JPH0471079B2 - - Google Patents
Info
- Publication number
- JPH0471079B2 JPH0471079B2 JP57175327A JP17532782A JPH0471079B2 JP H0471079 B2 JPH0471079 B2 JP H0471079B2 JP 57175327 A JP57175327 A JP 57175327A JP 17532782 A JP17532782 A JP 17532782A JP H0471079 B2 JPH0471079 B2 JP H0471079B2
- Authority
- JP
- Japan
- Prior art keywords
- ruthenium
- compound
- hypochlorite
- general formula
- glucofuranose
- 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 - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Saccharide Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明はグルコフラノース誘導体酸化物の製造
方法に関する。
一般式〔〕で示される化合物は一般式〔〕
で示される化合物を酸化することによつて得られ
る物質で、(a)で示すケトン体と(b)で示す水和物の
両者の形を取り得る。(b)を加熱脱水すると(a)とな
る。
The present invention relates to a method for producing glucofuranose derivative oxides. The compound represented by the general formula [] is the general formula []
It is a substance obtained by oxidizing the compound shown in (a) and can take the form of both a ketone body shown in (a) and a hydrate shown in (b). When (b) is heated and dehydrated, it becomes (a).
【式】又は
一般式〔〕の化合物は下記に示すようにＸ線
造影剤として用いられる３−デオキシ−３−ヨー
ド−Ｄ−グルコース〔〕の合成中間体として、
又３−デオキシ−３−アミノ−Ｄ−グルコース
〔′〕の合成中間体として有用な物質である。
一般式〔〕の化合物は公知の方法によりＤ−
グルコースをチタール化することにより容易に得
られる物質であるが、この〔〕の物質の酸化方
法として次の方法が知られている。
(1) 無水クロム酸−ピリジン錯体を用いる方法
〔Carbohydr.Res.、26 441−７（1973）〕
(2) DMSO−無水酢酸を用いる方法〔Can.J.
Chem.、44 836（1966）〕
(3) DMSO−五酸化リンを用いる方法〔J.Am.
Chem.Soc.、87 4651（1965）〕
(4) 四酸化ルテニウムによる方法〔Proc.Chem.
Soc.、342（1964）〕
(5) 二酸化ルテニウム−過ヨー素酸による方法
〔Can.J.Chem.、43 3452（1965）〕
(1)の方法はクロムの処理が必要なこと、(2)、(3)
の方法は収率が低く、悪臭を発すること、(4)、(5)
の方法は収率は高いが試薬が極めて高いこと等の
ため工業的生産に適していない。
本発明者等は工業的生産に適した酸化方法を種
種検討したところ、二酸化ルテニウム−次亜塩素
酸塩による方法が工業的生産に適していることを
見い出した。本発明の反応機構を示すと次の通り
である。
即ち次亜塩素酸塩が二酸化ルテニウムを酸化し
て四酸化ルテニウムとし、四酸化ルテニウムが一
般式〔〕の化合物を酸化すると同時に二酸化ル
テニウムとなる。この反応系により高価な二酸化
ルテニウムの使用を節減することができる。
本発明に使用する一般式〔〕の化合物のR1、
R2はメチル、エチル又はプロピル等の低級アル
キル基であるが、特にメチル又はエチル基が取扱
上好ましい。酸化剤として次亜塩素酸ナトリウ
ム、次亜塩素酸カルシウム等の次亜塩素酸塩と二
酸化ルテニウムを用いるが塩化ルテニウムや硝酸
ルテニウム等のルテニウム塩も次亜塩酸塩により
酸化され二酸化ルテニウムとなるので使用するこ
とができる。
次に酸化方法について述べると、一般式〔〕
の化合物とルテニウム化合物を水に混合させ、撹
拌下で次亜塩素酸塩水溶液を滴下しつつ酸又はア
ルカリでPHを２〜８を好ましくは３〜５に調節す
る。反応終了後残存する四酸化ルテニウムをイソ
プロピルアルコールにて二酸化ルテニウムに分解
した後、クロロホルム等の溶媒から抽出する。そ
の抽出物から溶媒を除去、結晶化せしめることに
より一般式〔〕の化合物を70〜80％の収率で得
ることができる。
反応時の一般式〔〕の化合物の濃度は水に対
する溶解度の関係で15％以下が好ましい。ルテニ
ウム化合物の量は多いほど反応時間を短縮できる
が、実用的には一般式〔〕の化合物に対して
0.2〜１％（ｗ／ｗ）である。又二酸化ルテニウ
ムは回収して再使用することができる。次亜塩素
酸の使用量は一般式〔〕の化合物１モルに対し
て１〜３モル好ましくは1.5〜２モルである。反
応時の温度は10〜50℃が好ましい。
本発明の酸化方法の特徴は悪臭、廃棄物等公害
をほとんど生じないため工業的生産に適すること
及び次亜塩素酸ナトリウムや次亜塩素酸カルシウ
ムが工業的に多量にかつ安価に製造されているこ
とより、目的の〔〕の化合物を安価に製造でき
る点にある。
実施例 １
１容の丸底フラスコに20ｇの１，２：５，６
−ジ−ｏ−イソプロピリデン−α−Ｄ−グルコフ
ラノース（化合物〔〕）、0.15ｇの二酸化ルテニ
ウム及び400mlの水を入れ25℃に保温した。
この混合液を撹拌しつつ、これに170mlの次亜
塩素酸水溶液（有効塩素として12％水溶液）を
180分で滴下した。滴下中は10％水酸化ナトリウ
ムでPHを3.5に調整した。更に60分間撹拌後、イ
ソプロピルアルコール10mlを加えて残存する四酸
化ルテニウムを分解した。反応液をクロロホルム
80mlで３回抽出した。クロロホルム層に無水硫酸
マグネシウム10ｇを加え乾燥した後、液を濃縮
して１，２：５，６−ジ−ｏ−イソプロピリデン
−α−Ｄ−リボヘキソフラノース−３−ウロース
（化合物〔〕）の含水結晶16.2ｇを得た。対理論
収率76.3％、融点112℃、純度97.8％（ガスクロ
マト分析による）。このものは薄層クロマトグラ
フイ（展開液ベンゼン：メタノール＝８：１）で
標準物質と同一物質であることが確認された。又
NMR分析の結果、１，２：５，６−ジ−ｏ−イ
ソプロピリデン−α−Ｄ−グルコフラノースのδ
＝2.50（Ｃ−3H）の消滅が見られた。
実施例 ２
１容の丸底フラスコに20ｇの１，２：５，６
−ジ−ｏ−イソプロピリデン−α−Ｄ−グルコフ
ラノース（化合物〔〕）、0.16ｇの三塩化ルテニ
ウム及び400mlの水を入れ25℃に保温した。この
混合液を撹拌しつつ、これを120mlの次亜塩素酸
ナトリウム水溶液（有効塩素として12％水溶液）
を150分で滴下した。以下実施例１と同じ方法で
行つたところ、１，２：５，６−ジ−ｏ−イソプ
ロピリデン−α−Ｄ−リボヘキソフラノース−３
−ウロース（化合物〔〕）の含水結晶15.2ｇを
得た。対理論収率71.6％、融点112℃、純度98.0
％（ガスクロマト分析による）。
実施例 ３
１容の丸底フラスコに20ｇの１，２：５，６
−ジ−ｏ−イソプロピリデン−α−Ｄ−グルコフ
ラノース（化合物〔〕）、0.15ｇの二酸化ルテニ
ウム及び400mlの水を入れ25℃に保温した。この
混合液を撹拌しつつ、これを200mlの次亜塩素酸
カルシウム（有効塩素として10％水溶液）を180
分にて滴下した。滴下中は10％水酸化ナトリウム
水溶液でPH４に調整した。以下実施例１と同じ方
法で行つたところ、１，２：５，６−ジ−ｏ−イ
ソプロピリデン−α−Ｄ−リボヘキソフラノース
−３−ウロース（化合物〔〕）の含水結晶15.0
ｇを得た。対理論収率70.6％融点112℃、純度
97.6％（ガスクロマト分析による）。[Formula] or The compound of the general formula [] is used as a synthetic intermediate for 3-deoxy-3-iodo-D-glucose [] used as an X-ray contrast agent as shown below.
It is also a useful substance as a synthetic intermediate for 3-deoxy-3-amino-D-glucose [']. Compounds of general formula [] can be prepared using D-
This substance is easily obtained by titalizing glucose, and the following method is known as a method for oxidizing this substance. (1) Method using chromic anhydride-pyridine complex [Carbohydr.Res., 26 441-7 (1973)] (2) Method using DMSO-acetic anhydride [Can.J.
Chem., 44 836 (1966)] (3) Method using DMSO-phosphorus pentoxide [J.Am.
Chem.Soc., 87 4651 (1965)] (4) Ruthenium tetroxide method [Proc.Chem.
Soc., 342 (1964)] (5) Ruthenium dioxide-periodic acid method [Can.J.Chem., 43 3452 (1965)] Method (1) requires treatment of chromium; (2) ), (3)
(4), (5) This method has low yield and produces a bad odor.
Although the method has a high yield, it is not suitable for industrial production because the reagents are extremely expensive. The present inventors investigated various oxidation methods suitable for industrial production and found that a method using ruthenium dioxide-hypochlorite is suitable for industrial production. The reaction mechanism of the present invention is as follows. That is, hypochlorite oxidizes ruthenium dioxide to produce ruthenium tetroxide, and ruthenium tetroxide simultaneously oxidizes the compound of general formula [] to produce ruthenium dioxide. This reaction system makes it possible to save on the use of expensive ruthenium dioxide. R 1 of the compound of general formula [] used in the present invention,
R 2 is a lower alkyl group such as methyl, ethyl or propyl, with methyl or ethyl groups being particularly preferred in terms of handling. Hypochlorites such as sodium hypochlorite and calcium hypochlorite and ruthenium dioxide are used as oxidizing agents, but ruthenium salts such as ruthenium chloride and ruthenium nitrate are also used because they are oxidized by hypochlorite and become ruthenium dioxide. can do. Next, regarding the oxidation method, the general formula []
The compound and the ruthenium compound are mixed in water, and the pH is adjusted to 2 to 8, preferably 3 to 5, with an acid or alkali while an aqueous hypochlorite solution is added dropwise under stirring. After completion of the reaction, remaining ruthenium tetroxide is decomposed into ruthenium dioxide using isopropyl alcohol, and then extracted from a solvent such as chloroform. By removing the solvent from the extract and crystallizing it, a compound of general formula [] can be obtained with a yield of 70 to 80%. The concentration of the compound of general formula [] during the reaction is preferably 15% or less in relation to its solubility in water. The larger the amount of ruthenium compound, the shorter the reaction time, but in practical terms, for compounds of general formula []
It is 0.2-1% (w/w). Additionally, ruthenium dioxide can be recovered and reused. The amount of hypochlorous acid used is 1 to 3 mol, preferably 1.5 to 2 mol, per 1 mol of the compound of general formula []. The temperature during the reaction is preferably 10 to 50°C. The oxidation method of the present invention is characterized by being suitable for industrial production as it hardly produces any pollution such as bad odor or waste, and sodium hypochlorite and calcium hypochlorite can be produced industrially in large quantities and at low cost. Above all, the desired compound [] can be produced at low cost. Example 1 20g of 1,2:5,6 in a 1 volume round bottom flask
-di-o-isopropylidene-α-D-glucofuranose (compound []), 0.15 g of ruthenium dioxide and 400 ml of water were added and kept at 25°C. While stirring this mixture, add 170ml of hypochlorous acid aqueous solution (12% aqueous solution as available chlorine).
It was dripped in 180 minutes. During the dropwise addition, the pH was adjusted to 3.5 with 10% sodium hydroxide. After further stirring for 60 minutes, 10 ml of isopropyl alcohol was added to decompose the remaining ruthenium tetroxide. Dilute the reaction solution with chloroform
Extracted three times with 80 ml. After adding 10 g of anhydrous magnesium sulfate to the chloroform layer and drying it, the liquid was concentrated to obtain 1,2:5,6-di-o-isopropylidene-α-D-ribohexofuranose-3-ulose (compound []). 16.2 g of water-containing crystals were obtained. Theoretical yield 76.3%, melting point 112°C, purity 97.8% (by gas chromatography analysis). This substance was confirmed to be the same as the standard substance by thin layer chromatography (developing solution benzene:methanol=8:1). or
As a result of NMR analysis, δ of 1,2:5,6-di-o-isopropylidene-α-D-glucofuranose
= 2.50 (C-3H) was observed to disappear. Example 2 20g of 1,2:5,6 in a 1 volume round bottom flask
-di-o-isopropylidene-α-D-glucofuranose (compound []), 0.16 g of ruthenium trichloride, and 400 ml of water were added and kept at 25°C. While stirring this mixture, add 120ml of sodium hypochlorite aqueous solution (12% aqueous solution as available chlorine).
was added dropwise over 150 minutes. The following procedure was carried out in the same manner as in Example 1, and 1,2:5,6-di-o-isopropylidene-α-D-ribohexofuranose-3
-15.2 g of hydrated crystals of ulose (compound []) were obtained. Theoretical yield 71.6%, melting point 112℃, purity 98.0
% (by gas chromatography analysis). Example 3 20g of 1,2:5,6 in a 1 volume round bottom flask
-di-o-isopropylidene-α-D-glucofuranose (compound []), 0.15 g of ruthenium dioxide and 400 ml of water were added and kept at 25°C. While stirring this mixture, add 200ml of calcium hypochlorite (10% aqueous solution as available chlorine) to 180%
It was dripped in minutes. During the dropping, the pH was adjusted to 4 with a 10% aqueous sodium hydroxide solution. The following procedure was carried out in the same manner as in Example 1, and 15.0% of hydrated crystals of 1,2:5,6-di-o-isopropylidene-α-D-ribohexofuranose-3-ulose (compound []) were obtained.
I got g. Theoretical yield 70.6% Melting point 112℃, Purity
97.6% (by gas chromatography analysis).
Claims (1)
基）で示されるグルコフラノース誘導体をルテニ
ウム化合物と次亜塩素酸塩で酸化することによる
一般式〔〕で示されるグルコフラノース誘導体
酸化物の製造方法。 【式】又は ２ ルテニウム化合物が二酸化ルテニウム又は三
塩化ルテニウム、硝酸ルテニウム等のルテニウム
塩である特許請求の範囲第１項記載の方法。 ３ 次亜塩素酸塩が次亜塩素酸ナトリウム又は次
亜塩素酸カルシウムである特許請求の範囲第１項
記載の方法。[Claims] 1. General formula [] (However, R 1 and R 2 are lower alkyl groups having 1 to 4 carbon atoms.) A glucofuranose derivative oxide represented by the general formula [ ] is obtained by oxidizing the glucofuranose derivative represented by the following with a ruthenium compound and hypochlorite. manufacturing method. [Formula] or 2. The method according to claim 1, wherein the ruthenium compound is a ruthenium salt such as ruthenium dioxide, ruthenium trichloride, or ruthenium nitrate. 3. The method according to claim 1, wherein the hypochlorite is sodium hypochlorite or calcium hypochlorite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57175327A JPS5967296A (en) | 1982-10-07 | 1982-10-07 | Preparation of glucofuranose derivative oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57175327A JPS5967296A (en) | 1982-10-07 | 1982-10-07 | Preparation of glucofuranose derivative oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5967296A JPS5967296A (en) | 1984-04-16 |
| JPH0471079B2 true JPH0471079B2 (en) | 1992-11-12 |
Family
ID=15994132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57175327A Granted JPS5967296A (en) | 1982-10-07 | 1982-10-07 | Preparation of glucofuranose derivative oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5967296A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4650714B2 (en) * | 2003-09-01 | 2011-03-16 | ナガセケムテックス株式会社 | Method for producing carbonyl compound |
| WO2026042861A1 (en) * | 2024-08-21 | 2026-02-26 | セトラスホールディングス株式会社 | Method for producing ketone body of diacetone glucose and diacetone allose |
-
1982
- 1982-10-07 JP JP57175327A patent/JPS5967296A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5967296A (en) | 1984-04-16 |
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