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Full-Text Articles in Physical Sciences and Mathematics

Co2 Production In The Bromate-1,4-Cyclohexanedione Oscillatory Reaction, Jiamin Feng, James R. Green, Samuel A. Johnson, Jichang Wang Jun 2011

Co2 Production In The Bromate-1,4-Cyclohexanedione Oscillatory Reaction, Jiamin Feng, James R. Green, Samuel A. Johnson, Jichang Wang

Chemistry and Biochemistry Publications

NMR and GC/MS spectroscopy of the organic extracts of the oscillatory bromate-1,4-cyclohexanedione reaction illustrate the presence of ring-opening products 5-(dibromomethylene)-2(5H)-furanone, (E)-5,5,5-tribromo-4-oxo-2-pentenoic acid, and dibromoacetic acid, particularly at elevated temperatures. The loss of a carbon atom from the six-membered ring after ring opening led to gas formation and such a process became more vigorous at >60 °C, with the direct observation of bubbles in a stirred batch reactor. Gravimetric experiments confirm that the amount of carbon dioxide gas produced increases rapidly with reaction temperature. Parallel experiments suggest that the ring-opening process involves the oxidation of brominated benzoquinones by bromate. Copyright © …


Dehydrotropylium-Co2(Co)6 Ion. Generation, Reactivity And Evaluation Of Cation Stability, Sheida Amiralaei, James Gauld, James R. Green Apr 2011

Dehydrotropylium-Co2(Co)6 Ion. Generation, Reactivity And Evaluation Of Cation Stability, Sheida Amiralaei, James Gauld, James R. Green

Chemistry and Biochemistry Publications

The dehydrotropylium–Co2(CO)6 ion was generated by the action of HBF4 or BF3OEt2 on the corresponding cycloheptadienynol complex, which in turn has been prepared in four steps from a known diacetoxycycloheptenyne complex. The reaction of the cycloheptadienynol complex via the dehydrotropylium–Co2(CO)6 ion with several nucleophiles results in substitution reactions with reactive nucleophiles (N>1) under normal conditions, and a radical dimerisation reaction in the presence of less reactive nucleophiles. Competitive reactions of the cycloheptadienynol complex with an acyclic trienynol complex show no preference for generation of the dehydrotropylium–Co2 …


Synthesis Of ‘Spacer’-Naproxen [2-(6-Methoxybiphenylen-2-Yl)Propanoic Acid] And -Isonaproxen [2-(7-Methoxybiphenylen-2-Yl)Propanoic Acid], Juan A. González Gómez, James R. Green, Peter C. Vollhardt Apr 2011

Synthesis Of ‘Spacer’-Naproxen [2-(6-Methoxybiphenylen-2-Yl)Propanoic Acid] And -Isonaproxen [2-(7-Methoxybiphenylen-2-Yl)Propanoic Acid], Juan A. González Gómez, James R. Green, Peter C. Vollhardt

Chemistry and Biochemistry Publications

The CpCo(CO)2-catalyzed cocyclization of 1,2-diethynyl- 4-methoxybenzene with alkynes can be applied to the synthesis of ‘spacer’-naproxen [2-(6-methoxybiphenylen-2-yl)propanoic acid] and its 7-methoxy isomer, ‘spacer’-isonaproxen. While unsymmetrical alkynes are incorporated without regioselectivity, the methoxy group in 6-methoxy-2,3-bis(trimethylsilyl)biphenylene directs electrophiles to C-3, thus allowing for regiochemical differentiation between the 2- and 3-positions.