Hydrolysis of bromine

To calculate the equilibrium constant for the hydrolysis of bromine in water from conductance measurements. 

The conductance of solutions of bromine in water at 25 C have been measured bj Grinnell Jones and BaeckstrSm (J. Amer. Chem. Soc. 1934, 56, 1520). Their results at low bromine concentrations are given in table 1, where b is the stoicheiometric concentration of bromine, and c is the specific conductance of the solution. 

The following values of molar conductances at 25 °C will be used 

The ionic concentrations in the above measurements are so low that variations of A with concentration may be disregarded. 

Our object is to determine the equilibrium constant K of the process Bra + HjO HOBr + H+ t- Br  

---

Hypobromous acid HOBr results from the hydrolysis of bromine with H2O and exists only in aqueous solution. The compound finds limited use as a germicide and in water treatment also it can be used as an oxidizing or brominating agent in the production of certain organic compounds. Although hypobromous acid is low in bromine content, concentrated hypobromite solutions can be formed by adding bromine to cooled solutions of alkalis. 

The generation of HOBr can be effected by the hydrolysis of bromine gas (Br2) or liquid bromine chloride (BrCl), as in the reaction below. This type of HOBr generation requires the use of large gas cylinders and associated equipment, similar to using chlorine. It is only appropriate for large industrial process cooling systems. 

Read the discussion of the hydrolysis of bromine in the preceding preparation. About one-third of the chlorine in chlorine water is hydrolyzed. The bleaching power of chlorine is due directly to the oxidizing action of the hypochlorous acid produced by the hydrolysis. The formation of chlorate in this preparation is also a result of the oxidizing action of hypochlorous add. 

The more halogenated a compound, the less likely it is to hydrolyze and the slower the reaction kinetics. Hydrolysis of brominated compounds is typically faster than that of chlorinated compounds [26]. 

The reaction above is reversible, for if the colorless basic solution is acidified, the elementary halogen is regenerated. Hypohalites will not survive in warm solution, but undergo further self-oxidation or dis-mutation. Typically, the OBr ion is converted to BrOi" and Br it follows, therefore, that basic hydrolysis of bromine results ultimately in bromide and bromate ions in about a 5 1 ratio ... 

Attempts by Smith and ToUens " to oxidize n-fructose with bromine by the method of Clowes and Tollens were unsuccessful a double compound of D-fructose and calcium bromide was obtained. No yield of this product was given. The reaction mixture of D-fructose, calcium carbonate, water and bromine was shaken until all the bromine had dissolved, after which the double compound was separated from the concentrated solution. The calcium bromide was formed from the interaction of calcium carbonate with hydrogen bromide in the reaction solution. The hydrogen bromide could be formed in two ways by the hydrolysis of bromine in water (reaction 1, page 134) or by the reduction of bromine during the oxidation of D-fructose. The former is the more probable explanation, but a blank run without the ketose was not attempted. 

Other alkali-metal chlorates are produced by analogous technology while sodium and potassium bromate are produced electrolytically starting both from bromide ion and bromine solutions. The production of bromate is, however, a very small-scale process and the cells have not been optimized to any extent for example while cells with lead dioxide and platinized titanium have been described, some plants still use solid platinum electrodes The mechanism of bromate formation is identical to that described for chlorate by reactions (5.10)—(5.13) the kinetics are, however, different. The hydrolysis of bromine is slower than chlorine but the disproportionation step is much faster (by a factor of 100) and it is therefore advisable to use a more alkaline electrolyte, about pH 11. 

Write equations representing the hydrolysis of bromine fluoride, trifluoride, and pentafluoride. 

The reaction is applicable to the preparation of amines from amides of aliphatic aromatic, aryl-aliphatic and heterocyclic acids. A further example is given in Section IV,170 in connexion with the preparation of anthranilic acid from phthal-imide. It may be mentioned that for aliphatic monoamides containing more than eight carbon atoms aqueous alkaline hypohalite gives poor yields of the amines. Good results are obtained by treatment of the amide (C > 8) in methanol with sodium methoxide and bromine, followed by hydrolysis of the resulting N-alkyl methyl carbamate ... 

Mono-substitution products of primary amines cannot easUy be prepared by direct action of the appropriate reagent for example, bromination of aniline yields largely the 2 4 6-tribomo derivative and nitration results in much oxidation. If, however, the amino group is protected as in acetanilide, smooth substitution occurs. Thus with bromine, />-bromoacetanilide is the main product the small quantity of the ortlio isomeride simultaneously formed can be easily eliminated by crystallisation. Hydrolysis of p-bromoacetanilide gives/ -bromoaniline ... 

Bromination of quinaldine (I) (Section V,2) with bromine in glacial acetic acid in the presence of anhydrous sodium acetate aflFords dilute sulphuric acid gives quinaltiinic acid (III). 

A new approach we found is based on the initial bromination of methane to methyl bromide, which can be effected with good selectivity, although still in relatively low yields. Methyl bromide is easily separated from exeess methane, whieh is readily recyeled. Hydrolysis of methyl bromide to methyl alcohol and its dehydration to dimethyl ether are readily achieved. Importantly, HBr formed as by produet ean be oxidatively reeycled into bromine, making the overall proeess cat-alytie in bromine. 

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. 

Bromine ttifluoride is commercially available at a minimum purity of 98% (108). Free Br2 is maintained at less than 2%. Other minor impurities are HF and BrF. Free Br2 content estimates are based on color, with material containing less than 0.5% Br2 having a straw color, and ca 2% Br2 an amber-red color. Fluoride content can be obtained by controlled hydrolysis of a sample and standard analysis for fluorine content. Bromine ttifluoride is too high boiling and reactive for gas chromatographic analysis. It is shipped as a Hquid in steel cylinders in quantities of 91 kg or less. The cylinders are fitted with either a valve or plug to faciUtate insertion of a dip tube. Bromine ttifluoride is classified as an oxidizer and poison by DOT. 

Excess of bromine converts each methylpteridine compound into the dibromomethyl derivative which on hydrolysis gives good yields of the corresponding aldehyde. An interesting variation of the reaction conditions was found in the treatment of the C- methylpteridines with POBra, which leads to the same mono- and di-bromomethyl derivatives. 6-Methylpterin reacts with more difficulty and with an excess of bromine in hydrobromic acid forms the... 

The bromination of />-acetotoluide, followed by hydrolysis of the resulting bromoacetotoluidei is the only practical method which has been used for making 3-bromo-4-aminotoluene, The present process is a modification of the method described by Feitler.2... 

It should be noted that although BrCl is mainly a brominating agent that is eompetitive with bromine, its ehemieal reaetivity makes its action similar to that of ehlorine (that is, disinfection, oxidation, and a bleaching agent). BrCl hydrolyzes exelusively to hypobromous aeid, and if any hydrobromie aeid (HBr) is formed by hydrolysis of the dissociated bromine, it quickly oxidizes to hydrobromous acid via hypochlorous acid. 

Liebbrandt have prepared arecaidine by bromination of methyl jV-methylpiperidine-3-carboxyIate, scission of hydrogen bromide from the resulting bromo-compound (VI) and hydrolysis of the resulting arecoline, but Preobrachenski and Fischer were unable to confirm this observation. 

Acetoxyandrost-5-en-17-one (59) is converted into the ethylene ketal (60) by treatment with ethylene glycol, triethylorthoformate and p-toluenesulfonic acid. The ketal is brominated with pyridinium bromide perbromide in THF and then treated with sodium iodide to remove bromine from the 5 and 6 positions. This gives the 16a-bromo compound (61) which is hydrolyzed in methanol to the free alcohol (62). Dehydrobromination is effected with potassium Fbutoxide in DMSO to give the -compound (63). Acid catalyzed hydrolysis of the ketal in aqueous acetone gives the title compound (64). ... 

The sensitivity of this ketol side chain to acid or base requires careful control of the hydrolysis of the epoxyacetate. Alternatively, the enol acetate can be brominated and the resulting bromo ketone converted to the 21-acetoxy-20-ketone ... 

Kurath described the conversion of 3a,17y5-diacetoxy-5)9-androstan-12-one (partial structure 78) to diketone (79) by bromination of (78) and hydrolysis of the C-11 epimeric bromo ketones... 

This method of bromination has been employed in the selective bromination (777) of the ketone (167). While direct bromination results in bromination not only in the position alpha to the ketone but also in the aromatic ring, bromination of the enamine (168) and subsequent hydrolysis gave only the monobrominated product (169). 

The interconversion with di- and tri-bromothiophenes is very selective. Thus 2,3,5-tribromothiophene gives exclusively 3,5-dibromo-2-thienyllithium, the hydrolysis of which affords a very convenient synthesis of 2,4-dibromothiophene. Similarly, 2,4- and 2,3-di-bromothiophene give interconversion selectively with the a-bromine. 

Direct bromination readily yields the 6-bromo derivative (111), just as with uracil. Analogous chlorination and iodination requires the presence of alkalies and even then proceeds in low yield. The 6-chloro derivative (113) was also obtained by partial hydrolysis of the postulated 3,5,6-trichloro-l,2,4-triazine (e.g.. Section II,B,6). The 6-bromo derivative (5-bromo-6-azauracil) served as the starting substance for several other derivatives. It was converted to the amino derivative (114) by ammonium acetate which, by means of sodium nitrite in hydrochloric acid, yielded a mixture of 6-chloro and 6-hydroxy derivatives. A modified Schiemann reaction was not suitable for preparing the 6-fluoro derivative. The 6-hydroxy derivative (115) (an isomer of cyanuric acid and the most acidic substance of this group, pKa — 2.95) was more conveniently prepared by alkaline hydrolysis of the 6-amino derivative. Further the bromo derivative was reacted with ethanolamine to prepare the 6-(2-hydroxyethyl) derivative however, this could not be converted to the corresponding 2-chloroethyl derivative. Similarly, the dimethylamino, morpholino, and hydrazino derivatives were prepared from the 6-bromo com-pound. ... 

In the presence of catalytic amounts of iodine, bromination of A-ethyl-phenote llurazine with bromine results in A-ethyl-2,8,10,10-tetrabromophenotellurazine 53. Structure 53 was proved by its synthesis by bromination of A-ethyl-2,8-dibromophenotellurazine and also by alkaline hydrolysis of 53 into 4,4-dibromo-A-ethyldiphenylamine. 

---