JPS62275199A - Non-phototoxic orange flower essential oil - Google Patents
Non-phototoxic orange flower essential oilInfo
- Publication number
- JPS62275199A JPS62275199A JP11625686A JP11625686A JPS62275199A JP S62275199 A JPS62275199 A JP S62275199A JP 11625686 A JP11625686 A JP 11625686A JP 11625686 A JP11625686 A JP 11625686A JP S62275199 A JPS62275199 A JP S62275199A
- Authority
- JP
- Japan
- Prior art keywords
- oil
- phototoxic
- essential oil
- orange flower
- flower essential
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000341 volatile oil Substances 0.000 title claims description 41
- 231100001183 nonphototoxic Toxicity 0.000 title claims description 19
- 239000003921 oil Substances 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 9
- 239000003456 ion exchange resin Substances 0.000 claims description 9
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012454 non-polar solvent Substances 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 239000000126 substance Substances 0.000 description 19
- 231100000760 phototoxic Toxicity 0.000 description 16
- ZCCUUQDIBDJBTK-UHFFFAOYSA-N psoralen Chemical compound C1=C2OC(=O)C=CC2=CC2=C1OC=C2 ZCCUUQDIBDJBTK-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000003205 fragrance Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- VXGRJERITKFWPL-UHFFFAOYSA-N 4',5'-Dihydropsoralen Natural products C1=C2OC(=O)C=CC2=CC2=C1OCC2 VXGRJERITKFWPL-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- 229920001429 chelating resin Polymers 0.000 description 4
- 239000002537 cosmetic Substances 0.000 description 4
- 208000007578 phototoxic dermatitis Diseases 0.000 description 4
- 231100000018 phototoxicity Toxicity 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 201000004624 Dermatitis Diseases 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 206010040880 Skin irritation Diseases 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000332 coumarinyl group Chemical class O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000010656 jasmine oil Substances 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000036556 skin irritation Effects 0.000 description 2
- 231100000475 skin irritation Toxicity 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- -1 5-dimethylpsoralen Chemical compound 0.000 description 1
- TUTMEHZVWWQNMW-UHFFFAOYSA-N 5-methylfuro[3,2-g]chromen-7-one Chemical compound C1=C2OC=CC2=CC2=C1OC(=O)C=C2C TUTMEHZVWWQNMW-UHFFFAOYSA-N 0.000 description 1
- BUNGCZLFHHXKBX-UHFFFAOYSA-N 8-methoxypsoralen Natural products C1=CC(=O)OC2=C1C=C1CCOC1=C2OC BUNGCZLFHHXKBX-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- QXKHYNVANLEOEG-UHFFFAOYSA-N Methoxsalen Chemical compound C1=CC(=O)OC2=C1C=C1C=COC1=C2OC QXKHYNVANLEOEG-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229960004469 methoxsalen Drugs 0.000 description 1
- SQBBOVROCFXYBN-UHFFFAOYSA-N methoxypsoralen Natural products C1=C2OC(=O)C(OC)=CC2=CC2=C1OC=C2 SQBBOVROCFXYBN-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 230000037380 skin damage Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
３、発明の詳細な説明
（ａ）産業上の利用分野
本発明は、例えば化粧品用香料として利用される際に皮
膚に有害作用を与える原因となるプソラレン類を含有し
ないことを特徴とする非光毒性オレンジ花精油および該
原因物質を、操作上のトラブルや副反応の生起などの欠
乏を伴うことなしに、オレンジ花精油の香気、その成分
バランス、収量などに悪影響を与えることなしに、工業
的に容易な手段で除去できる非光毒性オレンジ花精油の
製法にも関する。Detailed Description of the Invention 3. Detailed Description of the Invention (a) Industrial Application Field The present invention does not contain psoralen which causes harmful effects on the skin when used as a cosmetic fragrance, for example. It is possible to use non-phototoxic orange flower essential oil and its causative substances, which are characterized by the The present invention also relates to a method for producing non-phototoxic orange flower essential oil that can be removed by industrially easy means without being added.
（ｂ）従来の技術
オレンジ花精油は他の香料として良く調和し、多くの花
香調のベースとして使用されている。又合成香料や他の
天然香料と組み合わせて用いて、匂いの保留性を良くし
たり、又匂いの立ちゃ華やかさを出すのに優れた性質を
持っている。このためにその使用範囲が非常に広く、化
粧品、特に香水及びオーデコロンなどには欠くことので
きない極めて重要な精油になっている。(b) Prior Art Orange flower essential oil blends well with other fragrances and is used as a base for many floral fragrances. It also has excellent properties when used in combination with synthetic fragrances and other natural fragrances to improve the retention of odors and to create a gorgeous fragrance once the odor is released. For this reason, its range of use is very wide, and it has become an extremely important essential oil indispensable for cosmetics, especially perfumes and colognes.
例えば、ヘルガモット、レモンのごとき精油に含有され
ているクマリン核をもつプソラレン類が先番作用を呈し
、例えば皮Ｉ’ｌｌ炎の原因となることは知られている
。クマリン核をもつ化合物、例えば、プソラレン、４−
メチルプソラレン、４，４−ジメチルプソラレン、４，
５−ジメチルプソラレン、４，８−ジメチルプソラレン
、５，５−ジメトキシプソラレン、８−メトキシプソラ
レンなどのごときプソラレン類が関与することが知られ
ている。For example, it is known that psoralen compounds having a coumarin nucleus contained in essential oils such as hergamot and lemon exhibit a precipitant effect and cause, for example, skin irritation. Compounds with a coumarin nucleus, such as psoralen, 4-
Methylpsoralen, 4,4-dimethylpsoralen, 4,
It is known that psoralen such as 5-dimethylpsoralen, 4,8-dimethylpsoralen, 5,5-dimethoxypsoralen, 8-methoxypsoralen and the like are involved.
一般に精油を得る方法としては、例えば花を水蒸気蒸留
して得られるエラセンシアル油と、溶媒を用いて抽出さ
れるアブソリュート油（花精油）とがある。一般に、ア
ブソリュート（例えばアブソリュートジャスミン油）は
、近年化粧品皮膚炎の原因の一つとしてあげられ、皮膚
科学的にも接触感作原性が問題になっており、多くの報
告がある。Generally, methods for obtaining essential oils include, for example, elassenial oil obtained by steam distilling flowers, and absolute oil (flower essential oil) extracted using a solvent. In general, absolutes (eg, absolute jasmine oil) have recently been cited as one of the causes of cosmetic dermatitis, and contact sensitization has become a problem in dermatology, and there have been many reports.
例えば、特開昭５７−６４６０８に低接触感作原性ジャ
スミン油の製造法が提案されている。For example, Japanese Patent Application Laid-Open No. 57-64608 proposes a method for producing jasmine oil with low contact sensitization.
しかしながら、従来オレンジ花精油が皮Ｉｆｆ炎を生起
することは知られていない。又その原因物質が何である
かはもちろんのことその除去方法も当然知られていない
。However, it has not been known that orange flower essential oil causes skin irritation. Naturally, it is not known what the causative substance is, nor is it known how to remove it.
（Ｃ）発明が解決しようとする問題点
本発明者らは、今まで未知であったオレンジ花精油の皮
膚に対する先番作用について、その光毒性試験を行った
。その結果、オレンジ花精油が皮膚に対して先番作用を
呈することが判明し、オレンジ花精油のある特定部分に
皮膚に障害を与えろプソラレン類が存在しいることを確
認した。(C) Problems to be Solved by the Invention The present inventors conducted a phototoxicity test on the effect of orange flower essential oil on the skin, which was unknown until now. As a result, it was found that orange flower essential oil has a positive effect on the skin, and it was confirmed that psoralen compounds, which can cause skin damage, are present in certain parts of orange flower essential oil.
（ｄ）問題点を解決するための手段
本発明者らは、このような事情にかんがみ、皮膚に対す
る先番作用を呈しないオレンジ花精油を得るべく鋭意研
究を続けた。その結果、光毒性物質がオレンジ花精油中
の特定の部分に集中していることを見出し、種々の分離
手段を駆使して光毒性物質を除去することに始めて成功
し且つオレンジ花精油の先番作用が顕著に低減し、しか
もオレンジ花精油本来の香気バランスを保持しているこ
とを発見した。(d) Means for Solving the Problems In view of the above circumstances, the present inventors continued their intensive research in order to obtain orange flower essential oil that does not exhibit any adverse effects on the skin. As a result, they discovered that phototoxic substances were concentrated in specific parts of orange flower essential oil, and for the first time succeeded in removing phototoxic substances by making full use of various separation methods. It was discovered that the effects were significantly reduced, and the original aroma balance of orange blossom essential oil was maintained.
従って、本発明の目的は、プソラレン類を含有しないこ
とを特徴とする非光毒性オレンジ花精油及びその製法を
提供するにある。又、本発明は、非光毒性オレンジ花精
油を有効成分として含有する香料組成物を提供するにあ
る。Therefore, an object of the present invention is to provide a non-phototoxic orange blossom essential oil characterized by not containing psoralen compounds and a method for producing the same. Another object of the present invention is to provide a fragrance composition containing non-phototoxic orange blossom essential oil as an active ingredient.
本発明者らは、オレンジ花精油について蒸留等種々の分
画操作を行い、各分画邪について皮膚に対する光毒性試
験を実施し、紫外線吸収スペクトルにおいて３１０ｎｍ
に光毒性物質が存在していることを確認し、以下に説明
する方法により光毒性物質（プソラレン類）を容易に除
去できることが分った。The present inventors performed various fractionation operations such as distillation on orange flower essential oil, conducted a phototoxicity test on the skin for each fraction, and found that the ultraviolet absorption spectrum was 310 nm.
It was confirmed that phototoxic substances were present in the phototoxic substances, and it was found that the phototoxic substances (psoralens) could be easily removed by the method described below.
本発明の非光毒性オレンジ花精油を製造するには、例え
ば、オレンジ花精油を蒸留して、留出油（１）を得、一
方蒸留残査に無極性溶媒を加えて不溶解油部（Ａ）と溶
解油部（Ｂ）に分離し、該（Ｂ）をカラムクロマト（充
填剤；高分子吸着樹脂）処理して、流出油（Ｃ）を取得
し、該（Ｃ）から溶媒を除去して残油（２）を得る。又
一方上記高分子吸着樹脂を極性溶媒で溶出処理して、溶
媒層を採取し、該溶媒層から溶媒を除去して取得した残
油（Ｄ）と上記不溶解油部（Ａ）とをｔ昆合して、イオ
ン交換樹脂と接触処理して得られた処理油（３）と上記
（１）及び（２）とを合つして非光毒性オレンジ花精油
を容易に得ることができる。To produce the non-phototoxic orange flower essential oil of the present invention, for example, orange flower essential oil is distilled to obtain distillate oil (1), and a non-polar solvent is added to the distillation residue to obtain the insoluble oil portion (1). Separate A) and dissolved oil part (B), process this (B) with column chromatography (filler; polymer adsorption resin) to obtain spilled oil (C), and remove the solvent from this (C). to obtain residual oil (2). On the other hand, the polymer adsorption resin is eluted with a polar solvent, a solvent layer is collected, and the residual oil (D) obtained by removing the solvent from the solvent layer and the undissolved oil portion (A) are Non-phototoxic orange flower essential oil can be easily obtained by combining treated oil (3) obtained by contact treatment with an ion exchange resin and the above (1) and (2).
本発明の上述の非光毒性オレンジ花精油の製造例を工程
図で示すと例えば、以下のように表すことができる。An example of the production of the above-mentioned non-phototoxic orange blossom essential oil of the present invention can be expressed as follows, for example, in a process diagram.
（オレンジ花精油）
（１）＋（２）＋（３）＝非光毒性オレンジ花精油本発
明の非光毒性オレンジ花精油の製造例を上記製造工程図
に従って、以下に詳則に述べろ。(Orange flower essential oil) (1)+(2)+(3)=Non-phototoxic orange flower essential oil Describe in detail below an example of manufacturing the non-phototoxic orange flower essential oil of the present invention according to the above manufacturing process diagram.
本発明に使用するオレンジ花精油は、品質、産地に特別
のものは必要としないが、例えば、モロッコ産、エジプ
ト産のものが人手容易で有利である。The orange flower essential oil used in the present invention does not require any special quality or production area, but for example, those produced in Morocco or Egypt are advantageous because they are easy to handle.
オレンジ花精油の蒸留は、単蒸留、精密蒸留等の手段が
使用される。温浴温度は、例えば約１５０°Ｃ程度以下
の温度で行う方が好ましく、低温程オレンジ花精油の香
気に対する影響の観点から好ましい。又、減圧度も低い
程有利であるが、例えば通常約１０ｍｍＨｇ〜約Ｉ Ｘ
１０−’ｍｍＨｇ程度の減圧範囲で行うことができる
。留出油は、通常原油に対して約２５〜約５５％程度の
収率で、光毒性物質を含有しない留出油（１）を得るこ
とができる。For the distillation of orange flower essential oil, methods such as simple distillation and precision distillation are used. The hot bath temperature is preferably about 150° C. or lower, for example, and lower temperatures are more preferable from the viewpoint of the effect on the aroma of orange blossom essential oil. Also, the lower the degree of reduced pressure, the more advantageous it is, but for example, it is usually about 10 mmHg to about I
This can be carried out in a reduced pressure range of about 10-'mmHg. Distillate oil (1) that does not contain phototoxic substances can be obtained at a yield of about 25 to about 55% based on normal crude oil.
次に蒸留残査に例えば、ヘキサン、ペンタン、シクロヘ
キサンのごとき非極性有８１！溶媒を加え混合し、不溶
解油部（Ａ）と溶解油部（Ｂ）に分離する。ここに得ら
れた不溶解油部（Ａ）及び溶解油部（Ｂ）は、いずれも
光毒性物質及び非光毒性物質の混合物の状態でその存在
が認められた。なお、光毒性物質の確認は、紫外線吸収
スペクトルの測定により３１０ｎｍの吸収スペクトルが
認められるか否かにより決定した。（以後の測定も同様
に行った）、ここに使用する有機溶媒の使用量には、特
別の制限はなく適宜選択変更して行うことができるが、
上記蒸留残査に対して例えば、約５０〜約１０００重量
％程度の使用範囲を例示することができる。Next, the distillation residue contains nonpolar substances such as hexane, pentane, and cyclohexane. A solvent is added and mixed to separate into an insoluble oil part (A) and a dissolved oil part (B). The undissolved oil part (A) and the dissolved oil part (B) thus obtained were both found to exist in the state of a mixture of phototoxic substances and non-phototoxic substances. In addition, confirmation of the phototoxic substance was determined by whether or not an absorption spectrum of 310 nm was observed by measuring the ultraviolet absorption spectrum. (Subsequent measurements were carried out in the same way.) There is no particular restriction on the amount of organic solvent used here, and it can be selected and changed as appropriate.
For example, the range of use may be about 50 to about 1000% by weight based on the distillation residue.
次に、例えば上記のようにして分離して得ることのでき
る溶解油部（Ｂ）を、高分子吸着樹脂を充填したカラム
を用い、展開剤として非極性溶媒を用いてカラムクロマ
ト処理を行うことにより、該溶解油部（Ｂ）中に含有す
る光毒性物質を該高分子吸着剤に吸着させることにより
、容易に除去することができる。カラムクロマト処理に
使用する好ましい高分子吸着剤としては、例えば、オル
ガノ社製のアンバーライトＸＡＤ−７、アンバーライト
ＸＡＤ−４なとを挙げることができる。これら高分子吸
着剤の使用量は、処理する溶解油部（Ｂ）の量によって
適宜選択変更すればよい。又、上記非極性゛溶媒として
は、例えば、ヘキサン、ペンタン、シクロヘキサンなど
を例示することができる。上記のようにして、カラムク
ロマト処理により流出油（Ｃ）を取得し、該流出油（Ｃ
）から例えば、減圧もしくは常圧下に溶媒を留去して光
毒性物質を含有しない残７ｄ＋（２）を得る。一方、上
記高分子吸着樹脂を極性溶媒で溶出処理し、該溶媒を除
去して残油（Ｄ）を得る。ここに使用する極性溶媒とし
ては、例えばアセトン、エーテル、ジクロルメタンのご
とき溶媒が溶出剤として利用することができる。ここに
得られた残油（Ｄ）は光毒性物質及び非光毒性物質の混
合物の状帖でその存在が認められた。Next, for example, the dissolved oil part (B) that can be obtained by separation as described above is subjected to column chromatography using a column packed with a polymer adsorption resin and a non-polar solvent as a developing agent. Accordingly, the phototoxic substance contained in the dissolved oil part (B) can be easily removed by adsorbing it onto the polymer adsorbent. Preferred polymer adsorbents used in column chromatography include, for example, Amberlite XAD-7 and Amberlite XAD-4 manufactured by Organo. The amount of these polymer adsorbents to be used may be selected and changed as appropriate depending on the amount of dissolved oil portion (B) to be treated. Examples of the non-polar solvent include hexane, pentane, and cyclohexane. As described above, the spilled oil (C) is obtained by column chromatography, and the spilled oil (C) is
), for example, the solvent is distilled off under reduced pressure or normal pressure to obtain the residue 7d+(2) which does not contain any phototoxic substance. On the other hand, the polymer adsorption resin is eluted with a polar solvent, and the solvent is removed to obtain a residual oil (D). Examples of polar solvents that can be used here include acetone, ether, and dichloromethane as eluents. The residual oil (D) thus obtained was found to be present in the form of a mixture of phototoxic and non-phototoxic substances.
次に、上記で得られた光毒性物質の存在が認められた不
溶解油部（Ａ）と上記の残油（Ｄ）を合つして、イオン
交換樹脂と接触処理し、光毒性物質を該イオン交換樹脂
に結合させることにより、上記（Ａ）及び（Ｄ）中に存
在する光毒性？ｆｆ質を容易に除去することができる。Next, the insoluble oil part (A) in which the presence of phototoxic substances obtained above was confirmed and the above residual oil (D) are combined and contacted with an ion exchange resin to remove the phototoxic substances. The phototoxicity present in (A) and (D) above by binding to the ion exchange resin? ff quality can be easily removed.
イオン交換樹脂と接触処理する方法としては、カラム法
又はバッチ法のいずれても利用可能であるが、好ましく
はカラム法を挙ることができる。以下刃ラム法について
説明する。As a method for contact treatment with an ion exchange resin, either a column method or a batch method can be used, but preferably a column method can be mentioned. The blade ram method will be explained below.
カラムクロマト管にイオン交換樹脂を充てんする。イオ
ン交１４ｊ！樹脂の使用量は、処理すべき上記（Ａ）お
よび（Ｄ）の量によって、適当な量を選択すれば良い、
又、使用するイオン交換樹脂としては、例えば、オルガ
ノ社製のアンバーリス）Ａ−２７、アンバーリストＡ−
２１、アンバーリス）Ａ−２６などのごときイオン交換
樹脂を好ましく例示することができる。例えば、このよ
うに準備したカラムクロマト管の上部から、（Ａ）およ
び（Ｄ）の混合溶液をチャージし、例えば、エーテル、
ヘキサンなどのごとき展間剤で展開して、光毒性物質を
イオン交換樹脂に結合させる。流出した混合溶液を減圧
下もしくは常圧下に使用した溶媒を留去して光毒性を有
しない処理油（３）を得ることができる
例えば、上述のようにして製造した光毒性物質を含有し
ない上記（１）、（２）及び（３） ｔｔ合つすること
により、皮膚に対して光毒性を有しない非光毒性オレン
ジ花精油を容易に且つ好収率で製造することができる。Fill the column chromatography tube with ion exchange resin. Ion exchange 14j! The amount of resin used may be selected appropriately depending on the amounts of (A) and (D) to be treated.
In addition, examples of ion exchange resins used include Amberlyst A-27 and Amberlyth A-27 manufactured by Organo.
Preferred examples include ion exchange resins such as A-21 and Amberlis A-26. For example, a mixed solution of (A) and (D) is charged from the top of the column chromatography tube prepared in this way, and a mixed solution of, for example, ether,
The phototoxic substance is bound to the ion exchange resin by development with a spreading agent such as hexane. A non-phototoxic treated oil (3) can be obtained by distilling off the solvent used in the mixed solution that has flowed out under reduced pressure or normal pressure. By combining (1), (2) and (3) tt, a non-phototoxic orange flower essential oil that is not phototoxic to the skin can be easily produced with a good yield.
かくして、本発明によれば、光毒性物質が容易に除去さ
れ、他の有用成分に変化なく且つバランスよく香気成分
を含む良好な非光毒性オレンジ花精油を得ることができ
る。得られたオレンジ花精油の紫外線吸収スペクトルの
結果は、光毒性を示す３１０ｎｍのピークがなく、皮膚
炎を起さない利用価）直の高い品質のオレンジ花精油と
して利用することができる。Thus, according to the present invention, it is possible to obtain a good non-phototoxic orange flower essential oil in which phototoxic substances are easily removed, other useful components remain unchanged, and aromatic components are contained in a well-balanced manner. The result of the ultraviolet absorption spectrum of the obtained orange flower essential oil shows that there is no peak at 310 nm indicating phototoxicity, and it can be used as a high-quality orange flower essential oil that does not cause dermatitis.
（ｅ）実施例
２５０ｇのオレンジ花精油を３００ｍ１の蒸留フラスコ
で蒸留した。蒸留条件は、浴温 〜１５０°Ｃ１内温
〜１３６”Ｃ１減圧度０．２５ｍｍＨｇで行った。留出
油（１）９９．３ｇ （３９，６％）、残金１５０ｇ
（６０，１％）を得た。(e) Example 2 50g of orange blossom essential oil was distilled in a 300ml distillation flask. Distillation conditions are bath temperature ~150°C1 internal temperature
~136"C1 Conducted at vacuum degree of 0.25 mmHg. Distillate oil (1) 99.3 g (39.6%), balance 150 g
(60.1%) was obtained.
１５０ｇの残金に６００ ｍ ｌのヘキサンを加え良く
撹拌した後に濾過する。ヘキサン溶解；山部（Ｂ）は１
３１ｇ（５２，３％）、不溶解油部（Ａ）は１８．９ｇ
（７，５％）であった。次にアンバーライトＸＡＤ−
７２０００ｇをカラムに充填し、アセトン３０１、ヘキ
サン３０１にて洗浄した後に、ヘキサン溶解油部（Ｂ）
をチャージした。ヘキサン１５１を用いてカラムクロマ
トを行ない、ヘキサンを留去して残油（２）を６１．７
ｇ （２４，６％）得た。一方アンバーライトＸＡＤ−
７に吸着した部分をアセトンを用いて溶出させ、溶出部
からアセトンを留去して残油（Ｄ）６５．４ｇ （２６
，１％）を得た。Add 600 ml of hexane to the remaining 150 g, stir well, and then filter. Dissolved in hexane; Yamabe (B) is 1
31g (52.3%), undissolved oil part (A) is 18.9g
(7.5%). Next, Amberlight XAD-
After filling a column with 72,000 g and washing with acetone 301 and hexane 301, hexane-dissolved oil part (B)
I charged it. Column chromatography was performed using hexane 151, and the hexane was distilled off to obtain a residual oil (2) of 61.7
g (24.6%) was obtained. On the other hand, Amberlight XAD-
The part adsorbed on 7 was eluted using acetone, and the acetone was distilled off from the eluted part to give 65.4 g of residual oil (D) (26
, 1%).
不溶解油部（Ａ）と残油（Ｄ）を合わせた８４．３ｇの
うち５０ｇを用いて、イオン交換クロマトを行った。ア
ンバーリストＡ−２７１５００ｇをカラムに充填し、ｌ
Ｎ−ＮａＯＨ水１６１、イオン交換水１６１、メタノー
ル１６１．エーテル１６１を用いて洗浄した後、原油５
０ｇを１１のエーテルに？Ｉａ解してチャージした。エ
ーテル１８１にて展間させた後、エーテルを留去し、１
５．７ｇ（対原油１０．６％）の処理油（３）を得た。Ion exchange chromatography was performed using 50 g of the combined 84.3 g of the insoluble oil portion (A) and residual oil (D). Fill a column with 500 g of Amberlyst A-27,
N-NaOH water 161, ion exchange water 161, methanol 161. After washing with ether 161, crude oil 5
0g to 11 ether? I solved Ia and charged it. After exchanging with ether 181, the ether was distilled off and 1
5.7 g (10.6% of crude oil) of treated oil (3) was obtained.
上記で得られた留出油（１）ど残油（２）および処０！
！浦（３）を合わせて、収率７４．８％の非光毒性オレ
ンジ花精油を得た。該（１）、（２）および（３）の紫
外線吸収スペクトルの測定結果は、プソラレン類（３１
０ｎｍ）の吸収は認められなかった。Distillate oil (1) and residual oil (2) obtained above are 0!
! Ura (3) was combined to obtain non-phototoxic orange flower essential oil with a yield of 74.8%. The measurement results of the ultraviolet absorption spectra of (1), (2) and (3) indicate that psoralen (31
0 nm) was not observed.
高速液体クロマトグラフィー測定条件
機種 ；Ｗａｔｅｒｓ ６０００Ａ
カラム；Ｄｅｖｅｌｏｓｉｌ ８．０ｍｍＸ２５ｍｍ
検出器；紫外検出器 ＵＵＶ−３１０ｎ溶剤 ；へキサ
ン： Ｔ）（Ｆ：８０ ： ２０（ｆ）効果
本発明は、香粧品用香料として利用される際に皮Ｊｌに
有害作用を与える原因となるプソラレン類を含有しない
オレンジ花精油及び該原因ｆＩＪ質を、操作上のトラブ
ルや副反応の生起などを伴うことなしに、且つまたオレ
ンジ花精油の香気、その成分、バランス、収量などに悪
影響を与えることなしに、工業的に容易な手段で除去き
、かくして品質の優れた実質的にプソラレンを含有しな
い非光毒性オレンジ花精油の製法を提供することができ
る。High Performance Liquid Chromatography Measurement Conditions Model: Waters 6000A Column: Develosil 8.0mm x 25mm Detector: Ultraviolet Detector UUV-310n Solvent: Hexane: T) (F: 80: 20(f) Effect The present invention is directed to fragrances for cosmetics. Orange flower essential oil that does not contain psoralen compounds, which cause harmful effects on the skin when used as an oil, and orange flower essential oil, which causes harmful effects on orange peels, can be used without any operational trouble or side reactions, and without causing any operational troubles or side reactions. A method for producing a non-phototoxic orange flower essential oil that can be removed by industrially easy means without adversely affecting the aroma, components, balance, yield, etc. of the flower essential oil, and thus has excellent quality and substantially does not contain psoralen. can be provided.
Claims (2)
毒性オレンジ花精油。(1) Non-phototoxic orange flower essential oil characterized by not containing psoralens.
一方蒸留残査に無極性溶媒を加えて不溶解油部（Ａ）と
溶解油部（Ｂ）に分離し、該（Ｂ）をカラムクロマト（
充填剤；高分子吸着樹脂）処理して、流出油（Ｃ）を取
得し、該（Ｃ）から溶媒を除去して残油（２）を得る。 又一方上記高分子吸着樹脂を極性溶媒で溶出処理して、
溶媒層を採取し、該溶媒層から溶媒を除去して取得した
残油（Ｄ）と上記不溶解油部（Ａ）とを混合して、イオ
ン交換樹脂と接触処理して得られた処理油（３）と上記
（１）及び（２）とを合つして製造することを特徴とす
る非光毒性オレンジ花精油の製法。(2) Distilling orange flower essential oil to obtain distillate oil (1),
On the other hand, a nonpolar solvent is added to the distillation residue to separate it into an insoluble oil part (A) and a dissolved oil part (B), and this (B) is separated by column chromatography (
filler; polymer adsorption resin) to obtain spilled oil (C), and remove the solvent from this (C) to obtain residual oil (2). On the other hand, the above polymer adsorption resin is eluted with a polar solvent,
A treated oil obtained by collecting a solvent layer, removing the solvent from the solvent layer, mixing the residual oil (D) and the above-mentioned insoluble oil portion (A), and contacting the mixture with an ion exchange resin. A method for producing non-phototoxic orange flower essential oil, which is produced by combining (3) with the above (1) and (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61116256A JPH0816232B2 (en) | 1986-05-22 | 1986-05-22 | Manufacturing method of non-phototoxic orange flower essential oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61116256A JPH0816232B2 (en) | 1986-05-22 | 1986-05-22 | Manufacturing method of non-phototoxic orange flower essential oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62275199A true JPS62275199A (en) | 1987-11-30 |
| JPH0816232B2 JPH0816232B2 (en) | 1996-02-21 |
Family
ID=14682609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61116256A Expired - Lifetime JPH0816232B2 (en) | 1986-05-22 | 1986-05-22 | Manufacturing method of non-phototoxic orange flower essential oil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0816232B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01254628A (en) * | 1988-04-05 | 1989-10-11 | Shiseido Co Ltd | Agent for depressing consciousness level |
| JPH01254629A (en) * | 1988-04-05 | 1989-10-11 | Shiseido Co Ltd | Agent for raising consciousness level |
| JPH01282298A (en) * | 1988-05-09 | 1989-11-14 | Shiseido Co Ltd | Low-sensitizing orange flower oil |
| EP1334665A1 (en) * | 2002-02-08 | 2003-08-13 | Takasago International Corporation | Taste enhancer; process for its production; food, drink, composition for the oral cavity comprising said taste enhancer; method of taste enhancement |
| FR2960000A1 (en) * | 2010-05-12 | 2011-11-18 | Univ D Avignon Et Des Pays De Vaucluse | Reducing amount of furocoumarins in preparation of essential oil, comprises submitting portion of plant containing furocoumarins to microwave radiation, placing obtained extract to fall by gravity out of microwave oven and recovering oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5670096A (en) * | 1979-11-12 | 1981-06-11 | Takasago Perfumery Co Ltd | Manufacture of lemon oil having no phototoxicity |
| JPS58127797A (en) * | 1982-01-25 | 1983-07-29 | 小林香料株式会社 | Purification of bergamot oil |
| JPS59142297A (en) * | 1983-02-03 | 1984-08-15 | 長谷川香料株式会社 | Manufacture of natural essential oil containing no psoralens |
-
1986
- 1986-05-22 JP JP61116256A patent/JPH0816232B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5670096A (en) * | 1979-11-12 | 1981-06-11 | Takasago Perfumery Co Ltd | Manufacture of lemon oil having no phototoxicity |
| JPS58127797A (en) * | 1982-01-25 | 1983-07-29 | 小林香料株式会社 | Purification of bergamot oil |
| JPS59142297A (en) * | 1983-02-03 | 1984-08-15 | 長谷川香料株式会社 | Manufacture of natural essential oil containing no psoralens |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01254628A (en) * | 1988-04-05 | 1989-10-11 | Shiseido Co Ltd | Agent for depressing consciousness level |
| JPH01254629A (en) * | 1988-04-05 | 1989-10-11 | Shiseido Co Ltd | Agent for raising consciousness level |
| JP2652552B2 (en) * | 1988-04-05 | 1997-09-10 | 株式会社資生堂 | Composition for inhalation administration to calm the consciousness level |
| JPH01282298A (en) * | 1988-05-09 | 1989-11-14 | Shiseido Co Ltd | Low-sensitizing orange flower oil |
| EP1334665A1 (en) * | 2002-02-08 | 2003-08-13 | Takasago International Corporation | Taste enhancer; process for its production; food, drink, composition for the oral cavity comprising said taste enhancer; method of taste enhancement |
| US7122218B2 (en) | 2002-02-08 | 2006-10-17 | Takasago International Corporation | Taste enhancer |
| FR2960000A1 (en) * | 2010-05-12 | 2011-11-18 | Univ D Avignon Et Des Pays De Vaucluse | Reducing amount of furocoumarins in preparation of essential oil, comprises submitting portion of plant containing furocoumarins to microwave radiation, placing obtained extract to fall by gravity out of microwave oven and recovering oil |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0816232B2 (en) | 1996-02-21 |
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