Electronic structure of unstable intermediates

The geometry of the linear molecule HBO, has been investigated within the restricted Hartree-Fock LCAO-MO-SCF approximation. The calculated bond lengths for the near Hartree-Fock calculation were R(H-B)=2.1913 bohr, R(B-O)=2.2284 bohr. Several one electron properties have been calculated for the minimum energy configuration.     

Racemization of chiral amino alcohols III: Effect of Mg or Ca addition on the activity and stability of the Co/γ-Al2O3 catalyst

The racemization of R-(-)-2-amino-1-butanol in a reaction using Co/γ-Al₂O₃ catalysts and catalysts modified by Mg or Ca was investigated in this paper. Complete racemization was achieved with a yield of over 83% at using the Mg modified Co/γ-Al₂O₃ catalyst under optimized reaction conditions of 170°C and 2.5 MPa of H₂. The catalysts were thoroughly characterized by XRD, XPS, TPR, SEM and TEM. The addition of Mg and Ca may be advantageous for dispersing and stabilizing the active species of the Co/γ-Al₂O₃ catalyst, protecting from sintering, significantly improving its catalytic activity and stability.     

A comparison of electron ionization mass spectra obtained at 70 eV,low electron energies,and with cold EI and their NIST library identification probabilities

Electron ionization (EI) mass spectra of 46 compounds from several different compound classes were measured. Their molecular ion abundances were compared as obtained with 70‐eV EI, with low eV EI (such as 14 eV), and with EI mass spectra of vibrationally cold molecules in supersonic molecular beams (Cold EI). We further compared these mass spectra in their National Institute of Standards and Technology (NIST) library identification probabilities. We found that

1. Low eV EI is not a soft ionization method, and it has little or no influence on the molecular ion relative abundances for large molecules and those with weak or no molecular ions.
2. Low eV EI for compounds with abundant or dominant molecular ions in their 70 eV mass spectra results in the reduction of low mass fragment ions abundances thereby reducing their NIST library identification probabilities thus rarely justifies its use in real‐world applications.
3. Cold EI significantly enhances the relative abundance of the molecular ions particularly for large compounds; yet, it retains the low mass fragment ions; hence, Cold EI mass spectra can be effectively identified by the NIST library.
4. Different standard EI ion sources provide different 70 eV EI mass spectra. Among the Agilent technologies ion sources, the “Extractor” exhibits relatively abundant molecular ions compared with the “Inert” ion source, while the “High efficiency source” (HES) provides mass spectra with depleted molecular ions compared with the “Inert” ion source or NIST library mass spectra.

These conclusions are demonstrated and supported by experimental data in nine figures and two tables.     

Capillary electrophoresis determinative and GC-MS confirmatory method for water-soluble organic acids in airborne particulate matter and vehicle emission

Urban fine airborne particulate matter (PM2.5) and vehicle emission samples were studied for water-soluble low-molecular-weight carboxylic acids using CE with indirect UV detection. Further identification of these acids was achieved using GC-MS as their butyl esters (after derivatization with BF3/butanol). Several dicarboxylic acids in the range C2-C10 including straight-chain, branched-chain, cis- and trans-unsaturated, and aromatic acids were confirmed by GC-MS. In addition, aromatic acids such as benzoate, phthalate, terephthalate, isophthalate, and 4-methylphtalate were present in such samples, but some of these were not well resolved by the used CE method. Oxocarboxylic acids (Cn(w) with n > 4) were also identified by GC-MS but not determined by CE due to lack of standards. The rapidity and simplicity of the CE method were clearly demonstrated, and the method was observed to be advantageous for routine monitoring of water-soluble organic acids in airborne PM2.5 and vehicle emission at low microg/L levels.     

New designer drug 1-(3-trifluoromethylphenyl) piperazine (TFMPP): gas chromatography/mass spectrometry and liquid chromatography/mass spectrometry studies on its phase I and II metabolism and on its toxicological detection in rat urine

Studies are described on the phase I and II metabolism and the toxicological analysis of the piperazine-derived designer drug 1-(3-trifluoromethylphenyl)piperazine (TFMPP) in rat urine using gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/mass spectrometry (LC/MS). The identified metabolites indicated that TFMPP was extensively metabolized, mainly by hydroxylation of the aromatic ring and by degradation of the piperazine moiety to N-(3-trifluoromethylphenyl)ethylenediamine, N-(hydroxy-3-trifluoromethylphenyl)ethylenediamine, 3-trifluoromethylaniline, and hydroxy-3-trifluoromethylaniline. Phase II reactions included glucuronidation, sulfatation and acetylation of phase I metabolites. The authors' systematic toxicological analysis (STA) procedure using full-scan GC/MS after acid hydrolysis, liquid-liquid extraction and microwave-assisted acetylation allowed the detection of TFMPP and its above-mentioned metabolites in rat urine after single administration of a dose calculated from the doses commonly taken by drug users. Assuming similar metabolism, the described STA procedure should be suitable for proof of an intake of TFMPP in human urine.     

Synthesis of some sulfur-containing pyrido[1,2-α]pyrimidines

4-Methylthiopyrido[1,2-α]pyrimidin-2-one and 2-hydroxypyrido[1,2-α]pyrimidine-4-thione derivatives were synthesized by the addition ofN-(4-R-pyrid-2-yl)acetoacetamides (R = H, Me) to CS₂ under phase-transfer conditions followed by the alkylation of the reaction products with Mel. The molecular structure of 3-acetyl-4-methylthiopyrido[1,2-α]pyrimidin-2-one is established by X-ray analysis.     

Influence of quaternary onium salts,crown ethers and cryptands on olefin epoxidations promoted by HOCl/ClO− in the Presence of Mn(III)-tetrakis(2,6-dichlorophenyl)porphyrin chloride

Reaction rates of alkene epoxidations, promoted by aqueous NaOCl and catalyzed by Mn(III)-tetrakis(2,6-dichlorophenyl)porphyrin chloride1 (P) in the presence of a lipophilic axial ligand (L) (e.g.N-hexylimidazole) and carried out under H₂O/CH₂Cl₂ two phase conditions at 0°C, are strongly enhanced by lowering the pH of the aqueous phase from 12.7 to 9.5. Under these conditions, a further relevant increase in the reaction rates can be achieved by adding phase-transfer catalysts (PT), e.g. quaternary ammonium salt 3, lipophilic crown ether4 or cryptand5, provided that the amount of L is very small (L/P=1 for very reactive alkenes, e.g. cyclooctene, and 10 for poorly reactive ones, e.g. 1-dodecene). In the case of cyclooctene epoxidation, the use of 0.006–0.03 mol. equiv. of PT completes the reaction in 1–10 min., the initial rates being up to 600 turnovers/min. with (2.2.2,C₁₀) cryptand. In the absence of the axial ligand, the quaternary ammonium salt3 and cryptand5 show an inhibitory effect. Such an effect is due to the formation of the poorly reactive Mn(P)CI species, by Cl– extraction to the organic phase. However, dibenzo crown ether 4 does not show this effect. In the presence of 4, and with L/P =1, the 1-dodecene epoxidation reaches 94% in 1 min. The unique behavior of crown ethers can be explained by their ineffectiveness in extracting alkali chlorides, providing a very low concentration of Cl– in the organic phase and thus avoiding the Mn(III)-porphyrin deactivation.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

Complexing tendencies of UO 22+ and Th4+ in their mixed ligand complexes with aminopolycarboxylates and resorcinol or its derivatives

Formation contants (log K _MAL ^MA ) of mixed ligand complexes MAL, where M = UO ₂ ²⁺ or Th⁴⁺, A = IMDA, NTA, HEDTA, EDTA, CDTA or DTPA, and L = resorcinol (res), 2-methyl resorcinol (2-Me-res), 5-methyl resorcinol (5-Me-res) or 4-chloro resorcinol (4-Cl-res), have been determined pH-metrically by the Irving-Rossotti approach at 25°C and at an ionic strength,I = 0.2(moldm⁻³KNO₃). The observed stability sequences are IMDA > NTA > HEDTA > EDTA > CDTA > DTPA, and 4-Cl-res > 5-Me-res > 2-Me-res > res with respect to primary and secondary ligands, respectively. Th⁴⁺ forms more stable mixed complexes than UO ₂ ²⁺ . The A ΔlogK values are negative due mainly to the charge repulsion involved in the complexation MA + L⇋MAL.     

Kinetics ofEDTA substitution of N,N′-ethylenedisalicylamidato cuprate(II) in alkaline media

Summary The kinetics ofEDTA reaction with N,N-ethylenedisalicylamidato cuprate(II) is followed at 30°C in borate buffer and is found to be first order in each reactant. The reaction ispH dependent and involves protonation of a deprotonated peptide nitrogen followed by nucleophilic attack byEDTA.

---

Kinetik derEDTA-Substitution von N,N-Ethylendisalizylamidatokupfer(II) in alkalischem Medium (Kurze Mitt.)

Zusammenfassung Die Kinetik derEDTA-Reaktion mit N,N-Ethylendisalizylamidatokupfer(II) wurde bei 30°C in Borat-Puffer verfolgt. Es wurde erste Ordnung bezüglich jedes Reaktanden festgestellt. DiepH-abhängige Reaktion beinhaltet die Protonierung eines deprotonierten Peptid-Stickstoffs, gefogt von einem nucleophilen Angriff einesEDTA-Moleküls.

     

Spectroscopic and thermodynamic studies on solvatochromic nickel(II) complexes

Summary The solvatochromic and thermochromic behaviour of a series of mixed Ni(II) complexes with unsubstituted and substituted -diketones and diamines in the solvents 1,2-dichloroethane (DCE), acetonitrile (An), acetone (AC),n-butanol (n-BuOH), formamide (FA), N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO) and pyridine (PY) has been studied and characterized on the basis of electronic spectra. Spectrophotometric methods have been used to evaluate equilibrium constants and their enthalpic and entropic terms for the formation of Ni(-dik)(diam)L ⁺ and Ni(-dik)(diam)L ₂ ⁺ . Increasing donor strength of the donor-solvents (L) and (or) increasing electronwithdrawing parameters of the substituents at the -diketone and the diamine ligands lead to increasing formation constants, paralleled by relative increase in the stability of the five-coordinated species Ni(-dik)(diam)L ⁺. The results are discussed in terms of the extended donor-acceptor concept.On leave of absence from the Faculty of Education, Ain Schams University, Roxy, Cairo, Egypt