127239-63-8Relevant academic research and scientific papers
Novel Cycloadducts from the Reactions of benzyl Benzoate and ethyl Ethanoate with Furan
Barlow, Michael G.,Tajammal, Sabiha,Tipping, Anthony E.
, p. 1637 - 1639 (1989)
Reaction of furan with the dialkynyl ester (CF3CC)2CPhOCOPh (1a) in dichloromethane at 50 deg C affords a mixture of four 1:1 adducts, the (Z)-isomer of triene (4a) (major product), diketone (5a), and benzopentacyclononenes (3) and (6), via the common intermediate 2-benzoyloxy-2-phenyl-4,10-bis(trifluoromethyl)-7-oxapentacyclodec-3-ene (9) formed from the bis Diels-Alder adduct by intramolecular ( ? 2 s + ? 2 s + ? 2 s ) cycloaddition followed by retro-cleavage of furan; the corresponding reaction with the ester (CF3CC)2CMeOCOMe (1b) gives analogously diketone (5b) (major product) and a mixture of the (E)- and (Z)-isomers of triene (4b), a rearranged furan-dialkyne 2:1 adduct (7) or (8) also being formed.
Fluorinated Acetylenes. Part 10. Cycloaddition of α,α-Bis(3,3,3-trifluoropropynyl)benzyl Benzoate and 1,1-Bis(3,3,3-trifluoropropynyl)ethyl Ethanoate with Furan and Cyclopentadiene
Barlow, Michael G.,Tajammal, Sabiha,Tipping, Anthony E.
, p. 2485 - 2494 (2007/10/02)
Reaction between furan and the dialkynyl ester (CF3CC)2CPhO2CPh 1a in dichloromethane at 50 deg C gave four rearranged 1:1 adducts, (Z)-5-(α-benzoyloxybenzylidene)-1,4-bis(trifluoromethyl)-8-oxa-tricyclonona-3,6-diene 11a (major product), 4-benzoyloxy-3,8-bis(trifluoromethyl)-1,1a,2,8c-tetrahydro-4H-1,2,8b-epoxymethenocyclopropafluorene 15, the corresponding 3H-compound 16 and 8,9-dibenzoyl-4,7-bis(trifluoromethyl)-2-oxatetracyclonon-7-ene 13a via the common intermediate 2-benzoyloxy-2-phenyl-4,10-bis(trifluoromethyl)-7-oxapentacyclodec-3-ene 8a formed from the Diels-Alder adduct by intramolecular ( ? 2 S + ? 2 S + ? 2 S ) cycloaddition.The corresponding reaction with the ester (CF3CC)2CMeO2CMe 1b gave analogously the diketone 13b (major product) and a mixture of the (E)- and (Z)-isomers of the triene 11b; a 2:1 adduct, 4-acetoxy-3-methyl-5,11-bis(trifluoromethyl)-8,15-dioxahexacyclopentadeca-2,13-diene 10 was also isolated.A mixture of cyclopentadiene and the ester 1a (2:1 molar ratio), heated at 50 deg C, yielded mainly the bis-Diels-Alder adduct α,α-bis(3-trifluoromethylbicyclohepta-2,5-dien-2-yl)benzylbenzoate 7a, together with the rearranged 1:1 adduct, diketone 13c.Similarly, the major product from the reaction of an excess of cyclopentadiene with ester 1b at 50 deg C was the bis-Diels-Alder adduct 7b, but a 1: 1 molar ratio of reactants at 20 deg C gave the mono Diels-Alder adduct 1-(3-trifluoromethylbicyclohepta-2,5-dien-2-yl)-1-(3,3,3-trifluoropropynyl)ethyl ethanoate 6d in high yield.The bis adduct 7a was stable at 50 deg C, but the mono adduct 6d underwent slow intramolecular ( ? 2 S + ? 2 S + ? 2 S ) cycloaddition, cf., the furan reactions, and the intermediate 8d so formed rearranged to a mixture of 8,9-diacetyl-4,7-bis(trifluoromethyl)tetracyclonon-7-ene 13d and 1-acetoxy-1-non-7-en-9-yl>ethene 18.In the presence of traces of water, the ketone 13d was only a minor product with the major products being the substituted ethene 18 and two diastereoisomers of 1-acetoxy-1-non-7-en-9-yl)ethanol 19.
