173437-05-3Relevant academic research and scientific papers
Preference of the mesolytic cleavage over the nuclear substitution observed in the ozone-mediated nitration of bicumene with nitrogen dioxide. Implication to the electron transfer nature of the Kyodai-nitration of arenes
Suzuki, Hitomi,Mori, Tadashi
, p. 647 - 648 (1996)
Ozone-mediated reaction of bicumene with nitrogen dioxide in dichloromethane at low temperature results in almost complete mesolytic cleavage of the hydrocarbon, accompanied by little or no nuclear nitration, in accordance with operation of the electron transfer process involving the nitrogen trioxide as initial electrophile.
Ozone-mediated nitration of bicumene and derivatives with nitrogen dioxide. Preferential mesolytic bond cleavage over nuclear nitration in evidence for the electron transfer nature of the kyodai-nitration of arenes
Suzuki, Hitomi,Mori, Tadashi
, p. 1265 - 1274 (2007/10/03)
The ozone-mediated reaction of bicumene and some derivatives 1 with nitrogen dioxide in dichloromethane at low twmperatures resulted in the facile cleavage of the central C-C bond to give the corresponding benzyl nitrate and its descendants 4-6. mesolytic bond cleavage occured almost exclusively over nuclear substitution at temperatures as low as -20 deg C, especially at low concentration (2 x 10-3 mol dm-3).This result may be rationalized in terms of initial electron transfer between the aromatic substrate and nitrogen trioxide in situ to form the aromatic radical cation, which then undergoes C-C bond scission at the benzylic position.In contrast, bibenzyl 2a is simply nitrated on the aromatic ring under similar conditions, giving the expected nitration products 7 and 8a-c along with a small amount of benzaldehyde 9.Results obtained from semi-empirical calculations and cyclic voltammetry are also in accord with the electron transfer nature of the reaction.The C-Si bond fission of benzyltrimethylsilane, C-C bond fragmentation of cyclic acetals of aromatic carbonyl compounds as well as side-chain reactions of toluene and derivatives, have all previously been observed under certain conditions of the kyodai-nitration and can be understood on a similar basis as described above.The possible involment of electron transfer processes in aromatic nitration with acetyl nitrate has also been suggested.
Iron(III)-catalysed nitration of non-activated and moderately activated arenes with nitrogen dioxide-molecular oxygen under neutral conditions
Suzuki, Hitomi,Yonezawa, Shuji,Nonoyama, Nobuaki,Mori, Tadashi
, p. 2385 - 2389 (2007/10/03)
In the presence of molecular oxygen and a catalytic amount of tris(pentane-2,4-dionato)iron(III), non-activated and moderately activated arenes, which include alkylbenzenes, halogenobenzenes, phenolic ethers, naphthalene and derivatives, can be nitrated with nitrogen dioxide at ice-bath temperature or below to give the corresponding nitro derivatives in fair to good yields. An electron-transfer mechanism has been proposed, where an activated NO2-FeIII complex plays a key role in the cyclic process for converting arenes into nitroarenes.
