Purvi H. Kakrani, Department of Pharmacognosy, ARCP, Vallabh vidyanagar Dr. Harish N. Kakrani, Principal, CDCP , New Vallabhvidyanagar Definition: Glycosides are (usually) non-reducing compounds, on hydrolysis by reagents or enzymes yield one or more reducing sugars among the products of hydrolysis.
n ns g r o -ua ( e in gn ) g c s ic ly o id lin a e kg s gr ua ( ly o e g c n)

1- Alcoholic or phenolic (aglycone): e.g., O-Glycoside
C H H 2O O H

C 2O H H O C 6 H1 O5 1

C6 H1 O6 + 2 Sgr ua

- 2O H
S l cn ai i

G c sdcl n a e l oi i i k g y

2- Sulphur containing compounds: e.g., S-Glycoside
G lycosidic linkage SH S C 2 H N O SO 3 K C H C 2 H C N O SO 3 K C6 H11 O5

C 6 H12 O 6 Sugar

+ CH 2


C 2 H



3- Nitrogen containing compounds: e.g., N-Glycoside
2 2



O H H O H + N N N H


N N O H O H A e in dn e O H G c s iclin a e ly o id kg

4- C-Glycoside

C6 H12 O6

+ C 2O H H G lycosidic linkage C6 H11 O5 Barbaloin C 2O H H


1- Sugars exist in isomeric α and β forms. Both α and β Glycosides are theoretically possible. 2- All natural glycosides are of the β Type. 3- Some α linkage exists in sucrose, glycogen and starch. Also the glycoside K-strophanthoside (strophanthidin-linke to strophanthotriose (Cymarose + β-glucose + α- glucose).

1- According to the type of glycosidic linkage: α- glycoside (α-sugar) and β-glycosides (β-sugar). 2- According to the chemical group of the aglycone involved into the acetal union: a. O-glycoside (OH group) b. S-glycoside (SH group). c. N-glycoside (NH group). d. C-glycoside (C group). 3- According to the nature of the simple sugar component of the glycoside: a. Glucosides (the glycone is glucose). b. Galacosides (the glycone is galacose). c. Mannosides (the glycone is mannose). d. Arabinosides (the glycone is arabinose). 4- According to the number of the monosaccharides in the sugar moiety: a. Monoside (one monosaccharide) e.g., salicin. b. Biosides (two monosaccharide) e.g., gentobioside. c. Triosides (three monosaccharide) e.g., strophanthotriose. 5- According to the physiological or pharmacological activity ‘therapeutic classification) a. Laxative glsycosides. b. Cardiotonic glycosides. 6- according to the correlation to the parent natural glycoside: a. primary glycosides e.g., amygdalin, purpurea glycoside A, b. Secondary glycosides e.g., prunasin, digitoxin. 7- According to the plant families.

3 8- According to the chemical nature of the aglycone: a. Alcoholic and phenolic glycosides (aglycones are alcohols or phenols) b. Aldehydic G (aglycones are aldehydes). c. Cyanogenic G (aglycones are nitriles or derivatives of hydrocyanic acid). d. Anthracene or anthraquinone G (aglycones are anthracene der.). e. Steroidal G (aglycones are steroidal in nature, derived from cyclopentanoperhydrophenanthrene) . f. Coumarin G (aglycones are derivative of benzo α-pyrone). g. Chromone glycosides (aglycones are derivatives of benzo-δ-pyrone) h. Flavonoidal G (aglycones are 2-phenyl chromone structure). i. Sulphur containing or thioglycosides (aglycones are contain sulphur). j. Alkaloidal glycosides (aglycone is alkaloidal in nature) e.g., glucoalkaloids of solanum species. Sugars in glycosides: 1- Monosaccharide (glucose in salicin, rhamnose in ouabain) 2- Disaccharides (gentiobiose in amygdalin). 3- Trisaccharides (strophanthotriose). 4- Tetrasaccharides (purpurea glycosides) 5- Rare sugers (deoxy sugers) 6- Sugar linked in one position to the aglycone rarely in 2 positions as sennosides.

A- 6-deoxy sugars e.g., 1- methylpentoses
H H H O H O CO H H C O C O H C H C H C 3 H

2- α-L-rhamnose.




B- 2,6-deoxy sugars (called rare sugars) e.g., 1- D.digitoxose 2- D.cymarose 3- diginose

OH Diversity in structure makes it difficult to find general physical and chemical properties: 1.all glycosides are hydrolysable by acids non specific (except C-glycosides).Acetal linkage between the aglycon and glycone more unstable than that between two individual sugars within the molecule. d.Give positive Schiff’s test for aldehydes.Most glycosides are water soluble and soluble in alcohols.Positive Keller-Kelliani test. B. 2.C-glycosides are very stable (need oxidative hydrolysis).Alkali hydrolysis: .g. but when are susceptible to hydrolysis give reducing sugars (C-glycosides are exceptions).More sugar units in a glycoside lead to more soluble in polar solvents.Acid hydrolysis: a. 2. 1.4 CO H C H2 C C C C H 3 CO H C H2 C OH C C C C H 3 CO H C H2 3 O H O H O H H3 C O C H O H C C C H 3 O H O H O H C.Glycosides containing 2-deoxy sugars are more unstable towards acid hydrolysis even at room temperature.Either insoluble or less soluble in non polar organic solvents. C. b. 2-deoxy-D-ribose HOH2 C H O H OH H Characteristic of 2-deoxy sugers: 1.2-deoxy sugars e.Glycosides do not reduce Fehling’s solution. 2. c.A.

Enzyme hydrolysis: 1. 6.De-fating or purification of the plant material (in case of seeds). b. e. Cold acid pH treatment.Maltase and invertase are α-glycosidases. capable of hydrolyzing α-glycosides only.Glycosides are not precipitate from aqueous solutions by lead acetate. but α and β sterio-isomers of the same glycoside are usually not hydrolysed by the same enzyme.Purify aqueous extract: a.The same enzyme is capable to hydrolyze different glycosides. Boiling with acetone. 2.Emulsin is found to hydrolysed most β-glycoside linkages. those glycoside are attacked by emulsin are regarded as β-glycosides.Precipitate excess lead salts. .Destruction of hydrolysing enzymes. 3. 7. 1. at 100 C˚. Some times ether saturated with water for dry material. a. 5.Concentrate the alcoholic extract (to get rid of the organic solvent). 2. d. Add water (or hot water)→ filter any precipitate.5 1. c. Extract at very low temperature. 3. Place plant in boiling water or alcohol 10-20 min.Non-polar organic solvents are generally used for de-fating process.Extraction of the glycosidal constituents by alcohol.Water soluble impurities precipitate by lead acetate. Drying for 15-30 min. 2.Isolation of the glycosides from the purified aqueous solution.strong alkali 3.mild alkali 2. water or dilute alcohols. b.Extract non glycosidal impurities by org solvent. 1.Enzymatic hydrolysis is specific for each glycoside there is a specific enzyme that exerts a hydrolytic action on it. 4. by crystallization.Water mixed with different proportions of methanol or ethanol (most suitable extracting solvent). 4. 3.

Keller Killiani’s test for 2-deoxy sugers: Specificity of action of the hydrolyzing enzymes is often applied for the identification of the sugar moieties of glycosides or even the glycoside as alcohol. but reducing sugars upon hydrolysis. 5.By the use of α and β glycosidases. 1. Determination of the glycosidic linkages: 1. . 1.Prunasin [Prunase] →→→ glucose + HCN + H C O C C N 6H1 1 O5 3.Scillarin A [acid hydrolysis] →→→ Scillaridine A + Scillabiose Scillabiose [Scillabiase] →→→ Rhamnose + glucose. (by acids or enzymes) 1. characteristic reddish coloration with alkalies.6 They do not themselves reduce Fehling’s.Anthraquinone glycosides and/or aglycone: Give positive Borntrager’s test.Steroidal or cardiac glycosides: Give positive Liebermann’s test (steroidal structure). AlCl3.Sulphur containing glycosides give black precipitate of silver sulphate upon treatment with AgNO3 solution. Sinigrin and sinalbin. To test for the presence of glycosides Estimate reducing sugars before and after hydrolysis. NH4OH.g.Flavonoidal glycosides and/or aglycones: Characteristic color with. 4.glucosides e.Amygdalin [amygdalase] → Prunasin + glucose 4. 2. CHO 2.Cyanogenetic glycosides give upon hydrolysis hydrocyanic acid can be easily tested by change Na picrate paper (yellow) to red color.Myrosin enzyme is specific for thio D.. FeCl3. 3.

flavonoidal glycosides.Laxatives e.. increasing tone. anthraquinone glycosides of senna..Xanthydrol: xanthydrol in glacial acetic containing 1% HCl + glycoside [heat]→ red color. 6. 8. amygdalin known in the U.7 2.g. 7. frangula. immediate optical activity measurement of the resulting solution.g.g. cascara. thus allowing the weakened heart to function more efficiently.. the glycoside glycyrrhizin has a demulcent. 3. as Laetrile.g..Keller Killiani: glacialacetic acid containing + FeCl3 + H2SO4 → brown ring free from red (acetic acid a quire blue). that act as cardiotonic agents. strophanthus.g. N. excitability and contractility of this muscle. Color reactions based on the sugar moiety [2-deoxy sugars]: 1.Some glycosides are claimed to reduce the capillary fragility e.g.S.. 2. 1-The genins of all cardiac glycosides are steroidal in nature. U. rhubarb.More recently as an anticancer agent e.Analgesics e. digitalis glycosides. Stability indicating after extraction.S.g.B... 5.Cardiac drugs: cardiotonic glycosides e.g. Lactone ring 12 11 1 2 3 Sugar O 4 5 6 R 10 9 8 7 C 3 H 13 14 O H 15 17 16 . expectorant and antispasmodic action.Anti-inflamatory: e. hisperidin.Counter irritants e.Anti rheumatic e. aloes. 2-They are characterized by their highly specific action cardiac muscle. methylsalicylate ‘a hydrolytic product of gaultherin.P. rutin. thioglycosides and their hydrolytic products ‘allylisothiocyanate’ 4. Medicinal importance of glycosides: 1.By acid hydrolysis of glycosides.. squill. salicin. 2.

while strophanthus glycoside are characterized by presence of either an aldehydic (CHO) or primary alcoholic (C`H2OH) group at C-10.Cardiac glycosides that α-β unsaturated 5-membered lactose ring in position C-17 are known as cardenolides. C-11 and C-16. 2. These are represented by the digitalis and straphanthus group.Cardiac agents that have doubly unsaturated 6-membered lactone ring in position C-17 are referred to as Bufadienolides.The presence of another β-OH group at C-14.This group includes the squill glycosides and the toad venom.The A/B ring junction is usually (cis).membered lactone ring at position C-17.8 All cardio active glycosides are characterized by the following structural features: 1. O O O 12 H 11 1 2 3 R 10 4 5 6 9 8 7 C 3 H 13 14 O H 17 16 15 Sugar O Cardenolides Digitalis glycosides Strophanthus glycosides R=CH3 R=CHO OR CH2OH 3.The presence of β-OH at position C-3. OR tetra saccharide. which is always involved in a glycosidic linkage to a mono. 2.Digitalis glycosides contain angular methyl group at C-10. 3.Additional OH groups may be present at C-5. 4. 5. also in the β configuration.The presence of unsaturated 5 or 6. 4. di. Bufotoxin. while the B/C ring junction is always (trans) and the C/D ring junction is in all cases (cis). tri. . 1.

all the other sugars that are found in cardiac glycosides are uncommon deoxy-sugars e. Origin: D.. Cymarose. thapsi The structures of the common aglycones of the digitalis group are indicated below: . 2. D. which are extremely difficult to separate and purify. from a single genin one may have a monoside. R2=H R1 & R2 = ester group 5.9 O O O 1 H 2 1 1 1 2 3 Sgr ua O 4 5 6 1 0 9 8 7 1 3 1 4 R1 1 7 1 6 1 5 R2 Bufadienolides Squill glycosides Bufotoxin R1=OH.Major difficulty in the isolation of 1ry glycosides from the crude drug. 6. a bioside.Other difficulty is the existence of several closely related glycosides in the same drug.With the exception of D-glucose and L-rhamnose. Thevetose. purpurea. lutea and D.The glycone portion at position C-3 of cardiac glycosides may contain four monosaccharide molecules linked in series. D. Digitoxose.g. why? because 1ry glycosides are converted into secondary glycosides by hydrolysable enzymes. Thus. lanata.. a trioside or a tetroside. C O H C H2 C C C C 3 H O H O H O H C O H C H2 C O H 3 C C C C 3 H O H O H C O H HC O H C 3O C H H H H C C C 3 H O H O H Digitoxose Isolation difficulties: Cyamarose Thevetose 1.

Purpurea gly A = Digitoxigenin---DX---DX----DX---G 2.Digitoxin = Digitoxigenin------DX---DX----DX. c.Acetyl-digoxin = Digoxigenin---DX---DX----DX---(AC).Digoxin = Digoxigenin------DX---DX----DX. c. b.Deslanoside = Digoxigenin---DX---DX----DX---G .Glycosides derived from Digoxigenin: a.Acetyl-gitoxin = Gitoxigenin---DX---DX----DX---(AC). c.Glycosides derived from Gitoxigenin: a. DX (AC)=Acetyldigitoxose.Lanatoside B = Gitoxigenin---DX---DX----DX(AC)---G.Glycosides derived from Digitoxigenin: a.Lanatoside A = Digitoxigenin---DX---DX----DX(AC)---G.Acetyl-digitoxin = Digitoxigenin---DX---DX----DX---(AC). 1.Lanatoside C = Digoxigenin---DX---DX----DX(AC)---G.Purpurea gly B = Gitoxigenin---DX---DX----DX---G 3.G = Glucose. b. d. b.Gitoxin = Gitoxigenin------DX---DX----DX.10 O R1 11 1 2 3 H O 4 5 6 10 9 8 7 12 17 13 14 OH 16 15 R2 O Compounds Digitoxigenin Gitoxigenin Digoxigenin DX = Digit R1 H H OH R2 H OH H oxose. d. d.

B and C can be obtained by the alkaline hydrolysis of the corresponding lanatosides. Lanatoside B. 3. 3. Lanatoside C are acted by specific enzyme which split the terminal glucose. Lanatoside A purpurea gly. which on turn hydrolyze into the genin K-strophanthidin and the deoxysugar cymarose. K-strophanthin B (bioside) and cymarin (a monoside) were isolated from different strophanthus species.The later gives by hydrolysis one molecule of glucose and the tertiary glycoside cymarin. acetylgitoxin and acetyldigoxin respectively.The 1ry glycoside K-strophanthoside gives by hydrolysis one molecule of glucose and the 2ry glycoside K-strophanthoside B or K. give the 2ry glycosides acetyldigitoxin. .Digitoxin. 2.The glycoside K-strophanthoside (a trioside). A Specific enzyme Alkaline hydrolysis Digitoxin Acid hydrolysis Digitoxigenin + 3 digitoxose Specific enzyme Acetyldigitoxin Alkaline hydrolysis 1. 2.11 1. gitoxin and digoxin are obtained by the action of alkali on their acetylderivatives.The 1ry glycosides Lanatoside A.strophanthin B.The deacetyl-lanatosides A.

O O OH OH OH CH 2 2 3 Rhamnose O 4 5 OH 6 1 10 11 9 12 13 14 8 7 OH 17 16 15 Ouabain (G-strophanthin) This group of cardioactive agents includes the squill glycosides (the scillarins) and the Toad poison (Bufotoxin).strophanthin B K.strophanthidin Cymarin K. The genins of squill glycosides differ from those of the cardenolides in two important aspects: .12 O O 11 1 2 3 O 4 CHO 9 10 5 OH 6 12 17 13 14 16 15 K.strophanthoside 8 7 OH Cymarose B-glucose a-glucose The seeds of Strophanthus gratus contains another glycoside named Ouabain or (Gstrophanthin). which yield on hydrolysis rhamnose and the aglycone ouabagenin. Ouabagenin differs from K-strophanthidin in having 2 additional (OH) groups at C-1 and C11 and having a 1ry alcoholic group at C-10 instead of the aldehydic group.

They are usually soluble in water or aqueous alcohol and insoluble in the fat solvents with exception of chloroform and ethylacetate. the greater solubility in water but lower soluble in chloroform.They have six membered doubly unsaturated lactone ring in position C-17. 2. O O OH Glucose-Glucose-Rhamnose O Scillaridin A Proscillaridin A Scillarin A Glucoscillarin A The Bufadienolides of Squill Name of glycosides Glucoscillarin Scillarin A Proscillaridin A Structure Scillaridin A ---RH—G---G Scillaridin A ---RH—G Scillaridin A ---RH * The different cardiac glycosides show different solubilities in aqueous and organic solvents.They have at least one double bond in the steroid nucleus. * The higher number of sugar units in the molecule.13 1. .

The gitoxin has in addition to tertiary OH at C-14 another secondary OH at C-16.It is recommended to heat stabilize these CG. which may split the primary G into G with less sugar units. they are considered as the solvents of choice for the extraction of all CG from drugs.So it is required by many pharmacopoeias that CG containing drugs must contain not more than specified moisture content and that these drugs should be stored in sealed containers over dehydrating agents. 2. These with the double bond of the lactone ring from a conjugated double bond system that makes the compound fluorescent in UV light.Specific enzyme usually coexist with CG in plants. CG deteriorate during drying and storage unless special precautions are taken. * pet. 1.Acid hydrolysis cleavage of the glycosides into aglycones and sugar residues. Thus. Both OH gps split as water by the action of H2SO4 with the formation of two additional double bonds. 4.ether and ether are used for defatting process of drug. by destroying the enzymes at higher temperatures. they do not dissolve CG. the tertiary OH gp at C-14 may split off as water. leading to formation of an inactive anhydro-form of CG. At higher temperature. .14 * Alcohols are good solvents for both the glycosides and the aglycones. 3. Therefore. O O O O 12 11 1 R 2 10 3 O 4 5 6 9 8 7 CH 3 13 14 OH 17 11 16 15 12 CH 3 13 17 16 15 -H2O 2 3 1 R 10 5 9 8 7 6 14 Sugar Sugar O 4 5.

3.g. . picric acid. rheumatic heart disease.Cardiotonics.Diuretics (capillary of the kidneys are dialated). Kedde’s reagent. HTN. digitoxose and cymarose. 1.5 dinitrobenzoic. alkaline solution of sodium nitroprusside.CG that contain deoxy-sugars are distinguished by Keller Kiliani’s test.All these nitrocompounds react with the active methylene of the five membered lactone ring (in alkaline medium) to give characteristic colors. CHF.. 3. 2. that are all alkaline solutions of aromatic nitro compounds. 2. Raymond’s reagent.CGs are steroidal in nature.Cardenolides are distinguished from the scillarins by a group of color reagents. e. 4. namely. Baljet’s reagent. Legal’s test. metadinitrobenzene. 1. atherosclerosis.15 O O O O 12 11 1 2 R 10 3 O 4 5 6 9 8 7 CH3 13 14 OH 17 16 15 12 CH3 13 OH 11 17 16 15 -2H2 O 2 3 1 R 10 5 9 8 7 6 14 Sugar Sugar O 4 The detection of gitoxin in other digitalis G is based on the above mentioned reaction. give +Ve with Liebermann’s and Salkoviski’s test.

digitalis leaf (digitalis tablets) 2. 3The saturation and/or cleavage of the lactone ring. ouabain and squill.0025% digoxin 4.8 dihydroxyanthraquinone derivatives. Therefore. 2. the closely related CG..16 1. duration of action and their cumulative effect.O-glycosides where the aglycone moiety is 1. strophanthus. .The glycone part displays a great influence on the solubility and the rate of absorption and distribution of the glycosides to the site of action. deslanoside.gitalin.Small change in the molecules such as a change of the location of the OH gp.digoxin injection contain 0. differ greatly in the rate of absorption. strophanthin. modify the cardiac activity or even eliminate it completely.digitoxin tablets 200μg/tablet 3. lanatoside C. 1. A nthraquinone O 8 7 6 5 O 9 10 4 O 8 7 6 5 H 9 10 O H 4 1 1 2 3 8 A nthrone O 1 9 10 5 H H 4 2 3 A nthranol O H 4H 7 6 H 2H 2 3 O xanthrone 1. destroys the cardiac activity. e.g.digoxin tablets contain 250μg/tablet 5.

17 G l O O 9 10 5 O 4 O H 1 2 C 2O H H 5 G l O O 9 10 8 O H 1 2 C O O H G l O O 9 10 8 O H 1 2 C 3 H 8 4 O 5 O 4 A loe-em odin-8-glycoside R hein-8-glycoside C hrysoph ol-8-glycoside an 2. G l O H 7 6 5 O H 9 1 0 4 O O H 8 1 2 3 Emodin-oxanthrone-9-glucoside 3.O-glycosides where the aglycone moiety is di-anthrone der...) OH 7 6 5 H 8 O 9 10 OH 1 4 C6 H11 O5 2 3 CH 2 OH Barbaloin 4. e.g.8 dihydroxy anthraquinone.g. Oxanthrone-type.e. Sennoside A&B G l 7 6 5 H H C O O H O 8 O 9 10 O H 1 4 2 3 C O O H G l O O O H The most widely used drugs that contain anthracene compounds are: .. (i. dimmer) e. Sennosides where there is C-C bridge between the anthranol units.O-glycoside where the aglycone moiety partially reduced 1.C-glycoside where the aglycone structure (anthrone der.

. Thus it can be exist in two optical forms.form) & Sennoside B (meso form). one rhein-anthrone & one emodin anthrone. Sennoside C (L.Similar anthrone moiety (Homo-dianthrones) i..form) and Sennoside D (meso form).Or different (Hetero-dianthrones) i. Cassia senna (C.e.acutifolia). Constituents: Dimeric anthracene glycosides derived from two anthrones moieties which may be: O H O 9 10 5 4 O H 1 2 C 2O H H 5 O H 8 O 9 10 4 O H 1 2 C O O H 8 A loe-em in anth od rone R hein anthrone 1.18 Consists of the dried leaflet of Alexandrian or Khartoum senna.e.angustifolia). Tinnevelly senna (C. Sennoside A (L. G l 7 6 5 H H C O O H O 8 O 9 10 O H 1 4 2 3 C 2O H H G l O O O H Sennoside C&D . 2 rhein anthrone moieties condensate through two C-10 atomes. G l 7 6 5 H H C O O H O 8 O 9 10 O H 1 4 2 3 C O O H G l O O O H Sennosides A &B 2.

specified that the collection must be made at least one year before the bark is used (fresh bark contains an emetic principle)..Four primary glycosides: 1. .Free anthraquinones: Aloe emodin. chysophanol and emodin. Constituents: A. emodine oxanthrone. C. B. aloe emodin and chrysophanol.A number of O.cascarosides A&B (glycosides of barbaloin) 2. O H O O H O H O O H C 2O H H O O C 3 H A ee o in lo md Cr s p a o hyo h n l E.g.glycosides: e. P.cascarosides C&D (glycosides of chrysaloin) O H O O H G l O O O H H G l C 2O H H H G l C 2O H H B r a in a b lo O O H O C s a o id A B ac r s e & O O H O H G l H G l C 3 H H G l C 3 H C r sa in h y lo C sc r s eC&D a a o id B- Two aloins (secondary glycosides): Barbaloin derived from (C-10-C-glycoside) of aloe-emodin anthrone and chrysaloin derived from (C-10-C-glycoside) of chrysophanol anthrone. derived from emodin.19 The dried bark of Rhamnus purshiana Family Rhamnaceae.

the naturally occurring anthracene glycosides were found superior to the synthesis of numerous hydroxyl anthracene der. 3.The presence of tannins in rhubarb makes the drug constipating. 1. O H O O H O . Cascara is a purgative. contained by the crude drug are said to exert a synergistic action. The laxative action of the crude drugs is always higher than from their content of anthracene der.Consist of glycoside of rhein.20 1. C. The only compound which is used to some extent in current medicine is danthrone. 4. It is also used as a standared in colorimetric assays of anthraquinone glycosides. B. Rheidins.Frangulin (frangula emodin rhamnoside). O H O O H R O O F rangulin G lucofrangulin R R = ham nose C 3 H R R = ham nose-glucose 3.Glucofrangulin (frangula emodin glucorhamnoside). but large doses cause purgation. rhein anthrone. Thus.Hydrolysis of frangulin gives frangula emodin and rhamnose. So in small doses.Dianthrones of heteroanthrone types are palmidin A.hydrolysis of glucofrangulin yields frangulin and glucose. Some of these synthetic compounds act too drastically and also caused kidney damage. chrysophanol and aloe emodin. 2. rhubarb exerts no purgative action but acts only as intestinal astringent. elixir or as tablets prepared from a dry extract. sennosides A&B and their oxalate esters (sennosides E&F). mainly in the form of liquid extract. 2. The different anthracene der.

3.. aloins are very resistance to hydrolysis and are not easily hydrolysed (like other anthrones and anthranols) to corresponding anthraquinones.C-C glycosides. Complete reduction of C-10 &C-9 lead to complete loss of activity.Aloin type glycosides are present in aloes and other anthracene bearing drugs of the family liliaceae.Oxidation level: The degree of oxidation at positions C-9 & C-10 plays an important role in the pharmacological activity. However. as the sugar moiety serve to transport the aglycone to the site of action in the large intestine).Effect of storage on the active of anthracene glycosides: a. The latter more active than derivative with COOH substitution at C-3. 4.The nature of substances at C-3: Derivative with CH2OH (as in aloe emodin) are more active than those with CH3 substitution.21 Danthrone Note: 1. 2. the activity of drugs decreases by time. glycosylation is the main requirement for activity. Anthraquinone glycosides containing adimer more active than a monomer. i.Prolonged storage of anthracene bearing drugs may bring oxidation of anthranols and anthrones to give the less active anthraquinones. Higher oxidation level at C-9 & C-10 caused lowering of activity. C-8 is essential for activity.. anthraquinone glycosides do not cause any griping action (like . anthrones and anthranols are more potent than their corresponding oxanthrones. 1. Increase hydroxylation leading to increase solubility. 5. Thus.Hydroxylation: Hydroxylation of C-1.Glycosilation: The purgative action of anthracene bearing drugs is owed to their anthracene glycosidal content rather than their content of free anthracene aglycones (i.e. which in turn more active than their corresponding anthraquinones.The 1ry glycosides are more active than the aloins while the free anthraquinon have little purgative activity.e. 3. 2.

The aglycones are extracted from the acidic solution with ether or benzene.Cascara tablets. produce higher pharmacological activity.WHY? Stability is achieved as follows: 1. the C-10 position can not be easily oxidized and the anthrone structure is stabilized. Thus.S.: 1. c.Senna leaf & senna fruit (pod). elixir. The glycosides are extracted and hydrolyzed by boiling the drug with acids. liquid extract. dry exract.P and U.Danthrone 6.In the aloe. Borntrager’s reaction can distinguish anthraquinones from anthrones and anthranols which do not give the test unless they are converted to anthraquinone by oxidation with mild oxidants such as hydrogen peroxide or ferric chloride. 5. tincture. because of the formation of anthraquinone salts. Official anthraquinone drugs in B. the aloins (barbaloin & chrysaloin) contain C-C glycosidic linkage (anhydroglycosides) stabilise the anthrone structure. 2.22 anthranol and anthone).In cascara. 3. Upon shaking the ether or benzene layer with aqueous alkali or ammonia solution. The solubility of cascarosides is increased and thus. 2.Cascara and frangula must be aged for one year before it is used for medicinal preparation. b. Aloe and cascara preparations retain their activity for a long time.In senna.Aloes. cascarosides have an additional O-glycosidic linkage (beside the C-10-C glycosidic linkage. the aqueous layer assumes a deep red color.Rhubarb powdered. there is dimeric glycoside in which a C-C bridge between two anthrone units is formed (the C-10 position of one anthrone is involved in a C-C-covalent bonding with C-10 of the other anthrone).Frangula bark . thus no antispasmodic such as belladonna is prescribed with them. 4. 4.Drugs as senna.P.

chalcones and aurones.3double bond is lacking). True flavones. while flavanones are 2. Flavonols are 3-hydroxyflavones.23 Flavonoidal compounds are considered as the largest group of naturally occurring phenols. are 2-phenyl chromones (2-phenyl benzopyrone). Flavonoidal compounds are classified according to the oxidation level of central pyran ring they are classified into flavones. flavonols. chalcones and aurones are lack the typical flavone structure. while isoflavones are 3phenyl chromones der. thus they have a basic C-15 skeleton. (2-phenylbenzopyran) 8 7 6 5 9 1 O 2 10 4 3 2' 1' 6' 5' O (2-phenylbenzopyrone) 3' 4' O Flavan Flavone O O OH O O Flavonol O H H O Isoflavone Flavanone Anthocyanidines. Flavonoidals constitute the majority of the yellow colored plant pigments. This is responsible . Many flavonoidal compounds present as a glycosidic or as a free forms. 2-phenyl-benzopyran (flavan). of flavones (2. Anthocyanidins and its glycosides (anthecyanins) are ionic oxonium salts. isoflavones.3-dihydro der. flavanones. (true flavanoids) anthocyanidins. All derived from the same parent nucleus.

that usually show two main bands. Flavonoids exhibit strong fluorescence under UV light. 8 7 6 5 + O 3 2' 1' 6' 5' 3' R OH 4' OH R X 8 7 6 5 9 Cl + O 3 2' 1' 6' 5' 3' OH 4' OH 9 10 10 OH Anthocyanidins Cyanidin chloride OH Chalcones. purple. so they are not true flavonoidal compounds. fruits and leaves of higher plants. The parent compound chalcone. mauve. Anthocyanidins and anthecyanins are soluble in polar solvents.24 for the permanent blue. is chemically phenyl-styryl ketone. CHALCONE AURONE O C H O O Flavonoids dissolve in alkalis give intense yellow color solution. Flavonoidal glycosides are soluble in water and alcohol. and red color of flower. violet. aurones have five membered ring. on the addition of acid become colorless. have no central pyrone ring. or benzylidene acetophenone.Band at lower wavelength (band II) which is due to the benzoyl fraction of the flavonoidal structure. Flavonoids compounds may be characterized through the investigation of their UV Spectra. Aurones are oxidized forms that are obtained by enzymatic oxidation. 1.Band at higher wavelength (band I) which is attributed to the cinnamoyl fraction of the flavonoidal structure Why?. . Cyanidin chloride is an example of anthocyanidines . Instead of the central pyrone ring of the normal flavonoidal structure. 2. Ethylacetate is the solvent of choice for the extraction of flavonoids from aqueous solution.

More OH in ring B: Bathochromic shift in band I. Rutaceae. and in part to diosphenol. Shift reagents: Back to lab. . Barosma crenulata F.25 B enzoyl O A R B C am inn oyl O A II B d an 200 H ypsochrom shift ic W len ave gth I B d an 400 B ochrom shift ath ic Band I >> 300 nm If R= H Flavones Band I: 304-350 nm R=OH flavonols Band I: 352-385 R=O-substitution 3-sub flavonol Band I: 328-357 Band II << 300nm (250-280 nm) Note: More OH in ring A: Bathochromic shift in band II. Uses: diuretic and diaphoretic action of the leaves is owed in part to diosmin. 1.Diosmin: flavone glycoside Occurance: buchu leaves. the main constituent of the volatile oil of the leaf.

Rutin is used to 1.Rutin and quercetrin: are examples of flavonol glycosides a. The aglycone quercetin occurs in bearberry leaves (Uva Ursi) and has a diuretic action of the leaves. 2.It is a biflavonoids that plays a true vitamin function.Quercitrin is quercitin 3-O-rhamnoside. . b. glucose and hesperitin.Rutin occurs in the leaves of buckwheat. O H R O O A O H B OH C 3 O H prtn R e ei i s : H H prd e ei i s n R ui oy : tns l r Upon hydrolysis by acid.26 O H R. Quercitrin yield upon acid hydrolysis rhamnose and quercetin.l hG a O O A O H B OH C 3 O Diosmin Upon hydrolysis.Decrease capillary fragility.Hesperidin: it is an example of flavanones. It occurs in the bark of Quercus tinctoria. It is the 3-rhamnoglucoside (called rutinose) of the genin quercitin. 2. It gives on hydrolysis the aglycone (quercitin) beside one molecule of glucose. and one molecule of rhamnose. It is the main flavonoidal glycoside of citrus fruits. hesperidin gives rhamnose. diosmin yields rhamnose. O H HO O A O R O H O B O H Qe c t : u r ein Qe c t i : u r ern Rt : uin RH = R r a ns l = h moy R r tn s l = ui o y 3. glucose and diosmetin.

Genistein show significant oestrogenic activity.It is necessary for absorption and retention of vit C that lead to decrease capillary fragility. H O O O H O O H 2. Isoflavone: 1. 2. 2. 3.They are reported of value in the treatment of influenza.Rotenoids employed as insecticide. O H O A B O H O H + O R O H O F v n idmie y la o o o t Hm lig a mie e i.n n o ty O H O A B O O O H OH 3 C O H O O H F v n lig a la o o n n . Uses of flavonoids: 1.They are recommended in the treatment of thrombopenia (blood coagulation). O O O O Flavono-lignans Coupling of a flavonoid moiety with hemi-lignan molecule by oxidative coupling. when given with ascorbic acid.Increase capillary resistance and decrease vitamins C & P deficiency. 3.Hesperidin appears to be identical to vitamin P (citrin).Decrease CVD and HTN.27 Uses: 1.

It is used for treatment of liver cirrhosis caused by plant toxins (mushroom. 2. Genurin). silyhexal.It is a free radical scavenger.28 The leaves and fruits of Silybum marianum family Compositae contain silymarin (silybin). * Saponins are a group of amorphous colloidal glycodides which is wiedly distributed in the higher plants. . Trade name legalon.Supportive treatment of acute and chronic alcoholic poisoning and toxin induce hepatitis. silymarin is applied as intravenous injection. 4. Flavoxate tablets are available under several names: Urispas. silirex…etc. 3. 5. effervescent granules. * Have ability to form lasting foam when shaking in aqueous solution. amanita). Uronid.Silymarin is a very effective lipotropic and hepato protective therapy. O H O A O H O H O B O O O H O H C 3 Silybin O H 1. Spasurit. Synthetic flavonoids Flavoxate: N O O O A C H O 3 B Fvxt l oa a e Uses: To remove pain (anti-spasmodic) and anti-inflammatory of the genitor urinary tract. * They are excellent emulsifying agents (modify surface tension).Silymarin is available in the market in the form of tablets.

O O CO OH R2 H O D s e in io g n Q illa a id R= H . quillaia). Chemically: Saponins are classified according to the genin part into: 1.. Both types of saponins have the glycosidic linkage at position 3. . e. they are a suitable precursors in the partial synthesis of these hormones. they precipitate the cholesterol and lethicins that exist in the memberanes of the red blood cells and thus haemoglobin is liberated. Diosgenin (sapogenins) isolated from the rhizome of Dioscoria species.Triterpinoidal type C30. They form colloidal solution with water and are soluble in alcohol and dilute alcohols. they precipitated from solutions containing them by the addition of a solution of the sterol.Steroidal type C25.29 * Formerly used as detergents to replace soap (e.. * Saponins are colorless and optical active. filtering off the insoluble sterol-saponin compound and boiling it with toluene which resolves the compound again into sterol (which is soluble in toluene) and saponin (which is insoluble in toluene). However. However. So.The steroidal saponins are structurally related to modern synthetic compounds that have a therapeutic significance. saponins are extremely toxic when injected into the blood stream. * Saponins are difficult to purify.g. such as adrenocortecoids and the sex hormones.g. R O u ic c : 1 C O = H O n lica idR= H. they are not harmful when taken orally. 2. R= lia o c 1C 3 2H H O R1 Medicinal importance of saponins: 1. So. * Saponins have haemolytic properties.

b. is the main sweet principle of liquorice. glycyrrhizin. cardiac glycosides). which in tern is the diglucuronic acid glycoside of glycyrrhitinic acid. Ipeca. .. It is calcium and potassium salts of glycyrrhizic acid. glycyrrhizin.g. CO OH O G c rn . expectorant and antispasmodic action.l c rn lu u o icgu u o ic O BG c r h in . liquorice has demulcent.Beside being a valuable flavouring and sweetening agent..ly y r it ic G c r h ica id ly y r iz c G c r h in= a K ly y r iz C.Saponins increase the rate of absorption of many pharmacological active substances (e. a-The triterpenoidal saponin glycoside. Senaga and liquorice) as their contents of saponins stimulate bronchial secretion and also activate the ciliary epithelium of the bronchi. 3.Many saponin-containing drugs are used as expectorants (e.g. All these activities attributed to the saponin.30 C 3 H O H O O C O O H O O T sto r n e ste o e O P o e te o e r gs r n C 2O H H C O O H O O H O O D s e in io g n Cr o e o tis n 2.

3.P: 1.4d l .True tannin solutions have the ability of precipitating soluble proteins (gelatine).Recently..P and U.31 c. that usually coexist with true tannins. These simpler tannins like compounds are referred to as pseudotannins. 1. heavy metals. flavan-3.This will exclude simple molecular weight compounds such as gallic acid.4-diol and chlorogenic acid. glycyrrhizin was shown to be effectively in gastric ulcer treatment and have a cortisone like action in rheumatic arthritis and other inflammatory diseases.O O H O H H O O C lo o e ica id h r gn c O H O H F v n3 . It is more acceptable to define true tannins as those high molecular weight phenolic plant constituents that can be detected by Glodbeater’s skin tanning test. Saponins drugs officially in the B.Liquorice root: used as flavouring agent and expectorant. 2. and can be quantitatively estimated by absorption on standard hide powder.Tannins are widely distributed phenolic plant constituents. Only high molecular weight tannins that are capable of tanning hide. 2.S.Quillaia bark: used as emulsifier.io la a . catechin. It is characterized by being able to combine with proteins of animal hides thus preventing their putrefaction and converting them into leather (true tannins). 4. alkaloids and glycosides. H O H O O H H O H O O H CO OH CO OC 6 H1 1 O5 Gllica id a c G c g llin lu o a O H O H H O H O C = HC O HC .Tannins are detected qualitatively by Goldbeater’s skin test (a tanning test).

c.Gallitannins and ellagitannins react with ferric salts to give bluish color precipitate.Condensed tannins: a. C 2O H H G l O Salicin . d. e. it reacts with ferric salts to give greenish color precipitate.4-diol.Tannins of gallic acid are called gallitannins and those of ellagic acid is called ellagitannins. 2.Being phenolic. as it contains free primary alcoholic group.A phenolic glycoside.32 Hydrolysable tannins Condensed tannins 1. so called phenolic acid glycosides. b.These are more resistant to hydrolysis upon prolonged heating with acids. as its aglycone is phenolic in nature.These can be hydrolyzed by acids or enzymes to give phenolic acids (gallic or ellagic) and glucose.Dry distillation of condensed tannins gives catechol. d. This class is named catechol tannins. c.Condensed tannins are derived from catechin and flavan.Alcoholic glycoside.They undergo decomposition (not hydrolysis) to give a red soluble compound (phlobaphane). 3. This class is named pyrogallol tannins.Salicin: Salicin is classified as: 1. b. 1. 2.Hydrolysable tannins: a.Dry distillation of hydrolysable tannins gives pyrogallol.

asprin and other antipyretics and anti-inflammatory agents. 1. the principle commercial source is Salix fragilis.It is used as diuretic and also has bactericidal action. Acid hydrolysis of salicin gives glucose and a phenolic ether called saliretin which is a condensation product of two molecules of saligenin. which have largely displaced in medical practice. 3.Uva ursi leaf contains also methylarbutin (the methyl ether of arbutin). C 2O H H G l Ez m ny e O A id c C 2O H H HO +G c s lu o e C 2O H H O +G c s lu o e S lig n a e in C 2O H H S lir tin a e 6- Oxidation of saligenin gives salicylic acid and this accounts for the medicinal value of salicin. 45- Salicin is hydrolyzed by the enzyme emulsin into saligenin (Salicyl alcohol) and glucose. 3.Arbutin is a phenolic glycoside that occurs in bearberry leaves Arectostaphyllos uva ursi.When hydrolysed with acids or with emulsin it yields glucose and hydroquinone. . This activity is due to the hydroquinone given by hydrolysis. It is now used as an analgesic-antipyretic in case of periodic fever.33 123- Salicin is obtained from different species of Salix. Salicin is used for many years as a remedy in the treatment of fever and rheumatism. 2. It is better tolerated in the stomach than sodium salicylate. that also contributes to the diuretic and urinary antiseptic action of the leave.

The fruits of the plant (pods) are collected and carefully cured.From Eugenol CH 2 -CH=CH 2 CH=CH-CH 3 CHO KOH OCH 3 OH OH OCH 3 Oxidation OCH 3 OH Eugenol isoeugenol Vanillin . To permit enzymatic action on the glycoside with the liberation of vanillin (the aglycone) which is the principal flavouring constituent of the pods.From Coniferin and lignin C =C -C H H H H 2O C =C -C H H H H 2O C O H H ydrolysis O H3 C O l -G O H O H3 C O xidation O H3 C O H C oniferin C oniferyl alcohol V anillin 2. 2. lignin or from the phenolic volatile oil constituents eugenol. It may be obtained from vanilla pod or prepared from the glycoside coniferin. 3.34 O H O C H 3 Ol G A un r t bi Ol G M y run e l bt t a i h 1. C O H C O H OH C O l -G 3 OH C O H 3 G co a illin lu v n Vn a illin 1.Glucovanillin is a glycosidal constituent of green vanilla pods.Vanillin is widely used as a flavouring agent.

3.6 linkage. Lignin Hydrolysis coniferyl alcohol Lignin is obtained in extremely large amounts as a by product of timber industry. 2. which gives upon hydrolysis coniferyl alcohol. and is obtained from bitter almonds (Prunus amygdalus Var. Gentiobioside is a reducing disaccharide consisting of two molecules of β-glucose linked by β-1. 1.The majority of cyanogenic glycosides are derived of benzaldehyde cyanohydrin.35 The bulk of vanillin which is produced commercially is prepared from lignin. O C H HCN OH CH CN Sugars M andilonitrile glycosides Benzaldehyde M andilonitrile CH 3 C CH 3 O HCN CH 3 C CH 3 OH CN Sugars CH 3 C CH 3 O-Gl CN Acetone A cetone cyanohydrin Linam arin D-Mandelonitrile gentiobioside 123Amygdalin is the most widely distributed cyanophore glycoside.Plant containing these glycosides are toxic. It occurs in several Prunus species.These are glycosides that are yield hydrocyanic acid as one of their hydrolytic products. 4. . amara Family Rosaceae). Amygdalin is considered as gentiobioside of D-mandelonitrile.The aglycone part is cyanohydrin of a carbonyl compound (condensation product of HCN with an aldehyde or keton).

The latter decomposes spontaneously to form benzaldehyde and HCN.36 CN C O O 6 CH2 O H 5 3 4 O 2 4 1 H 6 C 2 H 5 3 O 2 1 H A ygdalin m CN C O 1 O 2 H 6 CH 2 OH 5 3 4 Prunasin 4- Acid hydrolysis of amygdalin split two molecules of glucose and one molecule of mandelonitrile. the flask is stoppered and incubated in a warm . 5- Different enzymes act upon amygdalin in different ways: Amygdalase Prunase Emulsin or acid Prunase Glocose + Prunasin Glucose + HCN +Benzaldehyde Gl-Gl-O C H CN Gentiobiose + Benzaldehyde + HCN Glucose + Benzaldehyde + HCN Amygdalin The plant material is cutted into small fragments and then a filter paper moistened with sodium picrate is then suspended in the neck of the flask.

37 place (40˚C) for about 30-60 min.The best known compounds Sinigrin and Sinalbin.The anion is called the glucosinolate ion. 3. glucose and the acid sulphate of a quaternary alkaloid. 4. They donot interact until they are brought together by the distruction of the cell walls. S-GL S-GL CH2 CH-CH2 -C N-OSO3 K HO CH2 C N-OSO3 .g.g. Hydrolysis of the glycoside sinalbin gives a phenolic isothiocyanate (Acrinyl isothiocyanate).The glycosides and their specific enzymes are found in different cell in the seeds. yield volatile genins of thiocyanate structure e.Hydrolysis of these. two glycosides occurring in black mustard and white mustard seed respectively. the sodium picrate paper convert to brick red color. sinapine. e. glucose. mustard oils. 2. allylisothiocyanate (volatile oil of mustard) and potassium acid sulphate. R may be aliphatic or aromatic. the coexisting enzymes act upon the glycosides with the liberation of HCN which turns. Thioglycosides 1. The cation (X) may be a simple metal ion or a complex organic cation. 5. By this time.The general structure of thioglycosides is: S L -G R C N S -O O 3 X + 6..A number of plants of the family Cruciferae yield glycosides containing sulphur. .Sinapine+ Sinigrin 67- Sinalbin Sinigrin gives upon hydrolysis. sinapine ion of sinalbin..

The oleo gum resin galbanum that contains umbelliferone in a free state is distinguished from asafoetida that contains only combind umbelliferone.Umbelliferone [7-hydroxy coumarin] is the lactone of umbellic acid which occurs both in the free state and in the form of glycosides in some resins of the Umbelliferae (Asafetida and galbanum). This is made use of in qualitative testing for coumarin. 3.H H . O O O O HO O O a-pyrone coumarin umbelliferone 4. 5. Aglycone 1.O C C C C N 2. Asafetida responds positive to the fluorescence test only after acid hydrolysis. These effects are attributed to their contents of thioglycosides.H 2- C H C H C H 3 3 3 C H 3O Sn l i ec to i apn ai n 8- Black and white mustard seeds are used as rubefacients and counter irritants.38 + C H 3O H O C.coumarin (benzo-α-pyrane).H O. 2-coumarin derivative (hydroxyl and methoxy coumarins). when the characteristic blue fluorescence is given.Coumarin and its derivatives give blue or violet fluorescence in aqueous ammonical solutions (conjugated double bond system). . by the addition of ammonia to its aqueous alcoholic extract. coumarin derivatives and coumarin glycosides and drugs containing them.

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