JP2001500854A - Substituted 2-cyclohexyl-propan-1-ols and their use in perfume compositions - Google Patents

Abstract

  (57) [Summary] The present invention relates to a novel compound 2- (4-tert-butyl-cyclohexyl) -propan-1-ol and perfumes and perfume-containing products containing this compound. It is a powerful fragrance substance with strong sandalwood and muguet scent characteristics. Perfumes preferably contain at least 0.01% (W / W) of the present compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION               Substituted 2-cyclohexyl-propan-1-ol                     And its use in perfume compositions   TECHNICAL FIELD OF THE INVENTION   The present invention relates to novel substituted 2-cyclohexyl-propan-1-ols and fragrances. And its use in perfume-containing products.   Background of the Invention   In the literature relating to perfumery, various substituted 2-cyclohexyl-propanes are described. -1-ols are known. For example, CH-652,113 (Firmenich) Is 2- (4-tert-butyl-cyclohexyl) -propan-1-ol and Its use in perfumery is described. This compound is musk-like, woody-like And sandalwood (sandalwood) -like aroma, with a profound oriental character. This 4-isopropyl analog was obtained from S. Arctander, Perfume and Flavor Chemicals. , Rose-like, balsamic, mild, floral and woody It is described as having a scent. Dialkyl having an alkyl group of C1 to C4 2-substituted 2-cyclohexyl-propan-1-ols are available from Woody and Flora EP-0,32 as a compound having a vetiverol-like scent 8, 116.   On the other hand, 1- (4-tert-alkyl-cyclohexyl) -ethanol and Pan-1-ol is GB-1,476,72 as a compound having a sandalwood scent. 0 is known. It contains the lowest homolog, 1- (4-tert-butyl). Tyl-cyclohexyl) -ethanol (having 12 carbon atoms) is the largest scent Strength and intensity, and the scent It is noted that the amount decreases as the amount increases. Has more than 15 carbon atoms Were considered too weak and had no detectable sandalwood odor.   Summary of the Invention   The present invention relates to 2- (4-tert-amylcyclohexyl) -propyl represented by the following formula: Fragrances containing lopan-1-ol and the present compound in an olfactory effective amount (Perfumes) and perfumed products. Detailed description of the invention   The novel substituted 2-cyclohexyl-propan-1-ol of the present invention is a strong sandalwood Powerful fragrance with an unusual combination of scents and muguet tones Incense) substance. Therefore, this scent is known from CH-652,113. Much fresher and less profound than the scent of the tert-butyl homolog. Also, Judging from the contents described in GB-1,476,720, this fragrance is Unexpectedly powerful despite the fact that the compound has 14 carbon atoms . This unusual combination of scent characteristics offers new creative opportunities in fragrance production. Offer.   The alcohols according to the invention impart a scent to a wide variety of products and the scent May be used as such to enhance or improve Used as an ingredient in such perfumes to give the overall scent its scent characteristics May be. For the purposes of the present invention, the fragrance may be, if desired, a suitable solvent. Mixed with or dissolved in, or mixed with a solid substrate It is intended to mean a mixture of fragrance substances, which And / or any product for which a pleasant scent is essential or desirable. Used to provide. Examples of such products include cloth cleaning powders, cleaning solutions, Fabric softeners and other fabric care products; surfactants and household cleaning, polishing and And sanitizing products; air fresheners, indoor sprays and pomanders; stones Ken, bath and shower gel, shampoo, hair conditioner and its Other personal cleansing products; creams, ointments, toilet water, pre-shave, after-sales Ave, Skin and other lotions, talcum powder, body deodorants and And cosmetics such as antiperspirants.   Other flavors that can be advantageously combined with the alcohols of the invention in perfumery Glance substances include, for example, extract, essential oil, absolute, resinoid Natural products such as, resins, concrete, etc., but with saturated and unsaturated compounds, Hydrocarbons, alcohols, aldehydes, including aliphatic, carbocyclic and heterocyclic compounds Of ketone, ketone, ether, acid, ester, acetal, ketal, nitrile, etc. It may be a substance.   Such fragrance materials are described, for example, in Arctander, Perfume and Flavor  Chemicals (Montclair, N.J., 1969), S. Arctander, Perfume and Flavor Materia ls of Natural Origin (Elizabeth, N.J., 1960) and "Flavor and Fragfanc e Materials-1991 ”, Allured Publishing Co., Wheaton, Ill, USA You.   Examples of fragrance substances that can be used in combination with the alcohols of the present invention Include: keraniol, keranyl acetate, lina Roll, linalyl acetate, tetrahydrolinalool, citronellol, cyto Ronerylacetate, dihydromyrcenol, dihydromyrcenyl acetate, Tetrahydromyrcenol, terpineol, terpinyl acetate, nopo (Nopol), nopyl acetate, 2-phenylethanol, 2 -Phenylethyl acetate, benzyl alcohol, benzyl acetate, Jillsalicylate, styrallyl acetate, benzyl Zonzoate, amyl salicylate, dimethylbenzyl-carbinol, triclo L-methylphenylcarbinyl acetate, p-tert-butyl-cyclohexylurea Acetate, isononyl acetate, vetiveryl acetate ), Vetiverol, α-hexyl cinnamaldehyd e), 2-methyl-3- (p-tert-butylphenyl) propanal, 2-methyl 3- (p-isopropylphenyl) -propanal, 3- (p-tert-butyl Ruphenyl) -propanal, 2,4-dimethyl-cyclohex-3-enyl- Carboxaldehyde (2,4-dimethyl-cyclohex-3-enyl-carboxyaldehyde), Licyclodecenyl acetate, tricyclodecenyl propionate, 4- (4- Hydroxy C-4-methylpentyl) -3-cyclohexenecarboxaldehyde, 4- ( 4-methyl-3-pentenyl) -3-cyclohexenecarboxaldehyde, 4 -Acetoxy-3-pentyl-tetrahydropyran, 3-carboxymethyl-2 -Pentylcyclopentane, 2-n-heptylcyclopentanone, 3-methyl- 2-pentyl-2-cyclopentenone, n-decanal, n-de Decanal (n-dodecanal), 9-decenol-1, phenoxyethyl isobuty Rate, phenylacetaldehyde dimethyl acetal, phenylacetoaldehyde Hydodiethyl acetal, geranyl nitrile, citronellyl nitrile, cedril Acetate (cedryl acetate), 3-isocamphyl cyclohexanol (3-i socamphyl-cyclohexanol, sedolyl methyl ether, isolongifolanone (is olongifolanone), obepinnitrile, obepin, heliotropin, Kumari , Eugenol, vanillin, diphenyl oxide, hydroxycitronellal , Yonones (ionones), methylyonones, isomethylyonones, irons, Cis-3-hexenol and its esters, indan musk, tetralin (te tralin) musk, isochroman musk, macrocyclic Ketone, macrolactone musk, ethylene brush rate.   Solvents that can be used in the fragrance containing alcohol of the present invention include, for example, ethanol , Isopropanol, diethylene glycol, monoethyl ether, dipro Pyrene glycol, diethyl phthalate, triethyl citrate, isopropyl Millistate and the like.   The alcohol of the present invention may be used in a fragrance or a product containing a fragrance. The amount that can be removed can vary within wide limits and depends, inter alia, on the nature of the product and the use of the compound. It depends on the nature and amount of the other ingredients in the perfume and the desired olfactory effect. Thus, although only a wide range of restrictions can be imposed, nonetheless, it is Enough information to be able to use the alcohols of the invention for physical purposes I will provide a. In the fragrance, generally 0.01% by weight or more of the alcohol of the invention is used. Has a clearly perceptible olfactory effect. Preferably, 0.1 to 80% by weight , More preferably at least 1%. Of the present alcohol present in the product The amount is generally at least 10 ppm by weight, preferably at least 100 ppm by weight. ,Than Preferably it is at least 1000 ppm. However, products that should contain fragrances Depending on the article, levels up to about 20% by weight may be used in certain cases.   The alcohol of the present invention exists in cis and trans isomers, Encompasses both separately as well as all mixtures thereof.   The alcohol of the present invention can be obtained by converting tritert-amylcyclohexanone to triethyl. -2-phosphonopropionate followed by catalytic reduction and Li AlH_FourMay be conveniently prepared by reduction with Alternatively, benzene Friedel-Crafts alkylation reaction with soamylene, followed by propylene oxide Alkylation of tert-amylbenzene with oxide and 2- (4-tert-amylfurf It may be prepared by catalytic reduction of phenyl) -propan-1-ol. Anti The reaction product consists of a mixture of cis and trans isomers, The separation may be performed by a routine method. However, its use as a fragrance substance Such a separation is not necessary. Example 1: Synthesis of 2- (4-tert-amylcyclohexyl) -propan-1-olA) Ethyl 2- (4-tert-amyl-citalohexidenyl) -propionate Synthesis of   Mechanical stirrer, condenser with calcium chloride guard tube, temperature Meter, and 2 liter 3 with pressure-equalised addition funnel In a neck flask, triethyl-2-phosphonopropionate (75 g, 0.31 5 mol) was added to a stirred solution of sodium ethoxide under nitrogen (250 ml ethanol). (Freshly prepared from 7.5 g sodium in water). Attachment During the addition, the temperature gradually increased and reached 48 ° C. Next, 4-tert-A Milcyclohexanone (53 g, 0.315 mol) was immediately stirred under nitrogen. While adding dropwise over an additional hour. This is 45-50 ° C It was enough to maintain the reaction temperature. Following completion of the addition, the reaction mixture was further Stir for 1 hour. 1 ml aliquots were mixed with 4 ml of 1/1 diethyl ether / water The mixture was quenched and the organic layer was separated by TLC (silica stationary phase, chloroform eluent) and And packed column GLC (SE52; 100-200C, 4C / min) Minute Was analyzed. These indicate that the reaction is complete and that GL Lance-ethyl 2- (4-tert-amylcyclohexylenyl) -propionate A mixture of 94.6%: 4.2% of the isomers, designated G, was recorded.   Most of the ethanol was removed under reduced pressure. The residue was dissolved in dichloromethane (500 ml) and water (50 ml). Separate the organic layer and add water (500 ml) ) And then dried over amorphous magnesium sulfate. Organic residue Rush chromatography provided a colorless oil (66.1 g, 83%). sample Was distilled in vacuo to give a colorless oil (bp 98 ° C./1 mbar).B) Synthesis of ethyl 2- (4-tert-amylcyclohexyl) -propionate   Ethyl 2- (4-tert-amylcyclohexylidenyl) propionate (60 . 0 g, 0.238 mol) in a 1 liter Buchi autoclave (250 ml) and 5% Pd / C (6 g) was added. The reaction mixture is The reaction was monitored by packed column GLC (SE52; 100-200 ° C, 4 C / min). While stirring, the mixture was stirred at ambient temperature under a hydrogen pressure of 6 bar for 6 hours. At the end of this time In the meantime, the reaction is completed and ethyl 2- (4-tert-amylcyclohexyl) propione The salt was converted to the three geometric isomers [retention time: 26.329 min (3.2%), 27.1]. 49 minutes (7.5%), 28.320 minutes (87.0%)].   The catalyst was removed by vacuum filtration through a bed of Celite and the bed of Celite was removed. Was thoroughly washed with ethanol. Removal of the solvent under reduced pressure gives a pale green oil This was used for flash chromatography (silica stationary phase, chloroform eluent). Upon application, the title compound was obtained as a colorless oil (54.9 g, 91%). Short Vgreu x colorless oil (bp 100 ° C./1 mba) by distillation under reduced pressure through a column. r) (47.8 g, 79%) was obtained.C) Synthesis of 2- (4-tert-amylcyclohexyl) propan-1-ol   Mechanical stirrer, condenser with calcium chloride guard tube, temperature Ethyl in a 2 liter 3-neck flask equipped with a pressure gauge and a pressure equalizing addition funnel -2- (4-tert-Amylcyclohexyl) propionate (110 g, 0.4 3 mol), while maintaining the temperature below 30 ° C. by cooling with ice water, Underneath lithium aluminum hydride (3 in tetrahydrofuran (300 ml) 0g, (0.79 mol) was added dropwise. After the addition is complete, The reaction mixture was cooled to 0 ° C and 50 ml of ethyl acetate was carefully added dropwise. did. This is followed by 50 ml of water, followed by 50 ml of a 15% aqueous NaOH solution. Was added dropwise. The reaction mixture was vacuum filtered through celite, The pad was thoroughly washed with 1 liter of diethyl ether. Solvent is removed under reduced pressure This gave a colorless oil (89.2 g). TLC (stationary phase: silica, eluent: CHC l 90%, ethyl acetate 10%) showed a clean reaction. Hula Color chromatography (as TLC) to give a colorless oil (84.1 g). , 91%).   The product was subjected to capillary GLC (SE54; 25 m × 0.2 mm, d_f3.3 × 10^-7m, 50-280 ° C, 3 ° C / min). This gives 2 The two major products make up 97% of the total and 2- (4-tert-amylsic) Rohexyl) propan-1-ol, the cis form of M + 212 (6.5%) and It was suggested that it was a lance type (90.2%) isomer. GC smelling ( g-c smelling technique, sandalwood aromas almost exclusively Small amounts of by-products accompanying the mer have a weak or vague scent It has been shown. ¹³ C NMR (CDCl ₃ ) 66.575 (CH_TwoOH), 45.571 (CH (CH_Three) CH_TwoOH), 40 . 962 (CHCH (CH_Three) CH_TwoOH), 39.728 (CHC (CH_Three)_Two C_TwoH_Five), 34.746 (quaternary), 33.025 (CH_TwoRing), 32.7 78 (CH_TwoRing), 30.264 (CH_Two, T-amyl), 27.336 (CH_Two ring), 27.191 (CH_Two, Ring), 24.350 (CH_Threex_Two, T-amyl), 13. 686 (CH_Three), 8.355 (CH_Three). Example 2:   I want to make a sandalwood base with fresh floral notes in the following recipe Prepared.(Q): Fleg marketed by Quest International, Ashford, Kent, UK Lance substance

[Procedure amendment] [Submission date] March 3, 1999 (1999.3.3) [Correction contents]                                The scope of the claims 1. 2- (4-tert-Amylcyclohexyl) -propan-1-ol. 2. cis and / or trans isomer forms and / or     The alcohol according to claim 1, which is a mixture of cis and trans isomers.     Rules. 3. FC alkylation of benzene with isoamylene and propylene oxide     And subsequently prepared by reduction with a catalyst.     alcohol. 4. It contains an olfactory effective amount of the alcohol according to any one of claims 1 to 3.     And a fragrance characterized by: 5. The alcohol according to any one of claims 1 to 3 or the fragrance according to claim 4     A fragrance-containing product characterized by containing.

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, L U, MC, NL, PT, SE), OA (BF, BJ, CF) , CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, KE, LS, MW, S D, SZ, UG, ZW), EA (AM, AZ, BY, KG) , KZ, MD, RU, TJ, TM), AL, AM, AT , AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, F I, GB, GE, GH, HU, IL, IS, JP, KE , KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, M X, NO, NZ, PL, PT, RO, RU, SD, SE , SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW

Claims (1)

[Claims] 1. (4-tert-Amylcyclohexyl) -propan-1-ol. 2. Claims which are in cis and / or trans isomer form     The alcohol according to 1. 3. The alcohol of claim 2, which is a mixture of cis and trans isomers.     Rules. 4. FC alkylation of benzene with isoamylene and propylene oxide     And subsequently prepared by reduction with a catalyst.     The alcohol according to claim 1. 5. An olfactory effective amount of the alcohol according to any one of claims 1 to 4.     And a fragrance characterized by: 6. The alcohol of claim 5, wherein the alcohol is present in an amount of at least 0.01% by weight.     Fragrances listed. 7. The scent of claim 6, wherein the alcohol is present in an amount of 0.1-80% by weight.     Fees. 8. The alcohol according to any one of claims 1 to 4 or any one of claims 5 to 7     A fragrance-containing product comprising the fragrance according to claim 1.