Organic compounds

Abstract

The present invention refers to 3,7-dimethyloct-6-en-1-yl methyl carbonate and its use as fragrance ingredient. The invention further refers to fragrance compositions and fragranced articles including it.

Claims

1. A method comprising utilizing 3,7-dimethyloct-6-en-1-yl methyl carbonate as a fragrance; the method comprising mixing 3,7-dimethyloct-6-en-1-yl methyl carbonate alone, as stereoisomeric mixture, or in combination with a base material.

2. A fragrance composition comprising: a) 3,7-dimethyloct-6-en-1-yl methyl carbonate; and b) at least one compound selected from 3,7-dimethyloct-7-en-1-yl methyl carbonate, (E)-3,7-dimethylocta-2,6-dien-1-yl methyl carbonate, (Z)-3,7-dimethylocta-2,6-dien-1-yl methyl carbonate and methyl phenethyl carbonate, and mixtures thereof.

3. The fragrance composition according to claim 2 comprising a mixture consisting essentially of 50-95 weight % of 3,7-dimethyloct-6-en-1-yl methyl carbonate, 5-50 weight % of 3,7-dimethylocta-2,6-dien-1-yl methyl carbonate, up to 20 weight % of 3,7-dimethyloct-7-en-1-yl methyl carbonate, and up to 20 weight % of methyl phenethyl carbonate.

4. A fragranced article comprising: a) 3,7-dimethyloct-6-en-1-yl methyl carbonate; b) a consumer product base; and optionally c) at least one compound selected from 3,7-dimethyloct-7-en-1-yl methyl carbonate, (E)-3,7-dimethylocta-2,6-dien-1-yl methyl carbonate, (Z)-3,7-dimethylocta-2,6-dien-1-yl methyl carbonate and methyl phenethyl carbonate, and mixtures thereof.

5. The fragranced article according to claim 4 wherein the consumer product base is selected from fine fragrance, household products, laundry products, body care products, cosmetic and air care products.

6. The fragranced article according to claim 5 wherein the consumer product base is fine fragrance.

7. A fragranced article comprising: a) 3,7-dimethyloct-6-en-1-yl methyl carbonate; b) a consumer product base; and c) at least one compound selected from 3,7-dimethyloct-7-en-1-yl methyl carbonate, (E)-3,7-dimethylocta-2,6-dien-1-yl methyl carbonate, (Z)-3,7-dimethylocta-2,6-dien-1-yl methyl carbonate and methyl phenethyl carbonate, and mixtures thereof.

8. The fragranced article according to claim 7 wherein the consumer product base is selected from fine fragrance, household products, laundry products, body care products, cosmetic and air care products.

9. The fragranced article according to claim 8 wherein the consumer product base is fine fragrance.

10. A method of improving, enhancing or modifying a consumer product base; the method comprising adding an olfactory acceptable amount of 3,7-dimethyloct-6-en-1-yl methyl carbonate to the consumer product base.

11. The method according to claim 10, further adding there to at least one compound selected from 3,7-dimethyloct-7-en-1-yl methyl carbonate, (E)-3,7-dimethylocta-2,6-dien-1-yl methyl carbonate, (Z)-3,7-dimethylocta-2,6-dien-1-yl methyl carbonate and methyl phenethyl carbonate, and mixtures thereof.

Description

EXAMPLE 1: PREPARATION OF 3,7-DIMETHYLOCT-6-EN-1-YL METHYL CARBONATE

(1) A solution of racemic Citronellol (3,7-dimethyloct-6-en-1-ol; 20.0 g, 128 mmol. 1 equiv.), pyridine (30.4 g, 384 mmol, 3 equiv) and 4-dimethylamino pyridine (0.4 g, 3.3 mmol, 2.5 mol %) in toluene (300 mL) was cooled to 10° C. Then a solution of methyl chloroformate (24.2 g, 256 mmol, 2.0 equiv.) in toluene (100 mL) was added dropwise over 15 min at an inside temperature of 15-18° C. The resulting white suspension was stirred at room temperature during 20 h, then cooled to 5° C. by means of an icebath before the addition of 2 N aqueous HCl-solution (220 mL, 440 mmol). The resulting biphasic mixture was stirred intensely at room temperature for 10 min., then the phases were separated and the aqueous layer was extracted with toluene. The combined organic layers were washed with water, then saturated aqueous NaHCO.sub.3-solution and finally three times with brine, dried over MgSO.sub.4 and concentrated in a rotatory evaporator under reduced pressure to yield a colorless liquid (28.8 g). The crude product was purified by a short path distillation over a 5 cm Vigreux column at 86° C./0.02 mbar followed by a second fine distillation over a 15 cm Widmer column at 82° C./0.02 mbar to yield the olfactorily pure product as a colorless oil (14.8 g, 54%) exhibiting a fruity-rosy odor with hints of pear and citronella.

(2) .sup.1H-NMR (400 MHz, CDCl.sub.3) 5.08 (m, 1H), 4.10-4.25 (m, 2H), 3.77 (s, 3H), 1.88-2.10 (m, 2H), 1.68-1.77 (m, 1H), 1.68 (d, J=1.0 Hz, 3H), 1.60 (s, 3H), 1.13-1.58 (series of m, 4H), 0.92 (d, J=6.6 Hz, 3H).

(3) .sup.13C-NMR (100 MHz, CDCl.sub.3) 155.8 (s), 131.3 (s), 124.5 (d), 66.6 (t), 54.5 (q), 36.9 (t), 35.5 (t), 29.2 (d), 25.7 (q), 25.3 (t), 19.3 (q), 17.6 (q).

EXAMPLE 2: PREPARATION OF (E)-3,7-DIMETHYLOCTA-2,6-DIEN-1-YL METHYL CARBONATE

(4) The procedure described in Example 1 was repeated with Geraniol ((E)-3,7-dimethylocta-2,6-dien-1-ol; 98% pure, 97 mmol). The crude product (colourless oil, 20.2 g) was purified by a short path distillation over a 10 cm Vigreux column at 91° C./0.02 mbar followed by a second fine distillation over a 15 cm Widmer column at 80-82° C./0.02 mbar to yield the olfactorily pure product as a colorless oil (10.0 g, 49%) exhibiting a fruity-rosy odor with a pear facet.

(5) .sup.1H-NMR (400 MHz, CDCl.sub.3) 5.32-5.42 (m, 1H), 5.03-5.11 (m, 1H), 4.58-4.68 (m, 2H), 3.76 (s, 3H), 1.98-2.17 (m, 4H), 1.71 (d, J=0.7 Hz, 3H), 1.67 (d, J=1.2 Hz, 3H), 1.59 (d, J=0.7 Hz, 3H).

(6) .sup.13C-NMR (100 MHz, CDCl.sub.3) 155.8 (s), 143.1 (s), 131.8 (s), 123.6 (d), 117.7 (d), 64.6 (t), 54.5 (q), 39.5 (t), 26.2 (t), 25.6 (q), 17.6 (q), 16.4 (q).

EXAMPLE 3: PREPARATION OF METHYL PHENETHYL CARBONATE

(7) The procedure described in Example 1 was repeated with 2-phenyl ethanol (164 mmol). The crude product (colourless oil, 29.7 g) was purified by a short path distillation over a 10 cm Vigreux column at 73-82° C./0.02 mbar followed by a second fine distillation over a 15 cm Widmer column at 81-82° C./0.02 mbar to yield the olfactorily pure product as a colorless oil (15.7 g, 53%) exhibiting a rosy-floral odor with a slight mushroom facet.

(8) .sup.1H-NMR (400 MHz, CDCl.sub.3) 7.32-7.38 (m, 2H), 7.25-7.31 (m, 3H), 4.39 (t, J=7.2 Hz, 2H), 3.80 (s, 3H), 3.02 (t, J=7.2 Hz, 2H).

(9) .sup.13C-NMR (100 MHz, CDCl.sub.3) 155.7 (s), 137.3 (s), 129.0 (d), 128.6 (d), 126.7 (d), 68.4 (t), 54.7 (q), 35.2 (t).

EXAMPLE 4: PREPARATION OF 3,7-DIMETHYLOCT-7-EN-1-YL METHYL CARBONATE

(10) To a solution of 3,7-dimethyloct-7-en-1-ol (2.4 g, 15.4 mmol; prepared according to G. Yu. Ishmuratov, M. P. Yakovleva, A. V. Galyautdinova, L. V. Faifer, R. Ya. Kharisov, V. V. Zorin, G. A. Tolstikov, Chemistry of Natural Compounds—translation of Khimiya Prirodnykh Soedinenii, 37, 5, 486-489), pyridine (2.19 g, 27.6 mmol, 1.8 equiv.) and 4-dimethylamino pyridine (0.19 g, 1.54 mmol, 0.1 equiv.) in cyclohexane (50 mL) was added dropwise over 25 min a solution of methyl carbonochloridate (2.18 g, 23.0 mmol, 1.5 equiv.). The temperature rose from 24° C. to 45° C. The resulting white suspension was stirred for 1 h at 24° C., then poured onto aqueous 2 M HCl-solution (50 mL). The aqueous layer was extracted twice with methyl t-butyl ether (MTBE) and the combined organic layers were washed with water and brine, dried over MgSO.sub.4 and concentrated in a rotatory evaporator under reduced pressure to yield a colorless liquid (2.8 g, 84%). The crude product was purified by automated flash column chromatography over a prepacked SiO.sub.2-cartridge with a gradient from 2-100% MTBE in hexane. The resulting product was bulb-to-bulb distilled at 80° C./0.05 mbar to yield analytically and olfactorily pure 3,7-dimethyloct-7-en-1-yl methyl carbonate (1.19 g, 36%) as a colorless oil exhibiting a fruity-rosy odor with pear and banana connotations.

(11) .sup.1H-NMR (400 MHz, CDCl.sub.3) 4.68-4.71 (m, 1H), 4.64-4.67 (m, 1H), 4.11-4.23 (m, 2H), 3.77 (s, 3H), 1.98 (br. t, J=7.6 Hz, 2H), 1.70 (br. s, 3H), 1.67-1.75 (m, 1H), 1.26-1.64 (m, 5H), 1.09-1.21 (m, 1H), 0.91 (d, J=6.6 Hz, 3H).

(12) .sup.13C-NMR (100 MHz, CDCl.sub.3) 155.9 (s), 145.9 (s), 109.8 (t), 66.6 (t), 54.6 (q), 37.9 (t), 36.4 (t), 35.5 (t), 29.5 (d), 24.8 (t), 22.3 (q), 19.4 (q).

EXAMPLE 5: PREPARATION OF METHYL CARBONATE MIXTURE FROM A MIXTURE OF ALCOHOLS

(13) The procedure described in Example 1 was repeated with a mixture of rac. Citronellol (38.5 g, 247 mmol), Geraniol (98%, 10.8 g, 70 mmol) and 2-phenyl ethanol (0.75 g, 6 mmol). The crude product (colorless oil, 29.7 g) was purified by 2 consecutive short path distillations over a 10 cm Vigreux column, the first one at 85-86° C./0.05 mbar and the second at 102° C./0.3 mbar to yield the olfactorily pure product as a colorless oil (29.3 g). It consists according to GC-MS analysis of 76.2% 3,7-dimethyloct-6-en-1-yl methyl carbonate, 20.7% (E)-3,7-dimethylocta-2,6-dien-1-yl methyl carbonate, 1.6% 3,7-dimethyloct-7-en-1-yl methyl carbonate and 1.4% Methyl phenethyl carbonate. The product exhibited a very natural fruity floral fragrance reminiscent of rose petals and pear.

EXAMPLE 6: PREPARATION OF A METHYL CARBONATE MIXTURE FROM CITRONELLOL AND GERANIOL

(14) The procedure described in Example 4 was repeated with a mixture of rac. Citronellol (10.0 g, 64 mmol) and Geraniol (98%, 9.87 g, 64 mmol). Of the crude product (colorless oil, 20.8 g), a part (3.0 g) was purified by automated flash column chromatography over a prepacked SiO.sub.2-cartridge with a gradient from 2-100% MTBE in hexane. The resulting product was bulb-to-bulb distilled at 100° C./0.05 mbar to yield analytically and olfactorily pure product (0.95 g colorless liquid) which consisted according to GC-MS analysis of 80% 3,7-dimethyloct-6-en-1-yl methyl carbonate, 19% (E)-3,7-dimethylocta-2,6-dien-1-yl methyl carbonate and 1% 3,7-dimethyloct-7-en-1-yl methyl carbonate. The product exhibited a fruity-rosy odour with pear aspects.

EXAMPLE 7: PREPARATION OF (E,Z)-3,7-DIMETHYLOCTA-2,6-DIEN-1-YL METHYL CARBONATE

(15) The procedure as described in Example 2 was repeated with a mixture of geraniol/nerol ((E)-3,7-dimethylocta-2,6-dien-1-ol/(Z)-3,7-dimethylocta-2,6-dien-1-ol in a ratio of 3:2; 100 mmol). The crude product (colourless oil, 20 g) was purified by a short path distillation over a 10 cm Vigreux column at 91° C./0.02 mbar followed by a second fine distillation over a 15 cm Widmer column at 90° C./0.06 mbar to yield the olfactorily pure product as a colourless oil (12.5 g, 59%). The product exhibited a fruity, floral, rosy odour.

(16) NMR spectra (E/Z mixture):

(17) 1H-NMR (400 MHz, CDCl3) 5.39 (dddt, J=7.1, 5.8, 2.8, 1.3, 1.3 Hz, 1H), 5.05-5.14 (m, 1H), 4.67 (d, J=7.3 Hz, 1.4H), 4.63 (dd, J=7.3, 0.8 Hz, 0.6H), 3.79 (s, 2.1H), 3.78 (s, 0.9H), 2.02-2.19 (m, 4H), 1.78 (d, J=1.0 Hz, 0.9H), 1.73 (d, J=0.8 Hz, 2.1H), 1.69 (s, 3H), 1.61 (s, 3H).

(18) 13C-NMR (100 MHz, CDCl3) 156.3 (s), 143.7 (s), 143.6 (s), 132.6 (s), 132.2 (s), 124.1 (d), 123.9 (d), 119.1 (d), 118.1 (d), 65.1 (t), 64.8 (t), 55.0 (q), 55.0 (q), 39.9 (t), 32.6 (t), 27.0 (t), 26.6 (t), 26.0 (q), 23.9 (q), 18.0 (q), 18.0 (q), 16.9 (q).

EXAMPLE 8: DETERMINATION OF GC-ODOR THRESHOLD VALUES

(19) According to standard procedures known to the person skilled in the art, threshold values for volatile perfumery compounds are determined on a gas chromatograph equipped with a sniff port by a panel of trained evaluators. The lowest concentration smelled by each panelist is recorded as the individual threshold value expressed in ng (absolute amount of compound delivered at the sniff port).

(20) Under identical conditions the odour threshold value for the individual compounds was measured. The results are given below.

(21) TABLE-US-00001 Number odour threshold value [ng] Compound of panelists geometric mean Citronellol 5 5.2 Citronellyl Acetate 5 241 Methyl Citronellyl Carbonate 5 16 Ethyl Citronellyl Carbonate 5 158

(22) It can be seen from the results that Methyl Citronellyl Carbonate (3,7-dimethyloct-6-en-1-yl methyl carbonate) has an odour threshold value which is 10 times lower compared to Ethyl Citronellyl Carbonate (3,7-dimethyloct-6-en-1-yl ethyl carbonate), and even 15 times lower compared to Citronellyl Acetate (3,7-dimethyloct-6-en-1-yl acetate). Based on this, a significant advance is achieved because much smaller amounts of the claimed compound are required to impart the same odour intensity.

EXAMPLE 9: A FEMALE FRAGRANCE ACCORD

(23) TABLE-US-00002 Ingredient parts per weight 1/1000 Benzyl acetate 10 Benzyl Salicylate 150 Cinnamic alcohol 1 Citronellol 30 Cyclohexal 60 Beta-Damascone 1.5 Delta-Damascone 0.4 Diprcpylene Glycole (PDG) 87.2 Ethyl Linalool 20 Eugenol 20 Galaxolide 45 Gardenol (1-phenylethyl acetate) 4 Hedione 30 Heliotropine (crystals) (benzo[d][1,3]dioxole-5-carbaldehyde) 45 Hexenyl-3-cis salicylate ((Z)-hex-1-en-1-yl 2-hydroxy-3-methylbenzoate) 30 Hydroxycitronellal 7 Indole 0.4 Beta-Ionone 65 Alpha-Irisone (4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one) 15 Iso-E-Super 145 (1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethan-1-one) Lilial (3-(4-(tert-butyl)phenyl)-2-methylpropanal) 120 Linalool 15 Linalyl acetate (3,7-dimethylocta-1,6-dien-3-yl acetate) 30 Lindenol (2-(4-methylcyclohex-3-en-1-yl)propan-2-ol) 5 Phenyl ethyl alcohol (2-phenylethan-1-ol) 20 Radjanol ((Z)-2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but-2-en-1-ol) 6 Tagetes oil 1 Thibetolide (oxacyclohexadecan-2-one) 20 Vanillin 1.5 3,7-dimethyloct-6-en-1-yl methyl carbonate (Example 1) 15 TOTAL: 1000

(24) The addition of 15 parts of 3,7-dimethyloct-6-en-1-yl methyl carbonate to the feminine floral rosy fruity accord with carnation undertones results in a strong and intense fruity pear rosy top note accord with slightly metallic and sharp undertones.

(25) Instead of adding 15 parts 3,7-dimethyloct-6-en-1-yl methyl carbonate a mixture of 3,7-dimethyloct-6-en-1-yl methyl carbonate and of (E)-3,7-dimethylocta-2,6-dien-1-yl methyl carbonate (1:1; 15 parts) were added to the fragrance accord, resulting again in a strong and intense fruity pear rosy top note accord, with less metallic and sharp undertones.

(26) Instead of adding 15 parts 3,7-dimethyloct-6-en-1-yl methyl carbonate 15 parts of a mixture obtained according to Example 5 was added, resulting in an accord wherein the rosy fruity character was reinforced. The fruity pear aspect of the mixture blends fully with the accord and brings freshness and a very pleasant natural feeling to the top note.