I. Kinetic and mechanistic study of the (4+4) dimerization of 2,3-dimethylene-2,3-dihydrofuran. II. Preparation of 2,3-dimethylene-2,3-dihydrogenzo(b)furan by the flash vacuum pyrolysis of 2-methyl-3-benzo(b)furylmethyl benzoate. III. Reaction of 2,3-dimethylene-2,3-dihydrofuran with triplet oxygen
A kinetic and mechanistic study of the (4+4) dimerization of 2,3-dimethylene-2,3-dihydrofuran (A) has been carried out based on the secondary deuterium kinetic isotope effects (2/sup 0/ D KIE), substituent effects and solvent effects. The 2/sup 0/ D KIE was studied by measuring the rate constants, k/sub 1/, k/sub 2/, k/sub 3/ and k/sub 4/, respectively, for the (4+4) dimerization of A, 2-methylene-3-dideuteriomethylene-2,3-dihydrofuran (B), 2-dideuteriomethylene-3-methylene-2,3-dihydrofuran (C) and 2,3-bis-(dideuteriomethylene)-2,3-dihydrofuran (D). 2-3-Dimethylene-2,3-dihydrobenzo(b)furan (E) was synthesized by the flash vacuum pyrolysis of 2-methyl-3-benzo(b)furylmethyl benzoate. The chemical reactions of E, which were investigated in this study, include thermal dimerization reactions and Diels-Alder reactions. The dimerization reaction of E gave both (4+2) and (4+4) dimers. The formation of cyclic peroxides from the reactions of A and its 5-methyl and 5-tert-butyl derivatives with triplet oxygen was investigated. Thermolysis of a cyclic peroxide gave dialdehyde, hydroxy aldehyde and diol as the products. 150 references, 28 figures, 70 tables.
- Research Organization:
- Ames Lab., IA (USA)
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 5949736
- Report Number(s):
- IS-T-1186; ON: DE85009234
- Resource Relation:
- Other Information: Portions of this document are illegible in microfiche products. Thesis
- Country of Publication:
- United States
- Language:
- English
Similar Records
Gas-phase intramolecular Diels-Alder reactions of 2,3-dimethylene-2,3-dihydrofurans. II. Formation of anthracene and other polycyclic aromatic compounds in the pyrolysis of 1,5-bidenzocyclooctadienes and related compounds. III. Formation of 9-methylanthracene and anthracene in the pyrolysis of 5,6,11,12-tetrahydrodibenzo(A,E)cyclooctene and other related compounds. IV. Preparation of cyclopentadienones by flash vacuum pyrolysis and their dimerization and intramolecular reactions
(4 + 4) dimerization of 2,3-dimethylene-2,3-dihydrofuran: secondary deuterium kinetic isotope effect evidence of a two-step mechanism
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BENZOFURANS
DIELS-ALDER REACTION
DIMERIZATION
DEUTERIUM
ISOTOPE EFFECTS
FURANS
ALDEHYDES
ALKENES
AROMATICS
BENZENE
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CYCLOALKENES
ESTERS
EXPERIMENTAL DATA
GEL PERMEATION CHROMATOGRAPHY
GLYCOLS
HIGH TEMPERATURE
HIGH VACUUM
INFRARED SPECTRA
ISOTOPIC EXCHANGE
METHANE
NUCLEAR MAGNETIC RESONANCE
ORGANIC OXYGEN COMPOUNDS
PEROXIDES
POLYMERIZATION
PYROLYSIS
PYROLYSIS PRODUCTS
THEORETICAL DATA
ALCOHOLS
ALKANES
CHEMICAL REACTIONS
CHROMATOGRAPHY
DATA
DECOMPOSITION
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
INFORMATION
ISOTOPES
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
REACTION KINETICS
RESONANCE
SEPARATION PROCESSES
SPECTRA
STABLE ISOTOPES
SYNTHESIS
THERMOCHEMICAL PROCESSES
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)