Hydroxylamine periodate

A mixture of 150 grams of 1-(3, 4 -dimethoxyphenyl)-2-propanone and 70 grams of hydroxylamine hydrochloride in 125 cc of water is stirred while a solution of 51.3 grams of sodium carbonate in 150 cc of water is added over the course of 15 minutes, and while maintaining the reaction mixture at 30°-40°C. The reaction mixture is stirred for an additional two and one-half hour period at room temperature, and is then diluted with an equal volume of water and extracted three times with 300 cc portions of ether. The combined ether extracts are washed with water, dried over anhydrous magnesium sulfate, and the... 

Hydrogenation catalyst, Acid, Fuel Riesthuis, P. et al., J. Loss Prev. Process Ind., 1997, 10(10), 67 In the presence of precious metal hydrogenation catalyst, hydroxylamine salts may disproportionate and form dinitrogen monoxide. Such a mixture is present in a process whereby the hydroxyamine is formed by hydrogenation of nitrate. An explosion in the degassing line, after a period of abnormal operation, was attributed to nitrous oxide build-up. Fuel, in the form of hydrogen and methane diluent, was already present. 

If hydroxylamine hydrochloride and sodium nitrite, of normal laboratory particle size, are swiftly shaken together and left to stand, a vigorous gas evolving reaction will start after a short induction period. This is a rare example of spontaneous reaction of solids See Ammonium salts, above... 

Acyl nitroso compounds (3, Scheme 7.2) contain a nitroso group (-N=0) directly attached to a carbonyl carbon. Oxidation of an N-acyl hydroxylamine derivative provides the most direct method for the preparation of acyl C-nitroso compounds [10]. Treatment of hydroxamic acids, N-hydroxy carbamates or N-hydroxyureas with sodium periodate or tetra-alkyl ammonium periodate salts results in the formation of the corresponding acyl nitroso species (Scheme 7.2) [11-14]. Other oxidants including the Dess-Martin periodinane and both ruthenium (II) and iridium (I) based species efficiently convert N-acyl hydroxylamines to the corresponding acyl nitroso compounds [15-18]. The Swern oxidation also provides a useful alternative procedure for the oxidative preparation of acyl nitroso species [19]. Horseradish peroxidase (HRP) catalyzed oxidation of N-hydroxyurea with hydrogen peroxide forms an acyl nitroso species, which can be trapped with 1, 3-cyclohexanone, giving evidence of the formation of these species with enzymatic oxidants [20]. 

NMR data on hydroxylamines, oximes and hydroxamic acids appeared at roughly the same periods as those of other types of compounds with a small delay for N relative... 

The chemical applications of ultrasound (Sonochemistry) have become an exciting new field of research during the past decade. Recently, Li and coworkers have found an efficient and convenient procedure for the preparation of oximes via the condensation of aldehydes and ketones in ethanol with hydroxylamine hydrochloride under ultrasound irradiation (Scheme 8). Compared with conventional methods, the main advantages of the sonochemical procedure are milder conditions, higher yields and shorter reaction periods. The reason may be the phenomenon of cavitations produced by ultrasound. 

In the oxidation of hydroxylamine by silver salts and mercurous salts, the nature of the reaction product apparently depends upon the extent to which catalysis participates in the total reaction. This is illustrated by some results obtained with mercurous nitrate as oxidizing agent. The reaction is strongly catalyzed by colloidal silver, and is likewise catalyzed by mercury. The reaction of 0.005 M mercurous nitrate with 0.04 M hydroxylamine at pH 4.85 proceeds rapidly without induction period. The mercury formed collects at the bottom of the vessel in the form of globules when no protective colloid is present, so the surface available for catalysis is small. Under these conditions the yield is largely nitrous oxide. Addition of colloidal silver accelerates the reaction and increases the yield of nitrogen. Some data are given in Table III. 

The reduction of silver chloride by hydrazine shows some points of similarity to the action of hydroxylamine, but also some important points of difference (James, 34). An induction period was obtained with the unnucleated precipitates which, under some conditions, was relatively large. However, exposure of the precipitate to actinic light had only a small effect upon the induction period and upon the subsequent course of the reaction. Previous nucleation of the precipitate by the action of hydroxylamine decreased the induction period without eliminating it, and produced little or no effect upon the subsequent course of the reaction. Addition of the dye, 3,3 -diethyl-9-methylthiacarbocyanine chloride, produced no effect until the surface of the precipitate was more than half covered. Further increase in the amount of dye added produced an irregular decrease in the reaction rate. Gelatin decreased the reaction rate, but to a smaller extent than in the hydroxylamine reaction, and a minimum rate was not attained. As the gelatin concentration increased, more and more reduced silver appeared in colloidal form in the solution. 

Pentafluoronitrosobenzene, 363, 410 Pentyl azide, 271 Peracid oxidation of amines, 323, 363,409 of azo compounds, 355-356 of hydrazones, 362 of hydroxylamines, 364,415 of imines, 406 of oxaziranes, 407 Perchloryl fluoride, 336 Perfluoroalkylureas, 162 Perfluoro-2-azopropene, oxidation of, 432 Periodic acid oxidation, 338 Permonosulfuric acid, see Caro s acid Phenazines, 321... 

The related Lossen reaction was used in studies on the core of a Salmonella lipopolysaccharide.105 Aldehyde groups formed on periodate oxidation were oxidized to carboxylic acid groups, these were esterified, the esters were treated with hydroxylamine, and the products finally subjected to the Lossen reaction by treatment with a water-soluble carbodiimide. 

The teichoic acid shows an infrared absorption band at 1751 cm.-1, characteristic of carboxylic ester groups, which is not observed in samples from which the D-alanine residues have been removed. Removal of the u-alanine was readily effected with ammonia or hydroxylamine, when D-alaninamide or D-alanine hydroxamate were formed. The kinetics of the reaction with hydroxylamine reveal the high reactivity of its D-alanine ester linkages, which, like those in most other teichoic acids, are activated by the presence of a neighboring phosphate group. That the D-alanine residue is attached directly to the ribitol residues, instead of to the d-glucosyl substituents, was also shown by oxidation with periodate under controlled conditions of pH, when it was found that the D-alanine residues protect the ribitol residues from oxidation. Under the same conditions, all of the ribitol residues were oxidized in a sample of teichoic acid from which the D-alanine had been removed, and it is concluded that the ester groups are attached to C-2 or C-3 of the ribitol residues. 

Trimethoxybenzaldehyde lc (0.196 g, 1.0 mmol), hydroxylamine hydrochloride (0.077 g, 1.1 mmol) and peroxymonosulfate (0.61 g, 1.0 mmol) doped on a neutral alumina (1.0 g) were mixed thoroughly on a vortex mixer. The reaction mixture was placed in an alumina bath inside a commercial microwave oven (operating at 2450 MHz frequency) and irradiated for a period of 7 min. After completion of the reaction (monitored by TLC) the inorganic support was separated by filtration, after eluting the product with dichloromethane (2x 15 mL). The solvent was removed and the residue on purification by column chromatography on silica gel gave the corresponding trimethoxybenzonitrile 2a in 95% yield and there was no evidence for the formation of any side products. 

The most usable and well-known pathway for the synthesis of five-membered nitrogen-containing heterocycles is condensation involving a,P-usaturated carbonyls and 1,2-binucleophilic compounds, e.g., derivatives of hydrazine and hydroxylamine (Scheme 2.8). The procedure based on these reactions was successfully applied for a long period [45, 46, 47, 48, 49, 50, 51, 52, 53]. 

Periodic acid is another important oxidant. It can selectively oxidize many organic compounds. Compounds containing aldehyde, ketone or alcoholic groups on adjacent carbon atoms are rapidly oxidized. Similarly, hydroxylamines are oxidized to aldehydes. Some of the half-reactions are shown below ... 

Oxidation of 2,3-dimethylbutane-2,3-bis-hydroxylamines with bromine or sodium periodate in aqueous solution at room temperature yielded 3,3,4,4-tetramethyl-A1-l,2-diazetine-l,2-dioxide <1972JA5077, 1975JOC1409> which can be reduced to diazetidine. 

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