Organic compounds -- part of the class 532-570 series – Organic compounds – Unsubstituted hydrocarbyl chain between the ring and the -c-...
Reexamination Certificate
2001-07-12
2002-08-27
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Unsubstituted hydrocarbyl chain between the ring and the -c-...
C540S450000, C540S465000, C556S138000, C556S146000
Reexamination Certificate
active
06441164
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to substituted crown ligands that are redox active, and methods of using the same.
BACKGROUND OF THE INVENTION
Macrocyclic polyethers, generally known as “crown ethers”, were first described by Charles Pedersen. See generally C. J. Pederson,
J. Am. Chem. Soc.
89:26, 7017 (Dec. 20, 1967). Numerous variations have been made to produce a group of compounds known as crown ligands or macrocyclic ligands.
The attachment of redox centers to crown ethers was first described by Dr. Fritz Vogtle. Such compounds are of interest because the coordinating ability (binding strength and/or selectivity) can be altered by physical or chemical means. Redox active macrocyclic ligands that have been produced to date include ferrocene derivatives, tetrathiafulvalene derivatives, and quinone derivatives. See generally P. Beer,
Chem. Soc. Rev.
18, 409 (1989); P. Beer.,
Chem. Soc. Rev.
39, 79 (1992); T. Jorgensen et al.,
Chem. Soc. Rev.
23, 41 (1994); R. Dieing et al.,
J. Chem. Soc., Perkin Trans.,
1587 (1996); Z. Chen and L. Echegoyen, in
Crown Compounds Toward Future Applications,
p. 27 (S. Cooper Ed. 1992).
SUMMARY OF THE INVENTION
Redox active macrocyclic ligands of Formula 1A and Formula 1B are disclosed:
In Formulas 1A and 1B, the rings A and B, respectively, are not indicative of any specific number of bonds or atoms, but instead represent the ring system of a macrocyclic ligand (e.g., a crown ether) substituted with a 1,4-phenylenediamine group as shown. As noted below, the methyl groups shown may be replaced with other C1-C4 loweralkyl groups.
A second aspect of the invention is a composition comprising a redox active compound as given above in a carrier solution.
Compounds of Formulas 1A and 1B and compositions containing the same are useful as redox switches, sensors, transport agents, and electrocatalysts.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention now will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown.
The term “macrocyclic ligand” as used herein means a macrocyclic molecule of repeating units of carbon atoms and hetero atoms (e.g., O, S, or NH), separated by the carbon atoms (generally by at least two or three carbon atoms). Macrocyclic ligands exhibit a conformation with a so-called hole capable of trapping ions or molecules, particularly cations, by coordination with the electrons of the hetero atom (e.g., a lone pair of electrons on the oxygen atoms when the hetero atoms are oxygen). In general, the macrocyclic ring contains at least 9, 12 or 14 carbon atoms and hetero atoms (e.g., O, S, NH), each hetero atom in the ring being separated from adjoining hetero atoms in the ring by two or more carbon atoms. The macrocyclic ring may be substituted or unsubstituted, and may be fused to additional rings (e.g., 1 to 4 additional rings such as phenylene, naphthylene, phenanthrylene, and anthrylene rings).
The term “crown ether” as used herein means a macrocyclic polyether whose structure exhibits a conformation with a so-called hole capable of trapping cations by coordination with a lone pair of electrons on the oxygen atoms (McGraw-Hill
Dictionary of Scientific and Technical Terms
(3d ed. 1984)). Crown ethers are a species of macrocyclic ligand.
The present invention may be carried out by substituting at least one hetero atom of a macrocyclic ligand or crown ether with a 1,4-phenylenediamine group by covalent bond to one, or both, of the amine nitrogen atoms, as shown above and below.
Any macrocyclic ligand or crown ether can be substituted as shown herein and used to carry out the present invention, including but not limited to those described in U.S. Pat. Nos. 5,252,733; 5,589,446; 5,587,499; 5,536,577; 5,478,953; 5,391,628; 4,876,367; 4,777,270; 4,652,399; 4,254,034; 4,104,275; 4,031,111; 4,024,158; 4,001,279; 3,997,562; 3,997,565; 3,987,061; and 3,687,978; the disclosures of which applicants specifically intend to be incorporated herein by reference in their entirety. The term “macrocyclic ligand” as used herein encompasses macrobicyclic ligands as well.
In general, compounds of the invention are prepared by combining N,N-dimethyl-1,4-p-phenylenediamine (for compounds of Formula 1A) or N,N′-dimethyl-1,4-p-phenylenediamine (for compounds of Formula 1B) with an acyclic precursor for a macrocyclic ligand (e.g., a polyether, polythioether, or polyaza fragment) (also called a di-substituted fragment) that is end-terminated on both ends with a sulfonate or halide (e.g., bromide, chloride or iodide, in that order of preference). The combination is carried out in a polar aprotic solvent such as acetonitrile or N,N-dimethylformamide under basic conditions, preferably with heat, to produce the compound of Formula 1A or 1B.
Acyclic precursors useful for carrying out the method may be generally represented by the formula Z—Y—Z, wherein Z is a sulfonate or halide group as described above, and Y is a macrocyclic ligand fragment such as a polyether, polythioether, or polyaza group that contains at least 8 or 11 carbon and hetero atoms, up to 120, 160, 200, 400, or 800 or more carbon and hetero atoms.
Examples of redox active macrocyclic ligands of the present invention are compounds of Formula 2:
wherein:
X is O, S, or NH and n is 1, 2 or 3 to 6, 10, 20, 30 or 40, subject to the proviso that at least one of X is a redox active substituent selected from the group consisting of:
Preferably, X is O. Preferably, 1, 2, 3 or 4 of X is a redox active substituent as given above. Preferably, where more than one redox active substituent is present, the redox active substituents are the same.
In Formula 2, the C2 alkylene groups shown between hetero atoms X may be replaced with different alkylene groups (e.g., C3 or C4 alkylene groups). All of the alkylene groups in the ring system may be the same, or they may differ. The resulting ring system may be symmetric or asymmetric. The alkylene groups may be unsubstituted or substituted (e.g., they may be substituted with any of the groups shown in the patents incorporated by reference above).
Compositions of the present invention comprise a redox-active compound as described above in a carrier liquid (e.g., an aqueous carrier solution, preferably one containing at least about 30, 40 or 50 percent by weight of water). The redox-active compound may be included in the composition in any suitable amount, which will vary depending upon the use of the composition, but is typically included in an amount of from about 0.001, 0.01, or 0.1 to 5, 10, 20 or 40 percent by weight of the total composition.
As discussed in greater detail below, the redox-active compounds of the present invention have a variety of applications, including but not limited to use as redox switches, sensors, transport agents and electrocatalysts. In general, the compounds are useful in binding substrates (e.g., metals, particularly metal ions such as anions and cations), by contacting a redox active compound of the invention to a substrate that is selectively bound by or coordinates with that compound. The contacting step may be carried out under any suitable conditions depending upon the particular application. For example, the contacting step may be carried out in a liquid solution such as an aqueous solution described above. The substrate may be included in the solution in any suitable amount (e.g., from about 0.01, 0.001, 0.0001, 0.00001, 0.000001 percent by weight or less, up to about 1, 5, 10 or 20 percent by weight or more, depending upon the particular application). As will be appreciated, the binding of the substrate may be manipulated by oxidizing or reducing the redox active compound before or after the binding step. For example, the redox active compound may be oxidized before the binding step and then reduced after the binding step, or the redox active compound may be reduced before the binding step and oxidized after the binding step. Oxidation and reduction can be carried out by physical and/or c
East Carolina University
Myers Bigel & Sibley & Sajovec
Patel Sudhaker B.
Raymond Richard L.
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