- Nucleophilic Amination of Methoxy Arenes Promoted by a Sodium Hydride/Iodide Composite
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A method for the nucleophilic amination of methoxy arenes was established by using sodium hydride (NaH) in the presence of lithium iodide (LiI). This method offers an efficient route to benzannulated nitrogen heterocycles. Mechanistic studies showed that the reaction proceeds through an unusual concerted nucleophilic aromatic substitution.
- Kaga, Atsushi,Hayashi, Hirohito,Hakamata, Hiroyuki,Oi, Miku,Uchiyama, Masanobu,Takita, Ryo,Chiba, Shunsuke
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supporting information
p. 11807 - 11811
(2017/09/20)
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- Iron-catalyzed tandem one-pot addition and cyclization of the blaise reaction intermediate and nitroolefins: Synthesis of substituted NH-pyrroles from nitriles
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The iron-catalyzed addition and cyclization of the Blaise reaction intermediate and nitroolefins to synthesize highly functionalized NH-pyrroles in a tandem one-pot manner from nitriles has been developed. This reaction shows good functional group tolerance and affords a broad spectrum of substituted NH-pyrroles in good yields. Copyright
- Zhao, Mi-Na,Liang, Hao,Ren, Zhi-Hui,Guan, Zheng-Hui
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supporting information
p. 221 - 226
(2013/03/13)
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- Primary kinetic hydrogen isotope effects in deprotonations of a nitroalkane by intramolecular phenolate groups
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Rate constants and kinetic isotope effects have been determined for the formation of nitronate anions from the ethers 1-(2-methoxyphenyl)-2- nitropropane, 7(X=H, L=H and D) and 1-(2-methoxy-5-nitrophenyl)-2-nitropropane, 7(X=NO2, L=H and D), and from the corresponding phenols, 1-(2-hydroxyphenyl)-2-nitropropane, 3(X=H, L=H and D), and 1-(2-hydroxy-5- nitrophenyl)-2-nitropropane, 3(X=NO2, L=H and D), in aqueous basic medium. For the ethers 7, rates of deprotonation by hydroxide are comparable with those found for deprotonations of 2-nitropropane, with kH/k D (25 °C)=7.7 and 7.8, respectively. In both the cases, the isotope effects are conventionally temperature dependent. For the corresponding phenols 3, conditions have been established under which the deprotonations of the nitroalkane are dominated by intramolecular deprotonation by the kinetically first-formed phenolate anion, with an estimated effective molarity EM ～ 250. For 3 (X=H, L=H or D), kH/kD (25 °C)=7.8, with EaD - EaH =6.9 kJ mol-1 and AH/AD=0.5. For 3(X=NO2, L=H or D), rates of intramolecular deprotonation are reduced 30-fold, and an elevated kinetic isotope effect is found (kH/kD (25 °C)=10.7). Activation parameters (EaD - EaH =17.8 kJ mol-1 and AH/AD=0.008) are compatible with an enhanced tunnelling contribution to reactivity in the H-isotopomer. Copyright
- Backstroma, Nicholas,Burtona, Neil A.,Watta, C. Ian F.
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experimental part
p. 711 - 722
(2011/05/06)
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- Porphyrin synthesis from nitrocompounds
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A new porphyrin synthesis starting from nitroalkenes or their equivalents is described. For example, octaethylporphyrin, coproporphyrin, porphyrin-1,2,3,4,5,6,7,8 octapropionic acid, and 2,7,12,17 tetraarylporphyrin are prepared in good yield from readily available materials such as 1-nitropropane, nitroethane, nitromethane, and aldehydes.
- Ono, Noboru,Kawamura, Hisayuki,Bougauchi, Masahiro,Maruyama, Kazuhiro
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p. 7483 - 7496
(2007/10/02)
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