Separation of the Halides

The alkali halide salts are those applied. Detection can be imdertaken with a pH-indicator or with a fluorescence indicator. Huoride is detected with the zirconium-alizarin lake. The anions appear as light yellow spots on a blue background when the pH indicator (below) is used. The migration sequence is  

Standard samples 1 p.1 of IM solutions of NaF, NaCl, ElBr and KI. Solvent Acetone-n-butanol-conc. NH40H-distilled water (66 + 20 + 10 + 6). 

Detection a) 0.1 % solution of bromocresol purple in ethanol, brought just to the colour change with a few drops of NH4OH. 

Gagliardi et al. [9] have separated halides and pseudohalides on MN silica gel S-HR (Firm 83). The same order of migration distances of the ions were observed in all the solvents used  

K salts were applied in all cases except for and which were applied as their Na salts. 

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The amine group in primary amines can be replaced by halogen by warming the benzoyl derivative with phosphorus pentachloride or phosphorus pentabromide. Oftentimes, the separation of the halide from the benzonitrile, which is also formed, is troublesome. The process has been applied mostly to high-moIecuIar-weight amines obtained by the Hofmann degradation of acid amides or by reduction of nitriles." Diamines lead to dihalogen derivatives." If N-benzoyl piperidines are treated, substituted pentamethylene halides are formed. An example is the synthesis of pentamethylene bromide by the action of phosphorus pentabromide on N-benzoyl piperidine (72%). ... 

The only olefinic acid isolated from the carbonation of the Grignard reagent prepared from the isomeric mixture of crotyl and methylvinylcar-binyl bromides is 2-methyl-3-butenoic acid (70%). Separation of the halides is unnecessary because of this fortunate allylic isomerization. 

In support of this mechanism it has been found that the rate of decomposition of substituted benzamides (and presumably the ease of rearrangement) is more rapid when electron-releasing groups arc introduced into the aromatic ring.74 Thus the separation of the halide ion must be the controlling step for the reaction. When there is an asymmetric carbon atom attached to the carbonyl group, configuration is retained and virtually no racemization occurs.75 (+)a-Methyl plienyl-... 

Methods for the separation of the halide ions are described in the Chapter on chlorine. 

A quantitative separation of the halide ions F , Cr, Br , and 1 has been obtained by means of a column of Sephadex G-15 gel/ Thin-layer voltammetric data for Pt electrodes indicate that these ions form chemisorbed layers which withstand rinsing with typical aqueous electrolytes/ The chemisorbed species are much less reactive towards electrochemical oxidation than the aqueous ions. 

Mix together 1 0 g. of pure p-naphthol and the theoretical quantity of 50 per cent, potassium hydroxide solution, add 0-5 g. of the halide, followed by sufficient rectified spirit to produce a clear solution. For alkyl chlorides, the addition of a little potassium iodide is recommended. Heat the mixture under reflux for 15 minutes, and dissolve any potassium halide by the addition of a few drops of water. The p-naphthyl ether usually crystallises out on cooling if it does not, dilute the solution with 10 per cent, sodium hydroxide solution untU precipitation occurs. Dissolve the p-naphthyl ether in the minimum volume of hot alcohol and add the calculated quantity of picric acid dissolved in hot alcohol. The picrate separates out on cooling. Recrystallise it from rectified spirit. 

Organosulfur Halides. When sulfur is directly linked only to an organic radical and to a halogen atom, the radical name is attached to the word sulfur and the name(s) and number of the halide(s) are stated as a separate word. Alternatively, the name can be formed from R—SOH, a sulfenic acid whose radical prefix is sulfenyl-. For example, CH3CH2—S — Br would be named either ethylsulfur monobromide or ethanesulfenyl bromide. When another principal group is present, a composite prefix is formed from the number and substitutive name(s) of the halogen atoms in front of the syllable thio. For example, BrS—COOH is (bromothio)formic acid. 

Attempts by Kao and others to enhance transparency by chemically removing impurities from glass met with little success the level of purity required was indeed comparable with that needed in silicon for integrated circuits. In the event, the required purification was achieved in the same way in which semiconductor-grade silicon is now manufactured, by going through the gas phase (silicon tetrachloride), which can be separated from the halides of impurity species because of dilTerences in vapour pressures. This breakthrough was achieved by R.D. Maurer and his... 

The charged species were in all cases found to concentrate at the surface of the liquid under vacuum conditions. Little surface separation of the anions and cations was observed. For the [PFg] and [BFJ ions, the cation ring was found to prefer a perpendicular orientation to the surface, with the nitrogen atoms closest to the surface. An increase in the alkyl chain length caused the cation to rotate so that the alkyl chain moved into the bulk liquid, away from the surface, forcing the methyl group closer to the surface. For halide ionic liquids, the data were less clear and the cation could be fitted to a number of orientations. 

Friedel-Crafts acylation reactions usually involve the interaction of an aromatic compound with an acyl halide or anhydride in the presence of a catalyst, to form a carbon-carbon bond [74, 75]. As the product of an acylation reaction is less reactive than its starting material, monoacylation usually occurs. The catalyst in the reaction is not a true catalyst, as it is often (but not always) required in stoichiometric quantities. For Friedel-Crafts acylation reactions in chloroaluminate(III) ionic liquids or molten salts, the ketone product of an acylation reaction forms a strong complex with the ionic liquid, and separation of the product from the ionic liquid can be extremely difficult. The products are usually isolated by quenching the ionic liquid in water. Current research is moving towards finding genuine catalysts for this reaction, some of which are described in this section. 

Theory. The anion exchange resin, originally in the chloride form, is converted into the nitrate form by washing with sodium nitrate solution. A concentrated solution of the chloride and bromide mixture is introduced at the top of the column. The halide ions exchange rapidly with the nitrate ions in the resin, forming a band at the top of the column. Chloride ion is more rapidly eluted from this band than bromide ion by sodium nitrate solution, so that a separation is possible. The progress of elution of the halides is followed by titrating fractions of the effluents with standard silver nitrate solution. 

The solubilities of the ionic halides are determined by a variety of factors, especially the lattice enthalpy and enthalpy of hydration. There is a delicate balance between the two factors, with the lattice enthalpy usually being the determining one. Lattice enthalpies decrease from chloride to iodide, so water molecules can more readily separate the ions in the latter. Less ionic halides, such as the silver halides, generally have a much lower solubility, and the trend in solubility is the reverse of the more ionic halides. For the less ionic halides, the covalent character of the bond allows the ion pairs to persist in water. The ions are not easily hydrated, making them less soluble. The polarizability of the halide ions and the covalency of their bonding increases down the group. 

After separation of excess amalgam a solution of MXj is added. Reaction is rapid and the desired product can be separated from the Na halide or NaCN produced. If the separation of the amalgam is incomplete it is possible for Hg to be incorporated into the product (see 8.3.3.4). To avoid this, other methods of preparing carbonyl anions can be used, such as reaction with NaBH4, Na-K and other reducing agents ", or phase-transfer methods. ... 

Ferrocene behaves in many respects like an aromatic electron-rich organic compound which is activated toward electrophilic reactions.In Friedel-Crafts type acylation of aromatic compounds with acyl halides, ferrocene is lO times more reactive than benzene and gives yields over 80%. However, ferrocene is different from benzene in respect to reactivity and yields in the Friedel-Crafts alkylation with alkyl halides or olefins. The yields of ferrocene alkylation are often very low. and the separations of the polysubstituted byproducts are tedious. 

Notes on the preparation of secondary alkylarylamines. The preparation of -propyl-, ijopropyl- and -butyl-anilines can be conveniently carried out by heating the alkyl bromide with an excess (2-5-4mols) of aniline for 6-12 hours. The tendency for the alkyl halide to yield the corresponding tertiary amine is thus repressed and the product consists almost entirely of the secondary amine and the excess of primary amine combined with the hydrogen bromide liberated in the reaction. The separation of the primary and secondary amines is easily accomplished by the addition of an excess of per cent, zinc chloride solution aniline and its homologues form sparingly soluble additive compounds of the type B ZnCl whereas the alkylanilines do not react with sine chloride in the presence of water. The excess of primary amine can be readily recovered by decomposing the zincichloride with sodium hydroxide solution followed by steam distillation or solvent extraction. The yield of secondary amine is about 70 per cent, of the theoretical. 

The separation of the sodium derivative of the phenol maybeavoided byheating the enol and all l halide in the presence of potassium carbonate and acetone, for example ... 

In the case of molten salts, the functional electrolytes are generally oxides or halides. As examples of the use of oxides, mention may be made of the electrowinning processes for aluminum, tantalum, molybdenum, tungsten, and some of the rare earth metals. The appropriate oxides, dissolved in halide melts, act as the sources of the respective metals intended to be deposited cathodically. Halides are used as functional electrolytes for almost all other metals. In principle, all halides can be used, but in practice only fluorides and chlorides are used. Bromides and iodides are thermally unstable and are relatively expensive. Fluorides are ideally suited because of their stability and low volatility, their drawbacks pertain to the difficulty in obtaining them in forms free from oxygenated ions, and to their poor solubility in water. It is a truism that aqueous solubility makes the post-electrolysis separation of the electrodeposit from the electrolyte easy because the electrolyte can be leached away. The drawback associated with fluorides due to their poor solubility can, to a large extent, be overcome by using double fluorides instead of simple fluorides. Chlorides are widely used in electrodeposition because they are readily available in a pure form and... 

An interesting method for obtaining a pure sample of terbium is to place one of the terbium halides (fluorine or chlorine) in a crucible and heat it in a helium atmosphere. The two elements will separate as a result of different densities. When the sample cools, the terbium can be separated from the halide. 

Reactions under quaternisation of exocyclic R2P-substituents have so far been applied exclusively to benzophospholide derivatives. The most convenient approach involves treatment of the substrate with an appropriate alkyl halide [27, 31, 35] or acrylic acid (Scheme 10) [27]. The quaternisation products formed are in general isolable without complication if pure starting materials have been employed as is normally the case for zwitterionic substrates. Anionic benzophospholides such as 29 and 30 are, in contrast, normally only accessible as crude product mixtures whose quaternisation affords mixtures of several phosphonium salts. Separation of the desired product may in these cases require lengthy work-up procedures and result in substantially lower yields [31]. 

In the method proposed by van Staden for the determination of three halides, these are separated in a short colunm packed with a strongly basic ion-exchange resin (Dowex i-X8) that is placed in an FI manifold. A laboratory-made tubular silver/silver halide ion-selective electrode is used as a potentiometric sensor. Van Staden compared the response capabilities of the halide-selective electrodes to a wide concentration range (20-5000 pg/mL) of individual and mixed halide solutions in the presence and absence of the ion-exchange column. By careful selection of appropriate concentrations of the potassixun nitrate carrier/eluent stream to satisfy the requirements of both the ion-exchange column and the halide-selective electrode, he succeeded in separating and determining chloride, bromide and iodide in mixed halide solutions with a detection limit of 5 /xg/mL [130]. 

The acyl halide (0.10 mol, freshly distilled) is added dropwise over 15 min to a solution (sometimes two-layer system) of 0.10 mol of alkynylzinc halide (p. 36) in THF and hexane, maintained between 5 and 10 C. After the addition, die cooling bath is removed and the temperature allowed to rise. Stilting is continued for 45 min at 20"C, then the mixture is cooled to -10 C and a solution of 20 g of NH4Cl in 200 ml of water is added with vigorous stirring After separation of the layers, three extractions with Et20 are earned out. The combined organic solutions are washed four times with a saturated aqueous solution of... 

In the alkylation reactions of the chiral 3-acyl-2-oxazolidinones, deprotonation to the lithium or sodium enolate is by treatment with lithium diisopropylamide or lithium or sodium hexamethyldisilazanide in tetrahydrofuran at low temperature (usually — 78 °C). The haloalka-ne, usually in excess, is then added to the enolate solution at low temperature (usually — 78 °C) for the sodium enolates and at higher temperatures (between —78 and 0CC) for the lithium enolates. When small, less sterically demanding halides, such as iodomethane, are used the sodium enolate is usually preferred 2 24 and in these cases up to five equivalents2,6- 24,26,27 of the halide are necessary in order to obtain good yields of the alkylation products. Conventional extractive workup provides the crude product as a diastereomeric mixture (d.r. usually > 90 10) which is relatively easy to separate by silica gel chromatography and/or by recrystallization (for crystalline products). Thus, it is possible to obtain one diastereomer in very high diastereomeric purity. 

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