JPH0420897B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel fragrance compositions containing norbornane derivatives. More specifically, the present invention relates to a fragrance composition containing a norbornane derivative represented by the following formula () as an active ingredient. Here, R ₁ ... represents an alkenyl group or alkylidene group having 3 to 10 carbon atoms, R ₂ and R ₃ represent a hydrogen atom or a methyl group, and 〓
Indicates a single or double bond, also +++++
is a bond that may be present, but when the bond is absent, R ₄ and R ₅ are hydrogen atoms, aliphatic hydrocarbon residues having 1 to 4 carbon atoms, phenyl groups, or cyclohexyl groups. and when the bond is present, R ₄ +++++R ₅ is an alkylene group having a total of 3 to 5 carbon atoms. The norbornane derivative used in the fragrance composition of the present invention is prepared by combining a norbornyl aldehyde represented by the following formula (), a carbonyl compound represented by the following formula (), and an aldol condensation catalyst in the presence of an aldol condensation catalyst.
It is a product obtained by reacting at 0 to 200°C, followed by dehydration and reduction. Here, R ₁ ... represents an alkenyl group or alkylidene group having 3 to 10 carbon atoms, R ₂ and R ₃ represent a hydrogen atom or a methyl group, and ++++++ is a bond that may exist. However, when this bond does not exist, R ₄ and R ₅ are hydrogen atoms,
Represents an aliphatic hydrocarbon residue, phenyl group, or cyclohexyl group having 1 to 4 carbon atoms, and when this bond is present, R ₄ +++++R ₅ represents a group with a total number of carbon atoms of 3 to 4. There are 5 alkylene groups. The norbornylaldehyde represented by the above formula () includes 5 or 6-propenylnorbornyl-2-aldehyde, 5 or 6-isopropenylnorbornyl-2-aldehyde, 5 or 6-propylidenenorbornyl -2-aldehyde, 5- or 6-isopropylidenenorbornyl-2-aldehyde, and the like. The norbornylaldehyde of the above formula () is disclosed in Japanese Patent Publications No. 46-33028, No. 51-26438, No. 52-
30512 or 52-32625, or the Diels-Alder reaction between cyclopentadiene and mono- or diolefin (for example, Journal of the Japan Petroleum Institute, 25, (1), 58 (1982)). The starting material can be alkenyl or alkylidene norbornene. For example, in the above-mentioned Special Publication No. 52-30512, C ₂ to _{C 10}
α-olefin and norbornadiene are reacted in the presence of a catalyst to produce alkenylnorbornadiene having a C ₃ to C ₁₀ alkenyl group.
Furthermore, alkenylnorbornene in which the alkenyl group has 3 to 10 carbon atoms can be obtained from the same Diels-Alder reaction between a diolefin having 5 to 10 carbon atoms and cyclopentadiene. Alkenyl or alkylidene norbornyl aldehydes of the formula () can be obtained by using these alkenyl or alkylidene norbornene as starting materials and using a transition metal compound catalyst described in Japanese Patent Application No. 56-29189 by a hydroformylation method or the like. It will be done. In addition, as the carbonyl compound of the above formula (), acetaldehyde, propionaldehyde,
Butyraldehyde, acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isopropyl ketone, ethyl propyl ketone, ethyl isopropyl ketone, ethyl butyl ketone, ethyl isobutyl ketone, methyl isobutyl ketone, dipropyl ketone, acetophenone,
These include propiophenone, methylbenzyl ketone, cyclopentanone, cyclohexanone, and cycloheptanone. An acidic substance or a basic substance is used as an aldol condensation catalyst for aldol condensation of the norbornyl aldehyde of the above formula () and the carbonyl compound of the formula (). Examples of acidic catalysts include inorganic acids such as sulfamic acid, hydrochloric acid, hydrobromic acid, phosphoric acid or sulfuric acid, Lewis acids such as boron fluoride, benzenesulfonic acid, trifluoromethanesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, Organic acids include trifluoroacetic acid and trichloroacetic acid. Basic substance catalysts include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide, and metal alkoxides such as lithium methylate and sodium methyl hydroxide. Acid salts, sodium ethylate, potassium methylate, aluminum isopropoxide, potassium t-butoxide, etc. are effective, and alkali salts of weak acids such as sodium carbonate, potassium carbonate, potassium acetate, potassium fluoride, etc. are also often used. . In addition, other basic catalysts include sodium hydride, lithium hydride, potassium hydride, lithium amide, sodium amide, potassium amide, tertiary amine, quaternary ammonium base, activated methylene alkali compound, alkali metal oxide. oxidants, alkaline earth metal oxides, and cyclic amines. Among these, the industrially important ones are alkali hydroxide, alkali carbonate, alkali alkoxide,
These include alkali amides, tertiary amines, cyclic amines, and alkali salts of weak acids. The reaction temperature for aldol condensation is 0 to 200°C, preferably 50 to 150°C, but when an aldehyde is used as the carbonyl compound of formula (), a slightly lower temperature is used to suppress the condensation of the aldehyde itself. For example, 0 to 100°C is suitable.
The reaction can be carried out at normal pressure, increased pressure or reduced pressure. In the aldol condensation reaction, it is not necessary to use a solvent, but a solvent can be used to bring the raw materials and catalyst into sufficient contact and to maintain a uniform reaction temperature. As a solvent, the carbonyl compound itself used in excess, alcohols,
Water, saturated hydrocarbons, ethers and halogenated hydrocarbons may be used alone or in a mixture of two or more thereof. In the present invention, it is necessary to dehydrate the aldol condensate after the aldol condensation of the compounds of formula () and formula (), but normally, the aldol condensation reaction can be achieved by appropriately selecting the reaction conditions. Since the dehydration reaction can be carried out continuously after the dehydration reaction, a special dehydration step is not necessary in such a case. However, depending on the reaction conditions, such as when the condensation reaction is set at a relatively low temperature, dehydration may be performed after the condensation reaction by heating or by adding a dehydrating agent. can. Examples of these reaction processes and subsequent reaction processes are as follows. In the figure, first, norbornyl- of the formula () is shown.
Using (') as an example of 2-aldehyde, (') as an example of the carbonyl compound of the above formula ()
was used for aldol condensation and dehydration to form α, β-
As an example of an unsaturated ketone we get () and further,
This shows that the norbornane derivative () of the present invention can be produced by reducing this. In the previous figure, 5- or 6-isopropenylnorbornyl-2-aldehyde is designated as ('), diethyl ketone is designated as ('), and the compounds corresponding to the formula () obtained from these are designated as () depending on the degree of reduction. ') or (''), both of which can be synthesized from the α,β-unsaturated ketone of formula () by appropriately changing the reduction operation. In the previous figure, the reduction in step A Therefore, it is important to selectively reduce only carbonyl groups to hydroxyl groups.Therefore, metal hydrides, aluminum alkoxides and alcohols, or alkali metal or alkaline earth metal alkoxides and alcohols are usually used as reducing agents. Catalytic hydrogen reduction may 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, hydride Preferred are lithium boron, lithium aluminum hydride, sodium aluminum hydride, aluminum hydride complex salts, lithium hydride, sodium hydride or calcium hydride, or bis(methoxyethyl)aluminum sodium hydride. Combination of alcohol and aluminum alkoxide. Isopropoxide and aluminum isopropoxide are used as solvents for the reduction reaction using these reducing agents, as well as 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, aromatics 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, the organic layer containing the target product is collected, and a purification operation such as precision distillation is performed to obtain the target product, norbornylalkenol. Further, in the reduction in step B of the previous figure, the carbon-carbon double bond is reduced under conditions that do not change the hydroxyl group, but catalytic hydrogenation under mild conditions is usually sufficient. As the catalyst for this catalytic hydrogenation, it is preferable to use a catalyst based on a metal from group 8 of the periodic table such as Raney nickel, ruthenium, rhodium or platinum, and these catalysts include activated carbon,
It is generally convenient to use barium sulfate, alumina, calcium carbonate, etc. as supports. The reaction pressure for this catalytic hydrogenation may range from normal pressure to 10 kg/cm ² , and the reaction temperature may range from 0 to 150°C. Further, the reduction in C of the above reaction formula involves simultaneously reducing a carbon-carbon double bond and reducing a carbonyl group to a hydroxyl group, and can be carried out by catalytic hydrogenation. in this case,
It is important to choose appropriate conditions so as not to cause hydrolysis of hydroxyl groups, but nickel, platinum, copper chromite, ruthenium, rhodium catalysts, etc. are usually used as catalysts, and activated carbon or alumina are used as supports. etc. can also be used. It is not necessary to use a particular solvent during the reaction, but
If used, alcohols such as ethanol, alicyclic saturated hydrocarbons such as cyclohexane, etc. are suitable. Further, the reaction temperature for catalytic hydrogenation is suitably 30 to 300°C, and the reaction pressure is suitably 2 to 300 kg/cm ² . Representative examples of the norbornane derivatives represented by the formula () obtained as described above for use in the fragrance composition of the present invention include the following compounds obtained by reacting with diethyl ketone. Further, the following compounds are obtained from propionaldehyde subjected to aldol condensation. Furthermore, the following norbornane derivatives can be obtained from cyclohexanone. The norbornane derivative used in the present invention is essentially based on an essential scent, but it can vary from a floral scent to a heavy scent. It can be conveniently incorporated into moss note, chypre note, leather note, tobacco note, animal note, citrus note, resinous note, green note, aldehyde note, etc., and various excellent fragrance compositions can be prepared. Therefore, the above-mentioned norbornane derivatives are important as various base fragrances, and these base fragrances are used as flavoring agents for perfumes, cosmetics, soaps, daily necessities, etc., as well as flavor components, synthetic essential oil components, It can also be widely used in applications such as deodorant components, deodorant components, and perfume diluents. Next, the present invention will be explained in further detail with reference to Examples. Note that the norbornane derivatives obtained in Production Examples 1 to 5 are summarized in Table 1. Production example 1 Dissolve 14.7 g (0.171 mol) of diethyl ketone in 15 ml of methanol and add 40% sodium hydroxide solution.
Add 0.5g and heat under reflux, then add 5g.
7.0 g (0.043 mol) of a mixture of -isopropenylnorbornyl-2-aldehyde and 6-isopropenylnorbornyl-2-aldehyde was gradually added dropwise. This mixture was heated under reflux for about 2 hours to perform aldol condensation. At this time, since a dehydration reaction was occurring subsequently, an α,β-unsaturated ketone was obtained in a yield of 75% by distillation under reduced pressure without any special dehydration operation. The IR and nmr spectra of this compound showed the presence of an α,β-unsaturated ketone carbonyl group, indicating that aldol condensation was followed by a dehydration reaction. Next, this α,β-unsaturated ketone was dissolved in a mixed solution of methanol and potassium hydroxide, and while the mixture was heated to about 40°C and stirred, an alkaline methanol solution of sodium borohydride was added, and the mixture was further stirred for 3 hours. After the reaction, methanol was distilled off from the reaction mixture, extracted with ether, washed with water, and dried. After distilling off the ether, column chromatography was performed using silica gel as a packing material and benzene-ethyl acetate (3:1) as an eluent. By separating and purifying the product, norbornane derivative A shown in Table 1 was obtained in a yield of 78%. Analysis results IR: O-H stretching vibration at ~3400cm ^-1 , 3090cm ^-1 and 1640
C-H stretching vibration of isopropenyl group in cm ^-1 and C=
C stretching vibration was observed, and the absorption (1665 cm ^-1 ) of the carbonyl group of the α,β-unsaturated ketone disappeared due to reduction. nmr ( _CCl4 ): 0.65-2.50δ (multiplet, 15H) 1.50δ (singlet, 3H) 1.65δ (singlet, 3H) 3.45δ (broad singlet, 1H) 3.65-3.95δ (triplet, 1H) ) 4.60~4.80δ (double line, 2H) 4.90~5.25δ (double line, 1H) Elemental analysis (as C ₁₆ H ₂₆ O): C (%) H (%) Calculated value 82.1 11.1 Actual value 82.0 11.3 Production Example 2 5 or 6 was prepared in the same manner as Production Example 1 except that methyl ethyl ketone was used instead of diethyl ketone.
-By aldol condensation with isopropenylnorbornyl-2-aldehyde and dehydration,
α,β-unsaturated ketone was obtained in 70% yield. This compound has α, β by IR and NMR spectra.
- It showed the presence of a carbonyl group of an unsaturated ketone, indicating that aldol condensation was followed by a dehydration reaction. Next, this α,β-unsaturated ketone was reduced with a sodium borohydride solution in the same manner as in Example 1, and a mixture of norbornane derivatives B and C shown in Table 1 was obtained as a crude product in a yield of 85%. Obtained. This was separated and purified by medium pressure liquid chromatography (filler: silica gel, eluent: benzene) to obtain norbornane derivative C as the main product. Analysis results ir: The characteristic absorption was almost the same as that of compound A. nmr ( _CCl4 ): 1.10-1.20δ (doublet, 3H) 1.55δ (singlet, 3H) 0.70-2.80δ (multiplet, 13H) 3.40δ (broad singlet, 1H) 3.65-3.95δ (triplet Line, 1H) 4.60~4.75δ (Double line, 2H) 4.95~5.25δ (Double line, 1H) Elemental analysis (as C ₁₅ H ₂₄ O): C (%) H (%) Calculated value 81.8 10.9 Actual measurement Value 81.9 10.7 Production Example 3 Aldol By performing condensation, dehydration, and subsequent reduction, the yield of norbornane derivative D shown in Table 1 can be obtained.
Got it at 55%. Analysis result ir: O-H stretching vibration was observed at ~3400 cm ^-1 and C═C stretching vibration of isopropylidene group was observed at 1655 cm ^-1 . nmr ( _CCl4 ): 0.80-2.50δ (multiplet, 14H) 1.48-1.50δ (doublet, 6H) 1.65δ (singlet, 3H) 3.50δ (broad singlet, 1H) 3.65-4.00δ (triplet Line, 1H) 4.90-5.25δ (Double line, 1H) Elemental analysis (as C ₁₆ H ₂₆ O): C (%) H (%) Calculated value 82.1 11.1 Actual value 81.9 11.0 Production example 4 Instead of diethyl ketone The norbornane derivative E shown in Table 1 was obtained in a yield of 45% by aldol condensation, dehydration, and reduction in the same manner as in Production Example 1 except that cyclohexanone was used. Analysis results ir: The characteristic absorption was almost the same as that of norbornane derivative A. nmr ( _CCl4 ): 0.70-3.10δ (multiplet, 21H) 3.40δ (broad singlet, 1H) 3.75-4.10δ (triplet, 1H) 4.60-4.75δ (doublet, 2H) 4.90-5.20δ (Double line, 1H) Elemental analysis (as C ₁₇ H ₂₆ O): C (%) H (%) Calculated value 82.9 10.6 Actual value 82.6 10.5

【table】

[Table] Example 1 A hyacinth-based fragrance was prepared according to the following formulation. Cis-β-hexenyl acetate 20g Dimethylbenzyl carbinyl acetate 15g Cinnamic alcohol 10g Linalool 10g Geraniol 10g Methylionone 10g Citronellol 5g Labdanum oil 10g Norbornane derivative A from Production Example 1 10g Total 100g This base fragrance is used as a room air freshener and soap fragrance. used as. Example 2 A Miuge base perfume was prepared according to the following formulation. Hydroxycitronellal 40g Rhodinol 30g Linalool 10g α-amyl cinnamic aldehyde 5g Ylang-ylang oil 5g Tetrahydrolinalool 5g Norbornane derivative C from Production Example 2 5g Total 100g This base fragrance is a blend of mixed fragrances such as daffodil, lily, lilac, and lily of the valley. Used as a raw material. It can also be used as a flavoring agent for toilet cleaners. Example 3 An aldehyde floral-based fragrance was prepared using the following formulation. Bergamot oil 3g Ylang-ylang oil 7g Rose oil 2g 10%C ₁₀ -Aldehyde/ethanol solution 1g 10%C ₁₁ -Aldehyde/ethanol solution 3g 10%C ₁₂ -Aldehyde/ethanol solution 4g 10% methylnonyl aldehyde/ethanol solution
3g Diasmine aldehyde 2g Oris Concrete 2g Linalool 8g Linalyl acetate 4g α-ionone 4g Methylionone 3g Hydroxycitronellal 5g Rhodinol 5g Benzyl acetate 4g Mixed diasmine oil 30g Norbornane derivative D from Production Example 3 10g Total 100g This base fragrance is a floral perfume It is useful for preparing aldehyde perfumes. Example 4 A neroli-based fragrance was prepared using the following formulation. Petitgrain oil 48g Methyl anthraanilate 2g Linalool 20g Falnesol 10g Methyl-β-naphthyl ketone 1g Auranthiol 3g Nerol 2g Hedeion 4g Norbornane derivative E from Production Example 4 10g Total 100g This base fragrance was used as a raw material for an orange-flowery mixed perfume. It will be done.

Claims (1)

[Claims] 1. A fragrance composition containing a norbornane derivative represented by the following formula () as an active ingredient, Here, R ₁ ... represents an alkenyl group or alkylidene group having 3 to 10 carbon atoms, R ₂ and R ₃ represent a hydrogen atom or a methyl group, and 〓 represents a single bond or a double bond. , also ++
+++ is a bond that may exist, but when this bond does not exist, R ₄ and R ₅ are hydrogen atoms,
Represents an aliphatic hydrocarbon residue, phenyl group, or cyclohexyl group having 1 to 4 carbon atoms, and when such a bond exists, R ₄ +++++R ₅ represents the total number of carbon atoms. 3 to 5 alkylene groups.