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KIMIA ORGANIK BAHAN ALAMTERPENOID
DRS I WAYAN SUIRTA MSI
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METABOLISME PRIMER DAN SEKUNDER PADA TUMBUHAN
Chlorofil + CO2 + Cahaya
Photosintesis
Karbohidrat
Siklopentosa
Asam posfoenolpiruvat
Glikolisis
Asam sikimat Asam piruvat
Asam amino aromatik ALKALOID Asetil Ko A
Siklus as sitrat Asam amino
Malonil Ko A
Asam sinamat
FLAVONOID
PENIL PROPANOID
POLIKETIDA
SENY PHENOLIK
Asam lemak
Poliasetilena
Asam Mevalonat
TERPENOIDSTEROIDKAROTENOID
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CH2OH
K
OH
TERPENOID
Asal Usul Tersusun dari unit ISOPREN
E
Isopren Unit isopren
didukung oleh reaksi pirolisis Limonen ( Reaksi Diels - Alder)
+
+/- Limonen
Kelompok terpenoid dan sumbernya
Monoterpen,C10 Minyak atsiri
Seskuiterpen, C15 Minyak atsiri
Diterpen, C20 Resin pinus
Triterpen, C30 Damar
Politerpen, C>40 Karet alam
Contoh Monoterpen
Mirsen Sitronelol Mentol Alfa pinen
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HO
Farnesol Bisabolen
HO
Eudesmol
Contoh Seskuiterpen
Contoh Diterpen
OH
MaloolCOOH
Asam abietat Pimaradien
Contoh Politerpen
n
Karet alam
Terpenoid tak teratur
X
Lavandulol
OH
Asam krisantematSantolintrien
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Kebanyakan terpena merupakan senyawa alipatik , alisiklik atau siklik dengan gugus fungsi biasa khususnya ikatan rangkap dan alkohol.Reaksi kimia penting dan menarik karbokation
Reaksi Biosintesis Terpenoid
CH3CO-SCoA + CH3CO-SCoA CH3-CO-CH2-CO-SCoA
Asetoasetil KoA
CH3-CO-SCoA
CH3-C(OH)-CH2-CO-SCoA
CH2-CO-SCoA
[H]CH3-C(OH)-CH2-CO-OH
CH2-CH2-OH
Asam mevalonat
ATP
ADP
CH3-C(OH)-CH2COOH
CH2-CH2OP
ATP ADP
CH3-C(OH)-CH2COOH
CH2CH2OPP
Asam mevalonat piroposfat
ATP ADP
COOH-CH2-C(OP)-CH2-CH2OPPCH3
-CO2
-OP
CH3-C-CH2CH2OPP
CH2
Isopentenil piroposfat(IPP)
C=CHCH2OPP
Dimetilalil piroposfat (DMAPP)
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OPP OPP
+
H
DMAPP IPP
OPP
Geranil piroposfat
Monoterpen
OPPH
OPP
Farnesil piroposfat
Seskuiterpen, C15
Triterpen,C30
OPP
Geranil-geranil piroposfat
Diterpen,C20
Tetraterpen
OPPH
Geranil geranil farnesil pirofosfat Sesterpen,C25
Poliisopren
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BEBERAPA CONTOH MONOTERPEN DAN ISOMERNYA
CH2OH
Geraniol/trans
CH2OH
Nerol/Cis
OH
Linalol
-H2O
Mirsen[H], [O]
CHO
Sitronelal
H+/-H2O
+
+
H2O
CHO
Sitral
+
-H+
LimonenH2O
OH
O
1,8-sineol alfa-terpineol OH
OH
1,8-terpin
-H2OOH
beta-terpeneol
[O]
H2O,H+
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+ H
-H+
Limonen
OH
alfa terpineol
-H2O
+ -H++
alfa-pinen
H2
pinan
+ -H+
Bornen
H2
Bornan
+H
hydride shif t
+
H -H+ [O]O
Tujon
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alfa-pinenbeta-pinen
[O]
CH2OH
Mirtenol
[O]
CHO
Mirtenal
alfa-pinen
HCl
CHCl3
Cl
Bornin klorida
AcONa
AcOH
Camphena
H2SO4AcOH
OOCCH3KOH
EtOH
OHCrO3
H2SO4
Campor
OH
Cl
Bornen
H2O,H+
Borneol
Isoborneol
O
Isobornil asetat
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Limonen - Karvon- Karvakrol- Mentol
NOCl
Limonen
ClNO
Limonen nitrosoklorida
DMF
(COOH)2NOH
O
KarvonKarvoksim
OH
Karvakrol
O
piperaton
O
Menton
OH
Mentol
S,panas
p-simen
H2
p mentan
HCl
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O
Karvon
H+OH
Karvakrol
Na/EtOH
OH
Dihidrokarveol
H2/Kat
O
Karvomenton
Sitronelal
HOCH2CH2OH
HCCHO O
O
SeOHC
COH
O
O
H2O/H+
CHO
CHO
COH
CHO
Iridodial
KOHO
O
Isoiridomirmesin
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BEBERAPA TIPE REAKSI DALAM TERPENA
1. C= CH+
C - C+
Kestabilan karbokation: tert > sek > primer
2. C - OHH+
C - +OH2 -C+ + H2O
3. C - O - CO-CH3 - C+ + CH3-COO-
4. Shif 1,2: 1,3
C C+H
C+ C- H
5. Kondensasi aldol
CH3-CO-CH3OH-
CH3-C(OH)CH2COCH3
- CH3-H2O
C = C - CO-
6.
( ada H alfa)
Kondensasi Claisen
CH3 - CO - OEtOH-
-CH2-COOEt + CH3-CO-OEt
CH3 - C - OEt
O-
CH2-COOEt
CH3 - CO- CH2 - COOEt
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BIOSINTESIS SESKUETERPEN
OPP
tran farnesil piroposfat
OPP
H
C+
Germakrena
H
OH
GuaianolBeta elemen
OPP
Humulena
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a.
PPO
+
A
+
+
B
b.
OPP
cis farnesil pp
trans pp
+
C
+
D
+
AGama-bisabolen
gama kurkumenaO
Turmaron
CH2OH
Lansea
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+
B
+ H
Kariof ilin
+
C
H2O
OH
OH
Occidentalol
OH
Occidol
CH2OH
Costol
CHO COOH
Costalasam costak
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+
D
-H+
Humulena
H+
+
+
++
H
Kuparena
+
H2O
OH
Widdrol
+
Tujopsena
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gama bisabolen
+
OH
CedrolCedren
O
OOH
Perezon: pigmen orange fam compositae
O
O
HO
O
HO
O
beta pipitzol
O
HO
O
alfa pipitzol
OH
O
O
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OPP
a.
+
X+
OH-
+
X
HOH
+OH
X
b.
+
X
HO
+
OH
X
+
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+
X
OH
+
X
+OH
X
+
OH
X
OH
+
C
D.
+ +
X
HO
E.
+
+
OH
X
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DITERPENOID C20
CH2OPP
Geranil-geranil piroposfat
Contoh senyawa yang mengandung unit diterpenoid
O
Tokoferol/ vitamin E
O
O
Vitamin K
DITERPEN MONOSIKLIK
CH2OH
Vitamin A (retinol)NADH
CHO
Retinal
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SINTESIS VITAMIN A
A. CH3C = O
CH3
1. HC C-Li+
2. H2/PdC
OH
C = C
diketon
C = C C
O O
CH3C C = C
OCOCH2COCH3
panas
C = C - CH2CH2COCH3
metil heptanon
C-Li+C
CHO
CH
Ac2OH+
C
OAc
CH HOAc
AgOAcC
CHOAc
H+/H2O
CHO
Sitral
(CH3)2CO
OH-O
Pseuduionon
O
Beta -ionon
+
O
Alfa-ionon
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O ClCH2COOEt
NaOEt O
COOEt
1.Saponif ikasi
2. H2O,H+
CHO
I
B.
C. CH3 - CO - C=CH2 + HC C-Li C C - C(OH) - C C
CH3
H+
C C- C = C - CH2OH
CH3
EtMgBrBrMgC C - C = CHCH2OMgBr
CH3
II
D. I + II
CH2OAc
Vit A acetat
CH2OH
Vitamin A
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Diterpen bisiklik Trisiklik
+ CH2OPPH+
OH
ManoolH2O
OH
OH
Selareol
CH2OPP
+
H+
Pimaradiena
+
H
COOHAsam abietat
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terpenoid
• Biosintesis terpenoid• Keberadaan terpenoid• Sifat-sifat terpenoid ; gugus-gugus aktif komponen penyusun• Cara pemisahan terpenoid• Cara identifikasi terpenoid• Manfaat terpenoid
Daftar Pustaka
Torssell, Kurt B.G., 1983, Natural Product Chemistry, A mechanistic and Biosinthetic Approach Secondary Metabolism
Geissman T.A. and Crout D.H.G.,1969, Organic Chemistry of Secondary Plant Metabolism
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