Synthesis of bis(ferrocenylamino)glyoxime and its nickel(II) complex

Bis(ferrocenylamino)glyoxime has been prepared by the reaction of amino ferrocene with anti-dichloroglyoxime. The nickel(II) complex of this new compound is also described.     

Unique self-assembled 2D metal-tetrazolate networks: crystal structure and magnetic properties of [M(pmtz)2](M = Co(II) and Fe(II); Hpmtz = 5-(pyrimidyl)tetrazole)

The title compounds, which have been prepared from M(II) salts (M = Co and Fe) and 5-(pyrimidyl)tetrazole under hydrothermal conditions, are isomorphous and exhibit a 2D square-grid-like structure; the cobalt complex is a spin-canted antiferromagnet with Tc= 15 K.     

Practically Perfect Asymmetric Autocatalysis with (2‐Alkynyl‐5‐pyrimidyl)alkanols

Extremely high enantioselectivity (>99.5% ee) and chemical yield (>99%) are achieved in an asymmetric autocatalytic reaction. A (5‐pyrimidyl)alkanol with a tert‐butylethynyl group at its 2‐position ( 1 ) is a very efficient asymmetric autocatalyst in the enantioselective alkylation in Equation (1).     

Unprecedented Trinuclear AgI Complex with 2,4,6‐Tris(2‐pyrimidyl)‐1,3,5‐triazine as an Efficient Catalyst for the Aziridination of Olefins

An unprecedented trinuclear heteroleptic Ag^I complex was isolated using a stable multidentate 2,4,6‐tris(2‐pyrimidyl)‐1,3,5‐triazine (TPymT) ligand. The obtained compound is an efficient catalyst for the direct aziridination of terminal olefins.     

Photoisomerization of bis(trifluoromethyl)thiophenes

The photolysis of 2,3-bis(trifluoromethyl)thiophene gave an equilibrium mixture of 2,3- and 3,4-bis(trifluoromethyl)Dewar thiophenes, while that of 2,5-bis(trifluoromethyl)thiophene gave 2,4-bis(trifluoromethyl)-thiophene, which seemed to be formed through an intermediate other than the Dewar form.     

Investigation of bisheteryl derivatives of piperazine and its analogs. 2. Synthesis and properties of bis(dialkyldithiocarbamoyl-5-nitro-4-pyrimidyl)piperazines

The corresponding 6-dialkyldithiocarbamoyl derivatives are obtained by reacting N,Nbis(2-R-6-chloro-5-nitro-4-pyrimidyl)-carbamates. in ont example it was shown that these products may be rearranged on heating with the formation of the bis(1,3-dithiolo[4,5-d]pyrimidyl)piperazine system, and in the presence of an alkaline catalyst may be converted by fission of the pyrimidine ring into the highly polarized N,N-bis(1-amino-2-cyano-2-nitro-1-ethenyl)-piperidine.For part 1 see [1].Center for Drug Chemistry, All-Russian Pharmaceutical Chemistry Research Institute (VNIKhFI), Moscow 119815. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 208–210, February, 1995. Original article submitted October 14, 1994.     

Coordination architectures and luminescent properties of 5-(pyrimidyl)tetrazolate (Hpmtz) with group 2 metal ions

Four alkaline earth metal-organic frameworks, [Mg(H₂O)₆]?·?(pmtz)₂ (1), [Ca(pmtz) ₂(H₂O)₃]?·?H₂O (2), [Sr(pmtz)₂(H₂O)₄] (3), and [Ba(pmtz)₂(H₂O)₂]?·?4H₂O (4) [pmtz?=?5-(pyrimidyl)tetrazole anion], were synthesized and characterized by elemental analysis, IR spectroscopy, and X-ray crystallography. The crystal structures reveal that 1–3 are mononuclear while 4 displays a 2-D layer structure by bis(bidentate) bridging pmtz^?. The luminescence properties of 1–4 were investigated in the solid state at room temperature.     

Synthesis of bis(glycosylamino)alkanes and bis(glycosylamino)arenes

The condensation of D-mannose and D-galactose with aliphatic and aromatic diamines afforded a series of bis(glycosylamino)alkanes and-arenes. A possible mechanism was proposed for the formation of 1,2-bis(β-D-glycosylamino)benzenes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2793–2801, December, 2005.     

Esters of phosphoric and thiophos phoricacids containing heterocyclic radicals Communication 1. Compounds with pyrimidyl and imidomethyluracil radicals

Summary A number of esters of phosphoric and thiophosphoric acids, containing pyrimidyl and imidouracil radicals, have been synthesized and studied.     

Study of the Coordination Properties of 1,2-Bis(2,6-dimethphenylamino) Glyoxime and Determine the Stability Constant of Its Complexes with Ni(II), Cu(II) and Zn(II) Metal Ions in Solution

This study aims to investigate the nature and type of complexes formed in solution between 1,2-bis(2,6-dimethphenylamino) glyoxime (DPG) and the ions Ni²⁺, Cu²⁺ and Zn²⁺. Potentiometric titration was used to follow the formation of complexes.The complexes formed were studied through the determination of stability constants of these complexes in mixed ethanol–aqueous solution at 25±0.1?°C and ionic strength of 0.1 mol?dm^?3 NaCl. The basicity of the ligand was also assessed by the determination of the dissociation constants of the ligand. All of the constants were determined by computer refinement of pH–volume data using the SUPERQUAD program. The species distribution diagrams were also calculated.Comparison with other vic-dioximes was made to provide reliable support for the formation of the proposed complexes in solution.     

A novel hydride-mediated reductive rearrangement of amide: a facile synthesis of pyrimidyl and triazinyl amines

LiAlH₄ and NaBH₄ were found to mediate the conversion of 2-(pyrimidyl-2-ylsulfanyl)-N-arylbenzamides and 2-(triazinyl-2-ylsulfanyl)-N-arylbenzamides into pyrimidyl and triazinyl amines under notably mild conditions via a novel reductive rearrangement mechanism. These reactions invent a new route to prepare amines, which are a kind of important biologically active compounds and provide the first insight into a novel hydride-promoted reductive rearrangement of amides.     

Reaction of sodium bis(trimethylsilyl)amide with 2-bromopyridine

A reaction of sodium bis(trimethylsilyl)amide with 2-bromopyridine leads to N,N-bis(trimethylsilyl)- and N,3-bis(trimethylsilyl)-2-pyridinamine.     

Aliphatic polyimides from phenylene bis(succinic anhydride) and bis(glutaric anhydride)

Meta and para derivatives of phenylene bis(succinic anhydride) and bis(glutaric anhydride) were obtained from 1,3- and 1,4-bis(β-cyano-β-carbethoxyvinyl)benzene with potassium cyanide or Meldrum acid followed by hydrolysis with concentrated hydrochloric acid and dehydration with acetic anhydride. Aliphatic polyimides were prepared from these anhydrides with six aromatic diamines through thermal ring closure of polyamic acids obtained by solution polymerization in dimethylacetamide, and thermal stability of these polyimides was examined by thermogravimetric analysis.     

Synthesis of new silylated sulfur-containing heterocycles through thionation of bis(acylsilanes)

The thionation of bis(acylsilanes) with spacers of variable size with hexamethyldisilathiane under cobalt(II) chloride or trimethylsilyl triflate catalysis affords 2,5-bis(trialkylsilyl)-thiophenes, 2,6-bis(trialkylsilyl)-4H-thiopyrans and 2,7-bis(trialkylsilyl)-4,5-dihydrothiepine generally along with a minor amount of the corresponding oxo analogue. The synthesis of both symmetrical and unsymmetrical bis(trialkylsilyl) derivatives was achieved.     

Difunctional heterocycles: A convenient one pot synthesis of novel bis(benzoxazoles) from bis(o-aminophenols)

New bis(benzoxazoles) 14 and 17 have been synthesized in excellent yields from the corresponding bis(o-aminophenols) by refluxing with triethyl orthoformate. 6,6′-Bis(benzoxazole) ( 14 ) has also been prepared utilizing Gold's reagent. Compound 14 is inert to Reissert reaction conditions. However, the Reissert reaction on 5,5′-bis(benzoxazole) (17) led to ring opened product 20 .     

Synthesis and desilylation of some bis(trimethylsilyl)alkenes and polymers bearing bis(silyl)alkenyl groups

The synthesis of various vinylbis(silanes) from some aryl and heteroaryl aldehydes and (Me₃Si)₃CLi in Et₂O is described. Friedel-Crafts reaction of 1,1-bis(trimethylsilyl)-2-(2-naphthyl)ethene with various acyl chlorides (RCOCl, R = Me, Et, i-Pr, i-Bu, n-pent) gave the corresponding α-silyl-α,β-unsaturated enones with high E steroselectivity. Moreover, poly(styrene)-co-[2,2-bis(trimethylsilyl)ethenyl(styrene)] obtained via the reaction of polymers bearing pendant enone functions and (Me₃Si)₃CLi, reacts with the same acyl chlorides in the presence of catalytic amount of AlCl₃ to give the new macromolecules bearing α-silyl-α,β-unsaturated enones and α,β-unsaturated enones.     

Peculiarities of the reaction of alkali metal bis(trimethylsilyl)amides with halobenzenes

Lithium and sodium bis(trimethylsilyl)amides react with fluoro-, bromo-, and chlorobenzenes in THF or toluene to give a mixture of N,N-bis(trimethylsilyl)aniline and N,2-bis(trimethylsilyl)aniline. The latter compound is resulted from 1,3-shift of the trimethylsilyl group from nitrogen to ortho-carbon atom of the benzene ring. Effects of the solvent, halogen, and alkali metal nature as well as the reaction conditions on the ratio of isomers were examined. Reaction of iodobenzene with sodium bis(trimethylsilyl)amide in THF produces N,N-bis(trimethylsilyl)aniline and 2-iodo-N,N-bis(trimethylsilyl)aniline, while in toluene a mixture of three products, two indicated above and N,N-bis(trimethylsilyl)benzylamine, was obtained.     

Direct N-nitration of bis(trifluoromethyl)-containing 2-azanorbornanes

Nitration of 6,7-disubstituted 3,3-bis(trifluoromethyl)-2-azanorbornanes affords the corresponding N-nitro derivatives.     

Evidence of asymmetric autocatalysis in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde using chiral pyrimidyl alkanol

Kinetic analysis of the relationship between the reaction time and the yields of the product in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde using chiral pyrimidyl alkanol proves that the reaction is autocatalytic.     

cis-Bis(7-methylnaphth-1-yl)bis(triphenylphosphan)platin(II)

From the reaction of cis-dichlorobis(triphenylphosphane)platinum(II) with the lithium compound obtained as the bromination product of 2-methylnaphthalene cis-bis(7-methylnaphth-1-yl)bis(triphenylphosphane)platinum(II) (6), has been isolated. The unexpected formation of 6 has been explained.