Organic compounds

Abstract

5,9-dimethyl-9-hydroxy-decen-4-al, having the formula (I) ##STR00001##

Claims

1. A personal care composition, a household care composition or a fine fragrance composition comprising the compound 5, 9-dimethyl-9-hydroxy-decen-4-al, having the formula (I) ##STR00008##

2. A personal care composition, a household care composition or a fine fragrance composition compounds according to formula (I) of claim 1, present in an E/Z isomer ratio of from 8:2 to 2:8.

3. A personal care composition, a household care composition or a fine fragrance composition comprising compounds according to claim 2, wherein the said personal care composition, a household care composition or a fine fragrance composition is free of cyclohexal.

4. A personal care composition, a household care composition or a fine fragrance composition according to claim 2, further comprising at least one adjuvant.

5. A personal care composition, a household care composition or a fine fragrance composition according to claim 4, wherein the at least one adjuvant is an anti-oxidant.

6. A method of imparting a muget odor note to a personal care composition, a household care composition or a fine fragrance composition, the method comprising the step of: adding to or including within the personal care composition, a household care composition or a fine fragrance composition compounds according to claim 2.

7. A personal care composition, a household care composition or a fine fragrance composition according to claim 1 further comprising one or more additional compounds selected from the group consisting of: 2-cyclohexylidene-2-phenylacetonitrile; 4-(octahydro-4,7-methano-5H-inden-5-ylidene)butanal; 4-Methyl-2-(2-methyl propyl)tetrahydro-2H-pyran-4-ol; and methyl 2-(2-hexyl-3-oxocyclopentyl)acetate.

8. A personal care composition, a household care composition or a fine fragrance composition according to claim 7 wherein 2-cyclohexylidene-2-phenylacetonitrile is present in 0.001 to 10 parts by weight per 1 part by weight 5, 9-dimethyl-9-hydroxy-decen-4-al.

9. A personal care composition, a household care composition or a fine fragrance composition according to claim 7 wherein 4-methyl-2-(2-methylpropyl)tetrahydro-2H-pyran-4-ol is employed in 0.001 to 20 parts by weight per 1 part by weight 5, 9-dimethyl-9-hydroxy-decen-4-al.

10. A personal care composition, a household care composition or a fine fragrance composition according to claim 7 wherein 4-(octahydro-4,7-methano-5H-inden-5-ylidene)butanal, is employed in 0.0001 to 0.5 parts by weight per 1 part by weight 5, 9-dimethyl-9-hydroxy-decen-4-al.

11. A personal care composition, a household care composition or a fine fragrance composition according to claim 7 wherein the 5, 9-dimethyl-9-hydroxy-decen-4-al compound is present in said perfume composition in an amount of 1 to 30% by weight based on the total weight of any of the said personal care composition, a household care composition or a fine fragrance composition.

12. A personal care composition, a household care composition or a fine fragrance composition according to claim 7 wherein methyl 2-(2-hexyl-3-oxocyclopentyl)acetate is present in an amount of 0.001 to 10 parts by weight per 1 part by weight of 5, 9-dimethyl-9-hydroxy-decen-4-al.

13. A personal care composition, a household care composition or a fine fragrance composition according to claim 1, further comprising at least one perfume ingredient.

14. A personal care composition, a household care composition or a fine fragrance composition according to claim 13, wherein said at least one perfume ingredient is not cyclohexal.

15. A personal care composition, a household care composition or a fine fragrance composition comprising a compound according to formula (I) of claim 1, wherein the said composition is free of cyclohexal.

16. A personal care composition, a household care composition or a fine fragrance composition according to claim 1, further comprising at least one adjuvant.

17. A personal care composition, a household care composition or a fine fragrance composition according to claim 16, wherein the at least one adjuvant is an anti-oxidant.

18. A process of forming a personal care composition, a household care composition or a fine fragrance composition, said process comprising the steps of: I) reacting hydroxylinalool with ethyl vinyl ether in acid under an inert gas atmosphere at 1 to 100 bar, and a temperature of () 10 to 200 degrees centigrade, to form a reaction mixture comprising acetals; II) acidifying the cooled reaction mixture at (20) to 40 degrees centigrade and atmospheric pressure to hydrolyse said acetals; III) neutralising the reaction mixture in a base before adjusting the pH of the reaction mixture to a slightly acidic pH of 2 to 7, to yield 5, 9-dimethyl-9-hydroxy-decen-4-al (I); and optionally IV) distilling the reaction mixture to isolate 5, 9-dimethyl-9-hydroxy-decen-4-al; and, V) incorporating the isolated 5, 9-dimethyl-9-hydroxy-decen-4-al within the personal care composition, or the household care composition or the fine fragrance composition.

19. A method of imparting a muget odor note to a personal care composition, a household care composition or a fine fragrance composition, the method comprising the step of: adding to or including within the personal care composition, a household care composition or a fine fragrance composition a compound according to formula (I) of claim 1.

Description

EXAMPLE 1

(E/Z)-5,9-dimethyl-9-hydroxy-decen-4-al (I)

a) 2,6-dimethyloct-7-yne-2,6-diol (2)

(1) The reactor was charged with water (1593 ml) and sulfuric acid (875 g, 8.7 mol) was added. The solution was cooled to 20 C. 3,7-dimethyloct-6-en-1-yn-3-ol (1, 2.45 kg, 16.1 mol) was added and the mixture was stirred at 25 C. for 48 hours.

(2) Water (1.5 l) and methyl tert.-butyl ether (1.6 l) was added and the mixture was stirred for 10 minutes. The layers were separated and the aqueous layer was extracted with methyl tert.-butyl ether (1.6 l). The organic layers were combined and washed with NaOH 2M (250 ml, pH 0), with saturated KHCO3 solution (700 ml, pH 8-9) and brine (800 ml). The solution was dried over MgSO4 and concentrated in vacuo. Residual 3,7-dimethyloct-6-en-1-yn-3-ol and volatile side products were removed by distillation over a 20 cm Vigreux column (b.p. 35-104 C. at 0.4 mbar). The crude product was wipe-film distilled (150 C. at 0.06 mbar) to afford (2) (1642 g, 69% yield) as a light yellow liquid. The product will crystallize upon standing. A sample was crystallized from hexane to afford white crystals, m.p. 48-49 C.

(3) 1H NMR: 3.36 (s, 1H); 2.40 (s, 1H); 2.20 (s, 1H); 1.67-1.39 (m, 6H); 1.43 (s, 3H); 1.16 (s, 6H). 13C NMR: 88.5 (s), 71.7 (d), 71.6, 68.1 (2s), 44.2, 44.0 (2t), 30.2, 29.6, 29.5 (3q), 19.8 (t).

(4) MS: 137 (10, M.sup.+-CH.sub.3, H.sub.2O), 109 (29), 79 (40), 77 (15), 71 (15), 69 (42), 66 (59), 59 (100), 56 (28), 43 (91), 41 (21).

b) 2,6-dimethyloct-7-ene-2,6-diol (3)

(5) A reactor equipped with an aeration stirrer was charged with 2,6-dimethyloct-7-yne-2,6-diol (2, 2.4 kg, 14.1 mol) and toluene (1.8 l). Palladium on activated carbon poisoned with lead (Lindlar catalyst, 25 g) was added and the reactor was flushed first with inert gas and then with hydrogen. The mixture was hydrogenated at 0.1-0.2 bar for 7.5 hours until the theoretical amount of hydrogen was consumed. Throughout the reaction the temperature was kept at 34-40 C. by means of a water bath. At the end of the reaction analysis by GC showed 6% over hydrogenated side product. The catalyst was removed by filtration and the toluene solution of (3) was used for the next synthetic step without further treatment. A sample of (3) was recrystallized from hexane for spectroscopic analysis, m.p. 46-47 C.

(6) 1H NMR: 5.83 (dd, J=17.4, 10.8, 1H); 5.12 (dd, J=17.4, 1.5, 1H); 4.95 (dd, J=10.8, 1.5, 1H); 2.29 (bs, 2H); 1.49-1.25 (m, 6H); 1.2 (s, 3H); 1.12 (s, 6H). 13C NMR: 145.6 (d), 111.9 (t), 73.6, 71.3 (2s), 44.5, 43.1 (2t), 29.6, 28.0 (3q), 19.0 (t).

(7) MS: 154 (1, M.sup.+-H.sub.2O), 121 (16), 81 (35), 71 (100), 69 (25), 68 (45), 59 (36), 56 (36), 55 (18), 43 (53), 41 (17).

c) (E/Z)-5,9-dimethyl-9-hydroxy-decen-4-al (I)

(8) In a pressure vessel with stirrer (Bchi, 5000 ml) a mixture of 2,6-dimethyloct-7-ene-2,6-diol in toluene (3, 2.25 l, 7 mol), from the previous hydrogenation reaction, ethyl vinyl ether (1.26 kg, 17 mol) and phenyl phosphonic acid (13 g, 82 mmol) were added. The autoclave was flushed and pre-pressurized to 2 bar with nitrogen and heated to 150 C. (pressure 4-6 bar) for 30 minutes. The temperature was then raised to 175 C. (pressure 8-10 bar) and maintained for 50 minutes. The reaction mixture was cooled and transferred to a 10 l jacketed reactor. Water (3 l) and HCl (2M, 300 ml) was added and the mixture was stirred at 50 C. until GC analysis showed the complete hydrolysis of the acetals of (I) in the mixture. The mixture was neutralized with saturated aqueous KHCO3 solution and the layers were separated. The aqueous layer was extracted with MtBE, the organic layers were combined and washed with acetic acid (10%, 500 ml) dried over MgSO.sub.4 and concentrated in vacuo. The crude product was wipe-film distilled (150 C., 0.06 mbar) to afford (I) (1077 g, 78% yield) as a light orange liquid.

(9) The crude material was distilled over a 50 cm, 1 diameter column with Sulzer packing (b.p. 109 C., 0.05 mbar) to afford olfactively pure (I) (514 g, 37% yield). Refractive index

(10) 1H NMR; mixture of E/Z isomers: 9.73 (t, J=1.77, 1H); 9.72 (t, J=1.77, 1H); 5.07 (t, J=7.07, 2H); 2.46-2.40 (m, 4H); 2.34-2.25 (m, 4H); 2.01 (m, 2H); 1.94 (m, 2H); 1.65 (q, J=1.27, 3H); 1.61 (bs, 2H (OH)); 1.59 (bs, 3H); 1.48-1.32 (m, 8H); 1.18 (s, 6H); 1.17 (s, 6H). 13C NMR; mixture of E/Z isomers: 203.0, 202.9 (2d), 137.3, 137.2 (2s), 123.2, 122.5 (2d), 71.2, 71.1 (2s), 44.5, 44.3, 44.0, 43.7, 40.3, 32.4 (6t), 29.6 (4q), 23.6 (q), 23.0, 22.9, 21.2, 21.0 (4t), 16.3 (q).

(11) MS; sum of E/Z isomers: 180 (1, M.sup.+-H.sub.2O), 96 (33), 93 (27), 81 (82), 69 (44), 68 (55), 67 (39), 59 (100), 55 (55), 43 (64), 41 (59).

(12) Odour: floral, green, muguet, hydroxy citronellal aspect

(13) The reported NMR spectra were measured in CDCl.sub.3 at 400 MHz if not otherwise stated; chemical shifts are reported in ppm downfield from TMS; coupling constants J in Hz. The GC/MS analyses were run using a ZB-5 column, if not stated otherwise. All purified products were either crystallized and isolated as white solids or purified by distillation in vacuo and isolated as colorless oils, the purity was confirmed by GC/MS. Samples for olfactory evaluation were purified by rectification over a distillation column with Sulzer packing.

EXAMPLE 2

(14) In this example, the methodology of Example 27 of GB 981,702 was followed and the product isolated and characterised.

(15) Crystalline hydroxy linalool (171 g, 0.993 mol, m.p. 46-47 C.) was dissolved in ethyl vinyl ether (240 g, 3.325 mol) and placed in a PARR autoclave. Phosphoric acid (0.6 g) was added and the mixture was heated at 180 C. for 30 minutes. The mixture was cooled to room temperature, neutralized with triethylamine (2.4 ml) and concentrated in vacuo (100 C., 14 mm). The residue (205.6 g) was added to a mixture of sodium sulfite (500 g) and water (2000 ml) and stirred for 1 hour. The pH was set to 7 by adding acetic acid (2 g) and the mixture was then extracted with MtBE three times. The combined ether extracts were concentrated in vacuo to afford the non-aldehydic constituents (90.6 g) In the patent the inventors reported 44 g of non-aldehydic material. The aqueous layer was treated with NaOH 30% (1000 ml) while cooling the mixture with an ice/water bath. The mixture (pH 14) was then extracted three times with MtBE, the organic layers were combined, washed with sodium bicarbonate solution and concentrated. The dark viscous residue (91.3 g), in the patent the inventors reported 182 g, was dissolved in acetone (500 ml) and 10% sulfuric acid (200 ml) was added. The mixture was left standing over night. The mixture was then diluted with water (2000 ml) and extracted five times with MtBE. The combined ether extracts were washed with sodium bicarbonate and concentrated in vacuo. The crude material was purified by distillation (bp. 85 C., 0.5 mbar) to afford a equally distributed mixture of (E/Z)-5,9-dimethyldeca-4,8-dienal and (E/Z)-5,9-dimethyldeca-4,9-dienal (5.66 g, 3.16% yield). Refractive index: n.sub.D.sup.20 1.4682

(16) Odour: Fruity, apple, citrus, fatty, aldehydic, metallic, slightly hot iron, long lasting

(17) 1H NMR; mixture isomers: 9.76 (q, J=1.77, 4H); 5.14-5.04 (m, 6H); 4.69 (m, 4H); 2.45 (m, 8H); 2.33 (m, 8H); 2.11-1.93 (m, 16H); 1.74-1.66 (m, 18H); 1.64-1.59 (m, 12H); 1.57-1.47 (m, 4H). 13C NMR; mixture of isomers: 202.92, 202.85, 202.83, 202.79 (4d), 146.23, 146.07 (2s), 137.41, 137.29, 137.21 (4s), 132.11, 131.83 (2s), 124.47, 124.42, 123.21, 123.18, 122.48, 122.40 (6d), 110.27, 110.20 (2t), 44.55, 44.35, 44.32, 39.99, 39.54, 37.98, 37.69, 32.29, 31.75, 26.95, 26.80, 26.23, 26.19 (14t), 26.07, 26.03, 23.70, 23.69, 22.76 (6q), 21.24, 21.21, 21.07, 21.03 (4t), 18.04, 18.00, 16.40, 16.31 (4q).

(18) MS 5,9-dimethyldeca-4,9-dienal; sum of E/Z isomers: 180 (1, M.sup.+-H.sub.2O), 96 (55), 81 (100), 79 (34), 69 (41), 68 (97), 67 (66), 55 (95), 53 (35), 41 (95), 39 (37).

(19) MS 5,9-dimethyldeca-4,8-dienal; sum of E/Z isomers: 180 (1, M.sup.+-H.sub.2O), 137 (1), 136 (1), 93 (14), 69 (100), 67 (11), 55 (24), 53 (11), 43 (1), 41 (66), 39 (11).

EXAMPLE 3

(20) To a 1000 mL multi-necked flask fitted with stirrer, condenser and dropping funnel is charged a solution of 180 g hydroxylinalool in 180 g toluene; 0.9 g phosphoric acid (85%); and 0.3 g triethanolamine. The flask is heated to 125 C. with stirring, and 150 g diethyleneglycol divinylether is added over 2 hours, and the mixture stirred whilst maintaining this temperature. After addition, 10 g of toluene is added to the flask and the mixture is stirred for a further 2.5 hours at the same temperature. Thereafter, the reaction mixture is washed 3 times at 70 C. with a solution of 10 g sodium chloride in 120 g water. After washing with 10% aqueous solution of Sodium bicarbonate and water, toluene is distilled off and the residue fractionated in vacuo to yield (E&Z)-9-hydroxy-5,9-dimethyldec-4-enal as a colorless to pale yellow oil.

EXAMPLE 4

(21) Sodium metabisulphite (9.59 g) was dissolved in water and 9-hydroxy-5,9-dimethyldec-4-enal (10 g) was added thereto. Ethanol (10 ml) was added to the solution and the mixture became turbid. The mixture was stirred for 30 minutes at room temperature. GC analysis of the organic material showed that almost all aldehyde was in the water phase in the form of its sulphonate adduct. The mixture was stirred for a further 30 minutes before adding 50 ml of MtBE. The layers were separated and the aqueous layer was extracted another 2 times with 10 ml MtBE. The pH of the aqueous phase was 4.4. A portion was taken, freeze dried and subjected to analysis:

(22) 1H NMR (MeOD); mixture of E/Z isomers: 5.19 (t, J=7.09, 2H); 4.25 (m, 2H); 2.32-1.94 (m, 10H); 1.77 (m, 2H); 1.71 (s, 3H); 1.65 (s, 3H); 1.46 (m, 8H); 1.18 (s, 12H). 13C NMR (MeOD); mixture of E/Z isomers: 136.0, 135.8 (2s), 124.0, 123.3 (2d), 83.4 (2d), 70.1 (2s), 43.1, 43.0, 39.9, 31.7, 31.4 (6t), 27.8 (4q), 23.7, 22.4, 22.3 (4t), 22.2, 14.66 (2q). mp>84 C. decomposition.

(23) Thereafter, to the remaining sample, sodium carbonate 15% in water was added in portions. An evolution of gas indicated that the sulphonate had decomposed. The pH was 7.1. More sodium carbonate was added in portions until the mixture reached a pH of 9.45, before the mixture was warmed to 40 C. for 30 minutes. The slightly basic aqueous solution was worked up by extraction with MtBE, and the organic phases were combined, washed with 10% acetic acid, dried and concentrated to yield 9-hydroxy-5,9-dimethyldec-4-enal once again.

EXAMPLE 5

(24) TABLE-US-00001 INGREDIENT/% Cpd (I) FLOROSA DUPICAL PEONILE PERFUME 80 20 COMPOSITION 1 PERFUME 80 19.99 0.01 COMPOSITION 2 PERFUME 80 19.90 0.1 COMPOSITION 3

(25) Application in Fine Fragrance

(26) Two fine fragrances, one male-type and one female-type containing cyclohexal were used as comparative formulations.

(27) Both the male-type and the female-type fragrances were modified by removing cyclohexal and replacing it with equal amounts of the perfume compositions set forth in the above table to provide three modified male-type fragrances and three modified female-type fragrances.

(28) The modified fragrances and the comparative formulations were each placed on a blotter. The odour characteristics of the modified fragrances and the comparative formulations were assessed by a panel of trained perfumers immediately and after 4 hours evaporation.

(29) All modified fragrances were assessed to have remarkably similar odour characteristics as the comparative formulations, demonstrating the perfume formulae set forth in the table are suitable as replacers for cyclohexal in a fine perfumery setting.

(30) Application in Fabric Softener

(31) An unperfumed fabric softener base was perfumed with cyclohexal to form a comparative formulation and with similar quantities each of the perfume compositions set forth in the above table to produce test formulations. The perfumed fabric softener compositions were diluted in water and the odour characteristics of these diluted compositions were assessed by a panel of trained perfumers.

(32) From the panel assessment it was found that the tests formulations exhibited remarkably similar odour characteristics to the comparative formulation, demonstrating the perfume formulae set forth in the table are suitable as replacers for cyclohexal in a fabric softener setting.

(33) Application in Shower Gel

(34) An unperfumed shower gel base was perfumed with cyclohexal to form a comparative formulation and with similar quantities each of the perfume compositions set forth in the above table to produce test formulations. The perfumed shower gel compositions were diluted in water and the odour characteristics of these diluted compositions were assessed by a panel of trained perfumers.

(35) From the panel assessment it was found that the tests formulations exhibited remarkably similar odour characteristics to the comparative formulation, demonstrating the perfume formulae set forth in the table are suitable as replacers for cyclohexal in a shower gel setting.

(36) Application in Shampoo

(37) An unperfumed shampoo base was perfumed with cyclohexal to form a comparative formulation and with similar quantities each of the perfume compositions set forth in the above table to produce test formulations. The thus perfumed shampoo compositions were diluted in water and the odour characteristics of these diluted compositions were assessed by a panel of trained perfumers.

(38) From the panel assessment it was found that the tests formulations exhibited remarkably similar odour characteristics to the comparative formulation, demonstrating the perfume formulae set forth in the table are suitable as replacers for cyclohexal in a shampoo setting.

EXAMPLE 6

(39) In the following perfume formulation 5,9-dimethyl-9-hydroxy-decen-4-al or the mixture described in Example 5, and cyclohexal (Lyra)) are interchangeable ingredients. 5,9-Dimethyl-9-hydroxy-decen-4-al adds, like cyclohexal, to the body, diffusivity and radiance of the fragrance composition.

(40) TABLE-US-00002 NIRVANOLIDE 329925-33-9 15.00 DIPROPYLENE GLYCOL 25265-71-8 1 3.96 CEPIONATE 24851-98-7 13.00 BENZYL SALICYLATE 118-58-1 10.00 SERENOLIDE 477218-42-1 9.00 FLORYMOSS 681433-04-5 9.00 GEORGYWOOD 185429-83-8 7.50 ISORALDEINE CETONE ALPHA 1335-46-2 4.50 TROPIONAL 1205-17-0 3.50 FLORHYDRAL 125109-85-5 1.00 ISOEUGENOL ACETATE CRYSTAL 93-29-8 0.90 CASHMERAN 33704-61-9 0.90 DECALACTONE GAMMA 706-14-9 0.35 PEACH PURE 104-67-6 0.30 NEOCASPIRENE EXTRA 89079-92-5 0.25 INDOLENE 50%/CASTOR OIL 0.20 AMBROFIX 6790-58-5 0.20 ETHYL VANILLIN 121-32-4 0.15 CYCLAL C 68039-49-6 0.14 DAMASCONE ALPHA 24720-09-0 0.09 FILBERTONE 10%/TEC 0.04 OXANE 50%/TEC 0.02 5, 9-Dimethyl-9-hydroxy-decen-4-al-- 10.00 100.00

EXAMPLE 7

(41) In the following perfume formulation 5,9-dimethyl-9-hydroxy-decen-4-al or the mixture described in Example 5, and cyclohexal (Lyral) are interchangeable ingredients. 5,9-Dimethyl-9-hydroxy-decen-4-al adds, like cyclohexal, to the body, diffusivity and radiance of the fragrance composition

(42) TABLE-US-00003 AMBROFIX 6790-58-5 0.20 BENZYL SALICYLATE 118-58-1 10.00 CASHMERAN 33704-61-9 0.90 CEPIONATE 24851-98-7 13.00 CYCLAL C 68039-49-6 0.14 DAMASCONE ALPHA 24720-09-0 0.09 DECALACTONE GAMMA 706-14-9 0.35 DIPROPYLENE GLYCOL 25265-71-8 13.96 ETHYL VANILLIN 121-32-4 0.15 FILBERTONE 10%/TEC 0.04 FLORHYDRAL 125109-85-5 1.00 FLORYMOSS 681433-04-5 9.00 GEORGYWOOD 185429-83-8 7.50 INDOLENE 50%/CASTOR OIL 0.20 ISOEUGENOL ACETATE CRYSTAL 93-29-8 0.90 ISORALDEINE CETONE ALPHA 1335-46-2 4.50 NEOCASPIRENE EXTRA 89079-92-5 0.25 NIRVANOLIDE 329925-33-9 15.00 OXANE 50%/TEC 0.02 PEACH PURE 104-67-6 0.30 SERENOLIDE 477218-42-1 9.00 5, 9-Dimethyl-9-hydroxy-decen-4-al-- 10.00 TROPIONAL 1205-17-0 3.50 100.00