Fluor-olefine durch Fluormethylenierung von Carbonylverbindungen
Stirred 10.25 g ClO3F in 300 ml MePh at -70 Deg, under N, was treated with 160 ml 0.41M triphenylphosphonium methylide to give 98% [Ph3P+CH2F]ClO3- (I), m. 131-4 Deg (CH2Cl2-AcOH-EtOAc). Satd. 1 equiv. I in Me2CO treated with 1.25 equivs. NaI in Me2CO gave 90% [Ph3P+CH2F]I- (II), m. 169-71 Deg. Stirred 29.5 g II in 450 ml tetrahydrofuran at -78 Deg was treated dropwise with LiBr-contg. LiPh in Et2O to give Ph3P+C-HF which reacted with BzH to give 65% PhCH:CHF (50:50 cis-trans ratio), b65 71-4 Deg. Similarly was prepd. C5H11CH:CHF 45:55 cis-trans ratio b. 100-4 Deg, as well as the following compds. in 50:50 cis-trans ratio: 3-F3CC6H4CH:CHF, 3-ClC6H4CH:CHF, b15 84-7 Deg, and III, m. 138-41 Deg, in 55, 25, 65 and 16% yields, resp. [on SciFinder (R)]
Keywords: Olefins Role: SPN (Synthetic preparation) ; PREP (Preparation) (fluoro ; by fluoromethylenation of carbonyl compds.); Methylenation (fluoro- ; of carbonyl compds. ; fluoro olefins by); Carbonyl compounds Role: RCT (Reactant) ; RACT (Reactant or reagent) (flu ; fluoromethylation carbonyls fluoro olefins; carbonyls fluoromethylation fluoro olefins; olefins fluoro fluoromethylation carbonyls; phosphorus org compds; triphenyl phosphonium fluoro methylides; phosphonium triphenyl fluoro methylides; methylides fluor
Noncondensed Aromatic Compounds
Org.-Chem. Inst.,Univ. Heidelberg,Heidelberg,Fed. Rep. Ger.
written in German.
20405-77-0P; 20405-78-1P; 28028-91-3P; 28028-92-4P; 28028-93-5P; 28028-94-6P; 28028-95-7P; 28028-96-8P; 28028-97-9P; 28096-31-3P; 28096-32-4P; 28096-33-5P; 28096-34-6P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of)
Record created on 2006-03-03, modified on 2016-08-08