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.     

Polarographic determination of some carcinogenic aminoazobenzenes

Summary The polarographic procedure can be used for the quantitative analysis of all the aminoazobenzenes tested in this study as indicated by proportionality between diffusion current and concentration. There is no significant correlation between the half-wave potential and carcinogenic potency for rat liver for three monosubstituted and seven disubstituted derivatives ofp-dimethylaminoazobenzene. These ring-substituted azocarcinogens rank from weak to very strong for carcinogenic potency against rat liver. Also aminoazobenzenes such as the noncarcinogenic 4-amino-4-dimethylaminoazobenzene and the carcinogenic N,N-dimethyl-4-amino-N-formyl-N-methyl-4-aminoazobenzene and N,N-dimethyl-4-amino-N-acetyl-N-methyl-4-aminobenzene have similar have-wave potentials. On the other hand, the noncarcinogenic 4-aminoazobenzene, 4-amino-N-methyl-4-aminoazobenzene and N-methyl-4-amino-N-methyl-4-aminoazobenzene have half-wave potentials that are about 100 mv more negative than that of all other aminoazobenzenes discussed in this report.

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Zusammenfassung Die Proportionalität zwischen Konzentration und Stromdurchfluß bietet die Grundlage zur polarographischen Bestimmung aller in dieser Arbeit geprüften Aminoazobenzole. Zwischen dem Halbwellenpotential und der carcinogenen Wirkung gegenüber Rattenleber besteht bei drei monosubstituierten und sieben disubstituierten Derivaten desp-Dimethylaminoazobenzols keine signifikante Korrelation. Diese ringsubstituierten Azocarcinogene zweigen schwache bis sehr starke carcinogene Wirkung gegenüber Rattenleber. Aminoazobenzole wie das nicht-carcinogene 4-Amino-4-dimethylaminoazobenzol und die carcinogenen Verbindungen N,N-Dimethyl-4-amino-N-formyl-N-methyl-4-aminoazobenzol und N,N-Dimethyl-4-amino-N-acetyl-N-methyl-4-aminoazobenzol haben ähnliche Halbwellenpotentiale. Andrerseits ist das Halbwellenpotential der nicht-carcinogenen Verbindungen 4-Aminoazobenzol, 4-Amino-N-methyl-4-aminoazobenzol und N-Methyl-4-amino-N-methyl-4-aminoazobenzol ungefähr um 100 mV negativer als das aller anderen hier behandelten Aminoazobenzole.

     

Solubilization of lanthanide ions by cyclodextrins in basic aqueous solutions

Cyclodextrins form complexes with lanthanide ions in basic aqueous solutions. This complex formation in basic solution dramatically enhances the solubility of lanthanide ions, which are otherwise insoluble due to the formation of hydroxide gels. Solutions of the -cyclodextrin-Ce³⁺ complex effectively hydrolyze 2-deoxyadenosine-5-monophosphate to 2-deoxyadenosine.     

Soluble polysaccharides of Rhodotorula flava

Conclusions 1. Xanthalin has been shown to have the structure of 2, 2-dimethyl-3, 4,-diangeloyloxy-3, 4-dihydropyrano-5, 6:6, 7-coumarin on the basis of the preparation of a number of derivatives and cleavage products.2. The following products of the alkaline hydrolysis of xanthalin have been isolated and characterized for the first time: (±)-3, 4-dihydroxy-3, 4-dihydroxanthyletin (isokhellactone), C₁₄H₁₄O₅, with mp 213–215° C and (–)-trans-3-hydroxy-4-methoxy-3, 4-dihydroxanthyletin (isomethylkhellactone, C₁₅H₁₆O₅, with mp 136.5–138° C and [] _D ²⁰ –47.7 (ethanol).Khimiya Prirodnykh Soedinenii, Vol. 6, No. 1, pp. 14–19, 1970     

Coordination polymers of cobalt(II) involving 4,4′-bipyridyl and its dioxide

Summary Analytical data, room temperature magnetic moment values, electronic and i.r. spectral measurements down to 200 cm^–1 on the coordination compounds formed by the interaction of cobalt(II) chloride, bromide, thiocyanate, acetate and nitrate with 4,4-bipyridyl and 4,4-bipyridylN,N-dioxide indicate that the isolated compounds are coordination polymers having tetrahedral or octahedral stereochemistry around cobalt(II) involving bridging 4,4-bipyridyl/4,4-bipyridylN,N-dioxide molecules. Terminally bonded acetato- and nitrato-ligands and bridging or terminally bonded chloro-, bromo- and thiocyanato-groups in the solid state.     

Use of electrostatic interaction for chiral recognition. Enantioselective complexation of anionic binaphthyls with protonated amino-β-cyclodextrin

The studies using NMR and capillary zone electrophoresis clearly reveal that protonated 6^A-amino- 6^A-deoxy--cyclodextrin recognizes the chirality of anionic binaphthyl derivatives such as 1,1-binaphthyl-2,2-diyl phosphate and 1,1-binaphthyl-2,2-dicarboxylate through electrostatic interaction between the host and the guest and simultaneous inclusion.     

Salicylaldehydo chelates of bis(cyclopentadienyl) zirconium(IV)

A new series of organometallic ionic chelates of the type [Cp ₂Zr(sal)]⁺ [ROCS₂/RRNCS₂]^–, where Hsal = salicylaldehyde;R =Me, Et, i-Pr ori-Bu andR =R =Me, Et, i-Pr;R =Me,R = benzyl orR =Et,R =m-tolyl, have been synthesized in aqueous medium by the reaction of [Cp ₂Zr(sal)]⁺Cl^– andROCS ₂ ^– K⁺/RRNCS ₂ ^– Na⁺. These compounds have been characterized by chemical analyses, electrical conductance, electronic, IR and¹H-NMR spectral studies. These studies indicate that the complexes are 1:1 electrolytes and the salicylaldehyde ligand is chelating in all these complexes. Therefore, a tetrahedral coordination about the zirconium atom is proposed.

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Salicylaldehydo-Chelate von Bis(cyclopentadienyl)-zirkonium(IV)

Zusammenfassung Eine neue Gruppe von organometallischen ionischen Chelaten vom Typ [Cp ₂Zr(sal)]⁺ [ROCS₂/RRNCS₂]^– (mit Hsal = Salicyladehyd;R =Me, Et, i-Pr oderi-Bu undR =R =Me, Et, i-Pr;R =Me,R = Benzyl oderR =Et,R =m-Tolyl) wurde in wäßrigem Medium mittels der Reaktion von [Cp ₂Zr(sal)]⁺Cl^– mitROCS ₂ ^– K⁺/RRNCS ₂ ^– Na⁺ hergestellt. Die erhaltenen Verbindungen wurden mittels chemischer Analyse, elektrischer Leitfähigkeit und der IR- sowie¹H-NMR-Spektren charakterisiert. Diese Untersuchungen zeigen, daß die Komplexe 1:1-Elektrolyte sind, wobei der Salicylaldehyd-Ligand in allen Fällen an der Chelatbildung beteiligt ist. Es wird daher für das Zirkoniumatom eine tetrahedrale Koordination vorgeschlagen.

     

Optisch aktive,aromatische Spirane, 8. Mitt.: Darstellung optisch aktiver, 5, 5′, 6′-trisubstituierter 2,2′-Spirobiindane bekannter Chiralität und enantiomerer Reinheit

Starting from (+) (2R) methyl 5-ethyl-2,2-spirobiindane-5-carboxylate of known enantiomeric purity 79 optically active, configurationally correlated 5,5,6-trisubstituted 2,2-spirobiindanes (2–7) were prepared for the purpose of testing a shortened polynomal Ansatz for chirality functions. Their optical rotations and¹H-nmr spectra are reported.In this context several 6-substituted 5-ethylindanes (1) were prepared as model compounds for synthetic transformations.

     

Fluorescence enhancement method for measuring anionic surfactants with a hydrophobic cyanine dye

A novel fluorimetric method based on use of a hydrophobic cationic cyanine dye has been developed for determination of the anionic surfactant sodium dodecylbenzenesulfonate (DBS). The method is based on the enhancement effect of DBS on the fluorescence of the hydrophobic cyanine dye 2-[-4-chloro-7-(1-ethyl-3,3-dimethylindolin-2-ylidene)-3,5-(propane-1,3-diyl)-1,3,5-heptatrien-1-yl]-1-ethyl-3,3-dimethyl-3H-indolium iodide. Under the optimum conditions the extent of fluorescence enhancement is proportional to the concentration of DBS in the range 0.05–5.0 mg L^–1; the detection limit is 0.014mg L^–1. The relative standard deviation for 0.35 mg L^–1 DBS was 1.1% (n=10). The proposed method, which avoided use of toxic solvents and tedious solvent-extraction, and was applied to the determination of DBS in natural water with recoveries between 99.9 and 107%. Preliminary research shows that the fluorescence enhancement is due to the formation of a dye aggregate facilitated by DBS.     

The structure effect of N,N,N′,N′-alkylamide in the extraction of uranium and thorium

In this paper, nine N,N,N,N-tetraalkyldiamides have been synthesized and the extracting ability for uranium and thorium under different conditions has been studied. All results were compared with those obtained by using tributyl phosphate (TBP) under exactly the same conditions. The extracting ability of thorium and uranium for different N,N,N,N-tetraalkyldiamides is discussed.     

Diazabicycloalkanes with nitrogen atoms in bridgehead positions. 16. Synthesis and properties of benzo[b]-1,4-diazabicyclo[2.2.2]octene and dibenzo[b,e]-1,4-diazabicyclo[2.2.2]octadiene,containing primary aromatic amino acids

4-Aminobenzo[1,2-b]-1,4-diazabicyclo[2.2.2]octene and 4-aminodibenzo[1,2-b, e]-1,4-diazabicyclo[2.2.2]octadiene have been prepared by cyclization reactions of N--chloroethyl derivatives of 1,2,4-triaminobenzene and aminophenazine, and subsequent catalytic hydrogenation of the corresponding 4-nitrobenzo[1,2-b]-1,4-diazabicyclo[2.2.2]octene and 4-benzylaminodibenzo[1,2-b,e]-1,4-diazabicyclo[2.2.2]-octadiene. Using the conversion of these compounds to azides as an example, we have demonstrated the feasibility of applying these primary aromatic amines for the synthesis of derivatives of these heterocycles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 831–837, June, 1988.     

Cracking of cumene on vanadium doped silica-alumina

The influence of small admixtures of vanadium on the activity of a silica-alumina catalyst in cumene cracking has been investigated. A correlation has been established between the catalytic and acidic properties of the vanadium doped catalyst.

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Investigations in the region of 2,3′-biquinoline. 3. Synthesis of 2′-alkyl(aryl)-1′,2′-dihydro-2,3′-biquinolines and 2′-alkyl(aryl)-2,3′-biquinolines

A method was developed for the synthesis of 2-alkyl(aryl)-1,2-dihydro-2,3-biquinolines, based on the addition of organolithium compounds to 2,3-biquinoline in the presence of tetramethylethylenediamine. Their oxidation with manganese dioxide led to 2-alkyl(aryl)-2,3-biquinolines.For Communication 2, see [1].Stavropol State University, Stavropol 355009, Russia. Russian Chemical-Technology University, Moscow 125190. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 350–354, March, 1998.     

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.     

Oxidative methods for synthesis ofα,α′-dioxygen-containing derivatives of dehydrodesthiobiotin

Conclusions The action of selenium dioxide in dioxane on the ethyl ester of-ketodebydrodesthiobiotin and of lead tetraacetate in glacial acetic acid on its N,N-diacetyl derivative give the corresponding ethyl esters of,-dioxodehydrodesthiobiotin and-oxo--acetoxy-N,N-diacetyldehydrodesthiobiotin.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2025–2028, September, 1972.     

Synthese des α,γ- und β,γ-Bipyridyls

Zusammenfassung P. Krumholz ¹⁵ hat kürzlich beim Vergleich physikochemischer Meßwerte erkannt, daß der als ,-Bipyridyl aufgefaßten Base die Formel des ,-Bipyridyls zuzuschreiben ist. Zur Prüfung dieser Frage und zur Kenntnis des wahren ,-Bipyridyls wurden die beiden Verbindungen auf eindeutigem Wege synthetisiert und ihre Konstanten mit denen der altbekannten Isomeren verglichen.Herrn Prof. Dr.F. Wessely zum 60. Geburtstag in alter Verbundenheit gewidmet.     

Ab initio studies of the low-lying π-states of borazine

Self-consistent-field and configuration-interaction studies were performed on borazine, using a double-zeta basis set augmented by six diffuse -functions. Low-lying singlet and triplet states of the A ₁ , A ₂ and E species were calculated, corresponding to ^* excited valence and Rydberg states. A selection out of singly and doubly excited configurations relative to a set of reference configurations was made for each species. Calculated vertical excitation energies (in eV) are 7.12 for ¹ A ₂(V), 8.45 for ¹ E (3p-R), 8.57 for ¹ A ₁(V), 8.9 for ¹ E(V-R), 9.55 for ¹ E(3d-R), 6.98 for ³ A ₁(_V), 7.27 for ³ E(V), 7.82 for ³ A ₂(V), 8.30 for ³ E(3p-R), and 9.5 for ³ E(3d-R), where V and R refer to valence or Rydberg character. The results are compared with experimental excitation energies, previous ab initio studies of borazine, and with recent ab initio studies of benzene.Dedicated to Professor Dr. H. Hartmann on the occasion of his 65th birthday.     

Nitration,amination, and halogenation of Di-O-methylphloracetophenone

Chlorination of the title compound gave 5- and 3-chloro-2-hydroxy-4,6-dimethoxyacetophenone. The nitration of its acetate, followed successively by reduction, diazotization, and reaction with cuprous chloride, gave the 3-substituted series, 2-acetoxy-4,6-dimethoxy-3-nitroacetophenone, 3-amino-2-hydroxy-4,6-dimethoxyacetophenone, and 3-chloro-2-hydroxy-4,6-methoxyacetophenone, respectively. The orientation of substituents in the products was proved. The amino and chloro members of the isomeric 5-substituted series were availablevia 2-hydroxy-4,6-dimethoxy-5-phenylazoacetophenone, the product of the reaction of the title compound with benzenediazonium chloride.

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Nitrierung, Aminierung und Halogenierung von Di-O-methylphloracetophenon

Zusammenfassung Chlorierung der Titelverbindung gab 5- und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Nitrierung des Acetats, gefolgt von Reduktion, Diazotierung und Reaktion mit CuCl ergab die 3-substituierte Reihe: 2-Acetoxy-4,6-dimethoxy-3-nitroacetophenon, 3-Amino-2-hydroxy-4,6-dimethoxyacetophenon und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Orientierung der Substituenten wird diskutiert. Die Amino- und Chlorderivate der isomeren 5-substituierten Reihe sind über 2-Hydroxy-4,6-dimethoxy-5-phenylacetophenon zugängig, dem Produkt der Reaktion der Titelverbindung mit Phenyldiazoniumchlorid.

     

Synthetic studies in the field of chlorobium chlorophyll

By the condensation of -halogenomethyl derivatives of pyrroles with -unsubstituted pyrroles the synthesis of the following unsymmetrical dipyrrolylmethanes has been effected: 5-benzyloxycarbonyl-5-ethoxycarbonyl-3, 3-di(-methoxycarbonylethyl)-4,4-dimethyl-2,2-dipyrrolylmethane (IIIa), 5-benzyloxycarbonyl-5-ethoxycarbonyl-3-(-methoxycarbonylethyl)-4, 4-diniethyl-3-n-propyl-2,2-dipyrrolylmethane(IIIb), 3-acetyl-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIIc), and 3-bromo-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIId). Hydrogenation of the unsymmetrical dipyrrolylmethanes IIIa, b, c, and d has given the corresponding monocarboxylic acids IVa, b, c, and d. The formylation of the dipyrrolylmethanemonocarboxylic acid IVa has given 5-ethoxycarbonyl-5-formyl-3,3-di(-methoxycarbonylethyl)-4, 4-dimethyl-2,2-dipyrrolylmethane (V).For communication II, see [1].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1045–1047, August, 1970.