593-75-9Relevant articles and documents
Reddy,Berry
, p. 111,112-114 (1977)
Tunneling Model for Hydrogen Abstraction Reactions in Low-Temperature Solids. Applications to Reactions in Alcohol Glasses and Acetonitrile Crysals
Roy, Robert J. Le,Murai, Hisao,Williams, Ffrancon
, p. 2325 - 2334 (1980)
A simple and internally consistent quantitative model for hydrogen-abstraction reactions in low-temperature solids, which implicitly incorporates zero point energy effects which allow for finite reaction rates at T=0 K, is derived and applied to new measurements of H-abstraction rate constants by methyl radicals in methanol and ethanol glasses at T=13-99 K and in acetonitrile and methyl isocyanide crystals at 69-128 K.Nonlinear least-squares fits of the model to the experimental data yield effective one-dimensional barriers to reaction whose heights are virtually independent of the analytic form used for the potential energy barrier, and are somewhat larger than the activation energies measured for the corresponding reactions in the gas phase.This model predicts that values of the isotopic rate constant ratio kH/KD will be larger than 1012 at T=0 K.
Single photon ionization of methyl isocyanide and the subsequent unimolecular decomposition of its cation: Experiment and theory
Bellili,Gouid,Gazeau,Bénilan,Fray,Guillemin,Hochlaf,Schwell
, p. 26017 - 26026 (2019)
Methyl isocyanide, CH3NC, is a key compound in astrochemistry and astrobiology. A combined theoretical and experimental investigation of the single photon ionization of gas phase methyl isocyanide and its fragmentation pathways is presented. Vacuum ultraviolet (VUV) synchrotron radiation based experiments are used to measure the threshold photoelectron photoion coincidence (TPEPICO) spectra between 10.6 and 15.5 eV. This allowed us to experimentally determine the adiabatic ionization energy (AIE) and fragment ion appearance energies (AE) of gas-phase methyl isocyanide. Its AIE has been measured with a precision never achieved before. It is found to be AIEexp = 11.263 ± 0.005 eV. We observe a vibrational progression upon ionization corresponding to the population of vibrational levels of the ground state of the methyl isocyanide cation. In addition, four fragment ion appearance energies (AEs) were measured to be AE (m/z 40) = 12.80 ± 0.05 eV, AE (m/z 39) = 13.70 ± 0.05, AE (m/z 15) = 13.90 ± 0.05 eV, AE (m/z 14) 13.85 ± 0.05 eV, respectively. In order to interpret the experimental data, we performed state-of-the-art computations using the explicitly correlated coupled cluster approach. We also considered the zero-point vibrational energy (ZPVE), core-valence (CV) and scalar relativistic (SR) effects. The results of theoretical calculations of the AIE and AEs are in excellent agreement with the experimental findings allowing for assignment of the fragmentations to the loss of neutral H, H2, CN and HCN upon ionization of CH3NC. The computations show that in addition to the obvious bond breakings, some of the corresponding ionic fragments result from rearrangements-upon photon absorption-either before or after electron ejection.
Coetzee et al.
, p. 1139,1141 (1962)
Pressure Dependence of the Laser-Initiated Isomerization of Methyl Isocyanide
Shultz, M. J.,Rock, Elizabeth J.,Tricca, Robert E.,Yam, Loretta M.
, p. 5157 - 5162 (1984)
The infrared laser-induced isomerization of methyl isocyanide has been investigated and found to exhibit a marked pressure dependence; i.e., for a given set of conditions, there exists a sharp threshold pressure above which there is massive isomerization.In the subthreshold region, it has been determined that the yield depends exponentially on the pressure for a multimode beam.Since other authors have suggested that this laser-induced reaction is a thermal explosion, we have also carried out a numerical simulation of this system as a thermal explosion.Both the experimental and theoretical results are presented, and the results show that the thermal explosion model does not fit the experimental data.
Synthesis and structure–activity relationship of α-keto amides as enterovirus 71 3C protease inhibitors
Zeng, Debin,Ma, Yuying,Zhang, Rui,Nie, Quandeng,Cui, Zhengjie,Wang, Yaxin,Shang, Luqing,Yin, Zheng
supporting information, p. 1762 - 1766 (2016/12/22)
α-Keto amide derivatives as enterovirus 71 (EV71) 3C protease (3Cpro) inhibitors have been synthesized and assayed for their biochemical and antiviral activities. structure–activity relationship (SAR) study indicated that small moieties were primarily tolerated at P1' and the introduction of para-fluoro benzyl at P2 notably improved the potency of inhibitor. Inhibitors 8v, 8w and 8x exhibited satisfactory activity (IC50= 1.32 ± 0.26 μM, 1.88 ± 0.35 μM and 1.52 ± 0.31 μM, respectively) and favorable CC50values (CC50> 100 μM). α-Keto amide may represent a good choice as a warhead for EV71 3Cproinhibitor.
