Ethyl acetate fluorene

The mechanism of this reaction has been adequately described (12). It is more pertinent to consider briefly the reaction of sodium with an ester such as ethyl acetate which possesses a rather acidic hydrogen in the a- position. The comparison between this reaction and the reaction of sodium with fluorene is rather striking. Ethyl acetate is more acidic than fluorene, but it is also more susceptible to an addition reaction. It is known that sodium brings about the formation of the anion which is the key intermediate in the Claisen condensation ... 

A mixture of 2-nitrosofluorene in ethyl acetate, triethylamine, acetyl chloride, and acetic anhydride hydrogenated with 10%-Pd-on-charcoal at room temp, and atmospheric pressure until slightly more than the equimolar amount of Hg has been absorbed N-fluoren-2-ylacetohydroxamic acid. Y 77%. F. e. s. Y. Yost and H. R. Gutmann, Soc. (C) 1970, 2497. 

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... 

To a solution of the S-(+)-4-acethoxy-9-[2-(5-ethyl-l,2,3,6-tetrahydro-pyridin-3yl)-l-(lH-indol-2-yl)-l-methoxycarbonyl-ethyl]-3a-ethyl-5-hydroxy-8-methoxy-6-methyl-3a,4,5,5a,6,ll,12,12b-octahydro-lH-6,12a-diaza-indeno[7,l-ca]fluorene-5-carboxylic acid methyl ester in dioxane and glacial acetic acid was added 37% aqueous formaldehyde and the mixture stirred at 35°C for 24 h. The solution was evaporated in vacuo and the residue suspended in chloroform and washed with cold aqueous 5% K2C03 solution. The chloroform layer was dried (MgS04), filtered, and evaporated. The residue was chromatographed eluting with EtOAc/MeOH, 10% NH4OH to give the product navelbine. 

The transfer constants (ox solvents vary by several orders of magnitude, from 2 X 10 for styrene in benzene to 5 700 for vinyl acetate in carbon tetrabromide. The constants increase with the number of transferable atoms per solvent molecule (series benzene-toluene-ethyl benzene), the weakness of the bond (carbon tetrachloride and carbon tetrabromide), and the resonance stabilization of the free radical produced (benzene-fluorene-pentaphenyl... 

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