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• 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
R C X R C X R C X
H H R
1O 2O 3O
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
CH3
Br
Cl
F2 – explosive
Cl2/Br2 – diffused light or heat
I2 - unreactive
H
HBr
R C CH2 R C CH2Br Anti-Markovnikov addition
H peroxide H
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
δ+
δ−
X
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
slow
Me Me
HO S Pr Pr R OH
(CH3)2HC X Rate
increase
(CH3)3C X
107
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]
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
H3C
HO I
H Et
CH3CH2 X Rate
decrease
(CH3)2HC X
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.
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
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
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
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