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Electronic effects (I, R, m, Hyperconjucation), Physical properties
Acidic strength & basic strength
ELECTRONIC EFFECT : The effect which appears due to electronic distribution is called electronic effect.
(A)
Inductive Effect Inductive Effect When a sigma covalent bond is formed between two atoms of
different electronegativity atom then the sigma () bond pair electron are shited towards more electronegative atom due to this shifiting of e a dipole is created between the two atoms.
Due to this dipole the bonds e in the chain are also shifted and the chain becomes polarised this effect of
polorisation in the chain due to a dipole is called inductive effect.
Diagram showing I effect
2.
(a)
I Effect :
The group which withdraws electron cloud is known as I group and its effect is called I effect. Various
groups are listed in their decreasing I strength as follows.
>
>
> NO2 > SO3H > CN > CHO > COOH > F > Cl > Br > I
> OR > OH > NH2 > C CH > C6H5 > CH = CH2 > H.
(b)
+ I Effect :
The group which repel (or release electron) cloud is known as + I group & this effect is + I effect.
>
> C(CH3)3 > CH (CH3)2 > CH2 CH3 > CH3 > D > H
Example-1 Since NO2 is I group it pulls or withdraws e from cyclohexane ring making it e deficient
(a) CH3
CH2
(c)
CH2
(b)
CN
CH2
(d)
(e)
(f)
(g)
(h)
(i)
(j)
CH 3
CH
CH
NO2
O
-
(k)
-
-
3.
-
-
(a )
H3 C H 2C H2 C CH COOH
|
Cl
(II)
CH 3 CH 2 CH CH 2 COOH
|
Cl
(III)
CH 3 CH CH2 CH 2 COOH
|
Cl
(IV)
Explanation :
We know that I effect increases acidic strength. Now morever it is distance based effect so where the I
group is nearest to COOH, It enters strong effect and makes acid strong.
Example :
(I)
O2N CH2 COOH
(III)
H3CO CH2 COOH
(II)
(IV)
F CH2 COOH
CH3 CH2 COOH
Since NO2 has strong I effect its influence will make corresponding acid strongest ( I effect acid
Page # 3
character).
Example :
Arrange for acidic strength order CH3COOH, ClCH2COOH, Cl2CHCOOH, Cl3CCOOH
Ans.
CH3COOH < ClCH2COOH < Cl2CHCOOH < Cl3CCOOH
(b)
Stability of alkyl carbocation : Carbocations are electron deficient species and they are stabilised by +
effect and destablised by effect. Because + effect tends to decrease the positive charge and effect
tends to increases the positive charge on
Example :
(c)
Stability : CH3
(carbocation)
Stability of carbon free radical : Carbon free radical are stabilised by + I effect.
Example :
CH2
< CH3
< CH3
CH3
LECTURE # 2
(B)
Resonance Effect
The delocalisation of adjacent (parallel) p-orbital electron is called resonanc. Through resonance the e
density in the molecule becomes uniform, due to uniformility of e density the stability of molecule increases.
Hence the phenomena of a resonance is a stabilising effect.
In resonance only parallel p-orbital e are involved. To explain the property of actual molecule different lewis
structure are drawn with the movement of p-orbital electrons.
This lewis structure are called resonating structure or canonical structure.
Resonance hybrid
Examples :
(I)
(II)
(III)
(IV)
(V)
(VI)
CH2 = CH
CH = CH2
Resonating structure are only hypothetical but they all contribute to a real structure which is called resonance
hybride. The resonance hybride is more stable than any resonating structure. The P.E. difference between
the most stable resonating structure and resonance hybride is called resonace energy. The stability of
molecule is directly proportional to resonance energy.
Page # 4
The most stable resonating structure contribute maximum to the resonance hybride and less stable resonating
structure contribute minimum to resonance hybride.
CH2 = CH CH = CH2
3.
CH2 = CH
4.
CH2 = CH CH = CH2
5.
CH2 = CH CH = CH2
CH3 CH = C = CH2
(Show resonance)
4.
5.
CH2 = C = CH2
Types of Conjugation:A given atom or group is said to be in conjugation with an unsaturated system if:(i) It is directly linked to one of the atoms of the multiple bond through a single bond.
(ii) It has bond, positive charge, negative charge, odd electron or lone pair electron.
1.
2.
CH2 = CH CH = CH2
+
CH 2 = CH CH 2
3.
..
CH 2 = CH NH 2
Q.
4.
CH2 = CH CH2
5.
CH2 = CH CH = CH CH2
O
||
(a) CH3 CH CH C CH3
(a)
..
(b) H 2 N CH CH C N
(b)
(c)
(c)
(d) CH3 O CH = CH
(d)
(e)
(e)
..
(f) CH3 C O :
(f)
(g)
(g)
(h)
(h)
(i)
(i)
(j)
(j)
Q.
CH2 = C = O
Ans.
+
CH3 C O
..
..
..
..
CH 3 C = O
CH 2 = C = O
C H2 C O N = N = N
N N N
Page # 6
LECTURE # 3
Mesomeric Effect : When a group releases or withdraw p orbital electron in any conjugated system then it is called
M effect group and effect is known as mesomeric effect.
+M group : (electron releasing group) : A group which first atom bears -ve charge or lone pair always shows
+M effect.
Relative order of +M group :
>
>
> NR2 > OH > OR > NHCOR > OCOR > Ph > x > NO > NC
e.g.
1.
2.
3.
4.
M group : (-electron withdrawing)
Relative strength of M group :
NO2 , CN , SO3H , CHO, CH = NH,
e.g.
1.
+
O N = .O:
.
+ . .
O N .O:
.
+ . .
O N .O:
.
2.
+ ..
O N .O:
.
+
+ ..
O N = O:
3.
Q
H 2C = CH C N:
H 2C CH = C = N:
..
By drawing resonating structures of following molecules, Judge whether the group attatched to ring exerts
+ m or m effect.
Page # 7
Ans.
NHCCH3
NHCCH3
NHCCH3
NHCCH3
NHCCH3
(a)
O
CCH3
(b)
Note:
1.
CH3
CH3
CH3
CH3
When a +m group and m group are at meta-positions with respect to each other then they are not in
conjugation with each other, but conjugation with benzene ring
etc.
2.
Q.
+M group increases electron density in benzene ring while M group decreases electron density in the
benzene ring.
Write electron density order in the following compound.
(a)
Ans. III > I > II > IV
(b)
Ans.
Ans.
(c)
Page # 8
CH2 = CH CH = O
I
Stability order I > II
II
2.
(3)
Negative charge on more electronegative atom and positive charge on less electronegative atom are more
stable.
e.g.
1.
Stability order II > I.
2.
(4)
Note : The rule of electronegativity and rule of octet is are contradictory to each other then priority is given
to the octet rule.
Two different compounds in which one compound has more conjugation is more stability (provided nature of
bonding is same).
CH2 = CH CH = CH2
CH2 = CH CH = CH CH = CH2
I
II
Stability order II > I.
Page # 9
(6)
In two compounds if one is aromatic and another is non aromatic and conjugation is equal in both the
compound the aromatic compound is more stable (nature of bonding is same)
(cyclic and conjugate)
Stability order
(7)
II
Structure with linear conjugation is more stable than cross conjugation (nature of bonding is same).
Cross conjugation : If two groups are in conjugation with a particular group but not conjugated with each other
then the system is called cross conjugation.
>
LECTURE # 4
2.
Hyperconjugation in alkene
3.
Hyperconjugation in carbocation
4.
Hyperconjugation in radical
H
CH 2 C H2
5.
H
CH2 = CH2
Hyperconjugation in toluene
Page # 10
1
HHydrogenat ion
6.
Applications of hyperconjugation
(a)
Stability of Alkenes:- Hyperconjugation explains the stability of certain alkenes over other alkenes.
Stability of alkenes Number of alpha hydrogens and Number of resonating structures
CH3
H3C
H3C
CH3
H3C
Example :
(b)
C = CH2
H3C
H3C
Heat of hydrogenation : Greater the number of hydrogen results greater stability of alkene. Thus
greater extent of hyperconjugation results lower value of heat of hydrogenation
Example :
(c)
H3C
C = CH CH3
C=C
(Heat of Hydrogenation)
Example :
(a)
< CH3
< CH3
(b) CH3
>
> CH3
CH3
Stability of free radical : Greater the number of -hydrogen results greater stability of carbon free radical
Example : 7
(a)
< CH3
(b) CH3
< CH3
>
>
(D)
CH3
Page # 11
(B) CH3
CH3
In the condition of (A) E effect is supported by + I effect similarly in the case of (B) E effect is opposed by
+ I effect. That is why (A) is easily possible in comparison to (B).
Case II : In the case of vinyl bromide :
(A)
CH =
(B) CH2
E
Br
Br
(A) is the condition of E effect supported by +m effect and opposed by I effect, (B) is the condition of E
effect opposed by + m effect and supported by - I effect.
Since + m > I effect, so the (A) is valid case.
Case III : If the multiple bond is present between two different atoms, the electromeric shift will take place
in the direction of the more electronegative atom.
(a)
(b)
+E and E effect : The electromeric effect is represented by symbol E, and is said to be + E when the
displacement of electrons is away from the atom or group, and E when displacement of electrons is
towards the atom or group.
+ E effect
E effect
NC
LECTURE # 5
Physical properties
(A)
Hydrogen Bonding
1.
Definition :
The hydrogen bond is an electrostatic attractive force between covalently bonded hydrogen atom of one
molecule and an electronegative atom (such as F, O, N) of another molecule.
eg:- Consider the hydrogen fluorine bond in hydrogen fluoride, HF. This bond is a polar covalent bond in
which hydrogen is attached to a strongly electronegative element.
H
F
The positive charge on hydrogen will be attracted electrostatically by the negative charge on F atom by
another molecule of HF.
H F ----- H F ------ H F
Covalent
hydrogen
bond
bond
Hydrogen bond is a very weak bond (strength about 2 10 kcal/mol)
2.
Conditions for hydrogen bonding:(a) The molecule must contain a highly electronegative atom linked to hydrogen atom.
(b) The size of electronegative atom should be small.
F, O and N atoms only form effective hydrogen bonding.
Example : 1
Greater the electronegativity and smaller the size of the atom (F, O, N), the stronger is the hydrogen bond.
H F ----- H > H O ----- H > H N ----- H
10 Kcal/mole 7 Kcal/mole
2 Kcal/mole
Page # 12
3.
(A)
Intermolecular hydrogen bonding:- In such type of linkages the two or more than two molecules of the
same compound combine together to give a polymeric aggregate.
This phenomena is also known as association.
Example : 2
(I) Hydrogen bonding in formic acid (Dimerisation)
O H ----- O
CH
HC
O ----- H O
(II) In m - Chlorophenol
O H ------ Cl
--Cl
(III) In water
H
OH ------
- - O H ------- O H ----- O H
O
+
N
O --------- H O
(IV) In p-Nitrophenol
----- H O
N
+
O -------
+
N
O --------- H O
H
O H ------ O H ----H
(B)
Intramolecular hydrogen bonding:- In this type, hydrogen bonding occur within two atoms of the same
molecule. This type of hydrogen bonding is commonly known as chelation.
O H
Example : 3
Cl
(I)
o-Chlorophenol
H
O
(II)
o-Nitrophenol
N
O
H
O
H
(III)
O
C
H
O
2, 6-Dihydroxybenzoic acid
Page # 13
4.
Conclusion:
(a) The chelation between the ortho substituted groups restricts the possibility of intermolecular hydrogen
bonding.
(b) Chelation does not take place in m & p isomers because the two groups far away from each other.
(c) Ortho isomers of hydroxy, nitro, carbonyl compounds have low M.P. than their corresponding m & p
isomers.
(B)
Dipole moment
Due to difference in electronegativity polarity developes between two adjacent atoms in the
molecule. The degree of polarity of a bond is called dipolemoment.
(a) Dipole moment is represented by .
=el
= Dipolemoment
l = internuclear distance between two atoms, i.e., bond length in cm.
e = magnitude of separated charge in e.s.u.
e = 1010 e.s.u.
d = 108 cm
So 1D = 1 1018 esu.cm
(b) The Debye (D) is the unit of dipole moment.
(c) The dipole moment is represented by arrow head pointing towards the positive to the negative end.
Cl
C
Cl
Cl
Cl
(d) Dipole moment of the compound does not depend only on the polarity of the bond but also depends on
the shape of the molecule.
(e) Dipole moment of symmetrical compound is always zero. ( = 0)
(f) Symmetrical compounds are those compounds which fulfill two conditions.
(i) Central atom is bonded with the same atoms or groups.
(ii) Central atom should have no lone pair of electrons.
Example : 4
O= C= O
Resultant = 0
F
B
Example : 5
Borontrifluoride
= 0.0
(g) Dipole moment of unsymmetrical compound is always greater than zero ( 0 ).
..
..
..
Example : 6
CHCl3
H 2.O.
H2 S
NH3
..
Page # 14
Unsymmetrical molecules:..
..
O
..
N
H
H
Water
= 1.84D
H
Ammonia
= 1.46D
(h) electronegativity of central atom or surrounding atoms present on the central atom of the
molecule.
(i) Dipole moment of the trans derivative of the compound will only be zero if both the atoms attached to
carbons are in the form a and b.
C=C
C=C
=0
Example : 7
Cl
H
C=C
Cl
H
C=C
Cl
= 1.85D
(cis)
Cl
H
= 0D
(trans)
(ii) If both will not be atoms then trans may or may not be zero.
(iii) If group have linear moments, then the dipolemoment of the trans isomer will be zero.
H3C
Example : 8
CH3
H
C=C
C=C
H
CH3
= 0.33D
H3C
= 0D
(iv) If group have non-linear moments, then the dipolemoment of the trans isomer will not be zero.
H
Example : 9
COOH
C=C
HOOC
= 2.38D
(j) Dipolemoment of disubstituted benzene are :Case I:- When both groups x and y are electron donating or both groups are electron withdrawing then: 12 2 2 21 2 cos
1 = dipolemoment of bond c x
2 = dipolemoment of bond c y
= angle between x and y
Page # 15
Example : 10
Cl
= 0
(ii) If x and y are same groups and group have linear moments then the dipolemoment of para derivative will
be zero.
CH3
CN
CH3
CN
= 0
= 0
Example : 11
Cl
Cl
Cl
Example : 12
= 2.54D
Cl
= 1.48D
(iii) If x and y are same groups and x = y and group have non-linear moments then the dipolemoment of para
derivative will not be zero.
OH
COOEt
OH
COOEt
Example : 13
0
0
Case-II:- When one group is electron withdrawing and the other group is electrondonating then: 12 2 2 21 2 cos
So
CH3
CH3
CN
Example : 14
CN
CN
in increasing order
Page # 16
LECTURE # 6
(C) Criteria of Boiling Points :
The boiling point of a liquid is the temperature where its kinetic energy is sufficient to overcome the
intermolecular attractive forces.
Boiling point (a) Intermolecular hydrogen bonding
(b) Molecular weight attraction
(c) dipole-dipole attraction
(d) Strength of vander waal's
Conclusion :
(a) Intermolecular hydrogen bonding increases the B.P. of the compound and also its solubility in water.
(b) Intramolecular hydrogen bonding (chelation) decreases the B.P. of the compound and also its solubility in
water.
(a) Hydrogen Bonding
(i) Water:- Water has the lowest molecular weight among hydrides of the VI group of periodic table, it has
the highest boiling point.
Water molecules associate through intermolecular hydrogen bonding and thus require more energy to separate the molecules for vaporization.
H
H
H
H
HO
Compound
B.P.
HO
HO
H2O
100C
HO
H2S
59.6
H2Se
42C
(ii) Alcohols :
The successive replacement of hydrogen atom of the OH group of alcohol by alkyl group to form ether
blocks the probability of hydrogen bonding reduces and thus B.P. of alcohols are higher than ether.
B.P.
CH2 OH
CH2 OCH3
CH2 OCH3
CH2 OH
197C
CH2 OH
125C
CH2 OCH3
84C
(I)
(II)
(III)
Ethene
Ethyne
(B.P. = 102C)
(B.P. = 75C)
(ii) Alkynes has higher B.P. than corresponding alkanes / alkenes, due to greater dipolemoment in alkyne
then in alkene.
Page # 17
(iii) Boiling point of cis isomer is always more than the trans isomer, dipole-dipole attraction in the cis isomer
is more than the trans isomer.
(c) As molecular weight increases B.P. of the homologue also increases
Example : 17
Cl
o-Chlorophenol : (B.P. = 178C)
HO
Cl ------ H O
Cl --------- H O
Cl -----
Example : 18
CH2 OH
CH2OCH3
CH2OCH3
CH 2OH
197C
CH 2OH
125C
CH 2OCH 3
85C
OH
CH3 C CH3
OH
CH3 CH CH2 CH3
99C
CH3
83C
CH3 I
CH3 Br
CH3 Cl
2.
CH3 CH2 OH
CH3 CH2 F
CH3 CH3
Ans.
CH3 F
(I)
(II)
OH
OH
OH
Cl
CHO
Ans.
(I)
>
(II)
>
>
CHO
Examples : 21
Ortho - hydroxy, nitro-, carbonyl, carboxylic or chloro compounds have lower melting and boiling points than
the respective meta or para isomer due to interamolecular, H-bonding in ortho substituted compound.
Page # 18
Reason:- Due to intramolecular hydrogen bonding association of molecules does not take place.
Chelation also explains the low boiling point of enolic form of acetoacetic ester than ketonic form.
O
O H ---- O
CH3 C = CH C OC2H5
(enol form) Chelation
(E)
Melting Point :
(a) Melting point:- The M.P. of a liquid is the temperature where its kinetic energy is sufficient to overcome
the intermolecular attractive forces.
The heavier the molecule and stronger the intermolecular forces, higher will be the M.P. of the compound.
M.P. generally increase with increase in number of carbon atoms in most of the homologues series.
Examples : 24
The M.P. of covalent compounds increases with increase in molecular weight except water.
Mol. wt.
M.P.
B.P.
H2O
18
0C
100C
H2S
34
83C
59.6C
H2Se
81
64C
42C
H2Te
130
54C
1.8C
Reason:- In water molecule, hydrogen bonding is present so become more compact and more energy is
required to get them seperated during evaporation / melting.
M.P. depends upon symmetry of compounds in isomers, more symmetric compound have higher M.P.
C
|
i.e. C C C > C C C C C > C C C C
|
|
C
C
LECTURE # 7
Relative strength of Organic Acids :
(a) Defination :
(1) Arrhenius Acid : The compounds which furnish H+ ion in aqueous solution are called Arrhenius acids.
Ex. H2SO4, HNO3, HCl, HClO4 etc.
(2) Bronsted Acids : The species which are H+ ion donors are called Bronsted acids. Ex. NH4+ , H3O+,
etc. All Arrhenius acids are Bronsted acids.
(3) Lewis Acids : The lone pair acceptors are known as lewis acids. They have vacant p or d orbitals. Ex.
BX3, AlX3, ZnX2 etc.
Page # 19
RCOO H
Ka
RCOOH
A strong acid is defined as the acid which furnish more number of H+ ion in aqueous solution
OR the acid which is more ionised in aqueous solution.
So, a stronger acid has higher value of Ka , or it has lower value of pKa.
pKa = log Ka
(c)
(i) Inorganic acids : The mineral acids are inorganic acids. These are considered as completely ionised
in aqueous solution and are described as strong acids. [H2SO4 > HCl > HNO3].
(ii) Organic acids : They are R SO3H > R COOH > Ph OH > ROH.
They are weakly ionised in water, so these are weaker acids then mineral acids.
(d) Prediction of Acid strength :
(i)
Anion/conjugate base of HX
(ii)
(Cb conjugate base)
A stronger acid has more stable anion, so a stronger acid forms a more stable conjugate base.
Factors affecting stability of conjugate base/anion :
(i) Presence of EWG in the alkyl (R) part of the acid increase stability of anion, and hence increases
acidic strength.
(Ka)
Conjugate base/Anion :
(stability)
Explanation :
>
>
in acidic character
Page # 21
LECTURE # 8
4.
(Ar Aromatic)
Ex.1
Ans.
(11) > (2) > (7) > (3) > (6) > (10) > (1) > (4) > (5) > (8) > (9)
Ex.2
Ex. 3
Ex.4
>
(a) HCOOH
(I = 0)
>
>
CH3COOH
(+I)
Page # 22
>
CH3CH2COOH
(+I)
>
(f) F CH2 COOH > Cl CH2 COOH > Br CH2COOH > I CH2 COOH
(g)
(h) CH3 CH2 COOH < CH2 = CH COOH < CH C COOH
sp3
sp2
sp
(ii)
Page # 23
LECTURE # 9
Acidic strength in Aromatic acid :
Acidic strength in aromatic acid depends upon following factors
(i)
Steric effect (steric inhibition of resonance) or Ortho effect
(ii)
Electronic effect of substituents
(iii)
Intermolecular and intramolecular hydrogen bonding.
Steric effect (ortho effect) : In case of 1,2-disubstituted benzene if the substituents are bulky then due to steric
repulsion (vanderwaal repulsion) the group go out of plane w.r.t. benzene ring. Due to this change in planarity
the conjugation between the substituents on benzene is slightly diminished. This effect is called steric
inhibition of resonance. (ortho effect) In case of ortho substituted benzoic acid due to steric inhibition of
resonance the conjugation between benzene and carboxylic group is diminished and the +m effect benzene
ring to the carboxylic is diminished and as the acidity increases w.r.t. benzoic acid and w.r.t. meta and para
substituent benzoic acid inspite any electronic effect of substituent
G may be NO2 , R , X , COOR , COOH
except OH , NH2, C N
O
OH
COOH
COOH
NO2
(c)
NO2 (b)
H+
H+
H+
O
NO2
O
N
I, m
O
I (m)
N
O
O
I (w), m
Page # 24
<
Ex.
Ex.
<
<
<
>
Electronic effect : In case of different O susbstituted benzoic acids the acidity is not decided by the basis of
ortho effect but it is decided by the. electronic effect of substituents.
Ex.1
+I
II
+m>I
III
I>+m
II
I,m
V
Ex.2
+I
II
I
III
I
II
I
V
Ex.3
+I
II
I
3.
I
III
I
II
I
V
COOH
Ex.1
COOH
H +
H+
OH O
C
OH
COO
o>p
o<p
o<p
o<p
Ortho is steam volatile.
Ex.2
Ortho effect is operative only in o-substituted Benzoic acids and not in o-substituted phenols.
Page # 26
LECTURE # 10
(3) Acid strength of Phenols (effect of substituents) :
There is no ortho effect in phenol
>
>
>
>
>
Page # 27
LECTURE # 11
Ex.1
>
(1)
>
>
(II)
(III)
>
>
(2)
(I)
(IV)
(V)
(VI)
only (I)
Page # 28
(3)
(I)
(II)
(III)
(IV)
(V)
(VI)
>
(4)
>
(5)
(No acidic H)
>
(6)
>
>
picric acid
Reaction of Acids with salts :
(1)
Ex.
NaX
+
Salt = NaOH + HX
Weak acid
HY
Strong
Acid
NaY
+
Salt = NaOH
+ H Y (S.A.)
HX
W.A.
Remark : A stronger acid displaces the weaker acid from any metal salt. The weaker acid is released out as a gas
or liquid or precipitates out as a solid. The weaker acid cannot displace the stronger acid from the salt.
Ex.
Q.
ONa
OH
(B)
Not possible
NO2
Page # 29
SO3Na
(C)
COOH
+
Not possible
LECTURE # 12
Basic strength
(I) DEFINITION:
Ex:
(a) Arrhenius base: Those compound which furinishes OH - ions in aquous solutions are known as arrhenius
base.
NaOH, KOH, Ca(OH)2 etc.
(b) Bronsted base:- e pair donor or H ion acceptor. :NH3, R N H2, R2 N H, R3 N , H2 O, R O H, R O R
(c) Lewis base:- e pair donor to H ion.
NH4
R O R + H+
+
R OR
H
NH 3 + H +
(II) BASICITY:
It is the tendency to accept H ion, or it is the case of acceptance of H ion.
H3N: + H __________easily..
Ex:
H O H + H __________less easily..
Thus, NH3 > H2O in basicity.
Less electronegative atom (N) donates electron pair easily.
+
R NH3 + OH Conjugate Acid (C.A.)
[RNH3 ][OH - ]
Kb =
[where Kb = Base dissociation constant].
[RNH2 ]
pKb = logKb
Note : A stronger base always has a weaker C.A. and vice versa.
CH2
(iv)
<
(Resonance
Stabilisation)
(localised
ve charge)
Ex.
Electrongeativity :
O
(iv) Amidines R C NH2
:NH
Among these, amides are the weakest bases.
(iv) > (i) > (ii) > (iii)
and become stabilised by H atom attatched to N atom greater is possibility of solvation via H bonding by
water. Alkyl groups are hydrophobic and inhibits H bond.
H
H
H
N:
+ = O, solvation = max., Steric Hinderance = min.
(1)
H
H
H
(2) R N: +, solvation, Steric Hinderance
H
H
H
(3) R N: + , solvation, Steric Hinderance
R
R
H
R
N:
+max., solvation min., Steric Hinderance max.
(4)
R
In aq. solvation, the general order of basic strength is R2NH > R3N > RNH2 > NH3. (R = Ethyl)
or, in some cases, it is R2NH > RNH2 > R3 N > NH3 (R = Methyl)
Explanation: It will be seen that the introduction of an alkyl group into ammonia increases the basic strength
markedly as expected. The introduction of a second alkyl group further increases the basic strength, but the
net effect of introducing the second alkyl group is very much less marked than with the first. The introduction
of a third alkyl group to yield a tertiary amine, however, actually decreases the basic strength in both the
series quoted. This is due to the fact that the basic strength of an amine in water is determined not only by
electron-availability on the nitrogen atom, but also by the extent to which the cation, formed by uptake of a
proton, can undergo solvation, and so become stabilised. The more hydrogen atoms attached to nitrogen in
the cation, the greater the possibilities of powerful solvation via hydrogen bonding between these and water:
Thus on going along the series, NH3 RNH2 R2NH R3N, the inductive effect will tend to increase the
basicity, but progressively less stabilisation of the cation by hydrating will occur, which will tend to decrease
the basicity. The net effect of introducing successive alkyl groups thus becomes progessively smaller, and
an actual changover takes place on going from a secondary to a tertiary amine.
Conclusion :
(1) Secondary amines are stronger bases than tertiary amines.
Reason:- Solvation is less in 3 amines and more steric hinderance to H ion.
(2) All alkyl amines (1, 2, 3) are stronger bases than ammonia (due to + effect of R group).
(3) In gaseous phase, the basic strength order is 3 > 2 > 1 > NH3 (+ effect of R group).
(4)
: NH3
> NH2 NH2 >
NH2 O H
Ammonia
Hydrazine Hydroxylamine
(3)
CH2 NH2
(2)
(1)
Ex.
N:
>
N:
(More compact)
Cyclic Amine is more basic than acyclic amine (if degree of N is same).
Page # 32
(5)
:NH2
:NH2
(6)
Kb order : I > II > III
(7)
I
Sulphonamide
II
Amide
III
Ar. Amine
IV
Aliphatic amine
CH3 CH NH2
|
Ph
CH3 CH2 NH
|
Ph
II
III
PhNH2
I
Ph2NH
II
Ph3N
III
(10)
II
III
IV
LECTURE # 13
(ii) Aromatic amines (Ph NH2) or Anilines :
When the lone pair lies in conjugation with a multiple bond, it resides in 2p atomic orbital, so that it can get
resonance stabilisation.
Aniline is a weaker base than NH3 because it has delocalised lone pair.
Page # 33
Ex.
Ex.
In pyrole lone pairs are involved in resonacne therefore it is less basic. But in pyridine lone pairs are in
perpendicular plane of orbitals therefore not involved in resonance
Substituted Anilines:(i) G = ERG (+m, HC, +)__________Kb
(ii) G = EWG (m, )__________Kb
Steric effect of ortho-substituted G (ortho effect) :
H2N:
H
+
HNH
G
(a) Ortho-substituted anilines are mostly weaker bases than aniline itself.
(b) Ortho-substituent causes steric hinderance to solvation in the product (conjugate acid i.e. cation).
(c) The small groups like NH2 or OH do not experience (SIR) due to small size.
(1) G = (m, ); NO2
NH2
(a)
(b)
(c)
(d)
Kb :
dbc a
NH2
(Aniline > p > m > o).
CCl3
CCl3
NH2
NH2
NH2
CCl3
(3) G = ( > +m); Cl
NH2
NH2
NH2
Cl
Cl
NH2
Ex.
Cl
Page # 34
NH2
O effect,
+
HC
+m
CH3
NH2
CH3
NH2
NH2
CH3
+w
HC more do min ating
LECTURE # 14
(iii) Amides :
In amides lone pair donation atom is oxygen which is more electronegative. so it can hold negative charge
more effectively, so it donation tendency decrease (kb decreases).
(iv) Amidines :
(a)
(b)
In case of amidines, the doubly-bonded N is more basic in nature. Although, both the N are sp2 hybridised.
The lone pair of most basic N lies in sp2 hybrid orbital (localised).
x R y
H2N C = NH
R
x
y
NH2 C = NH
(1) sp2
sp2
2
(2) lone pair in sp H.O. lone pair in 2p A.O.
(3) lone pair localised
lp delocalised
(4) Basicity y > x.
Strongest organic Nitrogenous base:(+m)
(+m)
NH 2 C NH 2
Guanidine
:NH2
Page # 35
+
:NH2 C = NH2
NH2
NH2
:NH
Heterocyclic Compounds (Nitrogenous base) :
(1) Pyridine (C5H5N:)
+
NH2 = C NH2
NH2
S.F.:- H
H
6e
Aromatic
Stronger base
N:
A.O. Diagram:-
H
NH2 C NH2 :NH2 C NH2
sp hybrid orbital
(lone pair)
localised
:N H (sp )
S.F.:-
(lp. in 2p A.O.)
A.O. Diagram:-
NH
Complete delocalisation of e
>
N
H
H
>
:NH2
H
3
N sp (4e )
H
H
Non-aromatic
NH3
Aromatic
+
N
H
Aromatic
1.
2.
3.
a>c>b>d
N
H
(c)
sp3/2 ()
(a)
(b)
sp3/2
sp2 localised
N
H
(d)
sp2
N
H
; RCR ;
:NH
(2)
sp2
NH
(3)
sp2
Kb order : (1) > (2) > (4) > (3) > (5)
:NH2(x)
4.
(y)
N(z)
H
Ex:-
Page # 36