Iodide kinetics

Clewell RA, Merrill EA, Yu KO, Mahle DA, Sterner TR, Mattie DR, Robinson PJ, Fisher JW, Gearhart JM. 2003. Predicting fetal perchlorate dose and inhibition of iodide kinetics during gestation a physiologically-based pharmacokinetic analysis of perchlorate and iodide kinetics in the rat. Toxicol Sci 73 235-255. 

Acetic acid + Methanol Hydrogen iodide Kinetic and reactor modeling Ronnback et al. (1997)... 

Figure 1. Parameters of iodide kinetics of the thyroid gletnd in two subjects with an daily iodine Intake of 100 Xg (left) and 20 jlg (right).

G. Ponchon, C. Beckers and M. De Visscher, Iodide kinetic studies in newborns and infants, J. Clin. Endocrinol. Metab., 26 1392 (1966). 

The Landolt reaction (iodate + reductant) is prototypical of an autocatalytic clock reaction. During the induction period, the absence of the feedback species (Irere iodide ion, assumed to have virtually zero initial concentration and fomred from the reactant iodate only via very slow initiation steps) causes the reaction mixture to become kinetically frozen . There is reaction, but the intemiediate species evolve on concentration scales many orders of magnitude less than those of the reactant. The induction period depends on the initial concentrations of the major reactants in a maimer predicted by integrating the overall rate cubic autocatalytic rate law, given in section A3.14.1.1. 

Nucleophilic reactivity of the sulfur atom has received most attention. When neutral or very acidic medium is used, the nucleophilic reactivity occurs through the exocyclic sulfur atom. Kinetic studies (110) measure this nucleophilicity- towards methyl iodide for various 3-methyl-A-4-thiazoline-2-thiones. Rate constants are 200 times greater for these compounds than for the isomeric 2-(methylthio)thiazole. Thus 3-(2-pyridyl)-A-4-thiazoline-2-thione reacts at sulfur with methyl iodide (111). Methyl substitution on the ring doubles the rate constant. This high reactivity at sulfur means that, even when an amino (112, 113) or imino group (114) occupies the 5-position of the ring, alkylation takes place on sulfiu. For the same reason, 2-acetonyi derivatives are sometimes observed as by-products in the heterocyclization reaction of dithiocarba-mates with a-haloketones (115, 116). 

Curiously enough, bulky substituents on nitrogen increase this reactivity towards methyl iodide (119). This has been related to a steric decompression of the thiocarbonyl group in the transition state. Furthermore, knowledge of the ratio of conformers in the starting 4-alkyl-3-i-Pr-A-4-thiazoline-2-thiones and in the resulting 4-alkyl-3-i-Pr-2-methylthiothi-azolium iodides combined with a Winstein-Holness treatment of the kinetic data indicates that in the transition state, the thiocarbonyl bond is approximately 65% along the reaction coordinate from the initial state... 

The kinetics of the reaction between 2-methylthiothiazoles and methyl iodide show that the nucleophilic center is the ring nitrogen. The 2-methylthio group decreases the nucleophilicity of the this atom (269). 

The first kinetic results in the area were obtained by studying the quatemization of 4-alkyl-, 5-alkyT, and 2-alkylthiazoles with methyl iodide (253-255). A deeper and more exhaustive study of this reaction has been carried out recently with more elaborate substrates (152). 

TABLE in-52. KINETIC DATA FOR THE OUATERNI-ZATION OF 2- AND 4-ALKYLTHIAZOLES WITH METHYL IODIDE IN NITROBENZENE AT 25°C (256)... 

Noncnzymc-Catalyzcd Reactions The variable-time method has also been used to determine the concentration of nonenzymatic catalysts. Because a trace amount of catalyst can substantially enhance a reaction s rate, a kinetic determination of a catalyst s concentration is capable of providing an excellent detection limit. One of the most commonly used reactions is the reduction of H2O2 by reducing agents, such as thiosulfate, iodide, and hydroquinone. These reactions are catalyzed by trace levels of selected metal ions. Eor example the reduction of H2O2 by U... 

The equihbrium constant of this reaction is 5.4 x 10 at 25°C, ie, iodine hydrolyzes to a much smaller extent than do the other halogens (49). The species concentrations are highly pH dependent at pH = 5, about 99% is present as elemental at pH = 7, the and HIO species are present in almost equal concentrations and at pH = 8, only 12% is present as and 88% as HIO. The dissociation constant for HIO is ca 2.3 x 10 and the pH has tittle effect on the lO ion formation. At higher pH values, the HIO converts to iodate ion. This latter species has been shown to possess no disinfection activity. An aqueous solution containing iodate, iodide, and a free iodine or triodide ion has a pH of about 7. A thorough discussion of the kinetics of iodine hydrolysis is available (49). 

Before coupling, excess nitrous acid must be destroyed. Nitrite can react with coupling components to form nitroso compounds causiag deHterious effects on the final dyestuff. The presence of nitrite can be detected by 4,4 -diamiQO-diphenyHnethane-2,2 -sulfone [10215-25-5] (Green reagent) or starch—iodide. Removal of nitrite is achieved by addition of sulfamic acid or urea [57-13-6], however, sulfamic acid [5329-14-6] has been more effective ia kinetic studies of nine nitrous acid scavangers (18). 

Alkylation of pyrazinones and quinoxalinones may be carried out under a variety of conditions and it is usually observed that while O-alkylation may occur under conditions of kinetic control, to yield the corresponding alkoxypyrazines or alkoxyquinoxalines, under thermodynamic control the A-alkylated products are formed. Alkylation using trialkyl-oxonium fluoroborate results in exclusive O-alkylation, and silylation under a variety of conditions (75MI21400) yields specifically the O-silylated products. Alkylation with methyl iodide or dimethyl sulfate invariably leads to A-methylation. 

Table 8-S. Kinetic Data on the Menschutkin Reaction of Triethylamine and Ethyl Iodide at 25°C...

Anotheranalogy between the enolate anions derived from a,)3-unsatura ted ketones and the corresponding enamines is encountered in their alkylation reactions (57), which proceed by the kinetically controlled attack at the a-carbon atom. For instance, Stork and Birnbaum (51) found that the alkylation of the morpholine enamine of /J -octalone-2 (117) with methyl iodide gave the C-1 methylated derivative (118). 

Thiopyrones and selenopyrones can be alkylated more readily than pyrones. Thus 2,6-dimethyl-4/f-pyran-4-thionc (4,6-dimethyl-4-thiopyrone) (23, Y = S) reacts rapidly with methyl iodide yielding a 4-methylmercaptopyrylium iodide (24, Y = S, R = Me, X = I). Many alkylating agents were investigated by King et al. The kinetics of the reaction between 2,6-dimethyl-4-thiopyrone and substituted phenacyl bromides was found to be described by the Hammett... 

Mukherjee studied the gas phase equilibria and the kinetics of the possible chemical reactions in the pack-chromising of iron by the iodide process. One conclusion was that iodine-etching of the iron preceded chromis-ing also, not unexpectedly, the initial rate of chromising was controlled by transport of chromium iodide. Neiri and Vandenbulcke calculated, for the Al-Ni-Cr-Fe system, the partial pressures of chlorides and mixed chlorides in equilibrium with various alloys and phases, and so developed for pack aluminising a model of gaseous transport, solid-state transport, and equilibria at interfaces. 

Shimidzu etal.111 studied the catalytic activity of poly (4(5)-vinylimidazole-co-acrylic add) 60 (PVIm AA) in hydrolyses of 3-acetoxy-N-trimethylanilinium iodide 61 (ANTI) and p-nitrophenylacetate 44 (PNPA). The hydrolyses of ANTI followed the Michaelis-Menten-type kinetics, and that of PNPA followed the second-order kinetics. Substrate-binding with the copolymer was strongest at an imidazole content of 30 mol%. The authors concluded that the carboxylic acid moiety not... 

The exceptionally large ionic conductivities characteristic of certain double iodides [1182] make them particularly attractive systems for kinetic and mechanistic studies of solid—solid interaction. Countercurrent migration of Ag+ and Hg2+ in the product phase has been identified as the rate-controlling process for [1209]... 

A positive iodinating species was postulated to account for the kinetics and isotope effect observed in the iodination of some amines by iodine in aqueous potassium iodide (in some cases in the presence of acetate, lactate, or phosphate ion). The isotope effects (kH/kD values in parenthesis) for these compounds studied were 2,4,6-trideutero-m-dimethylaminobenzenesulphonate ion, 25 °C (1.0) 2,4,6-trideutero-m-dimethyIbenzoate ion, 30 °C (1.4) 2,4,6-trideutero-dimethylaniline, 30 °C, lactate (3.0) 2,4,6-trideuteromethylaniline, 25 °C, acetate (3.2) 2,4,6-trideuteroaniline, 25 °C (3.5), phosphate (4.0) 2,4,6-trideutero-metanilate ion, 35 °C (2.0) 2,4,6-trideutero-m-aminobenzoate ion, 30 °C (4.8), phosphate (3.0) 2,6-dideutero-l-dimethylaminobenzene-4-sulphonate ion, 25 °C, phosphate (1.0) 4-deutero-l-dimethylaminobenzene-3-sulphonate ion, 25 °C, phosphate (1.0). The kinetics of these reactions was given by... 

Grimison and Ridd225 also suggested the preformation of a positive iodinating species as a means of explaining the results obtained in the iodination by iodine in aqueous potassium iodide, of imidazole at 25 °C. The kinetics of this reaction follow equation (121)... 

Additional kinetic evidence supporting molecular iodine as an iodinating species is sparse. Li325 found that the iodination of tyrosine in acetate buffers at 25 °C showed the mixed inverse dependence on iodide ion concentration noted above, so that part of the reaction appeared to involve the molecular species. Subsequently, Doak and Corwin326 found that the kinetics of the iodination of (N-Me)-4-carboethoxy-2,5-dimethyl- and (N-Me)-5-carboethoxy-2,4-dimethyl-pyrroles in phosphate buffers in aqueous dioxane at 26.5 °C obeyed equation (162), viz. 

The kinetics of iodination of azulene with iodine in dilute aqueous sodium iodide at 25 °C followed the equation... 

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