200726978-terpenoid.ppt

7/21/2019 200726978-terpenoid.ppt

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KIMIA ORGANIK BAHAN ALAMTERPENOID

DRS I WAYAN SUIRTA MSI

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METABOLISME PRIMER DAN SEKUNDER PADA TUMBUHAN

Chlorofil + CO 2 + Cahaya

Photosint sis

Kar!ohi"rat

Si#lo$ ntosa

Asa% $osfo nol$ir&'at

(li#olisis

Asa% si#i%at Asa% $ir&'at

Asa% a%ino aro%ati# ALKALOID As til Ko A

Si#l&s as sitrat Asa% a%ino

Malonil Ko A

Asa% sina%at

)LA*ONOIDPENIL PROPANOID

POLIKETIDA

SEN PHENOLIK

Asa% l %a#

Polias til na

Asa% M 'alonat

TERPENOIDSTEROIDKAROTENOID

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CH 2 OH

K

OH

TERPENOID

Asal Us&l T rs&s&n "ari &nit ISOPREN

E

Iso$r n Unit iso$r n

"i"&#&n, ol h r a#si $irolisis Li%on n - R a#si Di ls . Al" r/

+

+0. Li%on n

K lo%$o# t r$ noi" "an s&%! rnya

Monot r$ n1C 3 Minya# atsiri

S s#&it r$ n1 C 4 Minya# atsiri

Dit r$ n1 C23 R sin $in&s

Trit r$ n1 C53 Da%ar Polit r$ n1 C673 Kar t ala%

Contoh Monot r$ n

Mirs n Sitron lol M ntol Alfa $in n

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HO

)arn sol Bisa!ol n

HO

E&" s%ol

Contoh S s#&it r$ n

Contoh Dit r$ n

OH

MaloolCOOH

Asa% a!i tat Pi%ara"i n

Contoh Polit r$ n

n

Kar t ala%

T r$ noi" ta# t rat&r

X

La'an"&lol

OH

Asa% #risant %atSantolintri n

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K !anya#an t r$ na % r&$a#an s nya8a ali$ati# 1 alisi#li# ata& si#li# " n,an ,&,&s f&n,si !iasa#h&s&snya i#atan ran,#a$ "an al#ohol9R a#si #i%ia $ ntin, "an % nari# #ar!o#ation

R a#si Biosint sis T r$ noi"

CH5

CO.SCoA + CH5

CO.SCoA CH5

.CO.CH2

.CO.SCoA

As toas til KoA

CH 5 .CO.SCoA

CH 5 .C-OH/.CH 2 .CO.SCoA

CH 2 .CO.SCoA

:H;CH 5 .C-OH/.CH 2 .CO.OH

CH 2 -CH 2 -OH

Asa% % 'alonat

ATP

ADP

CH 5 .C-OH/.CH 2 COOH

CH 2 -CH 2 OP

ATP ADP

CH 5 .C-OH/.CH 2 COOH

CH 2 CH 2 OPP

Asa% % 'alonat $iro$osfat

ATP ADP

COOH.CH2.C-OP/.CH2.CH2OPPCH 3

.CO 2

.OP

CH 5 .C.CH 2 CH 2 OPPCH 2

Iso$ nt nil $iro$osfat-IPP/

C<CHCH2OPP

Di% tilalil $iro$osfat -DMAPP/

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OPP OPP

+

H

DMAPP IPP

OPP

( ranil $iro$osfat

Monot r$ n

OPP

H

OPP

)arn sil $iro$osfat

S s#&it r$ n1 C 4

Trit r$ n1C53

OPP

( ranil., ranil $iro$osfat

Dit r$ n1C23

T trat r$ n

OPP

H

( ranil , ranil farn sil $irofosfat S st r$ n1C24

Poliiso$r n

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BEBERAPA CONTOH MONOTERPEN DAN ISOMERN A

CH 2 OH

( raniol0trans

CH 2 OH

N rol0Cis

OH

Linalol

.H 2 O

Mirs n:H;1 :O;

CHO

Sitron lal

H + 0.H 2 O

+

+

H 2 O

CHO

Sitral

+

.H +

Li%on nH 2 O

OH

O

1=.sin ol alf a.t r$in ol OH

OH

1=.t r$in

.H 2 OOH

! ta.t r$ n ol

:O;

H 2 O1H +

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+ H

.H +

Li%on n

OH

alf a t r$in ol

.H 2 O

+ .H + +

alf a.$in n

H 2

$inan

+ .H +

Born n

H 2

Bornan

+

H

hy"ri" shift

+

H.H + :O;

O

T&>on

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alfa.$in n ! ta.$in n

:O;

CH 2 O H

Mirt nol

:O;

CHO

Mirt nal

alfa.$in n

HCl

CHCl 5

Cl

Bornin #lori"a

A?ONa

A?OH

Ca%$h na

H 2 SO 7A?OH

OOCCH 3KOH

EtOH

OHCrO 5

H 2 SO 7

Ca%$or

OH

Cl

Born nH 2 O1H +

Born ol

Iso!orn ol

O

Iso!ornil as tat

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Li%on n . Kar'on. Kar'a#rol. M ntol

NOCl

Li%on n

ClNO

Li%on n nitroso#lori"a

DM)

-COOH/ 2NOH

O

Kar'onKar'o#si%

OH

Kar'a#rol

O

$i$ raton

O

M nton

OH

M ntol

S1$anas

$.si% n

H 2

$ % ntan

HCl

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O

Kar'on

H +OH

Kar'a#rol

Na0EtOH

OH

Dihi"ro#ar' ol

H 2 0Kat

O

Kar'o% nton

Sitron lal

HOCH 2 CH 2 OH

HCCH O O

O

S OHC

COH

O

O

H2 O 0H +

CH O

CH O

COH

CHO

Iri"o"ial

KOHO

O

Isoiri"o%ir% sin

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BEBERAPA TIPE REAKSI DALAM TERPENA

9 C< CH +

C . C +

K sta!ilan #ar!o#ation@ t rt 6 s # 6 $ri% r

29 C . OHH +

C . + OH 2 .C+ + H 2 O

59 C . O . CO.CH 5 . C+ + CH5.COO .

79 Shif 12@ 15

C C+

H

C+ C. H

49 Kon" nsasi al"ol

CH 5 .CO.CH 5OH .

CH 5 .C-OH/CH 2 COCH 3

. CH 5.H 2 O

C < C . CO.

9

- a"a H alf a/

Kon" nsasi Clais n

CH5 . CO . OEtOH .

. CH 2 .COOEt + CH 5 .CO.OEt

CH5 . C . OEt

O -

CH 2 -COOEtCH 5 . CO. CH 2 . COOEt

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BIOSINTESIS SESKUETERPEN

OPP

tran f arn sil $iro$osf at

OPP

H

C +

( r%a#r na

H

OH

(&aianol B ta l % n

OPP

H&%&l na

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a9

PPO

+

A

+

+

B

!9

OPP

?is farn sil $$

trans $$

+

C

+

D

+

A (a%a.!isa!ol n

,a%a #&r#&% naO

T&r%aron

CH 2 OH

Lans a

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+

B

+ H

Kariof ilin

+

C

H 2 O

OH

OH

O??i" ntalol

OH

O??i"ol

CH 2 OH

Costol

CHO COOH

Costalasa% ?osta#

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+

D

.H +

H&%&l na

H +

+

+

++

H

K&$ar na

+

H 2 O

OH

i""rol

+

T&>o$s na

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,a%a !isa!ol n

+

OH

C "rolC "r n

O

O

OH

P r on@ $i,% n oran, f a% ?o%$osita

O

O

HO

O

HO

O

! ta $i$it ol

O

HO

O

alf a $i$it ol

OH

O

O

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OPP

a9

+

+

OH .

+

X

H

OH

+

OH

X

!9

+

X

HO

+

OH

X

+

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+

X

OH

+

X

+OH

X

+

OH

X

OH

+

C

D9

+ +

X

HO

E9

+

+

OH

X

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DITERPENOID C 23

CH 2 OPP

( ranil., ranil $iro$osfat

Contoh s nya8a yan, % n,an"&n, &nit "it r$ noi"

O

To#of rol0 'ita%in E

O

O

*ita%in K

DITERPEN MONOSIKLIK

CH 2 OH

*ita%in A -r tinol/ NADH

CHO

R tinal

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SINTESIS *ITAMIN A

A9 CH 5C = O

CH 3

9 HC C . Li +

29 H 2 0P"C

OH

C = C

"i# ton

C < C C

O O

CH 5 C C = C

OCOCH 2 COCH 5

$anas

C = C - C H 2 CH 2 COCH 3

% til h $tanon

C . Li +CC

HOCH

A?2OH +

C

OAc

CH HOA?

A,OA?

C

CHOA?

H + 0H 2 O

CHO

Sitral

-CH 5 / 2 CO

OH.

O

Ps &"&ionon

O

B ta .ionon

+

O

Alf a.ionon

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O ClCH 2 COOEt

NaOEt O

COOEt

9Sa$onif i#asi29 H 2 O1H +

CHO

I

B9

C9 CH 5 . CO . C<CH 2 + HC C.Li C C . C-OH/ . C C

CH 5

H +

C C. C < C . CH 2 OH

CH 5

EtM,Br BrM,C C . C < CHCH 2 OM,Br

CH5

II

D9 I + II

CH 2 OAc

*it A a? tat

CH 2 OH

*ita%in A

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Dit r$ n !isi#li# Trisi#li#

+ CH 2 OPPH +

OH

ManoolH 2 O

OH

OH

S lar ol

CH 2 OPP

+

H +

Pi%ara"i na

+

H

COOH

Asa% a!i tat

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7/21/2019 200726978-terpenoid.ppt


t !" n#$%

& B$#'$nt '$' t !" n#$%& K ( !)%))n t !" n#$%& S$*)t-'$*)t t !" n#$% + , , '-, , ' ).t$* .#/"#n n " n0 ' n& C)!) " /$')1)n t !" n#$%

& C)!) $% nt$*$.)'$ t !" n#$%& M)n*))t t !" n#$%

D)*t)! P 't).)

T#!'' ll2 K !t B G 2 45632 N)t !)l P!#% ct C1 /$'t!02 A / c1)n$'t$c)n% B$#'$nt1 t$c A""!#)c1 S c#n%)!0 M t)(#l$'/G $''/)n T A )n% C!# t D H G 245752 O!,)n$c C1 /$'t!0 #*

S c#n%)!0 Pl)nt M t)(#l$'/

7/21/2019 200726978-terpenoid.ppt


200726978-terpenoid.ppt

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