JP2632474B2 - 2- (2-t-butylcyclohexyloxy) -1-butanol and fragrance composition containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel aromatic compound, and more particularly to a compound having a lingering woody / amber-like odor and a fragrance composition containing the same.

[0002]

[Problems to be solved by the prior art and the invention]
Among the fragrances having an amber-like scent, those having a residual scent are used as base notes on the fragrance and are important materials that determine the scent as a framework of the compounded fragrance. However, many of these compounds, including natural products, are relatively expensive, which is a great limitation when used in inexpensive compounded fragrances. Therefore, it is extremely important to develop an inexpensive material having a woody / amber-like scent with a lingering scent.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have proposed an ortho- or para-form alkylcyclohexanol, alkylcyclohexanone, alkylcyclohexyl acetate, etc. derived from an alkylphenol as shown in the following formula.

[0004]

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(Wherein R represents a hydrogen atom or a methyl group) has a woody odor and is widely used as an inexpensive material (see Perf by S. Arctender).
Ume and Flavor Chemical
s "), and searched for a compound having a woody / amber-like odor which is more excellent in residual odor and can be produced at low cost. As a result, they have found that 2- (2-t-butylcyclohexyloxy) -1-butanol, which is a reduced product of ether carboxylic acid obtained from 2-t-butylcyclohexanol and 2-halobutyric acid, satisfies the above requirements. Thus, the present invention has been completed.

That is, the present invention provides the following formula (1)

[0007]

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It is intended to provide 2- (2-t-butylcyclohexyloxy) -1-butanol represented by the formula and a fragrance composition containing the same.

The 2- (2-t-butylcyclohexyloxy) -1-butanol (1) of the present invention can be produced, for example, according to any of the following reaction formulas.

(A) According to the following formula, 2-t-butylcyclohexanol (2) is converted into an alcoholate using a strong base, and then 2-halobutyric acid (3) is reacted. The compound (1) of the present invention can be obtained by reducing 4).

[0011]

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(Wherein, X represents a halogen atom)

The reaction solvent used in the production of the ether carboxylic acid (4) includes, for example, ether solvents such as diethyl ether, dibutyl ether and tetrahydrofuran; hydrocarbon solvents such as hexane, benzene, toluene and xylene. Is mentioned. As a strong base,
Alkali metal hydrides such as sodium hydride, lithium hydride and potassium hydride; alkali metal amides such as sodium amide, lithium amide and potassium amide; alkali metals such as sodium, lithium and potassium; alkyl lithium and alkyl magnesium halides And the like. The amount of the strong base used is 0.1 to 2 -t-butylcyclohexanol (2).
It is preferable to use 1 to 2.0 equivalents, particularly 1.0 to 1.2 equivalents. The amount of 2-halobutyric acid (3) to be used is preferably 0.1 to 2.0 equivalents, particularly preferably 0.5 to 1.0 equivalent, relative to compound (2). The reaction temperature is 30 to 150 ° C. for both the alcoholation reaction and the etherification reaction, and especially 50 to 1 ° C.
A range of 20 ° C. is preferred.

Next, examples of the reaction solvent used for the reduction of the ether carboxylic acid (4) include ether solvents such as diethyl ether, dibutyl ether and tetrahydrofuran. As the reducing agent, lithium aluminum hydride, sodium aluminum hydride,
And metal hydrides such as diborane. The amount of the reducing agent to be used is 0.5 to 2.0 equivalents to compound (4),
It is particularly preferable to use 0.5 to 1.0 equivalent. Further, the reaction temperature is preferably in the range of 0 to 100 ° C, particularly preferably 20 to 60 ° C.

When the starting material 2-t-butylcyclohexanol (2) is a mixture of isomers such as cis and trans, the resulting compound (1) of the present invention is also obtained as a mixture of isomers. In this case, they may be separated and used by column chromatography or the like, or may be used as a mixture.

(B) According to the following formula, 2- (2-t-butylphenyloxy) -1-butanol (7) is obtained by reacting 2-t-butylphenol (5) with epoxide (6) in the presence of a base catalyst. ) And 1- (2-t-butylphenyloxy) -2-butanol (8), and the resulting mixture was hydrogenated using a metal catalyst to give the present compound (1) as an isomer 1- (2
-T-butylcyclohexyloxy) -2-butanol (9).

[0017]

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The reaction solvent used in the epoxide addition reaction includes, for example, methanol, ethanol, n
Alcohol solvents such as propanol and isopropanol; ether solvents such as diethyl ether, dibutyl ether, and tetrahydrofuran; hydrocarbon solvents such as hexane, benzene, toluene, and xylene; and the like. it can. As the base, a powder or an aqueous solution of an alkali metal hydroxide such as sodium hydroxide, lithium hydroxide, or potassium hydroxide; an alkali metal carbonate such as sodium carbonate, lithium carbonate, or potassium carbonate can be used. The amount of the base to be used is 0.01 to 2.0 equivalents, particularly preferably 0.0 to 2.0 equivalents to compound (5).
It is preferably 5 to 0.5 equivalent. Epoxide (6)
Is used in an amount of 1.0 to 5.0 equivalents to compound (5),
In particular, it is preferably 1.0 to 1.2 equivalents. The reaction temperature is preferably in the range of 30 to 200 ° C, particularly preferably 50 to 150 ° C.

Next, as a reaction solvent used in the hydrogenation reaction of the mixture of the compounds (7) and (8), alcohol solvents such as methanol, ethanol, n-propanol and isopropanol; hexane, heptane, cyclohexane and methylcyclohexane And the like, but the reaction can be carried out without a solvent. Examples of the metal catalyst include a palladium catalyst, a ruthenium catalyst, a rhodium catalyst, a platinum catalyst, and a nickel catalyst.
The amount of the catalyst is 0.1 to the mixture of the compounds (7) and (8).
It is preferable to use from 0.01 to 10% by weight, particularly from 0.5 to 5% by weight. Further, the reaction temperature is 50 to 300 ° C., particularly 100
The range of -250 ° C is preferred. The hydrogen pressure is preferably in the range of 1 to 150 atm, especially 10 to 100 atm.

By this hydrogenation reaction, the compound (1) of the present invention is usually obtained as a mixture with the isomer (9). In this case, they may be separated and used by column chromatography or the like, or may be used as a mixture.

As described above, the compound (1) of the present invention can be produced using inexpensive raw materials and has a woody, amber-like or the like fragrance, and the fragrance has an excellent residual scent. Therefore, when compound (1) is blended as a base note, an excellent fragrance composition can be obtained. The compounding amount of the compound (1) in the fragrance composition of the present invention varies depending on other compounded fragrances, desired fragrance, and the like.
The amount is not particularly limited as long as it can impart a woody or amber-like fragrance, but it is generally preferable that 0.1 to 90% by weight be blended in the composition. In addition, the fragrance composition of the present invention is a perfume, soap, shampoo, rinse, detergent, cosmetics,
It can be widely used for sprays, fragrances and the like that require fragrance.

[0022]

EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.

Example 1 (a) A 300 ml round bottom flask equipped with a Dim funnel and a dropping funnel was charged with sodium hydride (62% by weight) under a nitrogen stream.
7.5 g (0.194 mol) of mineral oil and toluene 3
0 ml was added and heated to 90 ° C. This was followed by 2-t-butylcyclohexanol (cis: trans = 8: 2) 30.
A mixture of 0 g (0.192 mol) and 30 ml of toluene was added dropwise in about 30 minutes, and then the mixture was stirred under reflux for 2 hours until hydrogen generation ceased. 2-Bromobutyric acid was added to the reaction mixture.
0 g (0.096 mol) was added dropwise, and the mixture was further refluxed.
Stirred for hours. 100 ml of water was added to the reaction mixture, and the aqueous layer and the organic layer were separated. 200 ml of 3N hydrochloric acid was added to the obtained aqueous layer, and extracted twice with hexane. The hexane layers were combined and the solvent was distilled off to obtain 88 g of 2- (2-t-butylcyclohexyloxy) -butanoic acid (yield 38%).

IR (film, cm ^-1 ): 1710, 2938, 2400-3700 NMR (200 MHz, CDCl ₃ , ppm): 0.95 (s, 9H), 0.9-2.2 (m, 14H),
3.9-4.1 (m, 1H), 4.2-4.4 (m, 1H), 9.07 (s, 1H).

(B) 5 with gym funnel and dropping funnel
In a 00 ml round bottom flask, 6.5 g (171 mmol) of lithium aluminum hydride and 100 ml of ether were placed, and cooled to 0 ° C. under a nitrogen stream. 27.5 g of 2- (2-t-butylcyclohexyloxy) -butanoic acid (114
mmol) and 100 ml of ether were added dropwise over 1 hour. After stirring at 0 ° C. for 30 minutes, the mixture was further stirred at room temperature overnight. After the reaction mixture was cooled to 0 ° C., 30 ml of water and 150 ml of 3N hydrochloric acid were added, extracted twice with hexane, and the hexane layer was washed with a saturated aqueous solution of sodium hydrogen carbonate. After distilling off the solvent, distillation was carried out to give 23.4 g of 2- (2-t-butylcyclohexyloxy) -1-butanol (yield 90).
%, Boiling point 134-136 ° C / 4 mmHg, cis: trans =
8: 2). It had a woody / amber-like scent with lingering scent.

IR (film, cm ^-1 ): 1074, 1221, 1368, 1392,
1452, 2860, 2932, 3400 NMR (200 MHz, CDCl ₃ , ppm): 0.92 (t, J = 7 Hz, 3H), 0.98 (s, 9
H), 1.0-2.3 (m, 12H), 3.3-3.8 (m, 4H). GC-MS (M ⁺ ): 228

Example 2 (a) 2-t-butylphenol 3 was placed in a 1-liter round bottom flask equipped with a Dim funnel and a dropping funnel under a nitrogen stream.
50 g (2.33 mol) and 35 g of a 48% aqueous sodium hydroxide solution were added, and the mixture was heated to 120 ° C. To this,
176 g (2.45 mol) of butylene oxide was added dropwise over about 2 hours, and the mixture was stirred at 120 ° C. for 5 hours. After cooling the reaction mixture, the lower aqueous sodium hydroxide solution was separated from the organic layer, and distilled to obtain 2- (2-t-butylphenyloxy) -1-butanol and 1- (2-t-butylphenyloxy). ) Mixture of 2-butanol (5:95)
497 g (boiling point 130 ° C./4 mmHg, yield 96%) were obtained.

IR (film, cm ^-1 ): 744, 975, 1038, 1092, 1
134, 1233, 1290, 1362, 1392,1443, 1491, 1599, 295
6, 3058, 3412 NMR (60 MHz, CDCl ₃ , ppm): 1.07 (t, J = 7 Hz, 3H), 1.40 (s, 9
H), 1.5-1.8 (m, 2H), 2.15 (d, J = 4Hz, 1H), 3.8-4.1 (m, 3H),
6.8-7.4 (m, 4H).

(B) In a 500 ml autoclave, add 2-
50 g (0.23 mol) of a mixture of (2-t-butylphenyloxy) -1-butanol and 1- (2-t-butylphenyloxy) -2-butanol, 150 g of isopropanol and a 5% activated carbon-supported palladium catalyst [N. 5 manufactured by NE Chemcat
0% water-containing product] 1.0 g, hydrogen pressure 70 kg / cm ² ,
The reaction was carried out at 90 ° C. for 27 hours until hydrogen absorption ceased.
After completion of the reaction, the catalyst was filtered, distilled, and 2- (2-t
-Butylcyclohexyloxy) -1-butanol and 1
38.8 g of a mixture (5:95) of-(2-t-butylcyclohexyloxy) -2-butanol was obtained. This had a woody / amber-like scent with lingering scent.

[0030]

Table 1 Example 3 Fuzea-mixed perfume: Composition (parts by weight) Bergamot oil 250 2. Lavender oil 257 3. Sage flower oil 10 4. Rose oil base ¹⁾ 5 5. Geranium Bourbon 10 6. Jasmine base ²⁾ 130 7. Anisaldehyde 10 8. Amyl salicylate 20 9. Sandalwood oil 40 10. Okemos Absolute 50% DEP ³⁾ 40 11. Patchouli oil 30 12. Vetiver oil 20 13. Musk ketone 50 14. Coumarin 30 15. Vanillin 5 16. Civet base ⁴⁾ 3 totals 950 Note) 1), 2), 4) Kao-made base 3) Diethyl phthalate

By adding 50 parts by weight of the compound of the present invention to the above-mentioned fusea-formulated perfume, a prepared perfume with a soft quinoline characteristic of vetiver oil and increased in sweetness and gloss was obtained.

[0032]

Industrial Applicability The 2- (2-t-butylcyclohexyloxy) -1-butanol (1) of the present invention can be produced using inexpensive raw materials, and has a woody / amber-like state having excellent residual odor. It has an aroma. Therefore, the fragrance composition of the present invention containing it can be widely used for perfumes, soaps and the like which require fragrance.

 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Yoshiaki Fujikura 271-6 Yamamotocho, Utsunomiya City, Tochigi Prefecture

Claims (2)

(57) [Claims] 1. The following formula (1) 2- (2-t-butylcyclohexyloxy) -1-butanol represented by the formula: 2. A fragrance composition containing the 2- (2-t-butylcyclohexyloxy) -1-butanol according to claim 1.