Hydrogen, reaction with bromine iodine

Undoubtedly, the best method for the production of pure anhydrous lanthanide trihalides involves direct reaction of the elements. However, suitable reaction vessels, of molybdenum, tungsten, or tantalum, have to be employed silica containers result in oxohalides (27). Trichlorides have been produced by reacting metal with chlorine (28), methyl chloride (28), or hydrogen chloride (28-31). Of the tribromides, only that of scandium has been prepared by direct reaction with bromine (32). The triiodides have been prepared by reacting the metal with iodine (27, 29, 31, 33-41) or with ammonium iodide (42). 

Syntheses of 5-halogenotetrazoles from metallic derivatives have met with mixed fortunes. Lithiation of 1-methyltetrazole followed by reaction at -60°C with bromine, iodine, or cyanogen bromide gave the 5-bromo and 5-iodo compounds in 36-55% yields (71CJC2139). 1,2-Disubstituted tetrazolium tetraphenylborates were lithiated in the 5-position, but subsequent reaction with chlorine or bromine failed to trap the anion. Instead, oxidation produced a radical cation, which abstracted a hydrogen atom from the solvent [91 AG(E)1162]. 

The next more complicated system which yields laboratory flames is that of hydrogen-halogens. In practice, flames can be obtained from hydrogen mixed with bromine, chlorine, or fluorine. No hydrogen-iodine flame has been observed. These systems are identical in their chemistry and the failure to realize a hydrogen-iodine flame is connected with the dominance of the direct molecular reaction over the atom-catalyzed reaction which characterizes the other flames. This occurs because of the low reactivity of the iodine atom. 

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). 

At 225—275°C, bromination of the vapor yields bromochloromethanes CCl Br, CCl2Br2, and CClBr. Chloroform reacts with aluminum bromide to form bromoform, CHBr. Chloroform cannot be direcdy fluorinated with elementary flourine fluoroform, CHF, is produced from chloroform by reaction with hydrogen fluoride in the presence of a metallic fluoride catalyst (8). It is also a coproduct of monochlorodifluoromethane from the HF—CHCl reaction over antimony chlorofluoride. Iodine gives a characteristic purple solution in chloroform but does not react even at the boiling point. Iodoform, CHI, may be produced from chloroform by reaction with ethyl iodide in the presence of aluminum chloride however, this is not the route normally used for its preparation. 

Additions of halogen fluorides to the more electrophilic perfluonnated olefins generally require different conditions Reactions of iodine fluoride, generated in situ from iodine and iodine pentafluoride [62 102 103, /05] or iodine, hydrogen fluoride, and parapeiiodic aud [104], with fluormated olefins (equations 8-10) are especially well studied because the perfluoroalkyl iodide products are useful precursors of surfactants and other fluorochemicals Somewhat higher temperatures are required compared with reactions with hydrocarbon olefins Additions of bromine fluoride, from bromine and bromine trifluonde, to perfluonnated olefins are also known [lOti]... 

This enzyme [EC 1.11.1.10], also called chloride peroxidase, catalyzes the reaction of hydrogen peroxide with two RH and two Cl to produce two R—Cl and two water molecules. A heme group is one of the cofactors. This enzyme can also catalyze bromination and iodin-ation, but not fluorination. 

A similar reaction occurs with bromine at first copper(ll) bromide is formed which at red heat converts to copper(I) bromide. Fluorination yields CuF2. Heating the metal with iodine and concentrated hydriodic acid produces copper(l) iodide. When copper is heated in an atmosphere of hydrogen sulfide and hydrogen, the product is copper(I) sulfide, CU2S. 

The reaction is explosive with fluorine and occurs under all conditions. With chlorine and bromine reaction occurs rapidly when exposed to light, undergoing a photochemical chain reaction. With iodine, the reaction is very slow, even at elevated temperatures. Hydrogen is a strong reducing agent. At high temperatures, the gas reduces many metal oxides to lower oxides or metals ... 

Electrophilic addition to 9-vinylcarbazole occurs in the Markovnikov sense, thus hydrogen chloride,hydrogen bromide,chlorine, and bromine in carbon tetrachloride, and iodine chloride in pyridine are recorded as adding with initial electrophilic attack at the methylene. Mercuric acetate in methanol gave 9-(2-acetoxymercuri-l-methoxyethyl)carbazole. Although 9-vinylcarbazole gave an iodohydrin, comparable reaction with methanolic sodium hypochlorite led to 9-(2-chlorovinyl)carbazole. Catalytic reduction of the latter produced 9-(2-chloroethyl)carbazole. Tri-phenyltin hydride gave 96. ... 

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