Iodides s. a. Halides

Inversion s. Carboxy-inversion and under Configuration lodacetone as hydrogen iodide scavenger 21, 966 Iodides (s. a. Halides, Replacement)... 

Figure 7.4 Thermodynamic data needed in evaluation of the enthalpy of formation of MX(s). (a) Lattice enthalpy of sodium halides (b) lattice enthalpy of alkali iodides (c) electron gain and dissociation enthalpies of halides (d) ionization and atomization enthalpies of alkali metals.

In addition to the sensors dealt with in Section 3.3.1.1, which could equally have been included in this Section as they use consumable immobilized reagents and regenerable fluorophores, Frei et al. developed a sensor for HPLC determinations based on the solid-state detection cell depicted in Fig. 3.38.B, where they immobilized 1-bromonaphthalene for measuring phosphorescence quenchers. Experiments demonstrated the sensor s usefulness for determining nitrate with a detection limit of ca. 10" M and an RSD of 4% for an analyte concentration of M. However, the scope of application of this sensor to chromatographically separated anions is rather narrow owing to the low sensitivity of the quenched phosphorescence detection for iodide and other halides [268]. 

The ineffectiveness of hydrogen iodide as a catalyst promoter can now be rationalized, since HI reacts with Ru3(CO)12 or Ru(CO)s to produce Ru(CO)4I2 or [Ru(CO)3I3] , Ru(II) halide complexes which are stable under H2/CO and inactive as catalysts (191). These oxidized halide complexes can... 

When iodine is dissolved in hydriodic acid or a soln. of a metallic iodide, there is much evidence of chemical combination, with the formation of a periodide. A. Baudrimont objected to the polyiodide hypothesis of the increased solubility of iodine in soln. of potassium iodide, because he found that an extraction with carbon disulphide removed the iodine from the soln. but S. M. Jorgensen showed that this solvent failed to remove the iodine from an alcoholic soln. of potassium iodide and iodine in the proportion KI I2, and an alcoholic soln. of potassium iodide decolorized a soln. of iodine in carbon disulphide. The hypothesis seemed more probable when, in 1877, G. S. Johnson isolated cubic crystals of a substance with the empirical formula KI3 by the slow evaporation of an aqueous-alcoholic soln. of iodine and potassium iodide over sulphuric acid. There is also evidence of the formation of analogous compounds with the other halides. The perhalides or poly halides—usually polyiodides—are products of the additive combination of the metal halides, or the halides of other radicles with the halogen, so. that the positive acidic radicle consists of several halogen atoms. The polyiodides have been investigated more than the other polyhalides. The additive products have often a definite physical form, and definite physical properties. J. J. Berzelius appears to have made the first polyiodide—which he called ammonium bin-iodide A. Geuther called these compounds poly-iodides and S. M. Jorgensen, super-iodides. They have been classified 1 as... 

The following qualitative observations on the action of liquid ammonia on organic compounds are mainly by E. C. Franklin and C. A. Kraus, those in brackets are by G. Gore. Aliphatic compounds.—Halides methyl iodide, m. chloroform, reacts, and m. bromoform, m. iodoform, v.s., ethyl bromide and iodide, s. ethylene bromide, s. ethylidene chloride, m. isobutyl bromide, s. amyl bromide, s.s. tribromomethane, v.s. nitrotriohloromethane, m. perehloroethane (n.s.) perchloroethylene (m.) dichloroacetylene (s.). Alcohols methyl, m. ethyl, m. propyl, m. normal butyl,... 

In a parallel study, it was found that chelating chiral diamines 208 or 209 are well suited as ligands to promote Kumada-type couplings of primary and secondary alkyl halides 202 with aryl Grignard reagents 203 (entry 4) [281]. This reaction was applicable to alkyl bromides and alkyl iodides, while alkyl chlorides gave only low yields. Acetal and ester functions are tolerated. A notable feature is the stereoretentive arylation of fra s-a-bromo acetals with excellent diastereo-selectivity. The involvement of radicals is supported by the stereoconvergent formation of cxo-phenvI norbornane from both endo- or exo-bromonorbomane (cf. Part 1, Fig. 9) and radical 5-exo cyclizations (see below). 

A peculiai- case of phosphoryl radical addition to difluoroalkenes involves the reaction of trialkyl phosphites with l-bromo-2-iodo-l,l,2,2-tetfafluoroethane under ultraviolet irradiation (254 nm). Surprisingly, the corresponding 2-iodo-l,l,2,2-tetrafluoroethylphosphonates are formed in 42 8% yields with no detectable amount of the bromo derivative (Scheme 3.39). The proposed mechanism involves a halide-induced dealkylation of the trialkyl phosphite radical cation followed by addition of the product phosphoryl radical to tetrafluoroethene (generated by halide anion elimination) and iodide radical abstraction from the starting haloalkane. s... 

Three methods have been described for three halogens, two based on fluorescence and one on absorption. In the first [87], the fluorescence of rubrene in polystyrene is quenched by traces of iodine. This method is nonselective and the optode is also sensitive to oxygen. In another sensor, naphthoflavone in solution in a material of the silicone or PVC type serves as a sensitive layer for free halides [88]. The absorption technique uses a fiber with a liquid CS2 core [89] to detect 10 ng of iodide using a S m long capillary cell with sample circulation. The Hber itself constitutes the active optode (total reflection in the liquid core). A comparison of optodes based on dynamic quenching of absorbed Rhodamine 6G by iodide was reported [90]. Three solid supports for immobilization were used PTFE tape, XAD resin beads and crushed XAD-4 resin. The limits of detection are 0.18-0.30 and 1.1 mM respectively. Some anions (eg. Cl , Br , CN ) interfere at the 1-M level. 

Another very interesting point in connection with the reactions of the alkyl chlorides, bromides and iodides, is the fact that the iodides show a tendency to give a larger yield of olefin than do the chlorides in the presence of alkali [A. Lieben and A. Rossi, Lieb. Ann. 158, 164 (1871)]. This is the opposite to what would have been supposed from the behavior of the halides in the presence of catalysts such as aluminium chloride. Furthermore, the chlorides yield ether more readily than do the corresponding bromides or iodides [M. Wildermann, Z. phys. Chem. 8, 661 (1891) and S. Brussow, Ibid. 34, 129 (1900)]. 

In a comparative study, Wilkinson s catalyst (84) was employed in intermolecular ary-lation reactions of methyl acrylate (1) and styrene (2). Rhodium catalyst 84 was reported to be more efficient than a cobalt precursor. Note, however, that the reproducibility of these results was recently questioned [58]. Simple aryl iodides were efficiently converted at 110°C (Scheme 10.30), but crr/zo-substituted aryl iodides required a higher reaction temperature of 150 °C. Aryl bromides and chlorides, as well as aliphatic halides, could not be converted using rhodium catalyst 84 [47]. 

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