Thomas G. Archibald

Intramolecular reactions of nitroolefin-β-diketone Michael adducts : Formation of 3-oxo-2,3-dihydro-4H-1,2-benzoxazine and 4(5H)-benzofuranone derivatives

Abstract 1,3-Cyclohexanedione (3) undergoes Michael addition to β-nitrostyrene in methanolic sodium methoxide to form 3,5-dioxo-4-phenyl-2,3,5,6,7,8-hexahydro-4H-1,2-benzoxazine (5a). With 1-nitropropene 3 forms the corresponding 4-methyl derivative (5b). These substances had been designated as 4-substituted 5-oxo-5,6,7,8-tetrahydro-4H-1,2-benzoxazine-2-oxides (4a, b) by other workers. 5,5-Dimethyl-1,3-cyclohexanedione (9) under similar conditions adds to β-nitrostyrene to form 2-(2-nitro-1-phenylethyl)-5,5-dimethyl-1,3-cyclohexanedione (10); 9 and 2-nitro-1-phenylpropene yield 3-phenyl-2,6,6-trimethyl-6,7-dihydro-4(5H)-benzofuranone (12). In other reactions various β-diketones add to nitroolefins to yield normal Michael adducts, 4-nitro-1-alkanones (1, 2). Molecular ion fragmentation patterns and mechanisms of formation of the abnormal addition products are presented and their rationalizations discussed.

Reaction of diphenylacetylene with organophosphides - A stereospecific synthesis of vinyl phosphines.

Reaction of lithium diphenyl phosphide with diphenylacetylene producing high yields of stereochemically pure vinyl phosphides in presence of primary or secondary amine

Lithium cleavage of unsaturated vicinal di-tert-phosphines

Abstract Lithium metal in tetrahydrofuran has been found to react with ethynylenebis(diphenylphosphine) and cis - or trans -1,2-vinylenebis(diphenylphosphine) to produce lithium diphenylphosphide in high yield. Possible mechanistic paths are discussed. In this connection the reactions of the vinylenebis- and ethynylenebis(diphenylphosphines) with lithium diphenylphosphide have been examined and the results are discussed.