Halooalkanes & Halo aseneS Wosh Sheet

A ,2409/5023
Explain

4o1gnard seagents should be poepaved undey anhydsous

(a) )
conditions (NCERT)C20) 3
41gnasd seagents ase vesy seactiue " They seact with

AseGent in the appasatus os the ctasting mateials to qve

hydovcasbons
S
R-Hg X + H-0H R-H t M(oHx
acts as ba6e

Hence. qig nawd seagent muSt be poepa>ec undes anhydous

conditiong.
In-Butyl boomide has highes B"P. than t -butyl bsomicde
(2019, 2014)

88
(n-butyL bomide) J t t-butyl boomide)
Jt has lages Susface atea Lasgesm
magnitude of vandes
waal's fosces l bence higheo is the B-P.
(c) C-C bond lena in Os),
chloobenzene is Shostes than in CHyCL
In (2016)
chloobenzene, c- CL
bond cques pashal double bond
chatactes due to sesonance whilein CHCL C-CL bond hos
puse single bond chasactex Asa gest -cL
bond in
chlorobenzene iG shostesthan cH3CU

C-cL bond has pastial

double bond chasactes
(a) Racemic mituse
optically inactive. ( 2015, 20A)
oacemic mixtuse contains the 2
enantomeos d l n qucl
ancelle
Poopostons As the DDtation due to one enantiomes s
enantiomes,the sefoe
equal oppoSite ootation OF anothes
it is optically inactive 2013

pola ase m miscible wIth wates (2015)

le) Akyl ha lides though
the inability of alkyl halide molecule to (NCERT)
Bm
This is due to
intesmoleculay hydogen bond with wates molecules. In addtion

to this,the cttscton blw alkyl halide molecules is Stsonges

wates
the attaction blw alkyl halide &
than
haloatenes cCuÝ Sloly l2os)
(6) Electsophlic gxns in
Halogen in halo asenes withdoaws e thÝough -Ieffect &oel ease

e thoough +R effect NoedThetoinductye

ment on
eftect is stoonoes than
yeGonance effecin case of halogens.& Cavses net o
withdQual As a oesu lt , the electooph1lic oxns. /n halorene

occus Slowly
fos poepaing alkyl
(a) Thionyl chlotide method is poefetsed
(20/9)
chloides foom qlcohols
R-OH + SOcl, R-Cl t SO 1 t HCRT

The bypoducts of the kn ,ie SOz HCL being gases

escape into the atmosphese (eaving behind alKyl chloies
in qimost puse state. (Le chatelies principle)
Ch) p- dich loDbenzene has highes M"p. than those of atho k
meta iGomesS (2019) (NCERT)
pqsa - isomes so t
It is due to the qeateo symmetoy of
moleculeo. in its
has mde closely packed asTangenent of
cSystal Lattice Hence, p-dich loObenzene haghighes H P:
) the dipole moment of chlosobenzene is lowes than tht o5
cyclohexyl chloide CNCERT, SQP- 2016) (2013)

mownts are bond wo

CL
sp* hybbded L spa hybidised
chlooobenzene Cyclohexyl chlode
sp has mooe s chasactes than sp3. So sp is mo
electoonegative than sp3.
Fus thes, due to
TeSonance, C-Cl bond in
chlosobenzene
 shostes than cycloh exyl ch lode due to pa tal dou ble
Lond chasactes As d1pole moment a
Poduct of chage 2
distance Thesefose dipole moment of
chlosobenzene is leSS
than cydohexyl chlo de
j) chlozobenzene is
extoemely leSS teactwe towadds nucleophi lic
Substhtutuon oxn 2013, 2019)
mis iS due to the
following seasons Cafon
(i) Resonance effect in chiosoben zene
ond chasactes . which ceotesBastotsleble
makes it difficult fo the
to cleave the C-cL bond (Dsaw RS)
nucleophile
() The nucleophile SufesS sepulsion oom the
incoeased e
density on the benzene ng as a vesult the
unable to make a nucleophile is
cloGe appdoach fos the attack on
(k) chloofoom iS Stoed in
molecule
closed dask colouded bottles
completely lled so that að is kept out (2010
This is becauSe
chlosogom is slooly oxidised by ais in the
psesence of light to an
extoemely poisono s gas phosgene
2 CHCL3
2 COCLy t 2 HCL
chloofom Phosgene
(2) The psesence of nitso qp (- NO2) at olp positons
incSeases
the seactwity of haloasenes towdS nucleophilic
substitution
XxnS(2015 20|9)(NCERI)
The poesence of NOz gop at olp poSition, in
tmaenes helps
in the Stabilisaton of esulting
casbanion by -R 2-I effects
and hence incseases the teactivty of halo arenes to
wasds
-nucleo philie su bytitution oxns.
n) Athough cl is an E w6 yet it 1S olp isecting în
electsophilie asomatic substitution oxns (2015)(NCERT)
the weakeg sesonance effect o& cL which stabilize the
Casbocation fo3m ed tends to oppose the stsonges -I efect
oF Cl which deStabi /ze the catbocation at otp positions & mates

Oeactwation less fos olp positons

 2 Convest the following
(NCERT, 20I6)
(a) 1- Byomopopae 2 - Boomopropone & vice vessa
By
KOH (alc) /o HB

(dehydro halogenaion) Mayk: addn.

KOH (alc)/ H8l peroxide B

(dehydsohalogenation) Anti Haxk
addn
(NCERT)
(b) Poopene to Popan-1-ol o Paopan- 2- oL (2o13)

HBS|peroxile
Anti Hask addn
OH
+ HaSOy H20
boil

(c) Benzyl alcohol to 2-PhenyLetha noic acid (NCERT)s qu

cH20H CHCL CHCN

SOcle
-SO2, - HCL
KCNEtOH - Ha0
Nucleophiic
Substiution

H7 hydsolysis

(d) Ethanol to
Propanenitile (NGERT) (20IS)

CH3CHaOH a CHCHIKCN/ EtoH -Hz0

CHy CH,CN
Nucleophilic
(e) SUbstitution
Ethanol to But -Z-yne Lsimla to NCERT, HOTS)
cH3CHz0H SOcl2 cHaCH2cl KOH (alc/A cH,CH
(Ethanol)
(chlosoethane) (ethene A
E Ccly

CHgcL lexces) NaC =cNa NaNH2 in NaNH2 i

HCH CH2
(disodium scetylide) liq NH3
Br B8
CH-C-CH3eut -2 -yne)
() Poop1-ene to Fluoropoopane (2015)

cH-CH=CHa HB Ipesoxide
Ag f
Anti Hak addn CH3-CH, -CH Bo Swastz
Ran

(9) Aniine to Boomobenzene (NCERT) CHg -CH,-CH-f

NH2 NC Bo
Na NO | HCL cuB /HB
DiazotiSation Sand mey es Rxn
(Aniinc (8enzene diaZonibm
chlooide)
(8romobenzen)
I) Toluene to Benzy alcohol (NcERT)
CH3 CH2 Bs CH,OH
NBS

( Benz ene to Biphernyl

Bs Fe dust Bx
2 Na in
2 Na B
day ethes
(Fittiq RXn)
C) Chlodobenzene to O-ChloDO acetophenone l 201G)

t cHgCoCL anhyd. AICL

Fiedel coaft
coc3 +

acetylotion
(o) CocH3 Lp)

Fsactional
A distillation

Na Ca ( Na
coCH3
 3 Dsqw the majos po0duct Jos each of the
following Xn

OH
la)

HCL/A (NCER T)

CH, OH CH2 Cl

(b)
HB
cH3 (NCERT. 2016, 2017)
cHg Bo

lc) AgCN
CH -CH - B CHz- CH - Nc

Ethyl isocyantde
cL'I
id) Na -

(23 - Dimethylbutane)
doy ehes
Wustz Rxn

4 Dsauw the stouctuse of majos monohalo psoduct in each of

the gollowing
HBa
A
la)

HB
pezoxide

Fox A ) +
Mo se sta ble benzyic caxtocatior
Ph

Bo

Ph

Bo
Ph
 KCN
cHg-cH,cN (Ethyganide)

A9N D cH - CH2 NO (Ethyl iso cyaido )

(AGNO2 cH-ONO
NAND
CHa B
(NaNOg
Bs HgBs
Hg in . Co
doy eth es if. Hao/H+
(G)

S Identify A to D,inrthe foloying

alc. KOH H8S Na in doy ethet

A B

i. Mg in doy ethes

A =) ( 2 - Methyl psop- 1-ene)

B)
(2 - Bsomo - 2-
methylpropane
(22,3,3 -Tetsamethylbutane)

(2 - Methylpropane)in
(a) hy ase aoyl halides less
Teacte towasds nucle ophiic
sTutuon sxn than alkyl halides Hooo onho
Can oe en hance
ne seactivitu of axyl halides ? (N GERT, A
empla
In
haloatenes ,the Lone paid
Denzene nng SÍ, C-CL
of e on halogen ase in desanaa
bond acquises postiat clouble
which Stoengthen c-cL Ihesefoe, they a e
bo nd
 SubGhtuhon s n
less xeacue towasds nucieophiuc

be in coease by the
The veactivity of aoyl halides can
preGence o& Can electtorn with
dsawing group (E wo) ct
ty
ostho paza posittons . Howeves , no effect on seacty
of ha loasenes iG obseved by the presence of Ewh ct
meta poSition
(b> Psedict e explain the ozdes f oeactivty of the folloing
Substitution. (Exempla)
Compournde touatds nu cleophiic

NO2 NO2

NO
NO2 NOz NO2
liv)

Psesence of EwG at olp position incseases the stob1luty

(arbomon.
ntesmediate & hence incoeases eactuityisemheay
No W moe the no of EwGn at olp position , hiqhes will be
the oeactivity of allkyl hauide
Osdes

7. Assange the compounds of each set in osdex of seactivity

towasds Sn2 displacement (NCERT, 201|)
2-Boomo-2-methylbutarne , 15omopentane, 2- Boomopentane
1. 1-Bsomo-3- methylbUtane, 2-Baomo- 2-methylbutane,2-Bsoru
-3 -methylbutane
1-Bzomobutane, 1-Bomo-2,2 - dimethylpdopane , 1-Bxomo- 2
rmethylbutane , 1-Bromo-3 -methycbutane.
 Bs
8
2

(A) (c)

osdes f S2 seactiwity:ai> 2° >

wndame
0Ddes = B> C > A

Bo 2°
(A)
(B)

os des o8SN2 seactvity' 1 ° > > 2°

oDdesi=

B 8

(A) (B) Co)

Ste ic hindesarInce inG: wth dec. in c e J the subtnt

It n n
fsom the atom containing
Leaving gp
AlSo stesic hindesance iinc: with
nc in no of Substnt:
Inc. oDdes of steic
hindesance : A<
DKc<B S -
Osdes of SN2
8.
seactuity : B<c <D <A
AnSuwex the gollowing quesions :
(a) which one o
thefollowing compoundG is mote easily
hydyolyzed by KOH and Ohy?

CH3CHCtCH2H3. OR CH3cH2CHy ClSe2oi2). 3l

CH3 -CH-CHy -CH3
CH3-CH) -CH
2° casbocoation
1 cas
asbocation
mose Stas(e
Sec- butyl chlode 9et hydsoly zed mose easily than n-
chlode undes SN1 conditio
 (NCERT)
CçHgCHCL)¢H5
+
lonizathon
CGHG CH,-cl Ce Hs- CH2
casbocahon Stabilized by
delocaization oves 1 oHs ang.

C6Hs -CH- C6Hs lonization

GeHs - CH-CsHs t c
(8)
Casbocation Stoabiized by
delocalaation over 2 CGH ngs
Dndes Sl conditon
Teactivity depends upon stability of casbocationr
He se (B) is moze stable as t 9 segonance Stab1ized

by 2 ngs
C6Hg CHlcL) c6Hs gets hydsolyzed moe easily than
CeHs CHaCl undes 1 condition

Dndes SN2 condition,

reactivity depends on Stenc hindesane

CeHç CH2l gets hydoolyzed moTe easily than Cç Hs CHl)

co Hs unde S2 condition
(6) which one undergoes SN 2 SubstitutioD xn faStes euwhy?

(A) (6)
1-Iodopentane undesgo es SN2 oÝn fastes beauGe iodino
is a better Leaving gp
because of ts Lasge Gize, it will
be seleased at a faste sate in
the poesence of incomng
nucleophile.
h

4 Explain :
la) How do polas Solv ents help in the
fiÝst Step in S1
mechanism ? (NCERT Exemplav)
The S1 mechaniGm paoceeds thsough the fomation of
 casbocation Tt involves bseaking of C-x bond Soo which
enesgy is obtained thsough the salvation of haide
the pooton qf the pootic solvent ThusS polas Solvents help
ionization step by Stabiizing the (ion) by solvation
) which of the following compounds would undergo solvolysis
fastes and why ? (NCERr Exemplas)
CHcL

(A) (8)

(B) undesgoes S1 sXn faste than (A)

becausein case
of CB).the casbocation fomed aftes the loss of cL is
Gtabilized by
desoncance , wheseas , no such sta bilization iS
pO5Sible in the casbo cation obtained
fromlA)
10. Compaxe the sate of
Solvolysis o& the ollowing compounds:
CL C
(A)
(B) (c) (0)

2 RS
3°
SRS
Draw the
Rate o& solvolysis lSN 1) de pends on
rsnadng shuchas
stabiity of
casbocation
Osdes: C>A >B D
I CompoUnd A' with moleçulas
fomula Cy H Bo is toeated
with a koH So|. The sate of thiS Kn
cepends upon the
Onc of the compound "A' only when anothes
Somes B' t optically
A act
of this compound was tteate ag kOH So
oate 6f xn. was found to be depen dent on conc
Ompoond & KOH both: (NCERT Exemptas ) HOTS)
 wnte down the stouctual fomula of both co mpound a2
i Out of these 2 compoonds, which one oill be convested to th
pooduct wth invested configuzation ?
etst
RoR depends on conc of compoUnd A So xn pzocteds
thsough SN1 mechanism & alkyl ha lide is 2
CHg
Compound 'A: CH3- B

RoR O8 compound B depends upon boh conc of alkyl

halide & KoH. Hence SN2 mechanigm

Compound 8': CHa-CH,-CH CH

B

Beca use of SN2 Xn compound 8' will undesgo

configudation 2 produce an invested pooduct
to you i
12 Following compounds ade given
2- Boomopentane, 2-Bsomo-2 - methylbutane, 1- Baomopentane

i wite the compoun which is most seactiue towads SK2 SXn

i: Wite the compDund which iS opttcally actie
wite the compcund which ie most 2eactwe towoatds P
elimination xn. (201)

i. 1- Bsomopentane it is paimary halide theseto e ondegoes

S2 %n: fagtte
if 2 - Bsonopentane
Bo

casbon iS asymmetoic

2- Bsomo- 2-methylbutane , becavse 3 alkyl hadide on

dehydo qenation Jom most Substituted alkene ohich
ie moJe stoable
 (a) Identify the chioal molecule the fol\owing
13

and

Wte the stuctuÝe of the pooduct when chlosoben zene S

toete with methyl chloide in the poesence of Sodium metal
and doy ethes
S wite the stauctuse of the alkene fomed by
dehydoohalogena
-Hon o 1-Baomo-1 - methylcyclohexane wrth alcohoic KOH
trie (2018)
(a)i carbon
OH

(b) Wuxtz - Fittig Rxn

CL
CH3
2 Na in dsy ethes
t CH3Cl
+2Nacu

(c) Bo wCH3 CH2

alc KOH
t HB
no

(Minod)
Among all the SomezS of
moleculas fomula Cy H B,identb
(a) the one isomes,
which is optcally active
tb) the one iSomex
which is highls seactwe
(c) the One towasds S
ISomes which is highly geactwe
(d) the tuo towasds S'
isomess
-ation uwrth alc koH which gav game. pooduct on dehydsohalogen
(2019)
a) cH3 -CHaCn
-CH3 (2 -
B Bomobutane )
CHg -cHg -CHg-CH2 -Bo
(1-Boomobbutune)
 CH3 2-Bgomo - 2- methyl psopan (
(c) )
-0--;
H3C- C-CH3 tert butyl bT0 mide

CH3
CH3
(d) CH3- CHcHa- Bo and CrHg-c-CH3

B
IS Identify A 2
M9
Ha0
-B
in doy ethe

H9 B
B
B: +

mono
Cadbon of MH 2 9lmol gives a Single
l6 (a) A by dSO
dichloo desi vatives On photo chloi
-chloso deivativ e &2
stOUctuse of hydoocastbon. (Exemplas)
- nation Give the
CH3
Pentane
Cda- C-CH 3
(cgHi2
CH3
compounds fomed
(6) Wite the stuctues R names of the
when compound 'A' ith moleculas fomula , C H¡ is toeated
with Ca in the poesence of Feclg
CHg cH3
CH3
Feci3
dask

O-chloto toluene
p-chlosotolwene
c Name the alkene which will yield 1-Chlos0- 1- methylcyclo
-hexane by its sX oith HCL Wte the xn-also. ( 2023)
HCL
cH3

t1-Hethyleyclohexene
(d) A hydOcarbon CsHo doeen't Yeact wth chloine in dabk
but gues sing le mono chloo, ompOUndd' CgHaCL in big ht
hydoo caxbon. LNCERT)
Sunlight Identify the
CgHo alkene cycloalkane
since it doesnt eact wrth cl2 in dask. it con't be
alkene but must be Cyclo alkane

No DXn
dao k

1- (a) Which of the following halo al kanes vcto oith ag KOH

most easily ? Exploin giving oeason: (ExempLax)
i. 1- Boomobutane 2 - B8omo- 2
2 -Boomobutane
methylpzopane
iv: 2-Chlosobutane
CH3
Casbocation OH
’ (CH3)coH
Testiay CHgCH 3
Stable 3 Stable)
(6) Some alkyl halides undesgo Substittion wheseas Some
Undsgo elimination TXn on tseatment wrth baSes DiScUSS the
stsuctuyal featuses of alkyl halides with the
which aTe sesponsible fos this
help f exampl
difference. (Exe mplas)
Prmasy alkyl halides follow SN²
-phile attackg at B0 to the halog en
mechaniGm in which nucleo
atom A toansrtion
state is goomed 2 inally halogen
atom is pushed out
aq. koH H

H weak base HO----c-cL HO -C

ts£nsition state
Iestiagy alkyl halides follow 9' mechaniSm. Hese, 3° cadbo
*Caton is fomed i Now, if the eagent
uSed is a weak ta
then subs bitution occus while it it is a Sttong base than
in_tead of Subetitution, eliminatioh OCCUJS
CH3 CH3
Hac-c. aq: KoH

CH3 (3*)
CH3 cH3 cH3
+ OH
Hac OH CH3
CH3 CH3
Hese,the seagent used iG aq KOH , it is oeak base so
Substitution takes place
CHs
CH3
alC KOH
H 3 c aElimination Rn: Hz CHa:

CH3
CH3 CH3

HI

2 - Hethylprop-1- ene

As ale KOH is a staong base so elimination competes oua

Substitution alkene is med: rO

(c) The toetment of alkul chlodes with aq: KOH leads to

o ' 9 9 e gty.
alcohale i presence o& clcohoic ROH)
the Fobmation of
(NCERT'bTY ('enm
alkenesS aoe majos psoducts Ex plain.
9
In aq' Sol" KOH ig almost comoetoli to guue OH ons
which being a stTong nucleophile boings about a Substitrtion
yXn- on alkyl halides to fom alcohols. In the ag Son jOH
ions ae highly hydsated. This educes the basic chaactes
of oH ions which fail to, abstsact a hydsogen om the
p-casbon on the alkyl chlode to fom an alkene
On the other hand, an clcohoic Son of koH
containg
alKOxide (oR ions which being a much Staonges base thcu
OH ions poefedential y eliminatey a molecule of Ha Room an
al kyl chloide to foDm alKenes
a geSlt of:
..)hat type of poOducts a7e obtained as
optically active
S ' xn. of an compound
an
ophally active compound
Racemic mixtuse
1f Alcohol with opposite sign of otationinversior m
Conhgus ahon.
(e) which of the compounds will seact fastes in SNsxn with
yhe OH ion ? CH3-CH2-cL GeHg -CH-cl (Exemplao)
cçHs CHzCl yeadily undegoes ioni Zotion to give C6Hg CH2
casbocation, which is Stabiized by seSonance
CH2 CH2 cH2 CH2
Benzyl
casbocator

On the othes hand , CH2 CH,cl doesn't undesgo ionization to

give CHzCH casboation Thesefoe, CEHs CHcL eats
fastes than CHCH, C oitth OH ion
() of the 2 bOMo desivatiwes CeHs CH (CH) B8 and
CeHs CH CeHs) Bs, which one is moYe beactive in SN' Xn
anod
why ? (2011)
casbocaton: (C6Hs), cHT qnd CeHs (CH2) CHt
Resonance stabiized by Resonance stabi ized by
2 ben zene
angs 1 benzene ing
SN' Teactiuity depends upon stabiuty of
6Hg cH (CEHe)Bx is mose
cásbocation So
seactive in S' seacton.
CH2
CH CH2
I8 (a) chloxobenzene is foImed by oxn of chlonne ith benzen
in the poesence of ALCla. Identify the specues which attacka
the benzene ing in this nn (Exempa)
follouwed sxn
CliS an electsophile forned by the
ytiChleroniwm
AIClg + i2 [ALClu] c) L
chlosobenzene
CI* attacks the benzene sing to give
CL

(b) Ayyl chlodes & baomides can be eas1lY poepased by odtsn

electsophilic Substitution of aenes with cl B By espectively
in the pesence of lewis acicd atalysts But why does
Poepaoton of ayl iodides sequises psesence of an
oxidising agent? (Exemplo
lodination xn qe sevessIble in natue lo ad out sXh
n foswasd disection, HI fomed dung iodination ig
Semoved bu oxidation H)Oy is used as an oXIclizing qent
which is used to semove HI.
I
HIOy
+ I + HI

5HI + HIOZ 3I, + 3H20

(c) which of the folowing compounds (i)2 (in wil not beact
with a mixtuse of NaBo- HzSoy Explain why ?
() CHg-CH2 -CHaOH (Exemplas)
(i)CsHsoHb
2 NaBo + 3H,sOy 2NaHSOy + So t B,+ 2H,0

Bo
Bo H20 Bo

(3,46 -Tibsomophen)
Bo
 cH3Cn2 CH2OH doesnt eact withBo gas

d) ALthough cL is an Ewe,yet it iS ostho , pata disecting

.a electoophilic asomatio Substittion xn Explain ( 201G)
T is becaus e CL exhibitG positive mesome effect " By
vistue of eSo nance , cL tendds to
stalb1lize the casbocatic
incoeases the e densty moe at olp posrtions than
at meta 'position of the benzene ing
Thus, electoophilic
asomatic SubsiNcSia.
DXNS take place at olp positions

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