ISOMER MIXTURES OF UNSATURATED MACROCYCLIC MUSK COMPOUNDS

Abstract

Herein described are novel mixtures, containing or consisting of a first compound (E) and a second compound (Z), wherein compounds (E) and (Z) are compounds of formula (I) with identical constitutional formula

##STR00001## wherein it applies that one of the four wavy lines denotes a double bond and the remaining wavy lines denote a single bond, respectively, and X is selected from O, CH.sub.2 and OCH.sub.2, and the first compound (E) is trans-configurated and the second compound (Z) is cis-configurated, wherein the weight ratio of compound (E) to compound (Z) in the mixture is in the range of 10:90 to 65:30, preferably to 65:35, particularly preferably to 60:40, uses of such mixtures, methods for producing such mixtures as well as products containing such mixtures.

Claims

1. A mixture comprising a first compound (E) and a second compound (Z), wherein compounds (E) and (Z) are compounds of formula (I) with identical constitutional formula ##STR00009## wherein it applies that one of the four wavy lines denotes a double bond and the remaining wavy lines denote a single bond, respectively, and X is selected from O, CH.sub.2 and OCH.sub.2, and the first compound (E) is trans-configurated and the second compound (Z) is cis-configurated, wherein the weight ratio of compound (E) to compound (Z) in the mixture is in the range of 10:90 to 65:30, wherein the mixture comprises one or several compounds selected from the group consisting of cyclohexadec-8-en-1-one, oxacyclohexadecen-2-one, 17-oxacycloheptadec-9-en-1-one, particularly (9Z)-17-oxacycloheptadec-9-en-1-one, and cyclohexadec-5-en-1-one, with the proviso that in case of cyclohexadec-8-en-1-one the weight ratio of compound (E) to compound (Z) in the mixture is not 40.6:30.5 or 20:10, and with the proviso that in case of cyclohexadec-5-en-1-one the weight ratio of compound (E) to compound (Z) in the mixture is not 37:62.

2. A mixture according to claim 1, with the proviso that in case of cyclohexadec-8-en-1-one the weight ratio of compound (E) to compound (Z) in the mixture is not in the range of 35:25 to 45:35 or in the range of 19:9 to 21:11, and/or with the proviso that in case of cyclohexadec-5-en-1-one the weight ratio of compound (E) to compound (Z) in the mixture is not in the range of 32:57 to 42:67.

3. A mixture according to claim 1, wherein the mixture is a fragrance substance mixture comprising one or several additional fragrance substances.

4. A mixture according to claim 3, wherein the one, several or all of the additional fragrance substances is or are selected from the groups consisting of alcohols, aldehydes, ketones, ethers, esters and carboxylates.

5. A mixture according to claim 3, wherein the additional or one, several or all of the additional fragrance substances has or have a molar mass in the range of 150 to 285 g/mol.

6. A fragrance substance mixture according to claim 3, wherein the ratio of the total mass of fragrance substances that do not correspond to formula (I) to the total mass of compound(s) of formula (I) is higher than or equal to 80:20.

7. A mixture according to claim 1 producible by a method comprising the following steps: (i) providing a base mixture comprising a first compound (E) and a second compound (Z), wherein compounds (E) and (Z) are compounds of formula (I) with identical constitutional formula ##STR00010## wherein it applies that one of the four wavy lines denotes a double bond and the remaining wavy lines denote a single bond, respectively, and X is selected from O, CH.sub.2 and OCH.sub.2, and the first compound (E) is trans-configurated and the second compound (Z) is cis-configurated, wherein the weight ratio of compound (E) to compound (Z) in the base mixture is higher than 10:90, wherein the mixture comprises one or several compounds selected from the group consisting of cyclohexadec-8-en-1-one, oxacyclohexadecen-2-one, 17-oxacycloheptadec-9-en-1-one, particularly (9Z)-17-oxacycloheptadec-9-en-1-one, and cyclohexadec-5-en-1-one, (ii) performing an acid-catalyzed isomerization, on compound (E) contained in the base mixture, so that a mixture is obtained, wherein the weight ratio of compound (E) to compound (Z) in the mixture is in the range of 10:90 to 65:30, with the proviso that in case of cyclohexadec-8-en-1-one the weight ratio of compound (E) to compound (Z) in the mixture is not 40.6:30.5 or 20:10, and with the proviso that in case of cyclohexadec-5-en-1-one the weight ratio of compound (E) to compound (Z) in the mixture is not 37:62.

8. A method for producing a mixture comprising a first compound (E) and a second compound (Z), wherein compounds (E) and (Z) are compounds of formula (I) with identical constitutional formula ##STR00011## wherein it applies that one of the four wavy lines denotes a double bond and the remaining wavy lines denote a single bond, respectively, and X is selected from O, CH.sub.2 and OCH.sub.2, and the first compound (E) is trans-configurated and the second compound (Z) is cis-configurated, wherein the weight ratio of compound (E) to compound (Z) in the mixture is in the range of 10:90 to 65:30, wherein the mixture comprises one or several compounds selected from the group consisting of cyclohexadec-8-en-1-one, oxacyclohexadecen-2-one, 17-oxacycloheptadec-9-en-1-one, particularly (9Z)-17-oxacycloheptadec-9-en-1-one, and cyclohexadec-5-en-1-one, with the proviso that in case of cyclohexadec-8-en-1-one the weight ratio of compound (E) to compound (Z) in the mixture is not 40.6:30.5 or 20:10, and with the proviso that in case of cyclohexadec-5-en-1-one the weight ratio of compound (E) to compound (Z) in the mixture is not 37:62, comprising the following steps: (i) providing a base mixture comprising a first compound (E) and a second compound (Z), wherein compounds (E) and (Z) are compounds of formula (I) with identical constitutional formula ##STR00012## wherein it applies that one of the four wavy lines denotes a double bond and the remaining wavy lines denote a single bond, respectively, and X is selected from O, CH.sub.2 and OCH.sub.2, and the first compound (E) is trans-configurated and the second compound (Z) is cis-configurated, wherein the weight ratio of compound (E) to compound (Z) in the base mixture is higher than 10:90, wherein the mixture comprises one or several compounds selected from the group consisting of cyclohexadec-8-en-1-one, oxacyclohexadecen-2-one, 17-oxacycloheptadec-9-en-1-one, particularly (9Z)-17-oxacycloheptadec-9-en-1-one, and cyclohexadec-5-en-1-one, (ii) performing an acid-catalyzed isomerization, on compound (E) contained in the base mixture, so that a mixture is obtained, wherein the weight ratio of compound (E) to compound (Z) in the mixture is in the range of 10:90 to 65:30, with the proviso that in case of cyclohexadec-8-en-1-one the weight ratio of compound (E) to compound (Z) in the mixture is not 40.6:30.5 or 20:10, and with the proviso that in case of cyclohexadec-5-en-1-one the weight ratio of compound (E) to compound (Z) in the mixture is not 37:62.

9. A fragrance substance mixture according to claim 3, wherein the amount of compound (E) and compound (Z) is sufficient (a) to mask or reduce the or one or several unpleasant olfactory impression(s) of another fragrance substance in the fragrance substance mixture, and/or (b) to enhance the or one or several pleasant olfactory impression(s) of another fragrance substance in the fragrance substance mixture.

10. A fragrance substance mixture according to claim 3, wherein the total amount of compounds of formula (I) with regard to the total weight of the fragrance substance mixture is 1 wt. % or less.

11. A perfumed product, containing a mixture according to claim 1.

12. A perfumed product according to claim 11, wherein the product is selected from the group consisting of perfume extraits, eau de parfums, eau de toilettes, aftershaves, eau de colognes, pre-shave products, splash colognes, perfumed refreshing tissues, acidic, alkaline and neutral detergents, textile fresheners, ironing aids, liquid detergents, powdery detergents, laundry pretreatment agents, fabric softeners, laundry soaps, laundry tablets, disinfectants, surface disinfectants, air improvers, aerosol sprays, waxes and polishes, personal care agents, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products, deodorants and antiperspirants, products for decorative cosmetic, candles, lamp oils, incense sticks, insecticides, repellents and fuels.

13. A method for producing a perfumed product, comprising the following steps: i) providing a mixture according to claim 1, ii) providing one or several further components of the perfumed product to be produced, and iii) contacting or mixing the further components provided in step ii) with a sensorially effective amount of the components provided in step i).

14. A method (a) for masking or reducing one or several unpleasant olfactory impressions of one or several unpleasantly smelling substances comprising combining the one or several unpleasantly smelling substances with a mixture of claim 1, and/or (b) for enhancing one or several pleasant olfactory impressions of one or several pleasantly smelling substances comprising combining the one or several pleasantly smelling substances with a mixture of claim 1.

15. A method of claim 14, wherein the one or several unpleasantly smelling substances and/or the one or several unpleasantly smelling substances is or are selected from the group consisting of alcohols, aldehydes, ketones, ethers, esters and carboxylates, and/or has or have a molar mass in the range of 150 to 285 g/mol.

16. A mixture of claim 1, wherein the weight ratio of compound (E) to compound (Z) in the mixture is in the range of 10:90 to 60:40.

17. A mixture of claim 2, wherein the fragrance substance mixture is a perfume oil.

18. A mixture according to claim 5, wherein the one, several or all of the additional fragrance substances has or have a molar mass in the range of 210 g/mol or less

19. A mixture according to claim 6, wherein the ratio of the total mass of fragrance substances that do not correspond to formula (I) to the total mass of compound(s) of formula (I) is higher than or equal to 90:10.

20. A mixture according to claim 6, wherein the ratio of the total mass of fragrance substances that do not correspond to formula (I) to the total mass of compound(s) of formula (I) is higher than or equal to 95:5.

Description

EXAMPLES

Example 1: Perfume Oil P1 Aldehydes

[0121]

TABLE-US-00001 Component wt. proportion ALDEHYDE C 11 10% in DPG 16 ALDEHYDE C 11 UNDECYLENE 10% in 18 DPG ALDEHYDE C 12 LAURIN 10% in DGP 14 ALDEHYDE C 12 MNA 10% in DGP 12 HEXENAL TRANS-2 10% in DPG 1.5 HEXENYL ACETATE CIS-3 4 VERTOCITRAL 7.5 MAGNOLAN 130 MINTONAT 35 DIHYDROMYRCENOL 70 ORANGE OIL 30 NEROLIONE 10% in DPG 1 HEXYL ACETATE 30 JASMAPRUNAT 18 ALDEHYDE C14 SO-CALLED 50 FRUITATE 1.8 ETHYL METHYL BUTYRATE-2 8 MANZANATE 1.2 ALLYL CYCLOHEXYL PROPIONATE 7 APRIFLOREN 2 DUPICAL 10% in DPG 3.5 ETHYL LINALOOL 57 DIMETHYL BENZYL CARBINYL 6.5 BUTYRATE ROSE ABS. 30 ROSAFEN 20 DAMASCENONE 1.2 DAMASCONE ALPHA 1.8 BENZYL ACETATE 28 HEDIONE 60 HEXYL CINNAMIC ALDEHYDE ALPHA 140 PARMANYL 3.5 MYSORE ACETATE 35 ISORALDEINE 70 28 ISOEUGENOL METHYL ETHER 3.5 HELIOTROPIN 3 AGRUMEX LC 70 AMBROCENIDE 10% in DPG 0.6 AMBROXIDE 1.4 950

[0122] The composition has to be described as aldehyde-like, fresh-airy with leavy green, peach-like and ambergris-like scent impressions.

[0123] An addition of 10% (with regard to the total weight of the fragrance substances of the group of aldehydes contained in the judged fragrance substance mixture) of an isomer mixture of cyclohexadec-8-en-1-one (here: 60% trans-cyclohexadec-8-en-1-one: 40% cis-cyclohexadec-8-en-1-one) results in a distinct, unexpected increase of the green and fruity scent impressions that remind of green apples.

Example 2: Perfume Oil P2 Alcohols

[0124]

TABLE-US-00002 Component wt. proportion ALDEHYDE C 12MNA 5 LINOLAL 10 VERTOCITRAL 5 GALBANUM RESIN SYNTH. 5 MAGNOLAN 25 MINTONAT 30 DIHYDROMYRCENOL 50 ORANGE OIL 90 PETITGRAIN OIL PARAG. 10 LAVANDIN GROSSO RCO 30 HERBOXANE 30 FREESIOL 30 LINALOOL 70 GERANIUM RCO 30 PHENYL ETHYL ACETATE 10 PHENYL ETHYL ALCOHOL 70 CITRONELLOL 20 GERANIOL 20 ROSAFEN 60 BENZYL ACETATE 50 AMYL CINNAMIC ALDEHYDE ALPHA 60 YLANG MC TYPE BASE 20 AMYL SALICYLATE 50 PARMANYL 5 ISORALDEINE 70 30 EUGENOL 10 ANISALDEHYDE 10 HELIOTROPIN 10 CINNAMYL ACETATE 10 COUMARIN 10 CYCLABUTE 10 HERBAFLORAT 50 PATCHOULI OIL 10 AMBROXIDE 5 CITRYLAL 10 950

[0125] The composition has to be described as a floral accord of fresh garden flowers with citric scent notes reminding of garden herbs.

[0126] The addition of 10% (with regard to the total weight of the fragrance substances of the group of alcohols contained in the judged fragrance substance mixture) of an isomer mixture of cyclohexadec-8-en-1-one (here: 40% trans-cyclohexadec-8-en-1-one: 60% cis-cyclohexadec-8-en-1-one) makes the composition appear much more lively, lighter floral and less herbal.

Example 3: Production of a Mixture According to the Invention (Enrichment of Z-Isomer by Means of Isomerization (e.g. by Using Globalide, Ambrettolide or Velvione))

[0127] 45 g Ambrettolide (17-oxacycloheptadec-9-en-1-one) (here: 99% (E) and 0.6% (Z)) are dissolved in 225 ml isopropanol and 3.0 g of nitric acid (65%) are added. Subsequently, it is stirred for 8 h at room temperature.

[0128] Workup: Soda is added to the batch, it is concentrated on the rotary evaporator and distilled by means of Kugelrohr (KR) distillation.

[0129] It can be proceeded in a corresponding manner starting from an isomer mixture of Globalide or Velvioneinstead of Ambrettolide(see the table listed below for details).

Isomerization Results:

[0130]

TABLE-US-00003 GC-% GC-% Structure MG educt isomerization Globalide [00006] 238 72% E 22% Z 65% E 31% Z Ambrettolide [00007] 252 99.0% E 0.6% Z 67% E 31% Z Velvione [00008] 236 37% E 62% Z 21% E 78% Z

Example 4: Production of a Mixture According to the Invention (Enrichment of Z-Isomer by Means of Distillation (of e.g. Globanone))

Apparatus:

[0131] 4000 ml three-necked flask (DHK), magnetic stirrer (MGR), 1.5 m Sulzer column, mushroom heating hood
2013.2 g Globanone are finely distilled.

TABLE-US-00004 ST C. KT C. R:D mbar Yield in g Fraction 1 to 187 112.2 80:2 3.8 32.6 Fraction 2 to 191 140.7 80:2 3.0 12.8 Fraction 3 to 193 141.5 80:2 3.0 31.4 Fraction 4 to 196 142.0 80:2 3.0 21.9 Fraction 5 to 197 142.3 80:2 3.0 80.3 Fraction 6 to 198 141.7 100:2 2.9 26.7 Fraction 7 to 198 141.9 100:2 3.0 68.2 Fraction 8 to 198 142.2 100:2 3.0 25.5 Fraction 9 to 199 141.5 80:2 3.0 86.4 Fraction 10 to 200 140.4 80:2 2.7 95.1 Fraction 11 to 198 140.6 80:2 2.7 84.3 Sump sample 1 SP-1 Fraction 13 to 199 141.6 80:2 2.9 249.4 Fraction 14 to 198 141.6 40:2 3.0 198.0 Fraction 15 to 198 142.5 40:2 3.1 193.2 Sump sample 2 SP-2 Fraction 16 to 200 140.8 80:2 2.6 132.5 Fraction 17 to 203 139.7 80:2 2.6 83.6 Fraction 18 to 196 140.2 80:2 2.6 9.3 Hold Up 55.7 Residue 409
27.0 g of the residue are KR distilled.

TABLE-US-00005 27.0 g Input T C. R:D mbar Yield in g KRD-Fr. 150 0:1 1.4 21.4 KRD-Res. 5.8 used

KRD-2

[0132]

TABLE-US-00006 382 g Input T C. R:D mbar Yield in g KRD-Fr. 153 0:1 0.9 303.4 KRD-Res. 75.3
KRD-2 is distilled again! [0133] Apparatus: 500 ml DHK, MGR, 50 cm FKK (packed column) with Wilson spirals, mushroom heating hood

TABLE-US-00007 Use KRD-2 ST C. KT C. R:D mbar Yield in g RF 176 109 1:0 0.5 Fraction 1 to 174 122 80:2 0.8 11.5 Fraction 2 to 176 125 80:2 0.9 13.6 Fraction 3 to 179 127 80:2 1.0 19.9 Fraction 4 to 180 80:2 0.9 14.9 Fraction 5 to 177 130 80:2 1.1 24.0 Fraction 6 to 176 130 80:2 1.1 16.9 Fraction 7 to 175 129 80:2 1.1 13.2 Fraction 8 to 180 149 80:2 3.4 22.4 Sump sample SP-1 Fraction 9 to 184 19 60:2 3.4 30.1 Fraction 10 to 182 130 60:2 1.0 36.2 Fraction 11 to 194 135 40:2 1.3 57.3 Hold Up 10.0 Residue 34.2

Analyses:

[0134]

TABLE-US-00008 GC(FGC811)DB-1: Index Input Fr. 1 Fr. 2 Fr. 3 Fr. 4 Fr. 5 Fr. 6 Fr. 7 Fr. 8 Fr. 9 Fr. 10 % VL ca. 28 3.0 3.9 1.7 0.4 0.5 0.4 0.3 0.2 0.3 Forerun 1856 4.2 4.2 3.4 3.1 2.0 1.6 1.2 1.1 0.9 0.8 7-E 1883 68.0 60.3 81.7 80.8 82.4 83.7 85.1 83.5 82.9 81.9 82.0 trans 1888 29.8 7.5 11.0 11.8 12.8 13.9 12.8 14.9 15.7 17.0 16.9 cis Index Input Fr. 11 Fr. 12 Fr. 13 Fr. 14 Fr. 15 Fr. 16 Fr. 17 Fr. 18 Rue HU % VL 0.3 0.2 0.1 0.1 0.1 0.1 Forerun 1856 0.7 0.5 0.5 0.3 0.2 0.2 0.2 0.2 0.2 7-E 1883 68.0 81.9 80.5 79.3 76.5 71.3 63.7 60.0 59.3 30.5 51.4 trans 1888 29.8 17.1 18.8 20.2 23.2 28.5 36.1 39.8 40.4 62.9 46.3 cis Index Input KRD KRD-2 % VL Forerun 1856 7-E 1883 68.0 30.8 30.4 trans 1888 29.8 62.6 63.2 cis NL 6.6 6.4 Afterrun KRD-2-Distillation: Index KRD-2 Fr. 1 Fr. 2 Fr. 3 Fr. 4 Fr. 5 Fr. 6 Fr. 7 Fr. 8 SP-1 Fr. 9 Fr. 10 % VL 0.1 0.3 Forerun 1856 0.4 0.3 0.1 0.1 0.1 0.1 0.1 0.1 7-E 1883 30.4 34.2 35.2 40.2 35.1 34.9 35.7 33.9 32.9 26.9 32.0 32.7 trans 1888 63.2 63.4 62.4 54.8 63.1 63.1 62.0 63.8 64.3 62.5 65.5 62.2 cis NL 6.4 2.3 2.0 4.4 1.8 1.9 2.2 2.2 2.7 10.6 2.4 5.0 Afterrun Index KRD-2 Fr. 11 Rue HU % VL Forerun 1856 0.2 0.1 0.4 7-E 1883 30.4 28.6 15.4 24.7 trans 1888 63.2 66.4 46.0 61.5 cis NL 6.4 4.8 38.5 13.6 Afterrun