Biosynthesis of Volatile oils

Under supervision of:

Dr : Amina Hanem Abo Donia Dr :Hala Mostafa Abd Elghany Dr : Hatem Mohamed Miky

VOLATILE OILS
Volatile or essential oils, as their name implies, are volatile in steam. They differ entirely in both chemical and physical properties from fixed oils. They are secreted in oil cells, in secretion ducts or cavities or in glandular hairs.

Production and uses of volatile oils

The total annual production of volatile oils is estimated to be in the region of 45,000 tones, worth approximately US$700 million. There are about 100 commercially valuable volatile oils directly derived from plants. Volatile oils are used for their therapeutic action, for flavoring (e.g. oil of lemon), in perfumery (e.g. oil of rose) or as starting materials for the synthesis of other compounds (e.g. oil of turpentine).

 For therapeutic purposes they are administered as inhalations (e.g. eucalyptus oil), orally (e.g. peppermint oil), as gargles and mouthwashes (e.g. thymol) and transdermally (many essential oils including those of lavender, rosemary and bergamot are employed in the practice of aromatherapy). Those oils with a high phenol content, e.g. clove and thyme have antiseptic properties, whereas others are used as carminatives. Oils showing antispasmodic activity, and much used in popular medicine.

Composition of volatile oils

Volatile oils are generally mixtures of hydrocarbons and oxygenated compounds derived from these hydrocarbons. The odour and taste of volatile oils is mainly determined by these oxygenated constituents, which are to some extent soluble in water but more soluble in alcohol.

 Practically all volatile oils consist of chemical mixtures that are often quite complex; they vary widely in chemical composition. Almost any type of organic compound may be found in volatile oils (hydrocarbons, alcohols, ketones, aldehydes, ethers, oxides, esters, and others). usually volatile oils are classified according to the type of organic compounds. It is not uncommon for a volatile oil to contain over 200 components, and often the trace constituents are essential to the odor and flavor. The absence of even one component may change the aroma.

Essential oils are products of a secondary metabolism of plants, and are composed of :
1- Fragrant volatile materials consisting of complex mixtures of: mono- and sequi-terpenes, hydrocarbons, and oxygenated materials biogenically derived from them (i.e. terpenoids)

2- Phenyl propanoids from the Shikimic acid pathways, and their biotransformation products (i.e. aromatics )

3- Other compounds from the metabolism of fatty acids and amino acids
4- A large number of other types of chemical compounds, including nitrogen and sulphur

Chemical constituents of volatile oils

Chemical constituents of volatile oils may be divided into 2 broad classes, based on their biosynthetic origin: 1- Terpene derivatives formed via the acetate-mevalonic acid pathway. 2- Aromatic compounds formed via the shikimic acid-phenylpropanoid route.

Terpene pathway
1- Terpene derivatives formed via the acetate-mevalonic acid pathway.

Terpene derivatives
CH3 CH3 O CH3

OH H3C CH3 H3C CH2 H3C

OH CH3

Menthol (peppermint oil)

Carvone (caraway oil)

Thymol (thyme oil)

Photosynthesis
Is the process by which, with the help of sunlight, plants can produce carbohydrates in their chlorophyll-containing cells using water (from the soil) and carbon dioxide (from the air ) light 6CO2+6H2O C6H12O6+ 6O2

The product of these reactions, glucose, is then split through further reactions, from which a new compound - pyruvic acid (C3H4O3) is born. Pyruvic acid is further broken down to acetic acid (C2H4O2)

The path leading from carbohydrates to terpenes involved isoprene as a biogenic precursor.

Modern theories suggest that a compound called mavelonic acid might be the root source of many compounds in essential oils.

And here is a short summary of how it happens

Acetic acid is converted through a series of condensation and reduction reactions to mavelonic acid, which in turn - via series of redoc reactions - leads to monoterpenes. The terpene framework is then rearranged, oxidised, reduced, hydrated etc., to produce a range of terpenoid products

Mavelonic acid IPP (isopentenyl pyrophosphate) + DMAPP (3,3-dimethylallylpyrophosphate)

GPP (geranyl pyrophosphate) monoterpenes

Terpenoid class Hemiterpenoid C5

Example Prenol (syn. 3methyl-2-butenol), prenyl esters

Occurs in Ylang-ylang oils Cananga odorata subsp. genuina

Monoterpenoid C10
Sesquiterpenoid C15 Diterpenoid C20 Sesterterpenoid C25 Triterpenoid C30 Carotenoid C40

Limonene
beta-Caryophyllene Sclareol Ophiobolin A Isophytol

Citrus oils (Citrus spp.)

Clove oil Syzigium aromaticum Clary sage absolute Salvia sclarea Certain fungi Jasmin absolute, wax Jasminum grandiflorum Green plant tissues

beta-Carotene

The Mevalonate Independent Pathway

Pyruvate Hydroxy ethyl thiamine pyrophosphate + (3-glycerylaldehyde-3-phoshate)

1-deoxy-D-xylulose 5-phosphate
. IPP

Biosynthesis and chemical composition

Chemical constituents of volatile oils may be divided into 2 broad classes, based on their biosynthetic origin:
1. Terpene derivatives formed via the acetate-mevalonic acid pathway. 2. Aromatic compounds formed via the shikimic acid-phenylpropanoid route.

Shikimic Acid Pathway

Shikimic acid is formed from glucose in plants, and is the biogenic precursor of the amino acids L-phenylalanine, L-tyrosine and L-typtophan.

Pathways from shikimic acid generate

1- anthranilates e.g. in mandarin oil Citrus reticulata 2- Cinnamates e.g in peru balsam oil and other phenylpropanoids, and from this point on to other metabolites such as lignans & .flavononoids

3-carbon chain attached to a benzene ring are formed from trans or (E)-cinnamic acid via the elimination of ammonia from Lphenylalanine. Common phenylpropanoids in essential oils include methyl chavicol, methyl eugenol, eugenol, methyl cinnamate, vanillin & .anethole

An investigation of accumulation of phenylpropenes in the two types of glandular trichomes 1-(peltate & capitate) in two chemotypes of Sweet Basil 2- (eugenol & methyl chavicol) oil leaves

Aromatic compounds
OH OCH3 OCH3

CH2 Eugenol (clove oil)

CH3 Anethole (anise oils)

CHO Cinnamaldehyde (cinnamon oil)

Refrences

PDR hand books

www Faculty ksu eu pharmacognosy

Thank You

By : THANK YOU Doaa Mohamed shoshan By:

Doaa Mohamed shoshan