HALO ALKANES -

Nomenclaturce
(1) CoHant X IMonoalkane
eig.-cHg Cl= chloro methan R
(2) Cn tHon X2 Dihaloal kane
e-g.- CH,Cl, * Dichloromethan.
(3) Cn Han- X3 Tribaloalkone
e-g- (HClg Tràchlorco methan (chlorco foronyl)
(4) CnHn-2 X4 Tetrahaloalkane
P-a- Ccly Cartbo nt crachloride or Tetrach
lororpethane
Naming 0f sp° C-X Compound:
CHs
CH, CHCH-x
CH,sps CHs CHg-(H -CH,-X
CHg
Tett- butyl halide Jsopropylhalide
Isobutythalide
(3' alkyl halide ) (2° alks halide) (1 alkylhalide)
CH3- CH,- CH,-X
seC- butylhalide n- pro pyl halide
(2' alkyl halide) (3 alkyl halide)

Stabi lity Onderr Of Alksl halide

3' alkylhalide > a' alkylhalide, > 1'alkylhalide cH;-x

stable bu Reson ance )

((H CH-x) (CH=CH-CH,-X)
vinyl halide Allslhalide
 Natunt 0f C-X Bond
Bond length (-F(C- ( C- Bre ( C-1
Bond enthalpy ' (-F)-)(- Br )C-I
Dpolt moment ! -F(C-C) C- brt) C-1
Prcpanat iorn
(A} Haloqtnation Rcaction ’
presence of sunligh t ,thw one
Vhn an alkant undergoes alogenation in replaced
of more hydto gen atoms of alkone are by halogo atons
(sunlight)hV, -x +.HX
alkant )

(methane) (chlorornethant)
hv cl Cl2
(3) CHa-H +Cl -HCl
hVCt,cl,
-HU -HL -HL tarbon teta
chloride)
I undetqoes'Free radica!' reaction or mechanism which consist of
thru steps
step-1 - Chain initiation'
(Free radical )
Ste-2 Chain propagation
CHH c ’ . CH»t HCL
CH% t

Chain terunination !

CHg t CH,’CH;-CHy
(CL,) REnTIVITY & SELECTIVITY (Bro)
CH H-H, + l, , CH,-i-H3 t Hg- CH- CH,
CH3
2° 3
(minor) .(major)
1
CL, 1 : 3.5 5
BI,- 1 : 82: 1600
 h Brc
CHa-CH - (Ha t Brt,
(majon) (minor)

MARKOVNTKOV'S RULE

’ when symmetrical alkone acts with hydrogen hali de i-e HCl or HBr
to qive one addition product
’ when unsymmeric alkene acts with trydrogen halide to give '2' additior
Poducts out of which one is majort product and othèr is mìnord
?roduct js called Markovnikov's rule
’ H undet goes elec tro phyllic addition Reaction .
CH, CH, t HX
(cthent) N: orr Brt] (Halo ethane)
e9 CH, = CH t HCt H; CHa
(ethene)
CHa-CH = CH, t Ht CH;-CH-CH3 t CHg-CH,-CH
(propene )
(2-chiomoprtopant)
(majort ).
(1- chloropropane) (mi nor.
Mechanism’
H-Cl

CHg- CHCH, H°, tHy-C-cH3 t CHa-CH,-t,

CH3-tH-(H (HgCHminon
(major)
ANTI MARKOVNI KOV'5 RVLE REAC (o) PEROXIDE EFFECT
(or) KHARASCH EFFECT
When propPane eacts with H- Br in presene of ortqanic prodde to giv
ong- bromo propan as a majot product and two bromo proane as a
minor yroduct
ROOR + CH;-CHCHa
CH3-CH=CH, t HBr
(prco pere ) BIT
(1-Bromo propane ) (2- Bromo popane)
(najor. ) (minor)
’IH unde qots fre radicals mechanism.
RO-OR ’ 2R0
RO+ HBr R-OH + Brt
(Ha-
CHg- CHCH, Bn
Br tHa-CH 4-(H, + (Ha-(H-Hy CHs-(H, (H1
Brt BrL Br

CH,-(H-CHg t Br'
Brt
From Alco hol
Prefiq- Hydroy
(-OH) SLFfia 2 0l

(1) LU CAS TEST '

’ when alcohol eacts with concetrated HCt in presnce of anhydu

Zn Cl? to qive chlortOalkone
R-OH + Conc H n y 0 R-C+ H,0
(alkanol ) (chlortoa| koane )
Zn Cl2
(methan ol) {chalorconethane )
i) CHa-CHI, -OH t Conc HU anhy
Zn Cla
ethanol )
(chloro ethane)
i) CHg-(H-OH + conc HU anhy
CH3-CH-l+H0
(propan -2-ol ) (2- chlorto paopane)
(Isopropylalbhot) ->
iv) T31tH,
CH3-C-oH t cont Hcl CHa--Q.t H,0..

(2- methylpropane-2-ol) ( 2-chlorro *a- me thyl prop ane

R
eactivity onde of alcohol ’
° alcohol >2° alcobol >1' alcohol ) tHa-0H
Mc hanism
CHa
(Ha--0H
HO
-H,0
CHHa
CH,--cl

V) CHa-H-CH,-0H + ConC HCl Zncl, CHa--CH, +H-CH-CH,-l + H,0

cHig
2- methyl ProPano| (majort ) (minor )
Mechanism -’ 1,2
CHg-(H-CH, CH3-(-Hs
CHg hydide shift

Migration Ortdert H)Ph)3' )2° )1' >CH3

eH,- H, -OH

Mchanism’ 1,2
CHg--H, nthyl shift
Reaction with PCl3 '
when al cohol rtacts with PCl3 to qive chlorco al kan e
3R-OH t PCl3 3R-Cl t H,Oz
(alkanol ) (chtortoalt ont)
3 CH3-0H +PCl3
(mthanol)
(chlortomethant)
Reaction with PCts
whn alcohol reacts with PCs to qive chloroalkone
R-0 H + PCls R-l+ HCI t PO cl3
(alkonol) (chorcoalkane )
tH-0H+ Pels
(methanot) (chloorntant)
Rtaction with Soct ' DARZENS PROCE 55|
Thionyl chloride ( Soc I;)in pnesence ot ryucine
Whtn alto hol reacts with the best was fort preparation of dkyl
(1

to qive chlomoal kone 14 is

chlornde from alcohol
R-OH t S0CL; Py- ’ R-C1 t HCl + S0, (2
(alkanol) (chloroalkont)
CH3-0H +
t Socl, ry:cMcl+ HCl+ S0,
Py

FINKEL STAIN REAC N:- ( Haloqen rachange reac")

reacts with Nai in
when alkslhalide i. alkulthlonide v alkul brromidt
presence of acetone to give Iodoal kane
(thysl-cH,)
Rt-xt NaT
No*T acton p-I + NaX

(Todoalk ane)
CH3-C t NaJ a0Tone, cHI + Nacl
$WART'S REACN - (Halog en eachange Keac)
When alksl halide i- alksl chloride o alkyl brtomide eacts wi
Ag F (o0 coF (or) aktbtomide SbF, on) Hgfz'to glve fluonoalkane.
R- X t AgF ’R-F t AgX
(Fluonoalkane )
CHg- (l +AgfCHgF t Ag!
HUNSDIECKER REHCN
when silvut salt of acid eacts with BI In preSeNCe of tatbon
tetmachlorkde (ccu) to give Brcomoalkan :
RtC-Aq + Br,BIt ccly
((silver salt of aid)
R--oH t AqoH

CH3-l- 04qg + Brc-Brt Ccy

silvert satof ethanoic aud)
sìlver acetate
 PHYSI CAL PROPERT IES OF HALOALKANE
(0) Meht chloric e melhyl brOmide and, ehyl chlorude cu colourless
Alkulhalides up to Ci artt colountess liquid Bryond re o alkyl halidu
arte colouurless cystaline salt
(2) Alkulhali des arte slightly po lar in nature ;so 1hey one insoluble in votu
molecules but soluble in ortganic solvent like Benzene, alcohot, cther ct
This is because the alkyl halicdes have no suffici ent en trgy to break h
H-bond which arte alreacs enist in water moleeles.
(3) Alkylbromides and alksliodide have high density than water molecules
but alkylchloride has less density than watert molecule.
(4) (a) Biling point of alkylhalides art inceasS down the qrtoup This is
because two typts of Fotce oF attraction 1e. dipole- dipole ond vandnni
foree of attraction -eist in alkylhalide which art stable than their
parent hydno tarbon
(b) TF alkylhalides art highls branched then its boiling point decreases
due to decKease of its sucface area.

cder of. boiling Point of alkslhalide, R-I) R- Bre ) R-CL > R-F
CHg--cl ' CH,- CH-C ( CHg CH,-U

CHEMIC AL REACN

) Reduction -
when alkylhalide undurgoes rtduction 'in presen of reducing agtnrt fike
LÌALHG éru NaBHy (on) Na (c,HsoH (or) ZhCù/c,Hs 04 (r) Sh/HCL
(or) Red P/ HI
R-A
R-X + 2 H] ’ R-H+ H-X
(Haloalkant ) (alkan)
R-A
CHg-Cl+ 2[H]
(chloromethan) (Mthane)
For iodine,
Red
R-I HI
(al kan)
 )-Elemination Rtoc/Dehudrohaloqenation Reac
heoting with altoholic ko
B- hydr ogen on
When alkylhalide hoving
to give n alkene (KOH +(GHs0H) kX
alc koH CHg(H= CH, t Hz0t
CH;-"H,-tH,- X
(propene)
(Halo propone)
Mech’
(H,-CH -CH,-X ’ CH3-CH =CH,+ k + H,0

R-tH,-CH,-x e; oH, R-CH= CH, +t H,0 +t kX

(Ko CaHeoH)
t
e3-CHg-tH,-CH-! alt: koH ’ cH,-CH =(H + CHa-CH, - CH
CH- CH,
(majort) (mìnort)

ale- koH ytH-cH

(major)
alc koH

alc koH

(majort)

() Nucleo phi lic Substitution Reacn

Replace ment of one functional group by other is call ed substitution
reach
R-X+

weak bas, strong base

good leoving gocuy ich spieces

(strong Nu)
’ His of two types
ti) SN' unimoltcular nucleophilic substitution Rtacn)
(i) SN? ( Bimolec ular nucltophilic substitution meach)
i) SN'(unimolecw art Nucleophi lic substitution Rac)
Rote of neach depends ugon only tontertration of substrate
r(ate a substrate |
rate k [substrate
S0,it is a 1st orde eaction
’ Tt consists of 2 steps
8ttp-1 The C-x bond in halogl kan . tunder gots hetuolutic fission
to qive a cait bo cationSo,this
cation step is-called as rat
deterrninig step and also this is a slow step
RDS
Rt 4 x
s low
( anbo cotion
step2 - In this sty a Nu attacks tht tarbo cotion to giv final
product Thìs step is fast st.
Rt + Nu fast
FasT R- Ni
(Product)
’ Reactivits onder ’

) 3° halide> a halide>1' halide >a X

(Benzylhalide) Alkylhalide (Methyt
haide)
IF alksl halide is opticalls active then
cecenìc mìattur wil be forned
CH,
CHg
H

chiral carbon (mirrort )

(o)
A
Symmetric cartbon
 (Ha RDS
s low

Rtainstoh
CHa
Nu (,Hs--Nu + Nu-t-CGH5
H
(607-) (501:)
Jnveslon

D-(04/23
(i)SN² (Biomolecwar nucleophilie' substituton toc)
’ Rate of teach dpnds uDon both conc of. substae and conC- of Nu.
Rate d [substrateJ (NuJ
Rate k[substrote](Nu]
S0 H is a. 2nd ortdert eacn .
’ Stron qNu is a favowable condition For this reath.
E9- Hydro lysis of chloromethan
plHgcí ’ H0H,c H0-CHgtcl
T.5.(Tran sition state)
|Highly unstable and high enercgy stat
Riactivity ondur oF alkyl halides to wards sN'reach.
))
CHx)1 halide )2' halide )s' halide
Allyhalid Benzyl hal ide
In vertsion product will be foremed
Reaction With Aq. kOH
’ when alkyt halide eacts with aq, koH to give adeohol
R-X t a. koH ale KoHOH- baye
Naloal kane alcahol
CH:-0H +ke
chlorcomethane Methan o l
 S0dium Alkoide (RONO)(Williarnson syntheeis rtac]
(-) Rrach with
alkylhalide. htaBed with Sodiun al koide to give an ether:
when
prepanatio n oF unsymm etrical ethort occues in this reacion
’
R-X + R'-ONo R-0-R+ Nax
haloalkane Sodium
al koide
alkonyalkone ( Iong es4 chain )
+ CqHs ONa AcH-0-C,Hls t Nacl
chlorto methane sodium ethojde Methos than
thylmethyl ethane
’ Alkyl haljde must be primary
substitution.
In cose of 3 alkylhalide elimìn ation rach takeS place ovr
CH3--2
-Cl CHONa
CH
Teat butylchloride 2- methyl propene

CHa-CHiycl + CHgoNa AcHt -o-cH,-CH t Nact

chlorco ethant
2- ethoy- 2- methyl Propane
e) RRach with Alcoholic or Aquo, KCN
aq.K. so1" OF kCN to give
’ When dkslhalide eacts with alcoholic or
alkane nitrule
R-X t KCN R-CN t kx
Haloalkane Olkane nitrule

t-9:- CHg- Cl + kCN CH,+CN+ KCN

ethant nitrile (ort) methyl cuanide
chlorcomethant alc: oft aq

R-CN Partial R-C-NHz ( Alkanamide)

hydrolysis
9 (H-CN ’ CH;-B, (Ethanamice or Acetomide)
Complete
(1) RCN
hydrolysis R--OH (Alkonoic atid )
aid
CHg-CN ’ CH3--0H (Ethanoic acid (or) actic
()
R-CN tomplete RCH,-NH,
reduction AIkanamine (1 amine)
4[H) |Mndius Rtduction
Redch
tiAtH4 n) Na/ c,Hs0H
11
CH-CN cH-CH, NH,
(Ethanamint ort Ethyl amìne))
(1) H20+ R-C-H (Al kanol )

(Partla! reduction)
8tepheniRRacn.
Reduction
CH-(N ’ (H-l-H
Ethanol ot Acetaldehyde
CH3(EN+ 3H,0 .9- Hcl CHa--of+ NH3
J-H,0
tH--oH
Dt- 13-0423
(2) RRach with AqcN
When alkyl hali de neatts with AgcN to give alkyliso tyanid
R-X ’R-NEC + Aq X
Haloalkant
Alkylisocyanid?
Chlorto me thane
Methyl isocyanide
) Reach With AgNO,
whn alksl halidt reacts with AgNo, to qive nitro alkon e
R-X
Haloalkarn Nitroalkane

Nittomethane
t) Reacn with KNO,
when alkyl halide neocts with KNO, to give alkylnitrüte
R-X t KNO ’R-0-N=0 t kx
Haloalkan Alkylnitrüt
9: tHg (l+ kNO; (H-0-NE0+ kce
Mthylnitrit
 y.v1)
Rtach WHh Amnonia (HoIfnonn fononoltysis ynthests e0th)
when alkulbalidt htattd wi th 0q-an monia i4 qives 1, 2", and
quanter hars ammonitum sol!
R NH HY
R-Y t NH (a4) Gualed fubt A1kanamint (1'omint )
Haloalkant (adiobatic protess)
R-NH RX - ’ R-NH + HX
(1amint) K(2° amint)
R-NH
7 R-N-R 4 HX
(' amint)
R-N-R + R-Y
R R
quanternany amnoni um 9a4 ) (4 arnine)
(uvI)
REacn With Metal
() REach with M9 (Prepartation 0f Grign and Reagnt) :
when alksl halidt reacts with M in presence oF dry cther to qive
aJkyl magntsium haide
R-X t Mg dru
Haloalkane eth
Alkyl magnesium halide
Girignand re agent
H,0
R-MgX ’ R-Ht Ma(oH)X
alkane
Here it alkane is forming, S0 H0 can't be tak en
dy
CHgCl t+Mg Rthe
Methyl magnesium halide
(2) Reacn with Na Wudz Reacn)'
’ When alkylhalides eacts with each othÝ in pmeseNce of Na and drcs
thee to give an alkane
(Hrre, in Keactant onts 2molecule nill be taten alwaLy
R-X t Na t X-R dry. ’R-Rt aNax
thrc
Halo alkahe al kan e
 dry CHCHa + 2Nact
Rther Ethane
Chloro methane

) CzHs Ct
Cl Na
dmy ethen CytHo.6utane
Friedelcraft Alkylotion OF Benzen
acId e.
’ When benzene reacts with alkulhalide in presence of Lewis
nhydtouw ALXa of FeXa to qive alkyl benzene
H
H
+ R-X otnhy.Fe XAlX3
H
H (Lenis add) Alkylbenzene

+ CHgCt - anby. t H
ALCl,
Methyl benzeNt
Toluene
Dt- 14-04-a3
ALCÍ,
+ CH CH CH,-C{ anhy: ProPyl bernzene
(mìn orc )