Sodium hypobromite, preparation

A solution of sodium hypobromite, prepared by dissolving 42 g (1.05 mol) of sodium hydroxide in 200 mL of water and adding 15 mL (47 g, 0.29 mol) of bromine at 0 C, is added over a 30-min period to a stirred solution of 15.0 g (0.066 mol) of 4-(p-methoxyphenyl)acetophenone in 150 mL of dioxane. During the addition, the temperature is allowed to rise to 35-40 °C. After being stirred for an additional 15 min, the mixture is treated with enough sodium bisulfite to destroy the excess of sodium hypobromite. Water (1 L) is added, and 200 mL of water is distilled off to remove the bromoform and some dioxane. Acidification of the hot solution and subsequent cooling yields 13.8 g (91%) of 4-(p-methoxyphenyl)benzoic acid, mp 247-248 °C. 

The pinacolone may be employed for the preparation of trimethylacetlc acid (plvallc acid) by oxidation with sodium hypobromite solution ... 

Method 2 (from hydrazobenzene). Prepare a solution of sodium hypobromite by adding 10 g. (3-2 ml.) of bromine dropwise to a cold solution of 6-0 g. of sodium hydroxide in 75 ml. of water immersed in an ice bath. Dissolve 9-5 g. of hydrazobenzene (Section IV,87) in 60 ml. of ether contained in a separatory funnel, and add the cold sodimn hypobromite solution in small portions. Shake for 10 minutes, preferably mechanically. Separate the ether layer, pour it into a 100 ml. distilling flask, and distil off the ether by warming gently on a water bath. Dissolve the warm liquid residue in about 30 ml. of alcohol, transfer to a small beaker, heat to boiling on a water bath, add water dropwise to the hot solution until the azobenzene just commences to separate, render the solution clear again with a few drops of alcohol, and cool in ice water. Filter the orange crystals at the pump, and wash with a little 50 per cent, alcohol. Dry in the air. The yield is 8 g. 

Anthranilic acid. This substance, the ortho amino derivative of benzoic acid, may be conveniently prepared by the action of sodium hypobromite (or sodium hypochlorite) solution upon phthalimide in alkaline solution at 80°. The ring in phthalimide is opened by hydrolysis to phthalamidic acid and the latter undergoes the Hofmann reaction (compare Section 111,116) ... 

Good results are obtained by the oxidation of the commercially available cyclo-propyl methyl ketone with sodium hypobromite solution, and the preparation may be regarded as an excellent example of the oxidation of the —COCH, group to — OOH ... 

Hypobromites, the salts of hypobromous acid, do not keep well because they gradually disproportionate to bromide and bromate. Solutions are best prepared as needed from bromine and alkafl with cooling. Because disproportionation is catalyzed by cobalt, nickel, and copper (70), these impurities should be avoided. SoHd alkaline earth hypobromites, or more properly, bromide hypobromites such as calcium bromide hypobromite [67530-61 CaBr(OBr), have been known for many years, but the pure crystalline hydrates sodium hypobromite pentahydrate [13824-96-9] NaOBr 5H20, and potassium hypobromite tribydrate [13824-97-0], KOBr 3H20, were not described until 1952 (71). Hypobromites are strong bleaching agents, similar to hypochlorites. 

Alicyclic hydroxamic acids undergo several specific oxidative cleavage reactions which may be of diagnostic or preparative value. In the pyrrolidine series compounds of type 66 have been oxidized with sodium hypobromite or with periodates to give y-nitroso acids (113). Ozonolysis gives the corresponding y-nitro acids. The related cyclic aldonitrone.s are also oxidized by periodate to nitroso acids, presumably via the hydroxamic acids.This periodate fission was used in the complex degradation of J -nitrones derived from aconitine. 

The above procedure is essentially that of Ullmann and Bleier.2 2-Aminobenzophenone has also been prepared by reduction of 2-nitrobenzophenone,3 by the Hofmann reaction of the amide of o-benzoylbenzoic acid with sodium hypobromite,4 by the action of an excess of benzoyl chloride on aniline at 220°,6 and by hydrolysis of the acetyl derivative which is obtained by the action of phenylmagnesium bromide on 2-methyl-3,l,4-benzoxaz-4-one (from anthranilic acid and acetic anhydride).6 Various methods for the preparation of 2-aminobenzophenones have been summarized critically by Simpson, Atkinson, Schofield, and Stephenson.7... 

A. J. Balard 6 prepared a soln. of sodium hypobromite, NaOBr, by working in a similar manner to the process employed for the hypochlorite. When bromine is gradually added to soda lye, the bleaching power increases up to a maximum, and after that decreases owing to the conversion of the hypobromite into bromate. A. J. Balard also described a similar product, potassium hypobromite, obtained by the action of bromine on potassium carbonate. 

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. 

Most pyrimido[4,5-d]pyridazines are prepared from 4,5-disubstituted pyridazine precursors. The versatile intermediate pyrimido[4,5-cf]pyridazine-2,4-dione (85) can readily be formed in high yield from pyridazine-4,5-dicarboxamide (196) by reaction with sodium hypobromite in a Hofmann type reaction (68JHC53). 

By treatment of an amide with sodium hypobromite or sodium hypochlorite solution (or with halogen admixed with aqueous alkali), a primary amine having one less carbon atom is produced. Good yields are obtained when the reaction is applied to most aliphatic and aromatic amides. Examples are provided by the preparation of anthranilic acid and 3-aminopyridine (Expt 6.53). 

Cognate preparation. 3-Aminopyridine. Prepare a cold sodium hypobromite solution from 32 g (10 ml, 0.2 mol) of bromine and 25 g (0.62 mol) of sodium hydroxide in 250 ml of water. Add in one portion 20 g (0.163 mol) of finely powdered nicotinamide (Expt 6.169) and stir vigorously for 15 minutes. Warm the solution in a water bath at 75 °C for 45 minutes. Isolate the crude product by continuous ether extraction (Section 2.22) of the cooled reaction mixture after saturation with sodium chloride. Dry the extract over potassium hydroxide pellets and remove the ether. Crystallise the dark residue from a 4 1 mixture of benzene-light petroleum (b.p. 60-80 °C) with the aid of decolourising charcoal. The yield of almost colourless product, m.p. 63 °C, is 9.3 g (61%). 

Many of the iV-alkyl and iV-aryl derivatives of urazine have been synthesized and characterized, but the parent substance is not well known. In the past, urazine has been prepared by thermal deammonation of carbohydrazide-iV-carboxamide [eq. (I)],1 fusion of hydrazidicarbamide with hydrazinium hydrogen sulfate [eq. (2)],2 fusion of earbohy-drazide with urea [eq. (3)],3 action of sodium hypobromite on semicarbazide [eq. (4)],4 reaction of dichlorourea with concentrated ammonia [eq. (5)],5 and the reaction between 1,2 hydrazine carboxylic ester and hydrazine hydrate... 

Dimethylglutaric acid has been prepared by heating di-methylpropanetricarboxylic acid above its melting point 3 by hydrolysis of the condensation product of ethyl cyanoacetate and ethyl /3,/3-dimethylacrylate 7 by the action of sulfuric acid on diethyl /3,/3-dimethyl-a,a -dicyanoglutarate 8 by hydrolysis of the nitrile obtained by the action of calcium cyanide on /3,/3-di-methylbutyrolactone 4 by the action of sulfuric acid on /3,/3-di-methyl-a,c/-dicyanoglutarimide 9 and by the action of sodium hypobromite on methone.5 The present procedure is essentially that of Walker and Wood.6... 

The synthesis of BENZYL ISOCYANIDE from benzaldehyde via reductive amination with 5-aminotetrazole followed by oxidation of the resultant amine with sodium hypobromite provides a general method for the synthesis of isocyanides. The preparation of BIS(2,2,2-TRICHLOROETHYL) AZODICARBOXYLATE makes available an alternative to dimethyl azodicarboxylate that is not only more reactive in Diels-Alder reactions but whose ester groups can be removed under neutral conditions. 

If the solution of tetracyanonickelate(II) is heated with sodium hypobromite solution (prepared in situ by adding bromine water to sodium hydroxide solution), the complex decomposes and a black nickel(III) hydroxide precipitate is formed (difference from cobalt ions) ... 

Sodium hypobromite (0-25m). To 50 ml freshly prepared bromine water add 2m sodium hydroxide dropwise, until the solution becomes colourless (about 50 ml is needed). 

---