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 Geometry is tetrahedron.  All the valencies of Carbon are satisfied by  -bonds

All the valencies of Carbon are satisfied by -bonds Saturated Carbon.

Rotation about C C is free Conformational Isomers.

-bonds  Saturated Carbon.  Rotation about C  C is free  Conformational Isomers. Saw-Horse
-bonds  Saturated Carbon.  Rotation about C  C is free  Conformational Isomers. Saw-Horse

Saw-Horse projections

Newman Projections

Newman Projections Eclipsed 3 kcal (torsional energy) Staggered

Eclipsed

3 kcal (torsional energy)

Newman Projections Eclipsed 3 kcal (torsional energy) Staggered
Newman Projections Eclipsed 3 kcal (torsional energy) Staggered
Newman Projections Eclipsed 3 kcal (torsional energy) Staggered

Staggered

Potential Energy Changes during rotation

Potential Energy Changes during rotation 3 kcal Rotation
Potential Energy Changes during rotation 3 kcal Rotation
3 kcal
3 kcal
Potential Energy Changes during rotation 3 kcal Rotation
Potential Energy Changes during rotation 3 kcal Rotation

Rotation

Me Me H H H H
Me Me
H
H
H
H

Eclipsed

Me

Me Me H H H H Eclipsed Me H H H Me H Gauche H Me

H

H

H

Me

H

Gauche

H Me

Me Me H H H H Eclipsed Me H H H Me H Gauche H Me

H

H

Me Me H H H H Eclipsed Me H H H Me H Gauche H Me

H

Me

Partially Eclipsed

Me Me H H H H
Me Me
H
H
H
H

Me

Me H H H H Eclipsed Me H H H Me H Gauche H Me H

H

H

H

H

Me

Staggered

Potential Energy Changes during rotation

Potential Energy Changes during rotation Me H H H H 4.4-6.1 kcal Me 3.4 kcal Rotation

Me

H

H

Potential Energy Changes during rotation Me H H H H 4.4-6.1 kcal Me 3.4 kcal Rotation
Potential Energy Changes during rotation Me H H H H 4.4-6.1 kcal Me 3.4 kcal Rotation
Potential Energy Changes during rotation Me H H H H 4.4-6.1 kcal Me 3.4 kcal Rotation

H

H

4.4-6.1 kcal

Me

3.4 kcal

Potential Energy Changes during rotation Me H H H H 4.4-6.1 kcal Me 3.4 kcal Rotation
Potential Energy Changes during rotation Me H H H H 4.4-6.1 kcal Me 3.4 kcal Rotation
Potential Energy Changes during rotation Me H H H H 4.4-6.1 kcal Me 3.4 kcal Rotation
Potential Energy Changes during rotation Me H H H H 4.4-6.1 kcal Me 3.4 kcal Rotation
Potential Energy Changes during rotation Me H H H H 4.4-6.1 kcal Me 3.4 kcal Rotation

Rotation

Different arrangements of atoms that can be converted into one another by rotation

about single bonds are called conformations.

Conformers cannot be isolated

Always inter-converted. Positions not frozen.

sp 3 carbon is least electronegative of all other hybrid carbon atoms.

is least electronegative of all other hybrid carbon atoms.  Geometry is Triangular Planar.  All

All the valencies of Carbon are not satisfied by -bonds Unsaturated Carbon.

Rotation about C=C or C-C (in a ring) is restricted geometrical isomers are possible.

Me

Me Me H C  C H Me Me H H Me H C  C

Me

H

CC

Me Me H C  C H Me Me H H Me H C  C
Me Me H C  C H Me Me H H Me H C  C

H

Me Me
Me
Me

H

H

Me

Me Me H C  C H Me Me H H Me H C  C

H

CC

Me Me H C  C H Me Me H H Me H C  C
Me Me H C  C H Me Me H H Me H C  C

H

Me

Me H
Me
H

H

Me

Different arrangements of atoms in space arising out of hindered rotation about C-C

or C=C are called geometrical isomers.

sp 2 carbon has higher electronegativity than sp 3 carbon.

carbon has higher electronegativity than sp 3 carbon.  Geometry is Linear.  All the valencies

Geometry is Linear.

All the valencies of Carbon are not satisfied by -bonds Unsaturated Carbon.

Has highest electronegativity among carbon atoms of various hybridizations.

 Polarization of  - bonded electrons towards the atom of higher electronegativity.  The

Polarization of - bonded electrons towards the atom of higher electronegativity.

The standard of reference is H atom.

Pushing electrons away is +I effect while pulling electrons towards is I effect.

Lets check the inductive effect of CH 3

CH 3 has +I effect

+

H

H

 
 
 
 
  C

C

H

H

-

H
H
 

-

X

X

   - X    -   X
 

-

 
  X

X

   - X    -   X

Lets replace one H of CH 3 with another CH 3 and then check.

Increasing

C

chain

increases

+I

effect

but

the

rate

of

increase decreases.

H

effect but the rate of increase decreases. H H C  -   H    

H

H C  -

C

-

H C  -   H     CH 3 CH 2
 
 
 

H

 
 
 

CH 3

CH 3 CH 2

CH 2

C  -   H     CH 3 CH 2 X X  - 

X

X

-

-

Lets replace one H of CH 3 with another CH 3 and then one H of CH 2 with a CH 3 .

I

effect

and then one H of CH 2 with a CH 3 .  I effect CH

CH 3 decreases

H of CH 2 with a CH 3 .  I effect CH 3 decreases with

with distance.

CH 2

CH 3

CH 2 2 2

CH
CH

CH 3

X
X

H of CH 2 with a CH 3 .  I effect CH 3 decreases with

X

-

-

Lets replace the H with a sp 2 carbon.

H

+

H

2 CCH

H  + H 2 C  CH

X

-

sp 2 carbon has I effect. So does sp carbon.

Inductive effect is a particle effect. This means it is the manifestation of the particle nature of electrons.

Inductive effect dissipates with distance.

Inductive effect is a permanent effect.

Inductive effect is a weak effect.

Order of decreasing inductive effects:

Inductive effect is an ‘always’ effect.

+I groups: O - > CO - 2 > CR 3 > CHR 2 > CH 2 R > D -I groups: NR 3 + > SR 2 + > NH 3 + > NO 2 > SO 2 R > CN > CO 2 H > F > Cl > Br > I > OAr > COOR > OR > COR > SH > OH > C CR > Ar > CH=CR 2

 Delocalization of  electrons.  It arises out of the wave nature of electrons.

Delocalization of electrons.

It arises out of the wave nature of electrons.

Since wave nature cannot be drawn, we represent canonical forms which exhibit particle

nature and whose hybrid the actual structure can be assumed to be.

The actual structure of the molecule/ion is the weighted mean of the canonical or parent structures. But the energy of the molecule is lower than all the canonical forms.

While drawing the structures of canonical forms positions of atoms are to remain fixed while that of electrons changes.

Molecules showing resonance must be conjugated and the orbitals appropriately oriented.

Resonance effect is also called Mesomeric Effect.

Resonance effect is a permanent effect.

Resonance effect is a strong effect, generally stronger than Inductive Effect.

Resonance is a relative effect. It is a need based effect.

Basic movement of electrons:

: A + :A + A :A
:
A +
:A
+ A
:A
ABC
ABC

ABC

: A + :A + A :A ABC A  B  C : A 

:AB

+ AB - C

+

ABC -

+ AB -

A
A

A

- A

- A

1.

Double bond conjugated with +ve charge:

+ CCC

Double bond conjugated with +ve charge: + C  C  C + + CH 2

+

Double bond conjugated with +ve charge: + C  C  C + + CH 2

+ CH 2 CHCHCHCH 2 CH 2 CHCHCHCH 2

I

II

+

CH 2 CHCHCHCH 2

III

I = III > II Stability order of resonating structures having +1 charge:

1. Of all such resonating structures the one in which octet of all atoms is complete is most stable and therefore most contributing.

2. Next is that resonating structure in which +ve charge is on the most electropositive element. And then in that order.

3. Resonating structures which are similar have equal stability.

2.

Double bond conjugated with double bond:

CCCC

Double bond conjugated with double bond: C  C  C  C CH 2 
Double bond conjugated with double bond: C  C  C  C CH 2 

CH 2 CHCHCHCHCH 2 CH 2 CHCHCHCH + CH 2 II

I

-

 CH  CH  CH  CH +  CH 2 I I I -

CH 2 CHCH + CHCHCH 2 - III

+ CH 2 CHCHCHCHCH 2

IV

-

I > II > III > IV

Stability order of resonating structures having net charge zero:

1. Of all such resonating structures the one in which no atom has any charge is most stable.

2. Next is that resonating structure in which charge separation is the least and then in that order.

Evidences of resonance:

1. All bonds are between a single and a double bond.

2. On treating the molecule with Br 2 in CCl 4 we get 4 products, 1,2; 3,4; 1,4 and 1,6.

CH 2 CHCHCHCHCH 2

CH 2 CHCHCHCHCH 2

CH 2 CHCHCHCHCH 2

1,2 product

Br

Br

CH 2 CHCHCHCHCH 2

Br

Br

3,4 product

Br

Br

1,4 product

Br

Br

1,6 product

1,6 product > 1,2 product > 1,4 product > 3,4 product

1,6 product is most stable because the double bonds are conjugated and non-terminal. 1,2 is next since double bonds are conjugated but one of them is terminal. 1,4 is next as one of the double bonds is non-terminal, while 3,4 is the least as both the bonds are terminal.

3.

Double bond conjugated with ve charge:

- CCC

bond conjugated with – ve charge: - C  C  C - O  CH
bond conjugated with – ve charge: - C  C  C - O  CH

- OCHCHCHCH 2

I

-

 C  C - O  CH  CH  CH  CH 2 
 C  C - O  CH  CH  CH  CH 2 

OCHCHCHCH 2

II

I > II > III

-

OCHCHCHCH 2

III

Stability order of resonating structures having -1 charge:

1. Of all such resonating structures the one in which the ve charge is on the most electronegative atom is most stable and then in that order.

2. Resonating structures which are similar have equal stability.

3. Among resonating structures in which charge is on similar atoms but the structures are different, the stability is decided by inductive effects.

4.

Double bond conjugated with lone pair:

:CCC

4. Double bond conjugated with lone pair: : C  C  C - + H
-
-
Double bond conjugated with lone pair: : C  C  C - + H 2
Double bond conjugated with lone pair: : C  C  C - + H 2

+

H 2 NCHCHCHCH 2 H 2 NCHCHCHCH 2

I

II

I > II > III

+

-

H 2 NCHCHCHCH 2

III

Stability order of resonating structures having net charge zero:

1. Of all such resonating structures the one in which no atom has any charge is most stable.

2. Next is that resonating structure in which charge separation is the least and then in that order.

5.

Double bond conjugated with unpaired electron:

 5. Double bond conjugated with unpaired electron: C  C  C CH 2 

CCC

Double bond conjugated with unpaired electron: C  C  C CH 2  CH 
Double bond conjugated with unpaired electron: C  C  C CH 2  CH 
Double bond conjugated with unpaired electron: C  C  C CH 2  CH 
Double bond conjugated with unpaired electron: C  C  C CH 2  CH 
Double bond conjugated with unpaired electron: C  C  C CH 2  CH 

CH 2 CHCHCHO CH 2 CHCHCHO CH 2 CHCHCHO

I

II

III

I > II > III Stability order of resonating structures having no charge and having 1 unpaired electron:

1. Of all such resonating structures the one in which the unpaired electron is on the least electronegative atom is most stable and the in that order.

2. Resonating structures which are similar have equal stability.

3. Among resonating structures in which the unpaired electron is on similar atoms but the structures are different, the stability is decided by inductive effects.

6.

Lone pair conjugated with +ve charge:

:NC +

H

6. Lone pair conjugated with +ve charge: : N  C + H + 2 N
6. Lone pair conjugated with +ve charge: : N  C + H + 2 N

+

2 NCHCHCH 2

I

: N  C + H + 2 N  CH  CH  CH 2

+

+

H 2 NCHCHCH 2 H 2 NCHCHCH 2

II

III

III > I > II Stability order of resonating structures having +1 charge:

1. Of all such resonating structures the one in which octet of all atoms is complete is most stable and therefore most contributing.

2. Next is that resonating structure in which +ve charge is on the most electropositive element. And then in that order.

3. Resonating structures which are similar have equal stability.

7.

Lone pair conjugated with unpaired electron:

 7. Lone pair conjugated with unpaired electron: : N  C : NH 2 

:NC

Lone pair conjugated with unpaired electron: : N  C : NH 2  CH 2

:NH 2 CH 2 I

+-

NH 2 CH 2 II

I > II Stability order of resonating structures having no charge and having 1 unpaired electron:

1. Of all such resonating structures the one in which the unpaired electron is on the least electronegative atom is most stable and the in that order.

2. Resonating structures which are similar have equal stability.

3. Among resonating structures in which the unpaired electron is on similar atoms but the structures are different, the stability is decided by inductive effects.

The conjugation need not be necessarily via a single bond. It can be via a double bond as well.

CH 2 =C=C=CH 2 Wherever we have studied that a double bond is conjugated with something, the double bond could also be a triple bond.

 Molecules that satisfy the following conditions are said to be aromatic. Aromatic molecules have

Molecules that satisfy the following conditions are said to be aromatic. Aromatic molecules have extra stability compared to non-aromatic or anti-aromatic molecules.

1. The molecule should be cyclic.

2. It must have (4n+2) electrons in the periphery of the molecule.

3. The molecule must show cyclic delocalization.

4. All the atoms must be sp2 hybridized in at least one resonating structure.

In order to check whether a molecule is aromatic or not, we would first learn how to make a

molecule aromatic.

To do this we would first make an empty ring structure aromatic.

Lets start with the smallest ring structure, a 3 member ring.

We’ll first add one electron to each of the peripheral atoms.

We would add / remove electrons if required in order to make the electrons equal to (4n+2). In the present case the closest value of

(4n+2) to 3 is 2. So we remove one electron from any of the atom.

If

we

remove

then

put a ve charge.

we

put

a

+ve

charge,

if

we

add then +
add
then
+

we

Now we join the other electrons by bonds.

The structure made this way will be aromatic. The first 2 conditions are anyway met. The last condition is also met. Lets check the 3rd condition by drawing all the resonating structures of the compound.

To draw the resonating structures in a cyclic molecule, we first choose a direction of the arrow (clockwise or anticlockwise) and maintain this direction for moving electrons in all resonating structures. Next we choose whether we put the arrow inside or outside the ring.

+

we choose whether we put the arrow inside or outside the ring. +   +
  +
+
we choose whether we put the arrow inside or outside the ring. +   +
we choose whether we put the arrow inside or outside the ring. +   +

+

We can see that all bonds have become double once, each atom has had the positive charge once. Therefore the molecule shows cyclic delocalization.

once. Therefore the molecule shows cyclic delocalization.  The closest value of (4n+2) to 4 is

The closest value of (4n+2) to 4 is either 2 or 6. Since we have already seen the removal of electrons, lets add electrons this time.

We add or remove from adjacent atoms because we need to join the leftover electrons.

Lets draw all the resonating structures and then check.

-

-

-

-

-
-
 Lets draw all the resonating structures and then check. - - - - - 

 Lets draw all the resonating structures and then check. - - - - - 

-

 Lets draw all the resonating structures and then check. - - - - - 

-

-

-

-
-
 Lets draw all the resonating structures and then check. - - - - - 
 Lets draw all the resonating structures and then check. - - - - - 

-
-
 Lets draw all the resonating structures and then check. - - - - - 

- -

Benzene Naphthalene Anthracene - - + Phenanthrene + + Pyrene

Benzene

Naphthalene

Anthracene

- - +
-
-
+

Phenanthrene

+ +
+
+

Pyrene

Now let us find out how to assess whether a given molecule or ion is aromatic or not.

Count the no. of atoms that make up the ring and draw another ring of the same no. using only carbon atoms.

Now make this ring aromatic as done before.

If all that is present in your structure is present in the given structure then it is aromatic otherwise not. Remember a negative charge is equivalent to a lone pair.

+

N H
N
H
a negative charge is equivalent to a lone pair. + N H N N N Pyrrole
N N
N
N
a negative charge is equivalent to a lone pair. + N H N N N Pyrrole

N

negative charge is equivalent to a lone pair. + N H N N N Pyrrole H

Pyrrole

H Imidazole

Pyridine

N N
N
N

Pyrazine

N N
N
N

Pyrimidine

N N
N
N

Pyridazine

+ -
+
-
H H C  CH  CH H H < CH 3 CH 3 C

H

H

CCHCH

H H

< CH 3

CH 3

CCHCH

CH 3

H

Resonance involving single bonds.

Different as compared to resonance as it involves -bonds (generally CH bond).

Also known as no bond resonance.

Hyperconjugation is a permanent effect.

Weaker than Resonance but stronger than Inductive Effect.

1.

Single bond conjugated with double bond:

H

H CCHCH H H
H
CCHCH
H
H

H

 

-

+

H

CCHCH

H

+

H

H

H

-

CCHCH

H

H

H

H

CCHCH

+

-

H H

+

H

H +

C

H +

CH

-

CH 2

2.

Single bond conjugated with +ve charge:

3.

4.

H

H + CCH 2
H
+
CCH 2

H

H

H

CCH 2

H

+

 3.  4. H H + CCH 2 H H H C  CH 2

+

H

H

CCH 2

H

Single bond conjugated with unpaired electron:

H

H CCH 2
H
CCH 2

H

H

H

CCH 2

H

with unpaired electron: H H CCH 2 H H H C  CH 2 H H
with unpaired electron: H H CCH 2 H H H C  CH 2 H H
with unpaired electron: H H CCH 2 H H H C  CH 2 H H

H

H

CCH 2

H

H

+

H

CCH 2

H

H

H CCH 2
H
CCH 2

H

Single bond conjugated with -ve charge

Cl Cl CCH 2
Cl
Cl
CCH 2

Cl

Cl

Cl

CCH 2

Cl

-

-

Cl

Cl

CCH 2

Cl

Cl

Cl

CCH 2

-

Cl

 A sudden effect (temporary) due to the presence of other molecules or groups in

A sudden effect (temporary) due to the presence of other molecules or groups in the same molecule.

Causes permanent change in the nature of the molecule.

Responsible for reactions between a neutral molecule and charged ion or between two neutral molecules.

The movement of electrons due to the presence of another molecule or ion leading to the reaction is electromeric effect.

B

E

-

+

+ CH 2 CH 2
+
CH 2
CH 2