VOLATILE OIL I.
Definition Volatile oils, also known as ethereal oils, essential oils and in some instances as essences, are called so because they are the ones responsible for the odors or aromas present in the flowers and/or in other parts of many plants. They are the scented oils of plants Volatile oils are characterized as liquid, volatile, clear and rarely colored, lipid soluble and soluble in organic solvents with a generally lower density than that of water. They can be synthesized by all plant organs, i.e. buds, flowers, leaves, stems, twigs, seeds, fruits, roots, wood or bark, and are stored in secretory cells, cavities, canals, epidermic cells or glandular trichomes. They are frequently associated with other substances such as gums and resins. They readily volatilize at room temperature and distilled in steam. Moreover, they tend to resinify and become oxidized on exposure to air and light. II. General structures Main compounds of volatile oils are mainly derived from three biosynthetic pathways: a) mevalonate pathway leading to sesquiterpenes; b) methyl-erithrytol-pathway leading to mono- and diterpenes; and c) shikimic acid pathway leading to phenylpropenes. All terpenes are formed from 5-C elements or isoprene, which is the basic structural element.
R and R can link to other isoprene molecules, forming long molecular chains. Classification of Terpenes Monoterpene is a 10-Carbon terpene containing 2 isoprene units. Sesquiterpene is a 15-Carbon terpene containing 3 isoprene units. Diterpene is a 20-Carbon terpene containing 4 isoprene units. Triterpene is a 30-Carbon terpene containing 6 isoprene units. Tetraterpene is a 40-Carbon terpene containing 8 isoprene units.
Terpene derivatives
CH3 CH3 O CH3
OH H3C CH3 H3C CH2 H3C
OH CH3
Menthol (peppermint oil)
Carvone (caraway oil)
Thymol (thyme oil)
Aromatic compounds are derived from phenylpropene, making them occur less frequently than the terpenes.
OH OCH3 OCH3
CH2 Eugenol (clove oil)
CH3 Anethole (anise oils)
CHO Cinnamaldehyde (cinnamon oil)
III.
Classification The following is the classification of volatile oils based on the chemical constituents with corresponding examples. 1. Oils containing mainly Terpenes and Sesquiterpenes Turpentine - contains pinene and sylvestrene 2. Oils containing mainly Alcohols and their esters A. Aliphatic saturated alcohols Oil of Heracleum - contains octyl alcohol and octyl ester B. Aliphatic unsaturated alcohols Geranium contains geraniol and geranyl esters C. Monocyclic and dicyclic alcohols Peppermint contains menthol and menthone D. Aromatic alcohols and esters
Oil of Jasmine contains benzyl acetate and benzyl alcohol 3. Oils containing Aldehydes as characteristic constituents A. Aliphatic unsaturated aldehydes Lemon - contains citral and citronellal B. Aromatic aldehydes Cinnamon - contains cinnamaldehyde and eugenol 4. Oils containing Ketones as characteristics constituents A. Aliphatic saturated ketones Oil of Rue - contains methyl nonyl ketone B. Aliphatic unsaturated ketones Oil of Lemon grass - contains methyl heptenone C. Monocyclic and dicyclic ketones Spearmint - contains carvone 5. Oils containing Esters A. Aliphatic acids German Chamomile contains caproic acid esters B. Aromatic acid esters Sweet Birch - contains methyl salicylate C. Undetermined acids Oil of Celery contains sedanolide and lactone 6. Oils containing Phenols and Phenol Ethers A. Monatomic phenols and their ethers Anise contains anethol and methyl chavicol B. Diatomic phenols and their ethers Cloves contains eugenol and caryophyllene (a sesquiterpene) C. Triatomic phenols and their ethers Oil of Asarum contains asarone and methyl eugenol D. Tetratomic phenols and their ethers Oil of Parsley contains apiol 7. Oils containing Neutral Bodies Laurel leaves contains cineol and pinene 8. Oils containing Sulfur Onion - contains allyl propyl sulfide
IV.
Medicinal uses/Pharmaceutical uses/Other uses
Volatile oils are important because of the many uses. Some include the following with corresponding examples: Therapeutically (Oil of Eucalyptus) Flavouring (Oil of Lemon, Spearmint oil) Perfumery (Oil of Rose, Oil of Citrus) Starting materials to synthesize other compounds (Oil of Turpentine) Anti-septic (as gargles and mouthwashes) due to phenol content (Oil of Thyme) Preservative - oils interfere with bacterial respiration Anti-spasmodic (Ginger, Lemon balm, Rosemary, Peppermint, Chamomile, Fennel, Caraway) Aromatherapy oils directly applied to the affected parts like wounds and burns or massaged into the skin (Oils of lavender, rosemary and bergamot) Inhalations (Eucalyptus oil) Carminatives (Peppermint) Insect repellant (Citronella oil)
V.
Extraction procedure Volatile oils may be produced or extracted by: A) Steam - Simple steam distillation - Saturated steam distillation - Hydrodiffusion B) Expression The set-up for steam distillation is illustrated as follows:
In conducting steam distillation, the following procedures are followed: 1. Weigh 5 g of the plant part. Grind them to a coarse powder, using a mortar and pestle. 2. Transfer the ground plant part to a 100-mL round-bottom flask. 3. Add distilled water to the flask. Mix well with a glass-stirring rod. Mark the level of the mixture on the side of the flask. 4. Assemble the steam distillation apparatus. Use the 100-mL roundbottom flask as the pot. Use the 50-mL round-bottom flask as the receiver. 5. Pour 100 mL of water into the addition funnel. Start the flow of water through the condenser. 6. Adjust Bunsen burner flame to lessen the hot central cone. Heat the pot by waving the flame back and forth under the pot. 7. Maintain a distillation rate of approximately one drop every 35 s. 8. Add water to the pot at 10-min intervals to keep the water level at the mark. 9. Replenish the ice in the beaker that is used to cool your collection flask as necessary. Use a Pasteur pipet to remove some of the water before adding more ice. 10. The vapor should be cloudy when the natural products are codistilling with the water. When the vapor becomes clear you can remove the heat from the round bottom flask. 11. Stop the distillation when approximately 30 mL of distillate has been collected. A) Steam Distillation - Simple Steam Distillation Plant material is immersed directly in a flask filled with water. This is then brought to a boil. Heterogeneous vapours are condensed on a cold surface. Essential oil separates based on difference in density and immiscibility. - Saturated Steam Distillation In this type of distillation, steam is in equilibrium with heated water at the same pressure. Plant material does not come into contact with the water. Steam is injected through the plant material placed on perforated trays. It is possible to operate under moderate pressure. Using saturated steam distillation limits the alteration of the constituents of the oil, shortens the duration of the treatment and conserves energy. - Hydrodiffusion Hydro diffusion is a type of steam distillation. The difference lies in the way the steam is introduced into the still. With hydro diffusion, the steam is introduced from the top onto the plant material at very low pressure instead of from the bottom as in regular steam distillation. The condensation of the steam mixture containing the oil occurs below the area where the plant material is held in place.
The advantages of this method are: less steam used, shorter processing time and higher oil yield. But due to co extraction of other non-volatiles and polar components with the essential oils, the process is complicated. B) Expression The classic process of expression utilizes an abrasive action which is applied on the surface of the fruit in a flow of water. The solid waste is eliminated, and the essential oil is separated from the aqueous phase by centrifugation. Most facilities allow for the simultaneous or sequential recovery of the fruit juice and of the essential oil, by collecting the oil with a spray of water after the abrasion (scarification puncture by pins) before or during the expression of the fruit juice. Enzymatic treatment of the residual water allows recycling, and markedly increases the final yield of essential oil. Citrus oils are also obtained directly from the fruit juices by vacuum de-oiling. The vacuum thermal de-oiling furnaces are developed to remove oils by volatilization at low pressure and temperature. For removal of the oil, furnaces are fitted with a vacuum pumping system that produces the vacuum levels required for volatilization of the oils. The vacuum system is also configured to operate within the environment generated as the oil is pumped out of the chamber and discharged at the pump exhaust for collection. In operation, the internal walls of the vacuum de-oiling furnace are maintained in a hot condition to prevent condensation of oil vapors within the furnace.
