Synthesis of oligoarylamines, and uses and reagents related...

Details Synthesis of oligoarylamines, and uses and reagents related... Synthesis of oligoarylamines, and uses and reagents related...

1998-12-02

2001-05-22

Truong, Duc (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Treating polymer containing material or treating a solid...

C528S422000, C528S488000, C528S492000, C564S386000, C564S376000, C564S391000, C564S395000, C252S644000, C430S270100, C430S004000

Reexamination Certificate

active

06235871

ABSTRACT:

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 Willstätter-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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