96795-81-2

Upstream product

• 108-13-4 malonodiamide 
• 26642-57-9 1,1-bis(4-methoxyphenyl)-2-phenylethene 
• 41038-34-0 4,4’-(2-bromo-2-phenylethene-1,1-diyl)bis(methoxybenzene) 
• 127-09-3 sodium acetate 
• 123-54-6 acetylacetone 

Relevant academic research and scientific papers

Photoreactivity of Some α-Arylvinyl Bromides in Acetic Acid. Selectivity toward Bromide versus Acetate Ions as a Mechanistic Probe

The photochemical reactions of four α-anisyl-β,β-diarylvinyl bromides (1a-1d), three α-phenyl-β,β-diarylvinyl bromides (1e-1g), and 9-(α-bromo-p-methoxybenzylidene)anthrone (2) in acetic acid in the presence of sodium acetate and tetraethylammonium bromide (labeled with 82Br) have been studied quantitatively. Bromide exchange, acetate formation, E/Z isomerization, an anisyl 1,2-shift, stilbene-type cyclization to phenanthrenes, reductive debromination, and oxidation are observed as primary pathways. For all compounds 1, nucleophilic substitution, accompanied by E/Z isomerization in both starting material and product with 1b,c and 1f,g and an anisyl 1,2-shift in 1e but not in 1f,g, is quite efficient and by far the most important process. (Quantum yields range from 0.1 to 0.3 as compared to 0.01-0.02 for cyclization and 0.001-0.01 for reduction). The α-anisylvinyl bromide 2 is virtually inert for photosubstitution. The selectivity constants toward bromide and acetate ions, corrected for their temperature dependence, the amounts of E/Z isomerized starting material and product, the occurrence or nonoccurrence of an anisyl 1,2-shift, and the nature of the capturing nucleophile in the acetolysis are all in quantitative agreement with the corresponding data for the thermal reactions of 1 in the same medium. The results strongly support a mechanism for the nucleophilic vinylic photosubstitution reactions that involves the generation of a product-forming intermediate, which is exactly the same as the intermediate formed in the thermal reaction, a "cold" (thermally relaxed) linear free vinyl cation.

The Facile Synthesis of Dihydrofurans by the Oxidation of Olefins with Tris(2,4-pentanedionato)manganese(III)

Eleven olefins were oxidized with tris(2,4-pentanedionato)manganese(III) at the reflux temperature to give the corresponding 3-acetyl-2-methyl-4,5-dihydrofurans in good yields.The oxidation of 9-benzylidene-9,10-dihydroanthracene under the same reaction conditions did not produce the corresponding dihydrofuran, but 9--9,10-dihydroxyanthracene.When 1,1-diphenylethene was oxidized at room temperature, 3-acetyl-2-hydroperoxy-2-methyl-5,5-diphenyltetrahydrofuran was obtained in a high yield.The effects of the solvent and the additives on the yield of dihydrofuran, the comparable reactivities of other (2,4-pentanedionato)metal complexes, such as Co(III), Cr(III), Fe(III), and Cu(II), and the reaction mechanism are discussed.

Reaction of Olefins with Malonamide in the Presence of Manganese(III) Acetate. Formation of α,β-Unsaturated γ-Lactones and γ-Lactams

The reaction of olefins with malonamide in the presence of manganese(III) acetate gave 2-buten-4-olides and/or 1H-pyrrol-2(5H)-ones in one-step, short reaction time and moderate yields.The product distribution can be accounted for in terms of the stabilization of the intermediate carbocation in the oxidation process.The synthetic application and limitation, and the oxidation mechanism for the formations of α,β-unsaturated γ-lactones and γ-lactams are discussed.