WO1994004507A1 - Vehicules d'oxygene du type porphynine en forme de panier - Google Patents

Vehicules d'oxygene du type porphynine en forme de panier Download PDF

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WO1994004507A1
WO1994004507A1 PCT/US1993/007708 US9307708W WO9404507A1 WO 1994004507 A1 WO1994004507 A1 WO 1994004507A1 US 9307708 W US9307708 W US 9307708W WO 9404507 A1 WO9404507 A1 WO 9404507A1
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oxygen
complex
fiber
porphyrin
support
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PCT/US1993/007708
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English (en)
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Xumu Zhang
James P. Collman
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The Board Of Trustees Of The Leland Stanford Junior University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines

Definitions

  • the present invention relates to basket porphyrin compounds and their use as oxygen carriers.
  • a synthetic oxygen carrier or binding compound should be easy to synthesize, have a high oxygen-binding affinity and yet be amenable to deoxygenation under selected conditions, be resistant to oxidative degradation, and be able to withstand heating without isomerization.
  • metal porphyrins which have these qualities would have important commercial applications in a variety of areas, such as removal of oxygen from impure gases, oxygen-extraction from gases and liquids, and in oxygen sensors.
  • the present invention includes, in one aspect, a dioxygen-binding complex of the form, when oxygenated:
  • M is Fe or Co
  • L is a neutral, sigma-donating ligand
  • the complex in a toluene-soluble form, is characterized by a P ⁇ 2 (0 2 ) value, when measured in toluene containing 1,5-dicyclohexyl- imidazole, at 25°C, of less than about 40 Torr when M is Co, and less than about 0.5 Torr when M is Fe.
  • the amidophenyl rings in the porphyrin skeletal structure may be unsubstituted or substituted, for example, with sulfonate groups, to enhance the water- solubility of the compound.
  • a ring substituent may be used in anchoring the compound to a solid support.
  • Also forming part of the invention is a method for extracting oxygen from an oxygen-containing fluid.
  • the method includes exposing an oxygen- containing fluid to an oxygen-binding complex of the type described above.
  • the method is designed for removing dioxygen in free form from an aqueous solution.
  • the imidophenyl rings in the porphyrin skeletal structure of the oxygen-binding complex are substituted at one or more ring positions with substituents having terminal acid groups, preferably sulfonate groups, and the complex has an octanol/water partition coefficient less than 1.
  • the method is designed for extracting oxygen from an oxygen-containing gas mixture, where the oxygen-binding complex is attached to an oxygen-permeable membrane.
  • the method includes exposing the gas to the membrane, on one side of the membrane, and applying a vacuum to the opposite side of the membrane, to draw off oxygen bound to the membrane via said complex.
  • Another application is designed for concentrating oxygen from an oxygen-containing fluid, where said complex is bound to a solid support.
  • the support After exposing the solid support to the fluid, the support is separated from the fluid and treated to remove bound oxygen.
  • Fig. 1 shows a skeletal structure for oxygen- binding compounds of the present invention
  • Fig. 2 shows a reaction scheme used in synthesizing a porphyrin component for the oxygen- binding compounds of the present invention
  • Figs. 3A-3G show synthetic reaction schemes used in preparing a series of 'strap' structures for inclusion in the oxygen-binding compounds of the present invention
  • Fig. 4 shows a reaction scheme for converting a 'strap' tetraester to a tetraacid chloride via a tetraacid.
  • Fig. 5 shows a reaction scheme used in sythesizing an un-metalated form of the oxygen- binding compounds of the present invention
  • Fig. 6 illustrates a synthesis of a water- soluble oxygen-binding compound of the present invention in an unmetalated form.
  • Fig. 7 shows a scheme for preparing an oxygenated form of an oxygen-binding compound of the present invention.
  • Fig. 8 illustrates how an oxygen-binding compound of the invention can be modified in its strap region with a variety of chemical groups R.
  • Figs. 9A and 9B illustrate two types of covalent linkages of an oxygen-binding compound of the invention to a solid support.
  • Fig. 10 shows portions of a fiber-optic 0 2 sensor device utilizing the oxygen-binding compound of the invention.
  • FIG. 1 A skeletal structure (I) for a number of oxygen- binding compounds (also referred to herein as "picnic-basket porphyrins" or “porphyrin compounds”) of the present invention is shown in Fig. 1.
  • the oxygen-binding compounds of the invention generally comprise two main structural components: a 'phenylporphyrin' component (meso- ⁇ , ⁇ , ⁇ , ⁇ -tetrakis(o- aminophenyl)porphyrin) and a 'strap'component.
  • the phenylporphyrin component contains four pyrrole nitrogen atoms for tightly binding metal ions.
  • the 'strap' component includes two trivalent benzene rings linked to one another by a bridge linkage of variable length (one to four, and more preferably, one to three atoms) .
  • Amide bonds connect the four carboxy groups of the strap to the four ortho-amino groups of the phenylporphyrin.
  • Figs. 3A-3G show synthetic schemes for preparing a number of 'strap' precursors to be incorporated into oxygen-binding compounds of the present invention.
  • the straps are prepared first as tetraesters which are then converted via the tetracarboxylic acid to tetraacid chlorides for reaction with the phenylporphyrin of Fig. 2.
  • the strap can be prepared as a tetraacid, bypassing a tetraester species.
  • Fig. 3A shows a scheme for synthesizing a strap (VII) in which Y is 0CH 2 CH,0 (Collman et al., 1988).
  • the synthesis, detailed in Example 2A, involves the reaction of diethyl 5-hydroxyisophthalate (V) with 1,2-dibromoethane (VI).
  • Fig. 3B shows a scheme for synthesizing a smaller, asymmetric strap where Y is CH 2 0.
  • the tetraester X is obtained from diethyl-5-bromomethylisophthalate (VII) and diethyl- 5-hydroxyisophthalate (IX) in high yield. Details of the synthesis are given in Example 2B.
  • the scheme entails reacting 3,5-dicarbethoxybenzaldehyde XVII and diethyl 5- aminoisophthalate XVIII to form a Schiff base XIX, followed by reduction of the Schiff base with lithium cyanoborohydride to give tetraester XX.
  • Procedures for obtaining XX are outlined in Example 2D.
  • the amino nitrogen of the bridge can be alkylated using an alkylhalide or a mixture of alkylhalides to produce a tertiary or quaternary amine.
  • FIG. 3F A reaction scheme for preparing a strap containing an ethylene bridge is shown in Fig. 3F.
  • the scheme involves the reaction of 3,5- dicarbethoxybenzaldehyde (XVII) with diethyl 5- bromomethylisophthalate in an ylide procedure that produces olefin XXI. Subsequent reduction with Wilkinson's catalyst (RhCl(PPh 3 ) 3 ) results in the desired product (XXII) .
  • RhCl(PPh 3 ) 3 Wilkinson's catalyst
  • Figure 4 illustrates a general reaction scheme for converting a tetraester strap to a tetraacid chloride for subsequent reaction with the phenylporphyrin of Fig. 2 to give a picnic-basket porphyrin.
  • tetraester X is treated in a first step with concentrated aqueous sodium hydroxide in ethanol to precipitate the product tetraacid Xa as the sodium salt. The product is then dissolved in water and precipitated as the tetraacid Xa using 6 N HCl.
  • a second step the resultant tetraacid is treated with thionyl chloride under reflux conditions to yield the tetraacid chloride XXVI.
  • the strap is already produced as a tetraacid from monoaryl starting materials, only the second step (conversion of the tetraacid to the tetraacid chloride) is called for.
  • ⁇ , ⁇ , ⁇ ,Q.-tetra(o- aminophenyl)porphryin IV and tetraacid chloride XXVI are simultaneously added dropwise to a solution of CH 2 C1 2 containing a small amount of triethylamine to trap HCl produced by the reaction.
  • the reaction mixture is allowed to stir an additional 24 h at room temperature.
  • the solution is then washed with saturated NaHC0 3 and saturated NaCl solutions, dried over Na 2 S0 4 , filtered, and evaporated to dryness.
  • picnic- basket porphyrins prepared as above can be derivatized at one or more imidophenyl ring positions with substituents having terminal acid groups that impart water solubility to the porphyrin compound.
  • terminal acid groups are defined to include phosphonate, sulfonate, sulfinate, and carboxylate groups, which are attached either directly to the imidophenyl ring, or indirectly via 1 or 2 methylene groups.
  • the terminal acid groups are sulfonate groups.
  • Fig. 6 illustrates a reaction in which an unsubstituted porphyrin compound is treated with sulfuric acid to produce a sulfonated porphyrin derivative XXVIII containing sulfonate groups on the amidophenyl rings.
  • a major site of sulfonation in each amidophenyl ring is the ring position para to the amido group. Details of a method of sulfonation are given in Example 5.
  • a scheme for preparing oxygen-binding complexes of the present invention, in deoxygenated and oxygenated forms, is outlined in Fig. 7.
  • the scheme includes three steps: metalation of the metal-free porphyrin XXVII to give a metal-porphyrin complex; addition of ligand L, which binds to the axial position of the metal on the "open" side of the heme (on the opposite side from the strap) to form a pentacoordinate, deoxygenated ligand-metal complex; and addition of oxygen, which binds to the axial position of the metal on the "inner” side of the heme (on the same side as the strap) to produce a hexacoordinate, oxygenated ligand-metal complex XXIX.
  • Metalation also termed "metal insertion" of the metal-free (unmetalated) porphyrin compound
  • a water-soluble porphyrin compound may also be metalated using the above conditions, but the compound must first be converted to a tetraalkylammonium salt or the like to be rendered soluble in the organic solvents above. Such conversion can be accomplished readily by use of a cation-exchange column. Following metalation, the resultant metalloporphyrin can be converted back to a water-soluble form by a second cation-exchange column (e.g. , using an exchange column (Na + form) to produce the sodium salt of the metal-complex) .
  • a second cation-exchange column e.g. , using an exchange column (Na + form) to produce the sodium salt of the metal-complex
  • the oxidation pathway involves the formation of a ⁇ -peroxo-bridged metal-porphyrin dimer. Accordingly, it is desirable to construct a porphyrin complex so as to prevent the formation of a ⁇ -peroxo-bridged dimer, while still allowing binding of dioxygen.
  • ligands include substituted as well as non-substituted nitrogen- containing aromatic heterocycles such as imidazole, pyridine, and pyrazine, and, less preferably, primary, secondary, and tertiary amines.
  • L is a 1,5-dialkylimidazole such as 1,5-dicyclo- hexylimidazole.
  • Another preferred ligand is l- methylimidazole.
  • Other substituted i idazoles can also be used, provided that at least one of the imidazole nitrogens remains unsubstituted.
  • ligand is included in the solution typically in about a 100- to a 1000-fold excess, thereby minimizing the opportunity for oxygen to bind on the open face side of the metal.
  • the ligand can be present in stoichiometric amounts, or is provided by the solid phase itself.
  • the oxygen-binding affinities of porphyrin complexes of the present invention can be measured by a UV-Vis spectrophoto etric titration method. Measurements are performed with the sample in the closed atmosphere, of defined volume, that is provided by a tonometer equipped with a cuvette and a septum. A solution containing the sample porphyrin complex is placed in the cuvette portion of the tonometer under an inert atmosphere, and then oxygen is introduced into the tomometer in a series of aliquots.
  • the tonometer is shaken to allow equilibration (for a few minutes) of oxygen with the sample solution, and then a UV-Vis spectrum of the sample is recorded. Measurement of the changing intensities of the absorbance peaks corresponding to the deoxygenated and oxygenated complexes allows the determination of the oxygen-binding affinity, as detailed in Example 7.
  • the compounds of the present invention combine the unique features of (a) being thermal-resistant, in that they cannot be isomerized with heating and (b) having low P 1/2 (0 2 ) . This applies both to the Co and Fe complexes.
  • the invention includes a method for extracting oxygen from an oxygen-containing fluid.
  • the method includes exposing an oxygen- containing fluid to the above-described oxygen- binding complex, producing the oxygenated form of the binding complex.
  • the method is used in removing dioxygen in free form from an aqueous solution.
  • the oxygen-binding complex is derivatized, either at one or more of the imidophenyl rings in the porphyrin structure, or at a nitrogen atom in the strap in the structure, with chemical group(s) which result in good water solubility, preferably having an octanol/water partition coefficient of less than 1.
  • a water-soluble oxygen-binding compound suitable for use in an aqueous medium has been described above with respect to Fig. 6.
  • the compound shown there contains one sulfonate group per imidophenyl ring in the skeletal structure of the binding compound. More generally, one or more of the rings are derivatized with substituents having free acid groups.
  • Fig. 8 shows another approach to derivatizing the compound.
  • the compound contains a -N(H)-CH 2 strap, and allows for a variety of alkylated or acylated reactions at the strap amine, to produce a a desired R substituent on the strap, as indicated.
  • the compound is complexed with Zn +2 , to protect the porphyrin amines, prior to the alkylation or acylation reactions.
  • the R group may be, for example, a long-chain polyethylene oxide (PEO) or a water-soluble polypeptide.
  • PEO polyethylene oxide
  • the water-soluble compound may be used to sequester molecular oxygen, for example, in an aqueous chemical solution or suspension in which oxidative reactions are to be limited.
  • the oxygen- binding compound is coupled to a solid support, for removing dioxygen from a fluid which is in contact with the support.
  • Figs. 9A and 9B illustrate two general methods for attaching the compound to a support.
  • the compound is anchored to the solid support, indicated at 50, by a linker 52 connected covalently to an amine group in the compound strap.
  • Bifunctional linkers suitable for attaching the compound, e.g., through an amide linkage, to a solid support, e.g., through a carboxyl or OH group on the support, are well known.
  • Fig. 9A the compound is anchored to the solid support, indicated at 50, by a linker 52 connected covalently to an amine group in the compound strap.
  • Bifunctional linkers suitable for attaching the compound e.g., through an amide linkage, to a solid support, e.g., through a carboxyl or OH group on the support, are well known.
  • Fig. 9A the compound is
  • the compound is attached to a solid surface 56 via a ligand, such as an imidazole or pyridine ligand, using a suitable bifunctional reagent.
  • a ligand such as an imidazole or pyridine ligand
  • the compound may be adsorbed to the surface by non-covalent attachment.
  • the solid support may be used for purifying an oxygen-containing gas, such as for removal of 0 2 from N 2 , or for use in producing 0 2 in purified form.
  • the solid support may be formed on a shuttling structure which is operable between a collect position in which the solid support is in contact with an oxygen-containing fluid, such as air, and a release position, in which the bound oxygen is released from the support, e.g., by vacuum or heating.
  • the support may be part of an electrode. Oxygen binding to the support occurs with the iron in the reduced state. To release bound oxygen, the metal is converted electrochemically to its oxidized state.
  • the method of the invention is used to extract 0 2 from a liquid or gaseous medium, by extraction of 0 2 through an oxygen-permeable polymeric membrane.
  • Methods of forming porphyrin ring within an oxygen-permeable membrane are known (EPO 0464717 Al) .
  • the membrane is in contact with an oxygen- containing fluid on one side of the membrane, which may be a liquid from which 0 2 is to be extracted, or a gas containing 0 2 impurity, or a gas from which it is desired to obtain purified 0 2 .
  • Dioxygen in the fluid diffuses into the membrane and becomes bound to the oxygen-binding sites in the membrane.
  • Molecular oxygen bound to the membrane can be removed from the sites, at the other side of the membrane, by applying a pressure differential across the membrane.
  • Fig. 10 shows an oxygen-sensor apparatus 60 constructed according to the invention.
  • the apparatus includes an optical fiber probe 61 composed of a first fiber 62 having an end region which is prepared with a light-trans issive coating 65 of an oxygen-binding complex of claim 1, and a second fiber 64 which is adapted to receive light transmitted through the coating, when light is directed through the first fiber.
  • the coating in the probe is oxygenated, the spectral peak of the compound shifts.
  • the device further includes a light source or means 68 for producing a light in a selected wavelength between about 420 and 460 nm, and a sensor 70 for detecting light intensity directed from the distal end of fiber 64 back to a detection unit 72.
  • Unit 72 is also designed to determine oxygen concentration, at the site of the fiber probe, from the time-dependent change in light intensity received by the sensor.
  • the probe is guided to a selected target site, i.e., a site within the vascular system of a patient.
  • a selected target site i.e., a site within the vascular system of a patient.
  • the time dependent change in spectral shift in light transmission is monitored to determine oxygen pressure at the site.
  • Fe(II) porphyrin NMR samples were prepared as follows. To an Fe(II) porphyrin, freshly prepared by metalation in a glovebox (0 2 ⁇ lppm) , CDC1 3 and 4-10 equivalents of imidazole were added, and the five-coordinate Fe(II) complexes were identified by their characteristic paramagnetic contact-shifted NMR spectra. These solutions were exposed to an atmosphere of 0 2 at room temperature, and spectra were obtained, also at room temperature. Amide protons of the porphyrins were identified by deuterium exchange with D 2 0.
  • the combined extracts were washed with 1 L of dilute NH 4 OH, which washings in turn were extracted with two 50-mL portions of chloroform.
  • the combined organic portion was evaporated to 600 L on a rotary evaporator and then filtered by suction.
  • the filtrate and washings were concentrated to 250 mL, 150 mL of 95% ethanol containing 10 mL of cone, aqueous NH 3 was added, and the solvent slowly evaporated until the remaining volume was about 200 mL.
  • the sides of the flask were washed down with chloroform and 100 L of ethanol was added.
  • Reagent-grade benzene (85 mL) and 36 g of silica gel were added to a 250-mL 3-neck round-bottom flask fitted with a nitrogen inlet and reflux condenser. This was immersed in an oil bath maintained at 75- 80°C, with magnetic stirring and a steady flow of benzene-saturated dry nitrogen gas. After 2 h, 1 g of the mixture of atropisomers was added to the flask. After an additional 20 h, the dark slurry was cooled to room temperature and then poured into a 53- mm diameter chromatography column.
  • the coupling reaction is performed at an elevated temperature in the presence of K 2 C0 3 and a catalytic amount of a copper catalyst such as CuCl, as described generally by Moroz et al. (1974) . Oxidation of the methyl groups is then accomplished using KMn0 4 (Lee, 1980) , giving the tetraacid.
  • 3,5-dicarbethoxybenzaldehyde XVII is prepared from diethyl 5-bromomethylisophthalate VIII (Example 2B) following the procedure of Kornblum et al. (1959) . Briefly, the bromide is added to an acetonitrile solution of silver tosylate (Aldrich) at 0-5°C (protected from light) and the mixture is allowed to come to room temperature overnight. The mixture is then added to ice water and extracted with ether. The resultant ethereal solution is evaporated and concentrated to dryness.
  • benzyltosylate is then added to a fresh mixture of NaHC0 3 (20 g) DMSO (150 mL) heated at 150°C through which N 2 has been bubbling. After 3 minutes at 150°C, the reaction is rapidly cooled, and the benzaldehyde product XVII is purified by silica gel chromatography.
  • the Schiff base is converted to the product tetraester (XX) by the general method of Borch et al. (1971) .
  • To 10 mmol of Schiff base in 25 L absolute methanol is added 4 mL of 5 N HCl followed by 6 mmol LiBH 3 CN.
  • the solution is stirred at 25°C for 72 hours, after which the methanol is evaporated to dryness.
  • the residue is taken up in ether, washed with brine, and dried over MgS0 4 , and then evaporated to dryness under reduced pressure.
  • the crude product is purified by silica gel chromatography.
  • Olefin XXI is prepared from bromide VIII (Example 2B) and 3,5-dicarbethoxybenzaldehyde XVII (Example 2D) by the general ylide synthesis of Greenwald et al. (1963). Bromide VIII is reacted with PPh 3 to form the phosphonium salt. In a separate reaction flask, 25 mL DMSO is add to 0.05 moles NaH. The latter mixture is heated at 75-80°C for 45 minutes and then cooled in an ice bath. The phosphonium salt is then added (0.05 moles) as a DMSO solution (50 mL) .
  • Diarylthioether XXIV is prepared from 1-bromo- 3,5-dimethylbenzene XII and the sodium salt of 3,5- dimethyl-1-thiobenzene XXIII by adaptation of a method from Testaferri et al. (1983) .
  • a solution of XII (10 mmol) and XXIII (50 mmol) in DMF (30 mL) is stirred under nitrogen for 17 h at 100°C. The progress of the reaction is monitored by TLC. The mixture is cooled, poured into water (100 L) and extracted with ether (3 x 50 mL) . The organic layer is washed with water (2 x 50 mL) , dried with Na 2 S0 4 , and evaporated.
  • Tetraester X (i) Tetraacid Xa.
  • Tetraester X (7.4 g, 15.7 mmol) was added to 95% EtOH (100 mL) in a 250 mL round-bottom flask fitted with a magnetic stirrer, heating mantle, and condenser. After the mixture was heated to 55°C, a solution of NaOH (5 g) in H 3 0 (5 L) was added. The mixture was allowed to react for 12 h, cooled to room temperature, and filtered. The white precipitate was washed once with ethanol (25 mL) and then dissolved in H 2 0 (300 mL) .
  • Tetraacid Xa (5 g, 13.9 mmol), thionyl chloride (20 mL) and a drop of DMF were added to a 50 mL round-bottom flask under a N 2 atmosphere. The mixture was heated at reflux for 6 h until all of the solid dissolved. The excess S0C1 2 was removed under vacuum to give the product as a light tan solid (5.2 g, 86.3%).
  • ⁇ NMR (CDC1 3 ) ⁇ 8.87 (s, 1H) , 8.55 (s, 1H) , 8.52 ( ⁇ , 2H) , 8.02 (s, 2H) , 5.34 ( ⁇ , 2H) .
  • Porphyrin XXVII was prepared from ⁇ , ⁇ , ,cc- tetra(o-aminophenyl)porphryin IV and tetraacid chloride XXVI.
  • the reaction wa ⁇ run under rigorou ⁇ ly dry condition ⁇ . All glassware was dried in an oven at 120°C and then cooled in the antechamber of a glove box.
  • , ⁇ , ⁇ , ⁇ -Tetra(o-aminophenyl)porphyrin IV (2.74 g, 4.1 mmol) was dissolved in CH 2 C1 2 (200 mL) and stirred with 4 A molecular sieve pellets (Aldrich) (5 g) for 3 h in the glove box.
  • the acid chloride XXVI (1.71 g, 4.1 mmol) was dissolved in CH 2 C1 2 (200 mL) in a flask.
  • the porphyrin and acid chloride solutions were transferred by cannula into respective funnels.
  • the two reactants were added dropwise into the three-neck flask at 0°C under N 2 atmosphere over the course of 4 h. After the addition was complete, the solution was stirred an additional 24 h at room temperature.
  • the CH 2 C1 2 solution was reduced to 300 mL, washed once with saturated NaHC0 3 (100 L) and NaCl (100 L) solutions, dried over Na 2 S0 4 , filtered, and evaporated to dryness. The residue was dissolved in CH 2 C1 2 , loaded onto a silica gel flash column prepared from a CH 2 C1 2 slurry, and eluted using 20% acetone/CH 2 C1 2 to give the desired product (1.01 g, 25.8% yield).
  • UV-vi ⁇ (CH 2 C1 2 ) 405 (shoulder) , 424 (Soret) , 518 , 550 (shoulder) , 590 , 644 nm.
  • the filtrate i ⁇ slowly diluted with 150 mL of water and then cooled in a refrigerator. Once cool, the resultant emerald green precipitate is filtered onto a 0.5 inch Celite pad in a large Buchner funnel. The filtrate is pale green and translucent. The pad material is then dried by suction and then vigorously stirred in 300 mL of acetone. Any clumps in the mixture are broken up manually. The resultant suspension is filtered again onto Celite and dried by suction. The dry Celite pad impregnated with the sulfonated product i ⁇ placed in a beaker and stirred with about 200 mL of 25% cone. ammonium hydroxide in methanol.
  • the resultant red slurry is filtered through a frit to remove the Celite.
  • the porphyrin product is washed from the Celite with a minimum of solvent.
  • the resultant red filtrate is then mixed with 3 volumes of acetone to precipitate the porphyrin product which is then collected by vacuum filtration, washed with acetone, dried by suction, and dried under high vacuum to yield the purified, sulfonated product.
  • picnic-basket porphyrin XXVII 40 mg
  • 2,6-lutidine 20 mL
  • the oxygen concentration of the glove box was continually monitored and maintained at less than 1 ppm.
  • Water-soluble picnic-basket porphyrin ⁇ (e.g., made water- ⁇ oluble by ⁇ ulfonic acid substituents) are prepared by the same general procedures outlined above, except that the picnic- basket porphyrin i ⁇ first converted to the tetrabutylammonium salt by cation-exchange chromatography to render the porphyrin soluble in THF or THF/benzene.
  • Dioxygen affinities of metalated picnic-basket porphyrins were determined spectrophotometrically using a Hewlett-Packard 8452A diode array UV-Vis spectrometer equipped with a 7470A plotter.
  • a closed atmosphere was attained using a 100 L tonometer (Ace Glass, Vineland, N.J.) equipped with a teflon-coated septum, a screw-seal, and a l cm cuvette. Spectra were recorded in the range 360-650 nm.
  • the temperature of the cuvette was maintained at 25 ⁇ 0.1 °C with a circulating liquid bath.
  • Dioxygen binding affinities were measured by recording a series of absorbance spectra over a range of dioxygen concentrations and fitting the resultant data to an equation described further below.
  • the equilibrium between the oxygenated and oxygen-free forms of the metalloporphyrin may be expressed as:
  • P n (0 2 ) [(P n .,(0 2 ) .(V-v)) + 760V] /V
  • V is the volume of the tonometer (not including the volume of the solution)
  • v i ⁇ the volume of the gas displaced by addition of the aliquot
  • the pressure is held constant at 760 Torr.
  • the relationship between P n (0 2 ) and the equilibrium constant K can be expre ⁇ sed a ⁇ :
  • a metalated picnic-basket porphyrin was dissolved in toluene with a known excess of ligand L (generally 100 to 1000 times the concentration of the porphyrin) .
  • the sample concentration wa ⁇ selected to yield a maximum absorbance at the Soret band of about 1.2 absorbance units to ensure a linear respon ⁇ e.
  • the tonometer wa ⁇ removed from the inert- atmo ⁇ phere box and placed in the UV-Vi ⁇ spectrophotometer, and the ⁇ ample wa ⁇ allowed to temperature-equilibrate.
  • Dioxygen (2% in nitrogen) wa ⁇ added in known aliquots using a gas-tight syringe. An identical volume of gas wa ⁇ removed from the tonometer before addition of the dioxygen aliquot to maintain constant pressure in the tonometer. After each addition of dioxygen, the sample wa ⁇ shaken vigorously and then allowed to reach equilibrium before an absorbance spectrum was recorded. Thi ⁇ procedure wa ⁇ repeated for each dioxygen aliquot.
  • the range of oxygen partial pre ⁇ ure used depended upon the oxygen- binding affinity of the particular porphyrin under study. Sets of spectra which showed iso ⁇ bestic points were used to calculate equilibrium constant ⁇ for oxygen-binding affinity. The absorbance values were taken from the Soret maximum. Line plots and least-square ⁇ analyses were carried out using the program RS/1 (BBN Software Products Corporation) .

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Abstract

Complexe de liaison du dioxygène du type prophyrine en forme de panier. Le complexe comprend une structure de phénylporphyrine, un métal M lié à la structure de phénylporphyrine, M étant du fer ou du cobalt, une structure de sangle attachée à la structure de phénylporphyrine et comprenant une liaison Y en point dans laquelle Y représente X, X-CH2, ou CH2-X-CH2 où X représente 0, S, S(=O), S(=O)2, NR, ou =NRR', R et R' étant identiques ou différents et représentent un hydrogène ou un alcane inférieur, et un ligand neutre donneur sigma, L qui se fixe sur le métal sur le côté ouvert de la structure de polyprophyrine. Cette invention concerne également l'utilisation de ce complexe pour extraire l'oxygène d'un fluide et comme constituant d'un capteur d'oxygène.
PCT/US1993/007708 1992-08-21 1993-08-16 Vehicules d'oxygene du type porphynine en forme de panier WO1994004507A1 (fr)

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US07/933,459 1992-08-21

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0711598A3 (fr) * 1994-11-14 1996-05-29 Praxair Technology Inc
EP0853976A1 (fr) * 1997-01-15 1998-07-22 Praxair Technology, Inc. Adsorbants sélectifs pour l'oxygène
US6630128B1 (en) 1998-08-28 2003-10-07 Destiny Pharma Limited Porphyrin derivatives their use in photodynamic therapy and medical devices containing them
EP1600766A1 (fr) * 2003-02-24 2005-11-30 Makoto Yuasa Dispositif de mesure des especes actives de l'oxygene
US20110315551A1 (en) * 2001-12-20 2011-12-29 Makoto Yuasa Electrode for active oxygen species and sensor using the electrode
CN114735654A (zh) * 2022-04-20 2022-07-12 郭俊 一种变压吸附制氧机
US11572205B2 (en) 2017-01-20 2023-02-07 Ardagh Mp Group Netherlands B.V. Tool and method for closing a container and method for producing a container with several compartments

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EP0110396A2 (fr) * 1982-12-01 1984-06-13 Taiho Pharmaceutical Co., Ltd. Complexe fer-tétraphénylporphine ayant un groupe phosphocholine et agent d'adsorption et désorption de l'oxygène
US4952289A (en) * 1988-05-09 1990-08-28 Aquanautics Corporation Macrocyclic amine complexes for ligand extraction and generation

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EP0110396A2 (fr) * 1982-12-01 1984-06-13 Taiho Pharmaceutical Co., Ltd. Complexe fer-tétraphénylporphine ayant un groupe phosphocholine et agent d'adsorption et désorption de l'oxygène
US4952289A (en) * 1988-05-09 1990-08-28 Aquanautics Corporation Macrocyclic amine complexes for ligand extraction and generation

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Title
J. AM, CHEM. SOC., Vol. 104, issued 27 July 1981, HASHIMOTO et al., "Ligand Oxygen, and Carbon Monoxide Affinities of Iron(II) Modified 'Capped' Porphyrins", pages 2101-2109. *
J. AM. CHEM. SOC., Vol. 103, issued 22 September 1980, COLLMAN et al., "The 'Pocket', Porphyrin: A Hemoprotein Model with Lowered CO Affinity", pages 2450-2452. *
J. AM. CHEM. SOC., Vol. 110, issued 08 July 1987, COLLMAN et al., "Reversible Binding of Dinitrogen and Dioxygen by a Ruthenium 'Picnic-Basket' Porphyrin", pages 3486-3495. *
J. AM. CHEM. SOC., Vol. 110, issued 08 July 1987, COLLMAN et al., "Synthesis, Characterization, and X-Ray Structure of the Ruthenium 'Picnic-Basket' Porphyrins", pages 3477-3486. *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0711598A3 (fr) * 1994-11-14 1996-05-29 Praxair Technology Inc
US5945079A (en) * 1994-11-14 1999-08-31 Praxair Technology, Inc. Oxygen-selective sorbents
EP0853976A1 (fr) * 1997-01-15 1998-07-22 Praxair Technology, Inc. Adsorbants sélectifs pour l'oxygène
US6630128B1 (en) 1998-08-28 2003-10-07 Destiny Pharma Limited Porphyrin derivatives their use in photodynamic therapy and medical devices containing them
US20110315551A1 (en) * 2001-12-20 2011-12-29 Makoto Yuasa Electrode for active oxygen species and sensor using the electrode
EP1600766A1 (fr) * 2003-02-24 2005-11-30 Makoto Yuasa Dispositif de mesure des especes actives de l'oxygene
EP1600766B1 (fr) * 2003-02-24 2019-06-26 Makoto Yuasa Dispositif de mesure des especes actives de l'oxygene
US11572205B2 (en) 2017-01-20 2023-02-07 Ardagh Mp Group Netherlands B.V. Tool and method for closing a container and method for producing a container with several compartments
CN114735654A (zh) * 2022-04-20 2022-07-12 郭俊 一种变压吸附制氧机
CN114735654B (zh) * 2022-04-20 2023-12-19 贵阳睿亿泰医特工程有限公司 一种变压吸附制氧机

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