Crystallographic and computational study of the structure of copper(II) 2,2′-bis(2-oxidobenzylideneamino)-4,4′-dimethyl-1,1′-biphenyl

The reaction of M(OAc)₂ with 2,2′-bis(2-hydroxybenzylideneamino)-4,4′-dimethyl-1,1′-biphenyl (H₂L1) allows the synthesis of 2,2′-bis(2-oxidobenzylideneamino)-4,4′-dimethyl-1,1′-biphenyl complexes of Cu(II) (CuL1), Co(II) (CoL1) and Ni(II) (NiL1) that were characterized by elemental analysis, FTIR spectroscopy and for CuL1 also by X-ray crystallography verifying a tetradentate binding mode of L1 via an (ONNO) motif of the two phenolic oxygen atoms and two azomethine nitrogen atoms. Recrystallization from a solvent mixture of dichloromethane and methanol promotes the formation of methanol adducts. Different binding modes of the methanol–complex were investigated using density functional theory calculations and binding energies, and thermodynamic data of the interaction are reported. The results show that the favored interaction occurs when the methanol molecule acts as a Lewis acid weakly binding via an O–H···O hydrogen bridge to a phenoxide moiety leading to an elongation of the respective M–O bond.

     

Features of the synthesis of 1,1′-Phenylenebis(1H-tetrazoles) and their transformations in basic environment

Reactions of substituted 1,3- and 1,4-phenylenediamines with sodium azide and triethyl orthoformate in the presence of acetic acid led to the formation in high yields of the corresponding 1,12 -phenylenebis(1Htetrazoles). The presence of electron-acceptor groups in the molecules of the initial diamines reduces the yield of the target heterocycles. With 2-nitro-1,4-phenylenediamine the prevailing product was 2-nitro-4-(1H-tetrazol-1-yl)aniline. The obtained bistetrazoles in basic environment suffer an opening of one or both heterocycles forming cyanamides.     

A study of the mechanism of rhodium/phosphine-catalyzed hydroformylation: use of 1,1′-bis(diarylphosphino)ferrocene ligands

Rhodium/phosphine-catalyzed hydroformylation was studied using 1,1′-bis(diphenylphosphino)ferrocene and several derivatives containing substituents on the phenyl groups (p-Cl, m-F, and p-CF₃). The results with these disphosphine ligands suggest that the operative mechanism differs in several ways from the accepted mechanism for hydroformylation catalyzed by Rh/Ph₃P. The most important difference is that the most selective catalyst has three phosphorus atoms bound to each rhodium atom and is postulated to be a dirhodium complex. Using these ligands, selectivities to products were correlated by a Hammett σ-ϱ plot, with electron-withdrawing groups (less basic ligands) affording higher rates and higher linear : branched aldehyde ratios. This confirms previous work which qualitatively indicated that the linear : branched ratio increases as ligand basicity decreases.     

A theoretical study on tautomeric structures of 4′-nitroazobenzene-2,4-diol and 4-methyl-4′-nitroazobenzene-2,6-diol compounds

The goal of this study is to determine the most stable tautomeric forms, and their ground state conformers of 4′-nitroazobenzene-2,4-diol and 4-methyl-4′-nitroazobenzene-2,6-diol compounds. The calculations have shown that the most stable tautomeric forms of the compounds are hydrazo form for 4′-nitroazobenzene-2,4-diol and azo form for 4-methyl-4′-nitroazobenzene-2,6-diol. Besides, the vibrational frequencies, ¹H and ¹³C NMR shifts, frontier molecular orbital’s energies for the tautomeric forms of the compounds calculated by using density functional theory-B3LYP method with 6-311G(d) basis set were interpreted. All the assignments of the theoretical frequencies were identified by potential energy distribution (PED) analysis. Generally, theoretical spectral results were seen to be in a good agreement with the corresponding experimental data.     

Synthesis and Characterization of the Poly-(2-Methoxycyanurate) of 1,1′-Bis-(4-Hydroxyphenyl)-cyclohexane

The poly-(2-methoxycyanurate) of l, l′-bis-(4-hydroxyphenyl)-cyclohexane (PMCBC) was synthesized by the interfacial poly-condensation technique. The polymer was fractionated by preparative gel permeation chromatography (GPC). The fractions were characterized by viscometry, osmometry, and GPC techniques. The viscosity-molecular weight relationship was established in pure solvent and in different binary solvent mixtures. The unperturbed dimensions, (〈R²〉₀/M)^1/2, and the solvent-polymer interaction parameter, B, were computed by applying the two-parameter theories of the excluded-volume effect.     

Stable free radicals generated during the oxidation of 4-alkyl Hantzsch 1,4-dihydropyridines with nitrosonium — EPR evidence

Stable free radicals were observed by EPR technique during the oxidation of 4-isopropyl and 4-isobutyl Hantzsch 1,4-dihydropyridines with nitrosonium tetrafluoroborate (NO⁺BF^-4) in anhydrous and anaerobic acetonitrile at room temperature. These free radicals were assigned to diisopropyl aminoxyl and diisobutyl aminoxyl, respectively. A whole mechanism for the oxidation was suggested.     

Role of the transition metal complexes of 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) in asymmetric catalysis

Metal complexes of 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) are being used as a chiral catalysts in many organic reactions. This review highlights recent developments on synthesis of metal BINAPs and its application in various organic synthesis. The studies done on the application of metal BINAPs show a unique reactivity, which enables its use in entirely different sets of chemical transformation.     

Spectrophotometric study of the complexation equilibria of cobalt(II) with 4-(5′-methyl-3′-isoxazolylazo)-resorcinol and determination of cobalt(II)

The reaction of cobalt(II) with 4-(5′-methyl-3′-isoxazolylazo)-resorcinol (MIAR) in 4% v/v ethanol-water medium at I = 0.1 M (NaClO₄) was investigated spectrophotometrically. Graphical and numerical calculation methods were used to establish the equilibria in solution and to evaluate the stability constant of the complexes formed (log β₁₀₁ = 7.48±0.06, log β₁₁₁ = 12.77 max 12.99, log β₁₀₂ = 16.41±0.07). The optimum conditions for the spectrophotometric determination of Co(II) with MIAR were established and the method applied to its determination in some low alloy steels and hydrofining catalysts.     

Synthesis and applications of (R)- and (S)-7,7′-dimethoxy-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene

The synthesis of (R)- and (S)-7,7′-dimethoxy-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene 5a and 5b is described. The phosphorus atoms in (S)-(−)-5b are shown to be slightly more basic than the phosphorus atoms in (S)-BINAP by comparing the magnitude of the ¹J (³¹P–⁷⁷Se) coupling constant in their respective diselenide derivatives. (S)-(−)-5b behaved similarly to (S)-BINAP in asymmetric Heck reactions.     

Synthesis and some transformations of 2-(2′-thienyl)benzothiazole

Condensation of ortho-aminothiophenol with 2-thenoyl chloride in 1-methyl-2-pyrrolidone was used to synthesize 2-(2′-thienyl)benzothiazole. Its reactions of electrophilic (nitration, bromination, oxymethylation, formylation, acylation) and radical (nitration, arylation) substitution were studied.     

N′-(α-acetoximinoalkyl)diazene-N-oxides and some of their transformations

Nitroso compounds of the aromatic and aliphatic series react with O-acetylalkanoylamidoximes in the presence of dibromoisocyanurate, forming the previously unknown N-(-acetoximinoalkyl)diazene-N-oxides, which under gaseous NH₃ or oxalic acid in methanol lose the acetyl group and as a result are transformed into the previously unknown N-(-hydroximinoalkyl)diazene-N-oxides.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 109–114, January, 1991.     

One-Pot Synthesis of Functionalized 1,1′-(9-Selenabicyclo[3.3.1]nonane-2,6-diyl)dipyridinium Dibromides

Russian Journal of Organic Chemistry - Previously unknown functionally substituted 1,1′-(9-selenabicyclo[3.3.1]nonane-2,6-diyl)dipyridi­nium dibromides were synthesized in 90–98%...     

New approach to the synthesis of 2,6-difluorobenzoyl isocyanate and its use in the preparation of N-(2,6-difluorobenzoyl)-N′-(polyfluoroaryl)ureas

The treatment of 2,6-difluorobenzoyl chloride with trimethylsilyl isocyanate gave 2,6-difluorobenzoyl isocyanate. This product reacts with polyfluoroaromatic amines to give the corresponding N-(2,6-difluorobenzoyl)-N-(polyfluoroaryl)urea, which hold potential as inhibitors for the biosynthesis of insect chitin.Institute of Chemistry, Bashkir Science Center, Urals Branch, Russian Academy of Sciences, 450054 Ufa. Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 468–470, February, 1992.     

Tin,palladium and platinum derivatives of 1,1′-bis(diphenylphosphine)ferrocene. Crystal and molecular structures of 1,1′- bis-(diphenylphosphine)ferrocenedichloropalladium(II) and of 1,1′-bis(diphenylphosphine)ferrocenedichloroplatinum(II)

Summary Ten derivatives of 1,1-bis(diphenylphosphine)ferrocene (BDPF) are described in this paper. The first three, [BDPF·SnCl₄] (1), [BDPF·MeSnCl₃] (2) and [BDPF·PhSnCl₃] (3), present the two phosphorus atoms of the ligand directly bonded to a Sn centre. Two others, [BDPF-PdCl₂ (4) and [BDPF·PtCl₂] (5), similarly have the ligand BDPF acting as a bidentate species towards a transition metal. The crystal and molecular structures of (4) and (5) are presented here. Two other BDPF complexes were obtained with Pd and Pt, with the transition metals in the zerovalent state, namely [Pd(BDPF)₂] (6) and [Pt(BDPF)₂] (7). Finally, three trimetallic complexes are also described; [BDPF·Pd(-Cl)₂SnCl₂] (8), [BDPF· Pt(-Cl)₂SnCl₂] (9) and [BDPF·PdClSnCl₃] (10).     

Stereochemistry of the asymmetric reduction of (1′s)-1,3-dimethyl-4(1′-phenylethylimino)piperidine

The stereochemistry of the asymmetric reduction of the imine obtained from 1,3-dimethylpiperidin-4-one and (S)--phenylethylamine has been studied. It is shown that hydride reduction of imine 1 by sodium borohydride in methanol is asymmetric and gives the cis and trans diastereomeric pair 1,3-dimethyl-4-(-phenyl-ethylamino) piperidine in the ratio 3:1. Using sodium in isopropanol gives only one trans diastereomeric pair.¹H NMR has been used to identify the stereochemical structure and diastereomer excess of the cis and trans isomers of 1,3-dimethyl-4-(-phenylethylamino)piperidine which had been separated by column chromatography.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 219–221, February, 1996.     

Copper (II) chloride / tetrabutylammonium bromide catalyzed oxidation of 2,6-diisopropylnaphthalene and 4,4′-diisopropylbiphenyl

The oxidation processes of 2,6-diisopropylnaphthalene and 4,4′-diisopropylbiphenyl with oxygen in the presence of a catalyst, composed of copper(II) chloride and tetrabutylammonium bromide, were investigated. It was found that, in essence, only one isopropyl group undergoes oxidation, and obtained mixtures contained mainly peroxide, alcohol, ketone and only small amounts of hydroperoxide.      

Is the hypothiocyanite anion (OSCN)- the major product in the peroxidase catalyzed oxidation of the thiocyanate anion (SCN)-? A joint experimental and theoretical study

The hypothiocyanate anion (OSCN)(-) is reported to be a major product of the lactoperoxidase/H(2)O(2)/(SCN)(-) system, and this anion is proposed to have significant antimicrobial properties. The collision induced (CID) negative ion mass spectrum of "(OSCN)(-)" has been reported: there is a pronounced parent anion at m/z 74, together with fragment anions at m/z 58 (SCN)(-) and 26 (CN)(-). These fragment anions are consistent with structure (OSCN)(-). However there is also a lesser peak at m/z 42 (OCN(-) or CNO(-)) in this spectrum which is either formed by rearrangement of (OSCN)(-) or from an isomer of this anion. The current theoretical investigation of (OSCN)(-) and related isomers, together with the study of possible rearrangements of these anions, indicates that ground-state singlet (OSCN)(-) is a stable species and that isomerization is unlikely. The three anions (OSCN)(-), (SCNO)(-), and (SNCO)(-) have been synthesized (in the ion source of a mass spectrometer) by unequivocal routes, and their structures have been confirmed by a consideration of their collision induced (negative ion) and charge reversal (positive ion) mass spectra. The CID mass spectrum of (SCNO)(-) shows formation of m/z 42 (CNO(-)), but the corresponding spectra of (OSCN)(-) or (SNCO)(-) lack peaks at m/z 42. Combined theoretical and experimental data support earlier evidence that the hypothiocyanite anion is a major oxidation product of the H(2)O(2)/(SCN)(-) system. However, the formation of m/z 42 in the reported CID spectrum of "(OSCN)(-)" does not originate from (OSCN)(-) but from another isomer, possibly (SCNO)(-).     

A kinetic study of the aqueous phase oxidation of di-μ-oxo-bis(L-cysteine)-oxomolybdenum(V) by molecular oxygen

The molecular oxygen-mediated decomposition of the binuclear complex, prepared from oxomolybdate(V) and L-(+)-cysteine, was studied spectrophotometrically at pH 3.5–5.6. The formation of MoVI was detected. The effects of pH and [O2] on the decomposition kinetics are given by the equation: