Applications of oxaziridines in organic synthesis

A process for the epoxidation of olefinic compounds, consisting of reacting said compounds with hydrogen peroxide either introduced as such or produced by substances capable of generating it under the reaction conditions, in the presence of synthetic zeolites containing titanium atoms, of general formula: where x lies between 0.0001 and 0.04, and possibly in the presence of one or more solvents, operating at a temperature of between 0° and 150°C, and at a pressure of between 1 and 100 ata.

Process for the epoxidation of olefinic compounds

Two catalytic methods emerging newly for the production of e-caprolactam are reviewed: the ammoximation, and the vapor phase Beckmann rearrangement. These processes do not produce any ammonium sulfate as a by-product. The key for the processes are the catalysts used. The TS-1 zeolite comprising Ti and Si oxides with the structure of MFI is applied as an effective catalyst in the ammoximation reaction. This work reviews its catalysis and the features of the reaction. Although many solid acid catalysts have been tested for the Beckmann rearrangement, recently high silica MFI zeolites without so-called acidic sites are developed for the reaction. A brief history of the catalyst development on the rearrangement is presented, and the catalysis of high silica MFI zeolite is reviewed.

The development of new heterogeneous catalytic processes for the production of ε-caprolactam

Solid core particles encapsulated in a single coat of paraffin wax, the wax having a melting point of about 40° to about 50° C. and a solids content of from 100 to about 35% at 40° C. and from 0 to about 15% at 50° C. The paraffin coat may comprise 20 to 90% by weight of the particle and may be from 100 to 1,500 microns thick. The coat prolongs the time in which particles encapsulated therewith may remain active in aqueous environments. The encapsulated particle is made by spraying molten wax onto the particles in a fluidized bed. Liquid or powder cleaning compositions, particularly automatic dishwashing liquid detergents, may incorporate 0.01 to 20% by weight of the composition of the coated wax-encapsulated particles.

Wax-encapsulated particles

An oxysterol biomarker for 7-dehydrocholesterol oxidation in cell/mouse models for Smith-Lemli-Opitz syndrome

Ammonia and aldehydes or ketones are selectively oxidized by hydrogen peroxide to the corresponding azines when they are reacted in the presence of both (a) an amide of a carboxylic acid having a pK greater than about 4.3 and (b) a co-catalyst having the general formula H--X--Y=Z, wherein H is hydrogen, X and Z are each an atom of oxygen or nitrogen and Y is an atom of carbon, nitrogen, arsenic, antimony, phosphorus, sulfur, selenium or tellurium; the atoms of X, Y, and Z carrying other substituents necessary to obey the rules of valence. Preferred co-catalysts include di(alkali metal) hydrogen phosphates, lower dialkyl phosphate esters, bicarbonates and p-toluene sulfonic acid. When 1° or 2° amines are also present, hydrazones are also formed along with the azines. Uses of the resultant products include their hydrolysis to hydrazines with recycling of aldehyde or ketone.

Method for preparing azines and hydrazones

Novel percompound activators having the formula ##STR1## wherein R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are the same or different and are hydrogen or certain substituted or unsubstituted straight or branched chain alkyl radicals, cycloalkyl radicals, or hydrocarbon radicals containing at least one aromatic ring, or R 5 and/or R 6 are COR 7 , where R 7 is hydrogen or certain substituted or unsubstituted straight or branched chain alkyl radicals or hydrocarbon radicals containing at least one aromatic ring, the activators producing more rapid bleaching or oxidation at a given temperature or the same bleaching effect at a lower temperature and being useful for bleaching textile fibers, oils, fats, and waxes; hair and skin treatment; metal surface passivation; or purifying, sterilizing and disinfecting techniques.

Activators for percompounds

Continuous process for the synthesis of azines from aqueous hydrogen peroxide, ammonia and a reactant containing a CO group, (i) a working solution circulating in a loop between the azine reactor and a treatment device and (ii) the introduction of a product preferably chosen from acetic acid, ammonium acetate and acetonitrile. The azines are hydrolysed to obtain hydrazine hydrate.

Process for the synthesis of azines, its application in the production of hydrazine

Chimie des peroxydes en milieu basique I - oxydation des bases de schiff en oxaziridines avec le peroxyde d'hydrogene et un nitrile

1. Continuous process for the preparation of propylene oxide, which comprises the preparation of an organic solution of percarboxylic acid by reacting hydrogen peroxide with a carboxylic acid in the presence of a solvent which azeotropically entrains water, and the epoxidation of propylene by this percarboxylic acid solution, characterised in that : a) the organic solution of percaboxylic acid, containing less than 1% by weight of water and up to 1% by weight of hydrogen peroxide, is obtained by reacting, a between 90 and 100 degrees C, a solution of propionic acid in an organic solvent which is inert towards the peracid and capable of forming, with water, a hetero-azeotrope of boiling point below 100 degrees C under atmospheric pressure, with an aqueous solution containing from 30 to 75% by weight of hydrogen peroxide, in the presence of 0.0005 to 0.002 mole of a strongly acid catalyst per mole of hydrogen peroxide and of an inhibitor of radical reactions, and continuously removing the water by azeotropic distillation, the proportions of the reactants being so chosen that the molar ratio of hydrogen peroxide to propionic acid is between 0.2 and 1 and that the azeotropically entraining solvent represents from 50 to 75% by weight of the reaction mixture ; b) the crude organic solution of perpropionic acid which is obtained as the bottom product from the azeotropic distillation of stage (a) is reacted with an excess of propylene, so that the molar ratio of propylene to perpropionic acid is between 1.01 and 10, at a temperature of between 40 and 80 degrees C, under a pressure of between 2 and 20 bar, the pressure being so chosen that the reaction medium is kept in the liquid phase ; and c) the reaction mixture issuing from stage (b) is treated in a manner known per se so as to separate off successively unconerted propylene, which is recycled to stage (b), the propylene oxide, which is extracted, the organic solvent and the propionic acid, which are jointly recycled to the peracid synthesis stage (a).

Jean-Pierre Schirmann

Papers

Method for preparing azines and hydrazones

Activators for percompounds

Process for the synthesis of azines, its application in the production of hydrazine

Chimie des peroxydes en milieu basique I - oxydation des bases de schiff en oxaziridines avec le peroxyde d'hydrogene et un nitrile

Continuous process for the preparation of propylene oxide