JPS5968399A - Manufacture of low sensitive low irritant jasmine oil - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention The present invention relates to a method for producing hyposensitizing and hypoallergenic jasmine oil. Conventionally, natural jasmine oil is a natural essential oil that is best known and widely used as a fragrance material for cosmetics. However, it has been pointed out that this substance has sensitizing properties [Nakajiro et al., Koshokai Journal, 3. (Slow 2) 26-35 (1
980)).

Therefore, there are problems when using it as a fragrance ingredient in cosmetics such as perfumes, creams, and milky lotions that are applied directly to the skin.

Natural jasmine oil is composed of dozens of components, but it is believed that only a limited number of these components actually have sensitizing properties. Therefore, if these sensitizing substances can be selectively removed, jasmine oil that has virtually no sensitizing properties can be obtained.

On the other hand, distillation may be used to remove these sensitizing substances, but the aroma components in natural jasmine oil generally have poor thermal stability, and if the distillation temperature is high, the important aroma components will deteriorate and the aroma will deteriorate. There is a problem that quality is significantly impaired.

In order to identify the sensitizing substances present in natural jasmine oil as the first step, the present inventors conducted a combination of fractionation using vacuum distillation, molecular distillation, column chromatography, etc., and a sensitization test on animals. The relationship between each component in natural jasmine oil and its extensibility was investigated in detail. That is, natural jasmine oil is fractionated using the method described above, and each component is separated using preparative gas chromatography in order to more closely examine the sensitizing portion. Identification was performed using an analytical method.

As a result, the main causes of sensitization in natural jasmine oil are eugenol and pendyl salicylate, which were previously known as sensitizing phenols [Shiraki et al.
, (Chaos 6) 762-769C198j.

Eugenol Benzyl Salicylate Next, as a second step, the present inventors continued intensive studies to selectively remove sensitizing phenols from natural jasmine oil. The sensitizing phenols can be removed by fractionating the fractions containing individual sensitizing phenols using a method of If the treated oil obtained by distilling off the solvent is combined with other fractions, jasmine oil with good aroma reproducibility, industrially advantageous and inexpensive, from which sensitizing phenols have been removed can be obtained. I discovered that this could be obtained and filed a patent for it (Japanese Patent Application No. 46373/1983).

Now, in the present invention, as a result of intensive studies to further investigate the safety of natural jasmine oil on the skin, we have developed the use of highly irritating diterpene alcohols (inphytol, phytol, and geranyl linalool). By acetalizing the containing portion with ethyl vinyl ether under acidic conditions, we succeeded in obtaining jasmine oil with significantly reduced irritation.

That is, the inventors discovered that by combining this technology and the previously applied technology, a low-sensitizing and low-irritating jasmine oil with good aroma reproducibility and industrial advantages could be obtained, and the present invention was completed. .

The conditions for vacuum distillation in the present invention must be such that the aroma components of natural jasmine oil are not altered, and the conditions are such that the temperature is 130° C. or less and the degree of vacuum is 2 mmHg or less. In addition, the high boiling point portion is distilled by molecular distillation. The conditions for molecular distillation are a temperature of 120°C.
The following will be adopted.

Natural jasmine oil was distilled and fractionated under the conditions of vacuum distillation and molecular distillation described above, and the fraction containing eugenol and diterpene alcohols (isophytol, phytol,
The part containing geranyl linalool) and pendyl salicylate is subjected to the next process. As much as possible, the distillation conditions should be such that the amount of the fraction containing sensitizing phenols and irritating diterpene alcohols is minimized and the concentration of sensitizing phenols and irritating diterpene alcohols is maximized. It is to set.

The caustic alkali used to treat sensitizing phenols is caustic soda or caustic potash, and the concentration of the aqueous solution is 1 to 5.
Used in weight percent concentrations, preferably between 2 and
It is a 6-fold view percent. When increasing the concentration, adjust the reaction conditions by increasing the amount of nonpolar solvent used so as not to change other components. The amount of caustic alkaline aqueous solution used is 3 to 3 of the amount of sensitizing phenol m to be treated.
It is preferable to use 10 times the molar amount.

Examples of nonpolar solvents include pentane, isopentane,
Aliphatic hydrocarbons such as hexane, hebetane, octane, and cyclohexane can be used, but particularly preferred are pentane, isopentane, and hexane. The amount of solvent used is 1 to 10 times the weight of the area to be treated, preferably 2 to 5 times by weight. Reaction of the sensitizing phenols with the caustic is accomplished by stirring at room temperature for about 1-2 hours.

Next, the reaction solution is allowed to stand, the solvent layer is separated, washed with water, dried, and the solvent is distilled off to obtain a treated oil that does not contain sensitizing phenols.

In addition, pendyl salicylate and diterpene alcohols (
For parts containing diterpene alcohols (isophytol, phytol, geranyl linalool), ethyl vinyl ether is treated under acidic conditions, for example in the presence of phosphoric acid, hydrochloric acid, sulfuric acid, etc.
Generates acetaldehyde ethyl acetal compound of phytol/geranyllinalool.

The amount of ethyl vinyl ether used to produce the compound with the diterpene alcohol is preferably 6 to 5 times the mole of the diterpene alcohol to be reacted.

The reaction is accomplished by stirring for about 1-3 hours at a reaction temperature of 10-60'C.

Next, a solvent was added to the reaction solution, which was washed with water and treated with a 15 to 10 weight percent sodium carbonate aqueous solution and a 1 to 3 weight percent caustic alkali aqueous solution, and after drying, the solvent and excess ethyl vinyl ether were distilled off using sulphate. A treated oil is obtained which does not contain dilsalicylate and contains an a7taldehydonterbenylethyl acecool compound with significantly reduced irritation.

The order of the step of applying ethyl vinyl ether and the step of treating with alkali does not matter.

The sensitizing phenols were substantially removed by combining these treated oils thus obtained with the fraction containing no sensitizing phenols and irritating diterpene alcohols obtained through the above fractionation. A jasmine oil is obtained, which has no sensitizing properties and whose irritating properties are significantly reduced.

In addition, according to the method of the present invention, it has low sensitization and aroma
Although a hypoallergenic jasmine oil is obtained, an appropriate amount of fragrance components may be added as necessary, as shown in the formulation examples below.

As mentioned above, according to the present invention, the fragrance before natural jasmine,
Sensitizing substances and irritating substances can be easily removed from natural jasmine oil without any risk of adversely affecting the ingredients.

Next, the method of the present invention will be explained in more detail with reference to Examples.

〔Example〕

Egyptian natural jasmine (eugenol 1.67%)
, pendyl salicylate 006%, isophytol
4.75%, phytol 1155%, and geranyl linalool 329%) were subjected to vacuum distillation and molecular distillation, and fractionated as follows.

fi+ Vacuum distillation (natural jasmine oil 2005')
Fraction A (cold trap collected fraction) 22 Fraction B (boiling point below 53°C/0.8 mmHg) 5
1 as fraction C (boiling point 59-80-c/0.6 mmH
g; A゛Igenol-containing 142 fraction D (ff14 points 80-112-C102-C1O
602 (Contains residual Min-xc pendyl salicylate, isophytol, phytol, geranyl linalool) 1205' (2) Molecular distillation (residue R-11201iI) fraction E
(, JjH point 90゛C or less / 1.5 x 10-"
mmHg; Contains benzyl salicylate, isophytol, phytol, geranyl linalool) 642 Remaining: (n -II 551i' (The total loss in vacuum distillation and molecular distillation is 4
It was 7. ) Fraction C obtained by the above fractionation (containing eugenol)
141 was dissolved in 100Mt of hexane, 3% by weight aqueous sodium hydroxide solution 1507 was added, and the mixture was vigorously stirred for 1 hour at room temperature. After stirring, the reaction solution was allowed to stand and separated to obtain a hexane solution layer, which was washed with water and dried over sodium sulfate, and then the hexane was distilled off under reduced pressure to obtain treated oil X102. As a result of gas chromatography analysis of fraction C and treated oil X, eugenol found in fraction C was not found in treated oil X. (Figures 1 and 2) Next, 64 g of fraction E (containing pendyl salicylate, inphytol, phytol, and geranyl linalool) and 29 g of ethylvinylnylene are added. 0.51 of an 85% by weight aqueous phosphoric acid solution was charged into a 500 vrl four-cylinder flask equipped with a stirrer, a thermometer, and a reflux condenser.

Then stir vigorously for about 2 hours. At that time, the reaction temperature is 20~
The temperature was maintained at 50"C. After the reaction was completed, the reaction solution was dissolved in 100 mJ of hexane, washed with water, neutralized with a 10% by weight aqueous sodium carbonate solution, and then treated with a 3% by weight aqueous sodium hydroxide solution. After the treatment, the reaction solution was allowed to stand and separated to obtain a hexane solution layer, which was washed with water and dried over sodium sulfate. Hexane and excess ethyl vinyl ether were distilled off under M pressure to obtain treated oil Y. As a result of gas chromatography analysis of fraction E and treated oil Y, it was found that the diterpene alcohols found in fraction E were acetalized in treated oil Y. (Fig. 5, 4) (Figure) Furthermore, removal of penzyl lyricylate was confirmed by gas chromatography/mass spectrometry.

Finally, by combining fractions A1, B1, D, residual mR-■, treated oil Sensitizing/hypoallergenic jasmine oil 1842 was obtained. The final yield was also very high at 92%.

The jasmine oil obtained by the production method of the present invention, in which sensitizing phenols have been removed and irritating diterpene alcohols have been acetalized, has been tested in the Guinea Bisog and Maximization Tests of Magnusoson and Cleveman.
a Pig IAhxlrni-zation Te5
t) The sensitization test carried out in accordance with the law revealed that I('A production potential was naturally reduced); however, at the same time, the skin - The next stimulation was significantly reduced) and the force ('l'JJ 111) was increased.

The skin irritation test is shown below. Skin l14-
Next, in the tlilJ intense test, 5 rabbits of 2.5 to 30 yen were yr +), and trial f[ was 2
Continuous applications were made for 1.1 weeks. According to the reaction criteria, the average value was given as the 5R score.

The results are shown in Table 1. The samples used in the 5 eggplant test were 13 oz. by the method shown in the example.

Natural−↓−−−−−−□□□− Score Irritation test F) a degree frw −? I---'
-(fi, -1,1' +7), I'+J 'd Natural from Egypt, Ya7. Name 1+ 10% by weight 2.42.0
Existing fraction E 10% by weight 3.23・
0 Yes Treated oil Y 10% by weight 0.60
．． 6 None - or Til+ Sofusumi ■ As described above, the jasmine oil obtained by the present invention was found to be a hyposensitizing and hypoallergenic jasmine oil.

Examples of formulations in which the low-sensitizing and low-irritant jasmine oil obtained according to the present invention are blended with other aromatic components are shown below. In addition, the compounding ratio in the preparation example is shown in the heavy jet part.

[Formulation example]

Fraction A (cold trap collected fraction) 1° Fraction B (distillation section) 255 Fraction D (distillation section) 5° Residue R-1275 Processed oil X (desensitizing phenol 5° ) Treated oil Y (desensitizing phenol-275 and desensitizing diterpene alcohols) Methyldihydrojasmone-2,0 tocis-jasmone o,65cis-6
-hexenylbenzo 025 ethyl indole 0.75 acetaldehyde phytyl ethyl acetyl acetolydehyde isofidi 26 ethyl acecur heptataldehyde geranyl 07 naryl ethyl acecur squalene 0.25 other (
Raw materials for odor correction) 06 Total 1 0 0. 0

[Brief explanation of the drawing]

Figure 281 is a gas chromatogram of fraction C (containing eugenol) in Examples. FIG. 2 is a gas chromatogram of treated oil X (demeigenol) in Examples. FIG. 3 is a gas chromatogram of fraction E in Examples. FIG. 4 is a gas chromatogram of treated oil Y in Examples. 1... Eugenol 2... Isophytol 3... Geranyl linalool 4... Phytol 5... Acetaldehyde Isophythylethyl acecool 6... ... Acetaldehyde geranyl linalyl edyl acecool 7 ... Acetaldehyde phytylethyl acetal and above Applicant Kobayashi Kose Taiyo Fragrance Co., Ltd. 261.1U211.177. L.・A fl I(j: 1 15)U/“l
-1u+0 20
50 4U procedural amendment [voluntary]
6 June 14, 1980 7゜ Kazuo Wakaichi, Commissioner of the Patent Office 1 Indication of the case 1982 Patent Application No. 178476 2 Name of the invention Process for producing hyposensitizing/hypoallergenic jasmine oil 3 Amendment Patent applicant 4. Date of amendment order (voluntary) 5. Number of inventions increased by the amendment Contents of the quotient amendment to the "detailed description of the invention" in the specification subject to the amendment (1) Specification On page 4 of Shochuon, line 2-3, "fractionate the parts containing individual sensitizing phenols" to "parts not containing sensitizing phenols and parts containing sensitizing phenols" Correct to ``. (2) In the third line of page 4 of the specification, "the fractionated portion" is corrected to "the portion containing sensitizing phenols." 111 On page 4 of the specification, line 7, ``Good reproducibility of aroma when combined with other fractions, good reproducibility of aroma as natural jasmine oil when combined with a portion that does not contain Jer sensitizing phenols.'' Good,” he corrected. "In combination," and "in the second line of page 5 of the specification."
"Reproducibility of fragrance", "as natural jasmine oil"
Insert. (5) “Industrially advantageous” on page 5, line 3 of the specification
is corrected to "Ichiba is advantageous and inexpensive." (6) "Adopted" on page 5, line 9 of the specification is corrected to "preferred." (7) "Temperature 12" on page 5, lines 11-12 of the specification
0'C or less is adopted. " should be corrected to "Temperature 120°C or less, degree of vacuum 2x i Q-2M) (g or less is preferable."). (8) "Containing eugenol... Regarding the ・・・・・・ part,
amended to ``For parts containing sensitizing phenols and diterpene alcohols.'' (9) In the specification, page 6, lines 6-7, ``The caustic alkali used for treating sensitizing phenols'' has been changed to ``For the portion containing sensitizing phenols, dilute caustic alkali is used as described above.'' It is treated with a combination of non-polar solvents.The caustic alkali used in the treatment is corrected. αQ “Hepetane” in the fourth line from the bottom of page 6 of the specification is “
Heptane”. (Ill Delete “pendyl salicylate” on page 7, line 8 of the specification. 02 Delete “(isophytol, phytol, geranyllinalool)” on page 7, lines 9-10 of the specification. Oy Specification i (Delete ", that is, inphytol, phytol, geranyl linalool" on page 7, lines 13-14 of 5.0〇 "3-5 times" on lines 5-2 from the bottom of page 7 of the specification Correct it to "2 to 5 times." Add hydrocarbons," is corrected. θω "And 1 to 3 wt%
Treated with a caustic alkali solution, neutralized with water, washed with water,
” is corrected. αη In Specification 6, page 8, line 6, "does not contain pendyl salicylate" is deleted. Mark α On lines 10 to 12 of page 10-12 of the specification rj medium chain, "ethyl vinyl ether......I don't care what happens next." is changed to "In addition, sensitizing phenols and diterpene alcohols are shared Regarding the part where: x, q-ruhinyl ether is applied and alkali treatment are both performed, the order does not matter.'' ``Sensitizing phenols have been removed'' in lines 5-4 from the bottom of page 8 of the middle section of the paper is changed to ``does not contain sensitizing alcohols, t-ols, and stinging diterpene alcohols.'' Correct. (A) Specification V) Medium chain, page 8, line 1 from the bottom to page 9, line 3, ``According to the method of the present invention,... mountains...may be blended.'' is deleted. clD Insert "tojite" between "natural jasmine oil" and "fragrance," on page 9, lines 4-5 of the specification. ■ After line 8 on page 9 of the specification: ``In addition,
For the parts that do not contain sensitizing phenols that have been subdivided according to the fractionation conditions, all or part of them can be used in an appropriate amount depending on the purpose, and other aroma components can be added as appropriate to further enhance the aroma. May be added. ” is inserted.

Claims (1)

[Claims] Natural jasmine oil is fractionated by vacuum distillation and molecular distillation, and the part containing sensitizing phenols is treated with alkali, and the part containing irritating diterpene alcohols is treated with edyl vinyl ether under acidic conditions. A method for producing a hyposensitizing and hypoallergenic jasmine oil, which is characterized by combining the fraction containing no sensitizing phenols and irritating diterpene alcohols obtained by the fractionation.