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• 100-42-5 styrene 
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• 28531-58-0 (2-oxo-2-phenylethyl)mercury chloride 
• 46788-89-0 C₁₃H₁₅O₄^(1-) 

Relevant academic research and scientific papers

Oxidative dimerization of diethyl 3-thienylmalonate by high valent metal salts. Synthesis of benzo[1,2-b:4,5-b']dithiophene derivatives

The oxidation of diethyl 3-thienylmalonate (1) by metal oxidants (Fe(ClO4)3, Mn(OAc)3, MnO2 and CuO) in various solvents at 60 °C affords dimerization products arising from side-chain and nuclear coupling of the intermediate delocalized malonyl radicals 6. Metal to sulphur binding is suggested to play a role in controlling the distribution of dimers 2-5. The higher thermodynamic stability of unsymmetric dimer 3, along with its oxidative intramolecular 1,6-cyclization to 4, allows to develop a new simple synthesis of benzo[1,2-b:4,5-b']dithiophene derivatives 15-18.

Oxidative Dimerization of CH Acids

Anodic oxidation of alkyl- (1) and acylmalonic acid esters (7) yields the dehydrodimers 4 and 8, respectively.Preparative electrolyses are performed in acetonitrile in the presence of a base to generate the carbanion corresponding to the CH acid.The carbanions are oxidized to the radicals which dimerise on the electrode surface.The yields of the preparative electrolyses and the formation of the dehydrodimers 4 and 8 are discussed in terms of the CH acidity and enolization of the starting materials. - Key Words: Electrochemistry / Oxidation, anodic / CH Acids / Dehydrodimerization

Manganese(III)-Mediated Carbon-Carbon Bond Formation in the Reaction of Xanthenes with Active Methylene Compounds

Oxidation of xanthenes with manganese(III) acetate in the presence of active methylene compounds such as 1,3-dicarbonyl compounds, malononitrile derivatives, acetone, and nitromethane selectively gives 9-substituted xanthene derivatives in good yields.A similar oxidation of thioxanthene also yields 2-(9-thioxanthenyl)-1,3-dicarbonyl compounds in 57-91 percent yields.The obtained 2-(9-xanthenyl)-1,3-dicarbonyl compounds are readily converted to 2-(9-xanthenylidene)-1,3-dicarbonyl derivatives using manganese(III) complexes or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone.The mechanisms for the formation of 9-substituted xanthenes are discussed on the basis of the reaction intermediates, the electron-donating substituent effect on the xanthene ring system, effect of additives, and comparison with a reaction of radical-trapping reagents.

Radical and Ionic Reactions of (Benzoylmethyl)mercurials

Photolysis of PhCOCH2HgCl or (PhCOCH2)2Hg yields benzoylmethyl radicals which can be trapped by anions such as Me2C=NO2-, RC(CO2Et)2-, RC(O-)=CH2 or by other electron-rich systems such as (RO)3P, N-methylpyrrole, enamines, or norbornene.Electron transfer from the adduct radicals to the mercurials yields PhCOCH2A from the anions A-, PhCOCH2P(O)(OR)2 from P(OR)3, and the phenacyl derivative from N-methylpyrrole or enamines.Easily oxidized anions such as PhCOCPh2- or PhC(CH3)=NO2- react with PhCOCH2* by electron transfer to yield the dimer derived from the anion.Addition of PhCOCH2* to norbornene yields a substituted 3-benzoylpropyl radical which cyclizes at the ortho position of the benzoyl group to give the α-tetralone derivative.

Oxidation of Malonic Acid Derivatives by Manganese(III) Acetate. Aromatic Malonylation Reaction. Scope and Limitations

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.