.

PHARMACY PROGRAM (2019-23)

SEMESTER-II
Course Name : Pharmaceutical Organic Chemistry-I
Course Code : BP202T
Course Instructor : Dr. Sapna Jain
Till 27-Jan-2020, Covered: Lectures – 11 and Tutorial - 2
Hours: 3+1+0 Credits: 4

UNIT-I 07 Hours
· Classification, nomenclature and isomerism
Classification of Organic Compounds
Common and IUPAC systems of nomenclature of organic compounds
(up to 10 Carbons open chain and carbocyclic compounds)
Structural isomerisms in organic compounds
UNIT-II 10 Hours
· Alkanes*, Alkenes* and Conjugated dienes*
SP3 hybridization in alkanes, Halogenation of alkanes, uses of paraffins.
Stabilities of alkenes, SP2 hybridization in alkenes
E1 and E2 reactions – kinetics, order of reactivity of alkyl halides, rearrangement of carbocations,
Saytzeffs orientation and evidences. E1 verses E2 reactions, Factors affecting E1
and E2 reactions
Ozonolysis, electrophilic addition reactions of alkenes, Markownikoff’s orientation, free radical
addition reactions of alkenes, Anti Markownikoff’s orientation.
 
Stability of conjugated dienes, Diel-Alder, electrophilic addition, free radical addition reactions of
conjugated dienes, allylic rearrangement.
. 

UNIT-III 10 Hours
· Alkyl halides*
SN1 and SN2 reactions - kinetics, order of reactivity of alkyl halides,
stereochemistry and
rearrangement of carbocations.
SN1 versus SN2 reactions, Factors affecting SN1 and SN2 reactions
Structure and uses of ethylchloride, Chloroform, trichloroethylene,
tetrachloroethylene, dichloromethane, tetrachloromethane and iodoform.
 · Alcohols*- Qualitative tests, Structure and uses of Ethyl alcohol, Methyl alcohol,
chlorobutanol, Cetosteryl alcohol, Benzyl alcohol, Glycerol, Propylene glycol.
 
UNIT-IV 10 Hours
· Carbonyl compounds* (Aldehydes and ketones)
Nucleophilic addition, Electromeric effect, aldol condensation, Crossed Aldol condensation,
Cannizzaro reaction, Crossed Cannizzaro reaction, Benzoin condensation, Perkin condensation,
qualitative tests, Structure and uses of Formaldehyde, Paraldehyde, Acetone, Chloral hydrate,
Hexamine, Benzaldehyde, Vanilin, Cinnamaldehyde.
 
 
UNIT-V 08 Hours
Carboxylic acids*
Acidity of carboxylic acids, effect of substituents on acidity, inductive effect and qualitative
tests for carboxylic acids, amide and ester.
Structure and Uses of Acetic acid, Lactic acid, Tartaric acid, Citric acid, Succinic acid. Oxalic
acid, Salicylic acid, Benzoic acid, Benzyl benzoate, Dimethyl phthalate, Methyl salicylate and
Acetyl salicylic acid.
 Aliphatic amines* - Basicity, effect of substituent on Basicity. Qualitative test, Structure and
uses of Ethanolamine, Ethylenediamine, Amphetamine.
Complete the following road map problem and write the structures of each of the unknown compounds.

H2C C2H5MgBr
HBr KOH+H2O PCC D
CH3 A B C H2O

O3 / Zn KOH+Ethanol heating Conc.H2SO4

HCN
G
H+I L F E
H2C CH2 Br2/CCl4
NH2-NH2
light
J+K HBr
M N
Peroxide
O3 / Zn
O
ROH H+
P
 H3C H3C
H3C H3C
CH3 CH3
A CH3 CH3 C D
B HO C2H 5
Br HO O

Br
E H3C H3C CH3
H3C CH3 CH2
F
Br

H3C H3C H3C

H3C H2C
G J+K
CH3 H+I CH3 H2C N
H2C O
HO CN NH2 NH2
O
N
CH3
CH3
H2C H2C CH2
L CH3
M
Diels Alder H3C
OR
Br O OR
P
N O
H3C O H3C OR
H3C
OR
Synthesis Of Carboxylic acids
• 1) Hydrolysis of acid derivatives
• 2) Hydrolysis of nitriles
• 3) Oxidation of carbonyl compounds
• 4) Oxidation of alcohols
Hydrolysis of acid derivatives
• What are acid derivatives
• Condition for hydrolysis
• For acid chlorides: simple add water.
• Salts: addition of water and treatment with HCl
• Which acid derivative is least reactive?
• Carboxylic esters, nitriles, and amides are less reactive and typically must be
heated with water and a strong acid or base to give the corresponding carboxylic
acid. 
• Of these three types of acid derivatives, amides are the least reactive and require
the most vigorous treatment (i.e., higher temperatures and more prolonged
heating)
Oxidation of alcohols and aldehydes
• The oxidation of primary alcohols is a common method for the
synthesis of carboxylic acids: RCH2OH → RCOOH. 
• a strong oxidizing agent, the most common being chromic acid
(H2CrO4), potassium permanganate (KMnO4), and nitric acid (HNO3). 
• Aldehydes are oxidized to carboxylic acids more easily (by many
oxidizing agents), but this is not often useful, because the aldehydes
are usually less available than the corresponding acids.
Oxidation of alkyl benzene
• Oxidation of alkyl side chains of aromatic rings by strong oxidizing
agents such as chromic acid, potassium permanganate, and nitric acid
to yield aromatic carboxylic acids.
• Regardless of the number of carbon atoms in the side chain or the
presence of any groups attached to them, if the first carbon in the
alkyl chain is bonded to at least one hydrogen (and not to another
aromatic ring), all but one of the carbons are removed, and only a
COOH group remains bonded to the aromatic ring.
 O
H3C O H3C CH3
O + -
CH3 O Na O
CH3
O NH2 O CH3
H3C O
Cl O

A B C D E

HO
CH3
CH3
H3C
H3C CH3

F G H
 Carboxylic acids - Nomenclature
Common - names are related to the common source of the acid

• Monocarboxylic • Dicarboxylic
• Formic -->
• Acetic -->
• Oxalic O
• Malonic
• <--Propionic
• “protos””pion” propionibacteria
•
•
Succinic M
Glutaric
• Butyric
• <--Valeric
• Adipic Shanti
• Caproic -->
Valerian plant
G
A
Properties of Carboxylic acids
• They are acidic in nature (Ka / pKa ?????)
• Carboxylic acids dissociate in water to form carboxylate ion and
hydronium ion. The carboxylate ion formed is stabilized through
resonance by effective delocalization of the negative charge.
Question: Why carboxylic acids are more
acidic than phenols?
• Answer:
Carboxylate ion, the conjugate base of carboxylic acid is stabilized by two
equivalent resonance structures in which the negative charge is effectively
delocalized between two more electronegative oxygen atoms.
On the other hand in case of phenols, negative charge is less effectively delocalized
over one oxygen atom and less electronegative carbon atoms in phenoxide ion.
Therefore, the carboxylate ion exhibits higher stability in comparison to phenoxide
ion. Hence, the carboxylic acids are more acidic than phenols
Carboxylic acids are weaker than mineral acids but are strongest among the organic
compounds. Acidity of carboxylic acid is higher than alcohols and even phenols.
Factors affecting acidic nature of carboxylic
acids
• The acidity of carboxylic acids further depends on the nature of
substituent alkyl or aryl group attached to the carboxyl group. 
• An electron withdrawing group ensures effective delocalization of
negative charge through resonance or inductive effect. Thus, electron
withdrawing groups increase the stability of the conjugate base
formed and hence the acidity of carboxylic acids. 
• On the other hand, electron donating groups destabilizes the
conjugate base formed and hence decreases the acidity of carboxylic
acids.
 Arrange the following in decreasing order of
acidic nature
• CHCl2COOH
• NO2CH2COOH
• CF3COOH
• NC-CH2COOH
• CCl3COOH
Answer:
CF3COOH > CCl3COOH > CHCl2COOH > NO2CH2COOH > NC-CH2COOH
Qualitative tests for acids and
derivatives:
Test for acid chlorides
• Acyl chlorides release chloride ions very readily to give hydrogen
chloride gas. Add water to the sample slowly. If white misty fumes are
given off, an acyl chloride is present.
• Structure and Uses of Acetic acid, Lactic acid, Tartaric acid, Citric acid,
Succinic acid. Oxalicacid, Salicylic acid, Benzoic acid, Benzyl benzoate,
Dimethyl phthalate, Methyl salicylate and
• Acetyl salicylic acid.
Questions.
• 1) What will be the hydrolysis product of following given compounds.
II
II
I

III
IV
How will you synthesise?
• 1) Acetic acid from ethyl chloride
• 2) Benzoic acid from benzene [Give any two methods]
• 3) hex-3-enoic acid from 1,3-butadiene [you can use any other organic
compound with maximum three carbons in addition to 1,3-buta diene