IKIMIA ORGANIK BAHAN ALAMJURUSAN KIMIA S1-FMIPATERPENOIDSRURINI RETNOWATICHEMISTRY DEPARTMENTMATHEMATICS AND NATURAL SCIENCES FACULTYBRAWIJAYA UNIVERSITY

TERPENESTerpenes, or terpenoids, are the largest group of secondary products (metabolites).They are all formed from acetyl CoA or glycolytic intermediates.

CLASSIFICATION OF TERPENESAll terpenes are formed from 5-C elements

Isoprene is the basic structural element.

(2-methylbutadiene)isoprene unitHT

The Classification of Terpenoids**number of carbon atoms**

Hemiterpenoids C-5tailhead

Monoterpenoids C-10

geraniollimonene

Sesquiterpenoids C-15

zingiberene

cadinene

Diterpenoids C-20

Abietic acid

Sesterterpenoids C-25

Triterpenoids C-30sesquiterpenoid

lanosterol

carbon 40 atomsPolyterpenoidsTetraterpenoids(C5H8)n ; n > 8

HemiterpenoidsMonoterpenoidsSesquiterpenoidsDiterpenoidsSesquiterpenoidsTriterpenoidsTetraterpenoidsPolyterpenoidsVolatileLess volatileInvolatile

BIOSINTESIS ISOPRENOIDAda dua jalur biosintesis pada sel eukariotik yang telah diketahui, yaitu :Jalur MevalonatJalur DeoxyxyluloseKedua jalur tersebut terjadi melalui isopentenyl pyrophosphate (IPP)Jalur mevalonat disebut juga jalur sintesis isoprenoid klasik, biasanya terjadi di dalam sitoplasmaJalur deoxyxylulose biasa terjadi di dalam plastida (seperti kloroplast dan mitokondria)

Biosintesis IPP melalui jalur mevalonata. Pembentukan asam Mevalonat

b. Pembentukan IPPc. Isomerisasi IPP DMAPP

Biosintesis IPP melalui jalur deoxyxylulose

EXAMPLES OF TERPENESLIMONENEMENTHOLPATCHOULI ALCOHOL

i. LIMONENEStructural classification: Monocyclic terpene

Functional Classification: Unsaturated HC

Occurrence: Citrus fruit

ii. MENTHOLStructural classification:Monocyclic with hydroxyl group

Functional classification: Alcohol

Occurrence: Peppermint

MENTHOL

PATCHOULI ALCOHOL

Biosynthesis of ISOPRENE unitMevalonate pathway3 AcetateIPPDMAPP

Acetoacetyl CoAClaisen condensationketoenolPg.3

3S-HMG-CoAAldol condensation3R-mevalonatereduction of thioester

3R-mevalonate-5-PPDMAPPIPP

Pg.4

Hemiterpenoids isopentenol, 3,3-dimethylallyl alcohol artocarpin

amyl alcoholfalse hemiterpenoidsaliphatic amino acidangelic acidtiglic acid

Monoterpenoids

isoprene 2 units head-to-tail geranyl pyrophosphate (GPP) neryl pyrophosphate (NPP) volatile oils = essential oils = etherial oils

stereoselective coupling

Monoterpenoids

1. Acyclic monoterpenoids

Acyclic monoterpenoids myrcene : Cymbopogon nardus ocimene : Ocimum spp. citral : Cymbopogon citratus, Citrus citronellal : C. nardus, Citrus geranial : C. nardus, Citrus

Acyclic monoterpenoids citronellol : C. nardus, Citrus linalool : Thyme, linalyl acetate : Lavender nerol : Rose oil geraniol : Lavandula sp. lavandulol : Lavandula sp.

Cyclic monoterpenoids

borneol

fenchane

H

O

1,8

3,8

+

camphane

+

carane

pinene

pinane

+

2,8

1,2-hydride shift/2,4

10

9

8

7

6

5

4

3

2

1

thujene

thujane

+

menthane

+

+

NPP

GPP

P

P

O

P

P

O

2. Monocyclic monoterpenoidsMenthane

a-terpineolterpinolenelimonene

Monocyclic monoterpenoids limonene : l-form Citrus spp. d-form Pinus spp. a-phellandrene : Eucalyptus spp. carveol : Carum carvi thymol : Thymus vulgaris (Thyme)

Monocyclic monoterpenoids menthol : Mentha piperita menthone : M. piperita carvone : Carum carvi, M. spicata, cineol : Alpinia galanga, Boesenbergia pandurata Zingiber officinale

ascaridoleChenopodium ambrosioides var. anthelminticum herb

Chenopodium ambrosioides

3. Bicyclic monoterpenoids Thujane Carane Pinane Camphane (Bornane) Fenchane

Thujane1,2-hydride shift24

Thujane group

* Thuja spp. * Family Cupressaceae a-thujene : Thuja occidentalis thujone : T. occidentalis sabinene : Juniperus sabina

Carane38

Bornane Pinane8 21

Pinane group

* Pinus spp. * Family Pinaceae a-pinene : turpentine oil from wood & bark of Pinus palustris uses : rubefacient for rheumatic pain

Pinus palustris

Bornane group (Camphane) (+)camphor (Laurel Camphor) Cinnamomum camphora (Lauraceae)Uses: antipruritic, insect repellant, counter-irritant, carminative, CNS stimulant

Cinnamomum camphora

Bornane group (Camphane) borneol (Borneo Camphor) Dryobalanops aromatica Dipterocarpaceae Uses: topical applications use apply to injuries, burns, rheumatic pains, hemorrhoids, skin diseases, and ulcerations of the mouth, ear, eye, and nose

Dryobalanops aromatica

FenchaneFenchane group

fenchone : Foeniculum vulgare Fennel..

IRREGULAR MONOTERPENES Cyclopropane monoterpenoids Iridoids Cannabinoids

Cyclopropane monoterpenoids(Chrysanthemyl skeleton)chrysanthemic acidpyrethric acid

pyrethrin 1 : R = CH=CH2jasmolin 1 : R = CH2CH3cinerin 1 : R = CH3

PYRETHRIN terpenoidsPyrethrum (Insect Flower)Chrysanthemum cinerariaefolium Vis.C. coccineum Willd. Family Compositae

insecticide, parasitocide very toxic to fish! rapid paralytic action

Chrysanthemum cinerariaefolium

pyrethroids : decamethrindibromovinyl : photostablecyano group : activity3-phenoxybenzyl moiety : fat-solubility

IRIDOIDS Iridomyrmex : defensive secretioncyclopentanopyran ring Aucubin glycosides Aucuba sp. 1-O-glucosides

iridaneseco-iridane

iridoidsLoganin indole alkaloid

VOLATILE OILS

VOLATILE OILSAll official volatile oils are of vegetable origin. Normally pre-exist in the plant stored in a special secretory tissue (e.g. Citrus peel oil cells or oil ducts in umbelliferous fruits).EXCEPTION: Oil of bitter almond formed by hydrolysis of the glycosides.

USES OF VOLATILE OILSTherapeutically (Oil of Eucalyptus)Flavouring (Oil of Lemon)Perfumery (Oil of Rose)Starting materials to synthesize other compounds (Oil of Turpentine)Anti-septic due to high phenols (Oil of Thyme). Also as a preservative (oils interfere with bacterial respiration)Anti-spasmodic (Ginger, Lemon balm, Rosemary, Peppermint, Chamomile, Fennel, Caraway)Aromatherapy

DEFINITION OF VOLATILE OILSVolatile oils are products which are generally complex in composition, consisting of the volatile principles contained in plants, and are more or less modified during the preparation process.

Only 2 procedures may be used to prepare official oilsSteam distillationExpression

4 Main types of volatile oilsConcretesPomadesResinoidsAbsolutes

CONCRETESPrepared from raw materials of vegetable origin (bark, flowers, leafs, roots etc.)

Extracted by HC type solvents, rather than distillation or expression Becomes necessary when the essential oil is adversely affected by hot water or steam (e.g. jasmine).

Produces a more true-to-nature fragrance.

CONCRETESConcretes contain about 50 % wax and 50 % essential oil (jasmine).

Ylang ylang (concrete volatile) contains 80 % essential oil and 20 % wax.

Advantages of concretes: they are more stable and concentrated than pure essential oils.

POMADESTrue pomades are (volatile oil) products of a process known as enfleurage (hot or cold).Enfleurage is used for obtaining aromatic materials from flowers containing volatile oils to produce perfume long after they were cut.

ENFLEURAGE: METHODA glass plate is covered with a thin coating of especially prepared and odourless fat (called a chassis).

The freshly cut flowers are individually laid on to the fat which in time becomes saturated with their essential oils. The flowers are renewed with fresh material.

Eventually the fragrance-saturated fat, known as pomade, may be treated with alcohol to extract the oil from the fat.

RESINOIDSPrepared from natural resinous material (dried material) by extraction with a non-aqueous solvent, e.g. Petroleum ether or hexane.

E.g. Balsams Peru balsam or benzoin; resins (amber or mastic); Oleoresin (copaiba balsam and turpentine); Oleogum resins (frankincense and myrrh)

RESINOIDSCan be viscous liquids, semi-solid or solid.Usually homogeneous mass of non-crystalline character.

Uses: in perfumery as fixatives to prolong the effect of a fragrance.

ABSOLUTESObtained from a concrete, pomade, or a resinoid by alcoholic extraction.

The extraction process may be repeated.

The ethanol solution is cooled & filtered to eliminate waxes.

The ethanol is then removed by distillation.

They are usually highly concentrated viscous liquids.

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