Note: Descriptions are shown in the official language in which they were submitted.
0043
This invention relates to novel 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.
Increasing attention is being devoted to the prepar-
ation 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,
pharmaceuticals, and to~acco. This attention has been stimulated
not only because of the inadequate quantity of natural perfume
and flavouring materials available, but, perhaps even more import-
antly, because of the need for materials which can combine several
natural nuances, will blend better with other perfuming or
flavouring 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 con-
fers a major advantage to artificial perfuming and food flavouring
agents, since natural products, such as essential oils, extracts,
concentrates, 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;
~COO~I ~COOH ~COOl:
I ~l II ,~ III ~
"~f,~
For simplicity in referring to the various compounds of this
invention, in analogy with the isomers of safranic acid, the
following nomenclature is used throughout this specification:
~ COOR ~ = conjugated double bonds in ~ositions
5 ~ ~ / 2 2 (endocyclic) and 4;
4 ~ ~ ~ = conjugated double bonds in positions
~ = conjugated double bonds in positions
IV ~ , or -r. 2 (exocyclic) and 3.
~-safranic acid is described in Helv.Chim.Acta 31 (1948) 134
~-safranic acid in Berichte 74 (1941) 1242 and
~- 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 ~-safranate in Helv.Chim.Acta 31 (1948) 134;
- Methyl ~- and y-safranates and ethyl ~- and r-safranates 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 ~ -, and y-safranates are prepared in Helv.Chim.Acta
54 (1971) 1767;
- Esters of ~ -, and r-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,
nowwhere mention is made of the organoleptic properties of these
esters.
'~'; ' '
:10~0043
We have now found that the safranic acid esters and
some novel homologues thereof possess useful organoleptic pro-
perties and can be used for flavouring and perfuming a wide range
of products. The compounds of the invention may be used, combined
with other flavouring agents, diluents 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.
The odoriferous esters of this invention have the general
formula IV: 6
5 ~ / COOR2
4 ~ ``~ R
IV
wherein the dotted lines represent two conjugated double bonds
in the positions 2 (endocyclic) and ~ (~-isomer), 1 and 3
(~-isomer), or 2 ~exocyclic) and 3 (~-isomer); Rl represents an
alkyl group, or, the y-isomers an alkylidene group, with 1-3
carbon atoms; and R2 represents an alkyl- or alkenyl group with
1-4 carbon atoms. The compounds of formula IV wherein Rl is
CH3 (~- or ~-isomers) or CH2 (y-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 other
compounds of formula IV are new.
The compounds of this invention may be prepared by
methods described in the cited literature or for the homologues
of the safranic acid esters in an analogous way. The methods
described in the examples are modifications of the method given
in Dutch Patent Application 73.01451, pp 11-13, where the ~-,
~-, and ~-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.
.. .. ...
043
COOR2 ~'; +H2 2 ;~J/ 2 _~ IV
//\ R Rl H
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 or alkenyl aceto-
acetates a mixture of compounds IV (with Rl=CH3 or CH2) is obtainedpredominantly consisting of ~-isomer (ca 60 %), and about 20 ~
each of the ~- and ~-isomers. In the syntheses of the compounds
with general formula IV withRl containing two or three carbon
atoms, extension of the reaction time in the dehydration step
leads to the formation of a reaction mixture for over 90 %
consisting of the y-isomer. A shorter dehydration time gives a
higher content of the ~- and ~-isomers, although even then the
y-isomer will be the major component in the mixture obtained. The
three isomers of the compounds with the general formula IV can be
separated by preparative gas liquid chromatography. The prepar-
ation of the compounds of this invention is illustrated in Example 1
with the synthesis of a mixture of the ~ -, and y-isomers of
the compounds with formula IV, wherein R1 = C2H5 (a- or ~-isomers)
or C2H4 (~-isomer), and R2=C2H5.
By varying Rl an~ R2 in the condensation reaction bet-
ween mesityl oxide and an acylacetic 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.
Analogous to the method described in Example 1 the following
compounds of the general formula IV were prepared:
4 -
~050~43
_
_ Bo1ling 20
1 2 pointC n D
_ _ _. ._
CH3 or CH2 CH3 37-40/3 mm Hg 1.4820
id C2H5 70-76/5 mm Hg 1.4790
id CH2CH=CH2 78-79/2 mm Hg 1.4884
id CH2CH(CH3)2 68-73/2 mm Hg 1.4747
C3H7 or C3H5 C2H578-82/3 ~n Hg 1.4832
As already mentioned all reaction products obtained contain
~ -, and y-isomers. The y-isomers of formula IV with Rl
containing two or three carbon atoms exist in two geometrical
isomers, cis and trans, as shown in the following two formulae
(IV, with Rl = C2H~).
~OR2 ~COOR2
IV cis-y IV-trans-y
The amounts of the two y-isomers, formed by the reaction-sequence
described, are broadly equal.
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,
1 CH3 or CH2~ R2= C2H5)
The main impression of this mixture can be described as herbal,
;~ - 5 -
spicy (rosemary, spike, laurel) and ruity (apple, prune) with
a distinct undertone of roses and wood.
- Ethyl ~-safranate (Formula I~-~, Rl=C~3, R2=C2H5):
The woody, ionone-like undertone is somewhat stronger than in
the mixture of the three isomers.
- Ethyl ~-safranate (Formula IV-~, Rl=CH3, R2=C2H5):
The herbal, spicy character is more pronounced, although a great
similarity with the mixture does exist.
- Ethyl ~-safranate (Fo~mula 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 (Mixture) (Formula 1~, Rl=C~13 or CH2, R2=CH3):
has a ~ess fruity character than ethyl safranate. The herbal,
spicy aspects are stronger. In aftersmell there are some sweet
hints of tonka.
-Allyl safranate (~ixture) (Formula IV, Rl-CH3 or CH2, R2=C3H5):
The odour character is nearly identical with ethyl safranate,
but less intense.
- Isobutyl safranate (Mixture) (Formula IV, Rl=CH3 or CEI2, R2=
i~C4Hg):
The main aspects are herbal~ spicy with a striking pearlike
character. Especially suitable for flavouring purposes.
- Ethyl 6,6-dimethyl-2-ethylidene-3-cyclohexenecarboxylate
Formula IV, Rl = C2H4, R2 2 5
This ester shows a great odour similarity with ethyl safrana-te,
but its odour intensity is probably somewhat greater.
- Ethyl 6,6-dimethyl-2-propylidene-3-cyclohexenecarboxylate
Formula IV, Rl = C3H6 R2 2 5
In comparison with ethylsafranate the odour intensity is much
smaller. The fruity notes of ethyl safranate have almost complete-
ly disappeared, but the herbal, spicy notes are much stronger.
This ester also exhibits an earthy-woody note.
- 6 -
. ~ ~
~lLO~)043
The odour characteristi~s may give some general hints on the
usefulness of the compo~lnds of this invention. ilowever, the
compounds will nearly always be used in combination with other
flavour and fra~rance 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;
- the 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, descrihed in e.g.
British Patent Specificiation 1~240.309 and Dutch Patent Applica-
tion 72.11248, and with the homologues of the damascones and
damascenones, described in our co-pending Canadian Application
Number 220,558 filed Fehruary 21, 1975, the odour threshold value
of all these compounds and of some mixtures thereof were deter-
mined. The three compounds which are the subject of British
Patent Specification 1.240.309, in flavour compositions develop
fruity, herblike, winy, woody, floral or waxy flavour notes.
They can be used in e.g. berry flavour compositions, wines,
beverages and tobacco products. According to this Patent Specifi-
cation they also can be used in perfume compositions of the floral
type. The identification of these compounds, "damascones" and
"damascenones" (formulae 4,5 and 5)
_ q_
lOS,0043
o o o
4 5 6
~ -damascone ~-damascone ~-damascenone
(after "Rosa damascena", the essential oil of which contains
~-damascenone) is described in Helv.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.
~-Damascenone is a component of Bulgarian rose oil, Burley tobacco,
Greek tobacco, deer tongue, coffee, tea,'apple and raspberry.
In Dutch Patent Application 72.11248 some other
analogues are described which have the general formula
X~
~"
4 3
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 prope~ties of the new compounds show major
differences in comparison with the known ~- and ~-damascones, ~-
damascenone. This is rightfully explained by the unpredictability
of organoleptic properties in relation to chemical structures.
From the examples in this patent appllcation it becomes clear that
the differences in organoleptic properties do not show or give
only minor deviations in the use of the compounds in perfume and
flavour compositions.
The invention of copending Canadian application No.
220,558 filed February 21, 1975 relates to cycloaliphatic unsatur-
~ - 8 -
105()043
ated ketones, which may be
a) damasc(en)one homologues havin~ the general formula 10
- 8a -
~0(143
o
~ ,,,~
'I ~`
wherein R stands for a hydrogen atom or a methyl radical and
wherein the dotted lines represent one double bond in th~ 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
11 12
the dotted lines in the latter 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.
Specific compounds comprised by formulae are:
. .
l-crotonoyl-2-ethyl-6.6-dimethyl-1-cyclohexene;
l-crotonoyl-2-ethyl-6.6-dimethyl-2-cyclohexeIIe;
1-crotonoyl-2-ethylidene-6.6-dimethylcyclohexane;
l-crotonoyl-2-ethyl-6.6-dimethyl-1.3-cyclohexadiene;
l-crotonoyl-2-ethyl-6.6-dimethyl-2.4-cyclohexadiene;
r~ .
lOC~00~3
l-crotonoyl-2-ethylidene-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;
1-butanoyl-2-ethyl-6.6-dimethyl-2-cyclohexene;
l-butanoyl-2-ethylidine-6.6-dimethylcyclohexane;
l-butanoyl-2-ethyl~6.6-~imethyl-1.3-cyclohexadiene,
l-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 in described in: Manual on Sensory Testing
Methods, A.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:
3~
-- 10 --
1~500~
-
~ode Compound Odour threshold Odour description
value a) b)
A Ethyl safranate(Mixture, 6 x 10 6 General fruity,
~ y= 20:60:20) but not apple-like
B Ethyl 6,6-dimethyl-2- 10 x 10 6 Apple-like
ethylidene-3-cyclo-
hexenecarhoxylate
C ~-Damascone c) 1 x 10 Apple--like
D B-Damascenone d) 6 x 10 6 Apple-like
E Damascenone homologue e) 8 x 10 6 Near threshold:
fruity, in higher
concentration
coffee-like
F Damascone homologue f) 0a8 x 10 Apple-like
G A + E (5 : 2) 0~2 x 10 6 Distinctly
apple-like.
H B + E (5 : 2) 2 x 10 Apple-like
I A + D (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 Patent Specification 1.240.309.
e) = The reaction product of EY~ample 9 of our copending
Application Number
f) - The reaction product of Example 8 of our copending
Application Number
One can see from this table that the mixtures G, H, and I all
- 11 --
~" ~, ,
~ 4 ~
00~3
have considerably lower threshold values than the individual
components, this lowering being probably the ~irst occasion in
which synergism in the field of olfaction could be substantiated
by quantitative data. Equally striking is the fact that a com-
bination o~ the compounds with codes A and E 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 inven-
tion when used in combination with cycloaliphatic unsaturated
ketones such as ~-damascone, ~-damascenone, or one or more of the
homologues thereof, which are describea in our copending Canadian
Application Number 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 2D:l~
As will be understood by those skilled in the use of
flavouring materiàls 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 absol-
ute 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
- 12 -
~OS1~0~3
waters, toilet waters, face creams, body lotions, talcum powders,
sun cream preparations and shave lotions. Flavour compositions
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 2-11
are expressed on a weight basis. The Examples are not to be
considered as necessarily constituting a limitation on the present
invention.
EXAMPLE 1
-A- Preparation of Ethyl 6,6-dimethyl-2-ethyl-4-oxo-2-
cyclohexenecarboxylate.
A mixture of 294 g. of mesityl oxide, 432 g. of ~-
propionylacetic acid ethyl ester, 150 g. of cyclohexane and 75 g.
of zinc chloride was stirred at boiling temperature of the mixture
during 60 h. The water resulting from the reaction was separated
via a Dean-Stark tube.
At room temperature the mixture was stirred during 10
minute with 300 g. of a 10% HCl-solution and 150 g. of cyclohexane.
After washing with water, a NaHCO3-solution and again water,
cyclohexane was distilled off from the separated orga~ic layer
and the residue fractionated in vacuo which gave 272 g. of a pro-
duct, b.p. 126-135 C/2 Torr, n20 1.4788, which had a 90 % content
of ethyl 6,6-dimethyl-2-ethyl-4-oxo-2-cyclohexenecarboxylate, as
determined by GLC and NM~-analysis.
-B- Preparation of a mixture of
Ethyl 6,6-dimethyl-2-ethylidene-3-cyclohexenecarboxylate,
Ethyl 6,6-dimethyl-2-ethyl-1,3-cyclohexadienecarboxylate and
Ethyl 6,6-dimethyl-2-ethyl-2,4,-cyclohexadienecarboxylate.
A solution of 25 g. of NaBH4 and ~.25 g. of NaO~I in
- 13 -
l~)S~V043
100 g. o~ water was added dropwise in 30 minutes into a solution
of 270 g. of ethyl 6,6-dimethyl-2-ethyl-4-oxo-2-cyclohexene-
carboxylate in 100 g of ethanol. During the addition the re-
action vessel was cooled to 35-40 C. The reaction mixture
was stirred for an additional 4 hours without cooling, whereby
the temperature in the reaction vessel slowly reached room
temperature. The reaction mixture was diluted with 200 g. of
toluene and washed with 100 ml. of a 10 % acetic acid solution.
After separating and drying 2 g. of p-toluenesulphonic acid was
added and the solution was refluxed during 2 hours.
After washing with a 5 % NaHCO3 solution and water,
the volatile solvent was removed in vacuo yielding 263 g. of
an oily liquid which was subjected to fractional distillation.
The second fraction of the distillate (167 g.) had a boiling point
of 74-90 C/ 2 Torr and a nD of 1.4819. It consisted of a mixture
of the three title compounds. The ~- and 3-isomers formed 15 and
5 % respectively, the remaining 80 % being the y-isomer.
1) When the reflux time was extended to 7 hours, the only
reaction product wa~ the ~-isomer, b.p. 77-80 ~C/ 2 Torr, n20
1.4~35.
EXAMPLE 2.
Perfume compositions of the rose type.
Three rose type compositions were prepared by mixing the
following ingredients:
Compound Composition
A B C
Cinnamic alcohol 15 20 5
Phenyl ethylalcohol 400 380435
Rhodinol 260 280250
l-Citronellol 160 140150
Phenylacetaldehyde dimethylacetal 40 50 25
Methylionone ~ 15 - 5
- 14 -
1050043
Compound Composition
~ B C
Hydroxycitronellal 5 - 10
Gyrane (N) 1) 30 20 15
Phenylethyl propionate 15 30 25
Ger~nyl acetate 10 20 30
Citronellyl ethyl oxalate 20 10 5
Eugenol 10 % sol. 2) 15 5 10
Undecenal 10 % sol. 2) 5 - 5
10 Rose oxide 10 ~ sol. 2) 5 5 5
Methylionone y - 10
Linalool - 10
Lauric aldehyde 10 % sol. 2) - 10
Rosana NB 131 3) - 5
Geranium oil Bourbon - - 10
Rose absolute 10 % sol. 2) - - 5
. _
995 995 990
1) Fragrance material, available from Naarden International.
2) In diethyl phthalate.
3) Rose base, available from Naarden International.
A. By adding to 99.5 g. of mixture A 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.
B. By adding to 99.5 g. of mixture B 0.5 g. of a 1 ~ solution
in diethylphthalate of ethyl 6,6-dimethyl-2-ethylidene-3-cyclo-
hexenecarboxylate, the composition instantly becomes more power-
ful and full bodied. The composition obtained has an exceptional
brilliancy and a ~lowery, true to nature rose character.
C. By adding to 99 g. of mixture C 1 g. of a 1 % solution of
ethyl 6,6-dimethyl-2-propylidene-3-cyclohexenecarboxylate the
composition obtained has an improved richness and a more pronounced
~' ~, .
10~043
natural note than the basic composition.
EXAMPLE 3.
Perfume compositions of the Fougère type.
Three fougère type compositions were prepared by
mixing the following ingredients:
Compound Composition
A B C
Coumarine 30 25 15
Musk ketone 5 5 10
Phenyl ethylalcohol 80 90 100
Oak moss absolute 10 10 5
Amyl salicylate 30 20 40
Rosemary oil 30 35 40
Serpolet oil 10 15 20
Lavender oil French type 260 255 220
Bergamot oil 100 60 120
Lemon oil 40 60 30
Eugenol 10 15 5
Ylang-Ylang oil I 5 10 5
Coriander oil 5 5
Clary sage oil 5 10 10
Geranium oil Bourbon 20 25 20
Musk Rl 1) 10 % sol. 2) 20 30 40
Undecenal 10 % sol. 2~ 10 5 15
Linalool 70 50 75
Methyl nonyl acetaldehyde
10 ~ sol. 2) - 5
Methylionone ~ - 10 5
Tetradecanal 1 % sol. 2) - 5
Thyme oil 10 % sol. 2) - - 10
_
7~0 745 785
- 16 -
50043
1) Fragrance material, available from Naarden International
2) In diethylphthalate.
A. By adding 1 g. of a 1 ~ solution in diethylphthalate of
ethylsafranate to 74 g. of mixture A a considerable increase in
brilliancy is noted. The composition becomes richer in character
and obtains a striking fruity effect.
B. By adding 0.5 g. of a 1 % solution in diethylphthalate of
ethyl 6,6-dimethyl-2-ethylidene-3- cyclohexenecarboxylate to
74.5 g of composition B, the composition gets richer and more
full bodied. The composition obtains an enhanced brilliance and
the tonality of the perfume is accentuat~d.
C. By adding 1.5 g. of a 1 % solution in diethylphthalate of
ethyl 6,6-dimethyl-2-propylidene-3-cyclohexenecarboxylate to
78.5 g. of composition C the odour character of this composition
gets a more full and warm body and a remarkable increase in
brilliance is noted.
EXAMPLE 4.
Perfume comp itions of the pine-fantasy type.
Three pine-fantasy type compositions were prepared by
20mixing the following ingredients:
Compound Composition
A B C
Olibanum resinoid 20 10 10
Elemi oleoresin 20 25 10
Bornyl acetate liquid 550 580 600
Turpentine oil rectified 130 100 110
Orange oil terpenes 150 120 135
Rosemary oil French 5 20 20
Guaiyl acetate 15 10 10
Cistus absolute 10 % sol. 1)10 - 10
Methyl nonyl acetaldehyde 30 40 25
10 ~ sol. 1)
.
` f
~05C~3
Compound Composition
A B C
Ligustral (~) 2) 10 % sol. 1) 20 15
Juniperberry oil 20 30 20
Oak moss absoluce 10 % sol. 1)20 25 10
Thyme oil 10 % sol. 5 - -
Serpolet oil - 20
Origanum oil - - 10
Synthetic Geranium oil - - 5
La~ender oil French - - 5
Laurel leaf oil - - 5
995 995990
1) In diethyl phthalate
2) Fragrance material, available from Naarden International
A. The effect of adding 5 g. of a 1 % solution in diethyl -
phthalate of ethylsafranate to composition A (995 g.) is a
considerable increase in brilliancy and natural richness of
this basic composition.
B. Adding 5 g. of a 1 % solution in diethyl phthalate of ethyl
6,6-dimethyl-2-ethylidene-3-cyclohexenecarboxylate to 995 g of
composition B results in a fuller, warmer character of this
composition, a greater brilliancy and accentuation of the warm,
herbal notes.
C. By adding to 990 g. of mixture B 10 g. of a 1 % solution in
diethyl phthalate of ethyl 6,6-dimethyl-2-propylidene-3-cyclo-
hexenecarboxylate a composition with an enhanced, full bodied
natural character is obtained.
EXAMPLE 5.
Preparation of an imitation apple flavour.
An imitation apple flavour composition was prepared by
mixing the following ingredients:
.~ .
10~00~3
Amyl acetate 35
Ethyl butyrate 15
Hexyl acetate 3
Amyl propionate
Orange oil Florida o,a
Ethyl alcohol 96% 945,6
10~0
An apple beverage was prepared using 0,3 g. of this
flavour composition for each litre of finished beverage. Two
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 preference
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 beverage is far below the odour
threshold value 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 9)
EXAMPLE 6.
Preparation of_an_ imitation apple flavour composition.
3~ An imitation apple flavour composition was prepared
according to L. Bénézet, La Parfumerie Moderne, 43 (1951), No. 22,
P 61 - 78.
-- 19 --
~ ' ~`~ ,s
10'~0043
Ethyl acetate 50
Ethyl acetoacetate 200
Ethyl formiate 20
Ethyl butyrate 50
Ethyl hexanoate 20
Ethyl heptanoate 5~
Ethyl octanoate 20
Isoamyl formiate 50
Isoamyl acetate 50
Isoamyl pentanoate 100
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 prepared.
Part of this solution was used to prepare an apple beverage,
using 0.3 g of the ethanolic solution perlitre of finished
beverage.
To another part of the ethanolic solution 100 ppm ethyl
safranate were added. Using 0.3 ~. 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.
- 20 -
~S00~3
EXAMPLE 7.
. _
Preparation of a raspberry flavour composition.
. _ _
An imitation raspberry flavour composition was pre-
pared by mixing the following ingredients:
Geraniol 20
Vanilline 20
Maltol 20
Phenyl ethylalcohol50
p-Hydroxybenzyl acetone 50
Methylionone ~ 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 8.
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
, - 21 -
lOSOQ43
Isoamyl hexanoate 10
Hexyl acetate 10
Hexenyl acetate 10
Benzyl acetate 50
Isoamyl alcohol 10
Hexanol 5
Hexenol 5
Ionone ~ 25
Methylionone ~ 25
Orris (Concrète) oil 15
Anis aldehyde 5
Benzaldehyde 5
Phenyl ethylalcohol 50
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 bever-
age with a better raspberry flavour.
EXAMPLE 9
Perfume compositions of the rose type.
-
Three rose type compositions were prepared by mixing
- 22 -
10'0043
the following ingredients:
ound Com~osition
A B C
Cinnami.c alcohol 1510 20
Trichloromethylphenylcarbinyl acetate 5 5
Phenyl ethylalcohol 355 3~0 365
Rhodinol 180 160 170
Citronellol 170 140 12
Nerol 20 4~ 70
Phenyl acetaldehyde dimethylacetal 30 40 30
Methylionone a 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
lS 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 Number 220,558, to 98.5 g. of the basic compo-
sition. ~ -
b) Addition of 0.5 g. of a 1 % solution in diethyl phthalate of
- 23 -
l~C~043
ethyl safranate to 98.5 g. of the hasic com~osition.
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, Num~er 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 9~.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
composition B.
Finally three modifications of basic com osition C were
made:
a) Addition of 0.5 g. of a 1~ % solution in diethyl phthalate of
~-damascenone to 99.2 g. of the basic composition.
b) Addition of Q.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 hasic
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 im~roved by the addition of
the cycloaliphatic unsaturated ~etone (additions a), or by the
additions of ethyl safranate (additions b), but the effect of the
addition of both types of compounds to the hasic compositions
was in all three casQs judged as showing more than the sum of the
effects of addition a) and h), resulting in a composition with a
very natural rose character, ha~ing a radiant, warm body, and a
- 24 -
043
well balanced topnote.
XAMPLE 10.
Imitati n apple flavour.
Three modifications of the basic composition of
example 5 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 96 solution
in ethanol of ~-damascenone and 5 g of a 1 % solution in ethanol
of ethyl safranate wére added.
These three modifications and the basic composition
were compared in finished apple beverages by a panel of trained
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 is com-
parison with A and B.
The imitation apple flavours of Example 5 containing 25
or 50 ppm ethylsaffranate and modification C of this Example can
be used in flavouring tobacco products a~ described in: Merory,
Food Flavorings, Composition, Manufacture and Use, Westport 1968.
EXAMPLE 11.
Imitation raspberry flavour.
Three modifications of the basic composition of example 8
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
C~ N
homologue of example 9 of our copenaing ~}rrtIs~ Patent Application
25 -
. jf., ,
43
Number 220,558 was added.
C. 10 g. of the hasic composition were dissolved in 1~ 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 Number 220,558
were added.
From these three modifications and from the basic
compositions 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 composition C. In the heverages made from the basic
composition or from the mo~ifications A or B the odour and taste
of ~-ionone is clearly observable. The beverage made from
modification C is far more round in taste and odour and has a
rich natural raspberry character.
- 2~ -
