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Haloalkanes and Haloarenes
Haloalkanes and Haloarenes
Haloalkanes and Haloarenes
NOMENCLATURE OF HALDALkANES :
Common Name LUPAC Name
CHg- CL Methyl chlonude Chlo no muhant
CHCH,CH,B n-PMobyl BHomide BADm propane
CH3-CH- CH2-CL thobutyl chlontde 1- thlono à-mekhl
propant
3 heopentyl chlontde I-chloro-3, 2
Ch CH,-C oluimet hylL þropane
C (m Dichloro
benzen)
Dichloromethane
CHC2 Mtthylene Chloride
CHcH,CH,F n-Proby Pluoride -Pluonopropone
CHC Chloroform Tuhloro aethane
CH BM Tou bromo methane
Bromoporm
Moleuler srudure
orbilal
CRO
METHODS OF PREPARATION OF HALDAUkANES
From Alcohol
(a)By the ackion of balogenatid t
R-OH + HX R-Xt H,0
'8 altohols 0um chloroalkanesy when hydrocblo
aud ga 6 paase d theough dluhol i the
e &ence anhydrous Zncl Thi's Anown as
Grooves Procass"
Zhclh helh n the cleavage 0f C-o bond.
3al tohols aHe Vi Heauve, thu atact
With Come Hcl a Voom em wthout
Zn c
CH-CH,-0H Hcl hCH CH,-CL+ H,0
znt
H
CH CH -OH+Hc CH CH-cl +Ho
znC
CH-C-OH+ HC oo CH- Ccl +H, o
In tenms
From Alkenes
CtHx
3t 1 PoAsible an 8ymrne t a l 'alkenes (-CH=CH)
Markonikov's Rule:
In unsymmetnutal alkenea, the -Ve
pant of ihe addendum gos to that Carbon hawing
Lowen no- drogen
Negaiuve C)
owun Ch-CH-CH, t Hx Ch-CH- CH
Edltydregen
ANTI -MarkoniKov RuLE *
Apbheoble to HBr -0-
TaRes blate in the pAESence of ORganic ptxoxide
the
in unsymmetucal olkene, the negdive þant of
additivL goe to that corbon havhg dujhe
no h qduoqen
CH3-CH - CH t HBt Peroxide CHa-CH-CH
Are monRowniky Rule i also Rnovon as eroxide effet
09 kharash 2ed
i Nigahive)
T OHighet
Addution 0 Halgen
when Ba, & t added Ho alkene
dhe addiion occux a Ahe doude bond.oming
VUAnal dhalude
Bx
C B, Ccl (viunal da halide
TThis dest ib uied do check,unsatur avion beta
d When uealts
duso þpeaHe
Heddash coloun ef B4
wlh aVkene
6Y Halogen exchange
t Nal
Acetone R-T + NdA
{- l, Bo
R-X Heat
Pinkelskrin Reacdion
duaeclly dhrve
dilliull do pepane and "bromid
FluDs oalk anes ane alkyl chlonide
O DAepare d by dtaing CH4,f., Agf, Cofs» Sbt-
ith inougánic udrude sulh os"as warts Heaction
and dh sueaition is drmed
tX Halog enCaritr
310-3b(o+Hx Cr: cd, Bt)
Mechan ism
8teb-1-Generation electrophile
C,tFecl
formotion b tarbo cation
intermeda at
Be-d
J+ HI
Sandmeyer keaction:
N CUX X
+Na
CX-Cl,Bx
Hx
Gattermonn Keaction
Na
Cu + N
HX
Nc
tkTorm DtNt kcl
Balz-Schieman Reaction
-N'C+HBF NBFy +8, N
+Ct AgBr
butbaned uom phenol because
ole haloanenes,Cont be Thi's I du
i dlicult do aeplace-bH gp
Hesonance in phenol
Proberties o Halbalkanes-
Physical
colnuss (when þune)
n genera haloalk anes aHe
Sneet 8melling uqu'ds
soluble in watn becaust o Aow
They aneAlgbtly
erdenty o tOHm Hydrogen Bond
Dunsity f<cl<Bn<I
mone no oH atom, less 1& densty.
CHa Cl, <CHC3
Boilinq_point 8-t Mol Mass
Bt
Brancht
PhysicalPropertiesof Haloarenes
1These aHe generally ColourlessJiquid o Crystallin ingolud
9.The ay haudei8olubleane,heavy than wate, &0ld
in waten but in "on9onic 8ovent
3Them-bl bbbt e anyl hau'des aue nean ly ihe same
alkyl halude toitauning he Aame ho. o
Carbon aioms
meta
B-t3 0ntho> Para>
Para > Ortho > meta
M-pt
Hemical þroperibies o HaloalRanes-
Nucleotbilic Substitution Reaction
--x + N -C-Nu4
R-B«>R-Cd>R-f
Reacuvity 0den R-I>
V
Nurleophilic Sub Rex
SN' (Un.malecudon
Types- CBimoleulan
Sub
Nutleophr1le Rer"
SN,
8te- CHs
tNu dost
C NW
Attack ofl Nucleophile
CH3 Chs CM3
lan- bolari'Zed,
u'ght hormal bolani2ing
OSourte
ght ught
filte
Ondin ary ght tonsist of
eleetromagnetvic-
Abeam DVibratingtnall laneswhen as
Waves
Nitol þusm, Vtbrates in one plane
dhroug
Called PPL CPlane Polariedght)
Rotatory which Aolate PPL tonards sughi
Dexo
hich Motate PPL donardslet
Levo-Rotafory:
C
-
T
O
&Ubstituion by
Ub&titution Hmino 9roup
R-X 4 NH R-NH, t Hx
When halo alkanes is in exceM amount dhen al thnc
NH 1 aeplated oy oub R)
R-X +NH RaNKgN+ Hx
HoFfman Amanayu'i Reachon"
R-X+ knNO1 A R-0-N=0t kx
Substitutjon by alkoxy_rou
R-X tNa 0R AR-0-RA Nax
This neachien is Rno a Willhanson Synthesis
Substtution by Cyano grou
R-x+ kcCN R-CN tkxene Hd CHa CONH2Aide Acd
CaMs-L+ kcN CaHsCN Dil-H orNO CHa COOH
NO,CHs0 CHCH NH
'ACHy N/H amine
Mendius Reactjon
Theomation t omine amines by
by
educhon with nasScent "tydrogen
aduen
obtaned bs'ihe
dium 8m alehal
Substitutionby_1socyanide qroup.
ubsttviion
R-x 4 AgeN R-NTt Agx
Note A acvale Na 8acduvate C
Substitution by_azide gp
R-x+ NaN3 R-Na t Nax
Substitution by Carbory hs,
R- -oM1tX-R3Hc0H, R- -0R Agx
+
8 7 C CtBH + Xxe
(hene B base
X- leaving at)
3thext ds a bossibility of Onmatu on emoHe
dhan ne olkene due availabMty o
emoxe than One -H wually eme alkehe T
OHmed as mayon produet
CH3-CH, -CH = CH-CH
Reduction Reackion-
-x &tHJ-
+ R-H t Hx
Ca Hscl t 2th- (aH + HCl
Medutuon
Following dtajent ane Used on
ZnHC Na l HsOH, , LiÄIHy Red P/HI,
Kearrangement ReactionTso Reacthen
ResonaceEllect
Delg caliatio ef T e
.C
2.
2 Differena in hybridi'sation o C-x bond
R- CH-X Sp
m o e S- charadex m oHe electronegative, h0 hold
aiH moHe ughtly, so ess Meatlive
phens
Effect o subsutuent in Haloarenes on Reathivdy=
The puese nCe o ewithdra lki ing 9 Houpi such as
-N Da CN9 CooH ede a or-hs and ara postion
-NOa
to Lhe halogen odom gueatly aelirates the halosa
dowands Nuleophdiz zubiututon
pH
r)NaoH 693 0
i ) dal Hel 300 atm phunor
pH
) 157NaOH,V13
i ) dal Ht
NO2 NO
OH
NOANaoh,368t NO
) dh. H cL
NOz
NO
Note7 N qutu Nt,) t 1n 1 n t
GA
lor
denoted by*
C H OH
c
N at ortho position co 0
8l on C OH
9te
Ng at weta Position
C
DH
OH 0
76
OH
das NO
ste
Substitulion of Amino 9
4 d NH+ C4,0 o)t Cu cl, tH, o
Anu'line
Subsltutien by_yone_j"
fN
O+Cu
tNy d r
A15 k o + CuB
yunoben Zehe or BenZonitrile.
fONHO
Con-HL
alk.4,0 8enzumide CPartial Hydrolys)
Od NabH
the n
D
FHy Re
cl
c t SNa t Cl-CHsethen Ct3
Reduction-
o H NFA +HCl
NaOH
Benzen
+C
anby
pecls O
HCL
Cmayos) (mina)
Ntretion Cemc NO2
o]tHNG CConc) H,5Oy
m in o) NO2
Cmaj0dD
SulbbonaHon
A
+ HsOy
soH
Alkylation-y
Priedal craft
tCHc!
!Ank Anh t (o] +Hcl
Alc
CHs
Priedal cralt Acylahion
+CHclA
tats+ (o)+Mtk
AIcl
CocH
Finkelstein aeadlion
CH-I t Nacl
CHg-CH-cl +NaTI Aceton CH
Chlondet hant
Hunsdiecker heaction
CH3
CH3 C- OAg +BM, -CC CH -B + AgBx + lo,1
Biwen Acetate 350k
Methyl
Bromide
GHRtKCN GHCN++K'B
9HPA+AgCn sNC t Ag
ovale soanide
CN
ambdetate
CN-