Ethyl hydroperoxide

Peroxides. Compounds of the type R—O—OH are named (1) by placing the name of the radical R before the word hydroperoxide or (2) by use of the prefix hydroperoxy- when another parent name has higher priority. For example, C2H5OOH is ethyl hydroperoxide. 

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... 

Ethanol amine dinitrate Ethylene diamine diperchlorate Ethylene glycol dinitrate Ethyl hydroperoxide Ethyl nitrate Ethyl nitrite Ethyl perchlorate... 

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... 

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... 

See Ethyl hydroperoxide Hydriodic acid Perchloric acid Iodides Potassium chlorate Hydrogen iodide... 

Connell and Smithies (C2) have proposed a photometric peroxidase method with guaiacol as substrate and H202 instead of ethyl hydroperoxide. According to Nyman (N7), the method is less specific than Jayle s method. In the clinically interesting low range of HbBC (0-30 mg/100 ml) the method is unreliable. A simplification has been presented by Owen et al. (02). No report exists on its specificity, accuracy, or precision. 

The normality of the stronger solution is checked once a month in the following way 0.1 ml ethyl hydroperoxide solution +2 ml potassium iodide (20 g/100 ml) + 2 chops of glacial acetic add are placed in a porcelain crucible, covered with a lid, and allowed to stand at room temperature for 4 hours. The amount of iodine released is then titrated with 0.05 N sodium thiosulfate. 

Procedure. Ten tests are done in series 0.1ml of horse Hb solution is pipetted into each beaker 0.020 ml serum is added to nine of the beakers. The content of the remaining one is used as a blank. Three ml 0.1 M KI is added to each beaker. A mixture of 100 ml acetate buffer, 10 ml ethyl hydroperoxide solution and 10ml iodine solution (8) is then prepared. (This mixture is only fit for use for 20 minutes.) At 60-second intervals 10 ml of this mixture is added to the beakers. Nine minutes and 15 seconds after the addition, 2 drops of starch solution are added, and titration with 0.01 N Na2SaOa is started after 9 minutes and 30 seconds. The titration should last, as closely as possible, 30 seconds. The temperature is measured in the reaction mixture. 

Ethylhexyl nitrate, 2 23 2-Ethylhexylpotassium, 14 256 2-Ethylhexyl salicylate, 22 16 2-Ethylhexylsodium, 14 255 Ethyl hydroperoxides, decomposition hazards of, 18 490 Ethylhydroxyethylcellulose (EHEC),... 

Concerning the mode of formation of ES, we prefer the concept that the substrate in a monolayer is chemisorbed to the active center of the enzyme protein, just as the experimental evidence pertaining to surface catalysis by inorganic catalysts indicates that in these reactions chemisorbed, not physically adsorbed, reactants are involved. Such a concept is supported by the demonstration of spectroscopically defined unstable intermediate compounds between enzyme and substrate in the decomposition by catalase of ethyl hydroperoxide,11 and in the interaction between peroxidase and hydrogen peroxide.18 Recently Chance18 determined by direct photoelectric measurements the dissociation con-... 

Chlorophenyl)-l,l-dimethylethyl hydroperoxide, 3018 2-Cyclohexenyl hydroperoxide, 2435 1,1-Dichloroethyl hydroperoxide, 0794 3,5-Dimethyl-3-hexyl hydroperoxide, 3075 Ethyl hydroperoxide, 0925... 

O Sullivan, D.W., Lee, M., Noone, B.C.,andHeikes, B.G. Henry s law constant determinations for hydrogen peroxide, methyl hydroperoxide, hydrox3miethyl hydroperoxide, ethyl hydroperoxide, and peroxyacetic acid, J. Phys. Chem., 100(8) 3241-3247, 1996. 

The b value for peroxides was not evaluated in the original publication, but we can do so here from the experimental enthalpies of vaporization that are available. There are three such for the alkyl hydroperoxides 35 kJmor for methyl hydroperoxide, 43.1 kJmol for ethyl hydroperoxide and 47.7 kJmol for tert-butyl hydroperoxide. The corresponding b values are 27.3, 30.8 and 29.8 kJmol , respectively. The mean value, 29.0 4=... 

Disproportionation reaction 7 might be expected to be thermoneutral in the gas phase and perhaps less so in the liquid phase where there is the possibility of hydrogen-bonding. Only for gas phase dimethyl peroxide is the prediction true, where the reaction enthalpy is —0.2 kJmoD. The liquid phase enthalpy of reaction is the incredible —61.5 kJmoD. Of course, we have expressed some doubt about the accuracy of the enthalpy of formation of methyl hydroperoxide. For teri-butyl cumyl peroxide, the prediction for thermoneutrality is in error by about 6 kJmor in the gas phase and by ca 9 kJmoD for the liquid. The enthalpy of reaction deviation from prediction increases slightly for tert-butyl peroxide — 14kJmol for the gas phase, which is virtually the same result as in the liquid phase, — 19kJmol . The reaction enthalpy is calculated to be far from neutrality for 2-fert-butylperoxy-2-methylhex-5-en-3-yne. The enthalpies of reaction are —86.1 kJmoD (g) and —91.5 kJmol (Iq). This same species showed discrepant behavior for reaction 6. Nevertheless, still assuming thermoneutrality for conversion of diethyl peroxide to ethyl hydroperoxide in reaction 7, the derived enthalpies of formation for ethyl hydroperoxide are —206 kJmoD (Iq) and —164 kJmoD (g). The liquid phase estimated value for ethyl hydroperoxide is much more reasonable than the experimentally determined value and is consistent with the other n-alkyl hydroperoxide values, either derived or accurately determined experimentally. 

With substrates 16b and 17a, Hoft and coworkers observed only low ee values of up to 4% for the hydroperoxides. On the other hand, phenyl ethyl hydroperoxide (16a) could be isolated in high enantiomeric excess of >99% from the CPO-catalyzed reaction. The observed enantioselectivities of the sulfoxides varied, depending on the conversion of the sulfide and the hydroperoxide used, being highest with 16a (92% ee). Unfortunately, the CPO-catalyzed resolution of chiral hydroperoxides is difficult on a preparative scale because of the high dilution necessary (0.5ttmolmL ). In the CiP-catalyzed kinetic resolution of 16a better results were obtained compared to the CPO-catalyzed reaction (see Table 5). 

Compared to metal-catalyzed asymmetric epoxidation reactions, asymmetric versions of this reaction without the need of a catalyst (apart from a base) are rarely known. In 2000 Adam and coworkers reported a method for the asymmetric Weitz-Scheffer epoxidation of substituted enones 91 by the secondary, optically active hydroperoxide (5 )-(l-phenyl)ethyl hydroperoxide (equation 27, Table 10). ... 

TABLE 10. Enantioselective Weitz-Scheffer epoxidation of substituted enones p-XC6H4C(0)CH= CR with (5)-(l-phenyl)ethyl hydroperoxide... 

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