18341-40-7Relevant academic research and scientific papers
Synthesis of Succinonitrile Derivatives by Homocoupling from Cyanohydrin Derivatives with a Low-Valent Titanium Reagent
Endo, Ryusei,Kishida, Atsushi,Matsunaga, Kazuma,Nagasawa, Kokoro,Takatori, Kazuhiko
, (2022/02/07)
A method is described for synthesizing succinonitrile derivatives bearing alkyl or aryl substituents from cyanohydrin derivatives using low-valent titanium. The active species in this reaction is proposed to be a resonance hybrid of the TiIV nitrile enolate and TiIII alkyl radical.
Regioselectivity of the photochemical addition of ammonia, phosphine, and silane to olefinic and acetylenic nitriles
Guillemin, Jean-Claude,Breneman, Curt M.,Joseph, Jeffrey C.,Ferris, James P.
, p. 1074 - 1082 (2007/10/03)
An investigation of the regioselectivity and mechanisms of the photochemical addition of NH3, PH3, and SiH4 to olefinic and acetylenic nitriles is described. The photolysis of NH3 in the presence of acrylonitrile led to the α-addition product 2-aminopropanenitrile (2), propanenitrile, and 2,3-dimethylbutanedinitrile (3). When NH3 was photolyzed in the presence of substituted derivatives (crotononitrile, methacrylonitrile, or 1-cyclohexenecarbonitrile), the α-addition products were still obtained. However, under similar reaction conditions, only the β-addition products, 7 and 8, were obtained from acrylonitrile and PH3, or acrylonitrile and SiH4, respectively. On the other hand, the photolysis of 2-butynenitrile and NH3 gave the β-addition products, (Z)- and (E)-3-aminocrotononitrile (10). The photolysis of these acetylenic nitriles with PH3 or SiH4 also gave the β-adducts (12) and (13). The α-addition of NH3 proceeds by the stepwise addition of H· and ·NH2, respectively, to the α,β-unsaturated nitriles. The β-addition products are formed by a radical chain mechanism initiated by photochemically generated radicals. The radical chain pathway provides an explanation for a number of previously described photochemical additions to olefins and acetylenes. Photochemical processes similar to the addition of ammonia and phosphine to unsaturated organic compounds may have played a role in the evolution of the atmosphere of the primitive Earth, and may even be currently occurring in the atmospheres of other planets.
Broensted Correlations for Electron Transfer from Carbanions to Halomethyl Phenyl Sulfone and 1,1-Dinitroalkane-Type Acceptors
Bordwell, Frederick G.,Clemens, Anthony H.
, p. 2510 - 2516 (2007/10/02)
9-Substituted fluorenyl carbanions, 9-G-Fl(1-), with G = Ar or Me, have been dimerized to (9-G-Fl)2 by reaction in Me2SO solution with PhSO2CH2X and R2C(NO2)X electron acceptors.Rate measurements revealed the following electron-accepting abilities: c-C6H10(NO2)2 > Me2C(NO2)2 > PhSO2CH2Br, PhSO2CH2I > c-C6H10(NO2)CN > c-C6H10(NO2)SO2C7H7 > Me2C(NO2)SO2C7H7 > PhSO2CH2Cl.The rate-limiting step in these reactions is electron transfer from 9-G-Fl(1-) to the electron acceptor.Plots of log k vs. pKa of 9-G-FlH are linear with a slope near unity for all seven electron acceptors studied.We conclude that a Broensted β of unity is characteristic of electron transfer from carbanions to electron acceptors in Me2SO solution.This is interpreted to mean that the changes in ΔG0 brought about by changes in the basicity of the carbanion are matched by changes in ΔG(excit.), which correspond to the difference in the energy gap between the HOMO of the donor and the LUMO of the acceptor.
