Calcium hypochlorite ketones

Prepare a solution containing about 100 g, of potassium hypochlorite from commercial calcium hypochlorite ( H.T.H. ) as detailed under -Dimethylacrylic Acid, Section 111,142, Note 1, and place it in a 1500 ml. three-necked flask provided with a thermometer, a mechanical stirrer and a reflux condenser. Warm the solution to 55° and add through the condenser 85 g, of p-acetonaphthalene (methyl p-naphthyl ketone) (1). Stir the mixture vigorously and, after the exothermic reaction commences, maintain the temperature at 60-70° by frequent cooling in an ice bath until the temperature no longer tends to rise (ca. 30 minutes). Stir the mixture for a further 30 minutes, and destroy the excess of hypochlorite completely by adding a solution of 25 g. of sodium bisulphite in 100 ml. of water make sure that no hypochlorite remains by testing the solution with acidified potassium iodide solution. Cool the solution, transfer the reaction mixture to a 2-litre beaker and cautiously acidify with 100 ml. of concentrated hydrochloric acid. Filter the crude acid at the pump. 

Reaction of HOCl, formed from calcium hypochlorite and CO2, with highly substituted alkenes in CH2CI2 is a convenient route to aHyUc chlorides (111). Ketones are chlorinated to a-chloroketones by reaction with HOCl Acetone initially gives CH2COCH2CI (112). Methyl ethyl ketone gives 78% CH3CHCICOCH3, 15% CH3CH2COCH2CI, and 7% dichlorides (113). 

In a 3-I. round-bottomed flask 250 g. of commercial calcium hypochlorite is dissolved in i 1. of warm water and a warm solution of 175 g. of potassium carbonate and 50 g. of potassium hydroxide in 500 cc. of water is added. The flask is stoppered and shaken vigorously until the semi-solid gel which first forms become quite fluid. The suspended solid is removed by filtration on a large Buchner funnel, washed with 200 cc. of water, and sucked as dry as possible with the aid of a rubber dam and an efficient suction pump. The filtrate of approximately 1500 cc. is placed in a 3-I. round-bottomed flask and is ready for the addition of methyl /3-naphthyl ketone. 

The earliest methods for preparing cyclic a-diazo ketones involved the oxidation of the monohydrazones prepared from a-diketones, generally using mercuric oxide.7,8 Recent modifications of this procedure include the use of calcium hypochlorite in aqueous sodium hydroxide or activated manganese dioxide as oxidants.1 The latter reagent, especially, hoc ms preferable to mercuric oxide. The base-catalyzed decomposition of tile monotosylhydrazoneH of a-diketones has been... 

Rearrangement of NJV-dilmloanunesf N,N-Dichloro-tri-n-butylcarbinamine (2), prepared by treatment of tri-n-butylcarbinamine (I) with calcium hypochlorite, when treated with aluminum chloride in methylene chloride at - 30°, followed by acid hydrolysis, gives di-n-butyl ketone (3) and n-butylaminc (4) in high yield. The reaction is considered to involve alkyl migration to electron-deficient nitrogen. 

Amyl Alcohol 70 j 275 Calcium Hypochlorite (94%) 275 Diisobutyl Ketone ... 

Tomdogy LD50 (oral, rat) 6300 mg/kg, (skin, rabbit) > 2000 mg/kg severe eye irritant mild skin irritant inh. may irritate respiratory tract TSCA listed Precaution Incompat. with oxidizers, reactive metals, sodium or calcium hypochlorite, dehydrating agents reaction with peroxide may create explosion Hazardous decomp, prods. May generate toxic or irritating combustion prods., CO, COj, aldehydes, ketones HMIS Health 2, Flammability 1, Reactivity 0 Storage Store In cool, dry, ventilated area in closed containers Surfynol EP-830 [Air Prods./Perf. Chems.]... 

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