Fluoroamines

FLUORINECOMPOUNDS,ORGANIC - FLUOROETTiERS AND FLUOROAMINES] (Vol 11) 4(9H-Fluoren-9-ylidenemethyl)-N,N-bis(methylphenyl)benzenamine [ql[115838-15-8]... 

The observation by Yarovenko and Raksha " in 1960 that diethyl (2-chloro-1,1,2-trifluoroethyl) amine (hereafter called fluoroamine ) could replace hydroxyl groups by fluorine was first applied in the steroid field byAyer and Knox and co-workers. These workers found that a methylene... 

Under mild conditions and in a variety of solvents, tertiary steroid alcohols are inert to the fluoroamine. At elevated temperatures, however, they afford exclusively, and in high yield, products resulting from dehydration with or without rearrangement. Thus, 17a-methyltestosterone (10) furnishes in 42% yield the 18-norsteroid (11). 

Careful studies of the reaction of the fluoroamine with the homoallylic alcohols 3 -fluoro-19-hydroxycholest-5-ene and 3a- and 3j5-hydroxy-17j5-acetoxyestr-5(10)-ene which bear on the proposed mechanism have been reported recently. 

The A -fluoroamine salt reagents are also prepared by direct fluorination. Thus, N-fluoroquinuclidinmmsalts [71, 72],N-fluorotnethylenediammoniumsalts [73], and Af-tluoropyndinium salts [74] are prepared as shown in equations 32-34 (Table 3b, entries I, I, and K)... 

Reactions of benzylic a,P-aminoalcohols and a-hydroxyazindines with Olah s reagent provide a highly efficient way to a P-fluoroamines, a-fluoro-azindines, and ot,Y-difluoroamines [dS] (equations 43 and 44)... 

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