Basic Organic (1)
Basic Organic (1)
Basic Organic (1)
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,.
empty 2p orbital
of carbon
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
(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.
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°.
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* =
+
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