PROCESS retention

R on sock of R Ch t
soft hag
R on sock 52s R Ch t
soft hag
inerin
Fromhydroatimide

i freeradicalhalogeneticalkand
This reaction gives a complex mixture of
isomeric mono polyhaloalkanes which
is difficult to separate

Chalaza cuz dacha 43

quacks
niner major

order
of ease
of substitution of X
30 20 i
 Chlorination mono substitution
beyond maybe
supressed by controlling the ratio g Cla to
alkane

I it
Major product will be Markovnikovproduct

of Hbo with peroxide

in presence we

get antimarkovnikov product as major product

Involves carbocation intermediate hencereamayent
possible isomers
sines structural
minor
This reaction is regioselective as major
products

cis
additgtajdytjf.TTpresemeyCd4
anti addition Feddishbrown in
color
reddish brown color disappears on

reaction hence used as test for unsaturation

water
Bromine
test

vic dibromide are produced which are

colorless as
gives products
stereoisomers
Reaction is stereoselective
cis alkene at dtl mix

trans alkene meso compound

 iced t Br Brett ChBr
n
In
vic dibromide

Bonodine Hinsdiecker Reaction

R COO
Agt X R X coat Agx

x d Br Yield R X is
Silversalts of
of carboxylicacids F R X 7 20 R X 30R X

is
Usually Bra preferred

over da since Clegives

a
very poor yield of R X
Finkelstein Reaction halogen exchange

to
alkyl
R X Nal IE RI Max
iodides
only
d Br

Nabu precipitates in
Imax
Mace dry acetone
which facilitates the forward reaction
according to Lechatelier's principle

Swarts reaction
Sbf
Reagents Agf Agfa Cory or

for
any
funds only
R X Agf I RF Agt
I
 Cl Br
solvent Polar protic
Solvents
like 120 and Carson

The above methods are not suitable for makinghaloarenes

Electrophilic substitution of arenes

in Ii
Hidy y ee
my p halothane
major
o halothane

ortho and para isomers be easily separated

can
due to large difference in their map I b p
Reactions with 1 are reversible and require
presence of oxidising agents like KNO 11103
which oxidizes the HI produced to Iz
Fluorine compounds are not prepared by
this method due to explosive nature

Using diazonium salts Ar Nta

Eiti
Repair nitration nitrobenzene
aniline

N n a
 Éttice
Iga
aniline

ÉI
Benzene
diazonium
chloride

my

wsj t o

Etrigan

x
Cut HX
Cl Br
HBfy o
BA REELEMNANN
II
SATELLITE
Gta Hd
Sandmen'd's x Cl Br
better
is
yield
mangalter
I Nz

Q The reaction of Coty cut on cry with Mbr

produces
yeen cry
Br
Consumer
b
cons uz ers d Cotsaz a as
egg
Br
Colts cu on on Cons ayahs
majd
I Br

reaction
Q In the replacement
MI
Jc
F
Mf
I I
M happens
the reaction will be most favourable if
to be
k Nb Li
Na F
Li
to break
ER If easiest

reaction
Ghg undergoes the follony
Q the compound

Fee E
GHz 4 A B e
m bromotomere
The product c is
O bromothene
G ti chlorotoluene
3 Bromo 7,4
bromo toulene
p

É
43
halogendi

benzylic
thiosubstitutin
É
Al
Retremnotes
meta directing of
gee is a
It Rn
R
Philpott higher
ay
members
ans x
are
are

liquids
sees
or

solids
they are polar they
2
Solubility
are
Although
insoluble in water due
generally
their inability to form h bad with water
However they are soluble in alcohol ether
and benzene

3 BoilingPoint Haloalkanes have considerably

than alkanes having
higher boiling points
to nature
Same no
of carbons due polar
RI
order RF C RUC RBr L
Iannone boy
point
4 chlorides and fluorides are

lightener than water but

heavier
Bromides Iodides are
 reactive
5 Alkyl iodides are sufficiently
to be decomposed by light

t d d In
casket I
Glycerol to 2 iodopropane
Convert
Q
Ch on

In on

in
I
Glycerol

I s
Ing

Chemically maybe
divided into 3 Categories

Nucleophilic Substitution Sw
Elimination Reaction E
Reaction with metals

Nucleophilicsubstinh Sn
Unimosealyanngeophilissubstitutians
Rate KIR x
 Reactivity order depends on carbocation stability

R benzyl allyl 3072 i ax

carbocation intermediate
Rearrangement possible due to
kinetics
follows 1st order
Polar profit solvents required

No nucleophile strength on the rate

effect of reaction
of
Stereospecific Stereochemistry
Racemization dtd
Catalysts Lewis acids 9 theycapture
the c G x
Agnos Ald Inch Fell Bf eh easily

P
YE
x
stain

Stef Ifni Reg Nu

n Yr
Swa

Rate
Bifida KINDER x

Reactivity order less steric innings foster reach

Rex 3 C 2 C IC UX
Rearrangement
not possible
 y
follows 2nd order kinetics

Polarapron's solvents required

affects the rate reaction
nucleophile strength
of
Stereochemistry WALDEN INVERSION
Catalysts None
same thenpresencey EWG on X causa
if degree is increasesreadin

MI x
Ii É É Nu r i

Transition State
SN2 reaction with each y
Q KI in aletone undergoes
reaction will vary
rates
P Q R and S
The of

gt
as a

15 ee 7 a a

P y S

PSR a s
P a Rss
S s e r a r p s q
x and
reaction condition
Identify the setof reagent
Q set transformation
y in the following of
Br t Product tag ay
Cig in a
g
Y Hr acetic acid
X did ag Naoh 200 j
28 C
 alcoholic Naoh 28C t Mr
X an
acetic.gg

X did ag Naoh 28C

it By Chey
OC

X cont alcoholic Naoh 28C I By Chaz of

Cy in as Bratton may ay ay ay
By Long
as Y Br
up
UNREACTIVITY OF PHENYL AND VINYL HALIDES

I x yes
These halides cannot react by Snl since
carbocation
vinylic and phenylic
are

highly unstable and not formed

because
They also cannot react by Sn2
due to M effect of halide ion C X
bond in both cases acquire partial
double bond character and the an e
present in both the system repels
the incoming nucleophile thus hindering
the back side approach
optind
Sng prime
The subst abenzylic system under
Snl conditions proceeds with rearrangement

R on on KI r an Iti r Kientz
allyl 1
Ly Ly
R on ten can R Cna

fption
I Y
mins majny

Sight substitution
of allylic
benzylic

system may also proceed via Sw2

mechanism in which no rearrangements
take place
Conditions Nucleophile must attackon
carbon
f
A concerted movement

of 3 é pairs occurs
This reaction is particularly susceptible to
steric hinderance especially at L C

R R

MEEEE MI fRs
e
 Substrates
of
R C ch type prefer Snl
ay
k s
but
c c
a
c type prefer Snl
k pi 3

example Chs

aster
is mon

L
In

Eas as
IFI 1

Rent R x Nu R Nn tx
substitution Classof
product product
Reagent mudeopyen R Wu

NaOH R OH alcohol
on
9
go
1120 R on alcohol
120

Naor R'o R o r ether

 Nat I R I alkyl iodide
NH Ahs R Ny Primaryamine
Ramm

R NH R Secondary amine
R NHL R'NL
R Na R R Na R R N R tertiary amine
r
kin in non nine
cyanide
R NC isonitrile
Agen Ag CEN I isocyanidefoulsmelling
fromN

KNOL IN Firanging R onto Alkylnitrite

AAgno Ag O N
banyan
o R N
2
nitroalkane

R'CooAgt R'coo
Ricoor Ester

Little h hydride
R H hydrocarbon

R Mt Rt R R alkane
M metal

me ambidentate

Groups like CN cyanide and No nucleophiles

nitrites possess two nucleophilic

centres hencethey are called 9
structures
has following resonating
Cyanide group
LEEN c N
 when it links through c atom alkyl
cyanide R CN are produced while when
it bends through N isocyanide are

produced IR NEE
when Nitrite ion OE ni to
Similarly
results in alkyl
links through oxygen it
when nitrogen
nitrites ONO while through
it results in nitwalkanes R Nos

Gigggiptiream ced

Rate KIR xD
hence reawayent
carbocation is formed
is possible
solvents are required
polar protic
h is lost Zaitsevproduct
p giving
regioselective
as the mayor product
has no effect
Strength of base
on

the rate of reaction

follows 1st order reaction
Reactivity g R X
30 20 i Az x
R I R Bus R U S R F
 I i
a
Igt a Yg
X

might
I
aging's
Important
joy of have same firststep
Swt is preferred at low temp
while E is preferred at hightempo

CEa
Instynetimitireat
Rate K R xDBase

No remayent possible
solvents are required
polaraphotic
h is lost Zaitsevproduct
p giving
regioselective
as the
mayor product
rate of reaction
base affects the
Strength of
follows 2nd order reaction
Reactivity g R X
30 20 i Az X
 R I R Br R a R F
B

Ift Gx4 É ne t c tr

9 Which is the correct one of decreany St

reactivity

Rz Cx Rent Ray Rax Rex Rena

mi on
nom an

N
E
I
Since intramolecular Sn reactions are preferred
be decided by that
major product will
mechanism
 iftar YET I
to

E
i

d tr Msx

o
t
it's it
 Q s

I typ
Oy

E I I I

mim

r
 in conjugated
Tienes
I
Fadditin
takes place
II
to give maja
arming It Edgy
thermodynamically
controlled
products
if not addition
ariete 112 takes place
to give maja controlled
kinetically
at high
Imp products
O
É Eoe
g
 Reatchlorides
with
bromides
certain metals to give
iodides react
compounds carbon metal bonds
containing
are called organometallic compounds

4 R MEX Grignard Reagent

R X Mg dnt RingX
highly reactive
are

I My g They
and react with any
source
of proton H
to give hydrocarbons
i They must be protected
Reaction
of Grignardreagents for moisture

Ring itirIIgtforlom on
Is R n

LI R H mg
Meng
909
 t

pretty witharbonylcompond
hydrolysis
pm'jx
y
it É ng
In
n a
methanol
gin
1 alcohol
pm'sx
y
Iii É ng pi
R
aldehyde
gin r
In
20 alcohol

pm'd
f
REIER É ME pi
ketone
Er r
ER
30 aloud

jÉÉmx Leh
a
it I Eileen
MgX NH

É in
j
r n
Les R
K
fr met
CORD
MSX
pryx
ietmr
ij.fr sx r
q
R tr
3ahohd R
Er
 WURTZREACTION

2 Rx Na th R R 2Nax

Éemitmon fronts
2 Ro Nat t R'x ROR t Nat
sedumalkoxide
Williamson's Ether Synthesis

RI
3
Ago Ro t ZAgI
my R
Mosier
4 H LIC R
H C c Nat RX
Sodium alkynides Max
5 R X t Ken R CN t KX
6 R X t Agen R Nc Agt
7 ChzcooAg 21151 Aglet googles
8 R X t KNOL Rono Kx
R X t Agnos R
y Noz Agh
10 R x t A R
E thx
FRIEDEL CRAFTS ALKYLATION
 11 Malonic ester systhesis optimal
on
active ntyle
Y 00815 Nat 0062175

43 x
M
net COOcan
SNL Ctg hey COOCans
acidity

Next Shsioon
12 Acetoacetic ester synthesis aphid
methylene
active
cooks
ti
s
en x a
Coo
egg g no
I
cuz coochy
Next guy 1004

H NH m
13 x cn my ax
u Sn
methylamine
14 Ca
II
Br
211g H Reduction

15 Ch ay Br In ere cry
EL alkene

DIHALIDEI
oftwo types
VIC DIHALIDES GEM DIHALIDES

I I I d
 Preparation
UI
tags
p cham R Ch

Gtereopefin4
vic

R c c n thx
wit r
1
42
Riggen
Cha on Pcb or sock Cz Ce
du 20 hill
G
on
a
Vic diols

to ausczon E EEiimita
alcohol If pec
a a
aldehyde
ggg them

Chengalpropertic
Rcn L ZnXz
a
cy I Ézaron
I generis R CE as 2n
or Lig NY
R ay ay
 R ke r
Y Y Sir f In canoe
vic dihalides piked

Cy
Mff check n
thx c
3
dihalides aldehyde
gem geggingame

as
Sem
I cute as
Esiingame
g as as n
ketone
i
aids are veryunstable They lose thoto frm
dihalidgem

7
Cha or methylene chloride
Ijchloromethane as a solvent in
used as remover
paint
board manufacture of drugs in metal cleaning
etc
only
the central nervous system
it harms
inhaled
if
to low levels of azaz
in
exposure
hearing
air causes slightly impaired
vision
Directcontact with skin causes intense
burning or mild redness
burn cornea
Direct contact with eyes can
 Halo form

these y cyazon

a
ÉÉ
or
r coonat
t
Naox
R cats

any Moncton
alcohol
i Em enxstticoonat
aldehyde
ÉÉ
n
i

chloroform

Ca CH only NaOh clad t Hcoona 120

chloral t

defenylow

AMIT na is colorless liquid with sweet smell Er

in it
taste heavier than water idle
but soluble in ether acetone alcohol
creates ti bonds

CHBr CHI are pale yellow liquid

and bright yellow solids respectively
ppt
Chengfthes in air sunlight

119 t
202
0 ha I
flee
PHOSGENE
chloride
or carbonyl

Hydrolysis

cha t Naon Ish COO Na t Nacl

used to

Nth
carbylamiereadt.gl
a.niIinau
gongs aliphatic

R Chaz
i amine tho
carbylamine
or
isocyanide
Ph Nh
foul smelling
substance
 Reimer Tiemann Reaction
on

Naon Nacl
Chaz

Tag
a Carbylaminevan
alicyaldehyde
Major
120

KNO home T
Chaz tho t
af Nor
Chloropicrin

ans Eas
YI
c o n
optimal
ng ca
I
Chloretone
a hypnotic
sedative

d
Cha t 6 Agt catch
you
GAY
a 4ÉÉIÉI g g ie as
IODOFORM CCHI
antiseptic however the
was used as
due to liberation
antiseptic properties was

and not due to iodoformitself

of free I
discontinued due to objectionable smell
I was

TETRACHLOROMETHANICCdg or Carbon tetrachloride

used in manufacture of refrigerants

propellants for aerosol
cam
and
synthesisof CFC
used for chlorofluor carbons

liver cancer dizziness nausea

Can cause
cars coma unconsciousness
vomiting and in severe

or death
stupor
content and can make
irritate eyes on
may
or stop
heart beat
irregular
released in air it can cause
when
which causes
depletion of ozone layer
UV leading to
human exposure to rays
skin cancer eye diseases disruption of
immune system
 FREONSY compound
y cha Cats are

collectively called from

They are extremely stable unreactive
non toxic non corrosive and easily
liquefiable gasses
CLE
Most common freon is Freon 12
It is manufactured by Cay by SWARTS
REACTION
able to initiate free
it is
In stratosphere
radical chain reaction that can upset
the natural ozone balance
DDI pp
dichlorodiphenyltrichloroethane
in at
Preparation
2 Frat 13 a

d
i used to kill the mosquito

that spreads malaria

excessive use developed

g
a resistance to DDT in
a mosquitoes and it harmed
n
fishlife also
It is chemically stable
and soluble in fat
 I

R.IE ttm Igi

Cow's
PROCESS

u
melted
I Nor
k
reduces
hor nor e density
Cl on the
ring
N2
Eje
my
facilitating
LOL for Nucleophile
Ce attack

N 2

PICRIC ACID
how
ta stomaticacid
substitution Reactions
Electrophilic X op directing
Halogenation C 2 m

u u a

Fred de
major minor
 Nitration
u u a

NL

Its gig minor

Sulphonation
u

i
Sogn

major minor

Friedel Crafts alkylation acylation

u u a

ons

major minor
a a a

É cows

antyonsalas
cooks
major minor

IEwii.r.it reaain
R
2Na X R
2Nax
 Reaction
Fittig
anat
4 Diphenyl
2Nax
Ullmann Reaction
a
2
jdam Diphenyl
Cuz

it
Cine
Cine

A
oooo 0 pdirecting
no

I
we
TEIL
 i T
p

o 43

FEE s

Astci
aid
o xym e rcuration
demercuration
Mkor
addition

g to
without
any
Ph I 441 Phew