The reaction of 1,3-dibutyl-2-ethoxy-4,5-dimethyl-2-oxo-1,3,2-diazaphosphol-4-ene with tetracyanoethylene

The reaction of 1,3-dibutyl-2-ethoxy-4,5-dimethyl-2-oxo-1,3,2-diazaphosphol-4-ene with tetracyanoethylene gives 6-amino-1,3-dibutyl-5-cyano-2-ethoxy-4-(1-imino-2-cyanoethyl)-2-oxo-1,3,2-diazaphosphindane.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 303–305, February, 1994.     

Dichotomy in the reaction between cinnamyl dithiocarboxylates and tetracyanoethylene with the formation of 7,8-dithiabicyclo[3.2.1]octanes and dithioacyloxycyclopentanes

The reaction of cinnamyl dithiocarboxylates (1) containing electron-donating substituents at the central carbon atom of the dithioester group (R = p-MeOC₆H₄, EtO, andp-Tol) with tetracyanoethylene affords 2,2,3,3-tetracyano-4-endo-phenyl-7,8-dithiabicyclo[3.2.1]octanes (2) as well as isomeric 3,3,4,4-tetracyano-2-phenyl-trans-1-dithioacyloxycyclopentanes (3). Dithiabicyclooctanes2 rearrange to the corresponding cyclopentanes3 upon thermolysis.Dedicated to Academician of the RAS N. S. Zefirov (on his 60th birthday).Deceased in August, 1995.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1804–1808, September, 1995.This work was supported by the Russian Foundation for Basic Research (Project No. 93-03-04290), the International Science Foundation and the Russian Government (Grant M5Y 300), and the Russian State Committee on Higher Education (Scientific and Technical Program Fine Organic Synthesis, Project FT-12).     

Molecular complexes of crown ethers. Part 3. Effect of cations on charge transfer complexes with TCNE

The intermolecular charge transfer complexes (CT) of two crown ethers (CE), viz, B15C5 and DB18C6 (as donors), and tetracyanoethylene (TCNE), as acceptor, were studied in the UV-visible region in dichloroethane (DCE), at 298.2 K. The sequence of addition of the cation was varied in the case of B15C5 such that in one system the sequence was (CE+Cation)+TCNE and in the other (CE+TCNE)+cation. These two systems were found to be non-interchangeable, even under reflux conditions, giving differentK _c values which were explained as being due to the different geometries of the CE. For the first sequence, the values most affected depended on the fit of the metal cation with the ether cavity, thus in B15C5, Na⁺ showed the greatest effect, while for DB18C6 it was K⁺.     

Reactions of Selenobenzophenones with Olefins

Reactions of selenobenzophenones with methyl propiolate afforded two types of cycloadducts regioselectively. The reaction with tetracyanoethylene gave selenophene derivatives. Mechanisms of these reactions were discussed.     

High‐Yield Formation of Substituted Tetracyanobutadienes from Reaction of Ynamides with Tetracyanoethylene

A high‐yielding sequence of [2+2] cycloaddition–retroelectrocyclization of ynamides with tetracyanoethylene (TCNE) is described. The reaction provided tetracyanobutadiene (TCBD) species, which were characterized by various techniques. DFT and TD‐DFT calculations were also performed to complement experimental findings.     

Formation of Long,Multicenter π‐[TCNE]22− Dimers in Solution: Solvation and Stability Assessed through Molecular Dynamics Simulations

Purely organic radical ions dimerize in solution at low temperature, forming long, multicenter bonds, despite the metastability of the isolated dimers. Here, we present the first computational study of these π‐dimers in solution, with explicit consideration of solvent molecules and finite temperature effects. By means of force‐field and ab initio molecular dynamics and free energy simulations, the structure and stability of π‐[TCNE]₂^2? (TCNE=tetracyanoethylene) dimers in dichloromethane have been evaluated. Although the dimers dissociate at room temperature, they are stable at 175 K and their structure is similar to the one in the solid state, with a cofacial arrangement of the radicals at an interplanar separation of approximately 3.0 Å. The π‐[TCNE]₂^2? dimers form dissociated ion pairs with the NBu₄⁺ counterions, and their first solvation shell comprises approximately 20 CH₂Cl₂ molecules. Among them, the eight molecules distributed along the equatorial plane of the dimer play a key role in stabilizing the dimer through bridging C?H???N contacts. The calculated free energy of dimerization of TCNE ^{. ?} in solution at 175 K is ?5.5 kcal mol^?1. These results provide the first quantitative model describing the pairing of radical ions in solution, and demonstrate the key role of solvation forces on the dimerization process.     

Plasma polymerization of cyano compounds

Plasma polymerizations of three cyano compounds—acrylonitrile (AN), 1,2-dicyanoethylene (FN), and tetracyanoethylene (TCE)—were investigated by FT IR and XPS, and the transforamtion of cyano groups during the plasma polymerization was discussed. The results pointed out an aspect of the preparation of plasma films with cyano groups. Plasma polymerizations of AN, FN, and TCE deposited brown or dark brown films that contained carbon, nitrogen, and oxygen. The elemental composition of the plasma films, especially N/C atomic ratio, showed a monomer dependence but no rf power dependence. The plasma films contained amide and amino groups, and ketene-imine and conjugated — C = N — structures as well as cyano groups as nitrogen functionalities, and carbonyl and carboxyl groups as oxygen functionalities. For the preparation of plasma films with cyano groups, compounds with more than two cyano groups themselves are not suitable as monomers. The operation of plasma polymerization under mild plasma conditions at low rf power and in no oxygen atmosphere is favorable for the preparation of plasma films with cyano groups. © 1992 John Wiley & Sons, Inc.