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Preparation of 2,3-dimethylene-2,3-dihydrofurans by the flash vacuum pyrolysis of substituted furylmethyl esters

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00412a026· OSTI ID:5637975
; ;
Pyrolysis of 3-methylfurfuryl benzoate gives a 21% yield of 3-methyl-4-methylenecyclobutenone and a 24% yield of 4H,5H,9H,10H-cycloocta)1,2-b:6,5-b')difuran (8), the head-to-head, (4 + 4) dimer of 2,3-dimethylene-2,3-dihydrofuran (6). A similar pyrolysis of 2-methyl-3-furylmethyl benzoate (10) gives 8 in 51% yield. Low-temperature /sup 1/H and /sup 13/C NMR spectral studies show that 6 is the intermediate in the formation of 8. Compound 6 reacts with methyl acrylate to form a mixture of the isomeric Diels-Alder adducts. Pyrolysis of 2-methyl-3-furylmethyl-..cap alpha..,..cap alpha..-d/sub 2/ benzoate (10-d/sub 2/) gives 8-d/sub 4/ via the intermediacy of 6-d/sub 2/. Pyrolysis of 2,4-dimethyl-3-furylmethyl benzoate gives a 43% yield of 3,6-dimethyl-4H,5H,9H,10H-cycloocta(1,2-b:6,5-b') difuran (13), the head-to-head, (4 + 4) dimer of 4-methyl-2,3-dimethylene-2,3-dihydrofuran (14). Low-temperature /sup 1/H and /sup 13/C NMR studies show that 14 is the intermediate in the formation of 13. Compound 14 can be trapped with methyl acrylate to form a 3.1 to 1 ratio of the Diels-Alder adducts 15 and 16. The structure proof of 15 and 16 involves the conversion of 15 to the commercially available, natural product menthofuran and 16 to isomenthofuran, which is synthesized by an independent route.
Research Organization:
Iowa State Univ., Ames
DOE Contract Number:
W-7405-ENG-82
OSTI ID:
5637975
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:22; ISSN JACSA
Country of Publication:
United States
Language:
English

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Technical Report · Thu Feb 28 23:00:00 EST 1985 · OSTI ID:5949736
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Technical Report · Mon Jun 01 00:00:00 EDT 1987 · OSTI ID:6478303
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
ALDEHYDES
BARYONS
BENZOIC ACID
CARBON 13
CARBON ISOTOPES
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
DEUTERIUM
ELEMENTARY PARTICLES
ESTERS
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
FERMIONS
FURANS
FURFURAL
HADRONS
HETEROCYCLIC COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MONOCARBOXYLIC ACIDS
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUCLEONS
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PROTONS
PYROLYSIS
RESONANCE
STABLE ISOTOPES
THERMOCHEMICAL PROCESSES