Fluorene 1,2,3,4-tetrahydro

Loss of ethylene and subsequent formation of the stable 3//-pyrrolinine cation dominates the mass spectrum of 2,3,4,5-tetrahydro-l//-l-benzazepine <75OMS(10)992). Biphenylene (m/e 152), acridinium cation (m/e 179) and fluorene cation (m/e 165) are the major fragments in the mass spectra of dibenz[T>,/]azepines (74CJRV101). 

POLYHYDROGEN FLUORIDE REAGENT 1-FLUORO-ADAMANTANE. Dichloroalkane synthesis is shown in cis-DI-CHLOROALKANES FROM EPOXIDES cis-1,2-DICHLORO-CYCLOHEXANE. Nitrile functionality can be introduced from a ketone, as in NITRILES FROM KETONES CYCLOHEXANENITRILE, or from a reactive diene, as shown in 2,3-DICYANOBUTADIENE AS A REACTIVE INTERMEDIATE BY in situ GENERATION FROM 1,2-DICYANO CYCLOBUTENE 2,3-DICYANO-1,4,4a,9a -TETRAHYDRO-FLUORENE. 

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. 

Yet other reaction pathways may be involved in reaction (a). Fluorene, e.g., is reduced to a radical anion by Li metal at low T. When fluorene is treated with a limited amount of Li metal, fluorenyllithium is formed with no evolution of Hj gas, but tetrahydro- and hexahydrofluorenes are produced . 

Scheme 77 Sc(OTf)3-catalyzed synthesis of tetrahydro-benzo[h]fluoren-ll-ones...

Surprisingly small /hh couplings have been observed by Bender et for 2 1 adduct of benzyne with 2-methylanizole, which has been shown to have the bisbenzotricyclic structure 6,6a, 11,11 a-tetrahydro-5-methoy-6-methyl- 5,6,11 -metheno- 5/f-benzo[a]fluorene. 

Indene-3-carboxylic acid, butadiene, toluene, and a trace of ferf-butylcatechol heated 24 hrs. at 120° in a steel bomb -> l,4,4a,9a-tetrahydro-4a-fluorene-carboxylic acid. Y 81%. F. e., also from esters, s. E. F. Godefroi and L. H. Si-manyi, J. Org. Ghem. 28, 1112 (1963). 

Ferrocenyl-tetrahydro-2-furyl-maleic anhydride, 206 Fluidized bed, MA reactor, 23, 29 Fluorene, acylation with MA, 98 Fluorenone, 185... 

---