Hydrobromic acid, preparation

A solution of cuprous bromide may be prepared either by dissolving the solid in hot constant boiling point hydrobromic acid or by refluxing a mixture of 63 g. of crystallised copper sulphate, 20 g. of copper turnings, 154 g. of sodium bromide dihydrate, 30 g. (16-3 ml.) of concentrated sulphuric acid and 1 litre of water for 3-4 hours. If the colour of the solution has not become yellowish after this period of heating, a few grams of sodium sulphite should be added to complete the reduction. 

The hydrobromic acid sulphuric acid solution may be prepared by the reduction of bromine with sulphurous acid (Section 11,49, 1) distillation of the reaction product is unnecessary ... 

The dibrotnides of aliphatic glycols are best prepared by mixing the glycol with a cold hydrobromic acid - sulphuric acid mixture, allowing to stand for 24 hours, and heating on a steam bath for three hours ... 

The residue in the flask may be mixed with the aqueous layer of the first distillate, 40 g. of isopropyl alcohol added, and the slow distillation repeated. The yield of crude isopropyl bromide in the second distillation is only slightly less than that obtained in the original preparation. Subsequently most of the residual hydrobromic acid may be recovered by distillation as the constant boiling point acid (126°). 

In the preparation of bromo compounds by the Sandmeyer reaction, the amine is generally diazotised in sulphuric acid solution (or in hydrobromic acid solution), and the resulting aryldiazonium sulphate (or bromide) is treated with a solution of cuprous bromide in excess of hydrobromic acid the addition... 

Method 2. Prepare 40 g." of cuprous bromide according to Section 11,50,2 (about 75 g. of crystaUised copper sulphate are required) and dissolve it in 40 ml. of constant boihng point hydrobromic acid (48% HBr) contained in a 2 - 5 Utre rovmd-bottomed flask. 

In a 1 or 1-5 htre round-bottomed flask prepare a solution of 53-5 g. of o-toluidine in 170 ml. of 48 per cent, hydrobromic acid, cool to 5° by immersion in a bath of ice and salt. Diazotise by the gradual addition of a solution of 36 -5 g. of sodium nitrite in 50 ml. of water stopper the flask after each addition and shake until all red fumes are absorbed. Keep the temperature between 5° and 10°. When the diazotisation is complete, add 2 g. of copper powder or copper bronze, attach a reflux condenser to the flask, and heat very cautiously on a water bath. Immediately evolution of gas occurs, cool the flask in crushed ice unless the... 

The last-named reaction provides an excellent method for the preparation of a-substituted glutaric acids the intermediate alkyl (aryl) -2-cyanoethyl-malonate is both hydrolysed and decarboxylated re ily by boiling with an excess of 48 per cent, hydrobromic acid solution. 

Owing to the comparatively negligible difference in the cost of bromine and the equivalent quantity of constant boiling point hydrobromic acid, there is little to be gained—apart from the instructional value— in preparing the hydrobromic acid from bromine in the preparation of alkyl bromides. 

The synthesis of these disubstituied thioureas takes place in three steps. First the alkyl bromide is prepared by the action of hydrobromic acid on the corresponding alcohol (518). Then the dialkylcyanamide is obtained by treatment at 25°C with calcium cyanamide. The yields are of the order of 30 to 60%. Thioureas are obtained in a third step from the cyanamide by reaction at 40 C with HjS in the presence of pyridine. Yields ranged from 57 to 90% (518),... 

Bromoacetic acid can be prepared by the bromination of acetic acid in the presence of acetic anhydride and a trace of pyridine (55), by the HeU-VoUiard-Zelinsky bromination cataly2ed by phosphoms, and by direct bromination of acetic acid at high temperatures or with hydrogen chloride as catalyst. Other methods of preparation include treatment of chloroacetic acid with hydrobromic acid at elevated temperatures (56), oxidation of ethylene bromide with Aiming nitric acid, hydrolysis of dibromovinyl ether, and air oxidation of bromoacetylene in ethanol. 

Bromohydrins can be prepared direcdy from polyhydric alcohols using hydrobromic acid and acetic acid catalyst, followed by distillation of water and acetic acid (21). Reaction conditions must be carehiUy controlled to avoid production of simple acetate esters (22). The raw product is usually a mixture of the mono-, di-and tribromohydrins. 

Small quantities of pure sodium bromide can be prepared by neutralising solutions of either sodium hydroxide [1310-73-2] or sodium carbonate [497-19-8] usiug hydrobromic acid [10035-10-6] which is free of bromine, followed by evaporation and crystallisation. 

A hexahydrate is also known and may be prepared by the electrolytic reduction of the tetrabromide in hydrobromic acid solution. 

Bismuth tribromide may be prepared by dissolving Bi O in excess concentrated hydrobromic acid. The slurry formed is allowed to dry in air, then gendy heated in a stream of nitrogen to remove water, and finally distilled in a stream of dry nitrogen. Bismuth tribromide is soluble in aqueous solutions of KCl, HCl, KBr, and KI but is decomposed by water to form bismuth oxybromide [7787-57-7] BiOBr. It is soluble in acetone and ether, and practically insoluble in alcohol. It forms complexes with NH and dissolves in hydrobromic acid from which dihydrogen bismuth pentabromide tetrahydrate [66214-38-8] H2BiBr 4H2O, maybe crystallized at —lO C. 

Other Bromides. Alkali and alkaline earth bromides can be prepared by neutralizing a solution of the corresponding hydroxide or carbonate with hydrobromic acid. Alternatively, bromine and a reducing agent such as ammonia are used in the van der Meulen process (13) ... 

Cadmium Bromide. The hydrated bromide is prepared by dissolution of cadmium carbonate, oxide, sulfide, or hydroxide in hydrobromic acid. The white crystalline material is cadmium bromide tetrahydrate [13464-92-1], CdBr2 4H2O, Ai/ 29s —1492.55 kJ/mol (—356.73 kcal/mol) (3)... 

An equivalent amount of hydrobromic acid of greater strength may be used. Acid of lower concentration gives a much lower yield. The preparation of 48 per cent hydrobromic acid is described in Org. Syn. 1, 2. 

Ethylene bromohydrin has been prepared by the reaction between ethylene glycol and hydrobromic acid and phosphorus tribromide. It has also been prepared by the direct addition of hypobromous acid to ethylene, and by the reaction between ethylene and dilute bromine water. With ethylene oxide now available at a reasonable price, the method described is probably the best because of the high yields and the convenience of reaction. 

Pentaerythrityl bromide has been prepared by the action of phosphorus tribromide on pentaerythritol, - and of an acetic acid solution of hydrobromic acid on pentaerythritol tetraacetate. The iodide has been prepared by the action of red phosphorus and hydriodic acid on pentaerythritol and by treating the bromide with sodium iodide in acetone. ... 

It is common practice to refer to the molecular species HX and also the pure (anhydrous) compounds as hydrogen halides, and to call their aqueous solutions hydrohalic acids. Both the anhydrous compounds and their aqueous solutions will be considered in this section. HCl and hydrochloric acid are major industrial chemicals and there is also a substantial production of HF and hydrofluoric acid. HBr and hydrobromic acid are made on a much smaller scale and there seems to be little industrial demand for HI and hydriodic acid. It will be convenient to discuss first the preparation and industrial uses of the compounds and then to consider their molecular and bulk physical properties. The chemical reactivity of the anhydrous compounds and their acidic aqueous solutions will then be reviewed, and the section concludes with a discussion of the anhydrous compounds as nonaqueous solvents. 

The preparation of the less stable isomer (53b) of the oxazolone 53a involves a rather tedious procedure. It has been reported that 53a is rapidly isomerized to 53b in 48% hydrobromic acid saturated with gaseous HBr. In this way four azlactones have been converted into their isomers.It has been established, moreover, that the isomerization is radical-initiated and does not involve a carbonium ion intermediate. The isomerization can be reversed by pyridine. ... 

Amino-5-bromoselenazole is mentioned in a patent without further details. It is stated to be a starting material for pharmaceutical products. In analogy to the corresponding thiazole compounds, it is stated to be prepared by heating 2-aminoselenazole in aqueous hydrobromic acid under reflux and slow addition of an equivalent amount of bromine. 

Cadinene dihydrobromide, C,5H24.2HBr, is obtained by shaking cad-ine dissolved in acetic acid with fuming hydrobromic acid. It forms white needles melting at 124° to 125°, and having a specific rotation — 36 13°. The dihydriodide, C15H24.2HI, prepared in a similar manner, melts at 105° to 106° and has a specific rotation - 48°. 

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