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Physical Data: aqueous solution forms a constant boiling azeotrope containing ca. 48% HBr at 760 mmHg; d = 1.49 g cm-3. Anhydrous gas, d 2.71 g L-1; mp -86.9 °C; bp -66.8 °C.
Solubility: very sol water and protic solvents.
Form Supplied in: as anhydrous gas in cylinders; as aqueous solutions of various concentrations; widely available in all forms.
Analysis of Reagent Purity: titration.
Handling, Storage, and Precautions: hydrogen bromide is a corrosive, colorless, nonflammable gas which forms a white cloud when exposed to air; as concentrated solutions, hydrobromic acid is a colorless to light yellow corrosive liquid which fumes when exposed to air; the acid can cause severe skin burns, damage to the respiratory and digestive tract, and/or visual damage; repeated exposure may cause dermatitis and photosensitization; the gas and solutions of hydrobromic acid should be handled with adequate ventilation and proper skin and eye protection. Use in a fume hood.
Hydrogen Bromide is completely ionized in all but the most concentrated aqueous solutions, making it a strong Lewis acid. However, the expense of hydrobromic acid relative to Hydrochloric Acid and other mineral acids, as well as the greater nucleophilicity of bromide, has limited its use as an acid catalyst.
Addition to Single Bonds in Three-Membered Rings.
Addition to Single Bonds in Four-, Five-, and Six-Membered Rings.
Addition to Carbon-Carbon Multiple Bonds.
Thiols react with paraformaldehyde and hydrobromic acid to yield bromomethyl thioethers (see bromomethylation above). Benzenesulfonamides, benzenesulfonohydrazides, and benzenesulfinic acids can all react with hydrobromic acid to yield disulfides or sulfenyl bromides, depending upon the reaction conditions (eqs 36-38). Hydrogen bromide appears to be better than hydrogen chloride for the preparation of disulfides from benzenesulfonamides, but less satisfactory than hydrogen chloride for the conversion of benzenesulfonohydrazides to disulfides.38 Sulfoxides are converted into bromosulfonium bromides or sulfides (eq 39).39 Chloro(trifluoromethyl)sulfine reacts with anhydrous hydrogen bromide to produce 1-bromo-1-chloro-2,2,2-trifluoroethylsulfenyl bromide in high yield (eq 40).40 Additional information is included under the section on the in situ generation of Bromine (see below).
Organoselenium, Organogermanium, and Organorhenium Chemistry.
In Situ Generation of Bromine.
Dimethyl Sulfoxide reacts with hydrobromic acid at about 80 °C to produce dimethyl sulfide, water, and bromine (eq 54). The DMSO/HBr reagent has been used to oxidize 1,3-diketones to 1,2,3-triketones, acetophenones to phenylglyoxals, benzylamines to imines, and 4,5-dihydropyridazin-3(2H)-ones to pyridazin-3(2H)-ones.56 The combination is also effective in converting stilbenes, 1,2-dibromo-1,2-diarylethanes, and 2-bromo-1,2-diarylethanols to benzils.57 It is possible to use a catalytic amount of hydrogen bromide in some of these reactions.
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