Organic compounds -- part of the class 532-570 series – Organic compounds – Carbohydrates or derivatives
Patent
1992-05-12
1995-04-25
Redding, David A.
Organic compounds -- part of the class 532-570 series
Organic compounds
Carbohydrates or derivatives
536 111, C07H 100, C07H 302
Patent
active
054100380
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
The present invention relates to a method of preparing D-altrose, which is a rare sugar, more particularly, to a method of preparing D-altrose from levoglucosenone.
PRIOR ART
D-altrose is a pyranose type aldohexose represented by structural formula (4) given below. The D-altropyranose (4) is in equilibrium with D-altrofuranose (6) via a ring-opened aldohexose (5) as an intermediate. It should also be noted that each of pyranose (4) and furanose (6) has .alpha.- and .beta.-anomers. In other words, D-altrose is present as an equilibrium mixture of these plurality of anomers. ##STR2##
D-altrose is a rare sugar, which is present in nature in an extremely small amount. Altrose presently available on the market is a synthetic substance produced by, for example, Aldrich Inc. Naturally, altrose available on the market is markedly costly, compared with sugars present in nature in large amounts such as glucose. For example, the prices of altrose available on the market at present as a reagent are given below:
$62.40 (100 mg) for altrose produced by Aldrich Inc.
21,400 (100 mg) for altrose produced by Junsei Kagaku Inc.
Recently, sugar chains such as oligosaccharides and polysaccharides, which perform functions useful as a physiologically active substance, have attracted attention in the field of fine chemicals such as medicines and agricultural chemicals. Presently, the objects of researches on the sugar chain are restricted to those consisting of monosaccharides present in nature in large amounts and readily available to researchers, such as D-glucose, D-mannose and D-galactose. However, it is expected that various monosaccharides other than those present in nature will be required in the future in research on the synthesis of sugar chains performing more useful functions. Under the circumstances, it is highly significant and necessary to develop a method which permits preparing D-altrose, which is a rare sugar difficult to obtain, in high yield while diminishing the number of treating steps.
Various methods were proposed in the past in an attempt to synthesize D-altrose. For example, a method of synthesizing D-altrose based on the Kiliani-Fischer method, in which D-ribose is converted into D-altronic acid and, then, into D-altrose, is described in "P. A. Leven and W. A. Jacobs, Ber., 43, 3141 (1910)". In this method, however, involved is a reaction in which the 1-position of D-ribose is converted to cyanohydrin. Since this reaction is not stereoselective, D-allonic acid, which is a C-2 epimer of D-altronic acid, is also generated as a by-product, in addition to D-altronic acid which is an intermediate product generated in the synthesis of D-altrose. Thus, it is necessary to employ fractional crystallization in order to isolate D-altronic acid, with the result that the product yield is as low as only 3%.
Another method is described in, for example, "N. K. Richtmyer, C. S. Hudson, J, Am. Chem. Soc., 57, 1716 (1935)". In this method, the 2- and 3-positions of the D-glucose portion included in lactose are subjected to walden inversion so as to obtain neolactose consisting of D-altrose and D-galactose, followed by hydrolyzing neolactose so as to obtain the desired D-altrose product. The D-galactose contained in the mixture obtained after the hydrolysis is consumed by allowing yeast to act thereon and, thus, is removed. The remaining D-altrose is refined as a benzyl mercaptal derivative and, then, returned to D-altrose. It should be noted that this method necessitates a step of protecting the hydroxyl group which is irrelevant to the reaction and another step of releasing the protective group after the reaction. It follows that as many as eight steps are involved in this method starting with the Walden inversion of lactose. Naturally, troublesome operations are required for synthesizing the product D-altrose. In addition, the product yield is as low as only 8%.
Still another method of synthesizing D-altrose is described in, for example, "Methods in Carbohydrate Chemistry" Vol. I, Academic Press, New
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"Bulletin of the Chemical Society of Japan" vol. 64 No. 7-1991.
Ebata Takashi
Matsumoto Katsuya
Matsushita Hajime
Japan Tobacco Inc.
Redding David A.
White Everett
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