ARYL BETA DIKETONES AND THEIR USE AS ODORANTS

Abstract

The present invention refers to aryl beta diketones of the formula (I)

##STR00001## wherein Y, R.sup.1, R.sup.2 and R.sup.3 have the meaning R.sup.1 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4 alkyl, hydroxyl, methoxy, CF.sub.3 and F; R.sup.2 is selected from the group consisting of methyl and ethyl; R.sup.3 is selected from the group consisting of methyl and ethyl; and Y is a bivalent residue selected from the group consisting of C(O); CH.sub.2CH.sub.2C(O); CR.sup.IR.sup.IIC(O), wherein R.sup.I and R.sup.II are independently selected from hydrogen and methyl; and CHR.sup.IIICHR.sup.IVC(O), wherein R.sup.III and R.sup.IV are independently selected from hydrogen and methyl with the proviso, that R.sup.IIIR.sup.IV are hydrogen or either R.sup.III or R.sup.IV is methyl. The invention further refers to fragrance compositions and fragranced articles comprising them.

Claims

1. A method of utilizing as fragrance of a compound of formula (I) ##STR00010## comprising mixing or generating the compound of formula (I) in a fragrance composition or a fragranced article, wherein R.sup.1 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4 alkyl, hydroxyl, methoxy, CF.sub.3 and F; R.sup.2 is selected from the group consisting of methyl and ethyl; R.sup.3 is selected from the group consisting of methyl and ethyl; and Y is a bivalent residue selected from the group consisting of C(O); CH.sub.2CH.sub.2C(O); CR.sup.IR.sup.IIC(O), wherein R.sup.I and R.sup.II are independently selected from hydrogen and methyl; and CHR.sup.IIICHR.sup.IVC(O), wherein R.sup.III and R.sup.IV are independently selected from hydrogen and methyl with the proviso, that R.sup.IIIR.sup.IV are hydrogen or either R.sup.III or R.sup.IV is methyl.

2. The method according to claim 1 wherein the compound of formula (I) is selected from the group consisting of 2-methyl-1(p-tolyl)butane-1,3-dione, 2-methyl-1-phenylbutane-1,3-dione, 3-methyl-l-phenylbutane-2,4-dione, 3-methyl-6-phenylhexane-2,4-dione, 3-methyl-6-phenylhex-5-ene-2,4-dione, 1-(4-methoxyphenyl)-2-methylbutane-1,3-dione, 6-(4-methoxyphenyl)-3-methylhexane-2,4-dione, 6-(4-hydroxyphenyl)-3-methylhexane-2,4-dione, 2-ethyl-1-(p-tolyl)butane-1,3-dione, 1-(4-ethylphenyl)-2-methylbutane-1,3-dione, 2-methyl-1-(4-(trifluoromethyl)phenyl)butane-1,3-dione, and 2-methyl-1-(p-tolyl)pentane-1,3-dione.

3. A fragrance composition comprising a compound of formula (I) ##STR00011## wherein R.sup.1 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4 alkyl, hydroxyl, methoxy, CF.sub.3 and F; R.sup.2 is selected from the group consisting of methyl and ethyl; R.sup.3 is selected from the group consisting of methyl and ethyl; and Y is a bivalent residue selected from the group consisting of C(O); CH.sub.2CH.sub.2C(O); CR.sup.IR.sup.IIC(O), wherein R.sup.I and R.sup.II are independently selected from hydrogen and methyl; and CHR.sup.IIICHR.sup.IVC(O), wherein R.sup.III and R.sup.IV are independently selected from hydrogen and methyl with the proviso, that R.sup.IIIR.sup.IV are hydrogen or either R.sup.III or R.sup.IV is methyl; and at least one additional odorant.

4. A fragranced article comprising as odorant a compound of formula (I), or a mixture thereof, ##STR00012## wherein R.sup.1 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4 alkyl, hydroxyl, methoxy, CF.sub.3 and F; R.sup.2 is selected from the group consisting of methyl and ethyl; R.sup.3 is selected from the group consisting of methyl and ethyl; and Y is a bivalent residue selected from the group consisting of C(O); CH.sub.2CH.sub.2C(O); CR.sup.IR.sup.IIC(O), wherein R.sup.I and R.sup.II are independently selected from hydrogen and methyl; and CHR.sup.IIICHR.sup.IVC(O), wherein R.sup.III and R.sup.IV are independently selected from hydrogen and methyl with the proviso, that R.sup.IIIR.sup.IV are hydrogen or either R.sup.III or R.sup.IV is methyl; and a consumer product base.

5. The fragranced article according to claim 4 wherein the consumer product base is selected from products having a pH of 9 or lower.

6. The fragranced article according to claim 4 selected from shampoo, detergent, fabric conditioner, hair conditioner, liquid soap, bar soap, shower gel, tumble dryer sheet, body lotion, and skin care cream.

7. A method of improving, enhancing or modifying a consumer product base by means of addition thereto of an olfactory acceptable amount of a compound of formula (I) ##STR00013## wherein R.sup.1 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4 alkyl, hydroxyl, methoxy, CF.sub.3 and F; R.sup.2 is selected from the group consisting of methyl and ethyl; R.sup.3 is selected from the group consisting of methyl and ethyl; and Y is a bivalent residue selected from the group consisting of C(O); CH.sub.2CH.sub.2C(O); CR.sup.IR.sup.IIC(O), wherein R.sup.I and R.sup.II are independently selected from hydrogen and methyl; and CHR.sup.IIICHR.sup.IVC(O), wherein R.sup.III and R.sup.IV are independently selected from hydrogen and methyl with the proviso, that R.sup.IIIR.sup.IV are hydrogen or either R.sup.III or R.sup.IV is methyl or a precursor thereof.

8. A compound of formula (I) ##STR00014## wherein R.sup.1 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4 alkyl, hydroxyl, methoxy, CF.sub.3 and F; R.sup.2 is selected from the group consisting of methyl and ethyl; R.sup.3 is selected from the group consisting of methyl and ethyl; and Y is a bivalent residue selected from the group consisting of CH.sub.2CH.sub.2C(O), and CHR.sup.IIICHR.sup.IVC(O), wherein R.sup.III and R.sup.IV are independently selected from hydrogen and methyl with the proviso that R.sup.IIIR.sup.IV are hydrogen or either R.sup.III or R.sup.IV is methyl; 2-ethyl-1-(p-tolyl)butane-1,3-dione, and 2-methyl-1-(p-tolyl)pentane-1,3-dione.

9. A precursor having the formula (II) ##STR00015## capable of generating a compound of formula (I), ##STR00016## wherein R.sup.1 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4 alkyl, hydroxyl, methoxy, CF.sub.3 and F; R.sup.2 is selected from the group consisting of methyl and ethyl; R.sup.3 is selected from the group consisting of methyl and ethyl; Y is a bivalent residue selected from the group consisting of C(O); CH.sub.2CH.sub.2C(O); CR.sup.IR.sup.IIC(O), wherein R.sup.I and R.sup.II are independently selected from hydrogen and methyl; and CHR.sup.IIICHR.sup.IVC(O), wherein R.sup.III and R.sup.IV are independently selected from hydrogen and methyl with the proviso that R.sup.IIIR.sup.IV are hydrogen or either R.sup.III or R.sup.IV is methyl; and R.sup.4 and R.sup.5 are selected independently from linear or branched C.sub.1-C.sub.15 alkyl, aryl, and C.sub.3-C.sub.8 cycloalkyl, the cycloalkyl and aryl being optionally substituted with linear or branched C.sub.1-C.sub.7 alkyl groups; or R.sup.4 and R.sup.5 may, together with the nitrogen atom to which they are attached, form a 5- or 6-membered ring; or R.sup.4 and R.sup.5, together with the nitrogen atom to which they are attached, form part of a polymeric entity.

10. The method according to claim 1 comprising admixing to a fragranced article a compound of formula (II) ##STR00017## wherein R.sup.4 and R.sup.5 are selected independently from linear or branched C.sub.1-C.sub.15 alkyl, aryl, and C.sub.3-C.sub.8 cycloalkyl, the cycloalkyl and aryl being optionally substituted with linear or branched C.sub.1-C.sub.7 alkyl groups; or R.sup.4 and R.sup.5 may, together with the nitrogen atom to which they are attached, form a 5- or 6-membered ring; or R.sup.4 and R.sup.5, together with the nitrogen atom to which they are attached, form part of a polymeric entity; for the in situ generation of a compound of formula (I).

11. The method according to claim 10, wherein R.sup.4 and R.sup.5, together with the nitrogen atom to which they are attached, form a pyrrolidine or a piperidine ring.

12. The precursor according to claim 9, wherein R.sup.4 and R.sup.5, together with the nitrogen atom to which they are attached, form a pyrrolidine or a piperidine ring.

Description

EXAMPLE 1

2-methyl-1-(p-tolyl)butane-1,3-dione

1.1. 1-(p-tolyl)butane-1,3-dione

[0091] To the suspension of NaH (13.65 g of a 60% suspension in mineral oil, washed with hexane, 366 mmol, 1.1 equiv.) in toluene (210 ml) was added the solution of methyl 4-methylbenzoate (50.0 g, 333 mmol, 1 equiv) in N-methyl pyrrolidone (NMP, 100 ml) within 10 min at room temperature under intense stirring. The mixture was then warmed to 50 C. and the solution of acetone (27.1 g, 466 mmol, 1.4 equiv.) in toluene (100 ml) was added dropwise over 1 h (inside temperature ca. 45-55 C., gas evolution). After finished addition, the brown suspension was stirred at 50 C. for another 30 min, after which it was diluted with toluene (300 ml), stirred for 5 min at 50 C., then poored on a mixture of 2 N aqueous HCl solution (200 ml) and ice. The acidic aqueous layer was further extracted with toluene, and the combined organic layers were washed thoroughly three times with water (to extract most of the NMP), then dried over MgSO.sub.4. The solvents were removed in a rotary evaporator under vacuum and the orange residue was diluted with hexane/toluene 7:2 (90 ml) and left to stand in refrigerator over night. The crystalline precipitate was separated by filtration (mainly p-methyl benzoic acid) and discarded. The filtrate was concentrated (37.6 g of clear orange oil) and distilled over a 10 cm Vigreux column at 104-105 C./0.02 mbar to isolate the olfactorily pure 1-(p-tolyl)butane-1,3-dione (clear, slightly yellow oil, 17.6 g, 65%).

[0092] Odor description: anisic, fennel seed, with connotations of p-cresol and myrrh.

[0093] The NMR-spectra indicate the presence of 83% enol and 17% diketo form.

[0094] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.93-7.98 (m, 0.2H), 7.86 (d, J=8.3 Hz, 0.2H), 7.77-7.83 (m, 2H), 7.26 (dd, J=8.6, 0.7 Hz, 2.4H), 6.17 (s, 1H), 4.08 (s, 0.2H), 2.42 (s, 3.6H), 2.31 (s, 0.3H), 2.20 (s, 3.1H).

[0095] .sup.13C NMR (101 MHz, CDCl.sub.3): 202.5 (s), 193.4 (s), 193.0 (s), 183.7 (s), 143.0 (s), 132.1 (s), 129.4 (d), 129.3(d), 128.9 (d), 128.7 (d), 127.0 (d), 96.2 (d), 54.6 (t), 30.5 (q), 25.6 (q), 21.5 (q).

1.2. 2-methyl-1-(p-tolyl)butane-1,3-dione

[0096] To the solution of 1-(p-tolyl)butane-1,3-dione (25.1 g, 142 mmol) in THF (141 ml) was added lithium hydroxide hydrate (5.98 g, 142 mmol, 1 equiv.), which dissolved completely after stirring at room temperature for 15 min. Then methyl iodide (30.3 g, 214 mmol, 1.5 equiv.) was added at once. The resulting clear orange solution was warmed to 50 C. and stirred for 7 h. It was transferred into a separatory funnel and diluted with toluene. The organic layer was washed with water, then 2 N aq. HCl solution (80 ml, 160 mmol), and brine (three times). All aqueous layers were extracted once with toluene. The combined organic layers were dried over MgSO.sub.4, then the solvents were removed in a rotary evaporator under vacuum and the residue was purified by flash chromatography on silica gel with toluene/MTBE 29:1 to isolate the product as a clear, slightly yellow oil (21.6 g, 80%), which was further purified by distillation over a 10 cm Vigreux column at 90-110 C./0.02 mbar to isolate the olfactorily pure 2-methyl-1-(p-tolyl)butane-1,3-dione (clear, slightly yellow oil, 25.2 g, 43%).

[0097] The NMR-spectra indicate the presence of >95% diketo form.

[0098] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.80-7.98 (m, 2H), 7.24-7.36 (m, 2H), 4.48 (q, J=7.0 Hz, 1H), 2.37-2.48 (m, 3H), 2.10-2.20 (m, 3H), 1.45 (d, J=6.9 Hz, 3H).

[0099] .sup.13C NMR (101 MHz, CDCl.sub.3): 205.1 (s), 196.9 (s), 144.7 (s), 133.4 (s), 129.5 (d), 128.8 (d), 56.7 (d), 27.8 (q), 21.6 (q), 13.6 (q).

[0100] Odor description: floral creamy, buttery, jasmine, anisic, black tea.

EXAMPLE 2

2-methyl-1-phenylbutane-1,3-dione

[0101] To the suspension of NaH (4.36 g of a 60% suspension in mineral oil, washed with hexane, 100 mmol, 1.0 equiv.) in tetrahydrofurane (THF, 25 ml) was added the solution of ethyl benzoate (15.0 g, 100 mmol, 1 equiv). The suspension was heated to 50 C. and under intense stirring the solution of acetone (6.97 g, 120 mmol, 1.2 equiv.) in THF (25 ml) was added dropwise over 2 h. This resulted in an exothermic reaction with gas evolution (H.sub.2). The inside temperature was kept at 50-53 C. by temporarily removing the heating oil bath. The brownish suspension was stirred for additional 16 h at 50 C., then cooled to 10 C. and the solution of methyl iodide (15.61 g, 110 mmol, 1.1 equiv.) in THF (25 ml) was added dropwise over 30 min. The resulting beige suspension was stirred for additional 24 h at r.t., diluted with toluene and washed with water, sat. aq. NaHCO.sub.3 solution and brine/water 1:1 (3 times). The organic layer was dried over MgSO.sub.4 and the solvents were removed in a rotary evaporator under vacuum. The residual orange oil (10.2 g) was distilled first over a 10 cm Vigreux column at 80-90 C./0.06 mbar (7.2 g of a yellow oil), then over a 10 cm Widmer column at 92-93 C./0.05 mbar to yield the olfactorily pure 2-methyl-1-phenylbutane-1,3-dione (clear, slightly yellow oil, 4.4 g, 25%).

[0102] Odor description: floral, buttery, black tea, herbaceous, jasmone, minty, carvi, woody dry tobacco.

[0103] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.86-8.04 (m, 2H), 7.52-7.60 (m, 1H), 7.41-7.50 (m, 2H), 4.48 (q, J=7.1 Hz, 1H), 2.13 (s, 3H), 1.41 (d, J=7.1 Hz, 3H).

[0104] .sup.13C NMR (101 MHz, CDCl.sub.3): 204.8 (s), 197.2 (s), 135.8 (s), 133.5 (d), 128.7 (d), 128.5 (d), 56.5 (d), 27.8 (q), 13.4 (q).

EXAMPLE 3

3-methyl-1-phenylpentane-2,4-dione

[0105] The procedure described in Example 2 was repeated with ethyl 2-phenylacetate (16.42 g, 100 mmol). The crude product (orange oil, 10.0 g) was distilled first over a 10 cm Vigreux column at 93-103 C./0.06 mbar (5.3 g of a pale yellow oil), then over a 10 cm Widmer column at 94-97 C./0.05 mbar to yield olfactorily pure 3-methyl-1-phenylbutane-2,4-dione (clear, colourless oil, 3.3 g, 17%).

[0106] Odor description: honey, buttery, tobacco, dried leaves, honey, jasmone.

[0107] .sup.1H NMR (400 MHz, CDCl.sub.3): (mixture of diketo- and 2 regioisomeric enol forms) 16.48 (s, 0.2H), 7.15-7.41 (m, 5H), 3.71-3.83 (m, 2.6H), 2.14 (s, 0.9H), 2.09 (s, 0.5H), 2.06 (s, 1.6H), 1.89 (s, 1H), 1.42 (s, 1H), 1.32 (d, J=7.1 Hz, 1.7H).

[0108] .sup.13C NMR (101 MHz, CDCl.sub.3) (mixture of diketo- and 2 regioisomeric enol forms) 207.6 (s), 206.8 (s), 204.9 (s), 204.5 (s), 191.8 (s), 189.7 (s), 135.2 (s), 133.6 (s), 133.2 (s), 129.6 (d), 129.5 (d), 128.9 (d), 128.7 (d), 128.5 (d), 128.4 (d), 127.2 (d), 126.9 (d), 126.7 (d), 104.7 (s), 59.9 (d), 48.9 (t), 44.9 (t), 42.3 (t), 28.3 (q), 26.2 (q), 23.6 (q), 21.2 (q), 12.8 (q), 12.7 (q).

EXAMPLE 4

3-methyl-6-phenylhexane-2,4-dione

[0109] The procedure described in example 2 was repeated with ethyl 3-phenylpropanoate (17.82 g, 100 mmol). The crude product (orange oil, 14.0 g) was distilled first over a 10 cm Vigreux column at 87-105 C./0.06 mbar (10.1 g of an orange oil), then over a 15 cm Widmer column at 116-119 C./0.05 mbar to yield olfactorily pure 3-methyl-6-phenylhexane-2,4-dione (clear, pale yellow oil, 5.2 g, 26%).

[0110] Odor description: buttery, floral, black tea, dried leaves, cinnamon.

[0111] .sup.1H NMR (400 MHz, CDCl.sub.3): (mixture of ca. 65% diketo- and 2 regioisomeric enol forms) 7.17-7.34 (m, 5H), 3.65 (q, J=7.1 Hz, 0.6H), 2.88-3.00 (m, 2H), 2.70-2.87 (m, 2H), 2.12 (s, 0.9H), 2.10 (s, 1.8H), 1.97 (s, 0.3H), 1.79 (s, 0.9H), 1.32 (s, 0.6H), 1.30 (d, J=7.1 Hz, 2H).

[0112] .sup.13C NMR (101 MHz, CDCl.sub.3): (mixture of ca. 65% diketo- and 2 regioisomeric enol forms) 206.1 (s), 204.8 (s), 192.4 (s), 189.5 (s), 141.0 (s), 140.7 (s), 140.5 (s), 128.4 (d), 128.4 (d), 128.4 (d), 126.1 (d), 126.1 (d), 126.0 (d), 104.5 (s), 61.5 (d), 43.0 (t), 40.1 (t), 37.8 (t), 31.0 (t), 29.7 (t), 29.4 (t), 28.4 (q), 25.9 (q), 23.1 (q), 21.0 (q), 12.4 (q), 12.3 (q).

EXAMPLE 5

3-methyl-6-phenylhex-5-ene-2,4-dione

[0113] The procedure described in example 2 was repeated with ethyl cinnamate (17.62 g, 100 mmol). The crude product (orange oil, 11.5 g) was distilled first over a 10 cm Vigreux column at 85-138 C./0.05 mbar (6.6 g of a yellow, slightly turbid oil), then over a 15 cm Widmer column at 116-119 C./0.05 mbar to yield olfactorily pure 3-methyl-6-phenylhex-5-ene-2,4-dione (clear, pale yellow oil, 5.2 g, 26%).

[0114] Odor description: floral, buttery, tea, jasmine.

[0115] NMR-spectra indicate the presence of 57% enol and 43% diketo form.

[0116] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.67 (br d, J=15.9 Hz, 0.3H), 7.64 (d, J=15.7 Hz, 0.7H), 7.51-7.60 (m, 2H), 7.33-7.44 (m, 3H), 6.96 (dd, J=15.7, 1.3 Hz, 0.6H), 6.82 (d, J=15.9 Hz, 0.3H), 6.47 (d, J=15.7 Hz, 0.1H), 6.45 (d, J=15.9 Hz, 0.02H), 5.66 (s, 0.1H) 4.28 (q, J=7.1 Hz, 0.1H), 3.97 (q, J=7.0 Hz, 0.3H), 2.26 (s, 1.7H), 2.20 (s, 0.9H), 2.18 (s, 0.2H), 2.03 (s, 1.7H), 1.41 (d, J=7.1 Hz, 1.0H).

[0117] .sup.13C NMR (101 MHz, CDCl.sub.3): 205.0 (s), 200.4 (s), 196.1 (s), 172.8 (s), 144.6 (d), 139.7 (d), 135.6 (s), 134.0 (s), 130.9 (d), 129.6 (d), 129.0 (d), 128.8 (d), 128.8 (d), 128.6 (d), 127.8 (d), 127.8 (d), 123.8 (d), 119.5 (d), 105.7 (s), 60.2 (d), 28.2 (q), 26.4 (q), 12.8 (q), 12.5 (q).

EXAMPLE 6

1-(4-nnethoxyphenyI)-2-nnethylbutane-1,3-dione

6.1. 1-(4-nnethoxyphenyl)butane-1,3-dione

[0118] The procedure described in example 1.1. was repeated with methyl 4-methoxybenzoate (16.62 g, 100 mmol). A crystalline byproduct (4-methoxy benzoic acid) was separated from the crude by crystallization in hexane/toluene 4:1 and filtration. The mother liquor was concentrated and the residue purified by flash chromatography on SiO.sub.2 (toluene/hexane 1:1 to toluene 100% to toluene/MTBE 9:1) and further by recrystallization from hexane to yield 1-(4-methoxyphenyl)butane-1,3-dione as white crystals (5.15 g, 28%).

[0119] Odor description: floral fruity, anisic, saffron.

[0120] The NMR-spectra indicate the presence of 71% enol and 29% diketo form.

[0121] .sup.1H NMR (400 MHz, CDCl.sub.3): (enol-H not visible, out of range) 7.91-7.99 (m, 0.3H), 7.85-7.90 (m, 1.7H), 6.92-6.98 (m, 2H), 6.12 (s, 0.8H), 4.06 (s, 0.3H), 3.89 (s, 0.9H), 3.88 (s, 2.1H), 2.30 (s, 1H), 2.18 (s, 3H).

6.2. 1-(4-nnethoxyphenyl)-2-nnethylbutane-1,3-dione

[0122] The procedure described above for example 1.2. was repeated with 1-(4-methoxyphenyl)butane-1,3-dione (2.0 g, 10.4 mmol). Reaction time at 50 C. was 26 h. Bulb-to-bulb distillation of the crude product at 140-160 C./0.05 mbar yielded the product as a colourless viscous oil (2.05 g, 96%) which was further purified by flash chromatography on SiO.sub.2 (toluene/MTBE 29:1) followed by bulb-to-bulb distillation at 160-165 C./0.05 mbar to yield olfactorily pure 1-(4-methoxyphenyI)-2-nnethylbutane-1,3-dione (1.76 g, 82%) as a semicrystalline colourless oil.

[0123] Odor description: buttery, tea, floral.

[0124] The NMR-spectra indicate >95% diketo form.

[0125] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.93-8.00 (m, 2H), 6.93-6.99 (m, 2H), 4.43 (q, J=7.1 Hz, 1H), 3.88 (s, 3H), 2.14 (s, 3H), 1.44 (d, J=7.1 Hz, 3H).

[0126] .sup.13C NMR (101 MHz, CDCl.sub.3): 205.3 (s), 195.6 (s), 164.0 (s), 131.1 (d), 129.0 (s), 114.0 (d), 56.7 (d), 55.6 (q), 27.7 (q), 13.6 (q).

[0127] GC-MS (EI, 70 eV): 206 (3, M.sup.+), 163 (3), 107 (6), 92 (8), 77 (10), 64 (4), 43 (6).

EXAMPLE 7

6-(4-methoxyphenyl)-3-methylhexane-2,4-dione

7.1. 6-(4-methoxyphenyl)hexane-2,4-dione

[0128] To the suspension of sodium hydride (60% suspension in mineral oil, 2.47 g, 61.7 mmol, 1.1 equiv.) in THF (80 mL) was added the solution of methyl acetate (5.82 g, 78.6 mmol, 1.4 equiv.) in THF (40 mL) at room temperature. The suspension was then heated to 50 C. and the solution of 4-(4-methoxy)-2-butanone (10.0 g, 56.1 mmol, 1.0 equiv) in THF (80 mL) was added dropwise over 45 min. The suspension was then stirred at 60 C. for 24 h, then cooled to RT and poured on 200 mL 2 N aq. HCl-solution. The mixture was extracted twice with 200 mL MTBE and the combined organic layers were washed with water and brine, then dried over MgSO.sub.4. The solution was concentrated i. RV and the residue was distilled in a Kugelrohr oven at 160-170 C./0.04 mbar to yield 6-(4-methoxyphenyl)hexane-2,4-dione (10.07 g, 82%) as a slightly yellow oil.

[0129] Odor description: odorless.

[0130] The NMR-spectra indicate the presence of 80% enol and 20% diketo form.

[0131] .sup.1H NMR (400 MHz, CDCl.sub.3): 15.48 (br s, 0.8H), 7.08-7.15 (m, 2H), 6.81-6.87 (m, 2H), 5.48 (s, 0.8H), 3.79 (s, 2.4H), 3.79 (s, 0.6H), 3.55 (s, 0.4H), 2.92-2.84 (m, 2H), 2.84-2.72 (m, 0.4H), 2.53-2.60 (m, 1.6H), 2.20 (s, 0.6H), 2.05 (s, 2.4H).

[0132] .sup.13C NMR (101 MHz, CDCl.sub.3): 203.3 (s), 193.2 (s), 191.1 (s), 158.0 (s), 158.0 (s), 132.7 (s), 132.5 (s), 129.2 (d), 129.16 (d), 113.9 (d), 113.84 (d), 99.98 (d), 58.1 (t, 1 C), 55.2 (q), 45.4 (t), 40.2 (t), 30.8 (d), 30.6 (t), 28.5 (t), 24.8 (q).

[0133] GC-MS (EI, 70 eV): 220 (11, M.sup.+), 134 (18), 121(100), 91 (6), 85 (9), 108 (3), 77 (5), 43 (14).

7.2. 6-(4-methoxyphenyl)-3-methylhexane-2,4-dione

[0134] 6-(4-methoxyphenyl)hexane-2,4-dione (36.1 g, 164 mmol) was dissolved in acetone (500 mL) and K.sub.2CO.sub.3 (23.8 g, 172 mmol, 1.05 equiv.) was added. The suspension was stirred for 10 min, then iodomethane (34.9 g, 246 mmol, 1.5 equiv.) was added and the mixture stirred for 3 h at 50 C. Additional K.sub.2CO.sub.3 (10 g, 72 mmol) and iodomethane (16.0 g, 113 mmol) were added and stirring continued for 18 h at 50 C. The solution was then added to 2 M aqueous HCl-solution (350 mL) and the mixture extracted with MTBE (2350 mL). The organic layers were washed with brine and dried over MgSO.sub.4. The solvent was removed under vacuum and the residue was purified by short-path distillation at 131-136 C./0.05 mbar to yield a brown clear oil (30 g), which was further purified by fine distillation over a 20 cm packed distillation column at 134-138 C./0.06 mbar to yield 6-(4-methoxyphenyl)-3-methylhexane-2,4-dione (24.9 g, 65%) as a colorless oil. The product is ca. 90% pure, the remainder being 6-(4-methoxyphenyl)-3,3-dimethyl hexane-2,4-dione.

[0135] Odor description: buttery, fruity, raspberry, liquorice.

[0136] The NMR-spectra indicate the presence of keto and enol form in a 2:1 ratio.

[0137] .sup.1H NMR (400 MHz, CDCl.sub.3): (enol-H not visible; out of range); 6.99-7.19 (m, 2H), 6.74-6.88 (m, 2H), 3.79 (s, 0.9H), 3.78 (s, 2.1H), 3.62 (q, J=7.3 Hz, 0.7H), 2.61-2.95 (m, 4H), 2.12 (s, 0.9H), 2.08 (s, 2.1H), 1.77 (s, 0.9H), 1.28 (d, J=7.1 Hz, 2.1H).

[0138] .sup.13C NMR (101 MHz, CDCl.sub.3): 206.4 (s), 205.1 (s), 192.5 (s), 189.9 (s), 158.0 (s), 133.1 (s), 132.7 (s), 129.3 (d), 113.9 (d), 104.6 (s), 61.7 (d), 55.2 (q), 43.4 (t), 38.1 (t), 30.3 (t), 28.7 (t), 28.5 (q), 23.3 (q), 12.5 (q).

[0139] GC-MS (EI, 70 eV, 6-(4-methoxyphenyl)-3-methylhexane-2,4-dione): 234 (11, M.sup.+), 163 (12), 134 (45), 121 (100), 91 (9), 77 (7), 43 (23).

[0140] GC-MS (El, 70 eV, 6-(4-methoxyphenyl)-3,3-dimethylhexane-2,4-dione): 248 (6, M.sup.+), 163 (6), 134 (16), 121 (100), 86 (7), 43 (17).

EXAMPLE 8

6-(4-hydroxyphenyl)-3-methylhexane-2,4-dione

[0141] The solution of 6-(4-methoxyphenyl)-3-methylhexane-2,4-dione (as described in Example 7, 16.3 g, 70 mmol) in CH.sub.2Cl.sub.2 (150 mL) was cooled to 70 C. and BBr.sub.3 (1 M in CH.sub.2Cl.sub.2, 100 mL, 100 mmol) was added dropwise over 1.5 h. The solution was then added to 2 M aqueous HCl-solution (250 mL) the phases separated and the aqueous layer further extracted with ethyl acetate (stirring for 30 min). The combined organic layers were washed with brine and dried over MgSO.sub.4. The crude product obtained after removal of the solvents was purified by flash chromatography on SiO.sub.2 (hexane/MTBE 67:33) followed by bulb-to-bulb distillation at 185 C./0.07 mbar to yield olfactorily pure 6-(4-hydroxyphenyl)-3-methylhexane-2,4-dione (3.32 g, 22%) as an orange oil. The product was 80% pure, the remaining 20% were 6-(4-hydroxyphenyl)-3,3-dimethylhexane-2,4-dione.

[0142] Odor description: fruity raspberry, creamy, buttery, sweet powdery, brown sugar.

[0143] The NMR-spectra indicate the presence of mainly diketo form.

[0144] .sup.1H NMR (400 MHz, CDCl.sub.3, main product, diketo form): 6.98-7.09 (m, 2H), 6.72-6.80 (m, 2H), 5.82 (br s, 1H), 3.64 (q, J=6.9 Hz, 1H), 2.72-2.90 (m, 4H), 2.09 (s, 3H), 1.29 (d, J=7.1 Hz, 3H).

[0145] .sup.13C NMR (101 MHz, CDCl.sub.3, main product, diketo form): 206.9 (s), 205.8 (s), 154.1 (s), 132.4 (s), 129.4 (d), 115.3 (d), 61.6 (d), 43.4 (t), 28.6 (t), 28.5 (q), 12.5 (q).

[0146] GC-MS (EI, 70 eV): 220 (8, M+), 205 (1.5), 149 (17), 120(45), 107 (100), 77 (12), 72 (3), 43 (29).

EXAMPLE 9

2-ethyl-1-(p-tolyl)butane-1,3-dione

[0147] The procedure described above for example 1.2. was repeated with 1-(p-tolyl)butane-1,3-dione (2.25 g, 12.8 mmol) and ethyl iodide (2.99 g, 19.2 mml). Reaction time was 20 h at 70 C. Purification of the crude by flash chromatography on SiO.sub.2 (toluene/MTBE 29:1) followed by bulb-to-bulb distillation at 140 C./0.02 mbar yielded olfactorily pure 2-ethyl-1-(p-tolyl)butane-1,3-dione as a colourless oil (1.30 g, 50%).

[0148] Odor description: floral, green, anisic, heliotropin, buttery, tea.

[0149] The NMR-spectra indicate >95% diketo form.

[0150] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.86-7.92 (m, 2H), 7.27 (m, 2H), 4.32 (t, J=7.1 Hz, 1H), 2.41 (s, 3H), 2.12 (s, 3H), 1.94-2.10 (m, 2H), 0.94 (t, J=7.3 Hz, 3H).

[0151] .sup.13C NMR (101 MHz, CDCl.sub.3): 204.6 (s), 196.0 (s), 144.6 (s), 134.1 (s), 129.5 (d), 128.8 (d), 65.0 (d), 27.7 (q), 22.4 (t), 21.6 (q), 12.1 (q).

[0152] GC-MS (EI, 70 eV): 204 (<1, M.sup.+), 176 (3), 162 (2), 147 (8), 119 (100), 91 (27), 65 (12), 55 (8), 43 (11).

EXAMPLE 10

1-(4-ethylphenyl)-2-nnethylbutane-1,3-dione

10.1. 1-(4-ethylphenyl)butane-1,3-dione

[0153] The procedure described in example 1.1 was repeated with ethyl 4-ethylbenzoate (14.0 g, 79 mmol). A crystalline byproduct (4-methoxy benzoic acid, ca. 30%) was separated from the crude by extraction with saturated aqueous NaHCO.sub.3-solution. The crude product was distilled at 93-101 C./0.05 mbar to yield 1-(4-ethylphenyl)butane-1,3-dione (5.47 g, 37%) as a colourless oil.

[0154] Odor description: green, acetal, cardboard, saffron.

[0155] The NMR-spectra indicate the presence of 90% enol and 10% diketo form.

[0156] .sup.1H NMR (400 MHz, CDCl.sub.3): (enol-H not visible; out of range); 7.86-7.91 (m, 0.2H), 7.80-7.85 (m, 1.8H), 7.26-7.33 (m, 2H), 6.18 (s, 0.9H), 4.09 (br. s, 0.2H), 2.72 (q, J=7.6 Hz, 1.8H), 2.71 (q, J=7.4 Hz, 0.2H), 2.30 (s, 0.3H), 2.20 (s, 2.7H), 1.27 (t, J=7.6 Hz, 3H).

[0157] .sup.13C NMR (101 MHz, CDCl.sub.3): (*=diketo form, 10%) 202.4 (s*), 193.4 (s*), 193.0 (s), 183.6 (s), 150.9 (s*), 149.2 (s), 133.9 (s*), 132.3 (s), 129.6 (d*), 128.8 (d*), 128.2 (d*), 128.1 (d), 127.1 (d), 96.3 (d), 54.6 (t), 30.4 (d*), 29.6 (t*), 28.9 (t*)), 28.8 (t), 25.6 (q), 15.1 (q), 15.0 (q*).

[0158] GC-MS (EI, 70 eV): 190 (45, M.sup.+), 175 (48), 161 (48), 133 (100), 115 (8), 105 (18), 91 (15), 85 (11), 77 (21), 69 (64), 43 (27).

10.2. 1-(4-ethylphenyl)-2-nnethylbutane-1,3-dione

[0159] The procedure described above for example 1.2. was repeated with 1-(4-methoxyphenyl)butane-1,3-dione (2.0 g, 10.4 mmol). Reaction time at 50 C. was 7 h. The crude product was purified by flash chromatography on SiO.sub.2 (toluene) followed by bulb-to-bulb distillation at 104 C./0.05 mbar to yield olfactorily pure 1-(4-ethylphenyI)-2-methylbutane-1,3-dione (1.53 g, 32%) as a colourless oil.

[0160] Odor description: floral, green, anisic, buttery, tea, mushroom.

[0161] The NMR-spectra indicate >95% diketo form.

[0162] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.87-7.93 (m, 2H), 7.28-7.34 (m, 2H), 4.47 (q, J=7.1 Hz, 1H), 2.71 (q, J=7.6 Hz, 2H), 2.15 (s, 3H), 1.44 (d, J=7.1 Hz, 3H), 1.26 (t, J=7.7 Hz, 3H).

[0163] .sup.13C NMR (101 MHz, CDCl.sub.3): 205.1 (s), 196.9 (s), 150.8 (s), 133.6 (s), 128.9 (d), 128.3 (d), 56.7 (d), 28.9 (t), 27.8 (q), 15.1 (q), 13.6 (q).

[0164] GC-MS (El, 70 eV): 204 (<1, M.sup.+), 162 (2), 105 (11), 77 (10), 43 (9).

EXAMPLE 11

2-methyl-1-(4-(trifluoronnethyl)phenyl)butane-1,3-dione

11.1. 1-(4-(trifluoronnethyl)phenyl)butane-1,3-dione

[0165] The procedure described in example 1.1. was repeated with methyl 4-(trifluoromethyl)benzoate (9.0 g, 44.1 mmol). A crystalline byproduct was separated from the crude by crystallization from toluene and filtration. The mother liquor was concentrated and the residue purified by flash chromatography on SiO.sub.2 (toluene 100%) and further by recrystallization from hexane/toluene 1:1 to yield 1-(4-(trifluoronnethyl)phenyl)butane-1,3-dione (2.8 g, 28%) as an off-white crystalline solid.

[0166] Odor description: weak, floral fruity.

[0167] The NMR-spectra indicate the presence of 95% enol and 5% diketo form.

[0168] .sup.1H NMR (400 MHz, CDCl.sub.3): 16.0 (s, 0.95H), 7.9-8.0 (m, 2H), 7.7 (d, J=8.1 Hz, 2H), 6.2 (s, 0.95H), 4.1 (s, 0.1H), 2.2 (s, 3H).

[0169] .sup.13C NMR (101 MHz, CDCl.sub.3): 195.1 (s), 180.9 (s), 138.1 (s), 133.6 (q, J=33.2 Hz), 127.3 (d), 125.6 (q, J=3.3 Hz), 123.8 (q, J=272.8 Hz), 97.4 (s), 26.2 (q).

[0170] GC-MS (EI, 70 eV): 230 (52, M+), 218 (86), 188 (8), 173 (38), 161 (19), 151 (11), 145 (57), 119 (8), 85 (43), 125 (23), 75 (15), 69 (100), 43 (80).

11.2. 2-methyl-1-(4-(trifluoronnethyl)phenyl)butane-1,3-dione

[0171] The procedure described above for example 1.2. was repeated with 1-(4-methoxyphenyl)butane-1,3-dione (1.6 g, 7.1 mmol). Reaction time at 50 C. was 24 h. The crude product was purified by flash chromatography on SiO.sub.2 (toluene/MTBE 19:1) followed by bulb-to-bulb distillation at 120 C./0.02 mbar to yield olfactorily pure 1-(4-ethylphenyl)-2-nnethylbutane-1,3-dione (1.12g, 64%) as a white, low-melting solid.

[0172] Odor description: buttery, acidic, floral, jasmine, tea.

[0173] The NMR-spectra indicate >95% diketo form.

[0174] .sup.1H NMR (400 MHz, CDCl.sub.3): 8.07 (dd, J=8.8, 0.7 Hz, 2H), 7.74 (d, J=8.8 Hz, 2H), 4.49 (q, J=7.1 Hz, 1H), 2.18 (s, 3H), 1.48 (d, J=7.1 Hz, 3H).

[0175] .sup.13C NMR (101 MHz, CDCl.sub.3): 204.6 (s), 196.3 (s), 138.6 (s), 134.8 (q, J=33.2 Hz), 129.0 (s), 125.9 (q, J=4.1 Hz), 123.4 (q, J=272.8 Hz), 57.1 (d), 27.8 (q), 13.4 (q).

[0176] GC-MS (EI, 70 eV): 244 (2, M+), 225(4), 202 (23), 173 (100), 145 (69), 133 (28), 125 (11), 95 (9), 75 (15), 43 (39).

EXAMPLE 12

2-methyl-1-(p-tolyl)pentane-1,3-dione

[0177] To the suspension of potassium t-butoxide (44.8 g, 344 mmol, 1.7 equiv.) in THF (40 mL) was added the solution of 1-(p-tolyl)propan-1-one (30.0 g 202 mmol) in THF (30 mL) at 55 C. over 5 min. Stirring was continued for 1 h at 70 C. (batch temperature) to yield a clear orange solution, to which was added t-butyl propionate (27.3 g, 243 mmol, 1.2 equiv.) within dropwise over 10 min. The resulting solution was stirred at 75 C. for 2 days. The mixture was then diluted with toluene and the solution added to a ice/water mixture. Then 150 mL 2N aq. HCl-solution were added. The phases were separated and the aq. Layer was further extracted with toluene. The combined organic layers were washed with brine and dried over MgSO.sub.4.

[0178] After evaporation of the solvents, an orange oil was obtained, which was purified by short-path distillation (10 cm Vigreux column) at 52-70 C./0.02 mbar, followed by a fine distillation at 106-119 C./0.02 mbar to yield 2-methyl-1-(p-tolyl)pentane-1,3-dione (15.5 g, 38%) as a colourless oil.

[0179] Odor description: floral, tea, buttery.

[0180] The NMR-spectra indicate >95% diketo form.

[0181] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.8-7.9 (m, 2H), 7.3-7.3 (m, 2H), 4.5 (q, J=7.1 Hz, 1H), 2.35-2.60 (m, 2H), 2.4 (s, 3H), 1.4 (d, J=6.8 Hz, 3H), 1.0 (t, J=7.2 Hz, 3H).

[0182] .sup.13C NMR (101 MHz, CDCl.sub.3): 207.6 (s), 197.0 (s), 144.5 (s), 133.5 (s), 129.5 (d), 128.7 (d), 55.8 (d), 33.9 (t), 21.6 (q), 13.6 (q), 7.7 (q).

[0183] GC-MS (EI, 70 eV): 204 (<1, M.sup.+), 148 (10), 133 (11), 119 (100), 91 (30), 65 (13), 57 (11).

EXAMPLE 13

1-(benzo[d][1,3]dioxol-5-yl)-2-methylbutane-1,3-dione

[0184] The procedure described in Example 12 was repeated with 1-(benzo[d][1,3]dioxol-5-yl)propan-1-one (5.5 g, 30.9 mmol). The crude product was purified by flash chromatography on SiO.sub.2 (toluene/MTBE 19:1) followed by bulb-to-bulb distillation at 180 C./0.02 mbar to yield olfactorily pure-(benzo[d][1,3]dioxol-5-yl)-2-methylbutane-1,3-dione (2.52 g, 35%) as a colorless liquid.

[0185] Odor description: buttery.

[0186] The NMR-spectra indicate >95% diketo form.

[0187] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.56 (dd, J=8.2, 1.9 Hz, 1H), 7.42 (d, J=2.0 Hz, 1H), 6.84 (d, J=8.3 Hz, 1H), 6.05 (s, 2H), 4.27(q, J=6.9 Hz, 1H), 2.12 (s, 3H), 1.41 (d, J=7.1 Hz, 3H).

[0188] .sup.13C NMR (101 MHz, CDCl.sub.3): 205.1, 195.2, 152.3, 148.4, 130.7, 125.2, 108.2, 108.0, 102.0, 56.6, 27.6, 13.7.

COMPARATIVE EXAMPLE 14

2-methyl-1-(m-tolyl)butane-1,3-dione

[0189] 1-(m-tolyl)butane-1,3-dione was prepared from ethyl 3-methylbenzoate as described in Example 1.1. 1-(m-tolyl)butane-1,3-dione was then monomethylated as described in Example 1.2. The crude product was purified by flash chromatography on SiO.sub.2 (toluene/MTBE 39:1) followed by bulb-to-bulb distillation at 150-170 C./0.05 mbar to yield olfactorily pure 2-methyl-1-(m-tolyl)butane-1,3-dione (86%) as a colourless liquid.

[0190] Odor description: floral, fruity, rosy, yeast.

[0191] The NMR-spectra show >95% keto form.

[0192] .sup.13C NMR (101 MHz, CDCl.sub.3): 205.0 (s), 197.5 (s), 138.7 (s), 135.9 (s), 134.4 (d), 129.1 (d), 128.6 (d), 125.8 (d), 56.7 (d), 27.9 (q), 21.3 (q), 13.6 (q).

EXAMPLE 15

Preparation of a precursor (2-methyl-3-(tetradecylamino)-1-(p-tolyl)but-2-en-1-one)

[0193] 2-methyl-1-(p-tolyl)butane-1,3-dione (product of example 1.2., 3.28 g, 17.3 mmol, 1.0 equiv) and tetradecylamine (3.50 g, 16.4 g, 0.95 equiv.) were dissolved in toluene (30 mL) and p-toluene sulfonic acid was added (0.33 g, 1.73 mmol, 0.1 equiv.). The resulting solution was refluxed for 22 h over a Dean-Stark trap for the continous removal of water. The mixture was quenched with water (80 mL) and the aqueous layer was twice extracted with MTBE. The combined organic layers were washed with water and brine and dried over MgSO.sub.4.

[0194] After evaporation of the solvents, 2-methyl-3-(tetradecylamino)-1-(p-tolyl)but-2-en-1-one (4.93 g, 74%) was obtained as a viscous yellow liquid. The product consists of a main isomer (>90%) and some minor components.

[0195] .sup.1H NMR (400 MHz, CDCl.sub.3, main isomer): 7.13-7.39 (m, 4H), 3.34 (td, J=7.0, 5.5 Hz, 2H), 2.38 (s, 3H), 2.08 (s, 3H), 1.86 (s, 3H), 1.68 (quin, J=7.3 Hz, 2H), 1.22-1.37 (m, 22H), 0.91 (t, J=7.0 Hz, 3H).

[0196] .sup.13C NMR (101 MHz, CDCl.sub.3, main isomer): 192.3 (s), 165.1 (s), 140.5 (s), 138.1 (s), 128.3 (s), 127.1 (s), 97.4 (s), 43.7 (t), 31.9 (t), 30.0 (t), 29.7 (t), 29.6 (t), 29.6 (t), 29.5 (t), 29.3 (t), 27.0 (t), 22.7 (t), 21.3 (q), 16.6 (q), 15.7 (q), 14.1 (q).

[0197] GC-MS (El, 70 eV): 385 (8, M+), 368 (11), 266 (30), 238 (23), 188 (10), 119 (100), 105 (16), 91 (28), 57 (40), 43 (36).

EXAMPLE 16

A Floral Accord for a Feminine Fragrance

[0198]

TABLE-US-00001 parts by weight Compound/Ingredients 1/1000 Acetyl Isoeugenol .sup.1) (Crystals) 5 Benzyl Acetate 25 Benzyl Salicylate 140 Cashmeran .sup.2) 1 Citronellol 12 Coumarine (Pure Crystals) 1 Dimethyl Benzyl Carbinyl Acetate 17 Dimethyl Benzyl Carbinyl Butyrate 17 Florosa .sup.3) 50 Galaxolide .sup.4) 6 Geraniol .sup.5) 13 Geranium Oil 6 Hedione .sup.6) 50 Hexenyl-3-Cis Salicylate 55 beta - Ionone .sup.7) 1 Iso E Super .sup.8) 3 Linalool 55 Linalyl Acetate 100 Magnolan .sup.9) 14 Methyl Anthranilate 7 Methyl Cedryl Ketone 180 Muscenone .sup.10) 7 Nutmeg Oil 2 Orange Oil 15 Patchouli Oil Iron free @10% DEP (diethyl phthalate) 5 Peach Pure .sup.11) 1 Phenyl Ethyl Alcohol 75 Prunolide .sup.12) 1 Vanillin 13 Dipropylene Glycol (DPG) 123 Total: 1000 .sup.1) 2-methoxy-4-(prop-1-en-1-yl)phenyl acetate .sup.2) 1,1,2,3,3-pentamethyl-1,2,3,5,6,7-hexahydro-4H-inden-4-one .sup.3) 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol .sup.4) 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydro-cyclopenta[g]isochromene .sup.5) (E)-3,7-dimethylocta-2,6-dien-1-ol .sup.6) methyl 3-oxo-2-pentylcyclopentaneacetate) .sup.7) 4-(2,6,6-trimethylcyclohex-1-en-1-yl)but-3-en-2-one .sup.8) 1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone .sup.9) 2,4-dimethyl-4,4a,5,9b-tetrahydroindeno[1,2-d][1,3]dioxine .sup.10) (Z)-3-methylcyclopentadec-5-enone .sup.11) 5-heptyldihydrofuran-2(3H)-one .sup.12) 5-pentyldihydrofuran-2(3H)-one

[0199] The base accord above for a feminine fine fragrance, dosed at 10 weight % in ethanol (85%, containing 15% water) exhibits a white floral scent with musky and oriental powdery facets. The replacement of 10 parts DPG by 2-methyl-1-(p-tolyl)butane-1,3-dione (Example 1) brings a soft creamy floral impression, which softens the musky and powdery facet, and gives a creamy comfortable feel. The replacement of 10 parts DPG by 2-methyl-1-(p-tolyl)butane-1,3-dione (Example 1) brings a creamy floral gourmand note, reinforcing the white floral solar impression.

EXAMPLE 17

Strawberry Fragrance Accord for Shower Gel

[0200]

TABLE-US-00002 parts by weight Compound/Ingredients 1/1000 Agrumex .sup.13) 20 Allyl Caproate 3 Benzyl Acetate 5 Benzyl Benzoate 290 Citronellol 10 Damascenone .sup.14) @10% TEC 4 Delta Damascone .sup.15) 2 Gamma Decalactone .sup.16) 17 Diethyl Malonate 3 Dihydro Myrcenol 40 Dimethyl Benzyl Carbinyl Acetate 22 Dimethyl Benzyl Carbinyl Butyrate 23 Ethyl Butyrate 2 Ethyl Hexanoate 10 Ethyl Methyl-2-Butyrate 2 Florosa 8 Galaxolide 75 Geranyl Acetate 5 Hedione 60 Hexenol-3-Cis 2 Hexyl Acetate 15 Hexyl Butyrate 2 Hexyl Cinnamic Aldehyde .sup.17) 215 Linalool 110 Methyl Cinnamate 5 Orange Oil 14 Strawberry Pure .sup.18) 2 Tricyclal .sup.19) 2 Undecavertol .sup.20) 2 Dipropylene Glycol (DPG) 30 Total: 1000 .sup.13) 2-(tert-butyl)cyclohexyl acetate .sup.14) (E)-1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)but-2-en-1-one .sup.15) (E)-1-(2,6,6-trimethylcyclohex-3-en-1-yl)but-2-en-1-one .sup.16) 6-pentyltetrahydro-2H-pyran-2-one .sup.17) (E)-2-benzylideneoctanal .sup.18) ethyl 3-methyl-3-phenyloxirane-2-carboxylate .sup.19) 2,4-dimethylcyclohex-3-ene-1-carbaldehyde .sup.20) (E)-4-methyldec-3-en-5-ol

[0201] The base accord above dosed at 1 weight % in a shower gel imparts a strawberry impression, with a gourmand and juicy feeling. The replacement of 10 parts DPG by 2-methyl-1-(p-tolyl)butane-1,3-dione (Example 1) softens the top green fruity aspects of this accord, and brings a pleasant creamy impression. The replacement of 30 parts DPG by 2-methyl-1-(p-tolyl)butane-1,3-dione brings a clear creamy gourmand impression with a strawberry yoghurt or strawberry and cream impression.