ChemInform Abstract: Reactions of Halogen Fluorides. Part 9. Synthesis of Derivatives of α‐Fluoroacrylic Acid.

Chemical Modification of Oligonucleotides for Therapeutic, Bioanalytical and other Applications

“…The above type of reactions was also used for the synthesis of 2‐fluoroacrylic acid or acyl halide ( 32 ). The 1‐chloro‐2,3‐dibromopropane ( 33 ) was reacted with bromine trifluoride to form a mixture of 1‐chloro‐2‐fluoro‐3‐bromopropane ( 34 ) and 1‐chloro‐2,3,‐difluoropropane ( 35 ), which were then acetolized with AcOK, oxidized and dehydrohalogenated to yield 32 22. This important compound was also made by reacting α‐halo acids or esters with BrF 3 .…”

“…Boguslavskaya reacted unreactive double bonds such as in allyl chlorides, dibromo‐ and dichloroethylenes and got mixtures containing bromofluoro, 1,2‐difluoro and 1,1‐difluoro adducts each in relatively low yields (Scheme ). Based on these mixtures she believed that there were several independent transition states in operation 92…”

Selective Reactions of Bromine Trifluoride in Organic Chemistry

“…Based on these mixtures she believed that there were several independent transition states in operation. [92] Later on, under milder conditions the subject was revisited with more conclusive results. The additions to unsaturated aliphatic compounds such as 1-heptene (140) gave 1-bromo-2-fluoroheptane (141) in 50% yield, indicating an ionic Markovnikov regioselective mechanism.…”

“…The 1-chloro-2,3-dibromopropane (33) was reacted with bromine trifluoride to form a mixture of 1-chloro-2-fluoro-3-bromopropane (34) and 1-chloro-2,3,-difluoropropane (35), which were then acetolized with AcOK, oxidized and dehydrohalogenated to yield 32. [22] This important compound was also made by reacting a-halo acids or esters with BrF 3 . Boguslavskaya reacted a polyfluoroalkyl ester of 2,3-dibromopropionic acid (36a) with the reagent and after easy dehydrofluorination of the formed 2,3-difluoropropionate (37a) got the fluoroacrylic derivative 38.…”