Alkyl Halides

(haloalkanes)
RX
 Classification
Alkyl Halide

Primary Secondary Tertiary

Alkyl Halides Alkyl Halide Alkyl Halide

H H R"
  
R C X R C X R C X

H R' R'
2
 Nomenclature
A- Monohalogen Derivatives :

Common Name

CH3 CH 2 Cl Ethyl chloride

CH3CH2CH2Cl N-Propyl chloride

y3ni bdon tfro3at

CH2Cl Benzyl chloride

3
 Nomenclature (Contd)
IUPAC Name

CH3CH2CH2Cl 1-chloropropane

Br

CH3CH2CHCH2CH3  3-bromopentane
3-bromopentane

Br Br
3  23  12 1
CH2CHCH=
CH3CH 3CH2CHCH= CH2 
CH2  3-bromo-1-pentene
3-bromo-1-pentene
4
 Nomenclature (Contd)
B- Dihalogen Derivatives :
Dihalogen
Derivatives

Geminal Vicinal
Dihalides Dihalides

e.g. Br
e.g. H2C CH2
CH3CH
Cl Cl
Br
ethylidene bromide Ethylene chloride 5
 Nomenclature (Contd)
• Geminal Dihalides:
IUPAC
Br

CH3CH 1,1-Dibromoethane
Br Ethylidene bromide
Cl

CH3CCH3 2,2-Dichloropropane
Cl 6
 Nomenclature (Contd)
• Vicinal dihalides:

IUPAC
H2C CH2
1,2-Dichloroethane
Cl Cl

CH3
CH3CCH2Br 1,2-Dibromo-2-methylpropane
Br
7
Cl Cl
2,4-Dichlorohexane
 Synthesis
I- From Hydrocarbons:

e.g. h
CH4 H3C Cl (Free radical mechanism)
Cl2

II- From alkenes:

HCl H
e.g. H3C C CH2 H3C C CH3
H Markonikov
addition Cl
HCl / H2O2 (Allyl chloride)
AntiMarkonikov
addition

CH3CH2CH2Cl 8
 X
III- From alkynes:
HX
eg. : CH3 C CH CH3 C CH2
Markonikov. addition
1-propyne HX
HX, H2O2
X
Antimark.
addition
CH3 C CH3
H ejt mn HX tani
X
CH3 C CH - X
HX, H2O2
X
CH3 CH2 CH X = I, Br, Cl
X

or you can add HX to alcohol

IV- From alcohols:
ROH + SOCl2 RCl + SO2 + HCl
9
 Reactions

I- Preparation of Grignard reagent:

  Mg / Dry ether  
RX RMgX
10
 Reactions (Contd)
II- Nucleophilic substitution reaction:

RX + Nu RNu + X-
e.g. RBr + NaOH ROH + NaBr

can proceed through

SN1 OR SN2
11
 • Bimolecular nucleophilic substitution reaction
(SN2)

  Slow  
Nu R-X [Nu....C....X]
highly unstable T.S.

Fast

Nu-R + X

12
• Bimolecular nucleophilic substitution reaction
(SN2) (Contd)

e.g. CH3Br NaOH CH3OH NaBr

strong base (( NU ))
Mech.
H
H     
Slow step
Nu C Br Nu C Br unstable transition
H
state
H H
H
Nucleophile attacks the
back side of C
Fast
lo ma kan fe carbon cation wel
neucliophilic 9ar mkan el group ele ra7 H
y3ni sn2 Nu C Br
H
13
H
 e.g.2 CH3CH2CHCH3 Aq. NaOH CH3CH2CHCH3
Cl OH
(R)-2-Chlorobutane (S)-2-butanol
Mech.
CH3 H
H  
OH 
Cl H C Cl HO C Cl


Et
Et
strong base Et CH3
H3C
=
(R)
strong nuclio unstable transition
state

CH3
H
H OH HO C
Et
Et CH3
(S) inversion of configuration
14
Unimolecular nucleophilic substitution reaction
(SN1)

Slow
RX R + X
Fast
Nu

Nu-R

15
 Unimolecular nucleophilic substitution reaction
(SN1) (Contd)
CH3 CH3
e.g. H3C C Br H2O H3C C OH
CH3 weak base (( NU )) CH3
Mech.
CH3
b a
H3C
complete
C Br C
ionization sp2
H3C sp3c H3C CH3
H3C planar

Nu
attack from both sides

from b) att
ack front ack from
CH3 a) att side side
H3C
Nu C back C Nu
CH3 H3C
CH3 H3C
16
50 % 50 %
 Br H2O OH
e.g. H3CH2CH2C C CH2CH3 H3CH2CH2C C CH2CH3
CH3 CH3
(R)-3-bromo-3-methylhexane 50 % (R)-3-hydroxy-3-methylhexane
50 % (S)-3-hydroxy-3-methylhexane
Mech.
CH3
Et b a
H3C
Br CH3 C Br C
H3CH2CH2C sp3c H3CH2CH2C sp2 CH2CH3
Pr
H3CH2C planar

H2O
carbocation wo nucliophlie attack from
both sides
attatched m7l el group ele ra7t fr om b) at
k front tack from
y3ni sn1 ac
a) att side side
back
CH3 H3C
HO C C OH
CH2CH2CH3 H3CH2CH2C
CH2CH3 CH2CH3

50 % (R) 17
50 % (S)
Racemic modification
 Factors affecting nucleophilic
substitution reaction (SN2 &SN1)
1- Structure of alkyl halide:

H  
C X SN2 mechanism
Nu
H
H

Thus R R

CH3 > RCH2X > R

CH X
> R C X
R
18
 1- Structure of alkyl halide (Contd):

CH3
b a
H3C
complete
C Br C
ionization sp2c CH3
H3C sp3c H3C
H3C planar

SN1 mechanism

Thus
R R
R C X
> R
CH X
> RCH X > 2 CH3
R
lano ra7 ykoon fe carbocation wo ele 3ndo H akter ra7 take
el H bs n7na bdna el carbocation hoon yrtb6 bl x 19
 b polar protic solvent el LG will be stabillized by positve part of H2O
2- Solvent wel H lazm mrtb6 m3 O or N
bl polar aprotic el DMF has
Solvent
H attatched to C they cant participate
in H bonding

Non polar
Polar
e.g. benzene

Sn2 ma b9eer bl protic solvent

l2no el strong Nu will Polar protic Polar aprotic
be blocked e.g. H2O, ROH, e.g. DMF HCON(CH3)2
from attacking by the partly positiveCH3COOH DMSO (CH3)2SO
H

Polar protic solvents (which release H+ by ionization, e.g. H2O,

alcohol) favour SN1. have H bonding to O , N , F

Polar aprotic solvents (do not release H+ by ionization) as DMF,

DMSO favour SN2.
Dimethylformamide
20
3- Nature of nucleophile.

CN - > I- > OR- > OH- > Br- > Cl- > ROH > H2O

nucleophilicity increase

_ _
OR , OH strong Nu
ROH , H2O weak Nu
strong Nu favour SN2 reaction
weak Nu favour SN1 reaction which is not dependent on conc.
of Nu
 +
H 2C CH CH2Cl H2C CH CH2
does not undergo SN2 reaction but
undergo SN1 reaction due to
stabilization of the formed
+ H
carbocation by resonance H2C C CH2
N.B.
CH2=CHCH2Cl CH2=CHCH2 CH2-CH=CH2
allyl chloride
S1 bec of the stabilization by the c cation

CH2Cl CH2 CH2

benzyl chloride

CH2=CH__X CH2-CH-X
vinyl halide it is hard to
remove the X 23
N.B. (Contd):
 Neopentyl carbocation rearrangement for neo-carbon

CH3 CH3
weak Nu
H3C C CH2Cl H2O H3C C CH2
SN1
CH3 CH3
neopentyl chloride
el methide shifting mshan methide shift
y9eer staple lano fe +

CH3 H2O CH3

H3C C CH2CH3 H3C C CH2CH3
OH
2-hydroxy-2-methylbutane
24
 Applications
e.g.1 CH3 Cl CH3
weak Nu
H3C C C CH3 H2O H3C C CH CH3
H SN1
CH3 CH3

2-chloro-3,3-dimethyl methide shift

butane
CH3 CH3 CH3 CH3
H2O
H3C C CHCH3 H3C C CHCH3

OH

it is hard to remove I from vinyl but allyl can

because of the resonance for the formed carbocation
I
I
H2O
e.g.2 CHCH2I HC CHCH2OH
HC
SN1
1,3-diiodide-1-propene
25
 Applications (Contd)
e.g.3 leaving gro
Cl
H2O or EtOH
H2C C CHCH3 H2C C CHCH3
H SN1 H
O H
Et
o r
O H2C C CHCH3
H2 H
OH
H2C C CHCH3
H OH
OR H2C CH CHCH3

OEt
OR
H2C C CHCH3
H OEt

OET = ch3-ch2-0- (( ethoxy )) H2C CH CHCH3

Major 26
 Reactions (Contd) alpha carbon (Cα) in organic molecules
refers to the first carbon atom that attaches
III- Elimination reaction: to a functional group, such as a carbonyl .
The second carbon atom is called the beta carbon
Dehydrohalogenation of alkyl halide
H
  alc. KOH /  _
C C + B: C C + BH + X

X can proceed through

E1 OR E2

Dehalogenation of vicinal dihalide

Br acetic acid
Zn / HOAc
C C C C HC C
H NaI / acetone
Br 27
 • Bimolecular Elimination Reaction (E2)

Br
EtOH CH2=CHCH3
H3C C CH3 + NaOEt
H propylene

Mechanism

H H H
CH3 EtO H CH3 H H
EtO slow fast
C C C C C C
H H H Br H CH3
H Br

Rate-determining step + EtOH
-
+ Br
28
 • Unimolecular Elimination Reaction (E1)

CH3
H2O
H3C C Br H3C C CH2 + H3O+
here we have heat supply
CH3 CH3
Mechanism slow bec we are waiting a carbocation to be formed


H3C H3C H3C H H3C H OH2
  + H2O  H
C Br C Br C C H
H3C Slow Fast C C
CH3 H3C CH3 H3C H
T.S.1 H3C H

H3C T.S.2
H
H3O+ + C C
H3C H 29