A simple and efficient approach for highly selective preparation of nitrocyclohexane from cyclohexane with tert-butyl nitrite catalyzed by N-hydroxyphthalimide

Organocatalysis in Inert C–H Bond Functionalization

“… TBN acted as the nitrogen source as well as the oxidant, reacting with NHPI to generate PINO radical and NO species. Benzyl radical formed in situ coupled with NO radical to form nitrosomethyl arene intermediate . Detailed mechanistic studies indicated the aldoxime is the key intermediate in this transformation, which was converted into nitrile in the presence of palladium .…”

UV‐Induced C−H Functionalization of Alkanes with NO2 in Supercritical Carbon Dioxide

“…O 2 raised it to 39 %, which exceeds the known data significantly. [15] On the contrary, the yield of nitro compound 2 a decreased to trace amounts (2 %) (Figure 2). Interestingly, even in the rigorous oxygen-free conditions (in the reactor preliminary purged with argon), CÀ O "coupling" still occurs as the minor reaction.…”

“…[20] Recently developed liquid-phase radical nitration reactions, initiated at 25-70 °C by a catalyst (N-hydroxyphthalimide -NHPI) [19] or UV irradiation, [21] are of lesser explosion risks. Nitrogen oxide (IV), [22] dilute nitric acid, [23] or butyl nitrite [15] are usually employed as the reagents, and trifluorotoluene or excess of alkane (up to 20-fold) -as the suitable reaction media. The nitroalkanes yield [15,[21][22][23] based on the nitrating agent reached 20-70 %, whereas corresponding yields based on the alkane did not exceed 4 %.…”

“…Nitrogen oxide (IV), [22] dilute nitric acid, [23] or butyl nitrite [15] are usually employed as the reagents, and trifluorotoluene or excess of alkane (up to 20-fold) -as the suitable reaction media. The nitroalkanes yield [15,[21][22][23] based on the nitrating agent reached 20-70 %, whereas corresponding yields based on the alkane did not exceed 4 %. Moreover, the products are difficult to separate from the residual alkanes, the catalyst, and/ or fluorinated solvent.…”

“…[9][10][11][12][13][14] Furthermore, nitrate, hydroxyl, keto and some other functionalities can be introduced into alkanes by means of these reactions. [15,16] In industry, alkanes react with nitrogen oxides in gas phase at up to 450 °C. [17][18][19] These processes are hazardous, nonselective, and applicable only in obtaining the simplest molecules.…”