| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | May 22, 2001 |
| PATENT TITLE |
Synthesis of oligoarylamines, and uses and reagents related thereto |
| PATENT ABSTRACT |
The transition metal-catalyzed amination of aryl halides, in conjunction with an orthogonal protective group scheme, forms the basis of two routes to oligoaniline precursors. The oligoaniline precursors are soluble in a variety of common organic solvents, and are easily converted to the deprotected oligoanilines. The method allows the preparation of oligoanilines of even or odd chain lengths, and the incorporation of a variety of functional groups into the oligomers. Polyanilines of low polydispersity can also be prepared by this method. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | December 2, 1998 |
| PATENT REFERENCES CITED |
Amit, B. et al., "Photosensitive Protecting Groups of Amino Sugars and Their Use in Glycside Synthesis. 2-Nitrobenzyloxycarbonylamino and 6-Nitrobenzyloxycarbonylamino Derivities", J. Org. Chem. , 39:192-196 (1974). Chen S. et al., "Electrically Conductive Polyaniline-Poly(vinyl alcohol) Composite Films: Physical Properties and Morphological Structures", Macromolecules, 24:1242-1248 (1991). D'Aprano G. et al., "Synthesis and Characterization of Polyaniline Derivatives: Poly(2-alkoxyanilines) and Poly(2,5-dialkoxyanilines)", Chem. Mater. , 7:33-42 (1995). DeBerry, D. "Modification of the Electrochemical and Corrosion Behavior of Stainless Steels with an Electroactive Coating", J. Electrochem. Soc. , 132:1022-1026 (1985). Driver, M. S. et al., "A. Second Generation Catalyst for Aryl Halide Amination: Mixed Secondary Amines from Aryl Halides and Primary Amines Catalyzed by (DPPF)PdCl2", J. Chem. Soc, 118:7217-7218 (1996). Graf, D. et al., "From Monomers to .pi.-Stacks. A Comprehensive Study of the Structure and properties of Monomeric, .pi.-Dimerized, and .pi.Stacked Forms of the Cation Radical of 3', 4'-Dibutyl-2,5"-diphenyl-2,2':5',2"-terthiophene", J. Am. Chem. Soc. , 119:5888-5599 (1997). Guram, A. S. et al., "A Simple Catalytic Method For the Conversion of Ayrl Bromides to Arylamines", Agnew. Chem. Int. Ed. Engl. , 34:1348-1350 (1995). Hadek, V. et al., "Electric Properties of Donor-Acceptor Comlexes of Olgoanilinic Compounds", Collection Czechoslov. Chem. Commun. , 34:3139-3144 (1969). Huang, W. et al., "Polyaniline, a Novel Conducting Polymer",J. Chem. Soc., Faraday Trans. 1, 82:2385-2400 (1986). Izatt, R. et al., "Thermodynamic and Kinetic Data For Cation-Macrocycle Interation", Chem. Rev. , 85:271-339 (1985). Lu F.-L.et al., "Phenyl-Capped Octaaniline(COA): An Excellent Model for Polyaniline", J. AM. Chem. Soc., 108:8311-8313 (1986). Moll, T. and Heinze, J., "Electrochemical and spectroscopic properties of oligoanilines", 6001 Chemical Abstracts, 119:18, p. 708 (1993). Ochi, M. et al., "Preperation of Linear Oliganiline Dervatives Using Titanium Alkoxide as a Condensing Agent", Bull. Chem. Soc. Japan, 67:1749-1752 (1994). Pillai, V. N. R. "Photoremovable Protecting Groups in Organic Synthesis", Synthesis, Jan.:1-26 (1980). Sadighi, J. P. et al., "Palladium-Catalyzed Synthesis of Monodisperse, COntrolled-Length and Functionalized Oligoanilines", J. Am. Chem. Soc. , 120:20, pp. 4961-4976 (1998). Singer, R. A. eta al., "A General Synthesis oif End-Functionalized Oligoanilines via Palladium-Catalyzed Amination", J. Am. Chem. Soc. , 120:1, pp. 213-214 (1998). Swager, T. M. et al., "Molecular Recognition and Chemoresistive Materials", Adv. Mater, 6:595-597 (1994). Walton, D.R.M. "The Protection OF Aminophenyl Groups in Organometallic Syntheses", J. Chem. Soc. , C;1706-1707 (1966). Wolfe, J.P. et al., "An Ammonia Equivalent for the Palladium-Catalyzed Amination of Aryl Halides and Triflates", Tetrahedron Letters, 38:6367-6370 (1997). Wolfe, J.P. et al., "An Improved Catalyst System for Aromatic Carbon-Nitrogen Bond Formation: The Possible Involvement of Bis(Phosphine) Palladium Complexes as Key Intermediates", J. Am. Chem. Soc. , 118:7215-7216 (1996). Wolfe, J.P. et al., "Palladium-Catalyzed Amination of Aryl Triflates", J. Org. Chem , 62:1264-1267 (1997). Wudl, F. et al., "Poly(.rho.-phenyleneamineimine): Synthesis and Comparison to Polyaniline", J. AM. Chem. Soc. , 109:3677-3684 (1987). |
| PATENT GOVERNMENT INTERESTS |
GOVERNMENT FUNDING This invention was supported in part with funds provided by the Office of Naval Research. The government has certain rights in the invention. |
| PATENT PARENT CASE TEXT | This data is not available for free |
| PATENT CLAIMS |
We claim: 1. A method for the synthesis of compounds comprising alternating protected heteroatom and aryl moieties, comprising the reaction of an activated compound, comprising alternating heteroatom and aryl moieties and one activated carbon bearing an activated group, with an amino-substituted compound, comprising alternating heteroatom and aryl moieties and an amine, in the presence of a transition metal catalyst under conditions suitable for the transition metal catalyst to effect the formation of a new carbon-nitrogen bond between the activated carbon of said activated compound and the amine of said amino-substituted compound. 2. The method of claim 1, characterized by the general reaction scheme: ##STR98## wherein X represents an activated group which can be replaced by a nucleophilic nitrogen in a transition metal-catalyzed arylation reaction; W represents, independently for each occurrence, as valence and stability permit, NV, O, S, PR, or Se; Ar represents, independently for each occurrence, as valence and stability permit, a substituted or unsubstituted aryl group; V represents, independently for each occurrence, a nitrogen-protecting group; R represents, independently for each occurrence, as valence and stability permit, H, a substituted or unsubstituted alkyl, aryl, or alkenyl moiety, a formyl, acyl, or sulfonyl moiety, or --(CH.sub.2).sub.m --R.sub.8 ; R.sub.8 represents, independently for each occurrence, a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle; m is an integer in the range 0-8 inclusive; and q and r are integers greater than or equal to 1. 3. A method for the synthesis of compounds comprising alternating heteroatom and aryl moieties, comprising the reaction of a bis-activated compound, comprising alternating heteroatom and aryl moieties and two activated carbons bearing activated groups, with two or more equivalents of an amino-substituted compound, comprising alternating heteroatom and aryl moieties and an amine, in the presence of a transition metal catalyst under conditions suitable for the transition metal catalyst to effect the formation of new carbon-nitrogen bonds between the activated carbons of said activated compound and the nitrogens of said amino-substituted compounds. 4. The method of claim 3, characterized by the general reaction scheme: ##STR99## wherein X represents an activated group which can be replaced by a nucleophilic nitrogen in a transition metal-catalyzed arylation reaction; W represents, independently for each occurrence, as valence and stability permit, NV, O, S, PR, or Se; Ar represents, independently for each occurrence, as valence and stability permit, a substituted or unsubstituted aryl group; V represents, independently for each occurrence, a nitrogen-protecting group; R represents, independently for each occurrence, as valence and stability permit, H, a substituted or unsubstituted alkyl, aryl, or alkenyl moiety, a formyl, acyl, or sulfonyl moiety, or --(CH.sub.2).sub.m --R.sub.8 ; R.sub.8 represents, independently for each occurrence, a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle; m and n are integers in the range 0-8 inclusive; and q and r are integers greater than or equal to 1. 5. A method for the synthesis of compounds comprising alternating heteroatom and aryl moieties, comprising the reaction of two or more equivalents of an activated compound, comprising alternating heteroatom and aryl moieties and one activated carbon bearing an activated group, with a bis-amino-substituted compound, comprising alternating heteroatom and aryl moieties and two amines, in the presence of a transition metal catalyst under conditions suitable for the transition metal catalyst to effect the formation of new carbon-nitrogen bonds between the activated carbons of said activated compounds and the amines of said amino-substituted compounds. 6. The method of claim 5, characterized by the general reaction scheme: ##STR100## wherein X represents an activated group which can be replaced by a nucleophilic nitrogen in a transition metal-catalyzed arylation reaction; W represents, independently for each occurrence, as valence and stability permit, NV, O, S, PR, or Se; Ar represents, independently for each occurrence, as valence and stability permit, a substituted or unsubstituted aryl group; V represents, independently for each occurrence, a nitrogen-protecting group; R represents, independently for each occurrence, as valence and stability permit, H, a substituted or unsubstituted alkyl, aryl, or alkenyl moiety, a formyl, acyl, or sulfonyl moiety, or --(CH.sub.2).sub.m --R.sub.8 ; R.sub.8 represents, independently for each occurrence, a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle; m and n are integers in the range 0-8 inclusive; and q and r are integers greater than or equal to 1. 7. The method of claim 1, 3 or 5, wherein all heteroatom moieties are nitrogens bearing nitrogen-protecting groups and all aryl moieties are substituted or unsubstituted phenyl moieties. 8. The method of claim 7, characterized by the general reaction scheme: ##STR101## wherein X represents an activated group which can be replaced by a nucleophilic nitrogen in a transition metal-catalyzed arylation reaction; P represents, independently for each occurrence, a nitrogen-protecting group; Y represents, independently for each occurrence, as valence and stability permit, H, halogen, lower alky, lower alkenyl, carbonyl group (e.g. ester, carboxyl, or formyl), thiocarbonyl (e.g. thiolester, thiolcarboxylate, or thiolformate), ketone, aldehyde, amino, acylamino, amido, amidino, cyano, nitro, azido, sulfonyl, sulfoxido, sulfate, sulfonate, sulfamoyl, sulfonamido, phosphoryl, phosphonate, phosphinate, --(CH.sub.2).sub.m --R.sub.8, --(CH.sub.2).sub.m --OH, --(CH.sub.2).sub.m --O-lower alkyl, --(CH.sub.2).sub.m --O-lower alkenyl, --O--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --SH, --(CH.sub.2).sub.m --S-lower alkyl, --(CH.sub.2).sub.m --S-lower alkenyl, --S--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --NH.sub.2, --(CH.sub.2).sub.m --NH-lower alkyl, --(CH.sub.2).sub.m --NH-lower alkenyl, --NH--(CH.sub.2).sub.n --R.sub.8, or protected forms of the above, or a solid or polymeric support; R represents, independently for each occurrence, as valence and stability permit, H, a substituted or unsubstituted alkyl, aryl, or alkenyl moiety, a formyl, acyl, or sulfonyl moiety, or --(CH.sub.2).sub.m --R.sub.8 ; R.sub.8 represents, independently for each occurrence, a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle; m and n are integers in the range 0-8 inclusive; and q and r are integers greater than or equal to 1. 9. The method of claim 7, characterized by the general reaction scheme: ##STR102## wherein X represents an activated group which can be replaced by a nucleophilic nitrogen in a transition metal-catalyzed arylation reaction; P represents, independently for each occurrence, a nitrogen-protecting group; Y represents, independently for each occurrence, as valence and stability permit, H, halogen, lower alkyl, lower alkenyl, carbonyl group (e.g. ester, carboxyl, or formyl), thiocarbonyl (e.g. thiolester, thiolcarboxylate, or thiolformate), ketone, aldehyde, amino, acylamino, amido, amidino, cyano, nitro, azido, sulfonyl, sulfoxido, sulfate, sulfonate, sulfamoyl, sulfonamido, phosphoryl, phosphonate, phosphinate, --(CH.sub.2).sub.m --R.sub.8, --(CH.sub.2).sub.m --OH, --(CH.sub.2).sub.m --O-lower alkyl, --(CH.sub.2).sub.m --O-lower alkenyl, --O--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --SH, --(CH.sub.2).sub.m --S-lower alkyl, --(CH.sub.2).sub.m --S-lower alkenyl, --S--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --NH.sub.2, --(CH.sub.2).sub.m --NH-lower alkyl, --(CH.sub.2).sub.m --NH-lower alkenyl, --NH--(CH.sub.2).sub.n --R.sub.8, or protected forms of the above, or a solid or polymeric support; R represents, independently for each occurrence, as valence and stability permit, H, a substituted or unsubstituted alkyl, aryl, or alkenyl moiety, a formyl, acyl, or sulfonyl moiety, or --(CH.sub.2).sub.m --R.sub.8 ; R.sub.8 represents, independently for each occurrence, a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle; m and n are integers in the range 0-8 inclusive; and q and r are integers greater than or equal to 1. 10. The method of claim 7, characterized by the general reaction scheme: ##STR103## wherein X represents an activated group which can be replaced by a nucleophilic nitrogen in a transition metal-catalyzed arylation reaction; Ar represents, independently for each occurrence, as valence and stability permit, an aryl group; P represents, independently for each occurrence, a nitrogen-protecting group; Y represents, independently for each occurrence, as valence and stability permit, H, halogen, lower alkyl, lower alkenyl, carbonyl group (e.g. ester, carboxyl, or formyl), thiocarbonyl (e.g. thiolester, thiolcarboxylate, or thiolformate), ketone, aldehyde, amino, acylamino, amido, amidino, cyano, nitro, azido, sulfonyl, sulfoxido, sulfate, sulfonate, sulfamoyl, sulfonamido, phosphoryl, phosphonate, phosphinate, --(CH.sub.2).sub.m --R.sub.8, --(CH.sub.2).sub.m --OH, --(CH.sub.2).sub.m --O-lower alkyl, --(CH.sub.2).sub.m --O-lower alkenyl, --O--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --SH, --(CH.sub.2).sub.m --S-lower alkyl, --(CH.sub.2).sub.m --S-lower alkenyl, --S--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --NH.sub.2, --(CH.sub.2).sub.m --NH-lower alkyl, --(CH.sub.2).sub.m --NH-lower alkenyl, --NH--(CH.sub.2).sub.n --R.sub.8, or protected forms of the above, or a solid or polymeric support; R represents, independently for each occurrence, as valence and stability permit, H, a substituted or unsubstituted alkyl, aryl, or alkenyl moiety, a formyl, acyl, or sulfonyl moiety, or --(CH.sub.2).sub.m --R.sub.8 ; R.sub.8 represents, independently for each occurrence, a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle; m and n are integers in the range 0-8 inclusive; and q and r are integers greater than or equal to 1. 11. A method for the synthesis of polymers comprising alternating heteroatom and aryl moieties, comprising the polymerization of one or more different activated and amino-substituted compounds, comprising alternating heteroatom and aryl moieties, at least one amine, and at least one activated carbon bearing an activated group, in the presence of a transition metal catalyst under conditions suitable for the transition metal catalyst to effect the formation of a new carbon-nitrogen bond between amines and activated carbons of said activated and amino-substituted compounds. 12. The method of claim 11, characterized by the general reaction scheme: ##STR104## wherein X represents an activated group which can be replaced by a nucleophilic nitrogen in a transition metal-catalyzed arylation reaction; W represents, independently for each occurrence, as valence and stability permit, NP, O, S, PR, or Se; Ar represents, independently for each occurrence, as valence and stability permit, a substituted or unsubstituted aryl group; P represents, independently for each occurrence, a nitrogen-protecting group; Y represents, independently for each occurrence, as valence and stability permit, H, halogen, lower alkyl, lower alkenyl, carbonyl group (e.g. ester, carboxyl, or formyl), thiocarbonyl (e.g. thiolester, thiolcarboxylate, or thiolformate), ketone, aldehyde, amino, acylainino, amido, amidino, cyano, nitro, azido, sulfonyl, sulfoxido, sulfate, sulfonate, sulfamoyl, sulfonamido, phosphoryl, phosphonate, phosphinate, --(CH.sub.2).sub.m --R.sub.8, --(CH.sub.2).sub.m --OH, --(CH.sub.2).sub.m --O-lower alkyl, --(CH.sub.2).sub.m --O-lower alkenyl, --O--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --SH, --(CH.sub.2).sub.m --S-lower alkyl, --(CH.sub.2).sub.m --S-lower alkenyl, --S--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --NH.sub.2, --(CH.sub.2).sub.m --NH-lower alkyl, --(CH.sub.2).sub.m --NH-lower alkenyl, --NH--(CH.sub.2).sub.n --R.sub.8, or protected forms of the above, or a solid or polymeric support; R represents, independently for each occurrence, as valence and stability permit, H, a substituted or unsubstituted alkyl, aryl, or alkenyl moiety, a formyl, acyl, or sulfonyl moiety, or --(CH.sub.2).sub.m --R.sub.8 ; R.sub.8 represents, independently for each occurrence, a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle; m and n are integers in the range 0-8 inclusive; q is an integer greater than or equal to 1; and r is an integer greater than 1. 13. A method for the synthesis of polymers comprising alternating heteroatom and aryl moieties, comprising the polymerization of one or more different bis-activated compounds, each comprising alternating heteroatom and aryl moieties and two activated carbons bearing activated groups, with one or more different bis-amino-substituted compounds, each comprising alternating heteroatom and aryl moieties and two amines, in the presence of a transition metal catalyst under conditions suitable for the transition metal catalyst to effect the formation of new carbon-nitrogen bonds between amines of said bis-amino-substituted compounds and activated carbons of said bis-activated compounds. 14. The method of claim 13, characterized by the general reaction scheme: ##STR105## wherein X represents an activated group which can be replaced by a nucleophilic nitrogen in a transition metal-catalyzed arylation reaction; W represents, independently for each occurrence, as valence and stability permit, NP, O, S, PR, or Se; Ar represents, independently for each occurrence, as valence and stability permit, a substituted or unsubstituted aryl group; P represents, independently for each occurrence, a nitrogen-protecting group; Y represents, independently for each occurrence, as valence and stability permit, H, halogen, lower alkyl, lower alkenyl, carbonyl group (e.g. ester, carboxyl, or formyl), thiocarbonyl (e.g. thiolester, thiolcarboxylate, or thiolformate), ketone, aldehyde, amino, acylamino, amido, amidino, cyano, nitro, azido, sulfonyl, sulfoxido, sulfate, sulfonate, sulfamoyl, sulfonamido, phosphoryl, phosphonate, phosphinate, --(CH.sub.2).sub.m --R.sub.8, --(CH.sub.2).sub.m --OH, --(CH.sub.2).sub.m --O-lower alkyl, --(CH.sub.2).sub.m --O-lower alkenyl, --O--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --SH, --(CH.sub.2).sub.m --S-lower alkyl, --(CH.sub.2).sub.m --S-lower alkenyl, --S--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --NH.sub.2, --(CH.sub.2).sub.m --NH-lower alkyl, --(CH.sub.2).sub.m --NH-lower alkenyl, --NH--(CH.sub.2).sub.n --R.sub.8, or protected forms of the above, or a solid or polymeric support; R represents, independently for each occurrence, as valence and stability permit, H, a substituted or unsubstituted alkyl, aryl, or alkenyl moiety, a formyl, acyl, or sulfonyl moiety, or --(CH.sub.2).sub.m --R.sub.8 ; R.sub.8 represents, independently for each occurrence, a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle; m and n are integers in the range 0-8 inclusive; q and r are integers greater than or equal to 1; and t is an integer greater than 1. 15. The method of claim 11 or 13, wherein all heteroatom moieties are nitrogens bearing nitrogen-protecting groups and all aryl moieties are substituted or unsubstituted phenyl moieties. 16. The method of claim 15, characterized by the general reaction scheme: ##STR106## wherein X represents an activated group which can be replaced by a nucleophilic nitrogen in a transition metal-catalyzed arylation reaction; P represents, independently for each occurrence, a nitrogen-protecting group; Y represents, independently for each occurrence, as valence and stability permit, H, halogen, lower alkyl, lower alkenyl, carbonyl group (e.g. ester, carboxyl, or formyl), thiocarbonyl (e.g. thiolester, thiolcarboxylate, or thiolformate), ketone, aldehyde, amino, acylamino, amido, amidino, cyano, nitro, azido, sulfonyl, sulfoxido, sulfate, sulfonate, sulfamoyl, sulfonamido, phosphoryl, phosphonate, phosphinate, --(CH.sub.2).sub.m --R.sub.8, --(CH.sub.2).sub.m --OH, --(CH.sub.2).sub.m --O-lower alkyl, --(CH.sub.2).sub.m --O-lower alkenyl, --O--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --SH, --(CH.sub.2).sub.m --S-lower alkyl, --(CH.sub.2).sub.m --S-lower alkenyl, --S--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --NH.sub.2, --(CH.sub.2).sub.m --NH-lower alkyl, --(CH.sub.2).sub.m --NH-lower alkenyl, --NH--(CH.sub.2).sub.n --R.sub.8, or protected forms of the above, or a solid or polymeric support; R represents, independently for each occurrence, as valence and stability permit, H, a substituted or unsubstituted alkyl, aryl, or alkenyl moiety, a formyl, acyl, or sulfonyl moiety, or --(CH.sub.2).sub.m --R.sub.8 ; R.sub.8 represents, independently for each occurrence, a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle; m and n are integers in the range 0-8 inclusive; q is an integer greater than or equal to 1; and r is an integer greater than 1. 17. The method of claim 15, characterized by the general reaction scheme: ##STR107## wherein X represents an activated group which can be replaced by a nucleophilic nitrogen in a transition metal-catalyzed arylation reaction; P represents, independently for each occurrence, a nitrogen-protecting group; Y represents, independently for each occurrence, as valence and stability permit, H, halogen, lower alkyl, lower alkenyl, carbonyl group (e.g. ester, carboxyl, or formyl), thiocarbonyl (e.g. thiolester, thiolcarboxylate, or thiolformate), ketone, aldehyde, amino, acylamino, amido, amidino, cyano, nitro, azido, sulfonyl, sulfoxido, sulfate, sulfonate, sulfamoyl, sulfonamido, phosphoryl, phosphonate, phosphinate, --(CH.sub.2).sub.m --R.sub.8, --(CH.sub.2).sub.m --OH, --(CH.sub.2).sub.m --O-lower alkyl, --(CH.sub.2).sub.m --O-lower alkenyl, --O--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --SH, --(CH.sub.2).sub.m --S-lower alkyl, --(CH.sub.2).sub.m --S-lower alkenyl, --S--(CH.sub.2).sub.n --R.sub.8, --(CH.sub.2).sub.m --NH.sub.2, --(CH.sub.2).sub.m --NH-lower alkyl, --(CH.sub.2).sub.m --NH-lower alkenyl, --NH--(CH.sub.2).sub.n --R.sub.8, or protected forms of the above, or a solid or polymeric support; R represents, independently for each occurrence, as valence and stability permit, H, a substituted or unsubstituted alkyl, aryl, or alkenyl moiety, a formyl, acyl, or sulfonyl moiety, or --(CH.sub.2).sub.m --R.sub.8 ; R.sub.8 represents, independently for each occurrence, a substituted or unsubstituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle; m and n are integers in the range 0-8 inclusive; q and r are integers greater than or equal to 1; and t is an integer greater than 1. 18. The method of claim 15, wherein the polymer synthesized exhibits a polydispersity less than 5. 19. The method of claim 7 or 15, wherein the nitrogen-protecting groups are acyl groups. 20. The method of claim 7 or 15, wherein the nitrogen-protecting groups are carbamates. 21. The method of claim 7 or 15, wherein the carbamates are t-butyl carbamates. 22. The method of claim 1, 3, 5, 7, 11, 13, or 15, wherein the transition metal catalyst is selected from metals in Groups 5-12, inclusive. 23. The method of claim 22, wherein the transition metal catalyst is selected from the group consisting of Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, and Cu. 24. The method of claim 1, 3, 5, 7, 11, 13, or 15, wherein the transition metal catalyst is present in substoichiometric quantities relative to the limiting reagent among said activated compound, said amino-substituted compound, said activated amino-substituted compound, said bis-activated compound, or said bis-amino-substituted compound. 25. The method of claim 1, 3, 5, 7, 11, 13, or 15, wherein the transition metal catalyst is present in less than or equal to 50 mol % relative to the limiting reagent among said activated compound, said amino-substituted compound, said activated amino-substituted compound, said bis-activated compound, or said bis-amino-substituted compound. 26. The method of claim 1, 3, 5, 7, 11, 13, or 15, wherein the transition metal catalyst is present in less than or equal to 10 mol % relative to the limiting reagent among said activated compound, said amino-substituted compound, said activated amino-substituted compound, said bis-activated compound, or said bis-amino-substituted compound. 27. The method of claim 1, 3, 5, 7, 11, 13, or 15, wherein the transition metal catalyst is present in less than or equal to 5 mol % relative to the limiting reagent among said activated compound, said amino-substituted compound, said activated amino-substituted compound, said bis-activated compound, or said bis-amino-substituted compound. 28. The method of claim 1, 3, 5, 7, 11, 13, or 15, wherein the transition metal catalyst is present in less than or equal to 2.5 mol % relative to the limiting reagent among said activated compound, said amino-substituted compound, said activated amino-substituted compound, said bis-activated compound, or said bis-amino-substituted compound. 29. The method of claim 1, 3, 5, 7, 11, 13, or 15, wherein the activated group is selected from the group comprising halides and sulfonates. 30. The method of claim 29, wherein the activated group is selected from the group comprising chloride, bromide, iodide, tosylate, mesylate, triflate, and nonaflate. 31. The method of claim 1, 3, 5, 7, 11, 13, or 15, wherein the conditions comprise a supporting ligand. 32. The method of claim 31, wherein the ligand is selected from the set comprising phosphine and phosphite ligands. 33. The method of claim 31, wherein the ligand is selected from the set comprising achiral and chiral chelating ligands. 34. The method of claim 31, wherein the ligand is racemic or non-racemic BINAP. 35. The method of claim 1, 3, 5, 7, 11, 13, or 15, wherein a varied library of oligomers is produced via parallel, combinatorial synthetic methods. 36. The method of claim 34, wherein members of the library are attached to solid support. 37. The method of claim 2, 4, 6, 8, 9, 10, 12, 14, 16, or 17, wherein Y or R comprises functionality suitable for use in a sensor. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
BACKGROUND OF THE INVENTION Polyaniline has attracted much attention in the field of organic conducting polymers due to its robust nature in the doped emeraldine state. See, for example, Huang et al. (1986) J. Chem. Soc. Faraday Trans. 82:2385-2400; Chen et al. (1991) Macromolecules 24:1242-1248; and Chiang et al. (1986) Synth. Met. 13:193-205. Among the many industrial applications it has found are its use as components in rechargeable batteries (MacDiarmid et al. (1986) Mol. Cryst. Liq. Cryst. 121:187-190), electromagnetic interference shielding (Taka et al. (1991) Synth. Met. 41:1177-1180; Colaneri et al. (1992) IEEE Trans. Instrum. Meas. 41:291; and Joo et al. (1994) Appl. Phys. Lett. 65:2278-2280), and anticorrosion coatings for steel (DeBerry et al. (1985) J. Electrochem. Soc. 132:1022-1026; Ahmad et al. (1996) Synth. Met. 78:103-110; and Lu et al. (1995) Synth. Met. 71:2163-2166). In 1986, Wudl and coworkers demonstrated that synthetically prepared phenyl-capped octaaniline exhibited properties similar to bulk polyaniline (comparable UV/vis, IR, CV, and conductivity). See Lu et al. (1986) J. Am. Chem. Soc. 108:8311-8313; Wudl et al. (1987) J. Am. Chem. Soc. 109:3677-3684. Consequently, an octaaniline may be considered a good model or substitute for applications involving polyaniline. Aside from the modified Honzl condensation method employed by Wudl for synthesizing oligoanilines, other methods of preparation include titanium alkoxide-mediated couplings of aniline derivatives (Ochi et al. (1994) J. Bull. Chem. Soc. Jpn. 67:1749-1752), Ullmann couplings (Rebourt et al. (1997) Synth. Met. 84:65-66), and an adaptation of the Willstatter-Moore approach (Zhang et al. (1997) J. Synth. Met. 84:119-120). However, none of these methods have demonstrated generality in the choice of substrates for oligomerizations, and all lack the ability to functionalize end groups. BRIEF SUMMARY OF THE INVENTION New methods for the synthesis of electroactive polymers and the preparation of films thereof are disclosed. Oligomeric variants of these electroactive compounds are also prepared by similar methods here disclosed. Preparation of both types of compounds hinges upon the transition metal-mediated coupling of aryl amines with activated aryl compounds. The method disclosed herein provides for the synthesis of electroactive compounds which are stable to ambient atmosphere, are soluble in common organic solvents, and can be readily manipulated into useful forms. In one aspect of the invention, a process is described for the synthesis of compounds comprising alternating aryl and heteroatomic groups by means of the transition metal-mediated process described above. Another aspect of the invention provides for the synthesis of symmetrical compounds by means of the bidirectional chain extension of a core fragment comprising alternating aryl and heteroatomic functionalities. In another aspect of the invention, a process is described for the synthesis of polymeric compounds comprising alternating aryl and heteroatomic groups. A further aspect of the invention provides for the synthesis of protected oligoanilines by means of the transition metal-mediated coupling of an aryl amine with an activated aryl compound. Yet another aspect of the invention describes the preparation of protected symmetrical oligoanilines through the bidirectional chain extension of a core oligoaniline subunit. An additional aspect of the invention provides for the transition metal-mediated polymerization of oligoaniline subunits for the preparation of protected polyanilines. In another aspect of the invention, a process is described for the metallation and substitution of activated protected aniline rings. A further aspect of the invention provides compounds comprising chains of alternating heteroatomic and aryl moieties. Yet another aspect of the invention provides protected oligoanilines which can be deprotected and rendered electroactive under specific conditions. An additional aspect of the invention provides protected polyanilines of low polydispersity. In another aspect of the invention, protected versions of electroactive polyanilines which can be deprotected and activated under specific conditions are provided |
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