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ORG ANIC CHE MIST RY

CHEMISTRY

ORGANIC
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ORGANIC
1. Alkane
Wurtz reaction :
e.g., R1 X + R2 X + 2Na  R1 – R2 + 2NaX

Decarboxylation :
General reaction H
RCOONa  R – H + Na2CO3

O
– O
– ..

Mechanism R–C  R + C H
 R – H
O O

The thermal decarboxylation of free acids may be :

–
O–H O
+ + –
R–C  H +R–C  H + R + CO2 R – H + CO2

..
O O

2. Alkyl halide

Nucleophilic substitution Reaction (SN1, SN2)

SN1 reaction : R – OH + HX  R – X + H2O (R may rearrange)

Reactivity of HX : HI > HBr > HCl

Reactivity of ROH : allyl, benzyl > 3° > 2° > 1° (Carboocation)

Carbocation formed

H  H O 
Mechanism R –OH  R  O H2 2
  R R–X

CH3CHCH3
e.g. CH3 CHCH3 |
| Br
OH Isopropyl bromide
Isopropyl alcohol

SN2 reaction : Alkylhalide are hydrolysed to alcohol very solwly by water, but rapidly by silver
oxide suspended in boiling water.
RX + KOH  ROH + KX
– –
R – X  H O....R .... X  HO – R + X
—
Mechanism HO
—

a a a
– –
C H O.... C.... X C
HO— +   + X—
b d X b d HO d b

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Williamson’s synthesis :
It is the reaction in which sodium or potassium alkoxide is heated with an alkyl halide (SN2).
– –
R1O– + R2–X R 1 O........R 2 ....... X  R1OR 2  X – (g)
This method is particularly useful for preparing mixed ethers.

3. Grignard Reagents

R1H + Mg(OH)X  H2O 1 R2OH 1 2

 R MgX   R H + Mg(OR )X
The majority of Grignard reactions fall into two groups

(i) Addition of the Grignard reagent to a compound containing a multiple - bond group e.g.
C=O ;–CN C = S —N = O ; S=O
; ;

(ii) Double decompsition with compounds containing an active hydrogen atom or a reactive halogen atom.
2
H2O R OH
R1H + Mg(OH)X   R1MgX  R1H + Mg(OR2)X
Important chemical synthesis by Grignard reagent

H
1. Hydrocarbons : RMgBr + H2O  RH + Mg(OH)Br

H
RMgBr + RNH2  RH + RNHMgBr
2. Alcohols :

O 3 H O
(a) Primary alcohols RMgX 2 RMgX
 RO2MgX 
  2ROMgX   2ROH
OMgX
1 H O
(b) Secondary alcohols R CHO + R MgX  RCH
1 2 3 R1CHOHR2
R2

R
1
R
1 OMgX H O R
1 OH
(c) Tertiary alcohols : C = O + R3MgX  C 3 C
R2 R2 R
3
R2 3
R
3. Ethers :
R1OCH2Cl + R2MgX  R1OCH2R2 + MgXCl
4. Aldehydes :

H OMgX
H H O
C= O + RMgX  C 3 RCHO
R
EtO E+O

5. Ketones :

3 H O
R1C (OC2H5)3 + R2MgX  R1R2C (OC2H5)x + Mg (OC2H5)x   R1COR2

3 H O
3 H O
R1CN + R2MgX  R1R2C = NMgX   [R1R2C = NH]   R1COR2 + NH3
Ketimine
6. Acids :

O O H O
RMgX + C  R — C 3 RCO2H
O OMgX

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7. Esters :
Cl Cl OMgX H O
C=O + RMgX  C 3 RCO2Et
EtO EtO R

8. Alkyl Cyanides :
RMgX + (CN)2  RCN + Mg(CN)x
9. Primary amines :
3 H O
RMgX + RONH2  RNHMgX + RH + Mg(OCH3)Cl    RNH2 (40-90%)
RMgX + ClNH2  RNH2 + MgxCl

4. Alkene & Alkyne

Electrophilic addition reactions :
Mechanism
Step 1 : Attack of the electrophile on  bond forms a carbocation.
+ | +
C=C + E –C–C
|
E
+ on the more substituted carbon
Step 2 : Attack by a nucleophile gives the product of addition.
| + | |
–C–C + Nu: CC
| | |
E E Nu

e.g. (a) Addition of water + H2O

(b) Addition of hydrogen halides (where HX = HCl, HBr, HI)

H X
HX HX | |
R – C  C – R  R  CH  CX  R  R  C  C  R
(Markovniko v addition ) | |
H X

5. Aromatic compounds
Electrophilic aromatic substitution :
(a) Bromination of Benzene : Bromination follows the general mechanism for electrophilic aromatic substitu-
tion. Bromine itself is not sufficiently electrophilic to react with benzene, but a strong Lewis acid such as FeBr3
catalyzes the reaction.
Step 1 : Formation of a stronger electrophile.
 
: :

: :

: :

:
: :

:Br – Br : + FeBr3 :Br – Br – FeBr3

Step 2 : Electrophilic attack and formation of the sigma complex.

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H
H H +
: :

: :
:Br – Br: FeBr3
  + FeBr4¯
H H
H

Step :2 Loss of a proton gives the products.

H
H Br
+ HBr + FeBr3
H H
H
bromobenzene
T .S1
reactants T .S2
+ Br2
+ FeBr 3
H
energy Br¯FeBr4
+
intermediate products
Br + HBr
-10.8 kcal/mol + FeBr 3

reaction coordinate

(b) Nitration

H3O  +

H
+
NO2 NO2
+
( -complex)
( - complex)

H+ +

(c) Sulphonation :
The electrophilic reagent, SO3, attacks the benzene ring to form the intermediate carbocation.

2H2SO4 SO3 + +

(d) Friedel Craft reaction :

Alkylation mechanism

(i)

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(ii)

(iii) + AlCl4¯

Acylation mechanism
Acylation of benzene may be brought about with acid chlorides or anhydrides in presence of Lewis acids.

Step 1 : Formation of an acylium ion.

:O : :O:
|| .. || ..+ - + .. +
R – C – Cl: - [R – C = O R – C  O:]
.. + AlCl3 R – C – Cl
.. – AlCl3 AlCl4 + ..
acylchloride acylium ion
complex

Step 2 : electrophilic attack.

O
O ||
|| C
C+ R
H
| +
H
R
sigma complex

Step 3 : Loss of a proton. Complexation of the product.

.. ..
O
O ||
|| .. - C
C :Cl R
R .. – AlCl3
+ H
H acylbenzene
sigma complex
O CH3
O C
|| (1) AlCl3
e.g. CH2CH3
+ CH3 – C – Cl
(2) H2O
ethylbenzene acetyl chloride
CH2CH3
p-ethyl-acetophenone
(70 – 80%)

Note : Friedal - Crafts acylations are generally free from rearrangements and multiple substitution. They do not
go on strongly deactivated rings.

e.g.

Chemical Reactions of Benzene :

Conc. HNO 3
     
H2 SO 4 + H2O

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Conc. H2 SO 4  SO 3
        + H2O

Cl
 2
 + HCl
FeCl3

RCl
  + HCl Friedel-Crafts alkylation
AlCl3

RCOCl
 
AlCl3 + HCl Friedel-Crafts acylation
C6 H6

D / D O + H+
2 

HNO 2 + H2O
  

N=N – Ar
 –
ArN2 X + HX
  

Nucleophilic Aromatic Substitution :
The reaction is second-order in which nucleophilic sbustitution occurs on benzene ring. It is generally accepted
that the reaction proceeds via an intermediate -complex, the benzenonium carbanion (or the pentadienyl
anion), e.g.,
- –
Cl OH Cl OH OH
Cl Cl OH

OH– + slow –   – fast + Cl–

 
  
1. 2. 3.

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6. Chemical Reactions of Phenol

NaOH & Na2CO3
C6H5ONa

CH3COOH & CH3COCl

CH3COOC6H5
(CH3CO)2O
+
C6H5COOH / H
C6H5COOC6H5

Zn / 
C6H5

CH2N2
C6H5OCH3

NH3/ZnCl2
C6H5NH2

NaOH CH3I
C6H5OCH3

PCl5
C6H5Cl + POCl3 + HCl

OH

or
(ArOH)
(minor) + [Major is oxidative
cleavage]

(1)
(2) D

CHCl3 / NaOH / D

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Reimer-Tiemann reaction :
The reaction is conversion of phenol to salicylaldehyde. The mechanism of the Reimer-Tiemann reaction is
believed to involve the formation of dichloromethylene.

O– O O O– O–
2CCl CCl2 H OH –
CHCl2  CHO
   H O –H 
–
OH ; H2 O H 2 CHCl3  H 2O

Kolbe Reaction :
It is the industrial method of preparation of salicylic acid from phenol.
OH ONa OH
H+ OH
General reaction : NaOH CO2
COOH
COONa

O– O
OH + OH
O   H
–
Mechanism CO2  –
C CO2 COOH
H
O

7. Chemical reactions of aniline

Sandmyer’s Reaction :
When a diazonium salt solution is run into a solution of cuprous halide dissolved in the corresponding
halogen acid, the diazo-group is replaced by a halogen atom.
m – Chloronitrobenzene
+ —
NH2 N2 Cl Cl
NaNO2
  CuCl / HCl
  
 (68 – 71%)
HCl
NO2 NO2 NO2

p – Bromotoluene

CH3 CH3
CH3
NaNO2 CuBr / HBr
    
 (70 – 73%)
H2SO4
NH2 Br
N2+HSO4—

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Chemical Reactions of Aniline : HCl 

 [C 6H5NH3 ]Cl 


H SO4 2
2 
 [C6H5NH3 ] 2 SO 4


HAuCl4 
    [C6H5NH3 ] AuCl 4


H PtCl6 2
2   [C 6H5NH3 ] PtCl 6
CH3  CH3  
  C6H5NH(CH3
)   C 6H5N(CH3 )3 
 H  H
CH3COCl
   C6H5NHCOCH3


C H COCl
65  C6H5NHCOC6H5

C H MgBr
25  C2H6

C H SO Cl
65 2  C6H5 – SO2 – NH – C6H5

COCl2
    C6H5 – NH – C – NH – C6H5
||
O
CS2
   C6H5 – NH – C – NH – C6H5
NH2 ||
S
CS2 HCl
    C6H5 – N = C = S

Aniline Na

C 6H 5NH 2
C H CHO
65  C6H5CH = N – C6H5

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8. Aldehyde & ketone

Aldol condensation :
Carbonyl compounds having acidic - H shows this reaction in presence of dil. NaOH or dil. acid.
H
| OH
Dil. NaOH | H , 
2CH3  C  O     CH  C  CH  CHO    CH3 CH  CHCHO
3 2  H2O
|
Crossed aldol condensation H

(i) CH3CHO + HCHO  Dil. NaOH H / H2 O
   HOCH2  CH2  CHO     CH2  CH  CHO

Aerolein
(ii)
Dil. NaOH
CH3COCH3 + HCHO     CH CO  CH CH OH H / H2O
3 2 2    CH3CO  CH  CH2

 Methyl vinyl ketone
Cannizzaro reaction :
Carbonyl compounds not having -H shows following disproportion reaction
O
||
2H  C  H  NaOH  CH3  OH + HCOONa
( 50%)
2 C 6H5CHO + NaOH  C6H5CH2OH + C 6H5COONa
(50%) Sol. benzoate
Crossed Cannizzaro reaction :

+ HCHO + NaOH  + HCOONa

(50%) Sod. formate
Formation of hydrzones and azines
NHNH2 CO
–H2O
C=O + NH2NH2 C C= NNH2 C= N–N = C
OH
Amides formation :
RCO2H + CO(NH2)2  RCONH2 + CO2 + NH3 (g. –v.g.)
RCOCl + 2NH3  RCONH2 + NH4Cl (v.g.)
(RCO)2O + 2NH3  RCONH2 + RCO2NH4 (v.g.)
R1COOR2 + NH3  R1CONH2 + R2OH (g.)
Carbyl amine reaction
RNH2 + CHCl3 + 3KOH  RNC + 3KCl + 3H2O
Perkin reaction :
When benzaldehyde (or any other aromatic aldehyde) is heated with the anhydride of an aliphatic acid (contain-
ing two -hydrogen atoms) in the presence of its sodium salt, condensation takes place to form a
-arylacrylic acid ; e.g., with acetic anhydride and sodium acetate, cinnamic acid is formed.
CH3 CO2Na
C6H5CHO + (CH3CO)2O    C6H5CH = CHCO2H

–
CH3COOCOCH3 + CH3CO2– C H2 COOCOCH3  CH3 CO2H
O O OH
+
C6H5C + CH2COOCOCH3 C6H5CCH2COOCOCH3 H C6H5CCH2COOCOCH3 –H O
2
H H H
H2 O
C6H5CH = CHCOOCOCH3  C6H5CH = CHCO2H + CH3CO2H

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9. Ester formation

General reaction + R OH + H2O

Alcohol

 –
H3 O OH
Hydrolysis of ester R1CO 2H  R 2 OH   R1CO 2R 2  R1CO 2 –  R 2OH

10. Carboxylic Acids

Chemical Reactions of acids

Na Metal 1
R – CH2 – COONa + 2 H2
(1)

NaOH
R – CH2 – COONa + H2O
(2)

NaHCO3
R – CH2 – COONa + CO2 + H2O
(3)

CH3MgBr
R – CH2 – COOMgBr + CH4
(4)

NaOH (CaO) 
R – CH3 + Na2CO3
(5)

SOCl2
R – CH2 – COOH RCH2COCl + SO2
(6)

PCl5
R – CH2 – COCl
(7)

NH3, 
R – CH2 – C – NH2
(8) ||
O
P2O5, 
R – CH2 – C – O – C – CH2 – R
(9) || ||
O O
ROH / H2SO4
R – CH2 – C – OR
(10) ||
O
(i) P + X2 , (ii) H2O
R – CH – COOH
(11) |
X

(i) SOCl2 (ii) CH2N2

R – CH2 – CH2 – COOH
(iii) Ag2O (iv) H2O
(12)

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 Identification of Functional Groups by Laboratory Tests (POC)
Table :

Functional Reagent Reaction

Groups Observation Remarks

[Bayer’s reagent] Pink colour Hydroxylation

C=C/ alk. dil. cold KMNO4 Disappears
CC
Br2 / H2O Red colour decolourises white ppt Bromination

(a) Cuprous chloride + NH4OH Red ppt. R – C  CH + CuCl R – C  C Cu  (red)

R – C  CH
W h i t e p p t .
R – C  CH + Ag+ R – C  C Ag  (white)
(b) AgNO3 + NH4OH

ROH Lucas Reagent ( 3 ) ° C lo u d in e s s a p p e a r s Lucas Test

R – OH + HCl + H2O
i m m i d i a t e l y I. ter.alcohol
3° [Conc. HCl + anhyd. ZnCl2]
( 2 ° ) C l o u d i n e s s a p p e a r s w i t h i n
cloudiness II. sec. alcohol
2°
5 m i n . III. pri.alcohol
1°
( 1 ° ) C lo u d in e s s a p p e a r a f t e r

3 0 m i n .

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 Functional Reagent Observation Reaction Remarks
Groups
Coloured ppt. Test of
Ar – OH FeCl3 (Neutral)
(violet, blue, green buff) enols / phenols
Enols

+ H2
2, 4-Dinitrophenyl hydrazine
Yellow orange ppt. DNP-test
(2, 4-DNP) solution
H  (yellow orange ppt.)

Fehling solution Red ppt. RCHO + Cu+2  RCOOH + Cu2O  + 2H2O Fehling’s test
A&B Fehling soln. Red
R – CHO Tollen’s reagent Black ppt. or silver mirror RCHO + Ag+  RCOOH + 2Ag (Silver mirror) Tollen’s test

Schift’s Reagent * Pink colour resume

R – COCH3
or ArCOCH3
or
I2 / NaOH Yellow ppt of CHI3 (iodoform) Iodoform reaction
CH3CHO

Blue litmus Litmus change to red. Litmus test.

Conc. NaHCO3 solution Effervescence evolve. Sodium bicarbonate

H2O + CO2 test

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Schift’s reagent : p-Rosiniline hydrochloride saturated with SO2 so it is colourless. The pink colour is resumed by RCHO.
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