Synthesis of 3,3-bis(2-haloethyl) and 3,3,3′-tris(2-haloethyl) derivatives of 1,1′-[methylenebis(oxy)]bis(triaz-1-ene 2-oxides)

Synthetic procedures towards 3,3-bis(2-haloethyl) and 3,3,3′-tris(2-haloethyl) derivatives of 1,1′-[methylenebis(oxy)]bis(triaz-1-ene 2-oxides) via halogenation of the corresponding 2-hydroxyethyl derivatives of 1,1′-[methylenebis(oxy)]bis(triaz-1-ene 2-oxides) and iodination of the corresponding 2-bromoethyl derivatives were elaborated. The synthesized compounds are promising NO donors in the living organisms.     

Binuclear and mononuclear cobalt(II), nickel(II) and copper(II) complexes of 4,4′-bis(alkylaminoisonitrosoacetyl)diphenyl-methane derivatives

4,4-Bis(chloroacetyl)diphenylmethane has been prepared from ClCH₂COCl and Ph₂CH₂. 4,4-Methylenebis(phenylglyoxylohydroximoyl chloride has also been obtained. Four new substituted 4,4-bis(alkylaminoisonitrosoacetyl)diphenylmethanes (ligands) have been prepared from 4,4-methylenebis(phenylglyoxylohydroximoyl chloride) and the corresponding amines. The Ni^II, Cu^II and Co^II complexes of these ligands were prepared and their structures were identified using AAS, i.r., ¹H-n.m.r. spectral data, elemental analyses and magnetic susceptibility measurements.     

Synthesis of 3,3-bis(2-hydroxyethyl) and 3,3,3’-tris(2-hydroxyethyl) derivatives of 1,1’-[methylenebis(oxy)]bis(triaz-1-ene 2-oxides)

Synthetic procedures to access new potential NO donors that can generate NO in living systems, 3,3-bis(2-hydroxyethyl) and 3,3,3’-tris(2-hydroxyethyl) derivatives of 1,1’-[methylenebis(oxy)]bis(3,3-dialkyltriaz-1-ene 2-oxides), were elaborated. 3,3-Bis(2-acetoxyethyl)-1(chloromethoxy)triaz-1-ene 2-oxide reacts with 1-hydroxytriaz-1-ene 2-oxide sodium salts to give a series of alkylated 3,3-bis(2-acetoxyethyl) derivatives. Deacetylation of the latter produces 3-(2-hydroxyethyl)-11,11-dialkyl-6,8-dioxa-3,4,5,9,10,11-hexaazaundeca-4,9-dien-1-ol 4,10-dioxides and 11-alkyl-3-(2-hydroxyethyl)-6,8-dioxa-3,4,5,9,10,11-hexaazatrideca-4,9-diene-1,13-diol 4,10-dioxides.     

Synthesis and structures of 4,5-dimethyl-1,3-bis(pyridin-2-ylmethyl)-1H-imidazolium chloride and 1,1′-bis(pyridin-2-ylmethyl)-2,2′-bis(4,5-dimethylimidazole)

4,5-Dimethyl-1,3-bis(pyridin-2-ylmethyl)-1H-imidazolium chloride (1) was synthesized and characterized by IR and NMR spectroscopy and X-ray diffraction. An attempt to prepare the free tridentate N-heterocyclic carbene pincer ligand by the reaction of 1 with KN(SiMe₃)₂ resulted in the formation of 1,1′-bis(pyridin-2-ylmethyl)-2,2′-bis(4,5-dimethylimidazole) as a product of dimerization of the target carbene followed by the rearrangement accompanied by the elimination of dipyridylethane.

     

N,N′-(1,2-phenylene)bis­(pyridine-2-carboxamide) and N,N′-(1,2-cyclohexanediyl)bis(pyridine-2-carbox­amide) toluene hemisolvate

The crystal structures of N,N′-(1,2-phenyl­ene)­bis­(pyridine-2-carbox­amide), C₁₈H₁₄N₄O₂, (I), and N,N′-(1,2-cyclo­hexane­diyl)­bis­(pyridine-2-carbox­amide) have been determined, the latter compound as the toluene hemisolvate, C₁₈H₂₀N₄O₂·0.5C₇H₈, (II). In (I), the benzene ring is nearly coplanar with one of the pyridine rings and forms a dihedral angle of 59.4 (1)° with the other. However, in (II), the dihedral angle of the two pyridine rings is 70.0 (1)°.     

Synthesis of Macroheterocycles by Reaction of N,N′-(1,4-Phenylene)bis[N′-(4,4-diethoxybutyl)urea] with Resorcinol and Its Derivatives

An efficient procedure has been developed for the synthesis of macroheterocycles by acid-catalyzed reaction of N,N′-(1,4-phenylene)bis[N′-(4,4-diethoxybutyl)urea] with resorcinol, 2-methylresorcinol, and pyrogallol. The structure of the isolated compounds was proved by spectral methods.

     

Synthesis and Structure of bis(μ-2-aminopyridine N-oxide)-bis[dichlorocopper(II)]

1 INTRODUCTIONMany complexes of 2-aminopyridine N-oxide (apo) have been characterized by infrared spectra, X-ray powder diffraction spectra, and by magnetic measurements and electronic spectra at liquid nitrogen temperature, but very few of them are their crystal X-ray studies[1~3]. Recently, a number of bridged binuclear copper (II) complexes have been reported, some of which have important potential applications in bioinorganic chemistry and materials[4~6]. Particularly, the complexes …     

Synthesis and structure of N,N′-bis(dihexylphosphorylmethyl)-1,4-diaminobutane

Russian Journal of General Chemistry - N,N′-Bis(dihexylphosphorylmethyl)-1,4-diaminobutane has been obtained via the Kabachnik–Fields reaction. Crystal structure of its salt with nitric...     

Metal derivatives of 1,3-bis(2-pyridyl)-1,3-propanedione and N,N′-dimethyl-1,3-bis(2-pyridyl)-1,3-propanedione

Complexes of transition metal ions with the oxygen-nitrogen containing ligand 1,3-bis(2-pyridyl)-1,3-propanedione (bpypH) have been synthesized. These present stoichiometries which do not conform with the usual tendency manifested by β-diketones, since molecular formulas with the composition M(bpyp)X are found. A nitrogen methylated ligand N,N′-dimethyl-1,3-bis(2-pyridyl)-1,3-propanedione methyl sulphate [dimebpypH] (MeSO₄)₂ has also been synthesized and its complexes with transition metal ions studied. The stoichiometries now, resemble those of typical β-diketones, namely [dimepyp]₂MX₄ with four anions because of the dicationic nature of the original ligand. This, together with IR evidence suggests a dual type of coordination by bpip via the β-diketone and the pyridyl moieties.     

3,3-Bis(2-nitroxyethyl) derivatives of 1,1′-[methylenebis(oxy)]bis(triaz-1-ene 2-oxides) as a new type of NO donors

3,3-Bis(2-nitroxyethyl) derivatives of 1,1′-[methylenebis(oxy)]bis(triaz-1-ene 2-oxides) were synthesized by either nucleophilic substitution of the bromine atoms of parent 3,3-bis(2- bromoethyl) compounds or nitration of structurally related 3,3-bis(2-hydroxyethyl) derivatives. The synthesized compounds comprise two different NO donating moieties, namely, oxytriaz- 1-ene 2-oxide and nitrate groups, and, therefore, can be regarded as a new type of NO-donating agents.     

Synthesis of 4,4′-bis(dichloroamino)- and 4,4′-bis(chloroamino)-3,3′-azofurazans,the first representatives of dichloroamino- and chloroaminofurazans

First representatives of dichloroamino- and chloroaminofurazans, viz., 4,4′-bis(dichloroamino)- and 4,4′-bis(chloroamino)-3,3′-azofurazans, were synthesized by the chlorination of 4,4′-diamino-3,3′-azofurazan with sodium hypochlorite in the CH₂Cl₂—H₂O mixture.     

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.

     

Synthesis,Crystal Structure and Spectroscopic Properties of N,N′-Diphenyl-N,N′-bis(2-fluorophenyl)-1,1′-biphenyl-4,4′-diamine

A fluorinated tetraphenylbenzidine derivative, N,N′-diphenyl-N,N′-bis(2-fluorophenyl)-1,1′-biphenyl-4,4′-diamine (C36H26F2N2, Mr = 524.59) was synthesized via the palladiumcatalyzed Buchwald-Hartwig reaction of N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine with 2-fluoroiodobenzene (yield: 75%) and structurally characterized. It crystallizes in monoclinic, space group P21/n with a = 9.820(7), b = 14.305(11), c = 10.233(8) , β = 108.973(9)o, V = 1359.3(18) 3, Z = 2, Dc = 1.282 g/cm3, μ(MoKα) = 0.084 mm-1, F(000) = 548, S = 1.018, the final R = 0.0439 and wR = 0.0928. It presents a linear centrosymmetric framework constituted by a linkage of biphenyl as a bridge and two fluorinated diphenylamine moieties. The UV-Vis absorption and fluorescence spectra of the title compound were also investigated. This compound emits intense blue fluorescence with a peak wavelength of 406 nm in film.     

Dinuclear Nickel(II) and Zinc(II) Complexes of 2,6-[N,N′-bis(2-hydroxyphenylmethyl)-N,N′-bis(2-pyridylmethyl)aminomethyl]-4-methylphenol

Abstract

The symmetric 'end-off' compartmental proligand 2,6-[N,N′-bis(2-hydroxy-phenylmethyl)-N,N′-bis(2-pyridylmethyl)aminomethyl]-4-methylphenol (H₃L) has been used to generate homodinuclear nickel(II) and zinc(II) complexes. The crystal structures of the complexes reveal that the di-nickel(II) complex is donor asymmetric and the di-zinc(II) complex is coordination number asymmetric. In both complexes non-coordinated acetic acid molecules are tightly hydrogen-bonded to the pendant phenols of the ligand generating a double acid salt of the type[CH₃COO…H…L…H…OOCCH₃]^3? in the dinickel complex and a single acid salt of the type [CH₃COO…H…L]^3? in the dizinc complex. In both cases the ligand periphery has been extended to provide a supraligand in which the donor potential of the original ligand has been enhanced.     

Two 2-D copper(II) azido compounds: catena -poly[ di -μ1,1- azido,di -μN,O-(quinolinecarboxylato)(aqua)copper(II)] and 1-D catena -poly[ di -μN,N′-(quinoxaline)copper(II)nitrate]

We synthesized three copper(II) complexes with two structurally related polydentate ligands, quinoline-4-carboxylic acid (quCOOH) and quinoxaline (qux). The structures of these complexes were determined using X-ray single crystal crystallography. Complex 1, [Cu(quCOO)(N₃)(H₂O)] _n , has a 2-D polymeric structure through di-μ_1,1 azido groups forming (Cu₂N₂) dimeric units and di-μ_N,O quinoline carboxylate bridging the binuclear copper units. [Cu(quCOO)(N₃)(H₂O)] _n · 0.87MeOH, (2), has the same structure as 1 in addition to MeOH molecules separating the 2-D sheets of [Cu(quCOO)(N₃)(H₂O)] _n . [Cu(qux)(NO₃)₂] _n , (3), has no coordinated azido groups, but the quinoxaline is a bidentate bridging ligand giving a 1-D chain, while the μ_O,O′ chelating nitrato groups stabilize the chain structure by forming a square planar coordination sphere around copper. IR and UV–Vis spectra of the complexes are in agreement with the crystal structures.     

Complexes of αω-bis(3,3-dialkyldiaziridin-1-yl)alkanes and their bis(2-arylcarbamoyl) derivatives with cadmium and nickel salts

Complexes of αω-bis(3,3-dialkyldiaziridin-1-yl)alkanes and their bis(2-arylcarbamoyl) derivatives with Cd²⁺ and Ni²⁺ salts were synthesized. The X-ray diffraction study showed that only one molecule of the starting bis-diaziridine is involved in the complexation. The Cd²⁺ complexes have octahedral geometry. The Ni²⁺ complexes are either square-planar or octahedral. One of the octahedral Ni²⁺ complexes crystallizes in the chiral space group P2₁. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 53–59, January, 2008.     

Synthesis of N,N′-Bis(arylsulfanyl)cyclohexa-2,5-diene-1,4-diimines and N,N′-(Cyclohexa-2,5-diene-1,4-diylidene)bis(arenesulfinamides)

Russian Journal of Organic Chemistry - Reactions of (chlorosulfanyl)benzenes with benzene-1,4-diamines afforded new N,N′-bis(arylsul­fanyl)cyclohexa-2,5-diene-1,4-diimines which were...     

Synthesis of 1,1’-[methylenebis(oxy)]-bis[3-alkyl-3-(2-hydroxyethyl)triaz-1-ene 2-oxides]

Potential NO donors, 1,1’-[methylenebis(oxy)]bis[3-(2-hydroxyethyl)triaz-1-ene 2-oxides], were derived from 3-alkyl-3-(2-acetoxyethyl)-1-chloromethoxytriaz-1-ene 2-oxides and 3-alkyl-1-hydroxy-3-(2-hydroxyethyl)triaz-1-ene 2-oxide sodium salts.     

Coordination chemistry of a new imine-ether ligand,N,N′-bis(2-pyridylmethylene)-2,2′-(ethylenedioxy)bis(ethylamine): mono-helical and single-helical-strand coordination modes identified by X-ray crystallography

A new Schiff base ligand, N,N′-bis(2-pyridylmethylene)-2,2′-(ethylenedioxy)bis(ethylamine), L, and the complexes, [AgL](BF₄) (1), [Zn₂LCl₄] (2), [Hg₂LCl₄] (3), [Cd₂LI₄] (4), [Ni₂L₃](BF₄)₄ (5), and [M₂L₃](ClO₄)₄ with M=Co(II) (6) Fe(II) (7) and Zn(II) (8), have been synthesised and characterised crystallographically and spectroscopically. The silver(I) complex 1 consists of a mono-helical structure where one ligand molecule, coordinating in a tetradentate manner, wraps itself around the Ag(I) ion, giving rise to a distorted tetrahedral arrangement. Single-helical-strand binuclear complexes were obtained with zinc(II), mercury(II) and cadmium(II), 2, 3 and 4, respectively. Complexes 2 and 3 are isomorphous and both contain one ligand molecule coordinating to two metal atoms via the two pyridylimine N-atoms. The two remaining coordination sites on the metals are occupied by chlorine atoms. In the fivefold coordinate cadmium(II) complex, 4, the ligand coordinates in a bis-tridentate manner via the two pyridylimine units and the two oxygen atoms. The two remaining coordination sites on the metals are occupied by iodine atoms. It was possible to combine both coordination modes of the ligand, mono-helical and single-helical-strand, in the isomorphous binuclear octahedrally coordinated nickel(II), cobalt(II), iron(II) and zinc(II) complexes, 5–8, respectively. One ligand molecule is wrapped around each metal ion, which in turn are linked by a third ligand molecule, so forming mono-bridged species.