JPH0368699A - Jasmine oil composition containing fractionated lowly contact sensitinogenic natural jasmine oil - Google Patents

Abstract

PURPOSE:To obtain the title composition having high safety and an excellent fragrance comparable to that of natural jasmine oil by incorporating a specified synthetic perfume composition into a specified fractionated lowly contact sensitinogenic natural jasmine oil. CONSTITUTION:The title composition is obtained by incorporating one or more ester compounds of formulas I to X into a fractionated lowly contact sensitinogenic natural jasmine oil which has no peak present at 48.0-50.0 counts with a drop counter when confirmed by means of gel permeation chromatogram determined by gel permeation chromatography under specified measuring conditions. In formulas I to III, a is 1; b is 1 to 3; X is 0-2C saturated alkylene; Y is 2C saturated alkylene; Z is 3C saturated alkylene. In formula IV, R<1> and R<2> are each 1-3C saturated alkylene. In formulas V to VIII, X is 0-2C saturated alkylene; Y is 1-2C saturated alkylene; R<1> is H, CH3 or C2H5; R<2> is 3-6C saturated alkylene; and n is 1 to 4. In formulas IX and X, R<1> and R<2> are each a 6-14C saturated aliphatic alcohol residue.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a low contact sensitizing jasmine oil containing a low contact sensitizing fraction fractionated from natural jasmine oil. Regarding the composition. The natural jasmine oil fraction of the present invention is
In addition to being used as a fragrance itself, it is also used to create a fragrance that is highly safe and has an excellent odor comparable to natural jasmine oil, for example, by combining it with specific ester compounds.

[Prior Art] Jasmine oil is an extremely important flower essential oil that is indispensable for cosmetics, especially perfumes and colognes.

Natural jasmine oil has been cited as one of the causes of cosmetic dermatitis in recent years, and its contact sensitization has become a problem in terms of skin chemistry, and there have been many reports as shown in (1) to (4) below. is being done.

(1) Hideo Nakayama: Fragrance Allergy and Cosmetic Dermatitis, Journal of the Japanese Dermatological Association, Vol. 84, pp. 659-667, 19
1974 (2) Nakayama, H., Hanaoka,
H,,0hsiro, Å,: Allergen Condroldo System (AI IergenControlle)
d System: AC3) Page 19 Metal Publishing 19
Published in 2014 (3) Larsem J, G.: Dermatitis due to a perfume.
fume ), -1tact Dermatitis (C
contact Dermatitis) Volume 1, Volume 14
Pages 2-145 Published in 1975 (4) Chubu Batch Test Research Group (Kamijima, Ritsuko Hayayo)
Fragrance Batch Test, Skin, Vol. 20, No. 195-19
Page 9 In 1978, the present inventors conducted a provocation test on five types of common natural jasmine oils currently on the market (group 1). It was showing a reaction.

Under these circumstances, various commercially available products called low sensitogenic jasmine have been introduced.

However, in our tests, these also had contact sensitization properties. Some of them were low, but since it was synthetic jasmine oil, the odor was not very satisfactory compared to natural jasmine oil (Table 2).

Tables in the margin below Note that the contact sensitization test for Group 1 and Table 2 was carried out in the following manner.

Test method (A) Guinea pig contact sensitization A group of 10 healthy Hartley Alpino guinea pigs weighing 380 to 450 g was used, and the GPHT method of Hagnusson and IiBan (gu;nea I)io was used.
maximization test, 1970 Al
lergic contact dermatit
is 1nthe gurnaa l)ig,
sp=ng field, Iυ, C, C, dinghos
As).

For sensitization treatment, ■0゜hN complete Freund's adjuvant (
Freund's complete adjuvan
t is abbreviated as FCA.

Difco) water emulsion (FCA: 20=1
:1V/V), ■0.1. Q Test substance solution (IOW/V
%/FC^), ■0.1nN 120W/V% test substance in FCA:H20=1:1 (V/V) The emulsion was injected in this order into two rows on the left and right sides of the shoulder and mouth of each guinea pig, a total of six locations. After 7 days, test substance solution (IOW/V%/liquid paraffin) O, hN was applied under occlusion for 48 hours to the injection site where a small amount of 10W/V% sodium lauryl sulfate/white petrolatum was applied after brushing the day before. Sensitization treatment has been completed. The provocation test was conducted 2 weeks after the completion of the above procedure.
A 10 μm solution of the test substance in acetone at each concentration was applied to pricked back and abdominal skin for 24 hours in the open.

For each test, the same number of animals that had been subcutaneously injected with FCA alone were used as a control to distinguish non-specific skin irritation reactions. Judgments were made according to the criteria in Table 3 between 24 and 4B&iy after application.

Table 3 Judgment criteria (1) Erythema and skin formation rating No erythema at all...0 Slight erythema...1 Clear erythema... 2 Those with strong erythema...
3 Edema formation rating No edema...O Slight edema...1 Obvious edema...2 Chemical component analysis of diasmine oil Although some studies have already been reported regarding this, there have been no clear reports regarding the structure of the contact sensitizing substance contained in jasmine oil.

[W that the invention tries to solve! ! As mentioned above, there is currently no jasmine oil with a superior odor and low contact sensitization that is comparable to natural jasmine oil.

Fish Glazed Standing Shellfish 1 The present invention was made in view of the problems of the prior art, and its purpose is to provide a fragrance with excellent safety, especially an excellent odor comparable to natural jasmine oil, and to provide a fragrance with excellent safety. Our goal is to provide high-quality fragrances.

In order to achieve the above object, the present inventors have completed the present invention by searching for sensitizing substances and removing the substances by various specific methods.

[Means for Solving the Problem] That is, the present invention uses a gel permeation chromatogram measured by gel permeation chromatography (hereinafter referred to as GPC) set under specific conditions as a W1 recognition means. , a low contact sensitizing natural jasmine oil composition containing a low contact sensitizing natural jasmine oil composition that does not contain any sensitizing substances present in a specific count in a drop counter.

Here, the low contact sensitization jasmine oil fraction includes not only those having no contact sensitization at all, but also those having sufficiently reduced sensitization.

In terms of score, slight erythema is observed at 11 degrees and 10% of induction (not an obvious skin reaction), that is, the evaluation score in Table 3 is 1° or less.

The present inventors have earnestly conducted various basic studies in pursuit of sensitizing substances.

First, distillation and heating 5I! ! The sensitization potential of the samples that had been treated with water, hydrogenation, alkaline washing, adsorbent, etc. was reduced, and by GPC analysis we were able to find a difference between the samples before and after the treatment. .

That is, as a result of GPC analysis under the conditions shown in Table 4, UV
(280 nm) Differences were observed in the chromatograms (hereinafter abbreviated as UV chromatograms) obtained using an absorption detector. Note that no significant difference was observed in the case of a detector using a differential refractometer.

(Hereinafter, this chromatogram will be abbreviated as RI chromatogram.) Of these, the chromatograms obtained by GPC analysis when natural jasmine oil was washed with an alkaline aqueous solution such as caustic soda or caustic potash are shown in Figures 1 and 2. Ta. The samples used for measurement were untreated Abs, Jasmin
EGYPT (Figure 1) and jasmine oil (Figure 2) obtained by washing the n-hexane solution of the untreated natural jasmine oil with a caustic soda aqueous solution.

The horizontal axis is the count number. The count number is Elutio
It is equivalent to n rime and measures how much (amount) of the moving bed (tetrahydrofuran) flows per hour, and is used as a flow rate monitor (drop counter).
The flow velocity of the moving bed is checked each time, and the outflow position of the components can be accurately determined. If the analytical conditions in Table 4 used in the present invention are used, one count will be 1.2 m1.
It corresponds to n. Note that the moment when the Numble solution is injected into the GPC column is indicated as count O, and thereafter 1.
1 count approximately 1.2m1 at a flow rate of 0m12/min
Signals are received at intervals of n, (100 drops). That is,
At the column outlet, add 100 drops of tetrahydrofuran (
Alternatively, when tetrahydrofuran and separated components) pass through, a mark is written on the recording paper of the recorder as one count.

Comparing these two figures, there is almost no difference in the R1 chromatogram at the bottom of each figure, but in the UV and chromatograms at the top, there is a clear difference in the absorption peak (hereinafter simply referred to as peak) indicated by the arrow in the figure. Acceptable, especially
Drop counter around 48-49 count and 49
It is characteristic that the peak of ``only count display'' disappears after approximately 50 counts.

Table 4 0PC, analysis conditions Model: HLC-802UR (Toyo Sodako IK,
K) Column: Toyo Soda Kogyo G 2000 days 8
Column temperature: 40°C Solvent: Tetrahydrofuran Flow rate: 1.0. I2/Inner pressure
Power: J30k (1/C1') Sample amount: 100 μl of double-layer % tetrahydrofuran solution Detector: UV (280 tv) absorption The G 2000 8-port column manufactured by Toyo Soda Kogyo is as follows.

One column size: inner diameter 7.51mm length 600II
11 Filler: Styrene-divinylbenzene copolymer (porous polymer with average pore size of 2008 and particle size of 10 μm) Filler loading: 24 ml/number of theoretical plates per bottle: 16,000 plates The present inventors
As a result of focusing on and earnestly pursuing the disappeared peak component, we found that the disappeared peak component (hereinafter referred to as the index peak) has a deep relationship with sensitizing substances.

Experimental examples are shown in Table 5.

As shown in Table 5, the distillation residue was found to have contact sensitization properties in all cases.

Next, the distillation residue is subjected to various treatments, and single molecule distillation is one treatment that gives good results. This molecular vaporization has a slightly inferior separation power compared to distillation, but it causes less thermal decomposition and can be applied to the separation of high-boiling substances.

Table 6 shows the results of a contact sensitization test for each fraction when molecular distillation was carried out at 110° C. or lower, and it can be seen that the strength of sensitization varies depending on each fraction. That is,
Fractions 4 to 7 are highly sensitizing.

We believe that sensitizing substances are concentrated in fractions 4 to 7.
The following operations were performed.

Fractions 4 to 7 were separated by countercurrent partition extraction.

Equipment and separation conditions Machine: Double-rotating multi-stage countercurrent romatograph RLCC type (Tokyo Rika Kikai Niini) Separation tube: 11 mm (inner diameter) ·methanol(
Stationary phase) (10:90) Flow rate 1ii: 0.5nR/min Number of rotations: 20 times/min Sample output: 0.117-3g Detector: UV 280ns As shown in Table 7, surprising facts were confirmed. Ta. The mixture of molecular distillation fractions 4-7 has a high sensitization score of 2.8. However, the pentane extracted portion had a score of O, and no sensitization was observed. -10,000, water/methanol extraction part is 1.6 at 0.5% concentration
It shows a score of 5\, indicating that sensitizing substances are concentrated in this area. Furthermore, when the pentane extracted part and the water/methanol extracted part were mixed and a provocation test was performed at a concentration of 5%, the result was 10/10 (2,9), which coincided with the value before extraction. This shows that the sensitization potential of the water/methanol extract is brought out by the pentane extract.

Margin Table 6 Below: Molecular distillation experiment example Preparation sample: 32% was distilled off.Furthermore, we investigated the water/methanol extraction part where sensitizing substances were concentrated, and finally came to understand the sensitizing substances. Ta. It has been found that the U■ chromatogram of GPC analysis can best reveal the presence of a sensitizing substance, so this will be explained below.

FIG. 3 shows the results of GPC analysis of the water/methanol extracted portion under the measurement conditions shown in Table 4.

It was confirmed that the sensitizing substance was present in areas C, D, and F on the UV chromatogram, but not in areas Å, B, and E. Specifically, by GPC preparative separation, the water/methanol extracts of fractions 4 to 7 of molecular distillation were separated into Å, B, C1D.
, E, and F, and a sensitization test was conducted on each portion, and the results shown in Table 8 were obtained.

From the results of GC-H8 etc., the peak seen at 0 parts is coniferyl benzoate (Con1fervl Benz
oate), and the peak seen in part D is coniferyl acetate.
e).

Existence peak areas of the above sensitizing substances (parts C, D, F)
From the results of the GPC chromatogram (Figure 2) of the washed product with an alkaline aqueous solution with reduced sensitivity, the sensitizing substances in parts C and D present at least at 48.0 to 50.0 counts are removed. Based on the experimental findings that jasmine oil with low contact sensitization can be obtained by this method, the presence or absence of the peak of 48.0 to 50.0 counts is used to determine the presence or absence of low contact sensitization. It was found that it can be used as an indicator peak.

The sensitogenicity of part F is less than half of that of parts C or D, which is extremely small, and even if the sensitizing substance Fali were present, the amount contained in jasmine oil would be extremely small. Yes, almost no sensitization reaction is induced. Therefore,
There is no need to consider the influence of part F. In addition, other important components without sensitizing properties coexist.

Each method for producing a low sensitizing natural jasmine oil fraction according to the present invention by removing index peaks, ie, sensitizing substances, from natural jasmine oil will be described below.

(A> Method of vacuum distilling jasmine oil Natural jasmine oil was separated by vacuum distillation.

Generally, natural jasmine oil is considered to be heat unstable. However, the present inventors tried heat treatments such as distillation, and surprisingly found conditions that allowed distillation without foul odor and without decomposition.

Typical experimental examples are shown in Group 5. In this way, it was confirmed that there was a distillate that did not have any off-odor and did not cause contact sensitization by distillation under reduced pressure.

The degree of reduced pressure can be selected arbitrarily, but if the distillation temperature exceeds 110°C, an off-flavor will begin to appear, so it is preferable to select the degree of distillation so that it is distilled at 110°C or lower. For that purpose, approximately 5mm
)l or less is preferable, and about 064 to 0.7 mm q is particularly preferable.

Further, the amount of distillation is to be kept within 37 parts by weight, preferably within 33 parts by weight, based on the initial distillate fraction based on 100 parts by weight of the starting natural jasmine oil.

When distilled at a reduced pressure of 0.4 mm, the distillate reaches approximately 106°C. In terms of ingredients, BenZyI Ben
z.

It is desirable to cut before the ate is distilled out.

Here, the reason for using the above-mentioned distillation method is that when jasmine oil is suddenly distilled, it has been confirmed that if it is distilled more than 37 times, a foreign odor will be produced.

This is presumed to be due to the high boiling point substances contained in jasmine oil decomposing during distillation and causing the off-flavor.

In the chromatogram of this product measured under the conditions shown in Table 4, no index peak of 48.0 to 50.0 counts was observed.

The vacuum distillation referred to here refers to simple distillation, precision distillation, etc. in general.

(B) A method for producing jasmine oil by molecularly distilling the vacuum distillation residue of jasmine oil and treating the distillate with vacuum distillation or adsorption column. Less than 37 parts by weight of the obtained initial distillate fraction was removed, and the remaining 63 parts by weight or more was subjected to molecular distillation and fractionated into a distillate fraction and a residue.

The distillate fraction can be arbitrarily selected up to 17 parts by weight (based on 100 parts by weight of the starting jasmine oil) in addition to the initial vacuum distillation distillate fraction.

As shown in Table 9, the molecular distillation conditions are as follows: If carried out at 130°C or higher, a foreign odor will be produced; preferably if carried out at 110°C or lower, a product with a good odor will be obtained without any foreign odor. Decompression degree is 10X 1
0-2 mmHg or less is preferable.

As the molecular distillation device, a centrifugal type, a falling film type, a wiper type, a pot type, etc. can be used.

Margin Table 9 Below: Prepared sample: The distillate obtained by deep % distillation and then the molecular distillation is further processed by vacuum distillation or adsorption column, etc.
The treated product has a good odor, and the chromatogram of the treated product measured under the conditions shown in Table 4 shows:
No indicator peak between 48.0 and 50.0 counts was observed.

First, vacuum distillation of molecular distillation will be explained in detail.

It was found that the distillate obtained by the above-mentioned methods such as simple distillation and precision distillation had a good odor and did not contain any sensitizing substances. The degree of reduced pressure and distillation temperature are almost the same as the initial vacuum distillation conditions, but the fractional distillation temperature at which high-boiling substances are removed can be raised. According to the example, it was possible to collect the distillate up to 132°C.

In this way, the molecular distillate from which high-boiling substances have been separated in advance by the molecular distillation method is then distilled under reduced pressure to remove the important component cis-jasmon without any off-odor.
A distillate containing methyl jasmonate and jasmine lactone but not containing sensitizing substances is obtained.

Treatment with adsorbents also describes how to remove sensitizing substances.

The adsorbent used is generally ion exchange resin, synthetic adsorbent, etc.

Specifically, the ion exchange resins Amberlyst ■15, A-26, and A-, which can be used in non-aqueous solvent systems, sold by Organo Co., Ltd.
27, A-21, Amperlite ■ as a synthetic adsorbent
XAD-2, XAD-4 (styrene DV8>, XAD-
7, XAD-8 (acrylic acid ester polymer), etc. are used.

First, a sample is dissolved in a solvent such as n-pentane or n-hexane, and then passed through a column packed with an adsorbent. Then, take the eluted portion and distill off the solvent.

All of these adsorbents are effective in reducing sensitization, and the best adsorbent is Amparite XAD-7.
, XAD-8, and other synthetic adsorbents.

(C) A method of manufacturing by molecularly distilling the vacuum distillation residue of jasmine oil and treating the distillation residue obtained with an adsorption column. It was confirmed that there was no indicator peak of 48.0 to 50.0 counts in the chromatogram measured under the conditions shown in Group 4, that is, the sensitizing substance was removed. The molecular distillation residue used in the production method is 23 parts by weight or more based on 100 parts by weight of jasmine oil, which is a natural flower essential oil.

The adsorbent used, operations, etc. are the same as those applied to the above-mentioned fraction.

Among the adsorbents, a good one is Amparite ■XAD-
7. Synthetic adsorbents such as XAD-8.

The low sensitizing natural jasmine oil fraction of the present invention obtained by the above method has a good odor and can be used as a fragrance, but it cannot be put to practical use as it is as a substitute for natural jasmine oil. .

Synthetic aFl regulators represented by the following general formulas [I] to [X] (the general formulas [I] to [ll] are) described in the claims of the patent application filed previously No. general formula [■ is Japanese Patent Application No. 54-40705@, general formula [v
] ~ [■] are based on the general formula [IX
] to [X] are pending in Japanese Patent Application No. 54-40774), and if you add perfume from the perspective of odor, you can create an extremely safe product with low sensitization and an excellent odor equivalent to that of natural jasmine oil. The present invention was completed by confirming that it is possible to easily produce jasmine oil with high properties and that it is an industrially viable means. Of course, addition of other common flavor modifiers is also effective.

The following margin [11 [11] (In formula [1F-[I[1], a is 1, b is 1 or 3, X has 0 to 2 carbon atoms, Y has 2 carbon atoms, Z has 3 carbon atoms. [V] (Formula [V] ~[■], X is a saturated linear or side chain fullkylene group having 0 or 1 to 2 carbon atoms, and Y is a saturated linear or side chain alkylene group having 1 to 2 carbon atoms; ,R
I is a tox, Cl-1i, or C2H1 group, R2 is a saturated linear or side-chain fullkylene group having 3 to 6 carbon atoms, and n is an integer of 1 to 4. ) [VI] [■] (In formula [ff], [X], R1 or R2 has 6 to 1 carbon atoms
4 represents a saturated linear or gIII chain aliphatic alcohol residue. ) Specific examples of these fragrance regulators include 2-ethylhexylbenzoate, 2-ethylbutylbenzoate, 2-ethylhexyl-2-phenoxypropionate, 2-ethylbutyl-2phenoxypropionate. pionate, 3-phenylpropyl-2-ethylbutyrate, 3-
Phenylpropyl-2-ethylhexanoate, β-phenyl edyl phenoxy acetate, 3-phenylpropylphenoxy acetate, propylene glycol dibenzoate, dipropylene glycol diphenoxy acetate, di-2-ethyl butyl tartrate, Tri-2
-ethylbutyl citrate, tri-4-methyl-2-pentyl citrate, tri-2-ethylhexyl citrate, diisobutyl adipate, diisoamyl adipate, and the like.

The natural jasmine oil fraction obtained by the present invention may be used alone or in combination. From the viewpoint of ease of perfume preparation and economy, it is preferable to use all the natural jasmine oil fractions obtained by a series of production methods.

Jasmine oils that can be freed of contact sensitizers by the method of the invention include all natural jasmine oils (regardless of grade). Examples will be shown below, and the safety test results will also be explained in detail.

Hereinafter, "Example 1" refers to an example related to the production of a natural jasmine oil fraction, and an example related to the production of a jasmine oil composition using the same as a perfume example. The blending amount is in parts by weight.

[Example-1] Natural jasmine oil (produced in Egypt) 1,002 (J) was distilled, ~91°C / 0.511
(I'), remainder (It) 668! If, a cold trap collection fraction of 120 was obtained.

Fraction (I) and the fraction collected in the cold trap had no off-odor and no sensitization was observed. Figure 3 shows a chromatogram of fraction (I) measured under the GPC conditions shown in Table 4.
No indicator peak between 0 and 50.0 counts was observed.

Although no off-odor was observed in the residue (If), sensitization was observed.

Divide this remainder (It) 66h into three equal parts (each with 2221
J). One of them, 222g, was subjected to molecular distillation, and the distillate was 13L5!7 (pressure 2.6 ~
4.4X10-2 questions HaS wetness ~109℃), remaining 83
．． 5 (1) and 5.9 g of cold trap collection were obtained.

No off-odor was observed in any of these, but sensitization was observed.

The molecular distillation fraction was divided into three equal parts (43Q) and each was separated by distillation. In both cases, the distillate contained important components such as cis-jasmone, methyl jasmonate, and jasmine lactone, and no off-flavor was observed.

The results are shown in the table. The distillates from Experiments 11 and 12 were not found to be sensitizing. On the other hand, when the distillate portion was increased as in Experiment 13, sensitization was observed and it could not be used for perfume preparation. In addition, the distillate fractions of Experiments 11 and 12 both showed 48% in the chromatogram measured under the conditions shown in Table 4.
．． No indicator peak of 0 to 50.0 counts was observed.

Next, the molecular distillation residue 83. sg was divided into two equal parts of 401 J each, and 40 g of them were subjected to column treatment with a synthetic adsorbent. Synthetic adsorbent Amberlight ■X
AD-7 should first be thoroughly washed and dried to thoroughly remove the odor of the resin. Next, 600% of resin was added to the column according to a conventional method. 2 g and n-pentane as #A opening solution.
．． 000-flow and then concentrate the distillate. 26.1 g of non-sensitizing material was obtained.

In the chromatogram of this product measured under the conditions shown in Table 4, no index peak of 48.0 to 50.0 counts was observed.

Margin below Table A Amount of each: 43g triisostearic acid trimethylolpropane Glucam P-20 (manufactured by Amacol) 8, O This will be used for investigation as a synthetic adsorbent treated distillate section.

Example 1-1 Distillation section (1) 32.0 Distillation cooling trap collection section 1.2 Experiment 12
Distillate section 10. OAD-7 Synthetic adsorbent treatment distillation section 21. O Methyl dihydrojasmonate 3,0 Cis-jasmone 1.0 Alphahexyl cinnamic aldehyde 1.0 Diisobutyl adipate 5.0 Propylene glycol dibenzoate 8.0 Example 1-2 Distillation section distillation cooling Trap collection part Cis-3-hexenylbenzoate oignol Methylpal Titooctadecanol Benzylbenzoate Phytyl 7 Cetate Phytyl 7 Cetate Phytyl stearate Squalane Methyl dihydrdiasmonate Cis-Jasmone 32.0 1. 2 2.5 1.0 2.0 0.5 5.0 3.5 4.0 4.5 4.0 1.0 Alphahexyl cinnamic aldehyde adipate diisobutyl triisostearate trimethylol propane benzoate-2- Ethylhexylglucam P-20 Example 1-3 Experiment 12 Distillate section Ethanol cis-3-hexenyl acetate cis-3-hexenol trans-2-hexenol linalyl acetate linalool methyl benzoate pendyl acetate 1. 5 6.0 8.0 7.0 9.0 10.0 1.0 0.03 0.05 0.01 0.1 7.0 0.2 28.0 Methyl salicylate phenylethyl acetate benzyl alcohol Creosol cis-Jasmonehexylbenzoate Bala-Cresol cis-3-hexenylbenzoate eugenol Indolemethyl-N-acetyl anthranilate Squalane Phytyl acetate Phytyl palmitio Phytyl stearei 1~ Penzylbenzoate Geranyl linalool Methyl dihydrodi V sumonate alpha hexyl 0.05 0.1 2.0 0.01 4.5 0.5 0.8 2.0 2.5 3.0 1.0 7.0 3.0 4.0 3.0 4.0 3.0 2.4 Cinnamic aldehyde adipate diisobutyl benzoate-2-ethylhexyl dibenzoate pyrene glycol triisostearate trimethylol propane glucam F)-20 0,6 1,0 1,0 1,0 1,0 5,0 [Comparative Example-1] Natural jasmine oil (made in Egypt) 503a was distilled and 2
1 to b This fraction could not be used for perfume preparation because it had a strange odor and was sensitizing.

[Example-2] Molecular distillation was performed on 222 g of the distillation residue (II') of (Example-1), and the first fraction 64.7Q (pressure 2.8-4.8X 10-2 m- LoQ, temperature 42~
85°C), second fraction 59, h (pressure 2.6-2.8
X 10-2 miHg, temperature 85-110°C), 93.6 g of residue, and cold trap collection valve 4, OIJ were obtained. Although no off-odor was observed in any of these, sensitization was observed.

This molecular distillation first fraction, 64.71 J, was divided into three equal parts, each with a weight of 21.0(1), and each was separated by distillation.

The results are shown in Table B. Thus, in all cases, the distillate contained important components such as cis-jasmone, methyl jasmonate, and jasmine lactone, and no off-flavor was observed. The distillates from Experiments 21 and 22 were not found to be sensitizing.

On the other hand, as in Experiment 23, when the distillate amount was increased, sensitization was observed, and it could not be used for perfume preparation. Also, Experiment 21.
No peak of 48.0 to 50.0 counts was observed in the chromatograms of any of the distillates No. 22 measured under the conditions shown in Group 4.

Note that these distillation residues and the second fraction of molecular distillation were not used for perfume preparation because they mainly contain isophytol and phytol and are known to have sensitizing properties.

Next, using the molecular distillation residue 93.6Q, column treatment with a synthetic adsorbent was performed. Amber Light ■XAD-8
First, wash and dry thoroughly to remove the odor from the resin. Next, 1,500 ml of resin was added to the column according to a conventional method.
4000d filled with t12 and using n-pentane as a developing solution
, and then concentrate the distillate.

As a result, the number of non-sensitizing substances was 75.6+34%.

In this product, no peak of 48.0 to 50.0 counts was observed in the chromatogram measured under the conditions shown in Group 4.

This is used as a synthetic adsorbent treatment section for perfumery.

Example 2-1 Distillation section 32.0 Distillation cooling trap collection section 1,2AD-8 Synthetic adsorbent treatment distillation section 20.8 Methyl dihydrdiasmonate 3.0 Cis-jasmone 1.2 Alpha Hexyl cinnamic aldehyde 0.8 Cis-3-hexenyl benzoate Jasmone lactone Other (fragrance for odor correction) Citrate Triethyl adipate Diisobutyl Nonapropylene glycol Diglycerin Ether Triisostearate Trimethylol propane Dibenzoate Propylene glycol Implementation Example 2-2 Real lA22 Distillate section AD-8 Synthetic adsorbent treated distillate section Ethanol cis-3-hexenyl acetitocis-3-hexenol 0.1 o, oos O,895 6,0 8,0 6,0 5 ,0 5,O 10,0 20,8 0,05 trans-2-hexenol linalool pendyl acetate methyl benzoate phenylethyl acetate linary acetate benzyl alcohol creosole cis-jasmonhexylbenzoate bara-cresol cis -3-hexylbenzoate eugenol indole methyl-N- acetyl anthranilate methyl cibide O jasmonate Others (fragrance for odor correction) Diisobutyl citrate triethyl adipate 0.01 7.0 28.0 0.2 0.1 0.1 1.5 0.01 4.5 G, 8 2.8 2.5 1.0 0.4 0.8 1.2 Nonapropylene glycol diglycerin ether triisostearate trimethylolpropane phenoxyprobionic acid -2-Ethyl-hexyl 2.0 2.0 3.0 [Example-31 (Example-1) distillation residue (I), 2229, was subjected to molecular distillation, and the first fraction was 52.9 CI (pressure 3
．． 1~4.8x 10-2 *aHa, temperature 42~7
9℃), second fraction 44.7! If (pressure 2.8~3
．． tx 1O-2111HQ, m degree 79-97℃)
, residue 116.9 g, and cold trap collection valve 6, Og
I got it. No off-odor was observed in any of these.

This molecular distillation first fraction is 52.9! Divide J into approximately three equal parts (
17 each. oa). Each was then separated by distillation. In all cases, the distillate contained important components such as cis-jasmone, methyl jasmonate, and jasmine lactone, and no off-flavor was observed. The results are shown in Table C. Experiment 31.32
The distillate was not found to be sensitizing. On the other hand, experiment 3
As shown in 3, when the amount of distillate is increased, sensitization is observed,
It could not be used for perfumery. In addition, no peak of 48.0 to 50.0 counts was observed in the chromatograms of the distillates of Experiments 31 and 32 measured under the conditions shown in Table 4.

Example 3-1 Distillation section-(1> Distillation cooling trap collection section Experiment 32 distillation section Squalane phytyl acetate phytyl acetate Phytyl stearate Penzyl benzoate Geranyl linalool Methyl dihydrojasmonay 32.0 11.0 6.0 3.0 2.0 3.0 2.0 G 3.0 Sis-Jasmon alpha hexyl cinnamic aldehyde Diisobutyl adipate Triethyl citrate Benzyl phenoxy acetate Glucamru 20 citric acid tri1.3- 1.4 1.4 5.0 3.0 8.0 10.0 dimethylbutyl 4.0 total ioo,.

Below is a margin table 8. Each preparation amount 21. OQ Table C 17g each [Example-4] Natural jasmine oil (from Egypt) 100517 to 9
Distilled under the conditions of 1'C/0.5+go+H (l,
A distillate of 3220 g, a residue of 669 g, and a cold trap collection valve of 13 g were obtained.

No off-odor was observed in any of these. The distillate fraction 1 and the cold trap collection valve were not found to be sensitizing.7]1. Further, in the chromatogram measured under the conditions shown in Table 4, no peak of 48.0 to 50.0 counts was observed. The residue was found to be sensitizing. Divide the remaining 669 g into approximately 3 equal parts (222 Q each).

222g of one of them was subjected to molecular distillation under the same conditions as in Example 3, resulting in a distillate of 133.0g and a residue of 82.2g.
, 6.1 g of a cold trap collection valve was obtained. No off-odor was observed in any of these.

5 g of the distillate from this molecular distillation was taken and fractionated repeatedly by gas chromatography under the following conditions.

Gas chromatography conditions column; 10+gmx 1.5IIP E G20M
(20%) Celite 545-3, [1HC
S power ram temperature: 250°C Carrier gas: N 2 1.0k (J/Cf) As a result, 4.2 g was collected. This sample had no off-odor or sensitization properties. No peak between 4860 and 50.0 counts was observed in the chromatogram measured under these conditions.

Further, 40 g of the other distillate from the molecular distillation was taken and subjected to column treatment using a synthetic adsorbent. The synthetic adsorbent and method were carried out in accordance with Example-1. Non-sensitizing substances are 32.
41;l was obtained.

This product showed a chromatogram of 48% when measured under the conditions shown in Group 4. No peak of 0 to 50.0 counts was observed.

The molecular distillation residue was amparite ■XA as in Example-1.
D-7 was used.

An elution area of 52% was obtained based on the amount charged.

This product was found to have no off-odor or sensitizing properties.

Further, when measured under the conditions shown in Group 4, no peak of 48.0 to 50.0 counts was observed in the 0 madogram.

Example 4-1 Distillation distillation section 32.0 Distillation cooling trap collection section 1,3 Gas chromatography one-part collection section 33.6 (Fragrance for odor correction) Diisobutylglucamate adipate P-20 Propylene glycol dibenzoate Triethyl citrate Total Example 4-2 nortrans-2-hexenol linalyl acetate linalool methyl benzoate pendyl acetate methyl salicylate 1.0 0.5 1.5 5.0 5.0 5.0 3.0 13.0 1.0 0.03 0.05 0.02 0.2 8.5 0.2 30.0 0.1 1.5 0.01 4.5 0.5 0.8 2.0 3.2 2.5 1. 0 5.0 0.84 6.0 4.0 5.0 Phenylethyl acetate benzyl alcohol creosole cis-jasmonhexyl benzoate vara-cresol cis-3-hexenyl benzoate indole eugenol methyl-N-7 cetyl Anthranilate benzyl benzoate Others (fragrance for odor correction) Diisobutyl glucam adipate P-20 Triethyl phenylethyl phenoxy acetate citrate Total Example 4-3 Distillation distillation section 32.0 Distillation cooling trap collection section 1 .3XAD-
7 Synthetic adsorbent treatment section 33.6XAD-7 Synthetic adsorbent treatment 8I112.1 Methyl dihydrdiasmonate 1,0 cisdiasmonate
0.5 Others (fragrance for odor correction) 1.5 Diisobutyl adipate 5.0 Glucam P-205.0 Propylene glycol dibenzoate 5.0 Triethyl citrate 3.0 Total 100 Various types obtained in each experimental example Jasmine oil perfumed using the treated product (Example 1-1.1-2.1-3.2-1
．． 2-2.3-1.4-1.4-2 and 4-3) are
All products have the same odor as natural products, and the results of a provocation test with 10% acetone were 0/10 in both the sensitized and untreated animal groups, and no sensitization was observed. Ta.

[Effects of the Invention] The jasmine oil composition containing the fraction of the present invention exhibits an excellent odor comparable to natural jasmine oil, and has safety features that significantly reduce the conventional contact sensitization. Highly effective.

[Brief explanation of drawings]

Figure 1 shows unprocessed ^bs, Jas+gin EGYPT
The GPC chromatogram of FIG. Figure 2 shows Abs, J
The GPC chromatogram of asmin EGYPT alkali-treated product is shown. FIG. 3 shows a GPC chromatogram of the water/methanol extract of Molecular Distillation 4 to 7 fractions of Group 6. FIG. 4 shows a GPC chromatogram of fraction (I) obtained in Example 1. In each figure, the upper part shows UV (280
The n0 chromatogram is shown, and the lower part is the R1 chromatogram. Moreover, the horizontal axis shows the count number. a ・・Phytol+ 1so・Phytolb・・
Benzylbenzoate C...Linalool+aenzy+acetat
ePatent applicant Shiseido Co., Ltd. Figure 2 ml/min. Display of the case Hei rIi, 1st year patent application No. 261498 Name of the invention Jasmine oil containing low contact sensitization natural jasmine oil fraction 7-5-5 Ginza, Chuo-ku, Tokyo As shown in the appendix "Drawings" of the amendment.

Claims (1)

[Claims] (1) When using a gel permeation chromatogram measured by gel permeation chromatography set to the following conditions as a confirmation means, a peak exists between 48.0 and 50.0 counts using a drop counter. [Measurement conditions] Column: 4 G2000H8 manufactured by Toyo Soda Kogyo Co., Ltd., connected in series Column temperature: 40°C Solvent: Tetrahydrofuran Flow rate: 1 .0ml/min. Pressure: 80kg/cm^2 Sample amount: 2% by weight tetrahydrofuran solution 100μ
l Detector: UV (280 nm) absorption The G2000H8 column manufactured by Toyo Soda Kogyo is as follows. Size of one column: Inner diameter 7.5 mm Length 600 mm Packing material: Styrene-divinylbenzene copolymer (porous polymer with average pore size 200 Å and particle size 10 μm) Amount of packing material: 24 ml/Number of theoretical plates per column :16000 stages A low contact sensitization jasmine oil composition characterized by containing one or more ester compounds represented by the following general formulas [I] to [X]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [III] (In formulas [I] to [III], a is 1, b is 1 or 3, X is a carbon number of 0 to 2, Y is a carbon number of 2, and Z is a saturated linear or side chain alkylene group with a carbon number of 3. There are tables, etc.▼ [IV] (In the formula, R^1:R^2 represents a saturated linear or side chain alkylene group with 1 to 3 carbon atoms.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [ V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [VI] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [VII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [VIII] (Formulas [V] to [VIII] In, X has 0 or 1 to 12 carbon atoms.
is a saturated straight chain or side chain alkylene group, Y is a saturated straight chain or side chain alkylene group having 1 to 2 carbon atoms,
R^1 is H, CH_3, or C_2H_5 group, and R
^2 is a saturated linear or side chain alkylene group having 3 to 6 carbon atoms, and n is an integer of 1 to 4. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IX] [X] (In formulas [IX] and [X], R^1 or R^2 has a carbon number of 6 to
14 saturated linear or side chain aliphatic alcohol residues are shown. )