Ammonia chemical ionization tandem mass spectrometry in structural determination of alkaloids. II. Tetraponerines from pseudomyrmecine ants

Chemical ionization tandem mass spectrometry (CI-MS/MS) of alkaloids with ammonia reagent gas and collision-activated dissociation as well as EI-MS/MS were applied to the tetraponerine alkaloids in extracts from six pseudomyrmecine ants of the genus Tetraponera. The MS/MS techniques along with gas chromatography Fourier transform infrared (GC/FTIR) spectra allowed identification in two extracts of seven of the eight known tetraponerines. The EI-MS/MS fragmentations proved diagnostic for the ring system and the CI-MS/MS patterns for the C-8 or C-9 substitution, while the Bohlmann bands in FTIR spectra were diagnostic for the C-8 or C-9 configurations. An Indian ant (T. allaborans) had T-2, T-4 and T-8, while a Chinese ant (T. binghami) had T-5, T-6, T-7 and T-8. Four other ants, T. rufonigra (India), T. penzigi (Africa), T. clypeata (Africa) and T. sp. cf. emeryi (Africa), had no tetraponerines.     

Enhancement of distillate selectivity in Fischer-Tropsch synthesis by using iron and cobalt catalysts in a novel dual-bed reactor ?

Summary An integrated process for producing liquid fuels from synthesis gas via a two-stage Fischer-Tropsch (FT) reaction is disclosed. An iron catalyst was used in the first bed of a fixed-bed reactor followed by a ruthenium promoted cobalt catalyst in the second bed. The activity and selectivity of the dual-bed system were assessed and compared with those using catalysts in a single bed system, separately. The methane selectivity in the dual-bed reactor was about 11% less compared to that of the single-bed system. The C₅⁺ selectivity for the dual-bed reactor was 19.7% higher than that of the single-bed system.     

Pyrrole studies part 41. Reactivity of 3,4-diformyl-2,5-dimethylpyrrole with diaminoalkanes. An unusual formation of 2-azafulvenes

3,4-Diformyl-2,5-dimethylpyrrole (1) reacts with ,ω-diamino-alkanes, NH₂(CH₂)_nNH₂t' to form either the potentially tautomeric 2:2 macrocyclic adduct (7a) (8), when N = 2, or the potentially tautomeric 1:1 bicyclic adduct (18) (19), when N = 4, 5, 6, and 12. ¹H and ¹³C N.m.r. spectral data indicate that the 2-azafulvene structures predominate for both types of cycloadducts. Only polymeric material was obtained when N = 3.     

Organosilicon compounds : LI. Further studies of the base-catalysed solvolysis of N-(triorganosilyl)anilines

Relative rates of solvolysis of some N-triorganosilylanilines in mixtures of ethanol and aqueous potassium hydroxide have been determined, with results as follows. (i) For XC₆H₄NHSiEt₃ compounds in MeOH (5 vol) + aq. alkali (2 vol) at 50°: (X =) H, 1.0;p-Me, 0.80;p-OMe, 0.83;m-Me, 0.90; o-Me, 0.87; p-SMe, 1.90; p-F, 1.7; p-Cl, 2.8; o-Cl, 14; m-Cl, 4.2; m-NO₂, 18; p-CN, ca. 43; p-NO₂, ca. 120. (ii) For PhNHSi(C₆H₄Y)₃ compounds in MeOH (10 vol) + aq. alkali (1 vol) at 50°: (Y =) H, 1.0; p-OMe, 0.12; p-Cl, ca. 32; m-Cl, ca. 84. (iii) For PhNHSiR₃ compounds in MeOH (5 vol) + aq. alkali (2 vol) : (R₃ =) Et₃, 1.0; Et₂Me, 18 (at 30°); Me₂-i-Pr, 8 (at 30°);Me₂-t-Bu, 0.012 (at 50°);i-Pr₃, 0.006 (at 50°). In series (i) the relative rates correlate with σ, or where appropriate σ^?-constants, with a ? value of 1.6. It is suggested that in the transition state of the rate-determining step the OSi bond is fully formed, or almost so, the SiN bond approximately 20—50% broken, and the bond between the nitrogen atom and a proton from the solvent ca. 10—30% formed.     

Differential Pulse Polarographic Determination of Trace Amounts of Lead in Alloys and Biological Samples after Column Preconcentration Using Nitroso-S and TDBA

A highly selective, sensitive, rapid, and economical differential pulse polarographic method has been developed for the determination of trace amounts of lead in various standard alloys and biological samples after the adsorption of its 2-nitroso-l-naphthol-4-sulfonic acid (nitroso-S)—tetradecyldimethylbenzylammonium (TDBA) chloride on microcrystalline naphthalene in the pH range of 8.0–10.5. After filtration, the solid mass is shaken with 9.0 mL of 1 M hydrochloric acid, and lead is determined by differential pulse polarography (DPP). Lead can alternatively be quantitatively adsorbed on 2-nitroso-l-naphthol-4-sulfonic acid-tetradecyldimethylbenzylammonium-naphthalene adsorbent packed in a column and determined similarly. In this case, 1.0 g of lead can be concentrated in a column from 500 mL of an aqueous sample in which its concentration is as low as 2 ng/mL. Characterization of the electroactive process included an examination of the degree of reversibility. Various parameters, such as the pH effect, volume of aqueous phase, HCl concentration, reagent concentration, naphthalene concentration, shaking time, and the interference of a number of metal ions on the determination of lead were studied in detail to optimize the conditions for determination in standard alloys and standard biological samples.     

Column preconcentration of trace manganese with the ion pair of 2-nitroso-1-naphthol-4-sulfonic acid tetradecyldimethylbenzyl-ammonium chloride supported on naphthalene and determination by derivative spectrophotometry

A column preconcentration method has been developed for the determination of trace amounts of manganese by preconcentration on 2-nitroso-1-naphthol-4-sulfonic acid (nitroso-S)-tetradecyldimethylbenzylammonium (TDBA) naphthalene as an adsorbent using a simple funnel tipped glass tube. Manganese reacts with nitroso-S to form a water soluble brown colored chelate anion. The chelate anion forms a water insoluble Mn-Nitroso-S-TDBA ion pair on naphthalene packed in a column in the pH range 9.6-10.5 at a flow rate of 1-2 ml/min. The solid mass consisting of manganese complex and naphthalene is dissolved in 5 ml of dimethylformamide (DMF) and the metal determined by second derivative spectrophotometry. The calibration curve is linear in the concentration range 0.25-35.0 micrograms of Mn in 5 ml of the final DMF solution. Eight replicate determinations of 25 micrograms of standard manganese solution give a mean peak height of 4.0 with a correlation coefficient of 0.9995 and relative standard deviation of +/- 1.1%. The sensitivity was calculated to be 0.502(d2 A/d lambda 2)/microgram ml-1 from the slope of the calibration curve. The detection limit was 0.020 microgram ml-1 for manganese at the minimum instrumental settings (signal to noise ratio = 2). Various parameters effecting the method such as the effect of pH, volume of aqueous phase and interference of a number of metal ions on the determination of manganese have been evaluated to optimize the conditions for its determination in standard alloys and biological samples.     

The use of Nafion-H® as an efficient catalyst for the direct conversion of primary and secondary trimethylsilyl ethers to their corresponding ethers under mild and heterogeneous conditions

Primary and secondary trimethylsilyl ethers were converted to their corresponding ethers in the presence Nafion-H® with good to excellent yields under mild and heterogeneous conditions.     

Ammonium tetraphenylborate-naphthalene adsorbent for the preconcentration and trace determination of iron in alloys and biological samples using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol by third derivative spectrophotometry

A solid ion-pair material produced from ammonium tetraphenylborate on naphthalene (ATPB-naphthalene) provides a simple, rapid, economical and selective technique for preconcentrating iron from approximately 500 ml of aqueous solution of standard alloys and biological samples. Iron reacts with 2-(5-bromo-2-pryidlazo)-5-diethylaminophenol (5-Br-PADAP) to form a water-soluble cationic complex. When the aqueous solution of this cationic species in the pH range 3.2-8.5 is passed over the adsorbent ATPB-naphthalene at a flow rate of 1 ml min(-1), it is quantitatively retained on naphthalene as an uncharged ion-associated complex. The solid mass from the column was dissolved out with 5 ml of dimethylformamide (DMF) and iron is determined by third derivative spectrophotometry by measuring the signal d(3)A/ dlambda(3) between lambda(2)(773 nm) and lambda(3)(737 nm). The calibration curve is linear over the concentration range 0.10-25.0 mug of iron in 5 ml of DMF solution. Eight replicate determinations of 5 mug of iron gave a mean intensity (peak-to-peak signal between lambda(2) and lambda(3)) of 1.534 with a relative standard deviation of 0.90%. The sensitivity of the method is 0.307 (d(3)A/dnm(3) )/mug found from the slope of the calibration curve. The interference of a large number of anions and cations has been studied and the optimized conditions developed were utilized for the trace determination of iron in various standard alloys and biological samples.     

A study of the formation of silica-supported mixed magnesium-manganese spinel oxides from multicomponent gels

The effects of thermal treatment on composite materials prepared by the gelation of sols comprising large concentrations of metal oxide precursor salts have been investigated, in order to determine the compositional and thermal requirements for forming spinel magnesium manganates in such systems. The preparative technique has been found to give rise to derived gel materials in which the metal oxide phase, in the form of regular spherical particles, is dispersed throughout a continuous silica matrix. Silica-supported mixed magnesium and manganese spinel oxide phases were obtained for systems comprising at least 30 wt% metal nitrate after heating to temperatures between 700 and 850°C, but not without concomitant formation of Mn₂O₃ and modification of the silica network by magnesium.     

Synthesis, characterization, and electrochemical and electrochromic properties of sandwich dilutetium tetraphthalocyanine

A new sandwich-tpype dilutetium tetraphthalocyanine 4 has been synthesized by the reaction of dimeric lutetium(III) phthalocyanine 3 with two equiv. of dilithium octakishexylthiophthalocyanine in amyl alcohol. Compound 3 was prepared from 4',5',4",5"-tetraiminoisoindoline(1,4,7,10-tetrathia-12-crown-4) 1, 4,5-bis(hexylthio)-1,2-diiminoisoindoline and lutetium acetate in amyl alcohol. Compounds 3 and 4 were characterized by elemental analysis, UV/visible, IR, (1)H NMR and ESR spectroscopy. The electrochemical and electrochromic properties of 3 and 4 have been examined by cyclic voltammetry. Both 3 and 4 displayed well-defined electrochromic behavior.