JPH1171312A - New cyclohexylalkanols and perfume composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compounds having floral, woody, muguet fragrance excellent in lingering perfume useful for a perfuming agent for toiletries, etc. SOLUTION: The compound is expressed by the formula (R<1> to R<4> are each an 1 to 3C alkyl, H; R<5> is an 1 to 3C alkyl), for example, 1-(4- methoxymethylcyclohexyl)-1-ethanol. The compound of the formula, for example when R<3> , R<4> are each H, is obtained by changing the hydroxy group of p- bromobenzyl alcohol into alcoholate by reacting with a proper base such as sodium hydride, sodium hydroxide, potassium hydroxide, etc., then transferring the compound into ether by reacting with an alkylating agent such as alkyl sulfate, alkylhalide, etc. Reacting the compound with magnesium metal into arylmagnesium bromide, carrying out the reaction with a carbonyl compound to obtaining hydroxyether. The corresponding cyclohexylalkanol is obtained by hydrogenating the compound with a proper catalyst, preferably a catalyst containing ruthenium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel cyclohexylalkanol having a floral, woody and mugue fragrance excellent in lingering odor and useful as a perfuming ingredient for toiletries and the like, and a fragrance composition containing the same.

[0002]

2. Description of the Related Art
Useful perfume compounds are known for cyclohexylalkanols. For example, Japanese Patent Publication No. 55-23242 discloses 4
-Isopropylcyclohexylmethanol has a flowery odor reminiscent of lily of the valley flowers.
No. 7176 describes that 4-t-butylcyclohexylmethanol has a sandalwood-like aroma. Japanese Patent Publication No. Sho 60-7495 describes that various cyclohexylmethanols have an odor eliminating action.

[0003] However, the fragrance of compounds is generally completely different due to slight differences in structure. Therefore, it is extremely important to synthesize various compounds and study their fragrances in order to obtain a new fragrance.

[0004] There are various demands for compounding fragrance materials, such as low cost, chemical stability, and new flavor. Conventionally, many fragrance materials having a muge-like scent have been known, but a material that is stable and has excellent residual scent properties has been demanded. Therefore, an object of the present invention is to provide a novel compound which is useful as a fragrance material which is stable and has excellent residual scent properties.

[0005]

Under such circumstances, the present inventors have synthesized various 4-alkoxyalkylcyclohexylalkanols to solve the above-mentioned problems,
As a result of diligent examination of the fragrance and the blend system, it has floral, woody and mugue fragrances with excellent residual scent,
The present inventors have found novel 4-alkoxyalkylcyclohexylalkanols useful for flavoring a wide range of toiletry products, and have completed the present invention.

That is, the present invention provides a novel cyclohexylalkanol represented by the general formula (I) and a fragrance composition containing the novel cyclohexylalkanol.

[0007]

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(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and represent an alkyl group having 1 to 3 carbon atoms or a hydrogen atom).
However, this excludes the case where all of R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms. R ⁵ represents an alkyl group having 1 to 3 carbon atoms. )

[0009]

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

The novel cyclohexylalkanols of the present invention are represented by the above general formula (I). In the general formula (I), the number of carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ is 1 Examples of the alkyl groups (1) to (3) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

In the general formula (I), R ¹ and R ² are preferably a hydrogen atom or a methyl group, and R ³ and R ⁴
Is preferably a hydrogen atom, a methyl group or an ethyl group, particularly a hydrogen atom or a methyl group, and a preferable R ⁵ is a methyl group or an ethyl group, particularly a methyl group.

The process for producing the novel cyclohexyl alkanols of the present invention is described below. In the case of a compound in which R ³ and R ⁴ are both hydrogen atoms in the general formula (I), the compound can be produced, for example, by a method represented by the following reaction formula.

[0013]

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(Wherein X represents a halogen atom, and R ¹ , R ²
And R ⁵ are as defined above. That is, the hydroxyl group of p-bromobenzyl alcohol (II) is converted to an alcoholate with an appropriate base such as sodium hydride, sodium hydroxide, potassium hydroxide or the like, which is converted to an ether with an alkylating agent such as an alkyl sulfate or an alkyl halide. Body (III). Then, using metal magnesium, the compound is converted into arylmagnesium bromide, and reacted with various carbonyl compounds (IV) to obtain a hydroxyether compound (V). It can then be hydrogenated with a suitable catalyst, preferably a ruthenium-containing catalyst, to give the corresponding cyclohexylalkanol (VI).

When R ³ is not a hydrogen atom and R ⁴ is a hydrogen atom in the general formula (I), it can be produced, for example, by the method shown in the following reaction formula.

[0016]

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(In the formula, R ^{3 ′} represents an alkyl group having 1 to 3 carbon atoms, and R ¹ , R ² , R ⁵ and X have the same meaning as described above.) That is, p-bromobenzylalkylcarbinol (V
II) the hydroxyl group of sodium hydride, sodium hydroxide,
The alcoholate is converted to an alcoholate with an appropriate base such as potassium hydroxide, which is converted to an ether (VIII) with an alkylating agent such as an alkyl sulfate or an alkyl halide. Then, it is converted into arylmagnesium bromide using metallic magnesium, and reacted with various carbonyl compounds (IV) to obtain a hydroxyether compound (IX). It can then be hydrogenated with a suitable catalyst, preferably a ruthenium-containing catalyst, to give the corresponding cyclohexylalkanol (X).

In the case where both R ³ and R ⁴ in formula (I) are not hydrogen atoms, they can be produced, for example, by the method shown in the following reaction formula.

[0019]

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(In the formula, R ^{4 ′} represents an alkyl group having 1 to 3 carbon atoms, and R ¹ , R ² , R ⁵ , R ^{3 ′} and X have the same meaning as described above.) That is, p-bromo Benzylalkyl carbinol
The hydroxyl group of (XI) is protected with a suitable protecting group, for example, dihydropyran or the like to obtain a compound (XII), which is then converted to an arylmagnesium bromide using metal magnesium,
The compound is reacted with various carbonyl compounds (XIII) to obtain a hydroxyether compound (XIV). Next, the hydroxyl group is converted to an alcoholate with an appropriate base such as sodium hydride, sodium hydroxide, potassium hydroxide or the like, which is converted to an ether form (XV) with an alkylating agent such as an alkyl sulfate or an alkyl halide. The tetrahydropyranyl ether group of the ether compound (XV) is removed in a solvent such as methanol in the presence of a suitable acid catalyst such as sulfuric acid, phosphoric acid, p-toluenesulfonic acid to obtain a hydroxy ether compound (XVI). Hydrogenation with a suitable catalyst, preferably a ruthenium-containing catalyst, gives the corresponding cyclohexylalkanol (XVII).

In the general formula (I), those in which R ¹ and R ³ are methyl groups and R ² and R ⁴ are hydrogen atoms can be produced more easily by, for example, a method shown by the following reaction formula. .

[0022]

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(Wherein, R ⁵ has the same meaning as described above.) That is, the corresponding diol is obtained by hydrogenating 1,4-diacetoxybenzene (XVIII) with a ruthenium-containing catalyst.
(XIX). The hydroxyl group of this diol is converted to an alcoholate with 0.5 equivalent of a base, for example, sodium hydride, sodium hydroxide, potassium hydroxide or the like, and this is converted to an ether (XX) with an alkylating agent such as an alkyl sulfate or an alkyl halide. 1
-{4- (1-alkoxyethyl) cyclohexyl}-
1-ethanol can be obtained.

In the general formula (I), R ¹ , R ² , R ³
And those in which all of R ⁴ are methyl groups can be produced more easily, for example, by the following method.

[0025]

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(Wherein R ⁵ has the same meaning as described above.) That is, the corresponding diol (XXII) is obtained by hydrogenating α, α′-dihydroxy-p-diisopropylbenzene (XXI) with a ruthenium-containing catalyst. Get. The hydroxyl group of this diol is converted to an alcoholate with 0.5 equivalent of a base, for example, sodium hydride, sodium hydroxide, potassium hydroxide or the like, and this is converted to an ether (XXIII) with an alkylating agent such as an alkyl sulfate or an alkyl halide. By doing so, the desired 2- {4- (2-alkoxy-2-propyl) cyclohexyl} -2-propanol can be obtained.

The cyclohexyl alkanols represented by the general formula (I) of the present invention obtained by the above-mentioned production method have a flower-like, tree-like, mugue-like odor and an excellent lingering odor. Therefore, it can be used alone or in combination with other components as a flavoring component such as soap, shampoo, rinse, detergent, cosmetics, spray product, fragrance and the like.

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

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following examples, Me is a methyl group,
Et represents an ethyl group.

Example 1 Synthesis of 1- (4-methoxymethylcyclohexyl) -1-ethanol

[0031]

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200 ml with Dimroth cooler and thermometer
4.9 g of 60% sodium hydride (0.
13 mol) and 60 ml of tetrahydrofuran (THF)
While stirring, 19 g of 4-bromobenzyl alcohol (0.11
Mol) was dissolved in 30 ml of THF and added dropwise. After the addition, 18 g (0.13 mol) of methyl iodide was slowly added dropwise, and the mixture was stirred overnight at room temperature. The reaction was heated to 100 ° C., THF was distilled off, the mixture was cooled to room temperature, and water was added to decompose excess sodium hydride. Ethyl acetate was added to the reaction product, washed with water until the organic layer became neutral, and the solvent was distilled off to obtain 19 g of a methyl ether compound (yield: 92%).

200 ml with Jimroth condenser and thermometer
1.43g of magnesium powder (5.9 x
10 ^-2 mol) and 20 ml of dehydrated THF were added, and a solution of 10 g (5.0 x 10 ^-2 mol) of the methyl ether compound synthesized in the above manner in 40 ml of dehydrated THF was added dropwise with stirring at a rate at which THF slowly refluxed. After the dropwise addition, the mixture was refluxed for 30 minutes to prepare a Grignard reagent, which was returned to room temperature. Where acetaldehyde
2.6 g (6.0 × 10 ^-2 mol) was added dropwise and stirred at room temperature for 12 hours. Saturated aqueous ammonium chloride was added to the reaction product, ethyl acetate was added, and the mixture was washed with water until the organic layer became neutral, and the solvent was distilled off to obtain 7.3 g of a reaction mixture. The reaction mixture is subjected to silica gel column chromatography (ethyl acetate 1.5 / hexane 8.5).
Then, 6.43 g of a hydroxy ether compound was obtained (yield: 78).
%).

In a 300 ml pressure-resistant reactor, 6.3 g (3.8 × 10 ^-2 mol) of the hydroxyether compound synthesized by the above method, Ru /
0.6 g of C was suspended in 100 ml of isopropyl alcohol (IPA) and stirred for 3 days under a hydrogen pressure of 90 ° C./0.5 MPa. The catalyst was filtered from the reaction solution, and the solvent was distilled off to obtain 4.9 g of a reaction mixture. The reaction mixture was purified by silica gel column chromatography (ethyl acetate 1 / hexane 9) to give the desired 1-
3.5 g of (4-methoxymethylcyclohexyl) -1-ethanol were obtained (yield 54%, total yield 38%).

¹ H-NMR (CDCl ₃ , 200 MHz), δ: 0.80
~ 2.10 (11H, m), 1.17 (3H, d, J = 6.4Hz, Me), 3.32 (2H, d, J =
_{6.4Hz, CH 2), 3.33 (} 3H, s, Me), 3.50~3.80 (1H, m, CH) IR (KBr, neat, cm -1): 3412, 2926, 2746, 1665, 1
452, 1395, 1338, 1218, 1194, 1092, 933, 870 The obtained compound had a woody, flowery and light muge-like odor.

Example 2 Synthesis of 2- (4-methoxymethylcyclohexyl) -2-propanol

[0037]

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200 ml with Jimroth condenser and thermometer
1.7g magnesium powder (7.2 x
10 ^-2 mol) and 20 ml of dehydrated THF were added, and a solution of 12 g (5.9 x 10 ^-2 mol) of the methyl ether compound synthesized in Example 1 in 40 ml of dehydrated THF was added dropwise with stirring at a rate at which THF slowly refluxed. After the dropwise addition, the mixture was refluxed for 30 minutes to prepare a Grignard reagent, and the temperature was returned to room temperature. Here, dehydrated acetone
4.2 g (7.2 × 10 ^-2 mol) was added dropwise and stirred at room temperature for 2 hours. To the reaction product was added a saturated aqueous ammonium chloride solution, ethyl acetate was added, and the mixture was washed with water until the organic layer became neutral, and the solvent was distilled off to obtain 10 g of a reaction mixture. Silica gel column chromatography of the reaction mixture (ethyl acetate 1.5 / hexane 8.5)
To give 7.3 g of a hydroxy ether compound (yield 80
%).

In a 300 ml pressure-resistant reactor, 7.3 g (4.0 × 10 ^-2 mol) of the hydroxyether compound synthesized by the above method, Ru /
0.7 g of C was suspended in 150 ml of IPA and stirred for 3 days under a hydrogen pressure of 90 ° C./0.5 MPa. After filtering the catalyst from the reaction solution and evaporating the solvent, 3.3 g of a reaction mixture was obtained. The reaction mixture was purified by silica gel column chromatography (ethyl acetate 1 / hexane 9) to obtain 1.7 g of 2- (4-methoxymethylcyclohexyl) -2-propanol (30% yield, 22% overall yield).

¹ H-NMR (CDCl ₃ , 200 MHz), δ: 0.80
~ 2.10 (11H, m), 1.16 (6H, s, 2Me), 3.18 (2H, d, J = 6.6Hz, C
_{H 2), 3.34 (3H,} s, Me) IR (KBr, neat, cm -1): 3472, 2932, 2860, 1872, 145
2, 1568, 1197, 1149, 1110, 954, 912 The resulting compound had a woody odor.

Example 3 4- (1-methoxyethyl) cyclohexylmethanol

[0042]

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500 ml with a Dimroth cooler and thermometer
11.6 g of 60% sodium hydride (0.
30 mol) and 150 ml of THF were added, and 50 g (0.25 mol) of 4-bromo-α-methylbenzyl alcohol was dissolved in 100 ml of THF and added dropwise with stirring. After the addition, 42 g (0.30 mol) of methyl iodide was slowly added dropwise while paying attention to the generation of gas, and the mixture was stirred overnight at room temperature. Heat the reaction to 100 ° C,
After distilling off THF, the mixture was cooled to room temperature and water was added to decompose excess sodium hydride. Ethyl acetate was added to the reaction product, washed with water until the organic layer became neutral, and the solvent was distilled off to obtain 53 g of a methyl ether compound (yield 93%).

In a 200 ml four-necked flask equipped with a Dimroth condenser, a thermometer and a gas inlet tube, magnesium powder was added.
1.7 g (7.2 × 10 ^-2 mol) and 50 ml of dehydrated THF are added, and while stirring, 12 g of the methyl ether compound synthesized by the above method.
A solution of (5.6 × 10 ⁻² mol) in 30 ml of dehydrated THF was added dropwise at a rate at which THF slowly refluxed. After the dropwise addition, the mixture was refluxed for 30 minutes to prepare a Grignard reagent, which was returned to room temperature. Here, formalin gas generated by decomposing paraformaldehyde was introduced and stirred at room temperature for 2 hours. To the reaction product was added a saturated aqueous ammonium chloride solution, and ethyl acetate was added. The mixture was washed with water until the organic layer became neutral, and the solvent was distilled off to obtain 8.5 g of a reaction mixture. The reaction mixture was purified by silica gel column chromatography (ethyl acetate 2 / hexane 8) to obtain a hydroxyether derivative 7.5 g (80% yield).

In a 300 ml pressure-resistant reactor, 7.5 g (4.3 × 10 ^-2 mol) of the hydroxyether compound synthesized by the above method, Ru /
0.75 g of C was suspended in 150 ml of IPA and stirred at 90 ° C./0.5 MPa hydrogen pressure for 7 days. After filtering the catalyst from the reaction solution and evaporating the solvent, 3.3 g of a reaction mixture was obtained. The reaction mixture was purified by silica gel column chromatography (ethyl acetate 1.5 / hexane 8.5) to give the desired 4- (1-methoxyethyl).
1.5 g of cyclohexylmethanol was obtained (yield 20%, total yield 15%).

¹ H-NMR (CDCl ₃ , 200 MHz), δ: 0.80
~ 2.10 (11H, m), 1.09 (3H, d, J = 6.4Hz, Me), 2.90 ~ 3.30
(H, m, CH), 3.32 (3H, s, Me), 3.56 (2H, bd, J = 6.2Hz, CH ₂ ) IR (KBr, neat, cm ^-1 ): 3412,2926,2134,1938, 1
647, 1452, 1380, 1191, 1086, 960, 918, 897,840, 66
6 The resulting compound had a floral, woody, and light muge-like odor.

Example 4 4- (1-ethoxyethyl) cyclohexylmethanol

[0048]

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Dimroth cooler, 500ml with thermometer
11.6 g of 60% sodium hydride (0.
30 mol) and 150 ml of THF were added, and 50 g (0.25 mol) of 4-bromo-α-methylbenzyl alcohol was dissolved in 100 ml of THF and added dropwise with stirring. After dropping, 33 g (0.30 mol) of ethyl bromide was slowly dropped while paying attention to gas generation, and the mixture was stirred overnight at room temperature. The reaction was heated to 100 ° C and T
After distilling off HF, the mixture was cooled to room temperature and water was added to decompose excess sodium hydride. Ethyl acetate was added to the reaction product, washed with water until the organic layer became neutral, and the solvent was distilled off to obtain 50 g of an ethyl ether compound (yield 87%).

EXAMPLE 3 10 g of the obtained ethyl ether compound was used.
By reacting with formalin gas by the method described and hydrogenating, 3 g of desired 4- (1-ethoxyethyl) cyclohexylmethanol was obtained (total yield: 32%).

¹ H-NMR (CDCl ₃ , 200 MHz), δ: 0.80
~ 2.10 (11H, m), 1.09 (3H, d, J = 6.2Hz, Me), 1.18 (3H, t, J =
6.1Hz, Me), 3.12 (1H, dq, J = 6.2Hz, CH), 3.20-3.70 (4H, m,
CH ₂ ) IR (KBr, neat, cm ^-1 ): 3424, 2974, 2920, 2866, 2
320, 1578, 1452, 1377, 1338, 1200, 1104,1035, 975,
948, 897, 843, 792 The resulting compound had a floral, woody, and light muge-like odor.

Example 5 1- {4- (1-methoxyethyl) cyclohexyl}-
1-Production of ethanol

[0053]

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In a 500 ml pressure-resistant reactor, 30 g (0.19 mol) of 1,4-diacetylbenzene and 1.5 g of Ru / C were suspended in 250 ml of isopropyl alcohol, and the mixture was stirred under a hydrogen pressure of 90 ° C./0.6 MPa for 3 days. The catalyst was filtered from the reaction solution, and after evaporating the solvent, 26 g of a reaction mixture was obtained. The reaction mixture is subjected to silica gel column chromatography (ethyl acetate 3 / hexane 7).
Then, 16 g of 1- {4- (1-hydroxyethyl) cyclohexyl} -1-ethanol was obtained (63% yield).

300 ml with Jimroth condenser and thermometer
3.7 g of 63% sodium hydride (9.
4 × 10 ^-2 mol) was suspended in 60 ml of anhydrous THF, and 16 g (9.4 × 10 ^-2 mol) of the diol obtained above was suspended in 30 ml of anhydrous T
Add the solution dissolved in HF, then add 20g of methyl iodide
(0.14 mol) and stirred at 60 ° C. for 1 hour. After distilling off THF, 50 ml of ice water was added and extracted with ethyl acetate. The organic layer was washed with water until neutral, and the solvent was distilled off, followed by distillation to obtain 16 g of a reaction mixture. The reaction mixture was purified by silica gel column chromatography (ethyl acetate 3 / hexane 17) to obtain 5.4 g of the desired 1- {4- (1-methoxyethyl) cyclohexyl} -1-ethanol (46% yield, Overall yield 29%).

¹ H-NMR (CDCl ₃ , 200 MHz), δ: 0.80
~ 2.10 (11H, m), 1.15 (3H, d, J = 6.2Hz, Me), 1.20 (3H, d, J
= 6.2Hz, Me), 3.23 (1H, m, CH), 3.32 (3H, s, Me), 3.75 (1H,
m, CH) IR (KBr, neat, cm ^-1 ): 3432, 2932, 1456, 1376, 119
2, 1096 The resulting compound had a flower-like, mugue-like odor.

Example 6 1- {4- (1-methoxypropyl) cyclohexyl}
-1-ethanol

[0058]

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200 ml with Dimroth condenser and thermometer
, 25 g (0.12 mol) of 4-bromo-α-methylbenzyl alcohol, dihydropyran (DH
P) 11 g, paratoluenesulfonic acid 2 g, methylene chloride
100 ml was added and the mixture was stirred at room temperature overnight. The reaction mixture was cooled to 0 ° C., saturated aqueous sodium bicarbonate and ethyl acetate were added, and the mixture was washed with water until the organic layer became neutral.
I got The reaction mixture was purified by silica gel column chromatography (ethyl acetate 0.5 / hexane 9.5) to obtain 23 g of tetrahydropyranyl ether (67% yield).

11.5 g of tetrahydropyranyl ether (4.
1 × 10 ⁻² mol) was prepared in the same manner as in Example 1 to prepare a Grignard reagent, and 2.8 g of propionaldehyde was reacted. After purifying the obtained reaction mixture, sodium hydride
After methylation with 1.2 g (2.9 × 10 ^-2 mol) and 4.15 g of methyl iodide, the tetrahydropyranyl ether group was removed with 40 ml of paratoluenesulfonic acid in methanol. After neutralization with saturated aqueous sodium bicarbonate, the mixture was extracted with ethyl acetate. The obtained organic layer was washed with saturated saline, and the solvent was distilled off. 2.6 g of the methyl ether compound obtained by purification by silica gel column chromatography (ethyl acetate 1 / hexane 9) was hydrogenated and purified in the same manner as in Example 1 to give the desired compound.
-{4- (1-methoxypropyl) cyclohexyl}-
0.8 g of 1-ethanol was obtained (total yield: 7%).

¹ H-NMR (CDCl ₃ , 200 MHz), δ: 0.80
~ 2.10 (11H, m), 1.90 (3H, t, J = 6.2Hz, Me), 1.18 (3H, d, J
= 6.2Hz, Me), 2.80-3.25 (1H, m, CH), 3.35 (3H, s, Me), 3.5
0 to 3.90 (1H, m, CH) IR (KBr, neat, cm ^-1 ): 3466, 2932, 2452, 1578, 1
455, 1374, 1341, 1095, 936, 897, 675, 582 The obtained compound had a floral and mugue-like aroma.

Example 7 2- {4- (1-methoxyethyl) cyclohexyl}-
2-propanol

[0063]

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The desired 2- {4- (1-methoxyethyl) cyclohexyl}-was obtained in the same manner as in Example 3 except that anhydrous acetone was used instead of formalin gas.
2-propanol was obtained (36% overall yield).

¹ H-NMR (CDCl ₃ , 200 MHz), δ: 0.80
~ 2.20 (11H, m), 1.11 (3H, d, J = 6.2Hz, Me), 1.18 (6H, s, 2
Me), 3.02 (1H, q, J = 6.2 Hz, CH), 3.34 (3H, s, Me) IR (KBr, neat, cm ^-1 ): 3466, 2926,
2158, 1635, 1560, 1455, 1
380, 1197, 1110, 912, 849 The resulting compound had a woody and sandalwood-like aroma.

Example 8 4- (1-Methyl-1-methoxyethyl) cyclohexylmethanol

[0067]

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Dimroth cooler, 30 with thermometer
20 g (0.11 mol) of 4-bromobenzyl alcohol, 10 g of DHP, 2 g of paratoluenesulfonic acid, and 100 ml of methylene chloride were added to a 0 ml four-necked flask, and the mixture was stirred at room temperature overnight. The reaction was cooled to 0 ° C. and saturated aqueous sodium bicarbonate,
Ethyl acetate was added, and the mixture was washed with water until the organic layer became neutral, and the solvent was distilled off to obtain 30 g of a reaction mixture. The reaction mixture was purified by silica gel column chromatography (ethyl acetate 0.5 / hexane 9.5), and tetrahydropyranyl ether 17 g
Was obtained (yield 57%).

200 ml with a Dimroth condenser and thermometer
1.7g of magnesium powder (7.2 x
10 ^-2 mol) and 20 ml of dehydrated THF were added, and 17 g of tetrahydropyranyl ether (6.
A solution of 30 ml of dehydrated THF (1 × 10 ^-2 mol) was added dropwise at a rate at which THF slowly refluxed. After the dropwise addition, the mixture was refluxed for 30 minutes to prepare a Grignard reagent, which was returned to room temperature. 4.2 g (7.2 × 10 ^-2 mol) of anhydrous acetone was added dropwise thereto, and the mixture was stirred at room temperature for 2 hours. Saturated aqueous ammonium chloride was added to the reaction mixture, ethyl acetate was added, and the mixture was washed with water until the organic layer became neutral, and the solvent was distilled off to obtain 19 g of a reaction mixture. The reaction mixture was subjected to silica gel column chromatography (ethyl acetate 1.5 / hexane).
8.5) to give 11 g of alcohol (yield 65).
%).

200 ml with Dimroth condenser and thermometer
1.9 g of 60% sodium hydride (5.
1 × 10 ⁻² mol) was suspended in 25 ml of anhydrous THF, and a solution of 11 g (4.2 × 10 ⁻² mol) of the alcohol obtained above in 25 ml of anhydrous THF was added thereto.
7.2 g (4.2 × 10 ^-2 mol) was added, and the mixture was stirred at 60 ° C. for 1 hour. After distilling off THF, 50 ml of ice water was added and extracted with ethyl acetate. The organic layer was washed with water until neutral, and the solvent was distilled off, followed by distillation to obtain 11 g of a reaction mixture.

Next, 0.06 g of paratoluenesulfonic acid and 60 ml of methanol were added to the mixture, and the mixture was stirred at room temperature overnight to remove the tetrahydropyranyl ether group. Saturated sodium bicarbonate water was added to the reaction solution to neutralize the pH, methanol was distilled off, and the mixture was extracted with ether. The organic layer was washed with water until the organic layer became neutral, the solvent was distilled off, and then distilled to obtain 8.6 g of a reaction mixture ( Yield 99
%).

Next, this mixture was added to a 500-ml pressure-resistant reactor, and further 0.9 g of Ru / C and 250 ml of IPA were added, and the mixture was heated at 90 ° C./0.1.
The mixture was stirred for 3 days under a hydrogen pressure of 5 MPa. After filtering the catalyst from the reaction solution and distilling off the solvent, 4.4 g of a reaction mixture was obtained. The reaction mixture is subjected to silica gel column chromatography (ethyl acetate
1.5 / hexane 8.5) and purify the desired 4- (1-methyl-1-methoxyethyl) cyclohexylmethanol
1.1 g were obtained (19% yield, 7% overall yield).

¹ H-NMR (CDCl ₃ , 200 MHz), δ: 0.75
~ 2.00 (10H, m), 1.07 (6H, s, 2Me), 2.16 (1H, bs, OH), 3.
16 (3H, s, Me) 3.62 (2H, d, J = 6.4Hz, CH ₂ ) IR (KBr, neat, cm ^-1 ): 3412,2938,1452,1368,1
338, 1317, 1242, 1200, 1143, 1107, 1056,879, 816,
741 The resulting compound had a flowery odor.

Example 9 1- {4- (1-methyl-1-methoxyethyl) cyclohexyl} -1-ethanol

[0075]

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200 ml with Dimroth condenser and thermometer
25 g (0.12 mol) of 4-bromo-α-methylbenzyl alcohol, 11 g of DHP, 2 g of paratoluenesulfonic acid, and 100 ml of methylene chloride were added to the four-necked flask, and the mixture was stirred at room temperature overnight. The reaction was cooled to 0 ° C., saturated aqueous sodium bicarbonate and ethyl acetate were added, the mixture was washed with water until the organic layer became neutral, and the solvent was distilled off to obtain 38 g of a reaction mixture. The reaction mixture was subjected to silica gel column chromatography (ethyl acetate 0.5
/ Hexane 9.5) to obtain 11 g of tetrahydropyranyl ether (yield 31%).

200 ml with Dimroth condenser and thermometer
1.0g (4.3 × 10
^-2 mol) and 20 ml of dehydrated THF, and while stirring, 11 g of tetrahydropyranyl ether synthesized by the above method (3.6 ×
(10 ^-2 mol) in 30 ml of dehydrated THF was added dropwise at a rate at which THF slowly refluxed. After the dropwise addition, the mixture was refluxed for 30 minutes to prepare a Grignard reagent, which was returned to room temperature. 2.5 g (4.3 × 10 ^-2 mol) of dehydrated acetone was added dropwise thereto, and the mixture was stirred at room temperature for 2 hours. Saturated aqueous ammonium chloride was added to the reaction product, ethyl acetate was added, and the mixture was washed with water until the organic layer became neutral, and the solvent was distilled off to obtain 11 g of a reaction mixture. Silica gel column chromatography of the reaction mixture (ethyl acetate 1.5 / hexane 8.5)
Then, 7.6 g of an alcohol compound was obtained (yield: 72%).

200 ml with a Dimroth condenser and thermometer
1.3 g of 60% sodium hydride (3.4 g
× 10 ^-2 mol) in 20 ml of anhydrous THF, a solution of 7.5 g (2.8 × 10 ^-2 mol) of the alcohol obtained above in 25 ml of anhydrous THF was added, and then 4.8 ml of methyl iodide was added.
g (3.4 × 10 ^-2 mol) was added and the mixture was stirred at 60 ° C. for 1 hour. T
After distilling off HF, 50 ml of ice water was added and extracted with ethyl acetate.
The organic layer was washed with water until neutral, and the solvent was distilled off, followed by distillation to obtain 8.0 g of a reaction mixture.

Next, 0.04 g of paratoluenesulfonic acid and 40 ml of methanol were added to the mixture, and the mixture was stirred overnight at room temperature to remove the tetrahydropyranyl ether group. Saturated aqueous sodium bicarbonate was added to the reaction solution to neutralize the pH, methanol was distilled off, and 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 5.8 g of a reaction mixture ( Yield 97
%).

Next, this mixture was added to a 300 ml pressure-resistant reactor, 0.6 g of Ru / C (hydrous POLType) and 150 ml of IPA were further added, and the mixture was stirred for 3 days under a hydrogen pressure of 90 ° C./0.5 MPa. The catalyst was filtered from the reaction solution, and the solvent was distilled off to obtain 4.7 g of a reaction mixture. The reaction mixture was purified by silica gel column chromatography (ethyl acetate 1.5 / hexane 8.5) to give the desired 1
2.0 g of-{4- (1-methyl-1-methoxyethyl) cyclohexyl} -1-ethanol was obtained (yield 53%, total yield 11%).

¹ H-NMR (CDCl ₃ , 200 MHz), δ: 0.90
~ 2.20 (11H, m), 1.08 (6H, s, 2Me), 1.21 (3H, d, J = 6.2Hz,
Me), 3.16 (3H, s, Me), 3.54 (1H, dq, J = 6.2 Hz, CH) IR (KBr, neat, cm ^-1 ): 3400, 2932, 2734, 2632, 2134, 1944, 1887, 1647, 14
55, 1380, 1317,1269, 1245, 1203, 1110, 1074, 930,
891, 861, 831, 798, 741, 630, 534 The obtained compound had sandalwood-like odor.

Example 10 2- {4- (1-methyl-1-methoxyethyl) cyclohexyl} -2-propanol

[0083]

Embedded image

In a 500 ml pressure-resistant reactor, 25 g (0.13 mol) of α, α'-dihydroxy-p-diisopropylbenzene was added.
, Ru / C 2.5 g were suspended in IPA 350 ml, and 90 ° C / 0.6
The mixture was stirred under a hydrogen pressure of MPa for 3 days. The catalyst was filtered from the reaction solution, and the solvent was distilled off to obtain 18 g of a reaction mixture. The reaction mixture was recrystallized from IPA and an ethyl acetate solvent to give 2- {4- (1-
(Hydroxy-1-methylethyl) cyclohexyl} -2
-8.6 g of propanol were obtained (71% yield).

500 ml with a Dimroth cooler and thermometer
2.1 g (5.2%) of 60% sodium hydride
× 10 ^-2 mol) and 50 ml of THF, and while stirring, 8.6 g (4.3 × 10 ^-2 mol) of the diol synthesized by the above method was added to THF.
It was dissolved in 200 ml and added dropwise. After the dropwise addition, 7.3 g (5.2 × 10 ^-2 mol) of methyl iodide was slowly added dropwise while paying attention to the generation of gas, and the mixture was stirred overnight at room temperature. Heat the reaction to 100 ° C,
After distilling off THF, the mixture was cooled to room temperature and water was added to decompose excess sodium hydride. Ethyl acetate was added to the reaction mixture, and the mixture was washed with water until the organic layer became neutral.
8.9 g were obtained. The reaction mixture was purified by silica gel column chromatography (ethyl acetate 2 / hexane 8) to obtain 4.2 g of the desired 2- {4- (1-methyl-1-methoxyethyl) cyclohexyl} -2-propanol (yield).
55%, overall yield 39%).

¹ H-NMR (CDCl ₃ , 200 MHz), δ: 0.80
~ 2.00 (11H, m), 1.10 (6H, s, 2Me), 1.18 (6H, s, 2Me), 3.1
6 (3H, s, Me) IR (KBr, neat, cm ^-1 ): 3466, 1938, 2830, 2128, 1
635, 1464, 1368, 1134, 1068, 912, 852 The obtained compound had a woody aroma.

The compounds of the present invention obtained in the above Examples 1 to 10
Table 1 summarizes the duration of the fragrance and odor of (1) to (10). The number of days of odor was determined by the present compound on odor paper.
(1) to (10) were attached, and how many days the fragrance lasted was observed.

[0088]

[Table 1]

Next, examples of the fragrance composition of the present invention will be described. Examples 11 to 14 By adding 200 parts by weight of the compound of the present invention (1), (3), (4) or (5) to 800 parts by weight of the following Mugue-type compounded flavor, a floral / muege having softness and volume is obtained. A blended flavor of the type was obtained.

[0090] Examples 15-18 Compound of the present invention in 800 parts by weight of the following sandalwood-type compounded fragrance
By adding 200 parts by weight of (2), (7), (9) or (10), a sandalwood-type blended fragrance having floral softness, sweetness and volume was obtained.

[0091] Note) * 1: Kao Corporation product name 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran 19-20 Compound of the present invention (6) or 800 parts by weight of the following perfume for detergent
By adding 200 parts by weight of (8), a detergent fragrance having softness, cleanliness, floweriness and sweetness was obtained.

[0092]

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

Claims (5)

[Claims] 1. A novel cyclohexylalkanol represented by the general formula (I). Embedded image (Wherein, R ¹ , R ² , R ³ and R ⁴ are the same or different and represent an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, provided that R ¹ ,
Except when all of R ² , R ³ and R ⁴ are hydrogen atoms. R ⁵
Represents an alkyl group having 1 to 3 carbon atoms. ) 2. In the general formula (I), R ¹ and R ² are a hydrogen atom or a methyl group, R ³ and R ⁴ are a hydrogen atom, a methyl group or an ethyl group, and R ⁵ is a methyl group or an ethyl group. The novel cyclohexylalkanols according to claim 1, which is a group. 3. In the general formula (I), R ¹ and R ² are a hydrogen atom or a methyl group, R ³ and R ⁴ are a hydrogen atom or a methyl group, and R ⁵ is a methyl group. The novel cyclohexylalkanols according to the above. 4. A fragrance composition comprising the novel cyclohexyl alkanol according to any one of claims 1 to 3. 5. The fragrance composition according to claim 4, wherein the content of cyclohexylalkanols in the composition is 0.1 to 90% by weight.