Organic Reactions
S D Samant
Institute of Chemical Technology, Mumbai
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To understand organic chemistry it is necessary to know:
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Formation of molecule
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ATOM Nucleus (p+n)
Overlap
B
Molecular orbitals
(Mos)
Bond formation (ionic , covalent , coordinate )
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MOLECULE
MOLECULE + MOLECULE
Homolytic Heterolytic D
REACTION MECHANISM
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Atoms Molecule
Nuclei Framework
Electrons Orbitals
Reaction
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Atomic structure
versus
Molecular structure
AO vs MO
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n A.O.s n M.O.s
(s,p,d,f )
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Approximations
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Electronic Structure
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How is a CHEMICAL BOND formed?
Ionic bond
Covalent bond
Coordinate bond
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Hybridization
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FMO
LUMO (acceptor orbital ) Nu
-------------------
HOMO (donor orbital) E
Important orbital
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FMOs in :
Simple reactions
Pericyclic reactions
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ORGANIC REACTION MECHANISM
Desired reaction :
Reactant T, Catalyst, solvent Product
Reaction Mechanism
TESTING
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Mechanism
confirmed
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Important Symbols describing
Reaction Mechnaism
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Irreversible reaction to product
Reaction which does not processd
Forward & Backward reaction
Reaction with more than one step
Reversible reaction
Reversible reaction ; Equilibrium favours products
Indication of resonance
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Direction of
migration
Curly Arrow
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Using Curved Arrows in Polar Reaction Mechanisms
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Rules for Using Curved Arrows
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The electrophilic site can be neutral or positively charged
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Examination of a molecule
with respect to its electronic
structure
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Formal charge
Formal charge =
Valence electrons (1/2 bonding e- s + All lone pair e-s)
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Polarization effect Inductive effect
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Polarizability
It starts out neutral but when the right atom or molecule comes close
it becomes partial positive or partial negative.
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Polarization - change in electron distribution as a response to change in
electronic nature of the surroundings
Polarizability is the tendency to undergo polarization
Polar reactions occur between regions of high electron density and regions
of low electron density
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Resonance
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Resonance Structures
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Drawing of resonance structures
Electrons move
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Each resonance structure
contributes to some extent to
the actual structure of the
molecule
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Why do Organic
Reactions Happen?
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Energy change = Coulombic interaction + Orbital interaction
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How do the organic reactions occur: Mechanism
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Steps in Mechanisms
When several steps occur at the same time they are said to be
concerted
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Understanding unit steps
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Energy Frofile Diagram
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For the general reaction:
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Consider the following two step reaction:
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Ea is the energy barrier that must be exceeded for reactants to be
converted to products.
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Describing a Reaction: Intermediates
If a reaction occurs in more than one step, it must involve species that
are neither the reactant nor the final product
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Acids and Bases
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An electrophile
is electron-loving
is an electron-poor species
can form a bond by accepting a pair of electrons
may be either neutral or positively charged
is a Lewis acid
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A nucleophile
is nucleus-loving
is an electron-rich species
can form a bond by donating a pair of electrons
may be either neutral or negatively charged
is a Lewis base
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Generalized Polar Reactions
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Ambident Nucleophiles
O N O O N O (NO2)
O N O (NO2)
O N O
H2 C C O H2 C C O (enolate)
o o o
o o
(phenolate ion)
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Some species can act as an electrophile or a nucleophile
depending on the circumstances
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Bond Breaking
in anticipation of better bonds
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Types of Steps in Reaction Mechanisms
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General C-X Bond Breaking processes
C X
C X
Carbenium ion
C X C X C X
Carbanion
C X C X
Radical
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C X C X X Leaving group
Self dissociation
OR
C X + Z C XZ C XZ
assisted dissociation
Y C C Y C C
Addition
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Intermediates
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Structures
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General principles of stability:
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RADICAL REACTION
A] Propagation processes :
1) Abstraction . .
R + HC RH + C
2) Addition . .
R + C=C RCC
3) Decompostion .
RC=O R + O= C=O
.O
. .. .
R + Mol R + Mol
. ..
R Mol + R
B] Termination process :
1) Combination : . .
R + R RR
2) Disproportion : . . ..
R Mol + Mol
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C] Rearrangements : Not common
Characteristics
* Susceptible to radicals
* Chain mechanisms
* Conc. Of radicals is low
- Termination processes less frequent
- termination process have negligible E act
* Susceptible to inhibitors
* Ionic mechanism may compete.
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General Reaction of Free Radicals
Propagation processes Termination processes
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Radical Reactions
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Steps in Radical Substitution
Steps F Cl Br I
. .
X X X + X +150.6 +242.7 +188.3 +150.6
. .
X + CH4 CH3 + HX -146.4 -12.55 +50.21 +117.2
. .
CH3 + X2 H3C X +X -334.7 -83.68 -96.23 -62.76
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Act. E : . .
Cl + CH4 CH3 + HCl 16.11 Kj
. .
CH3 + Cl2 CH3Cl + Cl < 21 kj
Alternative mechanism :
. .
Cl + CH4 H3C-- Cl +H
. .
H + Cl2 HCl + Cl
(77)
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Radical addition to (C=C)
R + HX R H + X
+ HX
X bond
Radicals always attack less substituted (terminal) carbon atom of a double
H
+ HX X
X X
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X in HX F Cl Br I
(Kcal/mol)
-45 -26 -5 +7
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General Reaction of Carbenion Ion
Nucleophilic Elimination Rearrangement Additon to
attack of H+ from (common) C=C
C+ + : Nu position less stable (C+ ) C+ + C=C
H
C Nu C C+ more stable (C+ ) CCC+
C=C Wagner
olefins Meerwein
SN 1 (II)
AE1 (II) E1
(A) (B) (C) (D)
A or B A or B D
(polymn)
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CARBOCATION
Carbanion
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Self Dissociation:
K1
R-Cl R+Cl - ionization
* Stereochemical outcome:
Nu Nu
Nu-R R+ 80
R-Nu
PROTONATION PROCESSES
1. Protonation of alchols :
H
k1 R O protonium ion
R OH + H
H
k2 R OH2
R OH 2
k3
R OH2 R + H2O dissociation
2. Protonation of ethers :
+
k1
R O R +H R O R
H
+ +
k2 R HO R
R O R
H
+ +
R HO R R + HO R
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3. Protonation of a carbonyl group :
R R
C O + H C OH
R R
R R
C OH C OH
R R
R S R + H R S R
H
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5. Protonation of an olefin :
R C C R1 + H R C C R1
H H
H H H
H H2 H2 H
R C C R1 R C C R1 + R C C R1
H H
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An Example of a Polar Reaction: Addition of HBr to Ethylene
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First Step in Addition
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* With Acid halide:
O +O: AlCl3 -
.. AlCl3 ..
R Cl : + R Cl:
.. ..
R Cl: R Cl:
..
O O : -AlCl3
+ 86
R O R
+
Complexation of alkyl halide with a Lewis acid
+
.. -
.. K1
R-Cl : + AlCl3 R-Cl-AlCl3
.. ..
Complex
+ -
.. K2
R-Cl-AlCl3 R+(AlCl4)-
.. tight ion pair
K3 , solvent
R+(AlCl4)- R+ (AlCl4)-
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General Raction of Carbanion
At C=C At C=O
polymerisation Tetrahedral mechanism
(Anionic) (Aldol type reaction)
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T etrahedral Mechanism:
O O
+
-
Cl ?
+ -OH
R Cl R OH
(SN 2 type)
(a) O O-
+ -
R X Nu R Nu
X SP 3
tetrahedral
-
O O
SP2
R Nu R Nu
X
Planar
Substitution
Nu= -OH, H 2O, NH3 , R-NH2
O- OH
+ H+
R Nu R Nu
X X
X= H, akyl , NH 2
Addition
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ELECTRON BOOK KEEPING
Homogenic bond f ormations
H
(1) CH3-O-CH3 + H CH3-O-CH3