Resistance of supersulfated cement to strong sulfate solutions

One of the principal uses of supersulfated cement has been for structures exposed to sea water and sulfate bearing ground waters. The resistance to such environments has been related to the absence of calcium hydroxide and the combination of much of the free alumina into ettringite during hydration. This paper reports the resistance of SSC to sulfate solutions in which ettringite has been decomposed. Prism samples were subjected to initial water storage at 25°C for both 28 days and 6 months. Samples were also cured for 6 months at 95°C and at both 11% and 100% R.H. The control samples of 28 days were compared with the 6 months samples of a more mature undecomposed SSC paste. After curing the prisms were measured and all the samples were immersed in three sulfate solutions (0.7M Na₂SO₄ , 0.7M MgSO₄ and saturated CaSO₄), and water at the same time. Measurements of linear expansion over 6 months were carried out. Core and surface material following immersion was examined by DTG and XRD. The study indicated that SSC is resistant to sodium and calcium sulfate solutions. Strong magnesium sulfate solutions decomposed the samples under all conditions. A possible mechanism for this attack is suggested. This revised version was published online in July 2006 with corrections to the Cover Date.     

Poly(N‐Bromobenzene‐1,3‐Disulfonylamide), N,N,N′,N′‐Tetrabromobenzene‐1,3‐Disulfonylamide and DABCO‐Bromine Complex: As Novel Reagents for the Oxidative Coupling of Thiols to Disulfides

An efficient method for the oxidative coupling of thiols to their corresponding disulfides by new reagents poly(N‐bromobenzene‐1,3‐disulfonylamide) PBBS , N,N,N′,N′‐tetrabromobenzene‐1,3‐disulfonylamide TBBDA and DABCO‐bromine complex is described. The reaction was applicable to a variety of thiols with high chemoselectivity.     

Tribromoisocyanuric Acid (TBCA) and Oxone®‐MX Systems as Oxidizing Agents: Oxidative Coupling of Thiols to Their Corresponding Disulfides under Mild and Heterogeneous Conditions

Tribromoisocyanuric acid (TBCA) and Oxone^®‐MX systems were used as effective oxidizing agents for the oxidation of thiols to their corresponding disulfides under mild conditions at room temperature with good to excellent yields.     

About diastereoselective oxidations of ferrocenyl amino alcohols

Oxidation of some 2-(N,N-dimethylaminomethyl)ferrocenylalkylcarbinols by MnO₂ is totally diastereoselective: only one diastereomer is oxidized. A study was performed to highlight the influential factors of this phenomenon. Several ferrocenyl alcohols have been studied. First, two diastereomers of the ferrocenyl amino alcohol bearing a deuterium as an R group have been synthesized and oxidized. The good reactivity of both diastereomers displayed the importance of the size of the alkyl group, which needs to be bulkier than a deuterium. The synthesis and the oxidation of endo- and exo-α-hydroxy [4](1,2)ferrocenophane enabled the elimination of the hypothesis involving the spatial position of the hydroxy group, while the two diastereomers were oxidized. The replacement of the dimethylamino group by a methoxy or a methyl, the oxidation of these compounds, and the study of the preferential conformation of each diastereomer showed clearly the influence of an intramolecular hydrogen bond. So,the diastereoselectivity was shown to depend on the steric bulk of the alkyl group and on the presence of a strong intramolecular hydrogen bond between the hydroxy group and the nitrogen.     

Determination and fractionation of sulphur in a contaminated dredged sediment

Conversion of sulphur compounds in reduced, contaminated sediments that are brought in upland conditions may largely affect the potential mobility of heavy metal contaminants. We applied selected methods for the determination of total sulphur and sulphur fractions in a contaminated sediment in the reduced state and after gradual drying and oxidation during 1 month. Dry ashing, followed by ion chromatographic detection, was reliable for the determination of total sulphur. Good recoveries were obtained in both reference samples and spiked samples. Total sulphur was 14.5±0.6 g kg⁻¹ relative to dry sediment. Wet chemical methods that involve the determination of acid-volatile, Zn–HCl-reducible, chromium-reducible, acetone-soluble and HI-reducible sulphur were used to estimate specific sulphur forms. Results for acetone-soluble sulphur were to high and not consistent with results for other fractions. Major part of sulphur in the sediment (90%) was inorganic. Sulphides were converted partially to sulphate and to intermediary oxidised sulphur compounds upon oxidation of the sediment. The results suggested that the intermediary oxidised sulphur pool in the reduced sediment (2.5 g kg⁻¹) mainly consisted of pyrite, that was not converted during drying and oxidation. No significant changes in organic sulphur were detected.     

One-pot oxidative Mannich-type reaction of lactams with alkyl malonates

One-pot substitution of a C-H bond at the position next to the nitrogen atom of lactams with alkyl malonates proceeded effectively by dehydrogenation of lactams with N-tert-butylbenzenesulfinimidoyl chloride, followed by Mannich-type addition of alkyl malonates.     

Hybrid polymerization of iso-butyl vinyl ether

The radiation-induced hybrid polymerization in the presence of the N-alkoxypyridinium salt having relatively stable nonnucleophilic anion (PF₆⁻) has been investigated in the paper. Based on the analysis of experimental data and the GPC spectrum, the onium salts not only oxidize -alkoxyalkyl radicals, produced from IBVE in dichloromethane by irradiation, to the corresponding cations, but also give nonnucleophilic anions PF₆⁻ for the polymerization system. The experimental results clearly demonstrate that free radical and cationic polymerization mechanisms occurred simultaneously in IBVE/EMP⁺PF₆⁻/CH₂Cl₂ systems on irradiation with γ-ray.     

Synthesis of stable azomethine ylides by the rearrangement of 1,3-dipolar cycloadducts of 3,4-dihydroisoquinoline-2-oxides with DMAD

1-Aryl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolines were prepared according to a one-pot procedure involving the reaction of 2-(3,4-dimethoxyphenyl)-ethylamine with aromatic aldehydes in TFA at reflux. The tetrahydroisoquinolines were treated with H₂O₂-WO₄²⁻ in methanol at room temperature to give the corresponding 3,4-dihydroisoquinoline-2-oxides. Treatment of these cyclic nitrones with DMAD in toluene at room temperature gave the corresponding isoxazolo[3,2-a]isoquinolines. These compounds were heated in toluene at reflux to give the corresponding ylides in high yields (Method A). The effect of the substituents on the rate of the rearrangement of such compounds prompted us to discuss a new mechanism involving consecutive C-C bond heterolysis and 1,3-sigmatropic shift. A one-pot reaction involving the treatment of the nitrones with equimolar amounts of DMAD in refluxing toluene also gave the ylides (Method B). The structures of the prepared compounds were elucidated by spectral means and elemental analyses.     

The Catalytic Oxidative Coupling of Methane

One of the great challenges in the field of heterogeneous catalysis is the conversion of methane to more useful chemicals and fuels. A chemical of particular importance is ethene, which can be obtained by the oxidative coupling of methane. In this reaction CH₄ is first oxidatively converted into C₂H₆, and then into C₂H₄. The fundamental aspects of the problem involve both a heterogeneous component, which includes the activation of CH₄ on a metal oxide surface, and a homogeneous gas-phase component, which includes free-radical chemistry. Ethane is produced mainly by the coupling of the surface-generated CH radicals in the gas phase. The yield of C₂H₄ and C₂H₆ is limited by secondary reactions of CH radicals with the surface and by the further oxidation of C₂H₄, both on the catalyst surface and in the gas phase. Currently, the best catalysts provide 20% CH₄ conversion with 80% combined C₂H₄ and C₂H₆ selectivity in a single pass through the reactor. Less is known about the nature of the active centers than about the reaction mechanism; however, reactive oxygen ions are apparently required for the activation of CH₄ on certain catalysts. There is spectroscopic evidence for surface O^? or O ions. In addition to the oxidative coupling of CH₄, cross-coupling reactions, such as between methane and toluene to produce styrene, have been investigated. Many of the same catalysts are effective, and the cross-coupling reaction also appears to involve surface-generated radicals. Although a technological process has not been developed, extensive research has resulted in a reasonable understanding of the elementary reactions that occur during the oxidative coupling of methane.     

Efficient Oxidation of Alcohols to Carbonyl Compounds by N,N‐Dichloro‐4‐Methylbenzenesulfonamide under Mild Conditions

A number of aldehydes and ketones were prepared by oxidation of alcohol by N,N‐dichloro‐4‐methylbenzenesulfonamide under mild and neutral conditions in good to high yield in dichloromethane at room temperature.