The three-dimensional configuration of the ester heterocycle is basically the same as that of the carbocycle. Compound: 2-Bromopropanenitrile(SMILESS: CC(Br)C#N,cas:19481-82-4) is researched.Computed Properties of C7H3ClN2O2S. The article 《Ab Initio Evaluation of the Thermodynamic and Electrochemical Properties of Alkyl Halides and Radicals and Their Mechanistic Implications for Atom Transfer Radical Polymerization》 in relation to this compound, is published in Journal of the American Chemical Society. Let’s take a look at the latest research on this compound (cas:19481-82-4).
High-level ab initio MO calculations were used to study the thermodn. and electrochem. parameters relevant to the mechanism of atom transfer radical polymerization (ATRP). Homolytic bond dissociation energy (BDE) and standard reduction potential (SRP) were calculated for a series of alkyl halides (R-X; R = CH2CN, CH(CH3)CN, C(CH3)2CN, CH2COOC2H5, CH(CH3)COOCH3, C(CH3)2COOCH3, C(CH3)2COOC2H5, CH2Ph, CH(CH3)Ph, CH(CH3)Cl, CH(CH3)OCOCH3, CH(Ph)COOCH3, SO2Ph, Ph; X = Cl, Br, I) both in the gas phase and in two common organic solvents, acetonitrile and DMF. The SRP of the corresponding alkyl radicals, R•, was also examined The computational results are in a good agreement with the exptl. data. For all alkyl halides examined, , in the solution phase, one-electron reduction results in the fragmentation of the R-X bond to the corresponding alkyl radical and halide anion; a hypothetical outer-sphere electron transfer (OSET) in ATRP should occur via concerted dissociative electron transfer rather than a two-step process with radical anion intermediates. Both the homolytic and heterolytic reactions are favored by electron-withdrawing substituents and/or those that stabilize the product alkyl radical, which explains why monomers such as acrylonitrile and styrene require less active ATRP catalysts than vinyl chloride and vinyl acetate. The rate constant of the hypothetical OSET reaction between bromoacetonitrile and CuI/TPMA (tris[(2-pyridyl)methyl]amine) complex was estimated using Marcus theory for the electron-transfer processes. The estimated rate constant kOSET = ∼10-11 M-1 s-1 is significantly smaller than the exptl. measured activation rate constant (kISET = ∼82 M-1 s-1 at 25° in acetonitrile) for the concerted atom transfer mechanism (inner-sphere electron transfer, ISET), implying that the ISET mechanism is preferred. For monomers bearing electron-withdrawing groups, the one-electron reduction of the propagating alkyl radical to the carbanion is thermodynamically and kinetically favored over the one-electron reduction of the corresponding alkyl halide unless the monomer bears strong radical-stabilizing groups. Thus, for monomers such as acrylates, catalysts favoring ISET over OSET are required to avoid chain-breaking side reactions.
As far as I know, this compound(19481-82-4)Application In Synthesis of 2-Bromopropanenitrile can be applied in many ways, which is helpful for the development of experiments. Therefore many people are doing relevant researches.
Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI