Platinum complexes, process for the preparation thereof, and pha

Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing

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546 5, 546 11, 548402, 549206, 556 40, C07F 1702, A61K 31555, A61K 3128

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050345524

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BRIEF SUMMARY
The invention relates to platinum complexes, process for the preparation thereof, and phamaceuticals containing these. An essential structural element of the platinum complexes of the invention is the simultaneous presence of ligands containing N and phosphonic acid groups.
Phosphonic acids are employed not only in industry but also for medical purposes, cf. The Role of Phosphonates in Living Systems, CDC Press, Inc., Boca Raton, Fla. (1982); M.D. Francis et al., J. Chem. Educ 55 (12), 760-766 (1978).
It is known that certain phosphonic acids accumulate in bone and tumour tissue after intravenous administration. Thus, for example, Paget's disease of bone is treated with the disodium salt of 1-hydroxyethane-1,1-diphosphonic acid, cf. The Merck Index, Merck & Co., Inc., Rahway, N.J., U.S.A. (1983) 3812. The compound known under the INN of cisplatin, cis-diamminedichloroplatinum(II), is employed in particular for the treatment of testicular tumours, ovarian tumours or small-cell bronchial carcinomas.
It has now been found that platinum complexes of the general formula I
a) R.sup.1 denotes hydrogen, C.sub.1 -C.sub.8 -alkyl, C.sub.1 -C.sub.8 -alkenyl, C.sub.4 -C.sub.8 -cycloalkyl or C.sub.4 -C.sub.8 -cycloalkyl-C.sub.1 -C.sub.4 -alkyl, each of which can be substituted one or more times by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, hydroxyl, amino, halogen, amino-C.sub.1 -C.sub.2 -alkyl, hydroxyamino, carboxyl, C.sub.1 -C.sub.4 -alkoxycarbonyl, C.sub.4 -C.sub.8 -cycloalkyl, phenyl or phenoxy, it being possible for the substituents C.sub.4 -C.sub.8 -cycloalkyl, C.sub.4 -C.sub.8 -cycloalkyl-C.sub.1 -C.sub.4 -alkyl, phenyl and phenoxy in their turn to be substituted one or more times by hydroxyl, halogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy,
Y denotes a group of the formula II
R.sup.2 is defined as R.sup.1 with the exception of hydrogen and of nitrogen-containing meanings, it being possible for a further group (HO).sub.2 P(O)-- to be bonded to R.sup.2,
X denotes a singly negatively charged anion,
n the numbers 1 or 2, but the number 1 only if R.sup.1 has a nitrogen functionality which is able to coordinate with the central metal Pt,
m denotes the numbers 1 or 2, but the number 1 only if R.sup.2 has a group (HO).sub.2 P(O)-- which is able to coordinate with the central metal Pt, and
p denotes the numbers 0 or 2, but the number 2 only if Pt is present in oxidation state IV,
and q denotes the number 1,
b) Y denotes a group of the above formula II in which
R.sup.2 denotes a C.sub.1 -C.sub.4 -alkylamino-phosphono-methyl, 3-amino-1-phosphono-1-hydroxy-1-propyl, amino-p-hydroxymethyl-phosphono-methyl, iminobis(methylenephosphono) or N,N-bis(methylenephosphono)-amino group,
R.sup.1, X, n and p are as defined above, and
q denotes the number 1, and
m denotes the number 1,
c) Y is bis-(dihydroxyphosphonylmethyl)-aminoacetic acid,
R.sup.1, X, n and p are as defined above, and
q denotes the number 1, and m denotes the number 1,
d) q the number 2, m the number 1 and Y has one of the above meanings, with the proviso that Y contains at least 2 phosphono groups, and
R.sup.1, X, n and p are as defined above, or
e) n is the number 0 and q is the number 1, and
Y has one of the above meanings, with the proviso that Y contains at least 2 phosphono groups, and
x and p are as defined above
have advantageous therapeutic affects which make them suitable for the treatment of cancers, especially of bone tumours, osteosarcomas and bone metastases, liver tumors and tumours of the reticuloendothelial system (RES).
Alkyl, alkenyl and alkoxy radicals according to the abovementioned definitions can be straight-chain or branched, with straight-chain radicals being preferred. Preferred halogen atoms are chlorine atoms.
Depending on the pH of the reaction mixture, the phosphonic acids are present in the reaction product as neutral ligands or as singly or doubly negatively charged ligands. In the former case the charge on the complex is balanced by the anion of an acid, for example chloride. In the case where negatively charged

REFERENCES:
patent: 4845124 (1989-07-01), Kidani et al.
patent: 4870070 (1989-09-01), Bitha et al.
patent: 4882447 (1989-11-01), Tsojihara et al.
patent: 4921984 (1990-05-01), Nowatari et al.

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