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Chapter 11 - Amines

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عبدالرجمن عكاشة
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Chapter 11 - Amines

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عبدالرجمن عكاشة
Copyright
© © All Rights Reserved
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 Organic derivatives of ammonia, NH3

 Nitrogen atom with a lone pair of electrons, making amines both


basic and nucleophilic
 Occur in plants and animals
 Alkyl-substituted (alkylamines) or aryl-substituted (arylamines)
 Classified: 1⁰ (RNH2), 2⁰ (R2NH), 3⁰ (R3N)
 A nitrogen atom with four attached groups is positively charged
 Compounds are quaternary ammonium salts
 For simple amines, the suffix -amine is added to the name of the alkyl
substituent
 The suffix -amine is added to the name of the organic substituent
 The prefixes “di”, “tri”, etc. can be used as dictated by the structure
 Consider the –NH2 as an amino substituent on the parent molecule
 Symmetrical secondary and tertiary amines are named by adding the prefix di-
or tri- to the alkyl group
 Named as N-substituted primary amines
 Largest alkyl group is the parent name, and other alkyl groups are considered
N-substituents
 If the nitrogen atom occurs as part of a ring, the compound is
designated as being heterocyclic
 Each ring system has its own parent name
 Bonding to N is similar to that in ammonia
 N is sp3-hybridized
 C–N–C bond angles are close to 109⁰ tetrahedral value
 Amines with fewer than five carbons are water-soluble
 Primary and secondary amines form hydrogen bonds, increasing
their boiling points
 The lone pair of electrons on nitrogen makes amines basic and
nucleophilic
 They react with acids to form acid–base salts and they react with
electrophiles
 Amines are stronger bases
than alcohols, ethers, or water
 Amines establish an
equilibrium with water in
which the amine becomes
protonated and hydroxide is
produced
 The most convenient way to
measure the basicity of an
amine (RNH2) is to look at
the acidity of the
corresponding ammonium
ion (RNH3+)
 High pKa → weaker acid and
stronger conjugate base.
 Table 12.1: pKa values of ammonium ions

 Most simple alkylammmonium ions have pKa's of 10 to 11

 Arylamines and heterocyclic aromatic amines are considerably less basic than
alkylamines (conjugate acid pKa 5 or less)
 The N lone-pair electrons in arylamines are delocalized by
interaction with the aromatic ring  electron system and are less
able to accept H+ than are alkylamines
 Can be more basic or less basic than aniline
 Electron-donating substituents (such as –CH3, –NH2, –OCH3) increase the
basicity of the corresponding arylamine
 Electron-withdrawing substituents (such as –Cl, –NO2, –CN) decrease
arylamine basicity
 Amides (RCONH2) in general are not proton acceptors except in very
strong acid
 The C=O group is strongly electron-withdrawing, making the N a very
weak base
 Purification can be achieved owing to the basicity of amines
 Reduction of amides (Section 10.10) and nitriles (Section 10.11)
 Ammonia and other amines are good nucleophiles
 Treatment of an aldehyde or ketone with ammonia or an amine in the
presence of a reducing agent
 Ammonia, primary amines, and secondary amines yield primary,
secondary, and tertiary amines, respectively
 Arylamines are prepared
from nitration of an
aromatic compound and
reduction of the nitro
group
 Reduction by catalytic
hydrogenation over
platinum is suitable if no
other groups can be
reduced
 Iron, zinc, tin, and tin(II)
chloride are effective in
acidic solution
 Alkylation and acylation have already been presented
 Converts amines into imines (Section 9.9)
 Occurs in biological pathways
 A heterocycle is a cyclic compound that contains atoms of two or more
elements in its ring, usually C along with N, O, or S
 Pyrole is an amine and a conjugated diene,

however its chemical properties are not consistent with either of


these structural features
 Pyridine is the nitrogen-containing heterocyclic analog of benzene
 Lone pair is not part of the  orbital system
 Basic properties
 Important biologically such as the B6 complex
vitamins
 Naturally occurring amines
derived from plant sources
 Most have pronounced biological
properties
 Many are pharmaceutical agents
 Few of the total in existence have
been characterized
 Currently active area of research

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