Quadricyclane—thermal cycloaddition to polyfluorinated carbonyl compounds

Reactions of quadricyclane with fluorinated nitrogen-containing compounds. Synthesis of 3-aza-4-perfluoroalkyl-tricyclo[4.2.1.02,5]non-3,7-dienes

“…19 F NMR spectrum of minor isomer 7b is distinctly different. First of all, substantial downfield shift is observed for resonance of F-4 (d = À129.05 for 7b versus d = À141.70 for 7a; similar downfield shift for F-4 was previously observed in 19 F NMR spectra of minor isomers of cycloadducts of 1 and CF 3 C(O)F or FSO 2 CF 2 C(O)F, also having anti-orientation of F-4 in an oxetane ring relative to CH 2 bridge [14]). In 1 H NMR spectrum of 7b the signal of H-5 (d = 2.22, dd, J = 21.5, 5.7 Hz), coupled to H-2 (d = 3.87, d, J = 5.7 Hz) has also a substantial three-bond coupling constant to F-4 (J 3 H-5ÀF-4 ¼ 21:5 Hz).…”

“…In sharp contrast to hexafluoroacetone, which reacts with 1 exothermally [14], the reaction of imine of hexafluoroacetone (2) with 1 is very slow even at elevated temperature (110 8C, 16 h) leading to formation of trace of the cycloadduct 3.…”

“…(5)) having small but distinct difference in chemical shifts ($0.1 ppm); the value of coupling constants J 3 H-2ÀH-5 in 11-13 (determined in selective 1 H homodecoupling experiments) are smaller than similar coupling constant in 3, 7a,b [J 3 H-2ÀH-5 ¼ 2:6 for 11-13 versus 4.9 (7a) and 5.7 (7b) Hz; see Table 2 The C=N bond in compounds 11-13 is highly reactive towards nucleophiles. For example, the reaction with CF 3 Si(CH 3 ) 3 (14) in the presence of CsF catalyst proceeds exothermally in THF, giving products 15-17 in high yield.…”

“…In search for new monomers for preparation of functional polymers for the next generation microlithography [12,13], we started investigation of the reactivity of quadricyclane towards fluorinated substrates. Recently, we have demonstrated that fluorinated carbonyl compounds rapidly react with 1 with the formation of a variety of norbonenoxetanes [14]. In this study an investigation of the reactivity of nitrogen-containing substrates towards 1 was attempted.…”

New Amorphous Fluoropolymers of Tetrafluoroethylene with Fluorinated and Non-Fluorinated Tricyclononenes. Semiconductor Photoresists for Imaging at 157 and 193 nm

“…27 Thus, reactions of quadricyclane with hexafluoroisobutylene, tert-butyl acrylate, di-tert-butyl fumarate, di-tert-butyl maleate, hexafluoroacetone, FC(O)CF 2 SO 2 F, and bis(trifluoromethyl)ketene 28 provided monomers 1d, 1o, 1q, 1r, 2a, 2b, and 2c, respectively. Monomers 1l, 1m, and 1n were prepared by reaction of the corresponding fluorinated acrylic acid fluorides with quadricyclane followed by conversion of the acid fluoride to the tertbutyl ester using potassium tert-butoxide.…”