JPH093087A - Trehalose derivative and surfactant - Google Patents
Trehalose derivative and surfactantInfo
- Publication number
- JPH093087A JPH093087A JP8060076A JP6007696A JPH093087A JP H093087 A JPH093087 A JP H093087A JP 8060076 A JP8060076 A JP 8060076A JP 6007696 A JP6007696 A JP 6007696A JP H093087 A JPH093087 A JP H093087A
- Authority
- JP
- Japan
- Prior art keywords
- trehalose
- skin
- agent
- saturated
- surfactant
- 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
Landscapes
- Saccharide Compounds (AREA)
- Cosmetics (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規トレハロース
誘導体及び界面活性能力及び皮膚安全性に優れた界面活
性剤に関する。TECHNICAL FIELD The present invention relates to a novel trehalose derivative and a surfactant excellent in surface active ability and skin safety.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
界面活性剤として数多くの化合物が知られており、多方
面に使用されている。 しかしながら、これらの界面活
性剤の中には人体に直接接触するシャンプー、リンス、
石鹸等の香粧品に用いた場合、皮膚に対する刺激を示す
ものも多い。このため、より刺激性の低い界面活性剤の
開発が望まれていた。2. Description of the Related Art
Many compounds are known as surfactants and are used in various fields. However, some of these surfactants include shampoos, rinses, which come in direct contact with the human body.
When used in cosmetics such as soap, many of them cause skin irritation. Therefore, the development of a less irritating surfactant has been desired.
【０００３】一方、アルキルエステル化した多糖類は食
品、化粧品などに広く汎用されている界面活性剤であ
り、中でも糖骨格としてショ糖を用いたショ糖アルキル
エステルに関する報告は多く、また広く工業的に用いら
れている。また、トレハロース誘導体を界面活性剤とし
て、トレハロース−６，６’−ジアルキルエステル（特
開昭６０−２５８１９５号公報、特開昭６２−９１２３
６号公報）や、トレハロース−６−脂肪酸エステルを用
いることを報告もあるが（特開平５−１６８８９３号公
報）、これらはエステル結合を有していることからアル
カリに弱く、その用途範囲は限られる。On the other hand, alkyl esterified polysaccharides are widely used surfactants in foods, cosmetics, etc. Among them, there are many reports on sucrose alkyl esters using sucrose as a sugar skeleton, and they are widely used industrially. Is used for. In addition, a trehalose derivative is used as a surfactant, and a trehalose-6,6'-dialkyl ester (JP-A-60-258195 and JP-A-62-11233).
No. 6) and trehalose-6-fatty acid ester have been reported (JP-A-5-168893), but since they have an ester bond, they are weak against alkali and their application range is limited. To be
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記事情
に鑑み、鋭意研究を行った結果、下記の一般構造式
（１）で示されるトレハロース誘導体が、優れた界面活
性能力を持つと同時に皮膚に対する高い安全性を有する
ことを見出し、本発明を完成した。即ち、本発明は、下
記一般構造式（１）で示されるトレハロース誘導体、及
び該トレハロース誘導体からなる界面活性剤に関する。Means for Solving the Problems The inventors of the present invention have conducted extensive studies in view of the above circumstances, and as a result, found that a trehalose derivative represented by the following general structural formula (1) has excellent surface-active ability. At the same time, they found that they have high safety for the skin, and completed the present invention. That is, the present invention relates to a trehalose derivative represented by the following general structural formula (1) and a surfactant comprising the trehalose derivative.
【化２】 （但し、Ｒ1 は炭素数７〜２１の、Ｒ 2は水素原子、炭
素数１〜２２の、直鎖及び側鎖を有する飽和、不飽和炭
化水素基である。）Embedded image (Wherein, R 1 is 7 to 21 carbon atoms, R 2 is a hydrogen atom, having from 1 to 22 carbon atoms, saturated with linear and side chain, an unsaturated hydrocarbon group.)
【０００５】[0005]
【発明の実施の形態】本発明のトレハロース誘導体の一
つである上記一般構造式（１）で、Ｒ2 が水素原子であ
るトレハロース誘導体は、トレハロースと脂肪族炭化水
素鎖が直鎖及び側鎖を有する飽和、不飽和の炭素数８〜
２２のアセタールとを酸触媒下に縮合する事により得る
ことが出来る。また、上記一般構造式（１）でＲ2 が炭
素数１〜２２の直鎖または側鎖を有する飽和、不飽和の
炭化水素基をもつトレハロース誘導体は、下記一般構造
式（２）で示されるアセタール化合物とを酸触媒下に縮
合する事により得ることが出来る。BEST MODE FOR CARRYING OUT THE INVENTION The trehalose derivative represented by the above general structural formula (1), which is one of the trehalose derivatives of the present invention, in which R 2 is a hydrogen atom is a trehalose and an aliphatic hydrocarbon chain having a straight chain or a side chain Saturated or unsaturated carbon number of 8 to
It can be obtained by condensing the acetal of 22 with an acid catalyst. A trehalose derivative having a saturated or unsaturated hydrocarbon group in which R 2 has a straight chain or a side chain having 1 to 22 carbon atoms in the above general structural formula (1) is represented by the following general structural formula (2). It can be obtained by condensing the acetal compound with an acid catalyst.
【化３】 （但し、Ｒ1 は炭素数７〜２１の、Ｒ 2は炭素数１〜２
２の、直鎖及び側鎖を有する飽和、不飽和炭化水素基、
Ｒ3 はメチル基あるいはエチル基である。）Embedded image (However, R 1 has 7 to 21 carbon atoms, and R 2 has 1 to 2 carbon atoms.
2, a saturated or unsaturated hydrocarbon group having a straight chain and a side chain,
R 3 is a methyl group or an ethyl group. )
【０００６】本発明の上記界面活性剤は優れた界面活性
能力、安全性等から、皮膚洗浄剤、頭髪洗浄剤、皮膚手
入れ剤、頭髪手入れ剤、メイクアップ剤、入浴剤、石鹸
等の化粧料、医薬品、食品等に使用でき、剤型としても
液状、乳液状、クリーム状、粉末状、固形状、エアゾー
ル状等の各種剤型中に界面活性剤として配合が可能であ
る。The above-mentioned surfactants of the present invention are excellent in surface-active ability, safety and the like, and therefore, cosmetics such as skin cleansing agents, hair cleansing agents, skin care agents, hair care agents, makeup agents, bath agents and soaps. It can be used in pharmaceuticals, foods, etc., and can be added as a surfactant in various dosage forms such as liquid, emulsion, cream, powder, solid, and aerosol.
【０００７】以下、本発明の詳細について実施例に基づ
き説明する。尚、実施例に示すｗｔ％とは、重量％を表
す。The details of the present invention will be described below based on examples. In addition, wt% shown in the examples represents wt%.
【０００８】[0008]
実施例１ （４，６−Ｏ−ラウニリデン−トレハロース
の製造） α，α−トレハロース二水和物３７．８ｇを３００ｍｌ
のジメチルホルムアミド（ＤＭＦ）に溶解した後、１０
０ｍｌのＤＭＦを減圧下に除去し結合水を脱水した。こ
の溶液に１００ｍｇのｐ−トルエンスルフォン酸と２
５．８ｇドデカナールジエチルアセタールを加え、８０
℃にて生成するエタノールを除去しながら、２時間反応
した。反応溶液を冷却した後、２００ｍｌのヘキサンで
３回抽出して未反応のドデカナールジエチルアセタール
を除去した。ＤＭＦ溶液を減圧下において約５０ｍｌ程
度まで濃縮した後、１００ｍｌのアセトンを加え、触媒
として用いたｐ−トルエンスルフォン酸と未反応のトレ
ハロースを沈澱させ濾別除去した。沈澱を１００ｍｌの
ｎ−ブタノールにて洗浄し、洗浄液を濾液に加えた。濾
液を減圧蒸留する事により淡黄色な粘性シロップを得
た。Example 1 (Production of 4,6-O-laurylidene-trehalose) 300 ml of 37.8 g of α, α-trehalose dihydrate
10% after dissolving in dimethylformamide (DMF)
0 ml of DMF was removed under reduced pressure and the combined water was dehydrated. To this solution was added 100 mg of p-toluenesulfonic acid and 2
Add 5.8 g dodecanal diethyl acetal, add 80
The reaction was carried out for 2 hours while removing ethanol produced at ℃. The reaction solution was cooled and then extracted three times with 200 ml of hexane to remove unreacted dodecanal diethyl acetal. After concentrating the DMF solution under reduced pressure to about 50 ml, 100 ml of acetone was added, and p-toluenesulfonic acid used as a catalyst and unreacted trehalose were precipitated and removed by filtration. The precipitate was washed with 100 ml of n-butanol, and the washing solution was added to the filtrate. By distilling the filtrate under reduced pressure, a pale yellow viscous syrup was obtained.
【０００９】この粘性シロップをシリカゲルカラムクロ
マトグラフィー（展開溶媒：クロロホルム／メタノール
＝４／１）にて精製することにより、薄層クロマトグラ
フィーにおけるｒ．ｆ値０．７６（展開溶媒：クロロホ
ルム／メタノール＝３／１）のフラクションを濃縮する
事により、２６．４ｇの白色固体を得た。得られた固体
の１３Ｃ−ＮＭＲペクトル測定において１０３．２ｐｐ
ｍにアセタール基、また８０．９ｐｐｍにトレハロース
４位及び６８．５ｐｐｍにトレハロース６位のシグナル
を確認したことから、その構造を確認した。By purifying this viscous syrup by silica gel column chromatography (developing solvent: chloroform / methanol = 4/1), r.p. The fraction having an f value of 0.76 (developing solvent: chloroform / methanol = 3/1) was concentrated to obtain 26.4 g of a white solid. 103.2 pp in 13 C-NMR spectrum measurement of the obtained solid
The structure was confirmed by confirming the acetal group at m, the trehalose 4-position at 80.9 ppm and the trehalose 6-position at 68.5 ppm.
【００１０】実施例２ （４，６−Ｏ−（１０−ウンデ
シレニリデン）−トレハロースの製造） 実施例１で用いたドデカナールジエチルアセタール２
５．８ｇを１０−ウンデセナールジメチルアセタール２
４．２ｇに代えた以外は同様に行い２２．１ｇの白色固
体を得た。得られた固体の１３Ｃ−ＮＭＲ測定により本
発明の４，６−Ｏ−（１０−ウンデシレニリデン）−ト
レハロースの生成を確認した。Example 2 (Production of 4,6-O- (10-undecylenylidene) -trehalose) Dodecanal diethyl acetal 2 used in Example 1
5.8 g of 10-undecenal dimethyl acetal 2
22.1 g of white solid was obtained in the same manner except that the amount was changed to 4.2 g. The production of 4,6-O- (10-undecylenylidene) -trehalose of the present invention was confirmed by 13 C-NMR measurement of the obtained solid.
【００１１】実施例３ （４，６−Ｏ−（３，７ージメ
チルー６ーオクテニリデン）−トレハロースの製造） トレハロース２０ｇを４００ｍｌのＤＭＦに溶解した。
この溶液にシトロネラールジエチルアセタール１０ｇと
酸性イオン交換樹脂（アンバーライト）を加えた。８０
℃まで昇温した後、１８時間撹拌した。反応溶液を冷却
した後、イオン交換樹脂を濾別し、濾液に４００ｍｌの
ヘキサンで５回抽出してシトロネラールジエチルアセタ
ールを除去した。ＤＭＦ溶液を減圧下において約５０ｍ
ｌ程度まで濃縮した後、１００ｍｌのアセトンを加え、
未反応のトレハロースを沈澱させ濾別除去した。沈澱を
少量のｎ−ブタノールにて洗浄し、洗浄液を濾液に加え
た。濾液を減圧蒸留する事により淡黄色な粘性シロップ
を得た。この粘性シロップをシリカゲルカラムクロマト
グラフィー（展開溶媒：クロロホルム／メタノール＝４
／１）にて精製することにより、１５．３ｇの白色固体
として４，６−Ｏ−（３，７ージメチル−６−オクテニ
リデン）−トレハロースを得た。Example 3 (Production of 4,6-O- (3,7-dimethyl-6-octenylidene) -trehalose) 20 g of trehalose was dissolved in 400 ml of DMF.
To this solution, 10 g of citronellal diethyl acetal and an acidic ion exchange resin (Amberlite) were added. 80
After the temperature was raised to ° C, the mixture was stirred for 18 hours. After cooling the reaction solution, the ion exchange resin was filtered off, and the filtrate was extracted 5 times with 400 ml of hexane to remove citronellal diethyl acetal. About 50 m of DMF solution under reduced pressure
After concentrating to about 1, add 100 ml of acetone,
Unreacted trehalose was precipitated and removed by filtration. The precipitate was washed with a small amount of n-butanol, and the washing solution was added to the filtrate. By distilling the filtrate under reduced pressure, a pale yellow viscous syrup was obtained. This viscous syrup was subjected to silica gel column chromatography (developing solvent: chloroform / methanol = 4
/ 1) to obtain 4,6-O- (3,7-dimethyl-6-octenylidene) -trehalose as a white solid (15.3 g).
【００１２】実施例４ （４，６−Ｏ−オクタデカニリ
デン−トレハロースの製造） 実施例１で用いたドデカナールジエチルアセタール２
５．８ｇをオクタデカナールジメチルアセタール２５ｇ
に代えた以外は同様に行い１４．１ｇの白色固体を得
た。得られた固体の１３Ｃ−ＮＭＲ測定により本発明の
４，６−Ｏ−オクタデカニリデン−トレハロースの生成
を確認した。Example 4 (Production of 4,6-O-octadecanylidene-trehalose) Dodecanal diethyl acetal 2 used in Example 1
5.8 g of octadecanal dimethyl acetal 25 g
The same procedure was performed except that the above was changed to 14.1 g of a white solid. The production of 4,6-O-octadecanylidene-trehalose of the present invention was confirmed by 13 C-NMR measurement of the obtained solid.
【００１３】実施例５ （４，６−Ｏ−（２）−トリデ
シリデン−トレハロースの製造） α，α−トレハロース二水和物３７．８ｇを３００ｍｌ
のジメチルホルムアミド（ＤＭＦ）に溶解した後、１０
０ｍｌのＤＭＦを減圧下に除去し結合水を脱水した。こ
の溶液に１００ｍｇのｐ−トルエンスルフォン酸と２
４．４ｇの２，２−ジメトキシトリデカンを加え、７０
℃にて生成するメタノールを除去しながら、２時間反応
させた。反応溶液を冷却した後、２００ｍｌのヘキサン
で３回洗浄して未反応の２，２−ジメトキシトリデカン
を除去した。次いで、ＤＭＦ溶液を減圧下において約５
０ｍｌ程度まで濃縮した後、１００ｍｌのアセトンを加
え、未反応のトレハロースを沈澱させ濾別除去した。残
さを１００ｍｌのｎ−ブタノールにて洗浄し、洗浄液を
濾液に加えた。次いで、溶媒を減圧下で留去し、淡黄色
の粘性シロップを得た。Example 5 (Production of 4,6-O- (2) -tridecylidene-trehalose) 300 ml of 37.8 g of α, α-trehalose dihydrate
10% after dissolving in dimethylformamide (DMF)
0 ml of DMF was removed under reduced pressure and the combined water was dehydrated. To this solution was added 100 mg of p-toluenesulfonic acid and 2
Add 4.4 g of 2,2-dimethoxytridecane and add 70
The reaction was carried out for 2 hours while removing methanol produced at ° C. After cooling the reaction solution, it was washed 3 times with 200 ml of hexane to remove unreacted 2,2-dimethoxytridecane. Then, the DMF solution is reduced to about 5 under reduced pressure.
After concentrating to about 0 ml, 100 ml of acetone was added to precipitate unreacted trehalose, which was removed by filtration. The residue was washed with 100 ml of n-butanol, and the washing solution was added to the filtrate. Then, the solvent was distilled off under reduced pressure to obtain a pale yellow viscous syrup.
【００１４】この粘性シロップをシリカゲルカラムクロ
マトグラフィー（展開溶媒：クロロホルム／メタノール
＝４／１）にて精製する事により、薄層クロマトグラフ
ィーにおけるｒ．ｆ値０．３２（展開溶媒：クロロホル
ム／メタノール＝６／１）のフラクションを得た。次い
で、このフラクションを減圧濃縮する事により、２０．
９ｇの白色固体を得た。By purifying this viscous syrup by silica gel column chromatography (developing solvent: chloroform / methanol = 4/1), r.p. A fraction having an f value of 0.32 (developing solvent: chloroform / methanol = 6/1) was obtained. Then, this fraction was concentrated under reduced pressure to obtain 20.
9 g of white solid was obtained.
【００１５】得られた固体のＩＲ（ＫＢｒ）測定におい
て、図１に示す様に１３５０ｃｍ-1付近に糖骨格のＯＨ
基に由来するブロードなピークを、２９６０〜２８５０
ｃｍ-1にアルキル鎖に由来するピークを、１１５０〜９
８０ｃｍ-1に糖骨格及びアセタール基に由来するピーク
を確認した。また、１３Ｃ−ＮＭＲ測定において、１０
２．０ｐｐｍ及び１０２．７ｐｐｍにアセタール基のシ
グナルを、また、ＦＡＢ−ＭＳ測定において、〔Ｍ＋
Ｈ〕+ ：５２３が検出されたことから、４，６−Ｏ−
（２）−トリデシリデン−トレハロースの生成を確認し
た。In the IR (KBr) measurement of the obtained solid, as shown in FIG. 1, OH of the sugar skeleton was around 1350 cm -1.
The broad peak derived from the group is 2960 to 2850
the peak derived from the alkyl chain at 1 cm -1
A peak derived from a sugar skeleton and an acetal group was confirmed at 80 cm -1 . Moreover, in 13 C-NMR measurement, 10
Signals of acetal groups were obtained at 2.0 ppm and 102.7 ppm, and in FAB-MS measurement, [M +
H] + : 523 was detected, so 4,6-O-
The production of (2) -tridecylidene-trehalose was confirmed.
【００１６】実施例６ （４，６−Ｏ−（２）−ペンタ
デシリデン−トレハロースの製造） 実施例５で、２，２−ジメトキシトリデカン２４．４ｇ
を、２，２−ジエトキシペンタデカン３０．０ｇに代え
た以外は同様に行い、２２．０ｇの白色固体を得た。得
られた固体について実施例１と同様に、ＩＲ測定及び１
３Ｃ−ＮＭＲ測定、ＦＡＢ−ＭＳ測定を行い、本発明の
４，６−Ｏ−（２）−ペンタデシリデン−トレハロース
の生成を確認した。Example 6 (Production of 4,6-O- (2) -pentadecylidene-trehalose) In Example 5, 24.4 g of 2,2-dimethoxytridecane was used.
Was carried out in the same manner except that 30.0 g of 2,2-diethoxypentadecane was replaced with, to obtain 22.0 g of a white solid. For the obtained solid, IR measurement and 1 were conducted in the same manner as in Example 1.
3C-NMR measurement and FAB-MS measurement were performed to confirm the production of 4,6-O- (2) -pentadecylidene-trehalose of the present invention.
【００１７】実施例７ （４，６−Ｏ−（４）−オクタ
デシリデン−トレハロースの製造） 実施例５で、２，２−ジメトキシトリデカン２４．４ｇ
を、４，４−ジメトキシオクタデカン３４．２ｇに代え
た以外は同様に行い、２４．８ｇの白色固体を得た。得
られた固体について実施例１５同様に、ＩＲ測定及び１
３Ｃ−ＮＭＲ測定、ＦＡＢ−ＭＳ測定を行い、本発明の
４，６−Ｏ−（４）−オクタデシリデン−トレハロース
の生成を確認した。Example 7 (Production of 4,6-O- (4) -octadecylidene-trehalose) In Example 5, 24.4 g of 2,2-dimethoxytridecane was used.
Was carried out in the same manner except that 34.2 g of 4,4-dimethoxyoctadecane was used to obtain 24.8 g of a white solid. For the obtained solid, IR measurement and 1 were carried out in the same manner as in Example 15.
3C-NMR measurement and FAB-MS measurement were performed to confirm the production of 4,6-O- (4) -octadecylidene-trehalose of the present invention.
【００１８】実施例８ （４，６−Ｏ−（１１）−ドデ
セニリデン−トレハロースの製造） 実施例５で、２，２−ジメトキシトリデカン２４．４ｇ
を、１１，１１−ジメトキシドデセン２２．８ｇに代え
た以外は同様に行い２０．１ｇの白色固体を得た。得ら
れた固体について実施例５と同様に、ＩＲ測定及び１３
Ｃ−ＮＭＲ測定、ＦＡＢ−ＭＳ測定を行い、本発明の
４，６−Ｏ−（１１）−ドデセニリデン−トレハロース
の生成を確認した。Example 8 (Production of 4,6-O- (11) -dodecenylidene-trehalose) In Example 5, 24.4 g of 2,2-dimethoxytridecane was used.
Was replaced by 22.8 g of 11,11-dimethoxydodecene to obtain 20.1 g of a white solid. For the obtained solid, IR measurement and 13 were conducted in the same manner as in Example 5.
C-NMR measurement and FAB-MS measurement were performed to confirm the production of 4,6-O- (11) -dodecenylidene-trehalose of the present invention.
【００１９】実施例９ （４，６−Ｏ−（２）−シュー
ドイオニリデン−トレハロースの製造） シュードイオノン（６，９−ジメチル−３，５，８−ウ
ンデシルトリエン−２−オン）より得た、シュードイオ
ノン−２，２−ジメチルアセタール２１．３ｇを、実施
例５で用いた２，２−ジメトキシトリデカン２４．４ｇ
に代えて、同様に行い２０．２ｇの白色固体を得た。得
られた固体について実施例５と同様に、ＩＲ測定及び１
３Ｃ−ＮＭＲ測定、ＦＡＢ−ＭＳ測定を行い、本発明の
４，６−Ｏ−（２）−シュードイオニリデン−トレハロ
ースの生成を確認した。Example 9 (Production of 4,6-O- (2) -pseudoionylidene-trehalose) From pseudoionone (6,9-dimethyl-3,5,8-undecyltrien-2-one) 21.3 g of the obtained pseudoionone-2,2-dimethylacetal was used in Example 5, 24.4 g of 2,2-dimethoxytridecane.
In the same manner as above, to obtain 20.2 g of a white solid. For the obtained solid, IR measurement and 1 were conducted in the same manner as in Example 5.
3C-NMR measurement and FAB-MS measurement were performed to confirm the production of 4,6-O- (2) -pseudoionylidene-trehalose of the present invention.
【００２０】実施例１０ （４，６−Ｏ−（２）−ドデ
シリデン−トレハロースの製造） トレハロース２０ｇを４００ｍｌのＤＭＦに溶解した。
この溶液に２，２−ジメトキシドデカン１０ｇと酸性イ
オン交換樹脂（アンバーライト）を加え、８０℃まで昇
温した後、生成するメタノールを除去しながら１８時間
撹拌した。反応溶液を冷却した後、イオン交換樹脂を濾
別し、濾液を４００ｍｌのヘキサンで５回洗浄してして
未反応の２，２−ジメトキシドデカンを除去した。ＤＭ
Ｆ溶液を減圧下において約５０ｍｌ程度まで濃縮した
後、１００ｍｌのアセトンを加えて未反応のトレハロー
スを沈澱させ濾別除去した。残渣を少量のｎ−ブタノー
ルにて洗浄し、洗浄液を濾液に加えた。次いで、溶媒を
留去し淡黄色の粘性シロップを得た。この粘性シロップ
をシリカゲルカラムクロマトグラフィー（展開溶媒：ク
ロロホルム／メタノール＝４／１）にて精製することに
より、８．３ｇの白色固体として４，６−Ｏ−（２）−
ドデシリデン−トレハロースを得た。Example 10 (Production of 4,6-O- (2) -dodecylidene-trehalose) 20 g of trehalose was dissolved in 400 ml of DMF.
To this solution, 10 g of 2,2-dimethoxydodecane and an acidic ion-exchange resin (Amberlite) were added, and the temperature was raised to 80 ° C., then, stirring was performed for 18 hours while removing generated methanol. After cooling the reaction solution, the ion exchange resin was filtered off, and the filtrate was washed 5 times with 400 ml of hexane to remove unreacted 2,2-dimethoxydodecane. DM
After the F solution was concentrated under reduced pressure to about 50 ml, 100 ml of acetone was added to precipitate unreacted trehalose, which was removed by filtration. The residue was washed with a small amount of n-butanol, and the washing solution was added to the filtrate. Then, the solvent was distilled off to obtain a pale yellow viscous syrup. This viscous syrup was purified by silica gel column chromatography (developing solvent: chloroform / methanol = 4/1) to give 8.3 g of white solid 4,6-O- (2)-.
Dodecylidene-trehalose was obtained.
【００２１】次に、溶解性を確認する目的で、実施例６
にて得られた４，６−Ｏ−（２）−ペンタデシリデン−
トレハロースと、同一の炭素数を有するが分岐鎖を有し
ない４，６−Ｏ−ペンタデシリデン−トレハロースを実
施例１と同じ製造方法により合成し、これらを１ｗｔ％
の水溶液としその外観を肉眼で判定した。その結果、
４，６−Ｏ−ペンタデシリデン−トレハロースに比べ、
分岐鎖を有する４，６−Ｏ−（２）−ペンタデシリデン
−トレハロースは、極めて容易に水に溶け、水溶性に優
れている性質を示した。Next, in order to confirm the solubility, Example 6 was used.
4,6-O- (2) -pentadecylidene-
Trehalose and 4,6-O-pentadecylidene-trehalose having the same carbon number but no branched chain were synthesized by the same production method as in Example 1, and 1 wt%
As an aqueous solution of and the appearance was visually evaluated. as a result,
Compared to 4,6-O-pentadecylidene-trehalose,
4,6-O- (2) -pentadecylidene-trehalose having a branched chain was extremely easily soluble in water and exhibited excellent water solubility.
【００２２】次に、安全性試験として、皮膚に対する刺
激性を以下の方法で調べた。２０人の被験者に、上記実
施例で得られたトレハロース誘導体の０．２ｗｔ％水溶
液１ｍｌをしみこませたパッチテスト用絆創膏を２４時
間貼布し、貼布除去後２４時間後に刺激性を判定した。
判定結果は、はっきりと紅斑を示したものを陽性とし、
その陽性率で示した。また、対照としてラウリル硫酸ナ
トリウム塩を用いた。その結果を表１に示す。Next, as a safety test, irritation to skin was examined by the following method. Twenty test subjects were patch-applied with a patch test adhesive bandage impregnated with 1 ml of a 0.2 wt% aqueous solution of the trehalose derivative obtained in the above example for 24 hours, and the irritation was evaluated 24 hours after removal of the patch.
As for the judgment result, those showing clear erythema were regarded as positive,
The positive rate is shown. Further, sodium lauryl sulfate was used as a control. Table 1 shows the results.
【００２３】[0023]
【表１】 [Table 1]
【００２４】表１の如く、本発明のトレハロース誘導体
は皮膚刺激性はなく皮膚安全性は明らかに優れている。As shown in Table 1, the trehalose derivative of the present invention has no skin irritation and is obviously excellent in skin safety.
【００２５】応用例１、比較例１ （液状皮膚洗浄剤） 下記表２の組成からなる液状皮膚洗浄剤を調製した。
尚、応用例１で用いた４，６−Ｏ−ラウニリデン−トレ
ハロースは実施例１にて得られた物である。また、比較
例として６−Ｏ−ラウニリデン−トレハロースを含まな
い液状皮膚洗浄剤を調製した。そしてパネラー１０人が
応用例１と比較例１の液状皮膚洗浄剤で、身体を洗浄し
たときの比較官能評価試験を実施した。尚、比較官能評
価試験の判定基準は以下の通りである。 ◎；比較例に比べ極めて良好（良いと答えた人が９人以
上） ○；比較例に比べ良好（良いと答えた人が７〜 ８人） △；比較例に比べ同程度（良いと答えた人が４〜 ６
人） ×；比較例に比べ劣る（良いと答えた人が３人以下）Application Example 1 and Comparative Example 1 (Liquid skin cleansing agent) A liquid skin cleansing agent having the composition shown in Table 2 below was prepared.
The 4,6-O-laurylidene-trehalose used in Application Example 1 is the one obtained in Example 1. As a comparative example, a liquid skin cleanser containing no 6-O-laurylidene-trehalose was prepared. Then, 10 panelists carried out a comparative sensory evaluation test when the body was washed with the liquid skin cleansing agents of Application Example 1 and Comparative Example 1. The criteria for the comparative sensory evaluation test are as follows. ⊚: Very good compared to comparative examples (9 or more people answered good) ○: Good compared to comparative examples (7 to 8 people answered good) △: Similar to comparative examples (answered good) 4 to 6
×) Inferior to the comparative example (3 or less people answered good)
【００２６】[0026]
【表２】 [Table 2]
【００２７】応用例２ （水中油型スキンクリーム） 下記表３組成からなる水中油型スキンクリームを調製し
た。尚、用いた４，６−Ｏ−オクタデカニリデン−トレ
ハロースは実施例４にて得られた物である。このクリー
ムの乳化状態は極めて良好で、べたつかず肌なじみも良
好であった。Application Example 2 (Oil-in-water skin cream) An oil-in-water skin cream having the composition shown in Table 3 below was prepared. The 4,6-O-octadecanylidene-trehalose used was the one obtained in Example 4. The emulsified state of this cream was extremely good, and it was not sticky and had good skin compatibility.
【００２８】[0028]
【表３】 [Table 3]
【００２９】応用例３ （頭髪洗浄剤） 下記表４の組成からなる頭髪洗浄剤を調製した。尚、用
いた４，６−Ｏ−（ １０−ウンデシレニリデン）−ト
リハロースは実施例２にて得られた物である。この頭髪
洗浄剤で洗髪した結果、泡立ちは優れており感触も良好
であった。Application Example 3 (Hair Cleanser) A hair cleanser having the composition shown in Table 4 below was prepared. The 4,6-O- (10-undecylenylidene) -trihalose used is the one obtained in Example 2. As a result of washing the hair with this hair cleanser, foaming was excellent and the feel was also good.
【００３０】[0030]
【表４】 [Table 4]
【００３１】応用例４、比較例２ （洗顔剤） 下記表５の組成からなる洗顔剤を調製した。尚、用いた
４，６−Ｏ−（２）−トリデシリデン−トレハロースは
実施例５にて得られた物である。比較例２として、４，
６−Ｏ−（２）−トリデシリデン−トレハロースを含ま
ない洗顔剤を調製した。そしてパネラー１０人が応用例
４と比較例２の洗顔剤で洗顔し、前記の比較官能試験を
実施した。その結果を表５に示す。Application Example 4, Comparative Example 2 (Facial Cleanser) A facial cleanser having the composition shown in Table 5 below was prepared. The 4,6-O- (2) -tridecylidene-trehalose used was the one obtained in Example 5. As Comparative Example 2, 4,
A face wash without 6-O- (2) -tridecylidene-trehalose was prepared. Then, 10 panelists washed the face with the facial cleansers of Application Example 4 and Comparative Example 2 and carried out the comparative sensory test. The results are shown in Table 5.
【００３２】[0032]
【表５】 [Table 5]
【００３３】応用例５ （水中油型スキンクリーム） 前記表３組成において、４，６−Ｏ−オクタデカニリデ
ン−トレハロースの代わりに、実施例６で得られた４，
６−Ｏ−（２）−ペンタデシリデン−トレハロースを用
い、水中油型スキンクリームを調製した。このクリーム
の乳化状態は極めて良好で、べたつかず肌なじみも良好
であった。Application Example 5 (Oil-in-water type skin cream) In the composition of Table 3 above, 4, obtained in Example 6 instead of 4,6-O-octadecanylidene-trehalose was used.
An oil-in-water skin cream was prepared using 6-O- (2) -pentadecylidene-trehalose. The emulsified state of this cream was extremely good, and it was not sticky and had good skin compatibility.
【００３４】応用例６ （ヘアーリンス剤） 下記表６の組成からなるヘアーリンス剤を調製した。
尚、用いた４，６−Ｏ−（４）−オクタデシリデン−ト
レハロースは実施例７にて得られたものである。このヘ
アーリンスは乳化状態も極めて良好で、使用感に優れて
おり乾燥後の風合いも良好であった。Application Example 6 (Hair rinse agent) A hair rinse agent having the composition shown in Table 6 below was prepared.
The 4,6-O- (4) -octadecylidene-trehalose used was that obtained in Example 7. The hair rinse had an excellent emulsified state, an excellent feeling in use, and a good texture after drying.
【００３５】[0035]
【表６】 [Table 6]
【００３６】[0036]
【発明の効果】本発明のトレハロース誘導体は界面活性
能力及び皮膚安全性に優れており、界面活性剤として広
範囲に利用できる。INDUSTRIAL APPLICABILITY The trehalose derivative of the present invention has excellent surface-active ability and skin safety and can be widely used as a surfactant.
【図１】本発明の４，６−Ｏ−（２）トリデシリデン−
トレハロースのＩＲスペクトルを示す図である。FIG. 1 is 4,6-O- (2) tridecylidene of the present invention
It is a figure which shows the IR spectrum of trehalose.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ａ６１Ｋ 7/48 Ａ６１Ｋ 7/48 7/50 7/50 Ｂ０１Ｆ 17/56 Ｂ０１Ｆ 17/56 (72)発明者 西尾 裕幸 神奈川県小田原市寿町５丁目３番28号 鐘 紡株式会社化粧品研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI Technical indication location A61K 7/48 A61K 7/48 7/50 7/50 B01F 17/56 B01F 17/56 (72) Inventor Hiroyuki Nishio 5-3 28, Kotobuki-cho, Odawara-shi, Kanagawa Kanebo Co., Ltd.
Claims (2)
ス誘導体。 【化１】 （但し、Ｒ1 は炭素数７〜２１の、Ｒ 2は水素原子、炭
素数１〜２２の、直鎖及び側鎖を有する飽和、不飽和炭
化水素基である。）1. A trehalose derivative represented by the general structural formula (1). Embedded image (Wherein, R 1 is 7 to 21 carbon atoms, R 2 is a hydrogen atom, having from 1 to 22 carbon atoms, saturated with linear and side chain, an unsaturated hydrocarbon group.)
なる界面活性剤。2. A surfactant comprising the trehalose derivative according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06007696A JP3725233B2 (en) | 1995-04-18 | 1996-02-21 | Trehalose derivatives and surfactants |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-117764 | 1995-04-18 | ||
| JP11776495 | 1995-04-18 | ||
| JP06007696A JP3725233B2 (en) | 1995-04-18 | 1996-02-21 | Trehalose derivatives and surfactants |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH093087A true JPH093087A (en) | 1997-01-07 |
| JP3725233B2 JP3725233B2 (en) | 2005-12-07 |
Family
ID=26401133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06007696A Expired - Fee Related JP3725233B2 (en) | 1995-04-18 | 1996-02-21 | Trehalose derivatives and surfactants |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3725233B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002363064A (en) * | 2001-06-06 | 2002-12-18 | Kanebo Ltd | Skin cleansing agent |
| JP2002363060A (en) * | 2001-06-06 | 2002-12-18 | Kanebo Ltd | Bathing agent |
| WO2014097173A1 (en) * | 2012-12-18 | 2014-06-26 | Dsm Ip Assets B.V. | (6r,10r)-6,10,14-trimetylpentadecan-2-one prepared from 6,10-dimetylundeca-3,5,9-trien-2-one |
| JP2015537055A (en) * | 2012-12-18 | 2015-12-24 | ディーエスエム アイピー アセッツ ビー．ブイ． | Use of a mixture of E / Z isomers to obtain specific products quantitatively by combined asymmetric hydrogenation |
| JP2016505568A (en) * | 2012-12-18 | 2016-02-25 | ディーエスエム アイピー アセッツ ビー．ブイ． | Use of a mixture of E / Z isomers to obtain specific products quantitatively by combining asymmetric hydrogenation and isomerization |
| WO2021095741A1 (en) * | 2019-11-11 | 2021-05-20 | 国立大学法人九州大学 | Novel sugar derivative useful in freezing of cells |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014096063A1 (en) * | 2012-12-18 | 2014-06-26 | Dsm Ip Assets B.V. | (6r,10r)-6,10,14-trimetylpentadecan-2-one prepared from 3,7-dimetyloct-2-enal or 3,7-dimetylocta-2,6-dienal |
-
1996
- 1996-02-21 JP JP06007696A patent/JP3725233B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002363064A (en) * | 2001-06-06 | 2002-12-18 | Kanebo Ltd | Skin cleansing agent |
| JP2002363060A (en) * | 2001-06-06 | 2002-12-18 | Kanebo Ltd | Bathing agent |
| JP4582960B2 (en) * | 2001-06-06 | 2010-11-17 | 塩水港精糖株式会社 | Bath composition |
| JP4625595B2 (en) * | 2001-06-06 | 2011-02-02 | 塩水港精糖株式会社 | Skin cleanser |
| WO2014097173A1 (en) * | 2012-12-18 | 2014-06-26 | Dsm Ip Assets B.V. | (6r,10r)-6,10,14-trimetylpentadecan-2-one prepared from 6,10-dimetylundeca-3,5,9-trien-2-one |
| JP2015537055A (en) * | 2012-12-18 | 2015-12-24 | ディーエスエム アイピー アセッツ ビー．ブイ． | Use of a mixture of E / Z isomers to obtain specific products quantitatively by combined asymmetric hydrogenation |
| JP2016505568A (en) * | 2012-12-18 | 2016-02-25 | ディーエスエム アイピー アセッツ ビー．ブイ． | Use of a mixture of E / Z isomers to obtain specific products quantitatively by combining asymmetric hydrogenation and isomerization |
| WO2021095741A1 (en) * | 2019-11-11 | 2021-05-20 | 国立大学法人九州大学 | Novel sugar derivative useful in freezing of cells |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3725233B2 (en) | 2005-12-07 |
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