6788-63-2Relevant academic research and scientific papers
Determination of thermodynamic affinities of various polar olefins as hydride, hydrogen atom, and electron acceptors in acetonitrile
Cao, Ying,Zhang, Song-Chen,Zhang, Min,Shen, Guang-Bin,Zhu, Xiao-Qing
, p. 7154 - 7168 (2013/08/23)
A series of 69 polar olefins with various typical structures (X) were synthesized and the thermodynamic affinities (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the polar olefins obtaining hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the polar olefins (X ?-) obtaining protons and hydrogen atoms, and the thermodynamic affinities of the hydrogen adducts of the polar olefins (XH?) obtaining electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The pure Ci - 'C π-bond heterolytic and homolytic dissociation energies of the polar olefins (X) in acetonitrile and the pure Ci - 'C π-bond homolytic dissociation energies of the radical anions of the polar olefins (X?-) in acetonitrile were estimated. The remote substituent effects on the six thermodynamic affinities of the polar olefins and their related reaction intermediates were examined using the Hammett linear free-energy relationships; the results show that the Hammett linear free-energy relationships all hold in the six chemical and electrochemical processes. The information disclosed in this work could not only supply a gap of the chemical thermodynamics of olefins as one class of very important organic unsaturated compounds but also strongly promote the fast development of the chemistry and applications of olefins.
Synthesis of the First Crystalline Thiaanthracenes, 9-Cyano- and 9-(Ethoxycarbonyl)-10-methyl-10-thiaanthracenes, and Their Reactions with Electrophiles
Hori, Mikio,Kataoka, Tadashi,Shimizu, Hiroshi,Ohno, Sachio
, p. 2468 - 2473 (2007/10/02)
The isolable and crystalline thiaanthracene derivatives 9-cyano- (9) and 9-(ethoxycarbonyl)-10-methyl-10-thiaanthracene (12) were synthesized in high yield for the first time by proton abstraction from the corresponding thioxanthenium salts (8a or 8b and 11) with sodium hydride in THF under a nitrogen atmosphere.Upon standing in THF at 50 deg C, thiaanthracenes 9 and 12 underwent thermal 1,4-rearrangement to give the corresponding thioxanthenes 13 and 14, respectively.The ylidic property of the thiaanthracenes was manifested by spectral and chemical evidences.Reactions of the thiaanthracenes with electrophiles such as dimethyl acetylenedicarboxylate and tetracyanoethylene are also described together with the course of the reactions.
