Spirooxathiolanone compounds, their preparation method as well as their use in perfume-making and aromatics

Abstract

The present invention concerns new fragrant and aromatic compounds presenting peach, fruity and/or exotic fruit notes, but with no lactonic and fat aspects. More specifically, new spirooxathiolanone-type compounds responding to the following general formula (I) are disclosed: ##STR00001##
as well as a method for synthesising said compounds and their uses.

Claims

1. A compound of the following general formula (I): ##STR00009## wherein: R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6 and R.sub.7, represent independently a hydrogen atom or a methyl group; R.sub.5 represents a hydrogen atom or a saturated linear C.sub.1-C.sub.5 alkyl group; R.sub.4 and R.sub.5 could together form a cyclopentyl group; and the total number of carbon atoms is greater than 9, with the proviso that when R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.7 are all hydrogen, R.sub.5 is not t-butyl, wherein the compound has aromatic or olfactive properties.

2. The compound according to claim 1, wherein R.sub.5 represents a saturated linear C.sub.1-C.sub.5 alkyl group.

3. The compound according to claim 1, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6 and R.sub.7, represent a hydrogen atom.

4. The compound according to claim 1, wherein the total number of carbon atoms is 10 or 11.

5. The compound according to claim 1, wherein the compound is selected from the group consisting of 7,7-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-ethyl-3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8,8-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 3-methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one, oxathiolanone of spiro[4.5]decan-8-one, 7,7,9-trimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one and 8-pentyl-1-oxa-4-thiaspiro[4.5]decan-2-one.

6. A method for preparing a compound of formula (I) according to claim 1 comprising performing a cyclisation reaction between a cycloalcanone of formula (II) and a thiol acid of formula (III) in the presence of an acid as follows: ##STR00010## wherein: R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6 and R.sub.7, represent independently a hydrogen atom or a methyl group; R.sub.5 represents a hydrogen atom or a saturated linear C.sub.1-C.sub.5 alkyl group; R.sub.4 and R.sub.5 could together form a cyclopentyl group; and the total number of carbon atoms is greater than 9.

7. The method according to claim 6, wherein the thiol acid is thioglycolic acid.

8. The method according to claim 6, wherein the thiol acid is thiolactic acid.

9. The method according to claim 6, wherein the cyclization reactions is performed in the present of a sulphonic para-toluene acid.

10. A method of providing, modifying, or reinforcing the organoleptic properties of a substance, a composition, or an article comprising using at least one compound of general formula (I) according to claim 1 in the form of a stereoisomer, a mixture of stereoisomers, or a racemic mixture to provide, modify, or reinforce the organoleptic properties of a substance, a composition or an article.

11. The method according to claim 10 wherein at least one compound of formula (I) is used as a fragrant agent, individually or in combination with another component selected from the group consisting of an odorising substance, a solvent, and an additive.

12. The method according to claim 10 wherein at least one compound of general formula (I) is used as an aromatic compound, individually or in combination with another component selected from the group consisting of an aromatic substance, a solvent, and an additive.

13. A composition comprising a compound of the following general formula (I): ##STR00011## wherein: R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6 and R.sub.7, represent independently a hydrogen atom or a methyl group; R.sub.5 represents a hydrogen atom or a saturated linear C.sub.1-C.sub.5 alkyl group; R.sub.4 and R.sub.5 could together form a cyclopentyl group; and the total number of carbon atoms being strictly greater than 9, with the proviso that when R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.7 are all hydrogen, R.sub.5 is not t-butyl; and, wherein said composition further comprises an inert support material, wherein the compound has aromatic or olfactive properties.

14. The composition according to claim 13 wherein the compound is selected from the group consisting of 7,7-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-ethyl-3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8,8-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 3-methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one, oxathiolanone of spiro[4.5]decan-8-one, 7,7,9-trimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one and 8-pentyl-1-oxa-4-thiaspiro[4.5]decan-2-one.

15. The composition according to claim 13, wherein the compound of formula (I) is present in a concentration comprising between 0.000001 to 50% by weight with respect to the total weight of the composition.

16. The composition according to claim 13, wherein said composition is a perfume comprising at least one compound of formula (I) and at least one odorising substance.

17. The composition according to claim 13, wherein said composition is an aromatic composition comprising at least one compound of formula (I) and at least one aromatic substance.

18. The composition according to claim 13, wherein the compound of formula (I) is present in a concentration comprising between 0.000005 to 20% weight with respect to the total weight of the composition.

Description

EXAMPLE 1

Preparation of 7,7-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one

(1) 3,3-dimethylcyclohexanone (whose preparation is disclosed, for example, in the application WO 2010043522) is placed in 1.1 equivalents of thioglycolic acid and 4 volumes of cyclohexane. At ambient temperature, 0.05 equivalent of sulphonic para-toluene acid is added. The reaction media is brought to reflux while the water formed is removed by azeotropic distillation. When the reaction is ended, the reaction media is poured on an aqueous solution saturated in sodium bicarbonate. The organic phase is washed with water up to neutral pH. After drying on magnesium sulphate, filtration and concentration, the raw product is distilled under reduced pressure: its boiling point is 89° C. under 0.26 torr.

(2) Olfactive Description: Fruity, Peach, Raspberry Effect.

(3) 7,7-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained presents the following spectral features:

(4) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 3.73 (s, 1H), 3.72 (s, 1H), 2.10-1.90 (m, 2H), 1.85-1.58 (m, 4H), 1.46-1.29 (m, 1H), 1.34-1.16 (m, 1H), 1.04 (s, 3H), 0.97 (s, 3H).

(5) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 172.34, 92.16, 51.31, 39.82, 37.74, 32.23, 31.11, 28.37, 19.90.

(6) SM [EI.sup.+] (m/z) (%): 200 (M+, 9), 127 (100), 109 (55), 83 (25), 69 (34), 56 (10), 55 (35), 46 (12), 43 (26), 41 (25), 39 (10).

(7) IR (pure, cm.sup.−1): 2946m, 1765s, 1455w, 1215m, 1144m, 1060m, 1025m, 993m, 954m, 914w, 811w, 797w, 607w.

EXAMPLE 2

Preparation of 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one

(8) 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described I example 1 by using 4-ethylcyclohexanone instead of 3,3-dimethylcyclohexanone. The raw product, obtained in the form of two diastereoisomers in proportions 54:46, is distilled under reduced pressure: its boiling point is 98° C. under 0.18 torr.

(9) Olfactive Description: Exotic Fruits, Mango, Guava, Papaya.

(10) 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained presents the following spectral features:

(11) Major Isomer (54%):

(12) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 3.62 (s, 2H), 2.21-2.06 (m, 1H), 2.05-1.88 (m, 2H), 1.80-1.60 (m, 3H), 1.40-1.23 (m, 1H), 1.26-1.04 (m, 4H), 0.81 (td, J=7.2 Hz, 3H).

(13) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 172.24, 94.34, 38.70, 37.43, 31.69, 39.34, 11.57.

(14) SM [EI.sup.+] (m/z) (%): 200 (M+, 10), 127 (100), 109 (37), 67 (33), 55 (41), 46 (12), 43 (13), 41 (22).

(15) Minor Isomer (46%):

(16) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 3.69 (s, 2H), 2.21-2.06 (m, 1H), 2.05-1.88 (m, 2H), 1.80-1.60 (m, 3H), 1.40-1.23 (m, 1H), 1.26-1.04 (m, 4H), 0.81 (td, J=7.2 Hz, 3H).

(17) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 172.26, 91.48, 39.49, 37.17, 32.25, 29.12, 28.69, 11.47.

(18) SM [e/m (%)]: 200 (M+, 10), 129 (10), 127 (100), 109 (35), 67 (33), 55 (42), 46 (12), 43 (14), 41 (23).

(19) IR (pure, cm.sup.−1): 2926m, 1767s, 1442w, 1197m, 1139m, 1041m, 966m, 915w, 892w, 854w, 796w.

EXAMPLE 3

Preparation of 8-ethyl-3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one

(20) 8-ethyl-3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described in example 1 by using 4-ethylcyclohexanone instead of 3,3-dimethylcyclohexanone, thiolactic acid (1.3 equivalents) instead of thioglycolic acid and toluene instead of cyclohexane. The raw product, obtained in the form of two diastereoisomers in proportions 42:58 is distilled under reduced pressure: its boiling point is 88° C. under 0.4 mbar.

(21) Olfactive Description: Peach, Green, Tomato Leaf

(22) 8-ethyl-3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained presents the following spectral features:

(23) Major Isomer (58%):

(24) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 3.99 (q, J=7.0 Hz, 1H), 2.28-2.09 (m, 1H), 2.09-1.61 (m, 5H), 1.57 (d, J=7.0 Hz, 3H), 1.52-0.95 (m, 5H), 0.88 (t, J=7.0 Hz, 3H).

(25) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 175.19, 91.63, 40.90, 39.61, 38.96, 37.52, 29.78, 29.15, 28.71, 18.40, 11.60.

(26) SM [EI.sup.+] (m/z) (%): 210 (M+, 0.3), 195 (100), 137 (24), 109 (34), 101 (998), 93 (10), 91 (14), 81 (11), 79 (15), 76 (15), 67 (16), 43 (64), 41 (16).

(27) Minor Isomer (42%):

(28) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 3.99 (q, J=7.0 Hz, 1H), 2.28-2.09 (m, 1H), 2.09-1.61 (m, 5H), 1.58 (d, J=7.0 Hz, 3H), 1.52-0.95 (m, 5H), 0.87 (t, J=7.0 Hz, 3H).

(29) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 175.25, 88.74, 41.43, 40.27, 39.74, 37.28, 29.23, 29.06, 28.76, 18.54, 11.50.

(30) SM [EI.sup.+] (m/z) (%): 214 [M.sup.+] (6), 127 (100), 109 (19), 67 (12), 60 (20), 55 (23), 41 (15).

(31) IR (film, cm.sup.−1): 1039m, 1209m, 1447s, 1761s, 2928m.

EXAMPLE 4

Preparation of 8,8-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one

(32) 8,8-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described in example 1 by using 4,4-dimethylcyclohexanone instead of 3,3-dimethylcyclohexanone. The raw product is distilled under reduced pressure: its boiling point is 92° C. under 0.39 torr.

(33) Olfactive Description: Fruity, Green, Exotic Fruits.

(34) 8,8-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained has the following spectral features:

(35) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 3.71 (s, 2H), 2.19-2.01 (m, 2H), 1.98-1.80 (m, 2H), 1.63-1.30 (m, 4H), 0.94 (2s, 6H).

(36) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 172.35, 93.19, 36.05, 35.74, 31.95, 29.11.

(37) SM [EI.sup.+] (m/z) (%): 200 (M+, 12), 127 (100), 109 (35), 71(15), 67 (16), 55 (33), 46 (15), 43 (24), 41 (24), 39 (10).

(38) IR (pure, cm.sup.−1): 2950m, 1767s, 1444w, 1232m, 1215m, 1156m, 1045s, 1001m, 972m, 877m, 791w, 585w.

EXAMPLE 5

Preparation of 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one

(39) 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described in example 1 by using 4-propylcyclohexanone instead of 3,3-dimethylcyclohexanone. The raw product, obtained in the form of two diastereoisomers in proportions 46:54, is distilled under reduced pressure: its boiling point is 106-110° C. under 0.2 torr.

(40) Olfactive Description: Peach, Apricot, Juicy, Pulp.

(41) 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained presents the following spectral features:

(42) Major Isomer (54%):

(43) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 3.74 (s, 2H), 2.22-2.16 (m, 1H), 2.05-1.95 (m, 2H), 1.85-1.64 (m, 3H), 1.40-1.11 (m, 7H), 0.89-0.84 (t, J=7.2 Hz, 3H).

(44) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 172.38, 94.50, 38.79, 38.27, 31.78, 29.73, 20.12, 14.27.

(45) SM [EI.sup.+] (m/z) (%): 214 (M+, 7), 142 (10), 141 (100), 81 (43), 67 (20), 55 (28), 46 (10), 43 (10), 41 (18).

(46) Minor Isomer (46%):

(47) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 3.68 (s, 2H), 2.22-2.16 (m, 1H), 2.05-1.95 (m, 2H), 1.85-1.64 (m, 3H), 1.40-1.11 (m, 7H), 0.89-0.84 (t, J=7.2 Hz, 3H).

(48) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 172.38, 91.65, 39.58, 38.24, 32.24, 29.50, 20.00, 14.27.

(49) MS [e/m (%)]: 214 (M+, 9), 141 (100), 81 (39), 67(19), 55(22), 41 (15).

(50) IR (pure, cm.sup.−1): 2926m, 1768s, 1443w, 1223m, 1193m, 1137w, 1043m, 969m, 912w, 842w, 796w, 589w.

EXAMPLE 6

Preparation of 3-methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one

(51) 3-methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described in example 1 by using 4-propylcyclohexanone instead of 3,3-dimethylcyclohexanone, thiolactic acid (1.3 equivalents) instead of thioglycolic acid and toluene instead of cyclohexane. The raw product, obtained in the form of two diastereoisomers in proportions 44:56, is distilled under reduced pressure: its boiling point is 95° C. under 0.4 mbar.

(52) Olfactive Description: Peach, Fruity, Green.

(53) 3-methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained has the following spectral features:

(54) Major Isomer (56%):

(55) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 3.98 (q, J=7.0 Hz, 1H), 2.26-1.61 (m, 6H), 1.56 (d, J=7.0 Hz, 3H), 1.51-0.95 (m, 7H), 0.87 (t, J=7.0 Hz, 3H).

(56) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 175.12, 91.56, 41.39, 40.86, 39.60, 38.95, 38.25, 35.48, 30.12, 20.11, 18.38, 14.26.

(57) SM [EI.sup.+] (m/z) (%): 228 [M.sup.+] (3), 142 (10), 141 (100), 81 (20), 67 (10)

(58) Minor Isomer (44%):

(59) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 4.06 (q, J=7.0 Hz, 1H), 2.26-1.61 (m, 6H), 1.57 (d, J=7.0 Hz, 3H), 1.51-0.95 (m, 7H), 0.86 (t, J=7.0 Hz, 3H).

(60) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 175.18, 88.68, 41.39, 40.24, 39.73, 38.30, 35.22, 29.56, 29.40, 19.99, 18.52, 14.26.

(61) SM [EI.sup.+] (m/z) (%): 228 [M.sup.+] (3), 142 (10), 141 (100), 81 (20), 67 (10), 60 (13)

(62) IR (film, cm.sup.−1): 1036m, 1224m, 1443m, 1755s, 1926m.

EXAMPLE 7

Preparation of oxathiolanone of spiro[4.5]decan-8-one

(63) Oxathiolanone of spiro[4.5]decan-8-one is prepared according to the protocol described in example 1 by using spiro[4.5]decan-8-one instead of 3,3-dimethylcyclohexanone. The raw product is recrystallised in cyclohexane.

(64) Olfactive Description: Peach, Velvety, Green, Vanilla Effect.

(65) Oxathiolanone of spiro[4.5]decan-8-one thus obtained presents the following spectral features:

(66) .sup.1H-RMN (300 MHz, CDCl.sub.3): (ppm) 3.74 (s, 2H), 2.16-2.07 (m, 2H), 1.97-1.88 (m, 2H), 1.69-1.59 (m, 6H), 1.54-1.43 (m, 6H).

(67) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 172.42, 93.38, 41.20, 37.02, 34.68, 32.00, 24.45, 24.39.

(68) SM [EI.sup.+] (m/z) (%): 226 (M+, 6), 154 (11), 153 (100), 135 (10), 67 (14), 55 (15).

(69) IR (pure, cm.sup.−1): 2943m, 1771s, 1443m, 1267m, 1221s, 1209s, 1131m, 1041s, 978m, 933m, 900w, 838m, 794m, 608w.

EXAMPLE 8

Preparation of 7,7,9-trimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one

(70) 7,7,9-trimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described in example 1 by using 3,5,5-trimethylcyclohexanone instead of 3,3-dimethylcyclohexanone. The raw product, obtained in the form of two diastereoisomers in proportions 74:26, is distilled under reduced pressure: its boiling point is 87° C. under 0.04 torr.

(71) Olfactive Description: Peach, Woody, Camphor, Green.

(72) 7,7,9-trimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained presents the following spectral features:

(73) Major Isomer (74%):

(74) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 3.73 (s, 2H), 2.19-2.06 (m, 1H), 2.04-1.84 (m, 2H), 1.57-1.25 (m, 3H), 1.06 (s, 3H), 0.97-0.80 (m, 7H).

(75) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 172.53, 91.83, 51.48, 48.37, 46.93, 33.48, 32.74, 32.18, 26.67, 25.98, 21.89.

(76) SM [EI.sup.+] (m/z) (%): 214 (M+, 7), 142 (10), 141 (100), 123 (14), 83 (85), 69 (15), 55 (25), 46 (10), 43 (11), 41 (22).

(77) Minor Isomer (26%):

(78) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 3.65 (s, 2H), 2.19-2.06 (m, 1H), 2.04-1.84 (m, 2H), 1.57-1.25 (m, 3H), 1.04 (s, 3H), 0.97-0.80 (m, 7H).

(79) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 171.99, 93.57, 49.67, 47.62, 47.15, 33.56, 32.46, 32.29, 26.59, 26.38, 21.64.

(80) SM [EI.sup.+] (m/z) (%): 214 (M+, 5), 142 (11), 141 (100), 123 (16), 83 (88), 69 (16), 55 (25), 46 (10), 43 (13), 41 (24), 39 (10).

(81) IR (pure, cm.sup.−1): 2951m, 1766s, 1456w, 1210m, 1167m, 1139w, 1022m, 1005m, 958m, 896w, 859w, 798w, 612w.

EXAMPLE 9

Preparation of 8-pentyl-1-oxa-4-thiaspiro[4.5]decan-2-one

(82) 8-pentyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described in example 1 by using 4-pentylcyclohexanone instead of 3,3-dimethylcyclohexanone. The raw product, obtained in the form of two diastereoisomers in proportions 45:55, is distilled under reduced pressure: its boiling point is 135° C. under 0.2 torr.

(83) Olfactive Description: Peach, Fruity, Herbaceous.

(84) 8-pentyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained has the following spectral features:

(85) Major Isomer (55%):

(86) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 3.67 (s, 2H), 2.21-2.14 (m, 1H), 2.06-1.90 (m, 2H), 1.84-1.64 (m, 3H), 1.40-1.11 (m, 11H), 0.88-0.83 (t, J=7.2 Hz, 3H).

(87) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 172.32, 94.45, 38.79, 35.94, 35.76, 32.02, 31.99, 29.76, 22.60, 14.06.

(88) SM [EI.sup.+] (m/z) (%): 242 (M+, 4), 170 (12), 169 (100), 95 (24), 81 (24), 67 (12), 55 (24), 43 (12), 41 (23).

(89) Minor Isomer (45%):

(90) .sup.1H-RMN (300 MHz, CDCl.sub.3): δ (ppm) 3.73 (s, 2H), 2.21-2.14 (m, 1H), 2.06-1.90 (m, 2H), 1.84-1.64 (m, 3H), 1.40-1.11 (m, 11H), 0.88-0.83 (t, J=7.2 Hz, 3H).

(91) .sup.13C-RMN (75 MHz, CDCl.sub.3): δ (ppm) 172.32, 91.61, 39.58, 35.97, 35.49, 32.31, 31.75, 29.53, 26.58, 22.62, 14.27.

(92) SM [e/m (%)]: 242 (M+, 4), 170 (12), 169 (100), 95 (21), 81 (21), 67 (12), 55 (25), 43 (13), 41 (23).

(93) IR (pure, cm.sup.−1): 2922m, 2853m, 1769s, 1443w, 1209m, 1184m, 1133w, 1041m, 982m, 901w, 796w.

EXAMPLE 10

Perfumed Composition Comprising the Derivatives Obtained in Examples 2, 5 or 7 Applied in a Shampoo Base (at a Rate of 0.6%)

(94) In a rose match produced in the following table (Match A) are added: 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one (compound 16025-37, Example 5, Match B) 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one (compound 16025-43, Example 2, Match C) oxathiolanone of spiro[4.5]decan-8-one (compound 16025-56, Example 7, Match D)

(95) TABLE-US-00001 Ingredients A B C D CITRONELLOL 300 300 300 300 GERANIOL 150 150 150 150 PHENYLETHYL ALCOHOL 150 150 150 150 PHENOXYETHYL ISOBUTYRATE 80 80 80 80 DIPHENYL OXIDE 80 80 80 80 NEROL 75 75 75 75 ISOAMYL ACETATE 10% DPG 25 25 25 25 GERANIUM ESS 20 20 20 20 ROSE OXIDE 20 20 20 20 CITRAL 15 15 15 15 OXACYCLOHEXADECAN-2-ONE 15 15 15 15 MAGNOLAN ™ 7 7 7 7 DAMASCENONE 10% DPG 7 7 7 7 FRUCTONE ™ 5 5 5 5 RASPBERRY KETONE 5 5 5 5 METHYL PHENYLETHYL ETHER 10% 5 5 5 5 DPG OXANE 50% TEC 3 3 3 3 DIMETHYL SULPHIDE 3 3 3 3 VANILLINE 1 1 1 1 DIPROPYLENE GLYCOL - DPG 34 29 29 29 Compound 16025-37 — 5 — — Compound 16025-43 — — 5 — Compound 16025-56 — — — 5 1000 1000 1000 1000

(96) Adding 5 parts of the compound 16025-37 to the match A boosts the fruity-rose effect of the match elegantly, giving more petal, natural effect, while adding the compound 16025-43 in the same proportions gives a more woody and peach effect, giving a richer and opulent rose. Adding the compound 16026-56 gives a “harder” aspect, through the green. The match is less rosy than in the two preceding cases, fruitier, grapefruit, and still with more power than in the match A.

(97) In both cases, adding a molecule according to the invention gives power and a green note which blends well with the general match of the perfumed composition.

EXAMPLE 11

Perfumed Composition Comprising the Derivatives Obtained in Examples 2, 5 or 7 Applied in a Laundry Softener Base (at a Rate of 1%)

(98) In a fruity-gourmet match produced according to the following table (Match A) are added: 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one (compound 16025-37, Example 5, Match B) 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one (compound 16025-43, Example 2, Match C) xathiolanone of spiro[4.5]decan-8-one (compound 16025-56, Example 7, Match D)

(99) TABLE-US-00002 Ingredients A B C D HEXYLCINNAMIC ALDEHYDE 125 125 125 125 METHYL DIHYDRO JASMONATE 80 80 80 80 ETHYL VANILLINE 75 75 75 75 ISO E 45 45 45 45 HEXYL SALICYLATE 45 45 45 45 4 tBu CYCLOHEXYL ACETATE 40 40 40 40 HABANOLIDE 40 40 40 40 VANILLINE 38 38 38 38 VERDYL ACETATE 35 35 35 35 2 tBu CYCLOHEXYL ACETATE 50% 30 30 30 30 DPG ROSAFIX 25 25 25 25 TETRAHYDROLINALOL 25 25 25 25 ANISIC ALDEHYDE 25 25 25 25 FLOROL ™ 25 25 25 25 PHENOXYETHYL ISOBUTYRATE 25 25 25 25 ORANGE TERPENES 25 25 25 25 GERANIOL 23 23 23 23 GAMMA UNDECALACTONE 23 23 23 23 PHENYLETHYL ALCOHOL 18 18 18 18 ETHYL METHYL PHENYL GLYCIDATE 17 17 17 17 GAMMA NONALACTONE 17 17 17 17 ETHYL MALTOL 14 14 14 14 SILVIAL ™ 10% DPG 14 14 14 14 ALPHA ISOMETHYL IONONE 12 12 12 12 GERANYLE ACETATE 10% DPG 12 12 12 12 LINALYLE ACETATE 10 10 10 10 1-(2,3-DIMETHYL-BICYCLO[2.2.1]HEPT- 9 9 9 9 2-YL)-ETHANONE 1% DPG COUMARINE 7 7 7 7 CIS-3-HEXENYL SALICYLATE 7 7 7 7 BENZYL ACETATE 6 6 6 6 METHYL ANTHRANILATE 6 6 6 6 FRAMBINONE 6 6 6 6 DMBC BUTYRATE 6 6 6 6 ETHYL CINNAMATE 6 6 6 6 MADERAL ™ 5 5 5 5 DAMASCENONE 10% DPG 5 5 5 5 LIFFAROME ™ 10% DPG 5 5 5 5 ETHYL METHYLVALERATE 10% DPG 4 4 4 4 DELTA DAMASCONE 4 4 4 4 HELIOTROPINE 4 4 4 4 CYCLOGALBANATE ™10% DPG 4 4 4 4 PATCHOULY EO 2 2 2 2 6-[2,4,4-TRIMETHYL- 2 2 2 2 CYCLOPENTYLIDENE]-HEXANAL 1% DPG ORCANOX ™ 2 2 2 2 Compound 16025-37 — 3 — — Compound 16025-43 — — 3 — Compound 16025-56 — — — 3 DIPROPYLENE GLYCOL - DPG 50 47 47 47 1000 1000 1000 1000

(100) Adding 3 parts of the compound 16025-37 to the match A, brings a lot of power and gives a greener, fusing note, while adding the compound 16025-43 rounds the note even more, with a more present and powerful gourmet, vanilla effect.

(101) Adding the compound 16025-56 also rounds the match, while tamping down the fruity notes to this dosage.

EXAMPLE 12

Aromatic Composition Comprising the Derivative Obtained in Example 5 Applied in a Yogurt (at a Rate of 0.08%, that is 160 ppb)

(102) TABLE-US-00003 Ingredients A B ACETYL METHYL CARBINOL 50% PG 2 2 STRAWBERRY FURANONE 30% PG 3 3 PROPIONIC ACID 12.5 12.5 BUTYRIC ACID 15 15 BUTYLIC ALCOHOL 15.5 15.5 GAMMA DECALACTONE 17.5 17.5 C02 ACETIC ACID 20 20 ETHYL ACETATE 20 20 LINALOL 25 25 C05 METHYL 2 BUTYRIC ACID 25 25 APRICOT B.P.L. 48.5 48.5 GLYCOL PROPYLENE 796 794.5 Compound 16025-37 10% PG — 2 1000 1000

(103) Adding the compound 16025-37 to 160 ppb in the yogurt gives the peach flavour a more authentic, rounder, peach nectar profile.

EXAMPLE 13

Aromatic Composition Comprising the Derivative Obtained in Example 5 Applied in a Yogurt (at a Rate of 0.02%, that is 140 ppb)

(104) TABLE-US-00004 Ingredients A B BUTYRIC ACID 15 15 GAMMA DECALACTONE 7 7 C02 ACETIC ACID 12 12 LINALOL 1.5 1.5 C05 BUTYRIC METHYL 2 ACID 6 6 THIAZOLE ISOPROPYL METHYL 1% ALC 1 1 BUCHU ESSENCE DETERPENE 1% ALC 1.4 1.4 GERANYLE ACETATE 1.5 1.5 GAMMA HEXALACTONE S 2.5 2.5 HEXYL ACETATE 3 3 BENZOIC ALDEHYDE 3 3 DELTA DECALACTONE 3 3 MALTOL 3 3 GAMMA DODECALACTONE S 3.5 3.5 HEXENOL CIS 3 4.5 4.5 HEXENYL CIS 3 ACETATE 9 9 LIMONENE 9 9 ISOAMYLE ACETATE 15 15 C02 ETHYLIC ALCOHOL 899.1 897.1 Compound 16025-37 10% PG 7 1000 1000

(105) Adding the compound 16025-37 at a rate of 140 ppb complexifies the apricot profile, brings a very natural side, apricot flesh, juice, very tasty. The profile of this apricot flavour is very particular and has not been able to be reproduced using other compounds of the prior art.

EXAMPLE 14

Olfactometry Tests

(106) It is generally admitted that the ratio of the volatility by the detection threshold of an odour makes it possible to obtain an “odour value” with no unit, considering the olfactive power of a molecule. The greater this value is, the more powerful the molecule in question is. In order to calculate this odour value, the volatility, as well as the detection threshold must consequently be determined.

(107) In the present study, two molecules of the invention are tested in order to determine their power (via their odour value) with respect to a reference molecule of the prior art, gamma-undecalactone. The two molecules according to the invention which are tested are that of example 2 (8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one) and that of example 5 (8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one).

(108) Initially, the volatility values at 20° C. of the molecules of example 2 and example 5 are determined by ebulliometry. These values are respectively 19.8 μg.Math.l.sup.−1 and 7.8 μg.Math.l.sup.−1.

(109) Secondly, psychosensorial studies have been carried out, in order to determine the detection threshold of the two molecules according to the present invention and as well as that of gamma-undecalactone.

(110) The value of the detection threshold is obtained using a dynamic olfactometer constructed according to the guidelines of the standards ISO 13725 and ISO 13301. It corresponds to the critical statistical gaseous concentration to trigger a positive response for a set of eighteen panellists as a minimum, of which the age varies from 22 to 57 years old according to a model of a forced choice from among two. One of these choices is the controlled dilution of an airflow saturated in raw material, the other choice is a neutral airflow. The random repetition of these choices for a set of five to eight gaseous concentrations, thus allows the determination of the detection threshold after statistical treatment of the data obtained. Thus, the detection threshold for the molecules of example 2 and example 5 have been determined and are respectively 0.016 ng.Math.l.sup.−1 and 0.075 ng.Math.l.sup.−1.

(111) Thus, after these measurements, it is possible to calculate the odour value of the molecules according to the invention in comparison with that of gamma-undecalactone.
Odour Value=Volatility value/Detection threshold

(112) The Odour Value is equal to 1222223 for the molecule according to example 2, and to 104133 for the molecule according to example 5. Yet, for gamma-undecalactone, the Odour Value determined under identical experimental conditions is 5473.

(113) In conclusion, the Odour Value of the molecules according to the invention (of examples 2 and 5) is very clearly greater than that of gamma-undecalactone which indicates said molecules according to the invention are very clearly more powerful than gamma-undecalactone.

(114) Furthermore, the substantivity evaluated by the panellists is equal to 2.59 for the molecule according to example 2, and to 2.62 for the molecule according to example 5.