- Photochemical Nitration by Tetranitromethane. XV. Formation of Adducts and their Secondary Products in the Photochemical Reaction between Benzene and Tetranitromethane
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Photolysis of benzene/tetranitromethane in dichloromethane or acetonitrile with light of λ>435 nm gives four main product categories, namely, in dichloromethane at +20 deg C (relative yield, products): adducts 1 of hydroxy/trinitromethyl type (total 54percent, see below), nitro substitution products (total 8percent, nitrobenzene, 1,3-dinitrobenzene and 1,3,5-trinitrobenzene), trinitromethyl substitution products (26percent, trinitromethylbenzene, 1-nitro-4-trinitromethylbenzene, 1,3-dinitro-5-trinitromethylbenzene) and phenols (total 12percent, 2,4- and 2,6-dinitrophenol, 2,4,6-trinitrophenol). In acetonitrile at +20 deg C the same product groups comprised 15, 24, 39 and 18percent, respectively, and, in addition, a low yield (1.7percent) of what is formally a cycloaddition product between 4-nitrobenzonitrile N-oxide and acetonitrile, 5-methyl-3-(4-nitrophenyl)-1,2,4-oxadiazole 2. The structure of 2 was determined by single crystal X-ray analysis. The main adducts were assigned the structures of a cis/trans pair of 1-hydroxy-4-trinitromethylcyclohexa-2,5-diene (NMR). Their formation in both dichloromethane and acetonitrile shows that adduct formation from photolysis of tetranitromethane/aromatics is not only confined to polycyclic aromatics but can occur with a maximally resonance-stabilized system, like benzene itself. The high complexity of the product mixture can be explained partly by elimination reactions of adducts, combined with further thermal and photochemical transformations.
- Eberson, Lennart,Calvert, Jane L.,Hartshorn, Michael P.,Robinson, Ward T.
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p. 347 - 355
(2007/10/02)
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- REACTIONS OF NITRILE OXIDES WITH NITROGEN OXIDES. 2. REACTIONS WITH NITROGEN MONOXIDE AND NITROGEN SESQUIOXIDE
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We have studied the reactions of aromatic nitrile oxides with nitrogen monoxide and nitrogen sesquioxide.It was shown that the nitrogen monoxide removes an oxygen atom from the nitrile oxide with formation of the corresponding nitrile and nitrogen dioxide.The reaction products with nitrogen sesquioxide are formed as a result of reactions of the nitrile oxide with nitrogen monoxide and nitrogen tetroxide.
- Rakitin, O. A.,Ogurtsov, V. A.,Godovikova, T. I.,Khmel'nitskii, L. I.
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p. 1472 - 1474
(2007/10/02)
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- REACTIONS OF NITRILE OXIDES WITH NITROGEN OXIDES. 1. REACTIONS WITH NITROGEN TETROXIDE
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We have studied the reaction of nitrile oxides with nitrogen tetroxide.It was shown that the reaction is selective: acetonitrile oxide yields ethylnitrolic acid, α-oximinophenylacetonitrile oxide gives a mixture of isomers of phenylnitrofuroxan, and aromatic nitrile oxides give aryltrinitromethanes.
- Rakitin, O. A.,Ogurtsov, V. A.,Godovikova, T. I.,Khmel'nitskii, L. I.
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p. 1469 - 1471
(2007/10/02)
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