[reaction: see text] Reaction of a ketocalixarene with 2.2 equiv or an excess of PhLi affords diaddition and tetraaddition products, respectively. Ionic hydrogenation of the tetraalcohol 8a yields a calix[4]arene monosubstituted by phenyl groups at all four methylene bridges.
Reaction of dioxocalix[4]arene 7 with MeLi followed by 2-fold elimination of water yielded calixarene 8 possessing exocyclic double bonds at two adjacent bridges. Calixarene 8 exists in tetrachloroethane-d2 solution at rt, as a 2.3:1 mixture of the 1,3-alternate and partial cone conformers. Keto[n]calixarenes (n = 5, 6) were prepared via hydrolysis of the bromocalixarenes 11 and 12, followed by CrO3 oxidation of the respective hydroxymethylene derivatives. Addition of MeLi to the ketocalix[n]arenes (n = 4, 5 and 6) followed by elimination of water yielded the corresponding calix[n]radialenes. Calix[5]- and calix[6]radialenes adopt in the crystal irregular alternate (i.e., noncone) conformations.
Hexabromocalix[4]arene derivatives (3a and 3b) possessing pairs of dibromomethylene and bromomethylene groups located at distal or proximal positions of the calix scaffold were prepared via photochemical bromination of tetramethoxycalix[4]arene. The dibromomethylene groups undergo hydrolysis to afford calix[4]arenes possessing pairs of carbonyl groups and bromomethylene groups located at distal or proximal bridges (4a and 4b, respectively). The bromomethylene groups of 4 undergo reactions with nucleophiles under S(N)1 conditions to afford a wide array of derivatives possessing two different chemical modifications at the bridges.
The 400 MHz 1H NMR spectrum of the tetramethoxycalixarene 2 (possessing hydroxyl groups at the bridges) in commercial acetone-d6 displays five signals (an isotopic multiplet) for a pair of methoxy groups. Inspection of the X-ray structures of 2 and its isomer 3 indicates that in the adopted 1,3-alternate conformation, the methoxy groups intramolecularly hydrogen bonded to neighboring OH groups are oriented "in" (pointing toward the cavity). Upon dissolution of 2 in acetone-d6, none, some, or all of the OH protons exchange with the deuterium atoms present in the residual water of the solvent. Several species (mutually relating as isotopomers and isotopologues) differing in the number and positions of the deuterated hydroxyl groups are possible for 2. In three of these species, the "in"-"out"/"out"-"in" conformational equilibrium of a pair of methoxy groups is nondegenerate. The four external lines of the apparent multiplet are ascribed to a single- and double-isotopic perturbation of the "in"-"out" conformational equilibrium of a pair of methoxy groups. On the basis of the assignment of the signals to the individual species and their statistical distribution, the intensities of the components of the isotopic multiplet obtained at different isotopic enrichments of the hydroxyl groups could be simulated. A sample of 2 55% deuterated at the hydroxyl groups in CDCl3 displayed an isotopic multiplet consisting of nine signals. The isotopic multiplet observed for the OH groups of 2 in acetone-d6 was simulated at different deuteration enrichments.
The crowded methylene-functionalized calix[4]arenes 4 and 5 display restricted rotation of the tert-butyl substituents at the bridges. At low temperatures, separate signals were observed for the methyls of these groups in the (1)H NMR spectra.
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