Reaction of atomic fluorine with benzotrifluoride

Sams, Lewis C.

doi:10.1021/jo00425a021

Cited by 2 publications

(2 citation statements)

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“…However, SAMS and co-workers [8,9,10] have pointed out that F-for-H substitution in CgHsF, CfiHsBr andCsHsCFj by way of F atoms generated from F2 under cold plasma conditions, can still occur with considerable selectivity. Positional selectivity has also been observed in the radiolytic fluorination of toluene in the gaseous CF4 /CgHsCHj system [11] (cf.…”

Section: Halogen Replacementmentioning

confidence: 99%

“…This is particularly true for aromatic Compounds because of the intrinsic reactivity of the usual radical source Fj. More recently distinct positional selectivity has been reported for homolytic bromination [6,7] and fluorination [8,9,10,11 ] of halobenzenes by non-nuclear techniques. The use of nucleogenic atoms conceivably could shed more light on the role and nature of the attacking halogen atoms as well as on the particular effects displayed by different substituents in the aromatic target molecule.…”

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confidence: 99%

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Hot Atom Chemistry of ¹⁸F in Liquid Substituted Benzenes

Briνkman¹,

Visser²,

Lindner³

1979

Radiochimica Acta

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The reactions of nucleogenic '' F atoms recoiling in liquid substituted benzenes, toluenes and anilines among others, have been studied. In some cases the distribution of "F between organic and inorganic products depends markedly upon the type of substituents present. In particular the -NH^ and -CN group give rise to enhanced inorganic yields. With a few exceptions, the total replacement yield (hydrogen-, halogen-and group-replacement products) amounts to 10 to 15%. The unidentified 'polymer' fraction ranging from about 10% to about 60% is approximately complementary to the inorganic fraction. Highly fluorinated (substituted) benzenes generally give high polymer yields. The systems studied are not very sensitive with regard to the addition of I j. This is related to the intrinsic reactivity of recoiling "F atoms, particularly in aromatic systems. The main process is believed to be hot interaction with the 7r-electron system of the aromatic ring leading to excited TTor a-complexes. These intermediates are the precursors to the labeled organic products, possibly also partly to the inorganic fraction by way of H" F elimination. It is suggested that the polymer fraction may partly find its origin in ringopening and/or fragmentation of the excited complexes. Unlike the hot replacement reactions for substituent halogens or groups, a simple fast one-step hot mechanism does not fully explain '' F-for-H replacement. Positional selectivity in H-replacement is not very pronounced and is only slightly influenced by Ij. This suggests that the attacking '' F atoms exhibit some degree of electrophilic character.

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