Aziridination of alkenes using N-iodo-N-potassio-p-toluenesulphonamide as a nitrene precursor

N-Iodo-N-potassio-p-toluenesulphonamide was found to be a convenient nitrene precursor for the aziridination of alkenes in the presence of copper catalysts.     

Determination of bromide ions in seawater using flow system with chemiluminescence detection

A simple flow-based procedure with chemiluminescence (CL) detection is proposed for bromide ion determination in seawater. The procedure was based on the oxidation of bromide to bromine by chloramine-T followed by the reaction of bromine with luminol resulting in CL emission. Since no significant reaction within chloramine-T and luminol was observed, the detection was carried out without bromine extraction from the oxidant medium. The proposed flow system had a sampling rate of 40 determinations per hour, reagents consumption of 100 μg luminol and 60 μg chloramine-T per determination, a limit of detection of 0.5 mg l⁻¹ bromide ions, a linear concentration range (r = 0.999 and n = 7) between 0 and 100 mg l⁻¹, and a coefficient of variance better than 2.5% (for 10 measurements of a 10 mg l⁻¹ Br⁻ solution) were achieved. The analytical system was applied for the determination of bromide in seawater and estuarine-water samples, obtaining an analyte recovery ranging from 94 to 102% and comparing the results with a reference spectrophotometric method no significant difference was observed in 95% confidence level.     

Determination of Nitrite via Reaction with Pyridine-4-Carboxylic Acid Hydrazide

Abstract

Nitrite is determined by its reaction with a measured but excessive amount of pyridine-4-carboxylic acid hydrazide in acid medium (when the two substances react in a 1:1 molar ratio) and evaluation of the surplus hydrazide by titration with chloramine-T in the presence of acidified potassium bromide, the end-point being shown by the decolorization of the methyl red indicator. Nitrate, copper(II), mercury(II), etc. are found not to interfere, and the determination of nitrite in the presence of diazotized aromatic amines is demonstrated.     

An organocatalytic synthesis of N-sulfonyl imines using chloramine-T in aqueous medium

N-Sulfonyl imines have been synthesized in good to excellent yields from aldehydes and chloramine-T using proline as an organocatalyst in aqueous medium at ambient temperature. The protocol is applicable to a wide range of aldehydes, especially enals exhibit remarkable efficiency in the reaction. The reaction presumably occurs via iminium activation and opens new avenues for the synthesis of N-sulfonyl imines under environmentally benign and mild conditions.     

N-Bromosuccinimide-mediated reaction of cyclic styrenes with chloramine-T

A facile route toward substituted allylic sulfonamides 3 is developed from the N-bromosuccinimide (NBS)-mediated allylic amination of cyclic styrenes 2 with chloramine-T (1a). Skeleton 2 is prepared by Grignard addition of cyclic ketones with different arylmagnesium bromides in THF followed by dehydration of the resulting tertiary alcohols with BF₃·OEt₂ in CH₂Cl₂. The synthetic route obtained moderate yields from the one-step operation and the key structures of skeleton 3 were confirmed by X-ray crystallographic analysis.     

A new method for the generation of azoalkenes from ketohydrazones and its application to the synthesis of tetrahydropyridazine derivatives

The reaction of ketohydrazones containing an α-methylene group with chloramine-T followed by treatment with triethylamine leads to the formation of azoalkenes via an α-chloroazo-compound, which can react intermolecularly and in situ with olefinic compounds to produce tetrahydropyridazine derivatives in good yield.     

Ligand-assisted, copper-catalyzed enantioselective benzylic amination

Several classes of ligands, including α-amino acids, diamines, diphosphines, bis-oxazolines, and diimines, support efficient copper-catalyzed amination of benzylic hydrocarbons by anhydrous chloramine-T. Catalysts derived from homochiral ligands, particularly chiral diimines, effect aminosulfonation with low to moderate enantioselectivity.     

Effect of substituents on the oxidation of some alkyl-aryl sulphoxides by chloramine-T

The oxidation rates of some substituted phenyl methyl sulphoxides with chloramine-T have been studied in alkaline and neutral media. OsO₄ is used as catalyst in alkaline medium where the meta and para substituents show no effect on the reaction rate. This is explained on the basis of isokinetic relationship. In both the media, the orthosubstituents show steric effect.     

Electrophilic cyclization of N-alkenylamides using a chloramine-T/I2 system

A new protocol for the cyclization of N-alkenylamides using chloramine-T and iodine is described. When N-alkenylsulfonamides are treated with chloramine-T and iodine, three- to six-membered N-heterocycles are obtained with complete stereoselectivity. The method is compatible with the cyclization of the allylbenzamide or allylbenzthioamide to afford an oxazoline or thiazoline derivative, respectively. Mechanistic studies indicate that the chloramine-T/I₂ system functions as an effective iodonium species.     

Flow injection determination of anisidine value in palm oil samples using a triiodide potentiometric detector

A flow injection analysis (FIA) procedure for the determination of anisidine value (AV) in palm olein using a triiodide detector is described. Undiluted oil sample and chloramine-T reagent were added to a reaction chamber, and reaction was accelerated by applying a short vortex action (typically for 30 s). After allowing the emulsified oil phase to be separated from the aqueous phase (bottom layer), an aliquot of the aqueous phase (containing unreacted chloramine-T) was aspirated into a carrier stream that contained I⁻ where the chloramine-T oxidized the I⁻ to form I₃⁻ which was finally detected by a flow-through triiodide potentiometric detector. Variables that affect the FIA signals such as size of the reaction chamber, oil and reagent flow rates, chloramine-T concentration, vortex time, time for phase separation, carrier stream pH and injected volume were studied. The optimized FIA procedure is linear over 1.0-23.0 AV. The method exhibits good repeatabililty (R.S.D. of ±3.16% (n = 4) for the determination of 5.0 AV) and a sampling rate of 40 samples per hour was achieved. Good correlation (r² = 0.996 (n = 4)) between the proposed method and the manual American Oil Chemists’ Society procedure was found when applied to the determination of twenty different types of palm olein samples.