32501-56-7

Upstream product

• 858258-84-1 9-cyclohex-1-enyl-fluorene 
• 86-73-7 9H-fluorene 
• 108-93-0 cyclohexanol 
• 110-82-7 cyclohexane 
• 832-80-4 9-diazofluorenone 
• 108-85-0 1-bromocyclohexane 
• 1689-64-1 9-Fluorenol 
• 108-94-1 cyclohexanone 
• 931-50-0 cyclohexylmagnesium bromide 
• 486-25-9 9-fluorenone 
• 67-56-1 methanol 
• 67222-05-3 9-cyclohexylidene-fluorene 
• 20615-64-9 fluorene-9-carbaldehyde 
• 748187-21-5 9-cyclohexyl-fluoren-9-ol 

Downstream Products

• 789-24-2 9-Phenylfluorene 
• 162559-72-0 (C₅H₅)ZrCl₂(C₁₃H₈C₆H₁₁) 
• 187339-46-4 (pentamethylcyclopentadienyl)ZrCl₂(9-cyclohexylfluorenyl) 
• 162559-77-5 (C₁₃H₈(C₆H₁₁))2ZrCl₂ 

Relevant academic research and scientific papers

T -BuOK-catalysed alkylation of fluorene with alcohols: A highly green route to 9-monoalkylfluorene derivatives

A simple, mild and efficient protocol was developed for the alkylation of fluorene with alcohols in the presence of t-BuOK as catalyst, affording the desired 9-monoalkylfluorenes with near quantitative yields in most cases.

Activation of Molecular Hydrogen by Arylcarbenes

The hydrogenation reactions of diphenylcarbene 1, fluorenylidene 2, and dibenzocycloheptadienylidene 3 were investigated in solid H2 and D2 matrices and in H2- and D2-doped argon matrices at cryogenic temperatures. The reactivity of the carbenes towards H2 increases in the order 12, 2 and 3 react fast under the same conditions via quantum chemical tunneling. In D2 both 1 and 3 are stable, whereas 2 slowly reacts. The different reactivity of the three carbenes is rationalized in terms of differing carbene stabilization energies.

Aldehyde/ketone-catalyzed highly selective synthesis of 9-monoalkylated fluorenes by dehydrative C-alkylation with primary and secondary alcohols

By using aldehydes or ketones as the catalyst and screening CsOH out as the more effective base than KOH in many instances, an efficient 9-C-alkylation of fluorenes with alcohols was achieved to provide a green and practical method for general synthesis of the useful 9-monoalkylated fluorenes in high selectivities. This new method tolerates a wide range of substrates including activated and unactivated primary and secondary alcohols, thus solving the issues remaining in the field and largely broadening the diversity of the 9-monoalkylated fluorenes. Consequently, fine-tuning of the alkylated fluorenes was made possible to provide specific fluorene monomers for function-oriented polyfluorenes. Preliminary mechanistic studies revealed that the external carbonyl compounds can be quantitatively regenerated and recovered in the reaction cycle.

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.

The preparation and characterization of 9-substituted bis(fluorenyl) zirconium dichloride complexes

The preparation of new zirconocene dichloride complexes containing 9-substituted fluorenyl ligands is reported.The complexes were characterized by 1H and 13C NMR spectroscopy.Keywords: Bis(fluorenyl)complexes of zirconium; Multinuclear NMR spectroscopy

CONTRASTING CHEMISTRY OF DIPHENYLCARBENE AND FLUORENYLIDENE IN CYCLOHEXANE

The chemistry of diphenylcarbene and fluorenylidene in cyclohexane was investigated.An examination of the product distributions, radical scavening experiments and isotopic fractionation established that diphenylcarbene reacts with cyclohexane predominantly, if not exclusively, through its triplet state whereas fluorenylidene exhibits substantial chemistry from its low lying singlet state in addition to some triplet chemistry.The results indicate that the singlet-triplet splitting of fluorenylidene is smaller than in diphenylcarbene.The chemical studies are in accord with previous laser flash photolysis experiments.

Fluorenylidene: Kinetics and Mechanism

Laser irradiation of 9-diazafluorene in solution leads to the formation of a transient species with λmax=470 nm that has been characterized as the triplet carbene and is believed to be in thermal equilibrium with the singlet state, which lies within a few kcal/mol.The singlet carbene is frequently more reactive and tends to dominate the chemistry.For example, in hydrogen donors, the triplet state abstracts hydrogen leading to the 9-fluorenyl radical, which is the only species detected in the flash experiments.However, product studies demonstrate that the predominant reaction path is the insertion of the singlet into C-H bonds (e.g., in cyclohexane), a process that is transparent to the technique of nanosecond laser photolysis.Irradiation of 9-diazofluorene in nitrile solvents results in carbene addition to the nitrile function, leading to nitrile ylides that react rapidly with electron-deficient olefins and present a characteristic absorption band at ca. 400 nm.The singlet carbene has a lifetime of =5 ns and obeys the Skell-Woodworth rules.

On the Importance of Indiscriminate Insertion for Photoactivable Reagents - Photolysis of Diazofluorene in Mixed Organic Solvents

Photolysis of diazofluorene (I), a new fluorescent photoactivable reagent, in cyclohexane, cyclohexene, methanol and in mixtures of the solvents is reported.Quantitative analysis of products formed has been carried out.In bulk hydrophobic milieu diazofluorene does show some indiscriminateness in its insertion reactions.The importance of indiscriminate insertion in photoaffinity labeling studies has been dicussed.A simple method has thus been developed to test the indiscriminate properties of a photoactivable reagent by photolysing it first in simple organic solvents.Such studies should prove useful and photoactivable reagents can be tested before applying them directly to biological systems.

CHEMICAL AND PHYSICAL PROPERTIES OF FLUORENYLIDENE: EQUILIBRATION OF THE SINGLET AND TRIPLET CARBENES.

Irradiation of 9-diazofluorene, with a pulsed laser on a picosecond or nanosecond time scale at room temperature, or at 10 K in a glassy matrix, gives detectable fluorenylidene. This species is shown to exist, under most experimental conditions, as a rapi