DAY-1

Functional Groups and Their Properties

Carboxylic Acid
O
||
COOH or C OH or carboxylic acid
Alkanoicacid

Some Key Points

1. Acid turns Blue litmus paper red
2. Acid gives CO 2 with bi-carbonate

1.20
 NaHCO 3 + R COOH
R COONa + H 2 CO 3

H 2 O + CO 2()
3. Cyclic acid is

HO O
Dibasic Cyclic acid
HO O

4. Acid reacts with alcohol to give ester; In this case, in

presence of mineral acid :OH of COOH group and
H + of alcohol are removed.
H+
R CO OH + H OR' R COOR' + H2O

CH3CO OH + H O*R' H+ CH COOR' + H O

3 2

H+
R OH + HNO 3
Ester
( Acid)

O
R O H + HO N RONO2
O Ester
If any acid gives OH and alcohol gives H + in the reaction
then ester is formed.

CH2O H HO NO2 CH2ONO2

3HNO3
CH2O H H ONO2 CH2ONO2 Trinitro
CH2O H HO NO2 glycerene
CH2ONO2

1.21
5. Formic Acid in Vapour phase is known as Formaline.
6. CH 3COOH on solidification is known as Glacial acid.
7. In vinegar, CH 3COOH is 7%
8. In case of carboxylic acid it forms dimer due to H-bonding.
2 CH 3COOH
(CH 3COOH)2
Dimer

O HO
CH3C CCH3
OH O
9. Peroxy acid is a weaker acid as compared to carboxylic acid.

R COOOH R COOH
O O
H
RC RCOH
OO
Peroxy link
Acidic Nature of peroxy acid is lesser than their carboxy acid

] Reasons
In case of peroxy-acid, intra-molecular H-bonding is there, so
removal of H + is not easy.
And, the 2nd reason is no resonance in Peroxy- anion.
OH O
RC )120 O RC ) 120
109
O OH
O O
RC ) RCO H +
OO
No resonance stability of O

1.22
10. Carboxylic acid reacts with carbene to give ester.
CH2NH2
RCOOH R COOCH3 + N2
D
:CH2 carbene
+
RCOO H+ RCOO CH3

11. b- Keto acid or b- Unsaturated acid on heating gives CO 2

(de-carboxylation),
O O
|| D
||
CH 3 C CH 2 COOH CH 3 C CH 3 + CO 2
b a

12. Soda lime performs the given reaction

R COOH NaOH CaO

+ R H

CH 3COOH NaOH CaO

+ CH 4
CO 2

CH 3COOD NaOH CaO

+ CH 4
CO 2

NaOD + CaO
CH 3COOH
CH 3 - D

In this reaction lime absorb the H2O

1.23
] Reason
NaOH*+CaO
CH3COOH CH3H*

NaOH*

CH3COONa + H2O
CaO
NaOH*
(absorb water)

Na2CO3 + CH3H* (main product)

H2O

NaOH + H2CO3

H COOH NaOH CaO

+ H2
Soda lim e

H COOH NaOD CaO

+ H D

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1.24
 Do Yourself -1.4
Q.1 Find out the products of the following reactions.
O
|| COOH
(a) CH3 C CH
COOH

(b) CH COOH
|
CH2 COOH
O
|| COOH
NaOD
(c) A B
CaO
|
COOH

CH2 COOH D
(d) | 2 CH3OH A
CH2 COOH
Ans:

O
||
(a) CH3 C CH3 (b) CH2
|
CH2COOH
O O
|| ||
CH2 COOCH3
(c) (A) (B) (d) |
| | CH2 COOCH3
COOH D

1.25
 Final Shoot - 3
Q.1. IUPAC Name of following compounds:

(a) CH3COOH (b) HCOOH

CH2 COOH
(b) CH3 CH COOH (d) |
| CH2 COOH
CH3

Q.2. Which will turn blue litmus paper red ?.

(a) CH3COOH (b) HCOOCH3
(c) HCl (d) CH3CH2OH

Ans: 2. (a, c)

Sulphonic Acid
SO 3H (Alkane Sulphonic Acid)
CH 3 SO 3H Methan Sulphonic Acid
C H 3 C H 2 SO 3H Ethan sulphonic Acid
2 1

Some Key Points

1. Acidic Nature of R SO 3H >> R COOH

R SO 3H NaOH
R SO 3Na

R SO 3Na NaOH
R OH + Na2 SO 3 (always removed)

1.26
 Na2 SO 3 is removed

CH 3 SO 3Na NaCl
CH 3Cl + Na2 SO 3

CH 3 SO 3Na NaX
CH 3 X + Na2 SO 3

SO3H SO3Na OH

NaOH NaOH
+ Na2SO3

SO3Na

3. H2O/H+

H 2O / H +
CH 3 SO 3Na CH 3 H

ESTER
O
||
RCOOR '
Alkyl alkanoate R C OR '
Albanoate Alkyl

C H 3 C OO CH 3
Methyl ethanote
2 1

C H 3 C H 2 C OO CH 3
Methyl propanoate
3 2 1
O
2 1 O
Cyclo pentanoate.
3 5
4

1.27
 O
||
? Example: CH 3 O C O CH 3

General / Inorganic name : Methyl carbonate IUPAC:

Dimethyl methanoate (diester)
O
||
? Example CH 3 O C OC 2H 5 ethyl methyl methanoate.
1

Some Key Points:

1. Ester is neutral in nature with fruity smell.
2. Esters are formed from acids and alcohols in which OH
group of acid and H of alcohol are removed.
H+
CH 3COOH + HOCH 3
CH 3COOCH 3
O
COOH H+ C
*OH H O O*
2

Do Yourself -1.5
Q.1. Find out the products of the following reactions :
SO3H
|
NaOH H3O+
(a) excess
A B
HO |
COOH

COOH
H+
(b)
CH2 OH

1.28
 O
||
COOCH3 H3O+
(c) A+B+C E
COOC2H5

Find out the sum of molecular weights of A and C.

COOH
|
NaHCO3 NaHCO3
(d) gas
A+B gas
C+D
HO |
SO3H

Q.2 Which has Fruity smell ?

(a) CH 3 COOCH 3 (b) CH 3 CH 2 COOH (c) CH 3 CH 2 OH (d) CH 3 NH 2

O
SO3Na OH
||
| |
C
Ans: (a) A B (b) O
NaO | HO | CH2
COONa COOH
O O
|| ||
* COOH *
(c) A CH3OH B C2H5OH C E + CO2 + CO2
COOH
(d) 44 + 46 = 90 2. (a) *
A C

Amines
Alkane Amine
NH 2

2 1
C H 3 C H 2 NH 2 Ethane amine

C H 3 C H 2 NH Cl N-chloro ethan amine

2 1
C H 3 C H 2 C H 2 NH CH 3 N-methyl propan amine
3 2 1

1.29
 C2H5
CH3N N,N-dimethyl ethan amine
CH3

NH2 Cyclo propan amine

1 NH 5 N-cyclo pentan amine

2 4 (N is in cyclopentane)
3
NH2
2 1 5
Cyclo pentan amine
3 4
1 a min e (Primary)
CH 3 CH 2 CH 2 NH 2

CH 3 CH 2 NH CH 3 2 a min e (Secondary)

CH 3 N CH 3 3 a min e (Tertiaray)

|
CH 3

? P,S and T amine are functional isomers shawing

different properties.
? P,S and T- (alcohol and halides) are not functional
isomers.

Some Key Points:

1. Primary amine give "Mustard oil test"

2. 1 -amine give Carbylamine test in which chloroform reacts

with 1amine in presence of KOH to give isocyanide (bad smell)

1.30
 CHCl +KOH
CH 3NH 2 3
CH 3 NC
(Isocynide)

HNO
3. R NH 2
2
R OH
(NaNO 2 +HCl )

HNO
CH 3CONH 2
2
CH 3COOH
NH2 N2Cl

NaNO2 + HCl

CH2 NH2 CH2 OH

Double bonded carbon with NH 2 gives diazonium chloride

and single bonded one gives alcohol.

Imine: CH = NH : Alkanal imine

2 1
C H 3 C H = NH : ethanal imine

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1.31
 Do Yourself -1.6
Q.1 Find out the Products of the reactions?
O
|| HNO2
(a) NH 2 CH 2 C NH 2 A
NaNO +HCl
2 D
(b) NH 2 CH 2 CH CH = CH NH 2 A B
|
CONH 2

a b
Ans: (a) HO CH 2 COOH (b) HO CH 2 CH CH = CH N 2 Cl
|
COOH
(c) HO CH 2 CH 2 CH = CH N 2 Cl

1.32
 Final Shoot - 4
Q.1. Which is gives mustard oil test

(a) CH3 CH2 NH2 (b) CH3 NH CH3

(c) CH3 CH2 NH CH3 ) (d) CH3 N CH3

|
CH3
Q.2. Which shows formation of alcohol by HNO 2 .

(a) CH3CH2COOH (b) CH3 NH2 (c) CH3CONH2 (d) CH3 NH CH3

Q.3. If R CN on reduction gives CH3CH2 NH2 , then R CN is ?

(a) CH3CH2CN (b) CH3CN (c) HCN (d) None

Ans: 1. (a) 2. (b) 3. (b)

Amide
O
||
RCONH 2 R C NH 2 Alkan amide
O
||
C H 3 C NH 2 ethan amide
2 1
C H 3 C H 2 C H 2 C ONH 2 Butan amide
4 3 2 1
O
||
C H 3 C NH CH 3 N-methyl ethan amide
2 1
O
||
NH 2 C NH 2 : Methan diamide
(Urea)

1.33
Some Key Point
Hoffmann Degradation: It is also known as Hoffmann
bromide reaction, in this, in presence of KOH + Br 2 amide
gives P-amine.
KOH + Br 2
CH 3CONH 2 CH 3 NH 2
1a min e
P2 O 5
CH 3CONH 2 CH 3CN
dehydration

Alcohol
ROH : Alkanol
CH 3CH 2 OH : Ethanol
CH 3 CH CH 3 : Propane-2-ol
|
OH
CH 2 OH
| : Ethan-1, 2-diol
CH 2 OH

Some Key Points :

CH2OH
1. Glycol or ethan glycol or ethan-1, 2-diol
CH2OH

CH2OH
CHOH Propan glycol
CH3
CH2OH It is not
CH2 glycol
CH2OH
1.34
 In case of glycol two -OH groups are near each other.
2. Glycol have Oxidative cleavage with HIO 4 : (Periodic acid)
CH2OH HIO4 HCHO
CH2OH HCHO

CH2OH
HIO4
CHOH HCHO
CHO
CH3
CH3
For oxidative process.
* Alcohol [
0]
Aldehyde [
0]
acid [
0]
CO 2 + H 2 O
or Ketone
CH2OH (1 cleavage) HCHO
HIO4
CHOH (2 cleavage) HCOOH
CH2OH (1 cleavage) HCHO
CH2OH HIO4 HCHO
CHO HCOOH

CHO HCOOH
HIO4
CHOH (2) HCOOH
CH2OH HCHO
CH2OH HCHO
HIO4
C=O (2 cutting) CO2 +H2O
CHO HCOOH

1.35
 CH2 In this 3HIO4 are used.
No cutting
CHOH
(1)
CHOH 3HIO4
(2)
CHOH
(3)
CHOH
No cutting
CH2

3. 100% ethyl alcohol ; is known as, absolute alcohol

4. 95% absolute alcohol + 5% water ; is known as, Sprit.

5. If methyl alcohol is added in spirit, then it is known as
denatured sprit.
6. 80% petrol and 20% ethyl alcohol are known as power
Alcohol Used as Fuels.
7. Ethyl alcohol works on nervous system and cause of
unconsciousness but methyl alcohol is poisonous and it
is the cause of blindness on drinking.
8. Alcohol with group
OH OH
| |
CH 3 CH R and CH 3 CH H

Give haloform test (Iodoform, chloroform ; Bromoform test).

Alcohols give Lucas test
T > S > P Reagent is HCl (conc.)/ZnCl 2

1.36
 Example: Which will give haloform test?
OH OH
| |
(a) CH 3 C CH 3 (b) CH 3 CH CH 3
|
CH 3
OH
|
(c) CH 3 CH CH 2 CH 3
OH
|
(d) CH 3 CH 2 OH or CH 3 CH H

Ans: b, c, d

Do Yourself -1.7
Q.1. Which of the following is not on alcohol ?

(a) OH (b) CH2OH (c) CH3 CH2 OH (d) All

Q.2. Product of the reactions are ?

OH
OH OH OH
(a) HIO4 (b) HIO4

OH OH OH

OH
O

OH OH CH2 NH2
(c) HIO4 (d) HNO2 HIO4
A B
OH OH CH2 NH2

O
CHO CH2 OH
Ans: 1. (a) 2. (a) (b) s HCOOH (c) 4HCOOH + 2CO2 (d) A B 2HCHO
CHO CH2 OH

1.37
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Final Shoot - 5
Q.1. Which gives lucas test fast ?
CH3
|
(a) CH3CH2OH (b) CH3 CH OH

CH3
|
(c) CH3 C OH (d) CH3OH
|
CH3

Q.2. Which gives Idoform tast

(a) 2-butanol (b) 2-propanol
(c) ethanol (d) all
Q.3. Power alcohol has -- % alcohol
(a) 20% (b) 80%
(c) 100% (d) 10%
Ans. 1. (c) 2. (d) 3. (a)

1.38
 Lecture-4

Ether
R O R Alkoxy Alkane
Alkoxy of smaller and alkane of bigger.
CH 3 CH 2 O CH 3 Methoxy ethane

C 2 H 5 O C 3H 7 Ethoxy propane

CH 3 O CH 3 Methoxy methane

Some Key Points

1. Ethers are explosive in nature in air, due to peroxy formation.
2. They are used as solvents.

Thio Ether: R S R : Alkyl alkyl thio ether

CH 3 S CH 2 CH 3 : Ethyl, methyl thioether

CH 3 CH 2 CH 2 SCH 2 CH 3 : Ethyl propyl thioether

] Cyclic Ether
Epoxy alkane CC
O
CH3CHCH2 : epoxy propane
O
4 3 2 1
CH3CH2CH2CH3 : 2, 3-epoxy butane
1 2 3 4
O
1.39
 Aldehyde and Ketone
R\ R\
C = O - Alkanal or R CHO / C = O Alkanone
H/ R

Aldehyde Starts with 1 Carbon but ketone Starts with 3 carbons

O
||
CH 3 CHO : Ethanal CH 3 C CH 3
Pr opanone
CHO
| ethandial
CHO

Some Key Points:

1. Aldehydes without a-Hydrogen have Cannizaro reaction.
It is a redox reaction in presence of a base.

Q Which will give Cannizaro reaction?

(a) HCHO Do not have a - Carbon and a-hydrogen.
So, gives cannizaro reaction.
(b) CH CHO
Have a -Hydrogen, performs no
3
Cannizaro reaction

(c) CHO Do not have a-Hydrogen,

Performs cannizaro reaction.

(d) CHO Have a-Hydrogen, will not

Perform cannizaro reaction

1.40
 CH 3
|
2. (a) CH 3 C CHO Cannizaro reaction is given by this due
|
CH 3
to absence of a-hydrogen.
(b) CH 3 CH 2 CHO Cannizaro reaction is not given by this.

] Cannizaro Reaction:
Oxidation

NaOH*
2HCHO HCOONa + CH3OH*
Reduction

? Cannizaro Reaction is Performed by those which does not

have 'a' hydrogen. But only aldehyde with a Hydrogen

CH3
CHCHO Gives Cannizaro reaction even with having
CH3
a-Hydrogen.

a-Carbon with a-Hydrogen

] Aldol Condensation:
If aldehyde or ketone has a-hydrogen then it gives aldol
condensation in presence of base or acid.
O O OH O
|| || NaOH | ||
CH 3 C H + CH 3 C H CH 3 C CH 2 C H
or H + | Aldol
H

1.41
? Aldehydes except Benzaldehyde give Fehling solution test
and tollen's test (silver mirror test).
O OH
|| |
? a-Hydroxy ketone R C CH 2 also gives these tests.

Q . Which will undergo aldol condensation ?

(a) CH 3CHO (b) CH 3 COCH 3
O
(c) CH3C (d) HCHO

Ans: a, b, c

? Aldehyde or ketone with following groups will give haloform test.

O O
|| ||
CH 3 C H or CH 3 C R

R=CH3 C2H5, etc.

Any alkyl group

Q Which will give haloform test :

O O
|| ||
(a) CH 3 C CH 3 (b) CH 3 C NH 2 or CH 3CONH 2
O O
|| ||
(c) CH 3 C OH or CH 3COOH (d) CH 3 C CH 2 CH 3
Ans: a and d only because b and c are acid amides and acids.
? Carbonyl compounds gives Crystal with NaHSO 3
(Sodium bisulphite)
1.42
 Do Yourself -1.8
Q.1. Find out the products of the reactions ?

NH2
(a) HNO2 HIO4
A B
NH2

(b) NH2 NH2 HNO2 [O]

A B

CHO NaoD
(c) A
CHO
NaoD
(d) HCHO A+B
OH
CHO
Ans: (a) A- B-
CHO
OH

(b) A- HO OH B- O O

(c) COONa Cannizaro reaction (d) HCOONa + CH3OD

CH2OD

Cyanide / Isocyanide
CN NC
Alkane nitrile Alkan isonitrile
or Carbyla min e
2 1 1
C H3 CN C H 3 NC
ethan nitrile Methan isonitrile

3 2 1
C H 3 C H 2 C H 2NC : Propan isonitrile

1.43
 Some Key Points:
1. Isocyanids have bad ( irritating) smell.
2. RNC RCN

Reduction Reduction
RNHCH3 RCH2NH2
KCN
RCN
3. RCl AgCN
RNC
H2 O / H+
4. RCN RCOOH
H2 O / H+
RNC RNH2 + HCOOH

Do Yourself -1.9
KCN Reduction HNO
(a) CH 3 CH 2 Cl A B
2
C

AgCN H O+
(b) CH 3 Cl A 3
B

PCl KCN H O+
(c) CH 3 CH 2 OH
5
A B 3
C

Cl KCN H O+ D
(d) CH 2 A 3
B C
Cl
Ans: (a) A- CH 3 CH 2 CN B- CH 3 CH 2 CH 2 NH 2 C- CH 3 CH 2 CH 2 OH
(b) A- CH 3 NC B- CH 3 NH 2 + HCOOH C- CH 3 CH 2 NH 2
(c) A- CH 3 CH 2 Cl B- CH 3 CH 2 CN C- CH 3 CH 2 COOH
CN COOH
(d) A- CH 2 B- CH 2 C- O=C=C=C=O
CN COOH

1.44
 Final Shoot - 6
Q.1. Give the test to separate CH3CHO and HCHO

(a) Tollens test (b) Cannizaro reaction

(c) Idoform test (d) Fehling solution test

O
||
Q.2. CH3 C CH3 and CH3 CHO are separated by

(a) Tollens test (b) Fehling solution test

(c) Both (d) None

Q.3. Which will give Tollens test ?

O O OH
|| || |
(a) CH3 C H (b) CH3 C CH2

O
||
(c) CH3 C CH3 (d) a and b

AgCN
Q.4. CH3 Cl reduction
A B B is

(a) CH3CH2 NH2 (b) CH3 NH2

(c) CH3CH2CH2 NH2 (d) None

KCN
Q.5. X reduction
A
B B is CH3CH2 NH2 then X is

(a) CH3 Cl (b) CH3CH2 Cl

(c) H Cl (d) None

Ans. 1. (c) 2. (c) 3. (d) 4. (d) 5. (a)

1.45
 Degree of Unsaturation
It is the calculation of unsaturation in the compound in the
form of = or bond or cyclic structure formation.
If the compound is C n 1 H n 2
2n 1 n 2 + 2
1. C n 1 H n 2 D.U =
2
If D.U = 0 , Then all are single bonds.
If D.U = 1 , One double bond or one cyclic
If D.U = 2 , Two double bonds
One bond or Two cyclics
One (=) + one cyclic
8 - 10 + 2
Ex- (1) C 4H 10 D.U . = =0
2
D.U.= 0 means all single bonds.
H3 CCH2 CH2 CH3
2 structures
H3 CCHCH3
|
CH3
6-6+2
2. C 3H 6 D.U = =1
2
D.U.= 1 means one (=) bond or one cyclic.
H2 C=CHCH3 or

8-8+2
3. C 4H 8 D.U = =1
2
1.46
D.U.=1 means one (=) bond or cyclic
C
C
CC=C
CC=CC
C=CCC

D.U. with oxygen: (a) If D.U.=0 with oxygen it is

alcohol or ether
4 6 +2
Ex- C 2 H 6O D.U.= =0
2
CH 3OCH 3 or CH 3CH 2 OH
(b) If D.U.= 1 with oxygen then it is C=C, C=0 or cyclic
Ex- C 3H 6O D.U. =1 O
||
CH 3 CH 2 CHO , CH 3 C CH 3

CH 2 = CH CH 2 OH , CH 2 O
| |
CH 2 CH 2
(c) If two oxygen then
(i) Acid (ii) Ester (iii) Keto-alcohal
(iv) Keto-ether (v) Aldehyde-ether or alcohal
6 6 +2
Ex- C 3H 6O 2 D.U. = =1
2 O
||
It is CH 3CH 2 COOH or CH 3COOCH 3 or CH 3 C CH 2 OH
CH 2 CH 2 CHO etc .
|
OH

1.47
 Do Yourself -1.10
Q.1 Find out which will have aldehyde formation
(a) C6 H10 O (b) C4 H10 O (c) C5 H10 O 2
(d) C3 H 6 O (e) C n H 2n O
Q.2. Which formula may have iodoform formation
(a) C3 H 6 O (b) C4 H10 O (c) C5 H12 O (d) C2 H 6 O
Ans: 1. (a, c, d, e) 2. (a, b, c, d)

Final Shoot - 7
Q.1. Find out D.U. of Benzene

(a) 1 (b) 2

(c) 3 (d) 4

Q.2. Find out Cyclic structures of C4 H10

(a) 1 (b) 2

(c) 3 (d) None

Q.3. C4 H 8 has total number of cyclic structures

(a) 1 (b) 2

(c) 3 (d) 4

Q.4. C3 H 8O has total number of alcohols

(a) 1 (b) 2

(c) 3 (d) 4

Ans. 1. (d) 2. (d) 3. (b) 4. (b)

1.48
This content is a part of the Book Organic for Doctors with Video lectures
and solutions by Er. Dushyant Kumar (B.Tech, IIT-Roorkee)

1.21