Regiospecific addition of CH₂O at the radical site of the ^˙CH₂CH₂OHCH₃⁺ distonic ion

Abstract

The reaction of the 'CH,CH,OHCH,+ distonic ion with CH,O was studied by Fourier transform ion cyclotron resonance spectrometry. The process is induced by an initial regiospecific attack of the carbon CH,O at the radical site of the distonic ion, leading to an intermediate adduct ion which loses water. The mechanism was demonstrated by labelling, by studying the structure of the product ion and by examining independently the behaviour of the putative intermediate radical cation.

C−F Bond Cleavage by Mass-Selected Free Radicals at Fluorinated Self-Assembled Monolayer Surfaces

“…Gas-phase studies show that • CH 2 CH 2 OCH 2 + can abstract CH 3 S • from CH 3 SSCH 3 , and • CH 2 OCH 2 + can abstract methylene from ketene . The corresponding ions CH 3 CH 2 OCH 2 + and CH 3 OCH 2 + do not react in these ways, indicating that the distonic ion chemistry is dominated by the radical center. , Because distonic ions are also distonic radicals, they can be used to explore the surface reactivity of free radicals. The effects of collision energy are then conveniently investigated by mass spectrometry and the reactions of α- and β-distonic ions with F-SAM surfaces were studied with these objectives.…”

A Hidden Hydrogen Transfer in the Unimolecular Reaction of 1,2-Dimethoxyethane•+

“…In the presence of acetonitrile, a rapid transfer of ionized ethylene occurs 14,15 while, with methanal, a cycloaddition process yields ionized 1,3-dioxane ( m / z 88) followed by hydrogen radical loss, giving m / z 87 . The behavior of 5 differs also from that of the other isomers, whose formation is highly improbable in this system, such as the enol structure CH 3 C(OH)CH 2 •+ . , …”

“…16 The behavior of 5 differs also from that of the other isomers, whose formation is highly improbable in this system, such as the enol structure CH 3 C(OH)CH 2 •+ . 12,17 Intermediacy of 3 for Both Fragmentations. Energetic measurements, studied by synchrotron radiation give a clear demonstration of the existence of a common intermediate in the formation of both fragments, m/z 58 and m/z 60.…”

Hydrogen radical abstraction by small ionized molecules, distonic ions and ionized carbenes in the gas phase

“…•+ addition product then eliminates a water molecule [30]. Furthermore, iodine abstraction from allyl iodide (Eq.…”

“…A first example has been given by the reaction of the • CH 2 CH 2 OHCH 3 + ion with CH 2 O [30]. The first step of the reaction, of an H-bonded complex involving an acidic hydrogen of the ion and the oxygen atom of formaldehyde, followed by a C-C bond formation between the radical carbon of the ion and the carbon of the neutral.…”