CH627434A5 - POLYUNSATURATED ALIPHATIC ESTERS AND THEIR USE AS FLAVORING AND PERFUMING INGREDIENTS. - Google Patents

Description

The present invention relates to the field of aromas and to that of perfumery. It relates, in particular, to the use of polyunsaturated aliphatic esters of formula

O

Il 3 5

R - C - O - CH2 - CH2 - CH = CH - CH = CH2 (I)

in which the symbol R represents an alkyl radical, linear or branched, containing 1 to 5 carbon atoms and in which the double bond at position 3 has the configuration eis, as perfuming ingredients for the preparation of perfumes and perfumed products , and for flavoring food, beverages, pharmaceutical preparations and tobacco.

The invention also relates to a food containing, as a flavoring ingredient, a polyunsaturated aliphatic ester of formula (I).

The invention is defined as indicated in the claims.

The compounds of formula (I) are new compounds.

It has now been discovered that they have interesting organoleptic properties. They serve, in fact, to develop varied taste notes, especially fruity, and have the ability to improve the natural character of certain exotic fruits, especially pineapple, passion fruit and even orange. Their use, therefore, allows to reproduce more faithfully the proper taste of these fruits, especially their juices, enhancing their taste. The compounds of the invention find a highly appreciated use in the flavoring of foods and drinks of various nature, but especially in the flavoring of dairy products, yogurts, for example, fruit juices and syrups. They can also be used for flavoring products intended for baking or pastry making, or jams and sweets for example, or chewing gum in which the fruity note is desired.

The proportions in which the compounds of formula (I) develop interesting flavoring effects are included in a wide range of values. Preferably, they are used at concentrations of between approximately 0.5 and 50 ppm (parts per million) by weight relative to the total weight of the food in which they are incorporated. Of course, the limits indicated above cannot be interpreted restrictively, the user being able to determine the exact content desired according to the nature of the products subjected to the flavoring and the specific taste desired.

The compounds of the invention can be used in the isolated state or, preferably, in the form of a composition in admixture with other flavoring ingredients. They can be incorporated during any stage of manufacture of the selected food or drink and, preferably, they are added in the form of a solution in one of the usual edible solvents, such as ethyl alcohol, dipropylene glycol or triacetin.

Among the compounds of formula (I), acetate, butyrate and valerate of hexa-3-cis, 5-diene-1-yl represent the preferred compounds for any use as flavoring ingredients in accordance with invention.

When the compounds of formula (I) are used as perfuming ingredients, they develop fresh, floral and fruity, even green olfactory notes.

The compounds of formula (I) can also develop notes recalling certain aspects of the odor presented by the Roman chamomile.

When the compounds of the invention are used as perfuming agents, their preferred concentrations are between approximately 2 and 20% by weight relative to the total weight of the perfuming composition in which they are incorporated. Of course, the concentrations below the limits indicated above can be used, in particular when perfuming products such as soaps, bath foams, shampoos, body or air fresheners or cosmetic products in general.

The aliphatic esters of the invention can be prepared, in accordance with usual methods, by esterification of hexa-3-cis, 5-diene-1-ol, for example using an acyl chloride in the presence an organic base, for example nitrogenous, such as Pyridine or triethylamine.

The particular method used for the preparation of said compounds of formula (I) is described below by way of example. (The temperatures indicated are given in degrees centigrade.)

Hexa-3-cis, 5-diene-1-butylate

0.810 g (8.26 mM) of hexa-3-cis, 5-diene-1-ol in 7 ml of absolute pyridine were added dropwise, in approximately 10 min and with stirring, to a solution maintained at 0 -5 ° butyryl chloride in 9 ml of diethyl ether. The reaction mixture was kept stirring at 0-5 ° for an additional 30 min, then at room temperature for 30 min and finally heated to 60 ° during this same period. After cooling, the said mixture was poured onto ice and extracted with diethyl ether. The ethereal extracts were then washed with hydrochloric acid, then neutralized with a concentrated aqueous solution of NaHCO3 and finally with water, then dried over Na2SO4. Evaporation of the volatiles followed by distillation using a ball apparatus provided 1.3 g of a product having Eb. 80-100 ° / 0.01 Torr.

NMR (90 MHz) CDCl3: 0.96 (3H, t, 7 cPo); 1.65 (2H, m); 2.3 (2H, t, 7 cPo); 2.53 (2H, dxt, J1 = 7 cPo, J2 = 7 cPo); 4.13 (2H, t, J = 7 cPo); 4.9-5.62 (3H); 6.12 (1H, dxd, J, = 10 cPo, J2 = 10 cPo); 6.64 (1H, dxdxd, Jj -10 cPo, J2 = 10 cPo, J3 = 16 cPo) 8 ppm;

MS: M + = 168; m / e: 80 (100), 71 (52), 53 (7), 43 (71), 27 (23); IR (film): 3090,1735,1643,1595,1180,1000,905 and 785 cm- '.

Hexa-3-cis, 5-diene-1-ol, used as starting material in the preparation described above, can be prepared according to the method described by Meinwald and Nozaki in "J. Amer. Chem. Soc. ”, 80, 3132 (1958).

Hexa-3-cis acetate, 5-diene-l-yl

1.17 g (12 mM) of hexa-3-cis, 5-diene-1-ol, 1.55 g (15.6 mM) of acetic anhydride and 1.2 g of anhydrous pyridine were heated to about 100 ° for 2 h. The reaction mixture is then poured onto ice, then extracted with diethyl ether (2 x 50 ml). Once separated, the combined ether extracts were washed with IN HCl (3 x 50 ml), with water until neutral and finally dried over Na2SO4. After

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3

627,434

evaporation of the volatile parts, the residue obtained was subjected to distillation by means of a ball oven.

The desired acetate displayed Eb. 100-110 ° / 10 Torr; g. 1.25 (purity about 99%); yield 74%.

NMR (CDCI3; 90MHz): 2.03 (3H, s); 2.53 (2H, dxt, J, = 7 Hz, J2 = 7 Hz); 4.12 (2H, t, J = 2 Hz); 5-5.7 (3H); 6.12 (1H, dxd, J, = 10 Hz, J2 = 10 Hz); 6.66 (6H, dxdxd, Jj = 10 Hz, J2 = 10 Hz, J3 = 16 Hz) S ppm.

MS: M + (<1) = 140; m / e: 80 (70), 43 (100).

Hexa-3-cis, 5-diene-l-yl valerate

Said ester was prepared using valeryl chloride according to the method described for the preparation of the corresponding butyric ester.

Eb. 80-10070.01 Torr; g. 2.58; yield 94%.

NMR (CDCl3; 90 MHz): =: 0.9 (3H, t); 1.1-2.0 (6H, m); 2.3 (2H, t, J = 7 Hz); 2.53 (2H, dxd, Jt = 7 Hz, J2 = 7 Hz); 4.1 (2H, t, J = 7 Hz); 5.0-5.7 (3H); 6.1 (1H, dxd, Jj = 10 Hz, J2 = 10 Hz); 6.65 (1H, dxdxd, J! = 10 Hz, J2 = 10 Hz, J3 = 16 Hz) S ppm.

MS: M + (<1) = 196; m / e: 140 (<1), 99 (21), 80 (100), 71 (17), 55 (5), 43 (39), 29 (9).

The invention is illustrated in more detail by the following examples.

Example 1:

A basic flavoring composition of the fruity type was prepared by mixing the following ingredients (parts by weight):

5

Vanillin 20

Sweet orange essence 40

Lemon essence 10

Amyl acetate 20

io Butyl acetate 30

Ethyl propionate 30

Ethyl butyrate 50

Ethyl valerate 20

Ethyl enanthate 40

15 Benzyl alcohol 200

Propylene glycol 540

Total 1000

Using the above basic composition, two new compositions were prepared, defined respectively as control composition and test composition, the latter being obtained by adding hexa-3-cis, 5-diene- butyrate. l-yle as follows:

Composition A (control)

Composition A (test)

Basic composition

100

100

Hexa-3-cis, 5-diene-l-yl butyrate

-

50

Ethanol 95%

900

850

Total

1000

1000

These new compositions were subjected to an organoleptic evaluation in acidulated syrup (prepared by dissolving 650 g of sucrose in 1000 ml of water containing 10 ml of a 50% aqueous solution of citric acid), at a rate of 100 g of composition per 1001 of tangy syrup. The test composition had a characteristic note of pineapple, a note which was absent from the generic tutti frutti type control composition.

Example 2:

A basic fragrance composition of the flower type was prepared by mixing the following ingredients (part by weight):

Benzyl salicylate 100

P-ter-butylcyclohexyl acetate 80

Phenylethyl alcohol 70

Benzyl acetate 70

Linaloi 60

Heliotropin 50

Hydroxycitronellal synth 50

Geranyl acetate 40

Geraniol 40

Aid. œ-amylcinnamique 30

a-Isomethylionone 30

Undecalactone 10% * 30

Decanal 10% * 20

Bergamot essence 20

Nerolidol 20

Amyl salicylate 20

Lilial®2 20

Dodecanal 10% * 20

Cedrol 20

Tetrahydrolinalol 10

Undecanal 10% * 10

Undecenal 10% * 10

Methyl 2-Pentyl-3-oxocyclopentylacetate1 10

l, l-Dimethyl-4-acetyl-6-terbutylindane 10% * 1 .... 30

860

r

By adding 14 g of hexa-3-cis, 5-diene-1-yl butyrate to 86 g of the above basic composition, a new composition is obtained which has a very fruity and rising starting note. which recalls certain aspects of the odor developed by apricot or by peach.

40 Example 3:

4 A basic fragrance composition with a fruity character was prepared by mixing the following ingredients (parts by weight):

45 Dodecyl acetate 240

Geranyl propionate 150

Citronellyl propionate 100

Cyclopentadecanolide 10% * 100

Vanillin 10% * 70

50 Lemonellyl isobutyrate 40

Cinnamyl formate 40

"-Dorinone® 10% * 1 30

Benzyl propionate 30

Phenylethyl isobutyrate 30

55 Linalyl propionate 20

Amyl acetate 20

Hex-2-ene-l-ylacetate 20

ß-Dorinone® P / o * 1 20

Hexanal 10% * 20

60,940

* in diethylphthalate

1 origin: Firmenich SA, Geneva

2 origin: Givaudan & Cie, Vernier

65 By adding 6 g of hexa-3-cis, 5-diene-1-yl butyrate to 94 g of the above basic composition, a new composition is obtained whose fruity character was more natural, the fragrant note was also reinforced.

Claims (6)

627434 2. As a compound according to claim 1, hexa-3-cis, 5-diene-1-yl acetate. 2 CLAIMS 1. A polyunsaturated aliphatic ester of formula R - C - O - CH2 - CH2 - CH = CH - CH = CH2 (I) in which the symbol R represents an alkyl radical, linear or branched, containing 1 to 5 carbon atoms and in which the double bond at position 3 has the configuration eis. 3. As a compound according to claim 1, hexa-3-cis, 5-diene-1 -yl butyrate. 4. As a compound according to claim 1, hexa-3-cis, 5-diene-1 -yl valerate. 5. Use of a polyunsaturated aliphatic ester of formula (I), as indicated in claim 1, as perfuming ingredient for the preparation of perfumes and perfumed products, and for the flavoring of food, drinks , pharmaceutical preparations and tobacco. 6. Food resulting from the use according to claim 5.