Synthesis of new fluorinated 1,5-benzoxazepine derivatives

A simple approach to the fluorinated 1,5-benzoxazepine ring system is described. By reacting commercially accessible aminophenols 1 and the trifluoroacetylvinyl ether 2, high yields of enaminones 3 were obtained. Functionalization of methyl group of compounds 3 gave rise to dieneamines 4 that were cyclized in acidic environment to benzoxazepine derivatives 5.     

High-throughput chemistry toward complex carbohydrates and carbohydrate-like compounds

In the area of peptide and nucleic acid chemistry and biology, high-throughput synthesis has played an important role in providing useful small-molecule-based chemical probes in understanding the structure and function relationships. The past several years, there has been a constant rise in interest toward understanding the biological roles and functions of another important class of biomolecules, i.e., carbohydrates and carbohydrate conjugates. Although at early stages, in recent years, several groups have developed high-throughput synthetic methods to obtain complex carbohydrates or carbohydrate-like small-molecules. The present review article summarizes some of these developments.     

The determination of chlorinated biphenyls,chlorinated dibenzodioxins,and chlorinated dibenzofurans by GC-MS

High resolution gas chromatography, with mass selective detection, has been used for the analysis of PCB on methyl 50 % octyl polysiloxane (SB 50 Octyl), methyl octadecyl polysiloxane, and a smectic polysiloxane (SB Smectic); and for the analysis of polychlorodibenzodioxins and polychlorodibenzofurans with 1 to 8 chlorine substituents on 100 % cyanopropyl siloxane (SP 2331), smectic polysiloxane (SB Smectic), a new polar stationary phase (DB-Dioxin). The analysis has also been performed by column coupling.     

Nitrogen extrusion from pyrazoline-substituted porphyrins and chlorins using long wavelength visible light

Protoporphyrin reacts with diazomethane to give pyrazolines which at long wavelength (approximately 630 nm) extrude nitrogen to give the corresponding cyclopropyl derivatives.     

Rb7[SiO4][VO4]: ein Ortho‐Silicat‐Vanadat(V)

Rb₇[SiO₄][VO₄]: an Ortho‐Silicate‐Vanadate(V) Rb₇[SiO₄][VO₄] has been obtained from a redox reaction between CdO and vanadium metal in the presence of Rb₂O and SiO₂ at 600 °C in an Ag container as yellow‐greenish transparent single crystals. The crystal structure determination (IPDS data: P2₁/c, a = 637.6(1) pm, b = 1039.7(1) pm, c = 2076.8(4) pm, β = 93.21(2)°, Z = 4, wR2 = 0.1319) reveals the presence of isolated complex anions, [SiO₄]^4— and [VO₄]^3—.     

Ion pair charge-transfer complexes between anionic and cationic metal-dithiolenes [M(II) = Pd,Pt

New [M(R(2)pipdt)(2)](BF(4))(2) salts [R(2)pipdt = N,N'-dialkyl-piperazine-2,3-dithione; M = Pd(II), R = Me and M = Pt(II), R = Me, Et, Pr(i)] bearing redox-active cationic dithiolene complexes have been prepared and characterized. These cations react with the redox-active [M(mnt)(2)](2-) [M = Pd(II), Pt(II); mnt = maleonitrile-2,3-dithiolate] anionic dithiolenes to form salts describable as ion pair charge-transfer complexes. X-ray crystallographic studies have shown that [M(Me(2)pipdt)(2)][M(mnt)(2)] complexes, with M = Pd(II) and Pt(II), are isomorphous. Crystal data of the Pt salt (3a): triclinic, Ponemacr; (No. 2); Z = 1; T = 293(2) K; a = 6.784(7) A, b = 8.460(6) A, c = 13.510(5) A, alpha = 100.63(2) degrees, beta = 104.04(2) degrees, gamma = 96.90(2) degrees; R1 = 0.0691 [wR2 = 0.2187 (all data)]. Structural data show that approximately square-planar [Pt(Me(2)pipdt)(2)] dications and regular square-planar [Pt(mnt)(2)] dianions form an infinite anion-cation one-dimensional stack along axis a with a Pt...Pt a/2 distance of 3.392 A and a Pt...Pt...Pt angle of 180 degrees. Anions and cations arrange themselves face-to-face so as to take on a staggered arrangement. These salts exhibit strong absorptions in the visible-near-infrared region assigned to ion pair charge-transfer transitions. A relation between the optical and thermal electron transfer in the solid state is obtained using a "Marcus-Hush model", and a solid-state electrical conductivity in agreement with expectations is observed. Vibrational spectroscopy is in agreement with the existence of charge-transfer interactions between the cationic and anionic components of the salts.     

Heats of solution of 1∶1 electrolytes in 1-propanol,and derived enthalpies of transfer from water

Heats of solution of 13 11 electrolytes in 1-propanol have been determined calorimetrically at various electrolyte concentrations, and extrapolated to zero concentration to give H _s ^o values for these electrolytes. Together with literature data on three additional 11 electrolytes, these measurements yield a self-consistent set of single-ion enthalpies of transfer from water to 1-propanol. Values are tabulated for 10 univalent cations and five univalent anions. It is shown that the H _t ^o (Ph ₄ As⁺)=H _t ^o (Ph ₄ B^–) assumption yields chemically reasonable single-ion values. Using this assumption, it may be deduced that all the univalent ions studied have about the same enthalpy in 1-propanol as in methanol.     

Development and validation of a hydrophilic interaction liquid chromatography-tandem mass spectrometric method for the analysis of paroxetine in human plasma

A sensitive, simple, fast and rugged hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS) method for the determination of paroxetine was developed and validated over curve range 0.050-50 ng/mL using only 0.4 mL plasma. This is the first published LC-MS/MS method and the low limit of quantitation of this method is 10-fold lower than previously published methods. A simple liquid-liquid extraction method using methyl-tert butyl ether (MTBE) as the extraction solvent was used to extract paroxetine and the internal standard (IS) fentanyl-d(5) from plasma. The extract was evaporated to dryness, reconstituted and injected onto a silica column using a low aqueous-high organic mobile phase. The chromatographic run time was 2.0 min per injection, with retention times of 1.1 and 1.2 min for paroxetine and IS, respectively. The detection was by monitoring paroxetine at m/z 330 --> 192 and IS at m/z 342 --> 188, respectively. The inter-day precision and accuracy of the quality control (QC) samples were <5.0% relative standard deviation (RSD) and <2.9% relative error (RE). This method can be used for supporting therapeutical drug monitoring and pharmacokinetic or drug-drug interaction studies.     

Ozone-based sulfur chemiluminescence detection: Its applicability to gas,supercritical fluid,and high performance liquid chromatography

The sensitive detection of sulfur-containing analytes is of interest in many industrial applications; selective detection is also desirable since these compounds are usually present at trace levels in difficult matrixes. The purpose of this article is to review the use of the Sievers® ozone-based sulfur chemiluminescence detector, and its coupling with gas chromatography, supercritical fluid chromatography, and high performance liquid chromatography. Detection limits, linearity, response factors, and selectivity are discussed for each of these techniques. Critical operational parameters for the SCD are also described. The use of other sulfur selective detectors for SFC and HPLC is also briefly summarized.     

Coordination of 2,2'-bipyridyl and 1,10-phenanthroline to yttrium and lanthanum complexes based on a scorpionate ligand

Reaction of yttrium and lanthanum trichloride with 1 equiv of sodium or potassium hydrotris(3,5-dimethylpyrazolyl)borate and 1 equiv of 2,2'-bipyridine gives good yields of the complexes [MCl(2)(Tp(Me2))(C(10)H(8)N(2))] (M = Y (1), La (2)). The analogous compounds with 1,10-phenanthroline, [MCl(2)(Tp(Me2))(C(12)H(8)N(2))] (M = Y (3), La (4)), have been obtained by a similar procedure. The solid-state structures of 2-4 were determined by single-crystal X-ray diffraction and revealed that the compounds are all seven-coordinate with capped octahedral geometry. In contrast, reaction of yttrium trichloride with 1 equiv of sodium hydrotris(3,5-dimethylpyrazolyl)borate in the presence of 1 equiv of neocuproine affords [YCl(3)(Tp(Me2))][Na(neoc)(3))] (5). Compounds 1 and 2 provide an entry for the synthesis of complexes containing the bipyridyl ligand in a radical anionic form or in a dianionic form. Reaction of 1 and 2 with an excess of sodium amalgam gives [Y(Tp(Me2))(bipy)(THF)(2)] (6) and [La(Tp(Me2))(2)(bipy)] (7), respectively. The structures of both compounds have been determined by X-ray crystallography. Compound 7 can be oxidized with iodine to give [La(Tp(Me2))(2)(bipy)]I (8).