Komposisi nilai. Kuis : 20% Tugas : 50% UAS : 30%

Komposisi nilai

• Kuis : 20%

• Tugas : 50%

• UAS : 30%

Materi Kuliah

• Fenilpropanoid

• Flavonoid

• Alkaloid : 2

• Terpenoid

• Zat Pahit

Penugasan

• Membuat makalah dan presentasi terkait produk yg

mengandung metabolit sekunder tsb.

• Batasan tugas : profil produk (nama produk, foto,

komposisi, dosis, cara penggunaan, manfaat/khasiat),

kandungan metabolit yg terkandung, sumber

tumbuhan dan cara isolasi metabolit tsb, mekanisme

aksi metabolit dalam menimbulkan khasiat (bila

khasiatnya banyak, pilih 1 khasiat yg lengkap

mekanisme aksinya, min. Diperoleh dari 5 jurnal)

• Makalah lengkap : cover, daftar isi, isi, kesimpulan,

Klasifikasi fenilpropan

• Fenilpropanoid (C6-C3)

• Flavonoid (C6-C3-C6)

Klasifikasi fenilpropanoid

• Asam hidroksisinamat

• Fenilpropena

• Kumarin

• Fenilpropanoid pendek

• Turunan bifenilpropenoid

• Fenilpropanoid BM tinggi

biphenylpropane phenylpropane

Asam hidroksisinamat

• Asam para-kumarat

• Asam kafeat

• Asam ferulat

• Asam sinapat

Asam para-kumarat

• Sinonim : asam p-hidroksisinamat

• Sumber biologis : Lidah buaya (Aloe barbadensis

Mill), Mole plant (Euphorbia lathyris L.), Apel

(Malus sylvestris Mill.)

• Pemerian : berbentuk jarum dan memiliki titik

lebur 210-213°C. Mudah larut dalam etanol, eter,

dan air panas, sukar larut dalam air dingin, dan

praktis tidak larut dalam benzen.

• Manfaat : antioksidan, menghambat

Asam Kafeat

• Sinonim : Asam 3,4-dihidroksisinamat

• Sumber biologis : Kopi (Coffea sp.),

Wintergreen (Gaultheria procumbens L.), Red

clover (Trifolium pratense L.)

• Pembuatan : asam kafeat pada tumbuhan

hanya berada dalam bentuk terkonjugasi,

misal asam klorogenat. Asam ini juga telah

diisolasi dari kopi hijau dan kopi panggang

• Pemerian : bentuk kristal kuning dari larutan air pekat dan

bentuk monohidrat dari larutan encer. Asam kafeat melunak

pada 194°C dan mengurai pada 223-225°C. Mudah larut

dalam etanol dan air panas, agak sukar larut dalam air dingin

• Uji kimia :

1. Asam kafeat berubah warna dari kuning menjadi jingga

dalam media basa

2. Asam kafeat segera membentuk metil ester (C10H10O4) yg

diperoleh sebagai kristal tak berwarna dari air (titik lebur

152-153°C)

• Manfaat : antioksidan, menghambat xantin oksidase,

Asam ferulat

• Sinonim : asam kafeat 3-metil eter, asam

4-hidroksi-3-hidroksisinamat

• Sumber biologis : resin Asafoetida (Ferula

assafoetida L.), perdu Saw palmetto (Serenoa

repens (Bartel.), ranting ivy (Hedera helix L.), Pirus

laricio Poir. (Abietineae)

• Pembuatan : diisolasi dari Ferula foetida Reg

(Umbelliferae) dan Pirus laricio Poir. (Abietineae).

Asam ferulat jg dapat disiapkan melalui interaksi

vanilin, asam malonat, dan piperidin dalam

piridin selama 3 minggu dan kemudian endapkan

asam ferulat dengan HCl encer

• Pemerian :

– Bentuk cis : minyak kuning, UVmaks (dalam etanol) :

316nm

– Bentuk trans : jarum ortorombik yg diperoleh dari air,

titik leleh 174°C, UVmaks (dalam etanol) : 236 dan

322nm. Larut dalam air panas, etanol, dan etil asetat,

cukup larut dalam eter, agak sukar larut dalam benzen

dan PE

• Uji identifikasi : asam ferulat dengan larutan NaOH

membentuk garam natrium sehingga menyebabkan

kelarutannya cukup meningkat

• Kegunaan : asam ferulat digunakan sbg pengawet produk

makanan, antioksidan

Asam sinapat

• Sumber biologis : daun dan ranting European

mistletoe (Viscum album L.) (Loranthaceae)

• Pembuatan : hidrolisis ester kolin asam sinapat dari biji

mustard hitam (Brassica nigra Koch (Cruciferae), baik

dalam media asam maupun dg hidrolisis enzimatik.

• Kegunaan :

1. Asam sinapat digunakan sbg antiseptik,

antispasmodik, dan emetik

2. Asam sinapat juga digunakan pada arteriosklerosis,

stimulan jantung, kanker, hepatosis, dan hipertensi

3. Asam sinapat juga telah digunakan dalam

Fenilpropena

• Sinonim : sinamal, fenilakrolein, sinamat aldehid

• Sumber biologis : minyak kayu manis Sri Langka

(Cinnamomum verum J.S Presler) (Lauraceae),

balsam Peru (Myroxylon balsamum var.Pereirae

(Royle) Harms (Fabaceae), cengkeh (Syzygium

aromaticum (L.) Merr&Perry (Myrtaceae)

• Pembuatan : minyak kasia (Cinnamomum cassia

Blume) mengandung minyak atsiri 1-2%. Minyak

atsiri ini mengandung sinamaldehid 80-85% yg

diisolasi melalui distilasi fraksional dalam vakum.

• Pemerian : cairan berminyak kekuningan yg

memiliki bau kayu manis yg tajam. Parameter

fisiknya d

25₂₅

1,048-1,052; TD

₁₀₀

177,7°C; TD

₂₀₀

199,3°C and TD

₇₆₀

246°C. Sinamaldehid larut

dalam 700 bagian air dan 7 bagian etanol 60%.

Akan tetapi, sinamaldehid tdk bercampur dg

etanol, eter, kloroform, dan minyak.

• Uji kimia : penambahan setetes larutan FeCl3 1%

b/v menghasilkan warna cokelat yg khas

• Kegunaan :

1. Fenilpropena banyak digunakan pd industri

parfum

2. Fenil propena digunakan utk memberikan aroma

pada makanan dan minuman

Kumarin

• Kumarin

• Hidroksikumarin

– Umbelliferon

– Eskuletin

– Skopoletin

– Dafentin

– Fraksetin

• Furanokumarin

– Psoralen

– Metoksalen

– Bergapten

– Imperatorin

Kumarin

• Sinonim : asam cis-o-lakton kumarinat, kumarin,

kumarinat anhidrat, kamfer biji tonka

• Sumber biologis : Biji tonka (Dipteryx odorata (Aubl)

Willd), Anisi (Pimpinella anisum L.), Seledri (Apium

graveolens L.)

• Pemerian : kristal kumarin memiliki lempeng

ortorombik dan rektangular. Kumarin memiliki bau yg

enak dan wangi mirip dg biji vanili dan rasa terbakar.

• Karakter fisika : titik leleh 68-70°C dan titik didih

297-299°C. Kumarin larut dalam etanol, kloroform, eter,

minyak, dan larutan NaOH/KOH, agak sukar larut dlm

air panas (1:50), sukar larut dlm air dingin (1:400)

• Kegunaan : kumarin banyak digunakan sbg pemberi

aroma pada formulasi obat

Umbelliferon

• Synonyms Hydrangin; Skimmetin.

• Biological Sources Umbelliferone is present in a variety of medicinal plants, for instance: Apium graveolens L. (Apiaceae) Celery; Dipteryx

odorata (Aubl.) Willd. (Fabaceae)-Tonka Bean; Ferula sumbul Hook.

(Apiaceae)-Sumbul; Lavandule angustifolia Mill. (Lamiaceae)-Lavender;

Matricaria chamomilla L. (Asteraceae)-Hungarian Camomile; and Pimpinella anisum L. (Apiaceae)-Anise.

• Preparation Asafoetida contains resin (40-65%) which consits of chiefly a resin-alcohol asaresinotannol both in the free or combined form with

ferulic acid, and of course, free umbelliferone is totally absent in the drug. Thus, umbelliferone is prepared by treating ferulic acid with HCl which gets converted to umbellic acid and the latter loses a molecule of water to give rise to umbelliferone

• Umbelliferone may also be obtained by distillation of resin from

• Characteristic Features It is obtained as needles from water. It

develops the characteristic odour of coumarin on heating. Its mp is

225-228°C. It usually sublimes. Its solubility in water is very poor i.e., it dissolves 1 g in nearly 100 ml of boiling water. It is freely

soluble in ethanol, chloroform, acetic acid and dilute alkaline

solution. It is sparingly soluble in ether and the solutions exhibit a distinct blue fluorescence.

• Identification Test When 0.5 g of umbelliferone is triturated with pure sand (SiO₂) and 5 ml of HCl, added 5 ml of water, filtered and to the filtrate added an equal volume of ammonia solution, it gives a beautiful blue fluorescence.

• Uses

1. It is an important ingredient in most sunscreen lotions and creams. 2. It is most importantly used as an intracellular and pH sensitive

Esculetin

• Synonyms Aesculetin; Chicorigenin; 6, 7-Dihydroxy-coumarin.

• Biological Source It is the aglucon of esculin and cichorlin: Esculin is derived from two different plant sources, namely: (a) the barks of

Crataegus oxycantha L. (Rosaceae)-Hawthorn; and (b) the flowers

of Centarea cyanus Linn., (Compositae). It is a glucoside which upon hydrolysis gives the aglucon esculetin.

• Esculetin is also obtained from cichorlin, which is a glucoside and found to be isomeric with esculin. Cichorlin is present in the flowers of the chicory plant (Chichorium intybus L., family: Compositae).

• Uses : antioxidant, inhibitor human leukemia cell inhibitor, antiinflamation (in vivo and in vitro)

Skopoletin

• Synonyms Chrysatropic acid; Gelseminic acid;

Methoxyumbelliferone; β-Methylesculetin; 7-Hydroxy 6-methoxycoumarin

• Biological Sources It is the aglucone of scopolin. Scopoletin occurs in the roots of Arnica montana L. (Asteraceae)-Mountain Tobacco,

Leopard’s-bane; leaves of Artemesia abrotanum L. (Asteraceae)-Southernwood, Old Man; roots and leaves of Atropa belladona L.

(Solanaceae)-Belladonna, Deadly Nightshade; barks of Brunfelsia

uniflorus (Phol.) D. Don. (Solanaceae)-Manaca, Manacan; fruits

of Capsicum annuum L. (Solanaceae)-Chili, Sweet Peppers,

Paprika; oil of the plant Chamaemelum nobile (L.) All. (Asteraceae)-Roman Comomile; English Camomile, Comomile; and roots

• Preparation It is obtained by the hydrolysis of the glucoside

scopolin i.e., 7-(β-D

glucopyranosyloxy)-6-methoxy-2H-1-benzopyran-2-one as follows:

• Characteristic Features Scopoletin occurs as prisms or

needles from either acetic acid or chloroform. It melts at

204°C. It is slightly soluble in water or cold ethanol and

quite soluble in hot ethanol and hot glacial acetic acid. It is

moderately soluble in chloroform, but practically insoluble

in the non-polar solvent benzene.

• Uses :

– Antioksidant, antifungal, immunomodulator, hepatoprotective (in vitro and in vivo)

Dafentin

• Synonyms 7, 8-Dihydroxycoumarin

• Biological Sources It is the aglucon of daphnin. It is

obtained from the seeds and fruits of Daphne

mezereum L. (Thymelaeaceae)-Mezereon; and the seeds

of Euphorbia lathyris L. (Euphorbiaceae)-Mole Plant,

Petroleum Plant, Caper Spurge.

• Preparation Daphentin is prepared conveniently from its

glucoside known as daphnin i.e., 7, 8-dihydroxycoumarin

7-β-D-glucoside by treating the latter in three different

ways, namely: (i) By boiling with dilute mineral acids; (ii)

By enzymatic hydrolysis; and (iii) By sublimation as given

below:

• Characteristic Features The crystals obtained

from dilute ethanol has a mp 256°C

(decomposes). It undergoes sublimation on

heating. It is soluble in boiling water, hot dilute

alcohol and hot glacial acetic acid. It is found to

be sparingly soluble in ether, chloroform, and

benzene.

• Identification Tests

• 1. An aqueous solution of daphentin gives a

green colouration with FeCl3 solution, which

turns red on the addition of sodium carbonate.

• 2. An alkaline solution of daphentin in alkali

Fraksetin

• Synonyms 7, 8-Dihydroxy-6-methoxycoumarin.

• Biological Source It is the aglucon of fraxin. Fraxin is

present in the seeds of Acsculus hippocastanum L.

(Hippocastanaceae)-Horse Chestnut.

• Preparation Fraxetin is obtained by

heating fraxin with dilute sulphuric acid to affect the

hydrolysis of glucoside and get the desired aglucon

residue as shown here under:

• Characteristic Features Fraxetin is obtained as

plates from ethanol having mp 228°C. It has

been observed that it turns first yellow at

150°C and subsequently brown at mp. It is

soluble in 10 L of cold water, but in 300 ml of

boiling water. It is somewhat more soluble in

alcohol and practically insoluble in ether.

Furanokumarin

• Furanocoumarins, represent a class of

relatively more complex coumarins that occur

in various natural plant products. A few

important members of this particular class

are, namely: Psoralen; Methoxsalen;

Psoralen

• Synonyms Ficusin; 6-Hydroxy-5-Benzofuranacrylic acid d-lactone; Furo (3, 2-d)-coumarin.

• Biological Source Psoralen belongs to one of a group of

furanocoumarins occurring naturally in more than two dozen different plant sources, for instance: Rutaceae (e.g., Bergamot,

Limes, Cloves); Umbelliferae (Celery; Parsnips); Leguminosae (e.g., Psoralen coryfolia). It is also found in the Rue Oil obtained from Ruta graveolens L. (Rutaceae)-known as Rue (daun inggu). It is

obtained from the leaves of Ficus carica Linn. (Moraceae)-Figs. • Characteristic Features Psoralen crystals from ether have two sets

of melting points e.g., 163-164°C and 169-179°C (Spath). It is very soluble in chloroform, less soluble in alcohol, sparingly soluble in ether and practically insoluble in petroleum ether (60-80°C).

Identification Tests

• 1. Dissolve 1 mg of psoralen is 5 ml of ethanol and add to it 15 ml of a mixture made up of 3 parts of propylene glycol, 5 parts of acetic acid and 43 parts of water. The resulting mixture on being exposed to the uv-light in a uv-chamber, gives a distinct blue-fluorescence. • 2. When 1 mg is dissolved in 2 ml ethanol, mixed with two drops of

NaOH solution (0.1 M) and the resulting solution is subjected to uv-light, it emits a yellow fluorescence.

Uses

1. It is used in the treatment of leucoderma patches.

2. Psoralens have also exhibited photosensitizing and phototoxic effects in animals and human beings and, hence have been

employed extensively in photochemotherapy for the treatment and management of vitiligo, psoriasis and mycosis fungoides.

Metoksalen

Synonyms Xanthotoxin; Meloxine; Ammoidin; Meladinine;

8-Methoxypsoralen; 8-MOP; 8-MP; Oxsoralen.

Biological Source Methoxsalen is a naturally occurring analogue of psoralen,

found in various species of Rutaceae, Leguminosae, and Umbelliferae. It is obtained from the fruits of Fragara xanthoxyloides and the fruits of Ammi

majus belonging to the natural order Umbelliferae. It is also found in the

herb Ruta graveolens (Rutaceae).

Isolation The various steps involved are as under:

1. The A. majus fruits are dried, powdered, sieved and extracted with petroleum ether to complete exhaustion.

2. The petroleum ether extract is filtered and concentrated to obtain a dark green semi-crystalline solid mass (crude methoxalen) crystallizes out. 3. The residual dark-green solid mass is dissolved in minimum quantity of

ethanol and boiled over an electric water-bath for 45-60 minutes. The contents are filtered immediately and the filtrate is concentrated under vacuum. It is cooled in a refrigerator overnight when pale-green crystals separate out. The crystals of methoxsalen thus obtained are purified first by washing with boiling water and finally recrystallizing from ethyl acetate.

Characteristic Features

1. It is obtained in two forms: first—as silky needles either from hot water or benzene + petroleum ether; secondly—as long rhombic prisms from ethanol + ether, having mp 148°C.

2. It is odourless but has a distinct bitter taste followed by tingling sensation. 3. It has a pH 5.5.

4. Solubility Profile: It is practically insoluble in cold water; sparingly soluble in boiling water, liquid petroleum, ether; soluble in boiling ethanol, acetone, acetic acid, vegetable fixed oils, propylene glycol, benzene; freely soluble in chloroform; and soluble in aqueous alkalies with ring cleavage, but is reconstituted upon

neutralization.

Identification Tests These are as follows:

1. A few crystals of methoxsalen on being triturated with little sulphuric acid in a porcelain dish produces an orange-yellow colour that gets changed to light green finally.

2. Wagner’s Reagent Test: Xanthotoxin gives an instant precipitate with Wagner’s Reagent (I₂ + KI).

3. HNO₃ Test: It gives a distinct yellow colouration with dilute HNO₃, which on rendering to alkaline with KOH or NaOH, changes to crimson colour.

Uses

1. It is used extensively in the treatment of leukoderma. 2. It is employed as a pigmentation agent.

Bergapten

Synonyms Bergapten; Heraclin; Majudin; Psoraderm;

5-Methoxypsoralen; 5-MOP.

Biological Source Bergapten is the naturally occurring analogue of

psoralen and an isomer of methoxsalen, mostly found in a wide variety of plants, such as: roots and fruits of Angelica archangelica L. (Apiaceae)-Angelica, Garden Angelica, European Angelica; seeds of Apium graveolens L. (Apiaceae)-Celery; leaves, stems and fruits of Petroselinum crispum (Mill.) Nym. (Apiaceae)-Parsley; Rue Oil of

Ruta graveolens L. (Rutaceae)-Rue, Garden Rue, German Rue. Preparation Bergapten was first isolated from the oil of bergamot

from Citrus bergamia Risso., belonging to the natural order

Aurantiodiae*. It was also isolated from Fagara xanthoxyloides

Characteristic Features The crystals obtained from

ethanol are needle-shaped having mp 188°C. It

sublimes on heating. It is practically insoluble in boiling

water, slightly soluble in glacial acetic acid, chloroform,

benzene, and warm phenol. It is soluble in absolute

ethanol (1 part in 60).

Identification Test It gives a distinct yellow-gold

colouration when its solution is treated with a few

drops of concentrate H

₂

SO

₄

.

Uses

1. It is used in photochemotherapy of psoriasis.

2. It has been used to promote tanning in suntan

Imperatorin

Synonyms Ammidin; Pentosalen; Marmelosin;

Biological Sources It is obtained from the roots and fruits

of Angelica archangelica L. (Apiaceae) (Angelica,

Garden Angelica, European Angelica); from the roots

of Imperatoria osthruthium L. (Umbelliferae); from fruit

of Pastinaea sativa L. (Umbelliferae); and also in the

fruits of Ammimajus (Umbelliferae). However, the seed

oil of A. archangelica is said to contain upto 0.5%

imperatorin.

Isolation The various steps involved are as follows:

1. The petroleum ether mother liquor left after the separation of methoxsalen (Xanthotoxin), is concentrated under vacuo and allowed to cool in a refrigerator overnight when the crude imperatorin separates out.

2. The crude product is collected, dissolved in ether, filtered and concentrated under reduced pressure. It is kept in a refrigerator, and the crystals separating out are purified subsequently by recrystallization from ethanol.

Characteristic Features These are as given below:

1. It is obtained in two forms: First—as prisms from ether, and secondly—as long fine needles from hot water, having mp 102°C.

2. Solubility Profile: It is practically insoluble in cold water; very sparingly soluble in boiling water; freely soluble in chloroform; and soluble in benzene, ethanol, ether, petroleum, ether alkali hydroxides.

Identification Tests These are as stated below:

1. Sulphuric Acid Test: Imperatorin gives an intense deep orange colouration with a few drops of sulphuric acid which ultimately changes to brown colour.

2. Marqui’s Reagent: It gives an orange colouration with Marqui’s Reagent that rapidly changes to brown.

3. Tollen’s Reagent (Ammoniacal AgNO₃): It reduces Tollen’s Reagent to produce a silver mirror.

4. Fehlings Test: It reduces Fehling’s solution to give a brick-red precipitate of cupric oxide. 5. Nitric Acid Test: It gives a distinct yellow colour on boiling with dilute HNO₃, and this colour

O O O HO O O O O H O OH O HO HO OH O H3CO HO OCH3

Sebutkan nama, golongan senyawa, dan manfaat

dari struktur-struktur di bawah ini :

1

2

3 4

Fenilpropanoid Rantai Pendek

• Berbagai fenilpropanoid rantai pendek yg

terdapat pada banyak herba obat biasanya

diklasifikasikan menjadi 3 kelas utama yaitu :

1.Tidak memiliki rantai samping

2.Memiliki rantai samping dengan 1 atom C, dan

3.Memiliki rantai samping dengan 2 atom C

Fenilpropanoid tidak memiliki rantai

samping

• Katekol

• Sinonim : Pirokatekol, Pirokatekin,

1,2-dihidroksibenzen

• Sumber biologis : Anandenathera peregrina

L.speg (Mimosaceae)-Niopo, Yupa; korteks Melia

azedaraeh L.(Meliaceae)-Chinaberry; Rumex

crispus L.(Polygonaceae)-Yellow Dock

• Pembuatan : ekstrak air dapat diperlakukan dg

basa encer scr hati-hati, dan garam natrium yg

dihasilkan dinetralkan utk menghasilkan katekol

dari sumber tumbuhan alam

OH

• Pemerian : katekol diperoleh sbg tablet atau prisma

monoklinat dari toluena. Katekol biasanya mengalami

perubahan warna jika terpajan udara dan cahaya.

• Karakteristik fisik: titik lebur 105°C; d 1,344; TD₇₆₀ 245,5°C.

Katekol larut dlm 2,3bagian air, etanol, benzen, kloroform,

dan eter, sangat larut dlm larutan air alkali dan piridin.

Larutan air katekol diketahui segera berubah mjd cokelat.

• Uji identifikasi: larutkan 0,2g katekol dlm air dan

tambahkan beberapa tetes larutan air FeCl₃ (0,1%b/v).

Perubahan warna menjadi hijau menunjukkan adanya

katekol.

• Kegunaan :

1. Katekol digunakan sbg bahan antiseptik

2. Katekol diketahui digunakan dlm fotografi

Fenilpropanoid dg rantai samping 1 atom C

COOH benzoic acid COOH OH OH HO Asam galat O-D-Glukosa OH Salisin OH OCH₃ O H Vanilin

Asam Benzoat

• Sinonim : asam drasiklik, asam fenilformat, asam

benzen karboksilat

• Sumber biologis : asam benzoat ditemukan dlm

btk bebas dan kombinasi. Gom benzoin

mengandung asam benzoat 20%, buah buni

(berry) mengandung asam benzoat cukupbesar

0,05%. Minyak Cananga odorata (Lam.)

Hook.f&Thoms.(Fabaceae)-Kenanga; Piper