JPH10140179A - Modified jinkoh oil and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain Jinkoh oil emitting fragrant smoke like Kyara easily at a low cost by subjecting Jinkoh oil to an alkali treatment to remove acid components such as fatty acids and adding a chromone compd. to the oil. SOLUTION: A modified Jinkoh oil is produced by dissolving a fatty acid- contg. Jinkoh oil in an org. solvent, pref. an ether, and adding an aq. alkali soln. to the resultant soln. to cause extraction to remove acid components including fatty acids. Any org. or inorg. base can be used for preparing the aq. alkali soln., but, sodium hydrogencarbonate and sodium hydroxide are pref., the former being esp. pref. It is still pref. if the extraction is conducted twice: first with an aq. soln. of sodium hydrogencarbonate and then with that of sodium hydroxide. The org. solvent is removed by distillation from the resultant org. solvent layer to obtain the modified Jinkoh oil. The addition of 10wt.% chromone compd. e.g. 2-[2-(methoxyphenyl)ethyl]chromone} to the modified oil gives a product which emits fragrant smoke similar to Kyara oil.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified agarwood oil and a method for producing the same, and more particularly, to the modification of its smoke.

[0002]

2. Description of the Related Art Agarwood is an Aquilaria species that has been used in various Asian countries since ancient times as incense.
(Thymelaeceae) incense wood, which has been mainly used to enjoy the scent (smoke) of smoke. The fragrance is oriental and elegant, and is also used in aromatherapy and the like. Kyara is also a type of agarwood, also known as Kanankoh or Kikunosuka.
The quality of the smoke is very high in both mass and it has been used since ancient times to distinguish it from other agarwood (Jinkoh).

At present, both Kyara and Jinkoh are on the market as trees, ground wood, and the like, as well as oils extracted from them. There is a marked difference between the two prices, and the price of kara oil (including green oil, white-skin green oil, black oil, tea oil, etc.) is more than 10 times higher than that of agarwood oil (including horseshoe-shaped). . Although agarwood oil is inexpensive, its smoke is inferior in mass to that of kara oil, and often has a weak aroma, poor persistence, and an unpleasant odor. Therefore, it has been desired to improve the smoke of such inexpensive agarwood oil.

It is known that the difference between the smokes of Kyara and Jinkoh is due to their constituents. Kara includes chromones such as 2- [2- (4-methoxyphenyl) ethyl] chromone, 2- (2-phenylethyl) chromone, and 6-methoxy-2- [2- (4-methoxyphenyl) ethyl] chromone. These chromones are scarcely contained in agarwood (Jinkoh) while they are contained in large amounts (Japanese Journal of Pharmaceutical Sciences, 40 (3), 271-274).
Page (1986); Journal of Pharmaceutical Sciences, 41 (2), 142-1
46 (1987); J. Essent. Oil Res., 5 , 283-28.
9 (May / Jun 1993)). Chromones are non-volatile substances and are odorless at room temperature, but are thermally decomposed at 150 to 180 ° C., which is close to the temperature at which incense is usually burned, to produce benzaldehydes having aroma. From these facts, it is considered that chromone, together with other volatile substances, is a contributor to the gorgeous, graceful, strong and persistent smoke characteristic of chara (Chem. Pharm. Bull., 33 ( 11), 5088-5091 (198
Five)). However, simply adding chromones to conventional agarwood oils does not produce good quality smoke like chara,
At present, the agarwood oil has not been smoke-modified.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to improve the smoke of agarwood oil. It is an object of the present invention to provide a modified agarwood oil which emits smoke, and further to provide a modified agarwood oil which emits smoke of the same high quality as that of a chara.

[0006]

Means for Solving the Problems The present inventors considered that the presence of impurities contained in agarwood oil may have reduced the quality of smoke of agarwood oil, and therefore, the present inventors have proposed a method for modifying agarwood oil. As a result of studies and investigations, it was found that when the agarwood oil was treated with alkali to remove acidic components such as fatty acids, the smoke of the agarwood oil was greatly improved. Furthermore, it has been found that if chromones are added to such an alkali-treated agarwood oil, agarwood oil that emits very high-quality smoke equivalent to Kyara can be obtained, and the present invention has been completed. .

That is, the modified agarwood oil according to the present invention is characterized in that the fatty acid is removed from the agarwood oil containing a fatty acid by an alkali treatment. The chromone-added modified agarwood oil according to the present invention is characterized in that chromones are further added to the modified agarwood oil. It is preferable that 2- [2- (4-methoxyphenyl) ethyl] chromone is added as the chromone so as to be 1 to 20% by weight in the modified agarwood oil.

[0008] A method for producing a modified agarwood oil according to the present invention is characterized in that agarwood oil containing a fatty acid is treated with an alkali to remove the fatty acid. In the production method of the present invention, it is preferable to sequentially extract an ether solution of an agarwood oil containing a fatty acid with an aqueous solution of sodium hydrogen carbonate and an aqueous solution of sodium hydroxide to remove the fatty acid, and to remove the ether from the ether layer. .

Further, the method for producing a chromone-added modified agarwood oil according to the present invention is characterized in that chromones are further added to a modified agarwood oil obtained by alkali-treating a fatty acid-containing agarwood oil. . In addition, it is preferable to add 2- [2- (4-methoxyphenyl) ethyl] chromone as chromones so as to be 1 to 20% by weight in the modified agarwood oil.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The first feature of the modified agarwood oil according to the present invention is that it does not contain a fatty acid. Such a modified agarwood oil can be obtained by removing an acidic component containing a fatty acid from a fatty acid-containing agarwood oil by an alkali treatment. Currently, agarwood (Jinkoh)
Oils commercially available as oils usually contain fatty acids, and in the present invention, such fatty acid-containing agarwood oils can be used as a raw material of modified agarwood oils. Of course, a fatty acid-containing agarwood oil may be obtained by extracting from agarwood (Jinkoh) tree with a known method, for example, acetone. For agarwood (Jinkoh), Cambodia, Vietnam,
Mostly from Southeast Asia such as Hong Kong, A. agallocha Roxb., A.
Several species are known, such as sinensis (Lour.) Gilg. and A. malaccensis Lam.

In any case, the agarwood oil used as the raw material of the present invention contains at least one, usually several or more fatty acids. As a method for producing the agarwood oil of the present invention, first, such a fatty acid-containing agarwood oil is dissolved in an organic solvent, preferably ether, and an aqueous alkali solution is added thereto to perform an extraction operation to extract an acidic component containing a fatty acid. Remove. As the aqueous alkaline solution, any inorganic base or organic base can be used as long as it is generally used in an extraction operation, but an aqueous sodium hydrogen carbonate solution and an aqueous sodium hydroxide solution are preferable, and an aqueous sodium hydrogen carbonate solution is particularly preferable. After the extraction, it is preferable to perform another extraction with an aqueous sodium hydroxide solution. The organic solvent is distilled off from the obtained organic solvent layer under reduced pressure to obtain an agarwood oil from which fatty acids have been removed (modified agarwood oil).

Table 1 below shows gas-liquid chromatography of chara oil (green oil), Cambodian agarwood oil, and modified agarwood oil obtained by alkali-treating the Cambodian agarwood oil (Example 1 described later). It shows the results of analysis by chromatography (GLC) and gas chromatography-mass spectrometry (GC-MS). As shown in Table 1, pentanoic acid (peak No. 7), hexanoic acid (9),
Fatty acids such as heptanoic acid (11), dodecanoic acid (20), tetradecanoic acid (23), and hexadecanoic acid (25) are not contained, whereas Cambodian agarwood oil (before treatment) contains these fatty acids considerably. include. On the other hand, in the modified agarwood oil obtained by the alkali treatment, it can be seen that the fatty acids contained in the Cambodian agarwood oil were completely removed.

[0013] The smoke of the modified agarwood oil from which acidic components such as fatty acids have been removed by alkali treatment has a camphor-like aroma and a burnt aroma of wood, but is felt with the agarwood oil before the treatment. It has no unpleasant odor and emits a very good, well-balanced smoke. This suggests that the unpleasant odor of the conventional agarwood oil was attributable to the acid odor of fatty acids contained in the agarwood oil.

[0014]

[Table 1] Peak area (%) ** KARA OIL Agarwood oil produced from Camphorsia Modified agar oil oil No. Ingredient (green oil) (Before treatment) (Example 1) 1 Acetic acid 0.24 +-2 γ-Kurdishene--- 3 Henult human 0.41 0.09-4 Caralene---5 α-Humulene-0.18 0.15 6 δ-Quaien-0.13 0.117 7 Hentanoic acid-0.23-8 β-Acadrofuran * 0.97 3.97 3.62 9 Hexanoic acid-0.15-10 Hensil acetone-0.69 0.57 11 Heptanoic acid-0.12-12 Nor-keto acadufuran 0.51 0.48 0.27 13 Eremol---14 γ-Serinene-1.54 1.22 15 Akaloshydrol * 1.44 5.07 5.16 16 Cinco-Eremol * 1.35 0.93 0.92 17 Kusnol * 1.57 5.06 5.2 18 β- Oitesmall-1.51 1.51 19 Diethyl phthalate-1.96 1.43 20 Todecanoic acid-0.41-21 Diethyl peranone * 3.24 3.2 3.53 22 Karanone * 1.11 0.23 0.23 23 Tetradecanoic acid-0.39-24 Oxo-acetalosperol * 5.48--25 Hexatedecanoic acid-1.78-* Identified by MS data only. Others are specified by MS data and GLC data. ** In the peak area,-means undetectable, + means trace detection.

The chromone-added modified agarwood oil obtained by adding chromones to such a modified agarwood oil is also one of the modified agarwood oils of the present invention. Even if chromone was added to the fatty acid-containing agarwood oil before the alkali treatment, no kara-like smoke was emitted. However, when chromone is added to the modified agarwood oil from which the fatty acid has been removed by alkali treatment, it is possible to surprisingly obtain an agarwood oil that emits the same smoke as that of the kara. For example, as in Example 2 described later, when 2- [2- (4-methoxyphenyl) ethyl] chromone is added to the modified agarwood oil so as to be 10% by weight in the modified agarwood oil, Emits the same high quality and long lasting smoke.

From the above, the presence of fatty acids contained in conventional agarwood oils is one of the causes of unpleasant odor, and when chromone is added, it is combined with chromone and other components to give an overall aroma. It is probable that the quality of the smoke had been reduced. Usually, 2- [2-
(4-methoxyphenyl) ethyl] chromone is 20 to 3
About 0% by weight, and 4
About 0 to 60% by weight is contained. Therefore, when the modified agarwood oil according to the present invention is used, an agarwood oil that emits smoke equivalent to that of the karamon oil can be obtained by adding a smaller amount of chromones than that contained in the kara oil. And even considering the alkali treatment and the chromone addition process, it is possible to produce a chromone-added modified agarwood oil that emits karamon-like smoke at a lower cost than kara oil, which is a very inexpensive alternative to kara oil. Useful.

The chromones added in the present invention include 2- [2- (4-methoxyphenyl) ethyl] chromone, 2- (2-phenylethyl) chromone, and 6-methoxy-2- [2- (4 -Methoxyphenyl) ethyl]
Chromones and the like that are characteristically contained in Kyara, such as chromone, may be mentioned, but preferably 2- [2- (4-
[Methoxyphenyl) ethyl] chromone. In addition, these chromones can be easily produced by using a known method. The method for producing 2- [2- (4-methoxyphenyl) ethyl] chromone is described, for example, in Chem. Pharm.
l., 33 (11), 5088-5091 (1985), a method for producing 2- (2-phenylethyl) chromone is described, for example, in Aust. J. Che.
m., 29 , 2023 (1976), and other chromones can be synthesized in the same manner.

The amount of chromones to be added is 1 to 20% by weight, preferably 5 to 15% by weight of the total amount of the composition.
It is added so as to be a weight%. If the added amount of chromones is too small, it does not emit chara-like smoke. And she is far from the smoke of Kyara-sama. In addition,
When chromones are added to adjust the smoke tone of the modified agarwood oil obtained by the alkali treatment, the lower limit of the chromone addition amount is not limited to this.

The modified agarwood oil of the present invention can be used in applications in which agarwood oil or kara oil has been conventionally used. Therefore, it can be blended as a material of perfume and fragrance products.

[0020]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. Example 1 Production of Modified Agarwood Oil by Alkaline Treatment To a cambodia agarwood oil (0.51 g) dissolved by adding 20 ml of diethyl ether, 100 ml of a saturated aqueous solution of sodium hydrogen carbonate was added, and an extraction operation was performed. The aqueous layer was removed, 50 ml of a 5% aqueous sodium hydroxide solution was added to the obtained ether layer, and the extraction operation was performed again. The aqueous layer was removed, and diethyl ether was distilled off from the obtained ether layer under reduced pressure to obtain a modified agarwood oil (0.37 g).
(72.5% yield).

The components were analyzed by GLC and GC-MS, and as shown in Table 1, pentanoic acid (peak No. 7) and hexanoic acid in the agarwood oil produced in Cambodia (before treatment) were treated by alkali treatment, as shown in Table 1. (9), heptanoic acid (1
1), dodecanoic acid (20), tetradecanoic acid (23),
Fatty acids such as hexadecanoic acid (25) were completely removed. The measurement conditions of GLC and GC-MS are as follows.

<GLC measurement conditions> Model: Hewlett-Packard 5890 column; HP-INNOWax (60m × 0.25mm) Column temperature: 60 → 240 ° C (5 ° C / min temperature rise) Carrier gas: He (1.0ml / min) Detector; FID <GC-MS measurement conditions> Model: Hewlett-Packard G1800A column; HP-INNOWax (60m × 0.25mm) Column temperature; 60 → 230 ° C (5 ° C / min increase) Carrier gas: He (1.0ml / min)

Example 2 Smoke sensory test The modified agarwood oil produced in Example 1 and the Cambodian agarwood oil used as a raw material (before treatment) were mixed with
-[2- (4-methoxyphenyl) ethyl] chromone (synthesized by the method of Chem. Pharm. Bull., 33 (11), 5088-5091 (1985)) is used in an amount of 0 to 40% by weight in the agarwood oil. And the change in smoke with the amount of addition was examined. The smoking method is as follows. That is, each agarwood oil 5m
g was placed on an aluminum foil and heated in a gas incense furnace. The generated smoke was evaluated by 10 specialized panels. The evaluation criteria are as follows. <Evaluation Criteria> A: 9 or more out of 10 evaluated that the smoke was from Kara. …: 6 to 8 out of 10 persons evaluated that the smoke was from Kara-sama. Δ: 3 to 5 out of 10 persons evaluated that the smoke was from Kara-sama. ×: 3 or less out of 10 evaluated that the smoke was from Kara-sama.

[0024]

[Table 2] Agarwood oil Chromone addition amount Smoke sensory evaluation (% by weight) Modified agarwood oil 0 ○ (slightly camphor-like, burnt smell of wood) (Example 1) 10 ◎ (strong floral and fragrance) 20 ○ ( 40 Δ (acetophenone odor, camphor-like odor) Camphors agarwood agar oil 0 × (unpleasant odor, disharmony) (before treatment) 10 △ (unpleasant odor, disharmony) 20 × (unpleasant odor) Yes, disharmony)

As can be seen from Table 2, the smoke of the Cambodian agarwood oil before the alkali treatment was very inferior to that of the kara, containing an unpleasant odor and of low quality as a whole. On the other hand, the modified agarwood oil of Example 1 had a fragrance like the burning smell of a camphor-like tree, but was harmonious and good as a whole,
The smoke quality has been greatly improved.

Although karamon-like smoke cannot be obtained even if chromones are added to the agarwood oil before the treatment, if chromones are added to the modified agarwood oil which has been treated with alkali to remove fatty acids, the odor of smoke is reduced. The quality has been further improved and a quality equivalent to that of Kara has been obtained. If the chromone addition amount exceeds 20% by weight, the fragrance tends to be inconsistent with the whole,
Then, an acetophenone odor and a camphor-like odor can be felt. Therefore, the addition amount of chromones is preferably 1 to 20% by weight, particularly preferably 5 to 15% by weight.

[0027]

According to the present invention, it is possible to obtain a modified agarwood oil whose smoke quality is significantly improved by removing fatty acids contained in a conventional agarwood oil by alkali treatment. By adding chromones to this modified agarwood oil, it is possible to easily and inexpensively obtain an agarwood oil that emits a cara-like smoke.

Continued on the front page (72) Inventor Shoji Nakamura 1050 Nippa-cho, Kohoku-ku, Yokohama City, Kanagawa Prefecture Inside Shiseido Daiichi Research Center Co., Ltd.

Claims (7)

[Claims] 1. A modified agarwood oil characterized by removing fatty acids from agarwood oil containing fatty acids by alkali treatment. 2. The modified agarwood oil according to claim 1, further comprising chromones added thereto. 3. The modified agarwood oil according to claim 2, wherein 2- [2- (4-methoxyphenyl) ethyl] chromone as a chromone is added in an amount of 1 to 20% by weight in the modified agarwood oil. A chromone-added modified agarwood oil, characterized in that: 4. A method for producing a modified agarwood oil, comprising removing a fatty acid by treating an agarwood oil containing a fatty acid with an alkali. 5. The method according to claim 4, wherein the ether solution of the agar oil containing fatty acids is extracted sequentially with an aqueous solution of sodium hydrogen carbonate and an aqueous solution of sodium hydroxide to remove the fatty acids and remove the ether from the ether layer. A method for producing a modified agarwood oil, comprising: 6. The modified chromone addition method according to claim 4, wherein chromones are further added to the modified agarwood oil obtained by alkali-treating the agarwood oil containing a fatty acid. A method for producing agarwood oil. 7. The method according to claim 6, wherein 2- [2- (4-methoxyphenyl) ethyl] chromone is added as chromones in an amount of 1 to 20% by weight in the modified agarwood. A method for producing a chromone-added modified agarwood oil.