Aerojet-General Corporation

Ampac Fine Chemicals LLC

Aerojet Fine Chemicals LLC

Air Products and Chemicals, Inc.

Der-Shing Huang

Renato R Rindone

Edward E Hamel

Olivier Dapremont

Aslam A Malik

Thomas G Archibald

James C Barnard

George R Gettys

Barton Milligan

Patrick Berget

Benjamin Mendoza

Xa Her

Darin Sanchez

Mark H Pratton

The present invention provides compounds and methods that can be used to convert 1,2,4-triazole-3-carboxamides to the corresponding 3-cyano-1,2,4-triazoles reliably in one step, with high yields and without the need for elaborate purification.

Process for the preparation of 3-cyano-1,2,4-triazoles

High yields and purity are obtained in the purification of enantiomers of chiral carboxylic acids by preparative-scale chromatography by including a tertiary alcohol in the mobile phase in conjunction with an acidic modifier and a hydrophobic solvent. The tertiary alcohol is superior to other, more commonly used alcohols by reducing the extent of esterification of the enantiomer that otherwise lowers the yield and the purity.

Preparative-scale separation of enantiomers of chiral carboxylic acids

A halide salt of a 1-(hydroxyiminomethyl-1-pyridino)-3-(halomethyl)-2-oxapropane is prepared by adding a pyridinealdoxime to a bis-halomethylether in such a manner that the bis-halomethylether is maintained in excess throughout the addition. This procedure produces the halide salt of a 1-(hydroxyiminomethyl-1-pyridino)-3-(halomethyl)-2-oxapropanein high yield and purity, which facilitates its use as an intermediate in the manufacture of an asymmetrically substituted 1,3-di(1-pyridino)-2-oxapropane, a class of compounds that are generally useful antidotes to various toxic agents. A prominent member of the class is the dimethylsulfonate salt of 1-(2-hydroxyiminomethyl-1-pyridino)-3-(4-carbamoyl-1-pyridino)-2-oxapropane. The use of mercaptoalkyl-functionalized polymers is disclosed as a preferred metal ion scavenger for a final purification step in the manufacture of these compounds.

Process for halomethyl ethers of hydroxyiminomethyl quaternary pyridinium salts

A halide salt of a 1-(hydroxyiminomethyl-1-pyridino)-3-(halomethyl)-2-oxapropane is prepared by adding a pyridinealdoxime to a bis-halomethylether in such a manner that the bis-halomethylether is maintained in excess throughout the addition. This procedure produces the halide salt of a 1-(hydroxyiminomethyl-1-pyridino)-3-(halomethyl) -2-oxapropanein high yield and purity, which facilitates its use as an intermediate in the manufacture of an asymmetrically substituted 1,3-di (1-pyridino)-2-oxapropane, a class of compounds that are generally useful antidotes to various toxic agents. A prominent member of the class is the dimethylsulfonate salt of 1-(2-hydroxyiminomethyl-1-pyridino)-3 -(4-carbamoyl-1-pyridino)-2-oxapropane. The use of mercaptoalkyl-functionalized polymers is disclosed as a preferred metal ion scavenger for a final purification step in the manufacture of these compounds.

Alkyl-substituted polyarenes of the formula ##STR1## in which R is alkyl and Ar.sub.res is an aryl residue, are prepared from aryl ketones by reaction of the latter with 1-cyclohexenyloxytrimethylsilane in the presence of a Friedel-Crafts catalyst. When R is methyl and Ar.sub.res is a naphthyl residue, the reaction serves as a step in a reaction scheme leading to crisnatol mesylate, a pharmaceutical useful in the treatment of brain cancer.

Polyarenes from aryl ketones with application to synthesis of crisnatol

Diazomethane is prepared in a batch process on a scale of at least 50 gram-moles per batch, from an N-methyl-N-nitroso amine in an organic solvent and an inorganic base in an aqueous solution by the use of a phase transfer catalyst and by controlling the choice of solvent, reagent concentrations, addition rate and reaction temperature to cause codistillation of the product and the organic solvent in such a manner that the concentration of diazomethane in both liquid and vapor phases are controlled within limits that will prevent detonation of the diazomethane.

Large scale batch process for diazomethane

Methylazide-substituted 1,3-dioxolanes of the generic formula ##STR1## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are independently selected from H, C.sub.1 -C.sub.6 alkyl and CH.sub.2 N.sub.3 are disclosed as energetic plasticizers for rocket and gun propellants and explosives formulations. Methods of preparation of these compounds are also disclosed, in which halogen-substituted vicinal diols are reacted with aldehydes or ketones to form the halo-analog of the product, which is then converted to the product by reaction with a metal azide.

Energetic azidomethyl-substituted 1,3-dioxolanes

Hydroxy-terminated aliphatic polyethers having the formula ##STR1## in which R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from the group consisting of H, CH.sub.2 N.sub.3 and CHN.sub.3 CH.sub.2 N.sub.3, such that the total number of azide groups per monomer unit is two to four, and n is an integer from 2 to 40, display unique properties as energetic polymers. Co-polymers of the monomer units in the above formula with other, known azido-substituted monomer units further provide energy outputs at preselected levels based on the proportions of each type of monomer present.

High energy hydroxy-terminated polyazido polymers

Novel multi-azido formals, acetals and ketals are disclosed, having the following generic formula ##STR1## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are independently selected from H, CH.sub.3, and CH.sub.2 N.sub.3, and methods of preparation of these compounds.

Energetic azide plasticizer

Tocopherols are isolated from vegetable oil distillates and other saponifiable substances in which tocopherols are naturally present, by saponification in an alcoholic medium, followed by metathesis with a zinc halide. The resulting zinc salts of fatty acids are readily precipitated out of solution without mechanical granulation or the addition of powdering agents, leaving the tocopherols in alcoholic solution from which they are readily recovered. The sterols and glycerol are also recoverable for use in other applications.

Recovery of tocopherols from plant and animal oils

Cyclic nitramines of the formula ##STR1## in which R.sup.1, R.sup.2 and R.sup.3 are independently selected from the group consisting of H, NO and NO.sub.2, and acid salts of the compound in which R.sup.1, R.sup.2 and R.sup.3 are each H, are disclosed. These compounds are useful as components in energetic compositions, including rocket and gun propellants and explosives, and are of particular interest due to their combination of high energy output and insensitivity. Compounds in which R.sup.3 is H or NO are further useful as intermediates in the preparation of those in which R.sup.3 is NO.sub.2. Also disclosed is a method for producing such compounds involving the reaction between hexamethylenetetramine and nitroguanidine.

High-energy insensitive cyclic nitramines

High energy insensitive cyclic nitramines

This invention relates to an improvement in a process for the manufacture of a nitroaromatic compound produced by the mixed sulfuric-nitric acid nitration method. The improvement resides in the refining of the aqueous acid mixture and comprises the following sequential steps: (a) contacting the mixed aqueous acid mixture, after nitration, with an oxidizing or a reducing agent under conditions effective for removing contaminant nitrous acid; (b) contacting the aqueous acid mixture in step (a) with feed aromatic compound to remove contaminant organics and residual nitric acid and then, if necessary, (c) contacting the remaining acid mixture with sufficient oxidizing agent under oxidizing conditions to remove residual organic components.

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Carmichael, CA, United States of America

Der-Shing Huang