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Amines: Structure, Classification, Naming

• Amines are organic compounds derived from ammonia by replacing hydrogen atoms with alkyl/aryl groups.

• They are found naturally in proteins, vitamins, alkaloids, and hormones, and are used synthetically in polymers,
dye stuffs, and drugs.

• Amines have a pyramidal structure with nitrogen atom carrying an unshared pair of electrons.

• They are classified as primary (1o), secondary (2o), or tertiary (3o) depending on the number of hydrogen atoms
replaced.

• Naming conventions include common names and the IUPAC system, where primary amines are named as
alkanamines.

Nomenclature of Amines and Methods of Amine Preparation

• In the nomenclature of amines, if multiple amino groups are present, their positions are specified by giving
numbers to the carbon atoms bearing the -NH groups, and prefixes like di, tri, etc. are attached to the amine name.
The 'e' of the suffix of the hydrocarbon part is retained.

• Secondary and tertiary amines are named using a locant N to designate the substituent attached to the nitrogen
atom.

• In arylamines, the -NH group is directly attached to the benzene ring.

• Amines can be prepared by the reduction of nitro compounds using hydrogen gas or by ammonolysis of alkyl
halides in the presence of ammonia.

• Reducing nitro compounds with metals or iron scrap and hydrochloric acid can yield nitroalkanes, which can be
further reduced to alkanamines.

• Ammonolysis of alkyl or benzyl halides with ammonia results in cleaving the C-X bond and substituting the
halogen atom with an amino group.

• Ammonolysis can yield a mixture of primary, secondary, and tertiary amines, as well as quaternary ammonium
salts. Primary amines can be obtained as a major product by using excess ammonia.

Reactivity of Halides with Amines and Preparation of Amines

• The reaction of ethanolic NH with C H Cl is: NH3 + CH2Cl3 -> NH2CH2Cl + HCl

• The ammonolysis of benzyl chloride and the reaction of the amine with two moles of CH2Cl3 is: C6H5CH2Cl +
2NH3 -> C6H5CH2NH2 + NH4Cl and C6H5CH2NH2 + 2CH2Cl3 -> (C6H5CH2)2NCH2Cl + 3HCl

• Reduction of nitriles with LiAlH4 or catalytic hydrogenation to produce primary amines: R-C≡N + 4[H] ->
R-CH2NH2
• Reduction of amides with LiAlH4 to yield amines: RCONH2 + 4[H] -> RCH2NH2 + H2O

• Gabriel phthalimide synthesis: Phthalimide + KOH + R-X + NaOH -> R-NH2 + KOC(C6H4)CO2H + H2O

• Hoffmann bromamide degradation reaction: RCONH2 + Br2 + NaOH -> R-NH2 + NaBr + NaCHO2

• Conversion of CH3-CH2-Cl to CH3-CH2-CH2-NH3: CH3CH2Cl + NH3 -> CH3CH2CH2NH3Cl

• Conversion of C6H5-CH2-Cl to C6H5-CH2-CH2-NH6: C6H5CH2Cl + NH6 -> C6H5CH2CH2NH6Cl

• The amide that gives propanamine by Hoffmann bromamide reaction is butanamide

• The amine produced by the Hoffmann degradation of benzamide is aniline or benzenamine

• Lower aliphatic amines are gases, while primary amines with three or more carbon atoms are liquid. Aniline and
other arylamines are usually colorless but get colored on storage. Amines are soluble in water due to hydrogen
bonding, but solubility decreases with molar mass increase. Butan-1-ol is more soluble in water than butan-1-amine
due to stronger intermolecular hydrogen bonding. Amines are soluble in organic solvents like alcohol, ether, and
benzene.

Intermolecular Association and Boiling Points of Amines

• Primary amines have stronger intermolecular associations compared to secondary amines due to the presence of
two hydrogen atoms available for hydrogen bond formation.

• Tertiary amines do not have intermolecular associations since there are no hydrogen atoms available for
hydrogen bond formation.

• The order of boiling points for isomeric amines is as follows: Primary > Secondary > Tertiary.

• Intermolecular hydrogen bonding in primary amines is shown in Fig. 9.2.

• Boiling points of amines, alcohols, and alkanes with similar molar mass are compared in Table 9.2.

• The reactivity of amines is determined by the difference in electronegativity between nitrogen and hydrogen
atoms, as well as the presence of unshared electron pairs.

• The number of hydrogen atoms attached to the nitrogen atom also affects the reaction course of amines.

• Amines behave as nucleophiles due to the presence of unshared electron pairs.

• Amines react with acids to form salts and can be regenerated by treating the salts with a base.

• Amine salts are soluble in water but insoluble in organic solvents like ether.

• The basic character of amines is attributed to their ability to behave as Lewis bases.

• The strength of amines as bases can be determined by their K values or pK values.

• The pK values of specific amines are listed in Table 9.3.

• Interpreting the Kb values of amines based on the +I or -I effect of substituents may result in discrepancies.

Factors Affecting Basicity of Amines

• The basicity of amines is influenced by various effects like inductive effect, solvation effect, and steric hindrance.

• The basic character of an amine depends on the stability of the cation formed by accepting a proton from an acid.

• Alkylamines are stronger bases than ammonia due to the electron releasing nature of alkyl groups, which
increases the availability of the unshared electron pair for sharing with the proton.

• The order of basicity in the gaseous phase follows: tertiary amine > secondary amine > primary amine > NH3.

• In the aqueous phase, solvation with water molecules also affects the stability of substituted ammonium cations,
resulting in a different order of basicity.

• The basic strength of alkyl amines in the aqueous state is determined by the interplay of inductive effect, solvation
effect, and steric hindrance.

• Methyl substituted amines and ethyl substituted amines follow the order of basic strength: (CH3)2NH > (CH3)NH2
> CH3NH2 > NH3.

• The high pK value of aniline is because the -NH group is attached directly to the benzene ring, which conjugates
with the unshared electron pair on nitrogen, making it less available for protonation.

Reactions of Amines in Organic Chemistry

• Aniline exists as a resonance hybrid of five different structures and is more stable than the anilinium ion.

• Anilinium ion can only have two resonating structures (kekule).

• The basic strength of aromatic amines like aniline is lower than that of ammonia.

• Electron-releasing groups like -OCH3, -CH3 increase the basic strength of substituted aniline, while
electron-withdrawing groups like -NO2, -SO3H, -COOH, -X decrease it.

• The decreasing order of basic strength for the given amines and ammonia is: (CH3)2NH > CH3NH2 > NH3 >
C6H5NH2.

• Amines can undergo alkylation with alkyl halides and acylation with acid chlorides, anhydrides, and esters.

• Carbylamine reaction occurs for primary amines, forming isocyanides.

• Primary aliphatic and aromatic amines react with nitrous acid to form diazonium salts.
• Secondary and tertiary amines react with nitrous acid differently.

• Reaction with arylsulphonyl chloride forms sulphonamides.

Basic Strength of Aromatic Amines

• The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the presence of a strong
electron-withdrawing sulphonyl group. Hence, it is soluble in alkali.

• N,N-diethylbenzene sulphonamide does not contain any hydrogen atom attached to nitrogen, making it non-acidic
and insoluble in alkali.

• Tertiary amines do not react with benzenesulphonyl chloride, which is used to distinguish between primary,
secondary, and tertiary amines.

• Aniline reacts with bromine water at room temperature to give 2,4,6-tribromoaniline. Electrophilic substitution
occurs primarily at ortho and para positions due to the activating effect of the -NH group.

• Direct nitration of aniline yields tarry oxidation products and significant amounts of the meta derivative. Protecting
the -NH group by acetylation controls the nitration reaction to obtain the p-nitro derivative.

• Aniline reacts with concentrated sulphuric acid to form anilinium hydrogensulphate and heating it further produces
p-aminobenzene sulphonic acid as the major product. Aniline does not undergo Friedel-Crafts reaction due to salt
formation with aluminium chloride, making it a strong deactivating group.

• Arrange the following in increasing order of their basic strength: (i) C6H5NH2, C6H5CH2NH2, NH2,
C6H5NHCH2CH2NH2, and (C6H5)2NH. (ii) C6H5NH2, (C6H5)2NH, (C6H5)3N, C6H5CH2NH2.

Reactions and Properties of Diazonium Salts

• Diazonium salts have the general formula RN X where R is an aryl group and X^- can be Cl^-, Br^-, HSO^-4,
BF^-4, etc.

• Diazonium salts are named by adding "diazonium" to the name of the parent hydrocarbon and then the name of
the anion.

• Primary aliphatic amines form unstable alkyldiazonium salts, while primary aromatic amines form stable
arenediazonium salts at low temperatures.

• Benzenediazonium chloride is prepared by reacting aniline with nitrous acid, produced by the reaction of sodium
nitrite with hydrochloric acid.

• Diazonium salts can undergo displacement reactions, where the diazonium group is substituted with Cl^-, Br^-,
I^-, CN^-, or OH^-. The nitrogen is released as a gas.

Reactions involving diazonium salts and amines

• The Sandmeyer reaction has a better yield compared to the Gatterman reaction.
• Iodine is not easily introduced into the benzene ring directly, but when the diazonium salt solution is treated with
potassium iodide, iodobenzene is formed.

• When arenediazonium chloride is treated with fluoroboric acid, arene diazonium fluoroborate is precipitated, which
decomposes to yield aryl fluoride when heated.

• Certain mild reducing agents like hypophosphorous acid or ethanol can reduce diazonium salts to arenes and
oxidize themselves to phosphorous acid and ethanal.

• The diazonium salt solution can hydrolyze to phenol if the temperature rises to 283 K.

• The diazonium group can be replaced by -NO group when diazonium fluoroborate is heated with aqueous sodium
nitrite solution in the presence of copper.

• The coupling reaction between benzene diazonium chloride and phenol forms p-hydroxyazobenzene, and the
reaction with aniline yields p-aminoazobenzene.

• Diazonium salts are good intermediates for introducing various functional groups into the aromatic ring.

• Aryl fluorides and iodides cannot be prepared by direct halogenation.

• Cyano group cannot be introduced by nucleophilic substitution of chlorine in chlorobenzene, but cyanobenzene
can be obtained from diazonium salt.

• The replacement of diazo group by other groups is helpful in preparing substituted aromatic compounds.

• Amines can be considered as derivatives of ammonia obtained by replacing hydrogen atoms with alkyl or aryl
groups.

• Primary, secondary, and tertiary amines have different structures and behave as Lewis bases.

• Amines can be formed from various compounds and exhibit hydrogen bonding.

• The stability and basic nature of amines are influenced by electron releasing, steric, and H-bonding factors in
different solvents. Alkyl amines are stronger bases than ammonia.

Aromatic Amines and Reactions

• In aromatic amines, electron releasing groups increase their basic character, while electron withdrawing groups
decrease it.

• Aniline is a weaker base compared to ammonia.

• The reactions of amines are determined by the availability of unshared electrons on the nitrogen.

• The number of hydrogen atoms at the nitrogen atom affects the type of reactions and nature of products, allowing
for the identification and distinction between primary, secondary, and tertiary amines.

• p-Toluenesulphonyl chloride is used to identify primary, secondary, and tertiary amines.

• Acylation process using acetyl chloride or acetic anhydride can control the reactivity of aromatic amines.

• Tertiary amines like trimethylamine are used as insect attractants.

• Aryldiazonium salts derived from arylamines can undergo substitution reactions with nucleophiles, providing
methods for producing aryl halides, cyanides, phenols, and arenes.

• Coupling reactions of aryldiazonium salts with phenols or arylamines result in the formation of azo dyes. Subject:
IUPAC Names and Classification of Amines

• (i) IUPAC name: cyclohexylamine | Classification: secondary amine

• (ii) IUPAC name: 2-methylpropan-2-amine | Classification: tertiary amine

• (iii) IUPAC name: 4-methylpentan-2-amine | Classification: tertiary amine

• (iv) IUPAC name: cyclohexylamine | Classification: primary amine

• (v) IUPAC name: benzylamine | Classification: primary amine

• (vi) IUPAC name: 1-chloro-1-ethylbutan-2-amine | Classification: secondary amine

• (vii) IUPAC name: 2-bromo-4-chloroaniline | Classification: primary amine Subject: Tests to Distinguish Between
Amine Compounds

• Methylamine and dimethylamine can be distinguished using their odor. Methylamine has a fishy odor, while
dimethylamine has a pungent odor.

• Secondary and tertiary amines can be distinguished using the Hinsberg test. The Hinsberg test forms insoluble
products with secondary amines, while tertiary amines give soluble products.

• Ethylamine and aniline can be distinguished by their solubility in water. Ethylamine is soluble in water, while
aniline is not.

• Aniline and benzylamine can be distinguished using the ferric chloride test. Aniline reacts with ferric chloride to
form a blue precipitate, while benzylamine does not.

• Aniline and N-methylaniline can be distinguished by their reactivity towards acetyl chloride. Aniline reacts with
acetyl chloride to form acetanilide, while N-methylaniline does not. Subject: Explanations for Aniline and Related
Amines

• The pK value of aniline is higher than that of methylamine due to resonance delocalization of the nitrogen lone
pair in aniline.

• Ethylamine is soluble in water while aniline is not due to the formation of hydrogen bonds between ethylamine and
water molecules.
• Methylamine reacts with ferric chloride to precipitate hydrated ferric oxide due to the formation of a coordination
complex.

• Aniline, despite being o- and p- directing in electrophilic substitution reactions, still undergoes nitration to produce
a substantial amount of m-nitroaniline due to ortho-para directing groups activating the ortho and para positions.

• Aniline does not undergo Friedel-Crafts reaction due to its inability to form a stable carbocation intermediate.

• Diazonium salts of aromatic amines are more stable than those of aliphatic amines due to resonance stabilization
of the diazonium ion.

• Gabriel phthalimide synthesis is preferred for synthesizing primary amines because it allows for the introduction of
the primary amino group without any side reactions. Subject: Ranking of Amines

• In decreasing order of pK values: cyclohexylamine, 2-methylpropan-2-amine, benzylamine, cyclohexylamine.

• In increasing order of basic strength: benzylamine, 2-methylpropan-2-amine, cyclohexylamine, cyclohexylamine.

• In increasing order of basic strength: (a) p-toluidine, aniline, p-nitroaniline (b) cyclohexylamine,
1-chloro-1-ethylbutan-2-amine, 4-methylpentan-2-amine.

• In decreasing order of basic strength in gas phase: benzylamine, cyclohexylamine, 2-methylpropan-2-amine,

• In increasing order of boiling point: cyclohexylamine, 2-methylpropan-2-amine, methylamine.

• In increasing order of solubility in water: benzylamine, cyclohexylamine, 2-methylpropan-2-amine. Note: Due to

Amines - Notes on Various Reactions and Conversions

• Methanamine (ii) can be converted into hexanenitrile into 1-aminopentane (iii).

• Methanol can be converted into ethanoic acid (iv).

• Ethanamine can be converted into methanamine (v).

• Ethanoic acid can be converted into propanoic acid (vi).

• Methanamine can be converted into ethanamine (vi).

• Nitromethane can be converted into dimethylamine (vii).

• Propanoic acid can be converted into ethanoic acid (viii).

• Various methods for the identification of primary, secondary, and tertiary amines are described, along with the
chemical equations involved (9.6).
• Short notes are provided on carbylamine reaction, diazotisation, Hofmann's bromamide reaction, coupling
reaction, ammonolysis, acetylation, and Gabriel phthalimide synthesis (9.7).

• Conversions involving nitrobenzene, benzene, benzoic acid, aniline, benzyl chloride, and benzamide are
explained (9.8).

• Reactions involving compounds A, B, and C are described (9.9).

• The structures and IUPAC names of compounds A, B, and C are provided (9.10).

• Various reactions involving aromatic and aliphatic primary amines are completed (9.11).

• The reasons for aromatic primary amines not being prepared by Gabriel phthalimide synthesis are discussed
(9.12).

• Reactions of aromatic and aliphatic primary amines with nitrous acid are described (9.13).

• Explanations are given for the acidity of amines compared to alcohols, the boiling point differences between
primary and tertiary amines, and the stronger basicity of aliphatic amines compared to aromatic amines (9.14).