MXPA00006415A - Cyclopentylalkyl-nitriles and the use of odoriferous cyclopentylalkyl derivatives as fragrances - Google Patents

Abstract

Compounds of formula II the symbols of which have the definition given in claim 7 possess interesting olfactory properties mainly of the floral nature. They are used to impart odor to perfumery compositions.

Description

CICLOPENTILALQUILNITRILOS FIELD OF THE INVENTION The present invention relates to novel cyclopentylalkyl trilines and to the use of odoriferous or fragrant cyclopentylalkyl derivatives as fragrances.

BACKGROUND OF THE INVENTION Despite the common incidence of five-element carbon rings in perfumery ingredients, mainly of terpene origin (for example derivatives of canophyenic aldehyde from odor notes of sandalwood type) or resulting from condensation Diels-Alder with cheap cyclopentadiene, very few of them contain an unsubstituted cyclopentyl radical, isolated (ie, unprocessed part of a spiro or polycyclic fused system), cyclopentenyl or cyclopentylidene. The following products are among the few examples of such raw perfumery materials: REF.120359 CAS 4884-25-7 CAS 4884-24-6 CAS 6261-30-9 CAS 68039-73-6 CAS 40203-73-4 e CAS 6r5405-o69-8 These compounds are also described in EP 0 016 650, EP 0 770 671 and DE 2 729 121.

DESCRIPTION OF THE INVENTION There is a renewed interest in floral fragrances. Therefore, the object of the present invention is to provide new ingredients in perfumery that have original, intense, diffuse and substantive (ie, long-lasting) essences that belong to the floral family.

We have found that the new compounds of formula I, wherein R1, R2 and R3 are independently H, C1-C3 alkyl, but R1 and R2 are not at the same time H; R2 can also be methylene or ethylidene; n = 0 or 1 and remains for an individual or double link, with it, maximum 2 double links are present.

They have notes mainly of roses and lilies, very intense.

It has further been found that the compounds of formula II, where A is selected from the group of CR4R5OC (0) R5, C02R6, CN and C (0) R4; R1, R2, R3, R4, R5 and R6 are independently H or C1-C3 alkyl; R2 can also be methylene or ethylidene; R6 can also be a C2-4 alkenyl or alkynyl n = 0 or 1 and remains for a single or double bond, thereby maximum 2 double bonds are present.

They have interesting olfactory properties. The smells are mainly floral, for example, lilies of the valley, lilies or ilang-ilang and fruit trees, for example, citrus fruits. They are intense, diffuse and long lasting. All the compounds of the general formula II have substantive odors, a crucial quality for functional perfumery.

The heteroatoms in all the compounds of formula I and II are in a more remote position relative to the lipophilic cyclopentane ring, than the oxygen atom in the corresponding perfumery ingredients.

The compounds of formula II can be used to impart odor to any perfumery composition such as fine and functional perfumery, for example, perfume, detergent or fine fragrance, fabric softeners, bath gel, soap, cosmetics, scented candles , etc.

The compounds of formula I are new. The following compounds of formula II are also new: -cyclopentyl-3-methylpent- -en-l-ol 5-cyclopentyl-3-methylpent-4-enal 5-cyclopentyl-3-ethylpent-4-en-l-yl 5-cyclopentyl-3-methylpentan- acetate l-ol 4-cyclopentan-l-ol propanoate of 4-cyclopentyl-l-4-cyclopentanal 4-cyclopentanoate of ethyl 5-cyclopentylhexan-2-one 5-cyclopethylhexanal 5-cyclopentylhexan-l-ol 5- (2- methylcyclopent-l-enyl) pentan-1-ol 5- (5-methylcyclopent-l-enyl) pentan-1-ol 4-cyclopentylidenebutan-1-ol 6-cyclopentyl-3-methyl-3-exo-3-yl (cyclopentyl -1-enyl) -2-methylpentan-2-ol 5-cyclope-tylpentan-2-ol-5-cyclopentylidene-2-yl 5-cyclopentylidene-2-methylpentan-2-ol propanoate The following compounds of formula I are preferred: 5-cyclopentyl-3-methylpentanyl butyl 4-cyclopentylpentanonitrile 5-cyclopentylhexanoni trilo 5-cyclopentyldenohexaonitrile 5- (cyclopent-1-enyl) hexanone tryl The compounds of the general formulas I and II, they can be advantageously prepared by different synthetic ways. Thus, the five-element ring is introduced with the commercially available starting materials (cyclopentanone, cyclopentadiene, cyclopentylhalide and derivatives) or, for example, incorporated into the Grignard reagent derived from 1,4-dihalobutane to the lactones. Among the best methods or syntheses of the cyclopentyl-, cyclopentenyl- or cyclopentylidene-functionalized alkanes, are the addition of the cyclopentadienyl anion to the carbonyl group, followed by total or partial hydrogenation of the fulvenos structures thus formed, as shown in the Scheme of Reaction I (for example, Coe, J.; Vetelino, M.G .; Kemp, D.S. Te trah edron Le t t. 1994, 35, 6627). a) piperidine; b) hydrogenation Scheme 'of Reaction 1 The odorants or flavorants of the formula II can also be combined with numerous color or flavoring ingredients of synthetic and / or natural origin, thereby, the range of the natural odorants or flavors can include not only easily volatile components, but also, moderately and only slightly volatile, and synthetic ones can encompass representative of virtually all kinds of substances. The following list comprises examples of known odorants or flavors, which may be combined with the compounds of the invention: Natural products: such as absolute tree moss, basil oil, tropical fruit oil (such as bergamot oil or variety of good grass, mandarin oil, ect.), absolute mastix, myrtle oil, palm oil, galbanum oil, patchouli oil, petitgrain oil, wormwood oil, oil lavender, rose oil, jasmine oil, ilang-yang oil, etc .; alcohols: such as farsenol, geraniol, linalool, nerol, phenylethyl alcohol, rodinol, cinnamic alcohol, (Z) -hex-3-en-l-ol, menthol, a-terpineol, etc .; aldehydes: such as citral, α-hexyl cinnamaldehyde, Lilial® (Givaudan Roure), hydroxy-citronellal, methyl-n-acetyl-aldehyde, phenylacetaldehyde, anisaldehyde, vanillin, etc .; ketones: such as allylonones, α-ionone, β-ionone, Isoraldeine® (Givaudan Roure), methylionone, verbenone, nootcatone, geranylacetone, etc .; esters: such as allyl phenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, decyl acetate, dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, ethyl acetoacetate, cis-3-hexenyl isobutyrate, cis-3-salicylate hexenyl, linalyl acetate, methyl dihydroxylammonium, styralyl propionate, vetyveryl acetate, benzyl acetate ,. geranyl acetate, etc.; lactones: such as? -undecalactone, d-decalactone, pentadecanolide, 12-oxahexadecanolide, etc .; acetals: such as Viridine (phenylacetaldehyde dimethylacetal), etc .; various components: often used in perfumery, such as indole, p-mentha-8-thiol-3-one, methyleugenol.

Eugenol, anethole, etc.

The new colorings or aromatizers harmonize particularly well with all the other floral notes (lily of the valley, rose, lilies, jasmine, ilang-ilang, daffodil notes, tobacco-like and patchouli composition, etc.) The percentage in which they are used in the compositions can vary within wide limits ranging from a few parts to thousands in mass of commercialized products (for example, cleansers, deodorants), up to a few hundred in alcoholic extracts for perfumery (fine ). In all cases, in small quantities, they provide odorous or aromatic compositions with intense floral notes and increase the volume (vigor, diffusion capacity) and the substantivity of the odor. In particular, the manner in which they extend the form of diffusion and the olfactory duration of the composition is remarkable.

There is no restriction regarding the type of formulations and the destination of the current finished product, thus, they come into consideration, eau de cologne (cologne water), toilet water, perfumed water, perfume, cream, shampoo, deodorant, soap, powder of detergent, household cleaner, fabric softener, etc.

The invention will also be described by way of illustration in the following examples.

Suitable methods for the preparation of compounds of the invention are summarized in the examples without limitation of the invention to these.

All compounds were ambiguously identified by their 1H-NMR-, IR- and -MS spectra, which were measured under the following conditions: - IR- Ni col e t 51 0 FT-IR; pur; v in c -1, XH NMR: Bruker DPX-400; at 250 and 400 MHz; in CDC13 if they are not declared otherwise; chemical changes (d) in ppm low fields of TMS; constants of couplings J in Hz, MS and GC / MS: Fi nni gan MAT 212 (El, 70eV); intensities (in parentheses) in% of relation to the base peak.

They were always purified by fractional distillation, or by bulb-to-bulb distillation, after flash chromatography (Merck 60 silica gel, 230-400 mesh), and they were colorless, olfactoryly pure oils.

Example 1 -cyclopentyl-3-methylpent-4-en-l-ol A solution of ethyl 5-cyclopentyl-3-methylpent-4-enoate (16.8 g, 80 mmol, obtained according to Streinz, L .; Romanuk, M .; Soria, F .; Sehnal, F. DE 2 444 837 , priority 20.09.1973) in diethyl ether (30 ml) was added dropwise to a suspension of lithium aluminum hydride (3.0 g, 80 mmol) in the same solvent (110 ml), and the reaction mixture was stirred at room temperature. reflux for 1 hour. Water (3.5 ml), then 15% NaOH solution and again water (3.5 ml) were added, the precipitate was filtered and washed with water.

MTBE (30 ml). The combined organic phases were washed with IN HCl (200 ml) and brine (3 x 100 ml), dried (MgSO4), concentrated in vacuo, and distilled (79-82 ° C / 0.07 torr) to give 7.8 g (59% yield) of 5- cyclopent i 1-3-methylpent-4-en-l-ol . IR: 3329, 2953, 2869, 1453, 1373, 1052, 999, 969. lH-NMR: 0.98. { dt J - 6.7, 3H), 1.16-1.40 (m, 2H), 1.46-1.82 (n, 9H), 2.12-2.28. { m, 1H), 2.26-2.47. { m, 1H), 3.64 (t, J = 6. 6, 2H), 5.25. { dd, J = 15.3, 7.3, 1H), 5.41 (dd, J = 15.3, 7.0, 1K). MS: 168 (1.3,? F), 150 (3), 135 (8), 121 (9), 108 (8), 107. { 9), 95 (64), 93 (31), 82 (63), 81 (93), 79 (40), 69 (35), 67 (100), 55 (59), 41 (57).

Smell: floral, fruity, hesperidic / citric, very strong and substantive.

Example 2 -cyclopentyl-3-methylpent-4-enal Diisobutylaluminum hydride (95 ml of a 1.0 M solution in hexane) was added in a hexane solution (200 ml) of ethyl 5-cyclopentyl-3-methylpent-4-enoate (used in example 1, 20.0 g; mmol), at -65 ° C. After 3 hours of stirring at the same temperature, ethanol (3 ml) was added, and the reaction mixture was poured into an ice-cold NH 4 Cl solution (200 ml), and diluted with 2N HCl (100 ml). The organic layer was separated, washed with brine (3 x 200 ml), dried (MgSO), and concentrated in vacuo, and purified by flash chromatography (hexane / MTBE). : 1) to give 10.9 g (69% yield) of 5-cyclopentyl-3-methylpent-4-enal.

IR: 2954, 2870, 2716, 1727, 1453, 1375, 970. ^ -NMR: 1.06 (d, J = 7.0, 3H), 1.12-1.36 (m, 2H), 1.44-1.83. { m, 6H), 2.25-2.49 (m, 3H), 2.61-2.81 (, J = 6.7, 1H), 5.32 (dd, J = 15.4, 6.1, 1H), 5.44 (dd, J = 15.4, 6.4, 1H ), 9.71 (t, J-2.3, 1H). MS: 166 (1.5, Af *), 151 (3), 148 (3), 122 (61), 107 (15), 98 (43), 97 (57), 95 (44) 93 (64), 81 (63), 80 (36), 79 (47), 69 (47), 67 (100) 55 (71), 41 (88), 39 (41). Smell: aldehydic, citrus, geranium.

Example 3 -cyclopentyl-3-methylpent-4-en-l-yl acetate Acetyl chloride (1.7 g, 22 mmol) was added to a cooled solution of 5-cyclopentyl-3-methylpent-4-en-1-ol (obtained in Example 1, 2.6 g, 15 mmol), pyridine (2.4 g). 30 mmol), and DMAP (0.13 g, 0.1 mmol) in cyclohexane (65 ml). After 3 hours with stirring at room temperature, the reaction mixture was poured into IN HCl (130 mL) and MTBE (65 mL). The organic layer was separated, washed successively with 1 N HCl (130 ml), sodium bicarbonate solution (100 ml) and brine (2 x 100 ml) and treated as in Example 1 (distillation at 120 ° C / 0.8. torr) to give 3.05 g (yield 94%) of 5-cyclopentyl-3-methylpent-4-en-1-yl acetate. IR: 2954, 2869, 1743, 1454, 1366, 1238, 1048, 970. ^ -NMR: 0.99 < d, J == 6.7, 3H), 1.13-1.34 (f2H), 1.44-1.83 (m, 8H), 2.04 (s, 3H), 2.08-2.30 (m, J - 7.0, 1H), 2.26-2.47 (m, 1H), 4.05 (t, J = 6.8, 2H), 5.20 (dd, J = 15.4, 7.3, 1H), 5.37. { dd, J = 15.4, 7.0, 1H). MS: 195 (0.1, M "- CH3), 150 (10), 135 (13), 121 (18), 108 (13), 107 (11), 95 (18), 93 (29), 82 (22 ), 81 (100), 80 (23), 79 (25), 67 (43), 55 (28), 41 (27).

Smell: fruit, pear, pineapple, floral, E emplo 4 -Cyclopentyl-3-methylpentan-1-ol Ethyl 5-cyclopentyl-3-methylpent-4-enoate of Example 1 (22.4 g, 0.11 mol) was hydrogenated over 5% Pd / C in ethanol (220 ml), at room temperature and under atmospheric pressure. The catalyst was filtered, the solvent was evaporated in vacuo and the residue was distilled (59 ° C / 0.08 torr) to give 19.5 g (92% yield) of -cyclopentyl-3-methylpentanoate which was reduced with lithium aluminum hydride as in example 1 to give 5-cyclopentyl-3-methylpentan-ol in 76.5% yield IR: 3331, 2949, 2867, 1454, 1377, 1059, 1010. "H-NMR: 0.89 (d, J-6.4, 3H), 0.97-1.84 (m, 17H), 3.68 (m, 2H). 152 (0.4, Af * - H20), 137 (11), 124 (21), 123 (16), 110 (12), 109 (14), 95 (85), 82 (100), 71 (28), 69 (72), 67 (77), 55 (77), 41 (51).

Aroma: very strong, with roses, geranium, woods. Example 5 -cyclopenti1-3-methylpentanonitrile a) 5-cyclopentyl-3-methylpentanal oxime An aqueous solution (7 ml) of hydroxylamine hydrochloride (3.9 g, 56 mmol) was added to an ethanolic solution (20 ml) of 5-cyclopentyl-3-methylpentanal (8.0 g, 47 mmol), obtained from ethyl cyclopentyl-3-methyl-pentanoate of Example 4 by reduction of diisobutylaluminum hydride according to Example 2 (73% yield). The reaction mixture was heated to 50 ° C and treated with a solution of sodium hydroxide (2.7 g, 67 mmol) in water (5 ml). After 2 hours with stirring at room temperature, ice (25 g) was added and the mixture was saturated with carbon dioxide (solid). The organic layer was separated, dried (MgSO 4), concentrated in vacuo, and purified by flash chromatography (MTBE / hexane 1: 4) to give 5.8 g (67% yield) of 5-cyclopentyl-3-methylpentanal oxime. . b) 5-Cyclopentyl-3-methylanthaneditrile 5-Cyclopentyl-3-methylpentanalime (3.7 g, 20 mmol) and acetic anhydride (4.5 g, 40 mmol) were heated at 110 ° C for 1.5 hours, poured into ice water (100 ml) and extracted with MTBE (150 ml).

The organic phase was washed with brine (4 x 150 ml), dried (MgSO 4), concentrated in vacuo, and purified by flash chromatography (MTBE / hexane 1:15) to give 1. 9 g (57% yield) of 5-cyclopentyl-3-methylpentanonitrile.

IR: 2950, 2866, 2246, 1457, 1425, 1384. ^ -NMR: 1.06 (d, J = 6.7, 3H), 1.25-1.91 (, 14H), 2.22. { dd, J * > 16.7, 6.3, 1H), 2.33 (dd, J = 16.7, 6.0, 1H). MS: 165 (0.5, Af), 164 (5), 150 (12), 136 (23), 124 (100), 122 (26), 109 (14), 97 (27), 94 (19), 83 (14), 82 (15), 69 (48), 68 (45), 55 (66), 41 (88).

Aroma: citrus, geranitrile, peach, rose 4-cyclopentylpentan-l-ol a) 4-cyclopentylpentanoic acid The 4-cyclopenta-2, -dienylidenepentanoic acid (25 g, 0.15 mol, was obtained according to Coe, JM, Vetelino, M.G.; Kemp, DS, Te trah edron Le tt., 1994, 35, 6627. ) in ethyl acetate (270 ml) was hydrogenated as an example 4 to give 23.6 g (92% yield) of crude 4-cyclopentylpentanoic acid which was used in the next step without further purification. b) 4-cyclopentylpentan-l-ol A solution of 4-cyclopentylpentanoic acid (16 g, 94 mmol) in diethyl ether (30 ml) and THF (30 ml) was added within 20 min. to lithium aluminum hydride (3.6 g, 94 mmol) suspended in the same solvent (100 ml). After 2 hours at reflux, the reaction mixture was cooled with a cold bath and quenched successively with water (4 ml), 15% sodium hydroxide (12 ml) and water again (4 ml). The white solid was filtered and the mixture was diluted with MTB (300 ml), washed with IN HCl (300 ml), sodium bicarbonate solution (300 ml) and brine (2 x 300 ml), dried (MgSO4). , concentrated in vacuo, and distilled (59 ° C / 0.075 torr) to give 8.7 g (59% yield) d 4-cyclopentylpentan-l-ol.

IR: 3329, 2950, 2867, 1451, 1377, 1056, 894. ^ -N R: 0.88 (d, J = 6. 4, 3H), 1.0-1.81 (ip, 15H), 3.62 (? A, 2H); . MS: 138 (3, M + - H20), 123 (3), 110 (42), 109 (14), 97 (58), 96 (40), 95 (35), 87 (24), 81 (27) , 68 (38), 67 (51), 55 (60), 41 (43).

Aroma: floral, woods, citrus, metallic Example 7 4-cyclopentylpentyl-l-yl propane 4-Cyclopentylpentan-1-ol (4.0 g, 23 mmol) was esterified with propionyl chloride (3.1 g, 34 mmol) according to Example 3 to give 4.4 g (84.5 yield) of 4-cyclopentylpent-1-yl propanoate. .

IR: 2951, 2868, 1743, 1456, 1366, 1239, 1048. lH-N R: 0.87 (d, J = 6.4, 3H), 1.00-1.87 (m, 14H), 1.14 (t, J = 7.5, 3H), 2.32 (g, J = 7.6, 2H), 4.05 (t, < 7 - 6.6, 2H). MS: 226 (0.01, Af), 197 (4), 152 (10), 137 (12), 124 (17), 123 (18), 110 (22), 96 (32), 95 (88), 83 (50), 82 (100), 81 (42), 75 (40), 69 (44), 67 (59), 57 (67), 55 (53), 41 (32). Aroma: orange, fruity, ozonic, floral.

Example 8 Ethyl 4-cyclopentylpentanoate 1,1'-Carbonylimidazole (101 g, 0.62 mmol) was added portionwise to 4-cyclopentylpentanoic acid (100 g, 0.58 mol) in THF (500 mL). After evolution of the gas stopped, the reaction mixture was reacted with sodium ethylate solution prepared from sodium (0.3 g, 13 mmol) and ethanol (500 ml), stirred at room temperature by 2. 5 hours, and the solvent was evaporated in vacuo. The residue was dissolved in ether (300 ml), washed successively with water (300 ml), 1N NaOH (300 ml) and 1 N HCl (300 mL), dried (MgSO 4), concentrated in vacuo, and distilled over a 10 cm Vigreux column (66 ° C / 0.08 torr) to give 59.4 g 52% yield of 4-cyclopentylpentanoate of ethyl. IR: 2953, 2869, 1738, 1451, 1376, 1253, 1181, 1104, 1037, 939. ^ -NMR: 0.87 (d, «7 - 6.4, 3H), 1.26 (t, J = 7.2, 3H), 1.01 -1.91. { a, 12H), 2.23 (ddd, J = 15..3, 8.8, 6.4, 1H), 2.37 (ddd, J = 15.3, 9.8, 5.5, 1H), 4.12 (q, J = 7.1, 2HJ. 183 (0.1, Af-CH3), 153 (3), 141 (16), 135 (32), 129 Aroma: green, fruity (pineapple), floral (with roses).

Example 9 4-cyclopentylpentanal Ethyl 4-cyclopenti.lpentanoate was reduced to 4-Cyclopentylpentanal with diisobutylaluminum hydride as in Example 2 (68% yield).

IR: 2952, 2868, 2714, 1727, 1450, 1411, 1379, 1012. 1H-NMR: 0.88 (d, J • 6.4, 3H), 1.01-1.91 (ip, 12H), 2.29-2.57 (m, 2H) , 9.77 (t, J = 2.0, 1H). MS: 154 (4, Af), 139 (10), 136 (18), 121 (19), 110 (77), 97 (44), 95 (53), 85 (36), 81 (35), 69 (62), 68 (76), 67 (100), 55 (76), 41 (60).

Aroma: aldehydic, melon, tangerine, green ivy, floral.

Example 10 4-cyclopentylpentanenitrile 4-Cyclopentylpentanal in 4-cyclopentylpentanenitrile was converted as in Example 5 (56% yield).

IR: 2953, 2869, 2246, 1450, 1428, 1381. ^ -NMR: 0.91 (d, J = 6.1, 3H), 1.04-1.26 (m, 2H), 1.36-1.93 (m, 10H), 2.21- 2.49 . { m, 2H). MS: 151 (0.1, Af), 150 (0.5), 136 (4), 123 (3), 110 (45), 109 (43), 97 (11), 83 (18), 69 (63), 68 (19), 67 (21), 55 (83), 41 (100).

Aroma: hesperidic, floral, green, cumin Example 11 -cyclopentylhexanonitrile a) 5- (cyclopentane-2,4-dienylidene) haxanonitrile Pyrrolidine (18.5 g, 0.26 mol) was added to a solution of cyclopentadiene (10.8 g, 0.16 mol, recently prepared by thermal decomposition of dicyclopentadiene) and 5-oxohexanoni trilo (15.4 g, 0.13 mol) in methanol (175 ml) at 0 ° C. After 1 hour of stirring at this temperature, the reaction mixture was poured into 2 N HCl (500 mL) cooled on ice, saturated with sodium chloride and extracted with MTBE (400 mL). The organic phase was washed with brine (3 x 300 ml), dried (MgSO 4), concentrated in vacuo, and used in the next step without further purification. b) 5-cyclopentylhexanonitrile Hydrogenation as in Example 4 gave 5-cyclopentylhexanonitrile.

IR: 2952, 2868, 2245, 1458, 1427, 1378. XH-NMR: 0.88 (d, J * = 6.1, 3H), 1.01-1.86 (mr 14H), 2.28-2.37 (m, 2H). MS: 165 { 2, Af), 164 (12), 150 (25), 136 (17), 124 (67), 122 (39), 98 161), 97 (100), 96 (47), 82 (34), 69 (80), 68 (38), 67 (25), 55 (71), 41 (49).

Aroma: floral, lily, spicy, powdery, cumin Example 12 -Cyclopentylhexan-2-one 4-Cyclopentylpentanoic acid (3. g, 20 mmol, prepared in Example 6) in diethyl ether (90 mL) was added at 0 ° C to a 1.6 M solution of methyl diethyl diethyl ether (25 g). ml, 40 mmol) was diluted with the same solvent (75 ml). After 3.5 hours of stirring at 5 ° C, water (100 ml) was added and the separated organic cap was washed with brine (3 x 400 ml), dried with (MgSO 4), concentrated in vacuo, and dried. Bulb to bulb bulb (125 ° C / 0.2 torr) to give 1.8 g (53. yield) of 5-cyclopentylhexan-2-one.

IR: 2952, 2868, 1718, 1450, 1412, 1357, 1162. ^ -NMR: 0.86 (d, J = 6.1, 3H), 1.02-1.85 (m, 12H), 2.15 (s, 3H), 2.28- 2.57 (m, 2H). MS: 168 (5, Af), 150 (12), 135 (21), 121 (96), 111 (79), 110 (70), 108 (46), 81 (27), 71 (46), 69 (58), 67 (58), 58 (55), 55 (57), 43 (100), 41 (35).

Aroma: fruity, lavender, lily, lactonic, pineapple.

Example 13 -cyclopentyldenohexanoni trilo and 5- (cyclopent-1-enyl) hexanonitrile a) 5-cyclopentyl-5-hydroxyhexanonitrile 5-Oxohexanonitrile (11.1 g, 0.10 mmol) was added at 20 ° C to a suspension of anhydrous cerium III chloride (30 g, 0.12 mol) in THF (250 ml). After 1 hour of stirring at room temperature, cyclopentylmagnesium chloride (60 ml of 2M solution in diethyl ether, 0.12 mol) was added portionwise at 5 ° C and stirring was continued for 0.5 hours at the same temperature. 2 N HCl (60 ml) was added and the reaction mixture was extracted with MTBE (2 x 200 ml). The combined organic phase was washed with 2 N HCl (100 ml), and brine (2 x 100 ml), dried (MgSO 4) and concentrated in vacuo, to give 13 g of 5-cyclopentyl-5-hydro ^ crude hexahexanitrile (83% pure GC, 60% yield), used without further purification in the next step. b) 5-cyclopentylidenehexanonitrile and 5- (cyclopent-1-enyl) hexanone trile Crude 5-cyclopentyl-5-hydroxyhexanonitrile (18 g, 0.1 mol) in a solution of sulfuric acid (15 ml) in acetic acid was added. (150 ml). The reaction mixture was stirred at 5 ° C for 1 hour, then poured into ice (100 g), diluted with MTBE (100 ml), washed with saturated bicarbonate solution (5 x 300 ml), and brine ( 2 x 300 ml), dried (MgSO4), concentrated in vacuo, and bulb was distilled to bulbous to give a mixture of 2.1 and (13% yield) of 5-cyclopentylidene hexane and 5- (cyclopentane-1). enyl) -hexanitrile (GC: 43 + 57%) IR: 2953.2867.2245, 1457, 1433, 1377. ^ -IxMR: 1.03 (d, J = 6.7, 1.5H), 1.41-1.66 (m, 4H), 1.60 (s, 1.5H), 1.75 (m, J = 7.3, 1H), 1.84 (m, J = 7.4, 1H), 2.11- 2.38 (, 7.5H), 5.36 (m, 0.5 H): MS (Major Product): 163 (26, M +), 148 (62), 135 (20), 134 (23), 120 (32), 107 (66), 95 (77), 91 (24), 79 (32), 77 (25), 76 (100), 55 (29), 41 (42); MS (minor product): 163 (13, M +), 163 (6, 148 (28), 135 (18), 134 (12), 120 (38), 107 (31), 95 (199), 91 (18 ), 79 (24), 77 (20), 67 (93), 55 (20), 41 (33). Aroma: xamino, lily, spicy, floral, stronger than 5-cyclopentylhexanoni trilo.

Example 14 5 - Cyclcpentylhexanal Diisobutylaluminum hydride (60 ml of 1M hexane solution) was added at -65 ° C to a solution (50 ml) of 5-cyclopentylhexanonitrile hexane (5.0 g, 30 mmol, from example 11). ). After stirring at -70 ° C for 0.5 hour and at room temperature for 3 hours, methanol (1.8 ml) was added and stirring was continued for 20 minutes. 10% H 2 SO 4 (48 ml) was added and the reaction mixture was diluted with MTBE (150 ml). The organic layer was separated, washed with a saturated sodium bicarbonate solution (300 ml) and brine (3 x 300 ml), dried (MgSO 4), concentrated in vacuo, and bulb-to-bulb distilled (100 ° C). C / 0.2 torr) to give 2.6 g (51.5% yield) of 5-cyclopentylhexanal.

IR: 2950, 2867, 2715, 1727, 1452, 1410, 1377. lH-NMR: 0.90 (d, J = 6.4, 3H), 1.01-1.91 (, 14H), 2.35-2.46 (m, 2H), 9.77 ( t, J = 1.8, 1H). MS: 168 (19,? F), 150 (1), 135 (27), 121 (19), 109 (29), 97 (57), 96 (100), 95 (34), 81 (65), 69 (50), 68 (43), 67 (56), 55 (98), 41 (48).

Aroma: aldehydic, green, fresh, hesperidic, linear.

Example 15 -cyclopenthylene an-l-ol -Cyclopentylhexanal (4.2 g, 25 mmol) in ethanol (40 ml) was added to sodium borohydride (1.2 g, 32 mmol) suspended in the same solvent (50 ml) at 10 ° C and the reaction mixture stirred for 2 hours at room temperature. 1 N HCl (50 ml) at 0 ° C was added as drops. The mixture was diluted with MTBE (150 ml), the separated organic layer was washed with brine (3 x 250 ml), dried (MgSO 4), concentrated in vacuo, and bulb-to-bulb distilled (125 ° C / 0.2 torr). ) to give 3.4 g (80% yield) of 5-cyclopentylhexan-1-ol.

IR: 3326, 2949, 2865, 1452, 1376, 1059. Hí-NMR: 0.86 (d, J-6.4, 3H), 1.01-1.82 (JB, 17H), 3.63 (t, J = 6.5, 2H). MS: 152 (0.7, Af-H20), 137 (3), 123 (4), 110 (14), 109 (18), 101 (14), 97 (72), 96 (49), 95 (28) , 83 (80), 82 (53), 69 (33), 68 (33), 67 (47), 55 (100), 41 (35).

Aroma: floral, sweet, fruity, raspberry, powdery, with roses.

Example 16 - (2-methylcyclopent-l-enyl) pentan-1-ol JL 5- (5-methylcyclopent-1-enyl) pentan-l-ol 1,4-dibromopentane (76 g, 0.33 mol) dissolved in THF (450 ml) was added under reflux within 70 minutes at magnesium changes (15.8 g, 0.66 mol) in THF (50 ml). The mixture was refluxed for 90 minutes, cooled to room temperature and diluted with THF (250 ml). This solution was added within 160 minutes to caprolactone (37.6 g, 0.33 mol) dissolved in THF (400 ml), the temperature was maintained at 5 ° C.

After further agitation for 90 minutes, if cooling, the mixture was poured into ice water (1.2 1), acidified to pH 2 (HCl) and extracted with MTBE (2 x 600 ml). The organic phases were washed with water (4 800 ml), dried (Na 2 SO), and concentrated i vacuo and distilled (0.2 torr) over KHS04 (1.3 g) to give 23 g of an oil, which was further purified by flash chromatography (MTBE / hexane 1: 5) to give 4.8 g (9% yield) of a mixture of the two isomers. IR: 3334, 2930, 2856, 1456, 1379, 1072, 1052. ^ -NMR: 0.99 (d, J = 8, ca. 0.85H), 1.23-1.50 (m, ca. 5H), 1.52-1.69 ( m, ca. 5H), 1.72-1.79 (m, 1H), 1.91-2.32 (m, 5H, 3.58- 3.66 (ai, 2H), 5.29 (bs, ca. 0.3H) MS: 168 (18, A ), 81 (1), 95 (2), 67 (3), 55 (4), 41 (5) ', 107 (6), 135 (7), 121 (8).

Smell: floral, with roses, fruity (melon), marine.

Example 17 4- (cyclopent-1-enyl) butan-1-ol 4-cyclopentylidene-butan-1-ol 1,4-dibromobutane (64.8 g, 0. mol) was dissolved in THF (300 ml) was added within 45 minutes , magnesium (14.6 g, 0.6 mol) in the same solvent (3 ml). After 3 hours of stirring at reflux, the solution was cooled to room temperature and diluted with THF (30 ml), and ad valerolactone (30 g, 0.3 mol) dissolved in THF (450 ml) was added within 30 minutes, the temperature was maintained at 10 ° C. After stirring at room temperature for 2 hours, the reaction mixture was poured into ice water (500 ml), acidified to pH 2 (10% HCl) and extracted with MTBE (200 ml). The organic phases were washed with water (3 500 ml), dried (Na 2 SO 4), and concentrated and vacuumed and distilled (0.1 torr) onto KHS04 (0.5 g) to provide 1.5 g of an oil, which after flash chromatography (MTBE / hexane 1: 5) gave 3.4 g (8% yield) of the two isomers.

IR: 3334, 2934, 2844, 1652, 1436, 1056, 1032. aH-NMR: 1.46-1.69 (ijj, ca. 4.5H), 1.8-1.89 (m, ca. 1.5H), 2.0-2.12 (m, 2H), 2.14-2.32 (m, 4H), 2.78 (bm, 1H), 3.61 (t, J «7, 2H), 5.24 (m, ca. 0.25H), 5.33 (i, J = 1, ca. 0.75H); MS: 140 (19, Af), 79 (1), 67 (2), 93 (3), 41 (4), 53 (5), 31 (6), 107 (7), 122 (8).

Smell: roses, aldehyde, green Example 18 6-cyclopentyl-3-methylhexan-3-ol a) 1-ethenylcyclopentanol To a solution of vinyl bromide (146.6 g, 1.37 mol) in 250 ml of THF was added over 4 hours to a mixture of fine changes of magnesium (33.3 g, 1.37 mol) and an iodide crystal in 150 ml of THF a < 50 ° C. The resulting dark gray mixture was stirred for 1 hour, treated with a solution of cyclopentanone (104.8 g, 1.25 mol) in 100 ml of THF at 35-45 ° C, and stirred overnight at room temperature. A solution of saturated NH4C1 (11) was added. at ~ 0 ° C, and the reaction mixture was acidified to pH ~ 6-7 with IN HCl. The organic layer was separated, washed with brine (3 x 100 ml), dried over MgSO 4 and concentrated in vacuo. Distillation using a Widmer column (32 ° C / 0.06 torr) provided 67.6 g (48% yield) of 1-ethenylcyclopentanol. b) 5-cyclopentylidenepentan-2-one A 600 ml autoclave containing 1-ethenylcyclopentanol (172.0 g, 1.54 mol), isopropenyl ether (218.8 g; 3.04 mol), triethylamine (1.65 ml) and 85% H3P04 (0.72 ml), pressurized with N2 at 2 bar and heated to 125 ° C. An increase in pressure was observed at 7 bar. After 14 hours of stirring, the autoclave was cooled down to room temperature and depressurized. The mixture was taken up in MTBE (1.5 1), washed with H 0 (4 x 25 ml) to a neutral pH, dried (MgSO 4) and concentrated. Distillation (61 ° C / 0.1 torr) provided 161.3 g (69% yield) of 5-cyclopentylidenepentan-2-one. c) 6-cyclopentylidene-3-methylhex-l-in-3-ol Acetylene was pumped for 50 minutes, through a solution of tBuOK (33.8 g, 0.30 mol) in THF (240 ml), cooled down to 0 ° C. The resulting beige suspension was treated with 5-cyclopentylidenepentan-2-one (41.7 g, 0.27 mol) was added as drops for 15 minutes at 0 ° C. The resulting mixture was uniformly warmed to room temperature, and quenched with NH 4 Cl (180 mL). The aqueous phase was separated and extracted with MTBE (2 x 120 ml). The combined organic layers were washed with H20 (240 ml), brine (100 ml), dried over MgSO4 and concentrated in vacuo. Distillation (69-71 ° C / 0.09 torr) provided 38.95 g (81% yield) of 6-cyclopentylidene-3-methylhex-1-yn-3-ol. d) 6-cyclopentyl-3-methylhexan-3-o1 Hydrogenation of 6-cyclopentylidene-3-methylhex-1-yn-3-ol (5.0 g, 28 mmol) under standard conditions: H2 1 atmosphere, room temperature, over 5% Pd / C (0.57 g) in EtOH ( 30 ml) provided, after distillation (56 ° C / 0.66 torr) 4.57 g (89% yield) of 6-cyclopentyl-3-methylhexan-3-ol.

IR (pure): 3378, 2942, 2866. XH NMR: 0.89 (tf J = 7.5 Hz, 3H), 1.00-1.13 (m, 2H), 1.14 (s, 3H), 1.48 (g, J = 7.5 Hz, 2H), 1.24-1.65 (Jn, 11H), 1.69-1.84 (m, 3H). MS: 169 (2,? F-CH3), 155 (6), 137 (8), 95 (32), 81 (23), 73 (100), 67 (14), 55 (32), 43 (18 ), 41 (18).

Smell: floral (rosewood), fruity (apricot), hesperidic, neroli (essence of neroli).

Example 19 - (cyclopent-1-enyl) -2-methylphenyl-2-ol a) 5- (cyclopent-1-enyl) -2-pentanone A mixture of 5-cyclopentylidene-2-pentanone (9.92 g, 65 mmol) and p-TsOH (100 mg, 0.53 mmol) in toluene (150 mL) was heated at 90 ° C for 8 hours, then cooled down to Room temperature was diluted with MTBE (100 ml), washed with saturated NaHCO3 (50 ml), H20 (50 ml), brine (50 ml), dried over MgSO4 and concentrated in vacuo. Distillation under reduced pressure (48 ° C / 0.6 torr) yielded 7.13 g of 5- (cyclopent-1-enyl) -2-pentanone (purity ~ 80%), furthermore it was purified by flash chromatography to give 6.1 g ( 61%) of 89% pure product containing 11% 5-cyclopentylidene-2-pentanone. b) 5- (cyclopent-1-enyl) -2-methylpentan-2-ol - (cyclopent-1-enyl) -2-pentanone (5.95 g, 39 mmol) in ethyl ether (6 ml) was added dropwise to a 3M solution of methylmagnesium bromide in the same solvent (17 ml; mmol) for 15 minutes.

After 2 hours at reflux, the mixture was cooled to , down to room temperature, poured into ice (20 g), acidified with 5N HCl (20 ml) and extracted with MTBE (60 ml). The aqueous phase was separated and extracted again with MTBE (2 X 100 ml). The combined organic phases were washed with saturated NaHCO3 (80 ml), brine (80 ml), dried over MgSO4 and concentrated in vacuo. Bulb-to-bulb distillation (80 ° C / 0.06 torr) gave 5.84 g of 5- (cyclopent-1-enyl) -2-methylpentan-2-ol quantitatively containing 11% of 5-cyclopentylidene-2-methylpentan- 2-ol. IR: 3364, 2967, .2939, 2867, 2844, 1468, 1377, 1296, 1195, 1149, 1047, 910, 772. aH NMR: 1.21 (s, 6H), 1.41-1.56 (m, 4H), 1.80-1.90 (la, 2H), 2.02-2.11 (m, 2H), 2.18-2.26 (m, 2H), 2.26-2.33 (a, 2H), 5.31-5.35 (m, 1H). MS: 168 (0.5, Af), 150 (28), 135 (50), 95 (25), 94 (100), 93 (16), 81 (12), 80 (14), 79 (91), 69 (22), 67 (22), 59 (34), 43 (10), 41 (12). Smell: floral (with roses, geranium), fruity (plum), country.

Example 20 -cyclope tilpentan-2-ol a) 5-cyclopentylpentan-2-one The hydrogenation of 5-cyclopentylidene pentan-2-one synthesized in Example 18b (30.4 g, 0.2 mol under standard conditions (see Example 19d) gave, after distillation (61-67 ° C / 0.1 torr), 25.8 g (84 % yield) of 5-cyclopentylpentan-2-one. b) 5-cyclopentylpentan-2-ol NaBH portions (3.15 g, 83 mmol) were added portionwise to a solution of 5-cyclopentylpentan-2-one (16.0 g, 104 mmol) in MeOH (125 mL) at 0 ° C. The mixture was stirred at 0 ° C for 1 hour and then at room temperature for 2 hours. Water (100 ml) was added carefully, and the mixture was extracted with MTBE (3 x 250 ml). The organic phases were combined, washed with brine (3 x 50 ml), dried over MgSO 4, concentrated in vacuo and distilled (52-56 ° C / 0.045 torr) to give 14.5 g (90% yield) of 5%. -cyclopentylpentan-2-ol.

IR: 3347, 2947, 2861, 1453, 1374, 1308, 1116, 1077, 942. aH NMR: 1.00-1.12 (a, 2H), 1.18 (d, J «6.0, 3H), 1.23- 1.38 (a, 3H ), 1.38-1.64 (a, 7fl), 1.67 (bs, 1H), 1.70-1.80. { a, 3H), 3.73-3.85 (a, 1H). MS: 141 (6, Af-CH3), 123 (18), 111 (16), 110 (22), 96 (52), 95 (48), 83 (28), 82 (70), 81 (60) , 69 (42), 68 (36), 67 (84), 58 (12), 55 (34), 45 (100), 43 (16), 41 (35), 39 (12).

Smell: floral (tuberous), lily of the valley, coconut, celery.

E pg 21 -Cyclopentylidene-2-methylpentan-2-ol -cyclopentylidene-2-pentanone (13 * 4 g, 88 mmol) in ether (13 ml) was added portionwise for 30 minutes to a 3 M solution of methylmagnesium bromide in ether (38 ml, 114 mmol). ). After the addition of more ether (25 ml), the mixture was heated under reflux for 2 hours, then cooled down to room temperature, poured into ice (40 g), acidified with 5N HCl (50 ml) and it was extracted with MTBE (130 ml). The aqueous phase was separated and extracted with MTBE (2 x 130 ml). The combined organic phases were washed with NaHCO. saturated (2 x 130 ml), water (130 ml), dried over MgSO 4 and concentrated in vacuo. Distillation (52-55 ° C / 0.06 torr) yielded 11.24 g (76% yield) of 5-cyclopentylidene-2-methylpentan-2-ol.

IR: 3366, 2959, 2867, 1451, 1377, 1218, 1147, 910. lH NMR: 1.21 (s, 6H), 1.48-1.70 (a, 6H), 2.00-2.09 (a, 2H), 2.15-2, 24 (a, 4H), 5.20-5.28 (a, 1H). MS: 168 (0.5,?), 150 (65), 135 (100), 121 (12), 107 (26), 95 (46), 94 (68), 93 (32), 82 (30), 81 (13), 80 (10), 79 (63), 67 (40), 59 (42), 55 (10), 43 (12), 41 (16).

Smell floral ionone, linalool, raspberry, country, tea.

Example 22 -Cyclopentylidenepent-2-yl Propanoate a) 5-cyclopentylidenepentan-2-ol -cyclopentylidenepentan-2-one (22.1 g, 9 mmol) was reduced as in example 20b to give 24.5 g of the crude 5-cyclopentylidene-pentan-2-ol which was used without further purification in the next step. b) 5-cyclopentylidenepent-2-yl propanoate DMAP (0.03 g, 0.24 mmol, 0.8) was added to a mixture of 5-cyclopentylidene-pentan-2-ol (5-0 g, 32 mmol), propionic anhydride (6.7 mL, 52 mmol) and Et3N (7.2 ml, 52 mmol). After 1.5 hours of stirring at room temperature, the reaction mixture was diluted with MTBE (140 ml), washed with 2N HCl (60 ml), water (60 ml), saturated NaHCO 3 (60 ml), again with water ( 60 ml), and brine (60 ml), dried over MgSO 4 and concentrated in vacuo. Distillation under reduced pressure (87-92 ° C / 0.04 torr) provided 5.38 g (80% yield) of 5-cyclopentylidenepent-2-yl propionate IR: 2943, 2868, 1736, 1462, 1370, 1192, 1129, 1082. lH NMR: 1.14 (t, J-7.6, 3H), 1.21 (d, J-6.0, 3H), 1.46- 1.70 (a, 6H ), 1.91-2.07. { a, 2H), 2.10-2.18 (a, 2H), 2.18-2.25 (a, 2H), 2.30 (q, J - 7.6, 2H), 4.85-4.95 (a, 1H), 5.17-5.25. { a, 1H). MS: 195 (0.5,? F - CH3), 136 (100), 121 (57), 107 (60), 95 (54tS 94 (72), 93 (66), 91 (14), 81 (18), 80 (28), 79 (73), 77 (11), 68 (31), 67 (35), 57 (34), 41 (15).

Smell: floral, fruity, pear, ionone, apple Example 23 Perfume for bath gel -cislopentylhexanitrile DPG 10% 7.5 Aldehyde C 12 lauric 10% DPG 10 Ambretolide 10 Benzyl acetate 30 Bergamsto abergaptoacetite 115 Blackberry flower 3 Alpha Ketone 40 Citronelol E 20 Citronellyl acetate 10 Pure crystals of coumarin 20 Dipropylene glycol 117 Ethyl Linalool 35 Ethyl vanillin 5 Ethylene Brasilate 130 Eucalyptol 4 Eugenol pur 5 Givecona 3 Cinnamic andehyde hexyl 200 Beta ionone 10 Limonilo 3 Lilial 30 Miraldeno 3 Orange fluoride oil 30 Prunolido 10 Radj anol 40 Rodinol 70 10 Triciclal 3 Tuberous base (reconstitution) 7.5 Verdantiol 4 Vertofix coeur 50 Oil of ilang-ilang 35 1000 -cyclopentylhexanonitrile led to a diffusion batch for the fragrance, imparting a very rich ionone effect to the composition; the floral part of rose / lily of the valley of the fragrance, also increased considerably; This compound brought both, energy and elegance to this bath gel perfume.

Example 24 Fine fragrance for men -cyclopentylhexan-1-ol 10% DPG 30 Amiris oil 50 drops 50% Siam benzoin DEP 50 Italian bergamot oil 175 Caprionate 60 Citronellyl acetate 25 Damascenone 10% DPG 10 Dihydrolinalool 50 6-dimethylbenzylcarbinol isobutyrate Dimetol 40 Fenaldehyde 15 Fixa breno 4 Florhidral 5 Florol 50 Gardenol 5 Laurina 80 Italian lemon oil 40 Magnoliona 80 Vegan mandarin oil Italian 10 Olibanu res. 50% DEP 45 Florida Orange Oil 60 Tibetolide 10 Triciclal 10% DPG. 25 Tropional 40 Undecavertol 15 Velviona 20 1000 -cyclopentylhexan-1-ol led in the total top diffusion to the mixture. His notes hesperídicas increased, particularly of tangerine effect. The effect of aldehydic roses, adds to the transparency of the fragrance and its modernity through the low marine tones.

Example 25 Deodorant fragrance -Cyclopentylhexanal DPG 10% 30 Base Bergamot 50 Acetate of Caryl 25 Cepionate 50 Coumarin 5 Cyclohexium salicylate 12 Dipropylene glycol 105 Dinascona 10 15 Oil Ele i 5 Fixample 5 Folrosia 6 Hydro Rosa C (reconstitution of 300 rose oil) Iso E super 85 Blackberry Oil Junniper 20 Kefalis 30 Italian Lemon Oil 50 Absolute 10% PDG 35 Metambrace 45 Methyl Pamplemouse Ocoumal Nut Oil 10 Patchouli Oil SF 8 Sandalore 35 Pepper US PDG 10% 20 Tibetolide 30 1000 -cyclopentylhexanal brings superior harmony to the mixture; imparts anisic types, sage, nuances, along with its effect to natural roses / geraniums; through the evaporation of the low aniseed shades wrapped up to a floral, marine, anisic cocktail, which sums up the clean, transparent, modern effect of the fragrance in the deodorant application.

For the exact definition of the trivial names mentioned above, see Fl a vor and Fragrance Ma terial s 1998 r Allured Publishing Corporation, Carol, Stream, Illinois, U.S.A or Arctander, Perfume and Flavor Chemicals - 19679 published by the author, Montclair, New Jersey, U.S. TO.

It is noted that in relation to this date the best method known by the applicant to carry out the aforementioned invention, is that which was clear from the manufacture of the objects to which it refers.

Claims (9)

CLAIMS Having described the foregoing, the property contained in the following claims is claimed as property:

1. Compounds of the general formula I characterized in that R1, R2 and R3 are independently H, Ci-Cj alkyl, but R1 and R2 are not H at the same time; R2 can also be methylene or ethylidene; n = 0 or 1 and remains for an individual or double link, with it, maximum 2 double links are present.

2. 5-Cyclopentyl-3-methylpentanonitrile, according to claim 1.

3. 4-cyclopentylpentanenitrile according to claim 1.

4. 5-cyclopentylhexanonitrile according to claim 1.

5. 5-cyclopentylidenehexanonitrile according to claim 1. 10

6. 5- (Cyclopent-1-enyl) hexanonitrile according to claim 1.

7. Use of the compounds of formula II fifteen Wherein A is selected from the group of CR4R5OH, CR4R5OC (O) R6, C02R6, CN and C (O) R4; R1, R2, R3, R4, R5 and R6 are independently H or C1-C3 alkyl; R 2 can also be methylene or ethylidene; R6 can also be a C2- alkenyl or alkynyl n = 0 or 1 and remains for a single or double bond, thus, maximum 2 double bonds are present.

8. Use according to claim 7 as a fragrance.

9. Use according to claim 8 in fine and functional perfumery.