ORGANIC COMPOUNDS

Abstract

The present invention relates to compounds of formula (I) as herein defined, capable of releasing fragrant compounds in a controlled manner into the surroundings. The present invention is also concerned with a process for their production, and consumer products comprising them.

Claims

1. A compound of formula (I) ##STR00006## in which one of the dotted lines represents together with the carbon-carbon bond a double bond and each of the other two dotted lines represent together with the carbon-carbon bond a single bond.

2. A mixture comprising the compound of formula (I) as defined in claim 1 and a compound of formula (III) ##STR00007## wherein the dotted lines represent a double bond located at one of the alpha-, beta- or delta-positions on each of the cyclohexene rings.

3. A mixture according to claim 2 characterised in that the mixture comprises the compound of formula (I) and the compound of formula (III) in an ratio of 1:40 to 40:1.

4. A mixture according to claim 3 wherein the compound of formula (I) is ethyl S-(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl) cysteinate and the compound of formula (III) is ethyl N,S-bis(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl)cysteinate.

5. A mixture according to claim 2 further comprising a compound of formula (IV) ##STR00008## wherein the dotted lines represent a double bond located at one of the alpha-, beta- or delta-positions on each of the cyclohexene rings.

6. A mixture according to claim 5 wherein the compound of formula (IV) is ethyl N-(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)but-2-en-2-yl)-S-(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl)cysteinate.

7. A method of utilizing the compound of formula (I) as defined in claim 1 ##STR00009## as precursor for generating by spontaneous air oxidation, a damascone of formula (II), ##STR00010## wherein one of the dotted lines represents together with the carbon-carbon bond a double bond and each of the other two dotted lines represent together with the carbon-carbon bond a single bond.

8. A method of generating a compound of formula (II), ##STR00011## the method comprising exposing the compound of formula (I) as defined in claim 1 to oxygen.

9. A consumer product comprising the compound of formula (I) as defined by claim 1 and a consumer product base.

10. The consumer product according to claim 9 wherein the consumer product is not a food product, oral care product, tobacco product, confectionery, or pharmaceutical.

11. The consumer product according to claim 10 wherein the consumer product is a detergent or fabric conditioner.

12. A consumer product comprising the mixture as defined in claim 2 and a consumer product base.

13. The consumer product according to claim 12 wherein the consumer product is not a food product, oral care product, tobacco product, confectionery, or pharmaceutical.

14. The consumer product according to claim 12 wherein the consumer product is a detergent or fabric conditioner.

Description

[0036] The invention is now further described with reference to the following non-limiting examples. These examples are for the purpose of illustration only and it is understood that variations and modifications can be made by one skilled in the art.

Example 1: Ethyl S-(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl) cysteinate

[0037] In a 250 mL two-neck round-bottom flask were placed (E)-1-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)but-2-en-1-one (10 g, 52.0 mmol) and L-cysteine ethyl ester hydrochloride (15 g, 81 mmol) in water (100 ml). Under stirring at room temperature, potassium carbonate (8 g, 57.9 mmol) was added in one portion and the resulting mixture was stirred overnight at room temperature. MTBE (50 ml) was added to the mixture which was then stirred for an additional hour. The mixture was transferred to a separatory funnel, the phases were separated and the aq. phase was extracted with MTBE (2×50 ml). The org. phases were combined and washed with water (3×50 ml), water/brine (20 ml/30 ml) and brine (50 ml), dried over MgSO.sub.4, filtered and the solvent was evaporated to give ethyl S-(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl)-L-cysteinate (16.91 g, 49.5 mmol, 95% yield) as a mixture of four isomers and as a light yellow oil.

[0038] Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): fruity berry, reminiscent of stewed apple, slightly plastic, chemical.

[0039] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ=5.57-5.51 (m, 1H), 5.44 (br d, J=10 Hz, 1H), 4.20 (br q, J=7.1 Hz, 2H), 3.71-3.63 (m, 1H), 3.38-3.30 (m, 1H), 3.00-2.88 (m, 1.5H), 2.83-2.77 (m, 1H), 2.73-2.71 (m, 1H), 2.56-2.48 (m, 1.5H), 2.22 (d, J=10.5 Hz, 0.5H), 2.21 (d, J=10.6 Hz, 0.5H), 1.97 (br d, J=17.6 Hz, 1H), 1.8 (br s, 2H), 1.70 (br d, J=17.6 Hz, 1H), 1.32-1.30 (m, 3H), 1.29 (t, J=7.1 Hz, 3H), 1.01-0.87 (m, 9H) ppm.

[0040] .sup.13C-NMR (CDCl.sub.3, 100 MHz): δ=211.91, 211.80, 173.76, 131.59, 131.57, 131.51, 131.48, 124.04, 123.92, 123.9, 62.67, 62.64, 62.59, 61.00, 60.97, 55.03, 54.91, 54.89, 54.82, 54.32, 54.30, 54.06, 41.53, 41.50, 36.07, 36.03, 35.93, 35.86, 34.71, 34.67, 34.41, 32.97, 32.94, 32.92, 32.87, 31.57, 31.52, 31.43, 31.38, 29.65, 29.61, 29.58, 21.76, 21.74, 21.56, 21.50, 20.55, 20.53, 19.73, 19.68 ppm.

[0041] MS (EI, 70 eV): 341 ([M].sup.+., 2), 123 (67), 117 (69), 102 (65), 81 (51), 76 (49), 75 (80), 69 (100), 43 (60), 41 (58), 29 (56).

Example 2: Ethyl S-(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl) cysteinate (GR-87-1182-2) and Ethyl N,S-bis(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl)cysteinate)

[0042] In a 1500 mL sulfonation flask were placed (E)-1-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)but-2-en-1-one (200 g, 1.04 mol) and L-cysteine ethyl ester hydrochloride (98.1 g, 0.53 mol) in water (520 ml). Under stirring at room temperature, potassium carbonate (72.16 g, 0.52 mol) was added in one portion. The reaction mixture was then stirred overnight at room temperature. The solution was transferred into a separatory funnel, MTBE (100 ml) was added, the phases were separated and the aq. phase was extracted with MTBE (100 ml). The org. phases were combined and washed with brine (250 ml), dried over MgSO.sub.4, filtered and the solvent was evaporated to give a clear yellow oil containing a mixture of isomers of S-(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl)-L-cysteinate and isomers of ethyl N,S-bis(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl)-L-cysteinate in a ratio of 1:14 (255.39 g, 0.48 mol, 92% yield)

[0043] Odor description of the obtained mixture (dry-down of a 10% DPG solution after 24 hours on a smelling strip): fruity, damascone like, stewed apple, clean, pleasant

[0044] The activating conditions to release compounds of formula II comprise a combination of change of pH, elevated temperature and exposure to air. The combination of trigger conditions has the advantage of continuous release of odoriferous compounds of formula II from an early stage (e.g. on wet fabric in detergent application) to several days.

Example 3: Ethyl N-(4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)but-2-en-2-yl)-S-(4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)cysteinate)

[0045] Step 1: In a 250 ml sulfonation flask surmounted by a dean-stark, 3-hydroxy-1-(2,6,6-trimethylcyclohex-3-en-1-yl)but-2-en-1-onediketone (5.1 g, 24.5 mmol) and L-cysteine ethyl ester hydrochloride (4.46 g, 24 mmol) were suspended in toluene (50 ml). Acetic acid (10 ml, 175 mmol) was added and the mixture was heated to reflux (T.sub.bath=13° C.) overnight. The mixture was transferred into a separatory funnel and a mixture of water/brine (20 ml/30 ml) was added. The phases were separated and the aq. phase was washed with MTBE (30 ml). The org. phases were combined, washed with sat. aq. Na.sub.2CO.sub.3 (50 ml), brine/water (20 ml/10 ml) and brine (30 ml), dried over MgSO.sub.4, filtered and the solvent was evaporated to give ethyl-(4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)but-2-en-2-yl)cysteinate (8.3 g, 24.5, quant. yield) as a yellow oil.

[0046] MS (EI, 70 eV): 339 ([M].sup.+., 4), 216 (94), 174 (100), 142 (65), 116 (42), 107 (27), 84 (41), 67 (36), 58 (39), 41 (33), 29 (67).

[0047] Step 2: Ethyl-(4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)but-2-en-2-yl)cysteinate (3 g, 8.8 mmol) was placed in a 100 ml two-neck round-bottom flask together with (E)-1-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)but-2-en-1-one (1.7 g, 8.8 mmol). Water (50 ml), THE (10 ml) and potassium carbonate (1.2 g, 8.7 mmol) were added and the mixture was stirred at room temperature for three days. The orange mixture was transferred into a separatory funnel, the phases were separated and the aq. phase was washed with MTBE (2×30 ml). The org. phases were combined and washed with water/brine (2×20 ml/10 ml) and brine (20 ml), dried over MgSO.sub.4, filtered and the solvent was evaporated to give a yellow oil which was further purified by chromatography (eluent: heptane/MTBE, 8/2) to give ethyl-N-(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)but-2-en-2-yl)-S-(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl)cysteinate (1.54 g, 29 mmol, 32.8% yield) as a mixture of isomers and a light yellow oil.

[0048] Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): licorice, sweet, damascone.

[0049] .sup.13C-NMR (CDCl.sub.3, 100 MHz): δ=211.98, 211.95, 211.93, 211.90, 211.89, 211.84, 200.41, 200.37, 200.35, 170.32, 170.30, 170.28, 170.18, 170.15, 159.97, 159.86, 159.78, 159.72, 159.64, 132.55, 132.51, 131.71, 131.61, 124.17, 124.02, 123.89, 123.85, 100.21, 100.14, 62.81, 62.78, 62.73, 62.72, 62.56, 61.65, 61.63, 56.92, 56.82, 56.76, 56.69, 56.66, 55.28, 55.20, 55.13, 55.09, 55.07, 55.05, 55.01, 42.12, 41.67, 41.65, 41.62, 35.33, 35.26, 35.20, 35.12, 34.35, 34.27, 34.16, 33.97, 33.87 33.82, 33.74, 33.06, 33.04, 32.69, 31.80, 31.67, 31.65, 31.56, 31.53, 31.05, 31.02, 30.04, 30.01, 29.74, 29.69, 28.94, 22.62, 21.98, 21.95, 21.82, 21.77, 21.75, 21.72, 21.59, 21.53, 21.19, 20.66, 20.63, 20.08, 20.04, 19.85, 19.80, 19.34, 19.31, 19.29, 19.27, 14.05, 14.04 ppm.

[0050] MS (EI, 70 eV): 408 ([C.sub.22H.sub.34NO.sub.4S].sup.+, 2), 123 (100), 110 (36), 107 (32), 84 (44), 83 (34), 81 (95), 69 (54), 67 (43), 55 (27), 41 (26).

Example 4: Odor Assessment

[0051]

TABLE-US-00001 Dry-down after Dry-down after Wet 24 hours 3 days Compound A Nice, fruity, fruity berry, Damascone, damascone with a reminiscent of fresh slight plastic note stewed apple, slightly plastic, chemical Compound B fruity, damascone, Fruity, clean, Fruity, sweet, sweet damascone damascone Compound A + Damascone, fruity, damascone damascone compound B stewed apple, like, stewed apple, (ratio 1:14) strawberry clean, pleasant

[0052] Compound A: Ethyl S-(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl) cysteinate

[0053] Compound B: Ethyl N,S-bis(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl)cysteinate)

[0054] As can be seen from the odor description above, when combining the compound of formula (I) with a compound of formula (III) the plastic note disappeared.

Example 5: Fragrance Comprising a Compound of Formula (I)

[0055]

TABLE-US-00002 parts by weight Compound/Ingredient 1/1000 2-methyl-1-phenylpropan-2-yl acetate 20 4-(tert-butyl)cyclohexyl acetate 50 (2-(1-ethoxyethoxy)ethyl)benzene 2 AGRUMEX (2-(tert-butyl)cyclohexyl acetate) 25 2-phenylethan-1-ol 10 (E)-2-benzylideneoctanal 100 2-methylundecanal 1 AMBROFIX (3a,6,6,9a-tetramethyldodecahydronaphtho 1 [2,1-b]furan) methyl 2-aminobenzoate 2 AUBEPINE PARA CRESOL (4-methoxybenzaldehyde) 3 lemon terpens 10 Citronellol 80 delta damascone 2 DIHYDRO MYRCENOL 100 DIPHENYL OXIDE 10 DUPICAL (4-(octahydro-5H-4,7-methanoinden-5-ylidene) 2 butanal) EUCALYPTOL NATUREL 3 FLOROCYCLENE (3a,4,5,6,7,7a-hexahydro-1H-4,7- 75 methanoinden-6-yl propionate) GARDENOL (1-phenylethyl acetate) 20 ISO E SUPER 100 ISORALDEINE 25 JAVANOL @ 10% DPG 5 LEMONILE (3,7-dimethylnona-2,6-dienenitrile) 2 METHYL ACETOPHENONE (1-(p-tolyl)ethan-1-one) 2 4-(tert-butyl)cyclohexan-1-ol 10 PATCHOULI ESS SANS FER INDONESIE ORPUR 3 PHARAONE (2-cyclohexylhepta-1,6-dien-3-one) 10%/DPG 5 Hexyl salicylate 75 SERENOLIDE 30 (2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropyl cyclopropanecarboxylate) SPIROGALBANONE (1-(spiro[4.5]dec-6/7-en-7-yl)pent- 1 4-en-1-one STEMONE ((Z)-5-methylheptan-3-one oxime) 1 TETRAHYDRO LINALOL 50 UNDECAVERTOL 10 Dipropylen glycol (DPG) 165 Total: 1000

[0056] The fragrance composition above is a fresh floral green accord, reminiscent of fresh green muguet. This fragrance can be applied, e.g. in high density liquid detergent (HDLD, at 0.1-1.5 wt % (e.g. 0.6 wt %).

[0057] By replacing 45 parts of DPG of the accord above by a mixture of ethyl S-(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl) cysteinate and ethyl N,S-bis(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl)cysteinate (ration about 1:14), the overall character is now softer, fruitier, reminiscent of stewed apple on dry fabric. The fresh fruitiness is clearly enhanced over time, and last for several days.

[0058] By replacing 55 parts of DPG of the accord above by a mixture comprising ethyl S-(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl) cysteinate (2.7 parts), ethyl N,S-bis(4-oxo-4-(2′,6′,6′-trimethylcyclohex-3′-en-1′-yl)butan-2-yl)cysteinate (37.3 parts), and one additional precursor (4-(dodecylthio)-4-methylpentan-2-one (15 parts)), a very unusual and pleasant effect is the overall lift and radiance of the perfume on the dry fabric; with this combination the fresh fruitiness is not only enhanced and prolonged, but it furthermore has an enhanced volume and lift.

Example 6: Precursor Deposition Studies on Cotton in Heavy Duty Liquid Detergent Application

[0059] A liquid detergent composition (4.0 mg) was prepared with unperfumed heavy duty liquid detergent (HDLD) base containing 0.2% wt/wt of a mixture of Example 2. This liquid detergent composition was dissolved in 1 L of cold tap water to produce a wash liquor containing precursor. The wash liquor (100 mL) was placed in a 150 mL conical flask together with 2 cotton pads (10×10 cm.sup.2, each weighing 2.5 g). The flask was closed with a screwcap and shaken on a thermostated shaking table at 200 rpm and 40° C. for 1 h. The liquids were discarded and the cotton pads wrung out (wet weight 4.5 g) and put back in the conical flasks. After adding 75 mL of cold tap water, rinsing was effected by shaking for 30 min at RT. The cotton pads were wrung out and extracted with an accelerated solvent extractor (CH.sub.3CN, 60° C., 1500 psi), and the extracts (15-20 ml, precisely determined) were submitted to quantitative analysis by HPLC. The above process was repeated, with the difference that the towels were extracted after a period of 24 h line dry in ambient air.

[0060] The above two processes were repeated with liquid detergent composition containing 0.2% of 6-Damascone instead of the mixture of Example 2.

[0061] The quantification of 6-Damascone as such and the precursors thereof in the cotton pad extracts was effected by HPLC-UV with external calibration (0.3-20 ppm) of the reference materials in CH.sub.3CN. The results are shown in the Table below.

TABLE-US-00003 Mixture of Example 2 (δ-Damascone precursor + δ-Damascone HDLD released δ-Damascone) (comparison) wet (9 + 2)%   6% 24 h line dry (6 + 1)% 0.7%

[0062] The results show that the mixture of Example 2, which contains a mixture of bis- and mono adduct, leads to the release of a perceivable amount of δ-Damascone already on the wet stage. After 24 h line drying, the amount of δ-Damascone delivered from the precursor has exceeded the amount when using free δ-Damascone. In addition, a large reservoir of precursor is available for continued long lasting release of the odorant. Overall, the amount of bound and free δ-Damascone delivered from the precursor on dry fabric is over 5 times bigger than when using free δ-Damascone. The results suggest also that a combination of free δ-Damascone and precursor may produce advantageous effects.

Example 7: Precursor Deposition Studies on Cotton in Heavy Duty Liquid Detergent Application

[0063] Example 6 was repeated replacing the unperfumed heavy duty liquid detergent base with an unperfumed fabric conditioner base. The application involved a single cycle of shaking at 200 rpm at room temperature for 20 min, following by wringing out the cotton pads and ASE (accelerated solvent extractor) extraction.

[0064] The quantification of 5-Damascone as such and the precursors thereof in the cotton pad extracts was effected by HPLC-UV with external calibration (0.3-20 ppm) of the reference materials in CH.sub.3CN. The results are shown in the Table below.

TABLE-US-00004 Mixture of Example 2 (δ-Damascone precursor + δ-Damascone Fabric conditioner released δ-Damascone) (comparison) wet (43 + 7)%  14% 24h line dry (34 + 1.3)% 1.1%

[0065] The results show that the mixture of Example 2, which contains a mixture of bis- and mono adduct, leads to the release of a perceivable amount of δ-Damascone already on wet stage. After 24 h line drying, the amount of δ-Damascone delivered from the precursor had slightly exceeded the amount when using free δ-Damascone. Overall, the amount of bound and free δ-Damascone delivered from the precursor on wet fabric was 2.6 times higher than when using free δ-Damascone and over 25 times bigger on dry fabric. The results suggest also that a combination of free δ-Damascone and precursor may produce advantageous effects.