JP2977209B2 - Glucosamine derivative and method for producing the same - Google Patents
Glucosamine derivative and method for producing the sameInfo
- Publication number
- JP2977209B2 JP2977209B2 JP1218301A JP21830189A JP2977209B2 JP 2977209 B2 JP2977209 B2 JP 2977209B2 JP 1218301 A JP1218301 A JP 1218301A JP 21830189 A JP21830189 A JP 21830189A JP 2977209 B2 JP2977209 B2 JP 2977209B2
- Authority
- JP
- Japan
- Prior art keywords
- glucosamine
- nitrophenyl
- added
- producing
- trifluoroacetyl
- 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 - Fee Related
Links
Landscapes
- Saccharide Compounds (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、グルコサミン誘導体ｐ−ニトロフェニル
β−Ｄ−グルコサミニド及びその製造法に関するもので
ある。The present invention relates to a glucosamine derivative p-nitrophenyl
The present invention relates to β-D-glucosaminide and a method for producing the same.
（従来の技術） グリコシダーゼ、例えば、グルコシダーゼガラクトシ
ダーゼやＮ−アセチルグルコサミニダーゼは動物、植
物、微生物などに広く存在している糖質分解酵素であ
る。最近、これらのグリコシダーゼは、複合糖質糖鎖の
構造解析に有力な手段となるため広く用いられるように
なったばかりでなく、これら酵素の糖転移機能を利用し
た有用オリゴ糖の生産にも用いられており、フラクトオ
リゴ糖やガラクトオリゴ糖などは機能性食品素材として
すでに実用化されている。このように、グリコシダーゼ
は、糖質の利用を考える上で有用な酵素である。(Prior Art) Glycosidases, for example, glucosidase galactosidase and N-acetylglucosaminidase, are carbohydrate-degrading enzymes widely existing in animals, plants, microorganisms, and the like. Recently, these glycosidases have become widely used because they are a powerful tool for structural analysis of glycoconjugate sugar chains, and are also used for producing useful oligosaccharides utilizing the glycosyltransfer function of these enzymes. Fructooligosaccharides and galactooligosaccharides have already been put to practical use as functional food materials. Thus, glycosidase is a useful enzyme in considering utilization of carbohydrate.
（発明が解決しようとする課題） グリコシダーゼの活性測定法は、一般的に単糖誘導体
を用いて行われており、中でも、ｐ−ニトロフェニル
グリコシドは、これらの酵素の基質として最もよく用い
られている。しかしながら、このような合成基質がない
ため今までに見いだされていないグリコシダーゼも多く
存在している。その一つとしてβ−Ｄ−グルコサミニダ
ーゼが上げられる。(Problems to be Solved by the Invention) The method for measuring the activity of glycosidase is generally carried out using a monosaccharide derivative.
Glycosides are most often used as substrates for these enzymes. However, there are also many glycosidases that have not been found so far due to lack of such a synthetic substrate. One of them is β-D-glucosaminidase.
（課題を解決するための手段） 本発明者らは、このβ−Ｄ−グルコサミニダーゼの活
性測定用基質を合成すべく鋭意研究を行った結果、本発
明を完成するに至った 本発明におけるｐ−ニトロフェニル β−Ｄ−グルコ
サミニドは、下記の式 で示される新規化合物であって、以下の物理化学的性質
を示す。(Means for Solving the Problems) The present inventors have conducted intensive studies to synthesize the substrate for measuring the activity of β-D-glucosaminidase, and as a result, have completed the present invention. Nitrophenyl β-D-glucosaminide has the following formula: Which has the following physicochemical properties.
分子式:C12H16O7N2 分子量:300.3 融 点:181−182℃（分解） 比旋光度：▲〔ａ〕25 D▼＝−105.0（３％、水） 溶解性：水、メタノール水溶液、エタノール水溶液など
に可溶、アセトン、クロロホルム、ヘキサンなどに不
溶。Molecular formula: C 12 H 16 O 7 N 2 Molecular weight: 300.3 Melting point: 181-282 ° C. (decomposition) Specific rotation: ▲ [a] 25 D ▼ = -105.0 (3%, water) Solubility: water, aqueous methanol solution Soluble in aqueous ethanol solution, insoluble in acetone, chloroform, hexane, etc.
次に、新規化合物ｐ−ニトロフェニル β−Ｄ−グル
コサミニドの製造法について説明する。Next, a method for producing the novel compound p-nitrophenyl β-D-glucosaminide will be described.
本発明のグルコサミン誘導体は、グルコサミンを出発
材料とし、これをＮ−トリフルオロアセチル β−Ｄ−
グルコサミン テトラアセテート誘導体とした後、ハロ
ゲン化し、このハロゲン化誘導体とｐ−ニトロフェノー
ルとを縮合させることによってｐ−ニトロフェニル Ｎ
−トリフルオロアセチル β−Ｄ−グルコサミン トリ
アセテートを得、これを脱Ｎ−トリフルオロアセチル化
並びに脱Ｏ−アセチル化することによって製造すること
ができる。The glucosamine derivative of the present invention uses glucosamine as a starting material, and uses this as N-trifluoroacetyl β-D-
After forming a glucosamine tetraacetate derivative, it is halogenated, and by condensing this halogenated derivative with p-nitrophenol, p-nitrophenyl N
-Trifluoroacetyl β-D-glucosamine triacetate, which can be produced by de-N-trifluoroacetylation and de-O-acetylation.
例えば、Bergmannらの方法（Ber.64（1931）975）を
用いて２−アミノ−２−デオキシ−β−Ｄ−グルコース
テトラアセテートを調製し、これを無水トリフルオロ
酢酸でＮ−トリフルオロアセチル化するか、あるいは、
Wolfromらの方法（Carbhydr.Res.,11（1969）63）を用
いて、まずＮ−トリフルオロアセチル−Ｄ−グルコサミ
ンを調製し、これを無水酢酸−ピリジン中でＯ−アセチ
ル化することによって式（１）で示されるＮ−トリフル
オロアセチル β−Ｄ−グルコサミン テトラアセテー
トを得る。For example, 2-amino-2-deoxy-β-D-glucose tetraacetate was prepared using the method of Bergmann et al. (Ber. 64 (1931) 975) and N-trifluoroacetylated with trifluoroacetic anhydride. Do or
First, N-trifluoroacetyl-D-glucosamine is prepared using the method of Wolfrom et al. (Carbhydr. Res., 11 (1969) 63), and this is prepared by O-acetylation in acetic anhydride-pyridine. N-trifluoroacetyl β-D-glucosamine tetraacetate represented by (1) is obtained.
式（１） 次に、上記化合物を塩化水素を飽和させた酢酸−無水
酢酸（10:1）に溶解させ、室温で４−48時間反応を行
う。反応液にクロロホルムを加え、生成物を抽出する。
このクロロホルム層を十分に洗浄後、減圧乾固させ、式
（２）に示されるＮ−トリフルオロアセチル−トリアセ
チル−グルコサミン クロライドの白色残渣を得る。Equation (1) Next, the above compound is dissolved in acetic acid-acetic anhydride (10: 1) saturated with hydrogen chloride and reacted at room temperature for 4-48 hours. Chloroform is added to the reaction solution to extract the product.
After sufficiently washing the chloroform layer, it is dried under reduced pressure to obtain a white residue of N-trifluoroacetyl-triacetyl-glucosamine chloride represented by the formula (2).
式（２） 上記物質をアセトンに溶解後、ｐ−ニトロフェノール
を含むアセトン−水酸化ナトリウム（1:1）溶液を加
え、室温で２−16時間反応を行う。アセトンを減圧除去
した後、クロロホルムを加えて生成物を抽出する。この
有機溶媒層を飽和炭酸水素ナトリウム溶液で十分に洗浄
後、減圧乾固させる。これをエタノールから結晶化させ
式（３）に示されるｐ−ニトロフェニル Ｎ−トリフル
オロアセチル β−Ｄ−グルコサミン トリアセテート
を得る。Equation (2) After dissolving the above substance in acetone, an acetone-sodium hydroxide (1: 1) solution containing p-nitrophenol is added, and the mixture is reacted at room temperature for 2 to 16 hours. After removing acetone under reduced pressure, chloroform is added to extract the product. The organic solvent layer is sufficiently washed with a saturated sodium hydrogen carbonate solution and then dried under reduced pressure. This is crystallized from ethanol to obtain p-nitrophenyl N-trifluoroacetyl β-D-glucosamine triacetate represented by the formula (3).
式（３） 次に、式（３）の化合物をアンモニアを飽和したメタ
ノール中室温で３−６日間処理することにより脱Ｎ−ト
リフルオロアセチル化及び脱Ｏ−アセチル化し、本発明
のｐ−ニトロフェニル β−Ｄ−グルコサミニドを得る
ことができる。Equation (3) Next, the compound of formula (3) is de-N-trifluoroacetylated and de-O-acetylated by treatment in ammonia-saturated methanol at room temperature for 3-6 days to give p-nitrophenyl β-D of the present invention. -Glucosaminide can be obtained.
（実施例） 以下に実施例を示して本発明をさらに具体的に説明す
るが、かかる説明によって本発明が何ら限定されるもの
ではない。(Examples) Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the description.
Ｄ−グルコサミン塩酸塩100gを1.0N NAOH溶液470mlに
溶解後、ｐ−アニスアルデヒド72mlを加えて室温で１時
間撹拌しながら反応を行った。析出した沈澱を集め、冷
水及びエタノールで洗浄後、真空乾燥しＮ−アニシリデ
ン グルコサミン（ａ）124g（90）％を得た。m.p.159
−160℃（分解）。After 100 g of D-glucosamine hydrochloride was dissolved in 470 ml of 1.0 N NAOH solution, 72 ml of p-anisaldehyde was added and the reaction was carried out with stirring at room temperature for 1 hour. The precipitated precipitate was collected, washed with cold water and ethanol, and dried under vacuum to obtain 124 g (90)% of N-anisylidene glucosamine (a). mp159
-160 ° C (decomposition).
上記のＮ−アニシリデン グルコサミン（ａ）120gを
無水酢酸−ピリジン（1:2）900mlに溶解し、室温で一夜
反応を行った。反応液を減圧濃縮してシロップ状とし、
これにエタノール1000mlを加えて一夜冷蔵庫に放置し
た。析出した結晶を集めエタノールで洗浄後、乾燥しＮ
−アニシリデン β−Ｄ−グルコサミン テトラアセテ
ート（ｂ）41g（75％）を得た。m.p.183−185℃。120 g of the above N-anisidylene glucosamine (a) was dissolved in 900 ml of acetic anhydride-pyridine (1: 2), and the reaction was carried out at room temperature overnight. The reaction solution was concentrated under reduced pressure to a syrup,
1000 ml of ethanol was added thereto, and the mixture was left in a refrigerator overnight. The precipitated crystals are collected, washed with ethanol, dried and dried.
-Anisylidene [beta] -D-glucosamine tetraacetate (b) 41 g (75%) was obtained. mp 183-185 ° C.
次に、Ｎ−アニシリデン β−Ｄ−グルコサミン テ
トラアセテート（ｂ）100gをアセトン1500mlに溶解さ
せ、5N塩酸50mlを加えた。この溶液を30分間60℃で加温
後、冷却しジエチルエーテル500mlを加えて２時間撹拌
した。生じた沈澱物を集めジエチルエーテルで洗浄後乾
燥し、テトラアセチル−β−Ｄ−グルコサミン塩酸塩
（ｃ）80g（97％）を得た。そして、これを水1000mlに
溶解し、それに酢酸ナトリウム35gを加え、室温で２時
間撹拌した。反応液にクロロホルムを加えて生成物を抽
出し、このクロロホルム層を水で洗浄後濃縮乾固し、ジ
エチルエーテル200mlを加え結晶化した。析出した結晶
を集めジエチルエーテルで洗浄後乾燥し、β−Ｄ−グル
コサミン テトラアセテート（ｄ）58g（80％）を得
た。m.p.137−139℃。Next, 100 g of N-anisylidene β-D-glucosamine tetraacetate (b) was dissolved in 1500 ml of acetone, and 50 ml of 5N hydrochloric acid was added. The solution was heated at 60 ° C. for 30 minutes, cooled, added with 500 ml of diethyl ether, and stirred for 2 hours. The resulting precipitate was collected, washed with diethyl ether and dried to obtain 80 g (97%) of tetraacetyl-β-D-glucosamine hydrochloride (c). This was dissolved in 1000 ml of water, 35 g of sodium acetate was added thereto, and the mixture was stirred at room temperature for 2 hours. Chloroform was added to the reaction solution to extract the product. The chloroform layer was washed with water, concentrated and dried, and crystallized by adding 200 ml of diethyl ether. The precipitated crystals were collected, washed with diethyl ether and dried to obtain 58 g (80%) of β-D-glucosamine tetraacetate (d). mp 137-139 ° C.
アセトン−無水トリフルオロ酢酸（5:1）混合液100ml
を−10℃に冷却後、この溶液にβ−Ｄ−グルコサミン
テトラアセテート（ｄ）15gを徐々に添加した。反応液
をさらに30分間−10℃に保った後、水を滴下して過剰の
無水トリフルオロ酢酸を分解した。これを氷水500ml中
に注ぎ込み１時間撹拌した。析出した沈澱を集め水で洗
浄後乾燥し、Ｎ−トリフルオロアセチル−β−Ｄ−グル
コサミン テトラアセテート（ｅ）18g（92％）を得
た。m.p.168−169℃。Acetone-trifluoroacetic anhydride (5: 1) mixture 100ml
Was cooled to -10 ° C, and β-D-glucosamine was added to the solution.
15 g of tetraacetate (d) was gradually added. After keeping the reaction solution at -10 ° C for further 30 minutes, water was added dropwise to decompose excess trifluoroacetic anhydride. This was poured into 500 ml of ice water and stirred for 1 hour. The precipitated precipitate was collected, washed with water and dried to obtain 18 g (92%) of N-trifluoroacetyl-β-D-glucosamine tetraacetate (e). mp 168-169 ° C.
上記の化合物（ｅ）10gを０℃で塩化水素を飽和させ
た酢酸−無水酢酸（10:1）30mlに溶解後、室温で16時間
放置した。反応液にクロロホルムを加えて生成物を抽出
した。クロロホルム層を飽和炭酸水素ナトリウムで十分
洗浄後、冷水で洗浄した。この抽出液を減圧濃縮しシロ
ップ状とした後乾燥した。この残渣をアセトン50mlに溶
解後、ｐ−ニトロフェノール5.0gを含むアセトン−1.0M
水酸化ナトリウム（1:1）30mlを加え室温で８時間反応
させた。減圧濃縮してアセトンを除去後、クロロホルム
で生成物を抽出し飽和炭酸水素ナトリウムで十分洗浄し
た。クロロホルムを減圧除去後エタノールから結晶化
し、ｐ−ニトロフェニル β−Ｄ−グルコサミントリア
セテート（ｆ）4.9g（44％）を得た。m.p.196−198℃
（分解）。10 g of the above compound (e) was dissolved in 30 ml of acetic acid-acetic anhydride (10: 1) saturated with hydrogen chloride at 0 ° C., and then left at room temperature for 16 hours. Chloroform was added to the reaction solution to extract the product. The chloroform layer was sufficiently washed with saturated sodium hydrogen carbonate and then washed with cold water. The extract was concentrated under reduced pressure to form a syrup and dried. After dissolving this residue in 50 ml of acetone, acetone-1.0 M containing 5.0 g of p-nitrophenol was used.
30 ml of sodium hydroxide (1: 1) was added and reacted at room temperature for 8 hours. After concentration under reduced pressure to remove acetone, the product was extracted with chloroform and washed sufficiently with saturated sodium bicarbonate. After removing chloroform under reduced pressure, the residue was crystallized from ethanol to obtain 4.9 g (44%) of p-nitrophenyl β-D-glucosamine triacetate (f). mp196-198 ℃
(Disassembly).
さらに、上記の化合物（ｆ）4gを０℃でアンモニアを
飽和したメタノール70mlに溶解後密栓し室温で72時間反
応させた。反応液を減圧濃縮乾固後、エタノールから結
晶化させ本発明化合物ｐ−ニトロフェニル β−Ｄ−グ
ルコサミニド2.1g（93％）を得た。Further, 4 g of the above compound (f) was dissolved in 70 ml of methanol saturated with ammonia at 0 ° C., sealed, and allowed to react at room temperature for 72 hours. The reaction solution was concentrated under reduced pressure to dryness, and crystallized from ethanol to obtain 2.1 g (93%) of the compound of the present invention, p-nitrophenyl β-D-glucosaminide.
この化合物の物理化合物性質を以下に示す 分子式:C12H16O7N2 融 点:181−182℃（分解） 比旋光度：▲〔ａ〕25 D▼＝−105.0（３％、水） 溶解性：水、メタノール水溶液、エタノール水溶液など
に可溶、アセトン、クロロホルム、ヘキサンなどに不
溶。The physical compound properties of this compound are shown below. Molecular formula: C 12 H 16 O 7 N 2 Melting point: 181-282 ° C. (decomposition) Specific rotation: ▲ [a] 25 D ▼ = -105.0 (3%, water) Solubility: Soluble in water, aqueous methanol solution, aqueous ethanol solution, etc., insoluble in acetone, chloroform, hexane, etc.
（発明の効果） 本発明によれば、糖質の利用を考えるうえで有用な酵
素である、β−Ｄ−グルコサミニダーゼの活性を測定す
ることが可能となり、また、この新規なβ−Ｄ−グルコ
サミニダーゼの活性測定基質を効率よく経済的に製造す
ることができる。(Effects of the Invention) According to the present invention, it is possible to measure the activity of β-D-glucosaminidase, which is a useful enzyme in considering the utilization of saccharides, and it is also possible to measure the activity of this novel β-D-glucosaminidase. Can be efficiently and economically produced.
フロントページの続き (56)参考文献 特公 昭63−13440（ＪＰ，Ｂ２) 特公 昭54−3945（ＪＰ，Ｂ１) Ｍｏｌｅｃｕｌａｒ ａｎｄ Ｃｅｌ ｌｕｌａｒ Ｂｉｏｃｈｅｍｉｓｔｒ ｙ，Ｖｏｌ．86（Ｍａｒｃｈ 16, 1989）ｐ65−70 (58)調査した分野(Int.Cl.6，ＤＢ名) C07H 15/203 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)Continuation of the front page (56) References JP-B-63-13440 (JP, B2) JP-B-54-3945 (JP, B1) Molecular and Cellular Biochemistry, Vol. 86 (March 16, 1989) p65-70 (58) Fields investigated (Int. Cl. 6 , DB name) C07H 15/203 CA (STN) REGISTRY (STN)
Claims (2)
ド（ｐ−ニトロフェニル ２−アミノ−２−デオキシ−
β−Ｄ−グルコピラノシド）。1. The following formula: P-nitrophenyl β-D-glucosaminide (p-nitrophenyl 2-amino-2-deoxy-
β-D-glucopyranoside).
コサミン テトラアセテートをハロゲン化した後、この
誘導体とｐ−ニトロフェノールとを縮合させ、ｐ−ニト
ロフェニル Ｎ−トリフルオロアセチル−β−Ｄ−グル
コサミン トリアセテートを得、これを脱Ｎ−トリフル
オロアセチル化並びに脱Ｏ−アセチル化することを特徴
とするグルコサミン誘導体の製造方法。2. After halogenating N-trifluoroacetyl-β-D-glucosamine tetraacetate, this derivative is condensed with p-nitrophenol to give p-nitrophenyl N-trifluoroacetyl-β-D- A method for producing a glucosamine derivative, comprising obtaining glucosamine triacetate, and de-N-trifluoroacetylating and de-O-acetylating this.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1218301A JP2977209B2 (en) | 1989-08-24 | 1989-08-24 | Glucosamine derivative and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1218301A JP2977209B2 (en) | 1989-08-24 | 1989-08-24 | Glucosamine derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0381282A JPH0381282A (en) | 1991-04-05 |
| JP2977209B2 true JP2977209B2 (en) | 1999-11-15 |
Family
ID=16717695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1218301A Expired - Fee Related JP2977209B2 (en) | 1989-08-24 | 1989-08-24 | Glucosamine derivative and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2977209B2 (en) |
-
1989
- 1989-08-24 JP JP1218301A patent/JP2977209B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Ｍｏｌｅｃｕｌａｒ ａｎｄ Ｃｅｌｌｕｌａｒ Ｂｉｏｃｈｅｍｉｓｔｒｙ，Ｖｏｌ．８６（Ｍａｒｃｈ １６，１９８９）ｐ６５−７０ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0381282A (en) | 1991-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ferrier et al. | ] A potentially versatile synthesis of glycosides | |
| JPS6129359B2 (en) | ||
| JPS60208992A (en) | N-glycosylated carboxylic acid derivative | |
| Zurabyan et al. | Oxazoline synthesis of 1, 2-trans-2-acetamido-2-deoxyglycosides. Glycosylation of secondary hydroxyl groups in partially protected saccharides | |
| Pozsgay | A new strategy in oligosaccharide synthesis using lipophilic protecting groups: synthesis of a tetracosasaccharide | |
| AU638146B2 (en) | Alkylated oligosaccharides and acetyl derivatives of the same | |
| Bock et al. | Derivatives of methyl β-lactoside as substrates for and inhibitors of β-D-galactosidase from E. coli | |
| JP2977209B2 (en) | Glucosamine derivative and method for producing the same | |
| JPH09132585A (en) | Production of new amino sugar, chitooligasccharide and its analogous oligosaccharide | |
| Lubineau et al. | Synthesis of aryl d-gluco-and d-galacto-pyranosides and 1-O-acyl-d-gluco-and-d-gluco-pyranoses exploiting the mitsunobu reaction. Influence of the pKa of the acid on the stereoselectivity of the reaction | |
| Kusumoto et al. | Synthesis of. BETA.(1-4)-linked disaccharides of N-acetylglucosamine and N-acetylmuramic acid by their direct condensation. | |
| Ross et al. | Parasite glycoconjugates. Part 11. 1 Preparation of phosphodisaccharide synthetic probes, substrate analogues for the elongating α-D-mannopyranosylphosphate transferase in the Leishmania | |
| Lee et al. | Synthesis of allyl 3-deoxy-and 4-deoxy-β-D-galactopyranoside and simultaneous preparation of Gal (1→ 2)-and Gal (1→ 3)-linked disaccharide glycosides | |
| WO1993016113A1 (en) | Glycosides of cyclodextrines and processes for preparation | |
| Matta et al. | Synthesis of p-nitrophenyl 6-O-(2-acetamido-2-deoxy-β-d-glucopyranosyl)-β-d-galactopyranoside and p-nitrophenyl O-β-d-galactopyranosyl-(1→ 3)-O-(2-acetamido-2-deoxy-β-d-glucopyranosyl)-(1→ 6)-β-d-galactopyranoside | |
| Hirsch et al. | Improved synthesis of an aldobiouronic acid related to hardwood xylans, and preparation of a derivative thereof suitable for linking to proteins | |
| Wong et al. | The synthesis of derivatives of lactosamine and cellobiosamine to serve as probes in studies of the combining site of the monoclonal anti-I Ma antibody | |
| Lipták et al. | Synthesis of the tetrasaccharide core region of antigenic lipo-oligosaccharides characteristic of Mycobacterium kansasii | |
| Baer et al. | Reactions of nitro sugars. X. Novel furanoside synthesis. Conversion of methyl 6-deoxy-6-nitro-. alpha.-D-glucopyranoside into methyl 3-deoxy-3-nitro-. beta.-L-ribo-and-arabinofuranosides and corresponding amino sugars | |
| JPH0631291B2 (en) | S-neuraminic acid derivative | |
| Sarfati et al. | Synthesis of some 5-O-substituted 3-deoxyoct-2-ulosonic acids, and their response to thiobarbiturate during acidic hydrolysis | |
| JPH04282396A (en) | Antimycotic compound | |
| JP3884494B2 (en) | Method for producing cellotriose and cellotetraose monomers and oligomers therefrom | |
| US5773596A (en) | Preparation of ganglioside having ceramide moiety labeled with fluorescence | |
| Kornhauser et al. | Glycosyl esters of amino acids: Part I. Synthesis of 1-O-(2-acetamidoacyl)-2, 3, 4, 6-tetra-O-acetyl-β-d-glucopyranoses |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20070910 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080910 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |