Regioselective synthesis of 4- and 5-oxazole-phosphine oxides and -phosphonates from 2H-azirines and acyl chlorides

A simple and efficient regioselective synthesis of 4-oxazole-phosphine oxides 11 and -phosphonates 12 from 2H-azirine-phosphine oxides 1 and -phosphonates 6 is described. The key step for the synthesis of oxazoles 11 is a base-mediated ring closure of vinylogous α-aminophosphorus compounds derived from phosphine oxides 4 and from phosphonates 8. These derivatives 4 and 8 are obtained by reaction of functionalized azirines 1 and 6 with acyl chlorides 2 and subsequent acid-catalyzed ring opening of N-acylaziridine-phosphine oxides 3 and -phosphonates 7. Regioselective thermal ring cleavage of N-acylaziridine-phosphine oxides 3 leads α-chloro-β-(N-acylamido)-phosphine oxides 13 and their treatment with bases gives 5-oxazole-phosphine oxides 16.     

Crystal structure and single crystal EPR of (NH_4)_2(15-crown-5)_3[Cu(mnt)_2] and (NH_4)_2(benzo-15-crown-5)_4[Cu(mnt)_2]·0.5H_2O

The X-ray crystal structures of (NH4)2(15-crown-5)3[Cu(mnt)2] (1) and (NH4)2(benzo-15-crown-5)4- [Cu(mnt)2]·0.5H2O (2) were determined. Two single crystals are composed of distinct structures of ammonium-crown ether supramolecular cation and [Cu(mnt)2]2? anion. The triple-decker dication in complex 1 and a sandwich dimmer in complex 2 were observed. X-Band EPR studies on the single crystals of both complex 1 and complex 2 have been carried out at room temperature, which revealed that complex 2 showed a perfect hyperfine structure of Cu whereas that of complex 1 could not be observed. The principal values and direction cosines of the principal axes of the g and A tensors were computed by a least-squares fitting procedure. The spin density of Cu(II) was estimated according to the principal values of the A tensors and compared well with the results calculated based on DFT method.     

Correlation of antioxidant depletion and mechanical performance during thermal degradation of an HTPB elastomer

Thermal degradation studies of a stabilized HTPB based elastomer were conducted at temperatures from 50 °C to 110 °C. The concentration of extractable antioxidant (AO2246) in the polymer was quantified via AO extraction and a gas chromatography-based method using internal standards. The decrease in extractable AO levels as a function of time and temperature was evaluated and correlated with mechanical property changes. Most importantly, AO depletion features were found to be temperature dependent. At elevated temperatures (>80 °C) extractable AO levels decreased rapidly and faster than the concurrent loss in mechanical properties. While extractable AO concentrations decrease quickly, the material is able to maintain some useful mechanical properties, perhaps via non-extractable or grafted AO species formed during degradation providing additional protection. At lower aging temperatures extractable or free AO levels decreased more slowly than the mechanical properties. Therefore, for condition monitoring purposes a universal correlation between AO levels and aging state or material condition could not be established. Most importantly, however, loss of mechanical properties and oxidative degradation is observed at lower temperatures despite significant levels of free antioxidant in the material. The antioxidant appears to be limited in its effectiveness to completely prevent degradation reactions, or only fractions of the total AO available are actually involved in the inhibition process.     

Spectroscopic and quantum chemical studies on the structure of 2-arylquinoline-4(1H)-thione derivatives

The geometries of the title compounds were probed in solution, solid and gas states using spectroscopic methods, X-ray crystallography and quantum chemical techniques. The exclusive existence of the NH-4-thiones in solution (NMR and PCM-B3LYP(MP2)/6-31+G(d) calculations) and solid state (FT-IR and X-ray) is also corroborated by comparison of their spectroscopic data with those of the corresponding 2-aryl-1-methylquinoline-4(1H)-thione derivatives. The co-existence of the quinoline-4-thione and quinoline-4-thiol (4-mercaptoquinoline) isomers in the gas phase is confirmed by mass spectrometry and the preponderance of the 4-thiol is supported by quantum chemical techniques (PM3, MP2 and B3LYP).     

Quantitative determination of sotolon, maltol and free furaneol in wine by solid-phase extraction and gas chromatography-ion-trap mass spectrometry

A method for the analytical determination of sotolon [4,5-dimethyl-3-hydroxy-2(5H)-furanone], maltol [3-hydroxy-2-methyl-4H-pyran-4-one] and free furaneol [2,5-dimethyl-4-hydroxy-3(2H)-furanone] in wine has been developed. The analytes are extracted from 50 ml of wine in a solid-phase extraction cartridge filled with 800 mg of LiChrolut EN resins. Interferences are removed with 15 ml of a pentane-dichloromethane (20:1) solution, and analytes are recovered with 6 ml of dichloromethane. The extract is concentrated up to 0.1 ml and analyzed by GC-ion trap MS. Maltol and sotolon were determined by selected ion storage of ions in the m/z ranges 120-153 and 79-95, using the ions m/z 126 and 83 for quantitation, respectively. Furaneol was determined by non-resonant fragmentation of the m/z 128 mother ion and subsequent analysis of the m/z 81 ion. The detection limits of the method are in all cases between 0.5 and 1 microg l(-1), well below the olfactory thresholds of the compounds. The precision of the method is in the 4-5% range for levels in wine around 20 microg l(-1). Linearity holds at least up to 400 microg l(-1), and is satisfactory in all cases. The recoveries of maltol and sotolon are constant (70 and 64%, respectively) and do not depend on the type of wine. On the contrary, in the case of furaneol, red wines show constant and high recoveries (97%), while the recoveries on white wines range between 30 and 80%. Different experiments showed that this behavior is probably due to the existence of complexes formed between furaneol and sulphur dioxide or catechols. Sensory experiments confirmed that the complexed forms found in white wines are not perceived by orthonasal olfaction, and that the furaneol determined by the method can be considered as the free and odor-active fraction.     

Synthesis of 8-vinyladenosine 5′-di- and 5′-triphosphate: evaluation of the diphosphate compound on ribonucleotide reductase

The synthesis of 5′-di- and 5′-triphosphate of 8-vinyladenosine to be tested on ribonucleotide reductases requires the modification of known methods. The phosphate group was introduced by treatment with an in situ generated chlorophosphite. Protection of the 2′,3′ diol with acetyl groups suppressed depurination during acid removal of the phosphotriester protecting groups. The di- and triphosphate compounds were obtained by treatment of the activated adenylic acid with phosphate or pyrophosphate anions followed by removal of the acetate protecting groups. Preliminary studies were conducted on Escherichia coli ribonucleotide reductase and have shown that the diphosphate compound is efficiently reduced.     

Average electron momenta in many-electron atoms

In many-electron atoms, the average electron momentum p represents the mean momentum of a single electron when all the electron motions are averaged. If any two electrons are considered simultaneously, however, the average momentum p splits into two different momenta, low momentum p_< and high momentum p_>. For the 102 atoms He through Lr in their ground states, the momenta p_< and p_> are systematically examined at the Hartree–Fock limit level. It is also shown that the sum p_>+p_< and the difference p_>–p_< of the two momenta constitute upper and lower bounds to the electron-pair relative momentum p₁₂=|p₁–p₂| and to the electron-pair center-of-mass momentum P=|p₁+p₂|/2. The tightness of the bounds is discussed for the 102 atoms.     

Simultaneous Determination of Triptolide and Tripdiolide in Extract of Tripterygium wilfordii Hook. f. by LC–APCI-MS

A novel method using liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry in the negative selected ion monitoring mode has been developed and validated for rapid simultaneous determination of triptolide and tripdiolide in the extract of Tripterygium wilfordii Hook. f. The molecular ions m/z [M–H]⁻ 359 and 375 were selected for the quantification in selected ion monitoring mode for triptolide and tripdiolide. Standard calibration curve was linear over the concentration range of 0.12–24 and 0.15–30 μg mL⁻¹ for triptolide and tripdiolide. The relative standard deviations of intra- and inter-day were in the range of 4.7–9.9 and 8.9–12.6%. The average recoveries were between 96.4 and 104.6%. The limits of quantitation were 2.0 × 10⁻³ and 2.5 × 10⁻³ μg mL⁻¹ for triptolide and tripdiolide.     

Determination of long-lived radionuclides in concrete matrix by laser ablation inductively coupled plasma mass spectrometry

A laser ablation system using a Nd:YAG laser was coupled both to a quadrupole inductively coupled plasma (ICP) mass spectrometer and to a double-focusing sector field ICP mass spectrometer. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied for the determination of long-lived radionuclides in a concrete matrix. The investigated samples were two laboratory standards with a concrete matrix, which we doped with different long-lived radionuclides (e.g. ⁹⁹Tc, ²³²Th, ²³³U, ²³⁷Np) from the ng g⁻¹ to μ g⁻¹ concentration range and an undoped concrete material (blank). Detection limits for long-lived radionuclides in the 10 ng g⁻¹ range are reached for LA-ICP-MS using the quadrupole mass spectrometer. With double-focusing sector field ICP-MS, the limits of detection are in general one order of magnitude lower and reach the sub ng g⁻¹ range for ²³³U and ²³⁷Np. A comparison of mass spectrometric results with those of neutron activation analysis on undoped concrete sample indicates that a semiquantitative determination of the concentrations of the minor and trace elements in the concrete matrix is possible with LA-ICP-MS without using a standard reference material.     

Reaction of Pyrimidinonethione Derivatives: Synthesis of N‐Methyl‐2‐Hydrizinopyrimidine‐4‐One,Thiazolo[3,4‐b] N‐Methylpyrimidinone; 2‐(1‐Pyrazolonyl) N‐Methylpyrimidine‐4‐one and 2‐Hydrazino‐N‐Methyl Pyrimidine‐4‐One Derivatives

6‐Aryl‐5‐cyano‐4‐pyrimidinone‐2‐thion derivatives 1a‐c reacted with methyl iodide (1:2) to give the corresponding 2‐S,N‐dimethyl pyrimidine‐4‐one derivatives 2a‐c . Compounds 2a‐c were in turn, reacted with hydrazine hydrate to give the sulfur free reaction products 3a‐c . These reaction products were taken as the starting materials for the synthesis of several new heterocyclic derivatives. Reaction of 3a‐c with acetic anhydride and formic acid gave pyrimido triazines 4a‐c and 7a‐c , respectively. Their reactions with active methylene containing reagents gave the corresponding 2‐(1‐pyrazonyl)‐N‐methyl pyrimidine derivatives 9a‐c and 10a‐c , respectively. Their reactions with aromatic aldehydes afforded the corresponding 2‐hydrazono pyrimidine derivatives 11a‐c . The structure of these reactions products were established based on both elemental analysis and spectral data studies.