Synthesis of furoxan derivatives based on 4-aminofuroxan-3-carboxylic acid azide

A convenient preparative method was developed for the synthesis of 4-amino-3-furoxancarboxylic acid azide, which is a universal synthon for the preparation of functional furoxan derivatives. This method was used for preparing new azo-, azoxy-, azido-, cyano-, nitro-, carbonylamino-, and hydroxylamino-substituted furoxan derivatives, which have earlier been difficultly accessible.     

Coordination chemistry of macrocyclic multidentate Lewis acids. Synthesis and structures of complexes of cyclic trimeric perfluoro-o-phenylenemercury with N,N-dimethylacetamide and n-butyronitrile

Cyclic trimeric perfluoro-o-phenylenemercury (o-C₆F₄Hg)₃ readily reacts with N,N-dimethylacetamide and n-butyronitrile to form the complexes {[(o-C₆F₄Hg)₃](MeCONMe₂)₂} and {[(o-C₆F₄Hg)₃](PrⁿCN)}, respectively. According to X-ray diffraction data, the amide ligands are located above and below the plane of the macrocycle, each being coordinated to all Hg atoms of the macrocycle through the O atom. The nitrile ligand is bound to the macrocycle through the N atom, all Hg atoms being also involved in this bonding.     

A new method for the synthesis of nitriles enriched with the15N isotope

A new synthetic method for the preparation of¹⁵N-labeled nitriles from nonlabeled nitriles is proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 444–446, March, 1994.     

Oxidation of 2-(thiazol-2-yl)acrylonitrile derivatives with an H<Subscript>2</Subscript>O<Subscript>2</Subscript>—KOH system: Convenient route to new oxirane-2-carboxamides

An efficient procedure was developed for the synthesis of previously unknown 3-aryl(styryl)-2-(4-arylthiazol-2-yl)oxirane-2-carboxamides and 2-(4-arylthiazol-2-yl)-1-oxaspiro[2.5]octane-2-carboxamides based on treatment of (E)-3-aryl-2-(4-arylthiazol-2-yl)acrylonitriles and cyclohexylidene(4-arylthiazol-2-yl)acetonitriles with an H₂O₂—KOH system in EtOH. Oxidation of (E)-3-(4-chlorophenyl)-2-(4-phenylthiazol-2-yl)acrylonitrile with an H₂O₂—AcOH system affords 3-(4-chlorophenyl)-2-(4-phenylthiazol-2-yl)oxirane-2-carbonitrile in 55% yield. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2319–2322, October, 2005.     

Reductive activation of arenes

Stable cyanomethylcyclohexadienyl anions generated in two-electron reduction of isomeric tolunitriles by potassium in liquid ammonia were detected by NMR spectroscopy. The chemical shifts in these anions were obtained from density functional (PBE/3z) quantum chemical calculations and the electron density distributions for the anions were calculated in the framework of the NBO approach at the HF/6-31+G* level of theory. The experimental and calculated δ_C values are in good agreement. Changes in the δ_C values on going from the starting nitriles to the corresponding anions are linearly related to the calculated π-electron densities on the pentadienyl ring carbon atoms. Dedicated to the memory of Academician V. A. Koptyug on the occasion of the 75th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 940–944, June, 2006.     

A generic approach for the catalytic reduction of nitriles

The scope of nickel boride mediated reduction of nitriles has been extended further to allow the preparation of Boc protected amines via a mild catalytic process. It is noteworthy that the toxicity of this procedure is greatly reduced due to its catalytic nature in nickel(II) chloride used in combination with excess sodium borohydride. The protocol is marked by its resilience towards air and moisture and hence an easy and general practical protocol.     

Microwave-Assisted Efficient One-Pot Synthesis of Nitriles From Aldehydes in the Presence of P2O5/SiO2 in Solvent-Free Media

Abstract

A rapid and efficient procedure is developed for a one-pot synthesis of nitriles by condensation of aldehydes with hydroxylamine hydrochloride in the presence of P₂O₅/SiO₂ in solvent-free media under microwave irradiation.     

The Electronic Nature of the P=C Bond

Abstract

The influence of substituents at the carbon of the P=C bond of about 60 phosphaalkenes was investigated by ³¹P NMR spectroscopy. The P=C system is characterized as electronwithdrawing. All compounds were found to be configurationally stable.