 sugar ethers; heteropolysaccharides

 compounds that yield one or more sugars among

the products of hydrolysis
 both α and  glycosides are possible; only  form
occurs in plants
1) non-sugar portion - “Aglycone / Genin” portion
2) sugar portion - “Glycone”
 CLASSIFICATION BASED ON AGLYCONE COMPT
 have specific action on the cardiac tissues;
they increase force of systolic contraction
 aglycones: cardenolide, bufadienolide
(scillarenin)
 Derived from C21 steroid
 CPPP nucleus
 inhibit Na/K ATPase, thereby increasing the
Ca+2 inside the heart muscles (+ inotropic
effect)
 Deoxysugars at C3
 Digitalis (narrow therapeutic index)
 Digitoxin: very lipophilic, longer half-life (168 to
192 hours)
 Digoxin: more polar, shorter half-life (30 to 40
hours), excreted via kidneys (Lanoxin®)

Digitalis pupurea Digitalis lanata

Other name Foxglove Grecian Foxglove

Constituents Digitoxin, gitoxin, Digoxin, deslanoside

gitaloxin (desacetyllanatoside)
 Convallaria / Lily-of-the-valley Root
 rhizome and root of Convallaria majalis
 constituent: convallotoxin

 Apocynum / Black Indian Hemp / Dogbane /

Canadian Hemp
 rhizome and root of Apocynum canabinum
 constituent: cymarin

 Adonis / Pheasant’s eye

 Adonis vernalis
 constituent: adonitoxin, cymarin, K-strophantin
 Cactus grandiflorus / Night-blooming cereus
 stem of Selenicereus grandiflorus
 Black Hellebore / Christmas rose ( bufadienolide)
 rhizome and root of Helleborus niger,
Ranunculaceae
 constituent: hellebrin;helleborin,
 Abortifacient, cardiotonic
 * Green Hellebore: cardiac depressant

 Strophantus
 dried, ripe seed of Strophantus kombe
 preparation of arrow poisons (Africans);
 constituent: K-strophanthin
 Strophantus gratus: has ouabain (“G-strophanthin”)
 Squill / Squill bulb ( bufadienolide)
 Dried sliced bulb of the white variety of Urginea maritima,
Liliaceae
 constituent: scillaren A use: expectorant, emetic,
cardiotonic, diuretic

* Red squill: red variety of U. maritima

(use: rat poison – lack the vomiting reflex)

 Rose Bay / Oleander

 Nerium oleander; constituent: oleandrin
 DACCBASSO

Family L: LEA
DETECTION OF THIS GROUP:
1. Keller Kiliani Test - test for the presence of deoxy sugar
- blue or violet coloration
2. Liebermann Burchard Test – test for unsaturated sterol
group
- conc sulfuric and acetic anhydride
(+) green, blue
- pale yellow if saturated sterol
3. Salkowski’s Test – test for sterol
- conc sulfuric
(+) red or violet
4. Kedde’s test - unsaturated lactone
- std. – 0.025% digitoxin in MeOH
- blue – violet coloration
 AGLYCONE: Anthracene derivatives like
 chrysophanol ( rhubarb, cascara)
 Aloe- emodin ( rhubarb, senna)
 Rhein ( rhubarb, senna)
 Emodin ( rhubarb, cascara)

 use: stimulant cathartics to the large

intestine, delayed effect ( 6hrs or more)
 except for chrysarobin
 MOA: they increase tone of smooth
muscle in wall of large intestines,
inhibition of Cl ion channel
 O O OH
1. 2.

O
ANTHRAQUINONE ANTHRONE ANTHRANOL

OH O OH
OH O OH
4.

R' R
HO R
O
O
ALOE EMODIN
EMODIN R - CH 3 R -CH 2OH R' = 1
EMODIC ACID R -COOH PHYSICON R= CH 3 R' = OCH 3
5. Barbaloin ( C-glycoside)
 • ORANGE – RED COMPOUNDS
• SOLUBLE IN DILUTE ALCOHOL AND BOILING /
HOT WATER
•GIVE A CHARACTERISTIC RED, VIOLET, GREEN
COLOR WITH A BASE ( NH3 or NaOH)

-FIVE TYPES:
a) Anthraquinone (anthracene derivative)
dihydroxy phenol such as chrysophanol & rhein
trihydroxyphenol such as emodin

b) Anthranol / anthrone type

ex. Chrysarobin

c) Dianthrone ( 2 molecules of anthrone )

ex. Senna’s main const. – sennoside
d. Oxanthrone
Intermediate between anthraquinone and anthranol
-ex. Emodin – oxanthrone glucoside

e)Aloin type / C – glycoside

- ex. Barbaloin in cascara sagrada

BORNTRAGER’S TEST
( + ) red color on the lower alkaline layer
( - ) indicates a very stable form of anthraquinone esp. the
reduced types of anthranol but first the sample must be
hydrolyzed and oxidized.

MODIFIED BORNTRAGER’S TEST:

( + ) pink color or red color in the alkaline layer
indicates the presence of a very stable type of anthraquinone
1. Anthraquinone

OH O OH 4. Oxanthrone

R
O
CHRYSOPHANOL RHEIN
R = CH 3 R = COOH
 Cascara sagrada / Rhamnus purshiana /
 Sacred bark
 should be aged for at least 1 year prior to use
 dried bark of Rhamnus purshianus
 constituents: Cascarosides A and B –
optical isomers of barbaloin
 Cascarosides C and D – optical isomers
of chrysaloin
 to reduce its bitter taste, add MgO or alkaline
earths
 casanthranol: purified mixture of the anthranol
glycosides extracted from Cascara
 Frangula / Buckthorn bark
 dried bark of Rhamnus frangula
 component of Movicol® (Frangula + Karaya gum)
 Glucofrangulin A (7%); frangulin
 Aloes
 dried latex of leaves of Aloe barbadensis
(Curacao / Barbados Aloe), A. spicata (Cape
Aloe)
 constituents: barbaloin (aloe-emodin anthrone),
chrysophanic acid
 use: ingredient in compound benzoin tincture,
cathartic (drastic)
 Aloe vera Gel: treatment of burns, abrasions,
skin irritations, purgative, alopecia
 Rhubarb / Rheum / Chinese Rhubarb
 rhizome and root of Rheum officinale, R. palmatum, R.
rhaponticum
 constituent: rhein anthrones; glucorhein
 Glucogalli, gallic acid – astringent prop
 Rhapontic rhubarb – rhaponticin ( under UV –blue
flourescence, absence for other rhubarb)
 Senna / Senna leaves / Slimming tea
 dried leaflet of Cassia acutifolia (Alexandria senna)
 Cassia angustifolia (Tinnevelly senna); fabaceae
 constituent: sennosides A and B (more potent than cascara)
 Sennidin A, B - aglycone
 cultivated on WET lands resembling rice paddies; as
successor to rice
 Cochineal
 Dried female insect, Dactylopius coccus
 Carminic acid
 Hypericum perforatum ( St. john’s wort)
 Clusiaceae, dried aerial parts
 Hypericin emodin-anthrone
 Mild to moderate depression
 Chrysarobin
 mixture of neutral principles obtained from
Goa powder (Andira araroba); Fabaceae
 extracted using hot benzene
 use: keratolytic agent, for psoriasis,
trichophytosis, eczema
 foam upon shaking
 bitter, acrid taste
 irritating to mucuous membranes
 destroy RBC's of cold blooded animals-->
fish poisons
 -Aglycone: Sapogenin
 -Toxic Aglycone: Sapotoxin
 -Steroidal in nature
 One of the most toxic plant principles (Poisonous:
“sapotoxins”)
 Irritating to the mucus membranes; toxic to cold-
blooded animals (fish poisons)
 Hemolysis test: Destroy RBC
 Capillary test: measures fluidity of extract; (+)
saponins tend to ↓ surface tension

 Aglycone: “sapogenin”; Use: precursors in

preparation of steroids
2 types: a) Neutral saponins – derivative of steroids (M)
b) Acid saponins – derivative of triterpenoids (D)
CHARACTERISTICS: a) in aqueous solution it will form a
froth
b) can hemolyze RBC
1.Froth test – foam / lather formation
- honeycomb froth persisting for 10 min.
above 2 cm is positive for saponins
if froth is unstable add aqueous sod carbonate to
neutralize the free acids
2. Liebermann – Burchard test
- for steroidal type of saponins present in monocot
plants
(+) blue or green
- for triterpenoidal type present in dicot plants
(+) red, pink or violet

Pale yellow if saturated sterol or triterpenoid is present

-Use blood agar plate , gugo soln as std.
(+) forms a hemolytical halo ( white ring )
zone of hemolysis

4. Capillary tube test:

Saponins tend to lower the surface tension in
water.

5. Fehling’s
Formation of a brick red ppt of Cu2O.
Type

Steroidal Pentacyclic triterpenoidal

 Steroidal Type
 Dioscorea / Yam
 Mexican Yam: Dioscorea floribunda
 constituent: botogenin
 Dioscorea spiculiflora-contains diosgenin which is a
glucocorticoid precursor
 diosgenin; use: major precursors of glucocorticoids
 Dioscorea floribunda- Best source of STEROIDS
 Fenugreek (Trigonella foenum-graecum)
 Fabaceae, oily embryo of seeds
 Diosgenin
 Sarsaparilla root ( Smilax aristolochiaefolia),
Liliaceae, dried root
 Smilagenin, sarsasapogenin, parillin
 Tx of syphilis, rheumatism, skin diseases, psoriasis, eczema
 Panax ginseng, Araliaceae
 Panax quinquefolium ( USA)
 Aphrodisiac and an Adaptogen ( resistance to
stress)
 Constituents: Panaxosides, Ginsenosides and
Chikusetsusaponins
 Tx of anemia,diabetis, gastritis, sexual
impotence

 *Ginseng of Europe: Chamomile- dried

leaflet of Matricaria chamomila
 Glycyrrhiza / Licorice Root
 dries roots/ stolons of Glcyrrhiza glabra
 increases the foaminess of beer
 rhizome and root of Glycyrrhiza glabra (Spanish);
G. glabra var. glandulifera (Russian)
 constituent: glycyrrhizin (50X as sweet as sugar);
genin portion: glycyrrhetic acid
 4% glycyrrhizic acid
 use: expectorant, flavoring agent, mask taste of
bitter drugs (paralyze taste buds)
 glycyrrhetic acid: anti-inflammatory, for peptic
ulcer, Addison’s disease
 CAUTION in HTNsive patients: glycyrrhizin ↑ fluid
and Na+ retention, K+ depletion
 Centella asiatica ( Gotu kola, tiger grass)
 Dried aerial parts (Apiaceae)
 Asiaticoside, centelloside
 Diuretic,antirheumatic, vasodilator
 Quillaja bark/ Soap bark ( Q. saponaria)
 Rosaceae
 Dried inner bark
 Quillaia saponin ( 10%)
 Senega ( Polygala senega), Polygalaceae
 Dried root crown and root
 Senegin
 Stim expectorant in chronic bronchitis
 glycosides which yield hydrocyanic acid
as one of the products; derivatives of
mandelonitrile
 test for the presence of cyanogenic
glycosides: Grignard test
 uses: flavoring agents
 anticancer claims (amygdalin-
containing preparation: Laetrile /
Vitamin B17)
 possible control for sickle cell
anemia
 Amygdalin( H2O and amygdalase)-->
mandelonitrile glucose (H20 and prunase)-->
mandelonitrile + glucose -->benzaldehyde +
HCN

 **Amygdalase and Prunase are collectively

known as EMULSIN
 APE= A+ P = E
 Amygdalin - found in large quantities in:
Bitter Almond (Prunus amygdalus)
Apricot (Prunus armeniaca)
Wild Cherry / Prunus virginiana (Prunus serotina)
 flavored vehicle, expectorant and sedative

 Prunasin- dried stem bark of Prunus serotina /

Wild black cherry tree / Prunus virginiana
 prunasin: compound formed by the partial hydrolysis of
amygdalin
 enzyme emulsin: consists of a mixture of 2 enzymes
(prunase, amygdalase)
 Cassava
- Mannihot esculenta; constituent:
mannihotoxin, linamarin (toxic cyanogen)

 CAP
 AMYGDALIN

AMYGDALIN BENZALDEHYDE
Guignard’s test – non specific test for cyanophore
because there
are other substances that can liberate H2S,
SO2 or aldehyde.
- sodium picrate paper needed in the test
- yellow to brick red or any shade of red
- HCN has an odor of bitter almond / peach
kernels.
Result: if within 15 mins – (+)
after 3 hours – absence of cyanophore
glycoside
 use: condiments
from CRUCIFERAE family
 Black Mustard / Sinapis nigra / brown
mustard
 dried ripe seed of Brassica nigra
 constituent: sinigrin (potassium myronate) with the
enzyme Myrosin
 sinigrin (myrosin) allyl isothiocyanate (volatile)
(mustard oil)
 White Mustard / Sinapis alba
 dried ripe seed of Brassica alba
 constituent: sinalbin
 sinalbin (myrosin) acrinyl isothiocyanate(mustard
oil)(pungent-tasting, less volatile)
Isothiocyanate producing group or Mustard
oil glycoside
Family: Cruciferae (Brassicaceae)
R- SCN
a)Odor test - for the volatile type
- ex. Allicin ( in garlic )
ID test of garlic :
10 mL 1N NaOH + 10mL water + heat
use sodium nitroferricyanide t.s.
- red or orange color
b) Ferric chloride test - for the non-volatile type

- Fe(SCN)3 blood red

 Localirritant and emetic
 Rubefacient, vesicant and condiment
 flavonoids:rutin, quercetin, citrin
 bioflavonoids (hesperidin, hesperetin,
diosmin, naringen)
 Vitamin P / Permeability factors: Rutin +
hesperidin
 treatment of capillary bleeding and increased
capillary fragility; for HTN, radiation injuries
 flavonoid found in yellow flower pigment:
“chalcones”
 Rutin – yel crystalline powder, sol in alkali
 Yields quercetin, rhamnose, glucose
 Hesperidin – yields hesperitin, rhamnose, glucose
 Flavonoids or Bioflavonoids from Citrus
fruits and Soya
 Largest grp of naturally occurring phenols
 Flavones – yellow
 Flavonoids dissolve in alkali – yel soln + acid turn
to colorless
1. Rutin and Hesperidin- Vitamin P or
Permeability Factors( formerly known as
citrin found in paprika/ lemon peel)
 uses: treatment of capillary bleeding secondary
to capillary fragility
 treatment of symptoms of common colds
2. Hesperitin, diosmin and Naringen
 anti- H. pylori
 1
2

 Theyhave benzo-γ-pyrone moiety, except

charcone
 Flavonoidsrelated to flavones
 Anthocyanins- glycosides
 Sap pigments, the color of plant is determined by
pH of the sap
 Ppt in aq soln as Pb salts or picrates
 + 20% HCL- hydrolizes , crystallizes
 Bilberry ( Vaccinium myrtillus) Ericaceae
 Anthocyanins ( cyanidin- 3-glucoside Cl)
Wilstatter “cyanidin” test
- for the presence of gamma benzopyrone nucleus
(+) orange to red to crimson & magenta occasionally green/
blue.

Bate-Smith & Metcalf test

On addition of conc HCl – immediate red
-For the presence of chalcones & aurones
If no color is produced, sample boiled and an intense red color/
violet for leucoanthocyanins

For Anthocyanins w/ the flavylium ion: extract with 1% HCl

ffd by boiling
(+) at boiling pt an orange red to blue red coloration is
produced
 Vitex agnus, Verbenaceae, Chaste tree
 Whole ripe dried fruit
 Casticin, vitexin, penduletin
 For PMS
 Birch
leaf ( Betula pendula) Betulaceae; dried
leaves
 Hyperoside, quercitrin
 Irrigant of urinary tract in cases of inflammation,
for gout, astringent( mouthwash)
 Calendula flower
 C. officinalis, Asteraceae
 Whole dried fully opened flowers
 Hyperoside, quercetin
 GI disorders, tx of minor wounds
 Java tea, Orthosiphon stamineus, Labiatae
 Sinensetin
 Diuretic, DM and HPN
 Passiflora incarnata ( Passion flower)
 Dried aerial parts
 Vitexin, orientin
 Sedative action
 Visnaga ( Ammi visnaga), Apiaceae
 Dried ripe fruits
 Khellin
 Coronary vasodilator, tx of angina pectoris
 Salicin - produces saligenin / salicin alcohol
after hydrolysis with emulsin
 Aglycone: Saligenin
 glycoside from willow and poplar barks; most
from Salix purpurea and S. fragilis
 use: antirheumatic (like salicylic acid), anti-
inflammatory
 Populin
 glycoside from Populus tremula; “benzoyl-
salicin”

 Under phenolic glycosides ( Trease and Evans ,

2009)
 Viburnum prunifolium ( Caprifoliaceae)
 Black haw bark
 Dysmenorrhea, bleeding, asthma
 Has 0.2% salicin, isovaleric acid

 Humulus lupulus ( Cannabinaceae)

 Hops
 Dried strobiles
 Lupulin, reddish brown powder has bitter aromatic
taste (humulone (α –acids); lupulone (βacids) –
phloroglucinol der.
 Xanthohumol – cytotoxic effects on CA cells
 Bitterness of beer
 Kamala, trichomes and glands
 Mallotus philippinensis ( Euphorbiaceae)
 Dull red brown powdre w/o odor or taste
 Rottlerin, isorottlerin – anthelmintic
 Tapeworm infestation
 CH 2 OH CHO
O C 6 H 11 O5

OCH 3
SALICIN
OH

CH 3 VANILLIN

CH 3
CH 3 O
O
CH 3 O O O
O
SANTONIN CH 3 O

CANTHARIDIN
Detected by Ester Formation
C2H5-OH + CH3COOH CH3COOC2H5
Aldehyde Glycoside
Detected by General aldehyde reaction:
a) Fehling’s Test
Cu2O brick red ppt
b) Nessler’s Test
gray ppt of Hg
reagent: K2HgI4 t.s. alkaline
c) Tollen’s Test or Silver mirror Test or Ammioniacal AgNO3
Test
gradual deposition of silver mirror
d) Schiff’s Test
magenta-red color restored if there’s a aldehyde
complexation reaction
 Vanilla / vanilla bean/ pods
 unripe fruit of Vanilla planifolia (Mexican,
Bourbon vanilla); V. fragrans
 Vanilla tahitensis (Tahiti Vanilla)
 constituents: glucovanillin (avenein),
glucovanillic alcohol
 Curing activates the formation of the glycosides
 vanillin/ vanillic aldehyde: principle flavoring
 constituent (4-hydroxy-3-methoxybenzaldehyde)
 Synthesized via ferulic acid
 Confectionary, perfumery
 Coumarin
 Derivative of benzo-α-pyrone
 Lactone of O-hydroxycinnamic acid
 use: flavoring agent
 natural sources:
 Tonka Beans/ tonco seed (Dipteryx odorata) – dried
seeds
 coumarin, tobacco manuf, perfumery
Coumarin- from Tonka beans, Dipteryx odorata
 Cons: Dicoumarol, bishydroxycoumarin-->
anticoagulant, Warfarin
 Furanocoumarins- grape fruit juice – inhibitor of Cyt
P450 (CYP3A4, CYP3A5)
 Sweet vernal grass (Anthoxanthum odoratum)

 Sweet clover (Melilotus alba)
 Sweet-scented bedstraw (Galium triflorum)
 Red clover (Trifolium pratense)
 Melilot ( Fabaceae)
 Yel papilionaceous flower
 improperly cured leaves and flowering tops Melilotus
officinalis
 Melilotoside; melilotic acid, caffeic acids
 Skimmin (Jap. Star anise); Aesculin, aesculetin –
horse chestnut tree
 use: anticoagulant (now prepared
synthetically)
 Angelica root ( A. archangelica) ( Apiaceae)
 Angelicin, archangelicin, apterin
 Coronary vasodilator effects, Ca antagonist
 Cantharides / Spanish flies / Russian flies /
Blistering flies
 dried insect Cantharis vesicatoria
 constituent: cantharidin
 use: irritant, vesicant, rubefacient,
 aphrodisiac (irritates Urinary tract
  priapism), topical treatment of warts
 Psoralens- Methoxsalen, 8-
methoxypsoralen, xanthotoxin:
constituent of Ammi majus
 use: aid repigmentation in vitiligo, and
symptomatic control for psoriasis
For unsaturated lactone : Kedde’s Test
For saturated ones : Chromatography

Phenol Glycosides:
Detected by Millon’s Test
- peach / salmon / pink coloration mercury complex of
the nitrophenyl derivative

Chromatography : use spray of:

a)Folin Ciocalteau - blue spots

for the presence of catechol & hydroquinone type
b) Vanillin- HCl - pink spots
for the presence of resorcinol & phloroglucinol type
c) Gibb’s reagent - various colors of different phenols (2,6-
dichloroquinone 4-chloroimide)
 Uva ursi / Bearberry
 dried leaf of Arctostaphyllos uva -ursi (herbal
tea available)
 Ericaceae
 arbutin; methyl arbutin
 use: diuretic, astringent, weak urinary
antiseptic
O C 6H 11O5 OH

+ H2O + C 6H 12O6

Glucose
OH OH
Arbutin Hydroquinone
 Neutralglycosides – dried ripe seed of Anamirta
cocculus (Menispermaceae)
 Bitter
glycosides – heartwood of Quassia amara
(Simarubaceae) in Surinam (Bitter Wood, bitter ash)
quassin
 Bitter
glycosides – Picrasma excelsa (Jamaican)
picrasmin

- root & rhizome of

Gentiana lutea
(Bitter root)
 Sweet glycosides – Glycyrrhiza glabra var. typica &
var. glandulifera (Fabaceae)
 Coloringglycosides – dried stigmas
Crocus sativus (Iridaceae) picrocrocin

- heartwood Haematoxylon
campechianum (Fabaceae) hematoxylin
 Coloring
glycosides – Pterocarpus santalinus
(Fabaceae) santalin
 Coloringglycosides – dried female insect enclosing
a young larvae Coccus cacti (Coccidae) carminic
acid Dactylopius coccus
 Coloring
glycosides – natural source of litmus
powder Ochrolechia tartarea (Ochrolechiaceae)
 Miscellaneous Glycosides
 Volatile Oil-Containing Glycoside

ARNICA – dried flower heads of Arnica

montana (European); A. fulgens; A. sororia;
A. cordifolia (American) CALAMUS – the dried peeled rhizome of
SYN: Mountain tobacco Acorus calamus (Araceae)
CONST: Arnicin SYN: Sweet flag
CONST: Acorin
 Complex substances or polypeptides ,
mixture of polyphenols difficult to separate
because they do not crystallize
 usual source: barks / stems
 use: astringent, antidote to alkaloidal
poisoning, precipitants of proteins, tanning
and dyeing industry
 CAUTION: carcinogenic (e.g. chewing of
betel nut Areca catechu)
 TRUE TANNINS have a MW 1000 – 5000
 the polyphenol molecule must be neither too
large as to be unable to enter the interstices of
the collagen fibrils nor so small that it is unable to
cross-link between protein molecules of adjacent
fibrils at several points.
 Moderate sized molecule (1-2 per 100 mw) of
phenolic groups which are associated with o-
dihydroxy and o-trihydroxy orientation within a
phenyl ring.
TANNINS
 denote substances present in plant extracts able
to combine with protein of animal hides,
prevent putrefaction and convert them into
leather.
 Excludes simpler phenolic substances (gallic acid,
catechins & chlorogenic acid ( Pseudotannins)
often present with tannins.
 Low molecular weight compounds than true tannins
called pseudotannins.
 Test for Tannins
• Quantitatively detected by tanning test (Gold-
beater’s skin test), by its adsorption on std hide
powder.
 Can precipitate gelatin.
1. Hydrolyzable
 Hydrolyzed by acids or enzymes (tannase)
 Composed of phenolic acids (gallic and
hexahydroxydiphenic acids) united by ester linkages
to a central glucose molecule.
Principal types:
1) Gallitannins – gallic acid ex: red rose petals,
bearberry leaves, Turkish gall, hamamelis, chestnut
2) Ellagitannin – ellagic acid; lactonization of
hexahydroxydiphenic acids ex: pomegranate rind/
bark, Australian kinos, chestnut
on dry dist. Are converted into pyrogallol
turn bluish black with ferric chloride TS
 -D-glucose + gallic acid galloyl glucose pentagalloyl glucose
(gallitannin)

-D-glucose + ellagic acid ellagoyl glucose pentaellagoyl glucose

(ellagitannin)
 x2

Shikimic acid
2. Non-hydrolyzable
Condensed (proanthocyanidins)
not readily hydrolyzed to simpler molecules and
do not contain sugar moiety
related to flavonoid pigments and possess that
polymeric flavan-3-ol structures
treated with acids and enzymes, converted or
polymerized to a red insoluble compound called
phlobaphene.
dry distillation yield catechol; green with FeCl3 (
due to catechol)
Cinnamon bark, hamamelis bark
Krameria, male fern roots/ rhizomes
cocoa , kola, areca seed
flavan 3-ol
structure

phlobatannins
Trimeric procyanidin
Complex Tannins
 term applied by Okuda for a group of tannins
which are biosynthesized from both hydrolyzable (
ellagitannin) and condensed tannins.
 bond between C1 of glucose of ellagitannin and
C8or C6 of flavan-3-ol

Pseudotannins
compounds of lower molecular weight and does
not respond to Goldbeater’s skin test
exert inhibitory effect on many enzymes due to
protein precipitation.
Gallic acid, catechins, chlorogenic acid,
ipecacuanhic acid
 soluble in water, dilute alkalis, alcohol,glycerol and
acetone
 sparingly soluble in organic solvents
 WITH Ferric salts:
 hydrolyzable – blue black ppt
 condensed - brownish green ppt
 Other tests:
 Goldbeater’s test: goldbeater skin, 2%HCl,rinse w/ H20, place
in extract, rinse w/ water + 1%FeSO4 +R = black/brown
coloration
 Gelatin test: tannin/ extract + gelatin+ 10% NaCl +R= fleshy
ppt
 Phenazone test: tannin + Na2HPO4 heat, cool, filter + 2%
phenazone +R = ppt tannin
4. Test for catechin:
Catechin + acid = phloroglucinol
Dip matchstick in extract, dry, moisten w/ conc.HCL,
warm near a flame + R = pink or red wood on flame
( Test for Lignin)
5. Test for chlorogenic acid :
Extract + aq. NH3 +R= gradual change to green
color
6. Rxn with K3Fe(CN)6 & NH3 +R= deep red color
7. Ppted by salts of Cu++,Pb++, & Sn++ and by
strong aq. Pot dichromate or 1% chromic acid
 Inhibit peroxidation and trap free radicals
 Enzymatic inhibitors, stop cancer, inh replication of
virus
 Astringent prop
 Precipitate protein - styptics and internally for
protecting inflamed surfaces of mouth and throat
 Antidiarrheal
 Antidote – heavy metal poisoning, alkaloids, glycosides
 Precaution: absorbed tannic acid can cause severe
central necrosis of the liver (hepatotoxic)
 Condensed tannin (green&black tea) – antitumor activity
 Cranberry juice –reduced bacterial infections in the bladder.
1. Acidic
2. Sharp Puckering Taste
3. Causes Precipitation of Alkaloids
4. Can Precipitate proteins; used in the
tanning industry
5. Astringents- GI or skin
6. Treatment of burns
 HYDROLYZABLE NON-HYDROLYZABLE
TANNINS

Hydrolysis Easily hydrolyzed to sugar Polymerization to red insoluble

and phenolic acids compound: “phlobaphene
Results from the condensation of
catechin and leucocyanidins”
Other name Pyrogallotannin Phlobatannins, Condensed
When heated Yield pyrogallols Yield catechols
With FeCl3 Blue black color Green black color
Leather produced “bloom” “tanner’s red”
With Br2 No precipitate With precipitate
 SHIKIMIC ACID
PATHWAY

+ ++ - -
NAD , Co HO COO H2O COO

3-dehydroquinate 3-dehydroquinate
synthetase O OH dehydratase O OH
OH OH
3-dehydroquinate 3-dehydroshikimate
NADPH
3-dehydroshikimate
reductase +
NA DP +
+
H
- -
COO ADP + COO
Pi
ATP

shikimate
O
P O OH kinase HO OH
OH OH
shikimate 3-phosphate shikimate
 rearrangement
anthraquinones

1. Direct
transmination

Phenylalanine
Tyrosine
2. dehyration,
decarboxylation

hydroxylation

Oxid.
3.decarboxylation deamination
 Cinnamic acid
demethylation
hydroxylation
hydroxylation

reduction

benzaldehyde
reduction
methylation

Benzyl alcohol

methylation
 Hamamelis leaf / Witch Hazel Leaves
 leaf of Hamamelis virginiana
 constituent: hamamelitannin (bark only), galli/
ellagitannins; nlt 3% tannins
 use: astringent, hemostatic properties, anti-inflam
due to 5-LOX inhibition
 Hamamelis water or Distilled Witch Hazel Extracts –
 Use:
 Astringent
 Incorporated in hemorrhoidal products
 Treatment of insect bites and stings
 Teething preparation, sprains, bruise, superficial wounds,
ing of eye lotion
 Constituents: 2-hexen-1-al, safrole
 Hawthorn (Crataegus monogyna), Rosaceae
 Dried false fruits
 Procyanidin
 Mild cardiac tonic, used prior to Digitalis therapy
bec of being less toxic
 Rhatany ( Krameria triandra), Krameriaceae
 Dried root has Reddish brown bark
 Proanthocyanidin ( condensed tannin); krameria red
 Astringent, antimicrobial in mouth/ throat infections
 Pomegranate ( Punica granatum) Punicaceae
 Dried pericarp of fruit
 28% ellagitannin
 Astringent, diarrhea
 Nutgall/
turkish galls - excrescence from twigs
of Quercus infectoria (dyer’s oak), Fagaceae
 caused by the puncture and deposition of eggs of
gall-wasp Adleria gallaetinctoriae/ Cynips
tinctoriae
 Galls graded based on color – blue, green, white (
mature as the insect escape from the gall)
 White – has decomposed tannin, with circular
tunnel
 constituent: 50-70% gallotannic acid, gallic acid
 use: tanning and dyeing industry, astringent
 Syringic acid – CNS active comp of MeOH gall
extract
 Kino ( Pterocarpus marsupium) fabaceae
 Astringent
 Phlobatannin
 Dried juices
 Aspidospermaquebracho-blanco
(Apocynaceae)
 Bark
 Catechu/ gambir ( Uncaria gambir),
Rubiaceae
 Dried aq. Extract from leaves and young twigs
 In cubes, very friable
 Catechins, catechutannic acid, catechu red