Tetrabutylammonium hypochlorite

Secondary benzylic chlorides and bromides give aromatic ketones on oxidation with chromium trioxide [5<5f>] or with tetrabutylammonium hypochlorite [690] (equations 198 and 199). 

Hypochlorites are very good oxidizers of alcohols and are frequently selective enough to oxidize secondary alcohols in preference to primary alcohols see equations 288-291). Solutions of sodium hypochlorite in acetic acid react exothermically with secondary alcohols within minutes [693]. Calcium hypochlorite in the presence of an ion exchanger (IRA 900) oxidizes secondary alcohols at room temperature in yields of 60-98% [76 5]. Tetrabutylammonium hypochlorite, prepared in situ from 10% aqueous sodium hypochlorite and a 5% dichloromethane solution of tetrabutylammonium bisulfate, oxidizes 9-fluorenol to fluorenone in 92% yield and benzhydrol to benzophenone in 82% yield at room temperature in 35 and 150 min, respectively [692]. Cyclohexanol is oxidized to cyclohexanone by teit-butyl hypochlorite in carbon tetrachloride in the presence of pyridine. The exothermic reaction must be carried out with due precautions [709]. 

Nitrogen analogues of sulfoxides, sulfilimines, when protected by a tosyl group at the nitrogen, are converted into nitrogen analogues of sulfones, sulfoximines, by tetrabutylammonium hypochlorite, which is pre-... 

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... 

A number of new procedures have been developed for the oxidation of sulfur-linked substituents on the pyridine ring at sulfur. 2- and 4-Pyridinethiols may be oxidized to the corresponding sulfonyl chloride at low temperature using sodium hypochlorite in a mixture of dichloromethane and 1M aqueous HC1 <2006JOC1080>. Treatment of the crude solution of sulfonyl chloride in dichloromethane with benzylamine results in rapid conversion to the sulfonamide. Carrying out the oxidation in the presence of KHF2 and tetrabutylammonium sulfate results in conversion to the sulfonyl fluoride. For example, 2-pyridinethiol is converted to the sulfonamide in 98% yield and the sulfonyl fluoride in 70% yield using this procedure (Scheme 27). In the same manner, 4-pyridinethiol is converted to the sulfonyl chloride in 39% yield and 2-quinolinethiol is converted to the sulfonyl chloride and sulfonyl fluoride in 80% and 49% yield, respectively. 

Iodobenzene (1.01 g, 4.9 mmol) was dissolved in dichloromethane (75 ml) and stirred vigorously with hypochlorite solution (200 ml of commercial laundry bleach adjusted to pH 8.2 and containing 200 mg of tetrabutylammonium hydrogen sulphate) at room temperature for 45 min. The reaction mixture was allowed to stand for 1 h then the precipitate was filtered to give crude iodylbenzene (0.69-0.94 g, 59-81%). Purification may be effected by crystallization from water or acetic acid. 

The same 8-chloroadenosine (5) is also obtained with tetrabutylammonium iodotetrachloride (TBAIClJ or with tert-butyl hypochlorite (r-BuOCl) in dimethylformamide. Analogous chlorination of -methyladenosine, to give 6, and A. A -dimethyladenosine is also possible with the latter reagent. ... 

Hexylamine is converted into capronitrile in 73% yield on refluxing with nickel peroxide in benzene for 1.5 h [936]. Octylamine is dehydrogenated to octanenitrile in 60% yield by treatment with sodium hypochlorite and tetrabutylammonium hydrogen sulfate in ethyl acetate at room temperature for 35 min [692], The preparation of benzonitrile is shown in equation 514 [196, 381, 1136]. 

Hypochlorite ion is an effective oxidizing agent for a variety of substrates when the reactions are conducted under phase transfer conditions [13]. Tetrabutylammonium ion catalyzes the reaction of hypochlorite with benzylic alcohols in dichloromethane or ethyl acetate solution to yield alcohols and ketones. Likewise, secondary alcohols are oxidized to ketones according to equation 11.6. The results of a series of such... 

A variety of phenanthrenes have been oxidized to the K-region epoxides using a mixture of sodium hypochlorite, hydrogen peroxide, chloroform and tetrabutylammonium bisulfate at room temperature. Buffering to maintain pH in the range 8—9 was found efficacious and yields were generally in the range 70—90%. 

Sodium hypochlorite tetrabutylammonium hydrogen sulfate NaOCUBu N HSOf Phase transfer catalyzed oxidations with hypochlorite... 

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