Preparation of Halogenated Fluorescent Diaminophenazine Building Blocks

Koepf, Matthieu; Lee, Shin Hee; Brennan, Bradley J.; Méndez-Hernández, Dalvin D.; Batista, Victor S.; Brudvig, Gary W.; Crabtree, Robert H.

doi:10.1021/acs.joc.5b01339

Preparation of Halogenated Fluorescent Diaminophenazine Building Blocks

Journal Article · Mon Sep 21 00:00:00 EDT 2015 · Journal of Organic Chemistry

DOI:https://doi.org/10.1021/acs.joc.5b01339· OSTI ID:1370815

Koepf, Matthieu ^[1]; Lee, Shin Hee ^[1]; Brennan, Bradley J. ^[1]; Méndez-Hernández, Dalvin D. ^[1]; Batista, Victor S. ^[1]; Brudvig, Gary W. ^[1]; Crabtree, Robert H. ^[1]

Yale Univ., New Haven, CT (United States)

A short, convenient, and scalable protocol for the one-pot synthesis of a series of fluorescent 7,8-dihalo-2,3-diaminophenazines is introduced. The synthetic route is based on the oxidative condensation of 4,5-dihalo-1,2-diaminobenzenes in aqueous conditions. The resulting diaminophenazines could be attractive intermediates for the preparation of polyfunctional phenazines and extended polyheteroacenes. We find that the undesired hydroxylation byproducts, typically obtained in aqueous conditions, are completely suppressed by addition of a stoichiometric amount of acetone during the oxidation step allowing for selective formation of 7,8-dihalo-2,2-dimethyl-2,3-dihydro-1H-imidazo[4,5-b]phenazine derivatives with good to excellent yields. Under reductive conditions, the imidazolidine ring can be hydrolyzed into the desired 7,8-dihalo-2,3-diaminophenazines. Furthermore, we report a selective route under highly reducing conditions to monohydrodeaminate the 2,3-di(methylamino) phenazine derivatives, which allows for further structural variations of these phenazine building blocks. Finally, all of these derivatives are luminescent, with measured fluorescence quantum-yields of up to 80% in ethanol for the more rigid structures, highlighting the potential of such materials to provide new fluorophores.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FG02-07ER15909; SC0001059

OSTI ID:: 1370815

Journal Information:: Journal of Organic Chemistry, Journal Name: Journal of Organic Chemistry Journal Issue: 20 Vol. 80; ISSN 0022-3263

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Preparation of Halogenated Fluorescent Diaminophenazine Building Blocks

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