JPH0353357B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a low sensitizing diasmine oil. [Prior Art] Conventionally, natural diasmine oil is one of the most well-known and widely used natural essential oils as a fragrance material for cosmetics, but it has been pointed out that it has sensitizing properties. [Nakayama et al., Koshokai Journal,
3, (No. 2) 23-35 (1980)]. Therefore, there have been problems when using it as a fragrance ingredient in cosmetics such as perfumes, creams, and milky lotions that are applied directly to the skin. [Problems to be Solved by the Invention] Natural diasmine oil is composed of dozens of components, but only a limited number of these components actually have sensitizing properties. It is considered to be a substance. Therefore, if these sensitizing substances can be selectively removed, it is possible to obtain diasmine oil that has virtually no sensitizing properties. On the other hand, the aroma components in natural diasmine oil generally have poor thermal stability, and distillation is required to remove sensitizing substances from natural diasmine oil.
If the distillation temperature is high, important aroma components will change in quality.
There was a problem that the quality of the fragrance was significantly impaired. [Means for Solving the Problems] First, in order to identify the sensitizing substances present in natural diasmine oil, the present inventors conducted fractionation using vacuum distillation, molecular distillation, column chromatography, etc. The relationship between each component in natural diasmine oil and its sensitization properties was investigated in detail using the sensitization test in That is, natural diasmine oil is fractionated by the above-mentioned means, and each component is separated by preparative gas chromatography in order to more closely examine the sensitizing category. Identification was performed using an analytical method. As a result, the main causes of the sensitizing properties of natural diasmine oil were eugenol and benzyl salicylate, which were previously known as sensitizing substances [Yamamoto et al., Skin, 23 , (No. 6) 762-769]
(1981)]. Next, the present inventors continued intensive studies to selectively remove the sensitizing substances from natural diasmine oil, and as a result, they removed the sensitizing substances from natural diasmine oil using physical means such as vacuum distillation and molecular distillation. fractionated into a part that does not contain sensitizing substances and a part that contains sensitizing substances,
The part containing the sensitizing substance is dissolved in a non-polar solvent and then treated under mild conditions with alkaline washing, the sensitizing substance is removed by separating the liquids, and then the non-polar solvent is distilled off. By combining the resulting residual oil with the part that does not contain sensitizing substances, it is possible to obtain diasmine oil from which sensitizing substances have been removed, with good reproducibility of the aroma of natural diasmine oil, and which is industrially advantageous and inexpensive. They discovered this and completed the present invention. That is, in the present invention, natural diasmine oil is distilled under reduced pressure at a temperature of 130° C. or less and a degree of vacuum of 2 mmHg or less, using natural diasmine oil as a first step, to obtain an initial first fraction, a second fraction,
fractionating into a third fraction and one residue fraction, and distilling eugenol into the second fraction and leaving benzyl salicylate in the first residue fraction, and as a second step, separating the first residue fraction from the first residue fraction. The temperature below 120℃,
Molecular distillation is carried out under reduced pressure conditions of 2×10 ^-2 mmHg or less,
fractionation into a fourth fraction and a second residue fraction, and distilling benzyl salicylate into the fourth fraction, and as a third step, the second fraction and the fourth fraction are treated with a nonpolar solvent. After washing with an aqueous sodium hydroxide and/or potassium hydroxide alkali solution, the non-polar solvent layer is separated and washed with water. The present invention relates to a method for producing a low sensitizing diasmine oil, which is characterized by combining the residual oil fraction with the initial first fraction, third fraction, and second residue fraction. The conditions for the vacuum distillation in the present invention must be such that they do not alter the aroma components of natural diasmine oil, and are preferably at a temperature of 130° C. or less and a degree of vacuum of 2 mmHg or less. Under these conditions, natural diasmine oil is distilled under reduced pressure, and the parts that do not contain sensitizing substances, that is, the initial first and third fractions, and the parts that contain sensitizing substances, that is, eugenol. and the first residue fraction containing benzyl salicylate. Furthermore, the conditions for the molecular distillation in the present invention are:
Preferably, the temperature is 120° C. or less and the degree of vacuum is 2×10 ^-2 mmHg or less. Under these conditions, the first residue fraction after vacuum distillation is distilled and fractionated into a portion containing benzyl salicylate, ie, the fourth fraction, and a portion not containing benzyl salicylate, ie, the second residue fraction. Thereafter, the eugenol-containing portion (the second fraction) and the benzyl salicylate-containing portion (the fourth fraction) are subjected to the next operation.
The important point here is to minimize the loss of important aroma components as they are removed along with the sensitizing substances during the subsequent alkaline cleaning process to remove sensitizing substances, namely eugenol and benzyl salicylate. Care should be taken to minimize the amount of sensitizer-containing portion and maximize the sensitizer concentration. Next, the second fraction and the fourth fraction containing the sensitizing substance are dissolved by adding a nonpolar solvent and washed with alkali by adding an aqueous alkali solution. At this time, the second fraction and the fourth fraction may be treated together, or they may be treated separately and then mixed. As the nonpolar solvent, for example, aliphatic hydrocarbons such as pentane, isopentane, hexane, heptane, octane, and cyclohexane can be used, and particularly preferred are pentane, isopentane, and hexane. The amount of nonpolar solvent used is 1 to 10 parts by weight, preferably 2 to 5 times the amount by weight of the portion containing the sensitizing substance. In addition, the alkaline agent used in the alkaline cleaning treatment to form adducts with sensitizing substances is sodium hydroxide and/or potassium hydroxide;
The concentration in aqueous solution used is 1 to 5 weight percent, preferably 2 to 3 weight percent. The reaction conditions are relaxed by increasing the amount of nonpolar solvent used so as not to change other components when the concentration is increased. The amount of alkaline aqueous solution used is 3 to 10 times the amount of sensitizing substance to be treated.
It is preferable to use twice the molar amount. Formation of the sensitizer adduct is easily accomplished by stirring at room temperature for about 1-2 hours. Next, the reaction solution is allowed to stand still to separate the layers, and the nonpolar solvent layer is separated, washed with water, and dried if necessary.
Thereafter, the nonpolar solvent is distilled off to obtain a residual oil containing no sensitizing substances. By combining the residual oil obtained in this way with the portion that does not contain the sensitizing substance, that is, the initial first distillate fraction, the third distillate fraction, and the first residue fraction, the sensitizing substance, i.e. A diasmine oil from which eugenol and benzyl salicylate have been removed is obtained, which is a hyposensitizing diasmine oil. In addition, confirmation of the distillation or presence of the sensitizing substance in the above fractionation operation can be carried out using an appropriate analytical method such as gas chromatography. In addition, as for the parts that do not contain sensitizing substances, which are subdivided according to the above-mentioned fractionation conditions, all or part of them may be used in an appropriate amount depending on the purpose.
Furthermore, other aroma components may be added as appropriate to enhance the aroma. [Example] Next, the manufacturing method of the present invention will be explained in more detail with reference to Examples. Example Natural diasmine oil from Italy (eugenol)
Contains 0.82%, benzyl salicylate 0.03%, 1st
(See figure) 180g was distilled under reduced pressure at a degree of vacuum of 0.8mmHg.
It was fractionated as follows. Initial first fraction: Fraction A (fraction up to 75°C, see Figure 2) 37g Second fraction: Fraction B (fraction above 75°C to 80°C; contains 21% eugenol, Figure 3) Reference) 7g 3rd distillate: Fraction C (Fraction above 80°C to 130°C, 4th
(See figure) 17g First residue: Residue R (contains benzyl salicylate,
(See Figure 5) 114 g The residue R was then subjected to molecular distillation at a reduced pressure of 3 x 10 ^-3 mmHg and fractionated as described above. Fourth fraction: Fraction R-1 (fraction up to 120°C; containing 0.10% benzyl salicylate, see Figure 6) 57 g Second residue: Residue R-2 52 g (Note that the The loss is 5 each
It was hot at g. ) 7 g of fraction B (containing eugenol) obtained by the above fractionation and 57 g of fraction R-1 (containing benzyl salicylate) were combined (see Figure 7), and pentane was added.
Dissolved in 200g of 3% sodium hydroxide aqueous solution 60
g and stirred vigorously for 1 hour at room temperature. After stirring, the reaction solution was allowed to stand still and separated to obtain a pentane layer, which was washed with water and dried with sodium sulfate.
g (see Figure 8). Finally, by combining this residual oil with fractions A and C and residue R-2,
163 g of diasmine oil from which sensitizers of eugenol and benzyl salicylate have been removed (final yield
90.6%) (see Figure 9). The presence of distillate substances and sensitizing substances in each of the above operation steps was confirmed by gas chromatography analysis under the following conditions. Figures 1 to 9 are gas chromatograms at each stage. Equipment used and its conditions Model: Shimadzu GC-5A Column: PEG 20M (5%) 3mm x 2m Column temperature: 210℃ (temperature raised from 100℃ at 4℃/min) Carrier gas: Helium gas flow rate 35ml/min Detector: Hydrogen ion flame detector (FID) As a result, as is clear from the comparison between Figures 1 and 9, the diasmine oil obtained by the production method of the present invention is It was confirmed that the sensitizing substances eugenol and benzyl salicylate present in ) were removed. Example The procedure was carried out in the same manner as in Example except that 250 g of hexane was used instead of pentane and 100 g of 2% potassium hydroxide aqueous solution was used instead of 3% sodium hydroxide aqueous solution. Removed diasmine oil 162
g (90% final yield) was obtained. Reference Example A comparative test of sensitization between natural diasmine oil and diasmine oil obtained by the production method of the present invention was conducted.
This test was conducted according to the Gunia Pig Maximization Test method of Magnutsson and Kriegman. The experimental animals used were 10 healthy Hartley white guinea pigs weighing 300-400 g (1 group), and 2 0.05 ml each of Freund's Adjuvant emulsion, 20% sample, and an equal volume mixture of both were placed on the shoulder blades. Intradermal injections were given at a total of 6 sites. After 1 week, 25% to the injection site
The sample was applied in an occluded manner for 48 hours to complete the sensitization induction treatment. In the provocation test, 10% and 5% samples were applied to the back for 48 hours in an occluded manner, and judgments were made. The results were as shown in the table. Note that all the samples used in this test were those of Examples. [Table] [Table] As described above, it was found that the diasmine oil obtained by the production method of the present invention does not have sensitizing properties. [Effects of the Invention] As detailed above, according to the production method of the present invention, eugenol and benzyl can be easily extracted from natural diasmine oil without any risk of adversely affecting the aroma, components, etc. of natural diasmine oil, and on an industrial scale. The sensitizing substance of salicylate can be removed, and a low-sensitizing diasmine oil with a reproducible aroma can be obtained.

[Brief explanation of drawings]

Figure 1 shows the gas chromatogram of Italian natural diasmine oil (before treatment), and Figure 2 shows the fraction A.
Figure 3 shows the gas chromatogram of fraction B, Figure 4 shows the gas chromatogram of fraction C, Figure 5 shows the gas chromatogram of residue R, and Figure 6 shows the gas chromatogram of fraction B. Figure 7 shows the gas chromatogram of fraction B and fraction R-1 combined, and Figure 8 shows the gas chromatogram of fraction B and fraction R-1 combined and washed with alkali. Figure 9 shows the gas chromatogram of the residual oil after treatment.
Low sensitizing diasmine oil obtained by the production method of the present invention (fraction A, fraction C, residue R-2, and the residue after combining fractions B and R-1 and performing alkali washing treatment) Figure 2 shows a gas chromatogram of the mixture (mixed with oil). Each numbered peak in the figure indicates the following components. 1...cis-3-hexenylbenzoate, 2
...Eugenol, 3...Diasmine lactone,
4... Isophytol, 5... Phitylacetate, 6... Benzyl benzoate, 7... Phytol, 8... Benzyl salicylate In each figure, the horizontal axis indicates the retention time (minutes).

Claims (1)

[Claims] 1. Using natural diasmine oil as the first step, temperature
Distillation is carried out under reduced pressure at a temperature of 130° C. or lower and a degree of vacuum of 2 mmHg or lower, and the mixture is fractionated into an initial first fraction, a second fraction, a third fraction, and a first residue fraction, and eugenol is added to the second fraction. distillation, and leave benzyl salicylate in the first residue, and as a second step,
The first residue was heated to a temperature of 120°C or less and a degree of vacuum of 2x.
Molecular distillation is carried out under conditions of 10 ^-2 mmHg or less, fractionated into a fourth fraction and a second residue fraction, and benzyl salicylate is distilled out from the fourth fraction, and as a third step, the second fraction is fractionated into a fourth fraction and a second residue fraction. After dissolving the fraction and the fourth fraction in a non-polar solvent and washing with an alkali solution of sodium hydroxide and/or potassium hydroxide, the layers are separated, and the non-polar solvent layer is separated and washed with water. A method for producing a low sensitizing diasmine oil, which comprises combining the residual oil obtained by distilling off the nonpolar solvent after drying, and the initial first fraction, third fraction, and second residue.