Rh(III)-Catalyzed Olefination and Alkylation of Arenes with Maleimides: A Tunable Strategy for C(sp2)–H Functionalization

We herein report a new nitrogen-directed Rh(III)-catalyzed C(sp2)–H bond functionalization of N-nitrosoanilines and azoxybenzenes with maleimides as a coupling partner, in which the olefination/alkylation process can be finely controlled at room temperature by variation of the reaction conditions. This method shows excellent functional group tolerance, and presents a mild access to the resulting olefination/alkylation products in moderate to good yields.

Electrochemical synthesis of functionalized gem-difluoroalkenes with diverse alkyl sources via a defluorinative alkylation process

An electrochemical defluorinative alkylation protocol of α-trifluoromethyl alkenes is described. The present reaction enables the preparation of functionalized gem-difluoroalkenes with the use of diverse alkyl sources including organohalides, N-hydroxyphthalimide (NHP)...

Nonsteady-state mathematical modelling of H2SO4-catalysed alkylation of isobutane with alkenes

H2SO4-catalysed isobutane alkylation with alkenes is an important industrial process used to obtain high-octane alkylate. In this process, the concentration of H2SO4 is one of the main parameters. For alkylation, sulphuric acid containing 88%–98% monohydrate is typically used. However, only a H2SO4 concentration of 95%–96% enables alkylate with the maximum octane number to be obtained. Changes in H2SO4 concentration due to decontamination are the main cause of process variations. Therefore, it is necessary to maintain the reactor acid concentration at a constant level by regulating the supply of fresh catalyst and pumping out any spent acid. The main reasons for the decrease in the H2SO4 concentration are accumulation of high-molecular organic compounds and dilution by water. One way to improve and predict unsteady alkylation processes is to develop a mathematical model that considers catalyst deactivation. In the present work, the formation reactions of undesired substances were used in the description of the alkylation process, indicating the sensitivity of the prediction to H2SO4 activity variations. This was used for calculation the optimal technological modes ensuring the maximum selectivity and stability of the chemical–technological system under varying hydrocarbon feedstock compositions.

Stereoselective Synthesis of 2-Trifluoromethylated and 2-Difluoromethylated Dihydrofurans via Organocatalytic Cascade Michael/Alkylation Reaction

A highly stereoselective cascade Michael/alkylation process has been established to construct 2-trifluoromethylated and 2-difluoromethylated dihydrofurans from readily available starting materials. In the presence of a bifunctional squaramide, the annulation approach...

Nanoconfined Crosslinked Poly(ionic liquid)s with Unprecedented Selective Swelling Properties Obtained by Alkylation in Nanophase-Separated Poly(1-vinylimidazole)-l-poly(tetrahydrofuran) Conetworks

Despite the great interest in nanoconfined materials nowadays, nanocompartmentalized poly(ionic liquid)s (PILs) have been rarely investigated so far. Herein, we report on the successful alkylation of poly(1-vinylimidazole) with methyl iodide in bicontinuous nanophasic poly(1-vinylimidazole)-l-poly(tetrahydrofuran) (PVIm-l-PTHF) amphiphilic conetworks (APCNs) to obtain nanoconfined methylated PVImMe-l-PTHF poly(ionic liquid) conetworks (PIL-CNs). A high extent of alkylation (~95%) was achieved via a simple alkylation process with MeI at room temperature. This does not destroy the bicontinuous nanophasic morphology as proved by SAXS and AFM, and PIL-CNs with 15–20 nm d-spacing and poly(3-methyl-1-vinylimidazolium iodide) PIL nanophases with average domain sizes of 8.2–8.4 nm are formed. Unexpectedly, while the swelling capacity of the PIL-CN dramatically increases in aprotic polar solvents, such as DMF, NMP, and DMSO, reaching higher than 1000% superabsorbent swelling degrees, the equilibrium swelling degrees decrease in even highly polar protic (hydrophilic) solvents, like water and methanol. An unprecedented Gaussian-type relationship was found between the ratios of the swelling degrees versus the polarity index, indicating increased swelling for the nanoconfined PVImMe-l-PTHF PIL-CNs in solvents with a polarity index between ~6 and 9.5. In addition to the nanoconfined structural features, the unique selective superabsorbent swelling behavior of the PIL-CNs can also be utilized in various application fields.