- Radical-nucleophilic substitution (SRN1) reactions. Part 7. Reactions of aliphatic α-substituted nitro compounds
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α-Nitrothiocyanates R2C(SCN)NO2 have been prepared by oxidative addition of thiocyanate anion to nitronate anions and undergo SRN1 substitution reactions by loss of thiocyanate with nitronate anions, phenylsulfinate, azide and p-nitro- and p-chloro-benzenethiolates in dipolar aprotic solvents. 2-Nitro-2-thiocyanatopropane and other 2-substituted-2-nitropropanes [Me2C(X)NO2 with X = I, Br, Cl, NO2, PhSO2] react with thiolates by SRN1 reactions and/or redox reactions to give disulfides by a polar abstraction or chain SET (SET2) mechanisms. The products are dependent on the nucleophilicity of the thiolates, the polarisability of the α-substituent, the solvent and the presence of light catalysis, radical traps or strong electron acceptors. 2-Substituted-2-nitropropanes [Me2C(X)NO2 with X = N3, NO2, CN, p-NO2-C6H4-N=N] undergo SRN1 substitutions with thiolates by loss of nitrite. 2-Substituted-2-nitropropanes Me2C(X)NO2 and thiolates only yield disulfides in methanol due to solvation of the nitro groups.
- Al-Khalil,Bowman,Gaitonde,Marley,Richardson
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p. 1557 - 1565
(2007/10/03)
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- RADICAL-NUCLEOPHILIC SUBSTITUTION (SRN1) REACTIONS OF α-NITRO-THIOCYANATES
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α-Nitro-thiocyanates undergo substitution by a SRN1 mechanism with a range of anions to give loss of thiocyanate, corroborating behaviour observed for the intermediate α-nitro-thiocyanato radical-anions by e.s.r. spectroscopy.
- Al-Khalil, Suleiman I.,Bowman, W. Russell
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p. 2517 - 2520
(2007/10/02)
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