9- -9-fluorenol

A. 9-Phenyl-9-fluorenol. A flame-dried, 3-L, three-necked, round-bottomed flask equipped with an overhead stirrer, rubber septum, and glass stopper, under a nitrogen atmosphere, is charged with bromobenzene (158 mL, 1.5 mol, Note 2) and ethyl ether (800 mL, Note 2). The solution is cooled in an ice bath and stirred at 0°C. 

The relative amounts of 9-phenyl-9-fluorenol and 9-bromo-9-phenyl-fluorene were determined as follows A 13C NMR spectrum (CDCI3 solution, Bruker 400 MHz) of an authentic sample of 9-bromo-9-phenylfluorene was recorded and then doped in 1% increments with authentic 9-phenyl-9-fluorenol. A 13C NMR spectrum (CDCI3 solution, Bruker 400 MHz) was recorded after each doping, and the heights of the peaks at 120.3 ppm (bromide) and 120.0 ppm (alcohol) were monitored. These spectra were compared with a 13C NMR spectrum (CDCI3 solution, Bruker 400 MHz) of the sample in question. Application of this technique to an evaporated aliquot of the reaction mixture in Step B, indicated >97% conversion of alcohol to bromide after 24 hr. 

Phenyl-9-fluorenol Fluoren-9-ol, 9-phenyl- (8) 9H-Fluoren-9-ol, 9-phenyl- (9) (25603-67-2)... 

The properties of 9-phenyl-9-fluorenol are as follows TLC (1/3 EtOAc/hexane, aluminum backed silica) Rf 0.67 see ref. 4 for additional spectral and physical data. 

Exclusion of moisture from the reagents and apparatus is most important, as 9-bromo-9-phenylfluorene hydrolyzes to 9-phenyl-9-fluorenol, which is unreactive toward free amines. Accordingly, all glassware, K3PO4, Pb(N03)2 (which scavenges bromide ion), and substrates must be dried thoroughly (as described above) and kept under an inert atmosphere prior to use. In addition, solvents must be distilled immediately before use and transferred to the reaction vessel under an inert atmosphere. 

The methanol quench in Step B facilitates chromatographic purification by forming the known 9-methoxy-9-phenylf uorene,6 which is less polar than 9-phenyl-9-fluorenol, from 9-bromo-9-phenylfluorene (but not from 9-phenyl-9-fluorenol). Both 9-methoxy-9-phenylfluorene and 9-phenyl-9-fluorenol can be converted to 9-bromo-9-phenylfluorene by treatment with 48% hydrobromic acid (HBr).4... 

Bromo-9-phenylfluorene 9H-Fluorene, 9-bromo-9-phenyl (9) (55135-66-5) (S)-Dimethyl aspartate hydrochloride Aspartic add, dimethyl ester, hydrochloride, L- (8) L-Aspartic acid, dimethyl ester, hydrochloride (9) (32213-95-9) 9-Methoxy-9-phenylfluorene 9H-Fluorene, 9-methoxy-9-phenyl- (9) (56849-87-7) 9-Phenyl-9-fluorenol Fluoren-9-ol, 9-phenyl- (8) 9H-Fluoren-9-ol, 9-phenyl- (9) (25603-67-2)... 

Phthalic anhydride 9-Fluorenol, see Fluorene Fluorenone, see Fluorene... 

Refluxing of 9-fluorenone-l-carboxylic acid with zinc dust and copper sulfate in aqueous potassium hydroxide for 2.5 hours afforded 9-fluorenol-1-carboxylic acid in 94% yield [1004]. Reduction with sodium borohydride in aqueous methanol at 0-25° converted 5-ketopiperidine-2-carboxylic acid to /ra j-5-hydroxypiperidine-2-carboxylic acid in 54-61% yield [1005], On the other hand, reduction of V-benzyloxycarbonyl-5-ketopiperidine-2-carboxylic acid gave 89% yield of V-benzyloxycarbonyl-cis-5-hydroxypiperidine-2-car-boxylic acid under the same conditions [1005],... 

Some lactol-to-lactone oxidations were effected by TPAP/NMO/PMS/CH Clj [498, 499], or TPAP/NMO/PMS/CH3CN [159]. The system RUCI3 or RuO / Na(Br03)/aq. M Na3(C03) generates [RuO ]" in aqueous solution and oxidised secondary alcohols to ketones in high yield (Table 2.2) [213]. Kinetics of the oxidation of benzhydrol and 9-fluorenol by TPAP/NMO/CH3CN/30°C were measured. 

Oxidation of diphenylmethane in basic solutions involves a process where rate is limited by and equal to the rate of ionization of diphenylmethane. The diphenylmethide ion is trapped by oxygen more readily than it is protonated in dimethyl sulfoxide-text-butyl alcohol (4 to 1) solutions. Fluorene oxidizes by a process involving rapid and reversible ionization in text-butyl alcohol solutions. However, in the presence of m-trifluoromethylnitrobenzene, which readily accepts one electron from the carbanion, the rate of oxygen absorption can approach the rate of ionization. 9-Fluorenol oxidizes in basic solution by a process that appears to involve dianion or carbanion formation. Benzhydrol under similar conditions oxidizes to benzophenone by a process not involving carbanion or dianion formation. 

The present work demonstrates that the oxidation of diphenylmeth-ane in basic solution follows a pattern similar to triphenylmethane and not to fluorene. At high concentrations of good electron acceptors it is possible to realize a situation wherein the rate of oxidation of fluorene is limited by and equal to the rate of ionization. The oxidations of benzhydrol and 9-fluorenol in basic solution are considered the difference in acidity of the methine hydrogens has a pronounced effect on the course of these oxidations. 

Table III summarizes some information on the initial rates of oxidation of fluorene in several solvents. In the alcohol-containing solvents the stoichiometry was nearly one molecule of oxygen per mole of fluorene, an observation that excludes 9-fluorenol as an intermediate. In all solvents, including HMPA, interrupted oxidations yielded only fluorenone (or the DMSO-fluorenone adduct) and fluorene. Apparently Reaction 6 or 7 occurs readily in the presence of hydroxylic solvents. In HMPA the high...

Oxidation of 9-Fluorenol and 9-Xanthenol in Basic Solution. Fluor-enol and xanthenol react with base and oxygen to give high yields of the ketones, or in the case of fluorenol in DMSO solution, the DMSO-fluore-none adduct. The stoichiometry of the oxidation (Table XI) varies with... 

Figure 5. Oxidation of 0.15M 9-fluorenol in tert-butyl alcohol containing 0.4M potassium tert-butoxide...

No deuterium isotope effect was observed in the oxidations of 9-deuterio-9-fluorenol. The rates of oxidation varied considerably with solvent... 

The oxidation of benzhydrol and 9-fluorenol in basic solution again shows a difference in regard to mechanism that can be primarily attributed to a difference in acidity as carbon acids. In tert-butyl alcohol benzhydrol enters into an oxidation scheme as the mono (oxy) anion. The data strongly suggest a free radical chain. Under these conditions the more acidic fluorenol or xanthenol oxidizes via carbanions or dianions. These oxidations can be catalyzed to occur via a free radical chain process by one-electron acceptors, such as nitrobenzene, and a free radical chain process may well be involved in the absence of the catalyst. 

Methylfluorene has been prepared by cleavage of ethyl 9-methyl-9-fluorenylglyoxylate,4 by the decarboxylation of 9-methylfluorene-9-carboxylic acid,4 by the decarboxylation of 9-fluorenylacetic acid,6 by the cleavage of 9-methyl-9-acetyl-fluorene with alcoholic potassium hydroxide or soda-lime,6 by the reduction of 9-methyl-9-fluorenol with hydriodic acid in acetic acid,7 by the reaction of 9-fluorenyllithium 8 or -sodium 9 with methyl iodide or methyl sulfate,9 by the cyclization of diphenylmethyl carbinol over platinum-on-carbon at 300°,10 by the reaction of ethyl 9-methoxymcthyl-9-fluorcnylcarboxylate,11 by the diazotization and heating of 2-ethyl-2-aminobiphenyl,12 by the dehydration and then reduction of 9-mcthyl-9-fluorcnol,13... 

Fluorenyl)-9-fluorenol (69) has been converted into 6-(9-fluorenyl)phenanthridine (70) in low yield.120... 

A 200 ml reaction flask charged with 9-fluorenol (11 mmol), 180 ml of benzene, and triethylamine (13.75 mmol) was cooled to 6°C and then treated with the slow addition of methacryloyl chloride (13.75 mmol). Thereafter the mixture was stirred at ambient temperature for 24 hours. The solution was washed with water and saturated NaHCOs, and the organic layer was isolated, dried with MgS04, and concentrated. The residue... 

C19H140 9-phenyl-9-fluorenol 25603-67-2 692.65 62.670 2 31586 C19H2603 4-(methyloxymethyl)benzyl chrysanthemum mono 34388-29-9 476.65 41.645 2... 

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