Organic compounds -- part of the class 532-570 series – Organic compounds – Carbohydrates or derivatives
Patent
1992-10-21
1995-10-10
Beisner, William H.
Organic compounds -- part of the class 532-570 series
Organic compounds
Carbohydrates or derivatives
536 111, C07H 100, C07H 302
Patent
active
054571928
DESCRIPTION:
BRIEF SUMMARY
synthesizing a rare sugar, which rarely exists as a natural sugar and which is not easily accessible, in the form of a saccharide derivative with a structure applicable 8 oz to various uses.
An example of the above rare sugar is D-allose, and its 1,6-anhydride is D-allosan, represented by formula (IV) below: ##STR1##
D-allosan has the same configuration of the hydroxyl groups as that of D-allose. Since hydroxyl groups at the 1- and 6-positions are combined to form an anhydro bond, thereby constituting an acetal structure, hydroxyl groups at the 1-, 5-, and 6-positions have already been selectively protected. For this reason, the structure of D-allosan as a starting material for a saccharide-containing compound is a more effective structure than that of D-allose to shorten and facilitate the introduction of a protective group of the hydroxyl group in terms of positional selectivity.
Saccharide-containing compounds containing D-allose or D-allosan as a constituent element may be employed as anti-inflammatory agents, anti-tumor agents, anemic agents, and antibiotic substances.
Various methods of manufacturing D-allosan have been attempted. A method of synthesizing D-allosan from D-ribose via D-allose by a Killiani-Fischer synthesis method (J. Pratt and N. K. Richtmyer, J. Am. Chem. Soc., 77, 1906 (1955), and a method of obtaining D-allosan by thermally decomposing corn starch to obtain 1,6-anhydro-.beta.-D-glucopyranose (D-glucosan), oxidizing the hydroxyl group having a .beta.-configuration at the 3-position, and reducing it to obtain the hydroxyl group having an .alpha.-configuration (K. Heyns, J. Weyer, H. Paulsen, Chem. Ber., 100, 2317 (1967)) are known.
In the former method, however, since the step of obtaining D-allose as an intermediate product is not a stereoselective reaction, D-altronic acid having an altro-configuration as a C-2 epimer of D-allose is produced. For this reason, this D-altronic acid must be separated and crystallized for elimination. Moreover, the yield is low. In the step of obtaining D-allosan by forming an anhydride having a 1,6-anhydro bond from D-allose as the intermediate product in the presence of an acid catalyst, D-allosan and D-allose as the material are equilibrated at a ratio of about 14:86 in an acidic aqueous solution, so that the material is recovered in a larger amount. For this reason, the total yield is low. That is, the total yield is about 2.4% in five steps (the total yield is 12% even if the material recovery amount in the last step is taken into consideration).
In the latter method, the yields in the first step of obtaining D-glucosan and the next step of oxidizing the hydroxyl group having a .beta.-configuration at the 3-position of D-glucosan are as low as 25% and 14 to 19%, respectively. The last step of reducing the carbonyl group at the 3-position is not a stereoselective reaction, thereby also producing D-allosan in which the hydroxyl group is reduced in the .alpha.-configuration, and D-glucosan (i.e., the material) in which the hydroxyl group is reduced in the .beta.-configuration. The yield of this step is as low as 30%. For this reason, the total yield in the five steps is as very low as about 1.1%.
Disclosure of Invention
It is an object of the present invention to provide a method of selectively manufacturing D-allosan in high yield.
The present inventors have made extensive studies to achieve the above object and have found a route for obtaining D-allosan stereoselectively with a higher yield than that achieved by a conventional manufacturing method, in which levoglucosenone (Carbohydrate Research, 58(1977), 78-87) known as a thermally decomposed product of a cellulose, is used as a starting material and a hydroxyl group is introduced by reduction of a carbonyl group or an oxidative addition reaction in a double bond.
That is, the method of manufacturing D-allosan according to the present invention is characterized by comprising the steps of:
(a) reducing the carbonyl group at the 2-position of levoglucosenone represented by formula (I) below to
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Ebata Takashi
Matsumoto Katsuya
Matsushita Hajime
Beisner William H.
Japan Tobacco Inc.
White Everett
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