Hydrogen iodide iodination

Hydrogen iodide iodinates triaLkylsilanes in good yield in boiling carbon tetrachloride with no aluminum haUde present (116). This can perhaps be explained on the basis that some free iodine is always present in equiUbrium with hydrogen iodide. 

M. Miyamoto, M. Sawamoto, and T. Higashimura, Living polymerization of isobutyl vinyl ether with hydrogen iodide/iodine initiating system. Macromolecules 1984, 77(3), 265-268. 

Hydrogen Iodide-Iodine (Uving/ControUed Cationic Polymerization)... 

These values indicate a rapid fall in thermal stability of the halide from fluorine to iodine, and hydrogen iodide is an endothermic compound. If we now examine the various enthalpy changes involved. we find the following values (in kJ) ... 

Iodine and hydrogen react reversibly to give hydrogen iodide ... 

This equilibrium is established when hydrogen iodide is heated, hydrogen-iodine bonds being broken. 

Hydrogen iodide is prepared in a similar way to hydrogen bromide, by the action of water on a mixture of iodine and violet phosphorus. TTie hydrogen iodide evolved may be collected by downward delivery or may be condensed (b.p. 238 K) it reacts with mercury and so cannot be collected over the latter. 

An aqueous solution of hydrogen iodide, up to 50% strength, may be prepared by passing hydrogen sulphide (or sulphur dioxide) into a suspension of iodine in water ... 

Hence hydrogen iodide cannot be produced by the reaction of sulphuric acid with an iodide. Hydriodic acid is slowly oxidised by air (more rapidly in light) liberating iodine ... 

Hydrogen iodide. This gas may be conveniently prepared by allowing a solution of two parts of iodine in one part of hydriodic acid, sp. gr. 1 7 (for preparation, see Section 11,49,2), to drop on to excess of red phosphorus. The evolution of hydrogen iodide takes place in the cold when the evolution of gas slackens considerably, the mixture should be gently warmed. 

Comparable results are not obtained with the less reactive iodine, because the hydrogen iodide formed tends to reduce the iodo compound and a condition of equilibrium is produced ... 

This preparation illustrates the direct iodination of a primary aromatic amine by iodine the sodium bicarbonate removes the hydrogen iodide as formed ... 

For 2-amino-4- m-nitrophenyl) seienazole, the yield is particularly high. This has been explained by the oxidizing effect of the nitro group, which liberates iodine from the hydrogen iodide eliminated in the condensation reaction. 

Iodine reacts with hydrocarbons to form iodine compounds, but compared to the other halogens, the equiUbria are unfavorable because the displacement step with the iodine atom is endothermic, requiring 4066.3 J (971.9 cal) for methane and 799.9 J (191.2 cal) for toluene. Hydrogen iodide can be used to reduce an alkah iodide to hydrocarbon plus molecular iodine. 

Complete iodination of organic compounds can be achieved by preventing the formation of free hydrogen iodide through the addition of an oxidizing agent, neutralization of the HI with a base, or combination using mercuric salts. 

Hydroiodic acid, the colorless solution formed when hydrogen iodide gas dissolves in water, is prepared by reaction of iodine with hydrogen sulfide or hydrazine or by an electrolytic method. Typically commercial hydroiodic acid contains 40—55% HI. Hydroiodic acid is used in the preparation of iodides and many organic iodo compounds. 

Catalysts. Iodine and its compounds ate very active catalysts for many reactions (133). The principal use is in the production of synthetic mbber via Ziegler-Natta catalysts systems. Also, iodine and certain iodides, eg, titanium tetraiodide [7720-83-4], are employed for producing stereospecific polymers, such as polybutadiene mbber (134) about 75% of the iodine consumed in catalysts is assumed to be used for polybutadiene and polyisoprene polymeri2a tion (66) (see RUBBER CHEMICALS). Hydrogen iodide is used as a catalyst in the manufacture of acetic acid from methanol (66). A 99% yield as acetic acid has been reported. In the heat stabiH2ation of nylon suitable for tire cordage, iodine is used in a system involving copper acetate or borate, and potassium iodide (66) (see Tire cords). 

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