Silver hypochlorite

Silver hypochlorite, AgOCl.—A very unstable solution of the hypochlorite is formed by the action of chlorine-water on excess of silver monoxide. It soon decomposes into silver chloride and chlorate. 

Although silver hypochlorite is soluble iu H2O, it dismutates very quickly, hence adding Ag to CIO forms the white AgCl ... 

If a bromomethyl- or vinyl-substituted cyclopropane carbon atom bears a hydroxy group, the homoallyiic rearrangement leads preferentially to cyclobutanone derivatives (J. Sa-laun, 1974). Addition of amines to cydopropanone (N. J. Turro, 1966) yields S-lactams after successive treatment with tert-butyl hypochlorite and silver(I) salts (H.H. Wasserman, 1975). For intramolecular cyclopropane formation see section 1.16. 

Oxalic acid Furfuryl alcohol, silver, mercury, sodium chlorate, sodium chlorite, sodium hypochlorite... 

The dimethyl ethers of hydroquiaones and 1,4-naphthalenediols can be oxidized with silver(II) oxide or ceric ammonium nitrate. Aqueous sodium hypochlorite under phase-transfer conditions has also produced efficient conversion of catechols and hydroquiaones to 1,2- and 1,4-benzoquiaones (116), eg, 4-/-butyl-l,2-ben2oquinone [1129-21-1] ia 92% yield. 

Although no acyl hypochlorites [RCO2CI] have been isolated in pure form, they have been characterized in solution and employed as reactants via in situ generation from CI2O or HOCl and carboxyUc acids, or from CI2 and silver salts of carboxyUc acids (246,247). Perfluoroacyl hypochlorites have also been prepared (248). 

MIcrobiocldes. There are several microbiocides available commercially that can perform an effective function in controlling microbial activity. Some of these chemicals are inorganic, such as chlorine, sodium hypochlorite, calcium hypochlorite, hydrogen peroxide, chromates and compounds of mercury and silver. However, the organic chemicals find the highest use as microbiocides. Some examples of these organic compounds are peracetic acid, paraformaldehyde, polychlorophenols and quaternary ammonium derivatives, to name a few [208]. 

On heating in air, nickel forms a protective oxide and gives good service up to 700°C. Nickel is not recommended for exposure to chlorine, sulphur dioxide, nitric acid, sodium hypochlorite, mercuric or silver salts. 

Acridine-9-carbaldehyde (24%) is one of several products formed from the oxidation of 5//-dibenz[A/]azepine with tert-butyl hypochlorite in dichloromethane at — 70 C.229 The reaction is even more complex in the presence of silver(I) trifluoroacetate, and an analysis of the reaction mixture by GC-MS techniques reveals the presence of eleven products, the major ones being acridine (37%), an unidentified 5//-dibenz[/ ,/]azepinecarbaldehyde (23%) and acridine-9-carbaldehyde (9 %). 

Chiral alcohols have also been used in an asymmetric synthesis of sulphoxides based on halogenation of sulphides. Johnson and coworkers have found319 that the reaction of benzyl p-tolyl sulphide with JV-chlorobenzotriazole (NCBT) followed by addition of (—) menthol and silver tetrafluoroborate afforded diastereoisomeric menthoxysulphonium salts 267 which, upon recrystallization and hydrolysis, gave benzyl p-tolyl sulphoxide with 87% optical purity (equation 145). More recently, Oae and coworkers reported320 that optically active diaryl sulphoxides (e.e. up to 20%) were formed either by hydrolysis or thermolysis of the corresponding diaryl menthoxysulphonium salts prepared in situ from diaryl sulphides using ( —) menthol and t-butyl hypochlorite. 

Sodium chloride Hypochlorites Potassium dichromate Copper cyanide Nickel cyanide Potassium cyanide Silver cyanide Sodium cyanide Zinc cyanide Suds... 

Acetone Acetylene Alkali and alkaline earth metals, e.g. sodium, potassium, lithium, magnesium, calcium, powdered aluminium Anhydrous ammonia Concentrated nitric and sulphuric acid mixtures Chlorine, bromine, copper, silver, flourine or mercury Carbon dioxide, carbon tetrachloride, or other chlorinated hydrocarbons. (Also prohibit, water, foam and dry chemical on fires involving these metals - dry sand should be available.) Mercury, chlorine, calcium hypochlorite, iodine, bromine or hydrogen fluoride... 

Anon., Environment, Safety Health Bull., 1993, 93(2), 1 As part of an analytical procedure prior to silver recovery, 10 ml commercial hypochlorite solution (15% available chlorine ) was added to highly alkaline waste developer solution. The redox reaction was violent enough to spray the worker, causing alkali bums. 

Interaction of chlorine with methane is explosive at ambient temperature over yellow mercury oxide [1], and mixtures containing above 20 vol% of chlorine are explosive [2], Mixtures of acetylene and chlorine may explode on initiation by sunlight, other UV source, or high temperatures, sometimes very violently [3], Mixtures with ethylene explode on initiation by sunlight, etc., or over mercury, mercury oxide or silver oxide at ambient temperature, or over lead oxide at 100°C [1,4], Interaction with ethane over activated carbon at 350°C has caused explosions, but added carbon dioxide reduces the risk [5], Accidental introduction of gasoline into a cylinder of liquid chlorine caused a slow exothermic reaction which accelerated to detonation. This effect was verified [6], Injection of liquid chlorine into a naphtha-sodium hydroxide mixture (to generate hypochlorite in situ) caused a violent explosion. Several other incidents involving violent reactions of saturated hydrocarbons with chlorine were noted [7],... 

Treatment of D-glucoascorbic acid (XV) with diazomethane gives a 2,3-dimethyl derivative (LXXIX) and this upon repeated treatment with silver oxide and methyl iodide yields 2,3,5,6,7-pentamethyl-D-glucoascorbic acid (LXXX). Ozonization of the latter followed by hydrolysis gives oxalic acid and 3,4,5-trimethyI-D-arabonic acid (LXXXI). This acid was shown to possess a free hydroxyl group at C2 by reason of the fact that the amide of LXXXI gives a positive Weerman reaction for a-hydroxy amides, i.e., when the amide is treated with sodium hypochlorite, sodium isocyanate is produced, the latter being identified by... 

Nitropropane Nitrosyl fluoride Nitrosyl perchlorate Nitrourea Nitrous acid Nitryl chloride Oxalic acid See under Nitromethane chlorosulfonic acid, oleum Haloalkenes, metals, nonmetals Acetones, amines, diethyl ether, metal salts, organic materials Mercury(II) and silver salts Phosphine, phosphorus trichloride, silver nitrate, semicarbazone Ammonia, sulfur trioxide, tin(IV) bromide and iodide Furfuryl alcohol, silver, mercury, sodium chlorate, sodium chlorite, sodium hypochlorite... 

Baum and Archibald reported the synthesis of 2,2,6,6-tetranitrobicyclo[3.3.1]nonane (142). This synthesis starts from the dioxime (140), which on halogenation with chlorine, followed by oxidation with hypochlorite and reductive dehalogenation with hydrogen in the presence of palladium on carbon, yields 2,6-dinitrobicyclo[3.3.1]nonane (141). Oxidative nitration of (141) with sodium nitrite and silver nitrate under alkaline conditions yields 2,2,6,6-tetranitrobi-cyclo[3.3.1]nonane (142). The greater molecular freedom in 2,2,6,6-tetranitrobicyclo[3.3.1] nonane (crystal density-1.45 g/cm ) compared to the isomeric 2,2,6,6-tetranitroadamantane (crystal density-1.75 g/cm ) is reflected is their considerably different crystal densities. 

Phenyl-l,2,4-triazoline-3,5-dione has been prepared by oxidizing 4-phenylurazole with lead dioxide,7 and with ammoni-acal silver nitrate followed by an ethereal solution of iodine.8 The yields are low for both methods. 4-Substituted triazoline-diones can also be made by oxidation of the corresponding urazole with fuming nitric acid9 or dinitrogen tetroxide.10 Oxidation by <-butyl hypochlorite in acetone solution has also been described 1112 it, however, yields an unstable product, even after sublimation. Either dioxane12 or ethyl acetate are preferred as solvents for the reaction, since the product is obtained in a stable form. The latter solvent is superior since... 

Azetidin-2-one can be synthesized by treating 1-ethoxy-1-hydroxycy-clopropane with aqueous sodium azide at pH 5.5 (Scheme 8.7a). This type of construction has wider applications and A-substituted derivatives are formed from 1-amino-1-hydroxycyclopropanes in two steps first A-chlorination with tert- miy hypochlorite [2-methylpropan-2-yl chlo-rate(I)], and then treatment with silver ion in acetonitrile (ethanenitrile) to release chloride ion and trigger ring expansion of the tricycle (Scheme 8.7b). 

Other agents are also available, which are used to remove pigmentation of teeth e.g. weak ammonia solution is used to remove iodine stains, hypochlorite or iodine solution are used to remove silver stains, hypochlorites are used to remove iron stains of teeth and for dye stains, chlorinated lime and acetic acid are used. 

The following inorganic hypochlorites are described in literature aluminum (very unstable), ammonium (very unstable), barium, calcium, cupric, lithium, magnesium, potassium, silver (unstable), sodium, strontium and zinc. None of these salts is used in explosives or is explosive per se, but some of them are used in industry... 

Sodium hypochlorite reacts with (1) to give the 1-chloro derivative, which gives rise to a variety of products, including the bicyclic amine, pyrrolizidine, when treated with silver salts (72CJCH67). Quaternary salts derived from (3) react with sodium methoxide to give mostly the acyclic Hofmann elimination product (83%) minor amounts of (3) (14%) are also formed, together with a trace (2%) of the product of 5N2 attack on the a-methylene carbon (80JOC3952). 

A. J. Balard found mercury immediately decomposes hypochlorous acid without the disengagement of any gas, but mercury oxychloride is formed. P. Grouvelle reported previously that when chlorine acts on mercuric oxide suspended in water, mercury oxychloride, very slightly soluble in cold water, is formed. L. J. Thenard found that the liquid contained both chloride and chlorate of mercury, also in soln. A. J. Balard, however, believed that these bodies are formed consecutively, and that their existence was preceded by that of a mercuric hypochlorite, as takes place with the salts of silver, and, as previously indicated, he prepared hypochlorous acid by the action of chlorine on mercuric oxide suspended in water. No mercury hypobromite has yet been isolated. There is a possible formation of mercury hypoiodite, or more probably of hypoiodous acid, when iodine is shaken up with... 

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