Enamine and/or aminal fragrance precursors derived from (E/Z)-9-hydroxy-5,9-di-methyldec-4-enal

Abstract

A fragrance precursor of (E/Z)-9-hydroxy-5,9-dimethyldec-4-enal, comprising at least an enamine and/or an aminal as reaction product of (E/Z)-9-hydroxy-5,9-dimethyldec-4-enal (compound according to formula (I)) and a primary and/or secondary amine ##STR00001##
useful as a perfume ingredient.

Claims

1. A fragrance precursor of (E/Z)-9-hydroxy-5,9-dimethyldec-4-enal, comprising at least an enamine and/or an aminal as reaction product of (E/Z)-9-hydroxy-5,9-dimethyldec-4-enal and a primary and/or secondary amine.

2. The fragrance precursor according to claim 1, wherein the primary and/or secondary amine is selected from the group consisting of: aromatic amines; primary or secondary aliphatic amines; etheramines; ethylene- and propylene-amines; amino acids and derivatives; polyamines; N-(3-aminopropyl)imidazole, nipecotamide, skatole and indole.

3. The fragrance precursor of claim 2, wherein the aromatic amine is selected from: methyl 2-aminobenzoate (methyl anthranilate), 2-amino-acetophenone, ortho, meta or para aminobenzoates of formula II ##STR00005## wherein: R1=C1-C12 linear or branched alkyl, alkenyl, cycloalkyl, cycloalkenyl or alkylaryl and, R2=H, Me, or Et.

4. The fragrance precursor of claim 2, wherein the primary or secondary aliphatic amines are selected from: C8-C30 linear or branched alkylamines or alkyldiamines.

5. The fragrance precursor of claim 2, wherein the polyamines are selected from: primary and secondary polyetheramines, polyethyleneimines, polypropyleneimines, polyamidoamines, polyamino acids, polyvinylamines, poly(ethylene glycol) bis(amine) and amino substituted polyvinylalcohols.

6. The fragrance precursor according to claim 2, comprising at least one of: methyl 2-(((1E/Z, 4E/Z)-9-hydroxy-5,9-dimethyldeca-1,4-dien-1-yl)amino)benzoate; and, (E/Z)-dimethyl 2,2-((9-hydroxy-5,9-dimethyldec-4-ene-1,1-diyl)bis(azanediyl))dibenzoate.

7. The fragrance precursor according to claim 2 which is odiferous and which is a perfume ingredient.

8. A method of imparting a muguet odour characteristic to a personal care composition or household care composition, the method comprising the step of: including a fragrance precursor according to claim 2 in the personal care composition or household care composition.

9. A method of imparting a muget odour characteristic to a perfume composition comprising the step of: adding to said composition at least a fragrance precursor according to claim 2.

10. The fragrance precursor according to claim 1, comprising: at least one of: methyl 2-(((1E/Z, 4E/Z)-9-hydroxy-5,9-dimethyldeca-1,4-dien-1-yl)amino)benzoate, and, (E/Z)-dimethyl 2,2-((9-hydroxy-5,9-dimethyldec-4-ene-1,1-diyl)bis(azanediyl))dibenzoate.

11. The fragrance precursor according to claim 1 which is odiferous and which is a perfume ingredient.

12. The fragrance precursor according to claim 11, wherein perfume ingredient releases muguet odour characteristics.

13. A perfume composition comprising a fragrance precursor according to claim 1.

14. The perfume composition according to claim 13 that is substantially free of 4(4-hydroxy-4-methylphenyl) 3-cyclohexane carboxaldehyde.

15. The perfume composition according to claim 13 which further comprises: (E/Z)-9-hydroxy-5,9-dimethyldec-4-enal.

16. The perfume composition according to claim 13, which further comprises one or more additional fragrance ingredients.

17. The perfume composition according to claim 13, which is adapted to release an ingredient with muguet odour characteristics.

18. A personal care or household care composition comprising at least a fragrance precursor according to claim 1.

19. A method of imparting a muguet odour characteristic to a perfume composition comprising the step of: adding to said composition at least a fragrance precursor according to claim 1.

20. A method of imparting a muguet odour characteristic to a personal care composition or household care composition, the method comprising the step of: including a fragrance precursor according to claim 1 in the personal care composition or household care composition.

Description

Example 1: Mixing Methyl 2-aminobenzoate and (E/Z)-9-hydroxy-5,9-dimethyldec-4-enal (Molar Ratio 1:1)

(1) ##STR00004##

(2) A mixture of methyl 2-aminobenzoate (1.51 g, 10.0 mmol) and (E/Z)-9-hydroxy-5,9-dimethyldec-4-enal (1.98 g, 10.0 mmol) was stirred at 75 C. and 50 mbar for 7 h to yield 3.32 g of a bright yellow oil. No purification was needed as the product will be used in perfumery applications as is. Analysis of the crude reaction mixture revealed two major components, enamine methyl 2-(((1E/Z, 4E/Z)-9-hydroxy-5,9-di methyldeca-1,4-dien-1-yl)amino)benzoate and aminal (E/Z)-dimethyl 2,2-((9-hydroxy-5,9-dimethyldec-4-ene-1,1-diyl)bis(azanediyl))-dibenzoate (molar ratio enamine/aminal=2.4:1).

Methyl 2-(((1E/Z, 4E/Z)-9-hydroxy-5,9-dimethyldeca-1,4-dien-1-yl)amino)benzoate

(3) .sup.1H NMR (CDCl.sub.3, 400 MHz); mixture of (1E/Z, 4E/Z) isomers: =9.69 (br d, J=10.5 Hz, NH), 9.66 (br d, J=10.5 Hz, NH), 9.53 (br d, J=10.2 Hz, NH), 9.52 (br d, J=10.5 Hz, NH), 7.93-7.87 (m, 4H), 7.38-7.29 (m, 4H), 6.94-6.88 (m, 4H), 6.70-6.61 (m, 4H), 6.51-6.45 (m, 4H), 5.25-5.07 (m, 6H), 4.65-4.57 (m, 2H), 3.87 (s, 3H), 3.87 (s, 3H), 3.84 (s, 3H), 3.82 (s, 3H), 2.92-2.87 (m, 4H), 2.79-2.75 (m, 4H), 2.13-1.91 (m, 8H), 1.72-1.64 (m, 12H), 1.48-1.36 (m, 16H), 1.21-1-17 (m, 24H) ppm. .sup.13C NMR (CDCl.sub.3, 100 MHz); mixture of (1E/Z, 4E/Z) isomers: =168.9 (s), 168.8 (s), 168.8 (s), 168.7 (s), 146.6 (s), 146.6 (s), 146.4 (s), 146.4 (s), 136.1 (s), 135.8 (s), 135.8 (s), 135.7 (s), 134.5 (d), 134.5 (d), 134.5 (d), 134.5 (d), 131.6 (d), 131.5 (3d), 125.1 (d), 125.0 (d), 123.5 (d), 123.3 (d), 123.1 (d), 122.9 (d), 122.7 (d), 122.3 (d), 116.4 (2d), 116.1 (d), 116.0 (d), 111.7 (d), 111.7 (d), 111.6 (d), 111.6 (d), 110.5 (s), 110.5 (s), 110.4 (s), 110.1 (s), 109.4 (d), 109.2 (d), 107.3 (d), 107.3 (d), 70.8 (s), 70.7 (s), 70.7 (s), 70.7 (s), 51.7 (q), 51.6 (q), 51.5 (q), 51.4 (q), 43.5 (t), 43.4 (t), 43.4 (2t), 39.9 (t), 39.9 (t), 32.0 (t), 31.9 (t), 29.1 (2q), 29.1 (4q), 29.1 (2q), 28.3 (t), 28.3 (t), 24.5 (t), 24.5 (t), 23.3 (q), 23.2 (q), 22.6 (t), 22.5 (t), 22.4 (2t), 15.9 (q), 15.7 (q) ppm. MS (EI); sum of (1E/Z, 4E/Z) isomers: 331 (25, [M].sup.+.), 316 (4), 244 (5), 230 (21), 198 (13), 190 (8), 178 (12), 177 (100), 158 (10), 151 (24), 146 (10), 145 (26), 119 (19), 92 (8), 77 (6).

(E/Z)-Dimethyl 2,2-((9-hydroxy-5,9-dimethyldec-4-ene-1,1-diyl)bis(azanediyl))dibenzoate

(4) .sup.1H NMR (CDCl.sub.3, 400 MHz); mixture of E/Z isomers: =8.03 (br d, J=6.5 Hz, 4NH), 7.91 (dd, J=8.1, 1.5 Hz, 4H), 7.34-7.29 (m, 4H), 6.68 (d, J=8.6 Hz, 4H), 6.65-6.60 (m, 4H), 5.24-5.18 (m, 2H), 5.03-4.97 (m, 2H), 3.82 (s, 12H), 2.25 (quart, J=7.3 Hz, 4H), 1.99-1.92 (m, 8H), 1.68 (d, J=1.0 Hz, 3H), 1.51 (br s, 3H), 1.48-1.33 (m, 8H), 1.19 (s, 6H), 1.14 (s, 6H) ppm. .sup.13C NMR (CDCl.sub.3, 100 MHz); mixture of E/Z isomers: =168.8 (2s), 168.8 (2s), 149.4 (2s), 149.4 (2s), 136.6 (s), 136.6 (s), 134.6 (2d), 134.6 (2d), 131.7 (2d), 131.7 (2d), 123.6 (d), 122.8 (d), 115.3 (2d), 115.3 (2d), 111.8 (2d), 111.8 (2d), 110.7 (2s), 110.5 (2s), 70.8 (s), 70.7 (s), 62.5 (d), 62.3 (d), 51.5 (2q), 51.5 (2q), 43.5 (t), 43.4 (t), 40.0 (t), 35.7 (t), 35.4 (t), 31.9 (t), 29.2 (2q), 29.0 (2q), 23.7 (t), 23.6 (t), 23.2 (q), 22.5 (t), 22.5 (t), 15.7 (q) ppm. MS (EI); sum of E/Z isomers: 482 (2, [M].sup.+.), 332 (23), 331 (25, [M].sup.+.-.NH(C.sub.6H.sub.4)CO.sub.2CH.sub.3), 316 (8), 272 (4), 244 (12), 230 (38), 198 (17), 190 (10), 178 (13), 177 (100), 164 (20), 151 (64), 145 (30), 120 (18), 119 (56), 92 (25).

(5) Odour description of the crude reaction mixture: floral muguet, natural, orange flower

Example 2: Mixing Methyl 2-aminobenzoate and (E/Z)-9-hydroxy-5,9-dimethyldec-4-enal (Molar Ratio 2:1)

(6) A mixture of methyl 2-aminobenzoate (3.02 g, 20.0 mmol) and (E/Z)-9-hydroxy-5,9-dimethyldec-4-enal (1.98 g, 10.0 mmol) was stirred at 75 C. and 50 mbar for 7 h to yield 4.73 g of a bright yellow oil. No purification was needed as the product will be used in perfumery applications as is. Analysis of the crude reaction mixture revealed two major components, aminal (E/Z)-dimethyl 2,2-((9-hydroxy-5,9-dimethyldec-4-ene-1,1-diyl)bis(azanediyl))-dibenzoate and enamine methyl 2-(((1E/Z, 4E/Z)-9-hydroxy-5,9-dimethyldeca-1,4-dien-1-yl)amino)benzoate (molar ratio aminal/enamine=2:1).

(7) Spectral data of (E/Z)-dimethyl 2,2-((9-hydroxy-5,9-dimethyldec-4-ene-1,1-diyl)bis(azanediyl))-dibenzoate and methyl 2-(((1E/Z, 4E/Z)-9-hydroxy-5,9-dimethyldeca-1,4-dien-1-yl)amino)-benzoate are reported in Example 1.

(8) Odour description of the crude reaction mixture: floral orange flower, methyl anthranilate, muguet

Example 3: Preparation of a Feminine Oriental Fine Fragrance

(9) TABLE-US-00001 Compound/Ingredient parts by weight 1/900 cis-3-Hexenyl acetate 3 Isoeugenyl acetate 25 Phenyl acetic acid (at 1% in DPG) 3 1,2,3,4,4a,5,6,7-Octahydro-2,5,5-trimethyl-2- 35 naphthalenol (Ambrinol) (at 1% in DPG) Ambrofix (at 10% in DPG) 2 Animalis 1745 subst. PMF 2 15 2-Ethoxy-9-methylen-2,6,6-trimethylbicyclo 20 [3.3.1]-nonane (Boisiris) l-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-1,6- 3 heptadien-3-one (Cetone V) Coumarin 20 (2E)-1-(2,6,6-Trimethyl-1-cyclohexen-1-yl) 8 but-2-en-1-one (Damascone beta) (at 10% in DPG) 2,6-Dimethylheptan-2-ol (Dimetol) (at 25 10% in DPG) 2-Ethyl-3-hydroxy-4-pyranone (Ethyl 14 Maltol) (at 1% in DPG) 3-Ethoxy-4-hydroxybenzaldehyd 15 (Ethylvanillin) Ethyl 2-ethyl-6,6-dimethyl-2- 100 cyclohexenecarboxylate & Ethyl 2,3,6,6- tetramethyl-2-cyclohexenecarboxylate (Givescone) Methyl 2-(3-oxo-2-pentylcyclopentyl) 250 acetate (Hedione) l,3-Benzodioxole-5-carbaldehyde 4 (Heliotropine) cis-3-Hexenol 3 Indolene 50%/Castor oil 20 3-Methyl-4-(2,6,6-trimethylcyclohex- 25 2-en-1-yl)but-3-en-2-one (Isoraldeine 95) Patchouli Ess. 20 2-Ethyl-4-(2,2,3-trimethylcyclopent- 45 3-en-1-yl)but-2-en-1-ol (Radjanol) 4-(4-Hydroxyphenyl)butan-2-one 5 (Raspberry Ketone) 4-Methyl-2-(2-methylprop-1-enyl) 3 tetrahydro-2H-pyran (Rose Oxide) 2-[1-(3,3-Dimethylcyclohexyl) 45 ethoxy]-2-methylpropyl cyclopropanecarboxylate (Serenolide) Methyl Cedryl Ketone 55 Dipropylene glycol (DPG) 82 Product from Example 1 55 Total: 900

(10) The addition of the reaction mixture comprising at least methyl 2-((-9-hydroxy-5,9-dimethyldeca-1,4-dien-1-yl)amino)-benzoate and dimethyl 2,2-((9-hydroxy-5,9-dimethyldec-4-ene-1,1-diyl)bis(azanediyl))-dibenzoate as prepared in Example 1 reinforces the floral character of the composition and provides an orange flower facet and at the same time adds volume and performance to the whole composition. It blends very well with Hedione, Indolene and Patchouli and gives a subtle sensuality to this oriental feminine fine fragrance.