ORGANIC COMPOUNDS

Abstract

The present invention refers to dihydropyran derivatives, and to a process of making the same. The invention further refers to perfume compositions and fragranced articles comprising them.

Claims

1. A method comprising utilizing a compound of formula (I) in the form of any one of its stereoisomers or a mixture thereof ##STR00005## wherein R is hydrogen or methyl, and n is 1 or 3; as a fragrance, the method comprising mixing the compound of formula (I) with a consumer product base, or mixing a fragrance composition comprising the compound of formula (I) with a consumer product base.

2. The method of claim 1, wherein the compound of formula (I) is selected from the group consisting of 4-methyl-2-(3-phenylpropyl)-3,6-dihydro-2H-pyran, 4,6-dimethyl-2-(3-phenylpropyl)-3,6-dihydro-2H-pyran, 4,5-dimethyl-2-(3-phenylpropyl)-3,6-dihydro-2H-pyran, 2-benzyl-4-methyl-3,6-dihydro-2H-pyran, 2-benzyl-4,6-dimethyl-3,6-dihydro-2H-pyran, and 2-benzyl-4,5-dimethyl-3,6-dihydro-2H-pyran and mixtures thereof.

3. A fragrance composition comprising as odorant a compound of formula (I) as defined in claim 1 or a mixture thereof, and a base material.

4. The fragrance composition according to claim 3 further comprising a compound of formula (II) ##STR00006## wherein R is hydrogen or methyl, n is 1 or 3, and one of the dashed lines is a carbon-carbon double bond and the other dashed line is a carbon-carbon single bond.

5. A fragranced article comprising as odorant a compound of formula (I) as defined in claim 1 and a consumer product base.

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

7. A compound of formula (I) in the form of any one of its stereoisomers or a mixture thereof ##STR00007## wherein n is 3, and R is hydrogen or methyl.

8. A method of improving, enhancing or modifying a consumer product base comprising adding thereto an olfactory acceptable amount of a compound of formula (1), or a mixture thereof ##STR00008## wherein R is hydrogen or methyl, and n is 1 or 3,

9. The method according to claim 8, wherein the consumer product base is selected from the group consisting of fine fragrance, household products, laundry products, body care products, cosmetic and air care products.

10. A fragrance composition comprising as odorant a compound of formula (1) as defined in claim 2 and a base material.

11. A fragranced article comprising as odorant a fragrance composition as defined in claim 3 and a consumer product base.

12. The fragranced article according to claim 11 wherein the consumer product base is selected from fine fragrance, household products, laundry products, body care products, cosmetic and air care products.

Description

EXAMPLE 1

4-Methyl-2-(3-phenylpropyl)-3,6-dihydro-2H-pyran

[0058] To a solution of 4-phenylbutanal (3.0 g, 20.2 mmol, 1.0 equiv) and isoprene (1.52 g, 22.3 mmol, 1.1 equiv) in CH.sub.2Cl.sub.2 (50 mL) was added dropwise at room temperature a solution of Et.sub.2AlCl (30.4 mL, 30.4 mmol, 1.5 equiv, 1.0 M in hexanes). After stirring for 5 h at room temperature, the reaction mixture was poured onto ice and extracted with hexanes. The organic layer was washed with water, sat. NaHCO.sub.3 and brine. The combined organic extracts were dried over MgSO.sub.4, filtered and concentrated under reduced pressure to give a crude product (4.1 g). After Kugelrohr distillation (140° C./0.08 mbar) of the crude, the collected fraction was further purified by column chromatography (hexanes/MTBE 19:1) and a second Kugelrohr distillation (140° C./0.08 mbar) to afford 4-methyl-2-(3-phenylpropyl)-3,6-dihydro-2H-pyran (2.1 g, 48% yield) as a colorless oil.

[0059] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.32-7.17 (m, 5H), 5.44-5.40 (m, 1H), 4.21-4.09 (m, 2H), 3.52-3.45 (m, 1H), 2.67 (t, J=7.5 Hz, 2H), 2.01-1.80 (m, 3H), 1.78-1.60 (m, 2H), 1.71 (s, 3H), 1.58-1.49 (m, 1H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3): δ 142.4, 131.7, 128.4, 128.2, 125.6, 119.7, 73.6, 65.8, 35.9 (2CH.sub.2), 35.5, 27.4, 22.9 ppm. GC-MS (EI) m/z (%): 216 (0, [M].sup.+'), 147 (19), 105 (16), 104 (100), 99 (18), 97 (19), 91 (86), 69 (26), 68 (18), 67 (20), 41 (24).

[0060] Odor description: green, earthy, stemone, bell pepper, petitgrain, sligthly rosy.

EXAMPLE 2

4,6-Dimethyl-2-(3-phenylpropyl)-3,6-dihydro-2H-pyran

[0061] To a solution of 4-phenylbutanal (3.3 g, 22.3 mmol, 1.0 equiv) and 2-methylpenta-1,3-diene (2.68 g, 24.5 mmol, 1.1 equiv) in CH.sub.2Cl.sub.2 (50 mL) was added dropwise at room temperature a solution of Et.sub.2AlCl (33.4 mL, 33.4 mmol, 1.5 equiv, 1.0 M in hexanes). After stirring for 5 h at room temperature, the reaction mixture was poured onto ice and extracted with hexanes. The organic layer was washed with water, sat. NaHCO.sub.3 and brine. The combined organic extracts were dried over MgSO.sub.4, filtered and concentrated under reduced pressure . The crude product (4.0 g) was purified by column chromatography (hexanes/MTBE 19:1) and Kugelrohr distillation (140° C./0.08 mbar) to give 4,6-dimethyl-2-(3-phenylpropyl)-3,6-dihydro-2H-pyran (1.2 g, 23% yield, dr 85:15) as a colorless oil.

[0062] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of two diastereoisomers, dr 85:15): 7.32-7.11 (m, 5H), 5.37-5.32 (m, 0.15H), 5.31-5.26 (m, 0.85H), 4.35-4.26 (m, 0.15H), 4.18-4.06 (m, 0.85H), 3.72-3.63 (m, 0.15H), 3.54-3.44 (m, 0.85H), 2.63 (s, 2H), 1.95-1.32 (m, 6H), 1.66 (brs, 3H), 1.19 (2 x d, J=6.6 Hz and 6.9 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of two diastereoisomers, dr 85:15): δ 142.5, 131.8, 131.0 (minor), 128.4, 128.3 (minor), 125.6, 125.2, 124.5 (minor), 74.0, 71.0, 68.5 (minor), 67.3 (minor), 35.9, 35.9, 35.7, 35.5 (minor), 34.9 (minor), 27.6, 27.5 (minor), 23.1 (minor), 22.8, 21.6, 20.1 (minor) ppm. GC-MS (EI) m/z (%) formajor diastereoisomer: 230 (2, [M].sup.+.Math.), 147 (25), 131 (28), 105 (15), 104 (68), 91 (100), 82 (17), 81 (17), 67 (24), 43 (39), 41 (16); GC-MS (EI) m/z (%) for minor diastereoisomer: 230 (2, [M].sup.+.Math.), 147 (28), 131 (34), 117 (15), 104 (62), 95 (16), 91 (100), 82 (17), 81 (17), 67 (22), 43 (31).

[0063] Odor description: green, pyrazine like, rooty, petitgrain, chili pepper.

EXAMPLE 3.

2-Benzyl-4-methyl-3,6-dihydro-2H-pyran

[0064] To a solution of 2-phenylacetaldehyde (10.0 g, 83.2 mmol, 1.0 equiv) and 3-methylbut-3-en-1-ol (9.24 mL, 91.6 mmol, 1.1 equiv) in toluene (100 mL) was added dropwise at room temperature a solution of BF.sub.3 etherate (10.6 mL, 83.2 mmol, 1.0 equiv) in toluene (50 mL). After stirring for 30 min at room temperature, the reaction mixture was quenched with sat. NaHCO.sub.3 and extracted with MTBE. The combined organic extracts were washed with water and brine, dried over MgSO.sub.4, filtered and concentrated under reduced pressure. The crude product (18 g) was distilled under reduced pressure (0.04 mbar) over a Vigreux column (10 cm) to give an enriched fraction of product (4.5 g, bp 73° C. at 0.04 mbar). Further purification by column chromatography (pentane/MTBE 19:1) and Kugelrohr distillation (140° C./0.08 mbar) afforded 2-benzyl-4-methyl-3,6-dihydro-2H-pyran (2.7 g, 14% yield, 81% purity, along with 17% of 6-benzyl-4-methyl-3,6-dihydro-2H-pyran) as a colorless oil.

[0065] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.32-7.18 (m, 5H), 5.41-5.37 (m, 1H), 4.22-4.06 (m, 2H), 3.72 (dtd, J=3.4, 6.7, 10.1 Hz, 1H), 2.96 (dd, J=6.8, 13.7 Hz, 1H), 2.73 (dd, J=6.4, 13.7 Hz, 1H), 2.06-1.94 (m, 1H), 1.81-1.72 (m, 1H), 1.65 (s, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3): δ 138.5, 131.6, 129.3, 128.2, 126.1, 119.6, 74.6, 65.9, 42.4, 35.4, 22.9 ppm. GC-MS (EI) m/z (%): 188 (2, [M].sup.+.Math.), 97 (89), 96 (15), 92 (14), 91 (100), 69 (69), 67 (14), 65 (19), 41 (36), 39 (19), 29 (12).

[0066] Odor description: green, rosy, metallic, rose oxyde, gun powder, sharp, intense, fatty, floral.

EXAMPLE 4

(Comparison Example): 4-Methyl-2-(4-phenylbutyl)-3,6-dihydro-2H-pyran

[0067] To a solution of 5-phenylpentanal (3.0 g, 18.5 mmol, 1.0 equiv) and isoprene (1.39 g, 20.3 mmol, 1.1 equiv) in CH.sub.2Cl.sub.2 (20 mL) was added dropwise at room temperature a solution of Et.sub.2AlCl (15.1 mL, 27.7 mmol, 1.5 equiv, 25% in toluene). After stirring for 5 h at room temperature, the reaction mixture was poured onto ice and extracted with hexanes. The organic layer was washed with water, sat. NaHCO.sub.3 and brine. The combined organic extracts were dried over MgSO4, filtered and concentrated under reduced pressure . The crude product (3.1 g) was purified by column chromatography (hexanes/MTBE 19:1) and Kugelrohr distillation (160° C./0.08 mbar) to give 4-methyl-2-(4-phenylbutyl)-3,6-dihydro-2H-pyran (0.66 g, 15% yield) as a colorless oil.

[0068] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.30-7.22 (m, 2H), 7.21-7.13 (m, 3H), 5.43-5.36 (m, 1H), 4.20-4.03 (m, 2H), 3.49-3.38 (m, 1H), 2.62 (t, J=7.7Hz, 2H), 1.99-1.87 (m, 1H), 1.85-1.75 (m, 1H), 1.72-1.35 (m, 6H), 1.67 (s, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3): δ 142.6, 131.7, 128.3, 128.2, 125.6, 119.7, 73.6, 65.9, 35.9 (2CH.sub.2), 35.8, 31.5, 25.2, 23.0 ppm. GC-MS (EI) m/z (%): 230 (6, [M].sup.+.Math.), 144 (17), 117 (30), 104 (34), 97 (22), 92 (20), 91 (100), 69 (26), 68 (17), 67 (21), 41 (24).

[0069] Odor description: weak, green, crunchy, bell pepper, floral.

EXAMPLE 5

(Comparison Example): 4-Methyl-2-phenethyl-3,6-dihydro-2H-pyran

[0070] To a solution of 3-phenylpropanal (7.39 g, 55.1 mmol, 1.0 equiv) and isoprene (4.5 g, 66.1 mmol, 1.2 equiv) in toluene (15 mL) was added dropwise at 0 ° C. a pre-mixed suspension of BF.sub.3 etherate (0.99 mL, 7.87 mmol, 14 mol %) and Hünig's base EtN(iPr).sub.2 (0.30 mL, 1.76 mmol, 3 mol %). After stirring for 16 h at room temperature, the reaction mixture was poured onto ice and extracted with hexanes. The organic layer was washed with water, sat. NaHCO.sub.3 and brine. The combined organic extracts were dried over MgSO4, filtered and concentrated under reduced pressure . The crude product (11 g) was purified by Kugelrohr distillation (180° C./0.08 mbar), by column chromatography (hexanes/MTBE 19:1) and a second Kugelrohr distillation (150° C./0.08 mbar) to afford 4-methyl-2-phenethyl-3,6-dihydro-2H-pyran (1.0 g, 9% yield) as a colorless oil.

[0071] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.31-7.13 (m, 5H), 5.43-5.37 (m, 1H), 4.24-4.05 (m, 2H), 3.49-3.39 (m, 1H), 2.81 (ddd, J=13.9, 9.6, 5.4 Hz, 1H), 2.70 (ddd, J=13.8, 9.4, 7.1 Hz, 1H) , 2.04-1.71 (m, 4H), 1.67 (s, 3H). .sup.13C NMR (101 MHz, CDCI.sub.3): δ 142.1, 131.7, 128.4, 128.3, 125.7, 119.7, 72.7, 65.8, 37.5, 35.9, 31.7, 22.9 ppm. GC-MS (EI) m/z (%): 202 (5, [M].sup.+.Math.), 117 (26), 105 (26), 104 (18), 92 (35), 91 (100), 69 (29), 68 (19), 67 (24), 41 (29), 39 (20).

[0072] Odor description: green, rosy, metallic, geranium leaf.

EXAMPLE 6

Mixture of 4-methylene-2-(3-phenylpropyl)tetrahydro-2H-pyran, 4-methyl-2-(3-phenylpropyl)-3,6-dihydro-2H-pyran and 4-methyl-6-(3-phenylpropyl)-3,6-dihydro-2H-pyran

[0073] A pre-mixed solution of 4-phenylbutanal (9.00 g, 60.7 mmol, 1.0 equiv) and 3-methylbut-3-en-1-ol (6.13 mL, 60.7 mmol, 1.0 equiv) in toluene (40 mL) was added dropwise at reflux with a syringe pump (rate 10 mL/h) to a boiling solution of NaHSO.sub.4 (15 mg, 0.2 mol %) in toluene (60 mL) attached to a Dean-Stark trap. After refluxing for 2 h, the reaction mixture was concentrated under reduced pressure. The crude was purified by fractional distillation under high vacuum (0.06 mbar) to afford a mixture of alkene isomers (6.4 g, 49% yield, bp 89 ° C. at 0.06 mbar) as a colorless oil. The mixture was composed of 78% of 4-methylene-2-(3-phenylpropyl)tetrahydro-2H-pyran, 13% of 4-methyl-2-(3-phenylpropyl)-3,6-dihydro-2H-pyran and 9% of 4-methyl-6-(3-phenylpropyl)-3,6-dihydro-2H-pyran).

[0074] Odor description: green, fatty, rooty, fig, bigaryl, stemone, bud.

[0075] Analytical data for 4-methylene-2-(3-phenylpropyl)tetrahydro-2H-pyran: .sup.1H NMR (400 MHz, CDCl.sub.3): 7.28-7.22 (m, 2H), 7.20-7.12 (m, 3H), 4.73-4.65 (m, 2H), 4.04 (ddd, J=11.2, 10.1, 3.9 Hz, 1H), 3.34 (ddd, J=12.2, 10.9, 2.7 Hz, 1H), 3.27-3.18 (m, 1H), 2.61 (t, J=7.4 Hz, 2H), 2.37-1.89 (m, 4H), 1.86-1.38 (m, 4H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3): δ 144.7, 142.3, 128.3, 128.2, 125.6, 108.2, 78.6, 68.6, 41.1, 35.9, 35.8, 35.2, 27.3 ppm. GC-MS (EI) m/z (%): 216 (1, [M].sup.+.Math.), 131 (14), 130 (10), 112 (17), 105 (13), 104 (100), 97 (29), 91 (37), 67 (22), 53 (9), 41 (10).

[0076] Analytical data for 4-methyl-2-(3-phenylpropyl)-3,6-dihydro-2H-pyran: see Example 1.

[0077] Analytical data for 4-methyl-6-(3-phenylpropyl)-3,6-dihydro-2H-pyran: Characteristic .sup.1H NMR (400 MHz, CDCl.sub.3) signals are: 5.31-5.26 (m, 1H), 3.96 (ddd, J=11.2, 5.8 2.4 Hz, 1H), 3.59 (ddd, J=11.2, 10.1, 3.9 Hz, 1H) ppm. Characteristic .sup.13C NMR (101 MHz, CDCl.sub.3) signals are: δ 73.8 (CHO), 63.4 (CH.sub.2O) ppm. GC-MS (EI) m/z (%): 216 (1, [M].sup.+.Math.), 112 (40), 98 (7), 97 (100), 91 (31), 79 (9), 77 (8), 65 (8), 43 (7), 41 (17), 39 (8).

EXAMPLE 7

Determination of GC-Odor Threshold Values

[0078] 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).

[0079] Under identical conditions the odor threshold value for the individual compounds was measured. The results are given below.

TABLE-US-00001 odor threshold value formula (I) Compound n is [ng] 4-Methyl-2-(3-phenylpropyl)-3,6-dihydro-2H-pyran 3 0.02 4,6-Dimethyl-2-(3-phenylpropyl)-3,6-dihydro-2H- 3 0.03 pyran 2-Benzyl-4-methyl-3,6-dihydro-2H-pyran 1 0.03 4-Methyl-2-(4-phenylbutyl)-3,6-dihydro-2H-pyran 4 63 4-Methyl-2-phenethyl-3,6-dihydro-2H-pyran 2 45

[0080] As can be seen from the results above the compounds of the present invention have an odor threshold value which is at least about 1500 times lower compared to dihydropyran derivatives wherein the two rings are linked by a C2 or C4 alkyl chain. Based on this, a significant advance is achieved because much smaller amount of the claimed compounds is required to impart the same odor intensity.

EXAMPLE 8

Fragrance Composition

[0081]

TABLE-US-00002 parts by weight Compound/Ingredient 1/1000 Benzyl acetate 125 2-Methyl-1-phenylpropan-2-yl acetate 12 (Z)-hex-3-en-1-yl acetate 1 JASMACYCLENE 125 (3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-6-yl acetate) AGRUMEX (2-(tert-butyl)cyclohexyl acetate) 10 2-Phenylethan-1-ol 200 Nonanal 2 Guaiac wood essential oil 4 Citronellol 35 alpha-Damascone 2 delta-Damascone 2 Diphenyl oxide (oxydibenzene) 100 GALAXOLIDE (4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8- 60 hexahydrocyclopenta[g]isochromene) Eugenol 4 Beta Ionone 10 Diethyl Malonate 2 MYRALDENE (4-(4-methylpent-3-en-1-yl)cyclohex-3-ene-1- 2 carbaldehyde) ROSE OXIDE (4-methyl-2-(2-methylprop-1-en-1-yl)tetrahydro- 1 2H-pyran) Phenethyl 2-phenylacetate 5 ROSACETOL (2,2,2-trichloro-1-phenylethyl acetate) 10 Geraniol 20 PEONILE (2-cyclohexylidene-2-phenylacetonitrile) 10 TERPINEOL PUR 10 TETRAHYDRO LINALOL (3,7-dimethyloctan-3-ol) 25 TRICYCLAL (2,4-dimethylcyclohex-3-ene-1-carbaldehyde) 3 Dipropyleneglycol (DPG) 215 4-Methyl-2-(3-phenylpropyl)-3,6-dihydro-2H-pyran (Example 1) 5 Total: 1000

[0082] The fragrance composition is, for example, suitable to fragrance a detergent (e.g. powder detergent) at a dosage of about 0.3wt %.

[0083] By the addition of a compound of formula (I) such as 4-methyl-2-(3-phenylpropyl)-3,6-dihydro-2H-pyran, the performance of the fragrance is clearly improved on neat and wet. The rosy character becomes more vibrant, green rosy, geranium leaf with a vibrant green which reinforces the “fresh and clean” olfactive association