Catalytic,asymmetric Mannich-type reactions of alpha-imino esters bearing readily removable substituents on nitrogen

[reaction: see text] Catalytic, enantioselective Mannich-type reactions of alpha-imino esters bearing readily removable substituents on nitrogen are described. Several N-carbamate-protected alpha-imino esters, which are readily prepared from 2-bromoglycine esters using a polymer-supported amine, reacted with silicon enolates to afford the desired adducts in high yields with high enantioselectivity using a copper(II)-diamine complex. Easy deprotection of the product amine and transformation to free alpha-amino acid derivatives have also been demonstrated.     

Enantioselective Strecker-type reaction to sulfonylimines having a 2-pyridylsulfonyl group as a novel stereocontroller

A catalytic enantioselective Strecker-type reaction to N-(2-pyridylsulfonyl)imines in the presence of chiral bis(oxazoline)s afforded the products with a high enantioselectivity. A dynamically induced new chiral center on the sulfur by discriminative coordination of a chiral Lewis acid to one of the sulfonyl oxygens efficiently controlled the enantioselectivity.     

Solid sampling Fourier transform infrared determination of Mancozeb in pesticide formulations

A series of approaches have been assayed for FTIR determination of Mancozeb in several solid commercial fungicides using different calibration strategies. The simplest procedure was based on the use of the ratio between the absorbance of a characteristic band of Mancozeb and that of a KSCN internal standard measured in the FTIR spectra obtained from KBr pellets. It was employed the quotient between peak height absorbance values at 1525 cm⁻¹ for Mancozeb and 2070 cm⁻¹ for KSCN. In these conditions a precision as relative standard deviation (RSD) of 0.6% and a relative accuracy error of 0.8% (w/w) were found. For complex formulations, containing other compounds with characteristic absorption bands at different wavenumbers than Mancozeb, one of them was used as internal reference being employed the standard addition approach. In this case, the Mancozeb bands at 1525 cm⁻¹ or at 1289 cm⁻¹ were employed, being used the ferrocyanide band at 2075 cm⁻¹ as internal reference. RSD values between 0.7-1.4% and a relative accuracy error of 3% (w/w) were found. A third strategy was based on the use of partial least squares (PLS) calibration. A reference set was prepared mixing Mancozeb, Kaolin, Cymoxanil and KBr, being predicted the Mancozeb concentration in pesticide formulations by using the quotient between absorbance bands of Mancozeb and those of Cymoxanil. In these conditions a relative accuracy error of 0.6% (w/w) and a relative standard deviation of 1.3% were found.     

Spectroscopic and Electrochemical Characterization of Cytochrome P450st‐DDAB Films on a Plastic‐Formed Carbon Electrode

We have studied the characterization of thermophilic cytochrome P450 (P450st)‐didodecyldimethylammonium bromide (DDAB) films by using UV‐vis absorption, resonance Raman spectroscopy, and electrochemical methods. The observed Raman spectrum indicated near‐native conformation of the heme iron in DDAB film on the surface of a glass slide, while on the surface of a plastic‐formed carbon (PFC) electrode, the conformation of P450st‐DDAB was very similar to that of heme‐DDAB film, suggesting the release of heme from P450st in DDAB films on PFC electrodes. When NaBr was added as salt to the casting solution, the result of Raman spectrum indicated near‐native conformation of P450st in DDAB film even on the PFC electrode, but no redox potential of P450st which has near native structure was observed. This study suggests the essential experimental conditions when working with heme protein‐DDAB films as, in some cases, heme iron from proteins is released on the surface of the electrode.     

Rapid ruthenium-catalyzed synthesis of pyranopyrandiones by reconstructive carbonylation of cyclopropenones involving C[bond]C bond cleavage

Pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru3(CO)12 and NEt3 in THF under 15 atm of carbon monoxide at 140 degrees C for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions.     

High yield synthesis and reactivity of a phosphinidene bridged dimolybdenum complex

Protonation of [Mo2Cp2(mu-H)(mu-PHR*)(CO)4] (Cp = eta5-C5H5, R* = 2,4,6-C6H2tBu3) with HBF4.OEt2 gives the hydridophosphinidene complex [Mo2Cp2(mu-H)(mu-PR*)(CO)4]BF4, which is easily deprotonated with H2O to give the known phosphinidene complex [Mo2Cp2(mu-PR*)(CO)4] in 95% yield. Reaction of the latter with I2 gives the unsaturated phosphinidene complex [Mo2Cp2I2(mu-PR*)(CO)2], which exhibits an intermetallic distance of 2.960(2) A. Irradiation of solutions of [Mo2Cp2(mu-PR*)(CO)4] with UV light gives a mixture of the triply bonded [Mo2Cp2(mu-PR*)(mu-CO)2] and the hydridophosphido derivative [Mo2Cp2(mu-H){mu-P(CH2CMe2)C6H2tBu2}(CO)4] as major species. The latter complex results from an intramolecular C-H bond cleavage from a tBu group and has been characterized by spectroscopy and an X-ray study. Irradiation in the presence of HCC(p-tol) results in the insertion of the alkyne into the Mo-P bond to give [Mo2Cp2{mu-eta1:eta2,kappa-C(p-tol)CHPR*}(CO)4] structurally characterized through an X-ray study.     

Adsorption characteristics of bisphenol A onto carbonaceous materials produced from wood chips as organic waste

A single-chain amphiphile containing a rigid Schiff base segment, 3-cyano-N-benzylidene hexadecylamine (CNBHB) in the polar head group was synthesized and studied for its vesicle-forming properties. The dependence of the aggregation behavior of the vesicles as such and in the presence of manganese ions were studied as a function of temperature using differential scanning calorimetry and turbidity measurements. Transmission electron microscopy (TEM) was used to analyze the morphology of the vesicles, showed interesting features with fusion of regular structures, and were quite stable. In the presence of manganese ions, fusion of vesicles takes place. This could be due to the metal ions that are bound to the surface of the vesicles that cause a partial destruction of the hydration shell on the surface of the vesicles. The reduction in the hydration force could thus be responsible for the fusion.     

Fluorometric determination of tin(IV) with 3-hydroxychromone

Summary 3-Hydroxychromone reacts with tin(IV) to produce 11 complex in a weakly acidic-neutral medium. The complex exhibits intense fluorescence. A sensitive method is described for the fluorometric determination of tin(IV) with 3-hydroxychromone. The calibration graph is linear in the range of 0.4–8.0g/25 ml of tin(IV) (pH 4.5–5.0, Excitation wavelength: 365 nm, Measured total fluorescence). Chloride which generally decreases the fluorescence intensity in the fluorometric determination of tin can be tolerated at 300-mg level.

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Fluorometrische Bestimmung von Zinn(IV) mit 3-Hydroxychromon

Zusammenfassung 3-Hydroxychromon reagiert mit Zinn(IV) in schwach saurem bis neutralem Medium unter Bildung eines 11-Komplexes. Dieser fluoresziert intensiv. Ein empfindliches Verfahren zur Bestimmung von Sn(IV) auf dieser Grundlage wurde ausgearbeitet. Die Eichkurve verläuft in dem Gebiet zwischen 0,4 und 8,0g Sn/25 ml bei pH 4,5, einer Wellenlänge von 365 nm und bei Messung der Gesamtfluoreszenz geradlinig. Chloride, die die Fluoreszenzintensität bei Zinnbestimmungen im allgemeinen herabsetzen, können bis zu 300 mg toleriert werden.

     

SOLVENT EFFECTS ON THE TAUTOMERIZATION OF 5′-DEOXYPYRIDOXAL. A PHOTOPHYSICAL STUDY

Abstract— Absorption and fluorescence spectra of 5′-deoxypyridoxal (DPL) in various pure solvents and mixtures were recorded both at room temperature and over the range10–65°C. The areas under the absorption bands were analyzed to obtain the mole fraction (f_N, f_z) of two tautomers (the zwitterionic, Z, and neutral, N, forms) in the ground state. The following spectral parameters were determined from the fluorescence spectra: Stokes shift (Δv), fluorescence quantum yield of the neutral form (Q_N), fluorescence ratio of the neutral to the zwitterionic form (ø_N/ø_Z) and the rate constant of tautomerization (k₁) from Z to N in the excited state. Some of these parameters (f_N, Δv, Q_N, k₁) were found to depend on the proton donor character of the solvent, whereas others (ø_N/ø_Z) depended on its dipole moment. Thus, the absorption and fluorescence spectra of DPL allow one to obtain information on the polarity and the concentration of –OH groups on its environment.     

Mechanism of antioxidative activity of fluvastatin-determination of the active position

In order to clarify the mechanism of action for the antioxidative activity of fluvastatin sodium (FLV, (+/-)-sodium (3RS, 5RS, 6E)-7-[3-(4-fluorophenyl)-1-(1-methylethyl)-1H-indol-2-yl]-3, 5-dihydroxy-6-heptanoate) and its derivatives, reaction of the corresponding methyl ester of FLV with di-tert-butyl diperoxyoxalate was examined, and the corresponding keto derivative was isolated from the reaction mixture. On the basis of this result, it was concluded that the active site is the allylic carbon conjugated with the indole ring.