PRECURSORS OF PHENOLIC FRAGRANT COMPOUNDS

Abstract

There is provided a compound of formula (I)

##STR00001##

which is a homoallylic ether of a phenolic fragrant compound HX and which is able to release said phenolic fragrant compound HX and optionally a further fragrant.

Claims

1. A method of generating a phenolic fragment compound HX which is a compound of formula (II) ##STR00014## the method comprising exposing a compound of formula (I) to ambient air in the presence or absence of light ##STR00015## wherein R.sub.1-R.sub.7 is independently selected from the group consisting of H, Me, linear C2-C20 hydrocarbon groups and branched C2-C20 hydrocarbon groups, wherein the linear and branched C2-C20 hydrocarbon groups independently bear up to 4 heteroatoms selected from the group consisting of O, S, and N, and bearing up to three double bonds or two triple bonds and bear up to three rings, phenyl, benzyl, substituted aryl or hetero-aryl units, 1- or 2-naphthyl, or R.sub.6 and R.sub.7 form together a double bond to a carbon atom, which is bearing one or two C1-C10 alkyl or C2-C10 alkenyl substituents, while the other substituents have the same meaning as previously defined; or R.sub.1 and R.sub.6, R.sub.1 and R.sub.3, R.sub.1 and R.sub.5, R.sub.3 and R.sub.5, R.sub.3 and R.sub.6, R.sub.5 and R.sub.7, R.sub.6 and R.sub.7, R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, form together with the carbon atoms of the chain they are attached to a 5 or 6 membered ring bearing up to 2 heteroatoms selected from the group consisting of O, S and N, that is optionally substituted with an alkyl chain, while the other substituents have the same meaning as previously defined; and the sum of all carbon atoms of R.sub.1-R.sub.7 is at least 5; or R.sub.7 is CR.sub.3R.sub.4CR.sub.1R.sub.2X, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and X are selected from the corresponding groups of R.sub.1, R.sub.2, R.sub.3, R.sub.4, and X, while the other substituents have the same meaning as previously defined, and the sum of all carbon atoms of R.sub.1-R.sub.6 and R.sub.1-R.sub.4 is at least 5 or more; and wherein X is representing the following fragment ##STR00016## wherein R.sub.11-R.sub.15 is independently selected from the group consisting of H, linear or branched C1-C5 alkyl, linear or branched C2-C5 alkenyl, linear or branched C2-C5 alkynyl, OH, C1-C4-alkoxy, CHO, C(O)Me, C(O)Et, hexanoyl, heptanoyl, octanoyl, propanoyl, 3-phenylpropanoyl, 5-methylhexanoyl, (CH.sub.2).sub.2C(O)CH.sub.3, (4-methyl-3,6-dihydro-2H-pyran-2-yl), CH.sub.2O-Me, CH.sub.2O-Et, CH.sub.2O-iPr, CH.sub.2OH, Cl, Br, phenyl, and CH(OR.sub.16)(OR.sub.17) wherein R.sub.16 and R.sub.17 are independently selected from the group consisting of C1-C5 alkyl, R.sub.16 and R.sub.17 form together with the carbon atoms of the chain they are attached to a 5 or 6 membered ring, CNOR.sub.18 wherein R.sub.18 is C1-C5 alkyl, and CO.sub.2R.sub.19 wherein R.sub.19 is selected from the group consisting of linear or branched C1-C8 alkyl, linear or branched C2-C8 alkenyl, linear or branched C2-C8 alkynyl, cycloalkyl and aryl; or R.sub.11 and R.sub.12 or R.sub.12 and R.sub.13 may form together with the carbon atoms they are attached to C1-C5 alkyl substituted or unsubstituted, saturated or unsaturated 5 and 6 membered rings containing C, O and/or N atoms.

2. The method according to claim 1, wherein R.sub.1-R.sub.7 is independently selected from the group consisting of H, Me, C2-C20 branched or linear alkyl or alkenyl or alkynyl, cycloalkyl, cycloalkenyl, phenyl, benzyl, phenylethyl or substituted phenylethyl, substituted aryl or hetero-aryl units, 1- or 2-naphthyl, alkoxycarbonylates (O(CO)R), alkylcarboxylates ((CO)OR), ethers, aldehydes, ketones, and alcohols; or R.sub.6 and R.sub.7 form together a double bond to a carbon atom, which is bearing one or two C1-C10 alkyl or C2-C10 alkenyl substituents, while the other substituents have the same meaning as previously defined; or R.sub.1 and R.sub.6, R.sub.1 and R.sub.3, R.sub.1 and R.sub.5, R.sub.3 and R.sub.5, R.sub.3 and R.sub.6, R.sub.5 and R.sub.7, R.sub.6 and R.sub.7, R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, form together with the carbon atoms of the chain they are attached to a 5 or 6 membered ring bearing up to 2 heteroatoms selected from the group consisting of O, S and N, that is optionally substituted with an alkyl chain, while the other substituents have the same meaning as previously defined; and the sum of all carbon atoms of R.sub.1-R.sub.7 is at least 5; or R.sub.7 is CR.sub.3R.sub.4CR.sub.1R.sub.2X, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and X are selected from the corresponding groups of R.sub.1, R.sub.2, R.sub.3, R.sub.4, and X, while the other substituents have the same meaning as previously defined, and the sum of all carbon atoms of R.sub.1-R.sub.6 and R.sub.1-R.sub.4 is at least 5; and wherein X is representing the following fragment ##STR00017## wherein R.sub.11 is selected from the group consisting of H, C1-C5 alkyl, OH, OMe, OEt, O-n-Pr, O-iso-Pr, hexanoyl, heptanoyl, octanoyl, propanoyl, 3-phenylpropanoyl, 5-methylhexanoyl, Cl, Br, phenyl, and CO.sub.2R.sub.19, wherein R.sub.19 is selected from the group consisting of H, Me, Et, 2-methylpropyl, hexan-2-yl, 2-isopropoxyethyl, 3-methylbut-2-en-1-yl, n-pentyl, hexyl, benzyl, cyclohexyl, cis-3-hexenyl, 2-ethylhexyl, 3-methylhex-2-en-1-yl, 2-hept-4-enyl, 1-(3-methyl-2-hexenyl), (CH.sub.2).sub.2-phenyl, para-tolyl; R.sub.12 is selected from the group consisting of H, OH, C1-C5 alkyl, C2-C5 alkenyl, and C1-C5 alkoxy; R.sub.13 is selected from the group consisting of H, branched or linear C1-C5 alkyl, branched or linear C2-C5 alkenyl, CHO, CO.sub.2H, CO.sub.2Me, CO.sub.2Et, C(O)Me, C(O)Et, (CH.sub.2).sub.2C(O)CH.sub.3; (4-methyl-3,6-dihydro-2H-pyran-2-yl), CH.sub.2O-Me, CH.sub.2O-Et, CH.sub.2O-iPr, CH.sub.2OH, Cl, propanoyl, and CO.sub.2R.sub.19, wherein R.sub.19 is selected from the group consisting of H, Me, Et, 2-methylpropyl, hexan-2-yl, 2-isopropoxyethyl, 3-methylbut-2-en-1-yl, n-pentyl, hexyl, benzyl, cyclohexyl, cis-3-hexenyl, 2-ethylhexyl, 3-methylhex-2-en-1-yl, 2-hept-4-enyl, 1-(3-methyl-2-hexenyl), (CH.sub.2).sub.2-phenyl, and para-tolyl; R.sub.14 is selected from the group consisting of H, OH, C1-C5 alkyl, C2-C5 alkenyl, and C1-C5 alkoxy; R.sub.15 is selected from the group consisting of H, C1-C5 alkyl, and Br; or R.sub.11 and R.sub.12 or R.sub.12 and R.sub.13 may form together with the carbon atoms they are attached to C1-C5 alkyl substituted or unsubstituted, saturated or unsaturated 5 and 6 membered rings containing C, O and/or N atoms, as precursor for generating a phenolic fragrant compound HX which is a compound of formula (II) ##STR00018##

3. A compound of formula (I) ##STR00019## wherein R.sub.1-R.sub.7 is independently selected from the group consisting of H, Me, linear C2-C20 hydrocarbon groups and branched C2-C20 hydrocarbon groups, wherein the linear and branched C2-C20 hydrocarbon groups independently bear up to 4 heteroatoms selected from the group consisting of O, S, and N, and bearing up to three double bonds or two triple bonds and bear up to three rings, phenyl, benzyl, substituted aryl or hetero-aryl units, 1- or 2-naphthyl, or R.sub.6 and R.sub.7 form together a double bond to a carbon atom, which is bearing one or two C1-C10 alkyl or C2-C10 alkenyl substituents, while the other substituents have the same meaning as previously defined; or R.sub.1 and R.sub.6, R.sub.1 and R.sub.3, R.sub.1 and R.sub.5, R.sub.3 and R.sub.5, R.sub.3 and R.sub.6, R.sub.5 and R.sub.7, R.sub.6 and R.sub.7, R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, form together with the carbon atoms of the chain they are attached to a 5 or 6 membered ring bearing up to 2 heteroatoms selected from the group consisting of O, S and N, that is optionally substituted with an alkyl chain, while the other substituents have the same meaning as previously defined; and the sum of all carbon atoms of R.sub.1-R.sub.7 is at least 5 or more; or R.sub.7 is CR.sub.3R.sub.4CR.sub.1R.sub.2X, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and X are selected from the corresponding groups of R.sub.1, R.sub.2, R.sub.3, R.sub.4, and X, while the other substituents have the same meaning as previously defined, and the sum of all carbon atoms of R.sub.1-R.sub.6 and R.sub.1-R.sub.4 is at least 5 or more; and wherein X is representing the following fragment ##STR00020## wherein R.sub.11-R.sub.15 is independently selected from the group consisting of H, linear or branched C1-C5 alkyl, linear or branched C2-C5 alkenyl, linear or branched C2-C5 alkynyl, OH, C1-C4-alkoxy, CHO, C(O)Me, C(O)Et, hexanoyl, heptanoyl, octanoyl, propanoyl, 3-phenylpropanoyl, 5-methylhexanoyl, (CH.sub.2).sub.2C(O)CH.sub.3, (4-methyl-3,6-dihydro-2H-pyran-2-yl), CH.sub.2O-Me, CH.sub.2O-Et, CH.sub.2O-iPr, CH.sub.2OH, Cl, Br, phenyl, CH(OR.sub.16)(OR.sub.17) wherein R.sub.16 and R.sub.17 are independently selected from the group consisting of C1-C5 alkyl or R.sub.16 and R.sub.17 form together with the carbon atoms of the chain they are attached to a 5 or 6 membered ring, CNOR.sub.13 wherein R.sub.18 is C1-C5 alkyl, CO.sub.2R.sub.19 wherein R.sub.19 is selected from the group consisting of linear or branched C1-C8 alkyl, linear or branched C2-C8 alkenyl, linear or branched C2-C8 alkynyl, cycloalkyl and aryl; or R.sub.11 and R.sub.12 or R.sub.12 and R.sub.13 may form together with the carbon atoms they are attached to C1-C5 alkyl substituted or unsubstituted, saturated or unsaturated 5 and 6 membered rings containing C, O and/or N atoms.

4. The compound according to claim 3 wherein R.sub.1-R.sub.7 is independently selected from the group consisting of H, Me, C2-C20 branched or linear alkyl or alkenyl or alkynyl, cycloalkyl, cycloalkenyl, phenyl, benzyl, phenylethyl or substituted phenylethyl, substituted aryl or hetero-aryl units, 1- or 2-naphthyl, alkoxycarbonylates (RO(CO)R), alkylcarboxylates (R(CO)OR), ethers, aldehydes, ketones, and alcohols; or R.sub.6 and R.sub.7 form together a double bond to a carbon atom, which is bearing one or two C1-C10 alkyl or C2-C10 alkenyl substituents, while the other substituents have the same meaning as previously defined; or R.sub.1 and R.sub.6, R.sub.1 and R.sub.3, R.sub.1 and R.sub.5, R.sub.3 and R.sub.5, R.sub.3 and R.sub.6, R.sub.5 and R.sub.7, R.sub.6 and R.sub.7, R.sub.1 and R.sub.2, or R.sub.3 and R.sub.4, form together with the carbon atoms of the chain they are attached to a 5 or 6 membered ring bearing up to 2 heteroatoms selected from the group consisting of O, S and N, that is optionally substituted with an alkyl chain, while the other substituents have the same meaning as previously defined; and the sum of all carbon atoms of R.sub.1-R.sub.7 is at least 5; or R.sub.7 is CR.sub.3R.sub.4CR.sub.1R.sub.2X, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and X are selected from the corresponding groups of R.sub.1, R.sub.2, R.sub.3, R.sub.4, and X, while the other substituents have the same meaning as previously defined, and the sum of all carbon atoms of R.sub.1-R.sub.6 and R.sub.1-R.sub.4 is at least 5; and wherein X is representing the following fragment ##STR00021## wherein R.sub.11 is selected from the group consisting of H, C1-C5 alkyl, OH, OMe, OEt, O-n-Pr, O-iso-Pr, hexanoyl, heptanoyl, octanoyl, propanoyl, 3-phenylpropanoyl, 5-methylhexanoyl, Cl, Br, phenyl, and CO.sub.2R.sub.19, wherein R.sub.19 is selected from the group consisting of H, Me, Et, 2-methylpropyl, hexan-2-yl, 2-isopropoxyethyl, 3-methylbut-2-en-1-yl, n-pentyl, hexyl, benzyl, cyclohexyl, cis-3-hexenyl, 2-ethylhexyl, 3-methylhex-2-en-1-yl, 2-hept-4-enyl, 1-(3-methyl-2-hexenyl), (CH.sub.2).sub.2-phenyl, and para-tolyl; R.sub.12 is selected from the group consisting of H, OH, C1-C5 alkyl, C2-C5 alkenyl, and C1-C5 alkoxy; R.sub.13 is selected from the group consisting of H, branched or linear C1-C5 alkyl, branched or linear C2-C5 alkenyl, CHO, CO.sub.2H, CO.sub.2Me, CO.sub.2Et, C(O)Me, C(O)Et, (CH.sub.2).sub.2C(O)CH.sub.3; (4-methyl-3,6-dihydro-2H-pyran-2-yl), CH.sub.2O-Me, CH.sub.2O-Et, CH.sub.2O-iPr, CH.sub.2OH, Cl, propanoyl, and CO.sub.2R.sub.19, wherein R.sub.19 is selected from the group consisting of H, Me, Et, 2-methylpropyl, hexan-2-yl, 2-isopropoxyethyl, 3-methylbut-2-en-1-yl, n-pentyl, hexyl, benzyl, cyclohexyl, cis-3-hexenyl, 2-ethylhexyl, 3-methylhex-2-en-1-yl, 2-hept-4-enyl, 1-(3-methyl-2-hexenyl), (CH.sub.2).sub.2-phenyl, and para-tolyl; R.sub.14 is selected from the group consisting of H, OH, C1-C5 alkyl, C2-C5 alkenyl, and C1-C5 alkoxy; R.sub.15 is selected from the group consisting of H, C1-C5 alkyl, and Br; or R.sub.11 and R.sub.12 or R.sub.12 and R.sub.13 may form together with the carbon atoms they are attached to C1-C5 alkyl substituted or unsubstituted, saturated or unsaturated 5 and 6 membered rings containing C, O and/or N atoms.

5. A fragrance composition comprising at least one compound of formula (I) according to claim 3.

6. A consumer product comprising at least one compound of formula (I) according to claim 3 and a consumer product base.

7. A method to release a phenolic fragrant compound of formula (II), the method comprising exposing a compound of formula (I) as defined in claim 3 to ambient air in the presence or absence of light.

8. A method of making a compound of formula (I) according to claim 3, comprising the steps of: a) providing a phenolic fragrant compound HX, which is a compound of formula (II) ##STR00022## wherein R.sub.11 is selected from the group consisting of H, C1-C5 alkyl, OH, OMe, OEt, O-n-Pr, O-iso-Pr, hexanoyl, heptanoyl, octanoyl, propanoyl, 3-phenylpropanoyl, 5-methylhexanoyl, Cl, Br, phenyl, and CO.sub.2R.sub.19, wherein R.sub.19 is selected from the group consisting of H, Me, Et, 2-methylpropyl, hexan-2-yl, 2-isopropoxyethyl, 3-methylbut-2-en-1-yl, n-pentyl, hexyl, benzyl, cyclohexyl, cis-3-hexenyl, 2-ethylhexyl, 3-methylhex-2-en-1-yl, 2-hept-4-enyl, 1-(3-methyl-2-hexenyl), (CH.sub.2).sub.2-phenyl, and para-tolyl; R.sub.12 is selected from the group consisting of H, OH, C1-C5 alkyl, C2-C5 alkenyl, and C1-C5 alkoxy; R.sub.13 is selected from the group consisting of H, branched or linear C1-C5 alkyl, branched or linear C2-C5 alkenyl, CHO, CO.sub.2H, CO.sub.2Me, CO.sub.2Et, C(O)Me, C(O)Et, (CH.sub.2).sub.2C(O)CH.sub.3; (4-methyl-3,6-dihydro-2H-pyran-2-yl), CH.sub.2O-Me, CH.sub.2O-Et, CH.sub.2O-iPr, CH.sub.2OH, Cl, propanoyl, and CO.sub.2R.sub.19, wherein R.sub.19 is selected from the group consisting of H, Me, Et, 2-methylpropyl, hexan-2-yl, 2-isopropoxyethyl, 3-methylbut-2-en-1-yl, n-pentyl, hexyl, benzyl, cyclohexyl, cis-3-hexenyl, 2-ethylhexyl, 3-methylhex-2-en-1-yl, 2-hept-4-enyl, 1-(3-methyl-2-hexenyl), (CH.sub.2).sub.2-phenyl, and para-tolyl R.sub.14 is selected from the group consisting of H, OH, C1-C5 alkyl, C2-C5 alkenyl, and C1-C5 alkoxy; R.sub.15 is selected from the group consisting of H, C1-C5 alkyl, and Br; or R.sub.11 and R.sub.12 or R.sub.12 and R.sub.13 may form together with the carbon atoms they are attached to C1-C5 alkyl substituted or unsubstituted, saturated or unsaturated 5 and 6 membered rings containing C, O and/or N atoms; and b) reacting it with an unsaturated alkylhalide or an unsaturated alcohol.

9. A method to confer, enhance, improve or modify the hedonic properties of a fragrance composition or a consumer product, which method comprises adding to said composition or consumer product at least one compound of formula (I) as defined in claim 3.

Description

DESCRIPTION OF FIGURES

[0148] FIG. 1 shows the comparison of color stability of a precursor according to the invention and a free phenolic fragrant compound HX when used in a liquid detergent.

[0149] FIG. 2 shows the setup of a headspace vial used for analysis of volatiles.

EXAMPLES

General:

[0150] All reactions were performed under argon using solvents and reagents from commercial suppliers without further purification. Solvents for extraction and chromatography were technical grade and used without further purification. Flash chromatography was performed using commercially available prepacked silica gel cartridges. Unless otherwise noted, a mixture of Heptane:MTBE was used as eluent. NMR spectra were recorded with Bruker AW 400 MHz or Avance III HD 400 MHz instruments. The chemical shifts for .sup.1H NMR spectra was reported in (ppm) referenced to the residual proton signal of the deuterated solvent; coupling constants were expressed in Hertz (Hz). .sup.13C NMR spectra were referenced to the carbon signals of the deuterated solvent. The following abbreviations are used: s=singlet, d=doublet, t=triplet, q=quartet, quint.=quintuplet, m=multiplet, dd=double doublet, bs=broad singlet. GC/MS spectral data were obtained from an Agilent 6890 N and MSD 5975 using a column HP-5 MS, 30 m, 0.25 mm, 0.25 m.

Example 1: methyl (S,Z)-12-(2-ethoxy-4-formylphenoxy)octadec-9-enoate

[0151] To a solution of ethyl vanillin (10.0 g, 60.2 mmol, 1.0 equiv), methyl ricinoleate (22.6 g, 72.2 mmol, 1.2 equiv) and triphenylphosphine (20.5 g, 78.0 mmol) in THF (200 mL) was added DIAD (15.8 g, 78.0 mmol) slowly at r.t. The temperature was kept below 25 C. and the reaction mixture was stirred at r.t. for 16 hours under argon atmosphere. The reaction conversion was monitored by TLC and GC. The mixture was filtered, and the filtrate was condensed by rotary evaporation. The residue was purified by silica gel column chromatography (PE:MTBE=94:6) to give methyl (S,Z)-12-(2-ethoxy-4-formylphenoxy)octadec-9-enoate (33.9 mmol, 15.6 g, yield: 56%) as colorless liquid.

[0152] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.73 (s, 1H), 7.55-7.16 (m, 2H), 6.89 (d, J=8.3 Hz, 1H), 5.56-5.14 (m, 2H), 4.51-3.88 (m, 3H), 3.56 (s, 3H), 2.46-2.28 (m, 2H), 2.20 (t, J=7.5 Hz, 2H), 2.00-1.88 (m, 2H), 1.72-1.45 (m, 4H), 1.45-1.05 (m, 19H), 0.77 (t, J=6.3 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.8, 174.1, 154.1, 150.0, 132.6, 130.0, 126.2, 124.2, 114.3, 111.6, 79.5, 64.5, 51.3, 34.0, 33.7, 31.7, 31.6, 29.4, 29.2, 29.1, 29.1, 29.1, 27.4, 25.3, 24.9, 22.5, 14.7, 14.0 ppm. GC/MS (EI): m/z (%): 460 (1) [M.sup.+], 295 (10), 263 (18), 245 (9), 166 (100), 138 (37), 109 (14), 95 (17), 81 (26).

[0153] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanillin, green, fatty.

Example 2: methyl (S,Z)-12-(4-(3-oxobutyl)phenoxy)octadec-9-enoate

[0154] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (5.0 g, 30.4 mmol, 1.0 equiv) and methyl (Z)-12-hydroxyoctadec-9-enoate (11.4 g, 36.5 mmol, 1.2 equiv) according to the procedure of example 1 as colorless liquid (16.6 mmol, 7.6 g, 54% yield).

[0155] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.06 (d, J=7.9 Hz, 2H), 6.80 (d, J=7.9 Hz, 2H), 5.55-5.32 (m, 2H), 4.29-4.06 (m, 1H), 3.65 (s, 3H), 2.89-2.64 (m, 4H), 2.45-2.22 (m, 4H), 2.15-1.89 (m, 5H), 1.73-1.54 (m, 4H), 1.51-1.14 (m, 16H), 0.86 (s, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 208.0, 174.2, 156.8, 132.9, 132.3, 129.2, 124.7, 116.0, 77.8, 51.4, 45.4, 34.0, 33.8, 31.8, 31.5, 30.0, 29.5, 29.3, 29.2, 29.1, 28.9, 27.4, 25.4, 24.9, 22.6, 14.1 ppm. GC/MS (EI): m/z (%): 458 (3) [M.sup.+], 294 (7), 261 (19), 203 (19), 164 (100), 107 (63), 55 (30).

[0156] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery fruity raspberry, green, fatty

Example 3: methyl (S,Z)-2-hydroxy-4-((18-methoxy-18-oxooctadec-9-en-7-yl)oxy)-3,6-dimethylbenzoate

[0157] The compound was obtained from methyl 2,4-dihydroxy-3,6-dimethylbenzoate (5.0 g, 25.5 mmol, 1.0 equiv) and methyl (Z)-12-hydroxyoctadec-9-enoate (9.6 g, 30.6 mmol, 1.2 equiv) according to the procedure of example 1 as colorless liquid (16.7 mmol, 8.2 g, 66% yield).

[0158] .sup.1H NMR (400 MHz, CDCl.sub.3) 11.79 (s, 1H), 6.17 (s, 1H), 5.54-5.13 (m, 2H), 4.34-4.11 (m, 1H), 3.81 (s, 3H), 3.57 (s, 3H), 2.41 (s, 3H), 2.38-2.25 (m, 2H), 2.20 (t, J=7.5 Hz, 2H), 1.98 (s, 3H), 1.96-1.89 (m, 2H), 1.67-1.42 (m, 4H), 1.40-1.13 (m, 16H), 0.78 (t, J=6.7 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 173.2, 171.5, 161.5, 159.4, 138.7, 131.5, 123.3, 110.8, 106.8, 103.9, 76.5, 50.6, 50.4, 33.0, 32.7, 30.8, 30.7, 28.5, 28.3, 28.2, 28.1, 28.1, 26.4, 24.3, 23.9, 23.7, 21.6, 13.0, 7.0 ppm.

[0159] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery mossy, evernyl, green, fatty

Example 4: 3-ethoxy-4-((2-methylundec-2-en-5-yl)oxy)benzaldehyde

[0160] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (3.0 g, 18.1 mmol, 1.0 equiv) and 2-methylundec-2-en-5-ol (3.7 g, 19.9 mmol, 1.1 equiv) according to the procedure of example 1 as colorless liquid (7.2 mmol, 2.4 g, 41% yield).

[0161] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.83 (s, 1H), 7.49-7.33 (m, 2H), 7.04-6.85 (m, 1H), 5.18 (t, J=7.0 Hz, 1H), 4.45-4.25 (m, 1H), 4.13 (q, J=7.0 Hz, 2H), 2.57-2.21 (m, 2H), 1.81-1.59 (m, 8H), 1.50-1.20 (m, 11H), 0.93-0.76 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 191.0, 154.4, 150.1, 134.3, 129.9, 126.3, 119.4, 114.4, 111.8, 80.0, 64.6, 33.7, 32.6, 31.8, 29.3, 25.9, 25.4, 22.6, 18.0, 14.7, 14.1 ppm. GC/MS (EI): m/z (%): 332 (3) [M.sup.+], 263 (1), 167 (42), 137 (21), 111 (25), 69 (100), 55 (30).

[0162] Odour description (1% solution in EtOH on paper blotter, 24 h): vanilla (powdery, creamy) dry (dough)

Example 5: 4-(4-((5-methylocta-1,5-dien-4-yl)oxy)phenyl)butan-2-one

[0163] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (5.2 g, 31.4 mmol, 1.1 equiv) and 5-methylocta-1,5-dien-4-ol (4.0 g, 28.5 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (17.1 mmol, 4.9 g, 60% yield).

[0164] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers) 7.03 (d, J=8.0 Hz, 2H), 6.80 (d, J=8.0 Hz, 2H), 5.94-5.64 (m, 1H), 5.51-5.38 (m, 1H), 5.18-4.85 (m, 2H), 4.54-4.27 (m, 1H), 2.86-2.32 (m, 6H), 2.12 (s, 3H), 2.07-1.62 (m, 2H), 1.61-1.54 (m, 3H), 0.97-0.83 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers) 208.3, 156.9, 156.8, 136.5, 135.5, 134.8, 132.9, 132.9, 132.8, 130.4, 128.9, 128.9, 125.1, 116.7, 116.3, 116.2, 114.6, 85.1, 83.4, 45.5, 45.5, 38.8, 31.7, 30.1, 28.9, 27.1, 20.8, 13.9, 11.1, 11.1, 10.3 ppm. GC/MS (EI): m/z (%): 286 (1) [M.sup.+], 245 (2), 187 (11), 164 (21), 122 (67), 107 (71), 93 (75), 81 (100). Odour description (1% solution in EtOH on paper blotter, 24 h): fruity (powdery, sweet, raspberry)

Example 6: 2-methoxy-1-((5-methylocta-1,5-dien-4-yl)oxy)-4-(prop-1-en-1-yl)benzene

[0165] The compound was obtained from 2-methoxy-4-(prop-1-en-1-yl)phenol (5.2 g, 31.4 mmol, 1.1 equiv) and 5-methylocta-1,5-dien-4-ol (4.0 g, 28.5 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (13.6 mmol, 3.9 g, 47% yield).

[0166] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers) 6.86 (s, 1H), 6.83-6.70 (m, 2H), 6.31 (d, J=15.7 Hz, 1H), 6.15-6.00 (m, 1H), 5.93-5.64 (m, 1H), 5.49-5.31 (m, 1H), 5.18-4.85 (m, 2H), 4.53-4.32 (m, 1H), 3.85 (s, 3H), 2.81-2.38 (m, 2H), 2.05-1.66 (m, 5H), 1.59 (s, 3H), 0.98-0.83 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers) 150.4, 150.3, 147.0, 146.8, 136.5, 135.5, 134.9, 132.8, 131.6, 131.4, 130.9, 130.7, 125.4, 123.8, 123.7, 118.5, 116.9, 116.6, 114.6, 109.5, 109.4, 86.8, 85.1, 56.0, 56.0, 38.5, 31.7, 26.8, 20.8, 18.4, 13.9, 11.0, 10.4 ppm. GC/MS (EI): m/z (%): 286 (1) [M.sup.+], 245 (1), 166 (100), 149 (9), 81 (19), 55 (6).

[0167] Odour description (1% solution in EtOH on paper blotter, 24 h): woody (smokey, cedarwood, pyrogravure)

Example 7: methyl 2-hydroxy-3,6-dimethyl-4-((5-methylocta-1,5-dien-4-yl)oxy)benzoate

[0168] The compound was obtained from methyl 2,4-dihydroxy-3,6-dimethylbenzoate (6.2 g, 31.4 mmol, 1.1 equiv) and 5-methylocta-1,5-dien-4-ol (4.0 g, 28.5 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (9.7 mmol, 3.1 g, 34% yield).

[0169] .sup.1H NMR (400 MHz, CDCl.sub.3) 11.81 (s, 1H), 6.25 (s, 1H), 5.89-5.69 (m, 1H), 5.52-5.39 (m, 1H), 5.19-4.88 (m, 2H), 4.64-4.43 (m, 1H), 3.90 (s, 3H), 2.86-2.38 (m, 5H), 2.09 (s, 3H), 2.07-1.66 (m, 2H), 1.57 (s, 3H), 1.01-0.87 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 172.6, 162.2, 160.4, 160.2, 139.4, 139.4, 136.3, 135.2, 134.4, 132.6, 130.5, 125.1, 117.1, 114.7, 111.6, 111.5, 108.9, 108.8, 105.1, 105.0, 84.6, 83.0, 51.7, 38.8, 31.6, 27.1, 24.6, 20.8, 13.9, 11.1, 11.1, 10.2, 8.0 ppm. GC/MS (EI): m/z (%): 318 (4) [M.sup.+], 277 (4), 245 (8), 196 (31), 164 (76), 122 (43), 81 (100), 67 (28).

[0170] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery (evernyl)

Example 8: 4-(4-((1-phenylbut-3-en-1-yl)oxy)phenyl)butan-2-one

[0171] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (4.9 g, 29.7 mmol, 1.1 equiv) and 1-phenylbut-3-en-1-ol (4.0 g, 27.0 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (6.8 mmol, 2.0 g, 25% yield).

[0172] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.38-7.23 (m, 5H), 6.98 (d, J=8.3 Hz, 2H), 6.75 (d, J=8.3 Hz, 2H), 5.98-5.67 (m, 1H), 5.18-4.96 (m, 3H), 2.82-2.50 (m, 6H), 2.09 (s, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 208.2, 156.5, 141.5, 134.2, 133.1, 129.1, 128.5, 127.6, 126.1, 117.5, 116.0, 80.0, 45.4, 42.9, 30.1, 28.9 ppm. GC/MS (EI): m/z (%): 294 (3) [M.sup.+], 253 (6), 164 (58), 131 (100), 107 (73), 91 (73), 77 (51), 65 (20).

[0173] Odour description (1% solution in EtOH on paper blotter, 24 h): fruity (powdery, sweet, raspberry)

Example 9: 4-(4-((octadeca-9,11-dien-7-yl)oxy)phenyl)butan-2-one

[0174] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (1.3 g, 7.9 mmol, 1.5 equiv) and octadec-9-ene-7,12-diol (1.5 g, 5.3 mmol, 1.0 equiv) according to the procedure of example 1 as white solid (0.5 mmol, 0.2 g, 7% yield, by product, the main product is example 10).

[0175] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.00 (d, J=8.3 Hz, 2H), 6.74 (d, J=8.3 Hz, 2H), 6.36-5.16 (m, 4H), 4.21-3.83 (m, 1H), 2.82-2.70 (m, 2H), 2.68-2.57 (m, 2H), 2.51-2.24 (m, 2H), 2.10-2.01 (m, 4H), 1.62-1.52 (m, 2H), 1.38-1.10 (m, 17H), 0.85-0.74 (m, 6H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 207.2, 155.8, 134.8, 132.0, 130.0, 128.2, 128.1, 127.3, 115.2, 115.1, 76.8, 44.4, 36.2, 32.8, 30.8, 30.7, 29.1, 28.6, 28.3, 27.9, 27.9, 26.7, 24.4, 21.6, 21.6, 13.1, 13.0 ppm. GC/MS (EI): m/z (%): 412 (8) [M.sup.+], 261 (42), 203 (58), 179 (1), 164 (22), 107 (85), 91 (24), 81 (50), 67 (100), 55 (84).

[0176] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery fruity raspberry

Example 10: 4,4-((octadec-9-ene-7,12-diylbis(oxy))bis(4,1-phenylene))bis(butan-2-one)

[0177] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (1.3 g, 7.9 mmol, 1.5 equiv) and octadec-9-ene-7,12-diol (1.5 g, 5.3 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (1.9 mmol, 1.1 g, 35% yield).

[0178] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.05 (d, J=8.5 Hz, 4H), 6.78 (d, J=8.5 Hz, 4H), 5.64-5.43 (m, 2H), 4.24-4.02 (m, 2H), 2.87-2.77 (m, 4H), 2.75-2.64 (m, 4H), 2.43-2.23 (m, 4H), 2.11 (s, 6H), 1.69-1.53 (m, 4H), 1.37-1.21 (m, 16H), 0.90-0.82 (m, 6H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 208.0, 156.8, 132.9, 129.2, 128.6, 116.1, 77.7, 45.4, 37.0, 33.7, 31.8, 30.1, 29.4, 28.9, 25.4, 22.6, 14.1 ppm. GC/MS (EI): m/z (%): 576 (1) [M.sup.+], 412 (14), 355 (21), 261 (21), 203 (50), 164 (27), 107 (100), 97 (30), 55 (86).

[0179] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery fruity raspberry

Example 11: 3-ethoxy-4-((5-methylocta-1,5-dien-4-yl)oxy)benzaldehyde

[0180] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (5.0 g, 30.1 mmol, 1.0 equiv) and (E)-5-methylocta-1,5-dien-4-ol (7.9 g, 39.1 mmol, 1.2 equiv) according to the procedure of example 1 as colorless liquid (18.0 mmol, 5.2 g, 60% yield).

[0181] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers) 9.81 (s, 1H), 7.41-7.31 (m, 2H), 6.96 (d, J=8.2 Hz, 1H), 5.95-5.69 (m, 1H), 5.52-5.37 (m, 1H), 5.20-4.86 (m, 2H), 4.67-4.46 (m, 1H), 4.22-4.03 (m, 2H), 2.88-2.37 (m, 2H), 2.09-1.72 (m, 2H), 1.61 (s, 3H), 1.45 (t, J=7.0 Hz, 3H), 1.02-0.87 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers) 191.0, 154.1, 153.9, 150.0, 150.0, 136.2, 134.7, 134.3, 132.2, 131.3, 130.2, 130.1, 126.1, 126.1, 125.9, 117.2, 115.5, 115.2, 114.8, 111.7, 111.6, 86.6, 85.0, 64.7, 64.6, 38.5, 31.7, 26.8, 20.8, 14.8, 13.9, 11.1, 11.0, 10.2 ppm. GC/MS (EI): m/z (%): 288 (1) [M.sup.+], 247 (2), 189 (3), 166 (6), 137 (15), 122 (35), 93 (31), 81 (100).

[0182] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery (vanilla)

Example 12: (Z)-4-(deca-1,7-dien-4-yloxy)-3-ethoxybenzaldehyde

[0183] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (10.0 g, 60.2 mmol, 1.0 equiv) and (Z)-deca-1,7-dien-4-ol (10.2 g, 66.12 mmol, 1.1 equiv) according to the procedure of example 1 as colorless liquid (29.4 mmol, 8.9 g, 48% yield).

[0184] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.74 (s, 1H), 7.31 (s, 2H), 6.89 (d, J=8.6 Hz, 1H), 5.98-5.60 (m, 1H), 5.39-5.17 (m, 2H), 5.13-4.93 (m, 2H), 4.39-4.20 (m, 1H), 4.04 (q, J=6.8 Hz, 2H), 2.52-2.27 (m, 2H), 2.19-2.04 (m, 2H), 1.99-1.81 (m, 2H), 1.80-1.57 (m, 2H), 1.36 (t, J=6.9 Hz, 3H), 0.80 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 189.8, 153.0, 149.1, 132.7, 131.6, 129.2, 126.9, 125.2, 116.8, 113.5, 110.6, 77.5, 63.5, 37.2, 32.6, 21.8, 19.4, 13.7, 13.2 ppm. GC/MS (EI): m/z (%): 302 (12) [M.sup.+], 193 (1), 166 (100), 138 (51), 95 (23), 81 (20), 67 (19), 55 (13).

[0185] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery (vanilla)

Example 13: 2-methoxy-1-(((Z)-nona-1,6-dien-4-yl)oxy)-4-(prop-1-en-1-yl)benzene

[0186] The compound was obtained from 2-methoxy-4-(prop-1-en-1-yl)phenol (0.6 g, 3.7 mmol, 1.3 equiv) and (Z)-nona-1,6-dien-4-ol (0.4 g, 2.9 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (1.0 mmol, 0.3 g, 37% yield).

[0187] .sup.1H NMR (400 MHz, CDCl.sub.3): =6.88 (s, 1H), 6.80-6.87 (m, 2H), 6.33 (br d, J=15.8 Hz, 1H), 6.07-6.16 (m, 1H), 5.84-5.97 (m, 1H), 5.38-5.53 (m, 2H), 5.03-5.15 (m, 2H), 4.24 (quin, J=5.8 Hz, 1H), 3.84 (s, 3H), 2.37-2.51 (m, 4H), 2.03-2.06 (m, 2H), 1.86 (d, J=6.5 Hz, 3H), 0.95 (t, J=7.4 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 150.7, 146.7, 134.6, 134.1, 132.0, 130.6, 124.0, 124.0, 118.6, 117.3, 117.0, 109.6, 79.4, 55.9, 38.1, 31.4, 20.8, 18.4, 14.2 ppm. GC/MS (EI): m/z (%): 286 (10) [M.sup.+], 217 (1), 164 (100), 149 (11), 131 (6), 103 (8), 91 (11), 81 (7).

[0188] Odour description (1% solution in EtOH on paper blotter, 24 h): creamy, vanilla

Example 14: 4-(4-(((1S,2S,5R)-5-methyl-2-(prop-1-en-2-yl)cyclohexyl)oxy)phenyl)butan-2-one

[0189] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (5.0 g, 30.4 mmol, 1.0 equiv) and (1R,2S,5R)-5-methyl-2-(prop-1-en-2-yl)cyclohexan-1-ol (5.6 g, 36.5 mmol, 1.2 equiv) according to the procedure of example 1 as white solid (9.6 mmol, 2.9 g, 32% yield). .sup.1H NMR (400 MHz, CDCl.sub.3) 7.05 (d, J=8.5 Hz, 2H), 6.79 (d, J=8.6 Hz, 2H), 4.78 (s, 2H), 4.55 (d, J=2.1 Hz, 1H), 2.86-2.78 (m, 2H), 2.76-2.66 (m, 2H), 2.16-2.04 (m, 5H), 2.03-1.89 (m, 1H), 1.86-1.60 (m, 6H), 1.13-0.93 (m, 2H), 0.84 (d, J=6.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 208.3, 156.6, 147.3, 132.7, 129.2, 116.1, 110.9, 75.1, 48.0, 45.5, 37.9, 34.8, 30.1, 28.9, 26.1, 25.0, 22.3, 22.0 ppm. GC/MS (EI): m/z (%): 300 (23) [M.sup.+], 164 (100), 136 (45), 121 (35), 107 (75), 95 (26), 81 (54).

[0190] Odour description (1% solution in EtOH on paper blotter, 24 h): sweet fruity (raspberry)

Example 15: 3-ethoxy-4-((1-phenylnon-1-en-4-yl)oxy)benzaldehyde

[0191] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (0.3 g, 1.9 mmol, 1.3 equiv) and 1-phenylnon-1-en-4-ol (0.4 g, 1.5 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (0.3 mmol, 0.12 g, 21% yield).

[0192] .sup.1H NMR (400 MHz, CDCl.sub.3): =9.83 (s, 1H), 7.39-7.43 (m, 2H), 7.19-7.35 (m, 5H), 7.01 (d, J=8.1 Hz, 1H), 6.47 (d, J=15.8 Hz, 1H), 6.18-6.34 (m, 1H), 4.42-4.46 (m, 1H), 4.13 (q, J=6.8 Hz, 2H), 2.55-2.70 (m, 2H), 1.25-1.86 (m, 11H), 0.88 (br t, J=6.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 191.0, 154.1, 150.2, 137.4, 132.8, 130.2, 128.5, 127.3, 126.3, 126.1, 125.6, 114.9, 111.7, 79.9, 64.6, 37.6, 33.8, 31.8, 25.1, 22.6, 14.8, 14.0 ppm. GC/MS (EI): m/z (%): 366 (1) [M.sup.+], 249 (11), 201 (33), 165 (28), 117 (100), 91 (61).

[0193] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery (vanilla)

Example 16: 4-((2,6-dimethylhepta-4,5-dien-2-yl)oxy)-3-ethoxybenzaldehyde

[0194] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (1.5 g, 9.0 mmol, 1.0 equiv) and 2,2,5-trimethylhexa-3,4-dien-1-ol (1.3 g, 9.0 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (0.1 mmol, 0.04 g, 1% yield).

[0195] .sup.1H NMR (400 MHz, CDCl.sub.3): =9.88 (s, 1H), 7.40 (d, J=1.6 Hz, 1H), 7.38 (dd, J=8.0, 1.9 Hz, 1H), 7.16 (d, J=8.0 Hz, 1H), 5.00-5.21 (m, 1H), 4.09 (q, J=6.9 Hz, 2H), 2.39 (d, J=7.6 Hz, 2H), 1.64-1.74 (m, 6H), 1.43-1.52 (m, 3H), 1.36 (s, 6H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) =203.7, 191.3, 153.9, 151.2, 132.4, 124.9, 124.5, 111.5, 94.2, 84.5, 83.6, 64.2, 42.7, 26.0, 20.5, 14.7 ppm. GC/MS (EI): m/z (%): 288 (6) [M.sup.+], 166 (33), 137 (40), 123 (26), 107 (100), 81 (91), 67 (30).

[0196] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery (vanilla)

Example 17: (Z)-3-ethoxy-4-(undec-3-en-6-yloxy)benzaldehyde

[0197] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (0.5 g, 3.1 mmol, 1.3 equiv) and (Z)-undec-3-en-6-ol (0.4 g, 2.3 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (0.9 mmol, 0.3 g, 39% yield).

[0198] .sup.1H NMR (400 MHz, CDCl.sub.3): =9.83 (s, 1H), 7.40 (s, 1H), 7.41 (d, J=6.3 Hz, 1H), 6.97 (d, J=8.6 Hz, 1H), 5.36-5.54 (m, 2H), 4.39-4.33 (m 1H), 4.13 (q, J=6.9 Hz, 2H), 2.38-2.54 (m, 2H), 2.10-2.02 (m, 2H), 1.67-1.81 (m, 2H), 1.42-1.52 (m, 4H), 1.26-1.34 (m, 5H), 0.86-1.00 (m, 6H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) =191.0, 154.2, 150.1, 134.4, 130.0, 126.3, 123.7, 114.4, 111.7, 79.7, 64.6, 33.7, 31.8, 31.6, 25.0, 22.6, 20.8, 14.7, 14.1, 14.0 ppm. GC/MS (EI): m/z (%): 318 (6) [M.sup.+], 249 (2), 166 (100), 138 (47), 97 (26), 83 (21), 69 (34), 55 (36).

[0199] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery (dry, vanilla, chocolate)

Example 18: 3-ethoxy-4-((2,6,10-trimethylundeca-4,5,9-trien-2-yl)oxy)benzaldehyde

[0200] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (7.3 g, 43.7 mmol, 1.3 equiv) and 2,2,5,9-tetramethyldeca-3,4,8-trien-1-ol (7.0 g, 33.6 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (3.1 mmol, 1.1 g, 9% yield).

[0201] .sup.1H NMR (400 MHz, CDCl.sub.3): =9.88 (s, 1H), 7.40-7.36 (m, 2H), 7.16 (d, J=7.9 Hz, 1H), 5.10-5.23 (m, 2H), 4.09 (q, J=7.0 Hz, 2H), 2.41 (dd, J=7.6, 1.6 Hz, 2H), 2.13-1.93 (m, 4H), 1.68-1.71 (m, 6H), 1.59 (s, 3H), 1.41-1.53 (m, 3H), 1.37 (s, 6H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 203.2, 191.3, 153.9, 151.1, 132.4, 131.6, 124.9, 124.5, 124.2, 111.5, 98.5, 86.0, 83.6, 64.2, 42.9, 34.1, 26.3, 26.1, 25.7, 19.1, 17.7, 14.7 ppm. GC/MS (EI): m/z (%): 356 (1) [M.sup.+], 313 (2), 190 (53), 175 (62), 137 (100), 107 (69), 93 (90), 79 (49).

[0202] Odour description (1% solution in EtOH on paper blotter, 24 h): vanilla powdery

Example 19: (E)-3-ethoxy-4-(non-6-en-4-yloxy)benzaldehyde

a) (E)-non-6-en-4-ol

[0203] To a solution of (E)-hex-3-enal (12.5 g, 127.0 mmol, 1.0 equiv) in THF (150 mL) was added propylmagnesium bromide (37.5 g, 255.0 mmol, 2.0 equiv) dropwise in 0 C. Stir at rt for 4 h. Water (15 mL) was added to quench the reaction. Filter off the solid and purity the product by silica gel chromatography to give (E)-non-6-en-4-ol as colorless liquid (21.8 mmol, 3.1 g, 15% yield).

[0204] .sup.13C NMR (101 MHz, CDCl.sub.3) 136.2, 124.9, 70.7, 40.7, 38.9, 25.7, 18.9, 14.1, 13.8. GC/MS (EI): m/z (%): 142 (1) [M.sup.+], 124 (2), 114 (1), 100 (2), 81 (8), 70 (72), 55 (100).

b) (E)-3-ethoxy-4-(non-6-en-4-yloxy)benzaldehyde

[0205] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (0.2 g, 1.0 mmol, 1.3 equiv) and (E)-non-6-en-4-ol (0.1 g, 0.7 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (0.2 mmol, 0.07 g, 33% yield).

[0206] .sup.1H NMR (400 MHz, CDCl.sub.3): =9.83 (s, 1H), 7.40 (s, 1H), 7.41 (d, J=6.2 Hz, 1H), 6.98 (d, J=8.8 Hz, 1H), 5.51-5.61 (m, 1H), 5.38-5.50 (m, 1H), 4.35 (quin, J=5.9 Hz, 1H), 4.13 (q, J=6.9 Hz, 2H), 2.32-2.48 (m, 2H), 1.94-2.08 (m, 2H), 1.59-1.83 (m, 2H), 1.35-1.56 (m, 5H), 0.90-0.99 (m, 6H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 191.0, 154.4, 150.1, 135.5, 130.0, 126.3, 124.0, 114.6, 111.9, 79.7, 64.7, 37.1, 35.8, 25.7, 18.6, 14.7, 14.1, 13.7 ppm. GC/MS (EI): m/z (%): 290 (17) [M.sup.+], 221 (4), 166 (100), 138 (56), 83 (35), 69 (77), 55 (38).

[0207] Odour description (1% solution in EtOH on paper blotter, 24 h): vanilla powdery creamy

Example 20: 3-ethoxy-4-(((3E,7E)-4,8,12-trimethyltrideca-3,7,11-trien-1-yl)oxy)benzaldehyde

[0208] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (0.4 g, 2.4 mmol, 1.1 equiv) and (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trien-1-ol (0.2 g, 2.2 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (1.8 mmol, 0.7 g, 78% yield).

[0209] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers) 9.83 (s, 1H), 7.52-7.31 (m, 2H), 7.07-6.81 (m, 1H), 5.22 (t, J=7.3 Hz, 1H), 5.15-5.02 (m, 2H), 4.14 (q, J=7.0 Hz, 2H), 4.09-4.00 (m, 2H), 2.59 (q, J=7.3 Hz, 2H), 2.19-2.00 (m, 6H), 2.00-1.91 (m, 2H), 1.79-1.72 (m, 1H), 1.71-1.64 (m, 5H), 1.63-1.53 (m, 6H), 1.52-1.41 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers) 190.9, 154.4, 154.4, 149.2, 138.8, 138.7, 135.4, 135.1, 131.3, 131.3, 129.9, 126.6, 124.3, 124.3, 124.0, 123.9, 119.5, 118.7, 111.7, 110.9, 68.8, 68.6, 64.5, 39.7, 39.7, 32.1, 27.9, 27.8, 26.8, 26.7, 26.5, 25.7, 23.5, 17.7, 16.2, 16.0, 14.7 ppm. GC/MS (EI): m/z (%): 384 (1) [M.sup.+], 248 (4), 219 (2), 166 (5), 137 (16), 95 (18), 81 (51), 69 (100).

[0210] Odour description (1% solution in EtOH on paper blotter, 24 h): vanilla (powdery, creamy, chocolate, gourmand)

Example 21: 3-ethoxy-4-((2-methyl-1-phenylhex-4-en-2-yl)oxy)benzaldehyde

a) (E)-2-benzyl-2-methylpent-3-en-1-ol

[0211] To a suspension of LiAlH.sub.4 (3.0 g, 80.0 mmol, 0.75 equiv) in THF (200 mL) was added (E)-2-benzyl-2-methylpent-3-enal (20.0 g, 106.0 mmol, 1.0 equiv) in Tetrahydrofuran (100 ml) at 5 C. dropwise and the resulting mixture was stirred at r.t. for 3 h. Then reaction was quenched by adding some solution of NH4Cl, the mixture was extracted with MTBE (150 mL*3), the organic layers were combined, and dried over MgSO.sub.4 and the solvent was removed to give (E)-2-benzyl-2-methylpent-3-en-1-ol (17.2 g, 90.4 mmol, 85% yield).

[0212] .sup.13C NMR (101 MHz, CDCl.sub.3) 138.2, 136.6, 130.7, 128.6, 127.7, 127.0, 126.0, 125.1, 69.4, 43.7, 42.3, 20.8, 18.4. GC/M S (EI): m/z (%): 190 (2) [M.sup.+], 172 (18), 159 (17), 129 (22), 117 (55), 91 (100), 65 (32), 53 (12).

b) 3-ethoxy-4-((2-methyl-1-phenylhex-4-en-2-yl)oxy)benzaldehyde

[0213] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (4.8 g, 28.9 mmol, 1.1 equiv) and (E)-2-benzyl-2-methylpent-3-en-1-ol (5.0 g, 26.3 mmol, 1.0 equiv) according to the procedure of example 1 as light yellow liquid (0.6 mmol, 0.2 g, 2% yield).

[0214] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.76 (s, 1H), 7.29-6.75 (m, 8H), 5.76-5.26 (m, 2H), 3.97 (q, J=7.0 Hz, 2H), 3.17-2.82 (m, 2H), 2.98-2.11 (m, 2H), 1.74-1.55 (m, 3H), 1.41-1.29 (m, 3H), 1.11 (s, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 191.2, 153.8, 151.2, 137.7, 132.2, 131.0, 128.8, 127.9, 126.5, 126.4, 124.9, 124.0, 111.2, 85.4, 64.2, 46.1, 42.8, 23.5, 18.2, 14.8 ppm. GC/MS (EI): m/z (%): 338 (1) [M.sup.+], 283 (1), 172 (22), 157 (14), 143 (30), 91 (100), 55 (19).

[0215] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery (vanilla) creamy (milky).

Example 22: 4-(dec-1-en-4-yloxy)-3-ethoxybenzaldehyde

[0216] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (4.7 g, 28.2 mmol, 1.1 equiv) and dec-1-en-4-ol (4.0 g, 25.6 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (12.8 mmol, 3.9 g, 50% yield).

[0217] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.83 (s, 1H), 7.46-7.29 (m, 2H), 6.99 (d, J=8.4 Hz, 1H), 6.07-5.70 (m, 1H), 5.27-4.94 (m, 2H), 4.50-4.29 (m, 1H), 4.13 (q, J=6.9 Hz, 2H), 2.62-2.29 (m, 2H), 1.89-1.59 (m, 2H), 1.49-1.28 (m, 11H), 0.98-0.67 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9, 154.1, 150.1, 133.9, 130.1, 126.3, 117.7, 114.7, 111.7, 79.4, 64.6, 38.3, 33.6, 31.7, 29.2, 25.2, 22.5, 14.7, 14.1 ppm. GC/MS (EI): m/z (%): 304 (5) [M.sup.+], 263 (1), 166 (100), 138 (56), 81 (8), 55 (18).

[0218] Odour description (1% solution in EtOH on paper blotter, 24 h): dry powdery (cedarwood, vanilla)

Example 23: 4-(4-(dec-1-en-4-yloxy)phenyl)butan-2-one

[0219] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (4.6 g, 28.2 mmol, 1.1 equiv) and dec-1-en-4-ol (4.0 g, 25.6 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (13.9 mmol, 4.2 g, 55% yield).

[0220] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.07 (d, J=7.8 Hz, 2H), 6.81 (d, J=7.9 Hz, 2H), 5.95-5.68 (m, 1H), 5.15-5.05 (m, 2H), 4.29-4.09 (m, 1H), 2.83 (t, J=7.4 Hz, 2H), 2.72 (t, J=7.1 Hz, 2H), 2.44-2.35 (m, 2H), 2.13 (s, 3H), 1.74-1.52 (m, 2H), 1.44-1.27 (s, 8H), 0.87 (t, J=5.7 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 208.2, 156.8, 134.3, 133.0, 129.2, 117.3, 116.1, 77.5, 45.5, 38.2, 33.7, 31.8, 30.1, 29.3, 28.9, 25.4, 22.6, 14.1 ppm. GC/MS (EI): m/z (%): 302 (12) [M.sup.+], 261 (6), 203 (5), 164 (100), 149 (12), 107 (90), 94 (27), 55 (18).

[0221] Odour description (1% solution in EtOH on paper blotter, 24 h): fruity (raspberry, gourmand) sugary

Example 24: methyl 4-(dec-1-en-4-yloxy)-2-hydroxy-3,6-dimethylbenzoate

[0222] The compound was obtained from methyl 2,4-dihydroxy-3,6-dimethylbenzoate (5.5 g, 28.2 mmol, 1.1 equiv) and dec-1-en-4-ol (4.0 g, 25.6 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (14.7 mmol, 4.9 g, 57% yield).

[0223] .sup.1H NMR (400 MHz, CDCl.sub.3) 11.88 (s, 1H), 6.25 (s, 1H), 5.91-5.64 (m, 1H), 5.29-4.89 (m, 2H), 4.51-4.25 (m, 1H), 3.90 (s, 3H), 2.49 (s, 3H), 2.46-2.27 (m, 2H), 2.08 (s, 3H), 1.75-1.56 (m, 2H), 1.36-1.19 (m, 8H), 0.86 (s, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 172.6, 162.6, 160.4, 139.8, 134.0, 117.5, 111.9, 108.0, 105.0, 77.2, 51.7, 38.4, 33.7, 31.8, 29.3, 25.2, 24.7, 22.6, 14.1, 8.1 ppm. GC/MS (EI): m/z (%): 334 (6) [M.sup.+], 293 (2), 196 (25), 164 (100), 136 (19), 55 (11).

[0224] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery (mossy, evernyl)

Example 25: methyl 2-(tetradec-1-en-4-yloxy)benzoate

[0225] The compound was obtained from methyl salicylate (1.3 ml, 10 mmol, 1 equiv.) and tetradec-1-en-4-ol (2.12 g, 10 mmol, 1 equiv.) according to the procedure of example 1 as a clear, colorless liquid (1.56 g, 4.4 mmol, 44%).

[0226] .sup.1H NMR (400 MHz, CDCl.sub.3, 298 K) (ppm)=7.83-7.67 (m, 1H), 7.53-7.36 (m, 1H), 7.05-6.87 (m, 2H), 6.03-5.80 (m, 1H), 5.19-5.01 (m, 2H), 4.45-4.28 (m, 1H), 3.87 (s, 3H), 2.63-2.37 (m, 2H), 1.86-1.60 (m, 2H), 1.52-1.16 (m, 16H), 0.95-0.80 (m, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3, 298 K) (ppm)=167.2, 157.8, 134.2, 133.0, 131.6, 121.7, 120.0, 117.4, 114.8, 78.7, 51.8, 38.2, 33.5, 31.9, 29.6, 29.6, 29.6, 29.6, 29.3, 25.2, 22.7, 14.1. MS (EI, 70 eV): 346 (1, [M]+*), 305 (5), 152 (100), 120 (75), 92 (15), 81 (10), 67 (12), 55 (20), 41 (25), 29 (10). Odour description (1% solution in EtOH on paper blotter, 24 h): aldehydic, metallic, green, citrus.

Example 26: 1-(2-(tetradec-1-en-4-yloxy)phenyl)propan-1-one

[0227] The compound was obtained from 1-(2-hydroxyphenyl)propan-1-one (1.37 ml, 10 mmol, 1 equiv.) and tetradec-1-en-4-ol (2.12 g, 10 mmol, 1 equiv.) according to the procedure of example 1 as clear colorless liquid (1.12 g, 2.8 mmol, 28%).

[0228] .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=7.66 (dd, J=1.8, 7.6 Hz, 1H), 7.48-7.20 (m, 1H), 7.02-6.82 (m, 2H), 5.82 (br dd, J=10.2, 17.1 Hz, 1H), 5.20-5.01 (m, 2H), 4.55-4.35 (m, 1H), 2.99 (q, J=7.2 Hz, 2H), 2.61-2.40 (m, 2H), 1.79-1.64 (m, 2H), 1.53-1.23 (m, 16H), 1.20-1.13 (m, 3H), 0.97-0.81 (m, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=204.0, 156.9, 133.7, 132.9, 130.5, 129.5, 120.3, 117.9, 113.1, 77.3, 38.0, 37.2, 33.4, 31.9, 29.6, 29.6, 29.6, 29.5, 29.3, 25.3, 22.7, 14.1, 8.6. MS (EI, 70 eV): 344 (1, [M]+.Math.), 303 (5), 150 (70), 133 (2), 121 (100), 150 (2), 97 (4), 83 (6), 67 (7), 55 (20), 41 (25), 29 (7).

[0229] Odour description (1% solution in EtOH on paper blotter, 24 h): aldehydic, metallic, green, citrus.

Example 27: 3-ethoxy-4-(tetradec-1-en-4-yloxy)benzaldehyde

[0230] The compound was obtained from ethyl vanillin (4.15 g, 25 mmol, 1 equiv.) and tetradec-1-en-4-ol (5.31 g, 25 mmol, 1 equiv.) according to the procedure of example 1 as clear colorless liquid (2.23 g, 5.9 mmol, 24%).

[0231] .sup.1H NMR (400 MHz, CDCl.sub.3, 298 K) (ppm)=9.83 (s, 1H), 7.43-7.38 (m, 2H), 6.98 (d, J=8.7 Hz, 1H), 5.87 (tdd, J=7.0, 10.1, 17.1 Hz, 1H), 5.18-5.05 (m, 2H), 4.38 (quin, J=5.9 Hz, 1H), 4.13 (q, J=7.0 Hz, 2H), 2.56-2.39 (m, 2H), 1.81-1.63 (m, 2H), 1.53-1.19 (m, 19H), 0.92-0.84 (m, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=190.9, 154.1, 150.1, 133.9, 130.2, 126.2, 117.7, 114.7, 111.8, 79.5, 64.7, 38.3, 33.7, 31.9, 29.6, 29.6, 29.5, 29.5, 29.3, 25.3, 22.7, 14.7, 14.1. MS (EI, 70 eV): 360 (1, [M]+.Math.), 194 (1), 166 (100), 149 (3) 138 (40), 123 (1), 109 (5), 97 (4), 81 (5), 69 (5), 55 (10), 41 (12), 29 (6).

[0232] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, aldehydic, metallic, green, citrus, mandarin.

Example 28: (Z)-3-ethoxy-4-(Pentadec-3-en-6-yloxy)benzaldehyde

a) pentadec-3-yn-6-ol

[0233] A solution of Butyllithium (1.6 M in hexanes, 62 mL, 99 mmol) was mixed with THF (tetrahydrofuran) (150 mL) and cooled to 78 C. Gaseous but-1-yne (8.94 g, 165 mmol) was slowly bubbled through this solution at 78 C. over 15 min and the resulting mixture stirred for additional 15 min. The mixture was then treated slowly at 78 C. with 2-nonyloxirane (9.38 g, 55 mmol), followed by borontrifluoride etherate (5.7 mL, 45 mmol) and the resulting mixture stirred at 78 C. for 1.5 h. The mixture was finally poured onto sat. aq. NaHCO.sub.3 soln. (300 mL), diluted with water (200 mL), extracted with MTBE (2200 mL), washed with brine (100 mL), dried over MgSO.sub.4 and concentrated to give a crude that was purified by Kugelrohr distillation at 180 C. and 0.12 mbar followed by flash chromatography on silica gel eluting with a gradient of MTBE in heptane to give pentadec-3-yn-6-ol (8.58 g, 69% yield) as a pale yellow oil that was used without further purification in the next step.

[0234] MS (EI, 70 eV): 224 (1, [M]+.Math.), 209 (2), 195 (2), 157 (6) 125 (4), 97 (42), 68 (100), 67 (84).

b) pentadec-3-en-6-ol

[0235] A flask was charged with Lindlar catalyst (Palladium on calcium carbonate, poisoned with lead) (1.2 g), ethyl acetate (300 mL), quinoline (30 mL) and pentadec-3-yn-6-ol (7.35 g, 32.8 mmol) and the flask purged with nitrogen followed by hydrogen. The mixture was allowed to stir under hydrogen for 1 h at room temperature after which it was flushed with nitrogen and filtered through a plug of celite, rinsing with MTBE (methyl tert-butyl ether). The mixture was extracted with 2 M HCl (2100 mL) and the aqueous layer extracted with additional MTBE (250 mL). the combined organic layers were dried over MgSO.sub.4 and evaporated to give pentadec-3-en-6-ol (7.51 g, 97% purity, 98% yield) as a pale yellow oil that was used in the next step without purification.

[0236] MS (EI, 70 eV): 226 (1, [M]+.Math.), 208 (2), 184 (1), 157 (7) 70 (100), 69 (34).

c) (Z)-3-ethoxy-4-(pentadec-3-en-6-yloxy)benzaldehyde

[0237] The compound was obtained from pentadec-3-en-6-ol (8.75 g, 38.6 mmol), ethyl vanillin (3-ethoxy-4-hydroxybenzaldehyde) (6.42 g, 38.6 mmol), triphenylphosphine (15.21 g, 58 mmol) and DIAD (diisopropyl azodicarboxylate) (11.7 g, 58 mmol) according to the process of example 1 as a colorless oil (3.74 g, 26% yield).

[0238] .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=9.85 (s, 1H), 7.40-7.45 (m, 2H), 6.99 (d, J=8.6 Hz, 1H), 5.47-5.57 (m, 1H), 5.37-5.47 (m, 1H), 4.38 (quin, J=5.9 Hz, 1H), 4.15 (q, J=6.8 Hz, 2H), 2.40-2.56 (m, 2H), 2.03-2.13 (m, 2H), 1.64-1.84 (m, 2H), 1.22-1.53 (m, 17H), 0.98 (t, J=7.6 Hz, 3H), 0.86-0.92 (m, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=190.9, 154.2, 150.1, 134.3, 130.0, 126.3, 123.7, 114.4, 111.8, 79.7, 64.6, 33.7, 31.9, 31.6, 29.6, 29.6, 29.5, 29.3, 25.3, 22.7, 20.8, 14.7, 14.1, 14.1. MS (EI, 70 eV): 374 (1, [M]+.Math.), 167 (21), 166 (100), 138 (38), 137 (35), 97 (23), 83 (28), 69 (36), 55 (32), 43 (23), 41 (34).

[0239] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, creamy, vanilla, aldehydic, mandarin.

Example 29: (E)-3-ethoxy-4-(pentadec-3-en-6-yloxy)benzaldehyde

a) 3-ethoxy-4-(pentadec-3-yn-6-yloxy)benzaldehyde

[0240] The compound was obtained from pentadec-3-yn-6-ol (2.24 g, 10 mmol), ethyl vanillin (3-ethoxy-4-hydroxybenzaldehyde) (1.66 g, 10 mmol), triphenylphosphine (3.93 g, 15 mmol) and DIAD (diisopropyl azodicarboxylate) (3.03 g, 15 mmol) according to the procedure of example 1 as a colorless oil (1.17 g, 31% yield).

[0241] MS (EI, 70 eV): 372 (2, [M]+.Math.), 166 (100), 138 (40).

b) (E)-3-ethoxy-4-(pentadec-3-en-6-yloxy)benzaldehyde

[0242] A flask was charged with Lindlar catalyst (Palladium on calcium carbonate, poisoned with lead) (100 mg), toluene (30 mL), pyridine (3 mL) and 3-ethoxy-4-(pentadec-3-yn-6-yloxy)benzaldehyde (1.17 g, 3.14 mmol) and the flask purged with nitrogen followed by hydrogen. The mixture was allowed to stir under hydrogen for 3 h at room temperature after which it was flushed with nitrogen and filtered through a plug of celite, rinsing with toluene. The solvent was evaporated and the resulting material purified by chromatography on silica gel, eluting with a gradient of ethyl acetate in heptane to give (E)-3-ethoxy-4-(pentadec-3-en-6-yloxy)benzaldehyde (0.55 g, 97% purity, 45% yield) as a colorless oil.

[0243] .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=9.84 (s, 1H), 7.44-7.40 (m, 2H), 6.99 (d, J=8.6 Hz, 1H), 5.63-5.54 (m, 1H), 5.51-5.42 (m, 1H), 4.35 (quin, J=5.9 Hz, 1H), 4.15 (q, J=7.1 Hz, 2H), 2.52-2.33 (m, 2H), 2.06-1.98 (m, 2H), 1.81-1.62 (m, 2H), 1.52-1.22 (m, 17H), 0.97 (t, J=7.5 Hz, 3H), 0.92-0.86 (m, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=190.9, 154.3, 150.0, 135.4, 129.8, 126.3, 124.0, 114.6, 114.2, 111.9, 80.0, 64.7, 33.9, 33.9, 31.9, 29.6, 29.6, 29.5, 29.5, 25.3, 25.0, 22.7, 14.7, 14.1, 13.7. MS (EI, 70 eV): 374 (1, [M]+.Math.), 208 (3), 167 (18), 166 (100), 138 (39), 137 (22), 55 (32), 43 (28), 41 (30).

[0244] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, creamy, vanilla, aldehydic, mandarin.

Example 30: 3-ethoxy-4-(((3Z,6Z)-nona-3,6-dien-1-yl)oxy)benzaldehyde

[0245] The compound was obtained from (3Z,6Z)-nona-3,6-dien-1-ol (7.00 g, 49.9 mmol), ethyl vanillin (3-ethoxy-4-hydroxybenzaldehyde) (8.30 g, 49.9 mmol), triphenylphosphine (19.64 g, 74.9 mmol) and DIAD (diisopropyl azodicarboxylate) (15.4 g, 74.9 mmol) according to the procedure of example 1 as a colorless oil (4.20 g, 88% purity, 26% yield).

[0246] .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=9.85 (s, 1H), 7.46-7.40 (m, 2H), 7.01-6.95 (m, 1H), 5.68-5.29 (m, 4H), 4.20-4.07 (m, 4H), 2.87 (t, J=7.1 Hz, 2H), 2.73-2.61 (m, 2H), 2.15-2.00 (m, 2H), 1.49 (t, J=7.0 Hz, 3H), 0.99 (t, J=7.6 Hz, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=190.9, 154.3, 149.2, 132.2, 131.4, 130.0, 126.8, 126.5, 124.3, 111.8, 110.8, 68.4, 64.5, 27.3, 25.7, 20.6, 14.7, 14.2. MS (EI, 70 eV): 288 (1, [M]+.Math.), 137 (22), 122 (21), 93 (53), 81 (100), 79 (42), 69 (34), 67 (55), 55 (39), 41 (35), 29 (25).

[0247] Odour description (1% solution in EtOH on paper blotter, 24 h): green, leaf aldehyde, green apple, powdery, vanilla.

Example 31: 4-(4-(((3Z,6Z)-nona-3,6-dien-1-yl)oxy)phenyl)butan-2-one

[0248] The compound was obtained from (3Z,6Z)-nona-3,6-dien-1-ol (1.40 g, 9.98 mmol), raspberry ketone (4-(4-hydroxyphenyl)butan-2-one) (1.64 g, 9.98 mmol), triphenylphosphine (3.93 g, 15.0 mmol) and DIAD (diisopropyl azodicarboxylate) (3.03 g, 15.0 mmol) according to the procedure of example 1 as a colorless oil (1.13 g, 40% yield).

[0249] .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=7.14-7.08 (m, 2H), 6.87-6.81 (m, 2H), 5.45-5.44 (m, 1H), 5.60-5.29 (m, 3H), 3.96 (t, J=6.8 Hz, 2H), 2.90-2.82 (m, 4H), 2.78-2.71 (m, 2H), 2.62-2.53 (m, 2H), 2.15 (s, 3H), 2.14-2.03 (m, 2H), 1.00 (t, J=7.5 Hz, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=208.2, 157.3, 133.0, 132.1, 130.8, 129.2, 126.9, 125.0, 114.6, 67.4, 45.5, 30.1, 28.9, 27.5, 25.7, 20.6, 14.3. MS (EI, 70 eV): 286 (11, [M]+.Math.), 107 (96), 93 (96), 91 (32), 81 (100), 79 (56), 69 (33), 67 (61), 55 (47), 43 (71), 41 (46).

[0250] Odour description (1% solution in EtOH on paper blotter, 24 h): green, leaf aldehyde, green apple, fruity.

Example 32: 1-methoxy-2-(((3Z,6Z)-nona-3,6-dien-1-yl)oxy)benzene

a) (3Z,6Z)-1-chloronona-3,6-diene

[0251] A solution of (3Z,6Z)-nona-3,6-dien-1-ol (2.80 g, 20.0 mmol) in toluene (40 mL) was treated dropwise at 0 C. with pyridine (0.19 g, 2.4 mmol) and then thionyl chloride (2.85 g, 24.0 mmol). The resulting mixture was heated to 80 C. for 2 h and then cooled to room temperature, poured onto iced aqueous NaHCO.sub.3 solution (150 mL), extracted with MTBE (250 mL), dried over MgSO.sub.4, filtered and concentrated. The resulting material was purified by chromatography on silica gel eluting with a gradient of MTBE in heptane, followed by Kugelrohr distillation to give (3Z,6Z)-1-chloronona-3,6-diene (2.69 g, 88% purity, 75% yield) as a pale yellow oil which was used without further purification.

[0252] MS (EI, 70 eV): 158 (22, [M]+.Math.), 143 (2), 129 (7), 123 (3), 109 (19), 67 (100).

b) 1-methoxy-2-(((3Z,6Z)-nona-3,6-dien-1-yl)oxy)benzene

[0253] A mixture of guaiacol (2-methoxyphenol) (0.78 g, 6.30 mmol), K.sub.2CO.sub.3 (1.31 g, 9.45 mmol), tetrabutylammonium iodide (0.35 g, 0.945 mmol) and acetonitrile (8 mL) was treated at room temperature with (3Z,6Z)-1-chloronona-3,6-diene (1.00 g, 6.3 mmol) and the resulting mixture stirred overnight then heated to reflux for 4 h. The reaction mixture was then poured into saturated aqueous NH.sub.4Cl solution (50 mL), extracted with MTBE (250 mL), dried over MgSO4, filtered and evaporated. The resulting material was purified by chromatography on silica gel eluting with a gradient of MTBE in heptane, followed by Kugelrohr distillation to give 1-methoxy-2-(((3Z,6Z)-nona-3,6-dien-1-yl)oxy)benzene (0.27 g, 17% yield) as a colorless oil. .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=6.99-6.86 (m, 4H), 5.61-5.30 (m, 4H), 4.09-4.01 (m, 2H), 3.92-3.87 (m, 3H), 2.91-2.81 (m, 2H), 2.73-2.61 (m, 2H), 2.16-2.02 (m, 2H), 1.00 (t, J=7.5 Hz, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=149.5, 148.4, 132.2, 131.0, 126.9, 124.6, 121.1, 120.9, 113.3, 111.9, 68.3, 55.9, 27.5, 25.7, 20.6, 14.3. MS (EI, 70 eV): 246 (2, [M]+.Math.), 124 (100), 122 (38), 109 (25), 93 (42), 81 (53), 79 (27), 77 (27), 67 (29), 55 (23), 41 (26).

[0254] Odour description (1% solution in EtOH on paper blotter, 24 h): green, leaf aldehyde.

Example 33: 2-(((3Z,6Z)-nona-3,6-dien-1-yl)oxy)naphthalene

[0255] The compound was obtained from naphthalen-2-ol (0.91 g, 6.3 mmol), K.sub.2CO.sub.3 (1.31 g, 9.45 mmol), tetrabutylammonium iodide (0.35 g, 0.945 mmol) and (3Z,6Z)-1-chloronona-3,6-diene (1.00 g, 6.3 mmol) according to the procedure of example 32b as a colorless oil (0.33 g, 20% yield).

[0256] .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=7.85-7.73 (m, 3H), 7.47 (ddd, J=1.2, 6.8, 8.1 Hz, 1H), 7.37 (ddd, J=1.2, 7.0, 8.1 Hz, 1H), 7.22-7.14 (m, 2H), 5.70-5.33 (m, 4H), 4.18-4.08 (m, 2H), 2.96-2.81 (m, 2H), 2.74-2.60 (m, 2H), 2.20-2.07 (m, 2H), 1.03 (t, J=7.5 Hz, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=156.9, 134.6, 132.2, 131.0, 129.4, 129.0, 127.6, 126.9, 126.7, 126.3, 125.0, 123.6, 119.0, 106.7, 67.4, 27.5, 25.8, 20.6, 14.3. MS (EI, 70 eV): 266 (6, [M]+.Math.), 145 (15), 144 (100), 127 (33), 115 (42), 93 (38), 81 (28), 79 (20), 67 (19), 55 (16), 41 (18).

[0257] Odour description (1% solution in EtOH on paper blotter, 24 h): weak, green, leaf aldehyde.

Example 34: 3-methoxy-4-(((3Z,6Z)-nona-3,6-dien-1-yl)oxy)benzaldehyde

[0258] The compound was obtained from (3Z,6Z)-nona-3,6-dien-1-ol (2.81 g, 20.1 mmol), vanillin (4-hydroxy-3-methoxybenzaldehyde) (3.05 g, 20.1 mmol), triphenylphosphine (7.89 g, 30.1 mmol) and DIAD (diisopropyl azodicarboxylate) (6.08 g, 30.1 mmol) according to the procedure of example 1 as a colorless oil (1.71 g, 31% yield).

[0259] .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=9.88-9.85 (m, 1H), 7.48-7.41 (m, 2H), 6.99 (d, J=8.3 Hz, 1H), 5.63-5.28 (m, 4H), 4.12 (t, J=7.2 Hz, 2H), 3.94 (s, 3H), 2.90-2.76 (m, 2H), 2.74-2.58 (m, 2H), 2.08 (dquin, J=1.3, 7.4 Hz, 2H), 0.98 (t, J=7.5 Hz, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=190.9, 153.9, 149.8, 132.3, 131.6, 130.0, 126.7, 126.7, 124.0, 111.4, 109.3, 68.4, 56.0, 27.2, 25.7, 20.6, 14.2. MS (EI, 70 eV): 274 (2, [M]+.Math.), 152 (29), 122 (27), 93 (55), 81 (100), 79 (45), 77 (26), 69 (31), 67 (58), 55 (41), 41 (40).

[0260] Odour description (1% solution in EtOH on paper blotter, 24 h): green, leaf aldehyde, powdery, vanilla.

Example 35: 3-methoxy-4-(tridec-1-en-4-yloxy)benzaldehyde

[0261] The compound was obtained from tridec-1-en-4-ol (1.98 g, 15.0 mmol), vanillin (4-hydroxy-3-methoxybenzaldehyde) (1.52 g, 10.0 mmol), triphenylphosphine (3.93 g, 15.0 mmol) and DIAD (diisopropyl azodicarboxylate) (3.03 g, 15.0 mmol) according to the procedure of example 1 as a colorless oil (0.88 g, 26% yield).

[0262] .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=9.86 (s, 1H), 7.46-7.41 (m, 2H), 6.99 (d, J=8.8 Hz, 1H), 5.87 (tdd, J=7.1, 10.1, 17.1 Hz, 1H), 5.19-5.07 (m, 2H), 4.43 (quin, J=6.0 Hz, 1H), 3.93 (s, 3H), 2.59-2.41 (m, 2H), 1.86-1.69 (m, 2H), 1.55-1.21 (m, 14H), 0.93-0.86 (m, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=190.8, 153.7, 150.6, 133.8, 129.9, 126.5, 117.8, 113.5, 109.9, 79.1, 56.1, 38.3, 33.7, 31.9, 29.5, 29.5, 29.5, 29.3, 25.3, 22.7, 14.1. MS (EI, 70 eV): 332 (1, [M]+.Math.), 153 (13), 152 (100), 151 (24), 83 (4), 69 (6), 67 (5), 55 (11), 43 (10), 41 (13), 29 (4).

[0263] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, aldehydic, green, metallic, mandarin.

Example 36: 4-(4-(tridec-1-en-4-yloxy)phenyl)butan-2-one

[0264] The compound was obtained from tridec-1-en-4-ol (3.97 g, 20.0 mmol), raspberry ketone (4-(4-hydroxyphenyl)butan-2-one) (3.28 g, 20.0 mmol), triphenylphosphine (7.87 g, 30.0 mmol) and DIAD (diisopropyl azodicarboxylate) (6.07 g, 30.0 mmol) according to the procedure of example 1 as a colorless oil (2.11 g, 29% yield).

[0265] .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=7.14-7.06 (m, 2H), 6.84 (d, J=8.6 Hz, 2H), 5.94-5.79 (m, 1H), 5.19-5.05 (m, 2H), 4.24 (quin, J=5.9 Hz, 1H), 2.89-2.81 (m, 2H), 2.79-2.71 (m, 2H), 2.50-2.35 (m, 2H), 2.16 (s, 3H), 1.73-1.59 (m, 2H), 1.54-1.20 (m, 14H), 0.96-0.86 (m, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=208.1, 156.8, 134.3, 133.0, 129.2, 117.3, 116.1, 77.5, 45.5, 38.2, 33.7, 31.9, 30.1, 29.6, 29.6, 29.6, 29.3, 28.9, 25.4, 22.7, 14.1. MS (EI, 70 eV): 344 (4, [M]+.Math.), 165 (11), 164 (97), 149 (9), 121 (16), 107 (100), 94 (32), 69 (9), 55 (21), 43 (43), 41 (22).

[0266] Odour description (1% solution in EtOH on paper blotter, 24 h): fruity, juicy, raspberry, aldehydic, green, metallic.

Example 37: 2-ethoxy-4-(methoxymethyl)-1-(tridec-1-en-4-yloxy)benzene

[0267] The compound was obtained from tridec-1-en-4-ol (1.98 g, 10.0 mmol), 2-ethoxy-4-(methoxymethyl)phenol (1.82 g, 10.0 mmol), triphenylphosphine (3.93 g, 15.0 mmol) and DIAD (diisopropyl azodicarboxylate) (3.03 g, 15.0 mmol) according to the procedure of example 1 as a colorless oil (0.39 g, 2.7% yield).

[0268] .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=6.94-6.88 (m, 2H), 6.87-6.82 (m, 1H), 5.92 (tdd, J=7.0, 10.1, 17.2 Hz, 1H), 5.17-5.04 (m, 2H), 4.39 (s, 2H), 4.22 (quin, J=5.9 Hz, 1H), 4.09 (q, J=7.1 Hz, 2H), 3.40 (s, 3H), 2.52-2.35 (m, 2H), 1.78-1.59 (m, 2H), 1.57-1.22 (m, 17H), 0.95-0.85 (m, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=150.4, 147.7, 134.7, 131.9, 120.5, 118.1, 117.0, 113.9, 80.1, 74.7, 64.5, 58.0, 38.4, 33.8, 31.9, 29.7, 29.6, 29.6, 29.3, 25.3, 22.7, 15.0, 14.1. MS (EI, 70 eV): 362 (4, [M]+), 321 (0), 182 (100), 181 (7). Odour description (1% solution in EtOH on paper blotter, 24 h): citrus, mandarin, green.

Example 38: 3-methoxy-4-(tetradec-1-en-4-yloxy)benzaldehyde

[0269] The compound was obtained from tetradec-1-en-4-ol (2.12 g, 10.0 mmol), 4-hydroxy-3-methoxybenzaldehyde (1.52 g, 10.0 mmol), triphenylphosphine (3.93 g, 15.0 mmol) and DIAD (diisopropyl azodicarboxylate) (3.03 g, 15.0 mmol) according to the procedure of example 1 as a colorless oil (1.05 g, 90% purity, 27% yield).

[0270] .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=9.85 (s, 1H), 7.45-7.41 (m, 2H), 6.99 (d, J=9.0 Hz, 1H), 5.93-5.79 (m, 1H), 5.19-5.07 (m, 2H), 4.42 (quin, J=6.0 Hz, 1H), 3.92 (s, 3H), 2.58-2.41 (m, 2H), 1.85-1.66 (m, 2H), 1.54-1.22 (m, 16H), 0.92-0.86 (m, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=190.8, 153.7, 150.6, 133.7, 129.9, 126.5, 117.8, 113.5, 109.9, 79.1, 56.0, 38.3, 33.7, 31.9, 31.9, 29.6, 29.5, 29.3, 25.3, 22.7, 14.1. MS (EI, 70 eV): 346 (2, [M]+.Math.), 194 (1), 152 (100).

[0271] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, creamy, aldehydic, mandarin, madeleine.

Example 39: 4-(4-(pentadec-3-en-6-yloxy)phenyl)butan-2-one

a) 4-(4-(pentadec-3-yn-6-yloxy)phenyl)butan-2-one

[0272] The compound was obtained from pentadec-3-yn-6-ol (1.04 g, 4.63 mmol), 4-(4-hydroxyphenyl)butan-2-one (0.761 g, 4.63 mmol), triphenylphosphine (1.824 g, 6.95 mmol) and DIAD (diisopropyl azodicarboxylate) (1.41 g, 6.95 mmol) according to the procedure of example 1 as a colorless oil (0.100 g, 5.8% yield) which was used without further purification. MS (EI, 70 eV): 370 (6, [M]+.Math.), 303 (2), 245 (4), 164 (100), 107 (89), 43 (41).

b) 4-(4-(pentadec-3-en-6-yloxy)phenyl)butan-2-one

[0273] A flask was charged with Lindlar catalyst (Palladium on calcium carbonate, poisoned with lead) (27 mg), toluene (7 mL), pyridine (0.7 mL) and 4-(4-(pentadec-3-yn-6-yloxy)phenyl)butan-2-one (0.270 g, 0.729 mmol) and the flask purged with nitrogen followed by hydrogen. The mixture was allowed to stir under hydrogen for 1.5 h at room temperature after which it was flushed with nitrogen and filtered through a plug of celite, rinsing with MTBE (methyl tert-butyl ether). The solvent was evaporated and the resulting material purified by chromatography on silica gel, eluting with a gradient of ethyl acetate in heptane to give 4-(4-(pentadec-3-en-6-yloxy)phenyl)butan-2-one (0.151 g, 56% yield).

[0274] .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=7.12-7.06 (m, 2H), 6.86-6.81 (m, 2H), 5.64-5.34 (m, 2H), 4.29-4.14 (m, 1H), 2.91-2.80 (m, 2H), 2.80-2.70 (m, 2H), 2.48-2.32 (m, 2H), 2.15 (s, 3H), 2.07 (dqd, J=1.3, 7.5, 14.9 Hz, 2H), 1.70-1.59 (m, 2H), 1.54-1.21 (m, 14H), 1.03-0.94 (m, 3H), 0.93-0.86 (m, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=208.2, 156.8, 134.0, 132.9, 129.2, 124.0, 116.0, 77.9, 45.5, 33.8, 31.9, 31.5, 30.1, 29.7, 29.6, 29.5, 29.3, 29.3, 28.9, 25.5, 22.7, 20.8, 14.2, 14.1. MS (EI, 70 eV): 372 (5, [M]+.Math.), 303 (5), 245 (11), 164 (100), 149 (10), 121 (17), 107 (83), 69 (36).

[0275] Odour description (1% solution in EtOH on paper blotter, 24 h): raspberry, mandarin, citrus, aldehydic, fresh.

Example 40: ethyl 2-(2-ethoxy-4-formylphenoxy)hept-4-enoate

[0276] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (2.5 g, 15.0 mmol, 1.0 equiv) and ethyl 2-hydroxyhept-4-enoate (2.9 g, 16.6 mmol, 1.1 equiv) according to the procedure of example 1 as colorless liquid (6.6 mmol, 2.1 g, 44% yield).

[0277] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.75 (s, 1H), 7.39-7.24 (m, 2H), 6.94-6.74 (m, 1H), 5.69-5.33 (m, 2H), 4.80-4.59 (m, 1H), 4.21-3.96 (m, 4H), 2.77-2.55 (m, 2H), 2.09-1.82 (m, 2H), 1.37 (t, J=6.9 Hz, 3H), 1.17 (t, J=7.1 Hz, 3H), 0.88 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9 (d), 170.5 (s), 153.1 (s), 149.8 (s), 136.5 (d), 131.3 (s), 125.8 (d), 122.3 (d), 115.4 (d), 112.1 (d), 78.1 (d), 64.8 (t), 61.2 (t), 36.1 (t), 25.6 (t), 14.6 (q), 14.2 (q), 13.6 (q) ppm. GC/MS (EI): m/z (%): 320 (27) [M.sup.+], 247 (6), 219 (2), 166 (100), 138 (44), 109 (50), 55 (25).

[0278] Odor description (1% in alc, 24 h on blotter): powdery (vanilla)

Example 41: 3-ethoxy-4-(((3Z,8Z)-undeca-3,8-dien-6-yl)oxy)benzaldehyde

a) (3Z,8Z)-undeca-3,8-dien-6-ol

[0279] 1,2-Butadiene (70 g, 1.3 mol, 3 equiv.) was dissolved in THF (400 mL). A solution of butyllithium (2.5M in hexane, 400 mL, 1 mol, 2.3 equiv.) was added dropwise at 10 C. under stirring over a period of 40 min, upon which the temperature rose to 25 C. and a clear yellow solution formed. Stirring was continued for 22 hours at RT yielding a beige suspension. Epichlorohydrine (40 g, 0.43 mol, 1 equiv.) was added dropwise during 10 min and the resulting mixture was refluxed for 23 h. The resulting clear, yellow solution was poured on cold 1N aq. HCl-solution (300 mL). Extraction with MTBE, washing with water and brine, drying over MgSO.sub.4 and concentration i. RV. yielded a clear, yellow liquid (55.6 g, 78%). The crude product was distilled over a 15 cm Vigreux column (0.05 mbar/58 C.) to yield undeca-3,8-diyn-6-ol (31.9 g, 44%). The compound (6.5 g) was dissolved in hexane (100 mL) and Lindlar catalyst was added (0.20 g). Hydrogenation was effected under 1 bar H.sub.2 at RT for 2 h. The mixture was filtered and dried to yield (3Z,8Z)-undeca-3,8-dien-6-ol (6.5 g, 99%).

[0280] .sup.1H-NMR (400 MHz, CDCl.sub.3): 5.53-5.61 (m, 2H), 5.40 (dtt, J=10.8, 7.5, 7.5, 1.6, 1.6 Hz, 2H), 3.63-3.68 (m, 1H), 2.24-2.28 (m, 4H), 2.05-2.13 (m, 4H), 1.78 (d, J=3.7 Hz, 1H), 0.98 (t, J=7.5 Hz, 6H). .sup.13C-NMR (101 MHz, CDCl.sub.3): 134.9 (2s), 124.5 (2s), 71.2 (s), 34.5 (2s), 20.7 (2s), 14.2 (2s). MS (EI, 70 eV): 150(2; [M-H.sub.2O].sup.+), 99(26), 81(97), 70(60), 69(28), 55(100), 41(64), 29(20).

b) 3-ethoxy-4-(((3Z,8Z)-undeca-3,8-dien-6-yl)oxy)benzaldehyde

[0281] The compound was obtained from ethylvanillin (4.0 g), (3Z,8Z)-undeca-3,8-dien-6-ol (4.0 g), triphenyl phosphine (8.1 g) and diisopropyl azodicarboxylate (6.2 g) according to the procedure of example 1 as a clear yellow liquid (1.9 g, 25%).

[0282] .sup.1H-NMR (400 MHz, CDCl3): 9.83 (s, 1H), 7.35-7.44 (m, 2H), 6.98 (d, J=8.8 Hz, 1H), 5.33-5.61 (m, 4H), 4.39 (quin, J=6.0 Hz, 1H), 4.12 (q, J=7.0 Hz, 2H), 2.30-2.54 (m, 4H), 1.98-2.13 (m, 4H), 1.44 (t, J=7.0 Hz, 3H), 0.96 (t, J=7.5 Hz, 6H). .sup.13C-NMR (101 MHz, CDCl.sub.3): 190.9 (s), 153.9 (s), 150.1 (s), 134.5 (2s), 130.2 (s), 126.2 (s), 123.6 (2s), 114.6 (s), 111.7 (s), 79.3 (s), 64.6 (s), 31.3 (2s), 20.8 (2s), 14.7 (s), 14.1 (2s). MS (EI, 70 eV): 316(4; M.sup.+), 247(2), 166(41), 151(17), 137(56), 121(28), 109(65), 95(97), 81(100), 69(85), 55(39), 41(84), 29(22).

[0283] Odour description (1% solution in EtOH on paper blotter, 24 h): vanilla, powdery.

Example 42: 3-ethoxy-4-((4-methylnon-3-en-1-yl)oxy)benzaldehyde

[0284] To a solution of 3-ethoxy-4-hydroxybenzaldehyde (1.57 g, 9.45 mmol, 1.0 equiv) and potassium carbonate (1.97 g, 14.18 mmol) in DMF (15 mL) was added 1-bromo-4-methylnon-3-ene (2.69 g, 12.3 mmol, 1.4 equiv, prepared according to a procedure by Zarbin, P. H. G.; et al. Journal of Chemical Ecology 2012, 38, 825 using 1-cyclopropylethan-1-one and pentylmagnesium bromide) dropwise at r.t. and then stirred at 90 C. for 16 hours under argon atmosphere. The reaction conversion was monitored by TLC and GC. After cooling down the reaction solution to r.t., water (10 mL) and MTBE (10 mL) was added. The mixture was extracted with MTBE (210 mL), the organic layers were combined and washed with water (310 mL), and dried with MgSO.sub.4 and the solvent was removed to give yellow oil. It was then purified by silica gel column chromatography (hexane:MTBE=94:6) to get 3-ethoxy-4-((4-methylnon-3-en-1-yl)oxy)benzaldehyde (0.72 g, 25% yield, E/Z 84:16) as light yellow liquid. .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 9.83 (s, 1H), 7.42 (d, J=8.1 Hz, 1H), 7.40 (s, 1H), 6.97 (d, J=7.9 Hz, 1H), 5.23-5.17 (m, 1H), 4.18-4.03 (m, 4H), 2.58 (q, J=7.3 Hz, 2H), 2.09-1.95 (m, 2H), 1.76-1.64 (m, 3H), 1.50-1.20 (m, 9H), 0.92-0.84 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 190.9, 154.4, 154.3, 149.1, 149.1, 139.2, 139.0, 129.9, 129.9, 126.6, 119.0, 118.3, 111.7, 110.8, 110.8, 68.8, 68.6, 64.5, 39.7, 31.9, 31.8, 31.5, 27.9, 27.7, 27.7, 27.5, 23.5, 22.6, 22.5, 16.1, 14.7, 14.0 ppm.

[0285] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, sweet, sugary.

Example 43: 3-ethoxy-4-(undec-2-en-5-yloxy)benzaldehyde

[0286] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (1.00 g, 6.02 mmol, 1.0 equiv) and undec-2-en-5-ol (1.13 g, 6.62 mmol, 1.1 equiv) according to according to the procedure of example 1 as light yellow liquid (0.30 g, 16% yield, E/Z 73:27).

[0287] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 9.83 (s, 1H), 7.42-7.39 (m, 2H), 7.04-6.89 (m, 1H), 5.64-5.40 (m, 2H), 4.43-4.26 (m, 1H), 4.13 (q, J=6.9 Hz, 2H), 2.48-2.33 (m, 2H), 1.77-1.62 (m, 5H), 1.51-1.25 (m, 11H), 0.93-0.81 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 190.8, 154.2, 154.1, 150.0, 130.0, 128.2, 126.6, 126.2, 126.2, 125.2, 114.6, 114.4, 111.8, 111.7, 79.9, 79.6, 64.6, 64.6, 37.0, 33.7, 33.6, 31.7, 31.3, 29.2, 25.3, 25.2, 22.5, 18.0, 14.7, 14.0, 13.0 ppm.

[0288] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, creamy, vanilla.

Example 44: 4-(dodec-3-en-6-yloxy)-3-ethoxybenzaldehyde

[0289] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (1.07 g, 6.41 mmol, 1.0 equiv) and dodec-3-en-6-ol (1.30 g, 7.05 mmol, 1.1 equiv) according to the procedure of example 1 as light yellow liquid (0.50 g, 23% yield, E/Z 85:15).

[0290] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 9.83 (s, 1H), 7.44-7.37 (m, 2H), 6.97 (d, J=8.8 Hz, 1H), 5.68-5.27 (m, 2H), 4.40-4.28 (m, 1H), 4.13 (q, J=7.1 Hz, 2H), 2.50-2.32 (m, 2H), 2.08-1.97 (m, 2H), 1.76-1.64 (m, 2H), 1.50-1.23 (m, 11H), 0.99-0.93 (m, 3H), 0.90-0.85 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 190.9, 154.3, 154.1, 150.0, 135.4, 134.3, 130.0, 130.0, 126.2, 123.9, 123.6, 114.6, 114.3, 111.8, 111.7, 79.9, 79.6, 64.6, 64.6, 37.0, 33.7, 33.6, 31.7, 31.6, 29.2, 25.6, 25.3, 25.2, 22.5, 20.7, 14.7, 14.7, 14.1, 14.0, 13.7 ppm.

[0291] Odour description (1% solution in EtOH on paper blotter, 24 h): woody, cedarwood, vanilla.

Example 45: methyl (Z)-12-(2-methoxyphenoxy)octadec-9-enoate

[0292] The compound was obtained from 2-methoxyphenol (2.00 g, 16.1 mmol, 1.0 equiv) and methyl (Z)-12-hydroxyoctadec-9-enoate (5.54 g, 17.7 mmol, 1.1 equiv) according to the procedure of example 1 as pink liquid (2.65 g, 39% yield).

[0293] .sup.1H NMR (400 MHz, CDCl.sub.3): 6.97-6.83 (m, 4H), 5.53-5.40 (m, 2H), 4.27-4.15 (m, 1H), 3.85 (s, 3H), 3.67 (s, 3H), 2.51-2.35 (m, 2H), 2.31 (t, J=7.6 Hz, 2H), 2.08-1.97 (m, 2H), 1.62 (s, 4H), 1.56-1.46 (m, 1H), 1.43-1.22 (m, 15H), 0.92-0.84 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3): 174.2, 150.6, 147.9, 132.1, 124.9, 121.3, 120.8, 116.3, 112.3, 79.6, 55.9, 51.4, 34.1, 33.9, 31.8, 31.8, 29.5, 29.3, 29.1, 29.1, 29.1, 27.4, 25.4, 24.9, 22.6, 14.1 ppm.

[0294] Odour description (1% solution in EtOH on paper blotter, 24 h): phenolic, medicinal, guaiacol, vanilla absolute, peru balsam.

Example 46: 1-(dec-1-en-4-yloxy)-2-ethoxy-4-methylbenzene and 2-(dec-1-en-4-yloxy)-1-ethoxy-4-methylbenzene

[0295] The compound was obtained from a 1:1 mixture of 2-ethoxy-4-methylphenol and 2-ethoxy-5-methylphenol (1.33 g, 8.73 mmol, 1.0 equiv, prepared according to EP0179532) and dec-1-en-4-ol (1.50 g, 9.60 mmol, 1.1 equiv) according to the procedure of example 1 as a colorless liquid (0.9 g, 36% yield, mixture of regioisomers 55:45).

[0296] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of regioisomers): 6.88-6.78 (m, 1H), 6.77-6.65 (m, 2H), 6.00-5.85 (m, 1H), 5.18-5.04 (m, 2H), 4.27-4.12 (m, 1H), 4.05 (dd, J=6.2, 7.0 Hz, 2H), 2.54-2.35 (m, 2H), 2.29 (d, J=6.8 Hz, 3H), 1.79-1.59 (m, 2H), 1.56-1.39 (m, 5H), 1.36-1.24 (m, 6H), 0.90 (br d, J=1.2 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of regioisomers): 150.2, 148.1, 148.0, 145.8, 134.9, 134.8, 131.7, 130.6, 122.1, 121.1, 119.3, 118.8, 116.9, 116.8, 115.2, 114.7, 80.2, 79.8, 64.9, 64.4, 38.4, 33.8, 33.8, 31.8, 31.8, 29.4, 29.4, 25.3, 25.3, 22.6, 21.0, 20.8, 15.0, 15.0, 14.1 ppm.

[0297] Odour description (1% solution in EtOH on paper blotter, 24 h): medicinal, phenolic, vanilla.

Example 47: 3-ethoxy-4-((4-methyl-6-phenylhex-3-en-1-yl)oxy)benzaldehyde

a) (6-bromo-3-methylhex-3-en-1-yl)benzene

[0298] Magnesium powder (6.94 g, 285 mmol, 1.2 equiv) was added to a 500 mL-sulfonation flask and overlayed with THF (20 mL). Then a solution of (2-bromoethyl)benzene (52.8 g, 285 mmol, 1.2 equiv) in THF (100 mL) was added dropwise, after having started the Grignard reaction using a catalytic amount of iodine and by heating to reflux with a heatgun. The reaction mixture was refluxed for 1 hour. Then, a solution of 1-cyclopropylmethyl ketone (20.0 g, 238 mmol, 1.0 equiv) in THF (100 mL) was added dropwise to the Grignard reagent. After stirring for 1 hour at room temperature, a solution of 54 mL of 63% sulfuric acid (in water) was added dropwise at 0 C. and the reaction mixture was stirred for 18 hours at room temperature. After quenching with water (200 mL), the reaction mixture was extracted with MTBE (2250 mL). The combined organic layers were washed with 2M NaOH (250 mL), water (250 mL), brine (250 mL), dried over MgSO4 and the solvent was removed under reduced pressure. The crude product was distilled over a 3 cm Vigreux column under high vacuum (0.04 mbar) to give (6-bromo-3-methylhex-3-en-1-yl)benzene (40.6 g, 67 yield, E/Z 80:20) as a colorless liquid.

[0299] .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 142.0, 137.9, 137.5, 128.4, 128.3, 128.3, 128.2, 125.9, 125.7, 122.3, 121.4, 41.4, 34.5, 34.1, 34.1, 32.7, 32.6, 31.6, 31.5, 23.3, 16.4 ppm.

b) 3-ethoxy-4-((4-methyl-6-phenylhex-3-en-1-yl)oxy)benzaldehyde

[0300] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (6.56 g, 39.5 mmol, 1.0 equiv) and (6-bromo-3-methylhex-3-en-1-yl)benzene (10.0 g, 39.5 mmol, 1.0 equiv) according to the procedure of example 42 as a slightly yellow liquid (7.40 g, 55% yield, E/Z 82:18).

[0301] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 9.83 (s, 0.82H), 9.82 (s, 0.18H), 7.46-7.36 (m, 2H), 7.29-7.20 (m, 2H), 7.17 (s, 3H), 6.93 (d, J=8.1 Hz, 0.82H), 6.86 (d, J=8.1 Hz, 0.18H), 5.29-5.12 (m, 1H), 4.21-4.07 (m, 2H), 4.00 (t, J=7.1 Hz, 1.64H), 3.85 (t, J=7.2 Hz, 0.36H), 2.79-2.66 (m, 2H), 2.62-2.51 (m, 1.64H), 2.45 (dq, J=1.0, 7.3 Hz, 0.36H), 2.41-2.35 (m, 0.36H), 2.35-2.27 (m, 1.64H), 1.78 (d, J=1.2 Hz, 0.54H), 1.73 (s, 2.46H), 1.52-1.41 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 190.9, 154.3, 154.3 (Z), 149.1, 149.1 (Z), 142.1, 142.0 (Z), 137.9, 137.6 (Z), 129.9, 129.9, 128.4, 128.4, 128.2, 128.2, 126.5, 126.5, 125.8, 125.7, 120.3 (Z), 119.4, 111.8 (Z), 111.7, 110.8, 68.5, 68.5, 64.5, 41.6, 34.5, 34.2 (Z), 34.0 (Z), 27.8, 27.7 (Z), 23.5 (Z), 16.3, 14.7, 14.6 (Z) ppm. GC/MS (EI) major E isomer: m/z (%): 338 (0, [M].sup.+.Math.), 132 (5), 131 (49), 117 (10), 105 (6), 92 (8), 91 (100), 81 (7), 69 (6), 67 (7), 65 (6). GC/MS (EI) minor Z isomer: m/z (%): 132 (5), 131 (44), 117 (11), 105 (7), 92 (8), 91 (100), 81 (7), 69 (6), 67 (6), 65 (6).

[0302] Odour description (1% solution in EtOH on paper blotter, 24 h): sweet, vanilla, ice cream, powdery, fruity, raspberry, sorbet.

Example 48: (E)-3-ethoxy-4-((4-phenylpent-3-en-1-yl)oxy)benzaldehyde

[0303] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (1.00 g, 6.02 mmol, 1.0 equiv) and (5-bromopent-2-en-2-yl)benzene (1.36 g, 6.02 mmol, 1.0 equiv, prepared according to Brucher, O. et al. ACS Catalysis 2011, 1, 1448) according to the procedure of example 42 as a slightly yellow liquid (0.44 g, 26% yield, E/Z 82:18).

[0304] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 9.84 (s, 1H), 7.49-7.36 (m, 4H), 7.35-7.28 (m, 2H), 7.27-7.19 (m, 1H), 6.99 (d, J=8.1 Hz, 1H), 5.85 (qt, J=1.3, 7.3 Hz, 1H), 4.19 (t, J=7.1 Hz, 2H), 4.15 (q, J=7.0 Hz, 2H), 2.85-2.71 (m, 2H), 2.11 (d, J=1.2 Hz, 3H), 1.47 (t, J=7.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 190.9, 154.3, 149.2, 143.5, 137.9, 130.1, 128.2, 126.9, 126.5, 125.7, 122.5, 111.9, 110.9, 68.3, 64.5, 28.7, 16.1, 14.7 ppm.

[0305] Odour description (1% solution in EtOH on paper blotter, 24 h): sweet, powdery, vanilla, ice cream.

Example 49: 3-ethoxy-4-((4-(4-methoxyphenyl)pent-3-en-1-yl)oxy)benzaldehyde

[0306] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (1.89 g, 11.4 mmol, 1.0 equiv) and 1-(5-bromopent-2-en-2-yl)-4-methoxybenzene (2.90 g, 11.4 mmol, 1.0 equiv, prepared according to Bruecher, O. et al., Tetrahedron 2012, 6, 6968) according to the procedure of example 42 as a colorless liquid (1.17 g, 30% yield, E/Z 99:1).

[0307] .sup.1H NMR (400 MHz, CDCl.sub.3, major E isomer): 9.84 (s, 1H), 7.42 (d, J=2.9 Hz, 2H), 7.34 (d, J=9.0 Hz, 2H), 6.99 (d, J=8.1 Hz, 1H), 6.91-6.79 (m, 2H), 5.79 (qt, J=1.2, 7.3 Hz, 1H), 4.16 (m, 4H), 3.81 (s, 3H), 2.78 (q, J=7.1 Hz, 2H), 2.09 (d, J=1.2 Hz, 3H), 1.48 (t, J=7.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, major E isomer): 190.9, 158.6, 154.3, 149.1, 137.1, 135.9, 130.0, 126.6, 126.5, 120.8, 113.5, 111.8, 110.8, 68.4, 64.5, 55.2, 28.6, 16.0, 14.6 ppm. Odour description (1% solution in EtOH on paper blotter, 24 h): sweet, powdery, vanilla, ice cream, soft anisic, heliotropine, anethiol.

Example 50: 3-ethoxy-4-((4-methyl-5-phenylpent-3-en-1-yl)oxy)benzaldehyde

[0308] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (2.00 g, 12.0 mmol, 1.0 equiv) and (5-bromo-2-methylpent-2-en-1-yl)benzene (2.90 g, 12.0 mmol, 1.0 equiv, prepared according to Krafft, M. E. Tetrahedron Lett. 1989, 3, 539) according to the procedure of example 42 as a colorless liquid (0.72 g, 18% yield, E/Z 80:20).

[0309] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 9.83 (s, 1H), 7.40 (s, 2H), 7.26 (s, 2H), 7.17 (s, 3H), 6.97 (d, J=8.1 Hz, 1H), 5.41 (dt, J=1.2, 7.3 Hz, 0.2H), 5.34 (qt, J=1.2, 7.3 Hz, 0.8H), 4.24-4.00 (m, 4H), 3.54-3.38 (m, 0.4H), 3.33 (s, 1.6H), 2.73 (dq, J=1.0, 7.2 Hz, 0.4H), 2.62 (q, J=7.1 Hz, 1.6H), 1.65-1.59 (m, 3H), 1.50-1.39 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 190.9, 154.3, 149.1, 149.1, 139.9, 139.7, 138.0, 137.3, 130.0, 129.9, 128.8, 128.4, 128.4, 128.2, 126.6, 126.0, 126.0, 120.9, 120.9, 111.8, 111.7, 110.8, 68.7, 68.5, 64.5, 46.2, 37.9, 28.1, 28.0, 23.5, 16.1, 14.7, 14.6 ppm.

[0310] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, ice cream.

Example 51: (E)-3-ethoxy-4-((4-(naphthalen-2-yl)pent-3-en-1-yl)oxy)benzaldehyde

[0311] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (12.4 g, 74.6 mmol, 1.0 equiv) and (E)-2-(5-bromopent-2-en-2-yl)naphthalene (27.4 g, 74.6 mmol, 1.0 equiv, 75% purity, prepared according to Liu, X. et al., J. Am. Chem. Soc. 2018, 140, 4782) according to the procedure of example 42 as a colorless solid (12.2 g, 45% yield), after purification by fractional distillation under high vacuum (0.06 mbar).

[0312] .sup.1H NMR (400 MHz, CDCl.sub.3): 9.86 (s, 1H), 7.87-7.78 (m, 4H), 7.61 (dd, J=1.8, 8.7 Hz, 1H), 7.51-7.40 (m, 4H), 7.00 (d, J=8.6 Hz, 1H), 6.07-6.02 (m, 1H), 4.22 (t, J=7.1 Hz, 2H), 4.16 (q, J=7.1 Hz, 2H), 2.97-2.78 (m, 2H), 2.24 (d, J=1.2 Hz, 3H), 1.49 (t, J=7.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3): 190.8, 154.2, 149.1, 140.5, 137.5, 133.3, 132.4, 130.0, 127.9, 127.6, 127.4, 126.4, 126.0, 125.5, 124.2, 124.1, 123.1, 111.8, 110.8, 68.2, 64.4, 28.8, 16.0, 14.6 ppm. GC/MS (EI): m/z (%): 360 (7, [M].sup.+.Math.), 195 (100), 181 (21), 180 (24), 179 (45), 178 (32), 167 (23), 166 (39), 165 (76), 153 (32), 152 (21).

[0313] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, ice cream, floral, neroli, orange flower, baby cologne, madeleine, fougassette.

Example 52: 4-(4-((4-methyl-6-phenylhex-3-en-1-yl)oxy)phenyl)butan-2-one

[0314] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (6.49 g, 39.5 mmol, 1.0 equiv) and (6-bromo-3-methylhex-3-en-1-yl)benzene (10.0 g, 39.5 mmol, 1.0 equiv) according to the procedure of example 42 as a slightly yellow liquid (4.69 g, 35% yield, E/Z 80:20).

[0315] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 7.31-7.22 (m, 2H), 7.22-7.13 (m, 3H), 7.12-7.03 (m, 2H), 6.86-6.69 (m, 2H), 5.30-5.12 (m, 1H), 3.85 (t, J=7.1 Hz, 1.6H), 3.73 (t, J=7.0 Hz, 0.4H), 2.90-2.78 (m, 2H), 2.76-2.66 (m, 4H), 2.46 (q, J=6.8 Hz, 1.6H), 2.40-2.26 (m, 2.4H), 2.12 (s, 3H), 1.76 (d, J=1.5 Hz, 0.6H), 11.70 (s, 2.4H). .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 208.1, 157.3, 157.3 (Z), 142.2, 142.1 (Z), 137.3, 137.1 (Z), 132.9, 132.8 (Z), 129.1, 129.1 (Z), 128.4 (Z), 128.4, 128.2 (Z), 128.2, 125.8 (Z), 125.6, 121.0 (Z), 120.0, 114.5, 114.5 (Z), 67.6 (Z), 67.5, 45.4, 41.6, 34.6, 34.3 (Z), 34.1 (Z), 30.1, 28.9, 28.1, 28.0 (Z), 23.4 (Z), 16.3 ppm. GC/MS (EI) major E isomer: m/z (%): 336 (1, [M].sup.+.Math.), 164 (12), 131 (44), 117 (10), 107 (8), 105 (7), 92 (8), 91 (100), 69 (6), 67 (7), 43 (12). GC/MS (EI) minor Z isomer: m/z (%): 336 (2, [M].sup.+.Math.), 164 (13), 131 (41), 117 (9), 107 (8), 105 (7), 92 (8), 91 (100), 69 (6), 67 (6), 43 (11).

[0316] Odour description (1% solution in EtOH on paper blotter, 24 h): sweet, crystal sugar, fruity, raspberry.

Example 53: 4-(4-((4-(4-methoxyphenyl)pent-3-en-1-yl)oxy)phenyl)butan-2-one

[0317] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (1.87 g, 11.4 mmol, 1.0 equiv) and 1-(5-bromopent-2-en-2-yl)-4-methoxybenzene (2.91 g, 11.4 mmol, 1.0 equiv, prepared according to Bruecher, O. et al., Tetrahedron 2012, 6, 6968) according to the procedure of example 42 as a slightly yellow liquid (0.52 g, 13% yield, E/Z 93:7).

[0318] .sup.1H NMR (400 MHz, CDCl.sub.3, major E isomer): 7.42-7.30 (m, 2H), 7.16-7.02 (m, 2H), 6.91-6.74 (m, 4H), 5.79 (t, J=7.1 Hz, 1H), 4.03 (t, J=7.0 Hz, 2H), 3.82 (s, 3H), 2.88-2.80 (m, 2H), 2.77-2.64 (m, 4H), 2.14 (s, 3H), 2.07 (d, J=1.2 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, major E isomer): 208.2, 158.6, 157.3, 136.5, 136.1, 133.0, 129.3, 129.2, 129.1, 126.6, 121.7, 114.6, 113.5, 67.4, 55.3, 45.4, 30.1, 29.0, 28.9, 16.0 ppm.

[0319] Odour description (1% solution in EtOH on paper blotter, 24 h): sweet powdery, anisic aldehyde, fruity, raspberry ketone.

Example 54: 3-ethoxy-4-((6-(4-methoxyphenyl)-4-methylhex-3-en-1-yl)oxy)benzaldehyde

[0320] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (2.50 g, 15.0 mmol, 1.0 equiv) and 1-(6-chloro-3-methylhex-3-en-1-yl)-4-methoxybenzene (3.95 g, 16.5 mmol, 1.0 equiv, prepared according to Bruecher, O.; et al. Tetrahedron 2012, 68, 6968) according to the procedure of example 42 as a slightly yellow liquid (3.58 g, 65% yield, E/Z 80:20).

[0321] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 9.84 (2s, 1H), 7.48-7.35 (m, 2H), 7.13-7.04 (m, 2H), 6.95 (d, J=8.3 Hz, 0.8H), 6.87 (d, J=8.1 Hz, 0.2H), 6.84-6.77 (m, 2H), 5.24 (dt, J=1.2, 7.3 Hz, 0.2H), 5.19 (qt, J=1.2, 7.3 Hz, 0.8H), 4.21-4.09 (m, 2H), 4.01 (t, J=7.2 Hz, 1.6H), 3.83 (t, J=7.2 Hz, 0.4H), 3.77 (s, 2.4H), 3.75 (s, 0.6H), 2.72-2.64 (m, 2H), 2.57 (q, J=7.1 Hz, 1.6H), 2.46 (dq, J=0.9, 7.3 Hz, 0.4H), 2.36 (pseudo t, J=7.7 Hz, 0.4H), 2.33-2.26 (m, 1.6H), 1.79 (d, J=1.2 Hz, 0.6H), 1.74 (s, 2.4H), 1.48 (t, J=7.0 Hz, 2.4H), 1.45 (t, J=7.1 Hz, 0.6H). .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 190.9, 157.7, 157.6, 154.3, 154.3, 149.1, 149.0, 137.9, 137.6, 134.1, 134.0, 129.9, 129.8, 129.3, 129.2, 126.5, 120.2, 119.3, 113.6, 113.5, 111.6, 111.6, 110.7, 68.5, 68.5, 64.4, 55.1, 41.8, 34.2, 33.5, 33.2, 27.8, 27.7, 23.4, 16.2, 14.6, 14.6 ppm. GC/MS (EI) major E isomer: m/z (%): 368 (0, [M].sup.+.Math.), 203 (3), 122 (9), 121 (100), 91 (3), 81 (2), 78 (3), 77 (3), 67 (3), 65 (1), 41 (1). GC/MS (EI) minor Z isomer: m/z (%): 368 (0, [M].sup.+.Math.), 203 (3), 137 (2), 122 (9), 121 (100), 91 (3), 81 (2), 78 (3), 77 (3), 67 (3), 41 (1).

[0322] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla.

Example 55: 4-(4-((6-(4-methoxyphenyl)-4-methylhex-3-en-1-yl)oxy)phenyl)butan-2-one

[0323] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (2.50 g, 15.2 mmol, 1.0 equiv) and 1-(6-chloro-3-methylhex-3-en-1-yl)-4-methoxybenzene (4.00 g, 16.7 mmol, 1.0 equiv, prepared according to Bruecher, O.; et al. Tetrahedron 2012, 68, 6968) according to the procedure of example 42 as colorless liquid (1.95 g, 35% yield, E/Z 80:20).

[0324] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 7.17-7.01 (m, 4H), 6.89-6.74 (m, 4H), 5.34-5.15 (m, 1H), 3.88 (t, J=7.1 Hz, 1.6H), 3.79 (s, 2.4H), 3.77 (s, 0.6H), 3.74 (t, J=7.1 Hz, 0.4H), 2.90-2.81 (m, 2H), 2.79-2.64 (m, 4H), 2.54-2.45 (m, 1.6H), 2.42-2.26 (m, 2.4H), 2.15 (s, 3H), 1.79 (d, J=1.5 Hz, 0.6H), 1.72 (s, 2.4H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 208.1, 157.7, 157.6, 157.3, 137.3, 137.1, 134.2, 134.1, 132.8, 132.8, 129.3, 129.2, 129.1, 129.1, 120.9, 120.0, 114.5, 114.4, 113.6, 113.6, 67.5, 67.5, 55.1, 55.1, 45.4, 41.8, 34.2, 33.6, 33.3, 30.0, 28.9, 28.1, 28.0, 23.4, 16.3 ppm. GC/MS (EI) major E isomer: m/z (%): 366 (1, [M]+.Math.), 202 (2), 122 (9), 121 (100), 119 (1), 107 (2), 91 (3), 78 (3), 77 (4), 67 (3), 43 (4). GC/MS (EI) minor Z isomer: m/z (%): 366 (1, [M]+.Math.), 202 (2), 122 (9), 121 (100), 107 (2), 91 (4), 78 (3), 77 (3), 67 (3), 43 (5), 41 (1).

[0325] Odour description (1% solution in EtOH on paper blotter, 24 h): sweet, fruity, raspberry.

Example 56: methyl 2-((4-methyl-6-phenylhex-3-en-1-yl)oxy)benzoate

[0326] The compound was obtained from methyl 2-hydroxybenzoate (1.20 g, 7.90 mmol, 1.0 equiv) and (6-bromo-3-methylhex-3-en-1-yl)benzene (2.00 g, 7.90 mmol, 1.0 equiv) according to the procedure of example 42 as a yellow liquid (1.01 g, 39% yield, E/Z 80:20).

[0327] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 7.85-7.77 (m, 1H), 7.53-7.41 (m, 1H), 7.34-7.26 (m, 2H), 7.25-7.15 (m, 3H), 7.05-6.85 (m, 2H), 5.37-5.13 (m, 1H), 3.99 (t, J=7.1 Hz, 1.6H), 3.91 (s, 2.4H), 3.90 (s, 0.4H), 3.84 (t, J=7.1 Hz, 0.6H), 2.83-2.69 (m, 2H), 2.62-2.53 (m, 1.6H), 2.50-2.30 (m, 2.4H), 1.83-1.80 (m, 0.6H), 1.75 (s, 2.4H). .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 13C NMR (101 MHz, CDCl3, 298 K) Shift (ppm)=166.9, 158.4, 142.2, 137.3, 137.0, 133.2, 133.2, 131.5, 131.5, 128.4, 128.3, 128.2, 128.2, 125.8, 125.6, 120.8, 120.6, 120.1, 120.1, 119.9, 119.8, 113.4, 113.3, 68.6, 68.5, 51.9, 41.6, 34.5, 34.2, 34.0, 28.0, 27.9, 23.5, 16.3 ppm.

[0328] Odour description (1% solution in EtOH on paper blotter, 24 h): wintergreen, salicylate, slightly powdery, vanilla.

Example 57: 1-(2-((4-methyl-6-phenylhex-3-en-1-yl)oxy)phenyl)propan-1-one

[0329] The compound was obtained from 1-(2-hydroxyphenyl)propan-1-one (1.19 g, 7.90 mmol, 1.0 equiv) and (6-bromo-3-methylhex-3-en-1-yl)benzene (2.00 g, 7.90 mmol, 1.0 equiv) according to the procedure of example 42 as a slightly yellow liquid (0.82 g, 32% yield, E/Z 75:25).

[0330] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 7.73-7.64 (m, 1H), 7.45-7.35 (m, 1H), 7.30-7.22 (m, 2H), 7.20-7.12 (m, 3H), 6.97 (s, 1H), 6.91 (d, J=7.8 Hz, 0.75H), 6.83 (d, J=8.3 Hz, 0.25H), 5.30-5.12 (m, 1H), 3.99 (t, J=6.7 Hz, 1.5H), 3.80 (t, J=6.8 Hz, 0.5H), 3.04-2.92 (m, 2H), 2.77-2.66 (m, 2H), 2.58-2.48 (m, 1.5H), 2.41-2.26 (m, 2.5H), 1.78 (d, J=1.2 Hz, 0.75H), 1.71 (d, J=0.7 Hz, 2.25H), 1.15 (2t, J=7.1 Hz and J=7.3 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 203.6, 203.5, 157.9, 157.8, 142.0, 141.9, 137.4, 137.1, 133.1, 133.0, 130.2, 130.2, 128.4, 128.3, 128.3, 128.2, 125.9, 125.7, 121.1, 120.4, 120.4, 120.2, 112.2, 112.1, 68.1, 68.0, 41.6, 37.1, 34.5, 34.1, 34.0, 28.1, 27.8, 23.4, 16.3, 8.6 ppm.

[0331] Odour description (1% solution in EtOH on paper blotter, 24 h): wintergreen, salicylate, slightly powdery, vanilla.

Example 58: 3-ethoxy-4-((4-methyl-7-phenylhept-3-en-1-yl)oxy)benzaldehyde

a) (7-chloro-4-methylhept-4-en-1-yl)benzene

[0332] Magnesium powder (1.73 g, 71.3 mmol, 1.2 equiv) was added to a 100 ml-sulfonation flask and overlayed with THF (5 mL). Then a solution of (3-chloropropyl)benzene (11.0 g, 71.3 mmol, 1.2 equiv) in THF (30 mL) was added dropwise, after having started the Grignard reaction using a catalytic amount of iodine and by heating to reflux with a heatgun. The reaction mixture was stirred for 1 hour at room temperature. Then, a solution of 1-cyclopropylmethyl ketone (5.00 g, 59.4 mmol, 1.0 equiv) in THF (15 mL) was added dropwise to the Grignard reagent. After stirring for 3 hours at room temperature, a solution of 15 mL of 63% sulfuric acid (in water) was added dropwise at 3 C. and the reaction mixture was stirred for 18 hours at room temperature. After quenching with water (20 mL), the mixture was extracted with MTBE (30 mL). The organic layer was washed with water (30 mL), 2M NaOH (30 mL), water (30 mL), brine (30 mL), dried over MgSO4 and the solvent was removed under reduced pressure. The crude product was distilled using a Kugelrohr oven (130 C., 0.02 mbar) to give (7-chloro-4-methylhept-4-en-1-yl)benzene (11.1 g, 59% purity, 41% yield) as a colorless liquid, which was used in the next step without further purification.

b) 3-ethoxy-4-((4-methyl-7-phenylhept-3-en-1-yl)oxy)benzaldehyde

[0333] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (2.50 g, 15.0 mmol, 1.0 equiv) and (7-chloro-4-methylhept-4-en-1-yl)benzene (3.35 g, 15.0 mmol, 1.0 equiv) according to the procedure of example 42 as a yellow liquid (1.39 g, 26% yield, E/Z 75:25).

[0334] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 9.82 (2s, 1H), 7.44-7.36 (m, 2H), 7.30-7.23 (m, 2H), 7.22-7.12 (m, 3H), 7.01-6.86 (m, 1H), 5.31-5.14 (m, 1H), 4.20-3.99 (m, 4H), 2.65-2.50 (m, 4H), 2.18-2.01 (m, 2H), 1.79-1.64 (m, 5H), 1.50-1.41 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 190.9, 154.3, 154.3, 149.1, 149.1, 142.5, 142.3, 138.4, 129.9, 129.9, 128.4, 128.4, 128.4, 128.3, 128.3, 128.2, 126.5, 125.7, 125.6, 119.7, 119.0, 111.7, 111.7, 110.8, 68.7, 68.6, 64.5, 39.2, 35.8, 35.4, 31.6, 29.7, 29.5, 27.9, 27.7, 23.4, 22.7, 16.1, 14.6 ppm.

[0335] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, creamy, chocolate.

Example 59: 4-(4-((4-methyl-7-phenylhept-3-en-1-yl)oxy)phenyl)butan-2-one

[0336] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (2.50 g, 15.2 mmol, 1.0 equiv) and (7-chloro-4-methylhept-4-en-1-yl)benzene (3.39 g, 15.2 mmol, 1.0 equiv) according to the procedure of example 42 as a colorless liquid (0.89 g, 17% yield, E/Z 90:10). .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 7.31-7.23 (m, 2H), 7.23-7.13 (m, 3H), 7.12-7.03 (m, 2H), 6.86-6.74 (m, 2H), 5.34-5.06 (m, 1H), 3.98-3.84 (m, 2H), 2.90-2.77 (m, 2H), 2.75-2.66 (m, 2H), 2.62-2.53 (m, 2H), 2.52-2.38 (m, 2H), 2.16-2.00 (m, 5H), 1.78-1.68 (m, 2H), 1.65 (s, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 208.1, 157.3, 142.5, 137.6, 132.8, 129.1, 128.5, 128.4, 128.3, 128.3, 128.2, 128.2, 125.9, 125.7, 125.6, 120.4, 119.7, 114.5, 114.5, 114.5, 67.7, 67.6, 45.4, 39.2, 35.8, 35.4, 32.1, 31.6, 30.8, 30.1, 29.7, 29.5, 28.9, 28.2, 28.0, 23.4, 16.1 ppm.

[0337] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery fruity, raspberry.

Example 60: 4-((4,8-dimethylnona-3,7-dien-1-yl)oxy)-3-ethoxybenzaldehyde

[0338] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (1.086 g, 6.54 mmol, 1.1 equiv) and (E)-4,8-dimethylnona-3,7-dien-1-ol (1.0 g, 5.94 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (1.0 mmol, 0.3 g, 16% yield).

[0339] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.83 (s, 1H), 7.51-7.32 (m, 2H), 6.98-6.95 (m, 1H), 5.22 (t, J=7.1 Hz, 1H), 5.09 (t, J=6.6 Hz, 1H), 4.14 (q, J=7.0 Hz, 2H), 4.05 (q, J=6.9 Hz, 2H), 2.61-2.56 (m, 2H), 2.15-1.96 (m, 4H), 1.77-1.45 (m, 9H), 1.47 (t, J=7.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, E/Z mixtures) 191.0, 154.4, 154.4, 149.2, 138.7, 138.7, 131.8, 131.5, 129.9, 126.6, 124.1, 124.1, 119.5, 118.7, 111.8, 110.9, 68.8, 68.6, 64.6, 39.8, 32.1, 27.9, 27.8, 26.6, 26.6, 25.7, 25.7, 23.5, 17.7, 16.2, 14.7 ppm. GC/MS (EI): m/z (%): 316 (1) [M.sup.+], 166 (7), 151 (18), 109 (11), 95 (36), 69 (100).

[0340] Odour description (1% solution in EtOH on paper blotter, 24 h): gourmand (vanilla, rhum, vanilla bean) sweet (vanilla)

Example 61: 4-allyl-1-((4,8-dimethylnona-3,7-dien-1-yl)oxy)-2-methoxybenzene

[0341] The compound was obtained from 4-allyl-2-methoxyphenol (0.5 g, 3.1 mmol, 1.0 equiv) and (E)-4,8-dimethylnona-3,7-dien-1-ol (0.5 g, 3.1 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (1.8 mmol, 0.6 g, 59% yield).

[0342] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.74-6.60 (m, 3H), 5.91-5.82 (m, 1H), 5.14-4.91 (m, 4H), 3.89-3.74 (m, 5H), 3.24 (d, J=6.7 Hz, 2H), 2.49-2.42 (m, 2H), 2.03-1.91 (m, 4H), 1.68-1.45 (m, 9H). .sup.13C NMR (101 MHz, CDCl.sub.3, E/Z mixtures) 149.4, 149.4, 146.8, 146.8, 138.2, 138.1, 137.7, 132.8, 132.7, 131.7, 131.4, 124.2, 124.2, 120.5, 119.9, 119.1, 115.6, 113.2, 113.1, 112.4, 112.3, 68.8, 68.6, 56.0, 55.9, 39.8, 39.8, 32.1, 28.2, 28.1, 26.7, 26.6, 25.8, 25.7, 23.5, 17.7, 17.7, 16.2 ppm. GC/MS (EI): m/z (%): 314 (6) [M.sup.+], 177 (2), 164 (100), 149 (7), 115 (5), 95 (14), 69 (66).

[0343] Odour description (1% solution in EtOH on paper blotter, 24 h): spicy

Example 62: methyl (E)-4-((4,8-dimethylnona-3,7-dien-1-yl)oxy)-2-hydroxy-3,6-dimethylbenzoate

[0344] The compound was obtained from methyl 2,4-dihydroxy-3,6-dimethylbenzoate (1.0 g, 5.1 mmol, 1.0 equiv) and (E)-4,8-dimethylnona-3,7-dien-1-ol (0.9 g, 5.1 mmol, 1.0 equiv) according to the process of example 1 as colorless liquid (1.2 mmol, 0.4 g, 23% yield).

[0345] .sup.1H NMR (400 MHz, CDCl.sub.3) 11.74 (s, 1H), 6.14 (s, 1H), 5.13 (t, J=7.1 Hz, 1H), 5.00 (t, J=6.4 Hz, 1H), 3.85 (q, J=6.6 Hz, 2H), 3.80 (s, 3H), 2.46-2.35 (m, 5H), 2.05-1.88 (m, 7H), 1.64-1.51 (m, 9H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, E/Z mixtures) 172.6, 162.2, 161.0, 160.9, 141.0, 138.2, 138.0, 131.8, 131.4, 124.2, 124.1, 120.2, 119.4, 111.0, 106.8, 105.2, 68.0, 67.8, 51.7, 39.8, 32.1, 28.2, 28.1, 26.6, 26.6, 25.7, 25.7, 24.6, 23.4, 17.7, 17.6, 16.2, 7.9, 7.9 ppm. GC/MS (EI): m/z (%): 346 (3) [M.sup.+], 277 (2), 245 (5), 197 (38), 177 (16), 164 (24), 135 (14), 95 (20), 69 (100).

[0346] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery (mossy)

Example 63: (E)-3-ethoxy-4-((3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pent-4-en-2-yl)oxy)benzaldehyde

[0347] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (1.8 g, 11.0 mmol, 1.0 equiv) and (E)-4-(4-bromo-3-methylpent-1-en-1-yl)-1,5,5-trimethylcyclopent-1-ene (3.0 g, 11.0 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (1.1 mmol, 0.4 g, 10% yield).

[0348] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.83 (s, 1H), 7.41 (d, J=7.5 Hz, 2H), 6.99-6.95 (m, 1H), 5.67-5.30 (m, 2H), 5.23 (s, 1H), 4.74-4.08 (m, 3H), 2.92-0.74 (m, 22H) ppm. GC/MS (EI): m/z (%): 356 (5) [M.sup.+], 281 (5), 207 (13), 191 (42), 166 (50), 149 (36), 137 (99), 109 (100), 90 (70), 55 (72).

[0349] Odour description (1% solution in EtOH on paper blotter, 24 h): woody, sandalwoody, hay

Example 64: (Z)-3-ethoxy-4-(non-3-en-1-yloxy)benzaldehyde

[0350] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (5.0 g, 30.1 mmol, 1.0 equiv) and (Z)-1-bromonon-3-ene (6.2 g, 30.1 mmol, 1.0 equiv) according to the process of example 1 as colorless liquid (16.5 mmol, 4.8 g, 55% yield).

[0351] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.73 (s, 1H), 7.33-7.30 (m, 2H), 6.86 (d, J=8.1 Hz, 1H), 5.50-5.32 (m, 1H), 4.11-3.90 (m, 4H), 2.56-2.50 (m, 2H), 2.02-1.97 (m, 2H), 1.37 (t, J=7.0 Hz, 3H), 1.33-1.14 (m, 6H), 0.79 (t, J=6.8 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9, 154.3, 149.1, 133.3, 130.0, 126.5, 123.9, 111.8, 110.8, 68.5, 64.5, 31.5, 29.3, 27.3, 27.2, 22.5, 14.7, 14.0 ppm. GC/M S (EI): m/z (%): 290 (11) [M+], 192 (1), 166 (100), 151 (7), 138 (57), 83 (42), 69 (73), 55 (60).

[0352] Odour description (1% solution in EtOH on paper blotter, 24 h): vanilla (powdery, spicy, creamy)

Example 65: 2-ethoxy-4-methyl-1-((4,8,12-trimethyltrideca-3,7,11-trien-1-yl)oxy)benzene

[0353] The compound was obtained from 2-ethoxy-4-methylphenol (5.2 g, 27.4 mmol, 1.0 equiv) and 4,8,12-trimethyltrideca-3,7,11-trien-1-ol (7.8 g, 32.8 mmol, 1.2 equiv) according to the procedure of example 1 as colorless liquid (14.3 mmol, 5.3 g, 51% yield).

[0354] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.78 (d, J=8.0 Hz, 1H), 6.74-6.59 (m, 2H), 5.23-5.07 (m, 3H), 4.06 (q, J=7.0 Hz, 2H), 3.94 (t, J=7.2 Hz, 2H), 2.55-2.49 (m, 2H), 2.27 (s, 3H), 2.17-1.90 (m, 8H), 1.73-1.60 (m, 12H), 1.43 (t, J=6.9 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers) 148.7, 146.7, 138.0, 137.9, 135.1, 131.3, 130.7, 124.4, 124.1, 124.0, 121.1, 120.3, 119.5, 115.0, 115.0, 114.2, 69.0, 64.6, 39.8, 39.8, 32.1, 28.3, 28.2, 26.8, 26.7, 26.6, 25.7, 23.5, 21.0, 17.7, 16.2, 16.0, 15.0. GC/MS (EI): m/z (%): 370 (6) [M.sup.+], 234 (1), 214 (1), 152 (100), 137 (9), 124 (16), 81 (33), 69 (53).

[0355] Odour description (1% solution in EtOH on paper blotter, 24 h): phenolic (medicinal, ultravanil, balsamic vanilla bean, cough syrup)

Example 66: methyl 2-hydroxy-3,6-dimethyl-4-((4,8,12-trimethyltrideca-3,7,11-trien-1-yl)oxy)benzoate

[0356] The compound was obtained from methyl 2,4-dihydroxy-3,6-dimethylbenzoate (6.6 g, 33.8 mmol, 1.0 equiv) and 4,8,12-trimethyltrideca-3,7,11-trien-1-ol (8.0 g, 33.8 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (28.0 mmol, 11.6 g, 83% yield). .sup.1H NMR (400 MHz, CDCl.sub.3) 11.74 (s, 1H), 6.11 (s, 1H), 5.23-4.89 (m, 3H), 3.91-3.69 (m, 5H), 2.49-2.24 (m, 5H), 2.08-1.79 (m, 11H), 1.64-1.45 (m, 12H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers) 172.6, 162.3, 161.0, 140.0, 138.2, 138.0, 135.4, 135.1, 131.2, 131.2, 124.4, 124.4, 124.0, 123.9, 120.2, 119.5, 111.0, 106.7, 105.2, 68.0, 67.8, 51.6, 39.8, 32.1, 28.3, 28.1, 26.8, 26.7, 26.5, 25.7, 24.6, 23.5, 17.7, 16.2, 16.0, 7.9 ppm. GC/MS (EI): m/z (%): 414 (1) [M.sup.+], 389 (1), 244 (75), 217 (13), 201 (100), 173 (28), 145 (52), 119 (39), 55 (54).

[0357] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery mossy (evernyl)

Example 67: 4-(4-((4,8,12-trimethyltrideca-3,7,11-trien-1-yl)oxy)phenyl)butan-2-one

[0358] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (4.5 g, 27.5 mmol, 1.0 equiv) and 4,8,12-trimethyltrideca-3,7,11-trien-1-ol (6.5 g, 27.5 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (20.0 mmol, 7.8 g, 74% yield).

[0359] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.07 (d, J=8.6 Hz, 2H), 6.88-6.72 (m, 2H), 5.28-5.15 (m, 1H), 5.15-5.03 (m, 2H), 3.91-3.86 (m, 2H), 2.84-2.68 (m, 2H), 2.50-2.44 (m, 2H), 2.16-1.91 (m, 11H), 1.82-1.55 (m, 12H). .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers) 208.1, 157.4, 138.1, 137.9, 135.3, 135.1, 132.9, 131.3, 131.2, 129.2, 124.4, 124.4, 124.1, 124.0, 120.3, 119.5, 114.6, 114.6, 67.8, 67.7, 45.5, 39.7, 39.7, 32.1, 30.1, 29.0, 28.2, 28.1, 26.8, 26.7, 26.5, 26.5, 25.7, 23.5, 17.7, 16.2, 16.1, 16.0. GC/MS (EI): m/z (%): 414 (1) [M.sup.+], 382 (2), 246 (15), 219 (2), 187 (18), 164 (15), 82 (59), 69 (100).

[0360] Odour description (1% solution in EtOH on paper blotter, 24 h): fruity powdery (raspberry)

Example 68: 3-ethoxy-4-((1-phenylbut-3-en-1-yl)oxy)benzaldehyde

[0361] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (5.0 g, 30.1 mmol, 1.0 equiv) and 1-phenylbut-3-en-1-ol (5.4 g, 36.1 mmol, 1.2 equiv) according to the procedure of example 1 as colorless liquid (16.9 mmol, 5.0 g, 56% yield).

[0362] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.74 (s, 1H), 7.37-7.21 (m, 7H), 6.78 (d, J=8.2 Hz, 1H), 5.95-5.75 (m, 1H), 5.26-5.07 (m, 3H), 4.15 (q, J=7.0 Hz, 2H), 2.88-2.64 (m, 2H), 1.48 (t, J=7.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 191.0, 153.6, 149.9, 140.5, 133.7, 130.3, 128.6, 127.9, 126.2, 126.1, 118.0, 115.1, 111.6, 81.4, 64.8, 42.7, 14.8 ppm. GC/MS (EI): m/z (%): 296 (1) [M.sup.+], 255 (1), 225 (8), 166 (6), 149 (6), 131 (100), 115 (20), 103 (8), 91 (63), 77 (12).

[0363] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery (vanilla), green

Example 69: methyl (Z)-4-(deca-1,7-dien-4-yloxy)-2-hydroxy-3,6-dimethylbenzoate

[0364] The compound was obtained from methyl 2,4-dihydroxy-3,6-dimethylbenzoate (6.0 g, 30.6 mmol, 1.0 equiv) and (Z)-deca-1,7-dien-4-ol (5.2 g, 33.6 mmol, 1.1 equiv) according to the procedure of example 1 as colorless liquid (12.3 mmol, 4.1 g, 41% yield).

[0365] .sup.1H NMR (400 MHz, CDCl.sub.3) 11.78 (s, 1H), 6.16 (s, 1H), 5.76-5.68 (m, 1H), 5.40-5.12 (m, 2H), 5.09-4.89 (m, 2H), 4.35-4.25 (m, 1H), 3.81 (s, 3H), 2.40-2.34 (m, 5H), 2.07-1.60 (m, 9H), 0.82 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 171.5, 161.5, 159.2, 138.7, 132.7, 131.6, 126.9, 116.7, 110.9, 106.9, 104.0, 75.3, 50.7, 37.3, 32.7, 23.6, 21.9, 19.4, 13.2, 7.0 ppm. GC/MS (EI): m/z (%): 332 (10) [M.sup.+], 301 (1), 259 (1), 196 (29), 164 (100), 136 (22), 95 (12).

[0366] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery green marine (evernyl)

Example 70: Application in Liquid Detergent

a) Sample Preparation

[0367] 0.2% by weight of ethyl vanillin (3-ethoxy-4-hydroxybenzaldehyde, sample A) or (Z)-3-ethoxy-4-(pentadec-3-en-6-yloxy)benzaldehyde (compound of example 28, sample B) were incorporated respectively into unperfumed liquid detergent base by magnetic stirring at room temperature for 24 h.

b) Colour Stability

[0368] The above prepared samples were visually inspected in comparison to an unperfumed base sample (sample C). The ethylvanillin sample (A) showed strong purple coloration, whereas the sample containing the precursor (B) was optically identical to the unperfumed base (C). All three samples are shown in FIG. 1.

c) Washtest and Sensory Evaluation

[0369] A 40 C. machine wash cycle was performed using 55 g of the above prepared liquid detergent samples A and B and odour-neutral cotton/elastan mixed fabric T-shirts. The wet and line-dried fabric (1 and 4 days) was assessed by a panel of 4-6 experts with regard to odour intensity and quality. The odour intensity was recorded on an intensity scale of 0 (odourless) to 5 (extremely strong). As can be seen from Table 1 below, virtually no odour was released from the fabric washed with the colored ethyl vanillin detergent base, whereas the fabric washed with the color-neutral detergent base containing (Z)-3-ethoxy-4-(pentadec-3-en-6-yloxy)benzaldehyde exhibited a mandarin, vanilla and powdery fragrance after 1 and 3 days.

TABLE-US-00001 TABLE 1 Sample wet 1 day 4 days Ethylvanillin (A) 1.2 0.9 1 (Z)-3-ethoxy-4-(pentadec-3- 2.1 2.3 2.6 en-6-yloxy)benzaldehyde (B)

[0370] The experiment demonstrates that free ethylvanillin is not suitable for application in liquid detergent, as it colors the base and, due to its high water solubility, does not impart any fragrance to washed and dried fabric. These technical limitations are overcome by the compound of the present invention, which is not colorizing and imparts a mandarin and vanilla-powdery fragrance on dry fabric.

Example 71: Comparison of Regioisomeric Side Chain Olefins

[0371] In order to highlight the importance of the position of the double bond, a comparative assessment in liquid detergent application (as described in Example 70a and c) was carried out with ethylvanillin ethers (compounds of formula IV), having unsaturated side chains with the double bond placed in positions -2 or -4 in comparison to the compounds of the current invention which have the double bond positioned at -3.

[0372] The compound with the double bond in -2 position, 3-ethoxy-4-(((2Z,5Z)-octa-2,5-dien-1-yl)oxy)benzaldehyde, was prepared by stirring ethyl vanillin with (Z)-3-chloroocta-1,5-diene in the presence of potassium carbonate (1.5 equiv) and tetrabutyl ammonium iodide (0.15 equiv.) in acetonitrile under reflux for 40 h. Standard workup and purification yielded 3-ethoxy-4-(((2Z,5Z)-octa-2,5-dien-1-yl)oxy)benzaldehyde as a pale yellow oil (13%). GC/MS (EI, 70 eV): 274 (1, [M].sup.+), 166 (19), 137 (25), 109 (32), 79 (48), 67 (100), 55 (37).

[0373] The compound with the double bond in A-4 position, (Z)-3-ethoxy-4-(hexadec-3-en-7-yloxy)benzaldehyde, was prepared by reacting (Z)-hexadec-3-en-7-ol (from the reaction of (Z)-hex-3-en-1-ylmagnesium chloride with decanal) and ethyl vanillin according to the procedure of example 1 to yield (Z)-3-ethoxy-4-(hexadec-3-en-7-yloxy)benzaldehyde as a liquid (32%). GC/MS (EI, 70 eV): 388 (<1, [M].sup.+), 222 (1), 166 (100), 138 (18), 109 (12), 97 (31), 83 (43), 69 (42), 55 (43).

[0374] The odour intensity was recorded on an intensity scale of 0 (odorless) to 5 (extremely strong). The results are summarized in Table 2.

##STR00013##

TABLE-US-00002 TABLE 2 position of double 1 3 Entry Compound bond wet day days odour on dry fabric 1 3-ethoxy-4-(((2Z,5Z)-octa-2,5- -2 0.9 2.8 2.3 metallic dien-1-yl)oxy)benzaldehyde 2 3-ethoxy-4-(((3Z,6Z)-nona-3,6- -3 2.7 3.4 4.1 vanilla, green dien-1-yl)oxy)benzaldehyde (Example 30) 3 (Z)-3-ethoxy-4-(hexadec-3-en- -4 1.1 1.2 1.6 rubbery, metallic 7-yloxy)benzaldehyde

[0375] The results show that only the compound of the present invention with the double bond in the -3 position of the side chain (homoallylic ether, entry 2) releases a strong and pleasant odour on dry fabric, whereas comparable compounds with the double bond in the -2 or -4 position (entries 1 and 3), respectively, release only weak and unpleasant odours.

Example 72: Application in Liquid Detergent: Generation of Different Odour Profiles

[0376] Heavy duty liquid detergent samples were prepared and used in washtests and subsequent sensory evaluation of the washed and dried fabric as described in Example 60a and c. The odour intensity was recorded on an intensity scale of 0 (odourless) to 5 (extremely strong). The results are summarized in Table 3.

TABLE-US-00003 TABLE 3 1 4 odour on Entry wet day days dry fabric 1 (Z)-3-ethoxy-4-(pentadec-3-en-6- 2.1 2.3 2.6 mandarin, vanilla, yloxy)benzaldehyde powdery 2 3-ethoxy-4-(((3Z,6Z)-nona-3,6-dien-1- 2.7 3.4 4.1 green, powdery, yl)oxy)benzaldehyde vanilla 3 (E)-3-ethoxy-4-((4-methylnon-3-en-1- 2.1 2.8 3.3 vanilla, aldehydic, yl)oxy)benzaldehyde green 4 (Z)-4-(deca-1,7-dien-4-yloxy)-3- 0.4 3.0 3.7 green, violet, ethoxybenzaldehyde cucumber, vanilla 5 3-methoxy-4-(tetradec-1-en-4- 2.2 3.0 3.2 vanilla, mandarin, yloxy)benzaldehyde citrus, madeleine 6 (E)-4-(4-((4-methyl-6-phenylhex-3-en-1- 1.6 2.9 3.3 raspberry, sweet yl)oxy)phenyl)butan-2-one 7 (E)-3-ethoxy-4-((4-methyl-6-phenylhex-3- 1.5 2.7 3.0 sweet, vanilla, en-1-yl)oxy)benzaldehyde raspberry 8 4-allyl-2-methoxy-1-(tridec-1-en-4- 2.1 2.1 2.7 spicy, vanilla, yloxy)benzene green, oranger 9 methyl (Z)-4-(deca-1,7-dien-4-yloxy)-2- 0.5 1.9 2.5 mossy, woody hydroxy-3,6-dimethylbenzoate

[0377] The results illustrate that strong fragrance intensities are achieved on dry fabric with compounds of the current invention. The odour direction of a given parent phenol (e.g. ethylvanillin) can be modulated or even dominated by odorants released from the side chain. It also illustrates that other aromas can be generated through the appropriate combination of phenolic and side chain moieties. For example, the popular aroma of madeleine can be released by the compound of example 38, as shown in entry 5 in Table 3).

Example 73: Application in Shampoo Base

[0378] Hair shampoo samples (20 g) were prepared by adding 0.2% by weight of ethyl vanillin or compounds of the present invention to unperfumed clear hair shampoo base and mixing on a bottle roller for 24 h at room temperature. Odour-neutral human hair swatches were wetted with warm tap water and lathered delicately with 2 mL of the above hair shampoo samples for 30 sec by hand wearing gloves. The lathered hair swatches were left in a plastic bowl for 2 min, then rinsed under running tap water for 20 sec. After removing excess water by squeezing the hair swatches between two fingers, they were left to dry in open air. The wet and dried hair swatches (1 and 3 days) were assessed by a panel of 4-6 experts with regard to odour intensity and quality. The odour intensity was recorded on an intensity scale of 0 (odourless) to 5 (extremely strong). The results are summarized in Table 4.

TABLE-US-00004 TABLE 4 Entry wet 1 day 3 days odour on dry hair 1 ethylvanillin 4.2 3.0 2.5 vanilla, powdery 2 (Z)-3-ethoxy-4-(pentadec-3-en-6- 1.7 3.5 4.4 mandarin, vanilla yloxy)benzaldehyde (Example 28) 3 4-(4-(tridec-1-en-4- 2.3 1.9 1.6 raspberry, fruity, yloxy)phenyl)butan-2-one (Example floral 36) 4 3-ethoxy-4-((4-methyl-6-phenylhex-3- 1.4 2.7 2.1 vanilla, raspberry, en-1-yl)oxy)benzaldehyde (Example sweet, floral 47) 5 3-ethoxy-4-((4-methyldodec-3-en-1- 1.1 2.7 2.9 vanilla, sweet, yl)oxy)benzaldehyde (Example 90) chocolate 6 3-ethoxy-4-((4-methylnon-3-en-1- 1.0 1.4 1.9 vanilla, sweet yl)oxy)benzaldehyde (Example 42) 7 4-(4-((6-(4-methoxyphenyl)-4- 1.1 2.8 3.0 fruity, raspberry, methylhex-3-en-1- sweet yl)oxy)phenyl)butan-2-one (Example 55) 8 4-((5,9-dimethyldeca-3,8-dien-1- 0.7 2.7 3.6 vanilla, powdery, yl)oxy)-3-ethoxybenzaldehyde spicy (Example 84)

[0379] The experiment demonstrates that the precursors of the current invention are capable of releasing fragrance on dry hair, which is becoming stronger over time, whereas the odour of free ethylvanillin fades during the same time period.

Example 74: Headspace Analysis of Released Volatiles

[0380] A solution of the compound of formula (I) (100 g, 1.0 mg/mL solution in MTBE) was evenly applied through a displacement pipette to a paper strip (1 cm8 cm). The paper strip was left to dry (1 h at room temperature), then folded in the middle and inserted in V-shape into a 20 mL headspace vial (FIG. 2). The vial was closed with a septum screwcap and placed in a cabinet equipped with a fluorescent daylight imitation lamp and mirrored walls for 24 h (temperature 27-28 C.).

[0381] Extraction and analysis of the released organic volatiles was effected in automated mode on a Trace 1310 gas chromatograph equipped with a TriPlus RSH autosampler (Thermo Fisher Scientific), coupled to a ISQ LT mass spectrometer (Thermo Fisher Scientific). The extraction of the organic volatiles from the headspace with SPME (solid phase microextraction) was carried out during 1 h at 40 C. using a 50/30 m divinylbenzene/carboxen/polydimethylsiloxane SPME fibre (DVB/CAR/PDMS, Supelco P/N 57298-U), and subsequently desorbed in splitless mode at 250 C. for 1 min. GC-MS analysis (gas chromatography with mass spectrometric detection) was carried out with a VF-WAXms capillary column (Agilent, 30 m length, 0.25 mm I.D., 0.25 m film thickness). Helium was used as a carrier gas with a constant flow rate of 1 ml/min. The GC oven temperature was programmed from 35 C. with 2-min hold to 250 C. at 5 C./min with a 10-min final temperature hold. The mass spectrometer was operated at 70 eV in EI mode over a m/z range of 33-350, scanned at 0.2 s intervals and with a temperature of transfer line and ion source of 230 C. and 220 C., respectively. A list of identified volatiles released from the compounds of formula (I) is reported in the Table 5 (indicated are relative peak area %; in bold: main odor vector).

TABLE-US-00005 TABLE 5 Precursor Released Volatiles (MS-TIC peak area %) (Z)-4-(deca-1,7-dien-4-yloxy)-3- 2,6-Nonadienal (4.7%), ethylvanillin ethoxybenzaldehyde (0.03%) (E)-3-ethoxy-4-(pentadec-3-en-6- Decanal (4.7%), 2-dodecenal (1.2%), yloxy)benzaldehyde ethylvanillin (0.02%) 4-(dec-1-en-4-yloxy)-3- 2-Nonenal (4.1%), 1-decen-4-ol (25.5%), 3- ethoxybenzaldehyde decen-2-one (5.1%), ethylvanillin (0.05%) 3-ethoxy-4-(((3Z,6Z)-nona-3,6-dien-1- 2-Pentenal (13.1%), 1-penten-3-ol (11.8%), yl)oxy)benzaldehyde 2-hexenal (11.4%), nona-3,6-dien-1-ol, (8.0%), ethylvanillin (0.8%) 3-ethoxy-4-((1-phenylbut-3-en-1- benzaldehyde (12.7%), acetophenone yl)oxy)benzaldehyde (1.8%), 1-phenylbut-3-en-1-ol (21%), cinnamaldehyde (0.3%), ethylvanillin (0.3%) methyl 2-((4-methyl-6-phenylhex-3-en-1- methyl salicylate (21.7%), 4-phenyl-2- yl)oxy)benzoate (example 56) butanone (5.2%) 3-ethoxy-4-((4-(naphthalen-2-yl)pent-3-en- 2-acetyl naphtalene (Oranger Crystals, 1-yl)oxy)benzaldehyde (example 51) 12.8%), ethylvanillin (1.0%) 3-ethoxy-4-((4-methyl-6-phenylhex-3-en-1- benzylacetone (45.5%), yl)oxy)benzaldehyde (example 47) ethylvanillin (0.5%)

[0382] It should be noted that the indicated relative peak area % values are not related to molar release rates. The relative amount of each volatile in the gas phase depends mainly on volatility. Therefore, the sensory active phenols appear as minor components.

[0383] The results show that besides phenolic fragrant compounds like ethylvanillin or methyl salicylate, further sensorially active aldehydes, ketones and alcohols are released from compounds of formula (I).

[0384] The sensorially active phenols were observed also in samples which were not exposed to a light source under otherwise identical conditions indicating that the release can occur upon exposure to ambient air by oxidation in the presence or absence of light.

Example 75: Assessment of Biodegradability

[0385] The results of the biodegradability assessment by the manometric respirometry test (OECD guideline for the testing of materials No. 301F, Paris 1992) are summarized in Table 6.

TABLE-US-00006 TABLE 6 Compound Biodegra- of example Compound name dation in % result 29 (E)-3-ethoxy-4-(pentadec-3-en-6- 70 inherently yloxy)benzaldehyde biodegradable 17 3-ethoxy-4-(undec-3-en-6- 86 inherently yloxy)benzaldehyde biodegradable 1 methyl (Z)-12-(2-ethoxy-4- 90 readily formylphenoxy)octadec-9-enoate biodegradable 2 methyl (Z)-12-(4-(3- 88 readily oxobutyl)phenoxy)octadec-9-enoate biodegradable

[0386] The results show that compounds of the present invention with varying phenol moieties and side chains are biodegradable. A compound can be classified biodegradable, if it reaches the pass level of 60% oxygen consumption of theory required for complete mineralization.

[0387] It is readily biodegradable, if the pass level is reached within 10 days within the 28-day period of the test. The 10-day window begins when the degree of biodegradation has reached 10%. If the pass level is obtained after 28-day period of the test, the compound can be classified as inherently biodegradable.

Example 76: 4-(((3E,9Z)-dodeca-3,9-dien-1-yl)oxy)-3-ethoxybenzaldehyde

a) (Z)-1-cyclopropylnon-6-en-1-ol

[0388] To the suspension of magnesium (4.16 g, 171 mmol, 1.2 equiv.) in tetrahydrofurane (THF, 10 mL) was added a solution of bromocyclopropane (20.7 g, 171 mmol, 1.2 equiv) in THF (150 mL) in the following way: the first 10 mL were added at once, then the reaction was started by heating to reflux with a heat gun, then the remainder of the solution was added dropwise under stirring. The solution was stirred for 1 h after completed addition, then cooled to 5 C. The solution of 6-(Z)-nonenal (20.0 g, 143 mmol, 1.0 equiv.) in THF (60 mL) was added dropwise at 5-15 C. After completed addition, the solution was stirred for 40 min, then poured on 2 N aq. HCl-solution (250 mL). The mixture was extracted with methyl t-butyl ether (MTBE, 200 mL), the organic layer was washed with water and brine and dried over MgSO.sub.4. After removal of the solvent in a rotary evaporator, (Z)-1-cyclopropylnon-6-en-1-ol (26.25 g, >99%) was obtained as a clear yellow liquid. The product was used without purification in the subsequent step.

b) Preparation of (9Z)-1-bromododeca-3,9-diene

[0389] To the above prepared product (26.25 g, 143 mmol) was added dropwise aq. HBr solution (48% wt/wt, 32.6 mL, 288 mmol, 2.0 equiv.). After completed addition, the dark brown mixture was stirred at 50 C. for 24 h, then poured on cold 2N aq. NaOH solution (250 mL). Workup was effected as described above to yield a clear, brown liquid (30.7 g, 87%). The product was purified by filtration over silica, eluting with n-pentane. (9Z)-1-bromododeca-3,9-diene was obtained as a clear, yellow liquid (20.2 g, 57%, purity 89% according to GC-MS).

[0390] .sup.1H-NMR (500 MHz, CDCl.sub.3) 5.52-5.59 (m, 1H), 5.31-5.46 (m, 3H), 3.39 (t, J=7.2 Hz, 2H), 2.45-2.69 (m, 2H), 1.97-2.20 (m, 6H), 1.30-1.52 (m, 4H), 0.98 (t, J=7.6 Hz, 3H). .sup.13C-NMR (126 MHz, CDCl.sub.3) 133.9 (s), 131.7 (s), 129.1 (s), 126.5 (s), 36.1 (t), 32.9 (t), 32.4 (t), 29.2 (t), 28.9 (t), 26.9 (t), 20.5 (t), 14.4 (q). GC/MS (EI): m/z (%) 246 (<1, [M.sup.+]), 204 (3), 188 (2), 160 (7), 110 (55), 95 (33), 81 (90), 67 (100), 55 (56), 41 (96).

c) Preparation of 4-(((3E,9Z)-dodeca-3,9-dien-1-yl)oxy)-3-ethoxybenzaldehyde

[0391] To the solution of ethyl vanillin (1.13 g, 6.8 mmol, 1 equiv) in dimethyl formamide (DMF, 50 mL) was added K.sub.2CO.sub.3 (1.88 g, 13.6 mmol, 2 equiv.) followed by (9Z)-1-bromododeca-3,9-diene (1.83 g, 4.5 mmol, 1.1 equiv, as prepared above). The mixture was heated under stirring to 80 C. for 24 h, then cooled to room temperature and poured on water (100 mL). Workup was effected as described in chapter 1.1. to yield a clear, yellow liquid (1.71 g). The crude product was purified by column chromatography on silica with heptane/MTBE 84:16 to afford 4-(((3E,9Z)-dodeca-3,9-dien-1-yl)oxy)-3-ethoxybenzaldehyde (0.82 g, 37%) as a clear, colourless liquid with a purity of 95% according to GC-MS.

[0392] .sup.1H-NMR (500 MHz, CDCl.sub.3) 9.85 (s, 1H), 7.41-7.45 (m, 2H), 6.98 (d, J=8.1 Hz, 1H), 5.56-5.65 (m, 1H), 5.46-5.54 (m, 1H), 5.29-5.44 (m, 2H), 4.16 (q, J=6.8 Hz, 2H), 4.12 (t, J=7.3 Hz, 2H), 2.58 (q, J=6.6 Hz, 2H), 1.95-2.15 (m, 6H), 1.48 (t, J=7.0 Hz, 3H), 1.30-1.45 (m, 4H), 0.97 (t, J=7.5 Hz, 3H). .sup.13C-NMR (126 MHz, CDCl.sub.3) 190.9 (d), 154.4 (s), 149.2 (s), 133.8 (d), 131.7 (d), 130.0 (s), 129.1 (d), 126.6 (d), 124.8 (d), 111.9 (d), 111.0 (d), 68.9 (t), 64.6 (t), 32.5 (t), 32.3 (t), 29.2 (t), 28.9 (t), 26.9 (t), 20.5 (t), 14.7 (q), 14.4 (q).

[0393] GC/MS (EI): m/z (%) 330 (11, [M.sup.+]), 166 (77), 151 (6), 149 (9), 138 (43), 123 (32), 109 (48), 97 (12), 95 (75), 81 (90), 69 (65), 67 (80), 55 (100), 41 (95).

[0394] Odour description (1% solution in EtOH on paper blotter, 24 h): green, melon, powdery, vanilla.

Example 77: methyl 4-(((3E,9Z)-dodeca-3,9-dien-1-yl)oxy)-2-hydroxy-3,6-dimethylbenzoate

[0395] The procedure described in example 76c) was repeated with methyl 2,4-dihydroxy-3,6-dimethylbenzoate (2.0 g, 10 mmol), (9Z)-1-bromododeca-3,9-diene (2.70 g, 11.0 mmol, 1.1 equiv, as prepared in example 76b)) and K.sub.2CO.sub.3 (2.80 g, 20.0 mmol, 2 equiv.). After workup and purification (flash chromatography on silica, heptane/MTBE 6:1 to 1:1, followed by removal of volatile impurities at 110 C./0.04 mbar in a Kugelrohr oven), methyl 4-(((3E,9Z)-dodeca-3,9-dien-1-yl)oxy)-2-hydroxy-3,6-dimethylbenzoate (0.75 g, 19%) was obtained as clear, slightly yellow liquid with a purity of >99% according to GC-MS.

[0396] .sup.1H-NMR (400 MHz, CDCl.sub.3) 11.85 (s, 1H), 6.27 (s, 1H), 5.45-5.63 (m, 2H), 5.30-5.43 (m, 2H), 4.02 (t, J=6.7 Hz, 2H), 3.94 (s, 3H), 2.46-2.60 (m, 5H), 2.01-2.14 (m, 9H), 1.25-1.53 (m, 4H), 0.98 (t, J=7.5 Hz, 3H). .sup.13C-NMR (101 MHz, CDCl.sub.3) 172.6 (s), 162.2 (s), 160.9 (s), 140.0 (s), 133.4 (d), 131.7 (d), 129.1 (d), 125.4 (d), 111.1 (s), 106.8 (d), 105.3 (s), 67.9 (t), 51.7 (q), 32.6 (t), 32.6 (t), 29.2 (t), 29.0 (t), 26.9 (t), 24.6 (q), 20.5 (t), 14.4 (q), 7.9 (q). GC/MS (EI): m/z (%) 360 (11, [M.sup.+]), 196 (90), 164 (100), 136 (22), 81 (31), 69 (28), 67 (32), 55 (42), 41 (51).

[0397] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, oakmoss.

Example 78: 4-(deca-1,7-dien-4-yloxy)-3-ethoxybenzaldehyde

a) Deca-1,7-dien-4-ol

[0398] To a solution of allylmagnesium bromide (63 mL, 107 mmol, 0.5 M) in THF (150 mL) was added hept-4-enal (10.0 g, 89 mmol) slowly at 10 C. and stirred for 3 hours at rt. The mixture was quenched by adding NH.sub.4Cl solution, and extracted with MTBE (3*100 mL), the organic layers were combined, dried over MgSO.sub.4, filtered and solvent was removed by rotary evaporation, the residue was purified by column chromatography on silica gel (PE:MTBE=4:1) to give deca-1,7-dien-4-ol (7.6 g, yield: 55%) as colorless liquid.

[0399] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers) 5.90-5.70 (m, 1H), 5.58-5.28 (m, 2H), 5.20-5.07 (m, 2H), 3.73-3.55 (m, 1H), 2.35-2.22 (m, 1H), 2.21-1.95 (m, 5H), 1.88 (d, J=4.2 Hz, 1H), 1.60-1.47 (m, 2H), 0.96 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers) 134.9, 134.8, 132.6, 132.3, 128.6, 128.5, 118.0, 117.9, 70.3, 41.9, 41.9, 36.7, 36.5, 28.8, 25.6, 23.4, 20.5, 14.3, 13.9 ppm. GC/MS (EI): m/z (%): 154 (1) [M.sup.+], 136 (3), 95 (100), 69 (82), 55 (24).

b) 4-(Deca-1,7-dien-4-yloxy)-3-ethoxybenzaldehyde

[0400] 4-(Deca-1,7-dien-4-yloxy)-3-ethoxybenzaldehyde was obtained from 3-ethoxy-4-hydroxybenzaldehyde (5.9 g, 36 mmol) and deca-1,7-dien-4-ol (5.0 g, 32 mmol) according to the process of example 1 as light yellow liquid (6.1 g, 62% yield).

[0401] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers) 9.74 (s, 1H), 7.38-7.23 (m, 2H), 6.89 (d, J=8.7 Hz, 1H), 5.83-5.73 (m, 1H), 5.41-5.20 (m, 2H), 5.12-4.95 (m, 2H), 4.42-4.26 (m, 1H), 4.04 (q, J=7.0 Hz, 2H), 2.52-2.29 (m, 2H), 2.15-1.95 (m, 2H), 1.87-1.56 (m, 4H), 1.36 (t, J=7.0 Hz, 3H), 0.90-0.77 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers) 190.9, 154.1, 150.1, 133.8, 133.7, 133.0, 132.6, 130.2, 128.0, 127.9, 126.2, 117.8, 117.8, 114.7, 114.5, 111.8, 111.7, 78.6, 78.5, 64.6, 38.3, 38.2, 33.7, 33.6, 28.3, 25.6, 22.9, 20.4, 14.7, 14.2, 13.9 ppm. GC/MS (EI): m/z (%): 302 (7) [M.sup.+], 166 (100), 138 (51), 95 (31), 81 (25), 67 (23).

[0402] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla

Example 79: 4-((6-(benzo[d][1,3]dioxol-5-yl)-4-methylhex-3-en-1-yl)oxy)-3-ethoxybenzaldehyde

a) 5-(6-bromo-3-methylhex-3-en-1-yl)benzo[d][1,3]dioxole

[0403] To a suspension of magnesium (1.64 g, 67.6 mmol, 1.3 equiv) overlayed with THF (5 mL) was added dropwise a solution of bromocyclopropane (7.55 g, 62.4 mmol, 1.2 equiv) in THF (20 mL), after having started the Grignard reaction using a catalytic amount of iodine and by heating to reflux with a heatgun. The reaction mixture was refluxed for 40 minutes. Then, a solution of 4-(benzo[d][1,3]dioxol-5-yl)butan-2-one (10.0 g, 52.0 mmol, 1.0 equiv) in THF (75 mL) was added dropwise at 10-15 C. over 25 minutes to the Grignard reagent. After stirring for 1.5 hour at room temperature, a solution of 62% sulfuric acid (56 g, 6.8 equiv, solution in water) was added dropwise at room temperature and the reaction mixture was stirred for 30 minutes at room temperature. After quenching with water (50 mL), the reaction mixture was extracted with MTBE (330 mL). The combined organic layers were washed with water (350 mL), brine (50 mL), dried over MgSO.sub.4 and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (heptane/MTBE 8:2) to give 5-(6-bromo-3-methylhex-3-en-1-yl)benzo[d][1,3]dioxole (7.76 g, 50 yield, E/Z 80:17) as a yellow liquid.

[0404] .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 147.5, 147.4, 145.6, 145.5, 137.8, 137.5, 135.9, 135.8, 136.9, 122.4, 121.5, 121.1, 121.0, 108.9, 108.9, 108.8, 109.0, 108.1, 108.0, 100.7, 41.7, 34.3, 34.2, 33.9, 32.8, 32.7, 31.6, 31.5, 23.4, 16.4 ppm.

b) 4-((6-(benzo[d][1,3]dioxol-5-yl)-4-methylhex-3-en-1-yl)oxy)-3-ethoxybenzaldehyde

[0405] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (1.97 g, 11.9 mmol, 1.0 equiv) and 5-(6-bromo-3-methylhex-3-en-1-yl)benzo[d][1,3]dioxole (3.88 g, 13.1 mmol, 1.1 equiv) according to the procedure of example 42 as an orange liquid (3.14 g, 69% yield, E/Z 80:20).

[0406] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 9.87-9.80 (m, 1H), 7.45-7.37 (m, 2H), 6.95 (d, J=8.3 Hz, 0.8H), 6.89 (d, J=8.1 Hz, 0.2H), 6.73-6.57 (m, 3H), 5.92-5.84 (m, 2H), 5.28-5.14 (m, 1H), 4.20-4.09 (m, 2H), 4.01 (t, J=7.2 Hz, 1.6H), 3.88 (t, J=7.2 Hz, 0.4H), 2.70-2.43 (m, 4H), 2.37-2.23 (m, 2H), 1.81-1.69 (m, 3H), 1.52-1.42 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 190.9, 154.3, 154.2, 149.1, 149.0, 147.4, 147.3, 145.5, 145.4, 137.7, 137.5, 135.9, 135.8, 129.9, 126.5, 121.1, 121.1, 121.0, 120.4, 119.5, 111.6, 110.7, 108.8, 108.8, 108.0, 107.9, 100.6, 100.6, 68.5, 68.4, 64.4, 41.8, 34.2, 34.2, 33.9, 33.8, 31.8, 28.9, 27.8, 27.7, 23.4, 22.6, 16.2, 14.6, 14.6, 14.0 ppm.

[0407] Odour description (1% solution in EtOH on paper blotter, 24 h): sweet powdery, creamy, vanilla, vanitrope.

Example 80: 4-(4-((6-(benzo[d][1,3]dioxol-5-yl)-4-methylhex-3-en-1-yl)oxy)phenyl)butan-2-one

[0408] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (1.86 g, 11.3 mmol, 1.0 equiv) and 5-(6-bromo-3-methylhex-3-en-1-yl)benzo[d][1,3]dioxole (3.70 g, 12.4 mmol, 1.1 equiv) according to the procedure of example 42_as a colorless liquid (2.00 g, 46% yield, E/Z 80:20).

[0409] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers): 7.12-7.07 (m, 2H), 6.84-6.77 (m, 2H), 6.74-6.67 (m, 2H), 6.65-6.61 (m, 1H), 5.91 (s, 1.6H), 5.87 (s, 0.4H), 5.27-5.19 (m, 1H), 3.88 (t, J=7.1 Hz, 1.6H), 3.76 (t, J=7.0 Hz, 0.4H), 2.87-2.82 (m, 2H), 2.77-2.62 (m, 4H), 2.53-2.23 (m, 4H), 2.14 (s, 3H), 1.78-1.68 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers): 208.1, 157.3, 147.4, 147.4, 145.5, 145.4, 137.1, 136.0, 135.9, 132.8, 129.1, 129.1, 121.1, 121.0, 121.0, 120.1, 114.5, 114.4, 108.9, 108.9, 108.8, 108.0, 108.0, 108.0, 100.7, 100.6, 67.6, 67.5, 45.4, 41.8, 34.3, 30.1, 28.9, 28.1, 27.8, 28.0, 27.8, 23.4, 16.3 ppm.

[0410] Odour description (1% solution in EtOH on paper blotter, 24 h): fruity, raspberry, grenadine, berryflor, fresh, transparent.

Example 81: 3-ethoxy-4-((4-methyl-6-(2,6,6-trimethylcyclohex-1-en-1-yl)hex-3-en-1-yl)oxy)benzaldehyde

a) 2-(6-bromo-3-methylhex-3-en-1-yl)-1,3,3-trimethylcyclohex-1-ene

[0411] Magnesium turnings (1.50 g, 61.8 mmol, 1.2 equiv) were added to a 350 ml-sulfonation flask and overlayed with THF (10 mL). Then 10% of a solution of bromocyclopropane (7.47 g, 61.8 mmol, 1.2 equiv) in THF (40 mL) were added. Afterwards the Grignard was started with a heating gun and a few iodine crystals. Then the remaining THF solution of bromocyclopropane was added dropwise. After the addition was completed, the reaction mixture was stirred for 1 hour at reflux. Then, a solution of 4-(2,6,6-trimethylcyclohex-1-en-1-yl)butan-2-one (10.0 g, 51.5 mmol, 1.0 equiv) in THF (40 mL) was added dropwise at 0 C. (the temperature rose to 13 C.). After the addition was completed, the cooling bath was removed and the reaction mixture was stirred for 16 hours at room temperature. Then 63% aq. sulfuric acid (12.0 mL, 139 mmol, 2.7 equiv) was added dropwise at 3 C. to the reaction mixture (the temperature rose to 18 C.). After stirring for 3 hours at room temperature, the reaction mixture was added to 120 mL of water for quenching and extracted with MTBE (150 mL). The organic layer was washed once with 2M NaOH (100 mL), water (150 mL) and brine (150 mL). The organic layer was dried over MgSO.sub.4, filtered and the solvent was removed under reduced pressure. The crude was filtered over silica gel and eluted with 100% heptane to give 2-(6-bromo-3-methylhex-3-en-1-yl)-1,3,3-trimethylcyclohex-1-ene (6.96 g, 45% yield, mixture of isomers 63:14, 77% purity) as a yellow liquid.

[0412] GC/MS (EI) major isomer: m/z (%): 298 (1, [M].sup.+.Math.), 137 (100), 95 (50), 81 (32), 41 (15).

[0413] GC/MS (EI) minor isomer: m/z (%): 298 (0, [M].sup.+.Math.), 137 (100), 95 (52), 81 (32), 41 (14).

b) 3-ethoxy-4-((4-methyl-6-(2,6,6-trimethylcyclohex-1-en-1-yl)hex-3-en-1-yl)oxy)benzaldehyde

[0414] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (1.90 g, 12 mmol, 1.0 equiv) and 2-(6-bromo-3-methylhex-3-en-1-yl)-1,3,3-trimethylcyclohex-1-ene (3.5 g, 12 mmol, 1.1 equiv) according to the procedure of example 42 as a yellow liquid (1.96 g, 44% yield, 3 isomers 84:13:3).

[0415] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of isomers): 9.84 (s, 1H), 7.45-7.39 (m, 2H), 7.00-6.96 (m, 1H), 5.27-5.19 (m, 1H), 4.18-4.06 (m, 4H), 2.62-2.56 (m, 2H), 2.15-2.02 (m, 4H), 1.97-1.89 (m, 2H), 1.81-1.77-1.71 (m, 3H), 1.65-1.54 (m, 5H), 1.50-1.45 (m, 3H), 1.45-1.40 (m, 2H), 1.02-0.99 (m, 6H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of isomers): 190.9, 154.4, 149.2, 149.1, 139.6, 139.3, 136.9, 130.0, 129.9, 127.3, 127.1, 126.6, 126.5, 119.1, 117.9, 111.9, 111.8, 111.0, 110.9, 68.9, 68.6, 64.6, 40.2, 39.8, 39.8, 35.0, 34.9, 32.7, 32.7, 31.9, 29.0, 28.6, 28.6, 27.9, 27.7, 27.3, 23.4, 22.7, 19.9, 19.8, 19.5, 16.3, 14.7, 14.6, 14.1 ppm.

[0416] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla.

Example 82: 4-(4-((4-methyl-6-(2,6,6-trimethylcyclohex-1-en-1-yl)hex-3-en-1-yl)oxy)phenyl)butan-2-one

[0417] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (1.90 g, 11.6 mmol, 1.0 equiv) and 2-(6-bromo-3-methylhex-3-en-1-yl)-1,3,3-trimethylcyclohex-1-ene (3.46 g, 11.6 mmol, 1.1 equiv) according to the procedure of example 42 as a brown liquid (1.30 g, 29% yield, 3 isomers 83:13:4).

[0418] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of isomers): 7.11-7.07 (m, 2H), 6.85-6.80 (m, 2H), 5.30-5.14 (m, 1H), 3.94-3.90 (m, 2H), 2.86-2.81 (m, 2H), 2.74-2.70 (m, 2H), 2.53-2.46 (m, 2H), 2.13 (s, 3H), 2.12-2.00 (m, 4H), 1.98-1.89 (m, 2H), 1.80-1.68 (m, 3H), 1.68-1.54 (m, 5H), 1.46-1.40 (m, 2H), 1.03-0.99 (m, 6H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of isomers): 208.1, 157.4, 138.9, 138.7, 137.0, 132.8, 129.1, 127.2, 127.0, 119.8, 119.0, 118.7, 114.6, 67.9, 67.7, 45.4, 40.2, 39.8, 39.8, 35.0, 34.9, 32.8, 32.7, 30.1, 28.9, 28.6, 28.6, 28.2, 27.7, 27.3, 23.3, 19.9, 19.8, 19.5, 16.3, 16.2 ppm.

[0419] Odour description (1% solution in EtOH on paper blotter, 24 h): fruity, sweet, powdery, raspberry ketone.

Example 83: 3-ethoxy-4-((4-methyl-6-(2,6,6-trimethylcyclohex-1-en-1-yl)hexa-3,5-dien-1-yl)oxy)benzaldehyde

a) 2-(6-bromo-3-methylhexa-1,3-dien-1-yl)-1,3,3-trimethylcyclohex-1-ene

[0420] Magnesium turnings (1.52 g, 62.4 mmol, 1.2 equiv) were added to a 350 ml-sulfonation flask and overlayed with THF (10 mL). Then 10% of a solution of bromocyclopropane (7.55 g, 62.4 mmol, 1.2 equiv) in THF (40 mL) were added. Afterwards the Grignard was started with a heating gun and a few iodine crystals. Then the remaining THF solution of bromocyclopropane was added dropwise. After the addition was completed, the reaction mixture was stirred for 1 hour at reflux. Then, a solution of 4-(2,6,6-trimethylcyclohex-1-en-1-yl)but-3-en-2-one (10.0 g, 52.0 mmol, 1.0 equiv) in THF (40 mL) was added dropwise at 0 C. (the temperature rose to 11 C.). After the addition was completed, the cooling bath was removed and the reaction mixture was stirred for 1 hour at room temperature and refluxed for 1.5 hours. Then 63% aq. sulfuric acid (12.0 mL, 139 mmol, 2.7 equiv) was added dropwise at 3 C. to the reaction mixture. After stirring for 1 hour at room temperature, the reaction mixture was added to 120 mL of water for quenching and extracted with MTBE (150 mL). The organic layer was washed once with 2M NaOH (100 mL), water (150 mL) and brine (150 mL). The organic layer was dried over MgSO.sub.4, filtered and the solvent was removed under reduced pressure. The crude was filtered over silica gel and eluted with 100% heptane to give 2-(6-bromo-3-methylhexa-1,3-dien-1-yl)-1,3,3-trimethylcyclohex-1-ene (6.64 g, 43% yield, mixture of 4 isomers 74:16:2:1, 93% purity) as a yellow liquid.

[0421] GC/MS (EI) major isomer: m/z (%): 296 (10, [M].sup.+.Math.), 133 (45), 119 (100), 105 (46), 91 (45), 41 (30).

b) 3-ethoxy-4-((4-methyl-6-(2,6,6-trimethylcyclohex-1-en-1-yl)hexa-3,5-dien-1-yl)oxy)benzaldehyde

[0422] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (1.86 g, 11.2 mmol, 1.0 equiv) and 2-(6-bromo-3-methylhexa-1,3-dien-1-yl)-1,3,3-trimethylcyclohex-1-ene (3.32 g, 11.2 mmol, 1.0 equiv) according to the procedure of example 42 as a yellow liquid (0.78 g, 18% yield, 4 isomers 81:13:6 overlapping in GC-MS).

[0423] .sup.1H NMR (400 MHz, CDCl.sub.3, complex mixture of isomers): 9.84 (s, 1H), 7.47-7.37 (m, 2H), 7.01-6.92 (m, 1H), 6.55-6.37 (m, 0.4H), 6.26-5.98 (m, 1.6H), 5.69 (td, J=4.4, 16.1 Hz, 0.1H), 5.49 (dt, J=1.1, 7.5 Hz, 0.6H), 5.40 (t, J=7.2 Hz, 0.3H), 4.18-4.07 (m, 4H), 2.79-2.72 (m, 1.6H), 2.54-2.25 (m, 0.4H), 2.11-1.40 (m, 15H), 1.11-0.81 (m, 6H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, complex mixture of isomers): 190.9, 154.5, 154.3, 154.2, 149.1, 149.1, 138.0, 137.6, 137.3, 136.9, 135.4, 130.0, 129.7, 129.0, 128.6, 128.4, 126.5, 125.5, 124.7, 122.7, 119.6, 111.9, 111.8, 111.7, 110.9, 68.7, 68.3, 64.6, 40.6, 39.5, 39.4, 36.6, 34.2, 34.1, 32.9, 31.9, 29.0, 28.9, 28.9, 28.7, 28.6, 28.2, 27.3, 24.6, 22.8, 22.7, 21.7, 21.6, 20.5, 19.2, 19.2, 14.7, 14.7, 14.1, 12.5 ppm.

[0424] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, fruity, woody, ionone beta.

Example 84: 4-((5,9-dimethyldeca-3,8-dien-1-yl)oxy)-3-ethoxybenzaldehyde

[0425] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (2.00 g, 12.0 mmol, 1.0 equiv) and 5,9-dimethyldeca-3,8-dien-1-ol (2.20 g, 12.0 mmol, 1.0 equiv, prepared following a procedure by Gruenanger, C. U.; Breit, B. Angew. Chem. Int. Ed. 2008, 47, 7346-7349) according to the procedure of example 1 as a colorless liquid (1.78 g, 45% yield).

[0426] .sup.1H NMR (400 MHz, CDCl.sub.3): 9.84 (s, 1H), 7.42 (dd, J=2.0, 8.1 Hz, 1H), 7.40 (d, J=1.8 Hz, 1H), 6.97 (d, J=8.2 Hz, 1H), 5.49-5.41 (m, 2H), 5.09 (tdt, J=1.4, 2.8, 7.2 Hz, 1H), 4.18-4.07 (m, 4H), 2.62-2.52 (m, 2H), 2.11 (m.sub.c, 1H), 2.00-1.91 (m, 2H), 1.68 (d, J=1.2 Hz, 3H), 1.60-1.55 (m, 3H), 1.47 (t, J=7.0 Hz, 3H), 1.36-1.23 (m, 2H), 0.98 (d, J=6.7 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of isomers): 190.9, 154.3, 149.1, 139.6, 131.2, 129.9, 126.5, 124.6, 123.1, 111.8, 110.9, 68.8, 64.5, 37.0, 36.4, 32.3, 25.8, 25.7, 20.6, 17.6, 14.6 ppm.

[0427] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, chocolate milk, slightly fresh, fatty, watery, melon.

Example 85: 3-ethoxy-4-((6-phenylhex-3-en-1-yl)oxy)benzaldehyde

[0428] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (2.69 g, 12.0 mmol, 1.0 equiv) and (6-bromohex-3-en-1-yl)benzene (3.87 g, 16.2 mmol, 1.0 equiv, prepared according to Matsubara, Hiroshi; et al. Japan, JP2017014124 A, contains also (3-bromo-3-cyclopropylpropyl)benzene) according to the procedure of example 42 as a colorless liquid (2.0 g, 38% yield, 61% pure, E isomer along with 39% of 4-(1-cyclopropyl-3-phenylpropoxy)-3-ethoxybenzaldehyde).

[0429] .sup.1H NMR (400 MHz, CDCl.sub.3, signals for the mixture): 9.85 (s, 2H), 7.46-7.41 (m, 3H), 7.37 (dd, J=2.0, 8.1 Hz, 1H), 7.31-7.16 (m, 11H), 6.96 (dd, J=3.4, 8.1 Hz, 2H), 5.71-5.59 (m, 1H), 5.57-5.46 (m, 1H), 4.18-4.05 (m, 6H), 3.86 (dt, J=5.1, 7.3 Hz, 1H), 2.93-2.78 (m, 2H), 2.74-2.66 (m, 2H), 2.57 (dq, J=0.9, 6.9 Hz, 2H), 2.39-2.33 (m, 2H), 2.25-2.04 (m, 2H), 1.47 (q, J=6.8 Hz, 6H), 1.18 (tq, J=5.1, 8.1 Hz, 1H), 0.61-0.50 (m, 2H), 0.39-0.22 (m, 2H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, signals for the mixture): 190.9, 190.9, 154.3, 154.1, 150.5, 149.1, 141.8, 132.8, 130.6, 130.0, 128.4, 128.4, 128.2, 126.5, 125.9, 125.9, 125.8, 125.6, 116.7, 111.9, 111.7, 111.0, 83.2, 68.7, 64.6, 64.5, 36.6, 35.8, 34.5, 32.2, 31.5, 15.2, 14.7, 14.7, 3.5, 2.2 ppm.

[0430] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, creamy, balsamic, cinnamic).

Example 86: 3-ethoxy-4-((6-(4-isobutylphenyl)hex-3-en-1-yl)oxy)benzaldehyde

a) 1-cyclopropyl-3-(4-isobutylphenyl)prop-2-en-1-one

[0431] Sodium hydroxide (24.0 g, 594 mmol, 5.0 equiv) was added to a mixture of ethanol (90 mL) and water (60 mL) and stirred for a few minutes (the temperature rose to 70 C.). Then, cyclopropyl methyl ketone (10.0 g, 119 mmol, 1.0 equiv) was added dropwise to the suspension of base followed by 4-isobutylbenzaldehyde (19.3 g, 119 mmol, 1.0 equiv. After stirring for 3 hours at 60 C., the reaction mixture was added to ice cold water (120 mL) and extracted with MTBE (2150 mL). The organic layers were washed with 2M HCl (150 mL), water (150 mL) and brine (150 mL). The combined organic layers were dried over MgSO.sub.4, filtered and concentrated under reduced pressure to give crude 1-cyclopropyl-3-(4-isobutylphenyl)prop-2-en-1-one (25.8 g, yellow liquid).

b) 1-cyclopropyl-3-(4-isobutylphenyl)propan-1-one

[0432] To a solution of crude 1-cyclopropyl-3-(4-isobutylphenyl)prop-2-en-1-one (10.0 g) in MeOH (20 mL) was added Raney-Nickel (0.5 g, 5% wt/wt) in an autoclave and the reaction mixture was pressurized with hydrogen (30 bar) at 100 C. for 5 hours. The suspension was filtered and concentrated under reduced pressure to give crude 1-cyclopropyl-3-(4-isobutylphenyl)propan-1-one (9.9 g) as a colorless liquid.

c) 1-cyclopropyl-3-(4-isobutylphenyl)propan-1-ol

[0433] LiAlH.sub.4 (1.20 g, 0.8 equiv) was suspended in Et.sub.2O (90 mL) and a solution of crude 1-cyclopropyl-3-(4-isobutylphenyl)propan-1-one (9.9 g) in Et.sub.2O (30 mL) was added dropwise at 0 C. After stirring for 2 hours at room temperature, 2M aq. NaOH (9.9 mL) was added dropwise and slowly. After stirring for 20 minutes, one spatula of MgSO.sub.4 was added. After stirring for another 20 minutes, the reaction mixture was filtered and the solvent removed under reduced pressure to give crude 1-cyclopropyl-3-(4-isobutylphenyl)propan-1-ol (9.16 g) as a colorless liquid.

d) 1-(6-bromohex-3-en-1-yl)-4-isobutylbenzene

[0434] To a round-bottomed flask containing crude 1-cyclopropyl-3-(4-isobutylphenyl)propan-1-ol (8.48 g) was added dropwise at 15 C. 48% aq. HBr (12.3 g, 2.0 equiv). After stirring for 3 hours at room temperature, more 48% aq. HBr (2.0 g) was added and stirring was continued for 1 hour. The reaction mixture was quenched with ice-cold 2M aq. NaOH and extracted with MTBE (50 mL). The organic layer was washed with water (50 mL) and brine (50 mL). The combined organic extracts were dried over MgSO.sub.4, filtered and concentrated under reduced pressure to give crude 1-(6-bromohex-3-en-1-yl)-4-isobutylbenzene (9.4 g) as a yellow liquid, which was used in the next step without further purification.

e) 3-ethoxy-4-((6-(4-isobutylphenyl)hex-3-en-1-yl)oxy)benzaldehyde

[0435] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (2.50 g, 15.0 mmol, 1.0 equiv) and crude 1-(6-bromohex-3-en-1-yl)-4-isobutylbenzene (4.40 g, 14.9 mmol, 1.0 equiv) according to the procedure of example 42 as a colorless liquid (1.14 g, 20% yield, 15% pure along with 85% of 4-(1-cyclopropyl-3-(4-isobutylphenyl)propoxy)-3-ethoxybenzaldehyde). Characteristic signals for 3-ethoxy-4-((6-(4-isobutylphenyl)hex-3-en-1-yl)oxy)benzaldehyde: .sup.1H NMR (400 MHz, CDCl.sub.3): 5.74-5.58 (m, 1H), 5.56-5.45 (m, 1H). Characteristic signals for 4-(1-cyclopropyl-3-(4-isobutylphenyl)propoxy)-3-ethoxybenzaldehyde: .sup.13C NMR (101 MHz, CDCl.sub.3): 191.0, 154.2, 150.5, 139.2, 138.9, 130.6, 129.1, 129.0, 128.1, 126.0, 116.6, 111.7, 83.2 (CHO), 64.5, 45.0, 36.7, 31.1, 30.2, 22.4, 15.2, 14.7, 3.4, 2.3 ppm.

[0436] Odour description for the mixture (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, creamy, floral, muguet.

Example 87: 3-ethoxy-4-(3-(2-(2-(4-methylcyclohex-3-en-1-yl)propyl)cyclopentylidene) propoxy)benzaldehyde

a) 4-(1-(2-(3-bromopropylidene)cyclopentyl)propan-2-yl)-1-methylcyclohex-1-ene

[0437] Magnesium turnings (1.10 g, 44 mmol, 1.2 equiv) were added to a 350 ml-sulfonation flask and overlayed with THF (10 mL). Then 10% of a solution of bromocyclopropane (5.3 g, 44 mmol, 1.2 equiv) in THF (40 mL) were added. Afterwards the Grignard was started with a heating gun and a few iodine crystals. Then the remaining THF solution of bromocyclopropane was added dropwise. After the addition was completed, the reaction mixture was stirred for 1 hour at reflux. Then, a solution of 2-(2-(4-methylcyclohex-3-en-1-yl)propyl)cyclopentan-1-one (8.0 g, 36 mmol, 1.0 equiv) in THF (40 mL) was added dropwise at 0 C. (the temperature rose to 10 C.). After the addition was completed, the cooling bath was removed and the reaction mixture was stirred for 1 hour at room temperature and refluxed for 1.5 hours. Then 63% aq. sulfuric acid (8.0 mL, 98 mmol, 2.7 equiv) was added dropwise at 3 C. to the reaction mixture (the temperature rose to 18 C.). After stirring for 1 hour at room temperature, the reaction mixture was added to 120 mL of water for quenching and extracted with MTBE (150 mL). The organic layer was washed once with water (2150 mL) and brine (150 mL). The organic layer was dried over MgSO.sub.4, filtered and the solvent was removed under reduced pressure. The crude was filtered over silica gel and eluted with 100% heptane to give 4-(1-(2-(3-bromopropylidene)cyclopentyl)propan-2-yl)-1-methylcyclohex-1-ene (1.93 g, 16% yield, 63% pure) as a yellow liquid.

[0438] GC/MS (EI): m/z (%): 244 (12, [M].sup.+.Math.-HBr), 121 (100), 93 (94), 79 (80), 67 (40), 55 (35).

b) 3-ethoxy-4-(3-(2-(2-(4-methylcyclohex-3-en-1-yl)propyl)cyclopentylidene) propoxy)benzaldehyde

[0439] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (0.51 g, 3.1 mmol, 1.0 equiv) and 4-(1-(2-(3-bromopropylidene)cyclopentyl)propan-2-yl)-1-methylcyclohex-1-ene (1.0 g, 3.1 mmol, 1.0 equiv) according to the procedure of example 42 as a colorless liquid (0.29 g, 23% yield, 4 isomers 59:29:4:3).

[0440] .sup.1H NMR (400 MHz, CDCl.sub.3, complex mixture of isomers): 9.77 (s, 1H), 7.37-7.31 (m, 2H), 6.93-6.85 (m, 1H), 5.31 (br s, 1H), 5.24-5.07 (m, 1H), 4.18-3.91 (m, 4H), 3.41 (q, J=6.9 Hz, 1H), 2.62-0.90 (m, 24H), 0.89-0.62 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, complex mixture of isomers): 190.5, 154.3, 154.2, 152.7, 150.8, 150.4, 148.9, 146.8, 135.9, 135.2, 134.6, 133.6, 133.6, 133.5, 129.7, 129.7, 129.6, 129.6, 126.2, 124.0, 123.2, 121.0, 120.9, 120.8, 120.8, 120.7, 115.7, 113.8, 113.8, 113.5, 112.4, 111.5, 111.5, 111.4, 111.3, 111.2, 110.6, 110.6, 110.4, 68.5, 68.4, 68.3, 68.2, 68.2, 65.6, 64.2, 64.2, 56.3, 51.9, 50.5, 48.6, 45.8, 45.7, 44.2, 43.6, 42.2, 42.0, 41.8, 41.8, 39.5, 39.5, 39.3, 39.3, 39.2, 39.0, 38.9, 38.6, 38.3, 38.0, 36.9, 36.5, 35.8, 35.6, 35.4, 35.3, 35.1, 35.4, 35.1, 34.9, 34.6, 33.1, 33.1, 32.9, 32.6, 32.3, 30.9, 30.7, 30.7, 30.3, 30.3, 29.9, 29.8, 29.6, 29.4, 29.2, 29.2, 28.9, 28.8, 28.7, 27.9, 27.9, 27.5, 27.3, 27.1, 26.8, 26.5, 25.9, 25.8, 25.6, 25.0, 24.9, 24.3, 23.8, 23.8, 23.7, 23.7, 23.5, 23.4, 23.2, 22.3, 21.7, 20.3, 19.8, 16.5, 16.1, 15.7, 15.7, 15.4, 15.1, 14.6, 14.5 ppm. Odour description (1% solution in EtOH on paper blotter, 24 h): green, fatty, creamy, warm milk, fatty, powdery, vanilla, fruity, peachy.

Example 88: 4-((4-cyclopentylpent-3-en-1-yl)oxy)-3-ethoxybenzaldehyde

a) 1-cyclopentyl-1-cyclopropylethan-1-ol

[0441] Magnesium turnings (1.04 g, 42.8 mmol, 1.2 equiv) were added to a 100 mL-sulfonation flask and overlayed with THF (5 mL). Then 10% of a solution of bromocyclopentane (6.38 g, 42.8 mmol, 1.2 equiv) in THF (20 mL) were added. After the Grignard reaction had been started, the remaining THF solution of bromocyclopentane was added dropwise. The reaction mixture was refluxed for 1 hour. Then, a solution of 1-cyclopropylethan-1-one (3.00 g, 35.7 mmol, 1.0 equiv) in THF (20 mL) was added dropwise at 0 C. After stirring for 3 hours at room temperature, the reaction mixture was quenched with water (30 mL) and extracted with MTBE (40 mL). The organic layer was washed water (240 mL) and brine (40 mL). The organic layer was dried over MgSO.sub.4, filtered and the solvent was removed under reduced pressure to give crude 1-cyclopentyl-1-cyclopropylethan-1-ol (2.88 g) as a colorless liquid.

b) (5-bromopent-2-en-2-yl)cyclopentane

[0442] To a round-bottomed flask containing 1-cyclopentyl-1-cyclopropylethan-1-ol (2.88 g, 18.7 mmol) was added dropwise at 15 C. 48% aq. HBr (4.09 g, 24.3 mmol, 1.3 equiv). After stirring for 1 hour at room temperature, the reaction mixture was added onto ice cold 2M aq. NaOH (10 mL) and extracted with MTBE (20 mL). The organic layer was washed water (20 mL) and brine (20 mL). The organic layer was dried over MgSO.sub.4, filtered and the solvent was removed under reduced pressure to give crude (5-bromopent-2-en-2-yl)cyclopentane (3.08 g, 59% pure by GC) as a brown liquid.

c) 4-((4-cyclopentylpent-3-en-1-yl)oxy)-3-ethoxybenzaldehyde

[0443] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (2.36 g, 14.2 mmol, 1.0 equiv) and crude (5-bromopent-2-en-2-yl)cyclopentane (3.08 g, 14.2 mmol, 1.0 equiv) according to the procedure of example 42 as a yellow liquid (0.20 g, 5% yield, 2 isomers 86:13).

[0444] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of isomers): 9.75 (s, 1H), 7.34 (d, J=8.1 Hz, 1H), 7.32 (s, 1H), 6.89 (d, J=7.7 Hz, 1H), 5.21-5.11 (m, 1H), 4.08-3.94 (m, 4H), 2.57-2.46 (m, 2H), 2.37-2.28 (m, 1H), 1.69-1.44 (m, 9H), 1.42-1.25 (m, 5H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of isomers): 190.5, 154.2, 148.9, 141.2, 140.8, 129.7, 126.2, 119.2, 116.6, 111.5, 111.5, 110.7, 110.5, 68.6, 68.3, 64.2, 49.1, 48.7, 40.5, 30.7, 30.4, 27.6, 27.2, 26.7, 25.5, 25.0, 18.9, 14.4, 14.2 ppm. GC/MS (EI, major): m/z (%): 302 (1, [M].sup.+.Math.), 137 (25), 95 (100), 81 (73), 67 (28), 55 (30), 41 (28).

[0445] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, creamy, vanilla.

Example 89: 3-ethoxy-4-((4-methyldec-3-en-1-yl)oxy)benzaldehyde

a) 1-bromo-4-methyldec-3-ene

[0446] Magnesium turnings (1.04 g, 42.8 mmol, 1.2 equiv) were added to a 100 mL-sulfonation flask and overlayed with THF (5 mL). Then 10% of a solution of 1-bromohexane (7.06 g, 42.8 mmol, 1.2 equiv) in THF (20 mL) were added. After the Grignard reaction had been started, the remaining THF solution of 1-bromohexane was added dropwise. After the addition was completed, the reaction mixture was stirred for 1 hour at reflux. Then, a solution of 1-cyclopropylethan-1-one (3.00 g, 35.7 mmol, 1.0 equiv) in THF (20 mL) was added dropwise at 0 C. After the addition was completed, the cooling bath was removed and the reaction mixture was stirred for 2 hours at room temperature. 63% aq. sulfuric acid (15 mL, 96 mmol, 2.7 equiv) was added dropwise at 0 C. to the reaction mixture. After stirring for 16 hours at room temperature, the reaction mixture was quenched with water (40 mL) and extracted with MTBE (40 mL). The organic layer was washed water (240 mL) and brine (40 mL). The organic layer was dried over MgSO.sub.4, filtered and the solvent was removed under reduced pressure to give crude 1-bromo-4-methyldec-3-ene (6.06 g) as a yellow liquid.

b): 3-ethoxy-4-((4-methyldec-3-en-1-yl)oxy)benzaldehyde

[0447] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (4.32 g, 26.0 mmol, 1.0 equiv) and crude 1-bromo-4-methyldec-3-ene (6.06 g, 26.0 mmol, 1.1 equiv) according to the procedure of example 42 as an orange liquid (3.22 g, 39% yield, 2 isomers 89:11, 85% purity).

[0448] .sup.13C NMR (101 MHz, CDCl.sub.3, major): 190.9, 154.4, 149.1, 139.1, 129.9, 126.6, 118.4, 111.7, 110.9, 68.7, 64.5, 39.7, 31.8, 28.9, 27.9, 27.8, 22.6, 16.1, 14.7, 14.1 ppm. GC/MS (EI, major): m/z (%): 318 (3, [M].sup.+.Math.), 111 (31), 97 (100), 83 (71), 69 (75), 55 (62), 41 (37). GC/MS (EI, minor): m/z (%): 318 (1, [M].sup.+.Math.), 111 (36), 97 (100), 83 (74), 69 (79), 55 (63), 41 (32).

[0449] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, creamy.

Example 90: 3-ethoxy-4-((4-methyldodec-3-en-1-yl)oxy)benzaldehyde

a) 1-bromo-4-methyldodec-3-ene

[0450] Magnesium turnings (1.04 g, 42.8 mmol, 1.2 equiv) were added to a 100 mL-sulfonation flask and overlayed with THF (5 mL). Then 10% of a solution of 1-bromooctane (8.27 g, 42.8 mmol, 1.2 equiv) in THF (20 mL) were added. After the Grignard reaction had been started, the remaining THF solution of 1-bromooctane was added dropwise. The reaction mixture was refluxed for 1 hour. Then, a solution of 1-cyclopropylethan-1-one (3.00 g, 35.7 mmol, 1.0 equiv) in THF (20 mL) was added dropwise at 5 C. After the addition was completed, the cooling bath was removed and the reaction mixture was stirred for 2 hours at room temperature. 63% aq. sulfuric acid (8.15 mL, 96 mmol, 2.7 equiv) was added dropwise at 0 C. to the reaction. After stirring for 16 hours at room temperature, the reaction mixture was quenched with water (40 mL) and extracted with MTBE (40 mL). The organic layer was washed water (240 mL) and brine (40 mL). The organic layer was dried over MgSO.sub.4, filtered and the solvent was removed under reduced pressure to give crude 1-bromo-4-methyldodec-3-ene (7.47 g) as a yellow liquid.

b) 3-ethoxy-4-((4-methyldodec-3-en-1-yl)oxy)benzaldehyde

[0451] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (4.75 g, 28.6 mmol, 1.0 equiv) and crude 1-bromo-4-methyldodec-3-ene (7.47 g, 28.6 mmol, 1.1 equiv) according to the procedure of example 42 as a yellow liquid (2.58 g, 26% yield, 2 isomers 94:6).

[0452] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of isomers): 9.83 (s, 1H), 7.43-7.39 (m, 2H), 6.96 (d, J=8.1 Hz, 1H), 5.20 (ddd, J=1.2, 6.1, 8.6 Hz, 1H), 4.18-4.12 (m, 2H), 4.08-4.03 (m, 2H), 2.58 (q, J=7.3 Hz, 2H), 2.08-1.98 (m, 2H), 1.74-1.64 (m, 3H), 1.49-1.45 (m, 3H), 1.43-1.35 (m, 2H), 1.33-1.16 (m, 10H), 0.90-0.85 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of isomers: 190.9, 154.4, 154.3, 149.1, 139.2, 139.0, 129.9, 129.9, 126.5, 119.0, 118.3, 111.7, 110.8, 68.8, 68.6, 64.5, 39.7, 32.0, 31.9, 29.6, 29.5, 29.5, 29.3, 29.3, 28.1, 27.9, 27.8, 27.7, 23.5, 22.6, 16.1, 14.6, 14.1 ppm. GC/MS (EI, major): m/z (%): 346 (2, [M].sup.+.Math.), 111 (47), 97 (95), 83 (86), 69 (100), 55 (67), 41 (47). GC/MS (EI, minor): m/z (%): 346 (2, [M].sup.+.Math.), 111 (46), 97 (100), 83 (90), 69 (99), 55 (78), 41 (42).

[0453] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, creamy, slightly green, sesame seed, sharp, technical.

Example 91: 3-ethoxy-4-(tridec-1-en-4-yloxy)benzaldehyde

[0454] The compound was obtained from tridec-1-en-4-ol (5.00 g, 25.2 mmol), ethyl vanillin (3-ethoxy-4-hydroxybenzaldehyde) (8.12 g, 47.9 mmol), triphenylphosphine (7.93 g, 30.2 mmol) and DIAD (diisopropyl azodicarboxylate) (6.24 g, 30.2 mmol) according to the procedure of example 1 as a colorless oil (5.22 g, 60% yield).

[0455] .sup.1H NMR (400 MHz, CDCl3, 298 K) (ppm)=9.83 (s, 1H), 7.45-7.36 (m, 2H), 6.98 (d, J=8.8 Hz, 1H), 5.87 (tdd, J=7.1, 10.1, 17.1 Hz, 1H), 5.19-5.05 (m, 2H), 4.38 (quin, J=5.9 Hz, 1H), 4.13 (q, J=7.0 Hz, 2H), 2.56-2.38 (m, 2H), 1.82-1.63 (m, 2H), 1.50-1.20 (m, 18H), 0.91-0.83 (m, 3H). .sup.13C NMR (101 MHz, CDCl3, 298 K) (ppm)=191.0, 154.1, 150.1, 133.9, 130.1, 126.3, 117.7, 114.7, 111.7, 79.5, 64.6, 38.3, 33.7, 31.9, 29.6, 29.5, 29.5, 29.3, 25.3, 22.7, 14.7, 14.1. MS (EI, 70 eV): 346 (4, [M]+.Math.), 305 (1), 166 (100), 138 (44), 55 (16), 41 (17). Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, aldehydic, fruity, mandarin.