Butyl hypochlorite

Caution This preparation should be carried out in a hood to avoid exposure to the hypochlorite produced. To avoid vigorous decomposition the product should be handled only in dim light and should not be heated above its boiling point or be exposed to rubber. 

In a l-I. Erlenmcycr or round-bottomed flask equipped with a mechanical stirrer is placed 5(K) ml. of a commercial household 

The entire reaction mixture is poured into a 1-1. separatory funnel. The lower aqueous layer (Note 5) is discarded, and the oily yellow organic layer is washed first with a 50-ml. portion of 10% aqueous sodium carbonate and then with 50 ml. of water. The product is dried over 1 g. of calcium chloride and filtered. The yield of butyl hypochlorite, 99-100% pure, is 29.6-34 g. (70-80%) (Notes 1,6). The product can be stored conveniently in a freezer or refrigerator over calcium chloride in amber glass bottles (Note 7). 

Whereas the inorganic hypochlorite is rather stable to photodecomposition, i-butyl hypochlorite is much more readily decomposed. It is not necessary to work in a totally darkened mom, 

The t-butyl alcohol was a commercial product obtained from Matheson Coleman and Bell, and the glacial acetic acid a commercial product obtained from Union Carbide. 

Pale yellow liquid with irritating odor bp, 77-78°C.1 

Ampoules liable to burst unless stored in a cool, dark place. It should not be heated above its boiling point.2,3 Violent reaction if exposed to strong light or overheating.1 Rubber. Violent reaction.3 

Wear eye protection, laboratory coat, and nitrile rubber gloves. Work from behind heavy body shield. Cover spill with a 1 1 1 mixture by weight of sodium carbonate or calcium carbonate, clay cat litter (bentonite), and sand. Carefully scoop mixture into a beaker of cold water in the fume hood. Add a 10% solution of sodium bisulfite, allowing 10 mL of bisulfite solution for each 1 mL of hypochlorite spilled. Let stand until solids settle. Decant the liquid into the drain. The solid residue can be discarded as normal refuse.4 Wash the spill area thoroughly with soap and water. 

Wear nitrile rubber gloves, laboratory coat, and eye protection. Work in the fume hood. 

Slowly add the t-butyl hypochlorite to an excess of a stirred, cold 10% solution of sodium bisulfite. Allow 10 mL of the bisulfite solution for each 1 mL of hypochlorite. When reaction has ceased, wash into the drain.3 

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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. 

There are two sequences in which the reaction can be carried out. For most anilines the first step is /V-chlorination which can be done with t-butyl hypochlorite[9]. However, for anilines with ER substituents it may be preferable to halogenate the thioester. The halogenation can be done with Cl2[lbl or SOjCljCU]. For some anilines simply adding f-butyl hypochlorite to a mixture of the aniline and thioester is satisfactory (Entries 1, 4, Table 7.6). 

A solution of 2-aminobenzophenone (98 g, 0.50 mol) and methyl 2-(methyl-thio)propanoate (74 g, 0,50 mol) in CH Clj (21) was cooled to —70 C and 95% 7-butyl hypochlorite (56 g, 0.5 mol) was added dropwise at such a rate that the temperature did not rise above — 65 C. One hour after the addition was complete, EtjN was added and the mixture was allowed to come to room temperature. The solution w as mixed with 3 N HCl (800 ml) and stirred for 1 h. The organic layer was separated, dried (Na2S04 ) and filtered. The solution was evaporated in vacuo and the residue triturated with ether. Filtration gave the 3-(methylthio)oxindole intermediate (92 g) in 62% yield. 

The kinetics of formation and hydrolysis of /-C H OCl have been investigated (262). The chemistry of alkyl hypochlorites, /-C H OCl in particular, has been extensively explored (247). /-Butyl hypochlorite reacts with a variety of olefins via a photoinduced radical chain process to give good yields of aUyflc chlorides (263). Steroid alcohols can be oxidized and chlorinated with /-C H OCl to give good yields of ketosteroids and chlorosteroids (264) (see Steroids). /-Butyl hypochlorite is a more satisfactory reagent than HOCl for /V-chlorination of amines (265). Sulfides are oxidized in excellent yields to sulfoxides without concomitant formation of sulfones (266). 2-Amino-1, 4-quinones are rapidly chlorinated at room temperature chlorination occurs specifically at the position adjacent to the amino group (267). Anhydropenicillin is converted almost quantitatively to its 6-methoxy derivative by /-C H OCl in methanol (268). Reaction of unsaturated hydroperoxides with /-C H OCl provides monocyclic and bicycHc chloroalkyl 1,2-dioxolanes. 

Butyl hypochlorite has been used for the preparation of epoxides (269). 

Uses. /-Butyl hypochlorite has been found useful in upgrading vegetable oils (273) and in the preparation of a-substituted acryflc acid esters (274) and esters of isoprene halohydrins (275). Numerous patents describe its use in cross-linking of polymers (qv) (276), in surface treatment of mbber (qv) (277), and in odor control of polymer latexes (278). It is used in the preparation of propylene oxide (qv) in high yield with Httle or no by-products (269,279). Fluoroalkyl hypochlorites are useful as insecticides, initiators for polymerizations, and bleaching and chlorinating agents (280). 

Pyridazine-3,6-diones (diazaquinones) are prepared from cyclic hydrazides by oxidation with lead tetraacetate or other oxidizing agents, such as r-butyl hypochlorite, chlorine or nickel peroxide. 

In a similar manner to the formation of pyridazines from AT-aminopyrroles, cinnolines or phthalazines are obtainable from the corresponding 1-aminooxindoles or 2-amino-phthalimides. If the relatively inaccessible 1-aminooxindoles are treated with lead tetraacetate, mercuric acetate, r-butyl hypochlorite (69JCS(C)772) or other agents, cinnolones are formed as shown in Scheme 105. The reaction was postulated to proceed via an intermediate... 

In comparison to N—S bond formation, O—N bond formation by essentially oxidative procedures has found few applications in the synthesis of five-membered heterocycles. The 1,2,4-oxadiazole system (278) was prepared by the action of sodium hypochlorite on A(-acylamidines (277) (76S268). The A -benzoylamidino compounds (279) were also converted into the 1,2,4-oxadiazoles (280) by the action of r-butyl hypochlorite followed by base. In both cyclizations A -chloro compounds are thought to be intermediates (76BCJ3607). 

Treatment of a carborane derivative of thiirane with A-bromosuccinimide gives a j3-bromodisulfide (79MI50601). Chlorination of CM-2,3-di-f-butylthiirane by f-butyl hypochlorite proceeded differently to the reaction with chlorine itself (Scheme 41) (74JA3146). 

Diaziridinimines were made analogously. Tri-t-butylguanidine (281) with r-butyl hypochlorite gave (176) in 80% yield. (281) itself is a sufficiently strong base to deprotonate its Af-chloro derivative (69AG(E)448). This procedure also works with methyl- or phenyl-substituted guanidines. 

Syntheses of alkyldiazirines (287) must start from the diazirinotriazolidines (128) formed from an aldehyde, ammonia and (-butyl hypochlorite. Since the three-membered ring in (128) is much more stable towards acids than the five-membered ring (Section 5.08.3.2.2), the diazirines are obtained by acid hydrolysis of compounds (128) in the presence of an oxidant (62CB795). 

Another reagent which effects chlorination by a radical mechanism is f-butyl hypochlorite. The hydrogen-abstracting species in the chain mechanism is the f-butoxy radical. 

Ammonium sulfate triolein, oleic acid, androsten-3,17-dione, xanthanonic acid, cholesterol-propionate, N-methy Ipheny lalanine, D-glucose fluorescence after heating to 150 — 180 °C, exposure to tert-butyl hypochlorite [203]... 

Dipping solution I Dissolve 1 ml /ert-butyl hypochlorite in 100 ml carbon tetrachloride or cyclohexane. 

Dipping solution I may be stored in the refrigerator for a few days. tert-Butyl hypochlorite should be stored cool in the dark under an atmosphere of nitrogen. 

Caution ter/-Butyl hypochlorite is very reactive, e.g. it reacts violently with rubber seals particularly under the influence of light. 

Chlorohydnns and 1,2-dichloro denvatives are obtamed by oxidation of alkenes with fert-butyl hypochlorite when the reaction is performed in acetic acid instead of water, chlorohydrm acetate is formed [Ji] (equation 25)... 

Fluoroalkyl selenides are oxidized to higher oxidation states by tert-butyl hypochlorite under the mild conditions [115] (equation 105)... 

The amine hydrogens of polyfluorinated anilines can be replaced with chlorine by using tert-butyl hypochlorite [65,66]... 

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