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• 99-34-3 3,5-dinitrobenzoic acid 

Relevant academic research and scientific papers

Highly Energetic, Low Sensitivity Aromatic Peroxy Acids

The synthesis, structure, and energetic materials properties of a series of aromatic peroxy acid compounds are described. Benzene-1,3,5-tris(carboperoxoic) acid is a highly sensitive primary energetic material, with impact and friction sensitivities similar to those of triacetone triperoxide. By contrast, benzene-1,4-bis(carboperoxoic) acid, 4-nitrobenzoperoxoic acid, and 3,5-dinitrobenzoperoxoic acid are much less sensitive, with impact and friction sensitivities close to those of the secondary energetic material 2,4,6-trinitrotoluene. Additionally, the calculated detonation velocities of 3,5-dinitrobenzoperoxoic acid and 2,4,6-trinitrobenzoperoxoic acid exceed that of 2,4,6-trinitrotoluene. The solid-state structure of 3,5-dinitrobenzoperoxoic acid contains intermolecular O-H?O hydrogen bonds and numerous N?O, C?O, and O?O close contacts. These attractive lattice interactions may account for the less sensitive nature of 3,5-dinitrobenzoperoxoic acid.

POLYMER-SUPPORTED PERSULFONIC ACID AS OXIDISING AGENT

A polymer-supported persulfonic acid has been prepared and applied for the oxidation of carboxylic acids, ketones, olefins, and disulfide bonds of cystine and cystinyl peptides to their peracids, esters (lactones), epoxides and sulfonic acid derivatives respectively in good yields.The resin also effectively removed the formyl protection from formyl amino acids.Spent polymer was reactivated by simple reactions.

PHASE TRANSFER CATALYSED PEROXIDATION OF CARBOXYLIC ACIDS WITH POTASSIUM PERSULFATE

Aqueous solution of potassium persulfate converts water-insoluble carboxylic acids in ether (or dichloromethane), to peracids in a yield of 80-90percent under the catalytic influence of benzyltriethylammonium chloride (BTEAC) or polyethyleneglycol (PEG-400).The reaction is further catalyzed kinetically in presence of a sulfonated polymer.

Mechanistic and Preparative Studies on the Regio- and Stereoselective Paraffin Hydroxylation with Peracids

Reactions of more than 20 hydrocarbons with p-nitro- or, e.g., 3,5-dinitroperbenzoic acid in chloroform show regioselectivities of Rst = 90 (relative rates of attack at tertiary and secondary C-H bonds, after statistical correction) to 500 and configurational retention, if applicable, of typically 97-99.7percent.Radical side reactions are recognized by concomitant formation of, e.g., nitrobenzene and are responsible for a decrease in regio- and stereoselectivity.Steric effects are observed in attack at axial tertiary C-H bonds and at bridgehead positions.Electronegative and hydrogen-bonding substituents in the alkane diminish, and alkyl groups enhance the rates; the observed Taft ρ* value of -2.2 indicates substantial positive charge accumulation in the transition state in agreement with the high regioselectivity.A Hammett reaction constant of +0.63 is obtained from substituted perbenzoic acids; activation parameters of ΔH* = 15-19 kcal mol-1 and ΔS* = -22 to -29 eu with three alkanes of different flexibility and an isotope effect of kH/kD = 2.2 with methylcyclohexane are measured.Aromatic rings are usually not attacked but lead to deactivation of the peracid even at remote alkane C-H positions; similar deactivation is found in hydrogen-bonding solvents.Androstanes yield preferentially 9α- and 5α-hydroxy products, if, e.g., a 17β-acetoxy substituent is used to steer the reaction.Diols usually are only observed as a result of a proximity effect of a peracid associated at the first formed hydroxy group.The results point to relatively late and oxenoid transition states with substantial charge separation in the substrate.Attempts to achieve selective oxidations using macrocyclic azacyclophanes with attached carboxylic functions were not successful, although the host compounds showed selective complexation of hydrocarbons.