Process for the manufacture of...

C - Chemistry – Metallurgy – 07 – D

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C07D 487/08 (2006.01) C07F 9/6561 (2006.01)

Patent

CA 2226175

A process for producing 1-substituted-4-fluoro-1,4- diazoniabicyclo[2.2.2]octane salts having formula (I) wherein the Z substituent is OH, OR, OC(O)R, SO3, SO2R, NO2, NO, or PO(OR)2, wherein R is an aryl or C1-C8 alkyl group; n is 0, 1 or 2; each of R1, R2, R3, R4 and R5 independently represent hydrogen, C1 to C8 alkyl, or aryl. 1-substituted-1,4- diazoniabicyclo[2.2.2]octane or 1,4-diazoniabicyclo[2.2.2]octane mono-N-oxide is reacted to attach the Z group and then the result is reacted with molecular fluorine in the presence of a solvent that substantially does not react with fluorine and a fluoride scavenger that results in an X counter ion. These compounds are useful as fluorinating agents for the introduction of fluorine into organic compounds.

L'invention a trait à un procédé de fabrication de sels 4-fluoro-1,4-diazoniabicyclo [2.2.2] octane substitués en 1 répondant à la formule (I). Dans cette formule, le substituant de Z est OH, OR, OC(O)R, SO¿3?, SO¿2?R, NO¿2?, NO ou PO(OR)¿2?, R représentant un groupe aryle ou un groupe alkyle comportant de 1 à 8 atomes de carbone. Dans cette même formule, n vaut 0, 1 ou 2; R¿1?, R¿2?, R¿3?, R¿4? et R¿5? représentent chacun, de manière indépendante, un hydrogène, un alkyle comportant de 1 à 8 atomes de carbone ou un aryle. On fait réagir un 1,4-diazoniabicyclo [2.2.2] octane substitué en 1 ou un 1,4-diazoniabicyclo [2.2.2] octane mono-N-oxyde pour rattacher le groupe Z puis on fait réagir le produit résultant avec du fluor sous forme moléculaire en présence d'un solvant ne réagissant quasiment pas avec le fluor ainsi qu'avec un accepteur de fluorure, ce qui donne un contre-ion X. Ces composés se révèlent efficaces comme agents de fluoruration pour l'introduction de fluor dans des composés organiques.

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