Mechanism of base-induced gas-phase elimination reactions of ethers

Journal Article · Wed Mar 18 04:00:00 EST 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00240a019· OSTI ID:6869011

de Koning, L J; Nibbering, N M.M.

For the base-induced gas-phase elimination reactions of diethyl ether and cis- and trans-1-tert-butyl-4-methoxy-cyclohexane the kinetic isotope and leaving group effects have been determined as functions of the base strength using the method of Fourier transform ion cyclotron resonance mass spectrometry. The results are interpreted in terms of a variable E2 transition-state structure. Increasing the base strength causes the transition state to shift toward the carbanion or E1cb region of the E2 spectrum, which is also a general phenomenon in the condensed phase. Moreover, it appears that the elimination reactions most readily proceed via a transition state in which the ..beta.. hydrogen and leaving group are periplanar. If the substrate does not easily allow such a relationship, the transition state is found to shift toward the carbenium ion or E1 region of the E2 spectrum where the geometric restrictions of the substrate are less perceptible.

• Research Organization: Univ. of Amsterdam, Netherlands
• OSTI ID: 6869011
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:6; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ALKANES
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CYCLOALKANES
CYCLOHEXANE
CYCLOTRON RESONANCE
DATA
DEUTERIUM COMPOUNDS
ELEMENTS
ETHERS
FLUIDS
FOURIER TRANSFORM SPECTROMETERS
GASES
HYDROCARBONS
HYDROGEN
HYDROGEN COMPOUNDS
INFORMATION
ION CYCLOTRON-RESONANCE
ISOTOPE EFFECTS
KINETICS
MASS SPECTROSCOPY
MATHEMATICAL MODELS
MEASURING INSTRUMENTS
MOLECULAR MODELS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PH VALUE
PHASE STUDIES
REACTION KINETICS
RESONANCE
SPECTROMETERS
SPECTROSCOPY
THEORETICAL DATA