Method for the site specific synthesis of novel...

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Carbohydrate doai

Reexamination Certificate

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C514S023000, C514S345000, C536S017300, C536S022100, C546S314000, C568S852000

Reexamination Certificate

active

06177409

ABSTRACT:

This application is a Section 371 application of PCT/FR/97/01211, filed Jul. 4, 1997.
The present invention refers to a process for regiospecific preparation of new 3-hydroxypyridine-4(1H)-one derivatives starting from monosaccharides or itols.
It also regards the products obtained by this process, as well as their applications, namely as complexing agents of Fe
III
.
It is known that the compounds of the 3-hydroxypyridine-4(1H)-one type complex iron in the oxidation state III. These compounds are used, namely, in treatments on humans aimed at limiting forms of Fe
III
toxic overload (Kontoghiorghes G. J. et al.,
Lancet
, 1294-1295 (1987)). Such forms of toxic overload may be of endogenous origin, such as those found in patients affected by siderosis, or exogenous, as in the case of intoxications induced by the massive and frequent polytransfusions to which patients suffering, in particular, from &bgr;-thalassaemia are subjected.
It is likewise well known that the toxicity of these compounds for man is less when the -2 site of the pyridine cycle is substituted by an alkyl group, and this without modifying its chelating power in regard to Fe
III
(Hershko C. et al.,
Ann. N.Y. Acad. Sci
., 612, 351-360 (1990)).
Marquez et al. prepared glycoside derivatives of 2-methyl-3-hydroxypyridine-4(1H)-one by condensation of the benzylated maltol on D-ribose and D-arabinose. activated anomerically in the form of acetate, and of which the other hydroxylated groups are protected in the form of a benzoate or acetate (Marquez et al.,
J. Med. Chem
., 27 (2), 160-164 (1984)).
Using the same strategy, Miller et al. prepared two ribosides of 2-methyl- and 2-ethyl-3-hydroxypyridine-4(1H)-one of configuration &bgr;, by reacting 1-trimethylsilyl-2-alkyl-3-benzylpyridine-4(1H)-one on the 1,2,3,4-tetra-O-acetyl-&bgr;-D-ribopyranose and the 1-O-acetyl-2,3,5-tri-O-benzoyl-&bgr;-D-ribofuranose in the presence of SnCl
4
(Liu G. et al.,
Nucleosides, Nucleotide
, 14 (9-10), 1901-1904 (1995)).
One of the aims of the present invention is to describe a process for regiospecific synthesis of new 3-hydroxypyridine-4(1H)-one derivatives starting from amino monosaccharides or amino itols of general formula:
in which R represents an alkyl or alkylene or halo-alkyl or halo-alkylene radical, the halogens being preferably chosen from among chloride and fluoride, linear or branched, having from 1 to 4 carbon atoms and having hetero-atoms or not, and Sub represents a saccharide derivative, either cyclic or not, protected or not, chosen, for example, from among hexose, pentose, and preferably from among glucose, galactose, mannose, fructose, and xylose, or else an itol, either cyclic or not, protected or not, chosen, for example, from among hexitol, pentitol, tetritol or glycerol, and preferably from among glucitol, galacitol, mannitol, xylitol, erythritol, and glycerol, the hydrocarbon skeleton of which is bound to the nitrogen atom of the pyridinone either directly or by the intermediary of a spacing group of an alkylene or halo-alkylene type, the halogen being preferably chosen from among chloride and fluoride, linear or branched, having from 1 to 4 carbon atoms, and hetero-atoms or not.


REFERENCES:
Al-Refaie et al., “Efficacy and Possible Adverse Effects of the Oral Iron Chelator 1,2-Dimethyl-3-Hydroxypyrid-4-One (L1) in Thalassemia Major”, Blood, vol. 80, No. 3, pp. 593-599, Aug. 1992.
Fassos et al., “Urinary iron excretion depends on the mode of administration of the oral iron chelator 1,2-dimethyl-3-hydroxypyrid-4-one in patients with homozygous beta-thalassemia”, Clinical Pharmacology & Therapeutics, vol. 55, No. 1, pp. 70-75, 1994.
El-Khadem, Hassan. “Carbohydrate Chemistry”, published by Academic Press, Inc., pp. 19 and 24, 1988.
Collins, Peter M. and Robert J. Ferrier. “Monosaccharide”, published by John Wlley & Sons, p. 18, 1995.
Kontoghiorges G. J. et al., Lancet, 1294-1295, Jun. 6, 1987.
Hershko C. et al., Ann. N.Y. Acad. Sci., 612, 315-360 (1990).
Marquez et al., J. Med. Chem., 27 (2), 160-164 (1984).
Liu G. et al., Nucleosides, Nucleotide, 14(9-10), 1901-1904 (1995).

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