Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acids and salts thereof
Reexamination Certificate
2000-03-08
2002-01-01
Owens, Amelia (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acids and salts thereof
C549S314000, C536S004100
Reexamination Certificate
active
06335464
ABSTRACT:
TECHNICAL FIELD
This invention relates to a resin on which an amine oxide to be used as a catalyst in a selective oxidation reaction of an organic compound having primary hydroxyl group is adsorbed, a method for selectively oxidizing the primary hydroxyl group of an organic compound by using this resin, and a method for recovering the amine oxide used in the oxidation reaction. The present invention further relates to a method for producing uronic acid derivatives such as glucuronic acid derivatives and a method for producing glucuronic acid or glucuronolactone.
BACKGROUND ART
Glucuronic acid, glucuronolactone and derivatives thereof have been broadly used as drugs. To industrially synthesize glucuronic acid derivatives serving as intermediates in the synthesis of glucuronic acid and glucuronolactone, it has been a practice to selectively oxidize the primary hydroxyl group of a starting material (glucose derivative, saccharide such as starch, etc.) by using a nitrogen oxide (nitric acid, etc.) as an oxidizing agent to thereby convert the starting material into a carboxylic acid (Japanese Patent Publication for Opposition (Kokoku) 46-38781).
However, the above-described method suffers from some disadvantages. That is to say, expensive nitrogen oxide should be used therein as an oxidizing agent. In addition, it is feared that nitrogen oxide gases generated as by-products in the oxidation reaction might cause public pollution. Therefore, these gases are oxidized with air to give the original nitrogen oxide and then recovered and reused. Thus, troublesome operations and a device for the recovery of the nitrogen oxide are needed therefor.
In recent years, there have been disclosed a method for producing uronic acid derivatives by selectively oxidizing the primary hydroxyl group of a monosaccharide derivative (methyl glucoside, etc.) with 2,2,6,6-tetramethylpiperidine N-oxyl (hereinafter referred to simply as TEMPO) as an oxidizing catalyst (Tetrahedron Letters, 34(7), 1181-1184 (1993)) and a method for highly selectively oxidizing a primary alcohol by electrolytically oxidizing the primary alcohol together with an N-oxyl compound (TEMPO, etc.) (see, for example, Japanese Laid-open Patent Publication (Kokai) 2-107790). Namely, it has been indicated that amine oxides such as hindered nitroxide typified by TEMPO are useful as catalysts in selectively oxidizing primary hydroxyl group of compounds.
Also, there has been publicly known a method for producing a sugar carboxylic acid or a sugar lactone at a high yield under mild conditions by electrolyzing an liquid electrolysis mixture containing a saccharide with a ruthenium compound and a halogen salt dissolved in an electrolyte in an electrolysis cell and then collecting the sugar carboxylic acid or sugar lactone thus oxidized by the oxidation of the primary or secondary hydroxyl group of the saccharide (Japanese Patent Publication for Opposition (Kokoku) 63-46153).
However, these catalysts are generally expensive. In the industrial application, therefore, these catalysts are recovered and reused so as to cut down the production cost and reduce the waste. Since such a catalyst usually occurs as a solution in the reaction system, troublesome and inefficient procedures (azeotropic distillation with water, extraction with an organic solvent, etc.) should be performed to recover the catalyst and, moreover, a recovery device is needed therefor, thus bringing about problems in handling and cost.
Moreover, many amine oxides exert undesirable effects on the human body and, therefore, must be handled cautiously.
Accordingly, no satisfactory method has been developed so far for conveniently and efficiently oxidizing the primary hydroxyl group of an organic compound with the use of an amine oxide as a catalyst.
DISCLOSURE OF THE INVENTION
Under these circumstances, an object of the present invention is to provide an industrial method for selectively oxidizing the primary hydroxyl group of an organic compound wherein an amine oxide can be safely, conveniently and efficiently employed as a catalyst. Another object of the present invention is to provide a method for conveniently producing glucuronic acid or glucuronolactone, which are useful as drugs, involving the step of synthesizing an uronic acid derivative useful as an intermediate in the synthesis of glucuronic acid or glucuronolactone, while considering the environmental safeguards.
As the results of intensive studies, the present inventors have found that, in a method for producing glucuronic acid or glucuronolactone, a glucuronic acid or glucuronolactone intermediate can be produced by using an amine oxide as a catalyst in a reaction of oxidizing a saccharide without resort to any nitrogen oxide as an oxidizing agent.
The present inventors have further found that in a method for oxidizing the primary hydroxyl group of an organic compound such as a saccharide, the oxidization can be conveniently and efficiently, compared with the conventional methods, carried out by using as a catalyst a resin carrier (polyacrylic resin, polystyrene resin, polyalkylene resin, etc.) having an amine oxide adsorbed thereon and using as an oxidizing agent a halogen-containing oxidant or an electrolytically oxidized product of a halogen-containing compound. The present invention has been completed based on these findings.
Accordingly, the present invention relates to a resin on which an amine oxide is adsorbed as a catalyst to be used in the selective oxidation reaction of an organic compound having primary hydroxyl group.
The present invention further relates to a method for selectively oxidizing the primary hydroxyl group of an organic compound which comprises reacting the organic compound and a resin having an amine oxide adsorbed thereon with a halogen-containing oxidant or an electrolytically oxidized product of a halogen-containing compound. More particularly, it relates to the above-described oxidation method wherein an oxidation reaction cell for the organic compound containing the resin having the amine oxide adsorbed thereon is located separately from an electrolytic reaction cell for the halogen-containing compound. Still particularly, it relates to a method for producing an uronic acid derivative by using the above-described oxidation method.
The present invention further relates to a method for producing a glucuronic acid derivative which comprises reacting an optionally substituted saccharide and an amine oxide with an electrolytically oxidized product of a halogen-containing compound. More particularly, it relates to the above-described oxidation method wherein the resin is a polyacrylic resin, a polystyrene resin or a polyalkylene resin. Still particularly, it relates to the above oxidation method wherein the organic compound is an optionally substituted saccharide. It also relates to a method for producing a glucuronic acid derivative wherein an optionally substituted saccharide is electrolytically oxidized together with an amine oxide. The present invention furthermore relates to a method for producing a glucuronic acid derivative which comprises oxidizing by the use of a hologen-containing oxidant or electrolytically oxidizing an optionally substituted saccharide together with a resin having an amine oxide adsorbed thereon.
The term “organic compound” as used in the present invention involves organic compounds having primary hydroxyl group. Examples thereof include lower and higher alcohols having primary hydroxyl group (the term “lower” as used herein means having 1 to 10 carbon atoms, while the term “higher” as used herein means having 11 or more carbon atoms), alkoxyalkanoic aicds having primary hydroxyl group, polyoxyalkylene siloxanes having primary hydroxyl group, polyoxyalkyleneamines having primary hydroxyl group, alkylpolyoxyalkylenes having primary hydroxyl group, polyoxyalkylene block polymers having primary hydroxyl group, alkylamidopolyoxyalkylenes having primary hydroxyl group, alkyl polyglucosides having primary hydroxyl group and optionally substituted saccharides having primary
Fujisaki Isao
Ochi Kiyoshige
Ori Kazutomo
Sugiyama Hiroshi
Takahashi Hidenori
Browdy And Neimark, P.L.L.C.
Chugai Seiyaku Kabushiki Kaisha
Owens Amelia
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