General Organic Chemistry (Synopsis)

Inductive effect: The inductive effect is a permanent and involves the displacement of  electrons along a saturated
carbon chain due to presence of an electron withdrawing group(-I-effect) or an electron repelling group (+I-effect) at one
end of the chain resulting in the development of partial positive or negative charges in the decreasing order of magnitude.
 The order of –I-effect of some common groups is as follows, -NO2>-CN>-COOH>-F> - Cl>- Br > - I >- OH>C6H5 –
 The alkyl groups show +I-effect which decreases in the order 3o> 2o > 1o. i.e,(CH3)3C>(CH3)2CH -> CH3CH2 - > CH3 –
 Inductive effect explains the acidic character of carboxylic acids.
(i) More the –I-effect more is the acidic character of carboxylic acids. e.g. Cl3CCOOH > Cl2CHCOOH > ClCH2COOH
(ii) More the +I-effect weaker is the acid. For example HCOOH < CH3COOH < (CH3)2CHCOH < (CH3)3CCOOH.
Similarly, CH3OH < C2H5OH < (CH3)2CHOH < (CH3)3COH
 It explains the basic character of amines. More the +I-effect more is the basic character. eg.C2H5NH2 > CH3NH2 > NH3
 It explains the relative stabilities of carbocation and carbanion. More the number of alkyl groups attached to the
positively charged carbon more is the stability of carbocation. More the number of alkyl groups attached to the
negatively charged carbon lesser is the stability of carbanion.
Electromeric effect:The effect involving the complete transfer of a shared pair of electrons to one of atoms joined by a
multiple bond at the requirement of attacking reagent is known as electromeric effect. It is a temporary effect and comes
into play instantaneously at the demand of the attacking reagent and as soon as the reagent is removed, the original
condition is restored.
Mesomeric effect or M-effect is the permanent effect involving the transfer of electrons relayed through  - electrons of
multiple bonds in a chain of carbon atoms in a molecule. Or in Benzene ring.
 The group which withdraws the electrons from the benzene ring by resonance is known as –R-group. For e.g. NO2,
COOH, CHO, CN etc. –R-effect decreases the order NO2 > CN > SO3H > COOH > CHO
 The group which donates the electrons to the benzene ring by resonance is known as +R-group. Such groups have
negative charge or at least one lone pair of electrons is in conjugation with a -bond. For eg. O-, NH2, NHAc, OH, X
etc. +R-effect decreases in the order O- > NH2 > OH > OR > NHAc
Conjugated system and resonance: A given atom or group is said to be in conjugation with an unsaturated system if it
is directly linked to one of the atoms of the multiple bond through a single bond or it has a -bond, positive charge or
negative charge, odd electron or lone pair of electron. eg.CH2=CH-CH=CH2,CH2=CH-C N, CH2=CH-CH2+ ,CH2=CH-NH2
 Delocalization always increases the stability of the conjugated compound. More the number of resonating structure,
more is the stability
Hyperconjugation: Electron release by an alkyl group attached to unsaturated system (H – C – C = C) is called
hyperconjugation (involving delocalization of  and  bond orbitals, i.e., - conjugation) is called hyperconjugation
(Baker-Nathan effect or No bond resonance). It explains the stability of free radicals, carbocations.
(i) On the basis of heat of hydrogenation, the stability order of different alkenes is:
Tetrasubstituted > Trisubstituted > disubstituted > Monosubstituted > H2C = CH2
(ii) Stability order of different alkyl carbocations is in the following order:
Teritary > Secondary > Primary > Methyl
(iii) Stability of alkyl free radicals is also in the same order:
(CH3)3 Co > (CH3)2 CHo > CH3 CH2o > CH3o
i.e., more the number of hyperconjugation structures, the greater is its stability.
(iv) Alkyl group of alkyl benzene is o- and p-directing and activates aromatic SE reactions. This property of alkyl group
can be explained by hyperconjugation.
Free radicals: Carbon free radicals have no charge but the central carbon atom carries odd (unpaired) electrons. These
are produced by hemolytic fission of a covalent bond. The relative stabilities of free radicals are:
3o > benzyl > allyl > 2o > 1o> methyl, vinyl
Carbocations (carbonium ions): Organic ions carrying a positive charge on carbon atoms are known as carbocations.
Carbocations are very reactive and have six electrons, (sextet), therefore, it is electron deficient species. Carbocation is a
planar structure and the +vely charged carbon is sp2-hybridized (triagonal planar). The relative stability of carbocation are:
(C6H5)3 C+ > (C6H5)2CH+ > (CH3)3C+ > C6H5 CH2+ > CH2 = CH+CH2 > (CH3)2 CH+ > CH3CH2+ > CH3+
 It should be noted that the presence of electron attracting groups (-NO2, -CN and Br) which have –I effect reduces the
stability of carbocations. While groups having +I effect increases the stability of carbocations.
 Alkyl carbocation is more stable than vinyl carbocation because the carbon carrying positive charge in alkyl
carbocation is sp2-hybridized and is sp-hybridized in vinyl carbocation.
Carbanions: Organic ions containing a negatively charged carbon are known as carbanions. Carbanions are highly
reactive and contain eight electrons in the valency shell, i.e., complete octet. It has a pyramidal structure because the
carbon bearing –ve charge is sp3 hybridized. The relative stability of carbanions are:
(C6H5)3C- > (C6H5)2CH- > C6H5CH2- > CH2 = CH – CH2- > CH3- > CH3CH2- > (CH3)2CH- > (CH3)3C-
 The order of stability of alkyl, vinyl , acetelyenic carbanion is CHC- >CH2=CH- > CH3-CH2-
Carbenes: these are short lived, reactive, sp2-hybridized, natural species and transitory reaction intermediates in which
the carbon atom has six electrons in the outer shell, out of which two constitute a lone pair and two are shared. So they
are divalent carbon species containing two unpaired electrons and possess no charge. For example. :CH2 (Methylene
carbine) , :CHR (alkyl carbene) , :CCl2 (Dichlorocarbene)Carbenes are of two types ,.,Singlet and triplet carbenes
 The carbon atom is in sp2-hybridized in singlet carbene and has a bent structure. It is less stable and highly reactive.
Triplet carbene is a diradical, sp-hybridized and is believed to be a linear molecule. It is more stable.
 The decreasing order of stability of different type of singlet carbines are :CH2 , :CF2 > :CCl2 > :CBr2
Attacking reagents: These are of three types:
(i) Electrophiles (electrophilic reagent): These are electron loving species and carry either positive charge or neutral
molecules with electron deffecient centre. These are Lewis acids and can accept a pair of electrons in a reaction. For
example, H+, Cl+, NO2+, R+ etc are +ve electrophiles while SO3, BF3, CCl2 are neutral electrophiles.
(ii) Nucleophiles (Nucleophilic reagents): These are electron rich (donating) species and carry either negative charge
or neutral molecules with free electron pair to donate (N in NH3, and O in H2O). These are Lewis bases. For example,
Cl-, CN-, OH-, NH2- etc are –ve nucleophiles while NH3, H2O, ROH, RNH2 etc are neutral nucleophiles.
 (iii) Ambiphile (Ambident): They behave both like electrophiles and nucleophiles site and hence, have dual
(amphoteric) nature. The Nucleophiles which can attack through two or more atoms are called ambident nucleophiles.
For example, CN- can attack through N or C to give cyanide (RCN) or isocyanide (RNC).
Nucleophilicity: The reactivity of nucleophile is called its nucleophilicity. It can be compared as given below:
(i) A species with a negative charge is a stronger nucleophile than a similar species without a negative charge.
Therefore OH is stronger nucleophile than HOH and SH is a stronger nucleophile than HSH.
(ii) Nucleophilicity decreases on going from left to right in the periodic table. Therefore, CH3 is more nucleophilic than
NH2 which is more nucleophilic than OH which is more nucleophilic than F.
(iii) Nucleophilicity increases on going down in the group of the periodic table. Therefore:
I > Br > Cl > F. Similarly SeH > SH> OH and R3P > R3N
(iv) Bulky group present on nucleophile centre decreases nucleophilicity
HO > CH3-O > (CH3)2CH - O > (CH3)3C - O
Types of organic reactions: The important types of reactions are Substitution reactions, Addition reactions, Elimination
reacts, Rearrangement reactions. Alkyl halides undergo Nucleophilic Substitution reactions(SN),Alkenes and alkynes
undergo Electrophilic Addition reactions,Aromatic compounds undergo Electrophilic Substitution reactions(S E), carbonyl
compounds undergo Nuleophilic addition reactions
Isomerism: Two or more organic compounds having the same molecular formula but different physical and chemical
properties are called isomers and the phenomenon is known as isomerism.
 Structural isomers: The isomers differ only in the arrangement of atoms or groups within the molecule, without any
reference to space are called structural isomers and the phenomenon is known as structural isomerism.
 Chain or nuclear isomerism: It is due to the difference in the nature of carbon chain (straight or branched) which
forms the nucleus of the molecule. For example, n-butane and isobutene.
 Position isomerism: It is due to the difference in the position of the substituent atom or group or an unsaturated
linkage in the same carbon chain. For example, but-1-ene and but-2-ene.
 Ring chain isomerism: It is due to different modes of linking of carbon atoms i.e., the isomers process either open
chain or closed chain structures. For example, cyclobutane and butene.
 Functional isomerism: It is due to the difference in the nature of functional group present in the isomers. For
example, alcohols and ethers; carboxylic acids and esters; aldehydes and ketones.
 Metamerism: It is due to the difference in the nature of alkyl groups on either side of the same polyvalent atom or
functional group. For example, C2H5O C2H5 and CH3O C3H7.
 Tautomerism: It is the type of isomerism in which a single compound exists in two readily interconvertible different
structures to leading dynamic equilibrium. It is caused by the wandering nature (1,3-migration) of mobile hydrogen
atom from one polyvalent atom to the other within the same molecule. Keto-enol system is an important example of
tautomerism. For example, CH3COCH3 and CH2=CH(OH)CH3.Presence of  hydrogen is the necessary condition
for tautomerism.i.e.,hydrogen next to carbonyl or nitro group
Stereoisomerism: Compounds having the same structural formula but different relative arrangement of atoms or groups
in space (configuration) are called stereoisomerism. It is classified into (i) geometrical isomerism (ii) Optical isomerism
 Geometrical (or cis-trans) isomerism: Compounds possess the same structural formula but differ in the spatial
arrangement of atoms or groups (or differ in configuration) around the double bond. This isomerism is shown by
alkenes or their derivatives. For example, but-2-ene, pent-2-ene.
Geometrical isomerism is possible only when each of the double bonded carbon atoms is attached with two different
atoms or groups and carbon atoms joined by double bond cannot rotate freely.
Geometrical isomerism is also exhibited by compounds containing C = N bond (as in aldoxime) N = N bond (as in azo
compounds), cyclic compounds and dienes.
 E and Z system: If two groups having higher atomic number are on same side w.r.t C = C bond, we call the isomer
as (Z-) isomer (together) and if on the opposite side w.r.t C = C bond, we call it (E-) isomer (opposite or across)
 Optical isomerism: Compounds having similar physical or chemical properties and differ only in their behaviour
towards plane polarized light are called optical isomers. The optical isomer which rotates the plane of polarized light to
the right (clockwise) is known as dextrorotatory or d- form or +ve sign while that which rotates towards left
(anticlockwise) is known as laevorotatory or l- form or –ve sign.
 Enantiomers: d and l (optical) isomers of a compound are called enantiomers and optical isomerism is also called
enantiomerism. Dissymmetry is the necessary and sufficient condition for the existence of enantiomers.
 Chirality centre or stereogenic centre or asymmetric carbon atom: A carbon atom which is attached to four
different atoms or groups in a molecule is called a chiral centre or stereogenic centre and the compounds having one
chiral centre show optical isomerism. For example, lactic acid, tartaric acid, malic acid and butan-2-ol etc.
 The number of optical isomers in a molecule containing number of different asymmetric carbon atom is given by the
relation, 2n, when the molecule has no symmetry. Futhermore, there will be 2n-1, d- and l- forms.
 Resolution of racemic mixture: The process of separation of a racemic mixture (dl-) into d- and l-forms (its
enantiomers) is called resolution.
Walden inversion (optical inversion): the conversion of d- form of an optically active compound into l- form of the
same or different compound or vice versa is known as Walden inversion. For example, the conversion of d-malic acid
into l-malic acid
 Diastereomers: These are the stereoisomer that are neither identical nor mirror images of each other
 Conformational isomerism (conformers): The different arrangements of atoms in space that result from the free
rotation of groups about C – C bond ( bond) axis are called conformation (rotation) isomers and the phenomenon is
known as conformational isomerism. Out of the infinite number of possible arrangements of ethane, propane and
butane, two conformations represent the extremes. These are called (i) eclipsed conformation (ii) staggered
conformation. The eclipsed conformation is least stable while the staggered conformation is more stable. The order of
stability of these conformations is:
Anti > Skew or Gauche > Partially eclipsed > Fully eclipsed
 Conformations of cyclohexane: these are chair and boat conformations which are free from angle strain. Both
forms are interconvertible into each other. Chair conformation or Z form (staggered form) is more stable than boat
conformation or C form (eclipsed form)