JPS627176B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel α-hydroxyalkyl-4-tert-alkylcyclohexanes having sandalwood characteristics and utility as olfactory reagents; the present invention also relates to perfumes containing this compound. The present invention relates to a composition. Like many other natural materials that impart highly desirable nuances to perfume compositions, East Indian Sandalwood Oil is subject to the variations inherent in natural products. Due to its high cost and limited supply, perfumery necessarily has limited use of this valuable ingredient. Efforts therefore continue to provide synthetic materials with a distinctive aroma. α- and β-
Although it is known that santalol is a component of the desired main aromatic oil, there are no industrially available methods for the synthesis of these compounds. In short, any material with a bright fragrance that is economical and readily available is of immediate and considerable commercial interest as a substitute or partial replacement for natural bright oil in perfume compositions. According to the invention the formula: α of (wherein R ₁ and R ₃ are C _1-3 -alkyl groups, R ₂ is methyl or ethyl, and the total number of carbon atoms in the sum of R ₁ + R ₂ + R ₃ does not exceed 6) -Hydroxyalkyl-4-t-alkylcyclohexane is provided. Compounds of the invention can be prepared in a variety of ways.
The method which is preferred in each case will usually be determined by the cost and availability of the necessary starting materials. Thus, the new compound has the formula:

[Formula] or

[Formula] or

[Formula] (wherein R ₁ , R ₂ and R ₃ are as defined above), or by a method comprising hydrogenating a compound of formula: (wherein R ₁ and R ₂ are as defined above and R ₅ represents a group R ₃ ) or a compound of formula d in which R ₅ is hydrogen, R ₃ is It can be produced by reacting with a supplied organometallic derivative. The new compounds and the necessary starting materials can generally be prepared from the appropriate t-alkylbenzene or 4-t-alkylcyclohexanone by a variety of methods, some of which are shown in the chart below. In some cases, intermediates such as those shown in the chart are utilized when they are commercially available or are readily prepared by alternative methods known to those skilled in the art. As shown in Chert's Route A, the t-alkylbenzene is alkanoylated via Friedel-Crafts-type alkanoylation to provide a composition consisting essentially of the desired 4-t-alkylalkanoylbenzone a. The ketone thus produced is then hydrogenated in the presence of a suitable catalyst to provide the desired alcohol. As shown in Route B, 4-t-alkylcyclohexanone is a suitable acetylide, R ₄ -C≡CMe
[R ₄ = H, CH ₃ −, C ₂ H ₅ −, Me is Li, Na or K
] to provide ethyl alcohol, which is converted to the appropriate alkanoylcyclohexene via the well-known Loupé rearrangement (i.e. under the influence of formic acid). The 4-t-alkyl-1-alkanoylcyclohexene is then hydrogenated in either one or two steps to provide the desired alcohol. Route C shows how 4-t-alkyl-cyclohexane is converted to 4-t-alkylcyclohexene, but first reduced to an alcohol and then dehydrated to provide an olefin. This olefin is converted to a composition comprising 4-t-alkyl-1-alkanoylcyclohexene c via the following known Kondakov reaction, and the cyclohexene is then converted to the desired alcohol as described above. Route D converts the 4-t-alkylcyclohexanone to the aldehyde d (R ₅ =H) when using an ester of chloroacetic acid or to the ketone d (R ₅ =R ₃ ) when using a higher α-chloroacid. An alternative method using the well-known Dalzene reaction is shown. The ketones thus prepared can be converted to the desired alcohol by appropriate reduction of the carbonyl group (ie, by using a suitable reducing agent to reduce the ketone to alcohol). The aldehyde product of the reaction of Dalzene is a suitable, i.e. R _1-3 -alkyl-feeding organometallic derivative, e.g. an alkyllithium reagent or a Grignard reagent, e.g. R ₃ Li,
The desired alcohol can be converted by reacting R ₃ MgCl, R ₃ MgBr, R ₃ MgJ with an aldehyde. As mentioned above, the alcohols of the present invention can be produced in several ways. 1-alkanoyl-4-t-alkylbenzene, 1-alkanoyl-4-t-alkylcyclohexene, 1-alkanoyl-4-t-alkylcyclohexane, and 4-t-alkylcyclohexylcarboxylate, which are required as intermediates in the present invention. Aldehyde (1-formyl-
Many of the 4-t-alkylcyclohexane) derivatives are known to those skilled in the art or can be prepared using chemical reactions well known to those skilled in the art, such as those shown in Chart. For example: 1-acetyl-4-t-butylcyclohexene is manufactured by M.S.
MS Newman et al., J.Am.Chem.
Soc. 82 , 4098 (1960); 1-formyl-4-t-butylcyclohexane was reported in B. Cross et al., J. Chem. Soc., 3895 (1960); 4- t-Butylacetophenone was prepared by JC Butler et al. in J.Am.
Chem.Soc., 76 , 1906 (1954). In Chert Method A, it is preferred to reduce the 1-alkanoyl-4-t-alkylbenzene compound to the desired alcohol using either a rhodium or ruthenium catalyst to minimize hydrogenolysis. The requirements regarding amount of catalyst, solvent, reaction temperature, hydrogen pressure and reaction time (though perhaps not independent of each other) are not believed to be critical. It is preferred to use 5% rhodium on alumina catalyst in an amount ranging from 0.5 to 10% by weight of the ketone charged. Hydrogenation is preferably carried out at a temperature of 25 to 60°C and a pressure of 30 to 300 psi (1 psi = 0.068 atm). Use of a solvent is optional. This hydrogenation is carried out without solvent or in a suitable inert solvent such as ethanol, acetic acid, pentane, etc. The amounts of catalyst mentioned, the temperatures and pressures given, and the solvents used are illustrative and are not intended to limit the invention. Alternatively, the hydrogenation of the ketone is first carried out by methods known to those skilled in the art (e.g. NaBH ₄ ,
It is carried out in two steps by reduction of the carbonyl group to the alcohol (such as LiAlH ₄ , conventional catalytic reduction, etc.), followed by hydrogenation of the benzyl alcohol formed using a rhodium catalyst as described above. Hydrogenation of 1-alkanoyl-4-t-alkylcyclohexene to the new alcohol by many methods known in the hydrogenation art for hydrogenation of alpha-beta unsaturated ketones to saturated alcohols according to methods B and C of Chart. Can be added. A two-step process can be used in which one of the unsaturations is hydrogenated before the other. However, it is preferred to reduce the 1-alkanoyl-4-tert-alkylcyclohexene by hydrogenating both double bonds in a single step process. The requirements for a single-step process with respect to amount of catalyst, solvent, reaction temperature, hydrogen pressure and reaction time (although perhaps not independent of each other) do not appear to be critical. Many catalysts are known to those skilled in the art for converting α,β-unsaturated ketones into saturated alcohols, such as platinum, palladium, Raney nickel, rhodium, ruthenium. The use of economical Raney nickel is preferred since it has been unexpectedly found that this catalyst yields a product that is predominantly cis isomer, e.g. 60-85%. (1-(α-hydroxyethyl)-4-t to cis and trans isomers
The separation of -butylcyclohexane shows that the desired spreading fragrance properties of this compound are primarily due to the cis isomer. ) Furthermore, temperature, solvent pressure,
Conditions do not appear to be critical with respect to amount of catalyst and amount of catalyst. The preferred amount of catalyst is 5-15 of the amount of ketone charged.
%. The preferred temperature range is 80 to 120°C and the preferred pressure range is 60 to 600 psi. A solvent may be used, but is not necessary since the hydrogenation proceeds without a solvent. If a solvent is used, suitable solvents are those that have low vapor pressure under hydrogenation conditions. This list of temperature ranges, pressure ranges and catalyst amounts is provided to indicate suitable reaction conditions and is not intended to limit the invention. Conditions outside the given range are applicable in most cases. It was completely unexpected that the product formed when using Raney nickel as a catalyst was enriched in cis isomers. A 1:1 mixture was expected to be found with other methods attempted. In comparison, when using Raney Nickel,
The resulting alpha-hydroxyalkyl-4-t-alkylcyclohexane is enriched in cis isomers, with a ratio of cis to trans isomers in the range of about 2-3 to 1. According to Method D, 4-t-alkylcyclohexylcarboxaldehyde can be reacted with the appropriate metal alkyl R ₃ M using a number of methods known to those skilled in the art. The reaction is carried out by adding the aldehyde over a period of time to a solution of the metal alkyl in a suitable reaction-inert solvent and, at the end of the reaction, decomposing the first adduct with a protic source such as an acid. It is preferable to do so. The metal alkyl is suitably a Grignard reagent (e.g. R ₃ MgX, where X is Cl, Br or I) or a lithium alkyl (e.g. R ₃ Li), all of which are commercially available or readily available to those skilled in the art. It can be manufactured by a known method. The solvent is preferably an ether such as ethyl ether, THF, or ethyl ether-toluene,
These are ether-hydrocarbon mixtures such as THF-toluene and THF-benzene. This process is well known to those skilled in the art. The compounds of the invention find use as perfumes and can be used in perfumes, soaps and other cosmetic products. They are particularly useful as substitutes or partial substitutes, although not absolute, for natural oils. It is believed that these compounds of the formula, which have a single ring structure totally unrelated to the known structures of α- and β-santalol, are endowed with remarkable aromatic properties similar to natural oils. Very surprising and unexpected. It should also be noted that compounds with the structure R=H are in any case not significantly similar and completely lack the valuable aromatic properties inherent in the compounds of the invention. The perfume properties common to each of the chemicals of this invention are distinctive characteristics. All of the α-hydroxyalkyl-4-t-alkylcyclohexanes isolated had this characteristic. This feature is most effective and intense in the lower congeners of this series, 1-(α-hydroxyethyl)-4-tert-butylcyclohexane, and decreases with increasing molecular weight in the higher congeners. This has been shown to be the case as either the molecular weight of the hydroxyalkyl or the size of the t-alkyl group increases. Congeners with 15 or more carbon atoms are considered to have aromas that are too weak to detect distinct characteristics under normal conditions. The separation of 1-(α-hydroxyethyl)-4-t-butylcyclohexane into the cis and trans isomers, as reviewed above, indicates that the desired broad fragrance properties of this compound are due primarily to the cis isomer. shows. When mixed with aromatic oils, concentrates and chemicals used in perfumery technology, the novel α-hydroxyalkyl-4-t-alkylcyclohexane of the present invention imparts a natural fragrance character to the preparation. do. Their ability to replace and/or extend natural oils in this formulation is a particular advantage. The following examples are provided to further illustrate the practice of the present invention, but are for purposes of preferred embodiment only and should not be construed as limiting. Unless otherwise noted, temperatures are in °C, infrared bands are in reciprocal cm, nuclear magnetic resonance spectra were performed in chloroform- _d , and signals are
Reported in δ units relative to TMS (δ0.0), and molecular weights determined by mass spectrometry. Gas-liquid chromatography was also used to analyze the products. Example 1-acetyl-4-t-butylcyclohexene to 1-(α-hydroxyethyl)-4-t-butylcyclohexane A Two-step process 1-acetyl-4-t in 200 ml of ethynol
-A solution of 70 g (0.39 mole) of butylcyclohexene was hydrogenated with 0.5 g of 5% palladium on charcoal in a Parr hydrogenator under 50 psi hydrogen pressure. When the theoretical amount (0.39 mol) of hydrogen has been absorbed, the reaction is stopped, the mixture is filtered, concentrated, and distilled under reduced pressure to remove the cis and trans-
Giving about a 1:1 mixture of 1-acetyl-4-tert-butylcyclohexane: 64.6 g (yield 91
%); boiling point 64-92℃ (8 mm); molecular weight 182 (m
s); nmr. does not indicate vinyl hydrogen. cis and trans-1 in 30 ml of anhydrous ether
A solution of 30 g (0.16 mol) of this 1:1 mixture of -acetyl-4-t-butylcyclohexane was added dropwise to a stirred mixture of 4 g of lithium aluminum hydride in 200 ml of anhydrous ether. After the addition, the mixture was heated under reflux for 5 hours, allowed to cool, and saturated ammonium chloride solution was added dropwise until a clear ethereal layer was obtained. The mixture was filtered, washed with 10% sodium hydroxide solution, washed with water, dried, concentrated and distilled to cis and trans-1-(α-hydroxyethyl)-4-t-butylcyclohexane. gave a 1:1 mixture of:
25.0g (yield 83.3%); boiling point 75-85℃ (2
mm); molecular weight 184; nmr shows no absorption of 2.0-2.2 (acetylmethyl H); 3330 (hydroxyl). B One-step method with Raney-nickel in solvent. A mixture of 353 g (2.0 mol) of 1-acetyl-4-t-butylcyclohexane, 100 ml of n-butanol, and 35 g of Raney nickel (activated by repeated washings with methanol) was added until hydrogen uptake essentially ceased (was consumed). (3.1 moles of hydrogen, 78% of theory) was hydrogenated at 300 psi hydrogen pressure and 100 °C. The catalyst was removed by filtration, replaced with fresh catalyst, and the reaction restarted until the remaining 0.9 moles of hydrogen were consumed. After filtration and removal of solvent, the crude product 1-(α-hydroxyethyl)-
4-t-butycyclohexane is 77% cis isomer
and 23% trans isomer. C One-step method using Raney nickel without solvent A mixture of 200 g (1.11 mol) of 1-acetyl-4-tert-butylcyclohexane and 20 g of Raney nickel (activated by repeated washing with methanol) was injected until hydrogen uptake ceased (was consumed). hydrogen
2.2 mol) hydrogenated at 300 psi hydrogen pressure and 100°C. After filtration, the crude product 1-(α-hydroxyethyl)-4-t-butylcyclohexane was free from any contamination with 1-acetyl-4-t-butylcyclohexane and contained 64% cis isomer and 36% trans isomer. It was composed of Example cis-1-(α-hydroxyethyl)-4-t-
Butylcyclohexane and trans-1-(α
-Hydroxyethyl)-4-t-butylcyclohexane The mixture of cis and trans 1-acetyl-4-t-butylcyclohexane prepared in Example A was separated into pure components by vacuum distillation in a Nesterfaust spinning band distillation apparatus. The physical constants of the two isomers are as follows: cis-1-acetyl-4-t-butylcyclohexane; molecular weight 182 (ms); boiling point 84-86 °C (8
mm); nmr, 0.80 (9H, s, t-butyl H),
2.12 (3H, S, acetylmethyl H); ir, 1710,
1365, 1355, 1175, 1140. Trans-1-acetyl-4-t-butylcyclohexane; molecular weight 182 (ms); boiling point 92-93°C
(8mm); nmr, 0.85 (9H, S, t-butyl H),
2.10 (3H, S, acetylmethyl H); ir, 1710,
1365, 1250, 1168. Trans to this cis isomer in a refluxing solution of sodium carbonate in aqueous methanol; 90% of cis-1-acetyl-4-t-butylcyclohexane: 10
% mixture was epimerized. The spectral data for this mixture were essentially identical to those obtained for the pure trans isomer. Each of the pure 1-acetyl-4-t-butylcyclohexane isomers was converted to the respective alcohol with lithium aluminum hydride as described in Example A. The physical constants of the two isomers are as follows: cis-1-(α-hydroxyethyl)-4-t-
Butylcyclohexane; molecular weight 184 (ms); boiling point 75-77℃ (2 mm); nmr, 0.85 (9H, S, t-
Butyl H), 1.0-1.8 (13H, m, methyl d1.22
So, J = 6Hz), 3.93 (H for 1H, m, OH
α);ir, 3330, 1365, 1240, 1235, 1065,
935, 880. trans-1-(α-hydroxyethyl)-4-
t-Butylcyclohexane; molecular weight 184 (m
s); boiling point 80-85 (2mm); nmr, 0.85 (9H,
S, t-butyl H), 1.0-1.8 (13H, methyl d at m 1.16, J = 6.5Hz), 3.53 (Hα for 1H, m, OH); ir, 3340, 1365, 1235, 1150,
1068, 950, 940, 930, 900, 880. The desirable radiant fragrance properties of 1-(α-hydroxyethyl)-4-tert-butylcyclohexane are primarily due to this cis isomer. Example 4-t-Butylacetophenone to cis and trans-1-(α-hydroxyethyl)-4-t
-Butylcyclohexane A mixture of 17.6 g (0.10 mol) of 4-tert-butylacetophenone, 1.3 g of 5% rhodium on alumina, a few drops of acetic acid and 10 ml of absolute ethanol was heated at 50 psi hydrogen pressure at room temperature until hydrogen uptake ceased. Hydrogenation was carried out in a Pal apparatus. Gas-liquid chromatography (GLC) revealed that this hydride contained 8% 1-acetyl-4-t
-contained butylcyclohexane: therefore,
The catalyst was removed by filtration and the above steps were repeated until hydrogen uptake ceased. Filter this mixture and
Concentration under reduced pressure and distillation yielded 16.8 g of a 1:1 mixture of cis- and trans-1-(α-hydroxyethyl)-4-tert-butylcyclohexane (yield 91
%) was given. The spectral properties were identical to those described in the examples. When the solvent is acetic acid, ethanol, or pentane, when the catalyst is 5% rhodium on charcoal,
The same results were obtained when the temperature was 60° C. or when the pressure was 300 psi. 1- instead of 4-t-butylacetophenone
(Identical results were obtained when α-hydroxy-ethyl-4-t-butylbenzene was hydrogenated. To remove the small amount of 1-acetyl-4-t-butylcyclohexane present in the initial hydrogenation, Rather than repeating this hydrogenation, 1-
This impurity can be removed from (α-hydroxyethyl)-4-t-butylcyclohexane. EXAMPLE Cis- and trans-1-(1-hydroxypropyl)-4-t-butylcyclohexane 109 g of bromoethane in a mixture of 24 g (1.0 g) of magnesium flakes and 100 ml of anhydrous ethyl ether.
(1.0 mol) was added. The resulting solution was heated under reflux for 2 hours. Add 1-formyl-4- to the above solution.
109g (0.9mol) of t-butylcyclohexane
Added dropwise over time. After the addition the mixture was heated under reflux for 4 hours, allowed to cool, and then poured into a mixture of saturated ammonium chloride solution and ice.
Added to 100ml. This mixture was mixed with ether (3x
100 ml) and washed the extract with water, dried, concentrated and distilled to give cis and trans-1-(1-hydroxypropyl)-4-t.
- gave a 1:1 mixture of butylcyclohexane: 116 g (66% yield); boiling point 89-95 (1 mm);
Molecular weight 198 (ms); nmr, 0.85 (12H, S, methyl H), 3.1-3.9 (1H, broad, αH); ir,
3350, 1364, 970. Examples Cis and trans-1-(1-hydroxy-2
-methylpropyl-1-yl)-4-tert-butylcyclohexane 2-bromopropane in a mixture of 16.8 g (0.70 mol) magnesium and 200 ml anhydrous ethyl ether.
92.3 g (0.75 mol) was added. The resulting solution was heated under reflux for 2 hours. Add 89 g (0.5 g) of 1-formyl-4-t-butylcyclohexane to the above solution.
mol) was added dropwise over a period of 1 hour. After the addition, the mixture was heated under reflux for 4 hours, allowed to cool, added to a mixture of saturated ammonium chloride solution and ice, and extracted with ether (3x100ml). The extract was washed with water (1 x 25 ml), dried, concentrated and distilled into cis and trans 1-(1-hydroxy-2-methylpropyl-1-yl)-4-t-butylcyclohexane. gave a 1:1 mixture of: 77 g (73% yield); boiling point 98-110 (3 mm); molecular weight 212 (ms); nmr,
0.82 (15H, S, t-butyl and isopropylmethyl H), 3.0-3.8 (1H, wide, αH); ir,
3360, 1360, 1110, 1000, 980. EXAMPLE Cis and trans-1-(α-hydroxyethyl)-4-t-amylcyclohexane A 1-acetyl-4-t-amylcyclohexene 46 g of lithium acetylide in 200 ml of benzene
84.0 g (0.5 mol) of 4-t-amylcyclohexane was added to the mixture over a period of 3 hours.
After the addition, stir the mixture for 1 hour and add 500 ml of water.
ml was added dropwise and the mixture was heated under reflux for 1 hour. The mixture was allowed to cool, separated and the aqueous phase was extracted with ether. The combined organic phases were washed with water, dried over magnesium sulfate, filtered and concentrated under reduced pressure. Distillation of residual oil is carried out in cis and trans-4
-t-amyl-1-ethynylcyclohexanol; 49.8 g, yield 51%, boiling point 103-104
°C (0.5-1.0mm); nmr, 2.48 (1H, S, ethynyl H), 0.78 (9H, methyl H); ir, 3380,
3300, 1064 cm ^-1 cis and trans-4-t-amyl-1-ethynylcyclohexanol 24.0 g (0.12 mol)
A solution of 75 ml of 90% formic acid was heated under reflux for 2 hours. The solution was allowed to cool, excess 10% sodium hydroxide solution was added dropwise and the mixture was extracted with ether. The ether extract was extracted with water, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. Distillation of residual oil is 1
-Acetyl-4-t-amylcyclohexene was obtained: 13.2 g, yield 55%; boiling point 63-64 °C,
(0.1mm); molecular weight 194 (ms); nmr6.93
(1H, wide, vinyl H), 2.25 (3H, S,
acetyl methyl), 0.82 (9H, methyl H); ir
1662, 1639, 1385, 1248, 1068, 964, 907cm
^-1 . B Cis- and trans-1-(α-hydroxyethyl)-4-t-amylcyclohexane From 1-acetyl-4-t-amylcyclohexane, cis- and trans- A mixture of 1-(α-hydroxyethyl)-4-t-amylcyclohexane was obtained: yield 1.1% approximately 1:1 cis-trans; boiling point 89-94 (1 mm); molecular weight 198
(ms); nmr, 1.20 (0.5H, d, J=6Hz,
Methyl α for OH in cis isomer), 1.15
(0.5H, d, J = 6.5Hz, OH in trans isomer
methyl α), 0.77 (9H, sharp, methyl H); ir, 3360, 1455, 1070, ^{935 cm -1} . EXAMPLE Cis and trans-1- in a transparent composition
Use of (α-Hydroxyethyl)-4-tert-butylcyclohexane When used with the compositions described below, cis and trans-1-(α
-hydroxyethyl)-4-tert-butylcyclohexane contributes the main aromatic component to the formation of the synthetic aroma. Compound A 200 Sandera (trade name) ^* 700 Amyris oil 50 American cedar wood 50 1000 *Givaudan's trade name for a polycyclic alcohol product with a bright aroma. Addition of Compound A to the above formula produces a smooth, buttery, radiant aroma similar to that found in natural radiant oil. The natural radiant character that Compound A contributes to the above formulations is important for the formulation of fully synthetic radiant fragrances. Compound A can be used in this type of formulation in concentrations ranging from 10-60% by weight. EXAMPLES Use of Higher Analogs in Vivid Compositions Cis and trans-1-(1-hydroxypropyl)-4-tert-butylcyclohexane, cis and trans-1-(1
-Hydroxy-2-methylprop-1-yl)-
4-t-butylcyclohexane, and cis and trans-1-(1-hydroxyethyl)-4-t-
The use of amylcyclohexane showed similar effects on Compound A to those described in the Examples. However, the aroma intensity attributable to these compounds was weaker than that of Compound A. EXAMPLE Cis and trans-1- in woody-floral compositions
Use of (α-Hydroxyethyl)-4-tert-butylcyclohexane (Compound A) The spreading oil type effect of Compound A can be demonstrated in woody-floral compositions such as: Compound A 300 Amyl Cinnamic Aldehyde 21 Aldehyde C-12 (Laurik) in 10% propylene glycol. 8 Benzyl propionate 25 Natural bergamot 22 Methyl phenyl carbinyl acetate 14 Linalool, cour 5 Ylang Bourbon extract 14 γ-Methylionone 100 Synthetic diasmine 35 α-Methyl-β-(p-tert-butylphenyl)
Propionaldehyde 70 p-tert-butylcyclohexyl acetate 97 Vetiva acetate 97 3,7-dimethyl-7-octenol 56 1,1,4,4-tetramethyl-6-ethyl-7
-acetyl-1,2,3,4-tetrahydronaphthalene 56 undecalactone in dipyrropylene glycol
10% 8 1000 In this example, the addition of 20-30% of Compound A has a considerable effect on the composition; it makes the aroma richer and smoother, and is obtained by the addition of natural beetroot oil. The effect is similar to that of
Higher concentrations can also be used for unique or special effects. Examples Use of Compound A in Compositions of Wood Types Compound A 280 Orange juice 20 Limonene 38 Linalool 66 Linalyl acetate 95 Benzyl acetate 20 γ-Methylionone 152 p-Tertiary-butylcyclohexyl acetate 114 Vetiva acetate 115 Coumarin 40 1・1,4,4-tetramethyl-6-ethyl-7
-Acetyl-1,2,3,4-tetrahydronaphthalene 30 Aldehyde C-12, 10 in dipropylene glycol
% 4 undecalactone, 10 in dipropylene glycol
% 6 Diphenyl Oxide 10 Diphenyl Methane 10 1000 The aromatic effect of Compound A when added to this wood base is reminiscent of the yakudan oil used in the same manner. This gives a body,
Makes the woody properties fuller and richer, and provides a considerable overall effect. At concentrations lower than the 28% cited in this example, the effects are similar. (e.g. 14%). Higher concentrations can also be successfully used for unique and special effects.

Claims (1)

[Claims] 1. General formula (wherein R ₁ and R ₃ are C _1-3 alkyl groups, R ₂ is methyl or ethyl, and the total number of carbon atoms in R ₁ + R ₂ + R ₃ does not exceed 6). In the manufacturing method, the general formula (wherein R is [Formula] [Formula] or [Formula] and R ₁ , R ₂ and R ₃ are as defined above) is hydrogenated. . 2 General formula (wherein R ₁ and R ₃ are C _1-3 alkyl groups, R ₂ is methyl or ethyl, and the total number of carbon atoms in R ₁ + R ₂ + R ₃ does not exceed 6). In the manufacturing method, the general formula (In the formula, R ₁ and R ₂ are as defined above, and R ₅ is a group
The above-mentioned method is characterized in that the carbonyl group of the compound having R ₃ is reduced. 3 General formula (wherein R ₁ and R ₃ are C _1-3 alkyl groups, R ₂ is methyl or ethyl, and the total number of carbon atoms in R ₁ + R ₂ + R ₃ does not exceed 6). In the manufacturing method, the general formula (wherein R ₁ and R ₂ are as defined above and R ₅ is hydrogen) and R ₃ Li, R ₃ MgCl,
R ₃ MgBr or R ₃ MgJ (R ₃ is R _1-3 alkyl)
The above method is characterized by reacting with. 4 General formula (wherein R ₁ and R ₃ are C _1-3 alkyl groups, R ₂ is methyl or ethyl, and the total number of carbon atoms in R ₁ + R ₂ + R ₃ does not exceed 6). containing an aromatic composition. 5 General formula (wherein R ₁ and R ₃ are C _1-3 alkyl groups, R ₂ is methyl or ethyl, and the total number of carbon atoms in R ₁ +R ₂ +R ₃ does not exceed 6). 6. The compound according to claim 5, wherein R ₃ is methyl. 7. The compound according to claim 5, wherein R ₁ =R ₂ =R ₃ =methyl.