NOVEL ACETALS OF 1-(3,3-DIMETHYLCYCLOHEX-1-ENYL) ETHANONE, METHOD FOR THE PRODUCTION THEREOF AND USE OF SAME IN PERFUMERY

Abstract

The present invention concerns new fragrant compounds exhibiting animal or amber notes, without any woody aspect. More particularly, new acetal derivatives of 1-(3,3-dimethylcyclohex-1-enyl)ethanone are disclosed, which correspond to the following general formula I:

##STR00001##

as well as a method of synthesising said compounds, and their use in perfumery.

Claims

1. A compound of the following general formula I: ##STR00006## wherein: m and n represent a carbon number and are each independently 0 or 1; R.sub.1 represents a hydrogen atom or a saturated C.sub.1-C.sub.2 alkyl group; the carbon-carbon bond shown as a dotted line is present or absent, and when said bond is absent, R.sub.2 is present and represents a hydrogen atom or a saturated C.sub.1-C.sub.2 alkyl group, when said bond is present, R.sub.2 is absent; said compound being in the form of a stereoisomer, a mixture of stereoisomers, or a racemic mixture.

2. The compound according to claim 1, wherein said carbon-carbon bond shown as a dotted line is absent.

3. The compound according to claim 1, wherein n is 0 and m is 1.

4. The compound according to claim 1, wherein n and m are 0.

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

6. The compound according to claim 1, said compound being chosen from 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-1,3-dioxolane, 2-(3,3-dimethylcyclohex-1-enyl)-2,4-dimethyl-1,3-dioxolane, 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-1,3-dioxane, 2-(3,3-dimethylcyclohex-1-enyl)-2,5-dimethyl-1,3-dioxane, 2-(3,3-dimethylcyclohex-1-enyl)-2,5,5-trimethyl-1,3-dioxane, 2-(3,3-dimethylcyclohex-1-enyl)-5,5-diethyl-2-methyl-1,3-dioxane and 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-4,7-dihydro-1,3-dioxepine.

7. A composition comprising at least one compound of the following general formula I: ##STR00007## wherein: m and n represent a carbon number and are each independently 0 or 1; R.sub.1 represents a hydrogen atom or a saturated C.sub.1-C.sub.2 alkyl group; the carbon-carbon bond shown as a dotted line is present or absent, and when said bond is absent, R.sub.2 is present and represents a hydrogen atom or a saturated C.sub.1-C.sub.2 alkyl group, when said bond is present, R.sub.2 is absent; said compound being in the form of a stereoisomer, a mixture of stereoisomers, or a racemic mixture.

8. The composition according to claim 7, said composition comprising at least one compound chosen from 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-1,3-dioxolane, 2-(3,3-dimethylcyclohex-1-enyl)-2,4-dimethyl-1,3-dioxolane, 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-1,3-dioxane, 2-(3,3-dimethylcyclohex-1-enyl)-2,5-dimethyl-1,3-dioxane, 2-(3,3-dimethylcyclohex-1-enyl)-2,5,5-trimethyl-1,3-dioxane, 2-(3,3-dimethylcyclohex-1-enyl)-5,5-diethyl-2-methyl-1,3-dioxane and 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-4,7-dihydro-1,3-dioxepine.

9. The composition according to claim 7, wherein said compound is a fragrant agent; said composition further comprising at least one other fragrant agent.

10. The composition according to claim 7, wherein the compound of general formula I is present in a concentration of between 0.01 and 99 wt % of the total weight of the composition, more particularly between 0.1 and 30 wt % of the total weight of the composition.

11. The composition according to claim 7, said composition being a perfume composition.

12. A method of preparing a compound of general formula I according to claim 1, said method comprising the following steps of: a) cyclisation/rearrangement of dehydrolinalool by an acid into 1-(3,3-dimethylcyclohex-1-enyl)ethanone, and; b) acetalisation of 1-(3,3-dimethylcyclohex-1-enyl)ethanone by a diol to obtain the compound of general formula I.

13. The method according to claim 12, wherein the acid in step a) is chosen from phosphoric acid and methanesulfonic acid.

14. Method according to claim 12, wherein the diol in step b) is chosen from ethylene glycol, neopentyl glycol, 1,2-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-propanediol, or cis-2-butene-1,4-diol.

15. Use of at least one compound of general formula I according to claim 1 as a fragrant agent.

16. Use according to claim 15, wherein said compound of general formula I is used in combination with at least one other fragrant agent and/or at least one solvent and/or at least one additive.

17. Use according to claim 15 to confer, alter or reinforce the organoleptic properties of a substance, composition or item.

Description

EXAMPLE 1

Preparation of 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-1,3-dioxolane

[0045] In a flask, an equivalent of dehydrolinalool is placed in toluene. This solution is refluxed. Phosphoric acid (10% of the mass of dehydrolinalool) is then added slowly dropwise. After 20 hours of agitation under reflux, and once returned to ambient temperature, the reaction medium is poured onto a saturated aqueous solution of sodium bicarbonate. The phases are separated. The organic phase is washed in water until neutral. After drying on magnesium sulphate, filtration and evaporation of the solvent, the crude product is distilled under reduced pressure: its boiling point is 52° C. at 53.3 Pascal.

[0046] The 1-(3,3-dimethylcyclohex-1-enyl)ethanone thus obtained is placed in 4 equivalents of ethylene glycol and 2 equivalents of triethyl orthoformate. At ambient temperature, para-toluene sulfonic acid is added (1% of the mass of 1-(3,3-dimethylcyclohex-1-enyl)ethanone introduced). The reaction medium is left under agitation in these conditions for twenty hours, and then poured onto a saturated aqueous solution of sodium bicarbonate. This aqueous phase is extracted twice in cyclohexane. The combined organic phases are washed in water until neutral. After drying on magnesium sulphate, filtration and concentration, the crude product is distilled under reduced pressure: its boiling point is 46° C. at 53.3 Pascal.

Olfactory description: animal, amber, aromatic, terpenic.

[0047] The 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-1,3-dioxolane thus obtained exhibits the following spectral characteristics:

[0048] .sup.1H-NMR (200 MHz, CDCl.sub.3): δ (ppm) 0.94 (s, 6H), 1.34-1.37 (m, 2H), 1.41 (s, 3H), 1.57-1.61 (m, 2H), 1.91 (td, J=6.2 Hz, 1.6 Hz, 2H), 3.70-3.85 (m, 2H), 3.85-3.95 (m, 2H), 5.56 (s, 1H).

[0049] .sup.13C-NMR (50 MHz, CDCl.sub.3): δ (ppm) 19.85, 23.76, 23.96, 29.92, 31.34, 36.95, 64.18, 109.31, 132.60, 134.75.

[0050] MS [e/m (%)]: 196 (M+, 0.2), 181 (100), 109 (21), 87 (82), 73 (14), 43 (32).

[0051] IR (film, cm.sup.−1): 859m, 946w, 1043s, 1110w, 1187m, 1209m, 1371w, 2933m.

EXAMPLE 2

Preparation of 2-(3,3-dimethylcyclohex-1-enyl)-2,4-dimethyl-1,3-dioxolane

[0052] 2-(3,3-dimethylcyclohex-1-enyl)-2,4-dimethyl-1,3-dioxolane is prepared according to the protocol described in Example 1 using 1,2-propanediol instead of ethylene glycol. The crude product, made up of 2-(3,3-dimethylcyclohex-1-enyl)-2,4-dimethyl-1,3-dioxolane in the form of two diastereomers in proportions 62:38, is distilled under reduced pressure: its boiling point is 49° C. at 66.7 Pascal.
Olfactory description: animal, camphorated.

[0053] The 2-(3,3-dimethylcyclohex-1-enyl)-2,4-dimethyl-1,3-dioxolane thus obtained exhibits the following spectral characteristics:

[0054] Majority isomer (62%):

[0055] .sup.1H-NMR (200 MHz, CDCl.sub.3): δ (ppm) 0.93 (s, 6H), 1.25 (d, J=6.1 Hz, 3H), 1.33-1.38 (m, 2H), 1.42 (s, 3H), 1.59-1.61 (m, 2H), 1.88-1.95 (m, 2H), 3.37-3.42 (m, 1H), 3.86-3.90 (m, 1H), 4.02-4.08 (m, 1H), 5.55 (s, 1H).

[0056] .sup.13C-NMR (50 MHz, CDCl.sub.3): δ (ppm) 18.99, 19.87, 24.00, 24.71, 29.92, 29.96, 31.31, 36.98, 70.58, 71.48, 109.56, 132.28, 135.11.

[0057] MS [e/m (%)]: 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).

[0058] Minority isomer (32%):

[0059] .sup.1H-NMR (200 MHz, CDCl.sub.3): δ (ppm) 0.94 (s, 6H), 1.22 (d, J=6.1 Hz, 3H), 1.33-1.38 (m, 2H), 1.39 (s, 3H), 1.59-1.61 (m, 2H), 1.88-1.95 (m, 2H), 3.28-3.33 (m, 1H), 4.00-4.04 (m, 1H), 4.18-4.25 (m, 1H), 5.60 (s, 1H).

[0060] .sup.13C-NMR (50 MHz, CDCl.sub.3): δ (ppm) 18.35, 19.83, 24.00, 24.24, 29.80, 29.87, 31.35, 36.98, 70.92, 72.40, 109.50, 132.54, 136.30.

[0061] MS [e/m (%)]: 210 (M+, 0.3), 195 (100), 137 (25), 109 (33), 101 (58), 91 (13), 81 (11), 79 (14), 76 (14), 66 (14), 43 (54), 41 (15).

[0062] IR (film, cm.sup.−1): 866m, 937w, 953w, 1038s, 1085s, 1187s, 1210s, 1370m, 2930m.

EXAMPLE 3

Preparation of 2-(3,3-dimethylcyclohex-1-enyl)-2,5-dimethyl-1,3-dioxane

[0063] 2-(3,3-dimethylcyclohex-1-enyl)-2,5-dimethyl-1,3-dioxane is prepared according to the protocol described in Example 1, using 2-methyl-1,3-propanediol instead of ethylene glycol. The crude product, made up of 2-(3,3-dimethylcyclohex-1-enyl)-2,5-dimethyl-1,3-dioxane, is distilled under reduced pressure: its boiling point is 46° C. at 26.7 Pascal.
Olfactory description: amber, green, red fruits.

[0064] The 2-(3,3-dimethylcyclohex-1-enyl)-2,5-dimethyl-1,3-dioxane thus obtained exhibits the following spectral characteristics:

[0065] .sup.1H-NMR (200 MHz, CDCl.sub.3): δ (ppm) 0.64 (d, J=6.7 Hz, 3H), 0.85-1.06 (m, 1H), 0.98 (s, 6H), 1.32 (s, 3H), 1.41-1.43 (m, 2H), 1.61-1.65 (m, 2H), 1.84 (t, J=6.7 Hz, 1H), 1.97-2.07 (m, 1H), 3.26-3.34 (m, 2H), 3.63-3.68 (m, 2H), 5.56 (s, 1H).

[0066] .sup.13C-NMR (50 MHz, CDCl.sub.3): δ (ppm) 12.60, 20.05, 24.52, 28.69, 28.87, 29.91, 31.82, 37.08, 67.41, 100.23, 132.70, 136.17.

[0067] MS [e/m (%)]: 224 (M+, 0.2), 209 (54), 137 (22), 121 (10), 115 (100), 109 (22), 93 (14), 91 (13), 79 (15), 77 (12), 67 (11), 55 (26), 43 (41), 41 (14).

[0068] IR (film, cm.sup.−1): 860m, 1034m, 1052m, 1100m, 1121m, 1162s, 1181s, 1225m, 1368w, 1457w, 2862w, 2930m, 2952m.

EXAMPLE 4

Preparation of 2-(3,3-dimethylcyclohex-1-enyl)-2,5,5-trimethyl-1,3-dioxane

[0069] 2-(3,3-dimethylcyclohex-1-enyl)-2,5,5-trimethyl-1,3-dioxane is prepared according to the protocol described in Example 1, using neopentyl glycol instead of ethylene glycol. The crude product, made up of 2-(3,3-dimethylcyclohex-1-enyl)-2,5,5-trimethyl-1,3-dioxane, is distilled under reduced pressure: its boiling point is 68° C. at 26.7 Pascal.
Olfactory description: amber, musky, red fruits.

[0070] The 2-(3,3-dimethylcyclohex-1-enyl)-2,5,5-trimethyl-1,3-dioxane thus obtained exhibits the following spectral characteristics:

[0071] .sup.1H-NMR (200 MHz, CDCl.sub.3): δ (ppm) 0.67 (s, 3H), 0.98 (s, 6H), 1.17 (s, 3H), 1.35 (s, 3H), 1.39-1.43 (m, 2H), 1.61-1.65 (m, 2H), 1.85 (t, J=6.1 Hz, 2H), 3.25-3.28 (m, 2H), 3.42-3.50 (m, 2H), 5.56 (s, 1H).

[0072] .sup.13C-NMR (50 MHz, CDCl.sub.3): δ (ppm) 20.05, 22.15, 22.70, 24.42, 28.07, 29.51, 29.94, 31.79, 37.09, 71.41, 100.29, 132.63, 135.89.

[0073] MS [e/m (%)]: 238 (M+, 0.4), 223 (45), 137 (20), 129 (100), 109 (24), 93 (15), 91 (14), 81 (12), 79 (14), 77 (12), 69 (28), 67 (14), 55 (13), 43 (57), 41 (24).

[0074] IR (film, cm.sup.−1): 859m, 1013m, 1039m, 1083s, 1121m, 1174s, 1207w, 1239w, 1369w, 1470w, 2864w, 2951m.

EXAMPLE 5

Preparation of 2-(3,3-dimethylcyclohex-1-enyl)-5,5-diethyl-2-methyl-1,3-dioxane

[0075] 2-(3,3-dimethylcyclohex-1-enyl)-5,5-diethyl-2-methyl-1,3-dioxane is prepared according to the protocol described in Example 1, using 2,2-diethyl-1,3-propanediol instead of ethylene glycol. The crude product, made up of 2-(3,3-dimethylcyclohex-1-enyl)-5,5-diethyl-2-methyl-1,3-dioxane, is distilled under reduced pressure: its boiling point is 78° C. at 40.0 Pascal.
Olfactory description: slightly animal.

[0076] The 2-(3,3-dimethylcyclohex-1-enyl)-5,5-diethyl-2-methyl-1,3-dioxane thus obtained exhibits the following spectral characteristics:

[0077] .sup.1H-NMR (200 MHz, CDCl.sub.3): δ (ppm) 0.72 (t, J=7.5 Hz, 3H), 0.72 (t, J=7.6 Hz, 3H), 0.98 (s, 6H), 0.98-1.05 (m, 1H), 1.26-1.32 (m, 1H), 1.32 (s, 3H), 1.32-1.42 (m, 2H), 1.58-1.73 (m, 4H), 1.82-1.87 (m, 2H), 3.36-3.45 (m, 4H), 5.56 (s, 1H).

[0078] .sup.13C-NMR (50 MHz, CDCl.sub.3): δ (ppm) 6.61, 7.50, 20.05, 22.58, 24.42, 24.48, 27.97, 29.93, 31.76, 34.22, 37.10, 68.38, 100.47, 132.79, 135.79.

[0079] MS [e/m (%)]: 208 (M+, 0.1), 134 (19), 133 (46), 132 (17), 121 (11), 119 (13), 110 (11), 109 (10), 108 (13), 107 (17), 97 (17), 96 (10), 95 (13), 93 (23), 92 (11), 91 (34), 81 (26), 80 (10), 79 (35), 77 (14), 67 (28), 57 (100), 55 (23), 53 (11), 41 (49), 39 (12).

[0080] IR (film, cm.sup.−1): 838w, 1365m, 1459m, 1726s, 2715w, 2866m, 2928s, 2951s.

EXAMPLE 6

Preparation of 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-4,7-dihydro-1,3-dioxepine

[0081] 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-4,7-dihydro-1,3-dioxepine is prepared according to the protocol described in Example 1, using cis-2-butene-1,4-diol instead of ethylene glycol. The crude product, made up of 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-4,7-dihydro-1,3-dioxepine, is distilled under reduced pressure: its boiling point is 75° C. at 53.3 Pascal.
Olfactory description: amber, spicy, nutmeg, incense.

[0082] The 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-4,7-dihydro-1,3-dioxepine thus obtained exhibits the following spectral characteristics:

[0083] .sup.1H-NMR (200 MHz, CDCl.sub.3): δ (ppm) 0.98 (s, 6H), 1.37-1.41 (m, 2H), 1.38 (s, 3H), 1.58-1.66 (m, 2H), 1.91-1.96 (m, 2H), 4.10-4.26 (m, 4H), 5.65 (t, J=1.1, 2H), 5.76 (s, 1H).

[0084] .sup.13C-NMR (50 MHz, CDCl.sub.3): δ (ppm) 19.98, 22.41, 24.44, 30.06, 31.55, 37.08, 61.49, 103.40, 129.63, 133.88, 134.33.

[0085] MS [e/m (%)]: 222 (M+, 0.1), 207 (15), 154 (33), 152 (22), 137 (58), 109 (62), 93 (14), 91 (14), 81 (18), 79 (16), 77 (14), 70 (10), 69 (13), 67 (27), 55 (14), 53 (13), 43 (100), 42 (19), 41 (38), 39 (29).

[0086] IR (film, cm.sup.−1): 613m, 625m, 640m, 787m, 877m, 949m, 1049s, 1082s, 1117m, 1153s, 1200w, 1231m, 1280m, 1371m, 1451w, 2861w, 2930m.

EXAMPLE 7

Perfuming Composition Containing the Derivatives Obtained in Examples 1 and 4

[0087] To a rose chord made according to the following table (Chord A) are added 2-(3,3-dimethylcyclohex-1-enyl)-2,5,5-trimethyl-1,3-dioxane (Example 4, Chords B and C) and 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-1,3-dioxolane (Example 1, Chord D).

TABLE-US-00001 Chord Chord Chord Chord Ingredients A B C D CITRONELLOL 90% 100 100 100 100 ALPHA DAMASCONE 10% DPG 20 20 20 20 DIMETHYLBENZYLCARBINYL 35 35 35 35 ACETATE EUGENOL RECT. 5 5 5 5 GERANIOL 95% 150 150 150 150 GERANYL ACETATE 50 50 50 50 CIS-3-HEXENOL 30 30 30 30 NEROL 90% 25 25 25 25 ROSE OXIDE 10 10 10 10 PHENYLETHYL 50 50 50 50 PHENYLACETATE PHENYLETHYL ALCOHOL 400 400 400 400 2-(3,3-DIMETHYLCYCLOHEX-1- — 25 50 — ENYL)-2,5,5-TRIMETHYL-1,3- DIOXANE (Example 4) 2-(3,3-DIMETHYLCYCLOHEX-1- — — — 25 ENYL)-2-METHYL-1,3- DIOXOLANE (Example 1) DIPROPYLENE GLYCOL—DPG 125 100 75 100
Generally, the addition of the molecules boosts the chord, making it more powerful.
The addition of 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-1,3-dioxolane (Example 1, Chord D) gives an aromatic, camphorated effect (the rose is less opulent) whereas the addition of the derivative 2-(3,3-dimethylcyclohex-1-enyl)-2,5,5-trimethyl-1,3-dioxane (Example 4, Chords B and C) reinforces the rose note, giving it a lovely natural effect . . . .
Finally, Chords B and C are more spicy, cinnamic, sweet. Chord C is however more dry woody/amber, the note is less rosy than with Chord B (less balanced), but the dry woody effect fits the composition well, lending power and a floral woody note, with a very pleasant balmy effect.

EXAMPLE 8

Perfuming Composition Containing the Derivatives Obtained in Examples 1 and 4

[0088] To an apple chord made according to the following table (Chord A) are added 2-(3,3-dimethylcyclohex-1-enyl)-2,5,5-trimethyl-1,3-dioxane (Example 4, Chords B and C) and 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-1,3-dioxolane (Example 1, Chord D).

TABLE-US-00002 Chord Chord Chord Chord Ingredients A B C D GAMMA UNDECALACTONE 100 100 100 100 AMYL ISOBUTYRATE 7 7 7 7 GALAXOLIDE ™ 50% MIP 225 225 225 225 ISOAMYL ACETATE 22 22 22 22 STYRALLYL ACETATE 8 8 8 8 TRIPLAL ™ 8 8 8 8 2-t-BUTYL-CYCLOHEXYL 523 523 523 523 ACETATE 50% DPG ETHYL METHYLVALERATE 22 22 22 22 VERTENOL ACETATE 30 30 30 30 2-(3,3-DIMETHYLCYCLOHEX-1- — 25 50 — ENYL)-2,5,5-TRIMETHYL-1,3- DIOXANE (Example 4) 2-(3,3-DIMETHYLCYCLOHEX-1- — — — 25 ENYL)-2-METHYL-1,3- DIOXOLANE (Example 1) DIPROPYLENE GLYCOL—DPG 55 30 5 30
Generally, the addition of the molecules boosts the chord, making it more powerful and more natural.
The addition of 2-(3,3-dimethylcyclohex-1-enyl)-2-methyl-1,3-dioxolane (Example 1, Chord D) gives a natural apple, with a peel, acidulous effect.
The addition of the derivative 2-(3,3-dimethylcyclohex-1-enyl)-2,5,5-trimethyl-1,3-dioxane (Example 4, Chords B and C) gives a juicy, sugary, crisp effect.

EXAMPLE 9

Perfuming Composition Containing the Derivative Obtained in Example 4

[0089] To a woody chord made according to the following table (Chord A) is added 2-(3,3-dimethylcyclohex-1-enyl)-2,5,5-trimethyl-1,3-dioxane (Example 4, Chord B).

TABLE-US-00003 Ingredients Chord A Chord B ORCANOX ™ 8 8 PENTADECENOLIDE 125 125 HELIOTROPINE CRIST. 10% DPG 6 6 SANDELA ™ 200 200 METHYL DIHYDRO JASMONATE 100 100 MANDARIN ESS. DIST. COLOURLESS 50 50 IONONE ALPHA 70 70 DEHYDRO 2 CAMPHOLENYL PENTANOL 4 4 DEHYDRO CAMPHOLENYL BUTANOL 110 110 OCTAHYDRO-TETRAMETHYL 250 250 ACETONAPHTONE PERFUMERY VANILLIN 10 10 DIPROPYLENE GLYCOL—DPG 67 42 2-(3,3-DIMETHYLCYCLOHEX-1- — 25 ENYL)-2,5,5-TRIMETHYL-1,3- DIOXANE (Example 4)
Chord B, powdery, is a little less vanilla, more woody and masculine.