Diethylamine, oxidation

The kinetics of diethylamine oxidation by molecular oxygen catalyzed by Ru(III) ion and Ru(III)-EDTA complex has been studied in aqueous solution at 35 [16]. The main reaction products are the corresponding imine, N-hydroxyethylamine and acetaldehyde. The proposed mechanism involves formation of a ruthenium amide complex which undergoes -hydride elimination. 

Processes rendered obsolete by the propylene ammoxidation process (51) include the ethylene cyanohydrin process (52—54) practiced commercially by American Cyanamid and Union Carbide in the United States and by I. G. Farben in Germany. The process involved the production of ethylene cyanohydrin by the base-cataly2ed addition of HCN to ethylene oxide in the liquid phase at about 60°C. A typical base catalyst used in this step was diethylamine. This was followed by liquid-phase or vapor-phase dehydration of the cyanohydrin. The Hquid-phase dehydration was performed at about 200°C using alkah metal or alkaline earth metal salts of organic acids, primarily formates and magnesium carbonate. Vapor-phase dehydration was accomphshed over alumina at about 250°C. 

Methyl vinyl ketone can be produced by the reactions of acetone and formaldehyde to form 4-hydroxy-2-butanone, followed by dehydration to the product (267,268). Methyl vinyl ketone can also be produced by the Mannich reaction of acetone, formaldehyde, and diethylamine (269). Preparation via the oxidation of saturated alcohols or ketones such as 2-butanol and methyl ethyl ketone is also known (270), and older patents report the synthesis of methyl vinyl ketone by the hydration of vinylacetylene (271,272). 

A variety of substituted alkanolamines (Table 2) can also be made by reaction of oxide with the appropriate amine. Aminoethylethanolamine is made from the reaction of ethylenediamine [107-15-3J and ethylene oxide. Methyldiethanolamine is made from the reaction of ethylene oxide and methylamine [74-89-5J. Diethylethanolamine is made by the reaction of diethylamine [109-87-7] and ethylene oxide. 

Isoprene (2-methyl-1,3-butadiene) can be telomerized in diethylamine with / -butyUithium as the catalyst to a mixture of A/,N-diethylneryl- and geranylamines. Oxidation of the amines with hydrogen peroxide gives the amine oxides, which, by the Meisenheimer rearrangement and subsequent pyrolysis, produce linalool in an overall yield of about 70% (127—129). 

Complex nitrogen compounds are formed from the reaction of aLkylamines with ethylene oxide (61). Thus diethylamine and ethylene oxide react to yield diethylaminoethanol. The diaLkylarninoethanols can react with ethylene oxide to give amino poly(ethylene glycols) ... 

With Hydrogen Cyanide. Ethylene oxide reacts readily with hydrogen cyanide ia the presence of alkaline catalysts, such as diethylamine, to give ethylene cyanohydria. This product is easily dehydrated to give acrylonitrile ia 80—90% yield ... 

Diethylaminoethyl alcohol has been prepared by reduction of diethylaminoacetic ester with sodium and alcohol, by the action of ethylene chlorohydrin on diethylamine, and by the action of ethylene oxide on diethylamine. ... 

The reaction of benzofurazan iV-oxide with diethylamine affords 3-methyl-1,2,4-benzotriazine 4-oxide 160 (79T681, 82T1793). 

There is evidence from a detailed study of the photolyses of 2-alkyl-substituted aryl azides 40 in diethylamine that A3,7V-diethyl-1 //-azepin-2-amines are formed as oxygen-sensitive, meta-stablc intermediates that can give rise to a variety of byproducts, including 5-acyl- A%V-diethyl-pyridin-2-amines and 6-alkyl-7-(diethylamino)-2//-azepin-2-ones 11 however, formation of these oxidation products can be avoided by refluxing the photolysate mixture with methanol prior to exposure to oxygen, in which case practicable yields of the /V,/V-diethyl-3W-azepin-2-amines 41 result. 

The pyridines which are formed as minor products (1-8%) during the photolysis of 2-substituted phenyl azides in diethylamine are thought to be products of the aerial oxidation of nonisolable l//-azepine intermediates.11... 

The data on the determination of the number of the propagation centers on chromium oxide catalysts by the inhibition method were given in several papers water (61), carbon tetrachloride (167), and diethylamine (69) were used as inhibitors. It was found that the number of propagation centers is about 10% (61), 1% (167), and 20% (69) of the total content of chromium in the catalyst. 

DEHA oxidation products in LP boiler systems are primarily acetate and actaldehyde whereas in HP boilers diethylamine and aceteldehyde are produced. An outline reaction is shown below ... 

Contact of dicyanofurazan, or its A-oxide (dicyanofuroxan), with hydrazine, mono-or di-methylhydrazine, piperidine, piperazine, diethylamine or their mixtures is instantaneously explosive. 

The synthesis of 0-labelled phenylphosphonothioate (289) (Scheme 31) was achieved by reaction of dichlorophenylphosphine (287) with Et OH followed by addition of water to give (288). Oxidation with elemental sulfur in the presence of diethylamine then gave the salt of the O-ethylphenylphosphonothioate, which was alkylated with ethyl iodide to give the 0-labelled 0,S -diethyl... 

Amines such as diethylamine, morpholine, pyridine, and /V, /V, /V, /V -tetramethylethylene-diamine are used to solubilize the metal salt and increase the pH of the reaction system so as to lower the oxidation potential of the phenol reactant. The polymerization does not proceed if one uses an amine that forms an insoluble metal complex. Some copper-amine catalysts are inactivated by hydrolysis via the water formed as a by-product of polymerization. The presence of a desiccant such as anhydrous magnesium sulfate or 4-A molecular sieve in the reaction mixture prevents this inactivation. Polymerization is terminated by sweeping the reaction system with nitrogen and the catalyst is inactivated and removed by using an aqueous chelating agent. 

The 4,6-diamino-1,3,5-triaza-2-phosphapentalenes are deep red crystalline solids. For reactions, the 4,6-bis(diethylamino) derivative (99) was used (Scheme 34). The compound is not oxidized by air and does not react with sulfur or selenium. Alkylation takes place at the nitrogen atom adjacent to phosphorus. With diethylamine and alcohols no reaction is observed <86CB3213,87PS(30)780>. On simultaneous oxidation by sulfur or selenium, however, alcohols add to the P=N bond yielding... 

---