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Basic Organic (1)

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bonds 3usle andsingleIt requires reaction to occuT.

single bonds.conjugated system of alternate double and


[IV] Hyperconjugation
Hyperconjugation is an ofextension of
involves delocalisation n electronsresonance. It may be
or n clectrons andregarded as no bond resonance.
Resonance
Hyperconjugation
to an atom of involves delocalisation of -electrons of non-bonding electrons of a hetero atom.
unsaturated system or to an atom having C-H bond of an alkyl group which is attached
propene may be represented as follows : empty p-orbital. For example,
H
hyperconjugation in
H H
H-CH H, < H-C= CH-H, H--CH -CH,
H

H (=CH-H,
H H
The methyl group in propene (CH - CH= CH,) has
thtcugh the H ctoms present on the carbon atom next to the three a-H atoms. Hyperconjugation occurs
number of a -H aton s, morc are te double bond i.e., a-H atoms. Greater the
number of iyperconjugative structures.
It is important to note that
although a free proton (H) has been shown in the
structures of propenc, the H" is still bound to the t
of the double bond in propene which cloud and is not free to move. It is theiyperconjugative
T clectron pair
causes the
electron pair of C--H bond conjugates with the cleavage of the C-H bond of the methyl group. Then the
electron pair of the double bond.
Orbital concept of hyperconjugation : Let us take the
example of ethyl carbocation
(CH3 -CH,). The positively charged carbon atom has an
hypercc njugatlon
empty p-orbital. The carbon atom of CH group is in sp bond
hybridised state. The electrons in the C-H bond of CH3
group can be delocalised in the empty p-orbital of-CH,.

This type of overlap stabilises the CH CH, carbocation.


It is because the clectron pair from the adjacent C-H bond
H
helps in dispersing the +ve charge on carbon atom.

empty 2p orbital
of carbon

Orbital diagram showing hyperconjugation


in ethyl carbocation (CH, -CH,)
12.60)
Some Basic Principles and
H. H Techniques
HH H H
H H
H H
There is no H H
in which C H bonds hyperconjuation in
lie; hence it can
CH,. It is because the
vacant p -orbital is
Facts explained by
resonance cffect. It explainshyperconjugation
not overlap it. perpendicular to the plane
effect :
(a) Stability of many
characteristics Hyperconj
of organic ugati
compounds.
on effect is weaker than that of
secondary (2") > carbocations
methyl carbocation primary
and free
(19). Tertairy butylradicals : The order of their stability is:
have 9, 6, 3 and 0
a-H atoms.carbocation, isopropyl carbocation, ethyl tertiary (3°) >
CH, -C -CH,
carbocation and
CH, -C-CH,
a-H atoms H, 9
H CH -CH, +

CHa
Tertiary butyl carbocation has 9 6
number of alkyl groups hyperconjugative structures and
3
0
interaction stableattached
and more to the +vely is
most stable. In
is the charged
carbocation. Same is true for such freegreater is thegeneral, greater the
carbon atom,
+

CH3 -C-CH,
CH3 -C=CH,
redicals. hyperconjugation
CH; CH3
(9 equivaient structures)

Ch,
CCH,
H
(6 equivalent structures)

CH, -CH, H
CH, =CH,
(3 cquivalent structures)
(b) Ortho and para directing
nature of
directing forelectrophilic aromatic substitutionalkylreactions.
groups:CH group attached to benzene ring is o/p
3-hyperconjugative structures.
H
When one a-H atom is
involved, there are
H--H H
H
H

H-C-H

Morehyperconjugative structures are


IV

hyperconjuation possible due to the


the o/p positions become point of high electroninvolvement of other a- H atoms. Due to
electrophilic substitution takes place at these positions. density (negatively charged).
Therefore
yues

Substrate is that organic species which


reactant is called
is arbitrary, In reagent. If both the reactantssupplies carbon for the (124}
such cases, the
molecule supply
on which carbon for the formation
of new bond and the
During an organic reaction,
some other atom such as O, N, a covalent attention is focused is formation
called
of new bond, then other
etc. is broken and abetween two carbon atoms orsubstrate.
bond choice
Definition
in enthalpies
: A
sequential account of each
new bond is formed. between a carbon and
during bond cleavage and bond step, describing details of electron
reactants into products is called reaction formation, and the rates (kinetics) ofmovement, change
The knowiedge of reaction mechanism. transformation cf
and in planning
strategy for theirmechanism helps in understanding
synthesis. Some basic principles theof reactivity of organic compounds
discussed below. organic reaction mechanism are
1. Fission of a
Covalent Bond
A covalent bond is formed by
either by (i) heterolytic cleavagesharing
of electron pairs. On
or by (ii) homolytic cleavage.supplying energy, a covalent bond may cleave
1. Heterolytic cleavage
formed. The bond breaks in (Unsymmetrical fission): In this cleavage cations and anions are
such a fashion that the shared electron pair remains with the more
electronegative atom.
HcLBr CH, +Br
One atom has 6 electrons in its valence shell and
carries +ve charge (C atom in CH;). The octet of
other atom is complete and has at least one lone pair of
+ electron. This atom carries -ve charge e.g., Br
Thus CH; and Br are formed by the heterolytic fission of
goes to Br atom which is more eiceuo.tcgeive. Herolvtic fission
bromomethane. The shared pair of electron
usually occurs in polar covalent bonds.
2. Homolytic ission (Symmetrical fission): In this
fashion that each aton takes away one electron of the shared pair.cleavage the bcnd brenlks in such a
Thus movement of single electron takes
place instead of an electron pair. Therefore, in homolytic fission
formed. These species are called free radicals and they contain oneneutral species (atom or group) are
unpaired electron. Free radicals are
very reactive.
Heat or light
R + X*
Alkyl free
radical
Homolytic fission occurs in non-polar bonds and it is favoured by heat, ultraviolet radiations
(UV- radiations) and in the presence of peroxides.

Characteristics of heterolytic and homolytic fission


(1) Heterolytic fission takes place in polar covalent bonds and is favoured by polar solvents such as water
and alcohol. Homolytic fission takes place in 1n-polar covalent bonds and is most common in vapour
phase.
(2) Cations and anions are formed in heterolytic fission whereas neutral species (free radicals) are fomed
in homolytic bond fission.
AB Heterolytic cleavagey A + B
AB Homolytic cleavage A + B
Reactive Intermediates. Some Basic Principles and
Techniques
(Reaction
Kedeton intermediates are formed
Intermediates)
Therefore, reactive intermediates canduring organic reactions, They are
Important reactive intermediates are not be isolated. short lived and are highiy
reactive.
1.
Carbocations : carbocations, acarbanions,
free radicels,
and bearing positive chargeChemical
is calledspecies
a having carbon atom containing 6carbenes etc.in
goes to more formed by the carbocation,
electronCarbocations Earlier were called electrons its valence shell
are
heterolytic cleavage these carbonium ions.
CH, electronegative
r element. For example,
of a polar
covalent bond. The shared pair of
MethylCH3 Br
+

The names of carbocation


(ethyl carbocation), carbocations
are
derived from the alkyl group e.g..
CH, CH, CH, (n-propyl CHa (methyl carbocation),
(CH3 )3 Ct C2 Hs
(tert-butyl
of carbocation) :
etc. carbocation), CH, CH CH,
Classification
carbocations according carbocautions They are
(isopropyl carbocation),
charge presentclassified
to the tve as
on 1°, 2° orprimary (1),
3° carbon secondary (29) and tertiary (3°)
atom
CH; and CH, CH,
1° carbocation CH3respectively. For example,
CH, CHCH
Stability of
2° carbocation
H;CC- CH,
carbocations
stability. The stability of
: Any factor which
decreases
3° carbocation

(CH, ); carbocation the tve


decreases in the order 3° > 2° charge of
carbocation will incrcase its
Explanation C(C;
: There
), CH
are two ways to Cr;Ci CH,
> 1°.
C%j -CH,
() Based
upon +I effect: The explain stability of
thc >CHa
groups tend to increase the alkyl groups have + I effect carbocations
charge on it. Greater is the electron density on the tvely charged (electron releasing inductive effect).
will be the number
stability of carbocation. Thus, The groups, more will be thecarbon atom and, thus, disperseAlkyl
of alkyl
R
dispersal of tve charge and morethe
stability of carbocation decreases
R in the order :
H
X’ot > R-ct
Rt
H
(ii) Based upon
hyperconjugation Hyperconjugation
a.-H atom and it is least stable. CH;
:
depends upon the a-H atoms. CH3
CH, has 3- a-H atoms and is has no
H H
- H more stable.
H H"
’ HC=C-H
H H HC=C-H
Ht | ’ HC=C-H
H H H
H H
Isopropyl carbocation (CH
9a- H atoms. They are, -CH-CH;) has 6a.- H atoms and
tert.butyl carbocation (CHa) Chas
stability of carbocation therefore, more stable. Greater the delocalisation of +ve
charge, greater is the
nd Techniques
urith Reactivity of
carbocations :
anions and electron
the order of their pair Carbocations
donor
are electron
deficient
species to complete their octet.. and are highly reactive. They
[12.49

order Primary (1) > stability. Reactivity of Their combine


:
Secondary carbocations
(2°) > Tertiary decreases in the reactivity is reverse to that of
Orbital structure of carbocation : The (3°)
empty
is sp
hybridised. The sp hybridised orbitals +vely charged carbon atom P-orbital
formation of three o bonds. The are involved in the
unhybridised
carbocation has planar structure and bond p-orbital is vacant. A 120° ÞR
unhybridised p-orbital is perpendicular to the molecular angle is 120°. The sp hybridised carbon
Characteristics of plane.
carbocations : (1) The
in its valence shell, itcarbon atom
is electron carrying
charge has six electrons tve
is electrophile. deficient and Shape of carbocation
(2) The carbon atom
carrying +ve charge is sp hybridised, it is trivalent
(3) Greater the number of a H and has planar structure.
atoms, greater is the delocalisation of tve
greater is the stability of carbocation. charge of the carbon atom and
(4) Allyl and benzyl
carbocations are resonance stabilised and are more stable than methyl, ethyl and
many other carbocations.

CH, = CH-CH, CH, -CH = CH,


(5) Greater the number of benzene rings attached to
the tvely charged carbon atom, more are the
resonating structures and greater is the stability of carbocation. Thus, stability of carbocations
decreases in the order :

(CoHs ), C> CGH_ ), CH> CGH, CH, > C,H


CH, CH, CH, CH CH,

(6) Presence of electron attracting groups (H effect) such as -NO,, -CN, -CH0, -COOH etc. decrease
the stability of carbocation. Electron releasing groups increase the stability of carbocation.
2. Carbanions : Chemical species having a carbon atom containing 8 electrons in its valence
shell and bearing negative charge is called carbanion.
Carbanions are formed by the heterolytic cleavage of a covalent bond. The shared electron pair goes
to carbon atom.

OH + HLH, CHO E,0 + CH, CHO

H,N + C =CH ’ NH, + C = CH


The names of carbanions are derived from the alkyl groups e.g., CH, (Methyl carbanion), C2Hs
(ethyl carbanion) etc.
Classification of carbanions : They are classified as primary (1), secondary (20 ) and tertiary (30)
carbanions according to the -ve charge present on l°, 2º and 3° carbon atom respectively. For example,
12.50)
Some Base Princples end Techniques
CH, and Cls
'arbanion CH, CH CHly CH,
2arbaolon
(Iayeyyt earbanion) C, CCH
Shabilio f cardanions The onder of 3earbanion
free radicals,
Stability of carbanions decrcasesstability of carbanions is byleabanion)
(teriary
roverse to that of
CH, > CH, CH, > (CH, ), in the order 1 > 20 > 3, Por exanmple. carbooations and
Aplanation : t is CH> (CH)
releasing explained in tems of +
carbanion isThey incrcase the electron density on theI eeot of alkyl groups, AIkyl
decreased, Greater the number of alkyl negatively charged carbon atomgroups are electron
groups, Nmaller is the stability of
and stability of
>R >R carbanion.
R’
H
Reacivio ef
carbanions :
arbanions combine with cations or The reaction intemediates are short
stability. The reactivity of electron pair acceptors, Their lived and are very
Orbiral Structure ef carbanions deereases in the order 3" reactivity is roverse to the
order
reactive.
of their
charge is p hybridised, Three carbanion : The
sp hybrid carbon atom >20> 1"
bearing -ve one pale
The fourth sp orbitals form
hybrid orbital contains a lone pair of 3a bonds. sp hybrid orbltal
responsible for the
nyramidal strueture -velike charge on carbanion. The electron and is
ammonia carbanion has
Characteristies ef
chare ias &econscarbanions (1) The aarbon ote
(2) The i. its valence shell and is booring
(3) Presencecarbon-atom bearing -ve change is sp nucleophile. Shape of carbanion
of electron
releasing groups hybridised and has pyramidal structure.
(4) carbanion. (+1 effect) such as alkyl
groups decrcase the stability of
Presence of
electron attracting groups (
stability of carbanion. effect) such as -NO,, -CN,
(5) Allyl and
benzyt -CHO, -COOH eto. increase the
carbanions
are resonance stabilised.
CH; CH-CH, CH, -CH= CH,
CH,
CH,
CH2 CH,
ÇH,

6) Greater the number of benzene


stability of carbanion. Thus, the rings attached to the carbon atom
(CoHs ); C> (CHs ); CH > CH, stability of carbanions decreases inbearing -ve
the order :charge, greater is the
CH, > CoHs
( Stability of carbanion increases with the (12.31
increase ins-character of hybrid orbitals.
Stability CH, CH, CH, < CH, - CH= CH < CH,
Hybridisation sp C=C
% s-character sp' Sp
25 33.3
3. Free 50
radicals
: A free radical may be defined as an
atom or a
odd or unpaired electron. Free radicals are group of atoms which has an
produced on homolytic fission of a covalent bond.
Heat or light’ Cl" + CI'
Chlorine free radical
When a free radical attacks a covalent molecule, another free radical may be produced. For
example,
CI' + CH4 ’ HCI +
CH,
Methyl free radical
Classification of free radicals : The alkyl free radicals are classified as primary (19), secondary (2")
and tertiary (3°) according to the carbon atom carrying the unpaired electron is primary, secondary or
tertiary.
CH3
CH, and C2 H, CH, CH- CH3
1° free radical 2° free radical
(Isopropyl free radical)
H,C CH,
3° free radical
(Tertiary butyl free radical)

The names of free radicals are similar to those of carbocations or carbanions e.g., methyl free radical,
ethyl free radical etc.
Stability of free radicals : The oder of stability is same as those of carbocations. The stability of
free radicals decreases in the order : 3° > 20 > 1°.

(CH,); C > (CH, ), CH > CH, CH, CH, > C: Hs > CH


Explanatiun : It is explained on the basis of hyperconjugation. The number of hyperconjugated
structures depends upon the a-hydrogen atoms. CH3 has no -H atom and is least stable. CH, CH,
has 3 a-H atoms and is more stable. Isopropyl free radical (CH, ) CH and tert.butyl free radical
(CH, ) C have 6 and 9 aH atoms respectively. Therefore these free radicals are more stable.
H H H H H
H
H-C-C' H-C=C ’ HC=C ’ H-C=C etc.
H'
H H H H H H H

Greater the delocalisation of odd electron, greater is the stability of free radical
free radicals.
Allyl and benzyl free radicals are resonance stabilised and are more stable than the alkyl
the
Greater the number of benzene rings attached to the carbon atom carrying odd electron, greater is
stability of free radical. Stability of free radicals decreases in the order :
(CçHs ); C > (CçHs ), CH > CçHs CH, > C6 Hs
Reactivity of free radicals : Free radicals are short lived and are very reactive. They combine with
other free radicals to complete the octet.
CH, + CH, ’ CH; CH3 , CI' + CI' ’ Cl, , CH3 + CI' ’ CH, ClI
(CBSE-6CHEM-XI)
Some Basic Principles and 1Techniques
Free radicals may also undergo
C, Hs + C, Hs
disproportionation.
The order of ’ C,H, + CzH4
reactivity is same as those of carbocations i.e., 1°> 2°
Orbital Structure >3.
of Alkyl Free
The carbon atom carrying the Radicals
odd electron is sp Ro -unpaired electron
sp hybrid orbitals form 3
g bonds. The odd
hybridised. The three
unhybridised p-orbital. The alkyl free
electron is present in 120 6R
sp hybridised carbon
the presence of odd radical has planar structure. Due to R
electron, free radicals are paramagnetic.
Electrophiles and nucleophiles
Electrophiles and nucleophiles are the
attacking reagents. They attack the
Shape of RC free radical
substrate and produce reaction
1.
Electropiles (E) : Theyintermediates.
are
The important
attacking reagents are :
Electrophiles may be electron
cations or neutral species. loving species. They contain an electron deficient atom.
(a) Positively charged
electrophiles : H* , H,0*,NO, ,NO, R-C=0, x* etc.
(b) Neutral
radicals etc. electrophiles : BF3, AICl3, FeCl, SnCl4; R,C:
(Carbene), RN: (nitrenes), R (free
Electrophiles
Lewis Acids.
are electron deficient.
They have the tendency to attract the
2. Nucleophiles (Nu) : electrons and are, therefore,
either anions or neutral They are nucleus loving
species having at least one chemical species and are electron rich. They are
(a) Negative lone pair of electrons.
nucleophiles : E,H ,R ,Civ,R,RCOO ,X halide ion) etc.
(b) Neniral nucleophiles : H, 0: ,
R3 N: etc. RO-H, R-0-R, :NH, , R-NH,, (R), - NH,
Since nucleophiles contain at least
behave has Lewis base. Alkyl halide (RX one unshared pair of
) is a neutral electrons, they are electron pair donors and
partial tve charge is gençrated on the molecule.
may be attacked by a núcleophile. carbon atom., The carbon atomDue to the anpolarity of CX bond, a
becomes electrophilic centre and
EXAMPLE 1: Using curved-arrow notation, show the
the following covalent bonds
undergo heterolytic formation of reactive intermediates when
(a) CH, -S CH3 cleavage.
(b) CH, CN
(c) CH, Cu
SOLUTION : (a) CH, (NCERT)
CH, ’ CH, +SCH; (b) CH, L¯ +

CH, + CN
() H, \ cu ’CH, + Cu
EXAMPLE 2: Giving justification, categorise the
electrophile : HS , BF; , Cz H;0,(CH,)3 N:, CI" , following molecules/ions as nucleophile or
CHg C* =
+

SOLUTION: Nucleophiles : HS,C,H;0 (CH; ), N: ,H,N: 0, H,N:, NO, NCERT)


Electrophiles : BF , CI, CH; C* =0,N0,
CBSE-6/CHEM-X)

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