Search results for "nitrile"
showing 10 items of 1539 documents
Ab Initio Study of Stereo- and Regioselectivity in the Diels−Alder Reaction between 2-Phenylcyclopentadiene and α-(Methylthio)acrylonitrile
1997
Ab initio molecular orbital calculations have been used to investigate the Diels−Alder reaction between 2-phenylcyclopentadiene and α-(methylthio)acrylonitrile. Geometry optimizations were performed with the RHF/3-21G, RHF/3-21G*, and RHF/6-31G* calculations while the correlation energy has been calculated at MP2 and MP3 levels. Four asynchronous transition structures corresponding to the formation of different stereoisomers and regioisomers associated with the four reaction channels have been located. The observed endo/exo stereoselectivity and para/meta regioselectivity are correctly described at all levels of calculation, and the calculated activation energies reflect accurately the rela…
ChemInform Abstract: Poly(alkylidenamines) Dendrimers as Scaffolds for the Preparation of Low-Generation Ruthenium Based Metallodendrimers
2011
The aim of this article is to highlight the use of nitrile-functionalized poly(alkylidenamines) dendrimers as building blocks for the preparation of low-generation ruthenium based cationic metallodendrimers having in view potential biomedical applications. Air-stable poly(alkylidenamines) nitrile dendrimers, peripherally functionalized with the ruthenium moieties [Ru(η5-C5H5)(PPh3)2]+ or [RuCl(dppe)2]+, have been prepared, characterized and are being studied for their anticancer activity. The followed strategy is based on the biological advantages associated with low-generation dendrimers, the known activity of ruthenium compounds as anticancer drugs and the stability of these dendrimers at…
ChemInform Abstract: Heterocycles from α-Aminonitriles
2014
Owing to their various modes of reactivity, α-aminonitriles represent versatile building blocks for the construction of a wide range of nitrogen heterocycles. The present Concept article focuses on synthetic methodologies using their bifunctional nature which is the basis of their reactivity as α-amino carbanions and as iminium ions. Reactions exclusively taking place on either the amine or on the nitrile moiety will not be considered.
ChemInform Abstract: Rearrangements of Nitrile-Stabilized Ammonium Ylides
2014
Rearrangements of nitrile-stabilized ammonium ylides are useful reactions for the construction of alkylamines, nitrogen heterocycles, or carbonyl compounds. In spite of their attractive synthetic potential, they are much less frequently used than rearrangements of ammonium ylides either carrying charge-stabilizing carbonyl groups or being devoid of additional stabilization of the negative charge. This review focuses on different classes of rearrangements of nitrile-stabilized ammonium ylides as well as their application in synthetic organic chemistry. 1 Introduction 2 [1,2]-Stevens Rearrangements 3 [2,3]-Sommelet–Hauser Rearrangement 4 [2,3]-Stevens Rearrangements 5 Competitive [1,2]-, [2,3…
Mechanism of redox transformation of titanocene dichloride centers immobilized inside a polypyrrole matrix—EQCM and XPS evidences
2005
Abstract We report electrochemical quartz crystal microbalance (EQCM) results for electrodeposition of titanocene derivatized polypyrrole p(Tc3Py) films and redox transformation of polypyrrole matrix and titanocene centers immobilized in the film. Films of p(Tc3Py), Tc3Py = Tc(CH 2 ) 3 NC 4 H 4 (Tc = Cl 2 TiCpCp′, Cp = C 5 H 5 , Cp′ = C 5 H 4 ) were obtained from acetonitrile solutions of monomer on a Pt disc or thin Au layer evaporated on 10 MHz quartz crystals. Polymerization efficiency, derived from the slope of the change of resonant frequency as a function of the deposition charge ranged from 54% to 75%. A gradual loss of redox activity of Tc centers during consecutive redox cycles of …
Polymerisation von acrylnitril, methylmethacrylat und einigen substituierten acrylnitrilen mit anorganischen nitraten. Zur polymerisation von acryini…
1968
Die radikalische Polymerisation von Acrylnitril (AN), Methacrylnitril, α-Chloracrylnitril, Crotonsaurenitril und Methylmethacrylat wird unter Bestrahlung bei 60°C in An wesenheit von AgNo3 untersucht, und die Polymerisationsgeschwindigkeiten werden verglichen. Unterschiede in der Polymerisationsfahigkeit einzelner Monomerer lassen sich teilweise auf Komplexbildung mit AgNO3 zurackfahren. Es werden einige andere anorganische Nitrate als Initiatoren eingesetzt; ihre Aktivitat entspricht der Stellung der Kationen in der Spannungsreihe. Als Teil der Initiierungsreaktion wird eine Reduktion des Metallions angenommen; daher kann eine Abnahme der Kationenkonzentration bei AgNO3 und besonders bei C…
N-(Diphenylmethylene)benzenesulfonamide andN-(Diphenylmethylene)-4-methylbenzenesulfonamide
2008
[10398-99-9] C19H15NO2S (MW 332.42) InChI = 1S/C19H15NO2S/c21-23(22,18-14-8-3-9-15-18)20-19(16-10-4-1-5-11-16)17-12-6-2-7-13-17/h1-15H InChIKey = LECLPBHPQOFADH-UHFFFAOYSA-N (reagent used as an activated imine) Physical Data: mp 119–120 °C. Form Supplied in: colorless crystals. Not commercially available. Purification: recrystalization from CH3OH. [10399-00-5] C20H17NO2S (MW 346.45) InChI = 1S/C20H17NO2S/c1-16-12-14-19(15-13-16)24(22,23)21-20(17-8-4-2-5-9-17)18-10-6-3-7-11-18/h2-15H,1H3 InChIKey = ODLFJRFKAOOIKO-UHFFFAOYSA-N (reagent used as an activated imine) Physical Data: mp 103–104 °C1; 102–103 °C2; 101–102 °C5; 103 °C6; 102–104 °C.7 Solubility: soluble in pyridine, dimethylformamide, …
The reaction of amino-imidazoles, -pyrazoles and -triazoles with α,β-unsaturated nitriles
2005
The reactions of α,β-unsaturated nitriles (1, 9, 12) as bielectrophiles with aminoazoles (2, 4, 6) as binu-cleophiles were investigated. Acrylonitrile (1) reacts almost exclusively in a chemoselective Michael-type addition yielding the substituted azoles 3, 5 and 7, respectively. Cinnamonitriles 9a,b behave in a similar way, but the free CN group adds a second molecule 4 yielding 10a,b and its cyclocondensation product 11a,b as minor component. The attempted formation of azolopyrimidines is best achieved by the reaction of the benzylidenemalononitriles 12a - f with 2 or 4. The process is chemo- and regioselective. The structure determinations were based on NMR measurements including DEFT, C…
ChemInform Abstract: A New Versatile Synthesis of N,N′,N′′,N′′′-Tetra(2-carboxyethyl)- and N,N′,N′′,N′′′-Tetra(3-aminopropyl)-tetraazacycloalkanes by…
2010
Abstract A smooth and convenient one step synthesis of N,N′,N″,N″′-tetra-(2-carboxyethyl)-tetraazacycloalkanes is reported. These compounds are synthesized by Michael addition of tetraazacycloalkanes to acrylic acid. The same Michael addition of tetraazacycloalkanes to an excess of acrylonitrile also leads to the corresponding tetracyanoethylated derivatives. The reduction of such tetracyanoethylated compounds is a new way of preparation for the corresponding primary amines.
Towards a converged barrier height for the entrance channel transition state of the N(2D)+CH4 reaction and its implication for the chemistry in Titan…
2011
Abstract The N( 2 D) + CH 4 reaction appears to be a key reaction for the chemistry of Titan’s atmosphere, opening the door to nitrile formation as recently observed by the Cassini–Huygens mission. Faced to the controversy concerning the existence or not of a potential barrier for this reaction, we have carried out accurate ab initio calculations by means of multi-state multi-reference configuration interaction (MS-MR-SDCI) method. These calculations have been partially corrected for the size-consistency errors (SCE) by Davidson, Pople or AQCC corrections. We suggest a barrier height of 3.86 ± 0.84 kJ/mol, including ZPE, for the entrance transition state, in good agreement with the experime…