NOVEL FRAGRANCES WITH ROSE SCENT

Abstract

The present invention primarily concerns the use of compounds of the following formula (I)

##STR00001##

wherein X represents an oxygen atom, a —CHO, an —OH, or a —CH.sub.2OH group, a single bond or a double bond is present at the respective location of one of the dotted lines, at least one double bond is present when X is an OH group, and the 3-isopentyl or 3-isopent-2-enyl residue is connected to the ring in the ortho, meta, or para position to the X group, as perfuming and/or flavouring agents.

The invention further relates to fragrance and flavour compositions containing one or more of these compounds, perfumed or flavoured articles comprising one or more of these compounds and corresponding processes for imparting, modifying and/or enhancing certain odour notes.

Claims

1. A method comprising using a compound of formula (I), ##STR00043## where X represents an oxygen atom, a —CHO, an —OH, or a —CH.sub.2OH group, at the respective location of one of the dotted lines there is a single bond or a double bond, wherein when X═OH group, at least one double bond is present, and wherein the 3-isopentyl or 3-isopent-2-enyl residue is connected to the ring in ortho, meta, or para position to the X group, as a fragrance and/or flavour substance.

2. A method according to claim 1, wherein X represents an oxygen atom, a —CHO, an —OH, or a —CH.sub.2OH group, and at least one double bond is present at the respective location of one of the dotted lines.

3. A method according to claim 1, wherein X represents a CHO or a —CH.sub.2OH group, and a single bond or a double bond is present at the respective position of one of the dotted lines.

4. The method according to claim 1, wherein the fragrance is a rose note fragrance.

5. The method according to claim 1, comprising using the compound of formula (I) for imparting, modifying and/or enhancing one, two or more olfactory notes selected from the group consisting of the notes green, herbaceous, fresh, fruity, floral, woody, sweet, earthy, greasy, metallic and balsamic.

6. A fragrance and/or flavour composition, the fragrance and/or flavour composition comprising at least one compound of formula (I), ##STR00044## where X represents an oxygen atom, a —CHO, an —OH, or a —CH.sub.2OH group, at the respective location of one of the dotted lines there is a single bond or a double bond, wherein when X═OH group, at least one double bond is present, and wherein the 3-isopentyl or 3-isopent-2-enyl residue is connected to the ring in ortho, meta, or para position to the X group.

7. A fragrance and/or flavour mixture, the fragrance and/or flavour mixture comprising at least one fragrance and/or flavour composition according to claim 6, and further comprising one or more additional fragrances and/or flavouring substances, wherein the additional or one, more or all fragrances and/or flavouring substances are selected from the group consisting of: extracts from natural raw materials, essential oils, creams, absolutes, resins, resinoids, balms, tinctures and/or single fragrance substances; and mixtures thereof.

8. A fragrance and/or flavour composition, the fragrance and/or flavour composition comprising: a) one or more compounds of the formula (I), ##STR00045## where X represents an oxygen atom, a —CHO, an —OH, or a —CH.sub.2OH group, at the respective location of one of the dotted lines there is a single bond or a double bond, wherein when X═OH group, at least one double bond is present, and wherein the 3-isopentyl or 3-isopent-2-enyl residue is connected to the ring in ortho, meta, or para position to the X group and/or 2-(3-methylbutyl)cyclohexan-1-ol and/or 2-(3-methylbutyl)cyclohexan-1-one and/or 3-(3-methylbutyl)cyclohexan-1-ol and/or 3-(3-methylbutyl)cyclohexan-1-one and/or 4-(3-methylbutyl)cyclohexan-1-ol and/or 4-(3-methylbutyl)cyclohexan-1-one and/or 3-(3-methylbutyl)cyclohexan-1-ol, and/or 3-(3-methylbutyl)cyclohexan-1-one and (b) one or more other fragrance and/or flavour substances.

9. A fragrance and/or flavour composition according to claim 8, wherein the one or more further fragrance and/or flavour substance(s) is/are selected from the group consisting of: ethyl 2-cyclopent-2-en-1-yl acetate, 1-cyclohexylethyl (E)-but-2-enoate, (2-cyclopentylcyclopentyl) (E)-but-2-enoate, allyl 3-cyclohexylpropanoate, allyl hexanoate, 1,3-dimethylbutyl (E)-but-2-enoate, 1,3-dimethylbut-3-enyl 2-methyl propanoate, and/or (E)-1-(2,6,6-trimethylcyclohex-2-en-1-yl)but-2-en-1-one.

10. A perfumed or flavoured article, the perfumed or flavoured article comprising one or more compounds of the formula (I), ##STR00046## where X represents an oxygen atom, a —CHO, an —OH, or a —CH.sub.2OH group, at the respective location of one of the dotted lines there is a single bond or a double bond, wherein when X═OH group, at least one double bond is present, and wherein the 3-isopentyl or 3-isopent-2-enyl residue is connected to the ring in ortho, meta, or para position to the X group, and/or 2-(3-methylbutyl)cyclohexan-1-ol and/or 2-(3-methylbutyl)cyclohexan-1-one and/or 3-(3-methylbutyl)cyclohexan-1-ol and/or 3-(3-methylbutyl)cyclohexan-1-one and/or 4-(3-methylbutyl)cyclohexan-1-ol and/or 4-(3-methylbutyl)cyclohexan-1-one and/or 3-(3-methylbutyl)cyclohexan-1-ol, and/or 3-(3-methylbutyl)cyclohexan-1-one, one, two, three, four, five, six, seven, eight, nine, ten or more further fragrance and/or flavour substances, one or more further additives, excipients and/or active substances.

11. A perfumed or flavoured article according to claim 10, wherein the perfumed or flavoured article is selected from the group consisting of: perfume extracts, eau de parfums, eau de toilettes, aftershave lotions, eau de colognes, pre-shave products, splash colognes, perfumed refreshing tissues, acid, alkaline or neutral detergents, textile fresheners, ironing aids, liquid detergents, powder detergents, laundry pre-treatment products, fabric softeners, laundry soaps, washing tablets, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and polishes, personal care products, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair care products, deodorants, antiperspirants, decorative cosmetic products, candles, lamp oils, incense sticks, insecticides, repellents and fuels.

12. A perfumed or flavoured article according to claim 10, wherein the total amount of compounds of formula (I) and/or 2-(3-methylbutyl)cyclohexan-1-ol and/or 2-(3-methylbutyl)cyclohexan-1-one and/or 3-(3-methylbutyl)-icyclohexan-1-ol and/or 3-(3-methylbutyl)cyclohexan-1-one and/or 4-(3-methylbutyl)cyclohexan-1-ol and/or 4-(3-methylbutyl)cyclohexan-1-one and/or 3-(3-methylbutyl)cyclohexan-1-ol, and/or 3-(3-methylbutyl)cyclohexan-1-one is in the range from 0.00001 to 10 wt. % based on the total mass of the article.

13. A compound of formula (II) ##STR00047## wherein, X represents a —CHO or a —CH.sub.2OH group; and a single bond or a double bond is present at the location of any one of the dotted lines respectively, and wherein the 3-isopentyl or 3-isopent-2-enyl moiety is connected to the ring at a position ortho, meta, or para to the X group with the proviso that if a double bond is present in the ring, then the 3-isopentyl or 3-isopent-2-enyl moiety is directly connected to said double bond as an ortho or meta substituent.

14. A compound of formula (I), ##STR00048## where X represents an oxygen atom, a —CHO, an —OH, or a —CH.sub.2OH group, at the respective location of one of the dotted lines there is a single bond or a double bond, wherein when X═OH group, at least one double bond is present, and wherein the 3-isopentyl or 3-isopent-2-enyl residue is connected to the ring in ortho, meta, or para position to the X group, wherein the compound is present in the form of a cis:trans isomer mixture at the 2-, 3-, or 4-position, with predominant trans configuration.

15. A process for the preparation of a compound (II) ##STR00049## wherein, X represents a —CHO or a —CH.sub.2OH group; and a single bond or a double bond is present at the location of any one of the dotted lines respectively, and wherein the 3-isopentyl or 3-isopent-2-enyl moiety is connected to the ring at a position ortho, meta, or para to the X group with the proviso that if a double bond is present in the ring, then the 3-isopentyl or 3-isopent-2-enyl moiety is directly connected to said double bond as an ortho or meta substituent, comprising at least steps (i), (ii), characterized in that starting from 2-cyclohex-3-ene by: (i) Wittig reaction 1-isopentyl-2-(methoxymethylene)cyclohexane, 1-isopentyl-3-(methoxymethylene)cyclohexane, or 1-isopentyl-4-(methoxymethylene)cyclohexane is obtained, (ii) subsequent enol splitting leads to aldehyde (iii) and by optional subsequent reduction of the alcohol is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0128] The invention is described below by means of embodiments. As will be explained in more detail below, the compounds of formula (I) according to the invention can be synthesized in the following manner described below. Furthermore, it should be noted that the IUPAC nomenclature may differ from the previously used generic terms.

Example 1: 3-isopentylcyclohexanone (2)

[0129] Preparation of the Grignard reagent: Lightly grind magnesium shavings (16.5 g, 0.687 mol) in a mortar and place in a flask in 300 ml THF, add a spatula tip of iodine, heat under reflux (solution must decolorize) only then 1/10 of 3-methylbutyl bromide (93.8 g, 0.621 mol), after the Grignard reagent has started to form, drop the remaining 3-methylbutylbromide into 150 ml THF, reflux the preparation for 1 hour, and then allow the preparation to cool.

[0130] The Grignard solution is transferred via a cannula into a well stirred suspension of copper iodide (8.0 g, 0.042 mol) cooled to −5° C. in 300 ml THF. After dissolving the copper iodide, allow to cool to −20° C. and drop cyclohex-2-en-1-one (34 g, 0.354 mol) and stir at −20° C. for 4 hours (h), then thaw to RT and stir overnight. Preparation: Place the preparation in 600 ml ice-cold saturated ammonium chloride solution, add 300 ml MTBE. Phase separation; extract three times with 100 ml MTBE and wash, dry and concentrate the combined organic phases twice with 200 ml saturated (total) NaCl solution. The raw product (60.0 g) was fractionally distilled on a 15 cm Vigreux column under vacuum.

[0131] Yield: 52.0 g (87%)

[0132] .sup.1H-NMR (400 MHz, CDCl.sub.3) δ 2.42 (ddt, J=13.8, 4.0, 1.9 Hz, 1H), 2.35 (dddt, J=14.1, 5.0, 3.6, 1.5 Hz, 1H), 2.25 (dddd, J=14.1, 12.2, 6.1, 1.2 Hz, 1H), 2.04 (dddd, J=13.8, 8.0, 6.3, 3.9 Hz, 1H), 2.00 (ddt, J=13.7, 11.6, 1.1 Hz, 1H), 1.96-1.84 (m, 1H), 1.79-1.70 (m, 1H), 1.70-1.58 (m, 1H), 1.50 (dp, J=13.2, 6.6 Hz, 1H), 1.40-1.24 (m, 3H), 1.23-1.14 (m, 2H), 0.87 (d, J=6.6 Hz, 6H);

[0133] .sup.13C-NMR (101 MHz, CDCl.sub.3) δ 212.16 (C═O), 48.31 (CH.sub.2-ring), 41.55 (CH.sub.2-ring), 39.38 (CH-ring), 35.91 (CH.sub.2), 34.35 (CH.sub.2), 31.35 (CH.sub.2-ring), 28.08 (CH—(CH.sub.3).sub.2, 25.32 (CH.sub.2-ring), 22.58 (CH—(CH3).sub.2, 22.57 (CH—(CH3).sub.2.

Example 2: 3-isopentylcyclohexanol (3)

[0134] LAH (2.48 g, 0.065 mol) is presented in 200 ml THF at RT. At 0-10° C., compound 2 (10.0 g) is carefully added in 70 ml THF. It is stirred for 30 min at RT.

[0135] Preparation: Add preparation to 300 ml ice water (exothermic, H2 development). Add 150 ml MTBE and then 150 ml 25% sulfuric acid until the precipitate (Al(OH).sub.3) slowly dissolves, separate phases, extract aqueous phase 2× with 50 ml MTBE each, wash combined organic phases 1× with 100 ml soda solution and 1× with 100 ml saturated NaCl solution, dry over Na.sub.2SO.sub.4 and concentrate. The raw product (10.0 g) is fractionally distilled under vacuum at (60° C./500-10 mbar) using a Vigreux column.

[0136] Yield: 9.5 g (94%)

[0137] trans-isomer: NMR: .sup.1H-NMR (400 MHz, CDCl.sub.3) δ 4.09-4.01 (m, 1H), 1.78-1.57 (m, 5H), 1.56-1.45 (m, 3H), 1.25 (ddd, J=13.3, 10.5, 2.9 Hz, 1H), 1.21-1.15 (m, 4H), 1.04-0.92 (m, 1H), 0.86 (d, J=6.6 Hz, 6H)

[0138] .sup.13C-NMR (101 MHz, CDCl.sub.3) δ 67.08 (CH), 39.97 (CH.sub.2), 36.41 (CH.sub.2), 34.26 (CH.sub.2), 33.61 (CH.sub.2), 32.35 (CH.sub.2), 31.97 (CH), 28.36 (CH), 22.81 (CH.sub.3), 22.81 (CH.sub.3), 20.21 (CH.sub.2).

[0139] cis isomer: NMR: .sup.1H-NMR (400 MHz, CDCl.sub.3) δ 3.55 (tt, J=10.8, 4.2 Hz, 1H), 2.03-1.93 (m, 2H), 1.76 (dp, J=12.9, 3.2 Hz, 1H), 1.69-1.61 (m, 1H), 1.55-1.42 (m, J=6.5 Hz, 1H), 1.33-1.17 (m, 6H), 1.16-1.07 (m, 1H), 0.93-0.83 (m, 1H), 0.87 (d, J=6.6 Hz, 6H), 0.77 (tdd, J=12.6, 10.9, 3.5 Hz, 1H)

[0140] .sup.13C-NMR (101 MHz, CDCl.sub.3) δ 71.14 (CH), 42.93 (CH.sub.2), 36.90 (CH), 36.35 (CH.sub.2), 36.06 (CH.sub.2), 34.91 (CH.sub.2), 32.35 (CH.sub.2), 28.36 (CH), 24.33 (CH.sub.2), 22.83 (CH.sub.3) 22.81 (CH.sub.3).

Example 3: (3 E/Z)-1-Isopentyl-3-(methoxymethylene) cyclohexane (4)

[0141] Prepare methoxymethyltriphenylphosphonium chloride (84.2 g, 0.246 mol) in 500 ml THF and allow to cool to 0° C., add potassium tert-butylate (112 g, 0.40 mol) in portions at 0 to 5° C. Allow to stir for 30 minutes and then slowly drop 3-isopentylcyclohexanones (27.5 g, 0.164 mol) in 100 ml THF into the reaction solution, keeping the temperature below 10° C. Allow to stir for 30 minutes at <10° C. and then slowly warm up to RT over a period of 22 h.

[0142] Preparation: Quench the preparation with H.sub.2O, extract 3× with 1000 ml ethyl acetate, wash the combined organic phases with 200 ml total NaCl solution, dry and condense (60° C./500-10 mbar). The raw product (96.2 g) was distilled on a spherical tube. (150° C., 0.8 mbar).

[0143] Yield: 36.2 g (quantitative)

[0144] .sup.1H-NMR (400 MHz, CDCl.sub.3) δ 5.75 (d, J=1.7 Hz, 1H), 5.74 (t, J=2.0 Hz, 1H), 3.53 (s, 6H), 2.75-2.67 (m, 1H), 2.66-2.59 (m, 1H), 2.06 (dt, J=13.0, 2.3 Hz, 1H), 2.02-1.91 (m, 1H), 1.91-1.80 (m, 1H), 1.80-1.69 (m, 4H), 1.70-1.55 (m, 1H), 1.49 (dddd, J=12.8, 10.4, 6.3, 2.6 Hz, 2H), 1.43 (s, 2H), 1.40-1.11 (m, 13H), 1.10-0.94 (m, 2H), 0.94-0.81 (m, 12H).

[0145] .sup.13C-NMR (101 MHz, CDCl.sub.3) δ 138.95, 138.94.sub.isomer, 117.98, 117.93.sub.isomer, 59.28, 59.28.sub.isomer, 39.44.sub.isomer, 38.21.sub.isomer, 37.14, 37.43, 37.14.sub.isomer, 36.27, 36.24.sub.isomer, 34.68, 34.51.sub.isomer, 33.19, 31.38, 28.32, 28.30.sub.isomer, 28.25, 28.23.sub.isomer, 26.93.sub.isomer, 22.70, 22.67.sub.isomer, 22.65, 22.63.sub.isomer.

Example 4: 3-isopentylcyclohexanecarbaldehyde (5)

[0146] Compound 4 (35.0 g, 0.178 mol) in THF (400 ml) and 10% HCl solution (96 ml) was placed in a 11 stirrer, then the educts were added one after the other and the mixture was heated to boiling temperature, heating for 1 h under reflux.

[0147] Preparation: Quench the preparation with water and extract 3× with MTBE. Wash the combined organic phases once with H.sub.2O, dry and evaporate (60° C./500-10 mbar). The raw product (31.0 g) was distilled fractionated on Vigreux colons under vacuum.

[0148] Yield: 31.0 g (95%)

[0149] trans-isomer: NMR: 1H-NMR (400 MHz, CDCl.sub.3) δ 9.60 (d, J=1.57 Hz, 1H), 2.23 (ttd, J=12.17, 3.52, 1.62 Hz, 1H), 1.98 (mc, 3H), 1.75 (tq, J=14.30, 3.34, 1.72 Hz, 1H), 1.71 (mc, 1H), 1.64 (mc, 3H), 1.20 (mc, 5H), 1.14 (J=3.70 Hz, 1H), 0.86 (d, J=6.73 Hz, 6H).

[0150] .sup.13C-NMR (101 MHz, CDCl.sub.3) δ 204.83, 50.64, 37.13, 36.31, 36.05, 35.05, 33.58, 28.22, 26.12, 25.44, 22.63, 22.63

Example 5: (3-isopentylcyclohexyl) Methanol (6)

[0151] Under nitrogen (rinse apparatus thoroughly), LAH (3.2 g, 0.085 mol) is presented in 200 ml THF at RT. At 0-10° C., 3-isopentyl cyclohexane carbaldehyde (14.0 g, 0.077 mol) is carefully added in 70 ml THF. It is stirred for 30 min at RT.

[0152] Preparation: Add preparation to 300 ml ice water (exothermic, H2 development). Add 150 ml MTBE to the preparation, then add 150 ml of 25% sulfuric acid until the precipitate (Al(OH).sub.3) slowly dissolves, separate phases, extract aqueous phase twice with 50 ml MTBE each, wash combined organic phases once with 100 ml soda solution and once with 100 ml saturated NaCl solution, dry over Na.sub.2SO.sub.4, evaporate (60° C./500-10 mbar). The raw product (13.3 g) was distilled on a spherical tube still. (90° C., 1.0 mbar).

[0153] Yield: 12.7 g (90%)

[0154] .sup.1H-NMR (600 MHz, CDCl.sub.3) δ 3.46 (dd, J=10.5, 6.3 Hz, 1H), 3.44 (dd, J=10.6, 6.3 Hz, 1H), 1.82-1.71 (m, 3H), 1.56-1.45 (m, 2H), 1.45-1.36 (m, 2H), 1.31-1.21 (m, 2H), 1.21-1.12 (m, 3H), 0.88 (d, J=6.8 Hz, 1H), 0.86 (d, J=6.6 Hz, 6H), 0.85-0.77 (m, 2H), 0.57 (q, J=11.9 Hz, 1H);

[0155] .sup.13C-NMR (151 MHz, CDCl.sub.3) δ 68.93, 40.60, 37.50, 36.18, 35.46, 33.41, 32.77, 29.59, 28.54, 25.82, 22.71, 22.68.

Example 6: 1-isopentyl Cyclohexane Carbaldehyde (7)

[0156] Analogous to connection 3, connection 7 was established.

[0157] 1H-NMR (400 MHz, CDCl.sub.3) δ 9.81 (d, J=1.3 Hz, 1H), 9.55 (d, J=4.0 Hz, 1H), 2.45 (dtd, J=6.8, 3.9, 1.9 Hz, 1H), 2.01 (ddt, J=10.0, 10.1, 3.9 Hz, 1H), 1.93-1.81 (m, 4H), 1.80-1.66 (m, 3H), 1.65-1.59 (m, 4H), 1.59-1.51 (m, 3H), 1.51-1.43 (m, 2H), 1.42-1.30 (m, 5H), 1.29-1.20 (m, 4H), 1.19-1.08 (m, 3H), 0.92 (d, J=6.6 Hz, 3H), 0.87 (d, J=6.6 Hz, 3H), 0.86 (d, J=6.5 Hz, 3H), 0.84 (d, J=6.5 Hz, 3H).

[0158] .sup.13C-NMR (101 MHz, CDCl.sub.3) δ 206.13, 205.71, 70.63, 61.38, 55.81, 52.19, 51.07, 42.00, 41.96, 41.75, 37.26, 36.94, 36.72, 36.44, 35.70, 32.44, 30.34, 29.32, 28.73, 28.19, 28.14, 27.03, 26.52, 26.11, 25.27, 25.01, 24.77, 24.70, 24.21, 23.80, 23.69, 22.87, 22.71, 22.68, 22.62, 22.52, 22.28, 22.13.

Example 7: (1-isopentylcyclohexyl) Methanol (8)

[0159] Similar to connection 4, connection 8 was created from connection 7.

[0160] Yield: >90%

[0161] 1H-NMR (400 MHz, CDCl.sub.3) δ 3.71 (dd, J=10.8, 3.1 Hz, 1H), 3.67-3.58 (m, 3H), 1.871.64 (m, 9H), 1.64-1.44 (m, 5H), 1.04-1.29 (m, 18H), 0.84-0.89 (12H).

[0162] .sup.13C-NMR (101 MHz, CDCl.sub.3) δ 65.83, 63.35, 44.10, 42.09, 38.29, 37.08, 37.01, 35.57, 35.46, 31.57, 30.96, 29.59, 29.59, 28.83, 28.44, 28.30, 26.21, 25.97, 25.77, 23.01, 22.87, 22.87, 22.53, 22.37.

Example 8: 4-isopentyl Cyclohexane Carbaldehyde (9)

[0163] Analogous to connection 3, connection 9 was established.

[0164] 1H-NMR (400 MHz, CDCl.sub.3) δ 9.38 (s, 1H), 9.34-9.32 (m, 1H), 1.90-1.78 (m, 3H), 1.73-1.61 (m, 3H), 1.61-1.52 (m, 2H), 1.48-1.33 (m, 4H), 1.26-1.15 (m, 2H), 1.10-0.92 (m, 12H), 0.88 (d, J=6.6 Hz, 7H), 0.86 (d, J=6.6 Hz, 7H), 0.68-0.53 (m, 2H).

[0165] .sup.13C-NMR (101 MHz, CDCl.sub.3) δ 203.68, 202.89, 50.52, 47.39, 37.61, 36.95, 36.57, 36.48, 35.20, 34.12, 32.20, 32.20, 29.84, 29.84, 28.59, 28.54, 26.17, 26.17, 24.31, 24.31, 22.83, 22.83, 22.83, 22.83.

Example 9: (4-isopentylcyclohexyl) Methanol (10)

[0166] Similar to connection 4, connection 10 was created from connection 9.

[0167] Yield: >90%

[0168] 1H-NMR (400 MHz, CDCl.sub.3) δ 3.44 (d, J=6.3 Hz, 2H), 1.78 (d, J=9.1 Hz, 4H), 1.48 (ddt, J=11.4, 7.5, 4.5 Hz, 1H), 1.41 (dd, J=10.8, 5.3 Hz, 1H), 1.17 (d, J=3.1 Hz, 4H), 1.15 (d, J=3.5 Hz, 1H), 0.98-0.88 (m, 5H), 0.86 (d, J=6.6 Hz, 6H).

[0169] .sup.13C-NMR (101 MHz, CDCl.sub.3) δ 122.66, 68.83, 67.44, 66.47, 40.17, 38.44, 38.12, 36.77 36.32, 35.43, 35.11, 34.18, 33.82, 32.74, 31.83, 29.52, 28.97, 28.86, 28.28, 28.24, 25.76, 25.38, 22.70, 22.68.

Example 10: Shampoo

[0170] The compound from example 1 was incorporated into a shampoo base of the following composition in a dosage of 0.5 wt. %:

TABLE-US-00003 Sodium lauryl ether sulfate   12% (e.g. Texapon NSO, Cognis Deutschland GmbH) Cocamidopropyl betaine    2% (e.g. Dehyton K, Cognis Deutschland GmbH) Sodium Chloride  1.4% Citric acid  1.3% phenoxyethanol, methyl, ethyl, butyl and propyl  0.5% paraben Water 82.8%

[0171] The pH value of the shampoo base was about 6. 100 ml of a 20 wt % aqueous shampoo solution was prepared from this. In this shampoo solution, 2 hair strands were washed together for 2 minutes and then rinsed under lukewarm running water for 20 seconds. One strand of hair was wrapped wet in aluminium foil and the second strand of hair was dried with a hair dryer. Both strands of hair were evaluated by a panel for odour. Odor description of both hair strands: highly radiant, rose-like, fruity.

Example 11: Fabric Softener

[0172] The perfume composition from example 2 (after addition of 6% by weight of the ketone from example 1) was incorporated in a dosage of 0.5% by weight into a fabric softener base compound of the following composition

TABLE-US-00004 Quaternary ammonium methosulfate (esterquat),  5.5% approx. 90 (e.g. Rewoquat WE 18, Witco Surfactants GmbH) Alkyldimethylbenzylammonium chloride, approx. 50  0.2% (e.g. Preventol R50, Bayer AG) color solution, approx. 1%-ig  0.3% Water 94.0%

[0173] The pH value of the fabric softener base was in the range of 2 to 3. Two fabric cloths were rinsed with 370 g of a 1% aqueous fabric softener solution (based on the fabric softener base containing 0.5% by weight of the perfume composition from example 2) in a Linetest machine in the fabric softener program for 30 minutes at 20° C. The rags were wrung out and then spun for 20 seconds. One cloth was wet-wrapped and one hung to dry. Afterwards, both cloths were olfactorily evaluated by a panel. Description of the odour of both fabric flaps: floral, fresh, bright and woody aspects with slight fruity sweet undertones; rounded and harmonious olfactory impression.

Example 12: Washing Powder

[0174] The perfume oil composition from example 3 (after addition of 1 wt. %) was incorporated in a washing powder base of the following formulation in a dosage of 0.4 wt. %.

TABLE-US-00005 Linear Na-alkylbenzene sulfonate  8.8% Ethoxylated fatty alcohol C12-18 (7 EO)  4.7% Na Soap  3.2% Defoamer DOW CORNING 2-4248S POWDERED ANTIFOAM,  3.9% silicone oil on zeolite as carrier material zeolite 4A 28.3% Na-Carbonate 11.6% Na salt of a copolymer of acrylic and maleic acid (Sokalan CP5) 2.4 Na-Silicate  3.0% carboxymethyl cellulose  1.2% Dequest 2066  2.8% ([[(phosphonomethyl)imino]bis[(ethylene nitrilo)-bis(methylene)]]  0.2% tetrakis phosphonic acid, sodium salt) Optical brightener Na-Sulfate  6.5% protease  0.4% Sodium perborate tetrahydrate 22.0% Tetraacetylethylenediamine  1.0%

[0175] Two fabric cloths were washed with 370 g of a 1% aqueous washing powder lye based on the washing powder base comprising 0.4% by weight of the perfume oil composition from example 3 (the pH value of the washing powder lye is clearly in the alkaline range) in a Linetest machine in the main wash cycle for 45 minutes at 60° C. The rags were first rinsed with cold water for 5 minutes, wrung out and then spun for 20 seconds. One cloth was wet-welded and one was hung up to dry. Afterwards, both cloths were olfactory assessed by a panel.

[0176] Description of smell in each case: strong, brilliant, rose-like with natural notes and fruity undertones; rounded and harmonious olfactory impression.

Example 13: Perfume 1

[0177]

TABLE-US-00006 IONONES BETA 50% DPG 25.00 FARENAL ® 10% DPG 10.00 FLORAZON 1.00 HEXENOL CIS-3 1.00 HEXENYL ACETATE CIS-3 1.00 LIGUSTRAL 5.00 ALLYLAMYLGLYCOLATE 6.00 CYCLOGALBANAT ®. 6.00 MELONAL 10% DPG 6.00 DIHYDROMYRCENOL 32.00 LINALYLACETATE 10.00 OXANTHIA 50% IN TEC 10% DPG 3.00 HEXYLACETATE 25.00 ISOAMYLACETATE 2.00 ETHYLBUTYRATE 2.00 ETHYLCAPRONATE 2.00 ALDEHYDE C14 SO-CALLED 15.00 ALDEHYDE C18 SO-CALLED 1.00 DECALACTONE GAMMA 6.00 APPLE RED AROMATIC BASE 4.00 ETHYL METHYL BUTYRATE-2 5.00 MANZANATE 5.00 ALLYLCYCLOHEXYL PROPIONATE 5.00 ALLYL HEPTYLATE 7.00 PRUNELLA TYPE BASE 12.00 FRAMBINON ® 10.00 ETHYL MALTOL 1% DPG 10.00 CYCLAMEN ALDEHYDE 5.00 CALONE 10% DPG 6.00 HELIONAL 45.00 FLORHYDRAL 2.50 FLOROSA 25.00 ETHYLLINALOOL 50.00 DIMETHYLBENZYLCARBINYL ACETATE 8.00 TERPINEOL PURE 12.00 ROSE OXIDE 1.00 PHENYLETHYL ALCOHOL 56.00 PHENOXANOL 15.00 SYMROSE ® 1.00 DAMASCON ALPHA 1.00 DAMASCONE DELTA 1.00 BENZYLACETATE 10.00 HEDION 140.00 AMYLSALICYLAT 65.00 UNDECAVERTOL 2.50 IONON ALPHA 10.00 ISOEUGENOL ACETATE 6.00 AGRUMEX LC 30.00 SANDRANOL 6.00 EVERNYL 10% DPG 6.00 AMBROX DL 10% DPG 3.00 AMBRETTOLIDE 7.00 ETHYLENE BRASSYLATE 95.00 GLOBALIDE 50.00 INDOFLOR ® CRYSTAL. 10% DPG 5.00 DIPROPYLENE GLYCOL 119.00

Example 14: Perfume 2

[0178]

TABLE-US-00007 ALCOHOL C 6 KOSHER 6.00 OCTANONE-3 0.50 HEXENOL CIS-3 12.00 HEXENYL ACETATE CIS-3 8.00 VERTOCITRAL 8.00 CYCLOGALBANAT ®. 4.00 FLOROPAL 12.00 MAGNOLAN 10.00 MELONA 4.00 DIHYDROMYRCENOL 40.00 CITRONITRIL 3.00 OXANTHIA 50% IN TEC 1.00 THYMOL KRIST. 4.00 HEXYLACETATE 40.00 ISOAMYL ACETATE 100 5.00 PRENYLACETATE 4.00 ETHYLBUTYRATE 5.00 EXOVERT HIGH IMPACT 10% DPG 2.00 ALDEHYDE C14 SO-CALLED 15.00 DECALACTONE GAMMA 5.00 ETHYL METHYL BUTYRATE-2 5.00 MANZANATE 3.00 ALLYLCAPRONATE 5.00 ALLYLCYCLOHEXYL PROPIONATE 25.00 ALLYL HEPTYLATE 40.00 FRUITS 4.00 ALDEHYDE C16 SO-CALLED 2.00 FRAMBINON ® 10.00 MUGETANOL 10.00 CYCLOHEXYLMAGNOL 25.00 FREESIOL/CORPS 119 10.00 TETRAHYDROLINALOOL 190.00 DIMETHYLBENZYLCARBINYL ACETATE 8.00 DIMETHYLBENZYLCARBINYLBUTYRATE 10.00 ROSE OXIDE 5.00 PHENIRATE 30.00 SYMROSE ® 115.00 DAMASCONE DELTA 3.00 ETHYLSAFRANAT 3.00 DELPHONE 1.00 VELOUTONE 2.00 NONADIENOL-2.6 1% DPG 8.00 UNDECAVERTOL 8.00 IRIS NITRILE 10% DPG 3.00 AGRUMEX HC 120.00 ORYCLONE SPECIAL 165.00 HERBAL FLORATE 30.00 RHUBOFIX 0.50 BRAHMANOL 5.00 SANDRANOL 45.00 SYNAMBRAN ® R 50% IN IPM 1.00 GLOBALIDE 8.00 MACROLIDE ® SUPRA 12.00

Example 15: Perfume 3

[0179]

TABLE-US-00008 FLOROPAL 1.50 MAGNOLAN 12.00 DIHYDROMYRCENOL 8.00 LINALYLACETATE 25.00 TERPINYLACETATE 12.00 CITRAL FF 10% DPG 2.00 CINEOL 1.4 10% DPG 2.00 ORANGE BASE COLIPA NEW 1.00 AMAROCIT 14.00 TERPINOLEN DEXTRO 10% DPG 2.00 LAVENDER OIL CLONAL CENSO 2.00 EUCALYPTOL NAT. 6.00 CARDAMOM OIL RCO 0.80 MATE SUPERESSENCE 10% DPG 2.00 BORNEOL L/ISOBORNEOL 65/35 10% DPG 3.00 CAMPHOR DL 10% IPM 12.00 SULTANENE ® 1% DPG 5.00 HELIONAL 5.00 ETHYLLINALOOL 45.00 LINALOOL OXIDE 1.00 TETRAHYDROLINALOOL 35.00 DIMETHYLBENZYLCARBINYLBUTYRATE 1.00 TERPINEOL ALPHA 0.50 PHENYLETHYL ACETATE 0.50 PHENYLETHYL ALCOHOL 13.00 PHENOXANOL 3.00 SYMROSE ® 1.00 DAMASCENON TOTAL 10% DPG 2.00 GIVESCONE 2.00 HEDION 220.00 JASMONE CIS 10% DPG 8.00 METHYLOCTINE CARBONATE 10% DPG 1.00 UNDECAVERTOL 3.00 ALLYLIONON 3.00 IONON ALPHA 12.00 IONON BETA 80.00 IRON ALPHA 2.00 HELIOTROPIN/PIPERONAL 4.00 COUMARONE 10% IPM 2.00 KOUMALACTONES 10% TEC 1% DPG 4.00 OCTAHYDROCOUMARIN 4.00 TONKA BEANS ABS. 10% DPG 6.00 TABANON 1% DPG 2.00 ISO E SUPER 80.00 GUAJAKHOEL 10.00 GLOBALIDE 20.00 MACROLIDE ® SUPRA 2.00 GALAXOLIDE PURE 40.00 DIPROPYLENE GLYCOL 128.70

Example 16: Perfume 4

[0180]

TABLE-US-00009 IONONE BETA REPL BY DPG 5.00 VINEGAR 1.00 ALDEHYD C10 1.00 ALDEHYDE C11 UNDECANAL 0.50 ALDEHYDE C12 LAURINE 3.00 HEXENOL CIS-3 5.00 HEXENYL ACETATE CIS-3 5.00 VERTOCITRAL 5.00 VERTACETAL 0.50 STYROLYLACETATE 15.00 STYROLYLPROPIONATE 0.50 ISOPROPYLMETHYLTHIAZOLE-2.4 10% DPG 1.00 MELONAL 10% DPG 2.00 DIHYDROMYRCENOL 25.00 LEMON OIL ITAL. 5.00 ORANGE OIL 5.00 AMAROCIT 25.00 CITRORANGE BASE COLIPA 5.00 MENTHOL L DIST. 1.00 ETHYLACETATE 2.00 HEXYLACETATE 5.00 ISOAMYL ACETATE 100 1.00 ISOBUTYL ACETATE 10% DPG 2.00 JASMAPRUNAT 2.50 PRENYLACETATE 0.50 BUTYLBUTYRATE 2.00 HEXYL BUTYRATE 3.00 CAPROIC ACID NAT. 1.00 ALDEHYDE C14 SO-CALLED 15.00 DECALACTONE GAMMA 2.00 ETHYL METHYL BUTYRATE-2 1.50 SYMFRESH ® NX 25.00 ALLYLCAPRONATE 5.00 ALLYLCYCLOHEXYL PROPIONATE 8.00 ALLYL HEPTYLATE 4.00 THIOMENTHANONE-8.3 1% TEC 2.00 ETHYLMALTOL 5.00 PASSIONFRUIT TYPE BASE 25.00 MAJANTOL 15.00 TETRAHYDROLINALOOL 50.00 DIMETHYLBENZYLCARBINYL ACETATE 10.00 ROSE OXIDE L 1.00 SYMROSE ® 15.00 DAMASCONE DELTA 2.00 BENZYLACETATE 15.00 HEDION 150.00 VELOUTONE 1.50 HEXYLSALICYLATE 15.00 UNDECAVERTOL 2.50 ISOEUGENOL ACETATE 0.50 AGRUMEX LC 25.00 ORYCLONE SPECIAL 10.00 HERBYLPROPIONATE 2.00 SANDRANOL 25.00 ETHYLENE BRASSYLATE 25.00 GLOBALIDE 25.00 DIPROPYLENE GLYCOL 389.50

Example 17: Perfume 5

[0181]

TABLE-US-00010 IONONES BETA 50% DPG 25.00 FARENAL ® 10% DPG 10.00 FLORAZON 1.00 HEXENOL CIS-3 1.00 HEXENYL ACETATE CIS-3 1.00 LIGUSTRAL 5.00 ALLYLAMYLGLYCOLATE 6.00 CYCLOGALBANAT ®. 6.00 MELONAL 10% DPG 6.00 DIHYDROMYRCENOL 32.00 LINALYLACETATE 10.00 OXANTHIA 50% IN TEC 10% DPG 3.00 HEXYLACETATE 25.00 ISOAMYLACETATE 2.00 ETHYLBUTYRATE 2.00 ETHYLCAPRONATE 2.00 ALDEHYDE C14 SO-CALLED 15.00 ALDEHYDE C18 SO-CALLED 1.00 DECALACTONE GAMMA 6.00 APPLE RED AROMATIC BASE 4.00 ETHYL METHYL BUTYRATE-2 5.00 MANZANATE 5.00 ALLYLCYCLOHEXYL PROPIONATE 5.00 ALLYL HEPTYLATE 7.00 PRUNELLA TYPE BASE 12.00 FRAMBINON ® 10.00 ETHYL MALTOL 1% DPG 10.00 CYCLAMEN ALDEHYDE 5.00 CALONE 10% DPG 6.00 HELIONAL 45.00 FLORHYDRAL 2.50 FLOROSA 25.00 ETHYLLINALOOL 50.00 DIMETHYLBENZYLCARBINYL ACETATE 8.00 TERPINEOL PURE 12.00 AMAROCIT 1.00 PHENYLETHYL ALCOHOL 56.00 PHENOXANOL 15.00 3-(3-Methylbutyl)cyclohexan-1-one (2) 1.00 DAMASCON ALPHA 1.00 DAMASCONE DELTA 1.00 BENZYLACETATE 10.00 HEDION 140.00 AMYLSALICYLAT 65.00 UNDECAVERTOL 2.50 IONON ALPHA 10.00 ISOEUGENOL ACETATE 6.00 AGRUMEX LC 30.00 SANDRANOL 6.00 EVERNYL 10% DPG 6.00 AMBROX DL 10% DPG 3.00 AMBRETTOLIDE 7.00 ETHYLENE BRASSYLATE 95.00 GLOBALIDE 50.00 INDOFLOR ® CRYSTAL. 10% DPG 5.00 DIPROPYLENE GLYCOL 119.00

Example 18: Perfume 6

[0182]

TABLE-US-00011 IONONE BETA REPL BY DPG 5.00 VINEGAR 1.00 ALDEHYD C10 1.00 ALDEHYDE C11 UNDECANAL 0.50 ALDEHYDE C12 LAURINE 3.00 HEXENOL CIS-3 5.00 HEXENYL ACETATE CIS-3 5.00 VERTOCITRAL 5.00 VERTACETAL 0.50 STYROLYLACETATE 15.00 STYROLYLPROPIONATE 0.50 ISOPROPYLMETHYLTHIAZOLE-2.4 DPG 10% 1.00 MELONAL 10% DPG 2.00 DIHYDROMYRCENOL 25.00 LEMON OIL ITAL. 5.00 ORANGE OIL 5.00 AMAROCIT 25.00 CITRORANGE BASE COLIPA 5.00 MENTHOL L DIST. 1.00 ETHYLACETATE 2.00 HEXYLACETATE 5.00 ISOAMYL ACETATE 100 1.00 ISOBUTYL ACETATE 10% DPG 2.00 JASMAPRUNAT 2.50 PRENYLACETATE 0.50 BUTYLBUTYRATE 2.00 HEXYL BUTYRATE 3.00 CAPROIC ACID NAT. 1.00 ALDEHYDE C14 SO-CALLED 15.00 DECALACTONE GAMMA 2.00 ETHYL METHYL BUTYRATE-2 1.50 SYMFRESH ® NX 25.00 ALLYLCAPRONATE 5.00 ALLYLCYCLOHEXYL PROPIONATE 8.00 ALLYL HEPTYLATE 4.00 THIOMENTHANONE-8.3 1% TEC 2.00 ETHYLMALTOL 5.00 PASSIONFRUIT TYPE BASE 25.00 MAJANTOL 15.00 TETRAHYDROLINALOOL 50.00 DIMETHYLBENZYLCARBINYL ACETATE 10.00 DAMASCON ALPHA 1.00 3-(3-Methylbutyl) cyclohexan-1-one (2) 15.00 DAMASCONE DELTA 2.00 BENZYLACETATE 15.00 HEDION 150.00 VELOUTONE 1.50 HEXYLSALICYLATE 15.00 UNDECAVERTOL 2.50 ISOEUGENOL ACETATE 0.50 AGRUMEX LC 25.00 ORYCLONE SPECIAL 10.00 HERBYLPROPIONATE 2.00 SANDRANOL 25.00 ETHYLENE BRASSYLATE 25.00 GLOBALIDE 25.00 DIPROPYLENE GLYCOL 389.50

Example 19: Perfume 7

[0183]

TABLE-US-00012 IONONE BETA REPL BY DPG 5.00 VINEGAR 1.00 ALDEHYD C10 1.00 ALDEHYDE C11 UNDECANAL 0.50 ALDEHYDE C12 LAURINE 3.00 HEXENOL CIS-3 5.00 HEXENYL ACETATE CIS-3 5.00 VERTOCITRAL 5.00 VERTACETAL 0.50 STYROLYLACETATE 15.00 STYROLYLPROPIONATE 0.50 ISOPROPYLMETHYLTHIAZOLE-2.410% DPG 1.00 MELONAL 10% DPG 2.00 DIHYDROMYRCENOL 25.00 LEMON OIL ITAL. 5.00 ORANGE OIL 5.00 AMAROCIT 25.00 CITRORANGE BASE COLIPA 5.00 MENTHOL L DIST. 1.00 ETHYLACETATE 2.00 HEXYLACETATE 5.00 ISOAMYL ACETATE 100 1.00 ISOBUTYL ACETATE 10% DPG 2.00 JASMAPRUNAT 2.50 PRENYLACETATE 0.50 BUTYLBUTYRATE 2.00 HEXYL BUTYRATE 3.00 CAPROIC ACID NAT. 1.00 ALDEHYDE C14 SO-CALLED 15.00 DECALACTONE GAMMA 2.00 ETHYL METHYL BUTYRATE-2 1.50 SYMFRESH?+0 NX 25.00 ALLYLCAPRONATE 5.00 ALLYLCYCLOHEXYL PROPIONATE 8.00 ALLYL HEPTYLATE 4.00 THIOMENTHANONE-8.3 1% TEC 2.00 ETHYLMALTOL 5.00 PASSIONFRUIT TYPE BASE 25.00 MAJANTOL 15.00 TETRAHYDROLINALOOL 50.00 DIMETHYLBENZYLCARBINYL ACETATE 10.00 3-(3-Methylbutyl) cyclohexan-1-ol (3) 1.00 (4-ISOP ENTYLCYCLOH EXYL)M ETHANOL 15.00 DAMASCONE DELTA 2.00 BENZYLACETATE 15.00 HEDION 150.00 VELOUTONE 1.50 HEXYLSALICYLATE 15.00 UNDECAVERTOL 2.50 ISOEUGENOL ACETATE 0.50 AGRUMEX LC 25.00 ORYCLONE SPECIAL 10.00 HERBYLPROPIONATE 2.00 SANDRANOL 25.00 ETHYLENE BRASSYLATE 25.00 GLOBALIDE 25.00 DIPROPYLENE GLYCOL 389.50

Example 20: Perfume 8

[0184]

TABLE-US-00013 IONONES BETA 50% DPG 25.00 FARENAL ® 10% DPG 10.00 FLORAZON 1.00 HEXENOL CIS-3 1.00 HEXENYL ACETATE CIS-3 1.00 LIGUSTRAL 5.00 ALLYLAMYLGLYCOLATE 6.00 CYCLOGALBANAT ®. 6.00 MELONAL 10% DPG 6.00 DIHYDROMYRCENOL 32.00 LINALYLACETATE 10.00 OXANTHIA 50% IN TEC 10% DPG 3.00 HEXYLACETATE 25.00 ISOAMYLACETATE 2.00 ETHYLBUTYRATE 2.00 ETHYLCAPRONATE 2.00 ALDEHYDE C14 SO-CALLED 15.00 ALDEHYDE C18 SO-CALLED 1.00 DECALACTONE GAMMA 6.00 APPLE RED AROMATIC BASE 4.00 ETHYL METHYL BUTYRATE-2 5.00 MANZANATE 5.00 ALLYLCYCLOHEXYL PROPIONATE 5.00 ALLYL HEPTYLATE 7.00 PRUNELLA TYPE BASE 12.00 FRAMBINON ® 10.00 ETHYL MALTOL 1% DPG 10.00 CYCLAMEN ALDEHYDE 5.00 CALONE 10% DPG 6.00 HELIONAL 45.00 FLORHYDRAL 2.50 FLOROSA 25.00 ETHYLLINALOOL 50.00 DIMETHYLBENZYLCARBINYL ACETATE 8.00 TERPINEOL PURE 12.00 3-(3-Methylbutyl) cyclohexan-1-ol (3) 1.00 PHENYLETHYL ALCOHOL 56.00 PHENOXANOL 15.00 (1-ISOPENTYLCYCLOHEXYL)METHANOL 1.00 DAMASCON ALPHA 1.00 DAMASCONE DELTA 1.00 BENZYLACETATE 10.00 HEDION 140.00 AMYLSALICYLAT 65.00 UNDECAVERTOL 2.50 IONON ALPHA 10.00 ISOEUGENOL ACETATE 6.00 AGRUMEX LC 30.00 SANDRANOL 6.00 EVERNYL 10% DPG 6.00 AMBROX DL 10% DPG 3.00 AMBRETTOLIDE 7.00 ETHYLENE BRASSYLATE 95.00 GLOBALIDE 50.00 INDOFLOR ® CRYSTAL. 10% DPG 5.00 DIPROPYLENE GLYCOL 119.00

[0185] All perfume examples show fruity scent mixtures. The perfume examples 5 to 8 are characterized by particularly intensified fruity notes.