Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
  • C07D319/08—1,3-Dioxanes; Hydrogenated 1,3-dioxanes condensed with carbocyclic rings or ring systems
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B9/00—Essential oils; Perfumes
  • C11B9/0069—Heterocyclic compounds
  • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
  • C11B9/008—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing six atoms

Definitions

• the invention relates to the field of fragrances. More particularly, the invention relates to bicyclic dioxanes, their method of preparation, and their use in the fields of perfumery.
• examples of commercially available acetals comprise Methyl Pamplemousse® (1), Floropal® (2), and Oxane® (3). These compounds are widely used in the field of perfumery.
• rosy notes are quite important.
• One example of a cyclic dioxane having a floral note is Magnolan®. It is interestingly used to bring freshness, in particular to lily of the valley accords.
• Examples of cyclic dioxanes having ambery notes include Okoumal (6), Karanal (5), and Spirambrene (7). Okoumal possesses a powerful ambery fragrance which blends very well to woody accords. Karanal and Spirambrene also have a tenacious odour.
• the Applicant thus focused on the synthesis of new bicyclic acetals, more precisely bicyclic 1,3-dioxanes. Surprisingly and unexpectedly, the new 1,3-dioxane derivatives did not present the expected ambery notes, but mainly unexpected green notes.
• the invention is directed to the use of compounds of formula:
• R 3 and R 4 are independently a hydrogen atom, a C1-C6 alkyl group or a C2-C6 alkenyl group,
• R 5 is a C1-C6 alkyl group, a C2-C6 alkenyl group or a (CH 2 )o- 2 -aryl group,
• R 6 is a C1-C6 alkyl group, a C2-C6 alkenyl group, a (CH 2 )o- 2 -aryl group or a C5-C6 cycloalkyl or cycloalkenyl group, and
• R y is a hydrogen atom, a C1-C6 alkyl group or a C2-C6 alkenyl group
• R 3 , R 4 and R 5 are as above defined, and
• R 6 and R 7 together with the carbon atom to which they are attached form a C5-C6 cycloalkyl or cycloalkenyl group.
• This invention relates to the compounds of formula (I), as described above, as well as to any of their various stereoisomers.
• the invention is also directed to a method of preparation of compounds of formula (I) as defined above.
• R 3 and R 4 are independently selected from the group consisting of a hydrogen atom, methyl, ethyl, /-propyl, /-butyl, and /-butyl, more preferably from the group consisting of a hydrogen atom, methyl and /-butyl.
• R is preferably selected from the group consisting of methyl, ethyl, /-propyl,
• R is preferably selected from the group consisting of methyl, ethyl, w-propyl,
• 2,4-dimethylcyclohexen-3-yl more preferably from the group consisting of methyl, ethyl,
• R 7 is then preferably selected from the group consisting of a hydrogen atom, methyl, ethyl, ⁇ -propyl, /-propyl, «-butyl, /-butyl, /-butyl, «-pentyl and 1-propen-l-yl, more preferably from the group consisting of hydrogen atom, methyl and w-butyl.
• R 6 and R 7 together with the carbon atom to which they are attached form a cyclopentyl or cyclohexyl group, preferably a cyclopentyl group.
• R 3 and R 4 are hydrogen atoms. In this first embodiment, advantageously:
• R 5 is selected from the group consisting of methyl, ethyl, /-butyl and phenyl, and more preferably methyl,
• R 6 is selected from the group consisting of methyl, ethyl, /-propyl, phenyl, benzyl and
• R 7 is selected from the group consisting of a hydrogen atom, methyl and «-butyl, and more preferably a hydrogen atom.
• R 3 and R 7 are hydrogen atoms, and R 4 is /-butyl.
• R 3 and R 7 are hydrogen atoms, and R 4 is /-butyl.
• R 5 is methyl, ethyl or phenyl
• R 6 is methyl or /-propyl.
• R 3 and R 4 are methyls, and R 7 is a hydrogen atom.
• R 3 and R 4 are methyls, and R 7 is a hydrogen atom.
• R is methyl or ethyl
• R 6 is selected from the group consisting of methyl, /-propyl and 1-propen-l-yl.
• the compounds of formula (I) as defined above exhibit interesting olfactive properties. Very unexpectedly and surprisingly, they do not show the typical floral, ambery or fruity notes that the skilled person would have expected, but rather green and/or spicy notes.
• the invention therefore relates to the use of the compounds of formula (I) as described above as fragrant agents.
• This invention also relates to a fragrant composition containing at least one compound of formula (I) according to the invention.
• This invention includes any fragrant composition comprising, as a fragrant or flavouring agent, at least a compound of formula (I).
• the compounds of the invention may be used alone or in combination with other perfuming ingredients, solvents, additives or fixatives, commonly used and that the person skilled in the art is able to choose in regard of the desired effect and the nature of the product to perfume.
• the invention relates to the use of a compound of formula (I) according to the invention or a composition containing at least one of such a compound in the perfumery field for the preparation of perfumed bases and concentrates, fragrances, perfumes and similar products (e.g. topic compositions, cosmetic compositions such as for example face and body creams, cleansers, facial treatments, talc powders, hair oils, shampoos, hair lotions, bath oils and salts, shower and bath gels, soaps, body anti- perspirants and deodorizers, pre-shave, shaving and post-shave creams and lotions, creams, toothpastes, mouth baths, pomades, cleaning products, such as for example softeners, detergents, air deodorizers and household cleaning supplies. Therefore, the invention also relates to a fragrant composition including at least one compound of formula (I).
• a fragrant composition including at least one compound of formula (I).
• the invention relates to the use of the compounds or composition as described above, as masking agents of odours, and to any pharmaceutical or cosmetic composition containing at least one compound of formula (I) or one or more isomers of a compound of formula (I). Therefore, this invention also relates to any composition comprising at least one compound of formula (I), as herein described, in combination with any suitable excipient, especially pharmaceutical or cosmetic excipient. In another aspect, the invention also relates to a method of fragrancing a composition by adding an olfactory effective amount of a compound of formula (I) of the invention to said composition.
• Suitable compositions comprise perfumed bases and concentrates, fragrances, perfumes and similar products; topic compositions; cosmetic compositions such as for example face and body creams, cleansers, facial treatments, talc powders, hair oils, shampoos, hair lotions, bath oils and salts, shower and bath gels, soaps, body anti-perspirants and deodorizers, pre-shave, shaving and post-shave creams and lotions, creams, toothpastes, mouth baths, pomades; cleaning products, such as for example softeners, detergents, air deodorizers and household cleaning supplies.
• cosmetic compositions such as for example face and body creams, cleansers, facial treatments, talc powders, hair oils, shampoos, hair lotions, bath oils and salts, shower and bath gels, soaps, body anti-perspirants and deodorizers, pre-shave, shaving and post-shave creams and lotions, creams, toothpastes, mouth baths, pomades
• cleaning products such as for example softeners, detergents, air
• the invention also relates to a method of masking odours comprising adding an olfactory effective amount of at least a compound of formula (I) of the invention to a composition.
• Suitable compositions comprise particularly pharmaceutical, and cosmetic compositions.
• Suitable cosmetic composition include face and body creams, cleansers, facial treatments, talc powders, hair oils, shampoos, hair lotions, bath oils and salts, shower and bath gels, soaps, body anti-perspirants and deodorizers, pre-shave, shaving and post-shave creams and lotions, creams, toothpastes, mouth baths, and pomades.
• the compounds of the invention may be used in a concentration comprised in a range from 0.001% to 99% in weight, preferably from 0.1% to 50% in weight, more preferably from 0.1% to 30% in weight. It is known by the man skilled in the art that these values depend of the nature of the composition/article to be perfumed, the desired intensity of the perfume, and of the nature of the other ingredients present in said composition or article.
• the invention also relates to a process of preparing a compound according formula (I) as defined above, the process comprising the following steps of:
• Step a) of the process of the invention is carried out in an organic solvent, which may be selected from the group comprising toluene, xylene, trimethylbenzene, cyclohexane, and methylcyclohexane.
• the organic solvent is cyclohexane or toluene.
• step a) is advantageously carried out at refluxing temperature.
• Step b) is carried out in an organic solvent, which may be selected from the group comprising toluene, xylene, trimethylbenzene, cyclohexane and methylcyclohexane, in the presence of an amine, preferably triethylamine.
• the organic solvent is toluene.
• Step c) is advantageously carried out in the same solvent as step b).
• the diketone is directly reacted with the acid without previous purification.
• step d) The reduction of the diketone to the diol in step d) is carried out according to conventional reduction methods well known to the person skilled in the art, e.g. using NaBH 4 , Dibal-H, LiAlH 4 or H 2 . Particularly good results were obtained with NaBH 4 . [DEFINITIONS!
• fragment and “fragrant” are used interchangeably whenever a compound or a mixture of compounds is referred to, which is intended to pleasantly stimulate the sense of smell.
• olfactory effective amount means a level or amount of fragrant compound present in a material at which the incorporated compound exhibits a sensory effect.
• masking is meant reducing or eliminating malodour perception generated by one or more molecules entering in the composition of a product.
• the term “isomer” means molecules having the same chemical formula, which means same number and types of atoms, but in which the atoms are arranged differently.
• the term “isomer” includes structural isomers, geometric isomers, optical isomers and stereoisomers. It particularly includes the cis/trans isomers, the cis isomers being the ones where the bicyclic junction is cis, i.e. the substituents forming the acetal cycle are on the same side of the cyclohexyl cycle in (I).
• the trans configuration is the one where the substituents forming the acetal cycle are on two different sides of the cyclohexyl cycle in (I) - the bicyclic junction is trans.
• C1-C6 alkyl or "C1-C6 alkyl group” means any linear or branched saturated hydrocarbon chain having 1, 2, 3, 4, 5 or 6 carbon atoms, such as for example methyl, ethyl, n-propyl, /-propyl, «-butyl, sec-butyl, zso-butyl, tert-butyl, and n-pentyl.
• C2-C6 alkenyl or "C2-C6 alkenyl group” means any linear or branched mono or poly unsaturated hydrocarbon chain, having 2, 3, 4, 5 or 6 carbon atoms, such as for example ethenyl, prop-1-enyl, allyl, but-1-enyl, but-2-enyl or pentenyl.
• C5-C6 cycloalkyl or "C5-C6 cycloalkyl group”, means any cyclic saturated hydrocarbon chain having 5 or 6 carbon atoms (namely, a cyclopentyl or cyclohexyl), substituted or not by one or several alkyl and/or alkenyl groups as described above -preferably methyl and ethyl-.
• C5-C6 cycloalkenyl or "C5-C6 cycloalkenyl group” means any cyclic mono or poly unsaturated hydrocarbon chain having preferably 5, 6 or 7 carbon atoms, such as for example cyclopentenyl, cyclohexenyl and cycloheptenyl, substituted or not by one or several alkyl and/or alkenyl groups as described above -preferably methyl and ethyl-.
• aryl refers to a polyunsaturated, aromatic hydrocarbyl group having a single ring (i.e. phenyl) or multiple aromatic rings fused together (e.g. naphtyl) or linked covalently, typically containing 5 to 12 atoms; preferably 6 to 10, wherein at least one ring is aromatic.
• a preferred aryl group is phenyl.
• (CH 2 )o- 2 -aryl” thus includes any aryl group as defined above as well as any -CH 2 -aryl group and any -(CH 2 ) 2 -aryl group, wherein the aryl moiety is as defined above.
• a preferred -CH 2 -aryl group is the benzyl group and a preferred -(CH 2 ) 2 -aryl group is -(CH 2 ) 2 -phenyl.
• Cyclohexanone (98.14 g, l .OO mol) is added dropwise to a 12M solution of morpholine (118.48 g, 1.36 mol) in cyclohexane (120 ml) at 65-70 0 C.
• the reaction mixture is then heated under reflux and the completion of the reaction is followed by GC.
• the formed water is removed using a Dean-Stark apparatus.
• Compound III' (white solid) is obtained quantitatively according to Example 1, from 4-tert-butylcyclohexanone (77.12 g, 0.50 mol), morpholine (54.01 g, 0.62 mol) and cyclohexane (60 mL).
• Compound III (brown liquid) is obtained quantitatively according to Example 1, from 4,4-dimethylcyclohexanone (350.03 g, 2.76 mol), morpholine (327.01 g, 3.75 mol) and cyclohexane (330 mL).
• Compound IVb is obtained in 49% yield as a colourless oil, according to Example 4, from 4-cyclohex-l-enyl-morpholine (82.64 g, 0.50 mol, obtained in Example 1), triethylamine (71.33 g, 1.41 mol), propionyl chloride (64.76 g, 1.41 mol), toluene (770 mL) and 20% aqueous HCl (250 mL).
• Compound IVc is obtained in 50% yield as a yellow powder, according to Example 4, from 4-cyclohex-l-enyl-morpholine (40.96 g, 0.25 mol, obtained in Example 1), triethylamine (35.35 g, 0.35 mol), benzoyl chloride (49.19 g, 0.35 mol), toluene (380 mL) and 20% aqueous HCl (125 mL).
• Compound IVd is obtained in 90% yield as a pale yellow liquid, according to Example 4, from 4-cyclohex- 1 -enyl-morpholine (82.64 g, 0.5 mol, obtained in Example 1), triethylamine (71.34 g, 0.71 mol), isovaleryl chloride (85.01 g, 0.71 mol), toluene (760 mL) and 20% aqueous HCl ( 166 mL).
• Compound IVa is obtained in 53% yield as a yellow oil, according to Example 4, from morpholino-enamine III' (36.89 g, 0.17 mol, obtained in Example 2), triethylamine (24.25 g, 0.24 mol), acetyl chloride (18.84 g, 0.24 mol), toluene (26O mL) and 20% aqueous HCl (85 mL).
• Compound IVb is obtained in 58% yield as a yellow oil, according to Example 4, from morpholino-enamine III' (36.89 g, 0.17 mol, obtained in Example 2), triethylamine (24.25 g, 0.24 mol), propionyl chloride (22.2 g, 0.24 mol), toluene (260 mL) and 20% aqueous HCl (85 mL).
• Example 4 from morpholino-enamine III' (36.89 g, 0.17 mol, obtained in Example 2), triethylamine (24.25 g, 0.24 mol), benzoyl chloride (33.73 g, 0.24 mol), toluene (26O mL) and 20% aqueous HCl (85 mL).
• Compound IVe is obtained as white crystals, according to Example 4, from morpholino-enamine III' (55.33 g, 0.25 mol, obtained in Example 2), triethylamine (35.66 g, 0.35 mol), crotonyl chloride (36.85 g, 0.35 mol), toluene (380 mL) and 20% aqueous HCl (125 mL).
• Compound IVa is obtained in 33% yield as a pale yellow oil, according to Example 4, from morpholino-enamine III" (266.36 g, 1.36 mol, obtained in Example 3), triethylamine (194.04 g, 1.91 mol), acetyl chloride (149.93 g, 1.91 mol), toluene (2.09 L) and 20% aqueous HCl (685 mL).
• Compound IVb is obtained in 26% yield as a orange oil, according to Example 4, from morpholino-enamine III" (131.88 g, 0.67 mol, obtained in Example 3), triethylamine (95.59 g, 0.94 mol), propionyl chloride (86.96 g, 0.94 mol), toluene (1.03 L) and 20% aqueous HCl (340 mL).
• Diketone IVa (49.95 g, 0.36 mol, 1 eq., obtained in Example 4) is added dropwise to a 10-15 0 C molar suspension Of NaBH 4 (13.47 g, 0.36 mol, 1 eq.) in EtOH (360 ml). After completion of the reaction (followed by tic), acetone (65 ml) is added to the reaction mixture. Half of the solvents is then evaporated and the mixture is diluted in water and MTBE. 10% aqueous HCl is added and the aqueous phase is extracted three times with MTBE. The combined organic phases are then washed with saturated aqueous NaHCO 3 and with brine. After drying over magnesium sulphate, the organic phase is filtered and the solvents are evaporated to give crude diol Va as a pale yellow oil in quantitative yield. Compound Va is used in the next step without further purification.
• Compound Vb is obtained in 93% yield as a yellow oil, according to Example 4 from diketone IVb (37.73 g, 0.24 mol, obtained in Example 5), NaBH 4 (9.14 g, 0.24 mol), ethanol (240 mL) and acetone (40 mL).
• Compound Va is obtained in quantitative yield as a yellow oil, according to Example 14, from diketone IVa (15.5 g, 0.08 mol, obtained in Example 8), NaBH 4 (3.02 g, 0.08 mol), ethanol (80 mL) and acetone (15 mL).
• Example 14 from diketone IVb (16.7 g, 0.08 mol, obtained in Example 9), NaBH 4 (3.02 g, 0.08 mol), ethanol (80 mL) and acetone (15 mL).
• Example 14 from diketone IVc (14.56 g, 0.06 mol, obtained in Example 10), NaBH 4 (2.27 g, 0.06 mol), ethanol (60 mL) and acetone (10 mL).
• Example 14 from diketone IVa (72.17 g, 0.43 mol, obtained in Example 12), NaBH 4 (16.25 g, 0.43 mol), ethanol (430 mL) and acetone (85 mL).
• Compound Vb is obtained in quantitative yield as a pale yellow oil, according to Example 14, from diketone IVb (29.99 g, 0.16 mol, obtained in Example 13), NaBH 4 (6.05 g, 0.16 mol), ethanol (160 mL) and acetone (30 mL).
• Olfactory profile Green, earthy, roasted nuts, coffee
• Compound lab is obtained as a colourless oil in 20% yield, according to Example 23, from diol Va (28.63 g, 0.2 mol, obtained in Example 14), hexanal (24.03 g, 0.24 mol) and cyclohexane (85 ml). It consists in a mixture of 3 isomers with 2 major isomers (98%) in a 50:50 ratio.
• Compound lac is obtained as a colourless oil in 20% yield, according to Example 23, from diol Va (25.96 g, 0.18 mol, obtained in Example 14), crotonaldehyde (15.14 g, 0.21 mol) and cyclohexane (75 ml). It consists in a mixture of 5 isomers with 2 major isomers (85%) as cis and trans isomers in a 62:38 ratio.
• Bp 62°C / 0.6 ton- Olfactory profile: green, ripe fruit
• Compound lad is obtained as a pale yellow oil in 44% yield, according to Example 23, from diol Va (14.98 g, 0.1 mol, obtained in 14), benzaldehyde (21.22 g, 0.2 mol) and cyclohexane (50 ml). It consists in a mixture of 5 isomers with 2 major isomers (84%) as cisltrans isomers in a 60:40 ratio.
• Compound Iae is obtained as colourless oil in 30% yield, according to Example 23, from diol Va (25.96 g, 0.18 mol, obtained in Example 14), phenylacetaldehyde (25.23 g, 0.21 mol) and cyclohexane (75 ml). It consists in a mixture of 4 isomers with 2 major isomers (93%) as cisl trans isomers in a 75:25 ratio.
• Bp 90 0 C / 0.2 ton- Olfactory profile: Floral (mimosa, carnation), spicy (eugenol), honey.
• Compound laf is obtained as colourless oil in 60% yield, according to Example 23, from diol Va (25.96 g, 0.18 mol, obtained in Example 14), propionaldehyde (51 g, 0.88 mol) and cyclohexane (450 ml). It consists principally in a mixture of 5 isomers with 3 major isomers (78%) in a 47:31 :22 ratio.
• Bp 80-83 °C / 5.7 torr
• Olfactory profile powerful, spicy (curry, eugenol), hazelnut, fenugrec, coffee beans, celery, tagete, immortelle, fruity (pear, apple, carrot).
• Compound Iah is obtained as colourless oil in 14% yield, according to Example 23, from diol Va (40.57 g, 0.28 mol, obtained in Example 14), acetone (32.52 g, 0.56 mol) and cyclohexane (1 10 ml). It consists in a mixture of 4 isomers with 2 major isomers (96%) as cisltrans enantiomers in a 53 :47 ratio.
• Bp 44°C / 0.6 ton- Olfactory profile: green, minty, fresh.
• Compound Iai is obtained as colourless oil in 10% yield, according to Example 23, from diol Va (40.57 g, 0.28 mol, obtained in Example 14), 2-hexanone (33.65 g, 0.34 mol) and cyclohexane (1 10 ml). It consists in a mixture of 2 isomers (94%) as cis and trans enantiomers in a 56:44 ratio.
• Bp 60 0 C / 0.47 ton- Olfactory profile: Camphoraceous, pharmaceuticals, caoutchouc.
• Compound laj is obtained as colourless oil in 16% yield, according to Example 23, from diol Va (40.57 g, 0.28 mol, obtained in Example 14), cyclopentanone (28.26 g, 0.34 mol) and cyclohexane (1 10 ml). It consists in a mixture of 2 isomers (97%) as cisltrans enantiomers in a 57:43 ratio.
• Compound lak is obtained as colourless oil in 28% yield, according to Example 23, from diol Va (40 g, 0.278 mol, obtained in Example 14), 2,4-dimethylcyclohex-3- enecarbaldehyde (TriplalTM, 46 g, 0.333 mol) and cyclohexane (140 ml). It consists in a mixture of isomers, with 4 main isomers (85%) in a 42:31 : 16: 1 1 ratio (cis/trans ratio:
• Olfactory profile floral, green, a bit animalic.
• Compound IaI is obtained as colourless oil, according to Example 23, from diol Va
• Example 14 (40 g, 0.278 mol, obtained in Example 14) and cyclohexenone. It consists in a mixture of isomers in a 25:31 :20:24 ratio.
• Compound Ibg is obtained as colourless oil in 65% yield, according to Example 23, from diol Vb (35.65 g, 0.23 mol, obtained in Example 15), isobutyraldehyde (32.45 g, 0.45 mol) and cyclohexane (100 mL). It consists in a mixture of 6 isomers with 3 major isomers (85%) in a 63:20: 17 ratio. The major enantiomers have the cis configuration.
• Compound lea is obtained as white crystals in 25% yield, according to Example 23, from diol Vc (24.75 g, 0.12 mol, obtained in Example 16), acetaldehyde (17.29 g, 0.24 mol) and cyclohexane (50 mL). It consists in a mixture of 3 isomers with 1 major enantiomers (84%), as czs-isomers.
• Compound Ida is obtained as a colourless oil in 50% yield, according to Example 23, from diol Vd (24 g, 0.13 mol, obtained in Example 17), acetaldehyde (1 1.3 g, 0.26 mol) and cyclohexane (100 mL). It consists in a mixture of 6 isomers with 2 major isomers (75%) as cisltrans enantiomers in a 60:40 ratio.
• Olfactory profile leathery, cresol.
• Compound I'aa is obtained as a yellow oil in 26% yield, according to Example 23, from diol Va (48.74 g, 0.24 mol, obtained in Example 18), acetaldehyde (35.23 g, 0.49 mol) and cyclohexane (100 mL). It consists in a mixture of 6 isomers with 3 major isomers (65%) in a 42:29:29 ratio.
• Bp 58°C / 0.3 ton- Olfactory profile: Sulfur, fatty.
• Compound I'bg is obtained as a pale yellow oil in 21% yield, according to Example 23, from diol Vb (17.83 g, 0.08 mol, obtained in Example 19), isobutyraldehyde (7.19 g, 0.1 mol) and cyclohexane (40 mL). It consists in a mixture of 5 isomers with 2 major isomers (76%) as cisltrans enantiomers in a 63:37 ratio.
• Olfactory profile herbaceous, camomile, woody.
• Compound I'ca is obtained as white crystals in 21 % yield, according to Example 23, from diol Vc (1 1.55 g, 0.04 mol, obtained in Example 20), acetaldehyde (3.87 g, 0.09 mol) and cyclohexane (20 mL). It consists in a mixture of 3 isomers with 2 major isomers (77%) as cis isomers in a 56:44 ratio.
• the crude product was purified by column chromatography on SiO 2 (AcOEt/Hexane (5:95)) The cis isomers were obtained as white crystals, whereas the minor trans isomer was obtained as a colourless oil.
• Compound I"aa is obtained as a colourless oil in 58% yield, according to Example 23, from diol V"a (74.08 g, 0.43 mol, obtained in Example 21), acetaldehyde (61.95 g, 0.86 mol) and cyclohexane (180 mL). It consists in a mixture of 4 isomers with 2 major isomers (75%) as cisl trans enantiomers in a 55:45 ratio.
• Bp 52°C / 1.1 ton- Olfactory profile: Aromatic, woody, powerful.
• Compound I"ac is obtained as a yellow oil in 56% yield, according to Example 23, from diol V"a (31.01 g, 0.18 mol, obtained in Example 21), crotonaldehyde (14.72 g, 0.21 mol) and cyclohexane (80 mL). It consists in a mixture of 8 isomers with 2 major isomers (76%) as cisltrans enantiomers in a 55:45 ratio.
• Olfactory profile herbal, minty, fruity
• Compound I"bg is obtained as a colourless oil in 31% yield, according to Example 23, from diol V"b (29.81 g, 0.16 mol, obtained in Example 22), isobutyraldehyde (23.05 g, 0.32 mol) and cyclohexane (70 mL). It consists in a mixture of 4 isomers with 2 major isomers (74%) as cisltrans enantiomers in a 60:40 ratio.
• Example 43 Fragrance composition comprising the compound obtained in Example 28 A green woody fougere composition was prepared from the following ingredients:
• composition A was described as very aromatic, with a tarragon note and a cyste-moss dry-down note whereas composition B (containing 2-ethyl-4-methylhexahydro-4/7-benzo[ ⁇ i][l,3]dioxine) has a fresher note (hesperidic, grapefruit, with a slight sulphur undertone) and marine facets giving a more modern impact to the fragrance.
• compositions A and B show no real difference in the fragrance perception, however adding 2-ethyl-4-methylhexahydro- 4//-benzo[ ⁇ i][l,3]dioxine to the composition brings more power to the note.
• Example 44 Fragrance composition comprising the compound obtained in Example 28
• a floral hesperidic watery composition was prepared from the following ingredients:
• composition B was also described as having green acidulous facets with a more floral indolic middle note, imparting a nicer and less “technique” impact to the fragrance.
• Example 45 Fragrance composition comprising the compound obtained in Example 27 A wisteria accord was prepared from the following ingredients:
• Composition B brings a more floral, honey-like and natural aspect to the wisteria accord, giving a rounder, sugary facet, with some lily-of-the-valley undertone.
• Example 46 Fragrance composition containing the derivative obtained in Example 27 A rose accord was prepared from the following ingredients:
• Composition B Adding 2-benzyl-4-methyl-hexahydro-benzo[l,3]dioxine to Composition A (Composition B) gives a more natural and green aspect to the rose accord and adds sweet, powdery facets.
• Example 47 Fragrance composition comprising the compound obtained in Example 27 A mimosa accord was prepared from the following ingredients:
• Composition B Adding 2-benzyl-4-methyl-hexahydro-benzo[l,3]dioxine to Composition A (Composition B) really impacts the fragrance to a nice mimosa note, with powdery and green aspects.
• Example 48 Fragrance composition comprising the compound obtained in Example 27 A nenuphar accord was prepared from the following ingredients:
• composition B Adding 2-benzyl-4-methyl-hexahydro-benzo[l,3]dioxine to Composition A (Composition B) gives a more natural and sweet water-lily note, with a slight jasminic facet.

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• 2009
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