77197-64-9

Upstream product

• 13343-40-3 (2,2-difluoro-1-cyclopropyl)benzene 
• 917-54-4 methyllithium 
• 178425-56-4 1,1,2-tribromo-2-phenylcyclopropane 
• 74-88-4 methyl iodide 

Downstream Products

• 32123-84-5 3-phenylbut-3-en-2-one 
• 93-91-4 1-phenylbutan-1,3-dione 
• 62961-61-9 (Z)-4-hydroxy-4-phenyl-3-buten-2-one 
• 114646-77-4 1-(6-methyl-2,5-diphenyl-3,4-dihydro-2H-pyran-2-yl)ethanone 

Relevant academic research and scientific papers

Ene di- and trimerization of 1-methyl-2-phenylcyclopropene

1,2-Disubstituted cyclopropene, 1-methyl-2-phenylcyclopropene (18), was generated by bromo-lithium exchange of 1-bromo-2-phenylcyclopropene followed by treatment with methyl iodide. Compound 18 was oxidized by oxygen to give the α,β-unsaturated carbonyl product 25 and diketone 27 and the tautomeric, β-hydroxyl-α,β-unsaturated ketone 28. However, compound 28 reacted further with the cyclopropene 18 in a retro-Claisen-like reaction to generate adduct 26. Furthermore, compound 18 underwent ene dimerization in neat condition to form the endo-dimer 40 and exo-dimer 41 followed by oxidization with oxygen to give aldehyde 39. It is noteworthy that the endo-dimer 40 and exo-dimer 41 could be trapped with thiophenol to give adduct 42 and 43. In addition, the ene reaction of exo-dimer 41 with monomer 18 gave an exo-exo ene trimer 46 through an exo-transition state which was also trapped by thiophenol to give adducts 44 and 45.

REACTION OF 1,1-DIFLUOROCYCLOPROPANES WITH ORGANOLITHIUM COMPOUNDS

Substitued 1,1-difluorocyclopropanes react with organolithium reagents to provide either cyclopropenes or mono-substitued acetylenes depending upon the substitution patterns.