MXPA00001679A - 6-substituted 3-methyloct-6-enols - Google Patents

Abstract

The invention is concerned with mixtures of the (6E)- and (6Z)-isomers of 3,6-dimethyloct-6-en-1-ols and 6-ethyl-3-methyloct-6-en-1-ols and their mixtures as well as the use of these mixtures in odorant compositions. The mixtures are free from their corresponding oct-5-ene double bond isomers.

Description

3-METILOCT-6-ENOLES SUBSTITUTED IN POSITION 6 Description of the invention: The present invention concerns mixtures of the (6E) and (6Z) isomers of the 3,6-dimethyloct-6-en-1-ols and 6-ethyl-3-methyloct-6-en-1-ols, as well as the use of these mixtures in odorant compositions. The mixtures are free of their corresponding double-bond oct-5-ene isomers. Although it was not previously known that a compound can only imitate in a very natural way the complex olfactory impression of lily of the valley (lily of the valley), hydroxycitronellal (3, 7-dimeti I-7-hydroxyoctan-1-al) becomes a aroma markedly close to the smell of the lily of the valley. In combination with the other odoriferous compounds of lily of the valley, such as Lyral® [4 - (4-hydroxy-4-methyl-I -pent-l-yl) -cyclohex-3-en-l-carboxaldehyde], Lilial® [ 3 - (4-tert-butylphenyl) -2-methyl-propanal] and / or Dupical® [4 - (octahydro-4,7-methano-5H-inden-5-ylidene) butanal] (G. Fráter, JA B ajgrowicz, P. Kraft, Fragance Chemistry, Tetrahedron 1998, 54, 7633-7703), however, it is possible to come very close to the natural standard. The aldehyde group is common to all these odorants REF .: 32694 mentioned with the character of the lily of the valley. This results in instability of the compounds in oxidizing or strongly alkaline media. Some odorizers of the lily of the valley, without the aldehyde function, have been found in the alcohols Mayol® (4 - (1-meti I eti I) cic I ohexi I methane I), Majantol® (2,2-dimethyl-3-) (3-methylphenyl) propanol), Florol® (tetrahydro-4-methyl-2- (2-methylpropyl-2H-pyran-4-ol) and Mugetanol® [U. Harder, E. Oelkers, in: Recent Developments in Flavor and Fragrance Chemistry, published by VCH, Weinheim, 1993, pp. 162-163.] Furthermore, from patent WO 98/47842 the carbon analog has been known with Florol, with olfactory properties very similar to those of Florol®, however, these alcohols do not possess naturalness, radiant force and clarity, nor the olfactory strength of the aldehydes mentioned above and, therefore, there continues to be a need for a replacement substance for the aldehydes of the lily of the valley (lily of the valley). a requirement for additional odorant substances of lily of the valley (lily), especially with a functional group different from the aldehyde function, in order to obviate the aforementioned disadvantages.

In patent GB 1,167,776, one claims, among other things, a supposed compound having the general formulas la and Ib.

From the examples given there it is evident, however, that the compounds that fall within these formulas la and Ib, were never prepared in pure form. Now it has been established that this is also not possible at all from the preparation path that is described. In fact, in the dehydration of the 1,6-diols, which are the basis of the compounds la and Ib, a mixture of the three possible octan-1-oles is obtained, with respect to the double bond. For example, in the case of the compounds Ib, the alcohols (6 E) -6-et i I-3-methyl I or ct-6-en-1-ol (approximately 30) are obtained according to the process given. %), (6Z) -6-ethyl-3-methyloct-6-en-l-ol (approximately 30%) and 6-ethi I-3-methyloct-5-en-l-ol (approximately 40%). As mentioned in the patent, this mixture of compounds Ib has, in fact, the indicated smell similar to the lily of the valley and the rose, although the smell of the secondary notes of the rose is unpleasantly moldy. Due to this secondary note, of moldy rose, the mixture Ib can not completely satisfy the requirements of an odorizing substance of the lily of the valley, without an aldehyde function. Therefore, it has been used only sporadically in perfumery. Currently there is practically no commercial demand. For the time being, the production of the Ib mixture has been discontinued, for this reason. It has now surprisingly been found that the secondary notes of moldy rose, of the mixtures la and Ib, are due to oct-5-en-1 - or I is 6-eti I-3-meti I oc t- 5 -en -l-ol and (5 E / Z) - 3, 6-dimeti I oct-5-en-1 - or I and which, in the absence of these compounds, obtain mixtures which do not have the disadvantages mentioned above. The object of the invention, therefore, are the mixtures of the general formula II II Including all the R- and S- enantiomers, in which R can be a methyl or ethyl group. The class of compound, therefore, includes the two mixtures IIi and II2, and their mixtures.

II, The mixture 11 x has a floral, aldehydic, clear smell, typical of the lily of the valley, with a delicate citric nuance and a threshold value of 10 ng / L of air. More surprising, however, is the fact that the II2 mixture has a distinctive uniform, independent, floral, aldehydic, clear, uniform lily of the valley fragrance, with a uniform threshold value, somewhat lower, than that of the mixture IIi , that is, of 6 ng / L of air. The aspects of moldy rose, of the mixtures la and Ib, no longer appear; On the contrary, now new independent fragrance notes can be created. Therefore, mixtures 111 and II2 are suitable, ideally unlike the mixtures la and Ib- as odorants of lily of the valley (lily of the valley), without an aldehyde function, which exceeds the known aldehyde substitutes in terms of radiant force, clarity and olfactory uniformity. The olfactory citrus hue of the IIi mixture is a surprisingly new manifestation. It is assumed, therefore, that this was not previously recognized in the mixtures la and Ib, according to GB Patent 1, 167,776, because it was masked by the note of moldy rose. The mixtures IIi and II2, or their mixtures, are, then, remarkably suitable for perfumes of the clear floral type, especially those called Eaux Fraíches, as, for example, Eau d'Eden (Cacharel, 1996), Eau d'Issey ( I. Miyake, 1997), Eau belle (L. Azzaro, 1995), Eternity (C. Klein, 1988), Escape (C. Klein, 1991), New West for her (Aramis, 1990), and particularly those with a accented character of the lily of the valley (lily of the valley) as, for example, Diorissimo (Dior, 1956), Pleasures (E. Lauder, 1995), Agua di Gio (Armani, 1994), Hugo Woman (H. Boss, 1997), Envy (Gucci, 1996), Polo Sport Woman (R. La uren, 1996). The use, however, is not limited to these types of perfumes, nor to olfactory, odorant or special substances classes. The following are stated as examples of classes of substances that harmonize especially well with the mixtures, according to the invention.

- Ethereal extracts and extracts, e.g., bergamot oil, cedar oil, galbanum oil, absolute jasmine, rose oil, ilang-ilang oil. { Cananga odorata). Alcohols, e.g., Citronelol, Dimetol®, dimethylphenylethyl carbinol, Ebanol®, ethyl linalool, geraniol, Peonil®, phenylethyl alcohol, Radjanol®, Undecavertol®. -Aldehydes and Ketones, eg, Adoxal®, Alpha-Damascone, Dupical®, Florhydral®, Hedione®, Hydroxycitronella, cis-Jasmona, Lilial®, Lyral®, 4- (4-methoxyphenyl) -butan-2-one, Myraldene ®, Tropional®, Vertofix®. - Ethers and acetals, e.g., Acetal CD®, Ambrofix®, Caloñe®, diphenyl oxide, Folenox®, Galaxolide®, Glycolierral®, Limettol®, Magnolan®, Rhubafuran®, Spirambrene®.

-Esters and lactones, e.g. Agrumex®, benzyl acetate, benzyl salicylate, citronellyl acetate, Gardenol®, cis-3-hexenyl salicylate, Myraldilacetato®, Prunolide®, cis-jasmone lactone, Jasmonyl®, gamma-undecalactone.

Macrocycles, e.g., Ambettrolide®, Ambretona®, Ethylene Bilament®, Habanolide®, Muscone®, Musk CPD®, Musk 174®, Thibetolide®. -Heterocycles, e.g. Indole, Piralone®.

Mixtures 111 and II2 were produced by the reaction of the Grignard reagent, 5-b r o m or -3-methylpentan-1-ol, protected with THP, with acetaldehyde or propionaldehyde; subsequent oxidation of Dess-Martin; followed by a Wittig reaction, with a deprotection reaction with acid catalyzed ethyltriphenylphosphonium bromide. However, other protecting groups (e.g., tert-butyldimethylsilyl) or oxidizing agents (e.g., pyridinium chlorochromate) can also be used. This approximation, which gives the free compounds of the corresponding double bond isomers of oct-5-ene, is illustrated in the following reaction schemes: 3. Dess-Martin Peryodinate ll? Peryodinato of Dess-Martin Advantages, features and additional details will become apparent from the following description of the Examples for the production of the mixtures of preferred working examples, with respect to use of the mixtures.

EXAMPLE 1 (6E / Z) -3.6-Dimethyloct-6-en-l-ol (II X A solution of 182 mL (1.50 mol) of 3-meti I pe n ta no - 1, 5 - dio I (3) , in 3 mL of toluene, was treated in portions, with a total of 185 mL (1.6 mol) of 48% hydrobromic acid, and then heated to reflux (internal temperature of 100 to 110 ° C) in a water separator for 5 hours After 170 L of water had been removed, the reaction mixture was allowed to cool, was emptied over 400 mg of ice and treated with 500 mL of water and 30 mL of a sodium hydroxide solution at room temperature. 30% The organic phase was separated and washed with 750 mL of 2N hydrochloric acid, twice with 750 mL of water, each time, and then with 750 mL of saturated sodium chloride solution, after drying over sodium sulfate. and concentrating in a rotary evaporator, after rapid chromatography (tert-butyl methyl ether: n-pentane, 1: 1, R f = 0.57) on silica gel, 106 g (39%) of 5-bromine were obtained. -3-methylpentan -l-ol A solution of 1.48 g (0.82 mol) of 5-bromo-3-methylpentan-1-ol, from several analogous batches, in 1 L of dry dichloromethane, was treated under a nitrogen atmosphere, while stirring and it was cooled in an ice-water bath, with a solution of 107 g (1.27 mol) of 3, 4-dihydro pyran and 17.4 g (69.3 mmol) of to I uen-4-its pyridinium 1-fonate in 1 L of dry dichloromethane. After removal of the cooling, the reaction mixture was allowed to stir at room temperature for an additional 8 hours, then poured into 6 L of water and the product was extracted twice with 500 mL of tert-butyl methyl ether, each time. The combined organic extracts were dried over sodium sulfate and cleaned of the solvent in a rotary evaporator. Flash chromatography (n-pentane: tert-butyl methyl ether, 20: 1) on silica gel gave 197 g (91%) of 5'-bromo-3'-methylpent-1-yl tetrahydropyran-2-ether. ilo (4). IR (film): v = 1035/1077/1121/1135 cm "1 (v C -O), 1353/1381 cm '1 (vCH3), 1454/1441 cm" 1 (vCH2) - XH-NMR (CDCI3 ): d = 0.94 (d, J = 6.4 Hz, 3H, 3'-H3), 1.43-1.71 (m, 8H, 3 -, 4 -, 5 -, 2 '- H 2), 1.82 (mc, 2H , 3'-H, 4'-Hb), 1.93 (mc, ÍH, 4 * -Ha), 3.37-3.52 (m, 4H, 1'-, 5'-H2), 3.77-3.87 (m, 2H, 6-H2), 4.57 (mc, 1H, 2-H) .- 13 C-NMR (CDCl 3): 6 = 18.83 / 18.92 (2q, 3'-Me), 19.48 (2t, C-4), 25.35 (2t , C-5), 28.88 / 28.94 (2d, C-3 '), 30.61 (2t, C-3), 31.67 (2t, C-5'), 35.94 / 36.03 (2t, C-2 '), 39.82 /39.93 (2t, C-4 '), 62.15 / 62.18 (2t, C-l'), 65.16 / 65.34 (2t, C-6), 98.62 / 98.83 (2d, C-2) .- MS (El) : m / z (%) = 41 (30) [C3HS +], 55 (63) [C 4 H 7 +], 85 (100) [C5H9O +], 101 (3) [C5H902 +, supplementary am / z = 163/165], 163/165 (9) [C6H 12Br +, complementary to 101], 263/265 (2) [M + -H].

Approximately 5 ml of a solution of 50.0 g (200 mmol) of ether 5'-bromo-3'-methylpentyl-1-tetrahydro-pyran-2-yl (4), in 250 μl of dry tetrahydrofuran. , were added to 5.50 g (226 mmol) of magnesium shot in 40 μl of dry tetrahydrofuran and the mixture was heated while stirring slowly with a KPG shaker until the reaction was started. Subsequently, the heating source was removed and the rest of the solution of 5'-bromo-3'-methylpent-1-yl tetrahydropyran-2-yl ether was added slowly, dropwise. Subsequently, the mixture was heated to reflux for 20 hours and, after cooling, a solution of 11.0 g (250 mmol) of acetaldehyde in 70 mL of dry tetrahydrofuran was slowly added dropwise. After stirring for 3 hours, the reaction mixture was added to 1 L of saturated ammonium chloride solution, the organic phase was separated and the aqueous phase was extracted twice with 300 mL of tert-butyl methyl ether each time. The combined organic phases were washed twice with 300 mL of saturated sodium chloride solution each time, they were dried over sodium sulfate and concentrated to dryness in a rotary evaporator. By using flash chromatography (n-pentane: tert-butyl methyl, 5: 1, R f = 0.30) of the residue, on silica gel, 26.5 g (58%) of 5'-methyl ether were obtained. -2'-hydroxyhep-7'-yl tetrahydropyran-2-yl. This was recovered in 350 mL of dry dichloromethane and treated at room temperature with a solution of 73.1 g (173 mmol) of Dess-Martin periodinate in 350 mL of dry dichloromethane. After stirring at room temperature for 2 hours, the reaction mixture was treated with 1 L of tert-butyl methyl ether and a solution of 225 g (1.42 mmol) of sodium thiosulfate in 1 L of saturated sodium hydrogen carbonate solution . After stirring at room temperature for 10 minutes, the organic phase was separated, the aqueous phase was extracted twice with 500 mL of tert-butyl methyl ether, each time, the combined organic phases were washed with saturated sodium hydrogen carbonate solution and saturated solution of sodium chloride. After drying over sodium sulfate and removing the solvent in a rotary evaporator, they are obtained, by means of flash chromatography (n-pentane: tert-butyl methyl ether, 10: 1, Rf = 0.42), on silica gel, 23.1 g (88%) of 5'-methyl-2'-oxohept-7'-yl tetrahydropyran-2-yl ether (5). IR (film): v = 1717 cm "1 (vC = O), 1035/1078/1122/1136 cm "1 (vC-O), 1355 cm" 1 (vCH3), 1454/1441 cm "1 (v CH 2) .- H-NMR (CDCl 3): 6 = 0.91 (d, J = 5.6Hz, 3H, 5'-H3), 1.43-1.81 (m, 11H, 3-H2-5-H2 and 4'-H2-6'-H2), 2.15 (S, 3H, l'-H3 ), 2.42-2.48 (m, 2H, 3'-H2), 3.38-3.53 (m, 2H, 7'-H2), 3.74-3.88 (m, 2H, 6-H2), 4.56 / 4.57 (2t, 3 = 4.2 / 4.0 Hz, ÍH, 2-H) .- l 3C-NMR (CDCI3): 6 = 19.17 / 19.28 (2q, C-l '), 19.47 / 19.52 (2q, 5'-Me), 25.27 ( 2t, C-5), 29.37 / 29.41 (2d, C-5 '), 30.48 / 30.57 (2t, C-3), 36.18 / 36.22 (2t, C-6'), 41.14 / 41.11 (2t, C- 3 *), 62.14 / 62.21 (2t, C-7 '), 65.32 / 65.51 (2t, C-6), 98.61 / 98.94 (2d, C-2), 208.97 / 209.60 (2s, C-2 *). -MS (El): m / z (%) = 43 (48) [C3H7 +], 55 (15) [C4H7 +], 69 (27) [C5H9 +], 85 (100) [C5H90 +], 101 (18) [C8H? 5O +, complementary with / 77 / z = 127], 109 (43) [C8H 13 +], 127 (35) [M + -C8H 150, complementary with m / z = 101], 143 (8) [M + -C5H9O], 227 (1) [M + -H]. 14. 7 g (39.5 mmol) of bromide of thi 11 were added, under a nitrogen atmosphere, to a solution of 4.25 g (37.7 mmol) of potassium t-b u t t ion in 50 mL of dry tetrahydrofuran. The reaction mixture was heated to reflux and, at this temperature, a solution of 7.50 g (32.9 mmol) of 5'-methyl I-2 '- or xo hept-7'-ethyltetrahydropyran-2-yl ether (7.30 g) was allowed to drip ( 5), in 25 mL of dry tetrahydrofuran. After stirring at reflux for 2 hours and at room temperature for 8 hours, the reaction mixture was added to 400 mL of tert-butyl-methyl ether / water (1: 1), the organic phase was separated and the aqueous phase was extracted. three times with 100 mL of tert-butyl methyl ether, each time. The organic phases were combined, dried over sodium sulfate and concentrated in a rotary evaporator. By means of flash chromatography (n-pentane: tert-butyl methyl ether, 100: 1, R f = 0.44), on silica gel, 7.15 g (90%) of ether 3 ', 6'-dimethyloct-2'- were obtained. en-8'-yl tetrahydropyran-2-yl, as a colorless liquid. A solution of 7.00 g (29.1 mmol) of the 3 ', 6'-dimethyloct-2'-en-8'-yl tetrahydropyran-2-yl ether in 200 mL of dry methanol was treated with 10 g of Amberlyst® 15 and stirred for 20 hours, at room temperature. The ion exchanger was filtered and extracted twice with 100 mL of methanol. After concentration of the combined organic phases in a rotary evaporator, the following were obtained by flash chromatography (n-pentane: methyl tert-butyl ether), 10: 1, Rf = 0.14), 3.86 g (85%) of (6E / Z) ) -3,6-dimethyloct-6-en-l-ol (III), as a colorless liquid, with an intense odor. Smell: floral, clear aldehydic, similar to the lily of the valley (lily), with a slightly citrus hue. -IR (film): v = 3338 cm "1 (v OH), 1059 cm-1 (v CO), 1457 cm" 1 (v CH2), 1378 cm "1 (v CH3) .- 'H- MN ( CDI3): 6 = 0.89 / 0.90 (2d, J = 6.8 / 6.4 Hz, 3H, 3-Me), 1.26-1.18 (m, HI, 3-H), 1.35-1.43 (m, 2H, 4-H2) , 1.52- 1.66 (m, 2H, 2-H2), there 1.56 (d, J = 6.8 Hz, 3H, 8-H3), 1.59 / 1.67 (2s, 3H, 6-Me), 1.98-2.04 (m, 2H, 5H2), 2.42 (br s, 1H, OH), 3.61-3.70 (m, 2H, 1-H2), 5.19 (mc, 1H, 7-H) .- 13 C-NMR (CDCl 3): 6 = 13.03 / 13.20 (2q, C-8), 19.44 (2q, 3-Me), 15.48 / 23.27 (2q, 6-Me), 29.12 / 29.47 (2d, C-3), 28.70 / 35.03 / 35.33 / 36.93 (4t, C-4, -5), 39.68 / 39.71 (2t, C-2), 60.79 (2t, Cl), 117.93 / 118.51 (d, C-7), 136.24 / 135.96 (2s, C-6) .- MS (El): m / z (%) = 41 (100) [C3H5 +], 55 (88) [C4H7 +], 70 (73) [C5H10 +], 81 (35) [C6H9 +], 109 (19) [C8H1 3 +], 123 (4) [M + -H2O-CH3], 138 (2) [M + -CHO], 156 (8) [M + J.

Example 2 (6E / Z) -6-ethyl-3-methyloct-6-en-l-ol f 11 ^ The corresponding Grignard reagent was prepared, in analogy to Example 1, from 1.65 g (67.8 mmol) of magnesium shot and 18.9 g (67.8 mmol) of ether 5'-b ro mo-3'-meti I pent-1'-i I tetrahydropyran-2-yl (4), in 85 mL of tetrahydrofuran. After heating at reflux for 3 hours, the reaction mixture was allowed to cool to 30 ° C and treated, dropwise, with 4.32 g (74.6 mmol) of propionaldehyde dissolved in 30 mL of dry tetrahydrofuran. After the exothermic reaction had reduced, the mixture was stirred at room temperature for an additional 1 hour and subsequently it was added to 500 L of a saturated solution of sodium chloride. The organic phase was separated and the aqueous phase was extracted three times with 100 mL of tert-butyl methyl ether, each time. The combined organic phases were washed twice with 150 mL of saturated sodium chloride solution, each time, and then dried over sodium sulfate. After removing the solvent in a rotary evaporator, by means of flash chromatography (n-pentane: tert-butyl methyl ether, 5: 1, Rf = 0.30), the residue was obtained, on silica gel, 5.87 g (36%) of the 6'-methyl-3'-hydroxyoct-8'-yl tetrahydropyran-2-yl ether. This was dissolved in 75 mL of dry dichloromethane and treated at room temperature with 15.3 g (36.0 mmol) of Dess-Martin periodon while stirring vigorously. After stirring for 2 hours, 250 mL of tert-butyl methyl ether was added, followed by a solution of 48 g of sodium thiosulfate in 250 mL of saturated aqueous sodium hydrogen carbonate solution. After stirring for 10 minutes, the organic phase was separated, the aqueous phase was extracted twice with 200 mL of tert-butyl methyl ether and the combined organic extracts were washed with saturated sodium hydrogen carbonate solution and saturated chloride solution. of sodium. After drying over sodium sulfate and removal of the solvent in a rotary evaporator, by flash chromatography (n-pentane: tert-butyl methyl ether, 10: 1, Rf = 0.31), 5.00 g (94%) of the 6 '-methyl-3'-oxooct-8'-yl tetrahydropyran-2-yl ether (6), as a colorless oil. IR (film): v = 1716 cm "1 (v C = O), 1034/1078/1122/1136 cm "1 (v CO), 1353/1378 cm" 1 (v CH3), 1456 cm "1 (v CH 2) .- XH-NMR (CDI3): 6 = 0.91 (d, J = 6.0 Hz, 3H, 6'-H3), 1.05 (t, J = 7.4 Hz, 3H, l'-H3), 1.41-1.81 (m, 11H, 3-H2-5-H2 and 5'-H 2 - 7 '- H 2), 2.37-2.48 (m, 4H, 2' -, 4'-H2), 3.36-3.53 (m, 2H, 8'-H2), 3.74-3.88 (m, 2H, 6 -H2), 4.56 / 4.57 (2t, J = 3.5 / 4.0 Hz, ÍH, 2-H) .- 13C-NMR (CDCI3): 6 = 7.65 (2q, C-l '), 19. 19 / 19.30 (2q, 6'-Me), 19.48 / 19.52 (2t, C-4), 25.28 (2 t, C-5), 29.44 / 29.49 (2d, C-6 ') . 57 / 30.57 / 30.60 / 30.67 (4t, C-3, -5 '), . 62 / 35.64 / 36.19 / 36.24 (4t, C-2'-7 '), 39.75 / 39.77 (2t, C-4'), 62.14 / 62.21 (2t, C-8 '), 65.36 / 65.54 (2t, C -6), 98.62 / 98.84 (2d, C-2), 211.58 / 211.59 (2s, C-3 ').-MS (El): m / z (%) = 57 (53) [C4H5], 85 ( 100) [CsH90], 101 (10) [C5H80], 123 (19) [C8H nO], 141 (32) [M + -C5H902J, 158 (8) [M + -C5H80], 213 (1) [M + - C2H5], 241 (1) [M + - H]. Similarly, in analogy to Example 1, 9.10 g (24.6 mmol) of eti 11 rifeni I phosphonium bromide were added, under nitrogen, to a solution of 2.60 g (23.2 mol) of tert-butyl I potassium, in 40 μL of dry tetrahydrofuran. The reaction mixture was heated to reflux and, at this temperature, a solution of 9.10 g (24.6 mmol) of ether 6'-methyl I-3'-oxo or ct-8'-i was added to the hydroponic n - 2 - i ico (6), in 10 mL of tetrahydrofuran. After stirring at reflux for 33 hours and at room temperature for 8 hours, the reaction mixture was added to 300 mL of tert-butyl methyl ether / water (1: 1), the organic phase was separated and the aqueous phase was extracted three times. times with 100 mL of tert-butyl methyl ether, each time. The organic phases were combined, dried over sodium sulfate and concentrated on a rotary evaporator. After rapid chromatography (n-pentane: tert-butyl methyl ether, 100: 1, Rf = 0.39), on silica gel, 4.62 g (96%) of ether 3'-ethyl I-6'-methylate were obtained. oct-2'-en-8'-i I tetrahydropyran-2-yl, as a colorless liquid. A solution of 4.50 g (18.9 mmol) of the ether 3'-ethyl-6'-methyloct-2'-en-8'-yl tetrahydropyran-2-yl in 150 mL of dry methanol was treated with 7.50 g of Amberlyst ® 15 and stirred for 16 hours at room temperature. The ion exchanger was filtered and extracted twice with 150 mL of methanol. After concentration of the combined organic phases, in a rotary evaporator, by means of flash chromatography (n-pentane: tert-butyl methyl ether, 10: 1, Rf = 0.22), 2.52 g (78%) of (6E) were obtained / Z) -6-ethyl-3-methyloct-6-en-l-ol (II2), as a colorless liquid, with an intense odor. Smell: Extremely uniform and independent, specifically similar to lily of the valley (lily), floral, clear aldehydic. -IR (film): v = 3328 cm "1 (v O-H), 1058 cm" 1 (v C-0), 1459 cm (v CH2), 1377 cm -1 (v CH3) H- RM N (CDCl 3): 6 = 0.90-0.99 (m, 6H, 2'-H3, 3-Me), 1.18-1.26 (m, 1H) , 3-H), 1.35-1.45 (m, 2H, 4-H2), 1.51-1.66 (m, 2H, 2-H2), there 1.57 (d, J = 6.8 Hz, 3H, 8-H3), 1.96 -2.06 (m, 4H, 5-, l'-H2), 2.15 (br s, ÍH, OH), 3.60-3.71 (m, 2H, 1-H2), 5.17 (mc, ÍH, 7-H). -13 C-NMR (CDCl 3): 6 = 12.73 / 12.74 / 12.86 / 12.98 (4q, C-8, C-2 '), 19. 45 / 19.48 (2q, 3-Me), 22.62 / 27.17 (2t, C-l '), 29.27 / 29.67 (2d, C-3), 29.57 / 33.87 (2t, C-5), 35.48 / 35.61 (2t , C-4), 39.69 / 39.76 (2t, C-2), 60.90 (2t, Cl), 116.78 / 117.47 (2d, C-7), 141.97 (2s, C-6). -MS (El): m / z (%) = 31 (8) [CH2OH +], 41 (38) [C3H5 +], 55 (85) [C4H7 +], 69 (84) [C 5 H 9 + ], 84 (100) [C6H12 +], 97 (19) [C7H13 +], 123 (18) [M + - H 2 O - C 2 H s], 141 (5) [M + -CHO], 170 (21) [M +]. The compounds II are ideally suited for the creation of floral, clear, lily of the valley chords, as demonstrated in Example 3. Mixtures II, especially mixture 111, intensify the basic floral chord. The compounds II, especially the mixture Ilt, are probably ideally suited for use in cosmetological articles and body care agents, especially gels and foams for bathing, by the emphasis of a specific olfactory, floral, clear aldehydic impression of the lily of the valley (lily), whereby the odorant mixture, according to the invention, does not produce irritations or discoloration in the skin. On the other hand, the aldehydic odorants of the lily of the valley, of the current technique, frequently cause discolorations, as well as irritations, on the skin.

Eiemolo 3 Eau Fraíche (Aaua Fresca) Unisex Eau Fraíche Unisex with high hesperidic notes, a medium floral note, clear, with an aroma (bouquet) ionone and jasmine, lily of the valley, as well as green accent, marine-clear and a basic wooden note, similar to amber, reminiscent of lily and sandalwood: Compound / Ingredient Parts by weight, in% 1. Allylcyclohexylglycollate, 10% dipropylene 20 glycol 2. Bergamot oil 150 3-Butyltetrahydro-5-methyl-2H-50 pyran-4-yl acetate [Jasmonyl®] Lemon oil, Italian 25 2,6-Dimethylheptan-2- ol [Dimetol®] 35 3,7-Dimethylnone-1, 6-dien-3-ol [ethyl linalool] 50 Dipropylene glycol 60 Florhydral®, 10% dipropylene glycol 5 l, 3,4,6,7,8- Hexahydro-4,6,6,7,8,8- 100 hexamethylcyclopenta [g] -2-benzopyran [Galaxolide®] 50 PHT cis-Hex-3-en-l-ol, 10% in dipropylene glycol 5 beta -Ionona 35 Spearmint oil, EU, 10% in 5 dipropylene glycol Tangerine oil, Italian 10 7-Methyl-2H-1, 5-benzodioxepin-3 (4H) -one 5 [Caloñe 1951®], 10% dipropylene glycol Methyl dihydrojasmonate 200 l-Methyl-3- [4- (1, 1-dimethylethyl) phenyl] propanal 35 [Lilial®] 3-Methyl-5- (2,2,3-trimethyl-3-cyclopenten-l- 30 il) -4-penten-2-ol [Ebanol®], 10% in dipropylene glycol 18. l- (1, 2,3,4,5,6,7,8-Octahydro-l, 2.8, 8- 30 tetramethyl-2-naphthalenylethanone [Georgywood®] 19. 3a, 6,6,9a-Teramethyldecahydro [2, lb] 75 naphthofuran [Fixambrene®], 10% in dipropylene glycol 20. Tropional 25 21. Mixture IIj 50 1000 The basic floral chord is intensified by the mixture 111. The mixture gives it a clear, intense note of the lily of the valley, without secondary aspects to mold such as, for example, when the mixture is used or Ib. Therefore, the transparent aspects, which are reminiscent of tea, of composition, manifest themselves especially well.

Eje plo 4 Composition for perfume, with a clear floral odor, to be used in cosmetics and body care products Parts by weight, Com posed / Ing in 1/1250 Ethyl acetoacetate 25 Allylcyclohexylglycollate 2 Benzyl acetate, the purest 35 Cassis base 345 F 5 Caryl acetate 20 Citronellyl acetate, 10% dipropylene glycol 5 Cyclopentadecanolide [Thibetolide®] 5 2,4-Dimethyl-3-cyclohexencarboxaldehyde 4 [Tricyclal®] 2,6-Dimethylhept-5-enal [Melonal®], 10% in dipropylene glycol 3,7-Dimethyloct-6-en-l-ol [Rhodinol®] 35 Dipropylene glycol 446.5 Dodeca h id ro- 3a , 6,6, 9a-tetra methyl-napht [2,1b] -2-furan, 10% in dipropylene glycol 3,7-Dimethyl-1-l, 6-dien-3-ol [ethyl linalool] 50 l, 4-Dioxacycloheptadecan -5,17-dione [ethylene brasylate] 4-Ethyl-3- (4-ethylphenyl) -2,2-dimethylpropanal [Floralozone®] 1, 3,4,6,7,8-Hexahydro-4,6, 6,7,8,8-hexamethyl-150 cyclopenta [g] -2-benzopyran [Galaxolide®] 50 BB Hexyl salicylate 5 alpha-Hexylcinnamaldehyde 100 4- (4-Hydroxy-4-methylpentyl) cyclohex-3-en- l- 25 carboxaldehyde [Cyclohexal®] Indole, pure, 10% dipropylene glycol 3 cis-Jasmine 0.5 Linalool, synthetic 8 Methyl dihydrojasmonate 50 1- Met il -3- [4- (1,1-dimethyl and leil) phenyl] propan to I 80 [Lilial®] 8-Methyl-beta-ionone [Isoraldeine®] 35 4-Methyl-2- (2-methyl-ylpropyl) ) trahydropyran-4-ol 5 [Florol®] (4-Methylphenyl) acetaldehyde [Aldehyde Syringa®], 15 10% in diethyl phthalate 3-Methyl-5-phenylpentan-l-ol [Phenoxanol®] 10 Nerol, extra 15 l- (1, 2,3,4,5,6,7,8-Octahydro-2,3,8,8-tetramethyl-2-naphthalenyl) ethanone [Iso E super®] (10E) -l- Oxacicloheptadec-10-en-2-ona 10.5 [Ambrettolide®] 1-phenylethyl-l-acetate [Gardenol®] 2.5 Phenylethyl alcohol 20 Pepper oil, black 2 Rose TW 62/9 Norx 20 alpha-Terpineol [Lindenol® ] 5 10-Undecen-l-al, 1% in dipropylene glycol 10 Mixture II2 10 The light, clear, bright character of the lily of the valley, of the mixture II2, is clearly evident in the composition; surprisingly still at this relatively low dose, it provides elegance and clarity in the olfactory picture and emphasizes the careful nature of the product. The mixture II2 can even intensify the effect of other alcohols with less pronounced smell of the lily of the valley (lily of the valley), as shown here in the Florol® example. Neither Majantol®, nor Majol®, nor Mugetamol®, are able to produce in this composition, in similar doses, a natural note of the lily of the valley, and the mixtures la and Ib are not capable of this either. It is noted that, in relation to this date, the best method known to the applicant to carry out the aforementioned invention is the conventional one for the manufacture of the objects or substances to which it refers.

Claims (5)

REVIVAL DICTION ES Having described the invention as above, the content of the following claims is claimed as property. 1. Mixtures of general formula II:
1. II including all the R- and S- enantiomers, characterizes as because R represents methyl or ethyl, which are free of the corresponding oct-5-ene double-bond isomers.
2. 2. The mixture, according to claim 1, characterized in that it contains (6 E) -3,6-dimeti I oct-6-en-l-ol and (6 Z) -3,6-dimeti I or ct-6- en-1 - or I (IIX), and because it is free from (5E / Z) -3,6-dimethyloct-5-en-l-ol. II,
3. 3. The mixture, according to claim 1, characterized in that it contains (6E) -6-ethyl-3-methyloct-6-en-1-ol and (6 Z) -6-eti I-3-meti I oct-6 - in - 1 - or I (II2), and because it is free of (5 E / Z) - eti I - 3 - me ti I oct- 5 -en - 1 - or I. II,
4. 4. An odorant composition, characterized in that it contains a mixture according to any of claims 1 to 3.
5. 5. The use of the mixture, according to any of claims 1 to 3, as an odorant.