85157-85-3Relevant academic research and scientific papers
Iodine(III)-Mediated Oxidative Hydrolysis of Haloalkenes: Access to α-Halo Ketones by a Release-and-Catch Mechanism
Jobin-Des Lauriers, Antoine,Legault, Claude Y.
supporting information, p. 108 - 111 (2016/01/15)
An unprecedented iodine(III)-mediated oxidative transposition of vinyl halides has been accomplished. The products obtained, α-halo ketones, are useful and polyvalent synthetic precursors. There are only a handful of reported examples of the direct conversion of vinyl halides to their corresponding α-halo carbonyl compounds. Insights into the mechanism and demonstration that this synthetic transformation can be done under enantioselective conditions are reported.
One-step preparation of α-chlorostyrenes
Borate, Hanumant B.,Gaikwad, Abaji G.,Maujan, Suleman R.,Sawargave, Sangmeshwer P.,Kalal, Kamalakar M.
, p. 4869 - 4872 (2008/02/05)
α-Chlorostyrenes were prepared via a one-step method involving Friedel-Crafts reaction of various aromatic substrates with acid chlorides in the presence of a heterogeneous Si-Fe catalyst.
AN EFFICIENT METHOD FOR THE SYNTHESIS OF 1-ARYLALKYNES
Engler, Thomas A.,Combrink, Keith D.,Ray, James E.
, p. 1735 - 1744 (2007/10/02)
1-Arylalkynes are prepared from propiophenones in good yield via the sequence a) 2 equiv PCl5/Δ b) DBN or Δ and c) Mg metal.
Vinylcations, 39. Zinc Chloride Catalysed Addition of Hydrogen Chloride to Cyclopropylalkynes
Hanack, Michael,Weber, Erhard
, p. 777 - 797 (2007/10/02)
Zinc chloride catalysed addition of hydrogen chloride to 1-cyclopropylalkynes 5a-e (R = CH3, c-C3H5, phenyl, p-tolyl, 4-methoxyphenyl) is studied and the results are compared with those of the addition of HCl/ZnCl2 to several substituted arylalkynes 10a-h.Thus, the alkynes are reacted with HCl/ZnCl2 in dichloromethane and the reaction products are investigated also with respect to their stereochemistry.All alkynes yield predominantly the direkt hydrogen chloride addition products.The 1-cyclopropylalkynes 5a-d give (E)-1-chloro-1-cyclopropyl-1-alkenes 15, and (E)-1-chloro-2-cyclopropyl-1-(4-methoxyphenyl)ethene (16e) is obtained as the major product from 5e (R = 4-CH3OC6H4).Moreover, ring opening to homoallenyl chlorides 19 and, as a side reaction, formation of the ketones 17 and 18 by the addition of water are observed.In a secondary addition reaction, the dichlorides 20 are also obtained by homoallyl rearrangement.The arylalkynes 10a-g react preferentially with formation of (E)-1-aryl-1-chloroalkenes 21.Relative rates are obtained by inter- and intramolecular competition reactions of the alkynes 23 and 5b-e with HCl/ZnCl2 showing the order of stabilization by substituents of the intermediate vinyl cation 2 to be 4-ClC6H4 E2 mechanism.The preferential formation of the addition products E-15, E-16, and E-21 is attributed to a syn-vinyl cation ion pair and to steric approach control of the β-substituents in the vinyl cation intermediate 2.
