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2.6.5.

1 Hydrocarbon Volatile Oils


It has been observed that terpene hydrocarbons usually occur in most of the volatile oils
obtained from natural sources. They may be further classified into three categories, namely:
(a) Unsaturated acyclic hydrocarbons,
(b) Aromatic hydrocarbons, and
(c) Alicyclic hydrocarbons.
2.6.5.1A Unsaturated Acyclic Hydrocarbons Two typical examples of chemical constituents
belonging to the category of unsaturated acyclic hydrocarbons are given below:
(i) β-Myrcene

Chemical Structure It is 7-methyl-3-methylene-1, 6-octadiene.


Occurance It is found in several essential oils, such as: Oil of Bay (or Myrcia oil) – Myrcia
acris (Family : Myricaceae); Oil of Hops – Humulus lupulus Linn., (family: Moraceae); and Oil
of
Turpentine – Pinus logifolia Roxb., (family: Pinaceae).
Isolation The oil of bay is treated with sodium hydroxide solution and the remaining
undissolved portion which mostly contains myrcene, is repeatedly subjected to fractional
distillation under vacuo (it is also obtained by pyrolysis of β-pinene).
Characteristic Features It has a pleasant odour. It is lighter than water d420 0.794,
nD 1.4709 and UVmax (ethanol): 226 nm (ε16, 100). It is practically insoluble in water, but
20

soluble in alcohol, chloroform, ether and glacial acetic acid.


Identification
(a) β-Myrcene on reduction with sodium and alcohol (absolute) gives rise
to dihydromyrcene (C10H18) which on subsequent bromination
o
yields tetrabromodihydromyrcene (mp 88 C), and
(b) It readily forms addition compounds with α-naphthoquinone (mp 80-81.5oC) and with
maleic anhydride (mp 34-35oC).
Use It is used as an intermediate in the manufacture of perfumery chemicals.
(ii ) Ocimene (or trans-β-Ocimene)
Chemical Structure It is 2,6 dimethyl 2,5,7 octatriene.
Use It is used as an intermediate in the manufacture of perfumery chemicals.
(ii ) Ocimene (or trans- β-Ocimene)
Chemical Structure It is 2,6 dimethyl 2,5,7 octatriene.
Occurrence trans-β Ocimene is found in the volatile oil obtained from the leaves of Ocimum
basilium L., (Labiatae); Baronia dentigeroides Cheel (Rutaceae); Litsea zeylanica C & T
Nees(Lauraceae) and Homoranthus flavescens A. Cunn., (Myrtaceae).
Isolation The volatile oil obtained from the fresh leaves of O. basilicum is treated first with
NaOH solution to get rid of the phenolic constituents i.e; eugenol present in the range of 30-40%
of the oil. The undissolved fraction of the oil is taken up in an appropriate solvent, solvent
removed under vacuum and the resulting volatile oil is subjected to fractionation under vacuum
so as to obtain the desired main constituent.
Characteristic Features
trans-β-Ocimene : d420 0.799; nD20 1.4893; UVmax (ethanol)
232 nm (ε 27, 600)
cis-β-Ocimene : d420 0.799; nD20 1.4877; UVmax (ethanol)
237.5nm (ε 21, 000)
The Ocimene (trans- or cis-) undergo oxidation most readily and with relatively shorter
exposure to air to form a yellow resin. However, in an atmosphere free from oxygen ocimene
may be preserved unaltered. Its bp ranges between 176-178oC (decomposes).
Identification
(a) Reduction with sodium and absolute alcohol yields dihydromyrcene which on
bromination yields tetrabromodihydromyrcene (mp 88oC),
(b) It yields ocimenol – an alcohol on hydration with sulphuric acid (50%) in glacial acetic
acid solution,
(c) Its phenylurethane derivative has mp 72 oC, and
(d) Ocimene upon oxidation with KMnO4 in alkaline solution affects complete degradation to
form acids, the lead salts of which has a rhombic crystalline form, whereas the corresponding
lead salts of myrcene treated in a similar fashion has a needle form thereby differentiating
between ocimene and myrcene distinctly.
Uses It is used in perfumery.
5.2.6.5.1B Aromatic Hydrocarbons A typical example of aromatic hydrocarbon is that
of paracymene as detailed below:
(i) para-Cymene
Chemical Structure It is 1-methyl-4 (1-methyl ethyl) benzene (Syn: Dolcymene)
Occurrence It occurs in a number of essential oils, such as: oils of lemon, nutmeg, corriander,
cinnamon, sage and thyme. p-Cymene has been reported in a number of volatile oils either due
to conversion from cyclic terpenes e.g., pinene or terpinene or from various terpene
analogues e.g., citral, carvone, sabinol etc.
Isolation The p-cymene fraction obtained by the fractional distillation of volatile oils may be
freed from terpenes having identical boiling points by subjecting it to oxidation with cold
KMnO4 solution, whereby the former being resistant to the oxidising agent is recovered in its
pure form. However, pure p-cymene may be prepared from thymol.
Characteristic Features para-Cymene is a colourless liquid and is found to be inactive
optically. Its fragrance resembles to that of the aromatic hydrocarbons closely.
Identification
(a) Its boiling point is 177.10oC.
(b) It melts at –67.94oC.
(c) Its specific density d204 0.8573 and d254 0.8533.
(d) Its specific rotation n20D 1.4909 and n25D 1.4885.
(e) p-Cymene on oxidation with hot concentrated potassium permanganate solution gives rise
to p-hydroxy- isopropylbenzoic acid having a melting point 155-156oC.
Uses
(i) It is employed in the formulation of certain imitation (artificial) essential oils.
(ii) It is used profusely for the preparation of scented soaps and toileteries.
(iii) It also finds its application in the masking of undesirable odours