JPH1135969A - Perfume composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a perfume compsn. which has a flower-like aroma that reminds of muget, and has a high lingering scent by incorporating an 4- alkoxymethyl cyclohexyl methanol. SOLUTION: 1,4-Dimethylolcyclohexane is reacted with an alkyl, a cycloalkyl, or an alkenyl halide to etherify only one hydroxyl group. Thus, an 4- alkoxymethyl cyclohexyl methanol represented by the formula (wherein R represents a 1-10C alkyl group, a 3-10C cycloalkyl group, or a 2-10C alkenyl group) is synthesized. A blended perfume having a desired compsn. is blended with the 4-alkoxymethyl cyclohexyl methanol to obtain a contemplated aromatic perfume compsn. In the formula, pref., R represents a 1-5C alkyl group or a 3-5C alkenyl group with a methyl, ethyl, isopropyl, or allyl group being particularly pref.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fragrance composition,
More specifically, the present invention relates to a perfume composition containing a specific cyclohexylmethanol used in perfumes, soaps, shampoos, hair rinses, detergents, cosmetics, hair sprays, fragrances, and the like.

[0002]

2. Description of the Related Art
Cyclohexyl alkanols are known as useful fragrance compounds. For example, Japanese Patent Publication No. 55-23242 discloses that 4-isopropenylcyclohexylmethanol or 4-isopropylcyclohexylmethanol has a flowery odor reminiscent of a lily of the valley flower, and Japanese Patent Publication No. 62-7176 discloses an α- It is described that hydroxyalkyl-4-t-alkylcyclohexane has a sandalwood-like aroma. Japanese Patent Publication No. 60-7495 discloses that various cyclohexyl alkanols have an odor eliminating action.

[0003] Among cyclohexylalkanols, some 4-alkoxymethylcyclohexylmethanols, for example, 4-methoxymethylcyclohexylmethanol, are disclosed in JP-A-7-233113 as a raw material for nematic liquid crystal materials. Methylcyclohexylmethanol is J. Chem. Soc. C (1971), No. 15, 2730-2
Although it is disclosed as a reaction intermediate on page 731, the odor of each is not described at all.

[0004] The fragrance of compounds used in fragrances is generally quite different due to slight differences in structure. Therefore, it is extremely important to synthesize various compounds and examine their fragrances in order to obtain new fragrances. is there.

[0005] Further, there are various demands for a compounded fragrance material such as low cost, chemical stability, and a new fragrance. Conventionally, many fragrance materials having a flowery fragrance are known, but the trend of fragrance is constantly changing with the times, and finding a new fragrance material is extremely important in formulating.

Accordingly, an object of the present invention is to provide a novel fragrance composition having a flowery scent.

[0007]

Under these circumstances, the present inventors have synthesized various 4-alkoxymethylcyclohexylmethanols and studied their aroma and blending system. The present inventor has found that the perfume composition contained therein has an excellent flower-like odor reminiscent of muge, has an excellent residual scent, and is useful for perfuming a wide range of toiletry products, and has completed the present invention.

That is, the present invention provides a fragrance composition containing a 4-alkoxymethylcyclohexylmethanol represented by the general formula (I).

[0009]

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Wherein R is an alkyl group having 1 to 10 carbon atoms,
A cycloalkyl group having 3 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms is shown. )

[0011]

Embodiments of the present invention will be described below in detail.

In the 4-alkoxymethylcyclohexylmethanols represented by the general formula (I) according to the present invention, the alkyl group having 1 to 10 carbon atoms represented by R is a methyl group, an ethyl group, a propyl group, Isopropyl group, butyl group, t-butyl group, 1-methylpropyl group,
2-methylpropyl group, pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. As the cycloalkyl group,
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like, and as the alkenyl group having 2 to 10 carbon atoms, an allyl group,
Butenyl, 2-methyl-2-propenyl, hexenyl, octenyl and the like. Among these,
An alkyl group having 1 to 5 carbon atoms or an alkenyl group having 3 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, an isopropyl group or an allyl group is particularly preferable.

The 4-alkoxymethylcyclohexylmethanols represented by the general formula (I) are represented by the formula (II)

[0014]

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(The steric configuration of the two methylol groups of the cyclohexane ring in the formula may be any of cis, trans, or a mixture of cis and trans.)
It is obtained by etherifying only one hydroxyl group of dimethylolcyclohexane (hereinafter abbreviated as 1,4-dimethylolcyclohexane (II)).

In the etherification reaction, for example, as shown in the following reaction formula, 1,4-dimethylolcyclohexane (II) and an alkyl, cycloalkyl or alkenyl halide represented by the general formula (III) are used in an experiment. A method according to the general etherification reaction described in Kagaku Koza (Maruzen), Vol. 20, p.

[0017]

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(Wherein, R represents the above-mentioned meaning and X represents a halogen atom.) According to this method, for example, tetrahydrofuran (TH
F) or 1,4-dimethylolcyclohexane (toluene solvent) at a reaction temperature of 10 to 80 ° C. in the presence of 0.8 to 1.2 mol times of sodium hydride to 1,4-dimethylolcyclohexane (II) at a reaction temperature of 10 to 80 ° C. A reaction mixture is obtained by reacting an alkyl, cycloalkyl or alkenyl halide represented by the general formula (III) in an amount of 0.8 to 2.4 times the molar amount of II) for 30 minutes to 12 hours to obtain a reaction mixture, which is further purified by precision distillation or column chromatography. Thus, the desired monoether compound represented by the general formula (I) can be obtained.

The thus obtained general formula (I)
The 4-alkoxymethylcyclohexylmethanol represented by the formula (1) has an excellent flower-like odor reminiscent of mugue, and the fragrance composition of the present invention containing such 4-alkoxymethylcyclohexylmethanol is soap, shampoo, etc. , Rinsing, detergent, cosmetics, spray products, fragrance and the like.

The fragrance composition of the present invention is obtained by blending a compound represented by the general formula (I) with a compounded fragrance having a desired composition. The amount of the compound represented by the general formula (I) in the composition of the present invention varies depending on the type of the compounded flavor, the type of the intended flavor, the strength of the flavor, and the like.
90% by weight is preferred, and 0.5 to 50% by weight is particularly preferred.

The other components in the fragrance composition of the present invention are not particularly limited, but all of the components that are blended in a general fragrance composition can be blended in the fragrance composition of the present invention.

[0022]

The present invention will be described in more detail with reference to the following Synthesis Examples and Examples, which should not be construed as limiting the present invention. The parts in the examples are on a weight basis unless otherwise specified.

Synthesis Example 1 Production of 4-methoxymethylcyclohexylmethanol

[0024]

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500 ml with a Dimroth cooler and thermometer
8.3 g of 63% sodium hydride (0.3 g
5 mol) was suspended in 100 ml of anhydrous THF and the temperature was raised to 60 ° C. A solution of 50 g (0.35 mol) of 1,4-dimethylolcyclohexane in 100 ml of anhydrous THF was added, followed by addition of 49 g (0.35 mol) of methyl iodide, followed by stirring at 60 ° C. for 1 hour. After distilling off THF, 50 ml of ice water was added and extracted with ether. The organic layer was washed with water until neutral, the solvent was distilled off, and the residue was distilled to obtain 41 g of a reaction mixture. The reaction mixture was subjected to silica gel chromatography (ethyl acetate / hexane = 3/7).
(Volume ratio)) to give 20 g of the title compound (36% yield).

¹ H-NMR (CDCl ₃ , 200 MHz), δ; 0.80
~ 1.10 (3H, m), 1.30 ~ 2.00 (7H, m), 2.00 ~ 2.30 (1H, m, O
H), 3.20 (2H, d , J = 6.4Hz, CH 2), 3.32 (3H, s, Me), 3.43 (2
H, bd, CH ₂ ), IR (KBr, neat, cm ⁻¹ ); 3404, 2920, 2856, 1450, 138
6, 1192, 1118, 1064, 1036 The obtained compound had a flowery, slightly woody nuance and an aroma reminiscent of mugue.

Synthesis Example 2 Production of 4-ethoxymethylcyclohexylmethanol

[0028]

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200 ml with a Dimroth cooler and thermometer
1.7 g of 63% sodium hydride (6.
9 × 10 ⁻² mol) was suspended in 50 ml of anhydrous THF, and the temperature was raised to 60 ° C. 1,4-Dimethylolcyclohexane 10 g (6.9
(× 10 ⁻² mol) in 20 ml of anhydrous THF was added, followed by addition of 7.6 g (6.9 × 10 ⁻² mol) of ethyl bromide, followed by stirring at 60 ° C. overnight. After distilling off THF, add 25 ml of ice water.
The mixture was extracted with ether. The organic layer was washed with water until neutral, the solvent was distilled off, and the residue was distilled to obtain 14 g of a reaction mixture. The reaction mixture was purified by silica gel chromatography (ethyl acetate / hexane = 2/8 (volume ratio)) to obtain 3 g of the title compound (yield 27%).

¹ H-NMR (CDCl ₃ , 200 MHz), δ; 0.80
~ 1.10 (3H, m), 1.19 (3H, t, J = 7.1Hz, Me), 1.30 ~ 1.95 (7
H, m), 1.85~2.00 (1H , m, OH), 3.22 (2H, d, J = 6.7Hz, CH 2),
_{3.46 (2H, q, CH 2} ), 3.35~3.60 (2H, m, CH 2) IR (KBr, neat, cm -1); 3428, 2980, 2920, 2852, 145
0, 1380, 1356, 1214, 1110, 1064, 1036 The resulting compound had a floral, slightly woody nuance and an aroma reminiscent of muguet.

Synthesis Example 3 Production of 4-isopropoxymethylcyclohexylmethanol

[0032]

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200 ml with a Dimroth cooler and thermometer
1.7 g of 63% sodium hydride (6.
9 × 10 ⁻² mol) was suspended in 50 ml of anhydrous THF, and the temperature was raised to 60 ° C. 1,4-Dimethylolcyclohexane 10 g (6.9
× 10 ^-2 mol) in 20 ml of anhydrous THF was added, followed by 12 g (6.9 × 10 ^-2 mol) of ^2- propane iodide.
And stirred at 60 ° C. overnight. After distilling off THF, add ice water
25 ml was added and extracted with ether. The organic layer was washed with water until neutral, the solvent was distilled off, and the residue was distilled to obtain 14 g of a reaction mixture. The reaction mixture was purified by silica gel column chromatography (ethyl acetate / hexane = 2/8 (volume ratio)) to obtain 3.1 g of the title compound (yield: 42%).

¹ H-NMR (CDCl ₃ , 200 MHz), δ; 0.80
~ 1.10 (3H, m), 1.17 (6H, d, J = 6.2Hz, 2Me), 1.30 ~ 1.95 (8
H, m), 3.21 (2H , d, J = 6.4Hz, CH 2), 3.35~3.60 (3H, m) IR (KBr, neat, cm -1); 3370, 2968, 2920, 2854, 232
6, 1452, 1371, 1338, 1197, 1155, 1125, 1080, 1059,
1035 The resulting compound had a slightly Oris-like nuance and a scent reminiscent of Mugue.

Synthesis Example 4 Production of 4-allyloxymethylcyclohexylmethanol

[0036]

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200 ml with a Dimroth cooler and thermometer
1.7 g of 63% sodium hydride (6.
9 × 10 ⁻² mol) was suspended in 50 ml of anhydrous THF, and the temperature was raised to 60 ° C. 1,4-Dimethylolcyclohexane 10 g (6.9
(× 10 ⁻² mol) in 20 ml of anhydrous THF was added, followed by addition of 11.7 g (6.9 × 10 ⁻² mol) of allyl iodide, followed by stirring at 60 ° C. overnight. After distilling off THF, add 25 ml of ice water.
The mixture was extracted with ether. The organic layer was washed with water until neutral, the solvent was distilled off, and the residue was distilled to obtain 9.0 g of a reaction mixture. The reaction mixture was chromatographed on silica gel (ethyl acetate /
Hexane = 2/8 (volume ratio)) to give 3.8 g of the title compound (yield 45%).

¹ H-NMR (CDCl ₃ , 200 MHz), δ; 0.80
~ 1.20 (3H, m), 1.30 ~ 2.10 (8H, m), 3.25 (2H, d, J = 6.7Hz,
CH ₂ ), 3.43 (2H, d, J = 6.2Hz, CH ₂ ), 3.95 (2H, d, J = 5.7Hz, CH
_{2), 5.10~5.35 (2H, m} , CH 2), 5.80~6.05 (1H, m, CH) IR (KBr, neat, cm -1); 3380, 3084, 3016, 2920, 285
6, 2072, 1646, 1450, 1422, 1402, 1350, 1268, 1210,
1086, 1070, 1036 The resulting compounds had a flowery, slightly grassy Oris-like nuance and a scent reminiscent of muguet.

Example 1 To 800 parts of the following floral-type blended perfume, 200 parts of 4-methoxymethylcyclohexylmethanol obtained in Synthesis Example 1 was added to obtain a soft and voluminous mugue-type blended flavor. Was.

[0040] Example 2 To 800 parts of the following perfume for detergent was added 4-
By adding 200 parts of ethoxymethylcyclohexylmethanol, a detergent fragrance having softness, cleanliness, floweriness, volume and sweetness was obtained.

[0041] Example 3 By adding 300 parts of 4-isopropoxymethylcyclohexylmethanol obtained in Synthesis Example 3 to 700 parts of the following floral-type blended flavor, a floral-type blended flavor having softness, volume, and sweetness was obtained. Was done.

[0042] Example 4 To 800 parts of the following perfume for detergent was added 4-
By adding 200 parts of allyloxymethylcyclohexylmethanol, a detergent fragrance having softness, cleanliness, floweriness, volume and sweetness was obtained.

[0043]

[0044]

According to the present invention, a novel fragrance composition exhibiting excellent fragrance can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Nao Toi 2-1-3 Bunka, Sumida-ku, Tokyo Inside Kao Corporation Research Laboratory (72) Inventor Kazuyuki Fukuda 2-1-3 Bunka, Sumida-ku, Tokyo Kao Corporation Research Laboratory

Claims (3)

[Claims] 1. A fragrance composition comprising a 4-alkoxymethylcyclohexylmethanol represented by the general formula (I). Embedded image (Wherein, R is an alkyl group having 1 to 10 carbon atoms, 3 to 10 carbon atoms)
A cycloalkyl group or an alkenyl group having 2 to 10 carbon atoms. ) 2. The fragrance composition according to claim 1, wherein R is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 3 to 5 carbon atoms. 3. The fragrance composition according to claim 1, wherein R is a methyl group, an ethyl group, an isopropyl group or an allyl group.