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Amine
Contents

Classification and nomenclature

Amine bond

Physical and base properties of amine

Amine synthesis

Amine reaction
AMINE

 The compound containingtrivalennitrogen atom binding with

one/two/three carbon atom
 Amine is derivate of NH3 with one/two/three hydrogen atom replaced by
alkyl group (-R) or aryl (-Ar)
Amine Sources

 Morfina(painkiler)→ from opium, i.e. dried sap ofapiunraw

seed(Papaversamniferum)

 Putresina→ from rotten meat

 Efedrina(decongestant) that active in nose and influenza drug→ extracted

fromma-huangplant

 Meskalina→ isolated from peyotecactus

 Nikotina→ tobacco
Classification

 Classified : primary , secondary and tertiary based on the amount of alkyl

or aryl substituent bound to nitrogen

Amine nitrogen has 4 group or atom bound to itself → N has positive

charge

Divided into 2 :

1. Amine salt (if one or more bound are H)

2. Quaternary ammonium salt (if that four groups are alkyl or aryl = no

hydrogen in nitrogen)
Nomenclature

Simple amine named with mentioning alkyl group bound to

nitrogen and add –amine suffixalkylamine

Propylamine
t-butylamine(primary amine)

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IUPAC

 Amine named asalkanamine.

 Amine chain is numbered appropriate with amine group and its substituent

position.

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IUPAC

Fornaming of secondary and tertiary amine :

 Numbered the longest alkane chain

 Each alkyl group bound to N atom named as N-alkyl group.

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Practice

 Give name to the following compounds:

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Amine as substituent

 When it is found in a compound with functional group containing oxygen,

then:

 -NH2 amino

 -NHRN-alkylamino

 -NR2 N,N-dialkylamino

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Bond in Amine

 Analogwithbondin ammonium: sp3 nitrogen atomboundto3 atoms

oranothergroup(H or R) and pairofsingleelectronin

theremainingofsp3orbital.

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 Inamineorquartenaryammoniumsalt,

apairofsingleelectronformforthsigmabond.Kationhas analog with

ammonium ion.

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 An amine molecule having 3 different groups bound to nitrogen → chiral,

butenantiomerfrommostofaminecan’tbeisolatedbecausefast

inversionamongmirrorshadowatroomtemperature. That inversion occur

through flat transition condition(nitrogensp2)

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 If Namine bind 3 different substituent and there is a hindrance of reciprocal

conversion between both mirror shadow structure, maximum its pair of

enantiomer can be isolated

 Example: :

 MethylenechainbetweenbothNpreventreciprocalconversion(interconversion

)amongmirrorshadow.

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Physical Properties of Amine

 Form hydrogen bond

 Hydrogen bond in N------HN weaker than hydrogen bond inO-----HO

 Thusamineboilingpointisbetweenboilingpointofcompoundwithouthydrogenb

ond(ex.alkaneandether)andcompoundhavingstronghydrogenbond

(ex.alcohol) with similar molecular weight.

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 Liquid tertiary amine can not form H bond (because does not have NH

bond).

 Thus boiling point of tertiary amine <secondary<primary with equal

molecular weight, and its boiling point closer to boiling point of alkane

(with similar molecular weight)

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 Lower molecular weight of amine is water soluble because it can form

hydrogen bond with water.

 Tertiary, secondary, primary amine can formhidrogenbond because it has

pair single electron used to form H and water bonding.

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Base Property of Amine

 Amine has base property has pair of electron that does not used with

other atom. This electron pair cause electron density surround Nitrogen

atom. The bigger electron density, the higher base property of molecule.

Group donating will increase base property of amine.

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Gas phase(g):

 (CH3)3N > (CH3)2NH > CH3NH2> NH3

Most basic Least basic

Solution phase (aq) :

 (CH3)2NH > CH3NH2> (CH3)3N > NH3

Most basic Least basic

 This difference caused bysolvation effect, amine as an ammonium ion in

solution.

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 Aromatic amine (ex. Aniline) has baseproperty < aliphatic amine

because structure form of aromatic amine is stabilized by benzene

ring having ability to resonance

+ H2O + OH-
+
NH 2 NH 3
tak beresonansi

+ H2O + OH-
+ NH 2 NH 3
NH2
resonansi
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Amine Synthesis

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Synthesis withsubtitutionreaction

 Ammonium/aminereactionwithalkylhalide

 SN2reaction:

 Reactivity order of alkyl halide for SN2 reaction:

CH3X > primer > secondary

 Tertiary alkyl halide does not have substitute reaction with ammonium or

amine;resulteliminationproduct

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 Drawback of this route: amine salt product exchange proton with ammonium or earlier

amine.

 This proton exchange result two nucleophile or more, competing in reaction with alkyl

halide.

 The mixture of mono-, di-, tri-alkyl-amine andquartenaryammonium salt is obtained

from a reaction of ammonium and an alkyl halide.

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 If primary amine (mono-alkyl) is wanted, use excess amine.

 Ifquartenaryammonium salt iswanted,useexcessalkylhalide

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Amine Synthesis with Reduction

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Amine reaction with derivative of

carboxylic acid

 Reactionamong1and2aminewithester,chlorideacid,anhydrideacidresult

amide.

O O
CH3 C + CH3NH2 CH3 C + C2H5OH
OC2H5 NH CH3
N - metilasetamida

NH2
O
O
CH3 C + CH3 C NH + HCl
Cl
N - fenilasetamida

O O O
CH3 C O C CH3 + CH3NH2 CH3 C NH2 CH3 + CH3CO2H
anhidrida asam N - metilasetamida
Aminereactionwithnitritesacid

 Thisreactionisacid-

basereactionresultammoniumsalt,while2aminewithHNO2resultnitrosamine

CH3
H
CH3 N CH3 + HONO CH3 +N H O N O

CH3
trimetil ammonium nitrit

CH3 NH + H O N O CH3 N N O + H2O

CH3 CH3
N - nitrosodimetil amin