Reactivity of µ-Peroxo-Bridged Dimeric Vanadate in Bromoperoxidation

Diglycyl triperoxodivanadate [V2O2(O2)3(Gly H)2(H2O)2], a synthetic compound with μ-peroxo-bridge derived from H2O2and vanadate, oxidized bromide to a bromination-competent intermediate in phosphate buffer and physiological pH. This is in contrast to the requirement of acid medium with H2O2as the oxidant. Addition of its solid to bromide solution instantly produced a 262-nm-absorbing compound that converted phenol red (a trap) to its 592-nm-absorbing bromo-derivative. The high bromination activity was lost on dissolving this compound in water and the solution showed the presence of peroxovanadates (mono and di) and vanadates (V1and oligomeric V10) in51V-NMR spectrum. Of these, diperoxovanadate and vanadate together supported slow bromination activity by a second set of reactions including bromide-assisted reductive formation of vanadyl. Bromination activity dependent on vanadyl was sensitive to oxidation by excess H2O2and to complexation by EDTA, whereas that of triperoxodivanadate was relatively insensitive. Vanadyl and diperoxovanadate are capable of forming a μ-peroxo-bridged complex that is essentially similar to the synthetic vanadate dimer used in the present experiments. It appears that a μ-peroxo-intermediate is the proximal oxidant of bromide in vanadium-catalyzed bromoperoxidation.

A direct borohydride fuel cell employing Prussian Blue as mediated electron-transfer hydrogen peroxide reduction catalyst

A direct borohydride-hydrogen peroxide fuel cell employing carbon-supported Prussian Blue (PB) as mediated electron-transfer cathode catalyst is reported. While operating at 30 °C, the direct borohydride-hydrogen peroxide fuel cell employing carbon-supported PB cathode catalyst shows superior performance with the maximum output power density of 68 mW cm−2 at an operating voltage of 1.1 V compared to direct borohydride-hydrogen peroxide fuel cell employing the conventional gold-based cathode with the maximum output power density of 47 mW cm−2 at an operating voltage of 0.7 V. X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and Energy Dispersive X-ray Analysis (EDAX) suggest that anchoring of Cetyl-Trimethyl Ammonium Bromide (CTAB) as a surfactant moiety on carbon-supported PB affects the catalyst morphology. Polarization studies on direct borohydride-hydrogen peroxide fuel cell with carbon-supported CTAB-anchored PB cathode exhibit better performance with the maximum output power density of 50 mW cm−2 at an operating voltage of 1 V than the direct borohydride-hydrogen peroxide fuel cell with carbon-supported Prussian Blue without CTAB with the maximum output power density of 29 mW cm−2 at an operating voltage of 1 V.

The generalized anomeric effect in the 1,3-thiazolidines: Evidence forboth sulphur and nitrogen as electron donors. Crystal structures of various N-acylthiazolidines including mercury(II) complexes. Possible relevance to penicillin action

Evidence for the generalized anomeric effect (GAE) in the N-acyl-1,3-thiazolidines, an important structural motif in the penicillins, was sought in the crystal structures of N-(4-nitrobenzoyl)-1,3-thiazolidine and its (2:1) complex with mercuric chloride, N-acetyl-2-phenyl-1,3-thiazolidine, and the (2:1) complex of N-benzoyl-1,3-thiazolidine with mercuric bromide. An inverse relationship was generally observed between the. C-2-N and C-2-S bond lengths of the thiazolidine ring, supporting the existence of the GAE. (Maximal bond length changes were similar to 0.04 angstrom for C-2-N-3, S-1-C-2, and similar to 0.08 angstrom for N-3-C-6.) Comparison with N-acylpyrrolidines and tetrahydrothiophenes indicates that both the nitrogen-to-sulphur and sulphur-to-nitrogen GAE's operate simultaneously in the 1,3-thiazolidines, the former being dominant. (This is analogous to the normal and exo-anomeric effects in pyranoses, and also leads to an interesting application of Baldwin's rules.) The nitrogen-to-sulphur GAE is generally enhanced in the mercury(II) complexes (presumably via coordination at the sulphur); a 'competition' between the GAE and the amide resonance of the N-acyl moiety is apparent. There is evidence for a 'push-pull' charge transfer between the thiazolidine moieties in the mercury(II) complexes, and for a 'back-donation' of charge from the bromine atoms to the thiazolidine moieties in the HgBr2 complex. (The sulphur atom appears to be sp(2) hybridised in the mercury(II) complexes, possibly for stereoelectronic reasons.) These results are apparently relevant to the mode of action of the penicillins. (c) 2006 Elsevier B.V. All rights reserved.

Volumetric determination of tetraalkyl thiuram disulphides

A method for the volumetric determination of tetraalkyl thiuram disulphide is developed. It is based on its reaction with potassium cyanide in aqueous acetonitrile medium, when the corresponding tetraalkyl thiuram monosulphide and thiocyanate are formed. The former is removed by extraction with benzene and the latter converted into cyanogen bromide, which is estimated iodometrically.

Raman and infra-red spectra of crystalline ammonium sulphamate

Raman spectrum of a single crystal of ammonium sulphamate has been recorded for the two different orientations using λ 2537 resonance radiation of the mercury as the exciter. Thirty-four Raman lines have been observed of which eight belong to the lattice oscillations. Weak hydrogen bonding of NH2 group in the crystal was predicted. The infra-red absorption spectrum of the substance was taken in the powder form in potassium bromide disc, using Carl Zeiss UR10 IR spectrometer. Thirty-five absorption maxima could be identified.

Raman and infra-red spectra of crystalline potassium sulphamate

Raman spectrum of a single crystal of potassium sulphamate has been recorded for the first time using λ 2536 radiation of mercury as the exciter. Thirty-three Raman lines have been observed of which nine belong to the lattice oscillations. The infra-red absorption spectrum of the substance was taken in the powder form in potassium bromide disc using Carl Zeiss UR 10 IR spectrometer. Thirty-six absorption maxima could be identified of which twenty-five have been recorded for the first time. The analysis clearly shows that the N-H bond in the crystalline potassium sulphamate is not hydrogen-bonded to any appreciable extent.

Infrared spectra of substituted benzoyl chlorides and benzoyl bromides. Explanation of the anomalous carbonyl band-splittings

Infrared spectra of substituted benzoyl chlorides and benzoyl bromides have been studied. The extent of splitting of the carbonyl band in benzoyl chlorides varies with substitution. While benzoyl bromide shows the carbonyl band as a single peak, para-nitrobenzoyl bromide shows a doublet. The results are interpreted in terms of intramolecular vibration effects (Fermi resonance). The intense band in the 860–880 cm−1 region in benzoyl chloride and benzoyl bromide has been assigned to the Ph-C stretching vibration.

Synthesis and identification of a new class of (S)-2,6-diamino-4,5,6,7-tetrahydrobenzo[d]thiazole derivatives as potent antileukemic agents

Benzothiazoles are multitarget agents with broad spectrum of biological activity. Among the antitumor agents discovered in recent years, the identification of various 2-(4-aminophenyl) benzothiazoles as potent and selective antitumor drugs against different cancer cell lines has stimulated remarkable interest. Some of the benzothiazoles are known to induce cell cycle arrest, activation of caspases and interaction with DNA molecule. Based on these interesting properties of benzothiazoles and to obtain new biologically active agents, a series of novel 4,5,6,7-tetrahydrobenzo[d]thiazole derivatives 5(a-i) were synthesized and evaluated for their efficacy as antileukemic agents in human leukemia cells (K562 and Reh). The chemical structures of the synthesized compounds were confirmed by H-1 NMR, LCMS and IR analysis. The cytotoxicity of these compounds were determined using trypan blue exclusion, 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and lactate dehydrogenase (LDH) assays. Results showed that, these compounds mediate a significant cytotoxic response to cancer cell lines tested. We found that the compounds having electron withdrawing groups at different positions of the phenyl ring of the thiourea moiety displayed significant cytotoxic effect with IC50 value less than 60 mu M. To rationalize the role of electron withdrawing group in the induction of cytotoxicity, we have chosen molecule 5g (IC50 similar to 15 mu M) which is having chloro substitution at ortho and para positions. Flow cytometric analysis of annexin V-FITC/ propidium iodide (PI) double staining and DNA fragmentation suggest that 5g can induce apoptosis.

A new chiral oxazoline derived from camphor and its conversion to (R)-2-methylalkanoic acids

1S,5R,7R)-(-)-10, 10-Dimethyl-3-ethyl-4-oxa--atricyclo[5.2.1.0(1,5)]dec-2-ene 2 was prepared in 95% yield from (1S)-1-amino-2-exo-hydroxyapocamphane 1. The chiral oxazoline could be alkylated (Lhttp://eprints.iisc.ernet.in/cgi/users/home?screen=EPrint::Edit&eprintid=31175&stage=core#tDA/THF/-78 degrees C/RX, RX = ethyl, n-propyl, n-butyl iodides or benzyl bromide) to 3 in 95% yield and > 95% diastereoselectivity, and the products hydrolysed to (R)-2-methylalkanoic acids 4 (43-47% yield, 93-98% e.e.). (C) 2000 Elsevier Science Ltd. All rights reserved.

Novel phase-transition behavior in an aqueous electrolyte solution

We have investigated the near-critical behavior of the susceptibility of a ternary liquid mixture of 3-methylpyridine. water, and sodium bromide as a function of the salt concentration. The susceptibility was determined from light-scattering measurements performed at a scattering angle of 90 degrees in the one-phase region near the locus of lower consolute points. A sharp crossover from asymptotic Ising behavior to mean-field behavior has been observed at concentrations ranging from 8 to 16.5 mass% NaBr. The range of asymptotic Ising behavior shrinks with increasing salt concentration and vanishes at a NaBr concentration of about 17 mass%. where complete mean-field-like behavior of the susceptibility is observed. A simultaneous pronounced increase in the background scattering at concentrations above 15 mass%, as well as a dip in the critical locus at 17 mass % NaBr, suggests that this phenomenon can be interpreted as mean-field tricritical behavior associated with the formation of a microheterogeneous phase due to clustering of the molecules and ions. An analogy with tri critical behavior observed in polymer solutions as well as the possibility of a charge-density-wave phase is also discussed. In addition, we, have observed a third soap-like phase an the liquid-liquid interface in several binary and ternary liquid mixtures.

NMR study of ammonium halides under high pressure

Wide-line c.w. proton resonance investigations have been carried out on the ammonium halides, namely, ammonium chloride, ammonium bromide and ammonium iodide in the temperature range between 77 and 300 K and in the pressure range between 1 bar and 14 kbar. It has been found that the narrow iodide spectrum at 77 K broadens under the application of hydrostatic pressure. The barrier height for the ammonium ion motion in ammonium iodide under pressure has been estimated by carrying out a temperature variation study. The rotational potential for the motion of ammonium ion in ammonium iodide at 1 bar and 14 kbar has been calculated using earlier theoretical models and compared with values calculated for ammonium chloride and bromide. The barrier height in the case of ammonium iodide under pressure is found to be of the same order of magnitude as the value obtained in the case of ammonium bromide at atmospheric pressure indicating that the high pressure phase of ammonium iodide is likely to have the same structure as the low temperature ordered CsCl phase found in the case of the chloride and the bromide. The increase in the potential barrier height in the case of ammonium iodide under pressure indicates that the reorientational motion executed by the ammonium ions is inhibited by the application of pressure. This is also confirmed by the broadening of the spectral line at 77 K under the application of pressure.

Oxidation Of 1-(2-Hydroxybenzyl)-2-Naphthols

Condensation of salicyl alcohol with 2-naphthols (9a-d) furnishes 1-(2-hydroxybenzyl)-2-napthols (6a-d). Methylation of 6a gives the dimethyl ether 11, which has also been prepared by Grignard reaction of 2-methoxyphenylmagnesium bromide with 2-methoxy-1-naphthaldehyde followed by reduction with AlCl3-LiAlH4. Compounds 6a-d undergo facile oxidation with either K3Fe(CN)6 or KOBr to give spironaphthalenones 12a-d. Surprisingly, no reaction occurs with either DDQ or o-chloranil.

Radical cyclization strategies to terpenoids; syntheses of (±)-β-cuparenone, (±)-laurene and epilaurenes

Radical cyclization of the bromide Image , obtained in 5 steps from the ketone Image , furnished exclusively Image Image 6-endo trig cyclization with out any observable amount of 5-exo trig product Image . 5-Exo dig radical cyclizatlon of the bromo acetate Image , prepared from Image Image the aldehyde Image , followed by routine transformations furnished the cyclopentenone Image , an immediate precursor to β-cuparenone (Image ). Similarly, total synthesis of laurenes Image and Image was achieved Image the 5-exo dig radical cyclization of the xanthate Image , obtained from the aldehyde Image .Syntheses to title compounds based on 5-exo-dig radical cyclisation, along with two unsuccessful approaches to cuparene, are described.

Synthesis and Identification of a new class of antileukemic agents containing 2-(arylcarboxamide)-(S)-6-amino-4,5,6,7-tetrahydrobenzod]thiazole

Recently we have reported the effect of (S)-6-aryl urea/thiourea substituted-2-amino-4,5,6,7-tetrahydrobenzod]thiazole derivatives as potent anti-leukemic agents. To elucidate further the Structure Activity Relationship (SAR) studies on the anti-leukemic activity of (S)-2,6-diamino-4,5,6,7 tetrahydrobenzod]thiazole moiety, a series of 2-arlycarboxamide substituted-(S)-6-amino-4,5,6,7-tetrahydrobenzod]thiazole were designed, synthesized and evaluated for their anti-leukemic activity by trypan blue exclusion, 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT), lactate dehydrogenase (LDH) assays and cell cycle analysis. Results suggest that the position, number and bulkiness of the substituent on the phenyl ring of aryl carboxamide moiety at 2nd position of 6-amino-4,5,6,7-tetrhydrobenzod]thiazole play a key role in inhibiting the proliferation of leukemia cells. Compounds with ortho substitution showed poor activity and with meta and para substitution showed good activity. (C) 2010 Elsevier Masson SAS. All rights reserved.

Bubble formation at closely spaced orifices in aqueous solutions

A filter cloth with 182 holes per 10−4 m2 has been used to generate air bubbles both in pure water and in aqueous solutions of electrolytes and non-electrolytes at various air flow rates. Potassium bromide and ammonium perchlorate were the electrolytes used, while the non-electrolytes were isopropanol, urea and glycerol. Bubble diameters and their size distribution were measured from photographs. The role of solutes in affecting bubble sizes and their distribution compared to that of pure water is discussed in the light of a hypothesis. This hypothesis assumes that if the final bubble diameter is less than the inter-orifice distance, then bubbles do not coalesce; on the other hand, if it is greater, then coalescence occurs when tf greater-or-equal, slantedti+ts, but does not occur when t