ORGANIC LECTURE NOTES


(TOTAL NUMBER OF LECTURES -7)

TTTTT : TTTTTTTT TTTTTTTTT

 LECTURE NO.1
NUCLEOPHILE & NUCLEOPHILICITY
1. NUCLEOPHILE : It is the e– rich species having atleast one lone pair of electrons. It can be neutral
or –vely changed it is always a lewis base.

BASICITY : It is the tendency to donate e– pair to ion.

All bases are nucleophiles, but all nucleophlies are not base all the time.

(i)

(ii)

1.1 NUCLEOPHILICITY :
The tendency to give e– pair to an electron deficient carbon atom is defined as nucleophilicity.

(i) Criteria for Nucleophilicity :

1. The factors which increases e– density at ‘donor atom increases nucleophilicity’.
2. The more polarisable donar atom is a better nucleophile. Therefore, large size of donor atom
increases nucleophilicity.

(ii) Periodicity :
Nucleophilicity decreases from left to right in a period.

 In a group, nucleophilicity increases from top to bottom due to increases in size of donor atom, but
basicity decreases from top to bottom.
Acid strength : HI > HBr > HCl > HF
Basic strength : F¯ > Cl – > Br– > I –
Nucleophilicity : F¯ < Cl – < Br– < I –

(iii) Steric effects on nucleophilicity

Stronger base, yet weaker

nucleophile cannot approach
the carbon atom so easily.
(iv) The effect of the solvent  In polar protic solvent large nucleophiles are good, and the halide ions
show the following order

In DMSO, the relative order of reactivity of halide ions is

> > >

This effect is related to the strength of the interaction between nucleophile and solvent molecules of polar
protic solvent forms hydrogen bond to nucleophiles in the following manner :

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 (v) Relative nucleophilicity in polar protic solvent

> > > > > > > > > H2O

(vi)
Nucleophilicity Basicity Remarks
1. CH3¯ > NH2¯ > OH¯ > I¯ CH3¯ > NH2¯ > OH¯ > I¯ If donor atomis belong to
same period, nuclephilicity
and basicity order is same

2. SiH3¯ > PH2¯ > SH¯ > Cl¯ SiH3¯ > PH2¯ > SH¯ > Cl¯

3. F¯< Cl¯ < Br¯ < I¯ F¯> Cl¯ > Br¯ > I¯ In a group nucleophilicity
increases while basicity
decreases. on moving top to
bottom.

,,
4. OH¯ < SH¯ OH¯ > SH¯

,,
5. RO¯ < RS¯ RO¯ > RS¯

6. RO¯ > HO¯ Same If donor atom is same,

nucleophilicity and basicity
have same order
,,
7. , PhO¯, HO¯, RO¯ RO¯ > HO¯ > PhO¯ >

8. > (tetrahedral) (more resonance (extensive). [d–d bonds]

9. HO¯ > H2O

NH2¯ > NH3

CF 3SO 3¯ < PhCOO¯ < PhO¯ < RO¯ (Nucleophilicity)

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 LECTURE NO.2
LEAVING GROUP ABILITY
2. Leaving group Ability/Nucleofugality :
The best leaving groups are those that become the most stable ion after they leave, because leaving group
generally leave as a negative ion, so those leaving group are good, which stabilise negative charge most
effectively and weak base do this best, so weaker bases are good leaving groups. A good leaving group
always stabilize the transition state and lowers its free energy of activation and there by increases the rate
of the reaction.
(a) Order of leaving ability of halide ion

> > >

(b) Other leaving groups are

(c) Strongly basic ions rarely act as leaving group 

(strong base)

(It is not a leaving group)

(d) The weaker bases are better leaving groups.

(e) The leaving group should have lower bond energy with carbon.

(f) Negative charge should be more stable either by dispersal or declocalization.

(g) Leaving group ability :

1. F¯ < Cl¯ < Br¯ < I¯

2. CH3¯ < NH2¯ < OH¯ < F¯

3. R–COO¯ > PhO¯ > HO¯ > RO¯

4. SH¯ > OH¯

5. >

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 LECTURE NO.3
Nucleophilic substitution reaction (SN1)

3. Nucleophilic substitution reaction.

General reaction (RX + Nu¯  RNu + X¯)

3.1 Unimolecular nucleophilic substitution reaction (SN1) :

Nucleophilic substitution which involves two step process
(a) First step : - Slow step involves ionisation to form carbocation
R–g  R+ + g –
(b) Second step : - Fast attack of nucleophile on carbocation to result into product .
R+ + Nu –  R–Nu

3.1.1 SN1 Reaction of alkyl halide

Ionisation of
alkyl halide
  
Slow step (rds)

Characteristics of SN1 reactions :

1. It is unimolecular, two step process.
2. Carbocation intermediate is formed so rearrangement is possible in SN1 reaction.
3. It is first order reaction
4. Kinetics of the reaction Rate  [Alkyl halide]
Rate = k [(CH3)3C – X]
1
Rate of S N
reaction is independent of concentration and reactivity of nucleophile.
5. Energetics of the SN1

Figure : Free energy diagram for the SN1 reaction.

6. Factor's affecting the rates of SN1
(i) The structure of the substrate : The Rds of the SN1 reaction is ionization step, in this step form a
carbocation. This ionisation is strongly endothermic process, rate of SN1 reaction depends strongly on
carbocation stability because carbocation is the intermediate of SN1 reaction which determines the
energy of activation of the reaction.
SN1 reactivity : 3° > 2° > 1° > CH3 – X
(ii) Concentration and reactivity of the nucleophile  The rate of SN1 reactions are unaffected by the
concentration and nature of the nucleophile
(iii) Nature of nucleophile:-
 Weak, neutral, mostly solvents (protic) itself functions as nucleophiles in S N1 reaction.
# In SN1 reaction, mostly the solvent functions as nucleophile. So S N1 reaction are termed as solvolysis
reaction.
water  hydrolysis
C2H5OH  ethanolysis

Page # 5
 CH3COOH  acetolysis
NH3  ammonolysis
SN2 reaction is disfavoured by strong, anionic nucleophiles which attacks faster before ionisation takes
place leading to SN2 mechanism.
For SN1 reactions, weak neutral nucleophiles are suitable and mostly solvent molecules function as
nucleophiles with oxygen and nitrogen as donor atoms.
OH2 + – H
R – X + H2O  R+ R – O – H    R – OH + HX

–
H
(iv) Effect of the solvent : the ionizing ability of the solvent :
Because to solvate cations and anions so effectively the use of a polar protic solvent will greatly increase
the rate of ionization of an alkyl halide in any SN1 reaction. It does this because solvation stabilizes the
transition state leading to the intermediate carbocation and halide ion more than it does the reactant,
thus the energy of activation is lower.

R–X (Solvolysis)

Solvated ions
(v) The nature of the leaving group  In the SN1 reaction the leaving group begins to acquire a negative
charge as the transition state is reached stabilisation of this developing negative charge at the leaving
group stabilizes the transition state and ; this lowers the free energy of activation and thereby increases
the rate of reaction.

leaving ability of halogen is > > > >

7. Stereochemistry of SN1 reactions  In the SN1 mechanism, the carbocation intermediate is sp2
hybridized and planar, A nucleophile can attack on the carbocation from either face, if reactant is chiral
than after attack of nucleophile from both faces gives both enantiomers of the product, which is called
racemization.
Mechanism of racemization (SN1  

e.g. H O acetone
2   
 + HBr (3° alkyl halide hence no SN2 reaction)

e.g. (Racemic Mixture)

Page # 6
 LECTURE NO.4
Nucleophilic substitution reaction (SN2)

4. SN2 Reaction of alkyl halide :

Mechanism :

 +

Characteristic of SN2
1. It is bimolecular, one step process
2. It is second order reaction because in the RDS two species are involved
3. Kinetics of the reaction  rate  [alkyl halide] [nucleophile]
rate = k[alkyl halide] [nucleophile]
If the concentration of alkyl halide in the reaction mixture is doubled, the rate of the nucleophilic
substitution reaction is double. If the concentration of nucleophile is doubled the rate of reaction is also
double. If the concentration of both are doubled then the rate of the reaction quadriples.
4. Energetics of the reaction :

Figure : A free energy diagrams for SN2 reaction

5. No intermediates are formed in the SN2 reaction, the reaction proceeds through the formation of an
unstable arrangment of atoms or group called transition state.
6. The stereochemistry of SN2 reactions  As we seen earlier, in an SN2 mechanism the nucleophile
attacks from the back side, that is from the side directly opposite to the leaving group. This mode
of attack causes an inversion of configuration at the carbon atom that is the target of nucleophilic
attack. This inversion is also known as walden inversion.

Inversion
  

7. Factor's affecting the rate of SN2 reaction  Number of factors affect the relative rate of SN2 reaction,
the most important factors are
(i) Effect of the structure of the substrate 
Order of reactivity in SN2 reaction : – CH3 > 1° > 2° >> 3° (unreactive)
the important factor behind this order of reactivity is a steric effect. Very large and bulky groups can
often hinder the formation of the required transition state and crowding raises the energy of the transition
state and slows down reaction.
(ii) Concentration and reactivity of the nucleophile
As nucleophilicity of nucleophile increases rate of S N2 increases.
– Anionic nucleophiles mostly give S N2 reaction
– A stronger nucleophile attacks upon -carbon with faster rate than the rate of departing of leaving
group. R– > NH2– > OH– > F –

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 RO – > ROH
NaOH > H2O
NH3 > H2O

Table :

(iii) The effect of the solvent: Polar aprotic solvent have crowded positive centre, so they do not solvate
the anion appreciably therefore the rate of SN2 reactions increased when they are carried out in polar
aprotic solvent.
(iv) The nature of the leaving group  Weaker bases are good leaving groups. A good leaving group always
stabilize the transition state and lowers its free energy of activation and thereby increases the rate of
the reaction. Order of leaving ability of halide ion F¯ < Cl¯ < Br¯ < I¯
KOH
e.g. (CH3)2CHCH2CH2 – Br  
 (CH3)2CHCH2CH2 – OH
H2O

e.g.

Na PhCH Br CH2 – O – CH3

e.g. MeOH  2
   
Benzylmethyl ether
1 2
Comparision between S N / SN reaction
Conditions/ Characteristics :
SN2 SN1

1. Energetic

2. Kinetics r  [RX] [NU:] r  [RX]

3. Stereochemistry inversion racemisation
4. Rearrangement not possible possible
5. Activation energy Ea S > Ea SN1 (more) less
N2

6. Nature of R – X Me – X > R– CH 2 –X > R 2 – CH – X > R 3–CX R 3CX > R 2CHX > RCH 2X > CH3X

7. Nucleophile strong anionic Weak neutral

Page # 8
 R– > NH2– > OR– > OH– H2O > MeOH > EtOH > NH3
8. Leaving group – > Br– > Cl – > F – (same)
SN2 SN1
9. Solvent Polar aprotic Polar protic

10. Temperature High Low

LECTURE NO.5
Elimination reaction (E1)

5. Elimination reactions :
In an elimination reaction two atoms or groups (YZ) are removed from the substrate and generally
resulting into formation of  bond.
| |
E limination
CC    
 YZ
| |
Y Z
-elimination : When two groups are lost from the same carbon atom to give a carbene (or nitrene).
This is also called 1–1 elimination.
 C–C

-elimination : When two groups are lost from adjacent atoms so that a new  bond is formed. This
is also called 1–2 elimination.
 C=C

–elimination : It is also called 1–3 elimination, In this a three membered ring is formed.



5.1 E1 Reaction : Proton and leaving group depart in two different step.
(a) First step : - Slow step involves ionisation to form carbocation
(b) Second step : Abstraction of proton

5.1.1 E1 Reaction of alkyl halide :

Mech.

Step 1 : Formation of the carbocation (RDS)

Step 2 : Base ( ) abstracts a proton (fast)

+ B – H

Characteristics of E1 reaction :
(i) It is unimolecular, two step process.

Page # 9
 (ii) It is first order reaction.
(iii) Reaction intermediate is carbocation, so rearrangment is possible
(iv) In the second step, a base abstracts a proton from the carbon atom adjacent to the carbocation,
and forms alkene.
(v) Kinetics  Rate  [Alkylhalide]
Rate = k [Alkylhalide]

(vi) Energetics  The free energy diagram for the E1 reaction is similar to that for the SN1 reaction.

CH3
|
e.g. CH3  CH2  C  CH3  +
|
Br

e.g. 

e.g.

LECTURE NO.6
Elimination reaction (E2)
6. E2 Reaction :
6.1 E2 Reaction of alkyl halide :
Dehydrohalogenation is the elimination of a hydrogen and a halogen from an alkyl halide to form an
alkene. Dehydrohalogenation can take place by E1 and E2 mechanism.

(i) Hot alcoholic solution of KOH EtO¯ / EtOH (ii) NaNH2 (iii) t-BuO¯ K in t-BuOH
Mechanism

  + BH

Page # 10
Characteristics of E2 reaction 
1. This is a single step, bimolecular reaction
2. It is a second order reaction
3. Kinetics  Rate  [R – X] [Base]

Rate = k [R – X] [ ]
4. Rearrangment is not possible
5. For the lower energy of activation, transition state must be stable
6. E2 follows a concerted mechanism
7. The orientation of proton & leaving group should be antiperiplanar.
8. Here  – H is eliminated by base hence called  elimination
9. Positional orientation of elimination  In most E1 and E2 eliminations where there are two or more
possible elimination products, the product with the most highly substituted double bond will predominate.
This rule is called the saytzeff or zaitsev rule.

For example : Dehydrohalogenation of 2-bromo-2-methylbutane can yield two products.

Reactivity towards E2  R – I > R – Br > R – Cl > R – F

e.g. +

CH3
|
e.g. CH3  C  Br +  + H2O +
|
CH3

Page # 11
 Formation of the Hoffmann product
Bulky bases can also accomplish dehydrohalogenations that do not follow the saytzeff rule. Due to
steric hindrance, a bulky base abstracts the proton that leads to the most highly substituted alkene.
In these cases, it abstracts a less hindered proton, often the one that leads to formation of the least
highly substituted product, called the Hoffmann product.

H CH3
| |
CH3  C  C  CH2 +
| | |
H Br H

Stereospecific E2 reactions
The E2 is stereospecific because it normally goes through an anti and coplanar transition state. The
products are alkene, and different diastereomers of starting materials commonly give different diastereomers
of alkenes.

Base
H
Ph Ph
Ph H

CH3 Ph
H CH3
Br H
Br

CH3
Ph H
Ph Ph
CH3 Ph
H

LECTURE NO.7
1
E Cb Reaction (Unimolecular conjugate base reaction)

7. E1 Cb Reaction (Unimolecular conjugate base reaction)

In the E1 Cb, H leaves first and then the X. This is a two step process, the intermediate is a carbanion.

Mechanism :

Step - I Consists of the removal of a proton, , by a base generating a carbanion

H
| |
CC X
| |
Step - II Carbanion looses a leaving group to form alkene

 –C  C –
| |

Page # 12
Condition : For the E1 CB, substrate must be containing acidic hydrogens and poor leaving groups.

e.g. 

e.g.  X2C = CF2

e.g.  R2–C = O +

Page # 13