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Relative Basic Strength of Amines

The document discusses the relative basic strength of various amines and their derivatives, comparing their basicity based on structural factors such as resonance and inductive effects. It provides a series of comparisons indicating which structures are more basic than others, often highlighting the influence of substituents like phenyl and nitro groups. Overall, it concludes that the basic strength is affected by the presence of electron-donating or withdrawing groups and their spatial arrangement.

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Aashi Prasad
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27 views7 pages

Relative Basic Strength of Amines

The document discusses the relative basic strength of various amines and their derivatives, comparing their basicity based on structural factors such as resonance and inductive effects. It provides a series of comparisons indicating which structures are more basic than others, often highlighting the influence of substituents like phenyl and nitro groups. Overall, it concludes that the basic strength is affected by the presence of electron-donating or withdrawing groups and their spatial arrangement.

Uploaded by

Aashi Prasad
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

RELATIVE BASIC STRENGTH

1) CH
NH3 H2N CH3 H N CH H N 3
2 3 2
(i) (ii) (iii) (iv)
The basic strength is (iv) > (iii) > (ii) > (i).
2) NH2 NH2
H2C H2C

(i) (ii)
The basic strength is (ii) > (i).
Phenyl ring causes greater –I effect in (i) than the –I effect of cyclohexyl ring in(ii), so
(ii) is more basic.
H3C H3C
3) NH3 H2N CH3 NH CH3 N CH3
H3C
(i) (ii) (iii) (iv)

The basic strength is (iv) > (iii) > (ii) > (i) ( in GASEOUS STATE)

4)  C2H5 2 NH   C2H5 3 N  C2H5NH2  NH3

5)  CH3 2 NH  CH3NH2   CH3 3 N  NH3


6)

NH2 NH2

7)

(i) (ii)
The basic strength is (i) > (ii).
In (ii) lone pair is delocalized by resonance, so basic strength decreases.
8) H 3C CH2 H 3C CH H3C C C NH2
CH2 NH2 CH NH2
(i) (ii) (iii)
The basic strength is (i) > (ii) > (iii).

NH 2

9) R CH 2
NH 2
(i) (ii)

The basic strength is (i) > (ii).

NH2
H2C
NH2

10)

(i) (ii)
The basic strength of (ii) is more than (i), as lone pair on nitrogen doesnot
involve in resonance.
O NH NH
11) H3C CH2 H3C C H3C C H2N C
NH2 NH2 NH2 NH2
(i) (ii) (iii) (iv)
The basic strength is (iv) > (iii) > (i) > (ii).

O
C
O NH2
12)
H3C C NH2
(i) (ii)
The basic strength is (ii) > (i).
NH2

13)
N
H
(i) (ii)

The basic strength is (ii) > (i).


In (i) lone pair of electrons on nitrogen is part of aromatic sextet, so (i) is lessbasic.

N (ii)

14)
N
(i)
H
The basic strength is (ii) > (i).
In (i) lone pair of electrons on nitrogen is part of aromatic sextet, so (i) is less basic.

15)
CH3  CH2  NH2 CH3  CH  NH CH3  C  N
 i  ii   iii 
The basic strength is (i) > (ii) > (iii).

N
16) H3C CH3 N
CH3 Me

(i) (ii)
The basic strength is (ii) > (i).

H H
N
17) N

(i) (ii)
The basic strength is (ii) > (i).
H
H
N
18)
N

(i) (ii)
The basic strength is (ii) > (i).

19)
N
Et3N

(i) (ii)
The basic strength is (ii) > (i).
20)

Me3N (SiH3)3N
trimethyl amine trisilyl amine
N undergoes sp3 hybridisation N undergoes sp2 hybridisation
pyramidal structure planar structure

(i) (ii)

The basic strength is (i) > (ii).


In (ii) the lone pair of electrons on nitrogen involve in resonance with the empty
d-orbitals of silicon, so they are less available to accept proton, hence less basic.
Me Me
N
Me Me
O N O

21) N N
O O

N
O O

(i) (ii)
The basic strength is (i) > (ii).
In (i) due to bulky NO2 groups on both sides ortho to NMe2 on benzene ring the

NMe2 group is forced out of plane which inhibits resonance between lone pair

of electrons on nitrogen and the phenyl ring. This makes lone pair of electrons
on nitrogen in (i) more available than in (ii), to be donated to an acid.

H3C CH3 H3C CH3


22) NH2 N N
H3C CH3

(i) (ii) (iii)


The basic strength is (iii) > (ii) > (i).
NH2 NH2
23) H3C CH3

H3C CH3
NO2 NO2
(i) (ii)
The basic strength is (ii) > (i).
In (ii) NO2 group is forced out of plane due to sterichinderance, so it shows less

–R effect on phenyl ring, hence (ii) is more basic.

24) Me Me Me Me
N N
O 2N NO 2

(i) (ii)
The basic strength is (ii) > (i).

NH2 Me Me
N
25) O 2N NO 2 O 2N NO 2

NO 2 NO 2
(i) (ii)
The basic strength is (ii) > (i).

NH2 NH2
NH2
NO2 CH3
26)

(i) (ii) (iii)


The basic strength is (i) < (ii) and (iii) < (ii).

Basic strength of derivatives of aniline


‘+R’ and ‘+I’ groups on benzene ring enhances the basic strength of aniline, whereas
‘–R’ and ‘–I’ groups on benzene ring decreases the basic strength of aniline
27) NH2 NH2 NH2 NH2
NO2

NO2
ortho effect NO2
-R, -I effects -I effect -R, -I effects
(i) (ii) (iii) (iv)

The basic strength is (iv) > (iii) > (ii) > (i).

NH2 NH2 NH2 NH2


28)
CH3

CH3
ortho effect
+I effect +I effect CH3
hyperconjugation +I effect
hyperconjugation
(i) (ii) (iii) (iv)

The basic strength is (iv) > (iii) > (i) > (ii).

29) NH2 NH2 NH2 NH2


OMe

OMe
OMe
ortho effect
-I effect +R, -I effects
+R, -I effects
(i) (ii) (iii) (iv)

The basic strength is (iv) > (i) > (ii) > (iii).

Common questions

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The basic strength of nitrogen-containing compounds can differ based on the type of ring structure attached. For example, phenyl rings can exert a strong -I or -R effect, decreasing basicity compared to cyclohexyl rings, which have less electron-withdrawing impact. This is evident where cyclohexylamines show greater basic strength than their phenyl analogs due to differences in the electron-withdrawing capabilities of these rings .

Electron-releasing groups enhance the basic strength of aniline derivatives by increasing electron density on the nitrogen atom, making the lone pair more available for protonation. Such effects, including hyperconjugation or +R groups on the benzene ring, increase basic strength due to these groups enhancing the electron-donating capability of the nitrogen .

Basic strength decreases when the lone pair of electrons on nitrogen is involved in resonance or when there are electron-withdrawing groups (e.g., -I effect from phenyl rings) that decrease electron density availability. For instance, aromatic amines can have less basicity due to resonance stabilization of the lone pair, reducing its availability for proton acceptance .

Trimethylamine (Me3N) is stronger in basicity than trisilylamine (SiH3)3N. This difference arises because trimethylamine undergoes sp3 hybridization, resulting in a pyramidal structure where the lone pair is readily available for protonation. In contrast, trisilylamine has a planar sp2 hybridization structure, with the lone pair involved in resonance with empty d-orbitals of silicon, making it less available for bonding .

The basic strength is influenced by whether the lone pair of electrons on nitrogen is involved in the aromatic sextet. In compounds where the lone pair is part of the aromatic sextet, such as in aromatic amines, the basicity decreases because the electrons are less available for bonding. For example, in nitrogen-containing compounds where the lone pair of electrons participates in resonance, the basic strength is reduced due to decreased electron availability for protonation .

Basic strength decreases when lone pair electrons on nitrogen engage in resonance because this delocalization reduces the electrons' availability for bonding with protons. In cases such as trisilylamine, where lone pairs interact with d-orbitals of silicon, the electrons become part of a resonance system, thus diminishing their ability to be protonated and reduce basic strength .

Steric effects, such as ortho substitutions with bulky groups (e.g., NO2 groups), can inhibit resonance between the nitrogen's lone pair and the aromatic ring, thus maintaining the availability of the lone pair for protonation and increasing basicity. For example, the basic strength of an amine is higher when ortho-substituents inhibit resonance by forcing functional groups out of the plane of the ring .

Electron-withdrawing groups decrease basicity by pulling electron density away from the nitrogen atom, weakening its ability to donate a lone pair for protonation. In cases where the group has -I or -R effects, such as phenyl rings or nitro groups, these effects stabilize negative charge via resonance or induction, making the amine less basic as the nitrogen's lone pair becomes less available .

The basicity of nitrogen-containing molecules is affected by their hybridization states. In sp3 hybridized molecules like trimethylamine (Me3N), the nitrogen has a pyramidal structure, allowing its lone pair to be readily available for protonation. However, in sp2 hybridized structures like trisilylamine ((SiH3)3N), the nitrogen adopts a planar configuration, with lone pairs possibly engaged in resonance, which limits their availability for bonding and reduces basicity .

The 'ortho effect' describes how ortho substituents impact aniline basic strength by sterically hindering resonance. When bulky groups (e.g., NO2) are positioned ortho to the amine, they can force the amine out of the plane, reducing resonance interaction and making the lone pair on nitrogen more available to protons, enhancing basic strength .

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