AMINES vitamins, alkaloids and hormones.

Synthetic
Amines are the alkyl or aryl derivatives of ammonia. In nature, they occur among proteins,
examples include polymers, dyestuffs and drugs.
STRUCTURE
The nitrogen atom in amines is sp' hybridised with an unpairede. Thus amines are pyramidal in shape.
CLASSIFICATION
Amines
1 amine
-NH; group attached
toI alkyl group (R-NH:)
Simpl

Aliphatic
NH group altached
ple
Both alkyl groups
same

Mixed
Both alkyl groups
are different

AromaticC
N groupattached
to2 alkyl group (Ra-NH) to 3alkyl group (R3-N)D
Simple Mixed

ndd
NAMNALATUnE
 are same are different
NOMENCLATURE
Rules
1.In commonsystem, aliphatic aminesare named by prefixing alkylgroup to amine, i.e. alkyl amine.
In and tertiary amines,when thealkyl groups aresame, the prefix di ortri isused before the nameofthe alkyl group.
2.In secondary
TUPACsystem, aliphatic amines are calledalkanamine in which'e' of alkane is replaced byamine.
In thecaseof 2 and 3" amines, the alkyl group containing the maximum numberof C-atomistaken as the parent chain and the other
alkyl groups are taken as substituents.
While naming aryl amines according to IUPAC system, the suffix *e' of arene is replaced by 'amine', i.e. arenamine.
 Alyiamne
NH,-CH,-cH-cH
METHODs OF PREPARATION
1. Reduction of nitro compounds:
Nitro compounds are reduced to amines by passing H gas in the presence of finely divided nickel, palladium or platinum and also by
reducing with metals in acidic medium.
Pdl ethanol
R-NO2+H R-NH2
release HCI during the reaction.
Reduction with iron and HCI is preferred because FeClh formed gets hydrolysed to
2. Ammonolysis of alkyl halides (Hofmann's ammonolysis method):
mixture of
Alkyl halides when treatedwith alcoholic solution of ammonia at 373 K, undergo nucleophilic substitution give a
reaction to
1,2 and 3' amines along with 4" ammonium salt (RN'X ").
Here C-X bond is cleavage by ammonia (amunonolysis)
373 K
R-X+ NHs (ale.) R-NH2+ R2NH + R3N+ R,NX
3. Reduction of Nitriles:
Nitriles on reduction with lithium aluminium hydride (LiAlH,) or catalytic hydrogenation produce 1° amines.
i) LiAlH,
R-CN R-CH-NH
i) H2O
This reaction is used for ascending in amine series, i.e., for preparation of amines containing 1 C- atom more than the starting amine.
for www.hsslive.in. by: Minhad. M. Mubivudeen, #- 9846 29 22 27
4. Reduction of amides:
The amides on reduction with lithium aluminium hydride give amines.
i) LiAIH4
R-CO-NH2 R-CH-NH2
ii) H20
5. Gabriel's phthalimide synthesis:
which on heating with
Phthalimide on treatment with ethanolic solution of potassium hydroxide to form potassium salt of phthalimide
alkyl halide hydrolysis produces the corresponding 1" amine.
followed by alkaline
ONa R - NH,
N-H
C N-RNaOH{a)
ÓNa (1 amine)
Phthalimide Potassium phthalimide N-Alkylphthalimide
amines only. Aromatic primary amines cannot be prepared because
This method is used for the preparation of aliphatie primary
substitution with the anion formed by phthalimide.
aryl halides do not undergo nucleophilic
6. Hoffimann's bromamide reaction: amine.
An amide is treated with Bromine and ethanolic
solution of NaOH to give an
R-NH, + Na,COg +2 NaBr +2 H,0
R-CO-NH+Br +4 NaOH in the amide.
amide l'amine with 1 C. atom less than that present
This method is used for the conversion of an
to a
 This methodis used for the conversion of anamideto a ll amine with 1C-atom less than that presentin theamide.
PROPERTIES
Physical:
1. Colour andstate: Pure amines are almost colourless but get coloured on storage due to atmosphericoxidation. The lower aliphatic
amines are gases andsmell verymuch likeammonia. 1 amines withthree or more C-atoms areliquid andstill higher ones aresolid.
2.Solubility: 1 and2" aminesaresoluble inwater becausethey can form H-bonds with watermolecules.
However, solubility decreaseswith increasein molarmass of amines due toincrease insize of the hydrophobic alkylpart.
Higher amines areinsoluble inwater. Aminesare soluble in organicsolvents like alcohol, ether and benzene.
3. Boilingpoint: 1° and2" amineshavehigher boilingpoints dueto intermolecularH-bonding.3 amines do not haveintermolecular
association due to the absenceof H- atom. Therefore, the orderof boiling pointsof isomericaminesis
1"> 2" >3°
 Chemical:
Basice Nature:
Inamine, thereis an unshared pair of e' on N-atom andhence it candonate this e pair. Soit acts as a Lewisbase.
Basic characterof aminescan be expressed interms ofKy and pK. (pK,= -logKy). Greater the value ofKp, smaller willbe the pKa
valueand stronger will bethe base.
Aliphaticamines arestronger bases thanammonia. This is due to the +Ieffect of alkyl groupsleading to greater e density onthe N-atom.
Aromatic amines areweakerbasesthan ammonia. Thisisdueto the e' withdrawing natureof the aryl group.
Structure-basicity relationship of amines
Basicity ofamines is related totheir structure. Basic character of an amine depends upon the easeof formation of the cation by
accepting a protonfrom the acid. As the stabilityofthe cationincreases, the basicity also increases.
a) Basicityof Aliphatic Amines
.Inthe gaseousphase, due tothe e releasing natureof alkyl group (R)in alkyl amines,it (R)pushes e'towards Nandthus makesthe
unshared e pair moreavailable for sharing withthe proton of theacid.
The substituted ammoniumion formed from the amine getsstabilised chargeby the +I effectofthealky! group. Hence, alkyl
amines are stronger basesthan ammonia.
Thebasic natureof aliphaticamines shouldincrease withincrease inthenumber ofalkyl groups. But this trendisfollowed onlyin
gas phase. The order of basicity ofamines is 3" >2°>1" > NH3.
In the aqueoussolution, in addition toinductive effect,solvation effect and steric hindrancedetermine the basicity. Thegreater
thesize of the ion, lesser willbe the solvation andthe lessstabilisedis theion. So the basicity also decreases. Thus, the order of
basicityof aliphatic amines is1 >2 >3°.
>When the alkyl group issmall, thereis nosterichindrance toH-bonding.Incase thealkyl groupisbigger thanCH; group,there
will besteric hindrance to H-bonding. Therefore,the size of the alkyl group also determinesthe order of basic strength.
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b)Basicityof Aromatic Amines &Efectof Substituent on it
Aryl amines are lessbasicthan ammonia. This is inaryl the -NH: group isattacheddirectlyto the benzene ring. So
thelone paire"present in the N-atom entersinto thebecause
benzene ringamines,
andthe e' pairsareless availablefor protonation andhence aryl
amines are lessbasic.
NH, NH, NH,
I V
I nthe caseof substituted aryl amines, thee'releasing groups like-0CH,-CHincrease basicstrength whilee' withdrawing
groupslike
-NO2, -SOg, -COOH, -X etc. decreasethe basicstrength.
 REACTIONS
1. Salt formation with acids:Amines react with acidsto form salts.
R-NH +HX R-NH;'X
Salt
2. Alkylation:
Amines react withalkyl halides undergo nucleophilic substitutionreactionto form a mixtureof 2" and3 amines and 4 ammonium
salt. (Hofmann's Ammonolysis)
R-X+R-NH2 (alc) Rz-NH
2
+R,N + R,NTX
3 4salt
3. Acylation:
Aliphatic andaromatic 1° and2" amines react with acidchlorides, anhydridesand estersin presenceof base likepyridine (toremove
HCl in orderto favour forward reaction)to form substitutedamides. Thisreaction is known asacylation.
Acid chlorides base
1°/2 amine + Anhydrides/ Amide
Esters
Nal
 4. Electrophilic substitution in Benzene Nucleus:
bromine water at room temperature to give white precipitate of 2,4,6-tribromoaniline.
a) Bromination: Aniline
a
reacts with
NH, NH
Br
+3Br, Br,/H,O +3HBr
Aniline Br
2.4.6-Tribromoaniline
b)Nitration:
Directnitration ofaniline withconc. HNo, andconc. H,SO, gives a mixture ofortho,meta and para nitroanilinesand sometarry (tar-
like) products.
NH, NH, NH, NH,
NO,
HNO, HSo, 288K
NO,
(516) (476) (2%)
dSulphonation:
 c) Sulphonation:
Aniline reacts with concentrated sulphuric acidto form anilinium hydrogensulphate which onheating with sulphuricacid at 453-
473K produces p-aminobenzenesulphonicacid, commonly known as sulphanilic acid, asthe majorproduct.
NH, NH,ISO, NH, NH,
H,SO 453-473 KK
SO,H SO,
Anilinium Sulphanilic acid Zwitter ion
hydrogensulphate
Aniline doesnot undergo Friedel-Craftsreaction(alkylationandacylation)sinceitreact with AJCl, to form salt (catalyst
Anilinedoes notundergo Friedel-Crafts reaction(alkylation andacylation)sinceit react with AICl,to formsalt(catalyst).
IDENTIFICATION OF 10,20 AND 3° AMINES
Influence of the numberof H-atoms at N-atomonthe typeof reactions and nature of productsis responsible for identification and
distinction betweenamines. need tostudy
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Test 1aminesS 2 amines 3amines
Reaction with nitrous
Givealcohol with Gives oily nitroso-amine Formsnitrite in cold which
acid
effervescenceof N2 which gives Liebermann's is soluble inwater and on
gas nitroso-amine test heating gives nitroSO-amine.
Reactionwith benzene Gives N-alkylbenzene Gives N, N-dialkylbenzene
sulphonyl chloride sulphonamide soluble sulphonamideinsoluble in | No reaction
(linsberg's Test) in alkali alkali
Carbylamine reaction Formsfoul smelling
(Isocyanidetest) (like mustard oil)
No reaction No reaction
Reaction with chloroform| carbylamineor
and alcoholic KOH isocyanide (R-NC)