Dimeric peroxide

Rohrlich Sauermilch(Ref 6a) say that high sensitivity and extreme volatility of dimeric peroxide exclude it from practical consideration. It was recommended, however, by N ah sen (Addnl Ref a) for use in fuzes, detonators and caps and by Thiemann(Addnl Ref c) as an additive to Diesel fuels... 

Dilthey et al (Ref 3), by dropwise addn of cyclopentanone to amixt of acet, acetic anhydride, H2S04 H202 at 15° and stirring, obtd a Trimeric Peroxide, prisms (from ale), mp 172° (decomp) when the filtrate was poured into water, a Dimeric Peroxide, small ndls (from ale or benz), mp 105°. Both peroxides are powerful expls sensiti e to impact... 

Similarly, McCapra and Leeson (1976) have reported that reaction of some dimeric peroxides with 1,3,10-trimethylisoalloxazinium perchlorate [42] gives light. These authors suggest that this reaction proceeds by addition of the hydroperoxide to the lOa-position to give eventually the spirohydantoin [43] as shown in (50). 

The formation of the completely debrominated product, diacetyl peroxide 33, from the zwitterion intermediate, 26, probably proceeds via the dimeric peroxide of structure 32 in the manner depicted below ... 

Although the intermediate dimeric peroxide, 32, could not be isolated and rigorously proved, there are two items of evidence which favor the postulated reaction course. The first evidence comes from independent experiments in which tetracyanoethylene was used as a coreagent during the ozonolysis of 23. In these cases, the formation of diacetyl peroxide, 33, as well as that of 3,3-dibromobutanone, 31, was drastically reduced, and at the same time tetracyanoethylene epoxide was formed. Apparently, the reaction of tetracyanoethylene with the zwit-... 

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 reaction of p-nitro-N,N-dimethylaniline with ozone was studied. Only side-chain oxidation products, p-rafro-N-methylaniline, p-nitro-N-methylformanilide, and a dimeric peroxide, di- [(N-methyl-N-p-nitrophenyl)aminomethyl peroxide, were formed. No N-oxide could be obtained. For comparison 2-carboxy-4-nitro-N,N-dimethylaniline, p-chloro-N,N-dimethylaniline, and N,N-dimethylaniline were ozonized. A mechanism is proposed. 

In the ozonization of rubber, Harries135 obtained a peroxide which was shown by Pummerer et al.13e to be the dimeric peroxide of levulinic acid (133), and which can be synthesized from the acid with concentrated hydrogen peroxide.137 133 is partly converted into succinic acid on treatment with acid. 

To differentiate monomeric, dimeric, and polymeric products, a molecular weight determination is essential. The usual cryoscopic and osmometric techniques are applicable.In fact, these methods have been used for impure dioxe-tanes and at low temperatures.Furthermore, the dioxetane derived from the acridine (14) by singlet oxygenation (Eq. 27) was shown to be the dimeric peroxide (15) by cryoscopy. ... 

CA 39,2024(1945) (Effect of catalytic addns on the decomp of acet peroxide is discussed) f)M.Kolobielski,CR 237,1717-18(1935) CA 49,1696(1955) [Mixt of trimeric and dimeric peroxides may be obtained by total ozoniza-tion of 2,2,3,5-tetramethyl-2-(/3,/3-dimethyl-vinyl)—2.3—d ihydrofuran]... 

The nature of the products of oxidation of cyclophosphamide with Fenton s reagent has been further investigated and it now appears that the crystalline isolable product is the dimer peroxide (41). Both (41) and the hydroperoxide... 

In another process, a nonaqueous solution was the carrier of an initiator capable of generating a stable end group. For example, aqueous potassium persulfate solution was replaced by solvent-based solutions of hexafluoropropylene oxide (HFPO) dimer perox-ide.[i25]-[i37] Homopolymer and copolymers of tet-rafluoroethylene and other fluorinated monomers were synthesized by this technique. A homopolymer was produced in a 25 ml high pressure reactor, using HFPO dimer peroxide initiator in a similar manner to potassium persulfate initiator. A 0.018 mole solution (0.05 ml) of HFPO dimer peroxide in 1,1,2-trichlorotri-... 

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