Halogeno-compounds

Chapter 33
 Structures

Halogenoalkanes: X bond to sp3 carbon

H R R
R C H R C H R C R

X X X
1o Primary 2o Secondary 3o Tertiary
 Structures

Halobenzene: X bond to benzene, sp2 carbon

X
Reactions of Halogenoalkanes

Two major types:

•Nucleophilic Substitution (SN)

•Elimination (E)
Nucleophilic Substitution (SN)

H :Nu-
R Cδ+ H
•Polar C-X bond
Xδ-
•Cδ+ is attacked by :Nu-

H •C-X bond is broken to

R C H + X- give out X-
Nu
 Bimolecular Nucleophilic
Substitution (SN2)
H H -
HO -

Cδ+ Brδ- HO C Br
H
CH3 H CH
3
H

HO C H + Br-
CH3

If C is chiral, completed stereochemical inversion.

Bimolecular Nucleophilic
Substitution (SN2)
H -
HO C Br
H CH
3

OH- + CH3CH2Br CH3CH2OH + Br-

Rate law: Rate = k [OH-][CH3CH2Br]

(Bimolecular, 2nd order)
 Unimolecular Nucleophilic
Substitution (SN1)
R R

Cδ+ Brδ-  C+ + Br-

R (rds) R R
R (sp , trigonal planar)
2

R
R
C+ -H+
+ H2O: C OH
R R R
R
Unimolecular Nucleophilic
Substitution (SN1)
R3C---Br R3C---OH2+

R3C+ + Br- + H2O

R3C-Br + H2O: R3C-OH + HBr

Rate law: rate = k [R3CBr]

(1st order, Unimolecular)
Relative rates of SN1 and SN2

Compound S N1 SN 2

CH3X 1 30

CH3CH2X 1.6 1

(CH3)2CHX 32 0.2

(CH3)3CX 107 0.00001

Factors affecting relative rates

Structure - Steric Factor

The size of atoms or groups at/near the

reactive site affects SN2.

Bulky groups (-R) at the C-X site slow

down SN2 reaction.
Factors affecting relative rates

Structure - Stability of carbocation

R3C+ > R2CH+ > RCH2+ > CH3+

(R group is e- donating)

Stable carbocation favours SN1 mechanism.

 Factors affecting relative rates
(By electronic factor)
SN 1 Inc. stability of carbocation

R3C-X R2CH-X RCH2-X CH3-X

(3o) (2o) (1o) (methyl)
SN 2
Inc. easy of access (By steric factor)
Factors affecting relative rates

Effect of nucleophile

SN2 Strength and concentration have effect

RO:- > :OH- > ROH > H2O:

SN1 No effect
Factors affecting relative rates

Effect of leaving groups

•Relative rate of substitution

C-I > C-Br > C-Cl
•Explanation : Bond energy
C-I 238 C-Br 276 C-Cl 338

(*exp.1 p.235)
Factors affecting relative rates

Effect of solvent:

•Polar solvent stabilize the carbocation

and hence favour SN1 reaction

•Increase in polarity:
CH3COCH3 << R-OH < H2O
 Synthetic applications

Nitrile Formation
ethanol, reflux
R-Br + KCN  R-CN + KBr
H+ 1.LiAlH4
R-CN  RCOOH  RCH2OH
2.H2O

(Increase carbon chain length by one carbon)

Synthetic applications
Formation of C-O bond

R-Br + NaOH → ROH

R-Br + RO-Na+ → ROR

Formation of amine

RI + NH3 → R-NH2
 Elimination

H H H H
H C C H H C C H
H X
HO: -
+ H2O + X-
Competition between SN and E

H H
H C C H
H X
E SN
Nu:-

Good Nu:- are also good B:-

(SN always competes with E)
 Conditions favour E

• Highly substituted haloalkanes is more

likely to undergo elimination (Steric Effect)

Favor SN

3oRX 2oRX 1oRX

Favor E
 Conditions favour E

2. Use less polar solvent

e.g. 75% ethanol + 25% water is better than
25% ethanol + 75% water

Polar solvent favors the formation of highly

concentrated charged particles.

T.S. of SN2 reaction is Nuδ-….R….Xδ- is

more concentrated than Nuδ-…H – C - C….Xδ-
 Conditions favour E

3. Higher temperature and prolonged

refluxing
Breaking of C-H bond and C-X bonds
require greater Activation Energy.

45oC (47%)
(53%)
NaOH
CH3CHBrCH3 CH3CH=CH2 + (CH3)2CH-OC2H5
C2H5OH, H2O 100oC (or OH)
(64%) (36%)
 Conditions favour E

4. Stronger base: RO- > ROH

CH3 C2H5OH
(19%)
25oC
CH3 C Br (CH3)2C=CH2
CH3 (93%)
C2H5O /C2H5OH
-
 Applications of Elimination

Preparation of Alkenes
e.g.
C2H5O-Na+/C2H5OH
C2H5Br → C2H5OC2H5 + CH2=CH2
heat 99% 1%

C2H5O-Na+/C2H5OH
(CH3 )2CHBr → C2H5OCH(CH3)2 + CH2=CHCH3
heat 21% 79%
Applications of Elimination

Preparation of Alkenes
e.g.
C2H5O-Na+/C2H5OH
(CH3)3CBr → (CH3)2C =CH2
heat 100%
Applications of Elimination

Preparation of Alkynes
e.g.
Br2
CH3CH=CHCH3 → CH3CHBrCHBrCH3

C2H5O-Na+/C2H5OH
→ CH3C≡CCH3
heat
Uses of Halogeno-compounds

Please refer to Section 33.6 on p.253