F&F chemistry

Alcohols and Ethers

Flavor and odor characteristics and effects in
formulations

Michael Zviely and Chu Hong

Department of Applied Chemistry, School of Chemical & Material Engineering
Jiang Nan University, China

A
lcohols play a rather considerable role as flavor
and fragrance ingredients, including some of the
most important constituents in the industry. The
2 alcoholic function is seen in simple aliphatic molecules,
in acyclic and cyclic terpenes and in molecules containing
benzene rings.
The role of ethers is relatively less significant; however,
many are key ingredients in the creation of fragrances
and flavors. (Note: Thio alcohols and thio ethers are not
reviewed in this article.)
which is found in apples, citrus, strawberries, wine, beer
and tea, and which imparts a green leaf, fresh, fatty, grassy
flavor with fruity and juicy nuances; and 1-octen-3-ol
(see F-3) (Mitsutake alcohol), which occurs in tomatoes,
mushrooms, beef, milk, malt, pumpkin, licorice, dill, rice,
leeks and beans, and which has a powerful herbaceous,
earthy, mushroomlike flavor.
The different odor characteristics of the two enantiomers
of 1-octen-3-ol (see F-4) are as follows:1,**

Aliphatic Alcohols
n-Amyl alcohol, n-heptanol, 1-nonanol F-1
Aliphatic alcohols consist of
simple or branched chains, con-
taining double or triple bonds,
or those hanging on a ring. The
simple saturated alcohols n-amyl
VOL. 34 APRIL 2009

alcohol and n-heptanol are

presented here as examples (see
F-1). n-Amyl alcohol occurs in
fruits and baked, dairy, meat,
alcoholic and roasted food flavors.
The material has a soft, mild
fresh ethereal, somewhat yeasty
F-2
(-)-R-1-octen-
and moldlike odor and flavor. In high dilutions it has an 3-ol: fruity, genuine cis-3-Hexenol
intense fusel, fermented, bready and cereal character.* mushroomlike; also
n-Heptanol, on the other hand, occurs in foods and bev- desribed as having an
erages such as fruits, dairy products, beef, alcohol, and intense mushroom
tea, and has a mild, oily, slightly caprylic fatty flavor. Also note; fruity, soft; odor
represented in F-1 is alcohol C-9 nonylic (1-nonanol), threshold—10 ppb in
which has a floral, rosy, fatty and citruslike odor. aqueous ethanol.
Further along the aliphatic alcohol series are some (+)-S-1-octen-
PERFUMER & FLAVORIST

important unsaturated alcohols, the first being leaf alcohol
(cis-3-hexenol; see F-2), which occurs in freshly cut
green grass, apples, citrus, hops, peas, potatoes, etc., and
has a strong, fresh, green grass, raw fruity odor and flavor,
with a pungent freshness.
Two other important unsaturated alcohols, which are
primarily used in flavors, are: trans-2-hexenol (see F-3),
*Most of the information on occurrence, organoleptic properties and uses
are taken from: FRM 2001—Database of Flavour Raw Materials and PMP
96, Database of Perfumery Materials & Performance, Boelens Aroma
Chemicals Information Services, Netherlands. Some of the organoleptic
information is cited from suppliers specification sheets, e.g. IFF, Givaudan,
Firmenich, Takasago, KAO etc.
3-ol: moldy, grassy,
artificial; also described as herbaceous, green, musty; odor
threshold—100 ppb in aqueous ethanol.
Next, among longer chain alcohols, is 2-trans,cis-
6-nonadien-1-ol (Cucumber alcohol [synonym:
2-trans,6-cis-nonadien-1-ol]), Violet leaf alcohol [syn-
onym: 2-trans,6-cis-nonadien-1-ol] and 9-decen-1-ola
(see F-5).
2-trans,6-cis-Nonadien-1-ol occurs in melon,
cucumber, raw lean fish and prickly pear. It has an
**JC Leffingwell, Chirality & Odour Perception. In: The 1-Octen-3-ols;
www.leffingwell.com
intense, heavy fatty, green odor
and green, cucumberlike flavor.
9-Decen-1-ol is found in cognac
trans-2-Hexenol, 1-octen-3-ol
F-3
and cardamom, and has a fresh
rose-floral, slightly fatty flavor,
and fresh, green odor, with an
aldehydic dewy rose note. The
material imparts a waxy, aldehy-
dic character without being fatty
and maintains a constancy of odor
strength.
Two other alcohols, which are

F-4
primarily used in fragrances, are
2,6-dimethyl-2-heptanolb and (-)-R-1-Octen-3-ol, (+)-S-1-octen-3-ol
3,4,5,6,6-pentamethylheptan-
2-olc (see F-6). The former has a
strong fresh floral, citrus, woody,
lavender and lily of the valley 3
odor, whereas the latter possesses
an exquisite floral, woody odor
with dry, ambery, vetiver and
raisin nuances.
Two synthetic processes towards
2,6-dimethyl-2-heptanol are shown in F-7.
Alcohol C-11 undecylenic (10-undecen-1-ol) has a
fresh, citrus and slightly waxy odor (see F-8). This alcohol
2-trans,6-cis-Nonadien-1-ol, 9-decen-1-ol
F-5
gives volume and natural freshness to floral compositions
such as rose, jasmine and lilac.
Another 11-carbon-atom alcohol is 4-methyl-3-
decen-5-old, which possesses a fresh floral, green, violet
odor (see F-9). 4-Methyl-3-decen-5-ol was developed in
connection with structural elucidation work on unknown
trace components of lily of the valley. It has a powerful
green-floral character, somewhat related to lily of the
valley, with natural, fresh, fruity violet leaf and linden-
blossom aspects. It can be used successfully in rose
and fruity pear accords. Although easy to use in most
perfumery types, it requires careful dosage and blending
due to its exceptional strength.
An analysis conducted on the
two enantiomers of this chemical
revealed the differences in their
odor characteristics:2,***
2,6-Dimethyl-2-heptanol (Dimetol), 3,4,5,6,6-pentamethylheptan-2-ol
(Kohinool) F-6
(-)-(S)-4-Methyl-dec-3-en-5-ol
(ee = 75%):—weaker enantiomer;
fruity-green, pinefir balsam note
with aspects of tea, not so typical of
Undecavertol; odor threshold: 4.7
ng/L air (see F-10).
(+)-(R)-4-Methyl-dec-3-
en-5-ol (ee = 93%):—typical
Undecavertol odor, floral, green,
fresh, violet leaves, stronger and
greener than the racemic com-
mercial material, with aspects of
cucumber and Neofolionee (methyl non-2-enoate); odor Ethyl linalool is yet another important 11-carbon-
threshold: 0.31 ng/L air (see F-10). atom alcohol (see F-11). It has a fresh, floral, rich odor
and bergamotlike character, and is sweeter and less
***JC Leffingwell, Chirality & Odour Perception. In: The Undecavertols; agrestic than linalool. As with linalool, it is used in a wide
www.leffingwell.com variety of notes for floral bouquets.
F&F chemistry
Two synthetic processes towards 2,6-dimethyl-2-heptanol F-7

4
VOL. 34 APRIL 2009

floral note. It is very long-lasting and more similar to rose

10-Undecen-1-ol
F-8 than muguet (See F-13).
A closed ring molecule that is similar to
3,7-dimethyloctan-1,7-diol is 1-hydroxy-2-(1-methyl-1-
hydroxyethyl)-5-methylcyclohexaneg (see F-14). The
latter material has a geranium, rosy, fruity odor; it is a
complex mixture with a fresh geranium odor. A top note
ingredient, it has good diffusivity and increases the fruity
character of compositions.
4-Methyl-3-decen-5-ol
F-9 Another acyclic sesquiterpene is 3,7,11-trimethyl-
1,6,10-dodecatrien-3-olh (Nerolidol) (see F-15).
Nerolidol occurs in citrus oils, strawberry, tomato, ginger,
mint, pepper, thyme, hop, beer etc., and has a mild,
woody, floral, green odor and flavor.
PERFUMER & FLAVORIST

Several other well known cyclic monoterpenes and a

Terpenes—Acyclic and Cyclic
This group contains some of the most important alcohols
in the flavor and fragrance industry. Citronellol, geraniol,
nerol and linalool are a few examples of these materials
(see F-12).
3,7-Dimethyloctan-1,7-diolf is another monoterpene
that has a floral, balsamic, fatty odor, with a mild, clean,
sesquiterpene alcohol are listed in F-16.
The biosynthesis of alcoholic terpenes occurs by
dimerization of two isopentenyl-pyrophosphate units to
obtain a monoterpenic unit of geranyl pyrophosphate
(see F-17). This intermediate loses the pyrophosphatic
group to obtain the unstable geranyl carbocation, which
can stabilize by reaction with water to yield geraniol,
nerol, linallol, or, by cyclization and reaction with water,
a-terpineol.
Some of these commercially important alcohols can
be prepared from natural sources such as a-pinene and
b-pinene, as shown in F-18.
(-)-S-4-Methyl-dec-3-en-5-ol, (+)-R-4-methyl-dec-3-en-5-ol F-10

F-11
Hydrogenation of perillyl alcohol creates
Ethyl linalool
tetrahydroperillyl alcohol, or cis-4-(isopropyl)cyclo-
hexanemethanoli. This product has a floral, muguet odor,
and is used in applications requiring a stable muguet note.
Another commercial cis-4-(isopropyl)cyclohexanemeth- 5
anol materialj (see F-19) is described as having a fresh,
soft and clean floral odor reminiscent of the white petals
and blossoms of many flowers such as magnolia, tuberose
and muguet. The producer suggests this material harmo-
nizes wonderfully with muguet, lilac, tuberose, jasmine
florals, and with citrus notes such as bergamot. It com-
bines well with muguet ingredients, often
giving lift and smoothness to the fragrance.
Some important alcohols used in the F&F industry F-12 With woody and methylionone blends,
Mayol diffuses the woody character to the
top of the perfume. Small percentages give
floral freshness, and large amounts can
produce original effects.
cis-4-(Isopropyl)cyclohexanemethanol
can be prepared either from b-pinene ((S)-
4-Isopropenyl-1-cyclohexenylmethanol) or
cumminaldehyde, as shown in F-20.3
The following cyclic alcohols are
miscellaneous commercial fragrance
ingredients:
4-Isopropylcyclohexanolk has a dif-
fusive leathery, floral effect reminiscent of
lilac, rose and geranium (see F-21).
2,4-Dimethyl cyclohexane metha-
noll has a floral, minty, hyacinth, woody

3,7-Dimethyloctan-1,7-diol F-13
F&F chemistry
1-Hydroxy-2-(1-methyl-1-hydroxyethyl)-
5-methylcyclohexane F-14 3,7,11-Trimethyl-1,6,10-dodecatrien-3-ol
(Nerolidol) F-15

6
Other well known cyclic monoterpenes and
a sesquiterpene alcohol F-16 odor. It is a full-bodied floral bouquet with
minty nuances (see F-22).
2-tert-Butylcyclohexanolm has a piney,
camphoraceous, minty odor (see F-23).
This extremely powerful chemical pos-
sesses a minty, animalic, camphoraceous
odor in the pine and patchouli families.
3a,4,5,6,7,7a-Hexahydro-2,6(or
3,6)-dimethyl-4,7-methano-1h-
inden-5-oln also belongs to the family
of patchouli notes, imparting a woody,
patchouli, camphoraceous odor profile
(see F-24).
2-Naphthalenol, 1,2,3,4,4a,5,6,7-
octahydro-2,5,5-trimethyl-o has a very
strong and powerful note with a natural
ambergris quality; it is also somewhat
VOL. 34 APRIL 2009

musky, animal and earthy (see F-25). The

material is best used in small amounts. It
can be applied in all perfume types to add
depth, complexity and texture, particularly
in woody, oriental and floral creations.
Two more cyclic alcohols are 2,4-(and
3,5)-dimethylcyclohex-3-ene-1-methanolp
and 2,4,6-trimethyl-3-cyclohexene-
1-methanolq (see F-26). The dimethyl
cyclohexene methanol isomers have a floral,
green, spicy odor; it is also fresh, green and
floral, reminiscent of hyacinth, muguet and
mimosa. 2,4,6-Trimethyl-3-cyclohexene-1-
methanol is spicy, green, woody, floral and
belongs to the carnation family.
PERFUMER & FLAVORIST

Alcohols Containing Benzene Rings:

This group of flavor and fragrance ingredi-
ents includes many well known materials,
some of which are shown in F-27. (Note:
Phenols will be reviewed along with ben-
zene rings in a future article.)
Among additional fragrance ingredients
containing a benzene ring is 2,2-dim-
ethyl-3-(3-methylphenyl)propanolr,
which possesses a fresh, soft, intensely
floral fragrance reminiscent of lily of the
**** (S)-4-Isopropenyl-1-cyclohexenylmethanol
Biosynthesis of alcoholic terpenes
cis-4-(Isopropyl)cyclohexanemethanol
4-Isopropylcyclohexanol
F-17
F-19 valley; it imparts a slightly green odor with a fruity top
note (see F-28).
2,2-Dimethyl-3-phenylpropanols on the other hand,
has a fresh aromatic floral odor, with some aspects of
muguet (see F-28).
Another muguet product is 3-methyl-4-phenyl-2-bu-
tanolt (see F-29). The material has a floral, muguet, rose
odor; its floral muguet distinguishes itself in applications
in which aldehydic muguet ingredients are not stable.
In addition to these floral alcohols, additional materials
containing a benzene ring are mentioned in F-30. Dim-
F-21 ethylbenzylcarbinol (2-methyl-1-phenyl-propan-2-ol)
possesses a floral, rose, green, oily odor. 2-Methyl-4-
phenyl-1-pentanolu has citrus and grapefruit aspects.
o-Methyl, 2-phenethyl alcoholv features floral, rose
and mimosa odor charcteristics. Finally, 3-methyl-5-
phenyl-1-pentanolw can be described as floral, rose
and geranium. This last material can be prepared via the
routes shown in F-31, starting from benzaldehyde or
benzyl chloride.
F&F chemistry
a-Pinene as starting material, b-pinene as starting material F-18

8
VOL. 34 APRIL 2009

Preparing cis-4-(Isopropyl)cyclohexanemethanol from

b-pinene and cumminaldehyde F-20 2,4-Dimethyl cyclohexane
methanol F-22
PERFUMER & FLAVORIST

2-tert-Butylcyclohexanol F-23

3a,4,5,6,7,7a-Hexahydro-2,6(or
3,6)-dimethyl-4,7-methano-1h-inden-5-ol
2-Naphthalenol, 1,2,3,4,4a,5,6,7-octahydro-
2,5,5-trimethyl-
Other alcohols containing benzene rings
F-24
2,4-(and 3,5)-Dimethylcyclohex-3-
ene-1-methanol and 2,4,6-trimethyl-3-
cyclohexene-1-methanol
F-26
F-25
9
F-27 To conclude this section, no review
on alcohols in the flavor and fragrance
industry would be complete without
mentioning the family of sandalwood
molecules. F-32 shows some of the
most popular materials in this group.
Ethers as F&F Ingredients
Ethers are less common than alco-
hols, but still can be found among
flavor and fragrance ingredients. A
few examples of molecules that do not
contain a benzene ring are discussed
hereafter. The aromatic ethers will be
reviewed in future articles discussing
benzene-ring-containing molecules.
The first two ethers here are sim-
ple aliphatic materials—n-decanyl
methyl ether, which has an alde-
hydic, fatty, fresh odor, and methyl
n-hexyl etherx, which possesses
a floral, herbal, fruity organoleptic
character (see F-33).
Phenylethyl cyclohexyl ethery
is a simple molecule with a floral,
hyacinth, fruity odor. The material
features a refined floral note with
hyacinth associations and a modifying
fruity (raspberry) effect (see F-34).
3,3,5-Trimethylcyclohexyl ethyl
etherz has a green, fruity, herbal,
natural note and a diffusive odor
(see F-34).
Two cedarwood ethers are polycy-
clic molecules—cedrylmethyl ether,
F&F chemistry
2,2-Dimethyl-3-(3-methylphenyl)propanol
and 2,2-dimethyl-3-phenylpropanol F-28 3-Methyl-4-phenyl-2-butanol F-29

10 Dimethylbenzylcarbinol (2-methyl-1-phenyl-propan-2-ol);
2-methyl-4-phenyl-1-pentanol; o-methyl, 2-phenethyl alcohol;
3-methyl-5-phenyl-1-pentanol
F-30 with a fine cedarwood odor and a distinct
amber nuance, and a-cedrene epoxideaa,
with a woody, dry, patchouli precious odor
that is reminiscent of ambergris, tobacco
and sandalwood (see F-35).
Another tricyclic ether is
4,9,12,12-tetramethyl-5-oxatricy-
clo[8.2.0.0(4,6)]dodecanebb, which has
a dry, woody, amber-spice odor combina-
tion and a cigar box nuance (see F-36).
Another macrocyclic ether worth
mentioning is 1-methyl-1-methoxy-
cyclododecanecc, which has a woody,
tobacco, ambery and warm odor (see
VOL. 34 APRIL 2009

F-37).
2-Ethenyl-2,6,6-trimethyltetra-
hydropyranedd is a camphoraceous,
woody, cineole-limelike material (see
F-38). It is used where a lemon-woody

F-31
note is desired. It also offers pine needle
Preparation of 3-methyl-5-phenyl-1-pentanol (Phenoxanol) and lime nuances.
The camphane derivative exo
1-propanol,3-(2-bornyloxy)-2-meth-
ylee (see F-39) has a warm, woody, dry
amber, cedarwood odor is somewhat
structurally related to two other bicyclic
molecules—bicyclo[2.2.1]heptane,
2-ethylidene-6-isopropoxyff and
ethyl methoxy norbornanegg (see
PERFUMER & FLAVORIST

F-39). Bicyclo[2.2.1]heptane, 2-eth-

ylidene-6-isopropoxy has an unusual
combination of herbal, citrus, licorice
and petitgrain notes, modified by ani-
mal nuances of costus, whereas ethyl
methoxy norbornane is herbal, leafy and
green with citrus notes.
Finally, there is 2-ethoxy-9-meth-
ylen-2,6,6-trimethylbicyclo[3.3.1]
nonanehh, which is a rich woody
chemical with a distinct orris note. Its
ambery and tobacco undertones add to
its elegant character (see F-40).
Most popular sandalwood molecules F-32

11
F&F chemistry
n-Decanyl methyl ether and methyl n-hexyl ether F-33

Phenylethyl cyclohexyl ether and 3,3,5-trimethylcyclohexyl ethyl ether F-34

12

Cedrylmethyl ether and a-cedrene epoxide F-35 4,9,12,12-Tetramethyl-5-

oxatricyclo[8.2.0.0(4,6)]dodecane F-36
VOL. 34 APRIL 2009

F-37 F-38
PERFUMER & FLAVORIST

1-Methyl-1-methoxycyclododecane 2-Ethenyl-2,6,6-trimethyltetrahydropyrane
 exo 1-Propanol, 3-(2-bornyloxy)-2-methyl; bicyclo[2.2.1]heptane, 2-ethylidene-6-
isopropoxy; ethyl methoxy norbornane F-39

13

F-40
a Roslava is a trademark of IFF.
b Dimetol is a trademark of Givaudan.
2-Ethoxy-9-methylen-2,6,6-
c Kohinool is a trademark of IFF. trimethylbicyclo[3.3.1]nonane
d Undecavertol is a trademark of Givaudan.
e Neofolione is a trademark of Givaudan.
f Hydroxyol is a trademark of IFF.
g Geranodyle is a trademark of Givaudan.
h Nerolidol is a trademark of xxxxxxxxxxx.
i Meijiff is a trademark of IFF.
j Mayol is a trademark of Firmenich.
k Apo Patchone is a trademark of IFF.
l Dihydro Floralol is a trademark of IFF.
m Verdol is a trademark of IFF.
n Dimethyl Cyclormol is a trademark of IFF.
o Ambrinol was developed and trademarked by Fritzsche Dodge & Olcott Inc.
p Floralol is a trademark of IFF.
q Iso Cyclo Gernaiol is a trademark of IFF.
r Majantol is a trademark of Symrise.
s Muguet alcohol is a trademark of XXXXXXX.
t Muguesia is a trademark of IFF.
u Pamplefleur is a trademark of IFF. Metal (Rh, Ru)-Binap-Catalyzed Asymmetric Synthesis of Chiral
v Peomosa is a trademark of IFF. Compounds for Flavors and Fragrances and Their Associated Sensory
w Phenoxanol is a trademark of IFF. Properties. In: Current Topics in Flavours and Fragrances Towards
x Diola is a trademark of IFF. a New Millennium of Discovery, Edit., KA Swift, 33–58, Kluwer
y Phenafleur is a trademark of IFF. Academic Publishers, Dordrecht, Netherlands (2000)
z Herbavert is a trademark of XXX.
aa Andrane is a trademark of IFF. 2. A Abate, E Brenna and G Fregosi, Bio-catalysed synthesis of optically
bb Tobacarol is a trademark of IFF. active Undecavertol enantiomers. Tetrahedron: Asymmetry 16
cc Madrox is a trademark of Givaudan. (2005)
dd Limetol is a trademark of Givaudan.
ee Bornafix is a trademark of IFF.
3. Swiss patent CH581592, 1973, assigned to Firmenich
ff Isoproxen is a trademark of IFF; co-discovered by University of Florida

researchers.
gg Neoproxen is a trademark of IFF.
hh Boisiris is a trademark of Givaudan.

References

1. A Mosandl, G Heusinger and M Gessner, Analytical and Sensory

Differentiation of 1-Octen-3-01 Enantiomers. J Agric Food Chem,
34, 119–122 (1986); MH Boelens, H Boelens and LJ van Gemert,
Perfum Flavor, 18(6), 1–15, (1993); S Kawamata, M Nozaki and N
Suzuki, Sensory Evaluation of Optically Active 1-Alken-3-ols. In:
Proceedings of the 10th Weurman Flavour Research Symposium; To purchase a copy of this article or others,
Dijon, June (2002); T Yamamoto, Advances in the Transition visit www.PerfumerFlavorist.com/magazine.