79035-76-0Relevant academic research and scientific papers
Preparation of fluorohalomethylmagnesium halides using highly active magnesium metal and their reactions
Kví?ala, Jaroslav,?tambasky, Jan,Skalicky, Martin,Paleta, Old?ich
, p. 1390 - 1395 (2007/10/03)
Highly active magnesium (Rieke magnesium) reacts with fluorohalomethanes at -100°C forming the corresponding fluorohalomethylmagnesium halides, which undergo nucleophilic substitution with silyl halides or nucleophilic addition with aldehydes or ketones. Whereas the stability of dibromofluoromethylmagnesium bromide (2a) was sufficient to provide acceptable product yields with dimethylphenylsilyl chloride, benzaldehyde, butyraldehyde or acetophenone as electrophiles, other fluoroorganomagnesium halides, bromodifluoromethylmagnesium bromide (2b), bromochlorofluoromethylmagnesium bromide (2c) and trifluoromethylmagnesium iodide (2d) displayed only very limited stability and thus the corresponding yields of reactions with electrophiles were low.
REACTION OF (BROMODIFLUOROMETHYL)PHENYLDIMETHYLSILANE WITH ORGANOMETALLIC REAGENTS
Fuchikami, Takamasa,Ojima, Iwao
, p. 145 - 153 (2007/10/02)
A new fluorine-containing organosilicon compound, (bromodifluoromethyl)phenyldimethylsilane (II), was synthesized by the N-bromosuccinimide (NBS) bromination of (difluoromethyl)phenyldimethylsilane (I), which was prepared from phenyldimethylsilyllithium and chlorodifluoromethane.Compound II reacted with dimethyl sulfoxide to give dimethyl sulfide and phenyldimethylfluorosilane in quantitative yield.The reaction of II with nucleophiles, such as sodium ethoxide, Grignard or lithium reagents, afforded products arising from cleavage of the carbon-silicon bond.In contrast, the reaction of II with Grignard reagents in the presence of appropriate catalysts (Group VIII transition metal salts or complexes) afforded the homo-coupling product of II, 1,2-bis(phenyldimethylsilyl)-1,1,2,2-tetrafluoroethane (IV), in excellent yield.The silver(I) salt-catalyzed reaction of II with ethylmagnesium bromide gave the cross-coupling product, (1,1-difluoropropyl)phenyldimethylsilane (V) as well as III and IV.When cuprous bromide was employed as catalyst, the reaction of II with ethylmagnesium bromide afforded 1-phenyldimethylsilyl-1-propene (VI) and 3-phenyldimethylsilyl-2-pentene (VII) as main products.
