Patent Application
20110207835
The present invention refers to the use of short chain alk-2-enenitriles as perfuming ingredients and to flavour and fragrance compositions comprising them.
In the fragrance industry there is a constant demand for new compounds that enhance or improve on odour notes.
Short chain alk-2-enenitriles are known from the prior art. However, to the best of our knowledge, the prior art is completely silent with regard to their organoleptic properties or any use of this class of compounds in the field of perfumery.
The only short chain nitriles suitable in the field of perfumery described in literature are 3-butenenitrile and 4-pentenenitrile possessing onion-like and pungent mustard-like odour notes respectively (6th Int. Congr. Essent. Oils 1974, 73, W. S. Brud et al.).
Surprisingly, inventors found that certain short chain alk-2-enenitriles possess very interesting green, fruity odour notes.
Accordingly, the present invention refers in one of its aspects to the use as fragrance or flavour ingredient of a compound of formula (I)
wherein R is selected from linear, branched C3-4 alkyl and C3-4 cycloalkyl, such as propyl, prop-2-yl, butyl, 1-methylprop-1-yl, 2-methylprop-1-yl and cyclopropyl; and the double bond is in E or Z configuration; or a mixture thereof.
Whereas the (Z)- and (E)-isomers show similar olfactory profiles, the odour threshold of the (Z)-isomer compared to its corresponding (E)-isomer is higher. Accordingly, the use of the pure (E)-isomer is preferred. However, a mixture of both isomers, preferably enriched in the (E)-isomer, which is readily available synthetically, can also be used.
The term “enriched” is used herein to describe the compounds of the present invention having an isomeric purity greater than 1:1 in favour of the (E)-isomer. Particularly preferred are compounds having an isomeric purity of 1.5:1 (E:Z), more preferably 2:1 (E:Z) or 3:1 (E:Z), and most preferably 5:1 (E:Z) or greater.
The compounds according to the present invention may contain one stereocenter, and as such exist as mixtures of stereoisomers. They can be used as stereoisomeric mixtures, or may be resolved in diastereomerically and/or enantiomerically pure form. Resolving stereoisomers adds to the complexity of manufacture and purification of these compounds, and so it is preferred to use the compounds as mixtures of their stereoisomers simply for economic reasons. However, if it is desired to prepare individual stereoisomers, this may be achieved according to methodology known in the art, e.g. preparative HPLC and GC or by stereoselective syntheses.
In particular embodiments are the use as flavour or fragrance ingredient of compounds of formula (I) selected from the list consisting of hex-2-enenitrile, hept-2-enenitrile, 4-methylhex-2-enenitrile, 5-methylhex-2-enenitrile, 4-methylpent-2-enenitrile and 3-cyclopropylacrylonitrile, preferably enriched in favour of its (E)-isomer.
The compounds of formula (I) may be used alone, as mixtures thereof, or in combination with a base material. As used herein, the “base material” includes all known odorant molecules selected from the extensive range of natural products and synthetic molecules currently available, such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles, and/or in admixture with one or more ingredients or excipients conventionally used in conjunction with odorants in fragrance compositions, for example, carrier materials, and other auxiliary agents commonly used in the art, e.g. solvents such as dipropylene glycol (DPG), isopropyl myristate (IPM), and thriethyl citrate (TEC).
The following list comprises examples of known odorant molecules, which may be combined with the compounds of the present invention:
The compounds according to formula (I) may be used in a broad range of fragrance applications, e.g. in any field of fine and functional perfumery, such as perfumes, household products, laundry products, body care products and cosmetics. The compounds can be employed in widely varying amounts, depending upon the specific application and on the nature and quantity of other odorant ingredients. The proportion is typically from 0.001 to 20 weight percent of the application. In one embodiment, compounds of the present invention may be employed in a fabric softener in an amount of from 0.001 to 0.05 weight percent. In another embodiment, compounds of the present invention may be used in fine perfumery in amounts of from 0.1 to 20 weight percent, more preferably between 0.1 and 5 weight percent. However, these values are given only by way of example, since the experienced perfumer may also achieve effects or may create novel accords with lower or higher concentrations.
The compounds as described hereinabove may be employed into the fragrance application simply by directly mixing the fragrance composition with the fragrance application, or they may, in an earlier step, be entrapped with an entrapment material, for example, polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, or they may be chemically bonded to substrates, which are adapted to release the fragrance molecule upon application of an external stimulus such as light, enzyme, or the like, and then mixed with the application.
Thus, the invention additionally provides a method of manufacturing a fragrance application, comprising the incorporation of a compound of the present invention, as a fragrance ingredient, either by directly admixing the compound to the application or by admixing a fragrance composition comprising a compound of formula (I), which may then be mixed to a fragrance application, using conventional techniques and methods.
As used herein, “fragrance application” means any product, such as fine perfumery, e.g. perfume and eau de toilette; household products, e.g. detergent for dishwasher, surface cleaner; laundry products, e.g. softener, bleach, detergent; body care products, e.g. shampoo, shower gel; and cosmetics, e.g. deodorant, vanishing creme, comprising an odorant. This list of products is given by way of illustration and is not to be regarded as being in any way limiting.
The α/β-unsaturated nitriles according to formula (I) may be conveniently prepared by Wittig reaction of saturated aldehydes with (triphenylphosphoranilydene)acetonitrile under conditions known to the skilled person.
The invention is now further described with reference to the following non-limiting examples. These examples are for the purpose of illustration only and it is understood that variations and modifications can be made by one skilled in the art.
A mixture of (triphenylphosphoranilydene)acetonitrile (5 g, 16.6 mmol), distilled butyraldehyde (1.2 g, 16.6 mmol), and distilled dibenzyl ether (15 ml) was heated 4 h at 80° C. The reaction mixture (E/Z 70:30) was then cooled down and distilled using a Kugelrohr apparatus (ball-to-ball rotary distillation apparatus) at 40 mbar till 220° C. The main fraction (1.59 g) was then microdistilled in the presence of 1.6 g paraffin (15 mbar, oil bath temperature: 120° C.) giving a 63:37 mixture of (E/Z)-hex-2-enenitrile (0.6 g, 38%) having a boiling point of 79° C. at 15 mbar.
Odour description (E/Z)-hex-2-enenitrile: fruity, green, citrus.
Data of (E)-hex-2-enenitrile:
1H-NMR (400 MHz, CDCl3): δ6.72 (dt, J=6.9, 16.4, H—C(3)), 5.33 (dt, J=1.7, 16.4, H—C(2)), 2.21 (qd, J=1.7, 7.2, H—C(4)), 1.49 (sext., J=7.3, H—C(5)), 0.94 (t, J=7.3, MeCH2).
13C-NMR (100 MHz, CDCl3): δ155.91 (d, C(3)), 117.55 (s, CN), 99.78 (d, C(2)), 35.22 (t, C(4)), 20.90 (t, C(5)), 13.41 (q, C(6)).
MS (EI): 95 (3), 94 (1), 80 (3), 68 (4), 67 (22), 66 (7), 65 (3), 64 (5), 63 (3), 62 (1), 55 (14), 54 (100), 53 (12), 52 (9), 51 (7), 50 (4), 43 (3), 42 (8), 41 (28), 40 (9), 39 (23), 38 (6), 29 (15), 28 (3), 27 (15).
IR: νmax 2964, 2935, 2876, 2223, 1633, 1461, 1437, 1382, 1341, 1309, 1053, 967, 795 cm−1.
Data of (Z)-hex-2-enenitrile:
1H-NMR (400 MHz, CDCl3): δ6.49 (dt, J=7.7, 10.9, H—C(3)), 5.32 (dt, J=1.4, 10.9, H—C(2)), 2.41 (qd, J=1.3, 7.4, H—C(4)), 1.50 (sext., J=7.3, H—C(5)), 0.97 (t, J=7.3, MeCH2).
13C-NMR (100 MHz, CDCl3): δ154.97 (d, C(3)), 115.97 (s, CN), 99.63 (d, C(2)), 33.72 (t, C(4)), 21.52 (t, C(5)), 13.46 (q, C(6)).
MS (EI): 95 (2), 94 (2), 80 (4), 68 (4), 67 (33), 66 (5), 65 (3), 64 (4), 63 (2), 62 (1), 55 (11), 54 (100), 53 (13), 52 (9), 51 (7), 50 (4), 43 (2), 42 (7), 41 (35), 40 (9), 39 (23), 38 (6), 29 (12), 28 (3), 27 (14).
IR: νmax 2964, 2935, 2875, 2220, 1621, 1461, 1381, 1338, 1241, 1210, 1075, 1044, 1003, 970, 916, 874, 852, 735 cm−1.
Distilled valeraldehyde (1.43 g, 16.6 mmol) was added dropwise to a suspension of (triphenylphosphoranilydene)acetonitrile (5 g, 16.6 mmol) in distilled pentane (15 ml). After refluxing for 8 h, the reaction mixture was cooled down, filtered, and concentrated (rotary evaporator at 50° C. without vacuum). The residue (E:Z 70:30) was then distilled using a Kugelrohr apparatus (ball-to-ball rotary distillation apparatus) at 10 mbar and 81° C. giving two fractions of (E/Z)-hept-2-enenitrile (first fraction: 1.04 g, 58%, E:Z 64:36; second fraction: 0.45 g, E:Z 84:16, 25%) having a boiling point of 81° C. at 10 mbar.
Odour description: green, fruity, citrus, fatty.
Data of (E)-hept-2-enenitrile:
1H-NMR (400 MHz, CDCl3): δ6.73 (dt, J=7.0, 16.3, H—C(3)), 5.33 (dt, J=1.8, 16.3, H—C(2)), 2.23 (qd, J=1.6, 7.2, H—C(4)), 1.51-1.29 (m, 4H), 0.92 (t, J=7.3, MeCH2).
13C-NMR (100 MHz, CDCl3): δ156.14 (d, C(3)), 117.57 (s, CN), 99.59 (d, C(2)), 32.97 (t, C(4)), 29.66 (t, C(5)), 22.02 (t, C(5)), 13.67 (q, C(7)).
MS (EI): 109 (1), 108 (2), 94 (5), 81 (4), 80 (5), 69 (10), 68 (11), 67 (32), 66 (7), 65 (3), 64 (4), 57 (4), 56 (100), 55 (10), 54 (54), 53 (14), 52 (10), 51 (8), 50 (4), 43 (41), 42 (10), 41 (73), 40 (7), 39 (28), 38 (4), 29 (5), 28 (5), 27 (20).
Data of (Z)-hept-2-enenitrile:
1H-NMR (400 MHz, CDCl3): δ6.49 (dt, J=7.8, 10.9, H—C(3)), 5.31 (dt, J=1.3, 10.9, H—C(2)), 2.43 (qd, J=1.3, 7.3, H—C(4)), 1.51-1.29 (m, 4H), 0.93 (t, J=6.8, MeCH2).
13C-NMR (100 MHz, CDCl3): δ155.23 (d, C(3)), 116.96 (s, CN), 99.40 (d, C(2)), 31.55 (t, C(4)), 30.26 (t, C(5)), 22.09 (t, C(5)), 13.70 (q, C(7)).
MS (EI): 109 (1), 108 (3), 94 (7), 81 (6), 80 (7), 69 (12), 68 (13), 67 (76), 66 (6), 65 (4), 64 (4), 57 (4), 56 (100), 55 (9), 54 (55), 53 (18), 52 (13), 51 (10), 50 (5), 43 (49), 42 (12), 41 (82), 40 (8), 39 (30), 38 (5), 29 (6), 28 (6), 27 (23).
A mixture of (triphenylphosphoranilydene)acetonitrile (5 g, 16.6 mmol), distilled 2-methylbutyraldehyde (1.43 g, 16.6 mmol), and distilled pentane (15 ml) was heated for 18 h at reflux, filtered, and concentrated (rotary evaporator at 50° C. without vacuum). FC (pentane) of the crude product (1.2 g) gave a 85:15 mixture of (E/Z)-4-methylhex-2-enenitrile (0.9 g, 50%) having a boiling point of 50° C. at 10 mbar.
Odour description: green, slightly cucumber, slightly fruity, slightly fatty-oily.
Data of (E)-4-methylhex-2-enenitrile:
1H-NMR (400 MHz, CDCl3): δ6.63 (dd, J=7.8, 16.4, H—C(3)), 5.32 (dd, J=1.3, 16.4, H—C(2)), 2.23 (br. hept.t, J=1.1, 6.7, H—C(4)), 1.41 (quint., J=7.3, 2 H—C(5)), 1.05 (d, J=6.7, MeC(4)), 0.89 (t, J=7.4, MeC(5)).
13C-NMR (100 MHz, CDCl3): δ161.03 (d, C(3)), 117.64 (s, CN), 98.25 (d, C(2)), 39.25 (d, C(4)), 28.42 (t, C(5)), 18.37 (q, MeC(4)), 11.37 (q, C(6)).
MS (EI): 109 (1), 108 (1), 94 (3), 81 (8), 80 (20), 69 (6), 68 (25), 67 (13), 66 (7), 65 (4), 56 (100), 54 (22), 53 (24), 52 (10), 51 (8), 42 (12), 41 (22), 39 (14), 29 (7), 28 (3), 27 (10).
Data of (Z)-4-methylhex-2-enenitrile:
1H-NMR (400 MHz, CDCl3): δ6.25 (t, J=10.6, H—C(3)), 5.28 (dd, J=0.6, 10.6, H—C(2)), 2.75-2.62 (m, H—C(4)), 1.56-1.30 (m, 2H—C(5)), 1.07 (d, J=6.7, MeC(4)), 0.91 (t, J=7.3, MeC(5)).
13C-NMR (100 MHz, CDCl3): δ160.38 (d, C(3)), 118.41 (s, CN), 98.17 (d, C(2)), 38.56 (d, C(4)), 29.12 (t, C(5)), 19.56 (q, MeC(4)), 11.55 (q, C(6)).
MS (EI): 109 (1), 108 (1), 94 (4), 81 (16), 80 (35), 69 (7), 68 (52), 67 (16), 66 (7), 65 (5), 56 (100), 54 (37), 53 (30), 52 (13), 51 (11), 42 (20), 41 (25), 39 (18), 29 (9), 28 (4), 27 (13).
A mixture of (triphenylphosphoranilydene)acetonitrile (5 g, 16.6 mmol), distilled isovaleraldehyde (1.43 g, 16.6 mmol), and distilled pentane (15 ml) was heated for 6.5 h at reflux, filtered, and concentrated (rotary evaporator at 50° C. without vacuum). FC (pentane) of the crude product (2.1 g) gave a 66:34 mixture of (E/Z)-5-methylhex-2-enenitrile (1.0 g, 56%) having a boiling point of 64° C. at 10 mbar.
Odour description: green-fruity, fatty (isovalerianic).
Data of (E)-5-methylhex-2-enenitrile:
1H-NMR (400 MHz, CDCl3): δ6.70 (dt, J=7.6, 16.3, H—C(3)), 5.33 (dt, J=1.6, 16.3, H—C(2)), 2.12 (ddd, J=1.5, 6.8, 7.5, 2 H—C(4)), 1.77 (non., J=6.7, H—C(5)), 0.93 (d, J=6.7, 2 MeC(5)).
13C-NMR (100 MHz, CDCl3): δ155.00 (d, C(3)), 117.46 (s, CN), 100.56 (d, C(2)), 42.44 (t, C(4)), 27.63 (d, C(5)), 22.10 (q, 2 MeC(5)).
MS (EI): 109 (1), 108 (1), 94 (3), 81 (1), 68 (6), 67 (100), 66 (10), 65 (4), 56 (26), 53 (4), 52 (4), 51 (4), 43 (56), 41 (42), 39 (21), 27 (11).
Data of (Z)-5-methylhex-2-enenitrile:
1H-NMR (400 MHz, CDCl3): δ6.51 (dt, J=7.8, 10.8, H—C(3)), 5.36 (dt, J=1.4, 10.8, H—C(2)), 2.33 (ddd, J=1.3, 6.8, 8.0, 2 H—C(4)), 1.80 (non., J=6.7, H—C(5)), 0.96 (d, J=6.7, 2 MeC(5)).
13C-NMR (100 MHz, CDCl3): δ154.00 (d, C(3)), 116.10 (s, CN), 100.18 (d, C(2)), 40.66 (t, C(4)), 27.98 (d, C(5)), 22.10 (q, 2 MeC(5)).
MS (EI): 109 (1), 108 (1), 94 (2), 81 (1), 80 (1), 69 (1), 68 (5), 67 (100), 66 (6), 65 (3), 56 (6), 54 (2), 53 (3), 52 (3), 51 (3), 43 (24), 41 (28), 39 (15), 29 (1), 28 (1), 27 (7).
A mixture of (triphenylphosphoranilydene)acetonitrile (5 g, 16.6 mmol), distilled isobutyraldehyde (1.2 g, 16.6 mmol), and distilled pentane (15 ml) was heated for 18 h at reflux, filtered, and concentrated (rotary evaporator at 50° C. without vacuum). The residue (E/Z 87:13) was then distilled using a Kugelrohr apparatus (ball-to-ball rotary distillation apparatus) at 10 mbar and 50° C. giving two fractions of (E/Z)-4-methylpent-2-enenitrile (first fraction: 0.16 g, 10%, E/Z 83:17; second fraction: 0.32 g, E/Z 91:9, 20%).
Boiling point: 50° C. (10 mbar).
Odour description: green, fresh, fruity, slightly cuminic.
Data of (E)-4-methylpent-2-enenitrile:
1H-NMR (400 MHz, CDCl3): δ6.71 (dd, J=6.6, 16.4, H—C(3)), 5.28 (dd, J=1.5, 16.4, H—C(2)), 2.48 (oct.d, J=1.6, 6.8, H—C(4)), 1.07 (d, J=6.8, 2 MeC(4)).
13C-NMR (100 MHz, CDCl3): δ161.90 (d, C(3)), 117.69 (s, CN), 97.32 (d, C(2)), 32.05 (d, C(4)), 20.69 (q, 2 MeC(4)).
MS (EI): 95 (13), 94 (37), 80 (59), 68 (71), 67 (48), 55 (52), 54 (28), 53 (100), 52 (28), 51 (20), 42 (21), 41 (26), 39 (28), 27 (16).
Data of (Z)-4-methylpent-2-enenitrile:
1H-NMR (400 MHz, CDCl3): δ6.31 (dd, J=10.1, 10.9, H—C(3)), 5.21 (dd, J=0.6, 10.9, H—C(2)), 2.92 (dhept.d, J=0.5, 6.7, 10.1; H—C(4)), 1.09 (d, J=6.6, 2 MeC(4)).
13C-NMR (100 MHz, CDCl3): δ161.38 (d, C(3)), 117.69 (s, CN), 96.99 (d, C(2)), 31.57 (d, C(4)), 21.70 (q, 2 MeC(4)).
MS (EI): 95 (12), 94 (40), 80 (60), 68 (76), 67 (48), 55 (52), 54 (30), 53 (100), 52 (29), 51 (20), 42 (23), 41 (29), 39 (31), 27 (17).
A mixture of (triphenylphosphoranilydene)acetonitrile (5 g, 16.6 mmol), distilled cyclopropanecarboxaldehyde (1.16 g, 16.6 mmol), and distilled pentane (15 ml) was heated for 19 h at reflux, filtered, and concentrated (rotary evaporator at 50° C. without vacuum). The residue was then distilled using a Kugelrohr apparatus (ball-to-ball rotary distillation apparatus) at 10 mbar and 67° C. giving two fractions of (E/Z)-3-cyclopropylacrylonitrile (first fraction: 0.27 g, 18%, E/Z 76:24; second fraction: 0.12 g, 8%, E/Z 85:15) having a boiling point of 67° C. at 10 mbar.
Odour description: green, apple, fruity, slightly fatty.
Data of (E)-3-cyclopropylacrylonitrile:
1H-NMR (400 MHz, CDCl3): δ6.13 (dd, J=10.0, 16.0, H—C(3)), 5.36 (d, J=16.0, H—C(2)), 1.64-1.55 (m, CH—C(3)), 1.04-0.98 (m, 2H), 0.69-0.64 (m, 2H).
13C-NMR (100 MHz, CDCl3): δ159.94 (d, C(3)), 117.89 (s, CN), 95.88 (d, C(2)), 15.49 (d, CH—C(3)), 8.91 (t, 2C).
MS (EI): 94 (1), 93 (20), 78 (2), 67 (8), 66 (100), 65 (19), 64 (6), 63 (5), 54 (4), 53 (8), 52 (6), 51 (8), 50 (5), 41 (6), 40 (8), 39 (18), 38 (7), 37 (4), 27 (6).
Data of (Z)-3-cyclopropylacrylonitrile:
1H-NMR (400 MHz, CDCl3): δ5.80 (dd, J=10.8, 16.0, H—C(3)), 5.18 (dd, J=0.5, 10.8, H—C(2)), 2.06-1.95 (m, CH—C(3)), 1.10-1.05 (m, 2H), 0.70-0.64 (m, 2H).
13C-NMR (100 MHz, CDCl3): δ159.25 (d, C(3)), 117.83 (s, CN), 95.65 (d, C(2)), 14.84 (d, CH—C(3)), 8.78 (t, 2C).
MS (EI): 94 (1), 93 (21), 78 (2), 67 (8), 66 (100), 65 (18), 64 (6), 63 (5), 54 (4), 53 (7), 52 (6), 51 (8), 50 (5), 41 (6), 40 (8), 39 (19), 38 (7), 37 (4), 27 (6).
In this apple accord 2% of hex-2-enenitrile provides a typical green apple volume and makes it more fresh-natural and tasty.
| Number | Date | Country | Kind |
|---|---|---|---|
| 0618870.0 | Sep 2006 | GB | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/CH07/00472 | 9/26/2007 | WO | 00 | 5/4/2011 |
