General Organic Chemistry-III

GENERAL ORGANIC CHEMISTRY - III

Section (A) : Solvents, Reagents and Leaving groups
1. Solvents
(a) Non polar solvents (examples: Benzene, hexane, toluene, CCl4 etc.)
(b) Polar solvents: (i) polar protic (ii) polar aprotic
(i) Polar protic : A polar solvent which has acidic hydrogen and donate H+ ion.
(examples: H2O, ROH, RCOOH etc.)
(ii) Polar aprotic : A polar solvent which does not have acidic hydrogen.
(examples: Ether, acetone, DMF, DMA, DMSO etc.)
Note : Non polar solvents are always aprotic in nature.
Worksheet-1
Tick mark () in right columns
[Link]. Solvents Polar Protic Aprotic Remarks
1. H2O    Polar protic solvent
2. CH3OH   Polar protic solvent

3. CH3CH2OH   Polar protic solvent

4. H–COOH   Polar protic solvent

5. CH3–COOH   Polar protic solvent

6. NH3   Polar protic solvent

7. CH3COCH3 (Acetone)    Polar aprotic solvent

8.    Polar aprotic solvent

(CH3)2S=O (DMSO)

9.    Polar aprotic solvent

(DMF)

10.    Polar aprotic solvent

(DMA)

11.    Non-polar solvent

12.     Non-polar solvent

13. CH3–CH2–CH2–CH2–CH3    Non-polar solvent

 General Organic Chemistry-III
2. Reagents
Reagent generates three type of attacking species.
(a) Electrophiles: Electrophiles are electron deficient species, which can accept a pair of electron.
(b) Nucleophiles: Nucleophiles are electron rich species having atleast one unshared pair of electron.
(c) Radicals: It is an electron deficient species with odd electron around an atom.
CH3 , C2H5, C2H5O, CH3COO, X etc.

2.1 Nucleophiles
Nucleophiles are electron rich species having atleast one unshared pair of electron. It can be neutral or
negatively charged. It also acts as Lewis base.
CN–, OH–, Br –, I –, NH3 , etc.

** Ambident nucleophiles
The species which have more than one nucleophilic sites for reaction are called ambident nucleophiles.
CN , O–N=O , O–CH=S, HSO3

** Nucleophilicity: The tendency to give e– pair to an electron deficient carbon atom is defined as
nucleophilicity.
Criteria for Nucleophilicity
1. The factors which increases e– density (+, +M groups) at donor atom increases nucleophilicity.
2. The more polarisable donor atom is the better nucleophile. Therefore size of donor atom increases,
nucleophilicity also increases.
(a) Periodicity
Nucleophilicity decreases from left to right in a period because electron negativity of atoms increases.
CH3– > NH2– > OH– > F–
Top to bottom in a group nucleophilicity increases because size of donor atom and polarizability
increases.
** Basicity decreases from top to bottom in a group.
Acidic strength: HI > HBr > HCl > HF
Basic strength: F¯ > Cl¯ > Br¯ > ¯
Nucleophilicity: F¯ < Cl¯ < Br¯ < ¯
(Due to smaller size of F¯ it is more solvated (hydration) by polar protic solvent).
Hydration or solvation decreases gradualy down the group.
** Negative charge density increases, nucleophilicity increases.
(b) Nucleophilicity of halogens in polar aprotic solvents
Polar aprotic solvents do not hydrate or solvate the anions therefore nucleophilicity of smaller anion is
higher than that of larger anion. Hence order of nucleophilicity of halide ions is F¯ > Cl¯ > Br¯ > ¯
(c) Steric effects on nucleophilicity
If the steric crowding becomes very high, the nucleophilicity becomes so poor that the base may be
regarded as non-nucleophilic.
N
(i) < (ii) N <

Note-
(1) Strong bases but weak nucleophiles are t-BuO–, LDA [N(iPr)2Li], NEt3.
(2) Strong nucleophiles but very weak bases are , Br .

(3) Strong nucleophiles but moderate bases are HS, N2H4 .

 General Organic Chemistry-III
Worksheet – 2
Certain species are mentioned in each column in the table below. The student should mark
“>”, “<” or “=” signs in between given species to generate the correct order of the property
mentioned at the top.

Nucleophilicity Basicity Remarks / Reasons

The tendency to give e– pair

A base is a substance that
to an electron deficient carbon Basicity can be determine
can accept a proton by
atom is defined as by value of pKb and pKaH.
Def. donating a pair of electrons.
nucleophilicity. (We use pKaH to mean the
It is thermodynamic
It is kinetic controlled property pKa of the conjugate acid)
controlled property (TCP)
(KCP)

If donor atoms belong to

same period, then
1 CH3¯ NH2¯ OH¯ F¯ CH3¯ NH2¯ OH¯ F¯
nucleophilicity and basicity
order is same

2 SiH3¯ PH2¯ SH¯ Cl¯ SiH3¯ PH2¯ SH¯ Cl¯ " " "

Down the group

3 F¯ Cl¯ Br¯ I¯ F¯ Cl¯ Br¯ I¯ nucleophilicity increases
while basicity decreases.

" " "" "

4 OH¯ SH¯ OH¯ SH¯ "

5 RO¯ RS¯ RO¯ RS¯ " " "

If donor atom is same, then

6 RO¯ HO¯ RO¯ HO¯ generally nucleophilicity and
basicity order is also same.

7 RCOO– PhO¯ HO¯ RO¯ RCOO– PhO¯ HO¯ RO¯ " " "

8 " " "

Anion is better nucleophile

9 HO¯ H2O HO¯ H2O
and better base.

10 NH2¯ NH3 NH2¯ NH3

 General Organic Chemistry-III
2.2 Leaving groups and leaving ability (Nucleofugality)
Weaker bases are always good leaving groups (nucleofuse).
A good leaving group always stabilize the transition state and lowers its energy of activation hence
increases the rate of the reaction.

Note: (1) Strong bases rarely act as leaving group.

(Strong base, poor leaving group)

(Strong base but does not act as a leaving group)

(2) The leaving group should have lower bond energy with carbon.
(3) Negative charge is stabilized either by dispersal or delocalization in leaving group.

Worksheet – 3
The student should mark “>”, “<” or “=” signs in between given species to generate the correct
leaving group ability order.

+ +
1. 6. NR3 SR2

2. CH3¯ NH2¯ OH¯ F¯ 7. CF3SO3¯ PhCOO¯ PhO¯ EtO¯

3. R–COO¯ PhO¯ HO¯ RO¯ 8. H2O OH–

–
4. SH¯ OH¯ 9. N2 NH2

ONs–  Nosylate

5. OTs–  Tosylate
(ONs–) (OTs–)
OBs–  Brosylate

Other good leaving groups are -

2.3 Electrophiles
Electrophiles are electron deficient species, which can accept a pair of electron.
     
(a) Positively charged species are H , Cl, Br, NO2 , CH3 , H3 O
(b) Species with vacant orbital at central atom are PCl5, AlCl3, SO2, SO3, BH3 and carbenes.
(c) Disociable  and  bonds are CO2 and RCOCl.
 General Organic Chemistry-III
Generation of electrophiles
Compounds Reagents Electrophile Chemical reaction to generate electrophile
1. Alkane NA
H+ 
2. Alkene Carbocation H
(H2SO4…..)  R – C H – CH3
R–CH=CH2 

H+ 
3. Alkyne Carbocation H
(H2SO4…..)  R – C  CH2 (rarely formed)
R–CCH 

H+ 
4. Alcohol Carbocation H
(H2SO4…..) R–CH2–OH 
 R – C H2

Lewis acid
Carbocation 
5. Alkylhalide (AlCl3, ZnCl2, AlCl
RCH2X 
3
 R – C H2 + AlCl3X–
BF3,FeBr3 …)

Lewis acid
Acyl 
 R – C  O  AlCl3 X –
6. Acid halide (AlCl3, ZnCl2, AlCl
Carbocation R–COX 
3
BF3……)

Lewis acid
Acyl 
 R – C  O  AlCl3OH–
7. Acid (AlCl3, ZnCl2, AlCl
Carbocation R–COOH 
3
BF3……)

8. Halogen Lewis acid Halonium ion

 X   AlCl3 X –
AlCl
(Cl2,Br2,2, (AlCl3, ZnCl2, (X+) X2 
3

ICl,Br,BrCl) BF3……)

9. Carbonyl 
H+ Carbocation H
Compound R2C=O 
 R 2 C– OH

O
10. For nitration conc.HNO3 + Nitronium ion –H2O
O=N–OH + H–O–S–OH NO2+ + HSO4–
reaction conc.H2SO4 NO2+ 
O O

O O
11. For –H2O
sulphonation Conc. H2SO4 SO3(SO3H+) HO–S–OH + H–O–S–OH SO3H+ + HSO4–
reaction
O O

O
12. For –H2O
nitrosation HNO2 + H+ NO+ O=N–OH + H–O–S–OH NO+ + HSO4–
reaction
O

13. For
CO + HCl +  
Gattermann H–C  O CO + HCl + AlCl3  H – C  O + AlCl4
–
AlCl3
Koch reaction

14. For
HCN + HCl +  
Gattermann H – C  NH HCN + HCl + AlCl3  H – C  NH + AlCl4
–
AlCl3
reaction
 General Organic Chemistry-III
Worksheet-4 (A)
Generation of electrophiles :

S.N. Reactant Reagent Electrophile

Br
1  
AlCl3


Cl
2 
AlCl3

Ph

O
3

Anhyd. AlCl
3
CH3–C–Cl

Cl
4 
AlCl3

O

OH
5 
H2SO4


6 
H2SO4


7 
H2SO4


O O
8 
AlCl3

R–C–O–C–R

O O O
9 
AlCl3


Worksheet-4 (B)
Generation of electrophiles:

S.N. Reactant Reagent Electrophile

1 CH3–CH2–CH=CH2 
H2SO4


2 
H2SO4


Ph
3 
H2SO4



4 OCH3 
H




5
O 
H


 General Organic Chemistry-III


6 
H




7 
H




8 
H


Ph

9 D


O

Worksheet-4 (C)
Generation of electrophiles :

S.N. Reactant Reagent Electrophile


Anhy. AlCl3
1 CH3–CH2–CH2–Cl

2 CH3–CH2–CH2OH 
Conc.H2SO4




3 OH

H, H2SO4




4 
H


CH3


5 
H



6 OH 
H


H2O


7 
H


Ph
Cl
8 
AlCl3


Br

9 3 FeBr

O
 General Organic Chemistry-III
Worksheet-4 (D)
Generation of electrophiles :
S.N. Reactant Reagent Electrophile

1 
H


OH

 
2 3 HF, BF


FeBr
3
Br
 3

4 OH 
H2SO4



5 
H



Br
6 
AlCl3

O

OH

7 
H



Cl

8 3 FeCl

Section (B) : Types of organic reactions

3.1 On the basis of nature of reactants
(a) Addition reaction: Where two or more molecules combine to form a larger one (the adduct). Addition
reaction include such reactions as halogenation, hydrohalogenation, hydration etc.

R HCN R CN
C=O C
R R OH

HCl
(i) R–CH=CH–R R–CH–CH–R
H Cl
Br2
(ii) R–CC–R R–C=C–R
Br Br
 General Organic Chemistry-III
(b) Substitution reaction: In which one group in a chemical compound is replaced by another group.
Such reaction follows free radical substitution, aromatic electrophilic substitution (SE), nucleophilic
substitution (SN1, SN2, SNi, SN2Th) etc.
R–L 
Y
 R–Y + L
H H
C C
(1) H + Cl–Cl 
hv
H + H–Cl
H Cl
H H
(2) R–CH2–Br   R–CH2–OH + NaBr
NaOH


H NO2 NO2
(3)   + H+


(4) R–C–Cl 
EtO
R–C–OEt + Cl–
O O
(c) Elimination reaction: In which two substituent groups or atoms are removed from a molecule either
in a one or two-step mechanism. Such reactions include dehydration, dehalogenation etc.

R–CH–CH–R R–CH=CH–R + XY
X Y

3.2 On the basis of electronic nature of reagents

(a) Nucleophilic reaction: When attacking reagent is nucleophile in first step of mechanism then the
reaction is generally called nucleophilic reaction.
(b) Electrophilic reaction: When attacking reagent is electrophile in first step of mechanism then the
reaction is generally called electrophilic reaction.
(c) Free radical reaction: When attacking reagent is free radical then reaction is called free radical
reaction.

Types of reagents :
(a) Nucleophile ( Nu ): Electron rich species having lone pair of electrons & complete octet at donor
atom.
(b) Electrophile (E): Electron deficient species having vacant p or d-orbitals.
(c) Free radical (R): Electron deficient species having odd electron in valence shell.

Worksheet-5
Write the type of reactions for the followings.

1. CH3–CH2–Br 
NaOH
 CH3–CH2–OH [………………………………………………………]

CH3  CH  CH3   CH3–CH=CH2

Alc. KOH
2. [………………………………………………………]
|
Br

3. + Br2 
Fe
+ HBr [………………………………………………………]
Br
HBr
4. CH3–CH2–CH=CH2  CH3–CH2– CH2–CH2 [………………………………………………………]
Peroxide or light
Br
Br OH
aq. NaOH
5. CH3   CH3 [………………………………………………………]
SN1
 General Organic Chemistry-III
NaNH
6. CH3–C–Cl 
2
 CH3–C–NH2 + NaCl [………………………………………………………]
O O
KCN
7. R–CH=O  R–CH–CN + K2SO4 [………………………………………………………]
H2SO 4
OH
Br2
8.  2-Bromo-2-methylbutane
Isopentane  [………………………………………………………]
h

Section (C) : Applications of chemical kinetics in organic chemistry

Chemical kinetics is the branch of physical chemistry that deals with the study of rate of reactions and
the factors governing rate of reaction.

4.1 Rate of chemical reaction

The rate of reaction is the change in concentration of reactants or products per unit time.
Change in concentration c mol / lit.
Rate = = = = mol lit–1 time–1
Time taken t time

Rate is always defined in such a manner so that it is always positive value.

For a reaction R  P

[P]

Conc.
c [R] [P]
Rate = =– =
t t t
[R]

Time

Relation between the rates of reactions of different species taking part in a chemical
reaction
Rate of reaction of all the species taking part in a chemical reaction are not equal as evident from their
stochiometric coefficients. Rate of reaction is always defined for a balanced chemical equation.
aA + bB  cC + dD
1 d[A] 1 d[B] 1 d[C] 1 d[D]
Rate of reaction = – =– =+ =+
a dt b dt c dt d dt

Ex. N2 + 3H2  2NH3

* From above we can have the following relation between the rate of reactions of different species
d[N2 ] 1 d[H2 ] 1 d[NH3 ]
Rate of reaction = – =– =
dt 3 dt 2 dt

4.2 Molecularity
Molecularity is defined only for the elementary reactions which is equal to number of molecules
which make transition state or activated complex because of collisions in proper orientation and
with sufficient energy.
No elementary reactions involving more than three molecules are known, because of very low
probability of near-simultaneous collision of more than three molecules.
The rate law for the elementary reaction
aA + bB  products
rate = k[A]a[B]b, where a + b = 1, 2 or 3.
The mechanism of any complex reaction is always written in terms of elementary steps, so molecularity
of each of these steps will be defined but net molecularity of complex reaction has no meaning.
 General Organic Chemistry-III
4.3 Order of reaction
Let there be a reaction
n1 A + n2 B  products.
  Rate of reaction:
R  [A]P [B]q ............ (i)
R = k [A]P [B]q .......... (ii)
(Rate law equation) where k = rate constant
 Where p & q may or may not be equal to n1 & n2.
 p is order of reaction with respect to reactant A and q is order of reaction with respect to reactant B and
(p + q) is overall order of the reaction.
 Order of reaction is experimentally determined & may be positive, negative, zero or fractional.
Comparison between molecularity and order of reaction

Molecularity of reaction Order of reaction

1. It is defined as the sum of the power of

1. It is defined as the no. of molecules of
concentration terms that appear in the rate law
reactant taking part in a particular step.
equation.

2. It is always a whole number. It can neither be

2. It may be zero, fractional or any integer.
zero nor fractional.

3. It is derived for slowest step in the

3. It is derived from rate expression.
mechanism of reaction generally.

4. It is theoretical value. 4. It is experimental value.

4.4 Transition state & Activated complex

The transition state is the transitory of molecular structure in which the molecule is no longer a
substrate but not yet a product.
All chemical reactions must go through the transition state to form a product from a substrate molecule.
The transition state is the state corresponding to the highest energy along the reaction co-ordinate.

Transition state is unstable and cannot be isolated.

In equation : S  X  P,
X is the transition state, which is located at the peak of
the curve on the Gibbs free energy graph.

4.5 Activation energy

“It can be defined as, the minimum amount of energy that is required to activate atoms or
molecules to a condition in which they can undergo chemical transformation”.
In terms of transition state theory, the activation energy is the difference in energy content between
atoms or molecules in an activated or transition state configuration and the corresponding atoms and
molecules in their initial configuration.
 General Organic Chemistry-III

HR = Summation of enthalpies of reactants

HP = Summation of enthalpies of products
H = Enthalpy change during the reaction
Ea1 = Energy of activation of the forward
reaction
Ea2 = Energy of activation of the backward
reaction

Threshold energy: The minimum amount of energy which the colliding molecules must possess as to
make the chemical reaction to occur is known as threshold energy.
Ea = Threshold energy – Actual average energy of reactants
Ea is expressed in kcal mole–1 or kJ mole–1.
Greater the height of energy barrier, greater will be the energy of activation and slower will be the
reaction at a given temperature.

4.6 Reaction profile

The energy change as a function of the progress of the reaction is known as reaction profile or energy
diagram.

Elementary reactions: These reactions take place in single step without formation of any
intermediate.

T.S. = Transition state

In case of elementary reactions the sum of stoichiometric coefficients is equal to order of the reactions.
Complex reactions: Reaction which proceed in more than one steps are known as complex
reaction. These reactions take place in a sequence of a number of elementary reactions.

For complex reactions order is to be experimentally calculated.

 General Organic Chemistry-III
4.7 Factors affecting rate of chemical reaction
(i) Effect of concentration: It is seen by rate law equation which is experimental data.
r = k[A]m [B]n
(ii) Chemical nature of reactants: This is the point of detailed study in organic chemistry.
(In general rate: Gaseous > Liquid > Solid medium)
(iii) Effect of catalyst: Presence of positive catalyst lower down the activation energy hence increases
the rate of reaction.
(iv) Effect of temperature: rate of reaction generally increases with temperature.

Absence of catalyst
Ea Presence of catalyst
E'a
Energy

Products

Reaction Coordinate 
4.8 Rate determining step
The slowest step of the mechanism is called rate determining step of the reaction. Rate law of reaction
is calculated with the help of rate determining step (R.D.S).

Section (D) : Organometallic compounds and Grignard reagent

Organometallic compounds are the organic compounds in which a metal atom is directly attached to
carbon atom through covalent bond or ionic bond.
– 
For example C–M or C M ( R-MgX, R2CuLi, R2Zn, RNa, RLi)
Note: (1) RONa (Sodium alkoxide). CH3COONa (Sodium acetate), CH3COOAg (Silver acetate), RSK
(Potassium mercaptide) RNHK (N-Alkylpotassamide), (CH3COO)4Pb (Lead tetraacetate), etc are not
organometallic compounds.
(2) It should be noted that (CH3)4Si (Tetramethylsilane, TMS) is also not an organometallic compound
because silicon is a nonmetal.
(3) Most important examples of organometallic compounds are Grignard reagents. In Grignard
reagent, the carbon and magnesium atom are bonded with each other through polar covalent bond
(35% ionic character) and magnesium atom is also attached to halogen by ionic bond.

5.1 Grignard reagent

(a) Preparation of Grignard reagent (G.R.)
Dry and pure
RX + Mg 
 RMgX
Ether
Dry ether is used as a solvent because it is a Lewis base that donates its lone pair of electrons to
electron-deficient magnesium atom, therefore providing stability to the Grignard's reagent.


 General Organic Chemistry-III
Process: To an etherial solution of alkyl halide Mg metal is added at very low temp. (0-5°C). A vigorous
reaction takes place, and a solution of G.R. is obtained. It cannot be evaporated to get it in solid state
because reaction will be explosive. It is stable only in solution state.
Reactivity order with respect to X (For preparation of RMgX)

(b) Examples of Grignard’s reagent

1. Saturated Aliphatic Grignard's reagent
R–MgX (Alkylmagnesium halide)
CH3–MgI (Methylmagnesium iodide)

2. Unsaturated Aliphatic Grignard's reagent

(i) Alkenyl Grignard's reagent: CH2=CH–MgX
(ii) Alkynyl Grignard's reagent: CH3–CC–MgX
(iii) Allylmagnesium halide: CH2=CH–CH2–MgX

3. Alicyclic Grignard's reagent: ,

4. Aromatic Grignard's reagent: (Phenylmagnesium halide)

(c) Reactivity of Grignard reagent

* On having same hydrocarbon radical, the order of reactivity of Grignard's reagent will be as follows-
RMgI > RMgBr > RMgCl

* Reactivity order with different alkyl part is-

RMgX : (R = 3º > 2º > 1º > CH3 > C=C > CC)

* Reactivity order of Grignard reagent with respect to different reactants (Substrates) is-
Acidic hydrogen > RCOCl > RCHO > RCOR > RCOOR’

Note: (1) Except halogens all other functional groups which can react with Grignard reagent [including –NO2,
–CN, CHO] must be absent in the alkyl group otherwise G.R. will be destroyed by internal reactions.

(2) If the alkyl part has more stable negative charge, then RMgX is more stable and it will be less
reactive.

(d) Synthesis of other organometallic compounds from Grignard reagent

R–Mg–X + ZnCl2  R2Zn + MgX(Cl)
R–Mg–X + HgCl2  R2Hg + MgX(Cl)
R–Mg–X + SnCl4  R4Sn + MgX(Cl)
R–Mg–X + PbCl4  R4Pb + MgX(Cl)
R–Mg–X + CdCl2  R2Cd + MgX(Cl)
 General Organic Chemistry-III
llustrations

CH3

CH3–C–CH2–Br + Mg 
 product is
Dry Ether
1.

CH3
CH3
CH3 CH3

(A) CH3–C–CH2 Mg (B) CH3–C–CH2–MgBr (C) (CH3)3C–MgBr (D) CH3–C—CH2

CH3 BrMg CH3
2 CH3

2. CH3MgBr reacts most easily with -

(A) Phenol (B) Acetone (C) Ethyl ethanoate (D) CH3–CH2–Br

3. Which of the following Grignard reagent is most reactive?

(A) RMgCl (B) RMgBr (C) RMg (D) All have same reactivity

4. Which of the following is not organometallic compound?

(A) (CH3)2Cd (B) (CH3CH2)2Zn (C) Ph-MgBr (D) C6H5–ONa
5. Reactivity and stability of following Grignard reagents is -
(1) CH3–CH2–MgX (2) CH2=CH–MgX (3) CH3CC–MgX
Ans. 1. (B) 2. (A) 3. (C) 4. (D)
5. Reactivity order : 1 > 2 > 3 ; Stability order : 1 < 2 < 3

Section (E) : Acid base reaction

6.1 Test of acidic hydrogen (Liberation of H2 on reaction with Na metal)
All active-H (attached with O, S, X, Csp and active methylene) gives H2 gas with Na or K metals.
CH3COOH + Na  CH3COONa + ½H2 

llustrations
Na Na
1. H–O–H 
 NaOH + ½ H2  2. R–O–H 
 R–ONa + ½ H2
Na Na
3. RSH 
 RSNa + ½H2    4. NH3 
 NaNH2 + ½H2 

Na Na
5. CH3CONH2 
 CH3CONHNa + ½H2  6. 
 Na + ½H2 
N

Na  1
7. R–C–CH2–C–R 
 [R–C–CH–C–R]Na + H2
2
O O O O

6.2 Acid base reaction with Grignard reagent

Compounds having reactive or acidic hydrogen give acid base reaction with grignard reagent.
Z – H + R – MgX  R – H + Z – MgX
Note : If R = CH3 in R–Mg–Br then methane gas is released.
 General Organic Chemistry-III
The reaction is used for estimation of active hydrogen atoms present in a molecule. This method is
called Zerewitinoff method for estimation of active hydrogen atoms.
Z–H H–OC–R
RH + Mg(Br)Z
||
O
H–OH RH + Mg(Br)OC–R
RH + Mg(Br)OH H–NH–C–R ||
|| O
O
H–OR R–Mg–Br RH + Mg(Br)NH–C–R
RH + Mg(Br)OR
||
H O
H–OPh
RH + Mg(Br)OPh H
RH + Mg(Br)
O
D–OD ||
RD + Mg(Br)OD C–CH3
H–CH O
H–X C–CH3 ||
RH + Mg(Br)X ||
O C–CH3
RH + Mg(Br) CH
H–CN C–CH3
RH + Mg(Br)CN ||
H–NH2 O
RH + Mg(Br)NH2

H–SH H–NHR
RH + Mg(Br)SH RH + Mg(Br)NHR

H–SR H–NR2
RH + Mg(Br)SR RH + Mg(Br)NR2

H–CC–R
RH + Mg(Br)CC–R

6.3 Feasibility of reactions

Reaction is feasibile if product is more stable than reactant.

1. Write the products, if reaction is feasible.

NaHCO
(i) CH3SO3H 
3
CH3SO3Na + H2O+CO2

14 14
NaHC O
(ii) PhCOOH 
3
 PhCOONa + H2O+ CO 2

14
NaHC O
(iii) PhCH2OH 
3
 No reaction
OH
NaHCO
(iv) 
3
No reaction

Worksheet-6(A)
Mark E or Y or N, where *(E = Equilibrium, Y = Yes, N = No)

Bases Acids Ph–SH Ph–OH R–OH R–CC–H NH3 R–NH2

O
1. R–C–O
(Weak base in water)
2. Ph–O
(Weak base in water)
 General Organic Chemistry-III

3. OH
(Strong base in water)

4. R–O
(Strong base)

5. R–CC:
(Strong base)

6. H
(Very Strong base)

7. NH2
(Very Strong base)

8. R
(Strongest base)

Worksheet-6(B)

CH3–C–CH2–C– CH3
Bases Acids Ph–SO3H R–COOH H2CO3 H2O
O O

O
9. R–C–O
(Weak base in water)
10. Ph–O
(Weak base in water)

11. OH
(Strong base in
water)

12. R–O
(Strong base)
13. R–CC:
(Strong base)
14. H
(Very Strong base)

15. NH2
(Very Strong base)

16. R
(Strongest base)
 General Organic Chemistry-III

Answers
Worksheet-1

Polar Protic Aprotic Polar Protic Aprotic Polar Protic Aprotic

1.   – 6.   – 10.  × 
2.   – 7.  ×  11. × × 
3.   – 8.  ×  12. × × 
4.   – 9.  ×  13. × × 
5.   –       

Worksheet – 2
Nucleophilicity Basicity Nucleophilicity Basicity
1 CH3¯>NH2¯>OH¯>F¯ CH3¯>NH2¯>OH¯ >F¯ 6 RO¯ > HO¯ RO¯ > HO¯

2 SiH3¯>PH2¯>SH¯>Cl¯ SiH3¯>PH2¯>SH¯>Cl¯ 7 RCOO–<PhO¯<HO¯<RO¯ RCOO–<PhO¯<HO¯<RO¯

3 F¯< Cl¯ < Br¯ < I¯ F¯> Cl¯ > Br¯ > I¯ 8 RCOO– > RSO3– RCOO– > RSO3–

4 OH¯ < SH¯ OH¯ > SH¯ 9 HO¯ > H2O HO¯ > H2O
5 RO¯ < RS¯ RO¯ > RS¯ 10 NH2¯ > NH3 NH2¯ > NH3

Worksheet – 3

1. > > > 6. NR3+ < SR2+

2. CH3¯ < NH2¯ < OH¯ < F¯ 7. CF3SO3¯ > PhCOO¯ > PhO¯ > EtO¯
3. R–COO¯ > PhO¯ > HO¯ > RO¯ 8. H2O > OH–
–
4. SH¯ > OH¯ 9. N2 > NH2
5. (ONs–) > (OTs–)

Worksheet-4 A,B,C
S.N. Electrophile(4-A) Electrophile(4-B) Electrophile(4-C)

    1,2H
1  AlCl3Br CH3CH2 C HCH3 CH
 3  CH2  CH2 AlCl 4
  CH3  CH  CH3
   Shift

 –    1,2H 
  CH3  CH  CH3
2 Ph  AlCl4 CH3  CH2  CH2  
H   Shift


 Ph 1,2H
3   
CH3  C  O  AlCl4 H  Shift 
 
H +
4  AlCl4
–
OCH3 1,2H  +
C=O
  
 H CH3 Shift CH3
Ph
H 
 

1,2H
5    
H Shift
O
 General Organic Chemistry-III
  

6 1,2bond
H 
Shift
H


7 H   
1,2H
 
Ph Shift Ph
  
R  C  O  +  1, 2Me
   
8  Shift
O 
R–C–O–AlCl3 Ph
O 
–
9 OAlCl3 D 1,2H
 + FeBr4 
 
O O Shift O
C=O

Worksheet-4D


1  5 

 O
 
2 6
O AlCl3Br 

  
3  7



 
4 8 

Worksheet-5.
1. Substitution reaction. 2. Elimination reaction. 3. Substitution reaction. 4. Addition reaction.
5. Substitution reaction. 6. Substitution reaction. 7. Addition reaction. 8. Substitution reaction.
Worksheet-6A Worksheet-6B
1. N N N N N N 9. Y E N N N N
2. Y N N N N N 10. Y Y Y E N N
3. Y Y E N N N 11. Y Y Y Y E E
4. Y Y E N N N 12. Y Y Y Y E E
5. Y Y Y N N N 13. Y Y Y Y Y Y
6. Y Y Y Y N N 14. Y Y Y Y Y Y
7. Y Y Y Y N N 15. Y Y Y Y Y Y
8. Y Y Y Y Y Y 16. Y Y Y Y Y Y
General Organic Chemistry-III