Heterosubstituted or Functionalized Derivatives of 1- and 2-(Trifluoro­methyl)naphthalenes Emanating from Aryne Adducts

Abstract

More than two dozen new CF 3 -substituted naphthalene derivatives were prepared in an expedient way by employing 3-and 4-(trifluoromethyl)benzyne as the key intermediates. 2-and 4-Chlorobenzotrifluoride were treated with butyllithium and the organometallic species thus generated were allowed to decompose in the presence of furan. The resulting cycloadducts 1 and 14 were reduced to the (trifluoromethyl)naphthalenes 2 and 15, ring-opened to the (trifluoromethyl)naphthols 3, 16 and 17 and transformed to the dibromo adducts 5 and 18. The latter were stereoselectively converted into the bromo-1,4-epoxy-1,4-dihydro(trifluoromethyl)naphthalenes 6, 7, 19 and 20 and, by deoxygenation, into various bromo(trifluoromethyl)naphthalenes 8, 9, 21 and 22. Trifluoromethyl substituted naphthoic acids 10-13 and 23-26 were obtained when the bromo compounds 6-9 and 19-22 were subjected to a halogen/metal permutation followed by carboxylation.

Redefining the Robeson upper bounds for CO2/CH4 and CO2/N2 separations using a series of ultrapermeable benzotriptycene-based polymers of intrinsic microporosity

“…44 Monomers were prepared by adaptation of the classic benzotriptycene synthesis, involving the Diels-Alder reaction between 2,3,6,7-tetramethoxy-9,10-dimethylanthracene and the appropriate 1,4-dihydro-1,4-epoxynaphthalene 39 -with the latter prepared from the Diels-Alder reaction between the appropriate benzyne intermediate and furan. [45][46][47] PIM-TMN-Trip and PIM-HMI-Trip are both soluble in chloroform, facilitating analysis using Gel Permeation Chromatography (GPC) that confirmed that high molecular mass polymer was achieved for both polymers ( Table 1). In contrast, PIM-DM-Btrip, PIM-TFM-BTrip and PIM-DTFM-BTrip proved soluble only in quinoline.…”