MONOTERPENOID

Indah Yulia Ningsih, S.Farm., M.Farm., Apt.

Definisi
• Monoterpenoid : golongan terpenoid dgn 10
atom C yg secara biosintesis diturunkan dari
prekursor 2 isoprena yg terhubung secara
kepala-ekor.
• Monoterpenoid  komponen utama M. Atsiri
bersama dgn seskuiterpena
The precursor to C10 terpenoids (monoterpenes) is geraniol diphosphate,
which consists of two C5 “isoprene units ” that are joined “head-to-tail”

O O
head tail PP = P O P O
O O

OPP
head - tail head - tail
Distribusi
• Suku (familia) :
▫ Labiatae
▫ Pinaceae
▫ Rutaceae
▫ Umbelliferae
• Lokasi : glandula sekresi
Struktur sekretori khusus : sel-sel minyak,
rambut kelenjar & saluran resin
Trikom glanduler pada peppermint
Klasifikasi Monoterpena
• Berdasarkan struktur kimianya :
▫ Asiklik
▫ Monosiklik
▫ Bisiklik
▫ Tak beraturan
• Berdasarkan gugus fungsi yang ada :
▫ Hidrokarbon tak jenuh (ex : limonen)
▫ Ester alkohol (ex : linalil asetat)
▫ Aldehida (ex : sitronelal)
▫ Keton (ex : menton, karvon)
Monoterpenes in peppermint leaves
(Gershenzon et al., 2000)
Sifat umum
• Isomerisme optik
ex : nerol & geraniol, karvon.
• Sebagian besar substansi berminyak & tak
berwarna dgn td 140-180oC
• Sebagian berupa kristal
ex : kamfer
• Bau kuat & tajam
Biosintesis Monoterpenoid

(Bohlmann et al., 1998)

Jalur biosintesis
utama
monoterpena pada
rambut kelenjar
daun peppermint
(McConkey et al.,
2000)
Monoterpenes isolation
Isolation of (+)-Limonene from Citrus :
• Peel about 10 medium-sized citrus with a sharp
knife or peeler. Remove just the exterior, brightly
colored portion of the peel, called the zest, as the
white material underneath (the pith) contains little
or no limonene.
• Determine the mass of the peelings, then place
them in a blender. For best results, try to have
about 100 g of peelings. Add about 150 mL
deionized water, put the lid on the blender, and
blend the mixture until a smooth puree is obtained.
• Pour the mixture into a 500 mL round bottom flask
equipped with several boiling stones. Attach the
flask to the steam distillation system.
Monoterpenes isolation
• Note that instead of the thermometer adaptor, you will
be placing a separatory funnel containing water at the
top of the Y-adaptor. This allows you to add water to the
distillation pot as the distillation proceeds.
• Heat the contents of the distillation flask to boiling using
a heating mantle placed on a ring clamped to the ring
stand. Heat uniformly and slowly to avoid scorching the
mixture.
• Periodically add portions of distilled water from the
separatory funnel to the distillation flask to replace the
water that has been distilled over. Try to maintain a
fairly constant liquid level in the distillation flask.
Continue collecting distillate until the receiving flask is
about half full.
Monoterpenes isolation
• If the steam distillation was successful, you should notice
an upper layer of limonene in the receiving flask.
• If necessary, replace the receiving flask and collect more
distillate to improve your yield of limonene.
• When you are finished distilling, remove the heat source.
Transfer the distillate to a separatory funnel. Allow the
layers to separate and discard the lower, aqueous layer.
Dry the limonene over sodium sulfate
• Filter it through a Pasteur pipet equipped with a cotton
plug into a clean, tared vial and find the mass of the
isolated limonene.
Analisis Monoterpena
• KG
• KLT
 Contoh KLT monoterpena
Terpena UV Brom 2,4-DNP H2SO4P
Limonena - + - Coklat
α-Pinena - + - Coklat
Pulegon + + + Kuning
Geraniol - + - Lembayung
Karvon + + + Merah
Jambu
p-Simena + - - -
α-Terpineol - + - Hijau
1,8-Sineol - - - Hijau
Monoterpena Lakton (Iridoid)
• Umumnya terdapat sebagai glikosida
• Struktur : siklopentano [c] piran monoterpenoid
• Secara biogenetik dan kemotaksonomi
keterkaitan struktur antara terpena dgn alkaloid
• Marker beberapa genus : Plantago,
Plantaginaceae (aucubin); Galium,Rubiaceae
(asperuloside) & Scrophularia,Scrophulariaceae
(aucuboside/aucubin & harpagide)
Struktur kimia Iridoid
Siklopentana 
struktur utama iridoid

1a : β-cis-fused cyclopentanopyran ring system  paling umum

1b : seco-iridoids
1c
1d : iridoid glycoside
1e : iridodial  nenek moyang iridoid
1f : 8-epi-iridodial  nenek moyang iridoid
Contoh iridoid
Iridoid
• Penggunaan : bitter tonics (pahitan), sedatif,
antipiretik, obat batuk, obat luka, obat kulit &
hipotensif.
• Bioaktivitas penting : kardiovaskuler,
antihepatotoksik, koleretik, hipoglikemik,
hipolipidemik, antiinflamasi, antispasmodik,
antitumor, antivirus, immunomodulator &
purgatif
Analisis Iridoid
• Uji warna Trim-Hill
▫ Jaringan/serbuk 1 g + HCl 1% 5 ml  maserasi dlm
tabung reaksi
▫ Setelah 3-6 jam maserat dienaptuangkan + 1 ml pereaksi
Trim-Hill
▫ Panaskan tabung pada nyala api  warna
asperulin, aukubin & monotropein : biru, harpagid :
merah jadam (reddish violet)
▫ Trim-Hill : 10 ml as. asetat, 1 ml CuSO 4.5H2O 0,2% dlm
air & 0,5 ml HCl P.
Analisis Iridoid
KLT : contoh lihat Harborne (1987)
• Eluen :
▫ n-BuOH-HOAc-Air (4:1:5)
▫ isoProOH-Air (3:2)
• Penampak noda :
▫ Antimon klorida 15% dlm kloroform
▫ Anisaldehida-as. sulfat-EtOH (1:1:18)
Panaskan 100oC 2-5’
Thank You