Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
10~3'7
This invention relates to chemical compounds and their
use as flavour and odour agents. More specifically this invention
relates to cycloaliphatic unsaturated esters which are valuable
food and tobacco flavour agents and perfume odour agents.
This application is a divisional application of copend-
ing application No. 220,557 filed February 21, 1975.
Increasing attention is being devoted to the preparation
and utilization of artificial perfuming and odour-modifying agents
in perfumes and perfumed products, and of artificial flavouring
and taste modifying agents in foodstuffs, beverages, pharmaceu-
ticals, and tobacco. This attention has been stimulated not only
because of the inadequate quantity of natural perfume and flavour-
ing materials available, but, perhaps even more importantly,
because of the need for materials which can combine several
natural nuances, will blend better with other perfuming or flavour-
ing compositions, and will give perfumed or flavoured products
which can be specifically tailored to a given use and because they
can be duplicated at will. This latter factor confers a major
advantage to artificial perfuming and food flavouring agents,
since natural products, such as essential oils, extracts, concen-
trates, and the like are subject to wide variation because of
changes in the quality, type or treatment of the raw material.
This invention provides esters of safranic acid and
homologues thereof and with their use as flavour and odour agents.
Safranic acid occurs in three isomeric forms, known as
~ -, and y-safranic acid, having the structures I, II, and III
respectively: ~ \ ~ ~
~ COOH ~ COOH ~ ~ COOH
I~
For simplicity in referring to the various compounds of
this invention, in analogy with the isomers of safranic acid, the
lO~iO9'7
following nomenclature is used throughout this specification:
6 a = conjugated double bonds in positions
COOR2 2 (endocyclic) and 4;
~ = conjugated double bonds in positions
4 ~_~ ~ 1 and 3;
3 1 y = conjugated double bonds in positions
IV -a, -~, or - ~. 2 (exocyclic) and 3.
a-safranic acid is described in Helv.Chim.Acta 31 (1948) 134
~-safranic acid in Berichte 74 (1941) 1242 and
a- and y-safranic acids are mentioned in Helv.Chim.Acta 33 (1950)
1746.
Also some methyl- and ethyl esters of safranic acid are described
in the literature:
- Ethyl a-safranate in Helv.Chim.Acta 31 (1948) 134;
- Methyl - and y-safrantes and ethyl a- and y-safrantes are
mentioned in Helv.Chim.Acta 33 (1950) 1746;
- Ethyl ~-safranate is prepared in Helv.Chim.Acta 38 (1955) 1863;
- Methyl ~-safranate is mentioned in Compt.Rend.Ser. C 262 (1966)
1725, in Bull.Soc.Chim.France (1966) 3874, and in Agr.Biol.Chem.
34 (1970) 198~ ~
- Ethyl a.-, ~-, and y-safrantes are prepared in Helv.Chim.Acta
54 (1971) 1767;
- Esters of a-, ~-, and y-safranic acid with saturated alcohols
containing 1-4 carbon atoms are also mentioned in Dutch Patent
Applications 72.11248 and 73.01451, open to public inspection on
August 17th, 1972, and August 7th, 1973, respectively. In these
publications the safranates are used as intermediates in syntheses
of safranal, damascenones or abscisic acid. However, nowhere
mention is made of the organoleptic properties of these esters.
- We have now found that the safranic acid esters possess
useful organoleptic properties and can be used for flavouring and
perfuming a wide range of products. The compounds of the inven-
tion may be used, combined with other flavouring agents, diluents
l(lf~109'~
or carriers, for flavouring foodstuffs, beverages or tobacco
products, they may be compounded with other odoriferous compounds
to make perfumery compositions, in the manner conventional in
the perfumery art.
In copending application No. 220,557 there are disclosed
and claimed a safranic acid ester having the general formula IV
5 ~ COOR2
~ J~2
4 ~Y ~Rl
wherein the dotted lines represent two conjugated double bonds in
the positions 2 endocyclic and 4 (~-isomer), and l and 3 (~-isomer)
or 2 exocyclic and 3 ( ~isomer), Rl represents an alkyl group or,
in the ~isomers an alkylidene group with 1-3 carbon atoms and
R2 represents an alkyl- or alkenyl group with 1-4 carbon atoms,
provided that when Rl is CH3 or CH2, R2 is an alkenyl group with
1 to 4 carbon atoms.
According to the present invention there is provided a
perfume of flavouring composition containing at least one ester
having the general formula IV
~
5 ~ ~ COOR2
4 ~ Rl
wherein the dotted lines represent two conjugated double bonds in
the positions 2 (endocyclic) and 4 (a-isomer~, 1 and 3 (~-isomer),
or 2 (exocyclic) and 3 (y-isomer), Rl represents a methyl group,
or,in the ~isomers a methylidene group, and R2 represents an alkyl
group with 1-4 carbon atoms. The compounds of formula IV wherein
Rl is CH3 (~- or ~-isomers) or CH2 (~-isomers) and R2 is CH3 or
C2H5 are known compounds, as these esters are the methyl- and
ethyl safranates, described in the literature cited above.
The compounds of formula IV may be prepared by methods
~o~,~09'7
described in the cited literature. The methods described in the
examples are modifications of the method given in Dutch Patent
Application 73.01451, pp 11-13, where the ~ -, and y-safranic
acid ethyl esters are prepared from mesityl oxide and ethyl
acetoacetate according to reaction scheme A, as intermediates in
a synthesis of damascenone analogues.
coon2 ~ ~ ~coon2
// \ R R ll R
REACTION SCHEME A
We have found that the ratio of ~ y isomers in the
last step of this reaction sequence can be altered by varying the
reaction time. In general starting from alkyl acetoacetates a
mixture of compounds IV (with Rl=CH3 or CH2) is obtained pre-
dominantly consisting of ~-isomer (ca 60%), and about 20% each of
the ~- and ~-isomers. The three isomers of the compounds with the
general formula IV can be separated by preparative gas liquid
chromatography.
By varying R2 in the condensation reaction between
mesityl oxide and acetylacetic acid ester (see reaction scheme A)
- other compounds of general formula IV are obtainable. It will be
clear to those skilled in the art that other ways of reducing the
cyclohexenone (e.g. Meerwein-Ponndorf reduction) can be used.
Examples can be found in the cited journal references. The
following compound of the general formula IV was prepared:
Rl R2 Boiling n2o
CH3 or CH2 CH3 37~40/3 mm Hg 1.4820
CH3 or CH2 C2H5 70-76/5 mm Hg 1.4790
CH3 or CH2 CH2CH(CH3)2 68-73/2 mm Hg 1.4747
10~7
The compounds of the invention have been found to
possess very useful organoleptic properties. Although there are
minor differences in their flavour and fragrance character, it is
not always necessary to separate the isomers because the mixture
of isomers can be used as such for the purposes of this invention.
The isomers show closely related smells, as can be seen from the
following odour descriptions, drafted by skilled perfumers and
flavourists.
- Ethyl safranate (Mixture, ~ y = 20:60:20) (Formula IV,
Rl=CH3 or CH2~ R2 C2 5)
The main impression of this mixture can be described
as herbal, spicy (rosemary, spike, laurel) and fruity (apple,
prune) with a distinct undertone of roses and wood.
- Ethyl ~-safranate (Formula IV--~, Rl=CH3, R2=C2H5):
The woody, ionone-like undertone is somewhat stronger than in
the mixture of the three isomers.
- Ethyl B-safranate (Formula IV-~, Rl=CH3, R2=C2H5):
The herbal, spicy character is more pronounced, although a great
similarity with the mixture does exist.
- Ethyl y-safranate (Formula IV-y, Rl=CH2, R2= C2H5):
A more fruity character (apple, prune) can be observed, but the
difference with the mixture of the three isomers is small.
- Methyl safranate (~lixture) (Formula IV, Rl=C113 or CH2, R2=CH3):
has a less fruity character than ethyl safranate. The herbal,
spicy aspects are stron~er. In aftersmell there are some sweet
hints of tonka.
- Isobutyl safranate (Mixture) (Formula IV, Rl=CH3 or CH2, R2=
i C4~g):
The main aspects are herbal, spicy with a striking
pearlike character.
The odour characteristics may give some general hints on
~0~0~7
the usefulness of the compounds of this invention. However, the
compounds will nearly always be used in combination with other
flavour and fragrance materials. One can by no means predict
whether a compound with a well-defined odour will behave satis-
factorily in perfume or flavour compositions. Furthermore, the
mere possession of an odour is not sufficient for a compound to
be useful as a perfume- or flavour-ingredient. Some of the other
requirements are:
- compatability with other perfume and flavour materials and with
the substrate to be perfumed or flavoured;
- favourable toxicological and dermatological properties;
- power to give complicated perfume or flavour compositions a
general character or a specific note as conceived by a skilled
perfumer or flavourist.
The compounds of this invention fulfil these requirements.
When compounds are tested for possible use in perfume
or flavour compositions, threshold values are often determined.
As the compounds of this invention were found to blend very well
with the known damascones and damascenones, described in e.g.
British Patent Specification 1,24Q,309 and Dutch Patent Application
72.11248, and with the homologues of the damascones and damascen-
ones, described in our copending Canadian Application No. 220,558
filed February 21, 1975, the odour threshold value of all these
compounds and of some mixtures thereof were determined. The three
compounds which are the subject of British Patent Specification
1,240,309, in flavour compositions develop fruity, herblike, winy,
woody, floraI or waxy flavour notes. They can be used in e.g.
berry flavour compositions, wines, beverages and tobacco products.
According to this Patent Specification they also can be used in
perfume compositions of the floral type. The identification of
these compounds, "damascones" and "damascenones" (formulae 4, 5
and 6)
io~o9~
o o o
4 5 6
-dam~scone B-damascone B-damascenone
(after "Rosa damascena", the essential oil of which contains
B-damascenone) is described in ~elv.Chim.Acta 53 (1970) 541, id
54 (1971) 681, id 54 (1971) 1891, Id 55 (1972) 1866, and id 56
(1973) 1503.
~-Damascone was found in tea.
~-Damascone is a constituent of Burley tobacco and of tea.
B-Damascenone is a component of Bulgarian rose oil, Burley tobacco,
Greek tobacco, decr tongue, coffee, tea, apple and raspberry.
In Dutch Patent Application 72.11248 some other
analogues are described which have the general formula
4 ~ \~
wherein on two of the places indicated by dotted lines a double
bond is present, i.e. in the positions 1 and 4, the positions
1 and 3, the position 2 (exocyclic) and 3 or the position 2
(endocyclic) and 4. In this application the inventors state that
the organoleptic properties of the new compounds show major diff-
erences in comparison with the known ~- and B-damascones, ~-
damascenone. This is rightfully explained by the unpredictability
of organoleptic propertie~s in relation to chemical structures.
From the examples in this patent application it becomes clear that
the differences in organoleptic properties do not show or give
only ~inor deviations in the use of the compounds in perfume and
flavour com~ositions.
-- 7 --
~ 10~10~7
The invention of copending Canadian application No.
220,558 filed February 21, 1975 relates to cycloaliphatic unsat- ¦
urated ketones, which may be a) damasc(en)one homologues having
the general formula 10
o
~\f\~/;~
1~ ,.~
~ R
wherein R stands for a hydrogen atom or a methyl radical and
wherein the dotted lines represent one double bond in the positions
1, 2 endocyclic or 2 exocyclic, or two conjugated double bonds in
the positions 1 and 3, 2 endocyclic and 4, or 2 exocyclic and 3;
b) dihydrodamasc(en)ones having the general formulae 11 and 12
O O
(~S\/' ~\'
11 12
the dotted lines in the iatter formula representing one double
bond in the position 1, 2 endocyclic or 2 exocyclic, or two
conjugated double bonds in the positions 1 and 3, 2 endocyclic
and 4 or 2 exocyclic and 3; and
c) dehydrodamascenones having the general formula 13
13'
wherein the dotted lines represent two conjugated double bonds in
the positions 1 and 3, 2 endocyclic and 4 or 2 .exocyclic and 3.
1061(~9-7
Specific compounds comprised hy Lormulae are:
l-crotonoyl-2-ethyl-6.6-dimethyl-1-cyclohe.Yene;
l-crotonoyl-2-ethyl-6.6-dimetllyl-2-cyclohexene;
l-crotonoyl-2-ethylidene-6.6-dimethylcyclohexane;
l-crotonoyl-2-ethyl-6.6-dimethyl-1.3-cyclohexadiene;
l-crotonoyl-2-ethyl-~.6-dimethyl-2.4-cyclohexadiene;
l-crotonoyl-2-etllyli~ene-6.6-dimethyl-3-cyclohexene;
l-crotonoyl-2-propyl-6.6-dimethyl-1-cyclohexene;
l-crotonoyl-2-propyl-6.6-dimethyl-2-cyclohexene;
l-crotonoyl-2-propylidene-6.6-dimethylcyclohexane;
l-crotonoyl-2-propyl-6.6-dimethyl-1.3-cyclohexadiene;
l-crotonoyl-2-propyl-6.6-dimethyl-2.4-cyclohexadiene;
l-crotonoyl-2-propylidene-6.6-dimethyl-3-cyclohexene;
l-butanoyl-2-ethyl-6.6-dimethyl-cyclohexane;
l-butanoyl-2-ethyl-6.6-dimethyl-1-cyclohexene;
l-butanoyl-2-ethyl-6.6-dimethyl-2-cyclohexene;
l-butanoyl-2-ethylidine-6.6-dimethylcyclohexane;
l-butanoyl-2-ethyl-6.6-dimethyl-1.3-cyclohexadiene;
2 1-butanoyl-2-ethyl-6.6-dimethyl-2.4-cyclohexadiene;
l-but-2'-ynoyl-2-ethyl-6.6-dimethyl-1.3-cyclohexadiene;
l-but-2'-ynoyl-2-ethyl-6.6-dimethyl-2.4-cyclohexadiene;
~ l-but-2'-ynoyl-2-ethylidene-6.6-dimethyl-3-cyclohexene;
The procedure used is described in: Manual on Sensory Testing
Metllods, ~.S.T.M. Special Technical Publication No. 434, Phila-
delphia, 1968, Page 30, method 3b and on page 61. To show some
of the peculiarities of the compounds of this invention, and the
interactions of these compounds with other perfume and flavour
agents, results of these tests are given in the table:
lOf~ t~
Code Compound Odour threshold Odour des-
value a) cription b)
A Ethyl safranate -6 General fruity,
(Mixture,~ y= 6 x 10 but not apple-
20:60:20) like
B -Damascone c) 1 x 10 6 Apple-like
C ~-Damascenone d) 6 x 10 Apple-like
D Damascenone homo- -6 Near threshold:
logue e) 8 x 10 fruity, in higher
concentration
coffee-like
E Damascone homologue
f) 0.8 x 10 Apple-like
F A + D (5 : 2) 0.2 x 10 Distinctly
apple-like
G A + C (5 : 2) 0.6 x 10 Apple-like.
Notes:
a) All compounds and mixtures were dissolved in odourless diethyl
phthalate.
b) The threshold values were determined using layman-observers.
They were asked to give a general odour description. The descrip-
tions in the table are quite different from those given by experts.c) = trans 2,6,6-trimethyl-1-crotonyl-2-cyclohexene, see e.g.
British Patent Specification 1.240.309.
d) = trans 2,6,6-trimethyl-1-crotonyl-1,3-cyclohexadiene, see
e.g. British Patcnt Specification 1.240.309.
e) = The reaction product of Example 9 of our copending
~pplication Number 220,558
f) = The reaction product of Example 8 of our copending
~pplication Number 220,558. ~ -
One can see from this table that the mixtures F and I
both have considerably lower threshold values than the individual
components, this lowering being probably the first occasion in
-- 10 --
~ 10~i1097
which synergism in the field of olfaction could be substantiated
by quantitative data. Equally striking is the fact that a com-
bination of the compounds with codes A and D has a distinct
apple-like odour, whereas the individual components have a general
fruity odour, with no reminiscence of the odour of apples.
It turns out therefore that the esters of this invention
when used in combination with cycloaliphatic unsaturated ketones
such as ~-damascone, ~-damascenone, or one or more of the homo-
logues thereof, which are described in our copending Canadian
Application No. 220,558 specifically enhance the perfuming and
flavouring properties of these ketones, making optimal flavour and
odour effects attainable. The esters as well as the ketones may
be present as isomeric mixtures. To obtain these remarkable
effects the relative amounts of the esters of this invention and
of the unsaturated ketones can vary from about 1:20 to about 20:1.
As will be understood by those skilled in the use of
flavouring materials and perfume agents, it is not possible nor
feasible to give specific instructions for the use of the esters
of this invention either alone or in combination with said ketones
in such arts, as there are too many factors which govern the
absolute amounts of materials to be used.
Among such factors are the personal preference of the
flavour expert or perfumer, the cost of materials, the nature of
the particular composition, the flavour or odour effect to be
achieved, etc. Nonetheless, it will be readily apparent to experts
how to employ the esters of this invention in particular situations.
Perfumery compositions containing the esters of this
invention may find use in a wide variety of perfumed materials.
For example such compositions may be used in soap, detergent, or
deodorant compositions, in cosmetic preparations such as cologne
waters, toilet waters, face creams, body lotions, talcum powders,
sun cream preparations and shave lotions. Flavour compositions
lO~jlO~
containing esters of this invention may find use in the flavouring
of foodstuffs, beverages, pharmaceuticals or tobacco. The esters
may be used to improve the flavour of beverages such as fruit
juices.
In the following Examples, the invention is illustrated
in a more detailed manner. All quantities in the Examples 1 to
10 are expressed on a weight basis.
EXAMPLE 1
Perfume composition of the rose type.
A rose type composition was prepared by mixing the
following ingredients:
Compound Composition
Cinnamic alcohol 15
Phenyl ethylalcohol 400
Rhodinol 260
l-Citronellol 160
Phenylacetaldehyde dimethylacetal 40
Methylionone ~ 15
Hydroxycitronellal 5
Gyrane (N) 1) 30
Phenylethyl propionate 15
Geranyl acetate 10
Citronellyl ethyl oxalate 20
Eugenol 10% sol. 2) 15
Undecenal 10% sol. 2) 5
Rose oxide 10% sol. 2) 5
1) Fragrance material, available from Naarden International.
2) In diethyl phthalate.
By adding to 99.5 g of the mixture 0.5 g of a 1% solution
in diethyl phthalate of ethyl safranate the composition becomes
more brillant than the basic composition, with a more pronounced
natural character of roses, accentuated by a fruity topnote.
- 12 -
10~109'~
EXAMPLE 2
Perfume composition of the Fougère type.
A Fougere type composition was prepared by mixing the
following ingredients:
Compound Composition
Coumarine 30
Musk ketone 5
Phenyl ethylalcohol 80
Oak moss absolute 10
Amyl salicylate 30
Rosemary oil 30
Serpolet oil 10
Lavender oil French type 260
Bergamot oil 100
Lemon oil 40
Eugenol 10
Ylang-Ylang oil I 5
Coriander oil 5
Clary sage oil 5
Geranium oil Bourbon 20
Musk Rl 1) 10% sol. 2) 20
- Undecenal 10% sol. 2) 10
Linalool 70
1) Fragrance material, available from Naarden International.
2) In diethylphthalate.
By adding 1 g of a 1% solution in diethylphthalate of
ethylsafranate to 74 g of the mixture a considerahle increase in
brilliancy is noted. The composition becomes richer in character
and obtains a striking fruity effect.
EXAMPLE 3
Perfume composition of the pine-fantasy type.
A pine-fantasy type composition was prepared by mixing
the following ingredients:
- 13 -
1097
Compound Composition
Olibanum resinoid 20
Elemi oleoresin 20
Bornyl acetate liquid 550
Turpentine oil rectified 130
Orange oil terpenes 150
- Rosemary oil French 5
Guaiyl acetate 15
Cistus absolute 10% sol. 1)10
Methyl nonyl. acetaladehyde30
10% sol. 1)
Liqustral (N) 2) 10% sol. 1~
Juniperberry oil 20
Oak moss absolute 10 % sol. 1)
Thyme oil 10% sol.
1) In diethyl phthalate
2) Fragrance material, available from Naarden International.
The effect of adding 5 g of a 1% solution in diethyl-
phthalate of ethylsafranate to the composition (995 g) is a
considerable increase in brilliancy and natural richness of this
basic composition.
EXAMPLE 4
Preparation of an imitation apple flavour.
~ An imitation apple flavour composition was prepared by
mixing the following ingredients:
Amyl acetate 35
Ethyl butyrate 15
Hexyl acetate 3
Amyl propionate
Orange oil Florida 0,4
Ethyl alcohol 96% 945,6
1000
An apple beverage was prepared using 0.3 g of this
flavour composition for each litre of finished beverage. Two
)9'7
modifications of the apple flavour composition were made by
adding to the composition 25 or 50 ppm of ethyl safranate.
The apple beverages made from these two modifications
were compared with the unmodified beverage by a panel of exper-
ienced tasters. All members of this panel had a strong perference
for the beverages with the addition of ethyl safranate, these
beverages being more natural apple-like in odour and taste. No
significant preference existed between the beverages containing
ethyl safranate, although the difference in concentration was
notified.
As can be seen from this Example the concentration of
ethyl safranate in the finished ~everage is far below the odour
thresholdvalue of the pure compound. Nonetheless its influence
on the odour and taste of the beverage is clearly observable.
(25 ppm in the composition, 0.3 g of the composition for each
litre beverage; so the concentration of ethyl safranate in the
beverage is 7.5 x 10 ).
EXAMPLE 5
Preparation of an imitation apple flavour
composition.
An imitation apple flavour composition was prepared
according to L. Bénézet, La Parfumerie Moderne, 43 (1951), No.
22, P 51 - 78.
Ethyl acetate 50
Ethyl acetoacetate 200
Ethyl formiate 20
Ethyl butyrate 50
Ethyl hexanoate 20
Ethyl heptanoate50
Ethyl octanoate 20
Isoamyl formiate50
Isoamly acetate 50
Isoamyl pentanoate 100
- 15 -
iO~lOg'7
Isoamyl hexanoate 50
Isoamyl octanoate 100
- Acetaldehyde 50
Geraniol 10
Geranyl formiate 10
Geranyl acetate 10
Phenylethyl pentanoate 20
Benzaldehyde 5
Cinnamyl propionate 50
Diethyl malonate 64
Orange oil Florida 20
Rose oil
1000
From this composition a 1% solution in ethanol was pre-
pared. Part of this solution was used to prepare an apple
beverage, using 0.3 g of the ethanolic solution per litre of
finished beverage.
To another part of the ethanolic solution 100 ppm ethyl
safranate were added. Using 0.3 g of this solution per litre
finished beverage another apple flavoured beverage was prepared.
Comparison of the two beverages by a panel of trained
flavourist resulted in an unanimous preference for the beverage
with the addition of ethyl safranate.
EXAMPLE 6
Preparation of a rasFberry flavour composition.
An imitation raspberry flavour composition was prepared
by mixing the following ingredients:
Geraniol 20
Vanilline 20
Maltol 20
Phenyl ethylalcohol50
p-Hydroxybenzyl acetone 50
- 16 -
'7
Methylionone a 100
Ionone ~ 100
Benzyl acetate 100
Isobutyl acetate 100
Ethyl acetate 100
Amyl acetate 100
Ethanol 240
1000
A 1% solution in ethanol of this composition was used
as flavour in a raspberry beverage. Adding 100 ppm of ethyl
safranate to the ethanolic solution resulted in an improved
beverage, the taste and odour being more natural raspberry-like.
EXAMPLE 7
Preparation of an imitation raspberry flavour
_ composition.
An imitation raspberry flavour composition was prepared
as a modification of the recipe of L. Bénézet, La Parfumerie
Moderne, 43 (1951) No. 22, p 61-78.
Acetyl methyl carbinol 3
Diacetyl 2
Ethyl acetate 10
Isobutyl acetate 40
Ethyl hexanoate 10
Isoamyl hexanoate 10
Hexyl acetate 10
Hexenyl acetate 10
Benzyl acetate 50
Isoamyl alcohol 10
Hexanol 5
Hexenol 5
Ionone ~ 25
Methylionone a 25
io~io~
Orris (Concrète) oil15
Anis aldehyde 5
Benzaldehyde 5
Phenyl ethylalcohol50
Methyl salicylate 10
Bornyl salicylate 10
Clove bud oil 10
Orange oil sweet 50
~ Geranium oil 10
Coumarine 20
Vanilline 30
Aldehyde C-16 ("so-called") 400
Benzylidene mesityl oxide 100
Ethyl benzoate 10
- 940
0.3 g of a 1% solution in ethanol was used for each
litre of finished beverage. Addition of 100 ppm of ethyl safranate
to the alcoholic solution of the flavour composition resulted in
a beverage with a better raspberry flavour.
EXAMPLE 8
Perfume compositions of the rose type.
Three rose type compositions were prepared by mixing
the following ingredients:
Compound Composition
A _ C
Cinnamic alcohol 15 10 20
Trichloromethylphenylcarbinyl acetate 5 5
Phenyl ethylalcohol 355 370 365
Rhodinol 180 160 170
Citronellol 170 140 120
Nerol . 20 40 70
Phenyl acetaldehyde dimethylacetal 30 40 30
- 18 -
1()~105~
Methylionone ~ 10 10 10
Guaiyl acetate 10 5 10
Hydroxy citronellal 10 15 17
Gyrane (N) 1) 30 25 20
Phenylethyl propionate 20 25 15
Geranyl acetate 10 10 5
Citronellyl ethyl oxalate 20 25 35
Geranium oil Bourbon 20 20 15
Rose oxide 10% sol. 2) 15 10 5
Rosana NB 131 3) 60 70 80
Rose absolute 5 5 5
985 985 992
1) Fragrance material, available from Naarden International.
2) In diethyl phthalate.
3) Rose base, available from Naarden International.
Three modifications of composition A were made:
a) Addition of 1 g of a 10% solution in diethyl phthalate of the
damascone homologue from Example 8 of our copending Canadian
Patent Application No. 220,558, to 98.5 g of the basic composition.
b) Addition of O.5 g of a 1% solution in diethyl phthalate of
ethyl safranate to 98.5 g of the basic composition.
c) Addition of both 1 g of the solution mentioned under a) and
0.5 g of the solution mentioned under b) to 98.5 g of the basic
composition.
Three modifications of composition B were made:
a) Addition of 1 g of a 10% solution in diethyl phthalate of the
damascenone homologue from Example 9 of our copending Canadian
Patent Application No. 220,558, to 98.5 g of basic composition B.
b) Addition of 0.5 g of a 1% solution in diethyl phthalate of
ethyl safranate to 98.5 g of basic composition B.
c) Addition of both 1 g of the solution mentioned under a) and
0.5 g of the solution mentioned under b) to 98.5 g of basic
-- 19 --
10~109'~
composition B.
Finally three modifications of basic composition C were
made:
a) Addition of O.S g of a 10% solution in diethyl phthalate of
~-damascenone to 99.2 g of the basic composition.
b) Addition of 0.3 g of a 1% solution in diethyl phthalate of
ethyl safranate to 99.2 g of basic composition C.
c) Addition of both 0.5 g of the ~-damascenone solution and 0.3 g
of the ethyl safranate solution to 99.2 g of basic composition C.
A panel of 10 trained perfumers was asked to compare the
modifications with the basic compositions. In each case the basic
composition was judged as being improved by the addition of the
cycloaliphatic unsaturated ketone (additions a), or by the
additions of ethyl safranate (additions b), but the effect of the
addition of both types of compounds to the basic compositions was
in all three cases judged as showing more than the sum of the
èffects of addition a) and b), resulting in a composition with a
very natural rose character, having a radiant, warm body, and a
well balanced topnote.
EXAMPLE 9
- Imitation apple flavour.
Three modifications of the basic composition of Example
4 were made:
A. To 100 g of the basic composition 2.5 g of a 1% solution in
ethanol of ~-damascenone were added.
B. To 100 g of the basic composition 5 g of a 1% solution in
ethanol of ethyl safranate were added.
C. To 100 g of the basic composition 2.5 g of a 1% solution in
ethanol of ~-damascenone and 5 g of a 1% solution in ethanol of
ethyl safranate were added.
These three modifications and the basic composition were
compared in finished apple beverages by a panel of trained
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09~
flavourists. According to this panel compositions A and B were
improvements of the basic composition, but a strong preference
existed for the beverage containing composition C, this modification
giving the beverage a still more natural taste and odour in com-
parison with A and B.
The imitation apple flavours of Example 4 containing 25
or 50 ppm ethylsafranate and modification C of this Example can be
used in flavouring tobacco products as described in: Merory, Food
Flavorings, Composition, Manufacture and Use, Westport 1968.
EXAMPLE 10
Imitation raspberry flavour.
Three modifications of the basic composition of Example
7 were made:
A. 10 g of the basic composition were dissolved in 1000 g of
ethanol, 0.2 g of ethyl safranate was added.
B. 10 g of the basic composition were dissolved in 1000 g of
ethanol. 0.1 g of a 10% solution in ethanol of the damascenone
homologue of Example 9 of our copending Canadian Patent Application
No. 220,558 was added.
C. 10 g of the basic composition were dissolved in 1000 g of
ethanol. 0.2 g of ethyl safranate and 0.1 g of a 10% solution in
ethanol of the damascenone homologue of Example 9 of our copending
Canadian Patent Application No. 220,558 were added.
From these three modifications and from the basic com-
positions raspberry flavoured beverages were made, using 0.3 g of
the ethanolic solutions for each litre of finished beverage. The
beverages were compared by a panel of trained flavourists. Although
the beverages made from the modifications A and B were judged as
improvements over the beverage made from the basic composition,
an unanimous preference existed for the beverage made from com-
position C. In the beverages made from the basic composition or
from the modifications A or B the odour and taste of ~-ionone is
10~
clearly observable. The beverage made from modification C is
far more round in taste and odour and has a rich natural rasp-
berry character.
~.
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