26036-40-8

Upstream product

• 38395-09-4 1-(benzo[d][1,3]dioxol-5-yl)-3-phenylprop-2-yn-1-one 
• 932-90-1 Benzaldoxime 
• 3162-29-6 1-(benzo[d][1,3]dioxol-6-yl)ethanone 
• 98-88-4 benzoyl chloride 
• 15206-55-0 methyl 2-oxo-2-phenylacetate 
• 40288-65-1 1-(benzo[1,3]dioxol-5-yl)-2-bromoethanone 
• 6951-08-2 ethyl 1,3-benzodioxole-5-carboxylate 
• 98-86-2 acetophenone 

Downstream Products

• 856064-00-1 3⁽⁵⁾-(3',4'-methylenedioxyphenyl)-5⁽³⁾-phenylpyrazole 
• 29937-70-0 4-(1-benzo[1,3]dioxol-5-yl-3-oxo-3-phenyl-propyl)-5-methyl-2-phenyl-1,2-dihydro-pyrazol-3-one 
• 38320-77-3 3,5-diphenylisox-5-(benzo[d][1,3]dioxol-5-yl)-3-phenylisoxazole 
• 25856-13-7 3-(benzo[d][1,3]dioxol-5-yl)-5-phenylisoxazole 

Relevant academic research and scientific papers

Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils

The conversion of 1,3-diaryl-2-diazo-1,3-diketones to 1,2-daryl-1,2-diketones (benzils) is reported based on a rhodium(II)-catalyzed aerobic decomposition process. The reaction occurs at ambient temperatures and can be catalyzed by a few dirhodium carboxylates (5 mol %) under a balloon pressure of oxygen. Moreover, an oxygen atom from the O2 reagent is shown to be incorporated into the product, and this is accompanied by the extrusion of a carbonyl unit from the starting materials. Mechanistically, it is proposed that the decomposition may proceed via the interaction of a ketene intermediate resulting from a Wolff rearrangement of the carbenoid, with a rhodium peroxide or peroxy radical species generated upon the activation of molecular oxygen. The proposed mechanism has been supported by the results from a set of controlled experiments. By using this newly developed strategy, a large array of benzil derivatives as well as 9,10-phenanthrenequinone were synthesized from the corresponding diazo substrates in varying yields. On the other hand, the method did not allow the generation of benzocyclobutene-1,2-dione from 2-diazo-1,3-indandione because of the difficulty of inducing the initial rearrangement.

An effective preparation of both 1,3-diketones and nitriles from alkynones with oximes as hydroxide sources

An effective phosphine-catalyzed protocol has been established for the syntheses of 1,3-diketones and nitriles from alkynones with oximes as hydroxide surrogates. This method features the use of a phosphine catalyst, compatibility with various functional groups and ambient temperature, which makes this approach very practical. A plausible mechanism was proposed.

Room-Temperature Coupling/Decarboxylation Reaction of α-Oxocarboxylates with α-Bromoketones: Solvent-Controlled Regioselectivity for 1,2- and 1,3-Diketones

A transition-metal-free and room-temperature coupling/decarboxylation reaction between α-oxocarboxylates and α-bromoketones is reported herein. It represents the first mild and regioselective synthesis of either 1,2- or 1,3-diketones from the same starting materials. Notably, the regioselectivity is simply controlled by solvents. The preliminary experimental data and DFT calculations suggest sequential Darzens-type coupling, alkaline hydrolysis, KOH-promoted oxirane opening and decarboxylation in one pot. This method is efficient for the synthesis of α,β-epoxy-γ-butyrolactone and curcuminoids.

Transition-metal-free formal decarboxylative coupling of ?±-oxocarboxylates with ?±-bromoketones under neutral conditions: A simple access to 1,3-diketones

A transition-metal-free formal decarboxylative coupling reaction between ?±-oxocarboxylates and ?±-bromoketones to synthesize 1,3-diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal-based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the ?±-bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate-determining step is an unusual hydrogen-bond-assisted enolate formation by thermolysis.

Process for the preparation of aromatic beta-diketones

A process is disclosed for the preparation of aromatic beta-diketones by the reaction of an acetophenone and a molar excess of an aliphatic ester or an ester of benzoic acid in the presence of sodium alkoxide condensation agent in an aromatic hydrocarbon solvent at a temperature in the range 120-170oC. The solvent and excess ester reactant may be recycled after separation of the aromatic beta-diketone product.

Process for the preparation of aromatic beta-diketones

A process for the preparation of aromatic beta-diketones by the reaction of an acetophenone and a molar excess of an alphatic ester or an ester of benzoic acid in the presence of sodium alkoxide condensation agent in an aromatic hydrocarbon solvent. Also disclosed is a method of recycling the solvent and excess ester reactant after separation of the aromatic beta-diketone product.