phenol glycosides - PowerPoint Sunusu

PHENOL GLYCOSIDES

Any compound with a hydroxyl group linked directly to a benzene ring is called PHENOL.

PHENOL GLYCOSIDES

Some phenolic groups are found in the plants in the free state; e.g. thymol, carvacrol, eugenol…

There are those in the structure of diphenol such as Flavonoids; triphenols such as tannins

thymolquercetin

Epigallocatechin gallate (EGCG)

PHENOL GLYCOSIDES

There are dimerization derivatives of phenols in phenyl

propanoid structure; e.g. lignans

PHENOL GLYCOSIDES

Glycosidic bond between phenolic –OH and sugar is called PHENOL GLYCOSIDE

Identification and Properties

They are less soluble in water, polyphenols are slightly more soluble

They are soluble in alcohol and ether

Most of them are water-vapor drift volatile

They have weak acidic property

Alkaline phenolates occur with alkaline hydroxides(They dissolve in alkaline hydroxides) this feature distinguishes phenols from alcohols

PHENOL GLYCOSIDES

Unlike acids, they don’t dissolve in alkaline carbonates.

Identification with colour reactions:

Free phenols + aqueous ferric chloride

(FeCl3) neutral medium

blue/green/purple/red colour (But also

hydroxypyridine, some organic acids, enols,

oximes may give positive reaction)

PHENOL GLYCOSIDES

Phenols + amines dinitrozed by nitroso acid (e.g. P-nitranyline) coloured hydrasoics occur.

Phenols + aldehydes (e.g. Vaniline-HCl) and 2,6-dibromquinone

chlorimide in acidic medium give colour reactions.

Phenols + acetic acid and benzoic acid characteristic esters

and meyhyl derivatives occur.

Identification is also available by chromatographic techniques.

PHENOL GLYCOSIDES

QUANTIFICATION

1) Colorimetric: By using colouring reactions.

2) Chromatographic: Measured upon phenolic aglycones.

3) Titirmetric: Can be applied after extraction with alkaline hydroxides.

4) Gravimetrically: After phenolics precipated by aquaeous Br, is weighed out and the amount is calculated.

PHENOL GLYCOSIDES

USAGES

1) Some of them are antiseptic

2) Antipyretic and analgesic

3) Some phenolic aglycones are odorous; used as

aromatizan or odour improver in pharmaceutical and

food industries.

CORTEX SALICIS, Söğüt kabuğu(WHITE WILLOW)

The bark of the branches of Salix alba (Salicaceae) (Ak söğüt).

Grows in damp, temperate and cold regions

Widespread in Turkey

Shedding leaves in winter, generally grows near a

water source


Approximately, 25 Salix species are growing in TurkeyAmong these species the most common ones are:

S. alba (ak söğüt – white willow)

S. babylonica (salkım söğüt - Babylon willow or weeping willow)

S. caprea (keçi söğütü – goat willow)S. cinerea (boz söğüt – grey willow)

S. excelsa (yüksek söğüt - )

S. fragilis (gevrek söğüt – crack willow)

S. purpurea (erguvani söğüt – purple willow)

S. viminalis (bağ söğütü – common osier)


Contents

SALICIN (Phenol glycoside)

Tannins

Tonic property regarding tannin content.

Glycoside febrifuge, antirheumatic and

antineuralgic.

CH2OH

O Gl

SALIKOZIT

ENZ.HİDR.

ASİT

HİDR.

CH2OH

OH

SALİGENOL

CH2 O CH2

OH OH

SALİRETİN

+ Gl

(Aglikonun dimeri)

SALICIN

Enz. Hyd.

Acid Hyd.

SALIGENIN

(Salicyl alcohol)

SALIRETIN

Dimer of aglycone

POPULI GEMMAE (TK),Karakavak tomurcuğu, Black poplar

Flower and leaf buds of Populus nigra (Salicaceae) collected at the end of winter

1-3 cm length, conic shaped

Contents;

Phenol glycoside Populin (populoside) (benzoyl

salicoside)

Flavonoid Chrysine derivative (flavon derivative)

CH2OH

O

CH2OCO

O

POPULOZİT (BENZOİL SALİKOZİT)POPULIN (Benzoyl salicin)

CHRYSIN DERIVATIVE (Flavon)

salicin

POPULI GEMMAE (TK),Karakavak tomurcuğu, Black poplar

Used in the treatment of hemorrhoid as ointment

Populin painkiller

Chrysol derivative increases capillary

resistance

Approved by Commission E

FRUCTUS VANILLAE (TK), Vanilla fruit, Vanilya meyvesi

Boiled and then dried immature fruits of Vanilla planifolia (Orchidaceae).

Grows naturally and cultured in Meksika, Java, Madagaskar ve Antills.

15-25 cm, flat, sharp in 2 edges, bright black coloured

Doesn’t grow in Turkey

Contents;

VANILLIN (VANILLAL) -------%1.5-2.5 (Fragrant compound)

Its glycoside, found in fresh fruit is VANILLOSIDE (Glucovanillin)----β-glucosidase hydrolysis---Vanillin+gl

VANILLOLOSIDE-----Glycoside of Vanillicalcohol.


CHO

OGl

OCH3

VANİLOZİT (GLUKOVANİLİN) CH2OH

O

OCH3

OZ

VANİLOLOZİT

(VANİLİK ALKOL HET.)

VANILLOSIDE (Glucovanillin)

VANILLOLOSIDE (Vanillic alcohol

glycoside)

Weak choloretic activity

Digestion stimulant

Sexual power enhancer effect

Used for odour correction in the

pharmaceutical and food industries


FOLIA UVAE URSI, Ayı üzümü yaprağı, Bearberry leaf

Arctostaphylos uva ursi (Ericaceae)

Growing in mountainous regions

Europe, Asia, North America

Doesn’t grow in Turkey

Contents – Phenol glycosides;

ARBUTIN (hydroquinone derivative)----%5-10

METHYL ARBUTIN (methyl hydroquinone

derivative)


Contents – Phenol glycosides;

ARBUTIN (hydroquinone derivative)----%5-10

METHYL ARBUTIN (methyl hydroquinone

derivative)

O

O

HİDROKİNON

OGl

OH

ARBUTOZİT

OGl

OCH3

METİL ARBUTOZİT

HYDROQUINONE

ARBUTIN

METHYL ARBUTIN

Arbutin---hydrolysis---hydroquinol quickly oxidized to hydroquinone

Gallic tannin

Flavonoids Quercetin derivatives


Astringent due to tannin content

Antiseptic for urinary system; extracts of this

plant are used against cystitis, urethritis,

pyelitis

Antibacterial effect

Aqueous leaf extract is effective against

Helicobacter pylori due to tannic acid

content


FLORES SPIRAEAE ULMARIAE (MEADOWSWEET)

Filipendula ulmaria (Spiraea ulmaria) (Rosaceae) ----keçi sakalı

East Anatolia and Blacksea region

North and South Europe, North America and

North Asia

Perennial, with yellowish white flowers


Phenol glycoside MONOTROPITOSIDE---hydr.---methyl salicylate+gl+ks

Flavonoid-----Spireoside

(Quercetin 4’-O-glucoside)

Tannins

Essential oil

O

COOCH3

Gl Ks

MONOTROPİTOZİTMONOTROPITOSIDE


Antirheumatic due to phenol glycoside

Diuretic due to flavonoid content

Methyl salicylate antimicrobial, antipyreticand diuretic

Commision E approved the use of the drug in cold, bronchitis and fever

IRIDOIDS

Cyclopentanopyran main structure

C1 OH

The glycosidic bond is generally from the –OH on first position.

There is a double bond between C3-C4.

Number of C atom:

8

9 ---- substitution on C4 or C8

10 ------ substitution on both C4 and C8.

O

OH

1 2

3

456

7

8 9

-CH3, -CH2OH, -COOH, -CHO can be found as substituents.

Besides, –OH, epoxide or lacton can also be found as substituent.

Firstly isolated from an ant species, “Iridomyrmex detectus” thats why they are called as iridoids!

IRIDOIDS

There can be a double bond on cyclopentane ring at 7-8 position

O

OGl

CH2OHOH

1 2

3

45

7

8 9

DEKALOZIT (9 C'LU)

6

9

7

6 54

3

21 O9

7

6 54

3

21 O9

7

6 54

3

21 O

OGl

OHCH3

COOCH3

8

MUSSENOZIT(10 C'LU)

11

IRIDOIDS

DECALOSIDE (9 C) MUSSENOSIDE (10C)

9

7

6 54

3

21 O

OGl

COOH

OH

CH2OH

11

10

MONOTROPEOZIT

(10 C'LU)

8

98

7

6 54

3

21 O

OGl

O O

CH2

COOCH3

ASPERULOZIT

98

7

6 54

3

21 O

OGl

O

CH2OH

O CO OH

KATALPOZIT(9C'LU)

98

7

6 54

3

21 O

O

CH2OGl

HO

CH2OHC

O

CH2 CH

CH3

CH310

PATRINOZIT (10C'LU)

MONOTROPEOSIDE

(10 C)

CATALPOSIDE (9C) PATRINOSIDE (10 C)

ASPERULOSIDE

They can found in nature as monoglycosidic, diglycosidic or biosidic:

O

OHCH2OH

OH

OKUBIGENOL

O

OHCH2OGl

OGl

6

10

DIHETEROZIT

O

OCH2OH

OH

seratinoz

BIOZIT

1

IRIDOIDS

AUCUBIN BIOSIDIC GLYCOSIDE

DIGLYCOSIDIC

Non-glycosidic iridoids:

Valepotriates found in Radix Valerianae(valerian root) (esters of isovalerianicacid)

O

OCOCH2CH

O CH3

CH2OCOCH3

CHCH2COOCH3

CH3

CH3

78

4

1

VALTRATUM

IRIDOIDS

Secoiridoids can be regarded as being formed from iridoids by cleavage of the cyclopentane ring between C-7 and C-8(e.g. Gentiopicroside)

IRIDOIDS

DISTRIBUTION

SPERMATOPHYTA division

DICOTYLEDONAE class

1) APETALAE---Urticales--Eucommizceae

2) DIALYPETALAE--Geraniales-Meliaceae

--Rosales--Saxifragaceae

3) SYMPETALAE—Apocynaceae/ Gentianaceae /

Loganiaceae / Ericaceae / Caprifoliaceae / Labiatae

/ Scrophulariaceae / Verbenaceae etc.

IRIDOIDS

IDENTIFICATION

1) Colourless; but they give blue colour in acidic medium.

2) Colouring and precipitation by TRIM-HILLreaction

Trim-Hill Reagent consist of:

• 0.2% aqueous CuSO4 (1 ml)

• CH3COOH (10 ml)

• Conc. HCl (0.5 ml) mixture.

IRIDOIDS

Iridoids + Trim-Hill reagent heat firstlyblue or purple than this coloured mixture convert to a black precipitate in a few hours.

3) Chromatographic Assays:

-TLC: Revelator ---- Vanillin-H2SO4 or

Floroglusinol-HCl

-HPLC

IRIDOIDS

OBTAINING

Since being not stable, fresh plant material is used for obtaining.

The extraction medium shouldn’t be acid.

Polar solvents are used for extraction

Extract + washing by nonpolar solvents liphophilic compounds will be removed

Elimination of phenolic compounds and tannins by1- Precipation using Pb acetate or 2- Eluting from activated charcoal / Al2O3.

IRIDOIDS

By eluting from polyamide column free sugars and oligoholosides will be eliminated

Seperated iridoids are isolated using

chromatographic techniques.

IRIDOIDS

QUANTITATIVE ANALYSIS

GRAVIMETRIC

COLORIMETRIC (Trim-Hill Reaction)

CHROMATOGRAPHIC (GC and HPLC)

IRIDOIDS

EFFECT AND USAGES

1) Compounds without strong effects

2) Traditionally used for years as;

Insecticide

Hypotensive

Appetizer

Tonic

IRIDOIDS

3) Antimicrobial effect:

- AUCUBIN---- not effective----hydrolisis--

-AUCUBIGENIN (aglycone) or its dimer/

polymer----EFFECTIVE

- ASPERULOSIDE (glycoside)---- not

effective ---hydrolisis----AGLYCONE----

EFFECTIVE (against Staphylococcus

aureus; 600 I.U. Penicilline equivalent.

IRIDOIDS

4) Purgative effect:

Due to -OH on 6.

position

- free –COOH on 11.

position decreases

this effect

IRIDOIDS

11

O

COOCH3

OGlOH CH3

MUSSENOZIT

O

OGlCH2

O

O

COOCH3

ASPERULOZITO

OGlCH2OH

OH

6

OKUBOZIT

IRIDOIDS

AUCUBIN

MUSSENOSIDE

ASPERULOSIDE

5) Diuretic effect: Catalposide

6) Analgesic and

Antispazmodic

Harpagoside---

hydrolysis---

Aglycone---

Antiphlogistic effect.

6

O

OGl

OH

OH

OH

CH3

5

8

HARPAGOZIT

IRIDOIDS

HARPAGOSIDE

7) Appetizer and toniceffect: Loganoside

8) Sedative effect:

Nonglycosidic iridoids-

--- Valepotriates

9) Antileukemic effect:

Nonglycosidic iridoids

O

OGl

OH

CH3

COOCH3

7

8 1

4

LOGANOZIT

IRIDOIDS

LOGANOSIDE

FLOS VERBASCI (EP)

Scrophulariaceae – Verbascum sp. – Mullein

Drug is obtained from;

Verbascum phlomoides (Wooly mullein)

V. thapsus (great mullein/common mullein)

V. densiflorum (denseflower mullein) species.

Known as «Sığır kuyruğu» in Turkish.

Widely distributed in Europe, Africa, S. America and Turkey.

FLOS VERBASCI (EP)

1) Iridoid---- Aucubin---hydr.--- Aucubigenin+ Gl

Aucubigenin --- unstable --- polymerize---

browning.

2) Flavonoids --- Hesperidoside and

Verbascoside

3) Mucilage

4) Saponin

FLOS VERBASCI (EP)

Emollient

Antitussive, expectorant

German Comission E approved usage in

cold and bronchitis

HERBA MONOTROPAE

Monotropa hypopitys (Ericaceae)

A parasitic plant living on Coniferae plants

Common in Turkey

Up to 10-30 cm hight, with scale-like leaves,

yellowish-white coloured

HERBA MONOTROPAE

1) Iridoid glycosides---Monotropeoside

Monotropeoside

---hydr.---Aglycone+Gl

2) Phenol gly.---

Monotropitoside---hydr.--

-Methyl

salicylate+Gl+Xsy

O

OGl

COOH

OH

CH2OH

11

8 1

MONOTROPEOZIT

COOCH3

OGl Ks

MONOTROPITOZIT

MONOTROPEOSIDE

MONOTROPITOSIDE

HERBA MONOTROPAE

Drug;

Antispasmodic

Cough sedative

Aglycone of Phenol glycoside---methyl

salicylate---antirheumatic

Galium Sp., Yoğurtotu, Bedstraw

Galium aparine (cleavers, bedstraw)(Rubiaceae)

G. cruciata (star gentian)

G. mollugo (hedge bedstraw)

G. verum (lady's bedstraw)

Well known in Europe, wide distributed

in Anatolia

Iridoid---- Asperuloside

In Turkey; Gallium coronatum (Cruciatataurica)----asperuloside andmonotropeoside; also rutoside is identified


Antispasmodic

Diuretic

Antirheumatic


Plantago sp., Psyllium husk

Plantaginaceae

Plantago ovata (EP)

P. lanceolata (EP)

P. media

Sinirli ot, sinir otu,

20 species growing in: Europe, N. Africa,

E. Asia and Turkey

Stem and rosetteleaves of the plantcontain Iridoidglycosides

Aucubin, catalposide

O

OGlCH2OH

OH

6

OKUBOZIT6

O

OGlCH2OH

COO

O

OH

KATALPOZIT (%0.3-1.1)


CATALPOSIDE

AUCUBIN

Besides, leaves contain

Mucilage arabinogalactan (2-6.5%)

Tannin (6.5%)

Phenolic carboxylic acids protocatechuic

acid

Flavonoids

Minerals (Zn, K)


Traditionally;

Antiinflammatory

Fresh juice or plaster prepared from the

juice is used against itch caused by

insect bites

Infusion used as eyewash against

inflammations in the eyes


Used as mouthwash against throatinflammation

Cicatrizan in skin diseases

Used also against cough, bronchitis, upper

respiratory infections

Plantago psyllium, which is well known in

Turkey, used as laxative and emollient

regarding mucilage content


phenol glycosides - PowerPoint Sunusu

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