Central nervous system depressants. 15. 1,4-benzodiazepines

A number of 5-phenyl-1,4-benzodiazepines and a few 2-phenyl-1,4-benzodiazepines were prepared and screened for central nervous system activity in mice. Some were highly active. An unusual substitution of 7-chloro-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepin-2-one by trichloro-acetylisocyante is reported.     

Central nervous system depressants. 14. As-triazino-1,4-benzodiazepines

Seven series of as-triazino[4,3-a] [1,4]benzodiazepines were prepared which differed in the degree of unsaturation or the nature and position of oxygen function on the triazino ring. These were prepared by closing the triazino ring of appropriately substituted hydrazones from 2-hydrazinobenzodiazepines or by condensing substituted hydrazines with 2-thiobenzodiazepines. Most of these represent new ring systems. They were tested in a battery of tests designed to uncover central nervous system activities. Most of the activity was found in tests thought to be indicative of anxiolytic, hypnotic or sedative potential. Five of the series contained members more active than the standard, diazepam, and a few of the compounds were among the most potent benzodiazepines known. Some of the intermediate benzodiazepine hydrazones were also active.     

Synthesis of (5S)-5-methylfuran-2(5H)-one and its dihydro derivative

(5S)-5-Methylfuran-2(5H)-one and (5S)-5-methyltetrahydrofuran-2-one were synthesized starting from L-lactic acid ethyl ester.     

Reaction of zirconium(IV) with 2,3,4-trihydroxiphenylazo-5′-sulfonaphthalene in the presence of diantipyrilmethane and its homologues

The effect of diantipyrilmethane and its homologues on the complexation of zirconium(IV) with 2,3,4-trihydroxiphenylazo-5′-sulfonaphthalene is studied, and conditions for the formation of mixed-ligand complexes are determined. Correlations between the acidity constants of diantipyrilmethane and its homologues and the stability constants and the specific conductivity of complexes, and degree of contrast, and the change in the Gibbs free energy are found for the complexation reaction. A method is developed for the selective photometric determination of zirconium in pyrite containing modified quartz diorite.     

Nitration of 5(6)-hydroxybenzimidazole and its derivatives

Nitration of 5(6)-hydroxybenzimidazole and its derivatives takes place with the formation of mono- and dinitro-derivatives; in the latter case, the primary substitution is, as a rule, in position 4.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2329–2332, October, 1989.     

Adsorptive stripping voltammetry of trace manganese in the presence of 2-(5'-bromo-2'-pyridylazo)-5-diethylaminophenol (5-Br-PADAP)

Trace levels of manganese can be determined by voltammetry after controlled adsorptive accumulation of the manganese-2-(5'-bromo-2'-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) complex on a hanging mercury drop electrode. Optimal conditions include an ammonia buffer solution (pH 8.8) containing 1 x 10(-5)M 5-Br-PADAP and an accumulation potential of -1.20 V. The technique offers enhanced sensitivity over analogous measurements of the manganese-Eriochrome Black T chelate. The detection limit is 0.2 mug/1 with 1 min accumulation. The new adsorptive approach is characterized with new selectivity dimensions (compared to the Eriochrome Black T scheme), and is not affected by large excess of commonly coexisting calcium and magnesium cations (which severely interfere in the Eriochrome Black T procedure).     

6(5H)-phenanthridinones. III. halo-6(5H)phenanthridinones

Halogenation of 6(5H)-phenanthridinone or its 3,8-dihalo derivatives with N-bromo or N-chlorosuccinimide in dimethylformamide gives the corresponding 2-halophenanthridinones (I,V,XI-XIV). Further halogenation of 2-halo-6(5H)-phenanthridinone with the appropriate N-halosuccinimide, in the same medium, gives the corresponding 2,4-dihalo derivatives (II,VI). NXS/DMF is found to be a very convenient halogenating system in these preparations. 1,3,8-Trihalo-6(5H)-phenanthridinones (XIX,XX) are prepared from the 1-nitro derivatives which are obtained by a Schmidt rearrangement of 2,7-dihalo-4-nitro-9-oxofluorenes. Similarly, rearrangement and further reaction of 2-nitro-5-chloro-9-oxofluorene (XXI) leads to 3,10-dichloro-6(5H)-phenanthridinone (XXIV). UV absorptions as well as selected IR absorptions of these 6(5H)-phenanthridinones are described.     

Synthesis and properties of analogs of 5(4)-aminoimidazole-4(5)-carboxamide and purines. 14. Acylation of 5(4)-aminoimidazole derivatives

The acylation of 5(4)-aminoimidazole derivatives was studied. It is shown that acylation by means of carboxylic acid anhydrides and chlorides takes place at the amino group, whereas acylation by means of chlorocarbonic acid esters takes place at the nitrogen atoms of the imidazole ring. Methods for the selective introduction of a carbomethoxy group in the 1, 3, and 5 positions of the 5(4)-aminoimidazole-4(5)-carboxamide molecule were developed.See [1] for communication 13.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 247–252, February, 1984.     

Azo coupling of 5(6)-hydroxybenzimidazole and its derivatives

The azo coupling of 5(6)-hydroxybenzimidazole and its derivatives is directed toward C⁴.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 662–664, March, 1990.     

High-performance liquid chromatographic determination of 1-beta-D-arabinofuranosyl-E-5-(2-bromovinyl)uracil and its metabolite (E)-5-(2-bromovinyl)uracil in serum.

A high-performance liquid chromatographic method was developed to assay 1-beta-D-arabinofuranosyl-E-5-(2-bromovinyl)uracil and its metabolite (E)-5-(2-bromovinyl)uracil in serum. The chloro analogue of the parent drug is used as internal standard. Human serum samples were assayed to establish the pharmacokinetic parameters. Acetonitrile, used as a protein precipitant, was evaporated to dryness and the residue, containing the analytes and internal reference, was dissolved in mobile phase prior to chromatographic analysis. The minimum quantifiable level was 0.02 micrograms of each analyte per ml of serum.     

Solid state NMR characterization of individual compounds and solid solutions formed in Sc(2)O(3)--V(2)O(5)--Nb(2)O(5)--Ta(2)O(5) system

In this study, (51)V, (45)Sc and (93)Nb MAS NMR combined with satellite transition spectroscopy analysis were used to characterize the complex solid mixtures: VNb(9(1-x))Ta(9x)O(25), ScNb((1-x))Ta(x)O(4) and ScNb(2(1-x))Ta(2x)VO(9) (x = 0, 0.3, 0.5, 0.7, 1.0). This led us to describe the structures of Sc and V sites. The conclusions were based on accurate values for (51)V quadrupole coupling and chemical shift tensors obtained with (51)V MAS NMR/SATRAS for VNb(9)O(25), VTa(9)O(25) and ScVO(4). The (45)Sc NMR parameters have been obtained for Sc(2)O(3), ScVO(4), ScNbO(4) and ScTaO(4). On the basis of (45)Sc NMR and data available from literature, the ranges of the (45)Sc chemical shift have been established for ScO(6) and ScO(8). The gradual change of the (45)Sc and (51)V NMR parameters with x confirms the formation of solid solutions in the process of synthesis of VNb(9(1-x))Ta(9x)O(25) and ScNb((1-x))Ta(x)O(4), in contrast to ScNb(2(1-x))Ta(2x)VO(9). The cation sublattice of ScNb((1-x))Ta(x)O(4) is found to be in octahedral coordination. The V sites in VNb(9(1-x))Ta(9x)O(25) are present in the form of slightly distorted tetrahedra. The (93)Nb NMR parameters have been obtained for VNb(9)O(25).     

Indole derivatives. 124. 5-(2-phenylethenyl)indolines and 5-(2-phenylethenyl)indoles

5-(2-Phenylethenyl)indolines, the dehydrogenation of which leads to the formation of the corresponding compounds of the indole series, were obtained from 5-formyl-1-methyl(or benzyl)indolines via the Grignard reaction with benzyl-magnesium chloride and subsequent dehydration. The hormonal activity of the synthesized compounds was studied.See [1] for communication 123.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 4, pp. 466–469, April, 1984.     

Metal dimers as catalysts : III. The reaction between Fe(CO)5, and group V donor ligands in the presence of [(η5-C5H4R)Fe(CO)222]2 (R  H,Me) and [(η5-C5Me5)Fe(CO)2]2 as catalyst

The reaction between Fe(CO)₅, and group V donor ligands L, (L  PPh₃, AsPh₃, SbPh₃, PMePh₂, PMe₂Ph, Asme₂Ph, P(C₆H₁₁)₃, P(n-Bu)₃, P(i-Bu)₃, P(OPh)₃, P(OEt)₃, P(OMe)₃) in the presence of [(η⁵-C₅Me₅Fe(CO)₂]₂ (R  H, Me) or [(η⁵-C₅Me₅)Fe(CO)₂]₂ as catalyst in refluxing toluene, rapidly gives the complexes Fe(CO)₄L in yields > 85%. The reaction rate is essentially independent of the nature of L for [(η₅-C₅Me₅)Fe(CO)₂]₂ as catalyst. For the other catalysts, the rate is influenced predominantly by the steric properties of L. These results are interpreted in terms of the interaction between the catalyst and the ligand L to give derivatives of the type (η⁵-C₅H₄R)₂Fe₂,(CO)₃,(L). These derivatives were also found to catalyse the reaction between Fe(CO)₅, and L. The complexes [(η-C₅H₄R)Fe(CO)₂]₂ (R  H, Me) and [(η⁵-C₅Me₅)Fe(CO)₂]₂ also catalyse the reaction between Mn₂(CO)₁₀ and PPh₃ to give Mn₂(CO)₈- PPh₃)₂ in > 80% yield.     

Study on the supramolecular system of 5-(p-hydroxyphenyl)-10,15,20-tris-(4-chlorophenyl)porphyrin with cyclodextrins and its analytical characteristics

The supramolecular systems of 5-(p-hydroxyphenyl)-10,15,20-tris-(4-chlorophenyl)porphyrin (p-HTClPP) with beta-cyclodextrin (beta-CD), heptakis(2,3,6-tri-O-methyl)-beta-CD (TM-beta-CD), carboxymethyl-beta-cyclodextrin (CM-beta-CD) and sulfurbutylether-beta-CD (SBE-beta-CD) have been investigated by means of absorption, fluorescence and (1)H NMR spectroscopy. The formation of inclusion complexes has been confirmed on the base of changes of spectroscopy properties. "The double reciprocal method" has been used to determine the stoichiometry and the inclusion constants of p-HTClPP with the four cyclodextrins (CDs). The results show that p-HTClPP can form 1:1 inclusion complexes with the four CDs. Compared with parent native beta-CD, the inclusion abilities of modified beta-CDs with p-HTClPP are stronger. It indicates that the hydrophobic effect plays an important role in the inclusion procedure. The mechanism of inclusion interaction was examined by (1)H NMR technique. During the study of p-HTClPP-TM-beta-CD supramolecular complex, an efficient enhancement of fluorescence intensity was observed. Based on this phenomenon, fluorometric method for the determination of p-HTClPP was developed. The relationship between fluorescence intensity and the concentration of p-HTClPP is linear from 1.0 x 10(-9) to 7.0 x 10(-6)mol L(-1). The limit of detection is 8.3 x 10(-10)mol L(-1) and the relative standard deviation (R.S.D.) is 1.3% (n=8). This research will provide useful information for further application of p-HTClPP.     

Thermische disproportionierung von (η5-C5H5)2V2(CO)5. Tetrakis[carbonyl(η5-cyclopentadienyl)vanadium], (η5-C5H5)4V4(CO)4

The novel vanadium cluster tetrakis[carbonyl(η⁵-cyclopentadienyl)- vanadium has been prepared in 32% yield by thermal disproportionation of μ-dicarbonyltricarbonylbis(η⁵-cyclopentadienylvanadium) (V-V) in boiling tetrahydrofuran.