169178-80-7Relevant academic research and scientific papers
Thermal and photochemical decomposition pathways of trinitromethylarenes. part II. The effects of ethanol on the photolysis reactions of some alkoxy- and dialkoxyarenes in the presence of tetranitromethane. enhancement of adduct and trinitromethyl substitution product formation
Butts, Craig P.,Eberson, Lennart,Hartshorn, Michael P.,Persson, Ola
, p. 718 - 732 (2007/10/03)
The photolysis of the charge transfer (CT) complex of tetranitromethane with 1-methoxynaphthalene, 1,4-dimethoxybenzene, 1,2-dimethoxybenzene, 1,2-methylenedioxybenzene or 2-methylanisole is reported for dichloromethane, acetonitrile, dichloromethane-ethanol and acetonitrile-ethanol solvent systems. The effects of adding ethanol (8% v/v ? 1.4 mol dm-3) to dichloromethane or acetonitrile as reaction solvents include: (i) the stabilization of alkoxytrinitro-methylarenes, thus reducing their normal tendency for decomposition according to ArC (NO2)3→ArCOOH→ArNO2, (ii) a reduction in the nucleophilicity of trinitromethanide ion, and (iii) changes in the regioselectivity of trinitromethanide ion attack on the radical cations of alkoxyaromatic compounds away from attack ipso to the alkoxy substituent. Adducts are also stabilized, as shown by the photolysis of the CT complex of 1,4-dimethoxybenzene-tetranitromethane in dichloromethane-ethanol (8% v/v) which gives the epimeric 1,4-dimethoxy-3-nitro-6-trinitromethylcyclohexa-1,4-dienes and 1,4-dimethoxy-2-trinitromethylbenzene, in addition to 1,4-dimethoxy-2-nitrobenzene. The adducts are detected also among the products of photolysis reactions in neat dichloromethane or acetonitrile. Acta Chemica Scandinavica 1997.
Photochemical Nitration by Tetranitromethane. Part XXII. Adducts as Precursors of Nitro Substitution Products from the Photolysis of 1-Methoxynaphthalene-Tetranitromethane, Dehydrodimer Formation and the Regiochemistry of Trinitromethanide Ion Attack on the Radical Cation of ...
Butts, Craig P.,Eberson, Lennart,Hartshorn, Michael P.,Persson, Ola,Robinson, Ward T.
, p. 253 - 264 (2007/10/02)
The photolysis of 1-methoxynaphthalene with tetranitromethane in dichloromethane at 20 deg C gives mainly 1-methoxy-4-nitronaphthalene (2) and 1-methoxy-4-trinitromethylnaphthalene (5), together with smaller amounts of 1-methoxy-2-nitronaphthalene (1) and the two adducts, 4-methoxy-r-1-nitro-t-2-trinitromethyl-1,2-dihydronaphthalene (6) and 4-methoxy-r-2-nitro-t-1-trinitromethyl-1,2-dihydronaphthalene (7).Photolysis in the presence of trifluoroacetic acid under otherwise identical conditions gives initially exclusively 4,4'-dimethoxy-1,1'-binaphthalene (10) as the product, trinitromethanide ion being eliminated as a reactant by protonation to give nitroform.EPR spectral and cyclic voltammetric data indicate that the radical cation 10 is present in this reaction.Evidence is presented that, in the absence of trifluoroacetic acid, the reaction products 1, 2 and 5 all arise by decomposition of highly labile nitro-trinitromethyl or nitrito-trinitromethyl adducts 11, 12 and 14.The regiochemistry of attack of trinitromethanide ion on the radical cation of 1-methoxynaphthalene is discussed, and it is proposed that this step is reversible, the regiochemistry of attack being determined by the relative energies of the carbon radicals formed in the process.X-Ray crystal structures are reported for 1-methoxy-4-trinitromethylnaphthalene (5) and 4,4'-dimethoxy-1,1'-binaphthalene (10).
