Reaction of platinum (II) and palladium (II) nitrite complexes with potassium bromide

The reaction of nitrite-bridged binuclear platinum and palladium complexes and KBr in aqueous solution is studied. It is shown that the Pt-O-N bridging bond dissociates during the reaction to yield two mononuclear complexes. Rate constants of the reaction at 15°C are determined.     

Reactions of 2-pyridylphenylacetonitrile with copper(II) chloride,copper(II) bromide,cobalt(II) chloride and cobalt(II) bromide

Reaction of 2-pyridylphenylacetonitrile with copper(II) chloride and copper(II) bromide in dry ethanol gives the hitherto unreported compound 1,2-di(cyano,phenyl,2′-pyridyl)ethane. The cobalt halides react with 2-pyridylphenylacetonitrile to form 1:1 complexes containing O-ethyl-2-phenyl-2-(2′-pyridyl)acetimidate as ligand. Removal of the ligand by the action of dry liquid ammonia on the complexes provides a better route to the pure imidate than the well known Pinner method.     

Reaction of 2-dialkoxyphosphoryl-1,3,2-dithiaphospholanes (phosphorinanes) with nucleophilic reagents

Conclusions The reaction of 2-dialkoxyphosphoryl-1, 3, 2-dithiaphospholanes (phosphorinanes) with nucleophilic reagents proceeds with the initial cleavage of the p-p bond. The rate of reaction depends on the structure of the ring, and also on the type of substituents at the tetracoordinated P atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 423–427, February, 1986.     

Reaction of tris(alkylthio)cyclopropenyl cations with 2-pyridylmagnesium bromide as a new route to indolizines

The reaction of tris(isopropylthio)- and tris(tert-butylthio)cyclopropenylium perchlorates 1a and 1b with 2-pyridylmagnesium bromide in dry tetrahydrofuran at room temperature gave 1,2,3-tris(isopropylthio)- and 1,2,3-tris(tert-butylthio)indolizines 2a and 2b , respectively, in high yields.     

Reaction of elemental phosphorus with epoxides

Conclusions The reactions of P₄/propylene oxide/Me₃N/HX (mole ratio=150.81) leads to the formation of an oligomer. The chain of this oligomer features the sequence of -C-P(O)-O-fragments. Features were determined which control the rate of P₄ conversion depending on the composition of the reaction mixture. The oligomer composition was determined.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1399–1402, June, 1987.     

Reaction of 3-alkyl(aryl)-5-chloromethylisoxazoles with nucleophilic reagents

Previously unknown 3-alkyl(aryl)isoxazoles containing various functional groups in the 5-position were synthesized by reactions of 3-alkyl(aryl)-5-chloromethylisoxazoles with nucleophiles (2-aminoethanol, methylamine, sodium acetate, and sodium methoxide).     

Reaction of anthrapyridones with nucleophilic reagents

The present authors previously showed that anthrapyridone (7H-dibenz [f, ij] isoquinoline-2, 7 [3H] dione) (I) and N-methylanthrapyridone (II) react with aliphatic amines to give the corresponding 1-alkylaminoanthrapyridones [1]. Continuing the research, the reaction of anthrapyridones with other nucleophilic reagents has been studied. Boiling N-methylanthrapyridone with an aqueous dioxane solution of sodium hydroxide, gave a 50% yield of a compound which, after recrystallization from acetic acid had mp 299–300° C (decomp). Found: C 73.57, 73.71; H 3.80, 3.85; N 5.00, 5.22%. Calculated for C₁₇H₁₁NO₃: C 73.62; H 4.00; N 5.05%. The compound was identical in chemical properties, melting point, and IR spectrum with 1-hydroxy-N-methylanthrapyridone(III), prepared by the action of ethanolic alkali on 1-chloro-N-methylanthrapyridone(IV) by the method of [2].     

A novel palladium-catalyzed coupling of epoxides with allyl bromide mediated by indium(I) chloride: a cascade epoxide rearrangement-carbonyl allylation

A cascade epoxide rearrangement-aldehyde allylation was developed by using a combination of InCl and reusable heterogeneous mesoporous silica supported palladium catalysts.     

Reaction of aroylenebenzimidazoles with nucleophilic reagents

The reaction of aromatic mono- and bis(o-phenylenediamines), -(aminophenols), and -(o-aminothiophenols) with mono- and diaroylenebenzimidazoles in polyphosphoric acid was studied. The interrelationship between the structures and properties of the resulting compounds, which contain benzimidazole and other rings in the ortho position relative to one another, was investigated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 247–252, February, 1972.     

Reaction of Gelatin-immobilized Lead(II) Hexacyanoferrate(II) with Dithioxamide

Russian Journal of General Chemistry -     

Highly regioselective ring opening of epoxides and aziridines using (bromodimethyl)sulfonium bromide

Epoxides and aziridines undergo ring opening efficiently with (bromodimethyl)sulfonium bromide at room temperature to form the corresponding β-bromohydrins and β-bromoamines, respectively. The conversions are highly regioselective and afford the products in excellent yields within a short period of time.     

Guanidines as a nitrogen source for direct conversion of epoxides to aziridines

Direct conversion of epoxides to aziridines was achieved with guanidines as a nitrogen source. Stereochemical inversion at the chiral centers of epoxides was observed without loss of optical purity.     

Copper(II) tetrafluoroborate-catalyzed ring-opening of epoxides by amines

Copper(II) tetrafluoroborate catalyzes efficiently the selective opening of epoxides by amines leading to the synthesis of β-amino alcohols. The reaction works well with aromatic and aliphatic amines in high yields under solvent-free conditions.     

Synthesis of azolyl carboximidamides as ligands for Zn(II) and Cu(II): application of the Zn(II) complexes as catalysts for the copolymerization of carbon dioxide and epoxides

A series of novel S,N-heterocyclic (thiazolyl) substituted carboximidamides 3 and 4 was synthesized in yields up to 82% from specific triazinium salts 1 and primary or secondary amines 2 which additionally bear pyridine or imidazole units. These carboximidamides are used as tailor-made ligands for the complexation of Cu(II) and Zn(II). The coordination behavior of 3 and 4 and the properties of the resulting metal complexes are affected a significant extent especially by the nature of these amine substituents. The most important structural feature of the novel complexes is that the ligation of the metal cations is achieved by a 1,3,5-triazapentadienyl anion system, compare the X-ray structure of the model complex Cu-4d. Analogous Zn(II) complexes 5, 6a, 6b, 6c, 7a, and 7b were obtained from carboximidamides 3, 4a, 4b, 4c, 4d, and 4e after reaction with diethylzinc. Interestingly, these Zn(II) complexes possess an intrinsic activity to catalyze the copolymerization of cyclohexene oxide and carbon dioxide to give polycarbonates 15 (TON up to 113; Turn Over Number: moles of substrate 14 consumed per moles of zinc. Molecular weights: up to 206.10(3) Da). Contaminations of 15 by polyethers are produced only in remarkably small amounts.     

Mn(II) azamacrocyclic bromide complexes with different nuclearities

The coordination behaviour of a series of pyridyl azamacrocyclic ligands, some of them containing cyanomethyl and cyanoethyl pendant-arms, towards Mn(II) ion was studied. All the complexes were characterized by microanalysis, LSI mass spectrometry, IR, UV-Vis spectroscopy and magnetic measurements. Crystal structures of [MnL¹][MnBr₄] (1), [MnL³][MnBr₄] · 2CH₃CN (3), [Mn₂L⁵Br₄] · 2CH₃CN (5) and [Mn₂L⁶Br₄] (6) complexes have been determined. The X-ray studies show the presence of an ionic mixed octahedral-tetrahedral complex for 1 and 2, with the manganese ion of the cation complex, endomacrocyclicly coordinated by the six nitrogen donor atoms from the macrocyclic backbone in a distorted octahedral geometry. Instead, the complexes 5 and 6 are dinuclear, and both manganese ions are coordinated by one pyridinic and two amine nitrogen atoms from the macrocyclic backbone and two bromide ions, being the geometry around the metal better described as distorted square pyramidal. In all cases, the nitrile pendant-arms do not show coordination to the metal ion.