31
CHP AMINES
nn monia
whrn N H to
bate
d to CHg amine
cha
platin F>ot
nN- CH-N- cH aiethyl amin cH N-CH tviwut h
Aii nat dunivaluof ammonia obtairud by Lhe
placme nt o Hydogkn atom af ammonua by
alkyl/anyl qroup
Classificotion
aied fanc gup
Aminu
ammonial
-CET
Amines ae tlassifie d into PAimary, Setomdasy,lestiasy
1PAimasy Amine the&e In Cempounde nitogen atom
isattached to one
albyl/aryl
R-NH,
9p
Jhey ake AtpAcitntol by qtheral formula
Jhe urn ctien al qdup amine S
NH,
NH-
CH- NH
Iamine
C CH, NH CH-CHCH,
-
amine n PoPJ amine
mthy thyl
CH-CH-CH CH
NH CH-C NH
1So propyl amin CH
Tert. pr buty
amin
2. Secemd a amines -2 In thuit uempounds, ntroqrn
atom is tahid to alky' laryl geu
TE upnnted by qenenal Pormula R-N-R
Jhe fun ttional 3 p o4 2 amine NH
CH-N-CH CHs N-
H
CH
H
amune ethyl methy mine
dimtthyl
CeH-N-CH C Hs N-CHsF
H
phenyl anman diethyl aminne
Methyl
thes lomPounde,
3.Trtiosu omines In nitrogin
bem do o alkyl(ol groups.
- R- N-R
Rephdanted by GAnutal fovmuda
functi onol qeup 4 3amine-N-
g CH-N-CH C Hs N-CH3
CH CH
ethyl elimethyl
omue
Timuthyl amin
Naing
10
o
ouing
ethey
p amines in IUPAC aML
n UPAC System
eau. Loc
halogensubsh
CH-NH Methanamin
CH CH,-HNH,
popan-amine
CH- CH- CH,NH,
tal
annines
pvefix
system
Poof wDs
+Peot
h amd ace.Lo
ue3d t suffisx+ lnc.
CH-CH, NR
t
ethanamun
CH-CtH-CH propan)amin
C-
NH
CH
GH
CH-NH2
I utihyl p©p an-l-aminee 2, 2 cl imethyl propan-l-amin
CHN-CH
H
CH-CH -CH
H
amune N- mety
N.methyl methan ethtt ethunamin
RW
CH-NCH eH CH,-N-CH
(CH ethanamin
mulhanamne N, N climethyl
N,N dimthy -
NH N- CH
Benzanamn C Hs
CAniline) CH
CN phenyl amin N,NdLimebhy Benzenamin
ATomatie primavy a
ne
of A ineg t e.
Tenesal Methods of PAepaatnen VFE acaba
Co- NH
Bomidle Synthesis
.Hoffmann's nnid
5-CE NH, R-Co-NH
-Er+koH
amuen
ben2oid
hrac. amide is taRale o wth bioine and
In this
qt amine
ele. KOH to
R-Co-N H, +Br,+
R-NH2 +KBr +K,cO3 tH,o
H
+KBY +K,COt H,o
COz
CH- Co-NH +D7+KoH CH NH
Ac tamide + KBr +
C Hs-CO -NH, Br+koH
C6 H5N k,cOgtH,o
Benzami du Reae.beth ollip hati e
Not-By Hoft man Bomid
Can
a romatic amune
CTabriel phbhalimide Synth ess.
O COot
tooH
Phthali c aud
LOl N bose
Phthal antide 3 aud
In thiy tac., phtholamide eacts uth pota4 tum
hydao xide lo fosmnpotassium phthalamide
KOH
H,O for
N-H N-K
CO H,
Potassium phhalamidu w ALa t uth methyl
Lodide (alkyl holidu) to helm n methyl
acid nd
phthalomid.
which on hydao uAs am quves pthalc
muthy amine aEy ne )
CoOH
hy dkolysi
COOH
+CHN
phthalamide potossiu m N-methyl
phthalamide phthalamida
ntteuzation. NS P
ylallipha fie Ami CAn b ppare
Noti- by muthed amins
b pAponid. Onlythis
alliph atic can
amins, 3aminu é aromoduc
decandaAy aminrs Cannet
bppaitd Lhu mthod by
Papekatien
PE
o absob,
Aminu hom Natriu
ahemcaly nut
(Alkyl ayonide)
gcs is Paiid threuugh i
alky
Whin hydseqen
the pAlinu
R-CN
R-CEN
/R
2H-/N
N
Ni cata yst to feim
R-
CH, N H,
H
N
oamin
cyanide
H H
CHCN H/Ni CH CH N
(orC /N CH
C NH,
benzyl omine
hem
Jnom Amidus Huem by hedu
When omidu
(Lithium Alumi nium
cdion
tected i
th nducin q aqunt LiHLH
hydiade) tt undlug oe ducLion
te
koim CeULsponding Phimouy armine
R-CNH, LiAI Hy_ R-C-NH,+ H,O
O H
H
Annidh amint
CHGNH, CH,-CH-NH+H,o
AJH
ethyl amin
Acetanmi de beny
C.HCo-NH,H CeHsCØ-
H NH, H
H, o
ben 2aide
benzyl
amint
Pparalien
Sn+ha
o Amines
SnCl
em
tH)1
Nitno - hydro
Nttro benden
Ccben
Stanniccchleti o
ttaud
uui th uducing aenE
Nhun nitiohnzine
(Ton conc. HC) it undeiget uductten to oim
Aniline
NO Sna oneHC
ON (aroMau c amin
Ariun
enznaminu
lon paY
phopeaties e (ab
m
ty
oh donativn
fAmanas))
Basie Nalu O Amins, Basic
Chemicol
c N-CH3
CH-NH
bascily
NH
basic in natu duu o pArsence olome
a
Amine 3 mn 2amines
Poi Amon g tha amines which Ctrongey
baie than
Streng
than 3 amins.
3 amin ane weakeY bas theun
c
du
o
to
aty gaoups.
E2
stiiehindaan
ollip hatie amunetin the
thu olo wung
Anrang o bosi
incaiasing oidu N+CH
CH,- N-Ch3,CH
CH NH,
CH-N-cH > CH,NH2 > CH N-CH>NR
CHa
Not Aom cadie paim oy curins wLate
olu lo cau2ati
or-
bo thun am mOnia
bs cau&L
bL taure
oheso nan Ce
Lont NH
pcui
NH,
AlkylatiOn
12/8/2
e min
Ns> H
* E,N H-I CH,-Pr>CH,
NSR ccordinau
18- CovaCent Suastes.na
Ahen methyl amine is tacated usith exces o methy)
,iodidtCal kyl halide) hydho qtn atomi
Succesively Per tptacedby methy
tooim mixtiue
timethyl amre
OSe
gvou9 (AlEyqre
a( mtne) {dimethyl amen (9ami n
nd
nally (Quatainany Oumnonmum
auny
cOdidutetyamthy ammonium iodide.
CHN-H +CH-T
Ca Hs
T CH
HT
H
N-CH,
mudhey phinyl amure
ahiLin amine (2 cumine )mthey onlind
CHN -CH, CHHT CH-N-CH amine
H CH dimetny phny
amin 3 amin
3amne
When methy
in the
CH
Acylation
CH-N-H
H
CH
CH-N-CH, CH L, CHNCHs
plicenu
. ek
CH
Pyridin
amine A
P o
CH
C uatesnaiy ammonuum
C-C C,
ticalud
pyridine
H
ueith
torimithy
Sclt
aletyl Chleiid
Cotalyct to
pnedid.
pm
MMONiun
N autamide .
CH-NH
methyl
+ CuFco CtH,Pyide CH NH=Co-CH, + Ha
PasaLckane,
Dole 60D
Cc Hs NH
+ c-co-CH Pyridi CcHs -N- Co-CHs
H
oaCitamide
Anuline N-phAyl
ougs kech act
geinst 4ep anti bl otia.
benzyolatien
(Schotten bàhomann's Rra.
CHs CooOH
]
Anilin Racts uith berryot chlovidk in tu paeience
Sodium hydaoaidu to om
Nphtnyl btn2amid
Co CO-Clban2oie ahlonl
CaHsN-H He NaOH sHNH-Co-l
+C -CO-C.chlide +HCL
H Aniline Benzoyl N-pheny
benzamnde
CHN-H +C- Co-C He NaoOH CHN- H
CO-C Hs+ HC
Nmithul ke.o2amide
Carrbenytabmu
Rrac. IFE) rgAr
Canbylamine
+ +koHuhgdiet
nlogrn
R-NC +KC Ho N
R NH CHC NC
CHO,+KOHas
Rd C
K
C
-c cith th a muxtu
o
Whun amine tcatud tooim
teckrs pla C
kon, zeac. chleiide and water.
chloroeym cumine), potastium
(Cauby|
+ KCl + HO
isocyanude
+kOH R NCNC
R-NH,+ CHCI
KCL+H, O +
CH-N H, CHCl+KOH Co Hs-NC +K Cu H,O
Ca Hs N H, +CHct +KOH
ichloro
alkatinMethan
Acac isuaol aßa Fest
Caibyl amune
Not
2
s
& 3 amint dou
pimay uminus,Cboth cliphatie
hot cng we caby
in amune Aiae.
CYomatic)
amin SAac.
inteimidiats Calbyl
3.heAxactiondichleio mnethy un 18/9/22
is CC,
Nitreus acid (viFE)X ous a
with HNO icoid-O
Roc
Na CL +HNO, HNo,
NO,+HCL
Na il)
Sodium ia2cnum
nirite CH,-OH+N, +H,O
cH-NH O =N-O-H N=O
-N=o C-NEN-
Saia
ON-6H+He cH sfaba
O= N -H i nut
auphatic dianondum
niauve
NO nirozonuum on uact3 Cuith at
amine eez cert
Aiphatie ond oll.HCl ss)
NN C Soum nitrih altehel
et ce'Uuspondung
ahd wate
O-5C to foumn nit aogar
wth ibirati on of
Na NO, + HCL O-5C NaCl +HNO
N, 1t
CH NH, + H No, 5 cHOH H,Op
CHCH-OH +N+H,o
Ho-N= o
No CH-CHNA HNo,
[HO-N-Oo]
Diazotization [HNo,](VIFE) **
When auematic amini ttoatud uith C mmiuu
Sodium niti and hydho chlovic thisaid O-5'c te i a
Henu, Lac. i6 CaUd
blnzine diazOnium chletid
diazetizaisn.
NaNO, HC o-5C Natl +HNO,
+0F N-O H +HC 6. HsN-N-a
aHs N +2H,0
Nau Auiphatic dizonium Cemp eunds aR qu h untta
Stabl
etasuy undage hydo yais foim coespending
alcshob WhLas, aomatic diazoium thloiidu quit
to
a
RLac o
NENa
Amomatic
C
Cu
Cu
Dizonum
r+HBY
N
Comc HC
Chleiidr
N
NSR
ith Cull
Cull
Cupous
C
Cu
c
Cu,
chloid
CN+ HCN San dcoppA Salc
phiny ayanide
Nhun benzenn dizonium ehlorida wth uupreuy -
aste foim chloo
Chloride in Conc. Hè
eh Hydrochlorie
benzen aand nitrogn, thiu Nnac. is colleo Saandmneyer's
-
Reaetion
ON=N-a CucL+Ha
0-5°C +N
Cat cu
Reac sith Cu br
benzen dizo num chlotidu Kea ct tth
uprous bro mids
in HBr (hydsogen bromidi) to foim bro mo benzena,hu
HAaL.iS aulso caud Sandmyer Reac.
N=N-C CubY + HB Na
wtth cuphous canide
Benzen dironium chleiidu
in potasiium founidn to om
uact with
cyanobunzin
p hou
phenyl
anide
cAjcridu)
kncwr
O+
This Sandlmyer's Reac
CN KOH
CuCN + HEL,
[oFN=N N,
kT
with
Dn2tn A7 Onum cheiidi AO u i th pot a3sium
kC
Leelm iodo benze and ritrogtn &
fodidu
NN-C KT O - N +K
uwith Pt
ohoai c acid C Flouro borie ctid)
benun divou un
chlorik eact wi th leuro boxic aid to foim
to
DOEN, HCL, boxon bri
flowi de
Flouro benzen H
NN CL
A
Fu
[o + N,t Ha+ BF
H BF
ith HPO, (hy
B F
phosp horou
aid ) e
Is22
X: X
2p]
P
HPO
2s*3p 3
3)+
3p
4(-2) O Fab
Layt ene,.qu
to baale Lerd
phosphov
0.S
a cid
Tedue
3+
++3,+S
Ou
hypo
+5
(-8) =o
ma.O.s
HPOy-
ocidaliom
casi
l
ic
eteta
y O duinj jer
0ioAzirt
oen M PO HPO
1
.
0.s
o+
1f
oudadiom,
can
H,D
undug
Hboth
POg
H,PO,2H
- asi
Ozidoion
CH N
d tcn.
NC
veduion uith
ben 2enu dienium chlortd undego te foim benzene 4
acid (Redncing agint)
hyPopho sp hovous aid
Sed to phosphorous
tse Oridi
ANEN7aHP0,tH,°,
2 CHJ
o+ N,+ Ha+ hPO
LHPO, + H,O HPO, 2lHJ
134/8/22
with satin th s
chlerid wa mmd usi
When Benren
waa,haadusn
wih
dilonium
hydroysis
it undogass Ni
Chlesidk
troG o
toform phenel
E tet hydo n n
N=NT H,o OH HCL
wom + N,t
H OH
Couplinq Reac.
(Leput
Dtnzine
Htac. 4e fa.
azobenzin
fueoivg
dia1onu
o
an h
uwith
sae.
dizonun
BenztnCao
Levida
phunol
ohars
undsngoes CdpLn a
to form paohydoy
N ic
hlorid
aklosbes t
.
ON=N'-a +H-(OOH O-N=NO)n
HCL
para hydvo
azo ben
TLd ostalin,
Not N=a-C ovany
aio Compourds
C-N=N-
dia 20
eac.
ben tnu dizorium choride undesgos Coupkng
atrth Arnilin to fom pasa amino a20 benuna
CRrlina &phenol eati undngo ECR
N=N-CL +H-ON" HO N=N N,
Not Cull rHH
CuBrHDy
NN-P- CuCN +KCN CN
KT
HBFy
HPO+H,o
HO
TOH
CUnboyhkilie ub.Pua c)
romatie
N-He
Substitudion
done e
Reac. of hniine
dunsi y in ortho Por
.X
HEledbophiie Subs. Reac (NH, uoths
di recing qropl)
pa
HNO HNO
NO
o.na
5D
man
Ntthatien
loo of anilinui undfPtDni n be toms
NE HNO3 Meta
H-N Whun ati aniline statid with nitYaking
MituUr (conc HNO *Conc. H,SOu) to form
a mextun Ovtho -huto aniin muta nuto
anui ne pcAa nito oniline
NH
NH H SO -NO
HNo > (rminor)
OH N NH
ONo Cmajor
NH
Cmajor) aloc
Prepovua en
Subski
o Pa
tut bulk
nitao aniin X*X guse
toup steic hiudhena
NH NH ch dulo cali zati
tCL CO-CH bLocEing
.
Acy lati on Nitration hydro ysis
N-phenyl acutomid chloride in
chloide in
with
usith aclty
acttyl
is totud
When oaniline ko fotm
thephasena o PILdnu catalyst
acetaumide
(N- phany ntro actanud
Acetani lidu p oRa- is
di On nutaalien hoRms nitro anini
ACetounii On hy dao iis P H:OA
p-nito acutaliido NH CO-CH
foRmad
NH-CO-CH
[O).HNOt
H,So
H-N-H
PYTideres
HNO
+Cl-CO-CH Acetannide
NO NO
NH |Hgdrolysis
H O H
CH 0OH [oJ
NO
btLominatien-
uth Bhomin w ot ko ke*Lm
Hniline NoLdts
2,H,6- thibromo ani in
NH
H
NH Br + HB
-H BrH,O 2,,6 tinltro aniline
o mo Anilin
hLpaotion p-
Itinveluu the fellewing Sup
Btp Ahiline u tenvetud to Acetaneide
is bionatud bro munt in
bromune
2 Stp Autaniid
acuc acid
using
36 Clap: p-bromo acitanii on hydaoky d sis to
get
& acetic aud
Pbromo aniU NH
CO-CH,
H-N-H NH-CO-CHs atid
+C-Co-CH, Pyldi,
-Hc O
Acteuni
Bz/ncetie
lide Br
P-bromoa utarniide
26l8lo2
Sulp honaion
Antline hLacts wth COnc. H,SOy tefam
Sulphanilic
atid (p- amino ben2tne stulphenic acid) It existr as zuitor ion
dipala on) (+ve t-ve tepaatud by Carbon atom
NH NH otho do esn
HSOy NH becaue t1
Ytnct
H OH SoH
stphonie
acd
SoH SO
2ite iemn
VIFE
Hinsbng's uaqint t tst (Tut tor aines)
Rac. ith benun ch
SLilpho ny loride
Co HsSO - CI
CH-5o,-NGCh, S in NaOH
aCidicctis solve
Hs S0,-N-CH3,insolub
cH
e in NaOH ives ppE.
Hei
eagnt
nsbng 1omin 2 amin 3 amune
HomoqRnnsus
Amins benun PCpiteukr No reac.
Soln.
Sulphoyl ehloid|Ccasaln
NaOH
) ts Hermed
