Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Patent
1990-10-29
1993-03-16
Bond, Robert T.
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C07D48722
Patent
active
051946033
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
The present invention relates to porphyrin metal complexes which are used as artificial oxygen carriers and the like.
BACKGROUND ART
An iron (II) porphyrin complex contained in hemoglobin or myoglobin reversibly adsorbs and desorbs oxygen molecules. Many studies for producing synthetic complexes which have oxygen adsorption and desorption functions similar to those of natural porphyrin iron (II) complexes have been reported: J. P. Collman, Accounts of Chemical Research, 10, 265(1977), and F. Basolo, B. M. Hoffman and J. A. Ibers, ibid, 8, 384(1975). As a porphyrin iron (II) complex from which a stable oxygen complex is produced at room temperature, an iron (II) 5,10,15,20-tetra(.alpha., .alpha., .alpha., .alpha.-o-pivalamidephenyl)porphyrin complex is reported (J. P. Collman et al., The Journal of the American Chemical Society, vol. 97, p.1427(1975)).
However, the complex is unable to produce a stable oxygen complex because it is easily oxidized by oxygen in the presence of a small amount of water. Accordingly, an iron (II) porphyrin complex which produces a stable oxygen complex at room temperature has been continuously researched. The inventors of the present invention have found that oxygen is reversibly adsorbed and desorbed in an aqueous solution by inclusion of these iron porphyrin complexes in lipid molecular membranes. (Publication number of examined patent application: 59-25767/1984 and Publication number of laid-open patent application: 59-101490/1984).
DISCLOSURE OF INVENTION
As a result of an investigation into molecular designs for porphyrin metal complexes producible more stable oxygen complexes and the appearance of their functions, the present inventors considered that the behavior of oxidation and deterioration of the complexes was prevented by introducing bulky substituent groups in both sides of the porphyrin rings so that more stable oxygen complexes could be provided and they have found new porphyrin metal complexes.
Namely, the present invention provides a porphyrin metal complex (5,10,15,20-tetra(2',6'-dipivaloyloxyphenyl)porphinato metal complex) which is represented by the formula (1): ##STR2## wherein R is a pivaloyloxy group, M is a transition metal ion of the group IV and the group V metals, X is a halogen ion, and n is 0 or 1. The same marks under-mentioned show the same meanings.
As the transition metal ion, an iron ion or a cobalt ion is especially preferred. As the halogen ion, a chlorine ion or a bromin ion can be exemplified. The coordination number of the ion is given by the valence of metal ion M minus 2. The valence of the metal ion is generally 2 or 3.
A complex connectable with oxygen is embodied by a complex having a divalent metal ion of two valence and one or two basic axial ligands. The complex is represented by the formula (2): ##STR3## wherein L is a basic axial ligand, y and z are 0 or 1, respectively, and y+z is 1 or 2.
The porphyrin metal complexes represented by the formula (1 ) can be synthesized by the following process, for example; ##STR4##
In the above-mentioned process, 2,6-dimethoxybenzaldehyde and pyrrole (equimolecular quantities) are condensed in a suitable solvent to synthesize 5,10,15,20-tetra(2',6'-dimethoxyphenyl)porphyrin (in the above process, the compound represented by H.sub.2 T.sub.2,6-OMe PP).
As the solvent, acetic acid, propionic acid, butyric acid or the like is usable. The reaction temperature can be controlled by considering the kind of the solvent and the other conditions, usually a temperature of 80.degree.-120.degree. C. is selected. The reaction time is 5-12 hours, preferably 5-8 hours. After such condensation of these compounds, the tarry reaction mixture obtained by filtrating the reaction solution is purified by, for example, silica gel chromatography or the like to obtain 5,10,15,20-tetra(2',6'-dimethoxyphenyl)porphyrin. Then, 5,10,15,20-tetra(2',6'-dimethoxyphenyl)porphyrin is dissolved in a suitable dry solvent (dichloromethane, chloroform, tetrahydrofuran or the like), cooled in an ice-water bath 40
REFERENCES:
Chemistry Letters: "A bisfenced porphynatoring system . . . synthesis and ligand binding" pp. 1071-1074 (1990).
"Phosphocholine-substituted 5,10,15,20-Tetrapenylporphyrinatoiron Oxygen Carrier under physiological Conditions", J. Chem. Soc. Dalton Trans, 1985, Eishun Tsuchida et al., Tokyo, Japan.
"Lipsomal Heme as Oxygen carrier under Semi-physiological Conditions", Eishun Tsuchia et al., J. Chem. Soc. Dalton Trans, 1984, Tokyo, Japan.
Hasegawa Etsuo
Komatsu Teruyuki
Nishide Hiroyuki
Tsuchida Eishun
Bond Robert T.
Nippon Oil & Fats Co. Ltd.
Venkat Jyothsna
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