IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS AND THEIR USE AS FRAGRANCE INGREDIENTS

Abstract

A compound represented by the formula I

##STR00001##

wherein
is indicating a double bond either at C4 or at C5, or single bonds,
R.sub.1, R.sub.2, R.sub.3, R.sub.4 are independently selected from H or Me, and
R.sub.5, R.sub.6 are independently selected from Me or Et,
and wherein the compound is not 9-hydroxy-5,9-dimethyldec-4-enal or 9-hydroxy-5,9-dimethyldecanal.

Said compounds are useful as perfume ingredients in personal care and household care products.

Claims

1. A compound according to formula I ##STR00013## wherein: represents a double bond either at C.sub.4 or at C.sub.5, or represents single bonds: R.sub.1, R.sub.2, R.sub.3, R.sub.4 are independently selected from H or Me; and, R.sub.5, R.sub.6 are independently selected from Me or Et, and wherein the compound is not 9-hydroxy-5,9-dimethyldec-4-enal or 9-hydroxy-5,9-dimethyldecanal.

2. A pro-perfume, adapted to provide the compound represented by the formula I ##STR00014## wherein: represents a double bond either at or at, or represents single bonds; R.sub.1, R.sub.2, R.sub.3, R.sub.4 are independently selected from H or Me, and R.sub.5, R.sub.6 are independently selected from Me or Et, and wherein the compound is not 9-hydroxy-5,9-dimethyldec-4-enal or 9-hydroxy-5,9-dimethyldecanal.

3. A compound according to formula I which is a perfume ingredient.

4. The perfume ingredient of claim 3 which has muguet odour characteristics.

5. A perfume composition comprising a compound according to the formula I.

6. A perfume composition according to claim 5 comprising one or more additional fragrance ingredients.

7. A perfume composition according to claim 5 that is free of Lyral™.

8. A muguet perfume composition according to claim 5.

9. A personal care product or household care product or fine fragrance comprising at least a compound of formula 1 of claim 1.

10. A method of imparting muguet odour characteristics to a personal care product or household care product or fine fragrance, said method comprising the step of: including therein a compound according to claim 1.

11. A perfume composition according to claim 5 which additionally comprises an anti-oxidant.

12. The pro-perfume of claim 2 which is an aminal and/or enamine of the compound of formula I.

13. The pro-perfume of claim 2 which is a perfume ingredient.

14. The pro-perfume of claim 2 which had muguet odour characteristics.

15. A perfume composition comprising a pro-perfume according to claim 2.

16. A perfume composition according to claim 6, where the additional fragrance ingredient is (E/Z)-9-hydroxy-5,9-dimethyldec-4-enal.

17. A personal care product or household care product or fine fragrance comprising at least a pro-perfume according to claim 2.

18. A personal care product or household care product or fine fragrance comprising a perfume composition according to claim 5.

19. A personal care product or household care product or fine fragrance comprising a perfume composition according to claim 6.

20. A personal care product or household care product or fine fragrance comprising a perfume composition according to claim 7.

Description

EXAMPLE 1

Preparation of 9-Hydroxy-4,6,9-trimethyldec-4-enal

1a) 2,4,7-Trimethylocta-1,6-dien-3-ol

[0092] ##STR00005##

[0093] The solution of 2,5-dimethylhex-4-enal (10.0 g, 79 mmol) in THF (40 ml) was added to solution of prop-1-en-2-ylmagnesium bromide (0.5 N in THF, 190 ml, 95 mmol, 1.2 equiv.) at 5-10° C. (icebath) and the resulting mixture was stirred at room temperature for 20 h. Saturated aq. NH.sub.4Cl solution was added dropwise until pH 4, then the mixture was partitioned between MTBE and water, the aqueous layer was extracted with MTBE and the combined organic layers washed with brine and dried over MgSO.sub.4. The solvent was removed and the residual crude oil distilled at 46° C./0.06 mbar to yield a colourless liquid (7.4 g, 56%; 2 diastereomers, ratio 56:44).

[0094] .sup.1H-NMR (CDCl.sub.3, 400 MHz): 5.23-5.11 (m, 1H), 4.98-4.83 (m, 2H), 3.90 (t, J=4.6 Hz, 0.56H), 3.80 (dd, J=7.6, 4.4 Hz, 0.44H), 2.25 (s, 1H), 2.32-2.22 (m, 0.44H), 2.07 (td, J=14.4, 6.5 Hz, 0.56H), 1.96-1.80 (m, 1H), 1.73-1.70 (m, 6H), 1.69-1.66 (m, 1H), 1.63 (br. s, 1.3), 1.62 (br. s, 1.7H), 0.87 (d, J=6.6 Hz, 1.7H), 0.81 (d, J=6.8 Hz, 1.3H). .sup.13C-NMR (CDCl.sub.3, 100 MHz): 146.8 (s), 146.5 (s), 132.7 (s), 132.7 (s), 122.9 (d), 122.8 (d), 112.5 (t), 111.1 (t), 80.9 (d), 78.7 (d), 36.6 (d), 36.2 (d), 32.2 (t), 30.5 (t), 25.9 (q), 25.8 (q), 18.5 (q), 17.8 (q), 17.8 (q), 17.3 (q), 16.2 (q), 13.5 (q). MS (EI, 70 eV, main isomer): 168 (M.sup.+, 2), 153 (2), 135 (5), 125 (6), 107 (21), 96 (24), 81 (21), 69 (35), 55 (100), 41 (50).

1b) 4,6,9-Trimethyldeca-4,8-dienal

[0095] ##STR00006##

[0096] The mixture of 2,4,7-trimethylocta-1,6-dien-3-ol (6.0 g, 35.7 mmol), ethoxy ethene (28.3 g, 392 mmol, 11 equiv) and phenyl phosphonic add (20 mg) was heated in an autoclave to 180° C. (14 bar) during 1 h, then concentrated under vacuum and the residue was purified by two flash chromatographies, the first eluting with hexane/EtOAc 79:1, then hexane/EtOAc 39:1 to yield 4,6,9-trimethyldeca-4,8-dienal (2.1 g, 30%) as a colourless oil, and 3-(1-ethoxyethoxy)-2,4,7-trimethylocta-1,6-diene (yellow oil, 4.9 g, 57%, E/Z isomers, ratio ca. 4:1).

4,6,9-Trimethyldeca-4,8-dienal

[0097] .sup.1H-NMR (CDCl.sub.3, 400 MHz): 9.77 (t, J=1.7 Hz, 0.2H), 974 (t, J=2.0 Hz, 0.8H), 5.13-5.02 (m, 1H), 5.01-4.94 (m, 1H), 2.54-2.45 (m, 2H), 2.40-2.27 (m, 3H), 2.00-1.84 (m, 2H), 1.69-1.66 (m, 3.5H), 1.61 (d, J=1.2 Hz, 2.5H), 1.58 (s, 3H), 0.91 (d, J=6.6 Hz, 0.6H), 0.90 (d, J=6.6 Hz, 2.4H). .sup.13C-NMR (CDCl.sub.3, 100 MHz): 202.7 (d), 202.3 (d), 133.2 (d), 132.1 (d), 132.1 (s), 131.9 (s), 131.3 (s), 131.1 (s), 122.9 (d), 42.6 (t), 42.1 (t), 35.9 (t), 35.8 (t), 33.0 (d), 32.9 (d), 31.9 (t), 25.8 (q), 24.5 (t), 23.1 (q), 20.9 (q), 20.5 (q), 17.8 (q), 16.2 (q). MS (EI, 70 eV, main isomer): 194 (M.sup.+, <1), 178 (<1), 125 (100), 107 (52), 97 (16), 91 (18), 83 (27), 69 (32), 55 (96), 41 (56).

1c) 9-Hydroxy-4,6,9-trimethyldec-4-enal

[0098] ##STR00007##

[0099] The solution of 4,6,9-trimethyldeca-4,8-dienal (0.50 g, 2.57 mmol) in CH.sub.2Cl.sub.2(7 ml) was cooled to 0° C., trifluoroacetic acid (1.47 g, 12.9 mmol, 5 equiv.) was added and the resulting mixture stirred at 0° C. for 80 min. Then concentrated aq. Na.sub.2CO.sub.3 solution was added until pH 8 was reached and the mixture was extracted with MTBE, the organic layer was washed with brine, dried over MgSO.sub.4 and concentrated in vacuo. The residue was dissolved in methanol and sodium methoxide (139 mg, 2.57 mmol, 1 equiv.) was added. The mixture was stirred for 1 h at room temperature, then diluted with water and extracted with MTBE. The organic layer was washed with water, 10% aq. AcOH and brine, dried over MgSO.sub.4 and concentrated in vacuo. The residue was purified by flash chromatography on SiO.sub.2 eluting with hexane/EtOAc 14:1 to obtain 9-hydroxy-4,6,9-trimethyldec-4-enal (slightly yellow oil, 37 mg, 7%, E/Z isomers, ratio ca. 4:1).

[0100] .sup.1H-NMR (CDCl.sub.3, 400 MHz): 9.77 (t, 3=1.7 Hz, 0.2H), 9.73 (t, 3=2.0 Hz, 0.8H), 4.91 (qd, 3=1.2, 9.5 Hz, 1H), 2.57-2.43 (m, 2H), 2.40-2.21 (m, 3H), 1.67 (d, 3=1.2 Hz, 0.6H), 1.60 (d, 3=1.5 Hz, 2.4H), 1.41-1.32 (m, 4H), 1.30-1.15 (m, 1H), 1.18 (2× br. s, 6H), 0.92 (d, 3=6.9 Hz, 0.6H), 0.91 (d, 3=6.9 Hz, 2.4H). .sup.13C-NMR (CDCl.sub.3, 100 MHz): 202.7 (d), 202.2 (d), 133.3 (d), 132.2 (d), 131.6 (s), 131.5 (s), 70.8 (s), 42.1 (t), 41.7 (t), 41.6 (t), 32.7 (d), 32.2 (t), 32.1 (t), 31.9 (t), 29.2 (q), 29.2 (q), 24.5 (t), 23.0 (q), 21.6 (q), 21.2 (q), 16.3 (q). MS (EI, 70 eV, main isomer): 194 ([M-H.sub.2O+], <1), 179 (1), 161 (8), 138 (28), 121 (13), 109 (75), 96 (100), 81 (32), 67 (22), 59 (65), 53 (61), 43 (65).

[0101] Odour description: lily of the valley, rosy, aldehydic.

EXAMPLE 2

Preparation of 9-Hydroxy-9-methyldec-4-enal

[0102] ##STR00008##

9-Methyldeca-4,8-dienal was prepared according to X. Wei, Xudong, J. C. Lorenz, S. A. Suresh, N. Haddad, C. A. Busacca, C. H. Senanayake, J. Org. Chem. 2007, 72(11), 4250-4253.

[0103] Formic acid (2.49 g, 54.1 mmol, 10 equiv.) was added at 0° C. to 9-methyldeca-4,8-dienal (0.9 g, 5.4 mmol) and the mixture was stirred at 0° C. for 6 h, then extracted with ethyl acetate. The organic layer was washed with water, sat. aq. NaHCO.sub.3 solution and brine, dried over MgSO.sub.4 and concentrated in vacuo. The residue was purified by flash chromatography on SiO.sub.2 eluting with hexane/EtOAc/EtOH 15:4:1 to yield 9-hydroxy-9-methyldec-4-enal (slightly yellow oil, 101 mg, 10%, R.sub.f=0.13, >99% E-isomer).

[0104] .sup.1H-NMR (CDCl.sub.3, 400 MHz): 9.76 (t, 3=1.6 Hz, 1H), 5.52-5.34 (m, 3H), 2.49 (td, 3=6.4, 0.8, 1H), 2.35 (q, 3=6.4, 1H), 2.05-1.95 (m, 2H), 1.46-1.32 (m, 4H), 1.28-1.17 (m, 2H), 1.21 (s, 6H). .sup.13C-NMR (CDCl.sub.3, 100 MHz): 202.4 (d), 131.7 (d), 128.1 (d), 70.9 (s), 43.5 (t), 43.3 (t), 32.9 (t), 29.2 (q), 25.2 (t), 24.1 (t). MS (EI, 70 eV, main isomer): 169 ([M−CH.sub.3.sup.+], <1), 151 (1), 133 (5), 122 (7), 110 (24), 82 (31), 67 (27), 59 (100), 55 (31), 43 (40).

[0105] Odour description: floral-green, lily of the valley, aldehydic.

EXAMPLE 3

Preparation of 9-Hydroxy-9-methyldecanal

[0106] ##STR00009##

3a: 2-Methyltridec-10-en-2-ol

[0107] A solution of methyl-9-dodecanoate (20 g, 94 mmol) in THF (150 ml) was cooled to 0° C. and a solution of methyl magnesiumchloride (109.9 ml, 3M in THF) was added while keeping the temperature below 31° C. The mixture was stirred for 1.5 h and poured into a saturated solution of NH.sub.4Cl (200 ml). The mixture was extracted twice with MTBE (200 ml) and the combined organic phases were washed with water (200 ml) and brine (200 ml), dried (MgSO.sub.4) and evaporated in vacuo to yield crude 2-methyltridec-10-en-2-ol (19.33 g, 97%).

3b: 9-Hydroxy-9-methyldecanal

[0108] A solution of 2-methyltridec-10-en-2-ol (8.3 g, 39.1 mmol, crude) in a mixture of dichloromethane (60 ml) and methanol (60 ml) was cooled to −75° C. Ozone was bubbled though the solution until the color changed to slightly blue. A stream of oxygen was bubbled though the solution until the blue color disappeared. The reaction flask was twice evacuated and flushed with nitrogen to remove oxygen and palladium on charcoal (0.2 g) was added. The temperature was allowed to rise to −25° C., the nitrogen atmosphere was replaced with hydrogen and the mixture was hydrogenated while keeping the temperature at below 30° C. with help of an ice bath. The solution was filtered, evaporated in vacuo and the residue was purified by chromatography on silica gel (eluent:hexane:MTBE 1:1) to yield 9-hydroxy-9-methyl decanal (2.5 g, 33%) as a colorless oil.

[0109] .sup.1H-NMR (CDCl.sub.3, 400 MHz): 9.76 (t, J=1.9 Hz, 1H), 3.66 (bs, 1H), 2.42 (dt, J=1.9, 7.4 Hz, 2H), 1.66-1.58 (m, 2H), 1.47-1.43 (m, 2H), 1.38-1.26 (m, 8H), 1.20 (s, 6H) ppm. .sup.13C-NMR (CDCl.sub.3, 100 MHz): 202.9 (d), 71.1 (s), 43.8 (2t), 29.9 (t), 29.1 (2q), 29.1 (t), 24.2 (2t), 22.0 (t) ppm. MS (EI, 70 eV): 171 ([M−CH.sub.3].sup.+6), 135 (2), 110 (3), 95 (9), 83 (5), 69 (7), 59 (100), 43 (23), 29 (8).

[0110] Odor description: fresh, floral, muguet.

EXAMPLE 4

Preparation of 9-Hydroxy-9-methylundecanal

[0111] ##STR00010##

[0112] This compound was synthesized according to the proceeding described in Example 3, using 1 equivalent of methyl magnesium chloride and 1 equivalent of ethyl magnesium bromide.

[0113] .sup.1H-NMR (CDCl.sub.3, 400 MHz): 9.77 (t, J=1.7 Hz, 1H), 3.52 (bs, 1H), 2.43 (dt, J=1.7, 7.3 Hz, 2H), 1.67-1.60 (m, 2H), 1.48 (qm J=7.6 Hz, 2H), 1.45-1.41 (m, 2H), 1.37-1.26 (m, 8H), 1.14 (s, 3H) 0.89 (t, J=7.6 Hz, 3H) ppm. .sup.13C-NMR (CDCl.sub.3, 100 MHz): 202.9 (d), 72.9 (s), 43.9 (t), 41.3 (t), 34.2 (t), 30.0 (t), 29.3 (t), 29.1 (t), 26.4 (q), 23.8 (t), 22.1 (t), 8.2 (q) ppm. MS (EI, 70 eV): 185 ([M−CH.sub.3].sup.+3), 171 (11), 135 (4), 95 (15), 83 (6), 73 (100), 55 (43), 43 (44), 29 (9).

[0114] Odor description: floral, muguet, aldehydic.

EXAMPLE 5

Preparation of 9-Hydroxy-5,9-dimethylundec-4-enal

5a: 5,9-Dimethylundeca-4,8-dienal

[0115] ##STR00011##

[0116] Ethyl Linalool (70.0 g, 416 mmol) and ethyl vinyl ether (90.0 g, 1248 mmol) were placed in an autoclave and phenyl phosphonic acid (1.0 g, 6 mmol) was added. The autoclave was flushed with nitrogen and sealed. The mixture was heated to 220° C. (10 bar) for 1.5 h. The reaction mixture was concentrated in vacuo and the residual crude oil was distilled at 75° C./0.05 bar to afford 5,9-dimethylundeca-4,8-dienal as a colorless liquid (41.1 g, 51%; mixture of E/Z-isomers).

[0117] .sup.1H-NMR (CDCl.sub.3, 400 MHz): 9.76 (m, 1H), 5.10 (m, 2H), 2.45 (m, 2H), 2.32 (m, 2H), 2.16-1.90 (m, 6H), 1.68 (m, 3H), 1.61 (m, 3H), 0.97 (m, 3H). .sup.13C-NMR (CDCl.sub.3, 100 MHz): 202.6, 202.5, 202.4, 137.5, 137.2, 137.0, 136.9, 136.8 (3s), 123.7, 122.8, 122.5, 122.4, 122.0 (2d), 44.2, 44.0, 39.9, 39.6, 32.3, 32.2, 32.0, 26.4, 26.3, 26.2, 26.1, 24, (4t), 23.3, 22.9, 22.8 (q), 20.8, 20.7 (t), 16.0, 15.9, 12.8, 12.7 (2q). MS (EI, 70 eV, main isomer): 194 (M.sup.+, 2), 137 (15), 93 (16), 83 (68), 82 (10), 81 (10), 67 (15), 55 (100), 41 (36), 39 (12).

5b: 9-Hydroxy-5,9-dimethylundec-4-enal

[0118] ##STR00012##

[0119] 5,9-Dimethylundeca-4,8-dienal (33.0 g, 170 mmol) was placed in a reactor and dichloromethane (500 ml) was added. The mixture was cooled to 0° C. and trifluoroacetic acid (97.0 g, 849 mmol) was added drop wise over 20 minutes while keeping the temperature below 5° C. 10 minutes after the addition GC analysis of the reaction mixture indicated complete conversion. The reaction mixture was poured onto saturated, aqueous sodium carbonate solution (300 ml) and stirred for 10 minutes. Water was added (300 ml) and the mixture was extracted with ether. The organic layers were combined, washed with water and brine, dried over MgSO.sub.4 and concentrated in vacuo. The residual oil (44.0 g) was mixed with methanol (500 ml). Sodium methoxide (10.1 g, 187 mmol) was added in portions over the period of 30 minutes at room temperature. The temperature was kept below 25° C. by gently cooling with an ice/water bath. After the addition the mixture was stirred at room temperature for 20 minutes. The reaction mixture was poured onto water (600 ml) and extracted with ether. The organic layers were washed with water and brine, dried over MgSO.sub.4 and concentrated in vacuo to afford the crude product (36.0 g). Short path distillation yielded a yellow oil (10.5 g) which was purified by flash chromatography over SiO.sub.2 using hexane/EtOAc 7:3 as the eluent. The purified product (7.8 g) was dissolved in acetone (150 ml) and treated with HCl 2M (5 ml). The solution was heated to 50° C. for 10 minutes to hydrolyse the dimethyl acetal present in the product. Water (300 ml) was added and the mixture extracted with ether. The layers were separated; the organic layer was washed with water and brine, dried over MgSO.sub.4 and concentrated in vacuo. The residue was distilled bulb to bulb at 140° C., 0.05 mbar to afford the product as a colorless oil (3.5 g, 10%, E/Z isomers, ratio ca. 2:3).

[0120] .sup.1H-NMR (CDCl.sub.3, 400 MHz): 9.74 (s, 1H), 5.09 (t, J=7.09 Hz, 1H), 2.44 (m, 2H), 2.31 (m, 2H), 2.02 (m, 1H), 1.95 (m, 1H), 1.66 (s, 1.2H), 1.60 (s, 1.8H), 1.51-1.31 (m, 7H), 1.12 (s, 3H), 0.91-0.84 (m, 3H). .sup.13C-NMR (CDCl.sub.3, 100 MHz): 202.2 (d), 137.0, 136.7 (s), 122.8, 122.1 (d), 72.7 (s), 44.1, 43.9, 41.0, 40.8, 40.0, 34.3, 34.2, 32.0 (4t), 26.35, 23.3 (q), 22.111, 22.0, 20.8, 20.6 (2t), 15.9, 8.2 (2q). MS (EI, 70 eV, main isomer): 194 (M.sup.+-H.sub.2O, 1), 124 (70), 107 (42), 96 (59), 95 (39), 81 (100), 73 (78), 68 (37), 55 (77), 43 (58).

[0121] Odor description: floral, watery, aldehydic