JPS6017479B2 - Method for producing hyposensitizing ylang-ylang oil - Google Patents

Description

[Detailed description of the invention]

The present invention uses a combination of distillation, extraction, and adsorption methods to extract a substance contained in ylang-ylang oil that has properties that exceed contact skin allergy (hereinafter referred to as a seductive substance). The present invention relates to a method for producing ylang-ylang oil, which has a natural pleasant aroma and has low sensitizing properties. Ylang-ylang oil is an essential oil obtained by steam distilling the flowers of Cananga odorata (ylang-ylang tree), which is grown in Madagascar and Southeast Asia. This is one widely used method. In recent years, the presence of sensitizing substances in ylang-ylang oil, along with jasmine oil, cananga oil, etc., has been reported (Hideo Nakayama: Journal of the Japan Dermatology Society Vol. 8, No. 12, 65
Pages 9-66 Katana, Masaru Ishihara:. Journal of the Japanese Society of Transmitter Science, Volume 1,
No. 1, pp. 87-101). However, the nature of the sensitizing substance present in this ylang-ylang oil has not yet been elucidated. Traditionally, methods such as distillation and adsorption have been used to purify essential oils, but distillation can remove sensitizing substances since they exist in the high boiling point, but ylang-ylang oil The high boiling point part, which is important as a fragrance component, is lost, and the value as a fragrance essential oil is lost. In addition, in the adsorption method, sensitizing substances are adsorbed and removed, and a portion of the low molecular weight substances that are important aroma components are also adsorbed and removed, disrupting the aroma balance of ylang-ylang oil, which is also used as a fragrance essential oil. You don't get what you deserve. Regarding the removal of sensitizing substances from ylang-ylang oil, the present inventors conducted detailed research using animals on the fractionated components using distillation, column chromatography, and gas chromatography. When this method was applied to volunteers who were hypersensitive to Iranian oil, it was found that a strong source of sensitization was a highly polar compound with a carbon chain larger than that of sesquiterbene. Therefore, the present inventors have intensively studied methods for removing these causative substances, and have developed a method that does not impair the natural aroma of ylang-ylang oil and can easily remove the seductive substances on an industrial scale. The title book was completed. That is, the present invention performs vacuum distillation of ylang-ylang oil at a temperature that does not change the aroma components to obtain crab oil, adds a nonpolar solvent to the distillation residue, concentrates it, and extracts and separates the resulting solvent extraction. This is a method for producing low-sensitizing ylang-ylang oil, in which the liquid is treated by an adsorption method, and the solvent is removed from the treated extract, and the oil is combined with the crab extract oil. The present invention begins with vacuum distillation at a temperature that does not change the aroma components of ylang-ylang oil, in order to maintain the low-boiling aroma components of ylang-ylang oil in the same filtration balance that natural starch has. The temperature that does not change the aromatic components of ylang-ylang oil means that the temperature of the liquid in the evaporator of the distillation apparatus does not exceed 14 pi, preferably 2 pi or less. In this case, the higher the degree of operating vacuum, the better, but industrially it is 0.5~
1 Torr is often used. An appropriate amount of a nonpolar solvent, for example, 3 to 5 times the amount of the distillation residue, is added to the distillation residue after vacuum distillation, and Hashiyo extraction is performed at room temperature or with slight heating. Then, it is statically and vertically separated into a solvent extract mainly containing ylang-ylang oil high-boiling aroma components and a polymeric magnetic substance, and the polymeric polar substance is separated and removed. Although the static layer temperature is not determined in order to avoid increasing the separation efficiency, a temperature of 0 to 10:00 is suitable. In addition, a non-polar solvent is used as the extraction solvent since a polar solvent does not have an adsorption effect on the adsorbent in the next step. Examples of nonpolar solvents that can be used include chain hydrocarbons such as petroleum ether, n-hexane, and n-heptane, and cyclic hydrocarbons such as cyclohexane, benzel, and toluene, which can be easily recovered by distillation at low temperatures. Any grade may be used as long as it can be produced and does not leave any impurities. Next, an appropriate amount of adsorbent, for example, the same amount to half the amount of the distillation residual bamboo, is added to the separated solvent extract, and the adsorbent is adsorbed in a barrel at room temperature.The adsorbent is separated in a furnace, and the stagnation liquid is distilled to extract the solvent. is removed to obtain concentrated oil. In this case, the organic adsorbent is polystyrene,
Polymers with hydroxyl groups attached to polyethylene are used, but they are not industrially practical due to their cost, so inorganic adsorbents are more practically used. As the inorganic adsorbent, any of commercially available silica gel, alumina, and mixtures thereof may be used. The adsorption method may be the above-mentioned concentrated method, packed column downstream method, or any other commonly used adsorption method. After the adsorbent is separated in the furnace, the components attached to it are washed with the solvent used for extraction as necessary, and the cleaning furnace liquid is combined with the furnace liquid,
The solvent is removed, for example by distillation, to obtain a concentrated oil. This concentrated oil and the crab extract are combined to form a product. The hyposensitizing ylang-ylang oil obtained in this way has all the sensitizing substances removed and retains the aroma of natural ylang-ylang oil, so it can be used as a material for shipboard items. It is truly valuable as a fragrance. Next, Examples and Test Examples of the present invention will be shown, but the present invention is not limited thereto. Example 1 Ylang-ylang oil (made in Bourbon) 36 was evaporated under reduced pressure at a can temperature of 115°C to obtain fraction 2 with a boiling point of up to 90°C/0.5 Torr.
Get 8 points. Add 300 ml of n-hexane to the distillation residue of the 7th batch, stir well, and leave in the refrigerator (-7°C) overnight. Then, the upper layer separated into two layers is taken, 35 g of silica gel (manufactured by Merck & Co., Ltd. - T.7734) is added to this upper layer, and the mixture is heated for 1 hour and filtered. Wash the silica gel with 50 g of n-hexane and combine with the furnace solution. Silica gel 3 acid is added again to the combined furnace solution, concentrated for 1 hour, and then filtered. This silica gel was mixed with 50% of n-hexane.

[Wash with water and mix with furnace liquid. The combined furnace liquors were concentrated under reduced pressure to obtain two brown oils. This was combined with the crab extract oil to obtain 31 females of low sensitizing ylang-ylang oil. Yield 86%. Example 2 Ylang-ylang oil (from Bourbon) 36 female was distilled under reduced pressure at a can temperature of 115°C to obtain fraction 2 with a boiling point of up to 90°C/0.5 Torr.
Get 8 crabs. Add 300% of cyclohexane to the distillation residue of the 7th batch, stir well, and leave in the refrigerator (-7°C) overnight. Then, take the upper layer separated into two layers, add 3 sides of alumina (manufactured by Junsei Kagaku Co., Ltd., activated aluminum oxide 350 mesh) to this upper layer, and heat it for 1 hour. Wash the alumina with 50 ml of cyclohexane and combine with the furnace solution. Add alumina triacid again to the combined furnace liquid, stir for 1 hour, and filter through the furnace. Wash this alumina with 50% of cyclohexane,
Combine with furnace liquid. The combined furnace liquors were concentrated under reduced pressure to yield a brown oil. This was combined with the above-mentioned crab oil to obtain 30 volumes of low-wisteria ylang-ylang oil. Example 3 Ylang-ylang oil (produced in Bourbon) was distilled under reduced pressure at 116°C to the boiling point, and fraction 2 with a boiling point of 90°C/0.5 Torr was obtained.
Obtain 8 images. 7 pieces of distilled Kotou were loaded onto a column prepared with 300M hydroxyl group-attached polyethylene TSK gel -160 (manufactured by Toyo Soda), and the entire amount was adsorbed. Thereafter, the aromatic components were eluted with a 1:1 mixed solvent of n-hexane and ethyl acetate. The eluate was concentrated under reduced pressure to give a brown oil. This was combined with the crab extract oil to obtain a low sensitizing ylang ylang oil 31 crab. Yield 87
%. Test Example 1 The same ylang-ylang oil (made in Bourbon) as described in Example 1 was distilled under reduced pressure at a can temperature of 115°C, and the boiling point was 9.
/ 300 for 7 females excluding crabs up to 0.5 Torr
Add n-hexane, stir well, and leave in the refrigerator (-7°C) overnight. Then, in the lower layer separated into two layers, n-hexane is removed, and n-hexane is removed.
- One total hexane-insoluble portion was obtained. Also, add 3 ounces of silica gel (manufactured by Merck & Co., Ltd. - T.77 milk) to the upper layer, stir for 1 hour, and filter in the oven. Add 3 ounces of fresh silica gel to the furnace solution again, and stir for 1 hour, then pass through the oven. do. Put the silica gel together
- After washing thoroughly with hexane, silica gel is washed with methanol:
Elute with ether (1:1), concentrate the eluate, and transfer to silica gel adsorption section 25. got him. Commercially available ylang-ylang oil and hyposensitizing ylang-ylang oil prepared in Example 1 (Example 1)
A comparative test was conducted on the skin reactions of ylang-ylang oil), the n-hexane insoluble part, and the silica gel adsorbed part prepared as described above. The test method is Magnusson's Maximization Test.
test) was applied. The shoulder blades of Hartley guinea pigs weighing 350-40 kg were shaved and shaved 3x.
The following three types of solutions were intradermally injected into the hair removal area of 4 arcs to form a seduction treatment group. ■ Freund comp 6 adjuvan [) (
FCA) in two places on the left and right at a concentration of 0.05 ■ Untreated ylang-ylang oil only at two places on the left and right at a rate of 0.05 ■ Add sterile water at the same base to the FCA solution containing 40% untreated ylang-ylang oil and emulsify. The solution was injected intradermally at 0.05M each into two areas on the left and right, and in the control group, the following two types of solutions were intradermally injected into the same hair removal areas. ■ Secrete 0.05 FCA in two places on the left and right ■ Add the same amount of sterilized water to FCA and emulsify the solution, then secrete 0.05 in each place in two places on the left and right.
5. Always one week after these operations, the same part of the shoulder blade was shaved again and vaseline containing 10% sodium lauryl sulfate was applied. 2 hours after application, apply 10% untreated ylang-ylang oil to the same area.
A solution containing 0.2% FCN was applied using a 2x4 oven paper for 4 lead hours. For the control group, water was used instead of perfume. On the 21st day after the intradermal injection, the flanks of the guinea pigs were shaved and a sensitization induction test was conducted. The acetone solution of the test substance was added to the tampering treatment group and the control group in a 1. Mother's skin 0.
02 [Open application. Judgment was made based on the following scores after 2 hours and 4 hours after application. Score: No change to the naked eye
:0 Mild or mottled erythema :1 Moderate erythema
:2 Severe erythema and edema :3 The intensity of the reaction was calculated from the positive sensitization rate and the average score as follows. Sensitization positive rate (PR) = Total average score of guinea pigs' scores (M nagi): Used for experiments. The number of guinea pigs tested and the results are shown in Table 1.From the results in Table 1, it was found that ylang-ylang oil of Example 1 was not found to be more sensitizing than commercially available ylang-ylang oil. It was found that the source of sensitization was present in the n-hexane insoluble area. Table 1 (Note) Concentration of phosphorus indicates the sample concentration in the acetone solution. Test Example 2 Three types of sensitization: commercially available ylang-ylang oil and low-sensitizing ylang-ylang oil prepared in Example 2 and Example 3 (referred to as ylang-ylang oil of Example 2 and ylang-ylang oil of Example 3). A comparative test was conducted on productivity. Magnuson's maximization test was applied as the test method. Using female Hartley guinea pigs weighing 340-38, intradermal injection, application of vaseline containing 10% sodium lauryl sulfate, and occlusive application of FCA solution containing 10% ylang-ylang oil were performed in the same manner as described in Test Example 1. . For the control group, water was used instead of perfume. On the 21st day after the intradermal injection, the flanks of the guinea pigs were shaved and a sensitization induction test was conducted. An acetone solution of the test substance was applied to the skin of the sensitized group and the control group at a concentration of 0.02. Judgment was made on the same machine as described in Test Example 1 after 2 feeding hours and 4 anchoring hours after application. The results are shown in Table 2. From the results in Table 2,
It was found that the ylang-ylang oil of Example 2 and the ylang-ylang oil of Example 3 had no sensitizing properties compared to commercially available ylang-ylang oil. Table 2) Concentration Phosphorus indicates the sample concentration in the acetone solution. Test Example 3 A comparative test was conducted on the sensitization properties of commercially available ylang-ylang oil and the low-sensitizing ylang-ylang oil prepared in Example 1 (ylang-ylang oil of Example 1). As a test method, samples (5%
Concentration) was applied using a closed method in which the test was applied for 4 hours. Judgments were made 1 hour and 2 hours after removal. The criteria for patch testing are the ICDRG (abbreviation for International Contact Dermatitis Research Group) standards (written by Sigfrid Fregat, co-translated by Kunihiko Yoshikawa and Tetsuro Sugai, "Contact Dermatitis Manual", 1. March 30, Japanese Industrial Skin Hygiene). published by the association). Judgment criteria - 10 negative reactions? Suspicious reaction: weak erythema only 10 weak (non-vesicular) Intestinal reaction: erythema, infiltration, sometimes papules 10 strong (small vesicular) Positive reaction: erythema, infiltration, papules, vesicular carcinoma + 10 extremely Strong positive reaction: The results of the blistering reaction experiment are shown in Table 3. From the results in Table 3, it can be seen that commercially available ylang-ylang oil exhibits strong sensitizing properties, while the ylang-ylang oil produced by the present invention It can be seen that the sensitization of the low-sensitizing ylang-ylang pongee is significantly reduced. Test Example 4 A comparative test was conducted on the sensitization properties of three types of commercially available ylang-ylang oil, ylang-ylang oil of Example 2, and ylang-ylang oil of Example 3. The X test method was conducted using a closed method in which a sample (5% concentration in Vaseline) was applied to the upper backs of 20 patients with contact dermatitis caused by IQ Ryukin and 20 ordinary people. Judgment was made 3 hours after removal of the patch group using the DRG criteria described in Test Example 3. The experimental results are shown in Table 4. Table 4 From the results shown in Table 4, commercially available ylang-ylang oil exhibits strong sensitizing properties, whereas the sensitizing properties of the low-sensitizing ylang-ylang oil produced according to the present invention are significantly reduced. I understand that.

Claims (1)

[Scope of Claims] 1 Distillate oil is obtained by performing vacuum distillation at a temperature that does not change the aroma components of ylang-ylang oil, and a non-polar solvent is added to the distillation residue and stirred, followed by extraction and separation using solvent extraction. A method for producing a low-sensitizing ylang-ylang oil, which comprises treating the liquid with an adsorbent, and combining the oil obtained by removing the solvent from the treated extract with the distillate oil. 2. The method for producing a low-sensitizing ylang-ylang oil according to claim 1, wherein the temperature is 140° C. or lower without changing the aroma components of the ylang-ylang oil.