CH641143A5 - 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

II

R-C-0-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 or drink resulting from the above use.

The compounds of formula (I) are new compounds.

The invention is defined as indicated in the claims.

Best way to realize the invention

It has now been discovered that said compounds of formula (I) 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 clean taste of these fruits,

more especially of their juice, by reinforcing their gustatory character. The compounds of the invention find a very appreciated use in the flavoring of food 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 to flavor products intended for baking or pastry making, or for 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), the 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, 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 nitrogen, 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-l-yl butyrate

0.810 g (8.26 mmol) of hexa-3-cis, 5-diene-1-ol in 7 ml of absolute pyridine was 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, J = 7 cPo); 2.53 (2H, dxt, Jj = 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, Jx = 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-1.

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 mmol) of hexa-3-cis, 5-diene-l-ol, 1.55 g (15.6 mmol) 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). A

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641143

once separated, the combined ethereal extracts were washed with IN HCl (3 x 50 ml), with water until neutral and finally dried over Na2SO4. After 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; 1.25 g (purity about 99%); yield 74%.

NMR (90 MHz CDCl3): 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, Jj = 10 Hz, J2 = 10 Hz); 6.66 (H, dxdxd, Ja = 10 Hz, J2 = 10 Hz, J3 = 16 Hz) 8 ppm;

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

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

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

Eb. 80-100 ° / 0.01 Torr; 2.58 g; yield 94%.

NMR (90 MHz CDCl3): = 0.9 (3H, t); 1.1-2.0 (6H, m); 2.3 (2H, t, J = 7 Hz); 2.53 (2H, dxd, Ja = 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, Ji = 10 Hz, J2 = 10Hz, J3 = 16 Hz) 8 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):

Vanillin

20

Sweet orange essence

40

Lemon essence

10

Amyl acetate

20

Butyl acetate

30

Ethyl propionate

30

Ethyl butyrate

50

Ethyl valerate

20

Ethyl enanthate

40

Benzyl alcohol

200

Propylene glycol

540

Total

1000

Using the basic composition above, two new compositions were prepared, defined respectively as control composition and test composition, the latter being obtained by adding hexa-3-cis, 5-diene-1-butyrate. -yle as follows:

Composition A (control)

Composition B (test)

Basic composition Hexa-3-cis butyrate,

5-diene-l-yl Ethanol 95%

Total

100,900

ÏÔÔÔ

100 50 850

1ÖÖÖ

These new compositions were subjected to an or-ganoleptic 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 floral-type perfume composition was prepared by mixing the following ingredients (parts by weight):

5 Benzyl salicylate 100

P-Terbutylcyclohexyl acetate 80

Phenylethyl alcohol 70

Benzyl acetate 70

Linaloi 60

10 Heliotropin 50

Synthetic hydroxycitronellal 50

Geranyl acetate 40

Geraniol 40

A-amylcinnamic aldehyde 30

15 a-Isomethylionone 30

Undecalactone 10% * 30

Decanal 10% * 20

Bergamot essence 20

Nerolidol 20

20 Amyl salicylate 20

Lilial®2 20

Dodecanal 10% * 20

Cedrol 20

Tetrahydrolinalol 10

25 Undecanal 10% * 10

Undecenal 10% * 10

Methyl 2-Pentyl-3-oxocyclopentylacetate1 10

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

Total 860

30 * In diethyl phthalate.

1 Origin: Firmenich SA, Geneva.

2 Origin: Givaudan & Cie, Vernier.

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 having a very fruity and rising starting note which recalls certain aspects of the smell developed by apricot or peach.

Example 3:

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

Dodecyl acetate 240

Geranyl propionate 150

Citronellyl propionate 100

Cyclopentadecanolide 10% * 100

Vanillin 10% * 70

Lemonellyl isobutyrate 40

Cinnamyl formate 40

a-Dorinone® 10% * '30

Benzyl propionate 30

Phenylethyl isobutyrate 30

Linalyl propionate 20

Amyl acetate 20

Hex-2-ene-l-ylacetate 20

ß-Dorinone® 1% '20

Hexanal 10% * 20

Total 940

* In diethyl phthalate.

60 1 Origin: Firmenich SA, Geneva.

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

R

Claims (4)

641143 1. Polyunsaturated aliphatic ester of formula: O 11 R-C-0-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. 2. As an aliphatic ester according to claim 1, - hexa-3-cis, 5-diene-1-yl acetate, - hexa-3-cis, 5-diene-1-yl butyrate, and - hexa-3-cis, 5-diene-1-yl valerate. 2 3. Use of a polyunsaturated aliphatic ester of formula (I) according to claim 1, as a perfuming ingredient for the preparation of perfumes and perfumed products, and for the flavoring of food, drinks, preparations pharmaceutical and tobacco. 4. Food resulting from the use according to claim 3. Technical field and description of the invention