Hydroiodic acid, preparation iodide

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. 

The aHphatic iodine derivatives are usually prepared by reaction of an alcohol with hydroiodic acid or phosphoms trHodide by reaction of iodine, an alcohol, and red phosphoms addition of iodine monochloride, monobromide, or iodine to an olefin replacement reaction by heating the chlorine or bromine compound with an alkaH iodide ia a suitable solvent and the reaction of triphenyl phosphite with methyl iodide and an alcohol. The aromatic iodine derivatives are prepared by reacting iodine and the aromatic system with oxidising agents such as nitric acid, filming sulfuric acid, or mercuric oxide. 

Methylene iodide [75-11-6], CH2I2, also known as diio dome thane, mol wt 267.87, 94.76% I, mp 6.0°C, and bp 181°C, is a very heavy colorless Hquid. It has a density of 3.325 g/mL at 20°C and a refractive index of 1.7538 at 4°C. It darkens in contact with air, moisture, and light. Its solubiHty in water is 1.42 g/100 g H2O at 20°C it is soluble in alcohol, chloroform, ben2ene, and ether. Methylene iodide is prepared by reaction of sodium arsenite and iodoform with sodium hydroxide reaction of iodine, sodium ethoxide, and hydroiodic acid on iodoform the oxidation of iodoacetic acid with potassium persulfate and by reaction of potassium iodide and methylene chloride (124,125). Diiodoform is used for determining the density and refractive index of minerals. It is also used as a starting material in the manufacture of x-ray contrast media and other synthetic pharmaceuticals (qv). 

Lithium Iodide. Lithium iodide [10377-51 -2/, Lil, is the most difficult lithium halide to prepare and has few appHcations. Aqueous solutions of the salt can be prepared by carehil neutralization of hydroiodic acid with lithium carbonate or lithium hydroxide. Concentration of the aqueous solution leads successively to the trihydrate [7790-22-9] dihydrate [17023-25-5] and monohydrate [17023-24 ] which melt congmendy at 75, 79, and 130°C, respectively. The anhydrous salt can be obtained by carehil removal of water under vacuum, but because of the strong tendency to oxidize and eliminate iodine which occurs on heating the salt ia air, it is often prepared from reactions of lithium metal or lithium hydride with iodine ia organic solvents. The salt is extremely soluble ia water (62.6 wt % at 25°C) (59) and the solutions have extremely low vapor pressures (60). Lithium iodide is used as an electrolyte ia selected lithium battery appHcations, where it is formed in situ from reaction of lithium metal with iodine. It can also be a component of low melting molten salts and as a catalyst ia aldol condensations. 

Aluminum iodide [7884-23-8] AIL, is a crystalline soHd with a melting poiat of 191°C. The presence of free iodine ia the anhydrous form causes the platelets to be yellow or brown. The specific gravity of this soHd is 3.98 at 25°C. Aluminum iodide hexahydrate [10090-53-6] AIL -6H20, and aluminum iodide pentadecahydrate [65016-30-0], AIL -15H20, are precipitated from aqueous solution. They may be prepared by the reaction of hydroiodic acid [10034-85-2], HI, with aluminum or aluminum hydroxide. 

Other Reactions. Primary amyl alcohols can be halogenated to the corresponding chlorides by reaction with hydrogen chloride in hexamethylphosphoramide (87). Neopentyl chloride [753-89-9] is formed without contamination by rearrangement products. A convenient method for preparing / f/-amyl bromide and iodide involves reaction of / f/-amyl alcohol with hydrobromic or hydroiodic acid in the presence of Li or Ca haUde (88). The metal haUdes increase the yields (85 —95%) and product purity. 

Bismuth ttiiodide may be prepared by beating stoichiometric quantities of the elements in a sealed tube. It undergoes considerable decomposition at 500°C and is almost completely decomposed at 700°C. However, it may be sublimed without decomposition at 3.3 kPa (25 mm Hg). Bismuth ttiiodide is essentially insoluble in cold water and is decomposed by hot water. It is soluble in Hquid ammonia forming a red triammine complex, absolute alcohol (3.5 g/100 g), benzene, toluene, and xylene. It dissolves in hydroiodic acid solutions from which hydrogen tetraiodobismuthate(Ill) [66214-37-7] HBil 4H2O, may be crystallized, and it dissolves in potassium iodide solutions to yield the red compound, potassium tetraiodobismuthate(Ill) [39775-75-2] KBil. Compounds of the type tripotassium bismuth hexaiodide [66214-36-6] K Bil, are also known. 

Prepare zinc bromide and iodide in the same way, using hydro-bromic and hydroiodic acids instead of hydrochloric acid. 

Metocurine iodide may be prepared by the treatment of fi -tubocurarine with methyl iodide to effeet methylation, followed by reaction with bimolar coneentration of hydroiodic acid to form the offieial eompound. 

Propane-l,2- C, specific activity of about 110 mCi mmol" has been synthesized from doubly labelled acetylene in reaction series shown in equation 12. This synthesis included preparation of doubly labelled acetylene from barium carbonate-according to Cox and Warne, nearly quantitative hydrogenation of acetylene to ethylene, addition of hydroiodic acid to the latter to form iodoethane, preparation of ethylmagnesium iodide followed by carbonation to yield propionic acid and reduction o n-propanol with 70-75% yield. The latter yielded a tosylate which was finally reduced to doubly labelled propane 2 with sodium borohydride, and purified by gas chromatography on alumina or silica. Its specific activity was close to the maximal possible specific activity of acetylene (i.e. 124.9 mCi mmol " ). 

C]Methyl iodide (O Fig. 41.5) has been the most versatile of the secondary precursors (Bolton 2001). It can he prepared hy reduction of [ C] carhon dioxide with lithium aluminum hydride in tetrahydrofiiran or diethyl ether, followed hy reaction with hydroiodic acid (Langstrom and Lundqvist 1976 Crouzel et al. 1987a). 

In 1935 Evans and Smiles obtained 2-methyl-N-(2-nitrophenyl)benzothiazolium iodide (64) when 2-[N-acetyl-N-(2-nitrophenylamino)]benzenethiol (63) was treated with hydroiodic acid in acetone (scheme-18). The same salt was also isolated when 2-[N-acetyl-N-(2-nitrophenylamino)]benzenesulfinic add was reduced with hydriodic and sulfurous adds. The corresponding perchlorate was prepared by treating the benzenethiol with perchloric acid (Evans Smiles 1935). 

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