Functional Group Chemistry

• 11 Lectures
• Organic Chemistry By T. W. G. Solomons
• For success
(i) Understand concepts
(ii) memorize
Functional Group
An atom or a combined group of atoms which
impart specific chemical properties to organic
compounds
O

CH3CH2 OH CH3CH2C OH
C3H6O2
C2H6O O
CH3 O CH3
CH3 C OCH3
 Functional Group chemistry to be considered
• Alkyl Halides R CH2 X ( X = Br, F, Cl, I)

• Organometallic compounds
-Grignard Reagents RCH3 Mg X

Carbonyl Compounds O

- Aldehydes R C H

O
- Ketones
R C R

Carboxylic Acids O

R C OH

• Carboxylic acid Derivatives

• Amines
•Aromatic compounds
 ALKYL HALIDES
Structure
The alkyl halides are those compounds having a halogen
attached directly to the carbon of an alkyl group.
R CH2 X ( X = I, Br. Cl, F)
R CH2 X

F o rm ed b y o v erlap o f a carb o n sp 3 h y b rid ized o rb ital w ith a

h alo g en o rb ital

The H C X bond angle is near 109o Therefore the structure assumes a

teteahedral geometry

Halomethanes Bond length(Ao) Diss. Energy(kcal/mol)

CH3F 1.39 109
CH3Cl 1.78 84
CH3Br 1.93 70
CH3I 2.14 56
CLASSIFICATION
Classify according to the number of carbon atoms (alkyl
groups) attached to the carbon bearing the halogen.
H R R

R C X R C X R C X

H H R
1O 2O 3O

-they undergo the same kind of reactions but differ in their

rates of reaction.

Nomenclature
Alkane in which a hydrogen atom is replaced by a halogen.
The name is prefixed by the halogen attached.
CH3CH2CH2 Br
CH3CH2 CH CH3
bromopropane (1o)
Cl 2-chlorobutane (2o)
 CH3 CH3

H 3C C CH3 H 3C C CH2Cl

I CH3

2-iodo-2-methylpropane (3o) 1-chloro-2,2-dimethylpropane (1o)

CH3
Br

Cl

bromocyclopentane 1-chloro-3-methylcyclohexane (2o)

 PREPARATION

(i) Free radical halogenation of alkanes

Br
hν
R CH CH3 + Br2 R C CH3 + R CH CH2Br
or
∆ CH3
CH3 CH3
major (3o) minor (1o)

F2 – explosive
Cl2/Br2 – diffused light or heat
I2 - unreactive

Limitations: gives several products.

(ii) Addition of hydrogen halide to C-C multiple bonds
Br
HBr
R C CH2 R C CH3
Markovnikov addition
H H

H
HBr
R C CH2 R C CH2Br Anti-Markovnikov addition
H peroxide H

(iii) Nucleophilic substitution of alcohols

PBr3
(a) 3 RCH2 OH 3 RCH2 Br + P(OH)3

PCl5
(b) RCH2 OH RCH2 Cl + P(O)Cl3 + HCl

(c) HCl
RCH2 OH RCH2 Cl + H2O

SOCl2
(d) RCH2 OH RCH2 Cl + SO2 + HCl
 REACTIONS

Alkyl halides can undergo a number of important reactions.

• Since the halogen atom is more electronegative than carbon,
the carbon-halogen bond of the alkyl halide is polarized, hence
the carbon bears a partial +ve charge and the halogen atom a
partial –ve charge.

δ+
δ−
X

Nucleophilic Substitution (SN)

The carbon bearing the halogen is susceptible to attack by
groups carrying a lone pair of electrons.
The halogen will be substituted by such a group.
R CH2 X + Nu R CH2 Nu + x

There are two types of Nucleophilic Substitutions (SN)

SN1 SN2
Substitution nucleophilic Substitution nucleophilic
unimolecular bimolecular
(the rate determining, r.d.s., step entails (the rate determining step entails two
one molecule) species)
 Substitution nucleophilic unimolecular

CH3 CH3
H2O
H3C C I + OH H3C C OH + I
EtOH
CH3 CH3

30

Studies show that the rate of the reaction is dependent only on concentration
the alkyl halide

Rate α [tBuI]

Rate = t
κ[ BuI] unimolecular SN1
 Mechanism
In the first step, R-X dissociates, forming a carbocation, R⊕, and the leaving group X-. This is a
slow, rate determining step (r.d.s.) and entails only one species, R-X.
(i)
CH3 CH3
slow
H3C C I H3C C + I
RDS
CH3 CH3
carbocation

(ii) In the second step the carbocation and the nucleophile combine. This occurs rapidly.

CH3 CH3
fast
H3C C H3C C OH

CH3 OH CH3
 Stereochemistry
Et

The alkyl halide dissociates, in Chiral (R)

a slow r.d.s. to a 3o carbocation Me Optically active
Pr Br

slow

The positively charged carbon Et

in a carbocation is sp2
OH
hybridized and carbocations HO Me Pr A nucleophile, HO-, can
have trigonal geometry. add from either side of
the carbocation to give
two enantiomers in
equal amounts .
Et Et

Me Me
HO S Pr Pr R OH

Optically inactive (RACEMISATION)

 SN1 REACTIONS – OTHER CONSIDERATIONS

• RCH2X which form stable carbocation will undergo SN1

reactions and the reaction rates increases with increasing
carbocation stability.
H 3C X 1

(CH3)2HC X Rate
increase
(CH3)3C X
107

• SN1 reactions are very sensitive to solvent effects because the

transition state involves a carbocation (stabalize via dipolar
interactions). R +
R X X

ie. if solvent is able to pull equilibrium to the right then

the rate of the SN1 reaction will be accelerated.
(a) polar
(b) protic
eg. H2O, CH3OH
• Secondary alkyl halides that undergo SN1 reactions can give
rearranged products.. CH OCH 3 3

CH3 C C CH3
H
CH3 Br CH3
A (4%)
CH3 C C CH3 + CH3OH
H
CH3 CH3O CH3

CH3 C C CH3
H
slow
R.D.S. CH3
B (41%)
CH3
CH3O H
CH3 C C CH3 A
H (fast)
CH3
20
rearrangement

CH3
CH3O H
CH3 C C CH3 B
H (fast)
30 CH3
 Bimolecular nucleophilic Substitution (SN2

H2O
H3C I + OH H3C OH + I
EtOH

10

Studies show that the rate of the reaction is dependent on both the concentrations
of the alkyl halide and nucleophile.

Rate α -
[ OH][CH 3I]

Rate = κ[-OH][CH3I] bimolecular

SN2
 Mechanism
H3C H3C

RDS
HO I
H
Et I
HO H Et

Transition state
The nucleophile and the alkyl halide combine to form a
pentacoordinate transition state. This is the slow rate
determining step (r.d.s); it entails two species, R-X fast
and Nu-. The dotted lines indicate partially formed or
partially broken covalent bonds.

CH3

I +
H
HO Et
The pentacoordinate transition state dissociates to form
the product, Nu-R, and the halide ion (the leaving
group).
 Stereochemistry
H3C

The nucleophile attacks the

substrate from the side H
Optically active (R)
opposite to the leaving group. Et I
HO

H3C

HO I

H Et

The stereochemistry of the product CH3

is INVERTED relative to that of the
starting material.
H (S)
HO Et

Optically active (INVERSION OF CONFIGURATION)

 SN2 REACTIONS – OTHER CONSIDERATIONS

• Since SN2 reactions involves a transition state with a

pentacoordinate carbon, sterically hindered RCH2X do not
react via this mechanism.
H3C X 2 x 106

CH3CH2 X Rate
decrease
(CH3)2HC X

Tertiary alkyl halides do not undergo SN2 reactions

• Because the mechanism is bimolecular, more effective

nucleophiles will accelerate the reaction.

Reaction rate H 3C Br + CN CH 3Br + OR CH 3Br + OH

 SN2 reactions are less dependent on solvent so solvents used are
usually polar aprotic

eg. DMF, DMSO, CH3COCH3

The rate of SN2 reactions (involving negatively charged nucleophiles increases

when the reactions are carried out in polar aprotic solvents.

• No rearrangement is possible for the SN2 mechanism

 REVIEW

Summary SN1 SN2

Rate R = k[RX] R = k[RX][nu]
Stereochemistry racemisation inversion
Alkyl enhanced decreased
substituent
Solvent polar protic Polar aprotic
Rearrangement possible Not possible
 Elimination Reaction
When alkyl halides are boiled with ethanolic hydroxide,
alkenes are obtained.
EtOH
eg. CH3CH2CH2Br + KOH CH3HC CH2 + KBr + H2O
heat
1,2 or β-elimination

The elements of H-X are lost from neighboring carbon atoms and a C=C is
formed. The halogen atom is lost from the α carbon, and the hydrogen from
the β carbons.

Two important elimination mechanisms which operates

with alkyl halides.

E1 E2
Unimolecular mechanism Bimolecular Mechanism
Unimolecular
H R
R
-HX R
B + R C C R C C
β α
R R
R X

Rate α [HX]
Rate = κ[HX]
H R R R
slow
(a) R
β
C αC R HC C X
R.D.S.
R X R R

H R
R
fast R
(b) B + R C αC C C + BH
β
R R
R R
Mechanism

CH3
CH3
EtOH/H2O H
eg. H3C C Br C C
KOH
H CH3
CH3

H CH3 H CH3
(a) slow
H C αC CH3 H C C Br
β
R.D.S.
H Br H CH3

H CH3
CH3
fast H
(b) EtO + H C αC C C
β
CH3 H CH3
H
Bimolecular Elimination (E2)
H R
R
-HX R
B + R C C R C C
β α
R R
R X

-
Rate α [RX][B ]
-
Rate = κ[RX][B ]
Mechanism
H R
R
R
+ C C + BH + X
B R C Cα R
β
R R
R X

(i) Concerted Rxn

(ii) The two groups being eliminated are trans (anti) to

each other.
E1 & E2 Reaction conditions
(1) Two possible products for many alkyl halides

H CH3

H C C CH2CH3

H Br

E1

CH3 H CH3
H3C CH2CH3
H
C C C C
H C C CH2CH3
H3C H H CH3
H
zaytzeff product Hofman product
 B B
H CH3 H

H 3C C C C H

H Br H

E2
CH3 CH3

CH3CH C CH3 H3CH3CHC CH2

Zaytzeff prouct Hofmann product
(ii) If the base is extremely bulky (or large) eg (CH3)3CO-,
then the proportion of the Hofmann product can be increased.
Me

KO C Me
H CH H
β 3 CH(CH3)2
Me H
H3C C C C
β αC β
C H
H CH3
CH3 Br H
Hofman product

(iii) If the hydrogen on the β-carbon (whose elimination

leads to the Saytzeff product) is very crowded then the
proportion of the Hofmann product can be high.
CH3 H Br H CH3 H
CH2
β
H3C C C C C H H3C C C C
β
OEt CH3
CH3 H CH H CH3 H
β 3
(iv) For both E1 and E2 mechanisms.
Rate : 3o RX 2o RX 1o RX
(does'nt undergo E1)

Summary E1 E2
Base Weak base Strong base
will work
Solvent Good ionising Wide variety
solvent
Substrate 3o > 2o 3o> 2o > 1o
Kinetics R = k[RX] R = k[RX][B-]
Rearrangement common Not possible
Conditions for elimination reactions are quite similar to those
for substitution reactions.
• It is not easy to control SN1 vs E1
• It’s easier to optimise conditions to favour E2 in preference
to SN2

Generally elimination is favoured by:

(i) Strong base
(ii) High temperature
(iii) Relatively non polar solvents eg. EtOH vs H2O