Peroxy Derivatives of Aldehydes and Ketones

The reduction of hydroperoxides with LiAlH, yields the corresponding alcohols probably via an LiAl(OR)4 intermediate. However this reaction with Bz202 resulted in an explosion (Ref 1) Cumene hydroperoxide (91-95% pure) will not detonate even when strongly boostered. However, it is easily ignitable can burn with sufficient violence to rupture steel distillation equipment (Ref 4) 

272 CA 45, 8885 (1951) 2) R. Criegee, Herstelling und Umwanglung von Peroxyden in Houben-Weyl, Methoden der organischen Chemic, 4th edit, Stuttgart, Vol VIII, 6 (1952) 

Hydroquinone, Hydroquinol, 1,4-Benzenediol or p-Dihydroxybenzene (Hydrochinon in Ger). See 1,4-Dihydroxybenzene in Vol 5 of Encycl, p D1270-R 

Hydrous. A compd contg water, as opposed to anhydrous. In case of salts it is water of crystallization 

Azidohydroquinone, N3.c6H3(OH)2 mw 151.12, N 27.81%, OB to C02 -132.3 leaflets, mp-explodes violently on heating sol in ale or eth, insol in petr eth. It can be prepd from quinone and an excess of hydrazoic acid in benz Refs 1) Beil 6, (419) 2) E. Oliveri-Mandala  

Diazidodinitro hydroquinone. (OH)2C4H2(N3)2 (N02)2 (probably), mw 284.15, N 39.41%, OB-11.2, fme yellow needles (from mixed acid) 

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Safety. Since organic peroxides can be initiated by heat, mechanical shock, friction or contamination, an enormous problem in safety presents itself. Numerous examples of this problem have already been shown in this article. Additional examples include the foilowing methyl and ethyl hydroperoxides expld violently on heating or jarring, and their Ba salts also are extremely expl the alkylidene peroxides derived from low mw aldehydes and ketones are very sensitive and expld with considerable force polymeric peroxides of dimethyl ketene, -K>-0-C(CH3)2C(0)j-n, expld in the dry state by rubbing even at —80° peroxy acids, especially those of low mw, and diacetyl, dimethyl, dipropkmyl and methyl ethyl peroxides, when pure, must be handled only in small amts and... 

Chien and Kiang [44] carried out oxidative pyrolysis of PP at temperatures between 240 °C and 289 °C. The products were separated by GC and identified online by an interface GC peak-identification system. The major products were CO, H O, acetaldehyde, acetone, butanal, formaldehyde, methanol and other ketones and aldehydes. These identifications were confirmed by MS. Most of the products can be accounted for by well-known reactions of alkoxyl and peroxyl radicals the major products are derived from the secondary alkoxy and peroxy species. Oxygen starvation is manifested in diffusion-limited products of olefins and dienes, and the increase in the formation of CO and H O in an atmosphere of pure oxygen. The first-order rate constant at 240 °C is 2.4 x 10 Vs, with an overall activation energy of approximately 16 kcal/mol (67 kj/mol). If one assumes that the oxidative pyrolysis shares the same reaction pathways as autoxidation at lower temperatures, then the observed rate constants and activation energy may be calculated from kinetic... 

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