A new vicinal-dioxime and its mono and trinuclear complexes containing the monoazatetraoxa macrocyclic moiety

Mononuclear [Co(HL)2LCl)], [Co(LBF2)2LCl] or [Cu-(HL)2] H2L = {N,N-bis (4-N-phenylaza [15]crown-5)diaminoglyoxime} and a trinuclear, [Cu(L)2(CuL)2](NO3)2, complex of the ligand were synthesized and characterized. The mononuclear copper(II) species coordinates to two copper(II) ions through the deprotonated oximate oxygens to yield a trinuclear structure cis-bridged by the oximate groups, with 1,10-phenanthroline as an end-cap ligand. The terminal copper adopts an essentially planar configuration with the nitrogen atoms of H2L. The structure of the ligand and its complexes is proposed and formulated according to the elemental analyses, 1H- and 13C-n.m.r, i.r. and m.s. spectral data.     

Electrochemical behaviour of a series ofN,N′-1,2-Phenylenebis(salicylideneimin)ato transition metal complexes

Summary The electrochemistry of a series of nickel(II), copper(II), cobalt(II), manganese(II) and oxovanadium(IV) complexes with theN,N-1,2-phenylenebis(salicylideneimin)ate ligand has been studied in dimethyl sulfoxide solution. Kinetic and thermodynamic aspects of the electron-transfer processes are discussed, also with respect to those of the correspondingN,N-ethylenebis(salicylideneimin)ate and bis(salicylideneiminate-3-propyl)amine derivatives     

The effect of zinc(II) on the formation of 2,2′- and 2,3′-bipyridine complexes of [Ru2II(ttha)]2−(ttha6−=triethylenetetraminehexaacetate)

Ru2II(ttha)(H2O)2]2– (ttha6–= triethylene tetramine hexa-acetate), prepared by the reduction of the ruthenium(III) precursor, reacts with 2,2-bipyridine (2,2-bpy) in a multi-step fashion. The first 2,2-bpy equivalent (1:1) adds with bidentate chelation at one ruthenium(II) site as revealed by separate ruthenium(II)/(III) waves at 0.03 and 0.54V vs. n.h.e. A second equivalent of 2,2-bpy (1:2) is initially stored and retained as the [Zn(2,2-bpy)]2+ complex. Further addition of 2,2-bpy initiates coordination at the second ruthenium(II) site. [Ru2(ttha)-(2,2-bpy)(H2O)]2– forms a strong ion-pair with zinc(II) that is in rapid equilibrium with the Zn(H2O)62+/Zn(2,2-bpy)]2+ pool. The solubility of the ion-pair is low. The ion-pair exhibits a shifted ruthenium(II)/(III) wave at 0.60V. Higher amounts of 2,2-bpy recomplex the zinc(II), solubilizing the complex and returning the E1/2 value to 0.54V. Other ligands which either have a higher affinity for ruthenium(II) centres than for zinc(II) as bidentate donors (1,10-phenanthroline), or ligands that cannot form bidentate zinc(II) complexes [(2-methylpyrazine, 4,4-bipyridine (4,4-bpy), and 2,3-bipyridine (2,3-bpy)] do not exhibit the unusual competition by zinc(II). These ligands all add statistically to the ruthenium(II) centres forming 1:2 complexes with 1:2 stoichiometries. 1H-n.m.r. studies of the Ru(II)polyaminopolycarboxylate complexes [RuII(hedta)(H2O)]– complex, and [Ru2(ttha)(H2O)2]2– itself, reveal that substitution of 2,3-bpy at ruthenium(II) sites occurs with an initial kinetic split between the pyridyl rings of the 3- less-hindered and 2-more-hindered ring. A slower rearrangement occurs, producing the isomer of the more-hindered 2-substituted ring. A process is driven by forming a more -accepting system when ruthenium(II) binds to the 2-ring of 2,3-bpy. Understanding the unusual influence of zinc(II) on the substitution of 2,2-bpy with [Ru2(ttha)(H2O)2]2– clarifies the nature of the 1:1 complex – namely that the 2,2-bpy becomes bidentate at one ruthenium(II) centre rather than serving as a trans-bridging ligand between both ruthenium(II) centres within one [Ru2(ttha)]2– unit.     

Synthesis of 2,3,7,8-tetramethyldibenzofuran

3,4,3,4-Tetramethyldiphenyl ether readily forms 2,2-dihalo derivatives on bromination and iodination. Heating 2,2-diiodo-4,5,4,5-tetramethyldiphenyl ether with copper powder or oxidation, of 2,2-dilithio-4,5,4,5-tetramethyldiphenyl ether gives 2,3,7,8-tetramethyldibenzofuran, the structure of which was proved by alternative synthesis from 2,2-dinitroand 2,2-diamino-4,5,4,5-tetramethyldiphenyls.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1597–1599, December, 1972.     

Quantitative Bestimmung von Amingemischen durch multiplikative Verteilung

Zusammenfassung Es wird die quantitative Bestimmung der 5 Amine rac-N,N-Dibutyl-,-diphenyläthylendiamin (A), meso-N,N-Dibutyl-,-diphenyläthylendiamin (B), 1-Phenyl-1-butylamino-2-methyl-propan (C), N-Butyl-benzylamin (D) und Butylamin (E) in Reaktionsgemischen durch 54- und 95 stufige Craig-Nach-fraktionierungsprozesse in einer Verteilungsbatterie mit 35 Elementen nach Hecker [1] beschrieben. Durch graphische Auswertung der überlappenden Verteilungskurven wird eine quantitative Bestimmung auch bei 54 stufigen Prozessen, d.h. bei unvollständiger Trennung möglich.

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Quantitative determination of amine mixtures by multiplicative distributionOn the separation of organic bases by Craig distribution. IX

The quantitative evaluation of the 5 amines, rac-N,N-dibutyl-,-diphenylethylenediamine (A), meso-N,N-dibutyl-,-diphenylethylenediamine (B), 1-phenyl-1-butylamino-2-methyl-propane (C), N-butyl-benzylamine (D) and butylamine (E) in reaction mixtures by Craig after-fractionation processes of 54 and 95 steps in a distribution machine with 35 elements by Hecker [1] is described. By graphic evaluation of the overlapping distribution curves a quantitative determination is achieved, even with processes of 54 steps, i. e. incomplete separation.

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8.Mitteilung: Sohönenberger, H., Eder, M.: diese Z. 249, 117–120 (1970).

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Wir danken der Deutschen Forschungsgemeinschaft und dem Fonds der Chemischen Industrie für die Förderung unserer Untersuchungen.     

Study of furan compounds

Research on synthesis of polycyclic spirans of the 1, 6-dioxaspiro-[4, 4]nonane group is continued. Electrolysis of methanol solutions of 2-furylcyclopentanol, 2-(5-methyl-furfuryl)cyclopentanol, and 2-furfuryl-1-indanol, gives, by intramolecular alkoxylation, spiro{perhydrocyclopenta[b]furan-2, 2-(5dihydrofuran)}, spiro{perhydrocyclopenta[b]furan-2, 2-(5-methoxy-5-methyl-2, 5-dihydrofuran)}, and spiro{2, 3, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-(5-methoxy-2, 5-dihydrofuran)}, hitherto undescribed in the literature. Depending on the conditions, catalytic hydrogenation of these gives: spiro{perhydiocyclopenta[b]furan-2, 2-(5-methoxytetrahydrofuran)}, spiro{2, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-(5-methoxytetrahydrofuran)}, spiro{perhydrocyclopenta[b]furan-2, 2-tetrahydrofuran}, and spiro{2, 3, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-tetrahydrofuran}.For Part XXXI see [1].     

Simple and effective method for the synthesis of 3′,5′-substituted 1-β-D-arabinofuranosyluracil

3,5-Substituted arabinofuranosyluracil is a starting compound in 2-modifications. A convenient and effective method is proposed for the synthesis of 1-(3,5-di-o-trityl--D-arabinofuranosyl)uracil by successive reactions of 2,2-cyclization of uridine, 3,5-tritylation of the 2,2-anhydrouridine, and hydrolytic cleavage of the 2,2-anhydro bond.Institute of Organic Synthesis, Riga LV-1006. Odense Universitet, Kemisk Institut, Odense, Denmark. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 975–977, July, 1996. Original article submitted April 25, 1996.     

Podand-porphyrins with peripheral chelates

Alkylation of 5-(3-nitro-4-hydroxyphenyl)-10,15,20-triphenylporphyrin with chloropyridines[2,6-dichloromethyl-and 2-chloromethyl-6-(2-nitrophenoxymethylpyridine)] as well as condensation by a mixed-aldehyde method starting with formylpyridines [2-(2-nitro-4-formylphenoxymethyl)-6-(2-nitrophenoxy-methyl-) or 2,6-di(2-nitro-4-formylphenoxymethyl)pyridine], benzaldehyde, and pyrrole are used to synthesize previously unknown podand-porphyrins containing from one to four peripheral chelates.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 475–481, April, 1991.     

Benzoylation of 1,4-diaza-1,3-butadienes: Synthesis of representatives of a new chemical class—1,2-diamino-1-chloroethylenes

Trans-N,N-dialkyl-N,N-dibenzoyl-1,2-diamino-1-chloroethylenes — the first representatives of a new chemical class — and N,N-dialkyl-N,N-dibenzoyl-1,2-diaminoethylenes were obtained by benzoylation of N,N-dialkyl-1,4-diaza-1,3-butadienes. On increase in pressure to 10,000 atm, the yields of the N,N-dibenzoylated 1,2-diamino-1-chloroethylenes increase, and those of the N,N-dibenzoylated 1,2-diaminoethylenes decrease.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2038–2041, September, 1989.     

Demetallation of coordination compounds of nickel with tetradentate ligands based on S-substituted isothiosemicarbazides

The passage of dry gaseous hydrogen chloride through chloroform solutions or acetone suspensions of S-substituted N¹,N⁴-di(salicylidene)isothiosemicarbazidates of nickel (Ni(LRR)) has led to a demetallization reaction with the liberation in the free state of S-substituted N¹,N⁴-di(salicylidene)isothiosemicarbazides with the general formula N₂LRR (where R is H and R is CH₃ (I); R is H and R is C₂H₅ (II); R is H and R is C₃H₇ (III); R is H and R is C₇H₇ (IV); and R is CH₃ and R is CH₃ (V)). The IR spectra of (I-IV) each showed bands characteristic for an aromatic ring and groups in the 1600–1500 cm^–1 region, with a band of the deformation vibrations of an OH group at 1300 cm^–1. The PMR spectra in CDCl₃ each had two singlets at 12.15-11.25 and 9.00-8.36 ppm which were assigned, respectively, to the protons of an OH group and those of a =CH group. A multiplet in the 7.70-6.83 ppm region belonged to the protons of benzene rings. In the region of lower fields there were the signals of the substituents R and R. In the mass spectra of (I-V), the peaks of the molecular ions, and also the characteristic fragments OH, R, SR, and HSR have been detected.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 5, pp. 604–608, September–October, 1985.     

Synthesis of 1,4-diazabicyclo[2.2.2]octane

Double intramolecular cyclization of N,N-bis(2-chloroethyl)-N-N-bis(2-cyanoethyl)ethylenediamine leads to 1,4-bis(2-cyanoethyl)-1,4-diazoniabicyclo[2.2.2]octane dichloride, which undergoes decyanoethylation to 1,4-diazabicyclo[2.2.2]octane when it is heated. The structures of the compounds were confirmed by their IR and PMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 548–550, April, 1978.     

Investigations in the field of the chemistry of 2-hetarylbenzimidazoles. 6. Synthesis and properties of 1-methyl-2-(2′-selenienyl)benzimidazole

2-(2-Selenienyl)benzimidazole has been synthesized by a Weidenhagen reaction and converted into the N-methylated derivative. Electrophilic-substitution reactions (nitration, sulfonation, bromination, chloromethylation, and acylation) in the selenophene ring have been studied. It has been shown that the substituent enters the position of the selenophene ring in most cases. The bromination of 1-methyl-2-(2-selenienyl)benzimidazole in acetic acid produces the 3,5-dibromo derivative, whereas 1-methyl-5(or 6)-bromo-2-(3,5-dibromo-2-selenienyl)benzimidazole is obtained in polyphosphoric acid.For Report 5, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1531–1534, November, 1983.     

Spectrophotometric determination of vanadium with 4-(1′H-1′,2′,4′-Triazolyl-3′-azo)-2-methylresorcinol

Summary 4-(1H-1,2,4-Triazolyl-3-azo)-2-methylresorcinol reacts with vanadium(V) at pH 8.10 (Tris-HClO₄ buffer solution) to produce a pink-violet 11 complex ( _max=525 nm,=2.55×10⁴l·mol^–1· cm^–1) in a 50% (v/v) methanol-water medium, which allows the spectrophotometric determination of 0.1 to 1.51 ppm of vanadium. The method has been applied for the determination of the vanadium content in low alloy steels.

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Spectrophotometriscbe Bestimmung von Vanadin mit 4-(1H-1,2,4-triazo-lyl-3-azo)-2-methylresorcin

Zusammenfassung Vanadin bildet bei pH 8,10 (Tris-HClO₄-buffer) mit 4-(1H-1,2,4-tri-azolyl-3-azo)-2-methylresorcin ein rosenrot-violettes Chelat, dessen Absorptionsmaximum bei 525 nm in Gegenwart von 50% Methylalkohol gemessen wird. Dieser 11-Komplex entspricht bei einer Vanadin-Konzentration von 0,1–1,51g/ml dem Beerschen Gesetz; seine molare Absorptivität ist 2,55×10⁴l·mol^–1·cm^–1. Das Verfahren wurde zur Bestimmung des Vanadins in Stahl verwendet.

     

New biheterocyclic spiro system — Spiro-[1,4-benzodioxin-2 (3H),2′(3′H)-benzothiazole]

A convenient preparative method has been developed for obtaining 3-methylspiro[1,4-benzodioxin-2 (3H),2(3H)-benzothiazole], the first representative of biheterocyclic spiro compounds of a new type.Institute of Organic Chemistry, National Academy of Sciences of the Ukraine, Kiev 253660; e-mail: iochkiev@sovam.com Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1568–1570, November, 1999.     

Investigation of furan compounds XXX. Intramolecular alkoxylation of furfuryl-substituted mono- and bicyclic alcohols

On electrolysis mono- and bicyclic furfuryl-substituted alcohols undergo intramolecular alkoxylation, giving polycyclic spirans. Spiro[perhydrobenzofuran-2, 2-(5-methoxy, 5H)furan] and spiro[4H, 5H, 6H, 11H-naphtho-(,)-furan-2(3H)] [2-(5-methoxy, 5H)furan], hitherto not described, are prepared in this way. On catalytic hydrogenation they give the previously unknown spiro[perhydrobenzofuran-2, 2-tetrahydrofuran] and spiro[4H, 5H, 6H, 11H-naphtho-(,)-furan-2(3H)][2-tetrahydrofuran].For Part XXIX see [1].     

Optisch aktive,aromatische Spirane, 11. Mitt.: Synthese optisch aktiver mono- bis heptasubstituierter 5-Methyl- und 5-Ethyl-2,2′-spirobiindane und analoger Naphthalinderivate bekannter Chiralität und enantiomerer Reinheit

Starting from optically active 5,5-dimethyl, diethyl, and 5-ethyl-5-methyl-2,2-spirobiindane as well as from 5-ethyl-spirobiindane-5-carboxylic ester of known enantiomeric purity and configuration 75 mono to polysubstituted 2,2-spirobiindanes have been prepared. Amongst these are several compounds with rings anellated in the 6,7 (and 6, 7) positions, especially a spirohydrocarbon4 x with orthogonal naphthalene units the circular dichroism of which is reported and discussed.Several mono and disubstituted 5-methyl and ethylindanes (1,2) have been prepared as models for synthetic transformations in the spirobiindane series.From the molar rotations of symmetrically diacylated 5,5-dimethyl and diethyl spirobiindanes (4a, 7b, 7c) empirical ligand parameters for acetyl and methoxycarbonyl were determined which gave much better results in the calculation of the rotations of appropriate spirobiindanes (with the shortened polynomal Ansatz) than the -values deduced previously from 5,5-disubstituted spirobiindanes. The significance of these results is briefly discussed.

10. Mitt.:Neudeck, H., Schlögl, K., Angew. Chem.92, 318 (1980), Intern. Ed. Engl.19, 308 (1980).     

Synthesis and conversions of piperazine-2-carboxylic acid

A method has been developed for the synthesis of methyl piperazinium-2-carboxylate dihydrochloride (overall yield 46%) and piperazinium-2-carboxylic acid dihydrochloride (overall yield 36%), from ethylene diamine through N,N-di(trifluoroacetyl) ethylenediamine and methyl N,N-di(trifluoroacetyl)piperazine-2-carboxylate. The N,N-dinitroso derivatives were synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 833–836, June, 1985.     

Synthesis of novel heterocycles from thiazolecarbohydrazides

Cyclization of 2-methyl (or -phenyl)-5-phenylthiazole-4-carbohydrazides (1) and (2) under various conditions gives differing oxadiazoles: 2-(2-substituted-5-phenyl-4-thiazolyl)-1,3,4-oxadiazole-5-thiones (7) and (8), and 2-(2-substituted-5-phenyl-4-thiazolyl)-1,3,4-oxadiazoles (9) and (10). Cyclodehydration of thiazolecarbonyl-thiosemicarbazides (3)–(6) with NaOH givesthe 3-(2-substituted-5-phenyl-4-thiazolyl)-4-substituted-4H-5-mercapto-1,2,4-triazoles (11)–(14), while H ₃ PO ₄ gives the 2-(2-substituted-5-phenyl-4-thiazolyl)-5-phenylamino-1,3,4-thiadiazoles (15) and (16).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. 3, pp. 679–683, March, 1992.