24225-40-9

Upstream product

• 7677-24-9 trimethylsilyl cyanide 
• 4535-09-5 N-phenyl-fluorenoneimine-N-oxide 
• 17454-96-5 9‐cyano‐9,9'-bifluorenyl 
• 69813-78-1 9-hydroxy-9H-fluorene-9-carbonitrile 

Downstream Products

• 86-73-7 9H-fluorene 
• 486-25-9 9-fluorenone 
• 1529-40-4 9H-fluorene-9-carbonitrile 
• 1530-12-7 9,9'-bifluorenyl 
• 19126-15-9 9-methoxyfluorene 

Relevant academic research and scientific papers

Photochemical generation of 9-Fluorenyl radicals

A series of 9H-fluorenols and 9H, 9′H-bifluorenyls were irradiated in less polar solvents giving photoproducts derived from their corresponding 9H-fluorenyl radicals. These transient species were directly observed by laser flash photolysis and their UV/visible spectra compared with those of their corresponding cations. Theoretical calculations (density functional theory [DFT]) of these intermediates indicate their destabilizing nature in similar fashion to the antiaromatic character of the corresponding cations.

Photochemical generation of 9h-fluorenyl radicals

A series of 9-substituted fluorenols and 9,9′-disubstituted-9, 9′-bifluorenyls were irradiated to give products derived from fluorenyl radicals. Product distribution was solvent dependent. A TEMPO adduct was isolated from the photoexcitation of 9-fluorenol. An unusual unsymmetrical 3,9′-bifluorenyl was observed from the photolysis of 9- trifluoromethylfluorenol and 9,9′-di(trifluoromethyl)-9,9′- bifluorenyl in more polar or hydrogen-bonding solvents. The electronic nature of 9-substituted fluorenyl radicals was probed using theoretical calculations showing the dipolar character of species with electron-deficient groups. These constitute the first examples of "doubly destabilized" radicals. Substituted 9-fluorenols and 9,9′-bifluorenyls undergo photolysis to give products derived from 9-fluorenyl radicals. These intermediates decay by hydrogen abstraction giving 9H-fluorenes, or coupling to 9,9′bifluorenyls. The 9-trifluoromethyl-9-fluorenyl radical undergoes an unusual coupling to the unsymmetrical 9,3′-bifluorenyl.

Reactions of Trimethylsilyl Cyanide and N-(Trimethylsilyl)diphenylmethyleneamine with Nitrones and Thermal Decompositions of Their Adducts

Trimethylsilyl cyanide (1) and N-(trimethylsilyl)diphenylmethyleneamine (2) reacted with α-aryl-N-phenylnitrones to afford the corresponding 1:1 adducts 4 and 5 respectively.Thermal decomposition of 4 in refluxing xylene gave azoxybenzene, stereoisomers of 2,3-diarylsuccinonitriles, α-aminonitriles and/or benzanilides, whose yields depended on the nature of substituents on phenyl group of 4.On heating in benzene 5 afforded a mixture of azoxybenzene and meso-N,N'-bis(diphenylmethylene)-1,2-diarylethylenediamines.On the other hand, reactions of 1 and 2 with N-(diphenylmethylene)aniline N-oxide or N-(9-fluorenylidene)aniline N-oxide did not give the corresponding 1:1 adducts, but instead compounds arising from thermal decomposition of initial 1:1 adducts were directly obtained.The reaction of 1 with N-(p-diethylaminophenyl)-α-phenylnitrone leading to the corresponding α-imino nitrile is also described.