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MESOMERIC EFFECT/RESONANCE EFFECT
Q. Compare +M effect order:
(1)
(2)
(3)
(4)
Internal Resonance
MESOMERIC EFFECT/RESONANCE EFFECT
Q. Compare M effect order :
(1)
MESOMERIC EFFECT & INDUCTIVE EFFECT
Summary of M Effect and I effect
+M Atom/group directly attached to conjugate system has
lone pair/negative charge.
Atom/group directly attached to conjugate system has
-M polar bond or positive charge(vacant orbital).
+I Negatively charged > alkyl group > T,D,H
CH3
CH2> NH> O> C O> C CH3> CH CH3 > CH2 CH3 > CT3 > CD3 > CH3
O CH3 CH3
-I Positively charged > partial positive > neutral
2 2 3 3 2
> X ( F > Cl > Br > I) >
OR > OH > C CH > NH2 > > CH=CH2
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HYPERCONJUGATION EFFECT
Note :
1.Hyperconjugation is distance independent effect.
2.It is a permanent effect
3.Generally,It is more dominant than inductive effect but less
dominant than mesomeric /resonance effect
4. Inductive effect order CT3 > CD3 > CH3
But H-effect order CH3 > CD3 > CT3
Bond strength: C T> C D> C H
HYPERCONJUGATION EFFECT
5. I effect order :
H effect order :
Q. In which of the following case electron density on the ring will be maximum?
APPLICATIONS OF H-EFFECT
1. Stability of alkene
Isobutylene trans-but-2-ene cis-but-2-ene
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STABILITY OF ALKENE
Q.
Q.
Q. Conjugated alkadiene
Cumulated alkadiene
Isolated alkadiene
HEAT OF HYDROGENATION (HOH)
Amount of heat released during complete hydrogenation of 1 mole of unsaturated
hydrocarbon in the presence of a metal catalyst.
HEAT OF HYDROGENATION (HOH)
Compare HOH
Q. (A) (B)
Q. (A) (B)
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HEAT OF HYDROGENATION (HOH)
(A) (B)
Q.
Q. (A) (B) (C) (D)
Discussion of Home Work (HOH)
(A) (B)
Q. Stability : B > A
HOH : A > B
Cis Trans
Q. (A) (B) (C) (D)
10 -H 6 -H 3 -H 4 -H
Stability : A > B > D > C
HOH : C > D > B > A
HEAT OF HYDROGENATION (HOH)
Q. (A) (B) (C)
(A) (B) (C)
Q.
Expected order:
H (kJ/mol) -120 -232 -208
Actual order:
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HEAT OF HYDROGENATION (HOH)
Q. If heat of hydrogenation of 1-Butene is 30 kcal then what will be heat of
hydrogenation (HOH) for Buta-1,3-diene ?
(1) 29 (2) 30 (3) 60 (4) 57
HEAT OF COMBUSTION (HOC)
The amount of heat released when 1 mole of a given compound is completely
burnt in the presence of excess of O2 .
HEAT OF COMBUSTION (HOC)
Q. (A) (B) (C) (D)
Q. (A) (B) (C) (D)
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RESONANCE ENERGY
The energy difference between most stable resonating structure and resonance
hybrid is known as resonance energy.
Resonance hybrid is more stable than any of its resonating structures.
RESONANCE ENERGY
NOTE: Resonance energy depends on extent of conjugation.
(A) (B)
NOTE: If extent of conjugation is same then check stabilization by resonance.
(A) (B)
RESONANCE ENERGY
(A) (B)
(A) (B)
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RESONANCE ENERGY
(A) (B) (C) (D)
Benzene Naphthalene Anthracene
Phenanthrene
2 R.S. 3 R.S. 4 R.S. 5 R.S.
36 61 83 91
(Kcal/mol)
(A) CH2 = CH F (B) CH2 = CH Cl
RESONANCE ENERGY
(A) (B)
Extended conjugation Cross conjugation
Extended conjugation Cross conjugation
According to Bredt's rule, planarity cannot be achieved at bridge head position
(cannot be sp2) in bridged bicyclic compound unless one of the rings contain at least
8 carbon atoms.
Two rings share more
than 2 atoms.
Fused bicyclic compound Bridged bicyclic compound
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Applications:
Q. Compare stability of carbocation:
Q. What is the hybridization of nitrogen in the given structure?
Q. In which of the following compounds hyperconjugation is possible?
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STABILITY OF CARBOCATION
(A) (B) (C)
(A) (B) (C) (D)
STABILITY OF CARBOCATION
(A) (B) (C)
(A) (B) (C)
STABILITY OF CARBOCATION
(A) (B) (C)
(A) (B) (C)
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STABILITY OF CARBOCATION
(A) (B) (C)
(A) (B) (C)
STABILITY OF CARBOCATION
STABILITY OF CARBOCATION
(A) (B) (C)
(A) (B)
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STABILITY OF CARBOCATION
(A) (B) (C)
Cyclopropyl methyl carbocation
(CPM)
Bent bond.
STABILITY OF CARBOCATION
Cyclopropyl methylcarbocation
(CPM)
STABILITY OF CARBOCATION
Stability of Benzyl Carbocation
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STABILITY OF CARBOCATION
Ortho: M/H/I Para: M/H/I
If a group is present at meta position it can stabilize or destabilize
the carbocation through its I effect only.
STABILITY OF CARBOCATION
(A) (B) (C) (D)
(A) (B) (C) (D)
STABILITY OF CARBOCATION
(A) (B) (C) (D)
(A) (B) (C) (D)
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STABILITY OF CARBOCATION
(A) (B) (C) (D)
(A) (B) (C) (D)
STABILITY OF CARBOCATION
(A) (B) (C) (D)
Inductive effect CT3 > CD3 > CH3
H-effect order CH3 > CD3 > CT3
APPLICATION OF ELECTRONIC EFFECTS
2.STABILITY OF CARBON FREE RADICAL
(A) (B) (C) (D)
(A) (B) (C) (D)
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BOND DISSOCIATION ENERGY (B.D.E.)
It is the energy required to break a bond homolytically.
Q. For homolysis of C H bond compare bond dissociation energy
BOND DISSOCIATION ENERGY (B.D.E.)
STABILITY ORDER
B.D.E.
jjjjjjjjjj
jjjjjjjjjj
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APPLICATION OF ELECTRONIC EFFECTS
3. STABILITY OF ANION
Generally,
EN / Size > Resonance > Effects (M, H, I)
EN: Negative on more electronegative atom is more stable across the period.
Size: Negative on bigger size is more stable down the group.
Resonance: 1.Extent of resonance.
2.Quality of resonance.
STABILITY OF ANION
(A) (B) (C)
(A) (B)
(A) (B)
STABILITY OF ANION
(A) (B) (C)
(A) (B)
Phenoxide ion Carboxylate ion
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STABILITY OF ANION
(A) (B) (C) (D)
(A) (B) (C) (D)
STABILITY OF ANION
(A) (B) (C) (D)
STABILITY OF ANION
(A) (B) (C)
(A) (B)
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ACIDIC STRENGTH
Acids are substances which can donate H
HA(aq) H (aq) + A (aq)
[H ] [ A ]
Ka
[HA]
Acidic strength stability of conjugate base
Stronger the acid, weaker its conjugate base
ACIDIC STRENGTH
(A) (B) (C) (D)
ACIDIC STRENGTH
(A) (B) (C)
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ACIDIC STRENGTH
(A) (B) (C)
Pka: 3.77 4.21 4.76
NOTE: but
ACIDIC STRENGTH
ACIDIC STRENGTH OF PHENOL & SUBSTITUTED PHENOL
OH
(A) (B)
Phenol Cyclohexanol
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ACIDIC STRENGTH OF PHENOL & SUBSTITUTED PHENOL
(A) (B) (C) (D)
OH
(A) CH 3 (B) (C) (D)
ACIDIC STRENGTH OF PHENOL & SUBSTITUTED PHENOL
(A) (B) (C) (D)
Expected order:
Actual order:
(A) (B) (C)
ACIDIC STRENGTH OF PHENOL & SUBSTITUTED PHENOL
OH
(A) (B) (C)
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BENZOIC ACID & SUBSTITUTED BENZOIC ACIDS
ORTHO EFFECT
Generally ortho substituted benzoic acids are stronger acids than benzoic acids and
it is also more acidic than its meta and para isomers.
BENZOIC ACID & SUBSTITUTED BENZOIC ACIDS
Ortho effect due to S.I.R.
Resonance between ring
and COOH group almost
stops due to S.I.R. effect.
BENZOIC ACID & SUBSTITUTED BENZOIC ACIDS
(A) (B) (C) (D)
(A) (B) (C) (D)
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BENZOIC ACID & SUBSTITUTED BENZOIC ACIDS
(A) (B) (C)
2,5-Dihydroxybenzoic 2-Hydroxybenzoic acid
acid (Salicylic acid)
ACIDIC STRENGTH
Q. Arrange the following in decreasing order of acidic strength.
ACIDIC STRENGTH
(A) (B)
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ACIDIC STRENGTH ORDER
Picric acid
ACIDIC STRENGTH ORDER
Q. Arrange in acidic strength order of provided groups (x, y, z) ?
FEASIBILITY OF ACID-BASE REACTION
An acid-base reaction will be feasible, if it goes from strong acid to weak acid.
OH ONa
+ NaOH + H 2O
NOTE: Reaction with NaOH is feasible if acidic strength of acid is more
than H2O.
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FEASIBILITY OF ACID-BASE REACTION
CH3COOH + NaHCO3 H2CO3 + CH3COONa
Note:
1.Reaction with NaHCO3 is feasible if acidic strength off acid is more than H2CO3.
2.'C' of CO2 comes from NaHCO3.
3.Acids which are more acidic than H2CO3 are soluble in aqueous NaHCO3 due to salt
formation.
Q. Which of the following in not soluble in sodium hydrogen carbonate(NaHCO3)?
Picric acid Benzoic acid Phenol
Q. Can phenol and benzoic acid be distinguished using sodium bicarbonate?
FEASIBILITY OF ACID-BASE REACTION
HC CH + NaNH2 NH3 + HC CNa
NOTE: Reaction with NaNH2 is feasible if acidic strength of acid is more
than NH3.
FEASIBILITY OF ACID-BASE REACTION
Note:
Amines, ammonia and those compounds which are more acidic than ammonia can
produce hydrogen gas on treatment with sodium.
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FEASIBILITY OF ACID-BASE REACTION
Q. In which of following cases reaction is feasible?
Compound NaOH NaHCO3 NaNH2
HC CH
CH3 CH2 OH
Ph OH
Ph COOH
BASIC STRENGTH
Base Species which can share lone pair of electron to H+
Basic Strength Stability of conjugate acid
ability to donate electron
Generally,
(Guanidine) (Amidine) ( )
BASIC STRENGTH
3 equivalent resonating structures
Conjugate acid stable
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BASIC STRENGTH COMPARISON
(A) (B) (C)
(A) (B) (C)
BASIC STRENGTH COMPARISON
(A) (B) (C) (D)
BASIC STRENGTH COMPARISON
(A) CH3 NH2 (B) (C) (D)
Ph-CH2NH2 p-CH3O-C6H4-NH2 m-CH3O-C6H4-NH2
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BASIC STRENGTH COMPARISON
(A) (B)
(A) (B) (C) (D)
Compound which is most difficult to protonate?
BASIC STRENGTH COMPARISON
(A) Ph3N (B) Ph2NH (C) PhNH2 (D) PhCH2NH2
Diphenyl amine Aniline Benzyl amine
(A) (B)
STERIC INHIBITION OF PROTONATION (S.I.P.)
Difficulty in protonation by Bulky group (BG) is called as Steric Inhibition of
Protonation (S.I.P.).
SIP effect is observed in Ortho substituted aniline.
Ortho substituted aniline is less basic than aniline due to Steric Inhibition
of Protonation (S.I.P.)
N H2
BG
+ H
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BASIC STRENGTH
(A) (B) (C) (D)
o-Toluidine m-Toluidine
p-Toluidine
(A) (B) (C)
BOND LENGTH COMPARISON
Q. Compare the mentioned bond lengths
Note: In equivalent resonating structures, the same nature bonds
participating in resonance are equal in length.
BOND LENGTH COMPARISON
NOTE: If a single bond gets double bond character due to resonance then bond length
will be shorter.
Remember: Bond length order
Pure SB > SB (less reso) > SB (more reso) > DB (more reso) > DB (less reso) > pure DB
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BOND LENGTH COMPARISON
NOTE: If a double bond gets single bond character due to resonance then bond length
will be longer.
Remember: Bond length order
Pure SB > SB (less reso) > SB (more reso) > DB (more reso) > DB (less reso) > pure DB
BOND LENGTH COMPARISON
Remember: Bond length order
Pure SB > SB (less reso) > SB (more reso) > DB (more reso) > DB (less reso) > pure DB
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BOND LENGTH COMPARISON
Compare C1-C2 and C2 C3 bond length in Naphthalene
BOND LENGTH COMPARISON
NOTE: Due to hyperconjugation the double bond gets single bond character. More is
the hyperconjugation, more will be single bond character and more will be the bond
length.
ELECTROMERIC EFFECT (E-Effect)
Complete transfer of shared pair of electrons from one atom to another atom
in the presence of a reagent is called E-effect. It is a temporary effect.
1.Positive Electromeric effect (+E effect)
In this effect the electrons of the multiple bond are transferred to that atom
to which the reagent gets attached.
2.Negative Electromeric effect (-E effect)
In this effect the electrons of the multiple bond are transferred to that atom
to which the reagent does not get attached.
