Matrix-dependent instability of selenium(IV) stored in teflon containers

Solutions of selenium(IV) standards with different acid matrices were stored in containers constructed of boosilicate glass, conventional polyethylene, and fluorinated ethylenepropylene (teflon FEP). After 50 days of storage in FEP, there were highly significant losses of Se(IV) from standards in either 5% HCl/5% H₂SO₄, or 5% H₂SO₄. Increasing the hydrochloric acid concentration, e.g., 15% HCl/5% H₂SO₄, greatly reduced this loss. Addition of selenium-75 (selenate-free) indicated that the losses did not result from physical adsorption onto container surfaces. It is shown that the losses were caused by oxidation of Se(IV) to Se(VI).     

A new palladium catalyst system for the cyanation of aryl chlorides with K4[Fe(CN)6]

The development of a novel Pd-catalyzed synthesis of (hetero)aromatic nitriles from the corresponding aryl chlorides and potassium hexacyanoferrate(II) is described. This novel protocol avoids the use of highly toxic alkali cyanides and proceeds in the presence of small amounts of palladium catalysts. High yields and selectivities of the corresponding aryl nitriles were achieved applying di(1-adamantyl)-1-butylphosphine (cataCXium^® A) as the ligand.     

A simple cobalt catalyst system for the efficient and regioselective cyclotrimerisation of alkynes

The intermolecular cyclotrimerisation of terminal and internal alkynes can be catalysed by simple cobalt complexes such as a CoBr2(diimine) under mild reaction conditions when treated with zinc and zinc iodide with high regioselectivity in excellent yields.     

The Synthesis and Reactions of Yomogi Alcohol. Conversion of the artemisyl skeleton to the santolinyl skeleton by a 1,2-shift of a vinyl group. Synthesis of santolinatriene

The synthesis of yomogi alcohol (2, 5, 5-trimethylhepta-3,6-dien-2-ol, 2 ) is described, and experiments directed towards its allylic rearrangement to artemisia alcohol detervatives have been carried out. Acidic reagents open the ring of yomogi alcohol epoxide ( 16 ) at with participation of the 6,7-double-bond, a shift of the vinyl group results to yield a compound with the santolinyl skeleton. The same reagents are without effect when this double bond reduced. Action of butyllithium of the benzaldehyde acetal ( 41 ) of 2, 5-dimethyl-4-vinyl-2, dihydroxy-hex-5-ene ( 28 ), obtained by acid-catalyzed ring opening of yomogi alcohol epoxide in the presence of benzaldehyde, leads to santolinatriene ( 42 ). This vinyl shift is not observed in the case of O-acetyl yomogi alcohol epoxide ( 46 ), from white a compound believed to be an oxetan 48 (R ? COCH₃) is formed with concomitent shift of the acetate group. Further unusual reactions of the oxetan are described, and some observation about the epoxidation of sterically hindered allyl alcohols and their acetates are made.     

Synthesis of unsymmetrical 2,4-dialkylpyrazolo[1,5-a]-1,3,5-triazines

The reaction of 3-aminopyrazole with imidate esters such as ethyl acetimidate, gave N-(pyrazol-3-yl)acetamidine (1) rather than the isomeric 2-acetamidoyl-3-aminopyrazole. Ring closure of 1 with orthoesters such as ethyl propionimidate, afforded unsymmetrically substituted 2.4-dialkylpyrazolo[1,5-a]-1,3,5-triazines such as 4-ethyl-2-methylpyrazolo[1,5-a]-1,3,5-triazine (3). The structure of 1 was confirmed by several alternate syntheses. The unique feature of this two-step synthetic approach to the synthesis of pyrazolo[1,5-a]-1,3,5-triazines is that it is a convenient method of preparing fused triazines based on available pyrazoles rather than the less accessible dialkyltriazines.     

Stochastic coupling and thermodynamic inequalities

Let ₁ and ₂ be thermodynamic Gibbs measures on ^m and ⁿ , respectively. Diffusions are constructed having ₁, and ₂ as invariant measures. These diffusions are then coupled; inequalities between expectations of certain random variables on the two spaces result.Partially supported by NSF-MCS 74-07313-A03     

Measurement of theg-factor of the 4 1 + -state of202Pb

Theg-factor of the 4 ₁ ⁺ -state of²⁰²Pb was investigated by the IPAC-technique. Inspite of the long half-life, which was measured as:T _1/2(4 ₁ ⁺ -state)=1.97(2)ns and the strong applied external magnetic field of 95.0 kG no rotation of the 787 keV-(422keV)-961 keVγ-γ angular correlation could be observed. Theg-factor must therefore be very small. A computer fit gave the limits:g(4 ₁ ⁺ -state)=+0.002(4). This smallg-factor can be understood by the assumption of an accidental cancellation of a positive contribution by the main [f _5/2 ² ]₄-configuration and several negative contributions by admixtures of all other possible two neutron configurations.     

The volumetric analysis of phosphates

A method has been developed for the volumetric determination of orthophosphate, and a simple variation permits the determination of the average number of phosphorus atoms per molecule in condensed phosphates. For total P₂O₅ the phosphates are converted to the diacid orthosalt and precipitated as silver phosphate. The liberated acid is then titrated. For determination of chain length the condensed phosphate is converted to the diacid form and treated similarly, then hydrolysed and determined as orthophosphate. The ratio of the two titrations is equal to the average number of phosphorus atoms per molecule.     

Thermogravimetric and dynamic mechanical thermal analysis of pineapple fibre reinforced polyethylene composites

The thermal behaviour of pineapple leaf fibre (PALF) reinforced polyethylene composites was studied by thermogravimetric and dynamic mechanical thermal analysis. Fibre treatment was carried out using isocyanate, silane and peroxide to improve the interfacial adhesion between fibre and matrix. The effects of fibre loading and surface modification on the thermal properties were evaluated. It was found that at high temperature PALF degrades before the polyethylene matrix. The storage modulus increased with increase of fibre loading and decreased with increase of temperature. The treated fibre composites impart better properties compared to untreated system. Tan δ showed a distinct peak at low temperature ascribed to the glass transition temperature of polyethylene but no peak was observed for PALF fibre. The relative damping increased with fibre loading. Cole-Cole analysis was made to understand the phase behaviour of the composite samples.     

A Short Synthesis of (−)-Carbovir

(–)-Carbovir ((–)- 1 ) was synthesized via the cyclic carbonate 2 in four steps starting from enantiomerically enriched (–)-(S)-(cyclopent-2-enyl)methanol ((–)- 3 ).