JPH0226669B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention removes substances (hereinafter referred to as sensitizing substances) contained in ylang-ylang oil that have the property of causing contact skin allergy (hereinafter referred to as sensitizing substances) by vacuum distillation. By blending the distilled essential oil with a compound represented by the general formula below (dehydrodiisoeugenol derivative), ylang-ylang oil with excellent aroma (smell and residual fragrance) and low sensitization is produced. Relating to a method of manufacturing. (Prior art) Ylang-ylang oil is an essential oil obtained by steam distilling the flowers of Cananga odorata (Ylang-ylang), which is grown in Madagascar and Southeast Asia.
Since ancient times, colognes, perfumes, hair tonics,
It is widely used as a flavoring agent in general cosmetics such as creams. In recent years, the presence of sensitizing substances in ylang-ylang oil has been reported (Hideo Nakayama: Journal of the Japanese Dermatological Association, Vol. 84, No. 12, pp. 654-667; Masaru Ishihara: Journal of the Japanese Cosmetic Science Society, Vol. 1) Volume, No. 1, pp. 87-101). Furthermore, it has been confirmed that the sensitizing substances are present in the high boiling point part of ylang-ylang oil (Japanese Patent Application Laid-open No. 98400/1983), and dehydrodiisoeugenol is one of them. BACKGROUND ART Conventionally, a so-called distillation method is known as one of the methods for removing high boiling point parts from natural essential oils, in which the natural essential oil is distilled under reduced pressure and the distilled essential oil and the distillation residue, which is the high boiling point part, are separated. In the distillation method, sensitizing substances are present in the high boiling point parts and can be removed, but the high boiling point parts, which are important as aroma components of ylang-ylang oil, are lost, reducing its value as a fragrance essential oil, and the low boiling point (Distillate essential oil)
If you use it alone, you will not be satisfied with the smell (fragrance) and persistence (persistence of fragrance). (Problems to be Solved by the Invention) As a result of intensive research aimed at resolving the difficulties of the prior art, the present inventors have discovered that the essential oil (low boiling point) (distillate) obtained by vacuum distillation of ylang-ylang oil essential oil)
By blending at least one of the compounds represented by the general formula below (dehydrodiisoeugenol derivatives) into the ylang-ylang oil, it is possible to produce raw or distilled essential oil without adversely affecting the aroma, color tone, and component balance of ylang-ylang oil. We discovered that it is easier to obtain ylang-ylang oil, which has a higher fragrance persistence (persistence of fragrance), has a better odor (scent), and is less sensitizing.
The invention has been completed. An object of the present invention is to provide a method for industrially easily producing ylang-ylang oil with excellent aroma properties (smell and residual fragrance) and low sensitization. (Means for Solving the Problems) The present invention provides that after obtaining a distilled essential oil by performing vacuum distillation at a temperature that does not change the aroma components of ylang-ylang oil, the distilled essential oil is added with a general formula (In the above formula, R is an alkyl group having 1 to 10 carbon atoms,
It is a benzyl group or a phenylethyl group. ) (hereinafter referred to as a dehydrodiisoeugenol derivative for convenience) is a method for producing ylang-ylang oil having excellent aroma and low sensitization. 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 balance of the low-boiling aroma components of ylang-ylang oil as it is in natural essential oils. . The temperature that does not change the aroma components of ylang-ylang oil means that the temperature of the liquid in the distillation can of the distillation apparatus does not exceed 140℃, preferably 120℃.
A temperature below ℃ is appropriate. In this case, the lower the degree of reduced pressure, the better, but normally a condition of 10 mmHg or less is adopted.
Generally, it is preferable to select a lower temperature and reduced pressure. In addition, the distillation amount by vacuum distillation is generally about 80% of the ylang-ylang oil (crude refined oil) used. It is preferable to distill as much as possible without damaging the aroma. As mentioned above, when ylang-ylang oil (crude essential oil) is distilled under reduced pressure under appropriate conditions, the sensitizing substances in the ylang-ylang oil remain in the distillation residue together with high-boiling aroma components, etc. Separated. The distillate essential oil thus obtained does not contain sensitizing substances. Next, the dehydrodiisoeugenol derivative is usually blended into the distillate essential oil by adding the appropriate amount of the dehydrodiisoeugenol derivative to the distillate essential oil while stirring, and uniformly dissolving the dehydrodiisoeugenol derivative. It is carried out by. The blending amount (amount used) of at least one of the dehydrodiisoeugenol derivatives is 0.5 to 10% by weight, preferably 0.5 to 10% by weight based on the weight of the distilled essential oil.
It is 1.0-5.0% by weight. Examples of the compound (dehydrodiisoeugenol derivative) represented by the general formula used in the present invention include methoxy-dehydrodiisoeugenol (hereinafter referred to as compound-1), ethoxy-dehydrodiisoeugenol (hereinafter referred to as compound-1), and ethoxy-dehydrodiisoeugenol (hereinafter referred to as compound-1). 2), propyloxy-dehydrodiisoeugenol (hereinafter referred to as compound-3), butyloxy-dehydrodiisoeugenol (hereinafter referred to as compound-4), amyloxy-dehydrodiisoeugenol (hereinafter referred to as compound-5), hexyloxy-dehydrodiisoeugenol (hereinafter referred to as
(hereinafter referred to as compound-6), heptyloxy-dehydrodiisoeugenol (hereinafter referred to as compound-7),
Octyloxy-dehydrodiisoeugenol (hereinafter referred to as compound-8), nonyloxy-dehydrodiisoeugenol (hereinafter referred to as compound-9), decyloxy-dehydrodiisoeugenol (hereinafter referred to as compound-10), benzyloxy-dehydro Diisoeugenol (hereinafter, compound -
11), phenylethoxy-dehydrodiisoeugenol (hereinafter referred to as compound-12), and the like. In the dehydrodiisoeugenol derivative, the compound-1 is synthesized by reacting (alkylating) dehydrodiisoeugenol with methyl iodide in dimethylformamide in the presence of anhydrous potassium carbonate. Compound-2 to Compound-10 are synthesized by reacting in the same manner as Compound-1 except that the corresponding alkyl bromide is used in place of methyl iodide.
Compound-11 is synthesized by the same reaction as compound-1 except that benzyl bromide is used instead of methyl iodide. Compound-12 is synthesized by the same reaction as compound-1 except that phenylethyl bromide is used instead of methyl iodide. The dehydrodiisoeugenol derivative used in the present invention does not cause skin irritation or sensitization, is safe, and is easily soluble in the distilled essential oil. Below, various properties of the dehydrodiisoeugenol derivative (compound of the present invention) are shown.

[Table] (Effects of the invention) The ylang-ylang oil obtained by the method of the present invention has sensitizing substances removed, retains the aroma of natural ylang-ylang oil, and is rich in so-called naturality. It has a scent. Moreover, its residual fragrance (persistence of fragrance) is superior to that of the distilled essential oil or the crude essential oil before vacuum distillation. The odor (fragrance) was also better than that of the distilled essential oil and the raw essential oil, and no skin irritation or sensitization was observed. According to the present invention, high-quality ylang-ylang oil that does not adversely affect the aroma, color, and component balance of natural ylang-ylang oil, has excellent residual fragrance, has a pleasant odor, and is not sensitizing can be produced industrially. It can be obtained easily and with good reproducibility, and the specificity of its action and effect is remarkable. Examples will be described below. The % shown in the examples means % by weight. The test methods for sensitization, odor retention, odor, etc. are as follows. (1) Test method for sensitization A 4 x 6 cm area of skin on the shoulder blade of a female Hartley Guinea pig weighing 350 to 400 g was shaved.
Three intradermal injections per row were made in two rows in the following order: Freund's Complete Adjuvant was injected intradermally at 0.05 ml in two places on the left and right. 10 test samples of untreated ylang-ylang oil, etc.
% olive oil solution was injected intradermally at 2 sites on the left and right. 20 test samples of untreated ylang-ylang oil, etc.
Add the same amount of sterilized water to the % FCA solution and emulsify it, then inject 0.05ml intradermally into two places on the left and right. One week after these operations, the same area was shaved,
Vaseline containing 10% sodium lauryl sulfate was applied to cause mild irritation. 24 hours after application, 0.2 ml of an olive oil solution containing 10% of a test sample such as untreated ylang-ylang oil was applied to the same area on gauze, and an occlusive patch was applied for 48 hours. On the 21st day after the intradermal injection, the ventral region was shaved, and test samples such as untreated ylang-ylang oil were applied with 1%, 5%, and 10% olive oil solutions for 24 hours. Judgment was made visually after 24 and 48 hours according to the evaluation criteria shown in Table 1.

[Table] (2) Test method for scent lingering property In order to compare the scent lingering property of the essential oil of the present invention obtained by the method of the present invention with that of the raw essential oil, distilled essential oil, and adjusted essential oil, the following sensory test was conducted. Adopted. Apply 150 mg of the sample essential oil evenly to a 5.5 x 15 cm scented paper and leave it vertically in a sensory testing room (temperature 25°C, humidity 60%, wind speed 0.1 m/sec or less).
Appropriate time after application (e.g. 0 minutes, 30 minutes, 1 hour,
After 2 hours and 4 hours), we compared the residual scent intensity of the sample essential oils attached to each scented paper.
The judgment will be repeated 10 times by a panel of 10 perfume experts. (3) Test method for aroma (odor) In order to compare the aroma of the essential oil of the present invention obtained by the method of the present invention with the aroma of raw essential oil, distilled essential oil, and adjusted essential oil, the following sensory test was conducted. Adopted. A sample essential oil is made into an 80% alcohol solution, and the same amount is applied to a scented paper, and the fragrance of the sample essential oil adhered to each scented paper is compared and judged 10 times by a panel of 10 perfume experts. Example 1 1 kg of ylang-ylang oil (produced in Bourbon) was decompressed to 2
Distillation was carried out under reduced pressure at mmHg and a can temperature of 120°C to obtain 812 g of a colorless and transparent distilled essential oil. As a result of high performance liquid chromatography analysis of this distilled essential oil, no dehydrodiisoeugenol peak was observed. Next, 100% by weight of this distilled essential oil was uniformly dissolved in a proportion of 5% by weight of methoxy-dehydrodiisoeugenol to obtain ylang-ylang oil according to the present invention. Next, sensitization tests were conducted on ylang-ylang oil according to the present invention (essential oil of the present invention), commercially available ylang-ylang oil (crude essential oil) used in vacuum distillation, and the distilled essential oil. As a result, as shown in Table 2, it was confirmed that the ylang-ylang oil according to the present invention (essential oil of the present invention) does not have sensitizing properties.

[Table] Next, the essential oil of the present invention was tested using the above-mentioned fragrance lingering test method.
The residual fragrance of (1) was compared with that of distilled essential oil and raw essential oil. As a result, as shown in Table 3, it was confirmed that the essential oil of the present invention had a high (strong) residual fragrance strength and excellent fragrance persistence.

【table】

【table】

[Table] Number of people.
Next, a sensory test was conducted using the method described above to determine the aroma of the essential oil of the present invention, the distilled essential oil, and the raw essential oil. Table 4 shows the results.
It was shown to.

[Table] As is clear from the results in Table 4 above, the essential oil of the present invention is better in terms of aroma (smell) than the distilled essential oil and the raw essential oil, and is also preferable in terms of aroma. Example 2 For the distillate essential oil obtained by vacuum distilling the commercially available ylang-ylang oil used in Example 1 under the same conditions,
Each of the specific dehydrodiisoeugenol derivatives (above compounds 2 to 12) described later was added in the amounts shown in Table 5 and uniformly dissolved to obtain ylang-ylang oil according to the present invention (essential oil of the present invention). As a result of a sensitization test of these ylang-ylang oils (essential oils of the present invention), no sensitization was observed (no detection). In addition, as a result of a comparative test with the above-mentioned distillate essential oil regarding the residual fragrance after 2 hours of standing time, all of the essential oils of the present invention exhibited a higher residual fragrance intensity than the distilled essential oil. Furthermore, the results of a comparative test with respect to aroma (smell) with the above-mentioned raw essential oil showed that the essential oil of the present invention was better and superior in aroma.
These results are shown in Table 5.

【table】

[Table] Example 3 For the distillate essential oil obtained by vacuum distilling the commercially available ylang-ylang oil used in Example 1 under the same conditions,
A specific mixture of the dehydrodiisoeugenol derivatives (from compound-1 to compound-8) was blended as shown in Table 6 and uniformly dissolved to obtain ylang-ylang oil according to the present invention (essential oil of the present invention). When these essential oils of the present invention were tested for sensitization, no sensitization was detected in any of them. Furthermore, as a result of a comparative test with distilled essential oils regarding the residual aroma after 2 hours of standing time, all of the essential oils of the present invention exhibited higher residual aroma strength than distilled essential oils. Furthermore, the results of a comparative test with respect to odor (fragrance) with the above-mentioned raw essential oil showed that the essential oil of the present invention was better and superior in aroma. These results are shown in Table 6.

【table】

Claims (1)

[Scope of Claims] 1. After obtaining distilled essential oil by performing vacuum distillation at a temperature that does not change the aroma components of ylang-ylang oil, the distilled essential oil is added with the general formula (In the above formula, R is an alkyl group having 1 to 10 carbon atoms,
It is a benzyl group or a phenylethyl group. ) A method for producing ylang-ylang oil having excellent aroma and low sensitization properties, which comprises blending at least one of the compounds represented by: 2. The manufacturing method according to claim 1, wherein the temperature is 140° C. or lower, which does not change the aroma components of ylang-ylang oil. 3. The production method according to claim 1, wherein at least one of the compounds represented by the general formula is blended in an amount of 0.5 to 10% by weight based on the weight of the distilled essential oil.