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12 - Organic chemistry – Some basic principles and techniques

Isomerism
Two or more compounds having the same molecular formula, but different properties are called
isomers, and the phenomenon is called isomerism.

Structural Isomerism
 Compounds having the same molecular formula, but different structures are called structural
isomers.
 Chain isomerism:
Compounds having the same molecular formula, but different carbon skeletons are referred to
as chain isomers, and the phenomenon is called chain isomerism.

 Position isomerism:
Compounds with same MF but differing in the position of functional group on the carbon
skeleton are called position isomers, and the phenomenon is called position isomerism.

 Functional group isomerism:

Compounds with same molecular formula, but different functional groups are called functional
isomers
 Example − propanone (ketone) and propanal (aldehyde); both have the same molecular formula
C3H6O, but different functional groups

 Metamerism:
Compounds with same MF, same functional gp but different alkyl chains on either side of the
functional group in a molecule are called metamers, and the phenomenon is called metamerism.

Stereoisomerism
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Compounds having the same molecular formula and having the same structural formula, but differing
in relative positions of their atoms or groups in space are called stereoisomers.
 It can be classified as geometrical and optical isomerism.

Fundamental Concepts in Organic Reactions

Fission of a Covalent Bond

Heterolytic fission:
Bond breaks in such a way that the shared pair of electrons remains with one of the fragments
 Reactions which proceed by heterolytic fission are called ionic or heteropolar or polar
reactions.
 Intermediates are carbocation or carbonium ion and carbanion. Both are highly unstable
and reactive species.

Carbocation / Carbonium ion

A carbocation is the species having a carbon atom possessing sextet of electrons and a positive
charge. CH3+
 Carbocations are classified as primary, secondary and tertiary.

 Example: Primary carbocation − (ethyl cation)

Secondary carbocation − isopropyl cation,

Tertiary carbocation − tert-butyl cation,

Stability order

Q. Among 10, 20, 30 carbocation which is more stable and why ?. Why is methyl cation least
stable ? (or) Compare the stability of Carbonium ion.
The order of carbocation stability is 30 > 20 > 10 carbocation
Reason - Due to inductive and hyperconjugation effects, the alkyl groups directly attached to the
positively charged carbon stabilise the carbocations.
Methyl cation is least stable because in CH3+, the empty p- orbital is perpendicular to the plane of C-
H bonds and hence cannot overlap, thus lacks hyperconjugation stability.
Q. Draw the shape of methyl carbocation.
 The positively charged carbocation is sp2 hybridised hence have trigonal planar shape.
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 Carbanion

Carbanion is a carbon species carrying a negative charge on the carbon atom.

 The negatively charged carbanion is sp3 hybridised.

 Homolytic Cleavage:
One of the electrons of the shared pair in a covalent bond goes with each of the bonded atoms.
 The movement of the single electron takes place, instead of a pair of electrons.

 Reactions which proceed by homolytic fission are called free radical or homopolar or non-
polar reactions.
 Free radicals
Free radicals are the neutral species which contain an unpaired electron.

 Nucleophiles (Nu:) : [Electron rich species]

A nucleophile is a reagent that brings an electron pair, i.e., nucleus- seeking. (or)
Negative ions or neutral molecules with lone pair of electrons.

Example: HO− ,CN−, carbanion , NH3

 Electrophile (E+) [Electron deficient species]

An electrophile is a reagent that takes away an electron pair, i.e., electron- seeking. (or)
Positive ions or neutral molecules which are electron deficient.

Example: Cl+, BeF2, BF3, AlCl3, H+, Carbocation , neutral molecules having functional groups
like carbonyl group or alkyl halides

Electron Movement in Organic Compounds

Inductive Effect
The polarisation of σ- bond caused by the polarisation of adjacent σ- bond is called as the
inductive effect.

 Ability of the substituent(s) to either withdraw or donate electron density to the attached carbon
atom is related to inductive effect.
 On the basis of inductive effect, the substituent can be classified as electron-withdrawing or
electron donating groups relative to hydrogen.
 Electron withdrawing groups −−− Halogens, nitro (-NO2), cyano (-CN), carboxy (COOH),
ester (-COOR)
 Electron donating groups −−− Alkyl groups such as methyl (-CH3) and ethyl (-C2H5)
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Q. Using curved-arrow notation, show the formation of reactive intermediates when the
following covalent bonds undergo heterolytic cleavage.
(a) CH3–SCH3, (b) CH3–CN, (c) CH3–Cu

Q.Giving justification, categorise the following molecules/ions as nucleophile or electrophile:

HS- , C2H5O- , (CH3)3N:, H2 N:- ,BF3 , Cl+,CH3- C+=O ,NO2+.
Nucleophiles: HS- , C2H5O- , (CH3)3N:, H2 N:-
Electrophiles: BF3 , Cl+,CH3- C+=O ,NO2+.

Q.Identify electrophilic centre in the following: CH3CH=O, CH3CN, CH3I.

Among CH3HC*=O, H3CC*≡N, and H3C*–I, the starred carbon atoms are electrophilic centers as
they will have partial positive charge

Q. Which bond is more polar in the following pairs of molecules:

(a) H3C-H, H3C-Br (b) H3C-NH2, H3C-OH (c) H3C-OH, H3C-SH
(a) C–Br, since Br is more electronegative than H, (b) C–O, (c) C–O

Q. In which C–C bond of CH3CH2CH2Br, the inductive effect is expected to be the least?
Magnitude of inductive effect diminishes as the number of intervening bonds increases. Hence, the
effect is least in C2 – C3 bond.

 Resonance
Q. Draw the resonance structures of (i) Benzene

 Benzene has a uniform C − C bond length of 139 pm [an intermediate value between C − C
single (154 pm) and C = C double (134 pm) bonds].
(ii) Nitromethane [CH3NO2]

(iii) acetate ion [CH3COO-]

(iv) CH2=CH - CHO . Indicate relative stability of the contributing structures.

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Stability:
 The energy of the actual structure (resonance hybrid) of the molecule is lower than that of any
of the canonical structures.
 Resonance energy is the difference in energy between the actual structure and the lowest energy
resonance structure.
 More the number of resonance structures, more is the resonance energy.

Resonance Effect (or Mesomeric Effect)[ R or M effect]

Defined as the ‘polarity produced in the molecule by the interaction of two π-bonds or between
a π-bond and lone pair of electrons present on an adjacent atom’

 Positive Resonance Effect (+R Effect)

Transfer of electrons is away from an atom or substituent group attached to the conjugated
system.
 + R effect showing groups: − halogen, − OH, − OR, − OCOR, − NH2
Q. Draw the resonance structures of (i) Aniline [C6H5NH2]

(ii) Phenol [C6H5OH]

 Negative Resonance Effect (− R Effect)

Transfer of electrons is towards the atom or substituent group attached to the conjugated
system.
 − R effect showing groups: − COOH, − CHO, , − CN, − NO2
Q. Draw the resonance structures of (i) Nitrobenzene [C6H5NO2]

(ii) Benzaldehyde [C6H5CHO]

Electromeric Effect (+ E Effect)

 Temporary effect
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 Shown by the organic compounds having a multiple bond (a double or triple bond) in the
presence of an attacking reagent only
It is defined as the complete transfer of a shared pair of π-electrons to one of the multiple
bonded atoms on the demand of an attacking reagent

Positive Electromeric Effect (+ E Effect)

π- electrons of the multiple bonds are transferred to that atom to which reagent gets attached.

Negative Electromeric Effect (− E Effect)

π-electrons of the multiple bonds are transferred to that atom to which attacking reagent does
not get attached.

Hyperconjugation [No bond resonance]

 A permanent effect
It involves the delocalisation of σ − electrons of C − H bond of an alkyl group directly attached
to an unsaturated system or to an atom with an unshared p-orbital
Hyperconjugation in ethyl cation:

 On the basis of hyperconjugation effect, the relative stability of carbocations is

 Greater the number of alkyl groups attached to a positively charged carbon atom, greater
is the hyperconjugation and stabilization of the cation.

Qualitative Analysis
1.Detection of carbon and Hydrogen in organic compound
Organic compound containing Carbon gets oxidized to CO2 which turns lime water
Carbon & Hydrogen + CuO + Heat milky

Hydrogen gets oxidized to H2O which turns white

anhydrous CuSO4 to blue CuSO4.5H2O
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 2. Detection of Nitrogen
Sodium fusion extract + H2SO4 + Prussian blue colour due to ferric ferrocyanide
FeSO4 ---→ Fe4[Fe(CN)6]3

 3. Detection of Sulphur
i. Sodium fusion extract + Acetic acid + lead acetate-- Black ppt of PbS
→

ii. Sodium fusion extract + Sodium nitroprusside --→ Violet colour

 4. Detection of Halogens (Cl, Br, I)

Sodium fusion extract + HNO3 + White ppt of AgCl soluble in NH4OH-------Chlorine
AgNO3 Pale yellow ppt of AgBr partially soluble in NH4OH-----
Bromine
Yellow ppt of AgI insoluble in NH4OH-------Iodine
5. Discuss the chemistry of Lassaignes test / preparation of sodium fusion extract.
Organic Compound is fused with metallic sodium to convert covalent bond into ionic bond. It is then
boiled with distilled water to form sodium fusion extract.

6. Why is organic compound fused with metallic sodium for testing N, S, halogens?
To convert covalent bond to ionic bond.

7. Why is nitric acid added before adding silver nitrate for testing halogens?
To decompose sodium cyanide and sodium sulphide, otherwise these will interfere with silver
nitrate test.

Reader Questions
1. Draw the resonance structures. Show the electron shift using curved-arrow notation.
(a) CH3CH = CH – CHO (c) CH3 CH = CH CH2⊕
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(b) C6H5CH2⊕

2. Identify the reagents shown in bold as nucleophiles or electrophiles:

…HO– acts as a nucleophile as it is an electron-rich
species
……., –CN acts as a nucleophile as it is an electron-rich
species,

……, acts as an electrophile as it is an electron-

deficient species.

3. What is the relationship between the members of following pairs of structures? Are they
structural or geometrical isomers or resonance contributors?
(a)

….position isomers / metamers….structural isomers

(b)

….. Geometrical isomers

(c)

....Resonance structures

4. For the following bond cleavages, use curved-arrows to show the electron flow and classify
each as homolysis or heterolysis. Identify reactive intermediate produced as free radical,
carbocation and carbanion.
(a) …….. homolytic cleavage… intermediate is a free radical

(b) …… heterolytic cleavage….. carbanion.

(c) …….. heterolytic cleavage …….carbocation.

(d) …….. heterolytic cleavage …….carbocation.

5. Explain why alkyl groups act as electron donors when attached to a π system.
When an alkyl group is attached to a π system, it acts as an electron-donor group by the process of
hyperconjugation.

6. Which of the two: O2NCH2CH2O– or CH3CH2O– is expected to be more stable and why?
NO2 group is an electron-withdrawing group [–I effect], decreases the negative charge on the
compound, thereby stabilising it. On the other hand, ethyl group is an electron-releasing group [+I
effect]. This increases the negative charge on the compound, thereby destabilising it. Hence,
O2NCH2CH2O– is expected to be more stable than CH3CH2O–.
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7. Give the IUPAC names of the following compounds:

(a) (b) (c)

3–methylpentanenitrile
3–phenyl propane 2, 5–dimethyl heptane
(d) (e) (f) Cl2CHCH2OH
1, 1–dichloro–2–ethanol

3–bromo–3–chloroheptane 3–chloropropanal
8. Write bond line formulas for: Isopropyl alcohol, 2,3-Dimethyl butanal, Heptan-4-one.
(a) Isopropyl alcohol (b) 2, 3–dimethyl butanal (c) Heptan–4–one

9. Indicate the σ and π bonds in the following molecules:

(i) C6H6 (ii) C6H12 (iii) CH2Cl2

σ = 4, π = 0
σ = 12, π = 3 σ = 12, π = 0
(iv) CH2 = C = CH2 (v) CH3NO2 (vi) HCONHCH3

σ = 6, π = 2 σ = 6, π = 1 σ = 8, π = 1

10. What are hybridisation states of each carbon atom in the following compounds?
CH2=C=O, CH3CH=CH2, (CH3)2CO, CH2=CHCN, C6H6

(iii)
(i) (ii)
C–1 is sp2 ,C–2 is sp C–1 is sp3 , C–2 is sp2, C–3 is sp2 .

C–1, C–3 are sp3,C–2 is sp2 .

(v) C6H6
(iv) All the 6 carbon atoms are sp2 .
C–1 is sp2, C–2 is sp2 ,C–3
is sp.