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CHEM223 Basicity Amines

Amines are basic compounds that can be protonated by acids, with their basicity influenced by electron density on the nitrogen atom. Alkylamines are generally more basic than ammonia due to electron-donating effects, while arylamines and amides are less basic due to electron delocalization. The hybridization of the nitrogen's lone pair also affects basicity, with higher s-character leading to weaker bases.

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6 views21 pages

CHEM223 Basicity Amines

Amines are basic compounds that can be protonated by acids, with their basicity influenced by electron density on the nitrogen atom. Alkylamines are generally more basic than ammonia due to electron-donating effects, while arylamines and amides are less basic due to electron delocalization. The hybridization of the nitrogen's lone pair also affects basicity, with higher s-character leading to weaker bases.

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Basicity of Amines

CHEM 223 Organic Chemistry II

2nd Sem AY 2023-2024


Amines as Bases
• Equilibrium favors the products of an acid–base reaction when the weaker acid and base are
formed. Because the pKa of many protonated amines is 10–11, the pKa of the starting acid must be
less than 10 for equilibrium to favor the products. Amines are thus readily protonated by strong
inorganic acids and by carboxylic acids as well.
Extraction
• Because amines are protonated by aqueous acid, they can be separated from
other organic compounds by extraction using a separatory funnel. Extraction
separates compounds based on solubility differences. When an amine is
protonated by aqueous acid, its solubility properties change.
• An amine can be separated from other organic compounds by converting it to a
water- soluble ammonium salt by an acid–base reaction.
• Many water-insoluble amines with useful medicinal
properties are sold as their water-soluble
ammonium salts, which are more easily transported
through the body in the aqueous medium of the
blood.
Relative Basicity of Amines
• The weaker the conjugate acid, the higher its pKa
and the stronger the base.
• Any factor that increases the electron density on
the N atom increases an amines’ basicity
• Any factor that decreases the electron density on N
decreases an amine’s basicity.
Comparing an Amine and NH3
• Because alkyl groups are electron donating, they increase the electron density
on nitrogen,
• Primary (1°), 2°, and 3° alkylamines are more basic than NH3 because of the
electron- donating inductive effect of the R groups.
Exercise
• Which compound in each pair is more basic:

(a) (CH3)2NH and NH3


(b) CH3CH2NH2 and ClCH2CH2NH2
Alkylamine VS
Arylamine
• Arylamines are less basic
than alkylamines because
the electron pair on N is
delocalized.
• Delocalization of electrons
decreases the electron
density on N
Exercise
Solution
Alkylamine VS Amide
• With RNH2, the electron pair is localized on the N atom. With an amide, however, the
electron pair is delocalized on the carbonyl oxygen by resonance. This decreases the
electron density on N, making an amide much less basic than an alkylamine.
• In fact, amides are not much more basic than any carbonyl compound. When an
amide is treated with acid, protonation occurs at the carbonyl oxygen, not the
nitrogen, because the resulting cation is resonance stabilized. The product of
protonation of the NH2 group cannot be resonance stabilized.
• Amides are much less basic than amines because the electron pair on N is
delocalized
Amides
Heterocyclic Aromatic Amines
• lone pair of electrons in pyridine occupies an sp2 hybridized orbital, perpendicular to the plane
of the molecule, so it is not part of the aromatic system, whereas that of pyrrole resides in a p
orbital, making it part of the aromatic system. The lone pair on pyrrole, therefore, is delocalized
on all of the atoms of the five-membered ring, making pyrrole a much weaker base than
pyridine.
Hybridization Effects

• The hybridization of the orbital that contains an


amine’s lone pair also affects its basicity.
• The lone pair in piperidine resides in an sp3 hybrid
orbital that has 25% s-character. The lone pair in
pyridine resides in an sp2 hybrid orbital that has
33% s-character.
• The higher the percent s-character of the orbital
containing the lone pair, the more tightly the
lone pair is held, and the weaker the base.
Summary

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