Study of the reactivity of organonickel sigma-complexes towards nitriles

The reactivity of organonickel sigma-complexes of type [NiBr(Ar)(bpy)], where Ar = 2,6-dimethylphenyl (Xyl), 2,4,6-trimethylphenyl (Mes), 2,4,6-triisopropylphenyl (Tipp), 2,4,6-tricyclohexylphenyl (Tchp), bpy = 2,2´-bipyridine, towards nitriles (acetonitrile, propionitrile, chloroacetonitrile, benzonitrile) has been investigated. This reaction leads to imines by formation of new carbon—carbon bond between aromatic fragment and nitrile group C≡N.     

Synthesis of 4,5-dihydro-2-diethylamino-4-thioxo-4-phenoxy-5-chloro-1,3,4-thiazaphosphole and 3,7-bis(diisopropylamino)-1-thioxobicyclo[3.3.0]-4,6-dithia-2,8-diaza-1-phosphaocta-2,7-diene

The product of the reaction of 0-phenylisothiocyanatodichloromethylthiophosphonate with diethylamine in the presence of Et₃N is 4,5-dihydro-2-diethyl-amino-4-thioxo-4-phenoxy-5-chloro-1,3,4-thiazaphosphole. 3,7-Bis(diisopropyl-amino)-1-thioxobicyclo-[3.3.0]-4,6-dithia-2,8-diaza-1-phosphaocta-2,7-diene was obtained as the result of the reaction of diisothiocyanatodichloromethylthiophosphonate with diisopropylamine and triethylamine. IR, PMR, and³¹P NMR spectroscopy was used to demonstrate the structures of the products synthesized.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 462–463, February, 1992.     

Three-component condensation of pyridin-2-one, bis(2-chloroethyl)amine hydrochloride, and K2CO3 in DMF as a new method for oxazolidinylethylation

Three-component condensation of pyridin-2-one, bis(2-chloroethyl)amine hydrochloride, and K₂CO₃ in DMF unexpectedly gave N-and O-oxazolidinylethylation products of pyridin-2-one in the ratio 3: 2. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1047–1048, May, 2007.     

1-alkyl 3,5-diallyl isocyanurates as synthetic building blocks for sulfur-containing macroheterocycles

2-Sulfanylethanol was added to readily available 1-alkyl 3,5-diallyl isocyanurates to obtain 1-alkyl 3,5-bis[3-(2-hydroxyethylsulfanyl)propyl] isocyanurates. Treatment of the products with thionyl chloride gave 1-alkyl 3,5-bis[3-(2-chloroethylsulfanyl)propyl] isocyanurates whose reaction with thiourea followed by hydrolysis resulted in preparation 1-alkyl 3,5-bis[3-(2-sulfanylethylsulfanyl)propyl] isocyanurates. Oxiative cyclization of the latter gave macrocyclic disulfides in 56–75% yields. The composition and structure of the macrocyclic disulfides were established on the basis of the elemental and X-ray diffraction analyses, ¹H and ¹³C NMR and IR spectra, as well as MALDI-TOF and electron impact mass spectra.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1368–1376.Original Russian Text Copyright © 2004 by Fattakhov, Shulaeva, Saifina, Efremov, Rizvanov, Soloveva, Nafikova, Azancheev, Gubaidullin, Litvinov, Reznik.This revised version was published online in April 2005 with a corrected cover date.     

The reactions of 3-ethoxycarbonylmethylene-3,4-dihydroquinoxalin-2(1H)-one and its derivatives in the synthesis of benzodiazepines and benzimidazoles: reinvestigation,structural reassignment,and new insight

The reaction of 3-ethoxycarbonylmethylene-3,4-dihydroquinoxalin-2(1H)-one with the Vilsmeier reagent, the treatment of 3-(3,4-dihydroquinoxalin-2(1H)-on-3-yl)-1,2-dihydro-1,5-benzodiazepin-2(1H)-one hydrochloride with 10% sodium hydroxide and 3-benzimidazoylquinoxalin-2(1H)-one with both 1,2-phenylenediamine dihydrochloride, and the reactions of 1,2-phenylenediamine have been reinvestigated and the structures of these reaction products have been revised. It has been shown that in all the three cases other regioisomers of products have been formed as distinct from the literature data. The mechanisms to explain the formation of the products are suggested.