Ocimene - A Versatile Floral Ingredient

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4342 Fragrance Vol.38•January2013|Perfumer&Flavorist www.PerfumerFlavorist.com
Ocimene
A versatile floral ingredient
Michael Zviely, CIC; and Ming Li, The Key Laboratory of Food Colloids and
Biotechnology, Ministry of Education, Department of Applied Chemistry,
School of Chemical & Material Engineering, Jiang Nan University, China
O
cimene (F-1) has a warm-herbaceous, citrus, tropical,
green, terpene, woody odor that is very diffusive with
relatively low tenacity. Its sweetness is almost floral,
evoking an immediate similarity to neroli oil in the odor of pure
ocimene.
1
It also has vegetable nuances, and when tasted it has a
green, tropical, woody flavor with floral and vegetable nuances.
2
Ocimene occurs in ho leaf oil, hop oil, kumquat, mango, mint,
neroli, bigarde oil, parsley, pepper, petitgrain, bergamot oil,
lavender and more.
Pure ocimene can be used in numerous artificial essential
oils, bergamot, lavandin, neroli, orange, basil, etc., but it is also
in itself an interesting material for a new and powerful top-
note effect in citrus colognes, lavender and fougere. It also has
applications in mango and spicy-herbaceous fragrances, as well
as limited use in household product fragrances.
There is a very considerable difference in price between
ordinary grade ocimene and pure ocimene, but the terpene is
often used so sparingly that it compensates for its relatively high
cost. Commercial-grade ocimene is used as a starting material
for the manufacture of a number of perfume chemicals, and it
is also used occasionally as a perfume material since it creates
very pleasant effects with bay oil in modem spicy-herbaceous
fragrances.
1
(E)-β-Ocimene is recommended for use in fragrances at
levels up to 3%.
a, b
The ocimenes (trans- or cis-) undergo oxidation most read-
ily and with relatively shorter exposure to air to form a yellow
resin. However, ocimene may be preserved unaltered in an
Reproduction in English or any other language of all or part of this article is strictly prohibited. © 2013 Allured Business Media.
atmosphere free from oxygen. F-2 describes a list of additional
isomers of ocimene. Ocimene derivatives used in the F&F indus-
try are shown in F-3. The biosynthetic pathway for ocimene is
shown in F-4.
Monoterpene compounds, such as (E)-β-ocimene and myr-
cene, contribute significantly to the floral odors of numerous
plant species.
5
(E)-β-Ocimene constitutes 87% of the scent
of the orchid Laelia anceps, whereas the scent of Brugmansia
x candida, a member of Solanaceae, contains as much as 52%
(E)-β-ocimene.
6,7
In snapdragon (Antirrhinum majus), the
monoterpene fraction of the floral scent bouquet is dominated
by (E)-β-ocimene and myrcene, which account for 20% and
8% of total floral volatiles, respectively.
8
Snapdragon flowers
emit these two monoterpene olefins—myrcene and (E)-β-
ocimene—biosynthetically derived from geranyl diphosphate,
in addition to a major phenylpropanoid floral scent component,
methylbenzoate.
Emission of myrcene and (E)-β-ocimene is regulated
developmentally and follows diurnal rhythms controlled by a
circadian clock.
9
E-β-Ocimene is also a pheromone involved in social regula-
tion in the honey bee colony (Apis mellifera L. ). In honey bee
colonies, the brood is able to manipulate and chemically control
the workers in order to sustain their own development. A brood
ester pheromone produced primarily by old larvae was first
identified as acting as a contact pheromone with specific effects
Physical Data for Ocimene
a, b
Appearance: Colorless to straw-colored liquid
M.W.: 136.2
Assay (min.): 80%
Boiling point: 176°–178°C
Specific gravity: 0.801–0.805 (25°C)
Refractive index: 1.4780–1.4910 (20°C)
Acid value (mgKOH/g): 1.00 max.
Flash point: 143°F TCC
LogP(o/w): 4.70 (estd.)
a
The Good Scents Company site database www.thegoodscentscompany.com/
b
Ocimene PQ spec. sheet of Innospec for a product containing cis-β-ocimene >69%
F-1. 3,7-Dimethyl-1,3,6-octatriene; (E)-β-ocimene; C10H16;
CAS# 13877-91-3; FEMA# 3539
F-2. Ocimene isomers
F-3. Ocimene derivatives
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atmosphere free from oxygen. F-2 describes a list of additional
isomers of ocimene. Ocimene derivatives used in the F&F indus-
try are shown in F-3. The biosynthetic pathway for ocimene is
shown in F-4.
Monoterpene compounds, such as (E)-β-ocimene and myr-
cene, contribute significantly to the floral odors of numerous
plant species.
5
(E)-β-Ocimene constitutes 87% of the scent
of the orchid Laelia anceps, whereas the scent of Brugmansia
x candida, a member of Solanaceae, contains as much as 52%
(E)-β-ocimene.
6,7
In snapdragon (Antirrhinum majus), the
monoterpene fraction of the floral scent bouquet is dominated
by (E)-β-ocimene and myrcene, which account for 20% and
8% of total floral volatiles, respectively.
8
Snapdragon flowers
emit these two monoterpene olefins—myrcene and (E)-β-
ocimene—biosynthetically derived from geranyl diphosphate,
in addition to a major phenylpropanoid floral scent component,
methylbenzoate.
Emission of myrcene and (E)-β-ocimene is regulated
developmentally and follows diurnal rhythms controlled by a
circadian clock.
9
E-β-Ocimene is also a pheromone involved in social regula-
tion in the honey bee colony (Apis mellifera L. ). In honey bee
colonies, the brood is able to manipulate and chemically control
the workers in order to sustain their own development. A brood
ester pheromone produced primarily by old larvae was first
identified as acting as a contact pheromone with specific effects
Physical Data for Ocimene
a, b
Appearance: Colorless to straw-colored liquid
M.W.: 136.2
Assay (min.): 80%
Boiling point: 176°–178°C
Specific gravity: 0.801–0.805 (25°C)
Refractive index: 1.4780–1.4910 (20°C)
Acid value (mgKOH/g): 1.00 max.
Flash point: 143°F TCC
LogP(o/w): 4.70 (estd.)
(Z)-β-Ocimene
cis-3,7- dimethylocta-1,3,6-triene
[3338-55-4]
α-Ocimene
3,7-Dimethyl-1,3,7-octatriene
[502-99-8]
(E,E)-2,6-Alloocimene
(4E,6E)-2,6-dimethylocta-2,4,6-triene
[3016-19-1]
(E,Z)-Alloocimene
(4E,6Z)-2,6-Dimethylocta-2,4,6-triene
[7216-56-0]
β-Myrcene
7-Methyl-3-methylene-1,6-octadiene
[123-35-3]
α-Myrcene
2-Methyl-6-methylene-1,7-octadiene
Substance synonym
[CAS no.]
Structure Organoleptic properties
Warm, oral, herbaceous, sweet
Fruity, oral, wet cloth
Terpeny, sweet, fresh, oral
n.a.
Terpeny, herbaceous, woody with a
rosy celery and carrot nuance
3
n.a.
F-2. Ocimene isomers
Substance synonym
[CAS no.]
Structure Organoleptic properties
O
O
Ocimene oxirane
2,2-Dimethyl-3-(3-methylpenta-
2,4-dienyl)oxirane
Myroxyde
[69103-20-4]
Ocimene quintoxide
5-[(E)-but-2-en-2-yl]-2,2-dimethyloxolane
Sweet, metallic, fresh, herbal, lavender,
opoponax, clary, pear
a
Citrus, cooling, woody, camphoraceous,
minty, with a green and fresh spicy nuance
5
F-3. Ocimene derivatives
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on nurses in the colony. E-β-Ocimene has
been identified recently as a new volatile
brood pheromone, which partially inhibits
ovary development in workers.
10
Ocimene
is prepared by two main routes: 1) thermal
rearrangement of α-pinene (pyrolysis) (F-5)
and 2) by dehydration of linalool (F-6).
11, 12
References
1. Arctander’s Perfume and Flavor Chemicals,
Allured Business Media, Carol Stream, IL (1999)
2. G Mosciano, Organoleptic Characteristics of
Flavor Materials, Perfumer & Flavorist, 15(2),
69 (1990)
3. G Mosciano, Organoleptic Characteristics of
Flavor Materials, Perfumer & Flavorist, 25(6),
26 (2000)
4. G Mosciano, Organoleptic Characteristics of
Flavor Materials, Perfumer & Flavorist, 15(3),
51 (1990)
5. JT Knudsen, L Tollsten and G Bergstrom, Floral
scents: A checklist of volatile compounds isolated
by head-space techniques, Phytochemistry, 33,
253–280 (1993)
6. R Kaiser, The Scent of Orchids—Olfactory and
Chemical Investigations, Elsvier, Amsterdam
(1993)
7. GC Kite and C Leon, Volatile compounds emitted
from flowers and leaves of Brugmansia x candida
(Solanaceae), Phytochemistry, 40, 1093–1095
(1995)
8. N Dudareva, LM Murfitt, CJ Mann,
N Gorenstein, N Kolosova, CM Kish, C Bonham
and K Wood, Developmental regulation of methyl
benzoate biosynthesis and emission in snapdragon
flowers, The Plant Cell, 12, 949–961 (2000)
9. N Dudareva, D Martin, CM Kisha, N Kolosova,
N Gorensteina, J Fäldt, B Millerb and
J Bohlmann, (E)-b-Ocimene and Myrcene
Synthase Genes of Floral Scent Biosynthesis in
Snapdragon: Function and Expression of Three
Terpene Synthase Genes of a New Terpene
Synthase Subfamily, The Plant Cell, 15(5)
1227–1241 (2003)
10. A Maisonnasse, J-C Lenoir, D Beslay,
D Crauser, Y Le Conte, E-b-Ocimene, a Volatile
Brood Pheromone Involved in Social Regulation
in the Honey Bee Colony (Apis mellifera),
PLoS ONE 5(10): e13531, doi:10.1371/journal.
pone.0013531
11. A Boake, Preparation of Ocimene, NL 294903,
19650426 (1965)
12. SA Singh, et al, Amberlyst-15-Catalyzed Efficient
Cyclization of g- and d-Unsaturated Alcohols:
Green Synthesis of Oxygen Heterocycles,
Synthetic Communications, 40(1), 74–80 (2010)
Linalool
OH
2-Vinyl-2,6,6-trimethyl-
3,4,5,6-tetrahydro-2H-pyran
9%
O
Ocimene
40%
Allo-ocimene
30%
+
+
Amberlyst-15
50-70
0
C/5hr
F-6. Dehydration of linalool
α -Pinene
Dipentene
27%
Allo-ocimene
16%
Ocimene
48%
+
+
600
0
C
25mmHg
F-5. Thermal rearrangement of α-pinene (pyrolysis)
Geranyl diphosphate
P
O
O
OH
OP
O
OH
HO
(E)-β-Ocimene
F-4. General biosynthetic pathway for ocimene
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