Amine vanadates

A reaction which is very comparable to that which takes place with hydroxylamine consists in the formation of amine vanadates by the action of vanadium pentoxide on the alkylamines. The simplest of those that have been prepared are 8... 

For direct precipitation of vanadium from the salt-roast leach Hquor, acidulation to ca pH 1 without the addition of ammonia salts yields an impure vanadic acid when ammonium salts are added, ammonium polyvanadate precipitates. The impure vanadic acid ordinarily is redissolved in sodium carbonate solution, and ammonium metavanadate precipitates upon addition of ammonium salts. Fusion of the directly precipitated ammonium salts can yield high purity V20 for the chemical industry. Amine solvent extraction is sometimes used to recover 1—3 g/L of residual V20 from the directly precipitated tail Hquors. 

Aqueous solutions of vanadous chloride (vanadium dichloride) are prepared by reduction of vanadium pentoxide with amalgamated zinc in hydrochloric acid [213], Reductions are carried out in solution in tetrahydrofuran at room temperature or under reflux. Vanadiiun dichloride reduces a-halo ketones to ketones [214], a-diketones to acyloins [215], quinones to hydroquinones [215], sulfoxides to sulfides [216] and azides to amines [217] (Procedure 40, p. 215). 

Lithium aluminum hydride reduced )J-azidoethylbenzene to j8-aminoethyl-benzene in 89% yield [600], The azido group was also reduced with aluminum amalgam (yields 71-86%) [149], with titanium trichloride (yields 54-83%) [601], with vanadous chloride (yields 70-95%) [217] Procedure 40, p. 215), with hydrogen sulfide (yield 90%) [247], with sodium hydrosulfite (yield 90%) [259], with hydrogen bromide in acetic acid (yields 84-97%) [232], and with 1,3-propanedithiol (yields 84-100%) [602]. Unsaturated azides were reduced to unsaturated amines with aluminum amalgam [149] and with 1,3-propane-dithiol [602]. 

A I M aqueous solution of vanadous chloride (10 ml) is added to a stirred solution of I g of an aryl azide in 10 ml of tetrahydrofuran. After the evolution of nitrogen has subsided the mixture is poured into 30 ml of aqueous ammonia the resultant slurry is mixed with benzene, filtered with suction, and the filter cake is washed with benzene. The benzene layer of the filtrate is separated, the aqueous layer is extracted with benzene, the combined benzene solutions are dried, the solvent is evaporated and the residue is distilled to give 70-95% of the amine. 

Vanadium usually is recovered from its ores by one of two processes, (1) leaching raw mineral with hot dilute sulfuric acid, and (2) roasting ore with common salt to convert vanadium into water soluble sodium vanadates. In the sulfuric acid leaching process, vanadium is extracted from acid leach liquors by solvent extraction with an aliphatic amine or an alkyl phosphoric acid in kerosene. The organic solvent extract then is treated with an aqueous solution of ammonia in the presence of ammonium chloride to convert vanadium into ammonium metavanadate. Alternatively, the organic extract is treated with dilute sulfuric acid or an aqueous solution of soda ash under controlled conditions of pH. Vanadium is precipitated from this solution as a red cake of sodium polyvanadate. 

An indirect vanadometric method of assay for camphor was developed. The method involves the formation of 2, -dinitrophenylhydrazone of camphor. The nitro groups in the hydrazone are then reduced to amines by treatment with vanadium sulfate (VSOl ) and the excess of the reagent is back titrated with sodium dichromate (NapCrpO-y). The entire procedure is carried out in a modified separatory funnel into which standard vanadate, 6tJ and zinc amalgam... 

Vanadate reacts only very weakly with aliphatic amines such as ethylamine. As a consequence, reactions with aliphatic amines have not been extensively studied, but the information available suggests the reactions are analogous to those of alcohols. Additionally, there have been numerous studies of multidentate ligands where amino functionality is a critical component of vanadium ligation (Section 4.4). 

Unlike ethylene glycol, a-hydroxycarboxylic acids, and p-mercaptoethanol, ligands such as ethanolamine, ethylenediamine, amino acids, and 2-aminoethanethiol do not form V2L2 complexes with vanadate [46], However, weakly formed products of VL stoichiometry (—546 ppm, —556 ppm) are observed with a number of a-amino acids [47], Because the amine functionality in amino acids is not suitable for formation of the cyclic [VN]2 core expected for a dimer, then one or the other of these VL compounds may correspond to the monomeric precursor to such a dimeric product. Certainly, with the a-hydroxycarboxylic acids, the monomeric complex can be a major component in solution. Similar VL complexes have not been reported for the amino alcohols. Perusal of the available reports suggests that the amine derivatives were studied under conditions where the nitrogen functionality was protonated, so the results may be somewhat misleading. 

This book does not follow a chronological sequence but rather builds up in a hierarchy of complexity. Some basic principles of 51V NMR spectroscopy are discussed this is followed by a description of the self-condensation reactions of vanadate itself. The reactions with simple monodentate ligands are then described, and this proceeds to more complicated systems such as diols, -hydroxy acids, amino acids, peptides, and so on. Aspects of this sequence are later revisited but with interest now directed toward the influence of ligand electronic properties on coordination and reactivity. The influences of ligands, particularly those of hydrogen peroxide and hydroxyl amine, on heteroligand reactivity are compared and contrasted. There is a brief discussion of the vanadium-dependent haloperoxidases and model systems. There is also some discussion of vanadium in the environment and of some technological applications. Because vanadium pollution is inextricably linked to vanadium(V) chemistry, some discussion of vanadium as a pollutant is provided. This book provides only a very brief discussion of vanadium oxidation states other than V(V) and also does not discuss vanadium redox activity, except in a peripheral manner where required. It does, however, briefly cover the catalytic reactions of peroxovanadates and haloperoxidases model compounds. 

Aromatic amines, such as pyridine and imidazole, have been found to form weak complexes with vanadate.100 104 2 7 The fact that no vanadium(V) complexes with aliphatic amines, in the absence of stabilizing ligands, have been reported supports the expectation that such complexes will have low stability in aqueous solution. In the presence of ancillary ligands, both aliphatic119 and aromatic73 amines form stable ternary complexes in solution. 

Numerous studies on the interactions of peptides and peptide-like ligands with vanadate have been reported.68,382 384>446>447 Some of these ligands coordinate through the carboxylate, the amine functionalities and the deprotonated amide nitrogen of the peptide bond,238,23 382 447 448 and some examples were described above in the section on polydentate ligands with two oxygen donor atoms. 

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