Bismuth dendrimers, processes for their preparation, and their u

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From aluminum- or heavy metal-containing reactant

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534 10, 556 64, 424 94, 424 111, 424 165, 424 91, 424 93, 424 9411, 424 95, C08G 7900, A61K 4904

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061568732

DESCRIPTION:

BRIEF SUMMARY
The invention relates to dendrimeric organometallic bismuth compounds (bismuth dendrimers), which can advantageously be used as x-ray contrast media, as well as processes for their production.


PRIOR ART

The contrast media that are currently commonly used in diagnostic radiology contain either barium or iodine as an opacifying element. All of the contrast media that can be administered parenterally and that are currently approved contain iodine, either with three or with six iodine atoms per molecule (D. P. Swanson, H. M. Chilton, J. H. Thrall, "Pharmaceuticals in Medical Imaging," 1990, McMillan). In these compounds, the iodine atoms are always covalently coupled to the "carrier molecule," and they make possible the visualization of those vessels, organs and tissues that are achieved by the iodine-containing contrast media. The presence of the contrast medium increases the x-ray opacity of these tissues relative to their surrounding area in such a way that they are visible in the x-ray image and allow diagnoses relative to their shape or pathological changes. With these contrast media, a number of different diagnostic processes can be used, such as, e.g., for the water-soluble, iodine-containing compounds: angiography, urography, myelography and cholecystography.
Barium is used exclusively for the visualization of the gastrointestinal tract in the form of non-water-soluble barium sulfate as a formulation that is to be administered orally.
In the past, however, a number of novel types of contrast media were also proposed or studied that in a large number of cases represent metal complexes (e.g., R. M. Nalbandian, W. T. Rice, W. O. Nickels, Annals of N.Y. Acad. Sc., 1959, 79, 779-792; WO 90/03804; U.S. Pat. No. 4,310,507, U.S. Pat. No. 4,478,816, U.S. Pat. No. 4,647,447, U.S. Pat. No. 4,176,173, U.S. Pat. No. 5,417,958). The goal in the search for contrast media without iodine lies in avoiding the known side effects of the iodine-containing compounds such as pseudoallergic reactions, chemotoxic effects as well as the side effects of iodide that is released to the thyroid. The drawback of metal complexes lies in the usually relatively low metal content or the overly low solubility of the metal complexes, which is generally too low for use as x-ray contrast media.
Bismuth-organic compounds, which can sometimes also be used as x-ray contrast media, have been described in, e.g., EP 0 716 091 A1, JP A 4-154622, Vestn. Leningrad Univ., Fisz., Khim. Vol. 4, pp. 113-116 (1976), J. Chem. Soc., Chem. Commun., Vol. 16, pp. 1143-4 (1992), J. Coord. Chem., Vol. 12, pp. 53-57 (1982). Bismuth dendrimers have not yet been described, however.
The object of this invention now consists in designing contrast media for use in diagnostic radiology that do not contain any iodine and thus cannot cause the side effects that are induced by this element. It has now been found, surprisingly enough, that novel bismuth-organic compounds that have not yet become known, so-called bismuth dendrimers, can be used as x-ray contrast media.
The structure of these new compounds corresponds to general formula I aryl, heteroaryl, alkyl or cycloalkyl group, which can contain heteroatoms and/or alkyl, hydroxy, polyhydroxyalkyl substituents and/or ester, amide, thioester, thioamide, acetal, ketal, thioacetal, thioketal, disulfide, anhydride and/or urea groups, whereby X has base multiplicity b, hydroxy-substituted in zero to ten places, and can contain zero to ten aryl or heteroaryl, ether, ester, thioether, thioester, amide, thioamide, sulfonate, sulfonamide, phosphonate or phosphoric acid amid groups, formula Ia unbranched C.sub.6 -C.sub.10 aryl or benzyl group that is hydroxy-substituted in zero to six places, an ether group --OR.sup.3, ester group --COOR.sup.3, thioether group --SR.sup.3, thioester group --COSR.sup.3, amide group --CONR.sup.3 R.sup.4 or thioamide group --CSNR.sup.3 R.sup.4, in which C.sub.1 -C.sub.6 alkyl group that is hydroxy-substituted in zero to six places, a C.sub.6 -C.sub.10 aryl or benzyl group that is hydroxy-substitut

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