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.     

Enantioselective Nickel-Catalyzed Hydrocyanation of Homostilbenes

We investigated the previously unknown enantioselective Ni-catalyzed hydrocyanation of 1,3-diarylpropenes (homostilbenes). For this purpose, a series of (E)-homostilbenes were prepared by (microwave-assisted) Pd-catalyzed coupling of allylic alcohols with aryl-boronic acids. Employing our established catalyst system formed from Ni(cod)₂ and a TADDOL-derived chiral phosphine-phosphite ligand and using TMSCN as an in situ source of HCN, the hydrocyanation of various homostilbenes was studied. The synthetic usefulness of the methodology was demonstrated in a short synthesis of the new (allo-) colchicine analogue 7-cyano-11-methoxy-colchinol involving an PIDA-mediated oxidative cyclization of the corresponding hydrocyanation product to set up the 7-membered ring. The absolute configuration of 2,4-diphenylbutyronitrile was assigned by comparison of experimental and calculated ECD spectra.     

Antibacterial screening of new bis(pyrazolo[1,5-a]pyrimidine) hybrids linked to different spacers

A three-component protocol was adopted to efficiently prepare new bis(pyrazolo[1,5-a]pyrimidines) linked to different spacers in 80-92% yields from 1H-pyrazole-3,5-diamines, malononitrile and bis(aldehydes). The p-xylene-linked bis(pyrimidine) bearing 3-positioned 4-methoxy-benzyl substituent had the best antibacterial activity with MIC / MBC values up to 2.2 / 4.4 µm.     

Uniform silver nanoparticles on tunable porous N‐doped carbon nanospheres for aerobic oxidative synthesis of aryl nitriles from benzylic alcohols

Tunable N‐doped carbon nanospheres from sucrose as carbon source and Tris(2‐aminoethyl)amine (TAEA) as nitrogen source by a simple and easily reproducible method were prepared. It was demonstrated that the tunable N‐doping of carbon spheres could be realized by altering the ratio of TAEA in the raw materials. The content of doped nitrogen, surface area, pore volume and pore size of carbon nanospheres were increased with the increasing of TAEA amount in the hydrothermal process. Prepared N‐doped carbon nanospheres act as solid ligand for anchoring of Ag NPs which generated via chemical reduction of Ag ions. Benzylic alcohols and aldehydes were converted into the aryl nitriles by using Ag/N‐CS‐1 nanospheres as the catalyst and O₂ as the oxidant, efficiently. This catalyst was stable and could use for 6 successful runs.     

Ru (III) Schiff‐base complex anchored on nanosilica as an efficient and retrievable catalyst for hydration of nitriles

Transition metal catalyzed hydration of nitriles is an attractive methodology for amide synthesis, and hence recently attracted wide attention. It is one of the significant organic transformations as amides play a vital role in biological, pharmaceutical and industrial applications. In this work, we report the synthesis of a new solid supported Ru (III) Schiff base complex, Ru@imine‐nanoSiO₂ immobilized on nanosilica obtained from rice husk. The complex was characterized by FTIR, powder X‐ray diffraction, BET surface area measurement, UV–vis, SEM–EDX, TEM, ESR, X‐ray photoelectron spectroscopy and ICP‐AES analysis. Using Ru@imine‐nanoSiO₂ as the catalyst, the hydration of nitriles in i‐PrOH at 40 °C was studied which resulted in good isolated yields (60–99%). The catalyst can be recycled and reused up to 5^th cycle without any loss in activity. The products were characterized by FTIR, GC–MS and ¹H‐NMR spectroscopy and compared with authentic samples.     

Sulfuryl Fluoride Mediated Conversion of Aldehydes to Nitriles

Aliphatic, aromatic, and heteroaromatic aldehydes were readily converted to corresponding nitriles in a one-pot reaction sequence with hydroxylamine and sulfuryl fluoride. The reaction proceeds at room temperature, does not require metal catalysts and special precautions, and produces nitriles in excellent yields. It is compatible with a variety of functional groups, can be performed in aqueous and organic solvents, and is readily scalable to multigram quantities. Mild conditions and high selectivity of the reaction enabled the construction of polyfunctional probes containing nitrile, alkyne, azide, and fluorosulfate groups for further orthogonal derivatization.     

Synthesis of nitriles from acetonitrile and methanol in the presence of oxide catalysts

The promoting effect of potassium included in Cr/MgO catalysts for the synthesis of nitriles from acetonitrile and methanol was found. The 5% Cr-0.5% K/MgO catalyst exhibited the highest activity in the synthesis of nitriles. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1540–1542, August, 1997.     

Spectroscopic Calculation of CH Bond Dissociation Energies for Aliphatic Nitriles

The CH bond dissociation energies were calculated spectroscopically for acetonitrile, propionitrile, isobutyronitrile, and trimethylacetonitrile from the fundamental absorption bands in the anharmonic approximation using the variational technique with the Morse-harmonic basis set. A similar calculation was carried out for various associates of acetonitrile. Due to this, CH bond dissociation energies were determined for the liquid state of acetonitrile.Original Russian Text Copyright © 2004 by L. A. Gribov, I. A. Novakov, A. I. Pavlyuchko, V. V. Korolkov, and B. S. Orlinson__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 816–821, September–October, 2004.     

Trimethylsilylcyanation of Heterocyclic Aldimines - Derivatives of 2-Trifluoromethylaniline

The addition of trimethylsilyl cyanide to the CH=N bond of furan, thiophene, and pyridine azomethines in the presence of aluminum bromide as catalyst was studied. The effect of the CF₃ group in the aldimines produced by the condensation of O-, S-, and N-heteroaromatic aldehydes with 2-trifluoromethylaniline on the reaction and also other relationships of the investigated processes were studied. The corresponding furan, thiophene, and pyridine -amino nitriles were synthesized.