Chlorination and Bromination

Chlorination reactions are also highly exothermic and the use of microflow systems is quite effective for conducting the reaction in a controlled manner. Various chlorination reactions including chlorination of toluene derivative to obtain benzyl chlorides, chlorination of acetic acid to obtain chloroacetic acid, and radical chlorination of alkanes using microflow systems have been reported. 

For example, thermally induced radical chlorination of alkanes can be conducted in a microtube reactor having microheat transfer modules. 

Bromination is also exothermic, and microflow systems serve as an excellent way to conduct these reactions. For example, the aromatic electrophilic substitution reaction of toluene and thiophene with Br2 has been reported in the literature. 

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White and red phosphorus combine directly with chlorine, bromine and iodine, the red allotrope reacting in each case at a slightly higher temperature. The reactions are very vigorous and white phosphorus is spontaneously inflammable in chlorine at room temperature. Both chlorine and bromine first form a trihalide ... 

Phosphorus(III) oxide reacts slowly with oxygen at ordinary temperatures to give the pentoxide, P40,g. The reaction is rapid if the oxide is heated in air. It is oxidised vigorously by chlorine and bromine which form the oxidehalides, POX3. 

Many of the reactions of halogens can be considered as either oxidation or displacement reactions the redox potentials (Table 11.2) give a clear indication of their relative oxidising power in aqueous solution. Fluorine, chlorine and bromine have the ability to displace hydrogen from hydrocarbons, but in addition each halogen is able to displace other elements which are less electronegative than itself. Thus fluorine can displace all the other halogens from both ionic and covalent compounds, for example... 

Another teat, which indicates the reactivity of the halogen atom (chlorine and bromine), is based upon the fact that sodium chloride and sodium bromide are sparingly soluble in pure acetone ... 

The heats of formation of Tt-complexes are small thus, — A//2soc for complexes of benzene and mesitylene with iodine in carbon tetrachloride are 5-5 and i2-o kj mol , respectively. Although substituent effects which increase the rates of electrophilic substitutions also increase the stabilities of the 7r-complexes, these effects are very much weaker in the latter circumstances than in the former the heats of formation just quoted should be compared with the relative rates of chlorination and bromination of benzene and mesitylene (i 3 o6 x 10 and i a-Sq x 10 , respectively, in acetic acid at 25 °C). 

Kinetic data are available for the nitration of a series of p-alkylphenyl trimethylammonium ions over a range of acidities in sulphuric acid. - The following table shows how p-methyl and p-tert-h xty augment the reactivity of the position ortho to them. Comparison with table 9.1 shows how very much more powerfully both the methyl and the tert-butyl group assist substitution into these strongly deactivated cations than they do at the o-positions in toluene and ferf-butylbenzene. Analysis of these results, and comparison with those for chlorination and bromination, shows that even in these highly deactivated cations, as in the nitration of alkylbenzenes ( 9.1.1), the alkyl groups still release electrons in the inductive order. In view of the comparisons just... 

Another method for the hydrogenoiysis of aryl bromides and iodides is to use MeONa[696], The removal of chlorine and bromine from benzene rings is possible with MeOH under basic conditions by use of dippp as a ligand[697]. The reduction is explained by the formation of the phenylpalladium methoxide 812, which undergoes elimination of /i-hydrogen to form benzene, and MeOH is oxidized to formaldehyde. Based on this mechanistic consideration, reaction of alcohols with aryl halides has another application. For example, cyclohex-anol (813) is oxidized smoothly to cyclohexanone with bromobenzene under basic conditions[698]. 

This difference in selectivity between chlorination and bromination of alkanes needs to be kept in mind when one wishes to prepare an alkyl halide from an alkane... 

The reaction of chlorine and bromine with cycloalkenes illustrates an important stereo chemical feature of halogen addition Anti addition is observed the two bromine atoms of Br2 or the two chlorines of CI2 add to opposite faces of the double bond... 

In aqueous solution chlorine and bromine react with alkenes to form vicinal halohy drins, compounds that have a halogen and a hydroxyl group on adjacent carbons... 

Alkynes react with chlorine and bromine to yield tetrahaloalkanes Two molecules of the halogen add to the triple bond... 

Although alkenes typically react with chlorine and bromine by addition at room tern perature and below (Section 6 14) substitution becomes competitive at higher tempera tures especially when the concentration of the halogen is low When substitution does occur It IS highly selective for the allylic position This forms the basis of an industrial preparation of allyl chloride... 

Halogenation (Section 12 5) Chlorination and bromination of arenes are carried out by treatment with the appropriate halogen in the presence of a Lewis acid catalyst Very reactive arenes undergo halogenation in the absence of a catalyst... 

Aryl chlorides and bromides are con veniently prepared by electrophilic aro matic substitution The reaction is lim ited to chlorination and bromination Fluorination is difficult to control lodi nation is too slow to be useful... 

For other elements that occur with major relative abundances of more than one isotope in the natural state, the isotope pattern becomes much more complex. For example, with chlorine and bromine, the presence of these elements is clearly apparent from the isotopes Cl and for chlorine and Br and Br for bromine. Figure 47.2a shows the molecular ion region for the compound chlorodecane. Now, there are new situations in that C, C, C1, and Cl isotopes all have probabilities of occurring together. Thus, there are molecular ion peaks for + Cl, C + Cl, + Cl, and so on. Even so, the isotopic ratio of 3 1 for Cl to Cl is very clear... 

Partial mass spectra showing the isotope patterns in the molecular ion regions for ions containing carbon and (a) only one chlorine atom, (b) only one bromine atom, and (c) one chlorine and one bromine atom. The isotope patterns are quite different from each other. Note how the halogen isotope ratios appear very clearly as 3 1 for chlorine in (a), 1 1 for bromine in (b), and 3 4 1 for chlorine and bromine in (c). If the numbers of halogens were not known, the pattern could be used in a reverse sense to decide their number. 

Chlorine and bromine add vigorously, giving, with proper control, high yields of 1,2-dihaloethyl ethers (224). In the presence of an alcohol, halogens add as hypohaUtes, which give 2-haloacetals (225,226). With methanol and iodine this is used as a method of quantitative analysis, titrating unconsumed iodine with standard thiosulfate solution (227). 

The reaction with fluorine occurs spontaneously and explosively, even in the dark at low temperatures. This hydrogen—fluorine reaction is of interest in rocket propellant systems (99—102) (see Explosives and propellants, propellants). The reactions with chlorine and bromine are radical-chain reactions initiated by heat or radiation (103—105). The hydrogen-iodine reaction can be carried out thermally or catalyticaHy (106). 

Reactions of the Aromatic Ring. The aromatic ring of hydroxybenzaldehydes participates in several typical aromatic electrophilic reactions. Ha.logena.tlon, Chlorination and bromination yield mono- and dihalo derivatives, depending on reaction conditions. Bromination of / -hydroxy-benzaldehyde in chloroform yields 65—75% of the product shown (39). 

Chlorine and Bromine Oxidizing Compounds. The organo chlorine compounds shown in Table 6 share chemistry with inorganic compounds, such as chlorine/77< 2-3 (9-j5y and sodium hypochlorite/7 )< /-j5 2-5 7. The fundamental action of chlorine compounds involves hydrolysis to hypochlorous acid (see Cm ORiNE oxygen acids and salts). 

Iodine can be oxidized to iodate in acid solutions by concentrated nitric acid and, in more dilute solutions, by permanganate, bromates, chlorates, and even chlorine and bromine. 

The iodides of the alkaU metals and those of the heavier alkaline earths are resistant to oxygen on heating, but most others can be roasted to oxide in air and oxygen. The vapors of the most volatile iodides, such as those of aluminum and titanium(II) actually bum in air. The iodides resemble the sulfides in this respect, with the important difference that the iodine is volatilized, not as an oxide, but as the free element, which can be recovered as such. Chlorine and bromine readily displace iodine from the iodides, converting them to the corresponding chlorides and bromides. 

Most nonmetallic elements (except nitrogen, oxygen, chlorine, and bromine) are oxidized to their highest state as acids. Heated with concentrated acid, sometimes ia the presence of a catalyst, sulfur, phosphoms, arsenic, and iodine form sulfuric, orthophosphoric, orthoarsenic, and iodic acid, respectively. SiHcon and carbon react to produce their dioxides. 

The cycle accounts for - 30 and 20—30% of the halogen-controUed loss for chlorine and bromine, respectively. 

Confirmation of the destmetion of ozone by chlorine and bromine from halofluorocarbons has led to international efforts to reduce emissions of ozone-destroying CPCs and Halons into the atmosphere. The 1987 Montreal Protocol on Substances That Deplete the Ozone Layer (150) (and its 1990 and 1992 revisions) calls for an end to the production of Halons in 1994 and CPCs, carbon tetrachloride, and methylchloroform byjanuary 1, 1996. In 1993, worldwide production of CPCs was reduced to 50% of 1986 levels of 1.13 x 10 and decreases in growth rates of CPC-11 and CPC-12 have been observed (151). 

The reactions are general for chlorine and bromine. Iodine does not react to form pentavalent phosphoms compounds. Fluorides are best formed with less active fluorinating agents. 

Nitrogen and sodium do not react at any temperature under ordinary circumstances, but are reported to form the nitride or azide under the influence of an electric discharge (14,35). Sodium siHcide, NaSi, has been synthesized from the elements (36,37). When heated together, sodium and phosphoms form sodium phosphide, but in the presence of air with ignition sodium phosphate is formed. Sulfur, selenium, and tellurium form the sulfide, selenide, and teUuride, respectively. In vapor phase, sodium forms haHdes with all halogens (14). At room temperature, chlorine and bromine react rapidly with thin films of sodium (38), whereas fluorine and sodium ignite. Molten sodium ignites in chlorine and bums to sodium chloride (see Sodium COMPOUNDS, SODIUM HALIDES). 

Sanitizers. Spa and hot-tub sanitation is dominated by chlorine- and bromine-based disinfectants. Public spas and tubs usually employ automatic feeders, eg, CI2 gas feeders, to maintain a disinfectant residual. Private or residential spas and tubs can use automatic chemical feeding or generating devices, or they can be sanitized manually with granular or liquid products. The most widely used products for private spa and tub sanitation are sodium dichloroisocyanurate and bromochlorodimethylhydantoin. Granular products are normally added before and after use, whereas solids, eg, stick-bromine, are placed in skimmers or feeders. Bromine generating systems can also be used and are based on oxidation of bromide ions (added to the water as sodium bromide) by peroxymonosulfate, chloroisocyanurates, hypochlorites, or ozone to generate the disinfectant HOBr. 

Chlorine and bromine add to benzene in the absence of oxygen and presence of light to yield hexachloro- [27154-44-5] and hexabromocyclohexane [30105-41-0] CgHgBr. Technical benzene hexachloride is produced by either batch or continuous methods at 15—25°C in glass reactors. Five stereoisomers are produced in the reaction and these are separated by fractional crystallization. The gamma isomer (BHC), which composes 12—14% of the reaction product, was formerly used as an insecticide. Benzene hexachloride [608-73-17, C HgCl, is converted into hexachlorobenzene [118-74-17, C Clg, upon reaction with ferric chloride in chlorobenzene solution. 

The costs of building and maintaining a bromine plant are high because of the corrosiveness of brine solutions which contain chlorine and bromine and require special materials of constmction. The principal operating expenses are for pumping, steam, environmental costs, energy, and chlorine. The plants are very capital intensive. 

Since hypohalous acid is a much more effective disinfectant than hypohaUte, pH affects the disinfection efficiency. The fraction of hypohalous acid for aqueous chlorine and bromine is HOX/(HOX + XO ) = 1 — + where the pfC s of HOCl and HOBr at 25°C are 7.54 (2) and 8.70,... 

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