Beruflich Dokumente
Kultur Dokumente
GOC-II
PART-II
BASIC STRENGTH, INTERMEDIATE, TAUTOMERISM
Lecture 1
1. Aliphatic amines
2. Aromatic amines
(Ph N H2) or
Anilines
1. BASIC STRENGTH
2. DEFINITION
Lecture 2
3. BASICITY
4. SCALE OF BASICITY
BASIC STRENGTH:-
5. PERIODICITY IN Kb
(BASIC STRENGTH):
3. Amides
Lecture 3
Lecture 4
1. TAUTOMERISM
1. Carbanion
structure,stability 2. Keto-enol
tautomerism
2. Examples
3. Comparison of stability of Keto-enol
tautomers
4.
4. Amidines
5. Hetero Cyclic
6. CARBANION BASES
(:C - )
7. NITROGENOUS
BASES N: :-
Lecture 5
1. Properties of Keto
and enol forms
2. Examples
Lecture 6
1. Carbocation
structure,stability
2. Examples
Lecture 7
1. Carbocation
rearrangement
2. ring expansion.
3. Ring contraction
4. Examples
Lecture 8
1. Free radical
2. Stability of
radicals
Page # 2
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.
NH4
R O R + H+
+
R O R
H
NH 3 + H +
(II) BASICITY:
It is the tendency to accept H ion, or it is the case of acceptance of H ion.
Ex:
H3N: + H __________easily..
H O H + H __________less easily..
Thus, NH3 > H2O in basicity.
Less electronegative atom (N) donates electron pair easily.
R NH 2 + H2O
Base
Kb =
+
R NH3 + OH Conjugate Acid (C.A.)
[RNH3 ][OH - ]
[where Kb = Base dissociation constant].
[RNH2 ]
pKb = logKb
Note : A stronger base always has a weaker C.A. and vice versa.
Page # 3
CH2
(iv)
<
(Resonance
Stabilisation)
(localised
ve charge)
Ex.
:NH
Among these, amides are the weakest bases.
(iv) > (i) > (ii) > (iii)
H
H
+ = O, solvation = max., Steric Hinderance = min.
(1) H N:
H
Page # 4
H
H
(2) R N: +, solvation, Steric Hinderance
H
H
H
(3) R N: + , solvation, Steric Hinderance
R
R
H
(4) R N: +max., solvation min., Steric Hinderance max.
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).
(1)
CH2 NH2
N:
>
(4)
(3)
: NH3
> NH2 NH2 >
NH2 O H
Ammonia
Hydrazine Hydroxylamine
(2)
N:
(More compact)
Cyclic Amine is more basic than acyclic amine (if degree of N is same).
:NH2
(5)
Ex.
:NH2
Page # 5
(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
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.
Ex.
Page # 6
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
CCl3
NH2
NH2
NH2
CCl3
CCl3
(3) G = ( > +m); Cl
NH2
NH2
NH2
Cl
NH2
Cl
Ex.
Cl
Page # 7
NH2
NH2
CH3
NH2
NH2
+m
CH3
O effect,
+
HC
CH3
w
+
HC more do min ating
(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) sp
sp
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)
NH2 C NH2
Guanidine
:NH2
NH2
:NH
Heterocyclic Compounds (Nitrogenous base) :
+
NH2 = C NH2
NH2
+
:NH2 C = NH2
NH2
H
NH2 C NH2 :NH2 C NH2
Page # 8
H
N:
S.F.:- H
H
6 e
Aromatic
Stronger base
A.O. Diagram:-
sp hybrid orbital
(lone pair)
localised
:N H (sp )
2
A.O. Diagram:-
1.
NH
Complete delocalisation of e
>
N
H
H
:NH2
H
Aromatic
N
H
(c)
sp3/2 ()
(a)
(b)
sp3/2
sp2 localised
:NH
(2)
2
sp
N
H
(d)
sp2
a>c>b>d
N
H
NH3
3
N sp (4e )
H
H
Non-aromatic
+
N
H
Aromatic
3.
(lp. in 2p A.O.)
>
2.
S.F.:-
RCR ;
NH
(3)
2
sp
Kb order : (1) > (2) > (4) > (3) > (5)
:NH2(x)
4.
(y)
N(z)
H
Ex:-
6e
Aromatic
Very weak base
Non aromatic after it donates lone pair
Page # 9
Carbanion
Bond dissociation
1.
2.
,:
Carbanion
A carbon intermediate which contain three bond pair and a negative charge on it, is called carbanion.
,
Methyl carbanion
CH3
Ethyl carbanion
(CH3)2
Isopropyl carbanion
sp3
sp2
H2 C =
sp
HC
, CH2 = CH
(b)
(e)
(f)
(c)
(d) CH2 = CH
[Draw the orbital diagram and mention the type of hybridisation involved in each case]
Stability of carbanion :
Carbanions are stabilised by electron withdrawing effect as
(i)
I effect
(ii)
M effect
(iii)
Delocalisation of charge
If -position of a carbanion has a functional group which contains multiple bond (C = C, C = O, C N, NO2
etc) or carries an electronegative atom, such carbanions are stablised by resonance hence more stable than
simple aryl carbanion.
Page # 10
CH C ..
1
..
CH2
..
CH C
(B)
1
..
..
..
CH3
..
(C)
2
..
..
CH3
..
3
..
..
(D)
NO2
Cl
(E)
(F)
..
CCl3
1
..
CF3
2
(G)
..
Cl CH2 CH2
1
..
F CH2 CH2 CH2
2
..
CH3 CH
CH3
3
..
CH3 CH2 CH2
4
..
CH2 NO 2
1
CH C ..
3
..
CH
(Stability order) :
CHO
NO2
2
..
CH
+
SMe2
..
CH
+
NMe3
4>2>6>3>5>1
..
CH
(I)
..
CH
..
CH
2
(H)
CN
6
Page # 11
(J)
..
CH3 CH CH2CH3
b
..
(CH 3)3C
d
..
CH3 CH2 CH2 CH2
a
..
(CH 3)2C CH 2CH 3
c
(k)
O
..
CH2 C CH3
a
O
..
CH2 C H
b
a>b>d>c
O
..
..
CH2 C OCH
.. 3
c
e>b>a>c>d
O
..
CH2 C NH2
d
(L)
>
>
(Stability order)
Mg / ether
(b) R X
(c) R
Na / NH3 ( )
C H
(d) R CH2
R OH
(e)
(f) CH3 CH = O
(g) Decarboxylation of alkanoic acid by using sodalime dereasing order of decarboxylation
CH3 CH2 CH2 COOH > CH3 CH COOH
|
CH3
Page # 12
TAUTOMERISM
(1) Definition : Tautomers are two structural isomers (having different functional groups) which exist in dynamic
equilibrium with each other. The isomers change into each other by shifting of H-atom from one position to
another position and simultaneously the position of bond also changes.
(2) General formula of compounds showing tautomerism
|
C X Y H
X=Y
can be : C = O
C = NH
N=O
NO
(i)
(ii)
(iii)
(iv)
C = C OH
enol form
CC=O
H
Keto form
CH3
CH2 = C OH
CH3
(ii) CH3 C = O
CH2 = CH OH
(i) CH3 CH = O
Ex.-1
Page # 13
Enol form
|
CC
| ||
H O
|
C C
|
OH
The
In case of monocarbonyl compounds, the compound mainly exists in Keto form (99%). The enol form is
insignificant (less than 1%)
As stability of alkene increases (due to increase in hyper-conjugation or resonance)
% enol content (alkene content) increases.
The -dicarbonyl (or 1, 3-dicarbonyl) compounds have significant enol contents due to resonance stabilization of enol form
H3C C CH2 C CH3
O
keto form (
H3C C = CH C CH3
OH
O
enol form ( 75%)
O
25%)
Keto form
Enol form
I : CH3CH = O
CH2 = CH OH
II : CH3 CH2 CH = O
Sol.
Ex. 2
Ex. 3
III :
III > II > I
I :
II :
III :
Sol.
CH3 CH = CH OH
CH3 C CH3
||
O
..... (% enol)
CH2 C CH3
|
OH
CH3 C C CH3
|| ||
O O
CH2 C C CH3
| ||
OH O
CH3
|
< CH3 CH C CH3
||
O
CH3 C CH C CH3
|
||
OH
O
(enol content)
Page # 14
Ex. 4
>
Ex. 5
Boiling point :
>
Reason : The keto form is more polar and the enol form has intramolecular H-bonding
2.
Solubility : In polar solvents (like H2O). The more polar keto forms is more soluble in water, than the less
polar enol form. The enol form has intramolecular H-bonding
3.
Polarity
4.
Optical properties
The carbonyl compounds which have alpha asymmetric carbon (C*) atom and have H hydrogen atom,
racemise due to tautomerisation on keeping in aqueous solution.
5.
Chemical properties
The -dicarbonyl compounds in aqueous solution show chemical properties of both the forms. The lab tests
of following functional groups are positive.
(i)
(iii) OH
(ii) C = C
2.
In catechol
Page # 15
3.
In Resorcinol :
4.
In Quinol (Hydroquinol)
5.
Trihydroxy benzene
(a)
(b)
(1, 2, 4)
(c)
(1, 3, 5)
(% enol < % keto)
Q.1
Q.2
Me
|
Ph
C
C CH3
(C)
| ||
Et O
O
||
(C*) Ph C CD 3
O
||
(D*) Me 3 C C CH3
(C*)
(D)
Q.3
CH3
|
C CH3
Ph
C
(B*)
| ||
H O
(A*)
(B)
Page # 16
Q.4
OH
OH
OH
OH
HO
OH
HO
OH
OH
(A)
(B)
(C)
OH
Q.5
Sol.
Q.6
Sol.
Q.7
(D)
HO
OH
(E)
OH
X is the smallest dicarbonyl compound which has significant enol content. Predict S.F. of X.
X = H C CH2 C H
||
||
O
O
A (C6H10O2) is an optically active dicarbonyl compound which significantly exists in optically inactive enol
form. Identify A.
A = CH3 C CH C H
|| |
||
O C 2H 5 O
or
CH3 CH2 C CH C H
|| |
||
O CH3 O
An aromatic compound X of molecular formula C9H8O2 exists in keto form and predominantly in enolic form
Y. Write all the possible structure of X and Y.
Sol.
(X)
(Y)
Ph
|
X = OHC CH CHO
Q.8
Ph
|
Y = HO HC C CH O
(A*)
&
(B*)
and
Page # 17
Carbocation
Carbocation
A carbon intermediate which contain three bond pair & a positive charge on it is called carbocation.
,
Methyl carbocation
CH3
Characteristic
(i) sp2 or sp
(ii) Classical & non classical
(iii) Bond angle 120
(iv) Diamagnetic (6e )
Hybridisation : Carbocation may be sp2 & sp hybridised
Hybridisation
Example
sp2
sp
H2 C =
, HC
(Allyl)
(v)
(Benzyl)
(vi)
(Phenyl carbocation)
Draw their orbital diagram and mention the nature of hybridisation in each case.
Stability of carbocations
Factors affecting stability of carbocation
(i) + I effect
(ii) Hyperconjugation
(iii) Resonance stabilization
(iv) + m effect of substituent groups with lone pair (O, N)
>
>
>
>
>
>
>
>
and
aromatic
Page # 18
Practice problem :
+
CH2
+
CH2
+
CH2
OMe
Stability order : 1 > 3 > 2
(A)
OMe
OMe
2
+
CH2
+
CH2
+
CH2
(B)
CH
3
CH3
CH3
1
OMe
(C)
CN
CH3
+
CH2
Stability order :
6 5 1 2 4 3
CH3
+
CH2
+
CH2
(D)
CH
3
CH3
CH3
3
+
CH2
+
CH2
+
CH2
(E)
CH2D
NHCOCH3
OMe
CH3
1
..
CH3 C O
..
4
(G)
+
..
.O.
2
..
.O.
1
+ CH3
C
CH 3
+
CH
1
C+
+
(H)
.. +
O
..
3
(F)
+
2
3
Page # 19
+
+
CH3 CH2 CH2 CH2 CH 3 CH CH 2 CH 3
a
b
+
(CH3)2C CHCH3
CH3
c
+
(CH3)3C
d
+
Draw all isomeric form of C5H11 carbocation, which one is the most stable.
+
CCCCC
(b)
+
CCCCC
(c)
C
+
CCCC
(e)
C
CCCC
+ (f)
C
C C C+
C
(g)
C
+
CCCC
(d)
+
CCCCC
(a)
(J)
(I)
+
(f) C5H11 is most stable.
(K)
+
..
CH3 CH2 NH CH2 CH CH3
(b)
..
+
CH3 CH2 NH CH CH2 CH3
(a)
(L)
+
CH2
+
CH2
+
CH2
+
CH2
(M)
+
+
(N)
+
(a)
(O)
(b)
>
(c)
>
(P)
Page # 20
CH2 = CH CH2
CH2 = CH
CH3
One very stable carbocation reported is cyclopropylmethyl carbocation. This unique stabilisation is seen in
this case of three member ring only.
(more stable than Benzyl)
cyclopropyl methyl carbocation
Page # 21
Ring contraction : -
Complete octet :
CH3
+ ..
(i) CH3 C C = O
..
CH3
CH3
(IV) CH 3 CH CH N CH 3
+
(III)
CH3
..
(lI) CH3 CH2 O
. . CH CH CH3
+
CH3
+
..
(VI) CH3 CH CH Cl
..
..
+
..
(V) CH 3 CH 2 CH = O
..
CH3
(b)
CH3
(e)
(f)
+
(i) CH2 CH CH CH3
CH3
(j)
(d)
CH3
CH3
+
+
CH
2
(g)
(h)
+
CH2
CH3
+
(a) CH3 CH2 CH2
CH3
+
CH
Page # 22
Free radicals
Free radical
Ionic reactions are those in which covalent bonds break heterolytically and in which ions are involved as
reactants, intermediates, or products.
Another broad category of reaction mechanisms that involve homolysis of covalent bonds with the production
of intermediates possessing unpaired electrons called radicals (or free radicals):
Free radicals
(i) Homolytic cleavage
(ii) Condition for its generation
Sun light, peroxide, High temperature
(iii) Neutral species with odd e
(iv) Gaseous phase or non polar solvent
(v) Paramagnetic
(ii) + I, + M
(iii) Decreasing order of stability is ...... > 3 > 2 > 1 >
Stability of radicals
CH3 CH CH CH3
CH3
1.
2.
c>a>b
d>b>a>c>e
a
Page # 23
CH2 = CH
c>b>d>a
CH3
3.
c>d>a>b
4.
5.
d
CH 3 CH CH 2 CH 3
6.
Ans.
1 a, q, y
CH3
(CH3)2CCHCH3
b
(CH3)3C
d>c>b>a
2 a, q, x
3 b, p, z
Page # 24