Peroxides of acetone

The reaction of acetone with hydrogen peroxide gives various types of organic peroxides of acetone. The simple linear hydroperoxides and hydroxyperoxides form at first and then condense to the linear dimer and trimer analogs. The linear dihydroperoxide 2,2-dihydroperoxypropane (1) and its dimer bis(2-hydroperox-ypropane)peroxide (II) form as a main product in an acetone and hydrogen peroxide mixture, in the absence of an acidic catalyst [1]. 

Depending on the reaction conditions— primarily pH, concentration of reagents— the cyclic dimer, trimer form from their linear analogs. Cyclic dimer and trimer crystallize from the reaction mixture when catalyzed by an acid. The reaction mechanisms of cyclic peroxide formation have been investigated by several authors and are schematically summarized below [1-7]. 

The reaction conditions for the preparation of dimer and trimer peroxides are quite similar. This may seem a little confusing, as the same reactants and catalysts are used for preparation of TATP as well as for DADP. The issue of particular reaction conditions leading to dimer and trimer remains without a clear explanation. We found that the key factor governing the composition of the final product (which is either DADP, TATP, or a mixture of both) is the acidity of the reaction mixture. The trimer forms in a slightly or moderately acidic solution while the dimer (or mixture of both) forms in a highly acidic environment [8]. 

The formation of higher linear peroxides (oligoperoxides) of acetone as by-products in the preparation of the trimer has recently been published. Sigman et al. proved the presence of peroxides terminated by n hydroperoxygroups where n = 1-8. These peroxides have low thermal stability and convert into the trimer upon heating [9,10]. 

Linear peroxides of acetraie have never been used as primary explosives and therefore we have decided to focus exclusively on cyclic organic peroxides in the following sections. 

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CH3CH2OHCH3. B.p. 82 C. Manufactured by hydrolysis of propene. Used in the production of acetone (propanone) by oxidation, for the preparation of esters (e.g. the ethanoate used as a solvent), amines (diisopropylamines, etc.), glycerol, hydrogen peroxide. The alcohol is used as an important solvent for many resins, aerosols, anti-freezes. U.S. production 1978 775 000 tonnes. 

Alcohol autoxidation is carried out in the range of 70—160°C and 1000—2000 kPa (10—20 atm). These conditions maintain the product and reactants as Hquids and are near optimum for practical hydrogen peroxide production rates. Several additives including acids, nitriles, stabHizers, and sequestered transition-metal oxides reportedly improve process economics. The product mixture, containing hydrogen peroxide, water, acetone, and residual isopropyl alcohol, is separated in a wiped film evaporator. The organics and water are taken overhead and further refined to recover by-product acetone and the... 

Direct oxidation yields biacetyl (2,3-butanedione), a flavorant, or methyl ethyl ketone peroxide, an initiator used in polyester production. Ma.nufa.cture. MEK is predominandy produced by the dehydrogenation of 2-butanol. The reaction mechanism (11—13) and reaction equihbtium (14) have been reported, and the process is in many ways analogous to the production of acetone (qv) from isopropyl alcohol. 

Content of prime - tertiary peroxide groups was measured by the quantity of products of complete decay, which were measured by chromatography. It is known that the main contents in products of the complete decay of Oct-MA-TBPMM samples are acetone and 2,2-dimethylpropanol, which arise in reactions of chain fragmentation of tert-butylperoxy radical or in reaction of chain transfer of this radical. In this case the sum of acetone and 2,2-dimethylpropanol molecules is equal to the quantity of peroxide groups in polymer. As an internal standard we used chloroform. 

Dimethyl peroxide Diethyl peroxide Di-t-butyl-di-peroxyphthalate Difuroyl peroxide Dibenzoyl peroxide Dimeric ethylidene peroxide Dimeric acetone peroxide Dimeric cyclohexanone peroxide Diozonide of phorone Dimethyl ketone peroxide Ethyl hydroperoxide Ethylene ozonide Hydroxymethyl methyl peroxide Hydroxymethyl hydroperoxide... 

Because osmium tetroxide is expensive, and its vapors are toxic, alternate methods have been explored for effecting vic-glycol formation. In the aliphatic series, olefins can be hydroxylated with hydrogen peroxide with the use of only a catalytic amount of osmium tetroxide. Anhydrous conditions are not necessary 30% hydrogen peroxide in acetone or acetone-ether is satisfactory. The intermediate osmate ester is presumably cleaved by peroxide to the glycol with regeneration of osmium tetroxide. When this reaction was tried on a A -steroid, the product isolated was the 20-ketone ... 

An amount of enzyme preparation equivalent to 900 mg of wet cells was made up to 25 ml with the above potassium phosphate buffer solution. 150 mg (1.15 mmol) of 5-fluorouracil and 1.0 gram of thymidine (4.12 mmol) were dissolved in 15 ml of the above potassium phosphate buffer solution. The mixture was incubated at 37°C for 18 hours. After this time, enzyme action was stopped by the addition of four volumes of acetone and one volume of peroxide-free diethyl ether. The precipitated solids were removed by filtration, and the filtrate was evaporated under nitrogen at reduced pressure until substantially all volatile organic solvent had been removed. About 20 ml of aqueous solution, essentially free of organic solvent, remained. This solution was diluted to 100 ml with distilled water. 

The direct oxidation of propylene with oxygen is a noncatalytic reaction occurring at approximately 90-140°C and 15-20 atmospheres. In this reaction hydrogen peroxide is coproduced with acetone. At 15% isopropanol conversion, the approximate yield of acetone is 93% and that for H2O2 is 87% ... 

Study of the Explosive Characteristics of Acetone Peroxide , PATR 1202 (1942)... 

Dimethyl peroxide Diethyl peroxide Di-t-butyl-di-peroxyphthalate Difuroyl peroxide Dibenzoyl peroxide Dimeric ethylidene peroxide Dimeric acetone peroxide Dimeric cyclohexanone peroxide Diozonide of phorone Dimethyl ketone peroxide Ethyl hydroperoxide Ethylene ozonide Hydroxymethyl methyl peroxide Hydroxymethyl hydroperoxide 1-Hydroxyethyl ethyl peroxide 1 -Hydroperoxy-1 -acetoxycyclodecan-6-one Isopropyl percarbonate Isopropyl hydroperoxide Methyl ethyl ketone peroxide Methyl hydroperoxide Methyl ethyl peroxide Monoperoxy succinic acid Nonanoyl peroxide (75% hydrocarbon solution) 1-Naphthoyl peroxide Oxalic acid ester of t-butyl hydroperoxide Ozonide of maleic anhydride Phenylhydrazone hydroperoxide Polymeric butadiene peroxide Polymeric isoprene peroxide Polymeric dimethylbutadiene peroxide Polymeric peroxides of methacrylic acid esters and styrene... 

This last comment forces one to reconsider the interpretation given to the following accident. A mixture of acetone and isoprene gives rise to the formation of peroxides that detonated spontaneousiy. One can ask oneself what role acetone plays since the presence of acetone is hardly necessary to the formation of explosive peroxides by isoprene in the presence of oxygen (see Hydrocarbons on p.242). 

A great number of transformations has been performed on narceine imide (116) by Czech researchers. Oxidation with potassium permanganate in acetone or with nitric acid caused the cleavage of the alkaloid, giving rise to hemipinic imide (127). A similar result was noted by Rdnsch (129,130) during Lemieux-Johnson oxidation of ene lactam 152 (129,130) in this reaction the basic component (156) was isolated as well. The use of hydrogen peroxide in acetone converted 116 to (Z)-narceine imide N-oxide, which under the action of acetic anhydride underwent N-dealkylation (135). 

Distillation to small volume of a small sample of a 4-year-old mixture of the alcohol with 0.5% of the ketone led to a violent explosion, and the presence of peroxides was subsequently confirmed [1]. Pure alcohols which can form stable radicals (secondary branched structures) may slowly peroxidise to a limited extent under normal storage conditions (isopropanol to 0.0015 M in brown bottle, subdued light during 6 months to 0.0009 M in dark during 5 years) [2], The presence of ketones markedly increases the possibility of peroxidation by sensitising photochemical oxidation of the alcohol. Acetone (produced during autoxidation of isopropanol) is not a good sensitiser, but the presence of even traces of 2-butanone in isopropanol would be expected to accelerate markedly peroxidation of the latter. Treatment of any mixture or old sample of a secondary alcohol with tin(II) chloride and then lime before distillation is recommended [3], The product of photosensitised oxidation is 2-hydroperoxy-2-propanol [4]. 

Prevention of peroxidation of isoprene-acetone mixtures, and other hazards involved in the industrial preparation of synthetic citral, are discussed. 

Soluble fuels (acetone, ethanol, glycerol) will detonate on admixture with peroxide of over 30% concentration, the violence increasing with concentration. 

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