JPH045669B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel sesquiterpene alcohol and a fragrance composition containing the same.

[Conventional technology]

The present inventor has conducted intensive research on terpene compounds contained in various moss, and together with Jessef D. Connolly and others, we have discovered the weeping moss (Frullania tamarisci), which is widely distributed in Europe.
subsp. This sesquiterpene alcohol is called Tamarisol;
Tetrahedron Letters, Vol.25, No.13, pp1401−
102, 1984]. In addition, the present inventor previously discovered that tamarisol has a Woody note and a Powdery-Green note, as well as Moss, Foin, Fluvia, and Costus. ), Violet
It has a fantastic aroma that brings to mind a variety of aromas such as leaf), seaweed (marin), etc., and has strong diffusivity and fragrance retention, making it a material for blended fragrances that harmonizes well with many fragrance materials. discovered that it has excellent properties (Japanese Patent Application No. 59-87440
No. 60-228409) (see specification).

[Problem that the invention seeks to solve]

The present inventor has conducted intensive research to derive a compound from tamarisol, which is useful as a material for the above-mentioned prepared fragrance, that has a different aroma from tamarisol and can be used as a material for prepared fragrance.

One of the objects of the present invention is to provide a novel tamarisol derivative useful as a raw material for mixed fragrances, particularly a sesquiterpene alcohol having chypre-like and oriental-like aromas that evoke a variety of aromas. Another object of the present invention is to provide a use of the sesquiterpene alcohol as a blended fragrance material.

[Means for solving problems]

According to the present invention, the above object is achieved by using 3,7-dimethyl-2-(2-methyl-1,2-epoxypropyl)hexahydroindan-2-ol (hereinafter referred to as epoxy tamarisol). and by providing a fragrance composition containing epoxy tamarisol.

Epoxy tamarisol is produced by subjecting tamarisol to a conventional epoxidation reaction.
For example, epoxy tamarisol can be obtained by treating tamarisol with hydrogen peroxide, an organic peroxide such as tert-butyl hydroperoxide, or an organic peracid such as peracetic acid, perbenzoic acid, metachloroperbenzoic acid. These organic peroxides or organic peracids are about 0.1 to 2 per mole of tamarisol.
Molar amounts are used, preferably about 0.9 to 1.2 molar amounts. The reaction is usually carried out in a solvent, and the solvents include alcohols such as methanol and ethanol; ethers such as diethyl ether and tetrahydrofuran; acetone; hydrocarbons such as hexane, benzene and toluene; and halogenated compounds such as methylene chloride and 1,2-dichloroethane. Hydrocarbons and the like are used. The amount of solvent used is approximately 2 to 100 ml of tamarisol.
It is 100 times heavier. When using an organic peroxide, the reaction is carried out in the presence of vanadium pentoxide, vanadium monoxide acetylacetonate complex, etc., if necessary, within a temperature range of about -50°C to the boiling point of the solvent used, preferably at room temperature. and temperatures around that range. When an organic peracid is used, the reaction is carried out at a temperature of about -50°C to 50°C, preferably about 0 to 30°C. At the end of the reaction, sodium bisulfite is added to the reaction mixture to treat the remaining organic peroxide or organic peracid, and then the epoxy tamarisol can be separated by subjecting it to a conventional separation operation. For example, the reaction mixture treated with sodium hydrogen sulfite is extracted using a solvent such as diethyl ether, the extract is washed with water, dried over anhydrous magnesium sulfate, and the solvent is distilled off. You can get tamarisol.

Tamarisol used as a raw material is a compound contained in Frullania tamarisci subsp. tamarisci, which is distributed over a wide area in Europe. For example, ethers such as diethyl ether and dibutyl ether; methylene chloride, chloroform, , halogenated hydrocarbons such as dichloroethane;
It can be obtained by extraction using a solvent such as alcohol such as methanol, ethanol, and isopropanol. Extraction is usually carried out at a temperature of about 20 to 40°C for about 1 to 3 days. By distilling off the solvent from the extract, essential oil of weeping moss containing tamarisol is obtained. Tamarisol can be isolated by subjecting the essential oil to distillation or silica gel column chromatography using conventional methods.

The weeping moss containing tamarisol belongs to the moss order Jungermanniales and family Frullaniaceae, and is a thallus moss that grows on tree trunks or moist rock slabs, and is easy to collect. Furthermore, weeping moss is widely distributed in Europe, and it is possible to secure sufficient quantities as an industrial raw material.

Epoxy tamarisol is based on a very powdery day note with a moss-like green note, and has a chypre-like and oriental fragrance that brings to mind a variety of scents such as pachy lily, vetiver, oakmoss, and wood. Moreover, it has strong diffusivity and fragrance retention, and blends well with many fragrance materials, making it useful as a material for mixed fragrances.

The fragrance composition of the present invention contains epoxy tamarisol in an amount that allows the fragrance to be detected olfactory. The content of epoxy tamarisol may be within a wide range depending on the intended use of the fragrance composition, for example 0.005
It can vary between ~95% by weight. The perfume compositions of the invention can be used in a wide variety of ways. For example, it can be used for spatial spraying; perfumes; colognes; cosmetics such as soaps, lotions, and creams; bath products; hair cosmetics such as hair tonics, pomades, hair liquids, hair creams, and hair; hair washes such as shampoos and conditioners; detergents; ;
It can be used as a purifying agent. The compositions can also be used to scent substrates such as textiles, fabrics and paper products.

〔Example〕

The present invention will be specifically explained below using examples. Note that the present invention is not limited to these Examples.

Example 1 Synthesis of epoxy tamarisol 346 mg (1.56 mmol) of tamarisol was dissolved in 10 ml of methylene chloride, and a solution of 259 mg (1.51 mmol) of metachloroperbenzoic acid dissolved in 5 ml of methylene chloride was added dropwise to this solution, followed by stirring at room temperature for 1 hour. At the end of the reaction, 10 ml of a saturated aqueous solution of sodium bisulfite was added to the reaction mixture, stirred for 1 hour, and then extracted with 50 ml of diethyl ether. The extract was sequentially washed with sodium bicarbonate water and brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain epoxy tamarisol.
359 mg (1.51 mmol) was obtained. Yield 97%. The instrumental analysis data for the product is shown below.

Mass spectrum (m/z): 238 [M ⁺ ] ¹ H-NMR spectrum (90MHz) δ ^CDCl3 _ppn : 0.85-0.96 (m, 6H); 1.21 (bs, 1H); 1.45, 1.41 (each s, 6H) ;2.56~2.59(s,
1H) IR spectrum (CCl ₄ /cm ^-1 ): 3570, 1460, 1380, 1300, 1240, 1120.1090,
1060, 1035, 1020, 990, 950, 905, 865, 845,
670 Reference example 1 kg of dried weeping moss (Frullania tamarisci subsp. tamarisci) collected in Scotland was treated with diethyl ether 3 at 20℃ for 24 hours.
The extraction process took a long time. By distilling off the solvent from the extract, 50 g of a crude extract was obtained, which was subjected to column chromatography using 300 g of silica gel (eluent: n-hexane-ethyl acetate system).
1 g of a colorless viscous oil was obtained from the 10% ethyl acetate-90% hexane eluate. The instrumental analysis data for this oil is shown below. Based on these instrumental analysis data, the oily substance was identified as 3,7-dimethyl-2-(2-methyl-1-propenyl)hexahydroindane-2-
It was identified as Oar.

Specific optical rotation [α] _D : +19.7 ( c 1.1, CHCl ₃ ) Molecular weight: 222 [M ⁺ ] Infrared absorption spectrum νmax (CCl ₄ ): 3620 cm ^-1 Nuclear magnetic resonance spectrum ¹ H-NMR (360 MHz) δ ^CHCl3 _ppn : 5.07 (m, J=1.3Hz, 1H-10); 1.88 (d, J=1.2Hz, 3H-13); 1.75 (d, J=1.5Hz, 3H-12); 0.92 (d, J= 6.6Hz, 3H-15); 0.88 (d, J = 6.6Hz, 3H-14) ¹³ C-NMR (50MHz) δ ^CHCl3 _ppn : 59.0 (C-1), 79.0 (C-2), 46.0 (C- 3),
33.3 (C-4), 30.6 (C-5), 50.3 (C-6),
40.1 (C-7), 32.2 (C-8), 24.3 (C-9),
121.9 (C-10), 136.4 (C-11), 28.5 (C-12),
20.3 (C-13), 15.4 (C-14), 19.2 (C-15) Example 2 Chypre fragrance composition A fragrance composition having a Chypre fragrance was obtained according to the following formulation.

Parts by weight Bergamot oil 20 Lavender oil 2 Oakmoss oil 10 Geranium oil 3 Orange flower oil 2 Amyl salicylate 3 Phenethyl alcohol 5 Citronellol 5 Linalool 5 Methylionone 5 Benzyl acetate 3 Rose essential oil 2 Diasmine essential oil 3 Pachilily oil 5 Vetiver oil 2 Sandalwood oil 3 Coumarin 5 Vanillin 2 Amber Synthetic 5 Musk Synthetic 5 Epoxy Tamarisol 5 100 Example 3 Oriental Bouquet Perfume Composition A perfume composition having an Oriental Bouguet aroma was obtained according to the following formulation.

Parts by weight Bergamot oil 15 Carnation essential oil 5 Ylang-ylang oil 3 Neroli oil 3 Geranium oil 2 Aldehyde C-10 10% 3 Aldehyde C-11 10% 3 α-ionone 7 Methylionone 5 Iris oil 2 Eugenol 4 Rose base 7 Diasmine base 8 Hydroxycitronellol 5 Pachylily oil 5 Heliotropin 2 Amber synthetic 3 Musk synthetic 3 Civet tincture 2 Sandalwood oil 2 Vetiver oil 3 Epoxy tamarisol 8 100 Example 4 White rose-like fragrance composition White rose-like ( White
A fragrance composition having the aroma of ``Rose'' was obtained.

Parts by weight Rhodinol 30 Phenethyl alcohol 10 Phenethyl acetate 7 Linalool 10 Geraniol 10 Bergamot oil 5 Citronellyl acetate 3 Aldehyde C10 10% 2 Aldehyde C12 MNA10% 3 Rose essential oil 5 Rose synthetic 5 Pachu lily oil 1 Rose phenone 2 Musk tincture 2 Epo Kisitamari Sole 5 100 [Effects of the Invention] The epoxy tamarisol provided by the present invention has a chypre-like and oriental aroma that is reminiscent of the above-mentioned various aromas different from that of tamarisol, and also has a fragrance composition containing epoxy tamarisol. The product has a luxurious and modern scent that effectively utilizes the aroma of tamarisol.

Claims (1)

[Claims] 1 3,7-dimethyl-2-(2-methyl-1,
2-Epoxypropyl)hexahydroindane-
2-all. 2 3,7-dimethyl-2-(2-methyl-1,
2-Epoxypropyl)hexahydroindane-
A fragrance composition containing 2-ol.