Organic compounds

Abstract

A compound represented by the formula I ##STR00001##
R.sub.1 is (CHR.sub.4).sub.m(CHR.sub.5).sub.n(CHR.sub.6).sub.oCHO, with R.sub.4, R.sub.5, R.sub.6 being independently selected from H or Me, and with m, n, o being independently selected from 0 and 1; R.sub.2 is H or Me; and R.sub.3 is a C3-C6 branched, linear or cyclic alkenyl residue. Said compounds are useful as perfume ingredients in personal care and household care products.

Claims

1. A compound represented by formula I ##STR00010## wherein R.sub.1 is (CHR.sub.4).sub.m(CHR.sub.5).sub.n(CHR.sub.6).sub.oCHO, with R.sub.4, R.sub.5, R.sub.6 being independently selected from H or Me, and with m, n, o being independently selected from 0 and 1; R.sub.2 is Me; and R.sub.3 is a C3-C6 branched, linear or cyclic alk-2-enyl residue.

2. A pro-perfume, suitable to release at least one compound represented by formula I ##STR00011## wherein R.sub.1 is (CHR.sub.4).sub.m(CHR.sub.5).sub.n(CHR.sub.6).sub.oCHO, with R.sub.4, R.sub.5, R.sub.6 being independently selected from H or Me, and with m, n, o being independently selected from 0 and 1; R.sub.2 is Me; and R.sub.3 is a C3-C6 branched, linear or cyclic alk-2-enyl residue, the pro-perfume being optionally an aminal and/or enamine of the compound represented by the formula I.

3. A perfume composition comprising the pro-perfume according to claim 2.

4. The perfume composition according to claim 3 that is free of any aryl-substituted propanal odourants that are unsubstituted on the aryl ring at a position ortho to the substituent bearing the aldehyde functionality.

5. The perfume composition according to claim 3 comprising one or more additional fragrance ingredients, optionally 3-(4-isobutyl-2-methylphenyl)propanal.

6. A personal care or household care composition comprising at least a perfume composition as defined in claim 3.

7. The personal care or household care composition according to claim 6, further comprising enzymes.

8. The personal or household care composition according to claim 6, characterised in that it is a textile treatment product.

9. The personal or household care composition according to claim 6, characterised in that it is a detergent composition.

10. A method of imparting green odour characteristics to a fine fragrance or consumer product comprising the step of adding thereto a pro-perfume as defined in claim 2, and selectively excluding from said fine fragrance or consumer product any aryl-substituted alkanal compounds, which are unsubstituted on the ring at the position ortho to the substituent containing aldehyde functionality, said selective addition or exclusion being based on the susceptibility of said compounds to enzymatically-mediated degradation to their benzoic acid derivatives when incubated with hepatocytes isolated from rats, said compounds being suitable for addition on the basis that they do not degrade to their benzoic acid derivatives, whereas said compounds being excluded on the basis that they do degrade to their benzoic acid derivatives.

11. The perfume composition according to claim 3 that is free of 3-(4-tert-butylphenyl)-2-methylpropanal.

12. The compound according to claim 1 wherein R.sub.3 is a C3-C6 branched, linear or cyclic alk-2-enyl residue.

13. The compound according to claim 1 wherein R.sub.3 is a C3-C6 alk-2-enyl residue with an exo-methylene group.

14. The compound according to claim 1 wherein R.sub.3 is a C3-C6 branched, linear or cyclic alk-2-enyl residue carrying a CH.sub.2 group in alpha position to the phenyl ring.

15. The compound according to claim 1 wherein R.sub.3 is selected from the group consisting of allyl, 2-methylallyl, 2-methylenebutyl, 3-methylbut-2-en-1-yl, 3-methylbut-3-en-2-yl and but-2-en-1-yl.

16. A perfume composition comprising at least one compound according to claim 1.

17. The perfume composition according to claim 16 that is free of any aryl-substituted propanal odourants that are unsubstituted on the aryl ring at a position ortho to the substituent bearing the aldehyde functionality.

18. The perfume composition according to claim 16 that is free of 3-(4-tert-butylphenyl)-2-methylpropanal.

19. The perfume composition according to claim 16 comprising one or more additional fragrance ingredients, optionally 3-(4-isobutyl-2-methylphenyl) propanal.

20. A personal care or household care composition comprising at least one compound as defined in claim 1.

21. A method of imparting green odour characteristics to a fine fragrance or consumer product comprising the step of adding thereto at least one compound of formula I as defined in claim 1, and selectively excluding from said fine fragrance or consumer product any aryl-substituted alkanal compounds, which are unsubstituted on the ring at the position ortho to the substituent containing aldehyde functionality, said selective addition or exclusion being based on the susceptibility of said compound of formula I or said ortho unsubstituted compounds to enzymatically-mediated degradation to their benzoic acid derivatives when incubated with hepatocytes isolated from rats, said compound of formula I being suitable for addition on the basis that it does not degrade to its benzoic acid derivatives, whereas said compounds being excluded on the basis that they do degrade to their benzoic acid derivatives.

22. The personal care or household care composition according to claim 20, further comprising enzymes.

23. The personal or household care composition according to claim 20, characterised in that it is a textile treatment product.

24. The personal or household care composition according to claim 20, characterised in that it is a detergent composition.

25. A personal care or household care composition comprising at least a pro-perfume as defined in claim 2.

26. The personal care or household care composition according to claim 25, further comprising enzymes.

27. The personal or household care composition according to claim 25, characterised in that it is a textile treatment product.

28. The personal or household care composition according to claim 25, characterised in that it is a detergent composition.

Description

EXAMPLE 1

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

(1) ##STR00006##

(2) 2-(di-tert-butylphosphino)-1-phenyl-1H-indole (0.21 g, 0.61 mmol) and bis(dibenzylideneacetone)palladium(0) (0.131 g, 0.227 mmol) were dissolved in dimethyl formamide (9 ml) and the solution stirred under an argon atmosphere for 20 min. Then N-cyclohexyl-N-methylcyclohexanamine (3.55 g, 18.2 mmol), 1-bromo-4-(2-methylallyl)benzene (described in S. Yasuda, Materials 2009, 2(3), 978-991; 3.20 g, 15.2 mmol), and allyl alcohol (2.64 g, 45.5 mmol) were added and the resulting mixture was heated to 100? C. for 3 h, then cooled to room temperature. The mixture was diluted with methyl t-butyl ether and washed with water, 1 N aq. HCl solution and brine. The organic layer was dried over MgSO.sub.4 and concentrated i. RV. The residue was purified by flash column chromatography on SiO.sub.2 with hexane/ethyl acetate (19:1) as eluent to isolate 3-(4-(2-methylallyl)phenyl)propanal as a colourless oil (R.sub.f=0.19, 2.1 g, 73%).

(3) .sup.1H NMR (400 MHz, CDCl.sub.3): ?=9.83 (t, J=1.5 Hz, 1H), 7.14 (s, 4H), 4.82 (d, J=0.7 Hz, 1H), 4.78-4.65 (m, 1H), 3.31 (s, 2H), 2.96 (t, J=7.8 Hz, 2H), 2.82-2.75 (m, 2H), 1.72-1.66 (br. s, 3H) ppm. .sup.13C NMR (100 MHz, CDCl.sub.3): ?=201.7 (d), 145.1 (s), 137.9 (s), 137.7 (s), 129.1 (d), 128.2 (d), 111.8 (t), 45.3 (t), 44.2 (t), 27.7 (t), 22.0 (q) ppm. GC-MS (El, 70 eV): 188 (M.sup.+), 170 (5), 155 (5), 145 (60), 144 (60), 129 (100), 117 (66), 105 (66), 91 (72), 77 (21), 55 (24), 39 (22).

(4) Odour: floral, green, cyclamen, watery.

EXAMPLE 2

3-(4-(2-Methylallyl)phenyl)butanal

(5) ##STR00007##

(6) The above described procedure for example 1 was repeated with the same quantities of catalyst, amine, solvent and 1-bromo-4-(2-methylallyl)benzene but replacing allyl alcohol by (E)-but-2-en-1-ol (3.28 g, 45.6 mmol, 3 equiv.) to isolate 3-(4-(2-methylallyl)phenyl)butanal after flash column chromatography purification on SiO.sub.2 (elution with hexane/ethyl acetate 19:1) as a colourless oil (R.sub.f=0.22, 0.7 g, 23%).

(7) .sup.1H NMR (400 MHz, CDCl.sub.3): ?=9.70 (t, J=1.9 Hz, 1H), 7.13 (s, 4H), 4.80-4.78 (m, 1H), 4.72-4.71 (m, 1H), 3.33 (sext, J=7.2 Hz, 1H), 3.31 (s, 2H), 2.68 (qd, J=6.9, 2.3 Hz, 2H), 1.70 (br. s, 3H), 1.30 (d, J=7.0 Hz, 3H) ppm. .sup.13C NMR (100 MHz, CDCl.sub.3): ?=202.0 (d), 145.1 (s), 143.2 (s), 138.0 (s), 129.2 (d), 126.7 (d), 111.9 (t), 51.8 (t), 44.2 (t), 34.0 (d), 22.2 (q), 22.1 (q) ppm. GC-MS (El, 70 eV): 202 (M.sup.+, 4), 187 (3), 169 (2), 159 (48), 147 (100), 143 (17), 129 (28), 117 (48), 105 (23), 91 (45), 77 (9), 55 (41).

(8) Odour: floral, green, aldehydic, watery, buttery.

EXAMPLE 3

2-Methyl-3-(4-(2-methylallyl)phenyl)propanal

(9) ##STR00008##

(10) The above described procedure for example 1 was repeated with 47% of the quantities of catalyst, amine, solvent and 1-bromo-4-(2-methylallyl)benzene and replacing allyl alcohol by 2-methylprop-2-en-1-ol (1.0 g, 13.4 mmol, 3 equiv.) to isolate 2-methyl-3-(4-(2-methylallyl)phenyl)propanal after flash column chromatography purification on SiO.sub.2 (elution with with hexane/ethyl acetate 19:1) as a colourless oil (R.sub.f=0.38, 0.75 g, 80%).

(11) .sup.1H NMR (400 MHz, CDCl.sub.3): ?=9.70 (d, J=1.5 Hz, 1H), 7.13-7.03 (m, 4H), 4.80-4.79 (m, 1H), 4.72-4.71 (m, 1H), 3.28 (s, 2H), 3.06 (dd, J=13.4, 5.6 Hz, 2H), 2.67-2.55 (m, 2H), 1.67 (br. s, 3H), 1.08 (d, J=6.9 Hz, 3H) ppm. .sup.13C NMR (100 MHz, CDCl.sub.3): ?=204.5 (d), 145.1 (s), 137.9 (s), 136.5 (s), 129.1 (d), 128.9 (d), 111.9 (t), 48.1 (d), 44.2 (t), 36.3 (t), 22.1 (q), 13.2 (q) ppm. GC-MS (El, 70 eV): 202 (M.sup.+, 13), 184 (1.5), 169 (1.5), 159 (2), 145 (100), 129 (36), 117 (37), 105 (15), 91 (44), 77 (10), 55 (11), 39 (10).

(12) Odour: aldehydic, metallic, watery, fatty.

EXAMPLE 4

3-(2-Methyl-4-(2-methylallyl)phenyl) propanal

(13) ##STR00009##

(14) 3-(2-methyl-4-(2-methylallyl)phenyl)propanal was obtained in 3 steps as described below:

A) 2-methyl-4-(2-methylallyl) phenol

(15) o-Cresol (54.1 g, 0.5 mol) was suspended in water and KOH (36.5 g, 0.65 mol, 1.3 equiv.) was added under intense stirring. The temperature rose to 45? C. and a grey-yellow solution was formed, which was stirred for further 20 min then cooled to 10? C. At this temperature, 3-chloro-2-methylprop-1-ene (58.9 g, 0.65 mol, 1.3 equiv.) was added dropwise over 15 min. The resulting mixture was stirred intensely for 6 days, then diluted with toluene (300 ml). The organic layer was extracted 3 times with 2 N aq. NaOH solution (500 ml each). To the combined alkaline water layers was added toluene (300 ml), and, under ice bath cooling, conc. aq. HCl solution (350 ml). The layers were separated and the aqueous layer was further extracted with toluene. The combined organic layers were washed to neutrality with brine, then dried over MgSO.sub.4 and concentrated. The residue was distilled over a Vigreux column at 0.06 mbar/76-83? C. to isolate 2-methyl-4-(2-methylallyl)phenol (36.2 g, 45%, purity 92%, remainder was o-alkylated product) as a colourless oil.

(16) .sup.1H NMR (400 MHz, CDCl.sub.3): ?=6.92 (br. s, 1H), 6.87 (dd, J=8.0, 1.8 Hz, 1H), 6.87 (d, J=8.0, Hz, 1H), 4.90 (s, 1H), 4.78-4.77 (m, 1H), 4.71-4.70 (m, 1H), 3.20 (s, 2H), 2.20 (s, 3H), 1.66 (s, 3H) ppm. .sup.13C NMR (100 MHz, CDCl.sub.3): ?=152.1 (s), 145.7 (s), 132.0 (s), 131.6 (d), 127.5 (d), 123.7 (s), 114.8 (d), 111.6 (t), 43.9 (t), 22.0 (q), 15.8 (q) ppm.

B) Ethyl 3-(2-methyl-4-(2-methylallyl)phenyl)acrylate

(17) 2-methyl-4-(2-methylallyl)phenol (5.0 g, 30.8 mmol) was dissolved in dichloromethane (60 ml) and pyridine (4.63 g, 58.6 mmol, 1.9 equiv.) was added and the solution was cooled to 0? C. Then trifluoromethanesulfonic anhydride (1 M in dichloromethane, 32.4 ml, 32.4 mmol, 1.05 equiv) was added via dropping funnel and the resulting solution stirred for 3 h. Then 2 N aq. HCl solution (10 ml) was added dropwise. The aqueous layer was separated, and the organic layer was washed with diluted aq. NaHCO.sub.3 solution and brine, then dried over MgSO.sub.4 and concentrated i. RV. to yield 2-methyl-4-(2-methylallyl)phenyl trifluoromethanesulfonate (8.9 g, 98%) as a slightly yellow oil. For the subsequent Heck coupling reaction, this product (30.2 mmol) was dissolved in dimethyl formamide (50 ml), and ethyl acrylate (5.75 g, 57.5 mmol, 1.9 equiv) was added, followed by triethyl amine (15.0 g, 148 mmol, 4.9 equiv). The resulting solution was purged with argon for 10 min, then bis(triphenylphosphine)palladium(II) dichloride (1.06 g, 1.51 mmol, 5 mol %) was added and the mixture stirred for 6 days at 80? C. under an argon atmosphere. The mixture was diluted with MTBE, and washed with water and brine, then dried over MgSO.sub.4 and concentrated i. RV. The residue was purified by FC on SiO.sub.2 (elution with with hexane/ethyl acetate 19:1) to yield (E)-ethyl 3-(2-methyl-4-(2-methylallyl)phenyl)acrylate as a colourless oil (R.sub.f=0.21, 3.9 g, 53%).

(18) .sup.1H NMR (400 MHz, CDCl.sub.3): ?=7.95 (d, J=15.9 Hz, 1H), 7.48 (d, J=8.5 Hz, 1H), 7.02 (d, s, 2H), 6.34 (d, J=15.9 Hz, 1H), 4.83-4.82 (m, 1H), 4.75-4.74 (m, 1H), 4.26 (q, J=7.1 Hz, 2H), 3.28 (s, 2H), 2.42 (s, 3H), 1.67 (s, 3H), 1.34 (t, J=7.1 Hz, 3H) ppm. .sup.13C NMR (100 MHz, CDCl.sub.3): ?=167.2 (s), 144.6 (s), 142.2 (d), 142.0 (s), 137.7 (s), 131.4 (d), 127.0 (d), 126.4 (d), 118.5 (d), 112.3 (t), 60.4 (t), 44.4 (t), 22.1 (q), 19.8 (q), 14.4 (q) ppm.

C) 3-(2-methyl-4-(2-methylallyl)phenyl) propanal

(19) Ethyl 3-(2-methyl-4-(2-methylallyl)phenyl)acrylate (2.0 g, 8.2 mmol) was added dropwise to the suspension of LiAlH.sub.4 (0.47 g, 12.2 mmol, 1.5 equiv.) in Et.sub.2O (40 ml) at 10? C. The resulting mixture was stirred at room temperature under argon atmosphere during 18 h. Then water (0.47 g) was added carefully at 10? C., followed by 15% aq. NaOH solution (0.47 ml) and finally again water (0.9 ml). After stirring the formed suspension for 1 h, the precipitate was filtered off and the filtrate was concentrated to yield a colourless oil (1.7 g). This oil (8.3 mmol) was dissolved in dichloromethane (5 ml) and the solution added to the solution of Dess-Martin periodinane (4.24 g, 10 mmol, 1.2 equiv.) in dichloromethane (25 ml). The mixture was stirred for 2 h, then diluted with MTBE and washed with diluted aq. NaHCO.sub.3 solution, water and brined. The residue obtained after drying over MgSO.sub.4 and concentration was purified by FC on SiO.sub.2 (elution with with hexane/ethyl acetate 19:1) to yield the title compound as a colourless oil. (R.sub.f=0.14, 0.60 g, 36%).

(20) .sup.1H NMR (400 MHz, CDCl.sub.3): ?=9.84 (d, J=1.4 Hz, 1H), 7.04 (d, J=7.5, 1H), 6.97 (s, 1H), 6.96 (d, J=8.2, 1 H), 4.79 (m, 1H), 4.73-4.72 (m, 1H), 3.25 (s, 2H), 2.93-2.89 (m, 2H), 2.74-2.70 (m, 2H), 2.28 (s, 3H), 1.67 (s, 3H) ppm. .sup.13C NMR (100 MHz, CDCl.sub.3): ?=201.8 (d), 145.2 (s), 137.9 (s), 136.1 (s), 135.8 (s), 131.0 (d), 128.4 (d), 126.7 (d), 111.8 (t), 44.2 (t), 44.1 (t), 25.1 (t), 22.1 (q), 19.3 (q) ppm. GC-MS (El, 70 eV): 202 (M.sup.+, 36), 187 (8), 184 (18), 169 (21), 159 (86), 143 (100), 131 (88), 117 (33), 115 (48), 105 (39), 91 (33), 77 (15).

(21) Odour: floral, aldehydic, green, waxy, cinnamic, lilac