Acetone-derived peroxides

Some ketone-derived peroxides have explosive properties, of which the most interesting are obtained from acetone. Four acetone-derived peroxides have been synthesized. Acetone peroxide dimer (48) is obtained in 94 % yield by treating acetone with a slight excess of 86 % hydrogen peroxide in acetonitrile in the presence of concentrated sulfuric acid at subambient temperature. The reaction of acetone with potassium persulfate in dilute sulfuric acid also yields acetone peroxide dimer (48). Acetone peroxide trimer (49), also known as triacetone triperoxide (TATP), has been obtained as a by-product of these reactions or by the addition of... 

Payne and Smith59 studied the hydroxylation of cyclohexene with a mixture of 34% hydrogen peroxide and a little tungstic acid in acetone. In addition to trans-1,2-cyclohexanediol, they obtained a 25% yield of 3,3-dimethyl -1,2,4-trioxaacetone derivative of the intermediate hydroxyhydroperoxide. Hydrogenation of 71 leads to tm w-cyclo-hexane-l,2-diol. 

Recently Bartlett and Shimizu"3 demonstrated that triplet acetone derived from dioxetane lb chemisensitized the decomposition of benzoyl peroxide in carbon tetrachloride, affording chlorobenzene, which exhibited a photo-CINDP effect. Finally, we observed that the / -peroxylactone (60) afforded exclusively tetramethylethylene oxide when chemisensitized by lb, as shown in Eq. (46).116... 

Aminoanthracene forms a Schiff base with dimethylacetaldehyde (isobutyral-dehyde). This compound can be oxidized by peroxide under basic conditions to form 9-formamidoanthracene and acetone in dimethylformamide as a solvent [54, 55], CL from this system can be observed in other aprotic solvents as well. A limited amount of work has been done with the CLs of Schiff bases or anthracene derivatives. Presumably, this will change in the future. 

About 30 years ago, an enthalpy of formation was reported for 3,3,4,4-tetramethyl-l,2-dioxetane . Both by direct microcalorimetric combustion measurements of the neat solid and by reaction calorimetry (of the solid itself, and in acetone solution to form acetone), a consensus value was derived. Now, is the enthalpy of formation plausible , notwithstanding the very large error bars Consider reaction 6 for the dioxetane that produces 2,3-dimethyl-2,3-butanediol . The liquid phase enthalpy of reaction is —329 kJmoU. It is remarkable that this value is compatible with that for the dialkyl peroxides, ca —335 kJmoU, despite the ring strain that might be expected. 

This qualitative interpretation of structural and electronic similarity has also been employed to rationalize the fact that the quantum yield for the dioxetane derivative 6, in which the phenoxy substituent is directly linked to the peroxidic ring, is two orders of magnitude higher than for the dioxetane 7, in which the trigger function is separated by a methylene bridge. Furthermore, the different quantum yields were rationalized in terms of a competition between the intramolecular (pathway A) and intermolecular back-electron transfer (pathway B) in the decomposition of 7, whereas the intramolecular back-electron transfer was believed to occur exclusively in the decomposition of 6, due to the higher stability of the radical anion of the benzaldehyde derivative, as compared with the radical anion of acetone (Scheme 14). 

The first syntheses of 1,2-cfs-thioglycoses (a-D-gluco- and )3-D-manno- derivatives) have been achieved by the reaction in acetone of alkyl or benzyl xanthate or potassium thioacetate with the corresponding l,2-tra s-glycosyl halides [13]. More recently, tetra-O-acetyl-l-S-acetyl-l-thio-a-D-glucopyranose (10a) (Scheme 3) has been obtained i) by reaction of -acetochloroglucose (9 a) with either potassium thioacetate in HMPA or the tetrabutylammonium salt of thio-acetic acid in toluene [14] ii) by peroxide-induced addition of thioacetic acid to the pseudo-glucal (11) [15]. 

Both polonium derivatives are chemically very stable, requiring hot fuming nitric acid for their decomposition. However, they char rapidly under the intense alpha bombardment and attempted analyses with acetyl-acetone labeled with carbon-14 in the 1 and 3 positions were unsuccessful. It is interesting that the corresponding yellow oxide, prepared by treating (VI) with aqueous hydrogen peroxide, reverts to (VI) on treatment with aqueous alkali (12). 

Benzodioxines. The reaction of benzo-l,4-dioxanes with NBS catalyzed by dibenzoyl peroxide results in 2,3-dibromo derivatives, which undergo denomination to benzo-l,4-dioxines when treated with sodium iodide in acetone (equation I).1... 

Since the addition of formamide to olefins is induced photochemically as well as by peroxides at elevated temperatures, it may be safe to assume that we deal here with a free radical reaction. Let us apply this assumption to interpret the results. A reasonable free radical derived from formamide would be a carbamoyl radical CONH2 which can be formed by loss of a hydrogen atom from formamide. Experimental data show that irradiation of formamide in the presence of acetone and in the absence of an olefin leads to the formation of considerable amounts of oxamide. 

Cyclic peroxides with six-membered rings are obtained from acetyl-acetone and hydrogen peroxide.41,42 Rieche et al. 1 obtained the 1,2-dioxolan derivative (36) (85%), and replacement of the hydroxyl groups in 36 with —OOH leads to 37. 

Not surprisingly, adenine and guanine have been a major focus of many studies in this field and in alcohol solutions with irradiation at wavelengths >290 nm, 8-hydroxyalkyl derivatives are produced. The yields are improved by use of sensitizers such as acetone and di-f-butyl peroxide (73JOC3420). With substituted purines, attack may also occur at the substituent group as with caffeine which in 2-propanol produced (174). 

The rearrangement products derived from aromatic and non-aromatic heterocyclic amines crystallize readily from the lower alcohols. Unlike those of many of the A-substituted glycosylamines, the crystals are not solvated. On the other hand, the ketose derivatives of aralkyl- and alkyl-amines, such as 2-phenylethylamine, ethanolamine, diethanolamine, glycine ethyl ester, and phenylalanine (see Table II), are hydrated or alcoholated, or both, and are difficult to isolate in pure crystalline form. The crystals which have been isolated were hygroscopic. Alcohols, aqueous alcohols, and water are the most commonly used solvents for crystallization. Acetone, ether, or benzene have been added to the alcoholic media in order to increase the yield of crystalline compound. The use of solvents that contain peroxides promotes decomposition of the crystals during storage. ... 

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