17696-77-4Relevant academic research and scientific papers
Oxidation of Malonic Acid Derivatives by Manganese(III) Acetate. Aromatic Malonylation Reaction. Scope and Limitations
Citterio, Attilio,Santi, Roberto,Fiorani, Tiziana,Strologo, Sauro
, p. 2703 - 2712 (2007/10/02)
The oxidation of malonic acid derivatives RCH(COOR1)COOR2 (R1 = or R2 = H, Me, Et; R = H, Me, Et, n-Bu, i-Pr, C6H5, 4-OMeC6H4) by anhydrous or dihydrated manganese(III) acetate was studied in acetic acid in the presence of aromatic substrates at 20-80 deg C, generally with stoichiometric amounts of reagents.Electron-rich aromatics (IP 7.5 eV) underwent nuclear acetoxylation or quinone formation, the process being exclusive with anthracene and competitive with nuclear malonylation for 1- and 2-methoxynaphthalene.With other less electron-rich substrates (IP 8.5 eV) only the products coming from the oxidation of the malonic acid derivatives (aryl malonates, tartronates, etc., or dimerization and disproportionation products) were observed.The selectivity and the yield of aromatic substitution by the malonyl group was found to be affected by the electron density of the aromatic ring, the steric inhibition of substituents in the Mn(III) oxidation of the malonic acid derivative, the oxidizability of malonyl radical by Mn(III), the base (acetate ions or water) eventually present in the medium, and the further easy oxidation of the primary aryl malonate product, when unsubstituted dialkylmalonates or malonic acid were used.A mechanism is suggested in which inner-sphere electron transfer from Mn(III)-malonate complex affords Mn(II) malonyl radicals that are partitioned between oxidation, dimerization (or disproportionation), and reversible addition to the aromatics.
Reaction of Perfluoroalkyl Iodides with Electron Donor Nucleophiles. Addition of Perfluoroalkyl Iodides to Olefins Initiated by Electron Transfer
Feiring, Andrew E.
, p. 3269 - 3274 (2007/10/02)
The radical chain addition of primary and secondary perfluoroalkyl iodides to olefins is initiated by sodium arene- and alkanesulfinates.The process occurs at room temperature and is favored by the use of dipolar aprotic solvents.The reaction of perfluorooctyl iodide with sodium p-toluenesulfinate in the absence of olefin requires higher temperatures and gives only 1-H-perfluorooctane; no anion-perfluoroalkyl radical coupling products were detected.Reaction of perfluorooctyl iodide with the sodium salt of diethyl methylmalonate also gives no coupling product; only 1-H-perfluorooctane and a dimer of the malonate anion are produced.These results are compared with the reaction of perfluoroalkyl iodides with nitronate and thiolate anions where formation of SRN1 substitution products was observed.
