Reactions of the perfluoroalkyltriazapentadiene Ph2N3C2(C3F7)2H with acids, bases, and water

A R Siedle; Robert J Webb; Myles Brostrom; Shih-Hung Chou; David A Weil; Richard A Newmark; Fred E Behr; Victor G Young Jr

doi:10.1021/ic020716q

Reactions of the perfluoroalkyltriazapentadiene Ph2N3C2(C3F7)2H with acids, bases, and water

Inorg Chem. 2003 Apr 21;42(8):2596-601. doi: 10.1021/ic020716q.

Authors

A R Siedle¹, Robert J Webb, Myles Brostrom, Shih-Hung Chou, David A Weil, Richard A Newmark, Fred E Behr, Victor G Young Jr

Affiliation

¹ 3M Corporate Research Laboratories, St. Paul, Minnesota 55144, USA. arsiedle@mmm.com

PMID: 12691566
DOI: 10.1021/ic020716q

Abstract

Treatment of the bis(perfluoroalkyl)triazapentadiene PhN=C(C(3)F(7))-N=C(C(3)F(7))-NHPh, 2, with bases affords salts of the conjugate base. Alkylation of the Na(+) salt with CH(3)I yields PhN=C(C(3)F(7))-N=C(C(3)F(7))-NMePh. The crystal structure of [Bu(4)N][Ph(2)N(3)C(2)(C(3)F(7))(2)] demonstrates a twisted, zigzag geometry for the anion in the solid state, but in solution, it is conformationally unstable. Both compounds are stable in aqueous methanol, but hydrolysis occurs under acidic conditions. Protonation with CF(3)SO(3)H acid occurs at the sp(2) nitrogen to give [PhN-(H) HC(C(3)F(7))-C(C(3)F(7))-NHPh][CF(3)SO(3)]. Heating 2 in CF(3)SO(3)H produces 2,4-bis(heptafluoropropyl)-1,3-quinazoline.