Claisen rearrangement of allyl phenyl ether: heavy-atom kinetic isotope effects and bond orders in the transition structure

Journal Article · Wed Oct 12 04:00:00 EDT 1988 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00229a032· OSTI ID:5830295

Kupczyk-Subotkowska, L; Saunders, Jr, W H; Shine, H J

Kinetic isotope effects (KIE) were measured for the rearrangement at 220/degree/C of allyl ether (1) which was labeled successively at its oxygen atom ((/sup 18/O)-1), /alpha/-carbon atom ((/alpha/-/sup 14/C)-1), /gamma/-carbon atom ((/gamma/-/sup 14/C)-1), and ortho-carbon atom ((2-/sup 14/C)-1). The KIE were 1.0297 (/sup 18/O), 1.0306 (/alpha/-/sup 14/C), 1.0362 (/gamma/-/sup 14/C), and 1.0375 (2-/sup 14/C). KIE were determined from isotopic abundances in the product, o-allylphenol (2), which were measured by multiscan mass spectrometry (/sup 18/O) and scintillation counting (/sup 14/C). A model of the transition structure was then developed, whose bond orders gave calculated KIE in reasonably good agreement not only with the experimentally determined heavy-atom KIE but also with the deuterium KIE reported earlier by McMichael and Korver. A loose transition structure was thus found for the rearrangement of 1 into 2. In this transition structure the C/sub /alpha//-O bond is 50-60% broken while the C/sub /gamma//-C/sub ortho/ bond is only 10-20% complete. The results thus define this concerted, nonsynchronous rearrangement more explicitly than hitherto possible. 40 references, 8 tables.

• Research Organization: Texas Tech Univ, Lubbock (USA)
• OSTI ID: 5830295
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:21; 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
ALKYL RADICALS
ALLYL RADICALS
ARYL RADICALS
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CARBON 14
CARBON ISOTOPES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CLAISEN CONDENSATION
DATA
ETHERS
EVEN-EVEN NUCLEI
EXPERIMENTAL DATA
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN 18
OXYGEN ISOTOPES
PHENYL RADICALS
RADICALS
RADIOISOTOPES
REACTION KINETICS
STABLE ISOTOPES
YEARS LIVING RADIOISOTOPES