Lily of the valley odorant

Abstract

The present disclosure concerns a perfuming ingredient of a compound of formula (I) ##STR00001##
in the form of any one of its stereoisomers or a mixture thereof, and wherein X represents a CHO group when R1 represents a C1-2 alkyl group or X represents a CH(R6)CHO group when R1 represents a hydrogen atom or a C1-2 alkyl group. Each of R2, R3, R4, R5 and R6 represents, independently from each other, a hydrogen atom or a C1-2 alkyl group; or R3 and R4 represent, when taken together, a ethanediyl group; and —C(R3)(R4)—CH(R5)—OH group is, relative to position 1, an ortho, a meta, a para substituent of the aromatic ring or a mixture thereof. Also disclosed is the compound of formula (I) as part of a perfuming composition or of a perfumed consumer product.

Claims

1. A method to confer, enhance, improve or modify odor properties of a perfuming composition or of a perfumed article, the method comprising adding to said composition or article an effective amount of a compound of formula (I) use as a perfuming ingredient, wherein formula (I) is: ##STR00007## in the form of any one of its stereoisomers or a mixture thereof, and wherein X represents a CHO group when R.sup.1 represents a C.sub.1-2 alkyl group or X represents a CH(R.sup.6)CHO group when R.sup.1 represents a hydrogen atom or a C.sub.1-2 alkyl group; each R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 represents, independently from each other, a hydrogen atom or a C.sub.1-2 alkyl group; or R.sup.3 and R.sup.4 represent, when taken together, an ethanediyl group; and —C(R.sup.3)(R.sup.4)—CH(R.sup.5)—OH group is, relative to position 1, an ortho, a meta, a para substituent of the aromatic ring or a mixture thereof.

2. The method according to claim 1, characterized in that the —C(R.sup.3)(R.sup.4)—CH(R.sup.5)—OH group is a meta or para substituent of the aromatic ring, relative to position 1.

3. The method according to claim 1, characterized in that the compound (I) is a compound of formula II ##STR00008## in the form of any one of its stereoisomers or a mixture thereof, and wherein X, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 have the same meaning as defined in claim 1.

4. The method according to claim 1, characterized in that R.sup.1 is a methyl group when X represents a CHO group or R.sup.1 is a hydrogen atom or a methyl group when X represents a CH(R.sup.6)CHO group, R.sup.6 having the same meaning as defined in claim 1.

5. The method according to claim 1, characterized in that the compound (I) is a compound of formula (III) ##STR00009## in the form of any one of its stereoisomers or a mixture thereof, and wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 have the same meaning as defined in claim 1.

6. The method according to claim 1, characterized in that R.sup.2, R.sup.5, and R.sup.6 is a hydrogen atom or a methyl group.

7. The method according to claim 1, characterized in that R.sup.3 is a methyl group and R.sup.4 may be a hydrogen atom or a methyl group or R.sup.3 and R.sup.4 represent, when taken together, an ethanediyl group.

8. The method according to claim 1, characterized in that the compound (I) is a compound of formula IV ##STR00010## in the form of any one of its stereoisomers or a mixture thereof, and wherein R.sup.1, R.sup.2, R.sup.5, and R.sup.6 have the same meaning as defined in claim 1.

9. The method according to claim 8, characterized in that R.sup.1, R.sup.2, R.sup.5, and R.sup.6 represent, independently from each other, a hydrogen atom.

10. A compound of formula (I) as defined in claim 1 provided that 3-(4-(1-hydroxy-2-methylpropan-2-yl)phenyl)propanal, 3-(4-(2-hydroxyethyl)phenyl)propanal, 3-(4-(1-(hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(4-(1-hydroxy-2-methylpropan-2-yl)phenyl)butanal, 3-(4-(2-hydroxypropyl)phenyl)propanal, 3-(4-(1-(hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(3-(1-(hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(3-(1-(hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2-(1-(hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2-(1-(hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(3-(2-hydroxypropyl)phenyl)butanal, 3-(3-(2-hydroxypropyl)phenyl)propanal, 3-(3-(2-hydroxyethyl)phenyl)propanal, 3-(3-(2-hydroxyethyl)phenyl)butanal, 3-(3-(1-hydroxy-2-methylpropan-2-yl)phenyl)butanal, 3-(3-(1-hydroxy-2-methylpropan-2-yl)phenyl)propanal, 3-(2-(1-hydroxy-2-methylpropan-2-yl)phenyl)propanal, 3-(2-(1-hydroxy-2-methylpropan-2-yl)phenyl)butanal, 3-(2-(2-hydroxypropyl)phenyl)butanal, 3-(2-(2-hydroxypropyl)phenyl)propanal, 3-(4-(2-hydroxyethyl)phenyl)butanal and 3-(4-(2-hydroxypropyl)phenyl)butanal are excluded.

11. A perfuming composition comprising: i) at least one compound of formula (I), as defined in claim 1; ii) at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base; and optionally at least one perfumery adjuvant.

12. A perfumed consumer product comprising at least one compound of formula (I), as defined in claim 1.

13. The perfumed consumer product according to claim 12, characterized in that the perfumed consumer product is a perfume, a fabric care product, a body-care product, a cosmetic preparation, a skin-care product, an air care product or a home care product.

14. The perfumed consumer product according to claim 13, characterized in that the perfumed consumer product is a fine perfume, a splash or eau de parfum, a cologne, a shave or after-shave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtain-care product, a shampoo, a coloring preparation, a color care product, a hair shaping product, a dental care product, a disinfectant, an intimate care product, a hair spray, a vanishing cream, a deodorant or antiperspirant, a hair remover, a tanning or sun product, a nail product, a skin cleansing, a makeup, a perfumed soap, a shower or bath mousse, an oil or gel, a foot/hand care product, a hygiene product, an air freshener, a “ready to use” powdered, an air freshener, a mold remover, a furnisher care, a wipe, a dish detergent or a hard-surface detergent, a leather care product, a car care product.

15. A perfumed consumer product comprising at least the composition as defined in claim 11.

16. The perfumed consumer product according to claim 15, characterized in that the perfumed consumer product is a perfume, a fabric care product, a body-care product, a cosmetic preparation, a skin-care product, an air care product or a home care product.

17. The perfumed consumer product according to claim 16, characterized in that the perfumed consumer product is a fine perfume, a splash or eau de parfum, a cologne, a shave or after-shave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtain-care product, a shampoo, a coloring preparation, a color care product, a hair shaping product, a dental care product, a disinfectant, an intimate care product, a hair spray, a vanishing cream, a deodorant or antiperspirant, a hair remover, a tanning or sun product, a nail product, a skin cleansing, a makeup, a perfumed soap, a shower or bath mousse, an oil or gel, a foot/hand care product, a hygiene product, an air freshener, a “ready to use” powdered, an air freshener, a mold remover, a furnisher care, a wipe, a dish detergent or a hard-surface detergent, a leather care product, a car care product.

Description

EXAMPLES

(1) The invention will now be described in further detail by way of the following examples, wherein the abbreviations have the usual meaning in the art, the temperatures are indicated in degrees centigrade (° C.); the NMR spectral data were recorded in CDCl.sub.3 (if not stated otherwise) with a 500 MHz machine for .sup.1H and .sup.13C, the chemical shifts 8 are indicated in ppm with respect to TMS as standard, the coupling constants J are expressed in Hz.

Example 1

(2) Synthesis of Compounds of Formula (I)

3-(4-(1-hydroxy-2-methylpropan-2-yl)phenyl)propanal

Step 1: 2-(4-bromophenyl)-2-methylpropan-1-ol

(3) To a suspension of lithium aluminum hydride (2.95 g, 78 mmol, 2 equiv.) in THF (70 mL) at 0° C. was added a solution of methyl 2-(4-bromophenyl)-2-methylpropanoate (10 g, 39 mmol, 1 equiv.) in THF (60 mL) dropwise. After stirring at 0° C. for 1 h, the reaction was quenched sequentially with 3 mL of water, 9 mL of a 5% sodium hydroxide solution and 3 mL of water. It was filtered on a Celite pad using ether as an eluent. The solvent was evaporated and the residue was purified by bulb-to-bulb distillation (2-4 mbar, 130° C.) to afford 2-(4-bromophenyl)-2-methylpropan-1-ol (8.27 g, 93% yield).

(4) .sup.1H NMR: 1.30 (s, 6H), 3.57 (s, 2H), 7.25 (d, J=8.6 Hz, 2H), 7.45 (d, J=8.6 Hz, 2H).

(5) .sup.13C NMR: 145.6 (s), 131.4 (d, 2C), 128.2 (d, 2C), 120.1 (s), 72.8 (t), 39.9 (s), 25.2 (q, 2C).

Step 2: 3-(4-(1-hydroxy-2-methylpropan-2-yl)phenyl)propanal

(6) A solution of 2-(4-bromophenyl)-2-methylpropan-1-ol (5.0 g, 21.8 mmol, 1 equiv.) and N-cyclohexyl-N-methylaminecyclohexanamine (5.5 mL, 24.0 mmol, 1.1 equiv.) in DMF (44 mL) was degassed and stirred under an argon atmosphere for 20 min. Allyl alcohol (1.63 mL, 24.0 mmol, 1.1 equiv.) and bis(dibenzylideneacetone)palladium(0) (125 mg, 0.22 mmol, 0.01 equiv.) were added, followed by 2-(tert-butylphosphino)-1-phenyl-1H-indole (221 mg, 0.66 mmol, 0.03 equiv.) and the reaction was heated to 100° C. for 1 h. After cooling down to r.t., it was diluted with ether and washed three times with water. The organic layer was dried over sodium sulfate and the solvent was evaporated. The residue (GC ratio of linear/branched products: 5.6:1) was purified by flash column chromatography on silica gel (Heptane/AcOEt 7:3 to 65:35) and bulb-to-bulb distillation (0.35 mbar, 140-145° C.) to afford the desired aldehyde as an oil (2.57 g, 57% yield).

(7) .sup.1H NMR: 1.31 (s, 6H), 2.77 (t, J=7.5 Hz, 2H), 2.94 (t, J=7.5 Hz, 2H), 3.59 (s, 2H), 7.17 (d, J=8.3 Hz, 2H), 7.31 (d, J=8.3 Hz, 2H), 9.81 (t, J=1.4 Hz, 1H).

(8) .sup.13C NMR: 201.7 (d), 144.4 (s), 138.1 (s), 128.3 (d, 2C), 126.5 (d, 2C), 73.0 (t), 45.2 (t), 39.8 (s), 27.5 (t), 25.3 (q, 2C).

(9) Minor isomer: 2-(4-(1-hydroxy-2-methylpropan-2-yl)phenyl)propanal

(10) .sup.1H NMR: 1.33 (s, 6H), 1.44 (d, J=7.1 Hz, 3H), 3.61 (s, 2H), 3.62 (m, 1H), 7.19 (d, J=8.3 Hz, 2H), 7.40 (d, J=8.3 Hz, 2H), 9.67 (d, J=1.4 Hz, 1H).

(11) .sup.13C NMR: 201.2 (d), 145.8 (s), 135.4 (s), 128.3 (d, 2C), 127.0 (d, 2C), 73.0 (t), 52.5 (d), 39.9 (s), 25.3 (q, 2C), 14.5 (q).

3-(4-(1-hydroxy-2-methylpropan-2-yl)phenyl)-2-methylpropanal

(12) A solution of 2-(4-bromophenyl)-2-methylpropan-1-ol (2.0 g, 8.73 mmol, 1 equiv.) and N-cyclohexyl-N-methylaminecyclohexanamine (2.2 mL, 9.60 mmol, 1.1 equiv.) in DMF (17 mL) was degassed and stirred under an argon atmosphere for 20 min. Methallyl alcohol (0.81 mL, 9.60 mmol, 1.1 equiv.) and bis(dibenzylideneacetone)palladium(0) (50 mg, 0.087 mmol, 0.01 equiv.) were added, followed by 2-(tert-butylphosphino)-1-phenyl-1H-indole (88 mg, 0.26 mmol, 0.03 equiv.) and the reaction was heated to 100° C. for 1 h. After cooling down to r.t., it was diluted with ether and washed three times with water. The organic layer was dried over sodium sulfate and the solvent was evaporated. The residue was purified by flash column chromatography on silica gel (Heptane/AcOEt 7:3) and bulb-to-bulb distillation (0.35 mbar, 145-150° C.) to afford the desired aldehyde as an oil (1.49 g, 77% yield).

(13) .sup.1H NMR: 1.09 (d, J=7.0 Hz, 3H), 1.31 (s, 6H), 2.59 (A of ABX, J=13.8, 8.1 Hz, 1H), 2.67 (m, 1H), 3.06 (B of ABX, J=13.8, 6.1 Hz, 1H), 3.59 (s, 2H), 7.14 (d, J=8.3 Hz, 2H), 7.31 (d, J=8.3 Hz, 2H), 9.71 (d, J=1.6 Hz, 1H).

(14) .sup.13C NMR: 204.5 (d), 144.5 (s), 136.6 (s), 129.1 (d, 2C), 126.4 (d, 2C), 73.0 (t), 48.0 (d), 39.8 (s), 36.1 (t), 25.3 (q, 2C), 13.3 (q).

3-(4-(1-hydroxypropan-2-yl)phenyl)propanal

Step 1: ethyl 2-(4-bromophenyl)propanoate

(15) To a solution of ethyl 2-(4-bromophenyl)acetate (17.1 g, 70 mmol, 1 equiv.) in THF (235 mL) at −78° C. was added a solution of lithium bis(trimethylsilyl)amide (1 M in THF, 77 mL, 77 mmol, 1.1 equiv.) dropwise. After stirring at −78° C. for 15 min, iodomethane (5.5 mL, 88 mmol, 1.25 equiv.) was added dropwise. After stirring at −78° C. for 1 h30, the reaction was quenched with a saturated solution of ammonium chloride. It was extracted three times with ether, the combined organic extracts were dried over sodium sulfate and the solvent was evaporated. The residue was purified by flash column chromatography on silica gel (Heptane/AcOEt 98:2) and bulb-to-bulb distillation (2-3 mbar, 140° C.) to afford the desired ester as an oil (9.72 g, 54% yield).

Step 2: 2-(4-bromophenyl)propan-1-ol

(16) To a suspension of lithium aluminum hydride (1.42 g, 37 mmol, 2 equiv.) in THF (31 mL) at 0° C. was added a solution of ethyl 2-(4-bromophenyl)propanoate (4.8 g, 19 mmol, 1 equiv.) in THF (31 mL) dropwise. After stirring for 2 h at r.t., the reaction was cooled down to 0° C. and quenched successively with 1.4 mL of water, 4.2 mL of a 5% NaOH solution and 1.4 mL of water. It was filtered on a Celite pad using ether as an eluent and the solvent was evaporated. The crude product was used as such for the next step.

Step 3: 3-(4-(1-hydroxypropan-2-yl)phenyl)propanal

(17) A solution of 2-(4-bromophenyl)propan-1-ol (3.78 g, 17.6 mmol, 1 equiv.) and N-cyclohexyl-N-methylaminecyclohexanamine (4.42 mL, 19.3 mmol, 1.1 equiv.) in DMF (35 mL) was degassed and stirred under an argon atmosphere for 20 min. Allyl alcohol (1.31 mL, 19.3 mmol, 1.1 equiv.) and bis(dibenzylideneacetone)palladium(0) (101 mg, 0.18 mmol, 0.01 equiv.) were added, followed by 2-(tert-butylphosphino)-1-phenyl-1H-indole (178 mg, 0.53 mmol, 0.03 equiv.) and the reaction was heated to 100° C. for 1 h. After cooling down to r.t., it was diluted with ether and washed three times with water. The organic layer was dried over sodium sulfate and the solvent was evaporated. The residue (GC ratio of linear/branched products: 5.6:1) was purified by flash column chromatography on silica gel (Heptane/AcOEt 6:4) and bulb-to-bulb distillation (0.35 mbar, 140-145° C.) to afford the desired aldehyde as an oil (1.92 g, 57% yield).

(18) .sup.1H NMR: 1.25 (d, J=7.0 Hz, 3H), 2.77 (dt, J=7.6, 1.3 Hz, 2H), 2.93 (t, J=7.6 Hz, 2H), 2.93 (m, 1H), 3.67 (d, J=6.8 Hz, 2H), 7.16 (m, 4H), 9.81 (t, J=1.3 Hz, 1H).

(19) .sup.13C NMR: 201.7 (d), 141.7 (s), 138.6 (s), 128.5 (d, 2C), 127.7 (d, 2C), 68.7 (t), 45.2 (t), 42.0 (d), 27.7 (t), 17.6 (q).

3-(4-(2-hydroxypropyl)phenyl)propanal

Step 1: 1-(4-bromophenyl)propan-2-ol

(20) To a suspension of lithium aluminum hydride (891 mg, 23.5 mmol, 1 equiv.) in THF (30 mL) at 0° C. was added a solution of 1-(4-bromophenyl)propan-2-one (5.00 g, 23.5 mmol, 1 equiv.) in THF (17 mL) dropwise. After stirring at 0° C. for 1 h, the reaction was quenched sequentially with 0.9 mL of water, 2.7 mL of a 5% sodium hydroxide solution and 0.9 mL of water. It was filtered on a Celite pad using ether as an eluent. The solvent was evaporated and the residue was purified by bulb-to-bulb distillation (2-4 mbar, 130° C.) to afford 2-(4-bromophenyl)-2-methylpropan-1-ol (4.91 g, 97% yield).

(21) .sup.1H NMR: 1.22 (d, J=6.2 Hz, 3H), 2.65 (A of ABX, J=13.6, 7.8 Hz, 1H), 2.72 (B of ABX, J=13.6, 4.9 Hz, 1H), 3.98 (m, 1H), 7.08 (d, J=8.3 Hz, 2H), 7.42 (d, J=8.3 Hz, 2H).

(22) .sup.13C NMR (CDCl.sub.3, 125 MHz): 137.5 (s), 131.6 (d, 2C), 131.1 (d, 2C), 120.3 (s), 68.7 (d), 45.0 (t), 22.9 (q).

Step 2: 3-(4-(2-hydroxypropyl)phenyl)propanal

(23) A solution of 1-(4-bromophenyl)propan-2-ol (3.0 g, 13.9 mmol, 1 equiv.) and N-cyclohexyl-N-methylaminecyclohexanamine (3.5 mL, 15.3 mmol, 1.1 equiv.) in DMF (28 mL) was degassed and stirred under an argon atmosphere for 20 min. Allyl alcohol (1.04 mL, 15.3 mmol, 1.1 equiv.) and bis(dibenzylideneacetone)palladium(0) (80 mg, 0.14 mmol, 0.01 equiv.) were added, followed by 2-(tert-butylphosphino)-1-phenyl-1H-indole (141 mg, 0.42 mmol, 0.03 equiv.) and the reaction was heated to 100° C. for 1 h. After cooling down to r.t., it was diluted with ether and washed three times with water. The organic layer was dried over sodium sulfate and the solvent was evaporated. The residue (GC ratio of linear/branched products: 5.6:1) was purified by flash column chromatography on silica gel (Heptane/AcOEt 65:35) and bulb-to-bulb distillation (0.35 mbar, 140-145° C.) to afford the desired aldehyde as an oil (1.39 g, 52% yield).

(24) .sup.1H NMR: 1.23 (d, J=6.2 Hz, 3H), 2.66 (A of ABX, J=13.5, 7.9 Hz, 1H), 2.74 (B of ABX, J=13.5, 4.9 Hz, 1H), 2.77 (dt, J=7.6, 1.2 Hz, 2H), 2.93 (t, J=7.5 Hz, 2H), 3.99 (m, 1H), 7.14 (s, 4H), 9.81 (t, J=1.2 Hz, 1H).

(25) .sup.13C NMR: 201.6 (d), 138.4 (s), 136.5 (s), 129.6 (d, 2C), 128.5 (d, 2C), 68.8 (d), 45.3 (t), 45.2 (t), 27.7 (t), 22.8 (q).

3-(4-(3-hydroxybutan-2-yl)phenyl)propanal

Step 1: 3-(4-bromophenyl)butan-2-ol

(26) To a solution of 1,4-dibromobenzene (15.0 g, 63.6 mmol, 1 equiv.) in THF (212 mL) at −78° C. was added n-BuLi (2.45 M, 26.0 mL, 63.6 mmol, 1 equiv.) dropwise. After stirring at −78° C. for 30 min, 2,3-dimethyloxirane (6.84 mL, 76 mmol, 1.2 equiv.) was added dropwise. After stirring at −78° C. for 30 min, boron trifluoride etherate (9.67 mL, 76 mmol, 1.2 equiv.) was added dropwise. After stirring at −78° C. for 2 h, the reaction was quenched with a 10% w/w solution of Na/K tartrates and the mixture was allowed to reach room temperature overnight. It was extracted three times with ether, the combined organic extracts were dried over sodium sulfate and the solvent was evaporated. The residue was purified by bulb-to-bulb distillation (125-130° C., 2-4 mbar) to afford 3-(4-bromophenyl)butan-2-ol as an oil (2.85 g, 20% yield).

Step 2: 3-(4-(3-hydroxybutan-2-yl)phenyl)propanal

(27) A solution of 3-(4-bromophenyl)butan-2-ol (2.79 g, 12.2 mmol, 1 equiv.) and N-cyclohexyl-N-methylaminecyclohexanamine (3.07 mL, 13.4 mmol, 1.1 equiv.) in DMF (24 mL) was degassed and stirred under an argon atmosphere for 20 min. Allyl alcohol (0.91 mL, 13.4 mmol, 1.1 equiv.) and bis(dibenzylideneacetone)palladium(0) (70 mg, 0.12 mmol, 0.01 equiv.) were added, followed by 2-(tert-butylphosphino)-1-phenyl-1H-indole (123 mg, 0.36 mmol, 0.03 equiv.) and the reaction was heated to 100° C. for 1 h. After cooling down to r.t., it was diluted with ether and washed three times with water. The organic layer was dried over sodium sulfate and the solvent was evaporated. The residue (GC ratio of linear/branched products: 5.3:1) was purified by flash column chromatography on silica gel (Heptane/AcOEt 65:35) and bulb-to-bulb distillation (0.35 mbar, 140-145° C.) to afford the desired aldehyde as an oil (691 mg, 27% yield).

(28) .sup.1H NMR: 1.08 (d, J=6.3 Hz, 3H), 1.30 (d, J=7.0 Hz, 3H), 2.71 (s, 1H), 2.77 (dt, J=7.5, 1.3 Hz, 2H), 2.94 (t, J=7.6 Hz, 2H), 3.86 (m, 1H), 7.13 (s, 4H), 9.82 (t, J=1.3 Hz, 1H).

(29) .sup.13C NMR: 201.7 (d), 142.2 (s), 138.3 (s), 128.3 (d, 2C), 128.1 (d, 2C), 72.3 (d), 46.7 (d), 45.2 (t), 27.7 (t), 21.0 (q), 16.0 (q).

3-(4-(1-hydroxy-2-methylpropan-2-yl)-2-methylphenyl)propanal

Step 1: methyl 2-(4-bromo-3-methylphenyl)acetate

(30) To a mixture of 2-(4-bromo-3-methylphenyl)acetic acid (10.0 g, 43.7 mmol, 1 equiv.) and potassium carbonate (9.05 g, 65.5 mmol, 1.5 equiv.) in acetone (87 mL) was added iodomethane (5.46 mL, 87 mmol, 2 equiv.) and the reaction was stirred at r.t. for 4 days. Acetone was evaporated, a saturated solution of ammonium chloride was added and it was extracted three times with ether. The combined organic extracts were dried over sodium sulfate and the solvent was evaporated. The residue was purified by bulb-to-bulb distillation (130-135° C., 2-4 mbar) to afford methyl 2-(4-bromo-3-methylphenyl)acetate as an oil (9.24 g, 87% yield).

Step 2: methyl 2-(4-bromo-3-methylphenyl)-2-methylpropanoate

(31) To a solution of methyl 2-(4-bromo-3-methylphenyl)acetate (9.19 g, 37.8 mmol, 1 equiv.) in THF (126 mL) at −78° C. was added a solution of sodium bis(trimethylsilyl)amide (1 M in THF, 95 mL, 95 mmol, 2.3 equiv.) dropwise. After stirring at −78° C. for 15 min, methyl iodide (7.09 mL, 113 mL, 3 equiv.) was added dropwise. After stirring at −78° C. for 1 h30, the reaction was quenched with a saturated solution of ammonium chloride. It was extracted three times with ether, the combined organic extracts were dried over sodium sulfate and the solvent was evaporated. The residue was purified by flash column chromatography on silica gel (Heptane/AcOEt 98:2) and bulb-to-bulb distillation (2-3 mbar, 140° C.) to afford the desired ester as an oil (9.10 g, 89% yield).

Step 3: 2-(4-bromo-3-methylphenyl)-2-methylpropan-1-ol

(32) To a suspension of lithium aluminum hydride (2.53 g, 66.8 mmol, 2 equiv.) in THF (60 mL) at 0° C. was added a solution of methyl 2-(4-bromo-3-methylphenyl)-2-methylpropanoate (9.05 g, 33.4 mmol, 1 equiv.) in THF (51 mL) dropwise. After stirring for 2 h at r.t., the reaction was cooled down to 0° C. and quenched successively with 2.5 mL of water, 7.5 mL of a 5% NaOH solution and 2.5 mL of water. It was filtered on a Celite pad using ether as an eluent and the solvent was evaporated. The crude product was used as such for the next step.

Step 4: 3-(4-(1-hydroxy-2-methylpropan-2-yl)-2-methylphenyl)propanal

(33) A solution of 2-(4-bromo-3-methylphenyl)-2-methylpropan-1-ol (7.49 g, 27.1 mmol, 1 equiv.) and N-cyclohexyl-N-methylaminecyclohexanamine (6.83 mL, 29.8 mmol, 1.1 equiv.) in DMF (54 mL) was degassed and stirred under an argon atmosphere for 20 min. Allyl alcohol (2.03 mL, 29.8 mmol, 1.1 equiv.) and bis(dibenzylideneacetone)palladium(0) (156 mg, 0.27 mmol, 0.01 equiv.) were added, followed by 2-(tert-butylphosphino)-1-phenyl-1H-indole (274 mg, 0.81 mmol, 0.03 equiv.) and the reaction was heated to 100° C. for 1 h. After cooling down to r.t., it was diluted with ether and washed three times with water. The organic layer was dried over sodium sulfate and the solvent was evaporated. The residue (GC ratio of linear/branched products: 25:1) was purified by flash column chromatography on silica gel (Heptane/AcOEt 65:35) and bulb-to-bulb distillation (0.15 mbar, 140-145° C.) to afford the desired aldehyde as an oil (3.56 mg, 60% yield).

(34) .sup.1H NMR: 1.31 (s, 6H), 2.32 (s, 3H), 2.73 (dt, J=7.7, 1.2 Hz, 2H), 2.91 (d, J=7.7 Hz, 2H), 3.58 (s, 2H), 7.09 (m, 1H), 7.15 (m, 2H), 9.84 (t, J=1.2 Hz, 1H).

(35) .sup.13C NMR: 201.7 (d), 144.5 (s), 136.2 (s), 135.8 (s), 128.6 (d), 128.3 (d), 124.1 (d), 73.0 (t), 43.9 (t), 39.7 (s), 25.4 (q, 2C), 24.9 (t), 19.6 (q).

Example 2

(36) Preparation of a Perfuming Composition

(37) A woman's perfume, was prepared by admixing the following ingredients:

(38) TABLE-US-00001 Part by Ingredients weight Benzyl acetate 60 Ethyl 3-oxobutanoate and (2Z)-ethyl 3-hydroxy-2-butenoate 20 Allyl (3-methylbutoxy)acetate and 20 (+−)-allyl (2-Methylbutoxy)acetate (−)-(3aR,5aS,9aS,9bR)-3a,6,6,9a- 20 tetramethyldodecahydronaphtho[2,1-b]furan 10%* (+−)-ethyl 2-methylpentanoate 20 7-methyl-2H-1,5-benzodioxepin-3(4H)-one 20 Cassis base 120 3-methyl-2-[(2Z)-2-penten-1-yl]-2-cyclopenten-1-one 40 (+−)-3,7-dimethyl-6-octen-1-ol 100 Allyl (cyclohexyloxy)acetate 10 10%* (2e)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2- 60 buten-1-one (+−)-4-decanolide 20 10%* (+−)-(e)-8-decen-5-olide and (+−)-(Z)-8-decen-5-olide 20 (+−)-2,6-dimethyl-7-octen-2-ol 80 Dipropylene glycol 800 10%* 1-methoxy-4-(2-propen-1-yl)benzene 40 (Z)-3,7-dimethyl-1,6-nonadien-3-ol and (E)-3,7-dimethyl-1,6- 400 nonadien-3-ol (+−)-3-(3-isopropyl-1-phenyl)butanal 20 (+−)-4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-Hexahydrocyclo- 1000 penta[g]isochromene (E)-3,7-dimethyl-2,6-octadien-1-ol 300 10%* methyl 2-octynoate 20 Methyl 2-((1RS,2RS)-3-oxo-2-pentylcyclopentyl)acetate 1000 Methyl dihydrojasmonate with high amount of isomer cis 1000 (+−)-3-(1,3-benzodioxol-5-yl)-2-methylpropanal 600 (+−)-7-hydroxy-3,7-dimethyloctanal 200 10%* indole 40 10%* 2-methoxy-4-[(1e)-1-propen-1-yl]phenol 20 (+−)-2-methyl-3-[4-(2-methyl-2-propanyl)phenyl]propanal 1000 (+−)-3,7-dimethyl-1,6-octadien-3-ol 200 (+−)-2,6-dimethyl-5-heptenal 20 (+−)-(E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)- 400 3-buten-2-one (+−)-3-methylcyclopentadecanone 400 10%* (2RS,4SR)-4-methyl-2-(2-methyl-1-propen-1-yl)tetra- 10 hydro-2H-Pyran and (2RS,4RS)-4-methyl-2-(2-methyl-1-propen- 1-yl)tetrahydro-2H-pyran 2-phenylethanol 100 10%* (Z)-3-hexen-1-ol 80 Orange oil 10 (3Z)-3-hexen-1-yl salicylate 200 (+−)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1- 60 yl)-2-pentanol (+−)-1-(3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydro-2- 600 naphthalenyl)ethanone (+−)-(E)-4-methyl-3-decen-5-ol 800 (1RS,2RS)-2-(2-methyl-2-propanyl)cyclohexyl acetate and 60 (1RS,2SR)-2-(2-methyl-2-propanyl)cyclohexyl acetate 2,4-dimethyl-3-cyclohexene-1-carbaldehyde 10 10000 *in dipropyleneglycol

(39) The addition of 800 parts by weight of 3-(4-(1-hydroxy-2-methylpropan-2-yl)phenyl)propanal obtained in example 1 to replace 800 parts by weight of dipropylene glycol to the above-described composition imparted to the latter a floral muguet note in the direction of Lyral® while conferring in addition a creamier and powdery aspect. When instead of the invention's compound, the same amount of 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal was used to replace 800 parts by weight of dipropylene glycol, the composition acquired a remarkable radiance, and volume associated with a floral, wetty twist very close to the one obtained when instead of 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal was added Lyral®.

(40) Lyral® and 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal blend well with the ozone, watery and salicylate notes of the perfuming composition wherease 3-(4-(1-hydroxy-2-methylpropan-2-yl)phenyl)propanal blends particularly well with the salicylate and musky notes.

Example 3

(41) Preparation of a Perfuming Composition

(42) A men's perfume was prepared by admixing the following ingredients:

(43) TABLE-US-00002 Part by Ingredients weight 1,1-dimethyl-2-phenylethyl acetate 160 (+−)-1,5-dimethyl-1-vinyl-4-hexenyl acetate 160 (+−)-1-phenylethyl acetate 20 1%* hexyl acetate 40 (2E)-2-benzylideneoctanal 160 (−)-(3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydro- 80 naphtho[2,1-b]furan 1%* methyl 2-aminobenzoate 40 10%* (Z)-3,7-dimethyl-2,6-octadienal and (E)-3,7-dimethyl-2,6- 40 octadienal (+−)-3,7-dimethyl-6-octen-1-ol 40 2-chromenone 40 Allyl (cyclohexyloxy)acetate 20 10%* (+−)-(2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)- 80 2-buten-1-one (+−)-2,6-dimethyl-7-octen-2-ol 400 Dipropylene glycol 800 3-(4-ethylphenyl)-2,2-dimethylpropanal and 3-(2-ethylphenyl)- 40 2,2-dimethylpropanal (+−)-4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclo- 4600 penta[g]isochromene (E)-3,7-dimethyl-2,6-octadien-1-ol 40 Geranium rose oil 40 methyl 2-((1RS,2RS)-3-oxo-2-pentylcyclopentyl)acetate 400 (+−)-3-(1,3-benzodioxol-5-yl)-2-methylpropanal 300 1-(octahydro-2,3,8,8-tetramethyl-2-naphtalenyl)-1-ethanone 600 Lavandin oil 40 (+−)-2-methyl-3-[4-(2-methyl-2-propanyl)phenyl]propanal 800 Methyl 2,4-dihydroxy-3,6-dimethylbenzoate 80 10%* (2E,6Z)-2,6-nonadienal 40 2-Methylbutyl salicylate and pentyl salicylate 40 (3Z)-3-hexen-1-yl salicylate 40 (+−)-3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)- 400 2-pentanol (+−)-1-(3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydro-2- 400 naphthalenyl)ethanone 10%* (2E)-2-hexenal 20 10%* 2,4-Dimethyl-3-cyclohexene-1-carbaldehyde 40 10000 *in dipropyleneglycol

(44) The addition of 800 parts by weight of 3-(4-(1-hydroxy-2-methylpropan-2-yl)phenyl)propanal obtained in example 1 to replace 800 parts by weight of dipropylene glycol to the above-described composition imparted to the latter a floral muguet note in the direction of Lyral® while conferring in addition a creamier and powdery aspect.

(45) When instead of the invention's compound, the same amount of 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal was used to replace 800 parts by weight of dipropylene glycol, the composition acquired a remarkable radiance, and volume associated with a floral, wetty twist very close to the one obtained when instead of 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal was added Lyral®.

(46) Lyral® and 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal blend well with the ozone, watery, salicylate and oak moss notes of the perfuming composition wherease 3-(4-(1-hydroxy-2-methylpropan-2-yl)phenyl)propanal blends particularly well with the salicylate and musky notes.

Example 4

(47) Preparation of a Perfume Comprising the Invention's Composition

(48) The perfume was prepared by adding 5 to 15% by weight, relative to the total weight of the perfume, of the invention's composition of example 2 or 3 into ethanol under gentle shaking.