Reaction Of Tetracyanoethylene Research Articles

Condensation reactions of tetracyanoethylene and its monoanion promoted by Lewis acids: synthesis and crystal, molecular, and electronic structure of a novel heterocycle, the 2,3,6,7-tetracyano-5-(tricyanoethenylimino)-3H-1,4,7b-triazabenzo[i,j]pentalenide ion

From the condensation reaction of tetracyanoethylene (C6N4, TCNE) with its radical monoanion (C6N4˙–) promoted by a Lewis acid [ZnCl2, AlCl3, or V(bpy)3+2], a novel heterocyclic carbanion (C17N11–) has been synthesized and characterized by X-ray, 13C NMR, IR, and UV spectroscopy and cyclic voltammetry measurements. The crystal and molecular structure of the title anion has been determined for the tetraphenylarsonium salt, and its electronic structure and the mechanism of formation are discussed.

Reaction of 1-vinylpyrazoles with tetracyanoethylene

It was shown that in the reaction of tetracyanoethylene with 1-vinylpyrazoles in aprotic solvents, one of the first stages involves the formation of π-π complexes. The final products of the reaction are 1-(2,2,3,3-tetracyano-1-cyclobutyl)pyrazoles.

ChemInform Abstract: Electronic and Structural Properties of Novel Cyanocarbon Dyes Based on Tetracyanoethylene

Four novel cyanocarbon dyes derived from tetracyanoethylene (TCNE) have been studied. They are carbanions isolated as tetraphenylarsonium salts of formula C11N7H2–(1), C15N6H3–(2), C14N7H2–(3), and C13N8H–(4). Compound (1) was obtained by a condensation reaction of TCNE promoted by Ti(bpy)3 and its structure has already been reported. Compounds (2)–(4) are the 1,3-bistricyanovinyl derivatives of cyclopentadienyl, pyrrolyl, and imidazolyl anions, respectively. The tetraphenylarsonium salt of anion (3) gives crystals isomorphorus with the crystals of the analogous salts of anions (2) and (4), whose crystal structures are reported here. Structural and electronic properties of the four anions are discussed on the basis of 13C n.m.r., i.r., u.v., and electrochemical data; electrical and magnetic properties of their radical salts with the tetrathiafulvalenium cation (TTF˙+) are also reported and discussed.

Electronic and structural properties of novel cyanocarbon dyes based on tetracyanoethylene

Four novel cyanocarbon dyes derived from tetracyanoethylene (TCNE) have been studied. They are carbanions isolated as tetraphenylarsonium salts of formula C11N7H2–(1), C15N6H3–(2), C14N7H2–(3), and C13N8H–(4). Compound (1) was obtained by a condensation reaction of TCNE promoted by Ti(bpy)3 and its structure has already been reported. Compounds (2)–(4) are the 1,3-bistricyanovinyl derivatives of cyclopentadienyl, pyrrolyl, and imidazolyl anions, respectively. The tetraphenylarsonium salt of anion (3) gives crystals isomorphorus with the crystals of the analogous salts of anions (2) and (4), whose crystal structures are reported here. Structural and electronic properties of the four anions are discussed on the basis of 13C n.m.r., i.r., u.v., and electrochemical data; electrical and magnetic properties of their radical salts with the tetrathiafulvalenium cation (TTF˙+) are also reported and discussed.

ChemInform Abstract: 1,3‐Dipolar Cycloadditions. Part 92. Reactions of Aliphatic Diazo Compounds with Fourfold Acceptor‐Substituted Ethylenes.

AbstractThe reaction of tetracyanoethylene (Ia) with diazomethane (II) leads to the pyrazoline (III); the previously reported isomer (V) cannot be isolated although being present in a small quantity in the equilibrium with (III).

New Applications of Tetracyanoethylene in Organic Chemistry

Recent applications of tetracyanoethylene in organic chemistry are reviewed; this survey is mainly concerned with selected reactions of tetracyanoethylene which have use or potential use in organic synthesis. Among other topics, this survey includes new information on molecular complexes, ozonization of alkenes and acetylenes (the Criegee reaction) dehydrogenation and tricyanovinylation reactions, reactions of tetracyanoethylene oxide, reactions with ketones and diketones, synthesis of heterocycles, cationic polymerization reactions, and industrial, and analytical applications. Cycloaddition reactions and reactions of tetracyanoethylene with organometallics are not included in this survey. 1. Introduction 2. Scope of the Review 3. Methods of Preparation 4. Toxicity and Handling 5. Chemical Reactivity 6. Tetracyanoethylene Oxide (Tetracyanooxirane); Chemical Reactivity 7. The Ozonization of Alkenes in the Presence of Tetracyanoethylene (The Criegee Reaction) 8. Tetracyanoethylene as a Dehydrogenation Agent 9. Molecular Complexes between Aromatic and Heterocyclic Compounds and Tetracyanoethylene 10. Reaction of Ketones and Diketones with Tetracyanoethylene 11. Tricyanovinylation Reactions via Tetracyanoethylene 12. Synthesis of Heterocycles via Tetracyanoethylene 13. Cationic Polymerization in the Presence of Tetracyanoethylene 14. Industrial Applications of Polymeric Tetracyanoethylene Complexes 15. Analytical Application of Tetracyanoethylene 16. Addenda

Reactions of tetracyanoethylene (TCNE) with the three isodicyclopentadiene isomers

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReactions of tetracyanoethylene (TCNE) with the three isodicyclopentadiene isomersPaul D. Bartlett and Chengjiu WuCite this: J. Org. Chem. 1984, 49, 11, 1880–1886Publication Date (Print):June 1, 1984Publication History Published online1 May 2002Published inissue 1 June 1984https://doi.org/10.1021/jo00185a007RIGHTS & PERMISSIONSArticle Views143Altmetric-Citations16LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (925 KB) Get e-Alerts Get e-Alerts

ChemInform Abstract: REACTION OF TETRACYANOETHYLENE WITH 1‐VINYLINDOLE

AbstractTetracyanethylen (I) reagiert mit I‐Vinylindol (II) selektiv im Sinne einer [2 + 2l‐Cycloaddition zum N‐Cyclobutylindol (III).

Reaction of tetracyanoethylene with 1-vinylindole

It was established that [2 + 2] cycloaddition at the N vinyl group proceeds selectively in the reaction of tetracyanoethylene with 1-vinylindole in aprotic solvents. The resulting 1-(2,2,3,3-tetracyano-1-cyclobutyl)indole upon heating in aqueous media and in alcohols undergoes stereospecific conversion to trans-1-(3,4,4-tricyano-1,3-butadien-1-yl)indole.

Competitive dipolar cycloaddition of tetracyanoethylene to bicyclo[3.2.1]octa-2,6-diene

Reaction of tetracyanoethylene with bicyclo[3.2.1]octa-2,6-diene ( 1 produces three cycloadducts. Isolation and characterization of the products is described and possible mechanisms are discussed.

Reactions of tetracyanoethylene with transition-metal acetylides: synthesis and structure of Rh(CCPh) [η 2-C 2(CN) 4] (NCMe)(PPh 3) 2

The title complex was obtained from the adduct of C 2(CN) 4 and Rh(CCPh)-(CO)(PPh 3) 2 by simple substitution of CO in refluxing acetonitrile. Crystals of the complex are orthorhombic, with a 10.058(2), b 20.008(4), c 21.594(5) Å, space group P2 12 12 1, Z  4. The rhodium has approximate trigonal bipyramidal coordination, with apical NCMe and C 2Ph ligands: RhC 2Ph, 1.939(18); RhC(olefinic), 2.151, 2.157(19); RhN, 2.051(16); RhP, 2.377, 2.397(6) Å.

The nature of the product from the reaction of tetracyanoethylene with iron pentacarbonyl

The reaction of tetracyanoethylene with iron pentacarbonyl in mesitylene at 90° gave an insoluble product, Fe2C16H12N8O7. The Mössbauer and IR spectra, the magnetic susceptibilities over the temperature range 95–298 K, and the thermal decomposition temperatures in a nitrogen atmosphere were measured. The solid is best described as an iron (III) ketoamine polymer with hydroxo bridges between iron atoms.

Ene-type reaction through the intermediacy of the 1,4-dipolar ion in the reaction of tetracyanoethylene with nucleophilic double bonds in liquid sulfur dioxide

Ene-type reaction through the intermediacy of the 1,4-dipolar ion in the reaction of tetracyanoethylene with nucleophilic double bonds in liquid sulfur dioxide

Reduction-oxidation properties of organotransition-metal complexes : XI. Oxidation vs. carboncarbon bond formation in the reactions of tetracyanoethylene with electron-rich organometallic carbonyls

With tetracyanoethylene the electron-rich complexes [Cr(CO) 2l(η 6-C 6Me 6)] (I), [Ru(CO) 2L(η 4-2,3-(CH 3) 2 C 4H 4)] (II) and [Fe(CO) 3− n L n (η 4-COT)] (III, n = 1 or 2), (L = P-donor) undergo one-electron oxidation, RuC bond insertion, and 1,3-cyclo-addition, respectively.

Interaction of tetracyanoethylene with some organo-tin and -mercury compounds

The reactions of tetracyanoethylene (TCNE) with organo-tin and -mercury compounds containing carbonmetal, metalsulphur and metalmetal bonds have been studied. With completely substituted benzyl organometallics in CH 2Cl 2 the reaction proceeds via quantitative insertion of TCNE into the metalbenzyl bond to yield metallated derivatives of 1,1,2,2-tetracyanopropyl-benzene PhCH 2C(CN) 2C(CN) 2M (M  SnMe 3, HgCH 2Ph), whose structure was established by elemental analysis, IR and PMR spectra, and by a study of their chemical properties. The rate of the insertion reactions was found to depend both on the nature of the metal atom (Sn Hg) and on the type of the substituent in the benzene ring of dibenzylmercury ( p-CF 3<< H < p-CH 3). The data obtained are discussed in terms of the general problem of a dual (σ- or π-) regioselectivity of the reactions of π-acids with ambiofunctional organometallic donors. The reactions of TNCE with tin mercaptides either yield stable complexes, (PhS) 4Sn, or (as is the case with PhSSnMe 3) proceed via quantitative insertion into the SSn bond to give PhSC(CN) 2C(CN) 2SnMe 3 whose structure was established by elemental analysis, IR and PMR spectra, and by examination of its chemical properties. The products of TCNE insertion into the carbonmetal bond exhibit a dual reactivity in acid and thermal cleavage reactions, which can be attributed to the presence in their structure of two competing σ,π- and σ,σ-conjugated chains of the Cmetal bonds with neighbouring α- and β-nitrile groups. The reaction of TCNE with hexamethyldistannane in CH 2Cl 2 produces a colourless 1/2 adduct identified by elemental analysis, IR and PMR spectroscopy, and the results of acid cleavage, as dimetallated tetracyanoethane complexes with a second TCNE molecule (Me 3SnC(CN) 2C-(CN) 2SnMe 3 - TCNE). This latter compound exhibits extremely high susceptibility to homolysis resulting in the formation of the iminotricyanoallyl radical Me 3SnNCC(CN)C(CN) 2. This suggests a new two-stage mechanism for the formation of a radical species in the reaction of Me 6Sn 2 with TCNE. The mechanism involves the insertion of a π-acid into the tintin bond as the first stage with the subsequent homolysis or atmospheric oxidation of the unstable adduct.

The reaction of tetracyanoethylene with substituted 7-methylenecycloheptatriene complexes of tricarbonyliron

Mono and di-8-substituted derivatives of tricarbonyl(1-4-7-7-methylenecycloheptatriene)iron add tetracyanoethylene to give complexes containing an organic ligand which is derived from the azulene system. The application of orbital symmetry rules to this addition is discussed.

Thermal and photochemical reactions of tetracyanoethylene with NN-dimethyl-p-toluidine in methanol

Irradiation of tetracyanoethylene (TCNE) with NN-dimethyl-p-toluidine in methanol gave a biphenyl derivative together with N-cyanomethyl-N-methyl-p-toluidine through radical reactions of the thermal reaction products, NNN-trimethyl-p-toluidinium salts.

HIGH PRESSURE CELLS FOR THE STUDY OF MODERATELY FAST REACTION IN SOLUTION

Abstract A technique for the study of moderately fast reaction in solution up to 2000 kg/cm2 was developed. Two types of cells were devised and applied to the thermal measurement of the cationic polymerization of tetrahydrofuran and spectrophotometric one on the reaction of tetracyanoethylene with vinyl ethyl ether.

The oxidation of distannanes by the tetracyanoethylene and 7,7,8,8-tetracyanoquinodimethane

The reaction of tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) with distannanes result in the formation of complexes of the types R 3Sn(TCNE) and R 3Sn(TCNQ) (R = Me, Bu). Hexaphenylditin and TCNQ give the complex (Ph 3Sn) 2 · (TCNQ).

Metal complexes of cyanocarbons XI. Reactions of tetracyanoethylene with hydridoiridium complexes

Reactions of tetracyanoethylene(TCNE) with a number of hydrido-complexes of iridium have been studied. Displacement reactions are observed for most of the tervalent, octahedral iridium substrates such as IrHCl 2(CO)(PPh 3) 2, IrH 2Cl(CO)(PPh 3) 2, IrHCl(SnCl 3)CO(PPh 3) 2, and IrH 2(SnCl 3)CO(PPh 3) 2 where HCl, H 2 SnHCl 3, and SnH 2Cl 2 respectively are eliminated and the iridium-containing product in all cases is IrCl(CO)(TCNE)(PPh 3) 2. In the case of the univalent, trigonal bipyramidal substrates IrH(CO)(PPh 3) 3 and IrH(CO) 2(PPh 3) 2 as well as tervalent IrH 3(CO)(PPh 3) 2, a 1,4-addition to TCNE is formally observed, and the novel cyano(dicyanomethyl) keteniminato complex Ir(C 6N 4H)(CO)(TCNE)(PPh 3) 2 is isolated when the solvent is benzene. The presence of alcohol in the reaction mixture results in the formation of the cyano-complex Ir(CN)(CO)(TCNE)(PPh 3) 2 as well as the keteniminato-complex. The nature of the keteniminatoiridium bond is discussed and a rationale for the 1,4-addition is proposed.