PRECURSORS OF PHENOLIC FRAGRANT COMPOUNDS
20250243427 ยท 2025-07-31
Inventors
- Lijun ZHOU (Shanghai, CN)
- Nicolas COCITO ARMANlNO (Kemptthal, CH)
- An Chai (Shanghai, CN)
- Felix FLACHSMANN (Kemptthal, CH)
- Marc LINIGER (Kemptthal, CH)
Cpc classification
C07C251/48
CHEMISTRY; METALLURGY
C07C37/56
CHEMISTRY; METALLURGY
C11B9/0061
CHEMISTRY; METALLURGY
C07C49/255
CHEMISTRY; METALLURGY
C07C47/575
CHEMISTRY; METALLURGY
International classification
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.
Claims
1. A method of generating a phenolic fragment compound HX which is a compound of formula (II) ##STR00015## the method comprising exposing a compound of formula (I) to ambient air in the presence or absence of light ##STR00016## wherein R.sub.1-R.sub.7 is independently selected from the group consisting of H, linear C1-C4 hydrocarbon groups and branched C1-C4 hydrocarbon groups, wherein the linear and branched C1-C4 hydrocarbon groups independently bear up to 2 heteroatoms selected from the group consisting of O, S and N, and bear up to one double bond or triple bond, and bearing up to one ring; 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.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, 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 limited to 4; 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.1R.sub.4 is limited to 4; and wherein X is representing the following fragment ##STR00017## 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 (R.sub.18C1-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 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 use according to claim 1, wherein R.sub.1-R.sub.2 is independently selected from the group consisting of H, Me, Et, vinyl, ethynyl, allyl, iso-Pr, n-Pr, propenyl, propynyl, 2-methylprop-1-enyl, methylcarboxylate, ethylcarboxylate, and acetyl; R.sub.3-R.sub.5 is independently selected from the group consisting of H, Me, Et, iso-Pr, n-Pr, iso-Bu, n-Bu, tert-Bu, and sec-Bu; and R.sub.6-R.sub.7 is independently selected from the group consisting of H, Me, Et; iso-Pr, n-Pr, iso-Bu, n-Bu, tert-Bu, sec-Bu, propenyl, propynyl, methoxymethyl, cyclopropyl, cyclopropylmethyl, cyclobutyl, methylcarboxylate, ethylcarboxylate, carbaldehyde, hydroxymethyl, 1,3-butadienyl, 2-methylallyl, vinyl, ethynyl, and acetyl; 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.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, 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 limited to 4; 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, and the sum of all carbon atoms of R.sub.1-R.sub.6 and R.sub.1-R.sub.4 is limited to 4; and 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, 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 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.
3. A compound of formula (I) ##STR00018## wherein R.sub.1-R.sub.7 is independently selected from the group consisting of H.sub.1, linear C1-C4 hydrocarbon groups and branched C1-C4 hydrocarbon groups, wherein the linear and branched C1-C4 hydrocarbon groups independently bear up to 2 heteroatoms selected from the group consisting of O, S and N, and bear up to one double bond or triple bond, and bearing up to one ring; 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.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, 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 limited to 4; 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.1R.sub.4 is limited to 4; and wherein X is representing the following fragment ##STR00019## 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.13 (R.sub.13C1-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 independently 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; with the proviso that the compound is not (Z)-1-(tert-butyl)-4-(hex-3-en-1-yloxy)benzene, (Z)-1-(hex-3-en-1-yloxy)-4-methylbenzene, (Z)-1-(hex-3-en-1-yloxy)-3-methylbenzene, (Z)-1-(hex-3-en-1-yloxy)-2-methylbenzene, or (Z)-(hex-3-en-1-yloxy)benzene.
4. The compound according to claim 3, wherein R.sub.1-R.sub.2 is independently selected from the group consisting of H, Me, Et, vinyl, ethynyl, allyl, iso-Pr, n-Pr, propenyl, propynyl, 2-methylprop-1-enyl, methylcarboxylate, ethylcarboxylate, and acetyl; R.sub.3-R.sub.5 is independently selected from the group consisting of H, Me, Et, iso-Pr, n-Pr, iso-Bu, n-Bu, tert-Bu, and sec-Bu; and R.sub.6-R.sub.7 is independently selected from the group consisting of H, Me, Et; iso-Pr, n-Pr, iso-Bu, n-Bu, tert-Bu, sec-Bu, propenyl, propynyl, methoxymethyl, cyclopropyl, cyclopropylmethyl, cyclobutyl, methylcarboxylate, ethylcarboxylate, carbaldehyde, hydroxymethyl, 1,3-butadienyl, 2-methylallyl, vinyl, ethynyl, and acetyl; 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.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, 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 limited to 4; 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 can be are selected from the corresponding groups of R.sub.1, R.sub.2, R.sub.3, R.sub.4, and X, and the sum of all carbon atoms of R.sub.1-R.sub.6 and R.sub.1-R.sub.4 is limited to 4; and wherein R.sub.11 is selected from the group consisting of H, C1-C5 alkyl, OH, OMe, OEt, O-n-Pr, 0-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 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. The compound of formula (I) according to claim 3, wherein the residue attached to the fragment X is selected from the group consisting of cis-3 hexenyl, trans-3-hexenyl, cis or trans-pentenyl, prenyl (3-methyl-3-butyl) and cyclopent-3-enyl.
6. A fragrance composition comprising at least one compound of formula (I) according to claim 3.
7. A consumer product comprising at least one compound of formula (I) according to claim 3 and a consumer product base.
8. A method to release a phenolic fragrant compound of formula (II), the method comprising exposing a compound of formula (I) as defined in claim 1 to ambient air in the presence or absence of light.
9. A method of making a compound of formula (I) according to claim 1, comprising the steps of: a) providing a phenolic fragrant compound HX, which is a compound of formula (II) ##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, 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 (R.sub.18C1-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, b) reacting it with an unsaturated alkylhalide or an unsaturated alcohol.
10. A method to confer, enhance, improve or modify the hedonic properties of a fragrance composition or a consumer product, the method comprising adding to said fragrance composition or consumer product at least one compound of formula (I) as defined in claim 1.
Description
DESCRIPTION OF FIGURES
[0156]
[0157]
[0158]
EXAMPLES
General:
[0159] 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: (Z)-3-ethoxy-4-(hex-3-en-1-yloxy)benzaldehyde
[0160] To a solution of 3-ethoxy-4-hydroxybenzaldehyde (20.0 g, 120 mmol) and potassium carbonate (25.0 g, 180 mmol) in DMF (200 mL) was added (Z)-1-bromohex-3-ene (25.5 g, 156 mmol) 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 (150 mL) and MTBE (150 mL) was added. The mixture was extracted with MTBE (2100 mL), the organic layers were combined and washed with water (3100 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 (Z)-3-ethoxy-4-(hex-3-en-1-yloxy)benzaldehyde (24.5 g, 82% yield) as a colorless oil.
[0161] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.73 (s, 1H), 7.48-7.24 (m, 2H), 6.86 (d, J=8.1 Hz, 1H), 5.52-5.40 (m, 1H), 5.38-5.26 (m, 1H), 4.12-3.89 (m, 4H), 2.52 (q, J=7.0 Hz, 2H), 2.13-1.89 (m, 2H), 1.36 (t, J=7.0 Hz, 3H), 0.90 (t, J=7.6 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9 (d), 154.3 (s), 149.1 (s), 134.8 (d), 130.0 (s), 126.5 (d), 123.4 (d), 111.7 (d), 110.8 (d), 68.5 (t), 64.5 (t), 27.1 (t), 20.6 (t), 14.6 (q), 14.2 (q) ppm. GC/MS (EI): m/z (%): 248 (15) [M.sup.+], 219 (1), 166 (100), 149 (10), 138 (70), 109 (11), 83 (25), 67 (18). Odor description (1% solution in EtOH on paper blotter, 24 h): powdery (vanillin) creamy
Example 2: (E)-3-ethoxy-4-(hex-3-en-1-yloxy)benzaldehyde
[0162] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (5.0 g, 30.1 mmol, 1.0 equiv) and (E)-1-bromohex-3-ene (6.4 g, 39.1 mmol, 1.3 equiv) according to the procedure of example 1 as light yellow liquid (22.6 mmol, 5.6 g, 75% yield).
[0163] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.74 (s, 1H), 7.49-7.27 (m, 2H), 6.88 (d, J=8.1 Hz, 1H), 5.63-5.48 (m, 1H), 5.44-5.27 (m, 1H), 4.03 (m, 4H), 2.47 (q, J=6.9 Hz, 2H), 2.11-1.84 (m, 2H), 1.38 (t, J=7.0 Hz, 3H), 0.90 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9 (d), 154.4 (s), 149.2 (s), 135.4 (d), 130.0 (s), 126.6 (d), 123.8 (d), 111.9 (d), 111.1 (d), 68.9 (t), 64.6 (t), 32.2 (t), 25.6 (t), 14.7 (q), 13.7 (q) ppm. GC/MS (EI): m/z (%): 248 (12) [M.sup.+], 233 (1), 166 (75), 149 (7), 138 (43), 83 (32), 55 (100).
[0164] Odor description (1% solution in EtOH on paper blotter, 24 h): powdery (vanilla, creamy) slightly fruity (raspberry, strawberry)
Example 3: 3-ethoxy-4-(hex-3-en-1-yloxy)benzaldehyde
[0165] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (20.0 g, 120.3 mmol, 1.0 equiv) and 1-bromohex-3-ene (23.6 g, 144.4 mmol, 1.2 equiv) according to the procedure of example 1 as colorless liquid (89.0 mmol, 22.1 g, 74% yield, E/Z 3:1).
[0166] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers) 9.75 (s, 1H), 7.38-7.26 (m, 2H), 6.88 (d, J=8.1 Hz, 1H), 5.63-5.25 (m, 2H), 4.15-3.92 (m, 4H), 2.57-1.92 (m, 4H), 1.96 (s, 1H), 1.38 (t, J=7.0 Hz, 3H), 0.93-0.88 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers) 190.9 (d), 154.3 (s), 149.2 (s), 135.4 (d), 134.9 (d), 130.0 (s), 126.6 (d), 123.7 (d), 123.4 (d), 111.9 (d), 111.7 (d), 111.1 (d), 110.8 (d), 68.9 (t), 68.5 (t), 64.6 (t), 64.5 (t), 32.2 (t), 27.2 (t), 25.7 (t), 20.7 (t), 14.7 (q), 14.3 (q), 13.7 (q) ppm. GC/MS (EI): m/z (%): 248 (18) [M.sup.+], 166 (100), 149 (9), 138 (67), 83 (26), 67 (14), 55 (89).
[0167] Odor description (1% solution in EtOH on paper blotter, 24 h): powdery sweet (vanilla)
Example 4: (Z)-3-ethoxy-4-(hept-4-en-2-yloxy)benzaldehyde
[0168] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (10.0 g, 60.2 mmol, 1.0 equiv) and (Z)-6-bromohept-3-ene (10.66 g, 60.2 mmol, 1.1 equiv) according to the procedure of example 1 as colorless liquid (8.0 mmol, 2.1 g, 13% yield).
[0169] .sup.1H NMR (400 MHz, CDCl.sub.3) 59.83 (s, 1H), 7.51-7.34 (m, 2H), 6.96 (d, J=7.0 Hz, 1H), 5.64-5.38 (m, 2H), 4.52-4.47 (m, 1H), 4.13 (q, J=7.0 Hz, 2H), 2.64-2.28 (m, 2H), 2.19-1.99 (m, 2H), 1.45 (t, J=7.0 Hz, 3H), 1.38 (d, J=6.1 Hz, 3H), 0.96 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9 (d), 153.6 (s), 150.0 (s), 134.5 (d), 133.3 (d), 130.1 (s), 126.3 (d), 123.9 (d), 114.3 (d), 111.6 (d), 75.4 (d), 64.6 (t), 33.9 (t), 20.7 (t), 19.4 (q), 14.7 (q), 14.2 (q) ppm. GC/MS (EI): m/z (%): 262 (7) [M.sup.+], 233 (1), 166 (61), 149 (8), 138 (47), 121 (4), 109 (10), 97 (33), 81 (32), 55 (100).
[0170] Odor description (1% solution in EtOH on paper blotter, 24 h): sweet (brown sugar) powdery (vanillin, chocolate, ice cream)
Example 5: (Z)-4-(4-(hept-4-en-2-yloxy)phenyl)butan-2-one
[0171] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (4.0 g, 24.4 mmol, 1.0 equiv) and (Z)-6-bromohept-3-ene (6.5 g, 36.5 mmol, 1.2 equiv) according to the procedure of example 1 as colorless liquid (2.7 mmol, 0.7 g, 7% yield).
[0172] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.99 (d, J=8.5 Hz, 2H), 6.73 (d, J=8.5 Hz, 2H), 5.43-5.30 (m, 2H), 4.29-4.20 (m, 1H), 2.79-2.62 (m, 4H), 2.42-1.95 (m, 7H), 1.35-0.97 (m, 3H), 0.96-0.72 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 208.2 (s), 156.4 (s), 134.2 (d), 132.9 (s), 129.2 (d), 124.1 (d), 116.0 (d), 73.7 (d), 45.5 (t), 33.9 (t), 30.1 (q), 28.9 (t), 20.8 (t), 19.5 (q), 14.2 (q) ppm. GC/MS (EI): m/z (%): 260 (16) [M.sup.+], 191 (25), 164 (77), 133 (14), 107 (100), 94 (25), 55 (82).
[0173] Odor description (1% solution in EtOH on paper blotter, 24 h): raspberry (fruity, ripe, fresh)
Example 6: (Z)-4-(4-(hex-3-en-1-yloxy)phenyl)butan-2-one
[0174] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (20.0 g, 121.8 mmol, 1.0 equiv) and (Z)-1-bromohex-3-ene (23.8 g, 146.1 mmol, 1.2 equiv) according to the procedure of example 1 as colorless liquid (67.4 mmol, 16.6 g, 55% yield).
[0175] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.00 (d, J=8.3 Hz, 2H), 6.73 (d, J=8.3 Hz, 2H), 5.50-5.40 (m, 1H), 5.38-5.29 (m, 1H), 3.84 (t, J=6.9 Hz, 2H), 2.75 (t, J=7.5 Hz, 2H), 2.64 (t, J=7.5 Hz, 2H), 2.44 (q, J=6.9 Hz, 2H), 2.04 (s, 3H), 2.03-1.96 (m, 2H), 0.91 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 208.2 (s), 157.4 (s), 134.3 (d), 133.0 (s), 129.2 (d), 124.1 (d), 114.6 (d), 67.6 (t), 45.5 (t), 30.1 (q), 28.9 (t), 27.4 (t), 20.7 (t), 14.3 (q) ppm. GC/MS (EI): m/z (%): 246 (20) [M.sup.+], 190 (2), 164 (60), 149 (13), 121 (21), 107 (100), 94 (23), 77 (19), 55 (68).
[0176] Odor description (1% solution in EtOH on paper blotter, 24 h): raspberry
Example 7: (E)-4-(4-(hex-3-en-1-yloxy)phenyl)butan-2-one
[0177] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (5.0 g, 30.4 mmol, 1.0 equiv) and (E)-1-bromohex-3-ene (6.0 g, 36.5 mmol, 1.2 equiv) according to the procedure of example 1 as colorless liquid (16.2 mmol, 4.0 g, 53% yield).
[0178] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.00 (d, J=8.2 Hz, 2H), 6.73 (d, J=8.2 Hz, 2H), 5.61-5.46 (m, 1H), 5.45-5.31 (m, 1H), 3.85 (t, J=6.9 Hz, 2H), 2.75 (t, J=7.4 Hz, 2H), 2.63 (t, J=7.4 Hz, 2H), 2.37 (q, J=6.9 Hz, 2H), 2.04 (s, 3H), 1.99-1.88 (m, 2H), 0.90 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 208.2 (s), 157.4 (s), 134.8 (d), 132.9 (s), 129.2 (d), 124.5 (d), 114.6 (d), 67.9 (t), 45.5 (t), 32.6 (t), 30.1 (q), 28.9 (t), 25.7 (t), 13.8 (q) ppm. GC/MS (EI): m/z (%): 246 (20) [M.sup.+], 164 (69), 121 (25), 107 (92), 94 (24), 77 (24), 55 (100).
[0179] Odor description (1% solution in EtOH on paper blotter, 24 h): raspberry
Example 8: (Z)-4-(hex-3-en-1-yloxy)-3-methoxybenzaldehyde
[0180] The compound was obtained from 4-hydroxy-3-methoxybenzaldehyde (4.0 g, 26.3 mmol, 1.0 equiv) and (Z)-1-bromohex-3-ene (6.43 g, 39.4 mmol, 1.5 equiv) according to the procedure of example 1 as colorless liquid (21.3 mmol, 5.0 g, 81% yield).
[0181] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.84 (s, 1H), 7.54-7.35 (m, 2H), 6.97 (d, J=8.2 Hz, 1H), 5.75-5.52 (m, 1H), 5.47-5.26 (m, 1H), 4.09 (t, J=7.2 Hz, 2H), 3.92 (s, 3H), 2.64 (q, J=7.2 Hz, 2H), 2.23-1.92 (m, 2H), 0.99 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.8 (d), 153.9 (s), 149.8 (s), 135.0 (d), 130.0 (s), 126.7 (d), 123.1 (d), 111.4 (d), 109.3 (d), 68.4 (t), 55.9 (q), 27.1 (t), 20.7 (t), 14.2 (q) ppm. GC/MS (EI): m/z (%): 234 (10) [M.sup.+], 152 (100), 137 (5), 109 (5), 83 (22), 67 (15), 55 (75).
[0182] Odor description (1% solution in EtOH on paper blotter, 24 h): powdery (vanilla) slightly green
Example 9: methyl (Z)-4-(hex-3-en-1-yloxy)-2-hydroxy-3,6-dimethylbenzoate
[0183] The compound was obtained from methyl 2,4-dihydroxy-3,6-dimethylbenzoate (4.0 g, 20.4 mmol, 1.0 equiv) and (Z)-1-bromohex-3-ene (4.0 g, 24.5 mmol, 3.0 equiv) according to the procedure of example 1 as colorless liquid (7.2 mmol, 2.0 g, 35% yield).
[0184] .sup.1H NMR (400 MHz, CDCl.sub.3) 11.81 (s, 1H), 6.23 (s, 1H), 5.59-5.47 (m, 1H), 5.46-5.34 (m, 1H), 3.97 (t, J=6.7 Hz, 2H), 3.89 (s, 3H), 2.58-2.50 (m, 2H), 2.48 (s, 3H), 2.16-1.98 (m, 5H), 0.99 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 171.5 (s), 161.2 (s), 159.8 (s), 139.0 (s), 133.4 (d), 123.0 (d), 110.0 (s), 105.7 (d), 104.2 (s), 66.6 (t), 50.7 (d), 26.4 (t), 23.6 (q), 19.6 (t), 13.2 (q), 6.8 (q) ppm. GC/MS (EI): m/z (%): 278 (17) [M.sup.+], 231(15), 196 (58), 164 (100), 136 (44), 83 (17), 67 (14), 55 (43).
[0185] Odor description (1% solution in EtOH on paper blotter, 24 h): powdery mossy (Evernyl)
Example 10: (Z)-4-allyl-1-(hex-3-en-1-yloxy)-2-methoxybenzene
[0186] The compound was obtained from 4-allyl-2-methoxyphenol (4.0 g, 24.4 mmol, 1.0 equiv) and (Z)-1-bromohex-3-ene (5.2 g, 31.7 mmol, 1.3 equiv) according to the procedure of example 1 as light yellow liquid (17.0 mmol, 4.2 g, 70% yield).
[0187] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.72 (d, J=8.4 Hz, 1H), 6.66-6.56 (m, 2H), 5.99-5.76 (m, 1H), 5.50-5.40 (m, 1H), 5.38-5.26 (m, 1H), 5.06-4.88 (m, 2H), 3.90 (t, J=7.4 Hz, 2H), 3.76 (s, 3H), 3.24 (d, J=6.7 Hz, 2H), 2.50 (q, J=7.2 Hz, 2H), 2.04-1.97 (m, 2H), 0.89 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 148.4 (s), 145.7 (s), 136.7 (d), 133.4 (d), 131.8 (s), 122.8 (d), 119.4 (d), 114.5 (t), 112.2 (d), 111.4 (d), 67.5 (t), 54.9 (q), 38.8 (t), 26.4 (t), 19.6 (t), 13.2 (q) ppm. GC/MS (EI): m/z (%): 246 (15) [M.sup.+], 164 (100), 149 (25), 131 (16), 91 (21), 55 (35).
[0188] Odor description (1% solution in EtOH on paper blotter, 24 h): slightly spicy
Example 11: (Z)-4-allyl-1-(hex-3-en-1-yloxy)-2-methoxybenzene
[0189] The compound was obtained from (E)-2-methoxy-4-(prop-1-en-1-yl)phenol (4.0 g, 24.4 mmol, 1.0 equiv) and (Z)-1-bromohex-3-ene (5.2 g, 31.7 mmol, 1.3 equiv) according to the procedure of example 1 as light yellow liquid (17.5 mmol, 4.3 g, 71% yield).
[0190] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.92-6.75 (m, 3H), 6.33 (d, J=15.7 Hz, 1H), 6.16-6.01 (m, 1H), 5.58-5.48 (m, 1H), 5.47-5.33 (m, 1H), 3.98 (t, J=7.5 Hz, 2H), 3.86 (s, 3H), 2.58 (q, J=7.2 Hz, 2H), 2.18-2.01 (m, 2H), 1.86 (d, J=6.6 Hz, 3H), 0.97 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 149.4 (s), 147.5 (s), 134.5 (d), 131.3 (s), 130.7 (d), 123.8 (d), 118.7 (d), 113.1 (d), 109.1 (d), 68.5 (t), 55.9 (q), 27.4 (t), 20.7 (t), 18.4 (q), 14.3 (q) ppm. GC/MS (EI): m/z (%): 246 (10) [M.sup.+], 164 (100), 149 (17), 115 (8), 103 (14), 91 (20), 55 (27).
[0191] Odor description (1% solution in EtOH on paper blotter, 24 h): slightly spicy woody
Example 12: 4-(but-3-en-1-yloxy)-3-ethoxybenzaldehyde
[0192] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (5.0 g, 30.1 mmol, 1.0 equiv) and 4-bromobut-1-ene (5.3 g, 39.1 mmol, 1.3 equiv) according to the procedure of example 1 as colorless liquid (20.9 mmol, 4.6 g, 70% yield).
[0193] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.83 (s, 1H), 7.55-7.34 (m, 2H), 6.97 (d, J=8.1 Hz, 1H), 6.08-5.80 (m, 1H), 5.31-5.00 (m, 2H), 4.23-4.01 (m, 4H), 2.63 (q, J=6.8 Hz, 2H), 1.46 (t, J=7.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9 (d), 154.2 (s), 149.2 (s), 133.8 (d), 130.1 (s), 126.5 (d), 117.5 (t), 112.0 (d), 111.1 (d), 68.3 (t), 64.6 (t), 33.4 (t), 14.7 (q) ppm. GC/MS (EI): m/z (%): 220 (97) [M.sup.+], 192 (10), 166 (47), 137 (100), 109 (21), 81 (25), 55 (94).
[0194] Odor description (1% solution in EtOH on paper blotter, 24 h): powdery (vanilla, creamy, dough)
Example 13: 4-allyl-1-(but-3-en-1-yloxy)-2-methoxybenzene
[0195] The compound was obtained from 4-allyl-2-methoxyphenol (2.5 g, 15.2 mmol, 1.0 equiv) and 4-bromobut-1-ene (2.7 g, 19.8 mmol, 1.3 equiv) according to the procedure of example 1 as light yellow liquid (9.6 mmol, 2.1 g, 62% yield).
[0196] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.74 (d, J=7.9 Hz, 1H), 6.67-6.54 (m, 2H), 6.02-5.67 (m, 2H), 5.13-5.05 (m, 1H), 5.04-4.94 (m, 3H), 3.96 (t, J=6.9 Hz, 2H), 3.77 (s, 3H), 3.25 (d, J=6.4 Hz, 2H), 2.51 (q, J=6.4 Hz, 2H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 148.5 (s), 145.6 (s), 136.6 (d), 133.3 (d), 132.0 (s), 119.5 (d), 116.0 (s), 114.6 (s), 112.6 (d), 111.5 (d), 67.5 (t), 54.9 (q), 38.8 (t), 32.7 (t) ppm. GC/MS (EI): m/z (%): 218 (95) [M.sup.+], 203 (1), 164 (100), 149 (43), 131 (29), 103 (41), 91 (44), 77 (26), 55 (49).
[0197] Odor description (1% solution in EtOH on paper blotter, 24 h): slightly spicy (iso eugenol) fruity (berry)
Example 14: methyl 4-(but-3-en-1-yloxy)-2-hydroxy-3,6-dimethylbenzoate
[0198] The compound was obtained from methyl 2,4-dihydroxy-3,6-dimethylbenzoate (10.0 g, 51.0 mmol, 1.0 equiv) and 4-bromobut-1-ene (20.6 g, 152.9 mmol, 3.0 equiv) according to the procedure of example 1 as white solid (24.8 mmol, 6.2 g, 49% yield).
[0199] .sup.1H NMR (400 MHz, CDCl.sub.3) 11.75 (s, 1H), 6.14 (s, 1H), 5.91-5.63 (m, 1H), 5.32-4.83 (m, 2H), 3.94 (t, J=6.4 Hz, 2H), 3.81 (s, 3H), 2.52-2.42 (m, 2H), 2.40 (s, 3H), 1.98 (s, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 172.6 (s), 162.2 (s), 160.8 (s), 140.0 (s), 134.3 (d), 117.2 (t), 111.1 (s), 106.8 (d), 105.4 (s), 67.3 (t), 51.7 (q), 33.7 (t), 24.6 (q), 7.8 (q) ppm. GC/MS (EI): m/z (%): 250 (43) [M.sup.+], 218 (42), 196 (44), 164 (100), 136 (78), 107 (19), 91 (17), 77 (29), 55 (54).
[0200] Odor description (1% solution in EtOH on paper blotter, 24 h): slightly mossy
Example 15: 3-ethoxy-4-((3-methylbut-3-en-1-yl)oxy)benzaldehyde
[0201] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (4.0 g, 24.1 mmol, 1.0 equiv) and 4-bromo-2-methylbut-1-ene (4.3 g, 28.9 mmol, 1.2 equiv) according to the procedure of example 1 as colorless liquid (16.6 mmol, 3.9 g, 69% yield).
[0202] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.73 (s, 1H), 7.48-7.25 (m, 2H), 6.88 (d, J=8.2 Hz, 1H), 4.75 (d, J=15.2 Hz, 2H), 4.10 (t, J=7.0 Hz, 2H), 4.03 (q, J=7.0 Hz, 2H), 2.49 (t, J=7.0 Hz, 2H), 1.74 (s, 3H), 1.36 (t, J=7.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9 (d), 154.3 (s), 149.2 (s), 141.9 (s), 130.1 (s), 126.5 (d), 112.4 (t), 111.9 (d), 111.0 (d), 67.9 (t), 64.6 (t), 36.9 (t), 22.9 (q), 14.6 (q) ppm. GC/MS (EI): m/z (%): 234 (25) [M.sup.+], 191 (1), 166 (100), 149 (8), 138 (72), 109 (10), 81 (14), 69 (52).
[0203] Odor description (1% solution in EtOH on paper blotter, 24 h): mild, powdery, spicy
Example 16: 4-(4-((3-methylbut-3-en-1-yl)oxy)phenyl)butan-2-one
[0204] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (4.0 g, 24.4 mmol, 1.0 equiv) and 4-bromo-2-methylbut-1-ene (4.4 g, 29.2 mmol, 1.2 equiv) according to the procedure of example 1 as colorless liquid (11.2 mmol, 2.6 g, 46% yield).
[0205] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.00 (d, J=8.3 Hz, 2H), 6.74 (d, J=8.3 Hz, 2H), 4.82-4.62 (m, 2H), 3.96 (t, J=6.8 Hz, 2H), 2.75 (t, J=7.5 Hz, 2H), 2.64 (t, J=7.5 Hz, 2H), 2.40 (t, J=6.8 Hz, 2H), 2.04 (s, 3H), 1.72 (s, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 208.2 (s), 157.3 (s), 142.3 (s), 133.0 (s), 129.2 (d), 114.6 (d), 111.9 (t), 66.5 (t), 45.4 (t), 37.2 (t), 30.1 (q), 28.9 (t), 22.8 (q) ppm. GC/MS (EI): m/z (%): 232 (34) [M.sup.+], 164 (50), 149 (12), 121 (20), 107 (100), 94 (21), 77 (16), 69 (23).
[0206] Odor description (1% solution in EtOH on paper blotter, 24 h): fruity (raspberry) sweet
Example 17: (Z)-3-ethoxy-4-(oct-3-en-1-yloxy)benzaldehyde
[0207] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (5.0 g, 30.1 mmol, 1.0 equiv) and (Z)-1-bromooct-3-ene (5.75 g, 30.1 mmol, 1.1 equiv) according to the procedure of example 1 as colorless liquid (17.4 mmol, 4.8 g, 58% yield).
[0208] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.74 (s, 1H), 7.42-7.24 (m, 2H), 6.87 (d, J=8.1 Hz, 1H), 5.51-5.42 (m, 1H), 5.41-5.29 (m, 1H), 4.05 (q, J=7.0 Hz, 2H), 3.99 (t, J=7.1 Hz, 2H), 2.54 (q, J=7.1 Hz, 2H), 2.16-1.93 (m, 2H), 1.38 (t, J=7.0 Hz, 3H), 1.31-1.14 (m, 4H), 0.81 (t, J=7.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9 (d), 154.3 (s), 149.1 (s), 133.2 (d), 130.0 (s), 126.5 (d), 123.9 (d), 111.8 (d), 110.8 (d), 68.5 (t), 64.5 (t), 31.8 (t), 27.2 (t), 27.1 (t), 22.3 (t), 14.6 (t), 14.0 (t) ppm. GC/MS (EI): m/z (%): 276 (12) [M.sup.+], 166 (99), 138 (61), 110 (11), 81 (17), 69 (100), 55 (61).
[0209] Odor description (1% solution in EtOH on paper blotter, 24 h): vanilla (powdery, spicy, creamy)
Example 18: 4-(4-((4-methylpent-3-en-1-yl)oxy)phenyl)butan-2-one
[0210] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (3.02 g, 18.40 mmol, 1.5 equiv) and 5-bromo-2-methylpent-2-ene (2.0 g, 12.27 mmol, 1.0 equiv) according to the procedure of example 1 as colorless liquid (9.7 mmol, 2.4 g, 79% yield).
[0211] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.00 (d, J=8.5 Hz, 2H), 6.73 (d, J=8.6 Hz, 2H), 5.12 (t, J=7.1 Hz, 1H), 3.81 (t, J=7.1 Hz, 2H), 2.75 (t, J=7.4 Hz, 2H), 2.63 (t, J=7.4 Hz, 2H), 2.38 (q, J=7.0 Hz, 2H), 2.04 (s, 3H), 1.64 (s, 3H), 1.57 (s, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 207.1 (s), 156.4 (s), 133.3 (s), 131.8 (s), 128.1 (d), 118.6 (d), 113.5 (d), 66.6 (t), 44.4 (t), 29.1 (q), 27.9 (t), 27.3 (t), 24.7 (q), 16.8 (q) ppm. GC/MS (EI): m/z (%): 246 (14) [M.sup.+], 164 (84), 121 (13), 107 (53), 91 (16), 83 (66), 55 (100).
[0212] Odor description (1% solution in EtOH on paper blotter, 24 h): sweet fruity (raspberry ketone)
Example 19: 3-ethoxy-4-(hept-1-en-4-yloxy)benzaldehyde
[0213] To a solution of ethyl vanillin (19.2 g, 116 mmol), hept-1-en-4-ol (15.0 g, 105 mmol) and triphenylphosphane (35.8 g, 137 mmol) in THF (250 mL) was added DIAD (27.6 g, 137 mmol) portionwise at r.t., the temperature was kept below 25 C. during addition. The resulting suspension was stirred for 16 h under argon atmosphere at r.t. The reaction conversion was monitored by TLC and GC. The reaction mixture was filtered, and the solvent was removed by rotary evaporation, the residue was purified by silica gel column chromatography (PE:MTBE=94:6) to give 3-ethoxy-4-(hept-1-en-4-yloxy)benzaldehyde (15.9 g, yield: 58%) as colorless liquid.
[0214] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.72 (s, 1H), 7.47-7.21 (m, 2H), 6.88 (d, J=8.6 Hz, 1H), 6.08-5.59 (m, 1H), 5.04-4.96 (m, 2H), 4.60-4.20 (m, 1H), 4.01 (q, J=7.0 Hz, 2H), 2.55-2.16 (m, 2H), 1.81-1.50 (m, 2H), 1.46-1.18 (m, 5H), 0.83 (t, J=7.4 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.8 (d), 154.0 (s), 150.1 (s), 133.8 (d), 130.2 (s), 126.2 (d), 117.6 (t), 114.7 (d), 111.8 (d), 79.0 (d), 64.6 (t), 38.3 (t), 35.8 (t), 18.5 (t), 14.7 (q), 14.0 (q) ppm. GC/MS (EI): m/z (%): 262 (13) [M.sup.+], 166 (100), 149 (8), 138 (78), 109 (8), 93 (3), 81 (11), 55 (33).
[0215] Odor description (1% solution in EtOH on paper blotter, 24 h): powdery (dry, vanilla) fruity (metallic)
Example 20: 4-(cyclopent-3-en-1-yloxy)-3-ethoxybenzaldehyde
[0216] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (25.0 g, 150.4 mmol, 1.0 equiv) and cyclopent-3-en-1-ol (15.19 g, 181 mmol, 1.2 equiv) according to the procedure of example 19 as white solid (116.2 mmol, 27.0 g, 76% yield).
[0217] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.82 (s, 1H), 7.52-7.32 (m, 2H), 7.07-6.83 (m, 1H), 5.89-5.61 (m, 2H), 5.18-4.88 (m, 1H), 4.10 (q, J=5.0 Hz, 2H), 2.96-2.76 (m, 2H), 2.74-2.54 (m, 2H), 1.43 (t, J=5.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9 (d), 153.4 (s), 149.6 (s), 129.9 (s), 128.3 (d), 126.4 (d), 113.0 (d), 111.2 (d), 78.1 (d), 64.6 (t), 40.0 (t), 14.6 (q) ppm. GC/MS (EI): m/z (%): 232(23) [M.sup.+], 166(100), 138(100), 137(78), 109(10), 81(12), 67(61).
[0218] Odor description (1% solution in EtOH on paper blotter, 24 h): vanilla (powdery, spicy, creamy)
Example 21: 4-(4-(hept-1-en-4-yloxy)phenyl)butan-2-one
[0219] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (17.7 g, 107.9 mmol, 1.1 equiv) and hept-1-en-4-ol (14.0 g, 98.1 mmol, purity: 80%, 1.0 equiv) according to the procedure of example 19 as colorless liquid (67.6 mmol, 17.6 g, 69% yield).
[0220] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.97 (d, J=8.6 Hz, 2H), 6.72 (d, J=8.6 Hz, 2H), 5.88-5.60 (m, 1H), 5.06-4.91 (m, 2H), 4.23-4.02 (m, 1H), 2.80-2.68 (m, 2H), 2.67-2.55 (m, 2H), 2.41-2.20 (m, 2H), 2.02 (s, 3H), 1.63-1.20 (m, 4H), 0.83 (t, J=7.3 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 208.0 (s), 156.8 (s), 134.3 (d), 133.0 (s), 129.3 (d), 117.3 (t), 116.1 (d), 77.2 (d), 45.40 (t), 38.2 (t), 35.9 (t), 30.1 (q), 28.9 (t), 18.7 (t), 14.1 (q) ppm. GC/MS (EI): m/z (%): 260 (23) [M.sup.+], 219 (16), 177 (3), 164 (73), 149 (14), 121 (20), 107 (100), 94 (30), 77 (10), 55 (25).
[0221] Odor description (1% solution in EtOH on paper blotter, 24 h): raspberry
Example 22: 3-ethoxy-4-(hepta-1,6-dien-4-yloxy)benzaldehyde
[0222] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (3.9 g, 23.5 mmol, 1.1 equiv) and hepta-1,6-dien-4-ol (3.0 g, 21.4 mmol, 1.0 equiv) according to the procedure of example 19 as colorless liquid (13.8 mmol, 3.6 g, 65% yield).
[0223] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.72 (s, 1H), 7.44-7.12 (m, 2H), 6.90 (d, J=8.7 Hz, 1H), 5.98-5.58 (m, 2H), 5.08-4.99 (m, 4H), 4.40-4.28 (m, 1H), 4.06-3.95 (m, 2H), 2.54-1.85 (m, 4H), 1.44-1.12 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.8 (d), 153.6 (s), 150.3 (s), 133.6 (d), 130.5 (s), 126.0 (d), 117.9 (t), 115.4 (d), 111.9 (d), 78.7 (d), 64.6 (t), 37.8 (t), 14.7 (q) ppm. GC/MS (EI): m/z (%): 260 (16) [M.sup.+], 219 (2), 191 (1), 166 (100), 149 (19), 138 (78), 109 (13), 67 (25).
[0224] Odor description (1% solution in EtOH on paper blotter, 24 h): powdery (creamy, vanilla)
Example 23: 4-(4-(hepta-1,6-dien-4-yloxy)phenyl)butan-2-one
[0225] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (5.2 g, 31.4 mmol, 1.1 equiv) and hepta-1,6-dien-4-ol (4.0 g, 28.5 mmol, 1.0 equiv) according to the procedure of example 19 as colorless liquid (15.9 mmol, 4.1 g, 56% yield).
[0226] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.98 (d, J=8.5 Hz, 2H), 6.73 (d, J=8.5 Hz, 2H), 5.86-5.62 (m, 2H), 5.07-4.95 (m, 4H), 4.30-3.98 (m, 1H), 2.73 (t, J=7.5 Hz, 2H), 2.62 (t, J=7.5 Hz, 2H), 2.33 (t, J=6.4 Hz, 4H), 2.03 (s, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 208.0 (s), 156.5 (s), 134.1 (d), 133.3 (s), 129.3 (d), 117.6 (t), 116.3 (d), 76.9 (d), 45.4 (t), 37.8 (t), 30.1 (q), 28.9 (t) ppm. GC/MS (EI): m/z (%): 258 (25) [M.sup.+], 217 (15), 164 (64), 149 (64), 121 (21), 107 (100), 94 (29), 77 (16).
[0227] Odor description (1% solution in EtOH on paper blotter, 24 h): fruity (raspberry)
Example 24: 3-ethoxy-4-((6-methylhepta-1,5-dien-4-yl)oxy)benzaldehyde
[0228] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (5.8 g, 34.9 mmol, 1.1 equiv) and 6-methylhepta-1,5-dien-4-ol (4.0 g, 31.7 mmol, 1.0 equiv) according to the procedure of example 19 as colorless liquid (16.8 mmol, 4.6 g, 53% yield).
[0229] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.72 (s, 1H), 7.30-7.26 (m, 2H), 6.80 (d, J=8.0 Hz, 1H), 5.89-3.83 (m, 7H), 2.57-2.31 (m, 2H), 1.62 (s, 3H), 1.61 (s, 3H), 1.39-1.29 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9 (d), 153.7 (s), 150.0 (s), 136.2 (s), 133.8 (d), 130.2 (s), 126.2 (d), 124.5 (d), 117.6 (t), 115.1 (d), 111.5 (d), 76.5 (d), 64.6 (t), 40.0 (t), 25.6 (q), 18.5 (q), 14.7 (q) ppm. GC/MS (EI): m/z (%): 274 (1) [M.sup.+], 233 (3), 189 (2), 166 (54), 149 (4), 137 (30), 109 (100), 93 (27), 81 (37), 67 (76), 55 (16).
[0230] Odor description (1% solution in EtOH on paper blotter, 24 h): powdery (creamy, vanilla)
Example 25: 4-(4-(hex-5-en-3-yloxy)phenyl)butan-2-one
[0231] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (5.4 g, 32.9 mmol, 1.1 equiv) and hex-5-en-3-ol (6.0 g, 30.0 mmol, 1.0 equiv) according to the procedure of example 19 as colorless liquid (12.6 mmol, 3.1 g, 41% yield).
[0232] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.98 (d, J=8.4 Hz, 2H), 6.73 (d, J=8.4 Hz, 2H), 5.89-5.53 (m, 1H), 5.11-4.67 (m, 2H), 4.23-3.92 (m, 1H), 2.81-2.67 (m, 2H), 2.66-2.52 (m, 2H), 2.38-2.16 (m, 2H), 2.02 (s, 3H), 1.65-1.50 (m, 2H), 0.87 (t, J=7.4 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 208.1 (s), 156.8 (s), 134.3 (d), 133.1 (s), 129.2 (d), 117.3 (t), 116.2 (d), 78.6 (d), 45.4 (t), 37.8 (t), 30.1 (q), 28.9 (t), 26.4 (t), 9.6 (q) ppm. GC/MS (EI): m/z (%): 246 (22) [M.sup.+], 205 (16), 164 (59), 149 (14), 133 (1), 107 (100), 94 (28), 55 (17).
[0233] Odor description (1% solution in EtOH on paper blotter, 24 h): sweet (icing sugar cristal) raspberry
Example 26: 4-(4-(hepta-1,5-dien-4-yloxy)phenyl)butan-2-one
[0234] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (5.2 g, 31.4 mmol, 1.1 equiv) and (E)-hepta-1,5-dien-4-ol (4.0 g, 28.5 mmol, 1.0 equiv) according to the procedure of example 19 as colorless liquid (17.4 mmol, 4.5 g, 56% yield).
[0235] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers) 6.96 (d, J=8.1 Hz, 2H), 6.72 (d, J=8.1 Hz, 2H), 5.84-5.53 (m, 2H), 5.51-5.31 (m, 1H), 5.12-4.81 (m, 2H), 4.72-4.34 (m, 1H), 2.82-2.54 (m, 5H), 2.50-2.22 (m, 1H), 2.03 (s, 3H), 1.61-1.30 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers) 208.1 (s), 156.6 (s), 156.4 (s), 136.3 (d), 134.3 (d), 133.0 (s), 133.0 (d), 132.3 (d), 130.6 (d), 129.7 (d), 129.1 (d), 129.1 (d), 128.3 (d), 117.3 (t), 116.2 (d), 116.2 (d), 115.6 (t), 78.4 (d), 74.4 (d), 45.4 (t), 45.4 (t), 40.2 (t), 36.2 (t), 30.1 (q), 28.9 (t), 21.6 (q), 17.8 (q) ppm. GC/MS (EI): m/z (%): 258 (22) [M.sup.+], 217 (1), 164 (80), 107 (90), 94 (100), 79 (73), 67 (53), 55 (24).
[0236] Odor description (1% solution in EtOH on paper blotter, 24 h): sweet (icing sugar cristal) raspberry
Example 27: 4-(4-((6-methylhepta-1,5-dien-4-yl)oxy)phenyl)butan-2-one
[0237] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (6.0 g, 36.5 mmol, 1.0 equiv) and 6-methylhepta-1,5-dien-4-ol (10.1 g, 40.2 mmol, 1.1 equiv) according to the procedure of example 19 as colorless liquid (28.6 mmol, 7.8 g, 78% yield).
[0238] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.12-6.70 (m, 4H), 5.97-4.67 (m, 5H), 2.87-2.20 (m, 6H), 2.11 (s, 3H), 1.71-1.55 (m, 6H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 208.0 (s), 156.6 (s), 135.3 (s), 134.2 (d), 132.9 (s), 129.0 (d), 122.6 (d), 117.2 (t), 116.0 (d), 115.5 (t), 74.9 (d), 45.4 (t), 45.3 (t), 40.0 (t), 30.1 (q), 28.9 (t), 25.7 (q), 18.6 (q) ppm. GC/MS (EI): m/z (%): 272 (1) [M.sup.+], 231 (4), 164 (100), 107 (60), 93 (45), 77 (22), 67 (64).
[0239] Odor description (1% solution in EtOH on paper blotter, 24 h): fruity (powdery, sweet, raspberry)
Example 28: 3-ethoxy-4-((2-methylpent-4-en-2-yl)oxy)benzaldehyde
[0240] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (5.0 g, 30.1 mmol, 1.0 equiv) and 2-methylpent-4-en-2-ol (4.9 g, 39.1 mmol, 1.3 equiv) according to the procedure of example 19 as colorless liquid (30.1 mmol, 0.06 g, 1% yield).
[0241] .sup.1H NMR (400 MHz, CDCl.sub.3): =9.88 (s, 1H), 7.33-7.45 (m, 2H), 7.15 (d, J=8.0 Hz, 1H), 5.95-6.09 (m, 1H), 5.07-5.18 (m, 2H), 4.09 (q, J=6.9 Hz, 2H), 2.51 (br d, J=7.1 Hz, 2H), 1.47 (t, J=6.9 Hz, 3H), 1.34 ppm (s, 6H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) ppm 191.3 (d), 153.9 (s), 151.0 (s), 134.4 (d), 132.5 (s), 124.9 (d), 124.6 (d), 117.9 (t), 111.4 (d), 83.1 (s), 64.2 (t), 47.0 (t), 26.1 (q), 14.7 (q) ppm. GC/MS (EI): m/z (%): 248 (1) [M.sup.+], 207 (9), 166 (100), 149 (2), 138 (76), 121 (2), 109 (9), 93 (7), 82 (20), 67 (13), 55 (34).
[0242] Odor description (1% solution in EtOH on paper blotter, 24 h): powdery (vanilla)
Example 29: 3-ethoxy-4-((4-methylhepta-3,6-dien-1-yl)oxy)benzaldehyde and 3-ethoxy-4-((4-methylhepta-3,5-dien-1-yl)oxy)benzaldehyde
a) 7-chloro-4-methylhepta-2,4-diene and 7-chloro-4-methylhepta-1,4-diene
[0243] To a solution of 1-cyclopropylethan-1-one (8.00 g, 95 mmol, 1.0 equiv) in diethylether (60 mL) ether was added dropwise at 0 C. allylmagnesium chloride (57 mL, 114 mmol, 1.2 equiv, 2.0M in THF). After having completed the addition, the cooling bath was removed and the reaction mixture was stirred for 1 hour at room temperature. Then it was cooled to 0 C. and a mixture of 50 ml Water and 26 ml conc. sulfuric acid were added dropwise. After stirring for 1 hour, the reaction mixture was added to 100 mL ice cold 2M NaOH and stirred for 20 min. Then it was extracted with 2120 ml MTBE. The organic layer was washed with 1120 ml water and 1120 ml brine. The combined organic layers were dried over MgSO4, filtered and the solvent was evaporated. The crude product was distilled by Kugelrohr distillation (70 C./0.04 mbar) to afford a 2:1 mixture of 7-chloro-4-methylhepta-2,4-diene and 7-chloro-4-methylhepta-1,4-diene (8.79 g, 64% yield, each as E/Z isomers, overall >5 isomers) as a colorless liquid.
[0244] .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of isomers): 137.1, 136.5, 136.4, 135.5, 135.4, 134.9, 127.9, 126.7, 124.6, 123.6, 122.8, 121.4, 120.8, 116.0, 115.4, 113.7, 44.4, 44.3, 44.2, 44.0, 44.0, 36.5, 31.6, 31.4, 31.1, 30.8, 27.0, 23.4, 20.6, 18.6, 18.2, 16.2, 12.6.
b) 3-ethoxy-4-((4-methylhepta-3,6-dien-1-yl)oxy)benzaldehyde and 3-ethoxy-4-((4-methylhepta-3,5-dien-1-yl)oxy)benzaldehyde
[0245] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (2.00 g, 12.0 mmol, 1.0 equiv), the mixture of 7-chloro-4-methylhepta-2,4-diene and 7-chloro-4-methylhepta-1,4-diene (2.26 g, 15.7 mmol, 1.3 equiv) described above and 10 mol % of KI according to the procedure of example 1 as a colorless liquid (1.26 g, 38% yield).
[0246] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of isomers): 9.83 (s, 1H), 7.47-7.35 (m, 2H), 7.01-6.90 (m, 1H), 6.67-6.51 (m, 0.04H), 6.47 (d, J=14.9 Hz, 0.21H), 6.10 (dd, J=1.0, 15.7 Hz, 0.41H), 5.94-5.87 (m, 0.05H), 5.86-5.71 (m, 0.58H), 5.65 (qd, J=6.6, 15.6 Hz, 0.35H), 5.42 (t, J=7.3 Hz, 0.36H), 5.35-5.19 (m, 0.55H), 5.13-4.97 (m, 0.71H), 4.90 (d, J=14.2 Hz, 0.14H), 4.22-3.91 (m, 4H), 2.95-1.92 (m, 3H), 1.86-1.61 (m, 5H), 1.47 (2 major t, J=7.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of isomers): 190.9, 154.3, 154.2, 154.2, 149.1, 149.1, 145.1, 137.0, 136.5, 136.5, 135.7, 135.5, 134.9, 132.9, 130.0, 129.9, 129.9, 128.0, 126.5, 126.5, 126.4, 125.2, 123.6, 123.3, 121.8, 120.3, 119.7, 115.9, 115.3, 113.5, 111.8, 111.7, 111.7, 111.7, 110.9, 110.8, 110.8, 110.7, 110.7, 68.5, 68.3, 64.5, 64.5, 64.5, 44.0, 36.4, 28.4, 28.0, 27.9, 27.8, 27.6, 27.2, 23.5, 20.6, 18.6, 18.2, 18.1, 16.2, 14.6, 12.6 ppm.
[0247] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery (vanilla) sweet (sugary).
Example 30: 2-(hex-3-en-1-yloxy)-1-isopropyl-4-methylbenzene
[0248] A solution of thymol (2-isopropyl-5-methylphenol) (1.02 g, 6.79 mmol) in acetonitrile (MeCN) (10 mL) at room temperature was treated with K.sub.2CO.sub.3 (1.41 g, 10.18 mmol), tetrabutylammonium iodide (TBAI) (0.376 g, 1.02 mmol) and finally (Z)-1-Bromo-3-hexene (1.33 g, 8.15 mmol). The resulting mixture was heated to reflux for 46 h and then cooled to room temperature and poured into saturated aqueous NH.sub.4Cl solution (50 mL), extracted with methyl tert-butyl ether (MTBE) (250 mL), washed with water (20 mL) and brine (20 mL), dried over MgSO.sub.4, 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 at 130-140 C. at 0.06 mbar to give 2-(hex-3-en-1-yloxy)-1-isopropyl-4-methylbenzene (0.30 g, 18% yield) as a colorless oil.
[0249] .sup.1H NMR (400 MHz, CDCl.sub.3, 298 K, mixture of E and Z isomers) (ppm)=7.12 (d, J=7.6 Hz, 1H), 6.77 (d, J=7.6 Hz, 1H), 6.69 (s, 1H), 5.71-5.45 (m, 2H), 4.00 (dt, J=2.6, 6.7 Hz, 2H), 3.39-3.26 (m, 1H), 2.63-2.49 (m, 2H), 2.37-2.34 (m, 3H), 2.20-2.02 (m, 2H), 1.24 (d, J=6.8 Hz, 6H), 1.07-1.00 (m, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3, 298 K, mixture of E and Z isomers) (ppm)=156.1, 136.2, 134.6, 134.1, 134.1, 134.0, 125.8, 125.8, 125.0, 124.6, 121.0, 120.9, 112.3, 112.3, 67.8, 67.6, 32.8, 27.6, 26.7, 26.7, 25.7, 22.9, 22.7, 22.7, 21.4, 20.7, 14.3, 13.8. MS (EI, 70 eV): 232 (10, [M]+*), 217 (1), 150 (28), 135 (100), 83 (14).
[0250] Odour description (1% solution in EtOH on paper blotter, 24 h): aromatic, thymol, menthol
Example 31: 3-ethoxy-4-((6-methylhept-3-en-1-yl)oxy)benzaldehyde
a) 1-cyclopropyl-3-methylbutan-1-ol
[0251] A solution of cyclopropanecarbaldehyde (2.50 g, 35.7 mmol) in THF (tetrahydrofuran) (20 mL) was added slowly to a solution of isobutylmagnesium chloride (2 M in in THF, 19.6 mL, 39.2 mmol) at 5 C. The mixture was then allowed to reach room temperature and stirred for 2 h. The mixture was poured onto sat. aq. NH.sub.4Cl solution (200 mL), extracted with MTBE (2200 mL), washed with brine (100 mL), dried over MgSO.sub.4, filtered and concentrated to give 1-cyclopropyl-3-methylbutan-1-ol (4.6 g, quantitative yield) as a colorless oil which was used without further purification.
[0252] MS (EI, 70 eV): 113 (1, [M]+*-CH.sub.3*), 95 (3), 71 (100), 57 (21), 43 (58).
b) (E)-1-bromo-6-methylhept-3-ene
[0253] A solution of 1-cyclopropyl-3-methylbutan-1-ol (4.00 g, 31.2 mmol) in THF (tetrahydrofuran) (20 mL) was slowly added to a mixture of HBr (48% aqueous solution, 4.24 mL, 37.4 mmol) and sodium dodecyl sulfate (0.3 g, 1 mmol) at 5 C. The mixture was diluted with MTBE (100 mL), washed with water (5100 mL), dried over MgSO.sub.4 and concentrated to give (E)-1-bromo-6-methylhept-3-ene (4.71 g, 93% purity, 73% yield), which was used in the next step without further purification.
[0254] .sup.1H NMR (400 MHz, CDCl.sub.3, 298 K) (ppm)=5.58-5.47 (m, 1H), 5.42-5.33 (m, 1H), 3.37 (t, J=7.2 Hz, 2H), 2.56 (dq, J=1.0, 7.0 Hz, 2H), 1.90 (dt, J=0.9, 6.9 Hz, 2H), 1.67-1.55 (m, 1H), 0.88 (d, J=6.6 Hz, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3, 298 K) (ppm)=132.7, 127.5, 41.9, 36.1, 33.0, 28.3, 22.2. MS (EI, 70 eV): 192 (2), 190 (2, [M]+*), 175 (1), 148 (5), 133 (2), 111 (42), 79 (5), 69 (91), 56 (86), 43 (100).
c) 3-ethoxy-4-((6-methylhept-3-en-1-yl)oxy)benzaldehyde
[0255] A mixture of ethyl vanillin (3-ethoxy-4-hydroxybenzaldehyde) (3.90 g, 23.5 mmol), (E)-1-bromo-6-methylhept-3-ene (4.71 g, 24.6 mmol), tetrabutylammonium bromide (378 mg, 1.17 mmol) and K.sub.2CO.sub.3 (3.89 g, 1.2 Eq, 28.2 mmol) in water (20 mL) was heated up to reflux for 5 h. The reaction mixture was cooled and diluted with water (100 mL) and extracted with MTBE (methyl tert-butyl ether) (250 mL). The org. layers were washed with water (30 mL) and brine (30 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 under vacuum to give 3-ethoxy-4-((6-methylhept-3-en-1-yl)oxy)benzaldehyde (3.88 g, 60% yield) as a colorless oil.
[0256] .sup.1H NMR (400 MHz, CDCl.sub.3, 298 K) (ppm)=9.83 (s, 1H), 7.45-7.38 (m, 2H), 6.97 (d, J=8.2 Hz, 1H), 5.63-5.53 (m, 1H), 5.52-5.42 (m, 1H), 4.19-4.07 (m, 4H), 2.62-2.53 (m, 2H), 1.91 (dt, J=0.9, 6.8 Hz, 2H), 1.67-1.56 (m, 1H), 1.47 (t, J=7.0 Hz, 3H), 0.88 (d, J=6.6 Hz, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3, 298 K) (ppm)=191.0, 154.4, 149.2, 132.6, 130.0, 126.6, 125.9, 111.9, 111.0, 68.8, 64.6, 42.0, 32.3, 28.3, 22.3, 14.7. MS (EI, 70 eV): 276 (4, [M]+*), 166 (53), 138 (32), 69 (100), 55 (48).
[0257] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, green, hazelnut, chocolate.
Example 32: (E)-3-ethoxy-4-((5-methylhex-3-en-1-yl)oxy)benzaldehyde
a) (E)-1-bromo-5-methylhex-3-ene
[0258] A solution of isopropylmagnesium bromide (0.75 molar in THF, 38.8 mL, 29.1 mmol) was cooled to 5 C. and treated slowly with a solution of cyclopropanecarbaldehyde (1.70 g, 24.3 mmol) in THF (10 mL) and the resulting mixture stirred at room temperature for 1 h. The mixture was then treated slowly over 20 min with a solution of H.sub.2SO.sub.4 (16.4 g, 8.89 mL, 167 mmol) in Water (8 mL) and then heated to 50 C. for 4 h. The mixture was cooled and poured into iced 2M NaOH solution (200 mL), extracted with MTBE (2100 mL), washed with water (100 mL) and brine (50 mL), dried over MgSO.sub.4, filtered and concentrated to give (E)-1-bromo-5-methylhex-3-ene (3.83 g, 89% yield) as a pale yellow oil which was used without further purification.
[0259] MS (EI, 70 eV): 178 (4), 176 (4, [M]+*), 161 (1), 133 (1), 97 (27), 93 (4), 83 (4), 69 (100), 55 (41), 41 (47).
b) (E)-3-ethoxy-4-((5-methylhex-3-en-1-yl)oxy)benzaldehyde
[0260] The compound was prepared according to the procedure of example 31c from 3-ethoxy-4-hydroxybenzaldehyde (3.50 g, 21.1 mmol), (E)-1-bromo-5-methylhex-3-ene (3.73 g, 21.1 mmol), tetrabutylammonium bromide (339 mg, 1.05 mmol) and K.sub.2CO.sub.3 (3.49 g, 25.3 mmol) to give (E)-3-ethoxy-4-((5-methylhex-3-en-1-yl)oxy)benzaldehyde (1.83 g, 33% yield) as a colorless oil.
[0261] .sup.1H NMR (400 MHz, CDCl.sub.3, 298 K) (ppm)=9.83 (s, 1H), 7.45-7.39 (m, 2H), 6.97 (d, J=8.2 Hz, 1H), 5.61-5.52 (m, 1H), 5.48-5.38 (m, 1H), 4.15 (q, J=7.0 Hz, 2H), 4.10 (t, J=7.1 Hz, 2H), 2.55 (q, J=7.0 Hz, 2H), 2.27 (qd, J=6.7, 13.4 Hz, 1H), 1.47 (t, J=7.0 Hz, 3H), 0.98 (d, J=6.7 Hz, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3, 298 K) (ppm)=191.0, 154.4, 149.2, 141.0, 130.0, 126.6, 121.7, 111.9, 111.1, 68.9, 64.6, 32.2, 31.1, 22.4, 14.7. MS (EI, 70 eV): 262 (5, [M]+*), 166 (40), 138 (33), 96 (38), 55 (100).
[0262] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, green, hazelnut, chocolate.
Example 33: 3-ethoxy-4-(pent-3-en-1-yloxy)benzaldehyde
[0263] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (26.5 g, 159 mmol, 1.0 equiv) and 5-bromopent-2-ene (35.0 g, 223 mmol, 1.4 equiv, 95% purity) according to the procedure of example 1 as light yellow liquid (29.6 g, 78% yield, E/Z 93:7), after purification by fractional distillation under high vacuum.
[0264] .sup.1H NMR (400 MHz, CDCl.sub.3) for major E isomer: 9.77 (s, 1H), 7.42-7.30 (m, 2H), 6.90 (d, J=8.3 Hz, 1H), 5.63-5.50 (m, 1H), 5.50-5.38 (m, 1H), 4.07 (q, J=7.1 Hz, 2H), 4.02 (t, J=7.0 Hz, 2H), 2.54-2.40 (m, 2H), 1.69-1.58 (m, 3H), 1.40 (t, J=7.0 Hz, 3H) ppm.
[0265] Characteristic signal for minor Z isomer: .sup.1H NMR (400 MHz, CDCl.sub.3) 2.57 (pseudo q, J=6.8 Hz, 2H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) for major E isomer: 190.6, 154.1, 148.9, 129.8, 128.0, 126.3, 125.8, 111.7, 110.8, 68.6, 64.3, 32.1, 17.8, 14.4 ppm. Characteristic signals for Z isomer: .sup.13C NMR (101 MHz, CDCl.sub.3) for minor Z isomer: 154.1, 126.9, 124.8, 111.5, 110.6, 68.1, 64.3, 26.7, 12.7 ppm. GC/MS (EI) major E isomer: m/z (%): 234 (5, [M].sup.+*), 166 (43), 138 (38), 137 (40), 81 (10), 69 (100), 53 (11), 41 (78), 39 (15), 29 (18), 27 (12).
[0266] GC/MS (EI) minor Z isomer: m/z (%): 234 (10, [M]+*), 166 (68), 138 (67), 137 (68), 81 (12), 69 (100), 53 (14), 41 (88), 39 (20), 29 (23), 27 (18).
[0267] Odour description (1% solution in EtOH on paper blotter, 24 h): mild, powdery, vanilla, peppery.
Example 34: 3-ethoxy-4-((4-methylpent-3-en-1-yl)oxy)benzaldehyde
[0268] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (17.3 g, 104 mmol, 1.0 equiv) and 5-bromo-2-methylpent-2-ene (22.0 g, 135 mmol, 1.3 equiv) according to the procedure of example 1 as light yellow liquid (21.3 g, 82% yield), after purification by fractional distillation under high vacuum.
[0269] .sup.1H NMR (400 MHz, CDCl.sub.3): 9.81 (s, 1H), 7.38 (t, J=2.7 Hz, 2H), 6.94 (d, J=8.1 Hz, 1H), 5.20 (tt, J=1.3, 7.3 Hz, 1H), 4.13 (q, J=6.8 Hz, 2H), 4.03 (t, J=7.2 Hz, 2H), 2.55 (q, J=7.1 Hz, 2H), 1.72 (d, J=0.7 Hz, 3H), 1.67 (s, 3H), 1.45 (t, J=7.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.8, 154.3, 149.0, 134.9, 129.8, 126.5, 118.8, 111.6, 110.7, 68.5, 64.4, 27.9, 25.7, 17.8, 14.6 ppm. GC/MS (EI) m/z (%): 248 (2, [M].sup.+*), 166 (31), 138 (14), 137 (16), 83 (96), 67 (13), 55 (100), 41 (40), 39 (13), 29 (20), 27 (11).
[0270] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, chocolate.
Example 35: (Z)-2-ethoxy-1-(hex-3-en-1-yloxy)-4-methylbenzene and (Z)-1-ethoxy-2-(hex-3-en-1-yloxy)-4-methylbenzene
[0271] The compound mixture was obtained from a 1:1 mixture of 2-ethoxy-4-methylphenol and 2-ethoxy-5-methylphenol (3.00 g, 19.7 mmol, 1.0 equiv, prepared according to EP0179532) and (Z)-1-iodohex-3-ene (6.21 g, 29.6 mmol, 1.5 equiv) according to the procedure of example 1 as colorless liquid (1.68 g, 35% yield, 1:1 mixture of regioisomers).
[0272] .sup.1H NMR (400 MHz, CDCl.sub.3, for the 1:1 regioisomer mixture): 6.80 (2d, J=8.1 Hz, 1H), 6.75-6.66 (m, 2H), 5.61-5.50 (m, 1H), 5.49-5.39 (m, 1H), 4.11-4.02 (m, 2H), 4.02-3.95 (2t, J=7.1 Hz, 2H), 2.65-2.52 (m, 2H), 2.29 (s, 3H), 2.19-2.05 (m, 2H), 1.48-1.39 (m, 3H), 1.05-0.94 (2t, J=7.6 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 148.7, 148.7, 146.6, 146.6, 134.2, 134.2, 130.8, 130.7, 124.1, 124.1, 121.2, 121.0, 115.0, 114.9, 114.2, 114.2, 69.0, 68.6, 64.9, 64.5, 27.5, 27.5, 20.9, 20.9, 20.6, 14.9, 14.9, 14.3 ppm.
[0273] Odour description (1% solution in EtOH on paper blotter, 24 h): spicy, eugenol, clove, phenolic, vanilla, medicinal.
Example 36: 4-(4-((4-methylhex-3-en-1-yl)oxy)phenyl)butan-2-one
[0274] The compound was obtained from 4-(4-hydroxyphenyl)butan-2-one (2.00 g, 12.2 mmol, 1.0 equiv) and 1-bromo-4-methylhex-3-ene (2.80 g, 15.8 mmol, 1.3 equiv, prepared according to Zarbin, Paulo H. G.; et al., Journal of Chemical Ecology 2012, 38, 825) according to the procedure of example 1 as colorless liquid (1.12 g, 35% yield, E/Z 86:14).
[0275] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of isomers): 7.16-7.01 (m, 2H), 6.90-6.74 (m, 2H), 5.26-5.09 (m, 1H), 3.92 (2t, J=7.1 Hz, 2H), 2.88-2.79 (m, 2H), 2.78-2.69 (m, 2H), 2.54-2.42 (m, 2H), 2.14 (s, 3H), 2.11-1.96 (m, 2H), 1.75-1.64 (m, 3H), 1.07-0.95 (2t, J=7.6 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of isomers) 208.1, 157.4, 140.0 (Z), 139.8, 132.8, 129.1, 119.1 (Z), 117.9, 114.5, 114.5, 67.8 (Z), 67.7, 45.5, 32.3, 30.1, 28.9, 28.1, 27.9 (Z), 24.9 (Z), 22.9 (Z), 16.1, 12.8, 12.6 ppm.
[0276] Odour description (1% solution in EtOH on paper blotter, 24 h): fruity, raspberry, sweet, powdery.
Example 37: 3-methoxy-4-((4-methylpent-3-en-1-yl)oxy)benzaldehyde
[0277] The compound was obtained from 4-hydroxy-3-methoxybenzaldehyde (2.00 g, 13.2 mmol, 1.0 equiv) and 5-bromo-2-methylpent-2-ene (2.79 g, 17.1 mmol, 1.3 equiv) according to the procedure of example 1 as colorless liquid (2.54 g, 82% yield).
[0278] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of isomers): 9.84 (s, 1H), 7.44-7.41 (m, 1H), 7.40 (s, 1H), 6.96 (d, J=8.1 Hz, 1H), 5.22-5.17 (m, 1H), 4.06 (t, J=7.5 Hz, 2H), 3.92 (s, 3H), 2.58 (q, J=7.3 Hz, 2H), 1.73 (d, J=1.0 Hz, 3H), 1.66 (s, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of isomers) 190.8, 154.0, 149.8, 135.1, 129.9, 126.7, 118.5, 111.3, 109.2, 68.5, 56.0, 27.9, 25.7, 17.8 ppm.
[0279] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, creamy.
Example 38: 3-methoxy-4-((4-methylhept-3-en-1-yl)oxy)benzaldehyde
[0280] The compound was obtained from 4-hydroxy-3-methoxybenzaldehyde (1.32 g, 8.68 mmol, 1.0 equiv) and 1-bromo-4-methylhept-3-ene (2.16 g, 11.3 mmol, 1.3 equiv, prepared according to Zarbin, Paulo H. G.; et al., Journal of Chemical Ecology 2012, 38, 825) according to the procedure of example 1 as light yellow liquid (1.26 g, 55% yield, E/Z 81:19).
[0281] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of isomers): 9.85 (s, 1H), 7.46-7.42 (2d, J=8.1 Hz, 1H), 7.41 (2s, 1H), 7.00-6.95 (2d, J=8.1 Hz, 1H), 5.27-5.11 (m, 1H), 4.12-4.02 (m, 2H), 3.93 (s, 3H), 2.68-2.53 (m, 2H), 2.10-1.93 (m, 2H), 1.74-1.61 (m, 3H), 1.49-1.36 (m, 2H), 0.93-0.83 (2t, J=7.3 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of isomers) 190.9, 154.0, 154.0 (Z), 149.8, 149.8 (Z), 139.1 (Z), 138.9, 129.9, 126.7, 118.9 (Z), 118.2, 111.4, 111.3 (Z), 109.3, 109.2 (Z), 68.7 (Z), 68.6, 56.0, 41.8, 33.9 (Z), 27.8, 27.7 (Z), 23.4 (Z), 21.1 (Z), 20.9, 16.0, 13.9 (Z), 13.6 ppm.
[0282] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, chocolate.
Example 39: (Z)-1-ethoxy-2-(hex-3-en-1-yloxy)benzene
[0283] The compound was obtained from 2-ethoxyphenol (1.64 g, 11.9 mmol, 1.0 equiv) and (Z)-1-iodohex-3-ene (3.50 g, 16.7 mmol, 1.4 equiv) according to the procedure of example 1 as light yellow liquid (0.78 g, 30% yield).
[0284] .sup.1H NMR (400 MHz, CDCl.sub.3): 6.91 (s, 4H), 5.61-5.51 (m, 1H), 5.51-5.40 (m, 1H), 4.10 (q, J=6.9 Hz, 2H), 4.02 (t, J=7.2 Hz, 2H), 2.67-2.53 (m, 2H), 2.19-2.05 (m, 2H), 1.46 (t, J=7.0 Hz, 3H), 1.01 (t, J=7.6 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 148.9, 148.8, 134.3, 124.0, 121.1, 121.0, 113.9, 113.8, 68.6, 64.5, 27.4, 20.6, 14.9, 14.3 ppm.
[0285] Odour description (1% solution in EtOH on paper blotter, 24 h): medicinal, phenolic, vanilla.
Example 40: 3-ethoxy-4-((4-methylhex-3-en-1-yl)oxy)benzaldehyde
[0286] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (2.00 g, 12.2 mmol, 1.0 equiv) and 1-bromo-4-methylhex-3-ene (2.77 g, 15.7 mmol, 1.3 equiv, prepared according to Zarbin, Paulo H. G.; et al., Journal of Chemical Ecology 2012, 38, 825) according to the procedure of example 1 as colorless liquid (1.80 g, 57% yield, E/Z 82:18).
[0287] .sup.1H NMR (400 MHz, CDCl.sub.3): 9.83 (s, 1H), 7.44-7.40 (2d, J=8.1 and 8.3 Hz, 1H), 7.40 (2s, 1H), 6.99-6.94 (2d, J=8.3 and 8.1 Hz, 1H), 5.23-5.15 (m, 1H), 4.14 (q, J=6.9 Hz, 2H), 4.10-4.02 (2t, J=7.3 Hz, 2H), 2.58 (q, J=7.2 Hz, 2H), 2.13-1.98 (m, 2H), 1.75-1.65 (m, 3H), 1.47 (t, J=7.0 Hz, 3H), 1.01 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9, 154.4, 154.3 (Z), 149.1, 140.6 (Z), 140.4, 129.9 (Z), 126.5, 118.4 (Z), 117.2, 111.7, 111.7 (Z), 110.9, 110.7 (Z), 68.8 (Z), 68.6, 64.5, 64.5 (Z), 32.3, 27.8, 27.6 (Z), 24.9 (Z), 22.9 (Z), 16.1, 14.6, 12.9 (Z), 12.6 ppm.
[0288] Odour description (1% solution in EtOH on paper blotter, 24 h): powdery, vanilla, creamy, chocolate, slightly butyric.
Example 41: (Z)-1-(hex-3-en-1-yloxy)-3-methoxy-5-methylbenzene
[0289] The compound was obtained from 3-methoxy-5-methylphenol (2.0 g, 18.8 mmol, 1.0 equiv) and (Z)-1-iodohex-3-ene (3.95 g, 18.8 mmol, 1.3 equiv) according to the procedure of example 1 as colourless liquid (0.63 g, 20% yield).
[0290] .sup.1H NMR (400 MHz, CDCl.sub.3): 6.37-6.33 (m, 2H), 6.33-6.28 (m, 1H), 5.60-5.51 (m, 1H), 5.48-5.40 (m, 1H), 3.94 (t, J=7.0 Hz, 2H), 3.78 (s, 3H), 2.59-2.50 (m, 2H), 2.31 (s, 3H), 2.18-2.06 (m, 2H), 1.01 (t, J=7.6 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 160.6, 160.0, 140.1, 134.3, 124.1, 107.6, 107.1, 98.0, 67.4, 55.2, 27.4, 21.8, 20.7, 14.3 ppm.
[0291] Odour description (1% solution in EtOH on paper blotter, 24 h): green, bell pepper.
Example 42: 1-ethyl-4-((4-methylpent-3-en-1-yl)oxy)benzene
[0292] The compound was obtained from 4-ethylphenol (2.50 g, 20.5 mmol, 1.0 equiv) and 5-bromo-2-methylpent-2-ene (4.32 g, 22.5 mmol, 1.1 equiv, 85% purity) according to the procedure of example 1 as a colorless liquid (2.34 g, 56% yield).
[0293] .sup.13C NMR (101 MHz, CDCl.sub.3): 157.0, 136.3, 134.3, 128.6, 119.7, 114.4, 67.7, 28.3, 28.0, 25.7, 17.8, 15.9 ppm.
[0294] Odour description (1% solution in EtOH on paper blotter, 24 h): animalic, leathery, phenolic, paracresol.
Example 43: 1-methoxy-3-methyl-5-((4-methylpent-3-en-1-yl)oxy)benzene
[0295] The compound was obtained from 3-methoxy-5-methylphenol (2.50 g, 18.1 mmol, 1.0 equiv) and 5-bromo-2-methylpent-2-ene (3.82 g, 19.9 mmol, 1.1 equiv, 85% purity) according to the procedure of example 1 as a colorless liquid (2.20 g, 56% yield).
[0296] .sup.13C NMR (101 MHz, CDCl.sub.3): 160.6, 160.1, 140.1, 134.3, 119.6, 107.6, 107.1, 98.0, 67.6, 55.2, 28.2, 25.7, 21.8, 17.8 ppm.
[0297] Odour description (1% solution in EtOH on paper blotter, 24 h): animalic, leathery, phenolic, paracresol, green, hay, rooty.
Example 44: 1-methyl-4-((4-methylpent-3-en-1-yl)oxy)benzene
[0298] The compound was obtained from p-cresol (3.00 g, 27.7 mmol, 1.0 equiv) and 5-bromo-2-methylpent-2-ene (4.98 g, 30.5 mmol, 1.1 equiv) according to the procedure of example 1 as a colorless liquid (2.58 g, 49% yield).
[0299] .sup.13C NMR (101 MHz, CDCl.sub.3): 156.9, 134.3, 129.8, 129.7, 119.7, 114.4, 67.7, 28.3, 25.7, 20.4, 17.8 ppm.
[0300] Odour description (1% solution in EtOH on paper blotter, 24 h): animalic, leathery, phenolic, paracresol.
Example 45: 1-((4-methylpent-3-en-1-yl)oxy)-3-propylbenzene
[0301] The compound was obtained from 3-propylphenol (2.50 g, 18.4 mmol, 1.0 equiv) and 5-bromo-2-methylpent-2-ene (3.87 g, 20.2 mmol, 1.1 equiv, 85% purity) according to the procedure of example 1 as a colorless liquid (1.67 g, 42% yield).
[0302] .sup.13C NMR (101 MHz, CDCl.sub.3): 159.0, 144.3, 134.3, 129.1, 120.8, 119.7, 114.8, 111.5, 67.5, 38.1, 28.3, 25.7, 24.4, 17.8, 13.8 ppm.
[0303] Odour description (1% solution in EtOH on paper blotter, 24 h): animalic, leathery, phenolic, paracresol, green, hay, rooty.
Example 46: (Z)-1-(2-(hex-3-en-1-yloxy)phenyl)propan-1-one
[0304] The compound was obtained from 1-(2-hydroxyphenyl)propan-1-one (8.0 g, 53.3 mmol, 1.0 equiv) and (Z)-1-chlorohex-3-ene (9.5 g, 79.9 mmol, 1.5 equiv) according to the process of example 1 as colorless liquid (21.0 mmol, 5.0 g, 39% yield).
[0305] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.70-7.66 (m, 1H), 7.46-7.37 (m, 1H), 7.00-6.88 (m, 2H), 5.56-5.41 (m, 2H), 4.06 (t, J=6.7 Hz, 2H), 3.01 (q, J=7.3 Hz, 2H), 2.62-2.57 (m, 2H), 2.14-2.06 (m, 2H), 1.16 (t, J=7.3 Hz, 3H), 0.99 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 203.6, 157.9, 134.5, 133.1, 130.3, 128.5, 124.2, 120.6, 112.2, 68.1, 37.2, 27.3, 20.7, 14.2, 8.5 ppm. GC/MS (EI): m/z (%): 232 (1) [M.sup.+], 203 (5), 185 (5), 163 (11), 150 (27), 121 (100), 82 (26), 55 (38).
[0306] Odor description (1% solution in EtOH on paper blotter, 24 h): green, wintergreen
Example 47: 3-ethoxy-4-(((Z)-hex-3-en-1-yl)oxy)benzaldehyde O-methyl oxime
[0307] A mixture of (Z)-3-ethoxy-4-(hex-3-en-1-yloxy)benzaldehyde (1.0 g, 4.0 mmol, 1.0 equiv), O-methylhydroxylamine hydrochloride (0.5 g, 6.0 mmol, 1.5 equiv) and sodium acetate (1.0 g, 12.1 mmol) in Methanol (20 ml) and Water (10 ml) was stirred for 16 hours under argon atmosphere at r.t. The solvent was removed by rotary evaporation, the residue was purified by silica gel column chromatography (PE:MTBE=9:1) and give 3-ethoxy-4-(((Z)-hex-3-en-1-yl)oxy)benzaldehyde O-methyl oxime (4.0 mmol, 1.1 g, yield: 98%) as light yellow liquid.
[0308] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.89 (s, 1H), 7.14 (s, 1H), 6.90 (d, J=8.2 Hz, 1H), 6.75 (d, J=8.2 Hz, 1H), 5.49-5.31 (m, 2H), 4.03 (q, J=6.9 Hz, 2H), 3.92 (t, J=7.0 Hz, 2H), 3.86 (s, 3H), 2.54-2.46 (m, 2H), 2.08-1.99 (m, 2H), 1.37 (t, J=7.0 Hz, 3H), 0.91 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 150.4, 149.0, 148.5, 134.6, 125.1, 123.8, 121.5, 112.7, 110.2, 68.4, 64.5, 61.8, 27.3, 20.7 14.8, 14.3 ppm. GC/MS (EI): m/z (%): 277 (22) [M.sup.+], 195 (100), 179 (1), 167 (24), 140 (13), 125 (5), 55 (38).
[0309] Odor description (1% solution in EtOH on paper blotter, 24 h): vanilla (sweet, gourmand, carnation floral, chestnut cream)
Example 48: (Z)-2-ethoxy-4-(ethoxymethyl)-1-(hex-3-en-1-yloxy)benzene
a) (Z)-(3-ethoxy-4-(hex-3-en-1-yloxy)phenyl)methanol
[0310] To a solution of (Z)-3-ethoxy-4-(hex-3-en-1-yloxy)benzaldehyde (24.0 g, 96.6 mmol, 1.0 equiv) in methanol (200 ml) was added sodium borohydride (1.8 g, 48.3 mmol, 0.5 equiv) portionwsie at 10 C. and stirred for 16 hours under argon atmosphere at rt. The solvent was removed by rotary evaporation, and water 200 mL was added, the solution was extracted with MTBE (150 mL*3), the organic layer was dried with MgSO.sub.4, filtered, and concentrated, the residue was purified by silica gel column chromatography (PE:MTBE=4:1) to give (Z)-(3-ethoxy-4-(hex-3-en-1-yloxy)phenyl)methanol (85.0 mmol, 22.0 g, yield: 88%) as colorless liquid. .sup.1H NMR (400 MHz, CDCl.sub.3) 6.90 (s, 1H), 6.84 (s, 2H), 5.54-5.41 (m, 2H), 4.57 (d, J=5.5 Hz, 2H), 4.07 (q, J=7.0 Hz, 2H), 3.98 (t, J=7.2 Hz, 2H), 2.60-2.55 (m, 2H), 2.14-2.07 (m, 2H), 1.98 (t, J=5.7 Hz, 1H), 1.43 (t, J=7.0 Hz, 3H), 0.98 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 149.0, 148.3, 134.4, 133.9, 124.0, 119.6, 113.7, 112.8, 68.8, 65.2, 64.6, 27.5, 20.7, 14.9, 14.3 ppm. GC/M S (EI): m/z (%): 250 (24) [M+], 194 (1), 168 (100), 153 (2), 140 (27), 122 (36), 107 (4), 93 (17), 77 (6), 65 (12), 55 (43).
b) (Z)-2-ethoxy-4-(ethoxymethyl)-1-(hex-3-en-1-yloxy)benzene
[0311] To a solution of sodium hydride (0.7 g, 56% Wt, 16.0 mmol, 2.0 equiv) in DMF (50 mL) was added (Z)-(3-ethoxy-4-(hex-3-en-1-yloxy)phenyl)methanol (2.0 g, 8.0 mmol, 1.0 equiv) at 0 C. and the mixture was stirred for 5 hours under argon atmosphere at r.t. Then bromoethane (2.6 g, 24.0 mmol, 3.0 equiv) was added to the reaction solution at 0 C. and the resulting mixture was stirred at r.t for 16 h. The reaction was quenched by adding water, then extracted with MTBE (100 mL*3), the organic layer was dried with MgSO4, filtered, and concentrated, the residue was purified by silica gel column chromatography (PE:MTBE=98:2) and give (Z)-2-ethoxy-4-(ethoxymethyl)-1-(hex-3-en-1-yloxy)benzene (1.2 g, 4.2 mmol, yield: 52%) as colorless liquid.
[0312] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.90 (s, 1H), 6.84 (s, 2H), 5.54-5.41 (m, 2H), 4.42 (s, 2H), 4.09 (q, J=7.0 Hz, 2H), 3.98 (t, J=7.2 Hz, 2H), 3.51 (q, J=7.0 Hz, 2H), 260-2.55 (m, 2H), 2.14-2.06 (m, 2H), 1.44 (t, J=7.0 Hz, 3H), 1.23 (t, J=7.0 Hz, 3H), 0.98 (t, J=7.5 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) 148.9, 148.3, 134.4, 131.4, 124.1, 120.4, 113.6, 113.4, 72.6, 68.8, 65.5, 64.5, 27.5, 20.7, 15.3, 14.9, 14.3 ppm. GC/MS (EI): m/z (%): 278 (46) [M.sup.+], 196 (100), 179 (5), 151 (89), 135 (16), 123 (57), 83 (17), 55 (79).
[0313] Odor description (1% solution in EtOH on paper blotter, 24 h): spicy (eugenol, smokey), powdery (vanilla)
Example 49: (Z)-2-ethoxy-1-(hex-3-en-1-yloxy)-4-(methoxymethyl)benzene
[0314] The compound was obtained from (Z)-(3-ethoxy-4-(hex-3-en-1-yloxy)phenyl)methanol (3.0 g, 12.0 mmol, 1.0 equiv) and iodomethane (5.1 g, 36.0 mmol, 3.0 equiv) according to the process of example 48 as colorless liquid (5.5 mmol, 1.5 g, 46% yield).
[0315] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.89 (s, 1H), 6.86-6.82 (m, 2H), 5.59-5.47 (m, 1H), 5.47-5.37 (m, 1H), 4.37 (s, 2H), 4.09 (q, J=7.0 Hz, 2H), 3.99 (t, J=7.2 Hz, 2H), 3.36 (s, 3H), 2.60-2.55 (m, 2H), 2.14-2.07 (m, 2H), 1.44 (t, J=7.0 Hz, 3H), 0.98 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 148.9, 148.4, 134.4, 131.0, 124.0, 120.5, 113.5, 113.4, 74.6, 68.8, 64.5, 57.8, 27.5, 20.7, 14.9, 14.3 ppm. GC/MS (EI): m/z (%): 264 (31) [M.sup.+], 182 (100), 151 (61), 137 (14), 123 (3565 (11), 55 (43).
[0316] Odor description (1% solution in EtOH on paper blotter, 24 h): spicy (eugenol, smokey), powdery (vanilla)
Example 50: (Z)-2-ethoxy-1-(hex-3-en-1-yloxy)-4-(isopropoxymethyl)benzene
[0317] The compound was obtained from (Z)-(3-ethoxy-4-(hex-3-en-1-yloxy)phenyl)methanol (3.0 g, 12.0 mmol, 1.0 equiv) and 2-bromopropane (4.4 g, 36.0 mmol, 3.0 equiv) according to the process of example 48 as colorless liquid (0.5 mmol, 0.2 g, 4% yield).
[0318] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.90 (s, 1H), 6.84 (s, 2H), 5.57-5.47 (m, 1H), 5.47-5.36 (m, 1H), 4.42 (s, 2H), 4.09 (q, J=7.0 Hz, 2H), 3.98 (t, J=7.2 Hz, 2H), 3.66 (dt, J=12.2, 6.1 Hz, 1H), 2.60-2.54 (m, 2H), 2.14-2.06 (m, 2H), 1.44 (t, J=7.0 Hz, 3H), 1.20 (d, J=6.1 Hz, 6H), 0.98 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 148.9, 148.2, 134.3, 132.0, 124.1, 120.2, 113.7, 113.4, 70.6, 69.9, 68.8, 64.5, 27.5, 22.2, 20.7, 14.9, 14.3 ppm. GC/MS (EI): m/z (%): 292 (73) [M.sup.+], 233 (3), 210 (60), 152 (100), 139 (25), 123 (56), 55 (54).
[0319] Odor description (1% solution in EtOH on paper blotter, 24 h): spicy (eugenol, smokey), powdery (vanilla), green
Example 51: 4-(cyclohex-3-en-1-yloxy)-3-ethoxybenzaldehyde
[0320] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (10.0 g, 60.2 mmol, 1.0 equiv) and cyclohexane-1,4-diol (9.1 g, 78.3 mmol, 1.3 equiv) according to the process of example 19 as colorless liquid (8.1 mmol, 2.0 g, 13% yield).
[0321] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.83 (s, 1H), 7.49-7.33 (m, 2H), 7.02 (d, J=8.7 Hz, 1H), 5.88-5.49 (m, 2H), 4.74-4.53 (m, 1H), 4.12 (q, J=7.0 Hz, 2H), 2.59-2.44 (m, 1H), 2.39-2.23 (m, 2H), 2.22-2.03 (m, 2H), 1.95-1.79 (m, 1H), 1.44 (t, J=7.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9, 153.4, 150.1, 130.2, 126.9, 126.2, 123.6, 114.6, 111.9, 74.4, 64.7, 31.0, 27.6, 23.7, 14.7 ppm. GC/MS (EI): m/z (%): 246 (24) [M.sup.+], 192 (1), 166 (100), 149 (11), 138 (78), 81 (95), 53 (25).
[0322] Odor description (1% solution in EtOH on paper blotter, 24 h): powdery (vanilla)
Example 52: 4,4-(hex-3-ene-1,6-diylbis(oxy))bis(3-ethoxybenzaldehyde)
[0323] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (10.0 g, 60.2 mmol, 2.5 equiv) and 1,6-dibromohex-3-ene (5.8 g, 24.1 mmol, 1.0 equiv) according to the process of example 1 as colorless liquid (2.7 mmol, 1.1 g, 22% yield, E/Z mixture, E:Z=2:1).
[0324] .sup.1H NMR (400 MHz, CDCl.sub.3, E/Z mixture) 9.83 (s, 2H), 7.52-7.31 (m, 4H), 6.97-6.92 (m, 2H), 6.26-5.55 (m, 2H), 4.77-3.98 (m, 8H), 2.79-2.55 (m, 2H), 2.45-2.30 (m, 1H), 2.03-1.96 (m, 1H), 1.60-1.38 (m, 6H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, E isomer) 191.0, 154.2, 149.2, 130.0, 128.4, 126.6, 111.9, 110.9, 64.5, 64.4, 32.4, 14.7 ppm.
[0325] GC/M S (EI): m/z (%): 412 (6) [M.sup.+], 246 (11), 177 (23), 137 (40), 109 (16), 81 (100), 67 (15), 53 (15).
[0326] Odor description (1% solution in EtOH on paper blotter, 24 h): powdery (vanilla)
Example 53: 3-ethoxy-4-(pent-4-en-1-yloxy)benzaldehydeComparative Example
[0327] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (8.0 g, 48.1 mmol, 1.0 equiv) and 5-bromopent-1-ene (9.3 g, 62.6 mmol, 1.3 equiv) according to the procedure of example 1 as colorless liquid (43.9 mmol, 10.6 g, 91% yield).
[0328] .sup.1H NMR (400 MHz, CDCl.sub.3): 9.83 (s, 1H), 7.38-7.44 (m, 2H), 6.96 (d, J=8.1 Hz, 1H), 5.80-5.87 (m, 1H), 5.00-5.11 (m, 2H), 4.07-4.18 (m, 4H), 2.30-2.24 (m, 2H), 2.01-1.94 (m, 2H), 1.47 (t, J=7.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 191.0, 154.4, 149.2, 137.6, 130.0, 126.6, 115.4, 111.9, 110.9, 68.4, 64.6, 30.0, 28.1, 14.7 ppm. GC/M S (EI): m/z (%): 234 (65) [M.sup.+], 206 (1), 166 (65), 149 (10), 138 (100), 81 (25), 69 (18).
Example 54: (E)-3-ethoxy-4-(hex-2-en-1-yloxy)benzaldehydecomparative example
[0329] The compound was obtained from 3-ethoxy-4-hydroxybenzaldehyde (4.0 g, 24.1 mmol, 1.0 equiv) and (E)-1-bromohex-2-ene (5.9 g, 36.1 mmol, 1.5 equiv) according to the procedure of example 1 as colorless liquid (18.1 mmol, 4.5 g, 75% yield).
[0330] 1H NMR (400 MHz, CDCl.sub.3): 9.83 (s, 1H), 7.41-7.40 (m, 2H), 6.98 (d, J=8.1 Hz, 1H), 5.81-5.90 (m, 1H), 5.68-5.76 (m, 1H), 4.64 (d, J=5.8 Hz, 2H), 4.15 (q, J=7.0 Hz, 2H), 1.98-2.16 (m, 2H), 1.38-1.51 (m, 5H), 0.85-0.97 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.9, 154.0, 149.2, 136.1, 130.0, 126.4, 124.1, 112.3, 110.6, 69.8, 65.2, 34.4, 22.5, 14.6, 13.6 ppm. GC/M S (EI): m/z (%): 248 (15) [M+], 219 (1), 166 (100), 138 (70), 81 (25), 55 (35).
Example 55: Application in Liquid Detergent
a) Sample Preparation
[0331] 0.2% by weight of ethyl vanillin (3-ethoxy-4-hydroxybenzaldehyde, sample A) or (Z)-3-ethoxy-4-(hex-3-en-1-yloxy)benzaldehyde (compound of example 1, sample B) were incorporated respectively into unperfumed liquid detergent base by magnetic stirring at room temperature for 24 h.
b) Color Stability
[0332] The above prepared samples were visually inspected in comparison to an unperfumed base sample (sample C). The ethylvanillin sample (A) showed strong brown-purple coloration, whereas the sample containing the precursor (B) was optically identical to the unperfumed base (C). All three samples are shown in
c) Washtest and Sensory Evaluation
[0333] A 40 C. machine wash cycle was performed using 55 g of the above prepared liquid detergent samples A and B and odor-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 odor intensity and quality. The odor intensity was recorded on an intensity scale of 0 (odorless) to 5 (extremely strong). As can be seen from Table 1 below, virtually no odor was released from the T-shirts washed with the colored ethyl vanillin detergent base, whereas the T-shirts washed with the color-neutral detergent base containing (Z)-3-ethoxy-4-(hex-3-en-1-yloxy)benzaldehyde exhibited a strong vanilla, sweet, powdery and creamy fragrance after 1 and 4 days. The difference in odor strength between the two samples after 1 and 4 days was highly significant (Student's t-test, p<0.01).
TABLE-US-00001 TABLE 1 Sample wet 1 day 4 days Ethylvanillin (A) 1.2 0.9 1 (Z)-3-ethoxy-4-(hex-3-en-1- 1.3 3 3.7 yloxy)benzaldehyde (B) significance of difference p = 0.001 p = 0.003
[0334] The results are also visualized in
Example 56: Application in Liquid Detergent (Position of Double Bond in Side Chain)
[0335] In order to highlight the importance of the position of the double bond, a comparative assessment in liquid detergent application (as described in Example 55a and c) was carried out with ethylvanillin ethers (compounds of formula IV) having unsaturated side chains with the double bond placed in positions A-2 or A-4 in comparison to the compounds of the current invention which have the double bond positioned at A-3. The odour intensity was recorded on an intensity scale of 0 (odorless) to 5 (extremely strong). The results are summarized in Table 2.
##STR00014##
TABLE-US-00002 TABLE 2 length position of side of double 1 4 Entry Compound chain bond wet day days 1 3-ethoxy-4- C.sub.5 -4 1.5 1.3 1.2 (pent-4-en-1-yloxy) benzaldehyde (Example 53) 2 3-ethoxy-4- -3 1.1 3.2 3.8 (pent-3-en-1-yloxy) benzaldehyde (Example 33) 3 3-ethoxy-4- C.sub.6 -2 1.2 1.8 1.4 (hex-2-en-1-yloxy) benzaldehyde (Example 54) 4 3-ethoxy-4- -3 3.2 3.2 3.6 (hex-3-en-1-yloxy) benzaldehyde (Example 1)
[0336] The results show that only compounds of the present invention with the double bond in the -3 position of the side chain (homoallylic ethers, entries 2 and 4) release a strong odor on dry fabric. In contrast, only very weak odors were detected on dry fabric washed with similar compounds with identical chain lengths having the double bond either in the -4 or -2 position (entries 1 and 3).
Example 57: Application in Liquid DetergentGeneration of Different Odor Profiles
[0337] Liquid detergent samples were prepared and used in washtests and subsequent sensory evaluation of the washed and dried fabric as described in Example 45a and c. The odor intensity was recorded on an intensity scale of 0 (odorless) to 5 (extremely strong). The results are summarized in Table 3.
TABLE-US-00003 TABLE 3 Entry wet 1 day 4 days odor on dry fabric 1 3-ethoxy-4-((4-methylpent-3-en-1-yl)oxy) 1.5 3.3 3.4 vanilla benzaldehyde (Example 34) 2 methyl (Z)-4-(hex-3-en-1-yloxy)-2-hydroxy- 1.0 1.7 3.3 oakmoss 3,6-dimethylbenzoate (Example 9) 3 4-(4-(hex-3-en-1-yloxy)phenyl)butan-2-one 3.0 2.8 3.6 raspberry (Example 6) 4 1-(((Z)-hex-3-en-1-yl)oxy)-2-methoxy-4- 2.0 1.9 3.0 spicy, vanilla ((E)-prop-1-en-1-yl)benzene (Example 11) 5 4-(cyclopent-3-en-1-yloxy)-3- n.d. 3.0 3.7 vanilla, powdery ethoxybenzaldehyde (Example 20) 6 (Z)-4-allyl-1-(hex-3-en-1-yloxy)-2- 1.6 2.4 2.5 spicy, clove, methoxybenzene (Example 10) gingerbread
[0338] The results illustrate that strong fragrance intensities are achieved on dry fabric with compounds of the current invention. The odor direction is dominated by the given phenolic fragrant compound HX. In some cases, it can be slightly modulated by the side chain or its fragments.
Example 58: Headspace Analysis of Released Volatiles
[0339] 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 (
[0340] 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. The main sensorially active volatiles released from the compounds of formula (I) are reported in Table 4 (indicated are relative peak area %; in bold: main odor vector).
TABLE-US-00004 TABLE 4 Precursor Released Volatiles (Z)-3-ethoxy-4-(hex-3-en-1- (Z)-hex-3-en-1-ol (5.6%), ethyl vanillin yloxy)benzaldehyde (Example 1) (0.3%) 3-ethoxy-4-((4-methylpent-3-en-1- 3-methylbut-2-enal (0.1%), 4-methylpent-3- yl)oxy)benzaldehyde (Example 34) en-1-ol (2.7%), 5,5-dimethylfuran-2(5H)-one (0.3%), ethyl vanillin (0.5%) 3-ethoxy-4-(pent-3-en-1- (E,Z)-pent-3-en-1-ol (1.2%), ethyl vanillin yloxy)benzaldehyde (Example 33) (0.7%) (Z)-4-allyl-1-(hex-3-en-1-yloxy)-2- (Z)-hex-3-en-1-ol (1.9%), eugenol (1.0%) methoxybenzene (Example 10) (Z)-2-ethoxy-1-(hex-3-en-1-yloxy)-4- (Z)-hex-3-en-1-ol (0.8%), 2-ethoxy- (isopropoxymethyl)benzene 4(isopropoxymethyl)phenol ( Propyl (Example 50) Diantilis , 17.1%)
[0341] 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. 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 59: Assessment of Biodegradability
[0342] 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 5.
TABLE-US-00005 TABLE 5 Compound Biodegradation of example Compound name in % result 1 (Z)-3-ethoxy-4-(hex-3-en-1- 61 inherently yloxy)benzaldehyde biodegradable 33 3-ethoxy-4-(pent-3-en-1- 66 inherently yloxy)benzaldehyde biodegradable 34 3-ethoxy-4-((4-methylpent- 69 inherently 3-en-1-yl)oxy)benzaldehyde biodegradable 8 (Z)-4-(hex-3-en-1-yloxy)-3- 92 readily methoxybenzaldehyde biodegradable 6 4-(4-(hex-3-en-1- 82 readily yloxy)phenyl)butan-2-one biodegradable 18 4-(4-((4-methylpent-3-en-1- 91 readily yl)oxy)phenyl)butan-2-one biodegradable 20 4-(cyclopent-3-en-1-yloxy)- 74 inherently 3-ethoxybenzaldehyde biodegradable
[0343] 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.
[0344] A compound 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 60: methyl 5-(2-ethoxy-4-formylphenoxy)pent-2-enoate
[0345] To a solution of (Z)-3-ethoxy-4-(hex-3-en-1-yloxy)benzaldehyde (10.0 g, 40 mmol) and methyl but-2-enoate (8.1 g, 80 mmol) in DCE (50 mL) was added Zhan catalyst-1b (0.3 g, 0.4 mmol) and stirred at 70 C. for 16 hours under argon. The solvent was removed by rotary evaporation, and the residue was purified by column chromatography on silica gel (PE:MTBE=7:3) to give 5-(2-ethoxy-4-formylphenoxy)pent-2-enoate (9.0 mmol, 3.7 g, yield: 22%) as white solid.
[0346] .sup.1H NMR (400 MHz, CDCl.sub.3, mixture of E/Z isomers) 9.92-9.77 (m, 1H), 7.47-7.33 (m, 2H), 7.11-6.88 (m, 2H), 6.08-5.86 (m, 1H), 4.28-4.03 (m, 4H), 3.81-3.67 (m, 3H), 2.84-2.72 (m, 2H), 1.47 (t, J=7.0 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, mixture of E/Z isomers) 191.0, 191.0, 166.7, 154.1, 153.8, 149.4, 145.3, 144.2, 130.5, 130.3, 126.5, 126.4, 123.5, 121.5, 112.3, 112.2, 111.1, 111.0, 67.8, 67.1, 64.6, 64.6, 51.6, 51.2, 31.8, 28.8, 14.7, 14.6 ppm.
[0347] Odour description (1% solution in EtOH on paper blotter, 24 h): sweet powdery gourmand, vanilla, coffee, creamy, vanilla, milky
Example 61: ethyl 2-(2-ethoxy-4-formylphenoxy)pent-4-enoate
a) Ethyl 2-hydroxypent-4-enoate
[0348] To a solution of allyltrimethylsilane (11.2 g, 98 mmol) and ethyl 2-oxoacetate (5.0 g, 49 mmol) in DCM (100 mL) was added boron trifluoride diethyl etherate (10.4 g, 74 mmol) in DCM (50 mL) slowly at room temperature and stirred for 16 hours. The mixture was quenched by adding aqueous 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=9:1) to give ethyl 2-hydroxypent-4-enoate (2.3 g, yield: 33%) as light yellow liquid.
[0349] .sup.1H NMR (400 MHz, CDCl.sub.3) 5.89-5.74 (m, 1H), 5.20-5.09 (m, 2H), 4.35-4.16 (m, 3H), 2.89 (d, J=5.9 Hz, 1H), 2.64-2.35 (m, 2H), 1.33-1.25 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 174.4, 132.5, 118.7, 70.0, 61.7, 38.7, 14.2 ppm.
b) Ethyl 2-(2-ethoxy-4-formylphenoxy)pent-4-enoate
[0350] Ethyl 2-(2-ethoxy-4-formylphenoxy)pent-4-enoate was obtained from 3-ethoxy-4-hydroxybenzaldehyde (3.2 g, 19 mmol) and ethyl 2-hydroxypent-4-enoate (2.5 g, 17 mmol) according to the procedure of example 19 as colorless liquid (8.4 mmol, 2.5 g, 48% yield).
[0351] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.82 (s, 1H), 7.44-7.30 (m, 2H), 6.94 (d, J=8.1 Hz, 1H), 6.07-5.84 (m, 1H), 5.32-5.04 (m, 2H), 4.80 (t, J=6.1 Hz, 1H), 4.29-4.03 (m, 4H), 2.76 (t, J=6.5 Hz, 2H), 1.44 (t, J=7.0 Hz, 3H), 1.24 (t, J=7.1 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 190.8, 170.3, 152.9, 149.9, 132.2, 131.4, 125.7, 118.7, 115.7, 112.0, 77.6, 64.7, 61.3, 37.1, 14.6, 14.2 ppm. GC/MS (EI): m/z (%): 292 (100) [M.sup.+], 264 (1), 219 (9), 166 (38), 149 (42), 137 (67), 99 (61), 81 (29).
[0352] Odour description (1% solution in EtOH on paper blotter, 24 h): sweet powdery gourmand (vanilla, coffee) creamy (vanilla, milky)
Example 62: methyl 2-hydroxy-3,6-dimethyl-4-((4-methylpent-3-en-1-yl)oxy)benzoate
[0353] The compound was obtained from methyl 2,4-dihydroxy-3,6-dimethylbenzoate (1.5 g, 7.7 mmol) and 5-bromo-2-methylpent-2-ene (1.4 g, 8.4 mmol) according to the process of example 1 as white solid (0.5 g, 20% yield).
[0354] 1H NMR (400 MHz, CDCl3) 11.75 (s, 1H), 6.17 (s, 1H), 5.14 (t, J=7.2 Hz, 1H), 3.92-3.81 (m, 5H), 2.50-2.31 (m, 5H), 2.01 (s, 3H), 1.69-1.55 (m, 6H) ppm. 13C NMR (101 MHz, CDCl3) 171.6, 161.2, 159.9, 138.9, 133.5, 118.5, 110.0, 105.8, 104.2, 66.8, 50.7, 27.3, 24.7, 23.6, 16.8, 6.8 ppm. GC/MS (EI): m/z (%): 278 (2) [M.sup.+], 247 (1), 231 (4), 196 (22), 164 (47), 83 (66), 55 (100).
[0355] Odour description (1% solution in EtOH on paper blotter, 24 h): mossy (evernyl)
Example 63: methyl 2-hydroxy-3,6-dimethyl-4-(pent-3-en-1-yloxy)benzoate
[0356] The compound was obtained from methyl 2,4-dihydroxy-3,6-dimethylbenzoate (4.0 g, 20 mmol) and 5-bromopent-2-ene (3.0 g, 20.4 mmol) according to the procedure of example 1 as white solid (3.1 g, 58% yield).
[0357] 1H NMR (400 MHz, CDCl3) 11.75 (s, 1H), 6.25-6.06 (m, 1H), 5.60-5.32 (m, 2H), 3.96-3.79 (m, 5H), 2.54-2.30 (m, 5H), 1.99 (s, 3H), 1.67-1.54 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3) 172.6, 162.2, 160.9, 140.0, 127.9, 126.6, 111.1, 106.8, 105.3, 67.9, 51.7, 32.6, 24.6, 18.0, 7.8 ppm. GC/MS (EI): m/z (%): 264 (27) [M.sup.+], 217 (29), 196 (76), 164 (100), 136 (47), 69 (51).
[0358] Odour description (1% solution in EtOH on paper blotter, 24 h): mossy, evernyl, dry powdery
Example 64: Application in Shampoo Base
[0359] A hair shampoo sample (20 g) was prepared by adding 0.2% by weight of 3-ethoxy-4-(hex-3-en-1-yloxy)benzaldehyde (compound of example 3) to unperfumed clear hair shampoo base and mixing on a bottle roller for 24 h at room temperature. An odour-neutral human hair swatch was wetted with warm tap water and lathered delicately with 2 mL of the above hair shampoo sample for 30 sec by hand wearing gloves. The lathered hair swatch was 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 swatch between two fingers, it was left to dry in open air. The odour of the wet and dried hair swatch (1 and 3 days) was assessed by a panel of 7 experts. Five out of seven experts perceived a vanilla note on dry hair after 1 and 3 days.
[0360] The experiment demonstrates that precursors of the current invention are capable of releasing fragrance on dry hair.
Example 65: Malodour Reduction
[0361] Fabrics (18 cm14 cm cotton jersey) were stripped before use. They were then washed in European washing machines (40 C.1,000 spin/min) with one unit dose (65 g) used per wash load. The unit dose contained 2% of a 10% solution of the compound of formula 1 in trietylcitrate. [0362] a) Compound of example 33 [0363] b) Compound of example 34 [0364] c) Compound of example 1
[0365] The total wash load was 1.6 kg made up of test cloths and hand towels (100% cotton) as ballast. The cloth was line dried and left overnight in a perfume free room at 25 C., left to hang for 3 days and then wrapped in foil the day prior to the test (day 3). 30 minutes before the assessment, 50 L of the pure Male Sweat malodour was placed on top of a cotton pad and introduced into a 500 ml powder jar. One cotton jersey square was then placed over the top of the powder jar and secured with a rubber band. Every sample tested was coded with a random code number.
[0366] The malodour and fragrance perceived intensities were assessed by the trained sensory panel using a 0-100 line scale. All malodour and fragrance perceived intensities were scaled against the malodour control sample. The malodour perceived intensity was set at 40 for Male Sweat malodour and the fragrance perceived intensity was set at 0.
[0367] The order of samples assessed by the panelists was pre-determined using a balanced randomisation. The samples were assessed in a sequential monadic way. The products were assessed twice by 14 panelists, thus giving 28 assessments per sample.
[0368] Before analysis, the data was checked for outliers and extreme violations to normality.
[0369] Reliability of the data was checked and data of panelists with poor discrimination, consensus or repeatability may have been removed from the analysis. The data was analysed using analysis of variance (ANOVA). A 5% significance level (95% confidence level) was used. Separate ANOVAs were carried out for malodour and fragrance intensity. The ANOVA have product, panelist, and replicate as factors. Pairwise comparisons of the products were done using the Benjamini-Hochberg correction for multiple testing. The estimated product means are reported. It is indicated with letters if the product means are statistically significantly different from each other: if they are not, then they share the same letter.
a) Perceived Malodour Intensity
TABLE-US-00006 Perceived Malodour Significance of Sample Composition Intensity Differences 1 Compound of example 34 + 20.6 A Male Sweat Malodour 2 Compound of example 33 + 26.5 B Male Sweat Malodour 3 Compound of example 1 + 29.5 B Male Sweat Malodour 4 Male Sweat Malodour 37.0 C
[0370] Where the same letter is shown in the significance of differences column there are no statistically significant differences between the relevant figures.
[0371] When assessed from 4 day dry cloth, fabrics washed with any of the three products significantly reduced the perception of the Male Sweat Malodour (in comparison with sample 4). Sample 2 was not significantly different in perceived malodour intensity (PMI) than sample 3, but these two samples had a significantly higher PMI than sample 1.
b) Perceived Fragrance Intensity
TABLE-US-00007 Perceived Fragrance Significance of Sample Sample Intensity Differences 5 Male Sweat Malodour 3.0 A 6 Compound of example 1 + 18.3 B Male Sweat Malodour 7 Compound of example 33 + 22.3 B Male Sweat Malodour 8 Compound of example 34 + 31.1 C Male Sweat Malodour
[0372] Where the same letter is shown in the significance of differences column there are no statistically significant differences between the relevant figures.
[0373] When the 4 day dry cloth was assessed against sample 5 in the presence of the Male Sweat Malodour, the fabric washed with sample 8 was significantly stronger in perceived fragrance intensity (PFI) than fabric washed with sample 6 or sample 7, which were not perceived to be significantly different in PFI.
[0374] The compounds of the present invention significantly reduced the perceived intensity of the sweat malodour and were perceivable in the presence of the malodour.