Iodine complexes, precipitation

Tapioca and maize amylopectins have been sub-fractionated by fractional precipitation from aqueous solution with increasing amounts of methanol,64 71 and potato amylopectin by preferential precipitation on electrodialysis of the iodine complex.72 When these three amylopectins were subjected to chromatography, and eluted with a neutral buffer, all were found to consist of several sub-fractions.70... 

Several methods are available to access glycosyl iodides (Scheme 2.50). Anomeric hemiacetals bearing diverse protecting groups (Bn, Bz, Ac, N3, CMe2) upon treatment with a polymer-bound triphenylphosphine-iodine complex and imidazole can be converted into a-glycosyl iodides [179]. The precipitated by-products,... 

Synthetically useful phosphorane-derived phenyliodonium triflates have been synthesized from the highly electrophilic pyridinium complex 20 <2002TL2359>. Similarly, benziodoxole 21 reacts with trimethylsilyl trifluoro-methanesulfonate (TMSOTf) and pyridine to form a precipitate of complex 22 (Equation 6) <2002TL5735>. The first example of a pentavalent iodine complex with a chelating polydentate nitrogen ligand 24 was obtained from diacetate 23 under similar conditions (Equation 7) <2002TL5735>. 

Solid-state cellulose can also be noncrystalline, sometimes called amorphous. Intermediate situations are also likely to be important but not well characterized. One example, nematic ordered cellulose has been described [230]. In most treatments that produce amorphous cellulose, the whole fiber is severely degraded. For example, decrystallization can be effected by ball milling, which leaves the cellulose as a fine dust. In this case, some crystalline structure can be recreated by placing the sample in a humid environment. Another approach uses phosphoric acid, which can dissolve the cellulose. Precipitation by dilution with water results in a material with very little crystallinity. There is some chance that the chain may adopt a different shape (a collapsed, sixfold helix) after phosphoric acid treatment. This was concluded because the cellulose stains blue with iodine (see Figure 5.12), similar to the sixfold amylose helix in the starch-iodine complex. 

Cesium and ammonium hexachloro complexes precipitate when the component halides are reacted in thionyl chloride-iodine monochloride mixtures. 

When starch is fractionated into its two components, usually by precipitating the amylose from solution by means of an organic solvent (such as an alcohol), a third type of structure is found this survives drying, and ultimately reverts to the B structure upon rehydration. This structure has been termed the V form, and it yields an x-ray pattern that is distinctly different from the other two types. Essentially the same pattern was observed for the amylose-iodine complex. Bundle and coworkers studied the various V amyloses obtained by complexing with alcohols or iodine, and, on the basis of powder diagrams, suggested unit-cell parameters for both the wet and dry (hydrated and anhydrous) states, as shown in Table I (seep. 422). From these data, Bear had suggested earlier that the "V structure of amylose is helical. (Historically, it is of... 

Figure 9. Fractional precipitation of amyiose-iodine complexes DP 90 and 1800 (1 1). Elution curves of tricarbani-lates in THF from HPLC-GPC. (Amy-lose solution 200 mg DP 90 and 200 mg DP 1800 dissolved in 4 mL DMSO and diluted with water to 40 mL. Iodine solution 0.05M h, 0.76U KI, O./M KCl fractions a-d were obtained by successive addition of 1 mL iodine solution.)...

In case of potato starch it was necessary to dilute the solution (5 mg/ml - 4.0 ml + 80 ml Reagent-I) to avoid the precipitation of starch-iodine-complex. Attempts to avoid precipitation of potato starch-iodine-complex (5 mg/ml) by addition of amylopectin 2%) f sucrose (10-205 ) ethylene glycol (l0-40 ) were not successful. Only sodium dodecyl sulphate helped to keep the potato starch-SDS-lodlne-complex (5 mg/ml) in solution. Hence the influence of SDS concentration (3.5 x 10" - 3.5 x 10" M) on the retention of amylose-SDS-iodine-complex from potato starch was investigated. Under these conditions amylopectin-... 

The formation of solid polyoxyethylene glycol-iodine complexes is the cause of the incompatibility of potassium iodine-iodine solutions and certain glycol ointment bases [86]. A polyoxyethylene glycol 4000-iodine precipitate can be... 

Molecular Property Molecular weight Reduction value Osmotic properties Chem. reactivity Digestibility Ethanol precipit. Iodine complexing... 

The complexes, [Fe(py>4]X2 (X = Br, 1), have been prepared by oxidation of metallic iron with bromine or iodine in methanol. Pyridine is added to the resultant solution and the pyridine complexes precipitated.22 Interaction between metallic zinc or cadmium and an excess of arsenic pentafluoride in liquid sulfur dioxide leads to the formation of solvento-complexes containing two or four SO2 ligands depending on the experimental conditions.23/24 The reactions studied are summarized as follows, Eq.4.4 ... 

Decomposition of most cobalt(III) complexes by boiling with alkali gives a brown precipitate of the hydrated oxide C02O3. aq (p.402). This will quantitatively oxidise iodide to iodine. 

A similar procedure may also be used for the determination of antimony(V), whilst antimony (III) may be determined like arsenic(III) by direct titration with standard iodine solution (Section 10.113), but in the antimony titration it is necessary to include some tartaric acid in the solution this acts as complexing agent and prevents precipitation of antimony as hydroxide or as basic salt in alkaline solution. On the whole, however, the most satisfactory method for determining antimony is by titration with potassium bromate (Section 10.133). 

Discussion. Iodine (or tri-iodide ion Ij" = I2 +1-) is readily generated with 100 per cent efficiency by the oxidation of iodide ion at a platinum anode, and can be used for the coulometric titration of antimony (III). The optimum pH is between 7.5 and 8.5, and a complexing agent (e.g. tartrate ion) must be present to prevent hydrolysis and precipitation of the antimony. In solutions more alkaline than pH of about 8.5, disproportionation of iodine to iodide and iodate(I) (hypoiodite) occurs. The reversible character of the iodine-iodide complex renders equivalence point detection easy by both potentiometric and amperometric techniques for macro titrations, the usual visual detection of the end point with starch is possible. 

The reaction is a sensitive one, but is subject to a number of interferences. The solution must be free from large amounts of lead, thallium (I), copper, tin, arsenic, antimony, gold, silver, platinum, and palladium, and from elements in sufficient quantity to colour the solution, e.g. nickel. Metals giving insoluble iodides must be absent, or present in amounts not yielding a precipitate. Substances which liberate iodine from potassium iodide interfere, for example iron(III) the latter should be reduced with sulphurous acid and the excess of gas boiled off, or by a 30 per cent solution of hypophosphorous acid. Chloride ion reduces the intensity of the bismuth colour. Separation of bismuth from copper can be effected by extraction of the bismuth as dithizonate by treatment in ammoniacal potassium cyanide solution with a 0.1 per cent solution of dithizone in chloroform if lead is present, shaking of the chloroform solution of lead and bismuth dithizonates with a buffer solution of pH 3.4 results in the lead alone passing into the aqueous phase. The bismuth complex is soluble in a pentan-l-ol-ethyl acetate mixture, and this fact can be utilised for the determination in the presence of coloured ions, such as nickel, cobalt, chromium, and uranium. 

Careful observations of the course of iodo-de-diazoniation demonstrate that the detailed pathway of such reactions is still relatively complex. For instance, after adding a solution of KI to a solution of an arenediazonium salt, normally molecular iodine appears to be formed first, followed by a precipitate and evolution of N2. Carey and Millar (1960) isolated the salt ArNJIj- on adding iodide to the diazo-nium salt. Ion pairs (ArNjHlg-), suggested as primary products by Meyer et al. (1979), were identified for diazonium halides (Cl- and Br-) by Israel et al. (1983) as 1 1 complexes on the basis of JOB analyses of visible spectra (Benesi-Hildebrand method). Iodides were, however, not included in that investigation. 

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