Organic compounds -- part of the class 532-570 series – Organic compounds – Radioactive metal containing
Patent
1992-01-21
1993-10-12
Shah, Mukund J.
Organic compounds -- part of the class 532-570 series
Organic compounds
Radioactive metal containing
534 15, 534 16, 540465, 540472, 540145, 536 171, 536 174, 536 172, 548557, 564347, C07D48722, C07F 1900, C07H 2300
Patent
active
052527204
DESCRIPTION:
BRIEF SUMMARY
BACKGROUND OF THE INVENTION
The porphyrins and related tetrapyrrole macrocycles are among the most versatile of tetradentate ligands.sup.1. Attempts to stabilize higher coordination geometries with larger porphyrin-like aromatic macrocycles have met with little success..sup.2-13 Only the uranyl complex of "superphthalocyanine" has been isolated and characterized structurally,.sup.2 although several other large porphyrin-like aromatic macrocycles, including the "sapphyrins",.sup.3,6 "oxosapphyrins",.sup.6,7 "platyrins",.sup.8 "pentaphyrin",.sup.9 and "(26]porphyrin",.sup.10 have been prepared in their metal free forms. Large, or "expanded" porphyrin-like systems are of interest for several reasons: They could serve as aromatic analogues of the better studied porphyrins.sup.2-10 or serve as biomimetic models for these or other naturally occurring pyrrole-containing systems..sup.36,13a In addition, large pyrrole containing systems offer possibilities as novel metal binding macrocycles..sup.2,4,5,13b,35,14 For instance, suitably designed systems could act as versatile ligands capable of binding larger metal cations and/or stabilizing higher coordination geometries.sup.2 than those routinely accommodated within the normally tetradentate ca. 2.0 .ANG. radius porphyrin core..sup.21 The resulting complexes could have important application in the area of heavy metal chelation therapy, serve as contrast agents for magnetic resonance imaging (MRI) applications, act as vehicles for radioimmunological labeling work, or serve as new systems for extending the range and scope of coordination chemistry..sup.14,39 In addition, the free-base (metal-free) and/or diamagnetic metal-containing materials could serve as useful photosensitizers for photodynamic therapeutic applications. In recent years a number of pentadentate polypyrrolic aromatic systems, including the "sapphyrine",.sup.3,6 "oxosapphyrins",.sup.7 "smaragdyrins",.sup.3,6 "platyrins",.sup.8 and "pentaphyrin".sup.19 have been prepared and studied as their metal-free forms. For the most part, however, little or no information is available for the corresponding metallated forms. Prior to this invention the uranyl complex of "superphthalocyanine" was the only metal-containing pentapyrrolic system which has been prepared and characterized structurally..sup.2 The "superphthalocyanine" system is not capable of existence in either its free-base or other metal-containing forms..sup.2 Thus, prior to the present invention, no versatile, structurally characterized, pentadentate aromatic ligands were available,.sup.13b although a number of nonaromatic pyridine-derived pentadentate systems had previously been reported..sup.37,38
Gadolinium(III) complexes derived from strongly binding anionic ligands, such as diethylenetriamine pentaacetic acid (DTPA),.sup.40-42 1,4,7,10-tetraazacyclododecane N,N',N",N"'-tetraacetic acid (DOTA),.sup.40,43,44 and 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N,N'-diacetic acid (dacda),.sup.40,45 are among the most promising of the paramagnetic contrast agents currently being developed for use in magnetic resonance imaging (MRI).sup.40 The complex, [Gd*DTPA].sup.-, is now being used clinically in the United States in certain enhanced tumor detection and other imaging protocols..sup.40 Nonetheless, the synthesis of other gadolinium(III) complexes remains of interest since such systems might have greater kinetic stability, superior relaxivity, or better biodistribution properties than this or other carboxylate-based contrast agents. The water-soluble porphyrin derivatives, such as tetrakis(4-sulfonatophenyl)porphyrin (TPPS) cannot accommodate completely the large gadolinium(III) cation .sup.47 within the relatively small porphyrin binding core (r.congruent.2.0 .ANG..sup.48), and, as a consequence, gadolinium porphyrin complexes are invariably hydrolytically unstable..sup.33,34,46,49,50 Larger porphyrin-like ligands may offer a means of circumventing this problem..sup.51-59
A promising new modality for use in the control and treatment of tumors is pho
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The government has certain rights in the present invention pursuant to National Institutes of Health contract AI28845 and the National Science Foundation Presidential Young Investigator Award (1986) to J. L. Sessler, grant CHE-8552768.
Hemmi Gregory W.
Mody Tarak D.
Sessler Jonathan L.
Board of Regents , The University of Texas System
Shah Mukund J.
Ward E. C.
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