123003-33-8

Upstream product

• 50917-73-2 diethyl (N-benzylideneaminomethyl)phosphonate 
• 21086-26-0 1,1,5,5-tetraphenyl-1,4-pentadien-3-one 
• 917-54-4 methyllithium 
• 325770-91-0 ethyl 2-methyl-2-(2,2-diphenylvinyl)-4,4-diphenyl-3-butenoate 
• 325770-90-9 ethyl 2-(2,2-diphenylvinyl)-4,4-diphenyl-3-butenoate 
• 38503-54-7 1,1,5,5-Tetraphenyl-1,4-pentadiene 
• 325770-93-2 2-methyl-2-(2,2-diphenylvinyl)-4,4-diphenyl-3-butenol 

Downstream Products

• 325770-96-5 methyl 2-carbomethoxy-4-methyl-4-(2,2-diphenylvinyl)-6,6-diphenyl-2,5-hexadienoate 
• 119656-81-4 2-cyano-4-methyl-4-(2,2-diphenylvinyl)-6,6-diphenyl-2.5-hexadienenitrile 

Relevant academic research and scientific papers

Excited- and ground-state versions of the tri-π-methane rearrangement: Mechanistic and exploratory organic photochemistry

The di-π-methane rearrangement with two π-groups bonded to a single carbon leading to π-substituted cyclopropanes is now well established. The present research had as its goal the exploration of molecular systems having three π-moieties attached to an sp3-hybridized atom in a search for a tri-π-methane rearrangement. Indeed, it was found that such systems do rearrange photochemically to afford cyclopentenes. However, it was also established that vinylcyclopropanes ring-expand to cyclopentenes on direct irradiation. Since both three-ring and five-ring photoproducts often are found to be produced, it was important to establish that the observed photochemistry was really the result of a true single-step tri-π-methane rearrangement and not the consequence of two sequential rearrangements, first to form a vinyl cyclopropane which subsequently ring expanded to the cyclopentene. The general situation has three species - A, B, and C - corresponding to tri-π-methane reactant A, vinylcyclopropane photoproduct B, and cyclopentene photoproduct C. Three rate constants are involved, k1 for A → B, k2 for A → C, and k3 for B → C. The kinetics were applied to two examples with provision to avoid differential light absorption; this utilized singlet sensitization. It was determined that direct formation of the cyclopentene photoproduct proceeds more rapidly than the ring-expansion route. In contrast to the di-π-methane rearrangement, the tri-π-methane reaction was found to be preferred by the singlet, while in these sterically congested systems; the triplet led to di-π-methane reactivity. Finally, a ground-state counterpart of the reaction was obtained.

A ground state tri-π-methane rearrangement

An example of a ground state tri-π-methane rearrangement is described. (C) 2000 Elsevier Science Ltd.

A Study of the Competition between the Di-?-methane and the Azadi-?-methane Processes in 2-Vinyl-β,γ-unsaturated Oxime Derivatives. The Novel Azadi-?-methane Reactivity of β,γ-Unsaturated Oximes

A study aimed at detecting intramolecular competition between the di-?-methane (DPM) rearrangement and the azadi-?-methane (ADPM) process has been carried out.The results show that direct or acetophenone-sensitized irradiation of 2-(2,2-diphenylvinyl)-2-m