- Reactions of 4-Methyl-1-(1'-methylethyl)-4-nitrocyclohexa-2,5-dien-1-yl Acetates with Nitrogen Dioxide: Towards a Mechanism for the Formation of Polynitro Cyclohexenyl Esters on Reaction of p-Cymene with Nitrogen Dioxide in Acetic Anhydride
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The acetoxy nitro diene (21), the C3-epimeric 3,4,6-trinitro-5-nitratocyclohexenes (24) and (25) , the 3,6-dinitro-5-nitratocyclohexa-1,3-diene (29), and the 3,6-dinitro-5-acetoxycyclohexa-1,3-diene (32) are identified as probable intermediates in the formation of polynitro cyclohexenyl esters (4)-(13) on reaction of p-cymene with nitrogen dioxide in acetic anhydride; probable reaction pathways are discussed.The X-ray crystal analysis of 4-methyl-1-(1'-methylethyl)-t-5-nitrato-r-3,t-4,c-6-trinitrocyclohexene (24) is reported.
- Abell, Andrew D.,Hartshorn, Michael P.,Robinson, Ward T.,Waller, A. Grant,Wright, Graeme J.
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p. 2225 - 2242
(2007/10/02)
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- The Nitration of p-Cymene with Nitrogen Dioxide in Acetic Anhydride
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Reaction of p-cymene (1) with nitrogen dioxide in acetic anhydride gives polynitro nitrates (4)-(10), polynitro acetates (11)-(13), and nitro aromatic compounds (14)-(17).X-Ray crystal analyses are reported for compounds (5)-(9), (11) and (12).
- Hartshorn, Michael P.,Robinson, Ward T.,Waller, A. Grant,Wright, Graeme J.
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p. 2143 - 2160
(2007/10/02)
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- THE NITRATION OF p-CYMENE WITH NITROGEN DIOXIDE IN ACETIC ANHYDRIDE: THE ISOLATION AND X-RAY STRUCTURE DETERMINATION OF 6-METHYL-3-(METHYLETHYL)-t-5-NITRATO-1,r-3,c-4,t-6-TETRANITROCYCLOHEXENE
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Reaction of p-cymene (1a) with nitrogen dioxide in acetic anhydride gives 2-nitro-p-cymene (1b), p-nitrotoluene (2), and the tetranitronitratocyclohexene (3) as the major products; the X-ray crystal structure of (3) is reported.
- Hartshorn, Michael P.,Robinson, Ward T.,Waller, A. Grant,Wright, Graeme J.
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p. 1999 - 2000
(2007/10/02)
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- Electrophilic aromatic substitution. Part 24. The nitration of isopropylbenzene, 2- and 4-isopropyltoluene, 1-chloro-4-isopropylbenzene, 4-isopropylanisole, and 2-bromotoluene: Nitrodeisopropylation
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The kinetics and products of nitration in aqueous sulphuric acid of the title compounds have been studied. 4-Isopropyl-phenol and -anisole are nitrated at or near the encounter rate. In 65-79% H2SO4 2-isopropyltoluene suffers ca. 25% ipso-attack; the only fate of W iPri (ipso-Wheland intermediate) is nitrodeisopropylation. From 4-isopropyltoluene WiPri is also nitrodeisopropylated, but some 1,2-nitro-migration may occur. From the same compound WiMe may be captured by water, rearrange, or give 4-methylacetophenone; a mechanism is proposed for the formation of the last compound. Nitrodeisopropylation occurs without the assistance of water. With 4-isopropylanisole, demethoxylation and nitrodeisopropylation are consequences of the formation of WiPri. The results are consistent with increasing attack at C-4 with increasing acidity, loss of isopropyl without assistance from water, and decomposition of the unobserved intermediate, 4-isopropyl-4-nitrocyclohexa-2,5-dienone, by two processes. One, acid-catalysed process gives 4-nitrophenol and possibly 4-isopropyl-2-nitrophenol. The other, probably radical, process gives 4-isopropyl-2-nitrophenol. In contrast to 4-bromotoluene, 2-bromotoluene is not nitrodebrominated.
- Manglik, Ajay K.,Moodie, Roy B.,Schofield, Kenneth,Tobin, Geoffrey D.,Coombes, Robert G.,Hadjigeorgiou, Panicos
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p. 1606 - 1616
(2007/10/02)
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