JPH0378377B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel tricyclic aliphatic compound derivative having a specific substituent, a method for producing the same, and a fragrance composition containing the same. Conventionally, various fragrances have been synthesized in place of or as a supplement to various natural fragrance ingredients, and among these, many compounds with norbornane, that is, bicyclo[2.2.1]-heptane rings, have been synthesized. proposals have been made. Namely, U.S. Patent No. 3,673,261 and No.
No. 3,673,263 describes 2-methyl-3-(5'-hydroxyalkyl)-norbornane, and U.S. Pat. No. 3,748,344 describes cyclic acetals of norbornane carboxaldehyde. Further, U.S. Pat. No. 3,860,635 describes a method for producing vinylnorbornanone, and U.S.
No. 4076853 describes alpha-allyl or meta-allyl-3,3-dimethyl-2-norbornylmethanol. However, tricyclic aliphatic compound derivatives having specific substituents as in the present invention have not been known so far. The present inventors completed the present invention as a result of extensive research into tricyclic aliphatic compounds useful as fragrance ingredients. That is, the present invention relates to a tricyclic aliphatic compound derivative represented by the following formula (), a method for producing the same, and a fragrance composition containing the same. In the above formula, R ₁ represents hydrogen, a methyl group, or an ethyl group, R ₂ represents a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and the combination of solid lines and dotted lines indicates a single bond or a double bond. represent. The tricyclic aliphatic compound derivative of the formula () is a tricyclic aliphatic aldehyde, 6-ethyltricyclo[2.2.1.0 ^2,6 ]heptyl-3-aldehyde represented by the following formula (), and ethyl alkyl ketone or It is produced by reacting a methyl alkyl ketone at 0 to 200°C in the presence of an aldol condensation catalyst, followed by dehydration and reduction. The ethyl alkyl ketone or methyl alkyl ketone to be subjected to aldol condensation with the tricyclic aliphatic aldehyde of the above formula () includes ethyl lower alkyl ketones such as methyl ethyl ketone, diethyl ketone, ethyl propyl ketone, and ethyl isopropyl ketone, as well as acetone, methyl propyl ketones and methyl lower alkyl ketones such as methyl isopropyl ketone. In addition, the tricyclic aliphatic aldehyde of formula () is
6-ethyltricyclo[2.2.1.0 ^2,6 ]heptane-3
-one and an alkyl monohalogenoacetate are reacted in the presence of a basic catalyst to perform dehydrohalogenation to obtain the corresponding glycidic acid ester, which is then hydrolyzed and decarboxylated. be able to. An acidic substance or a basic substance is used as the aldol condensation catalyst. Examples of acidic catalysts include inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid or sulfamic acid, Lewis acids such as boron trifluoride, benzenesulfonic acid, trifluoromethanesulfonic acid, toluenesulfonic acid, and naphthalenesulfonic acid. , trifluoroacetic acid, trichloroacetic acid, and their salts. Basic substance catalysts include metal hydroxides, such as alkali hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide, and metal alkoxides, such as lithium methyl hydroxide. Acid, sodium methylate, sodium ethylate, potassium methylate, aluminum isopropoxide, potassium t-butoxide, etc. are effective, and weak alkalis, such as alkali carbonates such as sodium carbonate, potassium carbonate, and potassium acetate, and fluoride Potassium is also commonly used. Furthermore, other basic catalysts include alkali hydrides such as sodium hydride, lithium hydride, and potassium hydride, alkali amides such as lithium amide, sodium amide, and potassium amide, tertiary amines, and quaternary ammonium bases. , active methylene alkali compounds, alkali fluorides, alkali metal oxides, alkaline earth metal oxides, and cyclic amines. Among these, industrially important ones include alkali hydroxides, alkali carbonates, alkali alkoxides, alkali amides, tertiary amines, cyclic amines, and alkali salts of organic weak acids. The reaction temperature for aldol condensation is 0 to 200°C, preferably 50 to 150°C, and the reaction pressure may be normal pressure, increased pressure, or reduced pressure, as long as a predetermined temperature can be maintained. During the reaction, it is not necessary to use a solvent, but a solvent may be used to bring the raw materials and catalyst into sufficient contact and to maintain a uniform reaction temperature. As a solvent, the alkyl ketone itself used in excess, alcohols, saturated hydrocarbons,
Water, ethers and halogenated hydrocarbons may be used alone or in a mixture of two or more thereof. In the present invention, dehydration is carried out after the aldol condensation of the tricyclic aliphatic aldehyde and the ketone, but normally, if the reaction conditions are appropriately selected, the dehydration reaction can be continued after the aldol condensation is achieved. In such cases, no special dehydration step is necessary. However, depending on the reaction conditions, for example when the condensation reaction temperature is selected to be relatively low, it may be necessary to provide a step of heating or adding a dehydrating agent and heating after the condensation reaction. . By the above method, an α,β-unsaturated ketone represented by the formula () in the reaction formula below can be obtained. In the reaction formula below, 6-ethyltricyclo[2.2.1.0 ^2,6 ]
This is a schematic illustration of a process of reducing a ketone obtained by reacting heptyl-3-aldehyde with diethyl ketone. The tricyclic aliphatic compound derivatives () and () of the present invention can be obtained by reducing the formula () or the ketone represented by the formula () as shown in the reaction formula. In this reaction formula, it is important in the reduction in steps C and D that only carbonyl groups are selectively reduced to hydroxyl groups. It is therefore usually convenient to use metal hydrides, aluminum alkoxides and alcohols, or alkali metal or alkaline earth metal alkoxides and alcohols as reducing agents. Catalytic hydrogen reduction may also be carried out under mild conditions in the presence of a suitable catalyst, and electrolytic reduction may also be used. Examples of metal hydrides include sodium borohydride, lithium borohydride, lithium aluminum hydride, sodium aluminum hydride, aluminum hydride complex salts, lithium hydride, sodium hydride or calcium hydride, or sodium bis(methoxyethyl)aluminum. Hydride and the like are suitable. Isopropyl alcohol and aluminum isopropoxide are used as a combination of alcohol and aluminum alkoxide. Solvents for reduction reactions using these reducing agents include alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol;
Ethers such as dioxane, diethyl ether, ethylene glycol dimethyl ether, and tetrahydrofuran, saturated aliphatic hydrocarbons, aromatic solvents such as toluene, or a mixture of two or more fatty acid alkyl esters, or a mixture of these and water are used. . The reduction temperature is usually 0 to 150°C. After the reduction reaction is completed, unreacted components and solvent are separated, and the organic layer containing the target product is collected and subjected to purification operations such as precision distillation to obtain the tricyclic aliphatic compound derivative that is the target product. In addition, the reduction in steps B and E of the above reaction formula reduces the carbon-carbon double bond under conditions that do not change the carbonyl group or hydroxyl group, but usually catalytic hydrogenation under mild conditions is performed. It is enough. As the catalyst for this catalytic hydrogenation, it is preferable to use a catalyst based on a group 8 metal in the periodic table such as nickel, cobalt, ruthenium, rhodium or platinum. It is generally convenient to use it as a carrier. The reaction pressure of this catalytic hydrogenation ranges from normal pressure to 10
Kg/cm ² , and the reaction temperature may be 0 to 150°C. Furthermore, the reduction in step A of the reaction formula is
The reduction of a carbon-carbon double bond and the reduction of a carbonyl group to a hydroxyl group are carried out simultaneously, and can be easily carried out particularly by catalytic hydrogenation. In this case, it is important to select appropriate conditions so as not to cause hydrogenolysis of hydroxyl groups, but nickel, cobalt, platinum, copper chromite, ruthenium, rhodium catalysts, etc. are usually used as catalysts. Activated carbon, alumina, etc. can also be used as a support. In the reaction, it is not necessary to use a particular solvent, but if it is used, alcohols such as ethanol, alicyclic saturated hydrocarbons such as cyclohexane, etc. are suitable. In addition, the reaction temperature of catalytic hydrogenation is 30 to 300℃,
A suitable reaction pressure is 2 to 300 kg/cm ² . By the above reduction method, the tricyclic aliphatic compound derivative represented by the general formula () of the present invention can be produced. Examples of the tricyclic aliphatic compound derivative represented by the general formula () of the present invention include the following compounds. That is, 1-{6-ethyltricyclo[2.2.1.0 ^2,6 ]heptan-3-yl}-2-methyl-1-pentene-
3-ol, 1-{6-ethyltricyclo[2.2.1.0 ^2,6 ]heptan-3-yl}-2-methylpentan-3-ol, 4-{6-ethyltricyclo[2.2.1.0 ^{2, 6} ]Heptan-3-yl}-3-methyl-3-butene-2
-ol, 4-{6-ethyltricyclo[2.2.1.0 ^2,6 ]heptan-3-yl}-3-methylbutan-2-ol, 1-{6-ethyltricyclo[2.2.1.0 ^2,6 ] heptane-3-yl}-1-penten-3-ol, 1-{6-ethyltricyclo[2.2.1.0 ^2,6 ]heptan-3-yl}pentan-3-ol, 4-{6-ethyltricyclo Cyclo[2.2.1.0 ^2,6 ]heptan-3-yl}-3-buten-2-ol, 4-{6-ethyltricyclo[2.2.1.0 ^2,6 ]heptan-3-yl}butan-2- ol, 1-{6-ethyltricyclo[2.2.1.0 ^2,6 ]heptan-3-yl}-2-methyl-1-hexene-
3-ol, 1-{6-ethyltricyclo[2.2.1.0 ^2,6 ]heptan-3-yl}-2-methylhexan-3-ol, and the like. These tricyclic aliphatic compound derivatives essentially have a woody scent, but they vary from floral scents to heavy scents, and they have not only a weary note, but also a floral note and a fusea note. , moss note, chypre note, leather note, tobacco note, animal note, citrus note, resinous note, green note,
It can be suitably blended with aldehyde notes, etc., and various excellent fragrance compositions can be prepared. Therefore, the tricyclic aliphatic compound derivative of the present invention is important as a base fragrance of various kinds, and this base fragrance can be used for perfumes, cosmetics, detergents, daily necessities, toiletries, bleaches, antiperspirants, deodorants, and aerosols. In addition to being used as a flavoring agent for products, bath salts, aromatic products, etc., it can also be used in a wide range of applications such as flavor components, synthetic essential oil components, and fragrance diluents. In addition, in the tricyclic aliphatic compound derivative of the present invention, a hydrogen atom is also substituted on the carbon on the ring which is substituted with a side chain having a hydroxyl group, so due to the steric positional relationship between the hydrogen atom and the side chain, endo There are two stereoisomers, the endo and exo isomers, both of which are useful in the perfumery applications mentioned above. Next, the present invention will be explained in further detail with reference to Examples. Example 1 Synthesis of 1-{6-ethyltricyclo[2.2.1.0 ^2,6 ]heptan-3-yl}-2-methyl-1-penten-3-ol 6.9 g (0.08 mol) of diethyl ketone and 40% Dissolve 1.3g of potassium hydroxide in 28ml of ethanol,
-Ethyltricyclo[2.2.1.0 ^2,6 ]heptane-3-
After 4.6 g (0.03 mol) of aldehyde was added dropwise, the mixture was heated under reflux for 3 hours. Thereafter, ethanol was distilled off from the reaction mixture, and the residue was extracted with ether. The ether extract was washed with water, dried, the ether was distilled off, and then distilled under reduced pressure to obtain 1-{6-ethyltricyclo[2.2.1.0 ^2,6 ], which is an α,β-unsaturated ketone.
heptane-3-yl}-2-methyl-1-penten-3-ol 4.0 g (yield, 59.3%; boiling point 95~
96°C/0.25mmHg). This α,β-unsaturated ketone is IR (neat), NMR
(CCl ₄ ) spectrum confirmed that it had the structure of the above formula (). Elemental analysis (as C ₁₅ H ₂₂ O) C (%) H (%) Calculated value 82.6 10.1 Actual value 82.9 10.0 IR (neat): 1670 cm ^-1 (C=0 stretching vibration of α, β-unsaturated ketone) 1630 cm ^-1 (C=C stretching vibration) NMR (CCl ₄ ): 1.80δ (singlet, 3H) 0.80~2.00δ (multiplet, 16H) 2.40~2.80δ (quartet, 2H) 6.20~6.50δ ( Double line, 1H) Next, 1.3 g of lithium aluminum hydride was added to 200 ml of tetrahydrofuran, and while stirring under ice cooling, 7.0 g (0.03 mol) of α,β-unsaturated ketone obtained in the same manner as above was added. ) was gradually added dropwise.
After stirring the mixture at room temperature, ethyl acetate was added to remove excess reducing agent, and dilute sulfuric acid was added to make the mixture slightly acidic, followed by ether extraction. After washing the extract with water and drying, the ether was distilled off, followed by vacuum distillation to obtain the title 1-{6-ethyltricyclo[2.2.1.0 ^2,6 ]heptan-3-yl}-2-. 5.3 g of methyl-1-pentel-3-ol (yield,
74.6%; boiling point 109-111°C/0.4mmHg). Elemental analysis (as C ₁₅ H ₂₄ O) C (%) H (%) Calculated value 81.8 10.9 Actual value 82.1 10.7 IR (neat): Characteristic absorption of 3400 cm ^-1 (O-H stretching vibration) was observed, 1670cm ^-1 (C of α,β-unsaturated ketone
=O stretching vibration) had disappeared. NMR (CCl ₄ ): 1.60δ (singlet, 3H) 0.70~1.80δ (multiplet, 17H) 2.20~2.50δ (quartet, 2H) 3.60~3.90δ (triplet, 1H) 4.95~5.30δ (Double line, 1H) The resulting compound has a warm woody aroma and is extremely useful for blending in oriental fragrances, floral fragrances, daylily fragrances, etc. Examples 2-4 In Example 1, instead of dimethyl ketone,
α,β-unsaturated ketones were obtained by carrying out aldol condensation in the same manner except that the ketones shown in the following table were used. Then, in the same manner as in Example 1, this α,β-unsaturated ketone was reduced. The results are summarized in the table below.

[Table] Example 5 1-{6-ethyltricyclo[2.2.1.0 ^2,6 ]heptan-3-yl}-2 obtained in Example 1
-Methyl-1-penten-3-one 5.0g (0.023
mol) in 100 ml of methanol, put it in a 200 c.c. autoclave with 0.3 g of Raney nickel,
After repeating degassing and nitrogen substitution twice, hydrogen gas was introduced under pressure and the reaction was carried out at room temperature for 3 hours at a pressure of 4 kg/cm ² .
After separating the catalyst from the reaction mixture and distilling off methanol, 1-{6-ethyltricyclo[2.2.1.0 ^2,6 ]heptan-3-yl} was obtained by distillation under reduced pressure.
-2-methylpentan-3-ol 4.7 g (yield,
91.2%; boiling point, 96-97°C/0.2mmHg). Elemental analysis (as C ₁₅ H ₂₆ O) C (%) H (%) Calculated value 81.1 11.7 Actual value 81.2 11.4 IR (neat): 3300 cm ^-1 (O-H stretching vibration) NMR (CCl ₄ ): 0.70-2.50 δ (multiplet, 24H) 3.20δ (broad singlet, 1H) 3.55-3.80δ (triplet, 1H) Example 6 1-{6-ethyltricyclo[2.2.1.0 ^{2, [6} ] Heptane-3-yl}-2-methyl-1-penten-3-ol (hereinafter referred to as the "synthetic product") was used to prepare the following fragrance. β-Phenylethyl alcohol 140g α-Hexylcinnamic aldehyde 100g Benzyl acetate 100g Hydroxycitronellal 90g Lilial (manufactured by Givaudan) 85g Lavender oil 85g Nerol 65g Coumarin 40g Musk ketone 40g Musk ambrette 40g Linalool 25g Isoamyl salicylate 2 0g Eugenol 20g Iran・Ylang oil extra 20g Pachylily oil 15g Vanirin 10g β-Iron 5g Synthetic compound 100g Total 1000g The fragrance prepared with this compound is a bouquet-like exotic floral-based fragrance.
Excellent as a fragrance agent for soaps, cosmetics, room air fresheners, etc.

Claims (1)

[Scope of Claims] 1. A tricyclic aliphatic compound derivative represented by the following formula (), In the formula, R ₁ represents hydrogen, a methyl group or an ethyl group, R ₂ represents a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and the combination of a solid line and a dotted line represents a single bond or a double bond. . 2. The tricyclic aliphatic compound derivative according to claim 1, wherein the tricyclic aliphatic compound derivative is represented by the following formula (). 3 A tricyclic aliphatic aldehyde represented by the following formula () and an ethyl alkyl ketone or a methyl alkyl ketone are combined in the presence of an aldol condensation catalyst.
A method for producing a tricyclic aliphatic compound derivative represented by the following formula (), which comprises performing a reaction at ~200°C, followed by dehydration and reduction; In the formula, R ₁ represents hydrogen, a methyl group, or an ethyl group, R ₂ represents a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and the combination of solid lines and dotted lines represents a single bond or a double bond. represent. 4. The tricyclic aliphatic compound according to claim 3, wherein a tricyclic aliphatic compound derivative represented by the following formula () is produced by using diethyl ketone as the ethyl alkyl ketone or methyl alkyl ketone. Method for producing compound derivatives. 5 A fragrance composition containing a tricyclic aliphatic compound derivative represented by the following formula (), In the formula, R ₁ represents hydrogen or a methyl group, and R ₂
represents a methyl group, ethyl group, n-propyl group or isopropyl group, and a combination of a solid line and a dotted line represents a single bond or a double bond. 6. A fragrance composition comprising a tricyclic aliphatic compound derivative according to claim 5, wherein the tricyclic aliphatic compound derivative is represented by the following formula ().