Sodium hypochlorite/chloroform

The nitrile oxides can be generated by various methods. Generation from bromoaldoximes in a chloroform/sodium hypochlorite biphase medium is efficient. ... 

Similar [3 4-2] cycloadditions with C-aryl nitrile oxides and other terminal fiuoroalkylated al-kenes (RF = C2F5, C6F13) and fiuoroalkylated alkynes provide high yields of cycloadducts.86,87 The nitrile oxides can be generated by various methods. Generation from bromoaldoximes in a chloroform/sodium hypochlorite biphase medium is efficient.86... 

The reactions involved are similar in both cases, and closely parallel to those which give rise to chloroform. The sodium hypochlorite probably first oxidises the potassium iodide to potassium hypoiodite, which then oxidises the ethanol to acetaldehyde and then iodinates the latter to tri-iodo ... 

Acetone (R = CHj) when treated with sodium hypochlorite or bleaching powder solution yields chloroform, probably in accordance with the following mechanism ... 

The need for low levels of 3-isomer in 2-thiophenecarboxyhc acid [527-72-0] which is produced by oxidation of 2-acetylthiophene [88-15-3] and used in dmg appHcations, has been the driving force to find improved acylation catalysts. The most widely used oxidant is sodium hypochlorite, which produces a quantity of chloroform as by-product, a consequence that detracts from its simplicity. Separation of the phases and acidification of the aqueous phase precipitate the product which is filtered off. Alternative oxidants have included sodium nitrite in acid solution, which has some advantages, but, like the hypochlorite method, also involves very dilute solutions and low throughput volumes. 

A 5—6% sodium hypochlorite solution is sold for household purposes, of which the largest use is in laundry. Solutions of 10—15% NaOCl are sold for swimming pool disinfection, institutional laundries, and industrial purposes. Solutions of various strengths are used in household and industrial and institutional (I I) cleaners, disinfectants, and mildewcides. A small amount is used in textile mills. Sodium hypochlorite is also made on site with 30—40 g/L available chlorine for pulp bleaching, but its use is decreasing in order to reduce chloroform emissions (see Chlorine oxygen acids and salts). 

Efaloform Reaetion. Ethyl alcohol reacts with sodium hypochlorite to give chloroform [67-66-3] (haloform reaction). 

Carbodiimides have been prepared by desulfurization of thioureas by metal oxides, by sodium hypochlorite,4 or by ethyl chloroformate in the presence of a tertiary amine by halogena-tion of ureas or thioureas followed by dehydrohalogenation of the N,N -disubstituted carbamic chloride 8 and by dehydration of disubstituted ureas using -toluenesulfonyl chloride and pyridine.7 The method described above is a modification of that of Campbell and Verbanc. ... 

The flow-cell design was introduced by Stieg and Nieman [166] in 1978 for analytical uses of CL. Burguera and Townshend [167] used the CL emission produced by the oxidation of alkylamines by benzoyl peroxide to determine aliphatic secondary and tertiary amines in chloroform or acetone. They tested various coiled flow cells for monitoring the CL emission produced by the cobalt-catalyzed oxidation of luminol by hydrogen peroxide and the fluorescein-sensitized oxidation of sulfide by sodium hypochlorite [168], Rule and Seitz [169] reported one of the first applications of flow injection analysis (FTA) in the CL detection of peroxide with luminol in the presence of a copper ion catalyst. They... 

Tribromomethane [75-25-2] (bromoform), CHBr3, is usually sold mixed with up to 3—4% ethanol as a stabilizer. The pure liquid has mp, 7.7°C bp, 149.5°C cP A, 2.8912 g/mL 19D 1.5980 (87). Water solubility is about 0.3 g/100 g at 25°C. Bromoform is prepared from chloroform by the replacement procedures indicated (88). The classical method of preparation involves reaction of acetone and sodium hypobromite the latter may be generated from sodium hypochlorite and a bromide (89). Uses have been found in syntheses, in pharmacy as a sedative and antitussive, in gauge fluids, and as a dense liquid for separating minerals. Traces of bromoform and bromochloroforms are likely to be present in municipal waters and wastes as a result of chlorination in the presence of naturally occurring bromide ions and humic substances (90). Removal can be accomplished by adsorption on activated charcoal. 

MIX 5 ml ETHANOL WITH 5 ml SODIUM HYPOCHLORITE SOLUTION ("CLO-ROX"). HEAT MIXTURE GENTLY FOR A FEW MOMENTS WITHOUT 801 LING. THEN SNIFF CAREFULLY. YOU GET THE PECULIAR SWEETISH ODOR OF CHLOROFORM. THE C,HsOH HAS BEEN TURNED INTO CHCI,. 

Exercise 17-12 Trichloromethane (chloroform) at one time was synthesized commercially by the action of sodium hypochlorite on ethanol. Formulate the reactions that may reasonably be involved. What other types of alcohols may be expected to give haloforms with halogens and base ... 

Another synthetic method involves treating the parent aromatic hydrocarbon with sodium hypochlorite in water-chloroform, using phase transfer agents like tetrabutylammonium hydrogen sulfate or benzyltrimethylam-monium chloride.15 The epoxides are formed in high yields. The rate is pH dependent, and epoxide formation is most facile at pH 8-9. Many K-region arene oxides like 1,165, acenaphthylene 1,2-oxide (19), 1-azaphenanthrene 5,6-oxide (20), 4-azaphenanthrene 5,6-oxide (21), 1,10-phenanthroIine 5,6-oxide... 

Fit a 1-litre three-necked flask with two double surface condensers and a sealed stirrer unit. Place 25 g (29 ml, 0.25 mol) of mesityl oxide (Expt 5.213), 50 ml of dioxane and a cold (10 °C) solution of sodium hypochlorite in 750 ml of water (1) in the flask, and stir the mixture. Heat is evolved in the reaction and after about 5 minutes chloroform commences to reflux. As soon as the reaction becomes very vigorous, stop the stirrer and cool the flask with water so that the chloroform refluxes gently after 20-30 minutes, when the reaction has subsided, resume the stirring and continue it until the temperature of the mixture has fallen to that of the laboratory (2-3 hours). Decompose the slight excess of hypochlorite by the addition of sodium metabisulphite (about 1 g), i.e. until a test-portion no longer liberates iodine from potassium iodide solution. 

Catalyzed oxidations.1 In catalytic procedures with Ru04, periodate or hypochlorite are generally used as the stoichiometric oxidants. The addition of acetonitrile, which is inert to oxidation but an effective ligand for lower valent transition metals, results in much higher yields. A third solvent, chloroform, also plays a significant part. The ruthenium tetroxide is generated in situ from RuCl, (H20)n or Ru02 with sodium or potassium metaperiodate sodium hypochlorite is less effective. 

Reaction of compound (194) with sodium hypochlorite or lead tetraacetate gave the 2-oxide (195) in 70 and 90% yields, respectively (Scheme 16) <87H(26)292i>. Treatment of the 2,4-oxide (196) with phosphorus trichloride in chloroform at reflux selectively deoxygenated compound (196) at the pyridine nitrogen and gave the 2-oxide (195) (63%). 

Note If desired, the bleaching powder can be replaced with Clorox bleach or other Clorox like bleaches (that contain sodium hypochlorite only) however, because most bleach products only contain 5% or less of sodium hypochlorite it would take astronomical amounts of bleach to carryout the reaction, but nonetheless, if you would like to try this technique—by all means just remember to extract the entire huge reaction mixture with extra amounts of benzene, toluene, or xylene to properly recover all of the chloroform)... 

Bromide and iodide in the presence of each other and of chloride The presence of a chloride does not interfere with the reactions described below. To the soda extract, strongly acidified with dilute hydrochloric acid add 1-2 drops of chlorine water (the solution obtained by carefully acidifying a dilute solution of sodium hypochlorite with dilute hydrochloric acid may also be used) and 2-3 ml chloroform or carbon tetrachloride shake a violet colour indicates iodide. Continue the addition of chlorine water or of acidified sodium hypochlorite solution drop by drop to oxidize the iodine to iodate and shake after each addition. The violet colour will disappear, and a reddish-brown colouration of the chloroform or carbon tetrachloride, due to dissolved bromine (and/or bromine monochloride, BrCl), will be obtained if a bromide is present. If iodide alone is present, the solution will be colourless after the violet colour has disappeared. 

Test for iodide in the neutralized soda extract or in a solution of the sodium salts by the addition of a few drops of chlorine water (or acidified sodium hypochlorite solution) and 2-3 ml chloroform or carbon tetrachloride the latter is coloured violet. Add excess silver sulphate solution to another portion of the neutral solution and filter off the silver iodide remove the excess silver sulphate with sodium carbonate solution. Pass sulphur dioxide into the filtrate to reduce iodate to iodide, boil off the excess sulphur dioxide, and add silver nitrate solution and dilute nitric acid. A yellow precipitate of silver iodide confirms the presence of iodate in the original substance. 

Acetyl groups in desaurins may be oxidized to carboxylic acid groups by sodium hypochlorite without affecting the basic bis(methylene)dithietane structure. Treatment of 575 with bromine in chloroform effects replacement of the two methine hydrogen atoms by bromine atoms.An unusual methylene-1,3-dithietane reacts with bis(trifluoromethyl)thioketene to give a complex structure embodying a new methylene-l,3-dithietane and a 2-methylenethietane. Bis-... 

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