Organic Chemistry-Some Basic Principles and Techniques

which it forms four covalent bonds, is generally referred

INTRODUCTI0N to as tetracovalency of carbon. The unique capacity of
Organic chemistryisthechemistryofcarboncompoundsas carbon atom to form bonds with other carbon atoms, is
all organic compounds contain carbon as their essential called catenation.
constituent. Organic compounds may be
regarded as
Shapes
hydrocarbons i.e., compounds of carbon and hydrogen
only. A number of organic compounds also
large Geometry of
contain elements like N, 0, S, X, etc. which are derived Type of Orbitals the hybrid Bond Percentage
ofs-and
from hydrocarbons by replacing one or more hydrogen
atoms in their molecules with these atoms. Thus, the
hybridisation used
orbitalsangip-characters
formed
modern definition of the organic chemistry is "the 25% s+
one Tetrahedral 109.5
chemistry of the hydrocarbons and their derivatives three p 75% p

ORGANIC COMPOUNDS one +

twop
Trigonal
planar
120°
33.3% s +
66.7% p
Tetravalency of Carbon
one s+ 50%6s+
Carbon can complete its octet by sharing its valence P Linear 180
one p 50% p
electrons with the electrons of other atoms, by virtue of

Structural Representation
Complete Condensed
Bond-line formula Polygon 3D Representation
formula formula formula

H Dashed wedge
(bondaway
H- CH-CH
Bonds in
neplane.
paper H
from observer)

Solid wedge
Ethane n-Pentane Cyclopropane -(bond towards
Ethane observer)
Classification
Organic Compounds
(Acyclic or Openchain or Aliphatic) Closed chain or Cyclicor Ring
Saturated Unsaturated Homocyclic (Carbocyclic) Heterocyclic)
(Alkanes) (Alkenes, Alkynes)
Alicyclic Aromatie Alieylie Aromatic
Benzenoid Non-benzenoid
Homolagous Series Functional Groups
A series of organic compounds, each containing a An atom or agroup of atoms joined in a specific manner
characteristic functional group, forms a homologous which is responsible for the characteristic chemical
series in which each successive member differs by a properties of the organic compounds eg., hydroxyl
-CH, unit or by 12+ 2 xl =14 mass units. group (-0H), aldehyde group (-CHO), carboxylic
acid group(-COOH), etc.

IUPAC Nomenclature
word root +1suffx + 2sufix
IUPAC name 2° prefix 1°prefix

Some functional groups are Principal chain Indicates functional group

****
always treated as substituents -OH(-ol), -CHO(-al)
whether organic compound -C-- -c-
cO(-one).
****

is monofunctional or
polyfunctional eg, Fluoro (-F), If no. of C atoms is 1-meth, 2-eth, 3-propla), -CoOH (-olc acid),
Chloro(-CI), Bromo -Br),
lodo (-I). Nitro(-NO,).Nitroso
4-but(a), 5-pent(a),6-hex(a),7-hept(a), 8-oct(a). -cONH, (-amide),
9-non(a), 10-dec(a), 11-undec(a), 12-dodecla). -coCI (-oyl chloride),
(-NO), Diazo -N=N), Extra 'a' is added to word root if 1° sufix begins
-coOR (alkyl 0ate).
Alkoxy (-OR), Alkyl (-R). with a consonant.
Phenyl(-CsH), etc. -CN (nitrile),-SH (thiol).
-NH, (-amine).
Cyclo is used for carbocyclic Singlebond only- ane If 2° suffix begins with a
compounds. If cyclo is not 1 (Sbond-ene 1(bond-yne
used, it indicates acyclic 2(=bonds-diene 2(bonds-diyne vowel, the terminal 'e is
or 3 (=bonds-triene 3 (bonds-triyne
open chain compound. dropped
Compound IUPAC name Compound IUPAC name
CH,CH,CH,CH Butane CH,CH,OH Ethanol
CH C H Ethyne CH,CH,CH,NH; Propanamine
CH,COOH Ethanoic acid HC CCOOH Prop-2-yn-1-oic acid
CH,CH,Br Bromoethane CH,CH,COCH, Butan-2-one
CH,OCH Ethoxyethane cHs 2-Methylpropane
CH-CH-CH
 CH3 1,2-Dimethykyclopentane Cyclohexene

OH 2-Methylphenol OH 2.4,6-Trinitrophenol
CH3 NO,
0gO
NO
Isomerism
The phenomenon of existence of two or more compounds possessing the same molecular formula but different
properties is known as isomerism. It is classified broadly into structural isomerism and stereoisomerism.
Types ofstructural isomerism:

Name Difference Examples

Chain or nuclear or in the arrangement of C-atoms CH3
skeletal isomerism constituting the chain.
CH,CH,CH,CH,CH,
Pentane
CH-CH-CH,CH,
2-Methylbutanc

Position isomerism in the position occupied by a

CH-CH-CH=CH.
1-Butene
CH-CH=CH-CH
2-Butene
particular atom or group in the
same carbon chain. Ci
1-Chlorobutane
2-Chlorobutane

Functional isomerism in the nature of functional group CH,O: CHy,CH,OH. CH, -0-CH,
present Ethyl alcohol Dimethyl ether
CH,O: CH,COOH HCOOCH
Ethanoic acid Methyl mcthanoate

Metamerism in the nature of alkyl group CH0:CH -O- CH,CH,CH

attached to the polyvalent atom of Methyl propyl ether
the functional group CH-CH-0-CH-CH
Diethyl ether

Tautomerism in the position of H-atom linked to H-CEN

Hydrogen cyanide
H-N2C
Hydrogen isocyanide
one polyvalent atom to the other
within the OH
same molecule, arising
due to rearrangement of linkages. CH-C-H CH,=-H
Tautomers exist in dynamic Acetaldehyde Vinyl akohol
cquilibrium with each other

Ring-chain isomerism in the bonding of carbon atom

to form open chain and cyclic
structure.
CH-CH=CH2, CH,-H,
propene cydoprapane
Types of stereoisomerism:
Isomers have the same structural formula but
differ in the spatial arrangement of atoms or
groups of atoms about double bond. trans
(Similar groups on the same (Similar groups on the diflerent
Compounds containing C=N and N==N
side of the double bond) sides of the double bond)
bonds also show geometrical isomerism. In
these cases, 'syn' (for cis) and 'anti (for trans) HON=NOH HO N<N~OH
are more commonly used. syn anti

E and Z system of nomenclature is used for highly substituted alkenes,

having four different atoms or groups, attached to C=Cbond.
Eis assigned to an isomer in which high priority atoms or groups are on the opposite sides.
Zis assigned to an isomer in which high priority atoms or groups are on the same side.
Compounds having similar physical and chemical properties but differing only in the behaviour
towards polarised light are called optical isomers and the phenomenon is called optical isomerism.
Some substances have the ability to rotate the plane polarised light either to the right (clockwise) ie,
dextrorotatory or to the left (anticlockwise) i.e., laevorotatory are optically active substances and the
property is called optical activity.
I n order to exhibit optical activity, an object must be chiral.
The compound is said to have chirality if the central carbon atom 1-
is attached to four different groups and this centre is called chiral (
Chiral centre
(
Achiral centre
(asymmetric) centre or stereogenic centre or stereocentre.
(asymmetric) (symmetric)
If the central carbon atom has at least two identical groups then this
centre is called achiral (symmetric) centre.
Ifmolecule has a plane of symmetry. it is achiral and if molecule has no plane of symmetry, it is chiral.
Enantiomers or d-and lisomers are the optical isomers which are non-superimposable mirror images
(or dissymmetric). Equimolecular mixture of d- and l-forms is known as racemic mixture (dl-form). This
is optically inactive due to external compensation.
Diastereomers are the optical isomers which are not mirror images of each other. They have different|
physical properties and magnitude of specific rotation.
Meso compounds are those compounds which have two or more even number of chiral carbon atoms and
have an internal plane of symmetry. They are optically inactive due to internal compensation.
FUNDAMENTAL CoNCEPTS IN REACTION MecHaNISM
Reaction Intermediates
Name Structure Stability
1. Carbocations or
carbonium ions cHC CH,cH >
(CHJ,¢>cHEH, >CH,=CH-H,
(CH H CH,H,» H,>CH= H > HC=>¢H
(planar)
Tmpty parbital

2. Carbanions epan HCE(CH,C> (C,H,),

(pyramidal) gobital CH,= H> H,> CH,H,> (CHJ,H >(CH,),E

3. Free radicals npaind

trn (cH>CHJJH >(CH,Jh> CH,H,»CH,=CH-H,
(planar, HC=¢
paramagnetic) CHCH>CH,H, »H,>

ATTACKING REAGENTS
Attacking Reagents
Electrophiles Nucleophiles Ambiphiles
Positively charged or neutral Negatively charged or neutral Behave like both electrophiles
molecules, having electron molecules, having electron rich
as well as nucleophiles.
deficient atom. atomwith unshared electron pair.
Charged Neutral Charged Neutral Charged Neutral
H,[Link], BF. BeCl [Link] NH, H,O:, H,0',RNH ROH
NH, RCO COC=0 R, etc. RH, RCO, RSO. C-0,R-CN,
etc. etc. etc. etc. etc.

ELECTRON DisPLACEMENT EFFeCTS IN CovALENT BOND

Inductive effect: Displacement of-I
a-electrons along a saturated carbon chain
effect:RN-,-NO2-SO,R, -CN, -coOH, -F-CI,
-Br,-I,-OR,-COR,-OH,-CH-CH = CH,etc.
when an electron donating (+I
effect) or
electron withdrawing (-I cfect) group is
+ effect: (CH),C (CHJ,CH-, CH,CH .CH- ,

-CO0,etc
attached at the end of the carbon chain.
Electromericeffect: It involves complete +E effect: When electron transfer takes place towards the atom
transfer of n-electrons of a multiple bond to which the attacking reagent gets attached.
towards one of the bonded atoms in the -E effect: When electron transfer takes place away from the
presence of an attacking reagent. atom to which the attacking reagent gets attached.
Resonance or mesomeric effect It +R effect -C -NH2, -NHR, -NR2»
-Br, -1,
is defined as the polarity produced in -NHCOR,-OH,-OR,-SR,-SH, -OCH.-0cOR,etc.
the molecule by theinteraction oftwo
T-bonds or between a n-bond and a lone
-Reffect:-No,-CN,-CHo,-coOH,-cOR, ete.
pair of electrons present on adjacent atom.
 ********
***************************************************** **************** *****|
Hyperconjugation: It involves delocali- For an alkyl group attached to unsaturated system, it decreases
sation of a-electrons of C-H bond of an with decrease in number of a-hydrogens:
alkyl group directly attached to an atom of CH-CH,CH-> (CH,),CH-> (CH),C
unsaturated system or to an atom having
vacant p-orbital.

METHODS OF PURIFICATION OF ORGANMC CoMPOUNDS

Method Used for separating Examples
Crystallisation Mixtures with difference in the solubility of Sugar with impurity of common salt can
the organic compound and its impurities in be crystallised from hot ethanol at 348 K
a solvent. (sugar dissolves but salt does not).
Benzoic acid and naphthalene from
hot water (benzoic acid dissolves but
naphthalene does not).

Sublimation Mixtures of sublimable volatile compounds Purification of camphor, anthracene,

and non-sublimable impurities. naphthalene, benzoic acid, etc.

Simple Mixtures of liquids having sufficient Chloroform ([Link]. 334 K) and aniline (bpt.
distillation difference in their boiling points and contain 457 K).
non-volatile impurities. Ether (bpt. 308 K) and toluene (bpt. 384 K).

Fractional Mixtures of two or more miscible liquids Acetone ([Link]. 329 K) and methyl alcohol
distillation which have [Link]. close to cach other. (bpt. 338 K).
Benzene ([Link]. 353 K) and toluene ([Link].|
383 K).

Steam Mixtures ofsubstances which are (i) volatile Aniline and water.
distillation in steam, (ii) not miscible with water, Purification of nitrobenzene,
(ii) possess a vapour pressure of about 0-nitrophenol, bromobenzene, etc.
10-15 mm of Hg. and (iv) contain non-
volatile impurities.

Azeotropic Mixtures with constant boiling points i.e., Ethanol and water in ratio 95.87:4.13.
distillation azeotropic mixtures.

Vacuum Mixtures of high boiling liquids which Glycerol from spent-lye in soap industry
distillation decompose at or below their boiling points. (at 453 K under 12 mm Hg)
Concentration of sugarcane juice.

Chromatograph Mixtures with difference in the rates at ortho and para nitroaniline.
which the components of the mixture move Blue and red dyes.
through a porous medium. Plant pigmentsand other natural products.

Differential Mixtures of organic compounds from their Benzoic acid from its aqueous solution
extraction aqueous solutions using a solvent that should using benzene.

() be immiscible with water. (ii) dissolve the

organic compound.
 white copper sulphate to blue copper sulphate by
QUALITATIVE AMALYSIS OF ORGANIC GOMPOUNDS hydration.
Organic compounds mainly consistofcarbon, hydrogen, CO +Ca(OH),CaCo,+H,0
oxygen, nitrogen, halogen, sulphur and sometimes Lime wate Millky
phosphorus. The detection of various elements present 5H,0+CuSso, CusO5H,0
in a compound is called qualitative
analysis White Bluc

Detection of C and H Detection of N, S and X

Presence ofC and H is detected by combustion with These elements are tested in an organic compound by
cupric oxide. C converts to carbon dioxide and H assaigne's test. The organic compound is fused with
converts to water. sodium metal to convert these elements into ionisable
C+ 2CuO 2Cu+ CO inorganic substance, i.e., nitrogen into sodium cyanide,
2H+CuO H,0+ Cu sulphur into sodium sulphide and halogens into sodium
Evolved Co, turns lime water milky and water converts halides.

Element Sodium extract Confirmatory test

Na+C+NANaCN NaCN+ FeSO, + NaOH) + FeCly +[Link] or green colour.
Nitrogen Boil and cool

2Na+S Na,s () Na,S+ sodium nitroprusside A deep violet colour

Sulphur
(i) Na,S+ CH,COOH+ (CH,CO0),Pb Ablack ppt.
Halogen Na +X NaX NaX +HNO,+AgNO AgXt+ NaNO,
Ci) White ppt. soluble in aq. NH, confirms C.
(i) Yellow ppt. partially soluble in aq. NH, confirms Br.

(ii)Yellow Ppt. insoluble in [Link] I.

Nitrogen Na+C+N+S As in test for nitrogen; instead or blue
of green colour, blood red
and sulphur NaCNS Colouration confirms presence of Nand S both.
together

Beilstcin test for the detection of halogens: Organic H,PO+12(NH,),Mo0,

Ammonium molybdate
+21HNO,
compounds taken on copper wire, burning with
coloured flame (blue or green) show the presence of (NH,),PO, 12Mo0, + 21 NH,NO, + 12H,0
Ammonium
halogens. This test is not a very reliable test. Beilstein's phosphomolybdate
test is not given by fluorine, since copper fluorite is not
volatile.

Detection of Phosphorus
To detect the presence of phosphorus, the given organie
compound is fused with sodium peroxide (oxidising
agent). The fused mass is extracted with water. The
filtrate obtained is boiled with a few drops of conc.
HNO. Then the solution is treated with ammonium
molybdate. A yellow coloured precipitate (due to
ammonium phosphomolybdate. (NH,),PO, 12Mo0,
confirms phosphorus).
NaPO, + 3HNO,H,PO, +3NaNO
QUANTITATIVE AMALYSIS OF ORGANIC COMPOUNDS
Element Method
Carbon and Liebig's combustion method:
Hydrogen %of C 2massof CO; formed 100 ; %of H= mass of H20 formedx100
44 mass of compound taken 18 mass ofcompound taken

Nitrogen Dumas method:

%of N= x vol. of N2 at STP x100
22400 mass of compound taken

Kjeldahl's method:
of N=14xmolarity ofacid x vol ofacidused xbasicityofaecid
mass of compound taken

Halogens Carius method:

%of X=AL. mass ot Axmass of Agl formedv 100
108 +At. mass of X mass of compound taken

Sulphur Carius method

% of S= mass of BasO4 formed x100

233 mass of compound taken

Phosphorus Ignition method:

% of P 2mass of Mg,P,0, fomed <100

222 mass of compound taken

Oxygen lodine method:

16 mass CO, formed
of CO,
mass of
ofO=127 massmassof compound
of l formed x100
% ofO=6 tormeax 100 or % 5x16
44 massof compound taken taken

1. In Lassaigne's test for nitrogen, the blue colour is 3. The number of structural isomers for CH1 is
due to the formation of (a) (b) 4
(a) ferric ferrocyanide c) 5 (d)6
(b) potassium ferrocyanide 4. The IUPAC name of the compound
(c) sodium ferrocyanide
(d) sodium cyanide.
2. The number of sigma (o) and pi (n) bonds in
pent-2-en-4-yne is
H-
(a) 13 a bonds and no n bond (a) 5-formylhex-2-en-3-one
(b) 10 o bonds and 3 n bonds (b) 5-methyl-4-oxohex-2-en-5-al
(c) 8 o bonds and 5 t b ds (c) 3-keto-2-methylhex-5-enal
(d) 11 o bonds and 2 T bonds. (NEET 2019) (d) 3-keto-2-methylhex-4-enal. (NEET 2017)