598-71-0Relevant articles and documents
Induced Fitting and Polarization of a Bromine Molecule in an Electrophilic Inorganic Molecular Cavity and Its Bromination Reactivity
Hayashi, Yoshihito,Inada, Yasuhiro,Katayama, Misaki,Kikukawa, Yuji,Kitajima, Hiromasa,Seto, Kensuke,Watanabe, Daiki,Yamashita, Shohei
supporting information, p. 14399 - 14403 (2020/07/13)
Dodecavanadate, [V12O32]4? (V12), possesses a 4.4 ? cavity entrance, and the cavity shows unique electrophilicity. Owing to the high polarizability, Br2 was inserted into V12, inducing the inversion of one of the VO5 square pyramids to form [V12O32(Br2)]4? (V12(Br2)). The inserted Br2 molecule was polarized and showed a peak at 185 cm?1 in the IR spectrum. The reaction of V12(Br2) and toluene yielded bromination of toluene at the ring, showing the electrophilicity of the inserted Br2 molecule. Compound V12(Br2) also reacted with propane, n-butane, and n-pentane to give brominated alkanes. Bromination with V12(Br2) showed high selectivity for 3-bromopentane (64 %) among the monobromopentane products and preferred threo isomer among 2-,3-dibromobutane and 2,3-dibromopenane. The unique inorganic cavity traps Br2 leading the polarization of the diatomic molecule. Owing to its new reaction field, the trapped Br2 shows selective functionalization of alkanes.
Efficient Conversion of Alkyl Chlorides into Bromides
Yoon, K. B.,Kochi, J. K.
, p. 1013 - 1014 (2007/10/02)
The convenient and selective catalytic conversion of secondary and tertiary alkyl chlorides into bromides with hydrogen bromide in the presence of small amounts of anhydrous iron(III) bromide is described.
Gas-Phase Acid-Induced Nucleophilic Displacement Reactions. 4. A Stereochemical Probe for the Existence and the Relative Stability of Cyclic Halonium Ions in the Gas Phase
Angelini, Giancarlo,Speranza, Maurizio
, p. 3792 - 3799 (2007/10/02)
A comprehensive investigation on the existence and the relative stability of gaseous three-membered cyclic butene halonium ions was carried out by establishing the stereochemistry of the acid-induced displacement by nucleophilic such as H2O, H2S, etc., on a number of positively charged intermediates.The latter were obtained in the gas phase from the reaction of radiolytic formed Broensted (CH5+ and C2H5+) and Lewis (C2H5+ and CH3FCH3+) acids with 2,3-dihalobutanes.The stereoisomeric distribution of the neutral 3-halobutan-2-ols (or thiols) formed in these processes strongly implies the intermediacy of cyclic 2,3-butene halonium ions, whose stability in the gas phase depends on the nature of the halogen involved, increasing in passing from Cl to Br.No evidence for the occurrence of stable cyclic 2,3-butene fluoronium ions was obtained by the same procedure.Other factors, namely the strength of the radiolytic gaseous acid "catalysts" and the configuration of the starting dihalobutane, were found to play a role in determining the stereochemistry of the substitution processes investigated.A close correspondence does exist between the present results and those from strictly related mass spectrometric and condensed phase investigation.