Anthracene (Anthraquinone)

Glycosides
Anthracene glycosides are oxygenated derivativesof pharmacological
importance that are used as laxatives or cathartics, anti-inflammatory,
antibacterial, antifungal and also as natural dyes.
based on anthracene molecule
O OH O

tautomerization Oxidation

Reduction

H H H OH
Anthrone Anthranol Oxanthrone

Reduction

O Oxidation
8 1
9

10
5 4
O
Anthraquinone
 Anthranols and Anthrones

Reduced anthraquinone derivatives.

Occur either freely (aglycones) or as glycosides.
Isomers.

Anthrone: Parent structure (pale yellow, non-

soluble in alkali, non-fluorescent)

Anthronol: brown-yellow, soluble in alkali,

strongly fluorescent
Anthronol derivatives(e.g. in Aloe – have similar
properties – fluorescence used foridentification)
2
 Oxanthrones

Found in Cascara bark oxanthrone

Intermediate products (between

anthraquinones and anthranols)
When oxidised oxanthrones it form
anthraquinones
Oxanthrones are detected by Modified
Borntrager’s Test
(oxanthrones oxidised using hydrogen
peroxide)
3
 Dianthrones
Derived from 2 anthrone
molecules
2 molecules may/not be
identical
Dianthrones are form easily
due to mild oxidation of
anthrones
It form important
aglycones
Cassia
Rheum
 The activity decreases as oxidation level increase.

Forms of Anthracene derivatives in Plants:

Aglycones:

OH OH OH OH OH OH OH OH
O O O O

HO CH3 CH2OH CH3 COOH

O O O O
Emodin Aloe-emodin Chrysophanol Rhein
Glycosides:
O- glycosides:
e. g. Cascarosides A & B. They are both O- and C- glycosides. Each
one contain two sugar unites.
Glc O OH
O

CH2OH
R1 R
R= Glc, R1= H Cascaroside A
C- glycosides: R= H, R1= Glc Cascaroside B
e. g. Barbaloin it is formed from t he removal of one sugar from
Cascarosides.

OH OH
O

CH2OH
H Glc
 Introduction to Anthraquinones
Historically: Rhubarb, Senna, Aloes and
Cascara were all used as purgative drugs.

Monocotyledons: Only Liliaceae.

Most commonly C-glycoside: barbaloin.

Dicotyledons: Rubiaceae, Leguminosae,

Polygonaceae, Rhamnaceae, Ericaceae,
Euphorbiaceae, Lythraceae, Saxifragaceae,
Scrophulariaceae and Verbenacacea. Also in
certain fungi andlichen.
10
Reduced derivatives ofanthraquinones
Oxanthrones, anthranols and anthrones

Compounds formed by the union of 2

anthrone molecules
Dianthrones

Aglycones:
Chrysophanol/Chrysophanic acid : Rhubarb and
Senna.
Rhein : Rhubarb and Senna
Aloe-emodin : Rhubarb and Senna
11

Emodin : Rhubarb and Cascara

 Senna - Leguminosae
1) Consists of the dried
leaflets of Cassia acutifolia
(Alexandrian senna)

2) dried leaflets of Cassia

angustifolia (Tinnevelly
senna –indian senna).

Use: Laxative & purgative

 Alexandrian senna
Syn.: Folia senna, Cassia senna,
Egyptian senna, Nubian senna
B.S.: dried leaflets of Cassia acutifolia
Delile.
Family: Leguminosae
G.s.: Indigenous to Africa (tropical
regions), Sudan, middle and nile
territories
Used since 9thand 10th century
Itroduced into medicine by Arab
physicians (used both the leaves and
pods)
Exported by Alexandria – name of the
Sudanese drug.
 Indian Senna
Syn.: Cassia leaf, Sonmukhi, senai-ki-patti, bhumiari
B.S.: dried leaflets of Cassia angustifolia Vahl.
Family: Leguminosae
G.S.: South India, Tinneveley & Ramanathpurum district,
Pakistan
Morphology:
Color: yellowish green
Odour: Slight & characteristic
Taste: Bitter & mucilagenous
Shape: lanceolate to ovate lanceolate,
entire margin, uneven base, acute apex,
lamina pubesent.
Size: 2.5 cm-6 cm long & 5mm-8mm wide.
 Cultivation &collection
It is small shrub up to 1-1.5 mt. height. Twice a year & after
paddy crops.
Soil required is sandy loamy, coarse gravelly, loamy soil
which well ploughed, leveled & semi-irrigated.
Seeds sawn in October & February. Within 2-3 months plant
are ready for collection.
Leaflets are collected by hand before flowring. Dried in shade
to maintain natural green color.
1ststage: leaflet are greenish in color & thick
2ndstage: harvesting is done after 30 days of 1st stage
3rdstage: plant are uprooted
Packing: in bales with pressure that cause oblique impressions in
leaves. it remain less brittle and in good condition.
Fresh: anthron, dried at 20-50◦ - dianthron, above 50◦ -
anthraquinone
 Senna – chemical Constituents
Senna consist four types of glycosides:
Sennoside A
Sennoside B
Sennoside C
Sennoside D
In theiractivecostituentsare sennoside A, sennosidesB
Upon hydrolysis of sennosides it gives two molecules
glucose+aglycones: Sennidin A and Sennidin B. Rhein
8-glucosides, Rhein 8-diglucosides
Aloe-emodin
Crysophenic acid, myricyl alcohol, resin
Tinnevellin glycoside(indian senna), 6-hydroxy mucizin
glucoside
Chemical constituents:
 Comparison of
Alexandrian and Tinnevelly Senna
Macroscopical Macroscopical

larger than 4 cmin exceeds 5cm in length

length
Grey-green Yellow-green
Asymmetric at base Less asymmetric at
base
Broken and curled at broken and normally
edges flat
Few press markings Often shows
impressions (mid vein)
21
 Comparison between
Alexandrian and Tinnevelly Senna

Microscopical Microscopical

Hairs less numerous

Hairs – numerous (approximately six
(approximately three epidermal cells apart)
epidermal cells apart) Stomata have 2-3
Most stomata have subsidiary cells with
twosubsidiary cells
the respective ratio
7:3

22
 Senna – Allied Drugs &Substitutes
1. Bombay, Mecca and Arabian Sennas (found in Cassia
angustifolia from Arabia).
2. Palthe senna( Cassia Auriculata)
3. Dog senna – Cassia obovata
4. Cassia podocarpa
5. Argel leaves – Solenostemma argel
6. Coriario myrtifolia

24
 Senna Fruit

25
Chemical test:
Borntrager’s and Modified Borntrager’s test:

Boil plant material with dil. HCl for 10 min, filter and shake with
organic solvent (Ether or Benzene).Separate the organic solvent.
Add ammonia/ NH 4OH .Positive result indicated by Rose Red
colour in the aqueous alkaline layer.
 Cascara
Syn: Sacred bark, cortex rhamni, Californian buckthron, cascara
sagrada
B.S.; Rhamnus pershiana
Family: Rhamnaceae
G.S.: N.Colifornia, columbia, canada, Kenya
Morphology:
Color: outer surface: dark purple to brown (lichens & moss)
Inner surface: yellow to reddish brown
Odour: cherecterictic
Taste: bitter
Shape: Single squill, curved or channel
Size: 5-20 cm long, 2-3 cm wide, 1.2-4 mm thick
Chem const: Cascaroside A,B,C,D
Use: bark extractcollected, dried and stored for 12 months
(↓ anthraquinone content -> less toxic)
more violent purgative
griping action
harder to eliminate

Use: night before to clear bowels for x-rays.

Larg dose use as cathartic.
Chemical constituents:
(i) 4 primary glycosides
 O- and C- linkages

To get aglycones FeCl3

To get aloins oxidise withacid

(ii) C-glycosides - twoaloins

 barbaloin – derived from aloe-emodin
 chrysaloin – derived from chrysophanol
(iii) a number of O-glycosides
 derived from emodin oxanthrone, aloe-emodin, chrysophanol
(iv) various dianthrones
 incl. emodin, aloe-emodin, chrysophanol, herterodianthrones palmidin A
BC
(v) aloe-emodin, chrysophanol, emodin in free state
 Rhubarb
Syn.: Rheum, Radix rhei, da huang
B.S.: Peeled & dried rhizomes , root of Rheum officinale
Bail., R.palmetum L., R.rhaponticum Willd (chinese)
R.emodi Wall., R. webbianum Royale (Indian)
Family: Polygonaceae
G.S.: Tibet to south east china, germany, south europe,
kashmir, kullu, Sikkim, UP, panjab, nepal
 Morphology
Color: fresh surface after cut pink to dull grey in day
light & reddish brown UV
Odour: Characteristics
Taste: Bitter, gritty, astringent
Size: 8-10 cm in length, 3-4 cm thick
C.C.: rhein, glucorhein, emodin, aloe emodin and
chrysophenol
Palmidin A, B, C
Rheinoside A,B,C,D
 USE
Bitter, stomachic, laxative, purgative, diarrhoea,
eczema, psoriasis
ADULTRANTS
Rheum rhaponticum,
R. undulatum
R.copactum
Japanese rhubarb
 ALOE
Syn.: Kumari, musabar, korphad, Gheekunwar, Ghrit
kumara
B.S.: dried juce of leaves of Aloe barbadensis Miller(
Curacao Aloe), Aloe perryi Baker (Socotrine aloe),
Aloe ferox Miller., Aloe spicata Baker (Cape Aloe)
Family: Liliaceae
G.S.: Estern & southern Africa, west Indies, India,
western region.
Aloe perryi, barbadensis, ferox
 Preparation of Cape Aloes
 Cape Aloes are prepared from the wild plants of Aloe
ferox.

 Leaves are cut transversely near thebase.

 Twohundred leaves arranged around a shallow hole in

the ground (lined withcanvas or goatskin).

 Cut ends overlap &drain into the canvas.

After 6hrs all the juiceis collected.

 Transferred to adrum.

 Boiled for 4hrs on an open fire.

 P41oured into tins while hot  solidifies.

 Preparation of Cape Aloes

42
 Cape Aloes - Characteristics
Dark brown or Green-
brown

Glassy masses

Thin fragments have a

deep olive colour

Semi-transparent.
43
 Cape Aloes - Characteristics
Powder: green-yellow

When rubbed two pieces

of drug together – powder is
found on the surfaces.

Characteristic sour odour

(rhubarb/apple-tart odour).

Taste: nauseous and bitter.

Microscopy: powder in
lactophenol – amorphous.
44
 Characteristics of Curacao Aloes
Colour: yellow-brown – chocolate brown.
Cut at base, V shaped container of wood 1-2 mlong with cut
surface towards container.
Poor qualities (overheated) blackcolour.
Opaque
Breaks witha waxyfacture
Semi-transparent
More opaque on keeping.
Nauseous and bitter taste.
Thick hot juice taken completely in copper(metal) pan till it
become thick(hard)

45
 Socotrine aloe
Juice collected on goat skin and allow to dry for long
time without heating or boliling.
It forms viscous pasty mass which is filled in
container of wood.
Zinzibar aloe
Same as above
Also called monkey skin aloe.
 Aloes - Constituents
C-glycosides
Resins
Glycosides
Aloin
Barbaloin
Isobarbaloin
Aloe-emodin

Cape Aloes: Also Contain

Aloinoside A &Aloinoside B
(O-glycosides of
barbaloin)
47
 Aloe - Constituents

48
 Aloe Constituents &Chemical
Tests:
 Unlike C-glycosides, O-glycosides
of Aloe are not hydrolysed by
heating withdilute acids or alkali.
Can be decomposed withferric
chloride &dilute HCl
Modified Borntrager’s Test– oxidative
hydrolysis. Anthraquinones give a
red colour when shaken withdilute
ammonia.
General test for aloes.--All Aloes give
a stronggreen fluorescence with
borax (characteristic of
49
anthranols) -
 Aloe - Uses
Purgative, abortification,
emolient, stomachic,
stimulant &tonic.
Used in solar, tharmal,
radiation burns, in skin
irritation
Cosmetic

50
 Aloe vera Products
These are derived from
the mucilage gel –
parenchyma cells
Should not be confused
withaloes (juice of
pericycle – juice used for
laxative effect).
Cosmetic industry
(usefulness often
exaggerated) - Used as
suntan lotions, tonics and
food additives.
Mucilage =
52
polysaccharide of
glucomannans and pectin