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• embraces a wide range of plant substances which possess in common an aromatic ring bearing
one or more hydroxyl substituent. If the molecule contains two or more hydroxylic groups there
is polyphenols.
• Tend to be water –soluble, since they most frequently occur combined with sugar as glicosides.
Usually located in the cell vacuole
• Among the natural phenolic compounds, of which several thousand structure are known, the
flavonoids form the largest group but simple monocyclic phenols, phenylpropanoids amd
phenolic quinones all exist in plants
• Detecting simple phenol is by means of the intense green, purple, blue or black colours many
of them give in solution when 1% aqueous mixture of 1% ferric chlotide and 1% potassium
feericyanide, is till used as a general means of detecting phenolic compounds on paper
chromatograms.
• Th emajority of phenolic compounds can be detected on chromatograms by their colours of
fluorescences in UV light, the colour is being intensified of changed by fuming the papers with
ammonia vapour
• They are all aromatic show intense absorption in the UV region of the spectrum
Biosynthesis some natural compounds
Stilbens
Lignans
Lignins Coumarins Phlavonoids
Phenolic compounds with one benzoic nucleus
Basic skeleton Class Examples
C6 Simple phenols, Benzoquinones Catechol, Hydroquinone, 2,6-
Dimethoxybenzoquinone, phenol, pirocatechol
C6-1 Alkilphenol p-cresol
Phenolic alcohol Saligenin
Phenolic aldehydes Vanilin, Salicylic
Phenolic acids Gallic, salicylic
C6-C2 Acetophenones, Tyrosine 3-Acetyl-6-methoxybenzaldehyde, Tyrosol, p-
derivatives, Phenylacetic acids Hydroxyphenylacetic acid
C6-C3 Hydroxycinnamic acids,
Caffeic, ferulic acids, Myristicin, Eugenol,
Phenylpropenes, Coumarins,
Umbelliferone, aesculetin, Bergenon, Eugenin
Isocoumarins, Chromones
C6-C4 Naphthoquinones Juglone, Plumbagin
Phenolic compounds with two benzoic nucleus
Basic skeleton Class Examples
C6-C1-C6 Xanthonoids Mangiferin
C6-C2-C6 Stilbenoids, Anthraquinones Resveratrol, Emodin
C6-C3-C6 Chalconoids, Flavonoids, Quercetin, cyanidin, Genistein
Isoflavonoids, Neoflavonoids
(C6-C3)2 Lignans, Neolignans Pinoresinol, Eusiderin,
rosmarinic acid
OH OH CH3 OH
OH COOH
Br
OH OH COOH
OH
OH
OH
OH OH
Salicine Salidroside
Structure of phenylpropanoids
3' 3'
1'
B
4' Flavone
8 1
O
2'
1'
B
4'
5'
O 5'
7 7
2
• Composed of diphenylpropane units C6-
2 6' 6'
A C A C
6 3
C3-C6 6
4
3
5
5
B B
• Typically OH or OCH3 groups 8 1
O 1'
5'
8
O
1
1'
5'
7
• Typical to have OH on positions: 7
2 6'
A C
2 6'
A C
• 5 and 7 6 6
OH OH
• 3’, 4’ and 5 5 4 5
O
• Are also present as gylcosides
3'
2' 4'
Flavanone Isoflavone
8 1 B 8 1
1' O
O 5'
7 7
2 6' 2
A C A C 3'
6 6 1'
3 4'
5 5
B
O O 2' 5'
6'
• Istilah flavonoid berasal dari kata flavon yang merupakan salah satu jenis
flavonoid yang terbanyak dan lazim ditemukan (selain flavonol, antosianidin).
• Flavon mempunyai kerangka 2-fenilkroman.
• Berdasarkan tingkat oksidasinya, flavan adalah yang terendah dan digunakan
sebagai induk tatanama flavon.
1 B O
O O
2
A C
3
OH
4
katecin
2-fenilkroman flavan (flavan-3-ol)
OH
O
OH O
leukoantosianidin calkon
dihidrocalkon
(flavan-3,4-diol)
• Biogenesis berasal dari kombinasi antara jalur shikimat dan jalur asetat-mevalonat.
• Merupakan senyawa fenol terbanyak ditemukan di alam.
• Merupakan zat warna merah, ungu, biru, dan sebagian zat warna kuning.
• Kerangka dasar terdiri atas 15 atom karbon yang membentuk susunan C6-C3-C6
• Cincin B flavonoid seringkali mempunyai gugus gugus hidroksil atau alkoksil pada posisi 4’, atau 3’ & 4’.
• Adanya tiga gugus hidroksil atau alkoksil, atau tidak teroksigenasi sama sekali, atau teroksigenasi pada
posisi 2’, sangat jarang ditemukan.
• Hal tersebut disebabkan biogenesis dari flavonoid.
• Glikosida senyawa flavonoid berikatan dengan gula pada gugus hidroksil yang ada.
3
3 A
2
B A 2 1
3
A 1 B
2 B
1
R O O
OH
R=H daidzein O
R = OH genistein pterokarpin
rotenoid
kumestan
R
R2 O O O O
O
R3
R1 O R O
OH OMe
OMe
R1=R3=H R2=OH kumestrol R=H rotenon
R1=R3=OH R2=OMe medelolakton R = OH amorfigenin
• Ragam neoflavonoid:
4-arilkumarin dalbergion
MeO O O
MeO O
HO
O
R1
R1
4-metoksidalbergion
R1=R2=H dalbergin
R1=OH R2=OMe melanein
Klasifikasi Flavonoid
B
O
Apigenin = trihydroxy 5,7,4’ flavon A C
+
O 2
Ring B O 2 Ring B
A 2
A A
3
4 3 Ring B 4 3
4
O O
Isoflavone Chalcone Anthocyanin
15
Quercetin = pentahydroxy 3,5,7,3’,4’ flavonol
Flavonoids Biological Signifcance
• Not all flavonoids have same function in plants
• Anti-fungal
• Insects
• some feeding deterrents/some stimulants
• Antioxidant
• Color: bright colors in plants
Band I 3000-400 nm
O- Cinnamoyl chromophore
O
O-
18
BAND I & BAND II
Band I Band II
1. Flavon 240 - 285 304 - 350
2. Favonol 240 - 285 352 - 385
3. Isoflavon 245 – 270 300 – 340w
4. Flavanon &
Dihidroflavonol 270 – 295 310 – 340w
5. Chalcones 220 – 270m 340 – 390&
6. Aurones 240 – 300m 370 – 430
7. Catechins &
Flavan-3,4-diols ~ 280
8. Antosianin &
Antosianidin 270 – 280m 465 - 550
Pergeseran panjang gelombang absorpsi karena ditambah natrium
metoksida
atau natrium hidroksida
Flavon dan Flavonol
AURON OH
HO O
OH
OH
HO
O
C OH
H
OR
O
OH CYANIN (R=glucosyl) (Anthocyanin)
AURON
OH = MARITIMETIN
CYANIDIN (R=H) (Anthocyanidin)
OH
OH
HO O
O
HO
OH O
OH O
BIFLAVONOID
(GINKGETIN)
27
Coumarin Glycosides and Related Compounds
• Coumarins are derivatives of benzo--pyrone, or lactones of o-hydroxycinnamic acid (o-
coumaric acid).
• The parent compound is coumarin, umbelliferone is the 7-OH derivative of Coumrin.
• The glycoside of umbelliferone is called skimmin.
• These compounds are used to protect skin from UV light as they absorb short wave length
(280- 315 nm).
5 4
R1
6 3
7 2
O O R2 O O
8 1
R1=R3=H, R2=OH: Umbeliferon R3
R1=R3=H, R2=OCH3: Herniarin
R1=R2=OH, R3=H: Aeskuletin
R1=OCH3, R2=0H, R3=H: Skopoletin
R1=OCH3, R2=R3=OH: Fraksetin
Dicoumarol
• It is a phytoalexin formed due to fungal effect on Melilotus officinalis (Red Clover)
• It is a dimer of 4-hydroxycoumarin that is now produced synthetically under the trade
name of Dicoumarol.
• Uses: anticoagulant and rodenticide.
Furanocoumarins
• They are coumarin derivatives with additional furan ring.
• Ammi majus contain a group of furanocoumarins, the parent
compound is called Psoralene.
• They are used for the treatment of psoriases and leucodermia.
LIGNAN
Skeleton results from bonding between the β
carbons of the side chains of two units
derived from 1-phenylpropane (8-8’ bond)
NEOLIGNAN
Also condensation products of
phenylprophaneoid units, but the actual
bond varies and involves no more than one β
carbons (8-3’; 8-1’; 3-3’; 8-O-4’ for example).
LIGNAN
O
(BERASAL DARI KONIFERILALKOHOL) H3C CH3
CUBEBIN DARI Piper cubeba
OH
O O
O
O
(-) CUBEBIN
OH
HO O
CH2OH OCH3
OH
OH O
SILIKRISTIN