CH619140A5 - Perfume or flavouring. - Google Patents

Description

The invention relates to a fragrance or flavoring and to a method for producing the active ingredient components contained therein. These compounds are cycloaliphatic unsaturated esters, which are valuable flavorings for food and tobacco and fragrances for perfumes.

Growing attention is being paid to the production and use of synthetic fragrances and fragrance-modifying substances for perfumes and perfumed products. The same applies to synthetic flavorings and flavoring substances for foods, beverages, pharmaceuticals and tobacco. This increasing attention is due not only to the fact that the amount of natural fragrance, aroma or flavor substances available is not sufficient, but perhaps to an even greater extent to the fact that there is a great need for substances that have different natural nuances are able to combine, can be better mixed with other fragrances or flavors and result in perfumed or spiced products that can be specifically tailored to a specific purpose and can be produced in any quantity as desired. This last-mentioned factor means a great advantage for synthetic fragrances and flavorings for foodstuffs, since natural products, such as essential oils, extracts, concentrates and the like, are subject to major changes due to deviations in the quality, in the type or in the treatment of the starting material.

There are three isomeric forms of saffranic acid, which are called a-, ß- and y-saffranic acid and correspond to formulas I, II and III.

--- COOH

a-saffron acid

II

ß-saffron acid

COOH

60

65

.COOH

III

y-saffranic acid

3rd

619 140

a-Saffranic acid is described in Helv. Chim. Acta 31, 134 (1948), / 3-saffranic acid in reports 74, 1242 (1941), unda- and y-saffranic acid are described in Helv. Chim. Acta 33, 1746 (1950) mentioned.

Some methyl and ethyl esters of saffranic acid are also known from the literature:

Ethyl saffron is in Helv. Chim. Acta 31, 134 (1948);

Methyl-a- and -y-safranate and ethyl-a- and -y-safranate are described in Helv. Chim. Acta 33, 1746 (1950);

the production of ethyl /? - safranate is described in Helv. Chim. Acta 38, 1863 (1955);

Methyl - /? - safranate is in Compt. Rend. Ser. C 262, 1725 (1966), Bull. Soc. Chim. France 1966, 3874 and in Agr. Biol. Chem. 34: 198 (1970);

the production of ethyl-a-, -ß- and y-safranate is in Helv. Chim. Acta 54, 1767 (1971);

Furthermore, esters of α-, β- and y-saffranic acid with saturated alcohols having 1 to 4 carbon atoms are mentioned in NL-OS 72.11248 and 73.01451, which on August 17, 1972 respectively. August 7, 1973.

According to these publications, the saffranic acid esters are used as intermediates for the production of safranal, damascenones and abscisic acid. At no point is anything said about the organoleptic properties of these esters.

It has now been found that saffranic acid esters and some new homologues thereof have useful organoleptic properties and can be used to impart taste and fragrance to a variety of products. These compounds can be used in combination with other flavoring agents, diluents or carriers to impart flavor to foods, beverages or tobacco products; to produce fragrance compositions, they can be mixed with other fragrances in a manner customary in perfumery.

For the sake of simplicity, the following nomenclature is used throughout this patent specification when designating the saffranic acid esters contained as active ingredient components in the fragrances or flavorings according to the invention in analogy to the isomers of saffranic acid:

15

20th

25th

30th

35

. ^ xC ^ / C00R2

10th

(IV)

a-isomer = two conjugated double bonds in positions 2-endocyclic and 4 ^ -isomer = two conjugated double bonds in positions 1 and 3

y-isomer = two conjugated double bonds in the positions 2-exocyclic and 3.

In the formula IV, Rt denotes an alkyl group or in the y-isomers an alkylidene group with 1 to 3 carbon atoms and R2 denotes an alkyl or alkenyl group with 1 to 4 carbon atoms.

The compounds of the formula IV in which Rt is a methyl group (a or β isomer) or a methylene group (y isomer) and R2 is a methyl or ethyl group are known compounds; namely they are the methyl and ethyl esters of saffranic acid which are described in the literature cited above. The other compounds of formula IV are new.

The known compounds of formula IV can be prepared by methods which are given in the literature mentioned. The new homologues of the saffronate can be obtained in an analogous manner. According to the method specified in NL-OS 73.01451, pages 11 to 13, the a-, ß- and y-saffranic acid ethyl esters from mesityl oxide and ethyl acetoacetate according to reaction scheme A as intermediates in the production of dasmasce non-analogs shown:

* IV

Reaction scheme A

If one starts from acetoacetic acid alkyl or alkenyl esters, one usually obtains a mixture of the compounds of formula IV (with Ri = CH3 or CH2), which mainly consists of the /? - isomer (about 60%) and about 20% each of the a and y isomers. It has now been found that the ratio of the a, β and y isomers to one another can be varied by changing the reaction time in the last stage of this reaction sequence.

In the preparation of the compounds of the formula IV in which Rx is a radical having two or three carbon atoms, an extension of the reaction time in the dehydration stage leads to the formation of a reaction mixture which consists of over 90% of the y-isomer. A shorter dehydration time leads to a higher content of the a- and / 3-isomers, although even then the y-isomer is still the main component in the mixture obtained. The three isomers of the compounds of formula IV can be separated by preparative gas-liquid chromatography.

The process according to the invention for the preparation of a mixture of compounds of the formula IV which are contained as an active ingredient in a fragrance or flavoring according to the invention is therefore characterized in that a compound of the formula is hydrogenated and the 4-hydroxy compound obtained is treated with p -Toluenesulfonic acid heated to reflux.

The preparation of a mixture of the a, β and y isomers of the compound of the formula IV, in which Ri = ethyl (a or / 3 isomer) or ethylidene (y isomer) and R2 = ethyl, is described in Example 1 described. By choosing other residues Ri

55

60

619140

4th

and R2 in the condensation reaction between mesityl oxide and acylacetic acid ester (cf. reaction scheme A), further compounds of the formula IV can be prepared. It is clear to the person skilled in the art that other methods for hydrogenating the cyclohexenone of the formula VIII can also be used (for example the Meerwein-Ponndorf reduction). Examples of this can be found in the literature references mentioned.

The following compounds of the formula IV were prepared analogously to the method given in Example 1:

Ri

R2

Boiling point in ° C

nD

CH3 or CH2

id id id

C3H7 or C3H6

ch3

Q.h5

ch2ch = ch2

ch2ch (ch3) 2

c2h5

37-40 / 3 mm Hg 70-76 / 5 mm Hg 78-79 / 2 mm Hg 68-73 / 2 mm Hg 78-82 / 3 mm Hg

1.4820 1.4790 1.4884 1.4747 1.4832

As already mentioned, all reaction products contain a, β and y isomers. The y-isomers of Formula IV, in which Rx contains two or three carbon atoms, exist in two geometric isomers, the eis and trans isomers, as shown in the following two formulas (IV with Rx = ethylidene):

2nd

IV (cis-y)

IV (trans-y)

20th

25th

30th

The amounts of the two y-isomers which form after the reaction sequence described are largely the same.

It has been shown that the compounds of the formula IV have very advantageous organoleptic properties. Although there are slight differences in their fragrance and taste character, it is not always necessary to separate the isomers because the mixture of the isomers as such can be used for the purposes of the invention. The isomers have strongly related smells, as can be seen from the following fragrance descriptions, which come from experienced fragrance and flavor experts.

Ethyl saffronate (mixture a: ß: y = 20:60:20, formula IV, Rt = methyl or methylene, R2 = ethyl): The main impression of this mixture can be herb-like, spicy (rosemary, ears, laurel) and fruity (apples, Plum) with a certain undertone of roses and wood.

Ethyl a-safranate (formula IV-a, Rx = methyl, R2 =

Ethyl): The woody, Jonon-like undertone is somewhat more pronounced than in the mixture of the three isomers.

ÄthyI - /? - safranat (formula IV- /?, Ri = methyl, R2 = ethyl): The herb-like, spicy character is more pronounced, although there is a great similarity to the mixture.

Ethyl-y-safranate (formula IV-y, Ri = methylene, R2 = ethyl): A strong fruity character (apple, plum) is noticeable, but the difference to the mixture of the three isomers is slight.

Methyl safanate (mixture, formula IV, Ra = methyl or methylene, R2 = methyl) has a less fruity character than ethyl safanate. The herbal spicy notes are stronger. The aftertaste has some lovely tonal notes.

Allyl safanate (mixture, formula IV, Rt = methyl or methylene, R2 = allyl): The character of the fragrance is almost identical to that of ethyl saffronate, but less intense.

Isobutylsafranate (mixture, formula IV, Ri = methyl or methylene, R2 = isobutyl): the main directions are herbs35

40

similar, spicy with a striking pear-like character. The mixture is particularly suitable for flavoring purposes.

EthyI-6,6-dimethyI-2-ethylidene-3-cyclohexenecarboxylate (Formula IV, Ra = ethylidene, R2 = ethyl): This ester shows a great similarity in fragrance to ethylsafaranate, but the fragrance intensity is probably somewhat stronger.

Ethyl-6,6-dimethyl-2-propylidene-3-cyclohexenecarboxylate (Formula IV, Rj = propylidene, R2 = ethyl): The odor intensity is much lower compared to ethyl safanate. The fruity notes of ethyl saffron have almost completely disappeared, but the herbal, spicy notes are much stronger. This ester also shows an earthy note.

The fragrance descriptions can give some general information on the usefulness of the compounds of the formula IV. However, the compounds are almost always used in combination with other flavors and fragrances. Under no circumstances can you predict whether a combination with a particular fragrance will perform satisfactorily in fragrance or flavor compositions. Furthermore, it is not sufficient for a substance that is to be used as a fragrance or flavoring ingredient that it only has one fragrance. Some other requirements are:

Compatibility with other fragrances and flavors as well as with the substrate that is to be provided with a fragrance or taste;

favorable toxicological and dermatological properties;

45 the ability to give complex character or a specific note to complicated fragrance or flavoring compositions according to the ideas of an experienced fragrance or flavoring expert.

The connections of the formal IV fulfill these requirements.

When compounds are tested for their usability in fragrance or flavoring compositions, the threshold values are often determined. Since the compounds 55 of formula IV very well to the known damascones and damascenones, the z. B. in GB-PS 1240 309 and in NL-OS 72.11248, and match the homologues of Damascone and Damascenone, which are given in GB-PS 1 456 151, the threshold values 6o of all these compounds and some mixtures thereof. The procedure used for this is described in the Manual on Sensory Testing Methods, A.S.T.M. Special Technical Publication No. 434, Philadelphia, 1968, page 30, method 3b and on page 61. In order to show some peculiarities of the 65 compounds of formula IV and the interactions of these compounds with other fragrances and flavors, the results of these tests are shown in the following table:

5

619140

designation

connection

Fragrance threshold

Description of the fragrance

A

Ethyl saffronate (mixture)

6X10- «

generally fruity,

a: ß: y = 20:60:20

but not apple-like

B

Ethyl-6,6-dimethyl-2-ethylidene

10 x KT6

apple-like

3 -cyclohexenecarboxylate

1x10-®

C.

a-Damascon0

apple-like

D

/ 3-Damascenon d

6x10-®

apple-like

E

Damascenon homologes e

8x10 "6

in the amount of

Threshold:

fruity; in higher

concentration

coffee-like

F

Damascon homolog

0.8 x 10 "6

apple-like

G

A + E (5: 2)

0.2x10- «

clearly apple-like

H

B + E (5: 2)

2X10 "6

apple-like

I.

A + D (5: 2)

0.6x10- «

apple-like

Remarks:

a) All compounds and mixtures were dissolved in colorless diethyl phthalate.

b) The threshold values were determined by lay observers who were asked to give a general description of the fragrance. The descriptions in the table are very different from those given by experts.

c) = trans-2,6,6-trimethyl-l-crotonyl-2-cyclohexene, cf. GB-PS 1 240 309

d) = trans-2,6,6-trimethyl-l-crotonyl-l, 3-cyclohexadiene, cf. GB-PS 1 240 309

e) reaction product of Example 9 of GB-PS 1 456 151

f) reaction product of Example 8 of GB-PS 1 456 151

From this table you can see that the mixtures G, H and I have significantly lower threshold values than the individual components. This is probably the first case in which synergism in this area has been demonstrated through quantitative data. Also striking is the fact that the combination of compounds A and E has a certain apple-like smell, while the individual components on their own have a general fruit-like scent that is not reminiscent of the scent of apples.

It follows that the esters of formula IV, when used in combination with cycloaliphatic unsaturated ketones such as a-damascone, / 3-damascenone or one or more homologs thereof, which are described in GB-PS 1 456 151, specifically reinforce the fragrance and flavor properties of these ketones, which enables optimal taste and fragrance effects to be achieved. Like the ketones, the esters can be mixtures of isomers. In order to obtain these remarkable effects, the relative amounts of the esters of formula IV and the unsaturated ketones can vary between 1:20 and 20: 1.

It is clear to the person skilled in the art that when using flavorings and fragrances it is neither possible nor practical to give general instructions for the use of the esters of the formula IV either alone or in combination with the ketones mentioned in these fields because too many factors determine the absolute amounts of the substances to be used. These factors include the personal preference of the flavor or fragrance expert, the cost of the material, the nature of the particular composition, the taste or fragrance effect that is to be achieved, etc. Nevertheless, it is completely clear to the person skilled in the art how to use the esters of the formula IV will use in each situation.

Fragrance compositions containing the esters of formula IV can be used in a large number of perfumed products. For example, they can be used in soaps, washing and cleaning agents or deodorants or in cosmetic preparations such as colognes, toilets30

35

water, face creams, body lotion, talcum powder, sunscreen and aftershave. Flavor compositions containing the esters of Formula IV can be used to impart flavor to foods, beverages, drugs, or tobacco. The esters can also be used to improve the taste of beverages such as fruit juices.

The invention is explained in more detail in the following examples. All amounts in Examples 2 to 11 are based on weights.

40

example 1

A. Preparation of ethyl 6,6-dimethyl-2-ethyl-4-oxo-2-cyclohexenecarboxylate A mixture of 294 g mesityl oxide, 432 g a-propionyl-45-acetic acid ethyl ester, 150 g cyclohexane and 75 g zinc chloride was used for 60 hours stirred at the boiling point of the mixture. The water resulting from the reaction was drained through a Dean-Stark pipe. The mixture obtained was stirred at room temperature for 10 minutes with 300 g of a 10% HCl solution and 150 g of cyclohexane. After washing with water, a NaHCO 3 solution and again water, the cyclohexane was distilled off from the separated organic layer and the residue was fractionated in vacuo. This gave 272 g of a product, bp 55 126-135 ° C./2 Torr, nD 20 = 1.4788, which, according to gas-liquid chromatography and NMR analysis, was 90% ethyl-6,6-dimethyl- 2-ethyl-4-oxo-2-cyclohexenecarboxylate existed.

B. Preparation of a mixture of 60 ethyl 6,6-dimethyl-2-ethylidene-3-cyclohexenecarboxylate, ethyl 6,6-dimethyl-2-ethyl-l, 3-cyclohexadiene carboxylate and

Ethyl 6,6-dimethyl-2-ethyl-2,4-cyclohexadiene carboxylate. A solution of 24 g NaBH4 and 0.25 g NaOH in 100 g 65 water was added dropwise to a solution of 270 g ethyl 6,6-dimethyl-2-ethyl-4-oxo-2-cyclohexenecarboxylate in 100 g ethanol. During the addition, the reaction vessel was cooled to 35-45 ° C. The reaction mixture was

619 140

6

stirred for a further 4 hours without cooling, the temperature in the reaction vessel slowly reaching room temperature. The reaction mixture was diluted with 200 ml of toluene and washed with 100 ml of 10% acetic acid. The organic phase was separated and dried. Thereafter, 2 g of p-toluenesulfonic acid were added and the mixture was boiled under reflux for 2 hours.1 After washing with a 5% NaHCO 3 solution and water, the volatile solvent was removed in vacuo, leaving 263 g of an oily liquid which was fractionally distilled . The second fraction of the distillate (167 g) had a boiling point of 74-90 ° C / 2 Torr and the refractive index nD20 = 1.4819. It consisted of a mixture of the three compounds mentioned in the heading, namely they contained 15% a-isomer, 5% β-isomer and 80% / -isomer.

Example 2

Rose-type perfume composition Three rose-type perfume compositions were prepared by mixing the following ingredients.

Component composition

A

B

C.

Cinnamon alcohol

15

20th

5

Phenylethyl alcohol

400

380

435

Rhodinol

260

280

250

1-citronellol

160

140

150

Phenylacetaldehyde dimethylacetal

40

50

25th

a-methyl ionone

15

-

5

Hydroxycitronellal

5

-

10th

Gyrane (N), fragrance available

by Naarden International N.V.

30th

20th

15

Phenylethyl propionate

15

30th

25th

Geranyl acetate

10th

20th

30th

Citronellyl ethyl oxalate

20th

10th

5

Eugenol, 10% solution in

Diethyl phthalate

15

5

10th

Undecenal, 10% solution in

Diethyl phthalate

5

-

5

Rose oxide, 10% solution in

Diethyl phthalate

5

5

5

y-methyl ionone

-

10th

-

Linalool

-

10th

-

Laurinaldehyde, 10% solution in

Diethyl phthalate

-

10th

-

Rosana NB 131, Rosenbase

available from Naarden Inter

national N.V.

-

5

-

Geranium oil bourbon

-

-

10th

Rose absolutely, 10% solution in

Diethyl phthalate

-

-

5

995

995

990

A. Adding 9.5 g of a 1% solution of ethyl safanate in diethyl phthalate to 99.5 g of mixture A makes the composition more brilliant than the original mixture and gives it a more pronounced natural rose character with a distinctly fruity top note.

B. By adding 9.5 g of a 1% solution of ethyl 6,6-dimethyl-2-ethylidene-3-cyclohexenecarboxylate in diethyl phthalate to 99.5 g of mixture B, the composition is instantly stronger and fuller. The mixture

1 If the mixture is refluxed for 7 hours, the / isomer (bp 77-80 ° C / 2 Torr, nD 20 = 1.4835) is the only reaction product.

received an unusual brilliance and a floral, lifelike rose character.

C. Adding 1 g of a 1% solution of ethyl 6,6-dimethyl-2-propylidene-3-cyclohexenecarboxylate to 99 g of mixture C gave the mixture a greater fullness and a more pronounced natural note than the starting mixture.

Example 3

Perfume composition of the Gougère type.

Three perfume compositions of the Fougère type were made by mixing the following ingredients:

Component composition

A

B

C.

Coumarin

30th

25th

15

Musk ketone

5

5

10th

Phenylethyl alcohol

80

90

100

Absolutely oak moss

10th

10th

5

Amyl salicylate

30th

20th

40

Rosemary oil

30th

35

40

Serpolet oil

10th

15

20th

Lavender oil, French style

260

255

220

Bergamot essence

100

60

120

lemon oil

40

60

30th

Eugenol

10th

15

5

Ylang-ylang oil

5

10th

5

Coriander oil

5

5

-

Clary sage oil

5

10 '

10th

Geranium oil bourbon

20th

25th

20th

Musk Rl, fragrance available from

Naarden International N.V.,

10% solution in diethyl phthalate

20th

30th

40

Undecenal, 10% solution in

Diethyl phthalate

10th

5

15

Linalool

70

50

15

Methyl nonyl acetaldehyde,

10% solution in diethyl phthalate

-

5

-

y-methyl ionone

-

10th

5

Tetradecanal, 1% solution in

Diethyl phthalate

-

5

-

Thyme oil, 10% solution in

Diethyl phthalate

-

10th

740

745

785

A. After adding 1 g of a 1% solution of ethyl safanate in diethyl phthalate to 74 g of mixture A, a considerable increase in the brilliance can be observed. The composition becomes stronger in character and gets a strikingly fruity note.

B. By adding 0.5 g of a 1% solution of ethyl 6,6-dimethyl-2-ethylidene-3-cyclohexenecarboxylate in diethyl phthalate to 74.5 g of mixture B, the composition becomes stronger and fuller. The mixture becomes more brilliant and the character of the perfume is emphasized.

C. The addition of 1.5 g of a 1% strength solution of ethyl 6,6-dimethyl-2-propylidene-3-cyclohexenecarboxylate in diethyl phthalate to 78.5 g of the mixture C gives the fragrance character of this mixture a fuller and warmer core and there is a noticeable increase in brilliance.

Example 4

Perfume composition of the pine fantasy type

Three pine fantasy type perfume compositions were made by mixing the following ingredients:

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

7

619 140

component

Composition A B

C.

Incense resinoid

20th

10th

10th

Elemi oleoresin

20th

25th

10th

Bornyl acetate liquid

550

580

600

Turpentine oil, distilled

130

100

110

Orange oil terpenes

150

120

135

Rosemary oil, French

5

20th

20th

Guaiylacetate

15

10th

10th

Absolutely lemon, 10% solution

in diethyl phthalate

10th

-

10th

Methyl nonyl acetaldehyde,

10% solution in diethyl phthalate

30th

40

25th

Ligustral (N), fragrance available

by Naarden International N.V.,

10% solution in diethyl phthalate

20th

15

5

Juniper berry oil

20th

30th

20th

Oak moss absolutely,

10% solution in diethyl phthalate

20th

25th

10th

Thyme oil, 10% solution in

Diethyl phthalate

5

-

-

Serpolet oil

-

20th

-

Origanum oil

-

10th

Synthetic geranium oil

-

-

5

Lavender oil, French

-

-

5

Bay leaf oil

-

-

5

995 995 990

A. The addition of 5 g of a 1% solution of ethyl safanate in diethyl phthalate to mixture A (995 g) leads to a remarkable increase in the brilliance and natural fullness of this composition.

B. The addition of 5 g of a 1% solution of ethyl 6,6-dimethyl-2-ethylidene-3-cyclohexenecarboxylate in diethyl phthalate to 995 g of mixture B leads to a fuller, warmer character of this composition, to a large . serene brilliance and more emphasis on the warm herbal notes.

C. Adding 10 g of a 1% solution of ethyl 6,6-dimethyl-2-propylidene-3-cyclohexenecarboxylate in diethyl phthalate to 990 g of mixture B gives a composition with a stronger full natural character.

Example 5

Making an Apple Flavor Imitation

An apple flavor imitation was made by mixing the following ingredients:

Amylacetate

35

Ethyl butyrate

15

Hexyl acetate

3rd

Amyl propionate

1

Orange oil Florida

0.4

Ethanol 96%

945.6

1000

An apple drink was made using 9.3 g of this flavor composition per 1 finished drink. Two modifications to the apple flavor composition were prepared by adding 25 and 50 ppm ethyl safanate to the composition.

A group of taste experts compared these two modified apple drinks with the unmodified drink. All members of this group clearly preferred the drinks that contained an addition of the ethyl saffronate, since these resembled more natural apples in terms of fragrance and taste. No significant difference was made between the two drinks with ethyl saffronate, although the difference in concentration was announced.

From this example it can be seen that the concentration of ethyl saffronate in the finished beverage is far below the fragrance threshold value of the pure compound. Nevertheless, the influence on the fragrance and the taste of the drink can be clearly determined. (25 ppm in the composition; 0.3 g of the composition per 1 drink; this gives the concentration of ethylsafranate in the drink at 7.5 • io-9 g / 1.)

Example 6

Preparation of a composition with an imitated apple taste A composition with an imitated apple taste was prepared according to L. Bénézet, La Parfumerie Moderne 43 (1951) No. 22, 61-78:

Ethyl acetate 50

Ethyl acetoacetate 200

Ethyl formate 20

Ethyl butyrate 50

Ethyl hexanoate 20

Ethyl heptanoate 50

Ethyl octanoate 20

Isoamyl formate 50

Isoamyl acetate 50

Isoamyl pentanoate 100

Isoamylhexanoate 50

Isoamyl octanoate 100

Acetaldehyde 50

Geraniol 10

Geranyl formate 10

Geranyl acetate 10

Phenylethylpentanoate 20

Benzaldehyde 5

Cinnamyl propionate 50

Diethyl malonate 64

Orange Oil Florida 20

Rose oil 1

1000

A 1% solution in ethanol was prepared from this mixture. Part of this solution was used to make an apple drink, using 0.3 g of the ethanol solution per 1 finished drink.

Another part of the ethanol solution was added with 100 ppm ethyl safanate. With this solution, a second apple-flavored drink was prepared, which contained 0.3 g of the solution per 1 finished drink.

In a comparison of the two drinks by a group of experienced taste experts, the drink with the addition of ethyl saffronate was unanimously preferred.

Example 7

Preparation of a raspberry flavored composition

A raspberry flavored composition was made by mixing the following ingredients:

Geraniol 20

Vanillin 20

Maltol 20

Phenylethyl alcohol 50

p-hydroxybenzyl acetone 50

a-methyl ionone 100

/ 3-Jonon 100

5

10th

IS

20th

25th

30th

35

40

45

50

55

«0

65

619140

8th

Benzyl acetate 100

Isobutyl acetate 100

Ethyl acetate 100

Amyl acetate 100

Ethanol 240

1000

A 1% solution of this mixture in ethanol was used as a flavoring in a raspberry drink. The addition of 100 ppm ethyl saffronate to the ethanol solution resulted in an improved drink with a natural raspberry-like taste and smell.

Example 8

Preparation of a composition with an imitated raspberry taste A composition with an imitated raspberry taste was produced in a modification of the regulation by L.Bénézet, La Parfumerie Moderne 43 (1951) No. 22, 61-78:

Acetylmethylcarbinol 3

Diacetyl 2

Ethyl acetate 10

Isobutyl acetate 40

Ethyl hexanoate 10

Isoamylhexanoate 10

Hexyl acetate 10

Hexeny lace did 10

Benzyl acetate 50

Isoamyl alcohol 10

Hexanol 5

Hexenol 5

/ 3-Jonon 25

a-methyl ionone 25

Iris oil (heavy) 15

Anisaldehyde 5

Benzaldehyde 5

Phenylethyl alcohol 50

Methyl salicylate 10

Bornyl salicylate 10

Clove germ oil 10

Orange oil, sweet 50

Geranium oil 10

Coumarin 20

Vanillin; 30th

so-called «aldehyde C-16» 400

Benzylidene mesityl oxide 100

Ethyl benzoate 10

940

0.3 g of a 1% solution in ethanol was used per 1 finished drink. The addition of 100 ppin ethyl saffronate to the ethanol solution of the flavor composition resulted in a drink with a better raspberry taste.

Example 9

Perfume composition of the rose type Three compositions of the rose type were prepared by mixing the following ingredients:

connection

composition

A

B

C.

Cinnamon alcohol

15

10th

20th

Trichloromethylphenylcarbinylacetate

5

5

-

Phenylethyl alcohol

355

370

365

Rhodinol

180

160

170

connection

Composition A B

C.

Citronellol

170

140

120

Nerol

20th

40

70

Phenylacetaldehyde dimethyl acetal

30th

40

30th

a-methyl ionone

10th

10th

10th

Guaiylacetate

10th

5

10th

Hydroxycitronellal

10th

15

17th

Gyrane (N), fragrance available

by Naarden International N.V.

30th

25th

20th

Phenylethyl propionate

20th

25th

15

Geranyl acetate

10th

10th

5

Citronelly ethyl oxalate

20th

25th

35

Geranium oil bourbon

20th

20th

15

Rose oxide, 10% solution in

Diethyl phthalate

15

10th

5

Rosana NB 131, Rosenbase

available from Naarden Inter

national N.V.

60

70

80

Rose absolutely

5

5

5

985

985

992

Three modifications were made to composition A:

a) Add 1 g of a 10% solution of the Damascon homolog described in Example 8 of GB-PS 1456 151 in diethyl phthalate to 98.5 g of the basic mixture A.

b) Add 9.5 g of a 1% solution of ethyl safanate in diethyl phthalate to 98.5 g of the basic mixture A.

c) addition of both 1 g of the solution according to a) and 0.5 g of the solution according to b) to 98.5 g of the basic mixture A.

Three modifications were made from composition B:

a) addition of 1 g of a 10% strength solution of the damascenone homolog indicated in Example 9 of GB-PS 1456 151 in diethyl phthalate to 98.5 g of the basic mixture B.

b) Add 0.5 g of a 1% solution of ethyl safanate in diethyl phthalate to 98.5 g of the basic mixture B.

c) addition of both 1 g of the solution according to a) and 0.5 g of the solution according to b) to 98.5 g of the basic mixture B.

Finally, three modifications were made from composition C:

a) Add 0.5 g of a 10% solution of / J-Damas-cenon in diethyl phthalate to 99.2 g of the basic mixture C.

b) Add 0.3 g of a 1% solution of ethyl safanate in diethyl safanate to 99.2 g of the basic mixture C.

c) Add both 0.5 g of the / 3-damascenone solution and 0.3 g of the ethylsafranate solution to 99.2 g of the basic mixture C.

• A group of 10 experienced fragrance experts was asked to compare the modifications with the original blends. In any case, it was found that the basic mixture was improved by adding the cycloaliphatic ketones (additions a) or by adding ethylsafranate (additions b). In all three cases, however, it was concluded that by adding both additives (a + b) the effects were super-additive and compositions with a very natural rose character were obtained, which had a radiant warmth and a well-balanced top note.

Example 10 Apple Flavor Imitation

Three modifications of the basic composition of Example 5 were made:

s

10th

15

20th

25th

30th

35

40

45

50

55

60

65

9

619 140

A. 1.5 g of a 1% solution of / 3-damascenone in ethanol were added to 100 g of the basic mixture.

B. 5 g of a 1% solution of ethyl safanate in ethanol were added to 100 g of the starting mixture.

G. 2.5 g of a 1% strength solution of β-damascenone in ethanol and 5 g of a 1% strength solution of ethylsafranate in ethanol were added to 100 g of the basic mixture.

These three modifications of the basic mix were assessed in finished apple drinks by a group of experienced flavor experts. According to the statements of this 10 group, modifications A and B already showed an improvement in the basic composition; however, the beverage containing Modification C was much preferred. This modification gave the drink an even more natural taste and fragrance than A and B.

The apple flavor imitations of Example 5, which contain 25 or 50 ppm of ethyl saffronate, and Modification C of this example can be used to impart flavor to tobacco products as described in Memory, Food Flavorings, Composition, Manufacture and Use, Westport 1968 »20 is described.

Example 11 Raspberry Flavor Imitation

Three modifications of the basic composition of Example 8 were made:

A. 10 g of the basic mixture were dissolved in 1000 g of ethanol. 0.2 g of ethyl safanate was added.

B. 10 g of the basic mixture were dissolved in 1000 g of ethanol and 0.1 g of a 10% strength solution of the Damascenone homogen of Example 9 of British Pat. No. 1,456,151 in ethanol was added.

C. 10 g of the basic composition were dissolved in 1000 g of ethanol and 0.2 g of ethyl safanate and 0.1 g of a 10% strength solution of the damascenone homologue of Example 9 of British Pat. No. 1,456,151 in ethanol were added.

From these three modifications and from the basic composition, raspberry-flavored beverages were made by using 0.3 g of the alcoholic solutions per 1 finished beverage. The drinks were compared by a group of experienced flavor experts. Although the beverages made using Modifications A and B were considered improvements over the beverage made from the base composition, there was unanimous preference for the beverage made from Mixture C. The fragrance and taste of / 3-Jonon can be clearly determined in the drinks made from the basic mix or modifications A or B. The drink, which is made from modification C, is much more rounded in taste and fragrance and has a strong raspberry character.

s

Claims (5)

619 140 2. Fragrance or flavoring according to claim 1, characterized in that it contains at least one ester of the formula IV together with an effective amount of at least one compound of the formula 15 20th 25th 30th wherein the dashed lines represent a double bond in the 1-position or in the 2-position or two double bonds in the 1- and 3-position, and / or at least one compound 35 of the formula 0 40 45 50 0 C00R, R, VIII 10th hydrogenated and the resulting 4-hydroxy compound heated to reflux with p-toluenesulfonic acid for 2 to 7 hours. 2nd PATENT CLAIMS 1. Fragrance or flavoring, characterized in that it contains at least one saffronate of the formula as an active ingredient COOR, IV C0-CH = CH-CH- V VI wherein two of the dashed lines each represent a double bond, d. H. two double bonds in positions 1 and 4 or 1 and 3 or 2-exocyclic and 3 or 2-endocyclic and 4 are present, and / or at least one compound of the formula .6 0 5, VII where R is hydrogen or methyl and the dashed lines represent a double bond in the 1 or 2-endocyclic or 2-exocyclic position or two conjugated double bonds in the 1 and 3 or 2-endocyclic and 4 or 2-exocyclic and 3 positions, contains. 3. Fragrance or flavoring according to claim 2, characterized in that the amount of the ester or esters of the formula IV is in a ratio of 1:20 to 20: 1 to the amounts of the other substances. 4. Process for the preparation of a mixture of compounds of the formula IV which are used as active ingredient components in one Fragrance or flavoring according to claim 1 are contained, characterized in that a compound of the formula in which the dashed lines have two conjugated double bonds, namely in the a-isomer in the 2-endocyclic positions and 4, in the β-isomer in the positions 1 and 3 and in the y-isomer in the positions 2-exocyclic and 3, Rt is an alkyl group or in the y-isomer is an alkylidene group with 1 to 3 carbon atoms and R2 is an alkyl or alkenyl group with 1 to 4 carbon atoms , contains. 5. The method according to claim 4, characterized in that one starts from 6,6-dimethyl-2-ethyl-4-oxo-2-cyclohexencar-bonsäureäthylester.