The formation and reactions of adducts formed in the nitration of p-diethylbenzene

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dc.contributor.authorThompson, Robert Jamesen_US
dc.date.accessioned2024-08-15T20:09:17Z
dc.date.available2024-08-15T20:09:17Z
dc.date.copyright1978en_US
dc.date.issued1978
dc.degree.departmentDepartment of Chemistry
dc.degree.levelMaster of Science M.Sc.en
dc.description.abstractNitration of 𝑝-diethylbenzene by acetyl nitrate in acetic anhydride at -45°C gives the diastereoisomeric l,4-diethyl-4-nitrocyclohexa-2,5-dienyl acetates (IA and IB), 1-(p-ethylphenyl)-nitroethane (II), and 2,5-diethyl­nitrobenzene (III). The stereochemistry of the acetoxynitro adducts was studied using the n.m.r. shift reagent, tris­-(1,l,l,2,2,3,3-heptafluoro-7,7-dimethyl-d6-4,6-octane­-dionato)-europium. The formation of the dienyl adducts and the side-chain nitre product through the ipso attack of nitronium ion at the carbon bearing an ethyl group is discussed. The reactions of the ipso-cation, l,4-diethyl-l­-nitrocyclohexa-2,5-dienyl carbonium ion (IV) with water to form the l,4-diethyl-4-nitrocyclohexa-2,5-dienols (V), with methanol to form the dienyl methyl ethers (VI), and with acetic acid-d4 to form the trideuterated analogues (VII) of I are presented. The reactions of I under conditions which promote rearomatisation have been studied and discussed in terms of formation of IV or l-acetoxy-l,4-diethylcyclohexa-2,5-dienyl cation (VIII). Rearomatisation of I under acidic conditions gives III and p -ethylacetophenone (IX) derived from side-chain substituted products. Rearomatisation of I in aqueous methanol gives 2,5-diethylphenyl acetate (X) and methanolic sodium methoxide solvolysis of I gives V which rearomatises with a 1,2-alkyl shift to give 2,4-diethyl­-phenol (XI).en_US
dc.format.extent138 pages
dc.identifier.urihttps://hdl.handle.net/1828/19901
dc.rightsAvailable to the World Wide Weben_US
dc.titleThe formation and reactions of adducts formed in the nitration of p-diethylbenzeneen_US
dc.typeThesisen_US

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