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SIMPLY CONCISE
CHEMISTRY
GENERAL ORGANIC CHEMISTRY
Reagent
Substrate [Intermediate] Product + byproducts
C⁺, C⁻, C˙
C A
SIMPLY CONCISE
1) heterolytic cleavage -
+
C + A
-
1) Nucleophiles - nucleus loving
have a pair of e⁻ to donate
eg - CH₃⁻, X⁻, RO⁻, H₂O, NH₃
carbocation
-I Effect order:
+ + SIMPLY CONCISE
+
-NF₃ > -NR₃ > -NH₃ > -NO₂ > -SO₃H > -CN > -CHO > -COOH > -F > -Cl > -Br > -I > -OR > -OH>
≡
-C CH > -NH₂ > -Ar > -C=CH₂ > -H
+I Effect order:
- - - -
-CH₂ > -NH > -O > -COO > 3°R > 2°R > 1°R > -H
INDUCTIVE EFFECT
Applications of Inductive effect
- + .
1) To compare stability of C , C and C
+ + - - . .
C C C C C C
∝ ∝ ∝
SIMPLY CONCISE
stability +I & 1/-I stability -I & 1/+I stability +I & 1/-I
acidic
strength
∝ -I & 1/+I
INDUCTIVE EFFECT
Q. Compare acidic strength
F -I Cl Cl -I
effect of distance > number > power
OH < OH
OH -I SIMPLY CONCISE +I
alkenes: σ - π*
+
SIMPLY CONCISE
H H H H
- + - -
H C CH CH₂ H C CH CH₂ H C CH CH₂ H C CH CH₂
+
H H H H
carbocation: σ - p
+
H H H H
+ +
H C CH₂ H C CH₂ H C CH₂ H C CH₂
+
H H H H
HYPERCONJUGATION
delocalisation of e⁻ from filled BMO to adjacent empty orbital
+ .
requirement: α-H at sp³ C wrt C=C / C / C // no. of HCS = no. of α- H
free radical: : σ - p
.
SIMPLY CONCISE
H H H H
. .
H C CH₂ H C CH₂ H C CH₂ H C CH₂
.
H H H H
negative conjugation:
-
Cl Cl Cl Cl
+ - + +
Cl C CH CH₂ Cl C CH CH₂ Cl C CH CH₂ Cl C CH CH₂
-
Cl Cl Cl Cl
HYPERCONJUGATION
Applications of hyperconjugation
+ .
1) To compare stability of alkenes, C and C
stability ∝ no. of HCS = no. of α- H
effect of HC > I effect
SIMPLY CONCISE
2) To compare heat of hydrogenation of alkenes
C C + H₂ CH CH
3 3 3 3
+ > + 2
3
2
3
2 -I
3
3
> 3
NH₂
3
RESONANCE
delocalisation of πe⁻ & lp e⁻ of the molecule
+ δ+
+ δ+
O O O
..
..
..
O
..
..
..
..
..
+ δ+
resonating structures resonance hybrid
Note:
SIMPLY CONCISE
resonance increases stability of the molecule
stability of RH > stability of RSs
contribution of RS ∝ stability of RS
Condition:
molecule should be planar - sp²
σ
conjugation should be there - charge charge
- - + -
A B C A B C A B C D A B C D
+ +
A B C A B C
RESONANCE
Stability of resonating structures:
1) neutral RS is more stable than charged RS
+ -
Cl CH CH₂ > Cl CH CH₂
SIMPLY CONCISE
-OH, -OR, -NH-CO-R, -O-CO-OR, -NH₂ -NO₂, -CN, -SO₃H, -CHO, -CO, -COOR,
.. .. ..
.. ..
-Ph, -X -COOH, -CO-NH₂, -NO
.. , -NO, -R
.
order of M effect:
O cross conjugation
.. .. .. ..
H₂C CH OH
.. < H₂C CH NH₂ H₂C CH OH
.. > H₂C CH O
.. C CH₃
Note:
1) while comparing : M > HC > I 2) M effect doesn‘t operate at meta position
exception - halogens : -I > +M ..
OH CHO
-I : F > Cl > Br > I
+M : F > Cl > Br > I
⇒ F < Cl < Br < I δ- δ- δ+ δ+
withdrawing
nature δ- δ+
MESOMERIC EFFECT
Applications of mesomeric effect
1) To compare acidic strength of aromatic alcohols & carboxylic acids
O O
- -
C O H C O O H O
SIMPLY CONCISE H
+ acidic
strength
∝ -M & 1/+M H
+
Note -
1) Ortho effect in benzoic acids - 2) effect of H bonding -
O
COO
- OH
- G ≠ H, F, OH, CN ...
C O NO₂
OH
G
more acidic less acidic
NO₂
SIMPLY CONCISE
NO₂
-I, -M
ortho ortho ortho ortho
NO₂
COOH COOH OH OH
+
NH₂ G ≠ H, F, OH, CN ...
G
>
> > +I
SIMPLY CONCISE
+I, +M
.. .. .. - > -
NH₂ NH₂ NH₂
SIP
< +I <
+I, +M
AROMATICITY
Huckle’s Rule for Aromaticity:
1) Aromatic - ring + planar + cont. conjugation + (4n+2)πe⁻
2) Anti aromatic - ring + planar + cont. conjugation + (4n)πe⁻
3) Non aromatic - if any of the first three condition is not true
SIMPLY CONCISE
a) b) c) more
resonance
SIMPLY CONCISE
3) hybridisation : sp³ > sp² > sp
Q. Compare stability:
+
3
+ + +M, -I +
OCH₃
+ +
> > -I < .. < ..
+M, -I
OCH₃
↓ OCH₃ +
OH
BB
OH
BB
NH₂
CARBOCATIONS
Rearrangement in carbocation:
1) Shift - increases stability
SIMPLY CONCISE
1 1 1 1
H
+M, +I
SIMPLY CONCISE
3) hybridisation : sp³ < sp² < sp
Q. Compare stability:
- - -
- < - < - - -
- > >
+I +I +I sp sp² sp³ > >
-M +M
NO₂ OCH₃
FREE RADICALS
Stability:
1) M > HC > I
2) stability ∝ +M, +I, +HC
∝ 1
-M, -I, -HC
SIMPLY CONCISE
3) hybridisation : sp³ > sp² > sp