507-36-8Relevant articles and documents
THE MECHANISM OF 2-METHYLBUTENE-2 HYDROHALOGENATION IN SOLID PHASE
Sergeev, G. B.,Smirnov, V. V.,Rostovshchikova, T. N.,Komissarovan N. V.,Indoleva, Ye. V.
, p. 5853 - 5864 (1987)
Complexes and reactions of 2-methylbutene-2 with hydrohalogen (HCl, HBr) have been studied in solid phase at 80-150 deg K.It has been found that 2-methylbutene-2 forms with HX complexes of 1:1 and 1:2 composition.Hydrohalogenation proceeds via the rearrangement of complex 2HX*C5H10 into complex of addition product with HX.Kinetic equation depends on the reagents ratio.In excess of HX (1HX:C5H1010)reaction can be described by the first order kinetic equation.If the ratio HX:C5H10 is more then 10, reaction is described by polychronous kinetic law.The effective activation energy of solid phase hydrohalogenation does not exceed 20 kJ/mole.The molecular mechanism of hydrohalogenation in solid phase has been proposed
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Bailey,Saunders
, p. 3363,3366 (1973)
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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.
1,2-Dibromotetrachloroethane: An efficient reagent for many transformations by modified Appel reaction
Essiz, Sel?uk,Da?tan, Arif
, p. 150 - 156 (2019/05/16)
An efficient and facile method has been developed for the synthesis of alkyl bromides from various alcohols under mild conditions using a triphenylphosphine (PPh 3) /1,2-dibromotetrachloroethane (DBTCE) complex in excellent yields and very short time (5 min). This method can also be applied for the transformation of chiral alcohols to their corresponding bromides in very high enantiomeric excess. The PPh 3 /DBTCE complex is also successfully applied to ring-opening reactions of cyclic ethers in mild conditions. Esterification, amidation, and formation of acid anhydrides under very mild experimental conditions are also successfully accomplished by following a modification of the Appel reaction protocol in this work.
