Cyclopentanone compounds

Abstract

Described herein is a method of using as perfuming ingredients, e.g. to impart odor notes of the fruity, fruity-exotic types, cyclopentanone compounds of formula ##STR00001##
in a form of any one of its stereoisomers or a mixture thereof, and wherein n represents 1 or 2.

Claims

1. A method to confer, enhance, improve, or modify the odor properties of a perfuming composition or of a perfumed article, with odor notes that are fruity-lactonic, tropical fruits, mango, slight passionfruit, with a pineapple undertone but not floral-jasmonic odor notes, which method comprises adding to said composition or article an effective amount of at least a compound of formula ##STR00005## in a form of any one of its stereoisomers or a mixture thereof, and wherein n represents 1; wherein the compound of formula (I) possesses odor notes that are fruity-lactonic, tropical fruits, mango, slight passionfruit, with a pineapple undertone and lacks floral-jasmonic odor notes.

Description

EXAMPLES

(1) The invention will now be described in further detail by way of the following examples, wherein the abbreviations have the usual meaning in the art, the temperatures are indicated in degrees centigrade ( C.); the NMR spectral data were recorded in CDCl.sub.3 (if not stated otherwise) with a 360 or 400 MHz machine for .sup.1H and .sup.13C, the chemical shifts are indicated in ppm with respect to TMS as standard, the coupling constants J are expressed in Hz.

Example 1

Synthesis of compounds of formula (I)

(2) 2-(hex-5-en-1-yl)cyclopentan-1-one

(3) Step 1: ethyl 1-(hex-5-en-1-yl)-2-oxocyclopentane-1-carboxylate:

(4) To a solution of ethyl 2-oxocyclopentane-1-carboxylate (56 mL, 375 mmol, 1 equiv.) in acetone (871 mL) at r.t. was rapidly added potassium carbonate (118 g, 845 mmol, 2.25 equiv.) and potassium iodide (20 g, 120 mmol, 0.32 equiv.). After stirring for 10 min, a solution of 6-bromohex-1-ene (51 mL, 381 mmol, 1.01 equiv.) in acetone (232 ml) was added and the reaction was refluxed for 19 h. Diethyl ether (900 mL) was added, the mixture was filtered on a Celite pad and the solvent was evaporated. The residue was diluted with ether, washed with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo to afford ethyl 1-(hex-5-en-1-yl)-2-oxocyclopentane-1-carboxylate as an oil (93.3 g, 91% purity, 95% yield).

(5) .sup.1H NMR: 1.25 (t, J=7.1 Hz, 3H), 1.27-1.42 (m, 4H), 1.53-1.59 (m, 1H), 1.86-2.07 (m, 6H), 2.21-2.28 (m, 1H), 2.37-2.44 (m, 1H), 2.50-2.56 (m, 1H), 4.11-4.21 (m, 2H), 4.92-5.01 (m, 2H), 5.73-5.82 (m, 1H).

(6) .sup.13C NMR: 215.0 (s), 171.1 (s), 138.6 (d), 114.5 (t), 61.3 (t), 60.5 (s), 38.0 (t), 33.7 (t), 33.4 (t), 32.7 (t), 29.1 (t), 24.3 (t), 19.6 (t), 14.1 (q).

(7) Step 2: 2-(hex-5-en-)-yl)cyclopentan-1-one:

(8) To a solution of the keto-ester of step 1 (93.3 g, 91% purity, 356 mmol, 1 equiv.) in methanol (860 mL) at r.t. was added a 6 M aqueous HCl solution (428 mL, 2.57 mol, 7.2 equiv.) dropwise. The reaction was refluxed for 6 days. Diethyl ether was added and the aqueous layer was extracted with ether twice. The combined organic extracts were washed sequentially with water, a saturated solution of sodium bicarbonate, water and brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by distillation on a Vigreux column (92-93 C., 1.5 mbar) to afford the desired ketone as an oil (42.0 g, 71% yield).

(9) .sup.1H NMR: 1.21-1.44 (m, 5H), 1.46-1.56 (m, 1H), 1.71-1.83 (m, 2H), 1.96-2.15 (m, 5H), 2.18-2.33 (m, 2H), 4.91-5.02 (m, 2H), 5.74-5.85 (m, 1H).

(10) .sup.13C NMR: 221.5 (s), 138.9 (d), 114.4 (t), 49.1 (d), 38.2 (t), 33.6 (t), 29.6 (t), 29.5 (t), 28.9 (t), 27.0 (t), 20.8 (t). 2-(hept-6-en-1-yl)cyclopentan-1-one

(11) Step 1: ethyl 1-(hept-6-en-1-yl)-2-oxocyclopentane-1-carboxylate:

(12) To a solution of ethyl 2-oxocyclopentane-1-carboxylate (3.56 mL, 26.7 mmol, 1 equiv.) in acetone (62 mL) at r.t. was rapidly added potassium carbonate (8.43 g, 60.4 mmol, 2.25 equiv.) and potassium iodide (1.43 g, 8.55 mmol, 0.32 equiv.). After stirring for 10 min, a solution of 7-bromohept-1-ene (4.23 mL, 26.9 mmol, 1.01 equiv.) in acetone (17 ml) was added and the reaction was refluxed for 23 h. Diethyl ether (100 mL) was added, the mixture was filtered on a Celite pad and the solvent was evaporated. The residue was diluted with ether, washed with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo to afford ethyl 1-(hept-6-en-1-yl)-2-oxocyclopentane-1-carboxylate as an oil (6.37 g, 88% purity, 92% yield).

(13) Step 2: 2-(hept-6-en-1-yl)cyclopentan-1-one:

(14) To a solution of the keto-ester of step 1 (6.64 g, 88% purity, 24.5 mmol, 1 equiv.) in methanol (59 mL) at r.t. was added a 6 M aqueous HCl solution (29.4 mL, 177 mol, 7.2 equiv.) dropwise. The reaction was refluxed for 5 days. Diethyl ether was added and the aqueous layer was extracted with ether twice. The combined organic extracts were washed sequentially with water, a saturated solution of sodium bicarbonate, water and brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (Heptane/AcOEt 95:5) and bulb-to-bulb distillation (115 C., 0.8-0.9 mbar) to afford the desired ketone as an oil (3.06 g, 68 % yield).

(15) .sup.1H NMR (CDCl.sub.3, 400 MHz): 1.22-1.41 (m, 7H), 1.48-1.55 (m, 1H), 1.73-1.81 (m, 2H), 1.97-2.13 (m, 5H), 2.19-2.23 (s, 1H), 2.27-2.31 (m, 1H), 4.95-5.00 (m, 2H), 5.76-5.83 (m, 1H).

(16) .sup.13C NMR (CDCl.sub.3, 100 MHz): 221.6 (s), 139.0 (d), 114.3 (t), 49.1 (d), 38.2 (t), 33.7 (t), 29.7 (t), 29.6 (t), 29.1 (t), 28.7 (t), 27.4 (t), 20.8 (t).

Example 2

Preparation of a Perfuming Composition

(17) A perfuming composition was prepared by admixing the following ingredients:

(18) TABLE-US-00001 Ingredient Parts by weight Amyl acetate 40 Ethyl acetate 20 Hexyl acetate 200 Isobutyl acetate 60 Benzyl acetate 80 Geranyl acetate 160 Linalyl acetate 400 (Z)-3-hexen-1-ol acetate 60 Styrallyl acetate 80 10%* Methylbutyric acid 40 Benzoic aldehyde 40 10%* methyl anthranilate 40 Carbinol butyrate 80 (Z)-3-hexen-1-ol butyrate 20 Ethyl caproate 40 Hexyl caproate 80 (Z)-3-hexen-1-ol caproate 20 Lemon 160 Maltol 80 10%* Damascenon 40 -n-decalactone 800 1%* Dimethylsulfid 40 Dodecalactone 800 Ethylvanillin 100 3-(4-Methoxyphenyl)-2-methylpropanal 80 Gamma hexalactone 40 Gamma jasmolactone 10 Gamma nonalactone 40 Gamma undecalactone 600 Geraniol 400 Habanolide.sup.1 800 Hedione.sup.2 300 Helvetolide.sup.3 80 Ethyl isobutyrate 40 Limonene 160 Linalol 1600 Menthol 10 10%* Methylisopropylthiazol 20 Ocimene 40 10%* Orange aldehyde 80 1%*, (3Z)-1-(2-butenyloxy)-3-Hexene 80 Linalyl ether 80 10%* (2E,6Z)-2,6-nonadienal 40 (Z)-3-hexen-1-ol dist 160 Hexyl salicylate 800 (Z)-3-hexen-1-ol salicylate 100 Terpineol 600 Verdox.sup.4 80 Beta ionone 200 9920 *in dipropyleneglycol .sup.1pentadecenolide; origin: Firmenich SA, Geneva, Switzerland .sup.2Methyl dihydrojasmonate; origin: Firmenich SA, Geneva, Switzerland .sup.3(1S,1R)-2-[1-(3,3-dimethyl-1-cyclohexyl)ethoxy]-2-methylpropyl propanoate; origin: Firmenich SA, Geneva, Switzerland .sup.42-tert-butyl-1-cyclohexyl acetate; origin: International Flavors & Fragrances, USA

(19) The addition of 80 parts by weight of 2-(hex-5-en-1-yl)cyclopentan-1-one to the above-described composition imparted to the latter a fruity-exotic (mango and passionfruit like) connotation with a slightly acidulous facet which makes the fragrance more juicy and natural.

(20) When, instead of the invention's compound, 2-heptylcyclopentan-1-one (Fleuramone) was added, there is little effect observed in the above-described composition. The above-described composition becomes just slightly more floral (jasmine like).

(21) When, instead of the invention's compound, 2-pentylcyclopentan-1-one (Delphone) was added, the perfumery composition becomes much greener (celery like) and more floral (jasmine like).

Example 3

Preparation of a Liquid Detergent Comprising the Invention's Compound

(22) TABLE-US-00002 TABLE 1 Composition of the liquid detergent formulation Concentration Ingredients [wt %] Sodium C14-17 Alkyl Sec Sulfonate.sup.1) 7 Fatty acids, C12-18 and C18-unsaturated.sup.2) 7.5 C12/14 fatty alcohol polyglycol ether with 17 7 mol EO.sup.3) Triethanolamine 7.5 Propylene Glycol 11 Citric acid 6.5 Potassium Hydroxyde 9.5 Properase L.sup.4) 0.2 Puradax EG L.sup.4) 0.2 Purastar ST L.sup.4) 0.2 Acrylates/Steareth-20 Methacrylate 6 structuring Crosspolymer.sup.5) Deionized Water 27.4 .sup.1)Hostapur SAS 60; Origin: Clariant .sup.2)Edenor K 12-18; Origin: Cognis .sup.3)Genapol LA 070; Origin: Clariant .sup.4)Origin: Genencor International .sup.5)Aculyn 88; Origin: Dow Chemical

(23) The liquid detergent was prepared by adding 1.5% by weight, relative to the total weight of the liquid detergent, of the invention's composition of example 2 into the unperfumed liquid detergent formulation of Table 1 under gentle shaking.

Example 4

Preparation of a Fabric Softener Comprising the Invention's Compound

(24) TABLE-US-00003 TABLE 2 Composition of the softener formulation Ingredient Concentration [wt %] Methyl bis[ethyl (tallowate)]-2- 12.20 hydroxyethyl ammonium methyl sulfate.sup.1) 1,2-benzisothiazolin-3-one.sup.2) 0.04 CaCl.sub.2 (10% aqueous solution) 0.40 Water 87.36 .sup.1)Stepantex VL90 A Diester Quat; Origin: Stepan .sup.2)Proxel GXL; Origin: Arch

(25) The softener was prepared by weighting Methyl bis[ethyl (tallowate)]-2-hydroxyethyl ammonium methyl sulfate which was heated at 65 C. Then Water and 1,2-benzisothiazolin-3-one were placed in the reactor and were heated at 65 C. under stirring. To the above mixture was added Methyl bis[ethyl (tallowate)]-2-hydroxyethyl ammonium methyl sulfate. The mixture was stirred 15 minuted and CaCl.sub.2 was added. Then 0.5 to 2% by weight, relative to the total weight of the softener, of the invention's composition of example 2 was added. The mixture was stirred 15 minutes and was cooled down to room temperature under stirring (viscosity measure: result 35+/5 mPas. (shear rate 106 sec-1)).

Example 5

Preparation of a Transparent Isotropic Shampoo Comprising the Invention's Composition

(26) TABLE-US-00004 TABLE 3 Composition of the transparent isotropic shampoo formulation Concentration Phases Ingredients [wt %] A Water deionized 44.4 Polyquaternium-10.sup.1) 0.3 Glycerin 85%.sup.2) 1 DMDM Hydantoin.sup.3) 0.2 B Sodium Laureth Sulfate.sup.4) 28 Cocamidopropyl Betaine.sup.5) 3.2 Disodium Cocoamphodiacetate.sup.6) 4 Ethoxy (20) Stearyl Alcohol.sup.6) 1 C Sodium Laureth Sulfate.sup.4) 3 Glyceryl Laureate.sup.7) 0.2 D Water deionized 1 Sodium Methylparaben.sup.8) 0.1 E Sodium Chloride 10% aqueous sol. 15 Citric acid 10% aqueous sol. till pH 5.5-6 q.s. 1)Ucare Polymer JR-400, Origin: Noveon .sup.2)Origin: Schweizerhall .sup.3)Glydant, Origin: Lonza .sup.4)Texapon NSO IS, Origin: Cognis .sup.5)Tego Betain F 50, Origin: Evonik .sup.6)Amphotensid GB 2009, Origin: Zschimmer & Schwarz .sup.7)Monomuls 90 L-12, Origin: Gruenau .sup.8)Nipagin Monosodium, Origin: NIPA

(27) The shampoo was prepared by dispersed in water Polyquatemium-10. The remaining ingredients of phase A were mixed separately by addition of one after the other while mixing well after each adjunction. This pre-mix was added to the Polyquaternium-10 dispersion and mixed for another 5 min. Then, the premixed phase B and the premixed Phase C were added (Monomuls 90L-12 was heated to melt in Texapon NSO IS) while agitating. Phase D and Phase E were added while agitating. PH was adjusted with citric acid solution till pH: 5.5-6.0 leading to an unperfumed shampoo formulae.

(28) The perfumed shampoo was prepared by adding 0.4 to 0.8% by weight, relative to the total weight of the shampoo, of the invention's composition of example 2 into the unperfumed shampoo formulation of Table 3 under gentle shaking.

Example 6

Preparation of a Structured Shower Gel Comprising the Invention's Composition

(29) TABLE-US-00005 TABLE 4 Composition of the shower gel formulation Ingredients Amount (% wt) WATER deionised 49.350 Tetrasodium EDTA.sup.1) 0.050 Acrylates Copolymer.sup.2) 6.000 Sodium C12-C15 Pareth Sulfate.sup.3) 35.000 Sodium Hydroxide 20% aqueous solution 1.000 Cocamidopropyl Betaine.sup.4) 8.000 Methylchloroisothiazolinone and 0.100 Methylisothiazolinone.sup.5) Citric Acid (40%) 0.500 .sup.1)EDETA B POWDER; trademark and origin: BASF .sup.2)CARBOPOL AQUA SF-1 POLYMER; trademark and origin: NOVEON .sup.3)ZETESOL AO 328 U; trademark and origin: ZSCHIMMER & SCHWARZ .sup.4)TEGO-BETAIN F 50; trademark and origin: GOLDSCHMIDT .sup.5)KATHON CG; trademark and origin: ROHM & HASS

(30) The shower gel was prepared by adding 0.5 to 1.5% by weight, relative to the total weight of the shower gel, of the invention's composition of example 2 into the unperfumed shower gel formulation of Table 4 under gentle shaking.

Example 7

Preparation of a Transparent Shower Gel Comprising the Invention's Composition

(31) TABLE-US-00006 TABLE 5 Composition of the transparent shower gel formulation Ingredients Concentration (% wt) WATER deionized 52.40 Tetrasodium EDTA.sup.1) 0.10 Sodium Benzoate 0.50 Propylene Glycol 2.00 Sodium C12-C15 Pareth Sulfate.sup.2) 35.00 Cocamidopropyl Betaine.sup.3) 8.00 Polyquaternium-7.sup.4) 0.20 Citric Acid (40%) 1.00 Sodium Chloride 0.80 .sup.1)EDETA B POWDER; trademark and origin: BASF .sup.2)ZETESOL AO 328 U; trademark and origin: ZSCHIMMER & SCHWARZ .sup.3)TEGO-BETAIN F 50; trademark and origin: GOLDSCHMIDT .sup.4)MERQUAT 550; trademark and origin: LUBRIZOL

(32) The transparent shower gel was prepared by adding 0.5 to 1.5% by weight, relative to the total weight of the shower gel, of the invention's composition of example 2 into the unperfumed shower gel formulation of Table 5 under gentle shaking.

Example 8

Preparation of a Milky Shower Gel Comprising the Invention's Composition

(33) TABLE-US-00007 TABLE 6 Composition of the milky shower gel formulation Concentration Ingredients (% wt) WATER deionized 50.950 Tetrasodium EDTA.sup.1) 0.050 Sodium Benzoate 0.500 Glycerin 86% 3.500 Sodium Laureth Sulfate.sup.2) 27.000 Polyquaternium-7.sup.3) 1.000 Coco-Betaine.sup.4) 6.000 PEG-120 Methyl Glucose trioleate.sup.5) 1.000 Citric Acid (40%) 1.000 Glycol Distearate & Laureth-4 & 3.000 Cocamidopropyl Betaine.sup.6) Sodium Chloride 20% 5.000 PEG-40 Hydrogenated Castor Oil.sup.7) 1.000 .sup.1)EDETA B POWDER; trademark and origin: BASF .sup.2)Texapon NSO IS; trademark and origin: COGNIS .sup.3)MERQUAT 550; trademark and origin: LUBRIZOL .sup.4)DEHYTON AB-30; trademark and origin: COGNIS .sup.5)GLUCAMATE LT; trademark and origin: LUBRIZOL .sup.6)EUPERLAN PK 3000 AM; trademark and origin: COGNIS .sup.7)CREMOPHOR RH 40; trademark and origin: BASF

(34) The transparent shower gel was prepared by adding 0.5 to 1.5% by weight, relative to the total weight of the shower gel, of the invention's composition of example 2 into the unperfumed shower gel formulation of Table 6 under gentle shaking.

Example 9

Preparation of a Pearly Shampoo Comprising the Invention's Composition

(35) TABLE-US-00008 TABLE 7 Composition of the pearly isotropic shampoo formulation Concentration Phases Ingredients (% wt) A Water deionized 45.97 Tetrasodium EDTA.sup.1) 0.05 Guar Hydroxypropyltrimonium Chloride.sup.2) 0.05 Polyquaternium-10.sup.3) 0.075 B NaOH 10% aqueous sol. 0.3 C Ammonium Lauryl Sulfate.sup.4) 34 Ammonium Laureth Sulfate.sup.5) 9.25 Cocamidopropyl Betaine.sup.6) 2 Dimethicone (&) C12-13 Pareth-4 (&) 2.5 C12-13 Pareth-23 (&) Salicylic Acid.sup.7) D Cetyl Alcohol.sup.8) 1.2 Cocamide MEA.sup.9) 1.5 Glycol Distearate.sup.10) 2 E Methylchloroisothiazolinone & 0.1 Methylisothiazolinone.sup.11) D-Panthenol 75%.sup.12) 0.1 Water deionized 0.3 F Sodium Chloride 25% aqueous sol. 0.6 .sup.1)EDETA B Powder, Origin: BASF .sup.2)Jaguar C14 S, Origin: Rhodia .sup.3)Ucare Polymer JR-400, Origin: Noveon .sup.4)Sulfetal LA B-E, Origin: Zschimmer & Schwarz .sup.5)Zetesol LA, Origin: Zschimmer & Schwarz .sup.6)Tego Betain F 50, Origin: Evonik .sup.7)Xiameter MEM-1691, Origin: Dow Corning .sup.8)Lanette 16, Origin: BASF .sup.9)Comperlan 100, Origin: Cognis .sup.10)Cutina AGS, Origin: Cognis 11)Kathon CG, Origin: Rohm & Haas .sup.12)D-Panthenol, Origin: Roche

(36) The shampoo was prepared by dispersed in water and Tetrasodium EDTA, Guar Hydroxypropyltrimonium Chloride and Polyquaternium-10. NaOH 10% solution (Phase B) was added once Phase A was homogeneous. Then, the premixed Phase C was added. and mixture was heated to 75 C. Phase D ingredients were added and mixed till homogeneous. The mixture was cooled down. At 45 C., Phase E ingredients were added while mixing. Final viscosity was adjusted with 25% NaCl solution and pH of 5.5-6 was adjusted with 10% NaOH solution.

(37) The perfumed pearly shampoo was prepared by adding 0.4 to 0.8% by weight, relative to the total weight of the shampoo, of the invention's composition of example 2 into the unperfumed shampoo formulation of Table 7 under gentle shaking.

Example 10

Preparation of a Structured Shower Gel Comprising the Invention's Composition

(38) TABLE-US-00009 TABLE 8 Composition of the milky shower gel formulation Ingredients Amount (% wt) WATER deionised 49.350 Tetrasodium EDTA.sup.1) 0.050 Acrylates Copolymer.sup.2) 6.000 Sodium C12-C15 Pareth Sulfate.sup.3) 35.000 Sodium Hydroxide 20% aqueous solution 1.000 Cocamidopropyl Betaine.sup.4) 8.000 Methylchloroisothiazolinone and 0.100 Methylisothiazolinone.sup.5) Citric Acid (40%) 0.500 .sup.6)EDETA B POWDER; trademark and origin: BASF .sup.7)CARBOPOL AQUA SF-1 POLYMER; trademark and origin: NOVEON .sup.8)ZETESOL AO 328 U; trademark and origin: ZSCHIMMER & SCHWARZ .sup.9)TEGO-BETAIN F 50; trademark and origin: GOLDSCHMIDT .sup.10)KATHON CG; tradeark and origin: ROHM & HASS

(39) The transparent shower gel was prepared by adding 0.5 to 1.5% by weight, relative to the total weight of the shower gel, of the invention's composition of example 2 into the unperfumed shower gel formulation of Table 8 under gentle shaking.

Example 11

Preparation of a Eau De Toilette Comprising the Invention's Compound

(40) The eau de toilette was prepared by adding 5 to 20% by weight, relative to the total weight of the eau de toilette, of the invention's composition of example 2 into ethanol under gentle shaking.