Nitrous oxide in gas-phase ion-molecule chemistry: a versatile reagent for the determination of carbanion structure

Journal Article · Wed May 28 04:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00271a011· OSTI ID:5532849

Kass, S R; Filley, J; Van Doren, J M; DePuy, C H

Nitrous oxide has been found to undergo a wide variety of reactions with anions in the gas phase. The products of these reactions are highly characteristic of the ion's structure and, therefore, this reagent (N/sub 2/O) is especially useful in distinguishing between different types of ions. In general, primary carbanions react to produce diazo anions as the major products, secondary carbanions dehydrogenate, and tertiary carbanions afford adducts, oxygen atom transfer, and cleavage products. However, novel reaction channels can be brought about by modifying the reactant ion's structures. For example, deprotonation of methylene cyclopropane produces a strained allylic anion which reacts with N/sub 2/O to afford cyanide and the 2-nitrosoallyl anion, while removal of a proton from furan, which has a good ..cap alpha..-leaving group, generates the nitrogen atom transfer product, 3-cyanoacrolein radical anion, upon reaction with N/sub 2/O. It was observed that proton abstraction from cyclopentene, cyclohexene, and internal olefins without allylic methyl groups does not afford M - 1 ions in the flowing afterglow.

• Research Organization: Univ. of Colorado, Boulder
• OSTI ID: 5532849
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:11; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ADDUCTS
ANIONS
CARBANIONS
CHALCOGENIDES
CHARGED PARTICLES
CHEMICAL REACTIONS
DATA
EXPERIMENTAL DATA
FLUIDS
GASES
INFORMATION
IONS
MOLECULAR STRUCTURE
NITROGEN COMPOUNDS
NITROGEN OXIDES
NITROUS OXIDE
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
REACTION INTERMEDIATES