Glucosides &amp Tannins (Part-6)

Glycosides & Tannins Glycosides & Tannins
99//23 23//2011 2011 1 1

Dr. Harish & Dr. Harish & Purvi Purvi Kakrani Kakrani
Glycosides Glycosides
.4sides .4nsist 41 a sugar residue .4vaent .4sides .4nsist 41 a sugar residue .4vaent
b4und t4 a di11erent stru.ture .aed the b4und t4 a di11erent stru.ture .aed the aglvcone. aglvcone.
%he sugar residue is in its ..i. 14rm and the %he sugar residue is in its ..i. 14rm and the
p4int 41 atta.hment is the hdr4 gr4up 41 the p4int 41 atta.hment is the hdr4 gr4up 41 the
hemia.eta 1un.ti4n. hemia.eta 1un.ti4n.
%he sugar m4iet .an be i4ined t4 the ag.4ne in %he sugar m4iet .an be i4ined t4 the ag.4ne in
vari4us was: vari4us was:
1. 1. Ogen Ogen glvcoside) glvcoside)
2. 2. Suphur Suphur $ $ glvcoside) glvcoside)
3. 3. Nitr4gen Nitr4gen glvcoside) glvcoside)
4. 4. Carb4n ( Carb4n (CC- -glvcoside) glvcoside)
9 9//23 23//2011 2011 2 2 Dr. Harish & Purvi Kakrani Dr. Harish & Purvi Kakrani
-- lvcosides lvcosides and and .. glvcosides glvcosides are distinguished are distinguished
b the .4n1igurati4n 41 the hemia.eta hdr4 b the .4n1igurati4n 41 the hemia.eta hdr4
gr4up. gr4up.
%he mai4rit 41 natura %he mai4rit 41 natura 4..urring g.4sides 4..urring g.4sides
are are .. g.4sides. g.4sides.
lvcosides lvcosides .an easi be .eaved int4 sugar .an easi be .eaved int4 sugar
and ag.4ne b hdr4sis with a.ids 4r and ag.4ne b hdr4sis with a.ids 4r
enzmes. enzmes.
Am4st a pants that .4ntain g.4sides as4 Am4st a pants that .4ntain g.4sides as4
.4ntain enzmes that bring ab4ut their hdr4sis .4ntain enzmes that bring ab4ut their hdr4sis
( (glvcosidases glvcosidases. .
.4sides are usua s4ube in water and in .4sides are usua s4ube in water and in
p4ar 4rgani. s4vents, whereas ag.4nes are p4ar 4rgani. s4vents, whereas ag.4nes are
n4rma ins4ube 4r 4n sight s4ube in n4rma ins4ube 4r 4n sight s4ube in
water. water.
It is 41ten ver di11i.ut t4 is4ate inta.t It is 41ten ver di11i.ut t4 is4ate inta.t
g.4sides be.ause 41 their p4ar .hara.ter. g.4sides be.ause 41 their p4ar .hara.ter.
Man imp4rtant drugs are g.4sides and their Man imp4rtant drugs are g.4sides and their
pharma.44gi.a e11e.ts are arge determined pharma.44gi.a e11e.ts are arge determined
b the stru.ture 41 the ag.4ne. b the stru.ture 41 the ag.4ne.
%he term 'g.4side' is a ver genera 4ne whi.h %he term 'g.4side' is a ver genera 4ne whi.h
embra.es a the man and varied .4mbinati4ns embra.es a the man and varied .4mbinati4ns
41 sugars and ag.4nes. 41 sugars and ag.4nes.
M4re pre.ise terms are avaiabe t4 des.ribe M4re pre.ise terms are avaiabe t4 des.ribe
parti.uar .asses. S4me 41 these terms re1er t4: parti.uar .asses. S4me 41 these terms re1er t4:
1. 1. the sugar part the sugar part 41 the m4e.ue (e.g. 41 the m4e.ue (e.g. glucoside glucoside. .
2. 2. the ag.4ne the ag.4ne (e.g. anthraquin4ne. (e.g. anthraquin4ne.
3. 3. the phsi.a 4r pharma.44gi.a pr4pert the phsi.a 4r pharma.44gi.a pr4pert (e.g. (e.g.
sap4nin sap4nin " "s4ap s4ap ike ike , .ardia. , .ardia. " "having an a.ti4n 4n having an a.ti4n 4n
the heart the heart . .
M4dern sstem 41 naming g.4sides using the M4dern sstem 41 naming g.4sides using the
terminati4n ' terminati4n ' 4side' (e.g. senn4side. 4side' (e.g. senn4side.
Ath4ugh g.4sides 14rm a natura gr4up in that Ath4ugh g.4sides 14rm a natura gr4up in that
the a .4ntain a sugar unit, the ag.4nes are 41 the a .4ntain a sugar unit, the ag.4nes are 41
su.h varied nature and .4mpeit that g.4sides su.h varied nature and .4mpeit that g.4sides
var ver mu.h in their phsi.a and .hemi.a var ver mu.h in their phsi.a and .hemi.a
pr4perties and in their pharma.44gi.a a.ti4n. pr4perties and in their pharma.44gi.a a.ti4n.
99//23 23//2011 2011 6 6 Dr. Harish & Purvi Kakrani Dr. Harish & Purvi Kakrani
Anthracene glycosides Anthracene glycosides
Anthracene
A number 41 g.4sides in whi.h the ag.4nes are A number 41 g.4sides in whi.h the ag.4nes are
anthra.ene derivatives 4..ur as the pharma.44gi.a anthra.ene derivatives 4..ur as the pharma.44gi.a
a.tive .4nstituents 41 severa .atharti.s 41 pant 4rigin; a.tive .4nstituents 41 severa .atharti.s 41 pant 4rigin;
e.g. .as.ara, rhubarb, a4e and senna. e.g. .as.ara, rhubarb, a4e and senna.
%hese anthra.ene g.4sides are s4metimes re1erred t4 as %hese anthra.ene g.4sides are s4metimes re1erred t4 as
the anthraquin4ne g.4sides 4r the anthrag.4sides. the anthraquin4ne g.4sides 4r the anthrag.4sides. 9 9//23 23//2011 2011 7 7 Dr. Harish & Purvi Kakrani Dr. Harish & Purvi Kakrani
%hese anthraquin4ne derivatives are g.4sides, %hese anthraquin4ne derivatives are g.4sides,
41ten gu.4sides 4r rhamn4sides. 41ten gu.4sides 4r rhamn4sides.
%he presen.e 41 the sugar residue is a prerequisite %he presen.e 41 the sugar residue is a prerequisite
14r the pharma.44gi.a e11e.ts. 14r the pharma.44gi.a e11e.ts.
Anthraquin4nes are .44red substan.es and man Anthraquin4nes are .44red substan.es and man
41 them are used te.hni.a as des e.g. aizarin. 41 them are used te.hni.a as des e.g. aizarin.
Redu.ed 14rms 41 anthraquin4nes, whi.h ehibit Redu.ed 14rms 41 anthraquin4nes, whi.h ehibit
ket4 ket4 en4 taut4merism, are 41ten en.4untered. en4 taut4merism, are 41ten en.4untered.
%he anthra.ene derivatives 4..ur in vegetabe %he anthra.ene derivatives 4..ur in vegetabe
drugs in di11erent 14rms at di11erent 4idati4n drugs in di11erent 14rms at di11erent 4idati4n
eves; ike anthraquin4nes, anthr4nes, anthran4s, eves; ike anthraquin4nes, anthr4nes, anthran4s,
4r 4anthr4nes. 4r 4anthr4nes.
Interrelationship of anthraquinone derivatives Interrelationship of anthraquinone derivatives
O
O
OH
Anthrone (keto form)
Anthranol (enol form)
Anthraquinone
O
O
Dianthrone
O
H OH
Oxanthrone
A B C
1
2
3
4 5
6
7
8
9
10
4 H
2 H
2 H
Taut.
%hese anthra.ene .4mp4unds 4..ur in these drugs 4r pant %hese anthra.ene .4mp4unds 4..ur in these drugs 4r pant
materias in s4me .ases as the ag.4nes 41 materias in s4me .ases as the ag.4nes 41 g.4sides g.4sides (e.g. (e.g.
1ranguin, and in 4ther .ases as the ag.4nes 41 1ranguin, and in 4ther .ases as the ag.4nes 41 CC g.4sides g.4sides
(e.g. a4in. (e.g. a4in.
Biosvnthesis Biosvnthesis; natura anthraquin4nes are snthesized either via ; natura anthraquin4nes are snthesized either via
the a.etate the a.etate ma4nate pathwa (ike the medi.ina imp4rtant ma4nate pathwa (ike the medi.ina imp4rtant
purgative anthraquin4nes, 4r the are derived 1r4m shikimate purgative anthraquin4nes, 4r the are derived 1r4m shikimate
and meva4nate (ike aizarin. and meva4nate (ike aizarin.
O
O
OH
OH
AIizarin
OH O OH
HO
O
CH
3
FranguIa emodin
A Anthraquinones A Anthraquinones
Ath4ugh anthraquin4ne is n4t used etensive in Ath4ugh anthraquin4ne is n4t used etensive in
medi.a pra.ti.e, it is the starting materia 14r the medi.a pra.ti.e, it is the starting materia 14r the
preparati4n 41 severa sntheti. aatives and preparati4n 41 severa sntheti. aatives and
represent the basi. stru.ture 41 a number 41 represent the basi. stru.ture 41 a number 41
imp4rtant aatives and destu11s. imp4rtant aatives and destu11s.
Borntrager Borntragers test s test is 41ten used 14r their dete.ti4n. is 41ten used 14r their dete.ti4n.
%he derivatives 41 anthraquin4ne present in %he derivatives 41 anthraquin4ne present in
purgative drugs ma be dihdr4 phen4s su.h as purgative drugs ma be dihdr4 phen4s su.h as
.hrs4phan4, trihdr4 phen4s su.h as em4din .hrs4phan4, trihdr4 phen4s su.h as em4din
4r tetrahdr4 phen4s su.h as .armini. a.id. 4r tetrahdr4 phen4s su.h as .armini. a.id.
O
O
Anthraquinone
OH O OH
O
CH
3
Chrysophanol
OH O OH
HO
O
CH
3
Emodin
HO
OH
OH
O
O
CH
3
OH
COOH
O
HO
HO
OH
OH
Carminic Acid
B Anthrones & Anthranols B Anthrones & Anthranols
%hese redu.ed anthraquin4ne derivatives 4..ur %hese redu.ed anthraquin4ne derivatives 4..ur
either 1ree 4r .4mbined as g.4sides. either 1ree 4r .4mbined as g.4sides.
%he are is4meri. and 4ne ma be partia %he are is4meri. and 4ne ma be partia
.4nverted t4 the 4ther in s4uti4n. .4nverted t4 the 4ther in s4uti4n.
Anthran4s are .4nverted up4n 4idati4n int4 Anthran4s are .4nverted up4n 4idati4n int4
anthraquin4nes. Oidati4n takes pa.e in the .rude anthraquin4nes. Oidati4n takes pa.e in the .rude
drug during st4rage espe.ia i1 p4wdered. drug during st4rage espe.ia i1 p4wdered.
Schonteten Schontetens test s test is 41ten used 14r anthran4s is 41ten used 14r anthran4s
(green 1u4res.en.e. (green 1u4res.en.e.
Anthran4s and anthr4nes are the main .4nstituents Anthran4s and anthr4nes are the main .4nstituents
41 .hrsar4bin, a miture 41 substan.es. 41 .hrsar4bin, a miture 41 substan.es.
OH OH OH
CH
3
OH O OH
CH
3
rysarobin
(1,8-dihydroxy-3-methyl-9-anthrone; 3-methyl-1,8,9-anthracenetriol)
C Oxanthrones C Oxanthrones
OH O OH
H OH
%hese are intermediate pr4du.ts between %hese are intermediate pr4du.ts between
anthraquin4nes and anthran4s. anthraquin4nes and anthran4s.
%he give anthraquin4nes 4n 4idati4n with %he give anthraquin4nes 4n 4idati4n with
hdr4gen per4ide. hdr4gen per4ide.
An 4anthr4ne has been rep4rted as a .4nstituent An 4anthr4ne has been rep4rted as a .4nstituent
41 41 cascara cascara bark. bark.
D Dianthrones D Dianthrones
O OH
COOH
COOH
O
.-D-glucoseO
.-D-glucoseO OH
Sennosides
%hese are .4mp4unds derived 1r4m %hese are .4mp4unds derived 1r4m
tw4 anthr4ne m4e.ues, whi.h ma tw4 anthr4ne m4e.ues, whi.h ma
be identi.a 4r di11erent. be identi.a 4r di11erent.
%he are imp4rtant ag.4nes in %he are imp4rtant ag.4nes in
spe.ies 41 spe.ies 41 Cassia Cassia, , Rheum Rheum and and
Rhamnus Rhamnus..
One 41 the best kn4wn is senn4side One 41 the best kn4wn is senn4side
derived 1r4m tw4 m4e.ues 41 derived 1r4m tw4 m4e.ues 41
gu.4se and tw4 m4e.ues 41 rhein gu.4se and tw4 m4e.ues 41 rhein
anthr4ne. anthr4ne.
On hdr4sis, senn4side ieds the On hdr4sis, senn4side ieds the
ag.4ne sennidin. ag.4ne sennidin.
E Aloin E Aloin- -type or type or CC- -glycosides glycosides
A4in (Barba4in was 4btained A4in (Barba4in was 4btained
1r4m spe.ies 41 1r4m spe.ies 41 Aloe Aloe..
It is str4ng resistant t4 n4rma It is str4ng resistant t4 n4rma
a.id hdr4sis. a.id hdr4sis.
In a4in, the sugar is i4ined t4 In a4in, the sugar is i4ined t4
ag.4ne with a dire.t C ag.4ne with a dire.t C C inkage C inkage
(a (a CC g.4side. g.4side.
%w4 a4ins (A and B are kn4wn %w4 a4ins (A and B are kn4wn
and arise 1r4m the .hira .entre at and arise 1r4m the .hira .entre at
CC 10 10. .
OH O OH
OH
O
HO
OH
OH
HO
AIoin
22 Saponin glycosides Saponin glycosides
A gr4up 41 pant g.4sides kn4wn as sap4nins A gr4up 41 pant g.4sides kn4wn as sap4nins
share in varing degrees, tw4 .4mm4n share in varing degrees, tw4 .4mm4n
.hara.teristi.s: .hara.teristi.s:
(a (a %he 14am in aque4us s4uti4n. %he 14am in aque4us s4uti4n.
(b (b %he .ause haem4sis 41 red b44d .es. %he .ause haem4sis 41 red b44d .es.
%he ag.4nes 41 the sap4nins are .4e.tive %he ag.4nes 41 the sap4nins are .4e.tive
re1erred t4 as re1erred t4 as Sapogenins Sapogenins %he m4re p4is4n4us %he m4re p4is4n4us
sap4nins are 41ten .aed sap4nins are 41ten .aed Sapotoxins Sapotoxins
Pant materias .4ntaining sap4nins have 4ng Pant materias .4ntaining sap4nins have 4ng
been used in man parts 41 the w4rd 14r their been used in man parts 41 the w4rd 14r their
detergent pr4perties 14r eampe, in Eur4pe, the detergent pr4perties 14r eampe, in Eur4pe, the
r44t 41 r44t 41 $aponaria officinalis $aponaria officinalis (Fam. (Fam.
Carvophvllaceae Carvophvllaceae and and in S4uth Ameri.a, the bark in S4uth Ameri.a, the bark
41 41 Quillaia saponaria Quillaia saponaria (Fam. (Fam. Rosaceae). Rosaceae). Su.h Su.h
pants .4ntain a high per.entage 41 the g.4sides pants .4ntain a high per.entage 41 the g.4sides
kn4wn as sap4nins (Latin kn4wn as sap4nins (Latin $apo $apo, means S4ap , means S4ap
whi.h are .hara.terized b their pr4pert 41 whi.h are .hara.terized b their pr4pert 41
pr4du.ing a 1r4thing aque4us s4uti4n. pr4du.ing a 1r4thing aque4us s4uti4n.
Properties Properties: :
Sap4nins 14rm .44ida s4uti4n in water Sap4nins 14rm .44ida s4uti4n in water
(hdr4phii. .44ids whi.h 1r4ths up4n shaking. (hdr4phii. .44ids whi.h 1r4ths up4n shaking.
%hese substan.es m4di1 and 4wer the sur1a.e %hese substan.es m4di1 and 4wer the sur1a.e
tensi4n and there14re 14am when shaken. %his has tensi4n and there14re 14am when shaken. %his has
ed t4 their use t4 in.rease the 14aming 41 beer. ed t4 their use t4 in.rease the 14aming 41 beer.
Pra.ti.a industria appi.ati4ns 41 sap4nins Pra.ti.a industria appi.ati4ns 41 sap4nins
in.ude their use in .eaning industria equipment in.ude their use in .eaning industria equipment
and 1ine 1abri.s and as p4wer1u emusi1iers 41 and 1ine 1abri.s and as p4wer1u emusi1iers 41
.ertain resins, 1ats and 1ied 4is. .ertain resins, 1ats and 1ied 4is.
In genera, the have a bitter, a.rid taste and In genera, the have a bitter, a.rid taste and
drugs .4ntaining them are usua sternutat4r drugs .4ntaining them are usua sternutat4r
( (causing or producing sneezing causing or producing sneezing and irritating t4 the and irritating t4 the
mu.4us membranes 41 ees and n4se. mu.4us membranes 41 ees and n4se.
Chara.teristi. 14r a sap4nins is their abiit t4 Chara.teristi. 14r a sap4nins is their abiit t4
.ause haem4sis 41 red b44d .4rpus.es and t4 .ause haem4sis 41 red b44d .4rpus.es and t4
destr4 them. When inie.ted int4 the b44d destr4 them. When inie.ted int4 the b44d
stream, the are high t4i.. stream, the are high t4i..
When taken b m4uth, Sap4nins are When taken b m4uth, Sap4nins are
.4mparative harmess, being n4t abs4rbed 1r4m .4mparative harmess, being n4t abs4rbed 1r4m
the intestina tra.t. the intestina tra.t. Sarsaparilla Sarsaparilla, 14r eampe, is , 14r eampe, is
ri.h in sap4nins but is wide used in the ri.h in sap4nins but is wide used in the
preparati4n 41 n4n preparati4n 41 n4n- -a.4h4i. beverages. a.4h4i. beverages.
Sap4nins are t4i. espe.ia t4 .4d Sap4nins are t4i. espe.ia t4 .4d b44ded b44ded
animas e.g. 1r4gs. Man are used as 1ish animas e.g. 1r4gs. Man are used as 1ish p4is4ns. p4is4ns.
%he actual cause of the haemolvsis %he actual cause of the haemolvsis: :
%he red b44d .es .arr ster4s in their %he red b44d .es .arr ster4s in their
membranes, and when br4ught int4 .4nta.t with membranes, and when br4ught int4 .4nta.t with
sap4nins, the ster4s 41 the RBCs are pre.ipitated sap4nins, the ster4s 41 the RBCs are pre.ipitated
and the .44ida .hemi.a pr4perties 41 the and the .44ida .hemi.a pr4perties 41 the
membrane are s4 atered as t4 give hem4g4bin membrane are s4 atered as t4 give hem4g4bin
passage t4 the surr4unding medium. passage t4 the surr4unding medium.
Sap4nins have a high m4e.uar weight and their Sap4nins have a high m4e.uar weight and their
is4ati4n in a state 41 purit presents s4me is4ati4n in a state 41 purit presents s4me
di11i.uties. di11i.uties.
Structure of Saponins Structure of Saponins: :
A..4rding t4 the stru.ture 41 the ag.4ne 4r A..4rding t4 the stru.ture 41 the ag.4ne 4r
sap4genin, tw4 kinds 41 sap4nin are re.4gnized: sap4genin, tw4 kinds 41 sap4nin are re.4gnized:
1. 1. %he ster4ida tpe (.4mm4n tetra..i. %he ster4ida tpe (.4mm4n tetra..i.
triterpen4ids, C triterpen4ids, C 27 27. .
2. 2. %he triterpen4id tpe (penta..i. triterpen4ids, %he triterpen4id tpe (penta..i. triterpen4ids,
CC 30 30. .
B4th 41 these have a g.4sida inkage at C B4th 41 these have a g.4sida inkage at C 3 3
and have a .4mm4n bi4sntheti. 4rigin via and have a .4mm4n bi4sntheti. 4rigin via
meva4ni. a.id and is4prene units. meva4ni. a.id and is4prene units.
Steroid skeleton
3
25
26
27
1
18
19
21
17
Pentacyclic triterpenoid skeleton
23 24
25 26
27
28
29 30
3
1
A Steroidal saponins A Steroidal saponins
%he ster4ida sap4nins are ess wide distributed %he ster4ida sap4nins are ess wide distributed
in nature than the penta..i. triterpen4id tpe. in nature than the penta..i. triterpen4id tpe.
Ster4ida sap4nins are 41 great pharma.euti.a Ster4ida sap4nins are 41 great pharma.euti.a
imp4rtan.e be.ause 41 their reati4nship t4 imp4rtan.e be.ause 41 their reati4nship t4
.4mp4unds su.h as the se h4rm4nes, .4rtis4ne, .4mp4unds su.h as the se h4rm4nes, .4rtis4ne,
diureti. ster4ids, vitamin D and the .ardia. diureti. ster4ids, vitamin D and the .ardia.
g.4sides. g.4sides.
Eampes: Di4sgenin ( Eampes: Di4sgenin (ioscorea svlvatica ioscorea svlvatica, ,
Sarsap4genin ( Sarsap4genin ($milax $milax sp.. sp..
B Pentacyclic triterpenoid saponins B Pentacyclic triterpenoid saponins
%riterpen4id sap4nins m be .assi1ied int4 three %riterpen4id sap4nins m be .assi1ied int4 three
gr4ups represented b gr4ups represented b -- amrin, amrin, .. amrin and upe4. amrin and upe4.
Eampes: Primuagenin ( Eampes: Primuagenin (!rimula !rimula sp., Quiaia. a.id sp., Quiaia. a.id
( (Quillaia saponaria Quillaia saponaria and .rrhetini. a.id and .rrhetini. a.id
( (lvcvrrhiza lvcvrrhiza sp.. sp..
E
D
-Amyrin .Amyrin
Lupeol
20
19
17 13
14
33 Coumarin glycosides Coumarin glycosides
O O
1
2
3
4
5
6
7
8
Coumarin
(Benz4-pr4ne
%he .4umarins are shikimate %he .4umarins are shikimate derived metab4ites. derived metab4ites.
%he mai4rit 41 the .4umarins are 4genated at p4siti4n %he mai4rit 41 the .4umarins are 4genated at p4siti4n
CC77..
C4umarins have a imited distributi4n in the pant C4umarins have a imited distributi4n in the pant
kingd4m and have been used t4 .assi1 pants a..4rding kingd4m and have been used t4 .assi1 pants a..4rding
t4 their presen.e (.hem4ta4n4m. t4 their presen.e (.hem4ta4n4m.
C4umarins are .4mm4n 14und in the pant C4umarins are .4mm4n 14und in the pant
1amiies 1amiies piaceae piaceae, , Rutaceae Rutaceae, , steraceae steraceae and and
Fabaceae. Fabaceae.
S4me .4umarins are S4me .4umarins are phvtoalexins phvtoalexins and are and are
snthesized snthesized de novo de novo b the pant 144wing b the pant 144wing
in1e.ti4n b a ba.terium 4r 1ungus. in1e.ti4n b a ba.terium 4r 1ungus.
Phvtoalexins Phvtoalexins: : an 41 a gr4up 41 .4mp4unds an 41 a gr4up 41 .4mp4unds
14rmed in pants in resp4nse t4 1unga in1e.ti4n, 14rmed in pants in resp4nse t4 1unga in1e.ti4n,
phsi.a damage, .hemi.a iniur, 4r a phsi.a damage, .hemi.a iniur, 4r a
path4geni. pr4.ess. Pht4aeins inhibit 4r path4geni. pr4.ess. Pht4aeins inhibit 4r
destr4 the invading agent. destr4 the invading agent.
%hese pht4aeins are %hese pht4aeins are
br4ad antimi.r4bia; 14r br4ad antimi.r4bia; 14r
eampe, eampe, scopoletin scopoletin is is
snthesized b the p4tat4 snthesized b the p4tat4
$olanum tuberosum) $olanum tuberosum)
144wing 1unga in1e.ti4n. 144wing 1unga in1e.ti4n.
Khellin Khellin is an is an isocoumarin isocoumarin
(chromone) (chromone) natura pr4du.t natura pr4du.t
1r4m 1r4m mmi Jisnaga mmi Jisnaga
(Apia.eae and has a.tivit as (Apia.eae and has a.tivit as
a spasm4ti. and vas4diat4r. a spasm4ti. and vas4diat4r.
O O HO
H
3
CO
Scopoletin
O
O
CH
3
OCH
3
OCH
3
O
Khellin
It has 4ng been kn4wn that It has 4ng been kn4wn that
animas 1ed sweet .4ver animas 1ed sweet .4ver
elilotus officinalis. elilotus officinalis.
Faba.eae die 1r4m Faba.eae die 1r4m
haem4rrhaging. %he haem4rrhaging. %he
p4is4n4us .4mp4und p4is4n4us .4mp4und
resp4nsibe 14r this adverse resp4nsibe 14r this adverse
e11e.t was identi1ied as e11e.t was identi1ied as
dicoumarol dicoumarol..
A number 41 .4mp4unds have A number 41 .4mp4unds have
been snthesized based 4n the been snthesized based 4n the
di.4umar4 stru.ture, e.g. di.4umar4 stru.ture, e.g.
warfarin warfarin, whi.h is wide , whi.h is wide
used as anti.4aguant. used as anti.4aguant.
O O
OH
CH
3
O
arfarin
O O
OH OH
O O
DicoumaroI
%he ps4raens are .4umarins %he ps4raens are .4umarins
that p4ssess a 1uran ring and that p4ssess a 1uran ring and
are s4metimes kn4wn as are s4metimes kn4wn as
furanocoumarins furanocoumarins. e.g. . e.g.
ps4raen and bergapten. ps4raen and bergapten.
%hese .4mp4unds ma be %hese .4mp4unds ma be
pr4du.ed b the pant as a pr4du.ed b the pant as a
pr4te.ti4n me.hanism against pr4te.ti4n me.hanism against
high d4ses 41 sunight and high d4ses 41 sunight and
s4me .4umarins are s4me .4umarins are
14rmuated int4 suns.reens 14rmuated int4 suns.reens
and .4smeti.s 14r this and .4smeti.s 14r this
purp4se. purp4se.
O
O
O
ergapten
OCH
3
O
O
O
PsoraIen
44 Flavonoid glycosides Flavonoid glycosides
Biosynthesis: Biosynthesis:
1av4n4ids are pr4du.ts 1r4m a .innam4 1av4n4ids are pr4du.ts 1r4m a .innam4 C4A C4A
(C (C
66
CC
33
, pre.urs4r 1r4m the shikimate pathwa , pre.urs4r 1r4m the shikimate pathwa
starter unit, with .hain etensi4n using three starter unit, with .hain etensi4n using three
m4e.ues 41 ma4n m4e.ues 41 ma4n C4A. C4A.
Fav4n4ids are there14re 41 mied bi4snthesis, Fav4n4ids are there14re 41 mied bi4snthesis,
.4nsisting 41 units derived 1r4m b4th shikimate .4nsisting 41 units derived 1r4m b4th shikimate
and a.etate pathwas. and a.etate pathwas.
%he triketide starter unit underg4es ..izati4n b %he triketide starter unit underg4es ..izati4n b
the enzme .ha.4ne snthase t4 generate the the enzme .ha.4ne snthase t4 generate the
chalcone chalcone gr4up 41 1av4n4ids. C.izati4n .an gr4up 41 1av4n4ids. C.izati4n .an
then 4..ur t4 give a pran4ne ring .4ntaining then 4..ur t4 give a pran4ne ring .4ntaining
flavanone flavanone nu.eus, whi.h .an either have the C nu.eus, whi.h .an either have the C22
CC3 3 b4nd 4idized (unsaturated t4 give the b4nd 4idized (unsaturated t4 give the
flavones flavones 4r be hdr4ated at p4siti4n C 4r be hdr4ated at p4siti4n C3 3 41 the 41 the
pran4ne ring t4 give the pran4ne ring t4 give the flavanonol flavanonol gr4up 41 gr4up 41
1av4n4ids. %he 1avan4n4s ma then be 1urther 1av4n4ids. %he 1avan4n4s ma then be 1urther
4idized t4 ied the 4idized t4 ied the anthocyanins anthocyanins. . whi.h whi.h
.4ntribute t4 the briiant bues 41 14wers and the .4ntribute t4 the briiant bues 41 14wers and the
dark .44ur 41 red wine. dark .44ur 41 red wine.
%he 1av4n4ids .4ntribute t4 man 4ther .44rs %he 1av4n4ids .4ntribute t4 man 4ther .44rs
14und in nature, parti.uar the e4w and 14und in nature, parti.uar the e4w and
4range 41 petas; even the .44ur 4range 41 petas; even the .44ur- -ess 1av4n4ids ess 1av4n4ids
abs4rb ight in the UV spe.trum (due t4 their abs4rb ight in the UV spe.trum (due t4 their
etensive .hr4m4ph4res and are visibe t4 man etensive .hr4m4ph4res and are visibe t4 man
inse.ts. | inse.ts. |A A chromophore chromophore is the part (4r m4iet is the part (4r m4iet
41 a m4e.ue resp4nsibe 14r its .44r 41 a m4e.ue resp4nsibe 14r its .44r|. |.
It is ike that these .4mp4unds have high It is ike that these .4mp4unds have high
ecological ecological imp4rtan.e in nature as .44ur imp4rtan.e in nature as .44ur
attra.tants t4 inse.ts and birds as an aid t4 pant attra.tants t4 inse.ts and birds as an aid t4 pant
p4inati4n. p4inati4n.
Certain 1av4n4ids as4 marked a11e.t the taste Certain 1av4n4ids as4 marked a11e.t the taste
41 144ds: 14r eampe, s4me are ver bitter and 41 144ds: 14r eampe, s4me are ver bitter and
astringent su.h as the 1avan4ne g.4side astringent su.h as the 1avan4ne g.4side
naringin naringin, whi.h 4..urs in the pee 41 grape1ruit , whi.h 4..urs in the pee 41 grape1ruit
Citrus paradisi). Citrus paradisi). Interesting. the .4se Interesting. the .4se
reated .4mp4und reated .4mp4und naringin dihydrochalcone naringin dihydrochalcone, ,
whi.h a.ks the pran4ne ring 41 naringin, is whi.h a.ks the pran4ne ring 41 naringin, is
e.epti4na sweet, being s4me e.epti4na sweet, being s4me 1000 1000 times times
sweeter than tabe sugar (su.r4se. sweeter than tabe sugar (su.r4se.
the 1av4n4ids have imp4rtant dietar the 1av4n4ids have imp4rtant dietar
signi1i.an.e be.ause, being phen4i. .4mp4unds, signi1i.an.e be.ause, being phen4i. .4mp4unds,
the are str4ng anti4idant. the are str4ng anti4idant.
Man disease states are kn4wn t4 be ea.erbated Man disease states are kn4wn t4 be ea.erbated
b the presen.e 41 b the presen.e 41 free radicals free radicals su.h as su.h as
super4ide and hdr4, and 1av4n4ids have the super4ide and hdr4, and 1av4n4ids have the
abiit t4 s.avenge and e11e.tive abiit t4 s.avenge and e11e.tive m4p up m4p up these these
damaging 4idizing spe.ies. damaging 4idizing spe.ies.
F44ds ri.h in this gr4up have there14re been pr4p4sed t4 F44ds ri.h in this gr4up have there14re been pr4p4sed t4
be imp4rtant in amei4rating diseases su.h as .an.er and be imp4rtant in amei4rating diseases su.h as .an.er and
heart disease (whi.h .an be w4rsened b 4idati4n 41 heart disease (whi.h .an be w4rsened b 4idati4n 41
4w 4w densit ip4pr4tein; densit ip4pr4tein; quercetin quercetin. . a 1av4n4id present a 1av4n4id present
in man 144d in man 144d- -stu11s, is a str4ng anti4idant. C4mp4nents stu11s, is a str4ng anti4idant. C4mp4nents
41 mik thiste 41 mik thiste $ilvbum marianum). $ilvbum marianum). in parti.uar in parti.uar silybin silybin,,
are antihepat4t4ins; etra.ts 41 mik thiste are are antihepat4t4ins; etra.ts 41 mik thiste are
genera kn4wn as genera kn4wn as silymarin silymarin
O
OH
O OH
HO
OH
OH
"uercetin
O
O
O
HO
OH O
OH
OCH
3
OH
OH
SiIybin
Some action and therapeutic uses of Some action and therapeutic uses of
flavonoids flavonoids
Man 1av4n4id .4ntaining pants are Man 1av4n4id .4ntaining pants are::
1. 1. Diureti.. Diureti..
2. 2. Antispasm4di.. Antispasm4di..
3. 3. Diaph4reti.. Diaph4reti..
4. 4. In.rease tensie strength 41 .apiar was. In.rease tensie strength 41 .apiar was.
5. 5. Free radi.a s.avengers. Free radi.a s.avengers.
55 Cyanogenetic glycosides Cyanogenetic glycosides
(Cyanide glycosides) (Cyanide glycosides)
Can4genesis is the abiit 41 .ertain iving Can4genesis is the abiit 41 .ertain iving
4rganisms, pants in parti.uar, t4 pr4du.e 4rganisms, pants in parti.uar, t4 pr4du.e
hdr4.ani. a.id (HCN, prussi. a.id. hdr4.ani. a.id (HCN, prussi. a.id.
Can4genesis in pants is a .hemi.a de1ense Can4genesis in pants is a .hemi.a de1ense
me.hanism against 4rganism damaging 4r 1eeding me.hanism against 4rganism damaging 4r 1eeding
4n pant tissues and ead t4 reease 41 HCN gas, 4n pant tissues and ead t4 reease 41 HCN gas,
whi.h is t4i.. whi.h is t4i..
%he are distributed in 4ver %he are distributed in 4ver 2000 2000 pant spe.ies pant spe.ies
be4nging t4 be4nging t4 110 110 1amiies. 1amiies.
%hese .4mp4unds, in presen.e 41 enzmes su.h %hese .4mp4unds, in presen.e 41 enzmes su.h
as as ..- -glucosidase glucosidase, 4se their sugar p4rti4n t4 14rm , 4se their sugar p4rti4n t4 14rm
a a cyanohydrin cyanohydrin whi.h, in the presen.e 41 water whi.h, in the presen.e 41 water
and and hydroxynitrile lyase hydroxynitrile lyase, .an underg4 hdr4sis , .an underg4 hdr4sis
t4 give t4 give benzaldehyde benzaldehyde and the high t4i. and the high t4i.
hydrogen cyanide hydrogen cyanide (HCN. (HCN.
%he sugar p4rti4n 41 the m4e.ue ma be a %he sugar p4rti4n 41 the m4e.ue ma be a
m4n4sa..haride 4r a disa..haride su.h as m4n4sa..haride 4r a disa..haride su.h as
genti4bi4se 4r vi.ian4se. I1 a disa..haride, genti4bi4se 4r vi.ian4se. I1 a disa..haride,
enzmes present in the pant ma bring ab4ut enzmes present in the pant ma bring ab4ut
hdr4sis in tw4 stages, as in the .ase 41 hdr4sis in tw4 stages, as in the .ase 41
amygdalin amygdalin. .
%he are derivatives 41 %he are derivatives 41 -- hdr4nitrie 4r hdr4nitrie 4r 22
hdr4nitrie (.an4hdrins. hdr4nitrie (.an4hdrins.
In a .ases the 1irst sugar atta.hed t4 the ag.4ne is In a .ases the 1irst sugar atta.hed t4 the ag.4ne is
.. D D gu.4se. gu.4se.
RR
11
and R and R
22
are 41ten di11erent residues resuting in are 41ten di11erent residues resuting in
pairs 41 C pairs 41 C 2 2 epimers. epimers.
( (pimers pimers are diastere4mers that di11er in .4n1igurati4n at 4n 4ne are diastere4mers that di11er in .4n1igurati4n at 4n 4ne
41 their stere4geni. .enters. 41 their stere4geni. .enters.
#
1
#
2
CN
OSugar
M4st .an4geneti. g.4sides are bi4sntheti.a M4st .an4geneti. g.4sides are bi4sntheti.a
derived 1r4m the amin4 a.ids: vaine, eu.ine, is4eu.ine, derived 1r4m the amin4 a.ids: vaine, eu.ine, is4eu.ine,
tr4sine 4r phenaanine. tr4sine 4r phenaanine.
Can4geneti. g.4sides are eas t4 dete.t with a strip Can4geneti. g.4sides are eas t4 dete.t with a strip
41 1iter paper impregnated with reagents abe t4 give a 41 1iter paper impregnated with reagents abe t4 give a
.44r rea.ti4n with the hdr4.ani. a.id reeased up4n .44r rea.ti4n with the hdr4.ani. a.id reeased up4n
.rushing the pant materia (e.g., pi.ri. a.id/s4dium .rushing the pant materia (e.g., pi.ri. a.id/s4dium
.arb4nate 4r benzidine/.upri. a.etate. .arb4nate 4r benzidine/.upri. a.etate.
Ath4ugh hdr4.ani. a.id is a vi4ent p4is4n, it is Ath4ugh hdr4.ani. a.id is a vi4ent p4is4n, it is
imp4rtant t4 remember that 4ra intake 41 .an4geneti. imp4rtant t4 remember that 4ra intake 41 .an4geneti.
drugs d4es n4t ne.essari .ause severe int4i.ati4n, this drugs d4es n4t ne.essari .ause severe int4i.ati4n, this
is be.ause the range 41 danger4us .4n.entrati4ns ( is be.ause the range 41 danger4us .4n.entrati4ns (00..55
33..5 5 mg/kg .an 4n be a.hieved b rapid and massive mg/kg .an 4n be a.hieved b rapid and massive
ingesti4n 41 pant parts ri.h in .an4geneti. g.4sides. ingesti4n 41 pant parts ri.h in .an4geneti. g.4sides.
Eampes: Eampes:
Amygdalin Amygdalin in bitter am4nds ( in bitter am4nds (!runus amvgdalus !runus amvgdalus. It is . It is
bi4sntheti.a derived 1r4m phenaanine. bi4sntheti.a derived 1r4m phenaanine.
2 2 Linamarin Linamarin in inseed ( in inseed (inum usitatissimum inum usitatissimum. It is . It is
bi4sntheti.a derived 1r4m vaine. bi4sntheti.a derived 1r4m vaine.
O
HO
HO O
O
HO O
OH
HO
HO
OH
CN
AmygdaIin
CN
O
O
HO
OH
HO
OH
Linamarin
CH
3
CH
3
H
66 Steroidal cardioactive glycosides Steroidal cardioactive glycosides
Cardia. g.4sides are a gr4up 41 natura pr4du.ts Cardia. g.4sides are a gr4up 41 natura pr4du.ts
.hara.terized b their spe.i1i. e11e.t 4n m4.ardia .hara.terized b their spe.i1i. e11e.t 4n m4.ardia
.4ntra.ti4n and atri4ventri.uar .4ndu.ti4n. .4ntra.ti4n and atri4ventri.uar .4ndu.ti4n.
In arge d4ses the are t4i. and bring ab4ut .ardia. In arge d4ses the are t4i. and bring ab4ut .ardia.
arrest in sst4e, but in 4wer d4ses the are arrest in sst4e, but in 4wer d4ses the are
imp4rtant drugs in the treatment 41 imp4rtant drugs in the treatment 41 congestive heart congestive heart
failure failure..
%he have a diureti. a.tivit. Sin.e, the impr4ved %he have a diureti. a.tivit. Sin.e, the impr4ved
.ir.uati4n tends t4 impr4ve rena se.reti4n, whi.h .ir.uati4n tends t4 impr4ve rena se.reti4n, whi.h
reieves the edema 41ten ass4.iated with heart reieves the edema 41ten ass4.iated with heart
1aiure. 1aiure.
Distribution in nature Distribution in nature
Cardiac glycosides 4..ur in sma am4unts in
the seeds, eaves, stems, r44ts 4r barks 41 pants
41 wide ge4graphi.a distributi4n, parti.uar 41
the Fam. pocvanaceae (e.g. seeds 41
$trophanthus. r44ts 41 pocvnum and 1ruits 41
cokanthera), 4thers are 14und in the
$crophulariaceae (e.g. eaves 41 igitalis sp..
iliaceae (e.g. s.aes 41 the bubs 41 Urginea and
Convallaria. and Ranunculaceae donis).
Cardia. g.4sides are as4 14und in animas 4n
in e.epti4na .ases: Bu1adien4ides 4..ur in
t4ads (ufo.
Structure of glycosides Structure of glycosides
%he stru.ture .4mprise a ster4ida ag.4ne 41 the %he stru.ture .4mprise a ster4ida ag.4ne 41 the
(C (C
23 23
cardenolide cardenolide tpe 4r 41 the (C tpe 4r 41 the (C
24 24

bufadienolide bufadienolide tpe, and a sugar m4iet, m4st tpe, and a sugar m4iet, m4st
41ten an 4ig4sa..haride. 41ten an 4ig4sa..haride.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Lactone ring
O
Sugar moiety
A B
C
D
A Structure of the aglycones A Structure of the aglycones
A 41 the ag.4nes have in .4mm4n the .assi., A 41 the ag.4nes have in .4mm4n the .assi.,
tetra..i., ster4ida nu.eus. tetra..i., ster4ida nu.eus.
%he A, B, C and D rings n4rma have a %he A, B, C and D rings n4rma have a cis cis
trans trans cis cis .4n1igurati4n 4r ess 41ten, a .4n1igurati4n 4r ess 41ten, a trans trans
trans trans cis cis .4n1igurati4n. .4n1igurati4n.
As4 .4mm4n t4 a the ag.4nes is the presen.e As4 .4mm4n t4 a the ag.4nes is the presen.e
41 tw4 hdr4 gr4ups: 4ne is a 41 tw4 hdr4 gr4ups: 4ne is a 33.. se.4ndar se.4ndar
a.4h4, the 4ther is a a.4h4, the 4ther is a 14 14.. tertiar a.4h4. tertiar a.4h4.
A 41 the ag.4nes have a A 41 the ag.4nes have a .. .4nstituent at C .4nstituent at C 17 17: :
an an --,,.. unsaturated a.t4ne. unsaturated a.t4ne.
%he size 41 the a.t4ne ring distinguishes tw4 gr4ups 41 %he size 41 the a.t4ne ring distinguishes tw4 gr4ups 41
ag.4nes: the ag.4nes: the C C23 23 .arden4ides with an .arden4ides with an --,,.. unsaturated unsaturated
a.t4ne ( buten4ide and the a.t4ne ( buten4ide and the C C24 24 bu1adien4ides with bu1adien4ides with
a di a di unsaturated unsaturated 0 0 a.t4ne ( pentadien4ide. a.t4ne ( pentadien4ide.
O
O
O
O
14
15
16
17
20
21
22
23
14
15
16
17
20
21
22
23
24
La.t4ne ring 41
Cardenolide
La.t4ne ring 41
Bufadienolide
B Structure of the sugar moiety B Structure of the sugar moiety
%he sugar m4iet is genera inked t4 the ag.4ne %he sugar m4iet is genera inked t4 the ag.4ne
thr4ugh the hdr4 gr4up at C thr4ugh the hdr4 gr4up at C 33..
%he mai4rit 41 the sa..harides 14und in .ardia. %he mai4rit 41 the sa..harides 14und in .ardia.
g.4sides are high spe.i1i.: g.4sides are high spe.i1i.:
1. 1. 22,,66 dide4he4ses, e.g. D dide4he4ses, e.g. D digit44se digit44se
2. 2. 22,,66 dide4 dide4 33 methhe4ses, e.g. D methhe4ses, e.g. D digin4se digin4se
3. 3. 66 de4he4ses, e.g. L de4he4ses, e.g. L rhamn4se rhamn4se
4. 4. 66 de4 de4 33 methhe4ses, e.g. D methhe4ses, e.g. D digita4se digita4se
5. 5. He4se, e.g. gu.4se ( He4se, e.g. gu.4se (hen these is a glucose unit. it is alavs hen these is a glucose unit. it is alavs
terminal terminal. .
%he sugars .an m4di1 %he sugars .an m4di1 the a.tivit the a.tivit (p4ten., t4i.it, (p4ten., t4i.it,
the s4ubiit the s4ubiit, , the di11usi4n the di11usi4n thr4ugh membranes, the rate thr4ugh membranes, the rate
41 41 abs4rpti4n abs4rpti4n and and transp4rtati4n transp4rtati4n 41 the g.4sides. 41 the g.4sides.
C Structure C Structure- -Activity Relationships (SAR) Activity Relationships (SAR)
%he .ardia. a.tivit is inked t4 the ag.4ne. %he .ardia. a.tivit is inked t4 the ag.4ne.
%he sugar m4iet d4es n4t parti.ipate dire.t in the %he sugar m4iet d4es n4t parti.ipate dire.t in the
a.tivit, but its presen.e enhan.es the a.tivit and a.tivit, but its presen.e enhan.es the a.tivit and
m4duates it b m4di1ing the p4arit 41 the .4mp4und. m4duates it b m4di1ing the p4arit 41 the .4mp4und.
%he presen.e 41 a .ertain number 41 stru.tura eements is %he presen.e 41 a .ertain number 41 stru.tura eements is
required 14r, 4r at east 1av4rabe, t4 the a.tivit: required 14r, 4r at east 1av4rabe, t4 the a.tivit:
1. 1. %he a.t4ne at C %he a.t4ne at C 17 17, and it must be in the , and it must be in the .. .4n1igurati4n. .4n1igurati4n.
2. 2. %he .4n1igurati4n 41 the rings. %he a.tivit is maimized %he .4n1igurati4n 41 the rings. %he a.tivit is maimized
when the A, B, C and D rings are in the when the A, B, C and D rings are in the cis cis, , trans trans, , cis cis
.4n1igurati4n. %he C and D rings must be .4n1igurati4n. %he C and D rings must be cis cis 1used. 1used.
3. 3. %he substituents. %he inversi4n 41 the .4n1igurati4n at C %he substituents. %he inversi4n 41 the .4n1igurati4n at C
3 3 diminishes the a.tivit, but diminishes the a.tivit, but 33 de4 .4mp4unds are n4t de4 .4mp4unds are n4t
.4mpete ina.tive. .4mpete ina.tive.
HO
H
H
CH
3
H
H
CH
3
O
O
H
OH
Digitoxigenin
A/B cis B/C trans C/D cis
O
OH
HO
A B
C D
O
!!Biosynthetic origin Biosynthetic origin
Ag.4ne 41 the .ardia. g.4sides are derived Ag.4ne 41 the .ardia. g.4sides are derived
1r4m meva4ni. a.id but the 1ina m4e.ues arise 1r4m meva4ni. a.id but the 1ina m4e.ues arise
1r4m a .4ndensati4n 41 a C 1r4m a .4ndensati4n 41 a C
21 21
ster4id with a C ster4id with a C
22
unit (the s4ur.e 41 C unit (the s4ur.e 41 C 22 22 and C and C 23 23. .
Bu1adien4ides are .4ndensati4n pr4du.ts 41 a Bu1adien4ides are .4ndensati4n pr4du.ts 41 a
CC
21 21
ster4id and a C ster4id and a C
33
unit. unit.
Color reactions Color reactions
%he .an be due t4 the sugars 4r t4 the ag.4ne: %he .an be due t4 the sugars 4r t4 the ag.4ne:
A. A. Color reactions of the sugars Color reactions of the sugars. %he 4n .44r rea.ti4ns 41 . %he 4n .44r rea.ti4ns 41
the sugars that are 41 interest are th4se spe.i1i. t4 the sugars that are 41 interest are th4se spe.i1i. t4 22
de4he4ses. e.g. de4he4ses. e.g. Keller Keller- -Kiliani test Kiliani test..
B. B. Color reactions of the aglvcones Color reactions of the aglvcones (ster4ida nu.eus. (ster4ida nu.eus.
%hese are p4sitive with an .4mp4und .4ntaining a %hese are p4sitive with an .4mp4und .4ntaining a
ster4ida nu.eus in.uding .arden4ides 4r bu1adien4ide: ster4ida nu.eus in.uding .arden4ides 4r bu1adien4ide:
1 1 Antim4n tri.h4ride (SbC Antim4n tri.h4ride (SbC
33

2 2 Liebermann's test (14r bu1adien4ides Liebermann's test (14r bu1adien4ides
C. C. Color reactions of the aglvcones Color reactions of the aglvcones (a.t4ne ring. (a.t4ne ring.
%hese are .hara.teristi. 14r .arden4ides having a %hese are .hara.teristi. 14r .arden4ides having a
1ive 1ive membered a.t4ne ring: membered a.t4ne ring:
1. 1. Lega's test Lega's test
2. 2. Ram4nd's test Ram4nd's test
3. 3. Kedde's test Kedde's test
4. 4. Baiet's test Baiet's test
Pharmacological properties Pharmacological properties
Cardia. g.4sides in.rease the 14r.e and speed 41
.4ntra.ti4n 41 the heart. In patients with .ardia.
insu11i.ien., this p4sitive in4tr4pi. e11e.t
transates int4
1
an in.rease in .ardia. 4utput,
2
an
in.rease in .ardia. w4rk .apa.it with4ut an
in.rease in 4gen .4nsumpti4n,
3
a de.rease in
heart rate, and, indire.t,
4
a de.rease in arteria
resistan.e. (MOA %he g.4sides are th4ught t4
a.t at the membrane eve, b inhibiti4n 41 the a
%!ase, whi.h w4ud resut in an in.rease 41 the
intra.euar .a.ium i4n .4n.entrati4n.
Therapeutic indications Therapeutic indications
Cardia. g.4sides are .urrent indi.ated 14r Cardia. g.4sides are .urrent indi.ated 14r::
1. 1. Cardia. insu11i.ien. with 4w 4utput (genera Cardia. insu11i.ien. with 4w 4utput (genera
in .4mbinati4n with diureti.s, parti.uar when in .4mbinati4n with diureti.s, parti.uar when
there is atria 1ibriati4n. there is atria 1ibriati4n.
2. 2. Supraventri.uar rhthm abn4rmaities: t4 s4w Supraventri.uar rhthm abn4rmaities: t4 s4w
d4wn 4r de.rease atria 1ibriati4n 4r 1utter. d4wn 4r de.rease atria 1ibriati4n 4r 1utter.
Examples Examples
Strophanthus glycosides Strophanthus glycosides
%he name Strophanthus is %he name Strophanthus is
derived from the Creek derived from the Creek
strophos (a twisted cord or strophos (a twisted cord or
rope) and anthos (a flower) rope) and anthos (a flower)
eg eg Strophanthus kombe Strophanthus kombe
%he prin.ipe g.4sides are: %he prin.ipe g.4sides are:
KK- -strophanthoside strophanthoside
2 2 KK- -strophanthin strophanthin- -..
3 3 Cymarin Cymarin
CH
CH
3
OH
O
OH
H
H
O
O
O
Cymarose.-D-glucose --D-glucose
ymarin
K-stropantin-.
K-stropantoside
Squill glycosides Squill glycosides
&rginea maritima (L.
0.1 2.4 t4ta bu1adien4ides,
>15 g.4sides
White variety: average 0.20.4
pr4s.iaridin A, s.iaren A,
gu.4s.iaren A (ag.4ne:
s.iarenin
s.iiphae4side, s.iigau.4side
Red variety: 0.1
s.iir4side and gu.4s.iir4side
(ag.4ne: s.iir4sidin;
pr4s.iaridin A and s.iaren A as
in the white variet
Pharmacological properties of squill Pharmacological properties of squill
White squill: White squill:
it is an epe.t4rant, but it as4 p4ssesses emeti., it is an epe.t4rant, but it as4 p4ssesses emeti.,
.ardi4t4ni. ( .ardi4t4ni. (pr4s.iaridin A, and diureti. , and diureti.
pr4perties. pr4perties.
Red squill: Red squill:
it is used as a rat p4is4n ( it is used as a rat p4is4n (s.iir4side, be.ause , be.ause
r4dents a.k the v4miting re1e, whi.h makes r4dents a.k the v4miting re1e, whi.h makes
red squi parti.uar etha t4 these animas. red squi parti.uar etha t4 these animas.
CH
3
.-D-glucoseO
CH
3
O CH
3
O
O
O
H
OH
OH
SciIIiroside
(3.,6.)-6-(Acetyloxy)-3-(.-D-glucopyranosyloxy)-8,14-dihydroxybufa-4,20,22-trienolide
Digitalis glycosides Digitalis glycosides
Severa spe.ies 41 Severa spe.ies 41 igitalis igitalis ied pharma.44gi.a ied pharma.44gi.a
a.tive prin.ipes. %he m4st imp4rtant 41 these spe.ies are a.tive prin.ipes. %he m4st imp4rtant 41 these spe.ies are
igitalis purpurea igitalis purpurea and and igitalis lanata igitalis lanata..
1. Digitais purpurea 14ium (Red 14g4ve eaves
0.15 0.4 t4ta .arden4ides, > 30 g.4sides
Purpurea g.4sides A and B (>60, digit4in (>12,
git4in (>10 and gita4in (>10.
2. Digitais anata 14ium (White 14g4ve eaves
0.5 1.5 t4ta .arden4ides, > 60 g.4sides
Lanat4sides A and C (>50, anat4sides B, D, E as
we as digoxin and digitoxin.
Digitoxin Digitoxin is a .ardi4t4ni.
g.4side 4btained 1r4m .
purpurea. . lanata.
It is the m4st ipids4ube 41
the .ardia. g.4sides used in
therapeuti.s.
%he mai4r pharma.4kineti.
parameters 14r digit4in
in.ude .4mpete 4ra
abs4rpti4n, whi.h
distinguishes it 1r4m 4ther
.ardia. g.4sides.
Digit4in ma be indi.ated in
patients with impaired rena
1un.ti4n.
Digoxin Digoxin is the m4st wide
used 41 the .ardi4t4ni.
g.4sides, and it is 4btained
1r4m the eaves 41 . lanata.
It is a high p4tent drug and
sh4ud be handed with
e.epti4na .are.
Dig4in tabets are 60 t4
80 abs4rbed.
Dig4in is indi.ated when the
risk 41 digitais int4i.ati4n is
great, sin.e it is reative sh4rt
a.ting and rapid eiminated
when .4mpared with digit4in.
igitalis purpurea igitalis purpurea
77 Tannins Tannins
Hist4ri.a, the imp4rtan.e 41 tannin.4ntaining
drugs is inked t4 their tanning pr4perties, in
4ther w4rds their abiit t4 trans14rm 1resh hides
int4 an imputres.ibe materia: eather.
Tannins are "phen4i. natura pr4du.ts that
pre.ipitate pr4teins 1r4m their aque4us s4uti4ns".
%he .4nsequen.e 41 tanning is the 14rmati4n 41
b4nds between the .4agen 1ibers in the hide,
whi.h imparts resistan.e t4 water, heat, and
abrasi4n. %his .apabiit 41 tannins t4 .4mbine
with ma.r4m4e.ues epains wh the
pre.ipitate .eu4se, pe.tins, and pr4teins; it
as4 epains their .hara.teristi. astringen.
and tartness: b pre.ipitating the g.4pr4teins
.4ntained in saiva, tannins make the atter 4se
its ubri.ating p4wer.
M4st true tannins have m4e.uar weights
1r4m ab4ut 1000 5000.
Pseudotannins Pseudotannins
%he are .4mp4unds 41 4wer m4e.uar weight %he are .4mp4unds 41 4wer m4e.uar weight
than true tannins and the d4 n4t resp4nd t4 the than true tannins and the d4 n4t resp4nd t4 the
goldbeaters skin test goldbeaters skin test..
Eampes 41 drugs .4ntaining Pseud4tannins are Eampes 41 drugs .4ntaining Pseud4tannins are::
allic acid allic acid: Rhubarb : Rhubarb
Catechins Catechins: uarana, C4.4a : uarana, C4.4a
Chlorogenic acid Chlorogenic acid: Mate, C411ee : Mate, C411ee
pecacuanhic acid pecacuanhic acid:: ipe.a.uanha ipe.a.uanha
Gallic acid
COOH
OH
OH
HO
Catechin
O HO
OH
OH
OH
OH
Chlorogenic acid
O
O
OH
HO
OH HOOC
OH
OH
Function of tannins in plants Function of tannins in plants
1. 1. %annins are .4nsidered the %annins are .4nsidered the source of energv source of energv
thr4ugh their 4gen .4ntent. thr4ugh their 4gen .4ntent.
2. 2. %he serve as a %he serve as a protective protective t4 the pant (pant t4 the pant (pant
antisepti.s. antisepti.s.
3. 3. %he ma have %he ma have function in respiratorv activitv function in respiratorv activitv, i.e. , i.e.
in the me.hanisms 41 hdr4gen trans1er in pant in the me.hanisms 41 hdr4gen trans1er in pant
.es. .es.
4. 4. %annins pa an imp4rtant part in the %annins pa an imp4rtant part in the acceptance acceptance
of manv foods and beverages of manv foods and beverages b .4nsumers e.g. b .4nsumers e.g.
tea, .4.4a. tea, .4.4a.
Classification of tannins Classification of tannins
In higher pants, tw4 gr4ups 41 tannins are
genera distinguished, whi.h di11er b their
stru.ture, as we as their bi4sntheti. 4rigin:
hvdrolvsable hvdrolvsable tannins and condensed condensed tannins.
vdrolvsable tannins
Hdr4sabe tannins are esters 41 a sugar (4r
reated p44 and 41 a variabe number 41
phen4i. a.id m4e.ues.
%he sugar is m4st genera gu.4se.
%he phen4i. a.id is either gallic acid, in the .ase
41 gallitannins. 4r Ellagic acid, in the .ase 41 the
tannins .4nventi4na re1erred t4 as
ellagitannins.
Eagi. a.id .an arise b a.t4nizati4n 41
hexahvdroxvdiphenic a.id ( HHDP during
.hemi.a hdr4sis 41 the tannin.
Hydrolysable tannins Hydrolysable tannins ere formerlv knon as ere formerlv knon as
pvrogallol tannins pvrogallol tannins. because on drv distillation . because on drv distillation
gallic acid and similar components are converted gallic acid and similar components are converted
into pvrogallol into pvrogallol. .
Biosynthetically, gai. a.id ( 3,4,5
trihdr4benz4i. a.id arises 1r4m the
metab4ism 41 shikimi. a.id.
Eampes 41 drugs .4ntaining Hdr4sabe
tannins:
allitannins allitannins. rhubarb, .4ves, Chinese gas,
%urkish gas, hamameis, .hestnut and mape.
Ellagitannins Ellagitannins. p4megranate rind, p4megranate
bark, eu.aptus eaves, and 4ak bark.
Gallic acid
COOH
OH
OH
HO
OH
OH
HO
Pyrogallol
OH
OH
OH
HO
OH
COOH HO
HOOC
Hexahydroxydiphenic acid
O
O
O
O
OH
OH
OH
HO
Ellagic Acid
Condensed tannins (proanthocyanidins) Condensed tannins (proanthocyanidins)
C4ndensed tannins 4r proanthocvanidins are
p4meri. 1avans. %he .4nsist 41 flavan-3-ol
units inked t4gether b .arb4n.arb4n b4nds,
m4st 41ten 4F8 4r 4F6, whi.h resut 1r4m
.4uping between the ee.tr4phii. C4 41 a
1avan unit 1r4m a 1avan44 4r 1avan3,4di4
and a nu.e4phii. p4siti4n (C8, ess .4mm4n
C6 41 an4ther unit, genera a 1avan34.
Unlike hvdrolvsable tannins. these are not readilv
hvdrolvzed to simpler molecules and thev do not
contain a sugar moietv.
O HO
OH
OH
OH
OH
atecin (catechol)
O HO
OH
OH
OH
OH
OH
FIavan-3,4-dioI structure
O HO
OH
OH
OH
OH
O HO
OH
OH
OH
OH
A dimeric structure
Biosynthetically, 1av4n4ids are derived 1r4m
a.etate and shikimate pathwas.
C4ndensed tannins 4..ur due t4 p4merizati4n
(.4ndensati4n rea.ti4ns between 1av4n4ids.
%he p4mers ma in.ude up t4 50 m4n4mer
units.
n treatment ith acids or enzvmes condensed
tannins are converted into red insoluble
compounds knon as phlobaphenes.
Ph4baphenes give the .hara.teristi. red .44ur t4 Ph4baphenes give the .hara.teristi. red .44ur t4
man drugs su.h as red .innam4n bark. man drugs su.h as red .innam4n bark.
Eampes 41 drugs .4ntaining C4ndensed
tannins:
S4me drugs (e.g. tea, hamameis eaves and hamameis
bark .4ntain b4th hdr4sabe and .4ndensed tannins.
%he 144wing are ri.h in .4ndensed tannins.
(1 Barks: .innam4n, wid .herr, .in.h4na, wi4w, a.a.ia,
4ak and hamameis
(2 Roots and rhizomes: krameria (rhatan and mae 1ern
(3 Flowers: ime and hawth4rn
(4 Seeds: .4.4a, guarana, and k4a
(5 Leaves: hamameis, hawth4rn and tea, espe.ia green tea
(6 xtracts and dried juices: .ate.hu, a.a.ia and mangr4ve
.ut.hes
Properties and tests of tannins Properties and tests of tannins
%annins are s4ube in water, diute akais, a.4h4,
g.er4 and a.et4ne, but genera 4n sparing
s4ube in 4ther 4rgani. s4vents.
S4uti4ns pre.ipitate heav metas, aka4ids, g.4sides
and geatin.
With 1erri. sats, gaitannins and eagitannins give bue
ba.k pre.ipitates and .4ndensed tannins br4wnishgreen
4nes. f a verv dilute ferric chloride solution is graduallv
added to an aqueous extract of hamamelis leaves hich
contains both tvpes of tannin). a blue colour is produced
hich changes to olivegreen as more ferric chloride is
added. Other use1u tests are the 144wing:
. . Coldbeater's skin test Coldbeater's skin test
S4ak a sma pie.e 41 g4dbeater's skin in 2
hdr4.h4ri. a.id; rinse with distied water and
pa.e in the s4uti4n t4 be tested 14r 5 min.
Wash with distied water and trans1er t4 a 1
s4uti4n 41 1err4us suphate. A br4wn 4r ba.k
.44ur 4n the skin den4tes the presen.e 41
tannins. oldbeaters skin is a membrane
prepared from the intestine of the ox and
behaves similarlv to an untanned hide.
. . Celatin test Celatin test
S4uti4ns 41 tannins (ab4ut 0.51 pre.ipitate a
1 s4uti4n 41 geatin .4ntaining 10 s4dium
.h4ride. allic acid and other pseudotannins
also precipitate gelatin if the solutions are
sufficientlv concentrated.
. . Phenazone test Phenazone test
4. 4. %est for catechin %est for catechin
5. 5. %est for chlorogenic acid %est for chlorogenic acid
Medicinal and biological properties Medicinal and biological properties
%he appi.ati4ns 41 tannin.4ntaining drugs are
imited, and resut 1r4m their a11init 14r pr4teins.
%annin.4ntaining drugs wi pre.ipitate pr4tein
and have been used traditi4na as stpti.s and
interna 14r the pr4te.ti4n 41 in1amed sur1a.es
41 m4uth and thr4at.
%he a.t as antidiarrh4eas and have been
emp4ed as antid4tes in p4is4ning b heav
metas, aka4ids and g.4sides.
suma.

Glucosides &amp Tannins (Part-6)

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Glucosides &amp Tannins (Part-6)

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