CA1061097A - Cycloaliphatic unsaturated esters as flavour and odour agents - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
She present invention relates to a perfume or flavouring composition containing at least one safranic acid ester having the general formula IV

Description

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 -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.

~ 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\/' ~\' 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~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.

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.

10~109'~

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.

Perfume composition of the pine-fantasy type.
A pine-fantasy type composition was prepared by mixing the following ingredients:

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.

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 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 ).

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 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 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.

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 '7 Methylionone a 100 Ionone ~ 100 Benzyl acetate 100 Isobutyl acetate 100 Ethyl acetate 100 Amyl acetate 100 Ethanol 240 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.

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 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.

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 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 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 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.

- 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 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.

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.

~.

Claims (10)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A perfume or flavouring composition, containing at least one perfume or flavouring material and at least one ester having the formula wherein the dotted lines represent two conjugated double bonds in the position 2-endocyclic and 4 (.alpha.-isomer), 1 and 3 (.beta.-isomer) or 2-exocyclic and 3 (.gamma.-isomer) and wherein R1 represents a methyl group, or, in the .gamma.-isomers a methylidene group and R2 represents an alkyl group with 1-4 carbon atoms.

2. A composition as claimed in claim 1 in which the compound of formula IV is selected from an ethyl safranate, a methyl safranate, and an isobutyl safranate.

3. A composition as claimed in claim 1 or 2 which also contains at least one damascone or damascenone perfume or flavour-ing agent.

4. A composition as claimed in claim 1 which also contains an effective quantity of at least one compound selected from those of the formula .alpha.-damascone .beta.-damascone .beta.-damascenone

5. A composition as claimed in claim 1 which also con-tains at least one compound which have the general formula wherein on two of the places indicated by dotted lines a double bond is present in the positions 1 and 4, the positions 1 and 3, the position 2 (exocyclic) and 3 or the position 2 (endocyclic) and 4.

6. A composition as claimed in claim 1 which also contains at least one compound selected from a) damasc(en)one homologues having the general formula 10 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, the dotted lines in the latter formula representing one double bond in the positions 1, 2 endocyclic or 3 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 wherein the dotted lines represent two conjugated double bonds in the positions 1 and 3, 2 endocyclic and 4 or 2 exocyclic and 3.

7. A composition as claimed in claim 4, 5 or 6 in which the weight ratio of compounds of formula IV to the other compounds is from 1:20 to 20:1.

8. A perfumed or flavoured product containing a compound of formula IV given in claim 1 wherein R1 and R2 are as in claim 1.

9. A product as claimed in claim 8 which is a perfumed soap, a detergent, a deodorant or a cosmetic preparation.

10. A product as claimed in claim 8 which is a flavoured foodstuff, beverage, pharmaceutical or tobacco.