Diacetyl Peroxide Solution

Chemical Designations — Synonyms Diacetyl Peroxide Solution Chemical Formula CH3CO(Oi)OCCH3 in dimethyl phthalate. 

Denatured Alcohol 2,4-D Esters Detergent Alkylate = 2 Dextrose Solution Diacetic Ether Diacetone Diacetone Alcohol Diacetylmethane Diacetyl Peroxide Solution... 

ACETYL PEROXIDE SOLUTION Diacetyl Peroxide Solution Organic Peroxide 1 2 4 ... 

Diacetyl Peroxide Solution Acetyl Peroxide Peroxide... 

Following a published procedure [1], octene was treated with a solution of perox-yacetic acid in acetic acid for 8 h to form the epoxide, but the reaction mixture was then allowed to stand uncooled overnight. Next morning, when a 3pl sample was injected into a heated GLC injection port, the syringe shattered. This was attributed to formation of diacetyl peroxide during the overnight standing, and its subsequent explosion in the heated port [2],... 

Application of fluorine to aqueous sodium acetate solution causes an explosion, involving formation of diacetyl peroxide. 

During preparation of peracetic acid solutions for textile bleaching operations, the reaction mixture must be kept acid. Under alkaline conditions, highly explosive diacetyl peroxide separates from solution [1], An excess of the anhydride has the same effect [2],... 

The higher the viscosity of the solvent, the higher the amount of the parent molecules formed due to the geminate recombination of radicals. The observed rate constant of decomposition of the initiator decreases with an increase in viscosity [3,90], This was observed in the decomposition of peresters and diacetyl peroxide in various solutions. Subsequently, the fraction fT of the radical pairs recombining to the parent molecule increases with an increase in the viscosity ... 

A related procedure, which may be of value from the preparative standpoint, involves the preparation of /rans-nitrosomethane dimer by adding a solution of diacetyl peroxide in sec-butyl nitrite to warm sec-butyl nitrite [50]. From the product of the reaction it has been assumed that this preparation involves the generation of free methyl radicals which react with the nitrite to give nitrosomethane and alkoxy radicals. The latter disproportionate to ketones and alcohols, while the nitroso compound dimerizes. 

Tetraacetylethane has been prepared previously both by the use of sodium metal2 and of sodium hydride3 with acetylacetone followed by addition of iodine. Also, the compound has been prepared in low yield by the reaction of diacetyl peroxide with acetylacetone 4 and by the electrolysis of acetylacetone in an alcohol-water solution.2 The present method, although similar to those first mentioned, is somewhat more convenient and does not require anhydrous conditions. 

Procedure Transfer an accurately measured volume of sample, equivalent to about 25 mg of diacetyl, into a suitable flask. Add 3 drops of phenolphthalein TS, and neutralize the acidity by titrating with 0.05 N sodium hydroxide to a faint pink endpoint. Add 0.25 mL of 30% hydrogen peroxide solution and 3 drops of 0.01% Osmic Acid. Mix, cover the flask, and allow it to stand in an incubator held at about 38° for not less than 4 h. Cool to room temperature, and titrate with 0.05 N sodium hydroxide to a faint pink endpoint. Each milliliter of 0.05 N sodium hydroxide is equivalent to 8.6 mg of diacetyl. 

The second piece of evidence for the intermediacy of the dimeric peroxide, 32, stems from the low temperature ozonolysis of trans-2,3-dibromo-2-butene, 23. In contrast to the usual reactions which were carried out at ca. —35°C, the ozonolysis of 23 in pentane at —78°C yielded a solid white precipitate which exploded violently when we tried to isolate it. When the low temperature ozonolysis was carried out in methylene chloride, on the other hand, no precipitate appeared. However, when the methylene chloride solution of the ozonolysis product was allowed to warm up gradually, an exothermic reaction set in at around —50 °C, and the originally colorless solution showed the typical color of dissolved bromine. It is assumed that the explosive material is the dimeric peroxide, 32, which undergoes spontaneous debromination to form diacetyl peroxide, 33. 

The homolytic thermolyses of di-t-butyl peroxide [36, 37] and diacetyl peroxide [38, 39] have roughly the same rate constants and activation energies both in the gas phase and in solution in a variety of solvents. 

SYNS ACETYL PEROXIDE, not >25% in solution (UN 2084) pOT) ACETYL PEROXIDE, soUd, or >25% in solution pOT) DIACETONE PEROXIDES, solid, or >25% in solution (DOT) DIACETYL PEROXIDE (MAK)... 

Peroxide explosions are usually caused by heat, shock, impact, or catalysts, but the possibility of spontaneous explosions must not be left out of account, even with peroxides that are normally considered to be harmless. Among the most important protective measures in work with these substances is to wear protective glasses many organic peroxides (tert-butyl hydroperoxide, cumyl hydroperoxide, cyclohexanone peroxide, 2-butanone peroxide, diacetyl peroxide) cause serious injury on entry into the eye.315 If such an accident happens, the eye should be bathed at once with water or, better, 2% sodium hydrogen carbonate solution oily media must not be used. 

Contact with readily oxidizable substances may produce spontaneous combustion. Concentrated solutions can detonate on heating. The rate of decomposition increases by 1.5 times for every — 12°C (10°F) increase in temperature (NFPA 1997). Mixing with organic compounds may cause violent explosions. This includes alcohols, acetone and other ketones, aldehydes, carboxylic acids, and their anhydrides. With acetic acid and acetic anhydride, peroxyacetic acid is formed. In the presence of excessive anhydride, diacetyl peroxide is formed. Both the peroxy acids and the organic peroxides are shock-sensitive explosive compounds. Spontaneous ignition occurs when added to cotton (cellulose). 

Diacetyl peroxide diluted solutions with <25% strength are used as free-radical somces to initiate polymerizations and in organic syntheses. 

The concentrated compound is a severe eye hazard. An amount of 60 mg in a 1-minute rinse caused severe irritation in rabbit s eyes. Skin contact of its solution may cause irritation. Toxicity of this compound should be of low order. Diacetyl peroxide caused lung and blood tumors in rats. Its carcinogenic action on humans is not reported. 

Pure diacetyl peroxide is extremely shock sensitive and therefore stored as a 25% solution in dimethyl phthalate. It is a flammable compound, but it is the shock sensitivity that makes it a highly dangerous substance. It forms crystals from its solution below -5°C (23 °F) which are shock sensitive. Kunh (1948) reported an explosion of diacetyl peroxide while it was being removed from an... 

---