JPS6321645B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to perfume compositions comprising a group of novel compounds derived from alkenyl or alkylidene norbornanone acetals, such as vinyl or ethylidene norbornanone acetals. The usefulness of ethylidene norbornene and its derivatives in fragrance compositions was disclosed in Japanese Patent Application Laid-Open No. 52-10428.
No. 49-30105, but no examples of fragrance compositions containing alkenyl or alkylidene norbornanone acetal derivatives are known. In the process of researching the synthesis of alkenyl or alkylidene norbornanone acetals, such as vinyl or ethylidene norbornanone acetal derivatives, the present inventors discovered a group of novel compounds useful for fragrance compositions and developed the present invention. It has been completed. That is, the present invention provides the following formulas () and ()
The present invention relates to a fragrance composition containing an α-hydroxyalkylnorbornanone acetal represented by: [Here, R ₁ is a saturated hydrocarbon residue having 2 to 7 carbon atoms. ] Furthermore, the above α-hydroxy-alkylnorbornanone acetal is derived from an alkenylnorbornanone acetal represented by the following formula () or an alkylidene norbornanone acetal represented by the following formula () to the unsaturated bond of the compound. It can be produced by reduction and hydrolysis via an adduct. Here, R ₁ is a saturated hydrocarbon residue having 2 to 7 carbon atoms, R ₄ is a methyl group, and R ₅ to _{R 8} are all hydrogen atoms. The method for producing α-hydroxyalkylnorbornanone acetal of the above formula () from these alkenyl or alkylidene norbornanone acetals through addition to unsaturated bonds of the compound and hydrolysis is as follows: Mercuric salts such as mercury salts ()
or a method in which a compound of formula () is reacted, a mercuric salt is added to an unsaturated bond, and the mercuric salt is then hydrolyzed to remove the mercury; a thallium salt such as thallium nitrate; A method in which borane, etc. is added to the unsaturated bond of the compound of formula (2) and then oxidized and hydrolyzed, which is a method in which oxitaleation is carried out in the same manner as above, a method in which borane, etc. is added to the unsaturated bond of the compound of formula (2), and then oxidized and hydrolyzed, and a method in which peracid is used. There are methods such as epoxidation, in which oxygen is added to an unsaturated bond using molecular oxygen in the presence of a peroxide or a catalyst to form an epoxide, which is then reduced and hydrolyzed. According to these methods, the α-hydroxyalkylnorbornanone acetal of the formula () can be selectively obtained in good yield from the alkenyl or alkylidene norbornanone acetal of the formula () or (), and isomerization, etc. There are also fewer side reactions. Furthermore, since both are carried out under non-acidic conditions, the acetal moiety of the alkenyl or alkylidene norbornanone acetal as a raw material is hardly decomposed. In the above-mentioned method involving oxymer curing, water, tetrahydrofuran, acetonitrile, ethyl ether,
A mercuric salt such as mercuric acetate, mercuric trifluoroacetate, or mercuric nitrate is added to an alkenyl or Addition to alkylidene norbornanone acetal. The reaction is carried out at normal pressure, but the pressure may be slightly reduced or increased. The amount of mercuric salt used is 0.5 to 2.0 mol per mol of alkenyl or alkylidene norbornanone acetal to be added. Next, reductive demercury and hydrolysis is performed using sodium borohydride-sodium hydroxide or sodium-liquefied ammonia to obtain the α-hydroxyalkylnorbornanone acetal of the formula (). The reaction temperature is 0 to 50°C, preferably 0 to 30°C, and usually at normal pressure.
The pressure may be slightly reduced or increased. Also, the method of undergoing oxidation is
The above-mentioned method involving oximerization is carried out in the same manner except that a thallium salt such as thallium acetate, thallium trifluoroacetate, or thallium nitrate is used instead of the mercuric salt. be able to. In the method that involves further hydroboration, diborane or substituted boron compounds such as dicyamylborane, dicyclohexylborane,
Thexylborane, diisopinocampheylborane, 9-borabicyclo[3.3.1]nonane, dichloroborane, etc. are added to alkenylnorbornane acetal. The amount of diborane used is 0.1 to 1 mole of alkenyl or alkylidene norbornanone acetal.
1.0 mol, and for substituted boron compounds, 0.5 to 2.0 mol is sufficient. As the solvent in this case, ethers such as tetrahydrofuran, ethyl ether, dimethyl carbitol, and diethyl carbitol are usually used. The reaction temperature is -15~230℃, preferably -5~
The temperature is 60°C, and the reaction is carried out at normal pressure, but the pressure may be slightly reduced or increased. Oxidative hydrolysis is then carried out using hydrogen peroxide-sodium hydroxide, organic peracid-sodium hydroxide solutions in water or a mixture of water and dimethyl carbitol, diethyl carbitol, tetrahydrofuran or ethyl alcohol. Add . The temperature of this reaction is 0-80°C, preferably 5-50°C. In addition, in the above-mentioned method involving epoxidation, an epoxide of an alkenyl or alkylidene norbornanone acetal is obtained using a peracid or the like, separated by distillation or the like, then reduced, and then hydrolyzed. That is, in the reaction to obtain epoxide, chloroform, methylene chloride,
Halogenated hydrocarbons such as carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene, xylene,
Aliphatic hydrocarbons such as hexane, pentane, and heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, esters such as ethyl acetate and ethyl propionate, and ethers such as ethyl ether and tetrahydrofuran are used. In these solutions, organic peracids such as peracetic acid, trifluoroperacetic acid, perbenzoic acid, performic acid, m-chloroperbenzoic acid, permaleic acid, perphthalic acid, perlauric acid,
Epoxides of alkenyl or alkylidene norbornanone acetals with organic peroxides and transition metal oxides such as molybdenum or vanadium, with hydrogen peroxide and organic nitriles, or with oxygen in the presence of silver-, thallium-, or palladium-based metal catalysts. obtain. When using a silver-based, thallium-based, or palladium-based metal catalyst in a gas phase reaction, an inert gas such as nitrogen gas may be diluted. The amount of organic peracid used is per mole of olefin.
Use 0.5-2.0 mol. The reaction temperature is -15 to 100
℃, preferably -5 to 70℃. The reaction pressure may be normal pressure, or may be slightly reduced or increased. In this way, we obtain epoxide and distill it,
It is separated by extraction and subjected to subsequent reduction and then hydrolysis. This reduction is performed on various metal hydrides in ethers such as ethyl ether, tetrahydrofuran, dimethyl carbitol, and diethyl carbitol, aromatic hydrocarbons such as benzene, toluene, and xylene, and aliphatic hydrocarbons such as hexane and pentane. , for example, lithium aluminum hydride, lithium borohydride, sodium borohydride, aluminum hydride, dichloroaluminum hydride, diisobutyl aluminum hydride,
Reduction with diborane, sodium cyanoborohydride, lithium triethoxyaluminum hydride, tritertiarybutoxyaluminum hydride, sodium aluminum hydride, dicyamylborane, etc. The reduction temperature is -80 to 100°C, preferably -70 to 50°C. After reduction, α-hydroxynorbornanone acetal is obtained by subsequently adding methanol, ethanol, isopropanol, water, or the like for hydrolysis. After the reaction as described above, the solvent is distilled off and the residue is separated and purified according to a conventional method to produce the α-hydroxyalkylnorbornanone acetal of the formula (). By the way, in the reaction in the above-mentioned method ~, the introduction position of the hydroxyl group changes depending on how the alkyl group and hydrogen atom of the carbon-carbon double bond are substituted. For example, when the alkenyl norbornanone acetal of the formula () is used as a raw material and the substituent R ₇ or R ₈ is a hydrogen atom or a hydrocarbon residue with a small number of carbon atoms, the oxymer cleation of A good method is to undergo epoxidation with cation and epoxidation; conversely, substituents R ₇ and R ₈ are hydrocarbon residues with a large number of carbon atoms, and R ₆ is a hydrogen atom or a hydrocarbon residue with a small number of carbon atoms. A method involving hydroboration can introduce a hydroxyl group at the α-position with good yield. In addition, using the alkylidene norbornanone acetal of the formula () as a raw material, substituents R ₄ and R ₅
When is a hydrogen atom or a hydrocarbon residue having a small number of carbon atoms, the hydroboration method can yield the α-hydroxyalkylnorbornanone acetal of the formula () in a good yield. However, when both of the substituents R ₄ and R ₅ are hydrocarbon residues having a large number of carbon atoms, it is also possible to use a method involving oxymer cleavage, oxitaleation, and epoxidation. Incidentally, the alkenylnorbornanone acetal of the formula () can be synthesized using the following alkenylnorbornene as a starting material.

[Formula] Here, R ₆ , R ₇ and R ₈ are the same as in the above formula (). An acid such as sulfuric acid, formic acid, acetic acid, or propionic acid is added to the above alkenylnorbornene in the presence of an acid catalyst, and then hydrolyzed to obtain alkenylnorbornanol of the following formula.

[Formula] Here, R ₆ , R ₇ and R ₈ are the same as in the above formula (). Next, this alkenylnorbornanol is oxidized to obtain an alkenylnorbornanone of the following formula.

[Formula] Here, R ₆ , R ₇ and R ₈ are the same as in the above formula (). This alkenylnorbornene includes vinylnorbornene, propene-1'-yl-norbornene,
Examples include isopropenylnorbornene, 1'-methyl-propene-1'-yl-norbornene, 2'-methyl-propene-1'-ylnorbornene, and 1',2'-dimethyl-propene-1'-ylnorbornene. Then, it is acetalized with a diol in the presence of an acid catalyst to obtain the alkenylnorbornanone acetal of the formula (). The diol to be acetalized is 1,2-
diol and 1,3-diol. Here, 1,2-diol is a compound in which two hydroxyl groups are substituted on adjacent carbon atoms of a saturated hydrocarbon, and 1,3-diol is a compound in which two hydroxyl groups are substituted into one carbon atom of a saturated hydrocarbon. Each refers to a compound in which two carbon atoms are substituted on sandwiching carbon atoms. Typical examples of the above 1,2-diols are ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-,2,
3- or 3,4-hexanediol, 1,2-
or 2,3-pentanediol, 1,2-cyclohexanediol and methylcyclohexane-1,2-diol. In addition, as 1,3-diol, 1,3-propanediol, 1,3-butanediol, 2,2
-dimethyl-1,3-propanediol, 2,2
-diethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-
1,3-propanediol, 1,3-cyclohexanediol and methylcyclohexane-1,
3-diol, etc. In the above-mentioned acetalization, the above-mentioned diols can be used alone or in mixtures. Acetalization with 1,2-diol produces a 1,3-dioxolane ring, and 1,3-diol produces a 1,3-dioxane ring. Furthermore, the alkylidene norbornene acetal of the formula () can be synthesized using the alkylidene norbornene of the following formula as a starting material.

[Formula] Here, R ₄ and R ₅ are the same as in the above formula (). Examples of the alkylidene norbornene include methylene norbornene, ethylidene norbornene, propylidene norbornene, isopropylidene norbornene, isobutylidene norbornene, butylidene norbornene, secondary butylidene norbornene, pentylidene norbornene, and isopentylidene norbornene. From the above alkylidene norbornene, alkylidene norbornanol is obtained, then oxidized to form alkylidene norbornanone, and further acetalized with diol to obtain the formula ()
The alkylidene norbornanone acetal is obtained. That is, it can be carried out in substantially the same manner as the method for obtaining alkenylnorbornanone acetal of the formula () from alkenylnorbornene as described above. However, in order to obtain the intermediate alkylidene norbornanol with high purity, hydroboration is better than the method of acid addition and hydrolysis of alkylidene norbornene because it does not produce tricyclene compounds, polymers, etc. It's advantageous. Among the above-mentioned alkenyl or alkylidene norbornenes, 5-vinyl-2-norbornene and 5-ethylidene-2-norbornene can be easily obtained from the Diels-Alder reaction of butadiene and cyclopentadiene; Since it is also a tertiary copolymerization component, it is a preferred starting material because it can be obtained industrially at low cost and in large quantities. Here, as the alkenylnorbornene, 5
Examples of compounds represented by the formula () obtained by oxidation, hydrolysis, oxidation, and acetalization from vinyl-2-norbornene include spiro[1,3-dioxolane-2, 2' and 2,3'-(5'-vinylnorbornane)], spiro[4,5-dimethyl-1,3-dioxolane-2,2' and 2,3'-(5'-vinylnorbornane)], Spiro [1,3-dioxane-
2,2' and 2,3'-(5'-vinylnorbornane)], spiro[5,5-dimethyl-1,3-dioxane-2,2' and 2,3'-(5'-vinylnorbornane) ], spiro[4-methyl-1,3-dioxane-2,2' and 2,3'-(5'-vinylnorbornane)], spiro[5,5-diethyl-1,3
-dioxane-2,2' and 2,3'-(5'-vinylnorbornane)], spiro[4,5-tetramethylene-1,3-dioxolane-2,2' and 2,
3′-(5′-vinylnorbornane)]. Therefore, α of the formula () obtained from these vinylnorbornanone acetal compounds by addition to the vinyl group, reduction and hydrolysis.
-Hydroxyalkylnorbornanone acetals are as follows. That is, spiro{1,3-dioxolane-2,
2′ and 2,3′-[5′-(α-hydroxyethyl)
- norbornane]}, spiro {4,5-dimethyl-
1,3-dioxolane-2,2'- and 2,3'-
[5′(α-hydroxyethyl)-norbornane]},
Subiro {1,3-dioxane-2,2′ and 2,
3′-[5′-(α-hydroxyethyl)-norbornane]}, spiro{5,5′-dimethyl-1,3-dioxane-2,2′ and 2,3′-[5′-(α- hydroxyethyl)-norbornane]}, spiro{4
-Methyl-1,3-dioxane-2,2' and 2,3'[5'-(α-hydroxyethyl)-norbornane]}, spiro{5,5-diethyl-1,3-
Dioxane-2,2′ and 2,3′-[5′-(α-
hydroxyethyl)-norbornane]} and spiro{4,5-tetramethylene-1,3-dioxolane-2,2' and 2,3'-[5'-(α-hydroxyethyl)-norbornane]}. . The compound of formula (), which is the compound of the present invention, exists in stereoisomers of endo and exo forms. 5-(α-hydroxyethyl)-2
-Norbornanone ethylene acetal or spiro{1,3-dioxolane-2,2'-[5'-(α
-Hydroxyethyl)-Norbornane]} as an example, the following formula is obtained.

【formula】

[Formula] In the present invention, any of these stereoisomers is effective as a component of the perfume composition. Therefore, a mixture of stereoisomers of the compound obtained as described above can be used as a perfume component. Of course, it can also be used as a single compound. The compound represented by the above formula () is a colorless and transparent liquid substance, and has good compatibility with solvents commonly used for fragrances to the extent that it can be mixed in any proportion, and is also compatible with other solid or liquid fragrance materials. Dissolve well. In addition, these compounds are stable against oxidation and do not undergo any change even when left for a long period of time, and do not cause irritation when they come into contact with the skin and are not toxic during use. The α-hydroxyethyl alkylnorbornanone acetal of the present invention has a woody scent as its base, but it does not only have a midday note.
It can be conveniently combined with floral notes, fusea notes, moss notes, chypre notes, leather notes, tobacco notes, animal notes, citrus notes, resinous notes, green notes, fruity notes, aldehyde notes, ester notes, etc., and is a variety of excellent fragrances. Become a composition. In addition to being used as a flavoring agent for various perfumes, cosmetics, soaps, and daily necessities, this fragrance composition can also be widely used as flavor components, synthetic essential oil components, deodorant components, deodorant components, and perfume diluents. Can be done. Next, in order to further explain the technical content of the present invention, production examples and examples will be shown below as reference examples. It should not be construed as being limited to the following examples, and it goes without saying that the embodiments may be modified and implemented as desired without departing from the spirit and spirit of the present invention. First, a production example of the compound of the formula () is shown,
Next, the content of the present invention will be specifically explained with reference to Examples. Production example 1 Production of spiro{1,3-dioxolane-2,2' and 2,3'-[5'-(α-hydroxyethyl)-norbornane]} 5-vinyl-2 and 3-norbornanone were prepared using ethylene glycol. Acetalization was carried out by the method described above, with a yield of 92.0%, producing colorless green acrylic camphor-smelling 5-vinyl-2 and 3-norbornanone ethylene acetals, i.e. spiro[1,3-dioxolane-2,2' and 2,3'-
(5′-vinylnorbornane)] was obtained. Boiling point 61-62℃/0.7mmHg n ²³ _D : 1.4918 ir (neat method): 3050cm ^-1 (C-H stretching vibration of vinyl group), 1630cm ^-1 (Stretching vibration of C=C), and C=O The stretching vibration (1730 cm ^-1 ) disappeared due to acetalization. nmr ( _CDCl3 ): 3.8-4.5τ (sextet, 1H), 4.8-5.3τ (multiplet, 2H), 6.1τ (singlet, 4H), 7.2-8.7τ (multiplet, 9H). Next, 12.0 g of the ethylene acetal obtained above
(0.067 mol) was added dropwise at room temperature to a mixed solution of 21.2 g (0.067 mol) of mercuric acetate, 60 ml of water, and 60 ml of tetrahydrofuran. After the dropwise addition was completed, the mixture was stirred for about 10 minutes, and then 65 ml of an aqueous solution of 8.2 g of sodium hydroxide was added to the resulting colorless and transparent mixture, followed by 65 ml of an aqueous solution of 1.4 g of sodium borohydride and 8.2 g of sodium hydroxide, and the mixture was stirred for 1 hour. Stir at room temperature. Mercury was removed from the reaction mixture, sodium chloride was dissolved and saturated, and the mixture was extracted three times with a benzene-ether mixture. After washing the organic layer with a small amount of saturated aqueous sodium chloride solution to remove alkaline components,
It was dried with anhydrous magnesium sulfate. After distilling off the solvent, the residue was distilled under reduced pressure to obtain 10.5 g of a colorless floral cedar-like viscous liquid (yield: 79.1
%; boiling point, 104-105℃/ _0.25mmHg ; ^n22D , 1.4970)
I got it. ir (neat method): ~3500cm ^-1 (O-H stretching vibration). The C=C stretching vibration (1630 cm ^-1 ) of the vinyl group disappeared. nmr (CDCl ₃ ): 6.1τ (singlet, 4H), 6.2–6.4τ (multiplet, 1H), 7.6τ (broad singlet, 1H), 7.3–8.9τ (multiplet, 12H). Elemental analysis (as C ₁₁ H ₁₈ O ₃ ) C% H% Calculated value 66.7 9.1 Actual value 66.5 9.6 In addition, preparative gas chromatography analysis (column packing material: silicone SE-30, column length: stainless steel 0.25φ× 90m, column temperature: 150
℃), spiro{1,3-dioxolane-
2,2′-[5′-(α-hydroxyethyl)-norbornane]} is 70% and the rest is spiro{1,3-dioxolane-2,3′-[5′-(α-hydroxyethyl)-norbornane] ]}. The endo-body/exo-body composition ratio was approximately 30/70. In addition, according to gas chromatographic analysis, the ratios of corresponding positional isomers and stereoisomers were almost the same in Production Examples 2 to 4, which will be described later. Production Example 2 Synthesis of spiro{4,5-dimethyl-1,3-dioxolane-2,2' and 2,3'-[5'-(α-hydroxyethyl)-norbornane]} 5-vinyl-2 and 3 - Spiro obtained by acetalizing norbornanone with 2,3-butanediol [4,5-dimethyl-1,3-dioxolane-2,2'- and 2,3'-(5'-vinyl-norbornane)] was treated in the same manner as in Production Example 1,
The title spiro {4,5-dimethyl-1,3-dioxolane-2,2' and 2,3'-[5'-(α-hydroxyethyl)-norbornane]} was obtained in a yield of 75.6
Obtained in %. Boiling point 109-111℃/0.1mmHg n ²³ _D : 1.4765 ir (neat method): ~3500cm ^-1 (OH stretching vibration) C=C stretching vibration (1630cm ^-1 ) of vinyl group disappears. nmr (CDCl ₃ ): 6.0~6.3τ (quartet, 2H), 6.2~6.5τ (multiplet, 1H), 7.5τ (broad singlet, 1H), 7.3τ (multiplet, 12H), 8.8~ 9.0τ (double line, 6H). Elemental analysis (as C ₁₃ H ₂₂ O ₃ ) C% H% Calculated value 69.0 9.7 Actual value 68.8 9.9 Production example 6 Spiro{1,3-dioxane-2,2' and 2,3'-[5'-(α Synthesis of spiro[1,3-dioxane-2,2' and 2,3'-(5 '-(α-hydroxy)-ethyl-norbornane)] was treated in the same manner as in Example 1 to obtain the title spiro{1,3-dioxane-2,2' and 2,3'-[5'-(α- (hydroxyethyl)-norbornane]} was obtained in a yield of 70%. Boiling point 120-124℃/0.25mmHg n ²³ _D : 1.4995 ir (neat method): ~3500cm ^-1 (OH stretching vibration) C=C stretching vibration (1630cm ^-1 ) of the vinyl group disappears. nmr ( _CDCl3 ): 6.0-6.2τ (triplet, 4H), 6.2-6.5τ (multiplet, 1H), 7.4τ (broad singlet, 1H), 7.1-9.0τ (multiplet, 14H). Elemental analysis (as C ₁₂ H ₂₀ O ₃ ) C% H% Calculated value 67.9 9.4 Actual value 67.8 9.5 Production example 4 Spiro {5,5-dimethyl-1,3-dioxane-2,2' and 2,3'- Synthesis of [5'-(α-hydroxyethyl)-norbornane] Spiro[5,5] obtained by acetalizing 5-vinyl-2 and 3-norbornanone with 2,2-dimethyl-1,3-propanediol ―
Dimethyl-1,3-dioxane-2,2' and 2,3'-(5'-vinylnorbornane)] were treated in the same manner as in Production Example 1 to produce spiro{5,5-dimethyl-1,3-dioxane. -2,2' and 2,3'-
[5'-(α-hydroxyethyl)-norbornane] was obtained in a yield of 83%. Boiling point 109-112℃/0.25mmHg n ²³ _D : 1.4915 ir (neat method): ~3500cm ^-1 (OH stretching vibration), C=C stretching vibration (1630cm ^-1 ) of vinyl group disappears. nmr (CDCl ₃ ): 6.1τ (singlet, 4H), 6.2~6.4τ (multiplet, 1H), 7.4τ (broad singlet, 1H), 7.1~8.7τ (multiplet, 12H), 9.2τ ( Single line, 6H). Elemental analysis (as C ₁₄ H ₂₄ O ₃ ) C% H% Calculated value 70.0 10.0 Actual value 70.0 9.6 Example 1 Spiro{1,3-dioxolane-2,2' and 2,3'- obtained in Production Example 1 When [5'-(α-hydroxyethyl)-norbornane] was used to formulate the following formulation, the mixture was
It became a fragrance base for musk-like men's cosmetics. Cedarwood oil 16g Terpineol 13g Methylionone 12g Bergamot oil 10g Sandalwood oil 10g β-phenylethyl alcohol 6g Cedryl acetate 5g Geranium oil 4g Cyclopentadecanolide 4g Vetiver oil 3g Musk ketone 3g Pachylily oil 3g Bois de Rose oil 3g Benzyl salicylate 3g Oakmoss oil 2g Acetal of Production Example 1 3g Total 100g Example 2 Spiro{4,5-dimethyl- obtained in Production Example 2
1,3-dioxolane-2,2' and 2,3'-
[5'-(α-Hydroxyethyl)-norbornane] was blended as follows to obtain a diyasmine fragrance composition, which became a base fragrance used in soap fragrances and toiletry products. . Phenylethyl alcohol 25g Citronellol 20g Hydroxycitronellal 12g Benzyl acetate 10g Linalool 10g Methyl dihydrodiasmonate 5g α-hexylcinnamic aldehyde 5g Diasmone 4g 10% indole/ethanol solution 2g Cyclopentadecanolide 1g 10% ethylvanillin/ethanol Liquid 1g Acetal of Production Example 2 5g Total 100g Example 3 Spiro{1,3-dioxane- obtained in Production Example 3
When 2,2' and 2,3'-[5'-(α-hydroxyethyl)-norbornane] were blended in the following formulation, a floral bouquet-like chypre-based fragrance composition was obtained, and this composition Suitable for base fragrances such as hair oil, hair spray, and hand cream. Bergamot oil 16g Linalool 10g Phenylethyl alcohol 10g Vetivenyl acetate 8g Benzyl acetate 8g Sandalwood oil 6g Methylionone 5g Rose oil 5g Coumarin 5g 10% isobutylquinoline ethanol solution 4g Diasmone 3g Oakmoss oil 3g Musk ambrette 3g Isoamyl salicylate 3g Pachylily oil 2g Methyl dihydrodiasmonate 2g Labdanum oil 2g Acetal of Production Example 3 5g Total 100g Example 4 Spiro{5,5-dimethyl- obtained in Production Example 4
1,3-dioxane-2,2' and 2,3'-
When [5'-(α-hydroxyethyl)-norbornane] was blended as follows, a citrus fragrance was obtained, and this blend could be used as a base fragrance for eau de cologne and soap. Bergamotu oil 20g Orange oil 10g Lemon oil 10g Coumarin 8g Linalyl acetate 6g Petitgrain oil 6g Phenylethyl alcohol 6g Linalool 6g Sandalwood oil 5g Orange blossom oil 5g Aromatic oil 4g Mimosa oil 3g Methyl dihydrodiasmonate 2g L-limonene 2g Methyl anthraani Rate 1g Dimethylbenzyl carbinyl acetate 1g Waniline 1g Acetal of Production Example 4 4g Total 100g

Claims (1)

[Claims] 1. The following formulas () and () [Here, R1 is a saturated hydrocarbon residue having 2 to 7 carbon atoms. ] A fragrance composition containing an α-hydroxyalkylnorbornanone acetal represented by: 2 The compound represented by the above formula () is spiro[1,3-dioxolane-2,2'-[5'-(α-
hydroxyethyl)-norbornane)],
and the compound represented by the above formula () is spiro[1,3-dioxolane-2,3'-[5'-(α-
2. The fragrance composition according to claim 1, which is hydroxyethyl)-norbornane).