Hydrogen peroxide-triethylamine

Fig. 1. Time courses of the chemiluminescence intensity from oxalate—hydrogen peroxide systems in ethyl acetate as solvent, 0.7 mM TCPO. The curves correspond to the following concentrations of triethylamine (TEA) catalyst A, 0.05 mM B, 0.10 mM and C, 0.20 mM (70).

Similar hydroxylation-oxidations can be carried out using a catalytic amount of osmium tetroxide with A-methylmorpholine oxide-hydrogen peroxide or phenyliodosoacetate." A recent patent describes the use of triethylamine oxide peroxide and osmium tetroxide for the same sequence. Since these reactions are of great importance for the preparation of the di-hydroxyacetone side-chain of corticoids, they will be discussed in a later section. 

For the preparation of 3-benzothiepin 3,3-dioxide (11) a multiple-step synthesis has been described.82 Oxidation of 4,5-dihydro-3-benzothiepin-l(2//)-one to its S,S-dioxide with hydrogen peroxide in glacial acetic acid, is followed by the multiple-step preparation of dibromide 10, which is dehydrohalogenated by triethylamine to provide sulfone 11. 

A solution of 1 equivalent of the oxazolidinone in diethyl ether is cooled to —78 C. To the resultant suspension are added 1.4 equivalents of triethylamine. followed by 1.1 equivalents of dibutylboryl triflate. The cooling bath is removed and the reaction mixture is stirred at 25 °C for 1.5 h. The resultant two-phase mixture is cooled to — 78 "C with vigorous stirring. After 1 equivalent of aldehyde is added, the reaction is stirred at —78 °C Tor 0.5 h, and 0 "C for 1 to 2 h. The solution is diluted with diethyl ether, washed with 1 N aq sodium bisulfate, and concentrated. Following oxidation with 30% aq hydrogen peroxide (10 equivalents, 1 1 methanol/water, 0 C. 1 h), extractive workup and chromatographic purification, the aldol adduct is obtained with >99% diastcrcomeric purity. 

Triethylamine Hydrogen Peroxidate, CgHj 5N.4H202 Ibid Ibid... 

Two different approaches have been used to determine phenols without derivatization. In the first, the corresponding oxalate esters were synthesized in the traditional way (i.e., using oxalyl chloride and triethylamine) [111, 112]. Pen-tachlorophenol, 1-naphthol, bromofenoxim, bromoxynil, and /t-cyanophenol were treated this way, after which the POCL resulting from their reaction was measured in a static system. The second approach exploits the oxidation reaction between imidazole and hydroxyl compounds at an alkaline pH, where hydrogen peroxide is formed [113]. Polyphenols, e.g., pyrogallol, pyrocatechol, and dopa-... 

Aldehyde 26 was treated with hydroxylamine hydrochloride in refluxing methanol to give a mixture of (E)- and (Z)-pyrrolotriazine 40 in 59% and 21% yield, respectively. Dehydration of aldoxime 40 with trifluoromethanesulfonic anhydride and triethylamine in dichloromethane afforded triazine 41. Conversion of the nitrile 41 to the deprotected amide 42 was accomplished in 96% yield on treatment of 41 with basic hydrogen peroxide in ethanol <2001CAR77>. 

Rauhut and coworkers were the first to obtain rate constants from emission kinetic studies and to verify the dependence of kobsi and kobsi on the concentration of the base catalyst and on hydrogen peroxide, respectively. Schowen and coworkers , using TCPO, H2O2 and DPA, with triethylamine as catalyst, observed an oscillatory behavior in emission experiments and proposed a mechanism involving the formation of two HEIs (involved in parallel chemiluminescent reactions) to explain it. Other authors have also observed a similar oscillating behavior but have explained it as a complex... 

For example, when coned sulfuric acid is brought in contact with a mixt of KMn04 and some org substances, such as glycerin or sugar, the temp is raised to inflammation point and the detonator fires the main chge. The same happens when coned hydrogen peroxide is added to A1 + C or to thorium or when fuming nitric acid is added to triethylamine... 

Triethylamine hydrogen peroxidate, 2565 Triethylammonium nitrate, 2575 Triethylantimony, 2569 Triethylarsine, 2552 Triethylbismuth, 2556 Triethylborane, 2554 f Triethyl borate, 2555... 

Methylpiperidine Stannous chloride dihydrate 2-Ethoxybenzoyl chloride 4-Dimethylaminopyridine Triethylamine Hydrogen peroxide Chlorosulfonic acid 5-carboxylic acid ethyl ester... 

Nakushima et al. determined dipyridamole on the basis of its chemiluminescence intensity after injecting into a carrier stream of triethylamine in acetonitrile (1 mL/min) combined with a stream of bis-(2,4,6-trichlorophenyl)oxalate and hydrogen peroxide [47]. 

The standard oxidation procedure employs 30% hydrogen peroxide and 3 M sodium hydroxide. However, functionalities sensitive to strong alkali require milder conditions. In such cases, buffering, simultaneous addition of base and peroxide,492 or oxidation with Oxone ,493 triethylamine A-oxide,494-498 peracids,499,500 or sodium hypochlorite50 were recommended. Oxygen has been rarely used for such purpose,502 but trialkylboranes in bromoperfluorooctane were cleanly reacted with oxygen with the retention of configuration of the secondary alkylboranes (Equation (104)).503... 

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