The photochemical generation of elemental Br2 from brominated methanes is reported. Br2 was generated by the vaporization of carbon oxides and HBr through oxidative photodecomposition of brominated methanes under a 20 W low‐pressure mercury lamp, wherein the amount and situations of Br2 generation were photochemically controllable. Liquid CH2Br2 can be used not only as an organic solvent but also for the photoresponsive molecular storage of Br2, which is of great technical benefit in a variety of organic syntheses and in materials science. By taking advantage of the in situ generation of Br2 from the organic solvent itself, many organobromine compounds were synthesized in high practical yields with or without the addition of a catalyst. Herein, Br2 that was generated by the photodecomposition of CH2Br2 retained its reactivity in solution to undergo essentially the same reactions as those that were carried out with solutions of Br2 dissolved in CH2Br2 that were prepared without photoirradiation. Furthermore, HBr, which was generated during the course of the photodecomposition of CH2Br2, was also available for the substitution of the OH group for the Br group and for the preparation of the HBr salts of amines. Furthermore, the photochemical generation of Br2 from CH2Br2 was available for the area‐selective photochemical bleaching of natural colored plants, such as red rose petals, wherein Br2 that was generated photochemically from CH2Br2 was painted onto the petal to cause radical oxidations of the chromophoric anthocyanin molecules.
Transesterification reactions of acyclic oligoether esters E3-E10 with metal alkoxides were accelerated upon noncovalent complexation of the esters with metal ions. In the reaction of monovalent alkaline metal alkoxides, CH(3)ONa and CH(3)OK, plots of the observed rate constants k(obs) with respect to the chain length of E3-E10 showed selective acceleration of the transesterification. Compared with the shortest E3, which can hardly bind metal ion, 4.3- and 6.6-fold accelerations in the maxima were achieved in the combinations of E5/CH(3)ONa and E6/CH(3)OK, respectively. Supramolecular intermediate complex could be spectrometrically visualized by ESI-FT-ICR-MS in the course of reaction. Kinetic experiments, together with structural analyses by means of NMR, mass spectrometry, and DFT calculations of the intermediate complexes, indicate that a size-fit complex of host substitute with alkali metal ion allows strong electron withdrawing due to the close contact of the carbonyl oxygen to the metal ion, resulting in the selective rate enhancement of the reaction, while in the reaction of E3-E10 with a divalent alkaline earth metal alkoxide, (CH(3)CH(2)O)(2)Ba, the k(obs) values increased stepwise with elongation of the side arm to attain an dramatic large acceleration. In comparison with the k(obs) of E3, 4610-fold acceleration was achieved in the reaction of E10. The double activation of the host substrate and guest counter nucleophile at once brings about this extraordinary rate acceleration. The strong wrapping complexation of long oligoether ester with barium ethoxide allows for the effective electron withdrawal from the ester carbonyl group (host activation) as well as separation of the accompanying guest alkoxide anions (guest activation).
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