ALKOXYBENZALDEHYDE DERIVATIVES AND PRECURSORS THEREOF

Abstract

The present invention refers to alkoxybenzaldehyde derivatives and precursors thereof. The invention further refers to perfume compositions and fragranced article comprising them.

Claims

1. The use as fragrance of a compound of formula (I) ##STR00005## wherein R.sup.1 is selected from linear or branched C.sub.3-, C.sub.4- and C.sub.5-alkyl and C.sub.3-, C.sub.4- and C.sub.5-alkenyl.

2. The use as fragrance of a compound according to claim 1, obtained by spontaneous air oxidation of a compound of formula (II) ##STR00006## wherein R.sup.1 selected from linear or branched C.sub.3-, C.sub.4- and C.sub.5-alkyl and C.sub.3-, C.sub.4- and C.sub.5-alkenyl; R.sup.2 is selected from the group consisting of C.sub.4-C.sub.14 alkyl; C.sub.4-C.sub.14 alkyl substituted with one —OH group and/or up to two ether; C.sub.4-C.sub.14 alkenyl; C.sub.4-C.sub.14 alkenyl substituted with one —OH group or an ether group; C.sub.5-C.sub.6 cycloalkyl; C.sub.5-C.sub.8 cycloalkyl substituted with 1, 2, or 3 groups selected from C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.4 alkylidene; C.sub.5-C.sub.8 cycloalkenyl; C.sub.5-C.sub.8 cycloalkenyl wherein the cycloalkenyl-ring is substituted with 1, 2, or 3 groups selected from C.sub.1-C.sub.4 alkyl, C.sub.2-C.sub.4 alkylidene, and C.sub.3-C.sub.5 cycloalkyl; (C.sub.1-C.sub.3)alkyl(C.sub.5-C.sub.6)cycloalkyl wherein the cycloalkyl-ring is optionally substituted with one group selected from —OH group and ═O group, and/or one or two ether group(s), and/or up to four C.sub.1-C.sub.5 alkyl groups; (C.sub.1-C.sub.4)alkyl(C.sub.5-C.sub.6)cycloalkenyl wherein the cycloalkenyl-ring is optionally substituted with one —OH group, and/or one or two ether group(s), and/or up to four C.sub.1-C.sub.5 alkyl groups; (C.sub.2-C.sub.3)alkenyl(C.sub.5-C.sub.6)cycloalkenyl wherein the cycloalkenyl-ring is optionally substituted with one —OH group, and/or one or two ether group(s), and/or up to four C.sub.1-C.sub.5 alkyl groups; C.sub.6-C.sub.14 aryl; C.sub.6-C.sub.14 aryl wherein the aryl ring is substituted with up to 3 groups selected from C.sub.1-C.sub.4 alkyl, —O—CH.sub.2—O—, and —OR.sup.11 wherein R.sup.11 is independently selected from hydrogen and C.sub.1-C.sub.4 alkyl; (C.sub.1-C.sub.4)alkyl(C.sub.6-C.sub.14)aryl; (C.sub.1-C.sub.4)alkyl(C.sub.6-C.sub.14)aryl wherein the aryl-ring is substituted with up to 2 groups selected from C.sub.1-C.sub.4 alkyl, —O—CH.sub.2—O—, and —OR.sup.12 wherein R.sup.12 is independently selected from hydrogen and C.sub.1-C.sub.4 alkyl; (C.sub.2-C.sub.8)alkenyl(C.sub.6-C.sub.14)aryl; (C.sub.2-C.sub.8)alkenyl(C.sub.6-C.sub.14)aryl wherein the aryl-ring is substituted with up to 2 groups selected from C.sub.1-C.sub.4 alkyl, —O—CH.sub.2—O—, and OR.sup.13 wherein R.sup.13 is independently selected from hydrogen and C.sub.1-C.sub.4 alkyl; bi-, tri, or tetracyclic hydrocarbon ring comprising C.sub.8-C.sub.12 carbon atoms optionally substituted with up to 6 groups selected from C.sub.1-C.sub.4 alkyl, —O—CH.sub.2—O—, and —OR.sup.14 wherein R.sup.14 is independently selected from hydrogen and C.sub.1-C.sub.4 alkyl; and R.sup.3 is selected from hydrogen, C.sub.1-C.sub.5 alkyl, and C.sub.2-C.sub.5 alkenyl.

3. Compounds of formula (II) ##STR00007## wherein R.sup.1 selected from linear or branched C.sub.3-, C.sub.4- and C.sub.5-alkyl and C.sub.3-, C.sub.4- and C.sub.5-alkenyl; R.sup.2 is selected from the group consisting of C.sub.4-C.sub.14 alkyl; C.sub.4-C.sub.14 alkyl substituted with one —OH group and/or up to two ether; C.sub.4-C.sub.14 alkenyl; C.sub.4-C.sub.14 alkenyl substituted with one —OH group or an ether group; C.sub.5-C.sub.6 cycloalkyl; C.sub.5-C.sub.8 cycloalkyl substituted with 1, 2, or 3 groups selected from C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.4 alkylidene; C.sub.5-C.sub.8 cycloalkenyl; C.sub.5-C.sub.8 cycloalkenyl wherein the cycloalkenyl-ring is substituted with 1, 2, or 3 groups selected from C.sub.1-C.sub.4 alkyl, C.sub.2-C.sub.4 alkylidene, and C.sub.3-C.sub.5 cycloalkyl; (C.sub.1-C.sub.3)alkyl(C.sub.5-C.sub.6)cycloalkyl wherein the cycloalkyl-ring is optionally substituted with one group selected from —OH group and ═O group, and/or one or two ether group(s), and/or up to four C.sub.1-C.sub.5 alkyl groups; (C.sub.1-C.sub.4)alkyl(C.sub.6-C.sub.6)cycloalkenyl wherein the cycloalkenyl-ring is optionally substituted with one —OH group, and/or one or two ether group(s), and/or up to four C.sub.1-C.sub.6 alkyl groups; (C.sub.2-C.sub.3)alkenyl(C.sub.6-C.sub.6)cycloalkenyl wherein the cycloalkenyl-ring is optionally substituted with one —OH group, and/or one or two ether group(s), and/or up to four C.sub.1-C.sub.6 alkyl groups; C.sub.6-C.sub.14 aryl; C.sub.6-C.sub.14 aryl wherein the aryl ring is substituted with up to 3 groups selected from C.sub.1-C.sub.4 alkyl, —O—CH.sub.2—O—, and —OR.sup.11 wherein R.sup.11 is independently selected from hydrogen and C.sub.1-C.sub.4 alkyl; (C.sub.1-C.sub.4)alkyl(C.sub.6-C.sub.14)aryl; (C.sub.1-C.sub.4)alkyl(C.sub.6-C.sub.14)aryl wherein the aryl-ring is substituted with up to 2 groups selected from C.sub.1-C.sub.4 alkyl, —O—CH.sub.2—O—, and —OR.sup.12 wherein R.sup.12 is independently selected from hydrogen and C.sub.1-C.sub.4 alkyl; (C.sub.2-C.sub.8)alkenyl(C.sub.6-C.sub.14)aryl; (C.sub.2-C.sub.8)alkenyl(C.sub.6-C.sub.14)aryl wherein the aryl-ring is substituted with up to 2 groups selected from C.sub.1-C.sub.4 alkyl, —O—CH.sub.2—O—, and OR.sup.13 wherein R.sup.13 is independently selected from hydrogen and C.sub.1-C.sub.4 alkyl; bi-, tri, or tetracyclic hydrocarbon ring comprising C.sub.8-C.sub.12 carbon atoms optionally substituted with up to 6 groups selected from C.sub.1-C.sub.4 alkyl, —O—CH.sub.2—O—, and —OR.sup.14 wherein R.sup.14 is independently selected from hydrogen and C.sub.1-C.sub.4 alkyl; and R.sup.3 is selected from hydrogen, C.sub.1-C.sub.5 alkyl, and C.sub.2-C.sub.5 alkenyl.

4. A compound according to claim 3 selected from 1-butoxy-3-((1E,4Z)-hepta-1,4-dien-1-yl)benzene; 1-butoxy-3-((1E,7Z)-deca-1,7-dien-1-yl)benzene; 1-(4-(3-butoxyphenyl)but-3-en-1-yl)-4-isobutyl-2-methylbenzene; 1-(4-(3-butoxyphenyl)but-3-en-1-yl)-2-isobutyl-4-methylbenzene; 1-(sec-butoxy)-3-((1 E,4Z)-hepta-1 ,4-dien-1-yl)benzene; 1-((1 E,4Z)-hepta-1 ,4-dien-1-yl)-3-(pentyloxy)benzene; 1-((1 E,4Z)-hepta-1 ,4-dien-1-yl)-3-((2-methylallyl)oxy)benzene; 1-((1 E,4Z)-hepta-1 ,4-dien-1-yl)-3-isopropoxybenzene; 1-butoxy-3-(4-(4-(tert-butyl)phenyl)but-1-en-1-yl)benzene; 1-butoxy-3-(4-(4-(tert-butyl)phenyl)-3-methylbut-1-en-1-yl)benzene; 1-butoxy-3-(4-(3-isopropylphenyl)pent-1-en-1-yl)benzene; 11-(3-butoxyphenyl)-2,6-dimethylundeca-6,10-dien-2-ol; 1-butoxy-3-(3-methyldodec-1-en-1-yl)benzene; 5-(4-(3-butoxyphenyl)-2-methylbut-3-en-1-yl)benzo[d][1,3]dioxole; 1-butoxy-3-(tetradeca-1,3-dien-1-yl)benzene; 1-butoxy-3-(3-phenylprop-1-en-1-yl)benzene; 1-butoxy-3-((5E)-undeca-1,5-dien-1-yl)benzene; 5-(5-(3-butoxyphenyl)pent-4-en-1-ylidene)octahydro-1H-4,7-methanoindene; 1-butoxy-3-(4-(4-ethylphenyl)-3,3-dimethylbut-1-en-1-yl)benzene; 1-butoxy-3-(7-methoxy-3,7-dimethylnon-1-en-1-yl)benzene; and 1-butoxy-3-(4-(4-isobutylphenyl)but-1-en-1-yl)benzene.

5. A method of fragrancing a consumer product, comprising the addition to a consumer product base a compound of formula (I) as defined in claim 1, or precursor thereof.

6. A method according to claim 5, characterized in that the precursor of the compound of formula (I) is a compound of formula (II) as defined in claim 3.

7. A method according to claim 5, characterized in that the compound of formula (I) is generated by spontaneous air oxidation of a compound of formula (II) as defined in claim 3 when exposed to oxygen.

8. A consumer product comprising a compound of formula (I) as defined in claim 1, or a precursor thereof, preferably a compound of formula (II) as defined in claim 2 or claim 3, and a consumer product base.

9. A consumer product according to claim 8 wherein the consumer product is selected from home care products, personal care products and cleaning products.

Description

EXAMPLE 1

3-butoxybenzaldehyde and a precursor thereof

1.1: 3-butoxybenzaldehyde

[0102] A solution of 3-hydroxybenzaldehyde (20 g, 164 mmol, 1.0 equiv.) in DMF (100 mL) was treated with potassium carbonate (27.2 g, 197 mmol, 1.2 equiv.). The resulting mixture was heated to 80° C. and then slowly treated with 1-bromobutane (21.2 ml, 197 mmol, 1.2 eq.). The mixture was stirred at 80° C. for 1 h then cooled to 25° C., filtered to remove solids, diluted with MTBE (500 mL) and washed with water (3×100 mL). The organic layer was dried over MgSO.sub.4, filtered and concentrated. The resulting oil was vacuum-distilled over a 5 cm Vigreux column, collecting at 135-137° C. at 25 mbar to give 3-butoxybenzaldehyde (25.3 g, 142 mmol, 87%) as a clear, colorless liquid.

[0103] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ=9.99 (s, 1H), 7.44-7.47 (m, 2H), 7.39-7.42 (m, 1H), 7.17-7.21 (m, 1H), 4.04 (t, J=6.5 Hz, 2H), 1.76-1.85 (m, 2H), 1.46-1.58 (m, 2H), 1.00 ppm (t, J=7.3 Hz, 3H).

[0104] .sup.13C NMR (CDCl.sub.3, 101 MHz): δ=192.3, 159.7, 137.8, 130.0, 123.3, 122.0, 112.8, 68.0, 31.2, 19.2, 13.8 ppm.

[0105] MS (EI, 70 eV): 178 (30, [M]+•), 123 (11), 122 (100), 121 (100), 77 (9), 65 (13), 41 (18), 39 (12), 29 (22), 27 (9).

[0106] Odor description (10% solution in DPG on paper blotter, 24 h): fresh citrus, citral, lemongrass, verbena, green, slightly hot iron, slightly fatty.

1.2: 1-butoxy-3-((1E,4Z)-hepta-1,4-dien-1-yl)benzene

[0107] In a flask flushed with nitrogen were placed magnesium turnings (0.750 g, 31 mmol, 1.3 equiv.) and THF (2 mL). (Z)-1-chlorohex-3-ene (3.66 g, 31 mmol, 1.3 equiv.) in THF (60 mL) was added dropwise at reflux, the reaction mixture further heated to reflux for 12 h and then cooled to 0° C. 3-Butoxybenzaldehyde (4.00 g, 22 mmol, 1.0 equiv.) was added, the reaction mixture was stirred at 25° C. for 30 min and poured on ice-cold 1 M aq. HCl-solution (100 mL). The aqueous layer was extracted with MTBE (2×50 mL). The combined organic phases were washed with brine (50 mL), dried over MgSO.sub.4, filtered and concentrated. The resulting oil was dissolved in Toluene (50 mL), treated at 25° C. with p-Toluenesulfonic acid monohydrate (0.21 g, 1.12 mmol, 0.05 equiv.) and heated to reflux on a Dean-Stark apparatus for 3 h. The resulting mixture was cooled to 25° C., diluted with MTBE (100 mL), washed with saturated aqueous NaHCO.sub.3 solution (50 mL), brine (50 mL), the organic layer was dried over MgSO.sub.4, filtered and concentrated. The resulting crude material was purified by flash column chromatography eluting with a gradient of 1-7% MTBE in Hexanes to give 1-butoxy-3-((1E,4Z)-hepta-1,4-dien-1-yl)benzene (2.06 g, 8.43 mmol, 37.6%) as a clear, colorless liquid.

[0108] .sup.1H-NMR (CDCl.sub.3, 400 MHz): δ=7.22 (dd, J=8.2, 7.6 Hz, 1H), 6.90-6.98 (m, 2H), 6.77 (ddd, J=8.2, 2.6, 0.7 Hz, 1H), 6.39 (dt, J=15.9, 1.5 Hz, 1H), 6.22 (dt, J=15.9, 6.4 Hz, 1H), 5.39-5.58 (m, 2H), 3.99 (t, J=6.5 Hz, 2H), 2.94-3.01 (m, 2H), 2.08-2.18 (m, 2H), 1.75-1.84 (m, 2H), 1.46-1.56 (m, 2H), 1.02 (t, J=7.6 Hz, 6H), 1.00 ppm (t, J=7.6 Hz, 3H).

[0109] .sup.13C-NMR (CDCl.sub.3, 101 MHz): δ=159.4, 139.2, 133.0, 129.9, 129.4, 129.3, 126.0, 118.5, 113.1, 111.9, 67.6, 31.4, 30.6, 20.6, 19.3, 14.3, 13.9 ppm

[0110] MS (EI, 70 eV): 244 (34, [M]+•), 159 (49), 145 (100), 133 (16), 131 (24), 128 (18), 120 (39), 115 (27), 41 (20), 29 (21).

[0111] Odour description (1% solution in EtOH on paper blotter, 24 h): green, citrus, apple, lime, crushed leaves

1.3: 1-butoxy-3-((1E,7Z)-deca-1,7-dien-1-yl)benzene

[0112] The procedure described in Example 1.2. was repeated with the Grignard reagent derived from Z-9-bromonon-3-ene (13.8 g, 67 mmol, 1.2 equiv.) and magnesium (1.64 g, 67 mmol, 1.2 equiv.) in THF (150 mL) and 3-butoxybenzaldehyde (Example 1.1), followed by dehydration of the crude product with p-toluene sulfonic acid (500 mg) in toluene (100 mL). The crude product was purified by flash chromatography on silica gel with a gradient heptane 100% to heptane/MTBE 50:1 to yield (2.18 g, 28%) as a slightly yellow liquid.

[0113] .sup.1H-NMR (CDCl.sub.3, 400 MHz): δ=7.18 (t, J=7.9 Hz, 1H), 6.86-6.94 (m, 2H), 6.73 (ddd, J=8.2, 2.4, 0.7 Hz, 1H), 6.29-6.37 (m, 1H), 6.14-6.26 (m, 1H), 5.28-5.48 (m, 2H), 3.96 (t, J=6.5 Hz, 2H), 2.15-2.25 (m, 2H), 1.94-2.10 (m, 4H), 1.72-1.82 (m, 2H), 1.33-1.57 (m, 6H), 0.96 (td, J=7.5, 6.4 Hz, 6H).

[0114] .sup.13C-NMR (CDCl.sub.3, 101 MHz): δ=159.4 (s), 139.4 (s), 131.8 (s), 131.3 (s), 129.8 (s), 129.4 (s), 129.0 (s), 118.5 (s), 113.0 (s), 112.9-113.0 (m), 111.9 (s), 67.6 (s), 32.9 (s), 31.4 (s), 29.3 (s), 29.0 (s), 27.0 (s), 20.5 (s), 19.3 (s), 14.4 (s), 13.9 (s).

[0115] MS (EI, 70 eV): 286(16), 257(13), 230(6), 176(18), 164(46), 145(69), 127(100), 108(58), 107(58), 55(54), 41(92), 29(50).

[0116] Odour description (1% solution in EtOH on paper blotter, 24 h): melon, green, citrus, floral.

1.4: 1-(4-(3-butoxyphenyl)but-3-en-1-yl)-4-isobutyl-2-methylbenzene and 1-(4-(3-butoxyphenyl)but-3-en-1-yl)-2-isobutyl-4-methylbenzene

A) (3-butoxyphenyl)methanol

[0117] 3-Butoxybenzaldehyde (18.5 g, 104 mmol, 1.0 equiv.) in THF (80 mL) was added dropwise to a suspension of LiAlH.sub.4 (1.26 g, 31.5 mmol, 0.304 eq.) in THF (120 mL) at 25° C. After 1 h, the mixture was cooled to 0° C. and treated carefully with water (1.25 mL) followed by 15% aq. NaOH (1.25 mL) and finally water (3.75 mL). The mixture was warmed to 40° C. and treated with MgSO.sub.4 then filtered. The filtrate was concentrated to give (3-butoxyphenyl)methanol (17.3 g, 96 mmol, 92%) as a pale yellow oil.

[0118] .sup.1H-NMR (CDCl.sub.3, 400 MHz): δ=7.23-7.30 (m, 1H), 6.89-6.95 (m, 2H), 6.82-6.87 (m, 1H), 4.62 (s, 2H), 3.98 (t, J=6.6 Hz, 2H), 2.64 (br s, 1H), 1.74-1.84 (m, 2H), 1.46-1.59 (m, 2H), 1.02 ppm (t, J=7.3 Hz, 3H).

[0119] .sup.13C-NMR (CDCl.sub.3, 101 MHz): δ=159.4, 142.6, 129.5, 118.9, 113.7, 112.9, 67.7, 65.1, 31.4, 19.3, 13.9 ppm.

[0120] MS (EI, 70 eV): 180 (52, [M].sup.+•), 124 (100), 123 (39), 107 (19), 106 (37), 105 (25), 95 (50), 78 (18), 77 (20), 41 (13).

B) 1-(4-(3-butoxyphenyl)but-3-en-1-yl)-4-isobutyl-2-methylbenzene and 1-(4-(3-butoxyphenyl)but-3-en-1-yl)-2-isobutyl-4-methylbenzene

[0121] (3-butoxyphenyl)methanol (17.0 g, 94 mmol, 1.0 equiv.) was combined with triphenylphosphine hydrobromide (32.4 g, 94 mmol, 1.0 equiv.) and acetonitrile (100 mL) and the resulting mixture heated to reflux under nitrogen atmosphere for 20 h. The resulting mixture was concentrated then suspended in Et.sub.2O (70 mL) and placed in the fridge (4° C.) for 5 h. The precipitated solid was filtered and washed with Et.sub.2O (2×50 mL) and then dried under high vacuum at 25° C. for 2 h. The resulting solid was suspended in THF (350 mL), cooled to 5° C. and treated portion-wise with KOtBu (10.38 g, 92 mmol, 0.98 equiv.), maintaining the temperature between 0-5° C. The resulting bright red mixture was stirred for 20 min at 5° C. then treated dropwise over 40 min with a solution of 3-(4-isobutyl-2-methylphenyl)propanal (16.1 g, 78 mmol, 0.83 equiv.) and 3-(2-isobutyl-4-methylphenyl)propanal (2.84 g, 14 mmol, 0.15 equiv.) in THF (50 mL). The resulting mixture was allowed to warm to 25° C. and stirred for 2 h. The mixture was then poured onto a mixture of acetic acid (20 mL) and ice-water (500 mL), extracted with heptane (2×200 mL), the extracts washed successively with 70% methanol (3×100 mL), sat. aq. KHCO.sub.3 (2×100 mL), water (2×100 mL), dried over MgSO.sub.4, filtered and evaporated. The resulting crude material was purified by flash column chromatography eluting with a gradient of 1-7% MTBE in Hexanes to give an isomeric mixture of 1-(4-(3-butoxyphenyl)but-3-en-1-yl)-4-isobutyl-2-methylbenzene and 1-(4-(3-butoxyphenyl)but-3-en-1-yl)-2-isobutyl-4-methylbenzene (22.3 g, 63.6 mmol, 68%) as a clear, pale green liquid (isomers 1 to 4 obtained in ratio 3:25:9:63 (GC) (isomer 1:isomer 2:isomer 3:isomer 4))

[0122] .sup.1H NMR (CHLOROFORM-d, 400 MHz): δ=7.11-7.23 (m), 7.01-7.09 (m), 6.86-6.98 (m), 6.67-6.84 (m), 6.34-6.44 (m), 6.21-6.33 (m), 5.66-5.75 (m), 3.89-3.99 (m), 2.67-2.77 (m), 2.54-2.64 (m), 2.36-2.50 (m), 2.31 (s), 2.30 (s), 2.28 (s), 2.25 (s), 1.69-1.90 (m), 1.42-1.56 (m), 0.86-1.01 ppm (m)

[0123] .sup.13C NMR (BENZENE-d.sub.6, 101 MHz): δ=159.7, 159.7, 159.5, 159.4, 139.3, 139.4, 139.3, 139.3, 139.1, 139.1, 139.0, 139.0, 137.1, 136.9, 136.6, 136.5, 135.3, 135.2, 134.8, 134.8, 132.1, 131.0, 131.0, 130.9, 130.9, 130.5, 130.5, 130.1, 129.6, 129.4, 129.2, 129.2, 129.1, 129.1, 128.7, 128.7, 128.7, 128.7, 126.8, 126.8, 126.7, 126.7, 121.3, 121.1, 118.6, 115.4, 115.1, 115.0, 113.2, 113.1, 112.8, 112.8, 112.3, 111.5, 67.1, 67.1, 67.1, 67.0, 45.0, 41.9, 41.9, 34.9, 33.8, 33.0, 32.8, 32.4, 32.2, 31.3, 31.3, 30.4, 30.2, 30.2, 30.1, 29.9, 29.8, 29.3, 22.4, 22.4, 22.2, 21.2, 20.8, 20.8, 19.2, 19.2, 19.1, 19.1, 13.6, 13.6 ppm.

[0124] MS (EI, 70 eV) (Isomer 1): 350 (12, [M].sup.+•), 189 (9), 161 (58), 133 (29), 120 (10), 119 (100), 117 (9), 115 (9), 105 (17), 55 (15).

[0125] MS (EI, 70 eV) (Isomer 2): 350 (8, [M].sup.+•), 189 (6), 162 (13), 161 (100), 133 (19), 119 (25), 118 (9), 117 (5), 115 (6), 105 (11).

[0126] MS (EI, 70 eV) (Isomer 3): 350 (11, [M].sup.+•), 189 (10), 162 (8), 161 (62), 133 (35), 120 (10), 119 (100), 115 (8), 105 (18), 55 (16).

[0127] MS (EI, 70 eV) (Isomer 4): 350 (9, [M].sup.+•), 189 (8), 162 (13), 161 (100), 133 (23), 119 (25), 118 (9), 115 (6), 105 (11), 43 (5).

[0128] Odour description (1% solution in EtOH on paper blotter, 24 h): citrus, aldehydic, muguet, slightly fatty.

EXAMPLE 2

3-(sec-butoxy)benzaldehyde and a precursor thereof

2.1: 3-(sec-butoxy)benzaldehyde

[0129] The procedure described in Example 1.1. was repeated with 3-hydroxybenzaldehyde (6.0 g, 49.1 mmol, 1 equiv.), potassium carbonate (13.6 g, 98 mmol, 2 equiv.) and 2-bromobutane (10.1 g, 73.7 mmol, 1.5 equiv.) in DMF (60 mL). The crude product was purified by flash chromatography on silica gel with hexane/MTBE 93:7 followed by vacuum bulb-to-bulb distillation at 114° C./0.03 mbar to yield 3-(sec-butoxy)benzaldehyde (6.8 g, 77%) as a colorless liquid.

[0130] .sup.1H-NMR (CDCl.sub.3, 400 MHz): δ=9.80-10.16 (m, 1H), 7.42-7.46 (m, 2H), 7.38-7.41 (m, 1H), 7.14-7.20 (m, 1H), 4.40 (sxt, J=6.0 Hz, 1H), 1.61-1.84 (m, 2H), 1.33 (d, J=5.9 Hz, 3H), 1.00 (t, J=7.5 Hz, 3H).

[0131] .sup.13C-NMR (CDCl.sub.3, 101 MHz): b 192.2 (d), 158.8 (s), 137.8 (s), 130.1 (d), 123.1 (d), 123.0 (d), 114.2 (d), 75.3 (d), 29.1 (t), 19.1 (q), 9.7 (q).

[0132] MS (EI, 70 eV): 178 (15, M+), 122 (100), 121 (95), 93 (8), 77 (7), 65 (11), 57 (7), 41 (9), 29 (18).

[0133] Odour description (10% solution in DPG on paper blotter, 4 h): citrus, fruity, phenolic.

2.2: 1-(sec-butoxy)-3-((1E,4Z)-hepta-1,4-dien-1-yl)benzene

[0134] The procedure described in Example 1.2. was repeated with (Z)-hex-3-en-1-ylmagnesium chloride (0.65 M in THF, 26 mL, 16.9 mmol, 1.2 equiv.) and 3-(sec-butoxy)benzaldehyde (2.5 g, 14.3 mmol, 1 equiv.) in THF (50 mL), followed by dehydration of the crude product with p-toluene sulfonic acid (286 mg, 1.5 mmol, 0.1 equiv.) in toluene (100 mL). The crude product was purified by flash chromatography on silica gel with hexane/MTBE 100:1 to yield 1-(sec-butoxy)-3-((1E,4Z)-hepta-1,4-dien-1-yl)benzene (1.43 g, 39%) as a colorless liquid.

[0135] .sup.1H-NMR (CDCl.sub.3, 400 MHz): δ=7.22 (t, J=7.8 Hz, 1H), 6.91-6.98 (m, 2H), 6.78 (ddd, J=8.1, 2.5, 0.9 Hz, 1H), 6.36-6.44 (m, 1H), 6.18-6.27 (m, 1H), 5.41-5.59 (m, 2H), 4.34 (sxt, J=6.1 Hz, 1H), 2.99 (br. t, J=6.7 Hz, 2H), 2.14 (quind, J=7.4, 1.2 Hz, 2H), 1.60-1.85 (m, 2H), 1.33 (d, J=6.1 Hz, 3H), 1.03 (q, J=7.6 Hz, 3H), 1.00 (q, J=7.3 Hz, 3H).

[0136] .sup.13C-NMR (CDCl.sub.3, 101 MHz): δ 158.4 (s), 139.3 (s), 133.0 (d), 129.9 (d), 129.4 (d), 129.2 (d), 126.0 (d), 118.5 (d), 114.4 (d), 113.6 (d), 75.0 (d), 30.6 (t), 29.3 (t), 20.6 (t), 19.3 (q), 14.3 (q), 9.8 (q).

[0137] MS (EI, 70 eV): 244 (16, M.sup.+), 159 (62), 146 (17), 145 (100), 131 (22), 120 (56), 115 (27), 81 (19), 41 (18), 29 (16).

[0138] Odour description (1% solution in EtOH on paper blotter, 24 h): green, citrus, crushed leaves

EXAMPLE 3

3-Pentyloxybenzaldehyde and precursor thereof

3.1: 3-Pentyloxybenzaldehyde

[0139] The procedure described in Example 1.1. was repeated with 3-hydroxybenzaldehyde (6.0 g, 49.1 mmol, 1 equiv.), potassium carbonate (13.6 g, 98 mmol, 2 equiv.) and 1-bromopentane (8.9 g, 59.0 mmol, 1.2 equiv.) in DMF (60 mL). The crude product was purified by flash chromatography on silica gel with hexane/MTBE 93:7 followed by vacuum bulb-to-bulb distillation at 130° C./0.03 mbar to yield 3-Pentyloxybenzaldehyde (8.0 g, 84%) as a colorless liquid.

[0140] .sup.1H-NMR (CDCl.sub.3, 400 MHz): δ 9.98 (s, 1H), 7.43-7.47 (m, 2H), 7.38-7.42 (m, 1H), 7.15-7.22 (m, 1H), 4.03 (t, J=6.6 Hz, 2H), 1.78-1.88 (m, 2H), 1.35-1.52 (m, 4H), 0.96 (t, J=7.3 Hz, 3H).

[0141] .sup.13C-NMR (CDCl.sub.3, 101 MHz): δ 192.2 (d), 159.7 (s), 137.8 (s), 130.0 (d), 123.3 (d), 121.9 (d), 112.8 (d), 68.3 (t), 28.8 (t), 28.2 (t), 22.4 (t), 14.0 (d).

[0142] MS (EI, 70 eV): 192 (21, M+), 122 (100), 121 (78), 105 (5), 93 (6), 77 (9), 71 (3), 70 (8), 65 (9), 55 (10), 43 (30), 29 (23).

[0143] Odour description (10% solution in DPG on paper blotter, 4 h): floral, watery, citrus, fatty.

3.2: 1-((1E,4Z)-hepta-1,4-dien-1-yl-3-(pentyloxy)benzene

[0144] The procedure described in Example 1.2. was repeated with (Z)-hex-3-en-1-ylmagnesium chloride (0.65 M in THF, 38.4 mL, 25.0 mmol, 1.2 equiv.) and 3-(pentyloxy)benzaldehyde (4.0 g, 20.8 mmol, 1 equiv.) in THF (50 mL), followed by dehydration of the crude product with p-toluene sulfonic acid (432 mg, 2.3 mmol, 0.1 equiv.) in toluene (100 mL). The crude product was purified by flash chromatography on silica gel with hexane/MTBE 100:1 to yield 1-((1E,4Z)-hepta-1,4-dien-1-yl)-3-(pentyloxy)benzene (2.84 g, 47%) as a colorless liquid.

[0145] .sup.1H-NMR (CDCl.sub.3, 400 MHz): δ 7.18-7.32 (m, 1H), 6.87-7.00 (m, 2H), 6.78 (ddd, J=8.2, 2.4, 0.9 Hz, 1H), 6.34-6.47 (m, 1H), 6.16-6.29 (m, 1H), 5.40-5.61 (m, 2H), 3.99 (t, J=6.6 Hz, 2H), 2.99 (br. t, J=6.7 Hz, 2H), 2.10-2.20 (m, 2H), 1.77-1.87 (m, 2H), 1.37-1.54 (m, 4H), 1.04 (t, J=7.6 Hz, 3H), 0.98 (t, J=7.1 Hz, 3H).

[0146] .sup.13C-NMR (CDCl.sub.3, 101 MHz): δ 159.4 (s), 139.2 (s), 133.0 (d), 129.9 (d), 129.4 (d), 129.3 (d), 126.0 (d), 118.5 (d), 113.1 (d), 112.0 (d), 67.9 (t), 30.6 (t), 29.1 (t), 28.3 (t), 22.5 (t), 20.6 (t), 14.3 (q), 14.1 (q).

[0147] MS (EI, 70 eV): 258(21, M.sup.+),159(48), 145(100), 133(18), 131(22), 128(18), 120(41), 115(27), 43(25), 41(20).

[0148] Odour (1% solution in EtOH on paper blotter, 24 h): green, citrus, geranium leaves

EXAMPLE 4

3-((2-methylallyl)oxy)benzaldehyde and precursor thereof

4.1: 3-((2-methylallyl)oxy)benzaldehyde

[0149] The procedure described in Example 1.1. was repeated with 3-hydroxybenzaldehyde (5.0 g, 40.9 mmol, 1 equiv.), potassium carbonate (11.3 g, 82 mmol, 2 equiv.) and 3-Bromo-2-methylpropene (6.63 g, 49.1 mmol, 1.2 equiv.) in DMF (60 mL). The crude product was purified by flash chromatography on silica gel with hexane/MTBE 93:7 followed by vacuum bulb-to-bulb distillation at 129° C./0.03 mbar to yield 3-((2-methylallyl)oxy)benzaldehyde (5.2 g, 72%) as a colorless liquid.

[0150] .sup.1H-NMR (CDCl.sub.3, 400 MHz): δ 9.98 (s, 1H), 7.40-7.50 (m, 3H), 7.21 (dt, J=7.0, 2.5 Hz, 1H), 5.10-5.15 (m, 1H), 5.02 (td, J=2.1, 1.0 Hz, 1H), 4.50 (s, 2H), 1.85 (br. d, J=0.7 Hz, 3H).

[0151] .sup.13C-NMR (CDCl.sub.3, 101 MHz): δ 192.1 (d), 159.3 (s), 140.3 (s), 137.8 (s), 130.0 (d), 123.5 (d), 122.0 (d), 113.3 (d), 113.1 (t), 71.9 (t), 19.4 (q).

[0152] MS (EI, 70 eV): 176 (11, M+), 161 (31), 158 (8), 147 (11), 133 (10), 121 (18), 105 (5), 92 (5), 77 (8), 65 (12), 55 (100), 39 (33), 29 (29).

[0153] Odour description (10% solution in DPG on paper blotter, 4 h): fresh, floral, citrus, anisic.

4.2: 1-((1E,4Z)-hepta-1,4-dien-1-yl)-3-((2-methylallyl)oxy)benzene

[0154] The procedure described in Example 1.2. was repeated with (Z)-hex-3-en-1-ylmagnesium chloride (0.65 M in THF, 52.4 mL, 25.0 mmol, 1.2 equiv.) and 3-((2-methylallyl)oxy)benzaldehyde (5.0 g, 28.4 mmol, 1 equiv.) in THF (50 mL), followed by dehydration of the crude product with p-toluene sulfonic acid (584 mg, 2.3 mmol, 0.1 equiv.) in toluene (100 mL). The crude product was purified by flash chromatography on silica gel with hexane/MTBE 100:1 to yield 1-((1E,4Z)-hepta-1,4-dien-1-yl)-3-((2-methylallyl)oxy)benzene (1.49 g, 20%) as a colorless liquid.

[0155] .sup.1H-NMR (CDCl.sub.3, 400 MHz): δ 7.23 (t, J=7.8 Hz, 1H), 6.94-7.02 (m, 2H), 6.81 (ddd, J=8.3, 2.5, 1.0 Hz, 1H), 6.41 (dt, J=15.9, 1.5 Hz, 1H), 6.24 (dt, J=15.7, 6.6 Hz, 1H), 5.41-5.61 (m, 2H), 5.12-5.18 (m, 1H), 4.98-5.06 (m, 1H), 4.48 (br. s, 2H), 3.00 (t, J=6.7 Hz, 2H), 2.09-2.22 (m, 2H), 1.88 (br. s, 3H), 1.04 (t, J=7.6 Hz, 3H).

[0156] .sup.13C-NMR (CDCl.sub.3, 101 MHz): δ 159.0 (s), 141.0 (s), 139.2 (s), 133.1 (d), 129.8 (d), 129.4 (d), 129.4 (s), 126.0 (d), 118.8 (d), 113.4 (d), 112.7 (t), 112.3 (d), 71.7 (t), 30.6 (t), 20.6 (t), 19.5 (q), 14.3 (q).

[0157] MS (EI, 70 eV): 242(15, M.sup.+), 174(15), 159(32), 145(61), 131(44), 129(43), 128(42), 117(41), 115(60), 91(33), 55(100), 29(35).

[0158] Odour description (1% solution in EtOH on paper blotter, 24 h): green, citrus, anisic, floral.

EXAMPLE 5

3-isopropoxybenzaldehyde and precursor thereof

5.1: 3-isopropoxybenzaldehyde

[0159] The procedure described in Example 1.1. was repeated with 3-hydroxybenzaldehyde (6.0 g, 49.1 mmol, 1 equiv.), potassium carbonate (13.6 g, 98 mmol, 2 equiv.) and 2-bromopropane (7.25 g, 59 mmol, 1.2 equiv.) in DMF (60 mL). The crude product was purified by flash chromatography on silica gel with hexane/MTBE 93:7 followed by vacuum bulb-to-bulb distillation at 120° C./0.03 mbar to yield 3-isopropoxybenzaldehyde (5.88 g, 73%) as a colorless liquid.

[0160] .sup.1H-NMR (CDCl.sub.3, 400 MHz): δ=9.98 (s, 1H), 7.38-7.46 (m, 3H), 7.13-7.19 (m, 1H), 4.64 (spt, J=6.1 Hz, 1H), 1.37 (d, J=6.1 Hz, 6H).

[0161] .sup.13C-NMR (CDCl.sub.3, 101 MHz): δ=192.2 (d), 158.5 (s), 137.8 (s), 130.1 (d), 123.1 (d), 123.0 (d), 114.2 (d), 70.2 (d), 21.9 (2q).

[0162] MS (EI, 70 eV): 164 (13, M+), 122 (73), 121 (100), 93 (9), 77 (4), 65 (11), 43 (11), 39 (13), 27 (7).

[0163] Odour description (10% solution in DPG on paper blotter, 4 h): green, phenolic, citrus, medicinal.

5.2: 1-((1E,4Z)-hepta-1,4-dien-1-yl)-3-isopropoxybenzene

[0164] The procedure described in Example 1.2. was repeated with (Z)-hex-3-en-1-ylmagnesium chloride (1.3 M in THF, 29 mL, 37.5 mmol, 1.5 equiv.) and 3-isopropoxybenzaldehyde (4.0 g, 24.4 mmol, 1 equiv.) in THF (50 mL), followed by dehydration of the crude product with p-toluene sulfonic acid (432 mg, 2.3 mmol, 0.1 equiv.) in toluene (100 mL). The crude product was purified by flash chromatography on silica gel with hexane/MTBE 100:1 to yield 1-((1E,4Z)-hepta-1,4-dien-1-yl)-3-isopropoxybenzene (1.54 g, 29%) as a colorless liquid.

[0165] .sup.1H-NMR (CDCl.sub.3, 400 MHz): δ=7.22 (t, J=7.8, 1H), 6.90-6.98 (m, 2H), 6.78 (ddd, J=8.1, 2.5, 0.9 Hz, 1H), 6.39 (dt, J=15.7, 1.2, 1H), 6.22 (dt, J=15.9, 6.6 Hz, 1H), 5.42-5.59 (m, 2H), 4.59 (spt, J=5.6 Hz, 1H), 2.99 (br. t, J=6.8 Hz, 2H), 2.10-2.20 (m, 2H), 1.37 (d, J=5.9 Hz, 6H), 1.04 (t, J=7.6 Hz, 3H).

[0166] .sup.13C-NMR (CDCl.sub.3, 101 MHz): δ=158.1 (s), 139.3 (s), 133.0 (d), 129.9 (d), 129.4 (d), 129.3 (d), 126.0 (d), 118.6 (d), 114.4 (d), 113.6 (d), 69.8 (d), 30.6 (t), 22.1 (2q), 20.6 (t), 14.3 (q).

[0167] MS (EI, 70 eV): 230(18),159(60),145(100), 131(26), 120(54), 115(29), 107(18), 81(20), 43(21), 41(19).

[0168] Odour description (1% solution in EtOH on paper blotter, 24 h): green, citrus, metallic, fatty.

EXAMPLE 6a-6m

6a: 1-butoxy-3-(4-(4-(tert-butyl)phenyl)but-1-en-1-yl)benzene

[0169] The procedure described in example 1.4 can be repeated by replacing the solution of 3-(4-isobutyl-2-methylphenyl)propanal and 3-(2-isobutyl-4-methylphenyl)propanal in THF with a corresponding solution of 3-(4-(tert-butyl)phenyl)propanal to prepare the title product 1-butoxy-3-(4-(4-(tert-butyl)phenyl)but-1-en-1-yl)benzene.

6b: 1-butoxy-3-(4-(4-(tert-butyl)phenyl)-3-methylbut-1-en-1-yl)benzene

[0170] The procedure described in example 1.4 can be repeated by replacing the solution of 3-(4-isobutyl-2-methylphenyl)propanal and 3-(2-isobutyl-4-methylphenyl)propanal in THF with a corresponding solution of 3-(4-(tert-butyl)phenyl)-2-methylpropanal to prepare the title product 1-butoxy-3-(4-(4-(tert-butyl)phenyl)-3-methylbut-1-en-1-yl)benzene.

6c: 1-butoxy-3-(4-(3-isopropylphenyl)pent-1-en-1-yl)benzene

[0171] The procedure described in example 1.4 can be repeated by replacing the solution of 3-(4-isobutyl-2-methylphenyl)propanal and 3-(2-isobutyl-4-methylphenyl)propanal in THF with a corresponding solution of 3-(3-isopropylphenyl)butanal to prepare the title product 1-butoxy-3-(4-(3-isopropylphenyl)pent-1-en-1-yl)benzene.

6d: 11-(3-butoxyphenyl)-2,6-dimethylundeca-6,10-dien-2-ol

[0172] The procedure described in example 1.4 can be repeated by replacing the solution of 3-(4-isobutyl-2-methylphenyl)propanal and 3-(2-isobutyl-4-methylphenyl)propanal in THF with a corresponding solution of 9-hydroxy-5,9-dimethyldec-4-enal to prepare the title product 11-(3-butoxyphenyl)-2,6-dimethylundeca-6,10-dien-2-ol.

6e: 1-butoxy-3-(3-methyldodec-1-en-1-yl)benzene

[0173] The procedure described in example 1.4 can be repeated by replacing the solution of 3-(4-isobutyl-2-methylphenyl)propanal and 3-(2-isobutyl-4-methylphenyl)propanal in THF with a corresponding solution of 2-methylundecanal to prepare the title product 1-butoxy-3-(3-methyldodec-1-en-1-yl)benzene.

6f: 5-(4-(3-butoxyphenyl)-2-methylbut-3-en-1-yl)benzo[d][1,3]dioxole

[0174] The procedure described in example 1.4 can be repeated by replacing the solution of 3-(4-isobutyl-2-methylphenyl)propanal and 3-(2-isobutyl-4-methylphenyl)propanal in THF with a corresponding solution of 3-(benzo[d][1,3]dioxol-5-yl)-2-methylpropanal to prepare the title product 5-(4-(3-butoxyphenyl)-2-methylbut-3-en-1-yl)benzo[d][1,3]dioxole.

6q: 1-butoxy-3-(tetradeca-1,3-dien-1-yl)benzene

[0175] The procedure described in example 1.4 can be repeated by replacing the solution of 3-(4-isobutyl-2-methylphenyl)propanal and 3-(2-isobutyl-4-methylphenyl)propanal in THF with a corresponding solution of tridec-2-enal to prepare the title product 1-butoxy-3-(tetradeca-1,3-dien-1-yl)benzene.

6h: 1-butoxy-3-(3-phenylprop-1-en-1-yl)benzene

[0176] The procedure described in example 1.4 can be repeated by replacing the solution of 3-(4-isobutyl-2-methylphenyl)propanal and 3-(2-isobutyl-4-methylphenyl)propanal in THF with a corresponding solution of 2-phenylacetaldehyde to prepare the title product 1-butoxy-3-(3-phenylprop-1-en-1-yl)benzene.

6i: 1-butoxy-3-((5E)-undeca-1,5-dien-1-yl)benzene

[0177] The procedure described in example 1.4 can be repeated by replacing the solution of 3-(4-isobutyl-2-methylphenyl)propanal and 3-(2-isobutyl-4-methylphenyl)propanal in THF with a corresponding solution of (E)-dec-4-enal to prepare the title product 1-butoxy-3-((5E)-undeca-1,5-dien-1-yl)benzene.

6j: 5-(5-(3-butoxyphenyl)pent-4-en-1-ylidene)octahydro-1H-4,7-methanoindene

[0178] The procedure described in example 1.4 can be repeated by replacing the solution of 3-(4-isobutyl-2-methylphenyl)propanal and 3-(2-isobutyl-4-methylphenyl)propanal in THF with a corresponding solution of 4-(octahydro-5H-4,7-methanoinden-5-ylidene)butanal to prepare the title product 5-(5-(3-butoxyphenyl)pent-4-en-1-ylidene)octahydro-1H-4,7-methanoindene.

6k: 1-butoxy-3-(4-(4-ethylphenyl)-3,3-dimethylbut-1-en-1-yl)benzene

[0179] The procedure described in example 1.4 can be repeated by replacing the solution of 3-(4-isobutyl-2-methylphenyl)propanal and 3-(2-isobutyl-4-methylphenyl)propanal in THF with a corresponding solution of 3-(4-ethylphenyl)-2,2-dimethylpropanal to prepare the title product 1-butoxy-3-(4-(4-ethylphenyl)-3,3-dimethylbut-1-en-1-yl)benzene.

6l: 1-butoxy-3-(7-methoxy-3,7-dimethylnon-1-en-1-yl)benzene

[0180] The procedure described in example 1.4 can be repeated by replacing the solution of 3-(4-isobutyl-2-methylphenyl)propanal and 3-(2-isobutyl-4-methylphenyl)propanal in THF with a corresponding solution of 6-methoxy-2,6-dimethyloctanal to prepare the title product 1-butoxy-3-(7-methoxy-3,7-dimethylnon-1-en-1-yl)benzene.

[0181] 6m: 1-butoxy-3-(4-(4-isobutylphenyl)but-1-en-1-yl)benzene

[0182] The procedure described in example 1.4 can be repeated by replacing the solution of 3-(4-isobutyl-2-methylphenyl)propanal and 3-(2-isobutyl-4-methylphenyl)propanal in THF with a corresponding solution of 3-(4-isobutylphenyl)propanal to prepare the title product 1-butoxy-3-(4-(4-isobutylphenyl)but-1-en-1-yl)benzene.

EXAMPLE 7

Fragrance Comprising a Compound of Formula (I)

[0183]

TABLE-US-00001 parts by weight Compound/Ingredient 1/1000 Benzyl acetate 15 2-(4-Methylcyclohex-3-en-1-yl)propan-2-yl acetate 60 (E)-2-Benzylideneoctanal 30 Decanal 18 Allyl 2-(isopentyloxy)acetate 3 CASSYRANE (2-(tert-butyl)-5-methyl-2-propyl- 0.5 2,5-dihydrofuran) Triethylcitrate (TEC) 6.3 Citronellol 20 CYCLAL C (2,4-dimethylcyclohex-3-ene-1-carbaldehyde) 5 Delta Damascone 1 (E)-dec-4-enal 0.2 DIHYDRO MYRCENOL 60 DPG 296.3 EUCALYPTUS essential oil 10 FLORALOZONE (3-(4-ethylphenyl)-2,2-dimethylpropanal) 3 FLORHYDRAL (3-(3-isopropylphenyl)butanal) 2 FRESKOMENTHE (2-(sec-butyl)cyclohexan-1-one) 5 GALBANONE (1-(3,3/5,5-dimethylcyclohex-1-en-1- 4 yl)pent-4-en-1-one) ISO E SUPER 20 ISOBUTAVAN (4-formyl-2-methoxyphenyl isobutyrate) 0.2 ISORALDEINE 10 JAVANOL 1 LABIENOXIME.sup.1) 1%/IPM-TEC @ 10% DPG 3 LEMONILE (3,7-dimethylnona-2,6-dienenitrile) 35 Terpinolene (1-methyl-4-(propan-2-ylidene)cyclohex- 20 1-ene) Linalol 90 MANZANATE (ethyl 2-methylpentanoate) 2 METHYL PAMPLEMOUSSE (6,6-dimethoxy-2,5,5- 5 trimethylhex-2-ene) MYRALDENE (4-(4-methylpent-3-en-1-yl)cyclohex-3-ene- 10 1-carbaldehyde) NYMPHEALTM (3-(4-isoputyl-2-methylpehnyl)propanal) 8 Orange terpenes 240 Petalia (2-cyclohexylidene-2-(o-tolyl)acetonitrile) 7 RHUBAFURAN (2,4-dimethyl-4-phenyltetrahydrofuran) 0.5 ROSYFOLIA ® (1-methyl-2-(5methylhex-4-en-2- 3 yl)cyclopropyl)methanol SYLKOLIDE 5 ((E)-2-((3,5-dimethylhex-3-en-2-yl)oxy)-2- methylpropyl cyclopropanecarboxylate) TOSCANOL (1-(cyclopropylmethyl)-4-methoxybenzene) 1 Total: 1000

1) 3E,6E)-2,4,4,7-tetramethylnona-6,8-dien-3-one oxime

[0184] The fragrance composition above possesses a classical fresh green lemon character. This fragrance can be applied to, e.g., all-purpose cleaner (APC), at 0.1-1.5 wt % (e.g. 0.3 wt %).

[0185] By replacing 40 parts of DPG of the accord above by 3-butoxybenzaldehyde, i.e. a compound of formula (I), the overall odor character is now softer, more floral, rounder, and over all, the perception is easier, fresher, more comfortable.

[0186] By replacing 40 parts of DPG of the accord above by 3-butoxybenzaldehyde, i.e. a compound of formula (I), and replacing 110 parts of DPG of the accord above by a mixture comprising 1-butoxy-3-((1E,4Z)-hepta-1,4-dien-1-yl)benzene (60 parts) and two additional precursors (4-(dodecylthio)-4-methylpentan-2-one (10 parts) and ethyl N,S-bis(4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)cysteinate (40 parts)), the longlastingness of the accord is greatly improved, delivering a pleasant and very natural combination.

EXAMPLE 8

Fragrance Comprising a Compound of Formula (II)

[0187]

TABLE-US-00002 parts by weight Compound/Ingredient 1/1000 Nerolex ((Z)-3,7-dimethylocta-2,6-dien-1-ol) 11 PETALIA (2-cyclohexylidene-2-(o-tolyl)acetonitrile) 20 LABIENOXIME 1%/IPM-TEC @ 10% DPG 5 (3E,6E)-2,4,4,7-tetramethylnona-6,8-dien-3-one oxime) Benzyl acetate 15 (Z)-hex-3-en-1-yl acetate 2 Myraldyle acetate 20 ((4-(4-methylpent-3-en-1-yl)cyclohex-3-en-1- yl)methyl acetate) 2-phenylethan-1-ol 100 (E)-2-benzylideneheptanal 40 (E)-2-benzylideneoctanal 100 dodecanal 3 ROSYFOLIA ® (1-methyl-2-(5methylhex-4-en-2- 4 yl)cyclopropyl)methanol NYMPHEAL ™ (3-(4-isoputyl-2-methylpehnyl)propanal) 20 Cyclamen aldehyde (3-(4-isopropylphenyl)-2- 30 methylpropanal) Indol @ 10% TEC 7 Prunolide (5-pentyldihydrofuran-2(3H)-one) 2 Peach Pure (5-heptyldihydrofuran-2(3H)-one) 3 Nectaryl (2-(2-(4-methylcyclohex-3-en-1- 5 yl)propyl)cyclopentan-1-one) Citronellol 40 Dipropylen glycol (DPG) 195 ESTRAGOLE (1-allyl-4-methoxybenzene) 1 HEDIONE (methyl 2-(3-oxo-2-pentylcyclopentyl)acetate) 60 Grapefruit oil 20 Isoeugenol 9 Citral 3 Linalol 180 FLOROCYCLENE (3a,4,5,6,7,7a-hexahydro-1H-4,7- 10 methanoinden-6-yl propionate) Geraniol 45 PEONILE ® (2-cyclohexylidene-2-phenylacetonitrile) 50 Total: 1000

[0188] 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 0.3-1.5 wt % (e.g. 0.6 wt %).

[0189] By replacing 30 parts of DPG of the accord above by 1-butoxy-3-((1E,4Z)-hepta-1,4-dien-1-yl)benzene, i.e. a precursor of a compound of formula (I), the fresh green effect on wet fabric is clearly enhanced. And, in particular, the longlastingness of the accord on dry fabric is clearly enhanced when the dry fabric is assessed after one or three days.

[0190] By replacing 70 parts of DPG of the accord above by 1-butoxy-3-((1E,4Z)-hepta-1,4-dien-1-yl)benzene, the green freshness becomes very present and brings a surprising and unusual freshness on dry fabric, reminiscent of green leaf and fresh apple skin.

EXAMPLE 9

Fragrance Comprising a Compound of Formula (II)

[0191]

TABLE-US-00003 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-tetramethyldodecahydro- 1 naphtho[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- 2 ylidene)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) 5 10%/DPG Hexyl salicylate 75 SERENOLIDE (2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2- 30 methylpropyl cyclopropanecarboxylate) SPIROGALBANONE (1-(spiro[4.5]dec-6/7- 1 en-7-yl)pent-4-en-1-one STEMONE ((Z)-5-methylheptan-3-one oxime) 1 TETRAHYDRO LINALOL 50 UNDECAVERTOL 10 Dipropylen glycol (DPG) 165 Total: 1000

[0192] 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 powder detergent (HDPD), at 0.1-1.5 wt % (e.g. 0.3 wt %).

[0193] By replacing 100 parts of DPG of the accord above by 1-butoxy-3-((1E,4Z)-hepta-1,4-dien-1-yl)benzene, i.e. a precursor of a compound of formula (I), the performance and diffusion on wet towels is enhanced with a fresh green pleasant character. And on dry fabric, the substantivity is noticeably improved, with an unusual and very pleasant fresh green character.

[0194] By replacing 110 parts of DPG of the accord above by a mixture comprising 1-butoxy-3-((1E,4Z)-hepta-1,4-dien-1-yl)benzene (70 parts) and two additional precursors (4-(dodecylthio)-4-methylpentan-2-one (10 parts) and ethyl N,S-bis(4-oxo-4-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-2-yl)cysteinate (30 parts)), a very unusual and pleasant fresh green juicy fruity character is delivered on dry fabric. This fresh green juicy fruity character will lasts for few days, which is also novel and surprising.