IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS

Abstract

A fragrance precursor of 3-(4-isobutyl-2-methyl phenyl)propanal, comprising at least an enamine and/or an aminal as reaction product of 3-(4-isobutyl-2-methylphenyl)propanal (compound according to formula (I)) and a primary and/or secondary amine

##STR00001##

useful as a perfume ingredient.

Claims

1. A fragrance precursor of 3-(4-isobutyl-2-methylphenyl)propanal, comprising at least an enamine and/or an aminal as reaction product of 3-(4-isobutyl-2-methylphenyl)propanal and a primary and/or secondary amine.

2. A fragrance precursor according to claim 1, wherein the primary and/or secondary amine is selected from the group consisting of aromatic amines, ortho, meta or para aminobenzoates of formula II ##STR00005## in which R.sup.1═C1-C12 linear or branched alkyl, alkenyl, cycloalkyl, cycloalkenyl or alkylaryl and R.sup.2═H, Me, Et); primary or secondary aliphatic amines; etheramines; ethylene- and propylene-amines; amino acids and derivatives; polyamines, amino substituted polyvinylalcohols; N-(3-aminopropyl)imidazole, nipecotamide, skatole and indole ##STR00006##

3. A fragrance precursor according to claim 1 comprising at least (E/Z)-methyl 2-((3-(4-isobutyl-2-methylphenyl)prop-1-en-1-yl)amino)benzoate and/or dimethyl 2,2′-((3-(4-isobutyl-2-methylphenyl)propane-1,1-diyl)bis(azanediyl))-dibenzoate.

4. A perfume ingredient comprising a fragrance precursor according to claim 1.

5. A perfume ingredient comprising a fragrance according to claim 4, wherein the perfume ingredient can release an ingredient with muguet odour characteristics.

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

7. A perfume composition according to claim 6 that is substantially free of aryl-substituted propanals that are unsubstituted on the aryl ring at a position ortho to the substituent bearing the aldehyde functionality, in particular Lilial™.

8. A perfume composition according to claim 6 further comprising 3-(4-isobutyl-2-methylphenyl)propanal.

9. A perfume composition according to claim 6 comprising one or more additional fragrance ingredients.

10. A perfume composition according to claim 6 which can release an ingredient with muguet odour characteristics.

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

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

13. A perfume ingredient comprising a fragrance precursor according to claim 2.

14. A perfume ingredient comprising a fragrance precursor according to claim 3.

15. A fragrance precursor according to claim 2, wherein the primary and/or secondary amine is selected from the group consisting of methyl 2-aminobenzoate (methyl anthranilate), 2-amino-acetophenone, ortho, meta or para aminobenzoates of formula II.

16. A fragrance precursor according to claim 2, wherein the primary and/or secondary amine is selected from the group consisting of C8-C30 linear or branched alkylamines or alkyldiamines.

17. A fragrance precursor according to claim 2, wherein the primary and/or secondary amine is selected from primary and secondary polyetheramines, polyethyleneimines, polypropyleneimines, polyamidoamines, polyamino acids, polyvinylamines, poly(ethylene glycol) bis(amine), amino substituted polyvinylalcohols.

Description

EXAMPLE 1

Mixing methyl 2-aminobenzoate and 3-(4-isobutyl-2-methylphenyl)propanal (Molar Ratio 1:1)

[0109] ##STR00004##

[0110] A mixture of methyl 2-aminobenzoate (1.51 g, 10.0 mmol) and 3-(4-isobutyl-2-methylphenyl)-propanal (2.04 g, 10.0 mmol) was stirred at 75° C. and 50 mbar for 6 h to yield, after cooling to 25° C., 3.17 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” (E/Z)-methyl 2-((3-(4-isobutyl-2-methylphenyl)prop-1-en-1-yl)amino)benzoate and “aminal” dimethyl 2,2′-((3-(4-isobutyl-2-methylphenyl)propane-1,1-diyl)bis(azanediyl))-dibenzoate (molar ratio enamine/aminal=3:1).

[0111] (E/Z)-Methyl 2-((3-(4-isobutyl-2-methylphenyl)prop-1-en-1-yl)amino)benzoate:

[0112] .sup.1H NMR (CDCl.sub.3, 400 MHz); mixture of E/Z isomers: δ=9.85 (br d, J=11.0 Hz, NH), 9.59 (br d, J=10.8 Hz, NH), 7.94 (dd, J=8.1, 1.5 Hz, 1H), 7.89 (dd, J=8.1, 1.5 Hz, 1H), 7.38 (dddd, J=8.8, 7.1, 1.7, 0.5 Hz, 1H), 7.33 (dddd, J=9.1, 7.1, 2.5, 0.7 Hz, 1H), 7.15 (d, J=7.6 Hz, 1H), 7.09 (d, J=8.3 Hz, 1H), 7.02-6.84 (m, 4H), 6.70 (ddd, J=8.1, 7.1, 1.0 Hz, 1H), 6.67-6.44 (m, 5H), 5.28 (dt, J=13.5, 6.9 Hz, 1H), 4.72 (dtd, J=8.3, 7.3, 0.7 Hz, 1H), 3.87 (s, 3H), 3.85 (s, 3H), 3.47 (dd, J=7.1, 1.5 Hz, 2H), 3.36 (dd, J=6.9, 0.7 Hz, 2H), 2.41 (d, J=7.1 Hz, 2H), 2.41 (d, J=7.1 Hz, 2H), 2.31 (s, 3H), 2.30 (s, 3H), 1.89-1.78 (m, 2H), 0.90 (d, J=6.6 Hz, 6H), 0.90 (d, J=6.6 Hz, 6H) ppm. .sup.13C NMR (CDCl.sub.3, 100 MHz); mixture of E/Z isomers: δ=168.9 (s), 168.8 (s), 146.6 (s), 146.5 (s), 139.5 (s), 139.4 (s), 136.4 (s), 136.2 (s), 135.8 (s), 135.6 (s), 134.6 (d), 134.5 (d), 131.7 (d), 131.6 (d), 131.0 (d), 131.0 (d), 128.4 (d), 128.4 (d), 126.7 (d), 126.7 (d), 126.0 (d), 123.7 (d), 116.7 (d), 116.3 (d), 111.8 (d), 111.7 (d), 110.8 (s), 110.3 (s), 108.6 (d), 106.7 (d), 51.7 (q), 51.6 (q), 45.0 (t), 45.0 (t), 33.4 (t), 30.2 (d), 30.2 (d), 29.6 (t), 22.4 (2q), 22.4 (2q), 19.5 (q), 19.3 (q) ppm. MS (EI); sum of E/Z isomers: 338 (16), 337 (100, [M]•+), 322 (8), 262 (12), 186 (24), 151 (43), 143 (56), 131 (25), 129 (12), 117 (10), 57 (12).

[0113] Dimethyl 2,2′-((3-(4-isobutyl-2-methylphenyl)propane-1,1-diyl)bis(azanediyl))-dibenzoate:

[0114] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ=8.11 (br d, J=6.6 Hz, 2NH), 7.91 (dd, J=8.1, 1.7 Hz, 2H), 7.27-7.23 (m, 2H), 7.02 (d, J=7.6 Hz, 1H), 6.92 (d, J=1.7 Hz, 1H), 6.88 (dd, J=7.8, 1.7 Hz, 1H), 6.63-6.59 (m, 2H), 6.52 (d, J=8.6 Hz, 2H), 4.99 (quint, J=6.4 Hz, 1H), 3.81 (s, 6H), 2.83 (t, J=7.7 Hz, 2H), 2.40 (d, J=7.1 Hz, 2H), 2.23 (s, 3H), 2.19-2.14 (m, 2H), 1.83 (non, J=6.6 Hz, 1H), 0.89 (d, J=6.6 Hz, 6H) ppm. .sup.13C NMR (CDCl.sub.3, 100 MHz): δ=168.8 (2s), 149.3 (2s), 139.5 (s), 136.1 (s), 135.5 (s), 134.6 (2d), 131.7 (2d), 131.1 (d), 128.6 (d), 126.6 (d), 115.3 (2d), 111.7 (2d), 110.5 (2s), 62.2 (d), 51.4 (2q), 44.9 (t), 36.0 (t), 30.1 (d), 28.4 (t), 22.3 (2q), 19.1 (q) ppm. MS (EI): 488 (2, [M]+•), 338 (84), 337 (95, [M]+•-••NH(C6H4)CO2CH3), 322 (13), 306 (12), 262 (14), 186 (31), 161 (23), 151 (100), 143 (64), 131 (41), 120 (23), 119 (76), 92 (27), 57 (20).

[0115] Odour description of the crude reaction mixture: floral aldehydic, floral orange flower, methyl anthranilate, slightly green latex

EXAMPLE 2

Mixing methyl 2-aminobenzoate and 3-(4-isobutyl-2-methylphenyl)propanal (Molar Ratio 2:1)

[0116] A mixture of methyl 2-aminobenzoate (3.02 g, 20.0 mmol) and 3-(4-isobutyl-2-methylphenyl)-propanal (2.04 g, 10.0 mmol) was stirred at 75° C. and 50 mbar for 6 h to yield, after cooling to 25° C., 4.60 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” dimethyl 2,2′-((3-(4-isobutyl-2-methylphenyl)propane-1,1-diyl)bis-(azanediyl))dibenzoate and “enamine” (E/Z)-methyl 2-((3-(4-isobutyl-2-methylphenyl)prop-1-en-1-yl)amino)benzoate (molar ratio aminal/enamine=2:1).

[0117] Spectral data of dimethyl 2,2′-((3-(4-isobutyl-2-methylphenyl)propane-1,1-diyl)bis-(azanediyl))dibenzoate and (E/Z)-methyl 2-((3-(4-isobutyl-2-methylphenyl)prop-1-en-1-yl)amino)benzoate are reported in Example 1.

[0118] Odour description of the crude reaction mixture: floral orange flower, floral aldehydic, methyl anthranilate

EXAMPLE 3

Preparation of a Feminine Floral Fine Fragrance

[0119]

TABLE-US-00001 parts by weight Compound/Ingredient 1/900 Benzyl acetate 40 2-Phenylethanol 20 Decanal (at 10% in DPG) 8 10-Undecenal (at 10% in DPG) 8 Baume Perou Ess 25 Berga mote Ess 45 Coumarin 20 Methyl 2,4-dihydroxy-3,6-dimethyl benzoate (Evernyl) 3 1-Phenylethyl acetate (Gardenol) 35 Geranium Ess 2 Ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate & Ethyl 100 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate (Givescone) Methyl 2-(3-oxo-2-pentylcyclopentyl)acetate (Hedione) 70 (3E)-4-(2,6,6-trimethylcyclohex-1-en-1-yl)but-3-en-2-one 25 (Ionone beta) Jasmin absolute 2 (Z)-3-Methyl-2-(pent-2-enyl)cyclopent-2-enone (cis-Jasmone) 5 Lentisque oil 8 Musk ketone (Low MX) 4 2-Methylundecanoic acid (Mystikal) (at 1% in DPG) 1 Neroli oil bigarde 30 γ-Undecalactone 7 (3,7-Dimethylocta-1,6-dien-3-yl)-dimethylcarbamate 20 (Pepperwood) (E)-2-Methyl-4-(2,2,3-trimethyl-1-cyclopent-3-enyl)- 25 but-2-en-1-ol 6-Ethyl-3-methyl-6-octen-1-ol (Super Muguet) 25 Methyl cedryl ketone 200 Dipropylene glycol (DPG) 122 Product from Example 2 50 Total: 900

[0120] The addition of the reaction mixture comprising at least dimethyl 2,2′-((3-(4-isobutyl-2-methylphenyl)propane-1,1-diyl)bis-(azanediyl))dibenzoate and (E/Z)-methyl 2-((3-(4-isobutyl-2-methylphenyl)prop-1-en-1-yl)amino)-benzoate (as prepared in Example 2) nicely wraps the green character of the composition, provides a muguet and orange flower facet and increases the creaminess. At the same time, the product adds volume, diffusion and performance to the whole composition.

EXAMPLE 4

Preparation of a Feminine Floral Aldehydic Fine Fragrance

[0121]

TABLE-US-00002 parts by weight Compound/Ingredient 1/900 Decanal (at 10% in DPG) 8 10-Undecenal (at 10% in DPG) 8 2-Methylundecanal (at 10% in DPG) 3 Allyl amyl glycolate 2 (1R,2S,2′S,4R)-1,7,7-Trimethyl-2′- 8 (1-methylethyl)spiro[bicyclo[2.2.1]heptane- 2,4′-[1,3]dioxane] (Belambre) (at 50% in IPM) 6-Methoxy-2,6-dimethyloctanal (Calypsone) 20 3,7-Dimethyloct-6-en-1-ol (Citronellol) 25 Coumarin 20 3-Ethoxy-4-hydroxybenzaldehyd (Ethylvanillin) 10 (2E)-5-Methylhept-2-en-4-one (Filbertone) (at 10% in 4 TEC at 10% in DPG) 3-(3-Isopropylphenyl)butanal (Florhydral) 3 cis-1-(1,2,3,4,5,6,7,8)-Octahydro-1,2,8,8-tetramethyl- 55 2-naphthalenyl)-ethanone (Georgywood) Methyl 2-(3-oxo-2-pentylcyclopentyl)acetate (Hedione) 150 Indolene 50%/Castor oil 2 2-Methoxy-4-prop-1-en-2-yl-phenol (Isoeugenol) 2 3,7-Dimethyl-1,6-octadien-3-ol (Linalol) 55 Mandarine oil 25 3-Methyl-5-phenylpentan-1-ol (Mefrosol) 25 2-Methylundecanoic acid (Mystikal) (at 1% in DPG) 2 (10Z-13-Methyloxacyclopentadec-10-en-2-one (Nirvanolide) 30 Orange oil 10 (1-Methyl-2-(((1R,3R)-2,2,3-trimethylcyclopentyl) 20 methyl)cyclopropyl)methanol (3,7-Dimethylocta-1,6-dien-3-yl)-dimethylcarbamate 55 (Pepperwood) 2-Cyclohexylidene-2-o-tolylacetonitrile (Petalia) 45 (2E)-5,6,7-Trimethylocta-2,5-dien-4-one (Pomarose) 1 2-Ethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but- 45 2-en-1-ol (Radjanol) 2-[1-(3,3-Dimethylcyclohexyl)ethoxy]-2-methylpropyl 45 cyclopropanecarboxylate (Serenolide) 1-(Cyclopropylmethyl)-4-methoxybenzene (Toscanol) 4 3-Methoxy-4-hydroxybenzaldehyd (Vanillin) 15 Dipropylene glycol (DPG) 188 Product from Example 1 15 Total: 900

[0122] The addition of the reaction mixture comprising at least (E/Z)-methyl 2-((3-(4-isobutyl-2-methylphenyl)prop-1-en-1-yl)-amino)benzoate and dimethyl 2,2′-((3-(4-isobutyl-2-methylphenyl)propane-1,1-diyl)bis-(azanediyl))dibenzoate (as prepared in Example 1) leads to a more sophisticated accord by reducing the sharpness of the aldehydes and by providing an orange flower note together with a muguet facet. The product blends very well with Pepperwood, Mystikal and Pomarose and adds volume, diffusion and performance to the whole composition.