-13AMINES

( ·on .vou recoil '!

.
•. Write some examples of nitrogen
containing organic compounds.
' . .

• What are the types of amines? .·5~NH-CH' 3-,

··:. • • • • •·' • \J ~-.
'. .
·NH-C;H•·
I 6 5- , .
• ~· ' • ·.. • •.

•\
Amines are nitrogen containing organic , . O .
compounds having basic ch~racter.. Amines '

are present in niany natural ·compounds

., o·-'· . . .
like proteins, vitamins, hormones ~nd plant
products like nicotine. •• ,o> ..,./.~-
J'~; ~ -
,._ .•,

l 3 . 1 (~lo~siticotion· of 1\1niucs : Amines a_re

classified as. primary (1 °),. secondary ·{2°)
and tertiary (3°) amiµes. Their structures ·are
obtained in simple way by replacing one, two . <-~~---._ •)·qt:ber.. @.

or three hydrogen qtonis .of NH3 molecule by , . i::,f ..,·:.:, •,. , . .

:· '\i\'-t:.f~tli.~r . organic
•
compopun s
d
alkyl/aryl groups (see Tobi~ 13.1). :· l~. "'iv: lk.yl ·halides or alcohols are
Secondoiy and tertiary amines are further .,. f;ifis&J'fi.~d -cis 1·0 , • 2° ,· 3 ° depending upon
classified as simple I symmetrical amines and • th~fi,latu:re of the carbon atom to which.
. \.-.}_\ r· ':;·-·:·_,,? • • .. • ••• ,.

mixed / unsymmetrical amines~ When all the -:~if9VPl-,:~.group. is. q«:a~hed where as.
alkyl o~ aryl groups on nitrogen are same, it is -. ~µiij}~~ t9r~: clossified depe11dmg upon tne·
• a simple amine. If these •groups are different, n;pll\~:et:r
.\i
%-\\\:1,\
o.( .-alkyl·
-t • • ·,
1 •••
or•. aryl
• , ..
,,groups directly
\~'\ ·•..

then the amine is a niixed amine. 9tt~¢he~ to Jhe -n1tro-gen atom. Thus,
\\ 1 1 •,· 1 .\_11.\ .\ _.

Amines are also divided into two major

•i&PRfppyl Qtlline is 1° amine, but isopropyl
alcqhoLds 2° alco:hol.
classes, namely, alipl)atic and aromatic amines ·. ,.:; ,\~:.-~-- 't, - ''. -, ,, • ' •••. '
on the basis of nature of the groups attached to
the nitrogen atom.

'i'ohie 13._ I rr~n~cs of onlines

Functional group Examples

Type
Nome Formula Formula Common Name
\' •~\~tf: t,\ • • 'I '- •

Primqry amine, (1 °) .Arni.no : ''Ethy~a~e

Seconda,ry .amine,. (2°) . Imino ~etbylamine

Tertiary
Tertiary amine, (3°) • Trimethylamine
• nitrogen
 fJ.2 .~, un cnc lot ure _of .,\,nines : :
mm o? nam es :· Co . • . 1~l.J Prc.'llUr(1fio11. of An~inc~
13.2.~ C~ halides :
of abphat1~ am me s are giv tnrnon • names l3. 3.I : -By ~mmonolysis of alkyl
Writing the
name of alk yl gro up fol low e~~ by •• · Wh en alkyl halide is heated with alcoho
lic
' ."'In th Y: s_uffix -amine , undergoes
that is, '.alkyl am ine
th . e cas e of ,mi..xed solu~ion of ~xcess ammonia it
. which the
ammes, e. nam I
es of a11,-,,,t groups are .
~Y nucleophilic substitution reaction in
Writte n ino (-N H)
in a 1ph a b ett·ca order. If't wo or· thr • . halogen atom is repla~ed by an.am
ee identical process ~f
alkyl gro ups are att ach ed to n.1tr g~oup to form primary amine. This
.c. oge n atom, the is known
prefix 'di~' or 'tri -' is add. ed b e1o re the brealdng of C-?( l?ond· by· ammonia
•. name of . as ammonolysis. The reaction is also known
alkyl group. Th e par. ent -ary lami ne CH NH is
·.
ed as ani lin e. Ot her ·a ' . 6 s-
•
2, as alk yla tion. of ammonia. The reaction
is nam romattc e
·
ed as
·
der iva tiv es of an· i· • ( amines car rie d out .i~_a sealed tube at 373 K. It may·b
are nam . I ine see Table in the
13.2)~ not ed that the ·primary amine obtained·
. ' n ammonia.
. 1st step i~ stronger nucleophile tha
C system yl halide to
13_.2.2 IUPA_C .names ·: 1n· IUlb>A . , Hence,· it furt?e~. reac~s with alk
s_ •. ore nam ed . Y replac. ing . s an<;t finally
pru nar y amine , . f . • fo ~ sec_o_ndary and tertiary amine
th d"
~ng
,
e ~ .the . par e~t . alk ane by suffix . quaternary ammonium salt if NH3 is not used ••
e ~n •·- • .
(alfkan am 1ne ). A loc ant ind ·. t·tng the-.- ·-in large- excess. ; .• -
-am..me . . . _ 1ca
pos1tion o. -an uno _ gro up is add ed b_efiore- the - .. R~X +NH3(alc). ·,A ... R-NH2
. Wh . • •
• 1°amine
•
··n
re am1 o groups.
en tw . o or mo
' ·l .

•suffix am ine . .:. • • · (excess)' .

-', 'tri -' etc . are· used .. .

are pre sen t, th~ pre fix 'di

_l)i e order of· reactivity of alk yl halides • •
end ing 'e'·
with p~oper loc ant . In this· cas e the
• with ammonia 'is R-1 R-Br > R-C > l.
of par ent alk an e is ret.ain ed. .1
. ' \. •~~ ' \'\

·are nam ed /: ·-1._-.·

Se con dar y or .te rtia ry am ine s
of.- priincii-y '·
as N- sub sti tut ed der iva tiv e~
up att ach ed to .
amines. The lar ge st alk yl gro
ane ancfother· •
nitrogen is tak en as the pCJ!ent alk
. While naming ·_ ;:.
alk yl- gro ups as N- sub sti tue nts
is replaced· by . • :~
ary lam ine s en din g 'e' of are ne
ani lin e is also _• ,
'am ine '. Th e col l1m on na me of
•
accepted by IUPAC (see Table 13.2).
•
1b,·r.,.. · . ..

e na me am ine
of
n or IUPAC). is alwayS.\• •
· as on e . ·word. For ~xc;imple:
• l

- ~ EthYiamine (Ethanamine) .
.• l

...-.,_...,~-+~ •• I t
v- ~
. ._"
._ .~..._,-,, ~ .,..~ ' .••• \
. ... . ..
:

l~J~.
I
#f191 _ _ _._..,..

.• . ... .
fey this... wres of all - •
a..A'/1

· .· . . •
Draw possible strUC •
the isomers of· •CiI11N. Wnte the ir • I

· • p- A c nam es. .
mmon as well as JU ~ _
~-
CP
 I ond arylamines -
.Table 13.2 : Common and IUPAC names of some alky "' (UPAC names
;:
I'·
.... ... Zs;..

Amines Common names

-~
..

,
·--
.. .
---'f"1'--- •.
.,,,
a. Primary amines :
~~..... ~ i ; > , I ( ' / , ~ ... ~-~
•·
~~.-c--

r
.. . i
-··· Methanamtne ..,
-
CH3-NH2 Methylomine ,/·
Propan-f-amine
CH3-CH2-CH2:NH2 n-Propylam~ne ;
..,
..
. \

' . CH-CH-CH : Propait-2-arriine .

'
3 I 3 lsopropylamine .. ·I

' NH2 ,.

i !I!
.. Ethane-I, 2-dicunine
!I!
H2N-C8i-CH2-N~ Ethylenediamine ,~. '
;

. '
Prop-2-en-1-amine
CH2=CH-CH2-NH2 . Allylamine ~
I

l, . . J
NH2 Aniline or Benzenamine
""

@ Aniline/ Phenylamine ,.1,

.
i i
r.

' Hex~ne-1, 6-diamine

H2N-(CH2) 6-NH2 Hexainethylenediamitie
I'
,.

.. I
!
I • ·@CH3 ·,
p-Toluidine 4-Methyloniline ,

HN
2
• ,, ..... _;•,,, .'
'.
-,W"l' .,
lj
NH2
Cyclohexancnnine
0
'
Cyclohexylamine
'
., '· .
.
'
'.,:._
'·

CH2•NH2
. Phenylmethanamine
@ _.'.
Be~ylamiq~ ,i'

··,,.
;
.
-..- .
. - '
"
.
.,

.
OBr '· ~;\_
'·
4-Bromoaoiline or Ii
- p-BromoanUitje • .1
' .... '
4-Bromobenzenamine
H2N ~

-
I•· Oi
- .- ....
..-
.....
.,,....., --·-
·• ·-·· ----•.-,-~
~»:~ " ..
, :..,: - '-l-·'.:l! ·;
~--- . ..
'
·---

b. Secondary ~min~s ~ ;,~,,,

-;.;,'; *
'.,.
.,1~-
·,:~- ".-., ~

~-
;: ._,,
' --
~~~~-'._,..«,,w,)11"Q@»m1">?~.wn(,•;,~.9w,,w,¼,<,-,,·>X "),c,/Ki>,l).~0,,ox~>."'6t"f•~+w·~<),w,,..;,,~r, ~,);w.,...,,,,~.~-:,(..,',,•.t1,~,».·~i\"1">,:,;-».<iNM ~-.9),,,,;;;i,,>~~~"-'tl',.;~ -~......,.:., ~~
~ - " • - ....., ~~,~~o~~o~~,~~.t....~ ~ M ; . ~

•• . Dimethylamine .
'
CH-NH-CH
3 3
N-methylmethanamine '

I I:

CH3:..cff·-NH-CH
..
I
. Ethylmethy;lomine, ·N;-:m~thylethanamine I '
. 2 3 ... ·.r, ,;,. ·., .••
,, '
;
@NH-CH3 l

Methylphenylamine . . N-methylaniline or
'
,. ._,.
N;-methylbenzeoamine • ,, .
.
.l.. ''Id' I'

". ::-;; t'"

' \
I {

C6HS-NH-C6H5 j;
·o~phenylamine N-Phenylbenzenamine. ' 'l
:
. , ·u
--
•· i
·--- .•·.,
-·- ··-· ---· .,,-·-
c. Te~ary Amines , ' ' ' ..
I

I
~.-. . -- d •

CH3-~-CH3
,..., • ... , .,r, ....,,,•• ,, N ...
'
,,.,.w1,..,_• . . , , . . . . ~

. .
'Y,
"
..,,t••""""'~,......,,,w,.~19,(ffi:t;~,w~~•t•it,.,•M•i," '"...-.-~"-"''....-f,,Y,,,'""'"'f,~•~-.... -... ~,1-;.,~,;\,"·.>--w
"
t-·-"""'ll'"'' ~" ""w,v.;,.\\.n• .-....-.~ ,\ i'fl~-~~~')......,_"""''.., ----~~~',l(W,,.,.
'
......
--4;
;
I

Trimethylamine ;
CH3 r
' N, N--Dimethylmethanctmine l

... -· - .., -,-

,.
....
i'
'
C2H5-1;l-CH3 1

. CH3 , Ethylditnethylamine N, N-Dimethylethanamine

I
'
:
....,
-.
.. :i
- ·' - ... ·····;" ,. - I ... ·- .... . ·•"' -~ ,w ' \',
"

CH3-~-C3H7 N-~thyl-N-methyl propan-1-

'
(
Ethylmethyln-propylamine f
C2HS am.toe
~

' . .....
:,
} ... ... I

CH-CH-C~
3 I N-Ethyl-N-methyl
Ethylmethylisopropylamine
I
C2H5-N-CH3 \.
propan-2-amine
I

.. . . "

~-CH3
@ CH3
-- - -- --
N, Nr-Dimethylaniline
.. "
N, N-Dimethylbenzenomine
- -·-
- -
- •• -c... ··- - --- ""···-J...,. -
·-- ~
-- -· - ·-- '
,·----------

•
Solution•• Meth
tett-butyt bronud ~ ll.lt.,.,\,.. . • . yl bromide can be converted
~~~
. with al h e .• • • into ethyl amine in two stage reaction
-~ . .. _co olic NTJ seque_nce as shown below.
IS fonned • ThiS 1S. 0h 3,
,. reaction t e result CH3-Br + KCN • CH3-CN + K.Br
. . preferred over
substituti CH3-CN
.carboc ~n ~ou gb the stable Na/C2H,OH
(reduction) )II. CH3-CH2-NH2
atton intennedi
The starting. compound methyl bromide
conta~ns
• one carbon atom while the product

. .. ~C icr ~3C-~ ~~ ethylamine contains two carbon atoms.

1:- reaction in which number of carbons
bromide) I.,
.-ff$ increases involves a. step up reaction. The
•
overall conversion of methyl bromide into
~H2 ethy~ amine is a step up conversion.
H3C-C-CH
(isobutylene; ,

. 13.3 ~ ~ed~ ction ~f ni~rocompounds :

. Afiphati~ and aromatic nitrocompo ds
~
primary ami~.es by using
can. be redu
~ . . to
.d ced
ijiijiua-:<JCl tm~t_w'~ (Sn/HCI or Fe/HCI or Zn/
.
1161) or catalyt1c hydrogenation (H2/Ni or Pt
) or LiAI H in ether. • . •
. 4 • ~

0~.+6[H] Sn/HCI_► R-NH2+~2H20 .. _·

,3 Redu ction of alkyl cyanide · I

_13.3.4 By reduction of amides :.

'

enitri_les) :
Primary amines having same. number of
u recall? carbon a~oms can be obtained by the reduction
. of amides by LiAIH4 in ether or by Na/C2H50H~
w is alky l halide_ converted . .
.
011 • . LiAlH4,ether ~O-.
alky l cyan ide ? • •
4 C"3 -C8 i-~
, .. · _CH3-C-~2 + [H] orNa/C2H5OH
(Ethylamine)
• ·QIY amin es can be obtained by _the (Acetamide)
+8i0
·on of alkyl cyanide with sodium and
reduction. 13.3.5 Gabriel phtholim_ide synth esis : This
LThis is known as Mendius
met~od is used for the synthesis of primary
tion can also be broug~t •about ~y
amine. Jt involves the following three .stages.
oluminiUlll hydride.
i. • Formation of potassium salt of phthalimide
:N + 4[H] Na/C,_H .OH ► R-CH2-_NH2
or LiAIH • • • . from phthalimide on reaction with alcoholic
.
4
1° amine.
potassium hydroxide.
.ii.' ·Formation of N-alkyl phth~limide· from
m 13.1 : Write.reaction to-convert . the potassium salt by reaction with- alkyl
I mine ? Also, • •
l brom ide into ethy a • • t ms : , halide.
• umber of carbon a o .
=~:nt on the n d d the product. iii. Alkaline hydrolysts of N-alkyl phthaiimide
~ g coro poun an •.. ,.,.:fo·JQrm the corresponding primary amine.
 011
L (Xe, .

N-H alc~KOH JIii

· Q.Ic , 0
• II
em
NK
•
• The ove.rall resuIt is removal of the
• · -C-
.1d As the product contains
group from the aml e.than the original amide. .
0

Hp ~
CY'
II
.• . . . C/ one carbon atom ess
II
0 0 It is a step down react~n.______- -
• (Phthalimide) (Pot assiu ~
list;-~::tu rb rl;;;!,~+;,. :/:'· •,•• q•/ .~
salt of

~-,
.phthalimide)
·O
II
0
. W~te_ • the chemi~al equations for.;:·.~ .
l .
I.
ii. oC ,~0 EB
. ~ I . NK c,,,,
II
·o
ex
. c,,,, .
II
.o
N-R
\'
,,

._.
-.
. the following conv
,
. .
erston8-__ _. • . . ·· ·: •• •
.. ·1• ,,

.• l Methyl chloride· to e~y l~m ~. · : : · .-

•
,
•'·

.• \..
..

·_',
• •
\.

•.'• ·\x• .

(N-Alkylphthalimide)
•i1.: .B~ kii d~ to aniline~ - •, ,: ~

o·
0 • • 0
111 11 • II '.Iii'.} 1 •4-Di~ht~butone.to bCxane - 1, 6. -
• (XC, •
. N-R NaOH• (aq). ·. I C-ONa
eEB !....:.,.~--dim~'.ine. - ~.:. •:, ·: .;\ ·. :. · _.:_-:· ·:.-, . ..._· • .
C,,,, ~
• ·
;,'"~ •• \',I ' ', •

~
1,, \ ,, :

C-ONa
\ t •,:, \ .' ••

• ·i~.· Berizamid~ to ~erizylamine.

•

11 • · · ti
0 0 ..
.
l3 . 4 Ph)'slcul 1>1:~•1)crtics of ,\1nincs :
.
(sodium. phthalate).
. 1·3.4,1 Inter~~leculor (orce~, •boiling poin
+ R-NH2 · •and solubility. ts
.
: The N-H h~n d in amines
(1 ~ _o_mine)
Aro~atic amines cannot be prepared • i& polar bec<:ause •the electronegativ~ties of
by .this _method. ~ecause aryl_ h~lides do. not Nitrogen (3.0) andHydroget?-(2.1) are different.
undergo •riucleophilic substitution with the · Due to the polar nature of N-H bond primary
anion formed by phthalimide. and secondary· umines have • intermolecular
hydrogen. bonding._ • The intermol~cular
13.3.6 By Hof man n _degradation (Hofma . .

nn. hydrogen bonding is _to grea

rear ran gem ent / · Hof man n ·bro mam ter extent in
ide . primary amine than in • seco
deg rada tion • / . Hofmann_ hyp obr omi nda ry am~nes,
te because primary amines have
deg rada tion ) : two hydrogen
atoms bonded to nitrog~n for hydrogen bon
d
This is a good laboratory method for the formation (see ·Fig _13.1 ). •
conversion of an amlde it;1to primary ·amine
containing one carbon less. The re~ction is· 6EB 6EB
bro~ght about by wanning· _the amide with _· --~-~--11- 6EB 6e~ 6E0 69I;I-------
bromine and concentrated ~queous KOH
solution.
. R-N--H---------N-H------:--N-R
l I 6EB H----
I ---
•
•
·•v If·~ ·~r'\

Hydrogen bond -------H-N-R

0 . • I
II
R~C-NH2 + Br2 + 4KOH(oq) . !Ji H-------
• 1 lfJ~ .. . : II l'l'IIIO l'\'U l)'l l'Otjl'II JOII( IIIJ) 111
(~i de) (II'

R-NH2 + 2KBr+ ~co3 + 2H20 1n·l111ury un,hu's

(1° amine) Tertiary amines do not have intermolecular
hydrogen bonding as there is no hydrog_e
n
For example: atom on n~trogen of tertiary amine. But due
to po~ar N-C bonds, tertiary ~mines are pola
0 ~-
. . a molecules, and have intermolecular dipole-
CH:3-C:.NH2+ Br2 + 4KOH (oq) )Ill CH3~NH2
•. dipole attractive forces. Thus intermolecu
(ASeta~de) • (methyl~min~) lar
forces of attraction_ are_ ~tJongest in primary
+2KBr + K2C03+'2H20 amines end weakest in tertiary amines.
·• <$~~~
 tne ooserveu-oroer of bo·i· 1
. .
!..:~ c amine s is : Primary a . tng Points of T,,btc 13.3 Bollinu points of i,lk(Ul·l~, olcoh ol
. ,.....--- . . nune > second
.CJllline > tertiary amine (see Tabl 13 3 ary un_d unlincs of shnUur.anolur u1ossrs
.-.1111berS 1, 2, 3)~ It can be expie· • • oserial h St.
~ . wn~ ~olo r B.P. (K)
1,aSis of the mtennolecular force.s.1n them.n t e No Compound
moss
The lower aliphatic ami·nes are 9• • I • n-C H NH 73 350.8
lrith fishy odour, middle members are hq . ases 4 9 2
·d
and higher members are solids und . . uiarys 2 (C2H5) 2NH 73 329.3
. er ordin
~ e ~d pres~ure.
I
•

arylamines·a.re usually . 3 C2H5N(CH3) 2 73 310.5

Aniline and other
b '
. . .d •
colourless· 11qu1 s ut get ¢oloured as the 414.4
~ ~xidi~ed by _air. • Y are 4
'I
C2HSCOOH 74

Oue to their ability to rm hYdrogen c.

1 0 5 n-C4H9OH 74 390.3

l
• . •

•h .
•. •

. . cule, lower a11p attc .

with, -•water mole "

.. . ~e. solu~le 1n· water '(see Fig. 13 _2).- 6 (CH3) 3C-NH2 73 318.15
il~ ·of a~ne s ~ecrea~es with increase
lar mass. of amines due to increase in size 7 C~HSCH(CHJ~ 72 300.8
~ints
. phobic alkyl group. Ar~rnatic amines
unes 13.S _Hosicity- of 1\111incs
·gher _aliphatic a~ine s ·are insoluble in
s of . .
The basic nature of amines is due· to
I ,

rent.
;
I

prese~ce of .a lone: pair of electrons on the

I

nary . .

nitrogen atom. In te~s ofLewis theory, amines

' • '
• . • Hydrogen bond·
:ular are bases becaus~ they can share a lone pair of
;ular .- , . electrons·on ~N' atom with an electron defici ent
,•. H~- --~l !~-- --~: -~I ' ; .
. ' .
.t in I • I
H.· • species. For example :· Trimethylamine shares
. H H ..
1nes, ,. its· lone... pair of electrons with the electron
ogen • 1_3.2_ : I l) dro9e n lu~ndlng bet~ee~. . .
1

deficient boron trifluoride. •

~ 0111i11c oud ,vote r molecule ••. • , :. ·:.. ··,
Jond
ince N~H bonds in amine~ are Jes~ polar . . •' '' Me3N: + 'BF3 :' ~ Me3N-~F3
H boiid in alcohol,' water solubilitie~ of • ,. • ,

amines and ·alkanes of comparable •••• • ••- Basic strength of amines· is . expressed
' .
·:qua~ti~ativeiy·as K,, or p~ value. In terms of .
' • ' •

!JDOSS in.· wate r are in the decreasing

> the basic nature. of
ohols· > amin es olkones. • · t· •·: _. Lowry~Bronsted theory,
. .. . . · • . • Of lkanes . amines .is expla ined by writing the following 1

order of bo1bng points a .. ' •. 1'b • • • •

alcohols and carbo xylic· acid ':"of equ1 1 num._.' . EB . e'

• le moia r mass· is as follows: •• · ) . ?N:+ H2O , > ~N-H + OH .........._. (13.~) •
• •• (conjugate acid) •
< Amines < Alcohols < Ccirboxylic ' (amine)
le 13.3, seri~l _n~~~~- ' ?)_
6
. Inthi s equilibrium amine accepts H6',
1cutar hence an amine is a Lowry-Bronsted base.
· ,r,ver~:~·-:\.
rogen :. \ i. •:·.: ~: ~::;.. For , stronger .·base,\' this equilibrilllll~' shifts
t dU~ 0 W1119,.·r tow0rds right, thereby the_ K;, vallle is, larger
potar- --~~_---:-~.. : (·_- _ anq p~ value is smaller and vice ver:s·9._ (r~fer
pole-
1 P-~~-i},. t6,_~hc,tptei: 3). Table 13.4 gives l'~,Y ~~~ of
~cular ,~Ni ajt _ sJweamines.
101arY • """ /2..✓..., ~ 287 · +>·. ~0>
, - ., • • ••
~
 Tobie 13.4 : pKb Values of some amines in (Jqueous medium

Structural Formulo , , p~ value

IPrimary olkonomines :
Methanamine· CH3-NH2 3.38
·•Ethanamine CH3-CH2-NH2 3.29
Propan-2-amine (CH3) 2-CH-NH2 3.40
Phenylmethanam ine Q-cH2-NH2 4.70
I•
Secondary olkonomines :
N-Methylmetha namine (C~)2NH 3.27
~ N-Ethylethanam ine (CH3CH2)2Nfl 3.00
Tertiary olkonomines .:
N, N-Dimethylmeth anamine (CH3) 3N 4.22
N, N-Diethylethana mine (CH3CH2)3N 3.25
Ammonio 4.75
Arylomines :
IBenzenamine (aniline) .. O~ 9.38
.
N-Methylaniline ◊NHCH3 9.30
N, N-Dimethylanili ne Q-N(CH3) 2 ,
8.92

13.5.1 : Basic strength-of aliphatic amines :

Can you recoil ?
The trend in the observed P¾ values (see • What is meant by + I effect ?
table 13.4) and basic _strength of 1°, 2°, 3°
amines and NH3 can be represented as shown • Which of the following species is
better stabilized and by which effect ?
below:
EB EB
Order of P¾ values: CH3-CH2 and CH3-CH-CH3

NH3 > R-NH2 >~NH< ~N Basicity of amines is related to the structural

Order of basic strength: effects which influence stabilization of various
~pecies. Greater is the stabilizatio~ of the
NH3 < R-NH2 <~NH> ~N ......... (13.2)
protoncited amine, that is, the conjugate acid,
Thus as per the observed P¾ values of the greater i_s the ·basicity of the amine.
aliphatic amines, secondary omines ore the
stronges~ bos~s. Basic strength increases as
we move from NH3 to R-NH 2 and from R-NH2
to ~NH, but basic strength decreases as. we
move from ~NH to ~N (T~ble 13.4).
The basic strength qnd the corresponding
p:K., value depends upon the position. of the
equilibrium shown in Eq. (13.1). Greater the
stabHization of the conjugate acid ~ore on
right side the equilibri_um will lie and stronger
will be tli~ base and smaller will be its P¾
value.
r-. •-lhlence
,. ..... - . of +I effect
. on stab·i·
..llfl~l'ldt.e acids of aliphatic amine
.
1 tzation Of
- H, ;H
~..iJ-.---. d s and NH
can t,ere --piil"Pesente OS shown b.elow : 3 9·
I;IEB
II, . · • HIEB HIEB H R-N-R
a~N.:H . R~N-H R➔Nf-R
• I
'

~ L
Af'I
I

1 . group
·
H'
. H
I

exerts · electron re1eas1n

,
R➔Nf-R
R
.
EB
, ¥
H,..O,H

.ndl~·ve effect
· .. ~
(+I) which stabilizes p os1ttve The solvent water stabilizes the conjuga~e
on atom bonded to it. As we acid by hydrogen bonding through the 'H'
. .d f . move bonded.to the 'Ne\ The number of 'H' atoms·
~ugate act o ammonia (NH EB)
. • (» e 4 to bonded to the 'Ne' decre~es from 4 in NH4ED
tertiary anune ...~NH ), the number of
to 1 in_. R3NHe. ·As a result NH4ED is best .
~rom:,s (R) b~nded . to ~itrogen goes. on stabilized by solvation while the stabilization
steadily. Th1s results
· .
in increasing
by solvation is very poor in ~NHED. • • .
-~~ of t~e ·conjugate acids and
~crea~tng order of basic strength • c. Combined influence of +I effect and
solvation .on ·stabilization, if conjugate acids
tabilization : • of aliphatic ru;nines decides the observed basic
EB EB EB strength and p~ :value. These two influencing
-t < R~NH3 < ~NH2 < ~N~11 •fact~rs operate in opposite directions. •
order of basic strength : .
increases
. Solvation
<R-NH2 <~~<~N _ EB EB EB. EB
IEH_~ted order ofbasic_strength on 'the< _ • _. • NJ:14 • R-NH3 ~NH ~NH
ect differs from the observed order •• . +I effect • ~ - - - - - - - - - - . - .
.increases·
is seen that the observed increa~m:g
from ammonia to 1° amine ·and •- Toe net results is. .that as we move from
'·

e .to 2° amine is. ~xplai~ed on the_ • . NH3 • to RNH2 to ~NH, •the basic strength
sed stabilization of conjugate. increases due •to better stabilizatj.on of the
effect of increased number of corresponding conjugate •actds. l3ut 3° amine
ups. However, decreased ._basic is .weaker base- than 2° amine because the
0 amine implies that the conj~gate stabilization· of conjugate acid of 3~ amipe by
ami.ne is less stabilized even . solvation is very poor.
effect of three alkyl groups _.in· 13.5.2 Bosicity of orylomines :
ICU~ to be large. This is suggeSt ive
of another influencing factor .in Can you recoil ? •
.
of conjugate a~,ids of ciniin~s. Refer to Table 13.4 and answer:
· of .solvotion. by. water ~n Are the p.K,, values of aniline,
of conjugate acids of aliphatic N-methylaniline and N, N-dimethylaniline
ammonia con be represented as larger or smaller than those of NH~ and
CH3NH2 ?
~ich one of the two, aniline or CH3~ , is
-~
I
i
a stronger base ?
i

/H
·····O
'H ,.

.I
 From the pl(,, values we understand that As a result the equilibrium (13.3) is
arylamines in general are weaker bases than • shifted towards left side.- This ma~es aniline
ammonia • and aliphatic amines. •Strength (and also other ai-ylamines) weaker bases than
of arylamines is explained in accordance aliphatic ai;nines and ammonia.
with Lowery Bron_sted theory by writing the -------
following equilibrium (Eq. 13.3) For aniline
(similar to eq~ 13.1 ). Arrange the following amines
in decreasing order of their basic
EBNH3 e strength-

(Base)
, '
6 + OH ....... (13.3)
,

(Conjugate acid)
NH CH -NH (CH NH, C H NH
3
,

3 2
~

3
)

13.(, ('hl'nti\·ol pro1u.-1:th.'" of 01nin(·~

6
5 2
•

13.6.1 Laboratory test for amines :

Here, both the species base. and cotij':1gate
acid, are resonance stabilized but to different o. Test for amines as the 'hose': All amines
extent. 1°, 2° and 3° cire basic compounds. Aqueous
solution of water soluble amines turns red
In arylamiiles, the -NH2 gr~up is attached
directly to an aromatic ring. The lone pciir litmus blue.
of electrons on niµ-ogen ·is conjugated to The 'basic' nature of amines is detected in
the aromatic ring ~nd is less available for laboratory by reaction with aqueous solution
protonation. Aniline is resonance stabilized by of strong mineral acid HCl.
the following five resonance structures. . EB
)N: + HCl(aq)-... • )N-H(aq) + Cl8 (aq)
EB . EB · (amine) ( a substitute·d
• NH2 NH2 ammonium chloride)
2
EB
◄ JI, )N-H(aq)+Cl8 (aq).+NaOH(aq) • )N:+
. (excess)
NaCl(aq) + H20
(I) • (II)
•• Water insoluble amine dissolves in
NH2 aqueous HCl due to formatj.on of water
4 JI,

(IV)
4 JI,

6(V)
soluble substitµted ammonium chloride,
which on reaction with excess aqueous NaOH
regenerates the original insoluble amine.
b. Diozotizotion reaction/ Orange dye test:
On the other hand .anilinium ion obtained In a sample of aromatic primary amine,
by accepting. a proton does not have lone 1-2 mL of cone. HCl is added. The aqueous
pair of electrons on nitrogen. Hence it can be solution of NaNO2 is added with cooling~ This
. stabilized by only two resonance structures solution is transfered to a test tube containing
and therefore less stabilized than aniline. solution of .'3 naphthol in NaOH. Formation
of orange dye indicates presence of aromatic
EBNH3 primary amino group. (It may be noted that
temperature of all· the solutions and reaction
mixtures is maintined near 0°C throughout the
•reaction) ..
(I) (II)

290
 The reactions involved in th'
·
discussed in section 13.7.2. is test. ·1
Wt I be 1~· 6 3
• Hofmann Elimination :
13 .6.2: Alkylotlon of amines : llo When • tetraalkylammonium halide is
•houstlve olkylatlon: When a . flllonn's hetated with moist silve~ oxide, it gives
ex . Pnma am•
is heated with excess of primary alkylry h . in~ 'quantemary ammonium -hydroxide which is·
jves a mixture of secondary am· ah~e it a deliquescen~ crystalline solid, and strongly
g .
,..,,,ine along with tetraalkylanun ine,
.
.tertiary basic like NaOH or KOH. Quaternary
w•.. on1um halide
(also refer to sec. 13 .3 .1 ). ammoniu~ hydroxides on strong heating
undergo ~-elimination to give an alkene, the
R-X
R-NH2 -HX ►
R NH R-X R R reaction is called Hofmann elimination. The
-HX ► "3N ~ ► R NXe
El)
i~ ...
(lo Amine) (2o Amine) (3• Amine) least substituted alkene is obtained as major
(T:troolkyl
product (in contrast to Saytzeff elimination)
ammonium
· halide)
For example : •
If excess of alkyl halide is used tetr lk
. h I'd . . • EB
0rnmonnun a 1 e 1s obtained as aa .yl . ~H3CH2CH2-N(CH2CH ) 18 + AgOH
. Th . .. 3 3
produc~. e rea~tton is. known as exhaumaJorstive
(N,N,N-triethylpropylammonium iodide)
alkylatton of amines.· • . A.I moist
OtA9iO •
, I •

i;'he tetraalkylammonium halides are (l ~

CH-CH3 •
called quaternary ammonium salts which ·are P' a' EB I 2 0
CH-C H -CH -N-CH -CH OH
crystalline solids. They are the derivattves 3 2 2 I 2 3

of ammoium salt_s . in which all the four CH2~CH3

w ~ogen atO~$ attached to nitrogen in
(N,N,N-triethylpropanammonium hy~ox ide)

NH4 are replaced by four alkyl groups (same ~t·H,O

or different). Primary, second~ry and tertiary.
~

.CH2=~H2 + CH3CH2CH2-~-CH CH
. ..
2 3
amines consume three, two and one moles of (ethene) CH CH
2
alkyl halide respectively to get converted into (N,N-diethylpropan-1-amine)
3

quaternary ammonium salt. The •reaction is

carried ·out in. presence of mild base NaHCO ,
3
to neutralize the large quantity of HX formed.
Ifthe alkyl halide is methyl iodide, t~e reaction .
is called exhaustive methylation of amines.
For example : When methylamine is _heated
~ith excess methyl iodide,. it gives tetramethyl •
ammonium iodide. • \I \ \ \ \ ' I

CH3-NH2 + CH3-I ~ ► (CH3)2NH + HI nium 1solt wbic

I • ,>
ervous '1 ,~•

(CH3)2NH + CH -l ~ ► (CH ) 3N .+ Hl ~ ' ,,

3 3
\ tf,Qtl~' . '
(CH3) N + CH -I· ~ ► (CH '©0
3 3) 4NI · , ~,-t~Q-Cfl2-Cfl2• ,.(~ijl
3 --~-~--.-..,-
-I'\,-:, .... - -.......~ - - - - ~ .

P.o'"~,, -
...

lls11 ~·9...~ 1,~, , uatemary amm oni~ ~ f<J,{

resent ip cationic ~etergent
 13.6._4 Acylation of amines : primary amines. s~ondory and tertiary
amines do not give this teSt •
Con you recall ?
R-NH2•~ CHC13 + 3KOH.
• What is an acyl group ? (1° amine) • . A,... R-NC +JKCI + 3H20
• How are alcohols acylated ? (Alkyl isocyonide)

Aliphatic· and aromatic ·primary and

• secondary amines undergo acylation reaction.
These amines contain replaceable hydrogen
atoms (positively polarised H) on the nitrogen •
atom. These hydrogen atoms are ~eplaced . .

by •acyl .groups• such • as acefyl group.. OJ.?.: 13.6.6 Reacti_on with nitrous acid : Primary,
•_reaction of amines with acetyl chloride or s~condary and tertiary amines react differently
acetic anhydride, acetyl deriv.otive of amine ~ith nitrous acid. Reactions of. only primary
is obtained. It is also· called amide.· Amide
• ' I amines will be considered here.
is less basic. than the amine. Acylcition
.
is Q •
n~cleophilic substitution reaction. The reaction • Can. fOU teU ?
is carri~d out in presence· of strong ba~e like
pyridine, which neutralizes. the acid produced
•
• What is the formula· of nitrous
during the reaction. For· example : · acid?
(i) ·H .o~- • Can nitrous ocid ~- stored in bottle ?
•• .
·OII 1 I
CH -N-H + C-CH Pyridine• C2H-N~-C-CH
5 I
•
2 5 I
H ·. Cl
I . 3
•
I 3
Nitrous acid is an_ unstable compound.
·H CI'
. Hence it is prepared in situ by adding aqueous
(Ethan.amine) (Ethanoyi
chloride) 0II -! • sodium nitrite to hydrochloric -acid already
.
C2H5-N~C-CH
I . 3.
+ HCl •mix with the ~ubstrate, that is amine.
·H
a. Aliphatic primary
.
amines on reaction with
(N-E(hylethanamide) . .

..)
(11 . nitrous acid fom1: aliphatic diazonium salts as
. H o'"" O· . _ very unstable inte~idiates which decompose
H3C-N: + C-CH3 Pyridin~ H3C-N-C-CH
I
+ HCl.
3 • immediately by reaction· with _solvent water. -
I . I
. C6J:I5 Cl C6H5 •. Corresponding alcohol is formed as the.product
(N-Methylaniline) _ (N-methyl-N~phenylethananiide) -of the r~acti~n and nitrogen gas is liberate~ .
Benzoyl chloride also· gives •similar reaction
with amines. ·R~NH2 t HN02 (N~~::sH~I)► [R-~2 Cle] •
•(alkyl diazonium
chloride)
·8io ► R-OH + N2 + HCI t
b. ~omatic primary amines react with nitrous
• acid to form diazonium salts which have
13.6.S Carbylomine reaction : reasonable stability at 273. K. .
. '
Alip~atic or aromatic primary a~ines on .
(N~O!~HCl)►oN NCI
+ 273-278 K · ~ • EB 0
heating with chloroform
.
give foul (offensive) .• 2 HN02
smelling products called.alkyl/aryl isocyqnides . -
• • (benzene diazonium
or carbylamines. This reaction· is d test for . chloride)
.... I ( I . . -.. __ .______ J
... ' ' "'1 •

~~~<e>
I
f
AfY1 diazonium salts. are reson • .
useful as versatile intenn·ct~nce stabilized
011d 1 tote Reaction ·th fluoroboric acid :
variety of products. • • s to obtain . WI
0
EB~
EB 0
•• EB e fl Aren_e diazonium salt •on reaction with
N==N= N N: N:::N• ~e fl uorobo1:c acid gives precipitate of diazonium
~oroborate which on heating decompo ses to
yield fl uoroarene. On the other hand when .
aq ·d. . . • .. •
. • with ueous so tum n1tnte 1n presence
heated
of copJ'er tt •
• gives niq-oarene.
$

► Ar-N)F~
-o= Ar-N}~l HBF,

.. /fl.
Ar-F+ N 2t + B.F3
~aq. NaNO
L\~Cu

t
2

Ar-NO2 +N2 + BF3

t3 7 Reactions •of orene dioz i
Aryl diazonium solts •show twon0 um salts:
. types of
reactions.

JJ.7.1 Reacti~nTshin~olvin~ displacement of

dfazo group : .e d1azonnun group (-N/~) is
·t·
- due to the .pos11ve
0 very good .leaving group
charge on nitrogen atom bonded to aromatic
~9- As _a result, the arene diazonium salts
·undergo. nucleophilic substituti~n reaction·
13.7.2 Reactions involving rete~tion of diozo
with a variety •of !}Ucleophjles. Table 13 .5 group: (Coupling reactions) :,
. shows reactio1:1s of diazonium. salts il}volving
·Arene diazonium salts when treated
displacement of diazo group.
.
with certain reactive. aromatic compo,unds
such as phenols or aro~atic.amines;.·give azo
.

Table 13.5 Reactions of <irene diazonium salts

. --rrx ' . -~~-1'~'-':.' compounds. These have extended conjugated
Reagtf', ·ijuc(s
"❖'• •
system of double bonds .in which .two
aromatic rings are joined thro~gh. azo group
-N N-. This reaction is called ozo coupling~
Azo compounds are brightly coloured and
are used as dyes. )'his is an example of
electrophilic aromatic substitution reaction.
Here the electrophiles are positively charged
diazonium ions. Substitution usually occurs
para to the ring activating gr~up. For example:
_ ; Kl ~r Ar-I+N2 Benzenediazonium chloride react~ with phenol
in mild alkaline medium to give p-Hydroxy-
N2Cl {- .:
, azobenzene (orange dye).

0 :l&=NCle +OO H OHe,.

(Benzenediazonium
chloride)

O N NOO H + HCI .:: . .',

e • Hf' • Ar-OH+N2
+ HCl (p-Hydroxyazobenzene)
- Cl - 2s3 IC .,.
2
 Azo coupling with p-nophthol in ~oOH 0

O
►
S-Cl+ H-N-C2Hs
is used as a confirmatory test for pnmary
0" ' c' 2H5.
aromatic amines. Benzenediozonium chloride (2° amine)
reacts with aniline in mild alkaline mediUlD to
0
give p-ominoazo-benzene (yellow dye.)

0 ~"NCle + 0 NH, oHe ►

0 S-N-C2H5 + HCl
11 I
0 C2H5
(N' N-diethylbenzene sulfonamide)
(Benzenediozonium (Aniline)
chloride) N N-diethylbenzenesulfonamide does not
c~ntoin any H-atom attached to nitro~en ato~.
O N N-0-NH, + HCI Hence it is not acidic and does not dissolve tn
(p-Aminoazobenzene) alkali.

~
< •

Do you kno\v ·: tc-11 '!

( '1111 \'OU ~\
The acid-base n,dicotor • Do tertiary amines have 'H'"' •)~
orange is an ozo dye. bonded to 'N'?
(C~)N -@- N N -@-s6 ~a 3
• Why do tertiary amines not react with
benzene sulfonyl chloride ?
. ('hlo1 ide :
13.H Rrucfion ,\!ith ort•iu.·sulfonyl
(Hinsberg's te.st) Benzenesulfonyl
chloride (C6H5S02Cl) is known as Hinsberg's
. .,'., .distingµ.ish between
reagent. Qietl},.yl~m~e, dime~ylamine and
a. Ethyl amine (primary amine) reacts with .tpni'ethylainine by Hinsbergfs test ?
benzenesulfonyl chloride to form N-ethyl
benzenesulfonyl amide.
0 • ' I J.') l(l{'t·t rophilic.· suh~tit uHon in
nro1110Ht
nron,nti,· c11ui1u•,; . Amino group is ortho and
O S-Cl
11
0
+ .H-N-C
H
I
H
2 5

(Benzenesulfonyl • ( 1° amine)
► .
para directing and powerful ring activating
group. · As a result aromtic amines readily
chloride) undergo electrophilic substitution reactions.
0 .
a. Brominotion : Aniline reacts with bromine
0*-:ti-C2H5 + HCI
water at room temperature to give a white
OH
(N-Ethylbenzene sulfonamide)
precipitate of 2,4,6- tribromoaniiine.
(Soluble in alkali)
NH2 NH2 .

The hydrogen attachetl to nitrogen in · Br Br

sulfonamide ethanamine (a primary omine) is + 3Br2 Br/H20 ► + 3HBr
strongly acidic. Hence it is soluble in alkali.
(Aniline) Br
b. Diethyl amine reacts with benzene-sqlfonyl
(2,4,6-tribromoaniline)
c~,pride to give • N, N- diethyl benzene
sulfonamide. · ( .. :
J.I \ '

• I I
r.
~----.
IJ.1 : Write. the schem; c. . .
• n of p-bromoan1·1·me from • .~or NH2 •• . N~ ONH2 -_
•, ·.
ur answer. . .
On11tne

I ~ - group in aniline .is hight.

oting •and o-/p- directing due t~
•
6 (Aniline)
• Cone. HNO1 + Cone H S04
.. 288K
2
)Iii~
~

N02
I+
~
I
• NO·2
+

t of the lone pair of electrons (51%) ~47%)_ .

• (p-nitroaniline)(m-mtroamhne)
m: resona~~-. wi~h· the ring. As . NJ{l
on . reaction· with Br • it giv
.. T 2 es -~N02
mom11ne. •~ get a monobromo
• i~.. necessary to dec~eose the V
(2%)
~g ._effect o_f -NH2 g~oup. This (o-nitrooniline)
ocetylation of aniline. The lone
. .
l _in ~cetanilide is also involved in Internet n1y fri(\nd
1n the acetyl group. To that extent ••• Search the pK0 or p~ values
•on decreases. • • of ortho,. meta and para nitroaniline
o~ . . oe. on internet and arrange them m
-~
:C-C~3
.
► Q·. NH_ C-CH
~
•
•
1
EB I •

3
··inc~~asing order of their basic strength.

However, •to get p-nitroaniline as major

·"lide on bromination gives a- • ··product, •-NH2 g;oup_ is . first· protected by
. product · p-bromo~cetonilide~ acetylation, nitration is carried out and then
roµrination th~ original _-NH2 amide is hydrolysed. • . • •
nerate~. The_ prote~tion of . -.· o·
. .• II
in· the form of acetyl, group _is
aci~ catalyzed hydrolysis to ge~
• e,· ·as shown. in the foll~wing
,;s
V (cH,co\o► V Pyridine
;;c:~o,+c-~.
.·. ... 288 K

0.II
· • (Aniline) • . (Acetani.~ide) 9
• •• NH-C-CH3
NH-C-CH3

~-~
~-o- I a.r2
(Acetic acid .
► .
---; ·.'._. : I
~ . solvent) I •

(acetanilide) ' '· N02

(p-n1troaetanilide)

r~o~
.,NH2 .•
',

Br
'lide) (p-brpmoQniline) NO··.
2
-~ - (p-nitroaniline)
·1·
P.irect nitration of ant ine ·!.eilds
.
• d para nitroan1hnes. c. Sulfonotion : Aniline. reacts .. ~~---
o,metaan . td
-NH . grQUP is protona e conceintroted s.ul~c acid to ._fonn. anili~~~ ~; .
2 • and· hydrogen sulfate which ~n h~ot1ng ~•th sulfuric
which is. metQ-dire_cttng . acid at 4?3-473K produces p-Cimmobenzene
. . ble amount of
ence cons1dera , . . s~lfonic acid (sulfaniJic ~cid) .OS major pr~uct.
,.. •obtained~

I•
 EB e Sulfanilic acid exists as .a salt; called
NH2 NH3HSO4 NH2 • 1or 10• 0 or• zwt·tter ion. It 1s produced by.
d 1po . . .

,. 6
6-"2-SO.....:.•.. 453-473_K ,.': I
the reaction between an acidic group ~d a
• the .same molecule •
• . gro11:p present tn
baste
(Aniline) (Anilini~ SO3H.
hydrogensulfate) (Sulfanilic acid)

' SO38
(Zwitter ion)

' ~-- -- •
~xerc!ses Jt=:: >coc c-oo ~cac cc
•

t=:>C OOCC O~CO ::C:C (

1. Choose. the _most correct option.
i. The hybridisation of_ ni~ogen in primary vii. Which one of the following compounds
. 1s.
does not react with ocetyl chloride ?
am.me ............
•a. sp • . b. sp2 c._ sp3 . • d. sp3d • • . a~ CH3-CH2-NH2 • b. (CH3-CH2)iNH
ii. Isobutylamine is an example of ........... . ~- (CH3-Cl:f2)3N. ~- C6HS-NH2
..

viii. Which of the following . c_ompounds

•
0
.a. 2 amine: . b. 3° amine
C. 1°. amine • . will dissolve in aqueous· NaOH after
d. quaternary ammonium salt.. . undergoing reaction with Hinsberg_
. . reagent·? .
.111. .Which one ·of the following compounds • ·
has the highest boiling point ? ~- Ethylamine . . b. Triethylamine
a. n-Butylamine b. sec-Buty.lamine .. c. ~rimet4ylamine . d. Diethylmnine
..
c. isobutylamine · d. tert-Buty. lamine •ix. Identify 'B' in the following reactions
. .
Cff3-C .N Na/C H 0H ► A NaNO/dilHCI ► B .
2 5

iv.. Which of .the following has the highest .

basic strength ? a. CHt-~H2-NH2 . b. CH3-CH2-NO2

a. Trimethylamine • b. Methylamine •.. c. C~3~CH2N2~Cl8 • d. CH3-CH2-OH_
c. Ammonia •d. Dimethylamine .. x. Which ~ne· of the· following compounds
v. Which type o_f ~ine does produce N2 contains azo linkage ?
wh~n treated with HNO2 ? a. Hydrazine
a. Primary amine b. Se~ondary amine • b. p-Hydroxyazobenzene
c. Tertiary amine c. N-Nitrosodiethylamine
d. Both primary and secondary amines d. Ethylenediamine ,
vi. Carbylamine test is given by 2~ Answer in one sentence.
a. Primary amine . .
1. Write reaction of . p-toluenesulfonyl
b. Secondary amine chloride with diethylamine.
c. Tertiary amine • ii. • How •many moles o( methylbromide
. .
d. Both secondary and tertiary amines are required to convert ethanamine to
·N, N-dimethyl ethanamine?