37773-35-6Relevant articles and documents
Synthesis and Reactivity Studies of a Series of Nickel(II) Arylchalcogenolates
Cordeiro, Lauren L.,Dmitrenko, Olga,Yap, Glenn P. A.,Riordan, Charles G.
, p. 6327 - 6338 (2021/05/06)
Two series of high-spin nickel complexes, [TpPh,Me]Ni(EAr) (E = O, Se, Te; Ar = C6H5) and [TpPh,Me]Ni(SeC6H4-4-X) (X = H, Cl, Me, OMe), were prepared by metathetical reaction of the nickel(II) halide precursor with sodium salts of the corresponding chalcogen, NaEAr. X-ray crystallographic characterization and spectroscopic studies have established the geometric and electronic structures of these complexes. The observed spectroscopic and structural characteristics reveal distinct trends in accordance with the variation of the identity of the arylchalcogenolate and para substituent. Reaction of the [TpPh,Me]Ni(EAr) complexes with methyl iodide proceeded readily, producing the corresponding methylarylchalcogen and [TpPh,Me]NiI. A kinetic and computational analysis of the reaction of [TpPh,Me]Ni(SeC6H5) with MeI supports that the electrophilic alkylation reactions occur via an associative mechanism via a classical SN2 transition state.
FeCl3-Diorganyl dichalcogenides promoted cyclization of 2-alkynylanisoles to 3-chalcogen benzo[ b ]furans
Gay, Rafaela M.,Manarin, Flavia,Schneider, Caroline C.,Barancelli, Daniela A.,Costa, Michael D.,Zeni, Gilson
supporting information; experimental part, p. 5701 - 5706 (2010/10/03)
A general synthesis of 3-chalcogen benzo[b]furans from the readily available 2-alkynylanisoles, via FeCl3/diorganyl dichalcogenides intramolecular cyclization, has been developed. Aryl and alkyl groups directly bonded to the chalcogen atom were used as cycling agents. The results revealed that the reaction significantly depends on the electronic effects of substituents in the aromatic ring bonded to the selenium atom of the diselenide species. We observed that the pathway of reaction was not sensitive to the nature of substituents in the aromatic ring of anisole since both the electron-donating and the electron-withdrawing groups delivered the products in similar yields. In addition, the obtained heterocycles were readily transformed to more complex products by using a chalcogen/lithium exchange reaction with n-BuLi followed by trapping of the lithium intermediate with aldehydes, furnishing the desired secondary alcohols in good yields.
Methyl Transfers. 10. The Marcus Equation Application to Soft Nucleophiles
Lewis, Edward S.,McLaughlin, Mark L.,Douglas, Thomas A.
, p. 6668 - 6673 (2007/10/02)
The Marcus equation to methyl transfers is shown to cover reactions of " soft" nucleophiles, although small discrepancies occur.Rates and equilibria are reported for a series of reactions of arylmethylselenides with (p-chlorophenyl)dimethylselenonium ion.Experimental reaction rates between "hard" methylating agents and "soft" nucleophiles show small deviations from the calculated values, mostly but not always in the direction predicted by the HSAB principle.The Marcus equation fails to explain the previously reported "inversion" of reaction rates of 4-nitrothiophenoxide and of 4-nitrophenoxide with methyl iodide and dimethyl sulfate.Identity rates for dimethyl sulfate, methyl methanesulfonate (using 3He), methyl iodide (using 125I), and methyl triflate (using 35S) in sulfolane are reported.
