Hydrogen peroxide amines

Molecules containing reduced oxygen species, e.g. alkyl hydroperoxides, peracids, periodate, hypochlorite, hydrogen peroxide, amine oxides, and iodosoarenes, are also capable of reducing dioxygen in the presence of P450. It is this that gave the impetus to the development of models based on simple porphyrin systems. 

CH3CH2OHCH3. B.p. 82 C. Manufactured by hydrolysis of propene. Used in the production of acetone (propanone) by oxidation, for the preparation of esters (e.g. the ethanoate used as a solvent), amines (diisopropylamines, etc.), glycerol, hydrogen peroxide. The alcohol is used as an important solvent for many resins, aerosols, anti-freezes. U.S. production 1978 775 000 tonnes. 

With the aid of a small pipette or a fine-bore dropping-tube (Fig. 30, p. 60), add about 4 drops of the filtered enzyme solution to the amine acetate solution. Using another dropping-tube add i drop of 20 volume hydrogen peroxide solution and shake well. Note the colour change which takes place. 

Because of their use in the rubber industry various sulfenamido thiazoles (131) have been prepared. They are obtained in good yields through the oxidation of A-4-thiazoline-2-thiones (130) in aqueous alkaline solution in the presence of an amine or ammonia (Scheme 66) <123, 166, 255, 286, 308, 309). Other oxidizing agents have been proposed (54, 148. 310-313) such as iodine (152), chlorine, or hydrogen peroxide. Disulfides can also be used as starting materials (3141. 

With thionyl chloride as catalyst, hydrogen peroxide adds to vinyl ethers in anti-Markovnikov fashion, as do monothioglycols with amine catalysts... 

The presence of ammonia and hydrogen peroxide in permanent hair color products is a disadvantage. Both are considered by consumers to be harsh chemicals. The odor of ammonia is unpleasant for a personal care product. Monoethanol amine has been used as a substitute for ammonia in some commercial permanent hair color products. It is not as effective as ammonia in allowing the hair to be lightened but it does not have as strong an odor. 

Toxic or malodorous pollutants can be removed from industrial gas streams by reaction with hydrogen peroxide (174,175). Many Hquid-phase methods have been patented for the removal of NO gases (138,142,174,176—178), sulfur dioxide, reduced sulfur compounds, amines (154,171,172), and phenols (169). Other effluent treatments include the reduction of biological oxygen demand (BOD) and COD, color, odor (142,179,180), and chlorine concentration. 

Divalent copper, cobalt, nickel, and vanadyl ions promote chemiluminescence from the luminol—hydrogen peroxide reaction, which can be used to determine these metals to concentrations of 1—10 ppb (272,273). The light intensity is generally linear with metal concentration of 10 to 10 M range (272). Manganese(II) can also be determined when an amine is added to increase its reduction potential by stabili2ing Mn (ITT) (272). Since all of these ions are active, ion exchange must be used for deterrnination of a particular metal in mixtures (274). 

Obsolete uses of urea peroxohydrate, as a convenient source of aqueous hydrogen peroxide, include the chemical deburring of metals, as a topical disinfectant and mouth wash, and as a hairdresser s bleach. In the 1990s the compound has been studied as a laboratory oxidant in organic chemistry (99,100). It effects epoxidation, the Baeyer-Villiger reaction, oxidation of aromatic amines to nitro compounds, and the conversion of sodium and nitrogen compounds to S—O and N—O compounds. 

Organomineral hydroperoxides have been prepared from hydrogen peroxide and organomineral haUdes, hydroxides, oxides, peroxides, and amines (10,33). If HX is an acid, ammonia is used to prevent acidic decomposition. 

Amine oxides used in industry are prepared by oxidation of tertiary amines with hydrogen peroxide solution using either water or water and alcohol solution as a solvent. A typical industrial formulation is as follows ... 

EDTA (ethylenediaminetetraacetic acid, [60-00-4]) chelates any trace metals that would otherwise decompose the hydrogen peroxide [7722-84-1]. The amine is preheated to 55—65°C and the hydrogen peroxide is added over one hour with agitation the temperature is maintained between 60 —70°C. The reaction is exothermic and cooling must be appHed to maintain the temperature below 70°C. After all the peroxide has been added, the temperature of the reaction mixture is raised to 75°C and held there from three to four hours until the unreacted amine is less than 2.0%. The solution is cooled and the unreacted hydrogen peroxide can be destroyed by addition of a stoichiometric amount of sodium bisulfite. This may not be desirable if a low colored product is desired, ia which case residual amounts of hydrogen peroxide enhance long-term color stabiUty. 

Owiag to the lower basicity of the parent amines, aromatic amine oxides cannot be formed directiy by hydrogen peroxide oxidation. These compounds may be obtained by oxidation of the corresponding amine with a peracid perbenzoic, monoperphthaUc, and monopermaleic acids have been employed. 

Industrial specifications for aHphatic tertiary amine oxides generally requite an amine oxide content of 20—50%. These products may contain as much as 5% unreacted amine, although normally less than 2% is present. Residual hydrogen peroxide content is usually less than 0.5%. The most common solvent systems employed are water and aqueous isopropyl alcohol, although some amine oxides are available ia aoapolar solveats. Specificatioas for iadividual products are available from the producers. 

CH—NHOH) to oxime (C=NOH) and ultimately to the nitroalkane (CH—NO2). Hydrogen peroxide generates amine oxides from tertiary cycloaUphatic... 

Oxidation by Hydrogen Peroxide. This reaction produces amine oxides (qv) (1,7,33,34,36). 

Eatty amine oxides are most frequendy prepared from alkyldimethylarnines by reaction with hydrogen peroxide. Aqueous 2-propanol is used as solvent to prepare amine oxides at concentrations of 50—60%. With water only as a solvent, amine oxides can only be prepared at lower concentrations because aqueous solutions are very viscous. Eatty amine oxides are weak cationic surfactants. 

Nitroso compounds are formed selectively via the oxidation of a primary aromatic amine with Caro s acid [7722-86-3] (H2SO ) or Oxone (Du Pont trademark) monopersulfate compound (2KHSO KHSO K SO aniline black [13007-86-8] is obtained if the oxidation is carried out with salts of persulfiiric acid (31). Oxidation of aromatic amines to nitro compounds can be carried out with peroxytrifluoroacetic acid (32). Hydrogen peroxide with acetonitrile converts aniline in a methanol solution to azoxybenzene [495-48-7] (33), perborate in glacial acetic acid yields azobenzene [103-33-3] (34). 

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). 

This type of amination by an oxaziridine is assumed to be the key step of a novel process for hydrazine manufacture, in the course of which butanone in solution with ammonia is reacted with hydrogen peroxide and acetonitrile. The smooth formation of oxaziridines from Schiff bases and hydrogen peroxide-nitrile mixtures is as well known as NH transfer from an oxaziridine like (300), suggesting the intermediacy of (300) as the N—N forming agent (72TL633). 

EFFECTS OF AMINES IN OXIDATION OF HYDROQUINONE WITH HYDROGEN PEROXIDE CATALYZED BY COPPER(H)... 

This reaction provides a wide variety of products since decomposition of the deuterated alkylborane intermediate (164) can be achieved with hydrogen peroxide to yield labeled alcohols (165), with hydroxylamine-O-sulfonic acid leading to deuterated amines (166), as well as with boiling propionic acid or propionic acid-OD, to form mono- (167) or dideuterio (168) hydrocarbons, respectively. Furthermore, if a monodeuterium label at the sterically more accessible position (170) is sufficient, the use of expensive metal deute-... 

Extension of the hydration reaction to hydrogen peroxide has shown that stable peroxides are formed from enamines and the imonium salts derived from secondary amines and ketones (506,507). 

At low temperature a 1 1 adduct of thioacetic acid and an enamine could be prepared (709). The previously described reaction of aminomethylene ketones with hydrogen peroxide was extended to bisaminomethylene compounds. However, acylated cyclohexenamines led to cyclopentane-carboxamides (770), Trichloromethyl adducts of enamines and the rearranged amine derivatives were described in a further study (777). 

The stereochemical course of reduction of imonium salts by Grignard reagents was found to depend on the structure of the reagent 714). Hydro-boration of enamines and oxidation with hydrogen peroxide led to amino-alcohols (7/5). While aluminum hydrogen dichloride reacted with enamines to yield mostly saturated amines and some olefins on hydrolysis, aluminum hydride gave predominantly the unsaturated products 716). 

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