Chlorine dioxide amines

Chlorine dioxide is usually used in aqueous solution. It is a weaker oxidant than hypochlorite. Unlike chlorine it does not react with water to form hypochlorite or with amines to form A/-chloro compounds. Thus chlorine dioxide is easily removed from solutions by passing air through the solution or its headspace. Chlorine dioxide solutions decompose by equation 12 ... 

Iminium ions can be generated from tertiary amines and the free radical chlorine dioxide, a gas, which can be stored in aqueous solvents (equation 48)137. 

Wang P, He Y-L, Huang C-H (2010) Oxidation of fluoroquinolone antibiotics and structurally related amines by chlorine dioxide reaction kinetics, product and pathway evaluation. Water Res 44 5989-5998... 

Fungicide - [AMNES - LOWERALIPHATIC AMINES] (Vol 2) -castor oil derivative as [CASTOR OIL] (Vol 5) -copper(II) fluoridem [FLUORINE COMPOUNDS, INORGANIC - COPPER] (Vol 11) -as disinfectant [DISINFECTANTS AND ANTISEPTICS] (Vol 8) -use of chlorine dioxide [CHLORINE OXYGEN ACIDS AND SALTS - CHLOROUS ACID, CHLORITES, AND CHLORINE DIOXIDE] (Vol 5) -use ofpyrogallol m [POLYHYDROXY BENZENES] (Vol 19)... 

One-electron oxidants convert tertiary amines into aminium ions. Chlorine dioxide is an example of such a reagent this converts triethylamine and other tertiary alkylamines into aminium ions, which normally react further by the loss of hydrogen from an a-carbon atom. An example of a synthetic (plication of this reaction sequence is shown in Scheme 24, the inteimediate iminium ion being intercepted intramolecularly." Nitrosonium tetrafluoroborate and dioxygenyl hexafluoroantimonate, 02 SbF6, are also good one-electron oxidants which can be used at low temperature." ... 

DOT CLASSIFICATION 8 Label Corrosive SAFETY PROFILE Poison by inhalation. Moderately toxic by ingestion. A severe eye, skin, and mucous membrane irritant. Corrosive to body tissues. Flammable by chemical reaction. Explosive reaction with chlorine dioxide + chlorine, sodium, urea + heat. Reacts to form explosive products with carbamates, 3 -methyl-2-nitroben2anilide (product explodes on contact with air). Ignites on contact with fluorine. Reacts violently with moisture, CIO3, hydroxyl-amine, magnesium oxide, nitrobenzene, phosphorus(III) oxide, K. To fight fire, use CO2, dry chemical. Incompatible with aluminum, chlorine dioxide, chlorine. 

The use of sulfur dioxide as the solvent and low temperatures allows efficient and clean formation of the a-chloro nitroso compound4 6. The primary adducts, containing nitroso, nitro, or oxime functions, can be reduced to chlorine-free amines or /i-chloro amines 8. Additionally, chlorine readily undergoes substitution by nucleophiles (hydrides, alcohols, amines, etc.), such that halogen-free and /i-functionalized nitroso and nitro compounds, which can further be reduced to amines, can be prepared by this route. Recently, the conversion of nitroso compounds (RNO) to amines (RNHEt) using a triethylborane/borane mixture has been described9 10, although not applied specifically to /i-chloro nitroso compounds. 

Mechanistic studies of the chemical oxidation of aliphatic amines have been reviewed extensively by Chow et al. [22]. Many studies of the mechanism of oxidation of amines have been performed with chlorine dioxide or ferricyanide as oxidants, because they have absorption bands with maxima at 357 and 420 nm, respectively. Changes in the absorbance at these wavelengths for the respective oxidants can be conveniently used to follow the kinetics of the reactions. On the basis of these studies, the electron-transfer mechanism shown in Scheme 1 has been proposed for amine oxidation. 

Some other metal salts and other reagents which have been used to oxidize tertiary amines to enamines include palladiumfll) chloride copper(II) chloride , copperfi) chloride with oxygen , iodine, iodine pentafluoride , chlorine dioxide S permanganate ion , manganese dioxide , AT-bromosuccinimide , benzoyl peroxide , quinones and azodiformate . ... 

MERCURIC BROMIDE (7789-47-1) HgBfj Noncombustible solid. Light and heat cause decomposition keep out of sunlight. Violent reaction with strong oxidizers, including chlorine trifluoride. Aqueous solution is acidic. Incompatible with acetylene, ammonia, azides (may form mercury azide, a heat- and shock-sensitive explosive), bases, caustics, amines, amides, inorganic hydroxides calcium (forms amalgam) carbide, chlorine dioxide, copper and its alloys hydrazines, indium (violent at 662°F/350°C), lithiiun, potassium, rabidium, sodium. Note Be especially careful not to allow this compound to accumulate in sink traps with many of the above incompatible... 

EXPLOSION and FIRE CONCERNS not combustible flammable by chemical reaction NFPA rating Health 3, Flammability 0, Reactivity 2 contact with water will cause violent spattering and formation of toxic hydrogen chloride gas and phosphoric acid mist elevated temperatures may cause containers to burst pressure will develop in closed containers when exposed to moisture reacts explosively with chlorine dioxide and chlorine, sodium, and urea and heat ignites on contact with fluorine forms explosive products with carbamates and 3 -methyl-2-nitrobenzanilide reacts violently with water, acids, alkalies, alkali metals, alcohols, amines and organic acids incompatible with aluminum chlorine dioxide, chlorine, diphosphorus trioxide, fluorine, hydroxylamine, magnesium oxide, nitrobenzene, sodium, urea, and water hazardous... 

Rosenblatt DH, Hull LA, DeLuca DC, Davis GT, Weglein RC and Williams HKR, Oxidations of amines. II. Substituent effects in chlorine dioxide oxidations, JACS, 89 1158-1163 (1967). Cited in Perrin Bases suppl. no. 4961, ref. R22a. Used a glass electrode in a cell wiBi liquid junction potentials. Solutions were carbonate-free. No activity corrections were made. Calibrated pH meter at pH = 7.00 and 10.00. 

Robson (183) reported that the following compounds are known to repress the formation of chlorine dioxide from chlorous acid pyrophosphates (4) amines, especially ethylenediamine (184), and hydrogen peroxide, The repressors probably complex, or perhaps they react with one of the intermediates formed during the decomposition. The following compounds, on the other hand, are known to promote the production of chlorine dioxide from chlorous acid aldehydes, especially formaldehyde, and organic anhydrides such as acetic anhydride (3, 154). According to Masschelein... 

Chlorine dioxide exhibits a spectrum of reactivities toward organic compounds which is considerably different from the spectra exhibited by other oxidants commonly employed in the laboratory. In most cases, however, there is not enough information available to permit quantitative comparisons. For instance, it would appear that olefins react more rapidly with permanganate (k - lO -lO /T sec ) (66) than with chlorine dioxide (142, 143), whereas triethylamine is nearly 10 times as reactive with chlorine dioxide (186) as with permanganate (185). Among organic compounds extensively investigated thus far, the most reactive with chlorine dioxide are aliphatic tertiary amines (42, 103, 104, 186, 187) and phenols (1, 29,... 

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