Live Sahab20

GOC
General Organic Chemistry

By Singh Sahab
Organic chemistry is the study of hydrocarbons and their derivatives

H+C

CH4 C2H4 C2H2

Ability of carbon atom to form long chains or rings.

Carbon shows catenation due to

i. Higher C-C bond dissociation energy

ii. Carbon tetravalency

iii. Small Size

The ability of carbon atom to form four bonds is known as tetra valency.

To exhibit tetravalency carbon forms

i) All four single bonds
ii) Two double bonds
iii) One double bond, two single bonds
iv) One triple bond, one single bond
  and  Bonds
❑  Bond is formed by linear overlapping of atomic orbitals
or hybrid orbitals.

❑  Bond is formed by lateral overlapping of pure atomic

orbitals.
An sp3-hybrid orbital contains.

1) 1/4 s-character

2) 1/2 s-character

3) 1/3 s-character

4) 2/3 s-character
Hybridisation

4 - sp3 -> Tetrahedral

3 - sp2 -> Trigonal Planar

2 - sp -> Linear
General Formula → CnH2n+2 Methane (CH4)

H
n=1 → CH4 |
H–C–H
|
n=2 → C2H6 .
H

Similarly C3H8, C4H10… sp3

Tetragonal
General molecular formula → CnH2n.

H– C = C –H
| |
H H

sp2 Trigonal Planar

H3C – CH = CH2
General molecular formula → CnH2n-2.

H–CC–H

sp Linear
Which of the following is an alkene..

A. C2H6

B. C2H4
C. C2H2

D. C2H8
 Structural representation

1. Complete structural formula:

2. Condensed structural formula:

CH3CH3
Ethane

CH2 = CH2
Ethene
3. Bond line formula:

Butane Cyclo butane

 Contains how many carbon atoms..

1) 9

2) 10

3) 11

4) 8
Saturated Hydrocarbon

The hydrocarbons containing single bonds between two carbon atoms.

e.g : Alkanes & cyclo alkanes

H H
―

H―C―C― H
―

H H
Unsaturated Hydrocarbon

The hydrocarbons which contain Double bonds or triple bonds between two
adjacent carbon atoms .

e.g: Alkenes and Alkynes

H H
―
―

H― C = C ― H H― C  C ― H
Types of Carbon

Primary carbon (10 - carbon): Carbon is bonded to another one carbon.

Secondary carbon (20 - carbon): Carbon is bonded to another two carbon atoms.
Types of Carbon

Tertiary carbon (30 - carbon): Carbon is bonded to another three carbon atoms.

Quaternary carbon (40 - carbon): Carbon is bonded to another four carbon atoms.
 Contains how many 20 carbons….

1) 1

2) 2

3) 3

4) 4
Only saturated compound among the following is….

A. C6H6

B. C3H6

C. C6H10

D. C6H14
Types of Hydrogen

Primary hydrogen: Hydrogen attached to primary carbon.

Secondary hydrogen is attached to secondary carbon.

Tertiary hydrogen is attached to tertiary carbon.

Open chain compounds
Aliphatic or Acyclic Compounds
Closed chain compounds
Cyclic or Ring Compounds
Homocyclic Compounds
Ring structures that consist of only carbon atoms.
Heterocyclic Compounds

Rings containing at least one non-carbon atom

Aromatic Compounds
Conditions for Aromatic

•It must be cyclic.

•Every atom in the ring must be conjugated.

•The molecule must have [4n+2] pi electrons i.e. Follow Huckel’s Rule

•The molecule must be planar.

Examples
Benzenoid Aromatic Compounds

Contain at least one benzene ring

Non-Benzenoid Aromatic Compounds

Contain an aromatic ring other than benzene

Pyridine is.

1) Heterocyclic compound

2) Unsaturated compound

3) Carbocyclic compound

4) Homocyclic compound
Alicyclic Compounds

Organic compound that contains ring but are not aromatic.

The minimum number of carbon atoms which a cycloalkane
contain…
1) 1

2) 2

3) 3

4) 4
Homologous series
Successive members of the series differ from each other by methylene
group (–CH2 –)

For eg.
• Homologous can be
H – CH2 – H(Methane) represented by the same
general formula.
H – CH2 – CH2 – H (Ethane)
• Homologous have the
H – CH2 – CH2 – CH2 – H (Propane) same functional group.
Reaction Mechanism

General reaction
Basic Terminology

▪ There are two reactants

▪ Reactant which supplies carbon to the new bond is called substrate

▪ Other attacking reactant is called reagent.

▪ In a reaction a covalent bond between two carbon atoms or a carbon

and some other atom is broken and a new bond is formed.
Fission of Covalent Bond

Bond Fission

Breaking of a covalent bond is called bond fission.

They are of 2 types.

1. Heterolytic Fission

2. Homolytic Fission
 Heterolytic Fission (Heterolysis)

Breaking of a covalent bond in such a way that one of the atom or

species retains a pair of electrons depending upon electronegativity.

❖ Fission takes place in unsymmetrical manner

❖ Results in formation of ions. (i.e., cations and anions)

 Carbocation

+
CH3 ion is called methyl cation or methyl carbonium ion
 Carbocation

• Carbon atom is positively charged

• Electron deficient species

• Carbon atom posesses six electrons in its outermost shell.

• sp2 hybridisation.

• Its shape is triangular planar.

• It can accept an electron pair from a nucleophile to form a covalent

bond

• Lewis acid
Types:
1. Primary
2. Secondary
3. Tertiary

> > >

Stability of carbocation
In carbocation, carbon is _______hybridised..

1) sp3

2) sp2

3) sp

4) sp3d
Carbanion

Carbon species carrying a negative charge on carbon atom.

Unstable and reactive species

methyl anion
 –
Carbon atom is negatively charged. C

..
•

• Electron rich species.

• Carbon atom possesses eight electrons in its outermost shell.

• sp3 hybridization and carries a lone pair of electrons.

• Its shape is pyramidal.

• It is a Lewis base.
Stability of carbanions

- - -
(CH3)3C < (CH3)2CH < CH3CH2 < CH3
-
Homolytic Fission (Homolysis)

Breaking of a covalent bond in such a way that both the atoms or

species retain one electron each.
Results in the formation of free radicals.

Free radicals: neutral species (atom or group) which contains an unpaired

electron.

-very reactive species

 Homolytic Fission Heterolytic Fission

covalent bond breaks covalent bond breaks

symmetrically unsymmetrically

The more electronegative

Each species obtains and
atom retains the shared
retains one electron from
electron pair
shared electron pair

Electrically neutral free Electrically charged ions

radicals are formed which (cations and anions) are
carry an odd electron. formed

It takes place in the

It takes place in the presence
presence of sunlight, U.V.
of polar solvent.
light.
Homolytic fission takes place in ___ manner.

1) Symmetrical

2) Unsymmetrical

3) Both a and b

4) Can’t say
Nucleophiles

Molecule or ion which is electron rich and donates a pair of electrons

to form new covalent bond.

Examples

Nu- = OH-, H2O, NH3, CN-

Nucleophiles

✓ are Electron hating species.

✓ are Electron rich species.

✓ attack the site of low electron density in the substrate.

✓ are negatively charged ions (anions) or neutral molecules.

✓ Possess an atom with lone pair of electrons.

✓ are Lewis bases.

 Ambident Nucleophiles

Ex. = NO2- , CN-

CH3—Cl + KCN → CH3—CN (cyanide)

CH3—Cl + AgCN → CH3—NC (isocyanide)

 Electrophiles
Molecule or ion which is electron deficient and accepts a pair of
electrons to form new covalent bond.

Examples E+

H+, SO3H+, NO+, NO2+, X+, R+

BF3, AlCl3, SO3
+
CH3
Electrophiles

✓ are Electron loving species.

✓ are Electron deficient species.

✓ Attack the site of high electron density in the substrate.

✓ are + vely charged ions (cations) or neutral molecules

✓ Possess an atom with incomplete octet.

✓ are Lewis acids.

Which of the following not a nucleophile….

1) 𝑪𝑵− 2) 𝑶𝑯 −

3) 𝑵𝑯𝟑 4) 𝑩𝑭𝟑
Inductive Effect

Permanent polarization occurs due to partial displacement of sigma bonded

electrons along carbon chain toward the more electronegative atom.
 Characteristics of I-Effect

1. Permanent Effect

2. Distance dependent effect

3. Magnitude of I-Effect will decrease with increase in distance (practically

after two C – C, it becomes negligible)

4. It works only on  electrons

5.  electrons are not affected by inductive effect

6. Reason of I-Effect is difference in electronegativity

Types of Inductive Effect

1. +I -Effect

2. -I -Effect
 +I Effect
Group which push sigma electrons are called +I group and
this effect is called +I effect.

Example of +I groups: – O –, – COO –, –CR3, –CHR2

+I Effect order

-CH2- > -NH > – O– > – COO – > –CR3 > –CHR2 >
-

–CH2R > –CH3 > –CT3 > –CD3 > – T > –D > -H
-I Effect
Group which withdraw sigma electron density are called -I group
and this effect is called -I effect.

Example of -I groups: –NO2, – SO2R, –CN, –SO2Ar

-I Effect order

-NR3+ > -SR2+ > -NH3+ > –NO2 > – SO3H > –CN > –COOH > -CHO > -COR >

–F > – Cl > – Br > – I > –OR > -OH > -NR2 > -NHR > -NH3 > -CCH > -Ar >

-CH=CH2 > -H
Which group has the highest + Inductive effect….

1) 𝑪𝑯𝟑 - 2) 𝑪𝑯𝟑 𝑪𝑯𝟐 -

3) 𝑪𝑯𝟑 𝟐 CH- 4) 𝑪𝑯𝟑 𝟑 C-

Applications of inductive Effect

Acidic Strength

Acidic Strength  -I Effect  1

+ I Effect
Compare acidic strength

A. F – CH2 – COOH

B. Cl – CH2 – COOH

C. Br – CH2 – COOH

D. I – CH2 – COOH

Ans. A>B>C>D
Compare acidic strength

A. CH3 – COOH

B. Cl – CH2 – COOH

C. Cl2 – CH – COOH

D. CCl3 – COOH

Ans. D>C>B>A
Applications of inductive Effect

Basic Strength

Basic Strength  +I Effect  1

- I Effect
Compare Basic strength

A. NH3

B. CH3 – NH2

C. CH3 – N – H
|
CH3

Ans. C>B>A
Applications of inductive Effect

Stability of Carbocation

 +I Effect

 1
- I Effect
Compare Stability

+
A. CH3

+
B. CH3 – CH2
+
C. CH3 – CH – CH3

+
D. CH3 – C – CH3
|
CH3

Ans. D>C>B>A
Applications of inductive Effect

Stability of Free Radical

 +I Effect

 1
- I Effect
Compare Stability

.
A. CH3
.
B. CH3 – CH2

.
C. CH3 – CH – CH3

Ans. C>B>A
Applications of inductive Effect

Stability of Carbanion

 -I Effect

 1
+ I Effect
Compare Stability

-
A. CH3

-
B. CH3 – CH2

-
C. CH3 – CH – CH3

Ans. A>B>C
Applications of inductive Effect

Dipole Moment

As strength of inductive effect increase, then dipole moment also increase

CH3 – NO2 > CH3 – CN > CH3 – Cl > CH3 – Br

CH3 – F < CH3 – Cl > CH3 – Br > CH3 – I

Inductive effect is..

1) Temporary

2) Permanent

3) Both a and b

4) Can’t say
 Resonance
Delocalisation of  electrons or overlapping of parallel p orbitals.

Resonating Structure Resonance Hybrid

Resonance Energy

It is the difference of potential energy of resonance hybrid and

potential energy of most stable resonating structure.

• The more the number of important contributing structures, the more

is the resonance energy.

• Stability of molecule is directly proportional to resonance energy.

Which of the following statements regarding the resonance energy of
benzene is correct…
1) The energy is required to break the C – H bond in benzene

2) The energy is required to break the C – C bond in benzene

3) The energy is a measure of stability of benzene

4) The energy is required to convert

 Rules of writing Resonance Structure

1. In resonance, only  electrons are involved, sigma electrons are not

involved in resonance.

2. Position of atom should remain same

3. Resonance structure in which similar charge or opposite charge is

present on adjacent atom have less contribution in resonance hybrid.
4. Total no. of paired or unpaired electrons are always same in R.S.

5. In any R.S. , expansion of octet of second period element like Be, B, C, N, O, F

is not possible with 9, 10, 11,….. due to absence of d orbitals.

6. Resonance follow law of conservation means all resonating structures of a

particular species have similar charge.
-ve to 

- -
CH2 – CH = CH2 CH2 = CH – CH2
 to +ve

+ +
CH2 = CH – CH2 CH2 – CH = CH2
 to .
. .
CH2 = CH – CH2 CH2 – CH = CH2
 to +

+ - + -
CH2 = CH – N = O CH2 – CH – N – O

O O
Condition for resonance

1. Parallel p-orbitals should be present on adjacent atom.

2. Adjacent atoms should have sp or sp 2 hybridisation.

3. Parallel p-orbitals may be fully filled, half filled, may be vacant.

In which of the following resonance will be possible..

1) CH2 = CH – CH2 - CHO

2) CH2 = CH – CH = O

3) CH3COCH3

4) CH2 = CH – CH2 - CH = CH2

Stability of Resonating Structures

Follow in sequence

1. Aromatic R.S. are more stable than Non-Aromatic R.S.

2. More covalent bonds → more is the stability

+ -
CH2 = CH – CH = CH2 CH2 – CH = CH – CH2

better
3. R.S. in which all atoms have complete octet is more stable.
4. Neutral R.S. is more stable as compare to R.S. in which charge
separation is present
5. Stability of Charges R.S.

If charge is same
Stability  Distance b/w charge

If charge is opposite
Stability  1
Distance b/w charge
6. -ve charge present on larger atom is more stable compared to
present on smaller atom.
7. If -ve charge is present on higher EN atom than it is more stable
as compared to R.S. in which –ve charge is present on lower EN
atom.
8. +ve charge is more stable on present on lower EN atom as
compared to R.S. in which +ve charge is present on higher EN
atom.
Stability due to Resonance

1. Compounds having more no. of  electrons in Resonance are

more stable

> >
2. If no. of  electrons in resonance are same than aromatic
compound is more stable as compare to non-aromatic
compound.

>
3. If both compound are non-aromatic then compound having
linear conjugation is more stable as compare to compound having
cross conjugation

>
Some Important Points

1. If lone pair or –ve charge are involved in Resonance than they

are not counted in steric no.

2. Hybridisation does not change after resonance

3. Resonance increase stability of carbocation, carbanion and

free radical

4. Due to Resonance, bond length of C = C increase and C – C

decrease
Which of the following is more stable carbanion…

a) c)
b) d)


Select the correct answer using the codes given below:

1) a 2) d 3) b 4) a, b, c
The two bonds N=O and N-O in 𝑯𝟑 CN𝑶𝟐 are of same bond length due
to ….

1) Inductive effect 2) Hyperconjugation

3) Electrometric effect 4) Resonance effect

Mesomeric Effect

Group which can donate or pull  electrons density from conjugated

system is know as resonance group and this effect is known as resonance
effect or mesomeric effect.

Permanent and distance independent effect.

Types of Mesomeric Effect

1. + M Effect

2. - M Effect
+M Effect
Groups which can release  electrons towards conjugative system
shows + M effect.

Example: in Aniline
+M Effect Order

- -
–NH > –O > –NH2 > –NHR > –NR2 > –OH > –OR > –NHCOR >

–OCOR > ph > –CH=CH2 > -F > -Cl > -Br > -I
▪ +M group increases electron density in benzene ring, making
it electron rich

▪ +M group are ortho para directing

▪ +M is activating group

▪ +M stabilizes carbocation
-M Effect
Groups which pull  electron density from conjugative system are
called – M group and this effect is called –M effect.

Example: in Nitrobenzene
-M Effect Order

–NO2 > –CN > –SO3H > –CHO > –C=O > –COOCOR > –COOR >

–COOH > –CONH2 > –COO-

▪ -M group decreases electron density in benzene ring, making
it electron deficient

▪ -M group are meta directing

▪ -M is deactivating group

▪ -M stabilizes carbanion
In electrophilic substitution reaction of nitrobenzene,
electrophile will attack on ___ position..

a) Ortho

b) Meta

c) Para

d) Ortho and para

With respect to chlorobenzene, which of the following statements is NOT
Correct….

1) Cl is ortho/ para directing

2) Cl exhibits + M effect

3) Cl is ring deactivating 4) Cl is meta directing

Important Points to ponder-

1. Some groups have –M effect and +M effect both

Ex –NO, -NC

2. Mesomeric > Resonance > Inductive

There are some groups where I effect is dominant over M effect.

Ex- – N=O , —X , —NC

The order of decreasing reactivity towards an electrophilic
reagent, for the following…

i) Benzene ii)Toluene
iii) Chlorobenzene iv)Phenol
a) ii > iv > i > iii b) iv > iii > ii > i

c) iv > ii > i > iii d) i > ii > iii > iv

Which of the following is not deactivating among the following…

CCl3 R3 N + NH2
CHO
i) ii) iii) iv)

a) (ii) only b) (i) and (ii) only

c) (iv) only d) (ii), (iii), (iv)

Consider the following carbocation.
 
a) H2C OCH3 b) H2C

 
c) H2C CH3 d) CH3-CH2

the relative stabilities of these carbocation's are such that

1) d < b < c < a 2) b < d < c < a

3) d < b < a < c 4) b < d < a < c

The order of stability of the following carbocation’s….

CH2 JEE MAIN 2013

 
CH2=CH-CH2;CH3-CH2-CH2;
I II
III
1) III > II > I 2) II > III > I

3) I > II > III 4) III > I > II

Steric Inhibition of Resonance

SIR effect

• As size of group increases then SIR effect also increases

F Cl Br I
< < <
Hyperconjugation

.
If C – H bond lie in conjugation with C=C, CC, benzene, C+, C then it show
Resonance and this special type of resonance is called Hyperconjugation.

Permanent and distance independent effect.

Also known as No-Bond Resonance.

Condition for Hyperconjugation

.
At least one H-Atom should present on sp3 hybridised carbon which is
directly attached with -C=C, -CC, -ph, C+, C
Important Points for Hyperconjugation

1. In carbanion hyperconjugation is not possible.

2. D and T which are isotopes of H, are also involve in hyperconjugation.
3. H-atoms which are involved in hyperconjugation are known as -H
atom or hyperconjugating H-atom
4. No. of Hyperconjugating Structure of a molecule = -H atom
Important Point

• Mesomeric > Resonance > Hyperconjugation > Inductive

The stability of 2,3-dimethyl but-2-ene is more than 2-butene because of..

A. Resonance

B. Hyperconjugation

C. Electromeric effect

D. Inductive effect
Aromatic Compounds

Criteria for aromaticity

a) Cyclic
b) Planar (i.e., all atoms should be sp 2 hybridized)
c) Completely Conjugated
d) Huckel’s Rule :
Compounds must contain (4n+2) π electrons
where, n = 0,1,2,3,4…
Aromatic Compounds

• Cyclic

• Planar

• sp2
• Complete conjugation

• (4n+2) electrons
Anti-Aromatic Compounds

• Cyclic

• Planar

• sp2
• Complete conjugation

• 4n electrons
Non-Aromatic Compounds

• Cyclic or acyclic

• sp , sp2 , sp3

• Complete/incomplete conjugation
The chemical system that is non aromatic is ...

1) 2)

3)
+ 4)
+ -
Important Points-

• Aromatic > non-aromatic > Anti-aromatic

Anti aromatic compounds are unstable and do not exist at room temp.
Which of the following is aromatic .


a) b)

c) d)
Annulenes
Pyrene

Not involved in conjugation

Electromeric Effect

• Explains the displacement of electrons in multiple bonds.

[double bond or triple bond]

• The complete transfer of a pair of electrons towards one of the atoms in

the presence of attacking reagent is known as electromeric effect.

• It is a temporary effect.

• Its effect operates over a long distance.

Positive Electromeric Effect (+E effect)

π−electrons of the multiple bond are transferred to that atom to

which the reagent gets attached.

| | | |
C=C + H+ –C–C–
+
| | Attacking |
reagent
H
Negative Electromeric Effect (-E effect)

π - electrons of the multiple bond are transferred to that atom to which

the attacking reagent does not get attached

| | | |
C=C + CN- –C–C_ –
| | Attacking |
reagent CN
Important Point

When inductive and electromeric effects operate in opposite

directions, the electomeric effect predominates.
Which of the following is basically a temporary effect.

1) Electromeric effect 2) Inductive effect

3) Hyper conjugation 4) Mesomeric effect