JPH0363544B2 - - Google Patents
Info
- Publication number
- JPH0363544B2 JPH0363544B2 JP20189681A JP20189681A JPH0363544B2 JP H0363544 B2 JPH0363544 B2 JP H0363544B2 JP 20189681 A JP20189681 A JP 20189681A JP 20189681 A JP20189681 A JP 20189681A JP H0363544 B2 JPH0363544 B2 JP H0363544B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- amino
- ethanol
- chloro
- hydroxy
- 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.)
- Expired
Links
- -1 L-2-amino-5-chloro-6-hydroxy-4-hexenoic acid Chemical compound 0.000 claims description 6
- 150000001413 amino acids Chemical class 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 2
- 241000134916 Amanita Species 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 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 description 1
- 241000221198 Basidiomycota Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010008631 Cholera Diseases 0.000 description 1
- 241001138420 Fagus crenata Species 0.000 description 1
- 244000153234 Hibiscus abelmoschus Species 0.000 description 1
- 108010008292 L-Amino Acid Oxidase Proteins 0.000 description 1
- 102000007070 L-amino-acid oxidase Human genes 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- MHLMRBVCMNDOCW-UHFFFAOYSA-N acetic acid;butan-1-ol;hydrate Chemical compound O.CC(O)=O.CCCCO MHLMRBVCMNDOCW-UHFFFAOYSA-N 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- FEMOMIGRRWSMCU-UHFFFAOYSA-N ninhydrin Chemical compound C1=CC=C2C(=O)C(O)(O)C(=O)C2=C1 FEMOMIGRRWSMCU-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、新規なアミノ酸であるＬ−２−アミ
ノ−５−クロロ−６−ヒドロキシ−４−ヘキセン
酸に関するものである。
本発明者は、アマニタ属に属する担子菌の遊離
アミノ酸に関する一連の研究において、タマシロ
オニタケ（Amanita Sphaerobulbosa Hongo
sp.nov.）の子実体中に新規アミノ酸が多量に存
在することを見出し、これを純粋に単離すること
に成功した。このものは結晶性の物質で水−エタ
ノールから再結晶したものの物性は下記の通りで
ある。
色 ：無色
溶解性：水に可溶、有機溶媒に難溶
融 点：200−212℃（分解）
光学活性：Ｌ−アミノ酸酸化酵素の基質となる
ことからＬ型である。
MASS：TMS化物のGCMassでｍ／ｚ＝380に
脱メチルイオンのピークがあり、GC−
CIMassでは、ｍ／ｚ＝396にM+＋１イオ
ンの強いピークがある。一方、イオン強度
の比較からClの存在が示唆される。
ニンヒドリン反応：陽性
NMR：δ2.77（Oct，2H）〔−ＣＨ 2−〕、3.80
（ｔ，1H）
The present invention relates to a novel amino acid, L-2-amino-5-chloro-6-hydroxy-4-hexenoic acid. In a series of studies on free amino acids in basidiomycetes belonging to the genus Amanita, the present inventor discovered that Amanita Sphaerobulbosa Hongo
We discovered that a large amount of novel amino acids exist in the fruiting bodies of sp.nov. and succeeded in isolating them in pure form. This material is a crystalline substance that was recrystallized from water-ethanol, and its physical properties are as follows. Color: Colorless Solubility: Soluble in water, poorly soluble in organic solvents Melting point: 200-212°C (decomposed) Optical activity: L-type because it is a substrate for L-amino acid oxidase. MASS: There is a peak of demethylation ion at m/z = 380 in GCM ass of TMS compound, and GC-
In CIM ass , there is a strong peak of M + +1 ions at m/z = 396. On the other hand, a comparison of ionic strengths suggests the presence of Cl. Ninhydrin reaction: Positive NMR: δ2.77 (Oct, 2H) [ -CH 2 -], 3.80
(t, 1H)
【式】4.15（Ｓ，2H）
〔−ＣＨ 2OH〕、5.85（ｔ，1H）〔CH2−Ｃ
Ｈ＝〕
これらの結果から本物質は、Ｌ−２−アミノ−
５−クロロ−６−ヒドロキシ−４−ヘキセン酸と
決定された。
本発明の化合物は、タマシロオニタケの子実体
を水性溶媒で抽出し、抽出液をイオン交換樹脂を
用いたクロマトグラフイーにかけ、更にセルロー
スを用いたカラムクロマトグラフイーで精製した
後結晶化することにより容易に取得することがで
きる。
タマシロオニタケは、ブナ（Fagus crenata）
林中に産生し、コレラ型中毒をひきおこすキノコ
として知られている（植物研究雑誌44，８，230
−232、昭和44年）。
上記水性溶媒としては通常水または水−エタノ
ールが用いられるが、水−エタノールの代りに水
とメタノールやアセトン、メチルエチルケトン等
の親水性溶媒との混合溶媒を用いることもでき
る。また所望ならば親水性溶媒を単独で用いるこ
ともできる。抽出は常温で行うが加温してもよ
い。
本発明に係る化合物は、これまで知られていな
い新規な物質であり、塩素が付加した不飽和アミ
ノ酸でその構造が代射桔抗作用等の特異な生理活
性が期待される。
以下に実施例により本発明を更に詳細に説明す
るが本発明はその要旨を超えない限り以下の実施
例により限定されるものではない。
実施例 １
タマシロオニタケ16ｇに80％エタノール200ml
を加えミキサーにかける。液をＨ型のアンバー
ライトIR−120B（商標、ローム＆ハース社製品）
５mlを充填したカラムに通した。カラムを80％エ
タノール、次いで水で洗浄したのち、2N−
NH4OH50mlを通液してアミノ酸を溶出させた。
溶出液を減圧濃縮したのち、アビセル（商標、旭
化成工業(株)製品）を充填した11mmφ×970mmＬの
カラムに通した。
カラムをｎ−ブタノール−酢酸−水（63：10：
27）で展開し該物質を含む画分を集め、減圧濃縮
するとＬ−２−アミノ−５−クロロ−６−ヒドロ
キシ−４−ヘキセン酸の粗結晶11mgが得られた。 [Formula] 4.15 (S, 2H) [-C H 2 OH], 5.85 (t, 1H) [CH 2 -C
H=] From these results, this substance is L-2-amino-
It was determined to be 5-chloro-6-hydroxy-4-hexenoic acid. The compound of the present invention can be obtained by extracting the fruiting body of A. chinensis with an aqueous solvent, subjecting the extract to chromatography using an ion exchange resin, further purifying it with column chromatography using cellulose, and then crystallizing it. can be easily obtained. Fagus crenata
It is known as a mushroom that grows in forests and causes cholera-type poisoning (Botanical Research Journal 44 , 8, 230
−232, 1968). As the aqueous solvent, water or water-ethanol is usually used, but a mixed solvent of water and a hydrophilic solvent such as methanol, acetone, or methyl ethyl ketone can also be used instead of water-ethanol. Hydrophilic solvents can also be used alone if desired. Extraction is performed at room temperature, but may be heated. The compound according to the present invention is a novel substance that has not been known until now, and its structure is expected to have unique physiological activities such as anti-inflammatory action due to its structure, which is an unsaturated amino acid with added chlorine. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. Example 1 80% ethanol 200ml for 16g of Onitake mushrooms
Add to mixer. Liquid H type Amberlite IR-120B (trademark, Rohm & Haas product)
It was passed through a column packed with 5 ml. After washing the column with 80% ethanol and then water,
Amino acids were eluted by passing 50 ml of NH 4 OH through the solution.
After the eluate was concentrated under reduced pressure, it was passed through a 11 mmφ×970 mmL column packed with Avicel (trademark, product of Asahi Kasei Industries, Ltd.). The column was diluted with n-butanol-acetic acid-water (63:10:
27), and fractions containing the substance were collected and concentrated under reduced pressure to obtain 11 mg of crude crystals of L-2-amino-5-chloro-6-hydroxy-4-hexenoic acid.
第１図は実施例１で得られたＬ−２−アミノ−
５−クロロ−６−ヒドロキシ−４−ヘキセン酸の
再結晶品の赤外吸収スペクトルである。
Figure 1 shows the L-2-amino-
It is an infrared absorption spectrum of a recrystallized product of 5-chloro-6-hydroxy-4-hexenoic acid.
Claims (1)
ロロ−６−ヒドロキシ−４−ヘキセン酸。 [Scope of Claims] 1 L-2-amino-5-chloro-6-hydroxy-4-hexenoic acid represented by the following formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20189681A JPS58103347A (en) | 1981-12-15 | 1981-12-15 | amino acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20189681A JPS58103347A (en) | 1981-12-15 | 1981-12-15 | amino acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58103347A JPS58103347A (en) | 1983-06-20 |
| JPH0363544B2 true JPH0363544B2 (en) | 1991-10-01 |
Family
ID=16448613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20189681A Granted JPS58103347A (en) | 1981-12-15 | 1981-12-15 | amino acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58103347A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH079590A (en) * | 1993-06-29 | 1995-01-13 | Tanabe:Kk | Oblique folding device for blanks for automatic box making |
-
1981
- 1981-12-15 JP JP20189681A patent/JPS58103347A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58103347A (en) | 1983-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2504335B1 (en) | Process for the purification of methyl-{4,6-diamino-2-[1-(2-fluorobenzyl)-1H-pyrazolo[3,4-b]pyridin-3-yl]pyrimidin-5-yl}-carbamate | |
| EP0142739B1 (en) | Amino acid derivatives and their preparation | |
| JPH09316091A (en) | Production of arginylfructosylglucoses | |
| EP0036663A1 (en) | Oxiranebutanoic acid derivatives, their preparation and use, and medicaments containing them | |
| Lamb et al. | The Erlenmeyer synthesis of amino-acids | |
| JPH0363544B2 (en) | ||
| Zervas et al. | Preparation and disulfide interchange reactions of unsymmetrical open-chain derivatives of cystine | |
| US6147228A (en) | Convenient method for the large scale isolation of garcinia acid | |
| JPH0768163B2 (en) | Process for producing cyclopentenone derivative | |
| JP4770032B2 (en) | Sheatan derivative | |
| Kasai et al. | Two cysteine derivatives in asparagus shoots | |
| CH387022A (en) | Process for the preparation of 6-deoxy-tetracyclines | |
| DE1958383C3 (en) | Leupeptins, processes for their preparation and pharmaceuticals containing them | |
| JPS6281325A (en) | Purification of aescin | |
| US4656248A (en) | Cupric oxidation of 1,6-dimercapto-containing peptides | |
| SU786856A3 (en) | Method of preparing escine | |
| US4546203A (en) | Facile synthesis of β-hydroxy-β-methylglutaric acid | |
| IE45374B1 (en) | A procress for preparing [-cyano-3-pehnoxylbenzyl alcohol | |
| JPH1192492A (en) | Method for separating 3-o-glucopyranosyl-gamma-butyrolactone | |
| JPH0246598B2 (en) | SHINKINARUTANNIN | |
| DE2535766B2 (en) | Process for the preparation of racemic allethrolone | |
| Smith et al. | Aminotriazole metabolism in Cirsium arvense (L.) Scop. and Pisum sativum L. | |
| JPH0597834A (en) | 2,3,6-trimethyl-5-(tetrahydrofuran-2-yl)benzoquinone | |
| Haller et al. | Rotenone | |
| JPH0692392B2 (en) | New pseudouridine derivative |