JPS5849346A - Mycosporine-based amino acid and its derivative - Google Patents
Mycosporine-based amino acid and its derivativeInfo
- Publication number
- JPS5849346A JPS5849346A JP14758281A JP14758281A JPS5849346A JP S5849346 A JPS5849346 A JP S5849346A JP 14758281 A JP14758281 A JP 14758281A JP 14758281 A JP14758281 A JP 14758281A JP S5849346 A JPS5849346 A JP S5849346A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound shown
- ultraviolet
- mycosporine
- amino acid
- 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.)
- Pending
Links
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は新規なマイコスポリン系アミノ酸お種のマイ＝
ｙ２ボリン系（ｍｙｌｏｓｐｏｒｉｎｅ−１１ｋａ）ア
ミノ酸が存在することが報告されて−る。[Detailed Description of the Invention] The present invention provides a novel mycosporine amino acid species, Mycosporin.
It has been reported that y2 borine (mylosporine-11ka) amino acids exist.
を対象に検討した結果、紫外部に＝ｉりｉい吸収をもつ
新規なマイコスポリン系アミノ酸の存在を確社し、これ
を単離し、さらにその芳′ｌＦ族化日導体を得て本発明
を達成した。すなわち、本発明の要旨ｄ、Ｎ−（コーヒ
ドロキシエチル）−３−カルボキシメチルアミノ−ｊ−
ヒドロキシ−ｊ−ヒドロキシメチルーーーメトキシシク
ロへキシリデンアミンーコーエンおよびその芳香族化誘
導体、ｙ−（Ｊ−ヒドロキシエチルアミノ）−ダーメト
キシー！−メトキシカルボニルメチルアミノペンジルア
ルコールからなる鮮から選ばれ九マイコスポリン系アミ
ノ＃Ｉま九はその誘導体に存する。As a result of our investigation, we established the existence of a new mycosporine amino acid that has high absorption in the ultraviolet region, isolated it, and obtained its aromatic compound, thereby achieving the present invention. Achieved. That is, the gist of the present invention d, N-(cohydroxyethyl)-3-carboxymethylamino-j-
Hydroxy-j-hydroxymethyl-methoxycyclohexylideneamine-Cohen and its aromatized derivatives, y-(J-hydroxyethylamino)-dermethoxy! -Methoxycarbonylmethylaminopendyl alcohol selected from the group consisting of nine mycosporine amino #I and its derivatives.
本発明の詳細な説明するに、本発明のマイコスポリン系
アミノ虐は、たとえば、イトマキヒトデをホモジナイズ
して溶卸ｊにより抽出し、カラムクロマドグａ）フィー
、活性炭処理、高速液体クロマトグラフィー等の組合せ
によシ単離することができる。To explain the present invention in detail, the mycosporin-based amino acid of the present invention is obtained by, for example, homogenizing starfish and extracting it by elutriation, followed by a combination of column chromatography, activated carbon treatment, high-performance liquid chromatography, etc. It can be isolated.
本発明の物質は、後記実施例に示すように、紫外線吸収
スペクトル測定の結果、３３００ｎ の紫外部に極大吸
収を示し、またプロトン−ＮＭｆ（。As shown in the Examples below, the substance of the present invention shows maximum absorption in the ultraviolet region of 3300 nm as a result of ultraviolet absorption spectrum measurement, and also shows proton-NMf (.
マススペクトルおよび分子吸光係数の測定結果等から、
次式（１）で示されるｗ−（Ｊ−ヒドロキシエチル）−
３−カルボキシメチルアミノ−ｊ−ヒドロキシ−ｊ−ヒ
ドロキシメチルーコーメトキシシクロへキシリデンアミ
ンーコーエンであることが確聞された。From the mass spectrum and molecular extinction coefficient measurement results,
w-(J-hydroxyethyl)- represented by the following formula (1)
It was confirmed that it was 3-carboxymethylamino-j-hydroxy-j-hydroxymethyl-comethoxycyclohexylideneamine-Cohen.
この化合物は次式（１）′のような共鳴構造ｔ−有する
。This compound has a resonance structure t- as shown in the following formula (1)'.
前ｆ！（１）式で示される本発明のマイコスポリン系ア
ンノ酸をジアゾメタンと反応させると、脱水反応による
芳香族化とメチル化によって次式（■）で示宮れる３−
（−一ヒドロキシエチルアミノ）−亭一メトキシー！−
メトキシカルボニルメチルアＺノベンジルアルコールが
ｓられた。Front f! When the mycosporin-based annoic acid of the present invention represented by the formula (1) is reacted with diazomethane, the 3-
(-monohydroxyethylamino)-Teiichi methoxy! −
Methoxycarbonylmethylazinebenzyl alcohol was added.
この物質も、紫外部に強％ＡＷｊ収をもち、後記実施例
に示すように、その構造がｆ１認された。This substance also had a strong %AWj yield in the ultraviolet region, and as shown in the Examples below, its structure was recognized as f1.
前記式（１）および（ＩＪで示される本発明の化合物は
、紫外部に強い吸収をもつことから紫外線吸収剤として
期待される。The compounds of the present invention represented by formulas (1) and (IJ) have strong absorption in the ultraviolet region and are therefore expected to be used as ultraviolet absorbers.
以下に本発明を冥施例についてさらに詳細に収用する。In the following, the present invention will be described in more detail with reference to specific examples.
実施剰
青森県陸拠湾で採取したイトマキヒトデｌゆを破砕して
ホモジナイズし、２ｔ（０７０％１ｆｉノールを用いて
３回抽出処理を行い、抽出液を減圧下参〇℃以下で蒸発
乾固した。乾固物をメタノールに溶解し、不溶物をＰ去
した後、減圧下’ＩＱ℃以下で乾固し、乾固物を水に弓
隋しダイヤイオンｏｏ）ｉｐ−ｓＯ（三菱化成社製、ポ
ーラｘ街脂）ｌｔを充填したカラムにかけ虞外部吸堰（
３３ｏｎｍ） がなくなるまで水を流通した。Excess starfish collected from Rikuji Bay, Aomori Prefecture, was crushed and homogenized, extracted three times using 2t (070% 1finol), and the extract was evaporated to dryness under reduced pressure at 0°C or below. After dissolving the dried product in methanol and removing insoluble matter, it was dried under reduced pressure at a temperature below IQ°C. , Polar
33 onm) was used up.
流出液を活性炭（和光純桑社製）を充填したカラム（長
さｊ 、、００ ａｍ、直径３コＩ）にかけ、水先後１
０％エタノールで溶出し、溶出液を減圧下り０℃以下で
蒸発乾固し、乾固物を水に溶屏して、Ｉ）ｅｖｅｌｏｓ
ｉ％！り一〇ＤＳ （野村化字製）を担体゛とした高速
液体クロマトカラム（長さ４０θ踵、直径？、ｊｍ）に
かけ、０．−嗟酢酸で溶出し紫外線吸収画分を集め減圧
下亭θ℃以下で蒸発乾固し九。The effluent was applied to a column (length J, 00 am, diameter 3 columns) packed with activated carbon (manufactured by Wako Junkuwa Co., Ltd.), and
Elute with 0% ethanol, evaporate the eluate to dryness under reduced pressure at 0°C or less, dissolve the dried product in water, and prepare I) evelos.
i%! It was applied to a high performance liquid chromatography column (length: 40θ, diameter: ?, jm) using Ri-10DS (manufactured by Nomura Kaji) as a carrier. - Elute with acetic acid and collect the ultraviolet absorbing fraction and evaporate to dryness under reduced pressure below θ°C.
乾固物を水に浴着し、Ｄｏｗａｙ１■！０ｉｌＸＩＨ”
樹脂（ダウケミカル社製陽イオン交候衛脂）を充填した
カラム（長さコｊ Ｏｗｍ 、直径／ ＯＷ ）にかけ
、水洗後０．５’Ｍｍｔｉｌ！で溶出し、路外−画分を
集めて力性ソーダで中和した後、前記と同様鎧の活性炭
充填カラムにかけｊＯ囁エタノールで耐出し、浴出ｔｈ
分を染めて減圧下ａＯ℃以ドで乾固し、乾固′＠をさら
にＭｊ記と同様に高速流体クロマト７：７ンイーにか１
ｒｆＯ，／９６酢饋で溶出した。Soak the dry matter in water and doway1■! 0ilXIH”
It was applied to a column (length: owm, diameter: ow) filled with resin (cationic antihypertensive resin manufactured by Dow Chemical Company), and after washing with water, it was 0.5'Mmtil! After collecting the off-road fraction and neutralizing it with sodium hydroxide, it was applied to an activated carbon-filled column in the same manner as above and eluted with ethanol.
The sample was dyed and dried under reduced pressure at a temperature below 0°C, and the dried product was further subjected to high-speed fluid chromatography 7:7 in the same manner as described in Mj.
It was eluted with rfO,/96 vinegar.
このようにして無色シラツブ状の物質？智が得られた。Is this a colorless slag-like substance? I gained wisdom.
本品祉、紫外線吸収スペクトル測定の結果、水浴液にお
ｉてＪＪＯｎｍ（Ｄ紫外−に極大ｑ＆収を示し、また、
マススペクトルはコｔｏ、ｄｉλＯ！（Ｍ”−４冨０）
（計算値’ｔ！’＋ｓ”ｔＯｓ ：コツ０、Ｉｌλ／４
）を与え、この結果から分子式’１ｌＨ１ｅモ０．であ
ることがわかる。また、２７０メガヘルツ（ＭＨｇ）（
重水中で測定）の分解能を有する１０トンＮＭＲΦ動定
値社、 δ コ、７３、コ、ｆ４Ｉ （コＨ１ムＢｑｃ
ｅｎ＋ｃｅｒ、Ｊ＝７ｆ Ｈｔｓ）、λ、ゲλ（，２Ｈ
，ｓ）、Ｊ、！Ｉ（２Ｈ。As a result of ultraviolet absorption spectrum measurement of this product, the water bath liquid showed a maximum q&yield of JJOnm (D ultraviolet), and
The mass spectrum is diλO! (M”-4 0)
(Calculated value 't!'+s"tOs: Tip 0, Ilλ/4
), and from this result, the molecular formula '1lH1emo0. It can be seen that it is. In addition, 270 megahertz (MHg) (
A 10 ton NMR Φ dynamic fixed value with a resolution of δ (measured in heavy water), δ, 73,
en+cer, J=7f Hts), λ, geλ(,2H
,s),J,! I (2H.
ａ）、Ｊ、６（７（コＪｔ、Ｊ＝ｊ、４ｉ１ｇ）、、？
、！ｊ（ｊＨ，ａ）。a), J, 6(7(koJt, J=j, 4i1g),,?
,! j(jH, a).
て、本物質が前記（１）式で示される化合物であること
が確認された。It was confirmed that this substance was a compound represented by the above formula (1).
前売（１）式で示される・マイコス”ボリシ系アミノ酸
をメタノールに溶解し、これを過剰量のジアゾメタンの
エーテル溶液と混合、シ、寧温７で°−昼“夜装置し丸
後、減゛圧下室課で一蒸発乾固し、乾固物を、クロロホ
ルム−メタノール（デ：ｌ）を展開液として薄層クロマ
トグラフィー（シリカて
ゲル担体）にかけ壷精製して、前売（１）式で示される
３−（２−ヒドロキシエチルアミノ）−ダーメトキシー
！−メトキシカルボニルメチルアミノベンジルアルコー
ルかには定量的に得られ九〇
本品の紫外緑吸収スペクトルは、メタノール溶液におい
てλコアｎｍおよびコ９ＫｎｍＫ極大吸収を示し、また
マススペクトルは−ｌ参、＃１３デｌ（Ｍ”） （計算
値０１Ｍ”！。Ｎ、０．：Ｊｆ亭、／Ｊ？Ｊ）を与えこ
の結果から分子式’ｊｊＨｔｌ”！’ｓであることがわ
かる。また、コアＱメガヘルツ（ＭＨｚ）（重クロロホ
ルム中で測定）の分解能を有するプロトン夏ＭＲｏＩＷ
Ｊ定値は、δ３．３Ｊ（コＨ、ｔ 、 Ｊ＝ｓ、２Ｈｚ
） 。The ``Mycos'' amino acid represented by formula (1) was dissolved in methanol, mixed with an excess amount of an ether solution of diazomethane, and then heated at 7°C for a day and night. It was evaporated to dryness in the pressure chamber section, and the dried product was purified by thin-layer chromatography (silica gel carrier) using chloroform-methanol (D:L) as a developing solution, and the product was expressed by formula (1). 3-(2-hydroxyethylamino)-dermethoxy! -Methoxycarbonylmethylaminobenzyl alcohol is quantitatively obtained.The ultraviolet green absorption spectrum of this product shows a maximum absorption of λ core nm and 9K nmK in methanol solution, and the mass spectrum is -1, #13. Del(M") (calculated value 01M"!.N, 0.: Jftei, /J?J) is given, and from this result it can be seen that the molecular formula is 'jjHtl'!'s. Also, the core Q megahertz ( MHz) (measured in deuterochloroform).
The J constant value is δ3.3J (koH, t, J=s, 2Hz
).
ｓ、ｔｓ（３Ｈ，８）、Ｊ、？ｆ（ＪＨ，ａ）、１．ｙ
；ｚ３（ａｍ、 ｔ、Ｊ＝！、コＦｉｇ）、Ｊ、ｆｊ（
コＨ，ｂｒａ）、＜ｔ、ｊｕ（コ”＊’）１６．θＪ’
（／Ｈ，ｄ、Ｊ＝＝／、ｒＨｇ）、ｉ／？（／’Ｊｄ、
Ｔ＝／、ｒＨりであって、本物質が前記（１１７式で示
される化合物であることがｉ１Ｍ認された。s, ts (3H, 8), J,? f(JH, a), 1. y
;z3(am, t, J=!, koFig), J, fj(
koH,bra), <t,ju(ko"*')16.θJ'
(/H, d, J==/, rHg), i/? (/'Jd,
T=/, rH, and it was confirmed by i1M that this substance was a compound represented by the above formula (117).
出願人 三菱化成工業株式会社Applicant: Mitsubishi Chemical Industries, Ltd.
Claims (1)
メチルアミノーｊ−ヒドロキシ−！−ヒドロキシメテル
ーコーメトキシシクロへキシリデンアミンーコーエンお
よびその芳香族化誘導体３−（コーヒドロキシエテルア
ば））−Ｉｔ−メトキシ−！−メトキシカルボニルメチ
ルアξノベンジルアルコールからなる群よシ選ばれたマ
イコスポリン系アミン＃７Ｉまえはその誘導体111N-(cohydroxyether)-3-dimethylamino-j-hydroxy-! -Hydroxymethoxycyclohexylideneamine-Cohen and its aromatized derivatives 3-(cohydroxyetheraba))-It-methoxy-! - selected mycosporine amines #7 from the group consisting of methoxycarbonylmethylanobenzyl alcohols, derivatives thereof
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14758281A JPS5849346A (en) | 1981-09-18 | 1981-09-18 | Mycosporine-based amino acid and its derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14758281A JPS5849346A (en) | 1981-09-18 | 1981-09-18 | Mycosporine-based amino acid and its derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5849346A true JPS5849346A (en) | 1983-03-23 |
Family
ID=15433603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14758281A Pending JPS5849346A (en) | 1981-09-18 | 1981-09-18 | Mycosporine-based amino acid and its derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5849346A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002039974A1 (en) * | 2000-11-17 | 2002-05-23 | Natural Environment Research Council | Personal care compositions |
| ES2284344A1 (en) * | 2005-08-31 | 2007-11-01 | Universidad De Malaga | Use of a mycosporin-type amino acid (shinorine) as an antioxidant |
| CN103755589A (en) * | 2013-12-19 | 2014-04-30 | 中国科学院水生生物研究所 | Method for extracting mycosporine-like amino acid shinorine from microcystis |
-
1981
- 1981-09-18 JP JP14758281A patent/JPS5849346A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002039974A1 (en) * | 2000-11-17 | 2002-05-23 | Natural Environment Research Council | Personal care compositions |
| ES2284344A1 (en) * | 2005-08-31 | 2007-11-01 | Universidad De Malaga | Use of a mycosporin-type amino acid (shinorine) as an antioxidant |
| CN103755589A (en) * | 2013-12-19 | 2014-04-30 | 中国科学院水生生物研究所 | Method for extracting mycosporine-like amino acid shinorine from microcystis |
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