Synthesis and Reactions of 5-Amino-3-(3-methyl-5-oxo-1-phenyl-2-pyrazolin-4-yl)-7-phenyl-7 H -thiazolo[3,2- a ]pyrimidine-6-carbonitrile

5-Amino-3-(3-methyl-5-oxo-1-phenyl-2-pyrazolin-4-yl)-7-phenyl-7H-thiazolo[3,2-a]pyrimidine-6-carbonitrile was synthesized via the reaction of 4-(2-aminothiazol-4-yl)-3-methyl-1-phenyl-2-pyrazolin-5-one with benzylidene malononitrile and was then transformed to related fused heterocyclic systems. The antifungal and antibacterial studies revealed in some cases excellent biocidal properties.     

Organophosphorus chemistry,XII. Reaction of furil with alkyl phosphites and ylide-phosphoranes

Summary The reaction of furil (1) with trialkyl phosphites2 yielded caged phosphorane derivatives of types3a-c. Dry hydrogen chloride gas converted3a-c into the respectivea-hydroxyvinyl-phosphates8a-c which are equally produced by reacting furil with the appropriate dialkyl phosphite7. The reaction of furil with ylide-phosphoranes10 proceeded according to the Wittig reaction mechanism to give the respective ethylenes11a-c. The new compounds have been characterized by their spectroscopic data (IR, PMR,³¹P-NMR, MS) and elementary analyses.Dedicated to Prof. M. Sidky on the occasion of his 60th birthday     

Synthesis of Important New Pyrrolo[3,4‐c]Pyrazoles and Pyrazolyl‐Pyrrolines from Heterocyclic β‐Ketonitriles

Treatment of heterocyclic β‐ketonitriles 1a,b with hydrazine hydrate and phenylhydrazine afforded the hydrazine derivatives 2a‐d which cyclized in PPA into pyrrolo[3,4‐c]pyrazoles 3a‐d. Reaction of 1a,b with cyanoacetohydrazide furnished the cyanoacetyl pyrrolo[3,4‐c]pyrazoles 4a,b. The hydrazine 2c reacted with β‐diketone and β‐ketoesters to afford pyrazolyl‐pyrrolines 5‐7. Also the later hydrazine reacted with some D‐aldoses and aceteophenone to give the corresponding hydrazones 10‐12 and hydrazine carboxamide derivatives 15a,b respectively.     

A new phase in the Ag−O−S system

The investigations of reaction between Ag₂SO₄ and Ag₂S in air atmosphere have been carried. Results of DTA and X-ray phase powder diffraction of a reaction mixture have confirmed that in the Ag?O?S system exists a new phase. A formula of the phase is Ag₂SO₂.     

Kinetics of the Formation of Goethite in the Presence of Sulfates and Chlorides of Monovalent Cations

The synthesis of goethite by oxidation of Fe²⁺in presence of metallic iron was undertaken in an aqueous medium containing indifferent salts such as Na₂SO₄, (NH₄)₂SO₄, NaCl, and NH₄Cl. Temperature and bubbling air rate were maintained, respectively, at 70°C and 1 L/min. The influence of anions and cations on the kinetics of each step of the process has been followed distinctly, the iron dissolution rate has been determined by the variation of the medium acidity, and the precipitation of goethite has been determined by gravimetric measurements. With respect to Cl⁻, the SO₄²⁻anion decreases the rate of the two reactions. NH₄⁺acts as an inhibitor when it is present at low concentrations and as an accelerator for higher concentrations; the limit corresponding to the change of NH₄⁺behavior depends on the nature of the counter ion. The reaction product is composed of pure goethite in the presence of sulfate salts, whereas a mixture of goethite and lepidocrocite, respectively, 60–70 and 40–30%, was observed in the presence of chloride salts.     

Electrochemical oxidation of aliphatic amines and their attachment to carbon and metal surfaces

The electrochemical oxidation of aliphatic amines (primary, secondary, and tertiary) has been investigated by cyclic voltammetry and preparative electrolysis. The oxidation mechanisms have been established, and the lifetimes of the radical cations have been measured for secondary and tertiary amines. These results have been put in parallel with the attachment of amines to glassy carbon, Au, and Pt electrodes by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and infrared reflection-absorption spectroscopy (IRRAS). It is then possible to show that it is not the radical cation but the radical obtained after the deprotonation which reacts with the electrode surface. XPS results also point to the existence of a covalent bond between Au or Pt and the organic moiety.     

A novel synthetic route to 2-alkylpropane-1,3-sultones and its application to the synthesis of 2-alkyl derivatives of tramiprosate

A practical synthetic route to various 2-alkylpropane-1,3-sultones, the key intermediates for the preparation of 2-substituted homotaurines as analogs of tramiprosate, was developed.     

Tetrastrontium dimanganese copper nonaoxide,Sr4Mn2CuO9

Single crystals of Sr₄Mn_2.09Cu_0.91O₉ have been grown by flux synthesis and the structure, closely related to the hexagonal perovskite 2H, was solved from single‐crystal X‐ray data in space group P321. The structure of Sr₄Mn₂CuO₉ is composed of chains of face‐sharing polyhedra with a sequence of two octahedra and one trigonal prism. The octahedra are filled by Mn atoms and the Cu atoms are randomly distributed at the centres of the square faces of the trigonal prism. A stacking fault is observed within one of the two chains, which can be attributed to a shifting of the chain along the c axis.     

Adsorption of Molybdenum on Titania from Aqueous Solutions

The adsorption of Mo from dilute aqueous solutions (10(-3) to 3x10(-2) M) is effected on three samples of titania, two are anatase and the third is P25, which is composed of rutile and anatase. The adsorption isotherms at 298, 318, and 338 K are analyzed using a Langmuir linear equation. The isotherms on P25 showed a distinct inflection point that is reproduced by two linear portions, indicating different adsorption regimes. This adsorption behavior is explained as follows: with low amount adsorbed the adsorption is initiated by protonation of the basic hydroxyls on which the negatively charged MoO(4)(2-')s are adsorbed, and this is accompanied by an increase in the pH of the impregnating solution. At higher adsorption the coordinatively unsaturated Ti(4+) sites participate in the process, leading to a decline in the initial increase in pH. In the case of the two anatase samples the low surface area resulted in poor distribution of adsorption sites; consequently, the distinction between the two modes of adsorption was not entirely clear. The higher adsorption site density in the case of anatase is accompanied by a lower surface coverage, θ, than that for P25. The heat of adsorption, Q, on the three titania samples showed a linear increase with θ, which is represented by the regression equation: -Q=95.77θ-4.25 (R(2)=0.993). Copyright 2001 Academic Press.     

Synthesis of imidazoles as novel emivirine and S‐DABO analogues

5‐Alkyl‐4‐benzyl‐1,3‐dihydroimidazol‐2‐ones ( 3a‐d ) and 5‐alkyl‐4‐benzyl‐1,3‐dihydroimidazole‐2‐thiones (7a‐d) were prepared via Dakin West reaction on DL‐phenylalanine with the appropriate aliphatic acid anhydrides followed by hydrolysis and reaction with potassium cyanate or potassium thiocyanate. Compounds 3a‐d were alkylated with ethoxymethyl chloride to give the alkylated imidazoles 5a‐d which were considered analogues of Emivirine with deletion of carbonyl group at the 4‐position. Alkylation of 7a‐d afforded the corresponding S‐alkylated derivatives 8a‐p which in a similar way were considered analogues of S‐DABO. However all the imidazole derivatives were devoid of activity against HIV.