Topic : amine

Submittedto:- submitted by:-

Mrs.Deepti(ma’am) Arnav Saxena
Class-XIIth (PCM)

Roll no.— 07.

 -: Acknowledgement :-

I would like to express my special thanks of

gratitudeto my teacher Mrs. Deepti (Ma’am) as
well our principal Mrs. Veena Singh (Ma’am)
who gave me the golden opportunity to do this
wonderful project on topic Amine which also
helped me in doing a lot of research and I came
to know about so many new things, I am really
thankful to them.
Secondly I would like to thank my parents and
friends who helped me a lot in this project
within the limited time frame.
Welfare mission international
school

-: Certificate :-

This is to certify that Arnav Saxena of

Class-XII has successfully completed his
chemistry project on th topic “Amine” as
prescribed by Mrs. Deepti (Ma’am) ,
during the academic year 2019-2020. As
per the guidelines issued by the Central
Board of Secondary Education (CBSE)

Teacher’s Sign:- Examiner’s Sign:-

 -: Amine :-
In organiccompound, amines are compounds and functio
nal groups that contain a basic nitrogen atom with a lone
pair. Amines are formally derivatives of ammonia,
wherein one or more hydrogen atoms have been replaced
by a substituent such as an alkyl or aryl group[4] (these
may respectively be called alkylamines and arylamines;
amines in which both types of substituent are attached to
one nitrogen atom may be called alkylarylamines).
Important amines include amino acids, biogenic
amines, trimethylamine, and aniline. Inorganic derivatives
of ammonia are also called amines, such
as monochloramine (NClH2).
The substituent -NH2 is called an amino group.
Compounds with a nitrogen atom attached to
a carbonyl group, thus having the structure R–CO–NR′R″,
are called amides and have different chemical properties
from amines.

Classification of amine :-
 Amines can be classified according to the nature and
number of substituents on nitrogen. Aliphatic
amines contain only H and alkyl substituents. Aromatic
amines have the nitrogen atom connected to
an aromatic ring.
Amines, alkyl and aryl alike, are organized into three
subcategories based on the number of carbon atoms
adjacent to the nitrogen:
 Primary (1°) amines—Primary amines arise when one
of three hydrogen atoms in ammonia is replaced by
an alkyl or aromatic group. Important primary alkyl
amines include, methylamine, most amino acids, and
the buffering agent tris, while primary aromatic amines
include aniline.
 Secondary (2°) amines—Secondary amines have two

organic substituents (alkyl, aryl or both) bound to the

nitrogen together with one hydrogen. Important
representatives include dimethylamine, while an
example of an aromatic amine would
be diphenylamine.
 Tertiary (3°) amines—In tertiary amines, nitrogen has

three organic substituents. Examples

include trimethylamine, which has a distinctively fishy
smell, and EDTA.
A fourth subcategory is determined by the connectivity of
the substituents attached to the nitrogen:
 Cyclic amines—Cyclic amines are either secondary or
tertiary amines. Examples of cyclic amines include the
3-membered ring aziridine and the six-membered
 ring piperidine. N-methylpiperidine and N-
phenylpiperidine are examples of cyclic tertiary
amines.
It is also possible to have four organic substituents on the
nitrogen. These species are not amines but are quaternary
ammonium cations and have a charged nitrogen center.
Quaternary ammonium salts exist with many kinds of
anions.
Naming convention
Amines are named in several ways. Typically, the
compound is given the prefix "amino-" or the suffix: "-
amine". The prefix "N-" shows substitution on the
nitrogen atom. An organic compound with multiple amino
groups is called a diamine, triamine, tetraamine and so
forth.
Systematic names for some common amines:-
Lower amines Higher amines have the prefix amino as
are named with a functional group. IUPAC however
the suffix - does not recommend this convention, but
amine. prefers the alkanamine form, e.g. pentan-
2-amine.

methylamine 2-aminopentane
( pent-2-yl-amine or pentan-2-amine)
Physical properties :-
Hydrogen bonding significantly influences the properties
of primary and secondary amines. For
example, methyl and ethyl amines are gases under
standard conditions, whereas the
corresponding methyl and ethyl alcohols are liquids.
Amines possess a characteristic ammonia smell, liquid
amines have a distinctive "fishy" smell.
The nitrogen atom features a lone electron pair that can
bind H+ to form an ammonium ion R3NH+. The lone
electron pair is represented in this article by a two dots
above or next to the N. The water solubility of simple
amines is enhanced by hydrogen bonding involving these
lone electron pairs. Typically salts of ammonium
compounds exhibit the following order of solubility in
water:
(RNH+3) > (R2NH+2) > (R3NH+).
Small aliphatic amines display significant solubility in
many solvents, whereas those with large substituents are
lipophilic. Aromatic amines, such as aniline, have their
lone pair electrons conjugated into the benzene ring, thus
their tendency to engage in hydrogen bonding is
diminished. Their boiling points are high and their
solubility in water is low.
Spectroscopic identification :-
Typically the presence of an amine functional group is
deduced by a combination of techniques, including mass
spectrometry as well as NMR and IR spectroscopies. H
NMR signals for amines disappear upon treatment of the
sample with D2O. In their infrared spectrum primary
amines exhibit two N-H bands, whereas secondary amines
exhibit only one.

Structure

Alkyl amines :-
Alkyl amines characteristically feature tetrahedral
nitrogen centers. C-N-C and C-N-H angles approach the
idealized angle of 109°. C-N distances are slightly shorter
than C-C distances. The energy barrier for the nitrogen
inversion of the stereocenter is about 7 kcal/mol for a
trialkylamine. The interconversion has been compared to
the inversion of an open umbrella into a strong wind.
Amines of the type NHRR′ and NRR′R″ are chiral: the
nitrogen center bears four substituents counting the lone
pair. Because of the low barrier to inversion, amines of
the type NHRR′ cannot be obtained in optical purity. For
chiral tertiary amines, NRR′R″ can only be resolved when
the R, R′, and R″ groups are constrained in cyclic
structures such as N-substituted aziridines (quaternary
ammonium salts are resolvable).

Inversion of an amine. The

pair of dots represents the
lone electron pair on the
nitrogen atom.

Aromatic Amines:-
In aromatic amines ("anilines"), nitrogen is often nearly
planar owing to conjugation of the lone pair with the aryl
substituent. The C-N distance is correspondingly shorter.
In aniline, the C-N distance is the same as the C-C
distances.

Basicity
Like ammonia, amines are bases. Compared to alkali
metal hydroxides, amines are weaker (see table for
examples of conjugate acid Ka values).
 pKa of
Alkylamine or aniline protonated Kb
amine
4.17E-
methylamine (MeNH2) 10.62
04
4.37E-
dimethylamine (Me2NH) 10.64
04
5.75E-
trimethylamine (Me3N) 9.76
05
4.27E-
ethylamine (EtNH2) 10.63
04
4.17E-
aniline (PhNH2) 4.62
10
4-methoxyaniline (4- 2.29E-
5.36
MeOC6H4NH2) 09
N,N- 1.17E-
5.07
Dimethylaniline (PhNMe2) 09
3-Nitroaniline (3-NO2- 2.88E-
2.46
C6H4NH2) 12
4-Nitroaniline (4-NO2- 1.00E-
1
C6H4NH2) 13
4-trifluoromethylaniline 5.62E-
2.75
(CF3C6H4NH2) 12
The basicity of amines depends on:
1.The electronic properties of the substituents (alkyl
groups enhance the basicity, aryl groups diminish it).
2.The degree of solvation of the protonated amine,
which includes steric hindrance by the groups on
nitrogen.

Electronic effects :-
Owing to inductive effects, the basicity of an amine might
be expected to increase with the number of alkyl groups
on the amine. Correlations are complicated owing to the
effects of 11elocaliz which are opposite the trends for
inductive effects. Solvation effects also dominate the
basicity of aromatic amines (anilines). For anilines, the
lone pair of electrons on nitrogen 11elocalizes into the
ring, resulting in decreased basicity. Substituents on the
aromatic ring, and their positions relative to the amine
group, also affect basicity as seen in the table.

Solvation effects :-
Solvation significantly affects the basicity of amines. N-H
groups strongly interact with water, especially in
ammonium ions. Consequently, the basicity of ammonia
is enhanced by 1011 by solvation. The intrinsic basicity of
amines, i.e. the situation where solvation is unimportant,
has been evaluated in the gas phase. In the gas phase,
amines exhibit the basicities predicted from the electron-
releasing effects of the organic substituents. Thus tertiary
amines are more basic than secondary amines, which are
more basic than primary amines, and finally ammonia is
least basic. The order of pKb's (basicities in water) does
not follow this order. Similarly aniline is more basic than
ammonia in the gas phase, but ten thousand times less so
in aqueous solution.[11]
In aprotic polar solvents such as DMSO, DMF,
and acetonitrile the energy of solvation is not as high as in
protic polar solvents like water and methanol. For this
reason, the basicity of amines in these aprotic solvents is
almost solely governed by the electronic effects.

Special mthods to prepare amine :

Schmidt reaction :-
The Schmidt reaction is an organic reaction in which
an azide reacts with a carbonyl derivative, usually a
aldehyde, ketone, or carboxylic acid, under acidic
conditions to give an amine or amide, with expulsion of
nitrogen. It is named after KarlFriedrich Schmidt (1887–
1971), who first reported it in 1924 by successfully
converting benzophenone and hydrazoic
acid to benzanilide. Surprisingly, the intramolecular
reaction was not reported until 1991 but has become
important in the synthesis of natural products.

The reaction is effective with carboxylic acids to give

amines (above), and with ketones to give amides (below).

Gabriel synthesis :-
The Gabriel synthesis is a chemical reaction that
transforms primary alkyl halides into primary amines.
Traditionally, the reaction uses potassium
phthalimide. The reaction is named after the German
chemist Siegmund Gabriel, who first posited the synthesis
with the aid of his partner, James Dornbush.
The Gabriel reaction has been generalized to include the
alkylation of sulfonamides and imides, followed by
deprotection, to obtain amines
the alkylation of ammonia is often an unselective and
inefficient route to amines. In the Gabriel method,
phthalimide anion is employed as a surrogate of H2N−.
Traditional Gabriel synthesis
In this method, the sodium or potassium salt
of phthalimide is N-alkylated with a primary alkyl
halide to give the corresponding N-alkylphthalimide.

Upon workup by acidic hydrolysis the primary amine is

liberated as the amine salt. Alternatively the workup
may be via the Ing–Manske procedure, involving
reaction with hydrazine. This method produces a
precipitate of phthalhydrazide (C6H4(CO)2N2H2) along
with the primary amine:
C6H4(CO)2NR + N2H4 → C6H4(CO)2N2H2 + RNH2
Gabriel synthesis generally fails with secondary alkyl
halides.
The first technique often produces low yields or
products. Separation of phthalhydrazide can be
challenging. For these reasons, other methods for
liberating the amine from the phthalimide have been
developed.[11] Even with the use of the hydrazinolysis
method, the Gabriel method suffers from relatively harsh
conditions

Hofmann rearrangement :-
The Hofmann rearrangement is the organic reaction of
a primary amide to a primary amine with one
fewer carbon atom.

The Hofmann rearrangement.

The reaction is named after its discoverer – August
Wilhelm von Hofmann. This reaction is also sometimes
called the Hofmann degradation, and should not be
confused with the Hofmann elimination.

Hofmann elimination :-
Hofmann elimination, also known as exhaustive
methylation, is a process where a quaternary
ammonium reacts to create a tertiary amine and
an alkene by treatment with excess methyl
iodide followed by treatment with silver oxide, water, and
heat.
After the first step, a quaternary ammonium iodide salt
is created. After replacement of iodine by
a hydroxyl anion, an elimination reaction takes place to
form the alkene.
With asymmetrical amines, the major alkene product is
the least substituted and generally the least stable, an
observation known as the Hofmann rule. This is in
direct contrast to normal elimination reactions where
the more substituted, stable product is dominant
(Zaitsev's rule).
The reaction is named after its discoverer, August
Wilhelm von Hofmann.
An example is the synthesis of trans-cyclooctene:
Hoffmann reaction and cope reaction
 In a related chemical test called Herzig–Meyer
alkimide group determination a tertiary amine with
at least one methyl group and lacking a beta-proton is
allowed to react with hydrogen iodide to the
quaternary ammonium salt which when heated
degrades to iodomethane and the secondary amine.

Amine alkylation :-
Amine alkylation (amino-de-halogenation) is a type
of organic reaction between an alkyl
halide and ammonia or an amine.[1] The reaction is
called nucleophilic aliphatic substitution (of the halide),
and the reaction product is a higher substituted amine.
The method is widely used in the laboratory, but less so
industrially, where alcohols are often preferred alkylating
agents.

When the amine is a tertiary amine the reaction product is

a quaternary ammonium salt in the Menshutkin reaction:

Amines and ammonia are generally sufficiently

nucleophilic to undergo direct alkylation, often under
mild conditions. The reactions are complicated by the
tendency of the product (a primary amine or a secondary
amine) to react with the alkylating agent. For example,
reaction of 1-bromooctane with ammonia yields almost
equal amounts of the primary amine and the secondary
amine. Therefore, for laboratory purposes, N-alkylation is
often limited to the synthesis of tertiary amines. An
exception is the amination of alpha-halo carboxylic acids
that do permit synthesis of primary amines with
ammonia.[4] Intramolecular reactions of haloamines X-
(CH2)n-NH2 give
cyclic aziridines, azetidines and pyrrolidines.
N-alkylation is a general and useful route to quaternary
ammonium salts from tertiary amines, because
overalkylation is not possible.
Examples of N-alkylation with alkyl halides are the
syntheses of benzylaniline, 1-benzylindole, and azetidine.
Aniline and related aryl derivatives :-
2Alkylation using alcoholsTraditionally, aryl amination is
difficult reaction which usually requires "activated" aryl
halides, such as those with strong electron-withdrawing
groups such as nitro groups ortho or para to the halogen
atom. For the arylation of amines with unactivated aryl
halides, the Buchwald-Hartwig reaction is useful. In this
process, palladium complexes serve as catalysts.
Delépine reaction :-
The Delépine reaction is the organic synthesis of
primary amines by reaction of benzyl or alkyl halides
with hexamethylenetetramine followed
by acid hydrolysis of the quaternary ammonium salt .It is
named after the French chemist stephen marcel
delepine (1871–1965).

Advantages of this reaction are selective access to the

primary amine without side reactions from easily
accessible reactants with short reaction times and
relatively mild reaction conditions.
An example is the synthesis of 2-bromoallylamine from
2,3-dibromopropene.

Amide reduction :-
Amide reduction is a reaction in organic synthesis where
an amide is reduced to either an amine or
an aldehyde functional group.
Catalytic hydrogenation :-
Catalytic hydrogenation can be used to reduce amides
to amines; however, the process often requires high
hydrogenation pressures and reaction temperatures to be
effective (i.e. often requiring pressures above 197 atm and
temperatures exceeding 200 °C) Selective catalysts for the
reaction include Copper chromite, Rhenium trioxide,
and Rhenium(VII) oxide.
Non-catalytic routes to amines
Reducing agents able to affect this reaction include metal
hydrides such as lithium aluminium hydride, or lithium
borohydride in mixed solvents
of tetrahydrofuran and methanol,

Non-catalytic routes to aldehydes

N,N-disubstituted amides can be reduced to aldehydes by
using an excess of the amide:
R(CO)NRR' + LiAlH4 → RCHO + HNRR'
With further reduction the alcohol is obtained.
Some amides can be reduced to aldehydes in the Sonn-
Müller method.
Hydroamination :-
Hydroamination is the addition of an N-H bond of
an amine across a carbon-carbon multiple bond of
an alkene, alkyne, diene, or allene. In the ideal case,
hydroamination is atom economical and green. Amines
are common in fine-chemical, pharmaceutical, and
agricultural industries.

Examples of intramolecular hydroamination

Hydroamination can be used intramolecularly to
create heterocycles or intermolecularly with a separate
amine and unsaturated compound. The development
of catalysts for hydroamination remains an active area,
especially for alkenes. Although practical hydroamination
reactions can be effected for dienes and electrophilic
alkenes, the term hydroamination often implies reactions
metal-catalyzed processes.
Prototypical intermolecular hydroamination reactions

Synthesis

Alkylation :-
The most industrially significant amines are prepared
from ammonia by alkylation with alcohols:
ROH + NH3 → RNH2 + H2O
Unlike the reaction of amines with alkyl halides, the
industrial method is green insofar that the coproduct is
water. The reaction of amines and ammonia with alkyl
halides is used for synthesis in the laboratory:
RX + 2 R′NH2 → RR′NH + [RR′NH2]X
Such reactions, which are most useful for alkyl iodides
and bromides, are rarely employed because the degree of
alkylation is difficult to control. Selectivity can be
improved via the Delépine reaction, although this is rarely
employed on an industrial scale.
Disubstituted alkenes react with HCN in the presence of
strong acids to give formamides, which can be
decarbonylated. This method, the Ritter reaction, is used
industrially to produce tert-butylamine and tert-
octylamine.

Reductive routes :-
Via the process of hydrogenation, nitriles are reduced to
amines using hydrogen in the presence of a nickel
catalyst. Reactions are sensitive to acidic or alkaline
conditions, which can cause hydrolysis of the –CN group.
LiAlH4 is more commonly employed for the reduction of
nitriles on the laboratory scale. Similarly,
LiAlH4 reduces amides to amines. Many amines are
produced from aldehydes and ketones via reductive
amination, which can either proceed catalytically or
stoichiometrically.
Aniline (C6H5NH2) and its derivatives are prepared by
reduction of the nitroaromatics. In industry,hydrogen is
the preferred reductant, whereas, in the laboratory, tin and
iron are often employed.
Alkylation, acylation, and sulfonation :-

Aside from their basicity, the dominant reactivity of

amines is their nucleophilicity. Most primary amines are
good ligands for metal ions to give coordination
complexes. Amines are alkylated by alkyl halides. Acyl
chlorides and acid anhydrides react with primary and
secondary amines to form amides (the "Schotten–
Baumannreaction").

Similarly, with sulfonyl chlorides, one

obtains sulfonamides. This transformation, known as
the Hinsberg reaction, is a chemical test for the presence
of amines.
Because amines are basic, they neutralize acids to form
the corresponding ammonium salts R3NH+. When formed
from carboxylic acids and primary and secondary amines,
these salts thermally dehydrate to form the
corresponding amides.
Conversion to imines :-
Imine formation is an important reaction. Primary amines
react with ketones and aldehydes to form imines. In the
case of formaldehyde (R′ = H), these products typically
exist as cyclic trimers.
RNH2 + R′2C=O → R′2C=NR + H2O
Reduction of these imines gives secondary amines:
R′2C=NR + H2 → R′2CH–NHR
Similarly, secondary amines react with ketones and
aldehydes to form enamines:
R2NH + R′(R″CH2)C=O → R″CH=C(NR2)R′ + H2O

Biological activity :-
Amines are ubiquitous in biology. The breakdown of amino
acids releases amines, famously in the case of decaying fish
which smell of trimethylamine. Many neurotransmitters are
amines,
including epinephrine, norepinephrine, dopamine, serotonin,
and histamine. Protonated amino groups (–NH+3) are the most
common positively charged moieties in proteins, specifically in
the amino acid lysine. The anionic polymer DNA is typically
bound to various amine-rich proteins. Additionally, the terminal
charged primary ammonium on lysine forms salt
bridges with carboxylate groups of other amino acids
in polypeptides, which is one of the primary influences on the
three-dimensional structures of proteins.
Application of amines:-

Dyes :-
Primary aromatic amines are used as a starting material
for the manufacture of azo dyes. It reacts with nitrous acid
to form diazonium salt, which can undergo coupling
reaction to form an azo compound. As azo-compounds
are highly coloured, they are widely used in dyeing
industries, such as:
 Methyl orange
 Direct brown 138
 Sunset yellow FCF
 Ponceau

Drugs :-
Many drugs are designed to mimic or to interfere with the
action of natural amine neurotransmitters, exemplified by
the amine drugs:
 Chlorpheniramine is an antihistamine that helps to
relieve allergic disorders due to cold, hay fever, itchy
skin, insect bites and stings.
  Chlorpromazine is a tranquilizer that sedates without
inducing sleep. It is used to relieve anxiety,
excitement, restlessness or even mental disorder.
 Ephedrine and phenylephrine, as amine
hydrochlorides, are used as decongestants.
 Amphetamine, methamphetamine,
and methcathinone are psychostimulant amines that
are listed as controlled substances by the US DEA.
 Amitriptyline, imipramine, lofepramine and clomipra
mine are tricyclic antidepressants and tertiary amines.
 Nortriptyline, desipramine,
and amoxapine are tricyclic antidepressants and
secondary amines. (The tricyclics are grouped by the
nature of the final amine group on the side chain.)
 Substituted tryptamines and phenethylamines are key
basic structures for a large variety of psychedelic
drugs.
 Opiate analgesics such as morphine, codeine,
and heroin are tertiary amines.

Gas treatment :-
Aqueous monoethanolamine (MEA), diglycolamine
(DGA), diethanolamine (DEA), diisopropanolamine
(DIPA) and methyldiethanolamine (MDEA) are widely
used industrially for removing carbon dioxide (CO2)
and hydrogen sulfide (H2S) from natural gas and refinery
process streams. They may also be used to remove
CO2 from combustion gases and flue gases and may have
potential for abatement of greenhouse gases. Related
processes are known as sweetening.

Safety
Low molecular weight simple amines, such
as ethylamine, are only weakly toxic with between 100
and 1000 mg/kg. They are skin irritants, especially as
some are easily absorbed through the skin.