JPH0641593B2 - Low-contact sensitizing natural jasmine oil treated product for fragrance, method for producing the same, and low-contact sensitizing jasmine oil composition for fragrance containing the same - Google Patents

Description

The present invention relates to a low-contact sensitizing processed product obtained by treating natural jasmine oil, a method for producing the same, and a low-contact sensitizing jasmine oil composition containing the same. The natural jasmine oil-treated product of the present invention is used as a perfume itself, for example, by combining and perfume with a specific ester compound, it is highly safe, and a perfume with an excellent odor comparable to natural jasmine oil is obtained. Used to obtain.

Jasmine oil is a very important flower essential oil that is indispensable in cosmetics, especially perfumes and colognes.

However, jasmine oil has been cited as one of the causes of cosmetic dermatitis in recent years, and its contact sensitizing property (hereinafter abbreviated as sensitizing property) has become a problem in dermatology, and the following (1)
There are many reports as shown in (4).

(1) Hideo Nakayama: Fragrance allergy and cosmetic dermatitis, Journal of Japan Dermatological Sciences, Vol. 84, pages 659-667, 1974 (2) Nakayama, H., Hanaoka, H., Ohshiro, A .: Allergen control System (Allergen Controlled System: AC
S) Page 19, Published by Kanehara Publishing Co., Ltd., 1974 (3) Larsen, WG: Dermatitis due to fragrance
a perfume), Contact Dermatitis (Contact
dermatitis) Volume 1, 142-145, published in 1975 (4) Chubu patch test research group (Hiroshi Ueda, Ritsuko Hayakawa) Fragrance patch test, skin, Volume 20, pages 195-199 1978 The inventors Conducted a sensitization test on 5 kinds of common natural jasmine oils (samples 1 to 5) currently on the market.
The results are shown in Table 1. As is clear from Table 1, animal tests using guinea pigs show that they both have sensitizing properties and also show cross reaction with each other.

The sensitization test was carried out by the following method.

Test method Guinea pig sensitization test A group of 10 healthy Hartley albino guinea pigs weighing 380-450 g was used, and GPM of Magunusson and Kligman was used.
T method (guinea pig maximization Test, 1970 Allergic c
ontact dermatitis in the guinea pig.Spring field, I
ll, CC Thomas).

Freund's Complete Adj
uvant Difco (hereinafter abbreviated as FCA) emulsified with an equal amount of water (referred to as a liquid), 10 (W / W)% FCA solution of the test substance (referred to as a liquid), and 20 (W / W)% test substance FCA solution was emulsified with an equal amount of water to prepare 10 (W / W)% test substance emulsions.

, 0.1 m each of the solution is intradermally injected into the left and right two rows at a total of 6 places with the median line being symmetrical to the shaved scapular skin of the guinea pig.

Six days after the intradermal injection, the injection site was shaved, and 0.2 g of white vaseline of 10 (W / W)% sodium lauryl sulfate was applied.

The next day, 0.2 m of the liquid was applied to the injection site and left under occlusion for 48 hours to complete the sensitization treatment.

21 days after the intradermal injection, the induction test was carried out by applying 10 μL of a test substance acetone solution of each concentration to the shaved back skin in an open state.

In each test, as a control animal, 10 animals that had been intradermally injected with only the liquid at the time of the sensitization treatment were simultaneously subjected to the same induction test as described above to distinguish the nonspecific skin irritation reaction of the test substance. . The judgment was made 24 and 48 hours after application according to the following judgment criteria.

Criteria (1) Formation of erythema and crust Evaluation score: No erythema at all ……………… 0 Slight erythema ………………… 1 Clear erythema What is recognized ………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………… could be identified as a erythema. Scores No edema is observed …………………… 0 Slight edema is observed …………………… 1 Clear edema is observed ……………… 2 Strong edema is observed What can be done …………………… 3 In view of these circumstances, the present inventors have pursued a sensitizing substance and have made various basic studies to remove it, and as a result, the sensitizing substance has the following conditions shown in Table 5. Set gel permeation chromatography (Ge
(1) Permeation Chromatography (hereinafter abbreviated as GPC), it was found that the substances present in 47.5 to 49.5 counts and 49.5 to 50.5 counts, and these peaks are mainly composed of coniferyl benzoate and coniferyl acetate. It was found that the sensitizing substance disappears and the sensitizing property is reduced in the sample which has been subjected to treatment such as distillation, molecular distillation, gas chromatography (hereinafter abbreviated as GC) alkali washing, and column chromatography. The present invention has been completed based on the above findings.

That is, the present invention provides a low sensitizing natural jasmine oil treatment product for a fragrance in which coniferyl benzoate and coniferyl acetate are removed, a method for producing the same, and a low sensitizing jasmine oil composition containing the same. Is.

It was the first time that the present inventors found the causative agent of sensitizing property in natural jasmine oil, and isolated it and determined the structure, and further to remove these substances by a method that does not deteriorate the jasmine oil. It was the first successful production of a low sensitizing jasmine oil from which a new sensitizing substance was removed, and it is an epoch-making and industrially significant invention.

First, 510 g of natural jasmine oil for explaining the identification of the sensitizing substance was distilled to separate 161 g of a distillate up to 94 ° C./0.5 mmHg and 347 g of a residue.

No sensitization was found in the distillate, but strong sensitization was found in the distillation residue.

328 g of the above distillation residue was subjected to molecular distillation.

The conditions and the sensitization test results are shown in Table 2.

As is clear from Table 2, the sensitizing properties of the fractions 5 to 11 are strong,
It was found that many sensitizers were present in this area.

Next, the fractions 5 to 11 were fractionated by the countercurrent partition chromatography method under the conditions shown in Table 3 10 times for 3 g each.

While monitoring with a UV detector of 280 nm, the pentane part was concentrated to the point where benzyl benzoate was completely discharged. On the other hand, the effluent after that and the 90% (V / V) water-methanol layer were combined and concentrated as a water-methanol part.

By this operation, 27 g of pentane and 3 g of water-methanol were obtained. A sensitization test was performed on each fraction. The results are shown in Table 4.

As is clear from Table 4, no sensitizing property was found in the pentane part. On the other hand, a sensitizing property was observed in the water-methanol part, and it can be seen that the sensitizing substance is concentrated in this part.

In addition, (water-methanol part + pentane part) showed stronger sensitization than that of water-methanol part alone, and was as strong as molecular distillation 5-11 fraction before countercurrent partition chromatography separation. The workability was confirmed.

From this, it was found that the sensitizing property of the water-methanol part was enhanced by the pentane part.

Next, the GPC analysis conditions in which the water-methanol part is shown in Table 5 [Note that the G2000H8 column manufactured by Toyo Soda Kogyo Co., Ltd. is as follows. One column size: inner diameter 7.5mm, length 600m
m, filler: styrene-divinylbenzene copolymer (porous polymer with average pore size 200Å, particle size 10 μm), filling amount: 24 m / line, theoretical plate number per line: 16000 plates]
, 36.5 to 47.5 counts (fraction A), 47.5 to 51.5
Count (denoted as fraction B), 51.5-58 count (fraction C
Sensitization test. The results are shown in Table 6. As is clear from Table 6, the fraction B was strongly sensitized.

When this B fraction was analyzed by GPC under the conditions shown in Table 5, it was 47.5.
～49.5 count (and U _1), 49.5~50.5 count (U ₂
To), three large UV peak was observed at 50.5 to 51.5 count (and U _3). These U ₁ , U ₂ and U ₃ were fractionated and subjected to a sensitization test. The results are shown in Table 7.

As is clear from Table 7, strong sensitization was recognized in the U ₁ and U ₂ fractions, and no sensitization was recognized in U ₃ .

Therefore, to obtain a large amount of fractions equivalent to the U ₁ and U ₂ fractions,
For 2.5 g of water-methanol part, G under the conditions shown in Table 8
Repeated PC sorting to obtain 37.2-37.8 count fractions 40
to obtain mg.

40 mg of this preparative TLC (PLC Plate Silicagel 60: Mer
The product was separated with a developing solvent (chloroform manufactured by ck Co., Ltd.) and divided into a spotted Rf value of about 0.55 or more and an R value of about 0.35 or less.

The sensitization test results for these parts are shown in Table 9. Table 9
As is clear from the above, it was found that there was no sensitization in the area where the Rf value was about 0.35 or less, and the sensitizing substance was concentrated in the area where the Rf value was about 0.55 or more.

A portion of 10 mg with an Rf value of about 0.55 or more is further processed by TLC (Silic
agel 60, 0.25 mm, Merck, developing solvent,
When analyzed by chloroform), it was separated into two spots having an Rf value of about 0.65 (hereinafter referred to as E) and a spot having an Rf value of about 0.55 (hereinafter referred to as F), to obtain 3 mg and 5 mg, respectively.

As a result of analyzing E and F by gas chromatography (hereinafter referred to as GC), it was confirmed that each had one peak.

FT-IR, GC-MS, ¹ H-NMR and ¹³ C-NMR spectra of E and F were measured. MS of E, F trimethylsilyl compound and ¹ H of E
-NMR and ¹³ C-NMR spectra are shown in Figs.

As a result of analyzing these data, E is coniferyl benzoate (Coniferyl Benzoate) F is Coniferyl Acetate Was confirmed and identified.

Table 10 shows the results of a sensitization test conducted by synthesizing coniferyl benzoate and coniferyl acetate. table
As is clear from 10, it was confirmed that both substances are strong sensitizers.

Further, GPC analysis of the coniferyl benzoate and the coniferyl acetate under the conditions of Table 5 revealed that the coniferyl benzoate was 47.5 to 4 corresponding to the U ₁ fraction.
It has a strong UV absorption peak at 9.5 (this UV absorption peak is referred to as U ₁ peak). In addition, coniferyl acetate
It has a strong UV absorption peak at 49.5 to 50.5 counts corresponding to the U ₂ fraction (this UV absorption peak is the U ₂ peak).

In addition to coniferyl benzoate, there is almost no U ₁ peak in jasmine oil. Therefore,
Coniferylyl benzoate can be easily confirmed from jasmine oil in the UV chromatogram of GPC analysis under the conditions of Table 5.

However, there are other U ₂ peaks in jasmine oil besides coniferyl acetate. In particular, some of the low-sensitizing jasmine oils obtained by the present invention show a U ₂ peak, and the UV chromatogram of GPC analysis alone shows that
Coniferyl acetate in jasmine oil is difficult to identify.

Mass fragmentography analysis method (abbreviated as MF method)
The coniferyl acetate can be quantified accurately when analyzed under the conditions shown in Table 11.

The content of the sample is determined by analyzing a known concentration of coniferyl acetate (synthetic product) and then comparing the peak heights of the samples.

Next, as a measurement example, Table 12 shows a comparison between natural jasmine oil and the low-sensitized jasmine oil described below.

From FIGS. 5 and 6, from the peak height of a known concentration of 10 ppm, the natural jasmine oil (produced in Egypt) can be measured as about 1130 ppm.

Figure 10 shows the MF chromatogram of the low-sensitized jasmine oil in Table 12. In the GPC analysis, there is a non-sensitizing interfering peak at the U ₂ peak (coniferyl acetate) position, and accurate measurement cannot be performed. However, using the MF method, the residual amount of coniferyl acetate is significantly reduced. It turns out that the amount is undetectable.

Further, coniferyl benzoate in the low-sensitized jasmine oil in Table 13 was selected at a column temperature of 210 ° C., a selection ion m / 179 (selected because the S / N ratio was larger than the parent ion m / 356), and a retention time of 6.6 min. It was not detected when MF analysis was performed at.

According to Table 2, a strong sensitizing property was also found in the molecular distillation residue, but it was confirmed by MF analysis that it contained the sensitizing substances coniferyl benzoate and coniferyl acetate.

As described above, the main sensitizing substance could be understood. Next, the method of the present invention for removing these sensitizing substances from natural jasmine oil will be described.

Natural jasmine oil applicable to the present invention is produced in Egypt,
Common ones such as those from grass and Morocco.

The low sensitizing processed jasmine oil of the present invention is obtained by using a natural flower essential oil, jasmine oil, by methods such as distillation, molecular distillation, GC fractionation, column chromatography treatment, and alkali washing alone or in combination. be able to.

In the present invention, firstly, a method of using distillation and molecular distillation alone or in combination is effective.

In general, natural jasmine oil is heat labile and is produced in a method that uses as little heat as possible. However, the present inventors have challenged distillation, and surprisingly, have found conditions under which an offensive odor is not generated and distillation can be performed without decomposition.

For the distillation, general methods such as simple distillation and precision distillation are used.

For the molecular distillation, a general method can be used, and as a device, a centrifugal type, a falling film type, a wiper film type, a pot type or the like can be used.

By using this method, it is possible to obtain a treated product of jasmine oil having a low sensitizing property with a recovery rate of up to 50% by weight.

8 and 9 show basic process diagrams for the distillation and molecular distillation of the present invention. Hereinafter, description will be made based on these.

First, a method of distilling natural jasmine oil (referred to as distillation I) is used.

Table 13 shows a representative experimental example. As is clear from Table 13, it can be seen that distillation produces a jasmine oil having no odor and no sensitizing property.

It is necessary to keep the amount of distillate within 36 parts by weight with respect to 100 parts by weight of natural jasmine oil. (Distillation within 36 parts by weight of distillation I is designated as DI-1.) Preferably,
Within 34 parts by weight.

Next, a method of performing molecular distillation (referred to as molecular weight distillation I) on the residue obtained by removing the above DI-1 as DI-R) is also used. An experimental example of molecular distillation I is shown in Table 15. As is clear from Table 14, it can be seen that the molecular odor is produced when the molecular distillation is carried out at 130 ° C or higher. It is preferably performed at 110 ° C or lower. Molecular distillation I is D
If the amount of I-1 plus 45 parts by weight (with respect to 100 parts by weight of the starting natural jasmine oil, the same applies below) is distilled out, jasmine oil with low sensitization will be obtained. can get. However, at this time, within 30 parts by weight and DI-1
Combined with the above, the fraction distilled out within 45 parts by weight is designated as MDI-1.

Next, molecular distillation I was performed on DI-R to obtain an amount such that the amount of DI-1 and MDI-1 added as a second fraction after distilling MDI-1 was within 77 parts by weight. (DI-1 and MDI-
1 and 1 are combined to obtain a fraction MDI-2 distilled by molecular distillation I so as to have an amount of 77 parts by weight or less. ) This MDI-
If the method of further distilling 2 (distillation II) is used, jasmine oil with low sensitizing property can be obtained. At this time, MDI-2 is D
The total amount of I-1 and MDI-1 is preferably 56 parts by weight or less. At this time, the distillate II fraction was 36 parts by weight or less and DI-1 and MD
It is necessary to keep the amount of I-1 plus 45 parts by weight or less. (36 parts by weight or less, and DI-1 and MD
Distilled so that the total amount is 45 parts by weight with I-1.
Let the fraction distilled by I be DII-1. ) As a sample to be used for distillation II, MDI-
The distillate obtained without separating 1 and MDI-2 (referred to as MDI-12) may be used.

Residues of the distillation and molecular distillation obtained by the above method, that is, a residue obtained by molecular distillation of DI-R (referred to as MDI-R) and M
Distillation residue of DI-2 (referred to as DII-R) was sensitized.

Next, the low sensitizing jasmine oil of the present invention can be obtained by subjecting natural jasmine oil to direct molecular distillation (hereinafter referred to as molecular distillation II). It is necessary to keep the amount of distillate within 30 parts by weight. (Distillation within 30 parts by weight obtained by molecular distillation II is referred to as MDII-1) Next, the natural distillate II is subjected to molecular distillation II to distill MDII-1, and then the second distillate is obtained. As a result, the amount of MDII-1 added was within 77 parts by weight.
The fraction distillated by molecular distillation II so that the amount is within 77 parts by weight is referred to as MDII-2), and the sensitization is low if a method of distilling this MDII-2 (referred to as distillation III) is used. Jasmine oil is obtained. At this time, the distillate III fraction is 36 parts by weight or less, and it is necessary to keep the total amount including MDII-1 within 45 parts by weight. (The fraction distilled by distillation III so that the total amount is within 36 parts by weight and within 45 parts by weight is referred to as DIII-1.) At this time, MDII-1 was used as a sample to be subjected to distillation III.
And a distillate obtained without separating MDII-2 (hereinafter referred to as MDII-12) may be used.

Residue obtained by molecular distillation II of natural jasmine oil [referred to as MEII-R], and residue obtained by distillation III of (MDII-R) (DIII-R)
) Was sensitized.

In the present invention, a method combining the above distillations I, II and molecular distillation I, in particular, a low boiling point substance is distilled off by distilling natural jasmine oil, and then a high boiling point substance is removed by a molecular distillation method with low thermal decomposability. The sensitizing substance could be efficiently removed by the method of separating and distilling the distillate again.

Secondly, an alkali cleaning method is effective.

The alkali washing is a method in which a sample is dissolved in a water-insoluble solvent such as n-pentane, n-hexane and ether, and washed with an aqueous solution such as NaOH and KOH.

When natural jasmine oil is washed with alkali, the treated jasmine oil of the present invention having low sensitizing property can be obtained.

Further, it is more effective when used in combination with the above-mentioned methods of distillation and molecular distillation. The fraction which can be used is each of the above-mentioned fractions and all of the residues, but in particular MDI-2, MDI-12, MDII-2, MDII-
It is more effective to wash 12 with alkali. In addition, MD
The second fraction of distillation II (hereinafter referred to as DII-2) was obtained by distilling I-2 and distilling it so that the amount of DI-1, MDI-1, and DII-1 added was within 55 parts by weight. ) And MDII-2 by distillation III
It is also effective to wash the second distillate III fraction (referred to as DIII-2) distilled with an alkali so that the amount of MDII-1 and DIII-1 added is within 55 parts by weight. In addition, in distillation II
The distillate obtained without separating DII-2 (referred to as DII-12) and the distillate obtained without separating DIII-1 and DIII-2 during distillation III (referred to as DIII-12) are respectively It may be washed with an alkali.

Thirdly, GC fractionation is effective.

In GC fractionation, the sample is injected into a GC equipped with a polar column (for example, a column such as PEG20M, FFAP is used). Then
This is a method in which a column distillate is introduced into a collection tube and cooled to liquefy and collect it. It is presumed that the sensitizing component is removed by thermal decomposition or adsorption in the column.

When the natural jasmine oil is collected by GC, the processed product of jasmine oil of the present invention having a low sensitizing property can be obtained.

The portion which can be used in this treatment is all the above-mentioned fractions, but especially MDI-2, MDI-12, MDII-2 and DII-12, DIII-12.
Can be used for efficient processing.

Fourthly, the method of processing by column chromatography is effective.

The column chromatography method uses a sample as a synthetic adsorbent or
This is a method of treating with a nonpolar solvent (for example, n-pentane, n-hexane, etc.) using a column packed with an ion exchange resin.

As the ion exchange resin, for example, non-sold by ORGANO
Amberlist that can be used in water solvent system -15, A-26,
A-27, A-21, etc.
-Light XAD-2, XAD-4, (styrene DVB), XAD-7, XAD-
8 (acrylic acid ester polymer) and the like.

By subjecting natural jasmine oil to column chromatography, the sensitized processed jasmine oil of the present invention can be obtained.

Furthermore, a treated product having low sensitization property can be obtained by using the above-mentioned distillation or molecular distillation in combination.

Particularly, when the above (MDI-R) or (MDII-R) is subjected to column chromatography treatment, excellent effects are exhibited. At this time, MDI-R and MDII-R are preferably 30 parts by weight or less.

By this treatment, compounds such as coniferyl linolenate and coniferyl palmitate existing in the polymer part (MDI-R, MDII-R) are simultaneously removed.

The various low-sensitized jasmine oil-treated products of the present invention obtained by the above method did not contain U ₁ peak as a result of GPC analysis under the conditions of Table 5, and further under the conditions of Table 12.
It does not contain coniferyl benzoate and coniferyl acetate by GC-MF analysis, and can be put to practical use as a low sensitizing fragrance.

From the industrial and economical point of view, it is preferable to mix and use the treated products. Among them, a particularly preferable method is to use all processed products having low sensitizing properties obtained by removing sensitizing substances from natural jasmine oil by combining various methods.

For example, distilling natural jasmine oil, which is as follows,
32 parts by weight of DI-1 was collected, and 23 parts by weight of MDI-12 obtained by molecular distillation I of DI-R, and 15 parts by weight of the second distillate were obtained.

Next, 23 parts by weight of MDI-12 was distilled II to obtain 18 as DII-12.
Get parts by weight. Next, this DII-12 is washed with alkali to obtain 16 parts by weight of the treated part. Furthermore, the residue of molecular distillation I (MDI-
R) and 29 parts by weight are subjected to column chromatography to obtain 18 parts by weight of the treated part. And DI-1 with low sensitization obtained by these operations, alkali cleaning treatment section,
And the column chromatography processing section.

The recovery rate in this case is 66% by weight.

Note that the present inventors have found that the effects can be recognized in addition to the above-mentioned individual operations or combinations thereof, but have little industrial merit.

In the present invention, a fragrance adjusting agent represented by the following general formulas [I] to [IX] can be added for further flavoring. This makes it possible to obtain a highly safe jasmine oil composition having a low sensitizing property and an excellent odor.

(General formula I) II) Or III) (In the formula, m represents 1 or 3) IV) V) Or VI) VII) Or VIII) IX) Specific examples of these fragrance adjusting agents include, as the fragrance adjusting agent I, 2-ethylhexyl benzoate, 2-ethylbutyl benzoate, and fragrance adjusting agent II.
2-ethylhexyl-2-phenoxypropionate,
2-Ethylbutyl-2-phenoxypropionate, 3-phenylpropyl-2-ethylbutyrate, 3-phenylpropyl-2-ethylhexanoate as flavoring agent III, β-phenylethyl as flavoring agent IV Phenoxyacetate, 3-phenylpropylphenoxyacetate, perfume conditioner V as dipropylene glycol dibenzoate, perfume conditioner VI as dipropylene glycol diphenoxyacetate, perfume conditioner VII as di-2-ethylbutyl tartrate, Di-2-ethylhexyl tartrate, perfume modifier VIII, tri-2-ethylbutyl citrate, tri-4-methyl-2-pentyl citrate, tri-2-ethylhexyl citrate As perfume modifier IX, diisobutyl adipate , Diisoamylua Examples include japete. By blending the fragrance adjusting agent, it is possible to improve the retention property, the balance of odor, and the like. Compounding amount is 40% in low sensitizing jasmine oil
It is below, preferably 5 to 30%.

Examples will be shown below. In addition, the following [Example] refers to an example relating to the production of a natural jasmine oil-treated product, and an example relating to the production of a jasmine oil composition using the same is shown as a perfuming example. The blending amount is parts by weight.

Example 1 Distillation I of 1,002 g of natural jasmine oil (produced in Egypt),
(DI-1) 333g and (DI-R) 668g of -91 degreeC / 0.5 mmHg were obtained.

No offensive odor was observed in any of (DI-1) and (DI-R).

The GPC analysis result of (DI-1) is shown in FIG. 10, and the GPC analysis result of natural jasmine oil is shown in FIG. (The GPC analysis was performed under the conditions shown in Table 5 above.
The C analysis is performed under the conditions shown in Table 5. As is clear from FIGS. 10 and 11, the U ₁ peak of (DI-1) disappears as compared with natural jasmine oil.

Further, it was confirmed that the coniferyl acetate and the coniferyl benzoate have disappeared as a result of the MF analysis.

Then, when a sensitizing test was conducted (DI-1), no sensitizing property was observed.

The results are shown in Table 15.

Next, an example of perfume using DI-1 is shown. This product had a good odor.

Perfume Example 1 (DI-1) of Example 1 33.2 cis-jasmonate 0.3 methyl jasmonate 0.4 methyl dihydrojasmonate 4.0 jasmolactone 0.2 indole 1.0 methyl-N-acetylanthranilate 0.5 phytyl acetate 3.0 fi Cylpalmitate 4.5 Phytyl stearate 4.5 Geranyl linalool 3.0 Benzylbenzoate 6.0 Methyl palmitate 1.0 Squalane 7.0 Alphahexyl cinnamic aldehyde 2.0 Octadecanol 0.5 Absolute mimosa 0.01 Beeswax 0.1 Absoluteson 0.1 Nonapropylene glycol diglycerin ether 3.0 2-Ethylhexyl Benzoate 7.0 Diisobutyl Adipate 7.19 Propylene Glycol Dibenzoate 4.0 Glucam P-20 (manufactured by Amakor) 7.5 Total 100.0 Example 2 Natural Jasmine Oil The Egyptian) was fractionated odor important part by gas chromatography (GC).

Table 16 shows the equipment used and the fractionation conditions.

A branch pipe was attached in front of the detector of GC, the flow path was divided into two, one was connected to the detector and the other was connected to the collection pipe.

The collection tube has been cooled in advance with dry ice methanol, and natural jasmine oil 100μ is GC with a syringe.
And the fraction was retained as a GC preparative component until a retention time of 14 minutes.

The fractionation was repeated 40 times to obtain 2.1 g of GC fractionation treatment section.

The GC fractionation treatment section contained important odor components such as cis-jasmon, methyl jasmonate, and jasmine lactone, and no offensive odor was observed.

The results of GPC analysis are shown in FIG. As is clear from Fig. 12, the U ₁ peak disappears.

Further, as a result of MF analysis, it was confirmed that coniferyl acetate and coniferyl benzoate were not present.

Then, when a sensitization test was conducted, no sensitization was found in the GC fractionation treatment section.

The results are shown in Table 17.

Example 3 10.0 g of natural jasmine oil (produced in Egypt) was added to n-hexane.
Dissolve in 100m, 3m sodium hydroxide aqueous solution 150m
Was added and placed in a separating funnel.

This was shaken on a shaker for 15 minutes and then allowed to stand to fractionate the n-hexane layer. The n-hexane layer was washed with water three times, and after liquid separation, n-hexane was distilled off under reduced pressure with an evaporator to obtain 5.86 g of an alkali-treated portion.

Almost no offensive odor was observed in the alkali-treated part.

FIG. 13 shows the GPC analysis result. As is clear from FIG. 13, the U ₁ peak disappears. In addition, as a result of MF analysis, it was confirmed that coniferyl acetate and coniferyl benzoate were not present.

Then, a sensitization test was conducted, and it was confirmed that the alkali-treated part had a low sensitization property.

The results are shown in Table 18.

Example 4 Distillation I of 1000 g of natural jasmine oil (Egypt),
62 ° C / 0.4mmHg (DI-1) 102g, (DI-R) 897
g was obtained.

(DI-1) and (DI-R) have no offensive odor,
No sensitizing property was observed for (DI-1). (DI-
R) 880 g is subjected to molecular distillation I using a centrifugal type molecular distillation apparatus CMS-5A type manufactured by Bendix Co., Ltd., to -60 ° C./8.4 to 1
1.1 x 10 ^-2 mmHg (MDI-1) 148g, (MDI-R)
I got 731g.

Neither (MDI-1) ((MDI-R) had an offensive odor. Further, GPC analysis revealed that (DI-1) (MDI-
There was no U ₁ peak in 1), and it was confirmed by MF analysis that there was no coniferyl acetate or coniferyl benzoate.

Next, when a sensitization test was conducted, (DI-1) (MD
No sensitization was found in I-1).

The results are shown in Table 19.

Example 5 About 20.0 g of (DI-R) of Example 1, column chromatography treatment with a synthetic adsorbent was performed. First, wash the synthetic adsorbent Amberlite XAD-7 thoroughly with water.
It was dried to remove the offensive odor of the synthetic adsorbent.

The column was packed with 300m of deodorized synthetic adsorbent, and (DI
-R) 20.0 g was developed.

Pour n-pentane 1 as the developing solution, take the outflow part,
N-Pentane was distilled off under reduced pressure with an evaporator to obtain 14.2 g of a synthetic adsorbent-treated part. Almost no offensive odor was observed in the synthetic adsorbent-treated part, the U ₁ peak disappeared by GPC analysis, and the results of MF analysis confirmed that coniferyl acetate and coniferyl benzoate were absent.

Next, when a sensitization test was conducted, no sensitization was found in the synthetic adsorbent-treated part.

The results are shown in Table 20.

Example 6 1000 g of natural jasmine oil (produced in Egypt) was distilled I, and
61 ℃ / 0.5mmHg (DI-1) 102g, (DI-R) 896
g was obtained.

850 g of (DI-R) was subjected to molecular distillation I using a Cendent CMS-5A type molecular distillation apparatus at ~ 58 ° C / 8.3 ~ 12.4 x 10 ^-2 mmHg.
(MDI-1) 65g, 58-110 ℃ / 2.6-8.3 × 10 ^-2 mmH
472 g (MDI-R) 312 g of g of (MDI-2) was obtained.

50 g of (MDI-2) was distilled II to obtain 24 g of (DII-1) and 25 g of (DII-R) at -118 ° C / 0.4 mmHg.

(DI-1), (DI-R), (MDI-1), (MD
I-2), (DII-1), and (DII-R) did not have any offensive odor.

GPC analysis (DI-1), (MDI-1), (D
All of II-1) had no U ₁ peak, and it was confirmed by MF analysis that coniferyl acetate and coniferyl benzoate were not present.

Next, when a sensitization test was conducted, (DI-1), (M
Neither DI-1) nor (DII-1) was sensitized. The results are shown in Table 21.

Example 7 Distillation I of 500 g of natural jasmine oil (Egypt), ~ 6
0 ℃ / 0.4mmHg (DI-1) 51g, (DI-R) 447g
Got

400 g of (DI-R) was subjected to molecular distillation I using the same molecular distillation apparatus as in Example 4 to obtain 240 g of (MDI-12) and (MDI-R) 138 g of 108 ° C / 2.6 to 12.5 × 10 ^-2 mmHg. It was

50.0 g of (MDI-12) was distilled II to obtain 23.4 g of (DII-1) and 26.2 g of (DII-R) at -128 ° C / 0.5 mmHg.

(DI-1) (DI-R) (MDI-12) (MD-R)
No offensive odor was observed in any of (DII-1) and (DII-R).

Moreover, when GPC analysis is performed, U _{1 is} added to (DI-1) and (DII-1).
There was no peak, and it was confirmed by MF analysis that coniferyl acetate and coniferyl benzoate were not present.

Next, a sensitization test was conducted (DI-1), (DII
No sensitization was found in -1).

The results are shown in Table 22.

Example 8 600 g of (DI-R) of Example 1 was subjected to Molecular Distillation I in the same molecular distillation apparatus as in Example 4 ~ 110 ° C / 8.9-2.6 x 10 ^-2 m.
285 g of mHg (MDI-12) (313 g (MDI-R)) was obtained.

Amberlite XAD-8 was used as a synthetic adsorbent,
Column chromatography treatment of 20.0 g of (MDI-12) was carried out in the same procedure as in Example 5, and the synthetic adsorbent treatment section 18.0
g was obtained.

Almost no offensive odor was observed in the (MDI-12), (MDI-R) and synthetic adsorbent treated parts.

GPC analysis revealed that the synthetic adsorbent-treated part had no U ₁ peak, and MF analysis confirmed that coniferyl acetate and coniferyl benzoate were absent.

Next, a sensitization test was conducted, and it was confirmed that the sensitization property of the synthetic adsorbent-treated part was low.

The results are shown in Table 23.

Example 9 (MDI-12) of Example 8 was subjected to GC fractionation under the same apparatus and conditions as in Example 2 to obtain 1.1 g of GC fractionation treatment section.

The GC preparative processing unit has no odor, and when GPC analysis is performed, U ₁
There is no peak, and MF analysis shows coniferyl acetate,
It was confirmed that there was no coniferyl benzoate.

Next, a sensitization test was conducted. As a result, no sensitization was observed in the GC fractionation treatment section.

Example 10 10.0 g of (MDI-12) of Example 8 was melt | dissolved in n-hexane 100m, 1% sodium hydroxide aqueous solution 100m was added, and 500
Add to m separatory funnel. This was shaken with a shaker for 20 minutes and then separated into two layers with a centrifuge. The n-hexane layer is collected, washed three times with water, and then separated into liquids.
Hexane was distilled off under reduced pressure to obtain 7.1 g of an alkali-treated part.

In the alkaline treatment part, important odor components such as jasmine lactone are reduced, but there is no offensive odor, and GPC analysis shows U
There was no ₁ peak, and MF analysis confirmed that neither coniferyl acetate nor coniferyl benzoate was present.

Next, when a sensitizing test was conducted, no sensitizing property was recognized in the alkali-treated part. The sensitization results are shown in Table 25.

Example 11 Using Amberlite XAD-7 as a synthetic adsorbent,
The column chromatography treatment of 20.0 g of (MDI-R) of Example 8 was performed in the same procedure as in Example 5 to obtain 13.0 g of a synthetic adsorbent-treated part.

Almost no offensive odor was observed in the synthetic adsorbent treated part.

Figure 14 shows the GPC analysis results. As is clear from FIG. 14, the U ₁ peak disappears. As a result of MF analysis, it was confirmed that coniferyl acetate and coniferyl benzoate were not present.

Next, when a sensitizing test was conducted, no sensitizing property was observed in the synthetic adsorbent treated portion.

The results are shown in Table 26.

Example 12 500 g of natural jasmine oil (Egypt) was distilled I to ~ 9
3 ℃ / 0.5mmHg (DI-1) 158g, (DI-R) 340g
Got

330 g of (DI-R) was subjected to molecular distillation I by the same molecular distillation apparatus as in Example 4, and (MDI-) at ˜81 ° C./3.1 to 6.0 × 10 ⁻² mmHg.
12) 114 g, 73-g 2nd distillate of 81-109 degreeC / 2.6-3.1 * 10 ^<-2 > mmHg, and 141 g of (MDI-R) were obtained.

Distillation II of 30.0 g of (MDI-12) gave 22.6 g of (DII-12) and 6.9 g of (DII-R) at 130 ° C./0.5 mmHg.

Dilute 5.0 g of (DII-12) with 10 m of n-hexane to give 0.2
10 m of a normal potassium hydroxide aqueous solution was mixed and shaken well to separate the layers. The n-hexane layer was washed with water and then n-hexane was distilled off under reduced pressure with an evaporator to obtain 4.5 g of an alkali-treated portion.

Next, 20.0 g of (MDI-R) was subjected to column chromatography treatment in the same manner as in Example-5, and the synthetic adsorbent treatment section 12.4
g was obtained.

In the alkali-treated part, almost no offensive odor was observed, the U ₁ peak disappeared by GPC analysis, and as a result of MF analysis, it was confirmed that coniferyl acetate and coniferyl benzoate were not present.

Next, a sensitization test was conducted, and it was confirmed that the alkali-treated part had low sensitization.

The results are shown in Table 27.

Next, an example of perfume using (DI-1), an alkali treatment part, and a synthetic adsorbent treatment part is shown. This product had a good odor.

Perfume example 2 Example 13 1000 g of natural jasmine oil (Morocco) was subjected to molecular distillation II with the same molecular distillation apparatus as in Example 6, and the temperature was -60 ° C / 8.0-1.
2.5 × 10 ^-2 mmHg (MDII-1) 221g, 60-110 ℃ / 2.6
〜8.0 × 10 ^-2 mmHg (MDII-2) 475g, (MDII
-R) 303g was obtained.

230 g of (MDII-2) was distilled III to obtain 72 g of (DIII-1) and 156 g of (DIII-R) at 125 ° C./0.5 mmHg.

(MDII-1), (MDII-2), (MDII-R), (DIII-
Both 1) and (DIII-R) had no offensive odor.

In addition, GPC analysis shows that (MDII-1) and (DIII-1) are U
There was no ₁ peak, and MF analysis confirmed that neither coniferyl benzoate nor coniferyl acetate was present.

Next, when a sensitizing test was conducted, (MDII-1)
((DIII-1) had no sensitizing property. The results are shown in Table 28.

Example 14 Using 20.0 g of (MDII-2) of Example 13 as a synthetic adsorbent and using Amberlite XAD-8, the column chromatography treatment was performed in the same procedure as in Example 5 to obtain 16.4 g of the synthetic adsorbent treatment part. Obtained.

The synthetic adsorbent-treated part had no offensive odor and GPC analysis showed no U ₁ peak, and MF analysis confirmed the absence of coniferyl acetate and coniferyl benzoate.

Next, when a sensitization test was conducted, it was confirmed that the sensitization property of the synthetic adsorbent-treated part was low. The results are shown in Table 29.
It was shown to.

Example 15 (MDII-2) of Example 13 was subjected to GC fractionation under the same conditions as the GC fractionation of Example 2 to obtain a GC fractionation treatment section (1.5 g).

It was confirmed that there was no offensive odor in the GC preparative treatment section, there was no U ₁ peak in GPC analysis, and there was no coniferyl acetate or coniferyl benzoate in MF analysis.

Next, when a sensitization test was performed, no sensitization was recognized in the GC fractionation treatment section. The results are shown in Table 30.

Example 16 10.0 g of (MDII-2) obtained in Example 13 was washed with alkali under the same conditions as in Example 3 to obtain 8.5 g of an alkali-treated part.

It was confirmed that the alkali-treated part had no offensive odor, GPC analysis showed no U ₁ peak, and MF analysis showed no coniferyl acetate or coniferyl benzoate.

Next, when a sensitization test was conducted, no sensitization property was recognized in the alkali-treated part. The results are shown in Table 31.

Example 17 Distillation III of 150 g of (MDII-2) of Example 13
(DIII-12) 77g, (DIII-R) 71g at ℃ / 0.4mmHg
Got

30 g of (DIII-12) was diluted with 60 m of n-hexane to obtain 0.0
90 m of a 2N aqueous potassium hydroxide solution was mixed, shaken well, and after liquid separation, washing with water was repeated 3 times, and n-hexane was distilled off under reduced pressure with an evaporator to obtain 29 g of an alkali-treated portion.

It was confirmed that the alkali-treated part had no offensive odor, GPC analysis showed no U ₁ peak, and MF analysis showed no coniferyl acetate or coniferyl benzoate.

Next, a sensitization test was conducted, and it was confirmed that the alkali-treated part had low sensitization. The results are shown in Table 32.

Example 18 (MDII-R) of Example 13 (20.0 g) was subjected to column chromatography under the conditions of Example 5 to synthesize a synthetic adsorbent 13.2.
g was obtained.

It was confirmed that the synthetic adsorbent treated part had no offensive odor, GPC analysis showed no U ₁ peak, and MF showed no coniferyl acetate or coniferyl benzoate.

Next, when a sensitizing test was conducted, no sensitizing property was observed in the synthetic adsorbent-treated part. The results are shown in Table 33.

Example 19 1000 g of natural jasmine oil (made in Italy) CM manufactured by Bendix
Perform molecular distillation II with S-5A type molecular distillation apparatus, ~ 85 ℃
/4.0-13.2×10 ^-2 mmHg (MDII-12) 558g, (MDII-
R) 441 g was obtained.

500 g of (MDII-12) was distilled III, and (DIII-1) of -92 ° C / 0.4 mmHg (DIII-1) 313 g of 92-128 ° C / 0.4 mmHg (DIII-
2) 99 g and (DIII-R) 86 g were obtained.

Dilute 60 g of (DIII-2) with 120 m of n-hexane to obtain 0.0
150 m of a 2N aqueous potassium hydroxide solution was mixed, shaken well, separated, washed three times with water, and then n-hexane was distilled off under reduced pressure with an evaporator to obtain 56 g of an alkali-treated portion.

Column chromatography was performed on 20.0 g of (MDII-R) under the same conditions as in Example 5 to obtain 14.1 g of a synthetic adsorbent-treated part.

(MDII-12) (MDII-R) (DIII-1) (DIII-2)
(DIII-R), the alkali-treated part, and the synthetic adsorbent-treated part did not have an offensive odor.

It was confirmed by GPC analysis (DIII-1) that there was no U ₁ peak in the alkali-treated part and the synthetic adsorbent-treated part, and by MF analysis that there was no coniferyl acetate or coniferyl benzoate.

Next, when a sensitizing test was conducted, the sensitizing properties of (DIII-1), the alkali-treated part and the synthetic adsorbent-treated part were all low.

The results are shown in Table 34.

Next, an example of perfume using (DIII-1), an alkali treatment part, and a synthetic adsorbent treatment part is shown. This product had a good odor.

Fragrance Example 3 (DIII-1) of Example 19 35.0 Alkali-treated part of Example 19 6.5 Synthetic adsorbent-treated part of Example 19 29.8 Cisjasmon 0.3 Methyljasmonate 0.4 Methyldihydrojasmonateto 2.5 Jasmolactone 0.3 Indole 1.0 Methyl-N-acetylanthranilate 0.5 Phytyl acetate 3.0 Phytyl palmitate 2.0 Phytyl stearate 2.0 Geranyl linalool 3.0 Benzyl benzoate 6.0 Methyl palmitate 1.0 Cis-3-hexenyl benzoate 0.5 Eugenol 0.5 Absolute mimosa 0.01 Bees wax 0.1 Absoluteson 0.1 Alpha cinnamic aldehyde 1.2 Diisobutyl adipate 2.5 Propylene glycol 2.0 Total 100.0

[Brief description of drawings]

FIG. 1 shows the MS spectrum of the TMS compound of E. FIG. 2 shows the MS spectrum of the TMS compound of F. FIG. 3 shows the ¹ H-NMR spectrum of E. FIG. 4 shows the ¹³ C-NMR spectrum of E. FIG. 5 shows an MF chromatogram of a 10 ppm hexane solution of a coniferyl acetate synthetic product, and FIG. 6 shows an MF chromatogram of a 1% hexane solution of natural jasmine oil (produced in Egypt). FIG. 7 shows low sensitizing jasmine oil (Example
12 shows the MF chromatogram of 12 DI-1, the alkali treated part, and the synthetic adsorbent treated part). FIG. 8 shows the basic process drawing-1. FIG. 9 shows the basic process diagram-2. FIG. 10 shows a GPC chromatogram of DI-1 in Example 1. Figure 11 shows the GPC chromatogram of natural jasmine oil (Egypt). FIG. 12 shows a GPC chromatogram of the GC fractionation treatment section of Example 2. FIG. 13 shows a GPC chromatogram of the alkali-treated part of Example 3. FIG. 14 shows a GPC chromatogram of the synthetic adsorbent treatment part of MDI-R of Example 11.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsuyuki Umoda 3-8-7 Fuchinobehonmachi, Sagamihara-shi, Kanagawa Prefecture (72) Inventor Hideo Moroboshi 538-7, Kamishironecho, Asahi-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Seiichi Hirose 129, Soyado-cho, Kohoku-ku, Yokohama-shi, Kanagawa (72) Inventor Keiichi Uehara 33-2, Kashiwa-cho, Asahi-ku, Yokohama-shi, Kanagawa (72) Masanori Aizawa 338, Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa (72) Inventor Etsuhisa Sato 687, Kamoi-cho, Midori-ku, Yokohama-shi, Kanagawa 37 (72) Hideyuki Ichikawa 3-6-1, Sawamura, Matsumoto-shi, Nagano (72) Inventor Masayuki Teshima 5-chome, Wakabayashi, Setagaya-ku, Tokyo 40-7 (72) Inventor Kiyosaku Tsugeno 2--9-15 Matsunami, Chigasaki-shi, Kanagawa (56) Reference JP-A-57-64608 (JP, A)

Claims (3)

[Claims] 1. A low-contact sensitizing natural jasmine oil-treated product for perfumes from which coniferyl benzoate and coniferyl acetate have been removed. 2. Natural jasmine oil at 60 ° C. or lower, 12.5
Molecular distillation is performed at × 10 ^-2 mmHg or less to distill off 30 parts by weight or less as the first fraction (based on 100 parts by weight of natural jasmine oil), and further 110 ° C or less, 8.0 × 10 ^-2 mmHg or less Molecularly distilled at 77
Part by weight or less is distilled off, and the second distillate from the molecular distillation is further heated at 125 ° C. or less at 0.5 mm.
Distilled under reduced pressure under Hg to 36 parts by weight or less (45 parts by weight or less together with the first fraction of the molecular distillation), the distillation residue of the molecular distillation and the distillation residue of the reduced pressure distillation. A process for producing a low-contact sensitizing natural jasmine oil treatment product for perfumes, which comprises removing coniferyl benzoate and coniferyl acetate present in the powder. 3. A low-contact sensitizing natural jasmine oil-treated product for perfume from which coniferyl benzoate and coniferyl acetate have been removed, and one or two of ester compounds represented by the following general formulas (I) to (IX). A low-contact sensitizing jasmine oil composition for perfumes, characterized by being blended with one or more species. I) II) or III) (In the formula, m represents 1 or 3) IV) V) Or VI) VII) Or VIII) IX)